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Download Cyanates and Their Thio Derivatives: Volume 2 (1977) PDF

Content:
Chapter 17 Syntheses and preparative purposes of isocyanates (pages 619–818): Reinhard Richter and Henri Ulrich
Chapter 18 Syntheses and preparative functions of thiocyanates (pages 819–886): R. G. Guy
Chapter 19 Selenocyanates and comparable compounds (pages 887–922): E. Bulka
Chapter 20 organic formation and reactions of cyanates (pages 923–967): Sasson Cohen and Edna Oppenheimer
Chapter 21 Syntheses and reactions of isocyanide dilhalides (pages 969–1001): Henri Ulrich and Reinhard Richter
Chapter 22 The chemistry of the — NCS staff (pages 1003–1221): L. Drobnica, P. Kristian and J. Augustin

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Additional info for Cyanates and Their Thio Derivatives: Volume 2 (1977)

Sample text

The reaction of phosphorus amides with phosgene often results in the cleavage of the P-N bond with formation of a P-CI bond. However moderate yields of phosphorus isocyanates can be obtained in the dircct phosgenation of (EtO),P(O)NH,, (MeO),P(S)NH, and (ArO),P(S)NH, in the presencc of pyridine”’. Instead of the free amide the sodium salt of the corresponding amide or urea can be usedZl6. ’ ”. 33 (RO)s P(X)NHz + (COCI), - (RO), P(X)NHCOCOCI ilt (176) -HCI. x = 0,s \. s- CO c (RO), P ( X ) N C O The most general method of synthesis of phosphorus isocyanates involves the reaction of phosphorus halides with sodium.

Also isocyanato complexes of transition metals do not fall within the scope of this chapter. The main groups of the periodic system have been used in order to present a consistent picture and the elemcnts under discussion are summarized in Scheme 3. - -. - . - _- __- . -. -- - Boron Silicon. germanium. tin. lead Nitrogen, phosphorus. arsenic. ant imonp Oxygen, sulphur C h 1or i n e. b r o m i ne. i od in e The standard method of synthesis of inorganic isocyanates consists of reaction- thc corresponding halides with a cyanate salt.

A related but slow conversion of phenyl isocyanate to triphenyl isocyanurate via 1,3diphenyl-l,3-diazetidinedionewas observed in presence of a guanidine catalyst'*". Trialkylphosphines. which have been regarded as highly specific dimerization catalysts for aryl isocyanates, were recently shown to catalyse the conversion of dimer into triper on prolonged standing of the reaction mixtures'88. Pyridines and other basic catalysts have an even lower degree of specificity because at elevated temperature trimerization competes with dimerization.

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