CN103275073B - 2-(1,2,4-triazole-1-methyl)-2-(cumarone-5-base)-DOX and application thereof - Google Patents
2-(1,2,4-triazole-1-methyl)-2-(cumarone-5-base)-DOX and application thereof Download PDFInfo
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- PMVAXIIBJJKNTE-UHFFFAOYSA-N CC(C)(C1)Oc(cc2)c1cc2C(COS(C)(=O)=O)=O Chemical compound CC(C)(C1)Oc(cc2)c1cc2C(COS(C)(=O)=O)=O PMVAXIIBJJKNTE-UHFFFAOYSA-N 0.000 description 1
- PDGITLBMUFAVLU-UHFFFAOYSA-N CC1OC(COS(C)(=O)=O)(c(cc2)cc3c2OC(C)(C)C3)OC1 Chemical compound CC1OC(COS(C)(=O)=O)(c(cc2)cc3c2OC(C)(C)C3)OC1 PDGITLBMUFAVLU-UHFFFAOYSA-N 0.000 description 1
- GVIBVDPWSPTLLH-UHFFFAOYSA-N CC1OC(C[n]2ncnc2)(c(cc2)cc3c2OC(C)(C)C3)OC1 Chemical compound CC1OC(C[n]2ncnc2)(c(cc2)cc3c2OC(C)(C)C3)OC1 GVIBVDPWSPTLLH-UHFFFAOYSA-N 0.000 description 1
- NQWOPEOGZDGWHC-UHFFFAOYSA-N CCOc1c2OC(C)(C)Cc2cc(C(CBr)=O)c1 Chemical compound CCOc1c2OC(C)(C)Cc2cc(C(CBr)=O)c1 NQWOPEOGZDGWHC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to 2-(1 shown in chemical structural formula I, 2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX:
wherein R is selected from: C
1~ C
2alkyl, C
3~ C
4straight chained alkyl or branched-chain alkyl; R
1be selected from: H, C
1~ C
2alkyl; X is selected from: chlorine, bromine, iodine, mesyloxy, trifluoro-methanesulfonyl oxy, phenylsulfonyloxy, tolysulfonyl oxygen base; Y is selected from: hydrogen, C
1~ C
2alkoxyl group, C
3~ C
4unbranched alkoxy or branched alkoxy; Chlorine, bromine, fluorine or iodine.Chemical compounds I prepares through key intermediate II shown in chemical structural formula II.Chemical compounds I is applied preparing in sterilant.
Description
Technical field
The present invention relates to the preparation and application of new compound, specifically 2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX preparation and be the application of sterilant.
Background technology
Triazole class compounds has the fungicidal activity of wide spectrum, and it has interior suction function and protection, therapeutic action to triazole bactericidal agent, is thus widely used in by the control of the fungus-caused multiple diseases such as ascomycetes, basidiomycetes
[2].The ketal class agricultural chemicals such as the Wocosin 50TK gone on the market, etaconazole, oxygen ring azoles, difenoconazole and furconazole, demonstrate good fungicidal activity to different crops.
Benzofuranol (2,2-dimethyl-2,3-Dihydrobenzofuranes) derivative pesticide furathiocarb, carbofuran, benfuracarb and carbosulfan etc. are the class carbamate pesticides gone on the market for a long time; Such benzofuranol derivative has broad spectrum insecticide, nematocides, has and tags and stomach poison function.But they and Pseudocholinesterase are in conjunction with irreversible, and therefore toxicity is very high.
Benzofuranol 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.As everyone knows, the exploitation of a new varieties of pesticides needed for 8 ~ 10 years, add current new varieties of pesticides registration needed for data and project many, required expense reaches multi-billion dollar, therefore part energy is transferred to and is developed pesticide new variety with existing intermediate by world's New pesticides discovery company, be intended to shorten the construction cycle, reduce development cost.Thiazole compound has the effects such as antiviral, antibacterial and desinsection.Chinese patent describes the non-amino formate ester agricultural chemicals or other functional compounds researched and developed based on benzofuranol, and the preparation and application patent of particular compound lists table 1 in:
The Chinese invention patent that table 1 is applied based on benzofuranol
Research and develop a class high-level efficiency, novel furan phenol non-amino manthanoate ketal class agricultural chemicals that toxicity is low based on 2-methyl-2,3-Dihydrobenzofuranes, there is theoretical investigation value and market application demand.
Summary of the invention
The object of the present invention is to provide 2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-the base)-DOX shown in chemical structural formula I:
Wherein, R is selected from: C
1~ C
2alkyl, C
3~ C
4straight chained alkyl or branched-chain alkyl; R
1be selected from: H, C
1~ C
2alkyl; Y is selected from: hydrogen, chlorine, bromine, fluorine, iodine, C
1~ C
2alkyl, C
3~ C
4straight chained alkyl or branched-chain alkyl, C
1~ C
2alkoxyl group, C
3~ C
4unbranched alkoxy or branched alkoxy.
The object of the present invention is to provide 2-monochloromethyl-2-(the 2-methyl-2 shown in chemical structural formula II, 3-Dihydrobenzofuranes-5-base)-1,3-dioxolane or 2-sulphur acyloxymethyl-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX:
Wherein, R is selected from: C
1~ C
2alkyl, C
3~ C
4straight chained alkyl or branched-chain alkyl; R
1be selected from: H, C
1~ C
2alkyl; X is selected from: chlorine, bromine, iodine, mesyloxy, trifluoro-methanesulfonyl oxy, phenylsulfonyloxy, tolysulfonyl oxygen base; Y is selected from: hydrogen, chlorine, bromine, fluorine, iodine, C
1~ C
2alkyl, C
3~ C
4straight chained alkyl or branched-chain alkyl, C
1~ C
2alkoxyl group, C
3~ C
4unbranched alkoxy or branched alkoxy.
The 2-(1 that the object of the present invention is to provide, 2, 4-triazole-1-methyl)-2-(2-methyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane is selected from 2-(1, 2, 4-triazole-1-methyl)-2-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-(1, 2, 4-triazole-1-methyl)-2-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-propyl group-2-(1, 2, 4-triazole-1-methyl)-2-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 2-(1, 2, 4-triazole-1-methyl)-2-(7-oxyethyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-(1, 2, 4-triazole-1-methyl)-2-(7-oxyethyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-propyl group-2-(1, 2, 4-triazole-1-methyl)-2-(7-oxyethyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 2-(1, 2, 4-triazole-1-methyl)-2-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-(1, 2, 4-triazole-1-methyl)-2-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-propyl group-2-(1, 2, 4-triazole-1-methyl)-2-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 2-(1, 2, 4-triazole-1-methyl)-2-(7-chloro-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-(1, 2, 4-triazole-1-methyl)-2-(7-chloro-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane or 4-propyl group-2-(1, 2, 4-triazole-1-methyl)-2-(7-chloro-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane:
2-monochloromethyl-2-(the 2-methyl-2 that the object of the present invention is to provide, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane is selected from 2-brooethyl-2-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-brooethyl-2-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-propyl group-2-brooethyl-2-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 2-brooethyl-2-(7-oxyethyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-brooethyl-2-(7-oxyethyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-propyl group-2-brooethyl-2-(7-oxyethyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 2-brooethyl-2-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-brooethyl-2-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-propyl group-2-brooethyl-2-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 2-brooethyl-2-(7-chloro-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-brooethyl-2-(7-chloro-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane or 4-propyl group-2-brooethyl-2-(7-chloro-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane.
2-sulfonyloxy methyl-2-(the 2-methyl-2 that the object of the present invention is to provide, 3-Dihydrobenzofuranes-5-base)-1,3-dioxolane is selected from 4-methyl-2-methylsulfonyl oxygen methyl-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX or 4-methyl-2-tolysulfonyl oxygen methyl-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX:
The object of the present invention is to provide the preparation method of 2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX; Preparation feedback is as follows:
Wherein, R is selected from: C
1~ C
2alkyl, C
3~ C
4straight chained alkyl or branched-chain alkyl; R
1be selected from: H, C
1~ C
2alkyl; X is selected from: chlorine, bromine, iodine, mesyloxy, trifluoro-methanesulfonyl oxy, phenylsulfonyloxy, tolysulfonyl oxygen base; Y is selected from: hydrogen, chlorine, bromine, fluorine, iodine, C
1~ C
2alkyl, C
3~ C
4straight chained alkyl or branched-chain alkyl, C
1~ C
2alkoxyl group, C
3~ C
4unbranched alkoxy or branched alkoxy.
2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-the base)-DOX that the object of the present invention is to provide is preparing the application in sterilant.
The present invention compared with prior art tool has the following advantages:
Late Cambrian 2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX (I) has fungicidal activity, for the preparation of sterilant.
Embodiment
Following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
The preparation of 2-(1,2,4-triazole-1-methyl)-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4a)
1.50g (5mmol) 7-methoxyl group-5-acetyl bromide-2,2-dimethyl-2,3-Dihydrobenzofuranes (2a), 0.47g (7.5mmol) ethylene glycol, 20ml toluene and 0.10g tosic acid, stirring and refluxing 2.5h.After reaction solution is cooled to room temperature, washing, organic over anhydrous dried over sodium sulfate, precipitation, column chromatography obtains weak yellow liquid 2-brooethyl-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (3a), yield 79.3%.
1 of 0.28g (4mmol), 2,4-triazole, 15ml DMF, 0.75g salt of wormwood, 0.10g Tetrabutyl amonium bromide, stirring and refluxing 30min, drips 1.03g (3mmol) 2-brooethyl-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-1,3-dioxolane (3a) DMF solution, drips and finishes, and continues reaction 10h.Reaction solution cools, and suction filtration, adds 40ml water and 30ml methylene dichloride, separatory in filtrate; Dichloromethane layer, washing, dry, precipitation, column chromatography for separation obtains faint yellow solid 2-(1,2,4-triazole-1-methyl)-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4a).Fusing point 99.5 ~ 101.0 DEG C, yield 26.2%;
1h NMR (CDCl
3, 400MHz), δ: 1.52 (s, 6H, 2 × CH
3), 3.03 (s, 2H, furan nucleus CH
2), 3.74 (t, J=7.2Hz, 2H, OCH
2), 3.83 (t, J=7.2Hz, 2H, OCH
2), 3.86 (s, 3H, OCH
3), 4.50 (s, 2H, NCH
2), 6.86 (s, 1H, phenyl ring 4-H), 6.91 (s, 1H, phenyl ring 6-H), 7.96 (s, 1H, triazole ring 5-H), 8.22 (s, 1H, triazole ring 3-H).
Embodiment 2
The preparation of 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4b)
Experimental implementation is with embodiment 1, and condensation reaction 4h, obtains weak yellow liquid 4-methyl-2-brooethyl-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX 3b, yield 81.3%; Substitution reaction solvent is DMSO, and reaction 10h, obtains buff white solid 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-1,3-dioxolane 4b, m.p.107.5 ~ 108.5 DEG C, yield 71.1%;
1h NMR (CDCl
3, 400MHz), δ: 1.08 (d, J=6.4Hz, 3H, CH
3), 1.52 (s, 6H, 2 × CH
3), 3.03 (s, 2H, furan nucleus CH
2), 3.09 (dd, J=6.8Hz, J=7.6Hz, 1H, OCH
2), 3.91 (dd, J=6.8Hz, J=7.6Hz, 1H, OCH
2), 3.87 (s, 3H, OCH
3), 4.09 ~ 4.14 (m, 1H, OCH), 4.47 (s, 2H, NCH
2), 6.88 (s, 1H, phenyl ring 4-H), 6.92 (s, 1H, phenyl ring 6-H), 7.95 (s, 1H, triazole ring 5-H), 8.21 (s, 1H, triazole ring 3-H).
Embodiment 3
The preparation of 4-propyl group-2-(1,2,4-triazole-1-methyl)-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4c)
Experimental implementation is with embodiment 1, and condensation reaction 4.5h, obtains weak yellow liquid 4-propyl group-2-brooethyl-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX 3c, yield 80.4%; Substitution reaction 12h, obtains yellowish brown liquid 4-propyl group-2-(1,2,4-triazole-1-methyl)-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4c), yield 38.8%,
1h NMR (DMSO, 400MHz), δ: 0.82 ~ 1.28 (m, 7H, CH
2cH
2cH
3), 1.40 (s, 6H, 2 × CH
3), 3.00 (s, 2H, furan nucleus CH
2), 3.08 (t, J=7.2Hz, 1H, OCH
2), 3.82 (t, J=7.2Hz, 1H, OCH
2), 3.75 (s, 3H, OCH
3), 3.88 ~ 3.91 (m, 1H, OCH), 4.51 (s, 2H, NCH
2), 6.81 (s, 1H, phenyl ring 4-H), 6.89 (s, 1H, phenyl ring 6-H), 7.92 (s, 1H, triazole ring 5-H), 8.35 (s, 1H, triazole ring 3-H).
Embodiment 4
The preparation of 2-(1,2,4-triazole-1-methyl)-2-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4d)
Experimental implementation is with embodiment 1, and condensation reaction 4.5h, obtains colourless liquid 2-brooethyl-2-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (3d), yield 81.1%; Substitution reaction 10h, faint yellow solid 2-(1,2,4-triazole-1-methyl)-2-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4d), m.p.94.0 ~ 96.0 DEG C, yield 35.0%
1h NMR (CDCl
3, 400MHz), δ: 1.43 (t, J=7.2Hz, 3H, CH
3), 1.51 (s, 6H, 2 × CH
3), 3.02 (s, 2H, furan nucleus CH
2), 3.74 (t, J=7.0Hz, 2H, OCH
2), 3.81 (t, J=7.0Hz, 2H, OCH
2), 4.01 ~ 4.14 (m, 2H, OCH
2), 4.50 (s, 2H, NCH
2), 6.86 (s, 1H, phenyl ring 4-H), 6.89 (s, 1H, phenyl ring 6-H), 7.97 (s, 1H, triazole ring 5-H), 8.22 (s, 1H, triazole ring 3-H).
Embodiment 5
The preparation of 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4e)
Experimental implementation is with embodiment 1, and condensation reaction 4h, obtains weak yellow liquid 4-methyl-2-brooethyl-2-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (3e), yield 80.3%; Substitution reaction 11h, obtains faint yellow solid 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4e), m.p.92.0 ~ 93.0 DEG C, yield 36.1%
1h NMR (CDCl
3, 400MHz), δ: 1.07 (d, J=6.4Hz, 3H, CH
3), 1.43 (t, J=7.2Hz, 3H, CH
3), 1.51 (s, 6H, 2 × CH
3), 3.02 (s, 2H, furan nucleus CH
2), 3.08 (t, J=7.4Hz, 1H, OCH
2), 3.91 (t, J=7.6Hz, 1H, OCH
2), 4.09 ~ 4.15 (m, 3H, OCH and CH
2cH
3), 4.46 (s, 2H, NCH
2), 6.88 (s, 1H, phenyl ring 4-H), 6.92 (s, 1H, phenyl ring 6-H), 7.95 (s, 1H, triazole ring 5-H), 8.21 (s, 1H, triazole ring 3-H).
Embodiment 6
The preparation of 4-propyl group-2-(1,2,4-triazole-1-methyl)-2-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4f)
Experimental implementation is with embodiment 1, and condensation reaction 5h, obtains weak yellow liquid 4-propyl group-2-brooethyl-2-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (3f), yield 84.4%; Substitution reaction 12h, obtains sorrel liquid 4-propyl group-2-(1,2,4-triazole-1-methyl)-2-(7-oxyethyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4f), yield 69.5%,
1h NMR (CDCl
3, 400MHz), δ: 0.88 (t, J=7.0Hz, 3H, CH
2cH
2cH
3), 1.18 ~ 1.40 (m, 4H, CH
2cH
2cH
3), 1.43 (t, J=7.0Hz, 3H, CH
3), 1.52 (s, 6H, 2 × CH
3), 3.02 (s, 2H, furan nucleus CH
2), 3.15 (t, J=7.2Hz, 1H, OCH
2), 3.89 (t, J=7.2Hz, 1H, OCH
2), 3.95 ~ 3.98 (m, 1H, OCH), 4.12 (q, J=7.0Hz, 2H, OCH
2cH
3), 4.45 (s, 2H, NCH
2), 6.88 (s, 1H, phenyl ring 4-H), 6.90 (s, 1H, phenyl ring 6-H), 7.93 (s, 1H, triazole ring 5-H), 8.19 (s, 1H, triazole ring 3-H).
Embodiment 7
The preparation of 2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4g)
Experimental implementation is with embodiment 1, and condensation reaction 4h, obtains weak yellow liquid 2-brooethyl-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (3g), yield 77.2%; Substitution reaction 9h, obtains faint yellow solid 2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4g), m.p.103 ~ 105 DEG C, yield 85.4%;
1h NMR (CDCl
3, 400MHz), δ: 1.48 (s, 6H, 2 × CH
3), 3.00 (s, 2H, furan nucleus CH
2), 3.74 (t, J=3.6Hz, 2H, OCH
2), 3.80 (t, J=3.6Hz, 2H, OCH
2), 4.49 (s, 2H, NCH
2), 6.70 (d, J=8.4Hz, 1H, phenyl ring 4-H), 7.25 ~ 7.26 (m, 2H, phenyl ring 3,6-H), 7.96 (s, 1H, triazole ring 5-H), 8.21 (s, 1H, triazole ring 3-H).
Embodiment 8
The preparation of 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4h)
Experimental implementation is with embodiment 1, and condensation reaction 3.5h, obtains weak yellow liquid 4-methyl-2-brooethyl-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (3h), yield 82.6%; Substitution reaction 9h, obtains white solid 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4h), m.p.107 ~ 109 DEG C, yield 52.4%;
1h NMR (CDCl
3, 400MHz), δ: 1.07 (d, J=6.0Hz, 3H, CH
3), 1.48 (s, 6H, 2 × CH
3), 3.01 (s, 2H, furan nucleus CH
2), 3.07 (t, J=7.4Hz, 1H, OCH
2), 3.90 (t, J=7.4Hz, 1H, OCH
2), 4.09 ~ 4.10 (m, 1H, OCH), 4.47 (s, 2H, NCH
2), 6.71 (d, J=6.6Hz, 1H, phenyl ring 4-H), 7.25 (d, J=6.0Hz, 1H, phenyl ring 3-H), 7.26 (s, 1H, phenyl ring 6-H), 7.97 (s, 1H, triazole ring 5-H), 8.27 (s, 1H, triazole ring 3-H).
Embodiment 9
The preparation of 4-propyl group-2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4i)
Experimental implementation is with embodiment 1, and condensation reaction 4h, obtains weak yellow liquid 4-propyl group-2-brooethyl-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (3i), yield 81.6%; Substitution reaction 10h, obtains yellowish brown liquid 4-propyl group-2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX (4i), yield 58.0%;
1h NMR (CDCl
3, 400MHz), δ: 0.86 (t, J=7.2Hz, 3H, CH
3), 1.18 ~ 1.40 (m, 4H, CH
2cH
2), 1.49 (s, 6H, 2 × CH
3), 3.01 (s, 2H, furan nucleus CH
2), 3.33 (t, J=8.2Hz, 1H, OCH
2), 3.92 (t, J=8.0Hz, 1H, OCH
2), 3.61 ~ 3.63 (m, 1H, OCH), 4.42 (s, 2H, NCH
2), 6.69 (d, J=8.8Hz, 1H, phenyl ring 4-H), 7.25 ~ 7.27 (m, 2H, phenyl ring 3-H and phenyl ring 6-H), 7.94 (s, 1H, triazole ring 5-H), 8.19 (s, 1H, triazole ring 3-H).
Embodiment 10
The preparation of 2-(1,2,4-triazole-1-methyl)-2-(chloro-2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-bases of 7-)-DOX (4j)
Experimental implementation is with embodiment 1, and condensation reaction 4h, obtains weak yellow liquid 2-brooethyl-2-(chloro-2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-bases of 7-)-DOX (3j), yield 76.9%; Substitution reaction 14h, obtains yellow solid 2-(1,2,4-triazole-1-methyl)-2-(chloro-2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-bases of 7-)-DOX (4j), m.p.96 ~ 98 DEG C, yield 19.4%;
1h NMR (CDCl
3, 400MHz), δ: 1.48 (s, 6H, 2 × CH
3), 3.00 (s, 2H, furan nucleus CH
2), 3.74 (t, J=3.6Hz, 2H, OCH
2), 3.80 (t, J=3.6Hz, 2H, OCH
2), 4.49 (s, 2H, NCH
2), 6.70 (d, J=8.4Hz, 1H, phenyl ring 4-H), 7.25 ~ 7.26 (m, 2H, phenyl ring 3-H and 6-H), 7.96 (s, 1H, triazole ring 5-H), 8.21 (s, 1H, triazole ring 3-H).
Embodiment 11
The preparation of 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(chloro-2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-bases of 7-)-DOX (4k)
Experimental implementation is with embodiment 1, and condensation reaction 4h, obtains weak yellow liquid 4-methyl-2-brooethyl-2-(chloro-2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-bases of 7-)-DOX (3k), yield 88.0%; Substitution reaction 16h, obtains tawny liquid 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(chloro-2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-bases of 7-)-DOX (4k), yield 24.3%;
1h NMR (CDCl
3, 400MHz), δ: 1.16 (d, J=6.4Hz, 3H, CH
3), 1.54 (s, 6H, 2 × CH
3), 3.08 (s, 2H, furan nucleus CH
2), 3.28 (t, J=8.4Hz, 1H, OCH
2), 3.95 (t, J=8.4Hz, 1H, OCH
2), 3.70 ~ 3.75 (m, 1H, OCH), 4.42 (s, 2H, NCH
2), 7.14 (s, 1H, phenyl ring 3-H), 7.30 (s, 1H, phenyl ring 6-H), 7.93 (s, 1H, triazole ring 5-H), 8.20 (s, 1H, triazole ring 3-H).
Embodiment 12
The preparation of 4-propyl group-2-(1,2,4-triazole-1-methyl)-2-(chloro-2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-bases of 7-)-DOX (4l)
Experimental implementation is with embodiment 1, and condensation reaction 5h, obtains weak yellow liquid 4-propyl group-2-brooethyl-2-(chloro-2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-bases of 7-)-DOX (3l), yield 85.6%; Substitution reaction 16h, obtains tawny liquid 4-propyl group-2-(1,2,4-triazole-1-methyl)-2-(chloro-2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-bases of 7-)-DOX (4l), yield 36.8%;
1h NMR (CDCl
3, 400MHz), δ: 0.88 (t, J=7.0Hz, 3H, CH
3), 1.46 ~ 1.56 (m, 2H, CH
2cH
2), 1.70 ~ 1.76 (m, 2H, CH
2cH
2), 1.25 (s, 6H, 2 × CH
3), 3.73 (s, 2H, furan nucleus CH
2), 3.19 (t, J=7.2Hz, 1H, OCH
2), 3.87 (t, J=7.2Hz, 1H, OCH
2), 3.93 ~ 3.95 (m, 1H, OCH), 4.45 (s, 2H, NCH
2), 7.18 (s, 1H, phenyl ring 4-H), 7.37 (s, 1H, phenyl ring 6-H), 7.93 (s, 1H, triazole ring 5-H), 8.20 (s, 1H, triazole ring 3-H).
Embodiment 13
The preparation of 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX
Experimental implementation, with embodiment 1, obtains 4-methyl-2-methylsulfonyl oxygen methyl-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX through condensation; Be substituted again and be obtained by reacting 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX.
Embodiment 14
The preparation of 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX
Experimental implementation, with embodiment 1, obtains 4-methyl-2-tolysulfonyl oxygen methyl-2-(7-methoxyl group-2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX through condensation; Be substituted again and be obtained by reacting 4-methyl-2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX.
Embodiment 15
The fungicidal activity of 2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX measures
1 test objective
The virulence of new compound to various pathogenic bacteria under for examination concentration at indoor measurement, preliminary assessment its fungicidal activity.
2 test conditionss
2.1 for examination target
The bacterial classifications such as Sclerotinia sclerotiorum (Sclerotonia sclerotiorum) and tobacco brown spot pathogen (Alternaria alternata) are all kept in refrigerator (4 ~ 8 DEG C), within 2-3 days, be inoculated in culture dish from test tube slant before test, cultivate under optimal temperature and be for experiment.Experiment substratum is potato agar substratum (PDA).
Wheat powdery mildew (Blumeria graminis) is preserved spore with stem and leaf of Wheat and is for experiment.
2.2 culture condition
Culture condition for examination target and the rear target of test is temperature 25 ± 5 DEG C, relative humidity 65 ± 5%
2.3 plant and instrument
Beaker, transfer pipet, graduated cylinder, culture dish, high-pressure sterilizing pot, constant temperature biochemical cultivation case etc.
3 test design
3.1 test medicines: 2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX (I).
Wherein, R is selected from: C
1~ C
2alkyl, C
3~ C
4straight chained alkyl or branched-chain alkyl; R
1be selected from: H, C
1~ C
2alkyl; Y is selected from: hydrogen, chlorine, bromine, fluorine, iodine, C
1~ C
2alkyl, C
3~ C
4straight chained alkyl or branched-chain alkyl, C
1~ C
2alkoxyl group, C
3~ C
4unbranched alkoxy or branched alkoxy.
3.2 experimental concentration
In vitro drug concentration establishes 25mg/L.
3.3 medicament preparations
Former medicine: take aequum with ten thousand/electronic balance; Solvent: DMF (DMF), 0.2%; Emulsifying agent: Tween 80,0.1%;
General sieve measures: accurately take 0.0500g sample, dissolves, add the sterilized water 98.8ml containing 0.1%Tween80 emulsifying agent, stir, be mixed with 500mg/L strength solution for subsequent use with 0.20mLDMF.
4 test methods
With reference to " pesticide bioactivity evaluates SOP ".
Sclerotinia sclerotiorum and tobacco brown spot pathogen: survey standard method NY/T1156.2-2006 with reference to raw, adopt pastille medium therapy: get each 500mg/L compound liquid 2mL, add in the PDA of the 38mL being cooled to 45 DEG C, make the pastille culture medium flat plate that final concentration is 25mg/L.Then get 6.5mm diameter mycelia block from cultured test germ colony edge, move on pastille substratum, often process 4 times and repeat.Be disposed, the constant temperature biochemical cultivation case being placed in 28 DEG C is cultivated, and measures colony diameter after 4 days, calculates growth inhibition ratio.
Wheat powdery mildew: adopt pot-culture method with reference to the raw standard method NY/T1156.4-2006 that surveys; seedling is selected to grow to the susceptible variety stem and leaf of Wheat of 2 leaf ~ 3 leaf phases; with spray method by 500mg/L compound medicine liquid spray on stem and leaf of Wheat; naturally dry; evenly shake off to be inoculated on stem and leaf of Wheat by the Powdery Mildew Fresh spores produced in morbidity wheat leaf blade upper 24 hour, often process is no less than 3 basins, the strain of every basin 10; protectiveness test is inoculation in 24 hours after chemicals treatment, cultivates under then putting suitable condition.According to blank incidence classification investigation, calculate prevention effect.
Solvent control is established in test.
5 fungicidal activity evaluations
The incidence of the rear routine observation record blade of process, plant and mycelial growth situation, according to disease index and hyphal diameter, calculate preventive effect and inhibiting rate.
2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2, the 3-Dihydrobenzofuranes-5-base) inhibiting rate of-DOX to hyphal cluster germ and Powdery Mildew is listed in table 2 and table 3 respectively:
Table 2 2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX is to the inhibiting rate of hyphal cluster germ (25mg/L)
Table 3 2-(1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX is to the inhibiting rate of Powdery Mildew (500mg/L)
4-propyl group-2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2, the 3-Dihydrobenzofuranes-5-base) inhibiting rate of-DOX to brown spot pathogen (25mg/L) is 61.2%.
2-(1,2,4-triazole-1-methyl)-2-(2,2-dimethyl-2,3-Dihydrobenzofuranes-5-base)-DOX has good fungicidal activity, can be used as and applies preparing in sterilant.
Claims (2)
1.2-(2, 4-triazole-1-methyl)-2-(2-methyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, it is characterized in that it is selected from 2-(1, 2, 4-triazole-1-methyl)-2-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-(1, 2, 4-triazole-1-methyl)-2-(7-methoxyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-propyl group-2-(1, 2, 4-triazole-1-methyl)-2-(7-oxyethyl group-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 2-(1, 2, 4-triazole-1-methyl)-2-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-(1, 2, 4-triazole-1-methyl)-2-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-propyl group-2-(1, 2, 4-triazole-1-methyl)-2-(2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane, 4-methyl-2-(1, 2, 4-triazole-1-methyl)-2-(7-chloro-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane or 4-propyl group-2-(1, 2, 4-triazole-1-methyl)-2-(7-chloro-2, 2-dimethyl-2, 3-Dihydrobenzofuranes-5-base)-1, 3-dioxolane.
2. 2-according to claim 1 (1,2,4-triazole-1-methyl)-2-(2-methyl-2,3-Dihydrobenzofuranes-5-base)-DOX is preparing the application of killing in the sterilant of hyphal cluster germ or brown spot pathogen.
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