Montmorillonite Clays Catalysis. Part 12.1 An Efficient and Practical Procedure for Synthesis of Diacetals from 2,2-Bis(hydroxymethyl)propane-1,3-diol with Carbonyl Compounds

Article abstract of DOI:10.1039/a803046d

Preparation of diacetals from 2,2-bis(hydroxymethyl)propane-1,3-diol with aldehydes and ketones is catalysed by montmorillonite clays in refluxing benzene or toluene in good to excellent yield.

Full text of DOI:10.1039/a803046d

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640 J. CHEM. RESEARCH (S), 1998
Montmorillonite Clays Catalysis. Part 12.1
An Efficient and Practical Procedure for Synthesis
of Diacetals from 2,2-Bis(hydroxymethyl)propane-
1,3-diol with Carbonyl Compounds$
J. Chem. Research (S),
1998, 640±641$
Zhan-Hui Zhang,a,b Tong-Shuang Li,*a Tong-Shou Jina and Ji-Tai Lia
aDepartment of Chemistry, Hebei University, Baoding 071002, Hebei Province, P.R. China
bDepartment of Chemistry, Hebei Teachers University, Shijiazhuang 050091, Hebei Province,
P.R. China
Preparation of diacetals from 2,2-bis(hydroxymethyl)propane-1,3-diol with aldehydes and ketones is catalysed by
montmorillonite clays in refluxing benzene or toluene in good to excellent yield.
Pentaerythritol acetals are applied as plasticizers and vulca-
nizers of various polymeric materials, as raw materials for
production of valuable resins and lacquers, as physiologi-
cally active substances2 and as defoamers for washing
solution containing anionic surfactants.3 They can be used
as potential protective groups for aldehydes and ketones as
well as important derivatives of carbonyl compounds since
most are crystalline substances and have sharp melting
points. Several publications have described the preparation
of pentaerythritol diacetals under acidic conditions.4
Protic acids (hydrochloric acid,5 sulfuric acid,3,6,7 and p-
toluenesulfonic acid5,8,9) and Lewis acids (zinc chloride,10
anhydrous copper sulfate11) have been employed as cata-
lysts. However, these methods have not been entirely
satisfactory, owing to problems of corrosion, tedious work-
up, environmental pollution and non-recoverable catalysts.
diacetals in good to excellent yields. K-10 worked better
than KSF in terms of reaction time and yield. This may be
1
due to it having a greater surface area (220±270 m2 g
)
than that of KSF (20±40 m2 g 1). The reaction proceeds
cleanly and the work-up is simple, involving only ®ltration
of the catalyst and removal of solvent to obtain the product
in high purity.
The reaction rate is markedly dependent on temperature.
The reaction proceeded much more slowly in re¯uxing
benzene than in toluene. For example, complete conversion
of 3-chlorobenzaldehyde (1i) into the corresponding diacetal
(3i) needed 0.8 h in re¯uxing toluene, but 1.5 h in re¯uxing
benzene under catalysis by montmorillonite K-10. Ketones
show less reactivity than aldehydes for this reaction, for
example dibenzal pentaerythritol (3f ) was obtained in quan-
titative yield (98%) from re¯uxing benzene for 1 h whereas
acetophenone (1s) provided 89% yield of product from
re¯uxing toluene for 8 h in the presence of montmorillonite
K-10. It is worth noting that when 4-hydroxybenzaldehyde
(1l) and 4-(dimethylamino)benzaldehyde (1n) were treated
with 2,2-bis(hydroxymethyl)propane-1,3-diol in the presence
of K-10 the reactions took longer (>8 h) even under re¯ux-
ing in toluene. The explanation, we propose, is that the
strong donor groups hydroxy and dimethylamino reduce
the reactivity.
The catalysts are easily regenerated by washing with
ethanol followed by drying at 120 8C for 4 h. The catalyst
could be reused three times for the synthesis of penta-
erythritol diacetal 3f without signi®cant loss of activity.
In conclusion, the present procedure appears to be e-
cient for aldehydes and ketones. The operational simplicity,
use of inexpensive, non-corrosive and reusable catalysts and
high yields can make it a useful and attractive alternative to
the currently available methods.
Consequently, there is
a demand for environmentally
friendly acid catalysts to synthesize pentaerythritol diacetals
under mild conditions. Cation exchanger KU-22 and
12-tungstophosphoric acid12 have been used as catalysts for
the condensation of 2,2-bis(hydroxymethyl)propane-1,3-diol
with aldehydes and ketones. More recently, microwave
irradiation was applied to accelerate this reaction.13
Clay minerals are known to catalyse a variety of organic
reactions in which the catalyst acts as a solid Lewis acid or
Brùnsted acid.14 Recently, we have developed ecient
and convenient procedures for preparation15 and cleavage16
of 1,3-dioxolanes catalysed by montmorillonite K-10. As a
part of ongoing work on montmorillonite clay catalysis,17
we now describe a direct condensation of aldehydes and
ketones with 2,2-bis(hydroxymethyl)propane-1,3-diol cata-
lysed by montmorillonites K-10 and KSF.
Experimental
Melting points are uncorrected. 1H NMR spectra were deter-
mined on a Varian VXR-300 S (300 MHz) spectrometer using
CDCl3 as solvent and tetramethylsilane (TMS) as internal reference,
IR spectra on a FTS-40 spectrometer. Montmorillonite K-10 and
KSF were purchased from Aldrich and dried at 120 8C for 2 h prior
to use.
Scheme 1
General Procedure for Preparation of Diacetals.ÐA mixture
of carbonyl compound (1, 3.00 mmol), 2,2-bis(hydroxymethyl)-
propane-1,3-diol (2, 1.80 mmol) and montmorillonite K-10 or KSF
(300 mg) in benzene or toluene (20 ml) was stirred at re¯uxing tem-
perature for 0.6±12 h (Table 1) using a Dean±Stark apparatus
for water removal. The progress of the reaction was monitored
by TLC. After cooling, the catalyst was ®ltered o€ and washed
with CH2Cl2 (5 ml 2). Evaporation of the solvent under reduced
pressure a€orded the crude product. This was puri®ed by column
chromatography on silica gel [light petroleum (bp 60±90 8C)±
dichloromethane as eluent] or recrystallised to give diacetals 3, yield
70±98% (Table 1).
As summarized in Table 1, several aldehydes and
ketones in the presence of montmorillonites K-10 or KSF
were heated with 2,2-bis(hydroxymethyl)propane-1,3-diol in
re¯uxing benzene or toluene, resulting in the corresponding
*To receive any correspondence.
$This is a Short Paper as de®ned in the Instructions for Authors,
Section 5.0 [see J. Chem. Research (S), 1998, Issue 1]; there is there-
fore no corresponding material in J. Chem. Research (M).

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J. CHEM. RESEARCH (S), 1998 641
Table 1 Preparation of diacetals catalysed by montmorillonite clays
mp( 8C)
Substrate
Catalyst
Solvent
t/h
Yield (%)a
Found
Reported
n-C6H13CHO (1a)
n-C9H19CHO (1b)
K-10
K-10
KSF
K-10
KSF
K-10
KSF
K-10
K-10
KSF
K-10
K-10
K-10
K-10
K-10
K-10
K-10
K-10
K-10
K-10
K-10
K-10
K-10
KSF
K-10
KSF
K-10
K-10
K-10
K-10
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Toluene
Benzene
Toluene
Benzene
Benzene
Toluene
Toluene
Benzene
Benzene
Toluene
Benzene
Benzene
Benzene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
1
1
3
1
5
93
95
93
92
88
90
85
92
98
93
93
92
95
94
92
90
91
70b
95
89b
94
93
89
87
90
89
90
89
91
97b
62±63
75±76
636
77±7813
4-MeC6H4CHO (1c)
4-MeOC6H4CHO (1d)
211±213
182±184
1.5
6
1776
3,4-(OCH2O)C6H3CHO (1e)
C6H5CHO (1f)
1.5
0.6
2.5
2.5
1
1.5
0.8
2
3
1.5
10
2.5
6
8
3
3
7
3
6
4
8
8
12
192±193
155±156
1886
155±15613
2-O2NC6H4CHO (1g)
3-O2NC6H4CHO (1h)
3-ClC6H4CHO (1i)
164±165
185±186
121±122
163±16413
1856
4-ClC6H4CHO (1j)
2-HOC6H4CHO (1k)
200±201
160±161
197±19813
4-HOC6H4CHO (1l)
3-MeO-4-HOC6H3CHO (1m)
4-Me2NC6H4CHO (1n)
110±112
170±171
222±224
109±11013
22318
188±189
159±160
1956
.
E-C6H5CH CHCHO (1o)
2-Furaldehyde (1p)
158±15913
Cyclohexanone (1q)
113±114
112±1137
CH3(CH2)5COCH3 (1r)
C6H5COCH3 (1s)
(C6H5CH2)2CO (1t)
(C6H5)2CO (1u)
44±45
147±148
166±167
163±164
aYield refers to isolated pure products. bNet yield, conversion rate of 1l ˆ 33%; conversion rate of 1n ˆ 43%; conversion
rate of 1u ˆ 79%.
1
Selected spectral data.ÐFor 3c: ꢀ~max/cm
2910, 2862, 1600,
References
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2ÂHax), 5.424 (2 H, s, 2Â Ar CH), 7.181 (4 H, d, J 8.0, 2Â 3',5'
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J 11.4, 2Â Hax), 3.840 (4 H, d, J 11.4, 4 ÂHeq), 4.829 (2 H, d,
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1
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3.879±3.927 (4 H, m, 4Â Heq), 4.847 (2 H, d, J 11.8 Hz, 2Â Hax),
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1163, 1075, 1027, 864, 780; ꢁH 3.650 (2 H, d, J 11.5, 2Â Hax),
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d, J 11.5, 2Â Hax), 5.402 (2 H, s, 2Â Ar CH), 5.667 (2 H, br s,
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1
1.5, 2Â6' Ar H), 7.033 (2 H, s, 2 Â2' Ar H). For 3r: ꢀ~max/cm
2970, 2865, 1470, 1380, 1160, 1075; ꢁH 0.880 [6 H, t, J 6.5,
2Â(CH2)5CH3], 1.28 (16 H, m, 8Â CH2), 1.353 (6 H, s, 2Â CH3),
1.662 (4 H, t, J 7.9 Hz, 2Â CH2), 3.712±3.881 (8 H, m, 4 Â CH2O).
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1
For 3s: ꢀ~max/cm 2980, 2900, 1470, 1380, 1250, 1175, 890, 704;
ꢁH 1.502 (6 H, s, 2Â CH3), 3.150 (2 H, dd, J 11.1, 2.4, 2Â Heq),
3.248 (2 H, d, J 11.1, 2ÂHax), 3.631 (2 H, d, J 11.7, 2ÂHax), 4.474
(2 H, dd, J 11.7, 2.4 Hz, 2ÂHeq), 7.313±7.425 (10 H, m, Ph H).
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1
For 3t: ꢀ~max/cm 2990, 2855, 1600, 1480, 1075, 750, 702; ꢁH 2.878
(8 H, s, 4Â PhCH2), 3.589 (8 H, s, 4 ÂCH2O), 7.142±7.322 (20 H,
1
m, Ph H). For 3u: ꢀ~max/cm 2960, 2860, 1610, 1500, 1450, 1100,
780; ꢁH 3.879 (8 H, s, 4Â CH2O), 7.256±7.503 (20 H, m, Ph H).
15 T.-S. Li, S.-H. Li, J.-T. Li and H.-Z. Li, J. Chem. Res. (S),
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The project was supported by NSFC(29572039), Natural
Science Foundation of Hebei Province (297065) and Science
and Technology Commission of Hebei Province.
16 T.-S. Li and S.-H. Li, Synth. Commun., 1997, 27, 2299.
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Received, 23rd April 1998; Accepted, 17th June 1998
Paper E/8/03046D
18 D. Radulescu and I. Tanasescu, Bull. Soc. Stiinte Cluj, 1922, 1,
192.