Oct. 5, 1964
COMMUNICATIONS TO THE EDITOR
to leave a white, rubbery polymer containing 10.4% boron with vmln 2620 cm.-' (B-H stretching). Under identical conditions no terpolymer was formed when 1-methyl-2-nitrosocarboranewas used Acknowledgment.-We are indebted to the Atomic Energy Commission, Lawrence Radiation Laboratory, Livermore, Calif. for the support of this work under Contract X o . W-7405-EXG 48, and to M r . Richard Crooker, Mr. Raymond Storey, and Mr. Fred G. Hoffman of this laboratory for analyses and spectra. THIOKOL CHEMICAL CORPORATION REACTIOL MOTORS DIVISION DEYVILLE, SEW JERSEY
JOELM KAUFFMAS JOSEPHGREEN S COHES MURRAY MARVISM FEIS ERNESTL COTTRILL
RECEIVED JCLY23, 1964
2,3-Dimethyl-7,7-dimethoxyquadricyclo[2.2.1.02 OJS5]heptane
Szr: Although numerous publications have been devoted to the one-step syntheses of quadricyclane derivatives,l-6 relatively little is known about the chemical reactions of this highly strained system As part of a general program in the area of quadricyclane chemistry we desired to elucidate the nature and ultimate fate of carbonium ions generated on this quadricyclic skeleton. This communication reports the synthesis of %,3- Hirnethyl- 7.7-dimethoxyquadricyclo [2.2.1 O 2 O3 heptane (1) and the subsequent acid-catalyzed rearrangement of this tetrasubstituted quadricyclane This rearrangement gives the first positive evidence for the type of bond cleavage postulated by Richey and Buckley5 and by Story and Fahrenholtz6in accounting mechanistically for the conversion of 7-substrtuted quadricyclanes (2) to i-substituted norbornadienes in the solvolysis of 2 "I-
Me0
x
OMe
M e O y OMe
3
MeOv OMe
4
a, R = OTs;
b,R = C1
2
T h e synthesis of 1 originated with the known triene 3.' Dehalogenation according to published procedures* yielded 4 through a novel 1,4 reduction. T h e structure of 4 was substantiated in several ways. Catalytic hydrogenation over palladium on carbon resulted in the rapid uptake of one mole of hydrogen and the relatively slow uptake of a second mole of hydrogen. Near-infrared spectroscopy confirnied the presence of a norbornadiene structure with two olefinic hydrogens as indicated by the absorption a t 1.655 p with a molar absorptivity of 0 . 6 T B . g ~ ~ The D final definiJ . Cristol and R . I. Snell, J . A m . Chew Soc., 7 6 , 5000 (1954). J . Cristol and I
