Phosphorinane sulfides

Phosphorinane, 4-t-butyl-1 -phenyl-synthesis, 1, 500 Phosphorinane, I-chloro-synthesis, 1, 500 Phosphorinane, 1-hydrocarbyl-I-sulfide synthesis, 1, 500 Phosphorinane, 1-phenyl-synthesis, 1, 499 Phosphorinanes, 1, 497-506 bicyclic bridged derivatives synthesis, 1, 501 conformation, 1, 503-504 NMR, 1, 497 oxidation, 1, 498 reactions, 1, 497 structure, 1, 497, 503-504 sulfuration, 1, 499 synthesis, 1, 499... 

Unlike 1,3,5-dioxaphosphorinanes the relative population of the con-former with the axial phenyl group at phosphorus decreases in 1,3,5-diazaphosphorinanes both for P(III) and for P(IV) compounds. Conformational analysis of 5-phenyl-1,3,5-diazaphosphorinanes and their oxides, sulfides, and selenides showed that the conformational equilibrium shifted toward the conformer with the axial phenyl group on changing from P(III) to P(1V) derivatives. The same conclusion made for 5-phenyl-l, 3,5-dioxaphosphorinanes, but it is contrary to that made for 1-phenyl-phosphorinane-4-ones and their derivatives (83MI1). 

Tertiary amines or pyridine reacts with diphenylboryloxyalkyl(a-oxyal-kyl)phenylphosphine sulfide to give the corresponding ammonium dioxa-borataphosphorinanes [Eq. (114)] (83IZV2545). Ammonium dioxaborata-phosphorinane was obtained by refluxing betaine 104 in triethylamine [Eq. (115)] (92IZV1398). 

Monocyclic tetrahydrophosphorin derivatives can be prepared, for example by dehydration of tertiary alcohols which are available by the action of lithium alkyls on 4-oxophos-phorinane derivatives (equation (16)). P- Oxidation and dehydrogenation of the ketone with Se02 is also possible (equation (17)) (66AG(E)588). Electrophilic substitution in position 2 (6) of phosphorinane 1-oxides and 1-sulfides can be achieved by a Wittig-Horner a-deprotonation, e.g. equation (18) (72BSF(2)402l, 79CJC723). 

The diagnostic coupling constant /P c for conformational analysis of phosphorinanes (P-CN = 3) is lost with phosphorinanes where P-CN = 4. Shifts and /P c values of two non-rigid and two cis-trans rigid phosphorinane 1-oxides and 1-sulfides should be studied for comparison (Tables 2 and 3). The large differences between the two classes are then evident. 

Diethylamino-methyl)-l,3,2-dioxaphosphorinan-2-snlfid771 Zu 1,5 g (11 mmol) 2-Hydro-1,3,2(A°)-dioxa-phosphorinan-2-sulfid gibt man bei 0-2° 1,32 g (8,3 mmol) Bis-[diethylamino]-methan und erwarmt das Ge-misch 1 Stde. auf 60°. Dann wird das Diethylamin i. Vak. entfernt, der Ruckstand wird destilliert Ausbeute 1,45 g (78%) Sdp. 70-7370,008 Torr (1 Pa). 

Thiophosphorsaure-O.O-diester-jodide sind mit Jod in Ethanol in Gegcnwart von Kaliumhydrogencarbonat bei 40° zuganglich77 z.B. 5,5-Dimethyl-2-jod-1,3,2-dioxa-phosphorinan-2-sulfid (40% Schmp. 142-143°). 

Inch and co-workerspioneered, in the 1970s, the preparation of many phosphorinane oxides and sulfides derived from carbohydrates, confirming their utility in the study of stereochemical aspects in nucleophilic substitutions at phosphorus. Some of the compounds they prepared are shown in Figure 3.9. 

Figure 3.9 P-stereogenic phosphorinane oxides and sulfides derived from carbohydrates.

C11H13OPS, 1-Phenyl-4-phosphorinanone 1-sulfide, 45B, 731 C11H13O2P, 1-Phenyl-4-phosphorinanone 1-oxide, 45B, 731 Cl 1H1 aC10i,P, 2-Phenoxy-5-chloromethyl-5-methyl-2-oxo-1, 3,2-dioxa-phosphorinane, 39B, 495... 

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