REACTION OF DIVINYLSULFIDE WITH SILVER OXIDR
April, 1939
SUBSTITUTED
TABLEI AMMONIUM SALTS
O F SULPAMIC
9 I .5
ACID M p
Amine used
(uncorr.) OC.
Formula
hTH2S0z0H*NH2CH8 9 1-92 1 Methylamine" Dimethylamine" NH90zOH.NH (CH8)z 86-87 NHSOz0H.N (CH3)a 147.5-149 3 Trimethylamine NHzSOzOH.NHzCH$2Ha 65-70 4 Ethylamine" NHzSOzOH.NHz(CHz)zCHs 67-69 5 Propylamine NH~SOzOH*NHzCH(CHs)2 74-75 6 Isopropylamine" NHzSOzOH.NHz(CHz)sCHs 107-108 7 n-Butylamine 8 Isobutylamine NH#OzOH.NHzC(CHs)8 138-139 NHzSOzOH*NHz( CHz)rCH3 128-129 9 n-Amylamine h"zSOzOH.NHz(CHz)zCH(CH3)? 185 10 Isoamylamine NHZSOIOH*NHZ(CHZ)~CH~ 109-111 11 n-Hexylaminc 12 2-Ethylbutylamine NHzSOzOH*NHzCHzCH(CzHs)2 89-90 NH~SO~OH~NH~CH~CH~NH~~HOSOzhTH~ 156-158 13 Ethylenediamine .XHzSOzOH.NHzCH(CH~)CHzNH~~HOSOzr\r"~ lZ5-156 14 Propylenediamine NHzSO20H.NHzCeHi1 157-158 15 Cyclohexylamine I6 Dicyclohexylamine NHzSOzOH~NH(C6Iu)~ 160-162 NHZSOZOH*NHI( CH~)PCBHL 183-184 17 P-Phenylethylamine 104-105 18 7-Phenylpropylamine NHzSOzOH*NH2(CHz)sCsHr These sulfamates were found to be extremely hygroscopic.
1. Experimental evidence has been presented to demonstrate that sulfamic acid behaves as a dibasic acid in liquid ammonia. 2. A series of eighteen substituted ammonium
[CONTRIBUTION FROM
THE
Sitrogeu, % Calcd. Found
25.00 22.53 20.51 22.53 20.51 20.51 18.82 18.82 17.39 17.39 16.16 16.16 23.19 23.88 16.33 11.51 14.68 13.79
21.9 19.7 17.9 19.7 18.0 18.0 16.5 16.5 15.2 15.2 14.1 14.1 22.1 20.9 14.3 10.1 12.8 12.1
'3
2
Summary
Sulfur % Calcd. Found
25.59 24.15 20.60 23.21 20.60 21.54 18.83 18.81 17.65 17.65 16.25 16.18 25.22 24.03 16.40 11.61 14.63 14.00
21.9 19.2 17.8 19.3 17.6 18.3 16.1 17.1 15.0 15.1 14.3 14.3 22.0 21.5 14.3 10.0 12.4 11.8
sulfamates has been prepared. Various properties of these compounds, such as melting Point, solubilities in common solvents, and hygroscopicity have been determined. RECEIVED JANUARY 2 i , 193!t
URBANA, ILLINOIS
RESEARCH LABORATORIES, MERCK& CO., INC.]
The Reaction of Divinyl Sulfide with Silver Oxide BY WM. L. RUIGH'AND A. E. ERICKSON The first reference to the preparation of divinyl ether may be found in a paper by Semmler2 on the essential oil of the leek, Allium ursinmm L. When divinyl sulfide derived from this source was treated with dry silver oxide, Semmler obtained a colorless sulfur-free liquid which boiled a t 39' and with a molecular weight of 71 as indicated by two vapor density measurements. Without analysis or further characterization he claimed to have prepared divinyl ether (molecular weight 70) for the first time, giving the following equation for the reaction
and Menzies4 and over 10' lower than that reported by Semmler. On theoretical grounds we can find little support for the reaction as formulated by Semmler. It was therefore decided to reinvestigate this reaction. The repetition of Semmler's workon the natural sulfide was not possible due to the difficulty of obtaining the oil of A . ursinum. Synthetic divinyl sulfide, when treated with dry silver oxide a t 30' according to Semmler's procedure, failed to give divinyl ether. In one experiment, when the reaction mixture was heated (CzHdzS AgzO = (CzHa)?O AgzS to reflux the divinyl sulfide, a violent explosion Recently pure divinyl ether has been synthe- occurred. Moist silver oxide and divinyl sulfide sized,a fully characterized, and its boiling point likewise failed to give acetaldehyde and silver as found to be 28.3', a value confirmed by Miles stated by Semmler. We are indebted to Pro€. E. Emmet Reid for (1) Present address: Department of Physiological Chemistry, University of Pennsylvania, Philadelphia, 1'cnnsylvani;r. suggesting the use of p,P'-dibromodiethyl sulfide (2) Serumlrr, Aizn., 241, 02 (1887).
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