J. CHEM. RESEARCH (S), 1999 269
Table 1 Synthesis of diacetals catalysed by anhydrous ferrous sulfate
Mp/ꢀC
Isolated
Entry
1
Aldehydes or ketones
Solvent (t/h)
yield (%)
Found
62^63
Reported
635
n-C6H13CHO 1a
Benzene (1.2)
Toluene (0.8)
Benzene (1.5)
Toluene (0.8)
Benzene (1.5)
Toluene (1.0)
Benzene (1.5)
Toluene (0.8)
Benzene (2.5)
Toluene (1.5)
Benzene (2.0)
Toluene (1.5)
Benzene (3.0)
Toluene (2.0)
Benzene (3.0)
Toluene (2.0)
Benzene (2.5)
Toluene (1.5)
Benzene (3.5)
Toluene (2.5)
Toluene (7.0)
Benzene (3.0)
Toluene (2.0)
Toluene (8.0)
Benzene (3.0)
Toluene (2.0)
Benzene (3.0)
Toluene (6.0)
Toluene (8.0)
Toluene (10)
Toluene (8)
93
95
97
98
98
98
98
99
94
95
96
98
93
95
92
94
90
92
90
92
74
95
95
84
94
95
92
90
87
89
0
2
PhCHO 1b
155^156
211^212
180^182
190^192
121^122
196^197
162^164
185^186
160^161
155^15614
211^2131
1775
3
4-MeC6H4CHO 1c
4-MeOC6H4CHO 1d
3,4-(OCH2OC6H3CHO 1e
3-ClC6H4CHO 1f
4-ClC6H4CHO 1g
2-O2NC6H4CHO 1h
3-O2NC6H4CHO 1i
2-HOC6H4CHO 1j
4
5
1885
6
121^1221
197^19814
163^16414
1855
7
8
9
10
160^1611
11
12
4-HOC6H4CHO 1k
3-MeO-4-HOC6H3CHO 1l
108^110
170^172
109^11014
170^1711
13
14
4-Me2NC6H4CHO 1m
PhCHCHCHO 1n
223^224
190^192
2231
1935
15
16
17
18
19
2-Furaldehyde 1o
Cyclohexanone 1p
PhCOMe 1q
(PhCH2)CO 1r
Ph2CO 1s
157^159
111^113
145^146
165^167
158^15914
112^1136
147^1481
166^1671
obtained on a Perkin-Elmer 983G spectrometer.The products were also
characterised by comparison of their melting points with literature
values.
Received, 4th January 1999; Accepted, 19th January 1999
Paper E/9/00025I
General Procedure for the Preparation of Diacetals.öA mixture of
p-tolualdehyde 1c (2.00 mmol), 2,2-bis(hydroxymethyl)propane-1,3-
diol 2 (1.25 mmol) and anhydrous ferrous sulfate (100 mg) in benzene
(10 ml) was stirred at re£uxing temperature for 1.5 h (Table 1) using a
Dean^Stark apparatus for water removal. The reaction was moni-
tored by TLC. After cooling, the catalyst was removed by ¢ltration
and washed with CH2Cl2 (5 ml  2). The solvent was evaporated
under reduced pressure and the residue was chromatographied on
silica gel (light petroleum^dichloromethane as eluent) to give
diacetal 3c in 98% yield; mp 212^213 8C.
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2
3
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1
For 3c: nmax/cm 2910, 2862, 1600, 1460, 1390, 1050, 805; dH 2.346
(6H, s, Ar-CH3), 3.638 (2H d, J 11.7 Hz), 3.813 (2H, dd, J 11.7, 2.4 Hz),
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20,60-Ar-H). For 3f: nmax/cm 2986, 2856, 1601, 1578, 1479, 1381, 1335,
1249, 1205, 1160, 1120, 1075, 1035, 966, 896, 877, 796, 750, 703; dH 3.656
(2H, d, J 11.7 Hz), 3.680 (4H, d, J 11.7 Hz), 4.829 (2H, d, J 11.7 Hz), 5.432
(2H, s, CHO2, 7.330^7.381 (6H, m, Ar-H), 7.503 (2H, s, 2-0Ar-H). For
3j: dH 3.703 (2H, d, J 11.7 Hz), 3.903 (2H, dd, J 11.7, 2.4 Hz), 3.918 (2H,
d, J 11.7 Hz), 4.847 (2H, d, J 11.7 Hz), 5.655 (2H, s, CHO2), 6.872^7.284
(8H, A0ABB0, Ar-H), 7.565 (2H, s, Ar-OH). For 3q: dH 1.502 [6H, s,
CꢀCH3O2, 3.145 (2H, dd, J 11.1, 2.4 Hz), 3.255 (2H, d, J 11.7 Hz), 3.631
(2H, d, J 11.7 Hz), 4.477 (2H, dd, J 11.7, 1.8 Hz), 7.313^7.425 (8H, m,
Ar-H). For 3r: dH 2.878 (8H, s, Ar-CH2O), 3.589 (8H, s, CHO),
7.142^7.332 (20H, m, Ar-H).
8
9
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The project was supported by NSFC (29572039 and
29872011), Natural Science Foundation of Hebei Province
(297065) and Science and Technology Commission of Hebei
Province.