- Thermal studies on piperidinium hexathiocyanatochromate(III)
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Piperidinium hexathiocyanatochromate(III), (pipH)3[Cr(NCS)6], was synthesized using the molten salt pipHSCN and was found to contain nitrogen-bonded thiocyanate. The (pipH)3[Cr(NCS)6] decomposes in the range 250
- House Jr.,Marquardt, Lois A.
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p. 265 - 269
(2008/10/08)
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- SELECTIVITY OF NUCLEOPHILIC ADDITION TO AND SUBSTITUTION AT ISOTHIOCYANATOCARBONYL GROUP. REACTIONS OF 4-PENTINOYL- AND 2-(2-PROPINYL)-4-PENTINOYL ISOTHIOCYANATE WITH AMINES AND METHANOL
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4-Pentinoyl isothiocyanate reacts with primary and secondary amines by either nucleophilic addition to N=C=S group to yield the corresponding thioureas, or a nucleophilic substitution at the carbonyl group to give 4-pentinoic acid amides.The less nucleophilic diphenylamine reacts selectively to afford the product of nucleophilic addition only. 2-(2-Propinyl)-4-pentinoyl isothiocyanate, having a sterically hindered carbonyl group, furnished with primary amines a mixture of amides and thioureas, whereas the bulkier secondary amines react selectively to form thioureasonly.Both isothiocyanates afford with methanol as a nucleophile axclusively the corresponding O-methyl monothiocarbamates.
- Kutschy, Peter,Kristian, Pavol,Dzurilla, Milan,Koscik, Dusan,Nadaskay, Robert
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p. 995 - 1005
(2007/10/02)
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- Nucleophilic Substitution on 4-Methylbenzyl Thiocyanate with Nucleophiles
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The reactions of 4-methylbenzyl thiocyanate (1) with several nucleophiles have been investigated.Compound 1 possesses three electrophilic sites, i.e., benzylic carbon, sulfur and cyano carbon, to receive nucleophilic attack.PhS- and CN- which have HOMO's of high energy levels appear to attack preferentially the sulfur atom.MeO- was found to attack preferably the cyanide carbon, while amines which have HOMO's of low energy levels prefer benzylic carbon to attack.The nucleophilic substitution on the sulfur or the cyanide carbon generates CN- or p-xylene-α-thiolate anion, strong nucleophiles, as the primary products, which then initiate the complex secondary reactions.The selective reactivities of three attacking sites for nucleophiles in 1 have been rationalized in terms of MO theory.
- Oae, Shigeru,Yamada, Norihiro,Fujimori, Ken,Kikuchi, Osamu
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p. 248 - 256
(2007/10/02)
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