EP2880010A1 - Procede de preparation d'un acide carboxylique à partir d'un diol ou d'un epoxyde par coupure oxydante - Google Patents
Procede de preparation d'un acide carboxylique à partir d'un diol ou d'un epoxyde par coupure oxydanteInfo
- Publication number
- EP2880010A1 EP2880010A1 EP13756629.5A EP13756629A EP2880010A1 EP 2880010 A1 EP2880010 A1 EP 2880010A1 EP 13756629 A EP13756629 A EP 13756629A EP 2880010 A1 EP2880010 A1 EP 2880010A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- process according
- reaction
- diol
- oxidative cleavage
- 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.)
- Withdrawn
Links
- 150000002009 diols Chemical class 0.000 title claims abstract description 32
- 238000007248 oxidative elimination reaction Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 150000002118 epoxides Chemical class 0.000 title claims abstract 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 23
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- VACHUYIREGFMSP-UHFFFAOYSA-N (+)-threo-9,10-Dihydroxy-octadecansaeure Natural products CCCCCCCCC(O)C(O)CCCCCCCC(O)=O VACHUYIREGFMSP-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000005643 Pelargonic acid Substances 0.000 claims description 8
- -1 fatty acid ester Chemical class 0.000 claims description 8
- JPFGKGZYCXLEGQ-UHFFFAOYSA-N 1-(4-methoxyphenyl)-5-methylpyrazole-4-carboxylic acid Chemical compound C1=CC(OC)=CC=C1N1C(C)=C(C(O)=O)C=N1 JPFGKGZYCXLEGQ-UHFFFAOYSA-N 0.000 claims description 7
- VACHUYIREGFMSP-SJORKVTESA-N 9,10-Dihydroxystearic acid Natural products CCCCCCCC[C@@H](O)[C@@H](O)CCCCCCCC(O)=O VACHUYIREGFMSP-SJORKVTESA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- HXWJFEZDFPRLBG-UHFFFAOYSA-N Timnodonic acid Natural products CCCC=CC=CCC=CCC=CCC=CCCCC(O)=O HXWJFEZDFPRLBG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- VZCCETWTMQHEPK-QNEBEIHSSA-N gamma-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCC(O)=O VZCCETWTMQHEPK-QNEBEIHSSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229940090949 docosahexaenoic acid Drugs 0.000 claims description 2
- 235000020669 docosahexaenoic acid Nutrition 0.000 claims description 2
- 229960005135 eicosapentaenoic acid Drugs 0.000 claims description 2
- 235000020673 eicosapentaenoic acid Nutrition 0.000 claims description 2
- VZCCETWTMQHEPK-UHFFFAOYSA-N gamma-Linolensaeure Natural products CCCCCC=CCC=CCC=CCCCCC(O)=O VZCCETWTMQHEPK-UHFFFAOYSA-N 0.000 claims description 2
- 235000020664 gamma-linolenic acid Nutrition 0.000 claims description 2
- 229960002733 gamolenic acid Drugs 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- 229960003656 ricinoleic acid Drugs 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 claims 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims 2
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 claims 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims 1
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 claims 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims 1
- XJXROGWVRIJYMO-SJDLZYGOSA-N Nervonic acid Natural products O=C(O)[C@@H](/C=C/CCCCCCCC)CCCCCCCCCCCC XJXROGWVRIJYMO-SJDLZYGOSA-N 0.000 claims 1
- 235000021319 Palmitoleic acid Nutrition 0.000 claims 1
- 235000021342 arachidonic acid Nutrition 0.000 claims 1
- 229940114079 arachidonic acid Drugs 0.000 claims 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 claims 1
- GWHCXVQVJPWHRF-UHFFFAOYSA-N cis-tetracosenoic acid Natural products CCCCCCCCC=CCCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-UHFFFAOYSA-N 0.000 claims 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 claims 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 description 15
- 150000001299 aldehydes Chemical class 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 150000002924 oxiranes Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000005805 hydroxylation reaction Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000033444 hydroxylation Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229940031723 1,2-octanediol Drugs 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HOBAELRKJCKHQD-QNEBEIHSSA-N dihomo-γ-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCCCC(O)=O HOBAELRKJCKHQD-QNEBEIHSSA-N 0.000 description 2
- 238000005906 dihydroxylation reaction Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- SBHCLVQMTBWHCD-METXMMQOSA-N (2e,4e,6e,8e,10e)-icosa-2,4,6,8,10-pentaenoic acid Chemical compound CCCCCCCCC\C=C\C=C\C=C\C=C\C=C\C(O)=O SBHCLVQMTBWHCD-METXMMQOSA-N 0.000 description 1
- VXMDPLMIABGBQA-AFEZEDKISA-N (Z)-icos-9-enoic acid icos-11-enoic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCCC=CCCCCCCCCCC(O)=O VXMDPLMIABGBQA-AFEZEDKISA-N 0.000 description 1
- KSDMISMEMOGBFU-UHFFFAOYSA-N (all-Z)-7,10,13-Eicosatrienoic acid Natural products CCCCCCC=CCC=CCC=CCCCCCC(O)=O KSDMISMEMOGBFU-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-UHFFFAOYSA-N 9,12-Octadecadienoic Acid Chemical compound CCCCCC=CCC=CCCCCCCCC(O)=O OYHQOLUKZRVURQ-UHFFFAOYSA-N 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- YEBDWAHEIMUJQT-XVSDJDOKSA-N CCCCCC=CCC=CCC=CCC=CCCCC(O)=O.CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O Chemical compound CCCCCC=CCC=CCC=CCC=CCCCC(O)=O.CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YEBDWAHEIMUJQT-XVSDJDOKSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- RVJVAMZRPQBPEE-UHFFFAOYSA-N cyclohex-2-ene-1,1-diol Chemical compound OC1(O)CCCC=C1 RVJVAMZRPQBPEE-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- ZJVATSUMFCZSKA-KVVVOXFISA-N docos-13-enoic acid;(z)-docos-13-enoic acid Chemical compound CCCCCCCCC=CCCCCCCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O ZJVATSUMFCZSKA-KVVVOXFISA-N 0.000 description 1
- MBMBGCFOFBJSGT-SFGLVEFQSA-N docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C\C\C=C\C\C=C\C\C=C\C\C=C\C\C=C\CCC(O)=O MBMBGCFOFBJSGT-SFGLVEFQSA-N 0.000 description 1
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- JYDNQSLNPKOEII-CFYXSCKTSA-N hexadec-9-enoic acid;(z)-hexadec-9-enoic acid Chemical compound CCCCCCC=CCCCCCCCC(O)=O.CCCCCC\C=C/CCCCCCCC(O)=O JYDNQSLNPKOEII-CFYXSCKTSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 1
- RITHLQKJQSKUAO-UHFFFAOYSA-N methyl 9,10-dihydroxyoctadecanoate Chemical compound CCCCCCCCC(O)C(O)CCCCCCCC(=O)OC RITHLQKJQSKUAO-UHFFFAOYSA-N 0.000 description 1
- SBIGSHCJXYGFMX-UHFFFAOYSA-N methyl dec-9-enoate Chemical compound COC(=O)CCCCCCCC=C SBIGSHCJXYGFMX-UHFFFAOYSA-N 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- YZAZXIUFBCPZGB-KVVVOXFISA-N octadec-9-enoic acid;(z)-octadec-9-enoic acid Chemical compound CCCCCCCCC=CCCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YZAZXIUFBCPZGB-KVVVOXFISA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- DHEMVUXAYZGHFQ-KVVVOXFISA-N tetracos-15-enoic acid;(z)-tetracos-15-enoic acid Chemical compound CCCCCCCCC=CCCCCCCCCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O DHEMVUXAYZGHFQ-KVVVOXFISA-N 0.000 description 1
- VSLOIHHRIJJNOM-YSMBQZINSA-N tetradec-9-enoic acid;(z)-tetradec-9-enoic acid Chemical compound CCCCC=CCCCCCCCC(O)=O.CCCC\C=C/CCCCCCCC(O)=O VSLOIHHRIJJNOM-YSMBQZINSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- DTOSIQBPPRVQHS-UHFFFAOYSA-N α-Linolenic acid Chemical compound CCC=CCC=CCC=CCCCCCCCC(O)=O DTOSIQBPPRVQHS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- 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
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
-
- 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
-
- 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
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/18—Azelaic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
Definitions
- the invention relates to a process for preparing carboxylic acids, more particularly carboxylic acids having one or two acid functions, by oxidative cleavage of at least one diol or an epoxide.
- the oxidizing cleavage of olefins can generally be carried out in one or two stages, either directly from olefins, or following a hydroxylation step or prior epoxidation of these compounds.
- the document FR2086521 describes, in this sense, the oxidative cleavage of various vicinal diols, including the diol of oleic acid, with potassium monopersulfate and in the presence of a catalytic amount of nickel (20mol%). This technology uses nickel salts and remains toxic to the environment.
- US Pat. No. 4,006,173 discloses a continuous cleavage process using cobalt or ruthenium complexes under an atmosphere having pure oxygen and in the presence of a solvent.
- WO2008 / 138892 and WO2011 / 080296 both disclose a process for preparing monocarboxylic acids and triglycerides in the presence of solvent.
- the subject of the present invention is a process for preparing a carboxylic acid, or an aldehyde, by oxidative cleavage of at least one olefin, a vicinal diol, or an epoxide, the reaction being carried out in the presence a catalyst, an oxidant and in the absence of a solvent.
- the invention has the advantage of not using solvents. This makes it possible to reduce the costs of the reaction, to limit the risk of pollution of the environment and the danger of the reaction.
- the invention also allows the preparation of aldehydes or preferably carboxylic acids in a single step or by combining in the same reactor the dihydroxylation step and the oxidative cleavage step when the reaction is conducted directly from olefins.
- the subject of the invention is a process for preparing a carboxylic acid, by oxidative cleavage of at least one vicinal diol, or an epoxide, the reaction being carried out in the presence of a catalyst, a oxidizing and without added solvent.
- the oxidative cleavage reaction is preferably carried out on vicinal diols or on pure epoxides, this making it possible to obtain acids which also have a high degree of purity.
- the purity of the product obtained can thus be greater or equal to 95% by weight, preferably greater than or equal to 99%.
- solvents organic compounds comprising at least one carbon atom and inorganic carbon-free compounds which have the capacity to dissolve or dilute at least one of the products used or obtained by the process of the invention.
- absence of solvent must be understood in its most common sense as not excluding the presence of a minimal amount of solvent, or "trace”. Such an amount may for example be quantified as less than or equal to 10% by weight of the reaction medium, preferably less than 1%, or even less than 0.1%.
- the oxidative cleavage reaction used in the process of the invention is therefore advantageously carried out in the absence of a solvent, that is to say without adding any organic solvent or inorganic solvent, including water, to the solvent. any of the steps of the method. It makes it possible to obtain at least one, and preferably two, compounds such as carboxylic acids, aldehydes or other compounds comprising oxygen such as oxacycloalkanes. The production of carboxylic acids is particularly envisaged.
- carboxylic acid is meant any compound having a structure of varied nature, linear, branched or cyclic, having at least one carboxylic acid function.
- aldehyde any compound having a structure of varied nature, linear, branched or cyclic, having at least one aldehyde function.
- the reaction is conducted under an atmosphere comprising oxygen, the oxygen then being the oxidizer of the reaction.
- the reaction is conducted in the presence of air, or a gaseous mixture comprising oxygen in a proportion similar to air as well as inert gases, the oxygen included in the air being the oxidant of the reaction.
- air or a gaseous mixture comprising oxygen in a proportion similar to air as well as inert gases, the oxygen included in the air being the oxidant of the reaction.
- oxygen in the air is less hazardous and avoids the need for additional product additions that may be toxic or difficult to control or recycle.
- a particular aspect of the invention is therefore a process using no other oxidant than air or an equivalent mixture in danger.
- the reaction is carried out in the presence of a catalyst based on ruthenium, cerium, palladium, iron, copper, nickel, rhenium, manganese, rhodium, cobalt, vanadium or molybdenum. , gold, tungsten, lead, platinum or a mixture of these metals.
- a catalyst based on ruthenium, cerium, palladium, iron, copper, nickel, rhenium, manganese, rhodium, cobalt, vanadium or molybdenum. , gold, tungsten, lead, platinum or a mixture of these metals.
- the catalyst is of formula M (OH) x / Support, in which M is a metal as defined above, x is an integer from 0 to 8, and wherein the support is selected from carriers conventionally used in heterogeneous catalysis.
- M is a metal as defined above
- x is an integer from 0 to 8
- the support is selected from carriers conventionally used in heterogeneous catalysis.
- the metal M may be deposited on alumina, zirconia, coal, silica, a zeolite or a mixture thereof.
- the catalyst is chosen from low-toxicity catalysts and easy recycling. It is also advantageous to use a catalyst in solid form, or heterogeneous, during the process according to the invention.
- M is a metal chosen from the group consisting of palladium, iron, copper, nickel, rhenium, manganese, rhodium, platinum, vanadium, molybdenum, gold, tungsten, lead and a mixture thereof.
- the catalyst used is advantageously a catalyst based on ruthenium, iron, copper or palladium.
- x is a number, whole or not, ranging from 1 to 8, more particularly from 1 to 4 and preferably from 1 to 3.
- the catalyst used is a ruthenium / alumina catalyst of formula Ru (OH) x / Al 2 O 3 .
- the proportion of catalyst used is from 0.001% to 50% by mole relative to the substrate and / or from 0.001% to 50% by mass relative to the support.
- the proportion of catalyst is from 0.01% to 50% by mole relative to the substrate and / or from 0.01% to 50% by mass relative to the support.
- the metal used is ruthenium, iron, copper or palladium.
- the catalyst load used can range from 0.1 to 100 ppm (mass). Preferably it is chosen from 1 to 50 ppm, more particularly from 5 to 15 ppm, for example 10 ppm.
- the reaction is carried out at a pressure of 10 -3 mbar at 15 bar, preferably at 4 -10 bar, more preferably 8 bar ⁇ 0.2.
- the reaction is conducted at a temperature of 0 ° C to 200 ° C, preferably 90 ° C to 160 ° C, more preferably 90 to 110 ° C.
- the olefin used in the reaction comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, and has the following formula (I):
- the diol used comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, preferably from 1 to 24 carbon atoms, and has the following formula (II):
- p is an integer from 1 to 6, preferably from 1 to 3;
- n is an integer from 1 to 28, even more preferably from 1 to 12;
- alkyl or hydroxyalkyl group having from 1 to 27 carbon atoms, preferably from 1 to 12,
- R 1 and R 2 together form an alkylene group - (CH 2 ) m - in which m 'is an integer between 2 and 10, preferably between 2 and 6, and
- R 3 and R 4 together form a bond -O- (epoxide), or each represent a hydroxyl group.
- alkyl group is meant here a linear or branched, preferably linear, saturated hydrocarbon chain.
- hydroxyalkyl group is meant herein an alkyl group of which at least one of the hydrogen atoms is replaced by a hydroxyl group (-OH).
- the process according to the invention is generally useful for the oxidative cleavage of diols derived from monounsaturated or polyunsaturated acids and their derivatives, such as, for example, the corresponding fatty acid esters, in particular long-chain esters (having a number greater than 10 carbon atoms, preferably 10 to 30 carbon atoms), preferably originating from natural sources and in particular from oleaginous plants, for example, soybean oil, sunflower oil, rapeseed oil, linseed oil, olive oil, castor oil, peanut oil, or Palm oil.
- mono-unsaturated acid By way of example of mono-unsaturated acid, mention may be made of myristoleic acid (9-tetradecenoic acid), palmitoleic acid (9-hexadecenoic acid), oleic acid (9-octadecenoic acid), ricinoleic acid (12-hydroxy-9-octadecenoic acid), gadoleic acid (11-eicosenoic acid), erucic acid (13-docosenoic acid), nervonic acid (15-tetracosenoic acid).
- polyunsaturated acid By way of example of polyunsaturated acid, mention may be made of linoleic acid (9,12-octadecadienoic acid), alpha-linolenic acid (9,12,15-octadecatrienoic acid), gamma linolenic acid (6,9,12-octadecatrienoic acid), di-homo-gamma-linolenic acid (8,11,14-eicosatrienoic acid), arachidonic acid (5,8,11,14-eicosatetraenoic acid), timnodonic acid (5,8,11,14,17-eicosapentaenoic acid), cervonic acid (4,7,10,13,16,19-docosahexaenoic acid).
- This process can also be applied to dimeric or trimeric compounds derived from the dimerization or trimerization of fatty acids or esters of fatty acids present in rapeseed, flax, olive, castor or peanut oils.
- This process is particularly suitable for the oxidative cleavage of the diol of oleic acid (compound of formula I above in which p and n are 1, R 1 is a group - (CH 2 ) 6 -CH 3 , R 2 represents a group - (CH 2 ) 7-COOH and R 3 and R 4 represents an alcohol function) in pelargonic acid and azelaic acid.
- the starting material used in the process according to the invention may advantageously be a mixture of compounds, for example a mixture of olefins, in particular a mixture of fatty acids or of their hydroxylated derivatives.
- This method is also useful for the oxidative cleavage of diols derived from cyclic alkenes and in particular the cyclohexene diol which makes it possible to prepare adipic acid whose industrial use for the manufacture of nylon is well known.
- R 1 and R 2 represents a group - (CH 2 ) m --CO 2 A (A representing a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms and m, an integer of 1 to 26, preferably 5 and 9) and the other substituent represents an alkyl group having from 1 to 27 carbon atoms, preferably from 1 to 12, preferably from 5 to 9,
- A representing a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms and m, an integer of 1 to 26, preferably 5 and 9
- the other substituent represents an alkyl group having from 1 to 27 carbon atoms, preferably from 1 to 12, preferably from 5 to 9
- the oxidative cleavage of the Formula (I) results in a mixture of mono-carboxylic acid and dicarboxylic acid. This is the case, for example, when the starting material is oleic acid and a mixture of pelargonic acid and azelaic acid is obtained.
- the oxidative cleavage can also lead to a mixture of monocarboxylic acid and half ester. This is the case when the starting material is an alkyl oleate and a mixture of pelargonic acid and mono-alkyl azelate is obtained.
- the oxidative cleavage leads to a mixture of dicarboxylic acids. or even to a single di-carboxylic acid when the starting diol is symmetrical, that is to say when Ri represents a group - (CH 2 ) -C0 2 A and R 2 represents a group - (CH 2 ) - C0 2 A, with n equal to 1.
- the starting diol corresponds to formula (I) in which:
- n is an integer between 6 and 9 and A represents a hydrogen atom or an alkaline cation
- R 2 represents:
- n which is identical in R 1 and R 2 , is an integer between 6 and 9 and A represents a hydrogen atom or an alkaline cation; and p is preferably 1.
- the starting material is a ⁇ -unsaturated or ⁇ -dihydroxy fatty acid, that is to say a fatty acid consisting of or comprising an acyclic carbon chain, which comprises an unsaturation, or a vicinal double hydroxylation in end of the chain such as methyl 9-decenoate and the corresponding dihydroxy compound.
- the starting material is oleic acid and / or 9,10-dihydroxystearic acid.
- the process comprises a further prior step of hydroxylation of the olefin used.
- This step can be carried out by the use of electrophilic oxidants, such as potassium permanganate or osmium tetroxide, or by the hydrolysis of oxacyclopropanes (epoxides). It advantageously makes it possible to purify the diol obtained and to carry out the oxidative cleavage reaction according to the process of the invention on a purified diol which leads to obtaining carboxylic acids with a high degree of purity.
- the process according to the invention makes it possible to obtain a dicarboxylic acid, a dialdehyde and / or an aldehyde / acid, saturated or not.
- the process makes it possible to obtain an aldehyde or even more advantageously an unsaturated carboxylic acid.
- Such compounds can be obtained for example by the use of unsaturated vicinal diols as starting materials. These can optionally be obtained by selective epoxidation of an olefin having several unsaturations.
- the process according to the invention allows the preparation of a dicarboxylic acid.
- it allows the preparation of a monocarboxylic acid and a dicarboxylic acid.
- the carboxylic acid obtained has the following formula (II):
- n, n 'and n are identical or different, chosen independently of each other, from 0 to 10,
- A is a hydrogen atom, a carboxylic acid function - (COOH), and
- said carboxylic acid having 2 to 16 carbon atoms, preferably 3 to 12 carbon atoms, preferentially 5, 6, 7, 8, 9 or 10 carbon atoms.
- the reaction products obtained from oleic acid, its diol or epoxide derivative are pelargonic acid and azelaic acid.
- An advantageous aspect of the process is a conversion rate to carboxylic acid and / or high aldehyde, in particular greater than 90% and more particularly greater than 99%.
- Another advantageous aspect is a mass yield of bifunctional compounds, such as dicarboxylic acids, dialdehydes or aldehydes / acids, greater than 35%, preferably greater than 40%.
- the diol used is cyclohexane diol and, preferably, the process according to the invention makes it possible to obtain adipic acid.
- the carboxylic acid or aldehyde is obtained in a single reaction step.
- the resulting mixture is then heated at 40 ° C for 8 h and then allowed to stand at room temperature overnight.
- the oil is mixed in 150 mL of 1N potassium hydroxide (KOH) and then heated at 90 ° C for 1 hour.
- KOH potassium hydroxide
- the pH is adjusted to 2 of this solution by adding concentrated hydrochloric acid (37% by weight).
- the oily phase obtained is separated using a dropping funnel and is washed with 100 ml of water. 59 g of an oil are obtained.
- this oil is recrystallized from hexane and pure 9,10-dihydroxystearic acid is obtained in the form of a white solid.
- Alumina (2 g) is added in powder form (after calcination at 550 ° C. for 3 hours) in an aqueous solution of RuCl 3 at room temperature (8.3 mM). After 15 minutes, the pH is adjusted to 13 by adding a solution of NaOH (1 M).
- BCD 2 g (13.7 mmol) of 9,10-dihydroxystearic acid are added in the presence of 1 mol% of Ru (OH) x / Al 2 O 3 (1 x x 3 3 ) in an autoclave.
- the mixture is brought to 150 ° C. for 15 h under 8 bar of air pressure. After 15 hours, the reaction medium is diluted in 10 ml of methanol and then filtered.
- the filtrate obtained is esterified fatty acids not suitable for this type of analysis.
- 100 mg of Amberlyst® dry, Ref 79291 STREM chemicals are added to the filtrate and refluxed for two hours.
- the medium is then filtered to remove Amberlyst® (dry, ref 79291, STREM chemicals), and the filtrate is evaporated under reduced pressure.
- the expected ester mixture is then obtained for analysis with a quantitative yield (2.34 g) of a mixture having the same proportions of pelargonic acid and azelaic acid in ester form.
- the mixture is then heated at 140 ° C. for 18 hours under 8 bar of air pressure. After 15 hours, the reaction medium is diluted in 10 ml of methanol and then filtered. After evaporation of the organic phase, we obtain 2 g of products.
- the product F is thus obtained with a selectivity greater than 90%, which corresponds to the aldehyde obtained by oxidative cleavage of the diol protected by the diol itself.
- the Ru (OH) x / Al 2 O 3 catalyst is identical to that used in Examples 1 and
- the mixture is then heated to 150 ° C. for 15 h under 8 bar of air pressure. After 15h, the reaction medium is diluted in 40 mL of methanol and filtered. For analytical purposes, the filtrate is then esterified. For this, 400 mg of Amberlyst 15 (STREM chemicals) are added to the filtrate obtained, which is refluxed for two hours.
- Amberlyst 15 STREM chemicals
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1257421A FR2994178B1 (fr) | 2012-07-31 | 2012-07-31 | Procede de preparation d'un acide carboxylique ou d'un aldehyde |
PCT/FR2013/051842 WO2014020281A1 (fr) | 2012-07-31 | 2013-07-30 | Procede de preparation d'un acide carboxylique à partir d'un diol ou d'un epoxyde par coupure oxydante |
Publications (1)
Publication Number | Publication Date |
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EP2880010A1 true EP2880010A1 (fr) | 2015-06-10 |
Family
ID=46852295
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13756629.5A Withdrawn EP2880010A1 (fr) | 2012-07-31 | 2013-07-30 | Procede de preparation d'un acide carboxylique à partir d'un diol ou d'un epoxyde par coupure oxydante |
Country Status (6)
Country | Link |
---|---|
US (1) | US9359280B2 (fr) |
EP (1) | EP2880010A1 (fr) |
CN (1) | CN104640833A (fr) |
FR (1) | FR2994178B1 (fr) |
MY (1) | MY173010A (fr) |
WO (1) | WO2014020281A1 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3297985B1 (fr) | 2015-05-18 | 2021-08-11 | Rhodia Operations | Procédé d'oxydation d'alcools à l'aide de gaz contenant de l'oxygène |
EP3713908B1 (fr) | 2017-11-22 | 2023-06-28 | Novamont S.p.A. | Production d'acides carboxyliques à partir de diols vicinaux |
CN109942407B (zh) * | 2019-04-16 | 2022-04-01 | 中国日用化学研究院有限公司 | 一种合成9,10-二羟基十八碳硬脂酸的方法 |
FR3100809B1 (fr) | 2019-09-16 | 2023-06-02 | Demeta | Procédé de coupure oxydante d'oléfines utilisant comme catalyseur un halooxodiperoxométallate |
KR102303532B1 (ko) * | 2020-01-08 | 2021-09-23 | 애경유화주식회사 | 펠라르곤산 및 아젤라인산의 제조방법 |
CA3222829A1 (fr) * | 2021-12-16 | 2023-06-22 | Gabriele CANZI | Procedes de clivage dirige par metal de polynucleotides lies a une surface |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2086521A5 (en) | 1970-04-01 | 1971-12-31 | Air Liquide | Carboxylic acids prepn by oxidative cleavage of alpha-glycols |
DE2106913A1 (en) | 1971-02-13 | 1972-09-07 | Oxidn of vicinal diols - to yield carboxylic acids in high purity | |
DE2314454C2 (de) * | 1973-03-23 | 1987-04-23 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur kontinuierlichen Herstellung von Carbonsäuren |
IT1256989B (it) | 1992-10-29 | 1995-12-27 | Novamont Spa | Procedimento per la preparazione di acidi carbossilici o loro esteri mediante scissione ossidativa di acidi grassi insaturi o loro esteri. |
ITMI20051779A1 (it) | 2005-09-23 | 2007-03-24 | Novamont Spa | Processo migliorato per la produzione di derivati di acidi carbossilici saturi |
ITMI20070953A1 (it) | 2007-05-10 | 2008-11-11 | Novamont Spa | Processo di scissione catalitica di oli vegetali |
US8669385B2 (en) * | 2009-10-13 | 2014-03-11 | University Of Central Florida Research Foundation, Inc. | Oxidative cleavage of unsaturated carboxylic acids |
IT1397378B1 (it) * | 2009-12-30 | 2013-01-10 | Novamont Spa | Processo continuo di scissione ossidativa di oli vegetali |
IT1397379B1 (it) * | 2009-12-30 | 2013-01-10 | Novamont Spa | Processo continuo per la produzione di derivati di acidi carbossilici saturi |
FR2957074B1 (fr) * | 2010-03-05 | 2012-04-27 | Organisation Nationale Interprofessionnelle Des Graines Et Fruits Oleagineux O N I D O L | Procede de preparation d'acides carboxyliques par coupure oxydante d'un diol vicinal |
-
2012
- 2012-07-31 FR FR1257421A patent/FR2994178B1/fr not_active Expired - Fee Related
-
2013
- 2013-07-30 EP EP13756629.5A patent/EP2880010A1/fr not_active Withdrawn
- 2013-07-30 WO PCT/FR2013/051842 patent/WO2014020281A1/fr active Application Filing
- 2013-07-30 US US14/418,562 patent/US9359280B2/en not_active Expired - Fee Related
- 2013-07-30 CN CN201380040974.6A patent/CN104640833A/zh active Pending
- 2013-07-30 MY MYPI2015000085A patent/MY173010A/en unknown
Non-Patent Citations (2)
Title |
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None * |
See also references of WO2014020281A1 * |
Also Published As
Publication number | Publication date |
---|---|
FR2994178A1 (fr) | 2014-02-07 |
CN104640833A (zh) | 2015-05-20 |
US20150210623A1 (en) | 2015-07-30 |
US9359280B2 (en) | 2016-06-07 |
FR2994178B1 (fr) | 2015-08-07 |
WO2014020281A1 (fr) | 2014-02-06 |
MY173010A (en) | 2019-12-18 |
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