T H E R M A L D E C O M P O S I T I O N O F
C Y C L O P R O P Y L A C E T Y L P E R O X I D E
T . N. S h a t k i n a , K . S. M a z e [ ' ,
and O. A . R e u t o v
UDC 541.12.036:547.512=39
The thermal decomposition of cyctoprol~tacety[ peroxide has been studied in [1-3]. It has been found
[1, 2] that only the cyclopropylmethyl ester of cyctopropylacetic acid (I) is preser~ in the reaction products.
The author of [3] observed that during the decomposition of the peroxide in hexachloroaoetone, not only this
ester but also cyclopropytmethyl chloride and a product of a homoaUyUc rearrangement of the cyclopropyl-
methyl radical, 3-butenyl chloride, are formed.
During the study of the thermal decomposition of cyclopropy[acety[ peroxide in CHBr3 and benzene at
65-70°, we f i r s t observed the formation in this reaction of rearrangement products with a ring expansion,
i . e . , the cyclobtttyl ester of cyclopropylacetic acid (1I) and cyclobutyl bromide (IV). In CHBr3, besides (1I)
and (IV), the cyclopropytmethyl (I) 3-butenyl esters of cyclopropylacetic acid, cyctopropytmethyt bromide
(V) and 3-butenyl bromide (VI) are also formed, and in benzene a mixture of esters (I)-(m) is obtained.
Bromides (IV), (V), and (VI) were formed i n t h e r a t i o 7 : 8 4 : 9 , and esters (I), (II), and (HI) i n t h e r a t i o 80:
19:1 (in CHBr3) and 70:13:17 (in benzene).
(~)
(tl)
(nt)
Ciflk',
l
I~=CHzBr + ~ - - B r + CH~=CH---CHzCHzBr + (I) + (tl) + (lit)
The composition and structure of the products formed were confirmed by GLC (a 3 m column with t r i s -
cyanoethoxypropane on Chromaton N-AW, at 130 and 1 6 ~ in a He current, 80 ml/min); and by the PMR spec-
t r a of the products isolated (5, ppm): compound (IV) 2.26 multiplet (CH2), 4.46 (quadruplet) (CH); compound
(V) 0.55 and 1.23 multiplet (ring CH2), 3.28 doublet (ring CHz); compound (VI) 2.59 quadruplet (CH2--Br),
3.34 triplet (CH2), 4.97 multiplet (CH2 = CH), 5.19 and 5.72 multiplst (CH2=CH). The composition of the hy-
drocarbon fraction was not determined. The mechanism of the observed rearrangement is now being studied.
L I T E R A T U R E C I T E D
1.
2.
3.
H. Hart and D. P. Wyman, J. Am. Chem. Soc., 81, 4891 (1959).
S. Oae, K. FuJimori, and S. Kozuka, J. Chem. Soc. Perkin Trans., 2 ~ 1844 (1974).
R. ICaptein, J. Am. Chem. Soc., 94, 8251 (1972).
•
Institute of Hsteroorganfc C ( ~ n d s , A ~ d e m y ofSciem~es ofthe USSR, Moecow. TranelsJ;ed from
Izvestiya Akademii Nauk $88I!, Seriya Khtmieheskaya, No. 10, p.2397, October, 1976. Original article s u b -
mttted June 2, 1976.
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2240
Shatkina et al.
