EP1480934A2 - Production d'alcenones - Google Patents
Production d'alcenonesInfo
- Publication number
- EP1480934A2 EP1480934A2 EP03704499A EP03704499A EP1480934A2 EP 1480934 A2 EP1480934 A2 EP 1480934A2 EP 03704499 A EP03704499 A EP 03704499A EP 03704499 A EP03704499 A EP 03704499A EP 1480934 A2 EP1480934 A2 EP 1480934A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- onium
- acid
- salt
- substituted
- reaction
- 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- Withdrawn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
- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 25
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 18
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims abstract description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 114
- 238000006243 chemical reaction Methods 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000012071 phase Substances 0.000 claims description 27
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- LVKBHPIMBDSSNX-UHFFFAOYSA-N 2-methylpyridin-1-ium;2,2,2-trifluoroacetate Chemical compound CC1=CC=CC=N1.OC(=O)C(F)(F)F LVKBHPIMBDSSNX-UHFFFAOYSA-N 0.000 claims description 14
- -1 carboxylic acid anion Chemical class 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 2
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 3
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 88
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 84
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 30
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 22
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 14
- 238000005583 trifluoroacetylation reaction Methods 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 235000011089 carbon dioxide Nutrition 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- OMSBSIXAZZRIRW-UHFFFAOYSA-N 2-methylpyridine;hydrochloride Chemical compound Cl.CC1=CC=CC=N1 OMSBSIXAZZRIRW-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- NRTYMEPCRDJMPZ-UHFFFAOYSA-N pyridine;2,2,2-trifluoroacetic acid Chemical compound C1=CC=NC=C1.OC(=O)C(F)(F)F NRTYMEPCRDJMPZ-UHFFFAOYSA-N 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 4
- 238000009419 refurbishment Methods 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 2
- KAQJMEHRXVENSF-UHFFFAOYSA-N 2-(trichloromethyl)pyridine Chemical compound ClC(Cl)(Cl)C1=CC=CC=N1 KAQJMEHRXVENSF-UHFFFAOYSA-N 0.000 description 2
- YKYIFUROKBDHCY-UHFFFAOYSA-N 4-ethoxy-1,1,1-trifluorobut-3-en-2-one Chemical compound CCOC=CC(=O)C(F)(F)F YKYIFUROKBDHCY-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 2
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical group CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- ASAXRKSDVDALDT-UHFFFAOYSA-N propan-2-yl 2,2,2-trifluoroacetate Chemical compound CC(C)OC(=O)C(F)(F)F ASAXRKSDVDALDT-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- AHOJTPZHHMJMCW-UHFFFAOYSA-N 1-ethylpiperidin-4-ol Chemical compound CCN1CCC(O)CC1 AHOJTPZHHMJMCW-UHFFFAOYSA-N 0.000 description 1
- BAUWRHPMUVYFOD-UHFFFAOYSA-N 1-methylpiperidin-4-ol Chemical compound CN1CCC(O)CC1 BAUWRHPMUVYFOD-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- BUGNITMKWYOPCU-UHFFFAOYSA-N 1-propylpiperidin-4-ol Chemical compound CCCN1CCC(O)CC1 BUGNITMKWYOPCU-UHFFFAOYSA-N 0.000 description 1
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- PZASAAIJIFDWSB-CKPDSHCKSA-N 8-[(1S)-1-[8-(trifluoromethyl)-7-[4-(trifluoromethyl)cyclohexyl]oxynaphthalen-2-yl]ethyl]-8-azabicyclo[3.2.1]octane-3-carboxylic acid Chemical compound FC(F)(F)C=1C2=CC([C@@H](N3C4CCC3CC(C4)C(O)=O)C)=CC=C2C=CC=1OC1CCC(C(F)(F)F)CC1 PZASAAIJIFDWSB-CKPDSHCKSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KXKWKIWJNCLJGV-UHFFFAOYSA-N ClC(Cl)(Cl)C1(C)NC=CC=C1 Chemical class ClC(Cl)(Cl)C1(C)NC=CC=C1 KXKWKIWJNCLJGV-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-O phenylazanium Chemical compound [NH3+]C1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-O 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- HDOWRFHMPULYOA-UHFFFAOYSA-N piperidin-4-ol Chemical compound OC1CCNCC1 HDOWRFHMPULYOA-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- NGCRXXLKJAAUQQ-UHFFFAOYSA-N undec-5-ene Chemical compound CCCCCC=CCCCC NGCRXXLKJAAUQQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/18—Salts thereof
-
- 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
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
Definitions
- the invention relates to a process for the preparation of halogenated alkenone ethers.
- Halogenated alkenone ethers for example 4-ethoxy-1, 1, 1-trifluoro-3-buten-2-one / are building blocks in chemical synthesis, see for example EP-0 744 400. They can be prepared by adding an acid chloride with a Reacts vinyl ether with one another in the presence of a base, see the above-mentioned European patent application.
- the object of the present invention is to provide an improved method. This object is achieved by the method of the present invention.
- R 1 represents a Cl-C4-alkyl group or a C1-C4-alkyl group which is substituted by at least 1 halogen atom, or wherein R 1 represents CF 3 C (0) CH 2 , and where R 2 represents aryl, substituted aryl, a C1-C4-alkyl group or for a Cl-C4-alkyl group which is substituted by at least 1 halogen atom, provides that an acid anhydride or an acid halide of the formula (II)
- R 2 has the abovementioned meaning, in the presence of an "onium” salt of a carboxylic acid, or where one uses 1 or 2 Cl-C3-alkyl groups, optionally chlorinated pyridine, or where one uses an "onium” salt an inorganic acid.
- pyridine substituted by 1, 2 or 3 Cl-C3-alkyl groups preferably picoline, collidine or lutidine (ie pyridine which is substituted by 1, 2 or 3 methyl groups, all isomers being usable), preferably 2-Picolin
- the pyridine substituted by 1 to 3 Cl-C3-alkyl groups can also be substituted in the nucleus and / or the alkyl group (s) by one or more chlorine atoms.
- chloromethyl, dichloromethyl and trichloromethyl pyridine, in particular the picolines substituted in the 2-position is preferred.
- an "onium” salt of any amine of an inorganic acid is used. It has been found that adducts of amine and acid, including inorganic acid, are effective as acid scavengers in the present invention if the molar ratio of amine to acid is less than 3. For example, Oniur ⁇ hydrochlorid is able to 2 mol HCl, which comes from the reaction, intercept. In this variant, onium hydrochloride is preferred.
- a particularly preferred variant provides for the use of onium carboxylates of any amines. This method has the advantage of a milder reaction and a higher yield compared to the prior art method in which a trialkylamine is used as the base, and is further explained below.
- R 1 preferably represents methyl, ethyl, n-propyl or i-propyl or methyl, ethyl, n-propyl or i-propyl substituted by at least 1 fluorine atom.
- R 1 particularly preferably represents methyl, ethyl or methyl or ethyl substituted by at least 1 fluorine atom.
- R 1 very particularly preferably represents CF 3 , CF 2 H, CF 2 C1, C 2 F 5 , C 3 F 7 or CF 3 C (0) CH 2 .
- R 2 can represent aryl, for example phenyl or C1-C4 alkyl groups and / or halogen atoms substituted phenyl.
- R 2 is preferably linear or branched Cl-C4-alkyl.
- R 2 very particularly preferably denotes methyl, ethyl, n-propyl or i-propyl.
- the molar ratio of "onium” salt and acid halide or acid anhydride is advantageously between 0.1: 1 and 2: 1.
- the acid chloride is preferred as the acid halide.
- the invention is further explained on the basis of this preferred embodiment.
- the molar ratio of acid chloride or anhydride and vinyl ether is advantageously between 0.9: 1 and 1: 0.8.
- the implementation is e.g. B. at -15 to +80 ° C, advantageously carried out at a temperature in the range of 0 ° to 40 ° C. It can be exothermic, so that the reaction mixture may need to be cooled or the reaction may be carried out very slowly.
- a solvent is used in the reaction. This is particularly advantageous if first the vinyl ether and then the anhydride are added to the "onium" salt or amine.
- aliphatic linear or branched hydrocarbons or aliphatic linear or branched halogenated carbons are suitable.
- Halogenated carbon (hydrogen) compounds with 1 to 8 carbon atoms, for example, are particularly suitable.
- dichloromethane 1, 1, 1-trifluoro-2, 2, 2-trichloroethane, hexane, cyclohexane, trifluoroacetic acid ethyl or propyl ester are very suitable.
- no solvent is used in the reaction between anhydride and vinyl ether. This is particularly possible if the anhydride and then the vinyl ether are first added to the "onium" salt or amine.
- the advantage is that no solvent has to be separated, which is of course advantageous (no effort for recovery, lower energy consumption).
- the anion of the carboxylic acid of the "onium” salt preferably has the formula R 1 C (0) 0 ⁇ , where R 1 has the meaning given above.
- the carboxylic acid in the "onium” salt of the carboxylic acid used is preferably the acid which corresponds to the acid halide used.
- the term "onium” stands for cations with positively charged nitrogen, for example protonated aromatic nitrogen bases such as pyridinium or protonated alkyl, dialkyl or trialkyl ammonium cations or for cycloalkyl-substituted ammonium compounds or cycloaliphatic nitrogen bases such as piperidinium or quaternary ammonium cations.
- Onium salts are very suitable as carboxylic acid salts, where "onium” stands for a cation of the nitrogen of the formula R ⁇ 'R ⁇ R ⁇ " .
- R', R", R '"and R" independently of one another Hydrogen, alkyl having 1 to 20 carbon atoms, aryl or aralkyl.
- R 'and R “or R”' and R “”, or R ', R “and R”' or R ', R “, R'” and R “” can also form saturated or unsaturated ring systems, optionally including the nitrogen atom.
- Aryl here means in particular phenyl or phenyl substituted by 1 or more Cl-C2-alkyl groups.
- Amines substituted by hydroxy groups especially cycloaliphatic amines, especially hydroxy-substituted piperidines and N-Cl-C4-alkylpiperidines, can also be used.
- the ring can be substituted by one or more amino groups.
- Dialkylamino groups are preferred in which the alkyl groups can be the same or different and comprise 1 to 4 carbon atoms.
- the amino group can also represent a saturated ring system, for example a piperidino group.
- Representatives of monocyclic ring systems that can be used are dialkylaminopyridine, dialkylaminopiperidine and dialkylaminopiperazine.
- Onium cations of bicyclic compounds can also be used.
- 1, 2 or more nitrogen atoms can be integrated into the ring system.
- the compounds can be substituted by one or more amino groups.
- Dialkylamino groups are again preferred, the alkyl groups being the same or different and comprising 1 to 4 carbon atoms or together with the nitrogen atom forming a saturated ring system, such as the piperidinyl group.
- At least 2 nitrogen atoms in the useful compounds must have basic properties and, depending on the type of bonds, are bound to 2 or 3 carbon atoms.
- Onium salts of carboxylic acid with bicyclic amines in particular 1,5-diaza-bicyclo [4.3.0] non-5-ene (DBN) and 1,8-diazabicyclo [5.4.0] - are very particularly preferred. undec-7-cen (DBU).
- DBN 1,5-diaza-bicyclo [4.3.0] non-5-ene
- the "onium” salts of aromatic amines especially those with one, two or three electron-donating groups, such as Cl-C3-alkyl groups, are very useful, e.g.
- the "onium” salts of the carboxylic acids can be prepared by simply reacting the corresponding amines with the free acids.
- the process according to the invention for the preparation of alkanes of the formula (I) can be carried out at elevated pressure or else at ambient pressure. It can be carried out batchwise or semi-continuously.
- reaction mixtures are worked up by customary methods.
- the desired alkenone of the formula (I) can be distilled out of the mixture after the solvent (if present) has been separated off.
- Another possibility is to add water to the reaction mixture and to isolate the alkenone from the organic phase after water has been separated off by customary separating agents such as sodium sulfate.
- a preferred embodiment takes advantage of the workup with 2-phase formation.
- a variant provides for working up with the addition of water.
- An organic phase is formed which contains the desired product and the organic solvent used.
- the aqueous phase contains the spent "onium” salt. If the acid anhydride has been used as one of the starting materials, the "onium” salt is largely present as the “onium” salt of the carboxylic acid corresponding to the anhydride. If you have used the "onium” salt of the carboxylic acid as an acid scavenger, this is If there is an excess of acid in the aqueous phase.
- the ratio of "onium” cation to carboxylic acid content must be brought to the preferred range from 0.9: 1 to 1: 0.9.
- the easiest way to do this is to add as much alcohol, e.g. B. of Cl-C4-aliphatic alcohols, causes the acid present beyond the desired content to react with esterification and can be separated off by distillation together with the water present.
- the "onium” salt is largely in the aqueous phase as hydrochloride or as a chloride-enriched onium complex.
- carboxylic acid e.g. B. trifluoroacetic acid, preferably in a 5 to 10-fold molar excess. Released hydrochloric acid is evaporated at a higher temperature. Since an excess of the carboxylic acid is usually used in this regeneration, there is then again an "onium” salt of the carboxylic acid with an excess of acid, which is not very suitable for reuse.
- An alcohol is then added, as already described above, which reacts with the excess acid to form an ester. The ester can then be distilled off, with water also being distilled off.
- an organic solvent is added, which causes the formation of two phases.
- solvents which cause the reaction mixture to be in a homogeneous phase are first removed.
- a solvent or solvent mixture is added, which causes the splitting into two phases.
- the following have proven useful, for example: ethers, especially dialkyl ethers, especially diethyl ether; Esters of trifluoroacetic acid, for example isopropyl trifluoroacetate; aliphatic hydrocarbons, for example hexane; cyclic hydrocarbons, for example cyclohexane; halogenated carbon compounds, for example l, l, 2-trichloro-l, 2,2-trifluoroethane (CFC-113) or dichloromethane.
- phase contains the solvent and the alkenone formed, the other phase essentially the salt.
- the phase which contains the alkenone is separated off, the solvent is removed and the alkenone can then be purified in the customary manner, for example by distillation, if this is necessary at all, since the product is usually obtained in very high purity. It has been shown that the yield and purity of the product is very high in this embodiment too.
- regeneration can also be carried out by adding the anhydride of the carboxylic acid, e.g. B. by adding acetic anhydride or trifluoroacetic anhydride, preferably by adding the anhydride of the carboxylic acid that corresponds to the acid chloride used.
- the acid chloride and the "onium" salt of the carboxylic acid are then formed, which can then be reacted further with vinyl ethers in accordance with the process of the invention.
- the "onium” salt of the carboxylic acid can be prepared beforehand by reacting the free base with the carboxylic acid. It can also be prepared during the reaction by continuously or batchwise introducing the carboxylic anhydride of the carboxylic acid corresponding to the acid chloride into the reaction mixture.
- a modification of the process according to the invention provides that an aldehyde or acid chloride of the general formula (II) and a vinyl ether of the general formula (III) are reacted in the presence of an amine base, as described, for example, in EP-A- 0 744 400 loading is written.
- the resulting A hydrochloride is then preferably regenerated as described above and used again in this embodiment in a second stage in the process according to the invention.
- Another object of the invention are adducts of a carboxylic acid anion of the formula R 1 C (O) 0 ⁇ with a protonated cation of pyridine which is substituted by one, two or three C1-C3 alkyl groups, preferably by one, two or three methyl groups , Such adducts with the anion of trifluoroacetic acid are preferred. These adducts can additionally contain up to 1 mole of free acid per mole of "onium" salt.
- the protonated cation of the pyridine substituted by 1 to 3 Cl-C3-alkyl groups can also be chlorinated, especially in the alkyl groups. So it can be 2-chloroethyl, 2-dichloromethyl and 2-trichloromethylpyridinium.
- Another object of the invention is the use of pyridine, which is substituted by 1, 2 or 3 C-1-C3-alkyl groups, as an acid scavenger.
- 2-alkyl pyridine with alkyl methyl, ethyl or propyl is preferred.
- Examples 1 to 8 illustrate the preparation using trifluoroacetyl chloride
- Examples 9 to 12 the preparation using trifluoroacetic anhydride
- Example 13 illustrates the regeneration of the spent "onium” salt with trifluoroacetic acid.
- the pyridinium trifluoroacetate was first prepared in a 500 ml three-necked flask with a dry ice cooler. For this purpose, pyridine was introduced and TFA was added dropwise with stirring. So that the mixture did not become too hot (since the reaction is highly exothermic), it was cooled with a water bath. Then dichloromethane and ethyl vinyl ether were added and TFAC was introduced with stirring. The reaction temperature was kept at room temperature by means of a water bath. The approach turned slightly yellowish when TFAC was initiated. The mixture was then stirred for a further 2% at room temperature and then a GC sample was taken (sample was hydrolyzed). The turnover contributed 97.2%, the selectivity to 4-ethoxy-1,1,1-trifluoro-3-buten-2-one (ETFBO) was quantitative.
- ETFBO 4-ethoxy-1,1,1-trifluoro-3-buten-2-one
- the DBNxTFA was first prepared in a 250 ml three-necked flask with a dry ice cooler. For this purpose, DBN was introduced and TFA was added dropwise with stirring. So that the mixture did not become too hot (since the reaction is highly exothermic), it was cooled with a water bath, and DBNxTFA became solid. Then dichloromethane, ethyl vinyl ether was added and TFAC headed. The reaction temperature was kept at room temperature by means of a water bath. The approach turned yellow when TFAC was initiated. The mixture was then stirred for a further 1 h at room temperature and then a GC sample was taken (sample is hydrolyzed). EVE sales were quantitative, selectivity to ETFBO was 93.4%.
- the DBNxTFA was first produced in a 100 ml three-necked flask with a dry ice cooler. For this purpose, dichloromethane with DBN was introduced and TFA was added dropwise with stirring. To prevent the mixture from becoming too hot (since the reaction was highly exothermic), it was cooled with a water bath. Then ethyl vinyl ether was added and TFAC was introduced with stirring. The reaction temperature was kept at room temperature by means of a water bath. The approach turned yellow when TFAC was initiated. The mixture was then stirred for a further VA h at room temperature and then a GC sample was taken (sample is hydrolyzed). The sales of EVE was quantitative, the selectivity to ETFBO was 95%. Refurbishment as in example 1.
- ETFBO 4-ethoxy-l, 1, 1-trifluoro-3-butene-2-one
- the DBN x TFA was first prepared in a 250 ml three-necked flask with a dry ice cooler. For this purpose, MeCl 2 and DBN were introduced and TFA was added dropwise with stirring. So that the mixture did not become too hot (since the reaction is very exothermic), it was cooled with a water bath. Then ethyl vinyl ether was added and TFAC was introduced with stirring. The reaction temperature was kept at room temperature by means of a water bath. The approach turned orange when TFAC was initiated. The mixture was then stirred for a further 2 h at room temperature and then a GC sample was taken (sample is hydrolyzed). The ethyl vinyl ether had completely reacted.
- the solvent dichloromethane was then removed in vacuo in a rotary evaporator, and the remaining solution was divided into several partial volumes, which were worked up by adding a solvent which formed a second phase.
- the partial volumes were mixed with the same volume fractions of the following solvents, whereupon a second phase was formed:
- the desired product ETFBO was mainly in the organic phase; the used amine salt was quantitatively in the other phase.
- the ETFBO phase was separated off and now gently isolated on the rotary evaporator by removing the solvent in vacuo with a purity> 98%.
- the DBU x TFA was first produced in a 250 ml three-necked flask with a dry ice cooler. For this purpose, MeCl 2 and DBU were introduced and TFA was added dropwise with stirring. So that the mixture did not become too hot (since the reaction is very exothermic), it was cooled with a water bath. Then ethyl vinyl ether was added and TFAC was introduced with stirring. The reaction temperature was kept at room temperature by means of a water bath. The approach turned orange when TFAC was initiated. The mixture was then stirred at room temperature for a further 2 h and then a GC sample was taken (sample is hydrolyzed). A second sample was taken the next morning (batch had turned dark). The ethyl vinyl ether had completely converted to ETFBO. The isolation was carried out using the second phase method described in Example 4.
- the pyridinium trifluoroacetate was first prepared in a 500 ml three-necked flask with a dry ice cooler. For this purpose, pyridine was introduced and TFA was added dropwise with stirring. So that the mixture did not become too hot (since the reaction is very exothermic), it was cooled with a water bath. Then dichloromethane and ethyl vinyl ether were added and with stirring TFAC initiated. The reaction temperature was kept at room temperature by means of a water bath. The approach became slightly yellowish when ⁇ ron TFAC was introduced. The mixture was then stirred for a further 2% at room temperature and then a GC sample was taken (sample is hydrolyzed).
- Example 7 The workup described in Examples 4 to 6 by forming two phases led to particularly high yields, thermal stress on the reaction mixture being avoided.
- the picoline trifluoroacetate was first prepared in a 250 ml three-necked flask with a dry ice cooler. For this purpose, dichloromethane and 2-picoline were introduced and TFA was added dropwise with stirring. So that the mixture did not become too hot (since the reaction is very exothermic), it was cooled with a water bath. Then ethyl vinyl ether was added and TFAC was introduced with stirring. The reaction temperature was kept at room temperature by means of a water bath. The approach turned yellow when TFAC was initiated. The mixture was then stirred at room temperature for a further 272 h and then a GC sample was taken (sample was hydrolyzed). The ethyl vinyl ether had completely reacted. The batch was then added to 150 g of ice water, the organic phase was washed twice with water and distilled using a Rotavapor.
- the 4-ethoxy-l, 1, 1-trifluoro-3-buten-2-one distilled at 65 ° C water bath temperature and 15 mbar. According to the gas chromatogram, the purity was 97.4%. The ETFBO yield was 76.2%.
- the picoline trifluoroacetate was first prepared in a 250 ml three-necked flask with a water cooler. For this purpose, dichloromethane and 2-picoline were introduced and TFA was added dropwise with stirring. So that the mixture did not become too hot (since the reaction is very exothermic), it was cooled with a water bath. Then ethyl vinyl ether was added and TFAH was added dropwise with stirring. The reaction temperature was kept at room temperature by means of a water bath. The mixture turned yellow when TFAH was added dropwise. The mixture was stirred for a further 1 h and then a GC sample was taken (sample was hydrolyzed).
- the pyridine trifluoroacetate was first prepared in a 250 ml three-necked flask with a water cooler. For this purpose, dichloromethane and pyridine were introduced and TFA was added dropwise with stirring. So that the mixture did not become too hot (since the reaction is very exothermic), it was cooled with a water bath. Then ethyl vinyl ether was added and TFAH was added dropwise with stirring. The reaction temperature was kept at room temperature by means of a water bath. The mixture was stirred for a further 1 h and then a GC sample was taken (sample was hydrolyzed). The next morning, another sample was taken - the ethyl vinyl ether had fully reacted. The yield of ETFBO was 85.0%.
- the DBN x TFA was first produced in a 250 ml three-necked flask with a water cooler. For this purpose, MeCl 2 and DBN were introduced and TFA was added dropwise with stirring. So that the mixture did not become too hot (since the reaction is very exothermic), it was cooled with a water bath. Then ethyl vinyl ether was added and TFAH was added dropwise with stirring. The reaction temperature was kept at room temperature by means of a water bath. The approach turned yellow. The mixture was then stirred for a further 1.5 h at room temperature and then a GC sample was taken (sample was hydrolyzed). The ethyl vinyl ether had completely reacted.
- MeCl 2 was stripped off in vacuo at room temperature in a rotary evaporator and the remaining solution was extracted after division into partial volumes with various solvents forming two phases. Hexane, pentane, cyclohexane and 113 were used as 2-phase extractants.
- Picolin hydrochloride and TFA were placed in a 250 ml three-necked flask with a water cooler and boiled under reflux. Cl ⁇ samples were taken after 1 h and 7 h.
- the chloride is easier to exchange than pyridine.
- Example 12 a The reaction product from Example 12 a) was heated and excess trifluoroacetic acid was distilled off until picolinium trifluoroacetate was present as an adduct with further trifluoroacetic acid; Two moles of trifluoroacetic acid (amine x 3 TFA) were present in the residue per mole of picolinium trifluoroacetate. A further separation of trifluoroacetic acid from this adduct was not possible by distillation. 1 mol of ethanol was added per mol of acetic acid.
- the picoline trifluoroacetate was first prepared by introducing 2-picoline and adding TFA while stirring. So that the mixture did not become too hot (since the reaction is very exothermic), it was cooled with an ice water bath. Then TFAH was added and ethyl vinyl ether was added dropwise with stirring (reaction highly exothermic). The reaction temperature was kept at room temperature by means of an ice water bath. The reaction mixture turned yellow when TFAH was added. The mixture was stirred for another hour and then a GC sample was taken (sample is hydrolyzed). ETFBO sales were 91.3%.
- Example 13 was repeated. The reaction was carried out without a solvent, and dichloromethane was then added for even better phase separation. Again there was a high turnover to ETFBO.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Des éthers d'alcénone halogénés peuvent être obtenus par addition d'halogénures ou d'anhydrides d'acide carboxylique à un éther vinylique. L'amélioration apportée par la présente invention consiste à réaliser cette addition en présence d'un sel 'onium' d'un acide carboxylique, ce sel pouvant être régénéré. Les produits peuvent être obtenus avec un rendement élevé. On peut également utiliser une pyridine substituée par un, deux ou trois groupes alkyle C1-C3, ou d'autres sels 'onium'.
Priority Applications (1)
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EP11165289A EP2360136A1 (fr) | 2002-02-08 | 2003-01-30 | Production d'alcénones |
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DE10205224 | 2002-02-08 | ||
DE10205224 | 2002-02-08 | ||
DE10261471A DE10261471A1 (de) | 2002-02-08 | 2002-12-31 | Herstellung von Alkenonen |
DE10261471 | 2002-12-31 | ||
PCT/EP2003/000913 WO2003066558A2 (fr) | 2002-02-08 | 2003-01-30 | Production d'alcenones |
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US (1) | US7057079B2 (fr) |
EP (1) | EP1480934A2 (fr) |
JP (1) | JP4376061B2 (fr) |
CN (1) | CN1330622C (fr) |
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WO (1) | WO2003066558A2 (fr) |
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WO2009006211A1 (fr) * | 2007-06-29 | 2009-01-08 | Dow Agrosciences Llc | Procédé amélioré de préparation de 4-trifluoromethyl-2(1h)-pyridinone |
WO2009006217A1 (fr) * | 2007-06-29 | 2009-01-08 | Dow Agrosciences Llc | 4-chloro-4-alcoxy-1,1,1-trifluoro-2-butanones, leur préparation et leur utilisation pour la préparation de 4-alcoxy-1,1,1-trifluoro-3-buten-2-ones |
CN101801906A (zh) | 2007-08-16 | 2010-08-11 | 索尔维公司 | 制备4-氟取代的3-氧代-烷酸酯的方法 |
JP2011526899A (ja) * | 2008-07-01 | 2011-10-20 | ダウ アグロサイエンシィズ エルエルシー | 2−トリフルオロメチル−5−(1−置換)アルキルピリジンの調製のための改善された方法 |
EP2310350B1 (fr) | 2008-07-04 | 2017-09-06 | Solvay Sa | Processus de fabrication d'alcénones |
GB0903749D0 (en) * | 2009-03-04 | 2009-04-15 | Syngenta Participations Ag | Chemical process |
CA2765374C (fr) | 2009-07-06 | 2018-01-02 | Solvay Sa | Procede de fabrication d'alcenones |
US8957254B2 (en) | 2009-07-06 | 2015-02-17 | Solvay Sa | Process for chemical synthesis from an alkenone made from a halogenated precursor |
JP2012532182A (ja) * | 2009-07-06 | 2012-12-13 | ソルヴェイ(ソシエテ アノニム) | 特有の条件下でのアルケノンのハロゲン化前駆体の製造方法 |
US8426650B2 (en) | 2009-07-06 | 2013-04-23 | Solvay Sa | Process for the manufacture of halogenated precursors of alkenones in the presence of a solvent |
WO2012025548A1 (fr) | 2010-08-27 | 2012-03-01 | Solvay Sa | Procédé pour la préparation d'alcénones |
WO2012085195A1 (fr) * | 2010-12-23 | 2012-06-28 | Solvay Sa | Purification respectueuse de l'environnement d'une solution organique d'etfbo |
WO2015011728A1 (fr) | 2013-07-26 | 2015-01-29 | Srf Limited | Procédé de production d'éthers d'alcénone |
CN105237376A (zh) * | 2015-11-20 | 2016-01-13 | 江苏瑞邦农药厂有限公司 | 一种4-乙氧基-1,1,1-三氟-丁烯-2-酮的合成方法 |
CN106943183B (zh) * | 2017-04-26 | 2023-09-08 | 郑明辉 | 微创柔性穿刺管、微创通道穿刺组件 |
CN110526810A (zh) * | 2018-05-25 | 2019-12-03 | 浙江蓝天环保高科技股份有限公司 | 一种1,1,1-三氟-4-乙氧基戊-3-烯-2-酮的制备方法 |
CN111072463A (zh) * | 2019-12-03 | 2020-04-28 | 辽宁凯莱英医药化学有限公司 | 一种4-乙氧基-1,1,1-三氟-3-丁烯-2-酮的连续化合成方法 |
WO2021108999A1 (fr) * | 2019-12-03 | 2021-06-10 | 辽宁凯莱英医药化学有限公司 | Procédé de synthèse en continu de 4-éthoxy-1,1,1-trifluoro-3-butèn-2-one |
CN114956969B (zh) * | 2022-07-12 | 2024-04-16 | 永农生物科学有限公司 | 一种4-乙氧基-1,1,1-三氟-3-丁烯-2-酮的制备方法 |
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US4705801A (en) | 1984-10-16 | 1987-11-10 | Ciba-Geigy Corporation | Production for producing 3-cyano-4-phenyl indoles and intermediates |
US4847258A (en) | 1986-08-26 | 1989-07-11 | Ciba-Geigy Corporation | Substituted benzoylphenylureas compounds useful as pesticides |
ATE161819T1 (de) * | 1993-04-27 | 1998-01-15 | Solvay Fluor & Derivate | Verfahren zur herstellung von carbonsäureestern aus carbonsäurehalogeniden und alkoholen |
PT1254883E (pt) * | 1995-05-26 | 2009-10-02 | Ishihara Sangyo Kaisha | Processo para produção de 1,1,1-trifluoro-3-buten-2-onas substituídas |
GB2305174A (en) * | 1995-09-15 | 1997-04-02 | Zeneca Ltd | Chemical process |
DE19732031C1 (de) * | 1997-07-25 | 1999-04-22 | Solvay Fluor & Derivate | 2-Phasen-Herstellung von Carbonsäureestern |
DE10104663A1 (de) | 2001-02-02 | 2002-08-08 | Solvay Fluor & Derivate | Herstellung von Fluorverbindungen |
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- 2003-01-30 EP EP03704499A patent/EP1480934A2/fr not_active Withdrawn
- 2003-01-30 AU AU2003206803A patent/AU2003206803A1/en not_active Abandoned
- 2003-01-30 CN CNB038034042A patent/CN1330622C/zh not_active Expired - Fee Related
- 2003-01-30 JP JP2003565935A patent/JP4376061B2/ja not_active Expired - Fee Related
- 2003-01-30 WO PCT/EP2003/000913 patent/WO2003066558A2/fr active Application Filing
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JP4376061B2 (ja) | 2009-12-02 |
JP2005537219A (ja) | 2005-12-08 |
CN1628087A (zh) | 2005-06-15 |
WO2003066558A2 (fr) | 2003-08-14 |
US20050070716A1 (en) | 2005-03-31 |
US7057079B2 (en) | 2006-06-06 |
AU2003206803A1 (en) | 2003-09-02 |
CN1330622C (zh) | 2007-08-08 |
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