CN105906516B - Double Diethylaminoethanol ester citrate compounds of plant growth regulator succinic acid and preparation method thereof - Google Patents
Double Diethylaminoethanol ester citrate compounds of plant growth regulator succinic acid and preparation method thereof Download PDFInfo
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- CN105906516B CN105906516B CN201610349746.2A CN201610349746A CN105906516B CN 105906516 B CN105906516 B CN 105906516B CN 201610349746 A CN201610349746 A CN 201610349746A CN 105906516 B CN105906516 B CN 105906516B
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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
- 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
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Abstract
The present invention relates to double Diethylaminoethanol ester citrate compounds of a plant growth regulators succinic acid and preparation method thereof, the structure of the compound is shown below：
Description
Technical field
The present invention relates to the double Diethylaminoethanol ester citrate compounds of a plant growth regulators succinic acid and its
Preparation method.The compound, which has, to be promoted seed to sprout, promotes plant growth, enhancing photosynthesis, improve crop yield, improve
The purposes such as fruit quality and enhancing stress resistance of plant.
Background technology
China is a large agricultural country having a large population and a few land, and the yield for improving unit cultivated area is that solution food problem is important
One of measure.Plant growth regulator have dosage is small, effect is big, can stratification, control bloom, delaying senility course, carry
High yield, improve crop quality, increase resistance etc..Thus plant growth regulator has been the important composition portion of modern
Point, and be widely used.
Plant growth regulator is not endogenous hormones.It is artificial synthesized, has a kind of organic of Plant Hormone Action
Material, they can be penetrated into plant under relatively low concentration, and promotion or inhibitory action are shown to growing for plant.
In this area, most valued is the conditioning agent that can make crop yield, and they have shown in agricultural production
Very big efficiency is shown.The research of plant growth regulator and application are but its society's effects since the 1930s is just
Benefit and economic benefit are very big, so its development is very fast, to the sixties, that is, have formd " plant growth regulator work
Industry ".With the development of Chemical Engineering Technology and biotechnology, plant growth regulator changes to the output increased of agricultural, product quality
Kind, reduction labor intensity, raising labour productivity plays more and more important effect, as the prophesy of people：" 21 century is raw
Thing engineering century ", the change of bioengineering will be the changes of " transgenic engineering " and " chemical regulation " 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
Further expand.To the sixties, the species and object of application have increase again, but are concentrated mainly on cycocel in cotton and wheat
On application.After the seventies, multinomial great achievement is obtained to plant growth regulator basic theory and application study.The eighties
Latter half, the annual average rate of increase of all kinds of agricultural chemicals is 5%, and plant growth regulator is up to 9.8%.At present, the U.S. is by agriculture
Medicine research program is adjusted to three big field-Insecticides (tech) ＆ Herbicides (tech)s and plant growth regulator from original seven big fields, and its is bright
Really highlight plant growth regulator importance.Recent year studies plant growth regulator research and application development also very
It hurry up.But its kind, quantity can not all meet the needs of market.
At present by market using it is more be DCPTA N, N- diethyl -2-（3,4- dichlorophenoxies）Ethamine
And caproic acid Diethylaminoethanol ester (DCPTA)（DA-6）, inventor has found there is diethylamino ethoxy group in both structures,
According to " principle of hybridization ", itself and the succinic acid in tricarboxylic acid cycle are subjected to split, that is, obtained containing double diethylamino ethoxies
The double Diethylaminoethanol esters of the compound with bioactivity of structure --- succinic acid.It is polyfunctional group synergistic structure, fourth
Diacid also known as butanedioic acid, it is TCA important intermediate.Succinate dehydrogenase catalysis succinoxidase chemical conversion fumaric acid, is discharged
Energy and oxygen；The physiologically active of butanedioic acid and the physiologically active of diethylamino ethoxy produce cooperative effect, make it have more
Excellent plant growth regulation.
The content of the invention
An object of the present invention is to propose a kind of double Diethylaminoethanols of the compound succinic acid with bioactivity
Ester citrate.The compound have it is simple in construction, it is soluble 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.
For achieving the above object, present invention employs following technical scheme：
The double Diethylaminoethanol ester citrate compounds of a kind of succinic 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 succinic acid.
The preparation method has that technique is simple, and atom utilization is high, does not produce pollution, small investment of production equipment, is easy to mass produce.
The preparation method of the double Diethylaminoethanol ester citrates of succinic acid comprises the following steps that：
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 succinic acid and N, N- diethylaminoethanol of certain mol proportion, stir lower heating, the backflow 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（Recovery uses）, filtrate decompression distills out
Organic solvent（Recovery uses）, excessive diethylaminoethanol（Recovery uses）And low boilers, it is double that bottoms adds succinic acid
The double diethylin of yellow oily liquid succinic acid are filtered to obtain after Diethylaminoethanol ester Theoretical Mass 5%-10% activated decolorations
Ethanol ester.The double Diethylaminoethanol esters of succinic acid and twice mole of citric acid are put into reactor again, are heated with stirring to 115
DEG C, after citric acid melts, lower crystallisation by cooling is stirred, that is, obtains the double Diethylaminoethanol ester citric acids of white solid product succinic acid
Salt.
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 succinic anhydride and N, N- diethylaminoethanol of certain mol proportion, stir lower heating, flowed 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（Recovery uses）, filtrate decompression distillation
Go out organic solvent（Recovery uses）, excessive diethylaminoethanol（Recovery uses）And low boilers, bottoms add succinic acid
The double diethylamine of yellow oily liquid succinic acid are filtered to obtain after double Diethylaminoethanol ester Theoretical Mass 5%-10% activated decolorations
Base ethanol ester.The double Diethylaminoethanol esters of succinic acid and twice mole of citric acid are put into reactor again, are heated with stirring to
115 DEG C, after citric acid melts, lower crystallisation by cooling is stirred, that is, obtains the double Diethylaminoethanol ester lemons of white solid product succinic acid
Lemon hydrochlorate.
A certain amount of organic solvent as described above is dimethylbenzene or toluene, and its dosage volume milliliter number is succinic acid or fourth two
1-8 times of acid anhydrides quality grams.
The succinic acid and N, N- diethylaminoethanol of certain mol proportion as described above, the succinic anhydride of certain mol proportion and
N, N- diethylaminoethanol are succinic acid or succinic anhydride:The mol ratio of N, N- diethylaminoethanol is 1:2-1:3.
Proper catalyst as described above is titanyl sulfate, titanium dioxide or silica gel, and its dosage is succinic acid or succinic acid
The 2%-10% of acid anhydride quality grams.
The double Diethylaminoethanol esters of succinic acid of the present invention are yellow oily liquid, not soluble in water, index of refraction:nD 25=
1.6629 density（20℃）:0.7240g/cm3；Yield is 82.6%~88.8%, the double Diethylaminoethanol ester lemons of succinic acid
Phosphate compounds are white powdery solids, and fusing point is 112 DEG C, soluble in water.The double Diethylaminoethanol ester citric acids of succinic acid
The preparation principle of salt is shown below：
Or
Compared with prior art, the present invention is advantageous in that：
（1）Contain Liang Ge diethylaminoethanol esters functional group in one molecule of structure of the present invention, with recessive amber acid activity
Body structure carrier each other, atom utilization is high, active function groups superposition, the physiologically active of butanedioic acid and diethylamino ethoxy
Physiologically active produces cooperative effect, and it can play excellent plant growth regulation, significantly improve its active effect.
（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 has that dosage is few, small toxicity, it is free from environmental pollution the advantages that.
（4）The compounds of this invention preparation technology 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 technology 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.
Brief description of the drawings
In order to further illustrate that the structure of product and performance spy provide drawings described below.
Fig. 1 is the infrared spectrogram of the double Diethylaminoethanol esters of succinic acid；Fig. 1 shows, in 1750cm-1Nearby occur strong
Absworption peak, correspond 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 succinic 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 nitrogen2CH2The methylene hydrogen peak that C=O is connected with carbonyl；δ
4.12 ~ 4.19 be-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 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 one 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery 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 succinic acid pair
Diethylaminoethanol ester 27.27g, yield 86.3%.The double Diethylaminoethanol esters of succinic acid are mixed with twice mole of citric acid again
Conjunction is heated with stirring to 115 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 succinic acid.Its fusing point：112℃.
Embodiment 2 adds 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 another 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）And after low boilers, add 3.0g atlapulgites and stir
Mix 30 minutes, be cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 25.79g of yellow oily liquid succinic acid, yield
81.6%.The double Diethylaminoethanol esters of succinic acid and twice mole of citric acid are mixed and be heated to 115 DEG C again, makes lemon
After acid melts, stirring crystallisation by cooling obtains the double Diethylaminoethanol ester lemons of white powdery solids product succinic acid into salt
Hydrochlorate.Its fusing point：112℃.
Embodiment 3 adds 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 one 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery 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 succinic acid pair
Diethylaminoethanol ester 26.58g, yield 84.1%.The double Diethylaminoethanol esters of succinic acid are mixed with twice mole of citric acid again
Conjunction is heated with stirring to 115 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 succinic acid.Its fusing point：112℃.
Embodiment 4 adds 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 another 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery 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 succinic acid
Double Diethylaminoethanol ester 27.18g, yield 86.0%.Again by the double Diethylaminoethanol esters of succinic acid and twice mole of citric acid
Mixing is heated to 115 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 succinic acid.Its fusing point：112℃.
Embodiment 5 adds 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic acid, 29.3g (0.25mol) N, N- diethylaminoethanol, 1g silica gel, 40ml dimethylbenzene, is heated with stirring to 140
DEG C back flow reaction 6h, until separating 3.6g (0.2mol) water, Filtration of catalyst（Direct reuse）, filtrate is transferred to another
In 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery uses）And low boiling
After thing, the double Diethylaminoethanol ester 27.68g of yellow oily liquid succinic acid, yield 87.6% are obtained.Again by the double diethylamine of succinic acid
The citric acid of base ethanol ester and twice mole mixes and is heated to 115 DEG C, after melting citric acid, stir lower crystallisation by cooling into
Salt, that is, obtain the double Diethylaminoethanol ester citrates of white powdery solids product succinic acid.Its fusing point：112℃.
Embodiment 6 adds 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 individual 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery 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 succinic acid double two
Ethylamino ethanol ester 27.05g, yield 85.6%.The double Diethylaminoethanol esters of succinic acid are mixed with twice mole of citric acid again
115 DEG C are heated with stirring to, after melting citric acid, lower crystallisation by cooling is stirred into salt, that is, obtains white powdery solids product fourth
The double Diethylaminoethanol ester citrates of diacid.Its fusing point：112℃.
Embodiment 7 adds 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 individual 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery 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 succinic acid double two
Ethylamino ethanol ester 26.16g, yield 82.8%.The double Diethylaminoethanol esters of succinic acid are mixed with twice mole of citric acid again
115 DEG C are heated with stirring to, after melting citric acid, lower crystallisation by cooling is stirred into salt, that is, obtains white powdery solids product fourth
The double Diethylaminoethanol ester citrates of diacid.Its fusing point：112℃.
Embodiment 8 adds 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 one 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）And after low boilers, add the stirring of 3.0g atlapulgites
30 minutes, less than 80 DEG C are cooled to, filters to obtain the double Diethylaminoethanol ester 25.91g of yellow oily liquid succinic acid, yield
82.0%.The double Diethylaminoethanol esters of succinic acid and twice mole of citric acid are mixed and be heated to 115 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 succinic acid
Lemon hydrochlorate.Its fusing point：112℃.
Embodiment 9 adds 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 one 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery 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 succinic acid pair
Diethylaminoethanol ester 26.95g, yield 85.3%.The double Diethylaminoethanol esters of succinic acid are mixed with twice mole of citric acid again
Conjunction is heated with stirring to 115 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 succinic acid.Its fusing point：112℃.
Embodiment 10 adds 11.8g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery uses）And low boiling
After thing, the double Diethylaminoethanol ester 27.14g of yellow oily liquid succinic acid, yield 85.9% are obtained.Again by the double diethylamine of succinic acid
The citric acid of base ethanol ester and twice mole mixes and is heated to 115 DEG C, after melting citric acid, stirring crystallisation by cooling into
Salt, that is, obtain the double Diethylaminoethanol ester citrates of white powdery solids product succinic acid.Its fusing point：112℃.
Embodiment 11 adds 10.0g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 another 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery 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 succinic acid
Double Diethylaminoethanol ester 27.90g, yield 88.3%.Again by the double Diethylaminoethanol esters of succinic acid and twice mole of citric acid
Mixing is heated to 115 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 succinic acid.Its fusing point：112℃.
Embodiment 12 adds 10.0g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 another 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）And after low boilers, add 3.0g atlapulgites and stir
Mix 30 minutes, be cooled to less than 80 DEG C, filter to obtain the double Diethylaminoethanol ester 26.10g of yellow oily liquid succinic acid, yield
82.6%.The double Diethylaminoethanol esters of succinic acid and twice mole of citric acid are mixed and be heated to 115 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 succinic acid
Lemon hydrochlorate.Its fusing point：112℃.
Embodiment 13 adds 10.0g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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（Recovery uses）, excessive diethylaminoethanol（Recovery 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 fourth two
Sour double Diethylaminoethanol ester 27.18g, yield 86.0%.Again by the double Diethylaminoethanol esters of succinic acid and twice mole of lemon
Acid mixes and is heated to 115 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 succinic acid.Its fusing point：112℃.
Embodiment 14 adds 10.0g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 one 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery 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 succinic acid pair
Diethylaminoethanol ester 28.06g, yield 88.8%.The double Diethylaminoethanol esters of succinic acid are mixed with twice mole of citric acid again
Conjunction is heated with stirring to 115 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 succinic acid.Its fusing point：112℃.
Embodiment 15 adds 10.0g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 individual 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）And after low boilers, it is double to obtain yellow oily liquid succinic acid
Diethylaminoethanol ester 26.0g, yield 82.3%.The double Diethylaminoethanol esters of succinic acid are mixed with twice mole of citric acid again
Conjunction is heated with stirring to 115 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 succinic acid.Its fusing point：112℃.
Embodiment 16 adds 10.0g in the 250ml four-hole boiling flasks equipped with agitator and water knockout drum and reflux
(0.1mol) succinic 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 individual 250ml there-necked flask, solvent is evaporated under reduced pressure out（Recovery uses）, excessive diethylaminoethanol（Recovery uses）And low boiling
After point thing, the double Diethylaminoethanol ester 26.95g of yellow oily liquid succinic acid, yield 85.3% are obtained.Again by the double diethyls of succinic acid
Aminoethanol ester and twice mole of citric acid, which mix, is heated to 115 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 succinic acid.Its fusing point：112℃.
The succinic acid of table 1 is that raw material prepares main technologic parameters
The succinic anhydride of table 2 is that raw material prepares main technologic parameters
| Sequence number | Diethylaminoethanol | Catalyst | Solvent | Temperature DEG C | Time | Yield % |
| 1 | 35.1g(0.3mol) | 0.8g titanyl sulfates | 20ml dimethylbenzene | 145 | 3h | 88.3% |
| 2 | 23.4g(0.2mol) | 0.6g titanyl sulfates | 40ml dimethylbenzene | 145 | 5h | 82.6% |
| 3 | 29.3g(0.25mol) | 0.8g titanium dioxide | 40ml dimethylbenzene | 145 | 4h | 86.0% |
| 4 | 35.1g(0.3mol) | 0.8g titanium dioxide | 30ml toluene | 113 | 3h | 88.8% |
| 5 | 23.4g(0.2mol) | 1.0g silica gel | 40ml toluene | 113 | 5h | 82.3% |
| 6 | 29.3g(0.25mol) | 1.0g silica gel | 40ml toluene | 113 | 4h | 85.3% |
Note：The inventory of succinic anhydride is 10.0 g (0.1mol) in table 2
Inventor by the double Diethylaminoethanol ester citric acid hydrochlorates of the succinic acid of above-mentioned preparation be used for green vegetables, soya bean, wheat,
Rape, rice paddy seed reference《International seed inspection procedure》(1985)、《Crop seeds inspection procedure》(1995) as evaluation
The standard (to grow 1cm as germination) whether seed germinates, has made biological activity test, method of testing is as follows:
Using plate culture, by the double Diethylaminoethanol ester citrates of succinic acid be respectively prepared 100mg/L,
70mg/L, 40mg/L and 10mg/L various concentrations solution, it is studied to green vegetables, soya bean, wheat, rape, rice seedling root system
Growth regulating acts on.Make blank test with distilled water, the DA-6 solution of same concentrations makees standard control group, uses respective concentration respectively
Solution 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 incubated rooms culture 4d -6d, and count germination number, to
Lower formula calculates germination percentage and regulation percent activity.
Germination percentage=germinative number/seed sum
A=(N-N0)/N0×100%
A-it is sample regulation activity；
The overall average length of N-cultivated in the compound solution root measured and bud；
N0- the overall average length of the root measured and bud is cultivated in distilled water；
The double Diethylaminoethanol ester citrates of succinic acid prepared by the present invention are to plant growth regulating activity and germination percentage
Data be shown in Table respectively 3, table 4, table 5, table 6, shown in table 7.
The double Diethylaminoethanol ester citrates of the succinic acid of table 3 are used for green vegetables seed（50）Seed germination data
The double Diethylaminoethanol ester citrates of the succinic acid of table 4 are used for soya bean seed（10）Seed germination data
The double Diethylaminoethanol ester citrates of the succinic acid of table 5 are used for wheat seed（30）Seed germination data
The double Diethylaminoethanol ester citrates of the succinic acid of table 6 are used for rape seed（50）Seed germination data
The double Diethylaminoethanol ester citrates of the succinic acid of table 7 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 succinic 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 one
Determine the succinic anhydride and N, N- diethylaminoethanol of mol ratio, stir lower heating, the reflux water-dividing at a temperature of 110 DEG C~150 DEG C
Reaction, 3~5h is reacted, until the water separated reaches theoretical amount, Filtration of catalyst, filtrate decompression distills out organic solvent, mistake
The diethylaminoethanol and low boilers of amount, bottoms add the double Diethylaminoethanol ester Theoretical Mass 5%-10% activity of succinic acid
Carclazyte filters to obtain the double Diethylaminoethanol esters of slightly yellow liquid succinic acid after decolourizing；Again by the double Diethylaminoethanol esters of succinic acid
Citric acid with twice mole is put into reactor, is heated with stirring to 115 DEG C, after citric acid melts, stir lower crystallisation by cooling into
Salt, that is, obtain the double Diethylaminoethanol ester citrates of white solid product succinic acid, and the structure of the compound is shown below：
。
2. the double Diethylaminoethanol ester citrate compounds of a plant growth regulators succinic acid according to claim 1
Preparation method, it is characterised in that：Described a certain amount of organic solvent is dimethylbenzene or toluene, and its dosage volume milliliter number is
1-8 times of succinic acid or succinic anhydride quality grams.
3. the double Diethylaminoethanol ester citrate compounds of a plant growth regulators succinic acid according to claim 1
Preparation method, it is characterised in that：The succinic anhydride and N, N- diethylaminoethanol of described certain mol proportion are succinic anhydride:
The mol ratio of N, N- diethylaminoethanol is 1:2-1:3.
4. the double Diethylaminoethanol ester citrate compounds of a plant growth regulators succinic acid according to claim 1
Preparation method, it is characterised in that：Described proper catalyst is titanyl sulfate, titanium dioxide or silica gel, and its dosage is fourth two
The 2%-10% of acid anhydrides quality grams.
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| AT185371B (en) * | 1953-06-23 | 1956-04-25 | Chemie Linz Ag | Process for the production of new polymethylene or phenylene-bis-carbamic acid esters |
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