AU619901B2 - Phenyl nonatetraenoic acid derivatives - Google Patents
Phenyl nonatetraenoic acid derivatives Download PDFInfo
- Publication number
- AU619901B2 AU619901B2 AU42608/89A AU4260889A AU619901B2 AU 619901 B2 AU619901 B2 AU 619901B2 AU 42608/89 A AU42608/89 A AU 42608/89A AU 4260889 A AU4260889 A AU 4260889A AU 619901 B2 AU619901 B2 AU 619901B2
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- AU
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- Prior art keywords
- formula
- compound
- lower alkyl
- chlorine
- fluorine
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C57/42—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P37/00—Drugs for immunological or allergic disorders
- A61P37/02—Immunomodulators
- A61P37/06—Immunosuppressants, e.g. drugs for graft rejection
-
- 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
-
- 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
- C07C45/67—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 isomerisation; by change of size of the carbon skeleton
- C07C45/68—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/46—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings and other rings, e.g. cyclohexylphenylacetic acid
- C07C57/48—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings and other rings, e.g. cyclohexylphenylacetic acid having unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
-
- 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
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5456—Arylalkanephosphonium compounds
Description
Our Ref: 232847 Our Ref: 232847
AUSTRALIA
Patents Act 6 199 O"1 COMPLETE SPECIFICATION
(ORIGINAL)
Application Number: Lodged: *r a a, 0 000a a o Complete Specification Lodged: Accepted: Published: Priority: Related Art: i tcc~,~ci(z 0 C kA kROCM C\ C% a ro *a a a
Q
Applicant(s): Address for Service: .F-Hof-fmana-La-Reeohe-- -Go--Aklengese-l-e1a-fft 124-184 Grenzacherstrasse
BASLE
SWITZERLAND
ARTHUR S. CAVE CO.
Patent Trade Mark Attornerys Level 10, 10 Barrack Street SYDNEY NSW 2000 Complete specification for the invention entitled "Phenyl nonatetraenoic acid derivatives".
The following statement is a full description of this invention, including the best method of performing it known to me:- 0~1 57.5 05/ 10/89 1 5020 pj The present invention relates to compounds of the formula: R 7 I I
CH=CH-C=CH-IC(CCH-C-OR
1( 9 0
I
toot It t *i 1 tI 01 ttr.
Ot wherein
R
1 is hydrogen, loweralkyl trifluoromethyl, chlorine or fluorine;
R
2 is chlorine, fluorine, loweralkyl, trifluoromethyl, hydroxy, hydroxy protected with a hydrolizable ester group, loweralkoxyl, trifluoromethylloweralkoxy, hydrogen;
R
3 is hydrogen, lower alkyl, chlorine or fluorine;
R
7 and R 8 are individually hydrogen or lower alkyl; and
R
9 is lower alkyl.
The term "lower alkyl" as used herein designates both straight and branched chain lower alkyl groups containing from 1 to 7 carbon atoms. Among the preferred lower alkyl groups are methyl, ethyl, isopropyl, n-butyl, etc., with methyl and ethyl being especially preferred. The term "lower alkoxy" designates lower alkoxy groups containing from 1 to 7 carbon atoms such as methoxy, ethoxy, isopropoxy, isobutyoxy, etc. The term trifluoromethyl lower alkoxy designates a trifluoromethyl substituted lower alkoxy substituent where lower alkoxy is defined as above. A hydrolyzable ester Croup is, e.g. a lower alkanoyl group.
2 0158g/KLW The compound of formula I can be prepared from compounds of the formula R 2
CHO
OH
co 0g *c 0 o 00 o t 0t E0 §9 0 o o 00 0 *1 wherein R 1
R
2 and R 3 are as above, via the reaction scheme in Figure 1.
In the reaction scheme of Figure 1, R 1
R
2
R
3
R
7
R
8 and R 9 are as above, Y is aryl preferably phenyl; Z' is halo.
The compound of formula II is converted to the compound of formula III via reaction step by reducing the aldehyde group to the alcohol. This reaction is carried out utilizing a conventional reducing agent which converts aldehydes to alcohols. Any conventional reducing agent for this purpose can be utilized in the reaction of step In carrying out this reaction it is generally preferred to utilize an alkali metal borohydride such as sodium borohydride as the reducing agent.
Any of the conditions conventional in such reduction reactions can be utilized to carry out the reaction of step The compound of formulla III is converted to the compound of formula IV via reaction step by treating the compound of formula III with a triarylphosphine hydrohalide. In this manner the phosphonium salt of formula IV is produced. Any 3 0158g/KLW conventional method of reacting an allylic alcohol with a triarylphosphine hydrohalide can be used to carry out this reaction. The phosphonium salt of formula IV is reacted via a Wittig reaction with the compound of formula V in step to form the compound of formula I. Any of the conditions conventionally used in Wittig reaction can be utilized to carry out the reaction of step On the other hand the compound of formulla IP. may be directly converted to the compound of formula I via the reaction with the phosphonium salt of the compound of formula VI as in reaction step The reaction of the phosphonium salt of formula VI with the compound of formula II to produce the compound of formula I is carried out utilizing the same conditions as described in connection with reaction step The compounds of formula I are useful as intermediates in the preparation of pharmaceutically active compounds as described in our copending application No.45575/85.
The following examples are illustrative but not limitative of the invention. In the examples the ether is diethyl ether.
Referential Example [[(2-(Nonloxy)phenyllmethylltriphenylphosphonium bromide 2-Hydroxybenzaldehyde (110 was alkylated by mixing this compound with 1-bromononane (180 anhydrous potassiun carbonate and dimethylformamide (800 mL). This mixture was heated at 80 0 C for 14 hrs. Hexane and water were then added and the hexane extract was concentrated and the residue was 4 0158g/KLW *e at a
C~
at,, 'tee a Ce a a tate Ga a at at eta a a teat distilled to yield the 2-nonyloxybenzaldehyde (210g), bp 121*C.
(0.3mm Hg). A solution of 2-nonyloxybenzaldehyde prepared above (100 g) in ethanol (l(~1O mL) at 10 0 C was reduced by treating with an excess of sodiumn Lorohydride (6 g) and after stirring the mixture for a further 15-20 min. at room temperature, the compound 2-nonyloxybenzylalcohol was isolated by extraction into hexane. Removal of the hexane in vacuo yielded the crude 2-nonyloxybenzylalcohol (98 The resulting 2-nonyloxybenzylalcohol was added to a mixture of triphenyil-Xosphine hydrobrimide (144 g) in acetonitrile (500 mL) and the resultant solution was heated at reflux for 14 hours. Removal of the solvents in vacuo and crystallization of ,.he residue from a tetrahydrofuran/ethyl ether mixture gave the pure [[2-(nonyloxy)phenylllmethylltriphenylphosphonium bromide (208 g) Example 1 F(2-Hvdroxvphenvl)methlltriphenylphosphonium bromide 2-Hydroxybenzyl alcohol was treated with triphenylphosphine hydrobromide in acetonitrile as described above to yield I(2-Hydroxyphenyl)methyl] triphenylphosphonium bromide.
Example 2 ALL (2-Hvdroxyphenl)-3 7-dimethyl-2,4, 6, 8-nonatetraenoic acid ethyl ester A solution of [(2-hydroxyphenyl)methylltriphenylphosphonium bromide (1 mol) in tetrahydrofuran was converted to the ylide at -35 0 with a solution of n-butyllithium in hexane t t I 5 0158g/ICLW 0 (2.1 mol equiv.) and then exposed to 7-formyl-3-methyl-2,4,6octatrienoic acid ethyl ester (1 mol) and then stirred at 0for a further 15 min Isolation of the organic products with a hexane/ethyl acetate mixture (4:1 parts by volume) and dilute mineral acid (2M aqueous HCL) gave the pure all -9-(2-hydroxyphenyl) 7-dimethyl-2 8-nonatetraenoic acid ethyl ester (90% yield) after chromatography followed by crystallization from a dichloromethane/hexane mixture.
Example 3 AL(E) (-Hydroxy. henrl) 7-dimethyl-2.4,6. 8nottanc acid ethvl ester A mixture of 2-hydroxybenzaldehyde (0.5 mol), 7 -carboxy-2,6-dimethyl-2,4,6-heptatrien-1-yl)triphenylphosphonium bromide (0.6 mol) in 1,2-epoxybutane (750 mL) was heated at reflux for 30 min. cooled, poured into an ether/hexane mixture (1:1 parts by volume) filtered and concentrated. The residue was then crystallized from a hexane/ether mixture to yield all(F)-9-(2-hydroxyphenyl)-3, 7 -dimethyl-2,4,6,8-nonateraenoic acid ethyl ester (38% yield), mp 143-145.
at a atlt t o too.
00 0 00 00 *oa 0040 4 a C 0 -6 0158g/KLW
Claims (3)
1. A compound of the formula I R R7 R 1 7 1 R2 CrC=CH-C=CHI-CII=CH-C=CH- COOR 9
2 O S0 F1 R 3 wherein R 1 is hydrogen, loweralkyl trifluoromethyl, chlorine or fluorine; R 2 is chlorine, fluorine, loweralkyl, trifluoromethyl, hydroxy, hydroxy protected with a hydrolizable ester group, loweralkoxyl, trifluoromethylloweralkoxy, hydrogen; S. R 3 is hydrot'en, lower alkyl, chlorine or fluorine; I R 7 and R 8 are individually hydrogen or lower alkyl; *and R 9 is lower alkyl. S2. All (E)-9-(2-Hydroxyphenyl)-3,7-dimethyl-2,4,6,8- nonatetraenoic acid ethyl ester.
3. A compound of the formula I, substantially as herein defined, with reference to any one of the Examples. U DATED this 4th day of October, 1989. -F--Mo-ff-a-f- -ari- a--Rech Ak t4 -e n ee-1-s-eh-aft By Its Patent Attorneys ARTHUR S. CAVE CO. 7 0158g/KLW
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63510084A | 1984-07-27 | 1984-07-27 | |
| US635100 | 1984-07-27 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU45575/85A Division AU589130B2 (en) | 1984-07-27 | 1985-07-25 | Phenyl nonatetraenoic acid derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU4260889A AU4260889A (en) | 1990-01-25 |
| AU619901B2 true AU619901B2 (en) | 1992-02-06 |
Family
ID=24546455
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU45575/85A Ceased AU589130B2 (en) | 1984-07-27 | 1985-07-25 | Phenyl nonatetraenoic acid derivatives |
| AU42608/89A Ceased AU619901B2 (en) | 1984-07-27 | 1989-10-05 | Phenyl nonatetraenoic acid derivatives |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU45575/85A Ceased AU589130B2 (en) | 1984-07-27 | 1985-07-25 | Phenyl nonatetraenoic acid derivatives |
Country Status (23)
| Country | Link |
|---|---|
| EP (1) | EP0169571B1 (en) |
| JP (1) | JPH06716B2 (en) |
| KR (1) | KR930000112B1 (en) |
| AR (1) | AR242023A1 (en) |
| AT (1) | ATE32882T1 (en) |
| AU (2) | AU589130B2 (en) |
| CA (1) | CA1277332C (en) |
| CS (1) | CS256392B2 (en) |
| DE (1) | DE3561808D1 (en) |
| DK (1) | DK173287B1 (en) |
| ES (2) | ES8703825A1 (en) |
| FI (1) | FI84345C (en) |
| GR (1) | GR851841B (en) |
| HU (1) | HU195480B (en) |
| IE (1) | IE58735B1 (en) |
| IL (1) | IL75913A (en) |
| MC (1) | MC1692A1 (en) |
| NO (1) | NO161064C (en) |
| NZ (1) | NZ212868A (en) |
| PH (1) | PH21556A (en) |
| PT (1) | PT80876B (en) |
| ZA (1) | ZA854828B (en) |
| ZW (1) | ZW12185A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ232865A (en) * | 1989-03-21 | 1992-07-28 | Hoffmann La Roche | A mixed-micelle solution comprising a micelle former and an immunomodulator |
| DE4036779A1 (en) * | 1990-11-17 | 1992-05-21 | Basf Ag | USE OF ARYLPOLYCAN CARBONIC ACIDS AND THEIR DERIVATIVES AS LIGHT PROTECTION AGENTS IN COSMETIC PREPARATIONS |
| US7655699B1 (en) | 1992-04-22 | 2010-02-02 | Eisai Inc. | Compounds having selective activity for retinoid X receptors, and means for modulation of processes mediated by retinoid X receptors |
| US5369126A (en) * | 1993-01-06 | 1994-11-29 | Hoffmann-La Roche Inc. | Nonatetraenoic acid derivative for use in treating acne |
| CA2129773C (en) | 1993-09-02 | 2007-05-01 | Michael Klaus | Aromatic carboxylic acid derivatives |
| US7115728B1 (en) | 1995-01-30 | 2006-10-03 | Ligand Pharmaceutical Incorporated | Human peroxisome proliferator activated receptor γ |
| US7098025B1 (en) | 1997-07-25 | 2006-08-29 | Ligand Pharmaceuticals Incorporated | Human peroxisome proliferator activated receptor gamma (pparγ) gene regulatory sequences and uses therefor |
| KR101285483B1 (en) * | 2004-10-28 | 2013-07-12 | 상꾜 가부시키가이샤 | Optically active 4,4-disubstituted oxazolidine derivative and method for producing same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3334125A (en) * | 1964-02-26 | 1967-08-01 | Velsicol Chemical Corp | Esters of 3-6-dichloro-2-methoxy-benzyl alcohol |
| CH585166A5 (en) * | 1973-03-30 | 1977-02-28 | Hoffmann La Roche | |
| CH605562A5 (en) * | 1974-09-26 | 1978-09-29 | Hoffmann La Roche | |
| DE2933985A1 (en) * | 1979-08-22 | 1981-04-09 | Bayer Ag, 5090 Leverkusen | NEW 4-FLUOR-3-PHENOXY-BENZYL ETHERS AND METHOD FOR THEIR PRODUCTION AND NEW INTERMEDIATE PRODUCTS FOR THIS AND METHOD FOR THEIR PRODUCTION |
-
1985
- 1985-06-26 ZA ZA854828A patent/ZA854828B/en unknown
- 1985-07-25 CS CS855502A patent/CS256392B2/en not_active IP Right Cessation
- 1985-07-25 NZ NZ212868A patent/NZ212868A/en unknown
- 1985-07-25 CA CA000487547A patent/CA1277332C/en not_active Expired - Fee Related
- 1985-07-25 GR GR851841A patent/GR851841B/el unknown
- 1985-07-25 AR AR85301088A patent/AR242023A1/en active
- 1985-07-25 IL IL75913A patent/IL75913A/en not_active IP Right Cessation
- 1985-07-25 FI FI852899A patent/FI84345C/en not_active IP Right Cessation
- 1985-07-25 AU AU45575/85A patent/AU589130B2/en not_active Ceased
- 1985-07-25 DK DK198503404A patent/DK173287B1/en active
- 1985-07-25 ZW ZW121/85A patent/ZW12185A1/en unknown
- 1985-07-25 MC MC851787A patent/MC1692A1/en unknown
- 1985-07-26 AT AT85109383T patent/ATE32882T1/en active
- 1985-07-26 PT PT80876A patent/PT80876B/en not_active IP Right Cessation
- 1985-07-26 ES ES545565A patent/ES8703825A1/en not_active Expired
- 1985-07-26 PH PH32568A patent/PH21556A/en unknown
- 1985-07-26 IE IE188185A patent/IE58735B1/en not_active IP Right Cessation
- 1985-07-26 DE DE8585109383T patent/DE3561808D1/en not_active Expired
- 1985-07-26 JP JP60164183A patent/JPH06716B2/en not_active Expired - Lifetime
- 1985-07-26 EP EP85109383A patent/EP0169571B1/en not_active Expired
- 1985-07-26 HU HU852841A patent/HU195480B/en not_active IP Right Cessation
- 1985-07-26 KR KR1019850005366A patent/KR930000112B1/en not_active IP Right Cessation
- 1985-07-26 NO NO852980A patent/NO161064C/en not_active IP Right Cessation
-
1986
- 1986-02-17 ES ES552061A patent/ES8705355A1/en not_active Expired
-
1989
- 1989-10-05 AU AU42608/89A patent/AU619901B2/en not_active Ceased
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |