+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Phenonium ions from the addition of phenyl cations to alkenes. Photochemical synthesis of (rearranged) aminoalkylanilines from haloanilines in the presence of alkenes and amines



Phenonium ions from the addition of phenyl cations to alkenes. Photochemical synthesis of (rearranged) aminoalkylanilines from haloanilines in the presence of alkenes and amines



Journal of Organic Chemistry 68(3): 1067-1074



beta-Aminoalkylanilines are smoothly obtained by irradiation of 4-chloro- and 4-fluoroanilines (as well as the N,N-dimethyl derivatives) in the presence of alkenes (1-hexene, cyclohexene) and amines (butylamine, piperidine) in polar, protic solvents such as trifluoroethanol (yield 40-75%). The reaction involves photoheterolysis of the haloaniline, addition of the resulting phenyl cation to the alkene and trapping of the phenonium cation by amine. A fraction (up to ca. 20%) of aminoalkylanilines resulting from Wagner-Meerwein rearrangement of the phenonium cation is obtained in some cases. Reduction and direct trapping of the phenyl cation by the amine compete with the above three-component synthesis in a less stabilizing solvent such as acetonitrile, but not in CF(3)CH(2)OH.

Please choose payment method:






(PDF emailed within 0-6 h: $19.90)

Accession: 046973603

Download citation: RISBibTeXText

PMID: 12558436

DOI: 10.1021/jo026516d


Related references

Smooth Synthesis of Aryl- and Alkylanilines by Photoheterolysis of Haloanilines in the Presence of Aromatics and Alkenes. Organic Letters 1(8): 1299-1301, 1999

Efficient radical addition of tertiary amines to electron-deficient alkenes using semiconductors as photochemical sensitisers. Chemical Communications 2001(17): 1576-1577, 2001

TBAF-mediated reactions of 1,1-dibromo-1-alkenes with thiols and amines and regioselective synthesis of 1,2-heterodisubstituted alkenes. Journal of Organic Chemistry 76(8): 2448-2458, 2011

Synthesis of β-Amino Esters via Aza-Michael Addition of Amines to Alkenes Promoted on Silica: A Useful and Recyclable Surface. Synlett 2004(14): 2630-2632, 2004

Addition of benzylzinc halides to alkenyl(phenyl)iodonium triflates: stereoselective synthesis of trisubstituted alkenes. Organic Letters 2(11): 1521-1523, 2000

Intramolecular photoarylation of alkenes by phenyl cations. Chemistry 12(14): 3905-3915, 2006

Synthesis of silica-based sulfonic cation-exchangers by the reaction of the addition of hydrosulfite ions to immobilized alkenes and their use in chromatography. Journal of Analytical Chemistry 65(4): 352-358, 2010

Synthesis of substituted 1-methyl-2-cyanopyrroles via unprecedented addition of N,N-dimethylformamide to electron-deficient alkenes in the presence of copper(I) cyanide. Journal of Organic Chemistry 65(7): 2222-2224, 2000

Addition of Hexacarbonyldicobalt-Stabilized Propargyl Cations to Alkenes. Journal of Organic Chemistry 61(11): 3912-3915, 1996

Hydroamination: direct addition of amines to alkenes and alkynes. Chemical Reviews 108(9): 3795-3892, 2008

New systems for classical nitrosohalogenation of alkenes 1. Reactions of alkenes with ethyl nitrite in the presence of phosphorus halides and thionyl chloride. Russian Chemical Bulletin 54(9): 2133-2144, 2005

The synthesis of alkenes from carbonyl compounds and carbanions alpha to silicon part 5 stereoselective synthesis of e and z di substituted alkenes. Tetrahedron Letters 49: 4439-4442, 1976

The evaluation of some photochemical smog reaction mechanismsII. Initial addition of alkanes and alkenes. Atmospheric Environment. Part A. General Topics 26(4): 643-651, 1992

The evaluation of some photochemical smog reaction mechanisms ii. initial addition of alkanes and alkenes. Atmospheric Environment Part A General Topics 26(4): 643-651, 1992

Photoredox-Catalyzed C-H Arylation of Internal Alkenes to Tetrasubstituted Alkenes: Synthesis of Tamoxifen. Organic Letters 19(22): 6248-6251, 2017