CN104610236B - The preparation and application of furans amphyl containing triazolyl - Google Patents

The preparation and application of furans amphyl containing triazolyl Download PDF

Info

Publication number
CN104610236B
CN104610236B CN201510064706.9A CN201510064706A CN104610236B CN 104610236 B CN104610236 B CN 104610236B CN 201510064706 A CN201510064706 A CN 201510064706A CN 104610236 B CN104610236 B CN 104610236B
Authority
CN
China
Prior art keywords
bases
ketone
dimethyl
dihydrobenzofuranes
propylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201510064706.9A
Other languages
Chinese (zh)
Other versions
CN104610236A (en
Inventor
杨泽慧
李婉
杨子辉
邵丹凤
胡艾希
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo University of Technology
Original Assignee
Ningbo University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo University of Technology filed Critical Ningbo University of Technology
Priority to CN201510064706.9A priority Critical patent/CN104610236B/en
Publication of CN104610236A publication Critical patent/CN104610236A/en
Application granted granted Critical
Publication of CN104610236B publication Critical patent/CN104610236B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to the application of furans amphyl or its salt in herbicide is prepared containing triazolyl 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 or nitro；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine, iodine or nitro；X2、X4It is selected from：Hydrogen, C1~C2Alkyl or nitro.

Description

The preparation and application of furans amphyl containing triazolyl
Technical field
It is specifically that the benzofuranol containing triazolyl derives the present invention relates to new compound of a class and its preparation method and application Thing and preparation method thereof is used as the application for preparing herbicide with it.
Background technology
Chinese patent [CN103275073A, 2013.9.4 are disclosed] describes 2- (1,2,4- triazole -1- methyl) -2- benzos Furans-DOX and its application as bactericide.Chinese patent [CN102177897B, 2013.3.27 are authorized] is retouched 5- [2- (benzyl imido grpup) thiazole-4-yl] furans phenolic ethers have been stated as the application of bactericide.[institution of higher education's Science of Chemistry such as Luo Xianfu Report, 2011.32 (12), 2800~2805] report 4- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- Base) -2- fragrant aminos thiazole and its insecticidal activity.Shen Fang etc. [organic chemistry, 2012.32,388~392] reports compound 4- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -2- benzyl imino thiazoles have desinsection, sterilization and weeding Activity.
The content of the invention
It is an object of the invention to provide chemical constitution Formulas I or II shown in furans amphyl containing triazolyl or its salt Application in herbicide is prepared：
Wherein, R is selected from：Hydrogen, deuterium, C1~C2Alkyl, C3~C4Straight chained alkyl or branched alkyl；X1、X5It is selected from：Hydrogen, deuterium, C1 ~C2Alkyl, hydroxyl, C1~C2Alkoxy or nitro；X3It is selected from：Hydrogen, deuterium, C1~C2Alkyl, fluorine, chlorine, bromine, iodine or nitro；X2、X4 It is selected from：Hydrogen, deuterium, C1~C2Alkyl or nitro；Its salt is selected from：Hydrochloride, hydrobromate, sulfate, nitrate, phosphate, first sulphur Hydrochlorate, benzene sulfonate, tosilate, malate, lactate, succinate or butene dioic acid salt.
It is an object of the invention to provide chemical constitution formula III or IV shown in furans amphyl containing triazolyl or its Application of the salt in herbicide is prepared：
Wherein, X1、X5It is selected from：Hydrogen, C1~C2Alkyl, hydroxyl, C1~C2Alkoxy or nitro；X3It is selected from：Hydrogen, C1~C2Alkane Base, fluorine, chlorine, bromine, iodine or nitro；X2、X4It is selected from：Hydrogen, C1~C2Alkyl or nitro.
It is an object of the invention to provide chemical constitution Formula V or VI shown in furans amphyl containing triazolyl or its salt Application in herbicide is prepared：
Wherein, X1、X5It is selected from：Hydrogen, deuterium, C1~C2Alkyl, hydroxyl, C1~C2Alkoxy or nitro；X3It is selected from：Hydrogen, deuterium, C1 ~C2Alkyl, fluorine, chlorine, bromine, iodine or nitro；X2、X4It is selected from：Hydrogen, deuterium, C1~C2Alkyl or nitro.
It is an object of the invention to provide I or II shown in the furans amphyl containing triazolyl be selected from：1- (7- methoxies Base -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone, 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- ketone, 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- chlorphenyls) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone, 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) - 3- (2- nitrobenzophenones) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone, 1- (7- methoxyl groups -2,2- dimethyl -2,3- bis- Hydrogen benzofuran -5- bases) -3- (3- nitrobenzophenones) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone, 1- (7- methoxyl groups - 2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- nitrobenzophenones) -2- (1,2,4- triazol-1-yl) -2- propylene - 1- ketone, 1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- methoxyphenyls) -2- (1,2,4- Triazol-1-yl) -2- propylene -1- ketone, 1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- fluorine Phenyl) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone, 1- (7- ethyoxyl -2,2- dimethyl -2,3- dihydrobenzo furans Mutter -5- bases) -3- (4- chlorphenyls) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone or 1- (7- ethyoxyl -2,2- diformazans Base -2,3- Dihydrobenzofuranes -5- bases) -3- (4- bromophenyls) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone.
It is an object of the invention to provide III or IV shown in the furans amphyl containing triazolyl be selected from：4. right will Ask the application described in 1, wherein I or the furans amphyl containing triazolyl shown in II are selected from：1- (7- methoxyl group -2,2- diformazans Base -2,3- Dihydrobenzofuranes -5- bases) -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone, 1- (7- methoxyl groups - 2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- aminomethyl phenyls) -2- (1,2,4- triazol-1-yl) -2- propylene - 1- ketone, 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- chlorphenyls) -2- (1,2,4- tri- Azoles -1- bases) -2- propylene -1- ketone, 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- nitros Phenyl) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone, 1- (7- methoxyl group -2,2- dimethyl -2,3- dihydrobenzo furans Mutter -5- bases) -3- (3- nitrobenzophenones) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone or 1- (7- methoxyl group -2,2- diformazans Base -2,3- Dihydrobenzofuranes -5- bases) -3- (4- nitrobenzophenones) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone.
It is an object of the invention to provide V or VI shown in the furans amphyl containing triazolyl be selected from：1- (7- ethoxies Base -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- methoxyphenyls) -2- (1,2,4- triazol-1-yl) -2- Propylene -1- ketone, 1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- fluorophenyls) -2- (1,2, 4- triazol-1-yls) -2- propylene -1- ketone, 1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- Chlorphenyl) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone or 1- (7- ethyoxyl -2,2- dimethyl -2,3- dihydrobenzos Furans -5- bases) -3- (4- bromophenyls) -2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone.
The present invention has the following advantages that compared with prior art：The present invention is provided contains triazolyl shown in Formula I~VI Furans amphyl there is activity of weeding.
Embodiment
Following examples are intended to illustrate invention rather than limitation of the invention further.
Embodiment 1
1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- phenyl -2- (1,2,4- triazole -1- Base) -2- propylene -1- ketone (A1) preparation
The bromo- 1- of 0.14mol 2- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) ethyl ketone (Cl), 0.16mol1,2,4- triazoles, 4mmol PEG600,0.54mol potassium carbonate, 100mL ethyl acetate backflows 1.5h.Reaction solution suction filtration Obtain under brown liquid, condition of ice bath, 0.15mol nitric acid is added dropwise and obtains white precipitate, suction filtration obtains white solid, plus 500mL acetic acid second Ester dissolves, and 30%NaOH dissolvings are added dropwise, and adjusts pH to 7, and stirring to solution clarification, point liquid takes organic phase, vacuum distillation obtains 31.2g White solid 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -2- (1,2,4- triazole) ethyl ketone (Dl), Yield 88.0%, 152~155 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.57 (s, 6H, 2 × CH3), 3.11 (s, 2H, CCH2), 3.93 (s, 3H, OCH3), 5.64 (s, 2H, CH2), 7.45 (s, 1H, C6H2), 7.47 (s, 1H, C6H2), 8.04 (s, 1H, Triazole ring 3-H), 8.39 (s, 1H, triazole ring 5-H).
3.5mmol 1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -2- (1,2,4- triazole) Ethyl ketone (D1), 5.2mmol benzaldehydes and 30mL chloroforms, stirring, addition piperidines, flow back 6h.After reaction terminates, reaction solution is through water Wash, saturated common salt washing is dried, precipitation, column chromatography for separation obtains product (E)-A1 and (Z)-A1, yield 60.3%.(E)-A1：It is molten 175~177 DEG C of point,1H NMR (400MHz, CDCl3)δ：1.56 (s, 6H, 2 × CH3), 3.08 (s, 2H, CH2), 3.90 (s, 3H, OCH3), 6.95 (s, 1H, C6H24-H), 6.97 (s, 1H, C6H26-H), 7.29~7.39 (m, 5H, C6H5), 7.51 (s, 1H, C= CH), 8.17 (s, 1H, triazole ring 3-H), 8.20 (s, 1H, triazole ring 5-H)；EI-MS：376.0([M+1]+)；(Z)-A1：Fusing point 62~64 DEG C,1H NMR (400MHz, CDCl3)δ：1.48 (s, 6H, 2 × CH3), 2.93 (s, 2H, CH2), 3.85 (s, 3H, OCH3), 7.22~7.26 (m, 2H, C6H24,6-H), 7.29~7.46 (m, 5H, C6H5), 7.55 (s, 1H, C=CH), 8.07 (s, 1H, triazole ring 3-H), 8.29 (s, 1H, triazole ring 5-H)；EI-MS：376.0([M+1]+)。
Embodiment 2
(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- ketone (A2)
Be the same as Example 1 is operated, 5h, yield 67.3% is reacted.(E)-A2：158~159 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.56 (s, 6H, 2 × CH3), 2.34 (s, 3H, CH3), 3.07 (s, 2H, CH2), 3.89 (s, 3H, OCH3), 6.82 (d, J=8.0Hz, 2H, C6H43,5-H), 7.10 (d, J=8.0Hz, 2H, C6H42,6-H), 7.28 (s, 1H, C6H24-H), 7.37 (s, 1H, C6H26-H), 7.50 (s, 1H, C=CH), 8.14 (s, 1H, triazole ring 3-H), 8.18 (s, 1H, triazole ring 5-H)；(Z)-A2： 110~113 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.48 (s, 6H, 2 × CH3), 2.33 (s, 3H, CH3), 2.97 (s, 2H, CH2), 3.88 (s, 3H, OCH3), 7.02 (d, J=8.0Hz, 2H, C6H43,5-H), 7.19 (d, J=8.0Hz, 2H, C6H42, 6-H), 7.40 (s, 1H, C6H24-H), 7.47 (s, 1H, C6H26-H), 7.48 (s, 1H, C=CH), 8.05 (s, 1H, triazole ring 3- H), 8.26 (s, 1H, triazole ring 5-H).
Embodiment 3
(Z/E) -1- (7- methoxyl 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- ketone (A7)
Be the same as Example 1 is operated, 6h, yield 69.0% is reacted.(E)-A7：131~134 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.56 (s, 6H, 2 × CH3), 3.07 (s, 2H, CH2), 3.89 (s, 3H, OCH3), 6.89 (d, J=8.0Hz, 2H, C6H43,5-H), 7.28 (d, J=8.0Hz, 2H, C6H42,6-H), 7.35 (s, 1H, C6H24-H), 7.45 (s, 1H, C6H26-H), 7.50 (s, 1H, CCH), 8.17~8.18 (m, 2H, triazole rings 3,5-H)；13C NMR (100MHz, CDCl3)δ：28.19, 42.27,60.35,90.53,112.69,120.75,121.66,128.14,128.53,128.93,130.25,131.10, 132.83,134.88,137.41,144.58,145.04,152.60,189.05；(Z)-A7：85~88 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.50 (s, 6H, 2 × CH3), 2.95 (s, 2H, CH2), 3.87 (s, 3H, OCH3), 7.19 (d, J= 8.0Hz, 2H, C6H43,5-H), 7.25 (d, J=8.0Hz, 2H, C6H42,6-H), 7.30 (s, 1H, C6H24-H), 7.35 (s, 1H, C6H26-H), 7.46 (s, 1H, CCH), 8.07 (s, 1H, triazole ring 3-H), 8.25 (s, 1H, triazole ring 5-H)；13C NMR (100MHz, CDCl3)δ：28.25,42.62,56.07,89.96,112.17,122.46,122.59,128.14,128.19, 128.85,129.36,129.74,130.26,132.68,137.10,144.58,145.04,188.64.
Embodiment 4
(Z/E) -1- (7- methoxyl 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- ketone (A10)
Be the same as Example 1 is operated, 7h, yield 21.7% is reacted.(E)-A10：165~168 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.56 (s, 6H, 2 × CH3), 3.09 (s, 2H, CH2), 3.94 (s, 3H, OCH3), 7.18~7.81 (m, 4H, C6H4), 7.87 (d, J=1.2Hz, 1H, C6H24-H), 8.13 (d, J=1.2Hz, 1H, C6H26-H), 8.42 (s, 1H, C=CH), 10.17 (s, 1H, triazole ring 3-H), 10.42 (s, 1H, triazole ring 5-H)；(Z)-A10：Liquid,1H NMR (400MHz, CDCl3)δ：1.57 (s, 6H, 2 × CH3), 3.07 (s, 2H, CH2), 3.90 (s, 3H, OCH3), 7.21~7.89 (m, 4H, C6H4), 7.78 (s, 1H, C6H24-H), 8.13 (s, 1H, C6H26-H), 10.21 (s, 1H, triazole ring 3-H), 10.80 (s, 1H, triazole ring 5-H).
Embodiment 5
(Z/E) -1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (3- nitrobenzophenones) -2- The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- ketone (A11)
Be the same as Example 1 is operated, 5h, yield 43.8% is reacted.(E)-A11：154~155 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.56 (s, 6H, 2 × CH3), 3.08 (s, 2H, CH2), 3.89 (s, 3H, OCH3), 7.21~7.47 (m, 4H, C6H4), 7.48~7.51 (m, 2H, C6H24,6-H), 7.96 (s, 1H, C=CH), 8.17 (s, 1H, triazole ring 3-H), 8.22 (s, 1H, three Azoles ring 5-H)；13C NMR (100MHz, CDCl3)δ：28.21,42.52,56.05,90.13,112,67,120.89,124.79, 124.86,128.22,128.35,129.93,133.10,134.54,134.75,144.77,148.39,152.95,188.11； (Z)-A11：75~78 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.48 (s, 6H, 2 × CH3), 2.96 (s, 2H, CH2), 3.87 (s, 3H, OCH3), 7.35~7.45 (m, 4H, C6H4), 7.60~7.63 (m, 2H, C6H24,6-H), 8.10 (s, 1H, C= CH), 8.20 (s, 1H, triazole ring 3-H), 8.27 (s, 1H, triazole ring 5-H).
Embodiment 6
(Z/E) -1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- nitrobenzophenones) -2- The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- ketone (A12)
Be the same as Example 1 is operated, 8h, yield 22.6% is reacted.(E)-A12：85~88 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.56 (s, 6H, 2 × CH3), 3.07 (s, 2H, CH2), 3.89 (s, 3H, OCH3), 7.17~7.34 (m, 4H, C6H4), 7.36 (s, 1H, C6H24-H), 7.48 (s, 1H, C6H26-H), 8.10 (s, 1H, C=CH), 8.17 (s, 1H, triazole ring 3-H), 8.20 (s, 1H, triazole ring 5-H)；(Z)-A12：78~80 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.50 (s, 6H, 2 × CH3), 2.96 (s, 2H, CH2), 3.89 (s, 3H, OCH3), 7.46~7.48 (m, 4H, C6H4), 7.63 (s, 1H, C6H24-H), 8.09 (s, 1H, C6H26-H), 8.12 (s, 1H, C=CH), 8.15 (s, 1H, triazole ring 3-H), 8.24 (s, 1H, triazole ring 5-H).
Embodiment 7
(Z/E) -1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- methoxyphenyls) - The preparation of 2- (1,2,4- triazol-1-yl) -2- propylene -1- ketone (A15)
Be the same as Example 1 is operated, 7h, yield 20.8% is reacted.(E)-A15：50~53 DEG C of fusing point,1H NMR (400MHz, CDCl3)δ：1.40 (t, J=6.8Hz, 3H, CH3), 1.47 (s, 6H, 2 × CH3), 3.07 (s, 2H, CH2), 3.80 (s, 3H, CH3), 4.13 (q, J=6.8Hz, 2H, CH2), 6.78~6.91 (m, 2H, C6H24,6-H), 7.33~7.40 (m, 4H, C6H4), 7.80 (s, 1H, CCH), 8.08 (s, 1H, triazole ring 3-H), 8.21 (s, 1H, triazole ring 5-H)；(Z)-A15：Fusing point 127~130 DEG C,1H NMR (400MHz, CDCl3)δ：1.44 (t, J=6.8Hz, 3H, CH3), 1.56 (s, 6H, 2 × CH3), 2.90 (s, 2H, CH2), 3.80 (s, 3H, CH3), 4.04 (q, J=6.8Hz, 2H, CH2), 6.01~6.76 (m, 2H, C6H2, 7.14 4,6-H)~ 7.20 (m, 4H, C6H4), 7.72 (s, 1H, CCH), 8.16 (s, 1H, triazole ring 3-H), 8.38 (s, 1H, triazole ring 5-H).
Embodiment 8
(Z/E) -1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- fluorophenyls) -2- The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- ketone (A17)
Be the same as Example 1 is operated, 5h, yield 53.3% is reacted.(E)-A17：M.p.140~143 DEG C,1H NMR (400MHz, CDCl3)δ：1.45 (t, J=6.8Hz, 3H, CH3), 1.56 (s, 6H, 2 × CH3), 3.07 (s, 2H, CH2), 4.13 (q, J= 6.8Hz, 2H, CH2), 6.93~7.02 (m, 4H, C6H4), 7.28 (s, 1H, C6H24-H), 7.35 (s, 1H, C6H26-H), 7.49 (s, 1H, C=CH), 8.21 (s, 2H, triazole rings 3,5-H)；ESI-MS：408.2([M+1]+)；(Z)-A17：M.p.54~58 DEG C,1H NMR (400MHz, CDCl3)δ：1.42 (t, J=6.8Hz, 3H, CH3), 1.50 (s, 6H, 2 × CH3), 2.94 (s, 2H, CH2), 4.10 (q, J=6.8Hz, 2H, CH2), 6.92~7.00 (m, 4H, C6H4), 7.29 (s, 1H, C6H24-H), 7.31 (s, 1H, C6H26-H), 7.44 (s, 1H, C=CH), 8.14 (s, 1H, triazole ring 3-H), 8.40 (s, 1H, triazole ring 5-H)；ESI-MS： 408.2([M+1]+)。
Embodiment 9
(Z/E) -1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- chlorphenyls) -2- The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- ketone (A19)
Be the same as Example 1 is operated, 4h, yield 38.9% is reacted.(E)-A19：M.p.125~128 DEG C,1H NMR (400MHz, CDCl3)δ：1.43 (t, J=6.8Hz, 3H, CH3), 1.56 (s, 6H, 2 × CH3), 3.07 (s, 2H, CH2), 4.10 (q, J= 6.8Hz, 2H, CH2), 6.89 (s, 1H, C6H24-H), 6.90 (s, 1H, C6H26-H), 7.19~7.34 (m, 4H, C6H4), 7.85 (s, 1H, C=CH), 8.22 (s, 1H, triazole ring 3-H), 8.25 (s, 1H, triazole ring 5-H)；(Z)-A19：M.p.50~52 DEG C,1H NMR (400MHz, CDCl3)δ：1.43 (t, J=6.8Hz, 3H, CH3), 1.50 (s, 6H, 2 × CH3), 2.94 (s, 2H, CH2), 4.10 (q, J=6.8Hz, 2H, CH2), 7.22 (s, 2H, C6H24,6-H), 7.45 (d, J=8.0Hz, 2H, C6H43,5-H), 7.54 (d, J=8.0Hz, 2H, C6H42,6-H), 7.83 (s, 1H, C=CH), 8.11 (s, 1H, triazole ring 3-H), 8.31 (s, 1H, triazole Ring 5-H).
Embodiment 10
(Z/E) -1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- bromophenyls) -2- The preparation of (1,2,4- triazol-1-yl) -2- propylene -1- ketone (A21)
Be the same as Example 1 is operated, 5h, yield 54.1% is reacted.(E)-A21：M.p.153~156 DEG C,1H NMR (400MHz, CDCl3)δ：1.43 (t, J=7.2Hz, 3H, CH3), 1.56 (s, 6H, 2 × CH3), 3.07 (s, 2H, CH2), 4.12 (q, J= 6.8Hz, 2H, CH2), 6.80 (s, 1H, C6H24-H), 6.82 (s, 1H, C6H26-H), 7.28 (s, 1H, C=CH), 7.35~7.46 (m, 4H, C6H4), 8.19~8.22 (m, 2H, triazole rings 3,5-H)；(Z)-A21：M.p.48~51 DEG C,1H NMR (400MHz, CDCl3)δ：1.43 (t, J=7.2Hz, 3H, CH3), 1.51 (s, 6H, 2 × CH3), 2.94 (s, 2H, CH2), 4.10 (q, J= 6.8Hz, 2H, CH2), 7.16 (s, 1H, C6H24-H), 7.18 (s, 1H, C6H26-H), 7.34~7.50 (m, 4H, C6H4), 7.49 (s, 1H, C=CH), 8.10 (s, 1H, triazole ring 3-H), 8.30 (s, 1H, triazole ring 5-H).
Embodiment 11
The Herbicidal of furans amphyl containing triazolyl
Test sample：Furans amphyl containing triazolyl：
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 or nitro；X3It is selected from：Hydrogen, C1~C2Alkyl, fluorine, chlorine, bromine, iodine or nitro；X2、X4It is selected from：Hydrogen, C1~C2Alkyl or nitro.
Method of testing is shown in CN102105460A.
Tested weeds：Creeping bentgrass (Agrostis stolonifera, AGSST), odorless german chamomile (Tripleurospermum maritimum, MATIN) and annual bluegrass (Poa annua, POAAN).
Indoor general sieve compound：Culture vessel uses plastic tub alms bowl, and interior filling loamy sand and about 3.0% humus are made For culture medium, the seed of various test plants is sowed in basin alms bowl respectively.
Before seedling soil treatment (pre)：Suspend or be emulsifiable in the active component in water and sowing is uniformly sprayed at by spray nozzle Soil surface afterwards, and moisturizing is carried out to promote germination and growth to basin alms bowl, basin alms bowl is then covered with blister pack straight To plant establishment germination.Test plant can normally germinate, unless destroyed by active component.
After seedling cauline leaf process (post)：Test plant first grows into 3~15cm high (habit for depending on different plants), so Carry out after seedling cauline leaf process with the active component for suspending or being emulsifiable in water again afterwards.Test plant can be directly in same basin alms bowl Middle sowing and growth, can also first respectively length emerge, then before treatment several days again culture transferring to for examination basin alms bowl in.
According to the difference of target, the condition of culture of test plant is 10~25 DEG C or 20~35 DEG C of temperature, the testing time 2~ 4 weeks.During this period, growing state is taken care of and assessed to test plant.Inhibitory activity evaluation is using 0~100 scoring, 100 Refer to that no plant grows, or the cauline leaf of soil top is destroyed completely, 0 expression plant germination is not destroyed, or plant is just It is frequently grown.It is at least 70 with good activity of weeding, is at least 85 with extraordinary activity of weeding.
Test concentrations：2000g/ha (gram/acre).
Activity of weeding test result is shown：The after seedling stem of compound Z-A11, Z-A12, E-A15 and E-A17 to odorless german chamomile Leaf growth has preferable inhibitory activity, and inhibitory activity scoring is 80 points；Compound Z-A7 and E-A19 is to odorless german chamomile after seedling cauline leaf Growth has extraordinary inhibitory activity, and scoring is respectively 85 and 98 points；Before seedling soil treatments of the compound Z-A21 to odorless german chamomile There is certain inhibitory activity (65 points)；After seedling cauline leaf growths of the compound Z-A2 and Z-A10 to annual bluegrass has certain inhibitory activity, comments It is 60 points to divide.Furans amphyl containing triazolyl can be used as the application for preparing herbicide.

Claims (2)

1. chemical constitution Formulas I or furans amphyl containing triazolyl shown in II or its salt remove odorless german chamomile or precocity preparing Application in the herbicide of standing grain：
Wherein, R is selected from：Methyl or ethyl；X1、X5It is selected from：Hydrogen, methoxyl group or nitro；X3It is selected from：Hydrogen, methyl, fluorine, chlorine, bromine or Nitro；X2、X4It is selected from：Hydrogen or nitro；Its salt is selected from：Hydrochloride, hydrobromate, sulfate, nitrate, phosphate, methanesulfonic acid Salt, benzene sulfonate, tosilate, malate, lactate, succinate or butene dioic acid salt.
2. the furans amphyl containing triazolyl shown in the application described in claim 1, wherein Formulas I or II is selected from：
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- ketone,
1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- chlorphenyls) -2- (1,2,4- triazole - 1- yls) -2- propylene -1- ketone,
1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- nitrobenzophenones) -2- (1,2,4- tri- Azoles -1- bases) -2- propylene -1- ketone,
1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (3- nitrobenzophenones) -2- (1,2,4- tri- Azoles -1- bases) -2- propylene -1- ketone,
1- (7- methoxyl group -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- nitrobenzophenones) -2- (1,2,4- tri- Azoles -1- bases) -2- propylene -1- ketone,
1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (2- methoxyphenyls) -2- (1,2,4- Triazol-1-yl) -2- propylene -1- ketone,
1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- fluorophenyls) -2- (1,2,4- triazole - 1- yls) -2- propylene -1- ketone,
1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- chlorphenyls) -2- (1,2,4- triazole - 1- yls) -2- propylene -1- ketone or
1- (7- ethyoxyl -2,2- dimethyl -2,3- Dihydrobenzofuranes -5- bases) -3- (4- bromophenyls) -2- (1,2,4- triazole - 1- yls) -2- propylene -1- ketone.
CN201510064706.9A 2015-02-04 2015-02-04 The preparation and application of furans amphyl containing triazolyl Expired - Fee Related CN104610236B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510064706.9A CN104610236B (en) 2015-02-04 2015-02-04 The preparation and application of furans amphyl containing triazolyl

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510064706.9A CN104610236B (en) 2015-02-04 2015-02-04 The preparation and application of furans amphyl containing triazolyl

Publications (2)

Publication Number Publication Date
CN104610236A CN104610236A (en) 2015-05-13
CN104610236B true CN104610236B (en) 2017-08-04

Family

ID=53144916

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510064706.9A Expired - Fee Related CN104610236B (en) 2015-02-04 2015-02-04 The preparation and application of furans amphyl containing triazolyl

Country Status (1)

Country Link
CN (1) CN104610236B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102603726A (en) * 2012-01-18 2012-07-25 湖南化工研究院 5-(2-aminothiazole-4-yl) benzofuranol etheric compound with herbicidal activity and preparation method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102603726A (en) * 2012-01-18 2012-07-25 湖南化工研究院 5-(2-aminothiazole-4-yl) benzofuranol etheric compound with herbicidal activity and preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
4-(7-甲氧基-2,2-二甲基-2,3-二氢苯并呋喃-5-基)-2-苄亚氨基噻唑的合成与生物活性;沈芳等;《有机化学》;20121231;第32卷(第2期);388-392 *

Also Published As

Publication number Publication date
CN104610236A (en) 2015-05-13

Similar Documents

Publication Publication Date Title
US4837242A (en) Thiazoles and pyrazoles as fungicides
CN104163791B (en) N-pyridine (hetero) aryl amide compound and preparation method and application thereof
US5004816A (en) Aminopyrrole intermediates for fungicides
WO2007129454A1 (en) 1,2-benzisothiazole derivative, and agricultural or horticultural plant disease-controlling agent
JP7082709B2 (en) Quinazoline dione compounds, their use and pesticide herbicides
CN102816150B (en) Indole with bacteriostatic activity and derivatives thereof-triazole compounds, and preparation method thereof
RU2067395C1 (en) Iminothiazoline compounds, herbicide composition and weed control method
DE1964995A1 (en) N-Benzyltriazoles, process for their preparation and their use for regulating plant growth
CN104530036A (en) 5-piperonyl-4-alkyl-2-benzyliminothiazole and preparing method and application thereof
CN104610236B (en) The preparation and application of furans amphyl containing triazolyl
CN104557888B (en) Application of furan phenol allyl alcohol derivative used as herbicide
CN104072455A (en) 6-aryloxy acetoxy aurone compound and application thereof on pesticide
WO1997012863A1 (en) α-SUBSTITUTED BENZYL HETEROCYCLIC DERIVATIVES, INTERMEDIATES FOR PRODUCING THE SAME, AND PESTICIDES CONTAINING THE SAME AS ACTIVE INGREDIENT
CN107629012B (en) Phenazine-1-carboxylic acid bisamide compound and application thereof
CN105859698B (en) N- (oxoethyl) -2- [4- (pyridine -2- bases epoxide) phenoxy group] amide derivatives
BG97615A (en) New fungicides - derivatives of triazol and imidazole
CN104496973B (en) Benzofuranol propenone derivatives is as the application of insecticide
CN105859696B (en) 1- benzofuranols ether -3- phenyl -2- (1,2,4- triazol-1-yl) -2- propenone and its application
CN105859707B (en) (R)-N- (thiazol-2-yl) -2- [4- (quinoxaline -2- oxygroups) phenoxy group] amide derivatives and its preparation method and application
JPH02108686A (en) Substituted dioxoranylethylamine, its production, harmful organism control agent and novel intermediate product
JPWO2004022546A1 (en) Substances that inhibit the biosynthesis of jasmonic acid
CN106478613B (en) 2- [4- (pyridine -2- base oxygroup) phenoxy group] amide derivatives and the preparation method and application thereof
JPS6168487A (en) Carbamoylazole derivative, its production, and herbicide comprising it as active ingredient
CN114634456B (en) 5-nitroimino-4H-1, 2, 4-triazole compound and preparation method and application thereof
PT87371B (en) Process for the preparation of a fungicidal composition containing substituted and unsubstituted aminomethylheterocyclic derivatives and of novel derivatives substituted aminomethylheterocyclic derivatives

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170804

Termination date: 20180204

CF01 Termination of patent right due to non-payment of annual fee