DE2117680C3 - Process for the production of ß-ions - Google Patents
Process for the production of ß-ionsInfo
- Publication number
- DE2117680C3 DE2117680C3 DE2117680A DE2117680A DE2117680C3 DE 2117680 C3 DE2117680 C3 DE 2117680C3 DE 2117680 A DE2117680 A DE 2117680A DE 2117680 A DE2117680 A DE 2117680A DE 2117680 C3 DE2117680 C3 DE 2117680C3
- Authority
- DE
- Germany
- Prior art keywords
- hydrocarbons
- parts
- chlorine
- ions
- methylene chloride
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000007363 ring formation reaction Methods 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DHMOUXMWELWHEG-UHFFFAOYSA-N 6,10-dimethylundeca-3,5,10-trien-2-one Chemical compound CC(=C)CCCC(C)=CC=CC(C)=O DHMOUXMWELWHEG-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-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
- 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
- 230000000694 effects Effects 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
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-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
- 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)
Description
CH3 R2 CH 3 R 2
in der X Reste der allgemeinen Formelnin the X residues of the general formulas
R1— CH-C(CH3)=CH,R 1 - CH-C (CH 3 ) = CH,
oderor
R1—C=C(CH3)2 R 1 -C = C (CH 3 ) 2
R1 -CH —C(CH3)2 — OCH3 R 1 -CH-C (CH 3 ) 2 -OCH 3
2525th
3030th
3535
bedeutet undmeans and
R1, R2 und R3 die vorstehende Bedeutung haben, mit Schwefelsäure bei -30 bis +200C in Gegenwart von Kohlenwasserstoffen, deren Siedepunkte unterhalb 200°C liegen, und niedermolekularen Alkoholen nach dem Verfahren des Hauptpatents 20 23 294, dadurch gekennzeichnet, daß man solche Kohlenwasserstoffe benutzt, die durch Chlor substituiert sind.R 1 , R 2 and R 3 have the above meaning, with sulfuric acid at -30 to +20 0 C in the presence of hydrocarbons whose boiling points are below 200 ° C, and low molecular weight alcohols according to the process of the main patent 20 23 294, characterized that one uses those hydrocarbons, which are substituted by chlorine.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man ein Gemisch aus durch Chlor substituierten Kohlenwasserstoffen und von Chlor freien Kohlenwasserstoffen verwendet.2. The method according to claim 1, characterized in that there is a mixture of chlorine substituted hydrocarbons and chlorine-free hydrocarbons are used.
5050
Gegenstand des Hauptpatents 20 23 294 ist ein Verfahren zur Herstellung von jJ-Jononen der allgemeinen FormelThe subject of the main patent 20 23 294 is a process for the production of jJ -ionons of the general formula
CH2-R3 CH 2 -R 3
in der R', R2 und R3 Wasserstoffatome oder Methylgruppen bedeuten, durch Cyclisierung von Pseudojononenin which R ', R 2 and R 3 represent hydrogen atoms or methyl groups, by cyclization of pseudo-jonons
6060
6565
X-CH2-CH2-C=CH-CH=C-C-CH2-R^
CH3 R2 X-CH 2 -CH 2 -C = CH-CH = CC-CH 2 -R ^
CH 3 R 2
in der X Reste der allgemeinen Formeln
R1—CH-C(CH3)=CH,in the X residues of the general formulas
R 1 -CH-C (CH 3 ) = CH,
in der R1, R2 und R3 Wasserstoffatome oder Methylgruppen bedeuten, durch Cyclisierung von Pseudojononen der allgemeinen Formelin which R 1 , R 2 and R 3 are hydrogen atoms or methyl groups, by cyclization of pseudojonones of the general formula
IlIl
X-CH2-CH2-C=CH-CH=C-C-CH2-R3 X-CH 2 -CH 2 -C = CH-CH = CC-CH 2 -R 3
oderor
R1—C=C(CH3),R 1 -C = C (CH 3 ),
R1—CH-C(CH3),-OCH3 R 1 -CH-C (CH 3 ), -OCH 3
bedeutet undmeans and
R1, R2 und R3 die vorstehende Bedeutung haben, mit Schwefelsäure in Gegenwart von Kohlenwasserstoffen, deren Siedepunkte unterhalb 2000C liegen, bei —30 bis + 200C, das dadurch gekennzeichnet ist, daß man die Cyclisierung zusätzlich in Gegenwart von niedermolekularen Alkoholen vornimmt.R 1 , R 2 and R 3 have the above meaning, with sulfuric acid in the presence of hydrocarbons whose boiling points are below 200 0 C, at -30 to + 20 0 C, which is characterized in that the cyclization is also carried out in the presence of low molecular weight alcohols.
Es wurde nun gefunden, daß man das Verfahren der Hauptpatentanmeldung dadurch verbessern kann, daß man solche Kohlenwasserstoffe verwendet, die durch Chlor substituiert sind. Solche Kohlenwasserstoffe sind z. B. 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 der Reaktionstemperatur gasförmige Chlorkohlenwasserstoffe können durch erhöhten Druck während der Reaktion im flüssigen Zustand gehalten werden.It has now been found that the process of the main patent application can be improved in that such hydrocarbons are used which are substituted by chlorine. Such hydrocarbons are z. B. methyl chloride, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, Chlorocyclohexane or chlorobenzene. Mixtures of two or more of these by chlorine can also be used substituted hydrocarbons, optionally together with hydrocarbons free of chlorine, be used. At the reaction temperature, gaseous chlorinated hydrocarbons can through increased pressure to be kept in the liquid state during the reaction.
Bei der Cyclisierung gemäß der Hauptpatentanmeldung kommt es — abhängig von der Herkunft der Ausgangsverbindungen und damit von der Art der darin enthaltenen Verunreinigungen — in einigen Fällen zum Absetzen von Rückständen an den Reaktionsgefäßen. Bei Verwendung von chlorierten Kohlenwasserstoffen bei der Cyclisierung werden die Reaktionsgefäße weniger verschmutzt Dieser vorteilhafte Effekt tritt auch auf, wenn man dem im Hauptpatent beanspruchten Kohlenwasserstoff-Alkohol-Gemisch chlorierte Kohlenwasserstoffe hinzufügt.During the cyclization according to the main patent application, depending on the origin of the Starting compounds and thus on the type of impurities they contain - in some cases for Residues settle on the reaction vessels. When using chlorinated hydrocarbons the reaction vessels are less contaminated during the cyclization. This advantageous effect occurs also when you add chlorinated hydrocarbons to the hydrocarbon-alcohol mixture claimed in the main patent adds.
Im übrigen gelten sinnngemäß die Angaben der H auptpatentanmeldung.For the rest, the details of the main patent application apply mutatis mutandis.
220 Raumteile konzentrierte Schwefelsäure und 100 Raumteile Methylenchlorid werden unter kräftigem Rühren bei -10 bis -150C mit einer Lösung aus 80 Raumteilen 6,10-Dimethyl-undeca-3,5,10-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 — 100C gerührt. Das Reaktionsgemisch ist dabei vollständig emulgiert. Nach Abstellen des Rührers tritt mindestens 3 Minuten lang keine Phasentrennung ein.220 parts by volume of concentrated sulfuric acid and 100 parts by volume of methylene chloride are 6,10-dimethyl-undeca-3,5,10-trien-2-one with vigorous stirring at -10 to -15 0 C with a solution of 80 parts by volume 100 parts by volume of methylene chloride and 15.25 parts by volume of methanol are added within 5 minutes. The heat of reaction is dissipated with a methanol / dry ice bath. After the end of feed for 15 minutes at will - 10 0 C stirred. The reaction mixture is completely emulsified. After the stirrer has been switched off, no phase separation occurs for at least 3 minutes.
3 43 4
Das Reaktionsgemisch wird mit 1000 Teilen Eis erhält 61 Teile J?-Jonon (E |!°„ 526 bei 293 πιμ; Ausbeute:The reaction mixture is combined with 1000 parts of ice to obtain 61 parts of J? -Jonon (E |! ° „526 at 293 πιμ; yield:
hydrolysiert Die organischen Bestandteile werden mit 83%). Nach gaschromatographischer Analyse enthältThe organic components are hydrolyzed with 83%). According to gas chromatographic analysis contains
Methylenchlorid durch mehrmaliges Ausschütteln ex- das Produkt kein a-Jonon.Methylene chloride ex- the product no a-ion by shaking out several times.
trahiert und die vereinigten organischen Extrakte mit Kp. 0.03 73 —780C.tracted and the combined organic extracts with Kp. 00:03 73 -78 0 C.
Sodalösung neutral gewaschen. Der nach Abdampfen 5 Die gleichen Ergebnisse erhält man mit 1,2-Dichlor-Washed soda solution neutral. After evaporation 5 The same results are obtained with 1,2-dichloro
des Methylenchlorids verbleibende Rückstand wird äthan, tert-Butylchlorid oder Chlorbenzol anstattof the methylene chloride remaining residue is used instead of ethane, tert-butyl chloride or chlorobenzene
über eine einfache Destillationsbrücke destilliert. Man Methylenchlorid.distilled over a simple distillation bridge. One methylene chloride.
Claims (1)
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 DE2117680A1 (en) | 1972-10-19 |
| DE2117680B2 DE2117680B2 (en) | 1978-02-16 |
| DE2117680C3 true 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 |
|---|---|
| DE2117680A1 (en) | 1972-10-19 |
| DE2117680B2 (en) | 1978-02-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) |