Application of alkali metal hydroxides for the preparation of gem-chlorophenylcyclopropanes

Article abstract of DOI:10.1080/00397910600943550

gem-Chlorophenylcyclopropanes 3 are conveniently prepared by reaction of benzal chloride (1) with alkenes 2, carried out either in the presence of solid potassium hydroxide and 18-crown-6 as a catalyst or cesium hydroxide monohydrate, without solvent. Cop

Full text of DOI:10.1080/00397910600943550

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Application of Alkali Metal
Hydroxides for the Preparation of
gem‐Chlorophenylcyclopropanes
Andrzej Jończyk a , Hanna Karwowska a & Jolanta Furman a
a Faculty of Chemistry , Warsaw University of Technology , Warszawa,
Poland
Published online: 24 Nov 2006.
To cite this article: Andrzej Jończyk , Hanna Karwowska & Jolanta Furman (2006) Application of Alkali
Metal Hydroxides for the Preparation of gem‐Chlorophenylcyclopropanes, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:23, 3571-3579, DOI:
10.1080/00397910600943550
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Synthetic Communicationsw, 36: 3571–3579, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600943550
Application of Alkali Metal Hydroxides
for the Preparation of
gem-Chlorophenylcyclopropanes
´
Andrzej Jonczyk, Hanna Karwowska, and Jolanta Furman
Faculty of Chemistry, Warsaw University of Technology,
Warszawa, Poland
Abstract: gem-Chlorophenylcyclopropanes 3 are conveniently prepared by reaction of
benzal chloride (1) with alkenes 2, carried out either in the presence of solid potassium
hydroxide and 18-crown-6 as a catalyst or cesium hydroxide monohydrate, without
solvent.
Keywords: Cesium hydroxide, chlorophenyl carbene, gem-chlorophenylcyclopro-
panes, phase-transfer catalysis, potassium hydroxide
gem-Chlorophenylcyclopropanes easily undergo base-mediated dehydro-
chlorination affording phenyl-substituted cyclopropenes.[1,2]
gem-Chlorophenylcyclopropanes are usually prepared by cycloaddition
of chlorophenyl carbene (or carbenoide) to carbon–carbon double bonds.[3]
This species was generated by treatment of benzal chloride (1) with
potassium t-butoxide,[4–6] methyl-,[4,5] or butyllithium (in the latter case,
apart from 1, trichloromethylbenzene was also used)[7] from chlorophenyldia-
zirine[2] (thermally,[1,8] photochemically,[9,10] or using ultrasound[9]), from
phenyl(a,a-dichlorobenzyl)mercury,[11] phenyl(bromodichloromethyl)mer-
cury, and triphenylborane,[12] or (a,a-dichlorobenzyl)trimethyltin[13] (by
their thermal decomposition), or from (a,a-dichlorobenzyl)trimethylsilane
and potassium fluoride/cat. 18-crown-6.[14] All these methods suffer from dis-
advantages, requiring either a strong base, highly explosive diazirine, or toxic,
Received in Poland April 13, 2006
Address correspondence to Andrzej Jonczyk, Faculty of Chemistry, Warsaw
´
University of Technology, Koszykowa St. 75, 00-662 Warszawa, Poland. E-mail:
anjon@ch.pw.edu.pl
3571

´
A. Jonczyk, H. Karwowska, and J. Furman
3572
not easily available organometallic reagents. Furthermore, deprotonation of 1
with methyllithium is complicated by chlorine–lithium exchange, leading to
the formation of gem-methyl(phenyl)cyclopropanes,[5] while harsh thermal
conditions used for the decomposition of tin derivative transformed cyclopro-
panes into chain products.[13] Finally, the yield of the products from styrene
and its ring-substituted derivatives were disappointingly low.[6] A reasonable
alternative appeared to be phase-transfer catalysis (PTC)[15,16] but attempted
preparation of the title cyclopropanes by reaction of chloride 1 with alkenes
carried out in the presence of concentrated aqueous sodium or potassium
hydroxide and a catalyst, a quaternary ammonium salt (liquid–liquid PTC
system),[17] failed.
Reactions that could not be realized in liquid–liquid PTC systems were
often successfully performed in the solid–liquid variant of PTC (i.e., in the
presence of powdered sodium or potassium hydroxide and a PT catalyst, the
latter base usually proved more efficient). Thus, powdered potassium
hydroxide and a catalyst, benzyltiethylammonium chloride (TEBAC), was
applied for the preparation of the corresponding cyclopropanes from (2-
dichloromethyl)furane or thiophene and alkenes.[18]
Our preliminary experiments, which consisted of stirring a-methylstyrene
(2a) with an excess of 1 in the presence of powdered potassium hydroxide,
without any solvents, in benzene or in THF, at a temperature of ca. 808C,
revealed that 1-chloro-1,2-diphenylcyclopropane (3a, mixture of diastereoi-
somers) was indeed formed but its proportion in the reaction mixture did
not exceed 65% (determined by GC). A catalytic amount of Aliquat 336 did
not alter the results, but in the presence of 18-crown-6 (10 mol %), without
any solvent, practically quantitative conversion of 2a was noticed, and 3a
was isolated in 90% yield. Results of the reaction of chloride 1 with alkenes
2b–f carried out under these conditions are collected in Table 1.
Thus, powdered potassium hydroxide and 18-crown-6 as a catalyst
(solid–liquid variant of PTC) can be applied for the preparation of gem-
chlorophenylcyclopropanes 3 from chloride 1 and some alkenes 2, but their
yield and purity were sometimes unsatisfied. Hence, we turned our attention
to cesium hydroxide as a potentially useful base for the synthesis of gem-
chlorophenylcyclopropanes.
Recently, enantioselective enolate anion alkylation[19] and O-alkylation
of alcohols[20] under PTC conditions, chemoselective mono-N-alkylation of
di- and polyamines,[21] catalytic addition of alcohols and amine derivatives
to alkynes and styrene,[22] catalytic alkynylation of aldehydes and ketones,
inter- or intramolecular alkenylation of nitriles,[23] and intramolecular alkeny-
lation of aniline derivatives[24] (indole synthesis) have successfully been
carried out using cesium hydroxide.
We found now that commercial cesium hydroxide monohydrate is also a
suitable base for the synthesis of 1-chloro-1-phenylcyclopropanes 3 from 1
and alkenes 2. Thus, stirring of chloride 1 and alkenes 2 with solid cesium
hydroxide monohydrate in benzene or toluene at 80–858C for 24–70 h led

Table 1. gem-Chlorophenylcyclopropnaes 3 from 1 and 2 in the presence of solid potassium hydroxide and 18-crown-6
as a catalyst
3
1/2
(mol/mol)
Time
(h)
Yield
(%)
Purityb
(%)
Ratio of
diasteroisomersc
Entry
2, 3a
R1
R2
R3
R4
1
2
3
4
5
6
a
Ph
Ph
Ph
H
H
Me
H
3.6
3.6
3.6
3.6
0.2
3.6
6
6
5
4
3
6
91
64
39
69
98
27
99.9
91.5
99.9
96.3
99.9
91.5
1.9
1.3
1.1
1.5
—
b[1]
H
Me
H
c[6,8]
H
H
d[6]
f[5,11]
h[8]
4-MeC6H4
Me
BuO
H
H
H
Me
H
Me
H
Me
H
1.4
aLiterature concerns the products 3.
bDetermined by GC.
cMajor/minor diastereoisomers (for relative stereochemistry see Experimental), determined by GC in crude reaction
mixtures.

´
A. Jonczyk, H. Karwowska, and J. Furman
3574
to the formation of cyclopropanes 2 in yields of 19–88% (Table 2). The
reactions were carried out either with an excess of 1 or 2 (in the case of rela-
tively volatile alkenes 2f, g) to facilitate the isolation of 3. All products 3
prepared from unsymetrically substituted alkenes were formed as mixtures
of diastereoisomers. Detailed investigations revealed that reaction of 1
with a-methylstyrene (2a) is practically noncatalyzed by a quaternary
ammonium salt (Aliquat 336, TEBAC). Although this process afforded cyclo-
propanes 3 in satisfactory yields and in good purity, it had to be carried out
over a rather long time. However, the same reaction done without any
solvent for 5–24 h (except for the case of alkene 2f) gave products 3 in
comparable yields and purity (Scheme 1, Table 2).
The reaction of 1 with styrene and its ring-substituted derivatives carried
out in the presence of potassium t-butoxide gave the corresponding gem-chlor-
ophenylcyclopropanes in 1.3–4% yields,[6] much lower than by our method
(Table 2, Entries 3–5).
Concerning the pathway leading to 3, we were able to trap the intermedi-
ate dichlorophenyl anion with carbon tetrachloride as phenyltrichloromethane
in low yield.
Thus, we elaborated a new method for the synthesis of gem-chlorophenyl-
cyclopropanes 3 from easily available benzalchloride 1 and alkenes 2. In terms
of simplicity, yields of the products, and their purity, this method is competi-
tive to known ones.
EXPERIMENTAL
All melting points were measured on a capillary melting-point apparatus and
1
are uncorrected. H NMR spectra were recorded on a Varian Mercury (400-
MHz) or Varian Gemini (200-MHz), and 13C NMR spectra on a Varian
Mercury (100-MHz) spectrometer in CDCl3 with tetramethylsilane as an
internal reference. All chemical shifts are reported in parts per million
(ppm) (d ¼ 0.00); abbreviations used are as follows: s, singlet; d, doublet;
dd, double doubled; t, triplet; m, multiplet. Microanalyses were obtained
using a CHN/S Perkin-Elmer 2400 elemental analyzer. Column chromato-
graphy was performed on silica gel 60 (230–400 mesh ASTM, Merck) with
hexane as eluent. All alkenes (except of 2b, which was prepared[25]) were
commercial and distilled before use. Cesium hydroxide monohydrate and
crown ether 18-crown-6 were purchased from Fluka.
1-Chloro-1,2-diphenyl-2-methylcyclopropane (3a) under PTC
Conditions; Typical Procedure
Chloride 1 (3.0 g, 19 mmol), alkene 2a (0.6 g, 5 mmol), powdered KOH
(2.0 g, 35.6 mmol), and 18-crown-6 (0.12 g, 0.45 mmol) were vigorously
stirred with magnetic stirrer at 80–858C for 6 h, cooled, and diluted with

Table 2. gem-Chlorophenylcyclopropanes 3 prepared from 1 and 2 in the presence of solid cesium hydroxide monohydrate
3
Time 1/2
(h)
Yield
(%)
Purityb
(%)
Ratio of
diasteroisomersc
Entry
1
2, 3a
R1
R2
R3
R4
Solvent
PhH
(mol/mol)
a
Ph
Ph
Ph
H
H
Me
47
7
1.25
1.8
1.2
1.8
1.9
1.8
1.8
1.8
1.0
0.5
1.0
0.5
1.2
1.8
84
92
98
97
1.7
1.7
1.4
1.4
1.2
1.3
1.3
2.1
—
2
3
b[1]
H
H
Me
H
H
H
PhH
PhH
70
12
48
7
54
70
96.5
96.5
99.9
99.8
97.9
99.7
98
c[6,8]
87.5
72.5
60
4
5
6
d[6]
e[6]
f[5,11] Me
4-MeC6H4
4-ClC6H4
H
H
H
—
—
24
24
60
45
24
5
H
Me
H
Me
H
Me
68
48
PhH
34
19
99
80
—
7
8
g
(CH2)4
BuO
Me
H
H
H
PhH
1.8
1.5
1.1
1.7
29
63
90.5
95
h[8]
H
PhMe
45
7
60
93
aLiterature concerns the products 3.
bDetermined by GC.
cMajor/minor diastereoisomers (for relative stereochemistry see Experimental), determined by GC in crude reaction mixtures.

´
A. Jonczyk, H. Karwowska, and J. Furman
3576
Scheme 1. gem-Chlorophenylcyclopropanes 3 from chloride 1 and alkenes 2.
water (20 mL) and Et2O (10 mL). The phases were separated. The water phase
was extracted with Et2O (3 ꢀ 10 mL), the combined organic phases were
washed with water and dried (MgSO4), the solvent was evaporated, and the
residue was purified by column chromatography to give 3a.
1-Chloro-1,2-diphenyl-2-methylcyclopropane (3a) using Cesium
Hydroxide; Typical Procedure
Chloride 1 (1.4 g, 9 mmol), alkene 2a (0.6 g, 5 mmol), and cesium hydroxide
monohydrate (3.4 g, 20 mmol) were vigorously stirred with magnetic stirrer at
80–858C for 7 h. The mixture was worked up, and the product 3a was isolated
as described. Diastereoisomers of 3a were separated by repeated column
chromatography and fully characterized.
Analytical Data for Cyclopropanes 3
3a-minor: (Rꢁ)-1-chloro-(Rꢁ,Sꢁ)-1,2-t-diphenyl-(Sꢁ)-2-methylcyclopropane:
mp 133–1358C. 1H NMR (400 MHz, CDCl3): d ¼ 1.13 (s, 3H), 1.70
(d, J ¼ 6.4 Hz, 1H), 1.88 (d, J ¼ 6.4 Hz, 1H), 7.26–7.56 (m, 10H). Anal.
calcd. for C16H15Cl: C, 79.17; H, 6.18. Found C, 78.71; H, 6.23. 3a-major:
(Sꢁ)-1-chloro-(Sꢁ,Sꢁ)-1,2-c-diphenyl-(Sꢁ)-2-methylcyclopropane: mp 42–
1
448C. H NMR (400 MHz, CDCl3): d ¼ 1.87 (s, 3H), 1.46 (d, J ¼ 6.8 Hz,
1H), 2.33 (d, J ¼ 6.8 Hz, 1H), 7.04–7.26 (m, 10H). Anal. calcd. for
C16H15Cl: C, 79.17; H, 6.18. Found C, 78.98; H, 6.19.
3b-major: (Sꢁ)-1-chloro-(Sꢁ,Sꢁ)-1,2-diphenyl-(Rꢁ)-3-methylcyclopropane:
mp 94–958C (lit.[1] 98–998C). 1H NMR (400 MHz, CDCl3): d ¼ 1.63
(d, J ¼ 6.0 Hz, 3H), 2.02–2.08 (m, 1H), 2.47 (d, J ¼ 7.2 Hz, 1H), 6.76–
7.21 (m, 10H). 13C NMR (100 MHz, CDCl3): d ¼ 15.05, 24.56, 40.43,
55.31, 126.04, 127.50, 127.80, 127.86, 128.18, 130.15, 137.26, 139.10.
3b-minor: (Sꢁ)-1-chloro-(Sꢁ,Rꢁ)-1, 2-diphenyl-(Sꢁ)-3-methylcyclopropane).
1H NMR (200 MHz, CDCl3): d ¼ 1.07 (d, J ¼ 6.4 Hz, 3H), 2.04–2.11
(m, 1H), 2.49 (d, J ¼ 7.4 Hz, 1H), 7.26–7.58 (m, 10H).
3c-major: (Rꢁ)-1-chloro-(Rꢁ,Sꢁ)-1,2-t-diphenylcyclopropane). 1H NMR
(200 MHz, CDCl3): d ¼ 1.85 (dd, J ¼ 8.0 Hz, J ¼ 6.6 Hz, 1H), 1.92

gem-Chlorophenylcyclopropanes
3577
(dd, J ¼ 9.8 Hz, J ¼ 6.6 Hz, 1H), 2.66 (dd, J ¼ 9.8 Hz, J ¼ 8.0 Hz, 1H),
7.27–7.58 (m, 10H). 3c-minor: (Sꢁ)-1-chloro-(Sꢁ,Sꢁ)-1,2-c-diphenylcyclo-
1
propane: mp 76–788C (lit.[7] 788C). H NMR (200 MHz, CDCl3): d ¼ 1.92
(d, J ¼ 8.8 Hz, 2H), 2.98 (t, J ¼ 8.8 Hz, 1H), 6.79–6.84 (m, 2H), 7.04–
7.27 (m, 8H).
3d-major: (Sꢁ)-1-chloro-(Sꢁ,Sꢁ)-1-phenyl-2-(4-methyl-phenyl)cyclopropane:
1H NMR (400 MHz, CDCl3): d ¼ 1.94 (dd, J ¼ 6.8 Hz, J ¼ 14.4 Hz, 1H),
1.95 (dd, J ¼ 6.8 Hz, J ¼ 10.0 Hz, 1H), 2.25 (s, 3H), 2.99 (dd, J ¼ 8.0 Hz,
J ¼ 10.0 Hz, 1H), 6.74–6.75 (m, 2H), 6.93–6.95 (m, 2H), 7.18–7.26
(m, 3H), 7.29–7.32 (m, 2H). 13C NMR (100 MHz, CDCl3): d ¼ 20.91, 21.03,
33.57, 48.62, 127.52, 127.92, 128.15, 128.57, 129.96, 133.47, 135.74, 137.84.
3d-minor: (Rꢁ)-1-chloro-(Rꢁ,Sꢁ)-1-phenyl-2-(4-methyl-phenyl)cyclopropane:
1H NMR (400 MHz, CDCl3): d ¼ 1.83 (dd, J ¼ 6.8 Hz, J ¼ 8.0 Hz, 1H),
1.91 (dd, J ¼ 6.8 Hz, J ¼ 10.0 Hz, 1H), 2.38 (s, 3H), 2.63 (dd, J ¼ 8.0 Hz,
J ¼ 9.6 Hz, 1H), 7.19–7.21 (m, 2H), 7.26–7.28 (m, 2H), 7.29–7.41 (m, 3H),
7.53–7.56 (m, 2H). 13C NMR (100 MHz, CDCl3): d ¼ 21.00, 21.14, 31.92,
49.68, 127.51, 127.75, 128.59, 128.85, 129.12, 133.49, 136.57, 142.90.
3e-major: (Sꢁ)-1-chloro-(Sꢁ,Sꢁ)-1-phenyl-2-(4-chloro-phenyl)cyclopropane:
1H NMR (400 MHz, CDCl3): d ¼ 1.91 (dd, J ¼ 6.8 Hz, J ¼ 14.4 Hz, 1H),
1.96 (dd, J ¼ 6.8 Hz, J ¼ 10.0 Hz, 1H), 2.94 (dd, J ¼ 7.6 Hz, J ¼ 10.0 Hz,
1H), 6.72–6.76 (m, 2H), 7.04–7.08 (m, 2H), 7.19–7.42 (m, 5H). 13C NMR
(100 MHz, CDCl3): d ¼ 21.24, 33.27, 48.60, 128.00, 128.24, 128.32,
128.91, 129.87, 132.02, 135.21, 137.30. 3e-minor: (Rꢁ)-1-chloro-(Rꢁ,Sꢁ)-1-
1
phenyl-2-(4-chloro-phenyl)cyclopropane: mp 75–768C. H NMR (400 MHz,
CDCl3): d ¼ 1.79 (dd, J ¼ 6.4 Hz, J ¼ 8.0 Hz, 1H), 1.93 (dd, J ¼ 6.4 Hz,
J ¼ 10.0 Hz, 1H), 2.59 (dd, J ¼ 8.0 Hz, J ¼ 10.0 Hz, 1H), 7.26–7.41
(m, 7H), 7.51–7.53 (m, 2H). 13C NMR (100 MHz, CDCl3): d ¼ 21.29,
31.59, 49.52, 127.47, 127.94, 128.28, 128.66, 130.59, 132.78, 135.11, 142.47.
3f: 1-chloro-1-phenyl-2,2,3,3-tetramethylcyclopropane: mp 66–688C (lit.[5]
1
65.5–66.58C). H NMR (400 MHz, CDCl3): d ¼ 1.04 (s, 6H), 1.38 (s, 6H),
7.26–7.34 (m, 5H).
1
3g-major: anti-1-methyl-7-chloro-7-phenylnorcarane: H NMR (400 MHz,
CDCl3): d ¼ 0.90 (s, 3H), 1.30–1.43 (m, 2H), 1.40 (dd, J ¼ 8.8 Hz,
J ¼ 2.4 Hz, 1H), 1.47–1.63 (m, 2H), 1.73–1.91 (m, 2H), 2.0–2.18 (m, 2H),
7.25–7.31 (m, 1H), 7.33–7.38 (m, 2H), 7.39–7.43 (m, 2H). 13C NMR
(100 MHz, CDCl3): d ¼ 19.22, 21.0, 21.48, 23.27, 24.70, 26.06, 27.76,
58.76, 127.34, 128.22, 129.17, 142.48. 3g-minor: syn-1-methyl-7-chloro-7-
phenylnorcarane: 1H NMR (400 MHz, CDCl3): d ¼ 0.66–0.68 (m, 2H),
1.05–1.08 (m, 2H), 1.44 (dd, J ¼ 8.4 Hz, J ¼ 2.8 Hz, 1H), 1.57 (s, 3H),
1.65–1.72 (m, 2H), 1.81–1.98 (m, 2H), 7.27–7.42 (m, 5H). 13C NMR
(100 MHz, CDCl3): d ¼ 20.51, 20.66, 24.31, 25.80, 25.82, 28.85, 31.18,
55.07, 127.65, 128.68, 130.69, 139.59. Anal. calcd. for C14H17Cl: C, 76.19;
H, 7.71. Found C, 76.24; H, 7.98.

´
A. Jonczyk, H. Karwowska, and J. Furman
3578
3h-minor: (Sꢁ)-1-chloro-1-phenyl-(Sꢁ)-2-c-butoxycyclopropane: 1H NMR
(200 MHz, CDCl3): d ¼ 0.73 (t, J ¼ 7.2 Hz, 3H), 1.0–1.31 (m, 2H), 1.21–
1.35 (m, 2H), 1.56 (dd, J ¼ 7.8 Hz, J ¼ 7.6 Hz, 1H), 1.73 (dd, J ¼ 7.8 Hz,
J ¼ 4.4 Hz, 1H), 3.21–3.33 (m, 1H), 3.37–3.48 (m, 1H), 3.77 (dd,
J ¼ 7.6 Hz, J ¼ 4.4 Hz, 1H), 7.27–7.56 (m, 5H).
3h-major: (Rꢁ)-1-chloro-1-phenyl-(Sꢁ)-2-t-butoxycyclopropane: 1H NMR
(200 MHz, CDCl3): d ¼ 0.96 (t, J ¼ 7.2 Hz, 3H), 1.23–1.47 (m, 4H),
1.48–1.55 (m, 1H), 1.62–1.68 (m, 1H), 3.45 (dd, J ¼ 7.8 Hz, J ¼ 4.8 Hz,
1H), 3.59–3.70 (m, 1H), 3.79–3.90 (m, 1H), 7.23–7.83 (m, 5H).
ACKNOWLEDGMENTS
The financial support of this work by the Ministry of Education and Science,
Warszawa, Poland (Grant No. 3 T09B 084 29) is gratefully acknowledged.
The authors thank Tadeusz Zdrojewski (Warsaw University of Technology,
Faculty of Chemistry) for helpful discussions concerning the configuration
of the prepared cyclopropanes.
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