Isothiocyanates and Related Compounds

The Chemistry of Ethoxycarbonyl Isothiocyanate and Related Compounds R. Esmail and F. Kurzer, Synthesis, 1975, 301-314. 

Review "The Chemistry of Ethoxycarbonyl Isothiocyanate and Related Compounds"... 

The addition of isocyanides and azide to aldehyde-derived enamines has led to tetrazoles (533,536). On the other hand the vinylogous amide of acetoacetic ester and related compounds reacted with aldehydes, isocyanides and acids to give a-acylaminoamides (534). Iminopyrrolidones and imino-thiopyrrolidones were obtained from the addition of cyclohexylisocyanide and isocyanates or isothiocyanates to enamines (535). An interesting method for the formation of organophosphorus compounds is found in the reactions of imonium salts with dialkylphosphites (536). 

This approach to 1,2,4-dithiazolidine derivatives 124 was investigated in detail by L abbe and co-workers on the example of a reaction of 4-alkyl-5-arylimino-l,2,3,4-thiotriazolines 123 and related compounds with isothiocyanates and other heterocumulenes. In these reactions, in addition to compounds 124, l,2,4-thiadiazolidine-3-thiones 125 are formed (Equation 17) <1996CHEC-II(4)453>. 

Bis(imino) thietanes, 343, 344, are prepared by reaction of isonitriles with iminothiiranes or of ketenimines with p-tolylsulfonyl isothiocyanate. Reaction of phosphonium ketimine ylides, for example, 312, and related compounds with isothiocyanates also gives bis(imino) thietanes, for example, 345. " Treatment of arylsulfonyl isothiocyanates with trimethylacetoisonitrile yields tris(imino)-thietanes, for example, 341. ... 

See Tables of Compounds in Ellis and Honeyman for data on glycosyl isocyanates and isothiocyanates, and glycosyl-urethans, -thiourethans, -hydantoins, -thiohydantoins, and related compounds. 

Table 1 provides an update of the Chang-Scheuer summary and lists the structures of all new marine sesquiterpene isocyanides and related compounds including isothiocyanates, (1 - 67), by compound class,... 

Table 2 Isolation of Diterpene Isocyanides, Isothiocyanates, Formamides and Related Compounds 1976-1997...

Glycosyl-carbamates, -isothiocyanates, thioureas and Related Compounds... 

The first U.S, patent to cover dithiocarbamates for use as fungicides was issued in 1934 to Tisdale and Williams O). This patent covered Vapam and dithiocarbamates of the formula X-ljl-CS-Z where X is a hydrogen or an alkyl radical, Y is hydrogen, alkyl or aryl and Z may be a metal or a saltforming group such as ammonium and sodium. It is a known fact that Vapam and related compounds decompose to isothiocyanates and sodium hydrosulfide. 

Munday, R. and Munday, C.M. 2004. Induction of phase II detoxification enzymes in rats by plant-derived isothiooyanates comparison of allyl isothiocyanate with sulforaphane and related compounds. Journal of Agricultural andFood Chemistry, 52(1), 1867-71. doi 10.1021/ jf030549s. 

Haristoy X, Fahey JW, Scholtus 1 et al (2005) Evaluation of the antibacterial effects of several isothiocyanates ot Helicobacter pylori. Planta Med 71 326-330 Higdon IV, Delage B, WiUiams DE et al (2007) Cruciferous vegetables and human cancer risk epidemiologic evidence and mechanistic basis. Pharmacol Res 55 224-236 Holst B, WiUiamson G (2004) A critical review of the bioavailabihty of glucosinolates and related compounds. Nat Prod Rep 21 425-447... 

C Fj-NFa), trifluoromethyliminosulphur diiluoride [- - CFj-NFa, (CFa)2NF], pentafluoroethyliminosulphur difluoride CaFs NFa), cyanuric fluoride CFs-NF, (CFa)jNF], thiocyanuric acid [-< CFj-NFj, (CF8)aNF], melamine [- CF3 NF2, (CFs)aNF, CFa(NFa)a], methyl thiocyanate (-> CFa NFj), and methyl isothiocyanate CFs-NFa) carbon tetra-fluoride and nitrogen trifluoride were the major products from these fluorina-tions, and a study has been made of the production of the latter via electrochemical fluorination of urea and related compounds. Details of the production of AtALdifiuorotrifluoromethylamine via injection of carbon tetrafluoride into a nitrogen plasma at 1500—6000 K and direct fluorination of potassium cyanide" have appeared in the patent literature preparation of this difluoroamine by u.v. irradiation of a mbcture of hexafluoro-acetone and tetrafluorohydrazine has also been described, and the new compounds CFCla-NFa, CClj-NFg, and ClS-CCIj-NF, have been obtained by photolysis of the hydrazine in the presence of thiocarbonyl chloride. ... 

Resulting from studies on the antivaccinia activity of pterygo-spermln, a number of substituted potassium benzylaminothiomethane-sulphonates and related compounds were made of which several possessed antivaccinia and anti-influenza activity in tissue culture, ovo and in animals (89,90,91). Fart of the mode of action of these compounds appears to be due to the liberation of isothiocyanate. 

There may be some important health protective effects of glucosinolate derivatives and related compounds. The hydrolytic products of some glucosino-lates have been shown to display anticancer properties. Glucosinolates are hydrolyzed following exposure to the endogenous plant enzyme myrosi-nase (also found in the gut microflora) to form isothiocyanates. Isothiocyanates are biologically active compounds with anticancer properties and are more bioavailable than glucosinolates. 

Related to this process is the hydrolysis of isocyanates or isothiocyanates" where addition of water to the carbon-nitrogen double bond would give an N-substituted carbamic acid (3). Such compounds are unstable and break down to carbon dioxide (or COS in the case of isothiocyanates) and the amine ... 

ZHANG Y, WADE K L, PRESTERA T and TALALAY p (1996) Quantitative determination of isothiocyanates, dithiocarbamates, carbon disulfide, and related thiocarbonyl compounds by cyclocondensation with 1,2-benzenedithioT, Anal Biochem, 239 160-67. 

During our studies of the kalihinols (Sect. 4.2.2), isothiocyanate 28 was one of several isocyano-related compounds isolated from Acanthella klethra from Australia. Its structure was also published independently from a Ciocalypta sp. in Hawaii [37] and reported as a poster at the 1988 Gordon Research Confer-... 

Al-Dirbashi O, Kuroda N, Aldyama S, Nakashima K. 1997. High-performance liquid chromatography of methamphet-amine and its related compounds in human urine following derivatization with fluorescein isothiocyanate. J Chromatogr B Biomed Sci Appl 695(2) 251-258. 

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