Isothiocyanate morpholine

The reaction of the morpholine enamine of cyclohexanone with phenyl isothiocyanate led only to the tetrasubstituted isomer of the monoadduct (54), which failed to add any more of the phenyl isothiocyanate. The formation of only the tetrasubstituted isomer has been attributed by Hunig et al. (37) to the stronger conjugation of the C=S group with the enamine double bond than that of the C=0 group in the enamine (49). 

Condensation of the isothiocyanate (532) with ethylenediamine affords (533) (76M171). Treatment of a-(5-bromouracil-l-yl)-a-alanine (534) with an amine such as piperidine or morpholine results in the formation of (535) by an addition-elimination mechanism (80CHE418). 

Preparation from cyclohexyl isothiocyanate and N-(2-aniinoethyl)morpholine (Carbide and Carbon Chemicals Co.). ... 

N-(l-Gyclohexenyl) morpholine added all at once to an ice-cooled soln. of N-phenylbenzimidoyl isothiocyanate, and allowed to stand at room temp, over-... 

The interaction of enamines with sulphur in conjunction with carbon disulphide, isocyanates, or isothiocyanates results in the production of sulphur-containing heterocyclics. Cyanamide has now been shown to participate in this reaction. Treatment of enamines of type (24) with sulphur and cyanamide at room temperature in ethanol produces a range of 2-aminothiazoles (27) in 30—70% yield no catalyst is required. Initial formation of the thiolated intermediate (25) is probably followed by addition of cyanamide, yielding (26) elimination of amine finally produces the observed thiazoles (27). Since AW-dialkylcyanamides do not undergo this reaction, cyanamide may react as the tautomeric carbodi-imide. An actual example of the reaction employing the enamine derived from cyclohexanone and morpholine is also shown [(28) - (29)]. ... 

A number of derivatives of L-azetidine-2-carboxylic acid, a naturally occurring antimetabolite of proline, have been prepared. Its reaction with phenyl isothiocyanate gave the thiourea (187), which on treatment with dicyclohexylcarbodi-imide (DCC) formed 2-phenylimino-5-thiazolidinone (188). The thiazolidinone, which acylates morpholine at room temperature,... 

Morpholino- and 2-pyrrolidino-5-bromo-4-pyrimidinamine 156 (R2 = morpholine or pyrrolidine) were successfully reacted with various isothiocyanates (Scheme 76) in the presenee of NaNH2 in DMF to form thiazolo[4,5-djpyrimidines 157 [109],... 

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