KR890011839A - 16- 메톡시 16- 메틸 프로스타글란딘 e₁의 제조방법 및 이에 유용한 중간체 - Google Patents
16- 메톡시 16- 메틸 프로스타글란딘 e₁의 제조방법 및 이에 유용한 중간체 Download PDFInfo
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- KR890011839A KR890011839A KR1019890000795A KR890000795A KR890011839A KR 890011839 A KR890011839 A KR 890011839A KR 1019890000795 A KR1019890000795 A KR 1019890000795A KR 890000795 A KR890000795 A KR 890000795A KR 890011839 A KR890011839 A KR 890011839A
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- 238000004519 manufacturing process Methods 0.000 title claims 5
- 239000000543 intermediate Substances 0.000 title 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims 7
- -1 4-methoxy-4-methyl-1-octene Chemical compound 0.000 claims 6
- 239000012442 inert solvent Substances 0.000 claims 4
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 claims 3
- 150000004699 copper complex Chemical class 0.000 claims 3
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical compound C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 claims 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- 230000001476 alcoholic effect Effects 0.000 claims 2
- 150000001450 anions Chemical class 0.000 claims 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 2
- 238000007256 debromination reaction Methods 0.000 claims 2
- 229910052740 iodine Inorganic materials 0.000 claims 2
- 239000011630 iodine Substances 0.000 claims 2
- 239000012454 non-polar solvent Substances 0.000 claims 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims 2
- 239000011541 reaction mixture Substances 0.000 claims 2
- 238000010992 reflux Methods 0.000 claims 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims 2
- DHIKIKPYISACNV-QZTJIDSGSA-N (2r,3r)-3-methoxy-3,7-dimethyl-1-phenylmethoxyoct-6-en-2-ol Chemical compound CC(C)=CCC[C@@](C)(OC)[C@H](O)COCC1=CC=CC=C1 DHIKIKPYISACNV-QZTJIDSGSA-N 0.000 claims 1
- UEVUOWYDVVRLJZ-HZPDHXFCSA-N (2r,3r)-3-methoxy-3-methyl-1-phenylmethoxyhept-6-en-2-ol Chemical compound C=CCC[C@@](C)(OC)[C@H](O)COCC1=CC=CC=C1 UEVUOWYDVVRLJZ-HZPDHXFCSA-N 0.000 claims 1
- CTNVUJMSFFLEHB-DLBZAZTESA-N (2r,3s)-2-methyl-2-(4-methylpent-3-enyl)-3-(phenylmethoxymethyl)oxirane Chemical compound CC(C)=CCC[C@@]1(C)O[C@H]1COCC1=CC=CC=C1 CTNVUJMSFFLEHB-DLBZAZTESA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims 1
- 238000007239 Wittig reaction Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000005903 acid hydrolysis reaction Methods 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims 1
- 238000006266 etherification reaction Methods 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 238000006140 methanolysis reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- NJVFYRBRYZXABC-UHFFFAOYSA-N methyl 7-oxoheptanoate Chemical compound COC(=O)CCCCCC=O NJVFYRBRYZXABC-UHFFFAOYSA-N 0.000 claims 1
- 229940050176 methyl chloride Drugs 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims 1
- 125000006239 protecting group Chemical group 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000008707 rearrangement Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C405/00—Compounds containing a five-membered ring having two side-chains in ortho position to each other, and having oxygen atoms directly attached to the ring in ortho position to one of the side-chains, one side-chain containing, not directly attached to the ring, a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, and the other side-chain having oxygen atoms attached in gamma-position to the ring, e.g. prostaglandins ; Analogues or derivatives thereof
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
- C07C43/1782—Unsaturated ethers containing hydroxy or O-metal groups containing six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
- C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyrane Compounds (AREA)
Abstract
내용 없음
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (5)
- 다음 일반식(4b), (4a). (4) 및 (13)의 화합물.상기식에서, M은 (Bu)3Sm-,Li, 제2동 복합체 또는 유기 쿠프레이트 복합체이고, R은 THP(테트라히드로피라닐) 또는 TBS(3급-부틸디메틸실릴)이다.
- ⒜ (2S,3R) 2,3-에폭시-3,7-디메틸-6-옥텐-1-올 벤질 에테르를 산성 가메탄올분해시켜 (2R, 3R) 1-벤질옥시-3-메톡시-3,7-디메틸-6-옥텐-2-올을 제조하고, ⒝ 단계⒜의 생성물을 트리페닐포스핀의 존재하에 약 -50 내지 -80℃에서 오존과 반응시킴으로써 오존화시켜 (2R, 3R) 2-벤질옥시메틸-6-히드록시-3-메톡시-3-메틸-테르라히드로푸란을 제조하고, ⒞ 단계⒝의 생성물을 염기의 존재하에 실온에서 무수조건하에 메틸트리페닐 포스포늄 브롬화물과 비티히반응(wittig reaction)시켜 (2R,3R) 1-벤질옥시-3-메톡시-3-메틸-6-헵텐-2-올을 제조하고, (d) 단계(c)의 생성물의 2-OH 작용기를 테트라히드로피라닐 또는 3급-부틸디메틸실릴 보호그룹으로 에테르화시킴으로써 보호하여 (2R, 3R) 1-벤질옥시-2-OR-3-메톡시-3-메틸-6-헵텐을 제조하고, ⒠ 단계 ⒟의 생성물을 촉매적으로 수소화시킴으로써 화학적으로 환원시키고 탈벤질화시켜 (2R, 3R) 2-OR-3-메톡시-3-메틸-1-헵탄올을 제조하고, ⒡ 단계 ⒠의 알콜을 염화옥살릴의 존재하에 -80 내지 -40℃에서 불활성 대기하 무수매질중에서 디메틸설폭시드와 반응시킴으로써 이의 상응하는 알데히드로 전환시킨 후 트리에틸아민으로 처리하여 (2R,3R) 2-OR-3-메톡시-3-메틸헵탄알데히드를 제조하고, ⒢ 단계⒡의 생성물을, -20 내지 -10℃에서 테트라브로모메탄 및 트리페닐포스핀을 사용함으로써 디브로메틸렌화시켜(3R,4R) 1,1-디브로모-3-OR-4-메톡시-4-메틸-1-옥텐을 제조하고, ⒣ 단계⒢의 생성물을 불활성 용매 또는 불활성 용매중의 n-부틸리튬을 사용하는환류조건하에 요오드-활성화 마그네슘과 반응시킴으로써 탈브롬화 재배열시켜 이 연속반응의 목적하는 생성물을 제조하는 단계를 포함함을 특징으로 하여, R이 TBS 또는 THP인 에난티오머적으로 순수한 (3R, 4R) 3-OR-4-메톡시-4-메틸-1-옥틴을 제조하는 방법.
- (3R, 4R) 1,1-디브로모-3-OR-4-메톡시-4-메틸-1-옥텐을 환류조건하에 불활성 용매중에서 요오드-활성화 마그네슘과 반응시킴으로써 탈브롬화시키는 단계를 포함함을 특징으로 하여, R이 THP 또는 TBS인 에난티오머적으로 순수한 (3R, 4R) 3-OR-4-메톡시-4-메틸-1-옥틴을 제조하는 방법.
- (R)4-OR-2-(6-카보메톡시헥실)-2-시클로펜테논을 -80 내지 -60℃에서 불활성 대기하에 비극성 무수 용매중에서, (3R,4R) 3-OR-4-메톡시-4-메틸-1-옥텐의 1-리티오 유도체를 ThCuCNLi과 반응시킴으로써 형성된 유기쿠프레이트 복합체와 반응시킨 다음 임의로 산성 가알콜분해시키거나 가수분해함으로써 THP 또는 TBS 보호그룹을 제거함을 특징으로 하여, R이 THP 또는 TBS인 에난티오머적으로 순수한 (8R,11R, 12R,15R,16R)11,15-디-OR-16-메틸-16-메톡시-9-옥소프로스트-13-엔-1-오산 메틸 에스테르를 제조하는 방법.
- ⒜ (3R,4R) 3-OR-4-메톡시-4-메틸-1-옥텐의 1-리티오 유도체를 -80 내지 -30℃에서 불활성 대기하 불활성 비극성 용매중에서 반응물과 함께 접촉시킴으로써 CuI 및 트리-n-부틸포스핀과 반응시킴으로써 유기 구리 복합체를 제조하고, ⒝ 상기한 유기 구리 복합체를 단계⒜의 반응 혼합물중에서 (4R) 4-OR-2-시클로펜텐-1-온과 반응시켜 에놀레이트 음이온을 제조하고, ⒞ 상기한 음이온은 단계⒝의 반응 혼합물중에서 메틸-7-옥소-헵타노에이트와 반응시켜 (8R,11R,12R,15R,16R) 11,15-디-OR-7-히드록시-16-메톡시-16-메틸-9-옥소-13-엔-1-오산 메틸 에스테르를 제조하고, ⒟ 단계⒞의 생성물을 실온에서 불활성 비극성 용매중에서 메틸 염화물 및 4-디메틸아미노 피리딘과 반응시킴으로써 탈수시켜, (8R,11R,12R,15R,16R) 11,15-디-OR-16-메톡시-16-메틸-9-옥소-7,13-디엔-1-오산 메틸 에스테르를 제조하고, ⒠단계⒟의 생성물을 3급-부틸 과산화물의 존재하에 80 내지 120℃에서 불활성 용매중에서 트리-n-부틸스탄닐 수화물과 반응시킴으로써 환원시키고, ⒡ 임의로 산성 가수분해하거나 가알콜분해시킴으로써 THP 및/ 또는 TBS-히드록시 보호그룹을 제거하는 단계를 포함함을 특징으로 하여, 에난티오머적으로 순수한 (8R,11R,12R,15R,16R) 11,15-디-OR-16-메톡시-16-메틸-9-옥소프로스트-13-엔-1-오산 메틸 에스테르를 제조하는 방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP88400199.1 | 1988-01-28 | ||
| EP88400199A EP0325869B1 (en) | 1988-01-28 | 1988-01-28 | Novel processes and intermediates |
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| Publication Number | Publication Date |
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| KR890011839A true KR890011839A (ko) | 1989-08-22 |
| KR0141104B1 KR0141104B1 (ko) | 1998-07-01 |
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| KR1019890000795A KR0141104B1 (ko) | 1988-01-28 | 1989-01-26 | 16-메톡시-16-메틸 프로스타글란딘 e1 유도체의 제조방법 및 이에 유용한 중간체 |
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| Country | Link |
|---|---|
| US (1) | US5055592A (ko) |
| EP (1) | EP0325869B1 (ko) |
| JP (1) | JP2670545B2 (ko) |
| KR (1) | KR0141104B1 (ko) |
| AT (1) | ATE82748T1 (ko) |
| CA (1) | CA1308100C (ko) |
| DE (1) | DE3876230T2 (ko) |
| DK (1) | DK36689A (ko) |
| ES (1) | ES2052750T3 (ko) |
| GR (1) | GR3006806T3 (ko) |
| HU (2) | HU200751B (ko) |
| IL (1) | IL89048A (ko) |
| ZA (1) | ZA89551B (ko) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2917552B2 (ja) * | 1991-02-26 | 1999-07-12 | 史衛 佐藤 | α−メチレンシクロペンタノン誘導体の製造法 |
| IT1402047B1 (it) * | 2010-10-19 | 2013-08-28 | Cross Pharma Sa | Uso del mexiprostil nel trattamento delle malattie infiammatorie intestinali |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1162731B (it) * | 1979-04-10 | 1987-04-01 | Lepetit Spa | 16-metil-16-metossi-5,6-diidro-prosta-glandine della serie e1 ad attivita'antisecretoria |
| DE3275542D1 (en) * | 1981-11-13 | 1987-04-09 | Teijin Ltd | Process for prostaglandin e1, production and novel delta 7-prostaglandines e and 7-hydroxyprostaglandins e |
| DE3672424D1 (de) * | 1985-01-29 | 1990-08-09 | Teijin Ltd | Herstellungsverfahren 16-substituierter prostaglandine-e. |
-
1988
- 1988-01-28 DE DE8888400199T patent/DE3876230T2/de not_active Expired - Fee Related
- 1988-01-28 ES ES88400199T patent/ES2052750T3/es not_active Expired - Lifetime
- 1988-01-28 EP EP88400199A patent/EP0325869B1/en not_active Expired - Lifetime
- 1988-01-28 AT AT88400199T patent/ATE82748T1/de not_active IP Right Cessation
-
1989
- 1989-01-24 ZA ZA89551A patent/ZA89551B/xx unknown
- 1989-01-24 IL IL89048A patent/IL89048A/xx unknown
- 1989-01-26 KR KR1019890000795A patent/KR0141104B1/ko not_active IP Right Cessation
- 1989-01-27 HU HU89429A patent/HU200751B/hu not_active IP Right Cessation
- 1989-01-27 HU HU902026A patent/HU203885B/hu not_active IP Right Cessation
- 1989-01-27 DK DK036689A patent/DK36689A/da unknown
- 1989-01-27 JP JP1016543A patent/JP2670545B2/ja not_active Expired - Lifetime
- 1989-01-30 CA CA000589569A patent/CA1308100C/en not_active Expired - Lifetime
-
1990
- 1990-01-30 US US07/474,317 patent/US5055592A/en not_active Expired - Fee Related
-
1993
- 1993-01-14 GR GR930400061T patent/GR3006806T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK36689A (da) | 1989-07-29 |
| ES2052750T3 (es) | 1994-07-16 |
| IL89048A (en) | 1993-06-10 |
| HU200751B (en) | 1990-08-28 |
| HU902026D0 (en) | 1990-08-28 |
| GR3006806T3 (ko) | 1993-06-30 |
| JPH021471A (ja) | 1990-01-05 |
| HU203885B (en) | 1991-10-28 |
| KR0141104B1 (ko) | 1998-07-01 |
| ZA89551B (en) | 1990-01-31 |
| EP0325869B1 (en) | 1992-11-25 |
| EP0325869A1 (en) | 1989-08-02 |
| ATE82748T1 (de) | 1992-12-15 |
| CA1308100C (en) | 1992-09-29 |
| DE3876230T2 (de) | 1993-05-06 |
| DE3876230D1 (de) | 1993-01-07 |
| JP2670545B2 (ja) | 1997-10-29 |
| DK36689D0 (da) | 1989-01-27 |
| US5055592A (en) | 1991-10-08 |
| HUT49120A (en) | 1989-08-28 |
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