CN109096221B - Method for generating benzisothiazolinone compound by catalyzing molecular oxygen oxidation in water phase - Google Patents
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Abstract
The invention provides a method for synthesizing benzisothiazolinone compounds by catalyzing molecular oxygen oxidation in an aqueous phase, which takes a water-soluble transition metal phthalocyanine compound as a catalyst, and enables a thiosalicylic acid amide compound to react for 2-24 hours in the aqueous phase at the temperature of 80-100 ℃ in an oxygen environment to generate the benzisothiazolinone compounds. The reaction is carried out in a water phase, and other organic solvents are not required to be added; the catalyst has high catalytic activity and high reaction efficiency; the synthesis process is simple, the product selectivity is high, and the byproducts are few; less waste, environment-friendly and has stronger industrial application prospect.
Description
Technical Field
The invention relates to the technical field of organic sulfur-nitrogen bond synthesis, in particular to a method for synthesizing benzisothiazolinone compounds by catalyzing molecular oxygen oxidation in a water phase.
Background
Benzisothiazolinone derivatives are a very important class of organic heterocyclic compounds, which play an important role in medicine, agriculture, food science and industrial production [ Craine, l.; raban, M.chem.Rev.1989,89,689-712 ]. Since the first synthesis of benzisothiazolinone by Mckibben and mccleland in 1923 [ Mckibben, m.; McClelland, e.w. j.chem.soc., trans.1923,123,170-173, researchers have found that benzisothiazolinone derivatives have a broad spectrum of biological activity, such as antibacterial, antipsychotic, antiviral, antithrombotic, analgesic etc. [ Jorgensen, w.l.; trofimov, a.; du, x.; et al, Biorg. Med. chem.Lett.2011,21,4545-4549 ]. At present, the preservative is also widely used as a main component of the preservative in daily necessities, such as pigments, detergents, leather-making processes, pesticides and the like. A study in 2014 indicated that 96% of pigments from five european countries all contained benzisothiazolinone species [ Schwensen, j.f.; lundov, m.d.; bossi, r.; contact Dermatitis 2015,72, 127-. In addition, some benzisothiazolinone derivatives have been reported to have anti-aids biological activity [ Rice, w.g.; supko, J, g.; malspeis, l.; et al, science 1995,270,1194-1197 ]. There are two general methods for synthesizing benzisothiazolinone compounds, one is intramolecular cyclization, the used substrate includes N-substituted sulfenamide, 2, 2-dimercapto benzamide, N-substituted thiosalicylamide and sulfinyl substituted benzamide compound, and the used oxidant includes hydrogen peroxide, high-valence iodine reagent, trichloro-peroxy acetic anhydride or oxygen, etc. Another method is intermolecular ring closure by introducing an S source to a 2-halobenzamide or an N source to a substrate such as o-mercaptobenzoic acid (see FIG. 5).
However, these methods have very obvious disadvantages: toxic waste, excessive additives, lengthy steps or long reaction times, etc. More importantly, the above-mentioned metal-catalyzed processes have not been directed to other metal-catalyzed processes other than the use of metallic copper. Most oxidizing agents also use organic and inorganic oxidizing agents having strong oxidizing properties. And most of the organic solvents used in the existing reports are organic solvents. From the viewpoint of environmental friendliness and industrial cost, the development of a green and universal catalytic method for synthesizing the benzisothiazolinone derivatives still has great challenges and application values.
In the experimental process, a metal complex which is easy to dissolve in water is selected as a catalyst, and the oxidant is naturally-occurring oxygen, so that the target product can be efficiently obtained under a heterogeneous condition. In the reaction, only the oxygen with one atmosphere pressure is needed to be filled into the reaction container, and the reaction can be carried out and finished without a high-pressure reaction container.
In addition, the method takes water as a solvent, and the target product can be obtained by simple filtration in the post-reaction treatment process due to the extremely poor solubility of the target organic product in water. The target product is obtained through oxidative dehydrogenation coupling in the reaction, and the byproduct is mainly water, so that the aim of green synthesis is fulfilled.
Disclosure of Invention
The invention provides a method for synthesizing benzisothiazolinone compounds by catalyzing molecular oxygen oxidation in an aqueous phase.
The technical scheme for realizing the invention is as follows: a method for generating benzisothiazolinone compounds by catalyzing molecular oxygen oxidation in an aqueous phase is characterized in that a water-soluble transition metal phthalocyanine compound is used as a catalyst, and under an oxygen environment, a thiosalicylic acid amide compound is subjected to intramolecular cyclization reaction in the aqueous phase to generate the benzisothiazolinone compounds, wherein the reaction temperature is 80-100 ℃, and the reaction time is 2-24 hours.
The parent body of the water-soluble transition metal phthalocyanine compound is tetracarboxyl phthalocyanine, tetrasulfo-phthalocyanine, sodium salt of the tetracarboxyl phthalocyanine, potassium salt of the tetracarboxyl phthalocyanine, sodium salt of the tetracarboxyl phthalocyanine or potassium salt of the tetracarboxyl phthalocyanine; the metal center of the transition metal catalyst is any one of Cu, Fe, Co and Mn.
The structural formula of the thiosalicylic acid amide compound is as follows:
wherein R represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a halogen group, a heterocyclic group or an ester group.
The structure of the benzisothiazolinone compound is as follows:
wherein R represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a halogen group, a heterocyclic group or an ester group.
The catalyst is one or more than two of transition metal phthalocyanine compounds in any combination.
The dosage of the catalyst is 1-10% of the mass of the thiosalicylamide compound, and the dosage of the water is 10-30 times of the mass of the thiosalicylamide compound.
The method for synthesizing the benzisothiazolinone compound has the advantages that the reaction is carried out in a water phase, and other organic solvents are not required to be added.
In the method for synthesizing the benzisothiazolinone compound, the water-soluble transition metal phthalocyanine compound used as the catalyst can be one; two or more kinds of transition metal phthalocyanine compounds may be used in combination, and the mass ratio of the metal phthalocyanine compounds is not particularly limited and may be any ratio.
In the present invention, one or more water-soluble transition metal phthalocyanine compounds are used as a catalyst and directly used. The water-soluble transition metal phthalocyanine compound used for the catalyst can be directly purchased into corresponding chemical product complexes or can be synthesized for use.
In the using process of the invention, the reaction effect is improved along with the increase of the catalyst dosage, but the increase of the catalyst dosage also increases the production cost, and the excessive catalyst brings difficulty in separation. The dosage of the catalyst is 1-10% of the mass of the thiosalicylamide compound.
The method is carried out in the water phase, the increase of the water consumption can dissolve more catalysts to improve the reaction speed, reduce the viscosity of the reaction solution to improve the stirring effect, and further improve the reaction effect, but the excessive water consumption can reduce the reaction efficiency and increase the energy consumption. The amount of water is 10-30 times of the mass of the thiosalicylamide compound.
After the synthesis reaction is finished, the post-treatment process is not particularly limited, and the product can be separated and purified by the following method: and after the oxidation reaction is finished, standing and cooling, separating the product from the mother liquor containing the catalyst and unreacted raw materials by filtering, and washing, drying or recrystallizing to obtain the product.
The invention has the beneficial effects that: the reaction is carried out in a water phase, and other organic solvents are not required to be added; the catalyst has high catalytic activity and high reaction efficiency; the synthesis process is simple, the product selectivity is high, and the byproducts are few; less waste, environment-friendly and has stronger industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a diagram of the title product A prepared in example 11H NMR chart.
FIG. 2 is a diagram of the title product A prepared in example 113C NMR chart.
FIG. 3 is a diagram of the preparation of the desired product C from example 31H NMR chart.
FIG. 4 is a diagram of the target product C prepared in example 313C NMR chart.
FIG. 5 is a diagram showing the mechanism of the synthesis of benzisothiazolinone compounds.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of benzisothiazolinone compound A with the structural formula as follows:
a50 mL flask was charged with 2g N-tert-butylthiosalicylamide, 0.1g (5 wt%) of tetra sodium iron tetracarboxyphthalocyanine [ FePc (CO)2Na)4]0.02g (1 wt.%) of tetracarboxyl manganese phthalocyanine tetrasodium [ MnPc (CO)2Na)4]Adding 30mL of water, flushing oxygen, heating to 100 ℃, reacting for 2h, cooling after the reaction is finished, filtering, washing a filter cake with 20mL of water, drying to obtain 1.9 g of white solid, and determining the product by methods such as NMR and MSThe structure is a target product A, the yield is 96 percent, and the purity of a liquid chromatography analysis product is 99 percent.
1H NMR(600MHz,CDCl3,SiMe4)δ:7.96(d,J＝7.8Hz,1H),7.59-7.49(m,2H),7.36(t,J＝ 7.4Hz,1H),1.71(s,9H)；
13C NMR(150MHz,CDCl3,SiMe4)δ:165.5,139.3,131.3,126.8,126.0,125.1,119.7,58.6, 28.3。
Example 2
A preparation method of benzisothiazolinone compound B with the structural formula as follows:
into a 100mL flask was added 4g N-phenylthiosalicylic acid amide, 0.08g tetrasodium tetrasulfonate cobalt phthalocyanine [ CoPc (SO)3Na)4]0.08g of copper tetracarboxylphthalocyanine [ CuPc (CO)2H)4]0.12g of tetrasulfophthalocyanine manganese [ MnPc (SO)3H)4]And 50mL of water are added with oxygen, the mixture is heated to 80 ℃ and reacts for 12 hours, after the reaction is finished, the mixture is cooled and filtered, 40mL of water is used for washing a filter cake, and the filter cake is dried to obtain 3.1g of a target product B, wherein the yield is 78%, and the purity of a liquid chromatographic analysis product is 99%.
Example 3
A preparation method of a benzisothiazolinone compound C with the structural formula as follows:
into a 250mL flask was added 10g N- (2-methyl) phenyl thiosalicylic acid amide, 0.1g tetrapotassium manganese tetrasulfonate [ MnPc (SO)3K)4]And 100mL of water are added with oxygen, the mixture is heated to 90 ℃ and reacts for 24 hours, after the reaction is finished, the mixture is cooled, filtered, washed by water and dried to obtain 8.2g of a target product C, the yield is 82%, and the purity of a liquid chromatography product is 99%.
Example 4
A preparation method of benzisothiazolinone compound D with the structural formula as follows:
into a 100mL flask was charged 3g N- (4-nitro) phenylthiosalicylic acid amide, 0.15g of copper tetrasulfonate phthalocyanine [ CuPc (SO)3H)4]0.15g of Tetracarboxylphthalocyanine tetrapotassium [ MnPc (CO)2K)4]And 50mL of water are added, oxygen is added, the mixture is heated to 100 ℃, the reaction is carried out for 24 hours, after the reaction is finished, the mixture is cooled, filtered, washed by water and dried to obtain 2.8g of a target product D, the yield is 93 percent, and the purity of a liquid chromatography product is 99 percent.
The preparation of benzisothiazolones under different conditions is shown in Table 1.
TABLE 1 preparation of benzisothiazolones under different conditions
Note:arepresents the molar ratio of the following, namely the thiosalicylic acid amide compound: transition metal catalyst
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (2)
1. A method for generating benzisothiazolinone compounds by catalyzing molecular oxygen oxidation in a water phase is characterized in that: taking a water-soluble transition metal phthalocyanine compound as a catalyst, and carrying out intramolecular cyclization reaction on a thiosalicylic acid amide compound in a water phase under an oxygen environment to generate a benzisothiazolinone compound, wherein the reaction temperature is 80-100 ℃, and the reaction time is 2-24 h;
the parent body of the water-soluble transition metal phthalocyanine compound is tetracarboxyl phthalocyanine, tetrasulfo-phthalocyanine, sodium salt of the tetracarboxyl phthalocyanine, potassium salt of the tetracarboxyl phthalocyanine, sodium salt of the tetracarboxyl phthalocyanine or potassium salt of the tetracarboxyl phthalocyanine; the metal center of the water-soluble transition metal phthalocyanine compound is any one of Cu, Fe, Co and Mn; the catalyst is one or more than two of water-soluble transition metal phthalocyanine compounds which are randomly combined;
the structural formula of the thiosalicylic acid amide compound is as follows:
wherein R represents an alkyl group, an aryl group, a 2-pyridyl group;
the structural formula of the benzisothiazolinone compound is as follows:
wherein R represents alkyl, aryl, 2-pyridyl.
2. The method for catalyzing the oxidation of molecular oxygen in aqueous phase to produce benzisothiazolinone compounds according to claim 1, wherein: the dosage of the catalyst is 1-10% of the mass of the thiosalicylamide compound, and the dosage of the water is 10-30 times of the mass of the thiosalicylamide compound.
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| CN113200937B (en) * | 2021-05-14 | 2022-12-13 | 郑州大学 | Method for preparing 1,2-benzisothiazolin-3-one by catalytic oxidation |
| CN115608390B (en) * | 2021-07-16 | 2024-05-31 | 河南科技大学 | Simple preparation of nitrogen-doped transition metal carbon catalyst and application thereof in organic S-N bond synthesis |
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| CN106831750A (en) * | 2017-01-24 | 2017-06-13 | 郑州大学 | The method of catalytic molecular oxygen oxidation sulfenamide compound of the generation with S N keys in water phase |
| CN106866577A (en) * | 2017-01-24 | 2017-06-20 | 蔚林新材料科技股份有限公司 | The method that the oxidation of catalytic molecular oxygen prepares sulfenamide thiofide in water phase |
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