CN105801441B - Double Diethylaminoethanol ester citrate compounds of plant growth regulator adipic acid and preparation method thereof - Google Patents
Double Diethylaminoethanol ester citrate compounds of plant growth regulator adipic acid and preparation method thereof Download PDFInfo
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- CN105801441B CN105801441B CN201610349734.XA CN201610349734A CN105801441B CN 105801441 B CN105801441 B CN 105801441B CN 201610349734 A CN201610349734 A CN 201610349734A CN 105801441 B CN105801441 B CN 105801441B
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- adipic acid
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- 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
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- 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
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- 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
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- 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
Abstract
The present invention relates to double Diethylaminoethanol ester citrate compounds of a plant growth regulators adipic acid and preparation method thereof, the structure of the compound is shown below：
Description
Technical field
The present invention relates to a kind of double Diethylaminoethanol ester citrate compounds of new plant growth regulator adipic acid
And preparation method thereof.The compound have promote seed sprout, promote plant growth, enhancing photosynthesis, improve crop yield,
Improve the purposes such as fruit quality and enhancing stress resistance of plant.
Background technology
China is from nineteen thirty-seven from promoting cuttage root-taking to begin one's study plant growth regulator, but before 1949, always not
Applied in production.After 1949, introduce 2,4- dichlorphenoxyacetic acids, methyl α-naphthyl acetate etc. from foreign countries and be applied to apple, tomato
Deng crops to prevent falling stop flower, shedding.Later stage the 1950s, due to succeeding in developing for phenol conditioning agent, application range
Further expand.To the sixties, the species and object of application have increase again, but focus primarily upon cycocel in cotton and wheat
On application.After the seventies, China obtains multinomial great achievement to plant growth regulator basic theory and application study,
Great role has been played in production, thus has also caused the attention of domestic many pesticide researches and production unit.Plant growth regulator
Be widely used in crop to regulate and control its growth development, its major function has a dormancy for terminating seed, bud and stem tuber, stratification and
Growth promoting of taking root etc. acts on.
The many regional vegetables of south China, the rotten kind of flowers is short of seedling, and problem is very serious always, its reason is mainly seed harvest
Afterwards, basking seeds, in storage, seed vitality, which easily reduces, even to be lost.Water suction be seed sprout necessary condition, dry kind
Daughter cell is in gel state, and cell membrane is discontinuous and loses its selected area update strategy, and early imbibition seed turns to crystal from gelatinous
Shape, membranous system must be repaired.When seed is directly under water or sowing is in wetland, film fast due to absorbing water
Have little time to repair, lose the integrality of its original, sugar, organic acid, ion, the amino acid even infiltration of protein and enzyme occur
Phenomenon, this phenomenon will wait until that membranous system could be reduced after repairing.Therefore, plant growth regulator is added in vegetables, flowers
Have become trend to promote germination to take root.In recent years China plant growth regulator is studied and application development also very
It hurry up.But its kind, quantity cannot all meet the needs of market.
At present by market using it is more be increase production of amines N, N- diethyl -2-（3,4- dichlorophenoxies）Ethamine
(DCPTA) and caproic acid Diethylaminoethanol ester（DA-6）, inventor has found there is diethylamino ethoxy group in both structures,
According to " principle of hybridization ", itself and adipic acid are subjected to split, that is, obtain that there is biology containing double diethylamino ethoxy structures
The double Diethylaminoethanol esters of compound-adipic acid of activity.It is polyfunctional group synergistic structure, in structure with caproic acid diethylamine
Base ethanol ester（DA-6）It is similar, and the number of diethylamino ethoxy is added, make it have efficiently more excellent plant life
Long adjustment effect.
The content of the invention
It is an object of the present invention to propose a kind of double Diethylaminoethanols of biologically active compound adipic acid
Ester citrate.The compound have it is simple in structure, it is soluble easily in water, easily by cell membrane enter cell body in.With existing plant
Thing growth regulator, which is compared, has the advantages that amount of application is few, and significant effect is environmentally safe, less toxic, can overcome the prior art
In deficiency.
For achieving the above object, present invention employs following technical solution：
The double Diethylaminoethanol ester citrate compounds of a kind of adipic acid, it is characterised in that the structure of the compound is such as
Shown in following formula：
Another object of the present invention is to propose a kind of preparation method of the double Diethylaminoethanol ester citrates of adipic acid.
Its technique is simple, is easy to large-scale production, and raw material is cheap and easy to get, and equipment investment is few, of low cost, and atom utilization is high, right
Environmental pollution is small, and this method is：
A certain amount of organic solvent, proper catalyst are added in the reactor equipped with water knockout drum and reflux, then is added
Enter the adipic acid and N, N- diethylaminoethanol of certain mol proportion, stir lower heating, the reflux point at a temperature of 110 DEG C~150 DEG C
Water reacts, and 5~9h is reacted, until the water separated reaches theoretical amount, Filtration of catalyst（Recycling uses）, filtrate decompression distills out
Organic solvent（Recycling uses）, excessive diethylaminoethanol（Recycling uses）And low boilers, it is double that bottoms adds adipic acid
Diethylaminoethanol ester Theoretical Mass 5%-10% activated decolorations, stir 30 minutes, filter to obtain yellow oily liquid adipic acid
Double Diethylaminoethanol esters.The double Diethylaminoethanol esters of adipic acid and twice mole of citric acid are put into reactor again, are stirred
Mix and be heated to 120 DEG C, after citric acid melts, stir lower crystallisation by cooling into salt, that is, obtain the double diethyls of white solid product adipic acid
Aminoethanol ester citrate.
This method can also be：
A certain amount of organic solvent, proper catalyst are added in the reactor equipped with water knockout drum and reflux, then is added
Enter the adipic anhydride and N, N- diethylaminoethanol of certain mol proportion, stir lower heating, flow back at a temperature of 110 DEG C~150 DEG C
Divide water reaction, 3~5h is reacted, until the water separated reaches theoretical amount, Filtration of catalyst（Recycling uses）, filtrate decompression distillation
Go out organic solvent（Recycling uses）, excessive diethylaminoethanol（Recycling uses）And low boilers, bottoms add adipic acid
Double Diethylaminoethanol ester Theoretical Mass 5%-10% activated decolorations, stir 30 minutes, filter yellow oily liquid oneself two
Sour double Diethylaminoethanol esters.The double Diethylaminoethanol esters of adipic acid and twice mole of citric acid are put into reactor again,
120 DEG C, after citric acid melts are heated with stirring to, lower crystallisation by cooling is stirred into salt, that is, obtains white solid product adipic acid double two
Ethylamino ethanol ester citrate.
A certain amount of organic solvent as described above is dimethylbenzene or toluene, its dosage volume milliliter number be adipic acid or oneself two
1-8 times of acid anhydrides quality grams.
The adipic acid and N, N- diethylaminoethanol of certain mol proportion as described above, the adipic anhydride of certain mol proportion and
N, N- diethylaminoethanol are adipic acid or adipic anhydride:The molar ratio of N, N- diethylaminoethanol is 1:2-1:3.
Proper catalyst as described above is titanyl sulfate, titanium dioxide or silica gel, its dosage is adipic acid or adipic acid
The 2%-10% of acid anhydride quality grams.
The double Diethylaminoethanol esters of adipic acid of the present invention are yellow oily liquid, not soluble in water, but are dissolved in chloroform, oil
The organic solvents such as ether, ethanol, index of refraction:nD 25=1.6582, density（20℃）:0.7895g/cm3；Yield for 85.4%~
91.1%, the double Diethylaminoethanol ester citrates of adipic acid are white powder crystal, and fusing point is 117 DEG C, soluble easily in water, no
It is dissolved in chloroform.
The preparation principle of the double Diethylaminoethanol ester citrates of adipic acid is shown below：
Or
Compared with prior art, the invention has the beneficial effects that：
（1）Contain Liang Ge diethylaminoethanol esters functional group in one molecule of structure of the present invention, molecular structure carrier each other,
Atom utilization is high, and active function groups superposition, it can play excellent plant growth regulation, its active effect is carried at double
It is high.
（2）The compounds of this invention, which has, to be promoted seed to sprout, promotes plant growth, enhancing photosynthesis, improves and make produce
Amount, improve the effect such as fruit quality and enhancing stress resistance of plant, its is widely used, is broad spectrum type active regulator.
（3）The compounds of this invention have dosage it is few, small toxicity, it is free from environmental pollution the advantages that.
（4）The compounds of this invention preparation process used catalyst and solvent and the Diethylaminoethanol of excess are all directly to return
Receive and use, do not produce pollution, do not cause to waste, belong to green preparation process.
（5）When the compounds of this invention preparation process silica gel makees catalyst, itself has decolorization, can save to product
Decolorization.
（6）The compounds of this invention preparation method is simple, and raw material is cheap and easy to get, and cost is low, and equipment investment is few, is easy to scale
Production, there is good application and development prospect.
Brief description of the drawings
Drawings described below is provided in order to further illustrate the structure and performance spy of product.
Fig. 1 is the infrared spectrogram of the double Diethylaminoethanol esters of adipic acid；Fig. 1 shows, in 1750cm-1Nearby occur strong
Absworption peak, corresponds to the stretching vibration of ester carbonyl group；In addition, 2900cm-1Nearby there is CH2The stretching vibration of middle c h bond；
1350cm-1Nearby there is the stretching vibration of C-N-C keys；
Fig. 2 is the nuclear magnetic spectrum figure of the double Diethylaminoethanol esters of adipic acid；Fig. 2 shows, deuterochloroform is solvent, δ 0.98 ~
1.06 be N- (CH2CH3)2In methyl hydrogen peak；δ 2.50 ~ 2.65 is N- (CH2CH3)2The methylene hydrogen peak being connected with nitrogen；δ2.67
~ 2.72 be-OCH2CH2The methylene hydrogen peak and O=CCH that-N is connected with nitrogen2CH2CH2CH2The methylene hydrogen that C=O is connected with carbonyl
Peak；δ 4.12 ~ 4.19 is-OCH2CH2The methylene hydrogen peak that N is connected with oxygen.
Embodiment
Technical scheme is described further below in conjunction with specific embodiment.
Embodiment 1 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 35.1g (0.3mol) N, N- diethylaminoethanol, 0.8g titanyl sulfates, 20ml dimethylbenzene, agitating and heating
To 150 DEG C of back flow reaction 5h, until separating 3.6g (0.2mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to separately
In the there-necked flask of one 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）It is and low
After boiling point thing, add 3.0g atlapulgites and stir 30 minutes, be cooled to less than 80 DEG C, filter to obtain yellow oily liquid adipic acid pair
Diethylaminoethanol ester 31.10g, yield 90.4%.Again by the double Diethylaminoethanol esters of adipic acid and twice mole of citric acid
Mixing is heated to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powdery solids production
The double Diethylaminoethanol ester citrates of thing adipic acid.Its fusing point：117℃.
Embodiment 2 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 23.4 g (0.2mol) N, N- diethylaminoethanol, 0.8g titanyl sulfates, 40ml dimethylbenzene, stirring add
Heat is to 140 DEG C of back flow reaction 8h, until separating 3.6g (0.2mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to
In the there-necked flask of another 250ml, solvent is evaporated under reduced pressure out（Recycling uses）And after low boilers, add 3.0g atlapulgites and stir
Mix 30 minutes, be cooled to less than 80 DEG C, filter the double Diethylaminoethanol ester 29.55g of yellow oily liquid adipic acid, yield are
85.9%.The double Diethylaminoethanol esters of adipic acid and twice mole of citric acid are mixed and are heated to 120 DEG C again, makes lemon
After acid melts, lower crystallisation by cooling is stirred into salt, that is, obtains the double Diethylaminoethanol ester lemons of white powdery solids product adipic acid
Lemon hydrochlorate.Its fusing point：117℃.
Embodiment 3 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 35.1g (0.3mol) N, N- diethylaminoethanol, 0.8g titanium dioxide, 20ml dimethylbenzene, agitating and heating
To 150 DEG C of back flow reaction 8h, until separating 3.6g (0.2mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to separately
In the there-necked flask of one 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）It is and low
After boiling point thing, add 3.0g atlapulgites and stir 30 minutes, be cooled to less than 80 DEG C, filter to obtain yellow oily liquid adipic acid pair
Diethylaminoethanol ester 30.34g, yield 88.2%.Again by the double Diethylaminoethanol esters of adipic acid and twice mole of citric acid
Mixing is heated to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powdery solids production
The double Diethylaminoethanol ester citrates of thing adipic acid.Its fusing point：117℃.
Embodiment 4 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 29.3g (0.25mol) N, N- diethylaminoethanol, 0.6g titanyl sulfates, 40ml dimethylbenzene, stirring add
Heat is to 140 DEG C of back flow reaction 7h, until separating 3.6g (0.2mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to
In the there-necked flask of another 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）And
After low boilers, add 3.0g atlapulgites and stir 30 minutes, be cooled to less than 80 DEG C, filter to obtain yellow oily liquid adipic acid
Double Diethylaminoethanol ester 30.07g, yield 87.4%.Again by the double Diethylaminoethanol esters of adipic acid and twice mole of lemon
Acid is mixed and is heated to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powdery solids
The double Diethylaminoethanol ester citrates of product adipic acid.Its fusing point：117℃.
Embodiment 5 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 29.3g (0.25mol) N, N- diethylaminoethanol, 1.0g silica gel, 40ml dimethylbenzene, 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 is transferred to another
In the there-necked flask of a 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）And low boiling
After point thing, the double Diethylaminoethanol ester 30.03g of yellow oily liquid adipic acid, yield 87.3% are obtained.Again by adipic acid double two
Ethylamino ethanol ester and twice mole of citric acid, which are mixed, is heated to 120 DEG C, after melting citric acid, stirs lower cooling knot
Crystalline substance obtains the double Diethylaminoethanol ester citrates of white powdery solids product adipic acid into salt.Its fusing point：117℃.
Embodiment 6 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 35.1g (0.3mol) N, N- diethylaminoethanol, 0.7g titanyl sulfates, 30ml toluene, 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 is transferred to another
In the there-necked flask of a 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）And low boiling
After point thing, add 3.0g atlapulgites and stir 30 minutes, be cooled to less than 80 DEG C, filter to obtain yellow oily liquid adipic acid double two
Ethylamino ethanol ester 30.86g, yield 89.7%.The double Diethylaminoethanol esters of adipic acid are mixed with twice mole of citric acid again
Conjunction is heated with stirring to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powdery solids product
The double Diethylaminoethanol ester citrates of adipic acid.Its fusing point：117℃.
Embodiment 7 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 35.1g (0.3mol) N, N- diethylaminoethanol, 0.8g titanium dioxide, 30ml toluene, 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 is transferred to another
In the there-necked flask of a 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）And low boiling
After point thing, add 3.0g atlapulgites and stir 30 minutes, be cooled to less than 80 DEG C, filter to obtain yellow oily liquid adipic acid double two
Ethylamino ethanol ester 30.55g, yield 88.8%.The double Diethylaminoethanol esters of adipic acid are mixed with twice mole of citric acid again
Conjunction is heated with stirring to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powdery solids product
The double Diethylaminoethanol ester citrates of adipic acid.Its fusing point：117℃.
Embodiment 8 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 23.4 g (0.2mol) N, N- diethylaminoethanol, 0.8g titanyl sulfates, 40ml toluene, agitating and heating
To 110 DEG C of back flow reaction 9h, until separating 3.6g (0.2mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to separately
In the there-necked flask of one 100ml, solvent is evaporated under reduced pressure out（Recycling uses）And after low boilers, add the stirring of 3.0g atlapulgites
30 minutes, be cooled to less than 80 DEG C, filter the double Diethylaminoethanol ester 29.38g of yellow oily liquid adipic acid, yield are
85.4%.The double Diethylaminoethanol esters of adipic acid and twice mole of citric acid are mixed and are heated to 120 DEG C again, makes lemon
After acid melts, lower crystallisation by cooling is stirred into salt, that is, obtains the double Diethylaminoethanol ester lemons of white powdery solids product adipic acid
Lemon hydrochlorate.Its fusing point：117℃.
Embodiment 9 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 29.3g (0.25mol) N, N- diethylaminoethanol, 0.8g titanyl sulfates, 40ml toluene, agitating and heating
To 110 DEG C of back flow reaction 7h, until separating 3.6g (0.2mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to separately
In the there-necked flask of one 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）It is and low
After boiling point thing, add 3.0g atlapulgites and stir 30 minutes, be cooled to less than 80 DEG C, filter to obtain yellow oily liquid adipic acid pair
Diethylaminoethanol ester 30.31g, yield 88.1%.Again by the double Diethylaminoethanol esters of adipic acid and twice mole of citric acid
Mixing is heated to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powdery solids production
The double Diethylaminoethanol ester citrates of thing adipic acid.Its fusing point：117℃.
Embodiment 10 adds 14.6g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic acid, 29.3g (0.25mol) N, N- diethylaminoethanol, 1.0g silica gel, 40ml toluene, is heated with stirring to 110
DEG C back flow reaction 8h, until separating 3.6g (0.2mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to another
In the there-necked flask of 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）And low boiling point
After thing, the double Diethylaminoethanol ester 30.13g of yellow oily liquid adipic acid, yield 87.6% are obtained.Again by the double diethyls of adipic acid
Aminoethanol ester and twice mole of citric acid, which are mixed, is heated to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling
Into salt, that is, obtain the double Diethylaminoethanol ester citrates of white powdery solids product adipic acid.Its fusing point：117℃.
Embodiment 11 adds 12.8g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic anhydride, 35.1g (0.3mol) N, N- diethylaminoethanol, 0.8g titanyl sulfates, 20ml dimethylbenzene, stirring add
Heat is to 145 DEG C of back flow reaction 3h, until separating 1.8g (0.1mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to
In the there-necked flask of another 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）And
After low boilers, add 3.0g atlapulgites and stir 30 minutes, be cooled to less than 80 DEG C, filter to obtain yellow oily liquid adipic acid
Double Diethylaminoethanol ester 31.34g, yield 91.1%.Again by the double Diethylaminoethanol esters of adipic acid and twice mole of lemon
Acid is mixed and is heated to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powdery solids
The double Diethylaminoethanol ester citrates of product adipic acid.Its fusing point：117℃.
Embodiment 12 adds 12.8g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic anhydride, 23.4g (0.2mol) N, N- diethylaminoethanol, 0.6g titanyl sulfates, 40ml dimethylbenzene, stirring add
Heat is to 145 DEG C of back flow reaction 5h, until separating 1.8g (0.1mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to
In the there-necked flask of another 250ml, solvent is evaporated under reduced pressure out（Recycling uses）And after low boilers, add 3.0g atlapulgites and stir
Mix 30 minutes, be cooled to less than 80 DEG C, filter the double Diethylaminoethanol ester 29.76g of yellow oily liquid adipic acid, yield are
86.5%.The double Diethylaminoethanol esters of adipic acid and twice mole of citric acid are mixed and are heated to 120 DEG C again, makes lemon
After acid melts, lower crystallisation by cooling is stirred into salt, that is, obtains the double Diethylaminoethanol ester lemons of white powdery solids product adipic acid
Lemon hydrochlorate.Its fusing point：117℃.
Embodiment 13 adds 12.8g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic anhydride, 29.3g (0.25mol) N, N- diethylaminoethanol, 0.8g titanium dioxide, 40ml dimethylbenzene, stirring
145 DEG C of back flow reaction 4h are heated to, until separating 1.8g (0.1mol) water, Filtration of catalyst（Direct reuse）, filtrate turn
In the there-necked flask for entering another 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）
And after low boilers, add 3.0g atlapulgites and stir 30 minutes, be cooled to less than 80 DEG C, filter yellow oily liquid oneself two
Sour double Diethylaminoethanol ester 30.58g, yield 88.9%.Again by the double Diethylaminoethanol esters of adipic acid and twice mole of lemon
Lemon acid, which is mixed, is heated to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powder and consolidate
The double Diethylaminoethanol ester citrates of body product adipic acid.Its fusing point：117℃.
Embodiment 14 adds 12.8g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic anhydride, 35.1g (0.3mol) N, N- diethylaminoethanol, 0.8g titanium dioxide, 30ml toluene, agitating and heating
To 113 DEG C of back flow reaction 3h, until separating 1.8g (0.1mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to separately
In the there-necked flask of one 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）It is and low
After boiling point thing, add 3.0g atlapulgites and stir 30 minutes, be cooled to less than 80 DEG C, filter to obtain yellow oily liquid adipic acid pair
Diethylaminoethanol ester 30.86g, yield 89.7%.Again by the double Diethylaminoethanol esters of adipic acid and twice mole of citric acid
Mixing is heated to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powdery solids production
The double Diethylaminoethanol ester citrates of thing adipic acid.Its fusing point：117℃.
Embodiment 15 adds 12.8g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic anhydride, 23.4g (0.2mol) N, N- diethylaminoethanol, 1.0g silica gel, 40ml toluene, 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 is transferred to another
In the there-necked flask of a 250ml, solvent is evaporated under reduced pressure out（Recycling uses）And after low boilers, it is double to obtain yellow oily liquid adipic acid
Diethylaminoethanol ester 30.44g, yield 88.5%.Again by the double Diethylaminoethanol esters of adipic acid and twice mole of citric acid
Mixing is heated to 120 DEG C, after melting citric acid, stirs lower crystallisation by cooling into salt, that is, obtains white powdery solids production
The double Diethylaminoethanol ester citrates of thing adipic acid.Its fusing point：117℃.
Embodiment 16 adds 12.8g in the 250ml four-hole boiling flasks equipped with blender and water knockout drum and reflux
(0.1mol) adipic anhydride, 29.3g (0.25mol) N, N- diethylaminoethanol, 1.0g silica gel, 40ml toluene, 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 is transferred to another
In the there-necked flask of a 250ml, solvent is evaporated under reduced pressure out（Recycling uses）, excessive diethylaminoethanol（Recycling uses）And low boiling
After point thing, the double Diethylaminoethanol ester 30.31g of yellow oily liquid adipic acid, yield 88.1% are obtained.Again by adipic acid double two
Ethylamino ethanol ester and twice mole of citric acid, which are mixed, is heated to 120 DEG C, after melting citric acid, stirs lower cooling knot
Crystalline substance obtains the double Diethylaminoethanol ester citrates of white powdery solids product adipic acid into salt.Its fusing point：117℃.
1 adipic acid of table prepares main technologic parameters for raw material
2 adipic anhydride of table prepares main technologic parameters for raw material
The adipic acid diethylaminoethanol ester citric acid hydrochlorate of above-mentioned preparation is used for green vegetables, soya bean, wheat, oil by inventor
Dish, rice paddy seed reference《International seed inspection procedure》(1985)、《Crop seeds inspection procedure》(1995) as evaluation kind
Standard that whether son germinates (to grow 1cm for germinate), has made biological activity test, with the formula of A=(N-N0)/N0 × 100%
Calculate and adjust percent activity（A-it is that sample adjusts activity；The length of N-cultivated in the compound solution root measured；N0—
In distilled water culture measure with length.）.
First, experimental method
Using plate culture, adipic acid diethylaminoethanol ester citrate is configured to 100mg/L, 70mg/ respectively
L, the solution of 40mg/L and 10mg/L various concentrations, studies its growth to green vegetables, soya bean, wheat, rape, rice seedling root system
Adjustment effect.Make blank test with distilled water, the DA-6 solution of same concentrations makees standard control group, molten with respective concentration respectively
Liquid immersion green vegetables, soya bean, wheat, rape, rice paddy seed 6h -8h, be then respectively placed in temperature for 23 DEG C, 25 DEG C, 20 DEG C, 23
DEG C, measure the length of its root system and stem after 28 DEG C of constant temperature incubation rooms culture 4d -6d, and count germination number.
2nd, experimental result
Adipic acid diethylaminoethanol ester citrate prepared by the present invention distinguishes the data of plant growth regulating activity
Be shown in Table 3, table 4, table 5, table 6, shown in table 7.
The double Diethylaminoethanol ester citrates of 3 adipic acid of table are used for green vegetables seed（50）Seed germination data
The double Diethylaminoethanol ester citrates of 4 adipic acid of table are used for soya bean seed（10）Seed germination data
The double Diethylaminoethanol ester citrates of 5 adipic acid of table are used for wheat seed（30）Seed germination data
The double Diethylaminoethanol ester citrates of 6 adipic acid of table are used for rape seed（50）Seed germination data
The double Diethylaminoethanol ester citrates of 7 adipic acid of table are used for rice paddy seed（30）Seed germination data
Claims (4)
1. the preparation method of the double Diethylaminoethanol ester citrate compounds of a plant growth regulators adipic acid, its feature
It is, this method is：
A certain amount of organic solvent is added in the reactor equipped with water knockout drum and reflux, proper catalyst, adds and rub
You are than being 1:2-1:3 adipic anhydride and N, N- diethylaminoethanol, stirs lower heating, flows back at a temperature of 110 DEG C~150 DEG C
Divide water reaction, react 3~5h, until the water separated reaches theoretical amount, Filtration of catalyst, filtrate decompression distills out organic molten
Agent, excessive diethylaminoethanol and low boilers, bottoms add the double Diethylaminoethanol ester Theoretical Mass 5%- of adipic acid
10% activated decoloration, is stirred 30 minutes, filters to obtain the double Diethylaminoethanol esters of yellow oily liquid adipic acid；Again by oneself two
Sour double Diethylaminoethanol esters and twice mole of citric acid are put into reactor, are heated with stirring to 120 DEG C, citric acid melts
Afterwards, lower crystallisation by cooling is stirred into salt, that is, obtains the double Diethylaminoethanol ester citrates of white solid product adipic acid, the chemical combination
The structure of thing is shown below：
。
2. the double Diethylaminoethanol ester citrate compounds of a plant growth regulators adipic acid according to claim 1
Preparation method, it is characterised in that：A certain amount of organic solvent is dimethylbenzene or toluene, its dosage volume milliliter number is
1-8 times of adipic anhydride quality grams.
3. the double Diethylaminoethanol ester citrate compounds of a plant growth regulators adipic acid according to claim 1
Preparation method, it is characterised in that：The proper catalyst is titanyl sulfate, titanium dioxide or silica gel, its dosage be oneself two
The 2%-10% of acid anhydrides quality grams.
4. the double Diethylaminoethanol ester citrate compounds of a plant growth regulators adipic acid according to claim 1
Preparation method, it is characterised in that：The Filtration of catalyst, filtrate decompression distill out organic solvent, excessive diethyl
Ethylaminoethanol is catalyst, organic solvent, the diethylaminoethanol recycling being recovered to.
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| DE2260113A1 (en) * | 1972-12-08 | 1974-06-12 | Bayer Ag | DEGRADABLE HYDROPHILIC FOAMS FOR SOIL-LESS PLANT CULTURE |
| JP2583103B2 (en) * | 1988-05-17 | 1997-02-19 | 日東バイオン株式会社 | Plant growth promoter and method for producing the same |
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