POLYMERIZATION OF STYRENE
Dee. 20, 1962
ene.64*.' The colorless precipitate was filtered and washed repeatedly with dry ether under exclusion of moisture. I t was then dissolved in 500 ml. of anhydrous ethanol. This solution was treated with a solution of 82 g. (0.35 mole) of anhydrous silver perchlorate in 120 ml. of absolute ethanol. The mixture was filtered. Most of the N-cycloheqlidenepiperidiniun perchlorate was found with the silver bromide, from which it could be extracted with hot anhydrous acetone. Upon addition of ether to the acetone solution, 39.5 g. of colorless plates was obtained, m.p. 246-249'. Upon cooling of the ethanol solution (above) and addition of ether 2.8 g. additional iminium perchlorate was obtained; total yield 53%, v&Y1 1660 cm.-'. A solution of 5.0 g. (0.019 mole) of N-cyclohexylidenepiperidinium perchlorate in 300 ml. of anhydrous methanol was treated a t 0" with a solution of diazomethane, prepared from 5.0 g. (0.049 mole) of nitrosomethylurea, in 70 ml. of anhydrous ether. The yellow color of the diazomethane disappeared and gas was evolved. The addition was complete in 5 min., and the solution was allowed to stand in the refrigerator for 4 hr. After concentration to half-volume in vacua at 0" the solution was cooled to -40". The 1,l-pentamethylene-2,2-pentamethyleneaziridiniumperchlorate separated as colorless needles and w a s recrystallized from absolute ethanol, m.p. 236-238' dec., yield 3.8 g. (73'35), no in-
I
frared maxima corresponding to -N+-H
or
(65) C. Mannich and H. Davidsen, Bcr., 69, 2106 (1S36). (66) We are grateful t o Dr. W. P. Jackson of the Explosives Department, E. I. du Pont de Nemours and Cn.,Inc., for a generous gift of nitrocyclohexane. (67) W. E. Noland, J. K. Kneller and D . E . Rice, J . Org. Chcm., aa, 695 (1957).
THE
b.p. 82-83' (1.3-1.4 mm.), 112% 1.4951 (reported b.p. 84' (1 mm.), 1 ~ 1 1.4959). 6 ~ A mixture of 5.7 g. (0.044 mole) of 1aminocyclohexanemethanol, 13.8 g. (0.065 mole) of 1,4-dibromobutane and 4.9 g. (0.044 mole) of sodium carbonate in 20 ml. of absolute ethanol was heated under reflux for 84 hr. following the general directions for ring f a r m a t i ~ n . ~ , ~ ~ After the addition of 50 ml. of water the aqueous ethanolic solution was extracted with ether. The ether extract was washed with dilute aqueous hydrochloric acid. The aqueous layer was strongly basified with sodium hydroxide and extracted with ether. After drying and removal of the ether a pale yellow sludge was obtained. I n an attempt to distil it, 1.O g. of starting material was recovered and the rest solidified. Purification by sublimation a t 100' bath temperature and 0.2 mm. yielded 5.3 g. (7970 based on unrecovered starting material) of colorless prisms, m.p. 71-72', vFz1 3400 ern.-' (0-H). A n d . Calcd. for C I I H ~ I N O :C, 72.08; H, 11.55; N, 7.64. Found: C, 71.85; H, 11.54; N, 7.35. The perchlorate of 1-N-pyrrolidylcyclohesanemethanol crystallized as colorless prisms from absolute ethanol; m.p. 92-93';
v z l 3505 (0-H), 3125
(-A+-H).
I
Anal. Calcd. for C I I H ~ ~ C I N OC,~ :46.56; H, 7.82; N,
>C-&
