CN112939830B - Nucleophilic reaction method of alkenyl thioether to o-methylene benzoquinone - Google Patents
Nucleophilic reaction method of alkenyl thioether to o-methylene benzoquinone Download PDFInfo
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- -1 alkenyl thioether Chemical class 0.000 title claims abstract description 32
- 238000007344 nucleophilic reaction Methods 0.000 title claims abstract description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- UIYCHXAGWOYNNA-UHFFFAOYSA-N Divinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 239000012044 organic layer Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- XBXPATGJUNPLJA-UHFFFAOYSA-N 2-[hydroxy(phenyl)methyl]phenol Chemical class C=1C=CC=C(O)C=1C(O)C1=CC=CC=C1 XBXPATGJUNPLJA-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- CPBZARXQRZTYGI-UHFFFAOYSA-N 3-cyclopentylpropylcyclohexane Chemical compound C1CCCCC1CCCC1CCCC1 CPBZARXQRZTYGI-UHFFFAOYSA-N 0.000 claims 1
- 125000003884 phenylalkyl group Chemical group 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 18
- 239000000047 product Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005445 natural product Substances 0.000 description 3
- 229930014626 natural products Natural products 0.000 description 3
- 230000002194 synthesizing Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drugs Drugs 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
Abstract
The invention relates to a nucleophilic reaction method of alkenyl thioether p-o-methylene benzoquinone, which comprises the steps of dissolving a 2- (hydroxy (phenyl) methyl) phenol compound and a vinyl thioether compound in an organic solvent, adding a p-toluenesulfonic acid catalyst, and stirring and reacting for 5-10h at 25-80 ℃; extracting the reacted reaction liquid, combining organic layers, washing, drying, evaporating to remove the solvent, and performing silica gel column chromatography on the residue to obtain the product. The method has the advantages of mild reaction conditions, high efficiency, high reaction yield and easy separation and purification of products, and overcomes the defects of expensive catalyst and harsh conditions in the traditional method.
Description
Technical Field
The invention relates to a nucleophilic reaction method for catalyzing alkenyl thioether p-o-methylene benzoquinone by p-toluenesulfonic acid, belonging to the technical field of organic synthesis.
Background
The o-methylene benzoquinone compound is a very active and important intermediate and is widely applied to natural products and pharmaceutical chemistry. Because of the wide application of the o-methylene benzoquinone compound, the research on the preparation method of the o-methylene benzoquinone compound is always a focus of attention of organic synthesis experts. Such a reaction method requires neutralization to neutrality of the system after the reaction is completed, and the post-treatment operation is complicated.
Carbon-to-sulfur bondHave wide application in the synthesis of many sulfur-containing natural products and drug molecules. Among them, the sulfur Michael addition reaction is a simple and efficient synthesis method for synthesizing sulfur-containing organic compounds. In recent years, chemists have promoted this type of reaction primarily by noble metals, such as [ LNi 2 (CH 3 CN)(THF)](ClO 4 ) 3 ,Ru(acetone)(R,R-BIPHOP-F)Cp][SbF 6 ]And so on.
Therefore, the development of a new method for catalyzing the nucleophilic addition reaction of vinyl thioether to o-methylene benzoquinone by p-toluenesulfonic acid simply and efficiently has important significance.
Disclosure of Invention
The invention aims to provide a nucleophilic reaction method of alkenyl thioether to o-methylene benzoquinone, which has the advantages of mild condition, simple and convenient operation, less limitation on the substitution type of a functional group, and easy separation and purification of a product; has important significance for the methodology research of o-methylene benzoquinone.
The technical scheme adopted by the invention is as follows:
a nucleophilic reaction method of alkenyl thioether to o-methylene benzoquinone comprises the following steps:
(1) dissolving 2- (hydroxy (phenyl) methyl) phenol compounds and vinyl thioether compounds in an organic solvent, adding a p-toluenesulfonic acid catalyst, and stirring for reaction for 5-10h at 25-80 ℃; the structural formula of the 2- (hydroxy (phenyl) methyl) phenol compound is as follows:
in the formula R 1 And R 2 Same or different from H, C1-C5 alkyl, halogen X, -NO 2 Any one of-CN and-OR 4;
(2) extracting the reacted reaction solution, combining organic layers, washing, drying, evaporating to remove the solvent, and performing silica gel column chromatography on the residue to obtain the product.
In the above reaction method, the vinyl thioether compound in step (1) is as follows:
in the formula R 3 Is selected from any one of phenyl, benzyl and C1-C10 alkyl.
The R4 is selected from any one of alkyl groups of H, C1-C5. The adding proportion of the 2- (hydroxyl (phenyl) methyl) phenol compound, the vinyl thioether compound, the p-toluenesulfonic acid catalyst and the organic solvent is 1: 1.5-3: 0.05-0.2: 2.5-10; mmol: mmol: ml. The preferable adding proportion of the 2- (hydroxyl (phenyl) methyl) phenol compound, the vinyl thioether compound, the p-toluenesulfonic acid catalyst and the organic solvent is 1: 2: 0.1: 5; mmol: mmol: ml. The organic solvent is one of DMF, DMSO, toluene, acetonitrile, dichloromethane, chloroform, 1, 2-dichloroethane, ethyl acetate or tetrahydrofuran; 1, 2-dichloroethane is preferred.
The eluent of the silica gel column chromatography in the step (2) is one or a combination of more of petroleum ether, normal hexane and cyclohexane; preferably petroleum ether.
The reaction formula of the method is as follows:
in the formula, R 1 And R 2 Same or different from H, C1-C5 alkyl, halogen X, -NO 2 Any one of, -CN and-OR 4. R4 is selected from any one of alkyl of H, C1-C5. R 3 Is selected from any one of phenyl, benzyl and C1-C10 alkyl.
The invention has the beneficial effects that:
(1) the method uses the 2- (hydroxy (phenyl) methyl) phenol compound and the vinyl thioether compound to generate the o-methylene benzoquinone in situ under the catalysis of the p-toluenesulfonic acid and perform nucleophilic addition reaction, has mild reaction conditions and high efficiency, and avoids the defects of expensive catalyst and harsh conditions in the traditional method.
(2) The method has the advantages of simple raw materials and reagents, simple operation, high reaction yield, high product yield of 82-95 percent, easy separation and purification of the product, important value for the methodology research of o-methylene benzoquinone, and important significance in the synthesis of sulfur-containing natural products and drug molecules.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The invention is further described with reference to specific examples.
Example 1:
in a 100mL round bottom flask was added 2.00g (10mmol) of Compound I-1, 2.72g (20mmol) of Compound II-1, 0.17g (1mmol) of solid p-toluenesulfonic acid and finally 50mL of dry 1, 2-dichloroethane and the resulting mixture stirred at 30 ℃ for 10 h. The reaction mixture was cooled to room temperature, poured into ice water, extracted with 50mL of X3 dichloromethane, the organic phases combined, washed once with saturated brine, anhydrous Na 2 SO 4 Drying, concentrating to remove solvent to obtain crude product, and separating by column chromatography to obtain pure product of compound III-1. Oily liquid, 2.63g, yield 90%. 1 H NMR(400MHz,CDCl 3 )δ:7.45(d,J＝7.4Hz,2H),7.28(ddd,J＝16.7Hz,8.6Hz,3.6Hz,5H),7.20–7.05(m,5H),6.92–6.78(m,2H),6.39(s,1H),5.77(s,1H)； 13 C NMR(CDCl 3 ,100MHz)δ:154.16,139.15,134.58,131.09,130.03,129.08,128.92,128.70,128.66,127.60,127.30,125.89,120.94,117.15,53.67；HRMS(ESI)calcd for C 17 H 19 OS[M+H]+293.0995,found 293.0997.
Example 2:
a100 mL round bottom flask was charged with2.14g (10mmol) of Compound I-2, 2.72g (20mmol) of Compound II-1, 0.34g (2mmol) of solid p-toluenesulfonic acid, finally 25mL of dry DMF are added and the mixture is stirred at 30 ℃ for 3 hours until the reaction is complete. The reaction mixture was cooled to room temperature, poured into water, stirred, extracted with 50mL × 3 dichloromethane, the organic phases combined and washed once with saturated brine, anhydrous Na 2 SO 4 Drying, concentrating to remove solvent to obtain crude product, and separating by column chromatography to obtain pure product of compound III-2. Oily liquid, 2.69g, 88% yield. 1 HNMR(400MHz,CDCl 3 )δ7.39–7.27(m,4H),7.19–7.03(m,7H),6.87–6.77(m,2H),6.41(s,1H),5.73(s,1H),2.32(s,3H)； 13 C NMR(CDCl 3 ,100MHz)δ:154.21,137.36,136.02,134.69,131.01,130.03,129.40,129.02,128.90,128.49,127.23,125.99,120.89,117.19,53.56,21.12；HRMS(ESI)calcd for C 20 H 19 OS[M+H] + 307.1151,found 307.1150.
Example 3:
in a 100mL round bottom flask was added 2.14g (10mmol) of Compound I-3, 2.04g (15mmol) of Compound II-1, 0.09g (0.5mmol) of solid p-toluenesulfonic acid and finally 50mL of dry DMSO and the resulting mixture was stirred vigorously at 35 ℃ for 5 h. The reaction mixture was cooled to room temperature, poured into water, stirred, extracted with 50mL × 3 dichloromethane, the organic phases combined and washed once with saturated brine, anhydrous Na 2 SO 4 Drying, concentrating, evaporating to remove solvent to obtain crude product, and purifying by column chromatography to obtain pure product of compound III-3. Oily liquid, 2.66g, yield 87%. 1 H NMR(400MHz,CDCl 3 )δ:7.62–7.52(m,1H),7.30–7.07(m,11H),6.85(dd,J＝7.4,5.4Hz,2H),6.27(s,1H),5.92(s,1H),2.37(s,3H)； 13 C NMR(CDCl 3 ,100MHz)δ:154.11,137.28,136.34,135.53,130.70,130.07,129.95,128.96,128.92,128.72,127.58,126.89,126.43,125.81,121.03,116.88,49.69,19.39；HRMS(ESI)calcd for C 20 H 19 OS[M+H] + 307.1151,found 307.1150.
Example 4:
a100 mL round bottom flask was charged with 2.48g (10mmol) of Compound I-4, 2.04g (15mmol) of Compound II-1, 0.17g (1mmol) of solid p-toluenesulfonic acid, and finally 50mL of 1, 2-dichloroethane, and the resulting mixture was stirred vigorously at 40 ℃ for 7 hours. The reaction mixture was cooled to room temperature, poured into water, stirred, extracted with 50mL × 3 dichloromethane, the organic phases combined and washed once with saturated brine, anhydrous Na 2 SO 4 Drying, concentrating to remove solvent to obtain an oily residue, and purifying by column chromatography to obtain pure compound III-4. Oily liquid, 2.77g, 85% yield. 1 H NMR(400MHz,CDCl 3 )δ:7.38(d,J＝8.4Hz,2H),7.27(dt,J＝10.5Hz,5.7Hz,4H),7.23–7.09(m,5H),6.89–6.78(m,2H),6.22(s,1H),5.75(s,1H)； 13 C NMR(CDCl 3 ,100MHz)δ:153.85,137.97,134.34,133.31,131.14,130.02,129.79,129.20,129.00,128.76,127.44,125.73,121.10,117.05,52.65；HRMS(ESI)calcd for C 19 H 16 ClOS[M+H]+327.0605,found 327.0605.
Example 5:
in a 100mL round bottom flask was added 2.44g (10mmol) of Compound I-5, 2.72g (20mmol) of Compound II-1, 0.17g (1mmol) of solid p-toluenesulfonic acid, and finally 30mL of dry DMF, and the resulting mixture was stirred vigorously at 30 ℃ for 8 hours. The reaction mixture was cooled to room temperature, poured into water, stirred, extracted with 50mL × 3 dichloromethane, the organic phases combined and washed once with saturated brine, anhydrous Na 2 SO 4 Drying, concentrating to remove solvent to obtain an oily residue, and purifying by column chromatography to obtain pure compound III-5. Oily liquid, 2.56g, yield 86%. 1 H NMR(400MHz,CDCl 3 )δ:7.47(d,J＝7.4Hz,2H),7.33–7.22(m,4H),7.19–7.07(m,4H),6.79(t,J＝8.0Hz,1H),6.72(d,J＝8.0Hz,1H),6.03(s,1H),5.91(s,1H),4.17–3.95(m,2H),1.41(t,J＝7.0Hz,3H)； 13 C NMR(CDCl 3 ,100MHz)δ:145.64,142.93,140.85,136.72,129.66,128.67(d,J＝2.7Hz),128.69,128.66,128.45,128.42,128.39,127.05,126.83,126.11,121.04,119.64,110.29,64.58,49.60,14.91；HRMS(ESI)calcd for C 18 H 21 OS[M+H] + 285.1308,found285.1308.
Example 6:
in a 100mL round bottom flask was added 2.00g (10mmol) of Compound I-1, 1.76g (20mmol) of Compound II-2, 0.17g (1mmol) of solid p-toluenesulfonic acid and finally 50mL of dry 1, 2-dichloroethane and the resulting mixture stirred at 60 ℃ for 10 h. The reaction mixture was cooled to room temperature, poured into water, stirred, extracted with 50mL × 3 dichloromethane, the organic phases combined and washed once with saturated brine, anhydrous Na 2 SO 4 Drying, concentrating to remove solvent to obtain crude product, and purifying by column chromatography to obtain pure product of compound III-6. Oily liquid, 2.15g, 88% yield. 1 HNMR(400MHz,CDCl 3 )δ:7.40(d,J＝7.4Hz,2H),7.35–7.14(m,5H),7.05(dd,J＝7.6Hz,1.2Hz,1H),6.91(dd,J＝8.0Hz,0.7Hz,1H),6.88–6.78(m,1H),5.39(s,1H),2.52–2.39(m,2H),1.23(t,J＝7.4Hz,3H)； 13 C NMR(CDCl 3 ,100MHz)δ:155.15,139.31,130.17,129.21,128.39,128.67,128.53,128.51,127.55,125.16,120.76,117.60,50.47,26.36,14.19；HRMS(ESI)calcd for C 15 H 23 OS[M+H] + 251.1464,found251.1464.
The present invention has been described in detail with reference to the specific embodiments, but the scope of the present invention is not limited thereto.
Claims (7)
1. A nucleophilic reaction method of alkenyl thioether to o-methylene benzoquinone is characterized by comprising the following steps:
(1) dissolving 2- (hydroxy (phenyl) methyl) phenol compounds and vinyl thioether compounds in an organic solvent, adding a p-toluenesulfonic acid catalyst, and stirring for reaction for 5-10h at 25-80 ℃; the structural formula of the 2- (hydroxy (phenyl) methyl) phenol compound is as follows:
in the formula R 1 And R 2 Same or different from H, C1-C5 alkyl, halogen X, -NO 2 Any one of-CN and-OR 4; the structural formula of the vinyl thioether compound is shown as
R 3 Any one selected from phenyl and C1-C10 alkyl; r4 is selected from any one of alkyl of H, C1-C5;
(2) extracting the reacted reaction solution, combining organic layers, washing, drying, evaporating to remove the solvent, and performing silica gel column chromatography on the residue to obtain the product with the structural formula
2. The nucleophilic reaction method for alkenylthio-p-o-methylenequinone according to claim 1, wherein the 2- (hydroxy (phenyl) methyl) phenol compound, the vinyl thio-ether compound, the p-toluenesulfonic acid catalyst and the organic solvent are added in a ratio of 1 mmol: 1.5-3 mmol: 0.05-0.2 mmol: 2.5-10 ml.
3. The nucleophilic reaction method for alkenylthio-p-o-methylenequinone according to claim 1, wherein the 2- (hydroxy (phenyl) methyl) phenol compound, the vinyl thio-ether compound, the p-toluenesulfonic acid catalyst and the organic solvent are added in a ratio of 1 mmol: 2 mmol: 0.1 mmol: 5 ml.
4. The nucleophilic reaction method for an alkenyl thioether p-o-methylenequinone according to claim 1, wherein the organic solvent is one of DMF, DMSO, toluene, acetonitrile, dichloromethane, chloroform, 1, 2-dichloroethane, ethyl acetate, or tetrahydrofuran.
5. The method as claimed in claim 4, wherein the organic solvent is 1, 2-dichloroethane.
6. The method for nucleophilic reaction of alkenyl thioether to o-methylene benzoquinone according to claim 1, wherein the eluent from the silica gel column chromatography in step (2) is one or more of petroleum ether, n-hexane and cyclohexane.
7. The method as claimed in claim 6, wherein the eluent from the silica gel column chromatography in step (2) is petroleum ether.
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