Condensation of phenols and alcohols with 1,2-dichloroethyl-gem- dichlorocyclopropanes

Article abstract of DOI:10.1134/S1070363213020187

Dichlorocarbenation of 3,4-dichlorobut-1-ene by Makosza method results in the stereoisomeric 1,2-dichloroethyl-gem-dichlorocyclopropanes in a 1:1 ratio. The reaction of the mixture of stereoisomeric gem-dichlorocyclopropanes with phenols and alcohols in dimethylsulfoxide in the presence of solid sodium hydroxide gives rise to the corresponding ketals containing the exocyclic double and triple bonds. In this case, the acetylene compounds dominate in the reaction products. The ratio of the reaction products containing the double and triple bonds depends on the nucleophile nature.

Full text of DOI:10.1134/S1070363213020187

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 2, pp. 348–352. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.N. Kazakova, L.V. Spirikhin, S.S. Zlotsky, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 2, pp. 294–298.
Condensation of Phenols and Alcohols
with 1,2-Dichloroethyl-gem-dichlorocyclopropanes
A. N. Kazakovaa, L. V. Spirikhinb, and S. S. Zlotskya
a Ufa State Petroleum Technological University, ul. Kosmonavtov 1, Ufa, 450062 Russia
e-mail: a-kazakova@inbox.ru
b Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, Russia
Received December 12, 2011
Abstract―Dichlorocarbenation of 3,4-dichlorobut-1-ene by Makosza method results in the stereoisomeric 1,2-
dichloroethyl-gem-dichlorocyclopropanes in a 1:1 ratio. The reaction of the mixture of stereoisomeric gem-
dichlorocyclopropanes with phenols and alcohols in dimethylsulfoxide in the presence of solid sodium
hydroxide gives rise to the corresponding ketals containing the exocyclic double and triple bonds. In this case,
the acetylene compounds dominate in the reaction products. The ratio of the reaction products containing the
double and triple bonds depends on the nucleophile nature.
DOI: 10.1134/S1070363213020187
The chlorination of butadiene affords 3,4-
dichlorobut-1-ene I in a high yield, which is widely used
in organic synthesis [1].
compounds IIa (9.4 Hz) and IIb (5 Hz) indicate the
threo- and erythro- configuration of compounds IIa
and IIb, respectively
In the 13C NMR spectra of IIa the signals of the
carbon atoms of CHCl- and СH2Cl-groups are in a
weaker field at 60.54 and 47.96 ppm, than similar
signals of the carbon atoms in the spectrum of
compound IIb (60.27 and 47.48 ppm, respectively).
The upfield shift of the signals of the carbon atoms in
the spectrum of erythro-isomer indicates a stronger
syn-interaction between the atoms of CHCl- and
СH2Cl-groups than in the threo-structure. On the
contrary, the signals of the СН2- and СН-carbon atoms
of the cyclopropane ring in compound IIb are in a
weaker field as compared with the signals of similar
atoms in IIa (the chemical shifts of the СН2- and СН-
carbon atoms in the erythro- and threo-isomer are
28.07, 34.87 and 27.29, 34.45 ppm, respectively).
We used compound I to obtain the stereoisomeric
1,2-dichloroethyl-gem-dichlorocyclopropanes II by the
Makosza method [2].
The diastereoisomers IIa and IIb (1:1) were
separated by vacuum distillation and characterized by
the 1H and 13C NMR spectroscopy and mass spectrometry.
H H
Cl H
H
Cl
H
:CCl2
Cl
Cl
+
Cl
Cl H
H H
Cl
Cl
Cl
Cl
IIa
IIb
I
Thus, in the case of compound IIa, in the 1H NMR
spectrum the signal of the CH-proton of the
cyclopropane ring is observed as a doublet of doublets
of doublets at 2.5 ppm, with the spin-spin coupling
The resulting mixture of stereoisomeric gem-di-
chlorocyclopropanes IIa and IIb was we used in the
O-alkylation of phenols III in dimethyl sulfoxide
(DMSO) in the presence of solid NaOH.
3
3
3
constants J3а–2 7.7, J3b–2 10.4, J2–1' 9.4 Hz, whereas
the signal of the similar proton in the spectrum of
compound IIb appears at 2.05 ppm as a doublet of
The reaction is complete at room temperature
within 15–20 min and results in ketals with the exo-
cyclic double (IVa–IVc) and triple (Va–Vc) bonds.
3
doublets of doublets with the coupling constants J3b–2
3
3
7.7, J3а–2 10.4, J2–1' 5 Hz. According to the literature
data [3], the values of the spin-spin coupling constants
of the CH-proton of the cyclopropane ring for
The total yield of compounds IV and V equals 70–
80% and is independent of the nature of the aromatic
348

CONDENSATION OF PHENOLS AND ALCOHOLS
Cl
349
OH
R2
O
O
O
O
R1
R1
R1
R1
R1
DMSO
NaOH
+ IIa, IIb
_HCl
_HCl
R2
R2
IVa_IVc
R2
R2
Va_Vc
IIIa_IIIc
R1 = R2 = H (IIIa, IVa, Va); R1 = CH3, R2 = H (IIIb, IVb, Vb); R1 = H, R2 = Cl (IIIc, IVc, Vc).
reactant IIIa–IIIc. However, the nature and position of
the substituent affect the ratio of the ethylene and
acetylene structures (IVa–IVc/Va–Vc). In the reaction
with phenol IIIa the yield of acetylene ketal Va is
much higher, while in the reaction with p-chlorophenol
IIIc the yield of the fully dehydrochlorinated product
Vc is only 2-fold higher than that of the partially
dehydrochlorinated product IVc. However, in the case
of alcohols of linear structure [allyl (VIa) and butyl
(VIb)] the total yield of similar ketals VIIa, VIIb,
VIIIa and VIIIb) is much lower (20–30%).
In this case, the acetylene product VIII dominates
in the reaction products.
Earlier we mentioned the elimination of the
hydrogen halides in phenylpolyhaloalkyl ethers in the
study of the O-alkylation of phenols and alcohols with
polyhaloalkanes. [4]
The individual compounds IVa–IVc, Va–Vc, as
well as a mixture of isomers VIa, VIb and VIIa, VIIb
were isolated by column chromatography from the
reaction mixture of phenols IIIa–IIIc and alcohols
VIa, IVb with the reagents IIa, IIb.
Phenol
IIIа
Yield, %
In the 1H NMR spectrum of compound IVc the CH-
proton of the cyclopropane ring is observed at
2.40 ppm as a doublet of doublets with the spin-spin
coupling constants 3J2–3a 7.4, 3J2–3b 10.2 Hz. The trans-
positioned СН2-proton of the cyclopropane ring
6 (IVа)
15 (IVb)
23 (IVc)
71 (Vа)
58 (Vb)
47 (Vc)
IIIb
IIIc
DMSO
NaOH
Cl
R
+ IIa, IIb
OH
_HCl
_HCl
RO OR
RO
OR
VIa, VIb
VIIIa, VIIIb
VIIa, VIIb
R = CH2=CHCH2 (VIa, VIIa, VIIIa); C4H9 (VIb, VIIb, VIIIb).
appears as a doublet of doublets at 1.56 ppm (2J 6.9,
3J3a–2 7.4 Hz), while the cis-positioned СН2-proton
appears as a doublet of doublets in a weak field at
to the chlorine atom, is observed as a doublet at
5.28 ppm (2J 1.4 Hz), while the trans-positioned proton
is observed as a doublet in a weak field (5.41 ppm,
2J 1.4 Hz). A multiplet in the range of 7.08–7.27 ppm
belongs to the protons of the aromatic ring. The
structures of compounds VIa, IVb, VIIa, VIIb were
identified in a similar way.
3
1.75 ppm (2J 6.9, J3b–2 10.2 Hz). The proton of the
terminal double bond, which is cis-positioned relative
Alcohol
Yield, %
The mass spectra of compounds IVa–IVc contains
low-intensive peaks (<1%) of the molecular ions. The
main decay directions are caused by eliminating the
halogen ion and aryloxy radical. The most abundant
4 (VIIа)
6 (VIIb)
26 (VIIIа)
14 (VIIIb)
VIа
VIb
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350
KAZAKOVA et al.
ions are [ArOH]+· with m/z (83%), 108 (100%),
128/130 (100%) in the spectra of compounds IVa–
IVc, respectively.
length 2 m, 5% SE-30 on a Chromaton N-AW carrier).
The TLC analysis was performed using Silufol plates
(Merk) eluting with a hexane–AcOEt mixture, 98:2.
The preparative separation was carried out by column
chromatography on silica gel eluting with hexane with
increasing ethyl acetate content of 5 to 100%.
1
The H NMR spectrum of compound Vc contains
the CH-proton of the cyclopropane ring as a doublet of
doublets of doublets at 2.11 ppm (3J2–3a 6.9, 3J2–3b 10.5,
4J2–2' 2.2 Hz). The trans- positioned СН2-proton of the
cyclopropane ring appears as a doublet of doublets at
General procedure of dihalocarbenation. To a
mixture of 0.1 mol of 3,4-dichlorobut-1-ene I, 0.2 g of
a phase transfer catalyst (catamine AB in 300 ml of
chloroform) was added dropwise 320 g of 50% NaOH
solution at 40°C under stirring within 6 h. Then the
mixture was stirred for 2 h at the same temperature.
The reaction mixture was washed with water until the
neutral reaction. The extract was dried over calcined
MgSO4. The solvent was evaporated, and the residue
was distilled in a vacuum.
3
1.49 ppm (2J 6.3, J2–3a 6.9 Hz), while the cis-
positioned СН2-proton is observed as a doublet of
3
doublets in a weaker field at 1.70 ppm (2J 6.3, J2–3b
10.5 Hz). A doublet signal at 1.98 ppm (4J2–2' 2.2 Hz)
belongs to the proton of the terminal triple bond. A
multiplet at 7.05–7.27 ppm corresponds to the
aromatic ring protons. The structures of compounds
Va, Vb, VIIIa, VIIIb were identified in a similar way.
(2R*)-1,1-Dichloro-2-[(1S*)-1,2-dichloroethyl]-
cyclopropane (IIа, threo-diastereomer). Yield 40%,
colorless liquid, bp 96°С (2 mm Hg). 1Н NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.50 d.d (1Н, С3На,
2J 7.4, 3J 7.7), 1.88 d.d (1Н, С3Нb, 2J 7.4, 3J 10.4), 2.05
The mass spectra of compounds Va–Vc are
characterized by the low-intensive peaks (≤ 1%).
Acetylene ketals Va–Vc are capable of undergoing
cleavage of the СН2СО moiety from the ions produced
with the release of aryloxy radical from the М+· ion,
and the peaks of these ions have a maximum intensity
(100%) [m/z 115, 129, 149/151 for compounds Va–
Vc, respectively]. Compounds VIIa, VIIb, VIIIa,
VIIIb are characterized by the absence of the
molecular peaks (<0.1%). The main decay direction is
caused by the breaking of bonds with oxygen and the
formation of oxonium ions, which then loose the olefin
molecule from the second alkoxy group.
d.d. d (1Н, С2Н, J 7.7, J 10.4, J 9.4), 3.76–3.96 m
(3Н, С1'НСl, C2'H2Cl). 13С NMR spectrum (CDCl3),
δС, ppm: 27.29 (С3Н2), 34.45 (С2Н), 47.96 (С2'Н2Cl),
58.48 (С1Cl2), 60.54 (C1'HCl). Mass spectrum, m/e
(Irel, %): 206/208/210/212 (<1) [М]+, 171/173/175 (1)
[М – Cl]+, 157/159/161 (5/4/1) [М – СН2Cl]+, 144
(12/11/3), 135 (11/8/1), 109/111/113 (100/61/10),
96/98/100 (15/10/3), 75/77 (48/15), 51 (15).
3
3
3
(2R*)-1,1-Dichloro-2-[(1R*)-1,2-dichloroethyl]-
cyclopropane (IIb, erythro-diastereomer). Yield
Thus, the diastereoisomeric 1,2-dichloroethyl-gem-
dichlorocyclopropanes were obtained via the
dichlorocarbenation by the Makosza method. The
reactions of the obtained 1,2-dichloroethyl-gem-
dichlorocyclopropanes with phenols and alcohols in
DMSO are a convenient method of the synthesis of
ketals of chlorovinyl- and ethynylcyclopropanes.
1
40%, colorless liquid, bp 99°С (2 mm Hg). Н NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.50 d.d (1Н, С3Нa,
2J 7.4, 3J 7.7), 1.87 d.d (1Н, С3Нb, 2J 7.4, 3J 10.4), 2.05
3
3
3
d.d. d (1Н, С2Н, J 7.7, J 10.4, J 5.0), 3.75–3.94 m
(3Н, С1'НСl, C2'H2Cl). 13С NMR spectrum (CDCl3),
δС, ppm: 28.07 (С3Н2), 34.87 (С2Н), 47.48 (С2'Н2Cl),
58.48 (С1Cl2), 60.27 (C1'HCl). Mass spectrum, m/e
(Irel, %): 206/208/210/212 (<1) [М]+, 171/173/175
(0.5) [М – Cl]+, 157/159/161 (2/1/0.3) [М – СН2Cl]+,
144 (12/11/3), 135 (11/8/1), 109/111/113 (100/61/10),
96/98/100 (11/8/2), 75/77 (32/10), 51 (11).
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on a
Bruker AM-300 spectrometer (300.13 and 75.47 MHz,
respectively) in CDCl3 relative to internal TMS. The
GC-MS analysis was performed on a Shimadzu
GCMS-QP2010 Plus instrument (EI, 70 eV; an ion
source temperature 200°C, the direct input temperature
40–290°C, the heating rate 12 deg min–1). The GLC
analysis was performed on a LKhM-8MD chroma-
tograph equipped with a thermal conductivity detector,
carrier gas helium (flow rate 1.5 l h–1, the column
Reaction of phenols IIIа–IIIc and alcohols VIa
and VIb with a 1,2-dichloroethyl-gem-dichloro-
cyclopropanes IIa and IIb mixture. A mixture of
7.5 mmol of phenol IIIа–IIIc (or 12.5 mmol of
alcohol VIa or VIb), 15 mmol of NaOH (or 25 mmol
in the case of alcohols VIa or VIb) in 2.1 ml of DMSO
was stirred at 55–60°С for 1 h. Then to the mixture
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CONDENSATION OF PHENOLS AND ALCOHOLS
351
was added a solution of 2.5 mmol of IIa or IIb in 1 ml
of DMSO at 20°С. The reaction mixture was diluted
with 30 ml of water and extracted with chloroform.
The organic layer was washed with 20 ml of 20%
NaOH solution, then with water to pH 7, and dried
over MgSO4. Chloroform was evaporated in a vacuum.
The residue was chromatographed on silica gel (100–
400 µm, hexane–AcOEt, 98:2).
1,1'-[(2-Ethynylcyclopropane-1,1-diyl)bis(oxy)]-
bis(2-methylbenzene) (Vb). Yield 58%, colorless
liquid, Rf 0.32 (hexane–AcOEt, 98:2). 1Н NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.57 d.d (1Н, С3На,
2J 6.3, 3J 7.4), 1.85 d.d (1Н, С3Нb, 2J 6.3, 3J 10.3), 2.08
d (1Н, ≡С2'Н, J 1.9), 2.20 d.d.d (1Н, С2Н, J 7.4, J
10.3, 4J 1.9), 2.28 s (3Н, СН3), 2.37 s (3Н, СН3), 6.98–
7.57 m (8Н, Ph). 13С NMR spectrum (CDCl3), δС,
ppm: 16.36, 16.42 (CH3), 20.10 (С3Н2), 32.65 (С2Н),
66.52 (≡С2'Н), 80.71 (С1'≡), 86.94 (С1), 114.71, 114.89
(ortho-Ph), 122.02 (para-Ph), 126.78, 126.90, 130.88
(meta-Ph), 126.72, 127.23 (СН3–С), 153.77 (Ph). Mass
spectrum, m/e (Irel, %): 278 [М]+ (<1), 171 [М – PhO·]+
(6), 170 [М – PhOH]+ (3), 142 (6), 129 (100), 108
(53), 91 (23), 77 (8), 65 (14).
4
3
3
1,1'-[(2-(1-Chlorovinyl)cyclopropane-1,1-diyl)bis-
(oxy)]dibenzene (IVа). Yield 6%, colorless liquid, Rf
0.31 (hexane–AcOEt, 98:2). 1Н NMR spectrum (CDCl3),
δ, ppm (J, Hz): 1.57 d.d (1Н, С3На, 2J 6.6, 3J 7.4), 1.77
2
3
3
d.d (1Н, С3Нb, J 6.6, J 10.5), 2.40 d.d (1Н, С2Н, J
7.4, J 10.5), 5.30 d (1Н, =С2'На, J 1.5), 5.41 d (1Н,
=С2'Нb, 2J 1.5), 6.97–7.28 m (10Н, Ph). Mass
spectrum, m/e (Irel, %): 286/288 [М]+ (<1), 251
[М – Cl]+ (2), 193/195 [М – PhO·]+ (19/5), 157 (63),
151/153 (50/21), 129 (60), 115 (72), 94 (83), 77 (100),
65 (22), 51 (49).
3
2
1,1'-[(2-(1-Chlorovinyl)cyclopropane-1,1-diyl)bis-
(oxy)]bis(4-chlorobenzene) (IVc). Yield 23%, color-
1
less liquid, Rf 0.30 (hexane–AcOEt, 98:2). Н NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.56 d.d (1Н, С3На,
2J 6.9, 3J 7.4), 1.75 d.d (1Н, С3Нb, 2J 6.9, 3J 10.2), 2.40
1,1'-[(2-Ethynylcyclopropane-1,1-diyl)bis(oxy)]-
3
3
2
d.d (1Н, С2Н, J 7.4, J 10.2), 5.28 d (1Н, =С2'На, J
dibenzene (Vа). Yield 71%, white crystals, mp 63–
1.4), 5.41 d (1Н, =С2'Нb, J 1.4), 7.08–7.27 m (8Н,
2
1
65°С, Rf 0.26 (hexane–AcOEt, 98:2). Н NMR spec-
Ph). Mass spectrum, m/e (Irel, %): 354/356/358
2
trum (CDCl3), δ, ppm (J, Hz): 1.52 d.d (1Н, С3На, J
[М]+ (<1), 319/321/323 [М
–
Cl]+ (5/3/0.6),
6.2, 3J 7.0), 1.75 d.d (1Н, С3Нb, 2J 6.2, 3J 10.2), 2.01 d
227/229/231 [М – PhO·]+ (13/9/2), 191/193 (31/11),
185/187/189 (92/61/11), 163/165 (17/6), 149/151
(41/14), 128/130 (100/30), 111/113 (43/14), 99/101
(20/7), 75 (26), 63 (8).
4
3
3
(1Н, ≡С2'Н, J 2.1), 2.15 d.d.d (1Н, С2Н, J 7.0, J
10.2, 4J 2.1), 7.02–7.35 m (10Н, Ph). 13С NMR
spectrum (CDCl3), δС, ppm: 16.03 (С2Н), 21.48
(С3Н2), 66.5 (≡С2'Н), 80.26 (С1'≡), 87.42 (С1), 116.77,
117.22 (ortho-Ph), 122.59 (para-Ph), 129.27, 129.48
(meta-Ph), 155.60, 155.93 (Ph). Mass spectrum, m/e
(Irel, %): 250 [М]+ (<1), 157 [М – PhO·]+ (5), 156
[М – PhOH]+ (3), 128 (26), 115 (100), 94 (28), 77
(29), 65 (9), 51 (8).
1,1'-[(2-Ethynylcyclopropane-1,1-diyl)bis(oxy)]-
bis(4-chlorobenzene) (Vc). Yield 47%, colorless
1
liquid, Rf 0.27 (hexane–AcOEt, 98:2). Н NMR spec-
2
trum (CDCl3), δ, ppm (J, Hz): 1.49 d.d (1Н, С3На, J
6.3, 3J 6.9), 1.70 d.d (1Н, С3Нb, 2J 6.3, 3J 10.5), 1.98 d
4
3
3
(1Н, ≡С2'Н, J 2.2), 2.11 d.d. d (1Н, С2Н, J 6.9, J
1,1'-[(2-(1-Chlorovinyl)cyclopropane-1,1-diyl)bis-
(oxy)]bis(2-methylbenzene) (IVb). Yield 15%, white
crystals, mp 65–67°С, Rf 0.37 (hexane–AcOEt, 98:2).
1Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.62 d.d
(1Н, С3На, 2J 6.8, 3J 7.4), 1.87 d.d (1Н, С3Нb, 2J 6.8, 3J
4
10.5, J 2.2), 7.05–7.27 m (8Н, Ph). Mass spectrum,
m/e (Irel, %): 318/320/322 [М]+ (1), 191/193 [М – PhO·]+
(2/0.7), 190/192 [М – PhOH]+ (2/0.7), 162/164 (6/2),
149/151 (100/32), 128/130 (44/14), 111/113 (14/5),
99/101 (5/2), 75 (9), 63 (3).
3
3
10.2), 2.22 d (6Н, СН3), 2.43 d.d (1Н, С2Н, J 7.4, J
10.2), 5.36 d (1Н, =С2'На, J 1.4), 5.44 d (1Н, =С2'Нb,
A mixture of 1,1-bis(allyloxy)-2-(1-chlorovinyl)-
cyclopropane (VIIа) and 1,1-bis(allyloxy)-2-ethynyl-
cyclopropane (VIIIа). Yield 4 (VIIа) and 26%
(VIIIа), colorless liquid, Rf 0.24 (hexane–AcOEt,
2
2J 1.4), 6.90–7.62 m (8Н, Ph). 13С NMR spectrum
(CDCl3), δС, ppm: 16.21 (CH3), 21.63 (С3Н2), 32.65
(С2Н), 87.51 (С1), 114.26 (=С2'Н2), 115.16 (ortho-Ph),
122.08 (para-Ph), 126.57, 130.88 (meta-Ph), 127.65
(СН3–С), 137.59 (=С1'Сl), 154.22 (Ph). Mass
spectrum, m/e (Irel, %): 314/316 [М]+ (<1), 279 [М –
Cl]+ (6), 207/209 [М – PhO·]+ (25/8), 171 (26),
165/167 (63/21), 143 (26), 129 (42), 108 (100), 91
(59), 77 (15), 65 (31).
1
98:2). Н NMR spectrum (CDCl3), δ, ppm (J, Hz):
0.88 d.d [1Н, С3На, 2J 6.6, 3J 7.2 (VIIа)], 1.18 d.d [1Н,
С3На, 2J 5.5, 3J 6.4 (VIIIа); 1Н, С3Нb (VIIа)], 1.33 d.d
2
3
[1Н, С3Нb, J 5.5, J 10.0 (VIIIа)], 1.76 d.d. d [1Н,
С2Н, 3J 6.4, 3J 10.0, 4J 2.2 (VIIIа)], 1.91 d [1Н, ≡С2'Н,
4J 2.2 (VIIIа)], 2.09 d.d [1Н, С2Н, J 7.2, J 10.0
3
3
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KAZAKOVA et al.
4
3
(VIIа)], 4.07–4.19 m [4Н, СН2–О (VIIIа)], 4.20–4.38
m [4Н, СН2–О (VIIа)], 5.10–5.35 m [4Н, СН2=
(VIIIа); 4Н, СН2= (VIIIа), 2Н, =С2'На, =С2'Нb
(VIIIа)], 5.82–6.04 m [2Н, =СН (VIIIа); 2Н, =СН
(VIIIа)]. Mass spectrum (VIIа), m/e (Irel, %): 214/216
(<0.1) [М]+, 179 [М – Cl]+ (3), 173/175 (3/1)
≡С2'Н, J 2.3 (VIIIb)], 2.01 d.d [1Н, С2Н, J 7.0,
3J 10.0 (VIIb)], 3.53–3.62 m (8Н, СН2–О), 5.12 d
[1Н, =С2'На, J 1.3 (VIIb)], 5.23 d [1Н, =С2'Нb, J 1.3
(VIIb)]. Mass spectrum (VIIb), m/e (Irel, %): 246/248
[М]+ (<0.1), 211 [М – Cl]+ (<1), 210 [М – HCl]+ (<1),
173/175 [М – С4Н9O·]+ (<1), 155 (20), 134/136 (6/2),
117/119 (6/2), 99 (100), 89 (7), 57 (42). Mass
spectrum (VIIIb), m/e (Irel, %): 210 [М]+ (<1), 153
2
2
· +
[М – С3Н3 ] , 157/159 [М – С3Н5О·]+ (2/0.7), 155 (2),
151 (5), 137 (19), 131/133 (28/9), 127 (16), 121 (5),
117/119 (25/11), 115 (30), 113 (18), 109 (24), 97 (13),
95 (24), 93 (100), 91 (74), 88 (63), 81 (33), 79 (25), 77
(44), 75 (12), 67 (30), 65 (9), 55 (30), 53 (70), 42 (18).
Mass spectrum (VIIIа), m/e (Irel, %): 178 (<1) [М]+,
· +
[М – С4Н8 ] (3), 137 [М – С3Н5О·]+ (4), 135 (15), 107
(100), 83 (38), 81 (30), 79 (65), 74 (3).
REFERENCES
· +
137 [М – С3Н5 ] (4), 121 [М – С3Н5О·]+ (6), 119 (12),
109 (24), 95 (27), 93 (20), 91 (100), 81 (64), 79 (66),
77 (84), 67 (48), 65 (21), 57 (6), 55 (98), 52 (64), 42
(18).
1. Yukel’son, I.I., Tekhnologiya osnovnogo organiches-
kogo sinteza (Technology of Organic Synthesis),
Moscow: Khimiya, 1968, p. 712.
2. Zefirov, N.S., Kazimirchik, I.V., and Lukin, K.L.,
A mixture of 1,1-dibuthoxy-2-(1-chlorovinyl)
cyclopropane (VIIb) and 1,1-dibuthoxy-2-ethynyl-
cyclopropane (VIIIb). Yield 6 (VIIb) and 14%
(VIIIb), colorless liquid, Rf 0.27 (hexane–AcOEt,
Tsikloprisoedinenie
dikhlorkarbena
k
olefinam
(Cycloaddition of Dichlorocarbene to Olefins), Moscow:
Nauka, 1985.
1
3. Günther, H., NMR Spectroscopy: An Introduction,
98:2). Н NMR spectrum (CDCl3), δ, ppm (J, Hz):
2
3
0.93 t (12Н, СН3), 1.10 d.d [1Н, С3На, J 5.3, J 6.3
(VIIIb)], 1.24 m [8Н, СН2–СН3 (VIIb, VIIIb); 8Н,
СН2–СН2–СН3 (VIIb, VIIIb); 1Н, С3Нb (VIIIb); 2Н,
С3На, С3Нb (VIIb); 1Н, С2Н (VIIIb)], 1.87 d [1Н,
New York: Wiley, 1980.
4. Bogomazova, A.A., Zlotskii, S.S., and Kunakova, R.V.,
Izv. vuzov, Ser. Khim. i Khim. Tekhnol., 2011, vol. 54,
no. 4, p. 10.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 2 2013