EP4031554A1 - Procede de coupure oxydante d'olefines utilisant comme catalyseur un halooxodiperoxometallate - Google Patents
Procede de coupure oxydante d'olefines utilisant comme catalyseur un halooxodiperoxometallateInfo
- Publication number
- EP4031554A1 EP4031554A1 EP20781051.6A EP20781051A EP4031554A1 EP 4031554 A1 EP4031554 A1 EP 4031554A1 EP 20781051 A EP20781051 A EP 20781051A EP 4031554 A1 EP4031554 A1 EP 4031554A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- linear
- catalyst
- denotes
- chosen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000007248 oxidative elimination reaction Methods 0.000 title claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 150000002148 esters Chemical class 0.000 claims abstract description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 cyclic olefin Chemical class 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 11
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 45
- 230000008569 process Effects 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 8
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229960004488 linolenic acid Drugs 0.000 claims description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 4
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 4
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021319 Palmitoleic acid Nutrition 0.000 claims description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229960003872 benzethonium Drugs 0.000 claims description 3
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 claims description 3
- UCIYGNATMHQYCT-OWOJBTEDSA-N cyclodecene Chemical compound C1CCCC\C=C\CCC1 UCIYGNATMHQYCT-OWOJBTEDSA-N 0.000 claims description 3
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 claims description 3
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 claims description 3
- BESIOWGPXPAVOS-UPHRSURJSA-N cyclononene Chemical compound C1CCC\C=C/CCC1 BESIOWGPXPAVOS-UPHRSURJSA-N 0.000 claims description 3
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 3
- 239000004913 cyclooctene Substances 0.000 claims description 3
- GMUVJAZTJOCSND-OWOJBTEDSA-N cycloundecene Chemical compound C1CCCC\C=C\CCCC1 GMUVJAZTJOCSND-OWOJBTEDSA-N 0.000 claims description 3
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 claims description 3
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 150000003003 phosphines Chemical class 0.000 claims description 3
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 2
- 229940073769 methyl oleate Drugs 0.000 claims description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 2
- 229960002255 azelaic acid Drugs 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 235000021313 oleic acid Nutrition 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000005643 Pelargonic acid Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 150000003628 tricarboxylic acids Chemical class 0.000 description 4
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
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- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
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- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- 231100001231 less toxic Toxicity 0.000 description 2
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- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
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- CNVZJPUDSLNTQU-SEYXRHQNSA-N petroselinic acid Chemical compound CCCCCCCCCCC\C=C/CCCCC(O)=O CNVZJPUDSLNTQU-SEYXRHQNSA-N 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
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- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- OKBQUWUVZGPEQZ-UHFFFAOYSA-N tributyl(hexadecyl)phosphanium Chemical compound CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC OKBQUWUVZGPEQZ-UHFFFAOYSA-N 0.000 description 1
- NNENFOSYDBTCBO-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC NNENFOSYDBTCBO-UHFFFAOYSA-M 0.000 description 1
- PYVOHVLEZJMINC-UHFFFAOYSA-N trihexyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC PYVOHVLEZJMINC-UHFFFAOYSA-N 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- MDTPTXSNPBAUHX-UHFFFAOYSA-M trimethylsulfanium;hydroxide Chemical compound [OH-].C[S+](C)C MDTPTXSNPBAUHX-UHFFFAOYSA-M 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/66—Tungsten
Definitions
- the present invention relates to a process for the oxidative cleavage of a substrate consisting of at least one functionalized or non-functionalized linear olefin, in particular of a mono- or polyunsaturated aliphatic carboxylic acid, or one of its esters, or of other at least one unfunctionalized cyclic olefin, using hydrogen peroxide, in the presence of a metal catalyst, which consists of at least one onium halooxodiperoxometallate. It also relates to a new catalyst consisting of a particular onium halooxodiperoxometallate which can in particular be used in this process.
- the oxidative cleavage of olefins is a chemical reaction which allows the conversion of a carbon-carbon double bond into two separate oxidized functions, such as aldehydes, ketones or acids. carboxylic. This reaction is particularly useful in the upgrading of vegetable oils.
- the oxidative cleavage transforms unsaturated fatty acids in one step into high added value oxidation products, used in the polymer industry as well as in the food industry or even perfumery. For example, oleic acid is converted by oxidative cleavage to pelargonic acid and azelaic acid.
- Azelaic acid, or nonanedioic acid is a dicarboxylic acid used as a precursor in the manufacture of polymers such as polyesters or polyamides, or in the manufacture of lubricants. This compound is also of interest as a cosmetic and dermatological active agent, because of its antimicrobial properties.
- pelargonic acid, or nonanoic acid is a carboxylic acid which can be used as a herbicide, alone or in combination with azelaic acid, or alternatively as an emollient agent.
- Ozonolysis which uses ozone O3 as an oxidant, is the most widely used process for the oxidative cleavage of olefins. Although this process is clean and efficient, the use of ozone requires the implementation of strict safety measures, as well as the installation of equipment. expensive. The chemical industry has therefore turned to the development of catalytic systems based on transition metals and less toxic and dangerous oxidants. Several processes using catalysts based on precious metals, such as rhenium, ruthenium and gold, have been developed (WO 2014/020281). However, the high catalytic loads and the absence of recycling of these expensive catalysts make it difficult to envisage the development of such processes at the industrial level. Combined with hydrogen peroxide, an inexpensive oxidizer, molybdenum and tungsten have also demonstrated their potential in the oxidative cleavage of olefins.
- US Pat. No. 5,336,793 thus describes a process for preparing carboxylic acids or esters by oxidative cleavage of esters or unsaturated acids in a two-phase medium, in which the organic phase contains the reagents and the aqueous phase contains peroxide. hydrogen and a catalyst consisting of tungstic or molybdic acid.
- the process is characterized by the addition of an onium salt, such as tetraalkylammonium or tetraalkylphosphonium chloride, which serves as a phase transfer agent, allowing the catalyst to come into contact with the reactants and thus resulting in improved yield without requiring the use of an organic solvent.
- the reaction conditions implemented in this patent are however incompatible with industrial application.
- the reaction products are in fact extracted using ethyl ether in the presence of hydrogen peroxide, then the solvent is evaporated, potentially resulting in the formation of diethyl peroxides in the concentrated state and therefore of an extremely mixture. explosive.
- Patent application EP 0 122 804 also mentions a compound obtained by reacting an onium halide with tungstic acid or a salt, in the presence of hydrogen peroxide at a pH of less than 2, in particular at a pH of 1, which has now been shown to correspond to an onium halooxodiperoxotungstate.
- this compound is used as a catalyst in the oxidative cleavage of diols, as an alternative to an onium phosphotung State.
- Patent application JP 2013/144626 also describes the use of mononuclear catalysts, in particular an onium halooxodiperoxometallate, or binuclear, in combination with hydrogen peroxide in an olefin epoxidation process. Very low yields of epoxides are however obtained with mononuclear catalysts.
- the subject of the invention is thus a process for oxidative cleavage of a substrate consisting of at least one functionalized or non-functionalized linear olefin or of at least one non-functionalized cyclic olefin, consisting in converting a carbon-carbon double bond of the substrate.
- two separate oxidized functions chosen from aldehydes, ketones and carboxylic acids, using hydrogen peroxide, in the presence of a metal catalyst, characterized in that the catalyst consists of at least one salt onium of an oxodiperoxometallate halo.
- a subject of the invention is also new catalysts of formula (II):
- M is a metal chosen from W and Mo,
- X is a halogen atom
- L denotes a neutral ligand having at least one non-binding doublet
- Q + denotes an onium cation of formula N + (RIR 2 R 3 R 4 ) where:
- R 1 denotes a linear or branched, preferably linear, C 6 -C 20 alkyl group
- R 2 and R 3 each independently denote a linear or branched, preferably linear, C 1 -C 4 alkyl group
- R 4 denotes a linear or branched, preferably linear, C 1 -C 4 alkyl group or an aryl group, or else
- R 1 denotes a linear or branched, preferably linear, C 4 -C 14 alkyl group and R 2 , R 3 and R 4 together with the nitrogen atom form a pyridinium group.
- the oxidative cleavage process according to the invention uses as substrate at least one functionalized or non-functionalized linear olefin.
- unfunctionalized olefin is meant a hydrocarbon chain containing only carbon and hydrogen atoms and which comprises at least one unsaturation.
- the term “functionalized olefin” means a hydrocarbon chain containing carbon and hydrogen atoms, comprising at least one unsaturation, and furthermore carrying at least one, and generally from one to four, group (s) inert under the conditions of the oxidative cleavage reaction, in particular chosen from: a carboxyl group (-COOH), an alkoxycarbonyl group (- OCOR), a hydroxyl group (-OH), a nitro group (-NO2), an atom of halogen (in particular -Cl or -F), an alkoxy group (-OR), an alkylcarbonyl group (-COR), an amido group (- CONH2) or dialkylamino (-NR2) or a nitrile group (-CN), where R denotes a hydrocarbon group containing from one to nine carbon atoms.
- the oxidative cleavage process according to the invention consists in converting a carbon-carbon double bond of the substrate into two separate oxidized functions, and thus makes it possible to prepare carbonyl compounds of the aldehydes, ketones and / or carboxylic acids type, and more particularly of mono-, di- and / or tri-carboxylic acids.
- the olefin is functionalized with at least one carboxyl or alkoxycarbonyl group.
- the functionalized linear olefin is thus chosen from mono- or polyunsaturated aliphatic carboxylic acids and their esters.
- This carboxylic acid can contain from 6 to 60 carbon atoms, preferably from 6 to 32 carbon atoms, more preferably from 12 to 24 carbon atoms and more preferably still from 12 to 18 carbon atoms and it can contain from 1 to 6 unsaturations, preferably from 1 to 3 unsaturations.
- Examples of mono- or polyunsaturated aliphatic carboxylic acid include lauroleic acid, myristoleic acid, palmitoleic acid, sapienic acid, petroselaidic acid, oleic acid, elaidic acid, petroselinic acid, vaccenic acid, gadoleic acid, cetoleic acid, erucic acid, selacholeic or nervonic acid, ⁇ -linoleic acid, g-linolenic acid, rumenic acid, linolenic acid, stearidonic acid, eleostearic acid, catalpic acid, arachidonic acid, and mixtures thereof.
- the acid can optionally be mono- or poly-hydroxylated and chosen in particular from ricinoleic acid.
- the aforementioned acid can be obtained by chemical or enzymatic hydrolysis of at least one fatty acid triglyceride typically obtained from a vegetable oil. Alternatively, it can be derived from animal fat.
- the ester of the acid can be a triglyceride of the acid or it can be obtained by esterification of the acid or transesterification of a triglyceride using a monoalcohol.
- Examples of mono- or polyunsaturated aliphatic carboxylic acid esters include linear or branched C1-C6 alkyl esters, such as methyl, ethyl, propyl, iso-propyl, butyl esters. , tert-butyl, pentyl, iso-pentyl or hexyl, without this list being limiting.
- An example of a triglyceride is triolein.
- oleic acid palmitoleic acid, erucic acid, linoleic acid, ⁇ -linolenic acid, their mixtures and / or one of their esters, more preferably acid, are used.
- oleic or one of its esters in particular methyl oleate.
- vegetable oils mention may in particular be made of wheat germ, sunflower, argan, hibiscus, coriander, grape seed, sesame, corn, apricot, castor oil, shea, avocado, olive, peanut, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, jojoba, alfalfa, poppy oil, pumpkin, sesame, squash, blackcurrant, evening primrose, lavender, borage, millet, barley, quinoa, rye, safflower,nadooulier, passionflower, muscat rose, d ' Echium, camelina or camellia.
- one or more oils obtained from a biomass of microalgae can be used.
- the dicarboxylic acid obtained according to one embodiment of the invention is preferably azelaic acid.
- At least one non-functionalized cyclic olefin is used as substrate.
- unfunctionalized cyclic olefins which can be used as a substrate in this invention include: cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, dicyclopentadiene, norbornene and norbornadiene, without this list is not exhaustive.
- dicarboxylic acids capable of being obtained by oxidative cleavage of unfunctionalized cyclic olefins are collated in the table below.
- Tri-carboxylic acids can be obtained by oxidative cleavage of cyclic olefins having a constrained cyclic structure, in particular a bridged structure, such as norbornene, dicyclopentadiene, or norbornadiene.
- the oxidative cleavage of norbornene provides butane-1, 2, 4-tricarboxylic acid.
- substrate will be used for the sake of simplicity to refer both to functionalized or non-functionalized linear olefins as well as to unfunctionalized cyclic olefins which can be reacted in the process according to the invention.
- the chosen substrate is oxidized using hydrogen peroxide in the presence of a particular catalyst.
- the amount of hydrogen peroxide used in this process is generally between 4 and 20 molar equivalents, preferably between 4 and 10 molar equivalents and, better, between 4 and 8 molar equivalents, limits included, of hydrogen peroxide for one. molar equivalent of double bond present within the substrate.
- the substrate consists of a mixture of olefins, in particular of a mixture of functionalized linear olefins, as in the case of vegetable oils
- the number of double bonds can be calculated by referring to the indices of acid and iodine numbers of these fatty substances, for example according to the Wijs method using iodine monochloride.
- Hydrogen peroxide can be used at a concentration of between 1 and 70% (m / V), preferably between 30% (m / V) and 70% (m / V), limits included, preferably at 60% (m / V).
- the catalyst used in the process according to the invention consists of at least one onium halooxodiperoxometallate.
- the onium can be chosen from a tetraalkylammonium, a tetraalkylphosphonium and an alkylpyridinium, the alkyl groups of which independently contain 1 to 20 carbon atoms (preferably 1 to 18 carbon atoms), benzethonium and triphenylphosphoranylidene. In the present invention, it is preferred to use a tetraalkylammonium.
- onium ions used according to the invention include: the dodecyltrimethylammonium, the trioctylmethylammonium, the tetradecyltrimethylammonium, the hexadecyltrimethylammonium the dimethyldihexadecylammonium the octadécyltriméthyl- ammonium, dioctadecyldimethylammonium the benzyldimethyldodecylammonium, the benzyldimethyltetradecylammonium, benzyldimethylhexadecylammonium the the benzyldiméthyloctadécylammonium , dodecylpyridinium, hexadecylpyridinium, benzethonium, tetrabutylammonium, tetradecyltrihexylphosphonium, hexadecyl
- M is a metal chosen from W and Mo,
- X is a halogen atom
- L denotes a neutral ligand having at least one non-binding doublet.
- ligands L are water, amines, ethers and phosphines, without this list being limiting. It is preferred according to this invention that L is H2O.
- halooxodiperoxotungstates such as chlorooxodiperoxotungstate, fluorooxodiperoxotungstate, bromooxodiperoxotungstate and iodooxodiperoxotungstate, more preferably chlorooxodiperoxotungstate.
- the catalyst used according to the invention can be prepared as described by Ryo Ishimoto et al. in Chem. Lett. 2013, 42, 476-478. As a variant, it can be synthesized according to a process comprising:
- the catalyst can then be isolated:
- (c1) either by cooling the mixture to precipitate the catalyst which can then be recovered by filtration and then optionally rinsed with water and / or with the aid of an alcohol such as ethanol
- (c2) either by separation of the organic phase and of the aqueous phase obtained, extraction of the aqueous phase using a solvent immiscible with water such as dichloromethane, ethyl acetate, cyclohexane , toluene or methyl tert-butyl ether to obtain a second organic phase, then drying using a drying agent such as anhydrous sodium sulfate, and finally evaporation in vacuo of the combined organic phases.
- a solvent immiscible with water such as dichloromethane, ethyl acetate, cyclohexane , toluene or methyl tert-butyl ether
- sodium tungstate dihydrate as the metal salt and, as the strong acid, sulfuric acid.
- the amount of strong acid is adjusted so as to bring the pH of the reaction medium to a value between 0.5 and 2.0, preferably between 1.0 and 1.5.
- the hydrogen peroxide is preferably used in an amount representing from 1 to 10 molar equivalents, more preferably from 2 to 10 molar equivalents, better still from 3 to 8 molar equivalents, or even from 5 to 6 molar equivalents, relative to the amount molar metal acid salt.
- onium halides which can be used in the second step of this process are in particular: dodecyltrimethylammonium chloride, trioctylmethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dimethyldihexadecylammonium chloride, octyl ammonium chloride , dioctadecyl dimethyl ammonium chloride chloride, benzyldimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethylhexadecylammonium, benzyldiméthyloctadécylammonium chloride, dodecylpyridinium chloride, hexadecylpyridinium chloride, benzethonium chloride, tetrabutylammonium chloride, t
- the onium halide added in the second step is advantageously used in an equimolar amount with respect to the metal acid salt.
- the amount of catalyst used in the process according to the invention is generally between 0.1 and 10 mol%, preferably between 0.5 and 8 mol%, more preferably between 2 and 6 mol%, relative to the molar amount of double bonds present within the substrate. As a variant or in addition, it can represent from 0.1 to 15% by mass, preferably from 5 to 10% by mass, relative to the molar quantity of double bonds present within the substrate.
- the process according to the invention can thus be implemented under economically very advantageous conditions, insofar as it uses a small amount of catalyst, which can moreover be manufactured simply.
- the absence of toxic metals in this catalyst makes it possible to carry out this process under conditions which are more respectful of the environment and of human health than some of the processes of the prior art.
- M is a metal chosen from W and Mo,
- X is a halogen atom
- L denotes a neutral ligand having at least one non-binding doublet
- Q + denotes an onium cation of formula N + (R I R2R3R4) where: - Ri denotes a linear or branched, preferably linear, C 6 -C 20 (for example, C 12 -C 18 ), R2 and R 3 each independently denote a linear or branched, preferably linear, C 1 -C 4 alkyl group and R4 denotes a linear or branched, preferably linear, C 1 -C 4 alkyl group or an aryl group, or else
- R 1 denotes a linear or branched, preferably linear, C 4 -C 14 alkyl group and R2, R3 and R4 together with the nitrogen atom form a pyridinium group.
- L ligands are water, amines, ethers and phosphines, preferably L is H2O.
- R 1 denotes a linear or branched, preferably linear, C12-C18 (for example C12-C14) alkyl group
- R 2 and R 3 each independently denote a linear or branched alkyl group, of preferably linear
- C1-C4 and R4 denotes a linear or branched, preferably linear, C1-C4 alkyl group or an aryl group.
- R 1 denotes a linear or branched, preferably linear, C 6 -C 20 (for example C 12 -C 14 ) alkyl group
- R 2 and R 3 each denote a methyl group
- R4 denotes a methyl group an aryl group.
- R1 denotes a linear or branched, preferably linear, C1 2 -Ci 8 (for example, C 12 -C 14 ) alkyl group
- R2 and R 3 each denote a methyl group
- R4 denotes a methyl group an aryl group.
- the new catalysts above make it possible to obtain the desired dicarboxylic acid with a molar yield of at least 40 %, preferably at least 50%, at least 60%, at least 70% or even at least 80% or even at least 90%.
- halogen is preferably chlorine or fluorine, more preferably chlorine.
- catalysts corresponding to the definition above are given above.
- dodecytrimethylammonium chlorooxodiperoxotungstate is preferred for its ease of preparation without organic solvent and its efficiency.
- the oxidative cleavage process according to the invention generally comprises the steps consisting in:
- the substrate consists of at least one monounsaturated linear olefin, and is used in the preparation of at least one monocarboxylic acid.
- the olefin is non-functionalized, or else functionalized by any group other than a carboxyl.
- the substrate consists of at least one cyclic olefin (such as cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, dicyclopentadiene, norbomene and norbornadiene, without this list being limiting), and is used in the preparation of at least one di- or tri-carboxylic acid or one of its esters.
- cyclic olefin such as cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, dicyclopentadiene, norbomene and norbornadiene, without this list being limiting
- the substrate consists of at least one mono- or polyunsaturated aliphatic carboxylic acid, or one of its esters, and is used in the preparation of at least one dicarboxylic acid or one of its esters, and optionally at least one monocarboxylic acid.
- the oxidative cleavage method according to the invention generally comprises the steps consisting in:
- this process does not use an organic solvent, in particular chosen from 1,2-dichloroethane, dichloromethane, chloroform, ethyl ether, tert-butanol or acetonitrile.
- Dicarboxylic acid can be recovered by crystallization followed by filtration or centrifugation. To do this, the reaction mixture can be cooled, for example to 0-30 ° C and preferably to 15-25 ° C, to precipitate the dicarboxylic acid. This can then be optionally redissolved in water and then precipitated in an appropriate solvent, in particular an apolar organic solvent such as heptane which makes it possible to extract the mono-carboxylic acid formed simultaneously.
- an organic solvent in particular chosen from 1,2-dichloroethane, dichloromethane, chloroform, ethyl ether, tert-butanol or acetonitrile.
- dicarboxylic acids which can be prepared according to this preferred embodiment of the invention are in particular azelaic acid, adipic acid, succinic acid, sebacic acid, 1,7-heptanedioic acid, 1,8-octanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, brassylic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanedioic acid and thapsic acid, preferably azelaic acid, adipic acid, succinic acid, sebacic acid, 1,12-dodecanedioic acid, brassylic acid, and thapsic acid, more preferably l azelaic acid.
- dicarboxylic acids can be used in particular as a monomer in the manufacture of polymers such as polyesters or polyamides, as a plasticizer, in the manufacture of esters, lubricants or as a cosmetic or dermatological active.
- dicarboxylic acid consists of azelaic acid, it can also be used as an antibacterial active agent intended in particular for the treatment of acne or rosacea.
- the mono-, di- or tri-carboxylic acids prepared by the process of the invention can then be reduced to alcohols, for example by means of lithium tetrahydroaluminate, as described in Biomacromolecules 2010, 11, 911-918 (reduction of azelaic acid to 1,9-nonanediol), or by metallo-catalyzed hydrogenation (Chem. Commun., 2018, 54, 13319).
- FIG 1 represents the molecular structure of the compound described in Example 2, obtained by XRD and represented with ellipsoids at 50% probability.
- the reagents come from usual commercial suppliers (Sigma-Aldrich-Merck, Acros, Alfa-Aesar, Fisher) and were used without prior purification.
- GC-MS analyzes were performed with a Shimadzu QP2010SE instrument, using 3 ⁇ 4 as carrier gas, with a Zebron FAST GC column (Phenomenex) (20 mx 0.18 mm x 0.18 pm).
- GC-MS quantification was performed using octanoic acid as an internal standard.
- concentrations of azelaic, pelargonic and oleic acids were calculated by means of a calibration curve (R 2 > 0.99 in all three cases).
- NMR Nuclear Magnetic Resonance
- Na 2 WC> 4 .2H 2 0 (6.93 mmol, 1.00 eq.) Is introduced into a 50 mL flask, then 5 mL of distilled water are added in order to dissolve Na 2 W0 4 .2H 2 0.
- a solution of H 2 SO 4 (2M, 5 mmol; 0.72 eq.) immediately followed by the addition of hydrogen peroxide (30 w / v%; 37.48 mmol; 5.4 eq.).
- the solution turns yellow and then practically colorless.
- the pH of this is between 0.9 and 1.1, otherwise it can be adjusted with a few more drops of the H 2 SO 4 solution .
- the alkylammonium halide dissolved in 10 mL of dichloromethane is then added to the medium (7.28 mmol; 1.05 eq.). The solution is then stirred vigorously at 20 ° C. for 1 h 30 min. The phases are then separated and the aqueous phase is extracted with 15 ml of dichloromethane. The organic phase is dried over anhydrous sodium sulfate, then evaporated on a rotary evaporator. The solid obtained is dried under vacuum overnight. The yields obtained at the end of the above processes are collated in the following table.
- NaiWO- t ⁇ HiO (6.93 mmol, 1.00 eq.) Is introduced into a 50 mL flask, then 5 mL of distilled water are added in order to dissolve Na 2 W0 4 .2H 2 0. To this solution is then added a H2SO4 solution (2M, 5 mmol; 0.72 eq.) immediately followed by the addition of hydrogen peroxide (30 w / v%; 37.48 mmol; 5.4 eq.). The solution turns yellow and then practically colorless. The pH of this is between 0.9 and 1.1, otherwise it can be adjusted with a few more drops of the H2SO4 solution.
- the dodecyltrimethylammonium chloride dissolved beforehand in 5 mL of distilled water is then added dropwise (7.28 mmol; 1.05 eq.). A white precipitate forms and then redissolves.
- the medium is then stirred for 30 minutes at 20 ° C., then placed cold (4 ° C.) overnight.
- the precipitate formed is filtered off and then rinsed with H2O (4 ⁇ 50 mL), then with ethanol cooled to 0 ° C. (25 mL).
- the product is then pre-dried in a rotary evaporator, then left to dry under vacuum, in the presence of P2O5 overnight.
- the flask is then fitted with a condenser and the reaction mixture is brought to reflux by contact with a metal heating block (DrySyn block, Asynt) preheated to 90 ° C, with stirring at 1000 rpm, for 5 h.
- a metal heating block DrySyn block, Asynt
- the reaction medium remains two-phase, with a white lower phase and a colorless upper phase.
- the medium is allowed to cool to 22 ° C. After cooling, a white solid appears at the bottom of the flask.
- GC-MS analysis of the medium is carried out after derivatization with trimethylsulfonium hydroxide (0.2 mol / L in methanol), according to a procedure described in Journal of Chromatography A, 2004, 1047, 111-116.
- the molar yields are then calculated using a calibration curve using octanoic acid as internal standard: azelaic acid 98%, pelargonic acid 74%.
- Azelaic acid can be isolated using the following procedure: at the end of the reaction, 25 mL of deionized water are added to the reaction flask, then the mixture is heated to 90 ° C., with stirring at 300 revolutions / min. After 10 min. Upon heating, the white solid dissolves completely, thus giving a whitish solution.
- the purity of the azelaic acid obtained is calculated by GC-MS analysis after derivatization with N, 0-bis (trimethylsilyl) trifluoroacetamide with 1% of trimethylchlorosilane: 50 mg of azelaic acid are dissolved in 1 mL of THF, then 10 ⁇ L of this solution are introduced into a GC vial, followed by the addition of 100 ⁇ L of anhydrous pyridine, then 100 ⁇ L of N, O-bis (trimethylsilyl) trifluoroacetamide with 1% of trimethylchlorosilane. The mixture is heated and stirred in the GC vial at 40 ° C.
- the isolated molar yield corrected for azelaic acid is 97%.
- a reactor (16 mm external diameter, 15 mL) fitted with a 10 ⁇ 5 mm magnetic bar is charged with dodecyltrimethylammonium chlorooxodiperoxotungstate catalyst (44.7 mg; 0.08 mmol; 0.029 eq.)
- cyclohexene purity 99%
- To this mixture is then added hydrogen peroxide at 60% (m / V) (960 pL; 16.93 mmol; 5.9 eq.).
- the reaction mixture is heated by contact with a metal heating block (DrySyn block, Asynt) already preheated to 90 ° C., with stirring at 1000 revolutions / min, for 5 h.
- the reaction medium becomes monophasic and completely clear.
- the medium is allowed to cool to 25 ° C., allowing a white solid to appear at the bottom of the reactor.
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FR1910191A FR3100809B1 (fr) | 2019-09-16 | 2019-09-16 | Procédé de coupure oxydante d'oléfines utilisant comme catalyseur un halooxodiperoxométallate |
PCT/FR2020/051585 WO2021053289A1 (fr) | 2019-09-16 | 2020-09-14 | Procede de coupure oxydante d'olefines utilisant comme catalyseur un halooxodiperoxometallate |
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EP4031554A1 true EP4031554A1 (fr) | 2022-07-27 |
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EP20781051.6A Pending EP4031554A1 (fr) | 2019-09-16 | 2020-09-14 | Procede de coupure oxydante d'olefines utilisant comme catalyseur un halooxodiperoxometallate |
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US (1) | US20220315517A1 (fr) |
EP (1) | EP4031554A1 (fr) |
CN (1) | CN114787172A (fr) |
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WO (1) | WO2021053289A1 (fr) |
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IT1200002B (it) | 1983-04-15 | 1989-01-05 | Montedison Spa | Procedimento per la preparazione di acidi carbossilici a partire da olefine o diidrossicomposti vicinali |
IT1251708B (it) | 1991-12-11 | 1995-05-20 | Novamont Spa | Procedimento per la preparazione di acidi carbossilici o loro esteri mediante scissione ossidativa di acidi grassi insaturi o loro esteri. |
FR2984887B1 (fr) | 2011-12-22 | 2014-01-03 | Toulouse Inst Nat Polytech | Procede de scission moleculaire oxydative d'un compose gras |
JP5801727B2 (ja) * | 2012-01-16 | 2015-10-28 | 株式会社日本触媒 | ペルオキソ錯体 |
FR2994178B1 (fr) | 2012-07-31 | 2015-08-07 | Interoleagineuse D Assistance Et De Dev S I A Soc | Procede de preparation d'un acide carboxylique ou d'un aldehyde |
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FR3100809A1 (fr) | 2021-03-19 |
FR3100809B1 (fr) | 2023-06-02 |
CN114787172A (zh) | 2022-07-22 |
WO2021053289A1 (fr) | 2021-03-25 |
US20220315517A1 (en) | 2022-10-06 |
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