CN111892553A - Method for synthesizing ammonium acetate mediated benzothiazole compound - Google Patents
Method for synthesizing ammonium acetate mediated benzothiazole compound Download PDFInfo
- Publication number
- CN111892553A CN111892553A CN202010774855.5A CN202010774855A CN111892553A CN 111892553 A CN111892553 A CN 111892553A CN 202010774855 A CN202010774855 A CN 202010774855A CN 111892553 A CN111892553 A CN 111892553A
- Authority
- CN
- China
- Prior art keywords
- reaction
- iodo
- ammonium acetate
- synthesis method
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000005695 Ammonium acetate Substances 0.000 title claims abstract description 28
- 229940043376 ammonium acetate Drugs 0.000 title claims abstract description 28
- 235000019257 ammonium acetate Nutrition 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- -1 benzothiazole compound Chemical class 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 230000001404 mediated effect Effects 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 103
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001308 synthesis method Methods 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 54
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 16
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- UBPDKIDWEADHPP-UHFFFAOYSA-N 2-iodoaniline Chemical class NC1=CC=CC=C1I UBPDKIDWEADHPP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- ASINPZWBVCLVDK-UHFFFAOYSA-N 2-iodo-4-methoxyaniline Chemical compound COC1=CC=C(N)C(I)=C1 ASINPZWBVCLVDK-UHFFFAOYSA-N 0.000 claims description 3
- AJTUKWIQLKKRHE-UHFFFAOYSA-N 2-iodo-4-methylaniline Chemical group CC1=CC=C(N)C(I)=C1 AJTUKWIQLKKRHE-UHFFFAOYSA-N 0.000 claims description 3
- LOLSEMNGXKAZBZ-UHFFFAOYSA-N 2-iodo-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1I LOLSEMNGXKAZBZ-UHFFFAOYSA-N 0.000 claims description 3
- CYDBBGSUZRDOPE-UHFFFAOYSA-N 2-iodo-5-methoxyaniline Chemical compound COC1=CC=C(I)C(N)=C1 CYDBBGSUZRDOPE-UHFFFAOYSA-N 0.000 claims description 3
- KXPBTNCFONSVIA-UHFFFAOYSA-N 2-iodo-5-methylaniline Chemical compound CC1=CC=C(I)C(N)=C1 KXPBTNCFONSVIA-UHFFFAOYSA-N 0.000 claims description 3
- UUDNBWSHTUFGDQ-UHFFFAOYSA-N 3-iodopyridin-2-amine Chemical compound NC1=NC=CC=C1I UUDNBWSHTUFGDQ-UHFFFAOYSA-N 0.000 claims description 3
- UOWVTQFTEAYDLM-UHFFFAOYSA-N 4-amino-3-iodobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1I UOWVTQFTEAYDLM-UHFFFAOYSA-N 0.000 claims description 3
- FEOMAFDDLHSVMO-UHFFFAOYSA-N 5-chloro-2-iodoaniline Chemical compound NC1=CC(Cl)=CC=C1I FEOMAFDDLHSVMO-UHFFFAOYSA-N 0.000 claims description 3
- MRLVFVTVXSKAMX-UHFFFAOYSA-N Methyl 4-amino-3-iodobenzoate Chemical compound COC(=O)C1=CC=C(N)C(I)=C1 MRLVFVTVXSKAMX-UHFFFAOYSA-N 0.000 claims description 3
- VFKAZALEEBHHAG-UHFFFAOYSA-N 1-iodonaphthalen-2-amine Chemical compound C1=CC=CC2=C(I)C(N)=CC=C21 VFKAZALEEBHHAG-UHFFFAOYSA-N 0.000 claims description 2
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 claims description 2
- HHTYEQWCHQEJNV-UHFFFAOYSA-N 4-bromo-2-iodoaniline Chemical compound NC1=CC=C(Br)C=C1I HHTYEQWCHQEJNV-UHFFFAOYSA-N 0.000 claims description 2
- SSNQXCONXNVTJN-UHFFFAOYSA-N 4-chloro-2-fluoro-6-iodoaniline Chemical compound NC1=C(F)C=C(Cl)C=C1I SSNQXCONXNVTJN-UHFFFAOYSA-N 0.000 claims description 2
- FLEJOBRWKBPUOX-UHFFFAOYSA-N 4-chloro-2-iodoaniline Chemical compound NC1=CC=C(Cl)C=C1I FLEJOBRWKBPUOX-UHFFFAOYSA-N 0.000 claims description 2
- SETOTRGVPANENO-UHFFFAOYSA-N 4-fluoro-2-iodoaniline Chemical compound NC1=CC=C(F)C=C1I SETOTRGVPANENO-UHFFFAOYSA-N 0.000 claims description 2
- UCPDOOZBROQHME-UHFFFAOYSA-N 5-fluoro-2-iodoaniline Chemical compound NC1=CC(F)=CC=C1I UCPDOOZBROQHME-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000011403 purification operation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052799 carbon Inorganic materials 0.000 abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000005580 one pot reaction Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 description 53
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 26
- 229910052739 hydrogen Inorganic materials 0.000 description 26
- 239000001257 hydrogen Substances 0.000 description 26
- 238000004809 thin layer chromatography Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 238000011221 initial treatment Methods 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- 239000012044 organic layer Substances 0.000 description 13
- 239000007858 starting material Substances 0.000 description 13
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YJRSMJTVXWBFJJ-UHFFFAOYSA-N 2,4-dichloro-6-iodoaniline Chemical compound NC1=C(Cl)C=C(Cl)C=C1I YJRSMJTVXWBFJJ-UHFFFAOYSA-N 0.000 description 1
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960003116 amyl nitrite Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical class INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 description 1
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/84—Naphthothiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing an ammonium acetate mediated benzothiazole compound. The synthesis method comprises the following steps: adding an o-halophenylamine derivative, potassium sulfide, dimethyl sulfoxide, a catalyst, an additive 1 and an additive 2 into a reaction tube, stirring and reacting at 130-150 ℃, cooling to room temperature after the reaction is finished, and separating and purifying a product to obtain the benzothiazole compound. The invention develops the general formula of K2S is a sulfur source, DMSO is a carbon source and an oxidant, an o-halophenylamine derivative is a substrate, and an ammonium acetate mediated three-component one-pot method is used for synthesizing the benzothiazole compound. The method has the advantages of few reaction steps, mild reaction conditions, better functional group tolerance and the like.
Description
Technical Field
The invention belongs to the field of benzothiazole compounds, and particularly relates to a synthesis method of an ammonium acetate mediated benzothiazole compound.
Background
Benzothiazole is an important organic compound, and is a core skeleton of benzothiazole derivatives, so that the benzothiazole has important application value in the fields of medicines, chemical engineering and the like; secondly, because the benzothiazole at the 2-position is relatively active, a plurality of methods for synthesizing 2-substituted benzothiazole compounds have been developed by utilizing the functionalization of the 2-position C-H bond(A. Arora, J. D.Weaver,Org. Lett. 2016,18, 3996; X. Dai, Y. Zhu, Z. Wang, J. Weng,Chin. J. Org. Chem.2017,37,1924.), is an important raw material for synthesizing the 2-substituted benzothiazole compound. However, compared with the research reports on the synthesis method of 2-substituted benzothiazole compounds, the research reports on the synthesis method of benzothiazole compounds by chemical researchers are less, and the synthesis of benzothiazole compounds still remains to use organic sulfur reagents as sulfur sources. The more traditional method is to remove amino group by using 2-aminobenzothiazole as a substrate under the action of amyl nitrite to obtain a benzothiazole compound (G.M. Fischer, M.K. Klein, E. Daltrozzo, A. Zumbusch,Eur. J. Org. Chem. 2011,2011, 3421.). The reaction precursor 2-aminobenzothiazole of the method is not easy to obtain and can be obtained by utilizing aromatic amine to react under certain reaction conditions, which undoubtedly increases the cost of the reaction and limits the development of the reaction. Another reaction method is to use o-mercaptoaniline as a substrate and CO2(S, Chun, S, Yang, Y, K, Chung, Tetrahedron 2017, 73, 3438; X, Gao, B, Yu, Z, Yang, Y, ZHao, H, ZHang, L, Hao, B, Han, Z, Liu, ACS Catal 2015, 5, 6648.) or DMF (X, Gao, B, Yu, Q, Mei, Z, Yang, Y, ZHao, H, ZHang, L, Hao, Z, Liu,New J. Chem.2016,40,8282.) carbon source is provided, and the benzothiazole compounds are synthesized. The reaction substrate is unstable and the reaction conditions are harsh.
Therefore, it is very meaningful to develop a raw material which is easy to obtain and has better stability by using an inorganic sulfur reagent as a sulfur source, and synthesize the benzothiazole compound by a green and efficient method. The invention develops a method for synthesizing benzothiazole compounds by using o-iodoaniline as a substrate, potassium sulfide as a sulfur source, DMSO as a carbon source and performing a series reaction of three components in a one-pot method. The method has the advantages of few reaction steps, mild reaction conditions, better functional group compatibility and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an ammonium acetate mediated benzothiazole compoundThe method is provided. The invention develops a new medicine with K2S is a sulfur source, DMSO is a carbon source and an oxidant, an o-halophenylamine derivative is a substrate, and an ammonium acetate mediated three-component one-pot method is used for synthesizing the benzothiazole compound. The method has the advantages of few reaction steps, mild reaction conditions, higher functional group tolerance and the like, and develops a valuable path which is simple to operate, direct and atom-economical for the synthesis of the benzothiazole compounds.
The purpose of the invention is realized by the following technical scheme.
A method for synthesizing benzothiazole compounds mediated by ammonium acetate comprises the following steps:
adding an o-iodoaniline derivative, potassium sulfide, dimethyl sulfoxide, a catalyst, an additive and a solvent into a reaction tube, stirring and reacting at 130-150 ℃, cooling to room temperature after the reaction is finished, and separating and purifying a product to obtain the benzothiazole compound.
Further, the chemical reaction equation of the synthesis process is as follows:
wherein R is selected from one or more of unsubstituted C6-C10 aryl, methyl, cyano, nitro, methoxy, halogen and ester.
Preferably, in the synthesis method of the present invention, the iodoaniline derivative is 2-iodo-4-methylaniline, 2-iodo-4-cyanoaniline, 4-amino-3-iodobenzoic acid methyl ester, 2-iodo-4-nitroaniline, 2-iodo-4-methoxyaniline, 2-iodo-4-fluoroaniline, 2-iodo-4-chloroaniline, 2-iodo-4-bromoaniline, 2-iodo-5-methylaniline, 2-iodo-5-methoxyaniline, 2-iodo-5-fluoroaniline, 2-iodo-5-chloroaniline, 2, 4-dichloroaniline, 4-chloro-2-fluoro-6-iodoaniline, 2-amino-3-iodopyridine, 1-iodo-2-naphthylamine.
Furthermore, the molar ratio of the added potassium sulfide to the o-iodoaniline derivative is 2-4: 1, and preferably 3: 1.
Further, the amount of dimethyl sulfoxide added was 2 mL.
Further, the catalyst is one of cupric chloride, cupric bromide, cuprous iodide and cupric acetate, and is preferably cuprous iodide.
Furthermore, the molar ratio of the added amount of the catalyst to the o-iodoaniline derivative is 0.1-0.4: 1, and preferably 0.2: 1.
Further, the additive 1 is one of ammonium carbonate and ammonium acetate, and preferably ammonium acetate.
Furthermore, the molar ratio of the addition amount of the additive 1 to the o-iodoaniline derivative is 5-7: 1, and preferably 6: 1.
Further, the addition amount of the additive 2 is 40-120 ul, and preferably 80 ul.
Further, the stirring temperature is 130-150 ℃, and preferably 140 ℃.
Further, the stirring reaction time is 9-15 hours, preferably 10 hours.
Further, the separation and purification operations are as follows: and (2) enabling the reaction liquid to pass through a short column, extracting with ethyl acetate, combining organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating under reduced pressure to remove the organic solvent to obtain a crude product, and purifying by column chromatography to obtain the 2-substituted benzothiazole compound.
The invention develops a novel method for synthesizing benzothiazole compounds (6-m) by three-component 'one-pot' series reaction through the construction of C-S and C-N bonds under the mediation of ammonium acetate by using o-iodoaniline as a substrate, potassium sulfide as a sulfur source and DMSO (dimethyl sulfoxide) as a sulfur source and an oxidant.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention provides a method for synthesizing an ammonium acetate mediated benzothiazole compound. The invention provides a new medicine composition with K2S is a sulfur source, DMSO is a carbon source and an oxidant, an o-halophenylamine derivative is a substrate, and an ammonium acetate mediated three-component one-pot method is used for synthesizing the benzothiazole compound. The method has the advantages of few reaction steps, mild reaction conditions, higher functional group tolerance and the like.
(2) Benzothiazole is an important intermediate for synthesizing 2-substituted benzothiazole compounds, but the research on the synthesis method of benzothiazole compounds is less at the present stage, and the invention develops an efficient, simple and green method for synthesizing benzothiazole compounds.
Drawings
Fig. 1 and 2 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 1, respectively.
Fig. 3 and 4 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 2, respectively.
Fig. 5 and 6 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 3, respectively.
Fig. 7 and 8 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 4, respectively.
Fig. 9 and 10 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 5, respectively.
Fig. 11 and 12 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 6, respectively.
Fig. 13 and 14 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 7, respectively.
Fig. 15 and 16 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 8, respectively.
Fig. 17 and 18 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 9, respectively.
Fig. 19 and 20 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 10, respectively.
Fig. 21 and 22 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 11, respectively.
Fig. 23 and 24 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 12, respectively.
Fig. 25 and 26 are a hydrogen spectrum and a carbon spectrum of the objective product obtained in example 13, respectively.
Detailed description of the invention
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, but the scope and implementation of the present invention are not limited thereto.
Example 1
2-iodo-4-methylaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) were added sequentially to a dry Schlenk reaction tube, after the addition of the sample was completed, an oil pump was used to evacuate, nitrogen gas was injected for gas replacement, after three times of replacement, the reaction was stopped after 10 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) passing through a short column, extracting, collecting an organic layer, performing column chromatography to obtain a target product with the yield of 95%.
The hydrogen spectrum and the carbon spectrum of the obtained target product are respectively shown in fig. 1 and fig. 2, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)8.91 (s, 1H), 8.02 (d,J= 8.5 Hz, 1H), 7.75(s, 1H), 7.34 (dd,J= 8.0 Hz,J= 1.5 Hz, 1H), 2.51 (s, 1H);13C NMR (CDCl3,125 MHz)152.85, 151.35, 135.73, 133.87, 127.85, 123.03, 121.52, 21.49。
the structure of the target product is presumed to be as follows through the data:
example 2
2-iodo-4-methoxyaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) were sequentially added to a dried Schlenk reaction tube, and after the addition of the sample was completed, an oil pump was used to evacuate, and then nitrogen gas was injected for gas replacement, after which time the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) passing through a short column, extracting, collecting an organic layer, performing rotary powder chromatography to obtain a target product with the yield of 50%.
The hydrogen spectrum and the carbon spectrum of the obtained target product are respectively shown in fig. 3 and 4, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)8.82 (s, 1H), 8.00 (d,J= 8.5 Hz, 1H), 7.38(d,J= 2.5 Hz, 1H), 7.12 (dd,J= 9.0 Hz,J= 2.5 Hz, 1H), 3.88 (s, 3H);13CNMR (CDCl3, 125 MHz)157.93, 151.38, 147.77, 135.03, 123.93, 115.79,103.88,55.74。
the structure of the target product is presumed to be as follows through the data:
example 3
2-iodo-4-cyanoaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) were sequentially added to a dried Schlenk reaction tube, and after the addition of the sample was completed, an oil pump was used to evacuate, and then nitrogen gas was injected for gas replacement, after which time the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) passing through a short column, extracting, collecting an organic layer, performing column chromatography to obtain a target product with the yield of 95%.
The hydrogen spectrum and the carbon spectrum of the obtained target product are respectively shown in fig. 5 and 6, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)9.20 (s, 1H), 8.31 (d,J= 1.5 Hz, 1H), 8.20(d,J= 8.5 Hz, 1H), 7.76 (dd,J= 8.5Hz,J= 1.5 Hz, 1H);13C NMR (CDCl3, 125MHz)157.92, 155.39, 134.27, 129.19, 126.87, 124.47, 118.42, 109.23。
the structure of the target product is presumed to be as follows through the data:
example 4
4-amino-3-iodobenzoic acid methyl ester (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, nitrogen is injected for gas replacement, after the replacement is carried out for three times, the reaction is stopped after 11 hours at 140 ℃, and the reaction is cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) passing through a short column, extracting, collecting an organic layer, performing rotary powder chromatography to obtain a target product with the yield of 93%.
The hydrogen spectrum, the carbon spectrum and the fluorine spectrum of the obtained target product are respectively shown in fig. 7 and 8, and the nuclear magnetic data are as follows:
1H NMR (CDCl3, 500 MHz)9.15 (s, 1H), 8.69 (s, 1H), 8.19-8.15 (m, 2H),3.96 (s, 3H);13C NMR (CDCl3, 125 MHz)166.49, 157.25, 155.98, 133.74,127.47, 127.28, 124.20, 123.38, 52.39。
the structure of the target product is presumed to be as follows through the data:
example 5
2-iodo-4-nitroaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) were added sequentially into a dry Schlenk reaction tube, after the addition of the sample was completed, an oil pump was used to evacuate, nitrogen gas was injected for gas replacement, after three times of replacement, the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) passing through a short column, extracting, collecting an organic layer, performing column chromatography to obtain a target product, wherein the yield is 98%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 9 and fig. 10, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)9.27 (s, 1H), 8.92 (s, 1H), 8.40 (d,J= 9.0Hz, 1H), 7.24 (d,J= 9.0 Hz, 1H);13C NMR (CDCl3, 125 MHz)159.39, 156.74,145.47, 134.25, 124.06, 121.61, 118.58。
the structure of the target product is presumed to be as follows through the data:
example 6
2-iodine-4-fluoroaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) were added in sequence to a dried Schlenk reaction tube, and after the addition of the sample was completed, an oil pump was used for vacuum pumping, nitrogen gas was injected for gas substitution, and after the substitution was carried out three times, the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (4) passing through a short column, extracting, collecting an organic layer, performing rotary powder chromatography to obtain a target product with the yield of 62%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 11 and 12, and the nuclear magnetic data are as follows:
1H NMR (CDCl3, 500 MHz)8.94 (s, 1H), 8.08 (dd,J= 8.5 Hz,J= 4.5 Hz,1H), 7.63 (dd,J= 8.0 Hz,J= 2.5 Hz, 1H), 7.28 - 7.24 (m, 1H);13C NMR(CDCl3, 125 MHz)160.75 (d,J= 244.50 Hz), 153.53 (d,J= 3.00 Hz),149.93, 134.77 (d,J= 11.50 Hz), 124.54 (d,J= 9.50 Hz), 115.02 (d,J=24.75 Hz), 107.90 (d,J= 26.38 Hz)。
the structure of the target product is presumed to be as follows through the data:
example 7
2-iodo-5-methylaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) were added sequentially to a dry Schlenk reaction tube, after the addition of the sample was completed, an oil pump was used to evacuate, nitrogen gas was injected for gas replacement, after three times of replacement, the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) passing through a short column, extracting, collecting an organic layer, performing rotary powder chromatography to obtain a target product with the yield of 85%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 13 and 14, and the nuclear magnetic data are as follows:
1H NMR (CDCl3, 500 MHz)8.96 (s, 1H), 7.94 (s, 1H), 7.83 (d,J= 8.5 Hz,1H), 7.28 (d,J= 8.0 Hz, 1H);13C NMR (CDCl3, 125 MHz)153.95, 153.62,136.30, 130.63, 127.22, 123.51, 121.29, 21.41。
the structure of the target product is presumed to be as follows through the data:
example 8
2-iodo-5-methoxyaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) were sequentially added to a dried Schlenk reaction tube, after the addition of the sample was completed, an oil pump was used to evacuate, nitrogen gas was injected for gas replacement, after three times of replacement, the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (4) passing through a short column, extracting, collecting an organic layer, performing rotary powder chromatography to obtain a target product with the yield of 53%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 15 and 16, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)8.98 (s, 1H), 7.80 (d,J= 3.5 Hz, 1H), 7.61(d,J= 2.0 Hz, 1H), 7.10 (dd,J= 8.5 Hz,J= 2.0 Hz, 1H), 3.91 (s, 3H);13CNMR (CDCl3, 125 MHz)158.96, 155.01, 154.58, 125.49, 122.01, 116.08,105.54, 55.60。
the structure of the target product is presumed to be as follows through the data:
example 9
2-iodine-5-fluoroaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) were added in sequence to a dried Schlenk reaction tube, and after the addition of the sample was completed, an oil pump was used for vacuum pumping, nitrogen gas was injected for gas substitution, and after the substitution was carried out three times, the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) passing through a short column, extracting, collecting an organic layer, performing rotary powder chromatography to obtain a target product with the yield of 81%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 17 and fig. 18, and the nuclear magnetic data are as follows:
1H NMR (CDCl3, 500 MHz)9.04 (s, 1H), 7.88 (dd,J= 8.5 Hz,J= 5.0 Hz,1H), 7.81 (dd,J= 9.0 Hz,J= 2.5 Hz, 1H), 7.24 - 7.20 (m, 1H);13C NMR(CDCl3, 125 MHz)161.79 (d,J= 242.25 Hz), 156.21, 154.23 (d,J= 12.00Hz), 129.14, 122.53 (d,J= 9.75 Hz), 114.47 (d,J= 25.25 Hz), 109.67 (d,J= 23.38 Hz)。
the structure of the target product is presumed to be as follows through the data:
example 10
2, 4-dichloro-6-iodoaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, nitrogen is injected for gas replacement, after the replacement is carried out for three times, the reaction is stopped after 11 hours at 140 ℃, and the reaction is cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (4) passing through a short column, extracting, collecting an organic layer, performing rotary powder chromatography to obtain a target product with the yield of 58%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 19 and fig. 20, and the nuclear magnetic data are shown as follows:
1H NMR(CDCl3, 500 MHz)9.06 (s, 1H), 7.85(d,J= 1.0 Hz,.1H), 7.60 (d,J= 1.0 Hz, 1H);13C NMR(CDCl3, 125 Hz)155.09, 149.00, 135.94, 131.69, 128.99,126.99, 120.11。
the structure of the target product is presumed to be as follows through the data:
example 11
2-iodo-5-chloroaniline (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) were added sequentially to a dry Schlenk reaction tube, after the addition of the sample was completed, an oil pump was used to evacuate, nitrogen gas was injected for gas replacement, after three times of replacement, the reaction was stopped after 11 hours at 140 ℃, and the reaction was cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) passing through a short column, extracting, collecting an organic layer, performing column chromatography to obtain a target product with the yield of 83%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 21 and 22, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)9.02 (s, 1H), 8.12 (s, 1H), 7.86 (d,J= 9.0Hz, 1H), 7.41 (d,J= 9.0 Hz, 1H);13C NMR (CDCl3, 125 MHz)155.63, 154.10,132.29, 131.99, 126.11, 123.42, 122.53。
the structure of the target product is presumed to be as follows through the data:
example 12
1-iodine-2-naphthylamine (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, nitrogen is injected for gas replacement, after the replacement is carried out for three times, the reaction is stopped after 11 hours at 140 ℃, and the reaction is cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (3) passing through a short column, extracting, collecting an organic layer, performing column chromatography to obtain a target product with the yield of 95%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 23 and 24, and the nuclear magnetic data are shown as follows:
1H NMR(CDCl3, 500 MHz)9.07 (s, 1H), 8.16(d,J= 8.5 Hz,.1H), 8.07(d,J=8.0 Hz, 1H), 8.00 (d,J= 8.0 Hz, 1H), 7.91(d,J= 8.5 Hz, 1H), 7.64-7.57 (m,2H);13C NMR(CDCl3, 125 Hz)152.41, 151.41, 131.25, 131.09, 128.83, 127.97,127.25, 126.95, 126.13, 125.11, 121.74。
the structure of the target product is presumed to be as follows through the data:
example 13
2-amino-3-iodopyridine (0.2 mmol), potassium sulfide (0.6mmol), dimethyl sulfoxide (2 mL), cuprous iodide (0.04 mmol), ammonium acetate (1.2 mmol) and water (80 ul) are sequentially added into a dried Schlenk reaction tube, after the sample is added, an oil pump is used for vacuumizing, nitrogen is injected for gas replacement, after the replacement is carried out for three times, the reaction is stopped after 11 hours at 140 ℃, and the reaction is cooled to room temperature. The reaction was monitored by Thin Layer Chromatography (TLC) and when the starting material had reacted, the reaction was terminated and the mixture was cooled to room temperature in the reaction tube. Carrying out primary treatment on the mixed solution: and (4) passing through a short column, extracting, collecting an organic layer, performing rotary powder chromatography to obtain a target product with the yield of 52%.
The obtained hydrogen spectrum and carbon spectrum of the target product are respectively shown in fig. 25 and 26, and the nuclear magnetic data are shown as follows:
1H NMR (CDCl3, 500 MHz)9.31 (s, 1H), 8.80 (dd,J= 5.0 Hz,J= 1.5 Hz,1H), 8.34 (dd,J= 8.0 Hz,J= 1.5 Hz, 1H), 7.39 (dd,J= 8.0 Hz,J= 5.0 Hz,1H);13C NMR (CDCl3, 125 MHz)164.09, 157.45, 148.53, 131.15, 126.99,120.28。
the structure of the target product is presumed to be as follows through the data:
Claims (10)
1. a method for synthesizing benzothiazole compounds mediated by ammonium acetate is characterized by comprising the following steps:
adding an o-iodoaniline derivative, potassium sulfide, dimethyl sulfoxide, a catalyst, an additive 1 and an additive 2 into a reaction tube, stirring and reacting at 130-150 ℃, cooling to room temperature after the reaction is finished, and separating and purifying a product to obtain the benzothiazole compound.
3. The process according to claim 1 or 2, wherein the o-iodoaniline derivative is 2-iodo-4-methylaniline, 2-iodo-4-cyanoaniline, methyl 4-amino-3-iodobenzoate, 2-iodo-4-nitroaniline, 2-iodo-4-methoxyaniline, 2-iodo-4-fluoroaniline, 2-iodo-4-chloroaniline, 2-iodo-4-bromoaniline, 2-iodo-5-methylaniline, 2-iodo-5-methoxyaniline, 2-iodo-5-fluoroaniline, 2-iodo-5-chloroaniline, 2, 4-dichloroaniline, 4-chloro-2-fluoro-6-iodoaniline, 2-amino-3-iodopyridine, 1-iodo-2-naphthylamine.
4. The synthesis method according to claims 1-3, wherein the molar ratio of the added potassium sulfide to the o-iodoaniline derivative is 2-4: 1.
5. A synthesis method according to claims 1-3, characterized in that the dimethyl sulfoxide addition is 2 ml.
6. The synthesis method of claims 1-3, wherein the catalyst is one of cupric chloride, cupric bromide, cuprous iodide, cupric acetate; the molar ratio of the addition amount of the catalyst to the o-iodoaniline derivative is 0.1-0.4: 1.
7. The synthesis method according to claims 1-3, wherein the additive 1 is one of ammonium carbonate and ammonium acetate; the molar ratio of the addition amount of the additive to the o-iodoaniline derivative is 5-7: 1.
8. A synthesis method according to claims 1-3, characterized in that the additive 2 is water; the addition amount of the solvent is 40-120 ul.
9. The synthesis method according to claim 1 to 3, wherein the stirring temperature is 130-150 ℃; the reaction time is 8-12 hours.
10. The synthesis method according to claims 1 to 3, characterized in that the separation and purification operations are: and (3) enabling the reaction liquid to pass through a short column, extracting with ethyl acetate, combining organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating under reduced pressure to remove the organic solvent to obtain a crude product, and purifying by column chromatography to obtain the benzothiazole compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010774855.5A CN111892553A (en) | 2020-08-05 | 2020-08-05 | Method for synthesizing ammonium acetate mediated benzothiazole compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010774855.5A CN111892553A (en) | 2020-08-05 | 2020-08-05 | Method for synthesizing ammonium acetate mediated benzothiazole compound |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111892553A true CN111892553A (en) | 2020-11-06 |
Family
ID=73245539
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010774855.5A Pending CN111892553A (en) | 2020-08-05 | 2020-08-05 | Method for synthesizing ammonium acetate mediated benzothiazole compound |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111892553A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115260122A (en) * | 2022-08-31 | 2022-11-01 | 陕西科技大学 | Naphthothiazole derivative and synthesis method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104098528A (en) * | 2014-08-05 | 2014-10-15 | 内蒙古工业大学 | 2-mercapto benzothiazole derivative synthetic method with copper-catalyzed carbon disulfide |
-
2020
- 2020-08-05 CN CN202010774855.5A patent/CN111892553A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104098528A (en) * | 2014-08-05 | 2014-10-15 | 内蒙古工业大学 | 2-mercapto benzothiazole derivative synthetic method with copper-catalyzed carbon disulfide |
Non-Patent Citations (1)
Title |
---|
XIAOMING ZHU等: "K2S as Sulfur Source and DMSO as Carbon Source for the Synthesis of 2‑Unsubstituted Benzothiazoles", ORGANIC LETTERS, vol. 22, no. 10, pages 3789 - 3793 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115260122A (en) * | 2022-08-31 | 2022-11-01 | 陕西科技大学 | Naphthothiazole derivative and synthesis method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111205279B (en) | Polysubstituted benzodihydrofuran heterocyclic compound and preparation method and application thereof | |
CN108558692B (en) | Preparation method of amide compound | |
CN114634482B (en) | Diazonium difluoro methylation reagent and synthetic method and application thereof | |
CN114349674B (en) | Thiourea compound and preparation method thereof | |
CN114591194A (en) | Para-functional arylamine compound and synthesis method thereof | |
CN111892553A (en) | Method for synthesizing ammonium acetate mediated benzothiazole compound | |
CN111620808B (en) | 2-aldehyde indole compound and preparation method thereof | |
CN111704575B (en) | Synthesis method of quinoline-2-thiocarboxamide compound under conditions of no catalyst and no additive | |
CN111793042A (en) | Method for synthesizing benzothiazole compound by taking aromatic amine without halogen as substrate | |
CN111704591B (en) | Synthesis method of copper-catalyzed thionaphthothiazolone compound | |
CN113004178B (en) | Synthesis method of (E) -3-methylthio-2-iodoacrylate compound | |
CN110511193A (en) | A kind of α -one thioamide analog compound and its synthetic method | |
CN113735752B (en) | Method for preparing isothiourea compound based on substituted iodobenzene | |
CN108727323B (en) | Method for catalytically synthesizing trifluoromethyl substituted homoisoflavone compound by using N-heterocyclic carbene | |
CN108299384A (en) | Trifluoromethylthio transfering reagent compound and its synthetic method | |
CN107513056A (en) | A kind of synthetic method of the quinolines of the group containing tetrahydrofuran | |
CN109369553B (en) | Method for synthesizing N-3-isoxazole carbamic acid tert-butyl ester | |
JP6856471B2 (en) | A method for producing a lactone compound and a method for producing biotin using the lactone compound. | |
CN111269149A (en) | Production process of 5- (3,3-dimethylguanidino) -2-oxopentanoic acid | |
CN111517904A (en) | Preparation method of sulfonyl acetonitrile compound | |
CN111704590B (en) | Synthesis method of iron-catalyzed 2-arylbenzothiazole compound | |
CN108947995A (en) | A kind of preparation method of polysubstituted dxadiazine derivatives | |
CN110818647B (en) | Preparation method of heptatomic ring urea compound | |
CN110372718B (en) | Difluoromethane thiochromanonthiophene compound and preparation method thereof | |
CN111533694B (en) | Synthetic method of 2-imido hydantoin compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201106 |