Thio cyanates

Faneti/ole (122) is a biological response modifier with significant immunosuppressant activity It can be synthesized by conversion of 2 phen> lethylamine (120) with ammonium thio cyanate to the corresponding thiourea analogue 121 The synthesis of faneli/ole (122) concludes by thiazole nng formation of 121 by reaction with phenacylbromide Thus its synthesis involves use of the classic Hantzsch procedure in which a bromoacetone analogue and an appropriate thio urea denvative are reacted 143]... 

Sulfocyankalium, n. potassium thiocyanate, sulfocyansauer, a. of or combined with sulfo-cyanic (thiocyanic) acid, sulfocyanate (thio cyanate) of. 

Sulfocyan-saure, /. sulfocyanic acid (thiocyanic add), -verbindung, /. sulfocyanate (thio cyanate). 

It now appears that the most usual coordination mode in c/s-di(thio-cyanate) complexes is one N-bound and one S-bound thiocyanate, as an angular Pd—SCN bond minimizes interaction with the other bound thiocyanate and with the other ligands. 

Figure 6.51 Biflinctional (thio)urea-phoshine catalysts 166-168 prepared from (R)-2 -diphenylphosphanyl- [1,1 ]binaphthalenyl-2-ylamine and the corresponding iso(thio) cyanate the yield of the catalysts is given in parentheses. Catalyst screening results ofthe...

Azolines of type (13) undergo thermal decomposition in an analogous way to that already discussed for azolones (see Section 4.14.5.2) (Scheme 19). Path (i) is followed by those azolines having Z = S and path (ii) by those with Z = O. Path (i) is a typical retro-1,3-dipolar cycloaddition process, via an intermediate nitrile sulfide, while path (ii) might involve an acyl (Y = Z = O) or thioacyl (Y = S, Z = O) nitrene intermediate (136), which in turn rearranges to iso(thio)cyanate. However, no systematic attempts to trap this possible nitrene intermediate seem to have been made, and so a concerted pathway for the fragmantation cannot be ruled out. 

Mesoionic pyrido[2,l- >][1,3]oxazines (54) afforded 4-oxo-4//-pyrido[l,2-a]pyrimidin-l-iumolates (55) and 4//-quinolizin-4-one (56) with phenyl iso(thio)cyanates [78LA1655 79CB1585 82ZN(B)222] and dimethyl acetylenedicarboxylate (79CB1585), respectively. Reaction of 2-cyano-3-methyl-lH,6//-pyridol[l,2-a][3,l]benzoxazine-l,6-dione with ammonium acetate and hydroxylamine, hydrazines, primary aliphatic or aromatic amines, and (thio)ureas gave 5-unsubstituted and 5-substituted 2-cyano-3-methyl-l//,6H-pyrido[l,2-a]quinazoline-l,6-diones (93CCC1953). 

The reaction of phosgene [75-44-5] or thiophosgene [463-71-8] with ethyleneimine yields either a bisaziridine compound (l,l -carhonylhisaziridine [1192-75-2] on l,T-thiocarbonylhisaziridine [13163-23-0]) or a 2-chloroethyliso(thio)cyanate, depending on the reaction conditions. The former can he isomerized by catalysis with triiodide to give l-aziridinyl-2-oxazoline [19587-77-0] or l-aziridinyl-2-thiazoline [17205 18-0] (173—177). 

Indole, like benzothiophene, reacts with electrophiles to give preferentially -substituted products. Bromination241-243 in dioxane or pyridine, nitration by ethyl nitrate,244 chlorination by sulfuryl chloride,245 iodination in aqueous solution,246, 247 Vilsmeier and Reimer-Tiemann formylations,248-261 diazo coupling,252 thio-cyanation,263 and nitrosation254 all give the 3-substituted indoles, practically free from other isomers. 

As part of a study of a series of glycosylureides, Micheel and Haben-dorff212 treated methyl (2,3,4-tri-O -acetyl-/3-D-glucopyranosy 1 thio-cyanate)uronate with methanolic ammonia at 0°, and obtained, by way of the (nonisolated) isothiocyanate 105, the crystalline thiourea derivative 106 in 91.8% yield the structure assigned to 106 was supported... 

To facilitate the program it was decided to study the cobalt(II)-thio-cyanate complex system which was as accessible to direct assay in the exchanger phase as it was in the solution phase by absorption spectrophotometry in the visible region. Both Co(II) and Co(SCN) exhibit sizably different spectral absorption properties in the visible region. Assuming that the presence of higher complexes than one to one in the cation... 

The isomerism existing in the case of cyanides or nitriles and isocyanides or iso-nitriles, which we have just discussed, is found also, in part, in their oxidation products the iso-cyanates and in analogous sulphur compounds the thio-cyanates and iso-thio-cyanates. We have referred to the fact that hydrocyanic acid like hydrochloric acid yields an oxygen acid which though unknown itself is represented by well known salts. 

This same substitution of sulphur for oxygen occurs in the case of cyanic acid and its salts, e.g., potassium thio-cyanate and ammonium thiocyanate used as reagents in testing for ferric iron. 

Alkyl Thio-cyanates Alkyl Iso-thio-cyanates.—In the alkyl derivatives of thio-cyanic acid we again have isomerism exactly analogous to that in the unknown cyanates and the known iso-cyanates. 

Allyl Cyanide, Iso-thio-cyanate, etc.—From allyl chloride or the iodide there may be prepared by the customary reactions allyl cyanide and other of the cyanogen compounds. With potassium cyanide allyl iodide yields allyl cyanide. The reaction, however, instead of yielding a cyanide of the expected constitution is accompanied by a shifting of the double bond to the second carbon so that the cyanide has a constitution unlike that of the iodide from which it is made. 

Oil of Mustard.—Only the last compound named is important, viz., allyl iso-thio-cyanate, CH2 = CH—CH2NCS. Strange as it may seem, from statements made in connection with the cyanates and iso-cyanates of the saturated series, this compound is made by treating allyl-iodide, not with silver thio-cyanate, but with potassium thio-cyanate. As, however, the tautomeric iso-compounds are made from the cyanates and thio-cyanates by heat, the conversion of the first formed thio-cyanate into the iso-thio-cyanate can readily be understood. 

Allyl iso-thio-cyanate is found in nature as a glucoside constituent of mustard seed. It is known, therefore, as mustard oiL It is a liquid with a sharp odor and with a boiling point of 150.7 . The proof that it is iso-thio-cyanate is its conversion into allyl-amine, CH2 = CH—CH2NH2. 

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