May, 1937 [CONTRIBUTION FROM
TRANSFER OF THE CHEMICAL
/-ALKYLRADICALSFROM
PHENO1.S TO
LABORATORY OF THE WASHINGTON *WARE
HYDROCARBONS
890
COLLEGE OF NEW YORK UNIVERSITY]
The Migration of Alkyl Radicals. I. Transfer of Some Tertiary Alkyl Radicals from Phenols to Hydrocarbons BY RICHARD A. SMITH In a study of alkyl phenyl ether rearrangement the octyl group in 4-(1,1,.3,3-tetramethobutyl)it was found that the migrating alkyl group can phenol. a be introduced into a different molecule instead Procedure of merely rearranging to another part of the same I. The Action of Aluminum Chloride upon p-!-Butylmolecule.' I n this report the migration has been phenol.-A half mole of the phenol, two-thirds of a mole extended to apply to the change of position from of technical anhydrous aluminum chloride, and 150 cc. of the phenol nucleus to the benzene nucleus. As benzene were refluxed for eight hours. The whole was with the migration quoted, the reaction offers a then poured upon ice,the organic layer separated and water means of preparation of alkylated benzenes. In washed. The aqueous layers were extracted with ether, the ether layer dried with anhydrous sodium sulfate, the some studies of rearrangements performed in this ether evaporated on a steam-bath, and the residual liquid Laboratory by Niederl and the author, which have purified by distillntion and identified as phenol. The ornot been reported, i t has been observed that ganic layer was washed with Cloisen solution, water and alkyl groups in the phenolic ring can be made to €hen dried with anhydrous sodium sulfate. The product change ring position under the i d u e n c e of re- was purified by fractional distillation. A small Hempel was found useful. arranging agents such as are used to effect phenyl column t - B u t y l b ~ b. ~ ,p. 167-168'; nz'D 1.4958; 64' 0.868; ether isomerizations. I t was thought that this yield 70%. A d . Calcd. for Cl~H14:C, 89.6; H, 10.4. migration might be intermolecular, in which Found: C, 89.3; H, 10.1. II. The Action of Aluminum Chloride upon p-t-Amylcase i t should be possible to effect the migration phenol and correto a foreign nucleus. Para substituted tertiary phenol.-A half molar quantity of the I sponding quantities of aluminum chlonde and benzene as in alkyl phenols were chosen as being very likely (I) were allowed to stand at room temperature for twelve to undergo migration with the least possible days. The whole was then worked up as in (I). Phenol side reactions. The action of aluminum chloride was again obtained. The other product was purified by in the presence of benzene a t room temperature fractional distillation using appropriate sized columns. t-Amylbenzene, b. p. 188-190", n2% 1.5032; d2a 0.864; and a t reflux temperature upon p-t-butylphenol, yield 250J0. p-t-amylphenol and 4-(1,1,3,3-tetramethobutyl)- III. The Action of Aluminum Chloride upon 4-(1,1,3,3phenol has been studied. The products are Tetramethobuty1)-phenol.-A six molar quantity of the phenol and corresponding alkylbenzenes. With phenol was treated with equivalent amounts of aluminum the butylphenol a good yield of t-butylbenzene chloride and benzene a t room temperature as in (11). A was obtained; the reaction was carried out a t the half molar quantity was treated a t the reflux temperature as in (I). The products soluble in Claisen solution, in reflux temperature. The migration of the amyl- addition to phenol, are still under investigation. phenol was performed a t room temperature. The l-Butylbcnzene.-Yield in the cold (a) 50%; in the hot migration of the octylphenol was performed a t (b) 7070. Calcd. for CloHlr: C, 89.6; H, 10.4. Found: both room temperature and a t the reflux tem- (a) C, 89.9, 89.2; H, 10.4, 10.1. The author wishes to acknowledge the help of perature. There was no fundamental change in Jack Rosen who performed a part of this work the reaction. The products identified were free in connection with research for the degree of phenol and t-butylbenzene. I t will be noticed B.S. He wishes also to thank Miss R. T. Roth that the octyl group underwent scission. This for the micro-analyses performed is not unexpected as a Friedel-Crafts reaction between diisobutylene and benzene yields tsummary butyl substituted benzenes.Y If this migration I. The migration of alkyl groups from a is bimolecular, the results may be interpreted phenol nucleus to a benzene nucleus has been as additional evidence for the para position of demonstrated. ( 1 ) Smith, THISJOURNAL, 66, 714 (1934); alsq see Sowa, Hinton 2. The above migration has been performed and Nieuwland, rbid., 66, 3402 (1933); Behaghel and Freierwhner, Rer., 67, 1368 (1934). (2) Unpublished results of this Laboratory.
(3) Niedul. Smith and Whitmaa, Tars JOURNAL, 69, 7 1 6 7 1 8 (1937).
DO0
L. H. REYERSON AND BRUCEGILLESPIE
a t room temperature and a t the reflux temperature. 3. The scission of the octyl group of 4-(1,1, 3,3-tetramethobutyl)-phenol has been demonstrated. 4. l-Butylbenzeiie has been prepared from 4-t-butylphenol and from 4-(1,1,3,3-tetramethobutyl)-phenol. t-Amylbenzene has been pre-
[CONTRIRUTION FROM
THE SCHOOL OF
Vol. 59
pared from 4-t-amylphenol. 5. Further studies of this type of migration are being made. Systems now under investigation include migrations from phenol nuclei of different types of alkyl groups to simple and substituted (phenol, phenyl ether and naphthol) aromatic nuclei. NEW YORK,N. Y. RECEIVED JANUARY 19, 1936
CHEMISTRY OF THE UNIVERSITY
OF
MINNESOTA]
Equilibria of the Reactions between Acetylene and Heavy Water at 0 and 100' and the Heats of Reaction' BY L. H. REYERSON AND BRUCEG E L E S P ~ I n a previous communication2 the equilibrium constants for the reactions between acetylene and heavy water a t 25' were given. At equilibrium six different molecular species were involved in seven possible reactions and the constants for five of them were calculated from the experimental results. The experimental technique involved the accurate determination of the deuterium content of the heavy water before and after exchange. This investigation has been extended and the equilibria of the reactions have been determined a t 0 and 100'. The experimental methods with some small refinements remained much the same as in the previously reported study, except that a heavily insulated constant temperature air thermostat was substituted for the water-bath used in the earlier investigations. At 100' the normal alkaline solutions attacked the Pyrex glass bulbs so strongly that several of them broke during the time required for equilibrium. As a result quarter normal solutions of sodium hydroxide were used in the experiments run a t 100' and half normal solutions were used a t 0'. Because of the high partial pressure of water vapor a t 100' the partial pressure of the acetylene was kept a t about half an atmosphere to reduce the hazard of explosions. In all cases the bulbs containing the acetylene and heavy water solutions were made up and run a t room temperature for several days, after wbich they were run a t either 100 or 0' for from fortyeight to sixty hours. At the conclusion of a given
run the heavy water was recovered from the bulbs and its density determined in the same manner as previously reported.2 From the changes in the density of the heavy water solutions and a knowledge of the equilibrium constants Ka for the reaction D20 HzO S 2 H D 0 and K7for the reaction GDz C;H2 e 2 G H D it was possible to calculate the number of moles of each of the six reacting molecules a t equilibrium. According to Topley and Eyring3 KP,has a value of 3.118 a t 0' and 3.374 a t 100'. Glockler and Morrel14 gave the value of K7 a t 0' as 1.373 and a t 100' as 1.584. Tables I and I1 give the results of these calculations a t 0 and 100'. Using the values given in Tables I and I1 the equilibrium constants for the following exchange reactions were calculated.
( 1 ) This investigation was mude possible by a grant from the Graduate School of the University of Minnesota. (2) I.. H. Keyerson and Bruce Gillespie. THIS J O U R N A L , 08, 182 (1936).
(3) Topley and Eyring, 1.Chcrn. P h y s . , I, 217-230 (1934). (4) Glockler and Morrell, rbtd , 4, 15 (1936). ( 5 ) Hiroto and Okamoto, Bull. Chem. SOC.Jopa71, 11, 340-351
+ +
+ HDO e G H D + HzO + HDO e C ~ D +Z HzO + Dz0 ClHD + HDO + Dz0 CzDz + HDO + Dz0 a CzDz + H20
CIH~ CiHD CZHP CzHD GHz
(1)
(2) (3) (4) (5 )
Table I11 gives the equilibrium constants for the exchanges a t 0' and Table IV gives the values a t 100'. The equilibrium constants a t 100' are all higher than those previously reported a t 25' and the values a t 0' are all lower than a t 25'. It is of interest to note that Hiroto and Okamoto5 calculated the equilibrium constant K Ia t 2.5' from spectroscopic data. They obtained a value of 0.59 where our experimentally determined value was 0.599. The agreement is excellent and
(1936).
