CN110950836A - Preparation method of benzodithiol heterocyclic alkene skeleton compound - Google Patents
Preparation method of benzodithiol heterocyclic alkene skeleton compound Download PDFInfo
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Abstract
The invention discloses a preparation method of a benzodithiol heterocyclic alkene skeleton compound, which is prepared by reacting 2-bromothiobenzamide derivative with S8Adding the mixture into an organic solvent, adding a ligand and alkali, reacting in an inert atmosphere under the action of a copper catalyst, and then carrying out suction filtration and acidic hydrolysis treatment on a reaction system to obtain the catalyst. The method has the advantages of simple operation, easily obtained raw materials and reagents, mild conditions, green and environment-friendly reaction system and easy separation and purification of products, is suitable for synthesizing various benzodithiol heterocyclic alkene skeleton compounds, is particularly suitable for large-scale industrial production, can prepare the high-purity benzodithiol heterocyclic alkene skeleton compounds with high efficiency and high yield, and has the highest product yield of 91%.
Description
Technical Field
The invention relates to a preparation method of a sulfur-containing heterocyclic compound, in particular to a preparation method of a benzodithiol heterocyclic alkene skeleton compound.
Background
The sulfur-containing organic matter is a compound with wide biological activity and structural function and is widely present in animals and plants in nature; also has cancer-inhibiting and bactericidal effects in biological terms (organophosphorous Chemistry: Volume 42, Royal Society of Chemistry 2013.). For example, isothiocyanate can prevent the occurrence of cancer of tissues such as lung and liver; for example, penicillin and cephamycin are important synthetic antibiotics, which contain a thietane structural unit. Cysteine and methionine, which are widely present in life in nature, are also sulfur-containing organic substances. Among them, some sulfur-containing heterocyclic skeletons having specific structures, for example, benzodithiol abbreviated as BDT, are benzo-fused five-membered sulfur-containing heterocyclic compounds, generally having both 1, 3-and 1, 2-dithia structures. Certain BDT-like scaffold compounds generally have very good biological or pharmacological activities, such as anti-hepatitis b virus and antibacterial activity (j.med.chem.2004,47, 5265-. Therefore, the construction of the BDT sulfur-containing heterocyclic skeleton has important significance in organic synthesis and biological medicine.
In 2013, Chen et al used 2-mercaptobenzoate as a raw material and sodium persulfate as a sulfur source to successfully synthesize 3H-benzo [ c ] [1,2] dithiol-3-one (chem. Sci.2013,4, 2892-2896.). Similar 1,2-BDT compounds can also be synthesized by Beaucage group using 2-mercaptobenzoic acid instead of ester, thioacetic acid as a sulfur source under sulfuric acid catalysis, but both use thiophenol analogs, which are not easily prepared and have an odor tolerable (J.Org.chem.1990,55, 4693-4699.). Penenory et al optimized the process by using 2-iodobenzoic acid and excess potassium thioacetate as starting materials to construct 1,2-BDT by Ullmann reaction under CuI/o-phen catalysis, but at a lower yield (BeilsteinJ. org. chem.2013,9, 467-. In 2014, 3H-benzo [ c ] [1,2] dithiol-3-one is obtained in the process of preparing a fluorescent probe (reaction of 2-mercaptophenyl benzoate and sodium persulfate) by the Xian topic group, but good yield can be obtained only if a benzene ring is connected with a strong electron-withdrawing group (such as nitro); the other substituents all gave very low yields (phenyl 2-mercaptobenzoate, yield only 7%, J.Am.chem.Soc.2014,136, 7257-7260.).
The method for constructing 1,2-BDT has the defects of difficult acquisition of raw materials, difficult synthesis, low yield, limited substrates and the like, and the sulfur source is generally a sulfur-containing compound.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems, the invention provides a preparation method of the benzodithiol heterocyclic skeleton compound, which has the advantages of easily obtained raw materials, mild reaction conditions, environmental friendliness and high yield.
The technical scheme is as follows: the invention relates to a preparation method of a benzodithiol alkene skeleton compound shown as the following formula (2),
2-bromothiobenzamide derivative and S8Adding the mixture into an organic solvent, adding a ligand and alkali, reacting in an inert atmosphere under the action of a copper catalyst, and then carrying out suction filtration and acidic hydrolysis treatment on a reaction system to obtain the benzodithiol heterocyclic pentenyl skeleton compound, namely the BDT skeleton compound, wherein R is hydrogen, alkyl, alkoxy, aryl, heteroaryl or halogen, and X is carbon or nitrogen.
Wherein the reaction temperature of the reaction raw materials under the action of the copper catalyst is 40-120 ℃, the optimum temperature is 100 ℃, and the reaction lasts 8 hours.
After the reaction system is filtered, 2M HCl solution is used for hydrolysis for 2 h.
The ligand is selected from triphenylphosphine, phenanthroline, 2' -bipyridine or L-proline, and is preferably triphenylphosphine.
The base is selected from cesium carbonate, potassium carbonate or sodium bicarbonate, preferably potassium carbonate.
The copper catalyst is selected from copper powder, cupric oxide, cupric fluoride, cupric nitrite, cuprous iodide or cuprous bromide, preferably cuprous iodide.
The organic solvent is selected from 1, 2-dichloroethane, 1, 4-dioxane, N-dimethylformamide, acetonitrile, chloroform or dimethyl sulfoxide, and is preferably N, N-dimethylformamide.
The molar ratio of the S8 to the 2-bromothiobenzamide derivative shown in the formula (1) is 1.1-2: 1, preferably 1.2: 1; the molar ratio of the alkali to the 2-bromothiobenzamide derivative is 1-2: 1, preferably 1: 1; the amount of the ligand and the catalyst is respectively 20 mol% and 10 mol% of the amount of the 2-bromothiobenzamide derivative.
The invention develops a novel method for simply and efficiently synthesizing BDT skeleton compounds, and a simple and easily-obtained industrial raw material compound 2-bromothiobenzamide derivative is used for reacting with sulfur powder under mild conditions to obtain benzo [ c ] [1,2] dithiole-3-imine derivatives. Subsequently, the benzo [ c ] [1,2] dithiol-3-imine derivative is hydrolyzed to synthesize the BDT skeleton compound without separation. The invention opens up a brand-new path with low price and environmental friendliness for the synthesis of BDT skeleton compounds, and provides a guide for further developing biological medicines and functional sulfur-containing heterocyclic compounds.
Has the advantages that: compared with the prior art, the method has the advantages of simple operation, easily obtained raw materials and reagents, mild conditions, green and environment-friendly reaction system, easy separation and purification of products, suitability for synthesizing various BDT skeleton compounds, particular suitability for large-scale industrial production, capability of preparing high-purity BDT skeleton compounds with high efficiency and high yield, and the highest product yield of 91 percent.
Drawings
FIG. 1 shows a BDT skeleton compound 2a1Nuclear magnetic resonance spectrum of H-NMR;
FIG. 2 shows BDT skeleton compound 2a13Nuclear magnetic resonance spectrum of C-NMR;
FIG. 3 shows BDT skeleton compound 2b1Nuclear magnetic resonance spectrum of H-NMR;
FIG. 4 shows BDT skeleton compound 2b13Nuclear magnetic resonance spectrum of C-NMR;
FIG. 5 shows BDT skeleton compound 2c1Nuclear magnetic resonance spectrum of H-NMR;
FIG. 6 shows BDT skeleton compound 2c13Nuclear magnetic resonance spectrum of C-NMR;
FIG. 7 shows BDT skeleton compound 2d1Nuclear magnetic resonance spectrum of H-NMR;
FIG. 8 shows BDT skeleton compound 2d13Nuclear magnetic resonance spectrum of C-NMR;
FIG. 9 shows BDT skeleton compound 2e1Nuclear magnetic resonance spectrum of H-NMR;
FIG. 10 shows BDT skeleton compound 2e13Nuclear magnetic resonance spectrum of C-NMR.
Detailed Description
The invention is further described below with reference to the figures and examples.
Example 1
Preparation of BDT-like framework compound 2 a:
to a 25 mL round bottom flask equipped with a magnetic stirring apparatus was added DMF (4mL), 2-bromothiobenzamide 1a (146mg, 0.5mmol) and sulfur powder (154mg, 0.6mmol), cuprous iodide (10mg, 0.05mol), PPh3(26mg，0.1mmol)，K2CO3(69mg, 0.5mmol) was stirred well, argon (Ar) was evacuated three times, and the mixture was put into an oil bath at 100 ℃ to continue the reaction with stirring for 8 hours. Thin layer chromatography (TLC, developing solvent V)Petroleum ether:VEthyl acetate10:1) detection of substrate disappearance and reaction end. And then, carrying out suction filtration, reduced pressure distillation and concentration on the obtained reaction solution, adding the reaction solution into a 2M HCl aqueous solution (4mL), and stirring at normal temperature for 2h to obtain a new reaction system. Extracting the new reaction system with dichloromethane (3 × 10mL), mixing organic phases, drying with anhydrous calcium chloride, filtering, distilling under reduced pressure to obtain viscous solid, and performing silica gel column chromatography (eluent is V)Petroleum ether:VEthyl acetate10:1) was obtained as a white solid, which was confirmed by NMR and MS to be BDT-based skeleton compound 2a, and the yield thereof was 86%.
Spectrogram analysis of BDT skeleton compound 2 a:
The invention carries out related research aiming at the yield of the BDT skeleton compound 2a prepared under different conditions.
1. Influence of reaction temperature on yield of BDT skeleton compound 2a
The reaction materials and the procedure were the same as in example 1, except that the reaction materials were reacted in an oil bath at 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃ and 120 ℃ respectively, and the yields of the BDT-based skeleton compound 2a at different temperatures were shown in Table 1.
TABLE 1 influence of reaction temperature on the yield of BDT-based framework compound 2a
| Temperature (. degree.C.) | 20 | 40 | 60 | 80 | 100 | 120 |
| Yield (%) | 0 | 11 | 23 | 45 | 86 | 89 |
As can be seen from Table 1, the yields of the products were different at different reaction temperatures, with the highest yield at 120 ℃. The reaction temperature is increased from 40 ℃ to 100 ℃, the product yield is greatly improved, the reaction temperature is ultrahigh by 100 ℃, the product yield is not obviously improved, the yield and the preparation cost are comprehensively considered, and the optimal reaction temperature is 100 ℃.
2. Effect of ligand on the yield of BDT-like framework Compound 2a
The reaction raw materials and the process are the same as example 1, the difference from example 1 is that the ligands used in the reaction are triphenylphosphine, phenanthroline, 2' -bipyridine and L-proline respectively, and the yield of the BDT skeleton compound 2a prepared by adopting different ligands is shown in Table 2.
TABLE 2 influence of ligands on the yield of BDT-like framework compounds 2a
| Ligands | Triphenylphosphine | Phenanthroline diazepine | 2,2' -bipyridine | L-proline |
| Yield (%) | 86 | 72 | 54 | 32 |
As can be seen from Table 2, the yields of the products obtained with different ligands are different, and the highest yield is obtained when the ligand is selected from triphenylphosphine.
3. Influence of base on yield of BDT skeleton compound 2a
The reaction materials and procedures are the same as in example 1, except that the bases used in the reaction are cesium carbonate, potassium carbonate, diazabicyclo, triethylenediamine, triethylamine and sodium bicarbonate, respectively, and the yields of the BDT-based framework compound 2a prepared using the different bases are shown in table 3.
TABLE 3 influence of bases on the yield of BDT-like framework compounds 2a
| Alkali | Cesium carbonate | Potassium carbonate | Diazabicyclo compounds | Triethylenediamine | Triethylamine | Sodium bicarbonate |
| Yield (%) | 75 | 86 | 0 | 0 | 0 | 65 |
As can be seen from Table 3, the yields of the products obtained with different bases are different, with the highest yield being obtained when the base is selected from potassium carbonate.
4. Influence of copper catalyst on yield of BDT skeleton compound 2a
The reaction materials and procedures were the same as in example 1 except that the copper catalysts for the reaction were copper powder, copper nitrate, copper oxide, copper fluoride, copper phosphate, copper nitrite, copper acetate, copper trifluoromethanesulfonate, copper tetrafluoroborate, cuprous iodide and cuprous bromide, respectively, and the yields of the BDT-based skeletal compound 2a prepared using the different copper catalysts were as shown in table 4.
TABLE 4 influence of copper catalyst on the yield of BDT-based framework compounds 2a
| Catalyst and process for preparing same | Cu | Cu(NO3)2 | CuO | CuF2 | Cu3(PO4)2 | CuNO2 | Cu(OAc)2 | Cu(OTf)2 | Cu(BF4)2 | CuI | CuBr |
| Yield (%) | 51 | 0 | 30 | 21 | 0 | 65 | 0 | 0 | 0 | 86 | 37 |
As can be seen from table 4, the yields of the products obtained with different copper catalysts were different, and the highest yield was obtained when the copper catalyst was selected from cuprous iodide.
5. Influence of organic solvent on yield of BDT skeleton compound 2a
The reaction materials and processes were the same as in example 1, except that the reaction organic solvents were 1, 2-dichloroethane, 1, 4-dioxane, N-dimethylformamide, acetonitrile, chloroform and dimethyl sulfoxide, respectively, and the yields of the BDT-based skeleton compound 2a prepared using different organic solvents were as shown in table 5.
TABLE 5 influence of organic solvent on the yield of BDT skeleton compound 2a
| Organic solvent | 1, 2-dichloroethane | 1, 4-dioxane | N, N-dimethylformamide | Acetonitrile | Chloroform | Dimethyl sulfoxide |
| Yield (%) | 67 | 76 | 86 | 54 | 43 | 79 |
As can be seen from Table 5, the yields of the products obtained with different organic solvents were different, and the yield of the product was the highest when the organic solvent was selected from N, N-dimethylformamide.
6、S8Effect of molar ratio to 2-Bromothiobenzamide derivative on the yield of BDT-based skeleton Compound 2a
The reaction materials and procedures were the same as in example 1 except that in example 1, S8The molar ratios to the 2-bromothiobenzamide derivative were 1.1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, and 2:1, respectively, and the yields of the BDT-based skeleton compound 2a prepared using the different molar ratios are shown in table 6.
TABLE 6S8Effect of molar ratio to 2-Bromothiobenzamide derivative on the yield of BDT-based skeleton Compound 2a
| Raw material molar ratio | 1.1:1 | 1.2:1 | 1.4:1 | 1.6:1 | 1.8:1 | 2:1 |
| Yield (%) | 77 | 86 | 87 | 88 | 86 | 89 |
As can be seen from Table 6, S8The yield of the obtained product is different when the molar ratio of the compound to the 2-bromothiobenzamide derivative is different, and the yield of the product is the highest when the molar ratio is 2: 1. When the molar ratio is increased from 1.1:1 to 1.2:1, the product yield is greatly improved, and as the molar ratio is further increased, the yield increase from 1.2:1 is not obvious, and the optimal molar ratio is 1.2:1 in consideration of the yield and the preparation cost.
Therefore, according to the above-mentioned studies of different conditions, the optimal reaction conditions were determined as follows: the reaction temperature is selected from 100 ℃, the ligand is selected from triphenylphosphine, the base is selected from potassium carbonate, the copper catalyst is selected from cuprous iodide, the organic solvent is selected from N, N-dimethylformamide and S8The molar ratio to the 2-bromothiobenzamide derivative is selected from 1.2: 1.
Example 2
1a in example 1 was replaced by 1b, and the experimental results are shown in Table 7, except that the conditions were the same as in example 1.
Spectrogram analysis of BDT skeleton compound 2 b:
example 3
1a in example 1 was replaced with 1c, and the experimental results were shown in Table 7, under the same conditions as in example 1.
Spectrogram analysis of BDT type skeleton compound 2 c:
Example 4
1a in example 1 was replaced with 1d, and the experimental results were shown in Table 7, under the same conditions as in example 1.
Spectrogram analysis of BDT type skeleton compound 2 d:
example 5
1a in example 1 was replaced with 1e, and the experimental results are shown in Table 7, under the same conditions as in example 1.
Spectrogram analysis of BDT skeleton compound 2 e:
Example 6
1f was used instead of 1a in example 1, and the experimental results were shown in Table 7, except that the conditions were the same as in example 1.
Spectrogram analysis of BDT type skeleton compound 2 f:
example 7
1a in example 1 was replaced with 1g, and the experimental results were shown in Table 7, under the same conditions as in example 1.
Spectrogram analysis of 2g of BDT skeleton compound:
example 8
1a in example 1 is replaced by 1h, other conditions are the same as example 1, and the experimental results are shown in Table 7.
Spectrogram analysis of BDT skeleton compound 2 h:
TABLE 7 BDT-based skeleton compounds prepared in examples 1 to 8 and yield
Claims (10)
1. A method for preparing a benzodithiol alkene skeleton compound represented by the following formula (2),
2-bromothiobenzamide derivative and S8Adding the mixture into an organic solvent, adding a ligand and alkali, reacting in an inert atmosphere under the action of a copper catalyst, and then carrying out suction filtration and acidic hydrolysis treatment on a reaction system to obtain the benzodithiol heterocyclic alkene skeleton compound, wherein R is hydrogen, alkyl, alkoxy, aryl, heteroaryl or halogen, and X is carbon or nitrogen.
2. The method for producing benzodithiol alkene skeleton compounds according to claim 1, wherein the ligand is selected from triphenylphosphine, phenanthroline, 2' -bipyridine or L-proline.
3. The method of claim 2, wherein the ligand is triphenylphosphine.
4. The method of preparing benzodithiol alkene skeleton compounds according to claim 1, wherein the base is cesium carbonate, potassium carbonate or sodium bicarbonate.
5. The method of claim 4, wherein the base is selected from potassium carbonate.
6. The method for producing benzodithiol alkene skeleton compounds according to claim 1, wherein the copper catalyst is selected from copper powder, copper oxide, copper fluoride, copper nitrite, cuprous iodide and cuprous bromide.
7. The method of claim 6, wherein the copper catalyst is selected from cuprous iodide.
8. The method for producing benzodithiol alkene skeleton compounds according to claim 1, wherein the organic solvent is selected from 1, 2-dichloroethane, 1, 4-dioxane, N-dimethylformamide, acetonitrile, chloroform and dimethyl sulfoxide.
9. The method of claim 8, wherein the organic solvent is selected from the group consisting of N, N-dimethylformamide.
10. The method for producing benzodithiol alkene skeleton compound according to claim 1, wherein S is8The molar ratio of the 2-bromothiobenzamide derivative to the 2-bromothiobenzamide derivative is 1.1-2: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114524798A (en) * | 2022-01-14 | 2022-05-24 | 华南师范大学 | Benzodithiocarbazaheterocycle derivative and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187096A (en) * | 1975-09-30 | 1980-02-05 | The Ansul Company | Biocidally-active 1,3-benzodithiole-2-thione compounds |
| CN109503547A (en) * | 2018-12-20 | 2019-03-22 | 江苏师范大学 | The preparation method of two sulphur cyclopentadiene derivant of benzo |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187096A (en) * | 1975-09-30 | 1980-02-05 | The Ansul Company | Biocidally-active 1,3-benzodithiole-2-thione compounds |
| CN109503547A (en) * | 2018-12-20 | 2019-03-22 | 江苏师范大学 | The preparation method of two sulphur cyclopentadiene derivant of benzo |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114524798A (en) * | 2022-01-14 | 2022-05-24 | 华南师范大学 | Benzodithiocarbazaheterocycle derivative and preparation method and application thereof |
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