CN108191674A - A kind of synthetic method of benzidine compound - Google Patents
A kind of synthetic method of benzidine compound Download PDFInfo
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- CN108191674A CN108191674A CN201810141502.4A CN201810141502A CN108191674A CN 108191674 A CN108191674 A CN 108191674A CN 201810141502 A CN201810141502 A CN 201810141502A CN 108191674 A CN108191674 A CN 108191674A
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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
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/28—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with other reducing agents
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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
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The invention discloses a kind of synthetic methods of benzidine compound.Compound (I) obtains compound (II) through catalyzed coupling reaction；Compound (II) obtains compound (III) through alkalinity or acid hydrolytic reaction process；Compound (III) is reacted in organic system through catalytic hydrogenating reduction, obtains benzidine compound (V)；Or compound (V) is obtained by the reaction through catalytic hydrogenating reduction in organic solvent in compound (II), compound (V) obtains compound (IV) through alkalinity or acid hydrolytic reaction.The present invention discloses numerous shortcomings that method overcomes existing method, using conventional commercial catalyst, substantially reduces reaction time, raising production capacity.It is noted that organic solvent of the present invention is recyclable, applies mechanically, the hydroiodic acid or hydrobromate that coupling reaction generates, can the favourable conversions iodide higher for economic value or bromide salts through processing.Therefore, the disclosure method one is economical is easy to industrialized green method.
Description
Technical field
Preparation method more particularly to a kind of synthetic method of benzidine compound the present invention relates to organic compound.
Background technology
3,3', 4,4'- tetra-amino-biphenyls,It is a kind of high-grade high molecular material
Synthon, be mainly used for synthesizing heat-resisting macromolecule resin and synthetic fibers.With the macromolecule resin of its synthesis, fiber
With the properties such as chemical-resistant stability and snugness of fit under superelevation heat resistance, anti-flammability, dimensional stability, high temperature,
Be other materials it is incomparable and substitute.The country of developed country in recent years, particularly aerospace and military project prosperity,
Start such product of primary study in military project, the application of space industry, and acquire a great achievement.As a kind of economic value, section
Skill is worth very high chemicals, and the exploitation of the synthetic method of 3,3', 4,4'- tetra-amino-biphenyls is meaningful.
【US5041666】One kind is disclosed using biphenyl as predominant starting material, synthesizes 3,3', 4,4'- tetra-amino-biphenyls
Method.This method is referred to as " nitrification process ", and including six-step process, the core of method is using Beckmann- rearrangement reactions
The benzidine of acetylation is synthesized, then includes nitration mixture (mixture of nitric acid and sulfuric acid) nitrification, alkaline condition by main process
Hydrolysis, catalytic hydrogen reduction four-step reaction, are represented by with chemical equation,
【US5235105、CN105111092B】By bis- chloro- 4,4'- benzidines of 3,3'- and ammonia in high temperature and pressure item
It under part, is catalyzed through mantoquita, single step reaction obtains 3,3', 4,4'- tetra-amino-biphenyls, and this method is referred to as " ammonolysis process ", with chemistry
Equation is represented by,
【US7999112】A kind of method for preparing 3,3', 4,4'- tetra-amino-biphenyl of high-purity is disclosed, first anhydrous
Under the conditions of anaerobic argon atmospher, palladium bichloride, lithium chloride, absolute methanol are mixed and stirred 2.5 hours at 25 DEG C, adds acetic acid
The methanol solution of sodium and saccharin is added and is stirred 72 hours at 25 DEG C, and reaction terminates, and is obtained through distillation washing, negative pressure drying special
Palladium complex catalyst (yield 75%)；Secondly, by ortho-nitraniline and potassium iodide, potassium metaperiodate, sodium chloride, acetic acid,
Water mixes, and the iodo- 2- nitroanilines of 4- are obtained with 100% yield, the article pointed out this not in reaction process sodium chloride be must can not
Few；Again, the iodo- 2- nitroanilines of 4-, special palladium complex catalyst, toluene are under the conditions of anhydrous and oxygen-free nitrogen atmosphere, warp
Coupling reaction obtains 3,3'- dinitro -4,4'- benzidines, this step yield 79%；3,3'- dinitro -4,4'- diamino
Biphenyl, through nitro-reduction reaction, qualified 3 of purity is disposably obtained with 74% yield under the action of stannous chloride dihydrate,
3', 4,4'- tetra-amino-biphenyls, three-step reaction total recovery 58.46% (in terms of ortho-nitraniline), referred to as " autoimmunity syndrome method ",
It is represented by with chemical equation,
【US6979749】A kind of method for synthesizing 3,3,4,4- tetra-amino-biphenyls is disclosed, with the bromo- 2- nitros acetophenones of 4-
Amine, 4- boric acid -2- nitracetanilides (self-control needs to use organolithium reagent) are coupling reaction raw material, with through up to more than 70
A hour, be strict under the conditions of anhydrous and oxygen-free it is special go out palladium compound as catalyst (make by oneself catalyst yield≤
70%), synthesize crude product under the conditions of anhydrous and oxygen-free, gained crude product purifies that (solvent is petroleum ether-second by column chromatography
Acetoacetic ester system) obtain 3,3'- dinitro -4,4'- diacetylamino biphenyl sterlings；3,3'- bis- is obtained using basic hydrolysis
Nitro -4,4'- benzidine, single step yield 83.62%；Finally 3,3,4,4- tetra-amino-biphenyls are obtained by reduction reaction
Method, single step yield 80%.Referred to as " cross-coupling method ", is represented by with chemical equation,
It is experimentally confirmed, 3,3', 4,4'- tetra-amino-biphenyls can be prepared, but exist using above-mentioned four kinds of methods
Many deficiencies：
(1) " nitrification process " step is various, single step conversion ratio and the very poor, total recovery of selectivity are less than 5%, and intermediate steps
Product and finished product, which are both needed to purifying, could meet the requirement further used, and process costs are high, " three wastes " measure big, environment compatibility not
Foot；
(2) " ammonolysis process " is needed with copper salt catalyst, reaction temperature be up to 300 DEG C, reaction pressure more than hundreds of kilograms, work
Artistic skill consumption is big, safety is too low, and raw materials used 3,3'-, bis- chloro- 4,4'- benzidines have carcinogenicity and are not easy to obtain；
(3) " autoimmunity syndrome method ", the preparation time of special catalyst used in " cross-coupling method " is long, yield is low, cost is high,
Severe reaction conditions, meanwhile, 4- boric acid -2- nitracetanilides are needed in -78 DEG C, stringent anhydrous nothing in " cross-coupling method "
Oxygen, n-BuLi could obtain under the conditions of participating in, and be unfavorable for industrializing implementation.
In conclusion a kind of product yield is high, good quality, technological operation is simple, be easy to industrialization, environmental beneficial is high
3,3' is synthesized, the method for 4,4'- tetra-amino-biphenyls is urgently developed.
The present invention is on the working foundation of forefathers, by testing repeatedly, find with the halogenated -2- nitros-N-protected bases of 4- -
Arylamine is raw material, using commercially available palladium bichloride as catalyst, is reacted in organic solvent system, you can smoothly obtain target compound
3,3'- dinitros -4,4'- two (N-protected base) aminobphenyl.This method has but is not limited to following beneficial point：
(1) a kind of efficient convenient method that synthesis diphenyl amine compound is coupled by halogenated aryl hydrocarbon is disclosed, is effectively avoided
The tedious preparation process of expensive special catalyst and the process conditions for being difficult to industrialized harshness, reduce labor intensity,
Having releived, process conditions, product yield are high, quality is disposably up to standard, substantially increase the industrialization property of technique；
(2) it is not directed to the raw and auxiliary material for being difficult to obtain or market supply is limited in whole process route；Post-reaction treatment letter
Single, one-step reaction yield highest nearly reaches 100%, and whole process route total recovery may be up to 83.5%, disposable gained mesh
Compound 3,3,4,4- 4-aminobiphenyl product production purity is marked more than 99%；
(3) organic solvent is applied mechanically by recovery or directly in open method, reduction reaction uses catalytic hydrogenating reduction,
Meanwhile the hydroiodic acid or hydrobromate of coupling reaction generation are handled (see case study on implementation) through appropriate method, can smoothly be turned
The higher iodide of economic value or bromide salt are turned to, substantially increases the environmental beneficial of technique.
Invention content
A kind of synthetic method of benzidine compound, which is characterized in that include the following steps：
Compound (I) with acid binding agent is mixed in organic solvent, adds in or be added without activator, it is anti-through catalytic coupling
Should, obtain compound (II)；Compound (II) obtains compound (III) through alkalinity or acid hydrolytic reaction process；Compound
(III) it is reacted in a solvent through catalytic hydrogenating reduction, obtains benzidine compound (IV), represent as follows with chemical equation,
Wherein, R1For the acyl group of 1~8 carbon atom, alkyl, alkyl silyl one kind, X be chlorine, bromine, iodine one kind.
A kind of synthetic method of benzidine compound, which is characterized in that include the following steps：
Compound (V) is obtained by the reaction through catalytic hydrogenating reduction in solvent in compound (II), and compound (V) is through alkalinity or acidity
Hydrolysis, obtains compound (IV), represents as follows with chemical equation,
Wherein, R1For the carbonyl of 1~8 carbon atom, alkyl, alkyl silyl one kind.
A kind of synthetic method of benzidine compound, includes the following steps：
Compound (I) with acid binding agent is mixed in organic solvent, adds in or be added without activator, it is anti-through catalytic coupling
Should, obtain compound (II)；
Described compound (I) structural formula is：
Described compound (II) structural formula is：
Wherein, R1For the acyl group of 1~8 carbon atom, alkyl, alkyl silyl one kind, X be chlorine, bromine, iodine one kind.
The catalyzed coupling reaction carries out under reflux conditions, organic solvent for aromatic hydrocarbons, alkane, cycloalkane one kind or
Several mixtures, wherein organic solvent and the mass ratio 3~5 of compound (I):1；Catalyst be palladium and its derivative, wherein
Catalyst and the mass ratio of compound (I) are 0.001~0.005:1；The acid binding agent is tertiary amine, the alkali of 6~twelve carbon atom
The molar ratio of one or more of mixtures of metal carbonate compound, wherein acid binding agent and compound (I) is 0.5~1:1；It is described
Activator be iodine, one kind of potassium iodide, the wherein mass ratio of the quality of activator and compound (I) is 0.001~0.005:
1；The catalyzed coupling reaction is carried out under the conditions of being refluxed.
The R1For acetyl group；The X is iodine；The organic solvent is toluene, dimethylbenzene, alkane, cycloalkane
One or more of mixtures；The acid binding agent for triethylamine, diisopropylethylamine, N- methyldicyclohexyl amine one
Kind or several mixtures；The catalyst is palladium bichloride.
Alkali used in the basic hydrolysis is sodium hydroxide, one kind of potassium hydroxide, basic hydrolysis procedure body
It is pH>12；The basic hydrolysis terminates, with hydrochloric acid or sulfuric acid regulation system pH=6~8；The basic hydrolysis is anti-
Should be carried out under the conditions of being refluxed.
It is sour for sulfuric acid, wherein acid hydrolytic reaction process system pH used in the acid hydrolytic reaction<1；The acid
Property hydrolysis terminates, with sodium hydroxide or potassium hydroxide regulation system pH=6~8；The acid hydrolytic reaction is to return
It is carried out under stream stirring condition.
The alcohol of 1~4 carbon atom, one kind of phase transfer catalyst are added in during the alkalinity or acidic hydrolysis,
In, the mass ratio of alcohol and water is 5~10%, phase transfer catalyst and compound (II) or the mass ratio 0.001~0.005 of (V):
1。
The catalytic hydrogenating reduction reaction used catalyst is palladium carbon, platinum carbon, one kind of Raney's nickel, wherein, catalyst
With compound (II) or the mass ratio 0.001~0.005 of (III):1, the catalytic hydrogenating reduction reaction reaction temperature be
55~65 DEG C, operating pressure be 0.8~1.0MPa；The solvent for methanol, ethyl alcohol, water, N,N-dimethylformamide one
Kind or several mixtures, wherein solvent are 3~5 with the mass ratio of compound (II) or (III):1.
The present invention disclose method and overcomes numerous shortcomings, using the commercial catalyst of routine, it is relatively mild, be convenient for
Under the process conditions of industrialized production, the total recovery to be up to 83.5% disposably obtains the 3,3', 4 of more than 99.5% purity,
The product of 4'- tetra-amino-biphenyls.It is noted that in the disclosure method, organic solvent is recyclable, applies mechanically, coupling reaction
The hydroiodic acid or hydrobromate of generation are handled and (are sketched see embodiment 9) through appropriate method, can favourable conversions be economic valency
The higher iodide of value or bromide salt.Therefore, the disclosure method one is economical is easy to industrialized green method.
Specific embodiment
The following examples further illustrate some features of the present invention, but the present invention applies for the content of protection
It is not limited with range by following embodiments.
Embodiment 1
138 kilograms of ortho-nitranilines, 270 kilograms of methanol, 0.27 kilogram of sulfuric acid, 127 kilograms of iodine are mixed, it is public to add in 115
Jin hydrogen peroxide, is heated to reflux, and stirs 8 hours, and reaction terminates, and is distilled to recover methanol, adds in 300 kg of water, filters, obtains 280
Kilogram filter cake.
The 280 kilograms of filter cakes obtained using the above process flow back as predominant starting material in acetic acid, wherein
650 kilograms of acetic acid, 102 kilograms of aceticanhydride stir 6 hours, and reaction terminates, and are distilled to recover acetic acid, add in 650 kg of water, and centrifugation is done
It is dry, obtain 304 kilogram 99.3% of the iodo- 2- nitracetanilides of 4-, yield 98.65%.
Embodiment 2
The iodo- 2- nitracetanilides of 4- and 153 kilograms of dimethylbenzene, 10.1 kilograms of triethylamines for taking 30.6 kilogram 99.3% mix
It closes, adds in 0.153 kilogram of palladium bichloride, be heated to reflux, stir 6~7 hours, reaction terminates, filtering, filtrate recovery, filter cake
As compound 3,3'- dinitros -4,4'- acetylamino biphenyl.Dry to obtain 17.1 kilograms of amount, purity 99.7%, yield
95%.The nucleus magnetic hydrogen spectrum resonance data data of gained compound 3,3'- dinitro -4,4'- diacetylamino biphenyl：1HNMR
(500MHz, DMSO-d6)：δ8.52(s,2H)；8.14~8.18 (m, 4H)；7.23(br,2H)；2.04(s,6H).
17.1 kilograms of purity that the above process obtains be 99.7% 3,3'- dinitros -4,4'- diacetylaminos biphenyl with
50 kg of water, 7.6 kilograms of sodium hydroxide mixing, add in 2.5 kg ethanols, temperature rising reflux stirs 5 hours, and reaction terminates, cold
But, it with hydrochloric acid regulation system pH=8, filters, obtains 3,3'- dinitros -4,4'- diamino connection of 15 kilograms of purity 98.5%
Benzene tide product；
By the 3,3'- dinitro -4,4'- benzidine tide product of 15 kilograms of purity 98.5% and 45 kilograms of methanol,
0.075 kilogram of palladium carbon mixing, the hydrogen of 0.85~0.9MPa is passed through at 55~60 DEG C, is stirred 3 hours, reaction terminates, and recycling is urged
Agent recycles methanol, adds in 30 kg of water, and centrifugation, drying obtain the 3,3' of 9.3 kilograms of purity 99.3%, 4,4'- tetraminos
Biphenyl, yield 90.6% (with 3,3'- dinitro -4,4'- diacetylamino biphenyl meter).The nuclear magnetic resonance spectroscopy of gained compound
Data：1HNMR (500MHz, DMSO-d6)：δ 6.2~6.9 (m, 6H), 4.2~4.7 (br, 8H).
Embodiment 3
Take 30.6 kilogram 99.3% of the bromo- 2- nitracetanilides of 4- and 153 kilograms of hexamethylenes, 12.9 kilograms of diisopropyls
Ethamine mixing, 0.03 kilogram of iodine, add in 0.153 kilogram of triphenylphosphine palladium, are heated to reflux, and stir 8~9 hours, reaction
Terminate, filtering, filtrate recovery, filter cake is compound 3,3'- dinitro -4,4'- acetylamino biphenyl.Dry to obtain amount
20.3 kilograms, purity 97.9%, yield 93.96%.
Embodiment 4
Take 30.6 kilogram 99.3% of the iodo- 2- nitracetanilides of 4- and 153 kilograms of dimethylbenzene, 19.5 kilograms of N- methyl
Dicyclohexylamine mixes, and adds in 0.03 kilogram of palladium bichloride, is heated to reflux, and stirring is to the reaction was complete, filtering, filtrate recovery,
Filter cake is compound 3,3'- dinitro -4,4'- acetylamino biphenyl.Dry to obtain 17.3 kilograms of amount (purity 99.3%, receipts
Rate 95.7%) 3,3'- dinitro -4,4'- diacetylamino biphenyl.
17.3 kilograms of (purity 99.3%) 3,3'- dinitros -4,4'- diacetylaminos biphenyl that the above process obtains with
50 kg of water, 18.8 kilograms of sulfuric acid mixing add in 0.3 kilogram of PEG, and temperature rising reflux, to the reaction was complete, liquid caustic soda is used in cooling for stirring
Regulation system pH=6 filters, obtains 3,3'- dinitro -4,4'- benzidine tide product of 14.2 kilograms of purity 98.5%；
By the 3,3'- dinitro -4,4'- benzidine tide product of 14.2 kilograms of purity 98.5% and 45 kilograms of methanol,
0.05 kilogram of platinum carbon mixing, the hydrogen of 0.8~1.0MPa is passed through at 55~60 DEG C, and stirring is recycled catalyst to the reaction was complete, returned
Methanol is received, adds in 30 kg of water, centrifugation, drying obtain the 3,3' of 9.28 kilograms of purity 99.5%, and 4,4'- tetra-amino-biphenyls are received
Rate 89.9% (in terms of 3,3'- dinitro -4,4'- diacetylamino biphenyl).
Embodiment 5
3,3'- dinitro -4,4'- the diamino of 14.2 kilograms of purity 98.5% obtained by 5 operating process of embodiment is joined
Benzene tide product are mixed with 45 kilograms of n,N-Dimethylformamide, 0.07 kilogram of Raney's nickel, and 0.95~1.0MPa is passed through at 60~65 DEG C
Hydrogen, stirring recycles catalyst to the reaction was complete in 4 hours, recycles n,N-Dimethylformamide, adds in 30 kg of water, centrifugation,
It is dry, obtain the 3,3' of 9.42 kilograms of purity 99.5%, 4,4'- tetra-amino-biphenyls, yield 91.3% (with 3,3'- dinitro -4,
4'- diacetylamino biphenyl meter).
Embodiment 6
The bromo- 2- nitracetanilides of 4- and 153 kilograms of toluene, 10.1 kilograms of triethylamines for taking 30.6 kilogram 99.3% mix
It closes, adds in 0.153 kilogram of palladium bichloride, be heated to reflux, stirring is to the reaction was complete, and filtering, filtrate recovery, filter cake is chemical combination
Object 3,3'- dinitro -4,4'- acetylamino biphenyl.17.1 kilograms of (purity 98.9%, yields 94.5%) 3 of amount are dried to obtain,
3'- dinitro -4,4'- diacetylamino biphenyl.
Embodiment 7
The iodo- 2- nitracetanilides of 4- and 153 kilograms of heptane, 10.1 kilograms of triethylamines for taking 30.6 kilogram 99.3% mix
It closes, adds in 0.153 kilogram of palladium bichloride, be heated to reflux, stir 6~7 hours, reaction terminates, filtering, filtrate recovery, filter cake
As compound 3,3'- dinitros -4,4'- acetylamino biphenyl.Dry to obtain amount 17.1 kilograms of (purity 99.7%, yields
95.0%) 3,3'- dinitros -4,4'- diacetylamino biphenyl.
It is 99.7%3,3'- dinitro -4,4'- diacetylaminos biphenyl, 85 kg ethanols, 0.5 by 17.1 kilograms of purity
Kg of water, 0.0855 kilogram of Raney's nickel mixing, the hydrogen of 0.95~1.0MPa is passed through at 55~60 DEG C, is stirred 4 hours, reaction knot
Beam recycles catalyst, recycles ethyl alcohol, obtains residue；
30 kg of water are added in into residue, 8 kilograms of potassium hydroxide stir 6~7 hours, cooling, with sulfuric acid regulation system
PH=8, it is centrifugation, dry, obtain the 3,3' of 7.2 kilograms of purity 98.8%, 4,4'- tetra-amino-biphenyls, yield 70.6% (with 3,
3'- dinitro -4,4'- diacetylamino biphenyl meter).
Embodiment 8
Take 30.6 kilogram 99.3% of the chloro- 2- nitracetanilides of 4- and 153 kilograms of toluene, 17 kilograms of potassium carbonate, 0.5
The mixing of kilogram potassium iodide, adds in 0.153 kilogram of dicyan phenyl dichloro palladium, is heated to reflux, and stirs 24 hours, sample examination,
HPLC analysis results are：The 73.3% chloro- 2- nitracetanilides of 4-, 24.7% 3,3'- dinitro -4,4'- diacetyl ammonia
Base biphenyl.
Causing the possible cause that reaction rate is reacted, coupling product is few is：(1) by potassium carbonate, solubility is low in toluene,
After stirring 24 hours, stop stirring, the white potassium carbonate particle for largely having neither part nor lot in reaction is still had in discovery system；(2) by
Iodine and bromine are far below in the activity of chlorine, therefore, under the conditions of same reaction time or even longer reaction time, the chloro- 2- nitros of 4-
Antifebrin conversion ratio is far below the iodo- 2- nitracetanilides of 4-, the bromo- 2- nitracetanilides of 4-.
Embodiment 9
A certain amount of filtrate for handling generation after reaction by 1 coupling reaction of embodiment be distilled to recover organic molten
Agent, it is residue obtained, the water of 3 times of its quality is added in into residue, is stirred, with 50% liquid caustic soda regulation system pH>12, it stands, point
Layer, upper organic layer is triethylamine, is recycled, lower water haline water；
Gained haline water is recycled through appropriate coupling reaction solvent extraction, organic phase, and water phase is concentrated, salt extraction, obtains
Industrial sodium iodide or potassium iodide, mother liquor are recovered.
Contrast test 1
Take 30.6 kilograms of commercially available iodo- 2- nitroanilines of 4- and 153 kilograms of dimethylbenzene, 1 kilogram of N,N-dimethylformamide,
10.1 kilograms of triethylamine mixing, add in 0.153 kilogram of palladium bichloride, are heated to reflux, stir 24 hours, sample examination, HPLC analyses
The result shows that only having the iodo- 2- nitroanilines of 4- in system, i.e., there is not reaction.The contrast test illustrates that amino needs to protect
Effective coupling reaction could be carried out under the conditions of the present invention discloses.
Contrast test 2
Take 30.6 kilogram 99.3% of the iodo- 2- nitracetanilides of 4- and 75 kilograms of dimethylbenzene, 78 kilograms of N, N- dimethyl
Formamide, 10.1 kilograms of triethylamine mixing, adds in 0.153 kilogram of palladium bichloride, is heated to reflux, stir 10 hours.Sampling analysis,
HPLC analysis results are：The 83.3% iodo- 2- nitracetanilides of 4-, 3.7% 3,3'- dinitro -4,4'- diacetyl ammonia
Base biphenyl, remaining is multiple unknown impurity.Also, continue to extend the time, the content ratio of coupling reaction product can not be increased.
Contrast test 3
Take 30.6 kilogram 99.3% the iodo- 2- nitracetanilides of 4- and 153 kilograms of dimethyl sulfoxides, 10.1 kilograms of triethylamines
Mixing adds in 0.153 kilogram of palladium bichloride, is heated to reflux, and stirs 10 hours.Sampling analysis, HPLC analysis results are：98.5%
The chloro- 2- nitracetanilides of 4-, a small amount of unknown impurity.Also, continue to extend the time, have no significant change.
Contrast test 4
Take 30.6 kilogram 99.3% the iodo- 2- nitracetanilides of 4- and 153 kilograms of dimethyl sulfoxides, 17 kilograms of potassium carbonate,
0.5 kilogram of potassium iodide mixing, adds in 0.153 kilogram of dicyan phenyl dichloro palladium, is heated to reflux, stir 24 hours, sample examination,
HPLC analysis results are：24.1% iodo- 2- nitracetanilides of 4-, the iodo- 2- nitroanilines of 64.7% 4-, 9.8% adjacent nitre
Base aniline, remaining is multiple a small amount of unknown impurity.
Contrast experiment 2,3,4 compared with Example 2, illustrates that organic solvent selection has tremendous influence (to tie up acid coupling reaction
The type of agent and to whether there is influence of the activator to coupling reaction smaller).Catalyzed coupling reaction of the present invention is confirmed through many experiments
Organic solvent is aromatic hydrocarbons, one or more of mixtures of alkane, cycloalkane, wherein organic solvent and the quality of compound (I)
Than 3~5:1.
Claims (9)
1. a kind of synthetic method of benzidine compound, which is characterized in that include the following steps：
Compound (I) with acid binding agent is mixed in organic solvent, adds in or be added without activator, through catalyzed coupling reaction, is obtained
To compound (II)；Compound (II) obtains compound (III) through alkalinity or acid hydrolytic reaction process；Compound (III) exists
It is reacted in solvent through catalytic hydrogenating reduction, obtains benzidine compound (IV), represent as follows with chemical equation,
Wherein, R1For the acyl group of 1~8 carbon atom, alkyl, alkyl silyl one kind, X be chlorine, bromine, iodine one kind.
2. a kind of synthetic method of benzidine compound, which is characterized in that include the following steps：
Compound (V) is obtained by the reaction through catalytic hydrogenating reduction in solvent in compound (II), and compound (V) is through alkalinity or acidic hydrolysis
Reaction, obtains compound (IV), represents as follows with chemical equation,
Wherein, R1For the carbonyl of 1~8 carbon atom, alkyl, alkyl silyl one kind.
3. a kind of synthetic method of benzidine compound, which is characterized in that include the following steps：
Compound (I) with acid binding agent is mixed in organic solvent, adds in or be added without activator, through catalyzed coupling reaction, is obtained
To compound (II)；
Described compound (I) structural formula is：
Described compound (II) structural formula is：
Wherein, R1For the acyl group of 1~8 carbon atom, alkyl, alkyl silyl one kind, X be chlorine, bromine, iodine one kind.
4. the synthetic method of a kind of benzidine compound as described in claim 1 or 3, which is characterized in that the catalysis is even
Connection reaction carries out under reflux conditions, and organic solvent is aromatic hydrocarbons, one or more of mixtures of alkane, cycloalkane, wherein having
The mass ratio 3~5 of solvent and compound (I):1；Catalyst is palladium and its derivative, wherein catalyst and compound (I)
Mass ratio is 0.001~0.005:1；The acid binding agent is the tertiary amine of 6~twelve carbon atom, one kind of alkali metal carbonate compound or
The molar ratio of several mixtures, wherein acid binding agent and compound (I) is 0.5~1:1；The activator is iodine, potassium iodide
One kind, the wherein mass ratio of the quality of activator and compound (I) is 0.001~0.005:1；The catalyzed coupling reaction
It is carried out under the conditions of being refluxed.
A kind of 5. synthetic method of benzidine compound as claimed in claim 4, which is characterized in that the R1For acetyl group；
The X is iodine；The organic solvent is toluene, one or more of mixtures of dimethylbenzene, alkane, cycloalkane；It is described
Acid binding agent be triethylamine, one or more of mixtures of diisopropylethylamine, N- methyldicyclohexyl amine；The catalysis
Agent is palladium bichloride.
A kind of 6. synthetic method of benzidine compound as claimed in claim 1 or 2, which is characterized in that the alkaline water
Alkali used in solution reaction is sodium hydroxide, one kind of potassium hydroxide, basic hydrolysis process system pH>12；The alkaline water
Solution reaction terminates, with hydrochloric acid or sulfuric acid regulation system pH=6~8；The basic hydrolysis is under the conditions of being refluxed
It carries out.
A kind of 7. synthetic method of benzidine compound as claimed in claim 1 or 2, which is characterized in that the acid water
It is sour for sulfuric acid, wherein acid hydrolytic reaction process system pH used in solution reaction<1；The acid hydrolytic reaction terminates, and uses hydrogen-oxygen
Change sodium or potassium hydroxide regulation system pH=6~8；The acid hydrolytic reaction is carried out under the conditions of being refluxed.
8. a kind of synthetic method of benzidine compound as claimed in claim 1 or 2, which is characterized in that the alkalinity or
The alcohol of 1~4 carbon atom, one kind of phase transfer catalyst are added in during acidic hydrolysis, wherein, the mass ratio of alcohol and water is 5
~10%, the mass ratio 0.001~0.005 of phase transfer catalyst and compound (II) or (V):1.
9. a kind of synthetic method of benzidine compound as claimed in claim 1 or 2, which is characterized in that the catalysis adds
Hydrogen reduction reaction used catalyst is palladium carbon, platinum carbon, one kind of Raney's nickel, wherein, catalyst and compound (II) or (III's)
Mass ratio 0.001~0.005:1, the reaction temperature that the catalytic hydrogenating reduction reacts is 55~65 DEG C, operating pressure 0.8
~1.0MPa；The solvent is methanol, one or more of mixtures of ethyl alcohol, water, n,N-Dimethylformamide, wherein molten
Agent is 3~5 with the mass ratio of compound (II) or (III):1.
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| CN114478291A (en) * | 2022-03-10 | 2022-05-13 | 西安爱德克美新材料有限公司 | Preparation method of monomer diamine compound of polyimide |
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| US11981616B2 (en) | 2021-03-23 | 2024-05-14 | Hubei Huida High-Tech Co., Ltd | Method for preparing 3,3′-diaminobenzidine |
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