DE1210780B - Process for the production of polyunsaturated aldehydes - Google Patents
Process for the production of polyunsaturated aldehydesInfo
- Publication number
- DE1210780B DE1210780B DEB74476A DEB0074476A DE1210780B DE 1210780 B DE1210780 B DE 1210780B DE B74476 A DEB74476 A DE B74476A DE B0074476 A DEB0074476 A DE B0074476A DE 1210780 B DE1210780 B DE 1210780B
- Authority
- DE
- Germany
- Prior art keywords
- aldehydes
- reaction
- aldehyde
- parts
- production
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000001299 aldehydes Chemical class 0.000 title description 26
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 alkyl radicals Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000005840 aryl radicals Chemical group 0.000 claims description 2
- 150000001746 carotenes Chemical class 0.000 claims description 2
- 235000005473 carotenes Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000004291 polyenes Chemical class 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 4
- 229940088594 vitamin Drugs 0.000 claims 1
- 229930003231 vitamin Natural products 0.000 claims 1
- 235000013343 vitamin Nutrition 0.000 claims 1
- 239000011782 vitamin Substances 0.000 claims 1
- 150000003722 vitamin derivatives Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- NCYCYZXNIZJOKI-OVSJKPMPSA-N Retinaldehyde Chemical compound O=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-OVSJKPMPSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007239 Wittig reaction Methods 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 235000021466 carotenoid Nutrition 0.000 description 3
- 150000001747 carotenoids Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000004714 phosphonium salts Chemical class 0.000 description 3
- 235000020945 retinal Nutrition 0.000 description 3
- 239000011604 retinal Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PJEHRCCPERVGEC-VFZGIVFWSA-N 10'-Apo-beta,beta-carotin-10'-al Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=O PJEHRCCPERVGEC-VFZGIVFWSA-N 0.000 description 1
- PJEHRCCPERVGEC-FLHUAPOTSA-N 10'-apo-beta-carotenal Chemical compound O=C/C=C/C(/C)=C/C=C/C=C(\C)/C=C/C=C(\C)/C=C/C1=C(C)CCCC1(C)C PJEHRCCPERVGEC-FLHUAPOTSA-N 0.000 description 1
- DFMMVLFMMAQXHZ-DOKBYWHISA-N 8'-apo-beta,psi-caroten-8'-al Chemical compound O=CC(/C)=C/C=C/C(/C)=C/C=C/C=C(\C)/C=C/C=C(\C)/C=C/C1=C(C)CCCC1(C)C DFMMVLFMMAQXHZ-DOKBYWHISA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000007295 Wittig olefination reaction Methods 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000013735 beta-apo-8'-carotenal Nutrition 0.000 description 1
- 239000001652 beta-apo-8'-carotenal Substances 0.000 description 1
- 235000013734 beta-carotene Nutrition 0.000 description 1
- 239000011648 beta-carotene Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 235000002864 food coloring agent Nutrition 0.000 description 1
- 239000000576 food coloring agent Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- VBQCHPIMZGQLAZ-UHFFFAOYSA-N phosphorane Chemical class [PH5] VBQCHPIMZGQLAZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
-
- 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
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5352—Phosphoranes containing the structure P=C-
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. Gl.:Int. Eq .:
C07cC07c
Deutsche KL: 12 ο-7/03 German KL: 12 ο -7/03
Nummer: 1210 780Number: 1210 780
Aktenzeichen: B 74476IV b/12 οFile number: B 74476IV b / 12 ο
Anmeldetag: 30. November 1963Filing date: November 30, 1963
Auslegetag: 17. Februar 1966Opening day: February 17, 1966
Es gibt eine Reihe von Synthesen in der Polyen- und Carotinoid-Reihe, die sich der Wittigschen Olefinierungsreaktion zur Verknüpfung der Bruchstücke bedienen (vgl. zum Beispiel die Zusammenfassungen von H. P ο m m e r in Angew. Chem., 72 [1960], S. 811 und 911). Diesen Synthesen ist gemeinsam, daß nach der Verknüpfung die neuen Endgruppen der Ketten erst in geeigneter Weise umgewandelt werden müssen, bevor eine weitere Ketten Verlängerung mit Hilfe der Wittig-Reaktion ίο möglich ist.There are a number of syntheses in the polyene and carotenoid series, which are based on Wittig Use the olefination reaction to link the fragments (see, for example, the summaries by H. P ο m m e r in Angew. Chem., 72 [1960], pp. 811 and 911). These syntheses have in common that after the linkage, the new end groups of the chains are only converted in a suitable manner must be before another chain extension with the help of the Wittig reaction ίο is possible.
Es wurde nun gefunden, daß auf vorteilhafte Weise eine unmittelbare Kettenverlängerung von Aldehyden erzielt werden kann. Die Erfindung betrifft ein Verfahren zur Herstellung von mehrfach ungesättigten Aldehyden und ist dadurch gekennzeichnet, daß man phosphorhaltige Ylenale der allgemeinen FormelIt has now been found that a direct chain extension of Aldehydes can be achieved. The invention relates to a method for producing multiple unsaturated aldehydes and is characterized in that one phosphorus-containing ylenals of the general formula
ArAr
Ar — P = O-C =Ar-P = O-C =
ArAr
Ri R2 R3 HRi R 2 R 3 H
—Ire-Irishman
in der Ar einen gegebenenfalls durch Alkyl- oder Alkoxygruppen substituierten Arylrest, Ri, R2 und R3 Wasserstoff oder Alkylreste und η eine ganze Zahl von 1 bis 3 bedeuten, mit Aldehyden umsetzt.in which Ar is an aryl radical optionally substituted by alkyl or alkoxy groups, Ri, R2 and R3 are hydrogen or alkyl radicals and η is an integer from 1 to 3, is reacted with aldehydes.
Verfahren zur Herstellung von mehrfach
ungesättigten AldehydenProcess for the production of multiple
unsaturated aldehydes
Anmelder:Applicant:
Badische Anilin- & Soda-FabrikAniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen/RheinAktiengesellschaft, Ludwigshafen / Rhein
Als Erfinder benannt:Named as inventor:
Dr. Herwig Freyschlag,Dr. Herwig Freyschlag,
Dr. Werner Reif,Dr. Werner Reif,
Dr. Axel Nürrenbach,Dr. Axel Nürrenbach,
Dr. Horst Pommer, Ludwigshafen/RheinDr. Horst Pommer, Ludwigshafen / Rhine
Die Ylenale sind Phosphoranverbindungen, die im gleichen Molekül eine Phosphor-ylen-Gruppierung und eine dazu konjugierte Aldehydgruppe enthalten. Sie werden zweckmäßig nach den» Verfahren der Patentanmeldung B 74473 IV b/12 ο erhalten, indem man auf die entsprechenden Phosphoniumsalze Protonenakzeptoren einwirken läßt.The Ylenale are phosphorane compounds that have a phosphor-ylene group in the same molecule and contain an aldehyde group conjugated thereto. They are expedient according to the »Procedure of patent application B 74473 IV b / 12 ο obtained by clicking on the corresponding phosphonium salts Can act proton acceptors.
Die Reaktion bei dem Verfahren dieser Erfindung verläuft nach dem SchemaThe reaction in the process of this invention proceeds according to the scheme
R1-C +1R 1 -C +1
R4-CH = C-Ri R 4 -CH = C- Ri
IIII
In Formel II steht R4 für einen Rest, der keine mit dem Ylenal in unerwünschter Weise reagierenden Substituenten enthält und üblicherweise in Aldehydmolekülen vorhanden sein kann. Demnach kann er beispielsweise bedeuten einen gesättigten oder ungesättigten Alkyl- oder Cycloalkylrest, Aryl, Aralkyl oder eine Kombination dieser Gruppen. Der Rest R4 kann bereits die GruppeIn formula II, R4 stands for a radical which does not contain any substituents which react undesirably with the ylenal and which can usually be present in aldehyde molecules. Accordingly, it can mean, for example, a saturated or unsaturated alkyl or cycloalkyl radical, aryl, aralkyl or a combination of these groups. The remainder of R 4 can already be the group
RiRi
R2 R3 R 2 R 3
enthalten, und er kann Substituenten der oben R2 Rscontain, and it can substituents of the above R 2 Rs
IIIIII
bezeichneten Art tragen. Dialdehyde sind ebenfalls für das Verfahren dieser Erfindung geeignet, wenn 2 Moleküle Ylenal mit 1 Molekül Dialdehyd umgesetzt werden sollen.designated type. Dialdehydes are also suitable for the process of this invention if 2 molecules of Ylenal should be reacted with 1 molecule of dialdehyde.
Als Aldehyde R4 — CHO können daher praktisch alle Aldehyde benutzt werden, sofern sie keine Gruppen enthalten, mit denen die Ylenale in unerwünschter Weise reagieren oder die auf die Ylenale zerstörend wirken, wie z. B. starke Säuren. Da eines der wichtigsten Anwendungsgebiete des neuen Verfahrens die Kettenverlängerung von Aldehyden der Polyen- und Carotinoidreihe ist, sind als Beispiele geeigneter Aldehyde zunächst zu nennen: jS-Jonylidenacetaldehyd, /Ϊ-Retinen, α-Retinen, ß-Apo-As aldehydes R4 - CHO can therefore be practical all aldehydes are used, provided they do not contain any groups with which the Ylenale in undesirable React wisely or which have a destructive effect on the Ylenale, e.g. B. strong acids. There one the most important areas of application of the new process is the chain extension of aldehydes Polyene and carotenoid series are examples of suitable aldehydes: jS-Jonylidenacetaldehyd, / Ϊ-retins, α-retins, ß-apo-
609 508/278609 508/278
14'-carotinal (C22), j8-Apo-12'-carotinal (C25), jS-Apo-lO'-carotinal (C27), /?-Apo-8'-carotinal (C30), jS-Apo-o'-carotinal (C32), ferner die aus der Carotinchemie bekannten Cio-, Cm- und Ca)-Dialdehyde. 14'-carotinal (C22), j8-Apo-12'-carotinal (C 25 ), jS-Apo-10'-carotinal (C27), /? - Apo-8'-carotinal (C30), jS-Apo- o'-carotinal (C 32 ), also the Cio, Cm and Ca) dialdehydes known from carotene chemistry.
Geeignete Ylenale sind beispielsweise Triphenylphosphin-ß-formylcrotylen (IV), Triphenylphosphina-formyl-crotylen (V), Triphenylphosphin-2-methylpentadien-(l,3)-al-(5)-methylen, Triphenylphosphin-1 - methyl - pentadien - (1,3) - al - (5) -methylen, Triphenylphosphin - 2,6 - dimethyl - heptatrien - (1,3,5)-al - (7) - methylen (VI), Triphenylphosphin -1,5 - dimethyl - heptatrien - (1,3,5) - al - (7) - methylen (VU) und Triphenylphosphin - 1,6 - dimethyl - heptatrien-(l,3,5)-al-(7)-methylen. Die Ylenale bewirken die Verlängerung eines Aldehyds um mehrere Doppelbindungen. So eignen sich beispielsweise die Ylenale IV und V zur Herstellung von isoprenologen Verbindungen, Suitable Ylenals are, for example, triphenylphosphine-ß-formylcrotylene (IV), triphenylphosphine-formylcrotylene (V), triphenylphosphine-2-methylpentadiene (1,3) -al- (5) -methylene, triphenylphosphine-1 - methyl - pentadiene - (1,3) - al - (5) -methylene, triphenylphosphine - 2,6 - dimethyl - heptatriene - (1,3,5) -al - (7) - methylene (VI), triphenylphosphine -1,5 - dimethyl - heptatriene - (1,3,5) - al - (7) - methylene (VU) and triphenylphosphine - 1,6 - dimethyl - heptatriene- (1,3,5) -al- (7) -methylene. The Ylenals cause an aldehyde to be extended by several double bonds. For example, the Ylenale IV and V are suitable for the production of isoprenologous compounds,
Ar
Ar — P = CH — CH = C — CHOAr
Ar-P = CH-CH = C-CHO
/ I/ I
Ar CH3 Ar CH 3
IVIV
ArAr
Ar-P = CH-C = CH-CHOAr-P = CH-C = CH-CHO
ArAr
CH3 CH 3
denen in der Carotinoidreihe besondere Bedeutung zukommt. Wesentlich hierbei ist, daß auch die Einführung mehrerer Isoprenreste nacheinander in das gleiche Molekül möglich ist, da nach jeder Kettenverlängerung wieder eine freie Aldehydgruppe für eine neue Kondensationsreaktion zur Verfugung steht. Die Aldehyde können somit wiederholt verlängert werden. Man kann daher bei dem Verfahren dieser Erfindung einen Aldehyd benutzen, der selbst bereits durch Kettenverlängerung eines Aldehyds mit einem. Ylenal erhalten worden ist.which are of particular importance in the carotenoid series. It is essential that the introduction several isoprene residues one after the other in the same molecule is possible, since after each chain extension again a free aldehyde group is available for a new condensation reaction stands. The aldehydes can thus be lengthened repeatedly. One can therefore use the procedure this invention use an aldehyde, which is itself already by chain extension of an aldehyde with one. Ylenal has been received.
Man braucht den erhaltenen Aldehyd für die weitere Umsetzung nach dieser Erfindung nicht zu isolieren, sondern kann ihn unmittelbar im Reaktionsmedium wieder verwenden.You do not need the aldehyde obtained for the further reaction according to this invention isolate, but can use it again immediately in the reaction medium.
Man setzt die phosphorhaltigen Ylenale mit den Aldehyden bei Temperaturen von etwa 20 bis 180°C,
vorzugsweise 50 bis 10O0Cj um. Als Lösungsmittel eignen sich beispielsweise Alkohole, wie Methanol,
Äthanol, Isopropanol, aromatische Kohlenwasserstoffe, wie Benzol und Toluol, aliphatische und
alicyclische Kohlenwasserstoffe, wie Octan oder Cyclohexan, chlorierte Kohlenwasserstoffe, wie Methylenchlorid,
Chloroform und Chlorbenzol, Äther, wie Diäthyläther, Diisopropyläther oder Tetrahydrofuran,
Nitrile, wie Acetonitril oder Benzonitril, und Säureamide, wie Formamid, Dimethylformamid
oder Diäthylformamid. In manchen fallen kann auch Wasser benutzt oder mitbenutzt werden. Wenn
die Aldehydkomponente unter den Umsetzungsbedingungen flüssig ist, kann ein Überschuß von ihr
als Lösungsmittel ausreichen. Die Reaktionszeiten können sehr unterschiedlich seinr je nach der Art
der angewandten Verbindungen. Sie können x/2 bis
24 Stunden, vorzugsweise 1 bis 12 Stunden, betragen. Kürzere oder längere Zeiten sind jedoch ebenfalls
möglich. Die Reaktionsgemische lassen sich nach den üblichen Methoden aufarbeiten. Die Verfahrensprodukte können beispielsweise durch Kristallisation,
Destillation, Molekulardestillation oder Verteilung isoliert werden.
Für die Ausführung des Verfahrens dieser Erfindung ist es nicht erforderlich, daß man die Ylenale
vor ihrer Umsetzung mit den Aldehyden isoliert und gegebenenfalls reinigt; man kann sie auch ohne
weiteres in dem Medium anwenden, in dem sie hergestellt worden sind.It sets the phosphorus-containing Ylenale with the aldehydes at temperatures of about 20 to 180 ° C, preferably 50 to 10O 0 to Cj. Examples of suitable solvents are alcohols such as methanol, ethanol, isopropanol, aromatic hydrocarbons such as benzene and toluene, aliphatic and alicyclic hydrocarbons such as octane or cyclohexane, chlorinated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether or tetrahydrofuran , Nitriles such as acetonitrile or benzonitrile, and acid amides such as formamide, dimethylformamide or diethylformamide. In some cases, water can also be used or shared. If the aldehyde component is liquid under the reaction conditions, an excess of it may be sufficient as a solvent. The reaction times can r be very different depending on the kind of compounds used. They can be x / 2 to 24 hours, preferably 1 to 12 hours. However, shorter or longer times are also possible. The reaction mixtures can be worked up by the customary methods. The products of the process can be isolated, for example, by crystallization, distillation, molecular distillation or partitioning.
To carry out the process of this invention it is not necessary that the ylenals are isolated and, if necessary, purified before they are reacted with the aldehydes; they can also easily be used in the medium in which they were produced.
j 5 Man kann auch die bei der erfindungsgemäßen Umsetzung benötigten Ylenale in üblicher Weise aus ihren Phosphoniumsalzen in Gegenwart der Aldehyde herstellen, so daß die Ylenale in statu nascendi mit den Aldehyden reagieren.The ylenals required in the reaction according to the invention can also be used in a customary manner from their phosphonium salts in the presence of the aldehydes, so that the Ylenale in statu nascendi react with the aldehydes.
Wenn man den Aldehyd auf das Ylenal in molaren Mengen einwirken läßt, entstehen im wesentlichen unmittelbar einheitliche Verfahrensprodukte. Bei der Anwendung von Ylenal im Überschuß entstehen häufig Gemische von Verbindungen, deren Ketten um ganze Vielfache der Kettenlänge η + 2 des angewandten Ylenals verlängert sind.If the aldehyde is allowed to act on the ylenal in molar amounts, essentially uniform process products are formed. If Ylenal is used in excess, mixtures of compounds are often formed whose chains are lengthened by whole multiples of the chain length η + 2 of the Ylenal used.
Das Verfahren der Erfindung bietet eine Reihe von Vorteilen gegenüber den üblichen Wittig-Reaktionen. Der sorgfältige Ausschluß von Feuchtigkeit und Sauerstoff, wie er bei vielen Wittig-Olefinierungen erforderlich ist, kann hier unterbleiben. Eine weitere Schwierigkeit bei der Wittig-Reaktion liegt häufig darin, daß bei ihr die Aldehyde unter dem Einfluß des zur Ylidbildung benutzten alkalischen Reagenzes Nebenreaktionen geben (vgl. J. Org. Chem., 28, S. 372 [1963]), besonders dann, wenn es sich um empfindliche Aldehyde handelt. Solche Nebenreaktionen können bei Umsetzungen auch von sehr alkalilabilen Aldehyden mit Ylenalen ohne besonderen Aufwand vermieden werden, weil sich die Ylenale leicht und vollständig von Alkali reinigen lassen. Diese Vorteile haben zwei von S. M. M a k i η (Bar. Akad. Wiss. UdSSR, 138, S. 387 bis 389 [1961], und J. f. allgem. Chem. [russ.], 32 [94],The process of the invention offers a number of advantages over the usual Wittig reactions. The careful exclusion of moisture and oxygen, as is the case with many Wittig olefinations is required, can be omitted here. Another difficulty with the Wittig reaction This is often due to the fact that the aldehydes used for ylid formation under the influence of the alkaline reagent give side reactions (see. J. Org. Chem., 28, p. 372 [1963]), especially then, when it comes to sensitive aldehydes. Such side reactions can occur in reactions can also be avoided by very alkali-labile aldehydes with Ylenalen without any special effort, because the Ylenale can be easily and completely cleaned of alkali. These advantages have two of S.M. M a k i η (Bar. Akad. Wiss. USSR, 138, pp. 387 to 389 [1961], and J. f. General Chem. [Russ.], 32 [94],
S. 3159 bis 3161 [1962]) vor einiger Zeit beschriebene Phosphoniumsalze XI und XII nicht.Pp. 3159 to 3161 [1962]) phosphonium salts XI and XII described some time ago do not.
OC2H5OC2H5
(C6H5)P — CH2 — CH = C — CH
ΒΓθ (C 6 H 5) P - CH 2 - CH = C - CH
ΒΓθ
XIXI
CH3 OC2H5 CH 3 OC 2 H 5
OC2H5 OC 2 H 5
(C6Hs)3P — CH2 — C = CH — CH(C 6 Hs) 3 P - CH 2 - C = CH - CH
CH3 OC2H5 CH 3 OC 2 H 5
XIIXII
Die aus diesen Salzen hergestellten Ylide sind nicht isolierbar und sind unstabil sowie empfindlich gegen Feuchtigkeit und Sauerstoff. Eine Reinigung dieser Ylide und eine weitere Umsetzung ihrer Kondensationsprodukte ohne vorherige Veränderung der Endgruppen ist nicht möglich.The ylides produced from these salts cannot be isolated and are unstable and sensitive against moisture and oxygen. A purification of these ylides and a further conversion of their condensation products without changing the end groups beforehand is not possible.
Aus einer Publikation von T r i ρ ρ e 11 und Walker (J. Chem. Soc, 1961, S. 1266) sind zwei Verbindungen der allgemeinen Formel I, jedoch mit η = O und Ri = H oder Methyl, und deren Umsetzung mit Benzaldehyd bekannt. Nach den dort angegebenen Reaktionsbedingungen, z. B. 24 Stunden Rückfluß in Benzol, war es unwahrscheinlich, daß die höheren Glieder dieser Reihe, falls sie überhaupt noch beständig sein sollten, Umsetzungen mit Aldehyden unter ähnlichen Bedingungen aushielten; vielmehr war zu erwarten, daß die Ylenale vorher schon durch Nebenreaktionen, wie Polymerisationen oder Selbstkondensation zerstört werden. Es ist daher umso erstaunlicher, daß bei der Umsetzung von Ylenalen mit Aldehyden gemäß der Erfindung sehr hohe Ausbeuten erreicht werden und Nebenreaktionen der Ylenale unter Reaktionsbedingungen, die der Fachmann nach Kenntnis dieser Erfindung anwendet, praktisch nicht eintreten.From a publication by Tri ρ ρ e 11 and Walker (J. Chem. Soc, 1961, p. 1266) there are two compounds of the general formula I, but with η = O and Ri = H or methyl, and their reaction with benzaldehyde known. According to the reaction conditions specified there, for. B. 24 hours reflux in benzene, it was unlikely that the higher members of this series, if they were to be stable at all, could withstand reactions with aldehydes under similar conditions; rather, it was to be expected that the Ylenals would be destroyed beforehand by side reactions such as polymerizations or self-condensation. It is therefore all the more astonishing that very high yields are achieved in the reaction of ylenals with aldehydes according to the invention and side reactions of the ylenals practically do not occur under reaction conditions which the person skilled in the art applies to the knowledge of this invention.
Die Verfahrensprodukte werden z. B. als Lebensmittelfarbstoffe oder Provitamine verwendet. Beispielsweise entsteht aus der Verbindung IV und Retinen des ^-Apo-H'-carotinal (C25) und aus diesem durch weitere Umsetzung mit IV das ß-Apo-8'-carotinal (C30), das man auch direkt durch Umsetzung von Retinen und Triphenylphosphin-2,6-dimethylheptatrien - (1,3,5) - al - 7 - methylen (VIII) erhalten kann, beides Substanzen mit Provitamin-A-Wirkung, die sich zur Lebensmittelfärbung eignen. Aus /i-Jonyliden-acetaldehyd und der Verbindung V erhält man den Vitamin-A-Aldehyd (= Retinen). Durch Umsetzung von Ylenalen mit anderen Aldehyden können wertvolle neue Produkte gewonnen werden, die sich z. B. zur Herstellung von Farbstoffen, Heilmitteln, Pflanzenschutzmitteln und optischen Aufhellern eignen.The process products are z. B. as food colors or used provitamins. For example, from the compound IV and retins of the ^ -Apo-H'-carotinal (C25) and from this by further reaction with IV the ß-apo-8'-carotenal (C30), which can also be obtained directly by reacting retins and triphenylphosphine-2,6-dimethylheptatriene - (1,3,5) - al - 7 - methylene (VIII), both substances with provitamin A effect, which are suitable for food coloring. From / i-Jonyliden-acetaldehyde and the compound V the vitamin A aldehyde (= retins) is obtained. By reacting ylenalen with other aldehydes valuable new products can be obtained, which z. B. for the production of dyes, Medicines, pesticides and optical brighteners are suitable.
Die in den Beispielen angegebenen Teile sind Gewichtsteile. Sie verhalten sich zu Volumteilen wie Gramm zu Kubikzentimetern.The parts given in the examples are parts by weight. They relate to parts of volume like Grams to cubic centimeters.
2,84 Teile Vitamin-A-Aldehyd und 3,44 Teile Triphenylphosphin-2-formyl-propen-1 -yl-methylen werden in 100 Teilen trockenem Benzol in einer Stickstoffatmosphäre 12 Stunden zum Sieden erhitzt. Das Lösungsmittel wird unter vermindertem Druck abdestilliert, der Rückstand in Äther aufgenommen und mehrmals mit Methanol, das 60 Volumteile Wasser enthält, ausgeschüttelt. Nach Trocknen der Ätherlösung über Natriumsulfat und Abdampfen des Lösungsmittels bleiben 3,18 Teile eines gelborangen Öles zurück {Xmax = 410 πΐμ; E}*„ = 1440), aus dem das entstandene /f-Apo-12'-carotinal (C25) nach vorhergehender Isomerisierung durch Kochen in Ligroin in einer Stickstoffatmosphäre kristallin erhalten werden kann. F. = 87 bis 880C (aus Petroläther). Xmax = 415 ηΐμ; E}*m = 2140 (gemessen in Cyclohexan).2.84 parts of vitamin A aldehyde and 3.44 parts of triphenylphosphine-2-formyl-propen-1 -yl-methylene are heated to boiling in 100 parts of dry benzene in a nitrogen atmosphere for 12 hours. The solvent is distilled off under reduced pressure, the residue is taken up in ether and extracted several times with methanol containing 60 parts by volume of water. After drying the ether solution over sodium sulfate and evaporation of the solvent 3.18 parts remain a yellow-orange oil return {X m ax = 410 πΐμ; E} * "= 1440), from which the / f-apo-12'-carotenal (C25) can be obtained in crystalline form after prior isomerization by boiling in ligroin in a nitrogen atmosphere. F. = 87 to 88 0 C (from petroleum ether). X max = 415 ηΐµ; E} * m = 2140 (measured in cyclohexane).
3,5 Teile /?-Apo-12'-carotinal (C25) und 3,44 Teile Triphenylphosphin-2-formyl-propen-l -yl-methylen werden in 100 Volumteilen trockenem Acetonitril in einer Stickstoffatmosphäre 10 Stunden lang zum Sieden erhitzt. Man destilliert das Lösungsmittel unter vermindertem Druck ab, nimmt den Rückstand in Äther auf und extrahiert mehrmals mit Methanol, das 60 Volumteile Wasser enthält. Nach dem Trocknen der ätherischen Phase über Natriumsulfat wird das Lösungsmittel abdestilliert. Es bleiben 3,71 Teile eines tiefroten Öles zurück, aus dem das entstandene /J-Apo-S'-carotinal (Qo) nach vorhergehender Isomerisation durch Erhitzen in Ligroin in Stickstoffatmosphäre durch Kristallisation aus Benzol—Methanol erhalten werden kann. Violette, metallisch glänzende Blättchen vom F. 137°C. Xmax = 458 πΐμ; E}*m = 2590 (gemessen in Cyclohexan).3.5 parts of apo-12'-carotenal (C 25 ) and 3.44 parts of triphenylphosphine-2-formyl-propen-1-yl-methylene are heated to boiling in 100 parts by volume of dry acetonitrile in a nitrogen atmosphere for 10 hours . The solvent is distilled off under reduced pressure, the residue is taken up in ether and extracted several times with methanol which contains 60 parts by volume of water. After the ethereal phase has been dried over sodium sulfate, the solvent is distilled off. 3.71 parts of a deep red oil remain, from which the / J-apo-S'-carotenal (Qo) formed can be obtained after previous isomerization by heating in ligroin in a nitrogen atmosphere by crystallization from benzene-methanol. Purple, shiny metallic leaves with a temperature of 137 ° C. Xmax = 458 πΐµ; E} * m = 2590 (measured in cyclohexane).
2,8 Teile Vitamin-A-Aldehyd und 3,7 Teile Triphenylphosphin-2-methyl-pentadien-(l,3)-al-(5)-me- thylen werden in 100 Teilen trockenem Acetonitril in einer Stickstoffatmosphäre 10 Stunden lang zum Sieden erhitzt. Man destilliert das Lösungsmittel unter vermindertem Druck ab, nimmt den Rückstand in Äther auf und extrahiert mehrmals mit Methanol, das 60 Volumteile Wasser enthält. Nach dem Trocknen der ätherischen Phase über Natriumsulfat wird das Lösungsmittel abdestilliert. Es bleiben 3,5 Teile eines tiefroten Öles zurück, aus dem das entstandene ß-Apo-lO'-carotinal durch Chromatographie an Aluminiumoxyd in reiner Form erhalten werden kann. Rotes öl; Xmax = 436 πΐμ (in Cyclohexan); E}*m = 2030.2.8 parts of vitamin A aldehyde and 3.7 parts of triphenylphosphine-2-methyl-pentadiene- (1,3) -al- (5) -methylene are in 100 parts of dry acetonitrile in a nitrogen atmosphere for 10 hours Boiling heated. The solvent is distilled off under reduced pressure, the residue is taken up in ether and extracted several times with methanol which contains 60 parts by volume of water. After the ethereal phase has been dried over sodium sulfate, the solvent is distilled off. 3.5 parts of a deep red oil remain, from which the β-apo-10'-carotenal which has formed can be obtained in pure form by chromatography on aluminum oxide. Red oil; Xmax = 436 πΐμ (in cyclohexane); E} * m = 2030.
Claims (4)
Tetrahedron letters, 1963, Nr. 15, S. 979 bis 984.Considered publications:
Tetrahedron letters, 1963, No. 15, pp. 979 to 984.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL124613D NL124613C (en) | 1963-11-30 | ||
DEB74476A DE1210780B (en) | 1963-11-30 | 1963-11-30 | Process for the production of polyunsaturated aldehydes |
AT971964A AT249279B (en) | 1963-11-30 | 1964-11-17 | Process for chain extension of aldehydes |
CH1527364A CH440243A (en) | 1963-11-30 | 1964-11-26 | Process for chain extension of aldehydes |
BR164831/64A BR6464831D0 (en) | 1963-11-30 | 1964-11-26 | PROCESS FOR EXTENDING THE ALDEIDES CHAIN |
GB48228/64A GB1079217A (en) | 1963-11-30 | 1964-11-27 | Method of increasing the chain length of aldehydes |
FR996862A FR1453252A (en) | 1963-11-30 | 1964-11-30 | Process for lengthening the aldehyde chain |
BE656435D BE656435A (en) | 1963-11-30 | 1964-11-30 | |
ES0306554A ES306554A1 (en) | 1963-11-30 | 1964-11-30 | Procedure for the extension of the aldehyde chains. (Machine-translation by Google Translate, not legally binding) |
NL6413904A NL6413904A (en) | 1963-11-30 | 1964-11-30 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB74476A DE1210780B (en) | 1963-11-30 | 1963-11-30 | Process for the production of polyunsaturated aldehydes |
Publications (2)
Publication Number | Publication Date |
---|---|
DE1210780B true DE1210780B (en) | 1966-02-17 |
DE1210780C2 DE1210780C2 (en) | 1966-08-25 |
Family
ID=6978274
Family Applications (1)
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DEB74476A Granted DE1210780B (en) | 1963-11-30 | 1963-11-30 | Process for the production of polyunsaturated aldehydes |
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AT (1) | AT249279B (en) |
BE (1) | BE656435A (en) |
BR (1) | BR6464831D0 (en) |
CH (1) | CH440243A (en) |
DE (1) | DE1210780B (en) |
ES (1) | ES306554A1 (en) |
FR (1) | FR1453252A (en) |
GB (1) | GB1079217A (en) |
NL (2) | NL6413904A (en) |
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US4266073A (en) * | 1975-11-14 | 1981-05-05 | Hoffmann-La Roche Inc. | Fluorinated aromatic polyenes |
US4338253A (en) | 1975-11-14 | 1982-07-06 | Hoffmann-La Roche Inc. | Fluorinated aromatic polyenes |
US4201727A (en) | 1976-11-14 | 1980-05-06 | Hoffmann-La Roche Inc. | Fluorinated aromatic polyenes |
US4335248A (en) | 1975-11-14 | 1982-06-15 | Hoffmann-La Roche Inc. | Fluorinated polyenes |
US4321209A (en) | 1975-11-14 | 1982-03-23 | Hoffmann-La Roche Inc. | Fluorinated aromatic polyenes |
US4299995A (en) | 1979-05-10 | 1981-11-10 | Hoffmann-La Roche Inc. | Fluorinated polyenes |
US4395575A (en) | 1975-11-14 | 1983-07-26 | Hoffmann-La Roche, Inc. | 5(Halophenyl)-2-fluoro-pentadienals |
US4375563A (en) | 1975-11-14 | 1983-03-01 | Hoffmann-La Roche Inc. | Fluorinated aromatic polyenes |
CN112782309B (en) * | 2020-12-29 | 2022-10-28 | 常州大学 | Method for stabilizing long-chain unsaturated olefine aldehyde |
CN115490728B (en) * | 2022-10-17 | 2023-12-08 | 杭州师范大学 | Synthesis method of allyl phosphine derivative |
-
0
- NL NL124613D patent/NL124613C/xx active
-
1963
- 1963-11-30 DE DEB74476A patent/DE1210780B/en active Granted
-
1964
- 1964-11-17 AT AT971964A patent/AT249279B/en active
- 1964-11-26 BR BR164831/64A patent/BR6464831D0/en unknown
- 1964-11-26 CH CH1527364A patent/CH440243A/en unknown
- 1964-11-27 GB GB48228/64A patent/GB1079217A/en not_active Expired
- 1964-11-30 NL NL6413904A patent/NL6413904A/xx unknown
- 1964-11-30 FR FR996862A patent/FR1453252A/en not_active Expired
- 1964-11-30 ES ES0306554A patent/ES306554A1/en not_active Expired
- 1964-11-30 BE BE656435D patent/BE656435A/xx unknown
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Title |
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None * |
Also Published As
Publication number | Publication date |
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ES306554A1 (en) | 1965-04-01 |
CH440243A (en) | 1967-07-31 |
FR1453252A (en) | 1966-06-03 |
BE656435A (en) | 1965-05-31 |
NL6413904A (en) | 1965-05-31 |
AT249279B (en) | 1966-09-12 |
NL124613C (en) | |
GB1079217A (en) | 1967-08-16 |
BR6464831D0 (en) | 1973-08-09 |
DE1210780C2 (en) | 1966-08-25 |
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