Carbon disulfide reaction with ammonia

Carbethoxycyclohexanone, 46, 82 2-Carbethoxycyclononanone, 47, 22 2-Carbethoxycyclooctanone, 47, 20 2-Carbomethoxycyclopentanone, conversion to 2-benzyl-2-carbometh-oxycyclopentanone, 45, 8 Carbon disulfide, reaction with /i-chloro-aniline and aqueous ammonia,... 

Carbon disulfide, reaction with J>-chloro-aniline and aqueous ammonia,... 

Carbon disulfide reacts with concentrated ammonia to give ammonium thiocyanate [1762-95-4] and ammonium trithiocarbonate [13453-08-2] in a reaction promoted by alumina catalysts ... 

Chloroacetic acid, reaction with salicyl-aldehyde, 46, 28 Chloroacetone, 46, 3 Chloroacetyl fluoride, 45, 6 o-Chloroacetyl isocyanate, 46,16 -Chloroaniline, reaction with carbon disulfide and aqueous ammonia,... 

Acetone cyanohydrin, carbon disulfide and aqueous ammonia yield a product (D) with melting point 154—5° C while, with gaseous ammonia, together with (D) another product (E) with m.p. 297° C is formed. Christian (80) has repeated the reaction with aqueous ammonia, carbon disulfide and acetone cyanohydrin. He obtained a product with m.p. 153—4° C which he identified as 2,2,5,5-tetramethylimidazol-idine-4-thione (CLX, Ri=R2=Ra=R4=CH3 i.e. product D). It seems likely therefore that product (A) is 2,2,5,5-dipentamethyleneimidazol-idine-4-thione (CLX, Ri-l-R2=R3-(-R4= —(CHgjs—). 

Phosphoms trichloride and pentachloride form sodium chloride and sodium phosphide, respectively, in the presence of sodium. Phosphoms oxychloride, POCl, when heated with sodium, explodes. Carbon disulfide reacts violendy, forming sodium sulfide. Sodium amide (sodamide), NaNH2, is formed by the reaction of ammonia gas with Hquid sodium. SoHd sodium reacts only superficially with Hquid sulfur dioxide but molten sodium and gaseous... 

Manufacture. An extensive technology was developed initially ia the 1930s for isolation of ammonium thiocyanate from coke-oven gases, but this technology is no longer practiced ia the United States (372). However, such thiocyanate recovery processes are used iadustrially ia Europe. Likewise, the direct sulfurization of cyanides to thiocyanates is not practiced commercially ia the United States. The principal route used ia the United States is the reaction of carbon disulfide with aqueous ammonia, which proceeds by way of ammonium dithiocarbamate [513-74-6]. Upon heatiag, the ammonium dithiocarbamate decomposes to ammonium thiocyanate and hydrogen sulfide. 

Titanium(IV) iodide is extremely hygroscopic. It dissolves in water with decomposition, and it fumes in air owing to hydrolysis. It forms 2 1 adducts with ammonia,7 pyridine,33 and ethyl acetate.34 With excess ammonia it undergoes ammo-nolysis to give ammonobasic titanium(IV) iodides.7 Analogous aminolysis reactions occur when titanium(IV) iodide is treated with an excess of primary or secondary amine.36 Titanium(IV) iodide is sparingly soluble in petroleum ether, moderately soluble in benzene, and even more soluble in chlorinated hydrocarbons and carbon disulfide. At elevated temperatures it... 

In a 250-ml. round-bottomed flask fitted with mechanical stirrer, reflux condenser, and thermometer are placed 38.3 g. (0.30 mole) of -chloroaniline (Note 1), 41 ml. (0.6 mole) of concentrated aqueous ammonia (sp. gr. 0.9), and 21 ml. (0.3S mole) of carbon disulfide. The mixture is stirred vigorously, and when it is heated to 30° the reaction starts. The tempierature is maintained at 30-35° by external cooling (Note 2). The reaction mixture turns into a deep-red turbid solution within a few minutes, and then suddenly a heavy yellow precipitate of ammonium /(-chlorophenyldithiocarbamate separates. To the mixture 15 ml. of water is added, and stirring is continued for 1 hour. The mixture is filtered with suction, and the residue is washed with... 

In the reaction of 2-isopropylidene-l-cyclopentanone 201 with carbon disulfide and ammonia, the perhydrocyclopenta[e][l,3]thiazine-2-thione derivative 204 was formed. The probable intermediates of the reaction are the Michael adduct 202 and the 2-imino-l-cyclopentanedithiocarbamic acid derivative 203. Under similar conditions, the related alkylidene derivatives gave the corresponding 3-substituted-2-imino-l-cyclopentanedithio-carbamic acid derivatives. Further substituted derivatives and homologs of 204 were also synthesized (74AKZ319), but the stereochemistry of these compounds was not investigated [73JCS(P1)1009]. 

Ammonium thiocyanate is made in the United States by the reaction of carbon disulfide with aqueous ammonia. Ammonium dithiocarbamate is formed as an intermediate in this reaction, which upon heating, decomposes to ammonium thiocyanate and hydrogen sulfide. 

Aryldithiocarbamates (531), easily obtained by the reaction of ammonia and carbon disulfide on arylamines, are cyclized, with dehydrogenation, by heating with sulfur at 200 °C to 2-thiobenzothiazoles (532 Scheme 287). 

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