Trimethylphosphite

Cuprous iodide trimethylphosphite [34836-53-8] M 314.5, m 175-177°, 192-193°. Cuprous iodide dissolves in a C Hg soln containing trimethylphosphite to form the complex. The complex crystallises from C6Hg or pet ether. [Chem Ber 38 1171 7905 Bull Chem Soc Jpn 34 1177 7967.]... 

Tlie starting material for this Wittig-Horner-like olefination was easily accessible by reaction of benzo-l,3-dithiolium-tetrafluoroborate with trimethylphosphite in the presence of an equimolar amount of sodium iodide in dry acetonitrile under nitrogen at room temperature (93% yield). 

To a solution of 1.0 g (0.003 mole) of iridium tetrachloride in 0.5 ml of concentrated hydrochloric acid is added 15 ml of trimethylphosphite. This solution is added to a solution of 7.7 g (0.05 mole) of 4-/-butylcyclohexanone in 160 ml of isopropanol in a 500-ml flask equipped with a reflux condenser. The solution is refluxed for 48 hours, then cooled, and the isopropanol is removed on a rotary evaporator. The residue is diluted with 65 ml of water and extracted four times with 40-ml portions of ether. The extracts are dried with anhydrous magnesium sulfate, filtered, and the ether is removed on the rotary evaporator. The white solid residue is recrystallized from 60 % aqueous ethanol affording cis alcohol of greater than 99% purity, mp 82-83.5°. 

The ligand exchange kinetics between free and coordinated ligands were studied more thoroughly for the ligands trimethylphosphite and triphenylphosphine. The kinetics were analyzed using conventional NMR line shape technique 140). 

The bidentate formate ligand of OsH(K2-02CH)(CO)(P,Pr3)2 is converted into a monodentate group by carbonylation. Thus, the reaction of this compound with carbon monoxide gives 0sH K1-0C(0)H (C0)2(P Pr3)2. Similarly, the addition of a stoichiometric amount of trimethylphosphite yields 0sH k -0C(0)H (C0) P(OMe)3 (P Pr3)2, and the addition of a stoichiometric amount of ethyne di-carboxylic methyl ester leads to 0sH K1-0C(0)H (C0)(r 2-Me02CC=CC02Me) (P Pr3)2, which in solution partially dissociates the alkyne. As is shown in... 

The removal of oxygen from 1,2,4-oxadiazole 4-oxides and polymer-supported analogues 187 can be achieved with triethyl- or trimethylphosphite, as the example in Equation (30) shows <2005JC0887>. 

Metal vapor deposition of Fe atoms with a variety of acyclic and cyclic dienes, followed by treatment of the condensate with excess trimethylphosphite, give the corresponding (diene)Fe[P(OMe)3]3 complexes in low yield109. 

Acyloin condensation of diester 30a with sodium in liquid ammonia, followed by direct hydrogenation in the presence of Adam s catalyst, furnished the diol 32 in 49% yield. Diol 32 was transformed into the cyclic thiocarbonyl derivative (80% yield) which after heating with trimethylphosphite [14] afforded twistene 33 in 50% yield. Hydrogenation of 33 gave a compound identical in all respects with twistane 1. From the diester (-)-30a (+)-twistene was obtained, m.p. 35.5-36.5 °C, +... 

Transformation of diols to the corresponding olefins by sequential treatment with l,r-thiocarbonyldiimidazole and trimethylphosphite. Also known as Corey-Winter reductive elimination, or Corey-Winter reductive olefmation. 

Disappointingly, the trimethylphosphite-modified Wilkinson catalyst, which had proven effective for the allylic substitution reaction [30], furnished only a trace amount of the PK product. By screening various rhodium catalysts for both reactions, it was determined that [RhCl(CO)dppp]2 was the optimum complex for the sequential pro-... 

Reaction of oxyiminium cations with trimethylphosphite under catalysis with LiC104/ TMSCl results in the corresponding a-oxyaminophosphonates of type 71 (equation 45)... 

Treatment of o-phthaldialdehyde with triethylphosphite in the presence of Lewis acids yields 1-phosphoryl substituted isobenzofurans (96TL5963 see also 79JOC494). For the reaction of 3-chloro-3-phenylphthalide with trimethylphosphite see Groffits et al. [93ZOR(63)2245]. 

It was shown (17) that phosphine exchange occurred in [AuMe(PR3)l complexes, but species with a coordination number greater than two were not observed, even with bidentate phosphorus ligands. Although such species were not observed, an associative mechanism was thought to be operative (16, 18). With trimethylphosphite also, only the two-coordinate complex [AuMe P(OMe)3 l was detected in solution (19). 

Fig. 14. HOs5C(CO),j(OP(OCHj)2)(P(OCHj)j), 14 (34). The Os,C core is similar to that in Fig. 13. In this case Os(4) and Os(5) occupy apical sites and Os( I), Os(2), and Os(3) are three of the equatorial sites of the incomplete pentagonal bipyramid. The trimethylphosphite ligand is coordinated to Os(3), which also bears two carbonyls and the phosphonate oxygen atom. The hydride is assigned a bridging position on Os(l)-Os(2). The two metal-metal bonds to Os(3) are significantly longer [2.954(20) A] than the remaining five [mean 2.877(9) A]. The mean Os—Cpjrtjjdj distance is 2.07(7) A.

Trimethylphosphate Dimethylcyanamide, vinyl sulfone Methyl dichlorophosphate N-methy Iformamide Methyl methanesulfonate Trimethylphosphite... 

Our present evidence for the tetrahydride is derived from an experiment in which a large excess of trimethylphosphite was vacuum-transferred into a degassed, frozen solution of a known amount of the... 

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