CN105906516A - Plant growth regulator succinic bis-diethylamino glycolate citrate compound and preparation method thereof - Google Patents
Plant growth regulator succinic bis-diethylamino glycolate citrate compound and preparation method thereof Download PDFInfo
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- CN105906516A CN105906516A CN201610349746.2A CN201610349746A CN105906516A CN 105906516 A CN105906516 A CN 105906516A CN 201610349746 A CN201610349746 A CN 201610349746A CN 105906516 A CN105906516 A CN 105906516A
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- succinic acid
- diethylaminoethanol
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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 invention relates to a plant growth regulator succinic bis-diethylamino glycolate citrate compound and a preparation method thereof. The compound has a structure as shown in a formula in the specification. The preparation method comprises the following steps: adding an organic solvent into a reactor which is provided with a water distributor and a reflux device, controlling succinic acid or succinic anhydride and N,N-diethylamino alcohol to perform a reflex distribution reaction for 3-9 hours at 110-150 DEG C in a molar ratio of (1:2)-(1:3) in catalyst existence, filtering, distilling the filtrate at reduced pressure to obtain an organic solvent and excessive diethylamino alcohol, decolorizing the bottom substance with activated clay to obtain succinic bis-diethylamino glycolate; and salifying the succinic bis-diethylamino glycolate with twice molar amount of citric acid to obtain a white solid product. The compound has the effects of promoting seed germination, enhancing photosynthesis, promoting plant growth, increasing crop yield, improving fruit quality, strengthening plant stress resistance and the like, and is a broad-spectrum active regulator. The preparation method is simple in production process, and is easy to realize industrial production.
Description
Technical field
The present invention relates to the double Diethylaminoethanol ester citrate compound of a plant growth regulators succinic acid and
Preparation method.This compound has promotion seed germination, promotes plant growing, enhancing photosynthesis, raising crop yield, improvement
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 improving unit cultivated area is that solution food problem is important
One of measure.Plant growth regulator has that consumption is little, effect is big, can stratification, control to bloom, delaying senility course, carry
High yield, improvement 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.The class that it is synthetic, have a Plant Hormone Action is organic
Material, they can penetrate in plant under relatively low concentration, and the growth promoter of plant is shown promotion or inhibitory action.
In this area, the most valued regulator being to make crop yield, they have shown in agricultural production
Show the biggest efficiency.The research of plant growth regulator and application are from the beginning of the thirties in 20th century is, but its society's effect
Benefit and economic benefit are very big, so its development is very fast, to the sixties, the most define " plant growth regulator work
Industry ".Along with Chemical Engineering Technology and the development of biotechnology, plant growth regulator is to the output increased of agricultural, the changing of product quality
Kind, reduce labor intensity, raising labour productivity plays the most important effect, as the prophesy of people: " 21 century is raw
Thing engineering century ", bionic change will be the change of " transgenic engineering " and " chemical regulation " technology.
China from nineteen thirty-seven from promoting that cuttage root-taking begins one's study plant growth regulator, but before 1949, the most not
Apply on producing.After 1949, introducing 2 from external, 4-dichlorphenoxyacetic acid, naphthalene acetic acid etc. are applied to Fructus Mali pumilae, Fructus Lycopersici esculenti
Deng crops in case falling stop is spent, shedding.Later stage the 1950's, due to succeeding in developing of phenol regulator, range of application
Expand further.To the sixties, the kind of application and object have again increase, but are concentrated mainly on chlorocholine chloride at Cotton Gossypii and Semen Tritici aestivi
On application.After the seventies, plant growth regulator rationale and applied research are obtained multinomial great achievement.The eighties
Latter half, the annual average rate of increase of all kinds of pesticide 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) and plant growth regulators from original seven big fields, and it is bright
Really highlight plant growth regulator importance.Recent year to plant growth regulator research research and application development the most very
Hurry up.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
And caproic acid Diethylaminoethanol ester (DA-6) (DCPTA), inventor finds to have in both structures diethylamino ethoxy group,
According to " principle of hybridization ", it is carried out split with the succinic acid in tricarboxylic acid cycle, i.e. obtain containing double diethylamino ethoxies
Structure there is the double Diethylaminoethanol ester of bioactive compound succinic acid.It is polyfunctional group synergistic structure, fourth
Diacid has another name called succinic acid, is the important intermediate of TCA.Succinate dehydrogenase catalysis succinoxidase chemical conversion Fumaric acid, discharges
Energy and oxygen；The physiologically active of succinic acid produces cooperative effect with the physiologically active of diethylamino ethoxy so that it is have more
Excellent plant growth regulation.
Summary of the invention
An object of the present invention is that proposing one has the double Diethylaminoethanol of bioactive compound succinic acid
Ester citrate.This compound has simple in construction, soluble in water, is easily entered in cyton by cell wall.Plant with existing
Thing growth regulator compares the advantages such as to have amount of application few, and effect is notable, environmentally safe, low toxicity.
For achieving the above object, present invention employs following technical scheme:
The double Diethylaminoethanol ester citrate compound of a kind of succinic acid, it is characterised in that the structure of this compound such as following formula
Shown in:
Another object of the present invention is to propose the preparation method of the double Diethylaminoethanol ester citrate of a kind of succinic acid.This system
It is simple that Preparation Method has technique, and atom utilization is high, does not produce pollution, small investment of production equipment, it is easy to large-scale production.
The preparation method of the double Diethylaminoethanol ester citrate of succinic acid specifically comprises the following steps that
In the reactor equipped with water knockout drum and reflux, add a certain amount of organic solvent, proper catalyst, add one
Determining succinic acid and the N of mol ratio, N-diethylaminoethanol, the lower heating of stirring, at a temperature of 110 DEG C～150 DEG C, reflux water-dividing is anti-
Should, react 5～9h, until the water separated reaches theoretical amount, Filtration of catalyst (reclaims and uses), and filtrate decompression distills out organic
Solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess and low boilers, bottoms adds the double diethyl of succinic acid
The double Diethylaminoethanol of yellow oily liquid succinic acid is filtered to obtain after aminoethanol ester Theoretical Mass 5%-10% activated decoloration
Ester.Again the citric acid of double for succinic acid Diethylaminoethanol esters with twice mole is put in reactor, is heated with stirring to 115 DEG C,
After citric acid melts, the lower crystallisation by cooling of stirring, i.e. obtain the double Diethylaminoethanol ester citrate of white solid product succinic acid.
The method can be also:
In the reactor equipped with water knockout drum and reflux, add a certain amount of organic solvent, proper catalyst, add one
Determine succinic anhydride and the N of mol ratio, N-diethylaminoethanol, the lower heating of stirring, reflux water-dividing at a temperature of 110 DEG C～150 DEG C
Reaction, reacts 3～5h, until the water separated reaches theoretical amount, Filtration of catalyst (reclaims and uses), and filtrate decompression has distilled out
Machine solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess and low boilers, bottoms adds succinic acid double two
The double diethylin second of yellow oily liquid succinic acid is filtered to obtain after ethylamino ethanol ester Theoretical Mass 5%-10% activated decoloration
Alcohol ester.Again the citric acid of double for succinic acid Diethylaminoethanol esters with twice mole is put in reactor, be heated with stirring to 115
DEG C, after citric acid melts, the lower crystallisation by cooling of stirring, i.e. obtain the double Diethylaminoethanol ester citric acid of white solid product succinic acid
Salt.
A certain amount of organic solvent described above is dimethylbenzene or toluene, and its consumption volume milliliter number is succinic acid or fourth two
1-8 times of anhydride quality grams.
The succinic acid of certain mol proportion as above and N, N-diethylaminoethanol, the succinic anhydride of certain mol proportion and
N, N-diethylaminoethanol is succinic acid or succinic 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 succinic acid or succinic acid
The 2%-10% of acid anhydride quality grams.
The double Diethylaminoethanol ester of succinic acid of the present invention is yellow oily liquid, water insoluble, index of refraction: nD 25=
1.6629, density (20 DEG C): 0.7240g/cm3；Productivity is 82.6%～88.8%, the double Diethylaminoethanol ester Fructus Citri Limoniae of succinic acid
Phosphate compounds is white powdery solids, and fusing point is 112 DEG C, soluble in water.The double Diethylaminoethanol ester citric acid of succinic acid
The preparation principle of salt is shown below:
Or
Compared with prior art, the invention have benefit that:
(1) containing Liang Ge diethylaminoethanol ester functional group in one molecule of present configuration, with recessive succinic acid active body knot
Structure carrier each other, atom utilization is high, active function groups superposition, the physiologically active of succinic acid and the physiology of diethylamino ethoxy
Activity produces cooperative effect, and 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 that produce are made in plant growing, enhancing photosynthesis, raising
Measuring, improve fruit quality and strengthen the effects such as stress resistance of plant, 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 return
Receive and use, do not produce pollution, do not cause waste, belong to green preparation process.
(5) when catalyst made by the compounds of this invention preparation technology silica gel, self there is decolorization, can save product
Decolorization.
(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 scale
Produce.
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 succinic acid；Fig. 1 shows, at 1750cm-1Near occur in that strong
Absworption peak, corresponds to the stretching vibration of ester carbonyl group；Additionally, 2900cm-1Near CH occurs2The stretching vibration of middle c h bond；?
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 succinic acid；Fig. 2 shows, deuterochloroform is solvent, 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；δ2.67
~ 2.72 is-OCH2CH2Methylene hydrogen peak that-N is connected with nitrogen and O=CCH2CH2The 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 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 20ml dimethylbenzene, agitating heating
To 150 DEG C of back flow reaction 5h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds to separately
In the there-necked flask of one 250ml, decompression distilling off solvent (reclaim use), the diethylaminoethanol (reclaim and use) of excess and low
After boiling point thing, add 3.0g active hargil 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, productivity 86.3%.Again the citric acid of double for succinic acid Diethylaminoethanol esters with twice mole is mixed
Conjunction is heated with stirring to 115 DEG C, and after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids product
The double Diethylaminoethanol ester citrate of succinic acid.Its fusing point: 112 DEG C.
Embodiment 2 is adding 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 23.4 g (0.2mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 40ml dimethylbenzene, stirring adds
Heat is to 140 DEG C of back flow reaction 8h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds to
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
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, productivity
81.6%.Again the citric acid mix and blend of double for succinic acid Diethylaminoethanol esters with twice mole is heated to 115 DEG C, makes Fructus Citri Limoniae
After acid is melted, stirring crystallisation by cooling becomes salt, i.e. obtains the double Diethylaminoethanol ester Fructus Citri Limoniae of white powdery solids product succinic acid
Hydrochlorate.Its fusing point: 112 DEG C.
Embodiment 3 is adding 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.8g titanium dioxide, 20ml dimethylbenzene, agitating heating
To 150 DEG C of back flow reaction 8h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds to separately
In the there-necked flask of one 250ml, decompression distilling off solvent (reclaim use), the diethylaminoethanol (reclaim and use) of excess and low
After boiling point thing, add 3.0g active hargil 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, productivity 84.1%.Again the citric acid of double for succinic acid Diethylaminoethanol esters with twice mole is mixed
Conjunction is heated with stirring to 115 DEG C, and after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids product
The double Diethylaminoethanol ester citrate of succinic acid.Its fusing point: 112 DEG C.
Embodiment 4 is adding 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 29.3g (0.25mol) N, N-diethylaminoethanol, 0.6g titanyl sulfate, 40ml dimethylbenzene, stirring adds
Heat is to 140 DEG C of back flow reaction 7h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds to
In the there-necked flask of another 250ml, decompression distilling off solvent (reclaim use), the diethylaminoethanol (reclaim and use) of excess and
After low boilers, add 3.0g active hargil 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, productivity 86.0%.Again by the citric acid of double for succinic acid Diethylaminoethanol esters with twice mole
Mix and blend is heated to 115 DEG C, and after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids and produces
The double Diethylaminoethanol ester citrate of thing succinic acid.Its fusing point: 112 DEG C.
Embodiment 5 is adding 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 29.3g (0.25mol) N, N-diethylaminoethanol, 1g silica gel, 40ml dimethylbenzene, it 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 proceeds to another
In the there-necked flask of 250ml, decompression distilling off solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess and low boiling
After thing, obtain the double Diethylaminoethanol ester 27.68g of yellow oily liquid succinic acid, productivity 87.6%.Again by double for succinic acid diethylamine
Base ethanol ester is heated to 115 DEG C with the citric acid mix and blend of twice mole, and 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 succinic acid.Its fusing point: 112 DEG C.
Embodiment 6 is adding 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 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 to another
In the there-necked flask of individual 250ml, decompression distilling off solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess and low boiling
After some thing, add 3.0g active hargil 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, productivity 85.6%.Again double for succinic acid Diethylaminoethanol esters are mixed with the citric acid of twice mole
Being heated with stirring to 115 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids product fourth
The double Diethylaminoethanol ester citrate of diacid.Its fusing point: 112 DEG C.
Embodiment 7 is adding 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 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 to another
In the there-necked flask of individual 250ml, decompression distilling off solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess and low boiling
After some thing, add 3.0g active hargil 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, productivity 82.8%.Again double for succinic acid Diethylaminoethanol esters are mixed with the citric acid of twice mole
Being heated with stirring to 115 DEG C, after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids product fourth
The double Diethylaminoethanol ester citrate of diacid.Its fusing point: 112 DEG C.
Embodiment 8 is adding 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 23.4 g (0.2mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 40ml toluene, agitating heating
To 110 DEG C of back flow reaction 9h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds to separately
In the there-necked flask of one 250ml, after decompression distilling off solvent (reclaim and use) and low boilers, add the stirring of 3.0g active hargil
30 minutes, it is cooled to less than 80 DEG C, filters to obtain the double Diethylaminoethanol ester 25.91g of yellow oily liquid succinic acid, productivity
82.0%.Again the citric acid mix and blend of double for succinic acid Diethylaminoethanol esters with twice mole is heated to 115 DEG C, makes Fructus Citri Limoniae
After acid is melted, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester lemon of white powdery solids product succinic acid
Lemon hydrochlorate.Its fusing point: 112 DEG C.
Embodiment 9 is adding 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 29.3g (0.25mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 40ml toluene, agitating heating
To 110 DEG C of back flow reaction 7h, until separating 3.6g (0.2mol) water, Filtration of catalyst (direct reuse), filtrate proceeds to separately
In the there-necked flask of one 250ml, decompression distilling off solvent (reclaim use), the diethylaminoethanol (reclaim and use) of excess and low
After boiling point thing, add 3.0g active hargil 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, productivity 85.3%.Again the citric acid of double for succinic acid Diethylaminoethanol esters with twice mole is mixed
Conjunction is heated with stirring to 115 DEG C, and after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids product
The double Diethylaminoethanol ester citrate of succinic acid.Its fusing point: 112 DEG C.
Embodiment 10 is adding 11.8g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic acid, 29.3g (0.25mol) N, N-diethylaminoethanol, 1.0g silica gel, 40ml toluene, it 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 proceeds to another
In the there-necked flask of 250ml, decompression distilling off solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess and low boiling
After thing, obtain the double Diethylaminoethanol ester 27.14g of yellow oily liquid succinic acid, productivity 85.9%.Again by double for succinic acid diethylamine
Base ethanol ester is heated to 115 DEG C with the citric acid mix and blend of twice mole, and after making citric acid melt, stirring crystallisation by cooling becomes
Salt, i.e. obtains the double Diethylaminoethanol ester citrate of white powdery solids product succinic acid.Its fusing point: 112 DEG C.
Embodiment 11 is adding 10.0g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic anhydride, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.8g titanyl sulfate, 20ml dimethylbenzene, stirring adds
Heat is to 145 DEG C of back flow reaction 3h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate proceeds to
In the there-necked flask of another 250ml, decompression distilling off solvent (reclaim use), the diethylaminoethanol (reclaim and use) of excess and
After low boilers, add 3.0g active hargil 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, productivity 88.3%.Again by the citric acid of double for succinic acid Diethylaminoethanol esters with twice mole
Mix and blend is heated to 115 DEG C, and after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids and produces
The double Diethylaminoethanol ester citrate of thing succinic acid.Its fusing point: 112 DEG C.
Embodiment 12 is adding 10.0g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic anhydride, 23.4g (0.2mol) N, N-diethylaminoethanol, 0.6g titanyl sulfate, 40ml dimethylbenzene, stirring adds
Heat is to 145 DEG C of back flow reaction 5h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate proceeds to
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
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, productivity
82.6%.Again the citric acid mix and blend of double for succinic acid Diethylaminoethanol esters with twice mole is heated to 115 DEG C, makes Fructus Citri Limoniae
After acid is melted, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains the double Diethylaminoethanol ester lemon of white powdery solids product succinic acid
Lemon hydrochlorate.Its fusing point: 112 DEG C.
Embodiment 13 is adding 10.0g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic anhydride, 29.3g (0.25mol) N, N-diethylaminoethanol, 0.8g titanium dioxide, 40ml dimethylbenzene, stirring
Being heated to 145 DEG C of back flow reaction 4h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate turns
Enter in the there-necked flask of another 250ml, decompression distilling off solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess
And after low boilers, add 3.0g active hargil and stir 30 minutes, be cooled to less than 80 DEG C, filter to obtain yellow oily liquid fourth two
The double Diethylaminoethanol ester 27.18g of acid, productivity 86.0%.Again by the Fructus Citri Limoniae of double for succinic acid Diethylaminoethanol esters with twice mole
Acid mix and blend is heated to 115 DEG C, and after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids
The double Diethylaminoethanol ester citrate of product succinic acid.Its fusing point: 112 DEG C.
Embodiment 14 is adding 10.0g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic anhydride, 35.1g (0.3mol) N, N-diethylaminoethanol, 0.8g titanium dioxide, 30ml toluene, agitating heating
To 113 DEG C of back flow reaction 3h, until separating 1.8g (0.1mol) water, Filtration of catalyst (direct reuse), filtrate proceeds to separately
In the there-necked flask of one 250ml, decompression distilling off solvent (reclaim use), the diethylaminoethanol (reclaim and use) of excess and low
After boiling point thing, add 3.0g active hargil 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, productivity 88.8%.Again the citric acid of double for succinic acid Diethylaminoethanol esters with twice mole is mixed
Conjunction is heated with stirring to 115 DEG C, and after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids product
The double Diethylaminoethanol ester citrate of succinic acid.Its fusing point: 112 DEG C.
Embodiment 15 is adding 10.0g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic anhydride, 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 to another
In the there-necked flask of individual 250ml, after decompression distilling off solvent (reclaim and use) and low boilers, obtain yellow oily liquid succinic acid double
Diethylaminoethanol ester 26.0g, productivity 82.3%.Again the citric acid of double for succinic acid Diethylaminoethanol esters with twice mole is mixed
Conjunction is heated with stirring to 115 DEG C, and after making citric acid melt, the lower crystallisation by cooling of stirring becomes salt, i.e. obtains white powdery solids product
The double Diethylaminoethanol ester citrate of succinic acid.Its fusing point: 112 DEG C.
Embodiment 16 is adding 10.0g equipped with agitator in the 250ml four-hole boiling flask of water knockout drum and reflux
(0.1mol) succinic anhydride, 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 to another
In the there-necked flask of individual 250ml, decompression distilling off solvent (reclaim and use), the diethylaminoethanol (reclaim and use) of excess and low boiling
After some thing, obtain the double Diethylaminoethanol ester 26.95g of yellow oily liquid succinic acid, productivity 85.3%.Again by double for succinic acid diethyls
Aminoethanol ester is heated to 115 DEG C with the citric acid mix and blend of twice mole, after making citric acid melt, and the lower crystallisation by cooling of stirring
Become salt, i.e. obtain the double Diethylaminoethanol ester citrate of white powdery solids product succinic acid.Its fusing point: 112 DEG C.
Table 1 succinic acid is that main technologic parameters prepared by raw material
Table 2 succinic anhydride is that main technologic parameters prepared by raw material
| Sequence number | Diethylaminoethanol | Catalyst | Solvent | Temperature DEG C | Time | Productivity % |
| 1 | 35.1g(0.3mol) | 0.8g titanyl sulfate | 20ml dimethylbenzene | 145 | 3h | 88.3% |
| 2 | 23.4g(0.2mol) | 0.6g titanyl sulfate | 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: in table 2, the inventory of succinic anhydride is 10.0 g (0.1mol)
Double for the succinic acid of above-mentioned preparation Diethylaminoethanol ester citric acid hydrochlorates are used for green vegetable, Semen Glycines, Semen Tritici aestivi, oil by inventor
Dish, rice paddy seed are planted as evaluation with reference to " international seed inspection procedure " (1985), " crop seeds inspection procedure " (1995)
The standard (to grow 1cm for germinateing) whether son germinates, has made biological activity test, and method of testing is as follows:
Use plate culture, double for succinic acid Diethylaminoethanol ester citrates are joined be respectively prepared 100mg/L, 70mg/L,
40mg/L and 10mg/L variable concentrations solution, studies it and adjusts the growth of green vegetable, Semen Glycines, Semen Tritici aestivi, Brassica campestris L, rice seedling root system
Joint effect.Making blank assay with distilled water, the DA-6 solution of same concentrations makees standard control group, respectively with the solution of respective concentration
Soak green vegetable, Semen Glycines, Semen Tritici aestivi, Brassica campestris L, rice paddy seed 6h 8h, be then respectively placed in temperature be 23 DEG C, 25 DEG C, 20 DEG C, 23 DEG C,
The length of its root system and stem is measured in 28 DEG C of constant temperature culture rooms after cultivating 4d 6d, and adds up germination number, uses below equation meter
Calculate germination percentage and regulation percent activity.
Germination percentage=germinative number/seed sum
A=(N-N0)/N0×100%
A is sample regulation activity；
N cultivates the grand mean length of the root recorded and bud in compound solution；
N0The grand mean length of the root recorded and bud is cultivated in distilled water；
The double Diethylaminoethanol ester citrate of succinic acid prepared by the present invention is to plant growth regulating activity and the number of germination percentage
According to being shown in Table 3 respectively, shown in table 4, table 5, table 6, table 7.
The double Diethylaminoethanol ester citrate of table 3 succinic acid is for green vegetable seed (50) Seed germination data
The double Diethylaminoethanol ester citrate of table 4 succinic acid is for Semen Glycines seed (10) Seed germination data
The double Diethylaminoethanol ester citrate of table 5 succinic acid is for wheat seed (30) Seed germination data
The double Diethylaminoethanol ester citrate of table 6 succinic acid is for Semen Brassicae campestris (50) Seed germination data
The double Diethylaminoethanol ester citrate of table 7 succinic acid is for rice paddy seed (30) Seed germination data
Claims (7)
1. the double Diethylaminoethanol ester citrate compound of a plant growth regulators succinic acid, it is characterised in that this change
The structure of compound is shown below:
。
2. the preparation method of the double Diethylaminoethanol ester citrate compound of a plant growth regulators succinic acid, its feature
Being, the method is:
In the reactor equipped with water knockout drum and reflux, add a certain amount of organic solvent, proper catalyst, add one
Determining succinic acid and the N of mol ratio, N-diethylaminoethanol, the lower heating of stirring, at a temperature of 110 DEG C～150 DEG C, reflux water-dividing is anti-
Should, react 5～9h, until the water separated reaches theoretical amount, Filtration of catalyst, filtrate decompression distills out organic solvent, excess
Diethylaminoethanol and low boilers, it is white that bottoms adds succinic acid double Diethylaminoethanol ester Theoretical Mass 5%-10% activity
The double Diethylaminoethanol ester of yellow liquid succinic acid is filtered to obtain after soil decolouring；Again by double for succinic acid Diethylaminoethanol esters and twice
Mole citric acid put in reactor, be heated with stirring to 115 DEG C, after citric acid melts, the lower crystallisation by cooling of stirring becomes salt, to obtain final product
To the double Diethylaminoethanol ester citrate of white solid product succinic acid.
3. the preparation method of the double Diethylaminoethanol ester citrate compound of a plant growth regulators succinic acid, its feature
Being, the method is:
In the reactor equipped with water knockout drum and reflux, add a certain amount of organic solvent, proper catalyst, add one
Determine succinic anhydride and the N of mol ratio, N-diethylaminoethanol, the lower heating of stirring, reflux water-dividing at a temperature of 110 DEG C～150 DEG C
Reaction, reacts 3～5h, until the water separated reaches theoretical amount, Filtration of catalyst, filtrate decompression distills out organic solvent, mistake
The diethylaminoethanol of amount and low boilers, bottoms adds succinic acid double Diethylaminoethanol ester Theoretical Mass 5%-10% activity
The double Diethylaminoethanol ester of slightly yellow liquid succinic acid is filtered to obtain after hargil decolouring；Again by double for succinic acid Diethylaminoethanol esters with
The citric acid of twice mole is put in reactor, is heated with stirring to 115 DEG C, and after citric acid melts, the lower crystallisation by cooling of stirring becomes salt,
I.e. obtain the double Diethylaminoethanol ester citrate of white solid product succinic acid.
4. Citrated according to the double Diethylaminoethanol ester of a plant growth regulators succinic acid described in Claims 2 or 3
The preparation method of compound, it is characterised in that: described a certain amount of organic solvent is dimethylbenzene or toluene, its consumption volume milliliter
Number is succinic acid or 1-8 times of succinic anhydride quality grams.
5. Citrated according to the double Diethylaminoethanol ester of a plant growth regulators succinic acid described in Claims 2 or 3
The preparation method of compound, it is characterised in that: the succinic acid of described certain mol proportion and N, N-diethylaminoethanol, certain mole
The succinic anhydride of ratio and N, N-diethylaminoethanol is succinic acid or succinic anhydride: the mol ratio of N, N-diethylaminoethanol is 1:
2-1:3。
6. Citrated according to the double Diethylaminoethanol ester of a plant growth regulators succinic acid described in Claims 2 or 3
The preparation method of compound, it is characterised in that: described proper catalyst is titanyl sulfate, titanium dioxide or silica gel, and its consumption is
Succinic acid or the 2%-10% of succinic anhydride quality grams.
7. Citrated according to the double Diethylaminoethanol ester of a plant growth regulators succinic acid described in Claims 2 or 3
The preparation method of compound, it is characterised in that: described Filtration of catalyst, filtrate decompression distill out organic solvent, excess
Diethylaminoethanol be recovered to catalyst, organic solvent, diethylaminoethanol recycling.
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Cited By (3)
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| CN113045439A (en) * | 2021-03-25 | 2021-06-29 | 礼研科技(济南)有限公司 | Succinic acid mono- (2-diethylamino-ethyl) ester, preparation method and application |
| CN114133282A (en) * | 2021-11-23 | 2022-03-04 | 谭宏伟 | Preparation method of efficient magnesium polyphosphate fertilizer |
| CN114982757A (en) * | 2022-05-09 | 2022-09-02 | 郑州尼采生物科技有限公司 | Method for preparing ester or tertiary amine plant growth regulator aqueous solution |
Families Citing this family (1)
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| RU2759761C1 (en) * | 2021-04-28 | 2021-11-17 | Олег Владимирович Евсеенков | Plant growth regulator |
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Cited By (4)
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| CN113045439A (en) * | 2021-03-25 | 2021-06-29 | 礼研科技(济南)有限公司 | Succinic acid mono- (2-diethylamino-ethyl) ester, preparation method and application |
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| CN114133282A (en) * | 2021-11-23 | 2022-03-04 | 谭宏伟 | Preparation method of efficient magnesium polyphosphate fertilizer |
| CN114982757A (en) * | 2022-05-09 | 2022-09-02 | 郑州尼采生物科技有限公司 | Method for preparing ester or tertiary amine plant growth regulator aqueous solution |
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