CN108997181A - A kind of prosulfocarb and its synthetic method - Google Patents
A kind of prosulfocarb and its synthetic method Download PDFInfo
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- CN108997181A CN108997181A CN201810987275.7A CN201810987275A CN108997181A CN 108997181 A CN108997181 A CN 108997181A CN 201810987275 A CN201810987275 A CN 201810987275A CN 108997181 A CN108997181 A CN 108997181A
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- prosulfocarb
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- benzyl chloride
- sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/02—Monothiocarbamic acids; Derivatives thereof
- C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
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Abstract
The invention discloses a kind of prosulfocarb and its synthetic methods, the prosulfocarb includes following raw material: sulfuric acid, ammonium thiocyanate solution, water, di-n-propylamine and benzyl chloride, its synthetic method is the following steps are included: step 1, ammonium thiocyanate solution is added dropwise while stirring into sulfuric acid, obtains carbonyl sulfur gas and ammonium hydrogen sulfate；Step 2, water and di-n-propylamine are mixed, is stirred, benzyl chloride is added dropwise when being passed through carbonyl sulfur gas for cooling, reacts, obtains prosulfocarb semifinished product and hydrogen chloride gas；Step 3, the pH to 9-10 of prosulfocarb semifinished product is adjusted, heat preservation then cools down and adjusts pH to 5-6, stands, and removes lower water, obtains upper layer finished product；Upper layer finished product is dried, filters, obtains prosulfocarb.98% or more, yield raw material in 97% or more, synthetic method is easy to get the content of gained prosulfocarb, at low cost, easy to operate, easy to control, and by-product is less, environmental-friendly.
Description
Technical field
The present invention relates to the synthesis of fine chemical product and applied technical fields, and in particular to a kind of prosulfocarb and its synthesis
Method.
Background technique
Prosulfocarb (prosulfocarb) chemical name s- benzyl dipropyl thiocarbamate is thiocarbamic acid
Esters selectivity inner sucting conduction type soil processing herbicide.Prosulfocarb is chloropropham, and the mechanism of action is rouge
Class synthetic inhibitor, be mainly used for prevent and treat wheatland broadleaf weeds, can sensibility gramineae weed seedling, by thiocarbamate
The symptom of class compound harm is that seedling is dark green, plant distortion, inhibits the growth of seedling and root, and leaf is prevented to go out from bud scale
Come, for the plant with the above true leaf of 4~5 leaves, severe necrosis occurs in separate living tissue and its surrounding, soil treatment is tested and ground
Study carefully the result shows that, " depth " protective effect is depended on to the selectivity being administered before gramineous crop bud, analyzes result and biometric
The result shows that, since the leaching of prosulfocarb is low, therefore to prevent from contacting with gramineous crop bud in soil calmly.
Prosulfocarb category thiocarbamate herbicide can be used for transplanted rice field, live streaming field weeding, can effectively prevent and kill off
Gramineae weed, sedge weed and broadleaf weeds, as grass family Echinochloa, Sprangletop, Ma Tang category, setaria, Paspalum,
Herba eleusines indicae etc.；Annual and perennial nutgrass flatsedge such as Cyperus, Eleocharis, genus fimbristylis and firefly Lin, broadleaf weeds such as ludwigia,
Sagittaria, field grass category, Pontederiaceae category, flower Lin category and Drilgrass etc., especially have special efficacy to Monochoria vaginalis.
In the synthesis technology of existing prosulfocarb, the higher cost of synthesis, and foul smell can be generated in synthesis process, it pollutes
The content of environment, resulting prosulfocarb is lower, and yield is relatively low.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a kind of prosulfocarb and its synthetic method,
98% or more, yield raw material in 97% or more, synthetic method is easy to get the content of gained prosulfocarb, at low cost, operation letter
It is single, it is easy to control, and by-product is less, it is environmental-friendly.
In order to achieve the above object, the present invention is achieved by the following scheme.
(1) a kind of prosulfocarb, including following raw material: sulfuric acid, ammonium thiocyanate solution, water, di-n-propylamine and benzyl chloride.
Preferably, the dosage of the raw material are as follows: 800-1200 parts of sulfuric acid, 300-380 parts of ammonium thiocyanate solution, water 25-35
Part, 200-204 parts of di-n-propylamine and 120-132 parts of benzyl chloride.
It is further preferred that the dosage of the raw material are as follows: 1000 parts of sulfuric acid, 340 parts of ammonium thiocyanate solution, 30 parts of water, two
202 parts and 126 parts of benzyl chloride of n-propylamine.
Preferably, the concentration of the sulfuric acid is 70-90%, and the concentration of the ammonium thiocyanate solution is 40-60%.
(2) a kind of synthetic method of prosulfocarb, comprising the following steps:
Step 1, ammonium thiocyanate solution is added dropwise while stirring into sulfuric acid, obtains carbonyl sulfur gas and ammonium hydrogen sulfate；
Step 2, water and di-n-propylamine being mixed, is stirred, benzyl chloride is added dropwise when being passed through the carbonyl sulfur gas in cooling,
Reaction, obtains prosulfocarb semifinished product and hydrogen chloride gas；
Step 3, the pH to 9-10 of the prosulfocarb semifinished product is adjusted, is kept the temperature, is then cooled down and adjust pH to 5-6, is stood,
Lower water is removed, upper layer finished product is obtained；The upper layer finished product is dried, filters, obtains prosulfocarb.
Preferably, in step 1, the revolving speed of the stirring is 95 revs/min.
Preferably, in step 1, the dropping temperature of the ammonium thiocyanate solution is 80-85 DEG C, the dropwise addition of ammonium thiocyanate solution
Time is 5.5-6.5 hours.
Preferably, in step 2, the revolving speed of the stirring is 95 revs/min.
Preferably, in step 2, the cooling is to be cooled to 8-10 DEG C.
Preferably, in step 2, the benzyl chloride is added dropwise after being passed through 0.8-1.2 minutes in the carbonyl sulfur gas；Benzyl chloride
Time for adding is 5.8-6.2 hours, and the dropping temperature of benzyl chloride is 8-10 DEG C.
Preferably, in step 2, the time of the reaction is 4-6 minutes.
Preferably, in step 3, use concentration for 40-50% sodium hydroxide solution adjust prosulfocarb semifinished product pH to
9-10。
Preferably, in step 3, the temperature of the heat preservation is 35-45 DEG C, and the time of heat preservation is 35-45 minutes.
Preferably, in step 3, the cooling is to be cooled to 23-25 DEG C.
Preferably, in step 3, the adjusting pH to 5-6 is that concentration is used to adjust for the sulfuric acid of 30-40%.
Preferably, in step 3, the time of the standing is 25-35 minutes.
Preferably, in step 3, the drying is dried using anhydrous magnesium sulfate, and the dry time is 5-6 hours.
Preferably, in step 3, the vacuum degree of the suction filtration is-(0.085~0.090) MPa, and the time of suction filtration is 10-
15 minutes.
Compared with prior art, the invention has the benefit that
For the content of the resulting prosulfocarb of the present invention 98% or more, yield raw material in 97% or more, synthetic method is easy
, it is at low cost, it is easy to operate, it is easy to control, and by-product is less, it is environmental-friendly.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
It will be appreciated that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the invention.
Embodiment 1
A kind of synthetic method of prosulfocarb, comprising the following steps:
Step 1, the sulfuric acid 1000g that concentration is 80% is added into the four-hole bottle of 1000mL, then into sulfuric acid 95 revs/min
The ammonium thiocyanate solution 340g that concentration is 50% is added dropwise in the speed of clock while stirring, under the conditions of temperature is 82.5 DEG C in 6 hours
Ammonium thiocyanate solution is dripped, carbonyl sulfur gas and ammonium hydrogen sulfate are obtained, specifically as shown in formula (1).
NH4SCN+H2O+H2SO4→COS+NH2HSO4... ... formula (1)
Step 2,30g water and 202g di-n-propylamine are added in the four-hole bottle of 500mL, is stirred with 95 revs/min of revolving speed
Mixing, is cooled to 9 DEG C, starts that benzyl chloride is added dropwise when being passed through carbonyl sulfur gas 1 minute, is added dropwise when being passed through the carbonyl sulfur gas
Benzyl chloride, drips 126g benzyl chloride in 6 hours, and benzyl chloride stops being passed through carbonyl sulfur gas after dripping, in processing step 1
The waste water of generation, the reaction was continued 5 minutes, obtains prosulfocarb semifinished product and hydrogen chloride gas；Specifically as shown in formula (2).
Step 3, concentration is used to adjust the pH to 10 of prosulfocarb semifinished product for 40% sodium hydroxide solution, in 40 DEG C of conditions
Lower heat preservation 40 minutes, is then cooled to 25 DEG C, and uses concentration for 30% sulphur acid for adjusting pH to 5 and kept not at 30 minutes
Become, stand 30 minutes, removes lower water, obtain upper layer finished product；The anhydrous magnesium sulfate that 5g is added into upper layer finished product is dried, with
95 revs/min of revolving speed stirs 5 hours, then filters 10 minutes under the conditions of vacuum degree is -0.085MPa, and obtaining content is 98%
Prosulfocarb finished product 250g, yield 97%.
Embodiment 2
A kind of synthetic method of prosulfocarb, comprising the following steps:
Step 1, the sulfuric acid 1200g that concentration is 90% is added into the four-hole bottle of 1000mL, then into sulfuric acid 95 revs/min
The ammonium thiocyanate solution 380g that concentration is 60% is added dropwise in the speed of clock while stirring, under the conditions of temperature is 80 DEG C in 5.5 hours
Ammonium thiocyanate solution is dripped, carbonyl sulfur gas and ammonium hydrogen sulfate are obtained.
Step 2,25g water and 204g di-n-propylamine are added in the four-hole bottle of 500mL, is stirred with 95 revs/min of revolving speed
Mixing, is cooled to 9 DEG C, starts that benzyl chloride is added dropwise when being passed through carbonyl sulfur gas 0.8 minute, drips when being passed through the carbonyl sulfur gas
Add benzyl chloride, 132g benzyl chloride is dripped in 6.2 hours, benzyl chloride stops being passed through carbonyl sulfur gas, processing step after dripping
The waste water generated in rapid 1, the reaction was continued 5 minutes, obtains prosulfocarb semifinished product and hydrogen chloride gas.
Step 3, concentration is used to adjust the pH to 10 of prosulfocarb semifinished product for 50% sodium hydroxide solution, in 45 DEG C of conditions
Lower heat preservation 45 minutes, is then cooled to 23 DEG C, and uses concentration for 40% sulphur acid for adjusting pH to 5 and kept not at 30 minutes
Become, stand 30 minutes, removes lower water, obtain upper layer finished product；The anhydrous magnesium sulfate that 5g is added into upper layer finished product is dried, with
95 revs/min of revolving speed stirs 5 hours, then filters 15 minutes under the conditions of vacuum degree is -0.085MPa, obtaining content is
98.2% prosulfocarb finished product, yield 97.4%.
Embodiment 3
A kind of synthetic method of prosulfocarb, comprising the following steps:
Step 1, the sulfuric acid 800g that concentration is 70% is added into the four-hole bottle of 1000mL, then into sulfuric acid 95 revs/min
The ammonium thiocyanate solution 300g that concentration is 40% is added dropwise in the speed of clock while stirring, under the conditions of temperature is 85 DEG C in 6.5 hours
Ammonium thiocyanate solution is dripped, carbonyl sulfur gas and ammonium hydrogen sulfate are obtained.
Step 2,35g water and 200g di-n-propylamine are added in the four-hole bottle of 500mL, is stirred with 95 revs/min of revolving speed
Mixing, is cooled to 8 DEG C, starts that benzyl chloride is added dropwise when being passed through carbonyl sulfur gas 1.2 minutes, drips when being passed through the carbonyl sulfur gas
Add benzyl chloride, 120g benzyl chloride is dripped in 5.8 hours, benzyl chloride stops being passed through carbonyl sulfur gas, processing step after dripping
The waste water generated in rapid 1, the reaction was continued 6 minutes, obtains prosulfocarb semifinished product and hydrogen chloride gas.
Step 3, concentration is used to adjust the pH to 9.5 of prosulfocarb semifinished product for 45% sodium hydroxide solution, in 35 DEG C of items
35 minutes are kept the temperature under part, is then cooled to 24 DEG C, and uses concentration for 35% sulphur acid for adjusting pH to 5.5 and was kept at 30 minutes
It is constant, 35 minutes are stood, lower water is removed, obtains upper layer finished product；The anhydrous magnesium sulfate that 5g is added into upper layer finished product is dried,
It is stirred 6 hours, is then filtered 12.5 minutes under the conditions of vacuum degree is -0.087MPa, obtaining content is with 95 revs/min of revolving speed
98.5% prosulfocarb finished product, yield 97.4%.
Embodiment 4
A kind of synthetic method of prosulfocarb, comprising the following steps:
Step 1, the sulfuric acid 1200g that concentration is 90% is added into the four-hole bottle of 1000mL, then into sulfuric acid 95 revs/min
The ammonium thiocyanate solution 300g that concentration is 40% is added dropwise in the speed of clock while stirring, under the conditions of temperature is 80 DEG C in 6.5 hours
Ammonium thiocyanate solution is dripped, carbonyl sulfur gas and ammonium hydrogen sulfate are obtained.
Step 2,25g water and 200g di-n-propylamine are added in the four-hole bottle of 500mL, is stirred with 95 revs/min of revolving speed
Mixing, is cooled to 10 DEG C, starts that benzyl chloride is added dropwise when being passed through carbonyl sulfur gas 1 minute, drips when being passed through the carbonyl sulfur gas
Add benzyl chloride, 126g benzyl chloride is dripped in 6 hours, benzyl chloride stops being passed through carbonyl sulfur gas, processing step 1 after dripping
The waste water of middle generation, the reaction was continued 4 minutes, obtains prosulfocarb semifinished product and hydrogen chloride gas.
Step 3, concentration is used to adjust the pH to 9 of prosulfocarb semifinished product for 40% sodium hydroxide solution, in 35 DEG C of conditions
Lower heat preservation 45 minutes, is then cooled to 25 DEG C, and uses concentration for 30% sulphur acid for adjusting pH to 6 and kept not at 30 minutes
Become, stand 25 minutes, removes lower water, obtain upper layer finished product；The anhydrous magnesium sulfate that 5g is added into upper layer finished product is dried, with
95 revs/min of revolving speed stirs 5.5 hours, then filters 10 minutes under the conditions of vacuum degree is -0.090MPa, obtaining content is
98.7% prosulfocarb finished product, yield 97.9%.
In above embodiments, hydrogen chloride gas direct emission goes out, and sodium hydroxide solution is added and adjusts pH to 9-10, neutralizes anti-
Excessive carbonyl sulfur gas in answering；Sulphur acid for adjusting pH is added to 5-6, the prosulfocarb sodium salt generated after sodium hydroxide will be added and convert
At prosulfocarb, the anhydrous magnesium sulfate of addition is used to dry the moisture in prosulfocarb finished product, prevents prosulfocarb from aoxidizing.
Although the present invention is described in detail with a general description of the specific embodiments in this specification,
But on the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.
Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed model
It encloses.
Claims (10)
1. a kind of prosulfocarb, which is characterized in that including following raw material: sulfuric acid, ammonium thiocyanate solution, water, di-n-propylamine and chlorination
Benzyl.
2. prosulfocarb according to claim 1, which is characterized in that the dosage of the raw material are as follows: 800-1200 parts of sulfuric acid, sulphur
300-380 parts of cyanic acid ammonium salt solution, 25-35 parts of water, 200-204 parts of di-n-propylamine and 120-132 parts of benzyl chloride.
3. prosulfocarb according to claim 2, which is characterized in that the dosage of the raw material are as follows: 1000 parts of sulfuric acid, thiocyanic acid
340 parts of ammonium salt solution, 30 parts of water, 202 parts of di-n-propylamine and 126 parts of benzyl chloride.
4. a kind of synthetic method of prosulfocarb, which comprises the following steps:
Step 1, ammonium thiocyanate solution is added dropwise while stirring into sulfuric acid, obtains carbonyl sulfur gas and ammonium hydrogen sulfate；
Step 2, water and di-n-propylamine being mixed, is stirred, benzyl chloride is added dropwise when being passed through the carbonyl sulfur gas for cooling, it reacts,
Obtain prosulfocarb semifinished product and hydrogen chloride gas；
Step 3, the pH to 9-10 of the prosulfocarb semifinished product is adjusted, is kept the temperature, is then cooled down and adjust pH to 5-6, is stood, is removed
Lower water obtains upper layer finished product；The upper layer finished product is dried, filters, obtains prosulfocarb.
5. the synthetic method of prosulfocarb according to claim 4, which is characterized in that in step 1, the ammonium thiocyanate solution
Dropping temperature be 80-85 DEG C, the time for adding of ammonium thiocyanate solution is 5.5-6.5 hours.
6. the synthetic method of prosulfocarb according to claim 4, which is characterized in that in step 2, the carbonyl sulfur gas is logical
The benzyl chloride is added dropwise after entering 0.8-1.2 minutes；The time for adding of benzyl chloride is 5.8-6.2 hours, the dropping temperature of benzyl chloride
It is 8-10 DEG C.
7. the synthetic method of prosulfocarb according to claim 4, which is characterized in that in step 2, the time of the reaction is
4-6 minutes.
8. the synthetic method of prosulfocarb according to claim 4, which is characterized in that in step 3, use concentration for 40-
50% sodium hydroxide solution adjusts the pH to 9-10 of prosulfocarb semifinished product；The temperature of the heat preservation be 35-45 DEG C, heat preservation when
Between be 35-45 minutes.
9. the synthetic method of prosulfocarb according to claim 4, which is characterized in that in step 3, the cooling is to be cooled to
23-25℃；The adjusting pH to 5-6 is that concentration is used to adjust for the sulfuric acid of 30-40%.
10. the synthetic method of prosulfocarb according to claim 4, which is characterized in that in step 3, the time of the standing
It is 25-35 minutes；The drying is dried using anhydrous magnesium sulfate, and the dry time is 5-6 hours.
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| CN201810987275.7A CN108997181B (en) | 2018-08-28 | 2018-08-28 | Prosulfocarb and synthesis method thereof |
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| CN201810987275.7A CN108997181B (en) | 2018-08-28 | 2018-08-28 | Prosulfocarb and synthesis method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685334A (en) * | 2020-12-28 | 2022-07-01 | 南通泰禾化工股份有限公司 | Preparation method of prosulfocarb |
| CN116751146A (en) * | 2023-06-21 | 2023-09-15 | 韩城森绿环保新能源有限公司 | Method for preparing prosulfocarb by using coking gas desulfurization and decyanation waste liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697402A1 (en) * | 1994-08-19 | 1996-02-21 | Monsanto Europe S.A./N.V. | Manufacturing process for the production of prosulfocarb |
-
2018
- 2018-08-28 CN CN201810987275.7A patent/CN108997181B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697402A1 (en) * | 1994-08-19 | 1996-02-21 | Monsanto Europe S.A./N.V. | Manufacturing process for the production of prosulfocarb |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685334A (en) * | 2020-12-28 | 2022-07-01 | 南通泰禾化工股份有限公司 | Preparation method of prosulfocarb |
| CN114685334B (en) * | 2020-12-28 | 2024-05-14 | 南通泰禾化工股份有限公司 | Preparation method of prosulfocarb |
| CN116751146A (en) * | 2023-06-21 | 2023-09-15 | 韩城森绿环保新能源有限公司 | Method for preparing prosulfocarb by using coking gas desulfurization and decyanation waste liquid |
| CN116751146B (en) * | 2023-06-21 | 2024-01-26 | 韩城森绿环保新能源有限公司 | Method for preparing prosulfocarb by using coking gas desulfurization and decyanation waste liquid |
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