CN1666975A - Process for preparing dialkylamino ethanol carboxylate and its salts - Google Patents
Process for preparing dialkylamino ethanol carboxylate and its salts Download PDFInfo
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- CN1666975A CN1666975A CN 200510017414 CN200510017414A CN1666975A CN 1666975 A CN1666975 A CN 1666975A CN 200510017414 CN200510017414 CN 200510017414 CN 200510017414 A CN200510017414 A CN 200510017414A CN 1666975 A CN1666975 A CN 1666975A
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- reaction
- carboxylate
- acid
- dialkylaminoethanol
- citric acid
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- -1 dialkylamino ethanol carboxylate Chemical class 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 150000003839 salts Chemical class 0.000 title abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 22
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 16
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 12
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 11
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 4
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 4
- QJWQYOHBMUQHGZ-UHFFFAOYSA-N ethanol;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound CCO.OC(=O)CC(O)(C(O)=O)CC(O)=O QJWQYOHBMUQHGZ-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ZXWHANCSQZVZCM-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;methanol Chemical compound OC.OC(=O)CC(O)(C(O)=O)CC(O)=O ZXWHANCSQZVZCM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008635 plant growth Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 53
- 239000003814 drug Substances 0.000 description 20
- 229940079593 drug Drugs 0.000 description 16
- 239000012047 saturated solution Substances 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 10
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 10
- GPTPSPSJWBFWND-UHFFFAOYSA-N 1-(diethylamino)ethyl hexanoate Chemical compound CCCCCC(=O)OC(C)N(CC)CC GPTPSPSJWBFWND-UHFFFAOYSA-N 0.000 description 9
- ZUVUDORMKHUBBK-UHFFFAOYSA-N CCCC(=O)OC(C)N(CC)CC Chemical compound CCCC(=O)OC(C)N(CC)CC ZUVUDORMKHUBBK-UHFFFAOYSA-N 0.000 description 9
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 230000035784 germination Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000005648 plant growth regulator Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 2
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 2
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- PKHMTIRCAFTBDS-UHFFFAOYSA-N hexanoyl hexanoate Chemical compound CCCCCC(=O)OC(=O)CCCCC PKHMTIRCAFTBDS-UHFFFAOYSA-N 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- LOVYCUYJRWLTSU-UHFFFAOYSA-N 2-(3,4-dichlorophenoxy)-n,n-diethylethanamine Chemical compound CCN(CC)CCOC1=CC=C(Cl)C(Cl)=C1 LOVYCUYJRWLTSU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241001495453 Parthenium argentatum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- UQHKFADEQIVWID-UHFFFAOYSA-N cytokinin Natural products C1=NC=2C(NCC=C(CO)C)=NC=NC=2N1C1CC(O)C(CO)O1 UQHKFADEQIVWID-UHFFFAOYSA-N 0.000 description 1
- 239000004062 cytokinin Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention relates to a production method of a new style plant growth regulating agent, especially a production method of dialkyl aminoethyl alcohol carboxylate and its salt. It is got by the reaction of dialkyl aminoethyl alcohol and carboxylate, mezzo forte acid with amino is catalyst in the reaction, carboxylate type compound is solvent, and then dialkyl aminoethyl alcohol carboxylate is got through exsolution and distillation after reaction. After the reaction and exsolution, isodose saturated citric acid solution is reacted with dialkyl aminoethyl alcohol carboxylate which after exsolution, then the needed dialkyl aminoethyl alcohol carboxylate citrate is got. The catalyst can be easy got in market and is cheap, solvent is non toxic and is easy to propose when using this invention. The yield of dialkyl aminoethyl alcohol carboxylate and its salt is high and its appearance is fairness and twinkle, it is easy to store and packet and can be industrial produced, it has great economic benefit.
Description
The technical field is as follows: the invention relates to a preparation method of a novel plant growth regulator, in particular to a preparation method of dialkyl amino ethanol carboxylic ester and salt thereof.
Secondly, the background technology: the plant growth regulator is a key field of research in chemical, biological and agricultural communities at home and abroad at present, is considered to be one of the important components of super high yield of agriculture in the 21 st century, and the research and development of the plant growth regulator can effectively promote the second green revolution. The plant growth regulator is an organic compound which has regulating effect on plant growth except nutrient substances in plants, has small dosage and large effect, can promote germination, control flowering, delay and control aging process, increase yield, improve crop quality and increase stress resistance, and is an effective component for solving the problem of ultrahigh yield of grain crops and economic crops.
The dialkyl amino ethanol carboxylate is a novel cytokinin plant growth regulator, is widely applied to grain crops, economic crops, fruit trees, vegetables, flowers and edible fungi, can promote the metabolism of carbohydrates and the accumulation of substances by using the dialkyl amino ethanol carboxylate at a low concentration (10mg/L), greatly improves the yield of the crops, and obviously improves the quality of products. One of the most common processes for the preparation of carboxylic esters at present is: the carboxylic acid and the alcohol are synthesized by esterification reaction in the presence of sulfuric acid, but since the dialkylaminoethanol has strong alkalinity, when the sulfuric acid is added as a catalyst, the sulfuric acid preferentially reacts with the dialkylaminoethanol to generate equimolar ammonium sulfate salt, so that the catalytic effect is lost, meanwhile, the ammonium sulfate salt is insoluble in the carboxylic acid and an organic solvent, so that the reaction is not favorably carried out, and the use of the sulfuric acid is not only easy to corrode equipment but also brings corresponding trouble to post-treatment, so that the method is not suitable for preparing the dialkylaminoethanol carboxylic ester.
Several processes for preparing dialkylaminoethanol carboxylic acid esters are disclosed in the prior art. For example, Japanese laid-open patent publication No. JP-A-Hei 1-290606 discloses ｃA process for producing ｃA diethylaminoethanol carboxylic ester by reacting ｃA fatty acid chloride with an excess amount of diethylaminoethanol in ｃA large amount of chloroform solvent, stirring the reaction mixture in an ice bath, reacting the reaction mixture at room temperature for 2 hours, standing the reaction mixture overnight, neutralizing the reaction mixture with an alkali, washing the reaction mixture with water, and desolventizing the reaction mixture to obtain ｃA diethylaminoethanol carboxylic ester. In addition, it uses large amount of chloroform, and has high toxicity, low recovery rate and high product cost.
The invention name of Chinese patent CN1073429A is: "preparation method of dialkylaminoethanol carboxylate", patent No. 92112507.0 discloses a preparation method of dialkylaminoethanol carboxylate, which is to esterify carboxylic acid with dialkylaminoethanol using aromatic hydrocarbon as solvent and solid acid or heteropoly acid as catalyst, and the method has the following disadvantages: the production process of the solid acid or the heteropoly acid is complex, and the industrial product of the catalyst is not available in the domestic market at present and needs to be prepared on site. Meanwhile, the aromatic hydrocarbon solvent has high toxicity and is easy to cause leukemia; moreover, the reaction temperature is high, the reaction time is long, side reactions are more, and the yield is reduced.
The invention name of Chinese patent CN1305987A is: "preparation method of dialkyl amino ethanol carboxylic ester and its salt",patent No. 00101728.4 discloses a preparation method of dialkyl amino ethanol carboxylic ester and its salt, it adopts acyl chloride and dialkyl amino ethanol to esterify directly without solvent, its inevitable repetition is the disadvantage of acyl chloride method of Japanese patent, at the same time, have introduced the method for synthesizing dialkyl amino ethanol carboxylic ester of ester interchange in this patent, and the method for synthesizing dialkyl amino ethanol carboxylic ester with caproic anhydride, these two methods are quite high in cost, the ratio of caproic anhydride and acetic acid is about 20: 1 on the present market, and need to import.
The invention content is as follows:
the purpose of the invention is: overcomes the defects of the prior art and provides a novel preparation method of dialkyl amino ethanol carboxylic ester and salt thereof.
The technical scheme of the invention is as follows: a preparation method of dialkyl amino ethanol carboxylic ester is prepared by esterification reaction of dialkyl amino ethanol and carboxylic acid under the action of a catalyst, and the chemical reaction formula is as follows:
wherein R is1Is an alkyl group having 1 to 5 carbon atoms, R2Is CH3，C2H5，C3H7The medium-strong acid containing amino group is used as the catalyst for esterification reaction, the solvent for reaction is carboxylate compound, and the reaction temperature is highThe reaction temperature is 120-175 ℃, the reaction time is 3-5 hours, and after the reaction is finished, the diethyl aminoethyl alcohol carboxylate is obtained through desolventizing and distilling.
The medium-strong acid containing amino is sulfamic acid or ammonium dihydrogen phosphate, and preferably sulfamic acid.
The carboxylate compound solvent is butyl acetate, or ethyl propionate, or ethyl butyrate, and preferably butyl acetate.
After the esterification reaction is finished and the precipitation is carried out, reacting metered saturated citric acid solution with the dialkyl amino ethanol carboxylic ester after the precipitation, and after the complete reaction, decoloring, crystallizing and separating to obtain the needed dialkyl amino ethanol carboxylic ester citrate.
In the method for salifying the dialkyl amino ethanol carboxylic ester, the saturated citric acid solution is a citric acid aqueous solution, or a citric acid methanol solution, or a citric acid ethanol solution, and preferably a citric acid ethanol solution.
The solvent in the reaction salifying process is water, or methanol, or ethanol solution of citric acid.
The reaction temperature in the reaction salt forming process is 120-175 ℃,
the invention has the following positive beneficial effects:
1. the invention adopts sulfamic acid (H) which is a medium strong acid containing amino and is easy to obtain in the market and low in price2NSO3H) Or ammonium dihydrogen phosphate is used as the catalyst, the catalytic activity of the catalyst is not lower than that of sulfuric acid, but the defects of salt forming insolubility of the sulfuric acid catalyst, complexity in preparation of a solid acid catalyst and rigor of operation of an acyl chloride method are overcome, and the catalyst has the characteristics of high activity and high efficiency in an esterification reaction. Currently, the market price of sulfamic acid is 3.8 yuan/Kg, and the market price of ammonium dihydrogen phosphate is 2.3 yuan/Kg, so that the following can be known: the catalyst required by the invention has the advantages of low price, easily obtained raw materials and convenient use.
2. The esterification reaction of the invention takes carboxylic ester compounds as solvents, the dehydration performance of the esterification reaction is similar to that of aromatic hydrocarbon solvents, but the strong toxicity of the aromatic hydrocarbon solvents is avoided.
3. In the reaction salifying process, the used acid is a citric acid saturated solution, and the method can quickly generate large-particle dialkyl amino ethanol carboxylate citrate products, has high yield, and the products are white and shiny in appearance and are convenient to store and package.
4. The preparation method of the invention has the advantages of high yield of the dialkyl amino ethanol carboxylic ester, easily obtained catalyst raw materials, low cost, no strong toxicity of the solvent, simple treatment, capability of obtaining the product dialkyl amino ethanol carboxylic ester after exsolution, capability of further forming salt with acid to obtain the citrate of the dialkyl amino ethanol carboxylic ester, direct realization of industrial production and remarkable economic benefit.
The fourth embodiment:
the first embodiment is as follows: preparation of Diethylaminoethanol hexanoate:
153.2g of n-hexanoic acid, 140.4g of diethylaminoethanol, 45mL of butyl acetate and the catalyst sulfamic acid (H) were added to a reaction flask equipped with an electric stirrer, an oil-water separator and a thermometer2NSO3H)4.5g, starting stirring, slowly heating to 140 ℃, namely evaporating an azeotrope formed by water generated in the reaction and butyl acetate into an oil-water separator, when the temperature is continuously increased to 158 ℃, no water is generated (about 3.5 hours), and thenThe residual butyl acetate in the solution was extracted, the reaction was completed, and the reaction solution was cooled to room temperature, and then filtered (catalyst was removed) to obtain a light brown transparent liquid, 237.6g of diethylaminoethanol hexanoate, and the yield was 92.7%.
Example two: preparation of Diethylaminoethanol hexanoate:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: as a result of using 5.0g of ammonium dihydrogenphosphate as the catalyst sulfamic acid, 216.9g of dialkylaminoethanol hexanoate was obtained in 84.9% yield.
Example three: preparation of dimethylamino ethanol hexanoate:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: using 140.4g of diethylaminoethanol instead of 106.8g of dimethylaminoethanol, 206.8g of dimethylaminoethanol hexanoate was obtained in 93.1% yield.
Example four: preparation of Diethylaminoethanol hexanoate:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: ethyl propionate was used instead of butyl acetate as a solvent to obtain 227.3g of diethylaminoethanol hexanoate in 89.0% yield.
Example five: preparation of Diethylaminoethanol hexanoate:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: ethyl butyratewas used instead of butyl acetate as a solvent, whereby 230.4g of diethylaminoethanol hexanoate was obtained in a yield of 90.2%.
Example six: preparation of Diethylaminoethanol butyrate:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: 153.2g of n-hexanoic acid was changed to 114.3g of n-butanoic acid, resulting in 198.6g of diethylaminoethanol butyrate with a yield of 89.4%.
Example seven: preparation of Diethylaminoethanolproex ester:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: 153.2g of n-pentanoic acid was used instead of 153.2g of n-hexanoic acid, resulting in 209.0g of diethylaminoethanol valerate in 87.1% yield.
Example eight: preparation of Diethylaminoethanol butyrate:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: 153.2g of n-hexanoic acid was used in place of 114.3g of n-butanoic acid, and 5.0g of dihydrogenamine phosphate was used in place of sulfamic acid as a catalyst, whereby 187.4g of diethylaminoethanol butyrate was obtained in 85.2% yield.
Example nine: preparation of Diethylaminoethanol butyrate:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: 153.2g of n-hexanoic acid was changed to 114.3g of n-butanoic acid and ethyl propionate was used as a solvent for butyl acetate, whereby 195.2g of diethylaminoethanol butyrate was obtained in a yield of 87.9%.
Example ten: preparation of Diethylaminoethanol butyrate:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: 153.2g of n-hexanoic acid was changed to 114.3g of n-butanoic acid and ethyl butyrate was used as a solvent for butyl acetate, whereby 184.7g of diethylaminoethanol butyrate was obtained in 83.1% yield.
Example eleven: preparation of Diethylaminoethanolproex ester:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: 153.2g of n-pentanoic acid was used instead of 153.2g of n-hexanoic acid, and 5.0g of monoammonium phosphate was used instead of sulfamic acid as a catalyst, resulting in 198.5g of diethylaminoethanol valerate in 82.7% yield.
Example twelve: preparation of Diethylaminoethanolproex ester:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: 153.2g of n-pentanoic acid was used instead of 153.2g of n-hexanoic acid, and ethyl propionate was used instead of butyl acetate as a solvent, resulting in 204.7g of diethylaminoethanol valerate in 85.3% yield.
Example thirteen: preparation of Diethylaminoethanolproex ester:
the apparatus, the drug and the preparation method of the present embodiment are the same as those of the first embodiment, and the differences are that: 153.2g of n-pentanoic acid was used instead of 122.2g of n-hexanoic acid, and ethyl butyrate was used instead of butyl acetate as a solvent, resulting in 201.6g of diethylaminoethanol valerate in 84.0% yield.
Example fourteen: preparation of Diethylaminoethanolacaproate citrate:
230g of n-hexanoic acid, 211g of diethylaminoethanol, 67ml of butyl acetate as solvent and sulfamic acid (H) as catalyst were added to a reaction flask equipped with an electric stirrer, an oil-water separator and a thermometer2NSO3H)6.8 g. Stirring is started, the temperature is slowly raised to 140 ℃, and then an azeotrope formed by the water generated by the reaction and the butyl acetate is evaporated into an oil-water separator. When the temperature is further increased to 158 ℃, no water is generated (about 3.5 hours), and then residual butyl acetate in the solution is pumped out under negative pressure, so that the reaction is finished. The reaction mixture was cooled to room temperature, filtered (catalyst removed) to give a light brown clear liquid, which was then added slowly to a 60 ℃ ethanol saturated solution containing 317g of citric acid while stirring, and then addedAdding 10g of activated carbon, continuously stirring for 30 minutes, carrying out suction filtration while the solution is hot, and naturally cooling, crystallizing, separating and drying the filtrate to obtain 670g of diethylaminoethanol caproate citrate, wherein the product content is 99.3 percent, and the yield is 92.3 percent.
Example fifteen: preparation of Diethylaminoethanolacaproate citrate:
the device, the drug and the preparation method of the embodiment are the same as those of the fourteenth embodiment, and the differences are that: during the salt-forming reaction, the saturated solution of citric acid in ethanol was changed to saturated solution of citric acid in distilled water, resulting in 632g of citric acid salt of diethylaminoethanol hexanoate in 87.1% yield.
Example sixteen: preparation of Diethylaminoethanolacaproate citrate:
the device, the drug and the preparation method of the embodimentare the same as those of the fourteenth embodiment, and the differences are that: during the salt-forming reaction, the ethanol saturated solution of citric acid was changed to methanol saturated solution of citric acid, so that 686g of diethylaminoethanol caproate citrate was obtained in 94.5% yield.
Example seventeen: preparation of diethylaminoethanol butyrate citrate:
the device, the drug and the preparation method of the embodiment are the same as those of the fourteenth embodiment, and the differences are that: in the course of the esterification reaction, 114.3g of n-butyric acid was used instead of 230g of n-caproic acid, and in the course of the salt-forming reaction, 205g of an ethanol-saturated solution 317g of citric acid was used, as a result, 381.2g of citric acid salt of diethylaminoethanol butyrate was obtained in a yield of 94.8%.
Example eighteen: preparation of diethylaminoethanol butyrate citrate:
the device, the medicine and the preparation method of the embodiment are the same as those of the seventeenth embodiment, and the differences are that: during the salt-forming reaction, the ethanol saturated solution of citric acid was changed to a distilled water saturated solution of citric acid, resulting in 362.0g of diethylaminoethanol butyrate citrate with a yield of 90.0%.
Example nineteenth: preparation of diethylaminoethanol butyrate citrate:
the device, the medicine and the preparation method of the embodiment are the same as those of the seventeenth embodiment, and the differences are that: during the salt-forming reaction, the ethanol saturated solution of citric acid was changed to a methanol saturated solution of citric acid, resulting in 380.4g of diethylaminoethanol butyrate citrate with a yield of 94.6%.
Example twenty: preparation of Diethylaminoethanolproex ester citrate:
the device, the drug and the preparation method of the embodiment are the same as those of the fourteenth embodiment, and the differences are that: during the esterification reaction, 230g of n-hexanoic acid was changed to 122.2g of n-pentanoic acid, and during the salt formation reaction, 317g of citric acid was changed to 200g of ethanol saturated solution, resulting in 385.6g of diethylaminoethanol valerate citrate with a yield of 94.4%.
Example twenty one: preparation of diethylaminoethanol butyrate citrate:
the device, the medicine and the preparation method of the embodiment are the same as those of the twenty embodiment, and the same points are not repeated, except that: in the salt-forming reaction, the saturated solution of citric acid in ethanol was changed to saturated solution of citric acid in distilled water, resulting in 349.0g of diethylaminoethanol valerate citrate with 85.4% yield.
Example twenty two: preparation of diethylaminoethanol butyrate citrate:
the device, the medicine and the preparation method of the embodiment are the same as those of the twenty embodiment, and the same points are not repeated, except that: in the salt-forming reaction, the ethanol saturated solution of citric acid was changed to a methanol saturated solution of citric acid, resulting in 384.9g of diethylaminoethanol butyrate citrate with a yield of 94.2%.
Example twenty three: the effect of diethylaminoethanol hexanoate on the protein and ribose content of guayule, the results 20 days after treatment are given in the following table:
| treatment concentration (mg/kg) | Protein content (mg/g.Fw) | Bick (±％) | Ribose content (ug/g.Fw) | Bick (±％) |
| 0 | 3.10 | 0 | 0.71 | 0 |
| 2.0 | 3.19 | +2.9 | 0.89 | +23.35 |
| 5.0 | 3.34 | +7.74 | 1.09 | +53.52 |
| 10.0 | 3.23 | +4.19 | 0.82 | +15.49 |
Example twenty-four: the influence of diethylaminoethanol caproate on the germination rate, germination index, vigor index, seedling length and fresh weight of corn seeds is shown in the following table:
| treatment concentration (mg/kg) | Germination rate (％) | Index of germination (GI) | Vitality index (VI) | Seedling growing worker (cm) | Fresh weight (mg/dong) |
| 0 | 83.03±1.53 | 26.89±1.66 | 216.86±12.98 | 7.81±2.03 | 515±0.19 |
| 1 | 87.00±2.00 | 29.35±0.49 | 234.51±9.95 | 7.99±3.00 | 534±0.20 |
| 5 | 89.33±3.39 | 28.55±1.35 | 235.28±11.12 | 8.24±2.43 | 587±0.13 |
| 10 | 93.61±1.53 | 31.50±0.24 | 280.34±5.38 | 10.58±1.23 | 682±0.16 |
| 20 | 91.67±2.08 | 30.82±0.73 | 287.11±6.56 | 9.40±1.15 | 554±0.17 |
Claims (10)
1. A process for preparing dialkylamino ethanol carboxylate with molecular formula R1COOCH2CH2NR22，R1Contains 1 to 5Alkyl of carbon, R2Is CH3，C2H5，C3H7The catalyst is prepared by esterification reaction of dialkyl amino ethanol and carboxylic acid under the action of a catalyst, and is characterized in that: the method comprises the steps of adopting amino-containing medium-strong acid as a catalyst for esterification reaction, using a carboxylic ester compound as a reaction solvent, controlling the reaction temperature to be 120-175 ℃, controlling the reaction time to be 3-5 hours, and obtaining the diethyl aminoethyl alcohol carboxylic ester after the reaction is finished and through desolventizing and distilling.
2. The process for preparing a dialkylaminoethanol carboxylate according to claim 1, wherein: the medium-strong acid containing amino is sulfamic acid or ammonium dihydrogen phosphate.
3. The process for preparing a dialkylaminoethanol carboxylate according to claim 1, wherein: the medium-strong acid containing amino is sulfamic acid.
4. The process for preparing a dialkylaminoethanol carboxylate according to claim 1, wherein: the carboxylate compound solvent is butyl acetate, or ethyl propionate, or ethyl butyrate.
5. The process for preparing a dialkylaminoethanol carboxylate according to claim 1, wherein: the carboxylic ester compound solvent is butyl acetate.
6. A process for salifying a dialkylaminoethanol carboxylate as claimed in any one of claims 1 to 5, which comprises: after the esterification reaction is finished and the solution is desolventized, reacting saturated citric acid solution with the desolventized dialkyl amino ethanol carboxylic ester in equal amount, and after the complete reaction, decoloring, crystallizing and separating to obtain the required dialkyl amino ethanol carboxylic ester citrate.
7. A process for salifying a dialkylaminoethanol carboxylate according to claim 6 wherein: the saturated citric acid solution is citric acid aqueous solution, or citric acid methanol solution, or citric acid ethanol solution.
8. A process for salifying a dialkylaminoethanol carboxylate according to claim 6 wherein: the saturated citric acid solution is citric acid ethanol solution.
9. A process for salifying a dialkylaminoethanol carboxylate according to claim 6 wherein: the solvent in the reaction salifying process is water, or methanol, or ethanol solution of citric acid.
10. A process for salifying a dialkylaminoethanol carboxylate according to claim 6 wherein: the reaction temperature is 120-175 ℃,
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008238A (en) * | 2016-05-24 | 2016-10-12 | 苏州科技学院 | Plant growth regulator bis-diethylaminoethanol phthalate citrate compound and preparation method thereof |
| CN111362818A (en) * | 2020-03-06 | 2020-07-03 | 河南福联生物科技有限公司 | Preparation and application of butyric acid-N, N-diethylaminoethyl ester salt serving as plant growth regulator |
| CN113105345A (en) * | 2021-04-19 | 2021-07-13 | 鹤壁全丰生物科技有限公司 | Production process of diethyl aminoethyl hexanoate citrate |
-
2005
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008238A (en) * | 2016-05-24 | 2016-10-12 | 苏州科技学院 | Plant growth regulator bis-diethylaminoethanol phthalate citrate compound and preparation method thereof |
| CN111362818A (en) * | 2020-03-06 | 2020-07-03 | 河南福联生物科技有限公司 | Preparation and application of butyric acid-N, N-diethylaminoethyl ester salt serving as plant growth regulator |
| CN113105345A (en) * | 2021-04-19 | 2021-07-13 | 鹤壁全丰生物科技有限公司 | Production process of diethyl aminoethyl hexanoate citrate |
| CN113105345B (en) * | 2021-04-19 | 2023-07-07 | 鹤壁全丰生物科技有限公司 | Production process of diethyl aminoethyl hexanoate citrate |
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