Triphenyl phosphite methiodide

A solution of 45 g of triphenyl phosphite methiodide in 100 ml of dry di-methylformamide was heated at 100°C and 0.08 mol of the acetylenic alcohol (commercially available) was added in 2 min. After stirring for 30 min at 100°C the mixture was cooled. The flask was equipped for vacuum distillation. On the flask were placed a 25-cm Vigreux column and two stoppers and the column was connected with a condenser and a receiver. The DMF and the iodoallene distilled between... 

By the use of triphenyl phosphite methiodide, Rydon2 has obtained alkyl iodides according to the equation... 

N. K. Kochetkov and A. I. Usov, The reaction of carbohydrates with triphenyl phosphite methiodide and related compounds. A new synthesis of deoxy sugars, Tetrahedron 79 973... 

The method employing triphenyl phosphite methiodide, as adapted to carbohydrates,130 has been used for the synthesis of protected 4-deoxy sugars. From methyl 2,3-di-0-methyl-6-0-p-tolylsulfonyl-a-D-glucoside and the corresponding D-galactoside, epimeric 4-iodo derivatives were obtained these were both reduced to methyl 4-deoxy-2,3-di-0-methyl-b-0-p-tolyl-sulfonyl-a-D-zj/Zo-hexoside. 

The first of these methods involves the reaction of triphenyl phosphite methiodide with methyl 3-0-methyl-2-0-p-tolylsulfonyl-a-D-glucopyrano-side, hydrogenation of the resulting 4,6-diiodo derivative, and hydrolysis,186 as adapted to monosaccharides by Kochetkov and coworkers.1,0 In another approach,281 ethyl 2,3-anhydro-4,6-dideoxy-D-nbo-hexopyranoside, obtained from desosamine, was treated with sodium methoxide, to give a mixture of 2- and 3-methyl ethers. After fractionation and separation of side products,288 the 3-methyl ether was hydrolyzed, to give crystalline chalcose. McNally and Overend800 have described another synthesis, starting from methyl 4-deoxy-D-xj/Zo-hexoside.107... 

In addition to the sulfonyloxy displacement reaction which may occur on halogenation with triphenyl phosphite complexes, the possibility of acetal migration (with appropriate structure) should not be overlooked. Thus, 1,2 5,6-di-O-isopropylidene-a-D-glucofuranose with triphenyl phosphite dibromide in benzene for 48 hours afforded " (presumably) 6-bromo-6-deoxy-l,2 3,5-di-O-isopropylidene-a-D-glucofiiranose, which was hydrolyzed to 6-bromo-6-deoxy-D-glucose in 10% overall yield. In some compounds, steric factors may prevent the introduction of halogen. With vicinal glycols and triphenyl phosphite methiodide, phosphonic ester formation occurs instead of halide production, but this reaction may be eliminated by use of triphenylphosphine in carbon tetrachloride. 

Primary alcohols can be reduced to hydrocarbons in two steps conversion into the iodide with triphenyl phosphite methiodide (methyltriphenoxyphosphonium iodide, 1, 1249 2. 446 ), followed by reduction with sodium cyanoborohydride in HMPT. 

Phosphonitrile chloride Chlorophosphoranes (C,H,),PF2, (C,H,),-PCI2, (C,H,),PBr2 R2PCI, (C,H,)2PF, Triphenyl phosphite dibromide Triphenyl phosphite methiodide... 

Triphenyl phosphite dibromide Triphenyl phosphite methiodide F2I4... 

Triphenyl phosphite methiodide lodallenes from 2-acetylenealcohols... 

Sodium trihydridocyanoborate/triphenyl phosphite methiodide Hydrocarbons from alcohols s. 27, 74... 

Triphenyl phosphite methiodide s. under Na[BHgCN] Nickel... 

Triphenyl phosphite methiodide Iodides from alcohols... 

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