Metal cation-exchanged montmorillonite (Mn+-mont)-catalyzed friedel-crafts acylation of 1-methyl-1-cyclohexene and 1-trimethylsilyl-1- alkynes

Article abstract of DOI:10.1246/bcsj.77.1765

The acylation of 1-methyl-1-cyclohexene and 1-trimethylsilyl-1-alkynes with acyl chlorides has been investigated in the presence of a variety of metal cation-exchanged montmorillonites (abbreviated as Mⁿ⁺-monts), where the catalysts are recycla

Full text of DOI:10.1246/bcsj.77.1765

Short Articles
Bull. Chem. Soc. Jpn., 77, 1765–1766 (2004) 1765
O
O
catalyst
R
Metal Cation-Exchanged
+
Cl
R
benzene
r.t., 2 h
Montmorillonite (Mnþ-Mont)-
Catalyzed Friedel–Crafts Acylation
of 1-Methyl-1-cyclohexene and
1-Trimethylsilyl-1-alkynes
1
2
3
d: R = But
a: R = Et
b: R = Pr
c: R = Pri
e: R = Ph
f: R = trans- MeCH=CH-
Scheme 1.
Table 1. Acylation of 1 with 2b in the Presence of Mnþ-Mont
ꢀ
Isolated yield
of 3bb)/%
Takahiro Nishimura, Seiji Ohtaka, Keiji
Hashimoto,1 Takayoshi Yamauchi,2 Takuji
Entry
Mnþ-mont
(mmol)a)
TONc)
1
Fe3þ
In3þ
Zr4þ
La3þ
Al3þ
Ce3þ
Yb3þ
Dy3þ
—
0.105
0.059
0.220
0.060
0.159
0.042
0.097
0.018
—
45
25
13
13
1
Hasegawa,3 Kaori Imanaka,3 Jun-ichi Tateiwa,3
Hiroshi Takeuchi,3;4 and Sakae Uemura
2
ꢀ
3
9
Trace
4
0
5
0
0
0
0
0
0
Department of Energy and Hydrocarbon Chemistry,
Graduate School of Engineering, Kyoto University,
Nishikyo-ku, Kyoto 615-8510
6
0
7
0
8
9d)
0
0
1Osaka Municipal Technical Research Institute,
1-6-5 Morinomiya, Joto-ku, Osaka 536-8553
Reaction conditions: 1 (6.0 mmol), 2b (3.0 mmol), Mnþ-mont (300
mg), benzene (8 cm3), rt, 2 h. a) The amount of acid sites of Mnþ-mont
was estimated by NH3-TPD analysis. b) Mol of 3b/mol of acid sites.
c) Based on the mol of acid sites. d) 24 h.
2Nissei Chemical Inc., 2-18-110 Jyuhachijyo,
Yodogawa-ku, Osaka 532-0001
3Department of Molecular Science, Graduate School of
Science and Technology, Kobe University,
Rokkodai-cho, Nada-ku, Kobe 657-8501
(2{7 ꢁ 10ꢂ2 molar amounts) (Scheme 1, Table 1). Fe3þ and
In3þ-monts were revealed to be effective for this reaction
(entries 1 and 2), the TON (turnover number) being 13 in both
cases. The catalytic activity of Zr4þ and La3þ-monts was lower
(entries 3 and 4). On the other hand, Al3þ, Ce3þ, Yb3þ, and
Dy3þ-monts did not show any catalytic activity (entries 5–8).
No reaction proceeded in the absence of Mnþ-mont (entry
9). The amount of Fe3þ-mont slightly affected the product
yield and we found that the use of 0.012 molar amounts of
Fe3þ-mont (100 mg) gave the best result, a larger and a smaller
amount of it resulting in a decrease of the product yield.
Thus, Fe3þ and In3þ-monts were applied to the reaction of 1
with a variety of acyl chlorides 2a–2f (Scheme 1, Table 2). As
a result, the corresponding 6-acyl-1-methyl-1-cyclohexene was
obtained in up to 58% yield, but some unidentified isomeric
compounds were detected by GC–MS analysis.
4Department of Chemical Science and Engineering,
Faculty of Engineering, Kobe University,
Rokkodai-cho, Nada-ku, Kobe 657-8501
Received March 29, 2004; E-mail: uemura@scl.kyoto-u.ac.jp
The acylation of 1-methyl-1-cyclohexene and 1-tri-
methylsilyl-1-alkynes with acyl chlorides has been investigat-
ed in the presence of a variety of metal cation-exchanged
montmorillonites (abbreviated as Mnþ-monts), where the cat-
alysts are recyclable for several times after simple washing.
Organic transformation in the presence of a variety of solid
catalysts is of recent interest and many useful synthetic meth-
ods have been developed.1 Currently we have been much inter-
ested in the use of clay minerals as the solid catalysts, since
they are known as environmentally-friendly materials and
might work as the substitutes for several homogeneous cata-
lysts.2,3 Here we describe the result of our attempts for
Friedel–Crafts acylation of 1-methyl-1-cyclohexene and 1-tri-
methylsilyl-1-alkynes with various acyl chlorides in the pres-
ence of cation-exchanged montmorillonites (abbreviated as
Mnþ-monts), a kind of clay mineral. Although aromatic
Friedel–Crafts reactions have so far been investigated using
various Mnþ-monts as catalysts,4 there are no examples of
aliphatic acylation in the presence of Mnþ-monts to the best
of our knowledge.
The recovered Fe3þ-mont was successfully reused in the re-
action of 1 with 2b to afford 3b at least three times after wash-
ing it with 50% aqueous acetone and drying at 120 ꢃC for 24 h
(1st use, 45%: 2nd use, 40%: 3rd use, 40%).
Separately, we confirmed that the acylation of 1 with 2b
proceeded even in the presence of a catalytic amount of FeCl3
and InCl3, but the catalytic activity of these Lewis acids was
not as high as that of Fe3þ and In3þ-monts in terms of the
isolated yields of 3b (15–31%).
Next, we investigated the reaction of several 1-trimethyl-
silyl-1-alkynes 4 with 2b (Scheme 2, Table 3). Treatment of
4 with 2b in the presence of Fe3þ and In3þ-monts at room tem-
perature for 2 h produced the corresponding acyl compounds
in moderate yields by replacing a trimethylsilyl group with
an acyl group; the yield was up to 64% (entry 2). Even when
an excess amount of 2b to 4a was employed, only a monosub-
stituted product 5a was obtained without any formation of a
disubstituted product.
First, we examined Friedel–Crafts acylation of 1-methyl-1-
cyclohexene (1) (2 molar amounts) with butyryl chloride (2b)
(1 molar amount) in the presence of several Mnþ-monts
Published on the web September 10, 2004; DOI 10.1246/bcsj.77.1765

1766 Bull. Chem. Soc. Jpn., 77, No. 9 (2004)
Ó 2004 The Chemical Society of Japan
Table 2. Acylation of 1 with 2 in the Presence of Fe3þ and
The acyl compounds 3a–3f and 5a–5d are known and were
characterized by their spectral data after their isolation.5–13
General Procedure for Mnþ-Mont-Catalyzed Friedel–
Crafts Acylation of 1-Methyl-1-cyclohexene (1) with Acyl
Chloride 2. To a mixture of acyl chloride 2 (3 mmol) and ben-
zene (8 cm3) was added Fe3þ-mont (100 mg, 0.0349 mmol as acid
sites estimated by NH3-TPD) in one portion at room temperature
with magnetic stirring. After the mixture was stirred at the temper-
ature for a few minutes, 1-methyl-1-cyclohexene (1) (0.71 mL, 6
mmol) was added to it and the mixture was stirred vigorously at
room temperature for 2 h. The catalyst was filtered off and rinsed
with Et2O (50 cm3). The solvent in a mixture of the filtrate and the
ethereal washings was removed under the reduced pressure to
leave an oil, which was subjected to silica gel column chromatog-
raphy (eluent, hexane:diethyl ether = 10:1) to give the corre-
sponding 6-acyl-1-methyl-1-cyclohexene 3.
In3þ-Mont
Isolated yield
of 3/%
Entry
2
Mnþ-mont
TONa)
1
2
2a
2b
2c
2d
2e
2f
Fe3þ-mont
Fe3þ-mont
Fe3þ-mont
Fe3þ-mont
Fe3þ-mont
Fe3þ-mont
In3þ-mont
In3þ-mont
In3þ-mont
In3þ-mont
In3þ-mont
In3þ-mont
49
58
38
19
16
20
45
58
34
34
23
27
42
50
33
16
14
17
69
89
52
52
35
42
3
4
5
6
7
2a
2b
2c
2d
2e
2f
8
9
10
11
12
Reaction conditions: 1 (6.0 mmol), 2 (3.0 mmol), Mnþ-mont (100 mg;
Fe3þ-mont, 0.0349 mmol, 0.012 mol amt, In3þ-mont, 0.0197 mmol,
0.0066 mol amt), benzene (8 cm3), rt, 2 h. a) Mol of 3/mol of acid
sites.
References
1
a) M. Balogh and P. Laszlo, ‘‘Organic Chemistry Using
Clays,’’ Springer-Verlag, New York (1993). b) R. L. Augustine,
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Appl. Catal., A, 189, 163 (1999). d) J. H. Clark, Acc. Chem. Res.,
35, 791 (2002).
O
O
catalyst
+
R
SiMe3
R
Cl
Pr
benzene
r.t., 2 h
Pr
4
2b
5
a: R = SiMe3 c: R = Bu
b: R = Ph d: R = Me
2
a) J. Tateiwa, H. Horiuchi, K. Hashimoto, T. Yamauchi,
and S. Uemura, J. Org. Chem., 59, 5901 (1994). b) J. Tateiwa,
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and S. Uemura, J. Chem. Soc., Perkin Trans. 1, 1997, 2169.
Scheme 2.
Table 3. Acylation of 4 with 2a or 2b in the Presence of
Mnþ-Mont
Isolated yield
of 5/%
Entry
R
Mnþ-mont
TONa)
1
2
3
4
5
6
7
8
SiMe3
Ph
Bu
Fe3þ-mont
Fe3þ-mont
Fe3þ-mont
Fe3þ-mont
In3þ-mont
In3þ-mont
In3þ-mont
In3þ-mont
54
64
36
9
46
55
31
8
3
a) T. Nishimura, N. Kakiuchi, M. Inoue, and S. Uemura,
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and P. Landon, J. Chem. Soc., Chem. Commun., 1989, 1353. b) A.
Me
SiMe3
Ph
Bu
31
51
31
9
48
78
48
14
´
Cornelis, C. Dony, P. Laszlo, and K. M. Nsunda, Tetrahedron
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´
Me
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Reaction conditions: 4 (6.0 mmol), 2b (3.0 mmol), Mnþ-mont (100
mg; Fe3þ-mont, 0.0349 mmol, 0.012 mol amt, In3þ-mont, 0.020
mmol, 0.0066 mol amt), benzene (8 cm3), rt, 2 h. a) Mol of 5/mol
of acid sites.
5
6
J. K. Groves and N. Jones, J. Chem. Soc. C, 1968, 2215.
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We have applied this reaction to many other substrates, such
as cyclohexene, ꢀ-pinene, norbornene, trimethyl(vinyl)silane,
and allyltrimethylsilane, but all reactions resulted in a forma-
tion of many unidentified products unfortunately. The treat-
ment of 2-phenylpropene produced only the corresponding
dimer.2e
Fr., 1956, 1653.
7
(1980).
8
P. Beak and K. R. Berger, J. Am. Chem. Soc., 102, 3848
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9
3766.
Experimental
General Procedures. All commercially available organic and
inorganic compounds were used without further purification.
In3þ-mont was newly prepared from KunipiaÒ G (<100 mesh,
10 B. B. Snider and A. C. Jackson, J. Org. Chem., 47, 5393
(1982).
11 C. H. Wong and C. W. Bradshaw, U. S. Patent 5225339
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Chem. Soc., 123, 2074 (2001).
6 g) and In(NO3)3 3H2O (21.3 g, 60 mmol).2a The amount of acid
ꢄ
sites (Brꢀnsted and Lewis acid sites) was estimated by the temper-
ature-programmed desorption of ammonia gas (NH3-TPD) analy-
sis to be 0.195 mmol gꢂ1. The basal spacing (d001) of In3þ-mont
was estimated by a sharp peak obtained on XRD analysis to be
ꢁ
15.4 A, showing that the compound has an interlayer structure.