CN111039896A - 一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途 - Google Patents

一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途 Download PDF

Info

Publication number
CN111039896A
CN111039896A CN202010003268.6A CN202010003268A CN111039896A CN 111039896 A CN111039896 A CN 111039896A CN 202010003268 A CN202010003268 A CN 202010003268A CN 111039896 A CN111039896 A CN 111039896A
Authority
CN
China
Prior art keywords
benzothiazole
acyl
preparation
compounds
acyl thiourea
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
Application number
CN202010003268.6A
Other languages
English (en)
Other versions
CN111039896B (zh
Inventor
郝双红
王传平
姚晓芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Agricultural University
Original Assignee
Qingdao Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao Agricultural University filed Critical Qingdao Agricultural University
Priority to CN202010003268.6A priority Critical patent/CN111039896B/zh
Publication of CN111039896A publication Critical patent/CN111039896A/zh
Application granted granted Critical
Publication of CN111039896B publication Critical patent/CN111039896B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • 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
    • C07D417/12—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 linked by a chain containing hetero atoms as chain links

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth 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

本发明（名称为：一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途）涉及9种苯并噻唑酰基硫脲类化合物及其制备方法，以及在抑菌方面的用途。9种苯并噻唑酰基硫脲类化合物，通过硫氰酸胺先与不同酰氯缩合得中间体酰基硫氰酸酯，再与2‑氨基苯并噻唑衍生物发生加成反应得系列目标化合物。这些化合物可作为杀菌剂防治番茄灰霉病菌及苹果腐烂病菌。

Description

一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途
技术领域
本发明涉及一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途，具体的涉及农用杀菌剂领域。
背景技术
苯并噻唑类化合物在农业、医药以及工业等各个领域都被广泛应用。该化合物及其衍生物在农药领域也有多样生物活性，如杀虫、抑菌及除草作用等。酰基硫脲类化合物在农药、医药领域也具有广泛生物活性。该专利基于活性亚结构拼接思想，以苯并噻唑为先导，同时引入酰基硫脲基活性基团，设计合成了一类新型苯并噻唑酰基硫脲类化合物，并筛选了该类化合物的杀菌活性。
发明内容
本发明的目的在于提供一类苯并噻唑酰基硫脲类化合物及制备方法，它可应用于农业上以防治致病菌。
本发明的技术方案如下：
本发明提供的苯并噻唑酰基硫脲类化合物，其结构通式如下：
Figure 761730DEST_PATH_IMAGE001
Ⅰ
R1选自：6-甲氧基、6-硝基、5-硝基、4-硝基；
R2选自：环己基、环丙基、2-氯吡啶-5-基、3-硝基苯基、3-三氟甲基苯基、萘-2-基；
该苯并噻唑酰基硫脲类化合物合成反应式：
Figure 288658DEST_PATH_IMAGE002
Ⅱ Ⅲ
Figure 239034DEST_PATH_IMAGE003
Figure 634243DEST_PATH_IMAGE004
Ⅰ
式中R1及R2定义如上；
通式化合物制备方法：在适当溶剂中，适当温度下，加入适当催化剂，Ⅱ、Ⅲ和
Figure 183036DEST_PATH_IMAGE003
发生缩合，反应一定时间后，处理即得目的产物Ⅰ。
适当溶剂可选自苯、甲苯、二甲苯、二氯甲烷、三氯甲烷、二氯乙烷等；
适当温度指20℃至溶剂的沸点温度；
适当催化剂指无水碳酸钾、无水碳酸钠、三乙胺等；
反应时间为2小时至30小时。
本发明的化合物对番茄灰霉病菌及苹果腐烂病菌有一定抑制作用，同时对大肠杆菌有一定的抑制作用。
具体实施方式
实例1 化合物Ⅰ-1的制备
Figure 5499DEST_PATH_IMAGE005
Figure 944636DEST_PATH_IMAGE006
将91.2 mg（1.2 mmol）硫氰酸钾，175.3 mg（1.2 mmol）环己酰氯，6 mL甲苯，加入到25mL反应管中，再滴加1滴三乙胺，60-70 ℃搅拌，反应1 h，加入180.4 mg（1 mmol）6-甲氧基-2-氨基苯并噻唑，4 mL甲苯，TLC跟踪反应。反应完毕，抽滤，浓缩得黄色固体，通过柱层析[流动相为V（石油醚）：V（乙酸乙酯）= 4：1]分离获得。
化合物Ⅰ-2~Ⅰ-9按照与Ⅰ-1相似的方法合成，合成化合物MS及1H NMR数据列于表1。
表1 目标化合物MS及1H NMR数据
Figure 143536DEST_PATH_IMAGE007
Figure 920737DEST_PATH_IMAGE008
Figure 914101DEST_PATH_IMAGE009
实例2 抑菌活性初筛
称取5 mg化合物，加入2 mL丙酮（10%DMSO溶液），溶解配制成2500 mg/L浓度的药液；取1 mL 2500 mg/L的溶液，加入1 mL丙酮（10%DMSO溶液），溶匀配制成1250 mg/L浓度的药液，同法依次配置625、312.5、156.3、78.1、39.1、19.5 mg/L等8个浓度的药液。
用96孔板，每孔加180μL菌液，加20μL药液，设置三组平行，20μL丙酮（10%DMSO溶液）加入180μL菌液中做对照。封口，放置摇床培养12 h（苹果腐烂菌28 ℃，番茄灰霉菌25℃），肉眼观察菌液浑浊情况。菌液未浑浊的药液浓度为最低抑制浓度（MIC）。
化合物Ⅰ-1~Ⅰ-9的抑菌活性数据列于表2中。
表2 目标化合物抑菌活性初筛
Figure 340534DEST_PATH_IMAGE010
实例3 抑菌活性复筛
称取15 mg 化合物溶于15 mL丙酮（10%DMSO），配置成1000 mg/L浓度的药液，通过二倍稀释法配置500 mg/L、250 mg/L浓度的药液。取3 mL不同浓度的药液分别加入到27 mL熔融的马铃薯琼脂培养基中，然后趁热倒入培养皿，冷却形成带毒平板培养基，分别接种苹果腐烂病菌和番茄灰霉病菌，对照用等量丙酮（10%DMSO），每个处理（不同浓度药液及对照）每个菌种设置三个重复。放置适宜温度下（苹果腐烂菌28 ℃，番茄灰霉菌25 ℃）培养，十字交叉法量取菌落直径，求取平均值。按照下式得到不同浓度药液的抑菌率。
抑菌率公式：
抑菌率 =（对照菌落直径 - 处理菌落直径）/对照直径 * 100%
表3 目标化合物抑菌活性复筛
Figure 77546DEST_PATH_IMAGE011

Claims (2)

1.所述苯并噻唑酰基硫脲类化合物结构如通式所示：
Figure 891138DEST_PATH_IMAGE001
R1选自：6-甲氧基、6-硝基、5-硝基、4-硝基；
R2选自：环己基、环丙基、2-氯吡啶-5-基、3-硝基苯基、3-三氟甲基苯基、萘-2-基。
2.权利要求1所述化合物在防治植物病害方面的用途，所述的植物病害包括苹果腐烂病菌、番茄灰霉病菌。
CN202010003268.6A 2020-01-03 2020-01-03 一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途 Active CN111039896B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010003268.6A CN111039896B (zh) 2020-01-03 2020-01-03 一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010003268.6A CN111039896B (zh) 2020-01-03 2020-01-03 一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途

Publications (2)

Publication Number Publication Date
CN111039896A true CN111039896A (zh) 2020-04-21
CN111039896B CN111039896B (zh) 2022-04-05

Family

ID=70244164

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010003268.6A Active CN111039896B (zh) 2020-01-03 2020-01-03 一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途

Country Status (1)

Country Link
CN (1) CN111039896B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113698378A (zh) * 2021-10-05 2021-11-26 青岛农业大学 一类萘醌类化合物及其制备与杀螨、杀菌用途
CN114989057A (zh) * 2022-07-25 2022-09-02 江西农业大学 一种柠檬醛基酰基硫脲新型衍生物及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4057638A (en) * 1975-07-03 1977-11-08 E. I. Du Pont De Nemours And Company Benzothiazole allophanate fungicides
US4101575A (en) * 1975-03-20 1978-07-18 Bayer Aktiengesellschaft N-aryl-N'-(2,3-dihalogeno-alkanoyl)-ureas
CN102702135A (zh) * 2012-06-15 2012-10-03 中国农业大学 一种含苯并噻唑结构的苯甲酰基硫脲类化合物及其制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101575A (en) * 1975-03-20 1978-07-18 Bayer Aktiengesellschaft N-aryl-N'-(2,3-dihalogeno-alkanoyl)-ureas
US4057638A (en) * 1975-07-03 1977-11-08 E. I. Du Pont De Nemours And Company Benzothiazole allophanate fungicides
CN102702135A (zh) * 2012-06-15 2012-10-03 中国农业大学 一种含苯并噻唑结构的苯甲酰基硫脲类化合物及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘源发等: "1-芳酰基-3-( 2-苯并噻唑)硫脲化合物毒力测定", 《西北大学学报(自然科学版)》 *
孙小茹等: "《观赏植物病害识别与防治》", 30 June 2017, 中国农业大学出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113698378A (zh) * 2021-10-05 2021-11-26 青岛农业大学 一类萘醌类化合物及其制备与杀螨、杀菌用途
CN113698378B (zh) * 2021-10-05 2023-01-17 青岛农业大学 一类萘醌类化合物及其制备与杀螨、杀菌用途
CN114989057A (zh) * 2022-07-25 2022-09-02 江西农业大学 一种柠檬醛基酰基硫脲新型衍生物及其制备方法和应用

Also Published As

Publication number Publication date
CN111039896B (zh) 2022-04-05

Similar Documents

Publication Publication Date Title
Saeed et al. Synthesis, characterization and antimicrobial activity of some new 1-(fluorobenzoyl)-3-(fluorophenyl) thioureas
CN111039896B (zh) 一类苯并噻唑酰基硫脲类化合物及其制备与杀菌用途
Jarrahpour et al. Synthesis of novel β-lactams bearing an anthraquinone moiety, and evaluation of their antimalarial activities
CN104961781B (zh) 2‑脱氧‑2‑异硫氰酸酯‑1,3,4,6‑四‑O‑苄基‑β‑D‑吡喃葡萄糖及合成方法与用途
CN109251186B (zh) 一种含苯并噻唑的查尔酮类衍生物、其制备方法及应用
CN109942561A (zh) 4-(2-噻吩基)嘧啶衍生物及其制备方法和应用
CN112341365B (zh) 一种1-磺酰基萘酚类衍生物及其制备方法
CN109293616B (zh) 一种含香豆素查尔酮类衍生物、其制备方法及应用
CN106117180B (zh) 一种取代的吡啶联吡唑双酰肼类化合物及其制备方法和应用
CN106588871B (zh) 一种2-取代吡啶基喹唑啉酮类衍生物、其合成方法和用途
CN110447651B (zh) 一种喹唑啉酮类化合物及在制备或防治农业植物病害中的应用
CN110054579A (zh) 一种4-(1-h吲哚)苯酚衍生物的制备方法及其应用
CN111892511B (zh) N-（2-氯-4-氟苯基）-2-（2,4,6-三氯苯氧基）乙酰胺及其用途
US5889027A (en) 3(2H)-furanone derivatives
CN112608329A (zh) 青蒿素衍生物及其制备方法和应用
CN108570009B (zh) 3-卤素二芳胺基吡唑酰胺类化合物及其在农药中的应用
CN107033134B (zh) 含吡啶盐和1,3,4-噁二唑基的双酰胺类化合物及其制备方法及应用
CN108440510A (zh) 一种酰胺类杀菌剂
CN100569764C (zh) 一种取代苯甲酰胺基甲酸甲酯类化合物及其制备方法与应用
CN114957113B (zh) 2-氯喹啉-3-甲醛肟-o-(n-对氟苯基)氨基甲酸酯及其制备方法与应用
CN113896722B (zh) 含噻二唑基团的苯甲酰胺类化合物及其制备方法和应用
CN116178359B (zh) 一种基于杂环取代的二硫化物衍生物、其制备方法和用途
CN116730947B (zh) 2,4,5-三取代噻唑类化合物及其制备方法和应用
CN113683608B (zh) 具有杀菌活性的n-取代-2-氨基-4-糖精取代甲基噻唑类化合物、制备方法和应用
CN111747946B (zh) 5-苯并呋喃-1,3,4-噻二唑-2-取代酰胺类化合物及其制备方法与应用

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