CN113501805A - Application of benzene in preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene - Google Patents
Application of benzene in preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene Download PDFInfo
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- CN113501805A CN113501805A CN202110925918.7A CN202110925918A CN113501805A CN 113501805 A CN113501805 A CN 113501805A CN 202110925918 A CN202110925918 A CN 202110925918A CN 113501805 A CN113501805 A CN 113501805A
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- thiophene
- chlorobenzo
- bromomethyl
- benzene
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 101
- OFKWTWJUANJQNU-UHFFFAOYSA-N 3-(bromomethyl)-7-chloro-1-benzothiophene Chemical compound ClC1=CC=CC2=C1SC=C2CBr OFKWTWJUANJQNU-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 19
- PIURQZBTTSWWOY-UHFFFAOYSA-N 7-chloro-3-methyl-1-benzothiophene Chemical compound C1=CC=C2C(C)=CSC2=C1Cl PIURQZBTTSWWOY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005893 bromination reaction Methods 0.000 claims abstract description 7
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical group BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 230000031709 bromination Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 19
- 238000006467 substitution reaction Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000000950 dibromo group Chemical group Br* 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides application of benzene in preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene, wherein the benzene is used as a solvent in the process of preparing the 3-bromomethyl-7-chlorobenzo (b) thiophene from the 3-methyl-7-chlorobenzo (b) thiophene. The method uses benzene to replace carbon tetrachloride as a solvent for bromination reaction to prepare the 3-bromomethyl-7-chlorobenzo (b) thiophene, and the yield of the obtained product can reach more than 57 percent and is higher than that when the carbon tetrachloride is used as the solvent for bromination reaction to prepare the 3-bromomethyl-7-chlorobenzo (b) thiophene.
Description
Technical Field
The invention relates to a preparation method of a compound, in particular to application of benzene in preparing 3-bromomethyl-7-chlorobenzo (b) thiophene.
Background
The existing preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene adopts carbon tetrachloride as a reaction bearing solvent, and the reaction chemical formula is as follows:
in the above reaction, 3-bromomethyl-7-chlorobenzo (b) thiophene is produced by bromination using 3-bromomethyl-7-chlorobenzo (b) thiophene as a substrate and N-bromosuccinimide (NBS) as a brominating reagent. The inventor finds that the yield of the product can only reach 54 percent at most in the process of preparing 3-bromomethyl-7-chlorobenzo (b) thiophene by adopting the synthetic route.
Disclosure of Invention
The present inventors have conducted extensive experiments in order to further improve the yield of the above reaction, and have unexpectedly found that the yield of the product can be improved when benzene is used as a solvent, and have completed the present invention based on this.
The invention provides application of benzene in preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene, wherein the benzene is used as a solvent in the process of preparing the 3-bromomethyl-7-chlorobenzo (b) thiophene from the 3-methyl-7-chlorobenzo (b) thiophene.
In some embodiments of the invention, 3-bromomethyl-7-chlorobenzo (b) thiophene is prepared, comprising:
benzene is used as solvent, and 3-methyl-7-chlorobenzo [ b ] thiophene reacts with a bromination reagent in the presence of benzoyl peroxide to generate 3-bromomethyl-7-chlorobenzo [ b ] thiophene.
In some embodiments of the invention, the brominating reagent is N-bromosuccinimide.
In some embodiments of the invention, the molar ratio of 3-methyl-7-chlorobenzo [ b ] thiophene to brominating reagent is 1: (1-1.1), preferably 1: 1.05.
in some embodiments of the invention, the molar ratio of 3-methyl-7-chlorobenzo [ b ] thiophene to benzoyl peroxide is 1: (0.04-0.1), preferably 1: 0.05.
in some embodiments of the invention, the mass ratio of 3-methyl-7-chlorobenzo [ b ] thiophene to benzene is 1: (6-10), preferably 1: (7-8).
In some embodiments of the invention, the reaction product 3-bromomethyl-7-chlorobenzo (b) thiophene is in a molar yield of 57% or more.
Advantageous effects
The method uses benzene to replace carbon tetrachloride as a solvent for bromination reaction to prepare the 3-bromomethyl-7-chlorobenzo (b) thiophene, and the yield of the obtained product can reach more than 57 percent and is higher than that when the carbon tetrachloride is used as the solvent for bromination reaction to prepare the 3-bromomethyl-7-chlorobenzo (b) thiophene.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail with reference to specific embodiments. It should be understood that the present invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.
The embodiment of the invention provides an application of benzene in preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene, and benzene is used as a solvent in the process of preparing the 3-bromomethyl-7-chlorobenzo (b) thiophene from the 3-methyl-7-chlorobenzo [ b ] thiophene.
Screening experiments
The target product 3-bromomethyl-7-chlorobenzo (b) thiophene in the experiment is a product obtained by replacing one hydrogen atom of methyl on the 3-position of thiophene heterocycle by bromine, the target product is relatively active , and the bromine atom is easily oxidized or replaced by hydroxyl (-OH) to form alcoholate, so that a solvent which is very easy to absorb water and alcohol solvents (methanol, ethanol and the like) containing hydroxyl (-OH) are eliminated in a theoretical level and cannot be selected as a reaction solvent.
Then, the experiment was carried out comprehensively and systematically by classifying the structure from organic solvents including representative solvents among esters, halogenated hydrocarbons, aromatic hydrocarbons, ketones, ethers, and amides. Meanwhile, an HPLC (area normalization method) is adopted to track the reaction conversion path in the whole process, the relative retention time of each component in the reaction solution is determined through product and substrate (sample loading) positioning analysis, and the influence of each solvent on the reaction process is comprehensively investigated.
The procedure of this experiment was as follows:
adding 3-methyl-7-chlorobenzo (b) thiophene and an optional organic solvent into a reaction bottle, and irradiating by using a 200W bulb; adding benzoyl peroxide under stirring, heating to boil, adding N-bromosuccinimide (NBS) in batches, and continuing stirring for 5 hours under boiling (if no obvious reaction or impurity generation exists, the experiment can be stopped early).
Cooling, filtering, concentrating the filtrate until precipitate is separated out, standing for 4 hours, filtering, and washing a filter cake with petroleum ether (II) to obtain yellow 3-bromomethyl-7-chlorobenzo (b) thiophene powder.
Group A: the reaction is not initiated or only a small amount of target product is generated
From the above results, the toluene selected in this group hardly reacted, and the monobasic brominated product produced was very little, and the conversion was very low. Chlorobenzene partially reacts, but monobasic brominated products are formed in small proportions (up to 37.98%), with many unknown impurities. Therefore, the above two solvents are not suitable for use as reaction solvents.
Group B: the reaction takes place with monobromo/dibromo substitution
The results show that the monobromo products generated by trichloromethane, DMF and acetone selected by the group are very few, the dibromo products exceed 50 percent, the conversion rate is moderate, but the selectivity is poor, and the directional conversion function is poor.
The conversion of mono-brominated products by propylene oxide and DMA can reach 45%, but with the production of di-brominated products, binary substitution is not a good choice. Therefore, none of the above five solvents is suitable for use as a reaction solvent.
Group C: the reaction is carried out to generate monobromo/dibromo/tribromo substitution
The results show that the ester solvents selected in the group are subjected to ternary substitution, monobromo/dibromo/tribromide is generated, binary or ternary substitution is deviated from the target severity of directional conversion monobasic substitution, conversion is very low, and more than 20% of proportional equivalent of the substrate remains (normalization method). Therefore, for the purpose of screening experiments for monobromo substitution with high selectivity and high singleness, none of the above ester solvents is suitable for use as a reaction solvent.
Group D: reaction only occurs with monobromo substitution
The results show that the benzene selected by the group is used as a reaction solvent, and the benzene selected by the group and the existing carbon tetrachloride solvent adopt a high performance liquid phase and are subjected to sample loading, positioning, quantitative tracking, analysis and investigation, so that the aromatic hydrocarbon compound benzene selected by the group has a stereochemically balanced and symmetrical structure.
The experimental result shows that the conversion rate of the benzene substrate [ (1-substrate residual proportion) × 100% ] is very high, after 4 hours of reaction, the conversion rate reaches more than 95%, the monobromo product reaches more than 70%, and the conversion efficiency is also high.
In the above 4 reactions of groups A to D, reaction 0h means the time when NBS addition was completed.
The following preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene with benzene as the solvent
Example 1
228.54g of benzene, 29.30g of 3-methyl-7-chlorobenzo [ b ] thiophene and 200W of lamp bulb are added into a reaction bottle, 1.94g of benzoyl peroxide is added into the reaction bottle under stirring, the mixture is heated to boiling, 29.89g N-bromosuccinimide is added in batches, and the mixture is stirred for 5 hours under boiling. Cooling, filtering, concentrating the filtrate until precipitate is separated out, standing for 4 hours, filtering, and washing a filter cake with 21.8g of petroleum ether (II) to obtain 25.59g of yellow 3-bromomethyl-7-chlorobenzo [ b ] thiophene powder.
Example 2
Example 2 differs from example 1 in that the amount of benzene added is 293 g.
Example 3
Example 3 differs from example 1 in that the amount of benzene added is 180 g.
Comparative example 1
Comparative example 1 differs from example 1 in that the same amount of benzene was replaced with carbon tetrachloride.
The properties and molar yields of the products of examples 1 to 3 and comparative example 1 are shown in the following table.
| Product traits | Molar yield | |
| Example 1 | Deep yellow crystal | 57％ |
| Example 2 | Deep yellow crystal | 58％ |
| Example 3 | Deep yellow crystal | 61％ |
| Comparative example 1 | Deep yellow crystal | 54％ |
Wherein,
molar yield ═ moles of product 3-bromomethyl-7-chlorobenzo [ b ] thiophene/moles of substrate 3-methyl-7-chlorobenzo [ b ] thiophene.
As can be seen from the above table, in examples 1-3, compared with comparative example 1, the yield of the product is significantly improved after replacing carbon tetrachloride with benzene as the reaction solvent.
In the description herein, reference to the description of the terms "certain embodiments," "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and are not limitative. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. Use of benzene in the preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene, wherein benzene is used as a solvent in the preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene from 3-methyl-7-chlorobenzo (b) thiophene.
2. Use of benzene according to claim 1 for the preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene, wherein the preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene comprises:
benzene is used as solvent, and 3-methyl-7-chlorobenzo [ b ] thiophene reacts with a bromination reagent in the presence of benzoyl peroxide to generate 3-bromomethyl-7-chlorobenzo [ b ] thiophene.
3. Use of benzene in the preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene according to claim 2, wherein the brominating agent is N-bromosuccinimide.
4. Use of benzene in the preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene according to claim 2, wherein the molar ratio of 3-methyl-7-chlorobenzo [ b ] thiophene to brominating agent is 1: (1-1.1), preferably 1: 1.05.
5. use of benzene according to claim 2 for the preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene, wherein the molar ratio of 3-methyl-7-chlorobenzo [ b ] thiophene to benzoyl peroxide is 1: (0.04-0.1), preferably 1: 0.05.
6. use of benzene according to claim 2 for the preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene, wherein the mass ratio of 3-methyl-7-chlorobenzo [ b ] thiophene to benzene is 1: (6-10), preferably 1: (7-8).
7. The use of benzene in the preparation of 3-bromomethyl-7-chlorobenzo (b) thiophene according to claim 1, wherein the molar yield of the reaction product 3-bromomethyl-7-chlorobenzo (b) thiophene is not less than 57%.
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694470A (en) * | 2020-12-30 | 2021-04-23 | 海南海神同洲制药有限公司 | Preparation process of sertaconazole nitrate |
| CN113480517A (en) * | 2021-07-30 | 2021-10-08 | 海南海神同洲制药有限公司 | Synthetic method of 3-bromomethyl-7-chlorobenzo [ b ] thiophene |
-
2021
- 2021-08-12 CN CN202110925918.7A patent/CN113501805A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694470A (en) * | 2020-12-30 | 2021-04-23 | 海南海神同洲制药有限公司 | Preparation process of sertaconazole nitrate |
| CN113480517A (en) * | 2021-07-30 | 2021-10-08 | 海南海神同洲制药有限公司 | Synthetic method of 3-bromomethyl-7-chlorobenzo [ b ] thiophene |
Non-Patent Citations (2)
| Title |
|---|
| CUBERES, MARIA ROSA等: "Halogeno-substituted 2- and 3-methylbenzo[b]thiophenes use of proton NMR spectral analysis and 1H{1H} nuclear Overhauser effect for locating the halogen substituent", 《MAGNETIC RESONANCE IN CHEMISTRY》 * |
| VENKATESWARLU RAYUDU等: "An Easy, Efficient and Improved Synthesis of Sertaconazole Nitrate", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
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Application publication date: 20211015 |