PAPER
Synthesis of 1,1-Diacetates under Solvent-Free Conditions
3647
1
,1-Diacetoxy-1-phenylmethane (1b)
1,1-Diacetoxy-3-phenylprop-2-ene (17b)
IR (KBr): 3060, 1755, 1605, 1470, 1375, 1245, 1205, 1065, 1010,
7
IR (KBr): 3085, 2930, 1760, 1655, 1610, 1495, 1375, 1240, 1205,
–1
–1
60, 700 cm .
1110, 1005, 940, 750, 690 cm .
1
1
H NMR (CDCl ): d = 7.6 (s, 1 H), 7.4–7.2 (m, 5 H), 1.92 (s, 6 H).
H NMR (CDCl ): d = 7.65–7.15 (m, 6 H), 6.85 (d, J = 16 Hz, 1 H),
3
3
5
.9 (dd, J = 16, 7 Hz, 1 H), 2.1 (s, 6 H).
1
,1-Diacetoxy-1-(3-nitrophenyl)methane (3b)
IR (KBr): 3090, 1755, 1530, 1350, 1230, 1200, 1085, 1040, 950,
8
1,1-Diacetoxy-3-phenylpropane (18b)
–1
15, 730 cm .
IR (neat): 3070, 3050, 2930, 1750 (s), 1605, 1495, 1250 (s), 1020,
–
1
1
750, 700, 610 cm .
H NMR (CDCl ): d = 8.3 (s, 1 H), 8.2 (d, J = 7 Hz, 1 H), 7.8–7.5
m, 3 H), 2.0 (s, 6 H).
3
1
(
H NMR (CDCl ): d = 7.11 (s, 5 H), 6.8 (t, J = 6 Hz, 1 H), 2.80–2.55
3
+
(m, 4 H), 1.87 (s, 6 H).
MS (EI): m/z (%) = 210 (M – 43, 2), 194 (3), 150 (17), 134 (19),
1
05 (8), 77 (8), 51 (7), 43 (100).
1
,1-Diacetoxy-2-methylpropane (19b)
IR (neat): 2980, 1770 (s), 1480, 1385, 1230 (s), 1210, 1010, 610
cm .
1
,1-Diacetoxy-1-(4-nitrophenyl)methane (4b)
–
1
IR (KBr): 3095, 1765, 1610, 1530, 1345, 1210, 1200, 1090, 1000,
9
–1
1
60, 850 cm .
H NMR (CDCl ): d = 6.24 (d, J = 5.5 Hz, 1 H), 1.72 (s, 6 H), 0.8
3
1
(m, 1 H), 0.65 (d, J = 8.5 Hz, 6 H).
H NMR (CDCl ): d = 8.1 (d, J = 9 Hz, 2 H), 7.55 (d, J = 9 Hz, 2
3
+
H), 7.45 (s, 1 H), 2.1 (s, 6 H).
MS (EI): m/z (%) = 115 (M – 59, 23), 101 (12), 72 (28), 71 (100),
5
7 (40), 55 (53).
1
,1-Diacetoxy-1-(4-chlorophenyl)methane (6b)
IR (KBr): 3060, 3020, 1760 (s), 1605, 1480, 1210 (s), 1010, 780,
6
1,1-Diacetoxyhexane (20b)
–
1
20 cm .
IR (neat): 2970, 1755, 1460, 1375, 1235, 1205, 1090, 1020, 990,
–
1
1
650 cm .
H NMR (CDCl ): d = 7.55 (s, 1 H), 7.3–7.2 (s, 4 H), 2.1 (s, 6 H).
3
1H NMR (CDCl
): d = 6.6 (t, J = 5.5 Hz, 1 H), 2.0 (s, 6 H) 1.8–1.2
+
3
MS (EI): m/z (%) = 183 (M – 59, 10), 141 (45), 139 (100), 113 (8),
1
(m, 8 H), 0.9 (t, J = 5.5 Hz, 3 H).
11 (18), 104 (5), 77 (10), 75 (11), 57 (7), 51 (5).
1
,1-Diacetoxy-1-(2,6-dichlorophenyl)methane (7b)
Acknowledgment
IR (KBr): 3075, 1765,1600, 1490, 1385, 1250, 1200, 1020, 930, 815
cm .
–
1
We gratefully acknowledge the funding support received for this
project from the Isfahan University of Technology (IUT), IR Iran
1
H NMR: (CDCl ): d = 8.3 (s, 1 H), 7.35–7.10 (m, 3 H), 2.1 (s, 6 H).
3
(A.R.H.) and Grants GM 033138, MH 065503, NS 033650 (A.E.R.)
from the National Institutes of Health, USA. Further financial sup-
port from Center of Excellency in Chemistry Research (IUT) is
gratefully acknowledged.
1
,1-Diacetoxy-1-(4-cyanophenyl)methane (9b)
–
1
IR (KBr): 3070, 2210, 1760, 1380, 1230, 1205, 1010, 830 cm .
1
H NMR: (CDCl ): d = 7.68 (s, 4 H), 7.3 (s, 1 H), 2.14 (s, 6 H).
3
+
MS (EI): m/z (%) = 233 (M , 8), 190 (32), 174 (60), 130 (100), 102
References
(
40), 76 (17), 51 (12).
(
1) Green, T. W.; Wuts, P. G. M. Protective Groups in Organic
Synthesis, 3rd ed.; Wiley: New York, 1999.
2) Kochhar, K. S.; Bal, B. S.; Deshpande, R. P.; Rajadhyaksha,
1
,1-Diacetoxy-1-(3-methoxyphenyl)methane (11b)
IR (KBr): 3030, 2945, 2800, 1755 (s), 1610, 1500, 1380, 1220 (s),
1
(
–
1
205, 1015, 790, 720 cm .
S. N.; Pinnick, H. W. J. Org. Chem. 1983, 48, 1765.
1
H NMR (CDCl ): d = 7.55 (s, 1 H), 7.30 (t, J = 7.5 Hz, 1 H), 7.15–
(3) Held, H.; Rengstle, A.; Mayer, D. Ullmann’s Encyclopedia
of Industrial Chemistry, 5th ed, Vol. A 1; Gerhartz, W., Ed.;
VCH: Weinheim, 1985, 68.
3
7
.00 (m, 2 H), 6.80 (d, J = 7.5 Hz, 1 H), 3.70 (s, 3 H), 2.00 (s, 6 H).
1
,1-Diacetoxy-1-(4-acetoxy-3-methoxyphenyl)methane (13b)
(4) (a) Frick, J. G. Jr.; Harper, R. J. Jr. J. Appl. Polym. Sci. 1984,
1433. (b) Eanderson, W. R. European Patent Appl. EP
125781, 1985; Chem. Abstr. 1985, 103, 64010.
IR (KBr): 3050, 2950, 1770, 1750, 1610, 1500, 1465, 1385, 1250,
1
–
1
205, 1070, 990, 780 cm .
(
5) (a) Van Heerden, F. R.; Huyser, J. J.; Bradley, D.; Williams,
1
H NMR (CDCl ): d = 7.6 (s, 1 H), 7.25–7.05 (m, 3 H), 3.85 (s, 3
3
G.; Holzapfel, C. W. Tetrahedron Lett. 1998, 39, 5281.
H), 2.35 (s, 3 H), 2.2 (s, 6 H).
(
b) Sandberg, M.; Sydnes, L. K. Tetrahedron Lett. 1998, 39,
361.
6) Yadav, J. S.; Subba Reddy, V. B.; Srihari, P. Synlett 2001,
73.
7) Gregory, M. J. J. Chem. Soc. B 1970, 1201.
6
1
,1-Diacetoxy-1-(2-acetoxyphenyl)methane (14b)
(
(
IR (KBr): 3050, 2985, 1760, 1750, 1610, 1530, 1490, 1380, 1250,
6
–
1
1
205, 1160, 1070, 990, 950, 810, 750 cm .
1
H NMR (CDCl ): d = 7.75 (s, 1 H), 7.25–7.15 (m, 2 H), 7.1–7.0 (m,
3
(8) Freeman, F.; Karcherski, E. M. J. Chem. Eng. Data 1977,
2
H), 2.18 (s, 3 H), 1.94 (s, 6 H).
22, 355.
(
9) Michie, J. K.; Miller, J. A. Synthesis 1981, 824.
(10) Deka, N.; Kalita, D. J.; Borah, R.; Sarma, J. C. J. Org. Chem.
997, 62, 1563.
(11) Wang, C.; Li, M. Synth. Commun. 2002, 32, 3469.
1
,1-Diacetoxy-1-(2-furyl)methane (16b)
–
1
IR (KBr): 3100, 1750, 1500, 1240, 1200, 1060, 935, 830, 750 cm .
1
1
H NMR (CDCl ): d = 7.7 (s, 1 H), 7.4 (s, 1 H), 6.44–6.3 (m, 2 H),
3
(
(
12) Karimi, B.; Seradj, H.; Ebrahimian, R. G. Synlett 2000, 623.
13) Agarwal, V. K.; Fonquerna, S.; Vennall, G. P. Synlett 1998,
2
.1 (s, 6 H).
+
MS (EI): m/z (%) = 198 (M , 5), 155 (11), 139 (10), 113 (3), 97 (80),
5 (75), 43 (100), 39 (20).
8
49.
14) Chandra, K. L.; Saravanan, P.; Singh, V. K. Synlett 2000,
59.
9
(
3
Synthesis 2005, No. 20, 3644–3648 © Thieme Stuttgart · New York