CN111440074A - Hofmann rearrangement method for preparing m-phenylenediamine - Google Patents

Hofmann rearrangement method for preparing m-phenylenediamine Download PDF

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CN111440074A
CN111440074A CN202010217040.7A CN202010217040A CN111440074A CN 111440074 A CN111440074 A CN 111440074A CN 202010217040 A CN202010217040 A CN 202010217040A CN 111440074 A CN111440074 A CN 111440074A
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metal
additive
hydroxide
phenylenediamine
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王健
唐斌
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Shenzhen Youwei Technology Holding Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/54—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions
    • C07C209/56—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions from carboxylic acids involving a Hofmann, Curtius, Schmidt, or Lossen-type rearrangement
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention relates to the field of organic functional new material chemicals, and discloses a new process technology for preparing m-phenylenediamine from m-benzenedicarboxamide or a precursor compound thereof by a Hofmann rearrangement method for the first time. M-phenylenediamine is a large amount of key fine chemicals with wide application in related fields such as known dyes, pigments, medical, pesticide and building auxiliary materials and the like, and the innovative technology of the production process is widely concerned.

Description

Hofmann rearrangement method for preparing m-phenylenediamine
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of organic functional new material chemicals, and discloses a new process technology for preparing m-phenylenediamine from m-benzenedicarboxamide or a precursor compound thereof by a Hofmann rearrangement method for the first time. M-phenylenediamine is a large amount of key fine chemicals with wide application in related fields such as known dyes, pigments, medical, pesticide and building auxiliary materials and the like, and the innovative technology of the production process is widely concerned.
[ background of the invention ]
M-phenylenediamine, also known as 1, 3-diaminobenzene, is a small molecular compound (CAS 208-45-2) which is a white acicular crystal at normal temperature, and is also a large amount of key fine chemicals with wide application in the related fields of known dyes, pigments, medical and pesticide building auxiliary materials. The traditional manufacturing process of m-phenylenediamine relates to a double nitration reaction in a nitric acid/sulfuric acid strong corrosive medium starting from carcinogenic dangerous chemical benzene as a basic raw material and a subsequent metal catalysis and/or high-pressure hydrogenation double reduction reaction, and the technical route literature has quite abundant detail optimization disclosure, but the current industrial current situation is not fundamentally changed, and the m-phenylenediamine still belongs to disturbing unit reaction engineering with serious environmental pollution and high danger.
The large explosion accidents in shock surprise caused by m-phenylenediamine production enterprises in Chenjia harbor chemical industrial park in Xiangshui county of Jiangsu province in China in 2019, 3 and 21 days are direct reflection of the high risk of the process. Therefore, the preparation process technology and innovation of the composite material are important issues continuously pursued by technical personnel in the industry under the strong drive of the factors of safety, reliability, environmental protection, energy conservation, low cost, economic competitiveness and the like, and no significant breakthrough exists so far.
The latest application of the invention (application No. CN201910744081.9, application date 2019, 8 and 13, publication No. CN110437080A, publication date 2019, 11 and 12) entitled "method for producing m-phenylenediamine" claims that m-phenylenediamine is produced by a hofmann degradation reaction between m-phenylenediamine and sodium hypochlorite. However, the application describes in the claims, the text of the specification, the detailed description and the like that isophthalamide only reacts with sodium hypochlorite solid pure product at the alleged molar ratio, namely, the m-phenylenediamine target product can be obtained without any other core reaction factor (characterized by strong base), which is obviously contrary to the hofmann degradation reaction condition in principle from the chemical reaction technology. Further, if so, in view of the strong oxidizing property of sodium hypochlorite, an oxidation reaction should occur, not the alleged hofmann degradation reaction; secondly, we carefully and multiply arrange the technician to repeat all examples disclosed in the "detailed description" section of this application in parallel, and clearly show that there is no alleged production of m-phenylenediamine, nor even any evidence of significant chemical reactivity.
[ summary of the invention ]
In order to solve at least one of the above technical problems, the present invention provides a novel method for preparing m-phenylenediamine, wherein m-phenylenediamine is subjected to a hofmann rearrangement reaction under reaction conditions to directly produce m-phenylenediamine as shown in the formula (I):
Figure BDA0002423767540000021
the conditions comprise three elements, a first element being a base, a second element being a halogen and/or a hypohalite of the formula m (clo) n, and a third element being at least one, such as at least one, two, at least three, or all four, of a solvent, temperature, pressure, and additives.
In some embodiments of the invention, the base is selected from at least one, such as at least one, two, three, four, five, or all of a metal hydroxide, a metal carbonate, a metal (ene) carboxylate, a metal oxide, a metal sulfide, a metal halide, a metal alkoxide, a metal alkylaminate, a metal thiolate, ammonium hydroxide, ammonia, an organic tertiary amine, an organic secondary amine, and an organic primary amine of the base.
In some embodiments of the invention, M is an n-valent metal cation, and n is a positive integer from 1 to 6, i.e., 1, 2, 3, 4, 5, or 6.
In the invention, the isophthalamide is obtained by converting meta-substituted arylate with a structure RM under conditions a, and is shown as a formula (H):
Figure BDA0002423767540000022
in some embodiments of the invention, X and Y are each independently CO2H、C(O)OR、CHO、CN、C(O)Hal、C(OR)3、C(Hal)3Or C (OC (O) R)3。
In some embodiments of the invention, R is a straight or branched chain alkyl group containing 1 to 24 carbon atoms, or a substituted or unsubstituted aromatic group containing 6 to 24 carbon atoms.
In some embodiments of the invention Hal is the halogen atom fluorine, chlorine, bromine or iodine.
In some embodiments of the invention conditions a comprise two elements, the first element being NH3The second element is the same as said third element of the conditions mentioned above, i.e. at least one of solvent, temperature, pressure and additives, e.g. toOne, two, at least three or all four.
In some embodiments of the invention, the solvent is selected from at least one, such as at least two, three, four, five, six or all, of substituted or unsubstituted aromatic hydrocarbons, straight or branched chain aliphatic hydrocarbons, (sulfoxide), amides, ethers, esters, ketones, nitriles, carboxylic acids, water, amines, ionic liquids, and supercritical carbon dioxide containing 1 to 24 carbons. In some preferred embodiments of the present invention, the solvent is selected from at least one of dimethyl sulfoxide, dimethyl sulfone, benzyl sulfoxide, benzyl sulfone, cyclobutane sulfoxide, sulfolane, trichlorosilane, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, ethylbenzene, diethylbenzene, chlorobenzene, dichlorobenzene, anisole, nitrobenzene, heptane, hexane, petroleum ether, dioxane, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol methyl ether acetate, triethylamine, tributylamine, dimethyl isopropylamine, pyridine, N-tetramethyl ethylene diamine, N-alkyl morpholine, N-alkyl pyrrole, N-dimethyl formamide, formyl morpholine, N-diethyl formamide and N-methyl pyrrolidone, such as at least one, two, three, five, eight, ten, or all.
In the present invention, the reaction can also be carried out by heating and/or grinding the raw material solid phase, and/or by means of ultrasound and/or microwave irradiation, with little or no conventional "solvent" being used.
In some embodiments of the invention, the temperature is from-70 ℃ to 300 ℃. In a preferred embodiment of the invention, the temperature is from-30 ℃ to 250 ℃. In some more preferred embodiments of the invention, the temperature is from-20 ℃ to 200 ℃. In some embodiments of the invention, the temperature is 80 ℃. In other embodiments of the present invention, the temperature is 100 ℃. In yet another embodiment of the present invention, the temperature is 0 ℃.
In some embodiments of the invention, the pressure is from 0.001atm to 200 atm. In some preferred embodiments of the invention, the pressure is from 0.1atm to 100 atm. In some more preferred embodiments of the invention, the pressure is from o.oatm to 20 atm. In some embodiments of the invention, the pressure is 1 atm.
In the present invention, the additive means a reaction promoter, a synergist, a catalyst, an oxidant, a reductant and/or a functional assistant.
In some embodiments of the invention, the additive is a Lewis acid or Lewis base type (L ewisacids/bases) element or compound,
in some embodiments of the invention, the additive is an organic (tertiary) amine, fluoride, chloride, bromide, iodide, oxide, hydroxide, sulfide, or alkoxide of an alkali metal, alkaline earth metal, main group metal, or transition metal.
In some embodiments of the invention, the additive is an alkyl or aryl metal compound.
In some embodiments of the invention, the additive is a carbonate, bicarbonate, sulfite, bisulfate, sulfonate, or carboxylate of an alkali metal, alkaline earth metal, main group metal, or transition metal.
In some embodiments of the invention, the additive is a complex of a mono-or polyvalent organic phosphorus of an alkali metal, alkaline earth metal or transition metal, an organic amine, a hydroxyl group, a ketocarbonyl group, an ester carbonyl group or a carboxylic acid ligand.
In some embodiments of the invention, the additive is a tetraalkylammonium halide, a tetraalkylammonium hydroxide, or an Ionic liquid (Ionic L iquids).
In some embodiments of the invention, the additive is an inorganic protic acid, an organic carboxylic acid, an organic sulfonic acid, a heteropolyacid, a molecular sieve, a zeolite, diatomaceous earth, montmorillonite or kaolin.
In some embodiments of the invention, the additive is a fluoride, chloride, bromide, iodide, oxide, hydroxide, sulfide, or alkoxide of the boron or phosphorus element.
In other embodiments of the present invention, the additive is a mixture of any two or more of the above compounds or a combination thereof.
In some embodiments of the present invention, the additive is used in a catalytic amount equivalent or in an excess amount, based on the molar amount of the starting materials.
In some embodiments of the invention, the RM compound structure is selected from any one of:
Figure BDA0002423767540000051
in the present invention, the base, or halogen and/or hypochlorite M (ClO)nThe molar ratio of the isophthalamide to the isophthalamide is independently (1-1000)/1. In some preferred embodiments of the present invention, the molar ratios are each independently (1-100)/1.
In some embodiments of the invention, the base is a hydroxide of an alkali metal and an alkaline earth metal. In some preferred embodiments of the present invention, the base is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and aluminum hydroxide.
In some embodiments of the invention, the halogen is chlorine or bromine.
In some embodiments of the invention, the hypohalite is at least one of sodium hypochlorite, sodium hypobromite, calcium hypochlorite, calcium hypobromite, potassium hypochlorite, potassium hypobromite, lithium hypochlorite, lithium hypobromite, magnesium hypochlorite, and magnesium hypobromite.
The invention is detailed as follows:
as shown in the reaction formula (I), isophthalamide directly generates m-phenylenediamine through Hofmann Rearrangement (Hofmann Rearrangement) under proper reaction conditions; the process technology is simple, efficient, mild and environment-friendly, and has low cost and economic competitiveness.
Figure BDA0002423767540000061
Here the conditions comprise three elements, one being a base and the other being a halogen or of the formula M (ClO)nThe hypohalite of (a) or a combination of both, which is a combination of any one or any two or more of solvent, temperature, pressure, and/or additives; "base" means a basic metal hydroxide, metal carbonate, metal (ene) carboxylate, metal oxide, metal sulfide, metal halide, metal alkoxide, metal alkylaminate, metal mercaptide, ammonium hydroxide, ammonia, tertiary organic amine, secondary organic amine, primary organic amine; m is a metal cation with a valence of n, and n is an integer between 1 and 6.
Preferred bases are hydroxides of alkali metals and alkaline earth metals, more preferred bases are sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, aluminum hydroxide; preferred halogens are chlorine or bromine; preferred hypohalites are sodium hypochlorite, sodium hypobromite, calcium hypochlorite, calcium hypobromite, potassium hypochlorite, potassium hypobromite, lithium hypochlorite, lithium hypobromite, magnesium hypochlorite, magnesium hypobromite.
The reaction solvent is selected from substituted or unsubstituted aromatic hydrocarbon containing 1-24 carbon atoms, straight-chain or branched-chain aliphatic hydrocarbon, (sulfoxide), amide, ether, ester, ketone, nitrile, carboxylic acid, water, amine, ionic liquid, supercritical carbon dioxide, or a mixed solvent consisting of any two or more of the above solvents; preferred solvents are dimethyl sulfoxide, dimethyl sulfone, benzyl sulfoxide, benzyl sulfone, cyclobutane sulfoxide, sulfolane, trichlorosilane, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, ethylbenzene, diethylbenzene, chlorobenzene, dichlorobenzene, anisole, nitrobenzene, heptane, hexane, petroleum ether, dioxane, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol methyl ether acetate, triethylamine, tributylamine, dimethyl isopropylamine, pyridine, N, N-tetramethylethylenediamine, N-alkylmorpholine, N-alkylpyrrole, N, N-dimethylformamide, formylmorpholine, N, N-diethylformamide, N-methylpyrrolidone, or a mixture of any two or more of these solvents. The reaction can also be carried out with little or no conventional "solvent" and with solid phase heating and/or grinding of the starting materials and/or with promotion by ultrasound and/or microwave irradiation.
The reaction temperature involved in the process is selected from-70 ℃ to 300 ℃, preferably from-30 ℃ to 250 ℃, and more preferably from-20 ℃ to 200 ℃.
The "pressure" of the reaction involved in the process is selected from between 0.001 and 200atm, preferably from between 0.1 and 100atm, more preferably from between 0.1 and 20 atm.
The reaction "additives" referred to in the present process encompass reaction promoters, synergists, catalysts, oxidants, reductants, and/or functional auxiliaries which are lewis acid or lewis base type (L ewis acids/bases) simple substances or compounds, preferably organic (tertiary) amine, alkali metal, alkaline earth metal, main group metal, or transition metal fluorides, chlorides, bromides, iodides, oxides, hydroxides, sulfides, alkoxides, alkyl or aryl metal compounds, or alkali metal, alkaline earth metal, main group metal, or transition metal carbonates, bicarbonates, sulfites, bisulfates, sulfonates, or carboxylates, or alkali metal, alkaline earth metal, or transition metal mono-or polyvalent organophosphates, organic amines, hydroxyl groups, ketocarbonyl, ester carbonyl, or carboxylic acid ligands complexes, or tetraalkylammonium halides, tetraalkylammonium hydroxides, or liquid (Ionic L ids), or inorganic substances in acid, organic carboxylic acid, organic sulfonic acid, heteropolyacid, molecular sieve, zeolite, diatomaceous earth, bentonite, boron, silicon bromide, silicon, phosphorus, oxide, silicon, alkali metal, alkali.
Given that isophthalamide precursors are known to be readily prepared via inexpensive, readily available industrial Raw Materials (Raw Materials) described by structural formula RM in literature methods known to the skilled artisan [ for example: ester as starting material, jpn. kokai Tokkyo Koho, 07330700, 1995; acid is used as a raw material, as disclosed in the patent application 105016940; acyl chloride is used as a raw material, Journal of Applied Polvmer Science, 2012, 124(2), 1707-; nitrile as a raw material, Dalton Transactions, 2016, 45(34), 13590; the invention discloses a novel process technology described by a reaction general formula (II) by using aldehyde as a raw material, RSC Advances, 2013, 3(17), 5889-5894. the invention substantially simultaneously discloses that RM is firstly converted into a isophthalamide intermediate under conditions d, and the isophthalamide is then converted into m-phenylenediamine under conditions b through Hofmann rearrangement. The above steps may be performed in a batch distributed operation on the process flow; it is also possible, preferably, to carry out continuously in a "one-pot" manner:
Figure BDA0002423767540000081
wherein the substituents at the X and Y positions in the structure RM are each independently of the other CO2H，C(O)OR，CHO，CN，C(O)Hal，C(OR)3，C(Hal)3，C(OC(O)R)3(ii) a Where R is a linear or branched alkyl group having 1 to 24 carbon atoms or a substituted or unsubstituted aromatic group having 6 to 24 carbon atoms, and Ha1 is a halogen atom of fluorine, chlorine, bromine or iodine.
conditions a contain two elements, one of which is NH3And the other is the combined application of any one or any two or more of solvent, temperature, pressure, and/or additive. The definitions of solvent, temperature, pressure, and/or additives herein are the same as before.
conditions b are defined the same as the previous conditions.
In practice, some exemplary, but non-limiting structures of RM compounds are as follows:
Figure BDA0002423767540000082
in the examples we will further illustrate.
[ detailed description ] embodiments
The first embodiment is as follows: synthesis of m-phenylenediamine
Figure BDA0002423767540000091
Under the protection of nitrogen, 51.5 g of potassium hydroxide is placed in 350 ml of water and cooled to zero degree in an ice-water bath, 14.2 g of isophthalamide is added, 250 ml of 5.5% sodium hypochlorite solution prepared in advance is added in about 45 minutes under high-efficiency stirring, the reaction system is gradually heated to about 80 ℃ and is continuously heated for 1-2 hours, the thin-layer chromatography T L C method is used for tracking and monitoring the reaction process, the system is cooled to room temperature after the reaction is finished, the pH of the system is adjusted to near neutrality by using dilute hydrochloric acid under a good ventilation state, most of water is removed under reduced pressure, residues are extracted by using ethanol, crude products are concentrated by using ethanol, and the crude products are subjected to high-vacuum reduced-pressure distillation to obtain 7.1 g of m-phenylenediamine pure product.
Example two: synthesis of m-phenylenediamine
Figure BDA0002423767540000092
The intermediate isophthalamide was prepared from isophthalic acid and ammonia according to literature procedures.
Under the protection of nitrogen, 28 g of sodium hydroxide is placed in 35 ml of water, 20 g of chlorine is slowly introduced to prepare a fresh sodium hypochlorite solution in situ, 200 ml of water is added to adjust the concentration of a system for later use, 50 ml of the sodium hypochlorite reagent solution and 250 ml of water are mixed and then cooled in an ice water bath, 49 g of isophthalamide and 175 ml of 1% sodium hydroxide are added under rapid stirring, the reaction system is heated and reacted in a boiling hot water bath, the reaction process is tracked and monitored by a thin-layer chromatography T L C method, the system is cooled to room temperature after the reaction is finished, the pH of the system is adjusted to be nearly neutral by dilute hydrochloric acid under a good ventilation state, most of water is removed under reduced pressure, residues are extracted by ethanol, and a crude product after organic phase is concentrated is distilled under high vacuum and reduced pressure to obtain 2.4 g of an off-white m-.
Example three: synthesis of m-phenylenediamine
Figure BDA0002423767540000101
The intermediate isophthalamide was prepared from the reaction of methyl isophthalate and ammonia according to literature procedures. Referring to the example procedure, Hofmann rearrangement was performed from 6.4 g of isophthalamide to give 3 g of m-phenylenediamine.
Example four: synthesis of m-phenylenediamine
Figure BDA0002423767540000102
Referring to the procedure of example two, a Hofmann degradation reaction was performed at a molar ratio of isophthalamide/sodium hydroxide/chlorine of 1/24/10 to obtain 3.6 g of m-phenylenediamine from 7.8 g of isophthalamide by Hofmann rearrangement.
Example five: synthesis of m-phenylenediamine
Figure BDA0002423767540000103
Under the protection of nitrogen, 2.2 g of dry ammonia gas is slowly introduced into 19.4 g of m-trichlorotoluene to absorb hydrochloric acid gas discharged by the reaction, and the acid liquid and the reaction liquid are mixed and hydrolyzed to prepare 9.1 g of intermediate isophthalamide. Referring to the example procedure, the intermediate was subjected to Hofmann rearrangement to give 4.1 g of m-phenylenediamine.
Example six: synthesis of m-phenylenediamine
Figure BDA0002423767540000111
Under the protection of nitrogen, 6.4 g of isophthaloyl dichloride is added into a three-necked bottle provided with a constant-pressure dropping funnel, 13.2 g of ice-cold ammonia water is added dropwise under the cooling of ice water, and a reaction system is efficiently stirred and reacts overnight to obtain 4.8 g of isophthaloyl diamide. And adding 30 g of sodium hydroxide and 300 ml of deionized water into another three-necked flask with a stirrer, cooling to 0 ℃ by using ice water after stirring and dissolving, adding 16.8 g of bromine under stirring, continuing stirring for half an hour after the addition is finished, and adding 4.2 g of isophthalamide in batches for multiple times. After the addition, the temperature is raised, and the reaction is carried out for 3 hours at about 90 ℃. After the reaction is finished, a step-by-step reduced pressure distillation device is changed, and 2.4 g of m-phenylenediamine product is obtained by distillation.
It should be emphasized that the above-described embodiments are merely illustrative and not restrictive, and that any adjustments or variations, such as reaction conditions or parameters, which may be commonly employed by a person skilled in the art based on the disclosure of this application do not depart from the gist of the present invention, and the scope of protection of this patent shall be governed by the terms of the relevant claims.

Claims (15)

1. The preparation method of m-phenylenediamine is characterized in that as shown in a reaction formula (I), m-phenylenediamine is subjected to Hofmann rearrangement reaction under the conditions of reaction conditions to directly generate m-phenylenediamine:
Figure FDA0002423767530000011
the conditions comprise three elements, wherein the first element is alkali, the second element is halogen and/or the molecular formula is M (ClO)nThe third element is at least one of a solvent, temperature, pressure, and an additive.
2. The method according to claim 1, wherein the base is selected from at least one of basic metal hydroxides, metal carbonates, metal (ene) carboxylates, metal oxides, metal sulfides, metal halides, metal alkoxides, metal alkylamines, metal mercaptides, ammonium hydroxide, ammonia, tertiary organic amines, secondary organic amines, and primary organic amines; m is an n-valent metal cation, and n is 1 to 6.
3. The method of claim 1, wherein the isophthalamide is obtained by converting a meta-substituted aromatic compound having the structure RM under conditions a, as shown in formula (II):
Figure FDA0002423767530000012
wherein X and Y are each independently CO2H、C(O)OR、CHO、CN、C(O)Hal、C(OR)3、C(Hal)3Or C (OC (O) R)3(ii) a R is a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 24 carbon atoms; hal is the halogen atom fluorine, chlorine, bromine or iodine; conditions a comprise two elements, the first element being NH3The second element is the same as the third element of the conditions.
4. The production method according to any one of claims 1 to 3, wherein the solvent is at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbons having 1 to 24 carbons, linear or branched aliphatic hydrocarbons, (sulfoxide), amides, ethers, esters, ketones, nitriles, carboxylic acids, water, amines, ionic liquids, and supercritical carbon dioxide.
5. The method according to claim 4, wherein the solvent is selected from the group consisting of dimethyl sulfoxide, dimethyl sulfone, benzyl sulfoxide, benzyl sulfone, cyclobutane sulfoxide, sulfolane, trichlorosilane, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, ethylbenzene, diethylbenzene, chlorobenzene, dichlorobenzene, anisole, nitrobenzene, heptane, hexane, petroleum ether, dioxane, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol methyl ether acetate, triethylamine, tributylamine, dimethyl isopropylamine, pyridine, N-tetramethylethylenediamine, N-alkylmorpholine, N-alkylpyrrole, N-dimethylformamide, formylmorpholine, N-diethylformamide and N-methylpyrrolidone.
6. The method of any one of claims 1 to 3, wherein the temperature is from-70 ℃ to 300 ℃.
7. The production method according to any one of claims 1 to 3, wherein the pressure is from 0.001atm to 200 atm.
8. The method of any one of claims 1-3, wherein the additive is a reaction promoter, a synergist, a catalyst, an oxidant, a reductant and/or a functional promoter, and is an element or compound of Lewis acid or Lewis base type (L ewisacids/bases).
9. The method of claim 8, wherein the additive is a fluoride, chloride, bromide, iodide, oxide, hydroxide, sulfide or alkoxide of an organic (tertiary) amine, an alkali metal, a main group metal or a transition metal;
alternatively, the additive is an alkyl or aryl metal compound;
alternatively, the additive is an alkali, alkaline earth, main group or transition metal carbonate, bicarbonate, sulfite, bisulfate, sulfonate or carboxylate;
or, the additive is a complex of an alkali metal, alkaline earth metal, or transition metal mono-or polyvalent organophosphorus, organic amine, hydroxyl, ketocarbonyl, ester carbonyl, or carboxylic acid ligand;
alternatively, the additive is a tetraalkylammonium halide, a tetraalkylammonium hydroxide, or an Ionic liquid (Ionic L iquids);
or the additive is inorganic protonic acid, organic carboxylic acid, organic sulfonic acid, heteropoly acid, molecular sieve, zeolite, diatomite, montmorillonite or kaolin;
alternatively, the additive is a fluoride, chloride, bromide, iodide, oxide, hydroxide, sulfide or alkoxide of the boron or phosphorus element.
10. The method of claim 9, wherein the additive is a mixture of any two or more of the above compounds or a combination thereof.
11. The method of claim 10, wherein the additive is used in a catalytic equivalent or an excess equivalent based on the molar amount of the reaction raw materials.
12. The method according to claim 3, wherein said RM compound structure is selected from any one of:
Figure FDA0002423767530000041
13. process according to any one of claims 1 to 3, characterized in that the base, halogen and/or hypochlorite M (ClO)nThe molar ratio of the isophthalamide to the isophthalamide is independently (1-1000)/1, and preferably, the molar ratio is independently (1-100)/1.
14. The production method according to claim 13, characterized in that the base is a hydroxide of an alkali metal and an alkaline earth metal; the halogen is chlorine or bromine; the hypohalite is at least one of sodium hypochlorite, sodium hypobromite, calcium hypochlorite, calcium hypobromite, potassium hypochlorite, potassium hypobromite, lithium hypochlorite, lithium hypobromite, magnesium hypochlorite and magnesium hypobromite.
15. The method of claim 14, wherein the base is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and aluminum hydroxide.
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CN112174828A (en) * 2020-10-29 2021-01-05 山东兴强化工产业技术研究院有限公司 Method for preparing m-phenylenediamine
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Application publication date: 20200724