CN102010406B - 4-(benzofuran-5-yl)-2-aromatic aminothiazole and preparation method and application thereof - Google Patents
4-(benzofuran-5-yl)-2-aromatic aminothiazole and preparation method and application thereof Download PDFInfo
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- CN102010406B CN102010406B CN2010105538489A CN201010553848A CN102010406B CN 102010406 B CN102010406 B CN 102010406B CN 2010105538489 A CN2010105538489 A CN 2010105538489A CN 201010553848 A CN201010553848 A CN 201010553848A CN 102010406 B CN102010406 B CN 102010406B
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- 0 CC(C)(C1)Oc(c(O*)c2)c1cc2C(C)=O Chemical compound CC(C)(C1)Oc(c(O*)c2)c1cc2C(C)=O 0.000 description 2
- NVPXZAAIJLPUPJ-UHFFFAOYSA-N CC(C)(Cc1cc(-c2c[s]c(Nc3ccccc3)n2)c2)Oc1c2OC Chemical compound CC(C)(Cc1cc(-c2c[s]c(Nc3ccccc3)n2)c2)Oc1c2OC NVPXZAAIJLPUPJ-UHFFFAOYSA-N 0.000 description 2
- BSWBYBJFEZZSKY-UHFFFAOYSA-N CC(C)(C1)Oc(c(OC)c2)c1cc2-c1c[s]c(Nc(cc2)ccc2Cl)n1 Chemical compound CC(C)(C1)Oc(c(OC)c2)c1cc2-c1c[s]c(Nc(cc2)ccc2Cl)n1 BSWBYBJFEZZSKY-UHFFFAOYSA-N 0.000 description 1
- DKWMHMCCXGYLOK-UHFFFAOYSA-N CC(C)(C1)Oc(c(OC)c2)c1cc2-c1c[s]c(Nc(cccc2)c2OC)n1 Chemical compound CC(C)(C1)Oc(c(OC)c2)c1cc2-c1c[s]c(Nc(cccc2)c2OC)n1 DKWMHMCCXGYLOK-UHFFFAOYSA-N 0.000 description 1
- LCUWCJIGZPJAJS-UHFFFAOYSA-N CC(C)(Cc1cc(-c2c[s]c(Nc(cccc3)c3Br)n2)c2)Oc1c2OC Chemical compound CC(C)(Cc1cc(-c2c[s]c(Nc(cccc3)c3Br)n2)c2)Oc1c2OC LCUWCJIGZPJAJS-UHFFFAOYSA-N 0.000 description 1
- BJADKWHJQQXTHA-UHFFFAOYSA-N CC(C)(Cc1cc(-c2c[s]c(Nc3cc(C(F)(F)F)ccc3)n2)c2)Oc1c2OC Chemical compound CC(C)(Cc1cc(-c2c[s]c(Nc3cc(C(F)(F)F)ccc3)n2)c2)Oc1c2OC BJADKWHJQQXTHA-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses 4-(benzofuran-5-yl)-2-aromatic aminothiazole shown as a chemical structural formula I. The preparation method of the 4-(benzofuran-5-yl)-2-aromatic aminothiazole comprises the following steps of: heating and stirring 2-halogen-1-(7-hydroxyl/alkoxyl-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl) butanone and arylthiourea in acetone for reaction to obtain 4-(benzofuran-5-yl)-2-aromatic aminothiazole salt; and neutralizing the 4-(benzofuran-5-yl)-2-aromatic aminothiazole salt with stronger ammonia water to obtain the 4-(benzofuran-5-yl)-2-aromatic aminothiazole. The 4-(benzofuran-5-yl)-2-aromatic aminothiazole has high insecticidal activity and is applied to the preparation of pesticides.
Description
Technical field
The present invention relates to one type of new compound, specifically is 4-(cumarone-5-yl)-2-virtue Basedol and preparation method thereof and as the application of sterilant.
Background technology
Shao Ling etc. have described 4-aryl-5-triazolyl thiazole-2-imine compound, and the biological activity determination result shows that part of compounds has fungicidal activity (SCI, 2007,28,270) to apple wheel line bacterium.Michael etc. have described thiazolamine class breast cancer medicines (Bioorg & Med.Chem.2004,12,1029); Jiang Feng is superfine described the pair cell apoptosis have the active 4-aryl thiazole-2-imine derivative of inhibition (Acta Pharmaceutica Sinica, 2006,41:727).Lin etc. have described the schiff base compound COX-2 have been had selective inhibitory (Bioorg & Med Chem, 2008,16 (5): 2697).He Daohang etc. have described the synthetic and fungicidal activity [South China Science & Engineering University's journal natural science edition, 2008, (3): 60] of 4-aryl-2-(2-hydroxyl benzyl imino-) thiazole; Chinese patent (CN 101602761, and CN 200910226728.5) has been described the fungicidal activity and the anti-tumor activity of the 4-tertiary butyl-5-(1,2, the 4-triazol-1-yl)-2-benzyl imino-thiazole; Hu Aixi etc. have described synthetic and COX-2 active [Hunan University's journal natural science edition, 2009,36 (2), the 70-74 of 5-benzyl-4-tertiary butyl-2-benzyl imino-thiazole; Chinese patent, CN 101492426] and anti-tumor activity [CN 200910226774.5, and CN 101781269].4-(cumarone-5-yl)-2-virtue Basedol and preparation method and and do not research and develop report as the application of sterilant.
The present invention with pesticide efficacy base benzofuranol and thiazole amalgamation in a part, designing and preparing 4-(cumarone-5-yl)-2-virtue Basedol novel cpd.
Summary of the invention
The object of the present invention is to provide the 4-shown in the chemical structural formula I (cumarone-5-yl)-2-virtue Basedol.4-(cumarone-5-yl)-2-virtue Basedol chemistry 4-(7-hydroxyl/alkoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl) by name-2-virtue Basedol.
Wherein, R is selected from: H, C
1～C
2Alkyl, C
3～C
4Straight chained alkyl or branched-chain alkyl; Ar is selected from: phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl, 2-p-methoxy-phenyl, 3-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-acetylamino phenyl, 3-acetylamino phenyl, 4-acetylamino phenyl, 2-methanesulfonamido phenyl, 3-methanesulfonamido phenyl, 4-methanesulfonamido phenyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2; 4-3,5-dimethylphenyl, 3; 4-3,5-dimethylphenyl, 2; 6-3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 2-chloro-4-fluorophenyl, 2-chloro-3-fluorophenyl, 3-chloro-4-fluorophenyl, 2; 3-dichlorophenyl, 2; 6-dichlorophenyl, 3; 4-dichlorophenyl, 2; 4-two chloro-5-fluorophenyls, 2,6-dichlor-4-trifluoromethyl phenyl, 2-acetylaminohydroxyphenylarsonic acid 5-carbethoxy phenyl, 2-acetylaminohydroxyphenylarsonic acid 5-carboxyl phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl.
The objective of the invention is to also provide the preparation method of 4-(cumarone-5-yl)-2-virtue Basedol, its preparation comprises the steps:
(1) 1-(7-hydroxyl/alkoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, ethanol stir, and reflux, and add copper halide in batches, and reaction 2～4h makes 2-halogen-1-(cumarone-5-yl) ethyl ketone; Preparation is undertaken by following reaction formula:
In the reaction formula, X is selected from: Br, Cl; R is selected from: H, C
1～C
2Alkyl, C
3～C
4Straight chained alkyl or branched-chain alkyl.
(2) 2-halogen-1-(7-hydroxyl/alkoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl) ethyl ketone and aryl thiourea heats in acetone, stirring reaction makes 4-(cumarone-5-yl)-2-virtue Basedol salt; 4-(cumarone-5-yl)-2-virtue Basedol salt makes 4-(cumarone-5-yl)-2-virtue Basedol with the strong aqua neutralization; Preparation is undertaken by following reaction formula:
In the reaction formula, X is selected from: Br, Cl; R is selected from: H, C
1～C
2Alkyl, C
3～C
4Straight chained alkyl or branched-chain alkyl; Ar is selected from: phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl, 2-p-methoxy-phenyl, 3-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-acetylamino phenyl, 3-acetylamino phenyl, 4-acetylamino phenyl, 2-methanesulfonamido phenyl, 3-methanesulfonamido phenyl, 4-methanesulfonamido phenyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2; 4-3,5-dimethylphenyl, 3; 4-3,5-dimethylphenyl, 2; 6-3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 2-chloro-4-fluorophenyl, 2-chloro-3-fluorophenyl, 3-chloro-4-fluorophenyl, 2; 3-dichlorophenyl, 2; 6-dichlorophenyl, 3; 4-dichlorophenyl, 2; 4-two chloro-5-fluorophenyls, 2,6-dichlor-4-trifluoromethyl phenyl, 2-acetylaminohydroxyphenylarsonic acid 5-carbethoxy phenyl, 2-acetylaminohydroxyphenylarsonic acid 5-carboxyl phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl.
The 4-that the object of the present invention is to provide (cumarone-5-yl)-2-virtue Basedol has good insecticidal activity, can in the preparation sterilant, use.
The present invention compared with prior art has following advantage:
1. the present invention designs first and has prepared one type of 4-(cumarone-5-yl)-2-virtue Basedol.
2. find first that 4-(cumarone-5-yl)-2-virtue Basedol has insecticidal activity, can be used for preparing sterilant.
Embodiment
Following examples are intended to explain the present invention rather than to further qualification of the present invention.
Embodiment 14-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-phenylamino) preparation of thiazole
(1) preparation of 2-bromo-1-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl) ethyl ketone
0.02mol 1-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 80mL ethanol, stirring and refluxing adds the 0.04mol cupric bromide in batches; Reaction 2h, reacting liquor while hot is filtered, distillating recovering solvent, acetic acid ethyl dissolution, weak acid scrubbing; Filter, the washing of filtrating warp, separatory, drying, ethyl alcohol recrystallization gets 2-bromo-1-(7-methoxyl group-2; 2-dimethyl--2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, productive rate 50.0%, 90～91 ℃ of fusing points.
(2) preparation of 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-phenylamino thiazole
2.0mmol 2-bromo-1-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl) ethyl ketone, 1.8mmol phenylthiourea, 20mL acetone; Heated and stirred, reaction 2h, solid is separated out in the reaction solution cooling; Filter; Dry 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-the yl)-2-phenylamino thiazole hydrobromide salt that gets; 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-phenylamino thiazole hydrobromide salt makes 4-(7-methoxyl group-2 through the ammoniacal liquor neutralization; 2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl)-and 2-phenylamino thiazole, yield 93.2%, 177.8～178.7 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.53 (s, 6H, 2 * CH
3), 3.06 (s, 2H, CH
2), 3.94 (s, 3H, OCH
3), 6.62 (s, 1H, thiazole ring 5-H), 7.11 (m, 2H, C
6H
2), 7.36～7.37 (m, 5H, C
6H
5); EI-MS (m/z): 353.2 (M
+).
The preparation of embodiment 24-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-methylbenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2-tolylthiourea reaction 1.0h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-methylbenzene is amino) thiazole; Yield 92.4%, 146.5～147.5 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.53 (s, 6H, 2 * CH
3), 2.35 (s, 3H, CH
3), 3.06 (s, 2H, CH
2), 3.95 (s, 3H, OCH
3), 6.59 (s, 1H, thiazole ring 5-H), 7.10 (m, 2H, C
6H
2), 7.24～7.62 (m, 4H, C
6H
4); EI-MS (m/z): 367.2 (M
+).
The preparation of embodiment 34-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 3-methylbenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 3-aminomethyl phenyl thiocarbamide reaction 2.0h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 3-methylbenzene is amino) thiazole; Yield 87.8%, 177.9～178.5 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.43 (s, 6H, 2 * CH
3), 2.31 (s, 3H, CH
3), 3.05 (s, 2H, CH
2), 3.83 (s, 3H, OCH
3), 6.77～7.58 (m, 7H, C
6H
4, C
6H
2, thiazole ring 5-H), 10.14 (s, 1H, NH); EI-MS (m/z): 367.2 (M
+).
The preparation of embodiment 44-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 4-methylbenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 4-aminomethyl phenyl thiocarbamide reaction 2.0h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 4-methylbenzene is amino) thiazole; Yield 93.1%, 167.7～170.1 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.49 (s, 6H, 2 * CH
3), 2.34 (s, 3H, CH
3), 3.05 (s, 2H, CH
2), 3.94 (s, 3H, OCH
3), 6.58 (s, 1H, thiazole ring 5-H), 7.17～7.25 (m, 6H, C
6H
4, C
6H
2); EI-MS (m/z): 367.2 (M
+).
The preparation of embodiment 54-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 3-hydroxybenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 3-hydroxy phenyl thiocarbamide reaction 2.5h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 3-hydroxybenzene is amino) thiazole; Yield 74.9%, 183.7～184.6 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.43 (s, 6H, 2 * CH
3), 3.06 (s, 2H, CH
2), 3.83 (s, 3H, OCH
3), 6.36～7.38 (m, 7H, C
6H
4, thiazole ring 5-H, C
6H
2), 9.40 (s, 1H, OH), 10.09 (s, 1H, NH); EI-MS (m/z): 369.2 (M
+).
The preparation of embodiment 64-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-anisole is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2-p-methoxy-phenyl thiocarbamide reaction 2h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-anisole is amino) thiazole; Yield 90.3%, 121.0～122.3 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.54 (s, 6H, 2 * CH
3), 3.08 (s, 2H, CH
2), 3.91 (s, 3H, OCH
3), 3.97 (s, 3H, OCH
3), 6.61 (s, 1H, thiazole ring 5-H), 6.92～7.03 (m, 4H, C
6H
4), 7.04～7.30 (m, 2H, C
6H
2), 7.87 (s, 1H, NH); EI-MS (m/z): 383.2 (M
+).
The preparation of embodiment 74-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 4-anisole is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 4-p-methoxy-phenyl thiocarbamide reaction 3h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 4-anisole is amino) thiazole; Yield 88.4%%, 166.8～167.0 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.54 (s, 6H, 2 * CH
3), 3.07 (s, 2H, CH
2), 3.83 (s, 3H, OCH
3), 3.96 (s, 3H, OCH
3), 6.48 (s, 1H, thiazole ring 5-H), 6.93～7.30 (m, 6H, C
6H
4, C
6H
2); EI-MS (m/z): 383.2 (M
+).
The preparation of embodiment 84-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2-fluoroanilino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2-fluorophenyl thiocarbamide reaction 3h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2-fluoroanilino) thiazole; Yield 82.6%, 142.5～142.8 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.59 (s, 6H, 2 * CH
3), 3.08 (s, 2H, CH
2), 3.95 (s, 3H, OCH
3), 6.68 (s, 1H, thiazole ring 5-H), 7.02～8.08 (m, 6H, C
6H
4, C
6H
2); EI-MS (m/z): 371.2 (M
+).
The preparation of embodiment 94-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-chlorobenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2-chloro-phenyl-thiocarbamide reaction 2h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-chlorobenzene is amino) thiazole; Yield 87.2%, 139.5～141.3 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.54 (s, 6H, 2 * CH
3), 3.08 (s, 2H, CH
2), 3.96 (s, 3H, OCH
3), 6.70 (s, 1H, thiazole ring 5-H), 7.02～8.12 (m, 6H, C
6H
4, C
6H
2); EI-MS (m/z): 387.0 (M
+).
The preparation of embodiment 104-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 4-chlorobenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 4-chloro-phenyl-thiocarbamide reaction 3h; It is amino to make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-4-chlorobenzene) thiazole; Yield 90.8%, 194.4～195.1 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.53 (s, 6H, 2 * CH
3), 3.05 (s, 2H, CH
2), 3.93 (s, 3H, OCH
3), 6.64 (s, 1H, thiazole ring 5-H), 7.24～7.31 (m, 6H, C
6H
4, C
6H
2); EI-MS (m/z): 387.0 (M
+).
The preparation of embodiment 114-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-bromobenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2-bromophenyl thiocarbamide reaction 2h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-bromobenzene is amino) thiazole; Yield 91.4%, 140.1～141.2 ℃ of fusing points.
1H NMR (DMSO-d
6, 300MHz), δ: 1.42 (s, 6H, 2 * CH
3), 3.03 (s, 2H, CH
2), 3.80 (s, 3H, OCH
3), 7.00～8.23 (m, 7H, C
6H
4, C
6H
2, thiazole ring 5-H), 9.47 (s, 1H, NH); EI-MS (m/z): 433.0 (M
+).
The preparation of embodiment 124-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 3-bromobenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 3-bromophenyl thiocarbamide reaction 2.5h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 3-bromobenzene is amino) thiazole; Yield 87.9%, 184.6～185.1 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.53 (s, 6H, 2 * CH
3), 3.06 (s, 2H, CH
2), 3.93 (s, 3H, OCH
3), 6.66 (s, 1H, thiazole ring 5-H), 7.19～7.25 (m, 6H, C
6H
4, C
6H
2), 7.74 (s, 1H, NH); EI-MS (m/z): 433.0 (M
+).
The preparation of embodiment 134-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2-oil of mirbane is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2-nitrophenyl thiocarbamide reaction 5h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2-oil of mirbane is amino) thiazole; Yield 89.3%, 185.4～187.0 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.42 (s, 6H, 2 * CH
3), 3.03 (s, 2H, CH
2), 3.81 (s, 3H, OCH
3), 7.18～8.19 (m, 7H, C
6H
4, C
6H
2, thiazole ring 5-H), 10.45 (s, 1H, NH); EI-MS (m/z): 398.0 (M
+).
The preparation of embodiment 144-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(4-oil of mirbane is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 4-nitrophenyl thiocarbamide reaction 6h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(4-oil of mirbane is amino) thiazole; Yield 91.5%, 248.9～251.4 ℃ of fusing points.
1H NMR (DMSO-d
6, 300MHz), δ: 1.44 (s, 6H, 2 * CH
3), 3.07 (s, 2H, CH
2), 3.85 (s, 3H, OCH
3), 7.36～8.29 (m, 7H, C
6H
4, C
6H
2, thiazole ring 5-H), 11.04 (s, 1H, NH); EI-MS (m/z): 398.0 (M
+).
The preparation of embodiment 154-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(3-trifluoromethyl phenylamino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 3-trifluoromethyl thiocarbamide reaction 2h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(3-trifluoromethyl phenylamino) thiazole; Yield 81.2%, 163.2～163.8 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.54 (s, 6H, 2 * CH
3), 3.07 (s, 2H, CH
2), 3.96 (s, 3H, OCH
3), 6.66 (s, 1H, thiazole ring 5-H), 7.24～7.50 (m, 6H, C
6H
4, C
6H
2), 7.98 (s, 1H, NH); EI-MS (m/z): 421.2 (M
+).
The preparation of embodiment 164-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(4-trifluoromethyl phenylamino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 4-trifluoromethyl thiocarbamide reaction 3h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(4-trifluoromethyl phenylamino) thiazole; Yield 85.6%, 233.8～234.6 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.55 (s, 6H, 2 * CH
3), 3.09 (s, 2H, CH
2), 3.97 (s, 3H, OCH
3), 6.64 (s, 1H, thiazole ring 5-H), 7.24～7.67 (m, 7H, C
6H
4, C
6H
2, NH); EI-MS (m/z): 421.2 (M
+).
The preparation of embodiment 174-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2, the 4-xylidino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2,4-fenthiuron reaction 2h makes 4-(7-methoxyl group-2; 2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2, the 4-xylidino) thiazole; Yield 92.4%, 171.9～173.2 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.53 (s, 6H, 2 * CH
3), 2.26 (s, 6H, 2 * CH
3), 3.05 (s, 2H, CH
2), 3.94 (s, 3H, OCH
3), 6.57 (s, 1H, thiazole ring 5-H), 7.11～7.26 (m, 7H, C
6H
4, C
6H
2); EI-MS (m/z): 381.2 (M
+).
The preparation of embodiment 184-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(3, the 4-xylidino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 3,4-fenthiuron reaction 2h makes 4-(7-methoxyl group-2; 2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(3, the 4-xylidino) thiazole; Yield 92.9%, 171.3～171.7 ℃ of fusing points.
1H NMR (CDCl DMSO-d
6, 300MHz), δ: 1.43 (s, 6H, 2 * CH
3), 2.17 (s, 3H, CH
3), 2.22 (s, 3H, CH
3), 3.05 (s, 2H, CH
2), 3.82 (s, 3H, OCH
3), 7.07～7.39 (m, 5H, C
6H
3, C
6H
2), 7.50 (s, 1H, thiazole ring 5-H), 10.03 (s, 1H, NH); EI-MS (m/z): 381.2 (M
+).
The preparation of embodiment 194-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2, the 6-xylidino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2,6-fenthiuron reaction 2h makes 4-(7-methoxyl group-2; 2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2, the 6-xylidino) thiazole; Yield 94.2%, 172.8～173.5 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.52 (s, 6H, 2 * CH
3), 2.33 (s, 6H, 2 * CH
3), 3.01 (s, 2H, CH
2), 3.93 (s, 3H, OCH
3), 6.47 (s, 1H, thiazole ring 5-H), 7.16～7.26 (m, 5H, C
6H
3, C
6H
2); EI-MS (m/z): 381.2 (M
+).
The preparation of embodiment 204-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(3-chloro-4-fluoroanilino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 3-chloro-4-fluorophenyl thiocarbamide reaction 2h; Make 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(3-chloro-4-fluoroanilino) thiazole; Yield 91.8%, 187.1～188.6 ℃ of fusing points.
1H NMR (DMSO-d
6, 300MHz), δ: 1.43 (s, 6H, 2 * CH
3), 3.05 (s, 2H, CH
2), 3.84 (s, 3H, OCH
3), 7.20～7.49 (m, 5H, C
6H
3, C
6H
2), 8.25 (s, 1H, thiazole ring 5-H), 10.45 (s, 1H, NH); EI-MS (m/z): 405.0 (M
+).
The preparation of embodiment 214-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2, the 3-dichlorobenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2,3-dichlorophenyl thiocarbamide reaction 3h makes 4-(7-methoxyl group-2; 2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2, the 3-dichlorobenzene is amino) thiazole; Yield 89.4%, 130.3～132.1 ℃ of fusing points.
1H NMR (DMSO-d
6, 300MHz), δ: 1.47 (s, 6H, 2 * CH
3), 3.04 (s, 2H, CH
2), 3.81 (s, 3H, OCH
3), 7.24～8.50 (m, 6H, C
6H
3, C
6H
2, thiazole ring 5-H), 9.82 (s, 1H, NH); EI-MS (m/z): 421.1 (M
+).
The preparation of embodiment 224-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(3, the 4-dichlorobenzene is amino) thiazole
Press the method for embodiment 1,2-bromo-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 3,4-dichlorophenyl thiocarbamide reaction 3h makes 4-(7-methoxyl group-2; 2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(3, the 4-dichlorobenzene is amino) thiazole; Yield 81.7%, 213.7～215.3 ℃ of fusing points.
1H NMR (DMSO-d
6, 300MHz), δ: 1.44 (s, 6H, 2 * CH
3), 3.06 (s, 2H, CH
2), 3.84 (s, 3H, OCH
3), 7.24～7.59 (m, 5H, C
6H
3, C
6H
2), 8.34 (s, 1H, thiazole ring 5-H), 10.59 (s, 1H, NH); EI-MS (m/z): 421.1 (M
+).
The preparation of embodiment 234-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-pyridine is amino) thiazole
Press the method for embodiment 1,2-chloro-1-(7-methoxyl group-2,2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl) ethyl ketone and 2-pyridine thiocarbamide reaction 4h; Dry 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-pyridine is amino) thiazole hydrochloride that gets; 4-(7-methoxyl group-2; 2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl)-2-(2-pyridine amino) thiazole hydrochloride makes 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(2-pyridine amino) thiazole with system in ammoniacal liquor; Yield 86.5%, 200.3～201.4 ℃ of fusing points.
1H NMR (CDCl
3, 300MHz), δ: 1.52 (s, 6H, 2 * CH
3), 2.33 (s, 6H, 2 * CH
3), 3.01 (s, 2H, CH
2), 3.92 (s, 3H, OCH
3), 6.82～8.38 (m, 7H, C
6H
4, C
6H
2, thiazole ring 5-H); EI-MS (m/z): 354.1 (M
+).
Embodiment 244-(cumarone-5-yl)-2-virtue Basedol is measured mythimna separata, black bean aphid and two-spotted spider mite cytotoxicity
1 supplies the examination target
Mythimna separata (Mythimna sepatara) is to raise sensitive strain for many years with the fresh corn leaf; It is 3 instar larvaes that worm is used in test; Black bean aphid (Aphis fabae) is indoor with broad bean seedling raising sensitive strain for many years, and it is if that 3 ages in days are aphid that worm is used in test; Two-spotted spider mite (Tetranychus urticae) is indoor with broad bean seedling raising sensitive strain for many years.Test uses worm to become mite as health.
2 culture condition
Supplying the culture condition of examination target and test back target is temperature 25+5 ℃, relative humidity 65 ± 5%, periodicity of illumination 12/12h (L/D).
3 test medicines (former medicine): 4-(cumarone-5-yl)-2-virtue Basedol.
4 medicaments are prepared former medicine: take by weighing aequum with ten thousand/electronic balance; Solvent: N, N N (DMF), 0.2%; Emulsifying agent: Tween 80,0.2%; Add clear water and be diluted to desired concn.
5 TPs are with reference to " pesticide bioactivity is estimated SOP ".
The general sieve of mythimna separata: adopt spray method.In being lined with the petridish of filter paper (Φ 90mm), put into the leaf of Semen Maydis section of big or small basically identical, insert 10 of third-instar larvaes again, be put under the Potter spray tower and spray.Spray amount 1ml/10 head, 2 repetitions.Dispose, be put into the observation indoor cultivation.Regularly observe.Inspection and record death condition are calculated mortality ratio behind the 96h.
The general sieve of black bean aphid adopts pickling process.To have 3 age in days broad beans if the broad bean seedling of aphid is cut, dipping took out after 10 seconds in the soup for preparing, and was inserted on the sponge that suctions water, covered the lampshade that starts, and every processing repeats for 2 times.Dispose, be put into the observation indoor cultivation, regularly observe, inspection and record death condition are calculated mortality ratio behind the 72h.
Two-spotted spider mite is adopted pickling process.The broad bean seedling that will have red spider is cut, and in the soup for preparing, soaks taking-up in 10 seconds, inhales with filter paper and removes unnecessary soup around plant and the mite body, is inserted on the beaker that dress water sealed, and every processing repeats for 2 times.Dispose, be put into the observation indoor cultivation, regularly observe, inspection and record death condition are calculated mortality ratio behind the 72h.
6 cytotoxicities
The cytotoxicity of preferred compound: when effective constituent concentration was 1000mg/L, behind the dispenser 96h, 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-pyridine is amino) thiazole was 93.75% to the mortality ratio of mythimna separata; When effective constituent concentration is 500mg/L, behind the processing 72h, 4-(7-methoxyl group-2; 2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl)-and the 2-phenylamino) thiazole, 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(the 2-methylbenzene is amino) thiazole, 4-(7-4-(7-methoxyl group-2; 2-dimethyl--2; 3-Dihydrobenzofuranes-5-yl)-2-(2-fluoroanilino) thiazole and 4-(7-methoxyl group-2,2-dimethyl--2,3-Dihydrobenzofuranes-5-yl)-2-(3-chloro-4-fluoroanilino) thiazole be respectively 95.12%, 62.60%, 57.53% and 59.06% to the black bean aphid mortality ratio.4-(cumarone-5-yl)-2-virtue Basedol has good insecticidal activity, can be used as the preparation sterilant and on agricultural, uses.
Claims (3)
1. the 4-shown in the chemical structural formula I (cumarone-5-yl)-2-virtue Basedol:
Wherein, R is selected from: H, C
1～C
2Alkyl, C
3～C
4Straight chained alkyl or branched-chain alkyl; Ar is selected from: phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl, 2-p-methoxy-phenyl, 3-p-methoxy-phenyl, 4-p-methoxy-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2; 4-3,5-dimethylphenyl, 3; 4-3,5-dimethylphenyl, 2; 6-3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 2-chloro-4-fluorophenyl, 2-chloro-3-fluorophenyl, 3-chloro-4-fluorophenyl, 2; 3-dichlorophenyl, 2; 6-dichlorophenyl, 3; 4-dichlorophenyl, 2,4-two chloro-5-fluorophenyls, 2,6-dichlor-4-trifluoromethyl phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl.
2. the preparation method of the described 4-of claim 1 (cumarone-5-yl)-2-virtue Basedol; Its preparation comprises the steps: 2-halogen-1-(7-hydroxyl/alkoxyl group-2; 2-dimethyl--2,3-Dihydrobenzofuranes-5-yl) ethyl ketone and aryl thiourea heats in acetone, stirring reaction makes 4-(cumarone-5-yl)-2-virtue Basedol salt; 4-(cumarone-5-yl)-2-virtue Basedol salt makes 4-(cumarone-5-yl)-2-virtue Basedol with the strong aqua neutralization; Preparation is undertaken by following reaction formula:
In the reaction formula, X is selected from: Br, Cl; The definition of R and Ar according to claim 1.
3. the described 4-of claim 1 (cumarone-5-the yl)-application of 2-virtue Basedol in the preparation sterilant.
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| CN102952127B (en) * | 2010-12-02 | 2015-01-21 | 湖南大学 | 4-(2,3-dihydrobenzene benzofuran-5-yl)-2-(2-aminopyridine) chiral crystal |
| CN102127066B (en) * | 2010-12-10 | 2013-08-14 | 邵阳学院 | 4-(7-methoxy-2,2,-dimethyl-2,3-dihydrobenzofuran-5-yl)-2-(3,4-xylylazoamino)thiazole chiral crystal |
| CN102603726B (en) * | 2012-01-18 | 2014-08-13 | 湖南化工研究院 | 5-(2-aminothiazole-4-yl) benzofuranol etheric compound with herbicidal activity and preparation method |
| US9598389B2 (en) | 2013-03-06 | 2017-03-21 | Syngenta Participations Ag | Dihydrobenzofuran derivatives as insecticidal compounds |
| CN103141486B (en) * | 2013-04-01 | 2014-05-28 | 湖南大学 | Application of 4-(benzofuran-5-yl)-2-phenzyl aminothiazole as bactericide |
| CN103145700B (en) * | 2013-04-01 | 2015-04-01 | 湖南大学 | 2-(2-benzyl hydrazono)-4-(benzofuran-5-yl) thiazole and preparation method and application thereof |
| CN103739599B (en) * | 2014-01-15 | 2015-10-07 | 湖南大学 | 3-[[2-(2-benzyl hydrazono-) thiazole-5-base] methyl] quinoline-2 (1H)-one and preparation and application thereof |
| CN105859697B (en) * | 2015-01-19 | 2018-05-04 | 湖南大学 | 1- benzofuranols ether -3- phenyl -2- (1,2,4- triazol-1-yls) -2- propenyls and its application |
| CN105153134B (en) * | 2015-09-17 | 2017-10-10 | 宁波工程学院 | [1 (base of the furans phenolic ether 5) imido epoxide] acid amides of N alcyls 2 and its application |
| CN109180667B (en) * | 2018-09-10 | 2021-08-06 | 湖南大学 | 8- (benzofuran-5-yl) benzoxazinone derivative and application thereof |
| CN109096231A (en) * | 2018-09-12 | 2018-12-28 | 长沙理工大学 | 4- allyl -2- (benzofuran -5- base) phenol and its application |
| CN111978306B (en) * | 2019-05-24 | 2023-01-03 | 湖南大学 | Furanol pyrazole formamide derivative and preparation method and application thereof |
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