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Synthetic Communications: An
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Baeyer-Villiger Oxidation of -
Aryl Substituted Unsaturated
Carbonyl Compounds with
Hydrogen Peroxide and
Catalytic Selenium Dioxide
a a a
J. A. Guzmn , V. Mendoza , E. Garca , C. F.
a a b
Garibay , L. Z. Olivares & L. A. Maldonado
a
Instituto de Investigaciones Qumico-Biolgicas,
Universidad Michoacana de San Nicols de Hidalgo,
Edificio B-1, Ciudad Universitaria, 58030, Morelia,
Michoacn, Mxico
b
Divisin de Estudios de Posgrado, Facultad de
Qumica, UNAM, 04510, Mxico, D.F., Mxico
Version of record first published: 23 Sep 2006.

To cite this article: J. A. Guzmn, V. Mendoza, E. Garca, C. F. Garibay, L. Z. Olivares

& L. A. Maldonado (1995): Baeyer-Villiger Oxidation of -Aryl Substituted Unsaturated
Carbonyl Compounds with Hydrogen Peroxide and Catalytic Selenium Dioxide,
Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 25:14, 2121-2133

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 SYNTHETIC COMMUNICATIONS, 25( 14), 212 1-2133 (1995)

BAEYER-VILLIGER OXIDATION OF 8-ARYL SUBSTITUTED

UNSATURATED CARBONYL COMPOUNDS WITH HYDROGEN PEROXIDE
AND CATALYTIC SELENIUM DIOXIDE
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J.A. Guzrniin', V. Mendoza', E. Garcia', C.F. Garihay',

L.Z. Olivares' and L.A. Maldonadob

'Institute de Investigaciones Quimico-Biolcigicas,

Universidad Michoacana de San Nicolk de Hidalgo,
Edificio B-1,Ciudad Universitaria, 58030 Morelia,
Michoadn MCxico.
hDivisi6n de Estudios de Posgrado, Facultad de Quimica,
UNAM, 04510 MCxico, D.F. MCxico.

ABSTRACT: A simple and cheap oxidative procedure using 30% H,O, and catalytic
SeO, allows to transform 2-a~alkylideneeycloalkanones and hydroxy- or
alkoxyhenzaldehydes to give, in high yields, endlactones and arylformates,
respectively.

In a recent research project from our laboratory, we ohserved that ketal 1

was rapidly converted, in high yield, into the e-enollactone 3_11 on treatment with

30% H,O, and a catalytic amount of SeO, in t-hutyl alcohol. Compound 3 was

'TO whom correspondence should he addressed.

2121

Copyright 0 1995 by Marcel Dekker, Inc.

 2122 GUZMAN ET AL.

identified by its physical and spectroscopic data, as well as, by conversion to

ketoacid 4 by alkaline hydrolysis (reaction 1).

A simple explanation for the formation of 3 involves acid-catalyzed

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4
-
3d
A r = 2-fury1

hydrolysis of the ketal protecting group, followed by a Baeyer-Villiger type

oxidation of intermediate ketone 2. In agreement with this explanation is the fact,

that ketone when submitted to the above reaction conditions, also afforded

lactone 3 in high yield but was unchanged by treatment with 30% HzOI alone

(reaction 2). Hence, it follows that S e O , plays an important role in this reaction,

possibly via in siru formation of a peroxyselenic acid (the true oxidant), as bas been

suggested by other authors in related work.'

-
3d *
H,O,- SeOl(ol)
1-BuOH
s57,
bAr A
HO no
1-BuOH
reaction (2)

2d
A r = 2-1 u ryl

The simplicity and convenience of this method, which does not suffer from

the problems associated with the use of molar amounts of SeO,, prompted us to

investigate its application in the Baeyer-Villiger oxidation of other

aralkylidenecyclaalkanones.
 BAEYER-VILLIGER OXIDATION 2123

TABLE 1

-
2 a-i
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2
- R Ar n

H 2-fury1 I

H phenyl 1

H 4-methoxyphenyl 1

H 2-fury1 2

H phenyl 2

H 4-methoxyphenyl 2

CH, phenyl 2

H phenyl 3

H 4-rnethoxyphenyl 3

T h e substrates 2a-i shown in the table 1, prepared by Claisen-Schmidt

condensation of the proper aromatic aldehydes and cycloalkanones, were submitfed

to the 30% H,O,-SeO, oxidation. After some preliminary experiments with 2d, we

found as the optimal conditions the use of 1.7 equivalents of H,O, and 0.03
 2124 GUZMAN ET AL.

TABLE 2

Reaction o f Z-nralk~lidenec-ycloLllkanones2 (5.68 mmof) wlith H,O, (9.65 mmol) and

St.0, (0.18 mmol) in t-hfyl alcohol at room temperature.

Suhst rii t e t-BuOH Reaction Producth Yield

(ml) Time (h) (%I

2 2 .o 60
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3 7.0 72

3 2 .o 70

2 0.5 85

4 6.0 87

4 1.5 85

4 8 .o 88

3 7.0 92

13 9.0 88

hlinimum volume for complete disolution of the substrate.

Products were characterized hy their spectral data OR, H-NMR, C-NMR and
hlS). Lactone5 3h-f have heen described in the literature?
Yield of isohted pure product.
B t u u s e of its low soluhility, an excess o f reagents (twice) was required for
complete reaction.

equivalents of Se02 in t-hutyl alcohol at room temperature (see experimental). All

these reactions were remarkahly clean affording in good yield and reasonably short

reaction times, the corresponding enollactones 3 by regiospecific migration of the

alkenyl group (reaction 3; see table 2).
 BAEYER-VILLIGER OXIDATION 2125

e
R-

-
2a-i -
3a-i

Reactions using SeO, in catalytic amounts in conjunction with stoichiometric

quantities of H102, have been described in the literature. They include the ring
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contraction of cycloalkanones to norcycloalkane carboxylic acids3 (and related

rearrangements in acyclic ketones4 as well as 3-ketosteroidss), epoxidation and

hydroxylation of insaturated compounds6, allylic oxidation' and oxidation of

aldehydes to carhoxylic acids*. However, with the exception of a brief comment by

Syper', Baeyer-Villiger oxidation of carhonyl compounds with the reagents used in

this paper have not been reported previously'. In his extensive studies of Baeyer-

Villiger oxidations of aromatic aldehydes with H,O, and catalytic organoselenium

compounds in CH,CI,, Syper obtained excellent yields of the corresponding phenols

(after hydrolysis of the intermediate formates) but only after rather long reaction

times (9-168 h)'. Therefore, it was of interest to compare our homogeneous reaction

conditions with those of Syper (heterogeneous), in the Baeyer-Villiger oxidation of

aromatic aldehydes (reaction 4). Our results are summarized in table 3.

As is seen from table 3, most of the ortho (or para)-hydroxy and

alkoxyhenzaldehydes 5 afforded phenols rapidly and in good yield. In some cases

it is possihle to reduce the oxidation reaction time by carrying out the reaction at

temperatures slightly above room temperature. Thus, the oxidation time of was

reduced from 7 h at room temperature to only 0.5 h when performed at 45-50C

 2 126 GUZMAN ET AL.

TABLE 3

Oxidation of alkoxy and hydroxyhenzaldehydes 5 (7.3 mmol) with H,O, (12.4 mmol)
and SeO, (0.18 nimol) in t-hutyl alcohol at room temperature.

Aldehyde t-BuOH Reaction Phenol' Yieldb

(ml) Time (h) (%)

-
5a 2-HOC6H,CH0 3 4 80
-
5b 4-HOC6H,CH0 3 4 85
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5c
- 2-CH,0C,H4CH 3 5 86
5d
- 4-CH30C6H4CH0 3 7 85
-
5e 3-CH30C6H,CH0 3 17 0'
-
51 2-HO-3-CH30C6H3CH0 5 4 75
5 3-HO-4-CH,0C6H3CH0 10 12 75
-
5h 4-10-3-CH30C6H3CH0 3 I 72
4-CH,COz-3-CH30C,H,CH0 10 18 Od
3 2,3-(CH30),C,H3CH0 4 30 43'
5k
- 2 ,S-(CH30),C,H,C HO 3 3 90
51 3,4-(CH30),C6H,CH0 3 4 84
5rn' 4-PhCH,OC6H,CHO
- 7 10 6@

a Ohtained by alkaline hydrolysis of the initially produced formats.

Yield of isolated pure product.
c*d Only the corresponding clrrhoxylic acids were isolated in '81% and 86% yields.
2,3-Dirnethoxyhenzoic acid was isolated in 44% yield.
Because of its low solubility, the oxidation of &I was accomplished at 45-5OoC,
using the following ratio (mmol) of suhstrate and reagents (aldehyde/H,O,/SeO,):
2.26/7/0.09.
4-Benzyloxyhenzoic acid was isolated in 33% yield.

in about the same yield. Solubility prohlems of the starting material at room

temperature can also he overcome in this manner as shown for the oxidation of a.
On the other hand, meta-suhstituted or henzaldehydes carrying less effective
 BAEYER-VILLIGER OXIDATION 2127

electron-donating groups (& and 9 were slowly oxidized to the corresponding

arboxylic acids (table 3).

0 0
II 11 hydrol.
Ar-CH b Ar-OCH FAr-OH (4)
5 - -
6

In conclusion from the above results, we believe that the very simple and
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cheap oxidative procedure reported in this paper represents a useful alternative to

those commonly used for carrying out this type of conversions in the synthetic

field".

EXPERIMENTAL SECTION

The progress of the reactions was monitored by TLC, using glass coated

silica gel plates 60 FLU(hlerck). Sublimed S e O , and 30% H,O, were purchased from

Merck and were used without further treatment. The aralkylidenecycloalkanones

-
2a-i are known compounds and were prepared by alkaline aldol condensation of the

proper ketone and aldehyde. All the benzaldehydes used were commercially

available. hlelting points were taken using a Fisher-Johns apparatus and are

uncorrected. IR spectra were recorded on a Perkin-Elmer 5998 spectrophotometer.

'H and "CC-NMRspectra were obtained using P Varian Gemini 200 instrument.

Mass spectra were recorded on a Hewlett Packard 59854-A spectrometer at 70 eV.

Elemental analyses were performed by Galhraith Laboratories, Inc., Knoxville, TN.

 2128 GUZMAN ET AL.

TABLE 4

Analytical data of compounds 3

Pro- mp (C) Molecular Analvses

duct (solvent) Formula or C H N
Lit. mp (C) Cnlc. Found Calc. Found Calc. Found
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3a 108-109 C,,H,,0,N3 53.92 54.23 6.41 6.69 15.72 15.48

(Et,O) (267.3)

-
3b 76-78 79-SC?
(pentane)

& 76-77 72-73

(hexanel
EtzO)

Mb 147-148 1502
(MeOH)

-
3e 67-69 70-71
(hexane)

& 34-35 CI,Hl,O 77.74 77.66 7.45 7.42

(pentane) (216.3)

3h
- 44-45 Cl,Hl60* 77.74 77.86 7.45 7.67
(pentane) (216.3)

3i
- 67-68 ClSHI,O, 73.14 73.00 7.36 7.64
(hexanel (264.3)
EtZO)

* Analyzed as semicarhazone of methyl ketaester [Ar-CH,CO(CH,), COCH,]

produced by reaction with MtrONa.
Analized as semicarhazone of hydrolysis product.
 BAEYER-VILLIGER OXIDATION 2129

Oxidation of 2-araIkvlidenecvclo~lkanones2. General procedure.

To a magnetically stirred mixture of ketone m,SeO,and t-BuOH, aqueous

30% H,O, was added dropwise (see tahle 2 for specific reaction parameters). The

readion mixture was stirred at room temperature (water bath) and, after

consumption of the starting material (TLC, eluant: hexaneAcOEt), Et,O (20 ml)

was added. The mixture was washed with aqueous saturated NaCl (3 X 10 ml) and
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dried over anhydrous Na,SO,. After evaporation the crude product was purified,

either by recrystallisation and column chromatography of mother liquors (3b, pa

or column chromatography (silica gel, hexaneAcOEt) (3a and m.Because and

3 (which were oils at room temperature) suffer partial decomposition during

purification, the yield of these products was calculated after opening the lactone ring

hy treatment with CH,ONa and chromatographic purification of methyl ketoesters

produced. Tables 4 and 5 show the analytical and spectral data, respectively, for

lactones s.

Oxidation of henzaldehvdes 5 and hidrolvsis of the corresDondinP arvl formates to

phenols 6. General procedure.

Aldehydes 5 were oxidized as descrihed ahove for ennnes 2 (see tahle 3 for
specific reaction parameters). The residue ohtained after evaporation of solvents,

was dissolved in CH,OH (10 ml) and magnetically stirred. Then, a solution of

K,CO, (0.5-1 g) in H,O (5 ml) was added; the mixture was allowed to stand at room

tenperature for 0.5-1 h and then, the solvent was removed under reduced pressure.

To the residue, water (10 ml) was added and extracted with EGO (2 x 10 ml); the
 2130 GUZMAN ET AL.

TABLE 5

Selected spectral data of compounds 3

Pro- 1R 'H-NMR(CDC1JfM.S) 'C-NMR(CDCI,/TMS) MS

duct (CHCIJ G(CH,-C = 0; CH,C = C; bCH,-C = C; CH,-C =0; m/z (%)
v(cm-') vinylic CH)', J(Hz) vinylic CH; C=O)*
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1750 2.65 (t,J=6.7; 2.98 24.42; 30.76; 178(M+, 65)

1670 (t,J=6.7); 6.09 (s) 101.35; 168.52 108(100)

1740 2.66 (t,J=6.68); 2.75 23.93; 30.74; 188(M+,5.4)

1660 (t,J=6.5); 6.31 (s) 111.5; 168.56 55( 100)

1750 2.66 (t,J=6.76); 2.75 23.91; 30.76; 218(M+,9.5)

1660 (t,J=6.5); 6.26 (s) 111.13; 168.73 77(100)

1745 2.59-2.65(m); 2.74- 30.72; 33.67; 192(M+, 2)

1660 2.79(m); 6.18 (s) 108.03; 173.29 52(100)

1735 2.56-2.6 1(nil ; 2.63- 29.74; 33.8; 202(M+, 1.5)

1655 2.7 (m); 6.44 (s) 119.29; 173.36 90(100)

1740 2.55-2.61(m); 2.65- 29.75; 33.78; 232(M+, 4.9)

1660 2.7 (m); 6.38 (s) 118.1; 173.64 121(1 00)

1740 2.2-2.35 and 2.83- 29.35 CH,-C=C); 2 16(M+,18.9)

1660 2.88(2m, CH,-C=C); 36.75cH-C =O); 118 (100)
2.9-3.0 (m,CH-C=O); 118.88; 175.76
6.42 (s)

1730 2.59-2.65(m);2.68- 30.44; 32.23; 216(M+, 3)

1650 2.75(m); 6.39 (s) 120.57; 174.58 118(100)

1735 2.58-2.63(m);2.67- 30.37; 32.25; 246(M+, 10)

1660 2.74 (m); 6.32 (s) 120.09; 174.84 148(100)

'The assignment of methylene signals may be interchanged

 BAEYER-VILLIGER OXIDATION 2131

aqueous phase was saturated with NaCl and extracted again with EGO (2 x 10 ml).

The combinated organic phases were washed with aqueous saturated NaCl (2 x 5

ml) and dried over anhydrous Na,SO,. Removal of solvent gave the phenols in

almost pure form as judged by TLC and 'H-NMR; they were further purified by

recrystallisation (6a, b, d, h, 1, or column chromatography (silica gel, hexane-

AcOEt) (6c, I, g, j, kJ. All phenols 6 prepared are known. Phenols !lad,I, i, 1, m
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were characterized by comparison of their 'H-NMR spectra with those reported in

The AIdrich Library of NMR Spectra". Melting points ("C) and crystallisation

solvents were as follows: 6a,100-102, toluene (lit.'' 104-106); 6b, 170-172, hexane-

Et,O (lit." 172-175); & (as benzoate), 54-55, EtOH (lit." 58); &I,
51-52, hexane

(lit.'* 55-57); 6f,34-36, cyclohexane (lit." 40-43); 5,

64-66, CHCI, (lit.'4 67-68); &

(as diacetate), 60-61, hexane (lit.I4 63-64); a,85-86, CHCI, (lit." 89-91); (as

acetate), 64-65, pentane (lit.Ls 68-69); 6 3 , 77-78, hexaneEt0 (lit." 79-82); &I, 116-

118, hexaneEtO (lit." 120-122).

ACKNOWLEDGEMENTS

Financial support of the Coordinacih de la Investigacih Cientffica

(UhfSNH) is gratefully acknowledged. We thank Q.F.B. B. Nateras for experimental
assistance, Q.F.B. J.C. Calder6n and M.C. R.E. del Rio for obtaining IR, 'H and
"C-NMR spectra, Ing. L. Velasco (Instituto de Quirnica, UNAILI) for the mass
spectra and A.B. Alvarez for manuscript typing.

REFERENCES AND NOTES

1. Syper, L. Synthesis 1989, 167.

 2132 GUZMAN ET AL.

2. Enollactones s f have been prepared previously hy Baeyer-Viliiger

oxidation of aralkylidenecycloalkanones with peroxyacetic acid: Walton,

H.M. J . Org. Chem. 1957,22, 1161.

3. Payne, G.B. and Smith, C.W. J. Org. Chem. 1957, 22, 1680.

Ishii, Y., Adachi, A., Imai, R. and Ogawa, M. Chem. Lett. 1978, 611.

4. Hellman, H.M. and Rosegay, A. Tetrahedron Lett. l959, 1.

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Sonoda, N. and Tsutsumi, S. Bull. Chem. SOC.Jpn. 1959, 32, 505.

Sonoda, N. and Tsutsumi, S. Bull. Chem. SOC.Jpn. 1960,33, 1440.

5. Biellmann, J. and Rajic, M. Bull. SOC.Chim. Fr. 1962, 441.

Caspi, E. and Balasuhrahmanyam, S.N. Tetrahedron Lett. 1963, 745.

Caspi, E. and Balasubrahmanyarn, S.N. J. Org. Chem. 1963, 28, 3383.

Caspi, E., Shiniizu, Y. and Balasubrahmanyam, S.N. Tetrahedron 1964,20,

1271.

Hellmann, H.M. and Jerussi, R.A. Tetrahedron 1964, 20, 741.

6. Itakura, J., Tanaka, H., hlatsuhara, T. and Ito, H., Fr. Patent 1570838,

1969; Ckem. Abstr. 1970, 72, 89896.

Payne, G.B. World Petrol. Congr., Proc., Sth, N . Y. 1959, 4 , 185-196; Chem.

Abstr. 1963, 58, 4389.

7. Coson, J.M., Dansted, E. and Hartshorn, h1.P. Org. Syn. 1977, 56, 25.

8. Smith, C.W. and Holm, R.T. J. Org. Chem. 1957, 22, 746.

Ishii, Y., Murai, S. and Sonoda, N. Tecknol. Rep. Osaka Univ. 1976, 26,

623; Chem. Abstr. 1977, 86, 54738.

Pikh, Z.G., Denis, G.A. and Yatchishin, 1.1. Zh. Org. Kkiin. 1979, 15, 1831;

Chem. Ahstr. 1980, 92, 180633.

 BAEYER-VILLIGER OXIDATION 2133

Shi, X., Hao,T., Wang, Y. and Wang, R. Yingyong Huaxue 1986, 3 , 61;

Chem. Abstr. 1987,107, 175609.

9. For a Baeyer-Villiger oxidation of a a,B-unsaturnted aldehyde to an

enolformate with anhydrous H302in t-amyl alcohol in the presence of SeO,

(70, 2 h) see: Nakatsuho, F., Kishi, Y. and Goto, T. Tetrahedron Lett.

1970,381.
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10. Early, during the syntheses of some natural benzoquinones, we carried out

the conversion of an aromatic aldehyde into a phenol using these reagents:

Garcia, E., Mendoza, V. and Guzmin, J.A. J . Nat. Prod. 1987, 50, 1055.

11. Pouchert C.J. "The Aldrich Lihrary of NMR Spectra", 2nd ed., Aldrich

Chemical, Milwaukee, WI, 1983.

12. Aldrich Catalog Handhook of Fine Chemicals, 1994-1995.

13. Lide, D.R. "CRC Handbook of Chemistry and Physics", 74th ed., CRC

Press, B o a Raton, FL., 1993.

14. Velluz, L. and Amiard G. Bull. SOC. Chim. Fr. 1948, 1109; Chem. Abstr.

1949, 43,3823e.

1s. Bartram, C.A., Battye, D.A. and Worthing, C.R.J. Chem. SOC.1963,4691;

Chem. Abstr. 1963,.59, 12679~.

(Received i n t h e USA 31 October 1994)