E,E-arnesols, farnesyl bromides, and ethyl farnesenates, and also of oligomeric silyl ethers

(V)-(IX) prepared by ozonolysis and further conversion of natural rubber.

2. Criteria are proposed for identifying Z- and E-isoprene units in polyisoprenoids.
3. The thermal stability of the Z configuration of isoprenoid units in the ozonolysis
products of natural rubber is confirmed.

LITERATURE CITED
I. J. P. Dusza, J. Org. Chem., 25, 93 (1960).
2. R. B. Bates, D. M. Gale, and B. J. Gruner, J. Org. Chem., 28, 1086 (1963).
3. J. W. de Haan and L. J. M. van de Ven, Tetrahedron Lett., 2703 (1971).
4. A. V. Semenovskii, V. A. Smit, and V. F. Kucherov, Izv. Akad. Nauk SSSR, Ser. Khim.,
1424 (1965).
5. N. Ya. Grigor'eva, I. M. Avrutov, A. V. Semenovskii, V. N. Odinokov, V. R. Akhunova,
and G. A. Tolstikov, Izv. Akad. Nauk SSSR, Ser. Khim., 382 (1979).
. M. W. Duch and D. M. Grant, Macromolecules, 3, 165 (1970).
7. G. I. Vergunova, I. S. Glukhoded, L. L. Danilov, G. I. Eliseeva, N. K. Kochetkov,
M. F. Troitskii, A. I. Usov, A. S. Shashkov, and V. N. Shibaev, Bioorg. Khim., 3, 1484
(1977).
. G. A. T o l s t i k o v , V. N. Odinokov, V. K. I g n a t y u k , A. V. Semenovskii, and A. M. Moiseen-
kov, Dokl. Akad. Nauk SSSR, 236, 901 (1977).

SYNTHESIS OF CYLCLOPROPANES BY REDUCTIVE CYCLIZATiON

OF POLYCHLOROALKANES CONTAINING A CC13 OR CC12 GROUP

R. Kh. Freidlina, A. A. Kamyshova, UDC 542.91:547.512

N. N. Posledova, and E. Ts. Chukovskaya

It is known that the cyclization of 1,3-dichloroalkanes in the presence of zinc gives

low yields of cyclopropanes. We have proposed a new approach to the synthesis of cyclo-
Propanes from polychloro derivatives in which one of the chlorine,containing groups involved
in dechlorination is a geminal dichloro- [i] or trichloromethyl group [2]. Various mono-,
di-, and trisubstituted cyclopropanes can be obtained in quite high yields, depending on the
nature of the substituents. The starting materials are readily available and can be prepared
by radical addition of CC14 or RCCI3 to unsaturated compounds [3].
The object of the present investigation has been to extend the range Of gem-trichl0ro-
alkanes which can be subjected to reductive cyclization and to determine the effect of u sub-
stituents on the process. We were particularly interested in the involvement of reactive
benzylic C1 atoms in cyclization and in studying the behavior of the vicinal CHCICH2CI
grouping. We investigated the action of Zn in ethanol in an HCI stream on l,l,l,3-tetra-
chloropropane (I), l, I, 1,3-tetrachloro-3-phenylpropane (II), 2,2,4-trichloro-4-phenylbutane
(III), and l,l,l,3,4-pentachlorobutane (IV) (Table I). In the case of tetrachloropropane (I),
we showed that the main product of reductive cyclization is cyclopropane (V) (see Table i),
with n-propyl chloride being formed as a by-product by reduction of the CC13 group
CCI,CH~CH2CI---*cyclo- C~Hs-1-n-C~H~Cl ( 1)
(I) (V) (VI)
The CC13 group in conjunction with a benzylic CI atom undergoes reductive cyclization to
form substituted cyclopropanes
cl
\ (2)
CClaCH~CHC1C~Hs---, >--CeH~ q- C I ~ C6H5q- C I ~ C 6 H s
(II) (VII) (VIII) (IX)
Institute of Heteroorganic Compounds, Academy of Sciences of the USSR, Moscow. Trans-
lated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 392-395, February,
1979. Original article submitted August 25, 1977.

362 0568-5230/79/2802-0362507.50 9 1979 Plenum Publishing Corporation

 TABLE i. Reaction of Polychloroalkanes (I)-(IV) with
Zinc in Ethanol
m

i Reaction products and yields,*g

reduction, de-
Starting material eyclopropane chlorination I . ,,
derivativ~ yield and isomeriza- ] ymm
tion products /

CCI3CH2CH2C1(I) (v) 75 (vI) 22

CC13CHzCHC1C6H~(II) (vii) 38 (X) 6
ci,- (viii) it
tram- (VIII) 4
(ix) tt
CH3CCIzCH~CHCICeH5(III) eis- (XI) 39 (xIv)
tram- (XI) 17 (xuI)
eL,- (xII) 3
tram- (XII) 3
CCI~CH2CHCICH~CI(IV) (XlX) 7 (XV) 46
(XX) (XVl) 6
(XVIII) (XVlI) 4

The yield of cyclic products (VII)-(IX) is 64%, the major product being phenylcyclopropane
(VII) (see Table I). An interesting feature of this reaction is the formation of chlori-
nated cyclopropanes (VIII) and (IX), indicating that the mechanism of reductive cyclization
is the same for compounds with CC13 and CC12 groups (the formation of chlorinated cyclopro-
panes has already been noted for compounds with CC12 groups [i]). It is clear that in both
cases the reaction begins with the 1,3-dechlorination of the RCCI2CH2CCI~ (R = Alk or CI).

The formation of chlorinated cyclopropanes (VIII) and (IX) from (If) and the absence of
significant amounts of analogous products in the cyclication of CCI3CH2CHCIAIk [2] confirms
the difference in chemical behavior noted for alkyl- and phenylcyclopropanes in other reac-
tions [4]. The preferential formation of the cis form of (VIII) (see Table 1) in the reduc-
tive cyclization of (II) possibly indicates that the phenyl group exerts a steric effect.
For comparison, we also studied the reductive cyclization of polychloroalkane (III)
Cl
CH3CC12CH2CHCICcH5~ CHs-~---C6H s + C H s ~ C ~ H 5 (3)
(m) (xi) (xu)
As i n t h e c a s e o f p o l y c h l o r o a l k a n e ( I I ) ( r e a c t i o n 2), t h e b e n z y l i c C1 atom i n ( I I I ) a l s o
participates i n c y c l i z a t i o n , g i v i n g compound (XI) as t h e major p r o d u c t and forming o n l y a
small amount o f c y c l o p r o p a n e ( X I I ) , which i s a p r o d u c t o f f u r t h e r r e d u c t i o n . Both t h e c i s
and t r a n s forms o f (XI) a r e o b t a i n e d , w i t h t h e former p r e d o m i n a t i n g .
The r e d u c t i v e c y c l i z a t i o n o f ( I I ) and ( I I I ) i s accompanied by c o m p e t e t i v e t o t a l r e d u c -
t i o n o f t h e s t a r t i n g m a t e r i a l s , g i v i n g a l k y l b e n z e n e s (X) and (XIV) i n a y i e l d o f 5-6% (see
Table 1). In a d d i t i o n , 4 - p h e n y l - 2 - b u t e n e (XIII) i s d e t e c t e d d u r i n g t h e c y c l i z a t i o n o f ( I I I ) .
Compound (XIII) i s e v i d e n t l y formed, by a n a l o g y w i t h [2], by i s o m e r i z a t i o n o f (XII) w i t h r i n g
opening.
In c o n t r a s t t o t h e d e s c r i b e d examples, t h e r e a c t i o n o f p o l y c h l o r o a l k a n e (IV) with Zn i n
e t h a n o l does not g i v e s u b s t i t u t e d c y c l o p r o p a n e s as t h e major p r o d u c t s . The main r e a c t i o n
path in this case is reduction of the CC13 group, resulting in the formation of 1,2-dichloro-
butane (XV) (see Table I). According to GLC and PMR data, secondary reaction products of
intermediate cyclopropane compounds are formed in small amounts: reduction gives (XVIII);
alkoxylation gives (XIX); and isomerization with ring expansion gives (XX)

CCI3CH2CHCICH~CI~ [[>--CHzCI]~ [>--CHs (4)

(IV) ~ (XVIII)

(XIX)
-I-F
(XX)

363
 Compounds (V), (VI), (X), (XII), (XVI), (XVII), and (XVIII) were identified by GLC
using authentic samples. Compounds (V)-(IX), (XI), (XIV), and (XV) were isolated in pure
form. The structure of the compounds obtained was confirmed by their PMR spectra (see ex-
perimental section).
The assignment of cis and trans structures to (XI) was made on the basis of the chemi-
cal shift of the benzylic proton in the cyclopropane ring (Hb). A higher chemical shift is
observed for the proton which is cis to the C1 atom (by analogy with [I]), i.e., in the cis
form of (XI). The PMR spectrum of mixtures of (XII) and (XIII), besides containing signals
from the protons of (XII), which are the same as the signals from pure (XII), also contains
multiplets assignable to (XIII) (~, ppm): 5.50 (CH=), 3.30 (CH~C6Hs) (see [5]), and 1.63
(CH3). The PMR data are confirmed by the Raman spectrum, which contains an absorption band
at 1650 cm -x, characteristic of a CH=CH group.

EXPERIMENTAL
The PMR spectra were obtained using a Hitachi--Perkin--Elmer R-20 instrument (60 MHz) for
50% solutions of the compounds in CC14, TMS standard, CHCI3; the chemical shifts are given
on the ~ scale (ppm). The Raman spectrum was recorded with a Ramanor HG2 S instrument using
an A 5145 ~ laser (250 MW). Gas--liquid chromatography (GLC) was performed using an LKhM-8MD
chromatograph (katharometer). The following columns were used for analytical determinations:
A (2 m x 3 mm), containing 15% E-301 silicone on Chromaton N-AW (0.20-0.25 mm); B (I m x 3
mm), containing 15% Carbowax 20 M on Chromaton N-AW (0.16-0.20 mm); C (3 m x 3 mm), contain-
ing 15% triethylene glycol dibutyrate on Zeolite 545 (0.20-0.25 ~ ) . Preparative separations
were effected using 1.3 m • 8 mm columns containing 0.25-0.32 mm supports with phases ana-
logous to A and B.
The preparation of l,l,l,3-tetrachloro-3-phenylpropane (II) and 2,2,4-trichloro-4-
phenylbutane (III) was effected by addition of CC14 or CCI3CH3 to styrene in the presence
of Fe(CO)s and hexamethylphosphoramide as described in [6]: (If), bp 96~ mm, nD 2~ =
1.5552 (cf. [7]), d~ 2~ = 1.3804; (III), bp I05~ mm (cf. [8]), nD 2~ = 1.5418, d42~ =
1.2493. The PMR spectra of (II) and (III) were in accord with the literature [7,8]; l,l,l,3,4-
pentachlorobutane (IV) is described in [3].
Reductive Cyclization of (I)-(IV). Cyclization was effected by the general method de-
scribed in [2] with a polychloroalkane:zinc molar ratio of 1:4 in ethanol with vigorous
mixing and constant passage of HCI gas. Total conversion of (I)-(IV) was achieved after
heating for 1-2 h. Gaseous reaction products were collected in a cold trap. At the end of
the experiment, the reaction mixture was decanted, diluted with water, and extracted with
CH2C12. The extracts were dried over MgS04 and distilled. The yields of products (VII)-(XV),
(XIX) and (XX) were calculated from chromatograms of the fractions produced by distillation.
The yields of (V), (XVI), (XVII), and (XVIII) were calculated from the PMR spectrum of the
condensate. The results are given in Table I. Compounds (V)-(IX), (XI), (XIV), and (XV)
were isolated in pure form. Mixtures of (XII) and (XIII), and a mixture of (XIX) and (XX),
were obtained.
PMR spectrum of cyclopropane (V): 0.22 s [CH2, cyclopropane ring protons (H CPR)] (cf.
[9]). For propyl chloride (VI), nD 2~ = 1.3886; PMR spectrum: 1.00 t (3H, CH3), 1.75 m ~2H,
CH2), 3.50 t (2H, CH2CI).
Phenylcyclopropane (VII), bp 64~ mm; nD 2~ = 1.5337; d~ 2~ = 0.9428 (cf. [i0]); PMR
spectrum: 0.63 m, 0.83 m (4H, H CPR), 1.75 m (IH, Hb), 7.08 d (5H, C6Hs) (cf. [i]). l-
Chloro-2-phenylcyclopropane (VIII) (mixture of cis and trans isomers), nD 2~ = 1.5485 (cf.
[12]); d42~ = 1.1153; PMR spectrum: 0.85-1.45 (2H, H CPR), 2.10 m (IH, Hb), 3.00 m (IH, H
CPR, CHCI), 7.14 s, 7.23 s (5H, C6Hs cis and trans) (cf. [12]). l,l-Dichloro-2-phenylcyclo-
propane (IX), nD 2~ = 1.5518 (cf. [13]); d42~ = 1.2268; PMR spectrum: 1.63 d, 1.78 d (2H, H
CPR), 2.75 t (1H, H b). 7.25 s (5~, C6ns) (cf. [9]).
l-Chloro-l-methyl-2-phenylcyclopropane (XI) (mixture of cis and trans isomers), bp 79-
8!~ mm; nD 2~ = 1.5318. Found: C 71.87; H 6.74; C1 21.25%. CIoH:ICI. Calculated: C
72.07; H.6.65; C1 21.28%. For cis-(XI), nD z~ = 1.5301; d, 2~ = 1.0629; PMR spectrum: 1.13
t~ 1.50 m (2H, H CPR), 1.28 s (3H, CH~), 2.63 q (IH, Hb), 7.25 s (5H, C6H5). For trans-(XI),
nD 2~ = 1.5349: d42~ = 1.0714; PMR spectrum: 1.25 m, 1.43 m (2H, H CPR), 1.70 s (3H, CH3),
2.08 m (IH, H~), 7.30 s (5H, C6H5). PMR spectrum of authentic l-methyl-2-phenylcyclopropane
(XII) (40% cis, 60% trans): 0.35-0.88 (cis-CH3 and H CPR), 0.88-1.20 (trans-CH~ and H CPR),

364
1.43 q (trans-Hb), 1.98 m (cis-Hb), 7.07 d (cis-C6Hs), 7.16 s (trans-C6Hs) (cf. [12]). Pre-
parative GLC on column B gave a fraction with nD 2~ = 1.5204; d42~ = 0.9091. Found: C
90.42; H 9.13%. CIoH12. Calculated: C 90.85; H 9.15%. Besides signals assignable to
cis- and trans-(XII), the PMR spectrum of this fraction also contained signals belonging to
4-phenyl-2-butene (XIII): 1.63 d (CH___3CH=), 3.33 m (C6HsCH2CH=), 5.60 m (CH=). The cis-(XII)
:trans-(XII):(XIII) ratio was 42:38:19%. PMR spectrum of n-butylbenzene (XIV): 0.85 t (3H,
CH3), 1.4 m (4H, 2CH2), 2.46 t (2H, CHz), 7.15 s (5H, CsHs).
For 1,2-dichlorobutane (XV), nD 2~ = 1.4418; d42~ = 1.0895 (cf. [14]); PMR spectrum:
1.03 t (3H, CH3), 1.80 m (2H, CH2), 3.73 m (2H, CH2CI), 3.88 m (IH, CHCI). For a mixture
of cyclopropylmethyl ethyl ether (XIX) and cyclobutyl ethyl ether (XX) (~i:I). Found: C
71.10; H 12.05%. C6H120. Calculated: C 71.95; H 12.08%. Mixture's PMR spectrum: -0.15
m, 0.15 m, 0.48 m (5H, H CPR), 0.83 t, 0.85 t (6H, 2CH3), 1.48 m, 1.73 m (6H, cyclobutane
ring protons, H CBR), 2.92 d, 3.05 q, 3.15 q (6H, 30CH2), 3.58 m (IH, H CBR) (of. [15])o
The authors wish to thank L. D. Sychkova for supplying the sample of l-methyl-2-
phenylcyclopropane.

CONCLUSIONS
i. The reductive cyclization of polychloroalkanes of formula RCHCICH2CCI 3 (R = H or
C6H5) to form cyclopropane compounds is effected by treatment with zinc in ethanol.
2. The formation of chlorinated cyclopropanones by cyclization of polychloroalkanes of
the type RCCI2CH2CHCIC6H5 (R = C1 or CH3) indicates that the mechanism of reductive cycliza-
tions is the same for compounds with CC12 and CC13 groups, starting with 1,3-dechlorination.

3. The presence of a h C C i - C C l ~ f r a g m e n t in the y position to the CC13 group hinders

reductivecyclization.

LITERATURE CITED
1 A . A . Kamyshova, S. D. Polishchuk, E. Ts. Chukovskaya, and R. Kh. Freidlina, Izv. Akad.
Nauk SSSR, Ser. Khim., 185 (1977).
2. A . A . Kamyshova, E. Ts. Chukovskaya, and'R. Kh. Freidlina, Dokl. Akad. Nauk SSSR, 233,
122 (1977).
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5. F. A. Bovey, NMR Data Tables for Organic Compounds, Wiley-Interscience, New York, Vol.
l, No. 1995, p. 278.
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Nauk SSSR, Ser. Khimo, 174 (1977).
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8. T. Sato, M. Seno, and T. Asahara, Seisan Kenkyu, Mon. Inst. Ind. Sci. Uni--v. Tokyo, 24,
230 (1972).
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( i 9 7 4 ) , p. 20.
10. N. M. Kizhner, Zh. Russk. Fiz.-Khim. Obshch., 4_]7, 1106 (1915).
ii. K. B. Wiberg, D. E. Barth, and P. H. Schertler, J. Org. Chem., 38, 378 (1973).
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13. P. Weyerstahl, D. Klamann, C. Finger, F. Nerdel, and J. Buddrus, Ber., I00, 1858 (1967).
14. E. H. Huntress, Organic Chlorine Compounds, J. Wiley, Chapman and Hall (1948), p. 1063.
15. E. B. Whipple and G. R. Evanega, Org. Magn. Reson., 2, i (1970).

365