DE2117680A1 - Beta-ionones vitamin a intermediates - Google Patents
Beta-ionones vitamin a intermediatesInfo
- Publication number
- DE2117680A1 DE2117680A1 DE19712117680 DE2117680A DE2117680A1 DE 2117680 A1 DE2117680 A1 DE 2117680A1 DE 19712117680 DE19712117680 DE 19712117680 DE 2117680 A DE2117680 A DE 2117680A DE 2117680 A1 DE2117680 A1 DE 2117680A1
- Authority
- DE
- Germany
- Prior art keywords
- formula
- hydrocarbons
- chlorine
- sulfuric acid
- substituted
- 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
- 229940045997 vitamin a Drugs 0.000 title abstract 2
- 150000001588 beta-ionone derivatives Chemical class 0.000 title 1
- 239000000543 intermediate Substances 0.000 title 1
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 101000913968 Ipomoea purpurea Chalcone synthase C Proteins 0.000 claims 5
- 101000907988 Petunia hybrida Chalcone-flavanone isomerase C Proteins 0.000 claims 5
- 239000007858 starting material Substances 0.000 claims 1
- -1 aliphatic alcohols Chemical class 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 abstract 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 abstract 1
- 150000001381 alpha-ionone derivatives Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 235000019155 vitamin A Nutrition 0.000 abstract 1
- 239000011719 vitamin A Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 description 2
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Natural products CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-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
- UZFLPKAIBPNNCA-UHFFFAOYSA-N alpha-ionone Natural products CC(=O)C=CC1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-UHFFFAOYSA-N 0.000 description 1
- UZFLPKAIBPNNCA-BQYQJAHWSA-N alpha-ionone Chemical compound CC(=O)\C=C\C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-BQYQJAHWSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000003756 stirring Methods 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
- C07C403/16—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 not being part of —CHO groups
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Verfahren zur Herstellung von ß-Jononen Zusatz zum Patent . ... ... (Patentanmeldung P 20 23 294.4) Gegenstand des Hauptpatents . ... ... (Patentanmeldung P 20 23 294.4) ist ein Verfahren zur Herstellung von ß-Jononen der Formel in der R1, R2 und R3 Wasserstoffatome oder Methylgruppen bedeuten, durch Cyclisierung von Pseudojononen mit Schwefelsäure, indem man Pseudojonone der Formel in der X Reste der Formeln R1 - C,H - C(CH3) = CH2 R1 - C = C(CH3)2 oder R1 - CH - C(CH3)2 -OCH und 32 Y den Rest der Formel - C(CH3) = CH -bedeutet und R1, R2 und R3 dieselbe Bedeutung wie in Formel I haben, verwendet und die Cyclisierung in Gegenwart von Gemischen aus Kohlenwasserstoffen und niedermolekularen Alkoholen vornimmt.Process for the production of ß-ionons Addition to the patent. ... ... (Patent application P 20 23 294.4) Subject of the main patent. ... ... (patent application P 20 23 294.4) is a process for the production of ß-ionons of the formula in which R1, R2 and R3 denote hydrogen atoms or methyl groups, by cyclizing pseudojonons with sulfuric acid by using pseudojonons of the formula in which X radicals of the formulas R1 - C, H - C (CH3) = CH2 R1 - C = C (CH3) 2 or R1 - CH - C (CH3) 2 -OCH and 32 Y the radical of the formula - C (CH3 ) = CH - means and R1, R2 and R3 have the same meaning as in formula I, and the cyclization is carried out in the presence of mixtures of hydrocarbons and low molecular weight alcohols.
Es wurde nun gefunden, daß man als Kohlenwasserstoffe auch solche verwenden kann, die durch Chlor substituiert sind. Solche Kohlenwasserstoffe sind zum Beispiel Methylchlorid, Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, 1,2-Dichloräthan, Trichloräthan, Chlorcyclohexan oder Chlorbenzol. Es können auch Gemische von zwei oder mehr dieser durch Chlor substituierten Kohlenwasserstoffe, gegebenenfalls zusammen mit von Chlor freien Kohlenwasserstoffen, verwendet werden. Bei derReaktionstemperatur gasförmige Chlor-Kohlenwasserstoffe können durch erhöhten Druck während der Reaktion im flüssigen Zustand gehalten werden.It has now been found that hydrocarbons also include such can use, which are substituted by chlorine. Such hydrocarbons are for example methyl chloride, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, chlorocyclohexane or chlorobenzene. It can too Mixtures of two or more of these hydrocarbons substituted by chlorine, optionally together with chlorine-free hydrocarbons. Chlorine hydrocarbons which are gaseous at the reaction temperature can be increased by increased Pressure can be kept in the liquid state during the reaction.
Im übrigen gelten sinngemäß die Angaben des Hauptpatents.Otherwise, the information in the main patent applies accordingly.
Beispiel 220 Raumteile konzentrierte Schwefelsäure und 100 Raumteile Methylenchlorid werden unter kräftigem Rühren bei -10 bis -15 0C mit einer Lösung aus 80 Raumteilen 6.10-Dimethyl-undeca-3.5.1O-trien-2-on, 100 Raumteilen Methylenchlorid und 15,25 Raumteilen Methanol innerhalb von 5 Minuten versetzt. Die Reaktionswärme wird mit einem Methanol/Trockeneisbad abgeführt. Nach Beendigung des Zulaufs wird noch 15 Minuten bei -10°C gerührt. Das Reaktionsgemisch ist dabei vollständig emulgiert. Nach Abstellen des Rührers tritt mindestens 3 Minuten lang keine Phasentrennung ein. Example 220 parts by volume of concentrated sulfuric acid and 100 parts by volume Methylene chloride with vigorous stirring at -10 to -15 0C with a solution from 80 parts by volume 6.10-dimethyl-undeca-3.5.10-trien-2-one, 100 parts by volume methylene chloride and 15.25 parts by volume of methanol are added within 5 minutes. The heat of reaction is removed with a methanol / dry ice bath. After the inflow is finished Stirred at -10 ° C for a further 15 minutes. The reaction mixture is completely emulsified. After the stirrer has been switched off, no phase separation occurs for at least 3 minutes a.
Das Reaktionsgemisch wird mit 1000 Teilen Eis hydrolysiert. Die organischen Bestandteile werden mit Methylenchlorid durch mehrmaliges Ausschütteln extrahiert und die vereinigten organischen Extrakte mit Sodalösung neutral gewaschen. Der nach Abdampfen des Methylenchlorids verbleibende Rückstand wird über eine einfache Destillationsbrücke destilliert. Man erhält 61 Teile ß-Jonon (E 1 Xm 526 bei 293 m/u; Ausbeute: 83 %). Nach gaschromatographischer Analyse enthält das Produkt kein a-Jonon, Kp. 0>03 73-780C.The reaction mixture is hydrolyzed with 1000 parts of ice. The organic Components are extracted with methylene chloride by shaking out several times and the combined organic extracts washed neutral with soda solution. The after Evaporation of the residue remaining methylene chloride is via a simple distillation bridge distilled. 61 parts of β-ionone are obtained (E 1 Xm 526 at 293 m / u; yield: 83%). According to gas chromatographic analysis, the product does not contain any α-ionone, b.p. 0> 03 73-780C.
Die gleichen Ergebnisse erhält man mit 1.2-Dichloräthan, tert.The same results are obtained with 1,2-dichloroethane, tert.
Butylchlorid oder Chlorbenzol anstatt Methylenchlorid.Butyl chloride or chlorobenzene instead of methylene chloride.
Claims (5)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2117680A DE2117680C3 (en) | 1971-04-10 | 1971-04-10 | Process for the production of ß-ions |
| CH632371A CH548384A (en) | 1970-05-13 | 1971-04-29 | METHOD FOR PRODUCING (BETA) IONONS. |
| US00141348A US3845135A (en) | 1970-05-13 | 1971-05-07 | Manufacture of beta-ionones |
| CA112,631A CA962691A (en) | 1970-05-13 | 1971-05-10 | MANUFACTURE OF .beta.-IONONES |
| FR7116951A FR2093487A5 (en) | 1970-05-13 | 1971-05-11 | |
| NL7106467.A NL160249C (en) | 1970-05-13 | 1971-05-11 | PROCESS FOR PREPARING BETA -IONON OR HOMOLOGISTS THEREOF. |
| GB1437871*[A GB1340211A (en) | 1970-05-13 | 1971-05-12 | Manufacture of beta-ionones |
| BE767063A BE767063A (en) | 1970-05-13 | 1971-05-12 | PROCESS FOR THE PREPARATION OF BETA-IONONES |
| JP46031652A JPS5231863B1 (en) | 1970-05-13 | 1971-05-13 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2117680A DE2117680C3 (en) | 1971-04-10 | 1971-04-10 | Process for the production of ß-ions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2117680A1 true DE2117680A1 (en) | 1972-10-19 |
| DE2117680B2 DE2117680B2 (en) | 1978-02-16 |
| DE2117680C3 DE2117680C3 (en) | 1978-12-07 |
Family
ID=5804500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2117680A Expired DE2117680C3 (en) | 1970-05-13 | 1971-04-10 | Process for the production of ß-ions |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2117680C3 (en) |
-
1971
- 1971-04-10 DE DE2117680A patent/DE2117680C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2117680B2 (en) | 1978-02-16 |
| DE2117680C3 (en) | 1978-12-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) |