DE1212075B - Process for processing cis, trans, trans-cyclododecatriene (1, 5, 9) - Google Patents
Process for processing cis, trans, trans-cyclododecatriene (1, 5, 9)Info
- Publication number
- DE1212075B DE1212075B DEC29331A DEC0029331A DE1212075B DE 1212075 B DE1212075 B DE 1212075B DE C29331 A DEC29331 A DE C29331A DE C0029331 A DEC0029331 A DE C0029331A DE 1212075 B DE1212075 B DE 1212075B
- Authority
- DE
- Germany
- Prior art keywords
- trans
- cyclododecatriene
- compounds
- cis
- catalyst components
- 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 5
- XRLIZCVYAYNXIF-UHFFFAOYSA-N C/1=CC=CC=CCCCCCC1 Chemical compound C/1=CC=CC=CCCCCCC1 XRLIZCVYAYNXIF-UHFFFAOYSA-N 0.000 title 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkyl aluminum halides Chemical class 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000003701 inert diluent Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/273—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a twelve-membered ring
- C07C13/275—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a twelve-membered ring the twelve-membered ring being unsaturated
- C07C13/277—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a twelve-membered ring the twelve-membered ring being unsaturated with a cyclododecatriene ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Aufarbeitung von cis,trans,trans-Cyclododecatrien-(1,5,9) Es ist bekannt, cis,trans,trans-Cyclododecatrien-(1,5,9) neben anderen ringförmigen Kohlenwasserstoffen dadurch herzustellen, daß man auf Butadien ein Gemisch von Titanhalogeniden und Alkylaluminiumhalogeniden bei Temperaturen bis zu 150 C in Gegenwart von Lösungsmitteln einwirken läßt. Eine besonders vorteilhafte Darstellung besteht darin, daß man als Katalysatoren Titantetrachlorid in Konzentrationen von 67 bis 143 und Alkylaluminium-sesquichloride in Konzentrationen von 0,25 bis 5,7 mMol/kg Verdünnungsmittel einsetzt.Process for the processing of cis, trans, trans-cyclododecatriene- (1,5,9) It is known to have cis, trans, trans-cyclododecatriene- (1,5,9) among other ring-shaped To produce hydrocarbons by adding a mixture of titanium halides to butadiene and alkyl aluminum halides at temperatures up to 150 C in the presence of solvents can act. A particularly advantageous representation is that as Catalysts titanium tetrachloride in concentrations from 67 to 143 and alkyl aluminum sesquichloride used in concentrations of 0.25 to 5.7 mmol / kg of diluent.
Bei diesen Verfahren erhält man cis,trans,trans-Cyclododecatrien-(1,5,9), das geringe Mengen von Chlorverbindungen enthält. Im wesentlichen handelt es sich um eine Verbindung der Formel Cl2Hl9Cl, die vermutlich durch Einwirkung von Chlorwasserstoff auf das Cyclododecatrien entsteht. Versuche haben gezeigt, daß sich Chlorwasserstoff bilden kann, wenn während der Umsetzung Wasser in das Reaktionsmedium gelangt. Durch Arbeiten mit trockenen Lösungsmitteln und trockenem Butadien kann die Bildung von Chlorwasserstoff verhindert werden. These processes give cis, trans, trans-cyclododecatriene- (1,5,9), that contains small amounts of chlorine compounds. Essentially it is to a compound of the formula Cl2Hl9Cl, which is presumably caused by the action of hydrogen chloride on the cyclododecatriene arises. Experiments have shown that hydrogen chloride can form if water gets into the reaction medium during the reaction. By Working with dry solvents and dry butadiene can cause the formation of Hydrogen chloride can be prevented.
Bei der bisher üblichen Art der Aufarbeitung des Cyclododecatriens werden Verbindungen, die saure Wasserstoffatome enthalten, beispielsweise Alkohole oder Wasser, dem Cyclododecatrien zugesetzt, um die Katalysatoren unwirksam zu machen, worauf anschließend das Cyclododecatrien durch Destillation, gegebenenfalls mit Wasserdampf, von höhersiedenden Nebenprodukten abgetrennt wird. Bei der Zugabe von Verbindungen mit saurem Wasserstoffatom oder von Wasser entsteht Chlorwasserstoff, der an das Cyclododecatrien addiert werden könnte, wodurch die oben beschriebenen chlorhaltigen Verbindungen gebildet werden. Beobachtungen sprechen dafür, daß insbesondere das Cyclododecatrien, welches noch an eine Titankomplexverbindung gebunden ist, sich mit dem Chlorwasserstoff besonders leicht umsetzt. Eine der wichtigsten technischen Verarbeitungsprozesse des Cyclododecatriens ist die Hydrierung zum Cyclododecan. Erfahrungsgemäß beeinflussen nun Chlorverbindungen die geeigneten Hydrierungskatalysatoren empfindlich; schon verhältnismäßig geringe Mengen führen zu ihrer Inaktivierung. Es besteht zwar die Möglichkeit, durch eine fraktionierte Destillation die Chlorverbindungen abzutrennen, jedoch ist dies wegen der verhältnismäßig geringen Siedepunktdifferenzen schwierig, zumal die Chlorverbindungen die höhersiedenden Komponenten sind, so daß eine fraktionierte Destillation des gesamten Cyclododecatriens erforderlich ist. In the usual way of working up the cyclododecatriene are compounds that contain acidic hydrogen atoms, such as alcohols or water, the cyclododecatriene added to make the catalysts ineffective, whereupon the cyclododecatriene by distillation, optionally with Steam, is separated from higher-boiling by-products. When adding Compounds with an acidic hydrogen atom or from water form hydrogen chloride, which could be added to the cyclododecatriene, creating the above-described chlorine-containing compounds are formed. Observations suggest that in particular the cyclododecatriene, which is still bound to a titanium complex compound, reacts particularly easily with the hydrogen chloride. One of the most important technical The processing of cyclododecatriene is hydrogenation to cyclododecane. Experience has shown that chlorine compounds now influence the suitable hydrogenation catalysts sensitive; even relatively small amounts lead to their inactivation. It is possible to use fractional distillation to remove the chlorine compounds separated, but this is because of the relatively small boiling point differences difficult, especially since the chlorine compounds are the higher-boiling components, so that fractional distillation of all of the cyclododecatriene is required.
Die Verhinderung oder Unterdrückung der Bildung der obengenannten Chlorverbindungen würde demnach das Herstellungsverfahren für Cyclododecan wesentlich verbessern. The prevention or suppression of education the above Chlorine compounds would therefore be essential to the manufacturing process for cyclododecane to enhance.
Es wurde gefunden, daß man cis,trans,trans-Cyclododecatrien-(1,5,9), das aus Butadien mit Hilfe von Mischkatalysatoren aus Titantetrachlorid und Alkylaluminiumhalogeniden in inerten Verdünnungsmitteln hergestellt wurde, durch Zersetzung der Katalysatorkomponenten durch Verbindungen mit saurem Wasserstoffatom vorteilhafter aufarbeiten kann, indem man die übliche Zersetzung der Katalysatorkomponenten durch Verbindungen mit saurem Wasserstoffatom außerdem in Gegenwart von Aceton, gegebenenfalls zusätzlich in Gegenwart von Pyridin, vornimmt. It has been found that cis, trans, trans-cyclododecatriene- (1,5,9), that from butadiene with the help of mixed catalysts made from titanium tetrachloride and alkyl aluminum halides was prepared in inert diluents, by decomposition of the catalyst components can work up by compounds with an acidic hydrogen atom by the usual decomposition of the catalyst components by compounds with acidic Hydrogen atom also in the presence of acetone, optionally also in the presence of pyridine.
Das Aceton wird in der 0,05- bis 50fachen, vorzugsweise etwa der 0,5- bis Sfachen molaren Menge, bezogen auf die Katalysatorkomponenten, eingesetzt. The acetone is 0.05 to 50 times, preferably about 0.5 to S times the molar amount, based on the catalyst components, is used.
Das Verfahren kann sowohl diskontinuierlich als auch kontinuierlich durchgeführt werden. The process can be either discontinuous or continuous be performed.
Beispiel In 340 g trockenem Benzol werden 6,2 g (50 mMol) Äthylaluminium-sesquichlorid gelöst und bei 400 C im Verlauf von einigen Minuten 0,14 g (0,74 mMol) Titantetrachlorid (entsprechend einem Aluminium-Titan-Verhältnis von 67: 1), in 10 g Benzol gelöst, zugefügt. Im Verlauf von 3 Stunden werden dann bei 40"C 261 g Butadien eingeleitet. Nach einer Stunde Nachrühren wird dem Reaktionsgemisch eine Mischung von 20 cm3 (15,7 g; 270 mMol) Aceton in trockenem Benzol zugesetzt. Nach weiteren 30 Minuten werden mit 80 cm3 Methanol die Katalysatorkomponenten vollständig zerstört. Man gewinnt durch Wasserdampfdestillation und Destillation im Vakuum ohne Fraktionierung 212 g Cyclododecatrien-(1,5,9),entsprechend einer Ausbeute von 79,3 01,, bezogen auf das eingesetzte Butadien, mit einem Chlorgehalt von 13 ppm. Example 6.2 g (50 mmol) of ethylaluminum sesquichloride are added to 340 g of dry benzene dissolved and at 400 C in the course of a few minutes 0.14 g (0.74 mmol) of titanium tetrachloride (corresponding to an aluminum-titanium ratio of 67: 1), dissolved in 10 g benzene, added. 261 g of butadiene are then passed in at 40 ° C. in the course of 3 hours. After stirring for one hour, the reaction mixture becomes a mixture of 20 cm3 Added acetone (15.7 g; 270 mmol) in dry benzene. After another 30 minutes the catalyst components are completely destroyed with 80 cm3 of methanol. Man obtained by steam distillation and vacuum distillation without fractionation 212 g of cyclododecatriene (1,5,9), corresponding to a yield of 79,3 01 ,, based on the butadiene used, with a chlorine content of 13 ppm.
Arbeitet man in gleicher Weise ohne Zusatz von Aceton auf, so enthält das Cyclododecatrien-(1,5,9) etwa 500 bis 1000 ppm Chlor. Setzt man dem ausreagierten Ansatz außer 20 cm3 Aceton noch 10 cm3 einer 0,1molaren Lösung (1 mMol) von Pyridin in Benzol zu, so erhält man ein Cyclododecatrien-(1,5,9), das nur noch 6 ppm Chlor enthält. If you work up in the same way without the addition of acetone, it contains the cyclododecatriene (1,5,9) about 500 to 1000 ppm chlorine. If you put the reacted In addition to 20 cm3 of acetone, add 10 cm3 of a 0.1 molar solution (1 mmol) of pyridine in benzene, a cyclododecatriene (1,5,9) is obtained which contains only 6 ppm of chlorine contains.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC29331A DE1212075B (en) | 1963-03-08 | 1963-03-08 | Process for processing cis, trans, trans-cyclododecatriene (1, 5, 9) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC29331A DE1212075B (en) | 1963-03-08 | 1963-03-08 | Process for processing cis, trans, trans-cyclododecatriene (1, 5, 9) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1212075B true DE1212075B (en) | 1966-03-10 |
Family
ID=7018933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC29331A Pending DE1212075B (en) | 1963-03-08 | 1963-03-08 | Process for processing cis, trans, trans-cyclododecatriene (1, 5, 9) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1212075B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE615375A (en) * | ||||
| DE1080547B (en) * | 1958-12-27 | 1960-04-28 | Basf Ag | Process for the production of optionally methyl-substituted cyclododecatriene- (1, 5, 9) |
| DE1085523B (en) * | 1958-08-06 | 1960-07-21 | Studiengesellschaft Kohle Mbh | Process for the production of cyclododecatrienes (1, 5, 9) among other ring-shaped hydrocarbons |
| DE1106758B (en) * | 1960-01-13 | 1961-05-18 | Basf Ag | Process for the preparation of cyclododecatrienes (1, 5, 9) and higher-molecular oligomers from 1, 3-dienes |
| DE1109674B (en) * | 1959-12-22 | 1961-06-29 | Basf Ag | Process for the preparation of liquid oligomers from 1,3-dienes |
| FR1317859A (en) * | 1963-05-08 |
-
1963
- 1963-03-08 DE DEC29331A patent/DE1212075B/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE615375A (en) * | ||||
| FR1317859A (en) * | 1963-05-08 | |||
| DE1085523B (en) * | 1958-08-06 | 1960-07-21 | Studiengesellschaft Kohle Mbh | Process for the production of cyclododecatrienes (1, 5, 9) among other ring-shaped hydrocarbons |
| DE1080547B (en) * | 1958-12-27 | 1960-04-28 | Basf Ag | Process for the production of optionally methyl-substituted cyclododecatriene- (1, 5, 9) |
| DE1109674B (en) * | 1959-12-22 | 1961-06-29 | Basf Ag | Process for the preparation of liquid oligomers from 1,3-dienes |
| DE1106758B (en) * | 1960-01-13 | 1961-05-18 | Basf Ag | Process for the preparation of cyclododecatrienes (1, 5, 9) and higher-molecular oligomers from 1, 3-dienes |
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