CA2324186C - Direct fluorination process for preparing high purity 2-fluoro-1,3-dicarbonyl compounds using oxygen as a radical scavanger - Google Patents
Direct fluorination process for preparing high purity 2-fluoro-1,3-dicarbonyl compounds using oxygen as a radical scavanger Download PDFInfo
- Publication number
- CA2324186C CA2324186C CA002324186A CA2324186A CA2324186C CA 2324186 C CA2324186 C CA 2324186C CA 002324186 A CA002324186 A CA 002324186A CA 2324186 A CA2324186 A CA 2324186A CA 2324186 C CA2324186 C CA 2324186C
- Authority
- CA
- Canada
- Prior art keywords
- reactor
- beta
- methyl
- fluorinated
- product
- 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.)
- Expired - Fee Related
Links
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 14
- 239000001301 oxygen Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 20
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- -1 R2 is H Chemical group 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 14
- 125000000217 alkyl group Chemical group 0.000 abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 87
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 44
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 39
- XJMIXEAZMCTAGH-UHFFFAOYSA-N methyl 3-oxopentanoate Chemical compound CCC(=O)CC(=O)OC XJMIXEAZMCTAGH-UHFFFAOYSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 26
- 239000000758 substrate Substances 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 22
- 238000011068 loading method Methods 0.000 description 22
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 22
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 20
- ZHQHSDROMAJDFS-UHFFFAOYSA-N methyl 2-fluoro-3-oxopentanoate Chemical compound CCC(=O)C(F)C(=O)OC ZHQHSDROMAJDFS-UHFFFAOYSA-N 0.000 description 13
- 230000003068 static effect Effects 0.000 description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- OCJKUQIPRNZDTK-UHFFFAOYSA-N ethyl 4,4,4-trifluoro-3-oxobutanoate Chemical compound CCOC(=O)CC(=O)C(F)(F)F OCJKUQIPRNZDTK-UHFFFAOYSA-N 0.000 description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 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 description 5
- 239000000654 additive Substances 0.000 description 5
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000004989 dicarbonyl group Chemical group 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- GZJCDQYVIXPMAW-UHFFFAOYSA-N 1,2-dichloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1Cl GZJCDQYVIXPMAW-UHFFFAOYSA-N 0.000 description 2
- LELFVORHOKZNGY-UHFFFAOYSA-N 3-fluoropentane-2,4-dione Chemical compound CC(=O)C(F)C(C)=O LELFVORHOKZNGY-UHFFFAOYSA-N 0.000 description 2
- LIQBKSIZAXKCPA-UHFFFAOYSA-N 4,4,4-trifluoro-3-oxobutanoic acid Chemical compound OC(=O)CC(=O)C(F)(F)F LIQBKSIZAXKCPA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 108091027881 NEAT1 Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- QTLYPQZWYOHATR-UHFFFAOYSA-N 2-methyl-3-ketovaleric acid Chemical compound CCC(=O)C(C)C(O)=O QTLYPQZWYOHATR-UHFFFAOYSA-N 0.000 description 1
- ZXLSKTZECNUVIS-UHFFFAOYSA-M 4-methyl-3-oxopentanoate Chemical compound CC(C)C(=O)CC([O-])=O ZXLSKTZECNUVIS-UHFFFAOYSA-M 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 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 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/432,723 | 1999-11-01 | ||
| US09/432,723 US6455728B1 (en) | 1999-11-01 | 1999-11-01 | Direct fluorination process for preparing high purity 2-fluoro-1,3-dicarbonyl compounds using oxygen as a radical scavenger |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2324186A1 CA2324186A1 (en) | 2001-05-01 |
| CA2324186C true CA2324186C (en) | 2005-03-29 |
Family
ID=23717346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002324186A Expired - Fee Related CA2324186C (en) | 1999-11-01 | 2000-10-25 | Direct fluorination process for preparing high purity 2-fluoro-1,3-dicarbonyl compounds using oxygen as a radical scavanger |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6455728B1 (enExample) |
| EP (1) | EP1095928B1 (enExample) |
| JP (2) | JP4022041B2 (enExample) |
| AT (1) | ATE258910T1 (enExample) |
| CA (1) | CA2324186C (enExample) |
| DE (1) | DE60008059T2 (enExample) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1454900A1 (en) * | 2003-03-07 | 2004-09-08 | Sanofi-Synthelabo | Process for the preparation of pyridinyl and pyrimidinyl mono-fluorinated beta keto-esters |
| JP2022513032A (ja) * | 2019-08-22 | 2022-02-07 | フジアン ヨンジン テクノロジー カンパニー リミテッド | 直接フッ素化による無機又は有機化合物のフッ素化プロセス |
| CN120794834A (zh) * | 2025-09-15 | 2025-10-17 | 山东华氟化工有限责任公司 | 一种1,1,3,3-四氟-2-丙酮的合成方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2614129A (en) * | 1943-08-10 | 1952-10-14 | Purdue Research Foundation | Perfluorination |
| GB1513135A (en) * | 1974-06-04 | 1978-06-07 | Res Inst For Med & Chem Inc | Fluorination process and fluoro steroids |
| US5569778A (en) * | 1992-10-30 | 1996-10-29 | Daikin Industries Ltd. | Process for preparing fluorine-containing dicarbonyl compound |
| WO1995014646A1 (en) * | 1993-11-20 | 1995-06-01 | Bnfl Fluorochemicals Ltd | The preparation of dicarbonyls |
| JP3817605B2 (ja) * | 1996-03-26 | 2006-09-06 | 東ソ−・エフテック株式会社 | 含フッ素ジカルボニル化合物の製造方法 |
-
1999
- 1999-11-01 US US09/432,723 patent/US6455728B1/en not_active Expired - Lifetime
-
2000
- 2000-10-25 CA CA002324186A patent/CA2324186C/en not_active Expired - Fee Related
- 2000-10-31 DE DE60008059T patent/DE60008059T2/de not_active Expired - Lifetime
- 2000-10-31 EP EP00309606A patent/EP1095928B1/en not_active Expired - Lifetime
- 2000-10-31 AT AT00309606T patent/ATE258910T1/de not_active IP Right Cessation
- 2000-10-31 JP JP2000331935A patent/JP4022041B2/ja not_active Expired - Fee Related
-
2007
- 2007-02-21 JP JP2007040121A patent/JP2007126486A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP1095928A3 (en) | 2001-07-18 |
| CA2324186A1 (en) | 2001-05-01 |
| JP2007126486A (ja) | 2007-05-24 |
| JP2001131110A (ja) | 2001-05-15 |
| DE60008059D1 (de) | 2004-03-11 |
| DE60008059T2 (de) | 2004-07-01 |
| EP1095928B1 (en) | 2004-02-04 |
| JP4022041B2 (ja) | 2007-12-12 |
| ATE258910T1 (de) | 2004-02-15 |
| EP1095928A2 (en) | 2001-05-02 |
| US6455728B1 (en) | 2002-09-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed | ||
| MKLA | Lapsed |
Effective date: 20121025 |