H. MILTONWOODBURN AND F. C. WHITMORE
1394
TABLE I11 SUBSTITUTED DI-PHENYLETHYNYL MERCURYS Phenylacetylene
.
. .. .
+Methyl $-Ethylo 9-Isopropyla D-Chloron m-Chloron o-Chloro" &Bromoa m-Bromo" o-BromG."
Formula (CsIlsC-C)rHn (CHaCeHK=C)zHg (CzHrCsHtCEChHg (CsHGH4C=C)zHg (CICsHL!EC)2Hg (CICaHaCIChHg (CICoHL!~C)zHg (BrCaH&=C)rHg (BrCsH4CEC)zHg (BrCsHaCZSC)zHg
M . p., OC. 124.5-1 2 5 199-202* 142-143 109-110 221-222 138-130 213-214 25a-257 143-144 184-185
Vol. 56
summary
Mercury, % Calcd. Found
. .. . ..
... . ..
43.51 41.21 42.54 42.54 42.54 35.79 35.79 35.79
44.02 40 95 42.56 42.85 42 68 35.88 35. !J7 35.61
' New compound. *Johnson and McEwen, Ref. 6.
1. Four new substituted phenylacetylenes and three new phenylpropiolic acids have been described. 2. Eight mercury derivatives of substituted phenylacetylenes have been prepared, described and analyzed. 3. The properties of p-ethyl- and p-isopropylphenylacetylene have been reported. NOTRE DAME,INDIANA
[CONTRIBUTION FROM THE SCHOOL OF CHEMISTRY AND
PHYSICS OF
RECEIVED APRIL2, 1934
THE PENNSYLVANIA STATE COLLEGE]
The Hydrolysis of Tertiary Aliphatic Halides. I BY H. MILTONWOODBURN AND F. C. WHITMORE Our attention was drawn to this subject by 3. The hydrolysis of tertiary chlorides with difficulties which we experienced in attempting to hot water or sodium carbonate solution gives prepare tertiary amyl alcohol by the hydrolysis of olefins exclusively. With cold water or cold its chloride. We were further interested in this sodium hydroxide solution, a certain amount of process by statements made by Ayres regarding tertiary alcohol is formed along with the olefin. the hydrolysis of amyl chlorides.' A study of the 4. Tertiary halides are more resistant t o literature revealed considerable confusion on the hydrolysis than is ordinarily supposed. subject.2 In the present work experiments were Experimental conducted with tertiary butyl chloride, tertiary Preparation of the Halides.-Tertiary butyl chloride and amyl chloride and bromide, methyldibutylcarbinyl tertiary amyl chloride were prepared by the method of chloride3 and tri-n-butylcarbinyl ~ h l o r i d e . ~The N ~ r r i s . ~Tertiary amyl bromide was best made by the results of these experiments gave definite results action of hydrogen bromide gas with trimethylethylene which can be summarized in the following state- prepared by dehydrating commercial tertiary amyl alcohol5 with 15% sulfuric acid. The product boiled at 44-47' ments. 1. The ease of hydrolysis of a tertiary chloride (80 mm.). The higher tertiary chlorides were available from another research.3 with hot water or sodium carbonate solution Hydrolysis Experiments.-Measured amounts of the decreases with increasing molecular weighT, proba- halides and water or the aqueous reagents were stirred bly because of decreasing solubility. Comparable mechanically in the cold or at the refluxing temperature or experiments with tertiary butyl chloride and tri- were merely refluxed. The liberated inorganic halide (halogen acid or sodium butylcarbinyl chloride with hot water gave 5.7 and halide) was determined by titration with standard silver 0.05 g. of hydrochloric acid liberated, respectively. nitrate (0.1058 N) and potassium thiocyanate (0.1178 N) 2. The hydrolysis of tertiary chlorides is according to Volhard. The results of the experiments are summarized in dependent on their solubility in the hydrolyzing medium. Thus the rate of hydrolysis of tertiary Table I. TABLE I butyl and tertiary amyl chlorides is greater in pure Halogen Time, reacted, water than in 5% sodium carbonate solution. Tertiary halide Cc. Reagent Cc. Conditions mn. % The rate is still slower with 40% sodium carbonate BuCl 2 25 Water 50 Shake, cold 1.2 480 7 1 . 0 25 Water 50 Reflux BuCl solution. (1) Ayres, I n d . Eng. Chem., 21, 899 (1929). (2) Butlerow, Ann., 144, 6 , 33 (1867); Straus, i b i d , 370, 366 (1909): Michael and Leupold, ibid., 379, 287 (1911); Dobbin, J . Chem. Soc., 37, 237 (1880); Bauer, Ann., 220, 158 (1889); Friedel and Silva, Johrcsb , 339 (1873); Wislicenus, Ann., 219, 319 (1889); Slawjanow, Cfiem. Zentr., 11, 134 (1907); Mereshkowski, ibid., I, 1814 (1914); hluset, ibid., I, 1313 (1907). (3) Whitmore and Woodburn, THISJOURNAL, 66, 361 (1833).
BuCl AmCI AmCl AmCl AmCl AmCl
25 50 -50 50 50 50
5% NazCO? Water Water 5% NazC03 40% NazCOs 2 % Has01
50 100 100 100 100 100
Reflux
Shake, cold Reflux Reflux Reflux Reflux
480 2 540 540 1020 540
43.4 0.3 48.6 44.5 20.0 46.8
(4) Norris, "Organic Syntheses," 1928, Vol. VIII, p. 50. (5) Supplied by the Sharples Solvents Corp., Philadelphia, Pa
THEISOMERIZATION OF SOME OLEFINS
June, 1934 TABLEI Tertiary halide AmCl AmCl AmCl
AmCl
AmBr ArnBr MeBuzCCl BuaCCl
(Concluded)
Halogen Time, reacted, Cc. Reagent mtn. Cc. Conditions % 50 5% Narc03 100 Reflux, stirG 480 8 1 . 1 50 Water 100 Reflux, stir 450 8 1 . 8 125b Water 540 54.W 125 Stir, cold Water 240 2 4 . 2 125 Stir, cold 870 1 5 . 4 Water 100 Stir, cold ' 100 Stir, cold Water 420 1.2 Water 180 0.1 100 Stir, cold Total 2250 9 5 . 7 d - e 125/ 1.4 N NaOH 125 Stir, cold 540 60.0 240 2 3 . 9 1.4 N NaOH 125 Stir, cold 870 1 4 . 8 100 Stir, cold 100 Stir, cold 420 2.8 2070 100.50 m a l 270 87.Oi 57 g. Water 150 Reflux,h stir 270 46.53' 57 g. Water 150 Cold, stir 15 g. Water 450 1 4 . 0 35 Refiux 480 1.2 25 g. Water 100 Reflux 480 1.3 25 g. 5% NazC03 100 Reflux
' Vigorous mechanical stirring during the refluxing. In this experiment the organic layer was separated and shaken with a fresh portion of water. This was continued until practically no acid was removed by this treatment. e This and the other figures in this experiment were obA Volhard titained by titration with standard alkali.
[CONTRIBUTION FROM
THE
1393
tration of an aliquot part of the combined water layers gave 92%. e The combined aqueous layers were fractionated through a 60 X 1.5 cm. packed adiabatic column using a hcgh reflux ratio. The organic layer was similarly fractionated. The result was the isolation of 17.3 g. of trimethylethylene and 8.4 g. of tertiary amyl alcohol (b. p. 100-101", &' 1.4050). This was similar to the preceding experiment except that successive batches of standard alkali were used instead of pure water. Fractionation according to e gave 12 g. of trimethylethylene and 17.7 g. of tertiary amyl alcohol (b. p. 100-100.6", n2t 1.4035). The reflux condenser was kept a t 40" to allow the trimethylethylene to pass over to a cold condenser as fast as formed. The yield of olefin was 80%. The trimethylethylene boiled at 37-38.5". Only 1.5 g. of higher boiling material was obtained. ' The ratio of olefin to carbinol was 1:2.
'
'
Summary 1. Experiments have been conducted on the hydrolysis of several tertiary aliphatic halides under various conditions. STATECOLLEGE, PENNA.
SCHOOL OF CHEMISTRY AND PHYSICS OF
THE
RECEIVED APRIL3, 1932:
PENNSYLVANIA STATECOLLEGE]
Isomerization of Olefins. I. Conversion of t-Butylethylene, umym-Methylisopropylethylene and Tetramethylethylene to Equilibrium Mixtures of the Three Olefins' BY K. C. LAUGHLIN, C. W. NASHAND FRANK C. WHITMORE When the dehydration of an alcohol gives more gave a mixture of essentially the same composition than one olefin, these may be formed directly by as that obtained from the alcohol. The interthe action of the dehydrating agent with the conversion of the olefins probably takes place alcohol or one olefin may be formed from another through the addition of a proton from the catalyst by an isomerizing action of the dehydrating agent. to one olefinic carbon, leaving the other carbon While it has long been known that such "contact with only six electrons and thus inducing the isomerization" can shift the position of a double usual rearrangements. The changes involved bond in a given carbon skeleton,'" it has re- may be the following mained for the mesent ? @ study to prove that this A HG3 Me2C=CMez process can also involve Me&-CH=CHS J_ MeaC-CH-Me _1 Me&-CHMez A CHz=C--CHMe2 the rearrangement of an alkyl group to give Me a new carbon skeleton. The dehydration of methyl-t-butylcarbinol These results show that the formation of a given (pinacolyl alcohol) by a catalyst consisting of olefin from an alcohol must not be assumed to be phosphorus pentoxide on silica gel in a flow reactor a simple or direct process. a t 300' has been found to give tetramethylExperimental ethylene, unsym-methylisopropylethylene and tThe dehydration of dimethylisopropylcarbinol is the best butylethylene in the ratio 61:31:3. When each source of unsym-methylisopropylethylene. The carbinol of these olefins was prepared pure and passed over was prepared in 41 yo yield from isopropylmagnesium brothe same catalyst under the same conditions, it mide and acetone. I t formed an azeotropic mixture with
--
~
( 1 ) Original manuscript received October 2, 1933. ( l a ) Ipatief, Ber., 36, 2003 (1903). (2) Whitmore and Meunier, THISJOURNAL, 66, 3721 (1933).
mesityl oxide formed by the condensing action of the Grig(3) Whitmore, ibid., 64, 3274 (1932).
