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Zusammenfassung CH3PCl2 und C6H5PCl2 reagieren mit Brenzcatechin bei Anwesenheit von Triäthylamin als HCl-Akzeptor zu 2-Methylbzw. 2-Phenyl-1,3,2-benzodioxaphosphol. Dabei hängt die Ausbeute sehr stark von den Reaktionsbedingungen ab, da die Produkte ihrerseits mit Brenzcatechin unter H2-Entwicklung oder mit sich selbst unter Disproportionierung reagieren können, wobei 2-Organo-2,2-spirobi[1,3,2-benzodioxaphosphol] entsteht.
Reactions of catechol with methyl- and phenyldichlorophosphine
CH3PCl2 and C6H5PCl2 react in presence ofEt 3N with catechol with the formation of 2-methyl- and 1.3.2-benzodioxaphosphole (1) and 2-phenyl-1.3.2-benzodioxaphosphole (3), resp. The yields depend strongly on the reaction conditions because the said products are susceptible to a further reaction with catechol and to a disproportionation giving 2,2-spirobi-[1.3.2-benzodioxaphospholes] (2 and4, resp.). *** DIRECT SUPPORT *** A3615139 00012
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Zusammenfassung Bei der Aminoborierung von Carbonylsulfid erfolgt 1,2-Addition an die Carbonylgruppe, wobei in Tris(dimethylamino)boran zwei der B–N-Bindungen, in Bis(dimethylamino)chlorboran nur eine B–N-Bindung reagieren. In Tris(2,2-dimethylhydrazino)boran reagieren alle drei B–N-Bindungen mit CO2; mit CS2 erfolgt unter den gleichen Bedingungen keine Reaktion. Mit Phosgen und Thiophosgen reagiert Tris(dimethylamino)boran unter Bildung von Bis(dimethylamino)chlorboran und substituierter Carbamide.
Reactions of aminoboranes and hydrazinoboranes with carbonyl and thiocarbonyl compounds
Upon aminoboration of carbonyl sulfide 1,2-addition to the carbonyl group is observed. In tris(dimethylamino)borane insertion into two of the B–N bonds occurs, while in bis(dimethylamino)chloroborane only one B–N bond reacts with OCS. In tris(2,2-dimethylhydrazino)borane all three B–N bonds react with CO2, while with CS2 no insertion reaction is observed under comparable conditions. Tris(dimethylamino)borane reacts with phosgene and thiophosgene with formation of bis(dimethylamino)chloroborane and substituted carbamides.
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The compound [Cp′Mn(CO)2]Se2 (1) reacts with primary arsanes and phosphanes, and migration of the carbonylmetal fragment Cp′Mn(CO)2 (Cp′ = CH3C5H4) from the selenium to the arsenic or phosphorus center occurs. Products of these reactions are diselena-diarsetanes (4) or diselena-diphosphetanes (5). During the reaction of arsanes with 1, arsinidene complexes (2) are obtained in very good yields. Compounds with a PSeP unit (6) can be isolated as by-products of the reaction of phosphanes with 1.  相似文献   

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Reactions of Alcohols and Mercaptans with Tetraphosphorus Trichalcogenide Diiodides α-P4E3(I)R and α-P4E3R2 (R = -OCH3, -OC2H5, -OCH(CH3)2, -OC(CH3)3 and -OC6H5) have been detected in the reaction solutions of α-P4E3I2 (E = S, Se) with alcohols in the presence of triethylamine, or with trimethyltin alkoxides in CS2. β-P4S3I2 reacted with methanol at 243 K in CS2 to yield β-P4S3(I)OCH3, β-P4S3(OCH3)exo(OCH3)endo, and β-P4S3[(OCH3)exo]2. The thiolates α-P4Se3R2′ (R′ = -SC2H5, -n-SC5H11, -n-SC7H15, -SC(CH3)3 and -SC6H5) were found in reaction solutions of α-P4Se3I2 with thiols HR′. The 31P NMR data of these compounds are given.  相似文献   

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E.V. Dehmlow 《Tetrahedron》1972,28(1):175-179
Compared to dichlorocarbene from other sources the highly reactive dichloro carbene reagent of Makosza and Wawrzyniewicz gives better yields of bis- und tris-adducts even with compounds lacking activation. Compounds 4, 10, and 11 have been prepared for the first time; Compounds 10 and 11 show unusual long-range couplings between methyl protons 5 bonds apart.  相似文献   

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