Butyl isothiocyanates

Secondary butyl isothiocyanate, CH3. CH. CH(CH3). N C S, has been isolated from the oils of Cardamine amara and Cochlearia. It is a liquid with a powerful, irritating sulphur odour, having a specific gravity 0 9415 and boiling at 159° to 160°. Warmed with alcoholic solution of ammonia, it yields a thiourea, melting at 135° to 136°. 

The artificial cochlearia oil of commerce is not identical with secoudai-j-butyl isothiocyanate, but consists of isobutyl isothiocyanate. It is a liquid boiling at 162° and yields a thiourea, melting at 93-5°. 

The edible portion of broccoli Brassica oleracea var. italica) is the inflorescence, and it is normally eaten cooked, with the main meal. Over 40 volatile compounds have been identified from raw or cooked broccoli. The most influential aroma compounds found in broccoli are sulfides, isothiocyanates, aliphatic aldehydes, alcohols and aromatic compounds [35, 166-169]. Broccoli is mainly characterised by sulfurous aroma compounds, which are formed from gluco-sinolates and amino acid precursors (Sects. 7.2.2, 7.2.3) [170-173]. The strong off-odours produced by broccoli have mainly been associated with volatile sulfur compounds, such as methanethiol, hydrogen sulfide, dimethyl disulfide and trimethyl disulfide [169,171, 174, 175]. Other volatile compounds that also have been reported as important to broccoli aroma and odour are dimethyl sulfide, hexanal, (Z)-3-hexen-l-ol, nonanal, ethanol, methyl thiocyanate, butyl isothiocyanate, 2-methylbutyl isothiocyanate and 3-isopropyl-2-methoxypyrazine... 

Methylthio)propyl isothiocyanate 4- (Methylthio)butyl isothiocyanate [35] [35, 177]... 

Jimenez et al. [24] have synthesized receptors l,5-bis-N-(9,10-dioxo-9,10-di-hydroanthracen-l-yl)-AT-butylthiourea 18 and its urea analogue, 1,5-bis-AT-(9,10-dioxo-9,10-dihydroanthracen-l-yl)-N/-butylurea 19,by condensation of 1,5-diaminoanthraquinone with butyl isothiocyanate and butyl isocyanate, respectively. 

Sodium salt of acetylsulfaniamide N-Butyl isothiocyanate Sodium nitrite... 

The use of N-methyl-N -t-butylcarbodiimide as a diagnostic tool results in the formation of t-butyl isothiocyanate on fragmentation because addition of the C =S bond of the isothiocyanate occurs across the less sterically hindered 0=N group of the carbodiimide. ... 

C5H9I cis-1 -iodo-3-methyl-1 -butene 64245-25-6 410.66 35.026 2 5265 C5H9NS tert-butyl isothiocyanate 590-42-1 413.15 35.606 1,2... 

The root of Raphanus sativus var. niger (black radish) contains 0.0025% of essential oil with glycosides yielding allyl isothiocyanate and butyl isothiocyanate. 

However, this behavior is not completely general, since fragmentation of likewise substituted imidoyls 5 can follow two competitive pathways depending on the stability of the released radical (R or Y). For instance, addition of methylsulfanyl radicals to tcrt-butyl isonitrile does not afford tert-butyl isothiocyanate (6, R = tert-Bu, X = S) but instead methyl thiocyanate (7, XY = SMe), due to preferential formation of the more stable tert-huiyl radical [5f]. 

Mesoionic thiazoles such as (69) can be considered to be potential precursors in basic media of cyclic azomethine ylids. These mesoionic thiazoles can be generated from 5-(tert-butylamino)thiazolium chlorides (68). They can undergo 1,3-dipolar cycloaddition reactions with carbon disulphide. The initial cycloadducts (70) and (71) rapidly eliminate tert-butyl isothiocyanate at room temperature to give the thiazolium-... 

Reaction of o-phenylenediamine with phenyl isothiocyanate in CCI4 gave thiocarbamide 37 which underwent oxidative cyclization to benzothiadiazine 38 upon treatment with ethanolic iodine followed by basification with ammonium hydroxide solution (Scheme 2). Analogous results were obtained using a variety of ring-substituted phenyl isothiocyanates as well as /-butyl isothiocyanate in this sequence, with overall yields ranging from 69% to 87% <2004JIC775>. 

A soln. of diethyl N-butylphosphoramidate in benzene added dropwise with stirring to a suspension of NaH and a little tetra-A -butylammonium bromide in the same solvent over 30 min at 50, after 2 h CS2 added in 1 portion at room temp., the mixture refluxed for 2 h, and left overnight at 20-25° butyl isothiocyanate. Y 91 % (30-50% without Bu4NBr). F.e. incl. N-aryl derivs. s. B. Oleiniczak, A. Zwierzak, Synthesis 1989, 300-1. 

This reagent is prepared in good yield from the reaction of tert-butyl isothiocyanate (readily available commercially) with sodium azide (eq 1). ... 

Butyl isothiocyanate reacts with Bu3PbH at 0° C without precipitation of lead. After 3 hours the lead hydride is used up but not the isothiocyanate. The smell of isonitrile and the strong absorption in the N—H region at 3220 cm make it probable that reduction is the main reaction. The 1 1 adduct could not be isolated 152). 

The cancer chemopreventive effect of cruciferous vegetables is mainly attributed to ITCs. The most important ITCs found in cruciferous crops are sulforaphane (SFN), allyl isothiocyanate (AITC), phenethyl isothiocyanate (PEITC), benzyl isothiocyanate (BITC), iberin (4-meth-ylsulfinilpropyl isothiocyanate, MSPITC), and erucin (4-methylthio-butyl isothiocyanate, MTBITC) derived from aliphatic and aromatic GSLs. 

Ethylene glycol bis- (y-aminopropyl) ether added dropwise to er butyl isothiocyanate in ethanol, and stirred 1 hr. after heat evolution has subsided, the ethanol removed by distillation with dropwise replacement by water, dimethyl sulfate added to the resulting aq. suspension of the thiourea, refluxed 30 min., the soln. obtained added dropwise at 0-10° to excess Na-carbonate soln., stirred 1 hr., the resulting crude isothiourea heated 0.5 hr. at 175°, then refluxed 1 hr., and the mercaptan elimination completed by refluxing 0.5 hr. at 200°/12 mm 3,3 -bis-( ert-butylcarbodiimido) ethylene glycol dipropyl ether. Y 85%. F. e. and methods s. P. Schlack and G. Keil, A. 661, 164 (1963). 

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