CN108484551A - 一种螺环烯胺化合物及其用途 - Google Patents
一种螺环烯胺化合物及其用途 Download PDFInfo
- Publication number
- CN108484551A CN108484551A CN201810283918.XA CN201810283918A CN108484551A CN 108484551 A CN108484551 A CN 108484551A CN 201810283918 A CN201810283918 A CN 201810283918A CN 108484551 A CN108484551 A CN 108484551A
- Authority
- CN
- China
- Prior art keywords
- compound
- loop coil
- formula
- mite
- enamine compound
- 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.)
- Granted
Links
- -1 enamine compound Chemical class 0.000 title claims abstract description 12
- 239000000642 acaricide Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 4
- 241000238876 Acari Species 0.000 claims 1
- 239000003139 biocide Substances 0.000 claims 1
- 230000000895 acaricidal effect Effects 0.000 abstract description 18
- 102000002322 Egg Proteins Human genes 0.000 abstract description 10
- 108010000912 Egg Proteins Proteins 0.000 abstract description 10
- 210000004681 ovum Anatomy 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 230000001629 suppression Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- DTDSAWVUFPGDMX-UHFFFAOYSA-N spirodiclofen Chemical compound CCC(C)(C)C(=O)OC1=C(C=2C(=CC(Cl)=CC=2)Cl)C(=O)OC11CCCCC1 DTDSAWVUFPGDMX-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- PEQJBOMPGWYIRO-UHFFFAOYSA-N n-ethyl-3,4-dimethoxyaniline Chemical class CCNC1=CC=C(OC)C(OC)=C1 PEQJBOMPGWYIRO-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- RUAYXHSDAMWEDR-UHFFFAOYSA-N 2-(4-tert-butylphenyl)acetic acid Chemical compound CC(C)(C)C1=CC=C(CC(O)=O)C=C1 RUAYXHSDAMWEDR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002085 enols Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000012447 hatching Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ZDBRPNZOTCHLSP-UHFFFAOYSA-N 1-hydroxycyclohexane-1-carbonitrile Chemical compound N#CC1(O)CCCCC1 ZDBRPNZOTCHLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical class CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- FMEYLVYIPWGZRX-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1C(C(OC12CCCCC1)=O)=C2N Chemical compound CC(C)(C)c(cc1)ccc1C(C(OC12CCCCC1)=O)=C2N FMEYLVYIPWGZRX-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 239000005657 Fenpyroximate Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000005663 Pyridaben Substances 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- YYJNOYZRYGDPNH-MFKUBSTISA-N fenpyroximate Chemical compound C=1C=C(C(=O)OC(C)(C)C)C=CC=1CO/N=C/C=1C(C)=NN(C)C=1OC1=CC=CC=C1 YYJNOYZRYGDPNH-MFKUBSTISA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- ZYHMJXZULPZUED-UHFFFAOYSA-N propargite Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1C(OS(=O)OCC#C)CCCC1 ZYHMJXZULPZUED-UHFFFAOYSA-N 0.000 description 1
- DWFZBUWUXWZWKD-UHFFFAOYSA-N pyridaben Chemical compound C1=CC(C(C)(C)C)=CC=C1CSC1=C(Cl)C(=O)N(C(C)(C)C)N=C1 DWFZBUWUXWZWKD-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种螺环烯胺化合物杀螨剂,其结构如式I所示:
Description
技术领域 本发明属于农药杀螨剂领域,具体涉及一种螺环烯胺化合物及其用途。
背景技术 螨害会造成农作物的大量减产,是现代农业生产中主要虫害之一。目前广泛使用的杀螨剂有多种,如哒螨灵、唑螨酯、炔螨特、乙唑螨腈、螺螨酯等,该类杀螨剂化学结构有一共同特点,都含有叔丁基活性基团。专利WO 2001068625报道,螺螨酯(式Ⅱ)是拜耳公司开发的螺环季酮酸类杀螨剂,对多种作物的不同螨类均有优异的防效及持效期,螺螨酯是由中间体3-(2,4-二氯苯基)-2-氧代-1-氧杂螺[4,5]-癸-3-烯-4-醇(式Ⅲ)与2,2-二甲基丁酰氯反应制得。螺环己酮酸类杀螨剂中,其烯醇结构是其活性基团。根据活性基团拼接法和生物等电子法将螺环季酮酸类杀螨剂中的烯醇改变成烯胺,同时将活性基团叔丁基接到结构构中,设计并合成了本发明一种螺环烯胺化合物,其结构及其杀螨活性未见报道。
发明内容 本发明的目的在于提供一种结构新颖、高效、安全、经济的杀螨剂。
本发明的技术方案如下:
一种螺环烯胺化合物,结构如I所示:
式I化合物可由如下方法制备:
中间体A和缚酸剂在极性溶剂中升温至60℃左右,通过环合反应生成式I化合物。缚酸剂选自碱金属氢氧化物如氢氧化钠、氢氧化钾或叔丁醇钾、叔丁醇钠、甲醇钠、乙醇钠;反应过程所用极性溶剂溶剂选自二甲基甲酰胺(DMF)等。中间体A和式I化合物的具体制备过程见本说明书合成实例1和实例2。试验表明,本发明公开的螺环烯胺化合物对害螨螨卵有意想不到的高活性,因此本发明还包括式I化合物用于防治螨害的用途。
本发明的优点和积极效果:
随着螺螨酯等常规杀螨剂的大量和频繁使用,害螨对常规杀螨剂产生了不同程度的抗药性。本发明设计并制备了一种结构新颖的新型螺环烯胺类杀螨剂,在相同的药剂浓度下,本发明式I化合物对螨卵的抑杀效果显著优于螺环季酮酸类杀螨剂,式I化合物在1μg/mL和0.1μg/mL浓度下对朱砂叶螨螨卵的校正死亡率分别是96%和78%,对照药剂螺螨酯的相应为87%和32%(见表1)。式I化合物的制备方法比螺环季酮酸类杀螨剂更加简便,生产成本更低,环境污染小,是具有良好产业化前景的新型杀螨剂。
本发明还包括式I化合物作为活性组分的杀螨组合物,该组合物还包括农业或林业上可接受的载体。
本发明化合物在防治螨害时,可单独使用,也可与其它活性物质组合使用,以利于提高产品的综合功能。本发明的组合物可以以制剂的形式施用:式I化合物作为活性组分溶于或分散于载体或溶剂中,添加适当的表面活性剂配制成乳油、水乳剂、微乳剂、悬浮剂等。
应明确的是,在本发明的权利要求所限定的范围内,可进行各种变换和改动。
具体实施方式:
下列合成实例及生测结果可用来进一步说明本发明,但不意味着限制本发明。
合成实例
实例1中间体A的制备:
(1)对叔丁基苯乙酰氯的制备
向250mL单口烧瓶中分别加入28.8g(0.15mol)对叔丁基苯乙酸、100mL二氯甲烷和35.7g(0.3mol)氯化亚砜,回流3-4h,旋蒸除去二氯甲烷和氯化亚砜,得31g淡黄色液体。收率:98%。
(2)对叔丁基苯乙酸-1-氰基环己酯的制备:
向250mL单口瓶中加入20.8g(0.1mol)对叔丁基苯乙酰氯、12.5g(0.1mol)1-氰基环己醇、100g甲苯升温至回流。TLC监测反应完成后,旋蒸掉溶剂甲苯。得28g浅棕色粘稠状液体即为对叔丁基苯乙酸-1-氰基环己酯。收率93.6%
实例2螺环烯胺化合物的制备
向250mL三口烧瓶中加入29.9g(0.1mol)中间体A、4.8g(0.12mol)NaOH、80gDMF升温至60℃,反应液变成棕黄色,且反应液变黏。TLC监测反应完成后,冷却至室温,加入250mL水,有黄色固体析出。抽滤得黄色固体,用95mL异丙醇重结晶,得到18g白色固体即为目标产物。收率:60%。
式I化合物的表征:1H NMR(500MHz,DMSO-d6),δ(ppm):0.47(s,9H),0.64-0.67(d,2H),0.72-0.80(m,2H),0.86-0.88(m,2H),1.09-1.15(m,2H),1.68-1.70(m,2H),6.32(s,2H),6.54-6.56(m,2H),6.59-6.51(m,2H)。熔点:292.7~295.4℃。
生物活性测定
实例2、采用浸渍法和统计校正害虫死亡率的方法测定杀螨卵活性。具体过程是:将供试药剂按有效成分分别稀释至所需浓度,在无菌条件下各取50mL药液注入培养皿内,再分别浸入有朱砂螨卵(螨卵按室内标准化方法正常饲养的群体)的叶片,轻轻振荡5s后取出。以添加50mL灭菌水的平板做空白对照。将培养皿放在24±1℃恒温培养箱内。待对照卵孵化并发育至弱螨阶段时调查孵化数,统计死亡率。每处理3次重复,结果取平均值,试验结果见表1。
表1式I化合物与螺螨酯对朱砂叶螨卵活性数据
由表1试验数据可见,本发明化合物I具有优异的杀螨卵活性,在相同剂量下,化合物I的活性均高于或同于螺螨酯。
Claims (3)
1.一种螺环烯胺化合物,结构如式I所示:
2.根据权利要求1所述的一种螺环烯胺化合物的用途,其特征在于式I化合物用作杀螨剂防治农业害螨。
3.一种杀螨组合物,含有权利要求1所述的式I化合物为活性组分和农业上可接受的载体。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810283918.XA CN108484551B (zh) | 2018-04-02 | 2018-04-02 | 一种螺环烯胺化合物及其用途 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810283918.XA CN108484551B (zh) | 2018-04-02 | 2018-04-02 | 一种螺环烯胺化合物及其用途 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108484551A true CN108484551A (zh) | 2018-09-04 |
CN108484551B CN108484551B (zh) | 2019-09-20 |
Family
ID=63317520
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810283918.XA Active CN108484551B (zh) | 2018-04-02 | 2018-04-02 | 一种螺环烯胺化合物及其用途 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108484551B (zh) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060819A (zh) * | 2011-01-07 | 2011-05-18 | 青岛科技大学 | 螺环季酮酸类化合物及其制备与应用 |
CN104402850A (zh) * | 2014-12-19 | 2015-03-11 | 山东康乔生物科技有限公司 | 一种3-对丁基苯基2-氧代-1-氧杂螺[4,4]-壬-3-烯-4-醇衍生物及其应用 |
-
2018
- 2018-04-02 CN CN201810283918.XA patent/CN108484551B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060819A (zh) * | 2011-01-07 | 2011-05-18 | 青岛科技大学 | 螺环季酮酸类化合物及其制备与应用 |
CN104402850A (zh) * | 2014-12-19 | 2015-03-11 | 山东康乔生物科技有限公司 | 一种3-对丁基苯基2-氧代-1-氧杂螺[4,4]-壬-3-烯-4-醇衍生物及其应用 |
Non-Patent Citations (1)
Title |
---|
FENG XIAN-GUO等: "Spirodiclofen Derivatives as Highly Potential Acaricides: Synthesis, Structure and Bioactivity", 《CHEM. RES. CHINESE UNIVERSITIES》 * |
Also Published As
Publication number | Publication date |
---|---|
CN108484551B (zh) | 2019-09-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105001289B (zh) | 一种乙酰氨基阿维菌素的精制方法 | |
CN103130769B (zh) | 一种3-二氟乙氧基-吡唑酰胺类化合物及其应用 | |
CN1053233A (zh) | 作为杀虫剂的n-苯基吡唑衍生物 | |
CN109942561A (zh) | 4-(2-噻吩基)嘧啶衍生物及其制备方法和应用 | |
CN109503562A (zh) | 2-[4-(2-噻吩基)]嘧啶基脲衍生物及其制备方法和应用 | |
CN108484551B (zh) | 一种螺环烯胺化合物及其用途 | |
CN106986801A (zh) | 一种新型甲氧基丙烯酸酯类化合物及其制备方法和应用 | |
CN103664978A (zh) | 一种卤苯基芳香胺取代去甲斑蝥素及其制备方法和应用 | |
CN105037329B (zh) | 一种含氟四嗪吡唑类杀螨剂 | |
CN108117528B (zh) | 2,5-取代基-1,3,4-噁二唑砜类衍生物、其制备方法及应用 | |
CN105646421B (zh) | 一种含螺环的磺酸酯类杀螨剂 | |
CN108794462A (zh) | 一种含氟氰亚胺噻唑烷取代的噁二唑类杀虫杀菌剂 | |
CN111039878B (zh) | 一种4-氨基喹唑啉苯醚类化合物及其应用 | |
DE1670709A1 (de) | Pestizide Mittel | |
DE69823191T2 (de) | 1,2,3-thiadiazol-derivate, mittel zur kontrolle von pflanzenkrankheiten und methode zu seiner anwendung | |
CN110981817B (zh) | 喹唑啉酰胺类化合物及其应用 | |
CN85107900A (zh) | 新的2-氰基苯并咪唑衍生物的制备及其作为杀菌剂和杀螨剂的用途 | |
CN105924435B (zh) | 一种取代的吡唑乙酰胺类化合物及其制备方法和应用 | |
CN108675991B (zh) | 一种含氟吡啶哌嗪咪唑脲及其应用 | |
CN109535136A (zh) | 2-[4-(2-呋喃基)]嘧啶基脲类化合物及其制备方法和应用 | |
CN102827025B (zh) | 2-甲氧基-n-(4-氟苯基)苯甲酰胺及其制备方法和用途 | |
CN116982629B (zh) | 一种杀虫组合物、杀虫剂及其应用 | |
EP0420803A2 (de) | Benzo-1,2,3-thiadiazol-Derivate und ihre Verwendung zum Schutz von Pflanzen gegen Krankheiten | |
CN105061399B (zh) | 一种含氟四嗪吡啶类化合物及其用途 | |
CN109535142A (zh) | 2-(1-吡唑基)嘧啶衍生物及其制备方法和应用 |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |