DE699607C - Process for the alkylation of benzene or its homologues - Google Patents
Process for the alkylation of benzene or its homologuesInfo
- Publication number
- DE699607C DE699607C DE1936B0176208 DEB0176208D DE699607C DE 699607 C DE699607 C DE 699607C DE 1936B0176208 DE1936B0176208 DE 1936B0176208 DE B0176208 D DEB0176208 D DE B0176208D DE 699607 C DE699607 C DE 699607C
- Authority
- DE
- Germany
- Prior art keywords
- aluminum chloride
- benzene
- alkylation
- chloride
- homologues
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims description 24
- 238000005804 alkylation reaction Methods 0.000 title claims description 7
- 230000029936 alkylation Effects 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 5
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical group CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000006203 ethylation Effects 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
- C07C2/68—Catalytic processes with halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
- C07C2527/126—Aluminium chloride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/133—Compounds comprising a halogen and vanadium, niobium, tantalium, antimonium or bismuth
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Alkylierung von Benzol oder dessen Homologen Zur Alkylierung von Benzol oder dessen Homologen wird Aluminiumchlorid als Kondensationsmittel benutzt. Die Anlagerung der Alkylgruppen an die aromatischen Kohlenwasserstoffe geschieht in der Regel dadurch, daß diesen Aluminiumchlorid in einer Menge von too,ö und mehr zugegeben wird, worauf dann auf eine bestimmte Temperatur erhitzt wird und während des Erlützens die die Alkylgruppe liefernden Stoffe eingeleitet werden, und zwar in Gasform, z. B. Äthylen, Propylen.Process for the alkylation of benzene or its homologues For alkylation of benzene or its homologues, aluminum chloride is used as a condensing agent. The addition of the alkyl groups to the aromatic hydrocarbons takes place usually by having this aluminum chloride in an amount of too, ö and more is added, which is then heated to a certain temperature and during the release of the substances supplying the alkyl group are initiated, namely in gaseous form, e.g. B. ethylene, propylene.
Bei dieser Arbeitsweise sinkt die Temperatur dann ab, wenn die Zufuhr von Wärtne von außen unterbrochen wird; insbesondere ist es bei lebhaftem Gasstrom ohne gleichzeitige Wärmezufuhr nicht möglich, die Kondensation weiter durchzuführen.In this mode of operation, the temperature drops when the supply is interrupted by Wärtne from without; it is especially with a brisk gas flow Without the simultaneous supply of heat, it is not possible to continue the condensation.
Dieses Alkylierungsverfahren ist verhältnismäßig kostspielig infolge eines hohen Verbrauchs an Aluminiumchlorid und einer nicht zufriedenstellenden Ausbeute. Gemäß der Erfindung sollen diese übelstände beseitigt werden.This alkylation process is relatively expensive as a result a high consumption of aluminum chloride and an unsatisfactory yield. According to the invention, these inconveniences are to be eliminated.
Aluminiumchlorid ist in den zu alkylierenden aromatischen Kohlenwasserstoffen verhältnismäßig' wenig löslich; infolgedessen wirkt im wesentlichen nur die Oberfläche des zugesetzten Aluminiumchlorids.Aluminum chloride is in the aromatic hydrocarbons to be alkylated relatively little soluble; as a result, only the surface is essentially effective of the added aluminum chloride.
Die Alky lierung soll befördert werden 'dadurch, daß das Aluminiumchlorid ganz oder wenigstens teilweise in dem zu alkylierenden Kohlenwasserstoff gelöst wird durch Zugabe von Antimontrichlorid oder ähnlich wirkenden Stoffen, wie Wismutchlorid oder Zinnchlorür.The alkylation should be promoted 'by the fact that the aluminum chloride completely or at least partially dissolved in the hydrocarbon to be alkylated is made by adding antimony trichloride or similar substances such as bismuth chloride or tin chloride.
Bei Zusatz von Antitnontrichlorid geht das Aluminiumchlorid vollständig in Lösung, so daß also das Antimontrichlorid, das als solches im Benzol löslich ist, als Lösungsmittel oder als die Lösung vermittelnder Stoff für das Aluminiumchlorid wirkt.If antitnon trichloride is added, the aluminum chloride goes completely in solution, so that the antimony trichloride, which as such is soluble in benzene is, as a solvent or as the solubilizing substance for the aluminum chloride works.
Die Wirkung des Aluminiumchlorids als Kondensationsmittel wird dadurch in außerordentlichem Maße erhöht; infolgedessen kann. mit weit geringeren Zusatzmengen von Aluminiumchlorid gearbeitet werden: Wenn z. B. bisher für eine Kondensation ro% und mehr Aluminiumchlorid dem Benzol zugesetzt werden mußte; so erniedrigt sich diese Menge bei der zusätzlichen Benutzung von Antimonchlorid auf 3% und weniger. Besonders bei der Einführung von Äthylgruppen können noch geringere Mengen angewendet werden.The effect of the aluminum chloride as a condensing agent is thereby in extraordinary Dimensions increased; as a result, can. with far smaller amounts of aluminum chloride added: If z. B. so far ro% and more aluminum chloride can be added to the benzene for condensation had to; this amount is reduced with the additional use of antimony chloride to 3% and less. Especially with the introduction of ethyl groups, even lower Quantities are applied.
Außer der Erhöhung der Wirtschaftlichkeit durch Verringerung der Alurniniumchloridmenge «wird noch der Vorteil erreicht, daß die Alkylierung ohne Wärmezufuhr durchgeführt werden kann. Es ist sogar unter Umständen notwendig, den Gasstrom zu drosseln oder eine Kühlung des Kohlenwasserstoffs vorzunehmen, wenn die Einhaltung einer bestimmten Temperatur erwünscht ist. Zweckmäßig wird die Konstänthältung der Reaktionstemperatur durch Einregelung des zugeleiteten Gasstroms des die Alkylgruppe liefernden Stoffes durchgeführt.In addition to increasing the economy by reducing the amount of aluminum chloride «The advantage is also achieved that the alkylation is carried out without the supply of heat can be. It may even be necessary to throttle the gas flow or to undertake a cooling of the hydrocarbon if compliance with a certain Temperature is desired. It is expedient to keep the reaction temperature constant by regulating the supplied gas flow of the substance supplying the alkyl group carried out.
Die folgenden Vergleichsversuche zeigen die Überlegenheit des Verfahrens der zusätzlichen Benutzung von Antimonchlorid als Lösungsmittel für das Aluminiufnchlorid gegenüber dem bisherigen Verfahren des Zusetzens,von Aluminiumchlorid allein zu den zu alkylierenden aromatischen Kohlenwasserstoffen.The following comparative tests show the superiority of the process the additional use of antimony chloride as a solvent for the aluminum chloride compared to the previous method of adding aluminum chloride alone the aromatic hydrocarbons to be alkylated.
Es: ist vorgeschlagen worden, bei der Darstellung von Tertiärbutylxylol und Tertiärbutyltoluol durch Einwirkenlassen von m-Xylol oder Töluol auf Isobutyöen das Aluminiumchlorid im Gemisch mit Magnesiumchlorid; Chlorzink, Eisenchlorid und ähnlichen Körpern oder deren Bromiden zu verwenden. Dabei wird ein Inlösungbringen des Aluminiumchlorids weder bezweckt noch erreicht. Beispiel i Zu 20o,- Benzol wurden 3o g Aluminiumchlorid hinzugefügt und das Gemisch auf etwa 70 erhitzt.It: It has been proposed, in the preparation of tertiary butyl xylene and tertiary butyl toluene by allowing m-xylene or töluene to act on isobutylene, the aluminum chloride in a mixture with magnesium chloride; Use zinc chloride, ferric chloride and similar bodies or their bromides. Bringing the aluminum chloride into solution is neither intended nor achieved. Example i To 20o benzene was added 30 g of aluminum chloride and the mixture was heated to about 70.
Beim Einleiten von Äthylengas ging die Temperatur beim Abstellen der Wärmezufuhr sofort zurück. Die Äthylierung konnte nur bei gleichzeitiger Wärmezufuhr vorgenommen werden. Die Aufnahme von Äth@@len während einer Einleitungsdauer von 3 Stunden betrug , 10 g. -Beispiel z Zu. zoo g Benzol wurden 6 g Aluminiumchlorid und i o bis - 12,-, Antimontrichlorid hinzugefügt und das Gemisch auf 7o° erhitzt. Beim Einleiten von Äthylengas ging die Temperatur beim Abstellen der Wärmezufuhr nicht zurück, sondern stieg je nach der Menge des eingeleiteten Gases sehr rasch an. Je größer die Gaszufuhr dagegen bei Beispiel i war, desto schneller fiel die Temperatur. Die Aufnahme von Äthylengas während einer Einleitungsdauer von 3 Stunden betrug bei Beispiel 2 5o g.When ethylene gas was introduced, the temperature fell immediately when the heat supply was switched off. The ethylation could only be carried out with simultaneous supply of heat. The uptake of Äth @@ len during an induction period of 3 hours was 10 g. -Example z To. zoo g of benzene, 6 g of aluminum chloride and 10 to - 12, -, antimony trichloride were added and the mixture was heated to 70 °. When ethylene gas was introduced, the temperature did not decrease when the heat supply was switched off, but rose very rapidly depending on the amount of gas introduced. In contrast, the greater the gas supply in example i, the faster the temperature fell. The uptake of ethylene gas during an introduction period of 3 hours was 50 g in Example 2.
An Stelle der ungesättigten Kohlenwasserstofte können auch halogenierte Kohlenwasserstoffe verwendet werden:Halogenated hydrocarbons can also be used in place of the unsaturated hydrocarbons Hydrocarbons are used:
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1936B0176208 DE699607C (en) | 1936-11-12 | 1936-11-12 | Process for the alkylation of benzene or its homologues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1936B0176208 DE699607C (en) | 1936-11-12 | 1936-11-12 | Process for the alkylation of benzene or its homologues |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE699607C true DE699607C (en) | 1940-12-03 |
Family
ID=7007883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1936B0176208 Expired DE699607C (en) | 1936-11-12 | 1936-11-12 | Process for the alkylation of benzene or its homologues |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE699607C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2426665A (en) * | 1942-03-26 | 1947-09-02 | Universal Oil Prod Co | Alkylation of aromatic hydrocarbons |
-
1936
- 1936-11-12 DE DE1936B0176208 patent/DE699607C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2426665A (en) * | 1942-03-26 | 1947-09-02 | Universal Oil Prod Co | Alkylation of aromatic hydrocarbons |
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