CN115819301B - Method for preparing alkynyl sulfur (selenium) ether by coupling zinc-promoted disulfide (selenium) ether with alkynyl bromine - Google Patents
Method for preparing alkynyl sulfur (selenium) ether by coupling zinc-promoted disulfide (selenium) ether with alkynyl bromine Download PDFInfo
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 61
- -1 alkynyl bromine Chemical compound 0.000 title claims abstract description 26
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 125000000304 alkynyl group Chemical group 0.000 title claims abstract description 15
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 14
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 14
- 239000011669 selenium Substances 0.000 title claims abstract description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 38
- 238000005859 coupling reaction Methods 0.000 title description 3
- 230000008878 coupling Effects 0.000 title description 2
- 238000010168 coupling process Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010189 synthetic method Methods 0.000 claims abstract description 9
- 238000001308 synthesis method Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006880 cross-coupling reaction Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 3
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 229940102001 zinc bromide Drugs 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 55
- 239000007787 solid Substances 0.000 description 21
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- OBUPEYCFDRLOFR-UHFFFAOYSA-N 1-(2-bromoethynyl)-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C#CBr)C=C1 OBUPEYCFDRLOFR-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MWLDFOCAVDOKBW-UHFFFAOYSA-N 1-(2-bromoethynyl)-4-chlorobenzene Chemical compound ClC1=CC=C(C#CBr)C=C1 MWLDFOCAVDOKBW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of alkynyl sulfur (selenium) ether, which is to react disulfide (selenium) ether with a solution system of reduced zinc powder for a certain time under a protective atmosphere, then add alkynyl bromine and react to obtain alkynyl sulfur (selenium) ether. The synthetic method can make up for the series of defects of the existing synthetic method by promoting the reaction through the reduced zinc powder, and has the following advantages: (1) The simple, easily available and cheap reduced zinc powder is used as an additive, so that a noble metal catalyst can be avoided; (2) producing only zinc bromide by-product; (3) the operation is simple.
Description
Technical Field
The invention relates to a method for synthesizing alkynyl sulfur (selenium) ether, in particular to a method for synthesizing alkynyl sulfur (selenium) ether by inserting zinc into disulfide (selenium) ether bond and then cross-coupling with alkynyl bromine, belonging to the field of organic synthesis.
Background
The alkyne derivative has a conjugated system and a unique linear rigid structure, and has wide application in the fields of medicines, photoelectric materials and the like, such as: the rigid linear lipophilic alkyne derivative has certain bioactivity and can be used for resisting bacteria, resisting cancer and the like; the pi conjugated aromatic alkyne has a rigid framework and rich pi electrons, is commonly used in the field of organic photoelectric materials, and has important application in the fields of medicines, materials and the like; the cyclic aromatic polyacetylene has pi conjugated system, rigid planar structure and rich carbon atoms, is a synthetic precursor of multi-carbon functional molecules and polymer molecules, and has wide application in the fields of liquid crystal materials, organic photoelectric materials, high polymer materials and the like.
The introduction of heteroatoms in the acetylenic bonds has the following significance: (1) The introduction of an electron-rich heteroatom can enhance the reactivity of the alkyne bond, so that the alkyne can be applied to new transformations; (2) Changing the biological activity, photoelectric property and the like of alkyne compounds. S in the alkynyl thioether is directly connected with an acetylenic bond C atom, so that the reaction on sulfhydryl and acetylenic bonds can be carried out; the electron-rich sulfhydryl can enhance the reactivity of the alkyne bond, so that the alkyne bond in the alkynyl thioether can be subjected to new conversion; the introduction of mercapto groups may improve the physical properties of alkyne compounds.
The existing method for synthesizing alkynyl thioether mainly comprises the following steps: dehalogenation of halogenated olefins with thiols, csp-C coupling reactions of sulfhydryl or alkynyl electrophiles, and the like. Although the above reaction effectively constructs a Csp-C bond, it has disadvantages such as a severe reaction condition and a limited functional group tolerance range. Rhodium catalyzed alkyne and disulfide reactions successfully produce alkynyl sulfides, however, this reaction requires the use of noble metals and ligand catalysts. Therefore, the development of an economical, simple and efficient alkynyl thioether synthesis method has important significance.
Disclosure of Invention
The invention aims to provide a method for synthesizing alkynyl sulfur (selenium) ether with high yield and low cost by cross coupling under the action of reduced zinc powder by taking disulfide (selenium) ether and alkynyl bromine as raw materials, which can make up for the series of defects of the existing synthesis method.
In order to achieve the technical aim, the invention provides a synthesis method of alkynyl sulfur (selenium) ether, which is characterized in that disulfide (selenium) ether I reacts with reduced zinc powder for a certain time at a specific temperature in a solution system under a protective atmosphere. After the reaction is finished, cooling to room temperature, adding alkynyl bromine II into the reaction liquid, and reacting for a certain time at a specific temperature. After the reaction is finished, extracting by using a common organic solvent, drying, filtering, and obtaining the product alkynyl sulfur (selenium) ether III through column chromatography.
In the above synthetic method, the disulfide (selenium) ether I is the following compound:
in the above synthetic method, alkynyl bromine ii is the following compound:
in the above synthetic method, the solvent is one of the following solvents: THF, ethanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, DMF, DMSO, toluene.
The synthesis method of claim 1, wherein the molar addition amount of the reduced zinc powder is 1.2 to 2.2eq.
The method of claim 1, wherein the molar ratio of dithio (selenium) ether to alkynyl bromide is 2:1-2.4:1eq.
The synthetic method of claim 1 wherein the specified temperature is 60-140 ℃.
The method of claim 1, wherein the reaction is carried out for a period of time ranging from 6 to 30 hours.
The method according to claim 1, wherein the extraction solvent is one of n-hexane, dichloromethane, diethyl ether, ethyl acetate and toluene after the reaction.
The synthesis method provided by the invention opens up a new synthesis path for preparing the alkynyl sulfur (selenium) ether by cross-coupling of zinc-promoted disulfide (selenium) ether and alkynyl bromine, and has the advantages that: (1) The simple, easily available and cheap reduced zinc powder is used as an additive, so that a noble metal catalyst can be avoided; (2) producing only zinc bromide by-product; (3) the operation is simple.
Drawings
The drawing shows a path diagram of preparing alkynyl sulfur (selenium) ether by cross coupling of zinc-promoted disulfide (selenium) ether and alkynyl bromine.
Detailed Description
So that the manner in which the above recited features, advantages and objects of the present invention can be understood in detail, a more particular description of the invention, briefly summarized below, may be had by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Example 1
The structural formula of the target product is as follows:
0.2mmol of p-toluenedisulfide I-1, 0.24mmol of reduced zinc powder and 2mL of ethylene glycol diethyl ether are added into a 10mL reaction tube at room temperature, the reaction is carried out at 100 ℃ for 14h, the reaction liquid is cooled to room temperature, 0.1mmol of 1- (bromoethynyl) -4-nitrophenyl II-1 is added into the reaction liquid, the reaction is carried out at 100 ℃ for 14h, the reaction liquid is cooled to room temperature, 10mL of ethyl acetate is added for extraction and separation, and the ((4-nitrophenyl) ethynyl) (p-toluenesulfide) product is obtained through column chromatography, wherein the yield is 92%.
((4-nitrophenyl) ethynyl) (p-toluene) sulfide was a yellow powder.
1 H NMR(400MHz,CDCl 3 )δ8.19(d,J＝8.9Hz,2H),7.57(d,J＝8.8Hz,2H),7.39(d,J＝8.2Hz,2H),7.21(d,J＝8.1Hz,2H),2.36(s,3H). 13 C NMR(101MHz,CDCl 3 )δ146.76,137.53,131.49,130.29,129.90,127.83,127.32,123.70,95.44,84.02,21.03.
Example 2
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from p-toluenedisulfide I-1 and 1- (bromoethynyl) -4-chlorobenzol II-2.
The desired product was a yellow solid in 90% yield.
1 H NMR(400MHz,CDCl 3 )δ7.40(d,J＝8.6Hz,2H),7.36(d,J＝8.3Hz,2H),7.30(d,J＝8.6Hz,2H),7.16(d,J＝8.1Hz,2H),2.34(s,3H). 13 C NMR(101MHz,CDCl 3 )δ136.85,134.51,132.82,130.09,128.81,128.71,126.78,121.52,95.91,77.59,20.99.
Example 3
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from p-toluenedisulfide I-1 and 4- (bromoethynyl) -1,1' -biphenylII-3.
The desired product was a yellow solid in 88% yield.
1 H NMR(400MHz,CDCl 3 )δ7.62-7.53(m,6H),7.49-7.42(m,2H),7.38(t,J＝7.7Hz,3H),7.17(d,J＝6.2Hz,2H),2.34(s,3H). 13 C NMR(101MHz,CDCl 3 )δ141.26,140.27,136.67,132.11,130.06,129.22,128.87,127.69,127.03,127.01,126.63,121.92,97.12,77.32,77.00,76.83,76.68,20.99.
Example 4
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-5 and II-4.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 )δ2.54(s,3H),2.29(t,J＝7.0Hz,2H),1.55-1.46(m,2H),1.41-1.25(m,4H),0.94-0.88(m,3H).
Example 5
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-5 and II-5.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 )δ3.62(t,J＝6.4Hz,2H),2.47(t,J＝6.8Hz,2H),2.26(s,3H),1.96(m,J＝6.6Hz,2H).
Example 6
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-5 and II-6.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 )δ2.34(s,3H),2.57(t,J＝7.6Hz,2H),2.84(t,J＝7.6Hz,2H),7.19-7.23(m,3H),7.28-7.32(m,2H).
Example 7
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-5 and II-7.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 )δ2.42(s,3H),2.48(s,3H),7.10-7.15(m,1H),7.16-7.18(m,2H),7.38(d,J＝7.5Hz,1H)
Example 8
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-5 and II-8.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 )δ7.34(d,J＝8.0Hz,2H),7.13(d,J＝8.0Hz,2H),2.47(s,3H),2.36(s,3H).
Example 9
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-5 and II-9.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 ) Delta 7.42 (d, j=8.6 hz,2 h), 7.26 (d, j=8.6 hz,2 h), 2.48 (3 h, s). Example 10
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-5 and II-10.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 ) Delta 7.34 (d, j=8.8 hz, 2H), 7.29 (d, j=8.8 hz, 2H), 2.47 (s, 3H). Example 11
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-5 and II-11.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 )δ8.28(d,J＝8.2Hz,1H),7.85(d,J＝7.8Hz,1H),7.81(d,J＝8.2Hz,1H),7.65(dd,J＝7.2,1.1Hz,1H),7.56(td,J＝6.9,1.2Hz,1H),7.52(td,J＝7.4,1.1Hz,1H),7.40(dd,J＝8.3,7.2Hz,1H),2.58(3H,s).
Example 12
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-6 and II-12.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 )δ7.45-7.37(m,2H),7.30-7.26(m,3H)2.80(t,J＝7.2Hz,2H),1.78(q,J＝7.3Hz,2H),1.48(m,2H),0.97(t,J＝7.4Hz,3H).
Example 13
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-7 and II-12.
The desired product was a yellow solid in 76% yield.
1 H NMR(400MHz,CDCl 3 )δ7.45-7.39(m,2H),7.33-7.27(m,3H),3.01(tt,J＝10.9,3.8Hz,1H),2.15-2.08(m,2H),1.87-1.76(m,2H),1.67-1.58(m,1H),1.59-1.51(m,2H),1.43-1.32(m,2H),1.30-1.20(m,1H).
Example 14
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from p-toluenedisulphides I-1 and II-13.
The desired product was a white solid in 88% yield.
Melting point(M.P.):79℃–80℃； 1 H NMR(400MHz,CDCl 3 )δ7.88–7.82(m,4H),7.58–7.54(m,2H),7.50–7.46(m,4H),7.31(d,J＝6.9Hz,2H),7.15(d,J＝7.7Hz,2H),2.34(s,3H). 13 C NMR(101MHz,CDCl 3 )δ138.13,132.70(d,J＝122.2Hz),132.18(d,J＝3.0Hz),130.86(d,J＝11.1Hz),130.33,128.52(d,J＝13.1Hz),127.94,125.30(d,J＝2.0Hz),97.20(d,J＝27.3Hz),92.13(d,J＝163.6Hz),20.90. 31 PNMR(162MHz,CDCl 3 )δ7.58.HRMS-EI(m/z)[M + ]Calcd for C 21 H 17 OPS 348.0738；Found,348.0737.
Example 15
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-2 and II-13.
The desired product was a white solid in 74% yield.
Melting point(M.P.):90℃-92℃； 1 H NMR(400MHz,CDCl 3 )δ7.88–7.82(m,4H),7.60–7.56(m,2H),7.51–7.44(m,6H),7.27–7.26(m,2H). 13 C NMR(101MHz,CDCl 3 )δ132.61,132.36(d,J＝122.2Hz),132.34(d,J＝3.0Hz),130.84(d,J＝11.1Hz),128.91,128.60(d,J＝13.1Hz),128.38(d,J＝1.0Hz),121.85,95.28(d,J＝26.3Hz),93.68(d,J＝160.6Hz). 31 P NMR(162MHz,CDCl 3 )δ7.73.HRMS-EI(m/z)[M + ]Calcd for C 20 H 14 BrOPS 411.9686；Found,411.9685.
Example 16
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-3 and II-13.
The desired product was a white solid in 73% yield.
Melting point(M.P.):94℃–96℃； 1 H NMR(400MHz,CDCl 3 )δ7.88–7.82(m,4H),7.59–7.56(m,2H),7.52–7.48(m,4H),7.35–7.29(m,4H). 13 C NMR(101MHz,CDCl 3 )δ134.05,132.38(d,J＝3.0Hz),130.94(d,J＝123.2Hz),130.90(d,J＝12.1Hz),129.77,128.82,128.64(d,J＝13.1Hz),127.70(d,J＝2.0Hz),95.54(d,J＝26.3Hz),93.56(d,J＝160.59Hz). 31 P NMR(162MHz,CDCl 3 )δ7.73.HRMS-EI(m/z)[M + ]Calcd for C 20 H 14 ClOPS 368.0191；Found,368.0189.
Example 17
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-4 and II-13.
The desired product was a white solid in 80% yield.
Melting point(M.P.):86℃–88℃； 1 H NMR(400MHz,CDCl 3 )δ7.88–7.82(m,4H),7.57–7.54(m,2H),7.49–7.46(m,4H),7.35(m,4H),1.30(s,9H). 13 C NMR(101MHz,CDCl 3 )δ151.18,132.50(d,J＝122.2Hz),132.00(d,J＝2.0Hz),130.63(d,J＝12.1Hz),128.34(d,J＝13.1Hz),127.55,126.52,125.12(d,J＝1.0Hz),96.96(d,J＝27.3Hz),91.85(d,J＝164.6Hz),34.25,30.85. 31 P NMR(162MHz,CDCl 3 )δ7.49.HRMS-ESI(m/z)[M + ]Calcd for C 24 H 23 OPS390.1207；Found,390.1206.
Example 18
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-8 and II-13.
The desired product was a white solid in 80% yield.
Melting point(M.P.):122℃–124℃； 1 H NMR(400MHz,CDCl 3 )δ7.92–7.87(m,5H),7.82(d,J＝8Hz,2H),7.69–7.67(m,1H),7.60–7.56(m,2H),7.52–7.45(m,7H). 13 C NMR(101MHz,CDCl 3 )δ133.41,132.25,132.22(d,J＝3.0Hz),132.56(d,J＝123.3Hz),130.82(d,J＝11.1Hz),129.39,128.54(d,J＝13.1Hz),127.66,127.05,126.98,126.56,126.38,126.14(d,J＝2.0Hz),124.50,96.40(d,J＝27.3Hz),93.10(d,J＝162.6Hz). 31 P NMR(162MHz,CDCl 3 )δ7.66.HRMS-ESI(m/z)[M + ]Calcd for C 24 H 17 OPS 384.0738；Found,384.0737.
Example 19
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-9 and II-13.
The desired product was a yellow liquid in 80% yield.
1 H NMR(400MHz,CDCl 3 )δ7.89–7.84(m,4H),7.58–7.53(m,2H),7.50–7.46(m,4H),7.22–7.20(m,3H),7.09–7.07(m,1H),2.29(s,3H). 13 C NMR(101MHz,CDCl 3 )δ139.35,132.34(d,J＝122.2Hz),131.98(d,J＝3.0Hz),130.54(d,J＝11.1Hz),129.09,128.38,128.28(d,J＝13.1Hz),127.60,124.26,96.43(d,J＝27.3Hz),92.59(d,J＝163.6Hz),20.87. 31 P NMR(162MHz,CDCl 3 )δ7.40.HRMS-EI(m/z)[M + ]Calcd for C 21 H 17 OPS 348.0738; found,348.0735 example 20
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-10 and II-13.
The desired product was a white solid in 80% yield.
Melting point(M.P.):75℃–77℃； 1 H NMR(400MHz,CDCl 3 )δ7.88–7.82(m,4H),7.57–7.53(m,3H),7.49–7.48(m,4H),7.22–7.17(m,3H),2.36(s,3H). 13 C NMR(101MHz,CDCl 3 )δ136.55,132.50(d,J＝122.2Hz),132.06(d,J＝3.0Hz),130.66(d,J＝11.1Hz),130.56,128.39,128.38(d,J＝13.1Hz),127.96,127.04,96.56(d,J＝27.3Hz),91.85(d,J＝163.6Hz),19.52. 31 P NMR(162MHz,CDCl 3 )δ7.53.HRMS-EI(m/z)[M + ]Calcd for C 21 H 17 OPS 348.0738；Found,348.0736.
Example 21
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-11 and II-13.
The desired product was a yellow liquid in 80% yield.
1 H NMR(400MHz,CDCl 3 )δ7.86–7.80(m,4H),7.55–7.51(m,2H),7.49–7.44(m,4H),2.86(t,J＝7.5Hz,2H),1.77–1.70(m,2H),1.40–1.36(m,2H),1.25(br,8H),0.88(t,J＝7.5Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ132.98(d,J＝123.2Hz),132.02(d,J＝3.0Hz),130.76(d,J＝11.1Hz),128.44(d,J＝14.1Hz),100.88(d,J＝28.3Hz),88.22(d,J＝168.7Hz),35.68(d,J＝2.2Hz),31.58,29.24,28.91,28.80,27.98,22.4413.95. 31 P NMR(162MHz,CDCl 3 )δ7.16.HRMS-ESI(m/z)[M + ]Calcd for C 22 H 27 OPS 370.1520；Found,370.1521.
Example 22
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-12 and II-13.
The desired product was a yellow liquid in 80% yield.
1 H NMR(400MHz,CDCl 3 )δ7.86–7.80(m,4H),7.55–7.52(m,2H),7.49–7.45(m,4H),2.86(t,J＝7.5Hz,2H),1.77–1.70(m,2H),1.40–1.36(m,2H),1.25(br,16H),0.88(t,J＝10.0Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ133.06(d,J＝122.2Hz),132.07(d,J＝2.0Hz),130.86(d,J＝11.1Hz),128.50(d,J＝13.1Hz),100.93(d,J＝28.3Hz),88.29(d,J＝169.7Hz),35.76(d,J＝2.0Hz),31.83,29.54,29.53,29.46,29.34,29.32,29.26,28.93,28.08,22.61,14.05. 31 P NMR(162MHz,CDCl 3 )δ7.17.HRMS-ESI(m/z)[M + ]Calcd for C 26 H 35 OPS 426.2146; found,426.2145 example 23
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-13 and II-13.
The desired product was a yellow liquid in 80% yield.
1 H NMR(400MHz,CDCl 3 )δ7.85–7.80(m,4H),7.55–7.51(m,2H),7.48–7.46(m,4H),2.94–2.88(m,1H),2.74–2.68(m,1H),1.77–1.75(m,1H),1.53–1.44(m,1H),1.30–1.21(m,1H),1.01–0.98(m,3H),0.89–0.84(m,3H). 13 C NMR(101MHz,CDCl 3 )δ132.90(d,J＝123.2Hz),131.98(d,J＝3.0Hz),130.72(d,J＝11.1Hz),128.39(d,J＝14.1Hz),101.42(d,J＝29.3Hz),87.43(d,J＝169.7Hz),42.74,34.70,27.91,18.08,10.95. 31 P NMR(162MHz,CDCl 3 )δ7.15.HRMS-ESI(m/z)[M + ]Calcd for C 19 H 21 OPS 328.1051；Found,328.1052.
Example 24
The structural formula of the target product is as follows:
the procedure is as in example 1 starting from disulfide I-14 and II-13.
The desired product was a yellow liquid in 80% yield.
1 H NMR(400MHz,CDCl 3 )δ7.86–7.81(m,4H),7.55–7.51(m,2H),7.48–7.44(m,4H),3.11–3.07(m,1H),1.75–1.65(m,2H),1.42–1.39(m,3H),1.02–0.97(m,3H). 13 C NMR(101MHz,CDCl 3 )δ133.10(d,J＝123.2Hz),132.04(d,J＝3.0Hz),130.78(d,J＝11.1Hz),128.48(d,J＝13.1Hz),99.93(d,J＝28.3Hz),89.74(d,J＝169.7Hz),47.82,29.48,20.84,11.39. 31 P NMR(162MHz,CDCl 3 )δ7.14.HRMS-ESI(m/z)[M + ]Calcd for C 18 H 19 OPS 314.0894; found,314.0892 example 25
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from p-toluylene diselenide I-16 and 1- (bromoethynyl) -4-nitrobenzene II-1.
The desired product was a white solid in 86% yield.
1 H NMR(400MHz,CDCl 3 )δ8.19(d,J＝8.9Hz,2H),7.64-7.55(m,4H),7.40-7.29(m,3H)。
Example 26
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from p-toluylene diselenide I-16 and 1- (bromoethynyl) -4-nitrobenzene II-12.
The desired product was a white solid in 86% yield.
1 H NMR(400MHz,CDCl 3 )δ7.49-7.46(m,4H),7.33-7.30(m,3H),7.14(d,J＝8.0Hz,2H),2.33(s,3H).
Example 27
The structural formula of the target product is as follows:
the procedure is as in example 1, starting from I-17 and II-12.
The desired product was a white solid in 86% yield.
1 H NMR(400MHz,CDCl 3 )δ7.51-7.43(m,2H),7.40-7.29(m,3H),2.37(s,3H)。
Claims (7)
1. A method for preparing alkynyl sulfur (selenium) ether by cross-coupling zinc-promoted disulfide (selenium) ether and alkynyl bromine is characterized by comprising the following steps: under the protection atmosphere, the disulfide (selenium) ether I and the alkynyl bromine II are used as raw materials, the reaction is promoted by reducing zinc powder, the organic solvent is used as a solvent for reaction, the reaction is carried out under heating, and the organic solvent is used for extraction after the reaction is finished, so that the product alkynyl sulfur (selenium) ether III is obtained, wherein the structural formula of the alkynyl sulfur (selenium) ether III is as follows:
the disulfide (selenium) ether I is selected from the following compounds:
the alkynyl bromine II is selected from the following compounds:
2. the synthetic method according to claim 1, wherein the organic solvent used in the reaction is one of the following solvents: THF, ethanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, DMF, DMSO, toluene.
3. The synthesis method of claim 1, wherein the molar addition amount of the reduced zinc powder is 1.2 to 2.2eq.
4. The method of claim 1, wherein the molar ratio of dithio (selenium) ether to alkynyl bromide is from 2:1 to 2.4:1.
5. The synthetic method of claim 1 wherein the heating temperature of the reaction is 60-140 ℃.
6. The synthetic method of claim 1 wherein the heating time of the reaction is from 6 to 30 hours.
7. The method according to claim 1, wherein the organic solvent used for extraction after completion of the reaction is one of n-hexane, methylene chloride, diethyl ether, ethyl acetate and toluene.
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| Synthesis of Thiazinoimidazoles by Lewis Acid–Catalyzed [3+3] Cycloaddition Reactions of Propargyl Alcohols with 2-Mercaptoimidazoles;Naoya Mishima等;Eur. J. Org. Chem.;20191231;3117-3121 * |
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