Phosphite, trimethyl

The dimethyl allylphosphonate 352 is prepared by the reaction of allylic acetates with trimethyl phosphite[221]. 

Dialkylphosphonopropionamides. CeUulosic derivatives that closely resemble those based on the dialkylphosphonopropionamides have been prepared (71). The fabric was treated with AJ-hydrox raethylhaloacetamides (chloro, bromo, or iodo) in DME solution by a pad-dry-cure technique with a 2inc nitrate [10196-18-6] catalyst. It was then allowed to react in solution with trimethyl phosphite [121 -45-9] at about 140—150°C the reaction rates decreased in the order iodo > bromo > chloro. With phosphoms contents above 1.5%, good flame resistance, durable to laundering, was obtained without noticeable loss in fabric strength. 

Substituted Nickel Carbonyl Complexes. The reaction of trimethyl phosphite and nickel carbonyl yields the monosubstituted colorless oil, (CO)2NiP(OCH )2 [17099-58-0] the disubstituted colorless oil, (CO)2Ni[P(OCH )2]2 [16787-28-3] and the trisubstituted white crystalline soHd,... 

Reactive halogens in various series have been removed by catalytic hydrogenation with either platinum or palladium catalysts, and other nucleophiles which have been used in chloride displacements include hydroxide ion, alkoxides, hydrosulflde, hydrazine and toluene-p-sulfonylhydrazine, and trimethyl phosphite. 

TRtMETHYL NORPINANYL HYDROPEROXIDE TRIMETHYL PHOSPHITE TRIHETHYLACETYL CHLORIDE TRIKETHYLAMINE 1,3,5-TRIMETHYLBENZENE... 

Ironically, the reactor was used to produce Antiblaze 19, a flame retardant used in textiles and polyurethane foam. Antiblaze 19 is a cyclic phosphorate ester produced from a mixture of trimethyl phosphite, dimethyl methylphosphonate (DMMP), and trimethyl phosphate (TMOP). The final product is not considered flammable, but trimethyl phosphite is moisture sensitive and flammable, with a flash point of about 27 C. 

The reduction of keto steroids by treatment with chloroiridic acid, or sodium chloroiridate, and trimethyl phosphite has been studied in some detail.Ketones at the 2- and 3-positions are reduced predominantly to the corresponding axial alcohols, while ketones at 4,6,7,11,12,17 and 20 are not affected. The rate of reaction is increased by addition of aqueous sodium hydroxide. Replacement of sodium chloroiridate by tris(triphenylphos-phine)rhodium chloride gives a system which reduces a 3-keto steroid to the... 

A mixture of the ketone (4.62 g), iridium tetrachloride (1.23 g), trimethyl phosphite (15 ml), propan-2-oI (200 ml) and water (50 ml) is heated under reflux for 21 hr. Much of the solvent is then distilled off ca. 215 ml) and the organic products remaining are isolated by extraction with ether. If reduction is essentially complete, the product at this stage may be sufficiently pure for most preparative purposes. Pure components can be obtained by chromatography over alumina, a representative experiment (on the above scale) gives unchanged ketone (0.13 g), cw-alcohol (4.36 g) and tmns-2 co o (0.16 g) (eluted in this order by pentane, and then by pentane containing ether). 

To 1 g of 2j5-azido-3a-iodo-5a-cholestane ° in 10 ml benzene is added 0.4 g trimethyl phosphite. A boiling chip is added and the mixture allowed to stand at room temperature for 4 days. The solvent is removed in vacuo, with most of the trimethyl phosphite being removed at 0.1 mm. This crude product (100) is dissolved in 10 ml of dry ether and added dropwise to a stirred mixture of 0.5 g of lithium aluminum hydride in 10 ml of ether. After stirring at 25° for 3 hr, the excess of hydride is destroyed by the addition of 2 ml 20 % sodium hydroxide and the aluminum salts are filtered. The solution is washed with ether, and the ether removed in vacuo giving 0.71 g [76 %] of product (95) mp 101-103°. 

Trimethyl phosphite P(OMe)3 spontaneously iso-merizes to methyl dimethylphosphonate MePO-(OMe)2, whereas other trialkyl phosphites undergo the Michaelis-Arbusov reaction with alkyl halides via a phosphonium intermediate ... 

Heating 3,4-bis(phenylsulfonyl)furoxan with a solution of sodium butoxide in butanol followed by reduction with trimethyl phosphite gives furazan 281 (Scheme 183). Compound 281 was converted into dialkoxy derivative 282 with the lithium salt of ( )-l-azabicyclo[2.2.2]octan-3-ol in 33% overall yield (96W012711, 97EUP773021, 98JMC379). 

In addition there are certain other methods for the preparation such compounds. Upon heating of the thionocarbonate 2 with a trivalent phosphorus compound e.g. trimethyl phosphite, a -elimination reaction takes place to yield the olefin 3. A nucleophilic addition of the phosphorus to sulfur leads to the zwitterionic species 6, which is likely to react to the phosphorus ylide 7 via cyclization and subsequent desulfurization. An alternative pathway for the formation of 7 via a 2-carbena-l,3-dioxolane 8 has been formulated. From the ylide 7 the olefin 3 is formed stereospecifically by a concerted 1,3-dipolar cycloreversion (see 1,3-dipolar cycloaddition), together with the unstable phosphorus compound 9, which decomposes into carbon dioxide and R3P. The latter is finally obtained as R3PS ... 

Regioselective addition of bromine azide to dienes 38 at 25 °C gave the 1,4-adducts 39 or the 1,2-adducts 40 as thermodynamically favored products, their ratios depending on the substituent R on the terminal carbon (Scheme 2.12). These adducts were easily converted into vinylaziridines 41 on treatment with trimethyl-phosphite, although the stereochemistries of 39, 40, and 41 are unclear [23]. 

Racemic [l-(4-methylphenylsulfinyl)-2-propenyl]lithium, prepared with lithium diiso-propylamide in THF, adds to racemic chiral 2-methylalkanals with good a- and syn selectivity114, us Qn heating with trimethyl phosphite or triethylamine, the major isomer furnishes the ( )-.yvn-2-alkene-l,4-diol by Mislow rearrangement1 lb. 

Nickel, diiodotris(trimethyl phosphite)-strpeture, 1,45 Nickel, hcxaamminc-rcactions, 1,27 Nickel, hexaaqua-reactions, 1, 204 Nickel, hexafluoro-, 5,186 Nickel, hexakis(A, Ar -dimethylurea)-tetrachloronickelate isomerization, 1,470... 

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