Académique Documents
Professionnel Documents
Culture Documents
20, 1979
Notes
temp, "C
pressure,b
mmHg
% 2af
la
la
la
la
la
1ac
1ac
1 ad
400
500
630
500
582
614
600
600
0.4
0.6
0.7
33
760e
760e
0.5
0.5
2
11
28
4
2
3
21
0
enol forms and gave a positive ferric chloride test. Results for
pyrolysis of 7 at other temperatures are reported in Table 11. All
products were identified by comparison with authentic samples
(NMR, GC).
Registry No. la, 98-86-2;Za, 536-74-3;5 , 1021-45-0;6a, 93-55-0;
6b,673-32-5; 7, 2206-94-2; 8, 93-91-4; phenacyl chloride, 532-27-4;
triethyl phosphite, 122-52-1;isopropenyl acetate, 591-87-7.
reagent
temp, pressure,
"C
mmHg % 2 a
7
7
7b
7
7
7
8
2a
420
534
529
650
700
760
760
700
0.03
0.03
0.05
0.05
0.05
0.7
0.4
0.2
5
6
30
37
95
6
12
30
60
%7
%8
95
92
95
9
36
tr
tr
72
36
' Without
was placed in the reactor and allowed to flash distill through the
tube. Reactions at atmospheric pressure were carried out under
a nitrogen flow of 0.5 SCFM. Volatile products were collected
in dry ice/acetone. Then the products were dissolved in ether
and dried over anhydrous magnesium sulfate and the ether was
removed in vacuo under conditions where losses of phenylacetylene
or acetophenone were minimized. The products were analyzed
by NMR and GC on a 2-ft UCW 982 column and by comparison
with authentic samples. Results are shown in Table I.
Synthesis of Diethyl 1-Phenylvinyl Phosphate ( 5 ) . To 15.5
g (0.1 mol) of phenacyl chloride in a 200-mL one-neck flask was
added 16.6 g (0.1 mol) of triethyl phosphite. This was heated at
86 "C for 4 h with stirring. The product was then distilled at 121
"C (0.03 mm) [lit.Iobp 101-105 "C (0.005 mm)], and 21.9 g was
recovered 86% yield; NMR (CDC13)6 7.2-7.8 (m, 5 H, aromatic
H), 5.25 (d, 2 H, C=CH2, J = 3 Hz), 4.20 (9, 2 H, OCHZ, J = 8
Hz), 4.33 (4, 2 H, OCHZ, J = 8 Hz), 1.38 (t,6 H, CH3, J = 8 Hz).
Preparation of 1-Phenylvinyl Acetate (7). To 40 mL of
isopropenyl acetate in a flask equipped with a magnetic stirrer
and distillation head was added 24 g (0.2 mol) of acetophenone
and 0.2 g of p-toluenesulfonicacid. After heating for 7 h at 98-118
"C, 15 mL of acetone had distilled and approximately 75%
conversion to 7 was observed by NMR sampling of the product
mixture. The reaction was then cooled, extracted with ether, and
washed once with 10 g of sodium bicarbonate in 100 mL of ice
water. The ether was then dried over anhydrous magnesium
sulfate and removed in vacuo. The product distilled at 90 "C (4
mm)[lit. 92-95 "C (4.5 mm)]14and18 g was recovered 56% yield;
NMR (CDC13)b 7.4 (m, 5 H, ring H's), 5.60 (d, 1 H, C=CH, J
= 2 Hz), 5.10 (d, 1 H, C=CH, J1 = 2 Hz), 2.30 (s, 3 H, CH3).
Pyrolysis on 7 to Form l-Phenyl-1,3-butanedione.Enol
acetate (7; 2.0 g) was flash distilled through a quartz pyrolysis
tube at 650 "C at 0.5 mm of vacuum. The product 8 (1.81g, 90%
yield) was collected in an ice bath and recrystallized from ethanol-water: mp 56-57 "C (lit." mp 60 "C); NMR (CDC13)6 7.2-8.0
(in, 5 H, ring H), 6.20 (s, 1 H, vinyl H), 2.60 (9, 2 H, CH2 keto
form), 2.20 (s, 3 H, CH3). The product 8 was present in keto and
(14) D. S. Noyce and R. M. Pollack, J . Am. Chem. SOC.,91,119 (1969).
0022-3263/79/1944-3580$01.00/0
1 HaX,
Notes
RTJf-1
R
OCH,
OCH,
OCH,
OCH,
OCH,
f, OCH,
h, H
i, CF,
j,(l OCH,
k: CF,
1, CF,
amine (NR',)
NH,CH,CH( OEt),
NH,CH,CH,CH,CHI
NH,CH,Ph
NH(CH,CH,),
NH,Ph
"W
.a
NH,CH,Ph
NH,CH,Ph
NH,CH,CH,b
NH,CH,CH,b
NH ,CH,CH( OEt),
isolated
213 yield, %
100/0
87
48
78
39
41
lOO/O
68
Sol20
86
9O/lO
71
57
87
93
62
100/0
100/0
90/10
60140
100/0
80/20
82/18
90/10
30% aqueous
<
:R,~+-&XlXri
3582
General Procedure for the Preparation of a-Methylphenethylamines (Table I). The following are typical examples
of the aminomercuration-demercuration procedures used for the
preparation of 2a-1.
N-(2,2-Diethoxyethyl)-l-(3-methoxyphenyl)-2-propylamine (2a). To a stirred solution of Hg(N03)z.Hz0(51.4 g, 0.15
mol) in tetrahydrofuran (100 mL) under nitrogen was added
aminoacetaldehyde diethyl acetal (64.0 g, 0.48 mol) and then
3-methoxyallylbenzene (17.8 g, 0.12 mol), and the mixture was
heated to 60-65 "C for 24 h. After the solution was cooled to
ambient temperature, 10% NaOH (100 mL) and NaBH4 (12.0
g, 0.32 mol) were added, and the mixture was stirred for 18 h,
acidified to pH 1 with 10% HC1, stirred until no more gas evolution was observed upon the addition of small amounts of 10%
HCl (ca. 1-2 h), then basified to pH 11 with 20% NaOH, and
extracted with chloroform. The extracts were dried over MgS0,
and evaporated to an oil, which was distilled under vacuum to
remove the excess aminoacetaldehyde diethyl acetal and traces
of 3-methoxyallylbenzene (bp 45-68 "C (0.05 mm)). Distillative
or chromatographic (silica gel) purification of the residue affords
2a as a pale yellow oil (29.4 g, 87% yield): bp 135-142 "C (0.05
mm); IR (neat) 3330, 1600, 1582, 1258, 1150, 1055 cm-'; NMR
(CDCl,) 6 1 . e 1 . 4 (m, 9 H), 1.7 (s, 1 H), 2.5-3.2 (m, 5 H), 3.2-3.75
(m, 4 H), 3.8 (s, 3 H), 4.6 (t, 1 H), 6.5-7.0 (m, 3 H), 7.0-7.3 (m,
1 H).
Anal. Calcd for Cl6HZ7No3:C, 68.29; H, 9.67; N, 4.98. Found:
C, 68.06; H, 9.66; N, 4.92.
N-Ethyl-I-(3-(trifluoromethyl)phenyl)-2-propylamine(2k)
and N-Ethyl-3-(3-(trifluoromethyl)phenyl)-l-propylamine
(3k). To a stirred solution of Hg(C104)2.3H20(68.0 g, 0.15 mol)
in tetrahydrofuran (200 mL) under nitrogen at 0 "C was added
70% aqueous ethylamine (46.3 g, 0.72 mol) and then 3-(trifluoromethy1)allylbenzene (22.4 g, 0.12 mol), and the mixture was
heated to 65 "C for 72 h. After the solution was cooled to ambient
temperature, 10% NaOH (100 mL) and NaBH, (12.0 g, 0.32 mol)
were added, and the mixture was stirred for 18 h and acidified
with 10% HC1 to pH 1. An additional portion of concentrated
HCl (50 mL) was added, the mixture was stirred for 5 h and
extracted with petroleum ether, and the aqueous phase was
basified to pH 11with 20% NaOH and extracted with chloroform.
The chloroform extracts were dried over MgSO, and evaporated
in vacuo to a yellow oil (26.0 g, 93% yield) consisting (GLC) of
82% 2k and 18% N-ethyl-3-(3-(trifluoromethyl)phenyl)-lpropylamine (3k),which were separated by preparative column
chromatography on silica gel and isolated as the hydrochloride
salts from ethanol/ether.
2k: mp 166-167 "C (lit.12mp 166 "C); IR (KBr) 2900-2300,
1585, 1455,1330, 1160, 1065 cm-'; NMR (CDC13)6 1.19 (d, 3 H,
J = 7 Hz), 1.35 (t, 3 H, J = 7 Hz), 2.5-4.7 (m, 5 H), 7.65 (s, 4 H),
9.5 (br s, 2 H).
Anal. Calcd for Cl2HI7F3NC1:C, 53.83; H, 6.40; F, 21.28; N,
5.23; C1, 13.24. Found: C, 53.90; H, 6.30; F, 21.10; N, 5.22; C1,
13.42.
3k: mp 144-145 "C;IR (KBr) 2900-2300,1590,1450,1332,
1065 cm-'; NMR (CDC13)6 1.4 (t, 3 H), 2.3 (m, 2 H), 2.9 (m, 6
H), 7.4 (5, 4 H), 9.2 (br s, 2 H).
Anal. Calcd for C12H17F3NC1:C, 53.83; H, 6.40; F, 21.28; N,
5.23; C1, 13.24. Found: C, 53.74; H, 6.40; F, 21.42; N, 5.23; C1,
13.22.
Notes
N-Benzyl-l-(3-methoxyphenyl)-2-propylamine
(212): mp
143-143.5 "C; IR (KBr) 2930,2760,1600,1490,1445,1265,1165,
1040,990,835,785 cm-'; NMR (CDCl,) 6 1.33 (d, 3 H, J = 7 Hz),
2.8-3.6 (m, 3 H), 3.73 (s, 3 H), 4.10 (br t, 2 H), 6.5-7.8 (m, 9 H),
10.4 (br s, 2 H).
Anal. Calcd for Cl7Hz2C1NO:C, 69.97; H, 7.60; C1, 12.15; N,
4.80; 0, 5.48. Found C, 69.91; H, 7.62; C1, 12.16; N, 4.85; 0,5.40.
N,N-Diethyl-l-(3-methoxyphenyl)-2-propylamine
(2d): mp
123-124 "C; NMR (CDC13) 6 1.31 (d, 3 H, J = 6.7 Hz), 1.56 (t,
6 H, J = 7 Hz), 2.2-3.7 (m, 7 H), 3.80 (s, 3 H), 6.8-7.5 (m, 4 H),
12.4 (s, 1 H).
Anal. Calcd for Cl4H2,C1NO: C, 65.23; H, 9.38; C1, 13.75; N,
5.43; 0, 6.21. Found: C, 65.36; H, 9.46; N, 5.32; 0, 6.18.
N-Phenyl-1- (3-methoxyphenyl)-2-propylamine(2e): mp
176-177 "C; IR (KBr) 2940, 2830, 1600, 1490, 1450, 1260, 1165,
1035, 857, 780, 750 cm-'; NMR (MezSO-d6)6 1.17 (d, 3 H, J =
6.5 Hz), 2.7-3.6 (m, 2 H), 3.78 (s, 3 H), 3.8-4.2 (m, 1 H), 6.7-7.0
(m, 4 H), 7.0-7.8 (m, 6 H).
Anal. Calcd for Cl6Hz0C1NO:C, 69.17; H, 7.25; c1, 12.76; N,
5.04; 0, 5.75. Found: C, 68.96; H, 6.93; C1, 12.62; N, 5.16; 0, 6.24.
N - [2-(3-Methoxyphenyl)-1-methylethyl]morpholine (2f):
mp 14&146 "C; IR (KBr) 2950,2590,1600,1595,1490,1460,1260,
1175,1040,785,745cm-'; NMR (CDC13)6 1.31 (d, 3 H, J = 6 Hz),
2.4-3.0 (m, 1 H), 3.0-3.7 (m, 6 H), 3.77 (s, 3 H), 4.0-4.7 (m, 4 H),
6.6-7.5 (m, 4 H), 12.7 (s, 1 H).
Anal. Calcd for Cl4HZzC1NO2:C, 61.86; H, 8.15; C1, 13.04;N,
5.15; 0, 11.77. Found: C, 61.85; H, 8.14; C1, 13.07; N, 5.20; 0,
11.69.
c,
N-Benzyl-l-(3-(trifluoromethyl)phenyl)-2-propylamine
(2i): mp 165-166 "C (lit.14mp 170-172 "C); IR (KBr) 2940,2780,
1580, 1460, 1330, 1170, 1120, 795, 750 cm-'; NMR (CDC13/
MezSO-d6)6 1.38 (d, 3 H, J = 6.5 Hz), 3.0-3.9 (m, 3 H), 4.20 (br
d, 2 H), 7.4-7.9 (m, 9 H), 11.5 (s, 2 H); mass spectra m / e (intensity)
292 (l), 278 (2), 196 (3), 134 (53), 106 (121, 91 (loo), 89 (21, 77
(2).
N-Ethyl-1-( 3-methoxyphenyl)-2-propylamine (2j): mp
142-143 "C (lit.15 mp 137-139 "C); IR (KBr) 2960,2800, 1600,
1490, 1450,1265, 1025,870,790,700 cm-'; NMR (CDC13)6 1.38
(d, 3 H, J = 6 Hz), 1.55 (t, 3 H, J = 6.5 Hz), 2.5-3.7 (m, 5 H),
3.78 (s, 3 H), 6.6-7.4 (m, 4 H), 9.56 (br s, 2 H).
Anal. Calcd for C12H2&1NO: C, 62.73; H, 8.77; C1, 15.43; N,
6.09; 0,6.96. Found C, 62.66; H, 8.80; C1, 15.26; N, 6.12; 0, 7.02.
N-Ethyl-3-(3-methoxyphenyl)-l-propylamine
(3j): mp
103-104 "C; IR (KBr) 2950,2820,1600,1445,1260,1175,1035,
790,700 cm-'; NMR (DzO)6 1.40 (t,3 H, J = 6.5 Hz), 1.7-2.5 (m,
2 H), 2.70 (br d, 2 H, J = 7 Hz),3.09 ( q , 4 H, J = 7 Hz),3.87 (s,
3 H), 6.7-7.1 (m, 3 H), 7.1-7.5 (m, 1 H).
Anal. Calcd for Cl2Hz0C1NO:C, 62.73; H, 8.77; C1, 15.43;N,
6.09; 0,6.96. Found: C, 62.90; H, 8.84; C1, 15.54; N, 6.29; 0, 6.73.
Notes
Scheme I
7 (70%)
= Y
HE
8a, R = H (91%)
b, R = TBS (97%)
OMF
9, R = TBS (79%)
10,R = H (95%)
/u \
%&4
NoOCH3
Stereochemistry of t h e Diels-Alder Reaction of
Vinylcyclohexene o r
1-[a- ( tert -Butyldimet hylsilyloxy)vinyl]-A1-cyclohexene a n d 2-Methylcyclopentenone
Robert
E. Ireland* and W a y n e J. T h o m p s o n
S. M a n d e l a n d Gretchen S. M a n d e l
11 (85%)
.Q
OTBS
OTBS
4 (64%)
5 (100%)
II H
Q
0022-3263/79/1944-3583$01.00/0