WO2002088063A1 - Process for the production of ketones - Google Patents
Process for the production of ketones Download PDFInfo
- Publication number
- WO2002088063A1 WO2002088063A1 PCT/EP2002/004440 EP0204440W WO02088063A1 WO 2002088063 A1 WO2002088063 A1 WO 2002088063A1 EP 0204440 W EP0204440 W EP 0204440W WO 02088063 A1 WO02088063 A1 WO 02088063A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- choh
- alicyclic
- triazacyclononane
- branched
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000002576 ketones Chemical class 0.000 title description 8
- -1 peroxy compound Chemical class 0.000 claims abstract description 10
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 claims abstract 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003333 secondary alcohols Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 2
- BAUZLFKYYIVGPM-UHFFFAOYSA-N cyclononanone Chemical compound O=C1CCCCCCCC1 BAUZLFKYYIVGPM-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PZQGSZRQKQZCOJ-UHFFFAOYSA-N cyclobutane-1,3-dione Chemical compound O=C1CC(=O)C1 PZQGSZRQKQZCOJ-UHFFFAOYSA-N 0.000 description 1
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 description 1
- VIDCUPKHAMMBHZ-UHFFFAOYSA-N cyclodecane-1,3-dione Chemical compound O=C1CCCCCCCC(=O)C1 VIDCUPKHAMMBHZ-UHFFFAOYSA-N 0.000 description 1
- UOLUVQJHQREQCL-UHFFFAOYSA-N cyclodecane-1,4-dione Chemical compound O=C1CCCCCCC(=O)CC1 UOLUVQJHQREQCL-UHFFFAOYSA-N 0.000 description 1
- KTBLJTVYLAOMLE-UHFFFAOYSA-N cyclodecane-1,5-dione Chemical compound O=C1CCCCCC(=O)CCC1 KTBLJTVYLAOMLE-UHFFFAOYSA-N 0.000 description 1
- KBSGQTAYVRWUEO-UHFFFAOYSA-N cyclodecane-1,6-dione Chemical compound O=C1CCCCC(=O)CCCC1 KBSGQTAYVRWUEO-UHFFFAOYSA-N 0.000 description 1
- DBOVMTXPZWVYAQ-UHFFFAOYSA-N cycloheptane-1,3-dione Chemical compound O=C1CCCCC(=O)C1 DBOVMTXPZWVYAQ-UHFFFAOYSA-N 0.000 description 1
- JFZCBLXXTGLKOG-UHFFFAOYSA-N cycloheptane-1,4-dione Chemical compound O=C1CCCC(=O)CC1 JFZCBLXXTGLKOG-UHFFFAOYSA-N 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- YGVJHVAGBZEZFZ-UHFFFAOYSA-N cyclononane-1,3-dione Chemical compound O=C1CCCCCCC(=O)C1 YGVJHVAGBZEZFZ-UHFFFAOYSA-N 0.000 description 1
- DMWAGNKQUHYLMS-UHFFFAOYSA-N cyclononane-1,4-dione Chemical compound O=C1CCCCCC(=O)CC1 DMWAGNKQUHYLMS-UHFFFAOYSA-N 0.000 description 1
- PQOZOIXDFLJALL-UHFFFAOYSA-N cyclononane-1,5-dione Chemical compound O=C1CCCCC(=O)CCC1 PQOZOIXDFLJALL-UHFFFAOYSA-N 0.000 description 1
- OOOLFZKAFMJAJK-UHFFFAOYSA-N cyclooctane-1,3-dione Chemical compound O=C1CCCCCC(=O)C1 OOOLFZKAFMJAJK-UHFFFAOYSA-N 0.000 description 1
- LZTHLBQVLFQNKK-UHFFFAOYSA-N cyclooctane-1,4-dione Chemical compound O=C1CCCCC(=O)CC1 LZTHLBQVLFQNKK-UHFFFAOYSA-N 0.000 description 1
- HNIJGYLFFVBUNQ-UHFFFAOYSA-N cyclooctane-1,5-dione Chemical compound O=C1CCCC(=O)CCC1 HNIJGYLFFVBUNQ-UHFFFAOYSA-N 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- LOGSONSNCYTHPS-UHFFFAOYSA-N cyclopentane-1,3-dione Chemical compound O=C1CCC(=O)C1 LOGSONSNCYTHPS-UHFFFAOYSA-N 0.000 description 1
- VBBRYJMZLIYUJQ-UHFFFAOYSA-N cyclopropanone Chemical compound O=C1CC1 VBBRYJMZLIYUJQ-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
Definitions
- the invention relates to a process for the production of aliphatic and alicyclic ketones by oxidizing the corresponding secondary alcohols with a peroxy compound in the presence of a catalyst.
- ketones obtainable by the process of the invention have the general formula
- R is a linear or branched C ⁇ _ 10 -alkyl group and R is a linear or branched Cj_ 10 -alkyl group or a phenyl group
- m and j? independently are integers from 1 to 4 and n is 0 or 1, thus forming an alicyclic ring together with the carbonyl group of (I).
- ketones are valuable compounds for a large number of applications, for example as solvents, building blocks for organic syntheses, fragrances etc.
- Linear or branched -io-alkyl groups are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, -sec-butyl, tert-butyl, pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl- propyl, hexyl, heptyl, octyl, nonyl and decyl, including all isomers of these groups.
- alicyclic ketones include cyclopropanone, cyclobutanone, cyclo- pentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, 1,3-cyclobutane- dione, 1,3-cyclopentanedione, 1,3-cyclohexanedione, 1,4-cyclohexanedione, 1,3-cyclo- heptanedione, 1 ,4-cycloheptanedione, 1,3-cyclooctanedione, 1,4-cyclooctanedione, 1,5-cyclo- octanedione, 1,3-cyclononandione, 1,4-cyclononanedione, 1,5-cyclononanedione, 1,3-cyclo- decanedione, 1,4-cyclodecanedione, 1,5-cyclodecanedione and
- ketones (I) While some of the above mentioned ketones (I) are being produced by the chemical industry in large amounts (e. g. acetone, cyclohexanone) using processes giving good yields, some others are only available by tedious procedures and/or in poor yields.
- the object of the present invention was to provide a versatile process for the production of these ketones in good yields and without expensive reactants.
- rule-(CHOH) whenever the product is a alicyclic diketone, are together -(CH 2 ),
- m, n and j? are as defined above, can smoothly be oxidized by peroxy compounds in the presence of a carboxylic acid and a manganese(iv) complex of 1 ,4,7-trimethyl-l,4,7-triazacyclononane (Me 3 tacn) to give the corresponding ketones (I) in good to excellent yields.
- Preferred peroxy compounds are hydrogen peroxide and peroxycarboxylic acids and mixtures thereof. It should be noted that hydrogen peroxide reacts with carboxylic acids to give peroxycarboxylic acids in an equilibrium reaction.
- the most preferred carboxylic acid is acetic acid.
- the preferred manganese(iv) complex of Me 3 tacn is the dinuclear complex
- the process according to the invention may be carried out in polar aprotic solvents such as acetonitrile, nitromethane or mixtures thereof, acetonitrile being especially preferred.
- polar aprotic solvents such as acetonitrile, nitromethane or mixtures thereof, acetonitrile being especially preferred.
- the process of the invention may be carried out at or near room temperature, e. g., at 0 ⁇ 0 °C, the reaction times being typically a few hours or less.
- the work-up can be done according to methods well known in the art, preferably after addition of a suitable reducing agent to destroy any excess of peroxy compound in order to avoid further oxidation and potential explosion hazards.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Aliphatic or alicyclic monoketones or alicyclic diketones of formula (I): R1-C(=O)-R2, wherein R1 is a linear or branched C¿1-10?-alkyl group and R?2¿ is a linear or branched C¿1-10?-alkyl group or a phenyl group, or R?1 and R2¿ together are -(CH¿2?)m-[C(=O)]n-(CH2)P-, wherein m and p independently are integers from 1 to 4 and n is 0 or 1, thus forming an alicyclic ring together with the carbonyl group of (I), are produced by oxidizing an alcohol of formula (II): R?1'-CHOH-R2'¿, in which R?1' and R2'¿ either have the same meaning as R?1 and R2¿ above or, if R?1 and R2¿ together are -(CH¿2?)m-[C(=O]n-(CH2)p-, are together -(CH2)m-(CHOH)n-(CH2)p- wherein m, n and p are as defined above, with a peroxy compound in the presence of a carboxylic acid and a manganese(IV) complex of 1,4,7-trimethyl-1,4,7-triazacyclononane.
Description
Process for the Production of Ketones
The invention relates to a process for the production of aliphatic and alicyclic ketones by oxidizing the corresponding secondary alcohols with a peroxy compound in the presence of a catalyst.
The ketones obtainable by the process of the invention have the general formula
Rl-C(=0 -R2 (I)
1 in which R is a linear or branched Cι_10-alkyl group and R is a linear or branched Cj_10-alkyl group or a phenyl group, or R1 and R2 together are -(CH2)m-[C(=O)]„-(CH2)p- wherein m and j? independently are integers from 1 to 4 and n is 0 or 1, thus forming an alicyclic ring together with the carbonyl group of (I).
These ketones are valuable compounds for a large number of applications, for example as solvents, building blocks for organic syntheses, fragrances etc.
Linear or branched -io-alkyl groups are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, -sec-butyl, tert-butyl, pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl- propyl, hexyl, heptyl, octyl, nonyl and decyl, including all isomers of these groups. The ketones wherein R1 and R2 together are a group of the formula -(CH2),„-[C(=O)]„-(CH2)p- are in particular all alicyclic monoketones having 3 to 9 ring carbon atoms or diketones having 4 to 10 carbon atoms wherein the carbonyl groups are separated by at least one methylene group. These alicyclic ketones include cyclopropanone, cyclobutanone, cyclo- pentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, 1,3-cyclobutane- dione, 1,3-cyclopentanedione, 1,3-cyclohexanedione, 1,4-cyclohexanedione, 1,3-cyclo- heptanedione, 1 ,4-cycloheptanedione, 1,3-cyclooctanedione, 1,4-cyclooctanedione, 1,5-cyclo- octanedione, 1,3-cyclononandione, 1,4-cyclononanedione, 1,5-cyclononanedione, 1,3-cyclo- decanedione, 1,4-cyclodecanedione, 1,5-cyclodecanedione and 1,6-cyclodecanedione.
While some of the above mentioned ketones (I) are being produced by the chemical industry in large amounts (e. g. acetone, cyclohexanone) using processes giving good yields, some
others are only available by tedious procedures and/or in poor yields. The object of the present invention was to provide a versatile process for the production of these ketones in good yields and without expensive reactants.
According to the invention, this has been accomplished by the process of claim 1.
It has been found that secondary alcohols of the formula
R^-CHOH-R2' (II)
in which R and R either have the same meaning as R and R above or, if R and R together are -(CH2)m-[C(=O)]„-(CH2)p- (i.e., if the product is a alicyclic diketone), are together -(CH2),„-(CHOH)„-(CH2)p- wherein m, n and j? are as defined above, can smoothly be oxidized by peroxy compounds in the presence of a carboxylic acid and a manganese(iv) complex of 1 ,4,7-trimethyl-l,4,7-triazacyclononane (Me3tacn) to give the corresponding ketones (I) in good to excellent yields.
Preferred peroxy compounds are hydrogen peroxide and peroxycarboxylic acids and mixtures thereof. It should be noted that hydrogen peroxide reacts with carboxylic acids to give peroxycarboxylic acids in an equilibrium reaction.
It is also possible to use other peroxy compounds, for example, tert-butyl hydroperoxide.
The most preferred carboxylic acid is acetic acid.
The preferred manganese(iv) complex of Me3tacn is the dinuclear complex
[(Me3tacn)2Mn2O3]2+[PF6]2 with three bridging oxo ligands [= tri-μ-oxobis(l,4,7-trimethyl- l,4,7-triazacyclononane)dimanganese bis(hexafluorophosphate)] which has been described by K. Wieghardt et al, J. Am. Chem. Soc. 1988, 110, 7398.
The process according to the invention may be carried out in polar aprotic solvents such as acetonitrile, nitromethane or mixtures thereof, acetonitrile being especially preferred.
A particularly preferred application of the process of this invention is the production of 1,4-cyclohexanedione (I; R\R2 = -(CH2)m-[C(=O)]„-(CH2)p- m =p = 2, n = l) from
1,4-cyclohexanediol (II; Rr,R2' = -(CH2)m-(CHOH)„-(CH2)p- m = p = 2, n = 1) which is easily available from hydroquinone.
The process of the invention may be carried out at or near room temperature, e. g., at 0^ 0 °C, the reaction times being typically a few hours or less. The work-up can be done according to methods well known in the art, preferably after addition of a suitable reducing agent to destroy any excess of peroxy compound in order to avoid further oxidation and potential explosion hazards.
The invention is illustrated by the following non-limiting examples.
Example 1
Preparation of 1,4-Cyclohexanedione
To a solution of 0.5 g of 1,4-cyclohexanediol in 10 ml of acetonitrile were added 0.2 ml of a 6.32 mM acetonitrile solution of [(Me3tacn)2Mn2O3][PF6]2 and 0.4 ml of acetic acid (99%). A mixture of 2 ml of a 35% aqueous hydrogen peroxide solution in 11 ml of acetonitrile was added dropwise under vigorous stirring at 23 °C within one hour. After the addition the clear solution was stirred for additional 30 minutes, all volatiles removed in vacuo and the residue analysed by gas chromatography, 1H- and 13C NMR spectroscopy, showing >99% conversion and >99% selectivity. The analyses were compared with a commercially available (Fluka) sample of 1,4-cyclohexanedione.
Examples 2-9
In a procedure similar to that of example 1, several secondary alcohols were oxidized. In each case, a reaction mixture containing 0.23 M (1 M = 1 mol/1) of the respective alcohol, 1.0 M of hydrogen peroxide, 0.4χ 10"4 M of [(Me3tacn)2Mn2O3] [PF6]2 and 0.5 M of acetic acid in acetonitrile as solvent was reacted at 20 °C for 3 h. The yields of the products were measured by gas chromatography after treatment of the samples with triphenylphosphine. The results are given in Table 1. All yields are based on the initial amounts of alcohol.
Table 1
Claims
1. A process for the production of aliphatic or alicyclic monoketones or alicyclic diketones of the formula
R'-C(=O)-R2 (I)
in which R is a linear or branched Cj-jo-alkyl group, R is a linear or branched d-jo-alkyl group or a phenyl group, or R1 and R2 together are 
wherein m andp independently are integers from 1 to 4 and n is 0 or 1, thus forming an alicyclic ring together with the carbonyl group of (I), by oxidizing a secondary alcohol of formula
R1'-CHOH-R2' (II)
1 ' 0' 1 0 1 in which R and R either have the same meaning as R and R above or, if R and R together are 
are together -(CH2)/n-(CHOH)„-(CH2)p- wherein m, n and/» are as defined above, with a peroxy compound in the presence of a carboxylic acid and a manganese(iv) complex of l,4,7-trimethyl-l,4,7-triazacyclononane.
2. The process of claim 1 wherein the peroxy compound is selected from the group consisting of hydrogen peroxide and peroxycarboxylic acids and mixtures thereof.
3. The process of claim 1 or 2 wherein the carboxylic acid is acetic acid.
4. The process of any one of claims 1 to 3 wherein the manganese(iv) complex of 1,4,7-tri- methyl- 1 ,4,7-triazacyclononane is tri-μ-oxobis( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)- dimanganese bis(hexafluorophosphate).
5. The process of any one of claims 1 to 4 wherein the oxidation is conducted in a solvent selected from the group consisting of acetonitrile, nitromethane, and mixtures thereof. 1 0
6. The process of any one of claims 1 to 5 wherein R and R together are
-(CH2)2-C(=O)-(CH2)2- and R1' and R2' together are -(CH2)2-CHOH-(CH2)2-.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/476,025 US7015358B2 (en) | 2001-04-27 | 2002-04-23 | Process for the production of ketones |
| EP02735283A EP1385812A1 (en) | 2001-04-27 | 2002-04-23 | Process for the production of ketones |
| JP2002585367A JP2004525986A (en) | 2001-04-27 | 2002-04-23 | Method for producing ketone |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28653901P | 2001-04-27 | 2001-04-27 | |
| US60/286,539 | 2001-04-27 | ||
| EP01111776 | 2001-05-15 | ||
| EP01111776.9 | 2001-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002088063A1 true WO2002088063A1 (en) | 2002-11-07 |
Family
ID=56290274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2002/004440 WO2002088063A1 (en) | 2001-04-27 | 2002-04-23 | Process for the production of ketones |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US7015358B2 (en) |
| EP (1) | EP1385812A1 (en) |
| JP (1) | JP2004525986A (en) |
| WO (1) | WO2002088063A1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2273006A1 (en) | 2009-06-17 | 2011-01-12 | Unilever PLC | Bleaching of substrates |
| DE102009057220A1 (en) | 2009-12-05 | 2011-06-09 | Clariant International Ltd. | Non-hygroscopic transition metal complexes, process for their preparation and their use |
| DE102009057222A1 (en) | 2009-12-05 | 2011-06-09 | Clariant International Ltd. | Bleach catalyst compounds, process for their preparation and their use |
| US7972386B2 (en) | 2005-10-12 | 2011-07-05 | Conopco, Inc. | Bleaching of substrates |
| US7976582B2 (en) | 2007-01-16 | 2011-07-12 | Conopco, Inc. | Bleaching of substrates |
| EP2377614A1 (en) | 2010-04-16 | 2011-10-19 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Bleaching of substrates |
| US8455423B2 (en) | 2005-05-27 | 2013-06-04 | Conopco, Inc. | Process of bleaching |
| US9012630B2 (en) | 2009-09-18 | 2015-04-21 | Clariant International Ltd. | Method for producing bridged manganese complexes of triazacyclononane |
| US9469666B2 (en) | 2010-03-03 | 2016-10-18 | Catexel Limited | Preparation of bleaching catalysts |
| US10144005B2 (en) | 2011-09-08 | 2018-12-04 | Richard William Kemp | Catalysts |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100486950C (en) * | 2007-01-22 | 2009-05-13 | 河北大学 | Process of synthesizing 1,4-cyclohexyl dione |
| KR101708955B1 (en) | 2009-06-05 | 2017-02-21 | 솔베이(소시에떼아노님) | Process for the manufacture of oxidized starch, oxidized starch and its use |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10024617A1 (en) * | 1999-05-19 | 2000-12-28 | Basf Ag | Production of carboxylic acid and/or aldehydes comprises oxidation in the presence of a catalyst comprising a manganese salt, 1,4,7-tri(1-20C alkyl)-1,4,7-triazacyclononane and co-ligands |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69125310T2 (en) * | 1990-05-21 | 1997-07-03 | Unilever Nv | Bleach activation |
| US6620972B2 (en) * | 2001-06-28 | 2003-09-16 | The Board Of Trustees Of The University Of Illinois | Method of oxidizing an alcohol using a recyclable fluorous sulfoxide |
-
2002
- 2002-04-23 WO PCT/EP2002/004440 patent/WO2002088063A1/en active Application Filing
- 2002-04-23 JP JP2002585367A patent/JP2004525986A/en not_active Withdrawn
- 2002-04-23 US US10/476,025 patent/US7015358B2/en not_active Expired - Fee Related
- 2002-04-23 EP EP02735283A patent/EP1385812A1/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10024617A1 (en) * | 1999-05-19 | 2000-12-28 | Basf Ag | Production of carboxylic acid and/or aldehydes comprises oxidation in the presence of a catalyst comprising a manganese salt, 1,4,7-tri(1-20C alkyl)-1,4,7-triazacyclononane and co-ligands |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8455423B2 (en) | 2005-05-27 | 2013-06-04 | Conopco, Inc. | Process of bleaching |
| US8722608B2 (en) | 2005-05-27 | 2014-05-13 | Conopco, Inc. | Process of bleaching |
| US7972386B2 (en) | 2005-10-12 | 2011-07-05 | Conopco, Inc. | Bleaching of substrates |
| US7976582B2 (en) | 2007-01-16 | 2011-07-12 | Conopco, Inc. | Bleaching of substrates |
| EP2273006A1 (en) | 2009-06-17 | 2011-01-12 | Unilever PLC | Bleaching of substrates |
| US9012630B2 (en) | 2009-09-18 | 2015-04-21 | Clariant International Ltd. | Method for producing bridged manganese complexes of triazacyclononane |
| US8889611B2 (en) | 2009-12-05 | 2014-11-18 | Clariant International Ltd | Bleach catalyst compounds, method for the production thereof and use thereof |
| DE102009057222A1 (en) | 2009-12-05 | 2011-06-09 | Clariant International Ltd. | Bleach catalyst compounds, process for their preparation and their use |
| DE102009057220A1 (en) | 2009-12-05 | 2011-06-09 | Clariant International Ltd. | Non-hygroscopic transition metal complexes, process for their preparation and their use |
| US9469666B2 (en) | 2010-03-03 | 2016-10-18 | Catexel Limited | Preparation of bleaching catalysts |
| WO2011128649A1 (en) | 2010-04-16 | 2011-10-20 | Unilever Plc | Bleaching of substrates |
| EP2377614A1 (en) | 2010-04-16 | 2011-10-19 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Bleaching of substrates |
| US9115463B2 (en) | 2010-04-16 | 2015-08-25 | Catexel Limited | Bleaching of substrates |
| US10144005B2 (en) | 2011-09-08 | 2018-12-04 | Richard William Kemp | Catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040138506A1 (en) | 2004-07-15 |
| JP2004525986A (en) | 2004-08-26 |
| US7015358B2 (en) | 2006-03-21 |
| EP1385812A1 (en) | 2004-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Oxidation of alkynes by hydrogen peroxide catalyzed by methylrhenium trioxide | |
| EP1385812A1 (en) | Process for the production of ketones | |
| Suda et al. | High-valent metalloporphyrin, Fe (tpp) OTf, catalyzed rearrangement of α, β-epoxy ketones into 1, 2-diketones | |
| JP6101636B2 (en) | Method for producing farnesal using vanadium complex | |
| Al-Hunaiti et al. | From DNA to catalysis: a thymine-acetate ligated non-heme iron (III) catalyst for oxidative activation of aliphatic C–H bonds | |
| Tesevic et al. | An easily accessed class of recyclable hypervalent iodide reagents for functional group oxidations: bis (trifluoroacetate) adducts of fluorous alkyl iodides, CF 3 (CF 2) n− 1 I (OCOCF 3) 2 | |
| Sakaguchi et al. | Oxygenation of alkynes to α, β-acetylenic ketones with dioxygen catalyzed by N-hydroxyphthalimide combined with a transition metal | |
| KR20010006477A (en) | Oxidation Catalyst System and Method of Oxidation with the Same | |
| EP3184504B1 (en) | Methods of preparing alpha,beta-unsaturated or alpha-halo ketones and aldehydes | |
| Vermaak et al. | Catalytic oxidation of alcohols with novel non-heme N 4-tetradentate manganese (ii) complexes | |
| Bartholomew et al. | Neutral organocopper (III) complexes | |
| JP4793357B2 (en) | Process for producing β-hydroxyhydroperoxides and catalyst thereof | |
| US7196191B2 (en) | Catalytic oxidation of C—H bonds | |
| Lee et al. | Efficient synthesis of β-substituted α-haloenones by rhodium (ii)-catalyzed and thermal reactions of iodonium ylides | |
| Miyamoto et al. | CO2-activated NaClO-5H2O enabled smooth oxygen transfer to iodoarene: a highly practical synthesis of iodosylarene | |
| EP1544190B1 (en) | Method for producing carboxylic acids | |
| Phillips et al. | Synthesis of γ‐Butyrolactones by a Baeyer–Villiger Oxidation with Hydrogen Peroxide, Catalysed by Methyltrioxorhenium | |
| JP6002572B2 (en) | Method for producing farnesal using bis (acetylacetonato) dioxomolybdenum (VI) | |
| US6437180B1 (en) | Preparation of aliphatic α, ω-dicarboxylic acids | |
| JPH09124594A (en) | Production of cycloalkyl hydroperoxide | |
| EP0067258B1 (en) | The preparation of cyclic ketones by catalytic oxidation of deltacarene (-3) | |
| PT103592A (en) | PROCESS FOR THE ALIQUE OXIDATION OF INSATURATED COMPOUNDS | |
| PT104193A (en) | PROCESS FOR THE ALIQUE OXIDATION OF INSATURATED COMPOUNDS | |
| BE1012264A3 (en) | New naphthalenediones and use of same in the preparation of anthracenediones | |
| JP3570067B2 (en) | Process for producing 2,3,5-trimethylhydroquinone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 2002735283 Country of ref document: EP Ref document number: 10476025 Country of ref document: US Ref document number: 2002585367 Country of ref document: JP |
|
| WWP | Wipo information: published in national office |
Ref document number: 2002735283 Country of ref document: EP |
|
| REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |