With trimethyl phosphite

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. 

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). 

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. 

The reaction of 1,2-dithiolanes with 2- and 4-picolyllithium has been examined <96PS(112)101> and the reactions of thioanhydrides such as 94 with both thiols <95JOC3964> and amines <96TL5337> have been reported. Treatment of 1,2-dithiolium salts with lithium or thallium cyclopentadienide results in formation of a variety of bi-, tri- and tetracyclic products <96LA109>. Reaction of 95 with trimethyl phosphite gives some of the desired coupling product but also the phosphonates 96 <96PS(109)557>. 

The pyruvaldehyde and phenylglyoxal adducts (19) with trimethyl phosphite reacted with isocyanates to give the carbamoyl-1,3,2-dioxa-phospholens (20), probably as shown. These, with hydrogen chloride, gave phosphate esters of )3-keto-a-hydroxyamides. 

An allylic sulfenate, like 199, is known to be in equilibrium with allylic sulfoxide, like 196, although its concentration is usually low . Various allylic sulfoxides can be prepared by treatment of allylic alcohols with arenesulfenyl chlorides . Evans and coworkers prepared various allylic alcohols by treating the corresponding allylic sulfoxides with trimethyl phosphite. For example, the carbanion from a cycloalkenyl sulfoxide 201 was readily alkylated at the a-position by treatment with alkyl halide. The resulting alkylated derivative 202 was then treated with trimethyl phosphite and 3-substituted cycloalkenol was obtained. Alkylation of acyclic allylic sulfoxide 204 gave... 

Neruda, B. et al., J. Organomet. Chem., 1976, 111, 241-248 In the exothermic reaction with trimethyl phosphite to give r/.v-dimethyl-bis(trimethyl phosphito)platinum, the azide must be added to the phosphite in small portions with stirring. Addition of the phosphite to the solid azide led to a violent explosion, probably involving the transitory by-product methyl azide. 

Pyrido[2,l-r ][l,4,2]oxazaphosphorine derivatives 201 were prepared from perhydrooxazolopyridines 200 by treatment with trimethyl phosphite in the presence of SnCU. In this way, the product (R = H) was obtained as a mixture of two diastereomers originating from the different configuration on the phosphorus. In the case of a cyano substituted derivative (R = CN), a third diastereomer was also isolated in a very low yield (Equation 29) <1997T3627, 1997BML2477>. 

The cycloaddition of nitrile oxides to amidoximes 234 leads to 1,2,4-oxadiazole 4-oxides which can then be deoxygenated with trimethyl phosphite (Equation 48) <1997T1787>. 

Arbuzov, B.A., Sorokina, T.D., Fuzhenkova, A.V., and Vinogradova, V.S., Reaction of l,2-diphenyl-4-benzalpyrrolidine-3,5-dione with trimethyl phosphite and tris(dimethylamino)phosphine, Bull. Acad. Sci. U.S.S.R., 22, 2577, 1973. 

The cycloaddition of allenyl sulfoxide 135 and cydopentadiene occurred at room temperature, giving the single adduct 136. The initially formed allylic sulfoxide underwent a rapid [2,3]-sigmatropic rearrangement. Treatment of 136 with trimethyl phosphite furnished alcohol 137. It should be noted that the reaction of methyl 4-hydroxy-2-butynoate with cydopentadiene failed to give 137. Thus, the allene 135 is considered as a masked and more reactive alkyne equivalent. 

Attack on Oxygen. Nitrones have been deoxygenated to the parent imine with trimethyl phosphite under vigorous conditions.45 Virtually quantitative yields of the enol-phosphates (54) and (55) were obtained from the reaction of tris(trimethylsilyl) phosphite with a-diketones and /j-benzoquinone. 4 6... 

A report that 3-cyclopropyl-2-diethylamino-l//-azepine is formed either by thermolysis of o-azidocyclopropylbenzene, or by deoxygenation of o-nitrosocyclopropylbenzene with trimethyl phosphite in diethylamine, is unique, since, if correct, it is the first example of a stable A-unsubstituted l//-azepine (79JOU1272). 

Preparation of polycyclic ortho esters by the reaction of 1,2-hydroxy-benzene thionocarbonate with trimethyl phosphite [184, 185]. 

Bis(trifluoromethyl)-5(2//)-oxazolone undergoes decarboxylation on treatment with trimethyl phosphite. The resulting 1,3-dipole may be trapped by methyl propio-late [171]. The initial P-C bond formation is favored because the alternative mode of reaction would form a weak P-N bond. This counter-Michael addition also generates an a-d-ard system which becomes fragmentable. 

The present method is based on the earlier described ozonolysis of phenanthrene in methanol. The reduction of the peroxidic reaction mixture with trimethyl phosphite to give diphenaldehyde, isolated as the di- -nitrophenylhydrazone, in quantitative yield has been described recently.10 The disadvantage of this method is that the dialdehyde cannot be isolated in the free state in high yield. Diphenaldehyde has also been obtained by sodium... 

Figure 3. The percent of benzyl chlorines replaced in a reaction with trimethyl phosphite as a function of reaction time (measured by weight gain). The reaction time is measured from the time the reaction bath reached 100°C.

---