Synthesis, kinetic study, and reaction mechanism: nucleophilic substitution   reactions of butyl methyl chlorophosphate with substituted anilines and   deuterated substituted anilines in acetonitrile

Hasi Rani BARAI; Md. Mahbubur RAHMAN; Sang Woo JOO

Makale detayları

Synthesis, kinetic study, and reaction mechanism: nucleophilic substitution reactions of butyl methyl chlorophosphate with substituted anilines and deuterated substituted anilines in acetonitrile

Yazarlar:

Hasi Rani BARAI | Md. Mahbubur RAHMAN | Sang Woo JOO

Yayıncı:

TUBITAK

Ana Başlıklar:

Uygulamalı fizik

Dergi:

Turkish Journal of Chemistry 2019 Vol.43 Issue 2, pp.501-510

Belge Tipi:

Makale

Yayın Tarihi:

3/2019

Belge Dili:

İngilizce

Document ID (Org No.):

2000725788

Sıklık:

İki Aylık

eISSN:

1303-6130

pISSN:

1300-0527

Özet:

 

This study demonstrated the kinetics of nucleophilic   substitution reactions of butyl methyl chlorophosphate (2) with   X-anilines (XC66_{6}H44_{4}NH2)2)_{2}) and deuterated X-anilines   (XC66_{6}H44_{4}ND2)2)_{2}) in MeCN at 55.0 \textpm\ 0.1 \textdegree C together   with the general optimized method for the synthesis of 2 under mild   conditions. Different spectroscopic characterizations revealed the formation   of 2 with high purity. The free energy relationship with the   substituents X in the anilines exhibited biphasic concavity upwards with a   break point at X === H, which induced large negative ρXρX\rho_{X} and small   positive βXβX\beta_{X} values. The deuterium kinetic isotope effects   (DKIEs) were secondary inverse (kHkHk_{H}/kDkDk_{D}  \textless\ 1: 0.702--0.918)   and the magnitudes were increased with the change of nucleophiles from   weakly basic to strongly basic anilines. A concerted mechanism with a   rate-limiting leaving group departing from the intermediate is proposed   based on the selectivity parameters and the variation of DKIEs with X.

Makale detayları

Synthesis, kinetic study, and reaction mechanism: nucleophilic substitution reactions of butyl methyl chlorophosphate with substituted anilines and deuterated substituted anilines in acetonitrile

Yazarlar: Hasi Rani BARAI | Md. Mahbubur RAHMAN | Sang Woo JOO

Yayıncı: TUBITAK

Ana Başlıklar: Uygulamalı fizik

Dergi: Turkish Journal of Chemistry 2019 Vol.43 Issue 2, pp.501-510

Belge Tipi: Makale

Yayın Tarihi: 3/2019

Belge Dili: İngilizce

Document ID (Org No.): 2000725788

Sıklık: İki Aylık

eISSN: 1303-6130

pISSN: 1300-0527

Sayı

Yazarlar:

Hasi Rani BARAI | Md. Mahbubur RAHMAN | Sang Woo JOO

Yayıncı:

TUBITAK

Ana Başlıklar:

Uygulamalı fizik

Dergi:

Turkish Journal of Chemistry 2019 Vol.43 Issue 2, pp.501-510

Belge Tipi:

Makale

Yayın Tarihi:

3/2019

Belge Dili:

İngilizce

Document ID (Org No.):

2000725788

Sıklık:

İki Aylık

eISSN:

1303-6130

pISSN:

1300-0527