CN104230839A - Method for synthesizing N-substitued benzo-isothiazolone derivative - Google Patents
Method for synthesizing N-substitued benzo-isothiazolone derivative Download PDFInfo
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- CN104230839A CN104230839A CN201410495192.8A CN201410495192A CN104230839A CN 104230839 A CN104230839 A CN 104230839A CN 201410495192 A CN201410495192 A CN 201410495192A CN 104230839 A CN104230839 A CN 104230839A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
Abstract
The invention discloses a method for synthesizing an N-substitued benzo-isothiazolone derivative. The method comprises the following steps: using 2, 2'-dithiodibenzoic acid and triphosgene as raw materials to carry out acylating chlorination, reacting 2, 2'-dithiodibenzoyl chloride with an amine compound to obtain an amide compound, and then performing disproportionation cyclization reaction on the amide compound and an oxidant in a micro-channel reactor under alkaline conditions to obtain the N-substitued benzo-isothiazolone derivative. The synthesizing method has the advantages of 98% above selectivity, 62% above raw material conversion rate, 54% above yield rate, 99% above product purity, strong technical path operability, safe and simple operation process, stable product quality and high yield rate and is suitable for industrial production.
Description
Technical field
The present invention relates to the synthetic method that a kind of N-replaces benzo isothiazolinone derivatives.
Background technology
Isothiazolinone compounds is the novel high-effective broad-spectrum fungicide of a class, has the advantages such as efficient, low toxicity, duration of efficacy are long, environmentally safe, is therefore widely deployed and is applied to medicine, agricultural chemicals and industrial circle.Good kill algae bacteriostatic activity because this compounds has, also have broad application prospects in green marine antifoulant.
Both at home and abroad replace the synthesis report of benzo isothiazolinone derivatives seldom about N-, at present report be laboratory synthetic method, and industrialized production process there is not been reported.Existing laboratory synthetic method mainly contains three routes.Article three, route all with 2,2 '-phenyl disulfide formic acid for raw material.
Route 1:[Li Yu unicorn etc., South China Normal University's journal (natural science edition), 1997 (4): 53-57.]
Route 2:[side is forever diligent etc., chemistry world, 2009 (6): 361-363]
Route 3:[Tonne Peter, et al; Canadian Patent, O.Z.0050/37522,1990-06-05.]
Wherein route one and route two all will use bromine for raw material, cause larger danger and pollution to production process, serious to equipment corrosion, are therefore difficult to suitability for industrialized production.Although route three need not use bromine, and raw materials cost is lower, be applicable to large-scale industrial production, but find in test, the yield of this route is lower, especially when N substituting group is molecular chain longer derivative, yield is lower, and therefore, it is the technical problem being badly in need of solving that the N-designing optimization replaces benzo isothiazolinone derivatives synthetic route.
Summary of the invention
Technical problem to be solved by this invention is to provide the synthetic method that a kind of N-replaces benzo isothiazolinone derivatives; need to use by force, easily absorb water deliquescence, sulfur oxychloride that raw material availability is low of pungency to carry out acidylate and produce acyl chlorides to overcome in prior art; use bromine to carry out cystine linkage scission of link, cyclization generates corrodibility hydrogen bromide, it is the shortcoming that the derivative yield of long-chain is low that still reaction produces N substituting group.
Technical conceive of the present invention is such:
With 2; 2 '-phenyl disulfide formic acid, triphosgene are raw material; 2 are produced through acylation reaction; 2 '-phenyl disulfide formyl chloride; produce 2; 2 '-phenyl disulfide formyl chloride and aminated compounds react produces 2; 2 '-phenyl disulfide Carbox amide; the micro passage reaction of strengthening reaction is utilized to make amides and oxygenant carry out disproportionation annulation in the basic conditions; utilize the heat transfer of micro passage reaction excellence, mass transfer condition; improve the transformation efficiency of raw material and the selectivity of reaction, highly selective, with high yield synthesis N-replace benzo isothiazolinone derivatives.
In order to solve the problems of the technologies described above, main technical schemes of the present invention is as follows:
N-replaces a synthetic method for benzo isothiazolinone derivatives, comprises the steps:
1) 2,2 '-phenyl disulfide formic acid is dissolved in benzene kind solvent, control temperature-5 ~ 5 DEG C, was added drop-wise in the mixing solutions of triphosgene, catalyzer and benzene kind solvent in 2 ~ 3 hours; Then, reaction solution is warming up to 80 ~ 120 DEG C, stirring reaction 2 ~ 4 hours, reaction terminates decompression and steams 2,2 '-phenyl disulfide formyl chloride.
2) by 2,2 '-phenyl disulfide formyl chloride is dissolved in benzene kind solvent, be added drop-wise in the mixing solutions of aminated compounds, catalyzer and benzene kind solvent under room temperature, 80 ~ 120 DEG C are warming up to, stirring reaction 4 ~ 6 hours, through washing after dropwising, dry, remove solvent under reduced pressure, obtain 2,2 '-phenyl disulfide Carbox amide.
3) by 2,2 '-phenyl disulfide Carbox amide, alkali lye and benzene kind solvent are uniformly mixed, then above-mentioned mixing solutions and oxygenant are passed into micro passage reaction respectively, control temperature of reaction 50 ~ 80 DEG C, obtain target product N-through purifying after reaction solution circulation primary and replace benzo isothiazolinone derivatives, mother liquor reenters micro passage reaction after testing afterwards and carries out circulating reaction.
Further, step 1) described in 2, the mol ratio of 2 '-phenyl disulfide formic acid and catalyzer is 1:0.05 ~ 0.2, mol/mol.
Step 1) described in 2, the mass ratio of 2 '-phenyl disulfide formic acid and total benzene kind solvent is 1:2 ~ 5, g/g.
Step 1) described in catalyzer be pyridine, the derivative of pyridine or triethylamine,
Again, step 2) described in 2, the mol ratio of 2 '-phenyl disulfide formyl chloride and aminated compounds is 1:2 ~ 4, mol/mol.
Step 2) described in aminated compounds be aniline or anils.
Step 3) described in micro passage reaction, 2, the throughput ratio of 2 '-phenyl disulfide Carbox amide and oxygenant is 1:1 ~ 3, (g/min)/(ml/min).
Again, step 3) in oxygenant be 15 ~ 65wt% hydrogen peroxide, nitrogen containing 0.1 ~ 10% ozone, air or the nitrogen containing 1 ~ 15% oxygen.
Step 3) in 2, the mass ratio of 2 '-phenyl disulfide Carbox amide and benzene kind solvent is 1:3 ~ 5.
Step 3) in micro passage reaction 2, the throughput ratio of 2 '-phenyl disulfide Carbox amide and basic solution is 1:0.2 ~ 0.4, (g/min)/(g/min).
Step 3) described in basic solution be 0.1 ~ 1.0wt% sodium hydroxide solution or 0.1 ~ 1.0wt% potassium hydroxide solution.
Preferably, step 1), 2), 3) described in benzene kind solvent be toluene, dimethylbenzene, ethylbenzene or chlorobenzene.
After testing, the N-that the synthetic method adopting N-of the present invention to replace benzo isothiazolinone derivatives obtains replaces the selectivity > 98% of benzo isothiazolinone derivatives, raw material 2, the transformation efficiency > 62% of 2 '-phenyl disulfide Carbox amide, yield > 54%, N-replaces the purity > 99% of benzo isothiazolinone derivatives.
Beneficial effect of the present invention:
The present invention uses triphosgene to carry out acyl chloride reaction, overcome sulfur oxychloride feed intake inconvenience, easily to absorb water the shortcomings such as deliquescence, raw material availability be low, simple to operate, reaction solution corrodibility is low, can reduce the requirement to equipment, improves reaction operability; Use micro passage reaction strengthening disproportionation, ring closure reaction, single step reaction obtains target product, improve reaction preference, improve raw material availability, make reaction preference > 98%, raw material 2, the transformation efficiency > 62% of 2 '-phenyl disulfide Carbox amide; Synthetic method reaction temperature and, be easy to control, constant product quality, yield is high, is suitable for suitability for industrialized production.
Embodiment
Below by specific embodiment, the present invention is described further, but embodiment does not limit the scope of the invention.
Embodiment 1
Step 1): be furnished with thermometer, agitator, reflux condensing tube device, and in 500ml tetra-mouthfuls of reaction flasks of constant pressure funnel, add 59.4g (0.2mol) triphosgene, 100g dimethylbenzene, 6.1g (0.06mol) triethylamine, stirring and dissolving, hierarchy of control temperature is at-5 ~ 5 DEG C, by 91.8g (0.3mol) 2, 2 '-phenyl disulfide formic acid is dissolved in 200g dimethylbenzene, then it is slowly at the uniform velocity added dropwise in above-mentioned triphosgene mixing solutions, time for adding controls at 2 hours, then 100 DEG C are warming up to, stirring reaction 3 hours, 2 are obtained through underpressure distillation, 2 '-phenyl disulfide formyl chloride 86.6g, yield is 84.2%, purity 98.4%.
Step 2): be furnished with thermometer, agitator, reflux condensing tube device, and in 500ml tetra-mouthfuls of reaction flasks of constant pressure funnel, add 63.0g (0.6mol) aniline, 120ml dimethylbenzene, 50.5g (0.5mol) triethylamine, stirring and dissolving, hierarchy of control temperature is at-5 ~ 5 DEG C, slowly at the uniform velocity instillation is dissolved with 86.6g (0.25mol) 2, the 150ml xylene solution of 2 '-phenyl disulfide formyl chloride, time for adding controls at 1 hour, then 110 DEG C are warming up to, stirring reaction 4 hours, after having reacted, with 100ml distilled water wash twice, dry, distillation is except desolventizing and lower-boiling impurity, obtain 2 of 103.2g, 2 '-phenyl disulfide dimethylbenzene crude amide, yield is 90.5%, purity 89.7% (HPLC).
Step 3): by step 2) 103.2g (purity 89.7% produced, HPLC) (0.20mol) 2,2 '-phenyl disulfide dimethylbenzene acid amides is dissolved in 500ml dimethylbenzene (being labeled as reaction solution 1), preparation massfraction 0.5% sodium hydroxide solution 500ml (being labeled as reaction solution 2), air steel cylinder, output pressure controls 0.05MPa (being labeled as reaction gas 3).Arranging reaction solution 1 output speed is 5g/min, reaction solution 2 output speed is 1.5g/min, the output speed of reaction gas 3 is 10ml/min, to access in healthy and free from worry G1 micro passage reaction two-way pipeline after reaction solution 1 and reaction solution 2 pre-mixing respectively with reaction gas 3, temperature of reaction is 120 DEG C, the reaction solution of discharging in reactor leaves standstill, separatory, oxidant gas form is overflowed, basic solution is gone out through separatory, the organic phase obtained is product, the mixture of solvent and raw material acid amides, detect through GC, raw material 2, 2 '-phenyl disulfide dimethylbenzene acid amides transformation efficiency is 62.7%, selectivity 98.5%, organic phase washed with water twice, separatory, decolouring, dry, distillation is except desolventizing, sherwood oil recrystallization, obtain 49.3g white solid powder shape N-phenylisothiazole quinoline ketone, yield is 54.3%, purity 99.3% (HPLC).Mother liquor is through concentration and recovery recrystallization solvent, and substrate is unreacted 2,2 '-phenyl disulfide dimethylbenzene acid amides and a small amount of N-phenylisothiazole quinoline ketone, again prepares reaction solution 1, then enter micro passage reaction and carry out circulating reaction after GC analyzes.
Embodiment 2
Step 1): be furnished with thermometer, agitator, reflux condensing tube device, and in 500ml tetra-mouthfuls of reaction flasks of constant pressure funnel, add 59.4g (0.2mol) triphosgene, 150g chlorobenzene, 2.4g (0.03mol) pyridine, stirring and dissolving, hierarchy of control temperature is at-5-5 DEG C, by 91.8g (0.3mol) 2, 2 '-phenyl disulfide formic acid is dissolved in 220g chlorobenzene, then it is slowly at the uniform velocity added dropwise in above-mentioned triphosgene mixing solutions, time for adding controls at 2 hours, then 110 DEG C are warming up to, stirring reaction 3 hours, underpressure distillation obtains 2, 2 '-phenyl disulfide formyl chloride 89.2g, yield is 86.7%, purity 98.9%.
Step 2): be furnished with thermometer, agitator, reflux condensing tube device, and in 500ml tetra-mouthfuls of reaction flasks of constant pressure funnel, add 79.6g (0.624mol) 4-chloroaniline, 120ml dimethylbenzene, 41.1g (0.52mol) pyridine, stirring and dissolving, hierarchy of control temperature is at 0-5 DEG C, slowly at the uniform velocity instillation is dissolved with 89.2g (0.26mol) 2, the 150ml xylene solution of 2 '-phenyl disulfide formyl chloride, time for adding controls at 1 hour, then 110 DEG C are warming up to, stirring reaction 4 hours, after having reacted, with 100ml distilled water wash twice, dry, distillation is except desolventizing and lower-boiling impurity, obtain 2 of 126.3g, 2 '-phenyl disulfide dimethylbenzene crude amide, yield is 92.5%, purity 88.3% (HPLC).
Step 3): by step 2) 126.3g (purity 88.3% produced, HPLC) (0.21mol) 2,2 '-phenyl disulfide dimethylbenzene acid amides is dissolved in 600ml dimethylbenzene (being labeled as reaction solution 1), preparation massfraction 0.5% potassium hydroxide solution 500ml (being labeled as reaction solution 2), oxygen bottle (oxygen purity 10%) after nitrogen dilution, output pressure controls 0.05MPa (being labeled as reaction gas 3).Arranging reaction solution 1 output speed is 5g/min, reaction solution 2 output speed is 1.5g/min, the output speed of reaction gas 3 is 15ml/min, to access in healthy and free from worry G1 micro passage reaction two-way pipeline after reaction solution 1 and reaction solution 2 pre-mixing respectively with reaction gas 3, temperature of reaction is 120 DEG C, the reaction solution of discharging in reactor leaves standstill, separatory, oxidant gas form is overflowed, basic solution is gone out through separatory, the organic phase obtained is product, the mixture of solvent and raw material acid amides, detect through GC, raw material 2, 2 '-phenyl disulfide dimethylbenzene acid amides transformation efficiency is 64.5%, selectivity 98.2%, organic phase washed with water twice, separatory, decolouring, dry, distillation is except desolventizing, sherwood oil recrystallization, obtain 70.0g white solid powder shape N-phenylisothiazole quinoline ketone, yield is 56.1%, purity 99.5% (HPLC).Reclaim recrystallization solvent after mother liquor concentrations, substrate is unreacted 2,2 '-phenyl disulfide dimethylbenzene acid amides and a small amount of N-phenylisothiazole quinoline ketone, again prepares reaction solution 1, then enter micro passage reaction and carry out circulating reaction after GC analyzes.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (10)
1. N-replaces a synthetic method for benzo isothiazolinone derivatives, comprises the steps:
1) 2,2 '-phenyl disulfide formic acid is dissolved in benzene kind solvent, control temperature-5 ~ 5 DEG C, was added drop-wise in the mixing solutions of triphosgene, catalyzer and benzene kind solvent in 2 ~ 3 hours; Then, reaction solution is warming up to 80 ~ 120 DEG C, stirring reaction 2 ~ 4 hours, reaction terminates decompression and steams 2,2 '-phenyl disulfide formyl chloride.
2) by 2,2 '-phenyl disulfide formyl chloride is dissolved in benzene kind solvent, be added drop-wise in the mixing solutions of aminated compounds, catalyzer and benzene kind solvent under room temperature, 80 ~ 120 DEG C are warming up to, stirring reaction 4-6 hour, through washing after dropwising, dry, remove benzene kind solvent under reduced pressure, obtain 2,2 '-phenyl disulfide Carbox amide.
3) by 2,2 '-phenyl disulfide Carbox amide, alkali lye and benzene kind solvent are uniformly mixed, then above-mentioned mixing solutions and oxygenant are passed into micro passage reaction respectively, control temperature of reaction 50 ~ 80 DEG C, obtain target product N-through purifying after reaction solution circulation primary and replace benzo isothiazolinone derivatives, mother liquor reenters micro passage reaction after testing afterwards and carries out circulating reaction.
2. N-according to claim 1 replaces the synthetic method of benzo isothiazolinone derivatives, it is characterized in that, step 1) described in 2, the mol ratio of 2 '-phenyl disulfide formic acid and catalyzer is 1:0.05 ~ 0.2, mol/mol, step 1) described in catalyzer be pyridine, the derivative of pyridine or triethylamine.
3. N-according to claim 1 replaces the synthetic method of benzo isothiazolinone derivatives, it is characterized in that, step 1) described in 2, the mass ratio of 2 '-phenyl disulfide formic acid and total benzene kind solvent is 1:2 ~ 5, g/g.
4. N-according to claim 1 replaces the synthetic method of benzo isothiazolinone derivatives, it is characterized in that, step 2) described in 2, the mol ratio of 2 '-phenyl disulfide formyl chloride and aminated compounds is 1:2 ~ 4, mol/mol; Step 2) described in aminated compounds be aniline or anils.
5. N-according to claim 1 replaces the synthetic method of benzo isothiazolinone derivatives, it is characterized in that, step 3) described in micro passage reaction, 2, the throughput ratio of 2 '-phenyl disulfide Carbox amide and oxygenant is 1:1 ~ 3, (g/min)/(ml/min).
6. N-replaces the synthetic method of benzo isothiazolinone derivatives according to claim 1 or 5, it is characterized in that, step 3) described in oxygenant be 15 ~ 65wt% hydrogen peroxide, nitrogen containing 0.1 ~ 10wt% ozone, air or the nitrogen containing 1 ~ 15wt% oxygen.
7. N-according to claim 1 replaces the synthetic method of benzo isothiazolinone derivatives, it is characterized in that, step 3) described in 2, the mass ratio of 2 '-phenyl disulfide Carbox amide and benzene kind solvent is 1:3 ~ 5, g/g.
8. N-according to claim 1 replaces the synthetic method of benzo isothiazolinone derivatives, it is characterized in that, step 3) described in micro passage reaction 2, the throughput ratio of 2 '-phenyl disulfide Carbox amide and basic solution is 1:0.2 ~ 0.4, (g/min)/(g/min).
9. N-according to claim 1 or 8 replaces the synthetic method of benzo isothiazolinone derivatives, it is characterized in that, step 3) described in basic solution be 0.1 ~ 1.0wt% sodium hydroxide solution or 0.1 ~ 1.0wt% potassium hydroxide solution.
10. N-according to claim 1 or 3 or 7 replaces the synthetic method of benzo isothiazolinone derivatives, it is characterized in that, step 1), 2), 3) described in benzene kind solvent be toluene, dimethylbenzene, ethylbenzene or chlorobenzene.
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| WO2018040745A1 (en) * | 2016-08-29 | 2018-03-08 | 江苏扬农化工集团有限公司 | Method for synthesizing terephthaloyl chloride through continuous flow in micro-channel reactor |
| CN111440102A (en) * | 2020-04-26 | 2020-07-24 | 大连凯飞化学股份有限公司 | Preparation method of dithiodibenzoamide compound |
| CN111574472A (en) * | 2020-06-30 | 2020-08-25 | 大连百傲化学股份有限公司 | Synthesis method of 1, 2-benzisothiazolin-3-ketone compound |
| CN113801025A (en) * | 2021-10-18 | 2021-12-17 | 南京先进生物材料与过程装备研究院有限公司 | Method for carrying out reductive amination reaction by using microchannel reaction device |
| CN114478333A (en) * | 2022-01-28 | 2022-05-13 | 宜春新龙智慧高科有限公司 | Synthetic method and application of 2, 2' -dithio-dibenzoyl formamide |
| CN114478990A (en) * | 2022-01-19 | 2022-05-13 | 美瑞新材料股份有限公司 | High-biocompatibility body antibacterial and mildewproof TPU material and preparation method thereof |
| CN114933527A (en) * | 2022-05-25 | 2022-08-23 | 东南大学 | Method for continuously synthesizing o-methylbenzoyl chloride in microchannel |
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| WO2018040745A1 (en) * | 2016-08-29 | 2018-03-08 | 江苏扬农化工集团有限公司 | Method for synthesizing terephthaloyl chloride through continuous flow in micro-channel reactor |
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| CN111574472B (en) * | 2020-06-30 | 2022-03-08 | 大连百傲化学股份有限公司 | Synthesis method of 1, 2-benzisothiazolin-3-ketone compound |
| CN111574472A (en) * | 2020-06-30 | 2020-08-25 | 大连百傲化学股份有限公司 | Synthesis method of 1, 2-benzisothiazolin-3-ketone compound |
| CN113801025A (en) * | 2021-10-18 | 2021-12-17 | 南京先进生物材料与过程装备研究院有限公司 | Method for carrying out reductive amination reaction by using microchannel reaction device |
| CN113801025B (en) * | 2021-10-18 | 2023-08-25 | 南京先进生物材料与过程装备研究院有限公司 | Method for carrying out reductive amination reaction by adopting microchannel reaction device |
| CN114478990A (en) * | 2022-01-19 | 2022-05-13 | 美瑞新材料股份有限公司 | High-biocompatibility body antibacterial and mildewproof TPU material and preparation method thereof |
| CN114478990B (en) * | 2022-01-19 | 2024-04-05 | 美瑞新材料股份有限公司 | High-biocompatibility bulk antibacterial mildew-proof TPU material and preparation method thereof |
| CN114478333A (en) * | 2022-01-28 | 2022-05-13 | 宜春新龙智慧高科有限公司 | Synthetic method and application of 2, 2' -dithio-dibenzoyl formamide |
| CN114933527A (en) * | 2022-05-25 | 2022-08-23 | 东南大学 | Method for continuously synthesizing o-methylbenzoyl chloride in microchannel |
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