SK330692A3 - Method for preparation of 1r, cis-2,2-dimethyl-3-formyl- -cyclopropane-1-carboxylic acid lactone and intermediates - Google Patents

Method for preparation of 1r, cis-2,2-dimethyl-3-formyl- -cyclopropane-1-carboxylic acid lactone and intermediates Download PDF

Info

Publication number: SK330692A3
Authority: SK; Slovakia
Prior art keywords: acid; cis; dimethyl; alkaline earth; cyclopropane
Prior art date: 1991-11-08

Application number

SK3306-92A

Other languages

English (en)

Slovak (sk)

Other versions

SK278847B6 (sk

Inventor

Francis Brion

Colette Colladant

Jacques Lagouardat

Jacques Scholl

Original Assignee

Roussel Uclaf

Priority date (The priority date 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 date listed.)

1991-11-08

Filing date

1992-11-04

Publication date

1998-03-04

1992-11-04 Application filed by Roussel Uclaf filed Critical Roussel Uclaf

1998-03-04 Publication of SK278847B6 publication Critical patent/SK278847B6/sk

1998-03-04 Publication of SK330692A3 publication Critical patent/SK330692A3/sk

Links

238000000034 method Methods 0.000 title claims abstract description 31
238000002360 preparation method Methods 0.000 title claims abstract description 6
239000000543 intermediate Substances 0.000 title description 7
150000001875 compounds Chemical class 0.000 claims abstract description 22
239000007800 oxidant agent Substances 0.000 claims abstract description 9
239000002253 acid Substances 0.000 claims description 28
239000000203 mixture Substances 0.000 claims description 20
-1 alkali metal salt Chemical class 0.000 claims description 17
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
239000005708 Sodium hypochlorite Substances 0.000 claims description 13
229910052784 alkaline earth metal Inorganic materials 0.000 claims description 13
150000001342 alkaline earth metals Chemical class 0.000 claims description 13
SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 13
229910052783 alkali metal Inorganic materials 0.000 claims description 11
150000002596 lactones Chemical class 0.000 claims description 11
150000001340 alkali metals Chemical class 0.000 claims description 9
229910052749 magnesium Inorganic materials 0.000 claims description 8
239000011777 magnesium Substances 0.000 claims description 8
235000011121 sodium hydroxide Nutrition 0.000 claims description 8
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
JQLDXPJJQAIQCC-UHFFFAOYSA-N 3-[carboxy(hydroxy)methyl]-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)C(O)=O)C1C(O)=O JQLDXPJJQAIQCC-UHFFFAOYSA-N 0.000 claims description 5
238000002955 isolation Methods 0.000 claims description 5
DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
159000000003 magnesium salts Chemical class 0.000 claims description 4
KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 4
229910052708 sodium Inorganic materials 0.000 claims description 4
239000011734 sodium Substances 0.000 claims description 4
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
239000003795 chemical substances by application Substances 0.000 claims description 3
229910052700 potassium Inorganic materials 0.000 claims description 3
239000011591 potassium Substances 0.000 claims description 3
239000012286 potassium permanganate Substances 0.000 claims description 3
150000003839 salts Chemical class 0.000 claims description 3
OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
229910019142 PO4 Inorganic materials 0.000 claims description 2
150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
230000002378 acidificating effect Effects 0.000 claims description 2
229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
150000008045 alkali metal halides Chemical class 0.000 claims description 2
150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
239000008346 aqueous phase Substances 0.000 claims description 2
150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
229910052791 calcium Inorganic materials 0.000 claims description 2
239000011575 calcium Substances 0.000 claims description 2
AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
235000011116 calcium hydroxide Nutrition 0.000 claims description 2
150000001735 carboxylic acids Chemical class 0.000 claims description 2
KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 2
125000004122 cyclic group Chemical group 0.000 claims description 2
AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 2
229910052736 halogen Inorganic materials 0.000 claims description 2
ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 2
235000021317 phosphate Nutrition 0.000 claims description 2
150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
235000011118 potassium hydroxide Nutrition 0.000 claims description 2
JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims 2
238000011065 in-situ storage Methods 0.000 claims 2
VOVAKSXCTQYGIH-UHFFFAOYSA-N 2-formylcyclopropane-1-carboxylic acid Chemical compound OC(=O)C1CC1C=O VOVAKSXCTQYGIH-UHFFFAOYSA-N 0.000 claims 1
239000003513 alkali Substances 0.000 claims 1
OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 claims 1
239000007858 starting material Substances 0.000 claims 1
YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
239000000243 solution Substances 0.000 description 22
239000000047 product Substances 0.000 description 19
XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
230000003647 oxidation Effects 0.000 description 8
238000007254 oxidation reaction Methods 0.000 description 8
238000003756 stirring Methods 0.000 description 8
AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 7
235000019345 sodium thiosulphate Nutrition 0.000 description 7
IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
239000007864 aqueous solution Substances 0.000 description 6
238000002844 melting Methods 0.000 description 6
230000008018 melting Effects 0.000 description 6
230000020477 pH reduction Effects 0.000 description 5
BKUHNVYPRVILOX-UHFFFAOYSA-N 2,2-dimethyl-3-(2-oxopropyl)cyclopropane-1-carboxylic acid Chemical compound CC(=O)CC1C(C(O)=O)C1(C)C BKUHNVYPRVILOX-UHFFFAOYSA-N 0.000 description 4
BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
229910052921 ammonium sulfate Inorganic materials 0.000 description 4
235000011130 ammonium sulphate Nutrition 0.000 description 4
125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 4
238000000605 extraction Methods 0.000 description 4
QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 4
WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
239000012074 organic phase Substances 0.000 description 4
ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
PTQGFDXPHNRDCV-UHFFFAOYSA-N 3-formyl-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C=O)C1C(O)=O PTQGFDXPHNRDCV-UHFFFAOYSA-N 0.000 description 3
ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 3
239000004133 Sodium thiosulphate Substances 0.000 description 3
230000015572 biosynthetic process Effects 0.000 description 3
239000012043 crude product Substances 0.000 description 3
238000001035 drying Methods 0.000 description 3
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
239000012429 reaction media Substances 0.000 description 3
SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
150000007513 acids Chemical class 0.000 description 2
238000002425 crystallisation Methods 0.000 description 2
230000008025 crystallization Effects 0.000 description 2
XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
238000001704 evaporation Methods 0.000 description 2
230000008020 evaporation Effects 0.000 description 2
229920006395 saturated elastomer Polymers 0.000 description 2
239000002904 solvent Substances 0.000 description 2
OYUOWEBAHMVBKK-UHFFFAOYSA-N 3-oxabicyclo[3.1.0]hexane-2-carboxylic acid Chemical compound OC(=O)C1OCC2CC12 OYUOWEBAHMVBKK-UHFFFAOYSA-N 0.000 description 1
QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
238000010521 absorption reaction Methods 0.000 description 1
239000001166 ammonium sulphate Substances 0.000 description 1
239000012736 aqueous medium Substances 0.000 description 1
SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
239000003638 chemical reducing agent Substances 0.000 description 1
238000004587 chromatography analysis Methods 0.000 description 1
238000001816 cooling Methods 0.000 description 1
239000013078 crystal Substances 0.000 description 1
YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 1
150000002148 esters Chemical class 0.000 description 1
239000000706 filtrate Substances 0.000 description 1
238000010438 heat treatment Methods 0.000 description 1
238000004128 high performance liquid chromatography Methods 0.000 description 1
230000000749 insecticidal effect Effects 0.000 description 1
230000000670 limiting effect Effects 0.000 description 1
229910052744 lithium Inorganic materials 0.000 description 1
LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 description 1
YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 description 1
238000004519 manufacturing process Methods 0.000 description 1
239000002609 medium Substances 0.000 description 1
235000019260 propionic acid Nutrition 0.000 description 1
IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
238000000926 separation method Methods 0.000 description 1
PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 description 1
229960001922 sodium perborate Drugs 0.000 description 1
CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
238000003786 synthesis reaction Methods 0.000 description 1
238000004809 thin layer chromatography Methods 0.000 description 1
CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D307/32—Oxygen atoms
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Furan Compounds (AREA)
Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

SK3306-92A 1991-11-08 1992-11-04 Method for preparation of 1r, cis-2,2-dimethyl-3-formyl- -cyclopropane-1-carboxylic acid lactone and intermediates SK330692A3 (en)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
FR9113775A FR2683525B1 (fr)	1991-11-08	1991-11-08	Nouveau procede de preparation de la lactone de l'acide 1r, cis 2,2-dimethyl 3-formyl cyclopropane-1-carboxylique et intermediaires .

Publications (2)

Publication Number	Publication Date
SK278847B6 SK278847B6 (sk)	1998-03-04
SK330692A3 true SK330692A3 (en)	1998-03-04

Family

ID=9418740

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
SK3306-92A SK330692A3 (en)	1991-11-08	1992-11-04	Method for preparation of 1r, cis-2,2-dimethyl-3-formyl- -cyclopropane-1-carboxylic acid lactone and intermediates

Country Status (27)

Country	Link
US (1)	US5278322A (cs)
EP (1)	EP0541445B1 (cs)
JP (1)	JP3167811B2 (cs)
KR (1)	KR100245059B1 (cs)
CN (1)	CN1035819C (cs)
AR (1)	AR247739A1 (cs)
AT (1)	ATE134372T1 (cs)
AU (1)	AU652329B2 (cs)
BR (1)	BR9204313A (cs)
CA (1)	CA2082286C (cs)
CZ (1)	CZ282006B6 (cs)
DE (1)	DE69208425T2 (cs)
DK (1)	DK0541445T3 (cs)
ES (1)	ES2083713T3 (cs)
FI (1)	FI106125B (cs)
FR (1)	FR2683525B1 (cs)
GR (1)	GR3019109T3 (cs)
HU (1)	HU216976B (cs)
IL (1)	IL103414A (cs)
MX (1)	MX9206355A (cs)
NO (1)	NO301641B1 (cs)
PL (2)	PL171116B1 (cs)
RU (1)	RU2058310C1 (cs)
SK (1)	SK330692A3 (cs)
TR (1)	TR26720A (cs)
UA (1)	UA44884C2 (cs)
ZA (1)	ZA928569B (cs)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US1379008A (en) *	1919-11-17	1921-05-24	Albert B Frenier	Temperature-producing mechanism and controlling means therefor
US2726250A (en) *	1951-05-15	1955-12-06	Koege Kemisk Vaerk	5-monosubstituted 2-oxo-2, 5-dihydrofurans
FR1580474A (cs) *	1968-07-12	1969-09-05
SE386670B (sv) *	1968-07-12	1976-08-16	Roussel Uclaf	Sett att framstella inre hemiacylater av cis-3,3-dimetyl-2-formylcyklopropan-1-karbonsyra
US4014918A (en) *	1968-07-12	1977-03-29	Roussel-Uclaf	Process for the preparation of cyclopropane derivatives and compounds produced therein
US3694472A (en) *	1970-05-12	1972-09-26	Roussel Uclaf	Synthesis of pyrethric acid
US3965129A (en) *	1973-10-10	1976-06-22	Hoffmann-La Roche Inc.	Optical resolution of organic carboxylic acids
FR2396006A1 (fr) *	1977-06-27	1979-01-26	Roussel Uclaf	Nouveaux composes a noyau cyclopropanique, procede de preparation et application a la preparation de derives cyclopropaniques a chaine dihalovinyliques
US4132717A (en) *	1977-08-09	1979-01-02	Shell Oil Company	Enol lactone intermediate for the preparation of (1R,cis)-caronaldehydic acid
US4518797A (en) *	1978-10-23	1985-05-21	Shell Oil Company	Cyclopropanecarboxylate pesticides and their preparation
FR2479213A1 (fr) *	1980-03-28	1981-10-02	Roussel Uclaf	Procede de preparation d'acide pentenoique possedant une fonction aldehyde
FR2485000A1 (fr) *	1980-06-20	1981-12-24	Roussel Uclaf	4-methyl 3-formyl pentene 1-oates d'alcoyle inferieur, leur procede de preparation et leur application
DE3111849A1 (de) *	1981-03-26	1982-10-14	Bayer Ag, 5090 Leverkusen	Verfahren zur herstellung von caronaldehydsaeure und deren derivaten

1991
- 1991-11-08 FR FR9113775A patent/FR2683525B1/fr not_active Expired - Lifetime
1992
- 1992-10-06 AR AR92323365A patent/AR247739A1/es active
- 1992-10-08 RU SU925052808A patent/RU2058310C1/ru not_active IP Right Cessation
- 1992-10-13 IL IL10341492A patent/IL103414A/en not_active IP Right Cessation
- 1992-10-29 US US07/968,429 patent/US5278322A/en not_active Expired - Lifetime
- 1992-11-03 TR TR92/1063A patent/TR26720A/xx unknown
- 1992-11-04 SK SK3306-92A patent/SK330692A3/sk unknown
- 1992-11-04 CZ CS923306A patent/CZ282006B6/cs not_active IP Right Cessation
- 1992-11-05 ES ES92402994T patent/ES2083713T3/es not_active Expired - Lifetime
- 1992-11-05 AT AT92402994T patent/ATE134372T1/de not_active IP Right Cessation
- 1992-11-05 MX MX9206355A patent/MX9206355A/es unknown
- 1992-11-05 DK DK92402994.5T patent/DK0541445T3/da active
- 1992-11-05 EP EP92402994A patent/EP0541445B1/fr not_active Expired - Lifetime
- 1992-11-05 DE DE69208425T patent/DE69208425T2/de not_active Expired - Lifetime
- 1992-11-06 PL PL92312901A patent/PL171116B1/pl not_active IP Right Cessation
- 1992-11-06 FI FI925050A patent/FI106125B/fi not_active IP Right Cessation
- 1992-11-06 JP JP32137192A patent/JP3167811B2/ja not_active Expired - Lifetime
- 1992-11-06 AU AU28186/92A patent/AU652329B2/en not_active Ceased
- 1992-11-06 PL PL92296514A patent/PL171284B1/pl not_active IP Right Cessation
- 1992-11-06 BR BR929204313A patent/BR9204313A/pt not_active IP Right Cessation
- 1992-11-06 NO NO924276A patent/NO301641B1/no not_active IP Right Cessation
- 1992-11-06 ZA ZA928569A patent/ZA928569B/xx unknown
- 1992-11-06 HU HU9203489A patent/HU216976B/hu unknown
- 1992-11-06 CA CA002082286A patent/CA2082286C/fr not_active Expired - Lifetime
- 1992-11-07 CN CN92112856A patent/CN1035819C/zh not_active Expired - Lifetime
- 1992-11-07 KR KR1019920020869A patent/KR100245059B1/ko not_active Expired - Lifetime
1993
- 1993-11-08 UA UA93003082A patent/UA44884C2/uk unknown
1996
- 1996-02-27 GR GR950401766T patent/GR3019109T3/el unknown

Also Published As

Publication number	Publication date
PL296514A1 (en)	1993-07-12
BR9204313A (pt)	1993-05-18
MX9206355A (es)	1994-03-31
CA2082286A1 (fr)	1993-05-09
ES2083713T3 (es)	1996-04-16
HU9203489D0 (en)	1993-03-01
SK278847B6 (sk)	1998-03-04
FI106125B (fi)	2000-11-30
NO924276D0 (no)	1992-11-06
ATE134372T1 (de)	1996-03-15
HUT63156A (en)	1993-07-28
IL103414A (en)	1996-08-04
AU2818692A (en)	1993-05-13
IL103414A0 (en)	1993-03-15
CZ282006B6 (cs)	1997-04-16
JP3167811B2 (ja)	2001-05-21
PL171116B1 (pl)	1997-03-28
NO301641B1 (no)	1997-11-24
DE69208425D1 (de)	1996-03-28
FI925050L (fi)	1993-05-09
US5278322A (en)	1994-01-11
KR100245059B1 (ko)	2000-03-02
EP0541445A1 (fr)	1993-05-12
AR247739A1 (es)	1995-03-31
HU216976B (hu)	1999-10-28
CN1072930A (zh)	1993-06-09
NO924276L (no)	1993-05-10
KR930010018A (ko)	1993-06-21
CN1035819C (zh)	1997-09-10
FR2683525A1 (fr)	1993-05-14
TR26720A (tr)	1995-05-15
FR2683525B1 (fr)	1994-01-21
UA44884C2 (uk)	2002-03-15
JPH05222025A (ja)	1993-08-31
PL171284B1 (en)	1997-03-28
GR3019109T3 (en)	1996-05-31
EP0541445B1 (fr)	1996-02-21
DE69208425T2 (de)	1996-09-05
CZ330692A3 (en)	1993-08-11
DK0541445T3 (da)	1996-04-09
RU2058310C1 (ru)	1996-04-20
CA2082286C (fr)	2001-02-27
ZA928569B (en)	1993-11-08
FI925050A0 (fi)	1992-11-06
AU652329B2 (en)	1994-08-18

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