S-2,3-dichloroallyl di-isopropylthiocarbamate | 17708-57-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代羰基化合物
• 英文名称: S-2,3-dichloroallyl di-isopropylthiocarbamate
• 英文别名: avadex；S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate；2,3-dichloroallyl N,N-diisopropylthiocarbamate；2,3-dichloroallyl N,N-diisopropylthiolcarbamate；S-(2,3-dichloroallyl) N,N-diisopropylthiocarbamate；di-allate；Diallate；S-[(Z)-2,3-dichloroprop-2-enyl] N,N-di(propan-2-yl)carbamothioate
• CAS: 17708-57-5
• 化学式: C₁₀H₁₇Cl₂NOS
• 分子量: 270.223
• InChiKey: SPANOECCGNXGNR-UITAMQMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  45.6
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

代谢

鼠标肝微粒体代谢顺式和反式-(14)C=O-二醇酸盐，在NADPH依赖反应中，主要产生(14)CO2，在没有谷胱甘肽（GSH）的情况下，以及在GSH存在时产生(14)CO2和S-(二异丙基羧基)-GSH。给予任一异构体的老鼠除了排出(14)CO2（20%）外，还排出S-二异丙基羧基衍生物的巯基尿酸（62%）、半胱氨酸（7%）和巯基乙酸（1.5%）。这条途径似乎涉及亚磺氧化，亚磺酸盐与GSH和非酶促反应以及巯基尿酸的形成。

MOUSE HEPATIC MICROSOMES METABOLIZE CIS- & TRANS-(14)C=O-DIALLATE IN NADPH-DEPENDENT REACTION, YIELDING PRIMARILY (14)CO2 IN ABSENCE OF GLUTATHIONE (GSH) & (14)CO2 & S-(DIISOPROPYLCARBAMOYL)-GSH IN PRESENCE OF GSH. RATS ADMIN EITHER ISOMER EXCRETE S-DIISOPROPYLCARBAMOYL DERIV OF MERCAPTURIC ACID (62%), CYSTEINE (7%) & MERCAPTOACETIC ACID (1.5%) IN ADDN TO (14)CO2 (20%). PATHWAY APPEARS TO INVOLVE SULFOXIDATION, NONENZYMATIC REACTION OF SULFOXIDE WITH GSH & MERCAPTURIC ACID FORMATION.

来源:Hazardous Substances Data Bank (HSDB)

代谢

口服多种含有卤代烯基或卤代烷基取代基的致突变剂和致癌剂的实验鼠会排泄少量尿液中的2-卤代丙烯酸，例如2-氯丙烯酸和2,3-二氯丙烯酸，这些物质来自二丙烯酸酯。

RATS TREATED ORALLY WITH SEVERAL PROMUTAGENS & CARCINOGENS CONTAINING HALOALLYL OR HALOPROPYL SUBSTITUENTS EXCRETE SMALL AMT OF URINARY 2-HALOACRYLIC ACIDS SUCH AS 2-CHLOROACRYLIC ACID & 2,3-DICHLOROACRYLIC ACID FROM DIALLATE.

来源:Hazardous Substances Data Bank (HSDB)

代谢

二异丙酸酯异构体的代谢通过它们的亚砜形式，在小鼠肝微粒体氧化酶系统中形成2-氯丙烯醛，并在小鼠和大鼠体内及其肝脏氧化酶的制备中形成2,3-二氯-2-丙烯-1-磺酸。

METABOLISM OF DIALLATE ISOMERS PROCEEDS VIA THEIR SULFOXIDES TO FORM 2-CHLOROACROLEIN IN MOUSE HEPATIC MICROSOMAL OXIDASE SYSTEM & 2,3-DICHLORO-2-PROPENE-1-SULFONIC ACID IN MICE & RATS IN VIVO & THEIR LIVER OXIDASE PREPN.

来源:Hazardous Substances Data Bank (HSDB)

代谢

双丙氨、三丙氨和硫代丙氨的提出的代谢物通过高效液相色谱（HPLC）和气相色谱（GLC）顶空分析被鉴定和定量为氯代丙烯醛和氯代烯丙基硫醇。定量关系表明，硫代氨基甲酸盐在混合功能氧化酶系统单独作用下代谢激活产生氯代丙烯醛，而当谷胱甘肽/谷胱甘肽-S-转移酶系统存在时，中间的S-氧化产物被转化为氯代烯丙基硫醇，从而解毒。三种化合物的主要小鼠微体混合功能氧化酶代谢物通过高效液相色谱共相色谱被鉴定为相应的亚磺酸酯。结论是，致突变氯代丙烯醛的形成主要涉及双丙氨的亚磺化，随后是sigma键迁移重排-1,2-消除反应，以及三丙氨和硫代丙氨的S-亚甲基羟基化，然后是其α-羟基中间体的分解。谷胱甘肽-S-转移酶催化的与谷胱甘肽的结合竞争，将亚磺化的中间体从涉及氯代丙烯醛形成的激活转向氯代烯丙基硫醇释放的解毒。

The proposed metabolites of diallate, triallate, and sulfallate were identified and quantitated by HPLC and GLC headspace analysis as chloroacroleins and chloroallylthiols. The quantitative relationships indicate that the thiocarbamates yield chloroacroleins on metabolic activation with the mixed function oxidase system alone, while the intermediate S-oxidation products were detoxified on diversion to chloroallylthiols when the glutathione/glutathione-S-transferase system was also present. The major mouse microsomal mixed function oxidase metabolites of three compounds were identified by HPLC cochromatography as the corresponding sulfoxides. It was concluded that the formation of mutagenic chloroacroleins involves primarily sulfoxidation of diallate followed by sigmatropic rearrangement-1,2-elimination reactions and S-methylene hydroxylation of triallate and sulfallate and then decomposition of their alpha-hydroxy intermediates. Competing glutathione-S-transferase catalyzed conjugations with glutathione divert the sulfoxidized intermediates from activation involving chloroacrolein formation to detoxification on chloroallylthiol liberation.

来源:Hazardous Substances Data Bank (HSDB)

代谢

一般来说，硫代氨基甲酸盐可以通过皮肤、粘膜以及呼吸和消化系统被吸收。它们主要通过呼出气体和尿液快速排出体外。哺乳动物中硫代氨基甲酸盐的代谢主要有两条途径。一是通过亚砜化并与谷胱甘肽结合。结合产物随后裂解为半胱氨酸衍生物，该衍生物被代谢为巯基尿酸化合物。第二条途径是硫原子的氧化形成亚砜，然后进一步氧化为砜，或者是羟基化成为能够进入碳代谢池的化合物。

As a general rule, thiocarbamates can be absorbed via the skin, mucous membranes, and the respiratory and gastrointestinal tracts. They are eliminated quite rapidly, mainly via expired air and urine. Two major pathways exist for the metabolism of thiocarbamates in mammals. One is via sulfoxidation and conjugation with glutathione. The conjugation product is then cleaved to a cysteine derivative, which is metabolized to a mercapturic acid compound. The second route is oxidation of the sulfur to a sulfoxide, which is then oxidized to a sulfone, or hydroxylation to compounds that enter the carbon metabolic pool.

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

草甘膦、敌草隆和磺草灵的代谢产物似乎具有诱变或致癌性。特别是，2-氯代烯丙基团对这些除草剂的诱变活性负有责任。这些代谢物可能通过与DNA结合或破坏DNA导致碱基对替换。已经证明敌草隆在小鼠中是一种致癌物。一些硫代氨基甲酸盐（EPTC、 Molinate、Pebulate和Cycloate）具有共同的毒性机制，即抑制乙酰胆碱酯酶。乙酰胆碱酯酶抑制剂抑制乙酰胆碱酯酶的作用。由于其基本功能，干扰乙酰胆碱酯酶作用的化学物质是强效的神经毒素，在低剂量下会导致过度流涎和流泪。在高水平的暴露下，头痛、流涎、恶心、呕吐、腹痛和腹泻常常很明显。乙酰胆碱酯酶分解在神经和肌肉接头释放的神经递质乙酰胆碱，以允许肌肉或器官放松。乙酰胆碱酯酶抑制的结果是乙酰胆碱积聚并继续发挥作用，使得任何神经冲动不断传递，肌肉收缩不会停止。

The metabolic products of triallate, diallate and sulfallate appear to be mutagenic or carcinogenic. In particular, the 2-chloro-allyl group is responsible for the mutagenicity of these herbicides. These metabolites likely bind to or disrupt DNA causes base-pair subsitutions. Diallate has been shown to be a carcinogen in mice. Some thiocarbamates (EPTC, Molinate, Pebulate, and Cycloate) share a common mechanism of toxicity, i.e. the inhibition of acetylcholinesterase. An acetylcholinesterase inhibitor suppresses the action of acetylcholine esterase. Because of its essential function, chemicals that interfere with the action of acetylcholine esterase are potent neurotoxins, causing excessive salivation and eye-watering in low doses. Headache, salivation, nausea, vomiting, abdominal pain and diarrhea are often prominent at higher levels of exposure. Acetylcholine esterase breaks down the neurotransmitter acetylcholine, which is released at nerve and muscle junctions, in order to allow the muscle or organ to relax. The result of acetylcholine esterase inhibition is that acetylcholine builds up and continues to act so that any nerve impulses are continually transmitted and muscle contractions do not stop.

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

美国环保局健康与环境评估办公室的人类健康评估小组对敌草快进行了致癌性评估。根据他们的分析，敌草快的证据权重为C组，这是基于动物中的有限证据。在人类中没有可用数据。作为C组化学物质，敌草快被认为是一种可能的 human致癌物。

The Human Health Assessment Group in EPA's Office of Health and Environmental Assessment has evaluated diallate for carcinogenicity. According to their analysis, the weight-of-evidence for diallate is group C, which is based on limited evidence in animals. No data is available in human. As a group C chemical, diallate is considered to be a possible human carcinogen.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

没有关于人类的数据。动物致癌性的证据有限。总体评估：第3组：该物质对人类致癌性无法分类。

No data are available in humans. Limited evidence of carcinogenicity in animals. OVERALL EVALUATION: Group 3: The agent is not classifiable as to its carcinogenicity to humans.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

国际癌症研究机构致癌物：敌草快

IARC Carcinogenic Agent:Diallate

来源:International Agency for Research on Cancer (IARC)

毒理性

• 致癌物分类

国际癌症研究机构（IARC）致癌物分类：第3组：无法归类其对人类致癌性

IARC Carcinogenic Classes:Group 3: Not classifiable as to its carcinogenicity to humans

来源:International Agency for Research on Cancer (IARC)

吸收、分配和排泄

口服剂量大部分（88%）在48小时内消除。

ORAL DOSE LARGELY (88%) ELIMINATED IN 48 HR.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在野燕麦中，主要的吸收是通过新生的鞘片。在幼苗发育的早期阶段，吸收量极其微小。

IN WILD OAT, PRIMARY ABSORPTION IS THROUGH EMERGING COLEOPTILE. EXTREMELY MINOR UPTAKE AT EARLY STAGES OF SEEDLING DEVELOPMENT.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

...标记的二嗪烷被野生燕麦（Avena fatua L）、小麦（Triticum aestivum L var Selkirk）、大麦（Hordeum vulgare L var Trail）、亚麻（Linum usitatissimum L var Bolley）的根和鞘叶吸收与转运（14）碳的研究...已经完成并得出结论...吸收与移动的模式是相似的...

... UPTAKE & TRANSLOCATION OF (14)CARBON FROM LABELED DIALLATE BY ROOTS & COLEOPTILES OF WILD OAT (AVENA FATUA L), WHEAT (TRITICUM AESTIVUM L VAR SELKIRK), BARLEY (HORDEUM VULGARE L VOR TRAIL), FLAX (LINUM USITATISSIMUM L VAR BOLLEY), /WAS STUDIED/ & CONCLUDED ... PATTERN OF ... UPTAKE & MOVEMENT WAS SIMILAR ...

来源:Hazardous Substances Data Bank (HSDB)

反应信息

• 作为反应物：
  描述：

  S-2,3-dichloroallyl di-isopropylthiocarbamate 生成 1,2-dichloro-1-propen-3-al
  参考文献：
  名称：

  RUZO, L. O.;CASIDA, J. E., J. AGR. AND FOOD CHEM., 1985, 33, N 2, 272-276

  摘要：

  DOI：

文献信息

• Molecules having pesticidal utility, and intermediates, compositions, and processes, related thereto
  申请人：Dow AgroSciences LLC

  公开号：US20180279612A1

  公开（公告）日：2018-10-04

  This disclosure relates to the field of molecules having pesticidal utility against pests in Phyla Arthropoda, Mollusca, and Nematoda, processes to produce such molecules, intermediates used in such processes, pesticidal compositions containing such molecules, and processes of using such pesticidal compositions against such pests. These pesticidal compositions may be used, for example, as acaricides, insecticides, miticides, molluscicides, and nematicides. This document discloses molecules having the following formula (“Formula One”).

  这份披露涉及具有对节肢动物门、软体动物门和线虫门害虫具有杀虫效用的分子领域，用于生产此类分子的过程，用于此类过程的中间体，含有此类分子的杀虫组合物，以及使用此类杀虫组合物对抗此类害虫的过程。这些杀虫组合物可以用作螨虫剂、杀虫剂、螨虫剂、软体动物杀虫剂和线虫杀虫剂。本文件披露了具有以下式（“式一”）的分子。
• [EN] MOLECULES HAVING PESTICIDAL UTILITY, AND INTERMEDIATES, COMPOSITIONS, AND PROCESSES, RELATED THERETO<br/>[FR] MOLÉCULES PRÉSENTANT UNE UTILITÉ EN TANT QUE PESTICIDE, ET LEURS INTERMÉDIAIRES, COMPOSITIONS ET PROCÉDÉS
  申请人：DOW AGROSCIENCES LLC

  公开号：WO2017040194A1

  公开（公告）日：2017-03-09

  This disclosure relates to the field of molecules having pesticidal utility against pests in Phyla Arthropoda, Mollusca, and Nematoda, processes to produce such molecules, intermediates used in such processes, pesticidal compositions containing such molecules, and processes of using such pesticidal compositions aga inst such pests. These pesticidal compositions may be used, for example, as acaricides, insecticides, miticides, molluscicides, and nematicides. This document discloses molecules having the following formula ("Formula One").

  这份披露涉及具有对节肢动物门、软体动物门和线虫门害虫有用的分子领域，用于生产这种分子的过程，用于这种过程的中间体，含有这种分子的杀虫剂组合物，以及使用这种杀虫剂组合物对抗这些害虫的过程。这些杀虫剂组合物可以用作螨虫剂、杀虫剂、螨虫剂、软体动物杀虫剂和线虫杀虫剂。本文件披露了具有以下化学式（“化学式一”）的分子。
• MOLECULES HAVING PESTICIDAL UTILITY, AND INTERMEDIATES, COMPOSITIONS, AND PROCESSES, RELATED THERETO
  申请人：Dow AgroSciences LLC

  公开号：US20170210723A1

  公开（公告）日：2017-07-27

  This disclosure relates to the field of molecules having pesticidal utility against pests in Phyla Arthropoda, Mollusca, and Nematoda, processes to produce such molecules, intermediates used in such processes, compositions containing such molecules, and processes of using such molecules and compositions against such pests. These molecules and compositions may be used, for example, as acaricides, insecticides, miticides, molluscicides, and nematicides. This document discloses molecules having the following formula (“Formula One”).

  这份披露涉及具有对节肢动物门、软体动物门和线虫门害虫具有杀虫效用的分子领域，用于生产这种分子的过程，用于这种过程的中间体，含有这种分子的组合物，以及使用这种分子和组合物对抗这些害虫的过程。这些分子和组合物可以用作杀螨剂、杀虫剂、杀螨剂、杀软体动物剂和杀线虫剂。本文件披露了具有以下式（“式一”）的分子。
• HYDRAZONYL GROUP-CONTAINING CONDENSED HETEROCYCLIC COMPOUND OR SALT THEREOF, AGRICULTURAL AND HORTICULTURAL INSECTICIDE COMPRISING THE COMPOUND, AND METHOD FOR USING THE INSECTICIDE
  申请人：Nihon Nohyaku Co., Ltd.

  公开号：US20190177319A1

  公开（公告）日：2019-06-13

  An object of the present invention is to develop and provide a novel agricultural and horticultural insecticide in view of the still immense damage caused by insect pests etc. and the emergence of insect pests resistant to existing insecticides in crop production in the fields of agriculture, horticulture and the like. Provided is a hydrazonyl group-containing condensed heterocyclic compound or a salt thereof, preferably a condensed heterocyclic compound represented by the general formula (1): wherein R 1 represents, for example, an alkyl group, R 2 represents, for example, a hydrogen atom, R 3 and R 4 each represent, for example, an alkyl group, a haloalkyl group or an acyl group, A 1 represents, for example, a nitrogen atom, A 2 represents, for example, N-Me or an oxygen atom, A 3 represents, for example, a carbon atom or a nitrogen atom, A 4 represents, for example, C—H, m represents, for example, 2, and n represents, for example, 1}, or a salt thereof; an agricultural and horticultural insecticide comprising the compound or a salt thereof as an active ingredient; and a method for using the insecticide.

  本发明的一个目的是开发并提供一种新型农艺和园艺杀虫剂，鉴于昆虫害虫等造成的损害仍然巨大，以及在农业、园艺等领域作物生产中出现的对现有杀虫剂具有抗性的昆虫害虫。 提供了一种含有肼酰基的稠合杂环化合物或其盐，优选为通式(1)表示的稠合杂环化合物： 其中R1代表例如烷基，R2代表例如氢原子，R3和R4各自代表例如烷基、卤代烷基或酰基，A1代表例如氮原子，A2代表例如N-Me或氧原子，A3代表例如碳原子或氮原子，A4代表例如C—H，m代表例如2，n代表例如1}，或其盐；一种包含该化合物或其盐作为活性成分的农艺和园艺杀虫剂；以及使用该杀虫剂的方法。
• [EN] MACROCYCLIC PICOLINAMIDES AS FUNGICIDES<br/>[FR] PICOLINAMIDES MACROCYCLIQUES À UTILISER EN TANT QUE FONGICIDES
  申请人：DOW AGROSCIENCES LLC

  公开号：WO2017116954A1

  公开（公告）日：2017-07-06

  The invention relates to macrocyclic picolinamides of Formula (I) and their use as fungicides.

  本发明涉及式(I)所示的大环吡啶酰胺及其作为杀菌剂的应用。

表征谱图