CN107021935B - Benzisothiazolone derivatives, preparation method and application thereof - Google Patents
Benzisothiazolone derivatives, preparation method and application thereof Download PDFInfo
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- CN107021935B CN107021935B CN201710332229.9A CN201710332229A CN107021935B CN 107021935 B CN107021935 B CN 107021935B CN 201710332229 A CN201710332229 A CN 201710332229A CN 107021935 B CN107021935 B CN 107021935B
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- 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
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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Abstract
The invention belongs to the field of chemical mildew prevention and antibiosis, and discloses a benzisothiazolone derivative, a preparation method and application thereof, wherein the derivative is prepared by substituting a compound shown as a formula (1) for halogen atoms in at least one halogenated paraffin selected from chlorinated paraffin and brominated paraffin, the content of the halogen atoms in the halogenated paraffin is 10-80 wt%, and the number of carbon atoms in the halogenated paraffin is 13-30. The benzisothiazolone derivative provided by the invention has excellent mildew-proof and bactericidal effects, does not have the VOC problem caused by solvent compounding, is not easy to run off, is not easy to be absorbed by human bodies, is environment-friendly, and saves the production cost.
Description
Technical Field
The invention relates to the field of chemical mildew prevention and bacteria resistance, in particular to a benzisothiazolone derivative, a method for preparing the benzisothiazolone derivative, the benzisothiazolone derivative prepared by the method, and application of the benzisothiazolone derivative in mildew prevention and bacteria resistance.
Background
The structural formula of the 1, 2-benzisothiazole-3-ketone compound is as follows:
wherein R is1Represents H, Cl, Br, C1-C4Alkyl group of (1).
The 1, 2-benzisothiazole-3-ketone compound has good mildew-proof and sterilization effects, but the 1, 2-benzisothiazole-3-ketone compound is utilized and dissolved by using an organic solvent for compounding, so that the production cost is greatly increased, and the VOC problem is brought.
In addition, small molecular 1, 2-benzisothiazole-3-ketone compounds are easy to lose, and the small molecular bactericide is easy to be absorbed by human bodies.
CN201210552080.2 utilizes N-substituted 1, 2-benzisothiazole-3-ketone compounds containing double bonds to polymerize with monomers containing double bonds to obtain macromolecular 1, 2-benzisothiazole-3-ketone compounds, but N-substituted 1, 2-benzisothiazole-3-ketone compounds containing double bonds are difficult to obtain and have high production cost. In the actual production process, in order to obtain the double-bond-containing N-substituted-1, 2-benzisothiazol-3-one compound, the 1, 2-benzisothiazol-3-one compound is firstly required to react with double-bond-containing halogenated alkene, the obtained double-bond-containing N-substituted 1, 2-benzisothiazol-3-one compound is refined, and then the double-bond-containing N-substituted 1, 2-benzisothiazol-3-one compound is polymerized with a double-bond-containing monomer to obtain the macromolecular 1, 2-benzisothiazol-3-one compound. The preparation method in the prior art has the defects of multiple steps, high cost and more three wastes.
CN201010155166.2 relates to a benzisothiazolone compound and application thereof, in particular to a technical scheme of the benzisothiazolone compound or the benzisothiazolone compound mixed with resin as a marine antifouling agent. However, the benzisothiazolone compound or the mixture of the benzisothiazolone compound and the resin provided by the prior art is easy to run off in the application process and is easy to be absorbed by the human body.
Disclosure of Invention
The invention aims to overcome the defects of VOC (volatile organic Compounds) problem, easy loss and easy absorption by human bodies in the compounding of antifouling agents formed by benzisothiazolone compounds in the prior art, and provides a novel benzisothiazolone derivative which can overcome the defects and has good mildew-proof and bactericidal effects.
The compound containing benzisothiazolone compounds provided by the prior art has the defect of easy loss, and the macromolecular 1, 2-benzisothiazolone-3-ketone compound obtained by polymerizing the double-bond-containing N-substituted 1, 2-benzisothiazolone-3-ketone compound and the double-bond-containing monomer has the defects of complex preparation method and high production cost. The inventor of the invention unexpectedly discovers in research that substances which are obtained by performing substitution reaction on halogenated paraffin with 10-80 wt% of halogen atom and a benzisothiazolone compound and contain structural units of the benzisothiazolone compound and the halogenated paraffin can have excellent mildew-proof and sterilization effects, and simultaneously avoid the problem of VOC (volatile organic compound) caused by compounding solvents, and the macromolecular substances containing the structural units of the benzisothiazolone compound and the halogenated paraffin are not easy to lose and can not be absorbed by human bodies, so that the preparation method is environment-friendly, simple and low in cost. Based on this, the technical solution of the present invention has been completed.
In a first aspect, the present invention provides a benzisothiazolone derivative, which is prepared by substituting a compound represented by formula (1) for a halogen atom in at least one halogenated paraffin selected from chlorinated paraffin and brominated paraffin, wherein the halogen atom content in the halogenated paraffin is 10 to 80% by weight, and the number of carbon atoms in the halogenated paraffin is 13 to 30,
wherein, in the formula (1), R is H, Cl, Br or C1-C4Alkyl group of (1).
In a second aspect, the present invention provides a process for preparing benzisothiazolone derivatives comprising: in the presence of an organic solvent, performing nucleophilic substitution reaction on at least one halogenated paraffin selected from chlorinated paraffin and brominated paraffin and a compound shown in a formula (1) under an alkaline condition, wherein the content of halogen atoms in the halogenated paraffin is 10-80 wt%, and the number of carbon atoms in the halogenated paraffin is 13-30,
wherein, in the formula (1), R is H, Cl, Br or C1-C4Alkyl group of (1).
In a third aspect, the present invention provides benzisothiazolone derivatives prepared by the method of the second aspect.
In a fourth aspect, the present invention provides the use of the benzisothiazolone derivatives described in the first and third aspects in mildew resistance and bacteria resistance.
The benzisothiazolone derivative provided by the invention has excellent mildew-proof and bactericidal effects, does not have the VOC problem caused by compounding with a solvent, is not easy to run off, is not easy to be absorbed by a human body, is environment-friendly, and saves the production cost.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a benzisothiazolone derivative, which is prepared by substituting a compound represented by formula (1) for a halogen atom in at least one halogenated paraffin selected from chlorinated paraffin and brominated paraffin, wherein the halogen atom content in the halogenated paraffin is 10 to 80% by weight, and the number of carbon atoms in the halogenated paraffin is 13 to 30,
wherein, in the formula (1), R is H, Cl, Br or C1-C4Alkyl group of (1).
Preferably, in formula (1), R is H, Cl, Br, methyl, ethyl, isopropyl or tert-butyl. More preferably, in formula (1), R is H, Cl, Br or methyl.
The inventors of the present invention have found that when R in formula (1) is H, Cl, Br or methyl, in particular, benzisothiazolone derivatives obtained by substituting a compound represented by formula (1) for a halogen atom in a halogenated paraffin having 13 to 30 carbon atoms and a halogen atom content of 42 wt%, 52 wt% or 72 wt% are more excellent in mold-proofing and bactericidal properties.
Preferably, the molecular weight of the benzisothiazolone derivatives of the present invention is 300-10000.
In a second aspect, the present invention provides a process for preparing benzisothiazolone derivatives comprising: in the presence of an organic solvent, performing nucleophilic substitution reaction on at least one halogenated paraffin selected from chlorinated paraffin and brominated paraffin and a compound shown in a formula (1) under an alkaline condition, wherein the content of halogen atoms in the halogenated paraffin is 10-80 wt%, and the number of carbon atoms in the halogenated paraffin is 13-30,
wherein, in the formula (1), R is H, Cl, Br or C1-C4Alkyl group of (1).
In the second aspect of the present invention, in formula (1), preferably R is H, Cl, Br, methyl, ethyl, isopropyl, or tert-butyl; more preferably, in formula (1), R is H, Cl, Br or methyl.
Preferably, in the second aspect of the present invention, the halogenated paraffin and the compound represented by the formula (1) are used in a weight ratio of 1: (0.5 to 10); more preferably, the mass ratio of the halogenated paraffin to the compound represented by the formula (1) is 1: (1-10).
Preferably, the alkaline condition is formed by one or more alkaline substances selected from sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate.
Preferably, the weight ratio of the alkaline substance to the compound shown in the formula (1) is (0.25-3): 1.
preferably, the organic solvent is one or more selected from the group consisting of Dimethylformamide (DMF), acetonitrile, dimethyl sulfoxide, tetrahydrofuran, acetone, 1, 3-dimethyl-2-imidazolidinone, and hexamethylphosphoric triamide.
Preferably, the conditions of the nucleophilic substitution reaction include: the temperature is 50-120 ℃, and the time is 2-50 h.
The process of the present invention may also comprise subjecting the product obtained after the nucleophilic substitution reaction to a post-treatment conventional in the art, such as washing with water, decolorizing, and the like. The decolorization can be carried out by adding activated carbon and/or activated clay. Also, the amount of activated carbon and/or activated clay added for the decolorization is not particularly limited, and those skilled in the art can obtain the amount of activated carbon and/or activated clay based on the purpose of the decolorization in combination with the conventional technical means in the art.
In a third aspect, the present invention provides benzisothiazolone derivatives prepared by the method of the second aspect.
In a fourth aspect, the invention provides the application of the benzisothiazolone derivatives described in the first and third aspects in mildew resistance and bacteria resistance.
The benzisothiazolone derivative provided by the invention also has the following specific advantages:
1. large molecular weight, not easy to be absorbed by human body;
2. the mildew-proof and bactericidal performance is excellent;
3. the problem of solvent compounding does not exist, so that the problem of VOC is avoided, and the cost is saved;
4. is environment-friendly and has low toxicity;
5. the preparation method is simple.
The present invention will be described in detail below by way of examples.
In the following examples, various raw materials used are commercially available ones unless otherwise specified.
Example 1
185.5g of 5-chloro-1, 2-benzisothiazol-3-one and 80g of brominated paraffin (the halogen atom content is 40-44 wt%, which is purchased from Wuyi Diwang chemical auxiliary agent, Ltd.) are subjected to reflux reaction for 10h in the presence of 450g of DMF and 107g of sodium carbonate, and after the reaction is finished, the reaction product is washed with water (unreacted raw material 5-chloro-1, 2-benzisothiazol-3-one is washed away) to obtain a crude product, and the crude product is decolored to obtain benzisothiazol-one derivative M1, wherein the yield (based on 5-chloro-1, 2-benzisothiazol-3-one, the same applies below) is 92%.
Example 2
In the presence of 400g of DMF and 80g of lithium carbonate, 165g of 5-methyl-1, 2-benzisothiazol-3-one and 90g of chlorinated paraffin (halogen atom content of 50-54% by weight, available from Yangzhou Keli chemical Co., Ltd.) were subjected to reflux reaction for 15 hours, and after the reaction was completed, water was washed (unreacted raw material 5-methyl-1, 2-benzisothiazol-3-one was washed away) to obtain a crude product, which was decolorized to obtain benzisothiazol-one derivative M2 with a yield of 93%.
Example 3
In the presence of 500g of acetonitrile and 139g of potassium carbonate, 151g of 1, 2-benzisothiazol-3-one and 80g of chlorinated paraffin (having a halogen atom content of 68 to 72% by weight and available from Yangzhou Kokoku chemical Co., Ltd.) were subjected to a reflux reaction for 20 hours, and after the reaction was completed, washed with water (unreacted raw material, 1, 2-benzisothiazol-3-one, was washed away) to obtain a crude product, which was then decolorized to obtain benzisothiazol-one derivative M3 with a yield of 92%.
Example 4
This example was carried out in a similar manner to example 1, except that the compound represented by the formula (1) of this example was 5-isopropyl-1, 2-benzisothiazol-3-one, specifically:
193g of 5-isopropyl-1, 2-benzisothiazol-3-one and 80g of brominated paraffin (same as in example 1) were subjected to a reflux reaction in the presence of 450g of DMF and 107g of sodium carbonate for 10 hours, and after the reaction was completed, washed with water (unreacted raw material 5-isopropyl-1, 2-benzisothiazol-3-one was washed away) to obtain a crude product, which was decolorized to obtain benzisothiazol derivative M4 with a yield of 88%.
Example 5
This example was carried out in a similar manner to example 2, except that the compound represented by the formula (1) of this example was 5-tert-butyl-1, 2-benzisothiazol-3-one, specifically:
207g of 5-tert-butyl-1, 2-benzisothiazol-3-one and 80g of chlorinated paraffin (same as in example 2) were subjected to a reflux reaction in the presence of 400mL of DMF and 80g of lithium carbonate for 15 hours, and after the completion of the reaction, washed with water (unreacted raw material 5-tert-butyl-1, 2-benzisothiazol-3-one was washed away) to obtain a crude product, which was decolorized to obtain benzisothiazolinone derivative M5 in a yield of 92%.
Example 6
This example was carried out in a similar manner to example 3, except that the compound represented by the formula (1) of this example was 5-ethyl-1, 2-benzisothiazol-3-one, specifically:
179g of 5-ethyl-1, 2-benzisothiazol-3-one and 80g of chlorinated paraffin (same as in example 3) were subjected to a reflux reaction in the presence of 500g of acetonitrile and 139g of potassium carbonate for 20 hours, and after the completion of the reaction, washed with water (unreacted raw material 5-ethyl-1, 2-benzisothiazol-3-one was washed away) to obtain a crude product, which was decolorized to obtain benzisothiazolinone derivative M6 in a yield of 91%.
Comparative example 1
This comparative example was conducted in a similar manner to example 1 except that 80g of polyvinyl chloride (having a halogen atom content of 57% by weight) was used in place of 80g of the brominated paraffin wax in example 1.
The rest is the same as in example 1.
Benzisothiazolone derivative DM1 was obtained in 34% yield.
Test example
The benzisothiazolone derivatives obtained in the preceding examples and comparative examples were tested for their fungicidal efficacy using the method provided in example 4 of CN201210552080.2, specifically:
120g of benzisothiazolone derivatives obtained in each example, 10g of iron oxide red, 10g of titanium dioxide, 20g of talcum powder, 50g of toluene and 10g of dioctyl phthalate are put into a basket type dispersion grinder and ground at the rotating speed of 2000r/min, so that the particle size of the coating is smaller than 20 mu m, and the coating containing the benzisothiazolone derivatives can be obtained.
Respectively coating a polyacrylate resin commodity coating and a coating containing the benzisothiazolone derivative on a low-carbon steel plate with the thickness of 250 multiplied by 150 multiplied by 1.5 mm;
after being fixed according to the requirements of GB5370-2007 'antifouling paint sample plate shallow sea immersion test method', the sample plate is placed at 1m under water in the Weihai stone island sea area;
it was then observed at 1 month, 2 months, 3 months, 5 months and 6 months, respectively.
As a result, the fouling area ratios are shown in Table 1.
TABLE 1
The results show that the benzisothiazolone derivatives provided by the invention have excellent mildew-proof and bactericidal effects, and the benzisothiazolone derivatives have large molecular weight, are not easy to run off and are not easy to be absorbed by human bodies.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A benzisothiazolone derivative is prepared by substituting a compound shown as a formula (1) for a halogen atom in at least one halogenated paraffin selected from chlorinated paraffin and brominated paraffin, wherein the content of the halogen atom in the halogenated paraffin is 42-80 wt%, and the number of carbon atoms in the halogenated paraffin is 13-30,
wherein, in the formula (1), R is H, Cl or C1-C4The alkyl group of (a) is,
wherein the dosage weight ratio of the halogenated paraffin to the compound shown in the formula (1) is 1: (1-10).
2. The derivative according to claim 1, wherein, in formula (1), R is H, Cl, methyl, ethyl, isopropyl or tert-butyl.
3. The derivative according to claim 2, wherein, in formula (1), R is H, Cl or methyl.
4. A method for preparing benzisothiazolone derivatives is characterized in that: in the presence of an organic solvent, performing nucleophilic substitution reaction on at least one halogenated paraffin selected from chlorinated paraffin and brominated paraffin and a compound shown in a formula (1) under an alkaline condition, wherein the content of halogen atoms in the halogenated paraffin is 42-80 wt%, and the number of carbon atoms in the halogenated paraffin is 13-30,
wherein, in the formula (1), R is H, Cl or C1-C4The alkyl group of (a) is,
wherein the dosage weight ratio of the halogenated paraffin to the compound shown in the formula (1) is 1: (1-10).
5. The process according to claim 4, wherein, in formula (1), R is H, Cl, methyl, ethyl, isopropyl or tert-butyl.
6. The process according to claim 5, wherein, in formula (1), R is H, Cl or methyl.
7. The method according to any one of claims 4 to 6, wherein the alkaline condition is formed by one or two or more alkaline substances selected from sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate.
8. The method according to claim 7, wherein the basic substance is used in an amount of (0.25 to 3) by weight to the compound represented by the formula (1): 1.
9. the method according to any one of claims 4 to 6, wherein the organic solvent is one or more selected from the group consisting of dimethylformamide, acetonitrile, dimethyl sulfoxide, tetrahydrofuran, acetone, 1, 3-dimethyl-2-imidazolidinone, and hexamethylphosphoric triamide.
10. The method of any one of claims 4-6, wherein the conditions of the nucleophilic substitution reaction comprise: the temperature is 50-120 ℃, and the time is 2-50 h.
11. Benzisothiazolone derivatives prepared by the process according to any one of claims 4 to 10.
12. Use of the benzisothiazolone derivatives according to any one of claims 1 to 3 and 11 for combating fungi and bacteria.
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| US3012039A (en) * | 1958-03-14 | 1961-12-05 | Ici Ltd | 2-p-chlorobenzyl-1, 2-benzisothiazolone |
| JPS58177982A (en) * | 1982-04-09 | 1983-10-18 | Green Cross Corp:The | Benzoisothiazoline derivative and antitrichophytic |
| JPS58177915A (en) * | 1982-04-12 | 1983-10-18 | Green Cross Corp:The | Antithrombotic agent |
| EP0542489A3 (en) * | 1991-11-14 | 1993-08-04 | Rohm And Haas Company | Microbicidal compositions comprising 3-isothiazolones and polycations |
| GB9304903D0 (en) * | 1993-03-10 | 1993-04-28 | Zeneca Ltd | Compounds,preparation and use |
| IN177608B (en) * | 1994-03-10 | 1997-02-08 | Ici India Ltd | |
| CN102234251B (en) * | 2010-04-20 | 2013-04-24 | 中国科学院烟台海岸带研究所 | Benzisothiazolinone compound and application thereof |
| CN103044351B (en) * | 2012-12-06 | 2015-07-29 | 青岛大学 | A kind of N-replaces propylene acyloxy methyl benzisothiazolinone functional monomer and preparation method thereof |
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