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WO1997043041A1 - Catalyseur regioselectif de chloration nucleaire pour hydrocarbures aromatiques et procede de chloration nucleaire - Google Patents

Catalyseur regioselectif de chloration nucleaire pour hydrocarbures aromatiques et procede de chloration nucleaire Download PDF

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Publication number
WO1997043041A1
WO1997043041A1 PCT/JP1997/001609 JP9701609W WO9743041A1 WO 1997043041 A1 WO1997043041 A1 WO 1997043041A1 JP 9701609 W JP9701609 W JP 9701609W WO 9743041 A1 WO9743041 A1 WO 9743041A1
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Prior art keywords
integer
phenothiazine
group
benzene
chlorination
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Ceased
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PCT/JP1997/001609
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English (en)
Japanese (ja)
Inventor
Shigeru Mizusawa
Kazuhiko Sunagawa
Toshio Hozumi
Tsugio Nonaka
Toshiharu Matsuda
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Kureha Corp
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Kureha Corp
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Priority to JP54073297A priority Critical patent/JP3818321B2/ja
Publication of WO1997043041A1 publication Critical patent/WO1997043041A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0231—Halogen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • 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 catalyst for regioselective chlorination of aromatic hydrocarbons and a method for regioselective chlorination of aromatic hydrocarbons using the same.
  • Nuclear chlorinated aromatic hydrocarbons are important compounds as raw materials for polymers, pharmaceuticals and agricultural chemicals. Accordingly, various proposals have been made for a technique for nuclear chlorination of aromatic hydrocarbons with good regioselectivity.
  • JP 59 - The 206,051 discloses, 1 0- ⁇ reel carbonyl - 1 0H- phenothiazine, 10- Harokarubo two Lou 1 0H- Fuenochia gin and 1 0- CH T X, CO- 1 OH- phenothiazine [X is Black
  • JP-A-60-125251 describes 10-lower alkylcarbonyl 10H-phenothiazine, 10-arylcarbonyl 10H-phenothiazine and 10-haloalkylcarbonyl-1 10H-phenothiazine. Have been.
  • the present invention has the following structural features.
  • the first invention relates to a catalyst for regioselective chlorination of aromatic hydrocarbons, and more specifically relates to 10H-phenothiazine-10-carboxylic acid fuunyl esters represented by the following formula (I): And Lewis acids.
  • X represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or a cyano group,
  • n an integer of 0 to 5, and when n is greater than 2, Xs may be the same or different; s represents an integer of 0 to 5, t represents an integer of 0 to 4, u represents an integer of 0 to 4, and (n + s) is 5 or less. )
  • the second invention relates to 10H-phenothiazine-10-carbonic acid phenyl esters of the following formula (I).
  • X represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or a cyano group,
  • n an integer of 0 to 5, and when n is greater than 2, Xs may be the same or different;
  • s represents an integer of 0 to 5
  • t represents an integer of 0 to 4
  • u represents an integer of 0 to 4
  • (n + s) is 5 or less.
  • the third invention relates to a method for regioselective nuclear chlorination of aromatic hydrocarbons, which comprises, as a catalyst, 10H-phenothiazine-10-carboxylic acid phenyl ester represented by the above formula (I). Characterized in that aromatic hydrocarbons are chlorinated by using a combination of a compound and a Lewis acid.
  • the regioselective nuclear chlorination reaction of aromatic hydrocarbons of the present invention is a nuclear chlorination reaction of aromatic hydrocarbons serving as a substrate on a benzene ring, wherein a specific reaction is carried out for a substituent already existing.
  • a reaction that selectively nucleates nucleus For example, in nuclear chlorination, it means a para-selective chlorination reaction in benzene and toluene, which exhibit ortho and para orientation.
  • Examples of the substituent already existing in the aromatic hydrocarbon include a halogen atom selected from fluorine, chlorine, bromine and iodine, an alkyl group having 1 to 6 carbon atoms, preferably methyl, ethyl, propyl, Alkyl groups having 1 to 4 carbon atoms, including 1-methylethyl and 1,1-dimethylethyl, and alkoxy groups having 1 to 6 carbon atoms, preferably carbon atoms including methoxy, ethoxy, propoxy and (1-methylethyl) oxy
  • Examples thereof include an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and preferably an alkylthio group having 1 to 4 carbon atoms including methylthio and ethylthio.
  • the aromatic hydrocarbons to be nuclear-chlorinated according to the present invention are those in which the benzene ring is substituted with one to three of the above substituents. Further, a part of the alkyl group having 1 to 6 carbon atoms as a substituent may form a ring by a single bond with the ortho position on the benzene ring, and may form a hetero atom such as oxygen or sulfur. And may combine with each other to form a ring.
  • a part of the alkoxy group having 1 to 6 carbon atoms or a part of the alkylthio group having 1 to 6 carbon atoms as a substituent may form a ring by a single bond with the ortho position on the benzene ring. Also, they may be bonded via a heteroatom such as oxygen or sulfur to form a ring.
  • a compound consisting of a benzene ring and a ring containing oxygen and sulfur fused to the benzene ring is usually classified as a heterocyclic compound and is distinguished from aromatic hydrocarbons.
  • these compounds are also defined as being included in the range of aromatic hydrocarbons as modified substituents on the benzene ring.
  • Aromatic hydrocarbons that exhibit selectivity can also be used as substrates in the present invention.
  • the 10 H-phenothiazine-10-carboxylic acid phenyl esters represented by the formula (I) used as a catalyst in the present invention are, for example, substituted as defined in JP-A-59-26051. It has the structural similarity to a compound having a group, and 10-benzoyl-10H-phenothiazine described in JP-A-60-125251.
  • the compound represented by the formula (I) is a compound having a substituent having a structure in which an oxygen atom is inserted between the phenyl group and the carbonyl group of the benzoyl group at the 10-position.
  • Nzoruil 10 H—Phenothiazines differ in structure. Therefore, the present invention is a novel invention, since no proposal has been made on regioselective nuclear chlorination using the compound represented by the above formula (I) of the present invention.
  • the compounds of the present invention represented by the formula (I) show that the regioselectivity of nuclear chlorination thereby is unexpectedly large from the structurally similar 10-benzoyl 10H-phenothiazine.
  • the regioselectivity of nuclear chlorination by the compound represented by the formula (I) does not decrease even when nuclear chlorination is performed at a reaction temperature exceeding 45 ° C.
  • the degree of chlorination the number of moles of chlorine substituted with 1 mole of aromatic hydrocarbons as a substrate in the nuclear chlorination reaction of the present invention
  • the degree of chlorination the number of moles of chlorine substituted with 1 mole of aromatic hydrocarbons as a substrate in the nuclear chlorination reaction of the present invention
  • the compound represented by the formula (I) of the present invention is composed of 10H-phenothiazines (11) and phenyl chloroformates (111) as shown in the following reaction formula.
  • Chem. Ber., 11 1 , 1453-63 (1 978) (10 H-phenothiazine and phenyl chloroformate in benzene or xylene. It can be produced by an operation in accordance with the method described in).
  • the compound having the desired values of s, t and u is, as shown in the above reaction formula, a fuunothiazine (II) having the desired values of t and U and a chloroform having the desired value of s. It can be derived from acid humylates (111).
  • compounds (I) having less than the desired values of s, t and u can be converted to the desired values of s by nuclear chlorination (usually using chlorine or sulfuryl chloride and a Lewis acid). , T and u can also be derived.
  • n in the compound represented by the formula (I) 0 or 1 is preferable.
  • X is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and more preferably a fluorine atom, a chlorine atom, a methyl group and a methoxy group.
  • s is preferably an integer of 0 to 2
  • t and u are each preferably an integer of 0 to 3.
  • the nuclear chlorination of the present invention requires the use of a Lewis acid.
  • the Lewis acid used may be a Lewis acid generated in a reaction system from a metal element or a compound having the metal element as a constituent element.
  • Lewis acids ferric chloride, aluminum chloride It is preferred to use at least one Lewis acid selected from the group consisting of antimony and antimony trichloride.
  • benzene is used as the aromatic hydrocarbon as the substrate to be chlorinated in the present invention, since benzene formed in the reaction system from benzene is the substrate of the present invention, and benzene can also be used as the substrate.
  • Toluene is used as the aromatic hydrocarbon as the substrate to be chlorinated in the present invention, since benzene formed in the reaction system from benzene is the substrate of the present invention, and benzene can also be used as the substrate.
  • Toluene Toluene
  • p-xylene (1-chloro-2.5-dimethylbenzene generated from p-xylene in the reaction system is the substrate of the present invention, p-xylene can also be used), Preferably, at least one selected from the group consisting of toluene and o-dichlorobenzene and 1-chloro-2,5-dimethylbenzene is used.
  • chlorobenzene In the nuclear chlorination reaction of the present invention, chlorobenzene, dichlorobenzene, cyclotoluene, 1,2-dichloroethane, 1,2-dichloropropane, dichloromethane, chloroform, Halogenated hydrocarbons such as carbon chloride can be used as the reaction solvent.
  • the above-mentioned aromatic hydrocarbons and the above-mentioned halogenated hydrocarbons which are substrates can also be used as a solvent in a nuclear chlorination reaction of the compound represented by the formula (1).
  • the nuclear chlorinated isomer formed depends on the use ratio of the solvent and Z or Lewis acid to the compound of the formula (I) and the reaction conditions such as the chlorination rate. Can be controlled. For example, using a Lewis acid in an amount such that the molar ratio of the compound of formula (1) / ⁇ Lewis acid is 1-3 (preferably 1.5-2), the concentration of the compound of formula (I) If the nuclear chlorination reaction is carried out using an amount of a solvent that gives a concentration lower than 0.5% (preferably 2%), chlorine will also bind to position 1 of the phenothiazine ring. Can give priority to the generation of certain isomers.
  • the nuclear chlorination reaction of the compound represented by the formula (I) is usually carried out by fuunothiazine
  • the method for selective nuclear chlorination of the present invention is characterized in that the reaction is carried out by using the compound represented by the formula (I) and Lewis acids in combination as a catalyst.
  • the product is removed by distillation, the substrate is added again to the supernatant, and the substrate is re-added, and a nuclear reaction is performed by a repeated reaction method, or a part of the reaction mixture is added to the substrate to perform the nuclear chlorination.
  • Reaction methods are also possible. In the case of these reaction methods, the compound represented by the formula (I) and / or Lewis acids may be added during the reaction step.
  • the amount (millimol) of the Lewis acid to be used per 1 mol of the aromatic hydrocarbon as the substrate is from 0.03 to 6, preferably from 0.09 to 4, more preferably from 0.15 to 3 It is.
  • the amount of the compound represented by the formula (I) to be used per 1 mol of the Lewis acid (millimol) is from 0.3 to 20, preferably from 0.6 to: L5, and more preferably from 1 to 5. : L 0.
  • the nuclear chlorination in the present invention is carried out using a necessary or excess amount of gaseous or liquid chlorine, and is reacted in an amount corresponding to the following degree of chlorination.
  • the chlorination degree (in the nuclear chlorination reaction of the present invention, the number of moles of chlorine replaced by 1 mole of aromatic hydrocarbons as a substrate) is from 0.2 to 1.5, preferably from 0.3 to 1. 2, more preferably 0.4-1. Therefore, when benzene p-xylene is used as a substrate, the chlorination degree is 1.2
  • the reaction temperature in the present invention is preferably from 1 to 90 ° C, more preferably from 45 to 75 ° C.
  • ferric chloride is used in combination with 10H-phenothiazine 10-phenylphenyl carboxylate (used in Reference Production Example 1 below)]
  • ferric chloride is used in combination with 10H-phenothiazine-10-carboxylic acid (4-chlorofurnyl) ester (prepared in Production Example 8 below)]
  • ferric chloride is used in combination with 10H-phenothiazine 10-carboxylic acid (4-methylphenyl) ester (the one prepared in Production Example 9 below)]
  • ferric chloride is used in combination with 10H-phenothiazine- 10-hydroxycarboxylic acid (4-methoxyphenyl) ester (used in Production Example 10 below)]
  • the temperature was raised to 50 ° C, gaseous chlorine was blown at the same temperature, and chlorination was performed over a period of 8 hours to a chlorination degree of 1.58 based on benzene.
  • the reaction mixture was analyzed by gas chromatography, and it was confirmed that the reaction mixture had the following composition. Parentheses indicate the content (%) of each component.
  • ⁇ p + (o + p) x 100 ⁇ calculated from the above composition are as follows: dichloro-mouth benzene (52.54), tricyclo-mouth benzene (0.11)
  • ferric chloride is used in combination with 10-benzylazo 10H-phenothiazine (used in Reference Production Example 2 below)]
  • ⁇ p ⁇ (o + p) 100 ⁇ calculated from the above composition was 60 (%).
  • the yield determined by the marker method was 90.2%.
  • the reaction solution was cooled to room temperature, and benzene was distilled off under reduced pressure.
  • the crude crystals were recrystallized from ethyl acetate. Precipitated crystals are collected and dried under vacuum to obtain the desired product
  • the yield determined by the Marker-1 method was 79.3%.
  • the reaction solution was cooled to room temperature, and benzene was distilled off under reduced pressure.
  • the crude crystals were recrystallized from ethyl acetate.
  • the precipitated crystals were collected and dried under vacuum to obtain 6.2 g of the desired product.
  • the yield determined by the marker method was 78.0%.
  • the reaction solution was cooled to room temperature, and benzene was distilled off under reduced pressure.
  • the crude crystals were recrystallized from ethyl acetate.
  • the precipitated crystals were collected and dried under vacuum to obtain 5.8 g of the desired product.
  • the yield determined by the marker method was 84.1%.
  • Gasket GC manufactured by Shimadzu Corporation GC-14B Column: Glass column outer diameter 5 mm, inner diameter 3 mm, length 2 m
  • Carrier gas Helium, 120 kPa (at 280 ° C)
  • Detector FID (FID condition, hydrogen 55 kPa, air 50 kPa)
  • Retention time min
  • Tetralolor 10 H Phonothiazine 10 —Caprolubonic acid (4—Chlorophenyl) ester [mixture]
  • the distillation residue was dissolved in ethyl acetate, washed twice with saturated saline, and then separated. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a crystalline product. The crystal was dissolved in acetonitrile, fractionated by ODS column chromatography and silica column chromatography, and recrystallized from acetonitrile to obtain the following nucleated chloride.
  • the nuclei chloride of 10H-phenothiazine 110-carboxylic acid phenyl ester had 3 to 6 chlorine atoms on the funothiazine ring and the phenyl group.
  • Ethylbenzene (6.05), onolesok (35.60), parachloroethylbenzene (58.35)
  • the reaction solution was cooled to room temperature, and benzene was distilled off under reduced pressure.
  • the crude crystals were recrystallized from ethyl acetate.
  • the precipitated crystals were collected and dried under vacuum to obtain 7.21 g of the desired product.
  • the benzene layer was dried over anhydrous sodium sulfate, and benzene was distilled off under reduced pressure to obtain a crude crystal.
  • the crude crystals were recrystallized from benzene to give 6.68 g of needles.
  • the combined use of the 10H-phenothiazine-phenylene phenylesters of the present invention and Lewis acids is useful as a catalyst for regioselective nuclear chlorination of aromatic hydrocarbons. Furthermore, the catalyst for regioselective nuclear chlorination by this combination has the feature that the regioselectivity does not decrease even if the nuclei chlorination is carried out at a reaction temperature exceeding 45 ° C. This has the advantage of improving selectivity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Abstract

Nouveaux phényl-10H-phénothiazine-10-carboxylates représentés par la formule générale (I), dont les combinaisons avec des acides de Lewis sont utiles en tant que catalyseurs régiosélectifs de chloration nucléaire pour des hydrocarbures aromatiques. Ces catalyseurs présentent un avantage basé sur le fait que la régiosélectivité n'est pas diminuée, même quand la réaction de chloration nucléaire est effectuée à une température supérieure à 45 °C, et que la régiosélectivité est augmentée avec un degré croissant de chloration. Dans cette formule, X représente halogéno, alkyle C1-C4, alcoxy C1-C4, nitro ou cyano et n est un entier de 0 à 5, à condition que, quand n est égal ou supérieur à 2, les X puissent être semblables ou différents les uns des autres; s est un entier de 0 à 5; t est un entier de 0 à 4 et u est un entier de 0 à 4, à condition que le total de la somme de n et de s soit égal ou inférieur à 5.
PCT/JP1997/001609 1996-05-14 1997-05-14 Catalyseur regioselectif de chloration nucleaire pour hydrocarbures aromatiques et procede de chloration nucleaire Ceased WO1997043041A1 (fr)

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JP54073297A JP3818321B2 (ja) 1996-05-14 1997-05-14 芳香族炭化水素類の位置選択的核塩素化用触媒および核塩素化方法

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JP14513496 1996-05-14

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004022512A1 (fr) * 2002-09-04 2004-03-18 Kureha Chemical Industry Company, Limited Procede de production de p-dichlorobenzene
WO2006009662A3 (fr) * 2004-06-16 2006-07-27 Gen Electric Procede permettant de recycler des compositions catalytiques pour halogenation de noyau aromatique
JP2010100571A (ja) * 2008-10-24 2010-05-06 Tosoh Corp パラジクロロベンゼンの製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL246553B1 (pl) 2022-11-04 2025-02-10 Pcc Rokita Spolka Akcyjna Sposób selektywnego otrzymywania paradichlorobenzenu z ulepszonym odzyskiem układu katalitycznego

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60125251A (ja) * 1983-12-13 1985-07-04 Ihara Chem Ind Co Ltd アルキルベンゼンの核ハロゲン化用触媒
JPH08267928A (ja) * 1995-03-30 1996-10-15 New Oji Paper Co Ltd 感熱記録体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60125251A (ja) * 1983-12-13 1985-07-04 Ihara Chem Ind Co Ltd アルキルベンゼンの核ハロゲン化用触媒
JPH08267928A (ja) * 1995-03-30 1996-10-15 New Oji Paper Co Ltd 感熱記録体

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004022512A1 (fr) * 2002-09-04 2004-03-18 Kureha Chemical Industry Company, Limited Procede de production de p-dichlorobenzene
CN1301945C (zh) * 2002-09-04 2007-02-28 株式会社吴羽 对－二氯苯的制造方法
US7211704B2 (en) 2002-09-04 2007-05-01 Kureha Corporation Method for producing p-dichlorobenzene
WO2006009662A3 (fr) * 2004-06-16 2006-07-27 Gen Electric Procede permettant de recycler des compositions catalytiques pour halogenation de noyau aromatique
US7863209B2 (en) 2004-06-16 2011-01-04 Sabic Innovative Plastics Ip B.V. Methods for recycling catalyst compositions for aromatic ring halogenation
EP2305380A1 (fr) * 2004-06-16 2011-04-06 SABIC Innovative Plastics IP B.V. Procédés de génération et de recyclage de compositions de catalyseur d'halogénure métallique pour l'halogénation d'un cycle aromatique
JP2010100571A (ja) * 2008-10-24 2010-05-06 Tosoh Corp パラジクロロベンゼンの製造方法

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