Kinetics and Mechanism of Vinylation of ortho-Palladated NN-Dialkylbenzylamines by para-Substituted Styrenes

DOI: 10.1039/P29830001511

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 1511 - 1518 (1983)

Update date:2022-08-04

Topics:

Authors:

Ryabov, Alexander D.

Sakodinskaya, Inna K.

Yatsimirsky, Anatoly K.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/P29830001511

The kinetics of vinylation of ortho-palladated NN-dialkylbenzylamines (1a-g) by CH2=CHC6H4R³-p (R³=H,Cl, Br, Me, and MeO) to form the respective 2-dialkylaminomethylstilbenes (2) has been studied mainly at 30 deg C in acetic acid solvent.The reaction follows second-order kinetics: d<(2)>/dt=k₂<(1)>.The rate constants k₂ increase markedly in the presence of both alkali-metal perchlorates (MClO4) and small concentrations of perchloric acid, k₂ being directly proportional to .It is shown that the salt effect originates from the solvolytic reaction MClO4 + HOAc <*> MOAc + HClO4.Conversion of dimer (1a) into the respective monomer (3) stops the reaction, but the latter species readily forms ?-complexes with styrenes.The stability constants of 1:1 ?-complexes have been determined and their Hammett correlation with a slope of -1.87 is established.For a series of substituted styrenes lgk₂ is the linear function of Hammett ?_p values with a slope of ca. -1.For a series of ring-substituted complexes (1) lgk₂ correlates with the pK_a of the parent benzylamines with a slope of 0.98.The results are interpreted in terms of a mechanism involving intermediate protonation of (1), ?-co-ordination of alkene, and subsequent rate-determining intramolecular insertion of styrene into a Pd-C bond through a four-centred transition state.

Full text of DOI:10.1039/P29830001511

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

Products guided by the article

Product name:{2-[(E)-2-(4-Chloro-phenyl)-vinyl]-benzyl}-diethyl-amine

Cas No:95852-03-2

R&D Labs maybe for 95852-03-2

JIEJIE GROUP CO.,LTD.

Contact:+86 021-51698675

Address:1701, Jielong Plaza, No.618 Pingliang Rd, ShangHai,China
Huangshan Violet Biological Technology Co., Ltd

Contact:+86-559-2335676

Address:16-201 JinShanYuan,JiangNan New City,TunXi District,HuangShan City,AnHui Province,China
Anhui Eapearl Chemical Co., Ltd.

Contact:86-562-5858458

Address:358 South Huaihe Road
Changzhou Welton Chemical Co., Ltd,

Contact:0086-519-85910828,85920537,85912897

Address:No.8 Jinlong Road, Binjiang Park, Changzhou, Jiangsu, China.
Hubei Onward Bio-Development Co., Ltd.

Contact:+86-718-8417012

Address:No.517,Shizhou Avenue,Enshi City,Hubei Province,China,445002

Relevant to this article

Catch-and-release of porphyrins by photoswitchable self-assembled monolayers

Doi:10.1039/b708851e
(2007)
Doi:10.1016/0039-128X(64)90111-4
(1964)
Oxidative addition of CH₃I and CO migratory insertion in a series of ferrocene-containing carbonyl phosphine β-diketonato rhodium(I) complexes

Doi:10.1021/om800655j
(2009)
Phosphoramidite Ligands Based on Simple 1,2-Diols: Synthesis, Use in Copper-Catalyzed Asymmetric Additions, and Achirotopic Stereogenic Phosphorus Centres

Doi:10.1002/adsc.201600368
(2016)
Formal synthesis of the piperidine alkaloid (±)-prosophylline using polymer-supported dihydro-2H-pyridin-3-one

Doi:10.1016/j.tetlet.2007.09.075
(2007)
Impact of aggregation on fluorescence sensitivity of molecular probes towards nitroaromatic compounds

Doi:10.1039/c6tc00655h
(2016)

Article Doi