CN110467573A - A kind of synthesis processing method of pyrazoles disulphide - Google Patents
A kind of synthesis processing method of pyrazoles disulphide Download PDFInfo
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- CN110467573A CN110467573A CN201910856787.4A CN201910856787A CN110467573A CN 110467573 A CN110467573 A CN 110467573A CN 201910856787 A CN201910856787 A CN 201910856787A CN 110467573 A CN110467573 A CN 110467573A
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- pyrazoles
- disulphide
- filter cake
- synthesis processing
- processing method
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
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- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of synthesis processing methods of pyrazoles disulphide, arylpyrazole nitrile is dissolved in solvent I, sulfur monochloride reaction is added, it is passed through dry nitrogen after reaction and blows away the hydrogen chloride generated in the reaction of part, it is passed through ammonia again and is neutralized to pH value 6.5 ~ 7, then filters pressing obtains filter cake A and filtrate A；Filter cake A is further processed to obtain target product pyrazoles disulphide.The present invention removes the inorganic impurities such as the elemental sulfur in product with organic solvent method, then removes part organic impurities by recrystallization, obtains high-quality pyrazoles disulphide.Meanwhile the present invention does not use process water, production process does not generate technique waste water.
Description
Technical field
The present invention relates to a kind of synthesis processing methods of pyrazoles disulphide.
Background technique
5- Amino 3 cyano -1- (2,6- dichlor-4-trifluoromethyl-phenyl) pyrazoles disulfide structure formula is as follows:
5- Amino 3 cyano -1- (2,6- dichlor-4-trifluoromethyls-phenyl) pyrazoles disulphide also known as 1- (2,6- bis-
Chloro- 4- trifluoromethyl) -3- cyano -5- amino-pyrazole -4- disulfide is Fipronil, ethiprole, butene-fipronil etc.
The important intermediate of N- phenyl pyrazoles pesticide.
The N- phenyl pyrazoles action of agricultural chemicals principle such as Fipronil, ethiprole, butene-fipronil, is to pass through γ-aminobutyric acid
The channel of the chloride channel interference chloride ion of adjusting, destroys the activity of normal central nervous system, causes insect death.Due to this
Unique mechanism of action, so that this kind of pesticides is had the distinguishing feature different from common insecticides: the insecticide is to including half wing
The pests such as mesh, Lepidoptera, Thysanoptera, coleoptera and cyclopentadiene, pyrethroids class, carbamate insecticides are generated anti-
The pest of pharmacological property all has high sensibility, simultaneously with long-term effect (lasting period is generally 2~4 weeks, for up to 6 weeks),
The spies such as high activity (dosage is low, and per hectare only needs tens grams of effective components that can control pierce-suck type or pests with chewing mouthparts)
Point.What such pesticide was developed at first is Fipronil, multiple in recent years since Fipronil is more toxic aquatile and honeybee etc.
Limitation has been made to its scope of application by country.But its compound preparation is still widely used in crop pests prevention and treatment, for many years fluorine
Worm nitrile and its compound preparation total sales volume are in international pesticide market always within first 5.Except be used as pesticide in addition to, Fipronil also by
In domestic hygiene control of insect, the Fipronil of high-quality is for manufacturing pet insecticide, domestic hygiene agrochemical.
5- Amino 3 cyano -1- (2,6- dichlor-4-trifluoromethyl-phenyl) pyrazoles disulphide generally passes through 5- amino -
3- cyano -1- (2,6- dichlor-4-trifluoromethyls-phenyl) -1-H pyrazoles is reacted with sulfur monochloride to be made, such as " Shandong Agricultural University
Journal " method in (natural science edition) Zhang Changjun of volume 40 in 2009 etc. " study on the synthesis of Fipronil ": by 5- amino -3- cyanogen
Base -1- (2,6- dichlor-4-trifluoromethyls-phenyl) pyrazoles is dissolved in chlorobenzene/acetonitrile in the mixed solvent, after being reacted with sulfur monochloride,
It is neutralized to pH value 6.5~7 with ammonium hydroxide, then filters to isolate the filter cake of the disulphide containing product.Filter cake uses chlorobenzene, acetonitrile mixed again
Drying after solution washs is closed, target product pyrazoles disulphide is obtained.Industrialized production is by 5- Amino 3 cyano -1- (2,6- bis-
Chloro- 4- trifluoromethyl-phenyl) after -1-H pyrazoles reacts with sulfur monochloride, neutralized with ammonium hydroxide, ammonia or triethylamine, filters pressing separation,
Filter cake is dried to obtain pyrazoles disulphide after being washed with hot water.Due to containing a small amount of elemental sulfur, in addition monochlor(in)ate in sulfur monochloride
Reaction of moisture in sulphur and solvent, raw material or air may generate elemental sulfur, when producing pyrazoles disulphide using the technique, no
The impurity such as elemental sulfur can be removed, product quality is influenced；It simultaneously after the process, generates and contains a large amount of water in solvent, separation is tired
Difficult (acetonitrile, water azeotropic), generates a large amount of waste water after separation.Ammonia nitrogen, COD content are higher in waste water, and processing is difficult.
Summary of the invention
The purpose of the present invention is to provide a kind of reduction technique waste waters to generate, at the synthesis of the pyrazoles disulphide of high income
Reason method.
The technical solution of the invention is as follows:
A kind of synthesis processing method of pyrazoles disulphide adds it is characterized in that: arylpyrazole nitrile is dissolved in solvent I
Enter sulfur monochloride reaction, is passed through dry nitrogen after reaction and blows away the hydrogen chloride generated in the reaction of part, then be passed through ammonia
It is neutralized to pH value 6.5~7, then filters pressing, obtains filter cake A and filtrate A；Filter cake A is further processed to obtain two sulphur of target product pyrazoles
Compound.
Sulfur monochloride and arylpyrazole nitrile molar ratio are 1:2.01~2.30, and reaction temperature is no more than 45 DEG C.
Filtrate A is applied as reaction dissolvent.
Filter cake A is further processed method: solvent II is added after filter cake A is dry, after dissolving pyrazoles disulphide, then filters pressing,
Obtain liquor B and filter cake B；Filter cake B dried recovered solvent II is recycled, and the filter cake B after drying is containing elemental sulfur, ammonium chloride and portion
Divide the solid waste of organic impurities；Liquor B is further processed, and obtains target product.
It includes decrease temperature crystalline processing after concentration that liquor B, which is further processed method,.
Solvent I be toluene, carbon tetrachloride, acetonitrile, Benzene Chloride, ethyl acetate, o-dichlorohenzene, dichloroethanes, ortho-chlorotolu'ene,
The combination of one or more of p-chlorotoluene, p-chloro benzo trifluoride-99, p-chlorotrichlormethyl.
Solvent II is N, dinethylformamide, N, N- dimethyl acetamide, dimethyl sulfoxide, tetrahydrofuran, acetone, fourth
The combination of one or more of ketone, 2 pentanone, propione, N- crassitude equal solvent.
The present invention removes the inorganic impurities such as the elemental sulfur in product with organic solvent method, then has by recrystallization removing part
Machine impurity obtains high-quality pyrazoles disulphide.Meanwhile the present invention does not use process water, production process does not generate Waste
Water.
The present invention, after reaction, sulfur monochloride react completely, and excessive arylpyrazole nitrile is dissolved in reaction mother liquor,
And in filtrate A, when being applied as reaction dissolvent, raw material can be converted to and continued and chlorination reaction of Salmon-Saxl.Available higher product
Recovery rate.It can be used for manufacturing the preparing protodrugs such as high-quality Fipronil, ethiprole, butene-fipronil, while producing
Journey does not generate technique waste water, meets green production theory.
Below with reference to embodiment, the invention will be further described.
Specific embodiment
Embodiment 1
Mixed solvent (water content 0.15%) 400g of acetonitrile and chlorobenzene composition is added into dry 1000ml four-hole bottle,
It is added arylpyrazole nitrile 130.5g (98.46%, 0.40mol), stirring, ice bath is cooled to 20 DEG C, and sulfur monochloride 26.1g is added
(98.05%, 0.19mol).Temperature is added dropwise and rises to 32 DEG C, continues to be stirred to react 1 hour, is passed through drying nitrogen stripping 30
Minute, then it is passed through dry ammonia, pH value 6.8 is controlled, temperature is no more than 35 DEG C.It filters, filtrate applies (embodiment as solvent
2), filter cake is dried in vacuo, and obtains dry cake 148.9g, and filter cake is added to equipped with propione 600g with stirring and reflux unit
In four-hole bottle, 50 DEG C or so are warming up to, keeps the temperature 30 minutes, then filters pressing, filtrate tiny structure steams 475~520g3- pentanone, so
It moves back after being down to room temperature in water-bath, uses ice bath instead and be cooled to 10 DEG C hereinafter, heat preservation 1 hour or more, filters pressing, filter cake drying
Afterwards, pale yellow crystals sprills 124.6g is obtained, HPLC detects target product content 99.15% (external standard method), yield 87.67%.
Embodiment 2
(HPLC detects arylpyrazole nitrile content 2.01% to synthetic reaction mother liquor (filtrate) 346g of embodiment 1, rolls over pyrazoles nitrile
0.02mol detects mother liquor moisture 0.17%), fresh acetonitrile and chlorobenzene mixed solvent 61g is added, arylpyrazole nitrile is added
123.7g (98.21%, add up to pyrazoles nitrile 0.40mol), stirring, ice bath is cooled to 20 DEG C, and sulfur monochloride 26.1g is added
(98.05%, 0.19mol).If embodiment 1 is reacted and is handled, pale yellow crystals sprills 125.2g is obtained, HPLC detects target and produces
Object content 99.07% (external standard method), yield 88.01% calculate yield newly to put into arylpyrazole nitrile as 93.45%.
Embodiment 3
Such as embodiment 1, acetonitrile is put into, chlorobenzene adds up to 400g (water content 0.15%), addition arylpyrazole nitrile 130.4g
(98.52%, 0.4mol), stirring, ice bath are cooled to 20 DEG C, are added sulfur monochloride 26.1g (98.05%, 0.19mol).Strictly according to the facts
Example 1, until neutralization terminates.Synthetic is filtered, filter cake 227.3g is obtained.Filter cake room temperature washes twice, and adds water 100g, stirring half every time
Hour, it is dry after suction filtration, pale yellow powder 133.6g, HPLC detection are obtained, area normalization method calculates target product content
99.26%, external standard method calculates, target product content 96.23%, yield 91.25%.
Embodiment 4
Such as embodiment 2, acetonitrile is put into, chlorobenzene adds up to 400g (water content 0.15%), addition arylpyrazole nitrile 130.4g
(98.52%, 0.4mol), stirring, ice bath are cooled to 20 DEG C, are added sulfur monochloride 28.9g (98.05%, 0.21mol).Strictly according to the facts
Example 1, until neutralization terminates.Synthetic is filtered, filter cake 243.6g is obtained.Filter cake room temperature washes twice, and adds water 100g, stirring half every time
Hour, it is dry after suction filtration, pale yellow powder 145.2g, HPLC detection are obtained, area normalization method calculates target product content
98.45%, external standard method calculates, target product content 94.89%, yield 97.79%.
Embodiment 5
It by 4 product 100.1g of embodiment, is added in 100g50 DEG C of hot water, insulated and stirred half an hour, washes repeatedly twice,
Then dry after filtering, pale yellow powder 95.6g, HPLC detection are obtained, area normalization method calculates target product content 98.78%,
External standard method calculates target product content 96.35%, and yield 96.97% calculates total yield 94.83%.
Claims (8)
1. a kind of synthesis processing method of pyrazoles disulphide is added it is characterized in that: arylpyrazole nitrile is dissolved in solvent I
Sulfur monochloride reaction is passed through dry nitrogen after reaction and blows away the hydrogen chloride generated in the reaction of part, then is passed through in ammonia
With to pH value 6.5 ~ 7, then filters pressing obtains filter cake A and filtrate A；Filter cake A is further processed to obtain target product pyrazoles curing
Object.
2. the synthesis processing method of pyrazoles disulphide according to claim 1, it is characterized in that: sulfur monochloride and aryl pyrrole
Azoles nitrile molar ratio is 1:2.01 ~ 2.30, and reaction temperature is no more than 45 DEG C.
3. the synthesis processing method of pyrazoles disulphide according to claim 1 or 2, it is characterized in that: filtrate A is as reaction
Solvent is applied.
4. the synthesis processing method of pyrazoles disulphide according to claim 1 or 2, it is characterized in that: filter cake A further locates
Reason method: being added solvent II after filter cake A is dry, after dissolving pyrazoles disulphide, then filters pressing, obtain liquor B and filter cake B；Filter cake B is dry
Dry recycling design II is recycled；Liquor B is further processed, and obtains target product.
5. the synthesis processing method of pyrazoles disulphide according to claim 4, it is characterized in that: liquor B is further processed
Method includes decrease temperature crystalline processing after concentration.
6. the synthesis processing method of pyrazoles disulphide according to claim 1 or 2, it is characterized in that: solvent I be toluene,
Carbon tetrachloride, acetonitrile, Benzene Chloride, ethyl acetate, o-dichlorohenzene, dichloroethanes, ortho-chlorotolu'ene, p-chlorotoluene, to chlorine fluoroform
The combination of one or more of benzene, p-chlorotrichlormethyl.
7. the synthesis processing method of pyrazoles disulphide according to claim 4, it is characterized in that: solvent II is N, N- diformazan
Base formamide, N, N- dimethyl acetamide, dimethyl sulfoxide, tetrahydrofuran, acetone, butanone, 2 pentanone, propione, N- methyl
The combination of one or more of pyrrolidines equal solvent.
8. the synthesis processing method of pyrazoles disulphide according to claim 1 or 2, it is characterized in that: filter cake A further locates
Reason method: the washing of filter cake room temperature, and add water and stir, it is dry after suction filtration, obtain target product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149909A (en) * | 2021-03-24 | 2021-07-23 | 台州达辰药业有限公司 | Preparation method of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethyl-phenyl) pyrazole disulfide |
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2019
- 2019-09-11 CN CN201910856787.4A patent/CN110467573A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149909A (en) * | 2021-03-24 | 2021-07-23 | 台州达辰药业有限公司 | Preparation method of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethyl-phenyl) pyrazole disulfide |
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