EP0722432A1 - Procede de preparation de cyclopentanone mono- ou di-substituee en position 2 - Google Patents
Procede de preparation de cyclopentanone mono- ou di-substituee en position 2Info
- Publication number
- EP0722432A1 EP0722432A1 EP94931058A EP94931058A EP0722432A1 EP 0722432 A1 EP0722432 A1 EP 0722432A1 EP 94931058 A EP94931058 A EP 94931058A EP 94931058 A EP94931058 A EP 94931058A EP 0722432 A1 EP0722432 A1 EP 0722432A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- reaction
- compound
- acid
- symbol
- 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.)
- Ceased
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclo-pentanone Natural products O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 title claims abstract description 24
- BGTOWKSIORTVQH-HOSYLAQJSA-N cyclopentanone Chemical class O=[13C]1CCCC1 BGTOWKSIORTVQH-HOSYLAQJSA-N 0.000 title abstract 2
- -1 alkyl acetoacetate Chemical compound 0.000 claims abstract description 24
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 14
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims abstract description 13
- 238000005947 deacylation reaction Methods 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 230000020477 pH reduction Effects 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 150000001875 compounds Chemical class 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 33
- 239000007795 chemical reaction product Substances 0.000 claims description 33
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 21
- 239000010948 rhodium Substances 0.000 claims description 20
- 239000012429 reaction media Substances 0.000 claims description 17
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 16
- 239000008346 aqueous phase Substances 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 14
- 239000011707 mineral Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910052752 metalloid Inorganic materials 0.000 claims description 8
- 150000002738 metalloids Chemical class 0.000 claims description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- 150000007942 carboxylates Chemical group 0.000 claims description 7
- 150000003997 cyclic ketones Chemical class 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 7
- 150000003284 rhodium compounds Chemical class 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 229910052716 thallium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010908 decantation Methods 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- YQEPTNWSGJQCOK-UHFFFAOYSA-N 2-bis(2-sulfophenyl)phosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P(C=1C(=CC=CC=1)S(O)(=O)=O)C1=CC=CC=C1S(O)(=O)=O YQEPTNWSGJQCOK-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- PJKUVJSPRYXAFR-UHFFFAOYSA-N 2-[phenyl-(2-sulfophenyl)phosphanyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P(C=1C(=CC=CC=1)S(O)(=O)=O)C1=CC=CC=C1 PJKUVJSPRYXAFR-UHFFFAOYSA-N 0.000 claims description 2
- HXVJDHROZFWXHT-UHFFFAOYSA-N 2-diphenylphosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HXVJDHROZFWXHT-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000008378 aryl ethers Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000002609 medium Substances 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000004525 petroleum distillation Methods 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 230000001131 transforming effect Effects 0.000 claims description 2
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000003738 xylenes Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims 4
- 230000001376 precipitating effect Effects 0.000 claims 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 159000000007 calcium salts Chemical class 0.000 claims 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims 1
- FTGZMZBYOHMEPS-UHFFFAOYSA-N 2,2-dimethylcyclopentan-1-one Chemical compound CC1(C)CCCC1=O FTGZMZBYOHMEPS-UHFFFAOYSA-N 0.000 abstract description 5
- 230000020176 deacylation Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 244000309464 bull Species 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- BTVZFIIHBJWMOG-UHFFFAOYSA-N 2,2-dimethylhexanedioic acid Chemical compound OC(=O)C(C)(C)CCCC(O)=O BTVZFIIHBJWMOG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- WDFZWSZNOFELJY-OLQVQODUSA-N (1R,6S)-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=C[C@H]2O[C@H]21 WDFZWSZNOFELJY-OLQVQODUSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- LVAMVZXECCXUGI-UHFFFAOYSA-N acetic acid;thallium Chemical compound [Tl].CC(O)=O LVAMVZXECCXUGI-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/48—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation involving decarboxylation
Definitions
- the present invention relates to a process for the preparation of cyclopentanone mono- or di-substituted in position 2.
- the invention relates more particularly to the preparation of 2,2-dimethylcyclopentanone.
- Cycloalkanones such as, for example, cyclopentanones mono- or disubstituted in position 2, can advantageously serve as intermediate compounds in the synthesis of fungicides belonging to the family of benzylidene-azolylmethylcycloalkanes which is described in particular in document EP-A 0 378 953.
- the present invention relates to a process for the preparation of cyclopentanone mono- or di-substituted in position 2 of formula:
- R * represents: a hydrogen atom; a linear or branched alkyl or alkoxy radical having from 1 to 4 carbon atoms; a radical of formula (R2) p- ⁇ henyl ⁇ (-CR3R4-) q-- where R ⁇ is a linear or branched alkyl radical having from 1 to 3 carbon atoms, R3 and R ⁇ , which may be the same or different, each represent a hydrogen atom or a linear or branched alkyl radical having from 1 to 3 carbon atoms and p and q are whole numbers, which may be the same or different, ranging from 0 to 3; said process being characterized in that it consists in successively carrying out the following 4 steps (a) to (d) which can be linked as required in the same reactor:
- step (a) which consists of:
- step (b) which consists in using the reaction product of formula (IV), taken in the form of the crude product obtained in the organic phase at the end of the abovementioned stage (a2) or in the form of a pure product, and:
- step (c) which consists in using the acid of formula (VI), taken in the form of the crude product obtained in aqueous phase at the end of the abovementioned stage (b ⁇ ) or in the form of pure product, and:
- step (d) which consists in using the dicarboxylic acid of formula
- R 1 there may be mentioned, in addition to hydrogen: the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl radicals and the corresponding alkoxy radicals; as well as the phenyl, (o-, m- or p-) tolyl, xylyl and benzyl radicals.
- the symbol R 1 corresponds to the methyl radical
- the symbols R 1 and R 6> which are identical or different, correspond to the methyl and ethyl radicals.
- step (a) of the process according to the invention it is therefore a question of carrying out an addition reaction on carbon 4 of a 1,3-butadiene of formula (II), optionally carrying a substimant on the carbon 2, of a compound with active methylene group of formula (III).
- This reaction can be carried out in a known manner as indicated in particular in document EP-A 0 044 771, the content of which is incorporated here by reference; this reaction makes it possible to obtain an adduct of formula (TV) which is a mixture consisting essentially of the following two isomers:
- a soluble phosphine a compound taken from the group formed by the sodium, potassium, calcium, barium, ammonium, tetramethylammonium and tetraethylammonium salts of (sulfophenyl) diphenylphosphine, di (sulfophenyl) phenylphosphine and tri (sulfophenyl) phosphine;
- a water-soluble compound taken from the group formed by: rhodium oxide RI12O3 is used as the rhodium compound; rhodium chloride RJ1CI3; rhodium bromide RhBr3; rhodium sulfate Rl_2 (S ⁇ 4) 3; rhodium nitrate Rh (N ⁇ 3) 3; rhodium acetate Rh (CH3CO2) 3; rhodium tetracarbonyl
- an amount of rhodium compound is used, expressed by the number of atom-grams of elemental rhodium per 100 moles of butadiene, which is between
- an amount of phosphine is used, expressed by the number of moles of this compound relative to a gram atom of elementary rhodium, which is between 1 and 10;
- a base consisting of an alkali metal hydroxide, carbonate or bicarbonate, such as for example sodium, is added to the reaction medium, in order to improve the reactivity, in an amount ranging from 0.01 to 3 moles of base per liter of water used in the composition of the reaction medium;
- reaction temperature is in the range from 50 ° C. to 150 ° C., and it is maintained for a period which will depend on the temperature chosen and can vary for example between 2 hours by operating at 100 ° C. and 5 hours operating at 80 ° C.
- step (a) As regards the practical manner of carrying out the addition reaction of step (a), reference will be made for more details to the content of the aforementioned document EP-A 0 044 771.
- step (b) of the method according to the invention taken in its variant (bi), it is a matter of carrying out:
- step (b) of the process of the invention taken in its variant (b '), it is a matter of carrying out:
- solutions of alcoholate are used in the alcohol which gave birth to it which can contain up to 20 moles of alcohol, and more precisely which contain between 5 and 15 moles of alcohols for one mole of alcoholate base; 3. 1 to 1.5 moles of alcoholate base are used per mole of starting keto-ester of formula (IV);
- the deacylation reaction is carried out at a temperature which generally corresponds to the boiling temperature of the alcohol involved, for a sufficient time to eliminate, as and when it is formed in situ, the compound R ⁇ -CO-G in the structure of which the symbol G represents the organic residue of the alkali alcoholate set work (this residue G represents OCH3 when the alkaline alcoholate used is for example CH3 ⁇ N a ); this reaction time is for example between 2 hours and 6 hours;
- the alkaline hydrolysis reaction is carried out by adding to the reaction medium, after having completed the deacylation reaction, that is to say after elimination of the compound
- R6-CO-G water in an amount representing 10 to 30 moles of water per 1 mole of alkali metal alkoxide base
- the alkaline hydrolysis reaction is carried out at a temperature which generally corresponds to the reflux temperature of the reaction mixture, for a time sufficient to remove the alcohol present in said mixture by distillation;
- the hydrolysis reaction is terminated by acidifying the residual aqueous reaction mixture to a pH of value between approximately 1 and approximately 3 by addition of a determined quantity of a strong mineral mono- or polyacid, oxygenated or not, as for example hydrochloric, nitric and sulfuric acids.
- a strong mineral mono- or polyacid oxygenated or not, as for example hydrochloric, nitric and sulfuric acids.
- step (c) of the process according to the invention a carboxy group COOH is added to the carbon atom of the carboxylic acid of formula (VI) which carries the substituent R *.
- This synthesis requires globally providing 1 mole of carbon monoxide CO and one mole of water for each mole of carboxylic acid of formula (VI) to be functionalized.
- a first synthesis mode corresponding to variant (ci), consists in using formic acid as a vehicle for CO and water and in using a catalyst based on a strong acid; such a reaction is known in the prior art, cf. in particular the document New J. Chem. , 1992, 1 £, 521-524, the content of which is incorporated herein by reference, but it has never been applied to a substrate having the structure of the mono-carboxylic compound of formula (VI) in order to obtain the dicarboxylic acid of formula (VII).
- a strong mono-or polyacid, mineral or organic, oxygenated or not, is used as catalyst, at least one of the acid functions (when there are several) has an ionization constant in water, pKa , less than or equal to 3, such as for example: among mineral acids, hydrochloric, sulfuric, orthophosphoric, pyrophosphoric acids; among organic acids, organosulfonic acids (in particular paratoluenesulfonic, methanesulfonic, single naphthalenesulf), organophosphonic acids (in particular monoalkyl- or monoarylphosphonic acids such as methylphosphonic or benzenephosphonic), strong halogenated polycarboxylic acids (such as acids dihalogeno- and trihalogeno-, especially chloro- and fluoroacetic or propionic).
- a strong acid which is particularly suitable is sulfuric acid;
- the hydroxycarbonylation reaction is carried out using, for each mole of starting carboxylic acid of formula (VI), 1 to 15 moles of water and 10 to 50 H + ions;
- the water and the strong acid which are necessary for the reaction are introduced together into the reaction medium in the form of a concentrated aqueous solution of strong acid whose concentration by weight of pure acid and the quantity are determined so as to bring the required amount of water and the number of H + ions;
- the weight concentration of pure acid is in the range from 90 to 98%;
- the reaction temperature is in the range from room temperature (20 ° C) to 100 ° C and is maintained until the absorption of C0 ceases.
- the reactions can be carried out under the following advantageous conditions 1 to 6 which, preferably, will be taken in combination:
- an amount of formic acid is used, expressed by the number of moles of this compound relative to one mole of carboxylic acid of formula (VI), which is between 1 and 4 moles;
- the strong acid catalyst is used in the pure state or in the form of a concentrated aqueous solution whose weight concentration of pure acid is at least equal to 95%;
- an amount of strong acid catalyst is used, expressed in number of H + ions per mole of starting carboxylic acid of formula (VI), which is between 5 and 40 H + ions;
- reaction temperature is in the range from room temperature (20 ° C) to 100 ° C and is maintained for a period of the order of 3 hours to 6 hours depending on the temperature value.
- step (d) of the process according to the invention the dicarboxylic acid of formula (VII) is cyclized to obtain the cyclopentanone of formula (I).
- a first mode of synthesis corresponding to variant (d), consists in converting the diacid into a cyclic anhydride by reaction with a lower carboxylic acid anhydride which then loses CO2 during the reaction under the effect of temperature; such a reaction can be carried out in a known manner as indicated in particular in the documents, Compt. rend., 142, 1084-1085 (1906) and Compt. rend., 144. 1356-1358 (1907) the contents of which are incorporated herein by reference.
- Another mode of synthesis which is particularly used here and corresponds to variant (of i), consists in subjecting the diacid to a pyrolysis reaction in liquid or gas phase in the presence of a particular catalyst, such a reaction is known in the prior art, cf. especially Bull. Acad. dry. USSR, sci class. chem., (29-40), 489-493 (1947) and J. Org. Chem., 25., 1841-1844, (1960), but the particular catalyst used in this memo is not described there.
- the cyclizing decarboxylation reaction is carried out in the liquid phase, that is to say in the presence of a reaction solvent which is a solvent (or a mixture of solvents) organic (s) inert with respect to the dicarboxylic acid starting material and the cyclic ketone obtained, and each having a high boiling temperature of between 200 ° C and 500 ° C.
- a reaction solvent which is a solvent (or a mixture of solvents) organic (s) inert with respect to the dicarboxylic acid starting material and the cyclic ketone obtained, and each having a high boiling temperature of between 200 ° C and 500 ° C.
- suitable organic solvents there may be mentioned in particular: paraffinic hydrocarbons such as decane, undecane, dodecane or tetradecane; aromatic hydrocarbons such as xylenes, cumene, petroleum fractions consisting of a mixture of alkylbenzenes, in particular the Solvesso type fractions; heavy esters of mineral acids such as tricresyl phosphate or of carboxylic acids such as octyl phthalate; aromatic ethers such as biphenyl oxide or benzene oxide; paraffinic and / or naphthenic oils, petroleum distillation residues;
- paraffinic hydrocarbons such as decane, undecane, dodecane or tetradecane
- aromatic hydrocarbons such as xylenes, cumene, petroleum fractions consisting of a mixture of alkylbenzenes, in particular the Solvesso type fractions
- heavy esters of mineral acids such as tricresyl phosphate or of carboxy
- the concentration of the starting dicarboxylic acid of formula (VII) in the reaction mass, formed of the starting diacid, of the catalyst and of the organic solvent (s), generally represents from 10 to 50% of the weight of the reaction mass;
- a metal or a metalloid taken in the form: a metal or a metalloid; a single or double oxide or a single or double hydroxide; a single or double mineral salt such as for example a nitrate, a sulfate, an oxysulfate, a halide, an oxyhalide, a silicate, a carbonate; or of a single or double organic salt such as for example an acetylacetonate, an alcoholate such as for example a methylate or an ethylate, a carboxylate such as for example an acetate or an oxalate.
- a metal or a metalloid taken in the form: a metal or a metalloid; a single or double oxide or a single or double hydroxide; a single or double mineral salt such as for example a nitrate, a sulfate, an oxysulfate, a halide, an oxyhalide, a silicate, a carbonate;
- Suitable catalysts mention will be made in particular the following catalysts: sodium or potassium tetraborate; tin oxide; sodium or potassium stannate; bismuth, cesium or rubidium carbonate, molybdenum, aluminum, indium or antimony oxide; thallium acetate; - of type (2i), a phosphate or condensed phosphate, of pyrophosphate or polyphosphate type, in the structure of which the cation is a cation derived in particular from an element of the group la (with the exception of rubidium and cesium), 2a or 3b of the Periodic Table published in the Bulletin of the elaborate Chimique de France, n ° l (1966) or an ammonium cation.
- suitable catalysts mention may in particular be made of the following catalysts: phosphates, pyrophosphates, tripolyphosphates or pentapolyphosphate of sodium or potassium;
- an amount of catalyst is used, expressed in number of atom-grams of metal cation per 100 moles of dicarboxylic acid, which is between 0.1 and 30% and more precisely between 5 and 20%;
- the cyclizing decarboxylation reaction is carried out at a temperature between 200 ° C and 300 ° C which can be chosen equal to the reflux temperature of the reaction mixture;
- the cyclizing decarboxylation reaction is carried out by distilling off, as they are formed, the cyclic ketone, the carbon dioxide and the water formed; at the end of the reaction, the cyclic ketone is recovered from the distillate, according to the conventional techniques used in this technical field, in particular by decantation or by crystallization.
- the contents of the autoclave are transferred to a separatory funnel where an aqueous phase and an organic phase separate.
- the collected aqueous phase contains the catalyst and the catalyst-free upper orgasmic phase contains the desired adduct of formula (TV).
- the separated organic phase is washed with 20 ml of salt water.
- the aqueous phase is extracted with 50 ml of ethyl acetate, then it is then washed with 20 ml of salt water.
- the organic phases are combined, then dried over anhydrous Na2S ⁇ 4.
- step (b) of the method according to the invention illustrates the implementation of step (b) of the method according to the invention.
- 6OO ml of methanol is poured into a 1 liter three-necked flask, purged beforehand with argon, equipped with mechanical stirring, a thermometer, a 250 ml dropping funnel and a distillation column. anhydrous.
- the expected carboxylic acid of formula (VI) settles spontaneously.
- the aqueous phase is extracted twice in succession with each time 100 ml of CH2Cl2.
- the organic phases are combined and dried over anhydrous Na2S ⁇ 4.
- the CH2Cl2 is removed by evaporation under reduced pressure and the crude product obtained is purified by distillation under reduced pressure (70-74 ° C; 3.10 ⁇ Pa) to yield 108.3 g of a colorless liquid which contains, after analysis by NMR, IR and determination by vapor phase chromatography, 95% by weight of carboxylic acid of formula:
- the residual filtrate is diluted with 1 liter of water and kept for 12 hours at 4 ° C: this makes it possible to isolate an additional 3.17 g of the desired dicarboxylic acid taken in the pure state.
- distillate After filtration and rinsing with CH2CI2, the distillate is made up to 100 ml with
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9312153A FR2710908B1 (fr) | 1993-10-07 | 1993-10-07 | Procédé de préparation de cyclopentanone mono- ou di-substituée en position 2. |
FR9312153 | 1993-10-07 | ||
PCT/FR1994/001157 WO1995009830A1 (fr) | 1993-10-07 | 1994-10-04 | Procede de preparation de cyclopentanone mono- ou di-substituee en position 2 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0722432A1 true EP0722432A1 (fr) | 1996-07-24 |
Family
ID=9451769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94931058A Ceased EP0722432A1 (fr) | 1993-10-07 | 1994-10-04 | Procede de preparation de cyclopentanone mono- ou di-substituee en position 2 |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0722432A1 (fr) |
JP (1) | JPH09503219A (fr) |
KR (1) | KR960704829A (fr) |
CN (1) | CN1132503A (fr) |
AU (1) | AU675367B2 (fr) |
BR (1) | BR9407734A (fr) |
CA (1) | CA2173618A1 (fr) |
CZ (1) | CZ100796A3 (fr) |
FI (1) | FI961553A0 (fr) |
FR (1) | FR2710908B1 (fr) |
HU (1) | HUT74481A (fr) |
IL (1) | IL111166A0 (fr) |
WO (1) | WO1995009830A1 (fr) |
ZA (1) | ZA947879B (fr) |
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CN103086858B (zh) * | 2012-12-30 | 2015-03-04 | 浙江工业大学 | 一种3-甲基环戊酮的合成方法 |
CN112010744A (zh) * | 2019-05-29 | 2020-12-01 | 武汉臻智生物科技有限公司 | 法尼基丙酮及其制备方法 |
CN110981710B (zh) * | 2019-11-26 | 2022-11-08 | 万华化学集团股份有限公司 | 一种由异戊二烯合成甲基庚烯酮的方法 |
Family Cites Families (5)
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DE3163383D1 (en) * | 1980-07-10 | 1984-06-07 | Rhone Poulenc Sante | Process for the selective addition of a compound having an activated carbon atom to a substituted conjugated diene |
US4788333A (en) * | 1985-01-07 | 1988-11-29 | E. I. Du Pont De Nemours And Company | Hydrocarboxylation of unsaturated carboxylic acids to linear dicarboxylic acids |
DE3622012A1 (de) * | 1986-07-01 | 1988-01-07 | Basf Ag | Verfahren zur herstellung zyklischer ketone |
DE3638005A1 (de) * | 1986-11-07 | 1988-05-11 | Basf Ag | Verfahren zur herstellung von cyclopentanon |
DE3730185A1 (de) * | 1987-09-09 | 1989-03-23 | Basf Ag | Verfahren zur herstellung von cyclopentanon |
-
1993
- 1993-10-07 FR FR9312153A patent/FR2710908B1/fr not_active Expired - Fee Related
-
1994
- 1994-10-04 WO PCT/FR1994/001157 patent/WO1995009830A1/fr not_active Application Discontinuation
- 1994-10-04 JP JP7510645A patent/JPH09503219A/ja active Pending
- 1994-10-04 EP EP94931058A patent/EP0722432A1/fr not_active Ceased
- 1994-10-04 CA CA002173618A patent/CA2173618A1/fr not_active Abandoned
- 1994-10-04 CZ CZ961007A patent/CZ100796A3/cs unknown
- 1994-10-04 IL IL11116694A patent/IL111166A0/xx unknown
- 1994-10-04 AU AU79958/94A patent/AU675367B2/en not_active Ceased
- 1994-10-04 BR BR9407734A patent/BR9407734A/pt not_active Application Discontinuation
- 1994-10-04 CN CN94193694A patent/CN1132503A/zh active Pending
- 1994-10-04 HU HU9600905A patent/HUT74481A/hu unknown
- 1994-10-07 ZA ZA947879A patent/ZA947879B/xx unknown
-
1996
- 1996-04-04 KR KR1019960701794A patent/KR960704829A/ko not_active Application Discontinuation
- 1996-04-09 FI FI961553A patent/FI961553A0/fi not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO9509830A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2173618A1 (fr) | 1995-04-13 |
WO1995009830A1 (fr) | 1995-04-13 |
JPH09503219A (ja) | 1997-03-31 |
HU9600905D0 (en) | 1996-05-28 |
CZ100796A3 (en) | 1996-07-17 |
KR960704829A (ko) | 1996-10-09 |
FI961553A (fi) | 1996-04-09 |
HUT74481A (en) | 1997-01-28 |
BR9407734A (pt) | 1997-02-12 |
AU7995894A (en) | 1995-05-01 |
FR2710908A1 (fr) | 1995-04-14 |
AU675367B2 (en) | 1997-01-30 |
FI961553A0 (fi) | 1996-04-09 |
CN1132503A (zh) | 1996-10-02 |
IL111166A0 (en) | 1994-12-29 |
ZA947879B (en) | 1995-05-22 |
FR2710908B1 (fr) | 1995-11-17 |
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