CN107459515A - A kind of chiral 5,6-tetrahydropyridine derivative and its production and use - Google Patents
A kind of chiral 5,6-tetrahydropyridine derivative and its production and use Download PDFInfo
- Publication number
- CN107459515A CN107459515A CN201610402574.0A CN201610402574A CN107459515A CN 107459515 A CN107459515 A CN 107459515A CN 201610402574 A CN201610402574 A CN 201610402574A CN 107459515 A CN107459515 A CN 107459515A
- Authority
- CN
- China
- Prior art keywords
- agent
- chiral
- zyj05
- rice
- plant
- 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.)
- Pending
Links
- 0 CC(C(C1)C(*)=O)C=C(*)[N+]1S(c1ccccc1)(O)=O Chemical compound CC(C(C1)C(*)=O)C=C(*)[N+]1S(c1ccccc1)(O)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a kind of chiral 5,6-tetrahydropyridine derivative and its production and use, and the present invention relates to the tetrahydropyridine analog derivative of 4 thiazole 1,2,3,4, and they have the chemical structure of general formula as shown in I.
Description
Technical field
Technical scheme is related to 1,2,3,4- 5,6-tetrahydropyridine derivatives of chiral nitrogenous sulfur-bearing, and in particular to 4- thiophenes
Azoles -1,2,3,4- tetrahydropyridine analog derivatives.
Background technology
Heterocyclic compound is the important sources of novel pesticide guide, and wherein nitrogen-containing heterocycle compound has extensive bioactivity
Such as desinsection, sterilization, weeding, antiviral, active anticancer；Thiazole compound as nitrogenous heterocyclic important component, because
Its unique architectural feature and be widely used in agricultural chemicals and field of medicaments, desinsection (mite killing) agent of many commercializations, kill
Microbial inoculum and herbicide all (Sun little Jun, wait to have the progress of thiazole heterocyclic compounds of bioactivity containing thiazole ring
Agriculture of Anhui science, 2008,36 (33)：14389-14393).Pyridine compounds and their is due to its unique physicochemical property and biology
Activity had a wide range of applications in drug research field (Fan Zhijin, etc., one kind containing 1,2,3- thiadiazoles pyridine derivatives and
Preparation method and use, People's Republic of China's national inventing patent, Granted publication date：On March 4th, 2015, authorize public
Announcement number：CN103012392B), the pyridine research hydrogenated is relatively fewer, and wherein tetrahydropyridines also have potential
Bioactivity, there is good application prospect in terms of biological medicine, agricultural chemicals and organic synthesis.
The present invention is set using the principle of pesticide molecule design using Aza-Rauhut-Currier reaction cis-selectivities
Meter has synthesized a kind of chiral 5,6-tetrahydropyridine derivative, and has carried out preliminary bioactivity screening, to the initiative for novel pesticide
More efficient candidate compounds are provided.
The content of the invention
The technical problems to be solved by the invention are：The synthetic method of new chiral 5,6-tetrahydropyridine derivative is provided, there is provided
This kind of compound modulates agricultural, gardening and health and the bioactivity and its measure side of forestry plant insect and the phytopathy original
Method, while middle application of these compounds in agriculture field, horticultural field, field of forestry and health field is provided.
Technical scheme is used by the present invention solves the technical problem：With agriculture field, horticultural field, forestry and
Health field insecticidal activity, the general structure of chiral 5,6-tetrahydropyridine derivative of bactericidal activity are I：
Wherein：R1Selected from ethyl, benzyl, 4- methyl-benzyls, thiophene -2- bases, furans -2- bases, cyclohexyl, 4- fluoroforms
Base phenyl；R2Selected from 2- (4 '-tertiary butyl oxycarbonyl piperidines) thiazole-4-yl, 4- methylthiazol -5- bases, thiazole-4-yl；R3It is selected from
4- methoxyphenyls, phenyl, 4- nitrobenzophenones, cyclopropyl；
According to the difference of the substituent on thiazole, by R2After materialization, chiral 5,6-tetrahydropyridine derivative I of the invention points are
Following three type：
Wherein：R1Selected from ethyl, benzyl, 4- methyl-benzyls, thiophene -2- bases, furans -2- bases, cyclohexyl, 4- fluoroforms
Base phenyl；R3Selected from 4- methoxyphenyls, phenyl, 4- nitrobenzophenones, cyclopropyl；
The chiral 5,6-tetrahydropyridine derivative I of present invention synthetic method is as follows：
Wherein：R1Selected from ethyl, benzyl, 4- methyl-benzyls, thiophene -2- bases, furans -2- bases, cyclohexyl, 4- fluoroforms
Base phenyl；R2Selected from 2- (4 '-tertiary butyl oxycarbonyl piperidines) thiazole-4-yl, 4- methylthiazol -5- bases, thiazole-4-yl；R3It is selected from
4- methoxyphenyls, phenyl, 4- nitrobenzophenones, cyclopropyl；PPh3It is triphenylphosphine；
A. chiral 5,6-tetrahydropyridine derivative I preparation：
Sequentially add nitrogenous sulfur-bearing sulfimide derivative II into 100 milliliters of round-bottomed flasks, the triphenylphosphine of catalytic amount,
The 4- metoxyphenols of catalytic amount, are finally slowly added dropwise R1Corresponding ketene compound, the catalytic amount refer to mole as chirality
The 5%-20%, R of 5,6-tetrahydropyridine derivative II moles1The mole of corresponding ketene compound is nitrogenous sulfur-bearing sulfimide
1-5 times of derivative I I moles, reacted 24 hours in 30 degrees Centigrades；After reaction completely, residue is through 200~300 mesh
Silica gel column chromatography purifies to obtain chiral 5,6-tetrahydropyridine derivative I, yield 60-95%, and eluant, eluent is 60~90 degrees Celsius of petroleum ether:
Ethyl acetate, according to the difference of product, volume ratio 10: 1-6: 1；Amount and reaction prepared by chiral 5,6-tetrahydropyridine derivative I is held
The volume of device is expanded or shunk by corresponding proportion.
B. chiral 5,6-tetrahydropyridine derivative I of the invention bactericidal activity measure：
The chiral 5,6-tetrahydropyridine derivative I of present invention sterilization or bacteriostatic activity use thalli growth rate determination method, specifically
Step is：Take 1.8 milligrams of samples to be dissolved in 2 drop DMFs, then use and contain a certain amount of polysorbas20 emulsifying agent
The aqueous solution be diluted to the medicaments of 500 mcg/mls, reagent agent is aseptically respectively drawn to 1 milliliter in culture dish,
9 milliliters of PDA culture mediums are separately added into again, 50 mcg/ml drug containing flat boards are made after shaking up, with the flat of 1 milliliter of aqua sterilisa of addition
Plate does blank control, cuts bacterium disk along mycelia outer rim with 4 millimeters of card punch of diameter, moves on drug containing flat board, in equilateral triangle
Shape is put, and often processing is repeated 3 times, and culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivated, and colony diameter to be compareed expands
Each processing bacterium disk extension diameter is investigated after opening up 2-3 centimetres, averages, relative bacteriostasis rate is calculated compared with blank control, is supplied
Examination strain is the kind of most of typical plant pathogen that field actually occurs in China's agricultural production, and its code name and title are such as
Under：AS：Tomato early blight bacterium, its Latin are entitled：Alternaria solani、BC：Botrytis cinerea pers, its Latin are entitled：
Botrytis cinerea、CA：Peanut Cercospora bacteria, its Latin are entitled：Cercospora arachidicola、GZ：Wheat is red
Mildew bacterium, its Latin are entitled：Gibberella zeae、PI：Phytophthora infestans, its Latin are entitled：Phytophthora
infestans(Mont.)de Bary、PP：Botryosphaeria berengeriana f. sp, its Latin are entitled：Physalospora piricola、PS：
Rhizoctonia solani Kuhn, its Latin are entitled：Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin are entitled：
Rhizoctonia cerealis、SS：Sclerotinia sclerotiorum, its Latin are entitled：Sclerotinia sclerotiorum.
C. the measure of chiral 5,6-tetrahydropyridine derivative I of the invention to aphid cytotoxicity：
The chiral 5,6-tetrahydropyridine derivative I of the present invention uses infusion process to the measure of aphid cytotoxicity, and black bean aphid is room
The normal population of interior raising, the entitled Aphis laburni Kaltenbach (ALK) of Latin；Weigh 2.5 milligrams of test compound
In beaker, 1 drop DMF is added dropwise, be i.e. DMF, adds 5 milliliters of acetone vibration dissolving samples, has added Tween 80
Water be made into the solution to be measured of 200 mcg/mls；The bean plant that supplies to try with least 30 black bean aphids is cut from basin,
Being impregnated 5 seconds in each decoction to be measured, unnecessary decoction is gently got rid of in taking-up, is inserted in by moisturizing on water saturated sponge,
Escaped after decoction natural air drying with cloche cover, the opening of cloche upper end is sealed with gauze to prevent aphid, in culturing room
Interior raising checks aphid death state after 72 hours, and standard is：It can be creeped or can stood or six Tiao Tuineng strenuous exercises with test worm
Be worm living；Using clear water as control, corrected mortality is calculated.
The beneficial effects of the invention are as follows：Chiral 5,6-tetrahydropyridine derivative I has carried out guide's optimization, and to 4- thiazole -1,
2,3,4- tetrahydropyridines have carried out the screening of insecticidal activity, bacteriostatic activity.
The present invention passes through specific preparation and the more specific chiral 5,6-tetrahydropyridine derivative I of explanation of biological activity determination embodiment
Synthesis and bioactivity and application, the embodiment, which is only used for illustrating the present invention, to be not intended to limit the present invention, especially raw
Thing activity is merely illustrative of, and unrestricted this patent, embodiment are as follows：
Embodiment 1
The chiral 5,6-tetrahydropyridine derivative I of present invention preparation：
0.18 mM of nitrogenous sulfur-bearing sulfimide derivative II, 0.07 milli are sequentially added into 100 milliliters of round-bottomed flasks
Mole triphenylphosphine, 0.07 mM of 4- metoxyphenol, is finally slowly added dropwise 0.56 mM of R1Corresponding ketene compound,
Reacted 24 hours in 30 degrees Centigrades；Reaction completely after, residue through 200~300 mesh silica gel column chromatographies purify chiral four
Pyridinium hydroxide derivative I, yield 60-95%, eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, according to substituent
Difference, volume ratio 10: 1-6: 1, according to the difference of product, chiral 5,6-tetrahydropyridine derivative I yield is 60-95%；It is chiral
Amount and the volume of reaction vessel prepared by 5,6-tetrahydropyridine derivative I is expanded or shunk by corresponding proportion；Its physical and chemical parameter and structure
Parameter is shown in Table 1.
Embodiment 2
The chiral 5,6-tetrahydropyridine derivative I of present invention Antibacterial Activity result：
The code name and title for the frequently seen plants disease fungus that the present invention tests are as follows：AS：Tomato early blight bacterium, its latin name
For：Alternaria solani、BC：Botrytis cinerea pers, its Latin are entitled：Botrytis cinerea、CA：Peanut foxiness
Germ, its Latin are entitled：Cercospora arachidicola、GZ：Fusarium graminearum, its Latin are entitled：Gibberella
zeae、PI：Phytophthora infestans, its Latin are entitled：Phytophthora infestans(Mont.)de Bary、PP：Apple
Fruit Target spot pathogen, its Latin are entitled：Physalospora piricola、PS：Rhizoctonia solani Kuhn, its Latin are entitled：
Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin are entitled：Rhizoctonia cerealis、SS：Sclerotina Sclerotiorum in Winter Rape
Core germ, its Latin are entitled：Sclerotinia sclerotiorum, these strains have representativeness well, can represented
The kind for most of pathogen that field occurs in agricultural production.
It is worth noting that compound zyj05-105 is document Zugui Shi, Peiyuan Yu, Teck- in the present invention
Peng Loh, and Guofu Zhong, Catalytic asymmetric [4+2] annulation initiated by an
Aza-Rauhut-Currier reaction：Facile entry to highly functionalized
Tetrahydropyridines, Angew.Chem.Int.Ed.2012,51, the structure reported in 7825-7829 and the present invention
The immediate known compound of target compound structure, compound lfy006-39 are to be reported in patent document WO2008091594
High activity known compound, compound lfy004-47 is knownization of high activity reported in patent CN104650060A
Compound, for the bioactivity of the noval chemical compound more of the invention synthesized, the present invention has synthesized structure closest to target of the present invention
Known compound zyj05-105, lfy006-39 and lfy004-47 of compound, and carry out activity with target compound of the present invention
Compare.
Thalli growth rate method measurement result is shown in Table 2, and table 2 shows, in 50 mcg/ml, all hands of the invention synthesized
Property 5,6-tetrahydropyridine derivative I has different degrees of bactericidal activity, and the chiral 5,6-tetrahydropyridine derivative I of major part of the invention has
The activity of preferable bactericidal activity.For tomato early blight bacterium, compound zyj05-37, zyj05-39, zyj05-60,
Zyj05-86, zyj05-83, zyj05-112, zyj05-113 and zyj05-120 inhibitory activity are more than 35%, above-mentioned chemical combination
The thing bactericidal activity compound lfy004-47 similar higher than document report structure is more than 10%, wherein compound zyj05-
60th, zyj05-86 and zyj05-120 activity is more than 40%, and bactericidal activity is higher than document report and target chemical combination of the present invention
The immediate known compound zyj05-105 and lfy006-39 of chemical structure is more than 10%；To peanut Cercospora asparagagas
Speech, compound zyj05-37, zyj05-36, zyj05-62, zyj05-57, zyj05-38, zyj05-84, zyj05-86,
Zyj05-83, zyj05-89 and zyj05-112 inhibitory activity are more than 40%, and bactericidal activity is higher than document report and this hair
The immediate compound lfy006-39 and lfy004-47 of improving eyesight mark compound chemical structure is more than 20%, above-claimed cpd
Zyj05-37, zyj05-86, zyj05-83 and zyj05-120 bactericidal activity are higher than 50%, and bactericidal activity is higher than document report
With the immediate known compound zyj05-105 of target compound chemical constitution of the present invention more than 10%；To gibberella saubinetii
For germ, compound zyj05-25, zyj05-60, zyj05-81, zyj05-90 and zyj05-86 inhibitory activity are 40%
More than, and the bactericidal activity of above-claimed cpd is immediate with target compound chemical constitution of the present invention higher than document report
Know compound zyj05-105, lfy006-39, more than lfy004-4710%；For Botryosphaeria berengeriana f. sp, compound zyj05-
39 and zyj05-90 inhibitory activity more than 50%, the bactericidal activity of above-claimed cpd be significantly higher than document report with this
Subject invention compound chemical structure immediate known compound zyj05-105, and bactericidal activity higher than document report with
The immediate compound lfy006-39 of target compound chemical constitution of the present invention is more than 10%, compound zyj05-120 work
Property be 78.69%, it is immediate with target compound chemical constitution of the present invention higher than document report to be significantly higher than bactericidal activity
Compound lfy004-47；For Sclerotinia sclerotiorum, compound zyj05-37, zyj05-36, zyj05-39, zyj05-25,
For zyj05-86, zyj05-101, zyj05-113 and zyj05-120 inhibitory activity more than 50%, bactericidal activity is higher than document
Report with the immediate known compound zyj05-105 of target compound chemical constitution of the present invention, and compound zyj05-25,
Zyj05-101, zyj05-120 bactericidal activity are higher than the similar compound zyj05-105 of document report structure more than 10%,
Compound zyj05-25, zyj05-101 and zyj05-120 activity more than 60%, bactericidal activity higher than document report with
The immediate compound lfy006-39 of target compound chemical constitution of the present invention and compound lfy004-47, zyj05-25 work
Property is up to 93.85%；For botrytis cinerea pers, compound zyj05-57, zyj05-25, zyj05-81, zyj05-90,
Zyj05-83 and zyj05-101 inhibitory activity more than 50%, the bactericidal activity of above-claimed cpd higher than document report with
The immediate compound lfy006-39 of target compound chemical constitution of the present invention more than 10%, and compound zyj05-57,
Zyj05-81, zyj05-83, zyj05-101 bactericidal activity are higher than document report and target compound chemical constitution of the present invention
Immediate known compound zyj05-105 is more than 10%, and compound zyj05-81 activity is up to 91.07%, activity
Close to compound lfy004-47；For Phytophthora infestans, compound zyj05-37, zyj05-86 and zyj05-83's
Inhibitory activity is more than 30%, and the bactericidal activity of above-claimed cpd is higher than document report and target compound of the present invention chemistry
The immediate known compound zyj05-105 of structure；For Rhizoctonia cerealis, compound zyj05-54, zyj05-60,
Zyj05-86, zyj05-83, zyj05-122, zyj05-121 and zyj05-120 inhibitory activity are more than 60%, bactericidal activity
It is suitable with the immediate known compound zyj05-105 of target compound chemical constitution of the present invention with document report, and chemical combination
Thing zyj05-86 bactericidal activity is higher than document report and the immediate known chemical combination of target compound chemical constitution of the present invention
Thing zyj05-105 is more than 10%；For Rhizoctonia solani Kuhn, compound zyj05-60, zyj05-81, zyj05-83,
Zyj05-121 and zyj05-120 activity is more than 30%, and the bactericidal activity of above-claimed cpd is higher than document report and this hair
The immediate compound lfy006-39 of improving eyesight mark compound chemical structure is more than 10%, and bactericidal activity is higher than document report
Road with the immediate known compound zyj05-105 of target compound chemical constitution of the present invention.
Embodiment 3
The chiral 5,6-tetrahydropyridine derivative I insecticidal activities of the present invention：
Chiral 5,6-tetrahydropyridine derivative I insecticidal activity assay the results are shown in Table 3, and table 3 is visible：The chiral tetrahydrochysene pyrrole of the present invention
Piperidine derivatives I has preferable insecticidal activity, when reagent agent concentration is 100 mg/litre, after observation acts on 72 hours, changes
Compound zyj05-37, zyj05-36, zyj05-57, zyj05-38, zyj05-61, zyj05-54, zyj05-91, zyj05-60,
Zyj05-81, zyj05-85, zyj05-83, zyj05-101, zyj05-118, zyj05-122, zyj05-121 and zyj05-120
Activity more than 30%, insecticidal activity is immediate with target compound chemical constitution of the present invention higher than document report
Know compound zyj05-105, wherein compound zyj05-37, zyj05-36, zyj05-57, zyj05-38, zyj05-61,
Zyj05-54, zyj05-85, zyj05-83, zyj05-118, zyj05-122, zyj05-121 and zyj05-120 activity exist
More than 40%, the insecticidal activity of above-claimed cpd is immediate with target compound chemical constitution of the present invention higher than document report
Known compound zyj05-105 is more than 10%, and compound zyj05-83 activity is up to 70.28%.
The chiral 5,6-tetrahydropyridine derivative I of the present invention is also to Orthoptera, Isoptera, Semiptera, Homoptera, Thysanoptera, sheath
Wing mesh, Lepidoptera, Neuroptera, Diptera, Hymenoptera and the agricultural of Acarina and forestry and gardening plant insect evil mite have
Good insecticidal activity.
Embodiment 4
The chiral 5,6-tetrahydropyridine derivative I of the present invention is with insecticide composition in preventing and treating agricultural and forestry and gardening plant worm
Application in evil：
All chiral 5,6-tetrahydropyridine derivative I of the present invention combine formation with any one in commodity insecticide or two kinds
Pesticidal combination is used to prevent and treat agricultural and forestry and gardening plant insect pest, and the commodity insecticide is selected from：Chlopyrifos, it is sub-
Nong, Acetamiprid, emamectin benzoate, milbemectin, AVM, pleocidin, fenvalerate, esfenvalerate, chlorine
Cyano chrysanthemate, effective cypermethrin, Cyhalothrin, decis, Fenpropathrin, Beta- cyfloxylates, Lambda- tri-
Cyfloxylate, Permanone, permethrin, allethrin, Biphenthrin, Permethrin, ethofenprox, flumethrin,
Fluvalinate, imidacloprid, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Te
South, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization are grand, HEXAFLUMURON, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron,
Noviflumuron is noviflumuron, its No. CAS be 121451-02-3, flucycloxuron, Novaluron be Rimon, chlorfluazuron,
Bay sir 6874 are that { 1- [(3.5- bis- chloro- 4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzenes)-urea }, Bay SIR-8514 are
[1- (4- Trifluoromethoxyphen-ls) -3- (2- chlorobenzenes)-urea], piperazine worm urea, Bistrifluron are bistrifluron, furans worm acyl
Hydrazine, tebufenozide, chlorine tebufenozide, methoxyfenozide, ring tebufenozide, Rogor, flolimat, DDVP, orthene, triazole
Phosphorus, quinalphos, pyridaphethione, isazofos, isoprocarb, sevin, Aphox, MTMC, Mobucin, cartap, Bassa, leaf
Disperse, carbaryl, Benfuracard micro, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine,
Propargite, diafenthiuron, pymetrozine, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, phonamiphos,
Ethiprole, Cupric sulfate, dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, chlorfenapyr, pyrrole
Piperazine ketone, etoxazole, tebufenpyrad, rattle away young ketone, Nylar, emaricin；The chiral 5,6-tetrahydropyridine derivative I of the present invention kills described
Weight/mass percentage composition in worm composition is 1%-90%, chiral 5,6-tetrahydropyridine derivative I of the invention and foregoing commodity desinsection
The ratio of agent is mass percent 1%: 99% to 99%: 1%；The formulation of the Pesticidal combination processing is selected from：Seed treatment
Emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick agent, poison grain, block poison
Bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smoke candle, smoke candle, smog
Cylinder, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol, the agent of solid-liquid mixing dress, liquid liquid
Solid mixing dress agent, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil-dispersing property pulvis, dense jelly, bold and vigorous pour
Agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；The plant worm of the Pesticidal combination preventing and treating
Evil is selected from：Red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, Oriental burmeister, rice thripses,
Onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipes thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, cotton leaf
Cicada, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle plant hopper of sugarcane, cotten aphid, green bugs, grain aphid, black peach aphid,
Kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, perfume (or spice)
Any of several broadleaf plants lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, green rice bug, green plant bug, clover are blind
Stinkbug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, brown slug moth, thosea siensis, gelechiid, the red bell of cotton
Worm, brachmia triannuella, diamondback moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roll
Moth, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, corn borer, yellow rice borer, Oeobia undalis, rice leaf roller, bar snout moth's larva, Notarchaderogata,
Dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point spark, small ground are old
Brave, big cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, citrus
Swallowtail butterfly, Common Mormon, cabbage butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle,
It is the small buprestid beetle of pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, citrus, golden edge buprestid beetle, yellow meal worm, dark mealworm, red
Intend ostomatid, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori,
Pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice
As, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hang cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart
Ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melonfly, the latent fly of wheat leaf ash, America
Liriomyza bryoniae, Soybean stem borer, frit fly, Hylemyia Platura Meigen, onion fly, radish fly, full skirt Exorista civilis, corn borer are strict to post fly, armyworm；It is described to kill
The plant of worm composition for preventing and controlling is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, lotus
Lan Dou, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa,
Ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, oil
Dish, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper,
Banana, papaya, orchid, potted landscape.
Embodiment 5
The chiral 5,6-tetrahydropyridine derivative I of the present invention is with antimicrobial combination in preventing and treating agricultural and forestry and gardening plant disease
Application in evil：
All chiral 5,6-tetrahydropyridine derivative I of the present invention combine formation with any one in commodity bactericide or two kinds
Bactericidal composition is used to prevent and treat agricultural and forestry and gardening plant disease, and the commodity bactericide is selected from：Diazosulfide, thiophene
Acyl bacterium amine, it is abbreviated as TDL, tisocromide, first thiophene and lures amine, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiophenes two
Azoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, DL- beta-aminobutyric acids, isotianil, its English are general
It is entitled：Isotianil, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazoles of 3,4- bis- -
5- Ethyl formates, virazole, antofine, Ningnanmycin or salicylic acid, cymoxanil, thiram, ziram, Mancozeb, second phosphorus
Aluminium, thiophanate-methyl, Bravo, enemy can pine, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph,
Dimethomorph, mefenoxam, benalaxyl-M, double chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil, leaf
Withered phthalein, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid
Amine, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, benzene oxygen
Bacterium amine, orysastrobin, ZEN 90160, pyraclostrobin, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, the azoles of ring third
Alcohol, Difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, hexaconazole, Asia
Amine azoles, kind bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, triazole
Alcohol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, miaow
The white spirit of cycloheximide triazole, Evil imidazoles, pefurazoate, famoxadones, SYP-Z048, hymexazo, Evil, Guardian, Grandox fumigant, octhilinone,
Benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, pyridine
Acyl bacterium amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, Fenarimol, fluorine
Benzene ancymidol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, iprovalicarb,
It is benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, more anti-
It is mycin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, more
Bacterium spirit, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, ethirimol, difoltan, captan, sterilizing
It is pellet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, third gloomy
Zinc, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron,
Diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, more fruit pyridines, the pungent salt of biguanides, iminoctadine, chlorine nitre
Amine, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium,
Oppose line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, chlorazol
Phosphorus, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole；The present invention
Total weight/mass percentage compositions of the chiral 5,6-tetrahydropyridine derivative I in the bactericidal composition be 1%-90%, it is of the invention
The ratio of chiral 5,6-tetrahydropyridine derivative I and foregoing commodity bactericide is mass percent 1%: 99% to 99%: 1%；It is described
The formulation of bactericidal composition processing is selected from：Seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water solubility
Granula, granula subtilis, soluble thick agent, poison grain, block poison bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray
It is agent, oil in water emulsion, smoke candle, smoke candle, smoke cartridge, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, cold
Gu mist agent, aerosol, the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil
Suspension, oil-dispersing property pulvis, dense jelly, sprinkle pour agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam release
Agent；The plant disease of the bactericidal composition preventing and treating is selected from：Seedling blight of rice, tomato root rot, the late blight of potato, tobacco are black
Shin disease, millet powdery mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose；The bactericidal composition is fitted
Plant is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean,
Pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria,
Rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic,
Watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya,
Orchid, potted landscape.
Embodiment 6
The chiral 5,6-tetrahydropyridine derivative I of the present invention is combined with anti-plant virus agent in preventing and treating agricultural and forestry and gardening
Application in viral diseases of plants：
All chiral 5,6-tetrahydropyridine derivative I of the present invention combine with any one in commodity antiviral agent or two kinds
Antiviral composition is formed to be used to prevent and treat agricultural and forestry and gardening plant virus disease, the commodity antiviral agent choosing
From：Diazosulfide, tiadinil, TDL, isotianil are abbreviated as, its English is general entitled：Isotianil, 4- methyl isophthalic acid,
2,3- thiadiazoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid second
Ester, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- Ethyl formates of 3,4- bis-,
DL- beta-aminobutyric acids, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure amine or salicylic acid, cytosintetidemycin, dichloro different
Nicotinic acid, allyl isothiazole, well ridge azanol, jinggangmeisu；The chiral 5,6-tetrahydropyridine derivative I of the present invention is in the antiviral compound
Total weight/mass percentage composition in thing is 1%-90%, chiral 5,6-tetrahydropyridine derivative I of the invention and the anti-plant of foregoing commodity
The ratio of viral agent is mass percent 1%: 99% to 99%: 1%；The formulation of the antiviral composition processing is selected from：Kind
Subprocessing emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick agent, poison grain,
Block poison bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smoke candle, smoke candle,
Smoke cartridge, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol, solid-liquid mixing dress agent,
Solid liquid liquid mixing dress agent, solid/mixing dress agent, medicine paint, fine granule, follow the trail of pulvis, oil suspending agent, oil-dispersing property pulvis, dense jelly,
Sprinkle and pour agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；The antiviral composition preventing and treating
Virus disease is selected from：Rice dwarf virus disease, BYDV, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease, tobacco
Veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, citrus virosis, cymbidium mosaic virus, sword-leaved cymbidium ring spot
Poison；The plant that the antiviral composition is used to prevent and treat is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, Ma Ling
Potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet,
Sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery
Dish, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo
Bamboo shoot, hops, pepper, banana, papaya, orchid, potted landscape.
The chiral 5,6-tetrahydropyridine derivative I of the present invention of table 2 bacteriostatic activity (suppression/% of 50 mcg/mls)
| Sequence number | Test code number | AS | CA | GZ | PP | SS | BC | PI | RC | PS |
| 1 | zyj05-30 | 25.00 | 29.17 | 28.00 | 29.63 | 20.00 | 41.07 | 15.38 | 30.00 | 14.29 |
| 2 | zyj05-37 | 40.00 | 58.33 | 38.67 | 29.63 | 56.92 | 39.29 | 34.62 | 27.50 | 19.05 |
| 3 | zyj05-36 | 30.00 | 41.67 | 36.00 | 46.30 | 53.85 | 58.93 | 26.92 | 35.00 | 4.76 |
| 4 | zyj05-39 | 35.00 | 37.50 | 20.00 | 59.26 | 50.77 | 30.36 | 15.38 | 37.50 | 19.05 |
| 5 | zyj05-62 | 25.00 | 45.83 | 28.00 | 14.81 | 26.15 | 44.64 | 15.38 | 42.50 | 19.05 |
| 6 | zyj05-57 | 30.00 | 41.67 | 20.00 | 42.59 | 26.15 | 87.50 | 23.08 | 30.00 | 4.76 |
| 7 | zyj05-25 | 25.00 | 37.50 | 52.00 | 51.85 | 93.85 | 62.50 | 19.23 | 7.50 | 4.76 |
| 8 | zyj05-38 | 15.00 | 45.83 | 22.67 | 16.67 | 26.15 | 23.21 | 15.38 | 36.25 | 4.76 |
| 9 | zyj05-61 | 30.00 | 37.50 | 28.00 | 48.15 | 26.15 | 41.07 | 15.38 | 37.50 | 4.76 |
| 10 | zyj05-54 | 29.63 | 38.10 | 46.15 | 58.70 | 38.46 | 62.50 | 46.15 | 68.63 | 23.08 |
| 11 | zyj05-63 | 25.00 | 37.50 | 25.33 | 33.33 | 26.15 | 46.43 | 15.38 | 47.50 | 0 |
| 12 | zyj05-64 | 30.00 | 37.50 | 36.00 | 42.59 | 35.38 | 53.57 | 23.08 | 50.00 | 19.05 |
| 13 | zyj05-91 | 30.00 | 8.33 | 25.33 | 33.33 | 35.38 | 39.29 | 11.54 | 5.00 | 9.52 |
| 14 | zyj05-60 | 67.23 | 47.88 | 68.35 | 73.89 | 56.45 | 80.30 | 60.23 | 69.66 | 58.87 |
| 15 | zyj05-81 | 26.53 | 28.57 | 50.00 | 39.53 | 31.82 | 89.29 | 22.58 | 46.43 | 50.00 |
| 16 | zyj05-84 | 20.00 | 45.83 | 33.33 | 38.89 | 35.38 | 35.71 | 23.08 | 42.50 | 19.05 |
| 17 | zyj05-90 | 20.41 | 21.43 | 50.00 | 55.81 | 45.45 | 67.86 | 8.06 | 28.57 | 27.27 |
| 18 | zyj05-85 | 30.00 | 37.50 | 36.00 | 42.59 | 35.38 | 53.57 | 23.08 | 50.00 | 19.05 |
| 19 | zyj05-86 | 45.00 | 54.17 | 49.33 | 51.85 | 50.77 | 57.14 | 34.62 | 67.50 | 23.81 |
| 20 | zyj05-83 | 40.00 | 50.00 | 44.00 | 35.19 | 44.62 | 91.07 | 34.62 | 60.00 | 33.33 |
| 21 | zyj05-89 | 30.00 | 41.67 | 22.67 | 42.59 | 35.38 | 14.29 | 19.23 | 40.00 | 9.52 |
| 22 | zyj05-101 | 8.16 | 21.43 | 42.86 | 20.93 | 68.18 | 78.57 | 22.58 | 25.00 | 22.73 |
| 23 | zyj05-112 | 35.00 | 45.83 | 33.33 | 46.30 | 44.62 | 58.93 | 19.23 | 37.50 | 19.05 |
| 24 | zyj05-118 | 29.63 | 47.62 | 46.15 | 32.61 | 38.46 | 56.25 | 19.23 | 54.90 | 0 |
| 25 | zyj05-113 | 35.00 | 33.33 | 25.33 | 31.48 | 53.85 | 37.50 | 19.23 | 25.00 | 19.05 |
| 26 | zyj05-122 | 44.44 | 23.81 | 19.23 | 47.83 | 7.69 | 50.00 | 19.23 | 68.63 | 19.23 |
| 27 | zyj05-121 | 22.22 | 23.81 | 0 | 43.48 | 19.23 | 12.50 | 15.38 | 68.63 | 34.62 |
| 28 | zyj05-120 | 60.47 | 67.56 | 50.83 | 78.69 | 60.12 | 68.99 | 64.32 | 60.78 | 68.91 |
| 29 | zyj05-105 | 35.00 | 41.67 | 46.67 | 53.70 | 47.69 | 60.71 | 30.77 | 52.50 | 28.57 |
| 30 | lfy006-39 | 33.33 | 11.11 | 44.83 | 42.25 | 61.40 | 31.58 | 67.50 | 68.29 | 10.00 |
| 31 | lfy004-47 | 16.67 | 27.78 | 44.83 | 74.65 | 52.63 | 100 | 88.75 | 68.29 | 27.50 |
The chiral 5,6-tetrahydropyridine derivative I of the present invention of table 3 killing aphids are active (death rate, %, 100 mg/litres)
| Sequence number | Test code number | Death rate % | Sequence number | Test code number | Death rate % | Sequence number | Test code number | Death rate % |
| 1 | zyj05-30 | 22.84 | 12 | zyj05-64 | 21.28 | 23 | zyj05-112 | 14.83 |
| 2 | zyj05-37 | 45.78 | 13 | zyj05-91 | 33.18 | 24 | zyj05-118 | 58.92 |
| 3 | zyj05-36 | 48.7 | 14 | zyj05-60 | 35.86 | 25 | zyj05-113 | 26.29 |
| 4 | zyj05-39 | 9.41 | 15 | zyj05-81 | 34.81 | 26 | zyj05-122 | 64.73 |
| 5 | zyj05-62 | 21.28 | 16 | zyj05-84 | 17.93 | 27 | zyj05-121 | 70.28 |
| 6 | zyj05-57 | 46.98 | 17 | zyj05-90 | 28.70 | 28 | zyj05-120 | 40.56 |
| 7 | zyj05-25 | 14.83 | 18 | zyj05-85 | 48.70 | 29 | zyj05-105 | 30.48 |
| 8 | zyj05-38 | 45.37 | 19 | zyj05-86 | 27.73 | 30 | lfy006-39 | 0 |
| 9 | zyj05-61 | 60.37 | 20 | zyj05-83 | 68.70 | 31 | lfy004-47 | 74.60 |
| 10 | zyj05-54 | 55.20 | 21 | zyj05-89 | 24.63 | |||
| 11 | zyj05-63 | 27.27 | 22 | zyj05-101 | 39.24 |
Claims (7)
1. a kind of chiral 5,6-tetrahydropyridine derivative, it is characterised in that there is chemical structure of general formula shown in formula I：
Wherein, R1Selected from ethyl, benzyl, 4- methyl-benzyls, thiophene -2- bases, furans -2- bases, cyclohexyl, 4- trifluoromethylbenzenes
Base；R2Selected from 2- (4 '-tertiary butyl oxycarbonyl piperidines) thiazole-4-yl, 4- methylthiazol -5- bases, thiazole-4-yl；R3Selected from 4- first
Phenyl, phenyl, 4- nitrobenzophenones, cyclopropyl.
2. the synthetic method of the chiral 5,6-tetrahydropyridine derivative I described in claim 1, specific synthetic route are as follows：
Wherein, R1Selected from ethyl, benzyl, 4- methyl-benzyls, thiophene -2- bases, furans -2- bases, cyclohexyl, 4- trifluoromethylbenzenes
Base；R2Selected from 2- (4 '-tertiary butyl oxycarbonyl piperidines) thiazole-4-yl, 4- methylthiazol -5- bases, thiazole-4-yl；R3Selected from 4- first
Phenyl, phenyl, 4- nitrobenzophenones, cyclopropyl；PPh3It is triphenylphosphine；
Comprise the following steps that：
A. chiral 5,6-tetrahydropyridine derivative I preparation：
Nitrogenous sulfur-bearing sulfimide derivative II, the triphenylphosphine of catalytic amount, catalysis are sequentially added into 100 milliliters of round-bottomed flasks
The 4- metoxyphenols of amount, are finally slowly added dropwise R1Corresponding ketene compound, it is chiral tetrahydrochysene that the catalytic amount, which refers to mole,
The 5%-20%, R of pyridine derivate II moles1The mole of corresponding ketene compound derives for nitrogenous sulfur-bearing sulfimide
1-5 times of thing II moles, reacted 24 hours in 30 degrees Centigrades；After reaction completely, residue is through 200~300 mesh silica gel
Column chromatography purifies to obtain chiral 5,6-tetrahydropyridine derivative I, yield 60-95%, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: acetic acid
Ethyl ester, according to the difference of product, volume ratio 10: 1-6: 1；Amount prepared by chiral 5,6-tetrahydropyridine derivative I and reaction vessel
Volume is expanded or shunk by corresponding proportion.
3. the chiral 5,6-tetrahydropyridine derivative I described in claim 1 is with agriculturally acceptable auxiliary agent in insecticide is prepared
Purposes.
4. the chiral 5,6-tetrahydropyridine derivative I described in claim 1 is with agriculturally acceptable auxiliary agent in bactericide is prepared
Purposes.
5. the chiral 5,6-tetrahydropyridine derivative I described in claim 1 is with insecticide composition in preventing and treating agricultural and forestry and gardening
Purposes in insect pest of the plant：
All chiral 5,6-tetrahydropyridine derivative I described in claim 1 combine with any one in commodity insecticide or two kinds
Form Pesticidal combination to be used to prevent and treat agricultural and forestry and gardening plant insect pest, the commodity insecticide is selected from：Chlopyrifos,
Sub- Nong, Acetamiprid, emamectin benzoate, milbemectin, AVM, pleocidin, fenvalerate, esfenvalerate,
Cypermethrin, effective cypermethrin, Cyhalothrin, decis, Fenpropathrin, Beta- cyfloxylates, Lambda-
Cyhalothrin, Permanone, permethrin, allethrin, Biphenthrin, Permethrin, ethofenprox, fluorochlorobenzene chrysanthemum
Ester, fluvalinate, imidacloprid, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin,
Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization are grand, HEXAFLUMURON, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron,
Noviflumuron is noviflumuron, its No. CAS be 121451-02-3, flucycloxuron, Novaluron be Rimon, chlorfluazuron,
Bay sir 6874 are that { 1- [(3.5- bis- chloro- 4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzenes)-urea }, Bay SIR-8514 are
[1- (4- Trifluoromethoxyphen-ls) -3- (2- chlorobenzenes)-urea], piperazine worm urea, Bistrifluron are bistrifluron, furans worm acyl
Hydrazine, tebufenozide, chlorine tebufenozide, methoxyfenozide, ring tebufenozide, Rogor, flolimat, DDVP, orthene, triazole
Phosphorus, quinalphos, pyridaphethione, isazofos, isoprocarb, sevin, Aphox, MTMC, Mobucin, cartap, Bassa, leaf
Disperse, carbaryl, Benfuracard micro, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine,
Propargite, diafenthiuron, pymetrozine, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, phonamiphos,
Ethiprole, Cupric sulfate, dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, chlorfenapyr, pyrrole
Piperazine ketone, etoxazole, tebufenpyrad, rattle away young ketone, Nylar, emaricin；Chiral 5,6-tetrahydropyridine derivative I described in claim 1
Weight/mass percentage composition in the Pesticidal combination is 1%-90%, the chiral 5,6-tetrahydropyridine derivative I described in claim 1
Ratio with foregoing commodity insecticide is mass percent 1%: 99% to 99%: 1%；The formulation of the Pesticidal combination processing
It is selected from：Seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick
Agent, poison grain, block poison bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smog
Tank, smoke candle, smoke cartridge, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol, solid-liquid
Gu the agent of mixing dress, the agent of liquid liquid mixing dress, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil-dispersing property powder
Agent, dense jelly, sprinkle and pour agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；The Insecticidal combinations
The insect pest of the plant of thing preventing and treating is selected from：Red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, east
Square mole cricket, rice thripses, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipes thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper,
Green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle plant hopper of sugarcane, cotten aphid, green bugs, wheat
Macrosiphus spp, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Korea's ball are hard
It is a red-spotted lizard, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, green rice bug, green
Fleahopper, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, brown slug moth, thosea siensis,
Gelechiid, pink bollworm, brachmia triannuella, diamondback moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple top tip leaf roll
Moth, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, corn borer, yellow rice borer, Oeobia undalis, rice leaf roller, bar
Snout moth's larva, Notarchaderogata, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel
Point spark, black cutworm, big cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae,
Pelopidas mathias, Papilio xuthus, Common Mormon, cabbage butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans blister beetle, Venus ground beetle, wrinkle
Sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the small buprestid beetle of citrus, golden edge buprestid beetle,
Yellow meal worm, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer,
Longicorn beetle, nadezhdiella cantori, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea weevil,
Broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hang cocoon ichneumon wasp, bollworm
Tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melon are real
Fly, the latent fly of wheat leaf ash, Americal rice leaf miner, Soybean stem borer, frit fly, Hylemyia Platura Meigen, onion fly, radish fly, full skirt Exorista civilis, corn borer
It is strict to post fly, armyworm；The plant of the Pesticidal combination preventing and treating is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato,
Potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower,
It is beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, white
Dish, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, hill
Dish, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
6. the chiral 5,6-tetrahydropyridine derivative I described in claim 1 is with antimicrobial combination in preventing and treating agricultural and forestry and gardening
Purposes in plant disease：
All chiral 5,6-tetrahydropyridine derivative I described in claim 1 combine with any one in commodity bactericide or two kinds
Form bactericidal composition to be used to prevent and treat agricultural and forestry and gardening plant disease, the commodity bactericide is selected from：Benzo thiophene two
Azoles, tiadinil, it is abbreviated as TDL, tisocromide, first thiophene and lures amine, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid, 4- methyl isophthalic acids, 2,
3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, DL- beta-aminobutyric acids, isotianil, its English
Text is general entitled：Isotianil, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, 3,4- dichloros are different
Thiazole -5- Ethyl formates, virazole, antofine, Ningnanmycin or salicylic acid, cymoxanil, thiram, ziram, Mancozeb,
Aliette, thiophanate-methyl, Bravo, enemy can pine, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, fluorine
Quinoline, dimethomorph, mefenoxam, benalaxyl-M, double chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil,
Tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, double alkynes acyls
Bacterium amine, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, benzene
Oxygen bacterium amine, orysastrobin, ZEN 90160, pyraclostrobin, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, ring third
Azoles alcohol, Difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, hexaconazole,
Glyoxalin, kind bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, three
Azoles alcohol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid,
The white spirit of Fenamidone, Evil imidazoles, pefurazoate, famoxadones, SYP-Z048, hymexazo, Evil, Guardian, Grandox fumigant, pungent thiophene
Ketone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium
Amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, chlorobenzene pyrimidine
Alcohol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, isopropyl
Bacterium amine, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, spring thunder are mould
Element, polyoxin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, go out
Rust amine, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, ethirimol, difoltan, gram bacterium
Pellet, folpet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloro- nitro
Benzene, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone,
Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, more fruit pyridines, the pungent salt of biguanides, biguanides are pungent
Amine, botran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane,
Metham-sodium, enemy's line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, except line
The different thiophene of phosphorus, isazofos, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl
Azoles；Total weight/mass percentage compositions of the chiral 5,6-tetrahydropyridine derivative I in the bactericidal composition described in claim 1 be
1%-90%, the ratio of chiral 5,6-tetrahydropyridine derivative I and foregoing commodity bactericide described in claim 1 are mass percent
1%: 99% to 99%: 1%；The formulation of the bactericidal composition processing is selected from：It is seed treatment emulsion, aqueous emulsion, microemulsion, outstanding
Emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick agent, poison grain, block poison bait, granular poison bait, sheet poison bait,
Dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smoke candle, smoke candle, smoke cartridge, smog rod, smog piece, smog
Gu ball, foaming agent, ointment, thermal fog, harl agent, aerosol, the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, solid/mixing dress
Agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil-dispersing property pulvis, dense jelly, sprinkle pour agent, seed coat agent, liniment, film forming
Finish, ultra low volume liquids, steam releasing agent；The plant disease of the bactericidal composition preventing and treating is selected from：Seedling blight of rice, tomato
Root rot, the late blight of potato, tobacco black shank, millet powdery mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, Huang
Melon anthracnose；The applicable plant of the bactericidal composition is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, Ma Ling
Potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet,
Sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery
Dish, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo
Bamboo shoot, hops, pepper, banana, papaya, orchid, potted landscape.
7. the chiral 5,6-tetrahydropyridine derivative I described in claim 1 combined with anti-plant virus agent preventing and treating agricultural and forestry and
Purposes in gardening plant virus disease：
All chiral 5,6-tetrahydropyridine derivative I and any one in commodity antiviral agent or two kinds described in claim 1
Combination forms antiviral composition and is used to prevent and treat agricultural and forestry and gardening plant virus disease, the commodity antiviral agent
It is selected from：Diazosulfide, tiadinil, TDL, isotianil are abbreviated as, its English is general entitled：Isotianil, 4- methyl-
1,2,3- thiadiazoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid second
Ester, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- Ethyl formates of 3,4- bis-,
DL- beta-aminobutyric acids, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure amine or salicylic acid, cytosintetidemycin, dichloro different
Nicotinic acid, allyl isothiazole, well ridge azanol, jinggangmeisu；Chiral 5,6-tetrahydropyridine derivative I described in claim 1 is described anti-
Total weight/mass percentage composition in virus composition is 1%-90%, the chiral 5,6-tetrahydropyridine derivative I described in claim 1 with
The ratio of foregoing commodity anti-plant virus agent is mass percent 1%: 99% to 99%: 1%；The antiviral composition processing
Formulation be selected from：Seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, can
Dense dose of dissolubility, poison grain, block poison bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion,
Smoke candle, smoke candle, smoke cartridge, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol,
Gu the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil dispersed
Property pulvis, dense jelly, sprinkle pour agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；It is described disease-resistant
The virus disease of malicious composition for preventing and controlling is selected from：Rice dwarf virus disease, BYDV, stripe virus disease, fern leaf of tomato viral disease, capsicum
Leaf disease viral disease, tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, citrus virosis, sword-leaved cymbidium mosaic disease
Poison, cybidium ring spot virus；The plant that the antiviral composition is used to prevent and treat is selected from：Paddy, wheat, barley, oat, corn,
Sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame
Fiber crops, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, trailing plants
Fore-telling, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach
Tree, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610402574.0A CN107459515A (en) | 2016-06-06 | 2016-06-06 | A kind of chiral 5,6-tetrahydropyridine derivative and its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610402574.0A CN107459515A (en) | 2016-06-06 | 2016-06-06 | A kind of chiral 5,6-tetrahydropyridine derivative and its production and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107459515A true CN107459515A (en) | 2017-12-12 |
Family
ID=60545872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610402574.0A Pending CN107459515A (en) | 2016-06-06 | 2016-06-06 | A kind of chiral 5,6-tetrahydropyridine derivative and its production and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107459515A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371364A (en) * | 1999-09-03 | 2002-09-25 | 辛根塔参与股份公司 | Tetrahydropyridines as pesticides |
-
2016
- 2016-06-06 CN CN201610402574.0A patent/CN107459515A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371364A (en) * | 1999-09-03 | 2002-09-25 | 辛根塔参与股份公司 | Tetrahydropyridines as pesticides |
Non-Patent Citations (3)
| Title |
|---|
| GE WANG ET AL.: "Enantioselective [4+2] cycloaddition reaction of a,b-unsaturated imine and methyl vinyl ketone catalyzed by chiral phosphine", 《TETRAHEDRON》 * |
| ZUGUI SHI ET AL.: "[4+2] Annulation of Vinyl Ketones Initiated by a Phosphine-Catalyzed Aza-Rauhut–Currier Reaction: A Practical Access to Densely Functionalized Tetrahydropyridines", 《CHEM. EUR. J.》 * |
| ZUGUI SHI ET AL.: "Catalytic Asymmetric [4+2] Annulation Initiated by an Aza-Rauhut–Currier Reaction: Facile Entry to Highly Functionalized Tetrahydropyridines", 《ANGEW. CHEM. INT. ED》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105622422B (en) | A kind of bromo hexahydro indanone compounds and its production and use | |
| CN104650064B (en) | A kind of aminothiazole carboxylic acid derivates and its production and use | |
| CN104650060B (en) | A kind of piperidines thiazole and its production and use | |
| CN104650062B (en) | A kind of nitrogenous heterocyclic thiazole and its production and use | |
| CN104650061B (en) | A kind of thiazole aldoxime ether compound and its production and use | |
| CN109970650A (en) | Pyrazole phenyl formamide analog derivative and its preparation method and application | |
| CN105622597A (en) | Chloroisothiazole neonicotine compound, as well as preparation method and application thereof | |
| CN104649996A (en) | Isothiazole oxime ether derivatives as well as preparation method and application thereof | |
| CN110041260A (en) | A kind of multi-substituted pyrazol amide derivatives and its preparation method and application | |
| CN109970653A (en) | Methoxy acrylate derivative and its preparation method and application of the one kind containing difluoromethyl pyrazole | |
| CN104974150B (en) | A kind of carboxamidine derivatives of 3,4 2 chloroisothiazole 5 and its production and use | |
| CN109485618A (en) | A kind of 2 phenylsubstituted thiazoles derivatives and its preparation method and application | |
| CN105732606A (en) | Thiadiazole heterocycle-containing anabasine compound as well as preparation method and application thereof | |
| CN107226812A (en) | One class piperidines thiazole oxime ether methoxy base acrylate derivative and its production and use | |
| CN104650059B (en) | A kind of thiazolone oxime ether derivative and its preparation method and application | |
| CN110128346A (en) | A kind of biaryl amide pyrazole derivatives and its preparation method and application | |
| CN103641795B (en) | One class contains acetophenone derivs of 1,2,3-thiadiazoles and its production and use | |
| CN103483288B (en) | One class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use | |
| CN105503708B (en) | The heterocyclic compound of one kind containing bis-fluoro ethyls and its preparation method and application | |
| CN104447617B (en) | The synthesis of nitro contracting amino guanidine compound of the one kind containing 1,2,3 thiadiazoles and purposes | |
| CN107602547A (en) | Heterocycle triazole derivative and its production and use | |
| CN104496980B (en) | Novel thiazole heterocyclic compounds and its preparation method and application | |
| CN107459509A (en) | A kind of nitrogenous sulfur-bearing sulfimide derivative and its production and use | |
| CN103214475B (en) | One class contains 4-methyl isophthalic acid, α-(replacement) hydroxyamide derivatives of 2,3-thiadiazoles and its production and use | |
| CN106995417B (en) | A kind of isothiazole oxime ether methoxy base acrylate derivative and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171212 |