CN104592038A - Preparation method of 5,5-dimethyl-1,3-cyclohexamethylenediamine - Google Patents
Preparation method of 5,5-dimethyl-1,3-cyclohexamethylenediamine Download PDFInfo
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- CN104592038A CN104592038A CN201510014242.0A CN201510014242A CN104592038A CN 104592038 A CN104592038 A CN 104592038A CN 201510014242 A CN201510014242 A CN 201510014242A CN 104592038 A CN104592038 A CN 104592038A
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- hydroresorcinol
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- cyclohexanediamine
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Abstract
The invention relates to a preparation method of 5,5-dimethyl-1,3-cyclohexamethylenediamine, which comprises the following steps: 1. preparing 5,5-dimethyl-1,3-cyclohexyldione from 4-methyl-3-pentenyl-2-one and diethyl malonate; 2. adding the 5,5-dimethyl-1,3-cyclohexyldione into a polar organic solvent, carrying out condensation reaction with hydroxylamine hydrochloride under the action of an alkaline reagent to prepare 5,5-dimethyl-1,3-cyclohexyldiketodioxime; and 3. adding a polar organic solvent into the 5,5-dimethyl-1,3-cyclohexyldiketodioxime, and carrying out catalytic hydrogenation reduction reaction under the catalytic action of a metal catalyst to prepare the 5,5-dimethyl-1,3-cyclohexamethylenediamine. The total yield of the method is 50-55%, the gas-phase purity and content can reach 98.0% above, and the method has high safety and is simple to operate and beneficial to industrial production amplification.
Description
Technical field
The invention belongs to chemosynthesis technical field, particularly relate to a kind of simple to operate, be beneficial to the preparation method of 5,5-dimethyl-1, the 3-cyclohexanediamine that suitability for industrialized production is amplified.
Background technology
Cyclohexanediamine compounds is class application compound very widely, is widely used in medicine intermediate, epoxy curing agent (as coating, sizing agent, matrix material etc.), chiral synthesize reagent, catalyzer, polyamide resin, dyestuff, polyamide fiber etc.
5,5-dimethyl-1,3-cyclohexanediamine is the one in cyclohexanediamine compounds, and molecular formula is C
8h
18n
2, there is following structural formula: but this compound is in the international market but without commercially available.Therefore, the development and application of this compound will have larger prospect.
In prior art with intermediate 5,5-dimethyl-hydroresorcinol dioxime for raw material, utilize Lithium Aluminium Hydride (LiAlH
4) method of reducing prepares 5,5-dimethyl-1,3-cyclohexanediamine.Experiment proves LiAlH
4method of reducing security is low, and in the process that feeds intake, system heat release is fairly obvious, and in reaction process, reaction system sharply expands in container, cause system very easily to rush material, there is potential safety hazard, and aftertreatment is very loaded down with trivial details, and products obtained therefrom yield and purity are all lower.Therefore, the method is unsuitable for suitability for industrialized production amplification.
Summary of the invention
It is high that technical problem to be solved by this invention is to provide a kind of security, simple to operate, is beneficial to the preparation method of 5,5-dimethyl-1, the 3-cyclohexanediamine that suitability for industrialized production is amplified.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of preparation method of 5,5-dimethyl-1,3-cyclohexanediamine, comprises the following steps:
Step 1,4-methyl-3-amylene-2-ketone is joined in polar organic solvent, 4-methyl-3-amylene-2-ketone and diethyl malonate first time reflux generation condensation reaction under organic alkali agents effect, then second time reflux hydrolysis carbon dioxide removal in the inorganic alkaline aqueous solution, reactant pH is regulated to be that 1 ~ 2 generation tautomerism prepares 5,5-dimethyl-hydroresorcinol;
The structural formula of described 5,5-dimethyl-hydroresorcinol is as follows:
Step 2,5,5-dimethyl step 1 prepared-hydroresorcinol joins in polar organic solvent, and under alkaline reagents effect, 5,5-dimethyl-hydroresorcinol dioxime is prepared in 5,5-dimethyl-hydroresorcinol and oxammonium hydrochloride generation condensation reaction; Preferably, alkaline reagents is inorganic alkaline agents or organic alkali agents; More preferably, described alkaline reagents is anhydrous sodium acetate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, salt of wormwood, saleratus.
The structural formula of described 5,5-dimethyl-hydroresorcinol dioxime is as follows:
Step 3,5, the 5-dimethyl-hydroresorcinol dioxime prepared to step 2 adds polar organic solvent, under metal catalyst katalysis 5,5-dimethyl-hydroresorcinol dioxime carries out catalytic hydrogen reduction reaction preparation 5,5-dimethyl-1,3-cyclohexanediamine, the structural formula of described 5,5-dimethyl-1,3-cyclohexanediamine is as follows:
Preferably, in step 1, described organic alkali agents is selected from one or more in sodium ethylate, sodium methylate, sodium propylate, sodium isopropylate, sodium tert-butoxide, potassium tert.-butoxide, sodium tert-amyl alcohol, tertiary amyl alcohol potassium.
Preferably, in step 1, the described inorganic alkaline aqueous solution is sodium hydroxide solution or potassium hydroxide solution.
Preferably, described polar organic solvent is selected from any one or a few in methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, tetrahydrofuran (THF) and dioxane.
Preferably, in step 3, the mass ratio of described polar organic solvent and described 5,5-dimethyl-hydroresorcinol dioxime is 6 ~ 8:1.Mass ratio is controlled in this scope, its objective is and raw material is dissolved completely in solvent, if mass ratio is less than 6:1, then there will be product and can not dissolve completely and be attached in reactor vessel wall, cause raw material reaction incomplete, affect product purity and yield; If higher than 8:1, then can cause waste of solvent, and charging capacity can be caused to reduce in fixing reaction vessel, affect production efficiency.
Preferably, in step 3, described metal catalyst is selected from thunder Buddhist nun Nickel (Raney-Ni), palladium charcoal (Pd/C), platinum charcoal (Pt/C) and platinum oxide (PtO
2) in any one or a few.
Preferably, in step 3, the mass ratio of described metal catalyst and described 5,5-dimethyl-hydroresorcinol dioxime is 0.05 ~ 0.1:1.Mass ratio is controlled in this scope, its objective is and reach optimum response effect, if mass ratio is less than 0.05:1, then there will be the incomplete situation of raw material reaction, affect product purity and yield; If higher than 0.1:1, then catalyzer can be caused to waste, and the generation of other impurity can be caused.
Preferably, in step 3,5,5-dimethyl-hydroresorcinol dioxime carries out the temperature of reaction of catalytic hydrogen reduction reaction is 30 ~ 70 DEG C.Temperature controlled in this scope, object is that raw material is fully dissolved in polar organic solvent, and is conducive to catalyst activity and plays better.If temperature is lower than 30 DEG C, there will be raw material can not dissolve completely, reacts incomplete situation; If temperature is higher than 70 DEG C, the generation of other impurity can be caused.
Preferably, in step 3,5,5-dimethyl-hydroresorcinol dioxime carries out the reaction pressure of catalytic hydrogen reduction reaction is 5 ~ 50atm.By pressure-controlling in this scope, object is that raw material is fully reacted completely, and is conducive to catalyst activity and plays better.If pressure is lower than 5atm, there will be the incomplete situation of raw material reaction; If pressure is higher than 50atm, the generation of other impurity can be caused.
The method utilizing the present invention to prepare 5,5-dimethyl-1,3-cyclohexanediamine prepares 5,5-dimethyl-1,3-cyclohexanediamine, and total recovery is 50 ~ 55%, and gas phase (GC) purity and content all can reach more than 98.0%.Adopt technical scheme of the present invention, method is novel, and cost is low, and security is high, simple to operate, is beneficial to suitability for industrialized production and amplifies.
Embodiment
Be described principle of the present invention and feature below in conjunction with embodiment, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
Step 1, the preparation of 5,5-dimethyl-hydroresorcinol
By 64.4g (0.937mol) sodium ethylate, 138.4g (0.856mol) diethyl malonate, 80.0g (0.815mol) 4-methyl-3-amylene-2-ketone, 257.8g dehydrated alcohol adds in 2L there-necked flask, stirring and evenly mixing, be heated to backflow, return stirring 1 ~ 2h, TLC detect 4-methyl-3-amylene-2-ketone and have reacted completely without residue.Add the mixing solutions that 123.0g (1.972mol) KOH and 566g tap water is made into, return stirring 6 ~ 10h.Steam except the ethanol in system, in remaining aqueous solution system, drip 300g4mol/LHCl aq system pH is adjusted to 1 ~ 2, in system, have yellow solid to separate out gradually, be cooled to room temperature, suction filtration, filter cake is yellow solid, with tap water (100g × 5) drip washing filter cake.Micro-yellow particle shape solid 90.0g is obtained, yield 78.8% (in 4-methyl-3-amylene-2-ketone), GC purity 99.966% after filtration cakes torrefaction.
Step 2, the preparation of 5,5-dimethyl-hydroresorcinol dioxime
By 95.5g (0.681mol) 5,5-dimethyl-hydroresorcinol, 104.1g (1.498mol) oxammonium hydrochloride, 59.9g (1.498mol) sodium hydroxide, 1000g dehydrated alcohol adds in 2L there-necked flask, stirring and evenly mixing, forms white opacity liquid.Detect in 25 ~ 50 DEG C of reactions 3 ~ 5h, TLC, 5,5-dimethyl-hydroresorcinol has reacted completely without residue.Reaction solution is cooled to-5 ~ 0 DEG C, suction filtration, is transferred to by filter cake in 2L beaker, adds 1000g deionized water, room temperature (15 ~ 30 DEG C) making beating stirring 10 ~ 20min, suction filtration, filter cake deionized water (100g × 3) drip washing.White powdery solids 103.0g is obtained, yield 88.8% (with 5,5-dimethyl-hydroresorcinol meter), GC purity 99.237% after filtration cakes torrefaction.
Step 3, the preparation of 5,5-dimethyl-1,3-cyclohexanediamine
By 30.0g5,5-dimethyl-hydroresorcinol dioxime, 1.5gPd/C, 180.0gTHF add in 1L pressure vessel, in 30 ~ 50 DEG C, and catalytic hydrogenation 24h under 5 ~ 10atm condition.Filtration catalizer Pd/C, filtrate reduced in volume, obtains yellow oil 23.9g, yield 95.2% (with 5,5-dimethyl-hydroresorcinol dioxime meter), GC purity 98.5%, content 98.2%.
Embodiment 2
Step 1, the preparation of 5,5-dimethyl-hydroresorcinol
By 50.6g (0.937mol) sodium methylate, 138.4g (0.856mol) diethyl malonate, 80.0g (0.815mol) 4-methyl-3-amylene-2-ketone, 203g methyl alcohol adds in 2L there-necked flask, stirring and evenly mixing, be heated to backflow, return stirring 1 ~ 2h, TLC detect 4-methyl-3-amylene-2-ketone and have reacted completely without residue.Add the mixing solutions that 78.9g (1.972mol) NaOH and 363g tap water is made into, return stirring 6 ~ 10h.Steam except the methyl alcohol in system, in remaining aqueous solution system, drip 300g4mol/LHClaq system pH is adjusted to 1 ~ 2, in system, have yellow solid to separate out gradually, be cooled to room temperature, suction filtration, filter cake is yellow solid, with tap water (100g × 5) drip washing filter cake.Micro-yellow particle shape solid 88.5g is obtained, yield 77.5% (in 4-methyl-3-amylene-2-ketone), GC purity 99.705% after filtration cakes torrefaction.
Step 2, the preparation of 5,5-dimethyl-hydroresorcinol dioxime
By 95.5g (0.681mol) 5,5-dimethyl-hydroresorcinol, 104.1g (1.498mol) oxammonium hydrochloride, 83.9g (1.498mol) potassium hydroxide, 1200g n-propyl alcohol adds in 2L there-necked flask, stirring and evenly mixing, forms white opacity liquid.Detect in 25 ~ 50 DEG C of reactions 3 ~ 5h, TLC, 5,5-dimethyl-hydroresorcinol has reacted completely without residue.Reaction solution is cooled to-5 ~ 0 DEG C, suction filtration, is transferred to by filter cake in 2L beaker, adds 1000g deionized water, room temperature (15 ~ 30 DEG C) making beating stirring 10 ~ 20min, suction filtration, filter cake deionized water (100g × 3) drip washing.White powdery solids 101.5g is obtained, yield 87.5% (with 5,5-dimethyl-hydroresorcinol meter), GC purity 99.107% after filtration cakes torrefaction.
Step 3, the preparation of 5,5-dimethyl-1,3-cyclohexanediamine
By 30.0g5,5-dimethyl-hydroresorcinol dioxime, 2.5g thunder Buddhist nun Nickel, 200.0g n-propyl alcohol adds in 1L pressure vessel, in 40 ~ 60 DEG C, catalytic hydrogenation 24h under 30 ~ 40atm condition.Filtration catalizer thunder Buddhist nun Nickel, filtrate reduced in volume, obtains yellow oil 24.5g, yield 97.6% (with 5,5-dimethyl-hydroresorcinol dioxime meter), GC purity 98.7%, content 98.3%.
Embodiment 3
Step 1, the preparation of 5,5-dimethyl-hydroresorcinol
By 76.9 (0.937mol) sodium isopropylate, 138.4g (0.856mol) diethyl malonate, 80.0g (0.815mol) 4-methyl-3-amylene-2-ketone, 269.8g tetrahydrofuran (THF) adds in 2L there-necked flask, stirring and evenly mixing, be heated to backflow, return stirring 1 ~ 2h, TLC detect 4-methyl-3-amylene-2-ketone and have reacted completely without residue.Add the mixing solutions that 123.0g (1.972mol) KOH and 566g tap water is made into, return stirring 6 ~ 10h.Steam except the tetrahydrofuran (THF) in system, in remaining aqueous solution system, drip 300g4mol/L HCl aq system pH is adjusted to 1 ~ 2, in system, have yellow solid to separate out gradually, be cooled to room temperature, suction filtration, filter cake is yellow solid, with tap water (100g × 5) drip washing filter cake.Micro-yellow particle shape solid 87.2g is obtained, yield 76.4% (in 4-methyl-3-amylene-2-ketone), GC purity 99.951% after filtration cakes torrefaction.
Step 2, the preparation of 5,5-dimethyl-hydroresorcinol dioxime
By 95.5g (0.681mol) 5,5-dimethyl-hydroresorcinol, 104.1g (1.498mol) oxammonium hydrochloride, 122.8g (1.498mol) anhydrous sodium acetate, 1000g dehydrated alcohol adds in 2L there-necked flask, stirring and evenly mixing, forms white opacity liquid.Detect in 25 ~ 50 DEG C of reactions 3 ~ 5h, TLC, 5,5-dimethyl-hydroresorcinol has reacted completely without residue.Reaction solution is cooled to-5 ~ 0 DEG C, suction filtration, is transferred to by filter cake in 2L beaker, adds 1000g deionized water, room temperature (15 ~ 30 DEG C) making beating stirring 10 ~ 20min, suction filtration, filter cake deionized water (100g × 3) drip washing.White powdery solids 108.0g is obtained, yield 93.2% (with 5,5-dimethyl-hydroresorcinol meter), GC purity 99.212% after filtration cakes torrefaction.
Step 3, the preparation of 5,5-dimethyl-1,3-cyclohexanediamine
By 30.0g5,5-dimethyl-hydroresorcinol dioxime, 3.0gPt/C, 210.0g methyl alcohol adds in 1L pressure vessel, in 60 ~ 70 DEG C, and catalytic hydrogenation 24h under 45 ~ 50atm condition.Filtration catalizer Pt/C, filtrate reduced in volume, obtains yellow oil 24.0g, yield 95.6% (with 5,5-dimethyl-hydroresorcinol dioxime meter), GC purity 99.0%, content 98.6%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. the preparation method of dimethyl-1, a 3-cyclohexanediamine, is characterized in that, comprise the following steps:
Step 1,4-methyl-3-amylene-2-ketone is joined in polar organic solvent, 4-methyl-3-amylene-2-ketone and diethyl malonate first time reflux generation condensation reaction under organic alkali agents effect, then second time reflux hydrolysis carbon dioxide removal in the inorganic alkaline aqueous solution, reactant pH is regulated to be that 1 ~ 2 generation tautomerism prepares 5,5-dimethyl-hydroresorcinol;
Step 2,5,5-dimethyl step 1 prepared-hydroresorcinol joins in polar organic solvent, and under alkaline reagents effect, 5,5-dimethyl-hydroresorcinol dioxime is prepared in 5,5-dimethyl-hydroresorcinol and oxammonium hydrochloride generation condensation reaction;
Step 3, to 5,5-dimethyl-1 prepared by step 2, hydroresorcinol dioxime adds polar organic solvent, makes 5,5-dimethyl-1 under metal catalyst katalysis, hydroresorcinol dioxime generation catalytic hydrogen reduction reaction preparation 5,5-dimethyl-1,3-cyclohexanediamine.
2. according to claim 15,5-dimethyl-1, the preparation method of 3-cyclohexanediamine, it is characterized in that, in step 1, described organic alkali agents is selected from one or more in sodium ethylate, sodium methylate, sodium propylate, sodium isopropylate, sodium tert-butoxide, potassium tert.-butoxide, sodium tert-amyl alcohol, tertiary amyl alcohol potassium.
3. the preparation method of 5,5-dimethyl-1,3-cyclohexanediamine according to claim 1, is characterized in that, in step 1, the described inorganic alkaline aqueous solution is sodium hydroxide solution or potassium hydroxide solution.
4. according to claim 15,5-dimethyl-1, the preparation method of 3-cyclohexanediamine, is characterized in that, described polar organic solvent be selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, tetrahydrofuran (THF), dioxane any one or a few.
5. the preparation method of 5,5-dimethyl-1,3-cyclohexanediamine according to claim 4, is characterized in that, in step 3, the mass ratio of described polar organic solvent and described 5,5-dimethyl-hydroresorcinol dioxime is 6 ~ 8:1.
6. according to claim 15, the preparation method of 5-dimethyl-1,3-cyclohexanediamine, is characterized in that, in step 3, described metal catalyst is selected from thunder Buddhist nun Nickel (Raney-Ni), palladium charcoal (Pd/C), platinum charcoal (Pt/C) and platinum oxide (PtO
2) in any one or a few.
7. the preparation method of 5,5-dimethyl-1,3-cyclohexanediamine according to claim 6, is characterized in that, in step 3, the mass ratio of described metal catalyst and described 5,5-dimethyl-hydroresorcinol dioxime is 0.05 ~ 0.1:1.
8. the preparation method of 5,5-dimethyl-1,3-cyclohexanediamine according to claim 1, is characterized in that, in step 3, the temperature of reaction that 5,5-dimethyl-hydroresorcinol dioxime carries out catalytic hydrogen reduction reaction is 30 ~ 70 DEG C.
9. the preparation method of 5,5-dimethyl-1,3-cyclohexanediamine according to claim 1, is characterized in that, in step 3, the reaction pressure that 5,5-dimethyl-hydroresorcinol dioxime carries out catalytic hydrogen reduction reaction is 5 ~ 50atm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10597390B2 (en) | 2014-08-08 | 2020-03-24 | Janssen Sciences Ireland Uc | Indoles for use in influenza virus infection |
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2015
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Non-Patent Citations (3)
| Title |
|---|
| BIGDELI ET AL.: "Catalytic effect of wet molecular sieve 3Å in dry media on syntheses of oximes and 1,3-dioximes", 《JOURNAL OF CHEMICAL RESEARCH》 * |
| BIGDELI ET AL.: "Catalytic effect of wet molecular sieve 3Å in dry media on syntheses of oximes and 1,3-dioximes", 《JOURNAL OF CHEMICAL RESEARCH》, vol. 9, 31 December 2005 (2005-12-31), pages 605 - 607 * |
| HOSINO KOHEI: "Synthetic fibers. IV. Polyamide containing a ring. 2. Polycyclohexylene-5,5-dimethyl-1,3-adipamide", 《NIPPON KAGAKU KAISHI》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10597390B2 (en) | 2014-08-08 | 2020-03-24 | Janssen Sciences Ireland Uc | Indoles for use in influenza virus infection |
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