Water-Soluble Calixarenes as New Inverse Phase-Transfer Catalysts. Their Scope in Aqueous Biphasic Alkylations and Mechanistic Implications

Article abstract of DOI:10.1002/1615-4169(200206)344:3/4<370::AID-ADSC370>3.0.CO;2-3

Alkylation reactions of active methylene compounds, alcohols and phenols with alkyl halides in aqueous NaOH solution can be carried out without the need for any added organic solvents in most cases. The water-soluble calix[n]arenes, which contain trimethylammoniomethyl groups on the upper rim, were used as inverse phase-transfer catalysts, resulting in the corresponding alkylated products in good to high yields. The scope of this methodology in aqueous biphasic alkylation reactions and the mechanistic implications are discussed.

Full text of DOI:10.1002/1615-4169(200206)344:3/4<370::AID-ADSC370>3.0.CO;2-3

FULL PAPERS
Water-Soluble Calixarenes as New Inverse Phase-Transfer
Catalysts. Their Scope in Aqueous Biphasic Alkylations and
Mechanistic Implications
Shoichi Shimizu,* Takashi Suzuki, Seiji Shirakawa, Yasuyuki Sasaki, Choichiro
Hirai
Department of Applied Molecular Chemistry and High Technology Research Center, College of Industrial Technology,
Nihon University, Narashino, Chiba 275-8575, Japan
Fax: ( ‡ 81)-47-474-2579, e-mail: s5simizu@cit.nihon-u.ac.jp
Received: October 31, 2001; Accepted: December 20, 2001
SupportingInformation for this article is available on the WWW under http://asc.wiley-vch.de or from the author.
Dedicated to Professor Howard Alper on the occasion of his 60th birthday
Abstract: Alkylation reactions of active methylene ingin the correspondingalkylated products in good to
compounds, alcohols and phenols with alkyl halides in high yields. The scope of this methodology in aqueous
aqueous NaOH solution can be carried out without biphasic alkylation reactions and the mechanistic
the need for any added organic solvents in most cases. implications are discussed.
The water-soluble calix[n]arenes, which contain tri-
methylammoniomethyl groups on the upper rim, Keywords: alkylation; biphasic catalysis; calixarenes;
were used as inverse phase-transfer catalysts, result- host-guest systems; water as solvent
alkyl halides proceed smoothly in aqueous NaOH
solution without the need for any added organic solvent
usingwater-soluble calix[ n]arenes, p-(trimethylammo-
Introduction
The −greening× of global chemical processes has become niomethyl)calix[n]arene methyl ethers (n ˆ 4, 6, and 8;
a major issue in the chemical industry.[1,2] Biphasic TACnM, see Scheme 1) as catalysts,[10] as do the aldol-
catalysis has many advantages as a methodology for type condensation and Michael addition reactions of
organic reactions from the vantage points of the activated methyl and methylene compounds.[11] We have
effective two-phase separation of a catalyst and product, also reported that rhodium complexes with water-
as well as catalyst recycling.[2] Thus, the catalyst is soluble calix[4]arenes which contain two phosphine
immobilized in a liquid phase which can be separated moieties on the upper rim are able to function not only
from the product-containingphase. Amongsome of the
as homogeneous metal catalysts but also as inverse
possibilities, e.g., fluorous phases[3] and non-aqueous phase-transfer catalysts in aqueous biphasic hydrofor-
ionic liquids,[4] aqueous biphasic reaction systems are mylation reactions.[12,13]
appealingbecause of the −green× nature of water as a
We describe herein the scope of this methodology in
solvent and the fact that it is inexpensive.[5] However, its which TACnM is used in aqueous biphasic C- and O-
application is limited generally to substrates which have alkylations of active methylene compounds, alcohols
appreciable water solubility. To solve this problem,
polar water-miscible organic solvents (co-solvents)[6] or
surfactants[7,8] are frequently used. On the other hand,
N+Me3Cl–
CH2OH
use of these additives usually complicates work-up
procedures, particularly in regard to product separation
and the recovery of the catalyst and additive itself.
O
O
CH2
n
In order to circumvent this dilemma, we recently
OMe
OH
β-CD
HO
7
developed a new reaction system,[9-13,14] which is based
on the inverse phase-transfer catalysis (IPTC)[15,16] of
water-soluble calix[n]arenes.[17,18] For example, C-alkyl-
TACnM (n = 4, 6, 8)
Scheme 1. The structures of the water soluble calix[n]arenes,
ation reactions of active methylene compounds with TACnM, and b-cyclodextrin.
370
¹ VCH Verlagsgesellschaft mbH, 69451 Weinheim, Germany, 1615-4150/02/3443+4-370 378 $ 17.50-.50/0
Adv. Synth. Catal. 2002, 344, No. 3+4

Water-Soluble Calixarenes as New Inverse Phase-Transfer Catalysts
FULL PAPERS
and phenols with alkyl halides.[10] In this biphasic system of the startingmaterial in 85% yield (entry 1). The
which employs aqueous NaOH solutions, the TACnM addition of b-cyclodextrin (b-CD) as an inverse phase-
catalysts exhibit a selectivity for the size and/or shape of transfer catalyst gave poor yields of 3-phenyl-2-unde-
the acidic reactants, and the selective monoalkylations canone (entry 2). However, when the same reaction was
of active methylene compounds and aromatic diols can carried out in the presence of the water-soluble calix[4]-
be achieved. Finally, the mechanistic implications of arene TAC4M, the yield increased to 86% (entry 6). For
biphasic alkylation reactions are briefly discussed on the the sake of comparison, we examined reactions in which
basis of these remarkable features.
tetrabutylammonium bromide (TBAB) and hexadecyl-
tributylphosphonium bromide (HTPB) were employed
as normal phase-transfer catalysts,[19,20] and found that
there were significant increases in the yields of O-
alkylated products (entries 4 and 5).[21] When using
Results and Discussion
The activity and selectivity of water-soluble calix[n]ar- TBAB with dibutyl ether or HTPB, the reaction largely
enes TACnM ¥ nH2O (n ˆ 4, 6 and 8) were first tested in takes place in the organic phase in which the hydration
model alkylation reactions of phenylacetone with alkyl of the oxygen of the enolate is depressed. The data
halides in aqueous NaOH solution, and these results are clearly show that the TAC4M catalyst is more efficient
summarized in Table 1. The treatment of phenylacetone than TBAB and HTPB in terms of alkylation/hydrolysis
with octyl bromide in 4 N aqueous NaOH solution for and C-/O-alkylation selectivities in addition to the two
10 h at 100 8C afforded only trace amounts of 3-phenyl- major advantages of IPTC, viz. ease of separation of the
2-undecanone and octyl alcohol, alongwith the recovery
aqueous catalyst solution and no necessity of usingan
organic solvent. The observed order of reactivity of the
alkyl halides is I ꢀ Br ꢁ Cl (entries 6 8). This order
suggests that alkyl iodides can be used as alkylating
reagents in IPTC reaction systems, which is contrary
from that in normal PTC reaction systems. This is
presumably the result of a drop in the affinity of the
iodide ion for the quaternary cation in aqueous media,
that is, a diminished level of catalyst poisoning.[22] The
difference in reactivity between alkyl bromide and
chloride was confirmed by the reactions with 1-bromo-
4-chlorobutane and 1,4-dibromobutane, in which 7-
chloro-3-phenyl-2-heptanone and 1-(1-phenylcyclopen-
tyl)ethanone were obtained, respectively, as major
products (entries 9 and 10). When activated organic
halides, such as 4-tert-butylbenzyl, 4-bromobenzyl and
2-naphthylmethyl bromides, were used as alkylating
reagents, high to excellent yields were obtained, even at
60 8C (entries 13 15).
Some examples of TACnM-catalyzed alkylation reac-
tions of active methylene compounds are summarized in
Table 2. In all cases, the reactions proceeded smoothly in
aqueous NaOH solution to afford the corresponding
alkylated products in good to high yields. When 2,4-
pentanedione and benzoylacetonitrile were used as
substrates, an aqueous 2 N NaOH solution is sufficiently
basic to generate the corresponding carbanions to give
high yields of alkylated products (entries 3 and 4). In the
reaction of phenylacetonitrile, the monoalkylated prod-
uct was formed with excellent selectivity compared to
that for a normal PTC reaction (entry 6).[23] With 2-
chlorophenylacetonitrile and 1-naphthylacetonitrile,
complete selectivity for monoalkylation was achieved
(entries 8 and 14). Furthermore, the alkylation of indene
selectively gave the monoalkylated product 3-(1-naph-
thylmethyl)indene[24] even though it is known that
dialkylation takes place to a considerable extent under
PTC conditions in the case of highly activated organic
Table 1. C-Alkylations of phenylacetone in aqueous NaOH
solution.
R
Catalyst 1.0 mol %
4 N NaOH 3 mL
R OH
R
X
O
100 °C, 10 h
4.0 mmol
O
1
4.8 mmol
2
Isolated yield [%]
R-X
Entry Catalyst
1
2
1
2
none
CH3(CH2)7Br
CH3(CH2)7Br
CH3(CH2)7Br
CH3(CH2)7Br
CH3(CH2)7Br
CH3(CH2)7Br
CH3(CH2)7Cl
CH3(CH2)7I
Cl(CH2)4Br
trace
trace
β-CD[a]
TBAB[b]
TBAB[b]
HTPB[e]
TAC4M
TAC4M
TAC4M
TAC4M
trace
14
76 (+trace)[c] 17
3
4[d]
73 (+5)[c]
71 (+8)[c]
86
8
5
2
6
6
trace
12
7
8
84
65[f]
4
(9)[g]
9
(trace)[g]
TAC4M
TAC4M
TAC4M
TAC4M
Br(CH2)4Br
8 (+63)[h]
10
11
12[i]
13[j]
14[j]
15[j]
75
91
0
0
CH2=CH(CH2)3Br
c-C6H11CH2Br
trace
4-t-BuC6H4CH2Br
4-BrC6H4CH2Br
2-C10H7CH2Br
94
92
87
0
0
TAC4M
TAC4M
[a]
[b]
[c]
b-Cyclodextrin.
Tetrabutylammmonium bromide 4.0 mol %.
2-Methyl-3-oxa-1-phenyl-1-undecene was also formed as
an O-alkylated product.
Dibutyl ether (3 mL) was used as a solvent.
Hexadecyltributylphosphonium bromide 4.0 mol %.
7-Chloro-3-phenyl-2-heptanone was formed selectively.
7-Hydroxy-3-phenyl-2-heptanone.
[d]
[e]
[f]
[g]
[h]
[i]
1-(1-Phenylcyclopentyl)ethanone.
Reaction time 20 h.
Reaction temperature 60 8C.
[j]
Adv. Synth. Catal. 2002, 344, 370 378
371

Shoichi Shimizu et al.
FULL PAPERS
Table 2. C-Alkylations of various active methylene compounds in aqueous NaOH solution.
R R
R
TACnM
R2
R1
Br
R OH
R2
R1
R2
R1
4 N NaOH 3 mL
R = 1-C10H7CH2
4.0 mmol
4
2
3
Isolated yield [%]
R1–CH2–R2 [mmol]
Conditions
Entry
Catalyst [mol%]
2
3
4
1[a]
2[a]
3[a]
4[a]
5[a]
6
60 °C, 0.5 h
60 °C, 0.5 h
60 °C, 2 h
60 °C, 2 h
60 °C, 2 h
0
11 (+trace)[b]
50 (+2)[b]
88 (+3)[b]
0
none
CH3COCH2COCH3 (12.0)
CH3COCH2COCH3 (12.0)
CH3COCH2COCH3 (12.0)
C6H5COCH2CN (12.0)
C6H5COCH2CN (4.8)
C6H5CH2CN (12.0)
TAC6M (1.0)
trace
0
TAC6M (1.0)
TAC6M (1.0)
TAC6M (1.0)
TAC4M (1.0)
TAC4M (1.0)
3
0
82
69
12
22
(trace)[c]
(trace)[c]
0
90
70 °C, 10 h
70 °C, 10 h
8
C6H5CH2CN (4.8)
68
13
7
19
8
60 °C, 10 h
70 °C, 10 h
70 °C, 2 h
70 °C, 2 h
84
74[d]
2-ClC6H4CH2CN (4.8)
C6H4-1,2-(–CH=CH–CH2–) (4.8)
1-C10H7CH2CN (4.8)
TAC4M (1.0)
TAC4M (1.0)
none
0
0
trace[e]
4 (+6)[c]
9
10[f]
11[f]
12[f]
13[f]
14[f]
21
58
0
0
0
0
TAC4M (1.5)
1-C10H7CH2CN (4.8)
trace
70 °C, 2 h
TAC6M (1.0)
TAC8M (0.75)
TAC6M (1.0)
66
1-C10H7CH2CN (4.8)
trace
trace
trace
70 °C, 2 h
70 °C, 5 h
1-C10H7CH2CN (4.8)
1-C10H7CH2CN (4.8)
78
91
0
0
[a]
[b]
[c]
[d]
[e]
[f]
2 N Aqueous NaOH was used in the place of 4 N aqueous NaOH.
6-(1-Naphthyl)-2,4-hexanedione was isolated as a mixture with 3-(1-naphthylmethyl)-2,4-pentanedione.
Bis(1-naphthylmethyl) ether.
3-(1-Naphthylmethyl)indene.
1,3-Bis(1-naphthylmethyl)indene.
Dipropyl ether (3 mL) was used as a solvent.
halides, such as benzyl and allyl chlorides (entry 9).[25] out in the presence of the water-soluble calix[6]arene
The formation of 3-(1-naphthylmethyl)indene can be TAC6M, the yield increased to 75% (entry 3). When
ascribed to the basic isomerization of the initially cetyltrimethylammonium bromide (hexadecyltrimeth-
formed 1-alkylindene.[25] Takinginto account the molar
ylammonium bromide, CTAB) was used, in place of
amounts of catalysts added, the activities of catalysts TAC6M as a cationic surfactant, the yield of desired
TACnM increase in the order of TAC4M < TAC6M < unsymmetrical ether was diminished to 56% (entry 2)
TAC8M for the alkylation reactions of 1-naphthylace- accompanied by the formation of an emulsion during
tonitrile (entries 11 13). This may be a reflection of the the work-up. The TAC6M catalyst is superior to CTAB
followinginterfacial mechanism, because the distribu-
in terms of yield, selectivity and product separation. A
tion of TACnM in the organic phase was negligible.[9] In secondary alkyl halide was found to be unsuitable as an
the aqueous phase near the interface, the water-soluble alkylatingreagent (entry 6). In all other cases where
calix[n]arenes TACnM would form host-guest com- TACnM was used, the reactions proceeded smoothly to
plexes with a carbanion, produced via the deprotonation afford the corresponding O-alkylated products in good
of the active methylene compound by hydroxide ions, to high yields. When 1-bromo-4-chlorobutane is used,
and nucleophilic attack by the anion on an alkyl halide the butoxide ion reacts predominantly with the bromide
would take place at the interface.
substituent. Thus, 1-butoxy-4-chlorobutane is selective-
The water-soluble calix[n]arenes TACnM were also ly obtained as a monoether (entry 5). When phenol and
examined with respect to O-alkylation reactions of 4-methylphenol were used instead of alcohols, the
alcohols and phenols with alkyl halides in aqueous reaction afforded O-alkylated products in good yields
NaOH solution, and the results are summarized in (entries 9 and 10). The selective formation of O-
Table 3. Treatment of 1-hexanol with 4-tert-butylbenzyl alkylated products in our system is in sharp contrast to
bromide in 4 N aqueous NaOH solution for 3 h at 60 8C the reported reactions of allyl and benzyl halides with
afforded the 4-tert-butylbenzyl hexyl ether in 22% yield sodium phenoxide in water.[26] In the case of an aromatic
(entry 1). However, when the same reaction was carried diol, 1,4-benzenedimethanol, good selectivity for the
372
Adv. Synth. Catal. 2002, 344, 370 378

Water-Soluble Calixarenes as New Inverse Phase-Transfer Catalysts
FULL PAPERS
Table 3. O-Alkylations of various alcohols and phenols in aqueous NaOH solution.
Catalyst
R3
R X
R3
O R
OH
R O R
R OH
4 N NaOH 3 mL
5
6
2
Isolated yield [%]
R3–OH [mmol]
R–X [4.0 mmol]
Conditions
Catalyst [mol %]
Entry
5
6
2
1
2
trace
12
trace
0
trace
4-t-BuC6H4CH2Br
4-t-BuC6H4CH2Br
none
60 °C, 3 h
60 °C, 3 h
60 °C, 3 h
60 °C, 2 h
100 °C, 8 h
100 °C, 10 h
60 °C, 2 h
60 °C, 3 h
22
CH3(CH2)5OH (12.0)
CH3(CH2)5OH (12.0)
CTAB[a] (0.50)
TAC6M (0.50)
TAC4M (0.50)
TAC4M (1.0)
56
5
3
75
3
CH3(CH2)5OH (12.0)
CH3(CH2)3OH (12.0)
CH3(CH2)3OH (12.0)
CH3(CH2)3OH (12.0)
CH2=CHCH2OH (12.0)
CH3CHOMe(CH2)2OH (12.0)
4-t-BuC6H4CH2Br
4-BrC6H4CH2Br
Cl(CH2)4Br
4
87
3
79[b] (+8)[c]
0
5
0
6
17
86
78
0
6 (+6)[d]
CH3(CH2)5CHBrCH3 TAC4M (1.0)
7
4
5
4-t-BuC6H4CH2Br
4-t-BuC H CH Br
TAC4M (0.50)
TAC4M (0.50)
TAC4M (0.50)
TAC6M (0.50)
TAC4M (1.0)
HTPB[h] (1.0)
TAC6M (1.0)
8
4
6
6
4
2
9[e]
10[e]
11
12
13
4-t-BuC6H4CH2Br
4-t-BuC6H4CH2Br
CH3(CH2)7Br
60 °C, 7 h
60 °C, 7 h
100 °C, 2 h
100 °C, 2 h
100 °C, 2 h
82 (+trace)[f]
82 (+9)[g]
83
21 (+47)[i]
49 (+12)[i]
0
8
C6H5OH (4.8)
0
trace
3
4-MeC6H4OH (4.8)
0
C6H5CH2OH (12.0)
C6H4-1,4-(–CH2OH)2 (8.0)
C6H4-1,4-(–CH2OH)2 (8.0)
trace
trace
13
21
CH3(CH2)5Br
CH3(CH2)5Br
[a]
[b]
[c]
[d]
[e]
[f]
Cetyltrimethylammonium bromide (hexadecyltrimethylammonium bromide).
1-Butoxy-4-chlorobutane.
1,4-Dibutoxybutane.
2-Octene.
1 N Aqueous NaOH was used in the place of 4 N aqueous NaOH.
2-(4-tert-Butylbenzyl)phenol.
2-(4-tert-Butylbenzyl)-4-methylphenol.
Hexadecyltributylphosphonium bromide.
1,4-Bis(hexyloxymethyl)benzene.
[g]
[h]
[i]
mono-O-alkylated product was achieved by usingTAC 6 alkylation reaction is similar to that for the C-alkylation
M (entry 13). The monoether/diether ratio of 4.1 is 9.1 reaction. In the aqueous phase near the interface, the
times larger than that (0.45) observed in the presence of water-soluble calix[n]arenes TACnM form host-guest
HTPB. This selectivity of TAC6M as an inverse phase- complexes with alkoxide anions, and a nucleophilic
transfer catalyst, which is opposite to HTPB as a phase- attack by the anion on an alkyl halide takes place at the
transfer catalyst, is of interest.
interface. This is somewhat different from the interfacial
For mechanistic considerations, the effects of size and/ mechanism of normal phase-transfer catalysis as pro-
or shape of alcohol molecules and catalyst cavities on O- posed by Makosza, which involves a C-C bond-forming
alkylations in aqueous NaOH solution were examined, reaction within the bulk organic phase.[23] In the case of
and the results are summarized in Table 4. The effi- reactions of aliphatic alcohols, the size of the TAC4M
ciency of the TAC4M catalyst in terms of yield of desired cavity may be sufficiently large to accommodate meth-
unsymmetrical ether increases with an increase in the anol to butanol, but may be somewhat small to
molecular size of alcohols from methanol to butanol accommodate hexanol. In the case of reactions of 2-
(entries 1 4), whereas it decreases in the case of a (hydroxymethyl)naphthalene, the size of the TAC8M
reaction of hexanol (entry 5). In the reactions of cavity may be sufficiently large to accommodate the
methanol to butanol, the efficiency increases with a naphthyl ring, but those of TAC4M and TAC6M may be
decrease in the solubility of alcohols in water. Taking too small. This is reminiscent of the result where
into account the molar amounts of catalysts added, the relatively good selectivity for the mono-O-alkylated
activities of the TACnM catalysts increase in the order of product was achieved by usingTAC 6M in the reaction of
TAC4M < TAC6M < TAC8M for an alkylation reaction 1,4-benzenedimethanol, indicatingthat the size of the
using2-(hydroxymethyl)naphthalene (entries 7
9).
TAC6M cavity might be too small to accommodate the
These results show that the mechanism for the O- mono-O-alkylated product, 1-(hexyloxymethyl)-4-hy-
Adv. Synth. Catal. 2002, 344, 370 378
373

Shoichi Shimizu et al.
FULL PAPERS
Table 4. Effects of size and/or shape of alcohol molecules and catalyst cavities on O-alkylations in aqueous NaOH solution.
Catalyst
R3
R X
R3
O R
OH
R O R
R OH
4 N NaOH 3 mL
5
6
2
Isolated yield [%]
R3–OH [mmol]
R–X [mmol]
Conditions
Entry
Catalyst [mol %]
5
6
2
5
trace
trace
6
4-t-BuC6H4CH2Br (4.0) TAC4M (0.50)
60 °C, 3 h
60 °C, 3 h
60 °C, 3 h
60 °C, 3 h
60 °C, 3 h
100 °C, 2 h
100 °C, 2 h
32
48
73
81
62
19
68
72
81
–
1
2
CH3OH (12.0)
4-t-BuC6H4CH2Br (4.0)
9
5
CH3CH2OH (12.0)
CH3(CH2)2OH (12.0)
CH3(CH2)3OH (12.0)
CH3(CH2)5OH (12.0)
TAC4M (0.50)
3
4-t-BuC6H4CH2Br (4.0)
4-t-BuC6H4CH2Br (4.0)
TAC4M (0.50)
TAC4M (0.50)
4
4
3
trace
trace
trace
5
trace
4-t-BuC6H4CH2Br (4.0) TAC4M (0.50)
6
0
0
2-C10H7CH2OH (12.0) CH3(CH2)7Br (4.0)
none
CH3(CH2)7Br (4.0)
2-C10H7CH2OH (12.0)
TAC4M (1.0)
7
8
trace
trace
21
2-C10H7CH2OH (12.0)
TAC6M (0.67)
TAC8M (0.50)
none
100 °C, 2 h
100 °C, 2 h
60 °C, 5 h
60 °C, 5 h
60 °C, 5 h
0
0
CH3(CH2)7Br (4.0)
9
2-C10H7CH2OH (12.0) CH3(CH2)7Br (4.0)
10
11
12
trace
8
none
none
none
C6H5CH2Br (8.0)
C6H5CH2Br (8.0)
C6H5CH2Br (8.0)
β-CD[a] (0.25)
27
–
–
62
17
TAC4M (0.25)
[a]
b-Cyclodextrin.
elemental analyzer. Gas-liquid chromatography (GC) was
performed with a Hewlett-Packard GC 5890A usingcapillary
columns (DB-1701 and DB-WAX, 30 m  0.25 mm). Prepa-
rative gel-permeation chromatography (GPC) was done with a
JAI model 908 liquid chromatograph using JAIGEL-1H and
2H columns. Preparative thin layer chromatography (TLC)
and flash chromatography were carried out on precoated silica
gel 60 F254 plates (20 cm  20 cm  2 mm, E. Merck) and with
silica gel 60 (spherical 0.040 À0.100 mm, Kanto), respectively.
Tetrahydrofuran (THF) was freshly distilled from Na-benzo-
phenone. The 1-(bromomethyl)naphthalene used herein was
prepared by the reaction of 1-(chloromethyl)naphthalene with
CaBr2 in the presence of tetrabutylammonium bromide, and
purified by recrystallization from hexane-diethyl ether. Unless
otherwise noted, startingmaterials and substrates were
commercially available materials and were used without
further purification.
droxymethylbenzene. Thus, the efficiencyof the TACnM
catalyst varies dependingon the size and/or shape of the
acidic substrate molecules, but not the alkyl halide
molecules. This mechanistic consideration is supported
by the findingthat the selective formation of dibenzyl
ether was observed in the reaction of benzyl bromide in
aqueous NaOH solution (entry 12).
Conclusion
The water-soluble calix[n]arene TACnM was found to
catalyze alkylation reactions of active methylene com-
pounds, alcohols, and phenols with alkyl halides smooth-
ly in aqueous NaOH solution. This water-soluble
catalytic system employingTAC nM provides additional
options in aqueous biphasic reactions, in terms of
synthetic chemistry and process engineering.
Catalyst Preparation
Experimental Section
p-tert-Butylcalix[n]arenes (n ˆ 4, 6, and 8)[27] were prepared
[28]
followingliterature methods.
They were debutylated by
treatment with AlCl3 and phenol in toluene.[29] The calix[n]ar-
enes (n ˆ 4, 6, and 8) thus obtained were converted to their
methyl ether derivatives by treatment with CH3I and NaH.[29,30]
The methyl ether of the tetramer, 25,26,27,28-tetramethoxy-
calix[4]arene, was treated with paraformaldehyde, acetic acid,
concentrated HCl, and 85% phosphoric acid in dioxane to give
the chloromethyl derivative, 5,11,17,23-tetrakis(chlorometh-
yl)-25,26,27,28-tetramethoxycalix[4]arene, accordingto a pro-
cedure developed by Shinkai et al.[31] The chloromethyl
derivatives of the hexamer and octamer were prepared from
the correspondingmethyl ethers by treatment with chloro-
methyl methyl ether and ZnCl2 in CS2-CH2Cl2.[32]
General Remarks
Meltingpoints were determined on a Yazawa BY-1 micro
melting-point apparatus and are uncorrected. 1H and
13C NMR spectra were recorded with a JEOL JNM-EX90
À
spectrometer at 89.5 and 22.5 MHz, a JEOL JNM GX67S
spectrometer at 270 and 67.9 MHz, or Bruker Avance-400 at
400 and 100 MHz, respectively. IR spectra were recorded on a
Bio-Rad FTS-60A spectrometer. Mass spectra were obtained
on a JEOL JMS-AX500 mass spectrometer (EI, 70 eV) using
an interfaced GC-MS or a direct-insertion probe. Microanal-
yses were performed on a Perkin-Elmer 240C or 2400II
374
Adv. Synth. Catal. 2002, 344, 370 378

Water-Soluble Calixarenes as New Inverse Phase-Transfer Catalysts
FULL PAPERS
Na2SO4 and evaporated. The products were purified by pre-
parative GPC and/or TLC and the isolated yields were
determined.
25,26,27,28-Tetramethoxy-5,11,17,23-tetrakis(trimethyl-
ammoniomethyl)calix[4]arene Tetrachloride
Tetrahydrate (TAC4M ¥ 4 H2O)
3-Phenyl-2-undecanone:[20] 1H NMR (400 MHz, CDCl3):
d ˆ 7.19 7.34 (m, 5H), 3.59 (t, J ˆ 7.4 Hz, 1H), 2.04 (s, 3H),
1.13 1.27 (m, 14H), 0.86 (t, J ˆ 6.8 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d ˆ 208.65, 139.17, 128.86, 128.24, 127.16,
59.82, 31.85, 31.80, 29.55, 29.39, 29.24, 29.02, 27.46, 22.65, 14.10;
IR (KBr): n ˆ 2926, 2855, 1715, 1455, 1354, 1159, 757, 701 cmÀ1;
The procedure used for this material was analogous to the
literature method,[31] with minor modifications. Through a
stirred DMF solution (80 mL) of the chloromethylated tet-
ramer, 5,11,17,23-tetrakis(chloromethyl)-25,26,27,28-tetrame-
thoxycalix[4]arene, (4.00 g, 5.9 mmol) was bubbled gaseous
trimethylamine for 6 h at room temperature, which essentially
follows the established method. The precipitate was collected
by filtration, washed with diethyl ether, recrystallized from
ethanol-diethyl ether (11:4), and dried under vacuum to give
TAC4M as a white powder; yield: 4.27 g(4.3 mmol, 73%); mp
(decomp) > 253 8C [anhydrous TAC4M; lit.[31] mp (decomp)
‡
MS (EI, 70 eV): m/z ˆ 246 (M , 1), 203 (19), 147 (8), 134 (29),
119 (14), 105 (23), 91 (100), 69 (4), 57 (7), 43 (16).
2-Methyl-3-oxa-1-phenyl-1-undecene: 1H NMR (400 MHz,
CDCl3): d ˆ 7.76 (d, J ˆ 7.5 Hz, 2H), 7.1 7.5 (m, 3H), 5.33 (s,
1H), 3.94 (t, J ˆ 6.6 Hz, 2H), 2.07 (s, 3H), 0.89 1.78 (m, 15H);
‡
MS (EI, 70 eV): m/z ˆ 246 (M , 13), 155 (8), 134 (100), 117 (8),
1
> 270 8C]; H NMR (89.5 MHz, TSP, D2O): d ˆ 7.40 (s, 8H),
116 (7), 115 (8), 105 (7), 91 (23), 43 (35).
4.48 (s, 8H), 3.85 (s, 8H), 3.68 (s, 12H), 3.08 (s, 36H); IR (KBr):
n ˆ 3430, 873 cmÀ1; anal. calcd. for C48H72Cl4N4O4 ¥ 4 H2O: C
58.65, H 8.20, N 5.70; found: C 58.67, H 8.22, N 5.68.
3-Phenyl-7-octene-2-one: 1H NMR (400 MHz, CDCl3): d ˆ
7.19 7.34 (m, 5H), 5.69 5.79 (ddt, J ˆ 17.0, 10.3, 6.7 Hz, 1H),
4.90 5.01 (m, 2H), 3.60 (t, J ˆ 7.4 Hz, 1H), 2.01 2.07 (m, 6H),
1.66 1.75 (m, 1H), 1.18 1.37 (m, 2H); 13C NMR (100 MHz,
CDCl3): d ˆ 208.54, 138.96, 138.38, 128.98, 128.95, 128.91,
128.22, 127.24, 114.70, 59.64, 33.62, 31.22, 29.02, 26.71; IR
(KBr): n ˆ 3029, 2937, 2861, 1641, 1713, 1355, 1160, 912, 757,
37,38,39,40,41,42-Hexamethoxy-5,11,17,23,29,35-
hexakis(trimethylammoniomethyl)calix[6]arene
Hexachloride Hexahydrate (TAC6M ¥ 6 H2O)
‡
702 cmÀ1; MS (EI, 70 eV): m/z ˆ 202 (M , 6), 159 (17), 134 (9),
117 (24), 91 (100), 81 (19), 43 (27).
4-(4-tert-Butylphenyl)-3-phenyl-2-butanone:
1H NMR
This compound was prepared from the chloromethylated
hexamer (4.0 g, 4.0 mmol) following the procedure described
above for TAC4M and was obtained as a white powder from
ethanol-diethyl ether (4:3); yield: 3.12 g(2.1 mmol, 53%); mp
(decomp) > 248 8C; 1H NMR (89.5 MHz, TSP, D2O): d ˆ 7.29
(s, 12H), 4.42 (s, 12H), 4.1 (s, 12H), 3.50 (s, 18H), 3.10 (s, 54H);
IR (KBr): n ˆ 3410, 874 cmÀ1; anal. calcd. for C72H108Cl6N6O6 ¥
6 H2O: C 58.65, H 8.20, N 5.70; found: C 58.46, H 8.43, N 5.35.
(400 MHz, CDCl3): d ˆ 7.19 7.31 (m, 7H), 6.99 7.01 (m,
2H), 3.93 (t, J ˆ 7.3 Hz, 1H), 3.42 (dd, J ˆ 13.9, 8.0 Hz, 1H), 2.86
(dd, J ˆ 13.9, 6.6 Hz, 1H), 2.00 (s, 3H), 1.27 (s, 9H); 13C NMR
(100 MHz, CDCl3): d ˆ 207.72, 148.80, 138.68, 136.63, 128.86,
128.55, 128.27, 127.31, 125.12, 61.37, 37.75, 34.28, 31.33, 29.50;
IR (KBr): n ˆ 2923, 2869, 1715, 1493, 1356, 1155, 825, 751,
‡
701 cmÀ1; MS (EI, 70 eV): m/z ˆ 280 (M , 23), 265 (5), 237 (39),
147 (100), 132 (10), 117 (9), 105 (6), 91 (7), 57 (48).
4-(4-Bromophenyl)-3-phenyl-2-butanone:
1H NMR
(400 MHz, CDCl3): d ˆ 7.23 7.33 (m, 5H), 7.13 7.15 (m,
2H), 6.88 6.91 (m, 2H), 3.85 (t, J ˆ 7.4 Hz, 1H), 3.36 (dd, J ˆ
13.9, 7.2 Hz, 1H), 2.84 (dd, J ˆ 13.9, 7.5 Hz, 1H), 2.02 (s, 3H);
13C NMR (100 MHz, CDCl3): d ˆ 207.28, 138.67, 138.02,
131.28, 130.77, 129.00, 128.32, 127.54, 119.97, 61.36, 37.69,
29.45; IR (KBr): n ˆ 2910, 1716, 1486, 1354, 1219, 1154, 1008,
818, 741, 705 cmÀ1; MS (EI, 70 eV): m/z ˆ 304 (27), 302 (28),
261 (51), 259 (54), 223 (11), 180 (100), 171 (30), 169 (34), 165
(16), 90 (13), 89 (13), 77 (14), 43 (47).
49,50,51,52,53,54,55,56-Octamethoxy-
5,11,17,23,29,35,41,47-
octakis(trimethylammoniomethyl)calix[8]arene
Octachloride Octahydrate (TAC8M ¥ 8 H2O)
This compound was prepared from the chloromethylated
octamer (4.0 g, 3.0 mmol) following the procedure described
above for TAC4M and was obtained as a white powder from
methanol-ethanol-diethyl ether (7:3:5); yield: 3.26 g
1
4-(2-Naphthyl)-3-phenyl-2-butanone: H NMR (400 MHz,
(1.7 mmol, 56%); mp (decomp)
>
255 8C; 1H NMR
CDCl3): d ˆ 7.66 7.76 (m, 3H), 7.49 (s, 1H), 7.36 7.42 (m,
2H), 7.16 7.30 (m, 6H), 4.00 (t, J ˆ 7.3 Hz, 1H), 3.59 (dd, J ˆ
13.8, 7.5 Hz, 1H), 3.05 (dd, J ˆ 13.8, 7.2 Hz, 1H), 2.01 (s, 3H);
13C NMR (100 MHz, CDCl3): d ˆ 207.59, 138.40, 137.23,
133.42, 132.02, 128.92, 128.34, 127.77, 127.52, 127.49, 127.40,
127.39, 125.84, 125.28, 61.47, 38.49, 29.55; IR (KBr): n ˆ 2933,
1710, 1492, 1357, 1223, 1155, 961, 814, 751, 697 cmÀ1; MS (EI,
(89.5 MHz, TSP, D2O): d ˆ 7.37 (br s, 16H), 4.49 (br s, 16H),
4.06 (br s, 16H), 3.37 (s, 24H), 3.08 (s, 72H); IR (KBr): n ˆ 3410,
875 cmÀ1; anal. calcd. for C96H144Cl8N8O8 ¥ 8 H2O: C 58.65, H
8.20, N 5.70; found: C 58.59, H 8.47, N 5.16.
‡
70 eV): m/z ˆ 274 (M , 31), 231 (26), 215 (7), 153 (23), 141
Typical Procedure for C- and O-Alkylations under
Aqueous Biphasic Conditions
(100), 115 (8), 103 (5), 77 (5), 43 (7).
7-Chloro-3-phenyl-2-heptanone: 1H NMR (400 MHz,
CDCl3): d ˆ 7.31 7.35 (m, 2H), 7.24 7.28 (m, 1H), 7.19
7.21 (m, 2H), 3.60 (t, J ˆ 7.4 Hz, 1H), 3.46 3.49 (m, 2H), 2.00
2.09 (m, 4H), 1.66 1.82 (m, 3H), 1.22 1.42 (m, 2H); 13C NMR
(100 MHz, CDCl3): d ˆ 208.21, 138.75, 128.99, 128.19, 127.36,
59.57, 44.73, 32.48, 31.00, 29.09, 24.75; IR (KBr): n ˆ 2942, 2865,
1712, 1454, 1356, 1164, 755, 702 cmÀ1; MS (EI, 70 eV): m/z ˆ
A mixture of active methylene compound (4.8 mmol), alkyl
halide (4.0 mmol), a catalytic amount (1.0 mol %) of TACn M
¥ nH2O, and aqueous 4 N NaOH (3 mL) was heated to 60
100 8C for 0.5 10 h and stirred with a magnetic stirring bar (Æ4
 10 mm) at 1000 rpm. After the addition of water (5 mL), the
resultingmixture was extracted with chloroform (10 mL
Â
‡
4).[33] The combined extracts were dried over anhydrous
224 (M , 1), 181 (20), 145 (16), 91 (100).
Adv. Synth. Catal. 2002, 344, 370 378
375

Shoichi Shimizu et al.
FULL PAPERS
‡
7-Hydroxy-3-phenyl-2-heptanone: 1H NMR (400 MHz,
CDCl3): d ˆ 7.19 7.35 (m, 5H), 3.59 3.63 (m, 2H), 2.05 (s,
3H), 1.22 1.75 (m, 8H); 13C NMR (100 MHz, CDCl3): d ˆ
208.51, 138.93, 128.97, 128.22, 127.31, 62.65, 59.76, 32.56, 31.49,
29.12, 23.66; IR (KBr): n ˆ 3405, 2932, 2861, 1710, 1453, 1355,
1038, 791, 757cmÀ1; MS (EI, 70 eV): m/z ˆ 293 (2), 291 (M ,7),
141 (100), 115 (16), 91 (2), 63 (3).
2,3-Bis(1-naphthyl)propanenitrile: 1H NMR (400 MHz,
CDCl3): d ˆ 7.36 7.97 (m, 14H), 4.89 (t, J ˆ 7.3 Hz, 1H),
3.77 3.80 (m, 2H); 13C NMR (100 MHz, CDCl3): n ˆ 134.01,
133.93, 132.50, 131.50, 131.46, 130.14, 129.34, 129.20, 129.18,
128.30, 127.86, 126.95, 126.44, 126.14, 126.01, 125.79, 125.51,
125.48, 122.67, 122.06, 120.78, 37.88, 35.51; IR (KBr) 3059,
3051, 2936, 2241, 1598, 1512, 1397, 797, 776 cmÀ1; MS (EI,
‡
1159, 1069, 753, 701 cmÀ1; MS (EI, 70 eV): m/z ˆ 206 (M , 5),
188 (9), 161 (26), 145 (49), 117 (58), 105 (44), 91 (100), 77 (44),
43 (74).
7-Bromo-3-phenyl-2-heptanone: 1H NMR (400 MHz,
CDCl3): d ˆ 7.19 7.36 (m, 5H), 3.60 (t, J ˆ 7.4 Hz, 1H), 3.36
(t, J ˆ 6.8 Hz, 2H), 2.05 (s, 3H), 1.66 1.93 (m, 4H), 1.22 1.43
(m, 2H); 13C NMR (100 MHz, CDCl3): d ˆ 208.23, 138.73,
129.01, 128.20, 127.38, 59.57, 33.49, 32.65, 30.87, 29.11, 26.03; IR
(KBr): n ˆ 2940, 2863, 1713, 1454, 1355, 1162, 753, 702 cmÀ1;
MS (EI, 70 eV): m/z ˆ 227 (15), 225 (15), 145 (25), 134 (21), 91
(100), 77 (6), 43 (30).
‡
70 eV): m/z ˆ 307 (M , 9), 141 (100), 115 (11).
3-(1-Naphthylmethyl)indene: 1H NMR (270 MHz, CDCl3):
d ˆ 7.70 7.98 (m, 3H), 7.17 7.45 (m, 8H), 5.84 (s, 1H), 4.27 (s,
2H), 3.24 (s, 2H); 1H NMR (90 MHz, CDCl3): d ˆ 7.6 8.1 (m,
3H), 7.1 7.5 (m, 8H), 5.86 (t, J ˆ 2.0 Hz, 1H), 4.29 (d, J ˆ
2.2 Hz, 2H), 3.26 (d, J ˆ 2.2 Hz, 2H); 13C NMR (67.9 MHz,
CDCl3): d ˆ 145.21, 144.42, 143.00, 135.33, 133.80, 132.20,
130.44, 128.57, 127.03, 126.88, 126.07, 125.77, 125.54, 125.46,
124.67, 124.31, 123.76, 119.08, 37.70, 31.57; IR (KBr): n ˆ 3064,
2896, 2885, 1509, 1461, 1396, 968, 772, 717 cmÀ1; MS (EI,
3-(1-Naphthylmethyl)-2,4-pentanedione:
1H NMR
(400 MHz, CDCl3): d ˆ 7.17 8.13 (m, 7H), 4.06 (s, 2H), 2.03
2.09 (m, 7H); 13C NMR (100 MHz, CDCl3): d ˆ 192.30,
134.70, 133.77, 131.90, 128.93, 127.13, 126.20, 125.82, 125.72,
123.35, 122.68, 106.92, 29.63, 23.01; IR (KBr): n ˆ 3051, 2919,
1726, 1700, 1596, 1357, 1149, 795, 776 cmÀ1; MS (EI, 70 eV): m/
‡
70 eV): m/z ˆ 256 (M , 33), 239 (5), 141 (100), 128 (12), 115
(18).
1,3-Bis(1-naphthylmethyl)indene: 1H NMR (89.5 MHz,
CDCl3): ˆ d 7.6 8.1 (m, 6H), 7.1 7.5 (m, 12H), 5.79 (d, J ˆ
1.7 Hz, 1H), 4.27 (s, 2H), 2.8 4.0 (m, 2H); IR (KBr): n ˆ 3062,
3043, 2927, 1712, 1597, 1510, 1460, 1397, 1018, 789, 776 cmÀ1;
‡
z ˆ 240 (M , 22), 222 (9), 197 (74), 179 (57), 153 (17), 141 (43),
128 (12), 115 (14), 43 (100).
6-(1-Naphthyl)-2,4-hexanedione: MS (EI, 70 eV): m/z ˆ 240
‡
‡
(M , 1), 197 (3), 179 (6), 141 (100), 115 (14), 43 (6).
MS (EI, 70 eV): m/z ˆ 396 (M , 14), 255 (25), 237 (9), 141 (100),
3,3-Bis(1-naphthylmethyl)-2,4-pentanedione:
1H NMR
111 (11), 97 (22), 83 (25), 75 (23), 64 (24), 59 (31).
(400 MHz, CDCl3): d ˆ 7.84 (d, J ˆ 8.5 Hz, 2H), 7.79 (d, J ˆ
8.2 Hz, 2H), 7.71 (d, J ˆ 8.1 Hz, 2H), 7.21 7.42 (m, 8H), 3.91 (s,
4H), 2.00 (s, 6H); ); 13C NMR (100 MHz, CDCl3): d ˆ 207.35,
133.80, 132.61, 132.51, 128.78, 127.64, 126.45, 126.02, 125.67,
125.19, 123.38, 71.10, 33.25, 28.41; IR (KBr): n ˆ 3049, 1717,
1696, 1510, 1356, 1178, 797, 779 cmÀ1; MS (EI, 70 eV): m/z ˆ
4-tert-Butylbenzyl hexyl ether: 1H NMR (400 MHz, CDCl3):
d ˆ 7.35 7.38 (m, 2H), 7.26 7.28 (m, 2H), 4.47 (s, 2H), 3.46
(t, J ˆ 6.7 Hz, 2H), 1.61 (quint, J ˆ 7.1 Hz, 2H), 1.27 1.38 (m,
15H), 0.88 (t, J ˆ 6.9 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d ˆ 150.41, 135.68, 127.50, 125.26, 72.68, 70.51, 34.51, 31.73,
31.37, 29.77, 25.90, 22.65, 14.08; IR (KBr): n ˆ 2960, 2932, 2859,
1515, 1464, 1362, 1269, 1105, 1019, 817 cmÀ1; MS (EI, 70 eV): m/
‡
380 (M , 31), 337 (12), 239 (39), 209 (52), 141 (100), 115 (50).
‡
2-Benzoyl-3-(1-naphthyl)propanenitrile:
1H NMR
z ˆ 248 (M , 23), 233 (91), 191 (10), 147 (100), 133 (30), 117
(400 MHz, CDCl3): d ˆ 7.87
7.92 (m, 4H), 7.78 (d, J ˆ
(18), 92 (57), 57 (36), 43 (31).
8.1 Hz, 1H), 7.40 7.61 (m, 7H), 4.68 (dd, J ˆ 9.0, 5.9 Hz,
1H), 3.90 (dd, J ˆ 14.4, 5.9 Hz, 1H), 3.63 (dd, J ˆ 14.4, 9.0 Hz,
1H); 13C NMR (100 MHz, CDCl3): d ˆ 190.19, 134.59, 134.14,
133.98, 131.69, 131.16, 129.34, 129.03, 128.79, 128.51, 128.10,
126.75, 125.93, 125.59, 122.44, 117.06, 40.31, 32.42; IR (KBr):
n ˆ 3060, 2244, 1693, 1597, 1449, 1266, 779 cmÀ1; MS (EI,
4-tert-Butylbenzyl 3-methoxybutyl ether: 1H NMR
(89.5 MHz, CDCl3): d ˆ 7.2 7.5 (m, 4H), 4.46 (s, 2H), 3.4
3.7 (m, 2H), 3.30 (s, 3H), 1.6 1.9 (m, 2H), 1.31 (s, 9H), 1.14 (d,
J ˆ 6.2 Hz, 3H); IR (KBr): n ˆ 2966, 2868, 1514, 1464, 1364,
‡
1269, 1092, 1019, 817 cmÀ1; MS (EI, 70 eV): m/z ˆ 250 (M , 9),
203 (8), 176 (17), 163 (100), 161 (36), 147 (78), 131 (16), 117
(17), 91 (15), 59 (48).
‡
70 eV): m/z ˆ 285 (M , 33), 152 (7), 141 (74), 128 (7), 115 (12),
105 (100), 77 (44).
4-tert-Butylbenzyl 4-methylphenyl ether: 1H NMR
(400 MHz, CDCl3): d ˆ 7.35 7.41 (m, 4H), 7.06 7.08 (m,
2H), 6.86 6.89 (m, 2H), 4.98 (s, 2H), 2.28 (s, 3H), 1.32 (s, 9H);
13C NMR (100 MHz, CDCl3): d ˆ 156.81, 150.88, 134.17,
129.99, 129.87, 127.41, 125.49, 114.62, 69.89, 34.56, 31.34,
20.47; IR (KBr): n ˆ 3031, 2969, 2871, 1612, 1513, 1364, 1237,
1176,1121, 1110, 1004, 825, 806 cmÀ1; MS (EI, 70 eV): m/z ˆ
2-Benzoyl-3-(1-naphthyl)-2-(1-naphthylmethyl)propaneni-
trile: 1H NMR (400 MHz, CDCl3): d ˆ 8.10 (d, J ˆ 8.4 Hz, 2H),
7.82 (d, J ˆ 8.0 Hz, 2H), 7.78 (d, J ˆ 8.2 Hz, 2H), 7.38 7.55 (m,
8H), 7.27 À7.31 (m, 1H), 7.05 7.12 (m, 4H), 4.10 (d, J ˆ
14.2 Hz, 1H), 3.87 (d, J ˆ 14.2 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d ˆ 198.02, 136.60, 133.91, 132.64, 132.34, 130.73,
129.02, 128.78, 128.66, 128.30, 127.79, 126.31, 125.86, 125.24,
123.94, 121.44, 55.38, 40.12; IR (KBr): n ˆ 3051, 2936, 2232,
1682, 1597, 1447, 1232, 778 cmÀ1; MS (EI, 70 eV): m/z ˆ 425
‡
254 (M , 14), 239 (9), 147 (100), 132 (14), 117 (10), 105 (7), 91
(6), 77 (3).
2-(4-tert-Butylbenzyl)-4-methylphenol:
1H NMR
‡
(M , 9), 285 (6), 141 (100), 115 (10), 105 (42), 77 (17).
(400 MHz, CDCl3): d ˆ 7.28 7.31 (m, 2H), 7.14 7.16 (m,
2H), 6.89 6.94 (m, 2H), 6.65 6.67 (m, 1H), 4.70 (br s, 1H), 3.92
(s, 2H), 2.24 (s, 3H), 1.29 (s, 9H); 13C NMR (100 MHz, CDCl3):
d ˆ 151.52, 149.11, 136.80, 131.54, 130.03, 128.20, 128.16,
126.75, 125.56, 115.65, 35.92, 34.36, 31.36, 20.51; IR (KBr):
n ˆ 3530, 2963, 2868, 1611, 1510, 1363, 1264, 1203, 1115, 1099,
2-(2-Chlorophenyl)-3-(1-naphthyl)propanenitrile:
1H NMR (400 MHz, CDCl3): d ˆ 8.07 (d, J ˆ 8.2 Hz, 1H), 7.79
7.89 (m, 2H), 7.40 7.59 (m, 6H), 7.24 7.32 (m, 2H), 4.73 (dd,
J ˆ 9.9, 5.3 Hz, 1H), 3.71 (dd, J ˆ 14.0, 5.3 Hz, 1H), 3.46 (dd,
J ˆ 14.0, 9.9 Hz, 1H); 13C NMR (100 MHz, CDCl3): d ˆ 133.88,
133.47, 132.71, 131.95, 131.64, 130.04, 129.74, 129.22, 129.05,
128.46, 128.25, 127.77, 126.42, 125.78, 125.46, 122.85, 119.76,
37.49, 36.34; IR (KBr): n ˆ 3062, 2941, 2244, 1511, 1476, 1443,
‡
1020, 919, 812 cmÀ1; MS (EI, 70 eV): m/z ˆ 254 (M , 49), 239
(100), 198 (19), 197 (12), 121 (35), 120 (15), 106 (14), 91 (14), 77
(7), 57 (12).
376
Adv. Synth. Catal. 2002, 344, 370 378

Water-Soluble Calixarenes as New Inverse Phase-Transfer Catalysts
FULL PAPERS
1-(Hexyloxymethyl)-4-hydroxymethylbenzene: 1H NMR
(400 MHz, CDCl3): d ˆ 7.30 (s, 4H), 4.61 (s, 2H), 4.47 (s, 2H),
3.44 (t, J ˆ 6.7 Hz, 2H), 2.48 (br s, 1H), 1.56 1.63 (m, 2H), 1.24
1.38 (m, 6H), 0.88 (t, J ˆ 6.9 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d ˆ 140.26, 137.91, 127.84, 127.00, 72.57, 70.50, 64.89,
31.69, 29.68, 25.85, 22.63, 14.07; IR (KBr). n ˆ 3377, 3009, 2956,
2932, 2860, 1515, 1421, 1362, 1214, 1099, 1050, 1018, 807,
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‡
757 cmÀ1; MS (EI, 70 eV): m/z ˆ 222 (M , 8), 191 (6), 137 (6),
121 (100), 104 (59), 92 (50), 77 (17), 56 (9), 43 (41).
¬
Chem. Rev. 1999, 190 192, 587 605; e) I. T. Horvath, in
1,4-Bis(hexyloxymethyl)benzene: 1H NMR (400 MHz,
CDCl3): d ˆ 7.31 (s, 4H), 4.49 (s, 4H), 3.45 (t, J ˆ 6.7 Hz, 4H),
1.57 1.67 (m, 4H), 1.25 1.39 (m, 12H), 0.88 (t, J ˆ 6.9 Hz,
3H); 13C NMR (100 MHz, CDCl3): d ˆ 137.95, 127.68, 72.64,
70.46, 31.71, 29.75, 25.88, 22.64, 14.07; IR (KBr): n ˆ 2957, 2932,
2859, 1467, 1360, 1216, 1099, 1021, 807, 758 cmÀ1; MS (EI,
Aqueous-Phase Organometallic Catalysis: Concepts and
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pp. 555 563.
‡
70 eV): m/z ˆ 306 (M , 7), 221 (4), 205 (41), 191 (16), 121 (39),
107 (44), 104 (100), 85 (55), 58 (15), 43 (68).
4-tert-Butylbenzyl ethyl ether: 1H NMR (89.5 MHz, CDCl3):
d ˆ 7.2 7.5 (m, 4H), 4.47 (s, 2H), 3.53 (q, J ˆ 6.9 Hz, 3H), 1.1
1.4 (m, 12H); IR (KBr): n ˆ 2966, 2867, 2806, 1365, 1269, 1191,
‡
1107, 1019, 825 cmÀ1; MS (EI, 70 eV): m/z ˆ 192 (M , 29), 177
[5] a) B. Cornils, in Modern Solvents in Organic Synthesis,
(Ed.: P. Knochel), Springer, Berlin, 1999, pp. 133 152;
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4-tert-Butylbenzyl propyl ether: 1H NMR (89.5 MHz,
CDCl3): d ˆ 7.2 7.5 (m, 4H), 4.47 (s, 2H), 3.43 (t, J ˆ 7.1 Hz,
2H), 1.4 1.8 (m, 2H), 1.31 (s, 9H), 0.93 (t, J ˆ 7.5 Hz, 3H); IR
(KBr): n ˆ 2964, 2872, 1459, 1363, 1271, 1106, 824 cmÀ1; MS
‡
(EI, 70 eV): m/z ˆ 206 (M , 25), 191 (100), 163 (4), 147 (56), 132
(16), 117 (15), 107 (31), 92 (32), 57 (28), 43 (27).
Butyl 4-tert-butylbenzyl ether: 1H NMR (89.5 MHz, CDCl3):
d ˆ 7.2 7.5 (m, 4H), 4.46 (s, 2H), 3.47 (t, J ˆ 6.1 Hz, 2H), 1.2
1.7 (m, 13H), 0.91 (t, J ˆ 6.5 Hz, 3H); IR (KBr): n ˆ 2961, 2935,
2868, 1515, 1463, 1362, 1269, 1101, 1019, 818 cmÀ1; MS (EI,
‡
70 eV): m/z ˆ 220 (M , 22), 205 (100), 163 (19), 147 (57), 132
¬
2342 2344; e) F. Monteil, R. Queau, P. Kalck, J.
(16), 117 (18), 107 (38), 92 (48), 57 (50).
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2-Naphthylmethyl octyl ether: 1H NMR (400 MHz, CDCl3):
d ˆ 7.76 7.82 (m, 4H), 7.42 7.47 (m, 3H), 4.65 (s, 2H), 3.49 (t,
J ˆ 6.7 Hz, 2H), 1.63 (quint, J ˆ 7.1 Hz, 2H), 1.26 1.40 (m,
10H), 0.87 (t, J ˆ 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d ˆ 136.22, 133.31, 132.94, 128.09, 127.84, 127.67, 126.24,
126.00, 125.75, 125.72, 72.93, 70.54, 31.84, 29.81, 29.46, 29.29,
26.23, 22.67, 14.11; IR (KBr): n ˆ 3055, 2928, 2855, 1458, 1373,
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‡
1101, 853, 815, 748 cmÀ1; MS (EI, 70 eV): m/z ˆ 270 (M , 14),
158 (6), 142 (100), 129 (10), 115 (9), 69 (4), 43 (4).
Acknowledgements
The authors wish to thank Naoyuki Shimada,Asami Koga and
Atsushi Yamaguchi for their assistance in this study.
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