Preparation and Polymerization of Trifluoromethyl- and Chloro-(trifluoromethyl)-substituted Styrenes

Sept., 1950 CHLORO(TRIFLUROOMETHYL)-SUBSTITUTEDSTYRENES Acknowledgment.-This work was aided by a grant from the Corn Industries Research Foundation. The author wishes to thank Drs. W. 2 Hassid and I. L. Chaikoff for their helpful . assitance in this investigation. summary A simple method for the quantitative recovery 4053 of the carbon dioxide produced by the oxidation of certain glycosides and polyhydroxy compounds through the use of lead tetraacetate is described. This reaction is very useful and is now being used in the degradation of radioactive glucose, prepared photosynthetically. BERKELEY CALIFORNIARECEIVED 4, DECEMBER, 1949 5 [CONTRIBLJTIOX FROM THE DEPARTMENT CHEMISTRY AND THE PURDUE RESEARCH OF FOUNDATION, PURDUE UNIVERSITY ] Preparation and Polymerization of Trifluoromethyl- and Chloro-(trifluoromethyl) substituted Styrenes Downloaded by HENKEL KGAA on August 18, 2009 Published on September 1, 1950 on http://pubs.acs.org | doi: 10.1021/ja01165a059 BY EARL MCBEEAND ROBERT SANFORD~ T. A. In a study of the properties of chloro-(trifluoromethyl) -benzene and bis- (trifluoromethyl)-benzene, a number of bromo derivatives of these substances have been prepared.a The substitution of the bromine atom in these compounds by a vinyl group was accomplished and the resulting products were polymerized. Some trifluoromethyl-substituted styrenes have been reported p r e v i ~ u s l y . ~ The synthesis of the *~ monomers comprised the dehydration of substituted a-methylbenzyl alcohols which were prepared by means of the Grignard reagent. The Grignard reaction was conducted with bromo, bromochloro and bromodichloro derivatives of (tdluoromethy1)-benzene and bis-(trifluoromethy1)-benzenes. In each instance in which an organometallic compound was formed, the magnesium reacted with the bromine substituent. No reaction between magnesium and chlorine or fluorine was observed. A trifluoromethyl group ortho to the bromine atom may slightly retard the formation of the Grignard reagent. Otherwise, the trifluoromethyl group seemed to have little, if any, effect on the Grignard reaction. However, in no instance was a Grignard reagent formed from compounds in which a chlorine atom was ortho to the bromine. The compounds which failed to react with magnesium as well as those which did react are listed in Table I. The Grignard reagents were condensed with acetaldehyde and the product hydrolyzed to the substituted a-methylbenzyl alcohols. These alcohols are listed in Table 11. The dehydration of these alcohols was accomplished with a suspension of phosphorus(V) oxide in dry benzene at room temperature. The substituted styrene monomers were polymerized by an emulsion technique and the average molecular weights of the resulting polymers determined by the viscosity method. The monomers are listed in Table 111. (1) Abstracted from the doctoral thesis of Robert A. Sanford (2) E . T. McBee, R. A. Sanford and P.J, Graham, THIS ~ J K ~ . \ I , , Jo 72, 1661 (1950). (3) M. W. Renoll, i b i d . , 88, 1159 (1946). (4) G. B. Bachman and L. L. Lewis, ibid., 69, 2022 (1947). TABLE I REACTION SUBSTITUTED OF BROMOBENZENES MAGWITH NESIUM IN ETHER (Trifluoromethy1)-benzene (Trifluoromethy1)-benzene failed to react reacted 5-Bromo-2-chloro2-Bromo-5-chloro5-Bromo-2,3-dichloro2-Bromo-l,4-bis5-Bromo-l,3-bis4-Bromo-l,2-bis- 3-Bromo-4-chloro4-Bromo-3-chloro5-Bromo-2,4-dichloro5-Bromo-3,4-dichloro5-Bromo-4-chloro-1,3-bis2-Bromo-3,4-dichloro-l,5-bis- 2-Bromo-5-chloro-l,4-bis5-Bromo-2-chloro-l,3-bis- Since the bromination of 2,3-dichloro-(triiluoromethyl)-benzene did not produce 5-brorno-2,3-dichloro-(trifluorornethy1)-benzene, this compound was prepared by CF3 CF, CFa CFJ Acknowledgment.-The authors are indebted to the Ethyl Corporation and to the Westinghouse Electric Company for financial support which made this investigation possible. Experimental Preparation of Starting Materials ~-Brotiio-2-chloro-(tri~uoroi11ethyl)-Lenzene, 8-bromo- 4 -chloro - (trifluoronirthyl) -benzene, 2 - bromo-5 -chloro(trifluoromethyl) - benzene, 4-bromo -3 -chloro - (trifluoromethyl) -benzene, 5-bromo-2,4-dichloro-( trifluoromethyl) benzene, 5 -bromo -3,4 -dichloro - (trifluoromethyl) -benzene, 2 -bromo - 1,4 - bis (trifluoromethyl) -benzene, 5bromo -1,a-bis- (trifluoromethy1)-benzene, 4-bromo-1,2bis - (trifluoromethyl) -benzene, 2 -bromo - 5 -chloro 1,4his-(trifluoromethyl) -benzene, 5-bromo-2-chloro-l,3-bis(trifluoromethyl) -benzene, 5-bromo-4-chloro-l,3 -bis(frifluoromethyl) -benzene and 2-bromo-3,4-dichloro-l,5bis-(trifluoromethyl) -benzene were prepared by the bro- - - BARL MCBEEAND ROBERT SANFORD T. A. 40.54 Vol. 72 TABLE I1 SUUS? I1 UTEU ~-II[ETKIILRFVZTL-ALCOHOLS Chlorine, 5; Calcd Found Fluorine, $4 Caicd. Found Yieid, Compound L"c 4-Cl-3-CFa-CsHsO 71 5 4-Cl-3-CF3-a-CH3-CsHjO66 1 4-Cl-2-CFs-C~H80 78 s ~ , ~ - C I ~ - ~ - C F ~ - C B H (1 ~ 77. A 2,5-(CF3)rCsHsO 79 (i 3,5-(CF3)~-CsHs0 7