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Process for catalytically reducing carbonyl compounds

Assignee: Montedison SpA
•
Filing: 1980-03-07
•
Granted: 1981-09-22
•
Expires: 2000-03-07
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Abstract

Abstract Catalytic reduction of carbonyl compounds by transfer of hydrogen from alcohols to aliphatic, alicyclic, aromatic, homo- and heterocyclic ketones or aldehydes, catalyzed by rhodium or iridium complexes, characterized in that a primary or secondary alcohol of formula (I) or a glycol: ##STR1## is reacted with a ketonic compound of formula (II): ##STR2## in which R and R' and, respectively, R" and R'", optionally linked with each other according to homo- or heterocycles, indifferently represent a hydrogen atom or a hydrocarbyl group having up to 30 atoms of carbon, also substituted, provided that at least one of symbols R" and/or R'" is different respectively from R and/or R', in the presence of a complex catalyst of rhodium or of iridium selected from those having formulas (III) and (IV): ##STR3## wherein: M is selected from Rh and Ir; Chel is a chelating bidentate nitrogenous compound; L-L is a molecule of a preferably non-conjugated diolefin or two molecules of a monoolefin; X - is an anion selected from amongst Cl - , Br - , J - , PF 6 - , BF 4 - , C10 4 - , B(C 6 H 5 ) 4 - ; Y is a halogen, preferably it is Cl or Br; n is an integer from 0 to 3; and of a compound selected from amongst mineral alkalis and tertiary amines at a temperature ranging from about 20° C. to the boiling temperature of the reaction mass, preferably in an inert atmosphere. The products obtained are employed as intermediates for organic syntheses in the field of fine chemicals. Some terms of the classes of catalysts herein described are to be considered as new in themselves.

Inventors

  • 👤 Giovanni Mestroni
  • 👤 Grazia Zassinovich
  • 👤 Annamaria Camus

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-04 22:20
CPC Classifications
C; C07; C07J; C07J1/00; C07J1/0003; C07J1/0011; B; B01; B01J; B01J31/00; B01J31/16; B01J31/18; B01J31/1805; B01J31/181; B01J31/1815; B01J31/1825; B01J31/183; B01J31/22; B01J31/2282; B01J31/2291; C07C; C07C29/00; C07C29/132; C07C29/136; C07C29/143; C07C45/00; C07C45/27; C07C45/29; B01J2231/00; B01J2231/60; B01J2231/64; B01J2231/641; B01J2231/643; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/822; B01J2531/827; C07B; C07B2200/00; C07B2200/07; C07B2200/09; C07C2601/00; C07C2601/12; C07C2601/14

Claims Analysis

Total Claims: 23
Claim 1
Independent Claim 236 words
A process for catalytically reducing carbonyl compound by transfer of hydrogen from alcohols to aliphatic, alicyclic, aromatic homo- and heterocyclic ketones or aldehydes, catalyzed by complexes of rhodium or of iridium, comprising the reaction of a primary or secondary alcohol of formula (I) or a glycol: ##STR10## with a ketonic compound of formula (II): ##STR11## in which R and R' and respectively R" and R'", also linked with each other according to homo- or heterocycles, are indifferently a hydrogen atom or a hydrocarbyl group having up to 30 atoms of carbon, provided that at least one of the symbols R" and/or R'" is different respectively from R and/or R', in the presence of a complex catalyst of rhodium or of iridium selected from those having formulas (III) and (IV): ##STR12## in which: M is selected from Rh and Ir; Chel is a chelating bidentate nitrogenous compound; L-L is a molecule of a diolefin, or two molecules of a monoolefin; X - is an anion selected from Cl - , Br - , J - , FF 6 - , BF 4 - , ClO 4 - , B(C 6 H 5 ) 4 - ; Y is a halogen; and n is an integer from 0 to 3; and in the presence of a compound selected from among mineral alkalis, at a temperature ranging from about 20° C. to the boiling temperature of the reaction mass.
Claim 2
Dependent Claim 236 words
A process for catalytically reducing carbonyl compound by transfer of hydrogen from alcohols to aliphatic, alicyclic, aromatic homo- and heterocyclic ketones or aldehydes, catalyzed by complexes of rhodium or of iridium, comprising the reaction of a primary or secondary alcohol of formula (I) or a glycol: ##STR10## with a ketonic compound of formula (II): ##STR11## in which R and R' and respectively R" and R'", also linked with each other according to homo- or heterocycles, are indifferently a hydrogen atom or a hydrocarbyl group having up to 30 atoms of carbon, provided that at least one of the symbols R" and/or R'" is different respectively from R and/or R', in the presence of a complex catalyst of rhodium or of iridium selected from those having formulas (III) and (IV): ##STR12## in which: M is selected from Rh and Ir; Chel is a chelating bidentate nitrogenous compound; L-L is a molecule of a diolefin, or two molecules of a monoolefin; X - is an anion selected from Cl - , Br - , J - , FF 6 - , BF 4 - , ClO 4 - , B(C 6 H 5 ) 4 - ; Y is a halogen; and n is an integer from 0 to 3; and in the presence of a compound selected from among mineral alkalis, at a temperature ranging from about 20° C. to the boiling temperature of the reaction mass.
Claim 3
Dependent Claim 42 words
A process according to claim 1, characterized in that the mineral alkali is a mineral alkaline compound selected from NaOH, KOH, LiOH, NaHCO 3 in a molar ratio to the catalyst of from 0.1 to 200 moles per 1 mole of catalyst.
Claim 4
Dependent Claim 32 words
A process according to claim 1, characterized in that the tertiary amine is selected between triethylamine and dimethyl-benzylamine in a molar ratio of from 0.1 to 200 per 1 mole of catalyst.
Claim 5
Dependent Claim 51 words
A process according to claims 1 or 2, characterized in that it is conducted in a medium selected from the alcohol and the glycol donor in excess and a compound selected from amongst toluene, benzene, methanol and water, optionally in admixture with one another, preferably from the alcohol or glycol donor.
Claim 6
Dependent Claim 47 words
A process according to claim 1, characterized in that the catalyst of formula (IV): [Rh (Chel).sub.2 Y.sub.2 ].sup.+ X.sup.-.nH.sub.2 O (IV) wherein the symbols have the meanings specified in claim 1, is activated by heating in the reaction medium in the presence of the mineral alkaline compound.
Claim 7
Dependent Claim 55 words
A process according to claim 1, characterized in that the catalyst of formula (III): [M Chel (L-L)].sup.+ X.sup.- (III) wherein the symbols have the meanings specified in claim 1, is activated by oxidation with oxygen or a source thereof, and by successive heating in the reaction medium in the presence of the mineral alkaline compound.
Claim 8
Dependent Claim 26 words
A process according to claim 1, characterized in that the chelating nitrogenous compound is selected from 2,2'-dipyridyl, 3,3'-dimethyl-2,2'-dipyridyl, 4,4'-dimethyl-2,2'-dipyridyl, 1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2-pyridinalphenylethylimine, 4,7-diphenyl-1,10-phenanthroline, 2-pyridinalnaphthylethylimine.
Claim 9
Dependent Claim 83 words
A process according to claim 1, characterized in that the chelating nitrogenous compound is a compound selected from those having formulas (V) and (VI): ##STR13## in which groups R iv and R v , like or unlike each other, optionally linked according to homo- and heterocycles, are respectively selected from amongst H, alkyls and aryls and from amongst OH, NH 2 , alkyls and aryls, all having up to 30 carbon atoms, also containing functional groups selected from amongst carboxyls, esters and amides.
Claim 10
Dependent Claim 52 words
A process according to claims 1 to 8, characterized in that the prochiral ketonic compounds are reduced to chiral alcohols by employing chiral alcohols or glycols and/or catalysts of formula (III) as defined in claim 1, containing a chelating nitrogenous compound selected from those having formulas (V) and (VI) of claim 8.
Claim 11
Dependent Claim 19 words
A process according to claim 9, characterized in that the chelating nitrogenous compound is selected from pyridinalphenylethylimine and 2-pyridinalnaphthylethylimine.
Claim 12
Dependent Claim 32 words
A process according to claim 1, characterized in that in said complex catalyst L-L is a non-conjugated diolefin selected from 1,5-hexadiene, norbornadiene and 1,5-cyclooctadiene, or a monoolefin selected from cyclooctene and ethylene.
Claim 13
Dependent Claim 27 words
A process according to claim 1, characterized in that for 1 mole of carbonyl compound (II), from 1×10 -2 to 1×10 -6 moles of catalyst are employed.
Claim 14
Dependent Claim 40 words
A process according to claim 1, characterized in that the complex catalyst of rhodium or of iridium is prepared "in situ" in the reaction medium by adding the chelating compound to the halogenated olefinic complex of rhodium or of iridium.
Claim 15
Dependent Claim 28 words
A process according to claim 1, characterized in that the molar ratio between the reagents alcohol donor or glycol and carbonyl compound approximately ranges from 1:1 to 20:1.
Claim 16
Dependent Claim 29 words
A process according to claim 1, characterized in that the concentration of the carbonyl compound in the reaction medium approximately ranges from 10 to 10 -3 moles per liter.
Claim 17
Dependent Claim 26 words
A process according to claim 1, characterized in that the catalyst concentration approximately ranges from 10 -1 to 10 -6 moles per liter of reaction mass.
Claim 18
Dependent Claim 36 words
A process according to claim 1, characterized in that the acceptor carbonyl compound is selected from amongst cyclohexanone, 4-terbutylcyclohexanone, 3-methyl-cyclohexanone, 4-methyl-cyclohexanone, 2-methyl-cyclohexanone, acetophenone, propiophenone, isobutyrophenone, dihydrocarvone, methyl-isobutylketone, benzaldehyde and p.methoxy-benzaldehyde, benzophenone, benzyl, dehydro-epiandrosterone acetate, and 3-oxosteroids.
Claim 19
Dependent Claim 25 words
A process according to claim 1, characterized in that the alcohol donor is selected from among isopropyl alcohol, 2-butyl alcohol, benzyl alcohol and ethyl alcohol.
Claim 20
Dependent Claim 14 words
A process according to claim 1, characterized in that the glycol donor is 1,2-cyclododecandiol.
Claim 21
Dependent Claim 21 words
A process according to claim 1, characterized in that the catalytic system contains an auxiliary component selected from the chiral amines.
Claim 22
Dependent Claim 22 words
The process of claim 1, in which the compounds having formulae I and II are substituted at R, R', R" or R'''.
Claim 23
Dependent Claim 16 words
The process of claim 1, in which in said complex catalyst Y is Cl or Br.

References Cited (Backward Citations)

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USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1984-09-21 1985-03-23 1985-09-22 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1988-09-21 1989-03-23 1989-09-22 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1992-09-21 1993-03-23 1993-09-22 $7700.00 Window Closed / Lapsed

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