CN111217710B - Method for preparing 1, 5-pentanediamine by organic catalysis of L-lysine chemical decarboxylation - Google Patents

Method for preparing 1, 5-pentanediamine by organic catalysis of L-lysine chemical decarboxylation Download PDF

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CN111217710B
CN111217710B CN202010123455.8A CN202010123455A CN111217710B CN 111217710 B CN111217710 B CN 111217710B CN 202010123455 A CN202010123455 A CN 202010123455A CN 111217710 B CN111217710 B CN 111217710B
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lysine
pentanediamine
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hydrochloride
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CN111217710A (en
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陶友华
陈金龙
王献红
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Changchun Institute of Applied Chemistry of CAS
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    • 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
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Abstract

The invention provides a method for preparing 1, 5-pentanediamine by organic catalysis of L-lysine chemical decarboxylation, and belongs to the field of 1, 5-pentanediamine preparation methods. Taking L-lysine hydrochloride as an initial raw material, adding alkali liquor, performing neutralization reaction at room temperature, and then adding a solvent, or taking L-lysine as an initial raw material, and directly adding a solvent to obtain a reactant; adding a catalyst into the reaction system, and stirring for reaction; evaporating the solvent to dryness, dissolving in water, and extracting with organic solvent; adding hydrochloric acid into the water phase, and stirring for reaction; evaporating water to dryness to obtain a crude product, and washing with a solvent to obtain the 1, 5-pentanediamine hydrochloride. The method has the advantages of mild reaction conditions, simple operation, cheap and easily-obtained catalyst and solvent, recycling, low production cost, environmental friendliness and high product yield, and is suitable for large-scale preparation of the 1, 5-pentanediamine product.

Description

Method for preparing 1, 5-pentanediamine by organic catalysis of L-lysine chemical decarboxylation
Technical Field
The invention belongs to the field of preparation methods of 1, 5-pentanediamine, and particularly relates to a method for preparing 1, 5-pentanediamine by organic catalysis of chemical decarboxylation of L-lysine.
Background
Worldwide annual demand for nylon exceeds 700 million tons, and the market demand for hexamethylenediamine as a raw material for nylon has exceeded 200 million tons/year. Although the market demand is vigorous, the production raw materials are still monopolized by foreign companies, and the development of the nylon industry in China is seriously hindered. On the other hand, the production of the hexamethylene diamine takes petrochemical products as raw materials, and with the increasing exhaustion of petroleum resources, the trend of air pollution and global warming worsening, the search for a hexamethylene diamine substitute which can be produced from renewable resources has important significance.
The 1, 5-pentanediamine, also known as cadaverine, 1, 5-diaminopentane, pentamethylene diamine or cadaverine toxin, and the hexamethylene diamine are homologies, can replace the hexamethylene diamine and dicarboxylic acid to carry out polymerization reaction to prepare novel nylon 5X (nylon 54, nylon 56, nylon 510 and the like), has the performance comparable to or even superior to that of classical nylon 66, is an environment-friendly, sustainable development type and high temperature resistant bioplastic, and has wide application prospect.
Decarboxylation of lysine can produce 1, 5-pentanediamine. Lysine is a renewable resource from biomass, and with the development of bioengineering technology, the production of lysine is developed vigorously. At present, the domestic lysine productivity is over 60 percent, and the over-production condition is likely to be further aggravated. Therefore, the development of a new technology for producing 1, 5-pentanediamine by using lysine as a raw material is beneficial to solving the problem of excess lysine productivity, and can drive the development of upstream and downstream industries of lysine, prolong the industrial value chain and have important social and economic benefits.
At present, more reports are related to the preparation of 1, 5-pentanediamine by decarboxylation of lysine by a biological method. But the method has the problems of harsh operating conditions, complex fermentation process, difficult separation of the fermented thalli and the fermentation liquor, low yield, high industrial cost and the like. The chemical method for preparing 1, 5-pentanediamine by decarboxylation of lysine has fewer reports. Chinese patent CN110143882A reports a method for preparing 1, 5-pentanediamine by oxidative decarboxylation and cyano reduction using lysine as a starting material, but it requires a large excess of transition metal and the product purification process is complicated and the yield is low. U.S. Pat. No. 3, 7485756, 2 reports a process for the decarboxylation of lysine to 1, 5-pentanediamine, which, although the product can be purified by continuous distillation, neglects the recovery of the catalyst and has a high reaction temperature (240 ℃ C.) and a low product yield (52.1%). In U.S. Pat. No. 4, 9452954B2 and the references Synth. Commun.2015,45,2691-2700 |, a process for the preparation of 1, 5-pentanediamine by chemical decarboxylation of lysine with microwave assistance is reported, but still requires high temperature conditions of 190 ℃. A chemical decarboxylation of amino acids, including lysine, is reported in the chem.Lett.C 1986,15, 893-896, but there is no mention of catalyst recovery and product work-up. The document Eur.J.org.chem.2018, 4265-4271 also reports a method for preparing 1, 5-pentanediamine by microwave-assisted chemical decarboxylation of lysine, wherein the reaction temperature still needs 190 ℃, and the product yield is low and is only 31-37%. A process for the organocatalytic decarboxylation of amino acids is described in the document [ ChemCatchem 2019,11, 4297-4306 ], but in which the yield of lysine decarboxylation is only 28%. The reported methods for preparing 1, 5-pentanediamine by chemically decarboxylating lysine have certain limitations, and the feasibility of industrial production of the 1, 5-pentanediamine is reduced.
Disclosure of Invention
The invention aims to solve the problems of high use of a large amount of transition metals, high reaction temperature, low product yield and the like in the conventional method for preparing 1, 5-pentanediamine, and provides a method for preparing 1, 5-pentanediamine by organic catalysis of chemical decarboxylation of L-lysine.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for preparing 1, 5-pentanediamine by organically catalyzing chemical decarboxylation of L-lysine comprises the following steps:
(1) taking L-lysine hydrochloride as an initial raw material, adding alkali liquor, performing neutralization reaction at room temperature, and then adding a solvent, or taking L-lysine as an initial raw material, and directly adding a solvent to obtain a reactant;
(2) adding a catalyst into the reaction system in the step (1), and stirring for reaction;
(3) evaporating the solvent to dryness, adding water for dissolving, and extracting and separating liquid by using an organic solvent;
(4) adding hydrochloric acid into the water phase, and stirring for reaction;
(5) and evaporating the water to dryness to obtain a crude product, and washing the crude product with a solvent to obtain the 1, 5-pentanediamine hydrochloride.
Preferably, the alkali solution in step (1) is an aqueous solution prepared from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, potassium carbonate, sodium carbonate, potassium tert-butoxide or sodium tert-butoxide.
Preferably, when L-lysine hydrochloride is used as a starting material in the step (1), the molar ratio of the L-lysine hydrochloride to the base is 1 (0.5-5).
Preferably, the solvent in step (1) is one or two of N, N-Dimethylformamide (DMF) or N, N-Dimethylacetamide (DMAC), or a mixed solvent containing at least one of DMF or DMAC and other solvents; the other solvent is one or more of methanol, ethanol, N-propanol, isopropanol, cyclohexanol, N-butanol, tert-butanol, ethylene glycol, dimethyl sulfoxide (DMSO), acetonitrile, toluene, dibenzyltoluene, N-methylpyrrolidone, and sulfolane.
Preferably, the volume ratio of at least one of DMF or DMAC to other solvent is 1 (0.5-10).
Preferably, the catalyst in step (2) is indanone, tetralone, acetophenone, 2-bromoacetophenone, 4-bromoacetophenone, 2-methoxyacetophenone, 4-methoxyacetophenone, 1-acetyl-1-cyclohexene, 2, 4-pentanedione, 2, 5-hexanedione, benzaldehyde, benzophenone, butyraldehyde, acetone, isophorone, indole-3-formaldehyde, pyrrole-2-formaldehyde, mesityl oxide, 2, 6-dimethyl-2, 5-heptadiene-4-one, 2-cyclopentenone, 3-methyl-2-cyclopentenone, 2-cyclohexenone, 3-methyl-2-cyclohexenone, 3-phenyl-2-cyclohexenone, One or more of 3-methoxycarbonyl-2-cyclohexenone, R-carvone, cyclohexanone and fluorenone.
Preferably, the molar ratio of the catalyst to L-lysine hydrochloride or L-lysine in step (2) is from 0.1 to 10: 1.
Preferably, the reaction temperature in the step (2) is 50-200 ℃, and the reaction time is 0.5-48 h.
Preferably, the molar ratio of the hydrochloric acid to the L-lysine hydrochloride or L-lysine added in the step (4) is (1-15): 1.
Preferably, the reaction temperature in the step (4) is 25-100 ℃, and the reaction time is 1-24 h.
The invention has the advantages of
The invention provides a method for preparing 1, 5-pentanediamine by organically catalyzing L-lysine chemical decarboxylation, which takes cheap and reproducible L-lysine or L-lysine hydrochloride as a starting material and a solvent containing N, N-Dimethylformamide (DMF) or N, N-Dimethylacetamide (DMAC) as a reaction medium to form an amide intermediate during chemical decarboxylation, and then deprotection is carried out to efficiently prepare a 1, 5-pentanediamine product. Compared with the prior art for preparing the 1, 5-pentanediamine by a biological fermentation method and a chemical method, the method has the advantages of mild reaction conditions, simple operation, cheap and easily obtained catalyst and solvent, recovery and reutilization, low production cost, environmental friendliness, high product yield and suitability for large-scale preparation of the 1, 5-pentanediamine product.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1, 5-pentanediamine hydrochloride prepared in example 1 of the present invention.
FIG. 2 is a nuclear magnetic carbon spectrum of 1, 5-pentanediamine hydrochloride prepared in example 1 of the present invention.
FIG. 3 is a mass spectrum (ESI-MS) of 1, 5-pentanediamine hydrochloride prepared in example 1 of the present invention.
Detailed Description
A method for preparing 1, 5-pentanediamine by organically catalyzing chemical decarboxylation of L-lysine comprises the following steps:
(1) adding alkali liquor into L-lysine hydrochloride serving as an initial raw material, performing neutralization reaction at room temperature, wherein the reaction time is preferably 0.5-2 h, the molar ratio of the L-lysine hydrochloride to the alkali liquor is preferably 1 (0.5-5), and then adding a solvent, or directly adding the solvent into the L-lysine serving as the initial raw material to obtain a reactant, wherein the concentration of the reactant is preferably 0.01-5 mol/L;
the alkali liquor is preferably an aqueous solution prepared from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, potassium carbonate, sodium carbonate, potassium tert-butoxide and sodium tert-butoxide, and more preferably an aqueous solution of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and lithium hydroxide.
The solvent is preferably one or two of N, N-Dimethylformamide (DMF) and N, N-Dimethylacetamide (DMAC), or a mixed solvent containing at least one of DMF or DMAC and other solvents; the other solvent is one or more of methanol, ethanol, N-propanol, isopropanol, cyclohexanol, N-butanol, tert-butanol, ethylene glycol, dimethyl sulfoxide (DMSO), acetonitrile, toluene, dibenzyltoluene, N-methylpyrrolidone and sulfolane; the volume ratio of at least one of DMF or DMAC to other solvent is preferably 1 (0.5-10), more preferably 1: (1-3);
the invention selects at least one of DMF or DMAC as a solvent, because DMF or DMAC can participate in the reaction to form a stable amide intermediate product, the decarboxylation reaction is facilitated, and the yield of 1, 5-pentanediamine is improved.
(2) Adding a catalyst into the reaction system in the step (1), and stirring for reaction, wherein the reaction temperature is preferably 50-200 ℃, and more preferably 100-150 ℃; the reaction time is preferably 0.5h-48h, more preferably 6h-24 h; the molar ratio of the catalyst to L-lysine hydrochloride or L-lysine is preferably (0.1-10):1, more preferably (0.5-2): 1;
the catalyst is preferably indanone, tetralone, acetophenone, 2-bromoacetophenone, 4-bromoacetophenone, 2-methoxyacetophenone, 4-methoxyacetophenone, 1-acetyl-1-cyclohexene, 2, 4-pentanedione, 2, 5-hexanedione, benzaldehyde, benzophenone, butyraldehyde, acetone, isophorone, indole-3-formaldehyde, pyrrole-2-formaldehyde, isopropylidene acetone, 2, 6-dimethyl-2, 5-heptadiene-4-one, 2-cyclopentenone, 3-methyl-2-cyclopentenone, 2-cyclohexenone, 3-methyl-2-cyclohexenone, 3-phenyl-2-cyclohexenone, 3-methoxycarbonyl-2-cyclohexenone, One or more of R-carvone, cyclohexanone and fluorenone, more preferably isophorone, R-carvone, 2-cyclohexenone, 3-methyl-2-cyclohexenone, 3-phenyl-2-cyclohexenone, 2, 6-dimethyl-2, 5-heptadien-4-one, tetralone, acetophenone, 2-bromoacetophenone, 4-bromoacetophenone, 2-methoxyacetophenone, 4-methoxyacetophenone and 1-acetyl-1-cyclohexene.
(3) Evaporating the solvent to dryness, adding water for dissolving, and extracting and separating liquid by using an organic solvent;
according to the invention, if L-lysine hydrochloride is used as a starting material, suction filtration is firstly carried out, and the solvent is evaporated to dryness after insoluble salt is removed; if the L-lysine is used as the initial raw material, the solvent is directly evaporated to dryness.
The solvent is evaporated to dryness, and rotary evaporation or reduced pressure distillation can be selected according to different boiling points of the used solvent; the distilled solvent can be recycled. The organic solvent is preferably one or more of n-hexane, diethyl ether, petroleum ether, toluene, dichloromethane, trichloromethane and ethyl acetate, and preferably diethyl ether, ethyl acetate, dichloromethane and trichloromethane.
And (4) after the liquid separation in the step (3), spin-drying the solvent in the organic phase, and recovering the catalyst.
(4) Adding hydrochloric acid into the water phase, and stirring for reaction, wherein the reaction temperature is preferably 25-100 ℃, the reaction time is preferably 1-24 h, more preferably 1-12 h, and the molar ratio of the added hydrochloric acid to the L-lysine hydrochloride or L-lysine is preferably (1-15):1, more preferably (4-10): 1.
(5) And evaporating the water to dryness to obtain a crude product, and washing the crude product with a solvent to obtain the 1, 5-pentanediamine hydrochloride. The solvent used for washing the crude product is preferably one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, dichloromethane, chloroform, ethyl acetate, tetrahydrofuran and acetonitrile.
The technical solutions of the present invention are further described in detail with reference to the following embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, belong to the scope of protection of the present invention.
Example 1
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottom flask, 56g (1mol) of potassium hydroxide was weighed to prepare 50ml of an aqueous solution, the aqueous solution was added to the round-bottom flask, the reaction was stirred at room temperature for 30 minutes, and 1L of Dimethylformamide (DMF) was added thereto.
2) 220g (2mol) of 3-methyl-2-cyclohexenone is weighed and added into the reaction system, and stirred and reacted for 6 hours at 130 ℃.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. The DMF was distilled off under reduced pressure and the DMF was recovered. Adding water to the system for dissolving, extracting for three times by using ethyl acetate, drying the organic phase, and then spin-drying, thereby recovering the catalyst 3-methyl-2-cyclohexenone.
4) Hydrochloric acid (15mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 h.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-propanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (157g, the yield is 90%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz) delta 39.12,26.18,22.61 the nuclear magnetic hydrogen spectrum of 1, 5-pentanediamine hydrochloride prepared in example 1 of the present invention is shown in fig. 1, the nuclear magnetic carbon spectrum is shown in fig. 2, and the mass spectrum (ESI-MS) is shown in fig. 3.
Example 2
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottomed flask, 56g (1mol) of potassium hydroxide was weighed to prepare 50ml of an aqueous solution, and the aqueous solution was added to the round-bottomed flask and reacted for 30 minutes with stirring at room temperature. 1L of Dimethylformamide (DMF) was added.
2) 110g (1mol) of 3-methyl-2-cyclohexenone is weighed and added into the reaction system, and stirred and reacted for 12 hours at 100 ℃.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. The DMF was distilled off under reduced pressure and the DMF was recovered. Adding water to the system for dissolving, extracting for three times by using ethyl acetate, drying the organic phase, and then spin-drying, thereby recovering the catalyst 3-methyl-2-cyclohexenone.
4) Hydrochloric acid (15mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 h.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by methanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (140g, the yield is 80%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
Example 3
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottomed flask, 56g (1mol) of potassium hydroxide was weighed to prepare 50ml of an aqueous solution, and the aqueous solution was added to the round-bottomed flask and reacted for 30 minutes with stirring at room temperature. 1L of Dimethylformamide (DMF) was added.
2) 86g (0.5mol) of 3-phenyl-2-cyclohexenone was weighed out and added to the reaction system, and the reaction was stirred at 130 ℃ for 18 hours.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. The DMF was distilled off under reduced pressure and the DMF was recovered. Adding water to the system for dissolving, extracting for three times by using ethyl acetate, drying the organic phase, and then spin-drying, thereby recovering the catalyst 3-phenyl-2-cyclohexenone.
4) Hydrochloric acid (10mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 hours.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-propanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (151g, yield 86%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
Example 4
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottomed flask, 56g (1mol) of potassium hydroxide was weighed to prepare 50ml of an aqueous solution, and the aqueous solution was added to the round-bottomed flask and reacted for 30 minutes with stirring at room temperature. 1L of Dimethylformamide (DMF) was added.
2) 13.8g (0.1mol) of isophorone is weighed and added into the reaction system, and the reaction system is stirred at 130 ℃ for 24 hours.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. The DMF was distilled off under reduced pressure and the DMF was recovered. Adding water to the system for dissolving, extracting for three times by using ethyl acetate, drying the organic phase, and then spin-drying, thereby recovering the catalyst isophorone.
4) Hydrochloric acid (5mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 h.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-propanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (131g, the yield is 75%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
Example 5
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottomed flask, 56g (1mol) of potassium hydroxide was weighed to prepare 50ml of an aqueous solution, and the aqueous solution was added to the round-bottomed flask and reacted for 30 minutes with stirring at room temperature. 1L of Dimethylacetamide (DMAC) was added.
2) 344g (2mol) of 3-phenyl-2-cyclohexenone is weighed and added into the reaction system, and stirred and reacted for 12 hours at 150 ℃.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. The DMF was distilled off under reduced pressure and the DMF was recovered. Adding water to the system for dissolving, extracting for three times by using ethyl acetate, drying the organic phase, and then spin-drying, thereby recovering the catalyst 3-phenyl-2-cyclohexenone.
4) Hydrochloric acid (5mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 h.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-propanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (149g, the yield is 85%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
Example 6
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottom flask, 69g (0.5mol) of potassium carbonate was weighed to prepare 50ml of an aqueous solution, and the aqueous solution was added to the round-bottom flask, followed by stirring at room temperature for 30 minutes. Then adding 1L of mixed solvent of Dimethylformamide (DMF) and toluene, wherein the volume ratio of DMF to toluene is 1: 1.
2) 220g (2mol) of 3-methyl-2-cyclohexenone is weighed and added into the reaction system, and stirred and reacted for 12 hours at 120 ℃.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. Rotary evaporation is carried out firstly, toluene is recovered, reduced pressure distillation is carried out again, and DMF is recovered. Adding water to the system for dissolving, extracting for three times by using ethyl acetate, drying the organic phase, and then spin-drying, thereby recovering the catalyst 3-methyl-2-cyclohexenone.
4) Hydrochloric acid (5mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 h.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-propanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (154g, the yield is 88%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
Example 7
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottom flask, 69g (0.5mol) of potassium carbonate was weighed to prepare 50ml of an aqueous solution, and the aqueous solution was added to the round-bottom flask, followed by stirring at room temperature for 30 minutes. Then adding 1L of mixed solvent of Dimethylformamide (DMF) and isopropanol, wherein the volume ratio of DMF to isopropanol is 1: 1.
2) 344g (2mol) of 3-phenyl-2-cyclohexenone is weighed and added into the reaction system for reflux reaction for 15 h.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. Rotary evaporation is carried out firstly, isopropanol is recovered, then reduced pressure distillation is carried out, and DMF is recovered. Adding water to the system for dissolving, extracting for three times by using ethyl acetate, drying the organic phase, and then spin-drying, thereby recovering the catalyst 3-phenyl-2-cyclohexenone.
4) Hydrochloric acid (2mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 h.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-propanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (122g, the yield is 70%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
Example 8
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottom flask, 40g (1mol) of sodium hydroxide was weighed to prepare 50ml of an aqueous solution, and the aqueous solution was added to the round-bottom flask, followed by reaction with stirring at room temperature for 30 minutes. Then 0.5L of mixed solvent of Dimethylformamide (DMF) and n-butanol is added, wherein the volume ratio of DMF to toluene is 1: 3.
2) And 300g (2mol) of 4-methoxyacetophenone is weighed and added into the reaction system, and reflux reaction is carried out for 12 hours.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. Rotary evaporation is carried out firstly, n-butyl alcohol is recovered, reduced pressure distillation is carried out again, and DMF is recovered. Adding water to the system for dissolving, extracting for three times by using ethyl acetate, drying an organic phase, and then spin-drying to recover the catalyst 4-methoxyacetophenone.
4) Hydrochloric acid (2mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 h.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-butyl alcohol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (131g, the yield is 75%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
Example 9
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottomed flask, 56g (1mol) of potassium hydroxide was weighed to prepare 50ml of an aqueous solution, and the aqueous solution was added to the round-bottomed flask and reacted for 30 minutes with stirring at room temperature. 1L of Dimethylformamide (DMF) was added.
2) And 300g (2mol) of R-carvone is weighed and added into the reaction system, and the reaction is stirred at 130 ℃ for 6 hours.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. The DMF was distilled off under reduced pressure and the DMF was recovered. The system was dissolved in water and extracted three times with dichloromethane.
4) Hydrochloric acid (1mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 hours.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-propanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (154g, the yield is 88%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
Example 10
1) 183g (1mol) of L-lysine hydrochloride was weighed in a 2L round-bottomed flask, 56g (1mol) of potassium hydroxide was weighed to prepare 50ml of an aqueous solution, and the aqueous solution was added to the round-bottomed flask and reacted for 30 minutes with stirring at room temperature. 1L of Dimethylformamide (DMF) was added.
2) 240g (2mol) of acetophenone is weighed and added into the reaction system, and the mixture is stirred and reacted for 6 hours at the temperature of 130 ℃.
3) The reaction was stopped, cooled to room temperature, and the insoluble potassium chloride was removed by suction filtration. The DMF was distilled off under reduced pressure and the DMF was recovered. The system was dissolved in water and extracted three times with dichloromethane.
4) Hydrochloric acid (8mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 h.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-propanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (137g, the yield is 78%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
Example 11
1) 146g (1mol) of L-lysine were weighed into a 2L round-bottomed flask, and 1L of Dimethylformamide (DMF) was added.
2) 300g (2mol) of 2-methoxyacetophenone is weighed and added into the reaction system, and the reaction is stirred for 6 hours at 130 ℃.
3) The reaction was stopped and cooled to room temperature. The DMF was distilled off under reduced pressure and the DMF was recovered. Adding water to the system for dissolving, extracting for three times by using ethyl acetate, drying an organic phase, and then spin-drying to recover the catalyst 2-methoxyacetophenone.
4) Hydrochloric acid (6mol) was added to the aqueous phase, and the reaction was stirred at 90 ℃ for 4 h.
5) And water is dried in a rotating mode to obtain a crude product of the 1, 5-pentanediamine hydrochloride, and the crude product is washed by n-propanol to obtain a pure product of the 1, 5-pentanediamine hydrochloride (163g, the yield is 93%).1H NMR(D2O,300MHz)δ1.35-1.45(m,2H),1.60-1.70(m,4H),2.93-2.98(t,4H).13C NMR(D2O,100MHz)δ39.12,26.18,22.61.
The above embodiments are only for the purpose of helping understanding the method of the present invention and the core idea thereof, and it will be apparent to those skilled in the art that several modifications and modifications can be made to the present invention without departing from the principle of the present invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.

Claims (6)

1. A method for preparing 1, 5-pentanediamine by organic catalysis of chemical decarboxylation of L-lysine is characterized by comprising the following steps:
(1) taking L-lysine hydrochloride as an initial raw material, adding alkali liquor, performing neutralization reaction at room temperature, and then adding a solvent, or taking L-lysine as an initial raw material, and directly adding a solvent to obtain a reactant;
(2) adding a catalyst into the reaction system in the step (1), and stirring for reaction; the reaction temperature is 100-150 ℃; the reaction time is 6-24 h;
(3) evaporating the solvent to dryness, adding water for dissolving, and extracting and separating liquid by using an organic solvent;
(4) adding hydrochloric acid into the water phase, and stirring for reaction;
(5) and evaporating the water to dryness to obtain a crude product, and washing the crude product with a solvent to obtain the 1, 5-pentanediamine hydrochloride.
The solvent in the step (1) is one or two of N, N-dimethylformamide and N, N-dimethylacetamide, or a mixed solvent containing at least one of N, N-dimethylformamide and N, N-dimethylacetamide and other solvents; the other solvent is one or more of methanol, ethanol, N-propanol, isopropanol, cyclohexanol, N-butanol, tert-butanol, ethylene glycol, dimethyl sulfoxide, acetonitrile, toluene, dibenzyltoluene, N-methylpyrrolidone and sulfolane;
the alkali liquor in the step (1) is an aqueous solution prepared from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, potassium carbonate, sodium carbonate, potassium tert-butoxide or sodium tert-butoxide;
the catalyst in the step (2) is indenone, tetralone, acetophenone, 2-bromoacetophenone, 4-bromoacetophenone, 2-methoxyacetophenone, 4-methoxyacetophenone, 1-acetyl-1-cyclohexene, 2, 4-pentanedione, 2, 5-hexanedione, benzaldehyde, benzophenone, butyraldehyde, acetone, isophorone, indole-3-formaldehyde, pyrrole-2-formaldehyde, mesityl oxide, 2, 6-dimethyl-2, 5-heptadien-4-one, 2-cyclopentenone, 3-methyl-2-cyclopentenone, 2-cyclohexenone, 3-methyl-2-cyclohexenone, 3-phenyl-2-cyclohexenone, 3-methoxycarbonyl-2-cyclohexenone, and mixtures thereof, One or more of R-carvone, cyclohexanone and fluorenone.
2. The method for preparing 1, 5-pentanediamine by organically catalyzing the chemical decarboxylation of L-lysine according to claim 1, wherein the molar ratio of L-lysine hydrochloride to the base is 1 (0.5-5) when L-lysine hydrochloride is used as a starting material in the step (1).
3. The method for preparing 1, 5-pentanediamine by organically catalyzing the chemical decarboxylation of L-lysine according to claim 1, wherein the volume ratio of at least one of N, N-dimethylformamide or N, N-dimethylacetamide to other solvents is 1 (0.5-10).
4. The method for preparing 1, 5-pentanediamine by organically catalyzing the chemical decarboxylation of L-lysine according to claim 1, wherein the molar ratio of the catalyst to the L-lysine hydrochloride or the L-lysine in the step (2) is 0.1-10: 1.
5. The method for preparing 1, 5-pentanediamine by organically catalyzing the chemical decarboxylation of L-lysine according to claim 1, wherein the molar ratio of the added hydrochloric acid to the L-lysine hydrochloride or L-lysine in the step (4) is (1-15): 1.
6. The method for preparing 1, 5-pentanediamine by organically catalyzing the chemical decarboxylation of L-lysine according to claim 1, wherein the reaction temperature in the step (4) is 25-100 ℃, and the reaction time is 1-24 h.
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