Alkynylhalocarbenes 4. Generation of (alk-1-ynyl)halocarbenes from 3-substituted 1,1,1,3-tetrahalopropanes under the action of bases

Article abstract of DOI:10.1023/A:1020952513679

When treated with KOH under phase-transfer catalysis or with Bu ^tOK, 3-substituted (alkyl or phenyl) 1,1,3-tribromo-1-fluoropropanes 1a-c exclusively generate previously unknown (alk-1-ynyl)fluorocarbenes 5a-c, which react with olefins to give 1-(alk-1-ynyl)-1-fluorocyclopropanes 6a-h in 12-69% yields. Under analogous conditions, 3-alkyl- and 3-aryl-3-bromo-1,1,1-trichloropropanes 2a-c selectively afford (alk-1-ynyl)chlorocarbenes 7a-c, which are trapped by olefins to form the corresponding 1-(alk-1-ynyl)-1-chlorocyclopropanes 8a-k in 35-70% yields. (Phenylethynyl)chlorocarbene 7a is also selectively generated from 1,1,1,3-tetrachloro-3-phenylpropane (3a) upon its treatment with Bu ^tOK. With an excess of 2,3-dimethylbut-2-ene or 2-methylpropene, carbene 7a yields 1-chloro-1-(phenylethynyl)cyclopropanes 8a or 8c, respectively. In contrast, 1,1,1,3-tetrachloroheptane 3b and 3-alkyl- and 3-phenyl-1,1,1,3-tetrabromopropanes 4a,c,f react with bases in the presence of olefins to give, along with the corresponding 1-(alk-1-ynyl) -1-halocyclopropanes 8a,c,d and 11a-f, vinylidenecyclopropanes 12a,c-g, which suggests the generation, under these conditions, both (alk-1-ynyl)halocarbenes 7b and 9a-c and vinylidenecarbenes 10 and 11a-c. The composition and structures of intermediate products in the reactions of tetrahalides 1b, 2a, 2b, 3a, and 3b with Bu^tOK were determined and the mechanisms for carbene generation in these reactions were proposed.

Full text of DOI:10.1023/A:1020952513679

Russian Chemical Bulletin, International Edition, Vol. 51, No. 7, pp. 1237—1253, July, 2002
1237
Organic Chemistry
Alkynylhalocarbenes
4.* Generation of (alkꢀ1ꢀynyl)halocarbenes from
3ꢀsubstituted 1,1,1,3ꢀtetrahalopropanes under the action of bases**
ꢀ
K. N. Shavrin, V. D. Gvozdev, and O. M. Nefedov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5328. Eꢀmail: gvozdev@excite.com
When treated with KOH under phaseꢀtransfer catalysis or with ButOK, 3ꢀsubstituted
(alkyl or phenyl) 1,1,3ꢀtribromoꢀ1ꢀfluoropropanes 1a—c exclusively generate previously unꢀ
known (alkꢀ1ꢀynyl)fluorocarbenes 5a—c, which react with olefins to give 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀ
fluorocyclopropanes 6a—h in 12—69% yields. Under analogous conditions, 3ꢀalkylꢀ and
3ꢀarylꢀ3ꢀbromoꢀ1,1,1ꢀtrichloropropanes 2a—c selectively afford (alkꢀ1ꢀynyl)chlorocarbenes
7a—c, which are trapped by olefins to form the corresponding 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀchlorocycloꢀ
propanes 8a—k in 35—70% yields. (Phenylethynyl)chlorocarbene 7a is also selectively generꢀ
ated from 1,1,1,3ꢀtetrachloroꢀ3ꢀphenylpropane (3a) upon its treatment with ButOK. With an
excess of 2,3ꢀdimethylbutꢀ2ꢀene or 2ꢀmethylpropene, carbene 7a yields 1ꢀchloroꢀ1ꢀ(phenylꢀ
ethynyl)cyclopropanes 8a or 8c, respectively. In contrast, 1,1,1,3ꢀtetrachloroheptane 3b and
3ꢀalkylꢀ and 3ꢀphenylꢀ1,1,1,3ꢀtetrabromopropanes 4a,c,f react with bases in the presence of
olefins to give, along with the corresponding 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀhalocyclopropanes 8a,c,d and
11a—f, vinylidenecyclopropanes 12a,c—g, which suggests the generation, under these condiꢀ
tions, both (alkꢀ1ꢀynyl)halocarbenes 7b and 9a—c and vinylidenecarbenes 10 and 11a—c.
The composition and structures of intermediate products in the reactions of tetrahalides 1b,
2a, 2b, 3a, and 3b with ButOK were determined and the mechanisms for carbene generation
in these reactions were proposed.
Key words: 3ꢀsubstituted 1,1,1,3ꢀtetrahalopropanes; dehydrohalogenation, phaseꢀtransꢀ
fer catalysis, (alkꢀ1ꢀynyl)halocarbenes, (alkꢀ1ꢀynyl)halocyclopropanes, cycloaddition.
Earlier,1,4—6 we have proposed a general method for
the generation of (alkꢀ1ꢀynyl)halocarbenes by alkaline
solvolysis of 1,1ꢀdihaloalkꢀ2ꢀynes. This method affords
(alkꢀ1ꢀynyl)chloroꢀ and (alkꢀ1ꢀynyl)bromocarbenes with
alkyl, cycloalkyl, phenyl, and trimethylsilyl substituents
at the triple bond. Our recent studies2,3 revealed that
alkaline solvolysis of accessible 3ꢀsubstituted 1,1,1,3ꢀtetꢀ
rahalopropanes 1—4 also yields (alkꢀ1ꢀynyl)halocarbenes.
This paper presents detailed data on the reactions of variꢀ
* For Part 3, see Ref. 1.
** Preliminary results have been published previously.2,3
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1143—1158, July, 2002.
1066ꢀ5285/02/5107ꢀ1237 $27.00 © 2002 Plenum Publishing Corporation

1238
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
Shavrin et al.
tetrahalomethanes to accessible terminal olefins.7 To do
this, the latter were heated with a twoꢀ to fivefold molar
excess of a tetrahalomethane for 4—10 h in the presence
of catalytic amounts of azodiisobutyronitrile (AIBN) or
dibenzoyl peroxide (Scheme 1). 1,1,1,3ꢀTetrachloroꢀ3ꢀ
phenylpropane (3a) was synthesized by addition of CCl4
to styrene, with a mixture of CuCl2 and Et2NH2Cl as a
catalyst.8
Scheme 1
The reactions of 3ꢀalkylꢀ and 3ꢀphenylꢀ1,1,3ꢀtriꢀ
bromoꢀ1ꢀfluoropropanes 1a—c with KOH in CH2Cl2 at
20—40 °C or with ButOK in hexane at 20 °C proceed
through successive elimination of three HBr molecules
to give the corresponding (alkꢀ1ꢀynyl)fluorocarbenes
5a—c, which represent a new class of highly reactive
carbenes. Their trapping by alkenes (2ꢀmethylpropene,
2,3ꢀdimethylbutꢀ2ꢀene, or styrene) affords previously unꢀ
known alkynylfluorocyclopropanes 6a—h in 12—69%
yields (Scheme 2, Table 1). As expected, alkenes that are
unsymmetrical relative to the plane of the πꢀorbitals of
the double bond gave cyclopropanes 6b,e,f,h as mixtures
of cisꢀ and transꢀisomers.
R = Ph (a), Bu (b), But (c), (Et2O)2CH (d), 4ꢀClC6H4 (e), Me (f).
Reagents and conditions: i) CBr3F, AIBN; ii) CCl3Br, AIBN;
iii) CCl4, (PhCOO)2; iv) CCl4, MeCN, CuCl2, Et2NH2Cl;
v) CBr4, CCl4, AIBN.
Scheme 3
ous tetrahalides 1—4 with bases in the presence of olefins
as traps for carbenes generated under these conditions.
The starting tetrahalides 1—4, except for 3a, were
prepared by free radical addition of the corresponding
Scheme 2
2a, 7a: R1 = Ph; 2b, 7b: R1 = Bun; 2c, 7c: R1 = But;
2d, 7d: R1 = (EtO)2CH; 2e, 7e: R1 = 4ꢀClC6H4.
R1
R2
R3
R4
R5
8a
8b
8c
8d
8e
8f
8g
8h
8i
Ph
Ph
Ph
Bu
Bu
Bu
But
(EtO)2CH
(EtO)2CH
4ꢀClC6H4
Me
H
H
Me
Ph
H
Me
Me
H
Me
Me
Me
Me
H
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
Me
Me
Me
Me
Me
Me
Me
H
Me
H
1a, 5a: R1 = Ph; 1b, 5b: R1 = Bun; 1c, 5c: R1 = But.
R1
R2
R3
R4
R5
6a
6b
6c
6d
6e
6f
Ph
Ph
Bu
Bu
Bu
Bu
But
Me
—(CH2)4—
Me
H
—(CH2)4—
Me
Me
H
Me
Me
H
Me
H
Me
H
H
H
H
Me
Me
H
Me
Me
8j
Me
Me
Ph
Me
H
Me
H
Me
8k
4ꢀClC6H4
H
Me
Me
H
6g
Me
6h
But
—(CH2)4—
H
H
Reagents and conditions: i) ButOK, hexane, 20—60 °C;
ii) KOH, BTEAC (cat.), CH2Cl2, 20—40 °C;
iii) ButOK, benzene, 80 °C.
Reagents and conditions: i) ButOK, hexane, 20—60 °C;
ii) KOH, BTEAC (cat.), CH2Cl2, 20 °C.

Generation of (alkꢀ1ꢀynyl)halocarbenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
1239
Table 1. Reactions of 3ꢀsubstituted 1,1,3ꢀtribromoꢀ1ꢀfluoropropanes 1a—c and 3ꢀsubstituted 3ꢀbromoꢀ1,1,1ꢀtrichloropropanes
2a—e with bases in the presence of alkenes R2R4C=CR3R5
b
Source
of the
carbene
Base,
solventa
τ
T
/°C
Carbene
Alkene
Product
(transꢀtoꢀcis
ratio)
Yield
(%)
B.p./°C
(p/Torr)
M.p./°C
/h
R2
R3
R4
R5
1a
1b
A
B
0.5
2
20
20
5a
5a
Me
—(CH2)4—
Me
Me
H
Me
H
6a
6b
(4.5 : 1)
50c
69d
—
140—150 (2)
B
A
B
10
3
8
20
20
20
5b
5b
5b
Me
H
—(CH2)4—
Me
Me
Me
Me
H
Me
H
H
6c
6d
6e
48d
41d
54d
130—140 (20)
110—120 (25)
150—170 (12)
(3.7 : 1)
B
12
20
5b
Ph
H
H
H
6f
(3.5 : 1)
6g
49d
110—130 (2)
1c
2a
A
A
8
8
65—70
65—70
5c
5c
Me
—(CH2)4—
Me
Me
H
Me
H
43d
6d
130—150 (90)
103—105 (14)
6h
(4.4 : 1)
8a
A
A
1
1
20
20
7а
7а
Me
H
Me
Me
Me
Me
Me
Me
48c
45d
59—60
120—123 (2)
8b
(1.4 : 1)
8c
A
B
B
A
B
1
2
8
3
32
20
20
20
65—70
40—45
7а
7а
7а
7b
7b
H
Me
H
Me
Ph
Me
Me
Me
Me
H
Me
Me
Me
Me
H
H
Me
H
Me
H
43c
70e
34d
52d
49d
—
—
8a
8c
8d
8e
110—111 (2)
150—160 (10)g
130—140 (1)g
2b
(3.5 : 1)
8f
A
C
A
A
A
A
48
32
8
8
1
20
80
20
20
20
20
7b
7c
7d
7d
7e
7e
H
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
35d
48e
37c
35c
46c
42c
130—140 (15)g
2c
2d
Me
Me
H
Me
H
Me
Me
H
Me
H
8g
8h
8i
8j
—
—
—
—
—
2e
1
8k
a A for ButOK in hexane, B for KOH/BTEAC(cat.) in CH2Cl2, and C for ButOK in benzene.
b Reaction time.
c The product was isolated by column chromatography.
d The product was isolated by vacuum distillation.
e Determined from the GLC data with the use of an internal standard.
g The bath temperature for vacuum microdistillation.
Scheme 4
Analogously, when treated with bases, 3ꢀalkylꢀ and
3ꢀarylꢀ3ꢀbromoꢀ1,1,1ꢀtrichloropropanes 2a—e selectively
generate the corresponding (alkꢀ1ꢀynyl)chlorocarbenes
7a—e, which react with olefins to give alkynylchloroꢀ
cyclopropanes 8a—k in 35—70% yields (Scheme 3, see
Table 1). Cyclopropanes 8b,e were obtained as mixtures
of cisꢀ and transꢀisomers.
(Phenylethynyl)chlorocarbene (7a) was generated by
treating 1,1,1,3ꢀtetrachloroꢀ3ꢀphenylpropane (3a) with
an excess of ButOK in hexane at 20 °C in the presence of
2ꢀmethylpropene and 2,3ꢀdimethylbutꢀ2ꢀene; the corꢀ
responding cyclopropanes 8a,c were selectively obtained
Reagents and conditions: ButOK, hexane, 20 °C.
in 58 and 66% yields, respectively.
The reactions of 1,1,1,3ꢀtetrachloroheptane (3b),
1,1,1,3ꢀtetrabromoꢀ3ꢀphenylpropane (4a), 1,1,1,3ꢀtetraꢀ
bromoꢀ4,4ꢀdimethylpentane (4c), and 1,1,1,3ꢀtetraꢀ
bromobutane (4f) with ButOK in hexane or benzene at
20 °C give, along with (alkꢀ1ꢀynyl)halocarbenes 7b (from
3b) and 9a—c (from 4a, 4c, and 4f), halovinylideneꢀ
carbenes 10 and 11a—c. Their generation becomes eviꢀ

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Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
Shavrin et al.
Scheme 5
R = Ph (4a, 9a, 11a, 12a, 14a), But (4c, 9b, 11b, 12b, 14b), Me (4f, 9c, 11c, 12c, 14c).
Reagents, conditions, and yields: i) ButOK, hexane, 20 °C; ii) KOH, BTEAC (cat.), CH2Cl2, 20—40 °C; the total yield of
compounds 8d and 13 was 48—55%; iii) ButOK, benzene, 20 °C.
dent while analyzing the reaction products, namely,
1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀhalocyclopropanes 8d and 12a—e and
halovinylidenecyclopropanes 13 and 14a—d, which were
formed in the presence of alkenes in total 34—55% yields
(Scheme 5, Table 2). Individual 1ꢀbromoꢀ1ꢀ(phenylꢀ
ethynyl)cyclopropanes 12a,d were isolated in 33—51%
yields (12a by recrystallization from methanol and 12d
by distillation in vacuo). Unlike alkyne 12d, isomeric
vinylidenecyclopropane 14d could not be distilled, probꢀ
ably, because of its instability. Note that the reaction
mixture obtained from tetrabromide 4a with ButOK in
hexane in the presence of cyclohexene contained no
bromovinylidenecyclopropane like adduct 13 (GLC and
1H NMR data), which is probably due to its low stability
and decomposition during the reaction. Only 7ꢀbromoꢀ
7ꢀ(phenylethynyl)norcarane 12e was isolated by vacuum
distillation and characterized as a mixture of transꢀ and
cisꢀisomers.
ynyl)ꢀ1ꢀbromocyclopropanes 12a,d,e (see Table 2), its
reaction with KOH under conditions of phaseꢀtransfer
catalysis in the presence of 2,3ꢀdimethylbutꢀ2ꢀene gave
a 1.6 : 1 mixture of 1ꢀ[(bromo)phenylvinylidene]ꢀ2,2,3,3ꢀ
tetramethylcyclopropane (14a) and 2,2,3,3ꢀtetramethylꢀ
1ꢀ(phenylvinylidene)cyclopropane (15) (NMR and MS
data) in total 45% yield. This indicates that both broꢀ
mo(phenyl)vinylidenecarbene (11a) and phenylvinylꢀ
idenecarbene (16) are generated under these conditions
(Scheme 6).
1,1,1,3ꢀTetrabromoheptane (4b) reacts with ButOK
in benzene at 20 °C in the presence of an excess of
2ꢀmethylpropene to give a mixture of three products in
the 5 : 5 : 1 ratio in total 26% yield, which were identiꢀ
fied as 1ꢀbromoꢀ1ꢀ(hexꢀ1ꢀynyl)ꢀ2,2ꢀdimethylcycloꢀ
propane (12f), 1ꢀ(butyl)bromovinylideneꢀ2,2ꢀdimethylꢀ
cyclopropane (14e), and 1ꢀbromoꢀ1ꢀ(hexꢀ1ꢀenyl)ꢀ2,2ꢀ
dimethylcyclopropane (17) (NMR and MS data). When
diethyl ether or THF were used instead of benzene, a
mixture of the same cyclopropanes was obtained in total
27—31% yield, but the ratio between them was different
(see Table 2). The results obtained suggest that tetraꢀ
bromide 4b generates, under the above conditions,
carbenes 9d, 11d, and 18 (see Scheme 6).
Treatment of tetrachloride 3b with KOH in CH2Cl2
in the presence of an excess of 2,3ꢀdimethylbutꢀ2ꢀene at
40—45 °C gave the same products 8d and 13 as with
ButOK. The total yield of these cyclopropanes remained
virtually unchanged, but the content of allene 13 in the
reaction mixture increased from 20 to 50%.
Unlike the reactions of tetrabromide 4a with ButOK,
which mostly yield, in the presence of olefins, 1ꢀ(alkꢀ1ꢀ
The structures of the cyclopropanes synthesized were
proved by elemental analysis, GLꢀMS, and 1H and

Generation of (alkꢀ1ꢀynyl)halocarbenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
1241
Table 2. Reactions of 3ꢀsubstituted 1,1,1,3ꢀtetrachloropropanes 3a,b and 3ꢀsubstituted 1,1,1,3ꢀtetrabromopropanes 4a—f with
bases in the presence of alkenes R2R4C=CR3R5
b
Starting Base,
τ
T
/°C
Carbene
Alkene
R3
Product
(ratio)
Total
yield
(%)
B.p./°C
(p/Torr)
M.p./°C
comꢀ
solꢀ
venta
/h
R2
R4
R5
pound
3a
3b
A
A
A
1
48
48
20
20
20
7а
7а
7b, 10
Me
H
Me
Me
Me
Me
Me
Me
Me
Me
H
Me
8a
8c
8d : 13
66c
58d
50d
58—60
110—120 (2)e
150—160 (10)e
(4 : 1)
8d : 13
B
C
C
C
B
C
D
E
C
C
80
1
40—45
20
7b, 10
Me
Me
H
Me
Me
Me
Me
Me
Me
H
Me
Me
H
48d
150—160 (10)e
—
(1.1 : 1)
12a : 14a
(8 : 1)
12d : 14d
(10 : 1)
4a
9а, 11a
9а, 11a
9a
33f
(pure 12а)
51d
(pure 12d)
34d
1
20
118—120 (1)
155—158 (1)
—
1
20
—(CH2)4—
H
12e
(5 : 1)g
4
2
2
2
2
4
20
11a, 16
9d, 11d, 18
9d, 11d, 18
9d, 11d, 18
9b, 11b
9c, 11c
Me
H
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
H
14a : 15
(1.6 : 1)
12f : 14e : 17
(5 : 5 : 1)
12f : 14e : 17
(5 : 4 : 1)
12f : 14e : 17
(15 : 1 : 6)
12b : 14b
(1 : 1.4)
12c : 14c
(2.4 : 1)
45c
26d
31d
27d
24f
4b
20
120—130 (10)e
120—130 (12)e
120—130 (10)e
—
20
H
H
20
H
H
4c
4f
80
Me
Me
Me
Me
20
23d
100—110 (10)e
a A for ButOK in hexane, B for KOH/BTEAC(cat.) in CH2Cl2, C for ButOK in benzene, D for ButOK in Et2O, and E for ButOK
in THF.
b Reaction time.
c The product was isolated by column chromatography.
d The product was isolated by distillation.
e The bath temperature for vacuum microdistillation.
f The product was isolated by recrystallization from methanol.
g The ratio of transꢀ to cisꢀisomers.
13C NMR data (Tables 3—8). The mass spectra of bromoꢀ
and chlorocyclopropanes contain rather intense molecular
ion peaks composed of characteristic isotopic doublets
spaced at 2 amu (their intensity ratios are 1 : 1 and 1 : 3,
respectively). The 13C NMR spectra of alkynes 6, 8, and
12 show signals at δ 73—95 characteristic of the triple
bond, while the 13C NMR spectra of vinylidenecycloꢀ
propanes 13 and 14 contain signals at δ 95—110 and
180—186 characteristic of the terminal and central carꢀ
bon atoms in the allenic fragment, respectively. The
1H NMR spectra of the cyclopropanes obtained also
show signals for the protons, which are characteristic of
substituents at the cyclopropane fragment and the mulꢀ
tiple bonds in these compounds.
spectra and considering that JH,F(trans) < JH,F(cis) for
cyclopropanes9 (see Tables 3—5). The other NMR signals
were assigned to the corresponding cisꢀ and transꢀisomers
from their integral intensities. When the transꢀtoꢀcis raꢀ
tio only slightly differed from unity, the content of one
of the isomers in the mixture was increased by colꢀ
umn chromatography or distillation. An analysis of the
1H NMR spectra of these compounds shows that signals
for the protons in the cisꢀsubstituents relative to the
F atom are shifted downfield compared to signals for
analogous substituents in the transꢀposition. This differꢀ
ence for the cisꢀ and transꢀisomers is due to a strong
deshieldzing effect of the fluorine atom and correlate
with our previous data5 for (alkꢀ1ꢀynyl)bromoꢀ (12) and
(alkꢀ1ꢀynyl)chlorocyclopropanes (8). It was used to idenꢀ
tify the transꢀ and cisꢀisomers of new halocyclopropanes
8b,e and 12e.
The transꢀ and cisꢀisomers of (alkꢀ1ꢀynyl)fluorocycloꢀ
propanes 6b,e,f,h were distinguished by comparing viciꢀ
1
nal H—F coupling constants in their H and 19F NMR

1242
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
Shavrin et al.
Scheme 6
Reagents, conditions, and yields: i) KOH, BTEAC (cat.), CH2Cl2, 20—40 °C; the total yield of 14a+15 was 45%; ii) ButOK,
benzene, 20 °C; iii) ButOK, Et2O, 20 °C; iv) ButOK, THF, 20 °C; the total yield of 12f+14e+17 was 26—31%.
Table 3. 19F NMR spectra (CDCl3, 188 MHz) of
(alkꢀ1ꢀynyl)fluorocyclopropanes 6a—h
To elucidate the pathways through which the discovꢀ
ered carbenes are generated, we tried to determine the
structures of intermediate products in the reactions of
Compound
δ (J/Hz)
Compound
δ (J/Hz)
3ꢀsubstituted 1,1,1,3ꢀtetrahalopropanes 1—4 with bases.
It was shown that treatment of both 3ꢀbromoꢀ1,1,1ꢀ
trichloroꢀ3ꢀphenylpropane (2a) and 1,1,1,3ꢀtetrachloroꢀ
3ꢀphenylpropane (3a) with ButOK (0.5 equiv.) at room
temperature for 30 min affords a mixture containing,
along with the starting tetrahalide, 1,1,3ꢀtrichloroꢀ3ꢀ
6a
–192.0 s
–164.6 t (J = 19) cisꢀ6e
transꢀ6e
–162.4 t (J = 19)
–198.3 s
–175.4 s
–162.8 t (J = 19)
–197.9 s
transꢀ6b
cisꢀ6b
6c
–199.7 s
–191.0 s
6g
transꢀ6h
6d
–181.6 d (J = 18.3) cisꢀ6h
Table 4. Elemental analysis data for (alkꢀ1ꢀynyl)halocyclopropanes 6a—h, 8a—k, and 12a,d,e
Comꢀ
pound
Found
Calculated
Molecular
formula
Comꢀ
pound
Found
Calculated
Molecular
formula
Comꢀ
pound
Found
Calculated
Molecular
formula
(%)
H
(%)
H
(%)
H
C
C
C
6a
6b
6c
6d
6e
6f
83.35
8.09
7.92
7.17
C15H17F
C15H15F
C13H21F
C11H17F
C13H19F
C15H17F
C13H21F
C13H19F
8a
8b
8c
8d
8e
8f
77.24
7.46
7.36
6.74
6.91
5.91
6.04
9.82
9.95
7.52
7.36
9.38
9.28
10.17
9.95
C15H17Cl
C14H15Cl
C13H13Cl
C13H21Cl
C15H17Cl
C11H17Cl
C13H21Cl
8h
64.89
9.04
8.96
8.52
8.30
5.91
6.04
5.24
5.06
6.32
6.18
5.22
5.33
5.67
5.49
C14H23O2Cl
C12H19O2Cl
C15H16Cl2
C13H12Cl2
C15H17Br
83.29
83.89
84.08
79.36
79.54
78.74
78.52
80.60
80.37
83.47
83.29
79.28
79.54
80.19
80.37
77.41
76.91
76.88
67.13
67.43
73.51
73.39
77.23
77.41
71.70
71.53
73.22
73.39
64.98
62.59
62.47
67.13
67.43
65.21
65.29
65.17
64.99
62.61
62.85
65.61
65.47
8i
7.06
10.97
10.78
10.24
10.18
10.06
9.86
7.67
7.92
10.54
10.78
9.75
8j
8k
12a
12d
12e
C13H13Br
6g
6h
8g
C15H15Br
9.86

Generation of (alkꢀ1ꢀynyl)halocarbenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
1243
1
Table 5. H NMR spectra (CDCl3, 200.13 MHz, δ, J/Hz) of (alkꢀ1ꢀynyl)halocyclopropanes 6a—h, 8a—k, and 12a—f
Compound
1H NMR
R2
R1
R3
1.22 (s, 12 H, 4 Me)
1.20—2.10 (m, 12 H, 4 CH2 and 2 CH)
1.05 (d, 6 H, 2 Me, J = 2.2); 1.08 (d, 6 H, 2 Me, J = 1.5)
R4
R5
6a
7.30—7.50 (m, 5 H)
trans,cisꢀ6b
7.30—7.60 (m, 5 H)
6c
0.89 (t, 3 H, CH3, J = 7.3); 1.25—1.60 (m,
4 H, 2 CH2); 2.28 (dt, 2 H, CH2C≡,
J = 6.5, JH,F = 6.5)
6d
0.91 (t, 3 H, CH3, J = 7.4); 1.25—1.60 (m,
4 Н, 2 CH2); 2.28 (dt, 2 Н, CH2C≡,
J = 6.7, JH,F = 6.7)
0.94 (dd, 1 Н,
СН2, J = 6.5,
JH,F = 18.3)
1.21 (d,
3 H, CH3,
JH,F = 2.0)
1.15 (d,
3 H, CH3,
JH,F = 2.3)
0.73 (dd, 1 Н,
СН2, J = 6.5,
JH,F = 7.8)
transꢀ6e
cisꢀ6e
transꢀ6f
cisꢀ6f
0.89 (t, 3 H, CH3, J = 7.3); 1.05—1.60 (m,
4 H, 2 CH2); 2.22 (dt, 2 H, CH2C≡,
J = 6.5, JH,F = 6.5)
0.91 (t, 3 H, CH3, J = 7.3); 1.05—1.60 (m,
4 H, 2 CH2); 2.33 (dt, 2 H, CH2C≡,
J = 6.7, JH,F = 6.7)
0.76 (t, 3 H, CH3, J = 7.3); 1.00—1.80 (m,
4 H, 2 CH2); 2.07 (dt, 2 H, CH2C≡,
J = 6.8, JH,F = 6.8)
1.03—1.95 (m, 10 H, 4 CH2 and 2 CH)*
1.03—1.95 (m, 10 H, 4 CH2 and 2 CH)*
7.10—7.35
(m, 5 H)
1.00—1.80 (m, 2 H, CH2)*
1.00—1.80 (m, 2 H, CH2)*
2.68 (ddd, 1 H,
CH, J = 8.6, J =
17.7, J = 6.2)
2.41 (ddd, 1 H,
CH, J = 2.5,
0.91 (t, 3 H, CH3, J = 7.3); 1.00—1.80 (m,
4 H, 2 CH2); 2.26 (dt, 2 H, CH2C≡,
J = 6.8, JH,F = 6.8)
7.10—7.35
(m, 5 H)
J = 8.5, J = 11)
1.07 (d, 6 H, 2 Me, J = 2.2); 1.10 (d, 6 H, 2 Me, J = 1.5)
1.10—1.90 (m, 12 Н, 4 CH2 and 2 CH)
6g
1.24 (s, 9 H, But)
transꢀ6h
cisꢀ6h
8a
1.27 (s, 9 H, But)
1.21 (s, 9 H, But)
1.10—1.90 (m, 12 Н, 4 CH2 and 2 CH)
1.28 (s, 6 H, 2 Me); 1.31 (s, 6 H, 2 Me)
7.28—7.50 (m, 5 H)
transꢀ8b
cisꢀ8b
8c
1.22, 1.25 (both s, 6 H, CMe2); 1.25—1.45 (m, 4 H, CH, CHMe)
1.22, 1.26 (both s, 6 H, CMe2); 1.25—1.45 (m, 4 H, CH, CHMe)
7.20—7.40 (m, 5 H, Ph)
1.28 (d, 1 H,
1.42 (s,
1.39 (s,
1.19 (d,
J = 6)
3 H, Me)
3 H, Me)
1 H, J = 6)
8d
0.91 (t, 3 H, CH3, J = 7.0); 1.20—1.55 (m,
4 H, 2 CH2); 2.27 (t, 2 H, CH2C≡, J = 7.0)
0.81 (t, 3 H, CH3, J = 7.1); 1.00—2.00 (m,
4 H, 2 CH2); 2.19 (t, 2 H, CH2C≡, J = 7.0)
0.97 (t, 3 H, CH3, J = 7.1); 1.00—2.00 (m,
4 H, 2 CH2); 2.29 (t, 2 H, CH2C≡, J = 7.0)
0.88 (t, 3 H, CH3, J = 7.1); 1.2—1.6 (m,
4 H, 2 CH2); 2.23 (t, 2 H, CH2C≡, J = 7.0)
1.15 (s, 9 Н, 3 Me)
1.18 (s, 12 Н, 4 Me)
1.00—2.00 (m, 2 H)*
1.00—2.00 (m, 2 H)*
transꢀ8e
cisꢀ8e
8f
7.20—7.50
(m, 5 Н)
7.20—7.50
(m, 5 Н)
1.05 (d, 1 H,
J = 5.9)
2.80 (dd, 1 Н,
J = 8.0, J = 10)
2.75 (dd, 1 Н,
J = 8.5, J = 9.5)
1.00 (d, 1 H,
J = 5.9)
1.31 (s,
1.23 (s,
3 H, Me)
3 H, Me)
8g
8h
1.07 (s, 12 Н, 4 Me)
1.17 (s, 6 H, 2 Me); 1.23 (s, 6 H, 2 Me)
1.22 (t, 6 H, 2 CH2CH3, J = 7); 3.40—3.72 (m,
4 H, 2 СН2О); 5.32 (s, 1 H, CH)
8i
1.18 (t, 6 H, 2 CH2CH3, J = 7); 3.40—3.70 (m, 1.12 (d, 1 H,
1.27 (s,
1.22 (s,
1.02 (d, 1 H,
4 H, 2 СН2О); 5.24 (s, 1 H, CH)
7.20—7.40 (m, 4 H, Ph)
7.20—7.40 (m, 4H)
J = 6.5)
3 H, Me)
3 H, Me)
J = 6.5)
8j
8k
1.25 (s, 6 H, 2 Me); 1.28 (s, 6 H, 2 Me)
1.26 (d, 1 H,
1.40 (s,
1.37 (s,
1.18 (d, 1 H,
J = 5.9)
3 H, Me)
3 H, Me)
J = 5.9)
12a
12b
12c
12d
7.20—7.50 (m, 5 H, Ph)
1.22 (s, 9 H, 3 Me)
1.92 (s, 3 H, Me)
1.34 (s, 6 Н, 2 Me); 1.35 (s, 6 Н, 2 Me)
1.17 (s, 6 Н, 2 Me); 1.21 (s, 6 Н, 2 Me)
1.19 (s, 6 Н, 2 Me); 1.20 (s, 6 Н, 2 Me)
7.20—7.40 (m, 5 H, Ph)
1.38 (d, 1 H,
1.48 (s,
1.42 (s,
1.27 (d, 1 H,
J = 6)
3 H, Me)
3 H, Me)
J = 6)
trans,cisꢀ12e 7.20—7.50 (m, 5 H, Ph)
12f 0.92 (t, 3 H, CH3, J = 7.1); 1.20—1.60 (m,
4 Н, 2 CH2); 2.24 (t, 2 Н, CH2C≡, J = 6.9)
1.10—2.20 (m, 10 H, 4 CH2 and 2 CH)
1.14 (d, 1 Н,
СН2, J = 5.9)
1.26 (s, 3 H, CH3);
1.35 (s, 3 H, CH3)
1.09 (d, 1 Н,
СН2, J = 5.9)
* Overlap with signals for the Bu group.

1244
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
Shavrin et al.
Table 6. 13C NMR spectra (CDCl3, 50.32 MHz, δ, J/Hz) and mass spectra of (alkꢀ1ꢀynyl)halocyclopropanes 6a—h, 8a—k,
and 12a—f
Comꢀ
pound
13C NMR
MS,
m/z
C≡C
cycloꢀС3
R1
R2—R5
6a
83.5 (d, ≡CCF,
J = 32.5); 89.8 (d,
PhC≡, J = 10.2)
82.6 (d, ≡CCF,
J = 30); 93.4 (d,
≡CCH2, J = 10)
87.4 (d, ≡CCF,
J = 30); 85.9 (d,
≡CCH2, J = 10)
74.2 (d, ≡CCF,
J = 33); 90.8 (d,
≡CCH2, J = 10)
75.7 (d, CCF,
27.7 (d, 2 CMe2,
J = 11.5); 80.3 (d,
CF, J = 215)
22.4 (d, 2 CH,
J = 13.5); 76.9 (d,
CF, J = 208)
21.3 (d, 2 CH,
J = 13.5); 73.0 (d,
CF, J = 208)
26.6 (d, 2 CMe2,
J = 12); 80.6 (d,
CF, J = 214)
23.3 (d, CMe2, J =
11.7); 26.7 (d, CH2,
J = 12.2); 76.2 (d,
CF, J = 207.6)
21.3 (d, 2 CH,
J = 14); 77.1 (d,
CF, J = 203)
122.6 (d, C(1),
J = 3); 128.2,
128.4, 131.6
122.3 (d, C(1), Ph,
J = 3); 128.4, 128.7,
131.6 (Ph)
15.5 (d, 2 Me,
J = 8.6);
19.0 (2 Me)
19.0 (2 CH2);
20.8 (d, 2 CH2,
J = 3)
17.7 (d, 2 CH2,
J = 3); 21.4 (d,
2 CH2, J = 2)
15.6 (d, 2 Me,
J = 10);
19.1 (2 Me)
19.0 (d, (CH3)2C,
J = 9.5);
216 [M]+
214 [M]+
transꢀ6b
cisꢀ6b
6c
128.3, 128.5,
131.7 (Ph)
13.6 (CH3); 18.7 (d,
CH2, J = 2.4); 22.0,
30.8 (2 CH2)
13.6 (CH3); 18.6,
21.9, 30.6 (3 CH2)
196 [M]+
168 [M]+
6d
J = 31.2); 89.3 (d,
C≡CCF, J = 9.4)
22.6 ((CH3)2C)
transꢀ6e
cisꢀ6e
73.4 (d, ≡CCF,
J = 30); 94.7 (d,
≡CCH2, J = 10)
78.7 (d, ≡CCF,
J = 30); 86.6 (d,
≡CCH2, J = 10)
74.2 (d, ≡CCF,
J = 30); 91.4 (d,
≡CCH2, J = 10)
13.5 (CH3); 18.8 (d,
CH2, J = 2); 21.9,
30.6 (2 CH2)
13.5 (CH3); 18.5 (d,
CH2, J = 2)*
18.9 (2 CH2);
20.6 (d, 2 CH2,
J = 2)
17.6 (d, 2 CH2,
J = 3); 21.4 (d,
2 CH2, J = 2)
126.6, 128.0,
128.1 (Ph);
194 [M]+
20.5 (d, 2 CH,
J = 14)
transꢀ6f
20.2 (d, CH2, J =
14); 30.0 (d, CH,
J = 11); 73.7 (d,
CF, J = 213)
13.4 (CH3); 18.4 (d,
CH2, J = 2.5); 21.6,
30.2 (2 CH2)
216 [M]+
136.2 (C(1), Ph)
cisꢀ6f
77.4 (d, ≡CCF,
J = 32); 87.8 (d,
≡CCH2, J = 9)
30.8 (d, CH, J =
11); 19.6 (d, CH2,
J = 13.5); 70.6 (d,
CF, J = 213)
13.6 (CH3); 18.6 (d,
CH2, J = 2.5); 22.0,
30.5 (2 CH2)
126.8, 128.2,
128.5 (Ph);
134.7 (C(1), Ph)
6g
73.4 (d, ≡CCF,
J = 33); 99.1 (d,
≡C—But, J = 10)
72.0 (d, ≡CCF,
J = 31); 102.7 (d,
≡C—But, J = 10)
74.1 (d, ≡CCF,
J = 30); 98.3 (d,
≡C—But, J = 10)
85.2, 88.0
26.5 (d, 2 CMe2,
J = 12); 80.2 (d,
CF, J = 213)
21.4 (d, 2 CH,
J = 13); 76.9 (d,
CF, J = 204)
20.7 (d, 2 CH,
J = 13); 79.5 (d,
CF, J = 203)
30.2 (2 CMe2);
49.7 (CCl)
10.0 (CHMe);
28.9 (CMe2);
45.3 (CCl)
9.5 (CHMe);
27.7 (CMe2);
45.2 (CCl)
27.8 (d, С(СН3)3,
J = 2); 31.0 (3 CH3)
15.5 (d, 2 Me,
J = 10);
19.0 (2 Me)
18.9 (2 CH2);
20.7 (d, 2 CH2,
J = 3)
17.7 (d, 2 CH2,
J = 3); 21.4 (d,
2 CH2, J = 2)
18.8 (2 Me);
19.7 (2 Me)
17.3, 24.0,
196 [M]+
194 [M]+
transꢀ6h
cisꢀ6h
27.9 (d, С(СН3)3,
J = 2); 30.9 (3 CH3)
27.5 (d, С(СН3)3,
J = 2); 30.9 (3 CH3)
8a
123.0 (C(1));
128.2, 128.3
122.8 (C(1))
128.3,
128.4,
122.9 (C(1)) 131.7,
131.8
232, 234 [M]+
218, 220 [M]+
transꢀ8b
82.8, 86.0
86.6, 89.9
32.1 (3 Me)
cisꢀ8b
16.3, 25.0,
34.4 (3 Me)
8d
80.7, 83.7
77.6, 87.1
29.8 (2 CMe2);
48.4 (CCl)
25.0 (CH2);
18.6 (2 Me); 60.7
(2 CH2); 91.4 (CH)
13.6 (CH3);
15.1 (2 Me);
19.6 (2 Me)
136.1 (C(1))
212, 214 [M]+
128.1,
transꢀ8e
232, 234 [M]+
35.2 (CHPh);
33.5 (ССl)
18.5, 21.6,
30.3 (3 CH2)
128.7,
129.3
(to be continued)

Generation of (alkꢀ1ꢀynyl)halocarbenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
1245
Table 6 (continued)
Comꢀ
pound
13C NMR
MS,
m/z
C≡C
cycloꢀС3
R1
R2—R5
cisꢀ8e
82.7, 84.4
23.8 (CH2);
36.4 (CHPh);
34.1 (ССl)
25.4 (CMe2);
31.8 (CH2);
41.5 (CCl)
28.8 (2 CMe2);
49.9 (CCl)
29.8 (2 CMe2);
48.4 (CCl)
13.9 (CH3);
18.6 (CH2);
22.0, 30.6 (2 CH2)
13.5 (CH3);
18.5, 21.9,
30.7 (2 CH2)
27.7 (CMe3);
31.1 (3 Me)
18.6 (2 Me);
60.7 (2 CH2);
91.4 (CH)
133.7 (C(1)) 126.7,
128.0,
128.3
22.1, 23.1 (2 Me)
8f
79.6, 84.4
184, 186 [M]+
212, 214 [M]+
8g
8h
77.1, 94.2
80.7, 83.7
18.8 (2 Me);
19.6 (2 Me)
15.1 (2 Me);
19.6 (2 Me)
258, 260 [M]+,
213, 215
[M – EtOH]+
230, 232 [M]+,
185, 187
8i
78.8, 84.8
84.1, 89.1
82.3, 90.0
25.9 (CMe2);
31.8 (CH2);
39.8 (CCl)
30.4 (2 CMe2);
49.5 (CCl)
14.8 (2 Me); 60.4,
60.5 (2 CH2);
91.0 (CH)
121.5 (C(1)); 128.6,
133.0 (4 CH);
134.2 (CCl)
121.2 (C(1)); 128.6,
133.0 (4 CH);
134.4 (CCl)
21.7 (2 Me);
22.8 (2 Me)
[M – EtOH]+
266, 268 [M]+
8j
18.8 (2 Me);
19.7 (2 Me)
8k
26.7 (CMe2);
32.6 (CH2);
40.8 (CCl)
22.2, 23.3 (2 Me)
238, 240 [M]+
12a
12b
12c
12d
85.6, 89.3
78.5, 94.7
78.8, 82.1
83.6, 90.3
30.1 (2 CMe2);
43.2 (CBr)
28.8 (2 CMe2);
44.1 (CBr)
29.0 (2 CMe2);
44.7 (CBr)
26.1 (CMe2);
30.2 (CBr);
33.2 (CH2)
28.0 (2 CH);
34.7 (CBr)
25.3 (2 CH);
29.9 (CBr)
22.7 (CMe2);
32.7 (CH2);
31.2 (CBr)
123.1 (C(1)); 128.2,
128.3, 131.8 (Ph)
27.8 (CMe3);
31.1 (3 Me)
19.5 (2 Me);
21.4 (2 Me)
18.7 (2 CH2);
21.4 (2 CH2)
19.4 (2 Me),
21.4 (2 Me)
22.8 (Me);
276, 278 [M]+
256, 258 [M]+
214, 216 [M]+
248, 250 [M]+
4.0 (Me)
122.8 (C(1)); 128.3,
128.4, 131.8
24.9 (Me)
transꢀ12e
cisꢀ12e
12f
87.4, 89.3
80.5, 93.4
81.1, 84.9
122.8 (C(1)) 128.2,
128.3,
122.9 (C(1)) 128.4,
128.5
13.6 (CH3); 18.7,
22.0, 30.8 (3 CH2)
20.1 (2 CH2);
20.7 (2 CH2)
20.6 (2 CH2);
24.6 (2 CH2)
22.8 (Me);
274, 276 [M]+
228, 230 [M]+
24.9 (Me)
* The other signals overlap signals for transꢀ6e.
1
Table 7. H NMR spectra (CDCl3, 200.13 MHz, δ, J/Hz) of (organyl)halovinylidenecyclopropanes 13 and 14a—e
Comꢀ
pound
1H NMR
R2, R5
R1
R3, R4
13
0.89 (t, 3 H, CH3 in Bu, J = 7); 1.20—1.55 (m,
4 H, 2 CH2); 2.36 (t, 2 H, —CH2CCl=, J = 7)
7.15—7.60 (m, 5 H, Ph)
1.16 (s, 9 H, 3 Me)
2.31 (s, 3 H, Me)
7.15—7.60 (m, 5 H, Ph)
0.91 (t, 3 H, CH3 in Bu, J = 7); 1.20—1.55 (m, 1.52 (d, 1 H, CH2, J = 7.3);
4 H, 2 CH2); 2.47 (t, 2 H, —CH2CBr=, J = 7) 1.49 (d, 1 H, CH2, J = 7.3)
1.26 (s, 6 H, 2 Me); 1.29 (s, 6 H, 2 Me)
14a
14b
14c
14d
14e
1.43 (s, 6 H, 2 Me); 1.47 (s, 6 H, 2 Me)
1.25 (s, 6 Н, 2 Me); 1.28 (s, 6 Н, 2 Me)
1.27 (s, 12 Н, 4 Me)
1.78 (s, 2 H, СН2)
1.42 (3 H, Me); 1.45 (s, 3 H, Me)
1.29 (s, 3 H, Me); 1.27 (s, 3 H, Me)

1246
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
Shavrin et al.
Table 8. 13C NMR spectra (CDCl3, 50.32 MHz, δ) and mass spectra (m/z) of (organyl)halovinylidenecyclopropanes 13 and 14a—e
Comꢀ
pound
13C NMR
MS
C=С=С
=С=
180.8
cycloꢀС3
R1
R2—R5
13
107.3, 107.6
13.9 (СH3CH2—); 21.0, 21.1, 21.8, 29.3, 29.5,
36.9 (2 CMe2, 2 С(CH3), CH2—CH2—CH2 in Bu)
212, 214 [M]+
214, 216 [M]+
14a
94.7, 106.1
186.0
32.1 (2 C(Me)2)
125.9, 128.2, 128.8 (Ph);
135.9 (C(1))
21.1 (2 Me); 21.6 (2 Me)
14b
14c
14d
14e
105.7, 108.1
90.1, 105.8
180.3
182.0
29.0 (CMe2)
29.3 (CMe2)
29.1 (3 Me); 37.6 (CMe3) 20.9 (2 Me); 21.0 (2 Me)
26.4 (Me) 20.9 (2 Me); 21.3 (2 Me)
256, 258 [M]+
214, 216 [M]+
248, 250 [M]+
228, 230 [M]+
—
96.2, 98.0
183.4
13.9 (СH3CH2—); 21.7, 22.5, 23.9, 24.7, 30.3, 31.2 (CMe2, 2 С(CH3),
CH3—CH2—CH2— in Bu, CH2 in cycloꢀC3H2); 38.5 (СН2СBr=)
phenylpropꢀ1ꢀene (19a) (Scheme 7). The latter was obꢀ
tained in the individual state in 28% yield by refluxing
tetrahalide 2a with triethylamine for 8 h. Note that the
formation of trichloride 19a from 2a (and possibly
from 3a) is most probably due to the allylic rearrangeꢀ
ment10 of 1,1,1ꢀtrichloroꢀ3ꢀphenylpropꢀ2ꢀene (20a) iniꢀ
tially formed through elimination of HBr.
1H NMR spectroscopy. The spectrum of the reaction
mixture shows a singlet at δ 6.57 corresponding to the
allene proton and a multiplet for the phenyl protons at
δ 7.30—7.50. Its 13C NMR spectrum exhibits a sigꢀ
nal at δ 200.9 for the spꢀhybridized carbon atom in
the allene fragment, a signal at δ 127 for the CCl2
group, and a signal at δ 106 for the =CH group,
which, without proton decoupling, appears as a doublet
with a coupling constant of 165 Hz. Allene 22a is
rather labile and decomposes almost completely even in
deuterochloroform at ∼20 °C over a few days (GLC and
1H NMR data).
Scheme 7
The resulting mixture of compounds 21a and 22a
react with ButOK and an excess of 2,3ꢀdimethylbutꢀ
2ꢀene to give 1ꢀchloroꢀ2,2,3,3ꢀtetramethylꢀ1ꢀ(phenylꢀ
ethynyl)cyclopropane (8a) in 55% yield; the reaction
mixture contained no starting dichlorides. When the iniꢀ
tial ratio between dichlorides 21a and 22a was changed
from 3 : 1 to 1 : 1, the yield of cycloadduct 8a remained
unchanged, being the same as for dichloride 21a used
alone (55%).
Reagents and conditions: ButOK (0.5 equiv.), hexane, 20 °C.
The treatment of trichloride 19a with an excess of
ButOK in the presence of excess 2,3ꢀdimethylbutꢀ2ꢀene
gave the corresponding cyclopropane 8a in 46% yield.
During the course of the reaction, 3,3ꢀdichloroꢀ1ꢀphenylꢀ
propꢀ2ꢀyne (21a) and 1,1ꢀdichloroꢀ3ꢀphenylpropaꢀ
1,2ꢀdiene (22a) were detected in the reaction mixꢀ
ture. These compounds proved to be identical with
authentic samples obtained in an independent way
(GLC data).
We found5 that treatment of 3,3ꢀdichloroꢀ1ꢀphenylꢀ
propꢀ2ꢀyne (21a) with a deficient amount of ButOK in
hexane at ∼20 °C yields a mixture of dichloride 21a and
allene 22a in the ratios from 5 : 1 to 1 : 1, depending on
the amount of the base and the reaction time. However,
the conversion of the starting alkyne 21a into allene
22a was incomplete since the reaction mixture, for
ButOK > 0.5 equiv., undergoes significant resinification,
and no increase in the content of 22a resulted. The presꢀ
ence of allene 22a in the reaction mixture was proved by
Hence, it can be concluded that cyclopropane 8a is
formed both from dichloroalkyne 21a and from dichloroꢀ
allene 22a. Apparently, when treated with ButOK, both
lose the proton to give anion 23, which is transformed,
through the elimination of the chloride anion, into
chloro(phenylethynyl)carbene 7a; the latter is trapped
by 2,3ꢀdimethylbutꢀ2ꢀene (Scheme 8).
Moreover, using the Moss method,11 we demonstrated
that the carbenes generated from both dichloride 21a
and trichloro bromide 2a are of the same nature. For this
purpose, we used the method of competitive reactions to
determine the relative reactivities (ki/k0) of carbene 7a
generated under the action of ButOK from the above
halides with respect to a set of methylolefins with
2ꢀmethylpropene as a reference (ki/k0 = 1). The results
obtained are given in Table 9. While comparing the relaꢀ
tive reactivities of chloro(phenylethynyl)carbene generꢀ
ated from dichloride 21 and that from tetrahalide 2a,
one can see that they are equal to within the measureꢀ

Generation of (alkꢀ1ꢀynyl)halocarbenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
1247
Scheme 8
Scheme 9
Reagents and conditions: ButOK, hexane, 20 °C.
Thus, the results obtained indicate that the reactions
of halides 2a and 3a with ButOK in the presence of
alkenes follow Scheme 10, proceeding through an equiꢀ
librium mixture of dichloroallene 22a and dichloroꢀ
alkyne 21a.
Reagents and conditions: ButOK, hexane, 20 °C, 30—90 min.
When 1,1,3ꢀtribromoꢀ1ꢀfluoroheptane (1b) was
treated with an equimolar amount of ButOK in the abꢀ
sence of olefins, the reaction mixture contained, along
with the starting halide, transꢀ1,1ꢀdibromoꢀ1ꢀfluoroheptꢀ
2ꢀene (24) and the Eꢀ and Zꢀisomers of 1,3ꢀdibromoꢀ1ꢀ
fluoroheptꢀ1ꢀene (25) in the ratio 1 : 1.8 : 0.9 : 0.75,
respectively. Addition of ButOK to the resulting mixꢀ
ture gave 1ꢀbromoꢀ1ꢀfluoroheptaꢀ1,2ꢀdiene (26) and
1ꢀbromoꢀ1ꢀfluoroheptꢀ2ꢀyne (27).
Table 9. Relative reactivity of chloro(phenylꢀ
ethynyl)carbene 7a generated from dichloride 21a (A)
and from trichloro bromide 2a (B)
Alkene
A
B
2ꢀMethylpropene
2ꢀMethylbutꢀ2ꢀene
2,3ꢀDimethylbutꢀ2ꢀene
cisꢀButꢀ2ꢀene
1.0
1.0
2.1 0.13
4.9 0.21
0.34 0.02
1.9 0.15
5.0 0.17
0.36 0.03
The structures of all intermediate halides were proved
1
by H and 19F NMR spectroscopy and GLꢀMS analysis.
ment error, which confirms the identity of the resulting
intermediates.
The configuration of the double bond in compounds 24
and 25 was determined from the values of vicinal H—H
(for 24) and H—F (for 25) coupling constants.
It should be noted that a set of signals correspondꢀ
ing to the CH=CH fragment in compound 24 has a
very complex structure since the both protons have
close chemical shifts and there are a lot of H—H and
H—F spinꢀspin couplings. To calculate precise chemiꢀ
cal shifts and coupling constants, we calculated the
Direct evidence that 1,1ꢀdihaloꢀ3ꢀorganylꢀ1,2ꢀdienes
22 are precursors of (alkꢀ1ꢀynyl)halocarbenes was proꢀ
vided5 by the generation of chloro(3,3ꢀdiethoxypropꢀ1ꢀ
ynyl)carbene (7d) in the reaction of 1,1ꢀdichloroꢀ4,4ꢀ
diethoxybutaꢀ1,2ꢀdiene (22b) with ButOK. Its trapping
by 2,3ꢀdimethylbutꢀ2ꢀene afforded the corresponding
cyclopropane 8h in 48% yield (Scheme 9).
Scheme 10
Reagents and conditions: i) ButOK, hexane, 20 °C.

1248
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
Shavrin et al.
Scheme 11
Reagents and conditions: i) ButOK, hexane, 20—60 °C.
1
spectrum* and corrected the initial parameters to miniꢀ
mize a discrepancy between the calculated and experiꢀ
mental data. Based on the coupling constant between
the olefinic protons (15.5 Hz), obtained by this iterative
procedure, we unambiguously assigned the transꢀstrucꢀ
ture to alkene 24.
and CHBr groups at δ 4.6—4.8. The H NMR spectrum
of trichloroalkene 20b with the internal double bond
shows a set of signals (d and dt) characteristic of
the olefinic protons in the CH=CH—CH2 fragment.
The vicinal coupling constant (15.5 Hz) indicates the
transꢀconfiguration of the double bond in 20b.
For the major isomer of compound 25 in the reaction
mixture, JH,F = 28 Hz, while for the minor isomer this
value was 10 Hz. Insofar as Jcis < Jtrans for fluoroalkenes,9
Eꢀhalide 25 proves to be dominant.
Scheme 12
1
The H NMR spectrum of allene 26 contains a charꢀ
acteristic signal for the allene proton at δ 5.97 (td, JH,F
=
1.6 Hz); this coupling constant is consistent with the
19F NMR data for this compound. As expected, the
1H NMR spectrum of alkyne 27 shows a doublet of
triplets for the CHBrF group at δ 7 (JH,F = 52 Hz,
JH,H = 1.7 Hz) because of the spinꢀspin coupling of the
proton with the F atom and with the CH2 group through
the triple bond.
The data obtained suggest that carbene 5b is generꢀ
ated from tetrahalides 1b according to Scheme 11. Apꢀ
parently, the generation of other (alkꢀ1ꢀynyl)fluoroꢀ
carbenes 5 occurs analogously.
Reagents and conditions: ButOK, hexane, 20 °C.
Further reactions of the mixtures obtained with ButOK
resulted in carbene generation, and intermediate prodꢀ
ucts of their monodehydrohalogenation were not isoꢀ
lated or characterized. Insofar as tetrahalide 2b selecꢀ
tively generates only chloro(hexꢀ1ꢀynyl)carbene 7b (see
Scheme 3, Table 1), both chlorides 19c and 20b seem to
be its precursors. Thus, carbene 7b is probably generꢀ
ated by analogy with (alkynꢀ1ꢀyl)fluorocarbene (see
Scheme 11) through the formation of an equilibrium
mixture of 1,1ꢀdichloroheptꢀ2ꢀyne (21b) and 1,1ꢀdiꢀ
chloroheptaꢀ1,2ꢀdiene (22c) (Scheme 13).
The generation of butyl(chloro)vinylidenecarbene (10)
in the reaction of tetrachloride 3b with ButOK (see
Scheme 5) most probably proceeds via dehydrochlorinaꢀ
tion of trichloride 19b into 1,3ꢀdichloroheptꢀ1ꢀyne (28),
which undergoes γꢀelimination of HCl, by analogy
Unlike halides 2a and 3a, compounds 2b and 3b reꢀ
act with a deficient amount of ButOK (Scheme 12) to
give a mixture of isomeric alkenes containing the termiꢀ
nal (19b,c) and internal double bond (20b) in the ratios
1 : 1.2 and 1 : 3.5, respectively. Their structures were
1
determined from the H NMR spectra of the reaction
mixture. Trihalides 19b,c give doublets for olefinic proꢀ
tons at δ 5.95—6.10 and doublets of triplets for the CHCl
* To determine the chemical shifts and the coupling constants
for a multiplet corresponding to this fragment, the spectral
parameters were calculated and corrected to minimize a disꢀ
crepancy between the calculated and experimental data (the
NUTS program, version 4.35). The resulting chemical shifts
and coupling constants are δ(C(H)2CHb=) 5.95 (Ja,b = 6.9 Hz,
Jb,c = 15.5 Hz, JH,F = –1 Hz); δ(CBr2FCHc=) 6.04 (Ja,c
–1.5 Hz, Jb,c = 15.5 Hz, JH,F = 16.4 Hz).
=

Generation of (alkꢀ1ꢀynyl)halocarbenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
1249
Scheme 13
Reagents and conditions: i) ButOK, hexane, 20—60 °C.
with other vinylidenecarbenes,12 to give carbene 10
Scheme 15
(Scheme 14).
Scheme 14
Reagents and conditions: i) ButOK, hexane, 20—60 °C.
Reagents and conditions: i) KOH, CH2Cl2, BTEAC, 20 °C.
Apparently, the reactions of tetrabromides 4a,c,f with
ButOK proceed analogously, generating (alkꢀ1ꢀynyl)broꢀ
mocarbenes 9a—c and bromovinylidenecarbenes 11a—c
(see Scheme 5). These carbenes are trapped by alkenes
to give isomeric bromineꢀcontaining cyclopropanes 12
and 14. Phenylvinylidenecarbene (16) is most likely genꢀ
erated from tetrabromide 4a under conditions of phaseꢀ
transfer catalysis (see Scheme 6) via elimination of two
HBr molecules followed by KOHꢀinitiated debromination
of intermediate 1,1ꢀdibromoꢀ3ꢀphenylpropaꢀ1,2ꢀdiene
(29) (Scheme 15). The possibility of such processes has
been reported earlier.13
(phaseꢀtransfer catalysis) or ButOK exclusively give
(alkꢀ1ꢀynyl)fluorocarbenes, which belong to a new class
of carbene intermediates. Under analogous condiꢀ
tions, 3ꢀarylꢀ and 3ꢀalkylꢀ3ꢀbromoꢀ1,1,1ꢀtrichloroꢀ
propanes generate (alkꢀ1ꢀynyl)chlorocarbenes. However,
the behavior of 3ꢀsubstituted 1,1,1,3ꢀtetrachloroꢀ or
1,1,1,3ꢀtetrabromopropanes in the presence of bases is
Scheme 16
The formation of small amounts of a third product,
namely, cyclopropane 17, from tetrabromide 4b suggests
the generation of (transꢀhexꢀ1ꢀenyl)bromocarbene (18)
(see Scheme 6), which can be due to partial debrominaꢀ
tion of intermediate transꢀ1,1,1ꢀtribromoheptꢀ2ꢀene (30)
under the action of ButOK.
Hence, we found that the reactions of 3ꢀalkylꢀ and
3ꢀphenylꢀ1,1,3ꢀtribromoꢀ1ꢀfluoropropanes with KOH
Reagents and conditions: i) ButOK, hexane, 20—60 °C.

1250
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
Shavrin et al.
(3 Me); 36.3 (CMe3); 57.6 (d, CH2CBr2F, J = 18 Hz);
61.0 (CHBr); 94.3 (d, CBr2F, J = 324 Hz).
largely determined by the nature of both the 3ꢀsubstituꢀ
ent and the halogen atoms and also depend on the reꢀ
action conditions. When they are used as carbene
sources, halovinylidenecarbenes are generated along with
(alkynꢀ1ꢀyl)halocarbenes; in some cases, vinylideneꢀ and
bromo(vinyl)carbenes are also formed. The mechanisms
for these complex multistep reactions were proposed.
Synthesis of 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀfluorocyclopropanes (6a—h)
and 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀchlorocyclopropanes (8a—k) from 3ꢀsubꢀ
stituted 1,1,3ꢀtribromoꢀ1ꢀfluoropropanes (1a—c) and 3ꢀsubstiꢀ
tuted 3ꢀbromoꢀ1,1,1ꢀtrichloropropanes (2a—e) (general proceꢀ
dure). A. Using ButOK as a base. A solution of a starting
tetrahalide (2 mmol) in 1 mL of a solvent specified in Table 1
was added at ∼20 °C to a mixture of ButOK (1350 mg, 12 mmol)
and a starting alkene (6 mmol) in 6 mL of the same solvent.
The reaction mixture was stirred (the reaction duration and
temperature are given in Table 1) until the reaction was comꢀ
pleted (monitoring by GLC). Then the reaction mixture was
treated with water, and the organic layer was separated. The
organic material was extracted from the aqueous phase with
ether (3×10 mL). The combined organic layers were dried with
magnesium sulfate, and the solvent was removed. Cycloproꢀ
pane 6 or 8 was isolated from the residue by vacuum distillation
or by column chromatography in hexane (see Table 1). The
yields, boiling points, and the ratios between the cisꢀ and
transꢀisomers of compounds 6 and 8 are given in Table 1. Their
spectral characteristics are presented in Tables 3—5.
B. Using KOH as a base. A solution of a starting tetrahalide
(2 mmol) in 1 mL of CH2Cl2 was added to a mixture of KOH
(1.8 g, 30 mmol), one drop of water, BTEAC (50 mg), and a
starting alkene (6 mmol) in CH2Cl2 (10 mL). The solvent was
preliminarily refluxed over KOH with BTEAC and then disꢀ
tilled to remove an impurity of chloroform. The reaction mixꢀ
ture was stirred (the reaction duration and temperature are
given in Table 1) until the reaction was completed (monitoring
by GLC). The product was isolated as described above for
ButOK as a base (see Table 1). The yields, boiling points, and
the ratios between the cisꢀ and transꢀisomers of cyclopropanes
6 and 8 are given in Table 1. Their spectral characteristics are
presented in Tables 3—6.
Reaction of 1,1ꢀdichloroꢀ3ꢀphenylpropꢀ2ꢀyne (21a) with a
deficient amount of ButOK. Generation of chloro(phenylꢀ
ethynyl)carbene (7a) from a mixture of dichloride 21a and
1,1ꢀdichloroꢀ3ꢀphenylpropadiene (22a). Freshly prepared ButOK
(50 mg, 0.44 mmol) was added at ∼20 °C to a solution of
dichloride 21a (185 mg, 1 mmol) in 3 mL of hexane. After
10 min, the content of the starting dichloride was reduced to
82%, and allene 22a (18%) was detected in the reaction mixꢀ
ture (GLC data). The ratio of compound 21a to 22a became
1 : 1 after 30 min. When the reaction was carried out for a
longer period of time or with a larger amount of ButOK (in
separate experiments), the relative content of allene 22a in the
mixture did not increase because of intense resinification. The
mixture of the starting dichloride and allene 22a was isolated
by passing the reaction mixture through a thin layer of silica
gel. The solution obtained was then used in reactions with
ButOK in the presence of 2,3ꢀdimethylbutꢀ2ꢀene. Product 22a
was characterized by the NMR spectra of the reaction mixture.
1H NMR, δ: 6.57 (s, 1 H, PhCH); 7.20—7.50 (m, 5 H, 2 Ph).
13C NMR, δ: 106.1 (PhCH); 127.0 (CCl2); 127.4, 129.8,
132.0 (Ph); 139.4 (C(1), Ph); 201.0 (=C=).
Experimental
GLC analysis of the starting reagents and the products was
carried out on a HewlettꢀPackard 5890 Series II instrument
with a capillary column 30 m×0.153 mm and a HewlettꢀPackard
3396A automated integrator. When the yields of the known
compounds were determined by GLC, the products were idenꢀ
tified by comparing their retention times with those of authenꢀ
1
tic samples. H and 13C NMR spectra were recorded on Bruker
ACꢀ200p and Bruker AMꢀ300 spectrometers in CDCl3 with
tetramethylsilane as the internal standard. IR spectra were reꢀ
corded on a Perkin—Elmer 580 spectrophotometer in CCl4.
Mass spectra were recorded on a Finningan MAT INCOSꢀ50
GLꢀMS spectrometer.
The starting 3ꢀsubstituted 1,1,1,3ꢀtetrahalopropanes
2a—e, 3b, and 4a—c,f were prepared as described in Ref. 7;
1,1,1,3ꢀtetrachloroꢀ3ꢀphenylpropane (3a) was obtained accordꢀ
ing to the known procedure.8
1,1ꢀDichloroꢀ3ꢀphenylpropꢀ2ꢀyne (19a) and 1,1ꢀdichloroꢀ
4,4ꢀdiethoxybutaꢀ1,2ꢀdiene (22b) were prepared as described
earlier.5 Tetrabromomethane,14 tribromofluoromethane,15 and
bromotrichloromethane16 were synthesized according to the
known procedures.
Synthesis of 3ꢀsubstituted 1,1,3ꢀtribromoꢀ1ꢀfluoropropanes
(1a—c). Azodiisobutyronitrile (50 mg, 0.3 mmol) was added
to a mixture of a starting alkene (styrene, hexꢀ1ꢀene, or
3,3ꢀdimethylbutꢀ1ꢀene) (10 mmol) and tribromofluoromethane
(13.5 g, 50 mmol). The reaction mixture was heated at 75 °C
for 4—12 h, and the excess of tribromofluoromethane was reꢀ
moved at atmospheric pressure (b.p. 106—108 °C) and then at
10—15 Torr. The product was isolated from the residue by
vacuum distillation.
1,1,3ꢀTribromoꢀ1ꢀfluoroꢀ3ꢀphenylpropane (1a), b.p.
112—114 °C (1 Torr). The yield was 30% (from styrene).
1H NMR, δ: 3.71—3.84 (m, 2 H, CH2); 5.37 (dd, 1 H, CHBr,
J = 6.2 Hz, J = 7.4 Hz); 7.30—7.50 (m, 5 H, Ph). 13C NMR, δ:
47.7 (CHBr); 60.8 (d, CH2CBr2F, J = 18 Hz); 92.3 (d, CBr2F,
J = 324 Hz); 127.7, 128.9, 129.0 (Ph); 140.2 (C(1), Ph).
1,1,3ꢀTribromoꢀ1ꢀfluoroheptane (1b), b.p. 83—84 °C
1
(2 Torr). The yield was 78% (from hexꢀ1ꢀene). H NMR, δ:
0.93 (t, 3 H, CH3, J = 7 Hz); 1.25—1.65 (m, 4 H, 2 CH2);
1.70—2.05 (m, 2 H, CH2CHBr); 3.26 (ddd, 1 H, CH2CFBr2,
J = 17 Hz, J = 7.5 Hz, JH,F = 17 Hz); 3.43 (ddd, 1 H,
CH2CFBr2, J = 17 Hz, J = 6.2 Hz, JH,F = 23 Hz); 4.30 (ddt,
1 H, CHBr, J = 6.2 Hz, J = 7.5 Hz, J = 7 Hz). 13C NMR, δ:
14.0 (Me); 21.9, 29.2, 38.2 (3 CH2); 49.6 (CHBr); 60.4 (d,
CH2CBr2F, J = 18 Hz); 93.3 (d, CBr2F, J = 323 Hz).
2,3ꢀDimethylbutꢀ2ꢀene (252 mg, 3 mmol) and tridecane
(100 mg) were added to a solution of the aforesaid 1 : 1 mixture
of dichlorides 21a and 22a. The resulting mixture was analyzed
by GLC with a preꢀcalibrated detector. The amount of dichloꢀ
rides 21a and 22a in the mixture was determined from the ratio
1,1,3ꢀTribromoꢀ1ꢀfluoroꢀ4,4ꢀdimethylpentane (1c), b.p.
80—82 °C (3 Torr). The yield was 58% (from 3,3ꢀdimethylbutꢀ
1
1ꢀene). H NMR, δ: 1.11 (s, 9 H, 3 Me); 3.26—3.41 (m, 2 H,
CH2CBr2F); 4.00—4.07 (m, 1 H, CHBr). 13C NMR, δ: 27.2

Generation of (alkꢀ1ꢀynyl)halocarbenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
1251
of their peak areas to that of tridecane. Potassium tertꢀbutoxide
(224 mg, 2 mmol) was added, and the reaction mixture was
kept for 30 min and treated with 5 mL of water. The organic
layer was separated, and the organic material was extracted
from the aqueous phase with hexane (2×5 mL). The combined
organic layers were analyzed by GLC with a preꢀcalibrated
detector. The yield of 1ꢀchloroꢀ2,2,3,3ꢀtetramethylꢀ1ꢀ(phenylꢀ
ethynyl)cyclopropane (8a) (55% from both dichlorides 21a and
22a) was determined from the ratio of its peak area to that of
tridecane. In an analogous reaction involving a 3 : 1 mixture
of dichlorides 21a and 22a, the yield of cyclopropane 8a
was 56%.
B. When chloro(phenylethynyl)carbene (7a) was generated
from tetrahalide 2a (200 mg, 0.66 mmol), the corresponding
stoichiometric amount of ButOK (220 mg, 2 mmol) was taken.
The ki/k0 values obtained are given in Table 9.
Synthesis of cyclopropanes 8a and 8c by the reactions of
1,1,1,3ꢀtetrachloroꢀ3ꢀphenylpropane (3a) with ButOK in the
presence of alkenes. The reaction was carried out according to
the general procedure for the preparation of 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀ
chlorocyclopropanes (see above) with the use of ButOK as a
base. After the reaction was completed (over 1 h in hexane at
∼20 °C), the reaction product was isolated by column chromaꢀ
tography in hexane (cyclopropane 8a) or by vacuum microꢀ
distillation (cyclopropane 8c). The yields of compounds 8a and
When dichloride 21a was used alone (instead of a mixture
of chlorides 21a and 22a), the yield of cyclopropane 8a was
60% (GLC data).
1
8c were 66 and 58%, respectively. Their H NMR spectra are
identical with those of the same cyclopropanes obtained from
tetrahalide 2a.
While carrying out an analogous reaction without addition
of tridecane, cyclopropane 8a (98 mg, 42%) was isolated from
the reaction mixture by column chromatography in hexane.
The purity of the product was >95% (GLC and 1H NMR data).
Synthesis of 1ꢀchloroꢀ1ꢀ(3,3ꢀdiethoxypropꢀ1ꢀynyl)ꢀ2,2,3,3ꢀ
tetramethylcyclopropane (8h). A solution of 1,1ꢀdichloroꢀ4,4ꢀ
diethoxybutaꢀ1,2ꢀdiene (22b) (560 mg, 2.65 mmol) in 1 mL of
hexane was added at ∼20 °C to a mixture of 2,3ꢀdimethylbutꢀ
2ꢀene (670 mg, 8 mmol) and ButOK (582 mg, 5.2 mmol) in
5 mL of hexane. The reaction mixture was stirred for 2 h and
treated with water. The organic layer was separated, and the
organic material from the aqueous phase was extracted with
hexane (3×10 mL). The combined organic layers were dried
with magnesium sulfate, and the solvent was evaporated. Colꢀ
umn chromatography of the residue in hexane gave cycloproꢀ
pane 8h (327 mg, 48%). The spectral data of the product obꢀ
tained are given in Tables 4 and 5.
Determination of the relative reactivity of chloro(phenylꢀ
ethynyl)carbene (7a) generated from 3,3ꢀdichloroꢀ1ꢀphenylꢀ
propyne (21a) and 3ꢀbromoꢀ1,1,1ꢀtrichloroꢀ3ꢀphenylpropane (2a)
under the action of ButOK. A. Potassium tertꢀbutoxide (110 mg,
1 mmol) was added to a solution of 2,3ꢀdimethylbutꢀ2ꢀene and
2ꢀmethylbutꢀ2ꢀene (10—15 mmol) in 25 mL of benzene. The
reaction mixture was cooled to –10 to –20 °C, and 2ꢀmethylꢀ
propene (350—650 mg, 7—12 mmol) was added using an evapoꢀ
ration—condensation method. The flask was hermetically sealed
with a rubber plug and warmed to ∼20 °C. A solution of the
starting dichloride 21a (1 mmol) in 1—2 mL of hexane was
added. After 30 min, the reaction mixture was stratified by
adding water, and the organic layer was analyzed five times by
GLC. An outlier (if present) was rejected, while the other
results were averaged. The mass fractions of cyclopropanes 8
were determined with a detector preꢀcalibrated against authenꢀ
tic samples. The data obtained were used to calculate ki/k0 for
carbene 7a with respect to a corresponding alkene by the forꢀ
mula ki/k0 = (ni/n0) (m0/mi), where ni/n0 is the ratio between
the obtained amounts of adducts of carbene 7a with the ith
alkene and with 2ꢀmethylpropene and m0/mi is the molar ratio
of 2ꢀmethylpropene to the ith alkene. In each case, the data
from two analogous experiments were averaged. The confiꢀ
dence interval was calculated according to a standard proꢀ
cedure.17
Reactions of 1,1,1,3ꢀtetrachloroheptane (3b) with bases in
the presence of 2,3ꢀdimethylbutꢀ2ꢀene. A. Using ButOK as a
base. A solution of tetrachloride 3b (400 mg, 1.68 mmol) in
1 mL of hexane was added at ∼20 °C to a mixture of ButOK
(1120 mg, 10 mmol) and 2,3ꢀdimethylbutꢀ2ꢀene (420 mg,
5 mmol) in 5 mL of hexane. The reaction mixture was stirred at
∼20 °C for 48 h and then treated with water. The organic layer
was separated, and the organic material was extracted from the
aqueous phase with ether (3×10 mL). The combined organic
layers were dried with magnesium sulfate, and the solvent was
evaporated. Vacuum microdistillation (10 Torr, bath temperaꢀ
ture 120—130 °C) of the residue gave a 4 : 1 mixture of isoꢀ
meric cyclopropanes 8d and 13 (170 mg, a total yield of 50%).
The spectral characteristics of products 8d and 13 are given in
Tables 4—8.
B. Using KOH as a base. A solution of tetrachloride 3b
(800 mg, 3.36 mmol) in 1 mL of CH2Cl2 was added to a
mixture of KOH (2.8 g, 50 mmol), one drop of water, BTEAC
(50 mg, 0.22 mmol), 2,3ꢀdimethylbutꢀ2ꢀene (840 mg, 10 mmol),
and CH2Cl2 (10 mL). The reaction mixture was stirred at ∼20 °C
for 80 h (monitoring by GLC) and then treated with water. The
organic layer was separated, and the organic material was exꢀ
tracted from the aqueous phase with ether (3×10 mL). The
combined organic layers were dried with magnesium sulfate,
and the solvent was evaporated. Vacuum microdistillation
(10 Torr, bath temperature 120—130 °C) of the residue gave a
1.1 : 1 mixture of isomeric cyclopropanes 8d and 13 (325 mg, a
total yield of 48%). The spectral characteristics of products 8d
and 13 are given in Tables 4—8.
Synthesis of 1ꢀbromoꢀ1ꢀ(phenylethynyl)cyclopropanes
(12a,d,e) by the reactions of 1,1,1,3ꢀtetrabromoꢀ3ꢀphenylpropane
(4a) with ButOK in the presence of alkenes. A solution of
tetrabromide 4a (4.36 g, 10 mmol) in 10 mL of benzene was
added at ∼20 °C to a mixture of ButOK (5.6 g, 50 mmol) and a
starting alkene (30 mmol) in 30 mL of benzene. The reaction
mixture was stirred at ∼20 °C for 1 h and then treated with
water. The organic layer was separated, and the organic mateꢀ
rial was extracted from the aqueous phase with benzene
(2×30 mL). The combined organic layers were dried with magꢀ
nesium sulfate, and the solvent was evaporated. The resiꢀ
due was passed through an SiO2 layer in hexane cooled to
–10 °C, and the solvent was removed in vacuo (30—40 °C,
10—15 Torr).
The ki/k0 value for cisꢀbutene was determined in a separate
experiment. In this case, the starting mixture was prepared by
evaporation—condensation of cisꢀbutene and 2ꢀmethylpropene
after each other into a reaction flask cooled to –20 to –10 °C.
With 2,3ꢀdimethylbutꢀ2ꢀene as the alkene, the residue conꢀ
tained, along with cyclopropane 12a, vinylidenecyclopropane

1252
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
Shavrin et al.
14a (8%); in the case of 2ꢀmethylpropene, cyclopropane 12d
was accompanied by vinylidenecyclopropane 14d (11%) (NMR
and GLC data). Product 12a was isolated by recrystallization
from methanol, while cyclopropanes 12d,e were purified by
vacuum distillation. The yields, boiling and melting points,
and the ratios of the transꢀ and cisꢀisomers for products 12a,d,e
are given in Table 2. The spectral characteristics of cycloproꢀ
panes 12a,d,e and 14a,d are presented in Tables 4—7.
Reactions of 3ꢀbromoꢀ1,1,1ꢀtrichloroꢀ3ꢀphenylpropane (2a)
and 1,1,1,3ꢀtetrachloroꢀ3ꢀphenylpropane (3a) with a deficient
amount of ButOK. Potassium tertꢀbutoxide (56 mg, 0.5 mmol)
was added at ∼20 °C to a solution of a starting tetrahalide (2a or
3a) (1 mmol) in 5 mL of hexane. The reaction mixture was
stirred for 60 min and then passed through a thin layer of silica
gel; the sorbent was washed with hexane. After the solvent was
evaporated, the residue contained the starting tetrahalide and
1,1,3ꢀtrichloroꢀ3ꢀphenylpropꢀ1ꢀene (19a) in the ∼1 : 1 ratio
(GLC and NMR data). The latter was identified by comparing
Reactions of 3ꢀsubstituted 1,1,1,3ꢀtetrabromopropanes 4b,c,f
with ButOK in the presence of alkenes. A solution of a starting
tetrahalide (2 mmol) in 1 mL of a solvent specified in Table 2
was added at ∼20 °C to a mixture of ButOK (1350 mg, 12 mmol)
and a starting alkene (6 mmol) in 5 mL of the same solvent.
The reaction mixture was stirred (the reaction duration and
temperature are given in Table 2) until the reaction was comꢀ
pleted (monitoring by GLC). Then the reaction mixture was
treated with water, and the organic layer was separated. The
organic material was extracted from the aqueous phase with
ether (3×10 mL). The combined organic layers were dried with
magnesium sulfate and the solvent was evaporated. A mixture
of the reaction products was isolated from the residue by vacuum
distillation, recrystallization from methanol, or by column chroꢀ
matography in hexane. When compounds 4c,f were used, the
resulting mixtures contained two components, namely, broꢀ
mides 12b,c and 14b,c; with 1,1,1,3ꢀtetrabromoheptane (4b) as
the starting reagent, 1ꢀbromoꢀ1ꢀ(transꢀhexꢀ1ꢀenyl)ꢀ2,2ꢀdiꢀ
methylcyclopropane (17) was detected along with bromides 12f
1
its H and 13C NMR spectra with those of an authentic sample
(see below).
Synthesis of 1,1,3ꢀtrichloroꢀ3ꢀphenylpropꢀ1ꢀene (19a).
A mixture of tetrahalide 2a (2.5 g, 8.2 mmol) and triethylamine
(3.3 g, 33 mmol) was refluxed for 8 h. The reaction mixture was
diluted with 20 mL of Et2O and washed with aqueous 5% HCl.
The organic material was additionally extracted from the aqueꢀ
ous layer with ether (10 mL). The combined organic layers
were dried with magnesium sulfate, and the solvent was evapoꢀ
rated. Vacuum distillation of the residue gave product 19a (0.5 g,
1
28%), b.p. 92—93 °C (2 Torr). H NMR, δ: 5.72 (d, 1 H, CH,
J = 10.2 Hz); 6.30 (d, 1 H, CH, J = 10.2 Hz); 7.20—7.50 (m,
5 H, Ph). 13C NMR, δ: 58.4 (CHCl); 124.2 (=CCl2); 126.9,
128.8, 128.9, 129.4 (Ph, —CH=); 138.4 (C(1), Ph). MS, m/z:
185, 187 [M – Cl]+.
Synthesis of 1ꢀchloroꢀ2,2,3,3ꢀtetramethylꢀ1ꢀ(phenylꢀ
ethynyl)cyclopropane (8a) from 1,1,3ꢀtrichloroꢀ3ꢀphenylpropꢀ
1ꢀene (19a). Chloride 19a (152 mg, 0.687 mmol) was added at
∼20 °C to a mixture of 2,3ꢀdimethylbutꢀ2ꢀene (290 mg,
3.4 mmol), ButOK (310 mg, 2.74 mmol), and dodecane (100 mg)
in 3 mL of hexane. Approximately two minutes after the addiꢀ
tion was completed, the reaction mixture contained, along with
the starting trichloride and cyclopropane 8a, allene 22a and
alkyne 21a in the 1 : 1 ratio; their total content was 6% (GLC
data). The latter two compounds were identified by comparing
their retention times with those of authentic samples (see the
section "Reaction of dichloride 21a with a deficient amount of
ButOK"). The reaction mixture was stirred for 30 min and
analyzed by GLC, which showed the complete absence of the
starting trichloride 19a and intermediate compounds 21a and
22a. The yield of cyclopropane 8a was determined from the
ratio of its peak area with that of dodecane with a preꢀcaliꢀ
brated detector. The yield of 8a was 46%.
1
and 14e (GLC and H and 13C NMR data). The composition
of the mixtures obtained and the total yields and boiling points
of the reaction products are given in Table 2. The spectral
characteristics of cyclopropanes 12b,c,f and 14b,c,e are preꢀ
sented in Tables 4—8.
1
Compound 17. H NMR, δ: 0.91 (t, 3 H, CH3 in Bu, J =
7.0 Hz); 1.04 (s, 3 H, Me); 1.38 (s, 3 H, Me); 1.20—1.55 (m,
6 H, 3 CH2); 2.06 (dt, 2 H, —CH2CH=, J = 6.5 Hz, J =
6.5 Hz); 5.64 (dt, 1 H, —CH2CH=, J = 15.2 Hz, J = 6.5 Hz);
5.79 (d, 1 H, CBrCH=, J = 15.2 Hz). 13C NMR, δ: 14.0
(CH3CH2—); 21.4, 22.3, 22.8, 25.1, 26.2, 27.2, 31.3, 31.6
(CMe2, 2 C(CH3), 4 CH2, CBr); 131.3 and 133.6 (CH=CH).
MS, m/z: 230, 232 [M]+.
Reaction of 1,1,1,3ꢀtetrabromoꢀ3ꢀphenylpropane (4a) with
KOH in the presence of 2,3ꢀdimethylbutꢀ2ꢀene. A solution of
tetrabromide 4a (1 g, 2.3 mmol) in 1 mL of CH2Cl2 was added
to a mixture of KOH (1.8 g, 30 mmol), benzyltriethylammoꢀ
nium chloride (50 mg), and 2,3ꢀdimethylbutꢀ2ꢀene (570 mg,
6.8 mmol) in 10 mL of CH2Cl2. The reaction mixture was
stirred at ∼20 °C for 2 h. The course of the reaction was moniꢀ
tored by GLC. Then the reaction mixture was treated with
water, and the organic layer was separated. The organic mateꢀ
rial was extracted from the aqueous phase with ether (3×10 mL).
The combined organic layers were dried with magnesium sulꢀ
fate. Column chromatography of the residue on silica gel in
hexane gave a 1.7 : 1 mixture of bromides 14a and 15 (240 mg).
The spectral characteristics of cyclopropane 14a are given in
Tables 7 and 8.
Reactions of 3ꢀbromoꢀ1,1,1ꢀtrichloroheptane (2b) and
1,1,1,3ꢀtetrachloroheptane (3b) with a deficient amount of
ButOK. The reactions were carried out as described above for
the reactions of halides 2a and 3a with ButOK. After being
treated with water, the reaction mixture contained the starting
reagent (∼50%) and products 19c and 20b in the 1 : 3.5 ratio
(for 2b) or products 19b and 20b in the 1 : 1.2 ratio (for 3b)
(NMR and GLC data). The products were identified from the
1H NMR spectra of the resulting mixtures.
1
Compound 19b. H NMR, δ: 0.91 (t, 3 H, CH3 in Bu, J =
7.0 Hz); 1.20—2.00 (m, 6 H, 3 CH2); 4.75 (dt, 1 H, CHCl,
J = 11.1 Hz, J = 7.2 Hz); 6.10 (d, 1 H, CH=CCl2, J = 11.1 Hz).
Compound 19c. 1H NMR, δ: 0.91 (t, 3 H, CH3 in Bu,
J = 7.0 Hz); 1.20—2.00 (m, 6 H, 3 CH2); 4.66 (dt, 1 H,
CHBr, J = 11.1 Hz, J = 7.2 Hz); 5.98 (d, 1 H, CH=CCl2, J =
11.1 Hz).
2,2,3,3ꢀTetramethylꢀ1ꢀ(phenylvinylidene)cyclopropane (15).
1H NMR, δ: 1.40 (s, 6 H, 2 Me); 1.49 (s, 6 H, 2 Me); 6.20 (s,
1 H, CH=); 7.30—7.60 (m, 5 H, Ph). 13C NMR, δ: 21.3 (2 CH3);
22.0 (2 CH3); 31.4 (2 CMe2); 95.8 (=CH—); 99.1
(=C in cycloꢀC3); 126.4, 127.1, 128.5 (Ph); 136.8 (C(1), Ph);
182.9 (=C=). MS, m/z: 198 [M]+.
1
Compound 20b. H NMR, δ: 0.92 (t, 3 H, CH3 in Bu, J =
7.0 Hz); 1.20—1.55 (m, 4 H, 2 CH2); 2.18 (dt, 2 H, —CH2CH=,

Generation of (alkꢀ1ꢀynyl)halocarbenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 7, July, 2002
1253
J = 7 Hz, J = 6.5 Hz); 6.11 (d, 1 H, CHCCl3, J = 15.5 Hz);
6.27 (dt, 1 H, CH2CH=, J = 15.5 Hz, J = 7.2 Hz).
1ꢀBromoꢀ1ꢀfluoroheptꢀ2ꢀyne (27). 1H NMR, δ: 0.92 (t, 3 H,
CH3 in Bu, J = 7 Hz); 1.20—1.60 (m, 4 H, 2 CH2); 2.20—2.45
(m, 2 H, CH2C≡); 6.77 (dt, 1 H, —CHFBr, JH,F = 52 Hz, J =
1.7 Hz). 19F NMR, δ (CFCl3): –121.5 (d, —CHFBr, J =
52 Hz). MS, m/z: 113 [M – Br]+.
Reaction of 1,1,3ꢀtribromoꢀ1ꢀfluoroheptane (1b) with ButOK:
identification of intermediate products. Potassium tertꢀbutoxide
(158 mg, 1.41 mmol) was added at ∼20 °C to a solution of
tetrahalide 1b (500 mg, 1.41 mmol) in 5 mL of hexane. The
reaction mixture was stirred for 15 min and then treated with
water. The organic layer was separated, and the organic mateꢀ
rial was extracted from the aqueous phase with ether (3×10 mL).
The combined organic layers were dried with magnesium sulꢀ
fate, and the solvent was evaporated. The residue contained a
mixture of the starting compound 1b, transꢀ1,1ꢀdibromoꢀ1ꢀ
fluoroheptꢀ2ꢀene (24), and isomeric Eꢀ and Zꢀ1,3ꢀdibromoꢀ1ꢀ
fluoroheptꢀ1ꢀenes (25) in the 1 : 1.8 : 0.9 : 0.75 ratio (GLC and
NMR data). The total yield was 340 mg.
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos. 01ꢀ03ꢀ32674
and 00ꢀ15ꢀ97387).
References
1. K. N. Shavrin, V. D. Gvozdev, and O. M. Nefedov, Izv.
Akad. Nauk, Ser. Khim., 1998, 1185 [Russ. Chem. Bull.,
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2. K. N. Shavrin, V. D. Gvozdev, and O. M. Nefedov,
Mendeleev Commun., 1997, 144.
3. K. N. Shavrin, V. D. Gvozdev, and O. M. Nefedov, Izv.
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7. M. S. Kharash, O. Reinmuth, and W. H. Urry, J. Am.
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Compound 24. 1H NMR, δ: 0.88 (t, 3 H, CH3 in Bu,
J = 7 Hz); 1.20—1.55 (m, 4 H, 2 CH2); 2.06 (dt, 2 H,
—CH2CH=, J = 7 Hz, J = 6.5 Hz); 5.85—6.15 (m, 2 H,
—CH=CH—). 19F NMR, δ (CFCl3): –51.8 (d, CFBr2, J =
16.6 Hz). MS, m/z: 193, 195 [M – Br]+.
Compound Eꢀ25. 1H NMR, δ: 0.88 (t, 3 H, CH3 in Bu,
J = 7 Hz); 1.20—2.00 (m, 6 H, 3 CH2); 4.72 (dt, 1 H, CHBr,
J = 11.1 Hz, J = 7.2 Hz); 5.31 (dd, 1 H, CH=CFBr, J =
11.1 Hz, JH,F = 27.9 Hz). 19F NMR, δ (CFCl3): –69.2 (d,
=CFBr, J = 27.9 Hz). MS, m/z: 193, 195 [M – Br]+.
Compound Zꢀ25. 1H NMR, δ: 0.88 (t, 3 H, CH3 in Bu,
J = 7 Hz); 1.20—2.00 (m, 6 H, 3 CH2); 4.48 (dtd, 1 H, CHBr,
J = 10.9 Hz, J = 7.1 Hz, JH,F = 2.5 Hz); 5.71 (dd, 1 H,
CH=CFBr, J = 10.9 Hz, JH,F = 10.9 Hz). 19F NMR, δ (CFCl3):
–68.3 (dd, =CFBr, J = 10.9 Hz, J = 2.5 Hz). MS, m/z: 193,
195 [M – Br]+.
The mixture of the halides obtained (340 mg) was dissolved
in 5 mL of hexane, and ButOK (120 mg, 1.07 mmol) was added
at ∼20 °C. After 30 min, the starting tetrahalide 1b was comꢀ
pletely consumed (GLC data), and the reaction gave, along
with trihalides 24 and 25, two new products identified as
dihalides 26 and 27 in 12 and 5% yields, respectively. After
60 min, the reaction mixture contained transꢀ24 (45%), the
Eꢀisomer of 25 (25%), the Zꢀisomer of 25 (3%), allene 26
(15%), and alkyne 27 (5.5%) (GLC data). When the mixture
reacted with ButOK for 90 min, the relative content of prodꢀ
ucts 26 and 27 decreased to 12 and 5%, respectively. The reacꢀ
tion mixture was treated with water. The organic layer was
separated, and the organic material was extracted from the
aqueous phase with ether (3×10 mL). The combined organic
layers were dried with magnesium sulfate, and the solvent was
evaporated in vacuo at a bath temperature of no higher than
40 °C. The residue (164 mg) was analyzed by NMR spectrosꢀ
copy and GLꢀMS spectrometry.
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to, 1972.
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Sugimoto Kikuo, Fujimoto Tamotsu, Takashima Toshiyuki,
and Kondo Kiyosi, Bull. Chem. Soc. Jpn., 1986, 59, 221.
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Weyl), Stuttgart, Georg Thieme, 1989, B. E19b, Teil 1, 138.
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Weyl), Stuttgart, Georg Thieme, 1960, B. V/4, 773.
15. J. M. Birchall and R. N. Hasseldine, J. Chem. Soc., 1956, 16.
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J. Wiley and Sons, New York—London—Sydney—Toronꢀ
to, 1972.
1ꢀBromoꢀ1ꢀfluoroheptaꢀ1,2ꢀdiene (26). 1H NMR, δ: 0.92
(t, 3 H, CH3 in Bu, J = 7 Hz); 1.20—1.60 (m, 4 H, 2 CH2);
2.20—2.45 (m, 2 H, CH2CH=); 5.97 (dt, 1 H, —CH=, J =
6.5 Hz, JH,F = 1.6 Hz). 19F NMR, δ (CFCl3): –95.4 (d, =CFBr,
J = 1.6 Hz). MS, m/z: 150, 152 [M – C3H6]+.
Received December 21, 2001;
in revised form March 14, 2002