CN1907976A - Process for preparing 2-octyl-2H-isothiazol-3-one - Google Patents
Process for preparing 2-octyl-2H-isothiazol-3-one Download PDFInfo
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- CN1907976A CN1907976A CN 200610041116 CN200610041116A CN1907976A CN 1907976 A CN1907976 A CN 1907976A CN 200610041116 CN200610041116 CN 200610041116 CN 200610041116 A CN200610041116 A CN 200610041116A CN 1907976 A CN1907976 A CN 1907976A
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Abstract
The invention discloses a preparing method of N-positive octyl isothiazolanthrones, which comprises the following steps: adding NH4Cl/ammonia buffer and sodium disulfide in the reacting container A; dripping methyl acrylate; extracting blown liquid; adding filtrate in the sodium disulfide solution; reacting; removing water; adding anhydrous MgSO4 in the organic phase; drying; extracting to obtain dithiobolandiol methyl ester; adding dithiobolandiol methyl ester positive amino and water in the reactor B; extracting; drying to obtain disulfide-2 (N- positive octyl propionamide) white powder; adding acetic ester and disulfide-2 (N- positive octyl propionamide) in the reactor C; aerating chlorine gas; extracting white solid N- positive octyl propionamide hydrochlorate; putting hydrochlorate in the reactor C; adding acetic ester; extracting; laminating; distilling organic phase through depressing; removing acetic ester to obtain light yellow liquid.
Description
Technical field
The present invention relates to a kind of preparation method of N-n-octyl isothiazolinone.Belong to technical field of organic chemistry.
Background technology
N-n-octyl isothiazolinone is a kind of novel high-effective broad-spectrum fungicide.It is widely used in fields such as makeup, coating, tackiness agent, material of construction, weaving, fabric, health care, has efficient, low toxicity, effective drug duration is long, characteristics such as environmental sound.Find that by a large amount of literature searches preparation N-n-octyl isothiazolinone mainly is to synthesize by following steps:
Step 1, methyl acrylate and Sodium sulfhydrate reaction make the 3-mercapto-propionate,
Step 2,3-mercapto-propionate and n-octyl amine reaction make N-n-octyl-3-sulfydryl propionic acid amide,
Step 3, N-n-octyl-3-sulfydryl propionic acid amide and chlorine reaction generate N-n-octyl isothiazoline keto hydrochloride,
Step 4, above-mentioned hydrochloride add in ethyl acetate solvent in the alkali and generate N-n-octyl isothiazolinone, suction filtration, layering, get organic phase, and ethyl acetate is removed in distillation, promptly gets N-n-octyl isothiazolinone.
Prepare the 3-mercapto-propionate with Sodium sulfhydrate in the above step 1 reaction, produce a large amount of thiomethyl alcohols in the reaction process, toxicity is big, boiling point is low, flash-point is low, very easily blast, and the 3-mercapto-propionate is because of the sulfydryl instability, side reaction is big in rectifying, and yield is greatly affected; Prepare N-n-octyl-3-sulfydryl propionic acid amide by the 3-mercapto-propionate in the step 2 reaction, also because the influence of sulfydryl, side reaction is many, yield is low, the refining comparatively difficulty of product, influence quality product, and influence the quality and the yield of preparation N-n-octyl isothiazolinone in the step 3 reaction thus greatly.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, provide a kind of each step reaction steady and, respectively go on foot the preparation method of the N-n-octyl isothiazolinone that product stability is good, quality is good, yield is high, cost is low.
The object of the present invention is achieved like this: a kind of preparation method of N-n-octyl isothiazolinone is characterized in that this method comprises following processing step:
Step 1, methyl acrylate and sodium disulfide reaction generate dimethyl propionate of dithio
In reaction vessel A, add NH
4Cl/ ammoniacal liquor buffered soln and sodium disulfide solution, temperature is controlled at-10 ℃ ~ 5 ℃, and the dropwise addition of acrylic acid methyl esters dripped off in 1.5 ~ 2.5 hours, the control pH value is 10.5 ~ 11.5 in the reaction process, reaction finishes insulation 0.5 ~ 1.5 hour, and suction filtration gets brown liquid, and above-mentioned filtrate is added in the sodium sulfite solution, stirring reaction, leach precipitated impurities, the filtrate layering divides in the back organic phase of anhydrating and adds anhydrous MgSO
4Drying, suction filtration gets dimethyl propionate of dithio;
Step 2, dimethyl propionate of dithio and n-octyl amine reaction generate dithio two (N-n-octyl propionic acid amide)
Add dimethyl propionate of dithio, n-octyl amine and water in reaction vessel B, temperature is controlled at 25 ± 5 ℃, stirs 20 ± 5 hours, and is static, and suction filtration, oven dry get dithio two (N-n-octyl propionic acid amide) white powder;
Step 3, dithio two (N-n-octyl propionic acid amide) prepare N-n-octyl isothiazolinone with chlorine reaction.
In reaction vessel C, add ethyl acetate and dithio two (N-n-octyl propionic acid amide), control reaction temperature is at 0 ℃～15 ℃, fed chlorine 3 ± 0.5 hours, led to the back in 20 ± 5 ℃ of insulations 1 ~ 2 hour, suction filtration gets white solid N-n-octyl isothiazoline keto hydrochloride, N-n-octyl isothiazoline keto hydrochloride is dropped among the reaction vessel C, add ethyl acetate, stir, add NaOH and regulate PH to 6-7, suction filtration, layering, the organic phase underpressure distillation boils off ethyl acetate, get weak yellow liquid, be N-n-octyl isothiazolinone.
Advantage of the present invention is that raw material propylene acid methyl esters is easy to get, each step reaction steady and, each goes on foot, and product stability is good, quality is good, yield is high, cost is low.
Embodiment
One, the preparation of sodium disulfide
Add 200ml water, 135g sulphur powder and 46g sodium sulphite in the 500ml flask, heating up makes it dissolving, cooling, and suction filtration gets red clarifying sodium disulfide solution.
Two, the preparation of dimethyl propionate of dithio
In being housed, the 1000ml four-necked bottle of whipping appts, condenser, thermometer adds 100g NH
4Cl/ ammoniacal liquor buffered soln (3 gram ammonium chlorides, 5 gram ammonia, 92 gram water), add 380g sodium disulfide solution, temperature is controlled between-10 ℃ ~ 5 ℃, dropwise addition of acrylic acid methyl esters 150g, 1.5 dripped off in ~ 2.5 hours, the control pH value is 10.5 ~ 11.5 in the reaction process, reaction finishes insulation 0.5 ~ 1.5 hour, suction filtration gets brown liquid, above-mentioned filtrate is added in the sodium sulfite solution of 300ml 5%, stirring reaction leaches precipitated impurities, the filtrate layering divides in the back organic phase of anhydrating and adds anhydrous MgSO
4Drying, suction filtration gets dimethyl propionate of dithio.Product through gas chromatographic analysis content greater than 95%, yield 92.5%.
Three, the preparation of dithio two (N-n-octyl propionic acid amide)
In the 1000ml flask, add the 236g dimethyl propionate of dithio, the 250g n-octyl amine, 200g water, temperature is controlled at 25 ± 5 ℃, stirred 20 ± 5 hours, static, suction filtration, oven dry, get dithio two (N-n-octyl propionic acid amide) white powder, fusing point 126-129 ℃, yield 90%.
Four, the preparation of N-n-octyl isothiazolinone
In the three-necked bottle of the 1000ml that agitator, condenser, thermometer are housed, add ethyl acetate 600ml, dithio two (N-n-octyl propionic acid amide) 140g, control reaction temperature feeds chlorine 70g between 0 ℃-15 ℃, led in 3 ± 0.5 hours.Led to the back in 20 ± 5 ℃ of insulations 1 ~ 2 hour, suction filtration gets white solid N-n-octyl isothiazoline keto hydrochloride, and N-n-octyl isothiazoline keto hydrochloride is dropped in the 1000ml three-necked flask, add the 600ml ethyl acetate, stir, add NaOH and regulate PH between the 6-7, suction filtration, layering, the organic phase underpressure distillation boils off ethyl acetate, get weak yellow liquid, be N-n-octyl isothiazolinone, greater than 99%, yield is 85% through liquid chromatographic detection content.
Claims (2)
1, a kind of preparation method of N-n-octyl isothiazolinone is characterized in that this method comprises following processing step:
Step 1, methyl acrylate and sodium disulfide reaction generate dimethyl propionate of dithio
In reaction vessel A, add NH
4Cl/ ammoniacal liquor buffered soln and sodium disulfide solution, temperature is controlled at-10 ℃ ~ 5 ℃, and the dropwise addition of acrylic acid methyl esters dripped off in 1.5 ~ 2.5 hours, the control pH value is 10.5 ~ 11.5 in the reaction process, reaction finishes insulation 0.5 ~ 1.5 hour, and suction filtration gets brown liquid, and above-mentioned filtrate is added in the sodium sulfite solution, stirring reaction, leach precipitated impurities, the filtrate layering divides in the back organic phase of anhydrating and adds anhydrous MgSO
4Drying, suction filtration gets dimethyl propionate of dithio;
Step 2, dimethyl propionate of dithio and n-octyl amine reaction generate dithio two (N-n-octyl propionic acid amide)
Add dimethyl propionate of dithio, n-octyl amine and water in reaction vessel B, temperature is controlled at 25 ± 5 ℃, stirs 20 ± 5 hours, and is static, and suction filtration, oven dry get dithio two (N-n-octyl propionic acid amide) white powder;
Step 3, dithio two (N-n-octyl propionic acid amide) prepare N-n-octyl isothiazolinone with chlorine reaction.
In reaction vessel C, add ethyl acetate and dithio two (N-n-octyl propionic acid amide), control reaction temperature is at 0 ℃～15 ℃, fed chlorine 3 ± 0.5 hours, led to the back in 20 ± 5 ℃ of insulations 1 ~ 2 hour, suction filtration gets white solid N-n-octyl isothiazoline keto hydrochloride, N-n-octyl isothiazoline keto hydrochloride is dropped among the reaction vessel C, add ethyl acetate, stir, add NaOH and regulate PH to 6-7, suction filtration, layering, the organic phase underpressure distillation boils off ethyl acetate, get weak yellow liquid, be N-n-octyl isothiazolinone.
2, the preparation method of a kind of N-n-octyl isothiazolinone according to claim 1 is characterized in that NH in the step 1
4Cl/ ammoniacal liquor buffered soln is formulated by ammonium chloride, ammonia and water, and three's weight ratio is an ammonium chloride: ammonia: water=1: 1.5～1.8: 28～32, the weight ratio of itself and sodium disulfide solution is 1: 3～4.
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| CN 200610041116 CN1907976A (en) | 2006-08-04 | 2006-08-04 | Process for preparing 2-octyl-2H-isothiazol-3-one |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180819A (en) * | 2011-04-08 | 2011-09-14 | 李绍通 | 3,3'New process for synthesizing 3,3'-dithio-bispropionate |
| CN112110871A (en) * | 2020-11-03 | 2020-12-22 | 大连百傲化学股份有限公司 | Preparation method of 3-isothiazolinone compound |
| CN113582941A (en) * | 2020-04-30 | 2021-11-02 | 广州合成材料研究院有限公司 | Preparation method of 4, 5-dichloro-2-n-octyl-3-isothiazolinone |
| CN113651769A (en) * | 2021-08-31 | 2021-11-16 | 陕西中杰科仪化学科技有限公司 | Continuous production method of 2-methyl-4-isothiazoline-3-ketone |
| CN115838346A (en) * | 2022-10-08 | 2023-03-24 | 大连百傲化学股份有限公司 | Method for synthesizing N, N '-dialkyl-3, 3' -dithiodipropionamide by one-pot method |
-
2006
- 2006-08-04 CN CN 200610041116 patent/CN1907976A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180819A (en) * | 2011-04-08 | 2011-09-14 | 李绍通 | 3,3'New process for synthesizing 3,3'-dithio-bispropionate |
| CN113582941A (en) * | 2020-04-30 | 2021-11-02 | 广州合成材料研究院有限公司 | Preparation method of 4, 5-dichloro-2-n-octyl-3-isothiazolinone |
| CN113582941B (en) * | 2020-04-30 | 2023-09-08 | 广州合成材料研究院有限公司 | Preparation method of 4, 5-dichloro-2-n-octyl-3-isothiazolinone |
| CN112110871A (en) * | 2020-11-03 | 2020-12-22 | 大连百傲化学股份有限公司 | Preparation method of 3-isothiazolinone compound |
| CN113651769A (en) * | 2021-08-31 | 2021-11-16 | 陕西中杰科仪化学科技有限公司 | Continuous production method of 2-methyl-4-isothiazoline-3-ketone |
| CN113651769B (en) * | 2021-08-31 | 2023-07-28 | 陕西中杰科仪化学科技有限公司 | Continuous production method of 2-methyl-4-isothiazolin-3-ketone |
| CN115838346A (en) * | 2022-10-08 | 2023-03-24 | 大连百傲化学股份有限公司 | Method for synthesizing N, N '-dialkyl-3, 3' -dithiodipropionamide by one-pot method |
| CN115838346B (en) * | 2022-10-08 | 2024-06-04 | 大连百傲化学股份有限公司 | Method for synthesizing N, N '-dialkyl-3, 3' -dithiodipropionamide by one-pot method |
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