Rhodium catalyzed hydroformylation of linalool

被引：23

作者：

da Silva, Jose G. ^{[1
]}

Barros, Humberto J. V. ^{[1
]}

dos Santos, Eduardo N. ^{[1
]}

Gusevskaya, Elena V. ^{[1
]}

机构：

[1] Univ Fed Minas Gerais, ICEx, Dept Quim, BR-31270901 Belo Horizonte, MG, Brazil

来源：

APPLIED CATALYSIS A-GENERAL | 2006年 / 309卷 / 02期

关键词：

hydroformylation; linalool; rhodium catalysts;

D O I：

10.1016/j.apcata.2006.04.047

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The hydroformylation of linalool using [Rh(COD)(OAc)](2) as a catalyst precursor in the presence of triphenylphosphine or various diphosphines leads mainly to a mixture of cis and trans isomers of hemiacetal, which formally arise from the intramolecular cyclization of the primarily formed hydroxyl-aldehyde. An unexpected effect of the phosphorous ligands on the reaction rate was observed. With unmodified systems, linalool shows a very low reactivity under the hydroformylation conditions, probably due to the chelation of the substrate on rhodium. The introduction of (di)phosphine and the increase in its concentration exerts a great accelerating effect so that under optimized conditions at 40-50 degrees C and 20 atm of CO/H-2, a virtually complete conversion of linalool has been achieved in 4-6 h. A good control of chemo and stereoselectivity was attained through the appropriate choice of reaction variables. Each of two isomers of hemiacetal can be obtained in ca. 95% chemo- and 85% stereoselectivity. (C) 2006 Elsevier B.V. All rights reserved.

引用

页码：169 / 176

页数：8

共 31 条

[1] THE STEREOCHEMISTRY OF ORGANOMETALLIC COMPOUNDS .35. HYDROFORMYLATION OF ORTHO-PROPENYLANILINES AND ORTHO-PROPENYLPHENOLS - A NEW ROUTE TO 4,5-DIHYDRO-3H-1-BENZAZEPINES [J].

ANASTASIOU, D ;

JACKSON, WR .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1992, 45 (01) :21-37

[2] REASSIGNMENT OF THE COMPOUNDS REPORTED TO BE 4,5-DIHYDRO-3H-1-BENZAZEPIN-5-OLS AS 2,3,4,5-TETRAHYDRO-2,5-EPOXY-1H-1-BENZAZEPINES AND 3,4,5,6-TETRAHYDRO-1,6-BENZODIAZOCINES AS 2,3,3A,4-TETRAHYDRO-1H-PYRROLO[1,2-A]BENZIMIDAZOLES [J].

ANASTASIOU, D ;

CAMPI, EM ;

FALLON, GD ;

JACKSON, WR .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1993, 46 (10) :1623-1627

[3]

[Anonymous], CATALYSIS ORGANIC RE

[4] Catalytic hydroformylation of (1S,5S)-(-)- and (1R,5R)-(+)-beta-pinene: Stereoselective synthesis and spectroscopic characterization of (1S,2R,5S)-, (1S,2S,5S)-, (1R,2R,5R)- and (1R,2S,5R)-10-formylpinane [J].

Azzaroni, F ;

Biscarini, P ;

Bordoni, S ;

Longoni, G ;

Venturini, E .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 508 (1-2) :59-67

[5] Biphasic hydroformylation of monoterpenes employing Rh/TPPTS/CTAC: the role of the substrate in the mass transfer between the phases [J].

Barros, HJV ;

Hanson, BE ;

Gusevskaya, EV ;

dos Santos, EN .

APPLIED CATALYSIS A-GENERAL, 2004, 278 (01) :57-63

[6] Rhodium catalyzed hydroformylation of β-pinene and camphene:: effect of phosphorous ligands and reaction conditions on diastereoselectivity [J].

Barros, HJV ;

Ospina, ML ;

Arguello, E ;

Rocha, WR ;

Gusevskaya, EV ;

dos Santos, EN .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2003, 671 (1-2) :150-157

[7]

Bauer K., 1997, COMMON FRAGRANCE FLA

[8] Hydroformylation of linalool in a supported aqueous phase catalyst by immobilized rhodium complex:: kinetic study [J].

Benaissa, M ;

Jáuregui-Haza, UJ ;

Nikov, I ;

Wilhelm, AM ;

Delmas, H .

CATALYSIS TODAY, 2003, 79 (1-4) :419-425

[9]

BOTTEGHI C, 1998, TRANSITION METALS OR, V1, P25

[10]

CASEY CP, 1990, ISRAEL J CHEM, V30, P299

← 1 2 3 4 →