CN113880748B - Green preparation process of 3, 3-diindolylmethane - Google Patents
Green preparation process of 3, 3-diindolylmethane Download PDFInfo
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- CN113880748B CN113880748B CN202111348956.7A CN202111348956A CN113880748B CN 113880748 B CN113880748 B CN 113880748B CN 202111348956 A CN202111348956 A CN 202111348956A CN 113880748 B CN113880748 B CN 113880748B
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- diindolylmethane
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- VFTRKSBEFQDZKX-UHFFFAOYSA-N 3,3'-diindolylmethane Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4NC=3)=CNC2=C1 VFTRKSBEFQDZKX-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims abstract description 15
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000000967 suction filtration Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
The invention provides a green preparation process of 3, 3-diindolylmethane, which comprises the following steps: s1, indole and formaldehyde are used as raw materials, cyanuric acid is used as a catalyst, and the raw materials are added into acetone to react, so that a 3, 3-diindolylmethane crude product is prepared; s2, recrystallizing the 3, 3-diindolylmethane crude product prepared in the step S1 by using ethanol to obtain the purified 3, 3-diindolylmethane. Compared with the traditional method using the catalyst, the method has the advantages of mild reaction conditions, small catalyst consumption and reusable solvent.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a green preparation process of 3, 3-diindolylmethane.
Background
3, 3-diindolylmethane is widely present in natural products and has many pharmacological and physiological activities. For example, it can promote metabolism of female hormone in human body, and can regulate hormone metabolite secreted by some cancer cells, so that it is an effective anticancer medicine. Thus, the synthesis of 3, 3-diindolylmethane has attracted considerable attention.
At present, most of the preparation of the compounds is mainly carried out in traditional organic solvents, and methanol, ethanol and ethyl acetate are usually used, and meanwhile, the defects of long reaction time, low yield, serious environmental pollution and the like exist.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a synthesis method of 3, 3-diindolylmethane, which has the advantages of low cost, high yield, simple process and environmental friendliness, and compared with the method using the traditional catalyst, the method has the advantages of mild reaction conditions, small catalyst consumption and repeated use of the solvent.
In order to achieve the above object, the technical scheme of the present invention is as follows.
A green preparation process of 3, 3-diindolylmethane comprises the following steps:
s1, indole and formaldehyde are used as raw materials, cyanuric acid is used as a catalyst, and the raw materials are added into acetone to react, so that a 3, 3-diindolylmethane crude product is prepared;
s2, recrystallizing the 3, 3-diindolylmethane crude product prepared in the step S1 by using ethanol to obtain the purified 3, 3-diindolylmethane.
In S1, the molar ratio of indole to formaldehyde is 2-3: 1.
further, in S1, the amount of cyanuric acid is 0.5-1% of indole by mass percent.
Further, in S1, the mass ratio of indole to acetone is 1:1 to 2.
In S1, the reaction temperature is 20-30 ℃ and the reaction time is 1h.
The invention has the beneficial effects that:
1. the invention uses cyanuric acid as catalyst, which has high acidity, good catalytic activity, less reaction time and high yield.
2. The catalyst of the invention can be recycled, and the catalytic activity is almost unchanged in the recycling process.
3. The catalyst used in the invention has low price, less consumption, no three wastes in the production process and low energy consumption, and accords with the green production process.
4. The invention uses acetone as a reaction solvent, which can reduce the environmental pollution caused by using an organic solvent; and the repeated crystallization is not needed, and the product quality and the yield are greatly improved.
Drawings
FIG. 1 is a synthetic route diagram of a green preparation process of 3, 3-diindolylmethane provided by the invention.
FIG. 2 is a report of purity analysis of 3, 3-diindolylmethane prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1
A green preparation process of 3, 3-diindolylmethane comprises the following steps:
200g (1.71 mol) of indole, 25.5g (0.85 mol) of formaldehyde, 1g of cyanuric acid and 200g of acetone are taken and added into a 500mL three-necked flask with mechanical stirring, stirring is carried out at 20 ℃, HPLC tracking detection is carried out, the reaction time is 60min, and the reaction pressure is normal pressure. After the reaction is finished, carrying out suction filtration, recrystallizing the obtained filter residue by using absolute ethyl alcohol, and drying to obtain the purified 3, 3-diindolylmethane, wherein the yield is 94.2%, the purity of the product is more than 99.5%, and the purity analysis result is shown in figure 2.
The filtrate was used directly for the next reaction without any treatment.
Example 2
A green preparation process of 3, 3-diindolylmethane comprises the following steps:
200g (1.71 mol) of indole, 25.5g (0.85 mol) of formaldehyde, 1.6g of cyanuric acid and 200g of acetone are taken and added into a 500mL three-necked flask with mechanical stirring, stirring is carried out at 20 ℃, HPLC tracking detection is carried out, the reaction time is 60min, and the reaction pressure is normal pressure. After the reaction is finished, carrying out suction filtration, recrystallizing the obtained filter residue by using absolute ethyl alcohol, and drying to obtain the purified 3, 3-diindolylmethane, wherein the yield is 95.6%, and the purity of the product is more than 99.5%.
The filtrate was used directly for the next reaction without any treatment.
Example 3
A green preparation process of 3, 3-diindolylmethane comprises the following steps:
200g (1.71 mol) of indole, 25.5g (0.85 mol) of formaldehyde, 2g of cyanuric acid and 200g of acetone are taken and added into a 500mL three-necked flask with mechanical stirring, stirring is carried out at 20 ℃, HPLC tracking detection is carried out, the reaction time is 60min, and the reaction pressure is normal pressure. After the reaction is finished, carrying out suction filtration, recrystallizing the obtained filter residue by using absolute ethyl alcohol, and drying to obtain the purified 3, 3-diindolylmethane, wherein the yield is 95.0%, and the purity of the product is more than 99.5%.
The filtrate was used directly for the next reaction without any treatment.
Example 4
A green preparation process of 3, 3-diindolylmethane comprises the following steps:
200g (1.71 mol) of indole, 21g (0.70 mol) of formaldehyde, 1.6g of cyanuric acid and 250g of acetone are taken and added into a 500mL three-necked flask with mechanical stirring, stirring is carried out at 25 ℃, HPLC tracking detection is carried out, the reaction time is 60min, and the reaction pressure is normal pressure. After the reaction is finished, carrying out suction filtration, recrystallizing the obtained filter residue by using absolute ethyl alcohol, and drying to obtain the purified 3, 3-diindolylmethane, wherein the yield is 95.7%, and the purity of the product is more than 99.5%.
The filtrate was used directly for the next reaction without any treatment.
Example 5
A green preparation process of 3, 3-diindolylmethane comprises the following steps:
200g (1.71 mol) of indole, 17g (0.57 mol) of formaldehyde, 2g of cyanuric acid and 400g of acetone are taken and added into a 500mL three-necked flask with mechanical stirring, stirring is carried out at 30 ℃, HPLC tracking detection is carried out, the reaction time is 60min, and the reaction pressure is normal pressure. After the reaction is finished, carrying out suction filtration, recrystallizing the obtained filter residue by using absolute ethyl alcohol, and drying to obtain the purified 3, 3-diindolylmethane, wherein the yield is 93.5%, and the purity of the product is more than 99.5%.
The filtrate was used directly for the next reaction without any treatment.
Example 6
A green preparation process of 3, 3-diindolylmethane comprises the following steps:
200g (1.71 mol) of indole, 25.5g (0.85 mol) of formaldehyde and the filtrate obtained after suction filtration in example 1 are taken and added into a 500mL three-necked flask with mechanical stirring, the mixture is stirred at 20 ℃, the detection is carried out by HPLC, the reaction time is 60min, and the reaction pressure is normal pressure. After the reaction is finished, carrying out suction filtration, recrystallizing the obtained filter residue by using absolute ethyl alcohol, and drying to obtain the purified 3, 3-diindolylmethane, wherein the yield is 94.0%, and the purity of the product is more than 99.5%.
Example 7
The green preparation process of 3, 3-diindolylmethane is basically the same as the method of the example 6, except that the filtrate obtained by the suction filtration of the previous step (the reaction of the example 6 and the next step) is directly reacted, and the yield is basically maintained between 93.5 and 94.1 after the repeated use for 10 times, and the purity of the product is more than 99.5 percent.
As can be seen from the preparation reactions of examples 6 and 7, the catalyst contained in the filtrate after suction filtration was used directly for the next reaction without any treatment and could be reused many times without significant decrease in the catalytic efficiency of the catalyst.
The amounts of the materials charged and the yields of examples 1 to 5 are shown in Table 1.
TABLE 1 feed amount and yield results for examples 1 to 5
| Examples | Indole compounds | Formaldehyde | Catalyst | Yield rate |
| 1 | 200g | 25.5g | 1g | 94.2％ |
| 2 | 200g | 25.5g | 1.6g | 95.6％ |
| 3 | 200g | 25.5g | 2g | 95.0％ |
| 4 | 200g | 21g | 1.6g | 95.7％ |
| 5 | 200g | 17g | 2g | 93.5％ |
As can be seen from the combination of Table 1 and the preparation processes of examples 1 to 5, the preparation of 3, 3-diindolylmethane of examples 1 to 5 of the present invention mainly uses cyanuric acid as a catalyst, and the catalyst has high acidity, good catalytic activity, less reaction time and high yield. The preparation process of the invention in examples 6-7 shows that the catalyst can be recycled and the catalytic activity is almost unchanged during recycling.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. The green preparation process of the 3, 3-diindolylmethane is characterized by comprising the following steps of:
s1, indole and formaldehyde are used as raw materials, cyanuric acid is used as a catalyst, and the raw materials are added into acetone to react, so that a 3, 3-diindolylmethane crude product is prepared;
s2, recrystallizing the 3, 3-diindolylmethane crude product prepared in the step S1 by using ethanol to obtain the purified 3, 3-diindolylmethane.
2. The green process for preparing 3, 3-diindolylmethane according to claim 1, wherein in S1, the molar ratio of indole to formaldehyde is 2-3: 1.
3. the green preparation process of 3, 3-diindolylmethane according to claim 1, wherein in S1, the amount of cyanuric acid is 0.5-1% of indole in percentage by mass.
4. The green preparation process of 3, 3-diindolylmethane according to claim 1, wherein in S1, the mass ratio of indole to acetone is 1:1 to 2.
5. The green process for preparing 3, 3-diindolylmethane according to claim 1, wherein in S1, the reaction temperature is 20-30 ℃ and the reaction time is 1h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085757A (en) * | 2006-06-05 | 2007-12-12 | 姚清发 | Method for forming compound with indole truss by catalytic reaction |
| CN103342675A (en) * | 2013-05-17 | 2013-10-09 | 安徽工业大学 | Preparation method of diindolylmethane derivative through catalysis |
| CN104016900A (en) * | 2014-06-19 | 2014-09-03 | 罗田县新普生药业有限公司 | Preparation method of 3, 3'-diindolylmethane |
| CN107827804A (en) * | 2017-11-27 | 2018-03-23 | 菏泽海诺知识产权服务有限公司 | A kind of preparation method of diindolylmethane derivative |
| CN110256325A (en) * | 2019-07-16 | 2019-09-20 | 杭州志源生物科技有限公司 | A kind of process synthesizing 3,3 '-di-indole methyl hydrides |
-
2021
- 2021-11-15 CN CN202111348956.7A patent/CN113880748B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085757A (en) * | 2006-06-05 | 2007-12-12 | 姚清发 | Method for forming compound with indole truss by catalytic reaction |
| CN103342675A (en) * | 2013-05-17 | 2013-10-09 | 安徽工业大学 | Preparation method of diindolylmethane derivative through catalysis |
| CN104016900A (en) * | 2014-06-19 | 2014-09-03 | 罗田县新普生药业有限公司 | Preparation method of 3, 3'-diindolylmethane |
| CN107827804A (en) * | 2017-11-27 | 2018-03-23 | 菏泽海诺知识产权服务有限公司 | A kind of preparation method of diindolylmethane derivative |
| CN110256325A (en) * | 2019-07-16 | 2019-09-20 | 杭州志源生物科技有限公司 | A kind of process synthesizing 3,3 '-di-indole methyl hydrides |
Non-Patent Citations (4)
| Title |
|---|
| 3-取代吲哚衍生物的合成;李记太 等;《化学进展》;第19卷(第5期);第751-761页 * |
| A versatile and practical synthesis of bis(indolyl)methanes/ bis(indolyl)glycoconjugates catalyzed by trichloro-1,3,5-triazine;G. V. M. Sharma et al.;《Tetrahedron Letters》;第45卷;第7729–7732页 * |
| Pyridinium tribromide catalyzed condensation of indoles and aldehydes to form bisindolylalkanes;Qin Yang et al.;《Chinese Chemical Letters》;第22卷;第515–518页 * |
| 二吲哚甲烷及其衍生物的合成研究进展;孙大召 等;《精细石油化工》;第32卷(第5期);第78-84页 * |
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