CN111253335B - New synthetic method of N-substituted benzisothiazolin-3-one derivative - Google Patents

New synthetic method of N-substituted benzisothiazolin-3-one derivative Download PDF

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CN111253335B
CN111253335B CN202010179096.8A CN202010179096A CN111253335B CN 111253335 B CN111253335 B CN 111253335B CN 202010179096 A CN202010179096 A CN 202010179096A CN 111253335 B CN111253335 B CN 111253335B
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葛前建
林诗锐
汤文杰
吴红辉
张永彬
樊斌
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Zhejiang Yangfan New Materials Co ltd
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    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
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Abstract

The invention discloses a novel synthesis method of an N-substituted benzisothiazolin-3-one derivative. The method comprises the steps of taking dithiosalicylic acid derivatives and sulfur as raw materials, introducing chlorine or bromine to obtain halogenated thiobenzoyl halide derivatives, then preferably dropwise adding a mixed solution of primary amine and tertiary amine, and performing ring closure reaction to obtain the N-substituted benzisothiazole-3-ketone. The method disclosed by the invention has the advantages of simple process, safety and controllability and easiness in industrial mass production.

Description

New synthetic method of N-substituted benzisothiazolin-3-one derivative
Technical Field
The invention relates to a synthetic method, in particular to a novel synthetic method of an N-substituted benzisothiazolin-3-one derivative.
Background
Isothiazolinones are a class of efficient broad-spectrum bactericides, the most well-known commercial representatives being kathon, DCOIT, OIT, etc., which are widely used for antiseptic sterilization in cosmetics, paper making, metal cutting fluids, paints, coatings, plastic products. With the long-term use of isothiazolinones, resistance to some bacteria is caused. Phenyl-containing N-substituted benzisothiazolin-3-ones find wide application as well known products such as BIT, BBIT, MBIT and the like.
The synthesis method is concerned by large companies at home and abroad for a long time, and more synthesis methods are reported at present. However, for various reasons, many synthetic methods have more or less some drawbacks, resulting in poor product quality or difficulty in industrialization.
According to literature reports, N-substituted benzisothiazolin-3-ones are generally prepared by the following methods:
the method comprises the following steps: US2014/316141 uses 60% industrial sodium sulfide in NMP, high temperature nitrogen is blown to take out water at 190 ℃, then o-chlorobenzamide is added dropwise, sodium thiophenol is obtained through reaction, and then hydrogen peroxide is used for oxidation under alkaline condition to obtain BIT product, the yield is 80.8%.
Figure BDA0002411891220000011
The second method is as follows: sano Tomohumi et al, synyhesis,10 (2004), uses dithiosalicylic acid as a raw material, reacts with n-butylamine through dithiosalicylyl chloride to form amide, and then closes the ring to obtain the product BBIT.
Figure BDA0002411891220000012
And a third method: chinese patent CN104130206, CN107098870, etc. uses BIT as raw material, and adopts substitution reaction to obtain a series of N-substituted benzisothiazolinone derivatives. However, U.S. patent No. 8884024 of the same process illustrates that there are more byproducts to do so, by-products: the ratio of the products was 45:55.
Figure BDA0002411891220000013
The method four: sulfamethod patent EP2687520 describes the preparation of BIT from sulfonyl chloride after the formation of a thioether from o-chlorobenzonitrile and sodium alkyl mercaptide.
Figure BDA0002411891220000021
And a fifth method: the preparation of BBIT from the sulfonyl chloride with 2-alkylthio benzoylbutylamine is commonly used in China.
Figure BDA0002411891220000022
The method six: pietka-Ottlik et al, molecular, vol.15, 11, 2010, P8214-8288. And (3) cyclizing the 2-formyl chloride phenylthio chloride (CTBC) with various amines to obtain the N-substituted benzisothiazolinone compound.
Figure BDA0002411891220000023
In view of the above, there are more or less various problems associated with the methods reported in the literature. The first difficulty of the method is that the residual moisture has a great influence on the reaction, the dehydration of sodium sulfide is very important, the reaction temperature is very high, and the industrialization is difficult to realize due to the use of NMP with high boiling point; the second method is that the raw materials in each step are solid, and the raw materials are difficult to dissolve in the conventional solvent, so that the reaction process is complex; too much byproduct is produced in the method III; the fourth and fifth methods are generally adopted in the industrialization at present, but the sodium salt of the malodorous alkyl mercaptan is needed, and the low-boiling halohydrocarbon is released in the reaction, so that the method is unfavorable in the aspect of environmental protection; the sixth difficulty of the method is that raw materials such as thionyl chloride and sulfonyl chloride are commonly used at present, the raw materials are sensitive to air humidity, the environment of a use site is poor, a large amount of sulfur dioxide is discharged, and the pressure on environmental protection is high.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a novel synthesis method of the N-substituted benzisothiazolin-3-one derivative which has the advantages of simpler process, high yield and low pollution and is easy for industrial production.
The invention solves the technical problems by adopting the technical scheme that: a novel synthesis method of N-substituted benzisothiazolin-3-one derivatives, which comprises the following steps: adding organic solvent to make benzene ring have substituent R 1 Is prepared from dithiosalicylic acid derivative, sulfur and X 2 To obtain halogenated thiobenzoyl halide derivatives; then the solvent is removed under reduced pressure, and the R band is added dropwise 2 Primary amines of radicals or with R 2 And (3) reacting and closing the ring of the mixed solution of primary amine and tertiary amine of the group to obtain the N-substituted benzisothiazol-3-ketone.
Figure BDA0002411891220000031
Preferably, X 2 Is chlorine or bromine.
Preferably, R 1 R represents 11 、OR 11 、COR 11 、SR 11 、SO 2 R 11 、CO-N(R 11 )R 12 、NHR 11 、N(R 11 )R 12 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 11 And R is 12 Each independently represents hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, aldehyde, C 1 -C 10 Straight or branched alkyl, alkenyl, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkyl alkyl, C 7 -C 20 Aralkyl of (C) 6 -C 20 Aryl, C of (2) 2 -C 20 Heterocyclic groups of (C), and-CH in alkyl 2 Optionally interrupted by-O-, -S-, -SO 2 -NH-substitution, provided that any two of the linked-CH 2 -cannot be substituted simultaneously.
Preferably, R 2 R represents 21 、OR 21 、COR 21 、SR 21 、SO2R 21 、CO-N(R 21 )R 22 、NHR 21 、N(R 21 )R 22 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 21 And R is 22 Each independently is represented by hydrogen, C 1 -C 10 Straight or branched alkyl, alkenyl, C 3 -C 10 Cycloalkyl, C 4 -C 20 Cycloalkyl alkyl, C 7 -C 20 Aralkyl of (C) 6 -C 20 Aryl, C of (2) 2 -C 20 Heterocyclic groups of (C), and-CH in alkyl 2 Optionally interrupted by-O-, -S-, -SO 2 -NH-substitution, provided that any two of the linked-CH 2 -cannot be substituted simultaneously.
Preferably, R 1 The radicals may be in any position on the phenyl ring and R is in different positions on the phenyl ring 1 May represent different groups.
Preferably, the organic solvent is one or more of benzene, toluene, xylene, chlorobenzene, dichloromethane, dichloroethane and tetrachloroethylene, and the dosage of the organic solvent is 1-10 times, preferably 3-5 times, of the weight of the dithiosalicylic acid, so that the product can be dissolved and clear, and waste is avoided.
Preferably, the chlorine or bromine is measured by a flowmeter or a weighing method, and the dosage is 0.5-4 times of the mole amount of the dithiosalicylic acid derivative; the temperature of the reaction by introducing chlorine or bromine is 10-100 ℃, preferably 40-70 ℃. Too low a temperature results in slow reaction and too high a temperature results in more by-products.
Preferably, the sulfur is used in an amount of 0.7 to 1.5 times the molar amount of the dithiosalicylic acid derivative, and the molar ratio of the dithiosalicylic acid derivative to the chlorine is 1:2 to 1:4.
Preferably, the temperature of the dropwise addition of the amine mixture is from 10 to 80 ℃, preferably from 30 to 60 ℃, the amine amount being the total molar amount of primary amine and tertiary amine: molar amount of halothiobenzoyl halide derivative = 2-4.
The same quality of 2-formyl chloride phenylthio chloride (CTBC) is produced, if the sulphur, chlorine chlorination scheme is used, only 1 sulphur dioxide and 2 hydrogen chloride are produced, whereas if the method six in the background art is used, 3 sulphur dioxide and 2 hydrogen chloride are produced.
Figure BDA0002411891220000041
The invention has the beneficial effects that: the method abandons the sulfoxide chloride and sulfonyl chloride which are easy to hydrolyze, improves the atom economy in the reaction, greatly reduces the discharge amount of sulfur dioxide and hydrogen chloride gas, has cheaper raw materials, high activity and higher product content, and has extremely high economic benefit.
Detailed Description
The invention is further described below:
example 1
30.6 g of dithiosalicylic acid, 3.5 g of sulfur, 200ml of toluene is added, the temperature is raised to 40 ℃, 28.4 g of chlorine is introduced until the reaction liquid becomes clear, TLC (thin layer chromatography) detects that the raw material is converted, the solvent is removed under reduced pressure, 44.5 g of yellow oily substance is obtained, and the yellow oily substance is solidified into yellow solid after cooling. Yield 99%, content 97%; this is intermediate CTBC.
Example 2
30.6 g of dithiosalicylic acid, 2.3 g of sulfur, 200ml of chlorobenzene is added, the temperature is raised to 60 ℃, 18.5 g of chlorine is introduced, TLC detects the disappearance of the raw material, and the solvent is removed under reduced pressure to obtain 37.6 g of yellow solid, the yield is 90%, and the content is 95%, and the yellow solid is intermediate CTBC.
Example 3
30.6 g of dithiosalicylic acid, 2.9 g of sulfur, 200ml of dichloroethane are added, the temperature is raised to 50 ℃, 21.5 g of chlorine gas is introduced, the reaction solution becomes clear, and the solvent is removed under reduced pressure to obtain 40.2 g of yellow solid with 96 percent of yield and 97 percent of content, which is CTBC.
Example 4
30.6 g of dithiosalicylic acid, 4.8 g of sulfur, 200ml of tetrachloroethylene is added, the temperature is raised to 70 ℃ and 23.2 g of chlorine is introduced, the solution becomes clear, the solvent is removed under reduced pressure, 43.5 g of CTBC is obtained, and the yield is 99% and the content is 98%.
Example 5
20.7 g of CTBC prepared in examples 1-4 is taken, 100ml of dichloroethane is added for dissolving, the temperature is raised to 60 ℃, 15 g of ammonia gas is introduced for reaction for 3 hours. 30ml of water is added for washing for 3 times, dichloroethane is removed under reduced pressure, and then ethanol is used for recrystallization, so that pale yellow powder with the content of 98% and the yield of 84% is obtained. The reaction product was 1, 2-benzisothiazolin-3-one.
Figure BDA0002411891220000051
Example 6
Taking 20.7 g of CTBC prepared in examples 1-4, dissolving with 150ml of toluene, and heating to 55 ℃;11.2 g of methylamine gas was introduced until the reaction was completed. Washing with 50ml water for 3 times, removing part of toluene, cooling and crystallizing to obtain white powder with the content of 98% and the yield of 86%. The product is N-methyl benzisothiazolinone.
Figure BDA0002411891220000052
Example 7
Taking 20.7 g of CTBC prepared in examples 1-4, dissolving with 100ml of dichloromethane, and heating to 35 ℃; after 7.2 g of isopropylamine and 22.3 g of triethylamine were mixed, the mixture was slowly dropped into a CTBC dichloromethane solution and reacted for 6 hours. Washing with 50ml water for 3 times, removing part of dichloromethane, cooling and crystallizing to obtain white powder with 97% content and 79% yield. The product was N-isopropylbenzisothiazolinone.
Figure BDA0002411891220000053
Example 8
Taking 20.7 g of CTBC prepared in examples 1-4, dissolving with 100ml of chlorobenzene, and heating to 40 ℃;9.4 g of n-butylamine and 17.4 g of pyridine were mixed and then slowly dropped into the CTBC chlorobenzene solution to react for 5 hours. Washing with 50ml of water for 3 times and removing chlorobenzene to obtain reddish brown oily liquid with 96 percent of content and 90 percent of yield, wherein the product is N-N-butyl-1, 2-benzisothiazolin-3-one.
Figure BDA0002411891220000054
Example 9
Taking 20.7 g of CTBC prepared in examples 1-4, dissolving with 150ml of benzene, and heating to 45 ℃; after 10.2 g of aniline and 26.6 g of N, N-dimethylaniline were mixed, the mixture was slowly dropped into the CTBC benzene solution and reacted for 5 hours. Washing 3 times with 50ml of water and removing chlorobenzene gave a reddish brown oily liquid, content 95%, yield 75%. The product was N-phenyl-1, 2-benzisothiazolin-3-one.
Figure BDA0002411891220000061
Example 10
Taking 20.7 g of CTBC prepared in examples 1-4, dissolving with 150ml of xylene, and heating to 55 ℃;11.2 g of benzylamine and 29.6 g of N, N-dimethylbenzylamine were mixed and then slowly dropped into the CTBC xylene solution to react for 5.5 hours. Washing 3 times with 50ml of water, and removing xylene gave a yellow oily liquid, content 97%, yield 87%. The product was N-benzyl-1, 2-benzisothiazolin-3-one.
Figure BDA0002411891220000062
Example 11
Taking 20.7 g of CTBC prepared in examples 1-4, dissolving with 150ml of tetrachloroethylene, and heating to 60 ℃; 45.6 g of n-octylamine was slowly dropped into CTBC tetrachloroethylene solution and reacted for 4 hours. Washing 3 times with 50ml of water, removing the xylenes gave a brown oily liquid, content 98%, yield 88%. The product was N-N-octyl-1, 2-benzisothiazolin-3-one.
Figure BDA0002411891220000063
Example 12
20.7 g of CTBC prepared in examples 1-4 was taken and dissolved in 150ml of toluene, and 45.6 g of isooctylamine was slowly dropped into the CTBC toluene solution at 25℃for 5.5 hours. Washing 3 times with 50ml of water and removing toluene gave a pale yellow oily liquid, content 97%, yield 86%, the product was N-isooctyl-1, 2-benzisothiazolin-3-one.
Figure BDA0002411891220000064
Example 13
The CTBC prepared in examples 1-4 was taken as 20.7 g, dissolved in 200ml of toluene, and 9.9 g of cyclohexylamine and 40 g of 20% aqueous base were mixed at 45℃to slowly drop CTBC toluene into cyclohexane for reaction for 5.5 hours. Washing 3 times with 50ml of water, removing toluene to obtain a pale yellow oily liquid, the content of which is 97%, the yield of which is 89%, and the product is N-cyclohexyl-1, 2-benzisothiazolin-3-one.
Figure BDA0002411891220000071
Example 14
20.7 g of CTBC prepared in examples 1-4 was taken and dissolved in 200ml of toluene, 5.7 g of allylamine and 40 g of 20% liquid base were mixed at 45℃and CTBC toluene was slowly dropped into allylamine to react for 5.5 hours. Washing 3 times with 50ml of water, toluene removal gave a pale yellow oily liquid, content 94%, yield 84%. The product was N-allyl-1, 2-benzisothiazolin-3-one.
Figure BDA0002411891220000072
Example 15
20.7 g of CTBC prepared in examples 1-4 was taken and dissolved in 200ml of toluene, 6.0 g of cyclopropylamine and 16.5 g of pyridine were mixed at 60℃and CTBC toluene was slowly dropped into cyclopropylamine to react for 7 hours. Washing 3 times with 50ml of water, toluene removal gave a pale yellow oily liquid, content 97%, yield 85%. The product was N-cyclopropyl-1, 2-benzisothiazolin-3-one.
Figure BDA0002411891220000073
The invention has the innovation point that CTBC is prepared by utilizing the synergistic effect of chlorine and sulfur, and various N-substituted benzisothiazolin-3-one derivatives are synthesized without any purification and are applied downwards. Compared with other existing industrialized technologies, the method has the advantages of higher atom economy, simple and convenient operation and greater emission reduction significance.
In addition to the embodiments described above, other embodiments of the invention are possible. All technical schemes formed by equivalent substitution or equivalent transformation fall within the protection scope of the invention.

Claims (5)

1. A synthetic method of N-substituted benzisothiazolin-3-one derivatives comprises the following steps:
adding organic solvent to make benzene ring have substituent R 1 Is prepared from dithiosalicylic acid derivative, sulfur and X 2 To obtain halogenated thiobenzoyl halide derivativeA living being; then the solvent is removed under reduced pressure, and the R band is added dropwise 2 Primary amines of radicals or with R 2 The mixed solution of primary amine and tertiary amine of the group is reacted for closing the ring to obtain N-substituted benzisothiazole-3-ketone;
Figure FDA0004178760540000011
X 2 is chlorine or bromine;
R 1 is hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, C 1 -C 10 Straight or branched alkyl of (a);
R 2 is hydrogen, C 1 -C 10 Straight or branched alkyl, alkenyl, C 3 -C 10 Cycloalkyl;
the tertiary amine is pyridine, triethylamine, N-dimethylaniline or N, N-dimethylbenzylamine.
2. The method for synthesizing an N-substituted benzisothiazolin-3-one derivative according to claim 1, characterized in that: the organic solvent is one or more of benzene, toluene, xylene, chlorobenzene, dichloromethane, dichloroethane and tetrachloroethylene, and the dosage of the organic solvent is 1-10 times of the weight of the dithiosalicylic acid derivative.
3. The method for synthesizing an N-substituted benzisothiazolin-3-one derivative according to claim 1, characterized in that: chlorine or bromine is measured by a flowmeter or a weighing method, and the dosage is 0.5-4 times of the molar quantity of the dithiosalicylic acid derivative; the temperature of the reaction by introducing chlorine or bromine is 10-100 ℃.
4. The method for synthesizing an N-substituted benzisothiazolin-3-one derivative according to claim 1, characterized in that: the dosage of sulfur is 0.7-1.5 times of the mole of dithiosalicylic acid derivative.
5. The method for synthesizing an N-substituted benzisothiazolin-3-one derivative according to claim 1, characterized in that: the temperature of the dropwise adding mixed amine is 10-80 ℃, and the total mole amount of primary amine and tertiary amine is as follows: the molar weight of the halogenated thiobenzoyl halide derivative is 2-4.
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Inventor after: Ge Qianjian

Inventor after: Lin Shirui

Inventor after: Tang Wenjie

Inventor after: Wu Honghui

Inventor after: Zhang Yongbin

Inventor after: Fan Bin

Inventor before: Ge Qianjian

Inventor before: Lin Shirui

Inventor before: Tang Wenjie

Inventor before: Wu Honghui

Inventor before: Zhang Yongbin

Inventor before: Fan Bin