CN115925598B - Synthesis method of thiofluoro-formic acid amide - Google Patents
Synthesis method of thiofluoro-formic acid amide Download PDFInfo
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- CN115925598B CN115925598B CN202211549448.XA CN202211549448A CN115925598B CN 115925598 B CN115925598 B CN 115925598B CN 202211549448 A CN202211549448 A CN 202211549448A CN 115925598 B CN115925598 B CN 115925598B
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- acid amide
- trifluoromethylthio
- thiofluoro
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- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- -1 trifluoromethylthio ester Chemical class 0.000 claims abstract description 25
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 150000001408 amides Chemical class 0.000 claims abstract description 6
- 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 12
- 230000003213 activating effect Effects 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
- 150000003839 salts Chemical class 0.000 claims description 5
- 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
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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
- 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 7
- FBFTTXYJHNXDDZ-UHFFFAOYSA-N chloromethanethioyl fluoride Chemical compound FC(Cl)=S FBFTTXYJHNXDDZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002341 toxic gas Substances 0.000 abstract description 4
- 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
- 239000000376 reactant Substances 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 7
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- IOVCXBKSFCOUKK-UHFFFAOYSA-N O=C(C(C=C1)=CC=C1C1=CC=CC=C1)OSC(F)(F)F Chemical compound O=C(C(C=C1)=CC=C1C1=CC=CC=C1)OSC(F)(F)F IOVCXBKSFCOUKK-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 229960005286 carbaryl Drugs 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of synthesis of organic compounds, and relates to a method for synthesizing thiofluoro-formic acid amide. A method for synthesizing thiofluoro-formic acid amide uses secondary amine as a reaction substrate and trifluoromethylthio ester as a reaction reagent. The invention takes the trifluoromethylthio ester as a safe reactant, generates the trifluoromethylthio anion under the activation of the fluorine anion, and slowly decomposes and releases the fluorothiophosgene (CSF) by utilizing the trifluoromethylthio anion 2 ) And (3) carrying out acylation reaction with a reaction substrate amine, so as to realize safe preparation of the thiofluoro-formic acid amide. The synthesis method of the thiofluoformic acid amide has the advantages of easily available raw materials, stable and safe reaction reagent, no toxic gas, low cost and contribution to preparation and use in a laboratory.
Description
Technical Field
The invention belongs to the technical field of synthesis of organic compounds, and relates to a method for synthesizing thiofluoro-formic acid amide.
Background
The thiofluoro carboxylic acid amide is an important organic synthon and plays an important role in organic chemistry. The thiofluorocarboxylic acid amide is taken as a high-activity species and can be applied to the synthesis of thiourea compounds and carbamate compounds. However, the traditional synthesis method often needs 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 method for synthesizing the thiochlorofluoro acid amide is of great importance.
The present team developed a first generation low cost synthesis method (ZL 202011200750.5) of the important fluorine-containing sulfur-containing compound trifluoromethylthio ester in 2020, and subsequently developed various conversion methods (ZL 202110211672.7; ZL202110209605.1; ZL202110214011. X) of trifluoromethylthio ester. The use of the thiochloroformate amide as a sulfur-containing fluorine-containing compound can be presumed: it is certain that the thiochloroformate amide may be synthesized by using trifluoromethylthio ester by developing a new chemical reaction, and thus the team of the present invention conducted a study to develop the method for synthesizing a thiochloroformate amide according to the present invention.
Disclosure of Invention
The invention aims to provide a novel synthesis method of thiofluoro carboxylic acid amide, which aims at the defects and shortcomings of the existing synthesis method, and has the advantages of easily available synthesis raw materials and trifluoromethylthio reagent, low cost, safety, simple synthesis process and the like.
Traditional methods of synthesizing thiochloroformate amides require the use of toxic gases, such as amines, to react with the fluorothiophosgene. How to achieve safe use of the fluorothiophosgene synthesis in the laboratory has been a problem. Second, how to use low cost reagents for synthesis is also a problem: the trifluoromethyl thioester has low synthesis cost, and has more applicable scene if the compound can be used for synthesizing the thiofluoro-formic acid amide.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for synthesizing thiofluocarboxylic acid amide is characterized in that: synthesizing thiofluoro-formic acid amide by taking secondary amine as a reaction substrate and trifluoro methyl thioester as a reaction reagent in the presence of a fluoride 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 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 fluoride anion activating reagent, and then reacting with a compound shown in a formula (2) to generate a compound shown in a formula (1);
the fluoride anion activating reagent is any one of fluoride metal salt and fluoride organic salt or a mixture of fluoride metal salt, fluoride organic salt and crown ether;
the solvent is any one of 1, 2-dichloroethane, dichloromethane, acetonitrile, 1, 4-dioxane, benzene, toluene, xylene, benzotrifluoride, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and diethyl ether;
in the reaction system, the mol ratio range of the compound shown in the formula (2) to the trifluoromethyl thioester shown in the formula (3) and the fluoride anion activating reagent is 1 (1-10): 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 thiofluocarboxylic acid amide has the following beneficial effects:
(1) The reaction substrate adopted by the invention is commercially available, the price of the reaction reagent is low, and the cheap trifluoromethyl thioester is used as a sulfur element and carbon element donor, so that the invention is favorable for wide use;
(2) The synthesis method has mild conditions, can resist air and does not need inert gas protection;
(3) The operation is simple and safe, the reaction does not need the participation of transition metal and toxic gas, and the method is environment-friendly.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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.
Examples 1-3 are intended primarily to illustrate the applicability of the reaction substrates of the process of the present invention and examples 4-5 are intended primarily to illustrate the broad applicability of the trifluoromethylthio reagent used in the process of the present invention.
Example 1: in this example, 1a was synthesized using the reaction of secondary amine 2a with 4-chlorobenzoic acid trifluoromethylthio ester (S- (trifluoromethyl) 4-chlorofluoromethyl, 3 a):
the reaction equation is:
the synthesis steps are as follows: to a 10mL reaction tube equipped with a magnetic stirrer were added 3a (2 mmol,480 mg) of trifluoromethylthio 4-chlorobenzoate, potassium fluoride (2 mmol,116 mg), 18-crown-6 (2 mmol,528 mg) and 4.0mL of acetonitrile, and after stirring for 5 minutes until the solution became black, 2a (1 mmol,107 mg) was added; the reaction tube was fixed on a magnetic stirrer and reacted at 25℃for 8 hours, after which the structure of the product 1a was identified by gas chromatography mass spectrometry, and since it was vulnerable to separation, it was converted into thiocarbamate by using alcohol and then isolated to determine the yield, which was 77%.
Example 2: in this example, 1b was synthesized using the reaction of secondary amine 2b with 4-chlorobenzoic acid trifluoromethylthio ester (S- (trifluoromethyl) 4-chlorofluoromethyl, 3 a):
the reaction equation is:
the synthesis steps are as follows: to a 10mL reaction tube equipped with a magnetic stirrer were added 4-chlorobenzoic acid trifluoromethylthio ester 3a (2 mmol,480 mg), potassium fluoride (2 mmol,116 mg), 18-crown-6 (2 mmol,528 mg) and 4.0mL acetonitrile, and after stirring for 5min or more until the solution became black, 2b (1 mmol, 199mg) was added; the reaction tube was fixed on a magnetic stirrer and reacted at 30℃for 10 hours, after which the structure of the product 1b was identified by gas chromatography mass spectrometry, and since it was vulnerable to separation, it was converted into thiocarbamate by alcohol and then isolated to determine the yield, which was 38%.
Example 3: in this example, 1c was synthesized using a reaction of secondary amine 2c with 4-chlorobenzoic acid trifluoromethylthio ester (S- (trifluoromethyl) 4-chlorofluoromethyl, 3 a):
the reaction equation is:
the synthesis steps are as follows: to a 10mL reaction tube equipped with a magnetic stirrer were added 4-chlorobenzoic acid trifluoromethylthio ester 3a (2 mmol,480 mg), potassium fluoride (2 mmol,116 mg), 18-crown-6 (2 mmol,528 mg) and 4.0mL acetonitrile, and after stirring for 5min or more until the solution became black, 2c (1 mmol,137 mg) was added; the reaction tube was fixed on a magnetic stirrer and reacted at 15℃for 6 hours, after which the structure of the product 1c was identified by gas chromatography mass spectrometry, and since it was vulnerable to separation, it was converted into thiocarbamate by alcohol and then isolated to determine the yield, which was 74%.
Example 4: in this example, 1a was synthesized using a reaction of secondary amine 2a with trifluoromethylthio 4-phenylbenzoate (S- (trifluoromethyl) [1,1' -biphenyl ] -4-carbomate, 3 b):
the reaction equation is:
the synthesis steps are as follows: to a 10mL reaction tube equipped with a magnetic stirrer were added 3b (2 mmol,564 mg) of trifluoromethylthio 4-phenylbenzoate, potassium fluoride (2 mmol,116 mg), 18-crown-6 (2 mmol,528 mg) and 4.0mL of acetonitrile, and after stirring for 5 minutes until the solution became black, 2a (1 mmol,107 mg) was added; the reaction tube was fixed on a magnetic stirrer and reacted at 25℃for 8 hours, after which the structure of the product 1a was identified by gas chromatography mass spectrometry, and since it was vulnerable to separation, it was converted into thiocarbamate by using alcohol, and the yield was determined by separation, and the yield was 75%.
Example 5: in this example, 1a was synthesized using a reaction of secondary amine 2a with trifluoromethylthio laurate (S- (trifluoromethyl) dodecanethioate,3 c):
the reaction equation is:
the synthesis steps are as follows: to a 10mL reaction tube equipped with a magnetic stirrer were added 3c (2 mmol, 618 mg) of trifluoromethylthio laurate, 2mmol,116mg of potassium fluoride, 18-crown-6 (2 mmol,528 mg) and 4.0mL of acetonitrile, and after stirring for 5 minutes or more until the solution became black, 2a (1 mmol,107 mg) was added; the reaction tube was fixed on a magnetic stirrer and reacted at 25℃for 8 hours, after which the structure of the product 1a was identified by gas chromatography mass spectrometry, and since it was vulnerable to separation, it was converted into thiocarbamate by using alcohol, and the yield was determined by separation and found to be 55%.
Claims (1)
1. A method for synthesizing thiofluocarboxylic acid amide is characterized in that: synthesizing thiofluoro-formic acid amide by taking secondary amine as a reaction substrate and trifluoro methyl thioester as a reaction reagent in the presence of a fluoride 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 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 fluoride anion activating reagent, and then reacting with a compound shown in a formula (2) to generate a compound shown in a formula (1);
the fluoride anion activating reagent is a mixture of fluoride metal salt and crown ether;
the solvent is any one of 1, 2-dichloroethane, dichloromethane, acetonitrile, 1, 4-dioxane, benzene, toluene, xylene, benzotrifluoride, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and diethyl ether;
in the reaction system, the mol ratio range of the compound shown in the formula (2) to the trifluoromethyl thioester shown in the formula (3) and the fluoride anion activating reagent is 1 (1-10): 1-10;
the reaction temperature is 0-50 ℃ and the reaction time is 0.1-12h.
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| CN115925598B true 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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| 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 |
|---|
| EfficientSynthesisof TrifluoromethylAminesthroughaFormalUmpolungStrategyfromthe Bench-StablePrecursor (Me4N)SCF3;ThomasScattolin，等;Angew.Chem.Int.Ed.;第56卷;221-224 * |
| Synthesis of Thiocarbamoyl Fluorides and Isothiocyanates Using Amines with CF3SO2Cl;Jingjing Wei，等;J. Org. Chem.;第85卷;12374−12381 * |
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