CN115974735A - Synthesis method of carboxylic ester compound containing trifluoromethylthio group - Google Patents
Synthesis method of carboxylic ester compound containing trifluoromethylthio group Download PDFInfo
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- CN115974735A CN115974735A CN202211549377.3A CN202211549377A CN115974735A CN 115974735 A CN115974735 A CN 115974735A CN 202211549377 A CN202211549377 A CN 202211549377A CN 115974735 A CN115974735 A CN 115974735A
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- -1 carboxylic ester compound Chemical class 0.000 title claims abstract description 34
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000010189 synthetic method Methods 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
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 230000008569 process Effects 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 group 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 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
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001265 acyl fluorides Chemical class 0.000 abstract 2
- 238000002360 preparation method Methods 0.000 abstract 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000005917 acylation reaction Methods 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 3
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 3
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 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
- 206010059866 Drug resistance Diseases 0.000 description 1
- DGNFXAFTTHPOJI-UHFFFAOYSA-N FC(F)(F)S([Ag])(=O)=O Chemical compound FC(F)(F)S([Ag])(=O)=O DGNFXAFTTHPOJI-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- KAVUKAXLXGRUCD-UHFFFAOYSA-M sodium trifluoromethanesulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)F KAVUKAXLXGRUCD-UHFFFAOYSA-M 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000006692 trifluoromethylation reaction Methods 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 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 synthesis method of carboxylic ester compounds containing trifluoromethylthio. According to the method, an epoxy compound is used as a reaction substrate, trifluoromethyl thioester is used as a bifunctional reagent, and under the activation of fluorine anions, trifluoromethylthio anions and acyl fluorides are generated, the generated trifluoromethylthio anions quickly attack the epoxy compound to open the epoxy ring, and then the generated oxygen anions are regulated and controlled to quickly react with the acyl fluorides to realize an acylation reaction, so that the quick preparation of the carboxylic ester compound containing trifluoromethylthio is realized in one step, and the carboxylic ester compound containing trifluoromethylthio is obtained after separation and purification. According to the synthesis method of the carboxylic ester compound containing the trifluoromethylthio, raw materials and reaction reagents are easy to obtain, the reaction has good step economy, and the one-step rapid preparation of various carboxylic ester compounds containing the trifluoromethylthio can be realized.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and relates to a synthesis method of carboxylic ester compounds containing trifluoromethylthio.
Background
Fluorine atoms play an important role in modern drug design and synthesis (Liu X, xu C, wang M, et al. Trifluoromethyl. Nitrile: nucleoophilic fluorination and beyond [ J]Chem Rev,2015,115 (2): 683-730), statistically, 15-20% of modern drugs contain fluorine-containing groups(Hui R,Zhang S,Tan Z,et al.Research Progress of Trifluoromethylation with Sodium Trifluoromethanesulfinate[J]Chin J Org Chem (organic chemistry), 2017,37 (12): 3060-3075). The presence of fluorine-containing groups helps to increase the lipophilicity, metabolic stability of the drug molecule (Yang B, xu XH, qi FL. Cope-mediated chemical 1,2-bis (fluorination) of the drugs with sodium trifluoromethanesulfonate [ J]orgLett,2015,17 (8): 1906-1909.) also reduces the development of drug resistance, while trifluoromethylthio (-SCF) 3 ) Is one of the most lipophilic fluorine-containing functional groups (Hansch parameter pi) R = 1.44), the introduction of the group into the medicine can obviously change the liposolubility of the medicine, and improve the bioavailability and the biomembrane permeability of the medicine. (Glenadil Q, tlili A, billard T.Metal-Free Direct DeHydroxyytri-fluoromethlylation of alcoholic vista the reaction of fluoromethlyamines [ J].Eur J Org Chem,2016(11):1955-1957.)
Meanwhile, the team developed an important generation low-cost synthesis method of fluorine-containing sulfur-containing compound trifluoromethylthioester (ZL 202011200750.5) in 2020, and then developed a plurality of conversion methods of trifluoromethylthioester (ZL 202110211672.7; ZL202110209605.1; ZL202110214011. X). The trifluoromethyl thioester contains an acyl group and a trifluoromethylthio group, and if both are available, introduction of another molecule will allow rapid construction of a complex compound containing an acyl group and a trifluoromethylthio group, and will have good step economy and atom utilization.
Carboxylate compounds are frequently found in drug molecules and are important pharmacophore structures. Accordingly, the present invention has developed a synthetic method for producing a carboxylic ester compound containing a trifluoromethylthio group by using a trifluoromethylthio ester as an acyl donor and reacting the trifluoromethylthio donor with an epoxy compound.
Disclosure of Invention
The invention aims to provide a novel high-efficiency synthesis method for a novel carboxylic ester compound containing trifluoromethylthio. The synthesis method has the advantages of easily obtained synthesis raw materials and a trifluoro-methylthio reagent, low cost, no need of transition metal catalysis in the reaction, simple synthesis process, high step economy and the like.
The traditional method for synthesizing the carboxylic ester compound containing the trifluoromethylthio group mostly needs to introduce the trifluoromethylthio group and the ester group step by step, the steps are often more than two steps, the atom economy is often low, and reagents participating in the reaction cannot be generally introduced into a final molecule completely. Meanwhile, the traditional trifluoromethanesulfonyl reagent, such as trifluoromethanesulfonyl silver, is expensive, which increases the synthesis cost of the trifluoromethanesulfonyl compound. Therefore, the development of a synthetic method of the carboxylic ester compound containing the trifluoromethylthio group, which has economic steps, low cost and high atom economy, has important significance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a synthetic method of carboxylic ester compounds containing trifluoromethylthio is characterized in that: synthesizing carboxylic ester compounds containing trifluoromethylthio by taking an epoxy compound as a reaction substrate and trifluoromethylthioester as a reaction reagent in the presence of a fluorine anion activating reagent;
the reaction equation is:
in the formula (2), R 1 Is an aryl group;
in the formula (3), R 2 Is an aryl group;
the synthesis process of the compound shown in the formula (1) comprises the following steps: dissolving a compound shown as a formula (2) in a solvent in the presence of a fluorine anion activating reagent, and then mixing the compound with a compound shown as a formula (3) for reaction to generate a compound shown as a formula (1);
the fluorine anion activating reagent is any one of fluoride metal salt and fluoride organic salt containing univalent fluoride ions or a mixture thereof;
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 molar ratio of the epoxy compound shown in the formula (3), the trifluromethyl thioester shown in the formula (2) and the fluorine anion activating reagent is 1 (1-10) to 1-10;
the reaction temperature is 10-90 ℃, and the reaction time is 0.5-72 h.
Further preferably, the reaction system contains an additive, and the reaction equation is as follows:
the additive is crown ether;
the molar ratio of the compound shown in the formula (2) to the additive is 1: 0.25-10.
Compared with the existing synthesis method, the synthesis method of the carboxylic ester compound containing trifluoromethylthio has the following beneficial effects:
(1) The reaction reagent adopted by the invention is easy to prepare, and the trifluoromethyl thioester is taken as a trifluoromethyl sulfide donor, has low price compared with the prior noble metal salt type trifluoromethyl sulfide donor, and is beneficial to industrial production;
(2) The synthetic method has high atom utilization rate and economic step, and two functional groups are introduced in one step;
(3) The method is simple, convenient and safe to operate, mild in condition, free of transition metal catalysis in reaction, and 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1: in this example, an epoxy compound 3a was reacted with 4-benzenebenzoic acid trifluoromethylthioester (S- (trifluoromethyl) [1,1' -biphenyl ] -4-carbothioate) to synthesize a carboxylic ester compound 1a containing trifluoromethylthio group:
the reaction equation is:
the synthesis steps are as follows: 4-chlorobenzoic acid trifluoromethylthioester 3a (2mmol, 564mg), potassium fluoride (1.8mmol, 104.4mg), 18-crown-6 (1.8mmol, 475.2mg), and 3.0mL acetonitrile were added to a 10mL reaction tube equipped with a magnetic stirrer, and after stirring for 5min or more until the solution became black, 2a (1mmol, 120mg) was added; fixing the reaction tube on a magnetic stirrer, reacting for 12 hours at 70 ℃, separating and purifying to obtain a target product 1a with yield of 70%, and identifying the structure of 1a by using a gas chromatography-mass spectrometer and a nuclear magnetic resonance spectrometer.
The nuclear magnetic data for compound 1a is:
1 H NMR(600MHz,Chloroform-d):δ8.16-8.14(m,2H),7.68(d,J=10.2Hz,2H),7.62(d,J=10.2Hz,2H),7.48-4.39(m,8H),6.22-6.19(m,1H),3.54-3.37(m,2H)。
example 2: in this example, an epoxy compound 3a was reacted with 4-benzenebenzoic acid trifluoromethylthioester (S- (trifluoromethyl) [1,1' -biphenyl ] -4-carbothioate) to synthesize a trifluoromethylthio group-containing carboxylate compound 1a in gram-order:
the reaction equation is:
the synthesis steps are as follows: 4-chlorobenzoic acid trifluoromethylthioester 3a (20mmol, 5640mg), potassium fluoride (18mmol, 1044mg), 18-crown-6 (18mmol, 4752mg), and 30mL acetonitrile were added to a 100mL round-bottomed flask equipped with a magnetic stirrer, and after stirring for 10min or more until the solution became black, 2a (10mmol, 1200mg) was added; fixing the reaction tube on a magnetic stirrer, reacting for 15 hours at 70 ℃, and separating and purifying to obtain the target product 1a with the yield of 65%.
Claims (2)
1. A synthetic method of carboxylic ester compounds containing trifluoromethylthio is characterized in that: synthesizing carboxylic ester compounds containing trifluoromethylthio by taking an epoxy compound as a reaction substrate and trifluoromethylthioester 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;
in the formula (3), R 2 Is aryl;
the synthesis process of the compound shown in the formula (1) comprises the following steps: dissolving a compound shown as a formula (2) in a solvent in the presence of a fluorine anion activating reagent, and then mixing the compound with a compound shown as a formula (3) for reaction to generate a compound shown as a formula (1);
the fluorine anion activating reagent is any one of fluoride metal salt and fluoride organic salt containing negative univalent fluorine ions or a mixture thereof;
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 molar ratio of the epoxy compound shown in the formula (3), the trifluromethyl thioester shown in the formula (2) and the fluorine anion activating reagent is 1 (1-10) to 1-10;
the reaction temperature is 10-90 ℃, and the reaction time is 0.5-72 h.
2. The method for synthesizing carboxylic ester compounds containing trifluoromethylthio groups according to claim 1, wherein the reaction system contains an additive, and the reaction equation is as follows:
the additive is crown ether;
the molar ratio of the compound shown in the formula (2) to the additive is 1: 0.25-10.
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Citations (2)
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WO2021245005A1 (en) * | 2020-06-02 | 2021-12-09 | Bayer Aktiengesellschaft | Selective herbicides based on substituted isoxazolin carboxamides and cyprosulfamide |
CN114364666A (en) * | 2019-07-22 | 2022-04-15 | 拜耳公司 | Substituted N-phenyl-N-semicarbazides pyrimidines and salts thereof and their use as herbicides |
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CN114364666A (en) * | 2019-07-22 | 2022-04-15 | 拜耳公司 | Substituted N-phenyl-N-semicarbazides pyrimidines and salts thereof and their use as herbicides |
WO2021245005A1 (en) * | 2020-06-02 | 2021-12-09 | Bayer Aktiengesellschaft | Selective herbicides based on substituted isoxazolin carboxamides and cyprosulfamide |
Non-Patent Citations (1)
Title |
---|
TIAN QIN 等: "Chiral selenide-catalyzed enantioselective synthesis of trifluoromethylthiolated 2, 5-disubstituted oxazolines", ORGANIC &BIOMOLECULAR CHEMISTRY, 5 November 2018 (2018-11-05), pages 1763 * |
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