Phosphorins, tetrahydro

Phosphorins, tetrahydro-17, 798 Phosphorochloridates (s. a. Bis-(l-imidazolid-2-onyl)-phosphoryl chlorides, Phosporodichloridates, Pyrocatechyl phosphoro-trichloridate)... 

Phosphorin-3-carbonitrile, 4-amino-l-phenyl-1,2,5,6-tetrahydro-, 53, 99 Phosphorus heterocycles, 53,... 

The lithium salt of enantiomerically pure (2S,65)-6-methyl-tetrahydro-2//-l,3,2-oxaza-phosphorine-2-oxide was also alkylated with high diastcrcosclcctivity, whereas in the case of the (2/ ,6S)-isomer only moderate selectivities were observed. With the 3-isopropyl derivative even higher selectivities (97-98% de) were observed. 

Electrophilic attack occurred on the Re-face of lithiated (25,6S)-tetrahydro-2W-l,3,2-oxaza-phosphorine 2-oxides to give 7 -configurated products, as was confirmed by X-ray crystallo-... 

B. Preparation of 4-Amino-1,2,5,6-tetrahydro-l-phenyl-phosphorin-3-carbonitrile. To a nitrogen-flushed 1-1. threenecked flask equipped with a mechanical stirrer, a pressure-equalizing addition funnel, and a reflux condenser are added 25 g. (0.22 mole) of potassium room temperature, 250 ml. of water is added, and the resulting mixture is stirred for 30 minutes while the product crystallizes. The mixture is filtered, and the solid product is washed on the filter with two 50-ml. portions of cold ethanol to give, after drying at 78° (1 mm.), 36-38 g. (84-88%) of 4-amino-1,2,5,6-tetrahydro-1 -phenylphosphorin- 3-carboni-trile, m.p. 134.5-137° (Note 9). A small amount of product can be recovered from the filtrate (Note 10). 

C. Preparation of l-Phenyl-4-phosphorinanone. A solution of 35 g. (0.162 mole) of 4-amino-l,2,5,6-tetrahydro-l-phenyl-phosphorin-3-carbonitrile in 400 ml. of 6N hydrochloric acid... 

Phosphorinanones have been utilized as substrates for the preparation of alkenes,11 amines,12 indoles,5,13 and in the synthesis of a series of secondary and tertiary alcohols via reduction,10 and by reaction with Grignard6,11 and Refor-matsky11,14 reagents. Phosphorinanones have also been used as precursors to a series of 1,4-disubstituted phosphorins.15 The use of 4-amino-l,2,5,6-tetrahydro-l-phenylphosphorin-3-carbonitrile for the direct formation of phosphorino-[4,3-d] pyrimidines has been reported.16... 

Auf ahnliche Weise wird 4-Methyl-1-phenyl-1,2,3,4-tetrahydro-(benzo[b]phosphorin)-1-oxid (R = H, R2 = H, R3 = CH3) 70% Schmp. 114-115° erhalten. 

N,N,a-TRIMETHYL-10H-PHENOTHIAZINE-10-ETHANAMNE MONOHYDROCHLORIDE see PMI750 N,N,3-TRIS(2-CHLOROETHYL)TETRAHYDRO-2H-1,3,2-OXi3.PHOSPHORIN-2-AMINE-2-OXIDE see... 

Dichloro-1,2,3,6-tetrahydro-1,4,5-trimethy1-A --phosphorin 1-oxide, m.p. 84°, and some related compounds have been prepared (Y. Kashman and A. Rudi, Tetrahedron Letters, 1979, 1077). 

A niimber of 3,5-disubstituted and 3,4,5-trisubstituted X --phosphorins have been prepared from 1,2,3,6-tetrahydro-1- te2 t butylphosphorin-3-ones (Markl, Hock, and L. Merz, Ber., 1984, JM7, 763). 

A new method for the preparation (NPPh2)3 from KNPPh3 in the presence of M0O3 and 18-crown-6 has been described.S Novel l,2,5,6-tetrahydro-l,3-oxaza-4-phospha-2-phosphorine-2-oxides have been synthesized by metallation of linear phosphazenes R R C-P(Ph2)=N-P(0)(0Ph)2 with Bu"Li and subsequent quenching by aldehydes or ketones. ... 

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