O. G. Sinyashin

Reaction of dialkyl phosphites with N-2-methyl-2-chloropropylidenealkylamines

Organophosphorus compounds (OPCs) contain� ing aminoalkylphosphoryl fragments are of large prac� tical and theoretical interest. These compounds show a wide spectrum of useful properties. The addition of dialkyl phosphites to imines is one of the main meth� ods for the preparation of aminoalkylphosphonates. We have shown recently (1) that 2�halosubstituted alkylpropylidenamines react with dialkyl phosphites to form new types of OPCs, along with addition prod� ucts. It was found that the structure of final products is dependent on the halogen nature. To reveal the effect of the nature of substituents at P(IV) and N(III) on the structure of resulting products and the synthesis of polyfunctional OPCs of new types, we have studied the reactions of dimethyl, diethyl, diisopropyl, dinbutyl�, and di�2�chloroet� hyl phosphites (I) with (2�chloropropylidene)alkyl� amines ( II) containing tertbutyl, benzyl, and isopro� pyl substituents at the nitrogen atom. The reaction of dialkyl phosphites I with com� pounds II leads to the initial formation of addition products showing phosphorus resonance signals at 26-29 ppm. Addition product III with R 2 = tB u and R 1 = Me is a crystalline solid and can be stored in the pure state for a long time without change. When the reaction mixture was stored for 15- 20 days, the primary addition products undergo fur� ther transformations and the structure of the reaction products depends on the nature of the substituents at P(IV) and N(III). Thus, the ease of the transformation and the structure of the products are dependent on the nature of the substituents at N(III): if R 2 = iPr and Bz, further transformation of the addition product proceeds much more readily as compared with the compound with R 2 = tB u. It is likely that cyclic inter� mediate IV in the case of R 2 = tB u is more difficult to form as compared with R 2 = iPr and Bz on account of

Synthesis of Dialkyl (1-Hydroxy-2,2-dimethyl- 3-(dialkylamino)propyl)phosphonates

We found that compounds III can be prepared by reaction of dialkyl hydrogen phosphites I with 3-(dialkylamino)-substituted aldehydes II. Addition of ethanolic sodium ethylate or a little sodium to a mixture of compounds I and II gives rise to an exothermic reaction. After neutralization of the reaction mixture with acetic acid and evaporation of volatile substances in a high vacuum, compounds III were identified as crude materials, since they decomposed on attempted vacuum distillation. Compounds III can also be obtained by heating a mixture of compounds I and II at 80oC. Under these conditions, nucleophilic catalysis takes place due to the presence in the starting aldehydes of a tertiary amino group.

Transformation of Trichloromethyl Arenes to Methyl Arenecarboxylates and Arene-Carbonyl Chlorides Under the Action of Methyl Esters of Tetracoordinate Phosphorus Acids

Under the same conditions 3-(trichloromethyl)chlorobenzene Ib or 4-(trichloromethyl)chlorobenzene Ic gives a mixture of acid chloride and ester, IIIb, VIb and IIIc, VIc respectively, and some part of the starting trichloromethyl arene remains unreacted. From the obtained experimental results it follows that trichloromethylarenes under the action of methyl P(IV) acid ester firstly form arenecarbonyl chloride VIa3VIc. Their subsequent reaction with an excess of II gives ester IIIa3IIIc. Model reaction between the compounds II and VIa really leads to corresponding products IIIa and IV. According to the published data [133] reaction of carboxylic acid chloride with dialkyl alkylphosphonate yields carboxylic acid anhydride of and esteroanhydrides of alkylphosphonic acid. Considering these data, we have proposed that the transformation of acid chloride VIa to the ester IIIa includes the intermediate formation of benzoic acid anhydride VII. In the separate experiment it was shown that the reaction of anhydride VII with the phosphonate II finishes by the formation of the ester IIIa and anhydride IV.