N-Thiocarbamylation

Similar reactions have been carried out with amidines (67NEP6610627). Thus tri-chloroacetamidine (309) reacts with chlorothioformate esters to produce thioacyl products (310) which are readily oxidized to 5-alkoxy-3-trichloromethyl-l,2,4-thiadiazoles (311). The yields in both steps are about 80% (Scheme 111). The bromine oxidation of N-thiocarbamyl derivatives (312) of cyclic amidines (2-aminopyridine, 2-aminothiazole, 2-aminopyrimidine) yields thiadiazolium salts (313) (71JPR1148). In the 2-aminopyridine series, products of type (230 Scheme 81) are obtained in 20-73% yield when R is an ethoxycar-bonyl group (750PP55). 

N-Carbamyl- and N-thiocarbamyl-amidines from isocyanates and isothiocyanates respectively... 

C-Thiocarbamylation 28,836 N Thiocarbamyl group migration 27,338 Thiocarbamyl halides... 

Di(thiocarbomyi)-hydrazine. See N,Nf-Bis-(thiocarbamyl)-hydrazine In Vol 2 of Encycl, pp B158-R B159-L... 

Di (thiocarbamyl)-hydrazine see N. N -Bis (thio-carbamyl)-hydrazine 2 B158-B159... 

The only known compound of this type is a thiocarbamyl derivative. Bromomagnesium ethenetellurolate combined with /V.TV-dimethylamino-Lhiocarbonyl chloride to give orange-red, solid N,N-dimethylaminothiocarbonyl ethenyl tellurium, which is stable at 20° under an atmosphere of argon, but is decomposed by acids1. 

Cry Sts, mp 232—237° very si sol in w dissolves in bases from which solns it may be repptd by addition of acid. It was obt in yields up to 60% by deamination of bis-thiocarbamyl-hydrazide, H,N.CS.NH.NH CS.NH, in the presence of polyphosphocic acid contg 82—84% PjO, as the deaminating and cycliz-ing agent. This compd seems to be identical with the 234° mp form described in Beil... 

Difficulty finding conditions that would allow both efficient sequencing and suppression of the O-to-N shift led us to investigate tertiary amine catalysis of thiocarbamylation. Complete reaction of ONCS showed little effect of solvent on coupling. Adding 1.5 to 2.5 equivalents of acetic acid, however, decreased the fraction of the desired product (Table HI). 

The most representative general reactions of the amino group (see Figure 4.1) that are, more or less, easily reversible are acylation (+H3N—(CR R2—) C02 — R— CO—Nil—(CR R2—) C02H) and the analogoussulphonylation, thioacylation and thiocarbamylation. N-Benzylation can be reversed by catalytic hydrogenation. 

Morpholinothio)thioxomethyl)morpholine olinothiooarbonyl)thio)morpholine OTOS thiocarbamyl-N -oxydiethylene sulfenamide. 

Arriaga, E., Chen, D. Y, Cheng, X. L., and Dovichi, N. J., High-efficiency filter fluorometer for capillary electrophoresis and its application to fluorescein thiocarbamyl amino-acids, J. Chmmatogr. A, 652, 347, 1993. 

Thiocarb. See Sodium diethyidithiocarbamate Thiocarbamide. See Thiourea Thiocarbamoylhydrazine Thiocarbamylhydrazine. See Thi osem icarbazide Thiocarbamyl sulfenamide CAS 13751-51-7 Synonyms OTOS N-... 

Butylene carbonate Ethylene carbonate Propylene carbonate accelerator, elastomers Sodium di-n-butyl dithiocarbamate accelerator, EPDM Thiocarbamyl sulfenamide accelerator, EPDM cures Zinc dibutyl dithiophosphorate accelerator, epoxies... 

N-Cyclohexyl-2-benzothiazolesulfenamide 1,3-Dibutylthiourea Dicyclohexylbenzothiazyl-2-sulfenamide Dimethyl diphenyl thiuram disulfide 2,6-Dimethylmorpholine Diphenylamine 4,4 -Dithiodimorpholine 2-Ethylbutyraldehyde Ethyl morpholine Formaldehyde aniline 2,6-Lutidine N-Nitrosodimethylamine Paraldehyde p-Quinone dioxime Selenium Selenium dimethyidithiocarbamate Sodium diethyidithiocarbamate Sodium dimethyidithiocarbamate Sodium nitrite N,N,N, N -Tetrabenzylthiuram disulfide Tetraisobutylthiuram disulfide Tetramethylthiuram disulfide Thiocarbamyl sulfenamide Thiophenol Thiourea Triethanolamine Triethylamine Triethylenetetramine n-Valeraldehyde Zinc dialkyl dithiophosphate Zinc diamyidithiocarbamate Zinc dibenzyl dithiocarbamate Zinc diisobutyidithiocarbamate Zinc isopropyl xanthate Zinc 2-mercaptobenzothiazole Zinc oxide Zinc-N-pentamethylene dithiocarbamate Zinc peroxide accelerator, rubber articles for repeated use food-contact... 

Thio-Arbuzov rearrangement 43, 543 N,N -Thiobisimides, sym. 43, 490 Thiocarbamic acid esters s. Thionocar-bamic acid esters Thiocarbamylation, ar. 20, 510s44 Thiocarbamyl halides... 

Halogenosulfenamides Halogenothioformamidinium salts Isothiocarbamyl halides Thiocarbamyl halides N-Thioiminohalides... 

Carbamides s. Ureas Carbamidiom salts s. Dithio-carbamidium salts Carbamyl s. a. Thiocarbamyl N-Carbamylamidines... 

C-Thiocarbamylation. Dimethylformam-ide added dropwise with ice-cooling and stirring to a suspension of NaH in a soln. of benzyl methyl ketone in dry benzene, then a soln. of C-phenylsul-fonyl-N,N-dimethylthioformamide in dry benzene added portionwise, warmed to room temp., and after 1.5 hrs. heated... 

Antimony pentachloride Cyclodimerization of aryl isothiocyanates N-(2-Benzothiazolyl)thiocarbamyl chlorides... 

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