CN114105779A - Preparation method of asymmetric diaryl substituted p-phenylenediamine compound - Google Patents

Preparation method of asymmetric diaryl substituted p-phenylenediamine compound Download PDF

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CN114105779A
CN114105779A CN202010904961.0A CN202010904961A CN114105779A CN 114105779 A CN114105779 A CN 114105779A CN 202010904961 A CN202010904961 A CN 202010904961A CN 114105779 A CN114105779 A CN 114105779A
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compound
formula
fecl
reaction
hydroquinone
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邢金国
郭湘云
祁琦
刘燕祥
唐志民
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Sennics Co ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines
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    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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    • C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
    • C07C215/82—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the amino groups further bound to a carbon atom of another six-membered aromatic ring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
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    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention provides a preparation method of an asymmetric diaryl substituted p-phenylenediamine compound, which comprises the following stepsA structure according to formula a, the method comprising: (1) in a supported FeCl3Reacting hydroquinone with a compound of formula B in the presence of a catalyst to obtain a compound of formula C; and (2) in anhydrous FeCl3In the presence of a compound of formula C and a compound of formula D to give a compound of formula a; in formulas A-D, each group is as defined herein. The method can be used for efficiently and conveniently preparing the asymmetric diaryl substituted p-phenylenediamine compound.

Description

Preparation method of asymmetric diaryl substituted p-phenylenediamine compound
Technical Field
The invention belongs to the field of rubber anti-aging agents, and particularly relates to an asymmetric diaryl substituted p-phenylenediamine compound and a preparation method thereof.
Background
The research of the existing literature indicates that diaryl substituted p-phenylenediamine has long-acting anti-aging effect, and compared with widely used anti-aging agent 4020, diaryl p-phenylenediamine is not easy to volatilize and is extraction resistant, and the protection effect is more durable. For example, the antioxidant H and the antioxidant 3100 are typical after-aging long-acting antioxidants, and can supplement the disadvantages that the antioxidants 4010 and 4020 have good early-stage aging resistance and slightly poor later-stage aging resistance.
However, the antioxidant H is N, N' -diphenyl-p-phenylenediamine with a symmetrical structure, has stronger crystallinity and poorer compatibility with rubber, the using amount is not more than 1 part, otherwise, the antioxidant H is easy to precipitate to generate a blooming phenomenon, so that the color change pollution of the tire surface is caused, and the protection on the aging of the rubber is lost quickly. Blooming is a phenomenon in which a liquid or solid compounding agent in the rubber migrates to the surface and precipitates. The antioxidant 3100 is a mixture of approximately 45% of a symmetrical diaryl p-phenylenediamine (23% of N, N ' -diphenyl p-phenylenediamine and 22% of N, N ' -di (tolyl) p-phenylenediamine) and 45% of an asymmetrical N-phenyl-N ' -tolyl p-phenylenediamine, and therefore the antioxidant 3100 is also liable to cause blooming, and the amount is usually not more than 1.5 parts.
U.S. Pat. No. 3,34, 460 discloses a process for synthesizing diaryl hydroquinone anti-aging agent, which comprises, preparing anti-aging agent H from hydroquinone and aniline as reaction raw materials, using Lewis acid such as anhydrous ferric chloride as catalyst, refluxing toluene under high temperature and micro positive pressure to carry water, using the carried water amount as the mark for measuring the reaction end, cooling after the reaction end, adding saturated sodium carbonate aqueous solution to quench the reaction, filtering out organic phase, heating and distilling under reduced pressure to remove low-boiling-point substances, filtering while hot to remove inorganic substances, cooling and solidifying. If a mixture of aniline and o-toluidine is reacted with hydroquinone, a three-component mixture is obtained, namely the antioxidant 3100. According to the reaction principle, the single-component asymmetric diaryl p-phenylenediamine cannot be obtained according to the process.
EP0588060A2 discloses the synthesis of N-alkyl substituted phenyl-p-phenylenediamine, which is then condensed and dehydrogenated with different alkyl substituted cyclohexanones to form asymmetric diaryl substituted p-phenylenediamine. In the preparation method, the alkyl substituted cyclohexanone is difficult to synthesize and has higher cost, and a hydrogen acceptor is consumed, so that a large amount of byproducts are easily generated.
The U.S. Pat. No. 4, 4804783A discloses the preparation of the target product by the synthesis of N-alkyl substituted phenyl-p-phenylenediamine followed by condensation with different alkyl substituted phenols. The preparation method needs cyclohexanone as a hydrogen transfer reagent, has harsh reaction conditions and is not easy to carry out, and particularly, alkyl substituted phenol is difficult to react and can hardly obtain a product.
Therefore, the preparation method of the asymmetric diaryl substituted p-phenylenediamine compound with low cost, less side reaction, non-harsh reaction conditions and high yield is needed in the field.
Disclosure of Invention
In order to solve the problems, the invention provides a novel method for preparing asymmetric diaryl substituted p-phenylenediamine compounds. The asymmetric diaryl substituted p-phenylenediamine compound can be usually used as an anti-aging agent for rubber products, particularly rubber tires, and can prevent degradation and deterioration of the rubber products or the rubber tires caused by light, heat, oxygen, fatigue and the like in the long-term use process. Compared with the existing method for preparing the asymmetric diaryl substituted p-phenylenediamine compound, the method has the advantages of low cost, few side reactions, mild reaction conditions, high yield and the like.
Specifically, the invention provides a method for preparing an asymmetric diaryl substituted p-phenylenediamine compound, wherein the asymmetric diaryl substituted p-phenylenediamine compound has a structure shown in the following formula A:
Figure BDA0002661089040000021
in the formula A, each RaIndependently selected from hydrogen and C1-C6 alkyl, m is an integer selected from 0-5, each RbIndependently selected from hydrogen and C1-C6 alkyl, n is an integer selected from 0-5; the compound of formula A does not include (R)a)mSubstituted phenyl and (R)b)nSubstituted phenyl moieties of the same general formula;
the method comprises the following steps:
(1) in a supported FeCl3Reacting hydroquinone with a compound of formula B in the presence of a catalyst to give a compound of formula C:
Figure BDA0002661089040000031
(2) in anhydrous FeCl3To a compound of formula D in the presence of a compound of formula C to give a compound of formula a:
Figure BDA0002661089040000032
wherein in the compound of formula B, each RaIndependently selected from hydrogen and C1-C6 alkyl, and m is an integer selected from 0-5; in the compound of formula D, each RbIndependently selected from hydrogen and C1-C6 alkyl, n is an integer selected from 0-5; the compound of formula B is not the same as the compound of formula D.
In one or more embodiments, the supported FeCl3The catalyst is FeCl3And (3) a catalyst obtained by supporting on a carrier.
In one or more embodiments, the reaction of step (1) is carried out in a non-polar solvent.
In one or more embodiments, the reaction temperature of step (1) is from 200 to 240 ℃.
In one or more embodiments, the supported FeCl added in step (1)3FeCl contained in the catalyst3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.08-0.4): 1.
in one or more embodiments, the molar ratio of the compound of formula B added in step (1) to the hydroquinone added in step (1) is (0.8-1.2): 1.
in one or more embodiments, the reaction of step (1) is carried out in an inert gas atmosphere.
In one or more embodiments, the reaction of step (2) is carried out in a non-polar solvent.
In one or more embodiments, the reaction temperature of step (2) is 230 to 270 ℃.
In one or more embodiments, the anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.1-0.5): 1.
in one or more embodiments, the molar ratio of the compound of formula D added in step (2) to the hydroquinone added in step (1) is (1.0-1.8): 1.
in one or more embodiments, the reaction of step (2) is carried out in an inert gas atmosphere.
In one or more embodiments, the supported FeCl3The carrier of the catalyst is selected from hydrogen type molecular sieve, active silicon oxide and active aluminum oxide.
In one or more embodiments, the supported FeCl3In the catalyst, FeCl3The mass ratio of the carrier to the carrier is 1 (5-10).
In one or more embodiments, the reaction of step (1) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane.
In one or more embodiments, the reaction temperature of step (1) is 220 to 230 ℃.
In one or more embodiments, the supported FeCl added in step (1)3FeCl contained in the catalyst3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.1-0.25): 1.
in one or more embodiments, the molar ratio of the compound of formula B added in step (1) to the hydroquinone added in step (1) is (0.9-1.1): 1.
in one or more embodiments, the reaction of step (1) is carried out in a nitrogen atmosphere.
In one or more embodiments, the reaction of step (2) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane.
In one or more embodiments, the reaction temperature of step (2) is 240 to 260 ℃.
In one or more embodiments, the anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.2-0.3): 1.
in one or more embodiments, the molar ratio of the compound of formula D added in step (2) to the hydroquinone added in step (1) is (1.2-1.5): 1.
in one or more embodiments, the reaction of step (2) is carried out in a nitrogen atmosphere.
In one or more embodiments, the supported FeCl3The carrier of the catalyst is selected from hydrogen type molecular sieve, active silicon oxide and active aluminum oxide; the supported FeCl3In the catalyst, FeCl3The mass ratio of the carrier to the carrier is 1 (5-10); the reaction of step (1) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane; the reaction temperature of the step (1) is 220-230 ℃; in the reaction system of the step (1), supported FeCl3FeCl contained in the catalyst3The molar ratio of the hydroquinone is (0.1-0.25): 1, the molar ratio of the compound of formula B to hydroquinone is (0.9-1.1): 1; the reaction of the step (1) is carried out in a nitrogen atmosphere; the reaction in the step (2) is carried out in toluene,Xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane; the reaction temperature of the step (2) is 240-260 ℃; anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.2-0.3): 1; the molar ratio of the compound of formula D added in the step (2) to the hydroquinone added in the step (1) is (1.2-1.5): 1; and the reaction of step (2) is carried out in a nitrogen atmosphere.
The present invention also provides a process for preparing a compound of formula I:
Figure BDA0002661089040000051
in the formula I, R1、R3Each independently is hydrogen or C1-C6 alkyl; r2Is C1-C6 alkyl; compounds of formula I not including R1、R2Substituted phenyl and R3Substituted phenyl moieties of the same general formula;
the method comprises the following steps:
(1) in a supported FeCl3Reacting hydroquinone with a compound of formula II in the presence of a catalyst to give a compound of formula III:
Figure BDA0002661089040000052
(2) in anhydrous FeCl3To obtain a compound of formula I by reacting a compound of formula III with a compound of formula IV in the presence of:
Figure BDA0002661089040000053
wherein in the compound of formula II, R1、R2Each independently is hydrogen or C1-C6 alkyl; in the compound of formula IV, R3Is C1-C6 alkyl; the compound of formula II is not the same as the compound of formula IV; or
The method comprises the following steps:
(1) under loadFeCl of type3Reacting hydroquinone with a compound of formula IV in the presence of a catalyst to give a compound of formula III':
Figure BDA0002661089040000061
(2) in anhydrous FeCl3Reacting a compound of formula III' with a compound of formula II in the presence of:
Figure BDA0002661089040000062
wherein in the compound of formula II, R1、R2Each independently is hydrogen or C1-C6 alkyl; in the compound of formula IV, R3Is C1-C6 alkyl; the compound of formula II is not the same as the compound of formula IV.
In one or more embodiments of the process for preparing a compound of formula I, the supported FeCl3The catalyst is FeCl3And (3) a catalyst obtained by supporting on a carrier.
In one or more embodiments of the process for preparing compounds of formula I, the reaction of step (1) is carried out in a non-polar solvent.
In one or more embodiments of the process for preparing the compound of formula I, the reaction temperature of step (1) is 200 to 240 ℃.
In one or more embodiments of the process for preparing a compound of formula I, the supported FeCl added in step (1)3FeCl contained in the catalyst3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.08-0.4): 1.
in one or more embodiments of the process for preparing the compound of formula I, the molar ratio of the compound of formula II or the compound of formula IV added in step (1) to the hydroquinone added in step (1) is (0.8-1.2): 1.
in one or more embodiments of the process for preparing the compound of formula I, the reaction of step (1) is carried out in an inert gas atmosphere.
In one or more embodiments of the process for preparing compounds of formula I, the reaction of step (2) is carried out in a non-polar solvent.
In one or more embodiments of the process for preparing the compound of formula I, the reaction temperature of step (2) is 230 to 270 ℃.
In one or more embodiments of the process for preparing the compound of formula I, anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.1-0.5): 1.
in one or more embodiments of the process for preparing the compound of formula I, the molar ratio of the compound of formula IV or the compound of formula II added in step (2) or to the hydroquinone added in step (1) is (1.0-1.8): 1.
in one or more embodiments of the process for preparing the compound of formula I, the reaction of step (2) is carried out under an inert gas atmosphere.
In one or more embodiments of the process for preparing a compound of formula I, the supported FeCl3The carrier of the catalyst is selected from hydrogen type molecular sieve, active silicon oxide and active aluminum oxide.
In one or more embodiments of the process for preparing a compound of formula I, the supported FeCl3In the catalyst, FeCl3The mass ratio of the carrier to the carrier is 1 (5-10).
In one or more embodiments of the process for preparing compounds of formula I, the reaction of step (1) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane.
In one or more embodiments of the process for preparing the compound of formula I, the reaction temperature of step (1) is 220 to 230 ℃.
In one or more embodiments of the process for preparing a compound of formula I, the supported FeCl added in step (1)3FeCl contained in the catalyst3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.1-0.25): 1.
in one or more embodiments of the process for preparing the compound of formula I, the molar ratio of the compound of formula II or the compound of formula IV added in step (1) to the hydroquinone added in step (1) is (0.9-1.1): 1.
in one or more embodiments of the process for preparing the compound of formula I, the reaction of step (1) is carried out in a nitrogen atmosphere.
In one or more embodiments of the process for preparing the compounds of formula I, the reaction of step (2) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane.
In one or more embodiments of the process for preparing the compound of formula I, the reaction temperature of step (2) is 240 to 260 ℃.
In one or more embodiments of the process for preparing the compound of formula I, anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.2-0.3): 1.
in one or more embodiments of the process for preparing the compound of formula I, the molar ratio of the compound of formula IV or the compound of formula II added in step (2) to the hydroquinone added in step (1) is (1.2-1.5): 1.
in one or more embodiments of the process for preparing the compound of formula I, the reaction of step (2) is carried out in a nitrogen atmosphere.
In one or more embodiments of the process for preparing the compound of formula I, the support of the supported FeCl3 catalyst is selected from the group consisting of molecular sieve in hydrogen form, activated silica, and activated alumina; in the supported FeCl3 catalyst, the mass ratio of FeCl3 to the carrier is 1 (5-10); the reaction of step (1) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane; the reaction temperature of the step (1) is 220-230 ℃; in the reaction system in the step (1), the molar ratio of FeCl3 contained in the supported FeCl3 catalyst to hydroquinone is (0.1-0.25): 1, the molar ratio of the compound of formula II or the compound of formula IV to hydroquinone is (0.9-1.1): 1; the reaction of the step (1) is carried out in a nitrogen atmosphere; the reaction of step (2) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane; the reaction temperature of the step (2) is 240-260 ℃; the molar ratio of the anhydrous FeCl3 added in the step (2) to the hydroquinone added in the step (1) is (0.2-0.3): 1; the molar ratio of the compound of formula IV or II added in the step (2) to the hydroquinone added in the step (1) is (1.2-1.5): 1; and the reaction of step (2) is carried out in a nitrogen atmosphere.
In one or more embodiments of the process for preparing compounds of formula I, wherein R is1Is hydrogen, R2、R3Each independently is a C1-C6 alkyl group; or R3Is hydrogen, R1、R2Each independently is a C1-C6 alkyl group; or R1、R2、R3Each independently is a C1-C6 alkyl group.
In one or more embodiments of the process for preparing compounds of formula I, the C1 to C6 alkyl is selected from the group consisting of methyl, ethyl, propyl, and butyl.
In one or more embodiments of the process for preparing a compound of formula I, the C1-C6 alkyl group is selected from methyl and isobutyl.
In one or more embodiments of the process for preparing a compound of formula I, the compound of formula I is selected from:
Figure BDA0002661089040000091
Figure BDA0002661089040000092
Figure BDA0002661089040000093
Figure BDA0002661089040000094
Figure BDA0002661089040000095
Figure BDA0002661089040000096
the invention also provides a loaded FeCl3Catalyst, said supported FeCl3The carrier of the catalyst is selected from hydrogen type molecular sieve, active silica and active alumina, and the supported FeCl3In the catalyst, FeCl3The mass ratio of the carrier to the carrier is 1 (5-10).
In one or more embodiments, the supported FeCl3The carrier of the catalyst is made of anhydrous FeCl3And the carrier is prepared by heating reaction in an alcohol solvent.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as amounts, amounts and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Herein, unless otherwise specified, the ratio refers to a mass ratio, and the percentage refers to a mass percentage.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
As used herein, the terms "comprising," "including," or "containing" mean that the various ingredients can be used together in a mixture or composition of the invention. Thus, the terms "consisting essentially of … …" and "consisting of … …" are encompassed by the terms "comprising," including, "or" containing.
As used herein, alkyl refers to a straight or branched chain monovalent saturated hydrocarbon group, typically containing 1 to 16 carbon atoms (C1-C16 alkyl), for example, 3 to 16 carbon atoms (C3-C16 alkyl). Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 1, 4-dimethylpentyl, and tert-octyl.
Herein, the asymmetric diaryl-substituted p-phenylenediamine compound refers to a compound which can be regarded as a compound obtained by substituting hydrogen atoms on two amino groups on p-phenylenediamine with two different aryl groups. For example, the asymmetric diaryl-substituted p-phenylenediamine compound may have the structure shown in formula a below:
Figure BDA0002661089040000111
in the formula A, each RaIndependently selected from hydrogen and C1-C6 alkyl, m is an integer selected from 0-5, each RbIndependently selected from hydrogen and C1-C6 alkyl, n is an integer selected from 0-5; and (R)a)mSubstituted phenyl and (R)b)nThe substituted phenyl groups are not identical.
As used herein, the term "the same substituted phenyl group" means that the number of substituents on the phenyl group, the position of each substituent and the substituent group at the corresponding position are the same.
In the present invention, R isaOr RbThe C1-C6 alkyl group of (A) includes, but is not limited to, methyl, ethyl, propyl and butyl, wherein propylRadicals including n-propyl and isopropyl, butyl including n-, isobutyl and tert-butyl, i.e. each RaAnd RbEach may be independently selected from hydrogen, methyl, ethyl, propyl, and butyl. In some embodiments, as RaOr RbThe C1-C6 alkyl group of (A) is methyl or tert-butyl, i.e. each RaAnd RbEach independently selected from hydrogen, methyl and tert-butyl.
In the formula A, m is preferably an integer selected from 0 to 3, and more preferably an integer selected from 0 to 2. In the formula A, n is preferably an integer selected from 0 to 3, and more preferably an integer selected from 0 to 2.
The inventor of the invention finds that the asymmetric diaryl substituted p-phenylenediamine compound (compound I or compound I for short) shown as the following formula I not only can provide long-acting anti-aging performance similar to that of an anti-aging agent H or an anti-aging agent 3100, but also can improve blooming property:
Figure BDA0002661089040000112
wherein R is1、R3Each independently is hydrogen or C1-C6 alkyl; r2Is C1-C6 alkyl; and R is1、R2Substituted phenyl and R3The substituted phenyl groups are not identical.
In the present invention, R is1、R2Or R3C1 to C6 alkyl groups of (A) include, but are not limited to, methyl, ethyl, propyl and butyl, wherein propyl includes n-propyl and isopropyl and butyl includes n-butyl, isobutyl and tert-butyl, i.e., each R1、R2And R3Each may be independently selected from hydrogen, methyl, ethyl, propyl, and butyl. In some embodiments, as R1、R2Or R3The C1-C6 alkyl group of (A) is methyl or tert-butyl, i.e. each R1、R2And R3Each independently selected from hydrogen, methyl and tert-butyl.
In some embodiments, in formula I, when R is1When it is hydrogen, R2And R3The radicals indicated are not identical, or R2And R3Watch with clockThe indicated radicals are identical but differ in position on the respective substituted phenyl radicals.
In some embodiments, in formula I, when R is1When it is hydrogen, R2And R3The groups represented are not identical.
In some embodiments, in formula I, R1And R3Not hydrogen at the same time.
In some embodiments, in formula I, R1Is hydrogen, R2、R3Each independently is C1-C6 alkyl, and R2And R3Are not identical.
In some embodiments, in formula I, R3Is hydrogen, R1、R2Each independently is a C1-C6 alkyl group.
In some embodiments, in formula I, R1、R2、R3Each independently is a C1-C6 alkyl group.
In some embodiments, compound I has a structure as shown in any one of formulas I-1 through I-6 below:
Figure BDA0002661089040000121
Figure BDA0002661089040000122
Figure BDA0002661089040000123
Figure BDA0002661089040000124
Figure BDA0002661089040000125
Figure BDA0002661089040000126
the invention provides a method for preparing an asymmetric diaryl substituted p-phenylenediamine compound (a compound of formula A for short) with a structure shown in formula A:
Figure BDA0002661089040000131
in the formula A, each RaIndependently selected from hydrogen and C1-C6 alkyl, m is an integer selected from 0-5, each RbIndependently selected from hydrogen and C1-C6 alkyl, n is an integer selected from 0-5; the compound of formula A does not include (R)a)mSubstituted phenyl and (R)b)nSubstituted phenyl moieties of the same general formula;
the method comprises the following steps:
(1) in a supported FeCl3Catalyst (FeCl)3Support) with a compound of formula B to give a compound of formula C:
Figure BDA0002661089040000132
(2) in anhydrous FeCl3To a compound of formula D in the presence of a compound of formula C to give a compound of formula a:
Figure BDA0002661089040000133
wherein in the compound of formula B, each RaIndependently selected from hydrogen and C1-C6 alkyl, and m is an integer selected from 0-5; in the compound of formula D, each RbIndependently selected from hydrogen and C1-C6 alkyl, n is an integer selected from 0-5; the compound of formula B is not the same as the compound of formula D.
In the process for preparing the compound of the formula A of the present invention, each R is preferably in the compound BaM is preferred, R is preferred for the compound DbPreferably n may be as described in any embodiment herein.
The process for preparing the compound of formula a is also applicable to the preparation of the compound of formula I as described in any of the embodiments herein.
The process for preparing the compound of formula I may comprise the steps of:
(1) in a supported FeCl3Reacting hydroquinone with a compound of formula II in the presence of a catalyst to give a compound of formula III:
Figure BDA0002661089040000141
(2) in anhydrous FeCl3To obtain a compound of formula I by reacting a compound of formula III with a compound of formula IV in the presence of:
Figure BDA0002661089040000142
wherein in the compound of formula II, R1、R2Each independently is hydrogen or C1-C6 alkyl; in the compound of formula IV, R3Is C1-C6 alkyl; the compound of formula II is not the same as the compound of formula IV.
The process for preparing the compounds of formula I may also comprise the steps of:
(1) in a supported FeCl3Reacting hydroquinone with a compound of formula IV in the presence of a catalyst to give a compound of formula III':
Figure BDA0002661089040000143
(2) in anhydrous FeCl3Reacting a compound of formula III' with a compound of formula II in the presence of:
Figure BDA0002661089040000144
wherein in the compound of formula II, R1、R2Each independently is hydrogen or C1-C6 alkyl; in the compound of formula IV, R3Is C1-C6 alkyl; the compound of formula II is not the same as the compound of formula IV.
In the preparation method of the compound of the formula I, R is preferably selected from the compound II1And R2Preferred R in Compound IV3May be as described in any of the embodiments herein.
The invention adopts a two-step method to prepare asymmetric diaryl substituted p-phenylenediamine, and the first step reaction is carried out by using supported FeCl3Is a catalyst, because the ferric iron is stably bonded on the surface of the carrier, the catalytic activity is weaker than that of free FeCl3Therefore, the target product arylamino phenol is limited to further react with arylamine to generate symmetrical diaryl p-phenylenediamine; in addition, the pore structure of the support further limits the formation of diaryl p-phenylenediamine spatially.
The reaction of step (1) is carried out in a non-polar solvent; the nonpolar solvent may be, for example, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, etc., and is preferably toluene or xylene. The reaction of step (1) is carried out under the conditions of heating to reflux azeotropy and dehydration. The reaction temperature in the step (1) is preferably 200 to 240 ℃, and more preferably 220 to 230 ℃. The manner of dewatering may be conventional in the art, for example a water trap may be used. The reaction of step (1) is preferably carried out in an inert gas (e.g., nitrogen) atmosphere.
The invention discovers that in the first step of reaction for preparing asymmetric diaryl substituted p-phenylenediamine, supported FeCl is used3The catalyst can prepare arylamino phenol and limit the arylamino phenol to further react with arylamine to generate symmetric diaryl p-phenylenediamine. In the present invention, a supported FeCl is used3The catalyst refers to FeCl3And (3) a catalyst obtained by supporting on a carrier. Supported FeCl3In the catalyst, ferric iron is stably bonded with the carrier, and FeCl is used3The mass ratio of the carrier to the carrier is preferably 1 (5-10). Supported FeCl3The carrier of the catalyst can be hydrogen type molecular sieve, active silicon oxide or active aluminum oxide. As used herein, activated alumina and activated silica refer to porous solid silica and solid silica having hydroxyl groups on the inner and outer surfaces thereofBulk alumina. The hydrogen form of the molecular sieve may be, for example, GENERAL-REAGENT, 4A from Shanghai Tantan chemical Co. The activated silica may be, for example, GENERAL-REAGENT, G72651A, available from Shanghai Tantan chemical Co., Ltd. The activated alumina may be, for example, GENERAL-REAGENT, G21116K, available from Shanghai Tatan chemical Co.
Supported FeCl for use in the present invention3The catalyst can be prepared from anhydrous FeCl3And a carrier in a solvent through heating reaction. Preparation of Supported FeCl3The solvent used in the catalyst may be an alcoholic solvent, preferably a monohydric alcohol having from C1 to C3, for example methanol. FeCl in the reaction System3And the solvent are usually in a mass ratio of 1: 5 to 1: 20. for example, 1: 9 to 1: 19. FeCl in the reaction System3The mass ratio of the carrier to the carrier is usually 1 (5-10). The reaction is usually carried out under stirring and reflux. The reaction time is usually 5 to 10 hours, preferably 7 to 8 hours. After the reaction is finished, removing the solvent to obtain the supported FeCl3A catalyst. The solvent may be removed by, for example, evaporating the solvent under heating and vacuum.
In some embodiments, the supported FeCl3The catalyst is prepared by the following method:
weighing a certain amount of anhydrous FeCl3Preparing 5-10 wt% solution with methanol, adding into a four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, adding a certain amount of dried carrier, FeCl3And (3) starting mechanical stirring, gradually heating until methanol flows back, keeping the methanol flowing back for 7-8 h, then evaporating the methanol, heating to 140-150 ℃, vacuumizing to about 10kPa absolute pressure, keeping the absolute pressure for 5-6 h, cooling, then quickly pouring into a clean and dry reagent bottle, and putting into a dryer for storage.
In the step (1), the added supported FeCl3FeCl contained in the catalyst3The molar ratio to hydroquinone added is preferably (0.08-0.4): 1. more preferably (0.1-0.25): 1. in step (1), the molar ratio of the compound of formula B (e.g. compound of formula II or compound of formula IV) added to the hydroquinone added is preferably (0.8-1.2): 1. more preferably (0.9-1.1)：1。
Whether the reaction of step (1) is completed or not can be determined by detecting whether or not water is produced, and when water is no longer produced, the reaction is completed. After the reaction in the step (1) is finished, filtering out the catalyst while the catalyst is hot, and distilling off the solvent and the unreacted compound in the formula B (such as the compound in the formula II or the compound in the formula IV) under reduced pressure to obtain the compound in the formula C (such as the compound in the formula III or the compound in the formula III'); filtration and distillation under reduced pressure are preferably carried out at the reaction temperature of step (1); the degree of vacuum of the reduced pressure distillation is preferably less than 5 mmHg.
The reaction of the step (2) is carried out in a non-polar solvent; the nonpolar solvent may be, for example, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, etc., and is preferably toluene or xylene. The reaction of step (2) is carried out under the conditions of heating to reflux azeotropy and dehydration. The reaction temperature in the step (2) is preferably 230-270 ℃, and preferably 240-260 ℃. The manner of dewatering may be conventional in the art, for example a water trap may be used. The reaction of step (2) is preferably carried out in an inert gas (e.g., nitrogen) atmosphere.
Anhydrous FeCl added in step (2)3The molar ratio to hydroquinone added in step (1) is preferably (0.1-0.5): 1. more preferably (0.2-0.3): 1. the molar ratio of the compound of formula D (e.g. compound of formula IV or compound of formula II) added in step (2) to the hydroquinone added in step (1) is preferably (1.0-1.8): 1. more preferably (1.2-1.5): 1.
whether the reaction of step (2) is completed or not can be determined by detecting whether or not water is produced, and when water is no longer produced, the reaction is completed. After the reaction in the step (2) is finished, cooling to about 80-100 ℃, adding a proper amount of alkali liquor for neutralization, heating, decompressing and distilling to obtain water, a solvent and an unreacted compound (such as a compound shown in a formula IV or a compound shown in a formula II), filtering while hot, cooling and solidifying filtrate to obtain a compound (such as a compound shown in a formula I) shown in the formula A; the neutralization time is preferably 0.5-1.5 h; the lye may be, for example, an aqueous solution of a weakly basic salt; the weakly alkaline salt can be sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, etc.; the degree of vacuum of the reduced pressure distillation is preferably less than 5 mmHg; the temperature of reduced pressure distillation is preferably 250-300 ℃; the filtering temperature is preferably 130-160 ℃.
The method of the invention has the following advantages:
(1) the method can prepare the single-component asymmetric diaryl substituted p-phenylenediamine compound, while the single-component asymmetric diaryl p-phenylenediamine is difficult to prepare in the prior art;
(2) the cost is low: the substituted cyclohexanone with higher cost is not needed to be used as a reaction raw material;
(3) less side reaction and high yield: the reaction does not need to add a hydrogen acceptor, the side reaction is less, the yield can reach more than 80 percent, and the product purity can reach more than 85 percent;
(4) the reaction conditions are not harsh: reaction in heating and supported FeCl3Catalyst or anhydrous FeCl3Can be carried out under the catalysis of (3).
The compound I of the present invention is useful as a rubber antioxidant, providing more durable protection than conventional antioxidants, without producing blooming. Accordingly, the present invention provides rubber compositions comprising one or more of the compounds I of the invention. The raw materials of the rubber composition generally include a diene elastomer, a reinforcing filler, an antioxidant and a crosslinking agent. The amounts of diene elastomer, reinforcing filler, anti-ageing agent and crosslinking agent may be those conventionally used in the art. The amount of compound I to be used in the rubber composition may be 0.1 to 5 parts by mass, for example, 0.5 to 5 parts by mass, 1 to 3 parts by mass, or 1 to 2 parts by mass, based on 100 parts by mass of the diene elastomer. Herein, the rubber composition includes unvulcanized rubber and vulcanized rubber. The unvulcanized rubber is vulcanized (cured) to obtain a vulcanized rubber.
Diene elastomer means an elastomer whose monomers comprise dienes (e.g. butadiene, isoprene). The diene elastomer suitable for use in the present invention may be various diene elastomers known in the art, including, but not limited to, one or more selected from Natural Rubber (NR), Butadiene Rubber (BR), isoprene rubber, styrene-butadiene rubber (SBR), Chloroprene Rubber (CR), nitrile-butadiene rubber (NBR), isoprene/butadiene copolymer, isoprene/styrene copolymer, and isoprene/butadiene/styrene copolymer. In certain embodiments, the rubber composition of the present invention wherein the diene elastomer is comprised of natural rubber (e.g., SCR5) and butadiene rubber (e.g., BR 9000); the mass ratio of the natural rubber and the butadiene rubber is not particularly limited, and is, for example, 1: 9 to 9: 1. 2: 8 to 8: 2. 3: 7 to 7: 3. 4: 6 to 6: 4. or 1: about 1.
The reinforcing filler may be a reinforcing filler conventionally used for rubbers, including but not limited to one or more selected from carbon black, titanium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, clay and talc. The reinforcing filler may be used in an amount of 40 to 60 parts by mass per 100 parts by mass of the diene elastomer.
The cross-linking agent may be sulphur. The amount of the crosslinking agent to be used may be 1 to 3 parts by mass per 100 parts by mass of the diene elastomer.
The antioxidant can be used in an amount of 0.1 to 5 parts by mass, 0.5 to 5 parts by mass, 1 to 3 parts by mass, or 1 to 2 parts by mass per 100 parts by mass of the diene elastomer. In the rubber composition of the present invention, the antioxidant may be compound I or a combination of compound I and a conventional antioxidant.
The raw materials for the rubber composition may also include other ingredients commonly used in rubber, including but not limited to adjuvants and accelerators, and the like. The amounts of auxiliaries and accelerators may be those conventionally used in the art.
The auxiliary may include a softener used for improving processability. The softener may be a petroleum type softener such as aromatic oil, processed oil, lubricating oil, paraffin, liquid paraffin, petroleum pitch, vaseline, etc., or a fatty oil type softener such as castor oil, linseed oil, rapeseed oil, coconut oil, wax (e.g., beeswax, carnauba wax, and lanolin), tall oil, linoleic acid, palmitic acid, stearic acid, and lauric acid, etc. The auxiliary agent can also comprise an active agent, such as zinc oxide, and can play a role in accelerating vulcanization speed, improving rubber thermal conductivity, wear resistance, tearing resistance and the like. In general, the auxiliary is used in a total amount of 5 to 20 parts by mass per 100 parts by mass of the diene elastomer, and for example, 2 to 8 parts by mass of an aromatic oil, 2 to 8 parts by mass of zinc oxide and 1 to 4 parts by mass of stearic acid may be used.
The accelerator is usually a vulcanization accelerator, and may be at least one of sulfonamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldehyde amine, imidazoline and xanthate vulcanization accelerators. For example, the accelerator may be accelerator NS (N-tert-butyl-2-benzothiazolesulfenamide). Generally, the accelerator is used in an amount of 0.5 to 1.5 parts by mass per 100 parts by mass of the diene elastomer.
In addition, plasticizers such as DMP (dimethyl phthalate), DEP (diethyl phthalate), DBP (dibutyl phthalate), DHP (diheptyl phthalate), DOP (dioctyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), BBP (butylbenzyl phthalate), DWP (dilauryl phthalate), DCHP (dicyclohexyl phthalate), and the like may also be used in the rubber composition, if necessary. The amount of plasticizer used is that amount conventionally used in the art.
The unvulcanized rubber of the present invention can be prepared by a conventional rubber mixing method, for example, by a two-stage mixing method: mixing the mixture in a first-stage internal mixer, mixing the diene elastomer, the reinforcing filler, the auxiliary agent and the anti-aging agent, and discharging rubber at the temperature of more than 110 ℃; mixing the rubber obtained in the first stage with a cross-linking agent and an accelerant by a two-stage open mill. Generally, the diene elastomer is added into a thermo-mechanical mixer (such as an internal mixer), after a certain time of kneading, the reinforcing filler, the auxiliary agent and the anti-aging agent are added, and the kneading is continued until the mixture is uniform, the reinforcing filler, the auxiliary agent and the anti-aging agent can be added in batches, and the temperature during the kneading is controlled between 110 ℃ and 190 ℃, preferably between 150 ℃ and 160 ℃; then, the mixture is cooled to 100 ℃ or lower, the crosslinking agent and the accelerator are added, and kneading is carried out again while controlling the temperature to 110 ℃ or lower, for example, about 70 ℃ during kneading, to obtain an unvulcanized rubber.
The unvulcanized rubber of the present invention can be vulcanized by a conventional vulcanization method to obtain a vulcanized rubber; the vulcanization temperature is usually from 130 ℃ to 200 ℃, for example around 145 ℃; the vulcanization time depends on the vulcanization temperature, the vulcanization system and the vulcanization kinetics and is usually from 15 to 60 minutes, for example around 30 minutes. The unvulcanized rubber obtained by kneading may be subjected to conventional tableting prior to vulcanization.
The compound I and the rubber composition of the invention are used for rubber products, especially rubber tires, and can endow the rubber products or the rubber tires with more lasting ageing resistance without generating blooming. Accordingly, the present invention also provides a rubber article having the rubber composition of the present invention as its rubber component. The rubber product can be a tire, a rubber shoe, a sealing strip, a sound insulation board, a vibration-proof cushion and the like. In certain embodiments, the rubber article is a tire, such as a tread, belt, and sidewall of a tire. The belt of the tire may contain, in addition to the rubber composition of the present invention, reinforcing materials conventionally used in the art.
The asymmetric diaryl substituted p-phenylenediamine compound can prevent the rubber product from blooming in the using process. The invention also provides the use of the compounds I according to the invention for improving the ageing resistance and/or the blooming of rubber or rubber articles.
The invention will now be described by way of specific examples, which are intended to provide a better understanding of the contents of the invention. It is to be understood that these examples are illustrative only and not limiting. The starting materials and reagents used in the examples were, unless otherwise specified, those conventionally available on the market. The experimental methods, preparation methods and detection methods used in the examples are all conventional methods unless otherwise specified. The instruments and devices used in the examples are conventional in the art unless otherwise specified. In the examples, percentages refer to mass percentages unless otherwise specified.
FeCl supported by the examples3The catalyst is prepared by the following method:
weighing a certain amount of anhydrous FeCl3Preparing FeCl with concentration of 8 wt% by using methanol3Adding the methanol solution into a four-neck flask provided with a mechanical stirring device, a thermometer and a reflux condenser, adding a certain amount of dried carrier, FeCl3Starting mechanical stirring, gradually heating to methanol reflux, keeping refluxing for 8 hr, steaming out methanol, heating to 150 deg.C, vacuumizing to absolute pressure of 10kPa, and keepingAnd (5) holding for 6h, cooling, quickly pouring into a clean and dry reagent bottle, and storing in a dryer. Examples 1 to 11 used supported FeCl prepared using a hydrogen-type molecular sieve (GENERAL-REAGENT, 4A, Shanghai Tantan chemical Co., Ltd.) as a carrier3A catalyst, example 12, used a FeCl supported on active silica (GENERAL-REAGENT, G72651A, Shanghai Tantan chemical Co., Ltd.)3A catalyst, example 13, used a FeCl supported on activated alumina (GENERAL-REAGENT, G21116K, Shanghai Tantan chemical Co., Ltd.) as a carrier3A catalyst.
Example 1: preparation of N-phenyl-N' - (2, 3-dimethyl) phenyl-p-phenylenediamine (Compound I-1)
Figure BDA0002661089040000201
(1) 96.8g (0.8mol) of 2, 3-dimethylaniline, 110.0g (1mol) of hydroquinone and FeCl containing 12.96g (0.08mol) were charged into a 1L stainless steel reaction vessel equipped with a condenser and a water separator3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 200 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 3-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 16.2g (0.1mol) of anhydrous FeCl were added3111.6g (1.2mol) of aniline and 20mL of xylene, starting stirring after nitrogen replacement, heating to 230 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into 212g of block-shaped product (yield 81.0%), sampling, GC analyzing to obtain 88%, and detecting the molecular weight of the product by a mass spectrometer as 288.
Example 2: preparation of N-phenyl-N' - (2, 3-dimethyl) phenyl-p-phenylenediamine (Compound I-1)
(1) To 1L stainless steel equipped with condenser and water separator121g (1mol) of 2, 3-dimethylaniline, 110.0g (1mol) of hydroquinone and FeCl containing 12.96g (0.08mol) of3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 220 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 3-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 32.4g (0.2mol) of anhydrous FeCl were added393g (1mol) aniline and 20mL xylene, replacing with nitrogen, starting stirring, heating to 230 ℃, reacting until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying the cooled filtrate into 277g of block products (yield is 85.6%), sampling, analyzing by GC to obtain 89%, and detecting the molecular weight of the block products by a mass spectrometer to be 288.
Example 3: preparation of N-phenyl-N' - (2, 3-dimethyl) phenyl-p-phenylenediamine (Compound I-1)
(1) To a 1L stainless steel reaction vessel equipped with a condenser and a water separator were charged 121g (1mol) of 2, 3-dimethylaniline, 110.0g (1mol) of hydroquinone, and 16.2g (0.1mol) of FeCl3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 230 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 3-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 48.6g (0.3mol) of anhydrous FeCl were added393g (1mol) of aniline and 20mL of xylene, replacing with nitrogen, starting stirring, heating to 240 ℃, reacting until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into 278g of block-shaped product (yield 89.8%), sampling, GC analyzing to obtain 93%, and detecting the molecular weight of the product by a mass spectrometer to be 288.
Example 4: preparation of N-phenyl-N' - (2, 3-dimethyl) phenyl-p-phenylenediamine (Compound I-1)
(1) To a 1L stainless steel reaction vessel equipped with a condenser and a water separator were charged 133.1g (1.1mol) of 2, 3-dimethylaniline, 110.0g (1mol) of hydroquinone, and 16.2g (0.1mol) of FeCl3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 230 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 3-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 48.6g (0.3mol) of anhydrous FeCl were added3111.6g (1.2mol) of aniline and 20mL of xylene, starting stirring after nitrogen replacement, heating to 250 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into 280g of block-shaped product (yield 91.4%), sampling, analyzing by GC to obtain 94%, and detecting the molecular weight of the product by a mass spectrometer to be 288.
Example 5: preparation of N-phenyl-N' - (2, 3-dimethyl) phenyl-p-phenylenediamine (Compound I-1)
(1) To a 1L stainless steel reaction vessel equipped with a condenser and a water separator were charged 133.1g (1.1mol) of 2, 3-dimethylaniline, 110.0g (1mol) of hydroquinone, and FeCl containing 32.4g (0.2mol)3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 220 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 3-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 48.6g (0.3mol) of anhydrous FeCl were added3139.5g (1.5mol) of aniline and 20mL of xylene, replacing with nitrogen, starting stirring, heating to 250 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into 281g of block products (yield 91.7%), sampling, analyzing by GC to obtain 94%, and detecting the molecular weight of the product by a mass spectrometer to be 288.
Example 6: preparation of N-phenyl-N' - (2, 3-dimethyl) phenyl-p-phenylenediamine (Compound I-1)
(1) To a 1L stainless steel reaction vessel equipped with a condenser and a water separator were charged 133.1g (1.1mol) of 2, 3-dimethylaniline, 110.0g (1mol) of hydroquinone, and FeCl containing 64.8g (0.4mol)3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 230 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 3-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 64.8g (0.4mol) of anhydrous FeCl were added3139.5g (1.5mol) of aniline and 20mL of xylene, replacing with nitrogen, starting stirring, heating to 250 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into 280g of block-shaped product (yield 88.5%), sampling, analyzing by GC to obtain 91%, and detecting the molecular weight of the product by a mass spectrometer to be 288.
Example 7: preparation of N-phenyl-N' - (2, 3-dimethyl) phenyl-p-phenylenediamine (Compound I-1)
(1) 145.2g (1.2mol) of 2, 3-dimethylaniline, 110.0g (1mol) of hydroquinone and 64.8g (0.4mol) of FeCl were charged into a 1L stainless steel reaction vessel equipped with a condenser and a water separator3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 230 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 3-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 81g (0.5mol) of anhydrous FeCl were added3111.6g (1.2mol) of aniline and 20mL of xylene, starting stirring after nitrogen replacement, heating to 260 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into a blocky product 289g (yield 85.3%), sampling, analyzing by GC to obtain 85%, and detecting the molecular weight of the blocky product 288 by a mass spectrometer.
Example 8: preparation of N-phenyl-N' - (2, 3-dimethyl) phenyl-p-phenylenediamine (Compound I-1)
(1) 145.2g (1.2mol) of 2, 3-dimethylaniline, 110.0g (1mol) of hydroquinone and FeCl containing 32.4g (0.2mol) were charged into a 1L stainless steel reaction vessel equipped with a condenser and a water separator3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 230 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 3-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 64.8g (0.4mol) of anhydrous FeCl were added3167.4g (1.8mol) of aniline and 20mL of xylene, stirring after nitrogen replacement, heating to 250 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into 276g of block products (yield is 83.3%), sampling, analyzing by GC to obtain 87%, and detecting the molecular weight of the product by a mass spectrometer to be 288.
In examples 1 to 8, the amounts of hydroquinone charged were all 1mol, and the differences in other conditions and the results of the experiment are shown in Table 1.
Table 1: experimental conditions and results of examples 1 to 8
Figure BDA0002661089040000241
Example 9: N-phenyl-N' - (2, 6-dimethyl) phenyl-p-phenylenediamine (Compound I-2)
Figure BDA0002661089040000251
(1) To a 1L stainless steel reaction vessel equipped with a condenser and a water separator were charged 133.1g (1.1mol) of 2, 6-dimethylaniline, 110.0g (1mol) of hydroquinone, and 16.2g (0.1mol) of FeCl3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 230 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 6-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 48.6g (0.1mol) of anhydrous FeCl were added3111.6g (1.2mol) of aniline and 20mL of xylene, starting stirring after nitrogen replacement, heating to 250 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying the cooled filtrate into 275g of block products (yield is 90.7%), sampling, measuring the content by GC analysis to be 95%, and detecting the molecular weight of the block products by a mass spectrometer to be 288.
Preparation example 10: N-phenyl-N' - (2-tert-butyl-4-methyl) phenyl-p-phenylenediamine (Compound I-3)
Figure BDA0002661089040000252
(1) 179.3g (1.1mol) of 2-tert-butyl-4-methylaniline, 110.0g (1mol) of hydroquinone, and 16.2g (0.1mol) of FeCl were charged into a 1L stainless steel reaction vessel equipped with a condenser and a water separator3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 240 ℃ to react until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2-tert-butyl-4-methylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 48.6g (0.1mol) of anhydrous FeCl were added3111.6g (1.2mol) aniline and 20mL xylene, replacing with nitrogen, starting stirring, heating to 250 ℃ for reaction until no water separator existsSeparating out water and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into a block product 311g (yield is 87.6%), sampling, analyzing by HPLC to obtain the product with the content of 93%, and detecting the molecular weight of the product by a mass spectrometer to be 330.
Preparation example 11: N-o-tolyl-N' - (2, 3-dimethyl) phenyl-p-phenylenediamine (Compound I-4)
Figure BDA0002661089040000261
(1) To a 1L stainless steel reaction vessel equipped with a condenser and a water separator were charged 133.1g (1.1mol) of 2, 3-dimethylaniline, 110.0g (1mol) of hydroquinone, and 16.2g (0.1mol) of FeCl3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 230 ℃ for reaction until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 3-dimethylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 48.6g (0.1mol) of anhydrous FeCl were added3128.4g (1.2mol) of o-toluidine and 20mL of xylene, stirring after nitrogen replacement, heating to 250 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying the cooled filtrate into 290g of block products (yield is 90.3%), sampling, analyzing by GC, determining the content to be 94%, and detecting the molecular weight to be 302 by mass spectrometry.
Preparation example 12: N-o-tolyl-N' - (4-tert-butyl) phenyl-p-phenylenediamine (Compound I-5)
Figure BDA0002661089040000262
(1) 4-tert-butylbenzene was added into a 1L stainless steel reaction kettle equipped with a condenser and a water separator163.9g (1.1mol) of amine, 110.0g (1mol) of hydroquinone and 16.2g (0.1mol) of FeCl3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst by nitrogen, starting stirring, heating to 240 ℃ to react until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 4-tert-butyl aniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 48.6g (0.1mol) of anhydrous FeCl were added3128.4g (1.2mol) of o-toluidine and 20mL of xylene, stirring after nitrogen replacement, heating to 250 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into a block product 308g (yield 87.8%), sampling, analyzing by HPLC to obtain the product with the content of 94%, and detecting the molecular weight of 330 by mass spectrometry.
Preparation example 13: N-phenyl-N' - (2, 4-di-tert-butyl) phenyl-p-phenylenediamine (Compound I-6)
Figure BDA0002661089040000271
(1) To a 1L stainless steel reaction vessel equipped with a condenser and a water separator were charged 225.5g (1.1mol) of 2, 4-di-t-butylaniline, 110.0g (1mol) of hydroquinone, and FeCl containing 32.4g (0.2mol)3Supported FeCl3Adding 20ml of toluene into the catalyst, replacing the catalyst with nitrogen, starting stirring, heating to 240 ℃ to react until no water is separated from the water separator, filtering the catalyst while the catalyst is hot, and distilling the toluene and unreacted 2, 4-di-tert-butylaniline under reduced pressure at the temperature to finish the first-step reaction;
(2) 48.6g (0.1mol) of anhydrous FeCl were added3111.6g (1.2mol) of aniline and 20mL of xylene, starting stirring after nitrogen replacement, heating to 250 ℃ for reaction until no water is separated from the water separator, and finishing the reaction;
(3) cooling to 90 ℃, adding an aqueous solution containing 0.3mol of sodium carbonate, keeping the temperature and stirring for 1h, heating, distilling under reduced pressure to evaporate light components, filtering while the solution is hot, cooling the filtrate, solidifying into 330g of block-shaped product (yield is 82.5%), sampling, analyzing by HPLC to obtain 93%, and detecting the molecular weight by a mass spectrometer to be 372.
Test example:
the rubber compositions of test examples 1 to 4 were prepared according to the formulations shown in Table 2, specifically comprising the following steps:
1. adding natural rubber SCR5 and synthetic rubber BR into an internal mixer, kneading for a period of time, adding carbon black N550, aromatic oil, zinc oxide, stearic acid and an anti-aging agent (anti-aging agent H, compound I-1, anti-aging agent 3100 and compound I-6), and continuing kneading until the mixture is uniformly mixed; the temperature during kneading is controlled between 150 ℃ and 160 ℃;
2. cooling the whole mixture to below 100 ℃, then adding the crosslinking system (sulphur S and accelerator NS), kneading the whole mixture; controlling the temperature during kneading to not more than 110 ℃;
3. the resulting rubber composition was rolled into a sheet shape (thickness: 2 to 3mm), and vulcanized at a vulcanization temperature of 145 ℃ for 30 minutes.
The sources of the ingredients in table 2 are as follows:
SCR 5: simons banna rubber ltd, natural rubber SCR 5;
BR: south beijing Yangzi petrochemical rubber Co., Ltd, synthetic rubber BR 9000;
n550: cabot corporation, carbon black N550;
aromatic oil: shanghai Tantake Technique, Inc., general-purpose reagents;
stearic acid: shanghai Tantake technologies, Inc., general purpose reagents, stearic Acid (AR);
zinc oxide: shanghai Tantake technologies, Inc., general purpose reagents, zinc oxide (AR);
and NS: saint ao chemical science and technology ltd, vulcanization accelerator NS;
s: chemical agents corporation, national drug group, sublimed sulfur (AR);
an anti-aging agent H: saint chemical science and technology, Inc.;
compound I-1: the compound synthesized in example 4;
anti-aging agent 3100: acmechem Limited, India;
compound I-6: example 13 the compound synthesized.
Table 2: formulation of rubber composition (unit: parts by mass)
Figure BDA0002661089040000281
Figure BDA0002661089040000291
Evaluation of ozone aging resistance:
test pieces of various rubber compositions were subjected to an ozone deterioration test under conditions of a temperature of 40 ℃, an ozone concentration of 50pphm and an elongation of 20%. The time to the occurrence of grade 1c to 4c cracks was recorded. Longer time to form the same grade of crack indicates better ozone aging resistance. The results of the experiment are shown in table 3. In table 3, the numbers in "1 c to 4 c" represent the crack width grades, and the letters represent the crack number grades; 1 represents a crack width of more than 0mm and less than 0.1mm, 2 represents a crack width of 0.1mm or more and less than 0.2mm, 3 represents a crack width of 0.2mm or more and less than 0.4mm, and 4 represents a crack width of 0.4mm or more; c represents 40 or more cracks per centimeter.
Table 3: film ozone aging results
Test example 1 Test example 2 Test example 3 Test example 4
Grade 1c crack 3h 3h 3h 3h
2c grade crack 6h 6h 6h 6h
Grade 3c crack 22h 21h 21h 22h
Grade 4c crack 50h 60h 54h 62h
As can be seen from Table 3, the four test films showed almost the same time for the primary cracks, and the two films of test example 2 and test example 4 showed the longest time for the 4 c-stage cracks, indicating that the home-made compounds I-1 and I-6 had better ozone aging resistance than antioxidant H and antioxidant 3100.
Evaluation of blooming Performance:
the surface state of the film was observed after one week and two weeks, respectively, of the film formation, and the results are shown in Table 4.
Table 4: results of blooming Performance test
Test example 1 Test example 2 Test example 3 Test example 4
1 week Obvious blooming phenomenon No change in surface Slight blooming phenomenon No change in surface
2 weeks Large area white cream No change in surface Large-area white cream No change in surface
As can be seen from table 4, the two films to which the antioxidant H (test example 1) and the antioxidant 3100 (test example 3) were added were left standing for a while, while the two films to which the home-made compound I-1 (test example 2) and the home-made compound I-6 (test example 4) were added were left standing for two weeks without blooming, indicating that the compound of the present invention can improve blooming.

Claims (12)

1. A method for preparing an asymmetric diaryl-substituted p-phenylenediamine compound, characterized in that the asymmetric diaryl-substituted p-phenylenediamine compound has a structure represented by the following formula A:
Figure FDA0002661089030000011
in the formula A, each RaIndependently selected from hydrogen and C1-C6 alkyl, m is an integer selected from 0-5, each RbIndependently selected from hydrogen and C1-C6 alkyl, n is an integer selected from 0-5; the compound of formula A does not include (R)a)mSubstituted phenyl and (R)b)nSubstituted phenyl moieties of the same general formula;
the method comprises the following steps:
(1) in a supported FeCl3Reacting hydroquinone with a compound of formula B in the presence of a catalyst to give a compound of formula C:
Figure FDA0002661089030000012
(2) in anhydrous FeCl3To a compound of formula D in the presence of a compound of formula C to give a compound of formula a:
Figure FDA0002661089030000013
wherein in the compound of formula B, each RaIndependently selected from hydrogen and C1-C6 alkyl, and m is an integer selected from 0-5; in the compound of formula D, each RbIndependently selected from hydrogen and C1-C6 alkyl, n is an integer selected from 0-5; the compound of formula B is not the same as the compound of formula D.
2. The method of claim 1, wherein the method has one or more of the following features:
the supported FeCl3The carrier of the catalyst is selected from hydrogen type molecular sieve, active silicon oxide and active aluminum oxide;
the reaction of step (1) is carried out in a non-polar solvent;
the reaction temperature of the step (1) is 200-240 ℃;
in the reaction system of the step (1), supported FeCl3FeCl contained in the catalyst3The molar ratio of the hydroquinone is (0.08-0.4): 1;
in the reaction system of the step (1), the molar ratio of the compound shown in the formula B to hydroquinone is (0.8-1.2): 1;
the reaction of the step (1) is carried out in an inert gas atmosphere;
the reaction of the step (2) is carried out in a non-polar solvent;
the reaction temperature of the step (2) is 230-270 ℃;
anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.1-0.5): 1;
the molar ratio of the compound of formula D added in step (2) to the hydroquinone added in step (1) is (1.0-1.8): 1; and
the reaction of step (2) is carried out in an inert gas atmosphere.
3. The method of claim 2, wherein the method has one or more of the following features:
the supported FeCl3In the catalyst, FeCl3The mass ratio of the carrier to the carrier is 1 (5-10);
the reaction of step (1) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane;
the reaction temperature of the step (1) is 220-230 ℃;
in the reaction system of the step (1), supported FeCl3FeCl contained in the catalyst3The molar ratio of the hydroquinone is (0.1-0.25): 1;
in the reaction system of the step (1), the molar ratio of the compound shown in the formula B to hydroquinone is (0.9-1.1): 1;
the reaction of the step (1) is carried out in a nitrogen atmosphere;
the reaction of step (2) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane;
the reaction temperature of the step (2) is 240-260 ℃;
anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.2-0.3): 1;
the molar ratio of the compound of formula D added in the step (2) to the hydroquinone added in the step (1) is (1.2-1.5): 1; and
the reaction of step (2) is carried out in a nitrogen atmosphere.
4. The method of claim 1, wherein the supported FeCl is3The carrier of the catalyst is selected from hydrogen type molecular sieve, active silicon oxide and active aluminum oxide; the supported FeCl3In the catalyst, FeCl3The mass ratio of the carrier to the carrier is 1 (5-10); the reaction of step (1) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane; the reaction temperature of the step (1) is 220-230 ℃; in the reaction system of the step (1), supported FeCl3FeCl contained in the catalyst3The molar ratio of the hydroquinone is (0.1-0.25): 1, the molar ratio of the compound of formula B to hydroquinone is (0.9-1.1): 1; the reaction of the step (1) is carried out in a nitrogen atmosphere; the reaction of step (2) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane; the reaction temperature of the step (2) is 240-260 ℃; anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.2-0.3): 1; the molar ratio of the compound of formula D added in the step (2) to the hydroquinone added in the step (1) is (1.2-1.5): 1; and the reaction of step (2) is carried out in a nitrogen atmosphere.
5. A process for preparing a compound of formula I:
Figure FDA0002661089030000031
in the formula I, R1、R3Each independently is hydrogen or C1-C6 alkyl; r2Is C1-C6 alkyl; compounds of formula I not including R1、R2Substituted phenyl and R3Substituted phenyl moieties of the same general formula;
the method comprises the following steps:
(1) in a supported FeCl3Reacting hydroquinone with a compound of formula II in the presence of a catalyst to give a compound of formula III:
Figure FDA0002661089030000041
(2) in anhydrous FeCl3To obtain a compound of formula I by reacting a compound of formula III with a compound of formula IV in the presence of:
Figure FDA0002661089030000042
wherein in the compound of formula II, R1、R2Each independently is hydrogen or C1-C6 alkyl; in the compound of formula IV, R3Is C1-C6 alkyl; the compound of formula II is not the same as the compound of formula IV; or
The method comprises the following steps:
(1) in a supported FeCl3Reacting hydroquinone with a compound of formula IV in the presence of a catalyst to give a compound of formula III':
Figure FDA0002661089030000043
(2) in anhydrous FeCl3Reacting a compound of formula III' with a compound of formula II in the presence of:
Figure FDA0002661089030000044
wherein in the compound of formula II, R1、R2Each independently is hydrogen or C1-C6 alkyl; in the compound of formula IV, R3Is C1-C6 alkyl; the compound of formula II is not the same as the compound of formula IV.
6. The method of claim 5, wherein the method has one or more of the following features:
the supported FeCl3The carrier of the catalyst is selected from hydrogen type molecular sieve, active silicon oxide and active aluminum oxide;
the reaction of step (1) is carried out in a non-polar solvent;
the reaction temperature of the step (1) is 200-240 ℃;
in the reaction system of the step (1), supported FeCl3FeCl contained in the catalyst3The molar ratio of the hydroquinone is (0.08-0.4): 1;
in the reaction system of the step (1), the molar ratio of the compound of the formula II or the compound of the formula IV to hydroquinone is (0.8-1.2): 1;
the reaction of the step (1) is carried out in an inert gas atmosphere;
the reaction of step (1) is carried out in a non-polar solvent;
the reaction temperature of the step (2) is 230-270 ℃;
anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.1-0.5): 1;
the mole ratio of the compound of formula IV or the compound of formula II added in the step (2) or the compound of formula II added in the step (1) to the hydroquinone added in the step (1) is (1.0-1.8): 1; and
the reaction of step (2) is carried out in an inert gas atmosphere.
7. The method of claim 6, wherein the method has one or more of the following features:
the supported FeCl3In the catalyst, FeCl3The mass ratio of the carrier to the carrier is 1 (5-10);
the reaction of step (1) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane;
the reaction temperature of the step (1) is 220-230 ℃;
in the reaction system of the step (1), supported FeCl3FeCl contained in the catalyst3The molar ratio of the hydroquinone is (0.1-0.25): 1;
in the reaction system of the step (1), the molar ratio of the compound of the formula II or the compound of the formula IV to hydroquinone is (0.9-1.1): 1;
the reaction of the step (1) is carried out in a nitrogen atmosphere;
the reaction of step (2) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane;
the reaction temperature of the step (2) is 240-260 ℃;
anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.2-0.3): 1;
the molar ratio of the compound of formula IV or II added in the step (2) to the hydroquinone added in the step (1) is (1.2-1.5): 1; and
the reaction of step (2) is carried out in a nitrogen atmosphere.
8. The method of claim 5, wherein in formula I, R is1Is hydrogen, R2、R3Each independently is a C1-C6 alkyl group; or R3Is hydrogen, R1、R2Each independently is a C1-C6 alkyl group; or R1、R2、R3Each independently is a C1-C6 alkyl group.
9. The method of claim 5, wherein the supported FeCl3The carrier of the catalyst is selected from hydrogen type molecular sieve and hydrogen type molecular sieveSilica and activated alumina; the supported FeCl3In the catalyst, FeCl3The mass ratio of the carrier to the carrier is 1 (5-10); the reaction of step (1) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane; the reaction temperature of the step (1) is 220-230 ℃; in the reaction system of the step (1), supported FeCl3FeCl contained in the catalyst3The molar ratio of the hydroquinone is (0.1-0.25): 1, the molar ratio of the compound of formula II or the compound of formula IV to hydroquinone is (0.9-1.1): 1; the reaction of the step (1) is carried out in a nitrogen atmosphere; the reaction of step (2) is carried out in toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylcyclohexane, dimethylcyclohexane and/or trimethylcyclohexane; the reaction temperature of the step (2) is 240-260 ℃; anhydrous FeCl added in step (2)3The molar ratio of the hydroquinone to the hydroquinone added in the step (1) is (0.2-0.3): 1; the molar ratio of the compound of formula IV or II added in the step (2) to the hydroquinone added in the step (1) is (1.2-1.5): 1; and the reaction of step (2) is carried out in a nitrogen atmosphere.
10. The method of claim 5, wherein the compound of formula I is selected from the group consisting of:
Figure FDA0002661089030000061
Figure FDA0002661089030000071
11. load type FeCl3Catalyst, characterized in that the supported FeCl3The carrier of the catalyst is selected from hydrogen type molecular sieve, active silica and active alumina, and the supported FeCl3In the catalyst, FeCl3The mass ratio of the carrier to the carrier is 1 (5-10).
12. Supported FeCl as claimed in claim 113Catalyst, characterized in that the supported FeCl3The carrier of the catalyst is made of anhydrous FeCl3And the carrier is prepared by heating reaction in an alcohol solvent.
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