Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1997-11-12
1999-06-15
Reamer, James H.
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568321, 568360, 568402, 568 41, 568431, 568471, 546267, 549498, 549 70, C07C 4529
Patent
active
059123885
DESCRIPTION:
BRIEF SUMMARY
The present invention concerns a catalytic oxidative process for preparing aldehydes or ketones from alcohols. Aldehydes and ketones are important intermediates and products in the chemical industry.
The oxidation of certain alcohols to aldehydes or ketones using two equivalents of copper (I) chloride, an amine, oxygen and potassium carbonate is disclosed in Tetrahedron Letters (1977) No.14 1215-8 and Tetrahedron (1980) 36 1191-4.
The present invention provides a process for preparing an aldehyde or ketone comprising reacting a primary or secondary alcohol with oxygen in the presence of a base, a catalytic amount of a copper salt and a suitable ligand under anhydrous conditions.
In one particular aspect the present invention provides a process for preparing an aldellyde or ketone comprising reacting a primary or secondary alcohol with oxygen in the presence of a base, a product obtainable by mixing a catalytic amount of a copper salt and a suitable ligand; the process being conducted under anhydrous conditions.
In another aspect the present invention provides a process for preparing an aldehyde or ketone of formula (I), wherein R.sup.1 is hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryl(C.sub.1-4)alkyl, optionally substituted heteroaryl(C.sub.1-4)alkyl, optionally substituted aryloxy(C.sub.1-4)alkyl, optionally substituted heteroaryloxy(C.sub.1-4)alkyl; R.sup.2 is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryl(C.sub.1-4)alkyl, optionally substituted heteroaryl(C.sub.1-4)alkyl, optionally substituted aryloxy(C.sub.1-4)alkyl, optionally substituted heteroaryloxy(C.sub.1-4)alkyl, optionally substituted arylcarbonyl or optionally substituted heteroarylcarbonyl; or R.sup.1 and R.sup.2 join to form an optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring; comprising reacting an alcohol of formula (II), wherein R.sup.1 and R.sup.2 are as defined above, with oxygen in the presence of a base, a catalytic amount of a copper salt and a suitable ligand under anhydrous conditions.
The suitable ligand is a ligand suitable for copper. The ligand is preferably an amine. It is preferably a bidentate ligand such as 1,10-phenanthroline, a substituted 1.10-phenanthroline (for example 5-nitro- 1,10-phenanthroline, 5-chloro-1,10-phenanthroline or 5,6-dioxo-1,10-phenanthroline), a pyridine derivative (such as 2,2'-bipyridine, 4,4'dimethyl-2-2'-bipyridine, 4,4'-bipyridine, 2,2':6',2"-terpyridine or 2,2'-dipyridylamine) or a diamine (such as N,N,N,N-tetrametlhylethiylenediamine or ethyleniediamine).
Oxygen can be supplied in pure form or in the form of air.
It is preferred that the base is a salt such as a carbonate, bicarbonate, alkoxide (provided it is not oxidisable under the reaction conditions, for example tert-butoxide) or acetate of a metal (such as an alkali metal or a transition metal having an atomic number of 21-30). Preferred bases are potassium carbonate, potassium acetate, potassium tert-butoxide, caesium carbonate and sodium carbonate.
A catalytic amount of a copper salt in a sub-stoichiometric amount, preferably 0.9 equivalents or less, more preferably 0.5 equivalents or less. It is preferred that the molar ratio of copper salt:ligand is about 1:1.
In one particular aspect the present invention provides a process wherein the molar ratio of alcohol of formula (II):copper salt:ligand is in the range 1:(0.01-0.10):(0.01-0.10), especially about 1:0.05:0.05.
It is preferred that the copper salt is a copper (I) salt. Preferred counter ions are triflate, acetate, cyanide and, especially, chloride.
The copper salt and ligand interact to form a complex. Thus, in a further aspect the present invention provides a process for preparing an aldehy
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Brown Stephen Martin
Giles Paul Richard
Marko Istvan Ettienne
Tuskazaki Masao
Urch Christopher John
LeCroy David P.
Reamer James H.
Zeneca Limited
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