EP1311465A1 - Procede de chloration de cycle d'ortho-xylol - Google Patents

Procede de chloration de cycle d'ortho-xylol

Info

Publication number
EP1311465A1
EP1311465A1 EP01969561A EP01969561A EP1311465A1 EP 1311465 A1 EP1311465 A1 EP 1311465A1 EP 01969561 A EP01969561 A EP 01969561A EP 01969561 A EP01969561 A EP 01969561A EP 1311465 A1 EP1311465 A1 EP 1311465A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
atoms
alkyl
substituted
independently
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.)
Withdrawn
Application number
EP01969561A
Other languages
German (de)
English (en)
Inventor
Franz-Josef Mais
Alexander Klausener
Heinrich Schrage
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Chemicals AG
Original Assignee
Bayer AG
Bayer Chemicals AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG, Bayer Chemicals AG filed Critical Bayer AG
Publication of EP1311465A1 publication Critical patent/EP1311465A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds

Definitions

  • the present invention relates to a process for the core chlorination of o-xylene to a mixture of 4-chloro-1,2-dimethylbenzene and 3-chloro-1,2-dimethylbenzene with elemental chlorine in the presence of a catalyst and a co-catalyst.
  • Mono-core chlorinated o-xylenes are valuable intermediates for the production of agro- and pharmaceutical active ingredients as well as for the production of intermediate products of polymers.
  • 4-chloro-l, 2-dimethylbenzene is the more valuable isomer, so a number of methods for increasing the proportion of 4-chloro-l, 2-dimethylbenzene have been described.
  • the proportion of 4-chloro-1,2-dimethylbenzene can be increased, for example using Fe + S 2 C1 2 to a ratio of 4-chloro-1,2-dimethylbenzene to 3- Chlorine-1,2-dimethylbenzene of 1.78: 1 (Chemical Abstracts CA 1988, No. 472737).
  • EP 126 669 AI describes the core chlorination of o-xylene with SbCl as Lewis acid and N-chlorocarbonylphenothiazine as cocatalyst. A ratio of 4-chloro-l, 2-dimethylbenzene to 3-chloro-l, 2-dimethylbenzene of 2.3: 1 is achieved.
  • a fundamentally different process consists in the core chlorination of o-xylene with chlorine in the presence of L-zeolites as catalysts.
  • KL zeolite in m
  • Dinitrobenzene as solvent gives a ratio of 4-chloro-1,2-dimethylbenzene to 3-chloro-1,2-dimethylbenzene of 3.87: 1 (Chemical Abstracts CA 1991, No. 514135).
  • 1,2-dichloroethane as solvent an isomer ratio of up to 11.73: 1 can even be achieved, but in this case over 60% of the o-xylene used is not reacted (J. Catal. 150, 1994, 430-433) ,
  • a disadvantage of carrying out the process in the presence of zeolites is the use of a solvent and the heterogeneous catalyst, as a result of which additional distillation and filtration steps are necessary when working up the reaction mixture.
  • the object of the present invention was to provide a process for the core chlorination of o-xylene using an easy-to-use catalyst system, the highest possible ratio of 4-chloro-l, 2-dimethylbenzene to 3-chloro-l, 2-dimethylbenzene should be achieved.
  • the object is achieved in a surprisingly simple way by using benzo-condensed thiazepines or thiazocines as co-catalysts.
  • the invention accordingly relates to a process for the core chlorination of o-xylene with elemental chlorine in the presence of Friedel-Crafts catalysts, the co-
  • Catalysts benzo-condensed thiazepines or thiazocines are used.
  • Suitable Friedel-Crafts catalysts for the process according to the invention are known as such. Examples include: antimony chlorides, antimony oxides, aluminum chloride, iron (II) chloride, iron (III) chloride, tellurium chlorides, lead chlorides,
  • Molybdenum chlorides tin chlorides, tungsten chlorides, titanium chlorides, zinc chlorides, boron trichloride and boron trifluoride.
  • Precursors for Friedel-Crafts catalysts for example the metals or semimetals antimony, iron, lead, tin, zinc, molybdenum, tellurium or aluminum or their oxides, sulfides, carbonyls or salts, e.g. B. Carbonates.
  • metals or semimetals antimony, iron, lead, tin, zinc, molybdenum, tellurium or aluminum or their oxides, sulfides, carbonyls or salts e.g. B. Carbonates.
  • Examples of possible elementary compounds are: antimony oxides, iron oxides, iron sulfides, lead sulfides, tin sulfides, zinc sulfides, iron carbonyls, molybdenum carbonyls and
  • Antimony chlorides, iron, iron oxides, iron sulfides, iron carbonyls and iron (III) chloride are preferably used as Friedel-Crafts catalysts in the process according to the invention.
  • Iron (HI) chloride is particularly preferred.
  • Friedel-Crafts catalysts and / or their precursors can be used individually or as any mixtures with one another.
  • the amount of the Friedel-Crafts catalyst or its precursor can be varied within wide limits. A catalyst effect can often already be seen with the addition of 0.0005% by weight. On the other hand, 5% by weight or more of the Friedel-Crafts catalyst can also be added, but such high amounts generally do not offer any advantage, but may result in the workup
  • the Friedel-Crafts catalyst is usually used in an amount of 0.001 to 1.0% by weight, preferably 0.005 to 0.5% by weight. All of these amounts are based on the amount of o-xylene used.
  • benzothiazepines of the formulas can be used as co-catalysts
  • R 1 , R 2 , R 3 , R 4 are the same or different and are hydrogen, hydroxy, amino, cyano, halogen, nitro, nitroso, sulfonyl, sulfoxyl, tosyl, mercapto, carboxyl, carboxyamide, carbalkoxy, dithiocarboxyl, thiocarboxyamide , Dithiocarbalkoxy, optionally substituted alkyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, acyloxy, alkylthio, arylthio, heteroarylthio,
  • acylthio, acyl, thioacyl or acylamino can furthermore form one or more saturated or unsaturated, optionally substituted isocyclic or heterocyclic carbon rings with up to 8 C atoms,
  • R 5 , R 6 , R 7 and R 8 are the same or different and have the meaning of R 1 to R 4 , with the exception that they cannot form rings with one another,
  • Y is hydrogen, optionally substituted alkyl, aryl, heteroaryl, acyl,
  • X 1 , X 2 , or X 3 each independently of the other means one of the following groups:
  • R 9 and R 10 are identical or different and have the meaning of R 5 to R 8 ,
  • Z has the meaning of Y, with the exception that Z cannot be H,
  • A is the annealing of an optionally substituted saturated isocyclic or heterocyclic ring with up to 8 C atoms
  • B is the annealing of an optionally substituted unsaturated isocyclic or heterocyclic ring with up to 8 C atoms
  • n 0 or 1
  • R 21 and R 22 independently of one another hydrogen, hydroxy, amino, cyano, halogen, nitro, carboxyl, halocarbonyl, carboxyamide, alkoxycarbonyl, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, acylthio, acyl,
  • R 23 represents hydrogen or chlorine and can furthermore form an annulated saturated, unsaturated or aromatic isocyclic or heterocyclic ring with 5 to 8 ring atoms with one of the radicals R 21 or R 22 with adjacent substitution and together with the substituted C atoms,
  • R 24 denotes hydrogen, alkyl, aryl, halogen, alkylthio, arylthio, alkoxy, aryloxy, amino, hydrazino, alkylhydrazino or phenylhydrazino,
  • n and o can independently assume the value 0 or 1, but n and o cannot simultaneously assume the value 0,
  • R, R and R independently of one another are hydrogen, alkyl, alkoxy, phenyl, acyloxy, cyano, halogen, carboxyl, alkoxycarbonyl, phenoxy or acyl.
  • each T7 T7 - - Q ten where R and R or R and R together with the substituted C atoms can form a saturated, unsaturated or aromatic isoeyclic or heterocyclic ring with 5 to 8 ring atoms,
  • R 26 , R 28 and R 210 independently of one another mean hydrogen, alkyl or halogen, where R and R or R and R together can form a double formation, with R 25 and R 26 furthermore together being double-bonded
  • R 211 is alkyl, aryl, acyl, alkylamino or arylamino
  • R 31 and R 32 independently of one another are hydrogen, hydroxy, amino, cyano, halogen, nitro, -Cs-alkyl, unsubstituted or substituted by R and R phenyl (with the exception of renewed substitution by R 31 - and R 32 - substituted Phenyl), Ci-Cs-alkoxy, phenoxy, Ci-C ⁇ -acyloxy, Ci-Cs-acyl or CrCs-alkoxycarbonyl, R 33 represents hydrogen or chlorine and, together with one of the radicals R 31 or R 32 and together with the substituted C atoms, can form an annellated saturated, unsaturated or aromatic isocyclic or heterocyclic ring with 5-8 ring atoms,
  • R 34 , R 36 and R 40 independently of one another are hydrogen, d-Cs-alkyl, phenyl which is unsubstituted or substituted by R 31 and R 32 (with the exception of the renewed substitution by R 31 - and R 32 -substituted phenyl), -Cs- Acyl, -Cs-alkoxycarbonyl, cyano, halogen, carboxyl, -Cs-alkoxy, Q-Cs-alkylthio, phenylthio, benzylthio, phenoxy or -Cs-acyloxy,
  • R 35 , R 37 and R 39 independently of one another are hydrogen, Q-Cs-alkyl, halogen, C 1 -C 8 -alkoxy or d-Cs-alkylthio,
  • R 38 is hydrogen, -CC 8 alkyl, unsubstituted or substituted by R 31 - and R 32 -substituted phenyl (with the exception of renewed substitution by R 31 - and R 32 -substituted phenyl), Ci-C 8 -acyl , CrC 8 thioacyl, halocarbonyl or d-Cs-alkoxy carbonyl and
  • p represents one of the numbers 0 or 1
  • pairs of substituents R 34 and R 35 , R 36 and R 37 , as well as R 39 and R 40, independently of one another, may mean double-bonded oxygen, sulfur or R 38 -substituted nitrogen, and furthermore
  • the pairs of substituents R 35 and R 36 and R 38 and R 39 can independently form a double bond, and furthermore the substituent pairs R 34 and R 37 and R 38 and R 39 can independently form 3- to 5-membered alkylene in which 1 or 2 C atoms can be replaced by oxygen, sulfur or R 38 -substituted nitrogen, and furthermore
  • R 40 can also assume the meaning hydrazino, CrCs-alkylhydrazino or phenylhydrazino,
  • R 41 and R 42 independently of one another are hydrogen, cyano, halogen, carboxyl,
  • R 43 represents hydrogen, alkyl or chlorine, preferably hydrogen, and furthermore with one of the radicals R 41 and R 42 in the case of adjacent substitution and together with the substituted C atoms, an annulated saturated, unsaturated or aromatic, isocyclic or heterocyclic ring with 5 can form up to 8 ring atoms,
  • R 44 and R 45 independently of one another are hydrogen, alkyl, aryl, halogen, alkoxy,
  • Aryloxy, acyl or acyloxy, preferably hydrogen, methyl, ethyl, propyl or isopropyl or together with the substituted carbon atoms can form a saturated or unsaturated, isocyclic or heterocyclic ring with 5 to 8 ring atoms,
  • R 46 is hydrogen, alkyl, aryl or silyl substituted by alkyl or aryl, preferably hydrogen and
  • q can have the value 0 or 1
  • R 51 and R 52 independently of one another are hydrogen, hydroxy, amino, cyano, halogen, nitro, alkylsulfonyl, phenylsulfonyl, alkylsulfoxyl, phenylsulfoxyl, tosyl, mercapto, carboxyl, halocarbonyl, carboxyamide, alkoxycarbonyl, thiocarboxyamide, alkyl, aryl, heteroaryl, alkoxy Mean aryloxy, heteroaryloxy, acyloxy, alkylthio, arylthio, heteroarylthio, acylthio, acyl, thioacyl or acylamino,
  • R 53 represents hydrogen or chlorine and, together with one of the radicals R 51 or R 52 and together with the substituted C atoms, can form an annellated saturated, unsaturated or aromatic isocyclic or heterocyclic ring with 5 to 8 ring atoms
  • R 54 denotes hydrogen, alkyl, aryl, heteroaryl, acyl, thioacyl, halocarbonyl or alkoxycarbonyl
  • X 51 and X 52 independently of one another represent double-bonded oxygen, sulfur or R 57 -substituted nitrogen, where R 57 has the meaning of R 5 with the exception of hydrogen,
  • r, s and t can independently assume the value 0 or 1 and
  • R 55 and R 56 can stand independently of one another on one or on two of the C atoms located in the 8 ring between the S and the N atom, provided that these C atoms are not occupied by X 51 or X 52 , and have the scope of meaning of R 51 or R 52 , where in the case of adjacent substitution also with the substituted C atoms, a saturated, unsaturated or aromatic isocyclic or heterocyclic ring having 5 to 8 ring atoms can be formed, and R 55 and R 56 together can also mean double-bonded oxygen or sulfur,
  • R 1 , R 2 , R 3 , R 4 and Y represent hydrogen
  • R 9 represents hydrogen, methyl, ethyl, propyl or isopropyl
  • co-catalysts are compounds of the formula (VI), where
  • R 1 , R 2 , R 3 , R 4 are the same or different and represent hydrogen, methyl, ethyl, propyl or isopropyl,
  • R and R are hydrogen
  • n the number 0
  • A means annealing a saturated isocyclic ring with 6 carbon atoms.
  • R 21 , R 22 , R 26 , R 28 are the same or different and represent hydrogen, methyl, ethyl, propyl or isopropyl, R 23 represents hydrogen,
  • R 24 denotes methylthio, ethylthio, propylthio or isopropylthio
  • n assumes the value 1 and
  • R 25 and R 27 independently of one another are hydrogen or C 1 -C 4 -alkyl, where they can form a saturated isocyclic ring with 6 ring atoms together with the substituted C atoms.
  • cocatalysts in combination with other elements or compounds not described as cocatalysts in the process according to the invention.
  • the co-catalysts can be used both individually and in a mixture of several of them.
  • the amounts of cocatalyst used can vary within wide limits. Amounts below 0.0001% by weight are less advantageous since the co-catalytic effect then diminishes. Amounts of 5% by weight or more of cocatalyst can even be used, but these large amounts generally offer no advantage, but may cause disadvantages in the workup.
  • the cocatalysts to be used according to the invention can therefore, for example, in an amount of 0.0001-1.0% by weight, preferably 0.0005-0.5% by weight, particularly preferably 0.001-0.1% by weight, each based on the amount of o-xylene used.
  • the molar ratio of Friedel-Crafts catalyst (s) or precursors thereof and co-catalyst (s) can be varied within wide limits in the process according to the invention. Is suitable for. B. a molar ratio of Friedel-Crafts catalysts or precursors thereof to cocatalyst from 100: 1 to 1:50, preferably 75: 1 to 1:10, particularly preferably 50: 1 to 1: 2.
  • the process according to the invention is advantageously carried out in the liquid phase. If necessary, an inert solvent can be used in dilution.
  • Suitable solvents are those which are not attacked by chlorine under the conditions of a core chlorination and are known to the person skilled in the art, for example methylene chloride, chloroform, carbon tetrachloride, acetic acid. It is preferred to work without solvent.
  • the amount of chlorine is preferably chosen so that a degree of chlorination of not significantly higher than 1 results.
  • the core chlorination to be carried out according to the invention can in principle be carried out at a temperature from the solidification point to the boiling point of the reaction mixture.
  • the reaction temperature is from - 30 to 120 ° C, preferably from - 10 to 100 ° C, particularly preferably from 0 to 70 ° C.
  • the reaction pressure can be normal, reduced or increased and is basically not critical. Normal pressure is preferred because of the inexpensive implementation. Increased pressure can be indicated, for example, if work is to be carried out above the boiling point of a low-boiling solvent. In this case, it is possible, for example, to work under the self-adjusting pressure of the reaction mixture.
  • the water content of the reaction mixture is generally not critical. It is preferred not to dry all feedstocks specifically, but to use them with the low water content with which they are usually present in chemical engineering. However, it is possible to specifically dry some or all of the substances in the reaction mixture. Usually, the water content of the feed materials should not be above the saturation limits of the respective feed materials. According to the invention, water contents in the chlorination mixture are preferred up to 250 ppm, particularly preferably up to 150 ppm, very particularly preferably up to 100 ppm.
  • the order in which the individual components are added to the reaction mixture is arbitrary for the practical implementation of the process according to the invention.
  • the process can be carried out both continuously and batchwise. For example, o-xylene is initially introduced at the desired reaction temperature, Friedel-Crafts and co-catalyst are added and the chlorine is metered in to the desired degree of chlorination.
  • the chlorination mixture can then be worked up directly by distillation. The catalyst components remain in the sump.
  • the process according to the invention allows the core chlorination of o-xylene with an increased proportion of 4-chloro-1,2-dimethylbenzene with the lowest application rates of Friedel-Crafts and co-catalysts. Since the process is preferably carried out without a solvent, simple work-up by direct distillation of the product mixture is possible.
  • Example 1 The procedure of Example 1 was repeated, using 44 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • Example 1 The procedure of Example 1 was repeated, using 70 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • Example 1 The procedure of Example 1 was repeated using 52 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • Example 1 The procedure of Example 1 was repeated using 57 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • Example 1 The procedure of Example 1 was repeated using 57 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • Example 1 The procedure of Example 1 was repeated, using 40 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • 1,2-dimethylbenzene 5.1% dichlorinated o-xylenes and 0.7% unknown products.
  • the ratio of 4-chloro-1,2-dimethylbenzene to 3-chloro-1,2-dimethylbenzene was 2.73.
  • Example 1 The procedure of Example 1 was repeated, using 55 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • Example 1 The procedure of Example 1 was repeated, using 49 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • Example 1 The procedure of Example 1 was repeated, using 53 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • Example 1 The procedure of Example 1 was repeated, using 55 ppm of the cocatalyst of the formula instead of the cocatalyst there
  • Example 1 The procedure of Example 1 was repeated, using 43 ppm of the cocatalyst of the formula instead of the cocatalyst there

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé permettant la chloration de cycle d'o-xylol avec du chlore élémentaire en présence d'un catalyseur de Friedel-Craft et d'un co-catalyseur, des thiazépines ou thiazocines benzocondensées étant utilisées en tant que co-catalyseur.
EP01969561A 2000-08-14 2001-08-01 Procede de chloration de cycle d'ortho-xylol Withdrawn EP1311465A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10039722A DE10039722A1 (de) 2000-08-14 2000-08-14 Verfahren zur Kernchlorierung von ortho-Xylol
DE10039722 2000-08-14
PCT/EP2001/008889 WO2002014245A1 (fr) 2000-08-14 2001-08-01 Procede de chloration de cycle d'ortho-xylol

Publications (1)

Publication Number Publication Date
EP1311465A1 true EP1311465A1 (fr) 2003-05-21

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EP01969561A Withdrawn EP1311465A1 (fr) 2000-08-14 2001-08-01 Procede de chloration de cycle d'ortho-xylol

Country Status (5)

Country Link
US (1) US20020049357A1 (fr)
EP (1) EP1311465A1 (fr)
AU (1) AU2001289781A1 (fr)
DE (1) DE10039722A1 (fr)
WO (1) WO2002014245A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10242223A1 (de) 2002-09-12 2004-03-25 Clariant Gmbh Verfahren zur Hydrodechlorierung von kernchlorierten ortho-Xylolen
DE10242224A1 (de) 2002-09-12 2004-03-25 Clariant Gmbh Verfahren zur Kernchlorierung von ortho-Xylol
US8710045B2 (en) 2004-01-22 2014-04-29 The Trustees Of Columbia University In The City Of New York Agents for preventing and treating disorders involving modulation of the ryanodine receptors
DE102004010830A1 (de) * 2004-02-27 2005-09-15 Bioagency Ag Neue 1,4-Benzooxazepane oder 1,4-Benzothiazepane und Derivate
US20100028439A1 (en) * 2005-05-23 2010-02-04 Elan Pharma International Limited Nanoparticulate stabilized anti-hypertensive compositions

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2545004B1 (fr) * 1983-04-29 1987-04-17 Ugine Kuhlmann Derive n substitue de la phenothiazine comme catalyseur de chloration sur le noyau des hydrocarbures aromatiques
DE3718060A1 (de) * 1987-05-28 1988-12-08 Bayer Ag Verfahren zur kernchlorierung von aromatischen kohlenwasserstoffen
DE3800386A1 (de) * 1988-01-09 1989-07-20 Bayer Ag Verfahren zur herstellung von benzothiazepinon-derivaten
EP0340581B1 (fr) * 1988-05-06 1992-03-18 Bayer Ag Procédé de chloruration dans le noyau d'hydrocarbures aromatiques
DE58901634D1 (de) * 1988-11-05 1992-07-16 Bayer Ag Verfahren zur kernchlorierung von aromatischen kohlenwasserstoffen.
DE4004821A1 (de) * 1990-02-16 1991-08-22 Bayer Ag Verfahren zur kernchlorierung von aromatischen kohlenwasserstoffen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0214245A1 *

Also Published As

Publication number Publication date
AU2001289781A1 (en) 2002-02-25
WO2002014245A1 (fr) 2002-02-21
US20020049357A1 (en) 2002-04-25
DE10039722A1 (de) 2002-02-28

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