CN1089089C - Cyanoacrylate Compounds Containing Hydrocarbylthiopyridylmethylamine and Their Biological Activities - Google Patents
Cyanoacrylate Compounds Containing Hydrocarbylthiopyridylmethylamine and Their Biological Activities Download PDFInfo
- Publication number
- CN1089089C CN1089089C CN98117840A CN98117840A CN1089089C CN 1089089 C CN1089089 C CN 1089089C CN 98117840 A CN98117840 A CN 98117840A CN 98117840 A CN98117840 A CN 98117840A CN 1089089 C CN1089089 C CN 1089089C
- Authority
- CN
- China
- Prior art keywords
- mol ratio
- gram
- hours
- alkoxyalkyl
- chloro
- 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
Links
- 230000004071 biological effect Effects 0.000 title description 4
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- -1 cyanoacrylate compound Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 240000008042 Zea mays Species 0.000 claims abstract description 11
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 11
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 11
- 235000005822 corn Nutrition 0.000 claims abstract description 11
- 229920001651 Cyanoacrylate Polymers 0.000 claims abstract description 10
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 244000025254 Cannabis sativa Species 0.000 claims abstract description 7
- 241000196324 Embryophyta Species 0.000 claims abstract description 7
- 244000237956 Amaranthus retroflexus Species 0.000 claims abstract description 4
- 235000013479 Amaranthus retroflexus Nutrition 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- 244000058871 Echinochloa crus-galli Species 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- XPARFBOWIYMLMY-UHFFFAOYSA-N (6-chloropyridin-3-yl)methanamine Chemical compound NCC1=CC=C(Cl)N=C1 XPARFBOWIYMLMY-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- SKCNYHLTRZIINA-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)pyridine Chemical compound ClCC1=CC=C(Cl)N=C1 SKCNYHLTRZIINA-UHFFFAOYSA-N 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- HDOUGSFASVGDCS-UHFFFAOYSA-N pyridin-3-ylmethanamine Chemical compound NCC1=CC=CN=C1 HDOUGSFASVGDCS-UHFFFAOYSA-N 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000009333 weeding Methods 0.000 abstract description 8
- 230000002363 herbicidal effect Effects 0.000 abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 125000001188 haloalkyl group Chemical group 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract 2
- 235000001602 Digitaria X umfolozi Nutrition 0.000 abstract 1
- 235000017898 Digitaria ciliaris Nutrition 0.000 abstract 1
- 235000005476 Digitaria cruciata Nutrition 0.000 abstract 1
- 235000006830 Digitaria didactyla Nutrition 0.000 abstract 1
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 abstract 1
- 235000010823 Digitaria sanguinalis Nutrition 0.000 abstract 1
- 244000025670 Eleusine indica Species 0.000 abstract 1
- 235000014716 Eleusine indica Nutrition 0.000 abstract 1
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- 125000005081 alkoxyalkoxyalkyl group Chemical group 0.000 abstract 1
- 125000000278 alkyl amino alkyl group Chemical group 0.000 abstract 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 241000209140 Triticum Species 0.000 description 7
- 235000021307 Triticum Nutrition 0.000 description 7
- 230000002401 inhibitory effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 241000192043 Echinochloa Species 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000012010 growth Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 208000024891 symptom Diseases 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ULEVTQHCVWIDPC-UHFFFAOYSA-N 2-(methylamino)ethyl prop-2-enoate Chemical compound CNCCOC(=O)C=C ULEVTQHCVWIDPC-UHFFFAOYSA-N 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- 108010060806 Photosystem II Protein Complex Proteins 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- CFRPSFYHXJZSBI-DHZHZOJOSA-N (E)-nitenpyram Chemical compound [O-][N+](=O)/C=C(\NC)N(CC)CC1=CC=C(Cl)N=C1 CFRPSFYHXJZSBI-DHZHZOJOSA-N 0.000 description 1
- MTXSIJUGVMTTMU-JTQLQIEISA-N (S)-anabasine Chemical compound N1CCCC[C@H]1C1=CC=CN=C1 MTXSIJUGVMTTMU-JTQLQIEISA-N 0.000 description 1
- WDENHBKVUUOZOQ-UHFFFAOYSA-N 3-(methylamino)prop-2-enenitrile Chemical compound CNC=CC#N WDENHBKVUUOZOQ-UHFFFAOYSA-N 0.000 description 1
- NOVGJMMRLSCEOB-UHFFFAOYSA-N C(C1=CC=CC=C1)SC=CC#N Chemical compound C(C1=CC=CC=C1)SC=CC#N NOVGJMMRLSCEOB-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229930014345 anabasine Natural products 0.000 description 1
- MLIREBYILWEBDM-UHFFFAOYSA-N anhydrous cyanoacetic acid Natural products OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000005524 benzylchlorides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical class CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229940079888 nitenpyram Drugs 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical class CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a cyanoacrylate compound containing sulfenyl pyridine methylamino and herbicidal activity. The compound (II) has high Hill reaction activity and weeding activity and shows excellent selectivity to crops. The dosage of the composition is 20-100 g/muThe herbicide can be used as herbicide for rape, amaranthus retroflexus broadleaf weeds, barnyard grass, crabgrass grass and other weeds in corn fields. Wherein R is1: CN, COOX (X: alkyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkylthioalkyl, alkylaminoalkyl), CONY (Y: alkoxyalkyl); r2: alkyl, benzyl, or SR2H, aryl, alkenyl, haloalkyl.
Description
The present invention relates to contain the cyanoacrylate compound and the weeding activity of sulfenyl pyridyl-methanamine base.
Cyanoacrylate is class photosynthesis photosystem II (PSII) electron transfer inhibitor, and research in recent years is rather active.Existing research mainly launches (Huppatz J.L. around the compound of structure (I), McFadden H.G., Huber Marie-Luise, etal, Synthesis And Chemisrty of Agrochemicals II, 187,1992), only contain phenyl ring in the structure (I), also do not contain other heterocyclic report.
R
1: alkyl, alkoxyalkyl; R
2: H, alkyl R
3: alkyl, halogen, alkoxyl group etc.
(I)
The purpose of this invention is to provide a kind of cyanoacrylate compound (II) and preparation method and application that contains sulfenyl pyridyl-methanamine base, the present invention is to be model configuration with anabasine insecticide Nitenpyram, and then active group pyridyl-methanamine base induced one to have synthesized the cyanoacrylate compound (II) that contains sulfenyl pyridyl-methanamine base in the cyanoacrylate.Biological activity determination is the result show: compound (II) has very high weeding activity to broadleaf weeds and gramineous weeds, and crop is shown good selectivity, to corn growth safety.
The present invention is following general formula (II) compound:
Wherein, R
1: CN, COOX (X: alkyl, alkoxyalkyl, alcoxyl alkoxyalkyl, alkane sulfane base, alkyl amines alkyl), CONY (Y: alkoxyalkyl); R
2: alkyl, benzyl or SR
2=H, aryl, thiazolinyl, haloalkyl.
The compounds of this invention (II) synthetic route is as follows:
Concrete synthetic route of the present invention is described in detail as follows:
Cyan-acetic ester or propane dinitrile and dithiocarbonic anhydride, potassium hydroxide (mol ratio 1: 1: 2～2.1) are in dioxane or anhydrous acetonitrile solvent, and 0～10 ℃ was reacted 0.5～3 hour down.4～20 ℃ add haloalkanes (X=Cl, Br, I) or methyl-sulfate (only being used to methylate) (mol ratio 1: 2～2.1), 20～60 ℃ of reactions 6～10 hours down.Solid is separated out in the ice-water bath cooling, or the adding elutriation goes out oily matter in reaction system, is intermediate 2-cyano group-3,3-two sulfenyl acrylate or vinyl cyanide.
2-chloro-5-chloromethylpyridine is mixed with six methynes, four ammoniums, sodium iodide (mol ratio 1: 1～1.1: 1), and stirring at room is 20～24 hours in dehydrated alcohol, obtains white solid, is the salt compounded of iodine of 2-chloro-5-picolyl and six methynes, four ammoniums.This salt compounded of iodine and dehydrated alcohol, 36～38% hydrochloric acid (mol ratio 1: 30～40: 30～40) mix, and reflux 6～12 hours steams the acetal of excess ethanol and generation.Add chloroform in the residuum, the NaOH aqueous solution with 25% transfers to PH=11.Separatory, aqueous layer extracted, drying is sloughed solvent, promptly obtains 2-chloro-5-pyridyl-methanamine.
2-cyano group-3,3-two sulfenyl acrylate or vinyl cyanide and 2-chloro-5-pyridyl-methanamine (mol ratio 1: 1.1～1.2) react in dehydrated alcohol or tetrahydrofuran (THF) or chloroform solvent, reflux 8～12 hours, concentrate.As obtain solid, get final product with ethyl acetate-sherwood oil recrystallization; If obtain oily matter, separate purification with rapid column chromatography, can obtain target product.
Compound (II) can be used as the weedicide of gramineous weedss such as broadleaf weedss such as rape in the corn field, Amaranthus retroflexus and barnyard grass grass, lady's-grass under 20～100 gram/mu dosage.
Substantial characteristics of the present invention can be embodied from following embodiment, but it should not to be considered as be that the present invention is imposed any restrictions.
Embodiment 1:2-cyano group-3,3-diethyl sulfenyl ethyl propenoate synthetic
In the 250ml there-necked flask, add the potassium hydroxide powder (0.25mol) of 17.1 gram porphyrizes, the 100ml dioxane.Be cooled to 10 ℃, drip the mixed solution of 14.14 gram ethyl cyanacetates (0.125mol), 9.5 gram dithiocarbonic anhydride (0.125mol) and 60ml dioxane under the vigorous stirring, about 45min drips off.Stirring at room 30min has yellow solid to produce, and leaves standstill, and inclining the upper strata dioxane, adds cold acetone 50ml, filters, and drying gets solid 32 grams, yield 96.6%.
Get this sylvite 7.95 grams (30mmol), add 24ml 95% ethanol, 4ml water.Room temperature drips 6.54 gram monobromethanes (60mmol) and 6ml alcoholic acid mixed solution.Be heated to 60 ℃ of reactions 7 hours.Add 100ml water in the system, stir, have reddish-brown oily matter to separate out.Tell this oily matter, be product.Water layer with 2 * 20ml hexanaphthene extraction, can get portion of product again again, altogether 6.69 gram products, its structure warp
1The HNMR checking, H
1NMR:1.29～1.40 (m, 9H, 3CH
3), 3.11～3.25 (dq, 4H, 2SCH
2), 4.24～4.27 (q, 2H, CO
2CH
2).Thick yield: 91.1%.
Embodiment 2. 2-cyano group-3,3-diformazan sulfenyl vinylformic acid methoxyl group ethyl ester synthetic
In the 100ml there-necked flask, add the potassium hydroxide powder (0.04mol) of 2.74 gram porphyrizes, and the 12ml anhydrous acetonitrile.After being cooled to 5 ℃, drip 2.86 gram cyanoacetic acid methoxyl group ethyl esters (0.02mol), the mixed solution of 1.5 gram dithiocarbonic anhydride (0.02mol) and 5ml anhydrous acetonitrile, about 10min drips off.Stirring at room 3h, reaction system is yellow solidliquid mixture.Be cooled to 4 ℃, the methyl-sulfate (0.04mol) that Dropwise 5 .04 grammes per square metre is steamed, temperature of reaction can raise automatically.The about 6h of stirring at room, the TLC demonstration reacts completely, and adds 50ml water, tells the red oil of generation, is product, 3.7g, yield 74.9%.
Embodiment 3. 2-cyano group-3,3-two benzylthio-vinyl cyanide synthetic
In the 250ml there-necked flask, add the potassium hydroxide powder (0.25mol) of 17.1 gram porphyrizes, the 100ml dioxane.Be cooled to 10 ℃, drip the mixed solution of 8.25 gram propane dinitrile (0.125mol), 9.5 gram dithiocarbonic anhydride (0.125mol) and 60ml dioxane under the vigorous stirring, about 45min drips off.Stirring at room 30min has yellow solid to produce, and leaves standstill, and inclining the upper strata dioxane, adds cold acetone 50ml, filters, and drying gets solid 27 grams, yield 99%.
Get this sylvite 6.54 grams (30mmol), add 24ml 95% ethanol, 4ml water.Be cooled to 5 ℃, drip 7.6 gram Benzyl Chlorides (60mmol) and 6ml alcoholic acid mixed solution, be heated to 60 ℃ of reactions 7 hours.Stop heating, ice-water bath fully cools off, and stirs, and has yellow solid to separate out, filter, with 80% washing with alcohol, yellow solid 8.42 grams, m.p.:83～85 ℃, yield: 87.1%.
Synthesizing of embodiment 4. 2-cyano group-3-ethoxy ethyl acrylate
In the 100ml there-necked flask, add 113 gram ethyl cyanacetates (0.1mol), 17 gram triethyl orthoformates (0.12mol), 21 gram acetic anhydride (0.22mol).Heated and stirred refluxes, and keeps stable at 100 ℃ at last, reaction 8h.Water pump concentrates, and removes part material, and enriched material is put into refrigerator.Have a large amount of solids to separate out, filter, the anhydrous diethyl ether washing gets white crystal 8.9 grams, and m.p:50.5-52 ℃, yield: 52.6%.
Synthesizing of embodiment 5. 2-chloro-5-pyridyl-methanamines (2)
In the 100ml four-hole bottle, add 4 49 gram sodium iodides (0.03mol), 4.2 gram six methynes, four ammoniums (0.03mol) and 30ml dehydrated alcohols.Drip 4.86 gram 2-chloro-5-chloromethylpyridine (0.03mol) and be dissolved in 10ml alcoholic acid solution, stirring at room 24 hours obtains a large amount of white solids.Filter,, get 10.7 gram white solids with anhydrous diethyl ether washing, drying.Get this solid 9.8 grams (0.025mol) and add the 50ml dehydrated alcohols, the 30ml concentrated hydrochloric acid, reflux 7 hours steams the acetal of excess ethanol and generation then, steams till about 90 ℃ of the interior temperature.Residuum cooling back adds the 20ml chloroform, drips the 25%NaOH aqueous solution, transfers pH value to 11.Tell organic layer, water layer merges with 3 * 10ml chloroform extraction, and drying concentrates, and gets light yellow liquid 2.7 grams, and it is 95.6% that GC analyzes content, and putting into refrigerator becomes pale yellow crystals, yield 72.4%.
Synthesizing of embodiment 6. 2 cyano group-3-(2-chloro-5-pyridine) methylamino-ethyl propenoate (h)
In the 25ml there-necked flask, add 0.845 gram 2-cyano group-3-ethoxy ethyl acrylate (5mmol), 0.79 gram 2-chloro-5-pyridyl-methanamine (5.5mmol), back flow reaction is 11 hours in the 12ml dehydrated alcohol.Concentrate, obtain yellow oil, place and solidify.Use the dehydrated alcohol recrystallization, obtain light yellow solid 1.16 gram, m.p.:112～114 ℃, yield 87.4%.
Synthesizing of embodiment 7. 2-cyano group-3-methylthio group-3-(2-chloro-5-pyridine) methylamino-vinylformic acid ethoxy ethyl ester (k):
In the 25ml there-necked flask, add 1.30 gram 2-cyano group-3,3-diformazan sulfenyl vinylformic acid ethoxy ethyl ester (5mmol), 0.86 gram 2-chloro-5-pyridyl-methanamine (6mmol), the 12ml dehydrated alcohol, reflux 12 hours concentrates, obtain the reddish-brown dope, rapid column chromatography separates, (ethyl acetate: sherwood oil v: v=1: 2) obtain product, be white crystal 1.22 grams, yield 73.6%, m.p:60-61 ℃.
In the Synthetic 2 5ml there-necked flask of embodiment 8. 2-cyano group-3-ethylmercapto group-3-(2-chloro-5-pyridine) methylamino-vinyl cyanide (r), add 0.99 gram 2-cyano group-3,3-diethyl sulfenyl vinyl cyanide (5mmol), 0.86 gram 2-chloro-5-pyridyl-methanamine (6mmol), the 12ml anhydrous tetrahydro furan, reflux 10 hours, concentrate, place and be cured as the reddish-brown solid, filter, wash with ethyl acetate, get yellow solid 0.89 gram, yield 64%, ethyl acetate-sherwood oil recrystallization, pale yellow crystals, m.p:127～129 ℃.
With similar approach synthetic compound (II).Concrete outcome sees Table 1, table 2.Table 1: the materialization data of compound (II) and ultimate analysis value
*-be oily matter;
*Substituting group is H, does not contain S table 2: the nuclear magnetic data table of compound (II)
| Numbering | Substituent R 1 R 2 | Fusing point * ℃ | Yield % | Ultimate analysis (theoretical value) C H N | |
| a b c d e f g h i j k l m n o p q r s t u v w | CO 2Et CO 2Et CO 2Et CO 2Et CO 2Et CO 2Et CO 2Et CO 2Et CO 2CH 2CH 2OMe CO 2CH 2CH 2OMe CO 2CH 2CH 2OEt CO 2CH 2CH 2OEt CO 2CH 2CH 2OC 4H 9-n CO 2(CH 2) 2O(CH 2) 2OMe CONHC 2H 4OCH 3 CONHC 3H 6OCH 3 CN CN CN CN CN CN CN | CH 3 C 2H 5 CH(CH 3) 2CH 2CH(CH 3) 2 (CH 2) 4CH 3 (CH 2) 6CH 3 CH 2Ph H ** CH 3 C 2H 5 CH 3 C 2H 5 CH 3 CH 3 CH 3 CH 3 CH 3 C 2H 5 CH(CH 3) 2 CH 2CH(CH 3) 2 (CH 2) 4CH 3 CH 2Ph (CH 2) 6CH 3 | 93-95.5 58.5-59.5 50.5-52 — — — 67-69 112-114 49-50 46-48 60-61 51-53 — — 59-60.5 92.5-94 136-138 127-129 96-99 102-104 63-65 77-79.5 72.5-75 | 73.8 67.7 68.7 67.8 81.5 64.6 78.4 87.4 77.1 66.1 73.5 83.3 76.5 78.1 85.0 90.7 72.6 64.0 53.7 51.8 71.8 47.4 65.4 | 49.80(50.08)，4.16(4.53)，13.0713.48) 51.35(51.61)，5.15(4.95)，12.70(12.36) 53.10(53.02)，5.50(5.34)，12.22(12.36) 54.13(54.31)，5.84(5.69)，11.60(11.87) 55.40(55.50)，5.34(6.03)，11.17(11.42) 57.48(57.64)，6.33(5.62)，10.67(10.61) 58.80(58.83)，5.01(4.68)，10.45(10.83) 54.30(54.25)，4.65(4.55)，15.83(15.81) 48.95(49.19)，4.86(4.72)，11.95(12.29) 50.20(50.63)，5.04(5.09)，11.65(11.81) 50.33(50.63)，5.32(5.09)，11.68(11.81) 51.80(51.96)，5.63(5.45)，11.05(11.36) 52.94(53.19)，5.54(5.78)，10.84(10.95) 49.64(49.80)，5.34(5.22)，10.59(10.89) 49.03(49.34)，5.04(5.03)16.24(16.44) 50.30(50.77)，5.37(5.39)，15.51(15.79) 49.81(49.91)，3.39(3.43)，21.48(21.16) 51.80(51.71)，4.07(3.98)，19.82(20.10) 53.20(53.33)，4.46(4.48)，18.90(19.14) 54.32(54.81)，5.40(4.93)17.88(18.26) 55.91(56.15)，5.46(5.34)，17.16(17.46) 59.79(59.91)，3.86(3.84)，16.41(16.44) |
| Numbering | Nuclear magnetic data |
| a | 1.30(t，3H，CH 3)，3.18(s，3H，SCH 3)，4.19(m，2H，CO 2CH 2)，4.77(d，2H，CH 2N)， 7.34～8.31(m，3H，C 5H 3N)，10.37(w，1H，NH) |
| b | 1.25～1.33(m，6H，CH 3，CH 3)，3.20(q，2H，SCH 2)，4.17(q，2H，CO 2CH 2)，4.76(d，2H，CH 2N)， 7.34～8.28(m，3H，C 5H 3N)，10.4(w，1H，NH) |
| c | 1.29～1.34(m，9H，2CH 3，CH 3)，3.95(m，1H，SCH)，4.19(q，2H，CO 2CH 2)，4.78(d，2H，CH 2N)， 7.30～8.29(m，3H，C 5H 3N)，10.56(w，1H，NH) |
| d | 0.98(d，6H，2CH 3)，1.29(t，3H，CH 3)，1.90(m，1H，CH)，3.04(d，2H，SCH 2)，4.19(q，2H，CO 2CH 2)， 4.77(d，2H，CH 2N)，7.30～8.30(m，3H，C 5H 3N)10.4(w，1H，NH) |
| e | 0.86(t，3H，CH 3)，1.24～1.61(m，9H，3CH 2，CH 3)，3.13(t，2H，SCH 2)，4.17(q，2H，CO 2CH 2)， 4.76(d，2H，CH 2N)，7.33～8.29(m，3H，C 5H 3N)，10.48(w，1H，NH) |
| f | 1.33(t，3H，CH 3)，4.20(q，2H，CO 2CH 2)，4.35(s，2H，SCH 2)，4.49(d，2H，CH 2N)， 7.22～8.15(m，8H，C 6H 5C 5H 3N)，10.25(w，1H，NH) |
| g | 0.83(t，3H，CH 3)，1.21～1.31(m，11H，CH 3，4CH 2)，1.70(m，2H，CH 2)，3.11(t，2H，SCH 2)， 4.17(q，2H，CO 2CH 2)，4.76(d，2H，CH 2N)，7.32～8.27(m，3H，C 5H 3N)，10.3(w，1H，NH) |
| h | 2.64(d，3H，SCH 3)，3.36(d，3H，OCH 2)，3.62(t，2H，CH 2O)，4.26(t，2H，CO 2CH 2)， 4.75(d，2H，CH 2N)，7.34～8.29(m，3H，C 5H 3N)，10.25(w，1H，NH) |
| i | 1.29(t，3H，CH 3)，3.19(q，2H，SCH 2)，3.38(s，3H，OCH 3)，3.63(t，2H，CH 2O)， 4.28(t，2H，CO 2CH 2)，4.77(d，2H，CH 2N)，7.30～8.30(m，3H，C 5H 3N)，10.4(w，1H，NH) |
| j | 1.17(t，3H，CH 3)，2.65(s，3H，SCH 3)，3.53(q，2H，OCH 2)，3.66(t，2H，CH 2O)， 4.27(t，2H，CO 2CH 2)，4.75(d，2H，CH 2N)，7.31～8.29(m，3H，C 5H 3N)，10.3(w，1H，NH) |
| k | 1.15(t，3H，CH 3)，1.27(t，3H，CH 3)，3.18(q，2H，SCH 2)，3.51(q，2H，OCH 2)，3.64(t，2H，CH 2O)， 4.24(t，2H，CO 2CH 2)，4.75(d，2H.CH 2N)，7.32～8.27(m，3H，C 5H 3N)，10.3(w，1H，NH) |
| l | 1.25(t，3H，CH 3)，4.17(q，2H，CO 2CH 2)，4.46(d，2H，CH 2N)，7.30～8.31(m，4H，C 5H 3N，H-C＝) |
| m | 0.84(t，3H，CH 3)，1.28～1.49(m，4H，2CH 2)，2.62(s，3H，SCH 3)，3.43(t，2H，OCH 2)， 3.62(t，2H，CH 2O)，4.23(t，2H，CO 2CH 2)，4.73(d，2H，CH 2N)， 7.27～8.27(m，3H，C 5H 3N)，10.3(w，1H，NH) |
| n | 2.64(s，3H，SCH 3)，3.34(s，3H，OCH 3)，3.40～3.75(m，6H，CH 2OCH 2CH 2O)，4.26(t，2H，CO 2CH 2)， 4.75(d，2H，CH 2N)，7.29～8.29(m，3H，C 5H 3N)，10.25(w，1H，NH) |
| o | 1.77(m，2H，CH 2)，2.56(s，3H，SCH 3)，3.30～3.50(m，7H，CH 2，CH 2，OCH 3)，6.8(w，1H，CONH)， 4.71(d，2H，CH 2N)，7.29～8.28(m，3H，C 5H 3N)，11.25(w，1H，NH) |
| p | 2.55(s，3H，SCH 3)，3.31(s，3H，SCH 3)，3.40(w，4H，2CH 2)，4.69(d，2H，CH 2N)， 6.25(w，1H，CONH)，7.27～8.28(m，3H，C 5H 3N)，11.3(w，1H，NH) |
| q | 2.59(s，3H，SCH 3)，4.74(s，2H，CH 2N)，7.54～8.39(m，3H，C 5H 3N)，9.14(w，1H，NH) |
| r | 1.32(t，3H，CH 3)，3.19(q，2H，SCH 2)，4.70(d，2H，CH 2N)，7.33～8.32(m，4H，C 5H 3N，NH) |
| s | 1.32(d，6H，2CH 3)，3.94(m，1H，SCH)，4.69(d，2H，CH 2N)，7.31～8.30(m，4H，C 5H 3N，NH) |
| t | 0.98(d，6H，2CH 3)，1.90(m，1H，CH)，3.04(d，2H，SCH 2)，4.71(d，2H，CH 2N)， 7.33～8.33(m，3H，C 5H 3N) |
| u | 0.87(t，3H，CH 3)，1.29，1.36(2m，6H，3CH 2)，2.2(w，1H，NH)，3.15(t，2H，SCH 2)， 4.70(d，2H，CH 2N)，7.34～8.33(m，3H，C 5H 3N) |
| v | 4.36(s，2H，SCH 2)，4.55(d，2H，CH 2N)，7.26～8.14(m，8H，C 6H 5，C 5H 3N) |
| w | 0.88(t，3H，CH 3)，1.25～1.70(m，10H，5CH 2)，3.15(t，2H，SCH 2)，4.69(d，2H，CH 2N)， 7.33～8.33(m，3H，C 5H 3N) |
Embodiment 9.
The primary dcreening operation of weeding activity is measured
Adopt pot-culture method to measure the live body weeding activity of part of compounds (II): with rape and barnyard grass grass is the examination material, 1-1.5 leaf phase cauline leaf is handled after broadcasting preceding soil treatment of back seedling and seedling, medicament is converted 50 liters of (mu) sprayings of water and is handled, and handles back 10 days measurement results, calculates the fresh weight inhibiting rate.The results are shown in Table 3.Table 3: the weeding activity inhibiting rate (%) of part of compounds (II) (dosage 100 gram/mus)
| Numbering | Cauline leaf is handled | Soil treatment | ||
| Rape | The barnyard grass grass | Rape | The barnyard grass grass | |
| a b c d e f g h i j k l m n o p q r s u v | 96.8 88.0 50.9 27.7 40.3 32.1 7.8 0 96.8 100.0 100.0 100.0 100.0 95.7 31.9 98.3 26.4 26.4 30.8 84.0 32.7 | 94.7 75.5 29.8 19.1 25.5 25.5 8.9 5.4 89.2 100.0 94.6 100.0 80.4 80.4 55.4 89.3 11.7 0 19.1 56.7 25.5 | 46.2 69.0 17.6 15.0 14.6 8.8 0 3.2 38.0 61.3 53.1 62.5 0 0 0 41.2 22.5 13.6 14.4 6.3 20.8 | 11.6 0 0 0 0 0 0 0 11.7 0 17.6 11.7 0 0 0 0 0 0 0 11.7 0 |
The result shows: this compounds shows weeding activity preferably, its drug effect symptom is: handle the back weed growth and be subjected to obvious inhibition, new not regrowth of (heart) leaf, chlorisis, jaundice, withered, slowly dead, long action time, consistent with other photosynthesis weedicide symptom; Cauline leaf is handled active in soil treatment; Activity to the broad-leaved rape is higher than Gramineae barnyard grass grass.
Embodiment 10.
To the outstanding compound i of activity, j, k, l reduce dosage and carry out multiple sieve mensuration
Measuring method the results are shown in Table 4: table 4 with embodiment 7: the weeding activity of part of compounds (II) sieves result (inhibiting rate %) again
| Numbering dosage (g/mu) barnyard grass mare Tang Amaranthus retroflexus rape clover |
| 50 77.3 96.0 100.0 100.0 96.4 i 20 43.2 44.0 85.3 85.5 69.1 10 27.3 36.0 38.2 58.4 29.1 |
| 50 79.5 88.0 85.3 86.4 96.4 j 20 17.0 44.0 35.3 59.8 87.3 10 0 36.0 23.5 50.0 27.3 |
| 50 83.0 96.8 100.0 100.0 100.0 k 20 43.2 52.0 85.3 97.7 38.2 10 20.5 36.0 64.7 85.0 29.1 |
| 50 90.0 100.0 100.0 100.0 100.0 l 20 42.0 56.0 94.1 98.1 89.1 10 11.3 48.0 76.5 87.4 30.9 |
The result shows: when dosage was 20g/mu, compound still had good active, k, and l can reach more than 97% to the inhibiting rate of rape; When dosage was reduced to 10g/mu, l still reached 87.4% to the inhibiting rate of rape.
Above 4 compounds are carried out the stripped biological activity determination of Hill reaction, and the result shows that the Hill reactive behavior of compound is all very high, its PI
50Value reaches 7.42,7.27,7.60,7.55 respectively.
Embodiment 11.
The plant growth security is measured
Choose the highest active compound k, l, carries out the plant growth security of corn, wheat is measured with under the effective dose at mu: the corn of plantation rudiment in the basin (anti-No. five of Tang), wheat.Treat that corn, wheat 2-3 leaf phase handle.Mu is converted processings of spraying of 50 liters of the water yields, handles back 8-10 days mensuration medicament to the influence of plant growth, herbicidal effect etc.Observe symptom of chemical damage, strain and dispenser strain growth differences significance are not handled in statistical computation.Measurement result sees Table 5.
Table 5: corn, wheat growth security are measured
*For suppressing significantly,
*For suppressing extremely remarkable.
| Crop | Corn | Average heavy | Inhibiting rate % | Crop | Wheat | Average heavy | Inhibiting rate % |
| Not dispenser strain | 8.12 | Not dispenser strain | 3.91 | ||||
| Processed strain | k 50g/mu 20g/mu l 50g/mu 20g/mu | 7.86 8.06 7.54 8.08 | 3.2 0.7 7.1 0.5 | Processed strain | k 50g/mu 20g/mu l 50g/mu 20g/mu | 2.29 ** 3.58 * 1.80 ** 2.90 ** | 41.4 8.4 54.0 25.8 |
The result shows: compound k, and l is when 20 gram/mus, to corn growth safety; During 50 gram/mus, handling to measure in 10 days has some to suppress to fresh weight, but leaf age, the leaf look of corn do not had influence.Compound k, l cauline leaf under effective dose is handled dangerous to wheat, and the wheat fresh weight is had obvious inhibition.
Claims (3)
1. cyanoacrylate compound that contains picolyl is characterized in that it is that general formula is the compound of (II):
Wherein, R
1Be CN, COOX or CONY,
X is alkyl, alkoxyalkyl, alcoxyl alkoxyalkyl, alkane sulfane base, and Y is an alkoxyalkyl;
R
2Be alkyl or benzyl.
2. as the said preparation method who contains the cyanoacrylate compound of picolyl of claim 1, it is characterized in that it is through following step:
(1) with cyan-acetic ester or propane dinitrile and dithiocarbonic anhydride, potassium hydroxide, wherein mol ratio is 1: 1: 2～2.1, puts into dioxane or anhydrous acetonitrile solvent, 0～10 ℃ of reaction 0.5～3 hour down; Add haloalkane or methyl-sulfate at 4～20 ℃, wherein only be used to methylate, mol ratio is 1: 2～2.1, reacts 6～10 hours down in 20～60 ℃; Solid is separated out in the ice-water bath cooling, or the adding elutriation goes out oily matter in reaction system, is intermediate 3,3-two alkylthio acrylate or vinyl cyanide.
(2) 2-chloro-5-chloromethylpyridine and six methynes, four ammoniums, sodium iodide, mol ratio is 1: 1～1.1: 1, mixes, and stirring at room is 20～24 hours in dehydrated alcohol, obtains the salt compounded of iodine of 2-chloro-5-picolyl and six methynes, four ammoniums; This salt compounded of iodine and dehydrated alcohol, 36～38% hydrochloric acid, mol ratio is 1: 30～40: 30～40, mixes, reflux 6～12 hours steams the acetal of excess ethanol and generation; Add chloroform in the residuum, the NaOH aqueous solution with 25% transfers to PH=11, separatory, and aqueous layer extracted, drying is sloughed solvent, promptly obtains 2-chlorine 5-pyridyl-methanamine.
(3) make 3,3-two alkylthio acrylate or vinyl cyanide and 2-chloro-5-pyridyl-methanamine, mol ratio is 1: 1.1～1.2, reacts in alcohol or tetrahydrofuran (THF) or chloroform solvent anhydrous, refluxes 8～12 hours, concentrates; As obtain solid, get final product with ethyl acetate-sherwood oil recrystallization; If obtain oily matter, separate purification with rapid column chromatography, can obtain final product.
3. as the said application that contains the cyanoacrylate compound of picolyl of claim 1, it is characterized in that it under 20～100 gram/mu dosage, can be used as the weedicide of rape in the corn field, Amaranthus retroflexus broadleaf weeds, barnyard grass grass, lady's-grass gramineous weeds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117840A CN1089089C (en) | 1998-08-28 | 1998-08-28 | Cyanoacrylate Compounds Containing Hydrocarbylthiopyridylmethylamine and Their Biological Activities |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117840A CN1089089C (en) | 1998-08-28 | 1998-08-28 | Cyanoacrylate Compounds Containing Hydrocarbylthiopyridylmethylamine and Their Biological Activities |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1246474A CN1246474A (en) | 2000-03-08 |
| CN1089089C true CN1089089C (en) | 2002-08-14 |
Family
ID=5225749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98117840A Expired - Fee Related CN1089089C (en) | 1998-08-28 | 1998-08-28 | Cyanoacrylate Compounds Containing Hydrocarbylthiopyridylmethylamine and Their Biological Activities |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1089089C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317265C (en) * | 2004-07-30 | 2007-05-23 | 贵州大学 | Cyanoacrylate derivatives and their preparation method and biological activity |
| CN101967115B (en) * | 2009-12-17 | 2013-09-18 | 南开大学 | Synthesis and herbicidal activity of 3-substituted phenoxybenzamine-2-cyanoacrylate ethoxyethyl compound |
| CN102952066B (en) * | 2011-08-30 | 2014-06-04 | 南开大学 | Synthesis and biological activity of cyanoacrylate compound containing pyridylmethyl phenyl ether structure |
| CN103012289B (en) * | 2011-09-26 | 2014-12-31 | 南开大学 | Synthesis and biological activity of cyanoacrylate compound containing pyrimidine phenylate structure |
| CN103408478A (en) * | 2013-07-10 | 2013-11-27 | 南开大学 | Bactericidal activity of 2-aryloxy alanyl structure-containing cyano acrylamide compound |
| CN113439742B (en) * | 2020-03-24 | 2023-08-01 | 沈阳化工大学 | A kind of bactericidal preparation and its application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4201569A (en) * | 1977-10-03 | 1980-05-06 | Gulf Oil Corporation | 2,3-Disubstituted aralkylaminoacrylonitriles and use as herbicides |
-
1998
- 1998-08-28 CN CN98117840A patent/CN1089089C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4201569A (en) * | 1977-10-03 | 1980-05-06 | Gulf Oil Corporation | 2,3-Disubstituted aralkylaminoacrylonitriles and use as herbicides |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1246474A (en) | 2000-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6771116B1 (en) | m-diamide compounds, their preparation methods, and their use | |
| Song | Environment-friendly antiviral agents for plants | |
| KR100430695B1 (en) | Dihydropyridazinone and pyridazinone compounds, compositions containing them, and methods of controlling fungi using the same | |
| SU1428196A3 (en) | Method of producing 2-substituted phenyl-4,5,6,7-tetrahydro-2h-isoindole-1,3-dions | |
| EA029868B1 (en) | Alcohol alkoxylates as adjuvants for agrochemical formulations | |
| CN1089089C (en) | Cyanoacrylate Compounds Containing Hydrocarbylthiopyridylmethylamine and Their Biological Activities | |
| WO2015074615A1 (en) | Pyrazole amide compound and application thereof | |
| US12247017B2 (en) | Herbicidal uracilpyridines | |
| JPS626548B2 (en) | ||
| CN110078673B (en) | Aryl uracil compound, preparation method thereof and pesticide composition | |
| JPH08217777A (en) | 2-Pyrazolin-5-one derivatives, intermediates thereof and herbicides | |
| JPS5939401B2 (en) | Microbial control agent and its manufacturing method | |
| JP2613651B2 (en) | Oxa or thiazoline compound and insecticide and acaricide containing the same | |
| EP0174088A2 (en) | Biologically active amide derivatives | |
| JPS63503070A (en) | Use of malonic acid derivative compounds to increase crop yield | |
| JP2690816B2 (en) | Quinolinyl oxadiazole herbicide | |
| EP0524041A2 (en) | Pesticides | |
| CN114957166B (en) | Phenylacetamide compound and preparation method and application thereof | |
| US12466806B2 (en) | 2-substituted imidazolidine derivative containing aryl bipyridyloxy structure and preparation method and use thereof | |
| CA2218745A1 (en) | Novel .beta.-methoxy acrylic acid derivatives, method for preparing same, and use of said derivatives as pesticides | |
| EP0126235A1 (en) | Five-membered nitrogen-containing heterocycles, process for their preparation and their use as pesticides | |
| JP2522807B2 (en) | Cyclohexenone derivative and plant growth regulator containing the compound | |
| JPS6072871A (en) | N-substituted-5-(substituted phenyl)-1,3- oxazolidine and herbicidal detoxicant | |
| JPS6351142B2 (en) | ||
| US4581060A (en) | Compositions, which promote plant growth and protect plants, based on oxime ethers and oxime esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |