CN116332881B - Preparation method of thioester derivative - Google Patents
Preparation method of thioester derivative Download PDFInfo
- Publication number
- CN116332881B CN116332881B CN202310618787.7A CN202310618787A CN116332881B CN 116332881 B CN116332881 B CN 116332881B CN 202310618787 A CN202310618787 A CN 202310618787A CN 116332881 B CN116332881 B CN 116332881B
- Authority
- CN
- China
- Prior art keywords
- acid
- nuclear magnetic
- thioacid
- tetrahydrofuran
- bond donor
- 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.)
- Active
Links
- 150000007970 thio esters Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 16
- -1 sulfur radical Chemical class 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 claims description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims description 3
- FMKQPMDFNYNYAG-UHFFFAOYSA-N 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine Chemical compound FC1=CC(F)=CC=C1C1=CC=C(C(F)(F)F)C=N1 FMKQPMDFNYNYAG-UHFFFAOYSA-N 0.000 claims description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 3
- VSANUNLQSRKIQA-UHFFFAOYSA-K trichlororuthenium hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru](Cl)Cl VSANUNLQSRKIQA-UHFFFAOYSA-K 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 150000003254 radicals Chemical class 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 43
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 42
- 238000005481 NMR spectroscopy Methods 0.000 description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 238000004440 column chromatography Methods 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
- 238000004896 high resolution mass spectrometry Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 125000004192 tetrahydrofuran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- 150000002081 enamines Chemical class 0.000 description 5
- 238000005286 illumination Methods 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BKIOOWFLXKTUPY-UHFFFAOYSA-N 2-chlorobenzenecarbothioic s-acid Chemical compound OC(=S)C1=CC=CC=C1Cl BKIOOWFLXKTUPY-UHFFFAOYSA-N 0.000 description 1
- BHJWUUSAMQADIT-UHFFFAOYSA-N 2-methylbenzenecarbothioic s-acid Chemical compound CC1=CC=CC=C1C(O)=S BHJWUUSAMQADIT-UHFFFAOYSA-N 0.000 description 1
- PJHWTWHVCOZCPU-UHFFFAOYSA-N 4-methylbenzenecarbothioic s-acid Chemical compound CC1=CC=C(C(O)=S)C=C1 PJHWTWHVCOZCPU-UHFFFAOYSA-N 0.000 description 1
- 244000089409 Erythrina poeppigiana Species 0.000 description 1
- 229910004354 OF 20 W Inorganic materials 0.000 description 1
- 235000009776 Rathbunia alamosensis Nutrition 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- KXXALFSFISKXFX-UHFFFAOYSA-N furan-2-carbothioic s-acid Chemical compound SC(=O)C1=CC=CO1 KXXALFSFISKXFX-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/30—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms, not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/34—Sulfur atoms
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention is applied to the technical field of organic synthesis, and discloses a preparation method of a thioester derivative, which uses C (sp 3 ) The method comprises the steps of taking an H bond donor as a solvent, taking a photosensitizer as a catalyst, and reacting a thioacid with the C (sp 3) -H bond donor to prepare the thioester derivative. The invention develops a visible light-induced free radical relay catalysis strategy, unactivated C (sp 3 ) Direct conversion of H bond with thioacid to C (sp 3 ) S bond without the need for additional hydrogen atom transfer reagents, complex sulfur radical precursor compounds, metals and additives. The process exhibits good functional group tolerance, water-air compatibility, environmental friendliness and high yield. Thioacids and unactivated C (sp 3 ) The substrate range of the H donor is very widespread and widespread.
Description
Technical Field
The invention is applied to the technical field of organic synthesis, and relates to a preparation method of a novel thioester derivative. Under the irradiation of an LED lamp with the wavelength of 425-430nm, acridine compounds are used as photosensitizers, and the thioacid free radical and hetero atom (N, O, S) alpha sp are used 3 The carbon radicals undergo free radical coupling to give a series of thioester derivatives.
Background
Unactivated C (sp) 3 ) Functionalization of the H bond presents a great challenge and opportunity for organic synthesis, pharmaceutical chemistry and material science. The key issue is how to effectively destroy high-energy C (sp 3 ) H bond, linking the carbon atom directly to other atoms or groups. Mercapto group as an excellent hydrogen atom donor to give it a stable electron-withdrawing group with C (sp 3 ) During the free radical reaction, hydrogen atom transfer can occur very rapidly, which makes the mercapto group not be directly applied to the field of free radical coupling to form carbon-sulfur bond, so scientists construct a series of precursor compounds capable of providing sulfur free radicalJ. Am. Chem. Soc.2016, 138, 13854-13857; J. Am. Chem. Soc.2019, 141, 12815-12823; J. Am. Chem. Soc.2016, 138, 16200-16203; Angew. Chem. Int. Ed.2018, 57, 10357-10361; Nat. Commun.2019, 10, 4867; Angew. Chem. Int. Ed.2021, 602849-2854Green Chem.2023, 25, 960-965). However, the thiol-group-containing compound still cannot directly participate in the reaction at present, the process of constructing the sulfur radical precursor compound is very difficult, the steps are complicated, and the research on the sulfur ester compound is relatively less.
Among various sulfur-containing compounds, thioesters are not only ubiquitous building blocks in many drugs, proteins and materialsScience 1994, 266,776-779; Nature2000, 407, 215-218; Acc. Chem. Res.2011, 44, 752-761; Chem. Soc. Rev.2013, 427900-7942J. Am. Chem. Soc.2022, 1446709-6713) which can be used as key intermediates for various chemical modification and conversionJ. Am. Chem. Soc.2000, 122, 11260-11261; Angew. Chem. Int. Ed.2009, 48, 2276-2286;Angew. Chem. Int. Ed. 2017, 562482-2486ACS Catal.2023, 13, 1848-1855). Previously reported syntheses of thioesters have generally employed metal catalysts and elevated temperatures, with concomitant formation of large amounts of waste and byproducts, narrow substrate ranges, low atom economy and environmental unfriendly [ ] productsNat. Catal.2020, 3887-892Eur. J. Org. Chem.2022, 25E 202200452). Therefore, the development of a more green and efficient thioester synthesis method with a wide substrate application range has important significance.
The invention uses thioacid and different C (sp 3 ) The H bond donor is used as a raw material, the acridine compound is used as a photosensitizer, and under the irradiation of an LED lamp with the wavelength of 425-430nm, a series of thioester derivatives can be obtained by only reacting for 1 hour. Water is the only byproduct and is therefore environmentally friendly and has high atomic economy.
Disclosure of Invention
The invention aims to provide a method for preparing a thioester derivative.
The technical scheme of the invention is as follows:
a preparation method of a thioester derivative comprises the following steps:
with C (sp) 3 ) The method is characterized in that an H bond donor is used as a solvent, a photosensitizer is used as a catalyst, and thioacid reacts with different C (sp 3) -H bond donors to prepare a thioester derivative, wherein the reaction general formula is as follows:
wherein R is 1 Is aryl or alkyl, R 2 Is alkyl; 2 is different C (sp 3 ) H bond donors (e.g. tetrahydrofuran, methyl tert-butyl ether,N,NDimethylacetamide and tetrahydrothiophene).
The photosensitizer comprises bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine ] [2-2'' -bis (4-tert-butylpyridine) ] iridium (III) hexafluorophosphate, terpyridyl ruthenium chloride hexahydrate, rhodamine B, 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile, 3,6, -di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate and the like, preferably 3,6, -di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate; the photosensitizer is used in an amount of 0.2 to 2% equivalents, preferably 0.5% equivalents, of the thioacid.
The thioacid refers to an acid with a single sulfur atom to replace an oxygen atom on a hydroxyl group in the oxyacid, and concretely comprises thiobenzoic acid, thiobenzoic acid containing substituent groups, thiofurancarboxylic acid, thionaphthoic acid, thioheptanoic acid and the like.
The light sources are white light (6000-6500 k), red light (700-705 nm), yellow light (595-600 nm), green light (540-545 nm), blue light (460-465 nm, 425-430 nm), ultraviolet light (365-370 nm) and the like, and blue light (425-430 nm) is preferred.
The power of the light source is 10-40W, preferably 20W.
Said thioacids and C (sp 3 ) The feed ratio of H-bond donor 2 is: 0.2mmol:1-3ml, preferably 0.2mmol:3ml.
The reaction temperature is 25-60 ℃, preferably 25 ℃; the reaction time was 1h.
The post-treatment mode is as follows: the solvent was removed by distillation under reduced pressure, the residue was separated by column chromatography, and the product was dried to constant weight in a vacuum oven.
The invention has the beneficial effects that: the invention develops a visible light-induced free radical relay catalysis strategy, unactivated C (sp 3 ) Direct conversion of H bond with thioacid to C (sp 3 ) S bond without the need for additional hydrogen atom transfer reagents, complex sulfur radical precursor compounds, metals and additives. The process shows good functional group tolerance, water-air compatibility, environmental friendliness and high yields (up to 98%). Thioacids and unactivated C (sp 3 ) The substrate range of the H donor is very widespread and widespread.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of S- (tetrahydrofuran-2-yl) thiobenzoate.
FIG. 2 is a nuclear magnetic carbon spectrum of S- (tetrahydrofuran-2-yl) thiobenzoate.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of S- (tetrahydrofuran-2-yl) 4-methylthiobenzoate.
FIG. 4 is a nuclear magnetic carbon spectrum of S- (tetrahydrofuran-2-yl) 4-methylthiobenzoate.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of S- (tetrahydrofuran-2-yl) 4-iodothiophosphate.
FIG. 6 is a nuclear magnetic carbon spectrum of S- (tetrahydrofuran-2-yl) 4-iodothiophosphate.
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of S- (tetrahydrofuran-2-yl) 2-chlorothiophosphate.
FIG. 8 is a nuclear magnetic carbon spectrum of S- (tetrahydrofuran-2-yl) 2-chlorothiophosphate.
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of S- (tetrahydrofuran-2-yl) 2-methylthiobenzoate.
FIG. 10 is a nuclear magnetic carbon spectrum of S- (tetrahydrofuran-2-yl) 2-methylthiobenzoate.
FIG. 11 is a nuclear magnetic resonance hydrogen spectrum of S- (tetrahydrofuran-2-yl) furan-2-thiocarboxylate.
FIG. 12 is a nuclear magnetic carbon spectrum of S- (tetrahydrofuran-2-yl) furan-2-thiocarboxylate.
FIG. 13 is a nuclear magnetic resonance hydrogen spectrum of S- (tetrahydrofuran-2-yl) naphthalene-2-thioformate.
FIG. 14 is a nuclear magnetic carbon spectrum of S- (tetrahydrofuran-2-yl) naphthalene-2-thioformate.
FIG. 15 is a nuclear magnetic resonance hydrogen spectrum of S- (tetrahydrofuran-2-yl) heptanesulfonate.
FIG. 16 is a nuclear magnetic carbon spectrum of S- (tetrahydrofuran-2-yl) heptanesulfonate.
FIG. 17 is a nuclear magnetic resonance hydrogen spectrum of S- (tert-butoxymethyl) thiobenzoate.
FIG. 18 is a nuclear magnetic resonance spectrum of S- (tert-butoxymethyl) thiobenzoate.
FIG. 19 is a nuclear magnetic resonance hydrogen spectrum of S- ((N-methylacetamido) methyl) thio benzoate.
FIG. 20 is a nuclear magnetic carbon spectrum of S- ((N-methylacetamido) methyl) thio benzoate.
FIG. 21 is a nuclear magnetic resonance hydrogen spectrum of S- (tetrahydrothiophen-2-yl) thiobenzoate.
FIG. 22 is a nuclear magnetic carbon spectrum of S- (tetrahydrothiophen-2-yl) thiobenzoate.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1:
Spreparation of- (tetrahydrofuran-2-yl) thiobenzoate
3,6, -Di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate (0.6 mg,0.5 mol%) (An Naiji, purity 97%, cat. No. D055074), thiobenzoic acid (27.6 mg,0.2 mmol) (An Naiji, purity 95%, cat. A011115) and tetrahydrofuran (3.0 mL) (An Naiji, purity 99.5% ultra-dry, cat. W310075) were added to a vial containing the magnetons and the mixture was stirred for 1 hour at 25℃under LED lamp illumination at a power of 10W, wavelength 425-430 nm. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give colorless liquid 3a (41 mg, yield 98%).
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 7.93 (d,J = 7.8 Hz, 2H), 7.56 (t, J = 7.2 Hz, 1H), 7.43 (t, J = 7.7 Hz, 2H), 6.20 (dd, J = 7.1, 3.3 Hz, 1H), 4.05 – 3.89 (m, 2H), 2.46 (m, J = 16.0, 14.0, 7.3 Hz, 1H), 2.16 (m, J=18.1, 15.0, 6.6 Hz, 1H), 2.10-1.92 (m, 2H), (fig. 1)
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) delta 191.63, 137.13, 133.50, 128.61, 127.42, 83.68, 68.48, 32.80, 24.71 (fig. 2)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 11 H 12 O 2 SNa, 231.0456; measured value 231.0458
Example 2:
Spreparation of- (tetrahydrofuran-2-yl) 4-methylthiobenzoate
Bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine ] [2-2'' -bis (4-t-butylpyridine) ] iridium (III) hexafluorophosphate (0.4 mg,0.2 mol%) (An Naiji, purity 97%, cat# E062356), 4-methylthiobenzoic acid (30.2 mg,0.2 mmol) (Aituo chemical, purity 95%) and tetrahydrofuran (3.0 mL) (An Naiji, purity 99.5% ultra-dry type, cat# W310075) were added to a vial containing magnetons, and the mixture was stirred at 40℃for 1 hour under irradiation of an LED lamp having a power of 20W and a wavelength of 425-430 nm. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give colorless liquid 3b (37 mg, yield 85%).
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 7.83 (d,J = 8.2 Hz, 2H), 7.23 (d, J = 8.1 Hz, 2H), 6.19 (dd, J = 7.1, 3.4 Hz, 1H), 4.03 – 3.92 (m, 2H), 2.46 (m, J = 16.3, 14.4, 7.4 Hz, 1H), 2.40 (s, 3H), 2.21 – 2.11 (m, 1H), 2.11 – 1.92 (m, 2H), (FIG. 3)
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) delta 191.14, 144.34, 134.66, 129.25, 127.49, 83.56, 68.42, 32.81, 24.72, 21.69 (fig. 4)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 12 H 14 O 2 SNa, 245.0612; measured value, 245.0617.
Example 3:
Spreparation of- (tetrahydrofuran-2-yl) 4-iodothiophosphate
Terpyridyl ruthenium chloride hexahydrate (3.0 mg,2 mol%) (An Naiji, purity 98%, cat# E060194), 4-iodothiobenzoic acid (52.8 mg,0.2 mmol) (Enamine reagent Co., purity 95%, cat# MFCD 33441971) and tetrahydrofuran (3.0 mL) (An Naiji, purity 99.5% ultra-dry type cat# W310075) were added to a vial containing the magnetons, and the mixture was stirred at 25℃for 1 hour under irradiation of an LED lamp having a power of 20W and a wavelength of 425-430 nm. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give colorless liquid 3c (55 mg, yield 83%).
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 7.80 (d,J = 8.3 Hz, 2H), 7.64 (d, J = 8.3 Hz, 2H), 6.19 (dd, J = 7.0, 3.2 Hz, 1H), 4.04 – 3.93 (m, 2H), 2.53 – 2.35 (m, 1H), 2.16 (m, J=16.7, 8.3, 4.4 Hz, 1H), 2.10-1.95 (m, 2H), (fig. 5)
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) δ 190.94, 137.89, 136.48, 128.72, 101.29, 83.89, 68.53, 32.81, 24.66. (fig. 6)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 11 H 11 O 2 SINA, 356.9422; measurement 356.9418.
Example 4:
Spreparation of- (tetrahydrofuran-2-yl) 2-chlorothiophosphate
Rhodamine B (1.9 mg,2 mol%) (An Naiji, purity 95%, cat# E080871), 2-chlorothiobenzoic acid (34.2 mg,0.2 mmol) (Enamine reagent Co., purity 95%, cat# MFCD 33441502) and tetrahydrofuran (3.0 mL) (An Naiji, purity 99.5% ultra-dry type, cat# W310075) were added to the vials containing the magnetons, and the mixture was stirred at 60℃for 1 hour under irradiation of green light having a power of 20W and a wavelength of 540-545 nm. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give a colorless liquid 3d (35 mg, yield 73%).
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 7.64 (dd,J = 7.7, 1.4 Hz, 1H), 7.41 (m, J = 9.5, 8.0, 1.5 Hz, 2H), 7.31 (m, J = 7.4, 1.5 Hz, 1H), 6.18 (dd, J = 7.0, 3.2 Hz, 1H), 4.05 – 3.92 (m, 2H), 2.48 (m, J = 16.1, 14.1, 7.4 Hz, 1H), 2.17 (m, J=13.2, 7.6, 5.7, 3.3 Hz, 1H), 2.11-1.92 (m, 2H), (fig. 7)
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) δ 191.55, 137.47, 132.25, 130.87, 130.83, 129.31, 126.67, 84.37, 68.66, 32.89, 24.60. (fig. 8)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 11 H 11 O 2 SClNa, 265.0066, measured 265.0071.
Example 5:
Spreparation of- (tetrahydrofuran-2-yl) 2-methylthiobenzoate
2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile (0.8 mg,0.5 mol%) (Aladine, purity 99%, cat# T302842), 2-methylthiobenzoic acid (30.2 mg,0.2 mmol) (Enamine reagent Co., purity 95%, cat# BBV-77619924) and tetrahydrofuran (3.0 mL) (An Naiji, purity 99.5% ultra-dry type, cat# W310075) were added to a vial containing a magneton, and the mixture was stirred at 25℃for 1 hour under irradiation of an LED lamp having a power of 20W and a wavelength of 425-430 nm. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give 3e (32 mg, yield 71%) as a colorless liquid.
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 7.76 (d,J = 8.0 Hz, 1H), 7.37 (t, J = 7.4 Hz, 1H), 7.23 (t, J = 5.8 Hz, 2H), 6.13 (dd, J=6.8, 3.2 Hz, 1H), 4.04-3.91 (m, 2H), 2.51 (s, 3H), 2.49-2.39 (m, 1H), 2.19-2.09 (m, 1H), 2.09-1.92 (m, 2H) (fig. 9)
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) δ 193.59, 137.34, 137.16, 131.75, 131.64, 128.71, 125.71, 83.81, 68.44, 32.73, 24.74, 20.72 (fig. 10)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 12 H 14 O 2 SNa, 245.0612; measured value, 245.0620.
Example 6:
Spreparation of- (tetrahydrofuran-2-yl) furan-2-thiocarboxylate
3,6, -Di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate (0.6 mg,0.5 mol%) (An Naiji, purity 97%, cat# D055074), 2-furanthiocarboxylic acid (25.6 mg,0.2 mmol) (Alfa reagent Co., purity 97%) and tetrahydrofuran (3.0 mL) (An Naiji, purity 99.5% ultra-dry type cat# W310075) were added to a vial containing a magnet, and the mixture was stirred under irradiation of an LED lamp having a power of 20W and a wavelength of 425-430nm for 1 hour at 25 ℃. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give 3f (32 mg, yield 83%) as a colorless liquid.
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 7.57 (s, 1H), 7.19 (d,J = 3.5 Hz, 1H), 6.56 – 6.50 (m, 1H), 6.22 (dd, J=7.1, 3.3 Hz, 1H), 4.03-3.93 (m, 2H), 2.54-2.34 (m, 1H), 2.24-2.11 (m, 1H), 2.11-1.91 (m, 2H), (fig. 11)
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) δ 179.88, 150.87, 146.27, 115.97, 112.27, 83.07, 68.43, 32.78, 24.62 (fig. 12)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 9 H 10 O 3 SNa, 221.0248; measured value, 221.0252.
Example 7:
Spreparation of- (tetrahydrofuran-2-yl) naphthalene-2-thioformate
3,6, -Di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate (0.6 mg,0.5 mol%) (An Naiji, purity 97%, cat# D055074), 2-naphthiocarboxylic acid (37.2 mg,0.2 mmol) (Enamine reagent Co., purity 95%, cat# BBV-106087512) and tetrahydrofuran (3.0 mL) (An Naiji, purity 99.5% ultra-dry type, cat# W310075) were added to a vial containing magnetons, and the mixture was stirred at 25℃for 1 hour under LED lamp illumination at a power of 40W, wavelength of 425-430 nm. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give 3g (27, mg, yield 52%) of a colorless liquid.
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 8.50 (s, 1H), 7.97 (t,J = 7.3 Hz, 2H), 7.87 (dd, J = 8.4, 3.1 Hz, 2H), 7.57 (m, J = 14.8, 7.0 Hz, 2H), 6.27 (dd, J = 7.1, 3.3 Hz, 1H), 4.10 – 3.92 (m, 2H), 2.50 (m, J=20.8, 7.7 Hz, 1H), 2.28-2.15 (m, 1H), 2.15-1.76 (m, 2H), (fig. 13)
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) δ 191.48, 135.84, 134.51, 132.45, 129.60, 128.95, 128.51, 128.47, 127.82, 126.90, 123.23, 83.83, 68.50, 32.89, 24.72 (fig. 14)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 15 H 14 O 2 SNa, 281.0612; measured value, 281.0620.
Example 8:
Spreparation of- (tetrahydrofuran-2-yl) heptanesulfonate
3,6, -Di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate (0.6 mg,0.5 mol%) (An Naiji, purity 97%, cat# D055074), thioheptanoic acid (29.2 mg,0.2 mmol) (Enamine reagent Co., purity 95%, cat# BBV-165143731) and tetrahydrofuran (3.0 mL) (An Naiji, purity 99.5% ultra-dry type, cat# W310075) were added to a vial containing a magnet, and the mixture was stirred at 25℃for 1 hour under irradiation of an LED lamp having a power of 40W and a wavelength of 425-430 nm. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give a colorless liquid for 3h (32 mg, yield 73%).
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 5.40-5.25 (m, 1H), 4.09-3.88 (m, 2H), 2.70 (t,J = 7.4 Hz, 2H), 2.30 (m, J = 19.8, 12.4, 6.9 Hz, 1H), 2.17 – 1.97 (m, 2H), 1.97 – 1.84 (m, 1H), 1.79 – 1.63 (m, 2H), 1.29 (s, 6H), 0.88 (t, J=6.4 Hz, 3 h.) (fig. 15
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) delta 197.89, 89.39, 67.87, 42.52, 32.37, 31.36, 28.59, 25.45, 24.35, 22.40, 13.97 (fig. 16)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 11 H 20 O 2 SNa, 239.1082; measured value, 239.1084.
Example 9:
Spreparation of- (tert-butoxymethyl) thiobenzoate
3,6, -Di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate (0.6 mg,0.5 mol%) (An Naiji, purity 97%, cat. No. D055074), thiobenzoic acid (27.6 mg,0.2 mmol) (An Naiji, purity 95%, cat. A011115) and methyl tert-butyl ether (3.0 mL) (An Naiji, purity 99% ultra-dry, cat. W330162) were added to a vial containing magnetons and the mixture was stirred for 1 hour under LED lamp illumination at a power of 40W, wavelength 425-430 nm. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give colorless liquid 3i (28, mg, yield 63%).
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 7.98 (d,J = 8.0 Hz, 2H), 7.57 (t, J = 7.4 Hz, 1H), 7.45 (t, J=7.7 Hz, 2H), 5.22 (s, 2H), 1.30 (s, 9H), (fig. 17)
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) δ 190.61, 137.02, 133.52, 128.61, 127.51, 75.96, 62.79, 27.72 (fig. 18)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 12 H 16 O 2 SNa, 247.0769; measured value, 265.0773.
Example 10:
Spreparation of- ((N-methylacetamido) methyl) thiobenzoate
3, 6-Di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate (0.6 mg,0.5 mol%) (An Naiji, purity 97%, cat. D055074), thiobenzoic acid (27.6 mg,0.2 mmol) (An Naiji, purity 95%, cat. A011115) andN,Ndimethylacetamide (3.0 mL) (An Naiji, 99.8% purity ultra-dry, cat No. W610492) was added to a vial containing magnetons, the mixture was then mixedUnder the irradiation of an LED lamp with the power of 20 w and the wavelength of 425-430nm, stirring is carried out for 1 hour at 25 ℃. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give colorless liquid 3j (33 mg, yield 75%).
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chloroform) delta 8.06-7.88 (m, 2H), 7.67-7.55 (m, 1H), 7.55-7.42 (m, 2H), 5.10 (d,J = 4.7 Hz, 2H), 3.05 (d, J = 53.7 Hz, 3H), 2.18 (d, J=61.8 Hz, 3 h.) (fig. 19
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) δ 191.85, 171.55, 134.05, 133.73, 128.82, 128.70, 127.52, 127.46, 50.64, 46.60, 36.04, 21.69, 21.58 (fig. 20)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 11 H 13 NO 2 SNa, 246.0565; measured value, 246.0555.
Example 11:
Spreparation of- (tetrahydrothiophen-2-yl) thiobenzoate
3,6, -Di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate (0.6 mg,0.5 mol%) (An Naiji, purity 97%, cat# D055074), thiobenzoic acid (27.6 mg,0.2 mmol) (An Naiji, purity 95%, cat# A011115) and tetrahydrothiophene (3.0 mL) (An Naiji, purity 98%, cat# W330223) were added to a vial containing the magnetons and the mixture was stirred for 1 hour at 25℃under irradiation of a white light lamp having a power of 40W and a wavelength of 6000-6500 k. After the completion of the reaction, the solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography to give 3k (35 mg, yield 79%) as a colorless liquid.
Nuclear magnetic hydrogen spectrum: 1 h NMR (400 MHz, deuterated chlorine)Imitation) delta 7.94 (d,J = 7.5 Hz, 2H), 7.58 (t, J = 7.3 Hz, 1H), 7.45 (t, J = 7.5 Hz, 2H), 4.29 (dd, J = 12.5, 6.2 Hz, 1H), 3.34 (dd, J = 10.9, 6.1 Hz, 1H), 2.99 (t, J = 6.6 Hz, 2H), 2.88 (dd, J = 10.9, 6.5 Hz, 1H), 2.43 (m, J = 12.0, 6.0 Hz, 1H), 2.11 (m, J=13.8, 7.0 Hz, 1 h.) (fig. 21
Nuclear magnetic carbon spectrum: 13 c NMR (101 MHz, deuterated chloroform) delta 191.50, 136.87, 133.57, 128.68, 127.25, 46.10, 37.03, 36.62, 29.85 (fig. 22)
High resolution mass spectrometry: HRMS (ESI-TOF),m/z): [M+Na] + calculated value C 11 H 12 OS 2 Na, 247.0027, measured 247.0032.
Claims (3)
1. A method for producing a thioester derivative, comprising the steps of:
with C (sp) 3 ) -H bond donor as solvent, photosensitizer as catalyst, thioacid and C (sp 3 ) The reaction of H bond donor to prepare thioester derivative has the following general formula:
wherein R is 1 Is aryl or alkyl, R 2 Is alkyl; 2 is C (sp) 3 ) -an H-bond donor;
the dosage of the photosensitizer is 0.1-2% equivalent of the thioacid;
thio acid and C (sp) 3 ) The feed ratio of H-bond donor 2 is: 0.2mmol:1-3ml;
the power of the light source is 10-40W;
the reaction temperature is 25-60 ℃; the reaction time is 1h;
said C (sp 3 ) -H bond donor is tetrahydrofuran, methyl tert-butyl ether, N-dimethylacetamide or tetrahydrothiophene;
the photosensitizer comprises bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine ] [2-2' -bis (4-tert-butylpyridine) ] iridium (III) hexafluorophosphate, terpyridine ruthenium chloride hexahydrate, rhodamine B, 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile, 3,6, -di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate.
2. The method according to claim 1, wherein the thioacid is an acid having a single sulfur atom substituted for an oxygen atom on a hydroxyl group in the oxyacid, and includes thiobenzoic acid, substituted thiobenzoic acid, thiofurancarboxylic acid, thionaphthoic acid, and thioheptanoic acid.
3. The method of claim 1, wherein the light source is 6000-6500k white light, 540-545nm green light, 425-430nm blue light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310618787.7A CN116332881B (en) | 2023-05-30 | 2023-05-30 | Preparation method of thioester derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310618787.7A CN116332881B (en) | 2023-05-30 | 2023-05-30 | Preparation method of thioester derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116332881A CN116332881A (en) | 2023-06-27 |
| CN116332881B true CN116332881B (en) | 2023-08-08 |
Family
ID=86876308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310618787.7A Active CN116332881B (en) | 2023-05-30 | 2023-05-30 | Preparation method of thioester derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116332881B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1320256A (en) * | 1970-09-10 | 1973-06-13 | Lilly Co Eli | Thioester and method of preparing same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2299247A1 (en) * | 2000-02-25 | 2001-08-25 | Felix J. Baerlocher | Sulfur containing compounds |
| EP1274460A4 (en) * | 2000-04-15 | 2005-06-29 | Kolon Inc | Aqueous-prodrug compound comprising moiety of paclitxel or derivatives thereof, method of preparing same and pharmaceutical composition comprising same |
-
2023
- 2023-05-30 CN CN202310618787.7A patent/CN116332881B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1320256A (en) * | 1970-09-10 | 1973-06-13 | Lilly Co Eli | Thioester and method of preparing same |
Non-Patent Citations (1)
| Title |
|---|
| Vedejs.Diastereoselectivity in the Diels-Alder reactions of thio aldehydes.Journal of the American Chemical Society.1988,参见全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116332881A (en) | 2023-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Synthesis of trifluoroalkyl or difluoroalkyl phenanthridine derivatives via cascade reaction using an intramolecular cyano group as a radical acceptor under photoredox catalysis | |
| Lv et al. | Additive-free synthesis of S-substituted isothioureas via visible-light-induced four-component reaction of α-diazoesters, aryl isothiocyanates, amines and cyclic ethers | |
| CN104803898A (en) | Aryl-alkyl and aryl-aryl thioether compound and synthesis method thereof | |
| KR20040026626A (en) | New process for the industrial synthesis of tetraesters of 5-[bis(carboxymethyl)amino]-3-carboxymethyl-4-cyano-2-thiophenecarboxylic acid, and application to the synthesis of bivalent salts of ranelic acid and their hydrates | |
| CN112675919A (en) | Application of N-heterocyclic carbene-based mixed nickel (II) complex in synthesis of alpha-benzylbenzofuran compounds | |
| CN116332881B (en) | Preparation method of thioester derivative | |
| CN112442002B (en) | Method for synthesizing 11-sulfenyl naphtho [2,3-b ] benzofuran compound | |
| Wang et al. | Polysulfide synthesis via visible-light-induced heteroarene-migratory dithiosulfonylation reaction | |
| CN112457234B (en) | Visible light promoted synthesis method of 2-selenomethylpyrrolidine compound | |
| Xie et al. | Syntheses of 4-allyl-/4-allenyl-4-(arylthio)-1, 4-dihydroisoquinolin-3-ones via the photochemical Doyle–Kirmse reaction | |
| KR20140123070A (en) | Intermediate for acenedichalcogenophene derivative and method for synthesizing same | |
| CN116514621B (en) | Method for constructing C-C bond at ortho-position of aryl by metal-catalyzed sulfur ylide and aryl sulfur/selenoacetic acid ester rearrangement reaction | |
| Tang et al. | Multicomponent reactions to access S-aryl dithiocarbamates via an electron donor–acceptor complex under open-to-air conditions | |
| CN109180607B (en) | Method for synthesizing thiazine diketone heterocyclic compound by catalyzing carbonyl sulfide conversion with organic catalyst | |
| CN114292220B (en) | Photocatalytic synthesis method of thioether compound | |
| CN113845521B (en) | Method for synthesizing imidazo nitrogen-containing heterocyclic hydrazine derivative by aqueous phase photocatalysis one-pot method | |
| Kurbangalieva et al. | Reactions of 2-mercaptoacetic acid with mucochloric acid and its derivatives | |
| CN114874116A (en) | Preparation method of thiosulfonate | |
| Tareque Abedin et al. | Reactivity of the Unsaturated Triosmium Cluster [Os3 (CO) 8 {Ph2PCH2P (Ph) C6H4}(μ-H)] with Thiols | |
| Liu et al. | Selectfluor-Promoted Twofold Sulfination of Alcohols for the Synthesis of Sulfinic Ester from Diaryldisulfides | |
| CN111484476B (en) | 3-hydro-1, 2-dithio-2, 2-dioxide and preparation method thereof | |
| CN114213370B (en) | Method for synthesizing alkylated electron-rich heterocyclic aromatic hydrocarbon by photo-induced NHPI ester decarboxylation coupling | |
| WO2023134776A1 (en) | Iron-catalyzed highly enantioselective cis-dihydroxylation of quinones | |
| KR20200089965A (en) | New β-selenylated ketone derivatives and Synthetic method thereof | |
| CN114835674A (en) | Preparation method of aromatic thioether |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |