CN114835587A - Synthesis method of diamine compound and diamine compound prepared by synthesis method - Google Patents
Synthesis method of diamine compound and diamine compound prepared by synthesis method Download PDFInfo
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- CN114835587A CN114835587A CN202210575493.6A CN202210575493A CN114835587A CN 114835587 A CN114835587 A CN 114835587A CN 202210575493 A CN202210575493 A CN 202210575493A CN 114835587 A CN114835587 A CN 114835587A
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- 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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Abstract
The invention provides a synthesis method of a diamine compound and the diamine compound prepared by the same, and relates to the technical field of polyimide monomer synthesis. The diamine compound has the following structure:
Description
Technical Field
The invention relates to the technical field of polyimide monomer synthesis, in particular to a synthesis method of a diamine compound and the diamine compound prepared by the same.
Background
Polyimides (PI) are a class of polymers characterized by imide rings. The high polymer has outstanding heat resistance, excellent mechanical property, electrical property, stability and the like. The polyimide monomer products can be prepared into products such as films, adhesives, coatings, laminated plates, molding compounds and the like, and the products are widely applied to the fields of aerospace, electronics and electricians, automobiles, precision instruments and the like.
A diamine compound having a specific structure represented by the following formula:
in the prior patent, the compound similar to the above structure is referred to N, N' -bis (4-aminophenyl) -dimethylethylenediamine, and only one of the following synthetic routes can be referred to:
the scheme is that N, N '-di (4-nitrophenyl) -dimethylethylenediamine is subjected to hydrogenation reduction to obtain a product N, N' -di (4-aminophenyl) -dimethylethylenediamine. The adopted scheme is U.S. patent document with publication number US2017/0137604A1, which adopts activated carbon loaded Pd as a catalyst, and introduces hydrogen as a reducing agent, and the reaction temperature is 50 ℃ and the reaction time is 72 hours. The synthesis of N, N' -di (4-nitrophenyl) -dimethylethylenediamine in the patent has the disadvantages of slow reduction reaction and increased production cost.
Wherein, only one of the following synthetic routes of the intermediate N, N' -bis (4-nitrophenyl) -dimethylethylenediamine can be referred to:
the scheme is that N, N '-di (4-nitrophenyl) -ethylenediamine and methyl iodide are synthesized under the catalysis of sodium hydroxide to obtain the product N, N' -di (4-nitrophenyl) -dimethylethylenediamine. The adopted scheme is U.S. patent document with publication number US2017/0137604A 1.
The synthetic route of the intermediate N, N' -di (4-nitrophenyl) -ethylenediamine is as follows:
the first scheme is as follows:
the p-chloronitrobenzene is reacted with ethylenediamine in an ethanol solvent to synthesize N, N' -bis (4-nitrophenyl) -ethylenediamine, according to the scheme described in the documents Recueil des Travaux Chimiques des Pays-Bas, 1937, vol.56, p.541, 554, 863 and 871.
Scheme II:
the parafluoronitrobenzene and the ethylenediamine are heated to 100 ℃ in a DMF solvent under the action of a sodium hydroxide catalyst, and the reaction progress is judged by LC detection of a product N, N' -bis (4-nitrophenyl) -ethylenediamine. The adopted scheme is U.S. patent document with publication number US2017/0137604A 1. The method has the defects that the fluorine-containing compound is used, and the product is sodium fluoride, so that the method has great influence on the environment and the safety of operators.
The third scheme is as follows:
p-bromonitrobenzene reacts with ethylenediamine to synthesize N, N' -di (4-nitrophenyl) -ethylenediamine;
and the scheme is as follows:
p-nitroaniline was reacted with 1, 2-dibromoethane to synthesize N, N' -bis (4-nitrophenyl) -ethylenediamine using the scheme described in the document Chemische Berichte,1907, vol.40, p.5014.
The method for synthesizing diamine needs three steps for synthesis, and has the problems of more synthesis steps, raw material waste and long synthesis period time.
Disclosure of Invention
The invention aims to solve the technical problems of multiple synthesis steps and long synthesis period of the existing diamine synthesis method, and provides a novel diamine compound synthesis method and a diamine compound prepared by the same.
The invention solves the technical problems through the following technical means:
a method for synthesizing a diamine compound, comprising the steps of:
(1) adding the raw materials 1 and 2, alkali and a solvent into a flask, stirring and heating to a reaction temperature; the structural formula of the raw material 1 is
Wherein R1 is a hydrogen atom or an alkyl group of 1-6 carbon atoms, and X is fluorine, chlorine or bromine; the structural formula of the raw material 2 is
Wherein R2 and R3 are alkyl groups with 1-5 carbon atoms, and n is an integer of 1-6;
tracking the reaction process by liquid chromatography, cooling the mother liquor to room temperature after the reaction is finished, pouring high-purity water, continuously stirring, and stopping stirring after the dropwise addition is finished; filtering, washing with ethanol water to obtain a dinitro compound intermediate; the structural formula of the dinitro compound intermediate is shown in the specification
(2) Adding the dinitro compound intermediate prepared in the step (1) into a flask, adding ethanol, high-purity water and a catalyst, stirring and heating to reflux; slowly dripping hydrazine hydrate into the flask, and tracking the reaction process by liquid chromatography to obtain the diamine compound.
Has the advantages that: the method for synthesizing the diamine can be completed by only two steps, and compared with the traditional method for synthesizing similar diamine, the method simplifies the operation steps, shortens the synthesis period, greatly reduces the cost and improves the working efficiency.
Preferably, the solvent in step (1) is one or more of DMF, DMAC, NMP, DMSO.
Preferably, the base in step (1) is one or more of sodium hydroxide, sodium carbonate, potassium hydroxide, triethylamine, tetramethylammonium hydroxide and ethylenediamine.
Preferably, in the step (1), the weight of the raw material 1 is 31.5-42g, the weight of the raw material 2 is 8-11.62g, the weight of the alkali is 8-22g, and the weight of the solvent is 226-295 g.
Preferably, the reaction temperature in the step (1) is 80-180 ℃.
Preferably, the liquid chromatography in the step (1) detects the reaction progress, and the reaction is finished within 6-8 hours; the amount of high-purity water is 1000-1500ml, and the stirring is continued for 30-45 min.
Preferably, the amount of the ethanol in the step (1) is 100-200ml, and the concentration of the ethanol is 40-60%.
Preferably, the dinitro compound intermediate of the step (2) has a weight of 8 to 20g, ethanol in an amount of 20 to 40ml, high purity water in an amount of 10 to 30ml, and hydrazine hydrate in an amount of 15 to 35 g.
Preferably, the catalyst is 0.5 to 3g of palladium on carbon.
The invention also provides a diamine compound prepared by the diamine synthesis method, which has a structural formula as follows:
wherein R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; r2 and R3 are alkyl groups having 1 to 5 carbon atoms; n is an integer of 1 to 6.
The invention has the advantages that:
1. the invention provides a novel method for synthesizing diamine, which has the advantages of simple synthesis steps, raw material saving, short synthesis period and greatly reduced cost.
2. The invention also provides a novel diamine compound structure, wherein 2 nitrogen atoms are contained between two benzene rings, and lone pair electrons on the nitrogen atoms increase the electron cloud density between the two benzene rings, so that the diamine compound structure is beneficial to charge conduction: and no N-H bond exists on the nitrogen atom between the two benzene rings, so that the structure is stable and cannot be oxidized by oxygen in the air.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
p-chloronitrobenzene (31.5g, 0.2mol), N, N' -dimethylethylenediamine (8.815g, 0.1mol), sodium carbonate (21.2g, 0.2mol), 226g DMAC were added to the flask, stirred and heated to 140 ℃ and reacted for 8 hours, followed by detection of the end of the reaction by liquid chromatography; and cooling the mother liquor after reaction to room temperature, pouring the mother liquor into 1000ml of high-purity water, continuously stirring for 30min, and performing suction filtration to obtain N, N' -bis (4-nitrophenyl) -dimethylethylenediamine, washing a filter cake with 200ml of 50% ethanol, and sampling to detect that the purity is 95% and the yield is 91%.
Adding 10g N, N ' -bis (4-nitrophenyl) -N, N ' -dimethylethylenediamine into a flask, adding 20ml of high-purity water, 30ml of ethanol and 1g of palladium-carbon, heating and stirring to reflux, dropwise adding 18g of hydrazine hydrate to reduce a dinitro compound, detecting the reaction progress by liquid chromatography, preserving heat for 1 hour after complete reduction, covering diatomite with Buchner funnel filter paper while hot, filtering to remove the palladium-carbon, cooling the filtrate to 5 ℃, crystallizing the product out of the solution, performing suction filtration to obtain the product after 12 hours of crystallization, washing a filter cake by 100ml of 50% ethanol, wherein the filter cake is N, N ' -bis (4-aminophenyl) -dimethylethylenediamine, and the sampling detection purity is 99% and the yield is 82%.
Example 2:
adding p-bromonitrobenzene (40.402g, 0.2mol), N, N' -diethylethylenediamine (11.62g, 0.1mol), sodium hydroxide (8g, 0.2mol) and 295g DMSO into a flask, stirring and heating to 130 ℃ for dissolution, reacting for 6 hours, and detecting the reaction by liquid chromatography; cooling the mother liquor after reaction to room temperature, pouring the mother liquor into 1350ml of high-purity water, continuously stirring for 30min, and performing suction filtration to obtain N, N '-bis (4-nitrophenyl) -N, N' -diethylethylenediamine, washing a filter cake with 200ml of 50% ethanol, and sampling to detect the purity of 94% and the yield of 88%.
Adding 10g N, N '-bis (4-nitrophenyl) -N, N' -diethyl ethylenediamine into a flask, adding 20ml of high-purity water, 30ml of ethanol and 1g of palladium-carbon, heating and stirring to reflux, dropwise adding 18g of hydrazine hydrate to reduce a dinitro compound, detecting the reaction progress by liquid chromatography, preserving heat for 1 hour after complete reduction, covering diatomite with Buchner funnel filter paper while hot, filtering to remove the palladium-carbon, cooling the filtrate to 5 ℃, crystallizing the product out of the solution, performing suction filtration to obtain the product after 12 hours of crystallization, washing a filter cake with 100ml of 50% ethanol, wherein the filter cake is N, N '-bis (4-aminophenyl) -N, N' -diethyl ethylenediamine, and the sampling detection purity is 99% and the yield is 90%.
Example 3:
adding 5-chloro-2-nitrotoluene (34.316g, 0.2mol), N, N' -dimethylethylenediamine (8.815g, 0.1mol), sodium hydroxide (8g, 0.2mol) and 243g NMP into a flask, stirring and heating to 130 ℃ for reaction, and after 6.5 hours of reaction, detecting the reaction by liquid chromatography; and cooling the mother liquor after reaction to room temperature, pouring the mother liquor into 1000ml of high-purity water, continuously stirring for 30min, and performing suction filtration to obtain N, N' -bis (4-nitro-3-tolyl) -dimethylethylenediamine, washing a filter cake by 100ml of 50% ethanol, and sampling to detect the purity of 93% and the yield of 90%.
Adding 10g N, N '-di (4-nitro-3-methylphenyl) -dimethylethylenediamine into a flask, adding 20ml of high-purity water, 30ml of ethanol and 1g of palladium carbon, heating and stirring to reflux, dropwise adding 18g of hydrazine hydrate until the reduction is complete, then preserving heat for 1 hour, covering diatomite with Buchner funnel filter paper while hot to remove the palladium carbon, cooling the filtrate to 5 ℃, crystallizing the product from the solution, preserving heat for 4 hours, and then carrying out suction filtration to obtain the product, washing a filter cake with 100ml of 50% ethanol, wherein the filter cake is N, N' -di (4-amino-3-methylphenyl) -dimethylethylenediamine, and the purity is 99% by sampling detection and the yield is 86%.
Example 4:
adding p-chloronitrobenzene (42g, 0.2mol), N, N' -dimethylethylenediamine (8g, 0.1mol), sodium carbonate (22g, 0.2mol) and 226g DMAC into a flask, stirring and heating to 180 ℃, reacting for 8 hours, and detecting the reaction by liquid chromatography; and cooling the mother liquor after reaction to room temperature, pouring the mother liquor into 1500ml of high-purity water, continuously stirring for 35min, and performing suction filtration to obtain N, N' -bis (4-nitrophenyl) -dimethylethylenediamine, washing a filter cake with 150ml of 40% ethanol, and sampling to detect that the purity is 85% and the yield is 70%.
Adding 20g N, N ' -bis (4-nitrophenyl) -N, N ' -dimethylethylenediamine into a flask, adding 30ml of high-purity water, 40ml of ethanol and 3g of palladium-carbon, heating and stirring to reflux, dropwise adding 35g of hydrazine hydrate to reduce a dinitro compound, detecting the reaction progress by liquid chromatography, preserving heat for 1 hour after complete reduction, covering diatomite with Buchner funnel filter paper while hot, filtering to remove the palladium-carbon, cooling the filtrate to 5 ℃, crystallizing the product out of the solution, performing suction filtration to obtain the product after 12 hours of crystallization, washing a filter cake by 100ml of 50% ethanol, wherein the filter cake is N, N ' -bis (4-aminophenyl) -dimethylethylenediamine, and the sampling detection purity is 98%, and the yield is 94%.
Example 5:
adding p-chloronitrobenzene (31.5g, 0.2mol), N, N' -dimethylethylenediamine (8g, 0.1mol), sodium carbonate (10g, 0.2mol) and 226g DMAC into a flask, stirring and heating to 80 ℃, and reacting for 8 hours, and detecting the reaction by liquid chromatography; cooling the mother liquor after reaction to room temperature, pouring the mother liquor into 1500ml of high-purity water, continuously stirring for 45min, and performing suction filtration to obtain N, N' -bis (4-nitrophenyl) -dimethylethylenediamine, washing a filter cake with 200ml of 60% ethanol, and sampling to detect the purity of 83% and the yield of 65%.
Adding 8g N, N ' -bis (4-nitrophenyl) -N, N ' -dimethylethylenediamine into a flask, adding 10ml of high-purity water, 20ml of ethanol and 0.5g of palladium-carbon, heating and stirring to reflux, dropwise adding 15g of hydrazine hydrate to reduce a dinitro compound, detecting the reaction progress by liquid chromatography, preserving heat for 1 hour after complete reduction, covering diatomite with Buchner funnel filter paper while hot, filtering to remove the palladium-carbon, cooling the filtrate to 5 ℃, crystallizing out a product from the solution, performing suction filtration after 12 hours of crystallization to obtain the product, washing a filter cake by 100ml of 50% ethanol, wherein the filter cake is N, N ' -bis (4-aminophenyl) -dimethylethylenediamine, and sampling detection purity is 97% and yield is 89%.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for synthesizing a diamine compound, comprising the steps of:
(1) adding the raw materials 1 and 2, alkali and a solvent into a flask, stirring and heating to a reaction temperature; the structural formula of the raw material 1 is
Wherein R1 is a hydrogen atom or an alkyl group of 1-6 carbon atoms, and X is fluorine, chlorine or bromine; the structural formula of the raw material 2 is
WhereinR2 and R3 are alkyl with 1-5 carbon atoms, and n is an integer of 1-6;
detecting the reaction process by liquid chromatography, cooling the mother liquor to room temperature after the reaction is finished, pouring high-purity water, continuously stirring, and stopping stirring after the dropwise addition is finished; carrying out suction filtration and ethanol washing to obtain a dinitro compound intermediate; the structural formula of the dinitro compound intermediate is shown in the specification
(2) Adding the dinitro compound intermediate prepared in the step (1) into a flask, adding ethanol, high-purity water and a catalyst, stirring and heating to reflux; slowly dripping hydrazine hydrate into the flask, and detecting the reaction process by liquid chromatography to obtain the diamine compound.
2. A synthetic method for preparing the diamine compound of claim 1, wherein the solvent in the step (1) is one or more of DMF, DMAC, NMP, DMSO.
3. The method for synthesizing a diamine compound according to claim 1 or 2, wherein the base in the step (1) is one or a combination of sodium hydroxide, sodium carbonate, potassium hydroxide, triethylamine, tetramethylammonium hydroxide and ethylenediamine.
4. The method for synthesizing a diamine compound as claimed in claim 3, wherein the weight of the raw material 1 in the step (1) is 31.5 to 42g, the weight of the raw material 2 is 8 to 11.62g, the weight of the base is 8 to 22g, and the weight of the solvent is 226-295 g.
5. The method for synthesizing a diamine compound according to claim 4, wherein the reaction temperature in the step (1) is 80 to 180 ℃.
6. The method for synthesizing a diamine compound according to claim 1, wherein the progress of the reaction is detected by liquid chromatography in the step (1) and the reaction is completed within 6 to 8 hours; the amount of high-purity water is 1000-1500ml, and the stirring is continued for 30-45 min.
7. The method for synthesizing a diamine compound as claimed in claim 5, wherein the amount of ethanol in the step (1) is 200ml and the concentration of ethanol is 40-60%.
8. The method for synthesizing a diamine compound according to claim 1, wherein the dinitro compound intermediate in the step (2) has a weight of 8 to 20g, an amount of ethanol of 20 to 40ml, an amount of high purity water of 10 to 30ml, and a weight of hydrazine hydrate of 15 to 35 g.
9. The method for synthesizing a diamine compound according to claim 1, wherein the catalyst is 0.5 to 3g of palladium on carbon.
10. The diamine compound produced by the method for synthesizing a diamine compound according to any one of claims 1 to 9, which has a structural formula as follows:
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| US20170137604A1 (en) * | 2014-05-22 | 2017-05-18 | Otsuka Chemical Co., Ltd. | Rubber composition, tire, bisphenyldiamine compound, and anti-aging agent |
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2022
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| US4137080A (en) * | 1975-11-07 | 1979-01-30 | Konishiroku Photo Industry Co., Ltd. | Process for dye image production on a light-sensitive silver halide photographic material |
| US4211561A (en) * | 1978-12-08 | 1980-07-08 | E. I. Du Pont De Nemours And Company | Method of producing cross-linked polymeric images |
| CN102585843A (en) * | 2011-01-05 | 2012-07-18 | Jnc株式会社 | Liquid crystal alignment agents for photo-alignment, liquid crystal photo-alignment layers, and liquid crystal displays using the same |
| CN104974768A (en) * | 2014-04-14 | 2015-10-14 | 捷恩智株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element |
| US20170137604A1 (en) * | 2014-05-22 | 2017-05-18 | Otsuka Chemical Co., Ltd. | Rubber composition, tire, bisphenyldiamine compound, and anti-aging agent |
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