Primary amines reactions, carbon disulfide

N-Bis(methylthio)methylene derivatives of amines (iminodithiocarbonates) were first introduced by Hoppe and Beckmann468 for the synthesis of a-amino acids from glycine. The A bis(methylthio)methyleneamines are prepared by reaction of a primary amine with carbon disulfide (HAZARD) in the presence of triethylamine and iodomethane to form a methyl dithiocarbamate derivative, which is then S-alkylated with a second equivalent of iodomethane in the presence of potassium carbonate as the base. Scheme 8,233 illustrates an alternative one pot procedure applied to the synthesis of /erf-butyl N-[bis(methylthio)-methylene]glycinate and its use in diastereoselective conjugate addition under... 

When alkyl thiocyanates (39) are heated they isomerize to the corresponding isothiocyanates (43) (Scheme 24).5 Isothiocyanates (43) are better obtained by heating a primary amine with carbon disulfide (1) and mercury(II) chloride (Hofmann mustard oil reaction, 1868) (Scheme 25). 

The Schiff base or enamine reaction has been employed to modify aldehydes and ketones by condensation with a primary amine (reaction 1) and to condense primary amines with a carbonyl compound (reaction 2). A similar reaction between primary amines and carbon disulfide yields isothiocyanates or mustard oils (reaction 3). These three possibilities for derivative formation will be discussed in this chapter. 

Recently, it has been reported that l,3-dithiole-2-thione (12) reacts with primary amine to give the corresponding thiourea and A-4-thia2oline-2-thione (Scheme 5) (14). 5-Methylenethiazolidine-2-thione (13) obtained from the reaction of propargyl amine and carbon disulfide... 

Salts of dithiocarbamic acid can be prepared by the addition of primary or secondary amines to carbon disulfide. This reaction is similar to 16-9. Hydrogen sulfide can be eliminated from the product, directly or indirectly, to give isothiocyanates (RNCS). Isothiocyanates can be obtained directly by the reaction of primary amines and CS2 in pyridine in the presence of DCC. ° In the presence of diphenyl phosphite and pyridine, primary amines add to CO2 and to CS2 to give, respectively, symmetrically substituted ureas and thioureas ... 

Dithiocarbamic acids, R2NC(S)SH, are rather unstable and seldom isolated or used as such. Usually their alkali metal or (substituted) ammonium salts are prepared for further use as starting materials in the synthesis of various metal complexes or organometallic derivatives. The most common is the reaction of primary or secondary amines with carbon disulfide in alkaline medium. 

Isothiocyanates are readily made by reaction of a primary aromatic amine with carbon disulfide/triethylamine followed by ethyl chloroformate/triethylamine and by treatment of the amine either with thiophos-gene, calcium carbonate, chloroform, water [138, 139] or with carbon disulfide, N,N -dicyclohexylcarbodiimide, pyridine [140, 141],... 

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... 

Dithiocarbamates have been prepared by the reaction of carbon disulfide with primary or secondary amines. The addition of DMF, cesium carbonate and a sulfonamide to the crude dithiocarbamate, give di-, tri- and tetra-substituted thioureas in 65-76% yields (Scheme 41).121... 

Reaction of carbon disulfide with primary amines, using MCM-41-TBD (mesoporous MCM-41 silica, TBD l,5,7-triazabicyclo[4.4.0]dec-5-ene) as catalyst, has given symmetrical thioureas under heterogeneous conditions. The MCM-41-TBD could be reused as a catalyst (Scheme 43).123... 

Reaction of carbon disulfide with primary amine hydrochloride in the presence of dimethyl aminopyridine (DMAP) and A,A -dicyclohexylcarbodii-mide (DCC) affords symmetrical thioureas (Scheme 44).124,125... 

Hofmann mustard-oil reaction org chem Preparation of alkylisothiocyanates by heating together a primary amine, mercuric chloride, and carbon disulfide. haf-man mos-tord, 6il re,ak-sh3n ... 

Thirty-nine different dithiocarbamates have been efficiently prepared through a one-pot reaction of an aliphatic primary or secondary amine, carbon disulfide and an alkyl halide (Figure 2.16). " Typically, all reagents were liquids and the mixture slowly solidified upon reaction. Therefore, although the reaction does not use solvents, the reagents are probably acting as the solvent in this procedure. Additionally, the reactions were quenched with water and extracted with ethyl acetate, so solvent was used. Nevertheless, this is an excellent synthetic method for the preparation of S-alkyl dithiocarbamates, which are useful compounds for the pharmaceutical and agrochemical industries. 

Isothiocyanates. Primary aliphatic amines react with carbon disulfide and DCC in ether at 0° to give isothiocyanates and dicyclohexylthiourea.5 The reaction can also be applied to the less basic primary arylamines if the reaction is carried out in pyridine (in a few cases one molar equivalent of triethylamine is also added).6 Yields of isothiocyanates are in the range 70-95%. 

Reaction with carbodiimides 805 A primary aliphatic amine (0.1 mole) is added to a solution of dicyclohexylcarbodiimide (0.1 mole) and carbon disulfide (40 ml) in ether or tetrahydrofuran (100-200 ml) stirred at —10°. The temperature is allowed to rise to 20° during 3 h. The mixture is then set aside at room temperature for 12 h, after which the di-cyclohexylurea, is filtered off and washed with a little ether, the filtrate is evaporated, and the residual isothiocyanate is distilled in a vacuum or recrystallized. Yields are about 80%. 

The FMO does not catalyze epoxidation reactions or hydroxylation at unactivated carbon atoms of xenobiotics. Primary aromatic amines and amides, aromatic heterocyclic amines and imines, and the aliphatic primary amine phentermine are N-oxidized by CYP450 to hydroxylamines. The CYP450 oxidizes carbon disulfide to carbon dioxide and hydrogen sulfide and the antipsychotic phenothiazines to sulfoxides. 

Annulation reactions of 5 (X=PPhj) with isocyanates, carbon disulfide or carbon dioxide give rise to pyridino[3 2 4,5]-thieno[3,2-d]pyrimidine derivatives. Interesting selectivity is noted in the reactions of 10 with RNCX(X=0,S) in that when R=alkyl cyclization involving both phosphoranimines occurs whereas when R=aryl cyclilzation involves the phosphoranimine directly attached to the arene and the =CHAr center leaving one phosphoranimine intact. Hydrolysis of the remaining center results in formation of the primary amine. 

The mustard oil reaction is a well known test for the presence of primary amines. By the action of carbon disulfide under mild conditions (room temperature), the... 

Carbon disulfide as the thio-analog of carbonyl compounds reacts with primary amines, resulting in the formation of alkyl isothiocyanates, which have slightly lower RIs than those of other derivatives of primary amines, including A -trimethylsilylated amines (Table 5). The sole product of this reaction is gaseous hydrogen sulfide ... 

Another approach to reach rhodanine derivatives is depicted in Scheme 9.7, which begins with the reaction of aliphatic primary amines, carbon disulfide, and 1,2-diaza-1,3-dienes 9 (Scheme 9.9). Finally, this reaction leads to 5-hydrazinoal-kylidene rhodanine derivatives 10 [21]. 

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