ISSN:
0009-2940
Schlagwort(e):
Chemistry
;
Inorganic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Beschreibung / Inhaltsverzeichnis:
Reactions of (Organo)phosphorus-Oxygen Compounds with Diorgarno-hydro-boranes1)Trialkyl phosphites P(OR)3 [R=CH3 (2a), C2H5 (2b), CH(CH3)2 (2c), C4H9 (2d)] react with tetraalkyldiboranes(6) (R′2BH)2 [R′=C2H5 (1a)2, C3H7 (1b)2] in a temperature-dependent manner between 20 and 130°C to form the trialkyl phosphite-boranes (RO)3P-BHR′2, (RO)3P-BH2R′, and (RO)3P-BH3, which have various stabilities toward alcohols. With bis(9-borabicyclo-[3.3.1]nonane) (1c)2 the easily protolyzed addition compounds are obtained [e.g. 2a-1c, 2c-1c]. - Diorgano phosphites (RO)2P(O)H [R=CH3 (3a), C4H9 (3b), C6H5 (3c), CH2C6H5 (3d)], triorgano phosphates (RO)3PO [R=CH3 (4a), C4H9 (4b), C6H5 (4c), 2-CH3C6H4 (4d)], and the monosaccharide-diphenyl phosphates 4f, 4g, and 4h are reduced by (1a)2 or (1c)2 to give H2, PH3, and insoluble yellow phosphorus compounds, respectively. Phosphoric acid (4e), their derivatives OP(OBR2)3 [R=C2H5 (4ea), R2=C8H14 (4ec)], and phenylphosphonic acid C6H5P(O)-(OH)2 (6) are not deoxygenated at 130°C by (1a)2 to (1c)2. - Diorganophosphinic acids R2P(O)OH [R=C6H5 (5a), c-C6H11 (5b)] and phenylphosphinic acid C6H5(H)P(O)OH (5c) are reduced by (1a)2-(1c)2. Reaction of 5a with (1a)2 leads to the compounds [(C6H5)2P(BH3)O]B(C2H5)2 (8a-BH3), [(C6H5)2P-(BH3)O]BC2H5 [9a-(BH3)2], and [(C6H5)2P(BH3)O]3B [10-(BH3)3]. 5a reacts with (1c)2 under simultaneous formation of (C6H5)2PH (7) or (C6H5)2PH-HBC8H14 (7-1c) and (C6H5)2-POBC8H14 (8c) or (C6H5)2P(OBC8H14)-HBC8H14 (8c-1c). - 6 reacts with tetraethyldiboroxane (11a) to form a mixture of the oligomeric compounds -P(C6H5)(O)OB(C2H5)O]n-(6′a)n.
Notizen:
Trialkylphosphite P(OR)3 [R=CH3 (2a), C2H5 (2b), CH(CH3)2 (2c), C4H9 (2d)] reagieren mit Tetraalkyldiboranen(6) (R′2BH)2 [R′=C2H5 (1a)2, C3H7 (1b)2] in Abhängigkeit von der Temperatur (20 bis 130°C) unter Bildung der gegenüber Alkoholen unterschiedlich stabilen Trialkylphosphit-Borane (RO)3P-BHR′2, (RO)3P-BH2R′ und (RO)3P-BH3. Mit Bis(9-borabicyclo-[3.3.1]nonan) (1c)2 erhält man die protolytisch leicht spaltbaren Additionsverbindungen [z.B. 2a-1c, 2c-1c]. - Diorganophosphite (RO)2P(O)H [R=CH3 (3a), C4H9 (3b), C6H5 (3c), CH2C6H5 (3d)], Triorganophosphate (RO)3PO [R=CH3 (4a), C4H9 (4b), C6H5 (4c), 2-CH3C6H4 (4d)] sowie die Monosaccharid-Phosphorsäure-diphenylester 4f, 4g und 4h werden von (1b)2 bzw. (1c)2 unter Bildung von H2, PH3 und/oder unlöslichen, gelben Phosphor-Produkten reduziert. - Phosphorsäure (4e), deren Derivate OP(OBR2)3 [R=C2H5 (4ea), R2=C8H14 (4ec)] und Phenylphosphonsäure C6H5P(O)(OH)2 (6) lassen sich von (1a)2 - (1c)2 bis 130°C nicht desoxygenieren. - Diorganophosphinsäuren R2P(O)OH [R=C6H5 (5a), c-C6H11 (5b)], Phenylphosphinsäure C6H5(H)P(O)OH (5c) werden von (1a)2 bis (1c)2 reduziert. 5a und (1a)2 bilden [(C6H5)2P(BH3)O]B(C2H5)2 (8a-BH3), [(C6H5)2P(BH3)O]2BC2H5) [9a - (BH3)2] und [(C6H5)2P(BH3)O]3B [10-(BH3)3]. Mit (1c)2 reagiert 5a unter gleichzeitiger Bildung von (C6H5)2PH (7) bzw. (C6H5)2PH-HBC8H14 (7-1c) sowie von (C6H5)2POBC8H14 (8c) bzw. (C6H5)2P(OBC8H14)-HBC8H14 (8c-1c). - 6 bildet mit Tetraethyldiboroxan (11a) ein Gemisch oligomerer - [P(C6H5)(O)OB(C2H5)O]n-Verbindungen (6′a)n.
Zusätzliches Material:
6 Tab.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/cber.19871200707
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