CN106957226A - A kind of preparation method of Prohexadione calcium - Google Patents
A kind of preparation method of Prohexadione calcium Download PDFInfo
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- CN106957226A CN106957226A CN201710173438.3A CN201710173438A CN106957226A CN 106957226 A CN106957226 A CN 106957226A CN 201710173438 A CN201710173438 A CN 201710173438A CN 106957226 A CN106957226 A CN 106957226A
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- Prior art keywords
- naphthenic acid
- prohexadione calcium
- preparation
- adjust
- calcium
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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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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of Prohexadione calcium, it forms solution by adjusting naphthenic acid to be dissolved in solvent, will be slowly added dropwise in the solution into the aqueous solution of calcium carbonate to adjust naphthenic acid as raw material, and fully reaction is to terminating, and suction filtration washs to obtain target product Prohexadione calcium.The present invention is to adjust the method that Prohexadione calcium is made as raw material reaction for naphthenic acid and calcium carbonate, solvent environmental protection, stable reaction used by the present invention, purity is high, accurate, the measured Prohexadione calcium of matter that is conducive to obtaining structure, its reaction condition is simple, step convenience, stable yield, it is low for equipment requirements, prepare with low cost, environmental protection, be suitable for industrialized production.
Description
Technical field
The present invention relates to organic agricultural chemicals synthesis technical field, more particularly to a kind of preparation method it is simple, low for equipment requirements,
The preparation method for the Prohexadione calcium that product purity is high, structure is qualified.
Background technology
Prohexadione calcium is a plant growth regulators, can effective coordinate plant growth, prevent that plant from lodging, its structural formula
It is as follows：
In the route of current document report, the route with industrial prospect is main using diethyl maleate as raw material, passes through
Addition, condensation, acylation, rearrangement, obtain Prohexadione calcium into steps such as salt, react as follows：
The route has more maturation, but the product that domestic enterprise is produced by the route there is no method in structure and purity at present
Obtain international endorsement.Although final product is into salt, often chain, greatly influences its using effect, chain structure is such as
Under：
Therefore, purity and the qualified Prohexadione calcium of structure how are obtained, it is technical problem urgently to be resolved hurrily to improve its using effect.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of preparation method it is simple, to equipment
It is required that the preparation method for the Prohexadione calcium that low, product purity is high, structure is qualified.
The preparation method of described a kind of Prohexadione calcium, it is characterised in that to adjust naphthenic acid as raw material, will adjust naphthenic acid to be dissolved in molten
Solution is formed in agent, will be slowly added dropwise in the solution into the aqueous solution of calcium carbonate, fully reaction is to terminating, and suction filtration is washed
Target product Prohexadione calcium.
The preparation method of described Prohexadione calcium, it is characterised in that the molar ratio for adjusting naphthenic acid and calcium carbonate is 1.0：
0.5~1.5。
The preparation method of described Prohexadione calcium, it is characterised in that the molar ratio for adjusting naphthenic acid and calcium carbonate is 1.0：
0.9。
The preparation method of described Prohexadione calcium, it is characterised in that the reaction time is 2h ~ 10h.
The preparation method of described Prohexadione calcium, it is characterised in that the reaction time is 8h.
The preparation method of described Prohexadione calcium, it is characterised in that it is methanol, ethanol, acetic acid second that the solvent of naphthenic acid is adjusted in dissolving
Any one or a few mixture in ester, toluene, acetonitrile or water, solvent is 10 ~ 20 with adjusting the mass ratio of naphthenic acid：1.
The preparation method of described Prohexadione calcium, it is characterised in that the mixing that the solvent of naphthenic acid is second alcohol and water is adjusted in dissolving
Thing.
The preparation method of described Prohexadione calcium, it is characterised in that reaction temperature is 0 DEG C ~ 80 DEG C.
Its reaction equation is as follows：
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows：
The present invention is to adjust the method that Prohexadione calcium is made as raw material reaction for naphthenic acid and calcium carbonate, the green ring of solvent used by the present invention
Guarantor, stable reaction, purity is high, accurate, the measured Prohexadione calcium of matter that is conducive to obtaining structure, and its reaction condition is simple, step side
Just, stable yield, it is low for equipment requirements, prepare with low cost, environmental protection, be suitable for industrialized production.
Embodiment
The invention will be further described with reference to embodiments, but protection scope of the present invention is not limited to that：
Embodiment 1：
21.2 g (0.1 mol) are taken to adjust naphthenic acid to be dissolved in 212 g（Water：Ethanol=1：1, mass ratio）Mixture in form solution, and
It is transferred in dropping funel, 9g (0.09 mol) calcium carbonate and 100g water dissolves is added in 500 ml reaction bulb and obtain carbon completely
Sour calcium solution, the tune naphthenic acid solution prepared, about 1h completion of dropping, normal temperature are added dropwise into calcium carbonate soln by dropping funel
Lower reaction 8h, reaction terminates rear suction filtration, is washed with ethanol 2 times, dries, obtains faint yellow solid product Prohexadione calcium 23g, yield is
92%, purity 96%.
Embodiment 2：
Take 21.2 g (0.1 mol) to adjust naphthenic acid to be dissolved in 212g water and form tune naphthenic acid solution, and be transferred in dropping funel,
9 g (0.09 mol) calcium carbonate and 100 g water are added in 500 ml reaction bulb, are dripped into calcium carbonate soln by dropping funel
Plus the tune naphthenic acid aqueous solution prepared, about 1h completion of dropping, about 8h is reacted under normal temperature, and reaction terminates, and suction filtration is washed with ethanol
2 times, dry, obtain the g of faint yellow solid product Prohexadione calcium 22.5, yield 90%, purity 95%.
Embodiment 3：
Take 21.2 g（0.1 mol）Naphthenic acid is adjusted to be dissolved in 212 g water and ethanol（Water：Ethanol=1：1, mass ratio）Mixture in shape
Into tune naphthenic acid solution, and it is transferred in dropping funel, 9 g is added in 500 ml reaction bulb（0.09 mol）Calcium carbonate and
100 g water, the tune naphthenic acid solution prepared, about 1h completion of dropping, ice bath are added dropwise into calcium carbonate soln by dropping funel
Lower reaction about 8h, reaction terminates, and suction filtration is washed 2 times with ethanol, dries, obtains the g of faint yellow solid product Prohexadione calcium 23.3, receives
Rate 93.2%, purity 95%.
Embodiment 4：
Take 21.2 g to adjust naphthenic acid to be dissolved in the mixture of 212 g water and ethanol and form tune naphthenic acid solution, and be transferred to dropping funel
In, 9 g calcium carbonate and 100 g water are added in 500 ml reaction bulb, is added dropwise and matched somebody with somebody by dropping funel into calcium carbonate soln
The tune naphthenic acid solution made, about 1h completion of dropping reacts about 8h at 80 DEG C, reaction terminates, suction filtration, is washed with ethanol 2 times, does
It is dry, obtain faint yellow solid product Prohexadione calcium 22.3g, yield 93%, purity 95%.
Embodiment 5：
Take 21.2 g to adjust naphthenic acid to be dissolved in 318 g ethyl acetate and form tune naphthenic acid solution, and be transferred in dropping funel, 500
11 g calcium carbonate and 100 g water are added in ml reaction bulb, the tune prepared is added dropwise by dropping funel into calcium carbonate soln
Naphthenic acid solution, about 1h completion of dropping reacts about 2h at 100 DEG C, reaction terminates, suction filtration, is washed with ethanol 2 times, dries, obtains light
The g of yellow solid product Prohexadione calcium 23.0, yield 92%, purity 92%.
Embodiment 6：
Take 21.2 g to adjust naphthenic acid to be dissolved in 424g toluene and form tune naphthenic acid solution, and be transferred in dropping funel, 500 ml's
10g calcium carbonate and 100 g water are added in reaction bulb, the tune naphthenic acid prepared are added dropwise by dropping funel into calcium carbonate soln molten
Liquid, about 1h completion of dropping reacts about 10h at 0 DEG C, reaction terminates, suction filtration, is washed with ethanol 2 times, dries, obtains pale yellow colored solid
The g of body product Prohexadione calcium 23.1, yield 92.4%, purity 93%.
Embodiment 7：
Take 21.2 g to adjust naphthenic acid to be dissolved in 268g acetonitriles and form tune naphthenic acid solution, and be transferred in dropping funel, 500 ml's
12 g calcium carbonate and 100 g water are added in reaction bulb, the tune naphthenic acid prepared is added dropwise by dropping funel into calcium carbonate soln
Solution, about 1h completion of dropping reacts about 9h at 60 DEG C, reaction terminates, suction filtration, is washed with ethanol 2 times, dries, obtains faint yellow
The g of solid product Prohexadione calcium 23.9, yield 95.6%, purity 90%.
The content of Prohexadione calcium of the present invention is determined through liquid chromatogram.
Claims (8)
1. a kind of preparation method of Prohexadione calcium, it is characterised in that to adjust naphthenic acid as raw material, will adjust naphthenic acid to be dissolved in solvent and is formed
Solution, will be slowly added dropwise into the aqueous solution of calcium carbonate in the solution, and fully reaction is to terminating, and suction filtration washs to obtain target product
Prohexadione calcium.
2. the preparation method of Prohexadione calcium according to claim 1, it is characterised in that adjust naphthenic acid and feeding intake for calcium carbonate to rub
You are than being 1.0：0.5~1.5.
3. the preparation method of Prohexadione calcium according to claim 1, it is characterised in that adjust naphthenic acid and feeding intake for calcium carbonate to rub
You are than being 1.0：0.9.
4. the preparation method of Prohexadione calcium according to claim 1, it is characterised in that the reaction time is 2h ~ 10h.
5. the preparation method of Prohexadione calcium according to claim 1, it is characterised in that the reaction time is 8h.
6. the preparation method of Prohexadione calcium according to claim 1, it is characterised in that dissolving adjust the solvent of naphthenic acid for methanol,
Any one or a few mixture in ethanol, ethyl acetate, toluene, acetonitrile or water, solvent with adjust the mass ratio of naphthenic acid for 10 ~
20：1.
7. the preparation method of Prohexadione calcium according to claim 1, it is characterised in that it is ethanol that the solvent of naphthenic acid is adjusted in dissolving
With the mixture of water.
8. the preparation method of Prohexadione calcium according to claim 1, it is characterised in that reaction temperature is 0 DEG C ~ 80 DEG C.
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| CN201710173438.3A CN106957226B (en) | 2017-03-22 | 2017-03-22 | Preparation method of prohexadione calcium |
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| CN106957226B CN106957226B (en) | 2020-12-01 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087294A (en) * | 2019-12-18 | 2020-05-01 | 浙江工业大学 | Preparation method of high-purity prohexadione calcium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774906A (en) * | 2010-02-10 | 2010-07-14 | 江苏康恒化工有限公司 | Preparation method of 3,5-dioxo-4-propyl phthalidyl cyclohexane calcium amino acid |
| WO2011012495A1 (en) * | 2009-07-30 | 2011-02-03 | Basf Se | Granules containing prohexadione calcium and sulfate |
| WO2011012494A1 (en) * | 2009-07-30 | 2011-02-03 | Basf Se | Granulate containing a carboxylic growth regulator and a solid acidifier |
| CN104140368A (en) * | 2014-07-30 | 2014-11-12 | 江西农业大学 | Method for preparing calcium3-oxido-5-oxo-4-propionyl cyclohex-3-enecarboxylate |
-
2017
- 2017-03-22 CN CN201710173438.3A patent/CN106957226B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011012495A1 (en) * | 2009-07-30 | 2011-02-03 | Basf Se | Granules containing prohexadione calcium and sulfate |
| WO2011012494A1 (en) * | 2009-07-30 | 2011-02-03 | Basf Se | Granulate containing a carboxylic growth regulator and a solid acidifier |
| CN101774906A (en) * | 2010-02-10 | 2010-07-14 | 江苏康恒化工有限公司 | Preparation method of 3,5-dioxo-4-propyl phthalidyl cyclohexane calcium amino acid |
| CN104140368A (en) * | 2014-07-30 | 2014-11-12 | 江西农业大学 | Method for preparing calcium3-oxido-5-oxo-4-propionyl cyclohex-3-enecarboxylate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087294A (en) * | 2019-12-18 | 2020-05-01 | 浙江工业大学 | Preparation method of high-purity prohexadione calcium |
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