CN111100014A - Preparation method of 1, 3-cyclohexyldimethylamine - Google Patents
Preparation method of 1, 3-cyclohexyldimethylamine Download PDFInfo
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- CN111100014A CN111100014A CN201911124943.4A CN201911124943A CN111100014A CN 111100014 A CN111100014 A CN 111100014A CN 201911124943 A CN201911124943 A CN 201911124943A CN 111100014 A CN111100014 A CN 111100014A
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- cyclohexyldimethylamine
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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
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D245/00—Heterocyclic compounds containing rings of more than seven members having two nitrogen atoms as the only ring hetero atoms
- C07D245/04—Heterocyclic compounds containing rings of more than seven members having two nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D245/06—Heterocyclic compounds containing rings of more than seven members having two nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention provides a preparation method of 1, 3-cyclohexyldimethylamine, which comprises the following steps: step 1, performing a double Mannich reaction on cyclohexanone, formaldehyde and urea under an acidic condition to obtain an intermediate; step 2, reacting the intermediate prepared in the last step with hydrazine hydrate under an alkaline condition, wherein on one hand, the hydrazine hydrate reduces ketone carbonyl into methylene (Wolf-Kishner reduction), and meanwhile, the hydrazine hydrate performs hydrazinolysis on an amide group to expose two amine groups, so that 1, 3-cyclohexyldimethylamine is finally prepared; the present invention can efficiently convert cyclohexanone, formaldehyde and urea into 1, 3-cyclohexyldimethylamine without using high-pressure hydrogenation. The method is simple and convenient to operate, cheap and easily available in reagents, green, safe, efficient and environment-friendly, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of organic synthesis, materials, medicines and pesticides, and particularly relates to a preparation method of 1, 3-cyclohexyldimethylamine.
Background
1, 3-cyclohexyldimethylamine or 1, 3-diaminomethylcyclohexane, known under the english name 1, 3-bis (aminomethyl) cyclohexamine or 1, 3-cyclohexenedimethanamine, abbreviated to 1, 3-BAC. The 1, 3-BAC is colorless and slightly ammonia-flavored transparent liquid, and has a boiling point of 220 deg.C and a freezing point below-70 deg.C. It is soluble in water, alcohol, ether, n-hexane, cyclohexane, benzene, etc. The epoxy resin curing agent, the polyurethane intermediate and the anticorrosive antirust agent are mainly used in the fields of buildings, industry and the like, and also have application in the aspects of pesticides, medicines and the like.
There are two main methods of preparation at present: the first IPN method for preparing 1, 3-BAC, 1994 Mitsubishi gas application patent US5371293, which uses 5% supported ruthenium carbon or ruthenium alumina as a catalyst, carries out hydrogenation reaction under the reaction pressure of 100atm and the reaction temperature of about 100 ℃ in the presence of dioxane and liquid ammonia, and the molar yield of 1, 3-BAC is about 88%. In the patent US4070399, 5% supported Ru-Pd/C is used as a catalyst, lower aliphatic alcohol, dioxane, lower aliphatic amine and the like are used as solvents, the TPN is subjected to hydrogenation reaction in the presence of ammonia in a reaction system at the pressure of about 100atm and the temperature of 100-150 ℃, and the mass yield of 1, 4-BAC is up to 98%. The patent US3998881 uses 5 percent of load type rhodium alumina as a catalyst, uses dioxane, tetrahydrofuran, chloroform and the like as a solvent, has the reaction pressure of about 100atm, the reaction temperature of 100-150 ℃, and the total yield after rectification of 71 percent. The IPN method described above has a disadvantage of poor selectivity for 1, 3-BAC.
The second method is that 1, 3-BAC is prepared by MXDA method, patent EP0703213 uses supported ruthenium, nickel and rhodium catalyst, the solvent used in reaction is methylamine, dimethylamine, ethylenediamine, BAC, methanol and the like, the volume ratio of MXDA and solvent is 1: 3-1: 20, the reaction pressure is 50-150atm, the reaction temperature is 80-130 ℃, and the mass yield can reach 94%. The patent US4181680 uses a supported ruthenium catalyst, the mass of the metal ruthenium accounts for 0.1-10% of the total mass of the catalyst (including the catalyst and the carrier), the solvent used in the reaction is distilled water, the volume ratio of MXDA to the solvent is 1: 1-1: 10, the reaction pressure is 100-150atm, the reaction temperature is 75-130 ℃, and the molar yield can reach about 88%. Since MXDA is obtained by hydrogenation of IPN, the cost for producing 1, 3-BAC from MXDA as a raw material is too high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of 1, 3-cyclohexyldimethylamine.
The present invention achieves the above-described object by the following technical means.
A preparation method of 1, 3-cyclohexyldimethylamine specifically comprises the following steps:
step 1, performing a double Mannich reaction on cyclohexanone, formaldehyde and urea under an acidic condition to obtain an intermediate;
step 2, reacting the intermediate prepared in the last step with hydrazine hydrate under an alkaline condition, wherein on one hand, the hydrazine hydrate reduces ketone carbonyl into methylene (Wolf-Kishner reduction), and meanwhile, the hydrazine hydrate performs hydrazinolysis on an amide group to expose two amine groups, so that 1, 3-cyclohexyldimethylamine is finally prepared;
further, the ratio of the amount of the urea to the amount of the cyclohexanone in the first reaction is 1-1.2: 1;
further, the mass ratio of the formaldehyde to the cyclohexanone used in the first reaction is 2-2.2: 1;
further, the acid used in the first step reaction is common organic or inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid and the like, and the dosage of the acid is preferably controlled to be 3-4 of the pH value of the reaction system;
further, the solvent used in the first step reaction is one or more of water, ethanol, methanol, acetonitrile, dimethyl sulfoxide or N, N-dimethylformamide;
further, the amount ratio of hydrazine hydrate to intermediate substances used in the second step is 4-8: 1;
further, the alkali used in the second step is sodium hydroxide or potassium hydroxide, and the dosage of the alkali is preferably to control the pH value of the reaction system to 10-12;
further, the second step reaction is a solvent-free reaction, or 1, 4-dioxane, ethylene glycol dimethyl ether and the like are used as solvents;
further, the temperature of the second step reaction is 100-160 ℃, preferably 120 ℃.
The invention has the beneficial effects that:
the present invention provides a novel synthesis method which can efficiently convert cyclohexanone, formaldehyde and urea into 1, 3-cyclohexyldimethylamine without using high-pressure hydrogenation. The method is simple and convenient to operate, cheap and easily available in reagents, green, safe, efficient and environment-friendly, and is suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
200ml of solvent water, 9.8 g (0.1mol) of cyclohexanone, 6 g (0.1mol) of urea and 6 g (0.2mol) of formaldehyde were sequentially added to a 500ml reaction flask, and then an appropriate amount of hydrochloric acid was added to adjust the pH of the reaction system to 3, followed by reaction at 80 ℃ for 36 hours, followed by extraction with water and ethyl acetate three times, removal of the water layer, and drying of the organic layer with anhydrous sodium sulfate. Removing the solvent by a rotary evaporator, extracting the product by dichloromethane, and evaporating the solvent to obtain 16.2 g of an intermediate with the yield of 89%, and repeating the steps for multiple times to obtain a sufficient amount of the intermediate;
a500 ml reaction flask was charged with 200ml of a solvent, 1, 4-dioxane, 18.2 g (0.1mol) of an intermediate, 30 g (0.6mol) of hydrazine hydrate, followed by addition of an appropriate amount of sodium hydroxide to adjust the pH of the reaction system to 10, followed by reaction at 120 ℃ for 18 hours, followed by extraction with water and ethyl acetate three times, removal of the water layer, and drying of the organic layer with anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and the product was extracted with methylene chloride and then the solvent was distilled off to obtain 12.5 g of 1, 3-cyclohexyldimethylamine in a yield of 88%.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of 1, 3-cyclohexyldimethylamine is characterized by comprising the following steps:
step 1, performing a double Mannich reaction on cyclohexanone, formaldehyde and urea under an acidic condition to obtain an intermediate;
and 2, reacting the intermediate prepared in the last step with hydrazine hydrate under an alkaline condition, wherein the hydrazine hydrate reduces ketone carbonyl into methylene (Wolf-Kishner reduction), and the hydrazine hydrate performs hydrazinolysis on an amide group to expose two amine groups, so that the 1, 3-cyclohexyldimethylamine is finally prepared.
2. The method of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein the ratio of the amount of urea to cyclohexanone used in the first step is 1 to 1.2: 1.
3. the method of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein the ratio of the amount of formaldehyde to cyclohexanone used in the first step is 2 to 2.2: 1.
4. the method of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein the acid used in the first step is one of hydrochloric acid, sulfuric acid and phosphoric acid, and the amount thereof is controlled to 3 to 4.
5. The method of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein the solvent used in the first step is one or more selected from water, ethanol, methanol, acetonitrile, dimethylsulfoxide and N, N-dimethylformamide.
6. The method of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein the amount of hydrazine hydrate to intermediate in the second step is 4 to 8: 1.
7. the method of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein the alkali used in the second step is sodium hydroxide or potassium hydroxide, and the amount thereof is preferably controlled to 10 to 12 in terms of pH of the reaction system.
8. The method of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein the second step is a solvent-free reaction.
9. The method of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein the second step of the reaction uses 1, 4-dioxane, ethylene glycol dimethyl ether or the like as a solvent.
10. The method of producing 1, 3-cyclohexyldimethylamine according to claim 1, wherein the temperature of the second step is 100 to 160 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911062A (en) * | 2011-08-04 | 2013-02-06 | 上海泰禾化工有限公司 | Method for preparing 1,3-cyclohexyl dimethylamine |
| CN102909035A (en) * | 2011-08-04 | 2013-02-06 | 上海泰禾化工有限公司 | Catalyst for compositing 1,3-cyclohexyl dimethylamine and preparation method of catalyst |
| CN104788323A (en) * | 2014-01-17 | 2015-07-22 | 上海泰禾化工有限公司 | Method for synthesizing 1,4-cyclohexyldimethylamine |
| CN106810451A (en) * | 2015-11-29 | 2017-06-09 | 青岛森美克化工技术有限公司 | A kind of method for preparing 1,3- cyclohexyldimethylamines |
| CN107868007A (en) * | 2016-09-26 | 2018-04-03 | 青岛九洲千和机械有限公司 | A kind of method for preparing 1,3 cyclohexyldimethylamines |
| CN108203386A (en) * | 2016-12-20 | 2018-06-26 | 青岛祥智电子技术有限公司 | A kind of method for preparing 1,3- cyclohexyldimethylamines |
| CN109772312A (en) * | 2019-03-07 | 2019-05-21 | 北京化工大学 | A kind of selection of m-xylene diamine plus hydrogen prepare the catalyst of 1,3- hexamethylene dimethylamine |
| CN110105223A (en) * | 2019-05-15 | 2019-08-09 | 常州大学 | A kind of method that continuity method prepares 1,3- hexamethylene dimethylamine |
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- 2019-11-18 CN CN201911124943.4A patent/CN111100014B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911062A (en) * | 2011-08-04 | 2013-02-06 | 上海泰禾化工有限公司 | Method for preparing 1,3-cyclohexyl dimethylamine |
| CN102909035A (en) * | 2011-08-04 | 2013-02-06 | 上海泰禾化工有限公司 | Catalyst for compositing 1,3-cyclohexyl dimethylamine and preparation method of catalyst |
| CN104788323A (en) * | 2014-01-17 | 2015-07-22 | 上海泰禾化工有限公司 | Method for synthesizing 1,4-cyclohexyldimethylamine |
| CN106810451A (en) * | 2015-11-29 | 2017-06-09 | 青岛森美克化工技术有限公司 | A kind of method for preparing 1,3- cyclohexyldimethylamines |
| CN107868007A (en) * | 2016-09-26 | 2018-04-03 | 青岛九洲千和机械有限公司 | A kind of method for preparing 1,3 cyclohexyldimethylamines |
| CN108203386A (en) * | 2016-12-20 | 2018-06-26 | 青岛祥智电子技术有限公司 | A kind of method for preparing 1,3- cyclohexyldimethylamines |
| CN109772312A (en) * | 2019-03-07 | 2019-05-21 | 北京化工大学 | A kind of selection of m-xylene diamine plus hydrogen prepare the catalyst of 1,3- hexamethylene dimethylamine |
| CN110105223A (en) * | 2019-05-15 | 2019-08-09 | 常州大学 | A kind of method that continuity method prepares 1,3- hexamethylene dimethylamine |
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