Metal cation-exchanged montmorillonite (Mn+-mont)-catalysed aromatic alkylation with aldehydes and ketones

Article abstract of DOI:10.1039/a701744h

The alkylation of aromatic compounds with aldehydes and ketones in the presence of a variety of metal cation-exchanged montmorillonites (Mⁿ⁺-mont; Mⁿ⁺ = Zr⁴⁺, Al³⁺, Fe³⁺, Zn²⁺, H⁺, Na⁺) has been investigated. Al³⁺- and Zr⁴⁺-Monts are revealed to be effective as catalysts, while no reaction takes place with Na⁺-mont. Al³⁺-Mont-catalysed alkylation of phenol with several aldehydes produces mainly or almost solely the corresponding gem-bis(hydroxyphenyl)alkanes (bisphenols) in good yields, while that with several ketones affords selectively the corresponding alkylphenols in moderate to good yields. The alkylation always occurs at the carbonyl carbon without any skeletal rearrangement and the kind of products depends much on the steric hindrance of an electrophilic intermediary carbocation. The alkylation of anisole, veratrole and p-cresol proceeds well, while that of toluene, benzene, chlorobenzene and nitrobenzene scarcely occurs.

Full text of DOI:10.1039/a701744h

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Metal cation-exchanged montmorillonite (Mnϩ-mont)-catalysed
aromatic alkylation with aldehydes and ketones
Jun-ichi Tateiwa, Ei Hayama, Takahiro Nishimura and Sakae Uemura *
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering,
Kyoto University, Sakyo-ku, Kyoto 606-01, Japan
The alkylation of aromatic compounds with aldehydes and ketones in the presence of a variety of metal
cation-exchanged montmorillonites (M nϩ-mont; M nϩ = Zr4ϩ, Al3ϩ, Fe3ϩ, Zn2ϩ, H ϩ, N aϩ) has been
investigated. Al3ϩ- and Zr4ϩ-M onts are revealed to be effective as catalysts, while no reaction takes place
with N aϩ-mont. Al3ϩ-M ont-catalysed alkylation of phenol with several aldehydes produces mainly or
almost solely the corresponding gem-bis(hydroxyphenyl)alkanes (bisphenols) in good yields, while that
with several ketones affords selectively the corresponding alkylphenols in moderate to good yields. The
alkylation always occurs at the carbonyl carbon without any skeletal rearrangement and the kind of
products depends much on the steric hindrance of an electrophilic intermediary carbocation. The
alkylation of anisole, veratrole and p-cresol proceeds well, while that of toluene, benzene, chlorobenzene
and nitrobenzene scarcely occurs.
Introduction
R1
R1
R3
Selective organic transformation in the presence of various
solid catalysts including metal-cation exchanged clays is of
O
R1
R2
R2
R3
current interest in ensuring that synthetic processes are
Al3+–mont
100 °C, 48 h
environmentally friendly.1 In our course of studies on metal
cation-exchanged
montmorillonite
(Mnϩ-mont)-catalysed
R1
1
2
R2
R3
organic unit reactions, we reported the Mnϩ-mont-catalysed
rearrangement of 4-phenoxybutan-2-one to the correspond-
ing alkylphenol, namely 4-(4-hydroxyphenyl)butan-2-one
(raspberry ketone); we also noted the formation of a little
H
3
4
1
2
a R1 = OH
a R2 = Pr,
b R2 = Bu,
R3 = H
R3 = H
R3 = H
R3 = H
R3 = H
R3 = H
R3 = H
R3 = H
R3 = Me
R3 = Me
3,4-dihydro-4-methyl-2H-1-benzopyran
(4-methylchroman)
b R1 = OMe
c R1 = NMe2
d R1 = Me
e R1 = Cl
c R2 = CH3(CH2)4,
d R2 = CH3(CH2)5,
e R2 = CH3(CH2)6,
f R2 = Pri,
probably as a result of intramolecular reductive aromatic
alkylation with a carbonyl moiety.2 Intra- and inter-molecular
aromatic alkylations with aldehydes and ketones have been
less studied than the corresponding alkylations with alcohols,
alkyl halides or alkenes; this is because the former reactions
normally give a low yield of the expected products because
of polymeric by-product formation.3 Although the alkylation
of phenol with aldehydes and ketones in the presence of sev-
eral acid catalysts to produce gem-bis(hydroxyphenyl)alkanes
(bisphenols) has been investigated, few attempts have been
made to produce alkylphenols by the corresponding aromatic
alkylations.4,5 For example, the dry HCl-catalysed reaction of
phenol with aldehydes in glacial acetic acid produced poly-
meric products, the pyrolysis of which gave alkylphenols in
good yields by way of disproportionation.4,5 Such alkyl-
phenols and bisphenols find use in the pharmaceutical
and agrochemical industries.6 In view of this we have
developed a facile one-pot preparative method for alkylphenols
and/or bisphenols by intermolecular reductive alkylation of
phenol with aldehydes and ketones using Mnϩ-monts as
catalysts.7
f R1 = H
g R1 = NO2
g R2 = Cy,
h R2 = Ph,
i R2 = Et,
j R2 = Pr,
k R2 = R3 = Et
l R2 = CH3(CH2)4,
m R2 = Bu,
R3 = Me
R3 = Et
n R2 = R3 = Pr
o R2 = R3 = ᎐(CH2)5᎐
Scheme 1
ratio of 5:4:1) (Scheme 1). One of the characteristic features of
this reaction is that the alkylation always occurred at the car-
bonyl carbon without any skeletal rearrangement to give com-
pounds 3 and 4; thus, 2-, 3- and 4-(hydroxyphenyl)octanes and
the corresponding bisphenols were not formed. This is in sharp
contrast to the Ga2Cl4-mediated reductive Friedel–Crafts
alkylation of anisole 1b with aldehydes8 and the AlCl3-
mediated reaction of 1a with ketones,5 both reactions having
been reported to be accompanied by a skeletal rearrangement.
The reaction similarly proceeded with Zr4ϩ-, Zn2ϩ-, Fe3ϩ- and
Hϩ-mont (montmorillonite K10 or H2SO4-treated clay), but it
did not occur with Naϩ-mont (Kunipia® G).
Results and discussion
Alkylation of phenol 1a with aldehydes in the presence of Mnϩ
mont
-
Treatment of phenol 1a with octanal 2e in the presence of Al3ϩ
-
Although recovered Al3ϩ-mont could not be reused for this
reaction, it was successfully regenerated and reused at least
three times almost without a loss of activity after being washed
with 50% aqueous acetone and then dried at 120 ЊC.
mont at 100 ЊC for 48 h produced 1-(hydroxyphenyl)octanes 3ae
para-selectively (o-:p- = 8:92 estimated by GLC, 25% isolated
yield) and an isomeric mixture of 1,1-bis(4-hydroxyphenyl)-
octane, 1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)octane and
1,1-bis(2-hydroxyphenyl)octane 4ae (58% isolated yield, in a
The Al3ϩ-mont-catalysed reaction was then applied to the
reaction of phenol with butanal 2a, pentanal 2b, hexanal 2c,
J. Chem. Soc., Perkin Trans. 1, 1997
1923

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Table 1 Alkylation of aromatic compounds with aldehydes and ketones in the presence of Mnϩ-mont a
Products, isolated yield (%)b
Aromatic
compd.
Carbonyl
compd.
Alkylphenols
Bisphenols
Run
Mnϩ-Mont
(o-:p- ratio c)
(ratio of 3 isomersc)
Aldehyde
1
2
3
4
5
6
7
8
9
10
11
12
13
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
2a
2b
2c
2d
2e
2e
2e
2e
2e
2e
2f
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Zr4ϩ-mont
Fe3ϩ-mont
Zn2ϩ-mont
Hϩ-mont
3aa,
3ab,
3ac,
3ad,
3ae,
3ae,
3ae,
3ae,
3ae,
3ae,
3af,
3ag,
3ah,
6 (16:84);
4aa,
4ab,
4ac,
4ad,
4ae,
4ae,
4ae,
4ae,
4ae,
4ae,
4af,
4ag,
4ah,
69 (6:4:<0.1)
7 (10:90);
11 (8:92);
14 (7:93);
25 (8:92);
15 (9:91);
75 (5:4:1)
65 (5:4:1)
62 (5:4:1)
58 (5:4:1)
75 (5:4:1)
30 (5:4:1)
61 (5:4:1)
43 (5:4:1)
0
3
(9:91);
0;
0;
0;
Naϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
10 (16:84);
16 (16:84);
Trace;
Trace
Trace
90 (5:4:1)
2g
2h
Ketone
2i
2j
2j
2j
2j
2j
2j
2k
2l
2m
2n
2o
2e
2e
2j
2o
2j
2o
2j
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
5
Al3ϩ-mont
Al3ϩ-mont
Zr4ϩ-mont
Fe3ϩ-mont
Zn2ϩ-mont
Hϩ-mont
3ai,
3aj,
3aj,
3aj,
3aj,
3aj,
3aj,
3ak,
3al,
3am,
3an,
3ao,
3ae,
3be,
3bj,
3bo,
7,
27 (22:78)
51 (8:92)
39 (7:93)
6
0
0
0
(7:93)
Naϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
46 (0:100)
61 (3:97)
48 (0:100)
27 (0:100)
78 (23:77)
Trace;
12 (<1:>99);
32 (0:100);
32 (3:97)
Trace;
d
AlCl3
4ae,
4be,
4bj,
Trace
25 (8:2:<0.1)
12 (8:2:<0.1)
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
Al3ϩ-mont
8,
20
5
6
9,
10,
30
29
a
Aromatic compound (26.6 mmol), aldehyde or ketone (0.78 mmol), Mnϩ-mont (0.266 mmol as acid sites estimated by NH3-TPD) at 100 ЊC for 48 h.
b Based on 2. Bisphenol 4 ia an isomeric mixture. c Estimated by GLC. d 2.66 mmol.
heptanal 2d and benzaldehyde 2h. As a result, the corre-
sponding 1,1-bis(hydroxyphenyl)butanes 4aa, 1,1-bis(hydroxy-
phenyl)pentanes 4ab, 1,1-bis(hydroxyphenyl)hexanes 4ac, 1,1-
bis(hydroxyphenyl)heptanes 4ad and 1,1-bis(hydroxyphenyl)-1-
phenylmethanes 4ah were obtained as major products together
with a small amount of the corresponding alkylphenols 3 (see
Table 1). Compounds 4aa, 4ab, 4ac, 4ad and 4ah also consisted
of p,p- (the major), p,o- and o,o-isomers, respectively. In par-
ticular, the alkylation of 1a with 2h produced 4ah almost
exclusively in 90% isolated yield. For comparison, all reactions
pentane 3ak (o-:p- = 0:100) in 46% isolated yield, respectively
(Scheme 1, Table 1). In this case, Al3ϩ-mont was the most prom-
ising catalyst. Compound 3aj was obtained only in 29% yield
with Zr4ϩ-mont, while the reaction failed to proceed at all with
Zn2ϩ-, Hϩ- and Naϩ-mont. With heptan-2-one 2l, heptan-3-one
2m and heptan-4-one 2n compound 1a was similarly alkylated
para-selectively to produce 2-(hydroxyphenyl)heptanes 3al
(o-:p- = 3:97), 3-(hydroxyphenyl)heptane 3am (o-:p- = 0:100)
and 4-(hydroxyphenyl)heptane 3an (o-:p- = 0:100), respect-
ively, in moderate yield. The alkylation of 1a with cyclohex-
anone 2o afforded (hydroxyphenyl)cyclohexanes 3ao (o-:
p- = 23:77) in 78% isolated yield. Typical results using ketones
are also shown in Table 1. As in the case of ketones, the alkyl-
ation with aldehydes also occurred at the carbonyl carbon to
give the corresonding alkylphenols 3. In contrast to alkylation
with aldehydes, that with ketones 2i–o produced alkylphenols
3ai–ao almost exclusively, little of the corresponding bisphenols
4 being detected by GC-MS early in the reaction.
were carried out with Hϩ-mont as catalyst in place of Al3ϩ
-
mont, where 4aa, 4ab, 4ac, 4ad, 4ae and 4ah were obtained in
60, 60, 53, 48, 43 and 21% isolated yields, respectively, no alkyl-
phenols being produced. When phenol was treated with iso-
butyraldehyde 2f and cyclohexanecarbaldehyde 2g in the pres-
ence of Al3ϩ-mont, the corresponding alkylphenols 3 were the
major products, the corresponding bisphenols 4 being almost
completely absent.
Under the present conditions AlCl3 was not an effective
catalyst. For example, in the alkylation of 1a with 2e using
anhydrous AlCl3 (an equivalent amount to Al3ϩ-mont), none of
the expected alkylphenol 3ae or bisphenol 4ae was produced.
Use of an excess of AlCl3 gave only very low yields of 3ae and
4ae accompanied by large amounts of tarry products.
The AlCl3-mediated reaction of 1a with ketones was reported
to be accompanied by a skeletal rearrangement.5 Under the
reported conditions (at 120 ЊC for 3 h ) of the AlCl3-mediated
reaction, however, 1a reacted with 2j and 2k to give only
the corresponding non-rearranged alkylphenols 3aj and 3ak
in yields of 19% (o-:p- = 8:92) and 27% (o-:p- = 0:100),
respectively.
Alkylation of the phenol 1a with ketones in the presence of Mnϩ
mont
-
Alkylation of aromatic compounds with aldehydes and ketones in
the presence of Mnϩ-mont
The alkylation of 1a with ketones such as pentan-2-one 2j and
pentan-3-one 2k produced 2-(hydroxyphenyl)pentanes 3aj
(o-:p- = 8:92) in 51% isolated yield and 3-(hydroxyphenyl)-
In the presence of Al3ϩ-mont catalyst, the alkylation of anisole
1b with octanal 2e provided octylanisole 3be (12% isolated
1924
J. Chem. Soc., Perkin Trans. 1, 1997

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OMe
OH
OMe
with phenol and abstract a hydride much faster than the tertiary
carbocations I obtained from ketones. However, the experi-
mental results of the product distribution show that the steric
hindrance of I might control the kind of products in this inter-
layer reaction, and thus, the reaction rate between less hindered
secondary carbocations and phenol might be less affected than
that between tertiary carbocations and phenol, although the
details are not yet known.
OMe
OMe
5
6
7
Conclusion
OMe
OMe
OH
Al3ϩ-, Zr4ϩ and Fe3ϩ-Monts-catalysed aromatic alkylation of
phenol 1a with aldehydes gave the corresponding bisphenols
[gem-bis(hydroxyphenyl)alkanes] 4 either mainly or almost
exclusively in good yields; similar reactions with ketones
OMe
OMe
afforded selectively the corresponding alkylphenols
3 in
10
moderate to good yields. The alkylation always occurred at the
carbonyl carbon without any skeletal rearrangement and the
kind of products was greatly dependent on the steric hindrance
in the electrophilic intermediary carbocation. The catalyst was
re-used several times after being washed and dried. The alkyl-
ation of anisole 1b, veratrole 5 and p-cresol 6 proceeded simi-
larly to produce mainly the corresponding alkylphenols 3 in
moderate yields; under the present conditions such alkylations
failed with unactivated aromatic compounds such as toluene,
benzene, chlorobenzene and nitrobenzene.
9
MeO
OMe
8
yield; para-isomer, >99%), 1,1-bis(methoxyphenyl)octanes 4be
[25% isolated yield, a mixture of 3 isomers (8:2:<0.1)] and
unidentified tarry compounds. Treatment of 1b with pentan-2-
one 2j gave (1-methylbutyl)anisole 3bj (o-:p- = 0:100) and 2,2-
bis(methoxyphenyl)pentanes 4bj [a mixture of 3 isomers
(8:2:<0.1)] in 32 and 12% isolated yield, respectively. However,
on reaction with cyclohexanone 2o 1b produced the cyclo-
hexylanisoles 3bo (o-:p- = 3:97) in 32% isolated yield.
Similarly, veratrole 5 reacted with pentan-2-one 2j to give
2,2-bis(3,4-dimethoxyphenyl)pentane 8 in 19% isolated yield,
while it gave only 1-cyclohexyl-3,4-dimethoxybenzene 9 in 20%
isolated yield on reaction with 5. The reaction of p-cresol 6 with
pentan-2-one 2j produced 4-methyl-2-(1-methylbutyl)phenol 10
in 29% isolated yield, whilst it failed to react with 2o. The reac-
tion of toluene 1d with 2e or 2o was very sluggish to give only a
trace of products, whilst with chlorobenzene 1e, benzene 1f and
nitrobenzene 1g there was no reaction. Treatment of N,N-
dimethylaniline and N,N-diethylaniline with a variety of
ketones and aldehydes under similar conditions gave little of
the expected alkylated products, diarylmethanes and diaryl-
ethanes being the only identifiable and major compounds. Such
compounds were produced in similar yields (10–20% based on
anilines) even in the absence of carbonyl compounds. Similar
reactions have been recorded with clay catalysts.9
Experimental
NMR spectra were recorded on JEOL EX-400 (1H NMR, 400
MHz; 13C NMR, 100 MHz) and JEOL GSX-270 (1H NMR,
270 MHz; 13C NMR, 67.8 MHz) instruments for solutions in
CDCl3 or [2H6]acetone with Me4Si as an internal standard.
Coupling constants J are given in Hz; abbreviations are as
follows: s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet, br = broad. Mass spectra were measured on a
Shimadzu QP-5000S mass spectrometer equipped with a
Shimadzu GC-17 gas-liquid chromatograph (30 m × 0.254
mm, 0.25 µm film thickness, J&W Scientific fused silica capil-
lary column DB-1). The electron-impact method was used for
ionisation, the ionising voltage being 70 eV for all compounds.
High resolution mass spectra (HRMS) were obtained on a
JEOL JMS SX-102A instrument. The electron-impact method
was used for ionisation, the ionising voltage being 75 eV for
all compounds. GLC analyses were performed on a Shimadzu
GC-14A instrument (25 m × 0.33 mm, 5.0 µm film thickness,
Shimadzu fused silica capillary column HiCap CBP10-S25-050)
with flame-ionisation detectors and helium as carrier gas and
on a Shimadzu GC-14A instrument (2 m × 3 mm glass column
packed with 5% OV-17 on Chromosorb W) with flame-
ionisation detectors and nitrogen as carrier gas. Recycling pre-
parative high performance liquid chromatography (HPLC) was
performed on a JAI LC-908-G30 instrument (600 mm × 20
mm × 2, JAIGEL-1H and JAIGEL-2H dual styrene polymer
columns) equipped with ultraviolet (UV) and refractive-index
(RI) detectors and CHCl3 as an eluent. Column chrom-
atography on SiO2 was performed with Wakogel C-300 using
hexane, hexane–ethyl acetate and ethyl acetate as eluents. Melt-
ing points were determined on a Yanaco MP-S3 micro melting-
point apparatus and are uncorrected. Elemental analyses were
performed at the Microanalytical Center of Kyoto University.
All commercially available organic and inorganic compounds
were used without further purification except for the solvent,
which was dried and distilled by the known method before
use.13 Montmorillonite K10, namely Hϩ-mont, was com-
mercially available from the Aldrich Chemical Co., Inc., which
was used as obtained. Kunipia G, namely Naϩ-mont, was
obtained from Kunimine Industries Co., Ltd. Mnϩ-Mont
(Mnϩ = Zr4ϩ, Al3ϩ, Fe3ϩ, Zn2ϩ) was prepared by treatment of
Naϩ-mont with the corresponding metal oxychloride or nitrate
Plausible reaction pathway
We confirmed separately that the bisphenols 4aa, 4ae and 2,2-
bis(4-hydroxyphenyl)propane (commercially available bisphe-
nol A) were not converted into the corresponding alkylphenols
3 under the present reaction conditions (in phenol) and that the
bisphenol 4aa and bisphenol A were not produced by treatment
of 1a with 1-(hydroxyphenyl)butanes 3aa and 2-(4-hydroxy-
phenyl)propane, respectively. However, in the case of Al3ϩ
-
mont-catalysed aromatic alkylation of phenol 1a with 2a in the
presence of 4aa, the yield of 3aa increased. These results sug-
gested that the alkylphenols 3 and bisphenols 4 might be pro-
duced competitively. The plausible course of the reaction is
shown schematically in Scheme 2 with phenol as an aromatic
substrate. An intermediary carbocation I may be formed by the
effect of the Lewis acid sites of Al3ϩ-mont, although Mnϩ
-
monts have both Brönsted and Lewis acid sites.10 Such a carbo-
cation could be stabilised by negatively charged oxygen atoms
in the interlayer space of Al3ϩ-mont (between two silicate sheets
of Al3ϩ-mont), and then either react with 1a electrophilically to
produce 4 or possibly abstract a hydride11,12 from the bis-
phenols 4 or some other species to produce 3 competitively. The
secondary carbocations I produced from aldehydes might react
J. Chem. Soc., Perkin Trans. 1, 1997
1925

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silicate sheet
OH
OH
HO
[Al3+(H2O)n]
R2
R3
H2O
4
silicate sheet
silicate sheet
[Al3+(H2O)n]–
silicate sheet
HO
HO
HO
[Al3+(H2O)n]
R2
O
+
R2
R3
silicate sheet
I
R3
silicate sheet
silicate sheet
HO
[Al3+(H2O)n]–
HO
HCRR′R′′
H
+CRR′R′′
R2
3
R3
silicate sheet
Scheme 2
in aqueous acetone as described previously.14 ortho- and/or
para-Alkylphenols 3aa,15 3ab,15 3ac,15 3ad,16 3ae,15 3af,17 3ag,18,19
3ai,20 3aj,21 3ak,22 3al,23,24 3am,24 3an,24 3ao,25 3be,26 3bj,21 3bo,27
4bj,28 929 and 1030 are known compounds and were character-
ised from spectral data. New spectral data for the compounds
are shown below. The compounds 4aa, 4ab, 4ac, 4ad, 4ae, 4ah,
4be and 8 are new and were characterised from their mass
spectral data (GC-MS and HRMS) and combustion analytical
data. All bisphenols are unstable in air and the initial colourless
or pale yellow coloured oil changed gradually to pale-red oils
and/or tarry compounds. Therefore, it was sometimes difficult
to obtain correct combustion analytical data.
recycling preparative HPLC and identified by 13C NMR and
mass spectra (GC-MS); a pale-yellow crystalline solid; δC (100
MHz) 14.0 (q), 21.1 (t), 38.2 (t), 49.3 (d), 115.1 (d), 128.8 (d),
138.0 (s) and 153.6 (s); m/z 242 (Mϩ, 8%) and 199 (100) (Found:
m/z 242.1298. C16H18O2 requires m/z 242.1307) as a mixture of
isomers (Found: C, 78.68; H, 7.42%. C16H18O2 requires C,
79.31; H, 7.49%).
1,1-Bis(hydroxyphenyl)pentanes 4ab. A pale yellow oil (iso-
mer ratio 5:4:1) was characterised by mass spectroscopy
(GC-MS and HRMS) and combustion analysis; 1,1-bis(4-
hydroxyphenyl)pentane as a major component isolated by suc-
cessive recycling preparative HPLC and identified by 13C NMR
and mass spectroscopy (GC-MS); a pale-yellow crystalline
solid; δC (100 MHz) 14.0 (q), 22.7 (t), 30.2 (t), 35.8 (t), 49.6 (d),
115.2 (d), 128.9 (d), 138.1 (s) and 153.5 (s); m/z 256 (Mϩ, 7%)
and 199 (100) (Found: m/z 256.1464. C17H20O2 requires m/z
256.1463) (Found: C, 79.10; H, 7.87%. C17H20O2 requires C,
79.65; H, 7.86%).
1,1-Bis(hydroxyphenyl)hexanes 4ac. A pale yellow oil (isomer
ratio 5:4:1) was characterised by mass spectroscopy (GC-MS
and HRMS)and combustion analysis;1,1-bis(4-hydroxyphenyl)-
hexane as a major component isolated by successive preparative
HPLC and identified by 13C NMR and mass spectroscopy
(GC-MS); a pale-yellow crystalline solid; δC (100 MHz) 14.1
(q), 22.5 (t), 27.7 (t), 31.9 (t), 36.1 (t), 49.6 (d), 115.2 (d), 128.9
(d), 138.1 (s) and 153.6 (s); m/z 270 (Mϩ, 5%) and 199 (100)
(Found: m/z 270.1632. C18H22O2 requires m/z 270.1620)
(Found: C, 79.22; H, 8.28%. C18H22O2 requires C, 79.96; H,
8.20%).
1,1-Bis(hydroxyphenyl)heptanes 4ad. A pale yellow oil (iso-
mer ratio 5:4:1) was characterised by mass spectroscopy
(GC-MS and HRMS) and combustion analysis; 1,1-bis(4-
hydroxyphenyl)heptane as a major component isolated by suc-
cessive recycling preparative HPLC and identified by 13C NMR
and mass spectroscopy (GC-MS); a pale-yellow crystalline
solid; δC(100 MHz) 14.1 (q), 22.6 (t), 28.0 (t), 29.3 (t), 31.7 (t),
36.1 (t), 49.6 (d), 115.2 (d), 128.8 (d), 138.1 (s) and 153.6 (s); m/z
284 (Mϩ, 4%) and 199 (100) (Found: m/z 284.1780. C19H24O2
requires m/z 284.1776) (Found: C, 79.64; H, 8.35%. C19H24O2
requires C, 80.24; H, 8.51%).
General procedure for Mnϩ-mont-catalysed alkylation of
aromatic compound with aldehydes or ketones
As a typical example, alkylation of phenol 1a with octanal 2e in
the presence of Al3ϩ-mont is described below (Table 1, run 5).
To 1a (2.50 g, 26.6 mmol) in a 20 cm3 two-necked pear-shaped
flask equipped with an Allihn condenser with a silica gel tube
was added Al3ϩ-mont (white powder; 500 mg, 0.266 mmol as
acid sites estimated by NH3-TPD2) at ca. 40 ЊC with magnetic
stirring. The mixture was heated to 100 ЊC during ca. 15 min
and kept at this temperature for ca. 45 min. The aldehyde 2e
(100 mg, 0.78 mmol) was added dropwise to the mixture which
was then stirred vigorously for 48 h at 100 ЊC. After the mixture
had been cooled, the catalyst was filtered off and rinsed with
diethyl ether (20 cm3). Removal of unchanged 1a and 2e and
ether by distillation under reduced pressure left a brown oil
which was subjected to column chromatography (Wakogel
C-300, eluents: hexane, hexane–ethyl acetate and ethyl acetate)
and bulb-to-bulb distillation. The products were a colourless oil
of 1-(hydroxyphenyl)octanes 3ae (hexane–ethyl acetate as an
eluent; 40.2 mg, 25% isolated yield, o-:p- = 8:92 determined by
GLC) and a pale yellow oil of 1,1-bis(hydroxyphenyl)octanes
4ae [hexane–ethyl acetate and ethyl acetate as eluents; 135.1 mg,
58% isolated yield; a mixture of three isomers of ca. 5:4:1 ratio
in GLC; isolated by recycling preparative HPLC successively
and assigned by 13C NMR spectra and GC-MS as 1,1-bis-
(4-hydroxyphenyl)octanes, 1-(2-hydroxyphenyl)-1-(4-hydroxy-
phenyl)octanes and 1,1-bis(2-hydroxyphenyl)octanes, respect-
ively]. The isomers of other bisphenols were similarly assigned
by 13C NMR spectral and mass spectral (GC-MS and HRMS)
results and combustion analyses.
1,1-Bis(hydroxyphenyl)octanes 4ae. A pale yellow oil (isomer
ratio 5:4:1) was characterised by mass spectroscopy (GC-MS
and HRMS)and combustion analysis;1,1-bis(4-hydroxyphenyl)-
octane as a major component isolated by successive recycling
preparative HPLC and identified by 13C NMR and mass spec-
troscopy (GC-MS); a pale-yellow crystalline solid; δC(100
MHz) 14.1 (q), 22.6 (t), 28.0 (t), 29.2 (t), 29.6 (t), 31.9 (t), 36.1
1,1-Bis(hydroxyphenyl)butanes 4aa. A pale yellow oil (isomer
ratio 6:4:<0.1) was characterised by mass spectroscopy (GC-
MS and HRMS) and combustion analysis; 1,1-bis(4-hydroxy-
phenyl)butane as a major component isolated by successive
1926
J. Chem. Soc., Perkin Trans. 1, 1997

View Article Online
(t), 49.6 (d), 115.2 (d), 128.8 (d), 138.1 (s) and 153.6 (s); m/z 298
(Mϩ, 3%) and 199 (100) (Found: m/z 298.1934. C20H26O2
requires m/z 298.1933) (Found: C, 79.17; H, 8.73%. C20H26O2
requires C, 80.05; H, 8.78%).
7.1), 4.60 (1H, br s), 6.77 (2H, d, J 8.2) and 7.26 (2H, d, J 8.2);
m/z 150 (Mϩ, 21%), 135 (100) and 107 (52).
(Hydroxyphenyl)methylcyclohexanes 3ag. A pale yellow oil
identified by 1H NMR and mass spectroscopy (GC-MS).18,19
2-(Hydroxyphenyl)butanes 3ai. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 2-(4-
hydroxyphenyl)butane as a major component, δH (270 MHz)
0.80 (3H, t, J 7.1), 2.00 (3H, d, J 7.1), 1.55 (2H, quintet, J 7.1),
2.53 (1H, sextet, J 7.1), 4.83 (1 H, br s), 6.76 (2H, d, J 8.8) and
7.38 (2H, d, J 8.8); m/z 150 (Mϩ, 11%) and 121 (100).
2-(Hydroxyphenyl)pentanes 3aj. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 2-(4-
hydroxyphenyl)pentane as a major component, δH (270 MHz)
0.85 (3H, t, J 7.0), 1.19 (3H, d, J 7.0), 1.12–1.29 (2H, m), 1.50
(2H, q, J 7.0), 2.63 (1H, sextet, J 7.0), 4.80 (1H, br s), 6.75 (2H,
d, J 8.4) and 7.04 (2H, d, J 8.4); m/z 164 (Mϩ, 11%) and 121
(100).
3-(Hydroxyphenyl)pentanes 3ak. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 3-(4-
hydroxyphenyl)pentane as a major component, δH (400 MHz)
0.75 (6H, t, J 7.4), 1.42–1.55 (2H, m), 1.59–1.71 (2H, m), 2.24
(1H, tt, J 9.3, 5.4), 4.88 (1H, br s), 6.76 (2H, d, J 8.5) and 6.99
(2H, d, J 8.5); m/z 164 (Mϩ, 12%), 135 (86) and 107 (100).
2-(Hydroxyphenyl)heptanes 3al. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 2-(4-
hydroxyphenyl)heptane as a major component, δH (400 MHz)
0.84 (3H, t, J 6.8), 1.19 (3H, d, J 7.2), 1.21–1.28 (6H, m), 1.50
(2H, q, J 7.2), 2.60 (1H, sextet, J 7.2), 5.02 (1H, br s), 6.75 (2H,
d, J 8.3) and 7.03 (2H, d, J 8.3); m/z 192 (Mϩ, 6%), 121 (100)
and 107 (13).
3-(Hydroxyphenyl)heptanes 3am. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 3-(4-
hydroxyphenyl)heptane as a major component, δH (400 MHz)
0.75 (3H, t, J 7.3), 0.82 (3H, t, J 7.3), 1.03–1.14 (2H, m), 1.15–
1.27 (2H, m), 1.41–1.52 (2H, m), 1.53–1.67 (2H, m), 2.30 (1H,
m), 4.56 (1H, br s), 6.74 (2H, d, J 8.3) and 6.98 (2H, d, J 8.3);
m/z 192 (Mϩ, 7%), 163 (10), 135 (42) and 107 (100).
4-(Hydroxyphenyl)heptanes 3an. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 4-(4-
hydroxyphenyl)heptane as a major component, δH (400 MHz)
0.83 (6H, t, J 7.3), 1.08–1.17 (4H, m), 1.39–1.54 (4H, m), 2.45
(1H, m, J 7.3), 4.57 (1H, br s), 6.75 (2H, d, J 8.3) and 7.00 (2H,
d, J 8.3); m/z 192 (Mϩ, 4%), 149 (19) and 107 (100).
(Hydroxyphenyl)cyclohexanes 3ao. A pale yellow oil charac-
terised by 1H NMR and mass spectroscopy (GC-MS); (4-
hydroxyphenyl)cyclohexane as a major component, δH (270
MHz) 1.33–1.40 (4H, m), 1.78–1.88 (6H, m), 2.29–2.38 (1H, m),
4.59 (1H, br s), 6.75 (2H, d, J 8.3) and 7.07 (2H, d, J 8.3); m/z
176 (Mϩ, 34%), 133 (100), 120 (45) and 107 (46).
1-(Methoxyphenyl)octanes 3be. A pale yellow oil character-
ised by 1H NMR, 13C NMR and mass spectroscopy (GC-MS);
1-(4-methoxyphenyl)octane as a major component, δH (400
MHz) 0.88 (3H, t, J 7.3), 1.20–1.35 (10H, m), 1.52–1.62 (2H,
m), 2.54 (2H, t, J 7.3), 3.78 (3H, s), 6.82 (2H, d, J 8.3) and 7.09
(2H, d, J 8.3); δC(100 MHz) 14.1 (q), 22.7 (t), 29.3 (t), 29.3 (t),
29.5 (t), 31.8 (t), 31.9 (t), 35.1 (t), 55.2 (q), 113.6 (d), 129.2 (d),
135.1 (s) and 157.6 (s); m/z 220 (Mϩ, 11%) and 121 (100).
2-(Methoxyphenyl)pentanes 3bj. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 1-(4-
hydroxyphenyl)pentane as a major component, δH (270 MHz)
0.83 (3H, t, J 7.3), 1.15–1.29 (2H, m), 1.20 (3H, d, J 7.3), 1.50
(2H, q, J 7.3), 2.65 (1H, sextet, J 7.3), 3.79 (3H, s), 6.83 (2H, d,
J 8.5) and 7.10 (2H, d, J 8.5); m/z 178 (Mϩ, 15%) and 135 (100).
(Methoxyphenyl)cyclohexanes 3bo. A pale yellow oil charac-
terised by 1H NMR and mass spectroscopy (GC-MS); (4-
methoxyphenyl)cyclohexane as a major component, δH (270
MHz) 1.31–1.42 (4H, m), 1.80–1.90 (6H, m), 2.39–2.49 (1H, m),
3.77 (3H, s), 6.83 (2H, d, J 8.5) and 7.12 (2H, d, J 8.5); m/z 190
(Mϩ, 55%), 147 (100) and 121 (56).
1,1-Bis(hydroxyphenyl)-1-phenylmethanes 4ah. A pale yellow
oil (isomer ratio 5:4:1) was characterised by mass spectroscopy
(GC-MS and HRMS) and combustion analysis; 1,1-bis(4-
hydroxyphenyl)-1-phenylmethane as a major component iso-
lated by successive recycling preparative HPLC and identified
by 13C NMR and mass spectroscopy (GC-MS); a pale-yellow
crystalline solid; δC(100 MHz, [2H6]acetone) 55.9 (d), 115.7 (d),
126.6 (d), 128.8 (d), 129.9 (d), 130.9 (d), 136.2 (s), 146.0 (s) and
156.4 (s); m/z 276 (Mϩ, 100%), 199 (85) and 181 (91) (Found:
m/z 276.1150. C19H16O2 requires m/z 276.1150) (Found: C,
81.35; H, 5.73%. C19H16O2 requires C, 82.58; H, 5.84%).
1,1-Bis(methoxyphenyl)octanes 4be. A pale yellow oil (isomer
ratio 8:2:<0.1) was characterised by mass spectroscopy (GC-
MS and HRMS) and combustion analysis; 1,1-bis(4-methoxy-
phenyl)octane as a major component isolated by successive
recycling preparative HPLC and identified by 13C NMR and
mass spectroscopy (GC-MS); a colourless oil; δC(100 MHz)
14.1 (q), 22.7 (t), 28.1 (t), 29.2 (t), 29.6 (t), 31.9 (t), 36.1 (t), 49.6
(d), 55.2 (q), 113.7 (d), 128.6 (d), 138.0 (s) and 157.7 (s); m/z 326
(Mϩ, 3%) and 227 (100) (Found: m/z 326.2244. C22H30O2
requires m/z 326.2246) (Found: C, 80.95; H, 9.52%. C22H30O2
requires C, 80.94; H, 9.26%).
2,2-Bis(3,4-dimethoxyphenyl)pentane 8. A pale yellow oil was
isolated by successive recycling preparative HPLC and charac-
terised by 13C NMR spectroscopy, mass spectroscopy (GC-MS)
and combustion analysis; δC(67.8 MHz) 14.1 (q), 18.1 (t), 28.0
(q), 44.5 (t), 45.7 (s), 55.7 (q), 55.8 (q), 110.3 (d), 111.3 (d), 119.1
(d), 142.6 (s), 146.8 (s) and 148.3 (s); m/z 344 (Mϩ, 12%) and 301
(100) (Found: C, 72.68; H, 8.09%. C21H28O4 requires C, 73.23;
H, 8.19%).
1-(Hydroxyphenyl)butanes 3aa. A pale yellow oil character-
ised by1H NMR and massspectroscopy(GC-MS);1-(4-hydroxy-
phenyl)butane as a major component, δH (270 MHz) 0.91 (3H,
t, J 7.6), 1.34 (2H, sextet, J 7.6), 1.55 (2H, quintet, J 7.6), 2.53
(2H, t, J 7.6), 4.70 (1H, br s), 6.74 (2H, d, J 8.3) and 7.34 (2H, d,
J 8.3); m/z 150 (Mϩ, 12%) and 107 (100).
1-(Hydroxyphenyl)pentanes 3ab. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 1-(4-
hydroxyphenyl)pentane as a major component, δH (400 MHz)
0.89 (3H, t, J 7.2), 1.26–1.34 (4H, m), 1.57 (2H, quintet, J 7.6),
2.53 (2H, t, J 7.6), 4.59 (1H, br s), 6.74 (2H, d, J 8.3) and 7.04
(2H, d, J 8.3); m/z 164 (Mϩ, 10%) and 107 (100).
1-(Hydroxyphenyl)hexanes 3ac. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 1-(4-
hydroxyphenyl)hexane as a major component, δH (400 MHz)
0.86 (3H, t, J 6.8), 1.20–1.30 (6H, m), 1.56 (2H, quintet, J 7.6),
2.50 (2H, t, J 7.6), 4.68 (1H, br s), 6.74 (2H, d, J 8.3) and 7.04
(2H, d, J 8.3); m/z 178 (Mϩ, 8%) and 107 (100).
1-(Hydroxyphenyl)heptanes 3ad. A pale yellow oil character-
ised by 1H NMR and mass spectroscopy (GC-MS); 1-(4-
hydroxyphenyl)heptane as a major component, δH (400 MHz)
0.88 (3H, t, J 6.8), 1.19–1.30 (8H, m), 1.56 (2H, quintet, J 7.7),
2.53 (2H, t, J 7.7), 4.67 (1H, br s), 6.74 (2H, d, J 8.3) and 7.04
(2H, d, J 8.3); m/z 192 (Mϩ, 7%) and 107 (100).
1-(Hydroxyphenyl)octanes 3ae. A pale yellow oil character-
ised by 1H NMR, 13C NMR and mass spectroscopy (GC-MS);
1-(4-hydroxyphenyl)octane as a major component, δH (400
MHz) 0.87 (3H, t, J 7.3), 1.20–1.35 (10H, m), 1.56 (2H, m), 2.52
(2H, t, J 7.3), 5.24 (1H, br s), 6.74 (2H, d, J 8.3) and 7.02 (2H, d,
J 8.3); δC(100 MHz) 14.1 (q), 22.7 (t), 29.3 (t), 29.3 (t), 29.5 (t),
31.7 (t), 31.9 (t), 35.1 (t), 115.1 (d), 129.4 (d), 135.2 (s) and 153.3
(s); m/z 206 (Mϩ, 11%) and 107 (100).
1-(Hydroxyphenyl)-2-methylpropanes 3af. A pale yellow oil
characterised by 1H NMR and mass spectroscopy (GC-MS); 1-
(4-hydroxyphenyl)-2-methylpropane as a major component, δH -
(270 MHz) 0.88 (6H, d, J 6.6), 1.72–1.86 (1H, m), 2.40 (2H, d, J
2,2-Bis(methoxyphenyl)pentanes 4bj. A pale yellow oil charac-
J. Chem. Soc., Perkin Trans. 1, 1997
1927

View Article Online
8 Y. Hashimoto, K. Hirata, N. Kihara, M. Hasegawa and K. Saigo,
Tetrahedron Lett., 1992, 33, 6351; Y. Hashimoto, K. Hirata,
H. Kagoshima, N. Kihara, M. Hasegawa and K. Saigo, Tetrahedron,
1993, 49, 5969.
9 D. Krüger and F. Oberlies, Chem. Ber., 1941, 74, 1711.
10 J. A. Ballantine, in Solid Supports and Catalysts in Organic Synthesis,
ed. K. Smith, Ellis Horwood, London, 1992, part 2, ch. 4, pp. 101–
102; F. J. A. Kellendonk, J. J. L. Heinerman and R. A. van Santen, in
Preparative Chemistry Using Supported Reagents, ed. P. Laszlo,
Academic Press, New York, 1987, part 8, ch. 23, pp. 456–457;
J. M. Adams, in Preparative Chemistry Using Supported Reagents, ed.
P. Laszlo, Academic Press, New York, 1987, part 8, ch. 27, pp. 509–
511.
11 R. M. Roberts and A. A. Khalaf, in Friedel–Crafts Alkylation
Chemistry, Marcel Dekker, New York, 1984, ch. 8, pp. 701–762;
S. Saito, T. Ohwada and K. Shudo, J. Am. Chem. Soc., 1995, 117,
11 081.
terised by 1H NMR and mass spectroscopy (GC-MS); 1,1-
bis(4-methoxyphenyl)pentanes as a major component, δH (270
MHz) 0.87 (3H, t, J 7.3), 1.10 (2H, m), 1.57 (3H, s), 2.00 (2H,
m), 3.78 (6H, s), 6.79 (4H, d, J 9.1) and 7.10 (4H, d, J 9.1);
δC(100 MHz) 14.8 (q), 18.1 (t), 28.0 (q), 44.6 (t), 45.0 (s), 55.2
(q), 113.2 (d), 128.2 (d), 142.4 (s) and 157.3 (s); m/z 284 (Mϩ,
5%) and 241 (100).
(3,4-Dimethoxyphenyl)cyclohexane 9. A pale yellow oil char-
acterised by 1H NMR and mass spectroscopy (GC-MS);
δH (270 MHz) 1.35–1.44 (4H, m), 1.82–1.89 (6H, m), 2.39–
2.50 (1H, m), 3.86 (3H, s), 3.88 (3H, s) and 6.74–6.79 (3H, m);
m/z 220 (Mϩ, 100%), 177 (58) and 151 (36).
2-(2-Hydroxy-5-methylphenyl)pentane 10. A pale yellow oil
1
characterised by H NMR and mass spectroscopy (GC-MS);
δH (270 MHz) 0.89 (3H, t, J 7.1), 1.22 (3H, d, J 7.1), 1.25–1.37
(2H, m), 1.56 (2H, q, J 7.1), 2.27 (3H, s), 3.02 (1H, sextet, J 7.1),
4.52 (1H, br s), 6.64 (1 H, d, J 8.0), 6.84 (1H, d, J 8.0) and 6.95
(1H, s); m/z 178 (Mϩ, 15%), 135 (100) and 121 (17).
12 As examples for the aromatic alkylation of phenol with aldehydes in
the presence of hydrogen to produce alkylphenols, W. E. Smith,
USP 4 048 239, 1977 (Chem. Abstr., 1978, 88, 6545v); E. Takahashi
and K. Ozaki, JP 88 230 648, 1988 (Chem. Abstr., 1989, 110,
38742w).
13 D. D. Perrin and W. L. F. Armarego, Purification of Laboratory
Chemicals, 3rd edn., Pergamon Press, Oxford, 1988.
14 J. Tateiwa, H. Horiuchi, K. Hashimoto, T. Yamauchi and
S. Uemura, J. Org. Chem., 1994, 59, 5901.
15 G. Sandulesco and A. Girard, Bull. Soc. Chim. Fr., Sér. 4, 1930, 47,
1300.
Acknowledgements
The authors thank Kunimine Industry Co., Ltd. for gift of
Kunipia G and Mr Yasuaki Hisamoto of this department for
measurement of high resolution mass spectra.
16 C. E. Coulthard, J. Marshall and F. L. Pyman, J. Chem. Soc., 1930,
280.
17 T. I. Briggs, G. G. S. Dutton and E. Merler, Can. J. Chem., 1956, 34,
851.
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Paper 7/01744H
Received 12th March 1997
Accepted 27th March 1997
1928
J. Chem. Soc., Perkin Trans. 1, 1997