CN111333608B - Preparation method of polysubstituted naphtho [1,8-bc ] thiophene compound - Google Patents
Preparation method of polysubstituted naphtho [1,8-bc ] thiophene compound Download PDFInfo
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Abstract
The invention discloses a preparation method of polysubstituted naphtho [1,8-bc ] thiophene compounds, which comprises the steps of firstly taking 1-halogen-8-alkynyl naphthylamine compounds, a catalyst and a sulfur source according to the molar ratio of 1 (0.1-1.0) to 1-3, placing the 1-halogen-8-alkynyl naphthylamine compounds, the catalyst and the sulfur source in a reaction vessel, and then adding a solvent into the reaction vessel until the 1-halogen-8-alkynyl naphthylamine compounds are completely dissolved; the reaction vessel is placed at 0-150 ℃ and stirred for reaction for 0-24h, and the product of the polysubstituted naphtho [1,8-bc ] thiophene compound is obtained after post treatment. The method has the advantages of simple and efficient operation method, mild reaction conditions, good reaction selectivity, high yield, convenience in separation and purification, wide substrate universality, simple and easily-obtained reaction raw materials, low production cost and good application prospect.
Description
Technical Field
The invention relates to a preparation method for synthesizing a novel sulfur-containing fused heterocyclic compound, in particular to a preparation method for a polysubstituted naphtho [1,8-bc ] thiophene compound.
Background
Naphtho [1,8-bc]Thiophene compounds are an important class of organic compounds, and have very wide application in the industries of medicines, bioactive molecules, fluorescent materials, solar cell materials and the like (eur.j.med.chem.2014, 85,119 bioorg.med.chem.lett.2011,21,1052 j.porphyrins phthalocyanines.2013,17, 821). At present, the preparation of poly-substituted naphtho [1,8-bc ] has been published]The methods for preparing thiophene compounds are few, and mainly comprise the following methods. The most common method is to use 1, 8-naphthalene dicarboxylic anhydride as the starting material in an organic mercurial reagent such as HgO or Hg (OAc) 2 Synthesizing 8-iodine-1-naphthoic acid under the action of copper, and further reacting with 3-mercaptopropionic acid under the catalysis of copper to prepare naphtho [1,8-bc ]]Thiophene-2-ketone, finally preparing multi-substituted naphtho [1,8-bc ] through electrophilic substitution reaction and condensation reaction]Thiophene derivatives (J.Porphyrins Phonocyanines 2013,17,821, synthesis 1989,523, J.Org.chem.1989,54,4746, J.Am.chem.Soc.1983,105, 6096.. The final product can be obtained only through multi-step reaction, and the method uses a toxic organic mercury reagent, so that the reaction conditions are not green enough. Koichi Mitsudo and Seiji Suga et al reported an intramolecular Friedel-crafts acylation to produce naphtho [1,8-bc ] derivatives]Derivatization of thiophene-2-ketone to prepare polysubstituted naphtho [1,8-bc]The thiophene derivative is prepared through the reaction of naphthalene-1-thiol as material with bis (trichloromethyl) carbonate to produce naphthalene sulfonyl chloride compound and the final reaction of aluminum trichloridePreparation of naphtho [1,8-bc ] by intramolecular Friedel-crafts acylation]Thiophene-2-ketone, and further derivatization to prepare naphtho [1,8-bc]Thiophene derivatives (Synlett 2016,27, 2327). In the method, a highly toxic mercury reagent is not used as a catalyst, but the reaction step is still long and the operation is inconvenient.
Disclosure of Invention
The invention aims to provide a preparation method of a naphtho [1,8-bc ] thiophene compound aiming at the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of polysubstituted naphtho [1,8-bc ] thiophene compounds is characterized in that 1-halogen-8-alkynyl naphthylamine compounds, catalysts and sulfur sources are placed in a reaction vessel according to the molar ratio of 1 (0.1-1.0) to 1 (3); adding a solvent into a reaction vessel until the 1-halogen-8-alkynyl naphthylamine compound is completely dissolved; the reaction vessel is placed at 0-150 ℃ and stirred for reaction for 0-24h, and the product of the polysubstituted naphtho [1,8-bc ] thiophene compound is obtained after post treatment.
The invention also has the following additional technical features:
the technical scheme of the invention is further specifically optimized as follows: the 1-halogen-8-alkynyl naphthylamine compound is a 1-iodine-8-alkynyl naphthylamine compound or a 1-bromine-8-alkynyl naphthylamine compound; the solvent is an aprotic solvent.
The technical scheme of the invention is further specifically optimized as follows: the aprotic solvent is acetonitrile, toluene, tetrahydrofuran, dichloromethane, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide or dimethylsulfoxide. Specifically, the method comprises the following steps: the aprotic solvent is dimethyl sulfoxide.
The technical scheme of the invention is further specifically optimized as follows: the catalyst is Ag 2 O、AgOAc、AgNO 3 、AgTFA、AgOTf、Cu(OAc) 2 ·H 2 O、Cu(OAc) 2 、Cu(acac) 2 、CuBr 2 、CuSO 4 、CuF 2 、CuOTf、Cu(OTf) 2 、Cu(NO 3 ) 2 ·3H 2 O、CuCl 2 ·2H 2 O、CuI、CuBr、CuCl、Cu 2 O、Pd(OAc) 2 、Pd(OTf) 2 And PdCl 2 One or more of (a). Specifically, the method comprises the following steps: the catalyst is Cu (OAc) 2 。
The technical scheme of the invention is further specifically optimized as follows: the sulfur source is one or more of potassium xanthate, thiourea, sodium sulfide, elemental sulfur, ammonium sulfide, ammonium bisulfide and sodium bisulfide. Specifically, the method comprises the following steps: the sulfur source is potassium xanthate.
The technical scheme of the invention is further specifically optimized as follows: the reaction temperature is 0 ℃,10 ℃, 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃,60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 150 ℃. Specifically, the method comprises the following steps: the reaction temperature was 90 ℃.
The technical scheme of the invention is further specifically optimized as follows: the molar ratio of the 1-halogen-8-alkynyl naphthylamine compound to the catalyst to the sulfur source is 1.0.
The beneficial effects of the invention are:
the invention adopts a one-step method to synthesize the polysubstituted naphtho [1,8-bc ]]Thiophene compounds, the reaction operation is simple, the reaction condition is mild, the reaction raw materials are easy to obtain, and Cu (OAc) is used 2 The catalyst is prepared by taking potassium xanthate as a sulfur source, has low production cost, and is not only suitable for small-scale preparation in a laboratory, but also suitable for industrial large-scale production. The reaction reduces the process of separating and purifying the intermediate, and the invention takes 1-halogen-8-alkynyl naphthylamine compound as the initial raw material and Cu (OAc) 2 As a catalyst, potassium xanthate is used as a sulfur source; the reaction raw materials are simple and easy to obtain, and are convenient for polysubstituted naphtho [1,8-bc]The establishment of thiophene compound library provides a good method for screening the drug activity, and the polysubstituted naphtho [1,8-bc ] is]The thiophene compound also has solid fluorescence property, and provides help for searching novel fluorescent molecules.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below in order to provide a more thorough understanding of the present disclosure and to fully convey the scope of the present disclosure to those skilled in the art. While exemplary embodiments of the present disclosure have been shown, it should be understood that the invention is not limited to the embodiments set forth herein.
The structure of the polysubstituted naphtho [1,8-bc ] thiophene compound is shown as follows:
wherein: r is 1 ＝Ph，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-chlorophenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-methylphenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-fluorophenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-methoxyphenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝1-naphthyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝2-thienyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝3-thienyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝n-butyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝3-methylphenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝2-methylphenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝3-chlorophenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝2-chlorophenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝4-ethylphenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-propylphenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-tert-butylphenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-chlorophenyl，R 2 ＝D，R 3 ＝H，R 4 ＝H；R 1 ＝p-methylphenyl，R 2 ＝D，R 3 ＝H，R 4 ＝H；R 1 ＝3-fluorophenyl，R 2 ＝D，R 3 ＝H，R 4 ＝H；R 1 ＝p-chlorophenyl，R 2 ＝H，R 3 ＝NO 2 ，R 4 ＝H；R 1 ＝p-chlorophenyl，R 2 ＝H，R 3 ＝NH 2 ，R 4 ＝H；R 1 ＝p-chlorophenyl，R 2 ＝H，R 3 ＝Br，R 4 ＝H.
A preparation method of a polysubstituted naphtho [1,8-bc ] thiophene compound adopts a one-step synthesis mode, and specifically comprises the following steps: taking 1-halogen-8-alkynyl naphthylamine compounds, a catalyst and a sulfur source according to the molar ratio of 1 (0.1-1.0) to 1 (3), placing the 1-halogen-8-alkynyl naphthylamine compounds, the catalyst and the sulfur source into a reaction vessel, and adding a solvent into the reaction vessel until the 1-halogen-8-alkynyl naphthylamine compounds are completely dissolved; the reaction vessel is placed at 0-150 ℃ and stirred for reaction for 0-24h, and the product of the polysubstituted naphtho [1,8-bc ] thiophene compound is obtained after post-treatment.
In the synthesis method, the 1-halogen-8-alkynyl naphthylamine compound is a 1-iodine-8-alkynyl naphthylamine compound or a 1-bromine-8-alkynyl naphthylamine compound.
The solvent may be an aprotic solvent such as one or more of acetonitrile, toluene, tetrahydrofuran, dichloromethane, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, or dimethylsulfoxide. Among them, dimethyl sulfoxide is preferable.
The catalyst is Ag 2 O、AgOAc、AgNO 3 、AgTFA、AgOTf、Cu(OAc) 2 ·H 2 O、Cu(OAc) 2 、Cu(acac) 2 、CuBr 2 、CuSO 4 、CuF 2 、Cu(OTf) 2 、Cu(NO 3 ) 2 ·3H 2 O、CuCl 2 ·2H 2 O、CuI、CuBr、CuCl、Cu 2 O、Pd(OAc) 2 、Pd(OTf) 2 Or PdCl 2 . The catalyst is preferably Cu (OAc) 2 。
The sulfur source is potassium xanthate, thiourea, sodium sulfide, elemental sulfur, ammonium sulfide, ammonium bisulfide or sodium bisulfide, wherein the sulfur source is preferably potassium xanthate.
The reaction temperature is 0 ℃,10 ℃, 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃,60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃. The reaction temperature is preferably 90 ℃.
The molar ratio of the 1-halo-8-alkynylnaphthylamine compound, the catalyst and the sulfur source is preferably 1.0.
The invention is further illustrated by the following specific examples, which are not intended to limit the invention thereto.
Table 1 shows the structures of the polysubstituted naphtho [1,8-bc ] thiophenes in examples 1-5.
TABLE 1 polysubstituted naphtho [1,8-bc ] thiophenes examples 1-5
| Examples | R 1 | R 2 | R 3 | R 4 |
| 1 | Ph | H | H | H |
| 2 | p-chlorophenyl | H | H | H |
| 3 | p-methylphenyl | H | H | H |
| 4 | p-chlorophenyl | H | NO 2 | H |
| 5 | p-chlorophenyl | D | H | H |
Example 1
1-iodo-8-phenylethynylnaphthalene (0.1 mmol), cu (OTf) were added sequentially to the reaction vessel at room temperature 2 (0.01 mmol), potassium xanthate (0.24 mmol) and dimethyl sulfoxide (2 ml), after which the reaction was stirred at 100 ℃ until the reaction of 1-iodo-8-phenylethynylnaphthalene was complete. After the reaction is finished, standing at room temperature, adding 10 ml of water, extracting for 2-4 times by using 10 ml of ethyl acetate, combining filtrates, and distilling under reduced pressure to remove the solvent; the product is separated by a silica gel chromatographic column and distilled under reduced pressure, the yield is 89 percent, and the identification result is as follows:
Yellow solid. 1 H NMR(400MHz,CDCl 3 )δ7.86(d,J＝7.2Hz,1H),7.76–7.61(m,3H),7.61–7.50(m,2H),7.50–7.38(m,4H),7.34(d,J＝6.9Hz,1H),7.28(t,J＝7.4Hz,1H)； 13 C NMR(100MHz,CDCl 3 )δ140.02,139.55,137.28,136.44,133.84,132.44,128.69,128.64,128.07,127.86,127.10,125.83,122.00,118.58,117.97,117.00；IR(neat)3133,1734,1402,763cm -1 ；HRMS(ESI-TOF)calcd for C 18 H 13 S(M+H):261.0738,found 261.0739。
example 2
1-iodo-8-p-chlorophenylethynylnaphthalene (0.5 mmol), cu (OAc) were added sequentially to the reaction vessel at room temperature 2 (0.2 mmol), potassium xanthate (1.5 mmol) and N, N-dimethylformamide (5 ml) were then stirred at 130 ℃ until 1-iodo-8-p-chlorophenylethynylnaphthalene was reacted to completion. After the reaction is finished, standing at room temperature, adding 15 ml of water, extracting for 2-4 times by using 10 ml of ethyl acetate, combining filtrates, and distilling under reduced pressure to remove the solvent; separating by a silica gel chromatographic column, and distilling under reduced pressure, wherein the yield is 92 percent, and the identification result is as follows:
Yellow solid. 1 H NMR(400MHz,CDCl 3 )δ7.84(d,J＝7.3Hz,1H),7.70(d,J＝8.0Hz,1H),7.61–7.51(m,4H),7.48–7.38(m,4H),7.37–7.31(m,1H)； 13 C NMR(100MHz,CDCl 3 )δ139.13,135.99,134.94,133.76,132.57,132.41,131.96,129.74,128.85,128.78,128.12,127.88,126.09,122.19,118.10,117.20；IR(neat)3132,1733,1401,761cm -1 ；HRMS(ESI-TOF)calcd for C 18 H 12 ClS(M+H):295.0348,found 295.0349。
example 3
1-bromo-8-p-methylphenylethynylnaphthalene (1.0 mmol), pd (OAc) were added sequentially to the reaction vessel at room temperature 2 (0.2 mmol), sodium sulfide (2.0 mmol) and dimethylsulfoxide (6 ml), after which the reaction was stirred at 160 ℃ until the reaction of 1-bromo-8-p-methylphenylethynylnaphthalene was complete. After the reaction is finished, standing at room temperature, adding 20 ml of water, extracting for 2-4 times by using 10 ml of ethyl acetate, combining filtrates, and distilling under reduced pressure to remove the solvent; separating by a silica gel chromatographic column, distilling under reduced pressure, obtaining the yield of 65 percent, and identifying the result as follows:
Yellow solid. 1 H NMR(400MHz,CDCl 3 )δ7.84(d,J＝7.3Hz,1H),7.67(d,J＝8.0Hz,1H),7.60–7.49(m,4H),7.47–7.38(m,2H),7.33(d,J＝7.1Hz,1H),7.26(d,J＝7.3Hz,2H),2.40(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ140.16,139.70,137.15,136.18,133.64,132.46,130.68,129.43,128.60,128.04,127.86,125.55,121.88,118.65,117.74,116.85,21.36；IR(neat)3129,1733,1404,762cm -1 ；HRMS(ESI-TOF)calcd for C 19 H 15 S(M+H):275.0894,found 275.0891。
example 4
Sequentially adding 1-iodine-4-nitro-8-p-chlorophenylethynylnaphthalene (0.3 mmol) and CuCl into a reaction vessel at room temperature 2 (0.1 mmol), potassium xanthate (0.5 mmol) and N, N-dimethylacetamide (4 ml), followed by stirring at 80 ℃ until the reaction of 1-iodo-4-nitro-8-p-chlorophenylethynylnaphthalene was complete. After the reaction is finished, standing at room temperature, adding 15 ml of water, extracting for 2-4 times by using 10 ml of ethyl acetate, combining filtrates, and distilling under reduced pressure to remove the solvent; separating by a silica gel chromatographic column, distilling under reduced pressure, obtaining a yield of 45 percent, and obtaining an identification result as follows:
Red solid. 1 H NMR(400MHz,CDCl 3 )δ7.93(d,J＝8.1Hz,1H),7.75(dd,J＝16.7,7.6Hz,2H),7.68–7.58(m,3H),7.42–7.32(m,3H),6.60(d,J＝7.7Hz,1H)； 13 C NMR(100MHz,CDCl 3 )δ153.65,137.55,136.58,134.66,133.32,132.16,131.34,131.10,130.95,130.78,128.56,127.97,127.87,125.05,121.37；IR(neat)3134,1653,1401,768cm -1 ；HRMS(ESI-TOF)calcd for C 18 H 11 ClNO 2 S(M+H):340.0199,found 340.0198。
example 5
1-iodo-8-p-chlorophenylethynylnaphthalene (0.4 mmol), cu (OAc) were added sequentially to the reaction vessel at room temperature 2 (0.1 mmol), potassium xanthate (1.2 mmol) and dimethyl sulfoxide (2 ml), deuterium oxide (1 ml), after which the reaction is stirred at 90 ℃ until the reaction of 1-iodo-8-p-chlorophenylethynylnaphthalene is complete. After the reaction is finished, standing at room temperature, adding 20 ml of water, extracting for 2-4 times by using 10 ml of ethyl acetate, combining filtrates, and distilling under reduced pressure to remove the solvent; separating by a silica gel chromatographic column, distilling under reduced pressure, obtaining the yield of 85 percent, and obtaining the identification result:
Yellow solid. 1 H NMR(400MHz,CDCl 3 )δ7.87(d,J＝7.2Hz,1H),7.74(d,J＝7.9Hz,1H),7.63–7.54(m,4H),7.51–7.41(m,3H),7.38(d,J＝6.9Hz,1H)； 13 C NMR(100MHz,CDCl 3 )δ139.78,139.18,137.94,134.91,133.79,132.60,132.45,129.76,128.88,128.16,127.92,126.11,122.23,118.15,117.24；IR(neat)3130,1732,1399,759cm -1 ；HRMS(ESI-TOF)calcd for C 18 H 11 DClS(M+H):296.0411,found 296.0406。
in conclusion, the invention adopts a one-step method to synthesize the polysubstituted naphtho [1,8-bc ]]Thiophene compounds, the reaction operation is simple, the reaction condition is mild, the reaction raw materials are easy to obtain, and Cu (OAc) is used 2 The catalyst is prepared by taking potassium xanthate as a sulfur source, has low production cost, and is not only suitable for small-scale preparation in a laboratory, but also suitable for industrial large-scale production. The reaction reduces the process of separating and purifying the intermediate, and the invention takes 1-halogen-8-alkynyl naphthylamine compound as the initial raw material and Cu (OAc) 2 As a catalyst, potassium xanthate is used as a sulfur source; the reaction raw materials are simple and easy to obtain, and are convenient for polysubstituted naphtho [1,8-bc]The establishment of thiophene compound library provides a good method for screening the drug activity, and the polysubstituted naphtho [1,8-bc ] is]The thiophene compound also has solid fluorescence property, and provides help for searching novel fluorescent molecules.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described above in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments.
Claims (5)
1. A preparation method of polysubstituted naphtho [1,8-bc ] thiophene compounds is characterized in that 1-halogen-8-alkynyl naphthylamine compounds, catalysts and sulfur sources are placed in a reaction vessel according to the molar ratio of 1 (0.1-1.0) to 1 (3); adding a solvent into a reaction vessel until the 1-halogen-8-alkynyl naphthylamine compound is completely dissolved; the reaction vessel is placed at 0-150 ℃ and stirred for reaction for 0-24h, and the product of the polysubstituted naphtho [1,8-bc ] thiophene compound is obtained after post-treatment;
wherein the sulfur source is potassium xanthate, and the catalyst is Cu (OTf) 2 、Cu(OAc) 2 ；
The 1-halogen-8-alkynyl naphthylamine compound is 1-iodine-8-phenylethynyl naphthalene, 1-iodine-8-p-chlorobenzene ethynylnaphthalene, 1-bromine-8-p-methylbenzene ethynylnaphthalene or 1-iodine-4-nitro-8-p-chlorobenzene ethynylnaphthalene;
the structure of the polysubstituted naphtho [1,8-bc ] thiophene compound is as follows:
wherein R is 1 ＝Ph，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-chlorophenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-methylphenyl，R 2 ＝H，R 3 ＝H，R 4 ＝H；R 1 ＝p-chlorophenyl，R 2 ＝H，R 3 ＝NO 2 ，R 4 ＝H；R 1 ＝p-chlorophenyl，R 2 ＝D，R 3 ＝H，R 4 ＝H。
2. The process for producing polysubstituted naphtho [1,8-bc ] thiophenes according to claim 1, wherein the solvent is an aprotic solvent.
3. The method for producing polysubstituted naphtho [1,8-bc ] thiophenes compound according to claim 2, wherein the aprotic solvent is acetonitrile, toluene, tetrahydrofuran, dichloromethane, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide or dimethylsulfoxide.
4. The method for producing a polysubstituted naphtho [1,8-bc ] thiophene compound according to claim 1, wherein the reaction temperature is 0 ℃,10 ℃, 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃,60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃.
5. The method for producing polysubstituted naphtho [1,8-bc ] thiophenes based on claim 1, wherein the molar ratio of the 1-halo-8-alkynylnaphthylamine based compound, catalyst and sulfur source is 1.0.
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| CN111333608A (en) | 2020-06-26 |
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