CN1268603C - Process for preparing dialkylamino ethanol carboxylate and its salts - Google Patents
Process for preparing dialkylamino ethanol carboxylate and its salts Download PDFInfo
- Publication number
- CN1268603C CN1268603C CN 200510017414 CN200510017414A CN1268603C CN 1268603 C CN1268603 C CN 1268603C CN 200510017414 CN200510017414 CN 200510017414 CN 200510017414 A CN200510017414 A CN 200510017414A CN 1268603 C CN1268603 C CN 1268603C
- Authority
- CN
- China
- Prior art keywords
- preparation
- carboxylate
- ethanol
- reaction
- diethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 dialkylamino ethanol carboxylate Chemical class 0.000 title claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 123
- 150000003839 salts Chemical class 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 34
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 24
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 22
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical group CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229940043232 butyl acetate Drugs 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical group C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 63
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 abstract description 19
- 239000005648 plant growth regulator Substances 0.000 abstract description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 150000007942 carboxylates Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 125000003282 alkyl amino group Chemical group 0.000 description 48
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 48
- 239000003814 drug Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000012047 saturated solution Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229940005605 valeric acid Drugs 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000001263 acyl chlorides Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 125000004663 dialkyl amino group Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 230000035784 germination Effects 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-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
- 239000003513 alkali Substances 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
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 235000013305 food Nutrition 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
- 231100000567 intoxicating Toxicity 0.000 description 2
- 230000002673 intoxicating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 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 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 241000182534 Pericallis hybrida 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
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000470 constituent Substances 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
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000007226 seed germination Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a novel preparation method of a plant growth regulator, particularly to a preparation method of dialkyl aminoethanol carboxylate and salt thereof which are prepared from dialkyl aminoethanol and carboxylic acid by esterification reaction. In a reaction process, strong acid containing amino groups is adopted as a catalyst; a carboxylate compound is used as solvent; after reaction is finished, diethyl aminoethanol carboxylate is prepared by exsolution and distillation; after the esterification reaction and the exsolution are finished, needed dialkyl aminoethanol carboxylate citrate is prepared from a saturated citric acid solution with equal measurement and dialkyl aminoethanol carboxylate after exsolution by reaction. The preparation method of the present invention has the advantages of easy acquirement and low price of the raw material market of the catalyst, no strong toxicity of the solvent, simple treatment, high yield of the dialkyl aminoethanol carboxylate and salt thereof, white and bright product appearance and convenient storage and packaging, is capable of directly realizing industrial production and has obvious economic benefit.
Description
One. technical field: the present invention relates to a kind of preparation method of new plant growth regulator, particularly relate to the preparation method of a kind of dialkylamino ethanol carboxylate and salt thereof.
Two. background technology: plant-growth regulator is current domestic and international chemical boundary, organic sphere and agronomy circle priority fields of study, be considered to one of important component of 21 century agricultural super high-yielding, its research and development will effectively promote " Green Revolution " for the second time.Plant-growth regulator is meant in the plant materials except that nutritive substance plant-growth to be had the organic compound of regulating effect, its consumption is little, effect is big, energy stratification, control are bloomed, are delayed and controls aging course, increase output, improvement crop quality, increase resistance, are the effective constituent of solution food crop, cash crop super high-yielding.
Dialkylamino ethanol carboxylate is a kind of novel cytokinin plant-growth regulator, be widely used in food crop, cash crop, fruit tree, vegetables, flowers and edible mushrooms aspect, lower concentration (10mg/L) uses and just can promote the metabolism of carbohydrate and the accumulation of material, increase substantially the output of crop, significantly improve the quality of product.One of at present the most frequently used method for preparing carboxylicesters is: make carboxylic acid and alcohol generation esterification and synthesize in the presence of sulfuric acid, but because dialkylamino alcohol has stronger alkalescence, when the sulfuric acid that adds as catalyzer, sulfuric acid is preferential with the dialkylamino alcohol reaction equimolar ammonium sulfate of generation and lose katalysis, simultaneously, ammonium sulfate is insoluble to carboxylic acid and organic solvent, be unfavorable for that successful reaction carries out, and use not only corrosive equipment but also bring corresponding trouble of sulfuric acid, therefore be not suitable for being used for preparing dialkylamino ethanol carboxylate to aftertreatment.
Disclose some in the prior art and prepared the method for dialkylamino ethanol carboxylate.For example, reported a kind of method for preparing diethyl alkylamino alcohol carboxylate among the flat 1-290606 of Japan publication specification sheets JP-A-, it is to adopt fat acyl chloride and excessive diethyl alkylamino ethanol to react in a large amount of chloroform solvents, in ice bath, stir earlier, reacted 2 hours under the room temperature then, and place and spend the night, neutralize through alkali again, washing, get diethyl alkylamino alcohol carboxylate behind the precipitation, the shortcoming of this method is to use very easily hydrolysis, the acyl chlorides that transportation and keeping are all inconvenient, and acyl chlorides must carry out waterless operation simultaneously by the corresponding carboxylic acid preparation, and stronger to the corrodibility of equipment, this method produces equimolar hydrogenchloride, needs a large amount of alkali to neutralize in aftertreatment and washes.In addition, it has used a large amount of chloroforms, and toxicity is bigger, and the rate of recovery is lower, and product cost is increased.
Chinese invention patent CN1073429A, denomination of invention is: " preparation method of applying dioxan aminoethyl alcohol carboxylic ether ", the patent No. is the preparation method who discloses a kind of applying dioxan aminoethyl alcohol carboxylic ether in 92112507.0, it is that employing aromatic hydrocarbon is solvent, solid acid or heteropolyacid are catalyzer, and with carboxylic acid dialkylamino ethanol esterification, the shortcoming of this method is: solid acid or heteropolyacid complex manufacturing, still the industrialization product that does not have such catalyzer at present on the domestic market must existing system now be joined.Simultaneously, its aromatic hydrocarbon solvent toxicity is big, easily causes leukemia; And because the temperature of reaction height, long reaction time causes side reaction many, and yield is descended.
Chinese invention patent CN1305987A, denomination of invention is: " preparation method of dialkylamino ethanol carboxylate and salt thereof ", the patent No. is the preparation method who discloses a kind of dialkylamino ethanol carboxylate and salt thereof in 00101728.4, it is to adopt acyl chlorides and the direct solvent-free esterification of dialkylamino ethanol, it has inevitably repeated the shortcoming of the chloride method of Japanese Patent, in this patent, also introduced simultaneously the method for the synthetic dialkylamino ethanol carboxylate of transesterify, and the method for synthesizing dialkylamino ethanol carboxylate with caproic anhydride, the cost of these two kinds of methods is all quite high, the rate of exchange of caproic anhydride and acetate in the market are about 20: 1, and the need import.
Three. summary of the invention:
The objective of the invention is: overcome the deficiencies in the prior art, a kind of new dialkylamino ethanol carboxylate and the preparation method of salt thereof are provided.
Technical scheme of the present invention is: a kind of preparation method of dialkylamino ethanol carboxylate, and by dialkylamino ethanol and carboxylic acid esterification taking place under catalyst action makes, its chemical equation is:
Wherein, R
1For containing the alkyl of 1～5 carbon, R
2Be CH
3, C
2H
5, C
3H
7, adopting and contain the catalyzer of amino middle strong acid as esterification, the solvent of reaction is a carboxylic acid ester compound, temperature of reaction is 120～175 ℃, reaction times is 3～5 hours, after reaction finishes, promptly obtains diethyl alkylamino alcohol carboxylate through precipitation, distillation.
The described middle strong acid that contains amino is thionamic acid, or is primary ammonium phosphate, is preferably thionamic acid.
Described carboxylic acid ester compound solvent is a butylacetate, or is ethyl propionate, or is ethyl butyrate, is preferably butylacetate.
The salifying method of described dialkylamino ethanol carboxylate, behind esterification end and precipitation, with saturated citric acid solution that waits metering and the reaction of the dialkylamino ethanol carboxylate behind the precipitation, after the complete reaction, decolouring, crystallization, separation promptly obtain required dialkylamino ethanol carboxylate Citrate trianion.
The salifying method of described dialkylamino ethanol carboxylate, saturated citric acid solution are aqueous citric acid solution, or are the citric acid methanol solution, or are the citric acid ethanolic soln, are preferably the citric acid ethanolic soln.
Solvent in the reaction salification process is a water, or is methyl alcohol, or is ethanol, or is the ethanolic soln of citric acid.
Temperature of reaction in the reaction salification process is 120～175 ℃,
Positive beneficial effect of the present invention is:
1. the present invention adopts market to be easy to get, cheap contains amino middle strong acid---thionamic acid (H
2NSO
3H) or primary ammonium phosphate as catalyzer, its catalytic activity is not less than sulfuric acid, but the salify that has overcome sulfuric acid catalyst is insoluble and the shortcoming of the harshness of the complicacy of solid acid catalyst preparation and chloride method operation, and this catalyzer has the characteristics of high reactivity, high efficiency in esterification.At present, the market price of thionamic acid is 3.8 yuan/Kg, and the market price of primary ammonium phosphate is 2.3 yuan/Kg, and hence one can see that: catalyzer required for the present invention has cheap, and raw material is easy to get, advantage easy to use.
2. esterification of the present invention is solvent with the carboxylic acid ester compound, and its dewatering and aromatic hydrocarbon solvent are close, but has avoided the strong intoxicating of aromatic hydrocarbon solvent.
3. in the reaction salification process of the present invention, the acid of using is the citric acid saturated solution, and this method can generate oarse-grained dialkylamino ethanol carboxylate Citrate trianion product fast, the yield height, and product appearance is pure white glittering, is convenient to store, pack.
4. use preparation method of the present invention, the productive rate of dialkylamino ethanol carboxylate is higher, the catalyzer raw material is easy to get, inexpensive, solvent does not have strong intoxicating, handles simply, get final product behind the precipitation the product dialkylamino ethanol carboxylate, also can further get the Citrate trianion of dialkylamino ethanol carboxylate, can directly realize suitability for industrialized production having remarkable economic efficiency with sour salify.
Four. embodiment:
Embodiment one: the preparation of diethyl alkylamino ethanol capronate:
In the reaction flask that electric blender and water-and-oil separator and thermometer are housed, add the 153.2g n-caproic acid, 140.4g diethyl alkylamino ethanol, butylacetate 45mL, catalyzer thionamic acid (H
2NSO
3H) 4.5g opens and stirs, and slowly is warming up to 140 ℃, the azeotrope that the water that generates and butylacetate form that promptly responds is evaporated in the water-and-oil separator, when treating that temperature is increased to 158 ℃ continuously, no longer include water and generate (about 3.5 hours), extracting then goes out butylacetate residual in the solution, reaction promptly comes to an end, behind the reaction solution cool to room temperature, suction filtration (removing catalyzer) obtains the light brown transparent liquid, diethyl alkylamino ethanol caproate 237.6g, productive rate 92.7%.
Embodiment two: the preparation of diethyl alkylamino ethanol capronate:
The device of present embodiment, medicine and preparation method are identical with embodiment one, and something in common does not repeat, and difference is: the catalyzer thionamic acid is used primary ammonium phosphate 5.0g instead, and the result obtains dialkylamino ethanol caproate 216.9g, productive rate 84.9%.
Embodiment three: the preparation of diformazan alkyl monoethanolamine capronate:
The device of present embodiment, medicine and preparation method are identical with embodiment one, something in common does not repeat, difference is: 140.4g diethyl alkylamino ethanol is used the 106.8g dimethylaminoethanol instead, and the result obtains diformazan alkyl monoethanolamine caproate 206.8g, productive rate 93.1%.
Embodiment four: the preparation of diethyl alkylamino ethanol capronate:
The device of present embodiment, medicine and preparation method are identical with embodiment one, and something in common does not repeat, and difference is: the solvent acetic acid butyl ester is used ethyl propionate instead, and the result obtains diethyl alkylamino ethanol capronate 227.3g, productive rate 89.0%.
Embodiment five: the preparation of diethyl alkylamino ethanol capronate:
The device of present embodiment, medicine and preparation method are identical with embodiment one, and something in common does not repeat, and difference is: the solvent acetic acid butyl ester is used ethyl butyrate instead, and the result obtains diethyl alkylamino ethanol capronate 230.4g, productive rate 90.2%.
Embodiment six: the preparation of diethyl alkylamino ethanol butyric ester:
The device of present embodiment, medicine and preparation method are identical with embodiment one, and something in common does not repeat, and difference is: n-caproic acid 153.2g uses butanic acid 114.3g instead, and the result obtains diethyl alkylamino ethanol butyric ester 198.6g, productive rate 89.4%.
Embodiment seven: the preparation of diethyl alkylamino ethanol valerate:
The device of present embodiment, medicine and preparation method are identical with embodiment one, and something in common does not repeat, and difference is: n-caproic acid 153.2g uses positive valeric acid 122.2g instead, and the result obtains diethyl alkylamino ethanol valerate 209.0g, productive rate 87.1%.
Embodiment eight: the preparation of diethyl alkylamino ethanol butyric ester:
The device of present embodiment, medicine and preparation method are identical with embodiment one, something in common does not repeat, difference is: n-caproic acid 153.2g uses butanic acid 114.3g instead, the catalyzer thionamic acid is used phosphoric acid dihydro amine 5.0g instead, the result obtains diethyl alkylamino ethanol butyric ester 187.4g, productive rate 85.2%.
Embodiment nine: the preparation of diethyl alkylamino ethanol butyric ester:
The device of present embodiment, medicine and preparation method are identical with embodiment one, something in common does not repeat, and difference is: n-caproic acid 153.2g uses butanic acid 114.3g instead, and the solvent acetic acid butyl ester is used ethyl propionate instead, the result obtains diethyl alkylamino ethanol butyric ester 195.2g, productive rate 87.9%.
Embodiment ten: the preparation of diethyl alkylamino ethanol butyric ester:
The device of present embodiment, medicine and preparation method are identical with embodiment one, something in common does not repeat, and difference is: n-caproic acid 153.2g uses butanic acid 114.3g instead, and the solvent acetic acid butyl ester is used ethyl butyrate instead, the result obtains diethyl alkylamino ethanol butyric ester 184.7g, productive rate 83.1%.
Embodiment 11: the preparation of diethyl alkylamino ethanol valerate:
The device of present embodiment, medicine and preparation method are identical with embodiment one, something in common does not repeat, difference is: n-caproic acid 153.2g uses positive valeric acid 122.2g instead, the catalyzer thionamic acid is used primary ammonium phosphate 5.0g instead, the result obtains diethyl alkylamino ethanol valerate 198.5g, productive rate 82.7%.
Embodiment 12: the preparation of diethyl alkylamino ethanol valerate:
The device of present embodiment, medicine and preparation method are identical with embodiment one, something in common does not repeat, and difference is: n-caproic acid 153.2g uses positive valeric acid 122.2g instead, and the solvent acetic acid butyl ester is used ethyl propionate instead, the result obtains diethyl alkylamino ethanol valerate 204.7g, productive rate 85.3%.
Embodiment 13: the preparation of diethyl alkylamino ethanol valerate:
The device of present embodiment, medicine and preparation method are identical with embodiment one, something in common does not repeat, and difference is: n-caproic acid 153.2g uses positive valeric acid 122.2g instead, and the solvent acetic acid butyl ester is used ethyl butyrate instead, the result obtains diethyl alkylamino ethanol valerate 201.6g, productive rate 84.0%.
Embodiment 14: the preparation of diethyl alkylamino ethanol capronate Citrate trianion:
In the reaction flask that electric blender and water-and-oil separator and thermometer are housed, add the 230g n-caproic acid, 211g diethyl alkylamino ethanol, solvent acetic acid butyl ester 67ml, catalyzer thionamic acid (H
2NSO
3H) 6.8g.Open and stir, slowly be warming up to 140 ℃, the azeotrope that the water of the generation that promptly responds and butylacetate form is evaporated in the water-and-oil separator.When treating that temperature continues to be increased to 158 ℃, no longer include water and generate (needing 3.5 hours approximately), then extract residual acetic acid butyl ester in the solution under the negative pressure out, reaction promptly comes to an end.After reaction solution is cooled to room temperature, suction filtration (removing catalyzer), obtain light brown transparent liquid diethyl alkylamino ethanol capronate, under agitation this light brown liquid is slowly joined in 60 ℃ the alcohol saturated solution that contains the 317g citric acid, then add the 10g activated carbon and continue to stir 30 minutes, suction filtration while hot, the cooling of filtrate nature, crystallization, separation, drying obtain 670g diethyl alkylamino ethanol capronate Citrate trianion, product content 99.3%, productive rate 92.3%.
Embodiment 15: the preparation of diethyl alkylamino ethanol capronate Citrate trianion:
The device of present embodiment, medicine and preparation method are identical with embodiment 14, something in common does not repeat, difference is: in the salt-forming reaction process, the alcohol saturated solution of citric acid is used the distilled water saturated solution of citric acid instead, the result obtains diethyl alkylamino ethanol capronate Citrate trianion 632g, productive rate 87.1%.
Embodiment 16: the preparation of diethyl alkylamino ethanol capronate Citrate trianion:
The device of present embodiment, medicine and preparation method are identical with embodiment 14, something in common does not repeat, difference is: in the salt-forming reaction process, the alcohol saturated solution of citric acid is used the methyl alcohol saturated solution of citric acid instead, the result obtains diethyl alkylamino ethanol capronate Citrate trianion 686g, productive rate 94.5%.
Embodiment 17: the preparation of diethyl alkylamino ethanol butyric ester Citrate trianion:
The device of present embodiment, medicine and preparation method are identical with embodiment 14, something in common does not repeat, difference is: in esterification reaction process, n-caproic acid 230g uses butanic acid 114.3g instead, in the salt-forming reaction process, the alcohol saturated solution 317g of citric acid changes 205g into, and the result obtains diethyl alkylamino ethanol butyric ester Citrate trianion 381.2g, productive rate 94.8%.
Embodiment 18: the preparation of diethyl alkylamino ethanol butyric ester Citrate trianion:
The device of present embodiment, medicine and preparation method are identical with embodiment 17, something in common does not repeat, difference is: in the salt-forming reaction process, the alcohol saturated solution of citric acid is used the distilled water saturated solution of citric acid instead, the result obtains diethyl alkylamino ethanol butyric ester Citrate trianion 362.0g, productive rate 90.0%.
Embodiment 19: the preparation of diethyl alkylamino ethanol butyric ester Citrate trianion:
The device of present embodiment, medicine and preparation method are identical with embodiment 17, something in common does not repeat, difference is: in the salt-forming reaction process, the alcohol saturated solution of citric acid is used the methyl alcohol saturated solution of citric acid instead, the result obtains diethyl alkylamino ethanol butyric ester Citrate trianion 380.4g, productive rate 94.6%.
Embodiment 20: the preparation of diethyl alkylamino ethanol valerate Citrate trianion:
The device of present embodiment, medicine and preparation method are identical with embodiment 14, something in common does not repeat, difference is: in esterification reaction process, n-caproic acid 230g uses positive valeric acid 122.2g instead, in the salt-forming reaction process, citric acid 317g changes the alcohol saturated solution of 200g into, and the result obtains diethyl alkylamino ethanol valerate Citrate trianion 385.6g, productive rate 94.4%.
Embodiment 21: the preparation of diethyl alkylamino ethanol butyric ester Citrate trianion:
The device of present embodiment, medicine and preparation method are identical with embodiment 20, something in common does not repeat, difference is: in the salt-forming reaction process, the alcohol saturated solution of citric acid is used the distilled water saturated solution of citric acid instead, the result obtains diethyl alkylamino ethanol valerate Citrate trianion 349.0g, productive rate 85.4%.
Embodiment 22: the preparation of diethyl alkylamino ethanol butyric ester Citrate trianion:
The device of present embodiment, medicine and preparation method are identical with embodiment 20, something in common does not repeat, difference is: in the salt-forming reaction process, the alcohol saturated solution of citric acid is used the methyl alcohol saturated solution of citric acid instead, the result obtains diethyl alkylamino ethanol butyric ester Citrate trianion 384.9g, productive rate 94.2%.
Embodiment 23: diethyl alkylamino ethanol capronate is handled back 20 days result such as following table to the influence of cineraria protein and ribose content:
| Concentration of treatment (mg/kg) | Protein content (mg/g.Fw) | Than CK (± %) | Ribose content (ug/g.Fw) | Than CK (± %) |
| 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 |
Embodiment 24: diethyl alkylamino ethanol capronate is to corn seed germination rate, germination index, and vitality index, seedling is long and the influence of fresh weight, result such as following table:
| Concentration of treatment (mg/kg) | Percentage of germination (%) | Germination index (GI) | Vitality index (VI) | Seedling farm labourer (cm) | Fresh weight (mg/) |
| 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 (5)
1. the preparation method of a dialkylamino ethanol carboxylate, the molecular formula of dialkylamino ethanol carboxylate is R
1COOCH
2CH
2NR
2 2, R
1For containing the alkyl of 1～5 carbon, R
2Be CH
3, or C
2H
5, or C
3H
7Esterification takes place by dialkylamino ethanol and carboxylic acid and makes in it under catalyst action, it is characterized in that: adopt and contain the catalyzer of amino middle strong acid as esterification, the solvent of reaction is a carboxylic acid ester compound, temperature of reaction is 120～175 ℃, reaction times is 3～5 hours, after reaction finishes, promptly obtains diethyl alkylamino alcohol carboxylate through precipitation, distillation.
2. the preparation method of dialkylamino ethanol carboxylate according to claim 1 is characterized in that: described to contain amino middle strong acid be thionamic acid, or be primary ammonium phosphate.
3. the preparation method of dialkylamino ethanol carboxylate according to claim 1 is characterized in that: described to contain amino middle strong acid be thionamic acid.
4. the preparation method of dialkylamino ethanol carboxylate according to claim 1, it is characterized in that: described carboxylic acid ester compound solvent is a butylacetate, or is ethyl propionate, or is ethyl butyrate.
5. the preparation method of dialkylamino ethanol carboxylate according to claim 1, it is characterized in that: described carboxylic acid ester compound solvent is a butylacetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510017414 CN1268603C (en) | 2005-03-11 | 2005-03-11 | Process for preparing dialkylamino ethanol carboxylate and its salts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510017414 CN1268603C (en) | 2005-03-11 | 2005-03-11 | Process for preparing dialkylamino ethanol carboxylate and its salts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1666975A CN1666975A (en) | 2005-09-14 |
| CN1268603C true CN1268603C (en) | 2006-08-09 |
Family
ID=35038284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510017414 Expired - Fee Related CN1268603C (en) | 2005-03-11 | 2005-03-11 | Process for preparing dialkylamino ethanol carboxylate and its salts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1268603C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008238B (en) * | 2016-05-24 | 2018-05-04 | 苏州科技大学 | Double Diethylaminoethanol ester citrate compounds of plant growth regulator phthalic acid 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 |
| 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 |
-
2005
- 2005-03-11 CN CN 200510017414 patent/CN1268603C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1666975A (en) | 2005-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104119230B (en) | A kind of synthetic method of long-chain nipagin esters and application thereof | |
| CN1268603C (en) | Process for preparing dialkylamino ethanol carboxylate and its salts | |
| CN1847241A (en) | Synthesis process of 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolyl-2-imine | |
| CN1155543C (en) | Amino acid composite liquid fertilizer | |
| CN103896660B (en) | A kind of humic acid type fluid Chemical Mixed Fertilizer composition utilizing sugar refinery, grain distillery, Gourmet Powder Factory, yeast factory waste | |
| CN110668977B (en) | Preparation process of lauroyl arginine ethyl ester hydrochloride | |
| CN109810697B (en) | Dictyophora indusiata pileus carbon quantum dot and preparation method thereof | |
| CN114853593B (en) | Method for extracting high-purity nervonic acid from acer truncatum oil | |
| CN103881922B (en) | A kind of method of utilization microbial flocculant harvesting microalgae | |
| CN114009267B (en) | Pomegranate planting method rich in polyphenol | |
| CN1301967C (en) | Method of chiral separation for D,L-phenylalanine ester or its salt | |
| CN1793125A (en) | Dindoly methylane and preparation process thereof | |
| CN1164853A (en) | Process for crystallization from water of (S)-N,N'-bis[2-hydroxy-1-(hydroxymethyl) ethyl]-5-[(2-hydroxy-1-oxopropyl)amino]-2,4,6-triiodo-1,3-benzendicarboxamide | |
| CN101215194A (en) | Method for formulating long-acting microorganism leaf fertilizer | |
| CN115413531B (en) | Culture material for needle mushroom culture and needle mushroom culture method | |
| CN114933529B (en) | Method for separating and preparing high-purity ethyl nervonate from acer truncatum kernel | |
| CN101671704B (en) | Method for preparing L-selenomethionine by using enzyme separation method | |
| CN1162396C (en) | Process for preparing dialkylamino ethanol carboxylate and its salt | |
| CN111019980B (en) | Biosynthesis method of mono-p-nitrobenzyl malonate | |
| CN1208312C (en) | New process for preparing compound amino acid by using animal hoof and foot | |
| CN102656139B (en) | Methods for the production of L-carnitine | |
| CN1308286C (en) | Method for preparing diethylaminoethanol caproate | |
| CN1935826A (en) | Method for preparing S-adenosine-L-methioninel P-toluenesulfonate | |
| CN1298691C (en) | Production technology of high activity high purity chelate calcium | |
| CN1114344C (en) | Plant growth regulator, prepn. method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHENGZHOU TUO YANG BIOENGINEERING CO., LTD. Free format text: FORMER OWNER: XIE YUNMAN Effective date: 20081114 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20081114 Address after: No. 76, science Avenue, West Development Zone, Henan, Zhengzhou Patentee after: Zhengzhou Tuoyang Bioengineering Co., Ltd. Address before: No. 37, Jianshe East Road, Zhengzhou, Henan Patentee before: Xie Yunman |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Zhengzhou Tuoyang Bioengineering Co., Ltd. Assignor: Xie Yunman Contract fulfillment period: 2008.10.17 to 2024.10.17 contract change Contract record no.: 2008410000178 Denomination of invention: Process for preparing dialkylamino ethanol carboxylate and its salt Granted publication date: 20060809 License type: Exclusive license Record date: 2008.12.8 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.10.17 TO 2024.10.17; CHANGE OF CONTRACT Name of requester: ZHENGZHOU TUO YANG BIOENGINEERING CO., LTD. Effective date: 20081208 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060809 Termination date: 20120311 |