Phosphine, methyl trimethyl

SijInCijHj], Indium(III), tris[(trimethyl-silyl)methyl]-, 24 89 Si4ClPCuH , Phosphine, bis(trimethyl-silyl)methylene][chlorobis(trimethyl-silyl)methyl]-, 24 119... 

Colourless crystals of (6.973a), 3,5,8 trioxa-1-phosphabicyclo (2,2,2)octane, mp=88-89 C, can be made by heating tris(hydroxymethyl)phosphine with trimethyl orthofonnate in the presence of a little triethylamine (6.974). The methyl derivative, P(CH20)3 CMe can be obtained using MeC (OCHPa in this reaction. 

Stereochemistry. - There has been a far infra-red spectroscopic study of ethyl phosphine,130 and in combination with X-ray fluorescence, further work completed on the conformational analysis of dialkylphenyl phosphines.131 The influence of water on the conformational equilibria of trimethyl phosphate has received attention.132 There has been a low temperature solid state and matrix isolation study of methyl phosphorodichi oridate,133 and a conformational study of polymorphic modifications of diphenyl-phosphinyl acetic acid hydrazide. 34... 

Organophosphorus compounds. Phosphorus-carbon bond formation takes place by the reaction of various phosphorus compounds containing a P—H bond with halides or triflates. Alkylaryl- or alkenylalkylphosphinates are prepared from alkylphosphinate[638]. The optically active isopropyl alkenyl-methylphosphinate 778 is prepared from isopropyl methylphosphinate with retention[639]. The monoaryl and symmetrical and asymmetric diary lphosphi-nates 780. 781, and 782 are prepared by the reaction of the unstable methyl phosphinate 779 with different amounts of aryl iodides. Trimethyl orthoformate is added to stabilize the methyl phosphinate[640]. 

The alkylation of the zirconocene thioacetaldehyde complex 81a with excess Mel also yielded an 5-methylated product (122) [Eq. (26)]. In contrast, the protonation by methanol in excess gave ethanethiol, trimethyl-phosphine, and dimethoxyzirconocene, presumably via a [Zr(OMe)(SEt) (t75-C5H5)2] intermediate.70... 

PFeOC24H21, Ferrocene, [(diphenylphosphino) acetyl]-, [125798-01-8], 31 141 PGaClgH36, Gallium, trihydro(tricyclohexyl-phosphine)-, (T-4)-, [141727-22-2], 31 79 PI07ReC7H, Rhenium, tetracarbonyliodo (trimethyl phosphite-P)-, (OC-6-33)-, [134770-89-1], 31 249 PN02C24H42, Acetamide, Al,/V-bis(2-methyl-propyl>-2-(octylphenylphosphinyl)-, [83242-95-9], 31 145... 

The quinoline-2-one was then converted into the required 1-methyl-(o-azidophenyl)-quinoline-2-one via known synthetic manipulations. Cyclization of this intermediate to the target Cryptotackieine was performed under microwave irradiation at 180 °C for 30 min, in the presence of trimethyl phosphine. It is noteworthy that the same aza-Wittig reaction, when carried out under classical heating for 24 h, furnished inferior yields. The quinolin-2-one intermediate, when heated at 150 °C in o-xylene under conventional heating conditions, underwent a nitrene insertion at the C-4 position of the pyridinone ring. Subsequent Red-AI reduction of the carbonyl group furnished the Cryptosanguinolentine. 

C 3H27NPSi, Phosphinous amide P-methyl-P-phenyl-N,N-bis(trimethyl-sUyl)-, 25 72... 

NOPC12H12, Phosphinic amide, diphenyl-lanthanoid complexes, 23 180 NOPSiCi2H]9, Phosphinimidic acid, P-methyl-F-phenyl-iV-(trimethylsilyl)-2,2,2-trifluoroethyI ester, 25 72 NOSSiCsHj, Silanamine, 1,1,1-trimethyl-iV-sulfinyl-, 25 48... 

Si2NPCgH24, Phosphinous amide, P,P-di-methyl-A, A -bis(trimethylsilyl)-, 25 69 Si2N20QH24, Urea, N,N -dimethy -N,N -bis(trimethylsilyl)-, 24 120 Si2N2SQH,9, Sulfur diimide, bis(trimethyl-silyl)-, 25 44... 

Phosphonous acids have been alkylated with chloroacetic esters to give the phosphinic acid esters (136). The appropriately catalyzed reaction between trimethyl 1-phosphono-acrylate and methyl phenylphosphonite yields an intermediate... 

Reaction of white phosphorus with sodium hydroxide or sodium eth-oxide in ethanol generates a dark red solution of an uncharacterized metastable phosphorus compound (9) which possesses nucleophilic properties (10). The red product decomposes slowly even at 0 to hydrogen, phosphine, and sodium hypophosphite (9). But addition of methyl iodide to the freshly prepared solution is reported to give methylphos-phine, methylphosphonic acid, dimethylphosphinic acid, and trimethyl-phosphine oxide (10). Analogous products were reported from reaction with isoamyl iodide, where isoamylphosphonic acid was obtained in 59% yield based on the iodide. 

The data show that both techniques yield consistent results. However, different ionization ratios have been evaluated at the same acidity for methyl phenyl phosphinate by following the CH3 or OCH3 proton resonance chemical shifts with respect to the trimethyl-ammonium ion (Curci et al., 1973). This evokes a word of caution in the use of internal standards, although in many cases (see Fig. 1) very good results have been obtained. 

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