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Ministry of Higher Education and Scientific Research
University of Baghdad – College of Science

Department of Chemistry
Synthesis of Lubricant’s Additives
A Thesis
Submitted to the College of Science - University of Baghdad
In Partial Fulfillment of the Requirements for
Degree of Doctor Philosophy in Organic Chemistry
By
Zainab Abdulzahra Khuthair AL-Messri
B.Sc. (Baghdad University 1994)

M.Sc. (AL-Nahrain University 1999)
Supervisors
Prof. Dr. Mohammed R. Ahmad Prof. Dr. Abdul Halim A-K Mohammed
2013 A. D. 1434 A. H.
‫ﻴﻢ‬ ‫ﻲ ِ‬ ‫ﺻﺪق اﻟﻠﱠﻪ اﻟﻌﻠِ‬
‫اﻟﻌﻈ ُ‬
‫َ‬ ‫ﱡ‬ ‫َ ََ ُ َ‬
‫ﻣﻦ ﺳﻮرة اﻟﺸﻌﺮاء‬

Dedicate to:
The light of my life…

My father
with love and respect
&
The real friend and sister…

Israa
with appreciation
Zainab
ACKNOWLEDGEMENTS
I would like to express my gratitude to the many people that helped

in different ways towards the completion of this work. My primary thanks
to my supervisors Prof. Mohammed R. Ahmad and Prof. Abdul Halim
A-K Mohammed, for their support, guidance and discussion of my work.
I also thank Prof. Yousif Ali, who helped me not only with this thesis,
but with acquiring scientific knowledge and skills.
My deep gratitude to Prof. Mousa Almousawi, Prof. Abdul

Jabar Kadir, Prof. Issam M.A. Shakir, Ass. Prof. Basim .I. Al-
Abdali, Prof. M. Shanshal, and Ass. Prof. Mohammed H. Al-Ameri
for their supporting, and encouragement.
Sincere thanks to the Ministry of Higher Education and

Scientific Research for providing free, and full-text access to the
scientific journals according to Iraq Virtual Science Library.
Thanks are offered to the Department of chemistry, College of

Science, University of Baghdad for providing the facilities.
I gratefully acknowledge financial support by the Petroleum R&D

Center /Ministry of Oil. A special thanks to Mr. Salah M. Ali for his
assistance and encouragement.
I am very grateful to Dr. Abdulkareem Mohammed Ali, for

modifying a domestic microwave oven to microwave irradiation reactor.
My special thanks, and gratitude to Prof. Issam M.A. Shakir and
Prof. Nagham S. Turkie , for the (ANOVA) tests.
Thanks are also due to Midland Refineries Company/ Iraq for

providing the base oils and the analyses of oxidation stability, especially
Mr. Ayad A. Mohamad , Mr. Yousif T. Abdulhameed, and the lab
technicians and chemists (Bacil Al-Dabbagh, Mohammed Ahamad,
Basam Al-Qaicy, Mohammed Saaed, Mustafa Al-Bassam and Ahmed
Abdulzahra) who helped in the analysis.
I am very grateful, and appreciate for all the help and support from
Ass. Prof. Suaad M. Al-Majidi.
Sincere thanks to Prof. Intisar Altamemi, Prof. Ahlam M.

Farhan, Prof. Khulood Al-Saadie, Dr. Thanaa Almuamen, and Mrs.
Hanaa J. Hamoudi for their supporting and encouragement.
A special thanks to Dr. Ghadah A. Yiseen, Middle East Technical

university , Turkey and to Dr. Naeema J. Lami, Cardiff University, U.K.,
for NMR analysis. Also, I would like to thank Ms. Muneera, and Mrs.
Haifaa for their kind assistance in Infra red analysis.
Sincere thanks goes to my best friends (Israa, Saba, Nada, Jwan,

Thikra, Hind, Dalia, Huda, Nasreen, Hiba, and Yasmeen), and to my
colleagues (Mr. Ali Muayad, Muntader, Rafid, Ali Saad and Oday) for
their continuous support and help.
Finally, my respect and appreciation to my professor and mother

Prof. Suad M. AL-Aaraji, and to my dear father.
Summary
Overbased detergent additives were synthesized and investigated as
viscosity index improvers, and pour point depressant. New antioxidant
additives containing pyranopyrazole and pyranopyrimidine moieties were
synthesized and evaluated as lubricating oil additives.
A series of overbased magnesium fatty acids (D1-D7) such as

caprylate, caprate, laurate, myristate, palmitate, stearate and oleate, were
synthesized by the reaction of the fatty acids in toluene / ethanol solvent
mixture (9:1vol./vol.) with magnesium oxide and carbon dioxide gas at
60 oC in the presence of ammonia solution. Moreover overbased calcium
palmitate, stearate and oleate (D8-D10), were synthesized by the same
method, using calcium oxide and calcium hydroxide instead of
magnesium oxide.
The prepared detergent additives were characterized and confirmed

by FTIR, and 1HNMR. All these compounds were evaluated by blending
each additive in various concentrations (1-5% wt/wt) with medium
lubricant oil fraction (60 stock) supplied by Iraqi Midland Refineries
Company. The total base number (TBN, mg of KOH/g oil) was
determined. Overbased magnesium palmitate D5, oleate D6, and stearate
D7 detergents gave the higher TBN and efficiency.
The oil blends with 2% of overbased magnesium palmitate and

overbased magnesium stearate detergents were proved to have excellent
oxidation stability compared with the blends of standard antioxidant
supplied by Midland Refineries Company.
I
The efficiency of the prepared overbased magnesium palmitate and
overbased magnesium stearate as viscosity index improvers, were
investigated. It was found that the efficiency of the prepared compound as
viscosity index improvers increases with increasing the concentration of
additives and with increasing the molecular weight of prepared
compounds. The overbased magnesium stearate D7 in 5 wt.%
concentration gave the higher efficiency as viscosity index improvers,
and a good pour point depressant.
Antioxidant additives containing pyranopyrazole and

pyranopyrimidine moieties, were synthesized from 2-(4-
hydroxylbenzylidine) malononitrile (S3), which was obtained from the
reaction of 4-hydroxy benzaldehyde and malononitrile in presence of
pipridine in ethanol under microwave irradiation.
Reaction of S3 with three different types of carbanion compounds

3-methyl-1-phenyl-2-pyrazolin-5-one (S1), 3-methyl -2-pyrazolin-5-one
(S2), 5,5-dimethyl-1,3-cyclohexandion (dimedone) and pyrimidine-
2,4,6(1H,3H,5H)-trione (barbituric acid) under microwave irradiation
gave 6-amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl-1-phenyl-1,4-
dihydropyrano[2,3-c]pyrazole (A1), 6-amino-4-(4-hydroxy phenyl)-5-
cyano-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole (A11), 5-(4-
hydroxyphenyl)-8,8-dimethyl-8,9-dihydro-3H-chromeno-5-cyano-1,4-
dihydropyrano[2,3-c]pyrazole (A۱۷) and 7-amino-5-(4-hydroxyphenyl)-
2,4-dioxo-2,3,4,5-tetrahydro-1H-pyrano[2,3-d]pyrimidine-6-carbonitrile
(A26) respectively.
The compound A1 was reacted with formic acid, formamide and

ammonium thiocyanate under microwave irradiation to prepare 4-(4-
hydroxyphenyl)-3-methyl-1-phenyl-4,6-dihydro-pyrazolo[3',4':5,6]pyrano
II
[2,3-d]pyrimidine-5-one (A2), 4-(4-hydroxyphenyl)-3-methyl-1-phenyl-
4,6-dihydro-pyrazolo[3',4':5,6]pyrano[2,3-d]pyrimidine-5-imine (A3) and
N-[4-(4-hydroxyphenyl)-3-methyl-1-phenyl-7-thioxo-7,8dihydropyrazolo
[3',4':5,6]pyrano[2,3-d]pyrimidine-5-yl]thiourea (A4) respectively.
Moreover the compound (A1) was then reacted with different aromatic
aldehydes which gave the corresponding Schiff’s base derivatives (A5-
A10).
Schiff’s base derivatives (A12-A16) were obtained from the
reaction of the compound A11 with different aromatic aldehydes in the
presence of drops of acetic acid under microwave irradiation.
Compounds (A18-A20) and (A21-A25) were synthesized in a similar
manner that used for preparation of (A2-A4) and (A5-A10) respectively.
Most of the prepared compounds were characterized by FTIR,
1
HNMR, 13CNMR and evaluated as antioxidant additives by blending 1%
of each compound with base oil 60 stock.
The oxidation stability of blends was examined according to

Institute of Petroleum testing method IP 280. Inhibited oil was subjected
to severe oxidation condition in the presence of a soluble iron and copper
catalyst at 120ο C for 164 hours while being subjected to a constant one-
liter/hour flow of oxygen. From this test the volatile acids, the acidity of
the oil and the precipitated sludge were measured and their values were
used to calculate the total oxidation products (TOP).
The oxidation stability study revealed that many of the tested

compounds showed good to moderate antioxidant activities. While, the
derivatives A4, A5, A7, A20, A21, A23, and A26 showed better
oxidation stability than the standard antioxidant supplied by Midland
Refineries Company.
III
List of Contents
Chapter One
1.1 Lubricants 1
1.1.1 Lubricant Properties 2
1.1.1.1 Viscosity 2
1.1.1.2 Viscosity Index 2
1.1.1.3 Density and Gravity 3
1.1.1.4 Pour Point 4
1.1.1.5 Volatility and Flash Point 4
1.1.1.6 Total Base Number 4
1.1.1.7 Oxidation Stability 5
1.1.2 Lubricants chemistry 7
1.1.3 Lubricants production 9
1.1.4 Lubricants Formulation 11
1.2 Additives 13
1.2.1 Detergents 15
1.2.2 Dispersants 15
1.2.3 Antiwar Additives 15
1.2.4 Rust and Corrosion Inhibitors 16
1.2.5 Viscosity Modifiers 16
1.2.6 Pour Point Depressants 16
1.2.7 Foam Inhibitors 16
1.2.8 Oxidation Inhibitors 17
1.3 Overbased detergent 17
1.3.1 Synthesis of Overbased Detergents 18
1.3.2 Overbasing Description 19
IV
1.3.3 Overbased Detergent Structure 19
1.3.4 Overbased Detergent Types 20
1.3.4.2 Phenates 20
1.3.4.3 Carboxylate and Salicylates 21
1.4 Antioxidants 22
1.4.1 Oxidation Mechanism 24
1.4.1.1 Initiation of the Radical Chain Reaction 24
1.4.1.2 Propagation of the radical chain reaction 25
1.4.1.3 Chain branching 25
1.4.1.3 Chain branching 26
1.4.1.4 Termination of the radical chain reaction 26
1.4.2 Oxidation Inhibition 27
1.4.2.1 Radical Scavengers 27
1.4.2.1.1 Phenols 27
1.4.2.1.2 Amines 28
1.4.2.2 Peroxide Decomposers 30
1.4.2.3 Metal deactivators 31
1.5 Pyrazole 32
1.6 Pyranopyrazoles 33
1.7 Chromene 38
1.8 2-Amino-3-cycano-4-aryl-7,7-dimethyl-5,6,7,8-tetrahydro 40
chromene
1.9 Aim of the work 44
Chapter Two
2.1 Materials 45
2.1.1 Chemicals 45
V
2.1.2 Base Oil 46
2.2 Instrumentation 47
2.3 Test methods 49
2.3.1 Thin-layer chromatography (TLC) 49
2.3.2 Total base number (TBN) 49
2.3.3 Oxidation stability 49
2.3.4 Kinematic Viscosity 50
2.3.5 Viscosity Index (VI) 51
2.4. Experimental Methods 51
2.4.1 Synthesis of Overbased Magnesium Fatty Acid and Calcium 51
Fatty Acid Detergents (D1-D10)
2.4.2 Synthesis of the Starting Compounds for Antioxidants 54
Preparation
2.4.2.1 Synthesis of 3-methyl-1-phenyl-2-pyrazolin-5-one (S1) 54
2.4.2.2 Synthesis of 3-methyl -2-pyrazolin-5-one (S2) 54
2.4.2.3 Synthesis of 2-(4-hydroxylbenzylidine)malononitrile (S3) 55
2.4.3 Synthesis of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl- 56
1-phenyl-1,4-dihydropyrano[2,3-c]pyrazole (A1)
2.4.4 Synthesis of 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-4,6- 57
dihydropyrazolo[3', 4':5,6]pyrano[2,3-d]pyrimidine-5-one (A2)
2.4.5 Synthesis of 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-4,6- 57
dihydropyrazolo[3', 4':5,6]pyrano[2,3-d]pyrimidine-5-imine (A3)
2.4.6 Synthesis of N-[4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-7- 58
thioxo-7,8- dihydropyrazolo [3', 4':5,6] pyrano [2,3-d] pyrimidine-5-
yl] thiourea (A4)
2.4.7 Synthesis of Schiff base derivatives (A5-A10) 59
VI
2.4.8 Synthesis of 6-amino-4-(4-hydroxyphenyl)-3-methyl-2,4- 61
dihydropyrano[2,3-c]pyrazole-5-carbonitrile (A11)
2.4.10 Synthesis of 5-(4-hydroxyphenyl)-8,8-dimethyl-8,9-dihydro- 63
3H-chromeno-5-cyano-1,4-dihydropyrano[2,3-c]pyrazole (A۱۷)
2.4.11 Synthesis of 5-(4-hydroxyphenyl)-8,8-dimethyl-8,9-dihydro- 63
3H-chromeno[2,3-d]pyrimidine-4,6(5H,7H)-dione (A۱۸)
2.4.12 Synthesis of 5-(4-hydroxyphenyl)-4-imino-8,8-dimethyl 64
5,7,8,9-tetrahydro-3H-chromeno[2,3-d]pyrimidin-6(4H)-one (A19)
2.4.13 Synthesis of 1-(5-(4-hydroxyphenyl)-8,8-dimethyl-6-oxo-2- 65
thioxo-2,5,6,7,8,9-hexahydro-1H-chromeno[2,3-d]pyrimidin-4-yl)
thiourea (A20)
2.4.15 Synthesis of 7-amino-5-(4-hydroxyphenyl)-2,4-dioxo-2,3,4,5- 66
tetrahydro-1H-pyrano[2,3-d]pyrimidine-6-carbonitrile (A26)
2.5 Formulation of oil blends 68
Chapter Three
3.1 Overbased Detergents 69
3.1.1 Synthesis of Overbased Magnesium and Calcium Fatty Acid 69
Salts (D1-D10)
3.1.2 Evaluation of Overbased Magnesium Fatty Acid Salts (D1-D7) 85
as Detergents
3.1.3 Analysis of Variance (ANOVA) Tests 89
3.1.4 Evaluation of Overbased Magnesium Fatty Acid Salts (D5 and 93
D7) as Antioxidant
3.1.5 Evaluation of Overbased Magnesium Fatty Acid Salts (D5 and 95
VII
D7) as Viscosity Index Improvers and Pour Point Dipressant
3.1.6 Evaluation of Overbased Calcium Fatty Acid Salts (D8-D10) as 99
Detergents
3.3 Antioxidants 103
3.3.1 Synthesis of 2-(4-hydroxylbenzylidine)malononitrile (S3) 103
3.3.2 Synthesis of pyranopyrazoles and pyranopyrimidines derived 106
from 3-methyl-1-phenyl-2-pyrazolin-5-one (A1-A10)
3.3.2.1 Synthesis of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-3- 106
methyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazole (A1)
3.3.2.2 Synthesis of 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-4,6- 108
3.3.2.3 Synthesis of 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-4,6- 114
3.3.2.4 Synthesis of N-[4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-7- 119
yl] thiourea (A4)
3.3.2.4 Synthesis of Schiff base derivatives (A5-A10) 123
3.3.3 The comparison between conventional and microwave synthesis 131
3.3.4 Evaluation of pyranopyrazoles and pyranopyrimidines derived 132
from 3-methyl-1-phenyl-2-pyrazolin-5-one (A1-A7) as antioxidants
3.3.5. Synthesis of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl- 136
1,4-dihydropyrano[2,3-c]pyrazole (A11) and it Schiff base derivatives
(A12-A16)
3.3.6 Evaluation of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl- 148
1,4-dihydropyrano[2,3-c]pyrazole (A11) and it Schiff base derivatives
(A12-A14) as antioxidants
VIII
3.3.7 Synthesis of pyranopyrazoles and pyranopyrimidines derived 150
from 5,5-Dimethyl-1,3-cyclohexandion (A17-A25)
3.3.7.1 Synthesis of 5-(4-hydroxyphenyl)-8,8-dimethyl-8,9-dihydro- 151
3H-chromeno-5-cyano-1,4-dihydropyrano[2,3-c]pyrazole (A۱۷)
3.3.7.2 Synthesis of 5-(4-hydroxyphenyl)-8,8-dimethyl-8,9-dihydro- 156
3.3.7.3 Synthesis of 5-(4-hydroxyphenyl)-4-imino-8,8-dimethyl 156
3.3.7.4 Synthesis of 1-(5-(4-hydroxyphenyl)-8,8-dimethyl-6-oxo-2- 159
thiourea (A20)
3.3.7.5 Synthesis of Schiff base derivatives (A21-A25) 162
3.3.8 Evaluation of pyranopyrazoles and pyranopyrimidines derived 171
from 5,5-Dimethyl-1,3-cyclohexandion (A17-A25) as antioxidants
3.3.9 Synthesis of 7-amino-5-(4-hydroxyphenyl)-2,4-dioxo-2,3,4,5- 174
3.3.10 Evaluation of 7-Amino-6-cyano-5-(4-hydroxyphenyl)-5H- 179
pyrano [2,3-d]pyrimidine-2,4-diones (A26) as antioxidants
Conclusion 181
References 183
IX
List of Figure
Figure 1.1 A simplified refinery scheme 10
Figure 1.2 Lubricant composition 11
Figure 1.3 Overbased detergent structure 20
Figure 2.1 The modified microwave irradiation reactor 48
Figure 2.2 Capillary viscometer 50
Figure 2.3 Schematic diagram of the reactor 52
Figure 3.1 FTIR spectrum of overbased magnesium caprylate (D1) 72
Figure 3.2 FTIR spectrum of overbased magnesium caprate (D2) 73
Figure 3.3 FTIR spectrum of overbased magnesium caprylate (D3) 74
Figure 3.4 FTIR spectrum of overbased magnesium myristate (D4) 75
Figure 3.5 FTIR spectrum of overbased magnesium palmitate (D5) 76
Figure 3.6 FTIR spectrum of overbased magnesium oleate (D6) 77
Figure 3.7 FTIR spectrum of overbased magnesium stearate (D7) 78
Figure 3.8 FTIR spectrum of overbased magnesium stearate (D8) 79
Figure 3.9 FTIR spectrum of overbased Calcium oleate (D9) 80
Figure 3.10 FTIR spectrum of overbased Calcium stearate (D10) 81
Figure 3.11 1HNMR spectrum of overbased magnesium palmitate (D5) 82
Figure 3.12 1HNMR spectrum of overbased magnesium stearate (D7) 83
Figure.3.13 The TBN of oil blends with prepared overbased 85
magnesium fatty acid (D1–D7) detergents at different weight
percentages
Figure 3.14 The efficiency of oil blends with prepared overbased 87
magnesium fatty acid detergents (D1-D7)
Figure 3.15 Total sludge, acidity and oxidation products of D5andD7 94
Figure. 3.16 Viscosity index of D5andD7 at different concentrations 96
X
Figure. 3.17 Efficiency of D5 and D7 as VI improver 97
Figure. 3.18 The TBN of oil blends with prepared overbased calcium 100
fatty acid (D8–D10) detergents at different weight percentages
Figure. 3.19 Efficiency of oil blends with prepared overbased calcium 101
fatty acid detergents (D8-D10)
Figure. 3.20 TBN comparison of overbased magnesium detergents 102
with overbased calcium detergents
Figure. 3.21 Efficiency comparison of overbased magnesium 102
detergents with overbased calcium detergents
Figure 3.22 FTIR spectrum of (A1) 109
Figure 3.24 1HNMR spectrum of (A2) 112
13
Figure 3.25 CNMR spectrum of (A2) 113
13
Figure 3.28 CNMR spectrum of (A3) 118
Figure 3. 29 FTIR spectrum of (A4) 121
Figure 3.37 Total sludge, acidity and oxidation products of S3, A1-A7 135
Figure 3.38 FTIR spectrum of compound A11 140
XI
Figure 3.39 1HNMR spectrum of compound A11 141
13
Figure 3.40 CNMR spectrum of compound A11 142
Figure 3.46 Total sludge, acidity and oxidation products of A11-A14 149
Figure 3.48 1HNMR of A17 154
Figure 3.49 13CNMR of A17 155
Figure 3.50 FTIR spectrum of A18 157
Figure 3.52 1H- NMR spectrum of A19 160
Figure 3.59 1HNMR spectrum of A23 169
13
Figure 3.60 CNMR spectrum of A23 170
Figure 3.61 Total sludge, acidity and oxidation products of A17-A25 173
Figure 3.63 1HNMR spectrum of A26 177
13
Figure 3.64 CNMR spectrum of A26 178
XII
Figure 3.65Total sludge, acidity and oxidation products of 180
(B1,B2 and B3)
List of Table
Table 1.1 Lubricant properties for various applications 6
Table 1.2 Relationship between hydrocarbon structure and physical 8
properties in base oils.
Table 1.3 Typical composition of an engine lubes oil. 12
Table 1.4 Common lubricating oil additives 14
Table 1.5 Range of typical detergent lubricant additives 23
Table 1.6 Some commonly used hindered phenols 29
Table 1.7 Examples of metal deactivators 31
Table 2.1 Chemicals and their properties and manufactures. 45
Table 2.2 Properties of base lubricating oils 40 stock and 60 stock. 47
Table 2.3 Nomenclature, structure, and color of synthesized 53
overbased magnesium and calcium detergents
Table 2.4 The physical properties of the Schiff base derivatives (A5- 60
A10)
A16)
A25)
Table 3.1 : Major FTIR absorptions (cm-1) of synthesized overbased 71
detergents
Table ۳.۲ Total base number of synthesized overbased magnesium 84
and calcium detergents
XIII
Table 3.3 Total base number (mg of KOH/g) of blend oils with (D1- 86
D7) detergents
Table 3.4 The efficiency of overbased magnesium fatty acid detergents 88
(D1-D7)
Table 3.5 The effect on TBN by weight% added and carbon number in 89
the chain of D1-D7
Table 3.6 Multiple Comparison between weight% added of D1-D7 90
Table 3.7 Multiple Comparison between carbon number in the chain 92
Table 3.8 Oxidation stability results of blend oils D5 and D7 94
Table 3.9 Viscosity index of blend oils (D5 and D7) 96
Table 3.10 Efficiency of overbased magnesium fatty acid detergents 97
(D5 and D7) as VI improver
Table 3.11 Pour point (οC) of oil blend with 2and 3.5wt.% overbased 98
Mg-palmitate (D5) and stearate (D7)
Table 3.12 Total base number (mg of KOH/g) of blend oils (D8-D10) 100
Table 3.13 Efficiency of overbased calcium fatty acid detergents (D8- 101
D10)
Table 3.14 FTIR spectral data (cm-1) of Schiff-base derivatives (A5- 124
A10)
Table 3.15 Comparison of conventional and microwave synthesis 132
Table 3.16 Oxidation stability results of blend oils (A1-A7 and S3) 134
Table 3.17 FTIR spectral data (cm-1) of Schiff-base derivatives 139
(A12-A16)
Table 3.18 Oxidation stability results of blend oils (A11-A14) 149
Table 3.19 FTIR spectral data (cm-1) of Schiff-base derivatives 162
(A21-A25
XIV
Table 3.20 oxidation stability results of blend oils A17-A25 172
Table 3.21 Oxidation stability results of blend oils (B1, B2 and B3) 179
List of Scheme
Scheme 1.1 Synthesis of overbased sulfonates 21
Scheme 1.2 Synthesis of overbased metal phenates 21
Scheme 1.3 Synthesis of overbased fatty carboxylates 22
Scheme 1.4 Synthesis of overbased metal salicylates 23
Scheme 1.5 Mechanism of lubricant oxidation 25
Scheme 1.6 Formation of carboxylic acids 26
Scheme 1.7 the mechanism of hindered phenol as antioxidant 28
Scheme 1.8 The mechanism of diphenylamine (DPA) as antioxidant 28
Scheme 1.9 Synthesis routes of ADPAs antioxidants 30
Scheme 3.1 General mechanism of overbased magnesium or calcium 31
fatty acid salts synthesis
Scheme 3.2 Knoevenagel condensation mechanism 104
Scheme 3.3 Synthetic rout of compounds A1-A10 107
Scheme 3.4 Formation mechanism of compound (A1) 108
Scheme 3.7 General mechanism of Schiff-base formation 123
Scheme 3.8 Synthesis and reactions of compound (A11) 136
Scheme 3.9 Synthetic rout of compounds A17-A25 150
Scheme 3.10 Formation mechanism of A26 174
XV
Chapter One: Introduction
1.1 Lubricants
Lubricants are an important family among products of the refining

industry and they are widely used to reduce wear and frictions between
moving components in modern equipment to prolong its lifetime [1,2].
Lubricants are used in an important application, such as internal

combustion engines, vehicle, industrial gearboxes, compressors, turbines
or hydraulic systems [3].
A lubricant performs a number of functions. These include the

following [4]:
- Lubricant helps reduce friction and wear by introducing a

lubricating film between mechanical moving parts. Essentially, the
presence of a lubricating film minimizes the metal-to-metal contact
and reduces the force necessary to move one surface against the other.
- Lubricant acts as a heat transfer and dissipates the heat away from
the critical moving parts of the equipment, thereby decreasing the
possibility of the machine component deformation and wear.
- Lubricant facilitates smooth operation of the equipment by
removing and suspending potentially harmful products, such as
carbon, sludge, and varnish, and the other materials, such as dirt.
- Lubricant prevents metal damage due to oxidation products,
corrosion, and wear. It achieves protection by forming a physical film
on metal surfaces that is impervious to oxygen, water, and acids.
- Lubricant is used as a power transfer medium in some
applications, for example, in hydraulic systems. The lubricant
performs this function in addition to its normal function of lubrication.
۱
1.1.1 Lubricant Properties
Lubricant properties that are commonly considered for assessing

the suitability of a lubricant for a particular application include the
following:
1.1.1.1 Viscosity:
The role of viscosity in forming effective lubricating films makes it

one of the most important properties of the lubricant [5]. Viscosity is
defined as a fluid’s resistance to flow and, is primarily a consequence of
the internal friction of the fluid [6]. The property relevant to
measurements is called kinematic viscosity.
Kinematic viscosity is usually determined by measuring the time t

for a given amount of oil to flow at a constant rate through a capillary
held at constant temperature [7].
A number of factors can affect viscosity. Viscosity decreases with

increasing temperature, and increases with increasing pressure [8].
Viscosity also depends upon chemical structures that make up the
lubricant and their molecular size and shape. Within the same structural
type, it increases with the molecular size [9].
1.1.1.2 Viscosity Index:
Viscosity index (VI) is a measure of the viscosity-temperature

relationship. The oils whose viscosities have a high sensitivity to
temperature have a low VI and those whose viscosities have low
sensitivity to temperature have a high VI [10]. High VI oils are generally
preferred for use in most lubricants.
۲
Viscosity Index was established by Dean and Davis [11]. An

arbitrary scale from 0 to 100, is based upon kinematic viscosity and is
quite useful in comparing the VI characteristics of the different oils.
The viscosity index of oil is determined by comparing its 40°C and 100°C
kinematic viscosities with the viscosities of 0 and 100 VI oils. Viscosity
index of the new oil can be calculated from its 40°C viscosity by equation
1.1:
L−U
VI = × 100 ………. 1.1
L−H
Where, L is the 40°C viscosity of the 0 VI oil; U is the kinematic

viscosity of the oil of interest at 40°C; and H is the 40°C viscosity of the
100 VI oil [12]. The need to find oils that have the same 100°C viscosity
as the new oil is eliminated by the use of the ASTM Standards D2270
[12]. These standards contain VI data for many hypothetical reference
oils.
1.1.1.3 Density and Gravity
The density of a substance is the mass of a unit volume of it at a

standard temperature. The specific gravity (relative density) is the ratio
of the mass of a given volume of a material at a standard temperature to
the mass of an equal volume of water at the same temperature [10].
Density and gravity can be determined by means of hydrometers

[13]. In testing used oils, particularly used engine oils, a decrease in
specific gravity may indicate fuel dilution, whereas an increase in specific
gravity might indicate the presence of contaminants such as fuel soot or
oxidized materials.
۳
1.1.1.4 Pour Point:
The pour point measures the temperature at which a base stock no

longer flows, and for paraffinic base stocks, pour points are usually
between ( –12 °C and −15°C), and are determined by operation of the
dewaxing unit [14]. The pour points of naphthenic base stocks, which can
have very low wax content may be much lower (− 30°C to−50°C).
1.1.1.5 Volatility and Flash Point:
Volatility relates to base oil or its components to evaporate under

the influence of high temperatures. High volatility in modern lubricants is
not acceptable because of its negative effect on the environment and the
possibility of ignition. In general, the paraffinic oils have the lowest
volatility, the aromatic oils have the highest volatility, and the naphthenic
oils fall in between the two extremes [15].
Flash Point is used as a measure of oil’s volatility. The flash point

of oil is the temperature at which the oil releases enough vapor at its
surface to ignite when an open flame is applied.
1.1.1.6 Total Base Number:
The total base number (TBN) of oil is the quantity of acid,

expressed in terms of the equivalent number of milligrams of potassium
hydroxide, that is required to neutralize all basic constituents present in
one gram of oil. This test is normally used with oils that contain alkaline,
acid-neutralizing, and additives. TBN is an indication of the projected
serviceable life of the oil. With used oils, it indicates how much acid-
neutralizing additive remains in the oil [16].
٤
1.1.1.7 Oxidation Stability:
Oxidation is initiated by the reaction of oxygen with the

hydrocarbon materials to form precursors to harmful products. Wilson
[17] noted that the rate of oil oxidation is affected by oxygen availability,
temperature, the presence of catalysts and the composition of the base
stock.
The effects of excessive lubricant oxidation are noticeable by oil

thickening and the formation of the insoluble, such as sludge, varnish,
lacquer, and hard carbonaceous deposits on hot surfaces. Some oxidation
products are acidic and therefore cause corrosion of the metal surfaces.
In addition, there are other properties that are important in some

applications. These include color, viscosity-pressure relationship;
detergency, dispersant, and foaming and. Lubricant properties of high
importance for various applications are listed in Table 1.1[18].
٥
Table 1.1 Lubricant properties for various applications [18].
and wear control
temperature
Application
Dispersant
Corrosion
Oxidation
resistance
Viscosity
Friction
fluidity
control
control
Foam
Index
Low-
No.
Engine Oils:
1. Gasoline √ √ √ √ √ √ √
2. Diesel √ √ √ √ √ √ √
3. Stationary Gas √ √ √ √ √ √
Hydraulic fluids:
1. Tractor √ √ √ √ √ √ √
Hydraulic
2. Industrial √ √ √ √ √ √
Hydraulic
Gear oils:
1. Automotive √ √ √ √ √ √
2. Industrial √ √ √ √ √ √
Miscellaneous Lubricants:
1. Industrial Oils √ √ √ √ √
2. Turbine Oils √ √ √ √ √
٦
1.1.2 Lubricants chemistry
Chemical composition of the base oils depends upon the crude oil
source, and the refining process. Base oils consist of the following
organic compounds [14,17]:
- n-Paraffins: These are C18 and greater members of the n-paraffin

homologous series, which are present in significant quantities in feeds.
- Isoparaffins: These have n-paraffin backbones with alkyl branches.

Isoparaffins as a group are commonly said to have high VIs and low pour
points, and confer good oxidation resistance.
- Cycloparaffins (naphthenes): Contain one or more cyclohexane or

cyclopentane rings, or a combination thereof. Monocycloparaffins with
1,4 substituents are widely regarded as favorable structures, whereas
polynaphthenes are considered unfavorable for both VI and oxidation
resistance.
- Aromatics: Basic structures have one to six or more benzene rings with
alkyl substituent. Alkyl-substituted benzenes with 1,4 alkyl groups have
high VIs and good oxidation resistance, whereas fused polyaromatic
structures are undesirable.
- Sulfur-containing compounds: These may be thiols, sulfides,

thiophenes, benzo-thiophenes, and more complex structures. Lube
hydrocracking reduce sulfur to about 10 ppm or less in the base stocks.
- Nitrogen-containing compounds: Nitrogen largely appears in pyrroles,

carbazoles, pyridines, and quinolines. Lube hydrocracking reduces
nitrogen levels to parts per million.
۷
Table 1.2 presents the relationship between various lubricant properties

and chemical structures [4].
Table 1.2 Relationship between hydrocarbon structure and physical

properties in base oils [4].
No. Hydrocarbon Type Structure Main Properties

1. Straight chain paraffin - High viscosity index.
- Good oxidation
resistance.
- High pour point.
2. Branched chain - High viscosity index
paraffin - Good oxidation
resistance.
- May have low pour
point.
3. Naphthenic rings with - Low viscosity index.
short paraffinic side - Good oxidation
chains resistance.
- Low pour point.
4. Naphthenic rings with - High viscosity index.
long paraffinic side - Good oxidation
chains resistance.
- May have low pour
point.
5. Aromatic rings with - Low viscosity index.
short paraffinic side - Poor oxidation
chains resistance.
- Good thermal stability.
- Pour point varies
according to structure.
6. Aromatic rings with - Low viscosity index.
long paraffinic side - May have good
chains oxidation resistance if the
structure does not contain
too many rings.
- May have low pour
point.
۸
1.1.3 Lubricants production
The primary method to separate the useful fractions for lubricating

oil production from crude oil is distillation [19-21], which includes
atmospheric and vacuum distillation as shown in figure 1.1.
Lower-boiling fuel products (naphtha, gasoline, kerosene, and

diesel fuels) are distilled off in the atmospheric tower. The higher
molecular weight components which do not vaporize at atmospheric
pressure (atmospheric residue) are then fractionated by distillation at
reduced pressures from 10 to 50 mmHg (vacuum distillation). Thus the
“bottoms” from the atmospheric tower are fed to the vacuum tower,
where light, medium, and heavy lubricating oils are produced.
The thick, black residue remaining after vacuum distillation

(vacuum residue) can be solvent extracted to produce oil known as bright
stock by a process known as deasphalting (liquid propane deasphalting).
The VI of light, medium, and heavy lubricating oils, and bright

stock should be increased by extraction of low VI poly condensing
aromatic and naphthenic by furfural extraction process. Then the pour
point of these fractions should be decreased by dewaxing process. The
fractions obtained from dewaxing process must be hydrofinished to
remove sulfur and nitrogen compounds, and saturation of olefins.
Finally the oils fraction obtained from hydrofinishing process

(called basic lubricating oils) blended with different additives for quality
improving to produce different commercial lubricating oils.
۹
Figure 1.1 A simplified refinery scheme
۱۰
1.1.4 Lubricants Formulation:
Lubricants are formulated by blending base oils and additives to

meet a series of performance specifications. These specifications relate to
the chemical and physical properties of the formulated oil when it is new
and also ensure that the oil continues to function and protect the engine or
machinery in service [17]. A range of properties can be measured and
used to predict performance when selecting an appropriate base oil for
use in formulation, (e.g. VI, TBN, pour point, and oxidation stability).
A formulated lubricant comprises base oil, a performance package,

an additional viscosity modifier and pour point depressant. The amount of
each of these components varies based upon the application and the
desired service. Figure1.2 provides the approximate ranges of each in the
lubricant [22].
0-1%
Performance Package
2-20%
Viscosity Modifer
65-98%
0-30%
Base Oil
Pour Point Depressant
Figure 1.2 Lubricant composition
The performance package contains a number of additives, it can

make up to 20 %, and sometimes even higher, of the total lubricant
composition, depending upon the desired performance level and the
severity of the requirements [7]. Table 1.3 is reported the average
composition of a fully formulated engine oil [23].
۱۱
Table 1.3 Typical composition of an engine lubes oil [23].
Component Percentage
Base oil 80
Detergents 2
Dispersants 6
Viscosity modifiers 9
Antioxidant 1
Antiwear (ZDDP) 2
Base oil alone cannot satisfy the lubrication needs of modern

equipment. It requires the help of oil additives, which improve chemical
and physical properties of lubricating oil.
۱۲
1.2 Additives
Additives can be defined as substances which improve the

performance of lubricants, either by imparting new properties to a base
oil, or by enhancing properties already present.
The use of additives became common only after the 1930s when
more compact and faster engines were developed, and enormous growth
has been seen since in both their production rates and the scope of their
applications [17,24].
Additives are grouped into three general categories

according to the functions they perform:
- Protection the lubricated surface
Anti-wear additives, corrosion and rust inhibitors, detergents and

dispersants are included in this category.
- Improving lubricant performance
Viscosity index improvers, pour point depressants, and antifoaming

agents are examples.
- Protection the lubricant itself
Antioxidants reduce the tendency of oil to oxidize and form sludge and
acids. The most common additives are listed in table 1.4 [25].
۱۳
Table 1.4 Common lubricating oil additives [25].
No. Additive Type Compounds Used Function
1. Detergent Calcium sulfonates. Prevent deposition of carbon.
2. Dispersant Polyisobutylene Dispersing the insoluble

materials and prevent
deposition of sludge.
3. Antiwear Zinc dithiophosphates. Reduce wear. And prevent

(ZDDP) scuffing of rubbing surfaces.
4. Anticorrosion Zinc dithiophosphates. Form anticorrosion film. To

(ZDDP) reduce corrosion of lead and
copper metals.
5. Viscosity Organic polymers. Improve VI.

Index
Improvers
6. Pour point Methacrylate Lower pour point.

Depressant polymers.
7. Antifoam Silicones. Control foaming in force

feed systems.
8. Antioxidant Hindered phenols & Prolong oil life by slowing

Amines. oxidation.
۱٤
1.2.1 Detergents
These additives perform two major functions. They neutralize the

acidic by-products of combustion and lubricant oxidation and keep the
deposit precursors and contaminants, which have marginal oil solubility,
in oil. This minimizes deposit formation on engine or transmission parts.
It is their base reserve, that help neutralize acids and the soap content that
help suspend the polar products in oil. These materials are alkali metal or
alkaline earth metal salts of organic acids, with or without the reserve
base [24].
1.2.2 Dispersants
The role of dispersants is to prevent agglomeration of particles

produced by oil degradation and metallic parts wear (sludge) and
maintain them in suspension in the oil. Even if the principle of operation
is similar to detergents, they differ from detergents because they are by
definition free of metals. They disperse these species via their polar ester
or imide functionalities and keeping them dissolved in oil by associating
with it via their nonpolar hydrocarbon chains. The suspended harmful
products are removed when the oil is changed [26]. The main class of
dispersant is polyisobutylene derivatives [27, 28].
1.2.3 Antiwear Additives
To prevent wear due to metal-to-metal contact, anti-wear additives

found in most lubricants form a coating. However, heat from friction
between surfaces provides energy for a chemical reaction between the
additive and metal surfaces that result in a protective coating.
Zinc Dialkyl Dithiophosphates (ZDDPs) have been extensively

used as antiwear additive since 1940s [29-31].
۱٥
1.2.4 Rust and Corrosion Inhibitors
These additives protect metal surfaces against the attack of oxygen,

water, acids, bases, and salts. They achieve this by physically adsorbing
on the metal surfaces via their polar functional group and by maintaining
a resilient protective film on the surfaces by associating with the
lubricant. Rust inhibitors are additives that protect ferrous metals and
corrosion inhibitors are additives that protect nonferrous metals [32].
1.2.5 Viscosity Modifiers
Viscosity modifiers are polymers that help a lubricant maintain its

lubricating ability at high temperatures. They do so by increasing their
molecular size, hence increasing association with the oil so that it does
not flow away from the surfaces.
Examples of viscosity modifiers are: polymethacrylates (PMAs)

[33,34], olefins copolymers (OCPs) [35,36], and styrene-diene
copolymers [37].
1.2.6 Pour Point Depressants
Petroleum base oil-derived fluids contain waxes, which at low

temperatures start to crystallize to form network structures. These
structures absorb oil and impede its flow. Pour point depressants prevent
crystalline network formation and permit oil flow at low temperatures.
Common Pour point depressants include polymethacrylates
[38,39], and styrene-ester copolymers [40].
1.2.7 Foam Inhibitors
Formation of foam in most lubrication applications is undesirable

since it impedes lubrication, promotes lubricant oxidation, obstructs
۱٦
narrow passages, and reduces a lubricant’s cooling ability. Foam

inhibitors are additives that reduce the foam-forming tendency of the
lubricant. Common additives used to accomplish foaming control include
polysiloxanes [41,42].
1.2.8 Oxidation Inhibitors
An oxidation inhibitor is used to prevent or eliminate the oxidation

reactions of lubricating oil. These additives control the oxygen-initiated
degradation of the lubricant. They belong to three general classes’ free
radical scavengers, hydroperoxide decomposers, and metal deactivators.
1.3 Overbased detergent
Overbased detergent involves incorporating additional base reserve

into the original neutral detergent structure, usually in the form of a
colloidal dispersed metal carbonate such as CaCO3 or MgCO3.
The name "overbased" detergent comes from the fact that these
detergents contain more base than is required to neutralize the acidic
components [43]. The TBN indicates a detergent’s ability to neutralize
acids. In additives and formulated lubricants, the TBN is expressed as mg
KOH/g of additive [44].
During the early 1950s, methods were discovered by which fully

oil soluble detergents could be prepared that contain up to 30 times more
metal than the normal neutral detergents [45]. Overbased detergents
impart basicity to the oil to neutralize acids formed during the
combustion process and from the degradation of the lubricating oil. They
can also impart other performance benefits to the lubricant, such as
antiwear [46] and antioxidant [47], or act as rust and corrosion inhibitors
[48,49].
۱۷
1.3.1 Synthesis of Overbased Detergents
Detergents are identified as sulfonates, phenates, carboxylates, and

salicylates depending upon the acid precursor. These acids are called
detergent substrates [50].
Overbased detergents containing as much as 30 times the

stoichiometric amount of metals have been developed over recent years.
They can be prepared by reacting the substrate with an excess amount of
metal bases, such as metal oxides and metal hydroxides, in the presence
of carbon dioxide [51]. Common commercial detergents are derived from
calcium, magnesium, and barium. The metals are listed in order of
preference.
In general, the reaction between the organic acid and the inorganic
base is not good because of poor contact between the two reactants. A
number of compounds, called promoters, are used to facilitate salt
formation and the subsequent carbonation.
Common promoters include ammonium hydroxide; low-molecular-

weight carboxylic acids, such as formic acid and acetic acid; and low-
molecular-weight alkylphenols [52]. The role of promoters in the
overbasing reaction is not well understood.
To make overbased detergents, there are two processes: one-step

process, and two-step process. In the one-step process, the excess metal
base is charged to the reaction; once the neutral salt formation is
complete, carbon dioxide blowing (carbonation) of the reaction is
initiated. While in the two-step process, the neutral salt or the soap is
made first, which is subsequently overbased. Generally, the one-step
process is preferred over the two-step process [50].
۱۸
1.3.2 Overbasing Description
During the overbasing process, an enormous number,

approximately 1000 per cm3, of reverse micelles carry the promoters into
the oil. These micelles are the key to overbasing.
When the metal hydroxide is added, it does not immediately

dissolve into the micelle. Rather, it enters gradually, to replace the
hydroxide that is consumed in the neutralization of H2CO3. The metal
carbonate is insoluble, so once formed, it precipitates immediately. This
precipitation is the driving force for bringing in more metal hydroxide
and CO2, making mass transfer an important processing variable . Since
all these reactions occur within the micelle, the size of the resulting metal
carbonate particle is thus governed by two factors, the size of the reverse
micelle and the number of micelles that collide to form metal carbonate
aggregates [17]. Neuron scattering experiments show that the primary
size of the detergent particle is between 5 and 10 nm [53].
1.3.3 Overbased Detergent Structure
A reverse micelle structure was suggested by molecular dynamics

simulation, and direct evidence was given by Transmission Electron
Microscopy. This structure can be divided into three different regions.
The calcium carbonate mineral core sits at the centre of the structure,
which is amorphous carbonate. The second zone, is the polar organic
shell. It consists of the polar heads of the surfactant, and any residual
polar solvents, interacting with the outer calcium carbonate. The third, or
'outer' zone, contains the hydrophobic alkyl tails of the surfactants, which
help solublising the reverse micelle structure in the base oil. Figure 1.3
shows generalized overbased detergent structure [43,50].
۱۹
Figure 1.3 Overbased detergent structure
1.3.4 Overbased Detergent Types
There are three major classes of detergents: sulfonates, phenates,

carboxylate and salicylates.
1.3.4 .1 Sulfonates
Overbased sulfonates are metal salts of long-chain

alkylarylsulfonic acids with colloidal dispersed metal carbonate. Calcium
sulfonates are relatively cheap products with good general performance
[54-59]. Magnesium compounds distinguish by excellent anticorrosion
properties [60].
Scheme 1.1 shows the synthesis of overbased sulfonates.
۲۰
Scheme 1.1 Synthesis of overbased sulfonates
1.3.4.2 Phenates
Phenates represent an important class of detergents which are

synthesized by reaction of alkylated phenols with excess metal (calcium,
magnesium) oxides or hydroxides under carbonation [61- 67] as shown in
scheme 1.2 . Calcium phenates are currently the most widely used types.
Beside their good dispersant properties they also possess greater acid
neutralization potential.
Scheme 1.2 Synthesis of overbased metal phenates
۲۱
1.3.4.3 Carboxylate and Salicylates
Common carboxylic acids, which are used to make detergents,

include natural fatty acids, branched long-chain acids, naphthenic acids,
and alkylsalicylic acids [4].
High molecular weight carboxylic acids were the first substrates

used to prepare detergent additives such as calcium dichlorostearate.
Basic and overbased calcium alkylcarboxylates are still used in

certain applications. Recently new environmentally friendly overbased
detergents derived from fatty carboxylate were synthesized (scheme 1.3)
by Wang, Y., and coworkers [68-72].
Scheme 1.3 Synthesis of overbased fatty carboxylates.
Salicylates are a special class of carboxylates, which generally

prepared by carboxylation of alkylated phenols with subsequent
metathesis into divalent metal salts (scheme 1.4). Typically also these
products are overbased by an excess of metal carbonate (calcium and
magnesium) to form highly basic detergents that are stabilized by micelle
formation [73-75]. Salicylates are a combination of phenate and
carboxylate chemical functions, and exhibit additional antioxidant
properties and have proven effective in diesel engine oil formulations.
۲۲
Scheme 1.4 Synthesis of overbased metal salicylates
The typical ranges of parameters for commercially available

detergents[17] are collected together in Table 1.5.
Table 1.5 Range of typical detergent lubricant additives [17].
No. Parameter Sulphonates Phenates Carboxylates
1- TBN, mg KOH/g 0 - 500 50 - 400 50 - 400
2- Soap content,% 10 - 50 30 - 50 10 - 45
3- Metal ratio 1 - 30 0.8 – 10.0 1 - 10
4- Common metal cation Ca, Mg Ca Ca, Mg
5- Sulfur,% 0.5 – 4.0 0-4 -
6- Molecular weight 375 - 700 160 – 1000 250 – 1000
۲۳
1.4 Antioxidants
Lubricating oils are susceptible to degradation by oxygen. This

oxidation process, which is initiated by the formation of reactive free
radicals and peroxides, is the major cause of oil thickening and the for-
mation of sludge and varnish.
Three types of antioxidants are used, either separately or in

combination, to improve the oxidation stability (or resistance to
oxidation) of finished lubricants, these are:
radical acceptors or scavengers (primary antioxidants),
peroxide decomposers (secondary antioxidants), and
metal deactivators.
Oils for turbine, hydraulic, electro-insulating and similar, relatively

low temperature applications, are mostly blended with radical acceptors
and metal deactivators. In engine and other oils which work at high
temperatures, peroxide decomposers are predominantly used, sometimes
in combination with metal deactivators [43].
1.4.1 Oxidation Mechanism
The lubricating oil oxidation mechanism involves a free-radical

chain reaction [76]. It consists of four distinct reaction steps: chain
initiation, propagation, branching, and termination [77].
The mechanism of oxidation is illustrated in scheme 1.5.
۲٤
Scheme 1.5 Mechanism of lubricant oxidation
1.4.1.1 Initiation of the Radical Chain Reaction
The initiation step is characterized as the formation of free alkyl

radicals (R•). The reaction take place when hydrocarbons are exposed to
oxygen and energy in the form of heat, UV light, or mechanical shear
stress [78]. The ease of homolytic cleavage of an R–H bond follows this
order, as determined by the C–H bond strength and the stability of the
resulting radical [79]: primary < secondary < tertiary < allylic < benzylic.
1.4.1.2 Propagation of the radical chain reaction
An alkyl radical reacts irreversibly with oxygen to form an alkyl

peroxy radical. The rate of reaction of carbon-centered radicals with
oxygen depends on the type of substituent's attached to the C atom and
increases in the following order:
H3C· < C6H5(R)CH· < RCH=CH(R)CH· < R2CH· < R3C·
The next step in the chain propagation scheme is the hydrogen

abstraction by a peroxy radical from another hydrocarbon.
۲٥
1.4.1.3 Chain branching
The chain-branching steps begin with the cleavage of

hydroperoxide into an alkoxy radical (RO•) and a hydroxy radical (HO•).
Primary alkoxy radicals are so active that they abstract hydrogen atoms to
form alcohols. Secondary and tertiary alkoxy radicals prefer to form
aldehydes, and ketones [80].
Under high-temperature oxidation conditions, the aldehydes and

ketones can undergo further reactions to form acids and high molecular
weight species (scheme 1.6), that thicken the oil and contribute to the
formation of sludge and varnish deposits [81].
Scheme 1.6 Formation of carboxylic acids.
1.4.1.4 Termination of the radical chain reaction
As oxidation proceeds, oil viscosity will increase due to the

formation of high-molecular-weight hydrocarbons. When oil viscosity
has reached a level that diffusion of oxygen in oil is significantly limited,
chain termination reactions will dominate. Termination may be effected
by the combination of radical species such as peroxy radicals to yield
ketones and alcohols.
Generally, the rate of termination increases across the series:

tertiary peroxy < secondary peroxy < primary peroxy.
۲٦
1.4.2 Oxidation Inhibition
The more practical approach to control lubricant oxidation for most

lubricant applications is the trapping of catalytic impurities and the
destruction of alkyl radicals, alkyl peroxy radicals, and hydroperoxides.
This can be achieved through the use of a metal deactivator and an
appropriate antioxidant with radical scavenging or peroxide decomposing
functionality, respectively.
1.4.2.1 Radical Scavengers
The radical scavengers are known as primary antioxidants. They

function by donating hydrogen atoms to terminate alkoxy and alkyl
peroxy radicals, thus interrupting the radical chain mechanism of the
oxidation process.
Phenols and aromatic amines are two main classes of primary

antioxidants for lubricants [4].
1.4.2.1.1 Phenols
The most important compounds are sterically-hinderedphenolic

rings. The structures, and typical applications of some commonly used
hindered phenols are given in table 1.6.
Hindered phenols react with ROO and ROO. radicals and

eventually form stable quinones, via relatively stable semiquinone
radicalsaasashownainaschemea1.7.
۲۷
Scheme 1.7 The mechanism of hindered phenol as antioxidant.
1.4.2.1.2 Amines
Primary, and secondary aromatic amines and diamines are effective

antioxidants. The mechanism of amine action is illustrated in scheme 1.8.
Hydrogen transfer is assumed to be the first step, followed by the
formation of comparatively stable nitroxyl radicals :
Scheme 1.8 The mechanism of diphenylamine (DPA) as antioxidant.
۲۸
Table 1.6 Some commonly used hindered phenols
Phenol/ (Applications) Structure Ref.
2,6-Di-tert-butyl-phenol
82
(Industrial oils and
power transmission
fluids)
2,6-Di-tert-butyl-4-
methylphenol (BHT)
83
(Industrial oils and
power transmission
fluids)
3,5-Di-tert-butyl-4-
hydroxy hydrocinnamat
84-86
alkyl ( C7–C18) ester
(Engine oils, power
transmission fluids, and
industrial oils)
2,2′-Methylene bis(4-
methyl-6-tert-butyl-
87,88
phenol)
(Engine and industrial
oils)
Alkylated diphenyl amines (ADPAs) are the most important

classes of amine antioxidants being used today [17]. Scheme 1.9
illustrates the typical synthesis routes of some commonly used ADPAs.
۲۹
Scheme 1.9 Synthesis routes of ADPAs antioxidants
1.4.2.2 Peroxide Decomposers:
The peroxide decomposers are also called secondary antioxidants

[43]. They function by reducing alkyl hydroperoxides in the radical chain
to nonradical, less-reactive alcohols.
Common types of peroxide decomposer inhibitor include

organosulfur, such as benzyl sulphide [107], organophosphorus
compounds, such as phosphites [108, 109], and those containing both
elements, such as ZDDPs [110].
۳۰
1.4.2.3 Metal deactivators
Since transition metals are present in most lubrication system,

metal deactivators are usually added to lubricants to control the catalytic
activities of the metals. Metal deactivators for petroleum products can be
classified into two major types: chelators [111] and surface passivators.
The surface passivators act by attaching to metal surface to form a

protective layer, thus preventing metal–hydrocarbon interaction. While,
the chelators act by trapping metal ions to form an inactive or much less-
active complex. Table 1.7 lists examples of metal deactivators that are
commonly used in lubricating oils.
Table 1.7 Examples of metal deactivators
Metal deactivators Structure Ref.

Surface Passivators:
112
Triazole derivative
113
Benzotriazole
114,
2-Mercaptobenzothiazole 115
Chelators:
N,N′-Disalicylidene-1,2- 111
diaminopropane
۳۱
1.5 Pyrazole
The term pyrazole was given by Ludwig Knorr in1883[116].

Pyrazole refers to the class of simple aromatic ring organic compounds of
the heterocyclic series characterized by a 5-membered ring structure
composed of three carbon atoms and two nitrogen atoms in adjacent
positions. Being so composed and having pharmacological effects on
humans, they are classified as alkaloids [117].
Pyrazole derivatives are the subject of many research studies due to

their herbicidal, fungicidal, insecticidal, analgesic, antipyretic and anti-
inflammatory properties [118].
Pyrazolone moiety is a pyrazole derivative, containing a five-

membered lactam ring with two nitrogen atoms and a ketone group in the
same molecule. Edaravone, 3-methyl-1-phenyl-2-pyrazolin-5-one, is a
free radical scavenger and was used for treatment of patients with acute
brain infarction [119]. The radical scavenging capacity of various
derivatives of pyrazol-5-ols were reported [120].
Some methods to synthesize pyrazolone derivatives, 3-methyl-2-

pyrazolin-5-one (1), and 3-methyl-1-phenyl-2-pyrazolin-5-one (2) have
been developed in recent years, though the most important method is the
reaction between hydrazones and β-dicarbonyl compounds. This reaction
involves the double condensation of 1, 3-diketones or α, β-unsaturated
ketones with hydrazine or its derivatives [121].
۳۲
O O Me
NH2NH2
N
Me OEt O
N
(1)
O O Me
Ph NH NH2
N
Me OEt O
N
Ph
(2)
Mojtahedi et al. [122] used ultrasonic irradiation to facilitate the

formation of pyrazolone derivatives in good to excellent yield within very
short time periods by condensation of hydrazine derivatives with various
β-keto esters.
1.6 Pyranopyrazoles
Pyranopyrazoles are important class of biologically active

heterocyclic compounds. They find applications as antibacterial
[123,124], antifungal [125], antimicrobial [126], anti-inflammatory
[127,128], analgesic [129,130] and biodegradable agrochemicals like
insecticidal [131], and herbicidal agents [132].
Dihydropyrano[2,3-c]pyrazole was first synthesized by a reaction

between 3-methyl-1-phenylpyrazolin-5-one and tetracyanoethylene [133].
H. Otto reported a base catalyzed two-component Michael type

reaction between 4-arylidiene-1- phenyl-1H-pyrazol-5-one (3) and
malononitrile for the synthesis of various 4-aryl-4Hpyrano[2,3-
c]pyrazoles (4) [134,135].
۳۳
R R
CN
CN
N N
EtOH
N base
CN N
O O NH2
(3) (4)
Subsequently, 4-alkyl and 4-aryl-substituted pyranopyrazoles (6)

were synthesized from reaction of 3-methyl-1H-pyrazol-5-one (1) with
alkyl and arylidenemalononitrile (5) (Scheme 1.14),[136].
EtOH
N CN
base
CN
N
H O N
CN N
H O NH2
(1) (5) (6)
Y. Peng and co-workers [137] have developed a two-component

reaction involving pyran derivatives (7) and hydrazine hydrate to obtain
pyranopyrazoles (6) in water. The reaction was promoted by a
combination of microwave and ultrasonic irradiation.
6-Amino-5-cyano-dihydropyrano[2,3-c]pyrazoles (6) have been

identified as a screening hit for human Chk1 kinase inhibitors.
۳٤
3-Ethyl-1H-pyrazol-5(4H)-one (8) was reacted with benzylidene-

malononitrile (5) to yield 6-amino-3-ethyl-4-phenyl-2,4-
dihydropyrano[2,3-c]pyrazole-5-carbonitrile (9) [138].
O
H2N H H2N
O O
Ph CN N N
NH N NH
N
CN
CN CN
(8) (5)
(9)
Boghdadie et al. [139] reported that, 4-(hydroxyl-3-

methoxybenzylidine) malononitrile (10) was reacted with 3-ethyl-1-
phenyl-2-pyrazolin-5-one (11), in the presence of piperidine drops to
produce 6-amino-3-ethyl-4-(4-hydroxy-3-methoxyphenyl)-1-phenyl-4H-
pyrano[3,2-d] pyrazole-5-carbonitrile (12).
The antioxidant activity of the prepared compound (12), using the turbine
base oil, was evaluated. The formulated blend oil containing 1.6 wt.% of
۳٥
(12) gave higher oxidation stability than a blend containing 0.8 wt.% of
commercial antioxidant additive [139].
H3CO O
H3CO NC NH2
CN
HO C C N
H Ph EtOH/ Piperidine HO O
CN N
reflux, 2 h
H3C
N
(10) (11)
N Ph
H3C
(12)
The most common and convenient approach toward diverse

pyranopyrazoles is a base catalyzed three-component reaction of pyrazol-
5-one (1), arylaldehydes, and malononitrile. Yu. A. Sharanin et al.[140]
have first developed this three-component reaction protocol for
pyranopyrazole synthesis in ethanol using triethylamine (Et3N) as the
catalyst.
Heravi et al. [141] reported facile method for the synthesis of 1,4-
dihydropyrano[2,3-c] pyrazole derivatives (4) via three-component one-
pot condensation of 3-methyl-1-phenyl-2-pyrazolin-5-one (2),
arylaldehydes and malononitrile in the presence of heteropolyacid
(H14[NaPW12O40]), as a green and reusable catalyst in water or ethanol
under refluxing conditions.
۳٦
CH3
Ar
H3C
N CN CN
ArCHO H14[NaPW12O40]
N Water or Ethanol NH
CN
Refluxing
Ph O (13) N
O NH
2
Ph
(2)
(4)
J. Li et al. [142] report a highly efficient procedure for the

synthesis of 6- amino-5-cyano -4-aryl-1,4-dihydropyrano[2,3-c]
pyrazoles, via a one-pot grinding method under solvent-free conditions
using an inexpensive and commercially available D,L-proline as catalyst.
X. Wang et al. [143] used triethylbenzylammonium chloride

(TEBA) as catalyst in aqueous media to prepare 6-Amino-5-cyano-4-aryl-
1,4-dihydropyrano[2,3-c] pyrazoles by three-component reaction. While,
T-S Jin et al [144] used p-dodecylbenzenesulfonic acid (DBSA) as the
catalyst.
Green one pot solvent-free synthesis of pyrano[2,3-c]- pyrazoles

(6) was achieved by Al-Matar et al [145] via mixing four components,
ethyl acetoacetate, hydrazine hydrate, aldehydes or ketones and
malononitrile.
NC NH2 NC NH2
O O
Ar O Ar O
CH2(CN)2
H3C OEt + NH2.NH2.H2O
Ar-COH
NH N
H3C N H3C N
H
(6)
۳۷
K. Kanagaraj and K. Pitchumani [146] have utilized per-6-amino-

b-cyclodextrin (per-6-ABCD) as an excellent catalyst for the synthesis of
pyranopyrazole derivatives, in an efficient and eco-friendly four
component reaction protocol under solvent free conditions at room
temperature. It is also interesting to note that the catalyst can be
recovered and reused several times.
A simple, green and efficient protocol for synthesis of

dihydropyrano[2,3-c]pyrazole derivatives is developed by a four
component reaction using 3-methyl-1-(4-sulphonic acid)
butylimidazolium hydrogen sulphate as a catalyst, under solvent-free
conditions [147].
Recently M.A. Nasseri, and S.M. Sadeghzadeh prepared a

magnetic nanoparticle (MNP) supported hyperbranched polyglycerol
(HPG) catalyst from inexpensive starting materials in aqueous medium.
This catalyst (FeNi3/SiO2/HPG MNP) was used to synthesize
pyranopyrazoles from various aromatic aldehydes, malononitrile, ethyl
acetoacetate, and hydrazine hydrate at room temperature under solvent-
free-conditions [148].
1.7 Chromene
Benzopyran (known as chromene ) is a heterocyclic ring system

consisting of a benzene ring fused to a pyran ring. The benzopyran
nucleus include some structural skeletons such as chromane, 2H-
chromene and 4H-chromene [149]
۳۸
Chromene derivatives are an important class of compounds, widely

present in plants, including vegetables and fruits [150]. It constitutes the
basic backbone of various types of polyphenols and widely found in
natural alkaloids, flavonoids, and anthocyanins [151].
Chromenes (13) are generally prepared by reacting malononitrile,

aldehyde and activated phenol in the presence of organic bases
(piperidine, pyridine, ammonia, potassium carbonate, triethylamine,
magnesium oxide, etc) for several hours[152].
Synthetic analogues have been developed over the years, some of

them displaying remarkable effects as antifungal [153], anti-microbial
[154], anticancer [155] and antioxidant [156].
۳۹
1.8 2-Amino-3-cycano-4-aryl-7,7-dimethyl-5,6,7,8-
tetrahydro chromene
Tetrahydrochromenes derivatives, also known as

tetrahydrobenzopyrane (4H-pyrans ), which have attracted much attention
due to their wide range of biological properties.
2-Amino-chromenes represent an important class of compounds

being the main components of many naturally occurring products and are
widely employed as cosmetics, pigments, [157] and potential
biodegradable agrochemicals [158]. Fused chromenes are biologically
active compounds with a wide spectrum of activities, such as
mutagenicity [159], antitumor [160] and central nervous system activity
[161].
Kemnitzer, W. et.al. discovered a new series of 4-Aryl- 4H-

chromene as Apoptosis inducers using a cell and caspase based high
throughput screening assay [162].
The conventional synthesis of 2-amino-3-cyano-4H-pyrans (14)

use organic solvent and base catalyst [163].
O
CHO CN CN
catalyst
+ +
CN O O O NH2
(14)
In recent years, 2-amino-3-cyano-4H-pyrans have also been

synthesized under microwave [164], with ultrasonic irradiation [165].
٤۰
Some two-component and three-component condensations have been

introduced for the synthesis of 2-amino-3-cyano- 4H-pyrans.
Kumar et al. [166] have reported an environmentally friendly

synthetic process using magnesium oxide as the catalyst and by process
of grinding (Scheme 1.23). This is the classical reaction where,
benzaldehyde or ketone has first been reacted with a malanonitrile,
yielding the benzylidenemalanonitrile, and the reaction of benzylidene-
malanonitrile with 1,3-diketo compound afforded the 2-amino-3-
cyanochromene derivative. The only difference between this and
classical methodologies is the reaction has been carried at room
temperature and it is grinded without any solvent and this gives a higher
yield in limited time.
O
CHO CN CN
CN
MgO,R.T. O O
+
Grinding CN MgO,R.T.
CN NH2
Grinding O
(14)
Li et al. [165] report a highly efficient procedure for the synthesis

of 2-amino-3-cycano-4-aryl-7,7-dimethyl-5,6,7,8-tetrahydro-
benzo[b]pyrans via a one-pot grinding method under solvent-free
conditions using an inexpensive and commercially available D,L-proline
as catalyst.
The synthesis of 4H-benzo[b]pyran derivatives has also been

proposed by means of a basic ionic liquid-catalyzed three-component
approach involving malononitrile, aromatic aldehydes and dimedone. It
has been found that a small amount of N,N-dimethylaminoethylbenzyl-
٤۱
dimethylammonium chloride gave at 60 °C high yield by solvent-free

transformation [167].
Peng and Song conducted this three component reaction in a

mixture of catalytically active ionic liquid and water [168]. While,
Lingaiah and co-workers reported the use of a heterogeneous strong basic
Mg/La mixed oxide catalyst in methanol [169].
A mixture of an aromatic aldehyde, dimedone, and malononitrile

in aqueous media catalyzed by 1-butyl-3-methyl imidazolium hydroxide
[170] gave the 4H-benzo[b]pyran derivatives in excellent yields.
Gen Zhang et al [171] presented a highly efficient process for the

synthesis of 2-amino-4H-chromenes through an organocatalytic
Knoevenagel/Michael/cyclization sequence, and the preliminary
biological studies of these new heterocyclic compounds revealed potent
antibacterial activity.
A clean and efficient method for the synthesis of 2-amino-4-aryl-3-

cyano-5-oxo- 4H-5,6,7,8-tetrahydrobenzopyran derivatives using
hexadecyldimethylbenzyl ammonium bromide (HDMBAB) as the
catalyst was described by Tong-Shou Jin [172]. While X-Z Lian et al
used N-methylimidazole as the organocatalyst (20mol%) [173]. The
mixture of an appropriate aldehyde, malononitrile and dimedone in the
presence of the Zn(Phen)2Cl2 as an inorganic catalyst in water at room
temperature resulted excellent yields of the corresponding products in 5
min [174].
An efficient and convenient method has been developed for the

synthesis of 2-amino-4H tetrahydrobenzo[b]pyrans derivatives via one-
pot, three-component condensation of malononitrile, dimedone and
different aldehydes in the presence of a catalytic amount of potassium
٤۲
phthalimide-N-oxyl (POPINO), as a new organocatalyst, in aqueous

media. A variety of 2-amino-tetrahydrobenzo[b]pyrans derivatives were
obtained in high to excellent yields within short reaction times [175].
Recently, Nasseri and Sadeghzadeh [176] prepared and used

magnetic nanoparticle (FeNi3/SiO2/HPG MNPs) catalyst to synthesize 2-
Amino-3- cyanochromene derivatives from various benzaldehyde
derivatives, malononitrile, and dimedone at room temperature under
solvent free conditions.
S. Rostamnia et al used the water dispersed nanoparticles of γ-

Fe2O3 magnetic (nano-γ-Fe2O3), for three component condensation
reaction of 1,3-cyclohexanediones, arylaldehydes, and malononitrile to
give the corresponding tetrahydro-4H-chromenes in up to 95% yield
[177].
٤۳
1.9 Aim of the work
This work was designed to achieve the following targets:

1. Synthesis of overbased detergents of magnesium and calcium fatty
acids additives with high total base number and detergent
efficiency.
2. Evaluation of the prepared detergents as multifunction’s additives
such as antioxidants, viscosity index improvers, and pour point
depressant.
3. Synthesis of new different pyranopyrazole derivatives, derived
from 3-methyl -1- phenyl -2- pyrazolin-5- one, 3- methyl -2-
pyrazolin-5- one, and 5,5-dimethyl 1,3-cyclo hexandion.
4. Synthesis of new different pyranopyrimidine derivative, derived
from 6-amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl-1-phenyl-
1,4-dihydropyrano[2,3-c]pyrazoleaanda5-(4-hydroxyphenyl)-8,8-
dimethyl-8,9-dihydro-3H-chromeno-5-cyano-1,4-dihydropyrano
[2,3-c]pyrazole.
5. Evaluation of the prepared compounds as lubricating oil
antioxidant additives.
٤٤
Chapter Two: Experimental Work
2.1 Materials
2.1.1 Chemicals
Series of fatty acids (1-7) and many chemicals (8-14) were used to
synthesize different overbased detergents (D1-D10). The starting
compounds (S1, S2, and S3) were synthesized by using the chemicals
(16-22). These starting compounds and other chemicals (23-36) were
used to prepare the antioxidants (A1-A26).
The chemicals were used as received from suppliers except
ethylacetoacetate, which was purified by distillation [178].
Table 2.1 shows the properties and manufacturers of the used chemicals.
Table 2.1 Chemicals and their properties and manufactures.
Molecular
Mp. or Purity
No Chemicals weight, Supplier
Bp., οC %
g/mol
1. Octoic (Caprylic) acid 144.22 15-17 98 BDH
2. Decanoic (Capric) acid 172.27 29-31 99 BDH
3. Dodecanoic (Lauric) acid 200.32 43-44 98 H&W Ltd.
4. Tetradecanoic (Myristic) acid 228.38 53-54 97 H&W Ltd.
5. Hexadecanoic (Palmitic) acid 256.43 61-63 99 BDH
6. Octadecanoic (Stearic) acid 284.48 67-69 95 MERCK
7. 9-Octadecenoic (Oleic) acid 282.47 13-14 97 H&W Ltd.
8. Magnesium oxide 40.31 2852 99 BDH.
9. Ammonium hydroxide 35.04 37.7 98 Fluka AG
High National
10. Carbon dioxide gas 44 _ purity gas
(>90) company
11. Toluene 92.14 110-111 99 Fluka AG
12. Ethanol 46.07 79-81 95 BDH
13. Calcium oxide 56.08 2613 98 Fluka, AG
14. Calcium hydroxide 74.093 580 98 Fluka, AG
15. n-Hexane 86.18 68-69 99 BDH
16. 4-Hydroxybenzaldehyde 122.12 113-116 99 Fluka, AG
٤٥
17. Malononitrile 66.06 30-32 98 Fluka AG

18. pipridine 85.16 101 98 Fluka, AG
19. Ethylacetoacetate 130.14 180 99 BDH
Thomas
20. Hydrazine hydrate 50.06 114 80
Baker
21. Phenylhydrazine 108.14 243 99 Fluka, AG
22. Diethylether 74.12 34-36 99 BDH
23. Formic acid 46.03 99-101 98 Fluka, AG
24. Formamide 45.04 210 98 Fluka, AG
25. Dimethylformamide 73.09 153 99 Biosolve
26. Ammonium thiocyanate 76.12 149.5 97 H&W Ltd.
27. Acetic acid 60.05 116-118 98 Fluka, AG
28. Ethanol absolute 46.07 79 99.9 Fluka, AG
29. 1H-indole-2,3-dione (Isatin) 147.13 200 99 BDH
30. 4-Dimethylaminobenzaldehyde 149.2 74 99 BDH
31. 2-Hydroxy-1-naphthaldehyde 172.19 77-80 98 Schuchard
32. 4-Chlorobenzaldehyde 140.57 47-50 99 BDH
33. 4-nitrobenzaldehyde 151.12 103-106 99 BDH
34. Pyrrol-2-aldehyde 95.1 45-47 97 Fluka, AG
5,5-Dimethyl-1,3-cyclohexandion
35. 140.18 146-148 98 Fluka, AG
(Dimedone)
Pyrimidine-2,4,6(1H,3H,5H)-
36. 128.09 245 98 Fluka, AG
trione (Barbituric acid)
37. Olefin copolymer (OCP) - - - Afton
38. Hindered phenol (HP) - - - Afton
39. 2-Methyl-2-butanol
88.15 100-103 99 Fluka, AG
(t-Amyl alcohol)
2.1.2 Base Oil
Base lubricating oil 40 stock was used as diluents in preparation of

overbased detergents, while base lubricating oil 60 stock was used for
preparation of oil blends with the synthesized compounds. These oils
were supplied by Midland Refineries Company. The properties of base
lubricating oils 40 stock and 60 stock were listed in Table 2.2.
٤٦
Table 2.2 Properties of base lubricating oils 40 stock and 60 stock.
Standard test
No. Specification 40 stock 60 stock
method
Kinematic viscosity
1. 14 63.0 ASTM-D 445
at 40 °C, cSt (mm²/s)
Kinematic viscosity
2. 3.3 8.3 ASTM-D 445
at 100 °C, cSt (mm²/s)
3. Viscosity index 101 100 ASTM D- 2270
4. Specific gravity at 60/60 οF 0.856 0.884 ASTM D-4052
5. Pour point ,°C -21 -6 ASTM D-97
6. Flash Point, °C 202 250 ASTM D-92
7. Color 1.0 3.0 ASTM D-1500
2.2 Instrumentation
1. Melting points were measured using Stuart. Scientific. SMP1 melting
point apparatus and are uncorrected.
2. Infrared spectra were recorded on:
- Shimadzu FTIR-8400S Spectrophotometer as KBr disc, (Department of
Chemistry, College of Science, Baghdad University).
-Shimadzu FTIR prestige-21 Spectrophotometer as KBr disc, (Ibn-Sina
Center).
3. Proton and carbon-13 nuclear magnetic resonance 1H NMR and 13
C
NMR spectra were recorded on:
Bruker DPx-400, using CDCl3 as solvent and tetramethylsilane (TMS) as
internal reference (Cardiff University, Cardiff, U.K.).
٤۷
Bruker model ultra shield at 300 MHz using DMSO- d6 and CDCl3 as
solvents and TMS as internal reference (Middle East Technical
university, Ankara, Turkey).
4. Rotary evaporator Yamato RE 510 was used for evaporating solutions.
5. Galanz D90 D25 EL (800W) domestic microwave oven was modified
to use as microwave irradiation reactor as shown in figure 2.1. Infrared
thermometer Victor 305 B (- 50οC to 550οC ) was used to determine the
temperature.
Figure 2.1 The modified microwave irradiation reactor
٤۸
2.3 Test methods

2.3.1 Thin-layer chromatography (TLC)
Thin-layer chromatography was used to monitor the progress of the

reaction and to check the purity of the prepared compounds. TLC was
performed on aluminum sheets pre-coated with silica gel 60 supplied by
Merck. A mixture of ethanol and n-hexane solvents (2:8) was used as
elutant. Spots were detected with iodine vapors.
2.3.2 Total base number (TBN)
Total base number (mg of KOH/g oil) was determined according to

American Society of Testing and Materials ASTM D-4739. This
standard method is based on the potentiometric titration of the basic
constituents in an oil with standardized hydrochloric acid to a fixed end
point.
Total base number of the oil can be calculated by using the following
equation:
N × V × 56.1
TBN =
W
Where, TBN=Total base number (mg of KOH/g oil)
N =Normality of HCl (meq/mL)
V =Volume of HCl, mL, used to titrate the sample
56.1 =Equivalent weight of KOH
W =Weight of oil sample, g
2.3.3 Oxidation stability
Oxidation stability of the synthesized additives was determined

according to Institute of Petroleum testing method IP 280. 25 g of
inhibited oil were blended with 0.25 g of soluble metal catalyst (iron and
copper). An oxygen flow (1L/h) was passed through the oil for 164 hours
٤۹
at 120°C. After the test the volatile acids, the total acidity (T.A) of the oil
and the total precipitated sludge (T.S) were measured and their values
were used to calculate the total oxidation products (TOP).
T. A
TOP% = T. S + 180
561
Where, T.A = total acidity, mg KOH/g

T.S = total sludge, % weight
180 = the average molecular weight of oil oxidation acids.
2.3.4 Kinematic Viscosity
The kinematic viscosity (ν) in cSt or mm²/s at 40 °C (≈ 104 °F)

and 100 °C (≈ 212 °F) was determined according to American Society of
Testing and Materials ASTM D-445, by measuring the time t for a
volume of oil to flow at a constant rate through a capillary held at
constant temperature. The viscometer is calibrated with a fluid of known
viscosity (figure 2.2).
Figure 2.2 Capillary viscometer (a, b - timing marks, B - timing bulb)
The following equation applies for ν calculation:

ν=k.t
٥۰
Where, k = the viscometer constant derived by measuring the flow-rate

of the calibration fluid.
2.3.5 Viscosity Index (VI)
The viscosity index of an oil is determined according to ASTM D-

2270, by comparing its 40°C and 100°C kinematic viscosities with the
viscosities of 0 and 100 VI oils. To be useful in VI measurement, the 0
and 100 VI oils must have the same 100°C viscosity as the oil of interest.
ASTM Standards D2270 contain VI data for many hypothetical reference
oils.
2.4. Experimental Methods
2.4.1 Synthesis of Overbased Magnesium Fatty Acid and Calcium

Fatty Acid Detergents (D1-D10)
Different magnesium fatty acid detergents (D1-D7) were prepared,

using a three neck 500 mL round bottom flask fitted with a gas dispersion
tube, condenser, and mechanical stirrer as a reactor shown in figure 2.3.
The desired fatty acid (0.05 mol) and 20 g of diluents oil were
added to the flask and dissolved in 100 mL mixture of toluene and
ethanol (9:1), then active-60 magnesium oxide (20.15 g , 0.5 mol) was
added to the diluted mixture. The resulted mixture was stirred for 1 h and
then heated up to 65οC. 10mL of ammonia solution was added to the
mixture and 60 mL/min of gaseous CO2 for 3.5 hours was then
introduced into the reactor through gas dispersion tube via the gas flow
meter. The desired overbased magnesium fatty acid detergent was
obtained by filtration through fluted filter paper for residue removal, and
filtrate evaporation to remove the solvents.
٥۱
Overbased calcium palmitate, stearate, and oleate (D8, D9, and

D10) were synthesized by the same method described for the synthesis of
overbased magnesium fatty acid detergents (D1-D7), using calcium
hydroxide ( 22.2 g, 0.3 mol) and calcium oxide (5.6 g, 0.1 mol) instead
of magnesium oxide.
The nomenclature, chemical structure , and color for the prepared

overbased detergents are listed in table 2.3.
1= Three neck round bottom flask

2= Condenser
3= Gas dispersion tube
4= Mechanical stirrer
5= Flow meter
Figure 2.3 Schematic diagram of the reactor
٥۲
Table 2.3 Nomenclature, structure, and color of synthesized

overbased magnesium and calcium detergents
Comp. Common
Chemical structure Color
no. name
Magnesium (CH3(CH2)6COO)2Mg. Pale
D1
caprylate nMgCO3 yellow
Magnesium (CH3(CH2)8COO)2Mg.
D2 white
caprate nMgCO3
D3 white
laurate nMgCO3
D4
myristate nMgCO3 yellow
D5
palmitate nMgCO3 yellow
Magnesium (CH3(CH2)7CH=CH- Pale
D6
oleate (CH2)7COO)2Mg. nMgCO3 yellow
D7 white
stearate nMgCO3
Calcium (CH3(CH2)14COO)2Ca. Pale
D8
palmitate nCaCO3 yellow
Calcium (CH3(CH2)16COO)2Ca. Pale
D9
stearate nCaCO3 yellow
Calcium (CH3(CH2)7CH=CH-
D10 yellow
oleate (CH2)7COO)2Ca. nCaCO3
٥۳
2.4.2 Synthesis of the Starting Compounds for Antioxidants

Preparation
Three starting compounds S1,S2, and S3, which unavailable, were

synthesized according to the procedures discussed below.
2.4.2.1 Synthesis of 3-methyl-1-phenyl-2-pyrazolin-5-one (S1)
H3C N
N
The synthesis of 3-methyl-1-phenyl-2-pyrazolin-5-one (S1) was

taking place according to a reported method in literature [179].
A mixture of redistilled ethylacetoacetate ( 12.75 mL , 0.1 mol)

and phenylhydrazine (9.85 mL , 0.1 mol) was stirred and heated in an
evaporating dish for about two hours. The formed reddish syrup was
cooled, and 25 mL of ether was added with vigorously stirring. The syrup
was solidified and the solid was filtered and recrystallized from
ethanol/water to give 3-methyl-1-phenyl-2-pyrazolin-5-one as colorless
crystals (13.92 g; 79.91% ), m.p=126-128οC.
2.4.2.2 Synthesis of 3-methyl -2-pyrazolin-5-one (S2)
H3C HN
N
٥٤
Ethylacetoacetate ( 12.75 mL , 0.1 mol) was taken in a round

bottom flask and hydrazine hydrate ( 5 mL, 0.1 mol ) was added drop
wise with constant stirring at room temperature. A precipitate was formed
quickly, the reaction mixture was cooled and the resulting precipitate
was collected by filtration and recrystallized from ethanol to give 3-
methyl-2-pyrazolin-5-one as white crystals (9.15 g; 93.28%), m.p=222-
224οC.
2.4.2.3 Synthesis of 2-(4-hydroxylbenzylidine)malononitrile (S3)
CN
OH C C
H
CN
The 2-(4-hydroxylbenzylidine)malononitrile (S3) was prepared by

microwave irradiation of a mixture of 4-hydroxy benzaldehyde (12.2 g,
0.1 mol), malononitrile (6.6 g, 0.1 mol) and 5drops of pipridine in
ethanol (25 mL) for 1 minute at 160 W. After cooling the mixture, gray
precipitate was formed. The precipitate was filtered and recrystalized
from ethanol to give the starting compound S3 as gray crystalline (15.54
g; 91.32%), mp=184-186οC.
٥٥
2.4.3 Synthesis of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl-

NC NH2
HO O
H3C N
A mixture of 2-(4-hydroxylbenzylidine) malononitrile (8.5 g,

0.05mol) and 3-methyl-1-phenyl-2-pyrazolin-5-one (8.7g, 0.05mol) in
ethanol (25 ml), in the presence of few drops of pipridine was irradiated
in microwave for 2 minutes at 160 W. After cooling the solid product was
filtered and crystallized from ethanol to give off-white solid (14.81 g;
86.0%), mp=208-210οC.
Furthermore compound A1 was synthesized using the same
method, but instead of microwave irradiation heating for 2 hours on
hotplate. The yield of compound A1 by this method is 79.11%.
٥٦
2.4.4 Synthesis of 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-4,6-

HN
O C N
OH O
H3C N
A mixture of compound A1 (3.44 g, 0.01 mol) and formic acid (15

mL) was heated for 5 minutes under microwave irradiation at 160 W and
then left to cool at room temperature. The reaction mixture was poured
onto crushed ice, the solid product was filtered, dried, and crystallized
from ethanol to give yellow solid (2.65 g; 71.16%), mp=230-234οC.
Compound A2 was also prepared by using the same method, but
instead of microwave irradiation heating for 12 hours on hotplate, used
to yield 57.73% of compound A2.
2.4.5 Synthesis of 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-4,6-

HN
HN C N
OH O
H3C N
٥۷
A mixture of compound A1 (3.44 g, 0.01 mol) and formamide (10

mL) in dimethylformamide (10 mL) followed by few drops of piperidine.
The reaction mixture was heated for 5 minutes under microwave
irradiation at 160 W, then evaporated the excess solvent, cooled and
poured into ice cold water and neutralized by dilute hydrochloric acid for
complete precipitation. The precipitated solid was filtered, dried and
crystallized from aqueous ethanol to give white solid (2.34 g; 63.0%),
mp=180-184οC.
Furthermore compound A3 was synthesized using the same
method, but instead of microwave irradiation, heating for 8 hours on
hotplate. The yield of compound A3 by this method is 53.37%.
2.4.6 Synthesis of N-[4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-7-

yl] thiourea (A4)
S S
N
C
H2N N NH
H
HO O
H3C N
A mixture of compound A1 (3.44 g, 0.01 mol) and ammonium

thiocyanate (1.5 g, 0.02mol) in acetic acid (10 mL) was heated for 4
minutes under microwave irradiation at 160 W, the product cooled and
poured into ice cold water. The solid product was filtered, dried, and
٥۸
crystallized from ethanol to give yellow solid ( 3.54 g; 76.53%), mp=154-

156οC .
Also, heating for 10 hours on hotplate instead of microwave
irradiation, was used to prepare compound A4 to give 69.2 % yield.
2.4.7 Synthesis of Schiff’s base derivatives (A5-A10)
NC N C Ar
H
HO O
N
H3 C N
The appropriate aromatic aldehyde or ketone (0.005 mol) with two

drops of glacial acetic acid in ethanol (10 mL) was added to a solution of
compound A1 (1.72 g, 0.005 mol) in ethanol (10 mL), and the reaction
mixture was heated for 6-8 minutes under microwave irradiation at 320
W. The product cooled and the separated solid was filtered and
crystallized from ethanol.
Table 2.4 lists the physical properties of the Schiff’s base

derivatives (A5-A10).
٥۹
Table 2.4 The physical properties of the Schiff’s base derivatives (A5-A10)
Molecular
Comp. Mp., Yield,
Ar. Compound name Formula weight, Color ο
no. C %
g/mol
O
NH 4-(4-hydroxyphenyl)-3-methyl-6-((2-oxoindolin-3-
A5 172-
ylidene)amino)-1-phenyl-1,4-dihydropyrano[2,3- C28 H20 O3 N5 474.49 orange 68.92
174
c]pyrazole-5-carbonitrile
Me
6-(4-(dimethylamino) benzylideneamino)-4-(4-
A6 N 216-
hydroxyphenyl) -3-methyl-1-phenyl-1,4- C29 H25 O2 N5 475.54 red 60.57
220
Me dihydropyrano [2,3-c]pyrazole-5-carbonitrile
HO
6-((2-hydroxynaphthalen -1-yl) methyleneamino)-4- 160-

A7
(4-hydroxyphenyl) - 3-methyl-1-phenyl-1,4- C31 H22 O3 N4 498.53 yellow 162 50.96
dihydropyrano [2,3-c]pyrazole-5-carbonitrile Dec.
6-(4-chlorobenzylidene amino)-4-(4-hydroxyphenyl)-
A8 Off- 198-
Cl 3-methyl-1-phenyl-1,4-dihydropyrano [2,3- C27 H19 O2 N4 Cl 466.92 52.31
white 200
c]pyrazole-5-carbonitrile
6-(4-nitrobenzylidene amino)-4-(4-hydroxyphenyl)-3-
A9 NO2 220-
methyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazole-5- C27 H19 O4 N5 477.47 orange 82.68
224
carbonitrile
H 6-((1H-pyrrol-2-yl)methyleneamino)-4-(4-
N
hydroxyphenyl)-3 178-
A10 C25H19O2N5 421.45 yellow 66.32
-methyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazole- 182
5-carbonitrile
٦۰
2.4.8 Synthesis of 6-amino-4-(4-hydroxyphenyl)-3-methyl-2,4-

dihydropyrano[2,3-c]pyrazole-5-carbonitrile (A11)
Compound (A10) was prepared by the same method described for

the preparation of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl-1-
phenyl-1,4-dihydropyrano[2,3-c]pyrazole (A1), but instead of 3-methyl-
1-phenyl-2-pyrazolin-5-one, the 3-methyl -2-pyrazolin-5-one (4.9g,
0.05mol ) was used. Compound (A11) was obtained as white crystals
(12.154 g; 90.61%), with mp:216-218οC.
NC N C Ar
H
HO O
NH
H3C N
By using the same method described for the preparation of Schiff’s

base derivatives (A5-A10), the new Schiff’s base derivatives (A12-A16)
were synthesized by reaction of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-
3-methyl-1,4-dihydropyrano[2,3-c]pyrazole (A11) (1.34 g, 0.005 mol)
with appropriate aromatic aldehyde or ketone (0.005 mol) .
Table 2.5 lists the physical properties of the Schiff’s base

derivatives (A12-A16).
٦۱
Molecular
Comp. Mp., Yield,
Ar. Compound name Formula weight Color ο
no. C %
g/mol
H
N 6-(((1H-pyrrol-2-yl) methylene)amino)-4-(4-
A12 hydroxyphenyl)-3-methyl-2,4-dihydro- C19 H15 O2 N5 345.35 yellow 152-154 68.38
pyrano[2,3-c]pyrazole-5-carbonitrile
O
NH 6-((2-oxoindolin-3-ylidene)amino)- 4- (4-
hydroxyphenyl)-3-methyl-2,4-
A13 C22H16 O3 N5 398.39 yellow 178-180 70.21
dihydropyrano[2,3-c]pyrazole-5-carbonitrile
6-((4-chlorobenzylidene)amino)-4-(4-
A14 Cl hydroxyphenyl)-3-methyl-2,4-dihydro- C21 H15 O2 N4 Cl 390.82 white 208-210 50.73
6-((4-nitrobenzylidene)amino)-4-(4-
A15 NO2 hydroxyphenyl)-3-methyl -2,4- C21 H15 O4 N5 401.37 yellow 128-132 80.1
dihydropyrano[2,3-c]pyrazole -5-carbonitrile
6-((4-hydroxybenzylidene)amino)-4-(4-
A16 OH
hydroxyphenyl)-3-methyl-2,4-dihydro- C21H15 O3 N4 371.37 orange 200-204 52.83
٦۲
2.4.10 Synthesis of 2-amino-4-(4-hydroxyphenyl)-7,7-dimethyl-5-oxo-

5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile (A۱۷)
NC NH2
HO O
CH3
H3C
This compound (A17) was prepared by the same method

described for the preparation of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-
3-methyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazole (A1), using 5,5-
Dimethyl-1,3-cyclohexandion (Dimedone) (7 g, 0.05mol ) instead of 3-
methyl-1-phenyl-2-pyrazolin-5-one .
Compound (A17) was obtained as white crystals (12.98 g; 83.62
%), mp:212-214οC.
2.4.11 Synthesis of 5-(4-hydroxyphenyl)-8,8-dimethyl-8,9-dihydro-

HN
O N
HO O
CH3
H3C
٦۳
Following the same method described in section (2.4.4), compound

(A2) was prepared starting with 5-(4-hydroxyphenyl)-8,8-dimethyl-8,9-
dihydro-3H-chromeno-5-cyano-1,4-dihydropyrano[2,3-c]pyrazole (A17).
Compound (A18) was obtained as white needle crystals (2.12 g;

62.72 %), mp: 226-228οC.
2.4.12 Synthesis of 5-(4-hydroxyphenyl)-4-imino-8,8-dimethyl

HN
HN N
OH O
CH3
H3C
According to the same method described in section (2.4.5)

compound (A19) was prepared starting with 5-(4-hydroxyphenyl)-8,8-
dimethyl-8,9-dihydro-3H-chromeno-5-cyano-1,4-dihydropyrano[2,3-c]
pyrazole (A17).
Compound (A19) was obtained as yellow powder (1.97 g; 58.39
%), mp: 162-166οC.
٦٤
2.4.13 Synthesis of 1-(5-(4-hydroxyphenyl)-8,8-dimethyl-6-oxo-2-

thiourea (A20)
S S
N
C
H2N N NH
H
OH O
CH3
H3C
By using the same method described in section (2.4.6) compound

(A20) was prepared starting with 5-(4-hydroxyphenyl)-8,8-dimethyl-8,9-
dihydro-3H-chromeno-5-cyano-1,4-dihydropyrano[2,3-c]pyrazole (A17).
Compound (A20) was obtained as yellow powder (3.20 g; 74.67
%), mp: 198-200οC.
CN N C Ar
H
HO O
CH3
H3C
By using the same method described for the preparation of Schiff’s

base derivatives (A5-A10) in section (2.4.7), the new Schiff’s base
derivatives (A21-A25 ) were synthesized by using A17 as a starting
٦٥
compound instead of A1. Table 2.6 lists the physical properties of the
Schiff’s base derivatives (A21-A25).
2.4.15 Synthesis of 7-amino-5-(4-hydroxyphenyl)-2,4-dioxo-2,3,4,5-

NC NH2
HO O
O N H
H O
A mixture of 2-(4-hydroxylbenzylidine) malononitrile (8.5 g,

0.05mol) and pyrimidine-2,4,6(1H,3H,5H)-trione (Barbituric acid) (6.4g,
0.05mol) in DMF (25 ml), in the presence of few drops of pipridine was
irradiated in microwave for 8 minutes at 160 W. After cooling the solid
product was filtered and recrystallized from DMF/ethanol to give a
yellow solid (9.1 g; 61.0%), mp:254-256οC.
٦٦
Molecular
Comp.
Ar. Compound name Formula weight, Color Mp., οC Yield, %
no.
g/mol
O
NH 4-(4-hydroxyphenyl)-7,7-dimethyl -5-oxo-2-
A21 ((2-oxoindolin-3-ylidene)amino)-5,6,7,8- C26 H22 O4 N3 440.47 orange 180-184 69.37
tetrahydro-4H-chromene-3-carbonitrile
H
N 2-((1H-pyrrol-2-yl) methylene -amino)-4-(4-
Pale
A22 hydroxyphenyl)-7,7-dimethyl-5-oxo-5,6,7,8- C23 H21 O3 N3 387.43 154-158 57.85
green
tetrahydro -4H-chromene-3-carbonitrile
Me
2-(4-(dimethylamino) benzylidene -amino)-4-
N (4-hydroxyphenyl)-7,7-dimethyl-5-oxo-
A23 C27 H27 O3 N3 441.52 yellow 176-178 52.95
5,6,7,8-tetrahydro -4H-chromene -3-
Me
carbonitrile
NO2
4-(4-hydroxyphenyl)-7,7-dimethyl -2-(4-nitro
A24 benzylideneamino)-5-oxo-5,6,7,8-tetrahydro- C25 H21O5N3 443.45 yellow 168-172 77.02
4H-chromene-3-carbonitrile
HO
2-((2-hydroxy naphthalen -1-yl)

methyleneamino)-4-(4-hydroxyphenyl)-7,7- Deep 166
A25 C29 H24 O4 N2 464.51 56.56
dimethyl-5-oxo-5,6,7,8-tetrahydro-4H- yellow Dec.
chromene-3-carbonitrile
٦۷
2.5 Formulation of oil blends
Blends of different prepared overbased magnesium and calcium

fatty acid detergents (D1-D10) were prepared by dissolving each
detergent in 60 stock base oil with continuous stirring at 60οC for 1 hour.
The prepared 60 stock oil blends contain different dosages (1%, 2%,
3.5% and 5%) of each of synthesized detergent.
Blend oil with standard viscosity index supplied by Midland
Refineries Company was formulated by using the same method.
Blends of compounds (A1-A25 and S3) were prepared by

dissolving 1% of each compound in t-amyl alcohol and mixed with base
oil 60 stock at 80οC for 1 hour.
Blend oil with 1% standard antioxidant supplied by Midland
Refineries Company was formulated in the same method.
٦۸
Chapter Three : Result & Discussion
3.1 Overbased Detergents
3.1.1 Synthesis of Overbased Magnesium and Calcium Fatty Acid

Salts (D1-D10)
The synthesis of overbased magnesium and calcium fatty acid salts

(D1-D10) is similar to that described by Yonglei and coworkers [68,71],
but the xylene and methanol solvent change to toluene and ethanol,
respectively.
Scheme 3.1 describes a general mechanism for the approach used to

synthesize these compounds.
2RCOOH + MO → (RCOO)2Mg + H2O
MO + H2O → M(OH)2
(RCOO)2M + n M(OH)2 + nCO2 → (RCOO)2M·nMCO3+nH2O
Where, M = Mg or Ca
R = CH3(CH2)n - , n = 6, 8, 10, 12, 14, 16, or
CH3(CH2)7CH=CH(CH2)6CH2-
Scheme 3.1 General mechanism of overbased magnesium or calcium

fatty acid salts synthesis.
٦۹
This mechanism consists of a multiphase reaction, including the

neutralization reaction (between fatty acid and magnesium or calcium
oxide) and carbonation reaction. Magnesium or calcium carbonate
(nMCO3) is dispersed in particles smaller than 100 nm [180 ].
The structure of the synthesized compounds were confirmed by

FTIR (table 3.1), and 1H NMR spectroscopies.
FTIR spectra of the prepared compounds (figures 3.1-3.10) show

asymmetric 2927-2918 cm-1 for CH2 group, while symmetric stretching
band for CH2 group appeared between 2854-2850 cm-1. A band in the
region1448-1469 cm-1 refers to the methylene scissoring vibration, while
a band at 723-717 cm-1 refers to the methylene rocking vibration for
straight chain [181]. The carboxylate ion gave a strong asymmetrical
stretching band between 1578-1543 cm-1 [182].
1
H NMR spectra of two of the prepared compounds D5and D7
(figures 3.11 and 3.12), show the signals at d 0.8 for CH3 and d 1.2- 1.3
for (CH2)n because the long chain R group have resonances that occur
over a very narrow range. The two protons near to carboxylate
(CH2COO) appeared at d 1.9-2.0 [183].
۷۰
Table 3.1 : Major FTIR absorptions (cm-1) of synthesized overbased

detergents
No. δCH2 δCH2

Chemical structure nCH3 nCH2 n(C=O)
scissoring rocking
(CH3(CH2)6COO)2Mg. nas.2927 1458
D1 nas.2956 1577 723
nMgCO3 ns.2854
(CH3(CH2)8COO)2Mg. nas.2923 1460

D2 nas.2958 1560 721
nMgCO3 ns.2854
(CH3(CH2)10COO)2Mg. nas.2924 1454

D3 nas.2955 1578 721
nMgCO3 ns.2854
(CH3(CH2)12COO)2Mg. nas2920 1461

D4 nas. 2954 1560 721
nMgCO3 ns. 2850
(CH3(CH2)14COO)2Mg. nas.2918 1460

D5 nas.2954 1568 719
nMgCO3 ns.2850
(CH3(CH2)7CH=CH- nas.2955 1448.8

nas.2924
D6 (CH2)7COO)2Mg. n(=CH)at 1570 723
ns.2854
nMgCO3 3006.8
(CH3(CH2)16COO)2Mg. nas.2922 1456
D7 nas.2956 1571.8 721
nMgCO3 ns.2850
(CH3(CH2)14COO)2Ca. nas.2921 1467

D8 nas.2956 1572 721
nCaCO3 ns.2852
(CH3(CH2)7CH=CH- nas.2958 1448.6

nas.2927
D9 (CH2)7COO)2Ca. n(=CH)at 1577.7 721
ns.2854
nCaCO3 3008
(CH3(CH2)16COO)2Ca. nas.2920 1469
D10 nas.2955 1543 717
nCaCO3 ns.2851
۷۱
(CH3(CH2)14COO)2Mg.nMgCO3
Figure 3.1 FTIR spectrum of overbased magnesium caprylate (D1)
۷۲
(CH3(CH2)8COO)2Mg. nMgCO3
Figure 3.2 FTIR spectrum of overbased magnesium caprate (D2)
۷۳
Figure 3.3 FTIR spectrum of overbased magnesium caprylate (D3)
۷٤
Figure 3.4 FTIR spectrum of overbased magnesium myristate (D4)
۷٥
Figure 3.5 FTIR spectrum of overbased magnesium palmitate (D5)
۷٦
(CH3(CH2)7CH=CH-(CH2)7COO)2Mg. nMgCO3
Figure 3.6 FTIR spectrum of overbased magnesium oleate (D6)
۷۷
Figure 3.7 FTIR spectrum of overbased magnesium stearate (D7)
۷۸
(CH3(CH2)14COO)2Ca.nCaCO3
Figure 3.8 FTIR spectrum of overbased magnesium stearate (D8)
79
(CH3(CH2)7CH=CH-(CH2)7COO)2Ca. nCaCO3
Figure 3.9 FTIR spectrum of overbased Calcium oleate (D9)
80
(CH3(CH2)16COO)2Ca.nCaCO3
Figure 3.10 FTIR spectrum of overbased Calcium stearate (D10)
81
Figure 3.11 1HNMR spectrum of overbased magnesium palmitate (D5)
82
Figure 3.12 1HNMR spectrum of overbased magnesium stearate (D7)
83
Total base number (TBN) were determined for all the prepared
overbased magnesium and calcium fatty acid salts (D1-D10) according to
ASTM D-4739, and the results are listed in table 3.2.
Table ۳.۲ Total base number of synthesized overbased magnesium

and calcium detergents
Comp. TBN
Common name
no. mg KOH/g
Overbased magnesium
D1 76
caprylate
Overbased magnesium
D2 103
caprate
Overbased magnesium
D3 123
laurate
Overbased magnesium
D4 258
myristate
Overbased magnesium
D5 346
palmitate
Overbased magnesium
D6 398
oleate
Overbased magnesium
D7 420
stearate
Overbased calcium
D8 378
palmitate
D9 Overbased calcium oleate 426
Overbased calcium
D10
stearate 411
84
3.1.2 Evaluation of Overbased Magnesium Fatty Acid Salts (D1-D7)

as Detergents
Total base number (TBN) were determined for the 60 stock oil
blends with different overbased magnesium fatty acid detergents (D1-
D7) in different dosages (1, 2, 3.5, and 5 %), the results are shown in
table 3.3.
Figure 3.13 shows the TBN of oil blends with prepared overbased
magnesium fatty acid detergents. This figure show that the overbased
magnesium palmitate (D5), oleate (D6) and stearate (D7) detergents give
the higher TBN.
25
20
Total Base Number
Wieght (% )of detergent
15
10
in the oil
٥
5 ۳.٥
۲
0
۱
Figure.3.13 The TBN of oil blends with prepared overbased

magnesium fatty acid (D1–D7) detergents at different weight
percentages
۸٥
Table 3.3 Total base number (mg of KOH/g) of blend oils with (D1-D7) detergents
Oil with Oil with Oil with Oil with Oil with Oil with Oil with
Wt.,% of overbased overbased overbased overbased overbased overbased overbased
detergent Mg- Mg- Mg- Mg- Mg- Mg- Mg-
in the oil caprylate caprate laurate myristate palmitate oleate stearate
(D1) (D2) (D3) (D4) (D5) (D6) (D7)
1 1.63 1.41 1.63 1.66 1.69 1.71 2.84

2 1.28 2.34 2.7 2.74 2.9 4.93 4.85
3.5 4.9 5.6 5.8 5.9 8.8 10.4 10.9
5 6.8 7.55 10.38 12.8 15.9 24.5 20.6
*TBN of the blank = 0.87 mg of KOH/g
۸٦
The efficiency of oil blends with prepared overbased magnesium

fatty acid detergents was calculated by the following equation:
TBN of sample − TBN of blank

Effeciency, % = × 100
TBN of blank
Table 3.4 lists the efficiency of the overbased detergents (D1-D7)

blended with oils at different concentrations. Figure 3.14 obviously show
that the overbased magnesium palmitate (D5), oleate (D6), and stearate
(D7) detergents give the higher efficiency.
Palmitic and stearic acids are the most common saturated fatty
acids found in animals, and plants. Because they are inexpensively
available and environmentally friendly, so palmitic and stearic acids can
be recommended for lubricating oil detergent preparation.
3000 Wieght (% )of detergent in the oil

2500
Efficiency %
2000
1500
1000
500 ٥
0 ۳.٥
۲
۱
Figure 3.14 The efficiency of oil blends with prepared

overbased magnesium fatty acid detergents (D1-D7)
۸۷
Table 3.4 The efficiency of overbased magnesium fatty acid detergents (D1-D7)
Wt.,% of Overbased Overbased Overbased Overbased Overbased Overbased Overbased

detergent Mg- Mg- Mg- Mg- Mg- Mg- Mg-
in the oil caprylate caprate laurate myristate palmitate oleate stearate
(D1) (D2) (D3) (D4) (D5) (D6) (D7)
1 87.35 62.02 87.35 90.80 94.25 96.55 226.42

2 47.12 168.96 191.95 214.94 233.33 466.67 457.47
3.5 463.21 543.67 566.67 578.16 681.61 1095.40 1152.87
5 681.61 767.81 1093.10 1371.26 1727.58 2716.09 2267.81
۸۸
3.1.3 Analysis of Variance (ANOVA) Tests
The results of TBN were treated by using two-way F-test analysis

of variance (ANOVA) tests to measure the effects of two factors ,number
of carbons in the chain of synthesized overbased detergents (D1-D7) and
their concentrations (1-5% wt/wt) in the blended oil, simultaneously.
Table 3.5 shows the summarized ANOVA (sum of squares, degree

of freedom, mean squares, F-value) and significant test results of the
effect on TBN by weight% added and carbon number in the chain of
overbased detergents. The significant level of using different carbon
numbers in the chain have a value of 0.620 which means that there is no
significant difference because the significant level is greater than 0.05
(95% confidence), while the significant level obtained for blends with
different weight percentage of different additives have the value 0.00, and
this means that there is a significant difference in the effect of adding
different percentage of overbased detergent.
Table 3.5 The effect on TBN by weight% added and carbon number
in the chain of D1-D7
Sum. of Degree Mean

Source F-value Significant
Squares of freedom Square
Carbon number
167.467 6 27.911 0.745 0.620
in the chain
Weight% added 641.647 3 213.882 16.396 0.000
Moreover, all the TBN results were treated by using t-test analysis
for comparison between the weight percentages added of different
۸۹
prepared overbased magnesium detergents, according to Tukey HSD and

Scheffe methods as shown in table 3.6.
Table 3.6 Multiple Comparison between weight% added of D1-D7
Method (I) Weight added (J) Weight added Sig.*

Tukey 1.0% 2.0% 0.909
3.5% 0.047
5.0% 0.000
2.0% 1.0% 0.909
3.5% 0.174
5.0% 0.000
3.5% 1.0% 0.047
2.0% 0.147
5.0% 0.008
5.0% 1.0% 0.000
2.0% 0.000
3.5% 0.008
Scheffe 1.0% 2.0% 0.930
3.5% 0.036
5.0% 0.000
2.0% 1.0% 0.930
3.5% 0.238
5.0% 0.000
3.5% 1.0% 0.036
2.0% 0.238
5.0% 0.015
5.0% 1.0% 0.000
2.0% 0.000
3.5% 0.015
* Sig.˂ 0.05, there is a significant difference.
* Sig.˃ 0.05, there is no significant difference.
Based on the TBN values of 1% detergent blended oil with those

blends with 2%, 3.5%, and 5%, it could be concluded that there is a
۹۰
significant difference when the comparison with 3.5% and 5%, while
there is no significant difference with 2%. Also a significant difference in
the effect of adding 2% comparing with 5%, could be concluded, but
there is no significant difference comparing with 3.5%. A significant
difference in the effect of adding 3.5% comparing with 5% was observed.
According to t-test analysis of the TBN for the comparison

between carbon numbers in the chain of different prepared overbased
magnesium detergents (table 3.7), there is no significant difference for all
the used compounds.
۹۱
Table 3.7 Multiple Comparison between carbon number in the chain
Method (I) Carbon (J) Carbon Sig. Method (I) Carbon (J) Carbon Sig.
number number Compound Compound
Tukey D1 (C8) D2 (C10) 1.000 Scheffe D1 (C8) D2 (C10) 1.000
HSD D3 (C12) 1.000 D3 (C12) 1.000
D4 (C14) 0.999 D4 (C14) 1.000
D5 (C16) 0.989 D5 (C16) 0.997
D6 (C18:1) 0.710 D6 (C18:1) 0.869
D7 (C18:0) 0.786 D7 (C18:0) 0.910
D2 (C10) D1 (C8) 1.000 D2 (C10) D1 (C8) 1.000
D3 (C12) 1.000 D3 (C12) 1.000
D4 (C14) 1.000 D4 (C14) 1.000
D5 (C16) 0.996 D5 (C16) 0.999
D6 (C18:1) 0.784 D6 (C18:1) 0.909
D7 (C18:0) 0.850 D7 (C18:0) 0.942
D3 (C12) D1 (C8) 1.000 D3 (C12) D1 (C8) 1.000
D2 (C10) 1.000 D2 (C10) 1.000
D4 (C14) 1.000 D4 (C14) 1.000
D5 (C16) 1.000 D5 (C16) 1.000
D6 (C18:1) 0.877 D6 (C18:1) 0.954
D7 (C18:0) 0.925 D7 (C18:0) 0.974
D4 (C14) D1 (C8) 0.999 D4 (C14) D1 (C8) 1.000
D2 (C10) 1.000 D2 (C10) 1.000
D3 (C12) 1.000 D3 (C12) 1.000
D5 (C16) 1.000 D5 (C16) 1.000
D6 (C18:1) 0.932 D6 (C18:1) 0.977
D7 (C18:0) 0.963 D7 (C18:0) 0.988
D5 (C16) D1 (C8) 0.989 D5 (C16) D1 (C8) 0.997
D2 (C10) 0.996 D2 (C10) 0.999
D3 (C12) 1.000 D3 (C12) 1.000
D4 (C14) 1.000 D4 (C14) 1.000
D6 (C18:1) 0.980 D6 (C18:1) 0.994
D7 (C18:0) 0.992 D7(C18:0) 0.998
D6(C18:1) D1 (C8) 0.710 D6 (C18:1) D1 (C8) 0.869
D2 (C10) 0.784 D2 (C10) 0.909
D3 (C12) 0.877 D3 (C12) 0.954
D4 (C14) 0.932 D4 (C14) 0.977
D5 (C16) 0.980 D5 (C16) 0.994
D7 (C18:0) 1.000 D7 (C18:0) 1.000
D7 (C18:0) D1 (C8) 0.786 D7 (C18:0) D1 (C8) 0.910
D2 (C10) 0.850 D2(C10) 0.942
D3 (C12) 0.925 D3 (C12) 0.974
D4 (C14) 0.963 D4 (C14) 0.988
D5 (C16) 0.992 D5 (C16) 0.998
D6 (C18:1) 1.000 D6(C18:1) 1.000
۹۲
3.1.4 Evaluation of Overbased Magnesium Fatty Acid Salts (D5 and

D7) as Antioxidant
Usually the excepted percentage of detergent used for engine

crankcase lubricating oils is not less than 2% [184].
For further, evaluation of the selected overbased magnesium

palmitate (D5) and overbased magnesium stearate (D7), the base oil (60
stock) as well as its blends with 2% by weight of detergents were
subjected to severe oxidation condition in the presence of a soluble iron
and copper catalyst at 120 οC for 164 hours while being subjected to a
constant one-liter/hour flow of oxygen, according to IP280.
Results given in table 3.8 and figure 3.15 show that the blends with
2% by weight overbased Mg-palmitate (D5) or overbased Mg-stearate
(D7) have higher oxidation stability compared with the blend of the same
oil with standard antioxidant used by Midland Refineries Company.
Overbased detergents, especially organo-alkaline earth salt

compounds, are type of metal deactivators antioxidants, which act as
film-forming agents in two ways. First, they coat the metal surface, thus
preventing metal ions from entering the oil. Second, they minimize
corrosive attack of the metal surface by physically restricting access of
the corrosive species to the metal surface [4]. Thus, the overbased
magnesium palmitate and overbased magnesium stearate, can show an
antioxidant effect, because the carbonate in their structure performs acid
neutralization, and the linear structure of the chain forms the protective
surface film.
۹۳
Table 3.8 Oxidation stability results of blend oils D5 and D7
Oil with Oil with

overbased overbased
Characterization Blank
Mg-palmitate Mg-stearate Standard
(D5) (D7)
Volatile acidity, 0.0025

0.0037 0.0037 0.0060
(mg of KOH/g)
Soluble acidity, 0.2571
0.04939 0.01234 0.1230
(mg of KOH/g)
Total acidity, 0.259
0.05309 0.01604 0.1290
mg of KOH/g
Total sludge, 0.0880
0.280 0.01114 0.00
(wt,%)
Total Oxidation
Products (TOP,%) 0.363 0.0281 0.05146 0.1298
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
Blank Mg-palmitate Mg-stearate Standard
(D5) (D7)
Total sludge (wt%) Total oxidation product (TOP%)

Total acidity (mg KOH/g oil)
Figure 3.15 Total sludge, acidity and oxidation products of D5and D7
۹٤
3.1.5 Evaluation of Overbased Magnesium Fatty Acid Salts (D5 and

D7) as Viscosity Index Improvers and Pour Point Depressant
The viscosity index (VI) is an indicator of the change in viscosity

as the temperature is changed. The higher the VI, the less effect
temperature has on viscosity change.
The oil blends of overbased magnesium palmitate (D5) and stearate
(D7), in different concentrations, were evaluated as viscosity index
improver. It is clear from the VI data tabulated in table 3.9 and the plots
of VI vs. concentration (Figure 3.16), that VI values increases with the
increase in additive concentration in the base oils studied.
The VI values of the oil blends indicated that better performance is

obtained with the 5% overbased magnesium stearate (D7) having longer
carbon chain. This blend has approximately the same VI as the blend with
5% of the olefin co-polymer (OCP) standard.
Long chain n-paraffin give the highest viscosity index to an oil [7].
A possible explanation may be, as the temperature is raised, the lube oil
viscosity gets a decrease and as a result of that the size of the micelle
increase. This increase in micelle size counterbalanced the reduction of
the viscosity of the lube oil and hence, decreases the change of viscosity
with temperature of the mixture [185].
The efficiency of oil blends with D5 and D7 was calculated and the
results were listed in table 3.10. Figure 3.14 obviously shows that the
overbased magnesium stearate (D7) in 5 wt.% concentration gives the
highest efficiency.
۹٥
Table 3.9 Viscosity index of blend oils (D5 and D7)
Oil with Oil with

wt.% overbased overbased
Standard
in the oil Mg-palmitate Mg-stearate
(D5) (D7)
1 106 107 118
2 112 117 121
3.5 123 125 128
5 126 135 136
*Viscosity index of the blank =100
140
130
Viscosity Index
120
Blank
Mg-palmitate (D5)
110
Mg-stearate (D7)
100 Standard
90
۱ ۲ ۳.٥ ٥
Wt% in the oil
Figure. 3.16 Viscosity index of D5andD7 at different concentrations
۹٦
Table 3.10 Efficiency of overbased magnesium fatty acid detergents

(D5 and D7) as VI improver
Oil with Oil with

overbased overbased
wt.%
Mg-Palmitate Mg-stearate Standard
in the oil
(D5) (D7)
1 6 7 18
2 12 17 21
3.5 23 25 28
5 26 35 36
40
35
30
Efficiency %
25
20
15
٥
wt.% in the oil
10
۳.٥
5
۲
0
۱
Mg-
palmitate Mg-stearate
(D7) Standard
(D5)
Figure. 3.17 Efficiency of D5 and D7 as VI improver
۹۷
The pour point of oil blends with 2 and 3.5% overbased

magnesium palmitate (D5) and stearate (D7) was investigated. All this
additives depressed the oil pour point from -6 οC to -15 οC, as shown in
table 3.11.
Table 3.11 Pour point (οC) of oil blend with 2and 3.5wt.% overbased
Mg-palmitate (D5) and stearate (D7)
Oil with Oil with Oil with Oil with

2wt.% 3.5 wt.% 2 wt.% 3.5 wt.%
Blank overbased overbased overbased overbased
Mg-palmitate Mg-palmitate Mg-stearate Mg-stearate
(D5) (D5) (D7) (D7)
-6 -15 -15 -15 -15
۹۸
3.1.6 Evaluation of Overbased Calcium Fatty Acid Salts (D8-D10) as

Detergents
Table 3.12 lists TBN of the 60 stock oil blends with prepared
overbased calcium fatty acid detergents (D8, D9, and D10) in different
dosages (1, 2, 3.5, and 5 %). According the value of TBN, the efficiency
was calculated and lists in table 3.13.
Figures 3.18 and 3.19 obviously illustrate good TBN and

efficiency values of overbased calcium palmitate (D8), oleate (D9), and
stearate (D10) detergents.
TBN and efficiency of overbased calcium fatty acid detergents

(D8-D10) were comparing with overbased magnesium fatty acid
detergents (D5-D7) as shown in figures 3.18 and 3.19. The magnesium
detergents have greater TBN and efficiency than calcium detergents.
The greater neutralizing ability of magnesium detergents was

attributed to the fact that neutralization of inorganic acid could occur
within the aqueous phase, and that magnesium carbonate had greater
aqueous solubility than calcium carbonate [180, 186].
۹۹
Table 3.12 Total base number (mg of KOH/g) of blend oils (D8-D10)
Oil with Oil with Oil with

wt.% of
overbased overbase overbased
detergent
Blank Ca-palmitate Ca-oleate Ca-stearate
in the oil
(D8) (D9) (D10)
1 0.87 4.3 4.15 4.7

2 0.87 4.1 4.4 4.9
3.5 0.87 5.3 4.2 5.0
5 0.87 7.3 7.8 9.8
10
9
8
Total Base Number
7
6
Wieght (% )of detergent
5
4
in the oil
3 ٥
2 ۳.٥
1 ۲
0 ۱
Figure. 3.18 The TBN of oil blends with prepared overbased calcium
fatty acid (D8–D10) detergents at different weight percentages
۱۰۰
Table 3.13 Efficiency of overbased calcium fatty acid detergents (D8-

D10)
wt.% of Oil with Oil with Oil with
detergent overbased overbased overbased
in the oil Ca-palmitate Ca-oleate Ca-stearate
(D8) (D9) (D10)
1 354.25 377.01 440.22
2 371.26 405.74 463.21
3.5 509.19 382.75 474.71
5 739.08 796.55 1026.43
1200
1000
Efficiency %
800
600
٥
400
۳.٥ Wieght (% )
200
۲
0
۱
Figure. 3.19 Efficiency of oil blends with prepared overbased

calcium fatty acid detergents (D8-D10)
۱۰۱
25
20
Wieght (% )of detergent in the oil

TBN
15
10
5
٥
0 ۳.٥
۲
۱
Figure. 3.20 TBN comparison of overbased magnesium detergents

with overbased calcium detergents
3000
2500
2000
1500
Efficiency %
1000
Wieght (% )of detergent in the oil
500
٥
0 ۳.٥
۲
۱
Figure. 3.21 Efficiency comparison of overbased magnesium

detergents with overbased calcium detergents
۱۰۲
3.3 Antioxidants
3.3.1 Synthesis of 2-(4-hydroxylbenzylidine)malononitrile (S3)
2-(4-hydroxylbenzylidine) malononitrile (S3) was chosen as a

starting material for the synthesis of different pyranopyrazoles and
pyranopyrimidines derivatives.
The hydroxylbenzylidinemalononitrile S3 was prepared by

Knoevenagel condensation of malononitrile with 4-hydroxy
benzaldehyde in presence of pipridine as catalyst under microwave
irradiation.
Knoevenagel condensation [186] is one of the most important

methods for the formation of carbon-carbon double bond [187].
Knoevenagel condensation reaction is widely used in synthesis of
arylidenemalononitriles, the important intermediates for the synthesis of
various organic compounds, mainly by cyclization reactions [188].
Arylidenemalononitriles was obtained from the reaction of
methylene active compound (malononitrile) with aromatic aldehyde in
the precence of base; the mechanism is illustrated in scheme 3.2.
۱۰۳
Scheme 3.2 Knoevenagel condensation mechanism
The 2-(4-hydroxylbenzylidine) malononitrile (S3) was identified

by its FTIR spectrum and melting point which were identical with
literature [189]. The FTIR spectrum of S3 (figure 3.21) showed a
stretching bands at 3353.9 cm-1 for phenolic OH, and at 3028 cm-1 for
aromatic CH. Nitrile group appeared, as sharp and strong band at 2227.6
cm-1. The bands at the region 1610.4- 11519.8 cm-1 are due to (C=C), and
benzylidineringa[190].
۱۰٤
CN
OH C C
H
CN
Figure 3.21 FTIR spectrum of (S3)
۱۰٥
3.3.2 Synthesis of pyranopyrazoles and pyranopyrimidines derived

from 3-methyl-1-phenyl-2-pyrazolin-5-one (A1-A10)
The synthetic route of compounds (A1-A10) was started with 2-(4-

hydroxylbenzylidine)malononitrile (S3) in different reactions as shown in
scheme 3.3.
3.3.2.1 Synthesis of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl-

When 2-(4-hydroxylbenzylidine)malononitrile (S3) reacted with 3-

methyl-1-phenyl-2-pyrazolin-5-one (S1) in the presence of pipridine as
base under microwave irradiation, the 6-amino-4-(4-hydroxyphenyl)-5-
cyano-3-methyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazole (A1) was
obtained according to the mechanism illustrated in scheme 3.4.
۱۰٦
O NC NH2
CN
HO C C + H3C N ph HO O
H
N
CN
(S3) N
H3C ph
N
HN (A1)
H
HCOO O
O N NH 2
C
H
HN
4 CN
HO O
HS
HN N
2N
N
H3C ph
N HO O
(A2)
(Schif f base)
H
O
C
N
H3C ph
N
Ar
(A3)
S S
N
C
H2N N NH
H
HO O
Me
O , N N
H3C ph
N Me N
H
(A6)
(A5) (A4)
OH NC N C Ar
H
Ar = , Cl
(A7) HO O
(A8)
,
NO2 N
N
H3C ph
H N
(A9) (A10)
Scheme 3.3 Synthetic rout of compounds A1-A10
۱۰۷
Scheme 3.4 Formation mechanism of compound (A1)
Compound A1 was characterized by FTIR, and melting point

which were identical with literature [191]. FTIR spectrum (figure 3.22)
showed stretching bands at 3414 and 3317 cm-1 (NH2), 2179 cm-1
(C≡N), and at 1658 cm-1 due to C=N.
3.3.2.2 Synthesis of 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-4,6-

Treatment of compound A1 with excess formic acid under

microwave irradiation, gave 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-
4,6-dihydropyrazolo[3', 4':5,6]pyrano[2,3-d]pyrimidine-5-one (A2).
۱۰۸
NC NH2
HO O
H3C N
Figure 3.22 FTIR spectrum of (A1)

۱۰۹
The structures of the synthesized compounds were confirmed by FTIR,

1H NMR, and 13C NMR.
FTIR spectrum of compound A2 showed an absorption bands at

3250 cm-1 (OH), and 3176.5 cm-1 (NH). The NH2 and C≡N bands were
disappeared, while a characteristic (C=O) lactam band was appeared at
1701.8 cm-1 (figure 3.23).
The 1H- NMR spectrum (figure 3.24) showed the singlet signals at
δ10.81 and δ9.14 were assigned for OH and NH protons respectively.
Proton of CH pyrmidone appeared at δ 8.6. Aromatic protons appeared as
multiplet at δ7.95- δ6.6 and CH3 protons appeared at δ2.1 as singlet.
13
CNMR spectrum (figure 3.25) showed a characteristic signals at
173.7 ppm for C=O, the carbons of pyran ring (C-O-C) appeared at
163.5ppm and 162.4ppm, while carbons of C=N for pyrimidone and
pyrazol rings appeared at 148.9ppm and 138.9ppm, respectively.
Aromatic carbons attached to phenolic OH, and to N atom appeared at
152.3ppm, and 137.9ppm, respectively. The aromatic carbons of phenol
ring appeared at 129.4, 128.7, and 115.3ppm, while the aromatic carbons
of phenyl ring appeared at 125.4, 124.8, and 123.1ppm. Carbon of methyl
group appeared at 13.6ppm [181].
۱۱۰
۱۱۱
HN
O C N
OH O
H3C N
Figure 3.24 1HNMR spectrum of (A2)

۱۱۲
HN
O C N
OH O
H3C N
13
Figure 3.25 CNMR spectrum of (A2)
۱۱۳
۱۱٤
3.3.2.3 Synthesis of 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-4,6-

Reaction of compound A1 with formamide under microwave

irradiation, afforded 4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-4,6-
according to the mechanism illustrated in scheme 3.5.
OH
H2N CH
NH2 N C NH
NC
HO O H C NH2 HO O
N N
H3C H3C ph
ph N
N
(2)
OH2
N HN HN CH
H2N C N HN C N HN C NH
HO O HO O HO O
N N N
H3C ph H3C ph H3C ph
N N N
The structure of compound A3 was confirmed by FTIR, 1H- NMR,

and 13CNMR.
FTIR spectrum (figure 3.26) showed stretching bands at 3387 cm-1

(NH imine), and 3190.2 cm-1 (NH). The NH2 and C≡N bands were
disappeared.
۱۱٤
۱۱٥
In the 1H- NMR spectrum (figure 3.27) two signals for OH and NH
as a singlet at δ10.6 and δ9.1, respectively. The appearance of signal at
δ7.44 for 2H (NH2) indicates that compound A3 exist in a tautomeric
mixture as shown in scheme 3.5. Aromatic protons appeared as multiplet
at δ7.7- δ6.6. The signal at δ3.6 was assigned to pyran proton, while CH3
protons appeared at δ1.99.
13
CNMR spectrum (figure 3.28) showed signals at 164.3 and 155.7
ppm for C=N pyrazol and imine, while the C-OH appeared at 150 ppm.
Carbon of pyrimidin appeared at 148.4 ppm, while carbons of pyran ring
(C-O-C) appeared at 139.6 and 138 ppm. The aromatic carbons appeared
at 131.5-118.4ppm. A signal at 107.5 ppm was attributed to carbon
attached to the nitrogen atom of NH2 [181].
۱۱٦
HN
HN C N
OH O
H3C N
۱۱۷
HN
HN C N
OH O
H3C N
13
Figure 3.28 CNMR spectrum of (A3)
۱۱۸
3.3.2.4 Synthesis of N-[4-(4-hydroxyphenyl)- 3-methyl-1-phenyl-7-

yl] thiourea (A4)
The compound A4 was synthesized by reacting one mole of A1

with two moles ammonium thiocyanate in acetic acid. The formation of
A4 may be visualized by the mechanism presented in scheme 3.6.
NH
C S : NH4
NC NH
NC NH2
O
Ar
O NH4-S-C N
Ar
N
H3 C Ph
N N
H3 C Ph
N
H S H S H2N S
N N C
S
H
H2N C N N H HN N H N C NH
NH4-S-CN
O O
Ar O Ar
Ar
N N
N H3 C
H3 C Ph Ph
N H3 C Ph N
N
Ar = HO
۱۱۹
The structure of this compound was confirmed by FTIR and 1H-

NMR . FTIR spectrum showed a broad at 3340 cm-1 which was attributed
to overlap NH2 and OH bands. Stretching NH bands appeared at 3186.4
and 3167.1 cm-1. The IR spectrum also showed the disappearance of C≡N
band, and appearance of C=S at 1261.4 cm-1 [192] (figure 3.29).
1
H-NMR spectrum (figure 3.30) showed signals at δ10.8 for OH
and δ8.65 for NH. Protons of aromatic rings appeared as multiplet at the
region δ6.68- 7.95. Protons of NH2 appeared at δ7.3, while the proton of
pyran appeared at δ5.3. Protons of methyl group appeared as singlet at
δ2.3.
۱۲۰
Figure 3. 29 FTIR spectrum of (A4)
۱۲۱
S S
N
C
H2N N NH
H
HO O
H3C N
۱۲۲
3.3.2.4 Synthesis of Schiff base derivatives (A5-A10)
The reaction of compound A1 with different aromatic aldehydes or

ketone in absolute ethanol and few drops of glacial acetic acid, gave the
desired Schiff-base derivatives (A5-A10). The general mechanism of the
reaction illustrated in Scheme 3.7.
Scheme 3.7 General mechanism of Schiff-base formation
The reaction proceeds via nucleophilic attack of the amine on the

carbonyl carbon of the aldehyde or ketone with the loss of a water
molecule [193].
Schiff-base derivatives A5-A10 were identified by FTIR

spectroscopy.
The FTIR spectra of the prepared compounds are shown in figures (3.31-
3.36) and the characteristic absorption bands are listed in table 3.14.
۱۲۳
Table 3.14 FTIR spectral data (cm-1) of Schiff-base derivatives (A5-

A10)
NC N C Ar
H
HO O
N
H3 C N
Com. Ar. nCH nC≡N nC=N γ C-H Other

no. arom. & arom. bands
nC=C
O
NH ν N-H
1654.9 3201.8
A5 3066.8 2194.9 813.9
1612.5 νC=O
1728.2
Me
N 1668.3
A6 2210.3 -
Me 1614.3 817.6
HO
1654.8
A7 3068.5 2200.1 -
1618.2 817.7
1647.2 ν C-Cl
A8 Cl 2175.7
1612.5 678.9
810.1
ν NO2
1647.1 808.2 1514asym
A9 NO2 3072 2216
1612.4 1342.3sy
m.
H
N
ν N-H
A10 3058.9 2181.3 1656.7
813.9 3315.4
۱۲٤
۱۲٥
۱۲٦
۱۲۷

۱۲۸
۱۲۹
۱۳۰
3.3.3 The comparison between conventional and microwave

synthesis
Excitation with microwave radiation results in the molecules

aligning their dipoles within the external field. Strong agitation, provided
by the reorientation of molecules, in phase with the electrical field
excitation, causes an intense internal heating. Microwaves act as high
frequency electric fields and will generally heat any material containing
mobile electric charges, such as polar molecules in a solvent or
conducting ions in a solid. Polar solvents are heated as their component
molecules are forced to rotate with the field and lose energy in collisions.
The main advantages of microwave heating over conventional

heating are faster reaction, better yield, higher purity, and lower
energy usage [194].
The microwave can use higher temperatures than conventional

heating system, and consequently the reactions are completed in few
minutes instead of hours. During microwave irradiation, less
formation of side products are observed, and the product is recovered
in higher yield. Consequently, the purification step is faster and easier.
The two methods, conventional heating and microwave irradiation,

were used to prepare the compounds A1-A10. Table 3.15 shows
obviously the differences in reaction time, and yield which lead to
prefer microwave assisted organic synthesis.
۱۳۱
Table 3.15 Comparison of conventional and microwave synthesis
Conventional heating Microwave irradiation

Comp. Reaction Yield, % Power, Reaction Yield, %
no. time (h.) W. time
(min.)
A1 2 79.1 160 2 86.0
A2 12 57.7 160 5 71.1
A3 7 53.3 160 5 63.0
A4 10 62.2 160 4 76.5
A5 5 52.1 320 6 68.9
A6 6 48.5 320 6 60.5
A7 8 43.7 320 8 50.9
A8 8 41.9 320 8 52.3
A9 4 70.4 320 6 82.6
A10 6 56.6 320 6 66.3
3.3.4 Evaluation of pyranopyrazoles and pyranopyrimidines

derived from 3-methyl-1-phenyl-2-pyrazolin-5-one (A1-A7)
as antioxidants
Oil oxidation at elevated temperatures normally leads to the

formation of acidic components which are responsible for the sludge
deposition metal corrosion and fatigue [4]. The oxidation stability of the
blended oils was tested by IP 280. This method has been used for
determination of the resistance to oxidation under specified conditions of
unused inhibited mineral turbine oils. The value of the total oxidation
۱۳۲
products (TOP) was determined, the lower the TOP value the better the
oxidation stability. Total sludge (wt%), volatile acidity and soluble
acidity (mg KOH/g oil) are measured, a low result indicates good
performance [195].
The evaluation results of oil blends are shown in table 3.16, and
figure 3.37. The results showed that blend A5 has higher oxidation
stability compared with the base oil (blank) and approximately the same
oxidation stability as the blend with standard antioxidant, while blend A4
has higher oxidation stability than the blend with standard antioxidant.
According to the structure of compound A5, which has isatine ring, an
active scavenger of radicals [196], while compound A4 has a fused
pyranopyrimidine moiety with thiourea, and thiourea derivatives are
autooxidation inhibition and have a decomposition effect of
hydroperoxide [197].
Compound A6 shows a good oxidation stability comparing with

the blank, while compounds S3, A1, A2, A3 are not oxidation stable, and
compound A7 show a bad oxidation stability, and this may be due to low
decomposition point (162 οC).
۱۳۳
Table 3.16 Oxidation stability results of blend oils (A1-A7 and S3)
Characterization Blank S3 A1 A2 A3 A4 A5 A6 A7 Standard
Volatile acidity 0.0025 0.0025 0.0025 0.005 0.0197 0.0049 0.0148 0.0123 0.00 0.006
(mg KOH/g oil)
Soluble acidity 0.2571 0.1285 0.2571 0.1283 1.111 0.01234 0.087 0.111 0.385 0.123
(mg KOH/g oil)
Total acidity 0.2596 0.131 0.2596 0.1333 1.1307 0.01724 0.1018 0.1233 0.385 0.129
(mg KOH/g oil)
Total sludge 0.280 0.723 0.360 0.540 0.092 0.07989 0.1084 0.1664 0.878 0.088
(wt,%)
Total oxidation 0.363 0.765 0.4432 0.582 0.471 0.0854 0.1299 0.206 1.0015 0.1298
product (TOP,%)
۱۳٤
1.2
0.8
0.6
0.4
0.2
0
Blank S3 A1 A2 A3 A4 A5 A6 A7 Standard
Total sludge (wt%) Total oxidation product (TOP%) Total acidity (mg KOH/g oil)
Figure 3.37 Total sludge, acidity and oxidation products of S3, A1-A7
۱۳٥
۱۳٦
3.3.5. Synthesis of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl-

1,4-dihydropyrano[2,3-c]pyrazole (A11) and it Schiff base
derivatives (A12-A16)
2-(4-Hydroxylbenzylidine)malononitrile (S3) reacted with 3-

methyl-2-pyrazolin-5-one in the presence of pipridine as a base under
microwave irradiation, to synthesize 6-amino-4-(4-hydroxyphenyl)-5-
cyano-3-methyl-1,4-dihydropyrano[2,3-c]pyrazole (A11).
The compound A11was reacted with different aromatic aldehydes,

and isatine give the desired Schiff-base derivatives (A12-A16). All these
reactions were illustrated in Scheme 3.8.
Scheme 3.8 Synthesis and reactions of compound (A11)
۱۳٦
Compound A11 was characterized by FTIR, 1H- NMR, 13C- NMR

and melting point which were identical with literature [199].
FTIR spectrum (Figure 3.38) showed a split broad band at 3433,

3387, and 3305 cm-1, which was assigned to OH group, the asymmetric
and symmetric stretching bands of NH2, and NH groups. IR spectrum
also showed a stretching bands at 2179 cm-1 for C≡N group, and at
1658 cm-1 due to C=N [190].
The 1H- NMR spectrum (δ-ppm) of compound A11 (figure 3.39)

showed signals at δ1.79 (3H-singlet) for CH3, and δ4.48 (1H- singlet) for
C-H pyrane. The aromatic protons (9H- multiplet) appeared at δ6.97-
7.68, while the NH2 appeared as singlet at δ6.79. The spectrum showed
the singlet signals at δ12.05 and δ9.28 were assigned for NH and OH
protons, respectively.
13
161.1ppm, and 156.4ppm for the carbons of pyran ring (C-O-C) while,
C=N for pyrazol ring appeared at 156.4ppm. The carbon attached to OH
in aromatic ring appeared at 155.2ppm while, the other aromatic carbons
appeared at 135.2-115.5ppm. Carbon of methyl group appeared at
10.2ppm [198].
۱۳۷
The reaction of compound A11 with different aromatic aldehydes,

and isatine gave the desired Schiff-base derivatives (A12-A16), which
were identified by FTIR spectrum. The FTIR spectra of the prepared
compounds are shown in Figures 3.41, 3.4۲, 3.4۳, 3.4٤ and 3.45 and the
characteristic absorption bands are listed in Table 3.17.
۱۳۸
Table 3.17 FTIR spectral data (cm-1) of Schiff-base derivatives

(A12-A16)
nC=N
Comp. Ar. nN-H nCH nC≡N & γ C-H Other
no. arom. nC=C arom. bands
H
N nN-H
A12 3344.5 3020.5 2214 1643.5 810 3238.8
1612.4
nN-H
O
NH
3367.0 3032.1 2175.7 1647 815 3309
A13 1613
nC=O
1725
nC-Cl
Cl 3387.9 3012 2177 1627.2 813.9
A14 679.8
1612.5
nNO2
A15 NO2 3375.4 3074.5 2183 1668.6 796 1519asym
1600 1342sym
OH 3359.7 3066.8 2175.7 1647.2 810.1

A16
1612.4
۱۳۹
Figure 3.38 FTIR spectrum of compound A11
۱٤۰
12.053
9.283
6.971
6.950
6.792
6.708
6.687
4.479
3.377
2.513
2.508
1.792
NAME antep Z8
EXPNO 1
PROCNO 1
Date_ 20130225
Time 16.37
INSTRUM spect
PROBHD 5 mm DUL 13C-1
PULPROG zg
TD 65536
SOLVENT DMSO
NS 4
DS 0
SWH 8223.685 Hz
FIDRES 0.125483 Hz
AQ 3.9846387 sec
RG 57
DW 60.800 usec
DE 6.00 usec
TE 300.0 K
antep Z8
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========

NUC1 1H
P1 10.00 usec
PL1 -3.11 dB
PL1W 19.12242317 W
SFO1 400.1324710 MHz
SI 32768
SF 400.1300000 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
0.58
0.47
1.04
1.03
1.00
0.47
1.58
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
Figure 3.39 1HNMR spectrum of compound A11
۱٤۱
161.09
156.48
155.21
135.98
135.23
128.91
121.40
115.57
98.53
58.20
40.57
40.36
40.15
39.94
39.73
39.52
39.31
35.94
10.23
NAME antep Z8
EXPNO 2
PROCNO 1
Date_ 20130225
Time 16.40
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT DMSO
NS 285
antep Z8
DS 4
SWH 24038.461 Hz
FIDRES 0.366798 Hz
AQ 1.3631988 sec
RG 1030
DW 20.800 usec
DE 6.50 usec
TE 300.0 K
D1 2.00000000 sec
D11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========

NUC1 13C
P1 9.00 usec
PL1 -1.00 dB
PL1W 46.16925430 W
SFO1 100.6228298 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.11 dB
PL12 15.00 dB
PL13 16.00 dB
PL2W 19.12242317 W
PL12W 0.29549012 W
PL13W 0.23471613 W
SFO2 400.1316005 MHz
SI 32768
SF 100.6127690 MHz
WDW EM
SSB 0
LB 1.00 Hz
GB 0
PC 1.40
200 180 160 140 120 100 80 60 40 20 0 ppm
13
Figure 3.40 CNMR spectrum of compound A11
۱٤۲
H
N
NC N C
H
HO O
N
H3C N
H
Figure 3.41 FTIR spectrum of compound A12
۱٤۳
N NH
HO O
N
H3C N
H
Figure 3.4۲ FTIR spectrum of compound A1۳
۱٤٤
Figure 3.4۳ FTIR spectrum of compound A1٤
۱٤٥
NC N C NO2
H
HO O
N
H3C N
H
Figure 3.4٤ FTIR spectrum of compound A1٥
۱٤٦
NC N C OH
H
HO O
N
H3C N
H
Figure 3.4٥ FTIR spectrum of compound A1٦
۱٤۷
3.3.6 Evaluation of 6-Amino-4-(4-hydroxyphenyl)-5-cyano-3-methyl-

1,4-dihydropyrano[2,3-c]pyrazole (A11) and it Schiff base
derivatives (A12-A14) as antioxidants
The blended oils were subjected to severe oxidation condition by

IP 280 to evaluate their oxidation stability. The evaluation results of oil
blends are shown in Table 3.18 and Figure 3.46.
The results showed that all the blends A11-A14 has higher
oxidation stability compared with the base oil (blank), but still less than
the oxidation stability of the blend with standard antioxidant.
All the blends gave low total sludge, and total oxidation product
(TOP%), which were in the acceptable range. But they showed
unexpected high total acidity.
۱٤۸
Table 3.18 Oxidation stability results of blend oils (A11-A14)
Characterization Blank A11 A12 A13 A14 Standard
Volatile acidity 0.0025 0.0197 0.0191 0.0046 0.0069 0.0060

(mg KOH/g oil)
Soluble acidity 0.2571 0.7340 0.730 0.8144 0.5817 0.1230
(mg KOH/g oil)
Total acidity 0.2590 0.7537 0.7491 0.8190 0.5886 0.1290
(mg KOH/g oil)
Total sludge 0.2800 0.0344 0.0787 0.0416 0.0226 0.088
(wt%)
Total oxidation 0.3630 0.2760 0.3180 0.3044 0.2115 0.1298
product (TOP%)
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Blank A11 A12 A13 A14 Standard

Figure 3.46 Total sludge, acidity and oxidation products of A11-A14
۱٤۹
3.3.7 Synthesis of pyranopyrazoles and pyranopyrimidines derived

from 5,5-Dimethyl-1,3-cyclohexandion (A17-A25)
The synthetic route of compounds (A17-A25) was started with 2-

(4-hydroxylbenzylidine)malononitrile (S3) in different reactions as shown
in scheme 3.9.
Scheme 3.9 Synthetic rout of compounds A17-A25
150
3.3.7.1 Synthesis of 2-amino-4-(4-hydroxyphenyl)-7,7-dimethyl-5-

oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile (A۱۷)
The 2-(4-hydroxylbenzylidine)malononitrile (S3) was subjected to

Michael reaction with 5,5-dimethyl-1,3-cyclohexandion (dimedone) in
the presence of pipridine as base under microwave irradiation, to give 2-
amino-4-(4-hydroxyphenyl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-
chromene-3-carbonitrile (A17).
The formation of A17 follows the same mechanistic steps known

for the Michael addition reaction as shown in scheme 3.4. Compound
A17 was characterized by FTIR, 1H- NMR, and 13C-NMR.
FTIR spectrum (figure 3.47) showed stretching bands at 3410 and

3375.4 cm-1 (NH2), 2194.9 cm-1 (C≡N), 1681.9 cm-1 (C=O), and at 1651
cm-1.
The 1H- NMR spectrum (figure 3.48) of compound (A17) showed

signals at δ9.25 (1H- singlet) for O-H, and δ6.65- 7.00 for the aromatic
protons (4H- multiplet), while the two protons of NH2 group, and the 4-
H pyrane appeared as singlet at δ6.98 and, δ4.07 respectively. The
protons of CH2 and CH3 groups appeared at δ2.1-2.2, and δ0.95-1.03
respectively.
151
13
196.1ppm for C=O, 164.3ppm, and 160.9ppm for the carbons of pyran
ring (C-O-C), and 120.3ppm due to CN. The carbon attached to OH in
aromatic ring appeared at 156.4ppm while, the other aromatic carbons
appeared at 134.5-115.4ppm. Carbons of CH2, and CH3 groups appeared
at 35.1, 50.5, and 27.2ppm respectively[198].
152
NC NH2
HO O
CH3
H3C
153
9.258
7.002
6.980
6.946
6.925
6.676
6.655
4.071
3.371
2.544
2.500
2.486
2.442
2.266
2.225
2.117
2.077
1.037
0.999
0.984
0.952
NAME antep Z10
EXPNO 1
PROCNO 1
Date_ 20130225
Time 16.59
INSTRUM spect
PULPROG zg
TD 65536
SOLVENT DMSO
NS 4
DS 0
SWH 8223.685 Hz
FIDRES 0.125483 Hz
AQ 3.9846387 sec
RG 45.2
DW 60.800 usec
DE 6.00 usec
antep Z10
TE 300.0 K
D1 1.00000000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 1H
P1 10.00 usec
PL1 -3.11 dB
PL1W 19.12242317 W
SFO1 400.1324710 MHz
SI 32768
SF 400.1300000 MHz
WDW EM
SSB 0
LB 0.30 Hz
GB 0
PC 1.00
0.52
1.94
1.00
0.53
0.69
1.19
0.63
0.63
1.59
0.48
1.45
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
Figure 3.48 1HNMR of A17
154
196.13
164.37
162.46
160.99
158.85
156.45
135.64
134.35
129.62
128.62
123.27
120.36
117.10
115.46
114.66
113.65
102.89
59.23
50.50
40.59
40.38
40.18
39.97
39.76
39.55
39.34
35.17
32.25
28.89
28.41
27.23
NAME antep Z10
EXPNO 2
PROCNO 1
Date_ 20130225
Time 17.02
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT DMSO
NS 611
antep Z10
DS 4
SWH 24038.461 Hz
FIDRES 0.366798 Hz
AQ 1.3631988 sec
RG 1030
DW 20.800 usec
DE 6.50 usec
TE 300.0 K
D1 2.00000000 sec
D11 0.03000000 sec
TD0 1
======== CHANNEL f1 ========

NUC1 13C
P1 9.00 usec
PL1 -1.00 dB
PL1W 46.16925430 W
SFO1 100.6228298 MHz
======== CHANNEL f2 ========
CPDPRG2 waltz16
NUC2 1H
PCPD2 80.00 usec
PL2 -3.11 dB
PL12 15.00 dB
PL13 16.00 dB
PL2W 19.12242317 W
PL12W 0.29549012 W
PL13W 0.23471613 W
SFO2 400.1316005 MHz
SI 32768
SF 100.6127690 MHz
WDW EM
SSB 0
LB 1.00 Hz
GB 0
PC 1.40
200 180 160 140 120 100 80 60 40 20 0 ppm
Figure 3.49 13CNMR of A17
155
3.3.7.2 Synthesis of 5-(4-hydroxyphenyl)-8,8-dimethyl-8,9-dihydro-

The reaction of compound A17 with excess formic acid under
microwave irradiation, gave 5-(4-hydroxyphenyl)-8,8-dimethyl-8,9-
dihydro-3H-chromeno[2,3-d]pyrimidine-4,6(5H,7H)-dione (A۱۸).
The structure of the synthesized compound A18 was confirmed by

FTIR spectrum, which showed an absorption band at 3259 cm-1 due to
OH group. The NH2 and C≡N bands were disappeared, while a
characteristic (C=O) band was appeared at 1709.8 cm-1 (figure 3.50).
3.3.7.3 Synthesis of 5-(4-hydroxyphenyl)-4-imino-8,8-dimethyl

Reaction of compound A17 with formamide under microwave

irradiation, afforded 5-(4-hydroxyphenyl)-4-imino-8,8-dimethyl 5,7,8,9-
tetrahydro-3H-chromeno[2,3-d]pyrimidin-6(4H)-one (A19), which was
confirmed by FTIR, and 1H- NMR.
FTIR spectrum (figure 3.51) showed stretching bands at 3376.8

cm-1, and 3200.6 cm-1 for NH2 group of the tautomer of A19. While,
the nitrile (C≡N) band was disappeared.
۱٥٦
Figure 3.50 FTIR spectrum of A18
۱٥۷
HN
HN N
OH O
CH3
H3C
۱٥۸
The 1H- NMR spectrum (figure 3. 52) showed the singlet signals
at δ9.3 and δ8.8 were assigned for OH and CH pyrmidone protons
respectively. Aromatic protons appeared as multiplet at δ7.3- δ6.6 , while
the two protons of NH2 appeared as singlet at δ6.9. The protons of CH
pyran ring, CH2 and CH3 protons appeared as singlet at δ4.6, δ2.1- 2.2,
and δ0.9-1.1 respectively.
3.3.7.4 Synthesis of 1-(5-(4-hydroxyphenyl)-8,8-dimethyl-6-oxo-2-

thiourea (A20)
The compound A20 was synthesized by reacting one mole of A17

with two moles of ammonium thiocyanate in acetic acid. The structure
of this compound was confirmed by FTIR.
FTIR spectrum (figure 3.53) showed a broad band at 3300 cm-1
which was attributed to overlap NH2, NH, and OH bands. The IR
spectrum also showed the disappearance of C≡N band, and appearance
of C=S at 1234.4 cm-1.
۱٥۹
Figure 3.52 1H- NMR spectrum of A19
۱٦۰
۱٦۱
3.3.7.5 Synthesis of Schiff base derivatives (A21-A25)

The reaction of compound A17 with different aromatic aldehydes,
and isatine gave the desired Schiff-base derivatives (A21-A25), which
were identified by FTIR spectrum. The FTIR spectra of the prepared
compounds are shown in Figures (3.54-3.58). and the characteristic
absorption bands are listed in Table 3.19.
Table 3.19 FTIR spectral data (cm-1) of Schiff-base derivatives

(A21-A25
nC=O
Comp. Ar. nCH nC≡N & γ C-H Other
no. arom. nC=N arom. bands
(o.o.p.)
O
3060 2192.9 1683.7 844.7 nC=O
NH
A21 1650.9 1739.6
H
N 3031.9 2190.0 1683.2 846 n N-H
A22
1643 3182
Me
3072 2190.8 1679.8 815.8
A23 N -
1649
Me
3065 2200.6 1681.8 817.7 ν NO2

A24 NO2 1514asym
1660.8
1348sym
HO
3097.4 2192 1677.9 800.4
A25 -
1650.9 848.6
۱٦۲
Schiff-base derivative 2-(4-(dimethylamino) benzylidene -amino)-

4-(4-hydroxyphenyl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro -4H-
1
chromene -3-carbonitrile (A23) was characterized by H- NMR, and
13
CNMR.
In the 1H- NMR spectrum (figure 3.59) two signals for OH and CH
of imine as a singlet at δ9.67 and δ9.2, respectively. Aromatic protons
appeared as multiplet at δ7.7- δ6.6. The signal at δ4.06 was assigned to
pyran proton, while six protons of –N(CH3)2 appeared as singlet at δ3.09.
The CH2 and CH3 protons appeared as singlet at δ2.1- 2.2, and δ0.9-1.1
respectively.
13
CNMR spectrum (figure 3.60) showed signals at 196.5 for C=O,
188.3 ppm for C=N imine, while the C-OH and C-N(CH3)2 appeared at
155 ppm, and i54.1. Carbons of pyran ring (C-O-C) appeared at 158 and
164.5 ppm. The aromatic carbons appeared at 135 -113.1ppm. A signal at
58.7ppm was attributed to carbon attached to the nitrile group, while
carbon of nitrile appeared at 119.8 [183].
۱٦۳
Figure 3.54FTIR spectrum of A21
۱٦٤
۱٦٥
۱٦٦
۱٦۷
۱٦۸
Figure 3.59 1HNMR spectrum of A23
۱٦۹
Figure 3.60 13CNMR spectrum of A23
۱۷۰
3.3.8 Evaluation of pyranopyrazoles and pyranopyrimidines

derived from 5,5-Dimethyl-1,3-cyclohexandion (A17-A25) as
antioxidants
The blended oils were subjected to severe oxidation condition by

IP 280 to evaluate their oxidation stability. The evaluation results of oil
blends are shown in Table 3.20 and Figure 3.61.
The results showed that all the blends A17-A23 have higher
oxidation stability compared with the base oil (blank), while the blends
A20, A21, and A23 have highest oxidation stability than the blend with
standard antioxidant.
It was well known that fused chromenes are biologically active

compounds [159-162]. It is possible to say that the highest oxidation
stability of blends A17-A23 with the prepared additives, belongs to the
fused chromene ring in their structures.
۱۷۱
Table 3.20 oxidation stability results of blend oils A17-A25
Characterization Blank A17 A18 A19 A20 A21 A23 A25 Standard
Volatile acidity 0.0025 0.0120 0.0046 0.0040 0.0060 0.0049 0.0093 0.0060 0.006
(mg KOH/g oil)
Soluble acidity 0.2571 0.1250 0.2327 0.130 0.1210 0.0123 0.3490 0.1220 0.1230
(mg KOH/g oil)
Total acidity 0.2596 0.1370 0.2373 0.134 0.1270 0.0172 0.3583 0.1280 0.1290
(mg KOH/g oil)
Total sludge 0.280 0.3188 0.1324 0.1664 0.0330 0.0989 0.0204 0.5436 0.0880
(wt,%)
Total oxidation 0.3630 0.3627 0.2084 0.2093 0.1292 0.1044 0.1170 0.5846 0.1298
product (TOP,%)
۱۷۲
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Blank A17 A18 A19 A20 A21 A23 A25 Standard
Total sludge (wt%) Total oxidation product (TOP%) Total acidity (mg KOH/g oil)
Figure 3.61 Total sludge, acidity and oxidation products of A17-A25
۱۷۳
3.3.9 Synthesis of 7-amino-5-(4-hydroxyphenyl)-2,4-dioxo-2,3,4,5-

The 2-(4-hydroxylbenzylidine)malononitrile (S3) was subjected to

Michael reaction with pyrimidine-2,4,6(1H,3H,5H)-trione (barbituric
acid) in order to give 7-amino-5-(4-hydroxyphenyl)-2,4-dioxo-2,3,4,5-
tetrahydro-1H-pyrano[2,3-d]pyrimidine-6-carbonitrile (A26).
The formation of A26 follows the same mechanistic steps known

for the Michael addition [199] as shown in scheme 3.10.
Scheme 3.10 Formation mechanism of A26
۱۷٤
The structure of the synthesized compound A26 was confirmed by

FTIR,1HNMR,and 13CNMR spectrum.
FTIR spectrum (figure 3.62) showed stretching bands at 3405,

3311, 3178.5 cm-1 for NH2 and NH amide groups, while, the nitrile
(C≡N) band was appeared at 2190.9 cm-1, and the carbonyl groups
appeared at 1726 and 1691 cm-1.
The 1H- NMR spectrum (figure 3. 63) showed the singlet signals at
δ11.99 and δ9.26 were assigned for NH and OH protons respectively.
Aromatic protons appeared as multiplet at δ7.9- δ6.5, while the two
protons of NH2 appeared as singlet at δ6.98. The proton of CH pyran
ring appeared as singlet at δ4.1.
13
CNMR spectrum (figure 3.64) showed signals at 165 for C=O,
while the C-OH appeared at 156ppm. Carbons of pyran ring (C-O-C)
appeared at 158 and 160ppm. The aromatic carbons appeared at 135 -
113.1ppm. A signal at 53ppm was attributed to carbon attached to the
nitrile group, while carbon of nitrile appeared at 118.6 [198].
۱۷٥
NC NH2
HO O
O N H
H O
۱۷٦
NC NH2
HO O
O N H
H O
Figure 3.63 1HNMR spectrum of A26
۱۷۷
NC NH2
HO O
O N H
H O
Figure 3.64 13CNMR spectrum of A26
۱۷۸
3.3.10 Evaluation of 7-Amino-6-cyano-5-(4-hydroxyphenyl)-5H-

pyrano [2,3-d]pyrimidine-2,4-diones (A26) as antioxidants
Different concentrations of additive A26 (0.7, 1, and 1.5 wt%)

were blended with 60 stock base oil to produce blends B1,B2, and B3,
respectively. The oxidation stability of these blends were evaluated
according to IP280, oxygen is passed through the blends containing
soluble iron and copper catalysts. The blends is held at 120οC and test
time is 164 h. During the test, volatile acids formed are absorbed in an
absorption tube. At the end of the test, the acid numbers of the oil and the
absorbent are determined and combined to give the total acidity; the
sludge is determined as a weight percent. These may then be further
combined to give the total oxidation products.
The results are tabulated in Table 3.21, It was found from Table
3.21 and Figure 3.65 that the blends B1, B2, and B3 have higher
oxidation stability compared with the base oil (blank) and the blend with
the standard antioxidant.
It was well known that the pyrimidine-2,4-dione ring has a wide

range of biological activity [199,200], especially as antioxidant [201]. It
is possible to say that the highest oxidation stability of blends B1, B2, and
B3 with the prepared additive A26 belongs to pyrimidine-2,4-dione ring
in its structure.
The blend B1 with 0.7 wt% of A26 gave the higher oxidation
stability than B2and B3. So, the recommended percentage of this additive
A26 is 0.7 wt%, which is more lower than the percentage of standard
additive.
۱۷۹
Table 3.21 Oxidation stability results of blend oils B1, B2 and B3
Characterization Blank B1 B2 B3 Standard

Volatile acidity 0.0025 0.0061 0.0093 0.0046 0.0060
(mg KOH/g oil)
Soluble acidity 0.2571 0.0185 0.2327 0.2327 0.123
(mg KOH/g oil)
Total acidity 0.2596 0.0246 0.2420 0.2373 0.129
(mg KOH/g oil)
Total sludge 0.2800 0.0562 0.0272 0.0850 0.0880
(wt,%)
Total oxidation 0.3630 0.0642 0.1049 0.1116 0.1298
product
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
Blank B1 B2 B3 Standard

Figure 3.65 Total sludge, acidity and oxidation products of
B1, B2 and B3
۱۸۰
Conclusion
1. Overbased detergents of magnesium and calcium fatty acid salts

(D1-D10) were successfully synthesized and evaluated as a
lubricating oil additives by blending each additive in various
concentrations with 60 stock base oil, and the TBN was
determined.
2. The TBN measurements and detergent efficiency calculation,

revealed that the oil blends with prepared overbased magnesium
palmitate (D5) , oleate (D6) and stearate (D7) detergents gave the
higher TBN and efficiency.
3. Blends of 2% of D5 and D7 detergents showed better oxidation

stability than the standard antioxidant supplied by Midland
Refineries Company.
4. Blends of D5 and D7, in different concentrations, were evaluated

as viscosity index (VI) improver. VI values indicated that better
performance is obtained with the 5% D7, its VI is approximately
the same VI of the olefin co-polymer standard.
5. The pour point of oil blends with 2 and 3.5 wt.% D5, and D7 was
investigated. All these additives depressed the oil pour point from
-6 οC to -15 οC.
۱۸۱
6. Different pyranopyrazoles and pyranopyrimidines derivatives (A1-

A26) were synthesized and the assumed structures of the prepared
compounds are confirmed by the FTIR, 1H NMR, and 13C NMR.
7. Most of pyranopyrazoles and pyranopyrimidines derivatives were

evaluated as antioxidants for lubricating oils by blending 1% of
each compound with base lubricating oil 60 stock. The oxidation
stability study revealed that many of the tested compounds showed
good to moderate antioxidant activities, while the derivatives A4,
A5, A7, A20, A21, A23, and A26 showed better oxidation stability
than the standard antioxidant supplied by Midland Refineries
Company.
۱۸۲
Kinematic viscosity measurement apparatus (ASTM-D 445)
183
Pour point measurement apparatus (ASTM-D 97)
184
Oxidation stability apparatus (IP 280)
185
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188) Tietze, L.F., and Beifuss, U. "The Knoevenagel Reaction".

Comprehensive Organic Synthesis. 2nd ed. Oxford, Pergamon Press,
1991.
189) Campaigne, E. and Schneller, S.W., Synthesis, 11, 1976, p. 705.
190) Nakanishi, K., “Infrared Absorption Spectroscopy”, Holden Day,

Inc. San Francisco, 1962.
191) I. L. Firar “Organic Chemistry” Vol. 2, Fifth Edition, William

Clowes &Sons , Limited, London, 1975.
192) Dyke, S. F..; Floyd, A. J.; Sainsbury, M. and Thobald, R. S.,

“Oraginc Spectroscopy: An Introduction”, Penguin Books Ltd,
Harmondsworth, 1971.
193) Raber, D. J. and Raber, N. K. “Oraginc Chemistry”, West

Publishing Company, New York, 1998.
194) Laura Favretto, Basic Guidelines for Microwave Organic Chemistry

Applications, Milestone Srl., 2000, p. 2.
195) Institute of Petroleum (IP), "Standard Methods for Analysis and

Testing of Petroleum and Related Products", John Wiley and Sons,
U.K, Vol.1. 1993.
196) Prakash, C.R., Raja, S., Saravanan, G., Dinesh Kumar, P. and
Panneer Selvam,T., Asian J. Res. Pharm. Sci.,1(4), 2011, p.140.
۲۰٤
References
197) Sudzhaev, A. R., Rzaeva, I. A., Nadzhafova, R. A., Safarov, Yu. S.

and Allakhverdiev, M. A.. Russian Journal of Applied Chemistry,
84(8), 2011, p:1394.
198) Mistry, B.D., “A Handbook of Spectroscopic Data (UV, IR, PMR,

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CNMR and Mass Spectroscopy)”, Oxford Book Company, Jaipur,
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Amanlou, M., Journal of Pharmaceutical Sciences, 21(3), 2013, p.1.
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32 (3), 2011, p. 899.
201) Ilangovan, A. ; Muralidharan, S., and Maruthamuthu, S., Journal of

the Korean Chemical Society, 55(6), 2011, p.1000.
۲۰٥
‫ﺍﻟﺨﻼﺻﺔ‬
‫ﺗﻀﻤﻦ ﺍﻟﺒﺤﺚ ﺗﺤﻀﻴﺮ ﻣﺠﻤﻮﻋﺔ ﻣﻦ ﻣﻨﻈﻔﺎﺕ ﻓﻮﻕ ﺍﻟﻘﺎﻋﺪﻳﺔ ﻛﻤﺤﺴﻨﺎﺕ ﻟﺰﻳﻮﺕ ﺍﻟﺘﺰﻳﻴﺖ ﻭﺗﻢ‬
‫ﺍﺧﺘﺒﺎﺭﻫﺎ ﻛﻤﺤﺴﻦ ﻟﻤﺆﺷﺮ ﺍﻟﻠﺰﻭﺟﺔ ﻭﻣﺨﻔﺾ ﻟﺪﺭﺟﺔ ﺍﻻﻧﺴﻜﺎﺏ ‪ .‬ﻛﻤﺎ ﺣﻀﺮﺕ ﻣﺮﻛﺒﺎﺕ ﺟﺪﻳﺪﺓ ﻣﻦ‬
‫ﻣﺸﺘﻘﺎﺕ ‪ pyranopyrazole‬ﻭ ‪ pyranopyrimidine‬ﻛﻤﻀﺎﺩﺍﺕ ﻟﻸﻛﺴﺪﺓ‪.‬‬
‫ﺗﻢ ﺗﺤﻀﻴﺮ ﺳﻠﺴﻠﺔ ﻣﻦ ﺃﻣﻼﺡ ﺍﻟﻤﻐﻨﺴﻴﻮﻡ ﻓﻮﻕ ﺍﻟﻘﺎﻋﺪﻳﺔ ﻟﻠﺤﻮﺍﻣﺾ ﺍﻟﺸﺤﻤﻴﺔ )‪ (D7-D1‬ﻣﻦ‬
‫ﺗﻔﺎﻋﻞ ﺍﻷﺣﻤﺎﺽ ﺍﻟﺸﺤﻤﻴﺔ ﻣﻊ ﺍﻭﻛﺴﻴﺪ ﺍﻟﻤﻐﻨﺴﻴﻮﻡ ﻭ ﻏﺎﺯ ﺛﺎﻧﻲ ﺍﻭﻛﺴﻴﺪ ﺍﻟﻜﺮﺑﻮﻥ ﻋﻨﺪ ﺩﺭﺟﺔ ‪ 60‬ﻣﺌﻮﻳﺔ ‪،‬‬
‫ﺑﻮﺟﻮﺩ ﻣﺤﻠﻮﻝ ﺍﻻﻣﻮﻧﻴﺎ ﻛﻌﺎﻣﻞ ﻣﺴﺎﻋﺪ ﻭﻣﺰﻳﺞ ﺍﻟﺘﻠﻮﻳﻦ – ﺍﻳﺜﺎﻧﻮﻝ ﻛﻤﺬﻳﺐ ﺑﻨﺴﺒﺔ ﺣﺠﻤﻴﻪ )‪ .(1:9‬ﻛﻤﺎ‬
‫ﺣﻀﺮﺕ ﺑﻨﻔﺲ ﺍﻟﻄﺮﻳﻘﺔ ﻣﻨﻈﻔﺎﺕ ﻓﻮﻕ ﺍﻟﻘﺎﻋﺪﻳﺔ ﻟﻤﻠﺢ ﺍﻟﻜﺎﻟﺴﻴﻮﻡ ﻣﺸﺘﻘﺔ ﻣﻦ ﺣﻮﺍﻣﺾ ‪ palmitic‬ﻭ‬
‫‪ stearic‬ﻭ ‪ oleic‬ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﻭﻛﺴﻴﺪ ﺍﻟﻜﺎﻟﺴﻴﻮﻡ ﻭ ﻫﻴﺪﺭﻭﻛﺴﻴﺪ ﺍﻟﻜﺎﻟﺴﻴﻮﻡ ﺑﺪﻻ ﻣﻦ ﺍﻭﻛﺴﻴﺪ ﺍﻟﻤﻐﻨﺴﻴﻮﻡ‪.‬‬
‫ﺷﺨﺼﺖ ﺍﻟﻤﻨﻈﻔﺎﺕ ﺍﻟﻤﺤﻀﺮﺓ ﺑﻮﺳﺎﻁﺔ ﻣﻄﻴﺎﻓﻴﺔ ﺍﻷﺷﻌﺔ ﻓﻮﻕ ﺍﻟﺒﻨﻔﺴﺠﻴﺔ ﻭﺍﻟﺮﻧﻴﻦ ﺍﻟﻨﻮﻭﻱ‬
‫ﺍﻟﻤﻐﻨﺎﻁﻴﺴﻲ ﻟﻠﺒﺮﻭﺗﻮﻥ‪ .‬ﻭﺗﻢ ﺗﻘﻴﻴﻢ ﻛﻔﺎءﺓ ﻫﺬﻩ ﺍﻟﻤﻨﻈﻔﺎﺕ ﺑﻤﺰﺝ ﻛﻞ ﻣﻀﺎﻑ ﺑﺘﺮﺍﻛﻴﺰ ﻣﺨﺘﻠﻔﺔ ﻣﻊ ﺯﻳﺖ‬
‫ﺍﻟﺘﺰﻳﻴﺖ ﻧﻮﻉ )‪ (60 stock‬ﺍﻟﻤﺠﻬﺰ ﻣﻦ ﺷﺮﻛﺔ ﻣﺼﺎﻓﻲ ﺍﻟﻮﺳﻂ ﺍﻟﻌﺮﺍﻗﻴﺔ ﻣﻦ ﺧﻼﻝ ﻗﻴﺎﺱ ﺍﻟﻌﺪﺩ‬
‫ﺍﻟﻘﺎﻋﺪﻱ ﺍﻟﻜﻠﻲ )‪.(TBN‬‬
‫ﻋﻮﻟﺠﺖ ﻧﺘﺎﺋﺞ ﺍﻟﻌﺪﺩ ﺍﻟﻘﺎﻋﺪﻱ ﺍﻟﻜﻠﻲ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﻻﺧﺘﺒﺎﺭ ﺍﻹﺣﺼﺎﺋﻲ ﻟﻠﻤﺘﻐﻴﺮﺍﺕ )‪ (ANOVA‬ﻭ‬
‫ﻗﺪ ﻭﺟﺪ ﺃﻥ ﺗﺄﺛﻴﺮ ﻋﺪﺩ ﺫﺭﺍﺕ ﺍﻟﻜﺮﺑﻮﻥ ﻓﻲ ﺍﻟﺤﻮﺍﻣﺾ ﺍﻟﺸﺤﻤﻴﺔ ﺍﻟﻤﺴﺘﺨﺪﻣﺔ ﻓﻲ ﺗﺤﻀﻴﺮ ﺍﻟﻤﻨﻈﻔﺎﺕ‬
‫)‪ (D7-D1‬ﻛﺎﻥ ﻣﺤﺪﻭﺩﺍ‪ ،‬ﺑﻴﻨﻤﺎ ﺯﻳﺎﺩﺓ ﺍﻟﺘﺮﻛﻴﺰ )‪ (1-5%‬ﻟﻪ ﺗﺄﺛﻴﺮ ﻣﻠﻤﻮﺱ ‪.‬‬
‫ﺃﻅﻬﺮ ﻣﺰﻳﺞ ﺍﻟﺰﻳﺖ ﺍﻟﻤﺤﻀﺮ ﺑﻨﺴﺒﺔ ‪ 2%‬ﻣﻦ ﻣﻨﻈﻔﻲ ﻓﻮﻕ ﺍﻟﻘﺎﻋﺪﻳﺔ ﻟﻤﻠﺢ ﺍﻟﻤﻐﻨﺴﻴﻮﻡ ﻟﻠﺤﺎﻣﻀﻴﻦ‬
‫ﺍﻟﺸﺤﻤﻴﻴﻦ )‪ (palmitic , stearic‬ﺍﺳﺘﻘﺮﺍﺭﻳﺔ ﺗﺠﺎﻩ ﺍﻷﻛﺴﺪﺓ ﺃﻓﻀﻞ ﻣﻦ ﻣﺰﻳﺞ ﺍﻟﺰﻳﺖ ﻣﻊ ﺍﻟﻤﺎﺩﺓ ﺍﻟﻘﻴﺎﺳﻴﺔ‬
‫ﺍﻟﻤﺴﺘﺨﺪﻣﺔ ﻓﻲ ﺷﺮﻛﺔ ﻣﺼﺎﻓﻲ ﺍﻟﻮﺳﻂ‪.‬‬
‫‪ magnesium palmitate‬ﻭ‬ ‫ﺗﻢ ﺍﺧﺘﺒﺎﺭ ﻛﻔﺎءﺓ ﺍﻟﻤﻨﻈﻔﺎﺕ ﻓﻮﻕ ﺍﻟﻘﺎﻋﺪﻳﺔ ﺍﻟﻤﺤﻀﺮﺓ‬

‫‪ magnesium stearate‬ﻛﺮﺍﻓﻌﺎﺕ ﻟﻤﺆﺷﺮ ﺍﻟﻠﺰﻭﺟﺔ‪ .‬ﺣﻴﺚ ﻭﺟﺪ ﺇﻥ ﺍﻟﻜﻔﺎءﺓ ﺗﺰﺩﺍﺩ ﺑﺰﻳﺎﺩﺓ ﺗﺮﻛﻴﺰ‬
‫ﺍﻟﻤﻀﺎﻑ ﻣﻦ ﺍﻟﻤﺎﺩﺓ ﺍﻟﻤﺤﻀﺮﺓ ﻭﺑﺰﻳﺎﺩﺓ ﺍﻟﻮﺯﻥ ﺍﻟﺠﺰﻳﺌﻲ ﻟﻬﺎ‪ .‬ﺃﻋﻄﻰ ﺍﻟﻤﺮﻛﺐ ‪ D7‬ﺑﺘﺮﻛﻴﺰ ‪ %٥‬ﺃﻋﻠﻰ‬
‫ﻛﻔﺎءﺓ ﻛﺮﺍﻓﻊ ﻟﺰﻭﺟﺔ ﻭﻣﺨﻔﺾ ﺩﺭﺟﺔ ﺍﻧﺴﻜﺎﺏ‪.‬‬
‫‪ pyranopyrazole‬ﻭ‬ ‫ﺣﻀﺮﺕ ﻣﺠﻤﻮﻋﺔ ﻣﻦ ﻣﻀﺎﺩﺍﺕ ﺍﻷﻛﺴﺪﺓ ﺍﻟﻤﺸﺘﻘﺔ ﻣﻦ‬
‫‪ pyranopyrimidine‬ﺑﺎﺳﺘﺨﺪﺍﻡ ﻣﺮﻛﺐ ‪ 2-(4-hydroxy-benzylidine) malononitrile‬ﻛﻤﺎﺩﺓ‬
‫ﺃﺳﺎﺳﻴﺔ ﻭﻣﻔﺎﻋﻠﺘﻬﺎ ﻣﻊ ‪ 3-methyl-1-phenyl-2-pyrazolin-5-one‬ﺃﻭ ‪3-methyl-2-‬‬
‫‪ pyrazolin-5-one‬ﺃﻭ ﺍﻟﺪﻳﻤﻴﺪﻭﻥ ﺃﻭ ﺣﺎﻣﺾ ‪ barbituric‬ﻟﻴﻨﺘﺞ ﺍﻟﻤﺸﺘﻘﺎﺕ ‪ A1‬ﻭ‪ A11‬ﻭ ‪ A17‬ﻭ‬
‫‪ A26‬ﻋﻠﻰ ﺍﻟﺘﻮﺍﻟﻲ‪.‬‬
‫ﺗﻢ ﻣﻔﺎﻋﻠﺔ ﻛﻞ ﻣﻦ ‪ A1‬ﻭ ‪ A17‬ﻣﻊ ﺣﺎﻣﺾ ﺍﻟﻔﻮﺭﻣﻴﻚ ﻭﺍﻟﻔﻮﺭﻣﺎﻳﺪ ﻭﺛﺎﻳﻮ ﺳﻴﺎﻧﺎﺕ ﺍﻻﻣﻮﻧﻴﻮﻡ‬
‫ﺑﺎﺳﺘﺨﺪﺍﻡ ﺃﺷﻌﺔ ﺍﻟﻤﺎﻳﻜﺮﻭﻭﻳﻒ ﻟﺘﻨﺘﺞ ﺍﻟﻤﺮﻛﺒﺎﺕ ‪ A2‬ﻭ ‪ A3‬ﻭ ‪ A4‬ﻭﻛﺬﻟﻚ ‪ A18‬ﻭ ‪ A19‬ﻭ ‪ A20‬ﻋﻠﻰ‬
‫ﺍﻟﺘﻮﺍﻟﻲ‪.‬‬
‫ﺣﻀﺮﺕ ﻗﻮﺍﻋﺪ ﺷﻒ )‪ ( A16-A12‬ﻣﻦ ﺗﻔﺎﻋﻞ ﺍﻟﻤﺮﻛﺐ ‪ A11‬ﻣﻊ ﺍﻟﺪﻳﻬﺎﻳﺪﺍﺕ ﺍﺭﻭﻣﺎﺗﻴﺔ‬

‫ﻣﺨﺘﻠﻔﺔ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﻟﻤﺎﻳﻜﺮﻭﻭﻳﻒ‪ .‬ﻛﻤﺎ ﺣﻀﺮﺕ ﺍﻟﻤﺮﻛﺒﺎﺕ )‪ (A20-A18‬ﻭ )‪ (A25-A21‬ﺑﻨﻔﺲ‬
‫ﺍﻟﻄﺮﻳﻘﺔ‪.‬‬
‫ﺷﺨﺼﺖ ﺍﻟﻤﺮﻛﺒﺎﺕ ﺍﻟﻤﺤﻀﺮﺓ ﺑﻮﺳﺎﻁﺔ ﻣﻄﻴﺎﻓﻴﺔ ﺍﻷﺷﻌﺔ ﺗﺤﺖ ﺍﻟﺤﻤﺮﺍء ﻭﻗﺴﻢ ﻣﻨﻬﺎ ﺑﻤﻄﻴﺎﻓﻴﺔ‬
‫ﺍﻟﺮﻧﻴﻦ ﺍﻟﻨﻮﻭﻱ ﺍﻟﻤﻐﻨﺎﻁﻴﺴﻲ ﻟﻠﺒﺮﻭﺗﻮﻥ ﻭﺍﻟﻜﺮﺑﻮﻥ ﻛﻤﺎ ﺗﻢ ﺗﻘﻴﻴﻤﻬﺎ ﻛﻤﻀﺎﺩﺍﺕ ﻟﻸﻛﺴﺪﺓ ﺑﺨﻠﻂ ‪ %۱‬ﻣﻦ ﻛﻞ‬
‫ﻣﺮﻛﺐ ﻣﻊ ﺯﻳﺖ ﺍﻷﺳﺎﺱ ﻣﻦ ﻧﻮﻉ ‪ 60 stock‬ﺍﻟﻤﺠﻬﺰ ﻣﻦ ﺷﺮﻛﺔ ﻣﺼﺎﻓﻲ ﺍﻟﻮﺳﻂ‪.‬‬
‫ﺗﻢ ﺍﺧﺘﺒﺎﺭ ﺍﺳﺘﻘﺮﺍﺭﻳﺔ ﺍﻷﻛﺴﺪﺓ ﻟﻤﺰﻳﺞ ﺍﻟﺰﻳﻮﺕ ﺍﻟﻤﺤﻀﺮﺓ ﺑﺎﺳﺘﺨﺪﺍﻡ ﺍﻟﻄﺮﻳﻘﺔ ﺍﻟﻘﻴﺎﺳﻴﺔ ‪IP280‬‬
‫‪.‬ﺣﻴﺚ ﺑﻴﻨﺖ ﺍﻟﻨﺘﺎﺋﺞ ﺇﻥ ﻣﻌﻈﻢ ﺍﻟﻤﺮﻛﺒﺎﺕ ﺍﻟﻤﺤﻀﺮﺓ ﺃﻅﻬﺮﺕ ﺍﺳﺘﻘﺮﺍﺭﻳﺔ ﺃﻛﺴﺪﺓ ﻣﻦ ﻣﻌﺘﺪﻟﺔ ﺇﻟﻰ ﺟﻴﺪﺓ ﺑﻴﻨﻤﺎ‬
‫ﺍﻟﻤﺮﻛﺒﺎﺕ ‪ A4‬ﻭ ‪ A5‬ﻭ ‪ A7‬ﻭ ‪ A20‬ﻭ ‪ A21‬ﻭ ‪ A23‬ﻭ ‪ A26‬ﺃﻅﻬﺮﺕ ﺍﺳﺘﻘﺮﺍﺭﻳﺔ ﺃﻛﺴﺪﺓ ﺃﻓﻀﻞ ﻣﻦ‬
‫ﺍﻟﻤﺎﺩﺓ ﺍﻟﻘﻴﺎﺳﻴﺔ ﺍﻟﻤﺠﻬﺰﺓ ﻣﻦ ﺷﺮﻛﺔ ﻣﺼﺎﻓﻲ ﺍﻟﻮﺳﻂ‪.‬‬
‫ئﻙﺎﺡتئﻙﻊﻛ ﻠﻰ‬
‫بئﻙﺔﻊﻛﻱﻝئﻙﻊﺌﻙﻰ ه‬
‫ئذ‬
‫هر‬
‫ﺝﺌ ﻠﻊ ﺒ ﺎﻎخئخ – ﻘﻛﻱ ﺒئﻙﻊﻛهﻝ‬
‫ﻔ ﺯﻝئﻙﻘﻱ ﻠﻱﺌ ؟‬
‫ﺗﺨـﻠـــــﻴﻖ ﻣﺤﺴــــــﻨﺎﺕ ﺍﻟﺰﻳـــــــﻮﺕ‬
‫ﺃﻁﺮﻭﺣﺔ‬
‫ﻣﻘﺪﻣﺔ ﺍﻟﻰ ﻛﻠﻴﺔ ﺍﻟﻌﻠﻮﻡ‪ -‬ﺟﺎﻣﻌﺔ ﺑﻐﺪﺍﺩ‬
‫ﻛﺠﺰء ﻣﻦ ﻣﺘﻄﻠﺒﺎﺕ ﻧﻴﻞ ﺩﺭﺟﺔ ﺩﻛﺘﻮﺭﺍﻩ‬
‫ﻓﻠﺴﻔﺔ ﻓﻲ ﺍﻟﻜﻴﻤﻴﺎ ء ﺍﻟﻌﻀﻮﻳﺔ‬
‫ﻣﻦ ﻗﺒﻞ‬
‫ﺯﻳﻨﺐ ﻋﺒﺪ ﺍﻟﺰﻫﺮﺓ ﺧﻀﻴﺮ ﺍﻟﻤﺼﺮﻱ‬
‫ﺑﻜﺎﻟﻮﺭﻳﻮﺱ ﻋﻠﻮﻡ ﻓﻲ ﺍﻟﻜﻴﻤﻴﺎء ‪ -‬ﺟﺎﻣﻌﺔ ﺑﻐﺪﺍﺩ ‪۱۹۹٤ -‬‬

‫ﻣﺎﺟﺴﺘﻴﺮ ﻋﻠﻮﻡ ﻓﻲ ﺍﻟﻜﻴﻤﻴﺎء ‪ -‬ﺟﺎﻣﻌﺔ ﺍﻟﻨﻬﺮﻳﻦ ‪۱۹۹۹ -‬‬
‫ﺑﺈ ﺷﺮﺍﻑ‬
‫ﺃ‪.‬ﺩ‪ .‬ﻋﺒﺪ ﺍﻟﺤﻠﻴﻢ ﻋﺒﺪﺍﻟﻜﺮﻳﻢ ﻣﺤﻤﺪ‬ ‫ﺃ‪.‬ﺩ‪ .‬ﻣﺤﻤﺪﺭﻓﻌﺖ ﺍﺣﻤﺪ‬
‫‪ ۱٤۳٤‬ﻫـ‬ ‫‪ ۲۰۱۳‬ﻡ‬

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Ministry of Higher Education and Scientific Research

University of Baghdad – College of Science

Synthesis of Lubricant’s Additives

Zainab Abdulzahra Khuthair AL-Messri

B.Sc. (Baghdad University 1994)

‫ﻣﻦ ﺳﻮرة اﻟﺸﻌﺮاء‬

The light of my life…

The real friend and sister…

I would like to express my gratitude to the many people that helped

My deep gratitude to Prof. Mousa Almousawi, Prof. Abdul

Sincere thanks to the Ministry of Higher Education and

Thanks are offered to the Department of chemistry, College of

I gratefully acknowledge financial support by the Petroleum R&D

I am very grateful to Dr. Abdulkareem Mohammed Ali, for

Thanks are also due to Midland Refineries Company/ Iraq for

Sincere thanks to Prof. Intisar Altamemi, Prof. Ahlam M.

A special thanks to Dr. Ghadah A. Yiseen, Middle East Technical

Sincere thanks goes to my best friends (Israa, Saba, Nada, Jwan,

Finally, my respect and appreciation to my professor and mother

A series of overbased magnesium fatty acids (D1-D7) such as

The prepared detergent additives were characterized and confirmed

The oil blends with 2% of overbased magnesium palmitate and

Antioxidant additives containing pyranopyrazole and

Reaction of S3 with three different types of carbanion compounds

The compound A1 was reacted with formic acid, formamide and

The oxidation stability of blends was examined according to

The oxidation stability study revealed that many of the tested

Lubricants are an important family among products of the refining

Lubricants are used in an important application, such as internal

A lubricant performs a number of functions. These include the

- Lubricant helps reduce friction and wear by introducing a

1.1.1 Lubricant Properties

Lubricant properties that are commonly considered for assessing

The role of viscosity in forming effective lubricating films makes it

Kinematic viscosity is usually determined by measuring the time t

A number of factors can affect viscosity. Viscosity decreases with

1.1.1.2 Viscosity Index:

Viscosity index (VI) is a measure of the viscosity-temperature

Viscosity Index was established by Dean and Davis [11]. An

Where, L is the 40°C viscosity of the 0 VI oil; U is the kinematic

1.1.1.3 Density and Gravity

The density of a substance is the mass of a unit volume of it at a

Density and gravity can be determined by means of hydrometers

1.1.1.4 Pour Point:

The pour point measures the temperature at which a base stock no

1.1.1.5 Volatility and Flash Point:

Volatility relates to base oil or its components to evaporate under

Flash Point is used as a measure of oil’s volatility. The flash point

1.1.1.6 Total Base Number:

The total base number (TBN) of oil is the quantity of acid,

1.1.1.7 Oxidation Stability:

Oxidation is initiated by the reaction of oxygen with the

The effects of excessive lubricant oxidation are noticeable by oil

In addition, there are other properties that are important in some

Table 1.1 Lubricant properties for various applications [18].

and wear control

1.1.2 Lubricants chemistry

- n-Paraffins: These are C18 and greater members of the n-paraffin

- Isoparaffins: These have n-paraffin backbones with alkyl branches.

- Cycloparaffins (naphthenes): Contain one or more cyclohexane or

- Sulfur-containing compounds: These may be thiols, sulfides,

- Nitrogen-containing compounds: Nitrogen largely appears in pyrroles,

Table 1.2 presents the relationship between various lubricant properties