Process for the preparation of aldehydes and ketones

• US 6,023,000 A
• Filed: 05/21/1998
• Issued: 02/08/2000
• Est. Priority Date: 06/06/1997
• Status: Expired due to Fees

• Current Assignee: Consortium Fur Elektrochemische Industrie GmbH
• Original Assignee: Consortium Fur Elektrochemische Industrie GmbH
• Inventors: Fritz-Langhals, Elke, Freudenreich, Johannes
• Primary Examiner(s): Geist, Gary
• Assistant Examiner(s): PADMANABHAN, SREENIVASAN
• Application Number:
  US09/082,638
• Time in Patent Office: 628 Days
• Field of Search: 568/309, 568/320, 568/322, 568/323, 568/325, 568/326, 568/327, 568/328, 568/330, 568/331, 568/335, 568/338, 568/357, 568/361, 568/376, 568/383, 568/399, 568/403, 568/407 , 568/426, 568/431, 568/449, 568/470, 568/471
• US Class Current: 568/320
• CPC Class Codes: C07C 221/00 Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
• CPC Class Codes: C07C 223/06 having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
• CPC Class Codes: C07C 253/30 by reactions not involving the formation of cyano groups
• CPC Class Codes: C07C 255/56 containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
• CPC Class Codes: C07C 29/48 by oxidation reactions with formation of hydroxy groups
• CPC Class Codes: C07C 33/22 Benzylalcohol; phenethyl alcohol
• CPC Class Codes: C07C 45/28 of CHx-moieties
• CPC Class Codes: C07C 45/36 in compounds containing six-membered aromatic rings
• CPC Class Codes: C07C 47/575 containing ether groups, groups, groups, or groups
• CPC Class Codes: C12P 17/00 Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms C12P13/04 - C12P13/24 take precedence
• CPC Class Codes: C12P 7/24 containing a carbonyl group

Abstract

A process for the preparation of vinyl, alkynyl or aryl aldehydes or vinyl, alkynyl or aryl ketones includes reacting vinyl-, alkynyl- and aryl- and -methylene compounds with the aid of a mediator and an oxidant, wherein the mediator is selected from the group of the aliphatic, heterocyclic or aromatic NO or NOH containing compounds.

Claims

1. A process for the preparation of an aldehyde selected from the group consisting of vinyl aldehyde, alkynyl aldehyde, and aryl aldehyde and a ketone selected from the group consisting of vinyl ketone, alkynyl ketone, and aryl ketone comprising

reacting a compound selected from the group consisting of vinyl methyl, alkynyl methyl, aryl methyl, vinyl methylene, alkynyl methylene, and aryl methylene with an oxidant and with the aid of a mediator in a reaction medium,

wherein the mediator is selected from the group consisting of an aliphatic, heterocyclic, and aromatic NO and NOH containing compound.

2. A process as claimed in claim 1, wherein the aldehyde and the ketone are each a compound of the formula 1, and the methyl compound and the methylene compound are each a compound of the formula 2 ##STR22## where Y¹ and Y² can be identical or different and are radicals having up to 20 C atoms and up to 6 rings and at least one of the radicals Y¹ or Y² is vinyl, alkynyl, or aryl, and Y¹ and Y² may also be part of a ring system;

and

with the proviso that whenever the compound of formula 1 is an aldehyde, Y¹ or Y² is hydrogen.

3. A process as claimed in claim 2, wherein Y¹ is the following:

aromatic or a ring system having up to 6 rings and up to 20 C atoms, or an anthraquinonyl radical, it being possible for the aromatic radical Y¹ to be mono- to hexasubstituted,

it being possible for the substituents to be identical or different and to have the meaning of OH, a linear, branched or cyclic C₁ -C₁₂ -alkyl radical, it being possible for adjacent alkyl groups to form a 5-, 6- or 7-membered ring via a methylene group, or a linear or branched C₁ -C₁₂ -oxyalkyl or thioalkyl radical, it being possible for adjacent substituents to form a 5-, 6- or 7-membered ring via a methylene group, a H₂ N-- or a linear or branched C₁ -C₁₂ -N-alkylamino, a linear or branched C₁ -C₁₂ --N,N-dialkylamino group, NC--, O₂ N--, halogen, HOOC--, HO₃ S--, OHC--, H₂ N--COO--, H₂ N--CO--, H₂ N--CO--NH--, or a linear, branched or cyclic C₁ -C₁₂ --OCO--, C₁ -C₁₂ --COO--, C₁ -C₁₂ --CO--, C₁ -C₁₂ --NHCO--, C₁ -C₁₂ --NHCONH--, (C₁ -C₁₂)₂ NCO--, C₁ -C₁₂ --CONH-- group, or a linear or branched C₁ -C₁₂ --OSO₂ --, C₁ -C₁₂ --NH--SO₂ --, or (C₁ -C₁₂)₂ N--SO₂ -- group, or a phenyl, diphenylmethyl, phenyl-CH═

CH--, phenyl-N═

N--, phenyl-N═

CH--, phenyl-CH═

N--, phenoxy, phenyl-NH--, phenyl-O--CO--, phenyl-CO--, phenyl-NHCO--, phenyl-CONH--, phenyl-NHCONH--, phenyl-OSO₂ -- or phenyl-NH--SO₂ -- group whose phenyl radicals can be mono- to pentasubstituted, it being possible for the substituents to be identical or different and to have the meaning of OH, a linear, branched or cyclic C₁ -C₁₂ -alkyl radical, it being possible for adjacent alkyl groups to form a 5-, 6- or 7-membered ring via a methylene group, or of a linear or branched C₁ -C₁₂ -oxyalkyl or thioalkyl radical, it being possible for adjacent substituents to form a 5-, 6- or 7-membered ring via a methylene group, a H₂ N-- or a linear or branched C₁ -C₁₂ --N-alkylamino, a linear or branched C₁ -C₁₂ --N,N-dialkylamino group, NC--, O₂ N--, halogen, HOOC--, HO₃ S--, OHC--, H₂ N--COO--, H₂ N--CO--, H₂ N--CO--NH--, or a linear, branched or cyclic C₁ -C₁₂ --OCO--, C₁ -C₁₂ --COO--, C₁ -C₁₂ --CO--, C₁ -C₁₂ --NHCO--, C₁ -C₁₂ --NHCONH--, (C₁ -C₁₂)₂ NCO--, C₁ -C₁₂ --CONH--, or of a linear or branched C₁ -C₁₂ --OSO₂ --, C₁ -C₁₂ --NH--SO₂ -- or (C₁ -C₁₂)₂ N--SO₂ -- group, or of a phenyl, diphenylmethyl, phenyl-CH═

CH--, phenyl-N═

N--, phenyl-N═

CH--, phenyl-CH═

N--, phenoxy, phenyl-NH--, phenyl-O--CO--, phenyl-CO--, phenyl-NHCO--, phenyl-CONH--, phenyl-NHCONH--, phenyl-OSO₂ -- or phenyl-NH--SO₂ -- group or an optionally mono- to trisubstituted vinyl radical or optionally substituted ethynyl radical, in which the substituents can be identical or different and have the meaning of hydrogen, linear, branched or cyclic C₁ -C₁₂ -alkyl radical where one or more methylene groups can be replaced individually by CHOH, CO, O, S, NH or by a linear or branched C₁ -C₁₂ --N-alkylamine radical, or in which the vinyl group forms part of a ring or ring system, and Y² is the following;

hydrogen, linear, branched or cyclic C₁ -C₁₂ -alkyl radical where one or more methylene groups can be replaced individually by CHOH, CO, O, S, NH or by a linear or branched C₁ -C₁₂ --N-alkylamine radical, or an aromatic ring or ring system having up to 6 rings and up to 20 C atoms, or anthraquinonyl radical, or an optionally mono- to trisubstituted vinyl radical or optionally substituted ethynyl radical, in which the substituents can be identical or different and have the meaning of hydrogen, linear, branched or cyclic C₁ -C₁₂ -alkyl radical where one or more methylene groups can be replaced individually by CHOH, CO, O, S, NH or by a linear or branched C₁ -C₁₂ --N-alkylamine radical, or in which the vinyl group forms part of a ring or ring system, it furthermore being possible for the radicals Y¹ and Y² to be linked via a methylene group or an ether group or via an amino group which is optionally substituted by a linear, branched or cyclic C₁ -C₁₂ -alkyl radical.

4. A process as claimed in claim 2, wherein Y¹ is the following:

5-, 6- or 7-membered aromatic ring which can be fused to one or two further aromatic rings or an anthraquinonyl radical, it being possible for Y¹ to be mono- to tetrasubstituted, it being possible for the substituents to be identical or different and to have the meaning of OH, a linear, branched or cyclic C₁ -C₆ -alkyl radical, it being possible for adjacent alkyl groups to form a 5- or 6-membered ring via a methylene group, or a linear or branched C₁ -C₆ -oxyalkyl or -thioalkyl radical, it being possible for adjacent substituents to form a 5- or 6-membered ring via a methylene group, of a H₂ N--, or a linear or branched C₁ -C₆ --N-alkylamino, a linear or branched C₁ -C₃ -N,N-dialkylamino group, NC--, O₂ N--, halogen, HOOC--, HO₃ S--, OHC--, H₂ N--COO--, H₂ N--CO--, H₂ N--CO--NH--, or a linear, branched or cyclic C₁ -C₆ --OCO--, C₁ -C₆ --COO--, C₁ -C₆ --CO--, C₁ -C₆ --NHCO--, C₁ -C₆ --NHCONH--, (C₁ -C₆)₂ NCO--, C₁ -C₆ --CONH--, or of a linear or branched C₁ -C₆ --OSO₂ --, C₁ -C₆ --NH--SO₂ -- or (C₁ -C₃)₂ N--SO₂ -- group, or of a phenyl, diphenylmethyl, phenyl-CH═

CH--, phenyl-N═

N--, phenyl-N═

CH--, phenyl-CH═

N--, phenoxy, phenyl-NH--, phenyl-O--CO--, phenyl-CO--, phenyl-NHCO--, phenyl-CONH--, phenyl-NHCONH--, phenyl-OSO₂ -- or phenyl-NH--SO₂ -- group, it being possible for the phenyl radicals to be mono- to trisubstituted, it being possible for the substituents to be identical or different and to have the meaning of OH, a linear, branched or cyclic C₁ -C₆ -alkyl radical, it being possible for adjacent alkyl groups to form a 5- or 6-membered ring via a methylene group, or a linear or branched C₁ -C₆ -oxyalkyl or -thioalkyl radical, it being possible for adjacent substituents to form a 5- or 6-membered ring via a methylene group, of a H₂ N--, or a linear or branched C₁ -C₆ --N-alkylamino, a linear or branched C₁ -C₃ --N,N-dialkylamino group, NC--, O₂ N--, halogen, HOOC--, HO₃ S--, OHC--, H₂ N--COO--, H₂ N--CO--, H₂ N--CO--NH--, or a linear, branched or cyclic C₁ -C₆ --OCO--, C₁ -C₆ COO--, C₁ -C₆ CO--, C₁ -C₆ --NHCO--, C₁ -C₆ --NHCONH--, (C₁ -C₆)₂ NCO--, C₁ -C₆ --CONH--, or of a linear or branched C₁ -C₆ --OSO₂ --, C₁ -C₆ --NH--SO₂ -- or (C₁ -C₃)₂ N--SO₂ -- group, or of a phenyl, diphenylmethyl, phenyl-CH═

CH--, phenyl-N═

N--, phenyl-N═

CH--, phenyl--CH═

N--, phenoxy, phenyl-NH--, phenyl-O--CO--, phenyl-CO--, phenyl-NHCO--, phenyl-CONH--, phenyl-NHCONH--, phenyl-OSO₂ -- or phenyl-NH--SO₂ -- group, or an optionally mono- to trisubstituted vinyl radical or optionally substituted ethynyl radical,

it being possible for the substituents to be identical or different and to be hydrogen or linear, branched, or cyclic C₁ -C₆ -alkyl radical where one or two methylene groups can be replaced individually by CHOH, CO, O, S, NH or by a linear or branched C₁ -C₆ --N-alkylamine radical, or in which the vinyl group forms part of a 5- or 6-membered ring or of a ring system, and Y² is the following;

hydrogen or linear, branched or cyclic C₁ -C₆ -alkyl radical where one or two methylene groups can be replaced individually by CHOH, CO, O, S, NH or by a linear or branched C₁ -C₆ --N-alkylamine radical, or a 5-, 6- or 7-membered aromatic ring which can be fused to one or two further aromatic rings or an anthraquinonyl radical, or an optionally mono- to trisubstituted vinyl radical, or an optionally substituted ethynyl radical, it being possible for the substituents to be identical or different and to be hydrogen or linear, branched, or cyclic C₁ -C₆ -alkyl radical where one or two methylene groups can be replaced individually by CHOH, CO, O, S, NH or by a linear or branched C₁ -C₆ --N-alkylamine radical, or in which the vinyl group forms part of a 5- or 6-membered ring or of a ring system.

5. A process as claimed in claim 2, wherein Y¹ is the following:

phenyl, naphthyl, anthryl, phenanthryl, azulenyl, anthraquinonyl,

it being possible for Y¹ to be mono- to trisubstituted, it being possible for the substituents to be identical or different and to have the meaning of OH, a linear C₁ -C₆ -alkyl radical, it being possible for adjacent alkyl groups to form a 5- or 6-membered ring via a methylene group, or of a linear C₁ -C₆ -oxyalkyl radical, it being possible for adjacent substituents to form a 5- or 6-membered ring via a methylene group, a H₂ N--, or a linear C₁ -C₆ --N-alkylamino, a linear C₁ -C₃ --N,N-dialkylamino group, NC--, O₂ N--, halogen, HOOC--, HO₃ S--, OHC--, H₂ N--COO--, H₂ N--CO--, H₂ N--CO--NH--, or a linear C₁ -C₄ --OCO--, C₁ -C₄ --COO--, C₁ -C₄ --CO--, C₁ -C₄ --NHCO--, (C₁ -C₄)₂ NCO--, C₁ -C₄ --CONH--, C₁ -C₄ --NHCONH--, or C₁ -C₄ --OSO₂ --, C₁ -C₄ --NH--SO₂ -- or (C₁ -C₃)₂ N--SO₂ -- group, or of a phenyl, diphenylmethyl, phenyl-CH═

CH--, phenyl-N═

N--, phenyl-N═

CH--, phenyl--CH═

N--, phenoxy, phenyl-NH--, phenyl-O--CO--, phenyl-CO--, phenyl-NHCO--, phenyl-CONH--, phenyl-NHCONH--, phenyl-OSO₂ -- or phenyl-NH--SO₂ -- group, it being possible for the phenyl radicals to be mono- to trisubstituted, it being possible for the substituents to be identical or different and to have the meaning of OH, a linear C₁ -C₆ -alkyl radical, it being possible for adjacent alkyl groups to form a 5- or 6-membered ring via a methylene group, or of a linear C₁ -C₆ -oxyalkyl radical, it being possible for adjacent substituents to form a 5- or 6-membered ring via a methylene group, a H₂ N--, or a linear C₁ -C₆ --N-alkylamino, a linear C₁ -C₃ --N,N-dialkylamino group, NC--, O₂ N--, halogen, HOOC--, HO₃ S--, OHC--, H₂ N--COO--, H₂ N--CO--, H₂ N--CO--NH--, or a linear C₁ -C₄ --OCO--, C₁ -C₄ --COO--, C₁ -C₄ --CO--, C₁ -C₄ --NHCO--, (C₁ -C₄)₂ NCO--, C₁ -C₄ --CONH--, C₁ -C₄ --NHCONH--, or C₁ -C₄ --OSO₂ --, C₁ -C₄ --NH--SO₂ -- or (C₁ -C₃)₂ N--SO₂ -- group, or of a phenyl, diphenylmethyl, phenyl-CH═

CH--, phenyl-N═

N--, phenyl-N═

CH--, phenyl-CH═

N--, phenoxy, phenyl-NH--, phenyl-O--CO--, phenyl-CO--, phenyl-NHCO--, phenyl-CONH--, phenyl-NHCONH--, phenyl-OSO₂ -- or phenyl-NH--SO₂ -- group or

an optionally mono- to trisubstituted vinyl radical, or optionally substituted ethynyl radical, in which the substituents can be identical or different and are hydrogen or linear C₁ -C₆ -alkyl radical where one or two methylene groups can be replaced individually by CHOH, CO, O, S, NH or by a linear or branched C₁ -C₆ --N-alkylamine radical, or in which the vinyl group forms part of a 5- or 6-membered ring or of a ring system, and Y² is the following;

hydrogen or a linear C₁ -C₆ -alkyl radical where one or two methylene groups can be replaced individually by CHOH, CO, O, S, NH or by a linear or branched C₁ -C₆ --N-alkylamine radical, or is phenyl, naphthyl, anthryl, phenanthryl, azulenyl, anthraquinonyl, or an optionally mono- to trisubstituted vinyl radical, or optionally substituted ethynyl radical, in which the substituents can be identical or different and are hydrogen or linear C₁ -C₆ -alkyl radical where one or two methylene groups can be replaced individually by CHOH, CO, O, S, NH or by a linear or branched C₁ -C₆ --N-alkylamine radical, or in which the vinyl group forms part of a 5- or 6-membered ring or of a ring system, where, furthermore, the radicals Y¹ and Y² can be linked via a methylene group or an ether group or via an amino group which is optionally substituted by a methyl, ethyl, -- or iso-propyl radical, the linkage resulting in 5- or 6-membered rings.

6. A process as claimed in claim 1,

wherein the mediator is at least on compound selected from the group consisting of N-hydroxy-phthalimide, 1-hydroxy-1H-benzotriazole, violuric acid, N-hydroxyacetanilide, nitrosonaphthols, nitrosopyridinols and the derivatives thereof.

7. A process as claimed in claim 1,

wherein the mediator is at least one compound selected from the group consisting of 3-amino-N-hydroxyphthalimide, 4-amino-N-hydroxyphthalimide, N-hydroxyphthalimide, 3-hydroxy-N-hydroxyphthalimide, 3-methoxy-N-hydroxyphthalimide, 3,4-dimethoxy-N-hydroxyphthalimide, 4,5-dimethoxy-N-hydroxyphthalimide, 3,6-dihydroxy-N-hydroxyphthalimide, 3,6-dimethoxy-N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide, 4-methyl-N-hydroxyphthalimide, 3,4-dimethyl-N-hydroxyphthalimide, 3,5-dimethyl-N-hydroxyphthalimide, 3,6-dimethyl-N-hydroxyphthalimide, 3-isopropyl-6-methyl-N-hydroxyphthalimide, 3-nitro-N-hydroxyphthalimide, 4-nitro-N-hydroxy-phthalimide, 1-hydroxy-1H-benzotriazole, violuric acid and N-hydroxyacetanilide, 3-nitrosoquinoline-2,4-diol, 2,4-dihydroxy-3-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyridine, 2,4-dinitroso-1,3-dihydroxybenzene, 2-nitroso-1-naphthol-4-sulfonic acid and 1-nitroso-2-naphthol-3,6-disulfonic acid.

8. A process as claimed in claim 1,

wherein the oxidant is selected from the group consisting of air, oxygen, hydrogen peroxide, an organic peroxide, a peracid, a perborate and a persulfate with each oxidant in combination with an enzyme.

9. A process as claimed in claim 8, wherein the oxidant is selected from the group consisting of air and oxygen in combination with laccase.

10. A process as claimed in claim 1, wherein the oxidant is a metal oxide with a solubility of less than 1 g/l in the reaction medium.

11. A process as claimed in claim 1, further comprising

adding a cosolvent comprising water with one to three solvents which are at least partially miscible with water.