Acetylene chloride

It was discovered in 1940 that some acetylenic chlorides are converted into allenes by treatment with a zinc-copper couple in ethanol. This method appears to... 

We are indebted to BASF (Arnhem) for providing a sample of the acetylenic chloride. 

To a suspension of a tinc-copper couple in 150 ml of 100 ethanol, prepared from 80 g of zinc powder (see Chapter II, Exp. 18), was added at room temperature 0.10 mol of the acetylenic chloride (see Chapter VIII-2, Exp. 7). After a few minutes an exothermic reaction started and the temperature rose to 45-50°C (note 1). When this reaction had subsided, the mixture was cooled to 35-40°C and 0,40 mol of the chloride was added over a period of 15 min, while maintaining the temperature around 40°C (occasional cooling). After the addition stirring was continued for 30 min at 55°C, then the mixture was cooled to room temperature and the upper layer was decanted off. The black slurry of zinc was rinsed five times with 50-ml portions of diethyl ether. The alcoholic solution and the extracts were combined and washed three times with 100-ml portions of 2 N HCl, saturated with ammonium chloride. 

Note 1. For less volatile acetylenic chlorides (b.p. 3Q°C/15 mmHg) the thionyl... 

F0-E°/T 46.96 c ° 13.31 (all in cal/deg mol) S°56.40 eu, H0, F0, c° S° are respectively standard heat of formation, stand free energy of form heat capacity std entropy. E° is heat of formation of a perfect gas. at abs zero (Ref 10) Acetylene chloride behaves very unpredictably It is spontaneously flammable in air and it explodes when heated in air or shocked. On pyrolysis it gives off the very toxic phosgene (Ref 8). An attempt at defining its explosion limits is made m Ref 2... 

Acetylene Black. See under Carbon Blacks Acetylene Chloride or Chloroethyne. See... 

In addition to the commercially available 2,2,6,6-tetramethylpiperidine, di-tert-alkylamines have been prepared by Rathke7 by the copper-catalyzed coupling of acetylenic amines with acetylenic chlorides in an improvement of the procedure of Hennion.8 Di-tert-butylamine has been synthesized by the reaction of 2-methyl-2-nitropropane with sodium, followed by reduction. ... 

Amino-l-ethynylcyclohecane from the Corresponding Tertiary Acetylenic Chloride and Sodamide in Liquid Ammonia... 

Acetylene Chloride, Chloracetylene, Chloroethyne or Ethyny I Chloride, (called Chlor-athin or Chlor-acetylen in Ger), CICiCH mw 60.48 colorless gas, bp-29.6° Qyap 89 cal/g (at bp), d 2.0 (Ref 4). Sol in w ale (water soln jgives off 03 and glows in dark), nauseating odor and probably anesthetic if inhaled. Prepd from... 

A series of acetylenic acids has been made from the corresponding acetylenic chlorides by way of the cyanides in over-all yields of 52-84%. Few halo acids have been made by this method because of the reactivity of the halogen atom e.g., hydrogen chloride is removed from 7-chloro-... 

Tertiary acetylenic chlorides undergo self-coupling when they are treated with methylmagnesium bromide and cobalt(n) chloride, i.e. radical-generating conditions . Under these conditions, 4-chloro-4-methyl-2-pentyne (60) gave mainly the diyne 62 along with smaller amounts of another hydrocarbon tentatively identified... 

Acetylene reacts with fluorine with explosive violence. Reactions with other halogens, chlorine, bromine, and iodine are violent, too. Acetylene chloride, which is formed from addition reaction with chlorine, explodes spontaneously. It forms unstable acetylides with metals such as copper,... 

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