8394 J . Org. Chem., Vol. 64, No. 22, 1999
Notes
9H), 1.27 (d, 3H, J ) 6.3 Hz), 1.89 (m, 2H), 2.04 (s, 3H), 4.10 (t,
2H, J ) 6.4 Hz), 5.00 (m, 1H); for 1-methyl-3-acetoxypropyl
trimethyl acetate (11c) δ 1.19 (s, 9H), 1.22 (d, 3H, J ) 6.3 Hz),
1.89 (m, 2H), 2.05 (s, 3H), 4.10 (t, 2H, J ) 6.4 Hz), 5.00 (m, 1H).
13C NMR (CDCl3, 300 MHz): for 3-acetoxybutyl trimethyl
acetate (10o) δ 20.0, 21.1, 27.0, 34.6, 38.5, 60.5, 67.6, 170.3,
178.3; for 1-methyl-3-acetoxypropyl trimethyl acetate (11c) δ
19.8, 20.8, 26.9, 34.6, 38.5, 60.6, 67.2, 170.8, 177.8. GC-MS: for
3-acetoxybutyl trimethyl acetate (10o) EI 115.1 (8), 99.1 (10),
85.1 (25), 57.0 (100), 42.9 (76); CI 217 (M+ + 1, 3), 157 (100),
115 (45); for 1-methyl-3-acetoxypropyl trimethyl acetate (11c)
EI 115.1 (16), 85.1 (18), 71.0 (20), 57.0 (100), 55.0 (53), 43.0 (69);
CI 217 (M+ + 1, 1), 157 (35), 115 (100).
21.5, 26.5 and 27.0, 45.0, 67.5, 81.4, 128.1, 129.3, 131.5, 132.5,
165.5, 170.4; for 1,3-dimethyl-3-acetoxybutyl benzoate (11f) δ
21.5, 21.6, 26.4, 26.8, 45.6, 68.1, 81.0, 128.2, 129.4, 130.5, 132.8,
166.6, 170.4. GC-MS (EI): for 1,1-dimethyl-3-acetoxybutyl
benzoate (10r ) 204.2 (3), 188.6 (1), 142.2 (43), 105.0 (100), 83.2
(62), 77.0 (29); for 1,3-dimethyl-3-acetoxybutyl benzoate (11f)
204.1 (3), 189.1 (1), 105.0 (100), 82.0 (50), 77.0 (28), 67.0 (48),
54.6 (35).
G. P r ep a r a tion of Mixed Diester s of 1,2-P r op a n ed iol by
Rea ction s of Isola ted 4-Meth yl-2-m eth ylen e-1,3-d ioxola n e
(8f) w ith Ca r boxylic Acid s. Diesters of 1,2-propanediol were
prepared by reacting 4-methyl-2-methylene-1,3-dioxolane (8f)
with trimethylacetic acid and benzoic acid in THF as described
in section A.
Mixtu r e of 3-Acetoxybu tyl Ben zoa te (10p ) a n d 1-Meth yl-
3-a cetoxyp r op yl Ben zoa te (11d ). Isolated yield: 95.2% (97%
overall GC purity, clear oil). Composition (GC area): 78.4%
3-acetoxybutyl benzoate (10p ) and 21.6% 1-methyl-3-acetoxy-
propyl benzoate (11d ). FTIR (KBr): 3066, 2980, 1737, 1720,
2-Acetoxyp r op yl Tr im eth yl Aceta te (10s) a n d 1-Meth yl-
2-acetoxyeth yl Tr im eth yl Acetate (11g). Isolated yield: 87.7%
(93% overall GC purity, clear oil). Composition (GC area): 95%
2-acetoxypropyl trimethyl acetate (10s) and 5% 1-methyl-2-
acetoxyethyl trimethyl acetate (11g). FTIR (KBr): 2979, 1742,
1277, 1243, 1113, 1027 cm-1 1H NMR (CDCl3, 300 MHz): for
.
1
3-acetoxybutyl benzoate (10p ) δ 1.30 (d, 3H, J ) 6.3 Hz), 2.02
(s, 3H), 2.04 (m, 2H), 4.38 (m, 2H), 5.12 (m, 1H), 7.43 (m, 2H),
7.55 (m, 1H), 8.03 (m, 2H); for 1-methyl-3-acetoxypropyl benzoate
(11d ) δ 1.39 (d, 3H, J ) 6.3 Hz), 2.00 (s, 3H), 2.04 (m, 2H), 4.19
(m, 2H), 5.29 (m, 1H), 7.43 (m, 2H), 7.55 (m, 1H), 8.03 (m, 2H).
13C NMR (CDCl3, 300 MHz): for 3-acetoxybutyl benzoate (10p )
δ 20.0, 21.1, 34.8, 61.2, 67.9, 128.2, 129.4, 130.1, 132.8, 166.3,
170.4; for 1-methyl-3-acetoxypropyl benzoate (11d ) δ 20.0, 20.7,
34.8, 60.8, 68.6, 128.2, 129.4, 130.1, 132.8, 165.9, 170.6. GC-
MS: 3-acetoxybutyl benzoate (10p ) EI 236.2 (M+, 1), 193.2 (2),
176.1 (4), 161.1 (8), 122.1 (10), 105.1 (100), 99.1 (8), 77.1 (24),
71.1 (10), 43.0 (47); CI 237 (M+ + 1, 5), 177 (100), 115 (53); for
1-methyl-3-acetoxypropyl benzoate (11d ) EI 176.1 (3), 148.2 (2),
134.1 (8), 105.0 (100), 77.1 (25), 71.1 (16), 42.9 (42); CI 237 (M+
+ 1, 3), 177 (45), 115 (100).
F . P r ep a r a tion of Mixed Diester s of 2-Meth yl-2,4-p en -
ta n ed iol by Rea ction s of Isola ted 4,4,6-Tr im eth yl-2-m eth -
ylen e-1,3-d ioxa n e (8e) w ith Ca r boxylic Acid s. Diesters of
2-methyl-2,4-pentanediol were prepared on the same scale by
reacting 4,4,6-trimethyl-2-methylene-1,3-dioxane (8e) with tri-
methylacetic acid or benzoic acid in THF as described in section
A.
1739, 1285, 1240, 1154, 1082, 1020 cm-1. H NMR (CDCl3, 300
MHz): for 2-acetoxypropyl trimethyl acetate (10s) δ 1.20 (s, 9H),
1.25 (d, 3H, J ) 6.3 Hz), 2.04 (s, 3H), 4.04 (q, 1H, J ) 14.8 and
6.4 Hz), 4.14 (q, 1H, J ) 14.8 and 3.4 Hz), 5.15 (m, 1H). 13C
NMR (CDCl3, 300 MHz): for 2-acetoxypropyl trimethyl acetate
(10s) δ 16.4, 21.0, 27.1, 38.7, 65.8, 68.1, 170.3, 178.0.
2-Acetoxyp r op yl Ben zoa te (10t) a n d 1-Meth yl-2-a cetoxy-
eth yl Ben zoa te (11h ). Isolated yield: 84.4% (92% GC purity,
clear oil). Composition (GC area): 89% 2-acetoxypropyl benzoate
(10t) and 11% 1-methyl-2-acetoxyethyl benzoate (11h ). FTIR
(KBr): 3070, 2988, 1741, 1725, 1277, 1238, 1111, 1072, 1027
cm-1. 1H NMR (CDCl3, 300 MHz): for 2-acetoxypropyl benzoate
(10t) δ 1.34 (d, 3H, J ) 6.3 Hz), 2.06 (s, 3H), 4.31 (q, 1H, J )
14.8 and ) 6.4 Hz), 4.40 (q, 1H, J ) 14.8 and 3.4 Hz), 5.30 (m,
1H), 7.44 (m, 2H), 7.56 (m, 1H), 8.03 (m, 2H). 13C NMR (CDCl3,
300 MHz): for 2-acetoxypropyl benzoate (10t) δ 16.4, 21.0, 66.4,
68.1, 128.3, 129.5, 129.6, 133.0, 166.1, 170.3.
H. P r ep a r a tion of Mixed Diester s of 3,3-Dim eth yl-1,2-
bu ta n ed iol by Rea ction s of Isola ted 4-(ter t-Bu tyl)-2-m e-
th ylen e-1,3-d ioxola n e (8g) w ith Ca r boxylic Acid s. Diesters
of 3,3-dimethyl-1,2-butanediol were prepared by reacting 4-(tert-
butyl)-2-methylene-1,3-dioxolane (8g) with trimethylacetic acid
and benzoic acid in THF as described in A.
Mixtu r e of 1,1-Dim eth yl-3-a cetoxybu tyl Tr im eth yl Ac-
eta te (10q) a n d 1,3-Dim eth yl-3-a cetoxybu tyl Tr im eth yl
Aceta te (11e). Isolated yield: 52.1% (98% overall GC purity,
clear oil). Composition (1H NMR integration): 78.3% 1,1-
dimethyl-3-acetoxybutyl trimethyl acetate (10q) and 21.7% 1,3-
dimethyl-3-acetoxybutyl trimethyl acetate (11e). FTIR (KBr):
3,3-Dim eth yl-2-a cetoxbu tyl Tr im eth yl Aceta te (10u ) a n d
1-(ter t-Bu tyl)-2-a cetoxyeth yl Tr im eth yl Aceta te (11i). Iso-
lated yield: 90.2% (92% GC purity, colorless oil). Composition
(GC area): 98% 3,3-dimethyl-2-acetoxybutyl trimethyl acetate
(10u ) and 2% 1-(tert-butyl)-2-acetoxyethyl trimethyl acetate
(11i). FTIR (KBr): 2972, 1736, 1284, 1239, 1153, 1063, 1029
1
2979, 1738, 1726, 1290, 1246, 1128, 1050, 1018, cm-1. H NMR
(CDCl3, 300 MHz): for 1,1-dimethyl-3-acetoxybutyl trimethyl
acetate (10q) δ 1.16 (s, 9H), 1.24 (d, 3H, J ) 6.3 Hz), 1.44 (two
singlets, 6H), 2.02 (s, 3H), 2.05 (m, 2H), 5.08 (m, 1H); for 1,3-
dimethyl-3-acetoxybutyl trimethyl acetate (11e) δ 1.18 (s, 9H),
1.21 (d, 3H, J ) 6.3 Hz), 1.45 (two singlets, 6H, 1.97 (s, 3H),
2.05 (m, 2H), 5.08 (m, 1H). 13C NMR (CDCl3, 300 MHz): for 1,1-
dimethyl-3-acetoxybutyl trimethyl acetate (10q) δ 21.4, 21.5,
25.8, 26.8, 27.1, 39.2, 46.1, 67.7, 80.4, 170.3, 177.7; for 1,3-
dimethyl-3-acetoxybutyl trimethyl acetate (11e) δ 21.3, 22.5,
26.0, 26.9, 27.0, 38.7, 45.8, 67.4, 80.8, 170.3, 177.7. GC-MS
(EI): for 1,1-dimethyl-3-acetoxybutyl trimethyl acetate (10q)
169.2 (1), 143.1 (9), 85.0 (19), 83.0 (100), 56.6 (57); for 1,3-
dimethyl-3-acetoxybutyl trimethyl acetate (11e) 226.2 (5), 184.3
(6), 82.9 (100), 56.6 (95).
cm-1 1H NMR (CDCl3, 300 MHz): for 3,3-dimethyl-2-acetoxy-
.
butyl trimethyl acetate (10u ) δ 0.97 (s, 9H), 1.17 (s, 9H), 2.08
(s, 3H), 4.01 (q, 1H, J ) 14.5 and 9.0 Hz), 4.35 (q, 1H, J ) 14.5
and 3.2 Hz), 5.00 (q, 1H, J ) 9.0 and 3.2 Hz). 13C NMR (CDCl3,
300 MHz): for 3,3-dimethyl-2-acetoxybutyl trimethyl acetate
(10u ) δ 20.8, 26.0, 27.0, 33.5, 38.7, 63.4, 77.5, 170.3, 178.3.
3,3-Dim eth yl-2-a cetoxybu tyl Ben zoa te (10v) a n d 1-(ter t-
Bu tyl)-2-a cetoxyeth yl Ben zoa te (11j). Isolated yield: 82.6%
(90% GC purity, clear oil). Composition (GC area): 95% 3,3-
dimethyl-2-acetoxybutyl benzoate (10v) and 5% 1-(tert-butyl)-
2-acetoxyethyl benzoate (11j). FTIR (KBr): 3069, 2964, 1741,
1
1725, 1277, 1237, 1111, 1062, 1027 cm-1. H NMR (CDCl3, 300
MHz): for 3,3-dimethyl-2-acetoxybutyl benzoate (10v) δ 1.02 (s,
9H), 2.08 (s, 3H), 4.31 (q, 1H, J ) 14.5 and 9.0 Hz), 4.55 (q, 1H,
J ) 14.5 and 3.2 Hz), 5.15 (q, 1H, J ) 9.0 and 3.2 Hz), 7.43 (m,
2H), 7.55 (m, 1H), 7.99 (m, 2H). 13C NMR (CDCl3, 300 MHz):
for 3,3-dimethyl-2-acetoxybutyl benzoate (10v) δ 20.9, 26.0, 33.6,
64.1, 77.6, 128.4, 129.6, 129.9, 133.0, 166.4, 170.6.
I. P r ep a r a tion of Mixed Aceta te Ben zoa te Diester s of
1-P h en yl-1,2-eth a n ed iol by Rea ction s of Isola ted 4-P h en yl-
2-m eth ylen e-1,3-d ioxola n e (8h ) w ith Ben zoic Acid . Diesters
of 1-phenyl-1,2-ethanediol were prepared by reacting 4-phenyl-
2-methylene-1,3-dioxolane (8h ) with benzoic acid in THF as
described in section A. Two isomers (1-phenyl-2-acetoxyethyl
benzoate (10w ) and 2-phenyl-2-acetoxyethyl benzoate (11k ))
were obtained as a colorless oil in 92% combined yield. The
composition (GC area) of the mixture was 89% 10w and 11%
11k . 1H NMR (CDCl3, 300 MHz): for 1-phenyl-2-acetoxyethyl
benzoate (10w ) (major isomer) δ 2.03 (s, 3H), 4.42 (q, 1H, J )
Mixtu r e of 1,1-Dim eth yl-3-a cetoxybu tyl Ben zoa te (10r )
a n d 1,3-Dim eth yl-3-a cetoxybu tyl Ben zoa te (11f). Clear oil,
isolated yield: 59.4%. Composition (1H NMR integration): 85.0%
1,1-dimethyl-3-acetoxybutyl benzoate (10r ) and 15.0% 1,3-
dimethyl-3-acetoxybutyl benzoate (11f). FTIR (KBr): 3066, 2981,
1
1736, 1715, 1276, 1249, 1114, 1026 cm-1. H NMR (CDCl3, 300
MHz): for 1,1-dimethyl-3-acetoxybutyl benzoate (10r ) δ 1.25 (d,
3H, J ) 6.3 Hz), 1.60 (two singlets, 6H), 1.77 (s, 3H), 2.01 (q,
1H, J ) 15.2 and 2.9 Hz), 2.49 (q, 1H, J ) 15.2 and 8.9 Hz),
5.25 (m, 1H), 7.41 (m, 2H), 7.52 (m, 1H), 7.98 (m, 2H); for 1,3-
dimethyl-3-acetoxybutyl benzoate (11f) δ 1.36 (d, 3H, J ) 6.3
Hz), 1.49 (two singlets, 6H), 1.83 (s, 3H), 2.04 (q, 1H, J ) 15.2
and 2.9 Hz), 2.40 (q, 1H, J ) 15.2 and 8.9 Hz), 5.43 (m, 1H),
7.43 (m, 2H), 7.52 (m, 1H), 8.05 (m, 2H). 13C NMR (CDCl3, 300
MHz): for 1,1-dimethyl-3-acetoxybutyl benzoate (10r ) δ 21.1,