Diphenyl Phosphite Research Articles

Phosphorylation of diamines

Alkanediamines react with diphenyl phosphite (1 mol. equiv.) and triethylamine in carbon tetrachloride, or with diphenyl phosphorochloridothionate (1 mol. equiv.), to give bis(diphenoxyphosphinylamino)alkanes and related compounds, and not ω-aminoalkylphosphoramidic esters. m- and p-Phenylenediamines behave similarly, but m-phenylenediamine may also be monophosphorylated. o-Phenylenediamine behaves anomalously and gives phenyl hydrogen N-(2-aminophenyl)phosphoramidate. Piperazine and phenyl phosphorodichloridothionate give NN′-bis(phenoxyphosphinothioyl)piperazine or 7-phenoxy-1,4-diaza-7-phosphabicyclo[2,2,1]heptane-7-thione, depending on the reaction medium.

Action of diethyl phosphite on p-benzoquinone and 1,4-naphthoquinone

The addition of diphenyl phosphite to p-benzoquinone and to 1,4-naphthoquinone in presence of sodium alkoxide led to the formation of diethyl p-hydroxyphenyl phosphate and diethyl 4-hydroxy-1-naphthyl phosphate, respectively.

Effect of the size and structure of radicals present in phosphorus esters on the rate of isomerization of these substances

1. Some new dialkyl phenyl and alkyl diphenyl phosphites have been synthesized. 2. In the series of alkyl diphenyl phosphites, only the methyl and ethyl esters isomerize smoothly. The higher homologs decompose when they react with the corresponding alkyl iodides. 3. A number of new addition products of alkyl iodides with triphenyl phosphite has been prepared. 4. The products of the addition of methyl, ethyl, and n-butyl iodides to triphenyl phosphite decompose at 210–220° according to the scheme of the second stage of the Arbuzov rearrangement. 5. By the action of alcohol on the products of the addition of benzyl, isopropyl, n-butyl, and isobutyl iodides to tripbenyl phosphite, the diphenyl esters of the corresponding alkylphosphonic acids have been prepared, these reactions confirm the structures of the addition products. 6. The above facts (3,4, and 5) show that the Arbuzov rearrangement occurs in two stages with the formation of an intermediate addition product. 7. It has been shown that the isomerization products of phosphorous esters are substances that accelerate the isomerization process. The isomerization reaction is therefore autocatalytic. 8. Isobutyl iodide adds to triphenyl phosphite considerably more rapidly than n-butyl iodide does. The addition reaction of isobutyl iodide, unlike those of the other alkyl iodides examined, has a long induction period.