阅读说明：本技术 电化学氧化合成4-磺酸取代异喹啉酮衍生物的方法 (Method for synthesizing 4-sulfonic acid substituted isoquinolone derivative through electrochemical oxidation ) 是由 张振兴 董茹 李刚 秦丙昌 于 2019-10-31 设计创作，主要内容包括：电化学氧化合成4-磺酸取代异喹啉酮衍生物的方法,采用N-取代的苯甲酰胺与磺化学试剂在不分室的电解槽中进行电解制取,述的电解温度为25-80℃,电解用的阳极为石墨片电极或玻碳电极或铂网电极；电解用的阴极为石墨片电极或铝片电极或铁片电极或铜片电极或锌片电极本方法采用电化学氧化合成4-苯磺酸取代异喹啉酮衍生物。并且使用不分室的反应器,对设备要求低,不需要质子膜,无需金属催化剂和氧化剂,降低了产物中金属离子的含量。无需额外添加化学氧化剂,避免了化学氧化剂使用产生的废弃物污染,很适合工业化生产。(The electrochemical oxidation process of synthesizing 4-sulfonic acid substituted isoquinolone derivative includes electrolyzing N-substituted benzamide and sulfonating chemical reagent in no-compartment electrolytic bath at 25-80 deg.c with graphite sheet electrode, glassy carbon electrode or platinum net electrode as the anode; the cathode for electrolysis is a graphite sheet electrode or an aluminum sheet electrode or an iron sheet electrode or a copper sheet electrode or a zinc sheet electrode, and the method adopts electrochemical oxidation to synthesize the 4-benzenesulfonic acid substituted isoquinolinone derivative. And a reactor without a chamber is used, so that the requirement on equipment is low, a proton membrane is not needed, a metal catalyst and an oxidant are not needed, and the content of metal ions in a product is reduced. No additional chemical oxidant is needed, so that the waste pollution caused by the use of the chemical oxidant is avoided, and the method is suitable for industrial production.)

1. The method for synthesizing the 4-sulfonic acid substituted isoquinolone derivative through electrochemical oxidation is characterized in that the 4-sulfonic acid substituted isoquinolone derivative is of a structure shown in a formula III and is characterized in that: the N-substituted benzamide shown in formula I and the sulphonation chemical reagent shown in formula II are electrolyzed in a non-chambered electrolytic cell to prepare the compound, and the conversion formula is as follows:

in the conversion formula, Ar is an aromatic ring containing a substituent and not containing the substituent; r1 represents an alkyl or heteroatom or an aryl or acyl group; r2 represents H or alkyl; r3 represents alkyl or aryl or acyl; r4 represents alkyl or acyl or aryl; r5 represents an alkyl or heteroatom or an aryl or acyl group.

2. The method for synthesizing 4-sulfonic acid substituted isoquinolone derivative through electrochemical oxidation according to claim 1, characterized in that: the electrolysis temperature is 25-80 ℃.

3. The method for synthesizing 4-sulfonic acid substituted isoquinolone derivative through electrochemical oxidation according to claim 1, characterized in that: the anode for electrolysis is a graphite sheet electrode or a glassy carbon electrode or a platinum mesh electrode; the cathode for electrolysis is a graphite sheet electrode or an aluminum sheet electrode or an iron sheet electrode or a copper sheet electrode or a zinc sheet electrode.

Technical Field

The invention relates to a method for synthesizing 4-sulfonic acid substituted isoquinolone derivatives, belonging to the field of chemistry.

Background

4-sulfonic acid substituted isoquinolone and derivatives thereof are widely applied in pharmaceutical chemistry and synthetic chemistry, thereby attracting the attention of numerous chemists and always being the focus of synthetic chemistry. The main synthesis method of the 4-sulfonic acid substituted isoquinolone derivative comprises the following steps:

xiangsheng Xu et al reported that sulfonyl hydrazide as a raw material (org. biomol. chem., 2015, 13, 3308), tert-butyl peroxide as an oxidant, reacted in acetonitrile at 80 ℃ for 6 hours under the catalysis of tetrabutylammonium iodide, to obtain the target product in 24-89% yield.

Peipei Sun et al reported that sulfonyl chloride as a raw material (org. biomol. chem., 2016, 14, 9416-9422), added an excess of potassium hydrogen phosphate, irradiated with light catalyzed by iridium as a metal photosensitizer, acetonitrile as a solvent, and protected with argon, to obtain the target product in a yield of 72-96%.

Xiao-Feng Xia et al reported that thiophenol (adv. Synth. Catal. 2017, 359, 859-865) was used as a raw material, and an excess of potassium persulfate and oxygen were co-oxidized under the catalysis of silver nitrate, and DMF was used as a solvent, and reacted at 80 ℃ for 18 hours. The target product was obtained in 28-75% yield.

The reaction method needs the participation of a metal-containing reagent and a proton membrane, so that metal ions are easy to remain in the product, and the reaction method has the defects of low yield, long reaction time and the like.

Disclosure of Invention

The invention aims to overcome the problems in the synthesis of the existing 4-sulfonic acid substituted isoquinolinone derivatives and provides a method for synthesizing the 4-sulfonic acid substituted isoquinolinone derivatives by electrochemical oxidation.

In order to realize the purpose of the invention, the following technical scheme is adopted: the method for synthesizing the 4-sulfonic acid substituted isoquinolone derivative by electrochemical oxidation is characterized in that the 4-sulfonic acid substituted isoquinolone derivative has a structure shown in a formula III, and is prepared by electrolyzing N-substituted benzamide shown in a formula I and a sulfonation chemical reagent shown in a formula II in an electrolysis bath without a chamber, wherein the conversion formula is as follows:

in the conversion formula, Ar is an aromatic ring containing a substituent and not containing the substituent; r1 represents an alkyl or heteroatom or an aryl or acyl group; r2 represents H or alkyl; r3 represents alkyl or aryl or acyl; r4 represents alkyl or acyl or aryl; r5 represents an alkyl or heteroatom or an aryl or acyl group.

Further, the method comprises the following steps of; the electrolysis temperature is 25-80 ℃.

Further, the method comprises the following steps of; the anode for electrolysis is a graphite sheet electrode or a glassy carbon electrode or a platinum mesh electrode; the cathode for electrolysis is a graphite sheet electrode or an aluminum sheet electrode or an iron sheet electrode or a copper sheet electrode or a zinc sheet electrode.

The method adopts electrochemical oxidation to synthesize the 4-benzenesulfonic acid substituted isoquinolone derivative. And a reactor without a chamber is used, so that the requirement on equipment is low, a proton membrane is not needed, a metal catalyst and an oxidant are not needed, and the content of metal ions in a product is reduced. No additional chemical oxidant is needed, so that the waste pollution caused by the use of the chemical oxidant is avoided, and the method is suitable for industrial production.

Detailed Description

The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.