CN104642314A - Application of N-furan phenol methyl ether-5-yl) chromene-4-amide as sterilizing agent - Google Patents

Application of N-furan phenol methyl ether-5-yl) chromene-4-amide as sterilizing agent Download PDF

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CN104642314A
CN104642314A CN201510064670.4A CN201510064670A CN104642314A CN 104642314 A CN104642314 A CN 104642314A CN 201510064670 A CN201510064670 A CN 201510064670A CN 104642314 A CN104642314 A CN 104642314A
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chromene
base
acid amides
alkyl
dihydrobenzofuranes
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CN104642314B (en
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杨泽慧
邵丹凤
陈晓东
胡艾希
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Ningbo University of Technology
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Ningbo University of Technology
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Abstract

The invention relate to application of N-furan phenol methyl ether-5-yl) chromene-4-amide as shown in the chemical formulas I, II or III in specification in preparation of a sterilizing agent, wherein X1 is selected from hydrogen, C1-C2 alkyl, C3-C4 linear chain alkyl or C3-C4 branch chain alkyl, C1-C2 alkoxy, C3-C4 linear chain alkoxy or C3-C4 branch alkoxy; X2-X7 are selected from hydrogen, C1-C2 alkyl, C3-C4 linear chain alkyl or C3-C4 bran chain alkyl.

Description

N-(benzofuranol methyl ether-5-base) chromene-4-acid amides is as the application of bactericide
Technical field
The present invention relates to the novelty teabag of compound, specifically N-(benzofuranol methyl ether-5-base) chromene-4-acid amides is preparing the application in bactericide.
Background technology
Benzofuranol (chemical name 2,2-dimethyl-2,3-Dihydrobenzofuranes phenol) is the important intermediate of producing carbofuran, pacifying well the large-tonnage such as prestige and Benfuracard micro carbamate chemicals for agriculture.Carbamate chemicals for agriculture activity is high, is widely used, but toxicity is comparatively large, therefore needs lower, the active substitute products preferably of exploitation toxicity, to meet the demand in market.Part energy is transferred to the existing pesticide intermediate compound of exploitation and is being prevented and treated the purposes in entomogenous fungi grass as pesticide new variety by New pesticides discovery company of the world.Chinese patent describes the non-amino formate ester agricultural chemicals based on benzofuranol research and development: 4-(benzofuran-5-base)-2-virtue aminothiazole and preparation method thereof and application, and ZL201010553848.9,2012.7.4 authorize; 5-[2-(benzyl imino group) thiazole-4-yl] furans phenolic ether is as the application preparing bactericide, and ZL201110102467.3,2013.3.27 authorize; 5-[2-(benzyl imino group) thiazole-4-yl] furans phenolic ether and as the application preparing insecticide, ZL201110102455.0,2013.6.12 authorize; Have 5-(2-virtue aminothiazole-4-base) benzofuranol ether compound and the preparation method of activity of weeding, CN102603726A, 2012.7.25 are open; 4-(benzofuran-5-base)-2-phenylamino thiazole is as the application of bactericide, and CN103141486B, 2014.5.28 authorize.Tan Xiaosong describes 7 introducing active groups on benzofuranol ring and has synthesized benzofuranol phosphorylation derivates, and this compound has certain insecticidal activity [Tan Xiaosong, Master's thesis, Central China Normal University, Wuhan, 2000]; He Qixi describes and introduce oximes group on benzofuranol 7, has synthesized benzofuranol oxime ether derivatives; Under finite concentration, the certain bacteriostatic activity of this compounds exhibit [He Qixi, Master's thesis, Hunan University, Changsha, 2009].
Chinese invention patent describes N-[4-(benzofuran-5-base) thiazol-2-yl] preparation of acid amides and the application [CN103342703A, 2013.10.9 are open] as bactericide thereof; Chinese invention patent describes preparation and the active anticancer [CN103626747A, 2014.3.12 are open] of N-(2,3-Dihydrobenzofuranes-5-base) chromene-4-acid amides.
Summary of the invention
The N-shown in chemical structural formula I, II or III (benzofuranol methyl ether-5-base) chromene-4-acid amides is the object of the present invention is to provide to prepare the application in bactericide:
Wherein, X 1be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl, C 1 ~c 2alkoxyl, C 3~ C 4unbranched alkoxy or C 3~ C 4branched alkoxy; X 2~ X 7be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl.
The N-shown in chemical structural formula IV (benzofuranol methyl ether-5-base) chromene-4-acid amides is the object of the present invention is to provide to prepare the application in bactericide:
Wherein, X 1be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl; C 1~ C 2alkoxyl, C 3~ C 4unbranched alkoxy or C 3~ C 4branched alkoxy.
The object of the present invention is to provide N-(2, 2-dimethyl-7-methoxyl group-2, 3-Dihydrobenzofuranes-5-base) chromene-4-acid amides, N-(2, 2-dimethyl-7-methoxyl group-2, 3-Dihydrobenzofuranes-5-base)-8-methyl chromene-4-acid amides N-(2, 2-dimethyl-7-methoxyl group-2, 3-Dihydrobenzofuranes-5-base)-8-methoxychromen-4-acid amides and N-(2, 2-dimethyl-7-methoxyl group-2, 3-Dihydrobenzofuranes-5-base) benzo [h] chromene-4-acid amides preparing the application of killing in the bactericide of Rhizoctonia solani Kuhn.
The present invention compared with prior art tool has the following advantages:
Late Cambrian of the present invention N-(benzofuranol methyl ether-5-base) chromene-4-acid amides has higher bactericidal activity.
Embodiment
Following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
The preparation of benzodihydropyran-4-carboxylic acid (1)
Compound 1A ~ 10A is prepared by Chinese invention patent [CN103626747A, 2014.3.12 are open].
16.90g compound 1A, 23.10g 1,2-PD, 1.50g p-methyl benzenesulfonic acid, 100mL toluene, return stirring 8.0h, it is complete that TLC follows the tracks of ketal reaction, obtains compound 1B, when ketal reaction liquid is cooled to 80 ~ 90 DEG C, add 1.60g zinc oxide, heating distributes part toluene, makes temperature in bottle be increased to 126 ~ 130 DEG C, it is complete that insulation reaction 4.0h, TLC follow the tracks of rearrangement reaction, suction filtration, decompression distillation removing toluene, obtains pale red oily mater.Then 60mL30% sodium hydrate aqueous solution is added, 80mL methanol solution, back flow reaction 4.0h, TLC monitoring reacts completely, add 100mL cold water in reactant liquor, suction filtration, filtrate uses 50mL washed with dichloromethane, water layer watery hydrochloric acid adjusts pH2,100mL extraction into ethyl acetate, anhydrous sodium sulfate drying, is spin-dried for obtain solid benzodihydropyran-4-carboxylic acid 11.2g, yield 83.9%, m.p.93 ~ 95 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 2.12 ~ 2.18 (m, 1H, 3-H), 2.30 ~ 2.35 (m, 1H, 3-H), 3.81 (t, J=4.8Hz, 1H, 4-H), 4.24 ~ 4.27 (m, 2H, 2-H), 6.85 (d, J=8.4Hz, 1H, 8-H), 6.89 (t, J=7.6Hz, 1H, 6-H), 7.17 (t, J=8.4Hz, 1H, 7-H), 7.27 (d, J=7.6Hz, 1H, 5-H).
Embodiment 2
The preparation of 8-methyl benzodihydropyran-4-carboxylic acid (2)
By embodiment 1 method of operating, 5.10g compound 2A and 5.00g 1,2-PD and 0.50g p-methyl benzenesulfonic acid react 8.0h, obtain compound 2B, add 1.00g zinc oxide, and reaction 2.0h, obtains pale red oily mater.Then add the 30mL 30%NaOH aqueous solution, 40mL methanol solution reaction 4.0h, obtains 8-methyl benzodihydropyran-4-carboxylic acid, yield 83.2%, m.p.103 ~ 104 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 2.09 ~ 2.17 (m, 1H, 3-H), 2.18 (s, 3H, CH 3), 2.28 ~ 2.34 (m, 1H, 3-H), 3.81 (t, J=6.0Hz, 1H, 4-H), 4.26 ~ 4.29 (m, 2H, 2-H), 6.79 (t, J=7.2Hz, 1H, 6-H), 7.04 (d, J=7.6Hz, 1H, 7-H), 7.11 (d, J=7.6Hz, 1H, 5-H).
Embodiment 3
The preparation of 7-methyl benzodihydropyran-4-carboxylic acid (3)
By embodiment 1 method of operating, 10.20g compound 3A and 11.30g 1,2-PD and 1.50g p-methyl benzenesulfonic acid react 8.0h, obtain compound 3B.Add 1.00g zinc oxide, reaction 2.0h, obtains pale red oily mater.Then add the 40mL 30%NaOH aqueous solution, 60mL methanol solution reaction 4.0h, obtains 7-methyl benzodihydropyran-4-carboxylic acid, yield 65.0%, m.p.110 ~ 111 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 2.10 ~ 2.18 (m, 1H, 3-H), 2.28 (s, 3H, 7-CH 3), 2.29 ~ 2.34 (m, 1H, 3-H), 3.78 (t, J=4.8Hz, 1H, 4-H), 4.21 ~ 4.25 (m, 2H, 2-H), 6.67 (s, 1H, 8-H), 6.72 (d, J=8.0Hz, 1H, 6-H), 7.15 (d, J=8.0Hz, 1H, 5-H).
Embodiment 4
The preparation of 6-methyl chromene-4-carboxylic acid (4)
By embodiment 1 method of operating, 5.10g compound 4A and 6.20g 1,2-PD and 0.50g p-methyl benzenesulfonic acid react 8.0h, obtain compound 4B, add 1.00g zinc oxide, and reaction 2.0h, obtains pale red oily mater.Then add the 40mL 30%NaOH aqueous solution, 60mL methanol solution reaction 4.0h, obtains 6-methyl chromene-4-carboxylic acid, yield 91.9%, m.p.116 ~ 117 DEG C; 1hNMR (CDCl 3, 400MHz) and δ: 2.09 ~ 2.18 (m, 1H, 3-H), 2.26 (s, 3H, 6-CH 3), 2.28 ~ 2.34 (m, 1H, 3-H), 3.78 (t, J=8.4Hz, 1H, 4-H), 4.19 ~ 4.28 (m, 2H, 2-H), 6.75 (d, J=8.4Hz, 1H, 8-H), 6.98 (dd, J=2.0,8.4Hz, 1H, 7-H), 7.07 (d, J=2.0Hz, 1H, 5-H).
Embodiment 5
The preparation of 8-methoxychromen-4-carboxylic acid (5)
By embodiment 1 method of operating, 2.70g compound 5A and 2.50g 1,2-PD and 0.50g p-methyl benzenesulfonic acid react 8.0h, obtain compound 5B, add 1.00g zinc oxide, and reaction 2.0h, obtains pale red oily mater.Then add the 40mL 30%NaOH aqueous solution, 60mL methanol solution reaction 4.0h, obtains 8-methoxychromen-4-carboxylic acid, yield 34.8%, m.p.105 ~ 107 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 2.12 ~ 2.21 (m, 1H, 3-H), 2.31 ~ 2.37 (m, 1H, 3-H), 3.78 (t, J=4.8Hz, 1H, 4-H), 3.78 (s, 3H, 8-OCH 3), 4.29 ~ 4.39 (m, 2H, 2-H), 6.79 (dd, J=2.0,7.6Hz, 1H, 7-H), 7.17 (t, J=7.6Hz, 1H, 6-H), 6.89 (dd, J=2.0,7.6Hz, 1H, 5-H).
Embodiment 6
The preparation of 7-methoxychromen-4-carboxylic acid (6)
By embodiment 1 method of operating, 8.10g compound 6A and 7.90g 1,2-PD and 1.50g p-methyl benzenesulfonic acid, obtain compound 6B, add 1.00g zinc oxide, and reaction 2.0h, obtains pale red oily mater.Then add the 40mL 30%NaOH aqueous solution, 60mL methanol solution reaction 4.0h, obtains pale yellow oil 7-methoxychromen-4-carboxylic acid, yield 68.9%; 1h NMR (CDCl 3, 400MHz) and δ: 2.09 ~ 2.14 (m, 1H, 3-H), 2.28 ~ 2.32 (m, 1H, 3-H), 3.76 (s, 3H, 7-OCH 3), 3.78 (t, J=4.8Hz, 1H, 4-H), 4.22 ~ 4.25 (m, 2H, 2-H), 6.39 (d, J=2.4Hz, 1H, 8-H), 6.50 (dd, J=2.4,8.8Hz, 1H, 6-H), 7.17 (d, J=8.8Hz, 1H, 5-H).
Embodiment 7
The preparation of 6-methoxychromen-4-carboxylic acid (7)
By embodiment 1 method of operating, 5.40g compound 7A and 6.20g 1,2-PD and 0.50g p-methyl benzenesulfonic acid, obtain compound 7B, add 1.00g zinc oxide, and reaction 2.0h, obtains pale red oily mater.Add the 40mL 30%NaOH aqueous solution, 60mL methanol solution reaction 4.0h, obtains 6-methoxychromen-4-carboxylic acid, yield 67.0%, m.p.103 ~ 104 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 2.09 ~ 2.18 (m, 1H, 3-H), 2.26 ~ 2.34 (m, 1H, 3-H), 3.75 (s, 3H, 6-OCH 3), 3.78 (t, J=4.8Hz, 1H, 4-H), 4.20 ~ 4.23 (m, 2H, 2-H), 6.77 ~ 6.82 (m, 3H, 7-H, 8-H, 5-H).
Embodiment 8
The preparation of 6-chlorine chromene-4-carboxylic acid (8)
By embodiment 1 method of operating, 5.50g compound 8A and 4.60g 1,2-PD and 0.50g p-methyl benzenesulfonic acid, obtain compound 8B, add 1.00g zinc oxide, and reaction 2.0h, obtains pale red oily mater.Then add the 40mL 30%NaOH aqueous solution, 60mL methanol solution reaction 4.0h, obtains 6-chlorine chromene-4-carboxylic acid, yield 70.2%, m.p.90 ~ 92 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 2.08 ~ 2.17 (m, 1H, 3-H), 2.29 ~ 2.36 (m, 1H, 3-H), 3.78 (t, J=8.4Hz, 1H, 4-H), 4.22 ~ 4.27 (m, 2H, 2-H), 6.78 (d, J=8.8Hz, 1H, 8-H), 7.13 (dd, J=2.4,8.8Hz, 1H, 7-H), 7.28 (d, J=2.4Hz, 1H, 5-H).
Embodiment 9
The preparation of 3,4-dihydro-2H-benzo [h] chromene-4-carboxylic acid (9)
By embodiment 1 method of operating, 5.80g compound 9A and 4.70g1,2-propane diols and 1.00g p-methyl benzenesulfonic acid, reaction 8.0h, obtains compound 9B, adds 1.00g zinc oxide, and reaction 2.0h, obtains pale red oily mater.Then add the 40mL 30%NaOH aqueous solution, 60mL methanol solution reaction 4.0h, obtains 3,4-dihydro-2H-benzo [h] chromene-4-carboxylic acid, yield 54.0%, m.p.173 ~ 174 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 2.19 ~ 2.28 (m, 1H, 3-H), 2.39 ~ 2.46 (m, 1H, 3-H), 3.91 (t, J=4.4Hz, 1H, 4-H), 4.38 ~ 4.51 (m, 2H, 2-H), 7.32 ~ 7.38 (m, 2H, 7-H, 6-H), 7.44 ~ 7.48 (m, 2H, 9-H, 10-H), 7.73 ~ 7.75 (m, 1H, 8-H), 8.16 ~ 8.19 (m, 1H, 11-H).
Embodiment 10
The preparation of 3,4-dihydro-2H-benzo [g] chromene-4-carboxylic acid (10)
By embodiment 1 method of operating, 2.90g compound 10A and 2.40g 1,2-PD and 0.50g p-methyl benzenesulfonic acid, reaction 8.0h, obtains compound 10B, adds 1.00g zinc oxide, and reaction 2.0h, obtains pale red oily mater.Then add the 40mL 30%NaOH aqueous solution, 60mL methanol solution reaction 4.0h, obtains 3,4-dihydro-2H-benzo [g] chromene-4-carboxylic acid, yield 52.2%, m.p.170 ~ 171 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 2.21 ~ 2.30 (m, 1H, 3-H), 2.37 ~ 2.44 (m, 1H, 3-H), 4.07 (t, J=5.2Hz, 1H, 4-H), 4.28 ~ 4.32 (m, 1H, 2-H), 4.34 ~ 4.41 (m, 1H, 2-H), 7.24 (s, 1H, 10-H), 7.28 (t, J=8.0Hz, 1H, 7-H), 7.38 (t, J=8.0Hz, 1H, 8-H), 7.66 (d, J=8.0Hz, 1H, 9-H), 7.71 (d, J=8.0Hz, 1H, 6-H), 7.78 (s, 1H, 5-H).
Embodiment 11
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base) chromene-4-acid amides (11)
The preparation of (1) 2,2-dimethyl-7-methoxyl group-5-nitro-2,3-Dihydrobenzofuranes (21)
17.80g compound 21,50mL dichloromethane solution, stirs at-5 DEG C, drip 10mL red fuming nitric acid (RFNA), 30min dropwises, and temperature rises to 10 DEG C, continue reaction 30min, TLC monitoring to react completely, reactant liquor is washed, dichloromethane extraction, anhydrous sodium sulfate drying, absolute ethyl alcohol is recrystallized to obtain yellow solid 2,2-dimethyl-7-methoxyl group-5-nitro-2,3-Dihydrobenzofuranes (21) 19.20g, yield 92.6%, m.p.124 ~ 126 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.57 (s, 6H, 2 × CH 3), 3.11 (s, 2H, 3-H), 3.95 (s, 3H, 7-OCH 3), 7.70 (d, J=2.4Hz, 1H, 6-H), 7.77 (d, J=2.4Hz, 1H, 4-H).
The preparation of (2) 2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-amine (22)
6.00g compound 22 (27.00mmol), 60mL methyl alcohol, Raney's nickel, drips the hydrazine hydrate of 12.00g 80% at 20 DEG C, drip in 1.0h and finish, continue reaction 30min, TLC monitoring to react completely, suction filtration reclaims Raney's nickel, filtrate is spin-dried for, dissolve with 50mL carrene, 100mL water washing, 50mL dichloromethane extraction 3 times, anhydrous sodium sulfate drying, filter, be spin-dried for, dry 2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-amine (22) 4.92g, yield 94.5%, m.p.126 ~ 128 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.47 (s, 6H, 2 × CH 3), 2.94 (s, 2H, 3-H), 3.34 (s, 2H, NH 2), 3.81 (s, 3H, 7-OCH 3), 6.17 (s, 2H, 4-H, 6-H).
(3) preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base) chromene-4-acid amides (23a)
0.59g compound 1,0.66g compound 22,20mL carrene, 0.67g DCC, 0.09g DMAP, stirring at room temperature 1.0h, TLC monitoring reacts completely; Suction filtration, is spin-dried for, and absolute ethyl alcohol is recrystallized to obtain 0.40g white solid 11, yield 33.3%, m.p.178 ~ 180 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.48 (s, 6H, 2 × CH 3), 2.16 ~ 2.25 (m, 1H, 3-H), 2.54 ~ 2.60 (m, 1H, 3-H), 2.97 (s, 2H, 3 '-H), 3.77 (t, J=4.8Hz, 1H, 4-H), 3.84 (s, 3H, 7 '-OCH 3), 4.09 ~ 4.15 (m, 1H, 2-H), 4.29 ~ 4.34 (m, 1H, 2-H), 6.74 (d, J=2.0Hz, 1H, 6 '-H), 6.93 (dd, J=2.0,8.0Hz, 1H, 8-H), 6.94 (d, J=2.0Hz, 1H, 4 '-H), 6.95 ~ 6.99 (m, 1H, 7-H), 7.17 (s, 1H, NH), 7.19 (dd, J=2.0,8.0Hz, 1H, 5-H), 7.24 ~ 7.29 (m, 1H, 6-H).
Embodiment 12
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-8-methyl chromene-4-acid amides (12)
By the preparation method of embodiment 11,3.30mmol compound 2,3.40mmol compound 22, reaction 1.0h, obtains white solid 12, yield 53.4%, m.p.190 ~ 192 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.48 (s, 6H, 2 × CH 3), 2.15 ~ 2.20 (m, 1H, 3-H), 2.22 (s, 3H, 8-CH 3), 2.54 ~ 2.60 (m, 1H, 3-H), 2.96 (s, 2H, 3 '-H), 3.76 (t, J=4.8Hz, 1H, 4-H), 3.83 (s, 3H, 7 '-OCH 3), 4.08 ~ 4.14 (m, 1H, 2-H), 4.34 ~ 4.39 (m, 1H, 2-H), 6.73 (d, J=2.0Hz, 1H, 6 '-H), 6.87 (t, J=7.6Hz, 1H, 6-H), 6.95 (d, J=2.0Hz, 1H, 4 '-H), 7.03 (d, J=7.6Hz, 1H, 7-H), 7.12 (d, J=7.6Hz, 1H, 5-H), 7.21 (s, 1H, NH).
Embodiment 13
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-7-methyl chromene-4-acid amides (13)
By the preparation method of embodiment 11,3.30mmol compound 3,3.40mmol compound 22, reaction 1.0h, obtains white solid 13, yield 36.6%, m.p.195 ~ 197 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.48 (s, 6H, 2 × CH 3), 2.14 ~ 2.23 (m, 1H, 3-H), 2.33 (s, 3H, 7-CH 3), 2.51 ~ 2.56 (m, 1H, 3-H), 2.97 (s, 2H, 3 '-H), 3.73 (t, J=4.8Hz, 1H, 4-H), 3.84 (s, 3H, 7 '-OCH 3), 4.05 ~ 4.11 (m, 1H, 2-H), 4.26 ~ 4.32 (m, 1H, 2-H), 6,74 (s, 2H, 6 '-H, 8-H), 6.78 (d, J=8.0Hz, 1H, 6-H), 6.95 (d, J=2.0Hz, 1H, 4 '-H), 7.06 (d, J=8.0Hz, 1H, 5-H), 7.21 (s, 1H, NH).
Embodiment 14
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-6-methyl chromene-4-acid amides (14)
By the preparation method of embodiment 11,3.30mmol compound 4,3.40mmol compound 22, reaction 1.0h, obtains white solid 14, yield 39.5%, m.p.208 ~ 209 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.48 (s, 6H, 2 × CH 3), 2.14 ~ 2.23 (m, 1H, 3-H), 2.33 (s, 3H, 6-CH 3), 2.51 ~ 2.56 (m, 1H, 3-H), 2.97 (s, 2H, 3 '-H), 3.73 (t, J=4.8Hz, 1H, 4-H), 3.84 (s, 3H, 7 '-OCH 3), 4.06 ~ 4.13 (m, 1H, 2-H), 4.26 ~ 4.32 (m, 1H, 2-H), 6.74 (s, 1H, 6 '-H), 6.78 (d, J=8.0Hz, 1H, 8-H), 6.96 ~ 6.97 (m, 1H, 5-H, 4 '-H), 7.06 (dd, J=2.0,8.0Hz, 1H, 7-H), 7.19 (s, 1H, NH).
Embodiment 15
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-8-methoxychromen-4-acid amides (15)
By the preparation method of embodiment 11,3.30mmol compound 5,3.40mmol compound 22, reaction 0.7h, obtains white solid 15, yield 51.8%, m.p.212 ~ 214 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.48 (s, 6H, 2 × CH 3), 2.17 ~ 2.26 (m, 1H, 3-H), 2.56 ~ 2.62 (m, 1H, 3-H), 2.97 (s, 2H, 3 '-H), 3.78 (t, J=4.8Hz, 1H, 4-H), 3.83 (s, 3H, 7 '-OCH 3), 3.92 (s, 3H, 8-OCH 3), 4.13 ~ 4.20 (m, 1H, 2-H), 4.43 ~ 4.48 (m, 1H, 2-H), 6.75 (d, J=1.2Hz, 1H, 6 '-H), 6.80 (dd, J=1.2,8.0Hz, 1H, 7-H), 6.86 ~ 6.96 (m, 3H, 6-H, 5-H, 4 '-H), 7.19 (s, 1H, NH).
Embodiment 16
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-7-methoxychromen-4-acid amides (16)
By the preparation method of embodiment 11,3.30mmol compound 6,3.40mmol compound 22, reaction 0.3h, obtains white solid 16, yield 55.4%, m.p.166 ~ 167 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.48 (s, 6H, 2 × CH 3), 2.15 ~ 2.22 (m, 1H, 3-H), 2.51 ~ 2.56 (m, 1H, 3-H), 2.97 (s, 2H, 3 '-H), 3.70 (t, J=4.4Hz, 1H, 4-H), 3.81 (s, 3H, 7 '-OCH 3), 3.84 (s, 3H, 7-OCH 3), 4.04 ~ 4.11 (m, 1H, 2-H), 4.28 ~ 4.32 (m, 1H, 2-H), 6.47 (d, J=2.8Hz, 1H, 8-H), 6.57 (dd, J=2.8,8.4Hz, 1H, 6-H), 6.76 (d, J=2.0Hz, 1H, 6 '-H), 6.94 (d, J=2.0Hz, 1H, 4 '-H), 7.07 (d, J=8.4Hz, 1H, 5-H), 7.20 (s, 1H, NH).
Embodiment 17
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-6-methoxychromen-4-acid amides (17)
By the preparation method of embodiment 11,3.30mmol compound 7,3.40mmol compound 22, reaction 1.0h, obtains white solid 17, yield 80.2%, m.p.173 ~ 174 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.48 (s, 6H, 2 × CH 3), 2.15 ~ 2.25 (m, 1H, 3-H), 2.49 ~ 2.56 (m, 1H, 3-H), 2.97 (s, 2H, 3 '-H), 3.73 (t, J=4.8Hz, 1H, 4-H), 3.78 (s, 3H, 6-OCH 3), 3.84 (s, 3H, 7 '-OCH 3), 4.05 ~ 4.12 (m, 1H, 2-H), 4.25 ~ 4.29 (m, 1H, 2-H), 6.70 (d, J=2.0Hz, 1H, 6 '-H), 6.75 (d, J=2.0Hz, 1H, 4 '-H), 6.83 ~ 6.88 (m, 2H, 7-H, 8-H), 6.95 (d, J=2.4Hz, 1H, 5-H), 7.20 (s, 1H, NH).
Embodiment 18
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-6-chlorine chromene-4-acid amides (18)
By the preparation method of embodiment 11,3.30mmol compound 8,3.40mmol compound 22, reaction 0.6h, obtains white solid 18, yield 64.0%, m.p.163 ~ 165 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.49 (s, 6H, 2 × CH 3), 2.12 ~ 2.22 (m, 1H, 3-H), 2.50 ~ 2.56 (m, 1H, 3-H), 2.99 (s, 2H, 3 '-H), 3.74 (t, J=4.4Hz, 1H, 4-H), 3.85 (s, 3H, 7 '-OCH 3), 4.12 ~ 4.19 (m, 1H, 2-H), 4.28 ~ 4.32 (m, 1H, 2-H), 6.78 (d, J=1.6Hz, 1H, 6 '-H), 6.86 (d, J=8.4Hz, 1H, 8-H), 6.96 (d, J=1.6Hz, 1H, 4 '-H), 7.16 (s, 1H, NH), 7.17 (d, J=2.8Hz, 1H, 5-H), 7.21 (dd, J=2.8,8.4Hz, 1H, 6-H).
Embodiment 19
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base) benzo [h] chromene-4-acid amides (19)
By the preparation method of embodiment 11,3.30mmol compound 19i, 3.40mmol compound 22, reaction 0.6h, obtains white solid 19, yield 57.9%, m.p.245 ~ 247 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.47 (s, 6H, 2 × CH 3), 2.28 ~ 2.37 (m, 1H, 3-H), 2.63 ~ 2.67 (m, 1H, 3-H), 2.95 (s, 2H, 3 '-H), 3.81 (s, 3H, 7 '-OCH 3), 3.70 (t, J=4.4Hz, 1H, 4-H), 4.24 ~ 4.30 (m, 1H, 2-H), 4.54 ~ 4.59 (m, 1H, 2-H), 6.77 (d, J=2.0Hz, 1H, 6 '-H), 6.88 (d, J=2.0Hz, 1H, 4 '-H), 7.16 (s, 1H, NH), 7.24 (d, J=8.4Hz, 1H, 5-H), 7.46 (d, J=8.4Hz, 1H, 6-H), 7.52 ~ 7.56 (m, 2H, 8-H, 9-H), 7.80 ~ 7.82 (m, 1H, 7-H), 8.22 ~ 8.25 (m, 1H, 10-H).
Embodiment 20
The preparation of N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base) benzo [g] chromene-4-acid amides (20)
By the preparation method of embodiment 11,3.30mmol compound 10,3.40mmol compound 22, reaction 1.0h, obtains white solid 20, yield 54.2%, m.p.208 ~ 210 DEG C; 1h NMR (CDCl 3, 400MHz) and δ: 1.47 (s, 6H, 2 × CH 3), 2.25 ~ 2.33 (m, 1H, 3-H), 2.65 ~ 2.71 (m, 1H, 3-H), 2.95 (s, 2H, 3 '-H), 3.81 (s, 3H, 7 '-OCH 3), 4.03 (t, J=4.4Hz, 1H, 4-H), 4.19 ~ 4.26 (m, 1H, 2-H), 4.36 ~ 4.41 (m, 1H, 2-H), 6.73 (s, 1H, 10-H), 6.91 (s, 1H, 5-H), 7.20 (s, 1H, NH), 7.32 (s, 1H, 6 '-H), 7.35 (t, J=8.0Hz, 1H, 7-H), 7.45 (t, J=8.0Hz, 1H, 8-H), 7.72 ~ 7.77 (m, 3H, 4 '-H, 6-H, 9-H).
Embodiment 21
The bactericidal activity of N-(benzofuranol methyl ether-5-base) chromene-4-acid amides measures
1 test objective
The virulence of noval chemical compound to various pathogen under for examination concentration at indoor measurement, preliminary assessment its bactericidal activity.
2 experimental conditions
2.1 for examination target
Rhizoctonia solani Kuhn (Rhizoctonia solani); Bacterial classification is all kept in refrigerator (4-8 DEG C), within 2-3 days, is inoculated in culture dish from test tube slant, cultivates and be for experiment under preference temperature before test.Experiment medium is potato agar medium (PDA).
2.2 condition of culture
Condition of culture for examination target and the rear target of test is temperature 25 ± 5 DEG C, relative moisture 65 ± 5%
2.3 instrument and equipment
Beaker, pipette, graduated cylinder, culture dish, high-pressure sterilizing pot, constant temperature biochemical cultivation case etc.
3 experimental scheme
3.1 test medicines: N-(benzofuranol methyl ether-5-base) chromene-4-acid amides (I ~ III):
Wherein, X 1be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl, C 1~ C 2alkoxyl, C 3~ C 4unbranched alkoxy or C 3~ C 4branched alkoxy; X 2~ X 7be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl.
3.2 experimental concentration
Broad Bean Leaves method drug concentration establishes 500mg/L.
3.3 medicament preparations
Former medicine: take aequum with ten thousand/electronic balance; Solvent: DMF (DMF), 0.2%; Emulsifier: Tween 80,0.1%;
General sieve measures: accurately take 0.0500g sample, dissolves, add the sterile water 98.8ml containing 0.1%Tween80 emulsifier, stir, be mixed with 500mg/L strength solution for subsequent use with 0.20mLDMF.
4 test methods
Rhizoctonia solani Kuhn: adopt Broad Bean Leaves method with reference to the raw standard method NY/T1156.5-2006 that surveys; the blade of clip broad bean susceptible variety; put in culture dish; 500mg/L compound liquid medicine jet to be wet vacuum side of blade with sprayer; after natural air drying; be that 6.0mm bacterium cake has the one side of mycelia to be inoculated in process central vane with inoculator by diameter; protectiveness test is inoculation in 24 hours after chemicals treatment; inoculation is placed in climatic cabinate, cultivates under the condition of temperature 26 ~ 28 DEG C, relative moisture 80% ~ 90%.Depending on blank incidence, calculate control efficiency.
5 fungicidal activity evaluations
Rhizoctonia solani Kuhn: look blank incidence surveying record lesion diameter, calculates control efficiency (%).
P = D 0 - D 1 D 0 × 100
In formula: P represents control efficiency, D 0represent blank lesion diameter, D 1represent process lesion diameter.
According to survey data, formula (1) calculates control efficiency.
P ( % ) = CK - PT CK × 100 · · · ( 1 )
In formula: P represents control efficiency, CK represents blank disease index, and PT represents chemicals treatment disease index.
N-(benzofuranol methyl ether-5-base) the general sieve result of chromene-4-acid amides bactericidal activity: N-(2, 2-dimethyl-7-methoxyl group-2, 3-Dihydrobenzofuranes-5-base) chromene-4-acid amides, N-(2, 2-dimethyl-7-methoxyl group-2, 3-Dihydrobenzofuranes-5-base)-8-methyl chromene-4-acid amides N-(2, 2-dimethyl-7-methoxyl group-2, 3-Dihydrobenzofuranes-5-base)-8-methoxychromen-4-acid amides and N-(2, 2-dimethyl-7-methoxyl group-2, 3-Dihydrobenzofuranes-5-base) control efficiency of benzo [h] chromene-4-acid amides to Rhizoctonia solani Kuhn (500mg/L) be respectively 85.6%, 80.4%, 71.0% and 64.9%.
Active testing result shows, and N-(benzofuranol methyl ether-5-base) chromene-4-acid amides has good bactericidal activity, can be used for preparing bactericide.

Claims (7)

1. N-(benzofuranol methyl ether-5-base) chromene-4-acid amides shown in chemical structural formula I is preparing the application in bactericide:
Wherein, X 1be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl, C 1~ C 2alkoxyl, C 3~ C 4unbranched alkoxy or C 3~ C 4branched alkoxy; X 2~ X 4be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl.
2. N-(benzofuranol methyl ether-5-base) chromene-4-acid amides shown in chemical structural formula II is preparing the application in bactericide:
Wherein, X 2~ X 7be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl.
3. N-(benzofuranol methyl ether-5-base) chromene-4-acid amides shown in chemical constitution formula III is preparing the application in bactericide:
Wherein, X 2~ X 7be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl.
4. application according to claim 1, N-(benzofuranol methyl ether-5-base) chromene-4-acid amides shown in its Chinese style I is selected from the compound shown in formula IV:
Wherein, X 1be selected from: hydrogen, C 1~ C 2alkyl, C 3~ C 4straight chained alkyl or C 3~ C 4branched alkyl; C 1~ C 2alkoxyl, C 3~ C 4unbranched alkoxy or C 3~ C 4branched alkoxy.
5. application according to claim 1, N-(benzofuranol methyl ether-5-base) chromene-4-acid amides shown in its Chinese style I is selected from: N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base) chromene-4-acid amides, N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-8-methyl chromene-4-acid amides N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-8-methoxychromen-4-acid amides.
6. application according to claim 2, N-(benzofuranol methyl ether-5-base) chromene-4-acid amides shown in its Chinese style II is selected from: N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base) benzo [h] chromene-4-acid amides.
7. application according to claim 4, compound shown in its Chinese style IV is selected from: N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base) chromene-4-acid amides, N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-8-methyl chromene-4-acid amides N-(2,2-dimethyl-7-methoxyl group-2,3-Dihydrobenzofuranes-5-base)-8-methoxychromen-4-acid amides.
CN201510064670.4A 2015-02-04 2015-02-04 Application of N-furan phenol methyl ether-5-yl) chromene-4-amide as sterilizing agent Expired - Fee Related CN104642314B (en)

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