CN105859697B - 1- benzofuranols ether -3- phenyl -2- (1,2,4- triazol-1-yls) -2- propenyls and its application - Google Patents
1- benzofuranols ether -3- phenyl -2- (1,2,4- triazol-1-yls) -2- propenyls and its application Download PDFInfo
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- CN105859697B CN105859697B CN201510025727.XA CN201510025727A CN105859697B CN 105859697 B CN105859697 B CN 105859697B CN 201510025727 A CN201510025727 A CN 201510025727A CN 105859697 B CN105859697 B CN 105859697B
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Abstract
The present invention relates to 1 benzofuranol ether, 3 phenyl, 2 (1,2,4 triazole, 1 base) 2 propenyls or its salt shown in chemical constitution Formulas I or II：Wherein, R is selected from：Hydrogen, C1~C2Alkyl, C3~C4Straight chained alkyl or branched alkyl；X1、X5It is selected from：Hydrogen, C1~C2Alkyl, hydroxyl, C1~C2Alkoxy, fluorine, chlorine, bromine, iodine or nitro；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X2、X4It is selected from：Hydrogen, C1~C2Alkyl；1 benzofuranol ether 3 phenyl 2 (1,2,4 triazole, the 1 base) application of 2 propenyls or its salt in fungicide or insecticide is prepared.
Description
Technical field
The present invention relates to a new class of compound and its preparation method and application, be specifically 1- benzofuranol ether -3- phenyl -
2- (1,2,4- triazol-1-yl) -2- propenyls and preparation method thereof are with it as the application for preparing sterilization and insecticide.
Background technology
Uniconazole P is the efficient, plant growth regulator of wide spectrum, hypotoxicity, has sterilization and herbicide effect concurrently.Chinese patent
[201010553848.9] describe and a series of noval chemical compounds are researched and developed in non-amino formate ester pesticide is prepared based on benzofuranol
Application.Tao Weifeng [Nankai University, Master's thesis, 2002] describes the synthesis of alkene oxazolone (alcohol) class compound containing pyridine radicals
And bactericidal activity.
The content of the invention
The object of the present invention is to provide the 1- benzofuranol ether -3- phenyl -2- (1,2,4- shown in chemical structural formula I or II
Triazol-1-yl) -2- propenyls or its salt：
Wherein, R is selected from：Hydrogen, C1~C2Alkyl, C3~C4Straight chained alkyl or branched alkyl；X1、X5It is selected from：Hydrogen, C1~C2Alkane
Base, hydroxyl, C1~C2Alkoxy, fluorine, chlorine, bromine, iodine or nitro；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X2、X4
It is selected from：Hydrogen, C1~C2Alkyl；Its salt is selected from：Hydrochloride, hydrobromate, sulfate, nitrate, phosphate, mesylate, benzene sulphur
Hydrochlorate, tosilate, malate, lactate, succinate or butene dioic acid salt.
- 1- benzofuranol ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls shown in formula I are (Z) -1- (benzene
And furans -5- bases) -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol；- 1- benzofuranols ether shown in formula II-
3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls are (E) -1- benzofuranol ether -3- phenyl -2- (1,2,4- triazole -1-
Base) -2- propenyls.
The object of the present invention is to provide the 1- benzofuranol ether -3- phenyl -2- (1,2,4- shown in chemical structural formula III or IV
Triazol-1-yl) -2- propenyls：
Wherein, X1、X5It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine
Or iodine；X2、X4It is selected from：Hydrogen, C1~C2Alkyl.
The object of the present invention is to provide the 1- benzofuranol ether -3- phenyl -2- (1,2,4- shown in chemical structural formula V or VI
Triazol-1-yl) -2- propenyls：
Wherein, X1、X5It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine,
Bromine, iodine；X2、X4It is selected from：Hydrogen, C1~C2Alkyl.
The object of the present invention is to provide the 1- benzofuranol ether -3- phenyl -2- (1,2,4- shown in chemical structural formula VII or VIII
Triazol-1-yl) -2- propenyls：
Wherein, X1、X5It is selected from：Hydrogen, C1~C2Alkyl, hydroxyl, C1~C2Alkoxy, fluorine, chlorine, bromine, iodine or nitro；X3Choosing
From：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine, iodine or iodine；X2、X4It is selected from：Hydrogen, C1~C2Alkyl.
1- benzofuranols ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls provided by the invention are selected from：1-
(7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- aminomethyl phenyls) -2- (1,2,4- triazole -1-
Base) -2- propylene -1- alcohol, 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- chlorphenyls) -2-
(1,2,4- triazol-1-yl) -2- propylene -1- alcohol, 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -
3- (2,4- dichlorophenyl) -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol, (E) -1- (7- ethyoxyls -2,2- dimethyl -
2,3- Dihydrobenzofuranes -5- bases) -3- (2,4- dichlorophenyl) -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol, 1- (7-
Propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- chlorphenyls) -2- (1,2,4- triazol-1-yl) -2-
Propylene -1- alcohol, 1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2,4- chlorphenyl) -2- (1,
2,4- triazol-1-yls) -2- propylene -1- alcohol, 1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3-
(4- bromophenyls) -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol or 1- (7- propoxyl group -2,2- dimethyl -2,3- dihydrobenzenes
And furans -5- bases) -3- (2- nitrobenzophenones) -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol.
1- benzofuranols ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls provided by the invention are selected from：1-
(7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- methoxyphenyls) -2- (1,2,4- triazole -1-
Base) -2- propylene -1- alcohol or 1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- fluorophenyls) -
2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol.
The present invention provides 1- (benzofuran -5- bases) -3- phenyl -2- (1,2,4- tri- shown in chemical structural formula I or II
Azoles -1- bases) -2- propylene -1- alcohol preparation method, it is characterised in that it preparation reaction it is as follows：
Wherein, R is selected from：Hydrogen, C1~C2Alkyl, C3~C4Straight chained alkyl or branched alkyl；X1、X5It is selected from：Hydrogen, C1~C2Alkane
Base, hydroxyl, C1~C2Alkoxy, fluorine, chlorine, bromine, iodine or nitro；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X2、X4
It is selected from：Hydrogen, C1~C2Alkyl.
The present invention provides 1- benzofuranol ether -3- phenyl -2- (1,2, the 4- triazole -1- shown in chemical structural formula I~VIII
Base) the application of -2- propenyls in fungicide is prepared.
The present invention provides the 1- benzofuranol ether -3- phenyl -2- (1,2,4- tri- shown in chemical structural formula I, II, VII or VIII
Azoles -1- bases) the application of -2- propenyls in insecticide is prepared.
The present invention has the following advantages that compared with prior art：The present invention provide chemical formula I shown in 1- benzofuranols ether-
3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls have the activity of sterilization and desinsection.
Embodiment
Following embodiments are intended to illustrate invention rather than limitation of the invention further.
Embodiment 1
(Z/E) -1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- aminomethyl phenyls) -2-
The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- alcohol [(Z)-B1 and (E)-B1]
3.5mmol 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -2- (1,2,4- triazole)
Ethyl ketone (D1), 5.2mmol 4- tolyl aldehydes and 30mL chloroforms, stirring, be added dropwise catalytic amount piperidines, and flow back 6h.Reaction terminates
Afterwards, reaction solution is through washing, and saturated common salt washing, dry, precipitation, column chromatography for separation obtains product A1.
0.79mmol compounds A1,1.6mmol sodium borohydride is added in 100mL there-necked flasks, 20ml absolute ethyl alcohols, 40 DEG C anti-
15min is answered, is evaporated under reduced pressure precipitation, column chromatography for separation obtains product, yield 89.2%. (E)-B1:M.p.120~125 DEG C,1H
NMR (400MHz, CDCl3)δ:1.49 (s, 6H, 2 × CH3), 2.28 (s, 3H, CH3), 2.98 (s, 2H, CH2), 3.80 (s, 3H,
OCH3), 5.60 (s, 1H, CH), 6.65 (s, 1H, C6H24-H), 6.71 (d, J=8.0Hz, 2H, C6H43,5-H), 6.72 (s, 1H,
C6H26-H), 6.84 (s, 1H, CCH), 7.01 (d, J=8.0Hz, 2H, C6H42,6-H), 7.61 (s, 1H, triazole ring 3-H),
8.08 (s, 1H, triazole ring 5-H)；13C NMR(101MHz,CDCl3)δ:21.19,28.21,43.19,55.89,75.73,
88.02,109.15,115.40,126.54,128.20,128.34,129.53,129.75,132.02,132.76,136.20,
138.89,144.47,144.65,147.37,152.18；(Z)-B1:M.p.69~71 DEG C,1H NMR (400MHz, CDCl3)δ:
1.48 (s, 6H, 2 × CH3), 2.27 (s, 3H, CH3), 2.99 (s, 2H, CH2), 3.81 (s, 3H, OCH3), 5.12 (s, 1H, CH),
6.68 (s, 1H, C6H24-H), 6.72 (d, J=8.0Hz, 2H, C6H43,5-H), 6.82 (s, 1H, C6H26-H), 6.92 (d, J=
8.0Hz, 2H, C6H42,6-H), 7.06 (s, 1H, CCH), 7.46 (s, 1H, triazole ring 3-H), 7.98 (s, 1H, triazole ring 5-H)
；13C NMR(101MHz,CDCl3)δ:151.70,151.52,147.43,143.69,143.49,136.27,134.07,
132.27,129.25,128.49,126.96,114.85,110.93,110.52,87.75,68.81,64.47,43.25,
34.37,28.18,20.93,14.86。
Embodiment 2
(Z/E) -1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- chlorphenyls) -2-
The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- alcohol [(Z)-B4 and (E)-B4]
Operation reacts 0.5h, yield 87.1% with embodiment 1.(E)-B4:M.p.83~84 DEG C,1H NMR (400MHz,
CDCl3)δ:1.46 (s, 6H, 2 × CH3), 2.94 (s, 2H, CH2), 3.78 (s, 3H, OCH3), 5.96 (s, 1H, CH), 6.67~
6.80 (m, 2H, C6H24,6-H), 7.32 (m, 4H, C6H4), 7.07 (s, 1H, CCH), 8.01 (s, 1H, triazole ring 3-H), 8.49
(s, 1H, triazole ring 5-H)；(Z)-B4:M.p.69~72 DEG C,1H NMR (400MHz, CDCl3)δ:1.49 (s, 6H, 2 × CH3),
2.98 (s, 2H, CH2), 3.84 (s, 3H, OCH3), 5.83 (s, 1H, CH), 6.68~6.74 (m, 2H, C6H2, 7.32 4,6-H)~
7.51 (m, 4H, C6H4), 7.40 (s, 1H, CCH), 8.00 (s, 1H, triazole ring 3-H), 8.24 (s, 1H, triazole ring 5-H).
Embodiment 3
(Z/E) -1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2,4 dichloro benzene base) -
The preparation of 2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol [(Z)-B6 and (E)-B6]
Operation reacts 0.5h, yield 76.7% with embodiment 1.(E)-B6:M.p.72~75 DEG C,1H NMR (400MHz,
CDCl3)δ:1.49 (s, 6H, 2 × CH3), 2.98 (s, 2H, CH2), 3.83 (s, 3H, OCH3), 5.68 (s, 1H, CH), 6.62~
6.71 (m, 2H, C6H24,6-H), 6.75~7.42 (m, 3H, C6H3), 7.52 (s, 1H, CCH), 8.00 (s, 1H, triazole ring 3-
H), 8.43 (s, 1H, triazole ring 5-H)；(Z)-B6:M.p.84~87 DEG C,1H NMR (400MHz, CDCl3)δ:1.47 (s, 6H, 2
×CH3), 2.95 (s, 2H, CH2), 3.77 (s, 3H, OCH3), 5.84 (s, 1H, CH), 6.56~6.68 (m, 2H, C6H24,6-H),
7.15~7.77 (m, 3H, C6H3), 7.80 (s, 1H, CCH), 8.58 (s, 1H, triazole ring 3-H), 8.99 (s, 1H, triazole ring 5-
H)。
Embodiment 4
(E) -1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2,4 dichloro benzene base) -2-
The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- alcohol (E)-B11
Operation reacts 0.5h, yield 87.5% with embodiment 1.(E)-B11:M.p.63~65 DEG C,1H NMR (400MHz,
CDCl3)δ:1.24~1.25 (m, 3H, CH3), 1.42 (s, 6H, 2 × CH3), 2.94 (s, 2H, CH2), 3.14~3.31 (m, 2H,
CH2), 4.03 (q, J=7.6Hz, 2H, CH2), 5.96 (s, 1H, CH), 6.71~7.03 (m, 2H, C6H2), 7.30~7.45 (m,
4H, C6H4), 7.52 (s, 1H, C=CH), 8.08 (s, 1H, triazole ring 3-H), 8.24 (s, 1H, triazole ring 5-H).
Embodiment 5
(Z/E) -1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- methoxyphenyls) -
The preparation of 2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol [(Z)-B15 and (E)-B15]
Operation reacts 0.5h, yield 81.8% with embodiment 1.(E)-B15:M.p.152~155 DEG C,1H NMR
(400MHz, CDCl3)δ:1.00 (t, J=7.2Hz, 3H, CH3), 1.48 (s, 6H, 2 × CH3), 1.79~1.82 (m, 2H,
CH2), 2.96 (s, 2H, CH2), 3.79 (s, 3H, OCH3), 3.94~3.99 (t, J=7.2Hz, 2H, CH2), 4.58 (s, 1H,
OH), 5.66 (s, 1H, CH), 6.58~6.75 (m, 2H, C6H2), 6.79~7.03 (m, 4H, C6H4), 7.23 (s, 1H, C=
CH), 7.71 (s, 1H, triazole ring 3-H), 8.04 (s, 1H, triazole ring 5-H)；(Z)-B15:M.p.92~95 DEG C,1H NMR
(400MHz, CDCl3)δ:1.01 (t, J=7.6Hz, 3H, CH3), 1.51 (s, 6H, 2 × CH3), 1.80~1.83 (m, 2H,
CH2), 3.01 (s, 2H, CH2), 3.16~3.22 (d, J=7.2Hz, 2H, CH2), 3.27 (q, J=7.2Hz, 1H, CH), 3.27
(d, J=9.2Hz, 2H, CH2), 3.70 (s, 3H, CH3), 3.98 (t, J=7.2Hz, 2H, CH2), 4.78 (m, 1H, OH), 5.13
~5.17 (m, 1H, CH), 6.69 (s, 2H, C6H2), 6.70~7.16 (m, 4H, C6H4), 7.52 (s, 1H, C=CH), 7.62 (s,
1H, triazole ring 3-H), 7.93 (s, 1H, triazole ring 5-H).
Embodiment 6
(Z/E) -1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- fluorophenyls) -2-
The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- alcohol [(Z)-B16 and (E)-B16]
Operation reacts 0.5h, yield 88.2% with embodiment 1.(E)-B16:M.p.54~56 DEG C,1H NMR (400MHz,
CDCl3)δ:0.96 (t, 3H, J=7.2Hz, CH3), 1.46 (s, 6H, 2 × CH3), 1.75~1.82 (m, 2H, CH2), 2.95 (s,
2H, CH2), 3.71~3.74 (m, 2H, CH2), 5.58 (s, 1H, OH), 6.11 (s, 1H, CH), 6.66~6.74 (m, 2H,
C6H2), 6.82~7.40 (m, 4H, C6H4), 7.71 (s, 1H, CCH), 8.09 (s, 1H, triazole ring 3-H), 8.65 (s, 1H, triazoles
Ring 5-H)；(Z)-B16:M.p.145~48 DEG C,1H NMR (400MHz, CDCl3)δ:1.02 (t, 3H, J=7.2Hz, CH3),
1.50 (s, 6H, 2 × CH3), 1.80~1.83 (m, 2H, CH2), 2.99 (s, 2H, CH2), 3.97~3.99 (m, 2H, CH2),
4.61 (s, 1H, OH), 4.93~4.95 (m, 1H, CH), 6.69~6.72 (m, 2H, C6H2), 6.86~7.35 (m, 4H, C6H4),
7.75 (s, 1H, CCH), 8.15 (s, 1H, triazole ring 3-H), 8.39 (s, 1H, triazole ring 5-H).
Embodiment 7
(Z/E) -1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- chlorphenyls) -2-
The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- alcohol [(Z)-B18 and (E)-B18]
Operation reacts 0.5h, yield 71.4% with embodiment 1.(E)-B18:M.p.40~43 DEG C,1H NMR (400MHz,
CDCl3)δ:1.01 (t, 3H, J=7.2Hz, CH3), 1.50 (s, 6H, 2 × CH3), 1.78~1.82 (m, 2H, CH2), 2.99 (s,
2H, CH2), 3.92~3.97 (m, 2H, CH2), 5.11~5.12 (m, 1H, CH), 6.70~6.72 (m, 2H, C6H24,6-H),
6.81 (d, J=8.0Hz, 2H, C6H42,6-H), 7.14 (d, J=8.0Hz, 2H, C6H43,5-H), 7.20 (s, 1H, CCH),
8.04~8.25 (m, 2H, triazole rings)；(Z)-B18:M.p.56~58 DEG C,1H NMR (400MHz, CDCl3)δ:1.10 (t, 3H, J
=7.2Hz, CH3), 1.49 (s, 6H, 2 × CH3), 1.78~1.84 (m, 2H, CH2), 2.99 (s, 2H, CH2), 3.93~4.00
(m, 2H, OCH2), 4.34~4.37 (m, 1H, OH), 5.09~5.10 (m, 1H, CH), 6.65~6.70 (m, 2H, C6H24,6-
H), 6.72 (d, J=8.2Hz, 2H, C6H42,6-H), 7.12 (d, J=8.2Hz, 2H, C6H43,5-H), 7.45 (s, 1H, CCH),
7.97~8.10 (m, 2H, triazole rings).
Embodiment 8
(E) -1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2,4- chlorphenyls) -2-
The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- alcohol (E)-B19
Operation reacts 0.5h with embodiment 1, yield 91.7%, m.p.65~69 DEG C, 1.01 (t, J=6.8Hz, 3H,
CH3), 1.49 (s, 6H, 2 × CH3), 1.81 (m, 2H, CH2), 2.96 (s, 2H, CH2), 3.95~3.97 (m, 2H, CH2), 4.71
(br, 1H, OH), 5.01 (m, 1H, CH), 5.18 (s, 1H, C=CH), 6.58~6.73 (m, 2H, C6H24-H), 7.18 (s, 1H,
C6H26-H), 7.28~7.50 (m, 3H, C6H3), 8.07 (s, 1H, triazole ring 3-H), 8.46 (s, 1H, triazole ring 5-H).
Embodiment 9
(Z/E) -1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- bromophenyls) -2-
The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- alcohol [(Z)-B20 and (E)-B20]
Operation reacts 0.5h, yield 66.7% with embodiment 1.(E)-B20:M.p.135~137 DEG C,1H NMR
(400MHz, CDCl3)δ:0.99 (t, J=7.2Hz, 3H, CH3), 1.49 (s, 6H, 2 × CH3), 1.74~1.78 (m, 2H,
CH2), 2.95~2.97 (m, 2H, CH2), 3.93 (t, J=7.2Hz, 2H, CH2), 5.59 (s, 1H, OH), 6.12 (s, 1H, CH),
6.66 (s, 1H, C6H24-H), 6.70~6.73 (m, 2H, C6H43,5-H), 6.83 (s, 1H, C6H26-H), 7.36~7.37 (m,
2H, C6H42,6-H), 7.75 (s, 1H, C=CH), 8.12 (s, 1H, triazole ring 3-H), 8.78 (s, 1H, triazole ring 5-H)；(Z)-
B20:M.p.55~58 DEG C,1H NMR (400MHz, CDCl3)δ:0.97 (t, J=7.2Hz, 3H, CH3), 1.51 (s, 6H, 2 ×
CH3), 1.77~1.80 (m, 2H, CH2), 2.97 (s, 2H, CH2), 3.94 (t, J=7.2Hz, 2H, CH2), 5.60 (s, 1H,
OH), 6.18 (s, 1H, CH), 6.67~6.70 (m, 2H, C6H2), 6.78~6.83 (m, 2H, C6H42,6-H), 7.31~7.35
(m, 2H, C6H43,5-H), 7.56 (s, 1H, C=CH), 8.01 (s, 1H, triazole ring 3-H), 8.05 (s, 1H, triazole ring 5-H).
Embodiment 10
(Z/E) -1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- nitrobenzophenones) -2-
The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- alcohol [(Z)-B21 and (E)-B21]
Operation reacts 0.5h, yield 65.2% with embodiment 1.(E)-B21:M.p.123~126 DEG C,1H NMR
(400MHz, CDCl3)δ:0.98 (t, J=7.2Hz, 3H, CH3), 1.44 (s, 6H, 2 × CH3), 1.72~1.76 (m, 2H,
CH2), 2.90 (s, 2H, CH2), 3.87 (t, J=7.2Hz, 2H, CH2), 5.18 (s, 1H, OH), 5.75 (s, 1H, CH), 6.58~
6.59 (m, 2H, C6H2), 7.54~8.06 (m, 4H, C6H4), 8.06 (s, 1H, CCH), 8.24~8.26 (m, 1H, triazole ring 3-
H), 8.64 (s, 1H, triazole ring 5-H)；(Z)-B21:M.p.56~58 DEG C,1H NMR (400MHz, CDCl3)δ:1.02 (t, J=
7.2Hz, 3H, CH3), 1.48 (s, 6H, 2 × CH3), 1.80~1.82 (m, 2H, CH2), 2.97 (s, 2H, CH2), 4.02 (m, 2H,
CH2), 5.00 (s, 1H, OH), 5.20~5.25 (m, 1H, CH), 5.75 (s, 1H, C=CH), 6.68~6.70 (m, 1H, C6H24-
H), 6.80 (m, 1H, C6H26-H), 7.43~7.93 (m, 4H, C6H4), 7.98 (s, 1H, triazole ring 3-H), 8.11~8.13 (m,
1H, triazole ring 5-H).
Embodiment 11
The bactericidal activity measure of 1- benzofuranol ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls
Assay method is shown in CN101268059A.
Preparation for trying mother liquor：0.84mL cyclohexanone and dimethyl sulfoxide (1:1) 16.8mg samples to be tested, Ran Houjia are added
Enter 27.16mL water, acetone (10%), emulsifying agent Wettol (0.1%) and wetting agent Silwet (0.05%).
Sample is handled with 31mg/L active ingredients, the parameter of measurement and the control group of inactive component and sterile inactive
The growing state control of the blank group of component, determines corresponding the pathogen growth rate and inhibitory activity of each reactive compound.
Tested strain：Ash arrhizus bacteria (Botrytis cinerea, BOTRCI), late disease bacteria (Phytophthora
Infestans, PHYTIN), Pyricularia oryzae (Pyricularia oryzae, PYRIOR), wheat septoria bacterium (Septoria
Tritici, SEPTTR).
To the inhibitory activity test method of ash arrhizus bacteria：Mixed in proportion for examination mother liquor, micro drop is drawn into pipettor
On fixed board (MTP), normal concentration is then diluted with water to.By biological the malt aqueous solution or yeast of suspension ash arrhizus bacteria spore-
Bacterioprotein-glycerin solution adds, and plank is positioned over steam-laden room, maintains 18 DEG C of temperature.After inoculation 7 days,
Experimental plate is detected under 405nm using absorption spectrophotometer.
To the inhibitory activity test method of late disease bacteria：Mixed in proportion for examination mother liquor, micro drop is drawn into pipettor
On fixed board (MTP), normal concentration is then diluted with water to.By the pea juice solution or DDC media of suspension late disease bacteria spore
Add, plank is positioned over steam-laden room, maintains 18 DEG C of temperature.After inoculation 7 days, existed using absorption spectrophotometer
Experimental plate is detected under 405nm.
The test method of Pyricularia oryzae and wheat septoria bacterium is identical with ash arrhizus bacteria.
Bactericidal activity is the results show that under 31mg/L concentration, and compound E-B4, E-B6, Z-B6, E-B11 and E-B21 are to grey mold
The inhibiting rate of germ is 50%, and compound E-B19 is 60% to the inhibiting rate of ash arrhizus bacteria；Compound E-B1 is to late disease bacteria
Inhibiting rate be 60%；Compound E-B6 is 50% to the inhibiting rate of Pyricularia oryzae, compound Z-B6, E-B11, E-B18, Z-
B18 and Z-B20 is 60% to the inhibiting rate of Pyricularia oryzae, and compound E-B19 and E-B20 distinguishes the inhibiting rate of Pyricularia oryzae
For 80% and 70%, EDs of the compound E-B19 to Pyricularia oryzae50For 10.2mg/L.
1- benzofuranol ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls can be used as and prepare bactericide
Using.
Embodiment 12
The insecticidal activity assay of 1- benzofuranol ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls
Test sample：1- benzofuranol ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls：
Wherein, R is selected from：Hydrogen, C1~C2Alkyl, C3~C4Straight chained alkyl or branched alkyl；X1、X5It is selected from：Hydrogen, C1~C2Alkane
Base, hydroxyl, C1~C2Alkoxy, fluorine, chlorine, bromine, iodine or nitro；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X2、X4
It is selected from：Hydrogen, C1~C2Alkyl.
Test method is shown in：CN101453895B, CN101980607A.
Tested pest：Black peach aphid (Green Peach Aphid, GPA), anthonomus grandis (Anthonomus grandis, BW),
Aedes aegypti (Aedes aegypti, YFM).
Test concentrations：Under 2500mg/L concentration, the death rate of pest.
(1) the poisoning measure to black peach aphid (Myzus persicae)
Test compound is dissolved in cyclohexanone, is made into 1 × 105Mg/L solution is simultaneously loaded on 1.3mLGuan Zhong.By test tube
An automatic electrostatic atomizer with atomizer is inserted into, is using it for mother liquor configuration dilute solution, diluent during use
+ 50% water of 50% acetone (volume ratio), and in the solution add 0.01% (volume ratio) nonionic surfactant (
).The pimento plant of 1 heart stage of 1 leaf first accesses pest before medication, and the leaf of severe infections is placed on the top for examination plant,
Every plant of plant is infected 30~50 aphids by an evening, then will infect blade and remove.Liquid is passed through into automatic electrostatic spray
The atomizer of device is sprayed onto on infected plant, and plant removes after being spontaneously dried in spray tank, is put into culturing room, glimmering
Light irradiates 24h, maintains 25 DEG C of room temperature and relative humidity 20-40% to cultivate 5 days.Test worm is observed after 5 days, is calculated with reference to control group dead
Die rate.
(2) the poisoning measure to anthonomus grandis (Anthonomus grandis)
Test cell is made of the 96-well microtiter plate comprising insect meals and 5-10 anthonomus grandis ovum.
Test compound is configured to solution with the mixed solvent of 75% water and 25%DMSO (volume ratio), miniature with customization
The solution of various concentrations is sprayed on blade by sprayer with the amount of 5 μ l respectively, is repeated 2 times.After, titer plate is placed in
25 ± 1 DEG C of temperature, incubates 5 days in the environment of relative humidity 75 ± 5%.Visual assessment ovum and the death rate of larva.
(3) the poisoning measure to Aedes aegypti (Aedes aegypti)
Test cell is by the 96-well microtiter plate group comprising 200 μ l tap water and the 5-15 Aedes aegypti larvas newly hatched
Into.
Test compound is configured to solution with the mixed solvent of 75% water and 25%DMSO (volume ratio), with micro- spray of customization
The solution of various concentrations is sprayed on insect diet by day with fog with the amount of 2.5 μ l, is repeated 2 times, is placed in titer plate after
28 ± 1 DEG C of temperature, incubates 2 days in the environment of relative humidity 80 ± 5%.The death rate of visual assessment larva.
The results show：Under 2500mg/L concentration, compound Z-B15 has black peach aphid virulence, and the death rate of black peach aphid is
50%；E-B16 is 50% to the virulence of anthonomus grandis.
1- benzofuranol ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls can be used as and prepare insecticide application.
Claims (6)
1. 1- benzofuranols ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenyls shown in chemical structural formula I or II or
Application of its salt in fungicide or insecticide is prepared：
Wherein, R is selected from：Hydrogen, C1~C2Alkyl, C3~C4Straight chained alkyl or branched alkyl；X1、X5It is selected from：Hydrogen, C1~C2Alkyl, hydroxyl
Base, C1~C2Alkoxy, fluorine, chlorine, bromine, iodine or nitro；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X2、X4It is selected from：
Hydrogen, C1~C2Alkyl；Its salt is selected from：Hydrochloride, hydrobromate, sulfate, nitrate, phosphate, mesylate, benzene sulfonate,
Tosilate, malate, lactate, succinate or butene dioic acid salt.
2. the application described in claim 1,1- benzofuranol ether -3- phenyl -2- wherein shown in formula I or II (1,2,4- triazole -
1- yls) compound shown in the preferred chemical structural formula III or IV of -2- propenyls：
Wherein, X1、X5It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；
X2、X4It is selected from：Hydrogen, C1~C2Alkyl.
3. the application described in claim 1,1- benzofuranol ether -3- phenyl -2- wherein shown in formula I or II (1,2,4- triazole -
1- yls) compound shown in the preferred chemical structural formula V or VI of -2- propenyls：
Wherein, X1、X5It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine, iodine；
X2、X4It is selected from：Hydrogen, C1~C2Alkyl.
4. the application described in claim 1,1- benzofuranol ether -3- phenyl -2- wherein shown in formula I or II (1,2,4- triazole -
1- yls) compound shown in the preferred chemical structural formula VII or VIII of -2- propenyls：
Wherein, X1、X5It is selected from：Hydrogen, C1~C2Alkyl, hydroxyl, C1~C2Alkoxy, fluorine, chlorine, bromine, iodine or nitro；X3It is selected from：Hydrogen,
C1~C2Alkyl, fluorine, chlorine, bromine or iodine；X2、X4It is selected from：Hydrogen, C1~C2Alkyl.
5. the application described in claim 1,1- benzofuranol ether -3- phenyl -2- wherein shown in formula I or II (1,2,4- triazole -
1- yls) -2- propenyls are selected from following compounds：
1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- aminomethyl phenyls) -2- (1,2,4- tri-
Azoles -1- bases) -2- propylene -1- alcohol, 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- chlorobenzenes
Base) -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol, 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -
5- yls) -3- (2,4- dichlorophenyl) -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol, (E) -1- (7- ethyoxyls -2,2- bis-
Methyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2,4- dichlorophenyl) -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol,
1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- chlorphenyls) -2- (1,2,4- triazole -1-
Base) -2- propylene -1- alcohol, 1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2,4- chlorphenyls) -
2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol, 1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5-
Base) -3- (4- bromophenyls) -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol or 1- (7- propoxyl group -2,2- dimethyl -2,3-
Dihydrobenzofuranes -5- bases) -3- (2- nitrobenzophenones) -2- (1,2,4- triazol-1-yl) -2- propylene -1- alcohol.
6. the application described in claim 1,1- benzofuranol ether -3- phenyl -2- wherein shown in formula I or II (1,2,4- triazole -
1- yls) -2- propenyls are selected from following compounds：
1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- methoxyphenyls) -2- (1,2,4-
Triazol-1-yl) -2- propylene -1- alcohol or 1- (7- propoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- fluorine
Phenyl) -2- (1,2,4- triazol-1-yl) -2- propenyls.
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