CN105801441A - Plant growth regulator bis(diethylaminoethyl)adipate citrate compound and preparing method thereof - Google Patents
Plant growth regulator bis(diethylaminoethyl)adipate citrate compound and preparing method thereof Download PDFInfo
- Publication number
- CN105801441A CN105801441A CN201610349734.XA CN201610349734A CN105801441A CN 105801441 A CN105801441 A CN 105801441A CN 201610349734 A CN201610349734 A CN 201610349734A CN 105801441 A CN105801441 A CN 105801441A
- Authority
- CN
- China
- Prior art keywords
- diethylaminoethanol
- adipic acid
- double
- adipic
- plant growth
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/265—Citric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a plant growth regulator bis(diethylaminoethyl)adipate citrate compound and a preparing method thereof.The structure of the compound is shown as follow (see the formula in the description).The preparing method includes the steps that organic solvent is added into a reactor provided with a manifold and a reflux device, under the action of a catalyst, the molar ratio of adipic acid or adipic anhydride to N,N-diethylaminoethanol is controlled to be 1:2-1:3, reaction is conducted at the temperature of 110-150 DEG C in a reflux and water division mode, the product is filtered, reduced pressure distillation is conducted on filter liquor to obtain the organic solvent and excess diethylaminoethanol, a kettle substrate is decolored with activated clay to obtain bis(diethylaminoethyl)adipate, and bis(diethylaminoethyl)adipate reacts with citric acid to be salified so as to obtain the white solid product, wherein the mole number of citric acid is two times that of bis(diethylaminoethyl)adipate.The compound has the effects of promoting seed germination, enhancing photosynthesis, promoting plant growth, increasing crop yield, improving fruit quality, enhancing plant adverse resistance and the like and is a broad-spectrum active regulator.The production process is simple, and industrial production is easy to achieve.
Description
Technical field
The present invention relates to double Diethylaminoethanol ester citrate compound of a kind of new plant growth regulator adipic acid and preparation method thereof.This compound has promotion seed germination, promotes plant growing, strengthens photosynthesis, improves crop yield, improve fruit quality and strengthen the purposes such as stress resistance of plant.
Background technology
China, but before 1949, does not applies from promoting that cuttage root-taking begins one's study plant growth regulator from nineteen thirty-seven on producing.After 1949, introducing 2 from external, 4-dichlorphenoxyacetic acid, naphthalene acetic acid etc. are applied to the crops such as Fructus Mali pumilae, Fructus Lycopersici esculenti in case falling stop is spent, shedding.In later stage the 1950's, due to succeeding in developing of phenol regulator, range of application expands further.To the sixties, the kind of application and object have again increase, but focus primarily upon chlorocholine chloride application on Cotton Gossypii and Semen Tritici aestivi.After the seventies, China obtains multinomial great achievement to plant growth regulator rationale and applied research, has played great role, thus also cause domestic many pesticide researches and the attention of production unit on producing.Plant growth regulator is widely used in crop to regulate and control its growth promoter, and its major function has termination seed, bud and the dormancy of tuber, the effect such as stratification and growth promoting of taking root.
South China much area vegetables, the rotten kind of flowers problem of being short of seedling is the most serious, and after its reason is mainly seed harvest, basking seeds, in storage, seed vitality easily reduces even to be lost.Water suction is the essential condition of seed germination, and dry seed cell is in gel state, and cell membrane is discontinuous and loses its selected area update strategy, and early imbibition seed turns to lenticular from gel, and membranous system must be repaired.When seed is directly under water or sowing is in wetland, owing to water suction is fast, film has little time to repair, and loses the integrity of its original, sugar, organic acid, ion, aminoacid even protein and the phenomenon of osmosis of enzyme occur, this phenomenon membranous system to be waited until could reduce after repairing.Therefore, vegetable, flowers add plant growth regulator to promote that germination takes root and have become as trend.In recent years China to plant growth regulator research and application development the most quickly.But its kind, quantity all can not meet the demand in market.
At present the most being applied more by market is DCPTA N, N-diethyl-2-(3,4-dichlorophenoxy) ethamine (DCPTA) and caproic acid Diethylaminoethanol ester (DA-6), inventor finds to have in both structures diethylamino ethoxy group, according to " principle of hybridization ", it is carried out split with adipic acid, i.e. obtains, containing double diethylamino ethoxy structures, there is bioactive compound adipic acid pair Diethylaminoethanol ester.It is polyfunctional group synergistic structure, similar to caproic acid Diethylaminoethanol ester (DA-6) in structure, and adds the number of diethylamino ethoxy so that it is have the most excellent plant growth regulation.
Summary of the invention
An object of the present invention is that proposing one has the double Diethylaminoethanol ester citrate of bioactive compound adipic acid.This compound has simple in construction, soluble in water, is easily entered in cyton by cell wall.Compared with existing plant growth regulator, there is amount of application few, the advantages such as effect is notable, environmentally safe, low toxicity, deficiency of the prior art can be overcome.
For achieving the above object, present invention employs following technical scheme:
The double Diethylaminoethanol ester citrate compound of a kind of adipic acid, it is characterised in that the structure of this compound is shown below:
Another object of the present invention is to propose the preparation method of the double Diethylaminoethanol ester citrate of a kind of adipic acid.Its technique is simple, it is easy to large-scale production, and cheaper starting materials is easy to get, and equipment investment is few, with low cost, and atom utilization is high, and environmental pollution is little, and the method is:
A certain amount of organic solvent is added in the reactor equipped with water knockout drum and reflux, proper catalyst, add adipic acid and the N of certain mol proportion, N-diethylaminoethanol, the lower heating of stirring, reflux water-dividing reaction at a temperature of 110 DEG C～150 DEG C, reaction 5～9h, until the water separated reaches theoretical amount, Filtration of catalyst (reclaims and uses), filtrate decompression distills out organic solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess and low boilers, bottoms adds the double Diethylaminoethanol ester Theoretical Mass 5%-10% activated decoloration of adipic acid, stir 30 minutes, filter to obtain the double Diethylaminoethanol ester of yellow oily liquid adipic acid.Putting in reactor by the citric acid of double for adipic acid Diethylaminoethanol esters with twice mole again, be heated with stirring to 120 DEG C, after citric acid melts, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white solid product adipic acid.
The method can be also:
A certain amount of organic solvent is added in the reactor equipped with water knockout drum and reflux, proper catalyst, add adipic anhydride and the N of certain mol proportion, N-diethylaminoethanol, the lower heating of stirring, reflux water-dividing reaction at a temperature of 110 DEG C～150 DEG C, reaction 3～5h, until the water separated reaches theoretical amount, Filtration of catalyst (reclaims and uses), filtrate decompression distills out organic solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess and low boilers, bottoms adds the double Diethylaminoethanol ester Theoretical Mass 5%-10% activated decoloration of adipic acid, stir 30 minutes, filter to obtain the double Diethylaminoethanol ester of yellow oily liquid adipic acid.Putting in reactor by the citric acid of double for adipic acid Diethylaminoethanol esters with twice mole again, be heated with stirring to 120 DEG C, after citric acid melts, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white solid product adipic acid.
A certain amount of organic solvent described above is dimethylbenzene or toluene, and its consumption volume milliliter number is adipic acid or 1-8 times of adipic anhydride quality grams.
The adipic acid of certain mol proportion as above and N, N-diethylaminoethanol, the adipic anhydride of certain mol proportion and N, N-diethylaminoethanol is adipic acid or adipic anhydride: the mol ratio of N, N-diethylaminoethanol is 1:2-1:3.
Proper catalyst as above is titanyl sulfate, titanium dioxide or silica gel, and its consumption is adipic acid or the 2%-10% of adipic anhydride quality grams.
The double Diethylaminoethanol ester of adipic acid of the present invention is yellow oily liquid, water insoluble, but is dissolved in the organic solvents such as chloroform, petroleum ether, ethanol, index of refraction: nD 25=1.6582, density (20 DEG C): 0.7895g/cm3；Productivity is 85.4%～91.1%, and the double Diethylaminoethanol ester citrate of adipic acid is white powder crystal, and fusing point is 117 DEG C, soluble in water, insoluble in chloroform.
The preparation principle of the double Diethylaminoethanol ester citrate of adipic acid is shown below:
Or
Compared with prior art, the invention have benefit that:
(1) containing Liang Ge diethylaminoethanol ester functional group, molecular structure carrier each other in one molecule of present configuration, atom utilization is high, and active function groups superposition, it can play excellent plant growth regulation so that it is active effect significantly improves.
(2) the compounds of this invention has promotion seed germination, promotes plant growing, strengthens photosynthesis, improves crop yield, improve fruit quality and strengthen the effect such as stress resistance of plant, and it is of many uses, for broad spectrum type active regulator.
(3) to have consumption few for the compounds of this invention, the advantages such as toxicity is little, free from environmental pollution.
(4) Diethylaminoethanol of the compounds of this invention preparation technology used catalyst and solvent and excess is all directly to reclaim use, does not produce pollution, does not cause waste, belongs to green preparation process.
(5) when catalyst made by the compounds of this invention preparation technology silica gel, self there is decolorization, the decolorization to product can be saved.
(6) the compounds of this invention preparation method is simple, and cheaper starting materials is easy to get, low cost, and equipment investment is few, it is easy to large-scale production, has good application and development prospect.
Accompanying drawing explanation
Structure and performance spy in order to further illustrate product provide drawings described below.
Fig. 1 is the infrared spectrogram of the double Diethylaminoethanol ester of adipic acid；Fig. 1 shows, at 1750cm-1Near occur in that strong absworption peak, correspond to the stretching vibration of ester carbonyl group；Additionally, 2900cm-1Near CH occurs2The stretching vibration of middle c h bond；At 1350cm-1Near the stretching vibration of C-N-C key occurs；
Fig. 2 is the nuclear magnetic spectrum figure of the double Diethylaminoethanol ester of adipic acid；Fig. 2 shows, deuterochloroform is solvent, and δ 0.98 ~ 1.06 is N-(CH2CH3)2In methyl hydrogen peak；δ 2.50 ~ 2.65 is N-(CH2CH3)2The methylene hydrogen peak being connected with nitrogen；δ 2.67 ~ 2.72 is-OCH2CH2Methylene hydrogen peak that-N is connected with nitrogen and O=CCH2CH2CH2CH2The methylene hydrogen peak that C=O is connected with carbonyl；δ 4.12 ~ 4.19 is-OCH2CH2The methylene hydrogen peak that N is connected with oxygen.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 is adding 14.6g (0.1mol) adipic acid equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 20ml dimethylbenzene, it is heated with stirring to 150 DEG C of back flow reaction 5h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 31.10g of yellow oily liquid adipic acid, productivity is 90.4%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 2 is addition 14.6g (0.1mol) adipic acid in the 250ml four-hole boiling flask equipped with agitator and water knockout drum and reflux, and 23.4
G (0.2mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 40ml dimethylbenzene, it is heated with stirring to 140 DEG C of back flow reaction 8h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, after decompression distilling off solvent (reclaim and use) and low boilers, add 3.0g active hargil and stir 30 minutes, be cooled to less than 80 DEG C, filtering to obtain the double Diethylaminoethanol ester 29.55g of yellow oily liquid adipic acid, productivity is 85.9%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 3 is adding 14.6g (0.1mol) adipic acid equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.8g titanium dioxide, 20ml dimethylbenzene, it is heated with stirring to 150 DEG C of back flow reaction 8h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 30.34g of yellow oily liquid adipic acid, productivity is 88.2%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 4 is adding 14.6g (0.1mol) adipic acid equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 29.3g (0.25mol) N, N-diethylaminoethanol, 0.6g titanyl sulfate, 40ml dimethylbenzene, it is heated with stirring to 140 DEG C of back flow reaction 7h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 30.07g of yellow oily liquid adipic acid, productivity is 87.4%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 5 is adding 14.6g (0.1mol) adipic acid equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 29.3g (0.25mol) N, N-diethylaminoethanol, 1.0g silica gel, 40ml dimethylbenzene, it is heated with stirring to 140 DEG C of back flow reaction 6h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, obtain the double Diethylaminoethanol ester 30.03g of yellow oily liquid adipic acid, productivity is 87.3%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 6 is adding 14.6g (0.1mol) adipic acid equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.7g titanyl sulfate, 30ml toluene, it is heated with stirring to 120 DEG C of back flow reaction 6h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 30.86g of yellow oily liquid adipic acid, productivity is 89.7%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 7 is adding 14.6g (0.1mol) adipic acid equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.8g titanium dioxide, 30ml toluene, it is heated with stirring to 120 DEG C of back flow reaction 8h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 30.55g of yellow oily liquid adipic acid, productivity is 88.8%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 8 is addition 14.6g (0.1mol) adipic acid in the 250ml four-hole boiling flask equipped with agitator and water knockout drum and reflux, and 23.4
G (0.2mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 40ml toluene, it is heated with stirring to 110 DEG C of back flow reaction 9h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 100ml, after decompression distilling off solvent (reclaim and use) and low boilers, add 3.0g active hargil and stir 30 minutes, be cooled to less than 80 DEG C, filtering to obtain the double Diethylaminoethanol ester 29.38g of yellow oily liquid adipic acid, productivity is 85.4%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 9 is adding 14.6g (0.1mol) adipic acid equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 29.3g (0.25mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 40ml toluene, it is heated with stirring to 110 DEG C of back flow reaction 7h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 30.31g of yellow oily liquid adipic acid, productivity is 88.1%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 10 is adding 14.6g (0.1mol) adipic acid equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 29.3g (0.25mol) N, N-diethylaminoethanol, 1.0g silica gel, 40ml toluene, it is heated with stirring to 110 DEG C of back flow reaction 8h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, obtain the double Diethylaminoethanol ester 30.13g of yellow oily liquid adipic acid, productivity is 87.6%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 11 is adding 12.8g (0.1mol) adipic anhydride equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 20ml dimethylbenzene, it is heated with stirring to 145 DEG C of back flow reaction 3h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 31.34g of yellow oily liquid adipic acid, productivity is 91.1%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 12 is adding 12.8g (0.1mol) adipic anhydride equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 23.4g (0.2mol) N, N-diethylaminoethanol, 0.6g titanyl sulfate, 40ml dimethylbenzene, it is heated with stirring to 145 DEG C of back flow reaction 5h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, after decompression distilling off solvent (reclaim and use) and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 29.76g of yellow oily liquid adipic acid, productivity is 86.5%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 13 is adding 12.8g (0.1mol) adipic anhydride equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 29.3g (0.25mol) N, N-diethylaminoethanol, 0.8g titanium dioxide, 40ml dimethylbenzene, it is heated with stirring to 145 DEG C of back flow reaction 4h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 30.58g of yellow oily liquid adipic acid, productivity is 88.9%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 14 is adding 12.8g (0.1mol) adipic anhydride equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.8g titanium dioxide, 30ml toluene, it is heated with stirring to 113 DEG C of back flow reaction 3h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, add 3.0g active hargil to stir 30 minutes, it is cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 30.86g of yellow oily liquid adipic acid, productivity is 89.7%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 15 is adding 12.8g (0.1mol) adipic anhydride equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 23.4g (0.2mol) N, N-diethylaminoethanol, 1.0g silica gel, 40ml toluene, it is heated with stirring to 113 DEG C of back flow reaction 5h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, after decompression distilling off solvent (reclaim and use) and low boilers, obtain the double Diethylaminoethanol ester 30.44g of yellow oily liquid adipic acid, productivity is 88.5%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Embodiment 16 is adding 12.8g (0.1mol) adipic anhydride equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux, 29.3g (0.25mol) N, N-diethylaminoethanol, 1.0g silica gel, 40ml toluene, it is heated with stirring to 113 DEG C of back flow reaction 4h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate proceeds in the there-necked flask of another 250ml, decompression distilling off solvent (reclaims and uses), after the diethylaminoethanol (reclaim and use) of excess and low boilers, obtain the double Diethylaminoethanol ester 30.31g of yellow oily liquid adipic acid, productivity is 88.1%.Again the citric acid mix and blend of double for adipic acid Diethylaminoethanol esters with twice mole being heated to 120 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product adipic acid.Its fusing point: 117 DEG C.
Table 1 adipic acid is that main technologic parameters prepared by raw material
Table 2 adipic anhydride is that main technologic parameters prepared by raw material
The adipic acid diethylaminoethanol ester citric acid hydrochlorate of above-mentioned preparation is used for green vegetable, Semen Glycines, Semen Tritici aestivi, Brassica campestris L, rice paddy seed with reference to " international seed inspection procedure " (1985), " crop seeds inspection procedure " (1995) as evaluating the standard (to grow 1cm for germinateing) whether seed germinates by inventor, having made biological activity test, (A is sample regulation activity to calculate regulation percent activity with A=(N-N0)/N0 × 100% formula；N cultivates the length of the root recorded in compound solution；N0 cultivate in distilled water record with length.).
One, experimental technique
Use plate culture, adipic acid diethylaminoethanol ester citrate is configured to respectively the solution of 100mg/L, 70mg/L, 40mg/L and 10mg/L variable concentrations, studies it to green vegetable, Semen Glycines, Semen Tritici aestivi, Brassica campestris L, the growth regulating effect of rice seedling root system.Blank assay is made with distilled water, the DA-6 solution of same concentrations makees standard control group, respectively with the solution soaking green vegetable of respective concentration, Semen Glycines, Semen Tritici aestivi, Brassica campestris L, rice paddy seed 6h 8h, then be respectively placed in temperature be 23 DEG C, 25 DEG C, 20 DEG C, 23 DEG C, 28 DEG C of constant temperature culture rooms measure the length of its root system and stem, and add up germination number after cultivating 4d 6d.
Two, experimental result
Adipic acid diethylaminoethanol ester citrate prepared by the present invention is shown in Table 3 respectively to the data of plant growth regulating activity, shown in table 4, table 5, table 6, table 7.
The double Diethylaminoethanol ester citrate of table 3 adipic acid is for green vegetable seed (50) Seed germination data
The double Diethylaminoethanol ester citrate of table 4 adipic acid is for Semen Glycines seed (10) Seed germination data
The double Diethylaminoethanol ester citrate of table 5 adipic acid is for wheat seed (30) Seed germination data
The double Diethylaminoethanol ester citrate of table 6 adipic acid is for Semen Brassicae campestris (50) Seed germination data
The double Diethylaminoethanol ester citrate of table 7 adipic acid is for rice paddy seed (30) Seed germination data
Claims (7)
1. the double Diethylaminoethanol ester citrate compound of a plant growth regulators adipic acid, it is characterised in that the structure of this compound is shown below:
。
2. the preparation method of the double Diethylaminoethanol ester citrate compound of a plant growth regulators adipic acid, it is characterised in that the method is:
A certain amount of organic solvent is added in the reactor equipped with water knockout drum and reflux, proper catalyst, add adipic acid and the N of certain mol proportion, N-diethylaminoethanol, the lower heating of stirring, reflux water-dividing reaction at a temperature of 110 DEG C～150 DEG C, reaction 5～9h, until the water separated reaches theoretical amount, Filtration of catalyst, filtrate decompression distills out organic solvent, the diethylaminoethanol of excess and low boilers, bottoms adds the double Diethylaminoethanol ester Theoretical Mass 5%-10% activated decoloration of adipic acid, stir 30 minutes, filter to obtain the double Diethylaminoethanol ester of yellow oily liquid adipic acid；Putting in reactor by the citric acid of double for adipic acid Diethylaminoethanol esters with twice mole again, be heated with stirring to 120 DEG C, after citric acid melts, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white solid product adipic acid.
3. the preparation method of the double Diethylaminoethanol ester citrate compound of a plant growth regulators adipic acid, it is characterised in that the method is:
A certain amount of organic solvent is added in the reactor equipped with water knockout drum and reflux, proper catalyst, add adipic anhydride and the N of certain mol proportion, N-diethylaminoethanol, the lower heating of stirring, reflux water-dividing reaction at a temperature of 110 DEG C～150 DEG C, reaction 3～5h, until the water separated reaches theoretical amount, Filtration of catalyst, filtrate decompression distills out organic solvent, the diethylaminoethanol of excess and low boilers, bottoms adds the double Diethylaminoethanol ester Theoretical Mass 5%-10% activated decoloration of adipic acid, stir 30 minutes, filter to obtain the double Diethylaminoethanol ester of yellow oily liquid adipic acid；Putting in reactor by the citric acid of double for adipic acid Diethylaminoethanol esters with twice mole again, be heated with stirring to 120 DEG C, after citric acid melts, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester citrate of white solid product adipic acid.
4. according to the preparation method of the double Diethylaminoethanol ester citrate compound of a plant growth regulators adipic acid described in Claims 2 or 3, it is characterized in that: described a certain amount of organic solvent is dimethylbenzene or toluene, its consumption volume milliliter number is adipic acid or 1-8 times of adipic anhydride quality grams.
5. according to the preparation method of the double Diethylaminoethanol ester citrate compound of a plant growth regulators adipic acid described in Claims 2 or 3, it is characterized in that: the adipic acid of described certain mol proportion and N, N-diethylaminoethanol, the adipic anhydride of certain mol proportion and N, N-diethylaminoethanol is adipic acid or adipic anhydride: the mol ratio of N, N-diethylaminoethanol is 1:2-1:3.
6. according to the preparation method of the double Diethylaminoethanol ester citrate compound of a plant growth regulators adipic acid described in Claims 2 or 3, it is characterized in that: described proper catalyst is titanyl sulfate, titanium dioxide or silica gel, its consumption is adipic acid or the 2%-10% of adipic anhydride quality grams.
7. according to the preparation method of the double Diethylaminoethanol ester citrate compound of a plant growth regulators adipic acid described in Claims 2 or 3, it is characterized in that: described Filtration of catalyst, filtrate decompression distill out organic solvent, excess diethylaminoethanol be recovered to catalyst, organic solvent, diethylaminoethanol recycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610349734.XA CN105801441B (en) | 2016-05-24 | 2016-05-24 | Double Diethylaminoethanol ester citrate compounds of plant growth regulator adipic acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610349734.XA CN105801441B (en) | 2016-05-24 | 2016-05-24 | Double Diethylaminoethanol ester citrate compounds of plant growth regulator adipic acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801441A true CN105801441A (en) | 2016-07-27 |
| CN105801441B CN105801441B (en) | 2018-04-20 |
Family
ID=56451786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610349734.XA Active CN105801441B (en) | 2016-05-24 | 2016-05-24 | Double Diethylaminoethanol ester citrate compounds of plant growth regulator adipic acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801441B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112931143A (en) * | 2021-03-09 | 2021-06-11 | 广西大学 | Special seedling raising substrate for mangoes and preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT185371B (en) * | 1953-06-23 | 1956-04-25 | Chemie Linz Ag | Process for the production of new polymethylene or phenylene-bis-carbamic acid esters |
| FR2209501A1 (en) * | 1972-12-08 | 1974-07-05 | Bayer Ag | Polyurethane foam substrates for plant growth - which slowly release acid gps. and are softened when satd. with water |
| JPH01290606A (en) * | 1988-05-17 | 1989-11-22 | Nitto Baion Kk | Plant growth promoter and production thereof |
| CN1073429A (en) * | 1992-10-26 | 1993-06-23 | 厦门大学 | The preparation method of applying dioxan aminoethyl alcohol carboxylic ether |
| CN1305987A (en) * | 2000-01-17 | 2001-08-01 | 珠海真绿色技术有限公司 | Process for preparing dialkylamino ethanol carboxylate and its salt |
-
2016
- 2016-05-24 CN CN201610349734.XA patent/CN105801441B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT185371B (en) * | 1953-06-23 | 1956-04-25 | Chemie Linz Ag | Process for the production of new polymethylene or phenylene-bis-carbamic acid esters |
| FR2209501A1 (en) * | 1972-12-08 | 1974-07-05 | Bayer Ag | Polyurethane foam substrates for plant growth - which slowly release acid gps. and are softened when satd. with water |
| JPH01290606A (en) * | 1988-05-17 | 1989-11-22 | Nitto Baion Kk | Plant growth promoter and production thereof |
| CN1073429A (en) * | 1992-10-26 | 1993-06-23 | 厦门大学 | The preparation method of applying dioxan aminoethyl alcohol carboxylic ether |
| CN1305987A (en) * | 2000-01-17 | 2001-08-01 | 珠海真绿色技术有限公司 | Process for preparing dialkylamino ethanol carboxylate and its salt |
Non-Patent Citations (7)
| Title |
|---|
| 何节玉 等: "油酸-2-乙基己酯的催化合成及性能", 《精细石油化工》 * |
| 叶丽梅 等: "聚乙烯醇与顺丁烯二酸酐酯化反应的研究", 《中山大学学报》 * |
| 李卫华 等: "HPLC法测定烟草肥料中己酸二乙氨基乙醇酯柠檬酸盐", 《安徽农业科学》 * |
| 李海泉 等: "N,N-二乙氨基乙醇己酸酯的合成", 《北京化工大学学报》 * |
| 王铭琦: "新型植物生长调节剂DA-6的合成与活性研究", 《中国优秀硕士学位论文全文数据库 农业科技辑》 * |
| 赵黔榕 等: "纳米二氧化钛催化合成乙酸丁酯的研究", 《云南师范大学学报》 * |
| 钟建华 等: "无溶剂条件下的有机反应——催化条件下醇与酸酐的反应", 《化学试剂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112931143A (en) * | 2021-03-09 | 2021-06-11 | 广西大学 | Special seedling raising substrate for mangoes and preparation method |
| CN112931143B (en) * | 2021-03-09 | 2023-07-04 | 广西大学 | Seedling raising matrix special for mangoes and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105801441B (en) | 2018-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103461141A (en) | Method for improving culturing efficiency of japonica rice anther | |
| CN113079997B (en) | Hemerocallis fulva forcing culture method | |
| CN113754550B (en) | Compound for improving fertilizer absorption and utilization efficiency and preparation method and application thereof | |
| CN105906516A (en) | Plant growth regulator succinic bis-diethylamino glycolate citrate compound and preparation method thereof | |
| CN109006361A (en) | A kind of production method of bio-matrix | |
| CN103588517A (en) | Efficient sugarcane seedling cultivating matrix | |
| CN105130701A (en) | Rhododendron simsii cultivation matrix and preparation method thereof | |
| CN105028212B (en) | The method for building up of moss Zhu Zhu high-efficiency regeneration systems | |
| CN105075682A (en) | Method for grafting red plum and peach | |
| CN103004608B (en) | Culture medium for culturing hoya tissue and culture method | |
| CN105152760A (en) | Osmanthus fragrans culture medium and preparation method thereof | |
| CN105801441A (en) | Plant growth regulator bis(diethylaminoethyl)adipate citrate compound and preparing method thereof | |
| CN104396753B (en) | A kind of method of spermine breeding sugar-cane tissue culture seedlings | |
| CN103766039B (en) | Method for breaking dormancy of nervilis fordii schlecht bulb | |
| CN111234841A (en) | Preparation and application of novel disease and pest prevention soil conditioner | |
| CN112567923B (en) | Efficient germination accelerating and rapid seedling raising method for rice seeds | |
| CN105906518B (en) | The double Diethylaminoethanol ester citrate compounds of plant growth regulator fumaric acid and preparation method | |
| CN114836462A (en) | Efficient agrobacterium-mediated genetic transformation method for melons | |
| CN105906517A (en) | Plant growth regulator decanedioic acid double diethylamine alcohol ester acetate citrate compound and preparation method thereof | |
| CN105210883B (en) | A kind of culture medium of tuber crops and its application | |
| CN107466644A (en) | A kind of culturing sugarcane seedlings method | |
| CN106900743A (en) | The compound formulation of corn growth under a kind of promotion drought stress | |
| CN108464078B (en) | Moisture absorption and drying treatment method for improving melon seed quality | |
| CN102763685A (en) | Banana vascular wilt resistant fermentation liquor and preparation method and application thereof | |
| CN105085036A (en) | Containerized walnut seedling raising matrix and preparation method 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 | ||
| CB02 | Change of applicant information |
Address after: 215009 Suzhou City, Jiangsu province high tech Zone CREE Road, No. 1 Applicant after: SUZHOU University OF SCIENCE AND TECHNOLOGY Address before: 215009 Suzhou City, Jiangsu province high tech Zone CREE Road, No. 1 Applicant before: University of Science and Technology of Suzhou |
|
| COR | Change of bibliographic data | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Jing Inventor after: Wang Hao Inventor after: Wang Siyuan Inventor after: Qiu Yexian Inventor after: Wang Yanlin Inventor before: Wang Yanlin Inventor before: Wang Hao Inventor before: Wang Siyuan Inventor before: Qiu Yexian |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230515 Address after: 712000 Jingyang County industrial concentration zone, Xianyang City, Shaanxi Province Patentee after: SHAANXI GENGYUAN ECOLOGICAL AGRICULTURE Co.,Ltd. Address before: 215009 CREE Road, Suzhou hi tech Zone, Suzhou, Jiangsu Province, No. 1 Patentee before: SUZHOU University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right |