CN115925598A - Synthetic method of thiofluorocarboxylic acid amide - Google Patents
Synthetic method of thiofluorocarboxylic acid amide Download PDFInfo
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- CN115925598A CN115925598A CN202211549448.XA CN202211549448A CN115925598A CN 115925598 A CN115925598 A CN 115925598A CN 202211549448 A CN202211549448 A CN 202211549448A CN 115925598 A CN115925598 A CN 115925598A
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- acid amide
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- thiofluorocarboxylic
- synthetic method
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- 150000001408 amides Chemical class 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- -1 trifluoromethylthio anion Chemical class 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 13
- 230000003213 activating effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 150000003335 secondary amines Chemical class 0.000 abstract description 6
- 239000002341 toxic gas Substances 0.000 abstract description 4
- FBFTTXYJHNXDDZ-UHFFFAOYSA-N chloromethanethioyl fluoride Chemical compound FC(Cl)=S FBFTTXYJHNXDDZ-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000005917 acylation reaction Methods 0.000 abstract 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 5
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 235000003270 potassium fluoride Nutrition 0.000 description 5
- 239000011698 potassium fluoride Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- OFHCXWMZXQBQMH-UHFFFAOYSA-N trifluoro(trifluoromethylsulfanyl)methane Chemical compound FC(F)(F)SC(F)(F)F OFHCXWMZXQBQMH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 1
Classifications
-
- 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic compound synthesis, and relates to a synthetic method of thiofluorocarboxylic acid amide. A synthetic method of thiofluorocarboxylic acid amide is characterized in that secondary amine is used as a reaction substrate, and trifluoromethylthioester is used as a reaction reagent to synthesize the thiofluorocarboxylic acid amide. The invention takes trifluoromethylthioester as a safe reaction reagent, generates trifluoromethylthio anion under the activation of fluoride anion, and slowly decomposes the released fluorothiophosgene (CSF) by utilizing the trifluoromethylthio anion 2 ) And carrying out acylation reaction with a reaction substrate amine, thereby realizing the safe preparation of the thiofluorocarboxylic acid amide. The synthetic method of the thiofluorocarboxylic acid amide has the advantages of easily obtained raw materials, stable and safe reaction reagents, no need of toxic gas, low cost and contribution to preparation and use in a laboratory.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and relates to a synthetic method of thiofluorocarboxylic acid amide.
Background
The thiofluorocarboxylic acid amide is an important organic synthon and plays an important role in organic chemistry. The thiofluorocarbamic acid amide is a high-activity species and can be applied to synthesis of thiourea and carbamate compounds. However, the traditional synthetic method often needs to use toxic reagents, such as the common reagent of thiophosgene, which is a toxic gas and is not easy to operate. Therefore, the development of a safe synthesis method of the thiofluorocarboxylic acid amide is of great significance.
The team developed an important generation low-cost synthesis method of fluorine-containing sulfur-containing compound trifluoromethyl thioester in 2020 (ZL 202011200750.5), and subsequently developed a plurality of transformation methods of the trifluoromethyl thioester (ZL 202110211672.7; ZL202110209605.1; ZL202110214011. X). Thiofluorocarboxamide is a sulfur-containing fluorine-containing compound, and therefore it can be presumed that: it is certainly possible to synthesize thiofluorocarboxylic acid amides by using trifluoromethylthioesters through the development of a novel chemical reaction, and for this reason, the group of the present invention has made studies to develop the method for synthesizing thiofluorocarboxylic acid amides according to the present invention.
Disclosure of Invention
The invention aims to provide a novel synthetic method of thiofluorocarboxylic acid amide aiming at the defects and shortcomings of the existing synthetic method, and the synthetic method has the advantages of easily obtained synthetic raw materials and a trifluoromethyl sulfide reagent, low cost, safety, simple synthetic process and the like.
The conventional synthesis of thiofluorocarboxylic acid amides requires the use of toxic gases, such as amines, for example, by reaction with fluorothiophosgene. How to realize the safe use of the thiophosgene synthesis in the laboratory has been a problem. Secondly, how to use low-cost reagents for synthesis is also a problem: the synthesis cost of the trifluoromethyl sulfide is low, and the compound has a more suitable scene if the compound can be used for synthesizing the thiofluoro formic acid amide.
In order to achieve the purpose, the invention adopts the technical scheme that:
a synthetic method of thiofluorocarboxylic acid amide is characterized by comprising the following steps: synthesizing thiofluoro-formic acid amide by taking secondary amine as a reaction substrate and trifluoromethyl thioester as a reaction reagent in the presence of a fluorine anion activating reagent;
the reaction equation is:
in the formula (2), R 1 Is aryl or alkyl, R 2 Is aryl or alkyl;
in the formula (3), R 3 Is aryl orAn alkyl group;
the synthesis process of the compound shown in the formula (1) comprises the following steps: dissolving a compound shown in a formula (3) in a solvent in the presence of a fluorine anion activating reagent, and reacting with a compound shown in a formula (2) to generate a compound shown in a formula (1);
the fluorine anion activating reagent is any one of fluorinated metal salt and fluorinated organic salt or a mixture of the fluorinated metal salt and the fluorinated organic salt and crown ether;
the solvent is any one of 1, 2-dichloroethane, dichloromethane, acetonitrile, 1, 4-dioxane, benzene, toluene, xylene, trifluorotoluene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and diethyl ether;
in the reaction system, the molar ratio of the compound shown in the formula (2), the trifluromethyl thioester shown in the formula (3) and the fluorine anion activating reagent is 1 (1-10) to 1-10;
the reaction temperature is 0-50 ℃, and the reaction time is 0.1-12h.
Compared with the existing synthesis method, the synthesis method of the thiofluorocarboxylic acid amide has the following beneficial effects:
(1) The reaction substrate adopted by the invention is commercially available, the reaction reagent has low price, and the cheap trifluoromethyl thioester is used as a sulfur element and carbon element donor, so that the method is beneficial to wide application;
(2) The synthesis method has mild conditions, can tolerate air and does not need inert gas protection;
(3) The operation is simple, convenient and safe, the reaction does not need transition metal and toxic gas, and the method is green and environment-friendly.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1-3 are intended primarily to illustrate the applicability of the reaction substrate for the method of the invention, and examples 4-5 are intended primarily to illustrate the broad applicability of the triflouromethioester reagent used in the method of the invention.
Example 1: in this example, 1a was synthesized by reacting secondary amine 2a with 4-chlorobenzoic acid trifluoromethylthioester (S- (trifluoromethyl) 4-chlorobenzothioate,3 a):
the reaction equation is:
Example 2: in this example, 1b was synthesized by reacting secondary amine 2b with 4-chlorobenzoic acid trifluoromethylthioester (S- (trifluoromethyl) 4-chlorobenzothioate,3 a):
the reaction equation is as follows:
the synthesis steps are as follows: 4-chlorobenzoic acid trifluoromethylthioester 3a (2mmol, 480mg), potassium fluoride (2mmol, 116mg), 18-crown-6 (2mmol, 528mg), and 4.0mL of acetonitrile were added to a 10mL reaction tube equipped with a magnetic stirrer, and after stirring for 5 minutes or more until the solution became black, 2b (1mmol, 199mg) was added; fixing the reaction tube on a magnetic stirrer, reacting for 10 hours at 30 ℃, and identifying the structure of the product 1b by using a gas chromatography-mass spectrometer, wherein the product is easy to lose during separation, so that the yield is determined by separation after the product is converted into thiocarbamate by using alcohols, and the yield is 38%.
Example 3: in this example, 1c was synthesized by reacting 2c, a secondary amine, with 4-chlorobenzoic acid trifluoromethylthioester (S- (trifluoromethyl) 4-chlorobenzothioate,3 a):
the reaction equation is:
the synthesis steps are as follows: 4-chlorobenzoic acid trifluoromethylthioester 3a (2mmol, 480mg), potassium fluoride (2mmol, 116mg), 18-crown-6 (2mmol, 528mg), and 4.0mL of acetonitrile were added to a 10mL reaction tube equipped with a magnetic stirrer, and after stirring for 5 minutes or more until the solution became black, 2c (1mmol, 137mg) was added; fixing the reaction tube on a magnetic stirrer, reacting for 6 hours at 15 ℃, and identifying the structure of the product 1c by using a gas chromatography-mass spectrometer, wherein the product is easily lost during separation, so that the yield is determined by separation after the product is converted into thiocarbamate by using alcohols, and the yield is 74%.
Example 4: in this example, the synthesis of 1a:
the reaction equation is:
the synthesis steps are as follows: 4-Benzobenzoic acid trifluoromethylthioester 3b (2mmol, 564mg), potassium fluoride (2mmol, 116mg), 18-crown-6 (2mmol, 528mg) and 4.0mL of acetonitrile were added to a 10mL reaction tube equipped with a magnetic stirrer, and after stirring for 5 minutes or more until the solution became black, 2a (1mmol, 107mg) was added; fixing the reaction tube on a magnetic stirrer, reacting for 8 hours at 25 ℃, and identifying the structure of the product 1a by using a gas chromatography-mass spectrometer after the reaction is finished, wherein the product is easily lost during separation, so that the yield is determined by separation after the product is converted into thiocarbamate by using alcohols, and the yield is 75%.
Example 5: in this example, 1a was synthesized by reacting secondary amine 2a with lauric acid trifluoromethylthioester (S- (trifluoromethylthio) dodecanethioate,3 c):
the reaction equation is:
the synthesis steps are as follows: adding lauric acid trifluoromethylthioester 3c (2mmol, 568mg), potassium fluoride (2mmol, 116mg), 18-crown-6 (2mmol, 528mg) and 4.0mL of acetonitrile to a 10mL reaction tube equipped with a magnetic stirrer, stirring for 5min or more until the solution turns black, and then adding 2a (1mmol, 107mg); fixing the reaction tube on a magnetic stirrer, reacting for 8 hours at 25 ℃, and identifying the structure of the product 1a by using a gas chromatography-mass spectrometer, wherein the product is easy to lose during separation, so that the yield is determined by separation after the product is converted into thiocarbamate by using alcohols, and the yield is 55%.
Claims (1)
1. A synthetic method of thiofluorocarboxylic acid amide is characterized by comprising the following steps: synthesizing thiofluoro-formic acid amide by taking secondary amine as a reaction substrate and trifluoromethyl thioester as a reaction reagent in the presence of a fluorine anion activating reagent;
the reaction equation is as follows:
in the formula (2), R 1 Is aryl or alkyl, R 2 Is aryl or alkyl;
in the formula (3), R 3 Is aryl or alkyl;
the synthesis process of the compound shown in the formula (1) comprises the following steps: dissolving a compound shown in a formula (3) in a solvent in the presence of a fluorine anion activating reagent, and reacting with a compound shown in a formula (2) to generate a compound shown in a formula (1);
the fluorine anion activating reagent is any one of fluoride metal salt and fluoride organic salt or a mixture of the fluoride metal salt, the fluoride organic salt and crown ether;
the solvent is any one of 1, 2-dichloroethane, dichloromethane, acetonitrile, 1, 4-dioxane, benzene, toluene, xylene, trifluorotoluene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and diethyl ether;
in the reaction system, the molar ratio of the compound shown in the formula (2), the trifluromethyl thioester shown in the formula (3) and the fluorine anion activating reagent is 1 (1-10) to 1-10;
the reaction temperature is 0-50 ℃, and the reaction time is 0.1-12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211549448.XA CN115925598B (en) | 2022-12-05 | 2022-12-05 | Synthesis method of thiofluoro-formic acid amide |
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| CN202211549448.XA CN115925598B (en) | 2022-12-05 | 2022-12-05 | Synthesis method of thiofluoro-formic acid amide |
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| CN115925598A true CN115925598A (en) | 2023-04-07 |
| CN115925598B CN115925598B (en) | 2024-04-12 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836365A (en) * | 2019-01-15 | 2019-06-04 | 华东师范大学 | The thio acyl fluorides derivative of a kind of amine and its synthetic method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836365A (en) * | 2019-01-15 | 2019-06-04 | 华东师范大学 | The thio acyl fluorides derivative of a kind of amine and its synthetic method |
Non-Patent Citations (2)
| Title |
|---|
| JINGJING WEI，等: "Synthesis of Thiocarbamoyl Fluorides and Isothiocyanates Using Amines with CF3SO2Cl", J. ORG. CHEM., vol. 85, pages 12374 * |
| THOMASSCATTOLIN，等: "EfficientSynthesisof TrifluoromethylAminesthroughaFormalUmpolungStrategyfromthe Bench-StablePrecursor (Me4N)SCF3", ANGEW.CHEM.INT.ED., vol. 56, pages 221 - 224 * |
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