CN116082165A - Preparation method of 1, 3-cyclohexanediamine - Google Patents
Preparation method of 1, 3-cyclohexanediamine Download PDFInfo
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- CN116082165A CN116082165A CN202211740879.4A CN202211740879A CN116082165A CN 116082165 A CN116082165 A CN 116082165A CN 202211740879 A CN202211740879 A CN 202211740879A CN 116082165 A CN116082165 A CN 116082165A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- OXHOPZLBSSTTBU-UHFFFAOYSA-N 1,3-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC(CBr)=C1 OXHOPZLBSSTTBU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- GRJWOKACBGZOKT-UHFFFAOYSA-N 1,3-bis(chloromethyl)benzene Chemical compound ClCC1=CC=CC(CCl)=C1 GRJWOKACBGZOKT-UHFFFAOYSA-N 0.000 claims description 2
- XCJLUKSDTOVKII-UHFFFAOYSA-N 1,3-bis(iodomethyl)benzene Chemical compound ICC1=CC=CC(CI)=C1 XCJLUKSDTOVKII-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 description 23
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001540 azides Chemical group 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- -1 alicyclic amine Chemical class 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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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
- C07C209/68—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
- C07C209/70—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 reduction of unsaturated amines
- C07C209/72—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 reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- 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
- C07C209/42—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 nitrogen-to-nitrogen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of 1, 3-cyclohexanediamine, which comprises the following steps: (1) Reacting halogenated metaxylene with sodium azide in the presence of a first solvent to obtain an intermediate 1 shown in a formula I; (2) Reacting the intermediate 1, triphenylphosphine and water in the presence of a second solvent to obtain an intermediate MXDA shown in a formula II; (3) Reacting an intermediate MXDA with hydrogen in the presence of a third solvent, a catalyst and an alkali auxiliary agent to obtain 1, 3-cyclohexanediamine; the preparation method has the advantages of simple preparation process, mild conditions and easy laboratory operation;
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 1, 3-cyclohexanediamine.
Background
1, 3-cyclohexanedimethylamine or 1, 3-diamine methylcyclohexane, abbreviated as 1,3-BAC.1,3-BAC is alicyclic amine, is colorless transparent liquid, has slight ammonia smell, is quickly solidified at normal temperature, has low color and luster, has excellent yellowing resistance and can be operated in a humid environment. The 1,3-BAC is an excellent epoxy curing agent, has high curing speed and excellent yellowing resistance, and is widely applied to the fields of ceramic tile joint beautifying agents, automobile lightweight composite materials and the like. In addition, the 1,3-BAC can also be used as a chain extender for synthesizing high polymer materials such as polyurethane, polyamide and the like.
At present, the international production technology is only mastered in the hands of a few companies such as Mitsubishi gas, basv and the like, and the application of products is severely restricted. The preparation methods of 1,3-BAC are classified into an isophthalonitrile method (abbreviated as IPN method) and an m-xylylenediamine method (abbreviated as MXDA method) according to the classification of the raw materials used. The MXDA hydrogenation method has the advantages of high raw material conversion rate, high product selectivity, easy separation and purification of products and the like, and is the most reported method at present. The method comprises two steps, namely, MXDA is prepared in the first step, and the final product is prepared by hydrogenation of MXDA in the second step. In the first step, mixed gas of meta-xylene, ammonia and air is subjected to an ammoxidation method to prepare IPN, and then the IPN is subjected to hydrogenation reduction under Raney nickel catalysis to prepare MXDA. The IPN undergoes an intermediate link of hydrogenation to produce imine in the process of preparing MXDA by catalytic hydrogenation, the imine has high reactivity, and is easy to further react with reaction intermediate products and target products, various high-boiling byproducts are produced by condensation, ammonolysis, crosslinking and other reactions, and the reaction conversion rate, selectivity and yield are affected.
The MXDA hydrogenation method has the advantages of high raw material conversion rate, high product selectivity, easy separation and purification of products and the like, is an industrial production method of 1,3-BAC, and is also a place with more reports of the prior patents. US5741928, CN102688766, CN102690203 and CN102909035 all report on the preparation of 1,3-BAC by MXDA hydrogenation, and at present, liquid ammonia dangerous chemicals are commonly used in the existing preparation process, so that the problems of high investment cost of test equipment, high test operation pressure, liquid ammonia leakage risk and the like exist.
Disclosure of Invention
The invention aims to provide a preparation method of 1, 3-cyclohexanediamine, which comprises the steps of firstly preparing an intermediate azido meta-xylene through azide substitution of halogenated meta-xylene, preparing meta-xylylenediamine through azide reduction, and finally preparing 1,3-BAC through catalytic hydrogenation reduction. The preparation method has the characteristics of simple test operation, mild conditions and easy laboratory operation because no liquid ammonia is used.
In order to achieve the above object, the present invention provides a method for producing 1, 3-cyclohexanediamine, comprising:
(1) Reacting halogenated metaxylene with sodium azide in the presence of a first solvent to obtain an intermediate 1 shown in a formula I;
(2) Reacting the intermediate 1, triphenylphosphine and water in the presence of a second solvent to obtain an intermediate MXDA shown in a formula II;
(3) Reacting the intermediate MXDA with hydrogen in the presence of a third solvent, a catalyst and an alkali auxiliary agent to obtain 1, 3-cyclohexanediamine;
in the invention, as shown in a reaction equation I, (1) halogenated metaxylene is used as a raw material, and substitution reaction is carried out with sodium azide in the presence of a solvent to obtain an intermediate 1; (2) The intermediate 1 obtained in the step (1) is subjected to reduction reaction with triphenylphosphine and water to obtain an intermediate MXDA; (3) And (3) performing high-pressure hydrogenation reduction on the intermediate MXDA obtained in the step (2) in the presence of a catalyst, an alkali auxiliary agent and a solvent to obtain a final product 1, 3-cyclohexanediamine.
According to the present invention, preferably, in the step (1), the halogenated meta-xylene is at least one of 1, 3-di (chloromethyl) benzene, 1, 3-di (bromomethyl) benzene, and 1, 3-di (iodomethyl) benzene.
According to the present invention, preferably, in the step (1), the first solvent is at least one of N, N-dimethylformamide, acetonitrile, methanol, ethanol, dimethyl sulfoxide, and water.
According to the present invention, preferably, in the step (1), the molar ratio of the halogenated meta-xylene to the sodium azide is 1 (2 to 2.2);
the temperature of the reaction is 55-65 ℃.
According to the present invention, preferably, in the step (2), the molar ratio of the intermediate 1 to the triphenylphosphine is 1 (30 to 50);
the feed liquid ratio of the intermediate 1 to the water is 1mmol: 5-10 mL.
According to the present invention, preferably, in the step (2), the second solvent is at least one of tetrahydrofuran, N-dimethylformamide, acetonitrile, methanol and ethanol.
In the present invention, in the step (2), the reaction of the intermediate 1, triphenylphosphine and water is preferably carried out at 20 to 30 ℃.
According to the present invention, preferably, in the step (3), the catalyst is a supported metal ruthenium catalyst, and the supported metal ruthenium catalyst is preferably a carbon material supported ruthenium catalyst (5 wt% Ru/C) and/or an alumina supported ruthenium catalyst (5 wt% Ru/Al) 2 O 3 )；
The catalyst is used in an amount of 10 to 20wt% based on the total weight of the intermediate MXDA.
According to the invention, preferably, in the step (3), the alkali auxiliary agent is lithium nitrate and/or sodium nitrate;
the amount of the alkali auxiliary agent is 10-15 wt% based on the total weight of the intermediate MXDA.
According to the present invention, preferably, in the step (3), the third solvent is at least one of methanol, ethanol, isopropanol, tetrahydrofuran and dioxane.
According to the present invention, preferably, in the step (3), the pressure after the hydrogen is charged is 6 to 8MPa;
the temperature of the reaction is 120-130 ℃.
The technical scheme of the invention has the following beneficial effects:
(1) The invention provides a novel preparation method of 1,3-BAC.
(2) The preparation method provided by the invention has the advantages of simple preparation process, mild conditions and easiness in laboratory operation.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
Fig. 1 shows a nuclear magnetic spectrum of an intermediate 1 according to an embodiment of the invention.
FIG. 2 shows a nuclear magnetic spectrum of intermediate MXDA according to one embodiment of the present invention.
Figure 3 shows a GC-MS spectrum of intermediate MXDA according to one embodiment of the invention.
FIG. 4 shows a nuclear magnetic spectrum of 1,3-BAC (1, 3-cyclohexanediamine) according to one embodiment of the invention.
FIG. 5 shows a GC-MS spectrum of 1,3-BAC (1, 3-cyclohexanediamine) according to one embodiment of the invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention is further illustrated by the following examples:
al used in the following examples 2 O 3 The supported ruthenium catalyst was purchased from beijing enokic technologies limited.
Examples
The preparation method of the 1, 3-cyclohexanediamine comprises the following specific steps:
(1) Preparation of intermediate 1:
13.05g of 1, 3-bis (bromomethyl) benzene and 7.15g of sodium azide were weighed into 150mL of N, N-dimethylformamide and reacted at 60℃with stirring for 10 hours, and TLC detection showed complete reaction of the starting materials. The temperature was lowered, the solution was poured into 1L of deionized water to dilute, extracted with ethyl acetate (100 mL. Times.3), and the organic phase was washed three times with 100mL of water, dried over anhydrous sodium sulfate, filtered and rotary distilled to obtain 8.5g of intermediate compound 1 in a yield of 90.4% and repeated a plurality of times to obtain a sufficient amount of intermediate 1.
(2) Preparation of intermediate MXDA:
9.4g of intermediate 1 was dissolved in 250mL of tetrahydrofuran, 25g of triphenylphosphine and 15mL of deionized water were added to the above solution, and the reaction was stirred at room temperature at 25℃overnight. After the completion of the reaction, the solvent was removed by rotary evaporation, and 5.85g of the target compound MXDA was obtained by column chromatography, whereby the yield was 86%.
(3) Preparation of 1,3-BAC
5.5g of MXDA was weighed into a 100mL reaction vessel, 25mL of isopropanol was added as a solvent, and 0.55g of lithium nitrate and 550mg of Al were added 2 O 3 A supported ruthenium catalyst. The reaction kettle is replaced by nitrogen for 5 times and then replaced by hydrogen for three times, the reaction kettle cover is tightly sealed, and then hydrogen is filled to boost the pressure to 8MPa. The reaction was stopped after the pressure was no longer reduced at 120℃and the conversion of MXDA as measured by GCMS was 100%. After the reaction is cooled and decompressed, the catalyst is filtered and recovered, and the filtrate is rectified to obtain 5.0g of the product 1,3-BAC with the yield of 88 percent.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (10)
1. A method for preparing 1, 3-cyclohexanediamine, which is characterized by comprising the following steps:
(1) Reacting halogenated metaxylene with sodium azide in the presence of a first solvent to obtain an intermediate 1 shown in a formula I;
(2) Reacting the intermediate 1, triphenylphosphine and water in the presence of a second solvent to obtain an intermediate MXDA shown in a formula II;
(3) Reacting the intermediate MXDA with hydrogen in the presence of a third solvent, a catalyst and an alkali auxiliary agent to obtain 1, 3-cyclohexanediamine;
2. the production process according to claim 1, wherein in step (1), the halogenated meta-xylene is at least one of 1, 3-di (chloromethyl) benzene, 1, 3-di (bromomethyl) benzene and 1, 3-di (iodomethyl) benzene.
3. The production method according to claim 1, wherein in the step (1), the first solvent is at least one of N, N-dimethylformamide, acetonitrile, methanol, ethanol, dimethyl sulfoxide, and water.
4. The production process according to claim 1, wherein in the step (1), the molar ratio of the halogenated meta-xylene to the sodium azide is 1 (2 to 2.2);
the temperature of the reaction is 55-65 ℃.
5. The process according to claim 1, wherein in the step (2), the molar ratio of the intermediate 1 to the triphenylphosphine is 1 (30 to 50);
the feed liquid ratio of the intermediate 1 to the water is 1mmol: 5-10 mL.
6. The production method according to claim 1, wherein in the step (2), the second solvent is at least one of tetrahydrofuran, N-dimethylformamide, acetonitrile, methanol and ethanol.
7. The preparation method according to claim 1, wherein in the step (3), the catalyst is a supported metal ruthenium catalyst, and the supported metal ruthenium catalyst is preferably a carbon material supported ruthenium catalyst and/or an alumina supported ruthenium catalyst;
the catalyst is used in an amount of 10 to 20wt% based on the total weight of the intermediate MXDA.
8. The preparation method according to claim 1, wherein in the step (3), the alkali auxiliary agent is lithium nitrate and/or sodium nitrate;
the amount of the alkali auxiliary agent is 10-15 wt% based on the total weight of the intermediate MXDA.
9. The production method according to claim 1, wherein in the step (3), the third solvent is at least one of methanol, ethanol, isopropanol, tetrahydrofuran, and dioxane.
10. The production method according to claim 1, wherein in the step (3), the pressure after the hydrogen is charged is 6 to 8MPa;
the temperature of the reaction is 120-130 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116589363A (en) * | 2023-05-17 | 2023-08-15 | 河南省君恒实业集团生物科技有限公司 | Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN116589363B (en) * | 2023-05-17 | 2024-05-03 | 河南省君恒实业集团生物科技有限公司 | Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed |
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