DE1216862B - Process for the preparation of mono- or polyunsaturated aldehydes or their functional derivatives - Google Patents
Process for the preparation of mono- or polyunsaturated aldehydes or their functional derivativesInfo
- Publication number
- DE1216862B DE1216862B DEB79333A DEB0079333A DE1216862B DE 1216862 B DE1216862 B DE 1216862B DE B79333 A DEB79333 A DE B79333A DE B0079333 A DEB0079333 A DE B0079333A DE 1216862 B DE1216862 B DE 1216862B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- mono
- functional derivatives
- preparation
- aldehydes
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 7
- 150000001299 aldehydes Chemical class 0.000 title description 8
- 238000002360 preparation method Methods 0.000 title description 2
- 150000002373 hemiacetals Chemical class 0.000 claims description 5
- 150000004714 phosphonium salts Chemical class 0.000 claims description 4
- 150000001241 acetals Chemical class 0.000 claims description 3
- 150000008063 acylals Chemical class 0.000 claims description 3
- 150000007857 hydrazones Chemical class 0.000 claims description 3
- 150000002923 oximes Chemical class 0.000 claims description 3
- 150000007659 semicarbazones Chemical class 0.000 claims description 3
- 150000007854 aminals Chemical class 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 hydroxy-isopropoxy-methyl Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000020945 retinal Nutrition 0.000 description 2
- 239000011604 retinal Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 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 description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- HDRBTZRNAOBFDH-UHFFFAOYSA-N 2-tritylbut-3-enal Chemical compound C1(=CC=CC=C1)C(C(C=C)C=O)(C1=CC=CC=C1)C1=CC=CC=C1 HDRBTZRNAOBFDH-UHFFFAOYSA-N 0.000 description 1
- 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 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000005840 aryl radicals 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
- 238000001816 cooling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum 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
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5428—Acyclic unsaturated phosphonium 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/518—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of sulfur-containing compounds to >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
- C07F9/54—Quaternary phosphonium compounds
-
- 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- 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)
- 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
Verfahren zur Herstellung von ein- oder mehrfach ungesättigten Aldehyden oder ihren funktionellen Derivaten Zusatz zur Anmeldung: B 74477 IV b/12o -Auslegeschrift 1 211 616 Gegenstand der Hauptpatentanmeldung B 74477 IVb/ 120 (deutsche Auslegeschrift 1 211 616) ist ein Verfahren zur Herstellung von ein- oder mehrfach ungesättigten Aldehyden oder ihren Acetalen, Acylalen, Oximen, Hydrazonen, Semicarbazonen oder Schiffschen Basen, das dadurch gekennzeichnet ist, daß man Phosphoniumsalze der allgemeinen Formel in der Ar einen gegebenenfalls durch Alkyl- oder Alkoxygruppen substituierten Arylrest, R1, R2 und Rs Wasserstoff oder Alkyl, X ein einwertiges Anion und n eine ganze Zahl von 0 bis 3 bedeutet, in jeweils an sich bekannter Weise in vorstehend genannten Aldehydderivaten überführt, diese, gewünschtenfalls ohne Isolierung, mittels Protonenakzeptoren zu den entsprechenden Yliden umsetzt, die Ylide mit Aldehyden oder Ketonen zur Umsetzung bringt und die erhaltenen Aldehydderivate gewinnt oder gegebenenfalls zu den freien Aldehyden spaltet.Process for the preparation of mono- or polyunsaturated aldehydes or their functional derivatives mono- or polyunsaturated aldehydes or their acetals, acylals, oximes, hydrazones, semicarbazones or Schiff's bases, which is characterized in that phosphonium salts of the general formula are used in which Ar is an aryl radical optionally substituted by alkyl or alkoxy groups, R1, R2 and Rs are hydrogen or alkyl, X is a monovalent anion and n is an integer from 0 to 3, these are converted in a manner known per se into the aforementioned aldehyde derivatives , if desired without isolation, is converted to the corresponding ylides by means of proton acceptors, the ylides are reacted with aldehydes or ketones and the aldehyde derivatives obtained are obtained or, if appropriate, cleaved to give the free aldehydes.
Es wurde nun gefunden, daß man in Abwandlung des Verfahrens gemäß Hauptpatentanmeldung B 74477 IVb/120 die Phosphoniumsalze an Stelle der Umwandlung in die Acetale, Acylale, Oxime, Hydrazone, Semicarbazone oder Schiffschen Basen in die Halbacetale, Mercaptale oder Aminale in jeweils an sich bekannter Weise überführt. Die nach dem erfindungsgemäßen Verfahren aus den Phosphoniumsalzen in der ersten Verfahrensstufe herstellbaren Aldehydderivate haben demnach die allgemeine Formel in der Ar, R1, R2, Rs, n und X die vorstehend angegebene Bedeutung haben: A Alkoxy B Hydroxy A Alkylmercapto B Alkylmercapto A N(R')2 B N(R')2 R' = Alkyl Die Beispiele erläutern das erfindungsgemäße Verfahren. Im übrigen gelten die Angaben der Hauptpatentanmeldung.It has now been found that, in a modification of the process according to main patent application B 74477 IVb / 120, the phosphonium salts, instead of converting them into the acetals, acylals, oximes, hydrazones, semicarbazones or Schiff's bases, into the hemiacetals, mercaptals or aminals in each case known per se Way convicted. The aldehyde derivatives which can be prepared by the process according to the invention from the phosphonium salts in the first process stage accordingly have the general formula in which Ar, R1, R2, Rs, n and X have the meaning given above: A alkoxy B hydroxy A alkyl mercapto B alkyl mercapto AN (R ') 2 BN (R') 2 R '= alkyl The examples illustrate the process according to the invention. Otherwise, the information in the main patent application applies.
Beispiel 1 10 Teile Triphenyl - 3 - formyl - buten - (2) - yl - (1)-phosphoniumchlorid werden mit 20 Teilen Isopropanol und einem Kriställchen p-Toluolsulfonsäure zum Sieden erhitzt. Das Lösungsmittel wird langsam über 4 Stunden hinweg abdestilliert. Es bleiben als durchkristallisierendes Dl 11,6 Teile Triphenyl-3-(hydroxy-isopropoxy-methyl)-buten-(2)-yl-(1)-phospho niumchlorid zurück. Nach Umfällen aus einer Methylenchloridlösung mit Tetrahydrofuran schmilzt das Halbacetal bei 87 bis 90°C. Das NMR-, das UR-Spektrum und die Analyse sichern die Konstitution. Example 1 10 parts of triphenyl - 3 - formyl - buten - (2) - yl - (1) - phosphonium chloride are p-toluenesulfonic acid with 20 parts of isopropanol and a crystal Boiling heated. The solvent is slowly distilled off over 4 hours. 11.6 parts of triphenyl-3- (hydroxy-isopropoxy-methyl) -butene- (2) -yl- (1) -phospho remain as fully crystallizing Dl nium chloride back. After reprecipitation from a methylene chloride solution with tetrahydrofuran the hemiacetal melts at 87 to 90 ° C. The NMR, the UR spectrum and the analysis secure the constitution.
Analysenwerte: Gefunden ... C 70,3, P 6,9°/o; berechnet . . . C 70,7, P 7,00/0.Analysis values: Found ... C 70.3, P 6.9%; calculated . . . C 70.7, P 7.00 / 0.
4,4 Teile des Triphenyl-3-(hydroxy-isopropoxy-methyl)-buten-(2)-yl-(1)-phosphoniumchlorids werden in 20 Teilen Methanol gelöst und mit 0,23 Teilen Natrium in 10 Teilen Methanol sowie mit 2,84 Teilen Vitamin A-Aldehyd versetzt. In einer Stickstoffatmosphäre wird 1 Stunde unter Rückfluß gekocht. 4.4 parts of triphenyl-3- (hydroxy-isopropoxy-methyl) -butene- (2) -yl- (1) -phosphonium chloride are dissolved in 20 parts of methanol and 0.23 part of sodium in 10 parts of methanol and 2.84 parts of vitamin A aldehyde are added. In a nitrogen atmosphere is refluxed for 1 hour.
Das erhaltene Gemisch wird mit Wasser versetzt und mit Äther extrahiert. Zur Spaltung des Halbacetals wird die ätherische Lösung 1/2 Stunde mit 2n-Schwefelsäure gerührt. Nach Trocknen der Atherphase und Abdestillieren des Lösungsmittels bleiben 3,3 Teile eines orangeroten Ols zurück.The mixture obtained is mixed with water and extracted with ether. To split the hemiacetal, the ethereal solution is treated with 2N sulfuric acid for 1/2 hour touched. After drying the ether phase and distilling off the solvent stay 3.3 parts of an orange-red oil.
Nach Kristallisation aus tiefsiedendem Petroläther kann das ,B-Apo-12'-carotinal kristallin erhalten werden. Gelborange Kristalle, F. 88 bis 92°C; Amax 414 mp; E:S, = 2130 (gemessen in Cyclohexan).After crystallization from low-boiling petroleum ether, the 'B-apo-12'-carotenal can can be obtained in crystalline form. Yellow-orange crystals, m.p. 88 to 92 ° C; Amax 414 mp; IT, = 2130 (measured in cyclohexane).
Beispiel 2 7,6 Teile Triphenyl 3 - formyl - buten - (2) - yl - (1)-phosphoniumchlorid werden in 50 Teilen Methanol mit 2,1 Teilen o-Ameisensäuremethylester und einem Kriställchen p-Toluolsulfonsäure 2 Stunden erhitzt. Example 2 7.6 parts of triphenyl 3-formyl-buten- (2) -yl- (1) -phosphonium chloride are in 50 parts of methanol with 2.1 parts of methyl o-formate and one Crystals of p-toluenesulfonic acid heated for 2 hours.
Nach dem Abkühlen versetzt man mit 0,36 Teilen Wasser und engt die Mischung zur Trocknung ein.After cooling, it is mixed with 0.36 parts of water and concentrated Mixture to dry.
Es bleiben 8,2 Teile einer kristallinen Substanz zurück, bei der es sich nach UR- und NMR-Spektrum um das Halbacetal handelt. F. 113 bis 115"C.8.2 parts of a crystalline substance remain in which it is the hemiacetal according to the UR and NMR spectrum. F. 113 to 115 "C.
Analysenwerte: Gefunden ... C 69,6, P 6,4°/o; berechnet . . C 69,8, P 6,30/0.Analysis values: Found ... C 69.6, P 6.4%; calculated . . C 69.8, P 6.30 / 0.
4,3 Teile des so erhaltenen Methyl-halbacetals des Triphenyl-3-formylbuten-(2)-yl-(1)-phosphoniumchlorids werden mit 30 Teilen Methanol und 0,23 Teilen Na in 10 Teilen Methanol versetzt. Nach Zugabe von 3,5 Teilen ß - Apo - 12' - carotinal erhitzt man 2 Stunden in einer Stickstoffatmosphäre unter Rückfluß. Das erkaltete Reaktionsgemisch wird mit Wasser und verdünnter Schwefelsäure versetzt und mit Octan extrahiert. Nach dem Trocknen der Octanphase über Natriumsulfat und Abdestillieren des Lösungsmittels bleiben 4,2 Teile eines tiefroten Kristallbreis zurück. Nach Umkristallisieren aus Benzol-Methanol erhält man das ß-Apo-8'-carotinal in kristalliner Form. F. 137"C; Ämaz 458 my; % = 2600 (gemessen in Cyclohexan). 4.3 parts of the methyl hemiacetal of triphenyl-3-formylbutene- (2) -yl- (1) -phosphonium chloride thus obtained 30 parts of methanol and 0.23 part of Na in 10 parts of methanol are added. After adding 3.5 parts of ß-apo-12 '-carotinal, the mixture is heated for 2 hours in a Nitrogen atmosphere under reflux. The cooled reaction mixture is washed with water and dilute sulfuric acid are added and the mixture is extracted with octane. After drying the octane phase over sodium sulfate and distilling off the solvent remain 4.2 parts of a deep red crystal pulp. After recrystallization from benzene-methanol the ß-apo-8'-carotenal is obtained in crystalline form. F. 137 "C; Ämaz 458 my;% = 2600 (measured in cyclohexane).
Beispiel 3 Man versetzt 10 Teile Triphenyl-3-formyl-buten-(2)-yl-(1)-phosphoniumchlorid mit 30 Teilen Chloroform und 2,5 Teilen Dithioglykol. Nach Einleiten einer Spur Chlorwasserstoff wird bei Zimmertemperatur 5 Stunden gerührt. Nach Einengen erhält man 12,1Teile des Mercaptals als Dl, das in 50 Teilen Methanol gelöst und mit 0,61 Teilen Natrium in 10 Teilen Methanol sowie mit 7,5 Teilen Vitamin A-Aldehyd versetzt wird. In einer Stickstoffatmosphäre wird 3 Stunden unter Rückfluß gekocht. Zur Spaltung des Mercaptals wird die erkaltete Lösung mit Quecksilber(II)-chlorid in Aceton versetzt und unter Erwärmen auf 40"C weitere 2 Stunden gerührt. Example 3 10 parts of triphenyl-3-formyl-buten- (2) -yl- (1) -phosphonium chloride are added with 30 parts of chloroform and 2.5 parts of dithioglycol. After initiating a track Hydrogen chloride is stirred at room temperature for 5 hours. Receives after narrowing one 12.1 parts of the mercaptal as Dl, dissolved in 50 parts of methanol and with 0.61 Parts of sodium in 10 parts of methanol and 7.5 parts of vitamin A aldehyde are added will. The mixture is refluxed for 3 hours in a nitrogen atmosphere. To split of the mercaptal, the cooled solution is mixed with mercury (II) chloride in acetone and stirred for a further 2 hours while warming to 40 ° C.
Nach Extrahieren der Mischung mit Octan, Trocknen und Abdestillieren des Lösungsmittels bleiben 8,2 Teile eines roten uns zurück (Ämaz 414 m). Nach Kristallisation aus tiefsiedendem Petroläther kann das BApo-12'-carotinal in kristalliner Form erhalten werden; gelborange Kristalle, F. 91 bis 94"C; Ämax 414mm; E:C, = 2160 (gemessen in Cyclohexan).After extracting the mixture with octane, drying and distilling off of the solvent, 8.2 parts of a red us remain (Ämaz 414 m). After crystallization The BApo-12'-carotenal can be obtained in crystalline form from low-boiling petroleum ether will; yellow-orange crystals, m.p. 91 to 94 "C; Ämax 414mm; E: C, = 2160 (measured in cyclohexane).
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB79333A DE1216862B (en) | 1964-11-14 | 1964-11-14 | Process for the preparation of mono- or polyunsaturated aldehydes or their functional derivatives |
| US413617A US3471569A (en) | 1963-11-30 | 1964-11-24 | Process for producing acetals and hemiacetals of phosphonium salt compounds |
| SE14375/64A SE328861B (en) | 1963-11-30 | 1964-11-27 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB79333A DE1216862B (en) | 1964-11-14 | 1964-11-14 | Process for the preparation of mono- or polyunsaturated aldehydes or their functional derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1216862B true DE1216862B (en) | 1966-05-18 |
Family
ID=6980257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB79333A Pending DE1216862B (en) | 1963-11-30 | 1964-11-14 | Process for the preparation of mono- or polyunsaturated aldehydes or their functional derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1216862B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8222458B2 (en) | 2008-06-13 | 2012-07-17 | University Of Maryland, College Park | Process or synthesis of (3S)- and (3R)-3-hydroxy-beta-ionone, and their transformation to zeaxanthin and beta-cryptoxanthin |
-
1964
- 1964-11-14 DE DEB79333A patent/DE1216862B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8222458B2 (en) | 2008-06-13 | 2012-07-17 | University Of Maryland, College Park | Process or synthesis of (3S)- and (3R)-3-hydroxy-beta-ionone, and their transformation to zeaxanthin and beta-cryptoxanthin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0378068A1 (en) | New polyfunctional alpha-diazo-beta-keto esters, process for their preparation and their use | |
| DE1418577B1 (en) | Process for the preparation of ring-substituted o- (alpha-alkylol) -phenols | |
| DE2261751C3 (en) | Process for the preparation of cyclohexanedione (1,3) | |
| DE2003461A1 (en) | Process for the preparation of 2-alkylpyridazinium compounds | |
| DE1216862B (en) | Process for the preparation of mono- or polyunsaturated aldehydes or their functional derivatives | |
| DE2211436A1 (en) | Process for the preparation of 2-alkoxy-5-methoxybenzaldehydes | |
| DE681505C (en) | Process for the production of cyanine or styryl dyes | |
| DE1918253A1 (en) | 3-hydroxyisoxazoles (soil fungicides) prodn | |
| DE1720042A1 (en) | Process for the production of new 5-nitroimidazole ethers | |
| DE960813C (en) | Process for the production of unsaturated ª † and ª € lactones | |
| DE1948550A1 (en) | Fluorinated pyridazine derivatives and processes for their preparation | |
| DE706692C (en) | Process for the preparation of ª ‰ derivatives of pyridine which are not substituted in the 6-position | |
| DE1470102A1 (en) | 2-Hydroxymethyl-5-nitroimidazoles and process for their preparation | |
| DE1567046A1 (en) | Parasiticides, especially fungicides | |
| DE2721401A1 (en) | THIOAETHER, METHOD OF MANUFACTURING AND USING THEREOF | |
| DE2413189C2 (en) | Process for the preparation of benzohydroquinones | |
| DE931652C (en) | Process for the preparation of 5-cycloalkylidene-pseudothiohydantoins | |
| DE822552C (en) | Process for the preparation of alkyl derivatives of diketooxazolidines | |
| DE1192647B (en) | Process for the production of thiol or thionothiolphosphonic acid esters | |
| DE1643506C (en) | N to the power of 1 acylphenyl hydrazine, their salts, process for their preparation and medicinal products containing these compounds, by means of excretion from 1620441 | |
| Niemann | Isomerization of Sphingosine Sulfate1 | |
| DE1768603A1 (en) | Polycyclic compounds with the norbornene core and process for their preparation | |
| AT319200B (en) | VZH OF NEW SUBSTITUTED 1,1-DIPHENYL-2-NITROPROPANES AND BUTANES | |
| CH632263A5 (en) | METHOD FOR PRODUCING CYCLIC 2-METHYL-2,4-DIALKOXY-3-BUTEN-1-AL-ACETALS AND USE THEREOF. | |
| DE903212C (en) | Process for the production of substituted cyclohexenone compounds for combating pests |