Three-Component Reaction of Benzylamines, Diethyl Phosphite and Triethyl Orthoformate: Dependence of the Reaction Course on the Structural Features of the Substrates and Reaction Conditions.

Ilona Turowska-Tyrk,Patrycja Miszczyk,Ewa Chmielewska,Paweł Kafarski

doi:10.3390/molecules22030450

Ilona Turowska-Tyrk, Patrycja Miszczyk + Show 2 more

Open Access

https://doi.org/10.3390/molecules22030450

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Abstract

The reaction between benzyl amines, triethyl orthoformate, and diethyl phosphite affords either bisphosphonic (compound 1) or N-benzylaminobenzylphosphonic (compound 2) acid depending on the reaction conditions. The final output of the reaction can be manipulated by the choice of reaction conditions, particularly the molar ratio of substrates.

Highlights

BisBpihspohspohspohnoatneasteasrearae aprpormomineinnetnctlacslasssofoforogragnaonpohpohsopshpohroursuscocmompopuonudnsd.s.ThTeyheayrearme omstost comcommomnolynluyseudsetdo ttoretaret aptopsotmstemneonpoapuasuals-ala-nadndglugcluoccoocrtoirctoicido-iidn-dinudcuedceodstoesotepooproosriossibsybiynhinibhiitbinitging thethme imneirnaelrizaalitzioantioonr roersorerpsotiropntioofnboofnebo[1n–e4][.1–R4e]c.enRtleyc,etnhtelyy, hthaveye ahlasovebeaelsnoubseeednasusderdugasstdorturegast to botnreeatprboobnleempsrobaclecmoms paacncoyminpganfryoimng mfroumltipmleulmtipyleelommyaelo[5m,6a] [a5n,6d] aansd paasllpiaatlilviaetivaegeangtsent[s7,8[7].,8]
The same results and formation of products 16 were observed for o-chlorobenzylamine used as a substrate
Reaction of o-chlorobenzylamine with triethyl orthoformate, provided the derivative of MNo,Nlec’u-ldesi(2o0-1c7h, 2lo2,rxoFbOeRnzPyEEl)RimREinVoIElWformamide 15 obtained as the major product with satisfactory 7yoief l1d2 (31% yield). Reaction of this compound with diethyl phosphite (1:2 molar ratio) followed by the hacyiddrohlyydsrisoloyfsitshoef rtheaecrteioanctimonixmtuirxetuprreopvriodvedidetwd otwporopdroudctusct(s30(3%0%totoatlayl iyeiledl;d;SSchchememee88),),nnaammeellyy, amino phosphonate 6d and a side-product that was not isolated from the reaction mixture

Summary

Reactions of Benzylamines with Substituents on the Phenyl Ring

Reactions were carried out under conditions that provided mixtures of products 5 and 6 (1:2:1 molar ratio, 135 ◦C, 12 h of heating). The same results and formation of products 16 were observed for o-chlorobenzylamine used as a substrate This compound is the hydrolysed form of one of intermediates that was identified earlier [19]. Reaction of this compound with diethyl phosphite (1:2 molar ratio) followed by the acid in high (95%) yield. Reaction of o-chlorobenzylamine with triethyl orthoformate, provided the derivative of MNo,Nlec’u-ldesi(2o0-1c7h, 2lo2,rxoFbOeRnzPyEEl)RimREinVoIElWformamide 15 obtained as the major product with satisfactory 7yoief l1d2 (31% yield). Reaction of this compound with diethyl phosphite (1:2 molar ratio) followed by the hacyiddrohlyydsrisoloyfsitshoef rtheaecrteioanctimonixmtuirxetuprreopvriodvedidetwd otwporopdroudctusct(s30(3%0%totoatlayl iyeiledl;d;SSchchememee88),),nnaammeellyy,, amino phosphonate 6d and a side-product that was not isolated from the reaction mixture. RReeaaccttiioonn ooff NN,,NN’’--ddii((oo--cchhlloorroobbeennzzyyll))iimmiinnoo ffoorrmmaammiiddee wwiitthh ddiieetthhyyll pphhoosspphhiittee

General Information

Crystallography

General Procedure for the Synthesis

Findings

Conclusions