CN117776929A - Preparation method of N, N-bis (3-aminoalkyl) cyclohexylamine - Google Patents
Preparation method of N, N-bis (3-aminoalkyl) cyclohexylamine Download PDFInfo
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- CN117776929A CN117776929A CN202311720708.XA CN202311720708A CN117776929A CN 117776929 A CN117776929 A CN 117776929A CN 202311720708 A CN202311720708 A CN 202311720708A CN 117776929 A CN117776929 A CN 117776929A
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- cyclohexylamine
- bis
- aminoalkyl
- preparation
- alkali
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- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- BQUQUASUHNZZLS-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-cyclohexylpropane-1,3-diamine Chemical group NCCCN(CCCN)C1CCCCC1 BQUQUASUHNZZLS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000013064 chemical raw material Substances 0.000 abstract description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 9
- -1 dicyanoethyl tertiary amine Chemical class 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 150000003946 cyclohexylamines Chemical class 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ZTGQZSKPSJUEBU-UHFFFAOYSA-N 3-bromopropan-1-amine Chemical compound NCCCBr ZTGQZSKPSJUEBU-UHFFFAOYSA-N 0.000 description 1
- PQIYSSSTRHVOBW-UHFFFAOYSA-N 3-bromopropan-1-amine;hydron;bromide Chemical compound Br.NCCCBr PQIYSSSTRHVOBW-UHFFFAOYSA-N 0.000 description 1
- AYIHVGHQMYIGRH-UHFFFAOYSA-N 3-ethylcyclohexan-1-amine Chemical compound CCC1CCCC(N)C1 AYIHVGHQMYIGRH-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ITZPOSYADVYECJ-UHFFFAOYSA-N n'-cyclohexylpropane-1,3-diamine Chemical compound NCCCNC1CCCCC1 ITZPOSYADVYECJ-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic synthesis and chemical raw material preparation, and particularly relates to a preparation method of N, N-bis (3-aminoalkyl) cyclohexylamine. The invention takes cyclohexylamine and 3-bromoalkylamine hydrobromide as raw materials, and carries out nucleophilic substitution reaction under the conditions of solvent and alkali. The technical route has the advantages of high efficiency, high product yield, convenient post-treatment and purification, and simple and safe operation.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and chemical raw material preparation, and particularly relates to a preparation method of N, N-bis (3-aminoalkyl) cyclohexylamine.
Background
Along with the continuous development of epoxy resin in high-end fields such as electronic products, electrical insulation materials, automobile weight reduction, road and bridge construction and the like, the curing agent is taken as an important component of the epoxy resin, and higher requirements on the quality of the epoxy resin are required. The existing amine epoxy resin curing agents have various defects of long gel time, high curing temperature, poor mechanical properties and the like in the actual use process, and still cannot meet the requirements of high-end fields, so that the amine curing agents are modified to become research hot spots in the field of epoxy resins.
The cyclohexylamine derivative has good water solubility, high curing speed, high hardness of a cured product and good thermal-oxidative aging resistance. The related patents in the prior art mostly take cyano-containing cyclohexylamine derivatives as raw materials under the action of catalysts, and H is introduced 2 And (3) carrying out hydrogenation reaction. CN 113372241A discloses a method for synthesizing dicyanoethyl tertiary amine, which is to synthesize dicyanoethyl tertiary amine by using glycollic acid as catalyst. CN 114907216A discloses a hydrogenation method of dicyanoethyl tertiary amine, which takes Raney nickel and Raney cobalt as catalysts, and introduces H under the action of free amine adsorbent and organic solvent 2 Hydrogenation reaction is carried out, but the catalyst is used in a large amount and is easy to deactivate in the reaction process. The method described in the publication No. CN 114835588B uses dicyanoethyl alicyclic amine as raw material, and uses an anionic ligand catalyst [ M 1 M 2 (NH 3 ) X1 ] m+ X2 [M 2 A1(OH) Y1 ] n- Y2 Under the action, the target product is prepared through hydrogenation. The method disclosed in the patent with publication number CN 115677509A uses N, N-dicyanoethyl cyclohexane as a raw material, raney nickel as a catalyst, and hydrogenates to obtain N, N-bis (3-amino ethyl) cyclohexane.
In summary, the reaction conditions are harsh in the hydrogenation process of cyanoethyl alicyclic amine, the catalyst is easy to deactivate, the service life is short, the activation procedure is complex, the product is easy to decompose, and the like, which seriously affects the application of the modified amine in the field of high-end epoxy resin curing agents, so that the preparation route of the modified amine under the low-cost and low-temperature conditions is imperative.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of N, N-bis (3-amino alkyl) cyclohexylamine. The preparation method has milder reaction conditions, does not involve cyano hydrogenation reaction, and does not involve catalyst which is difficult to use or has high cost.
The technical scheme provided by the invention is as follows:
a process for the preparation of N, N-bis (3-aminoalkyl) cyclohexylamine, comprising the steps of: sequentially adding cyclohexylamine, 3-bromoalkylamine hydrobromide and alkaline components into an organic solvent, heating for full reaction to obtain suspension, filtering, concentrating the obtained filtrate, and distilling and purifying to obtain the target product N, N-bis (3-amino alkyl) cyclohexylamine.
The technical scheme is that cyclohexylamine and 3-bromoalkylamine hydrobromide are used as raw materials, and nucleophilic substitution reaction is carried out under the conditions of solvent and alkali. The technical route has the advantages of high efficiency, high product yield, convenient post-treatment and purification, and simple and safe operation.
Specifically, the number of carbons of the 3-aminoalkyl group in the N, N-bis (3-aminoalkyl) cyclohexylamine is 1 to 5, such as 1, 2, 3, 4, 5.
Based on the technical scheme, different 3-bromoalkylamine hydrobromides can be adopted for reaction to obtain various N, N-bis (3-amino alkyl) cyclohexylamines.
Preferably, the N, N-bis (3-aminoalkyl) cyclohexylamine is N, N-bis (3-aminopropyl) cyclohexylamine, which has the following structural formula:
based on the above technical scheme, an important alicyclic amine compound of N, N-bis (3-aminopropyl) cyclohexylamine can be obtained.
Taking the preparation of N, N-bis (3-aminopropyl) cyclohexylamine as an example, the reaction equation involved is as follows:
specifically, the alkaline component is alkali or alkali salt.
Specifically, the alkali is selected from any one or more of potassium hydroxide, potassium carbonate, sodium carbonate or brilliant carbonate.
Specifically, the alkali salt is selected from any one or a mixture of two of lithium tert-butoxide and sodium tert-butoxide.
Specifically, the mole ratio of cyclohexylamine to 3-bromoalkylamine hydrobromide is 1 (2.2-3).
Specifically, the molar ratio of the alkaline component to the cyclohexylamine is 1 (2-15).
Specifically, the organic solvent is selected from any one or a mixture of more of dimethyl sulfoxide, N-dimethylformamide, methanol, ethanol or acetonitrile.
Specifically, the reaction temperature is 60-160 ℃; the reaction time is 24-96 h.
In the technical scheme, the reaction temperature and the alkaline reagent are changed, so that the yield of N, N-bis (3-aminopropyl) cyclohexylamine is reduced, and the yield of N- (3-aminopropyl) cyclohexylamine is increased.
The invention has the beneficial effects that:
the method takes alkali as a catalyst, and the reaction is carried out at normal pressure and normal temperature, so that the yield is high, the post-treatment is simple, and the method is suitable for industrial mass production.
Drawings
FIG. 1 is a product of example 1 of the present invention, N-bis (3-aminopropyl) cyclohexylamine 1 H NMR spectrum.
FIG. 2 is a HRMS spectrum of the product N, N-bis (3-aminopropyl) cyclohexylamine of example 1 of the present invention.
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present invention.
In the following examples, the starting materials are commercially available products
Example 1
The preparation method of the N, N-bis (3-aminopropyl) cyclohexylamine comprises the following specific steps:
1g K was added to a round bottom flask 2 CO 3 25mL acetonitrile, continuing to add 3-bromopropylamine hydrobromic acid2.38g of salt, 0.495g of cyclohexylamine was added dropwise thereto, and the mixture was reacted at 80℃under reflux for 72 hours. After the reaction is finished, cooling to room temperature, filtering to obtain filtrate, and removing solvent by reduced pressure distillation to obtain light yellow liquid, namely N, N-bis (3-aminopropyl) cyclohexylamine, wherein the yield is 83%. Which is a kind of 1 The H NMR spectrum is shown in FIG. 1, and the HRMS spectrum is shown in FIG. 2.
Example 2
The preparation method of the N, N-bis (3-aminopropyl) cyclohexylamine comprises the following specific steps:
1g K was added to a round bottom flask 2 CO 3 25mL of dimethyl sulfoxide, 2.38g of 3-bromopropylamine hydrobromide was further added, and then 0.495g of cyclohexylamine was added dropwise thereto for reaction at 140℃for 72 hours. After the reaction is finished, cooling to room temperature, filtering to obtain filtrate, and removing solvent by reduced pressure distillation to obtain light yellow liquid, namely N, N-bis (3-aminopropyl) cyclohexylamine, wherein the yield is 86%.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A process for the preparation of N, N-bis (3-aminoalkyl) cyclohexylamine, characterized in that it comprises the following steps: sequentially adding cyclohexylamine, 3-bromoalkylamine hydrobromide and alkaline components into an organic solvent, heating for full reaction to obtain suspension, filtering, concentrating the obtained filtrate, and distilling and purifying to obtain the target product N, N-bis (3-amino alkyl) cyclohexylamine.
2. Process for the preparation of N, N-bis (3-aminoalkyl) cyclohexylamine according to claim 1, characterized in that: in the N, N-bis (3-aminoalkyl) cyclohexylamine, the number of carbons of the 3-aminoalkyl group is 1 to 5.
3. Process for the preparation of N, N-bis (3-aminoalkyl) cyclohexylamine according to claim 2, characterized in that: the N, N-bis (3-aminoalkyl) cyclohexylamine is N, N-bis (3-aminopropyl) cyclohexylamine.
4. Process for the preparation of N, N-bis (3-aminoalkyl) cyclohexylamine according to claim 1, characterized in that: the alkaline component is alkali or alkali salt.
5. The process for producing N, N-bis (3-aminoalkyl) cyclohexylamine according to claim 4, wherein:
the alkali is selected from any one or a mixture of a plurality of potassium hydroxide, potassium carbonate, sodium carbonate or brilliant carbonate;
the alkali salt is selected from any one or a mixture of two of lithium tert-butoxide and sodium tert-butoxide.
6. Process for the preparation of N, N-bis (3-aminoalkyl) cyclohexylamine according to claim 1, characterized in that: the mol ratio of the cyclohexylamine to the 3-bromoalkylamine hydrobromide is 1 (2.2-3).
7. Process for the preparation of N, N-bis (3-aminoalkyl) cyclohexylamine according to claim 1, characterized in that: the molar ratio of the alkaline component to the cyclohexylamine is 1 (2-15).
8. Process for the preparation of N, N-bis (3-aminoalkyl) cyclohexylamine according to claim 1, characterized in that: the organic solvent is selected from any one or a mixture of more of dimethyl sulfoxide, N-dimethylformamide, methanol, ethanol or acetonitrile.
9. Process for the preparation of N, N-bis (3-aminoalkyl) cyclohexylamine according to any one of claims 1 to 8, characterized in that:
the reaction temperature is 60-160 ℃;
the reaction time is 24-96 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311720708.XA CN117776929A (en) | 2023-12-14 | 2023-12-14 | Preparation method of N, N-bis (3-aminoalkyl) cyclohexylamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311720708.XA CN117776929A (en) | 2023-12-14 | 2023-12-14 | Preparation method of N, N-bis (3-aminoalkyl) cyclohexylamine |
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| Publication Number | Publication Date |
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| CN202311720708.XA Pending CN117776929A (en) | 2023-12-14 | 2023-12-14 | Preparation method of N, N-bis (3-aminoalkyl) cyclohexylamine |
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| CN (1) | CN117776929A (en) |
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- 2023-12-14 CN CN202311720708.XA patent/CN117776929A/en active Pending
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