1,3-二氯丙烯 | 542-75-6

• 物质功能分类: 化学农药原药 - 除草剂 - 氨基甲酸酯类除草剂
• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 中文名称: 1,3-二氯丙烯
• 中文别名: 1,3-二氯-1-丙烯；3-氯丙烯基氯；滴滴混合剂；2-氯丙烯基氯；1,3二氯丙烯；滴滴混剂；滴滴剂；邻二氯丙烯
• 英文名称: 1,3-Dichloropropene
• 英文别名: E/Z-1,3-Dichloropropene；1,3-dichloroprop-1-ene
• CAS: 542-75-6
• 化学式: C₃H₄Cl₂
• mdl: MFCD00000985
• 分子量: 110.971
• InChiKey: UOORRWUZONOOLO-UHFFFAOYSA-N

物化性质

• 熔点：
  -60 °C
• 沸点：
  97-112 °C(lit.)
• 密度：
  1.2
• 闪点：
  78 °F
• 溶解度：
  易溶于可溶于氯仿、甲醇
• 暴露限值：
  ACGIH: TWA 1 ppm (Skin)NIOSH: TWA 1 ppm(5 mg/m3)
• LogP：
  2.040
• 稳定性/保质期：

  1. 稳定性：稳定。

  2. 禁配物：强氧化剂、酸类。

  3. 避免接触的条件：受热。

  4. 聚合危害：可能发生聚合。

  5. 分解产物：氯化氢、光气。

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  5
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.333
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

对小鼠肝脏毒性的研究表明，摄入的1,3-二氯丙烯通过细胞色素P-450进行生物转化，其代谢物诱导肝脏损伤，并且谷胱甘肽在1,3-二氯丙烯的解毒中发挥重要作用。

Studies of hepatic toxicity in mice suggest that ingested 1,3-dichloropropene is biotransformed via cytochrome P-450, with metabolites inducing liver damage, and that glutathione plays an important role in the detoxification of 1,3-dichloropropene.

来源:Hazardous Substances Data Bank (HSDB)

代谢

给予大鼠1,3-二氯-2-丙烯的主要尿液代谢物是巯基尿酸。

The major urinary metabolite in rats given 1,3-dichloro-2-propene was a mercapturic acid.

来源:Hazardous Substances Data Bank (HSDB)

代谢

(14)C-1,3-二氯丙烯((14)C-DCP)在给予F344雄性大鼠和B6C3F1小鼠口服1或50 mg/kg(大鼠)或1或100 mg/kg(小鼠)后，能迅速被吸收并排出。这两种动物都会对(14)C-DCP进行广泛的代谢。尿液排泄是主要的消除途径，分别占大鼠和小鼠给药剂量的50.9-61.3%和62.5-78.6%。尿液排泄的半衰期在大鼠中为5至6小时，在小鼠中为7至10小时。通过粪便或作为(14)CO2排出的分别占给药剂量的14.5-20.5%和13.7-17.6%。来自谷胱甘肽结合的代谢物分别占从大鼠和小鼠排泄的给药剂量的36-55%和48-50%。DCP的3-氯基团的 hydrolysis 分别占给予大鼠和小鼠的剂量的24-37%和29%。还发现了两种新的低水平的二巯基尿酸结合物，可能是由于DCP的初步 hydrolysis 或DCP-谷胱甘肽结合物或DCP本身的环氧化作用产生的。通过分析雄性F344大鼠中D4-DCP的氘保留，获得了这些二巯基尿酸的结构确认。在这两个物种中，DCP的整体代谢图谱只有定量差异。

(14)C-1,3-dichloropropene ((14)C-DCP) is rapidly absorbed and eliminated in both the male F344 rat and B6C3F1 mouse following oral administration of 1 or 50 mg/kg (rat) or 1 or 100 mg/kg (mouse). It is extensively metabolized in both species. Urinary excretion was the major route of elimination, accounting for 50.9-61.3 and 62.5-78.6% of the administered dose in rat and mouse, respectively. Urinary elimination half-lives ranged from 5 to 6 hr (rat) and from 7 to 10 hr (mouse). Elimination via feces or as (14)CO2 accounted for 14.5-20.5 and 13.7-17.6% of the administered dose, respectively. Metabolites arising from glutathione conjugation account for 36-55 and 48-50% of the administered dose in excreted from rats and mice, respectively. Hydrolysis of the 3-chloro moiety of DCP accounted for 24-37 and 29% of the dose administered to rats and mice, respectively. Two novel dimercapturic acid conjugates were also identified at low levels that might arise via initial hydrolysis of DCP or of epoxidation of DCP-glutathione conjugate or of DCP itself. Structural confirmation of these dimercapturates was obtained via analysis of deuterium retention from D4-DCP in the male F344 rat. Only quantitative differences are seen between the overall metabolic profile of DCP in these two species.

来源:Hazardous Substances Data Bank (HSDB)

代谢

1,3-二氯丙烯（1,3-DCP）在全球范围内被用作土壤杀线虫剂。工业级1,3-DCP具有基因毒性/致突变性和致癌性。/之前的一项研究/报道称，经过硅胶柱色谱纯化后，1,3-DCP样品的致突变活性消失。我们发现，经过硅胶纯化后，大肠杆菌PM 21株的致突变性和SOS修复能力显著降低，且致突变性和SOS修复的诱导依赖于氧化杂质和次级产物。1,3-DCP的两种异构体（E型和Z型）被氧化成1,3-二氯丙烯环氧化物（1,3-DCP-Ox）。环氧化物会迅速发生内部重排形成2,3-二氯丙醛（2,3-DCPA），后者自发脱除HCl并生成极具致突变性、基因毒性和致癌性的2-氯丙烯醛（α-氯丙烯醛）α-ClA。因此，未纯化的1,3-DCP样品的基因毒性和致突变性主要取决于α-ClA。其潜在的基因毒性和致突变机制是α-ClA形成促突变的外环1,N(2)-丙烷脱氧鸟苷加合物。纯化的1,3-DCP样品在 trifluoroacetic 酸溶剂解反应、水解和计算反应性方面只有很低的S(N)1反应性，但在使用4-(对硝基苄基)吡啶（NBP）和N-甲基巯基咪唑（MMI）等亲核试剂进行的烷基化测试中表现出中等的S(N)2反应性。显然，低的S(N)1反应性不足以形成Salmonella typhimurium TA1535株回复突变所需的O(6)-烷基鸟嘌呤DNA加合物的必要量。然而，S(N)2反应性可能导致形成其他DNA加合物，例如N7-鸟嘌呤加合物，这可以在S. typhimurium TA100株中诱导出错倾向修复，从而在该株中引起回复突变。在农业中使用1,3-DCP样品必须被视为突变风险，因为样品可能会被氧化并形成极具致突变性的α-ClA。因此，是否有任何稳定剂能在应用过程中防止氧化是值得怀疑的。

1,3-Dichloropropene (1,3-DCP) is used as a soil nematocide worldwide. Technical grade 1,3-DCP is genotoxic/mutagenic and carcinogenic. /A previous study/ reported that mutagenic activity is lost after purification of 1,3-DCP samples via silica gel column chromatography. We found that mutagenicity and SOS repair in Escherichia coli, strain PM 21, are strongly reduced after purification via silica gel and that mutagenicity and induction of SOS repair depend on oxidative impurities and secondary products. Both isomers (E and Z) of 1,3-DCP are oxidized to 1,3-dichloropropene epoxide (1,3-DCP-Ox). The epoxide is subjected to rapid internal rearrangement to 2,3-dichloropropanal (2,3-DCPA), which spontaneously eliminates HCl and forms the extremely mutagenic, genotoxic, and carcinogenic 2-chloroacrolein (alpha-chloroacrolein) alpha-ClA. Thus, the genotoxic/mutagenic effects of unpurified 1,3-DCP samples mainly depend on alpha-ClA. The underlying genotoxic and mutagenic mechanism is formation of promutagenic exocyclic 1,N(2)-propanodeoxyguanosine adducts of alpha-ClA. Pure 1,3-DCP samples have only a very low S(N)1 reactivity as measured in trifluoroacetic acid solvolysis reactions, hydrolysis, and computed reactivities but possess a moderate S(N)2 reactivity as determined in alkylation tests with the nucleophiles 4-(p-nitrobenzyl)pyridine (NBP) and N-methyl-mercaptoimidazole (MMI). Evidently, the low S(N)1 reactivity is not sufficient to form necessary amounts of O(6)-alkylguanine DNA adducts required for back-mutation in Salmonella typhimurium strain TA1535. The S(N)2 reactivity may, however, lead to other DNA adducts, e.g., N7-guanine adducts, which can induce error prone repair in S. typhimurium strain TA100 and thus lead to back-mutation in this strain. Application of 1,3-DCP samples in agriculture must be considered as a mutagenic risk because the samples can be oxidized and form the extremely mutagenic alpha-ClA. As a consequence, it is questionable whether any stabilizers can prevent oxidation during application.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别和使用：1,3-二氯丙烯是一种无色至琥珀色液体，具有刺激性、刺激性的氯仿气味。它已被广泛应用于农业中，作为一种种植前土壤熏蒸剂，用于控制蔬菜、土豆和烟草中的线虫。它通常作为包含1,2-二氯丙烷的混合物的一部分出现。主要应用方式是通过土壤注射。 人类暴露和毒性：暴露后眼睛和上呼吸道粘膜会出现急性炎症。皮肤暴露导致严重的皮肤刺激。吸入可能导致严重的毒害症状，低剂量暴露会导致中枢神经系统抑制和呼吸系统刺激。一些中毒事件中，有人因粘膜刺激、胸痛、头痛、恶心、呕吐、眩晕，偶尔还出现意识丧失和性欲减退而住院。从事氯化三碳化合物生产的工人的生育状况与对照组进行了比较。没有迹象表明生育能力下降与暴露有关。 动物研究：1,3-二氯丙烯在动物体内的急性口服毒性为中等至高。急性皮肤暴露具有中等毒性。急性中毒表现为中枢神经和呼吸系统受累。家兔皮肤和眼刺激试验中观察到严重反应。在小鼠和大鼠的吸入研究中，观察到嗅上皮变性增生。顺式和反式-1,3-二氯丙烯及其混合物在有和没有代谢激活的细菌中具有诱变性。在小鼠中，观察到尿路上皮、前胃和鼻粘膜增生的发生率增加。良性肺肿瘤的发生率有所增加。在大鼠的嗅粘膜中也看到了一些毒性变化，但没有增加肿瘤发生率。 生态毒性研究：1,3-二氯丙烯对咸水水生生物的急性毒性在浓度低至790 mg/L时发生。在针对混合群体绿鱼和胖头鱼的1,3-二氯丙烯测试中，100%的鱼在1,000微克/升下存活了3天，而在10,000微克/升下没有存活。1,3-二氯丙烯在20微克/毫升空气中，经过30小时的培养后杀死了100%的微菌核，在100微克/克土壤水分下经过3天的培养后。温度升高增加了毒性。

IDENTIFICATION AND USE: 1,3-Dichloropropene is a colorless to amber colored liquid with a penetrating, irritating, chloroform-like odor. It has been widely used in agriculture as a pre-plant soil fumigant for the control of nematodes in vegetables, potatoes, and tobacco. It often appears as part of a mixture also including 1,2-dichloropropane. Application is primarily by soil injection. HUMAN EXPOSURE AND TOXICITY: Irritation of the eyes and the upper respiratory mucosa appears promptly after exposure. Dermal exposure caused severe skin irritations. Inhalation may result in serious signs and symptoms of poisoning with lower exposures resulting in depression of the central nervous system and irritation of the respiratory system. Some poisoning incidents have occurred in which persons were hospitalized with signs and symptoms of irritation of the mucous membrane, chest discomfort, headache, nausea, vomiting, dizziness and, occasionally, loss of consciousness and decreased libido. The fertility status of workers employed in the production of chlorinated three-carbon compounds was compared with a control group. There was no indication of an association between decreased fertility and exposure. ANIMAL STUDIES: The acute oral toxicity of 1,3-dichloropropene in animals is moderate to high. Acute dermal exposure is moderately toxic. Acute intoxication showed central nervous and respiratory system involvement. Severe reactions were seen in rabbit skin and eye irritation tests. Degeneration of the olfactory epithelium and hyperplasia were seen in inhalation studies with mice and rats. Cis- and trans-1,3-dichloropropene and mixtures were mutagenic in bacteria with, and without, metabolic activation. In mice, increased incidences of hyperplasia of the urinary bladder, the forestomach, and the nasal mucosa were observed. There was an increase in the incidence of benign lung tumors. Some toxic changes in the olfactory mucosa of the nasal cavity were also seen in rats, but no increase in tumor incidence. ECOTOXICITY STUDIES: The acute toxicity of 1,3-dichloropropene to saltwater aquatic life occurs at concn as low as 790 mg/L. In a test conducted on a mixed assemblage of emerald shiners and fathead minnows exposed to 1,3-dichloropropene, 100% of the fish survived 3 days at 1,000 ug/L, and none survived at 10,000 ug/L. 1,3-Dichloropropene at 20 ug/mL of air, killed 100% of microsclerotia after incubation for 30 hr, and at 100 ug/g of soil moisture after incubation for 3 days. Higher temperatures increased the toxicity.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

评估：关于1,3-二氯丙烯的致癌性，没有可用的流行病学数据。混合异构体的1,3-二氯丙烯（工业级）在实验动物中具有充分的致癌性证据。总体评估：1,3-二氯丙烯（工业级）可能对人类具有致癌性（2B组）。

Evaluation: No epidemiological data relevant to the carcinogenicity of 1,3-dichloropropene were available. There is sufficient evidence in experimental animals for the carcinogenicity of mixed isomers of 1,3-dichloropropene (technical grade). Overall evaluation: 1,3-Dichloropropene (technical grade) is possibly carcinogenic to humans (Group 2B).

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

癌症分类：B2组可能的人类致癌物

Cancer Classification: Group B2 Probable Human Carcinogen

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

证据权重特征：人类数据不足以评估1,3-二氯丙烯对人类潜在致癌性的影响，因为唯一可用的人类数据是病例研究。在慢性动物生物试验中，1,3-二氯丙烯在高剂量灌胃时在F344大鼠（前胃、肝脏）和B6C3F1小鼠（前胃、膀胱和肺）中产生了肿瘤，在较低膳食剂量时在F344大鼠中产生了肝脏肿瘤，通过吸入途径在雄性小鼠中产生了良性肺肿瘤。尽管1,3-二氯丙烯在添加S9的细菌试验中诱发了正向突变反应，最有力的突变性证据是从高剂量（约LD50）的小鼠肝脏中分离出突变性环氧化代谢物。因此，根据当前的风险评估指南（USEPA, 1987），由于缺乏人类数据和动物致癌性的充分证据，1,3-二氯丙烯被归类为B2，可能的的人类致癌物。尽管现有的人类数据不足，根据拟定的致癌风险评估指南（USEPA, 1996），1,3-二氯丙烯被定性为“可能”是人类致癌物。这种特征是基于慢性动物生物试验中观察到的通过吸入和口服途径的肿瘤。尽管慢性膳食和吸入生物试验表明在低剂量下可能不会发生肿瘤，但现有机制数据不支持肿瘤形成的非线性机制。实际上，1,3-二氯丙烯的致突变特性表明了一种基因毒性作用机制。致突变特性和缺乏支持肿瘤形成非线性机制的数据要求定量评估默认为线性模型。人类致癌性数据：不足。动物致癌性数据：充分。

WEIGHT-OF-EVIDENCE CHARACTERIZATION: Human data are inadequate for assessment of the potential human carcinogenicity of 1,3-dichloropropene because the only human data available are case studies. In chronic animal bioassays, 1,3-dichloropropene produced tumors in F344 rats (forestomach, liver) and B6C3F1 mice (forestomach, urinary bladder, and lung) at high gavage doses, liver tumor in F344 rats at lower dietary doses, and benign lung tumors in male mice exposed via inhalation. Although 1,3-dichloropropene elicited a positive response for mutagenicity in bacterial assays with the addition of S9, the most compelling evidence for mutagenicity is the isolation of mutagenic epoxide metabolites from mouse liver at high (~LD50) doses. Thus, under the current Risk Assessment Guidelines (USEPA, 1987), 1,3-dichloropropene is a B2, probable human carcinogen, because of the lack of data in humans and sufficient evidence of carcinogenicity in animals. Although the available human data are inadequate, 1,3-dichloropropene is characterized as "likely" to be a human carcinogen in accordance with the Proposed Guidelines for Carcinogen Risk Assessment (USEPA, 1996). This characterization is based on tumors observed in chronic animal bioassays for both inhalation and oral routes of exposure. Although the chronic dietary and inhalation bioassays suggest that tumors may not occur at low doses, a nonlinear mechanism of tumor formation is not supported by the available mechanistic data. In fact, the mutagenic properties of 1,3-dichloropropene suggest a genotoxic mechanism of action. The mutagenic properties and the absence of data to support a nonlinear mechanism of tumor formation require that the quantitative assessment default to a linear model. HUMAN CARCINOGENICITY DATA: Inadequate. ANIMAL CARCINOGENICITY DATA: Sufficient.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

A3；已确认对动物有致癌性，但对人类的相关性未知。

A3; Confirmed animal carcinogen with unknown relevance to humans.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

吸入研究在人类和老鼠中都显示二氯丙烯（DCP）很容易被吸收，通过谷胱甘肽S-转移酶（GST）与谷胱甘肽（GSH）结合，并迅速以N-乙酰-S-(顺-3-氯丙烯基)-半胱氨酸（3CNAC）的形式在尿液中排出，这是一种巯基尿酸代谢物。一项对六名男性志愿者在1 ppm商业Telone II（50.6%顺式异构体，45.2%反式异构体）暴露6小时的研究发现，顺式-DCP的吸收率为72%至80%，而反式-DCP的吸收率为77%至82%。在大鼠以136 mg/立方米DCP暴露3小时后，发现了类似的吸收百分比。DCP在体内不会生物累积。大鼠和人类在血液中清除和巯基尿酸代谢物排出的半衰期相似。/一项研究/发现，在暴露的第一个小时内，呼出空气中的DCP浓度和血液中的浓度达到平台，并在暴露后迅速下降，在不到一小时内降至不可检测的水平。在大鼠和小鼠中，DCP的尿液排出半衰期大约为5.5小时。口服放射性标记的DCP在大鼠体内，治疗后的24小时内尿液中有82%至84%的放射性。这其中的大部分（14）C（92%）以N-乙酰-S-((Z), 3-氯丙烯基)半胱氨酸（Z）-DCP巯基尿酸的形式存在。在4天内，每个异构体的剂量约有1%在尸体中被发现。

Inhalation studies with both humans and rats have shown that dichloropropene (DCP) is readily absorbed, conjugated with glutathione (GSH) via glutathione S-transferase (GST), and rapidly excreted in the urine as N-acetyl-S-(cis-3-chloroprop-2-enyl)-cysteine (3CNAC), a mercapturic acid metabolite. A study of six male volunteers exposed at 1 ppm commercial Telone II (50.6% cis-isomer, 45.2% trans-isomer) for 6 hours found the absorption of cis-DCP was 72% to 80%, while the absorption of trans-DCP was 77% to 82%. A similar percent absorption was found in rats exposed at 136 mg/cu m DCP for 3 hours. DCP does not bioaccumulate in the body. Half-lives were similar for both rats and humans for removal from the blood and for excretion of mercapturic acid metabolites. /A study/ found that the concentration of DCP in expired air and concentration in blood plateaued in the first hour of exposure and declined rapidly postexposure to nondetectable levels in less than an hour. A urinary excretion half-life of approximately 5.5 hours for DCP in rats and mice was calculated. Radio-labeled DCP, when dosed orally in rats, yielded 82% to 84% of the radioactivity in the urine within 24 hours after treatment. Most of this (14)C (92%) was present as N-acetyl-S-((Z), 3-chloroprop-2-enyl) cysteine (Z)-DCP mercapturic acid). Within 4 days, about 1% of the dose of each isomer was found in the carcass.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

一些研究已经得出结论，接触二氯丙烯（DCP）期间和之后的尿液收集可能代表了对DCP的接触。测量了12名职业接触DCP的应用者在尿液中的硫醚排泄，并将其与巯基尿酸代谢物的排泄进行了比较。对DCP的Z-异构体和E-异构体的8小时时间加权平均暴露量在1到11小时的工作班次中从0.3到18.9毫克/立方米不等。累积的尿硫醚排泄和尿后班次水平减去前班次水平与DCP暴露相关性很好。平均尿硫醚浓度比平均DCP巯基尿酸代谢物浓度高出1.38倍，这表明存在一种未知的硫醚代谢物。硫醚分析很好地与相对较高的DCP暴露相关。

... /Some/ studies have concluded that urine collection during and after exposure may be representative of exposure to dichloropropene (DCP). Urinary excretion of thioethers was measured in 12 applicators occupationally exposed to DCP and was compared to excretion of the mercapturic acid metabolites. The 8-hour time weighted average exposures to the Z-isomer and the E-isomer of DCP ranged from 0.3 to 18.9 mg/cu m over 1- to 11-hour shifts. Cumulative urinary thioether excretions and urinary postshift levels minus preshift levels correlated well with DCP exposures. Mean urinary thioether concentrations were 1.38-fold greater than the mean DCP mercapturic acid metabolite concentration, suggesting the presence of an unidentified thioether metabolite. The thioether assay correlated well with relatively high DCP exposures.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

荷兰花卉球茎文化行业中对二氯丙烯（DCP）的职业和非职业暴露进行研究，发现吸入暴露与DCP的巯基尿酸完全累积尿排泄之间存在强烈相关性。亚慢性DCP暴露可能存在亚临床肾脏毒性作用。血液中谷胱甘肽和谷胱甘肽-S-转移酶（GST）活性显著降低，这表明DCP暴露可能影响谷胱甘肽结合能力。

Studies conducted on occupational and non-occupational exposure to dichloropropene (DCP) in the Dutch flower bulb culture industry found a strong correlation between inhalation exposure and the complete cumulative urinary excretion of the mercapturic acids of DCP. A possible subclinical nephrotoxic effect of subchronic DCP exposure was noted. There was a notable decrease of glutathione and GST activity in blood, suggesting that DCP exposure may affect the glutathione conjugating capacity.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在一项针对15名二氯丙烯（DCP）施用者的个人空气监测研究中，研究了DCP代谢物3CNAC的排泄和肾小管酶NAG（N-乙酰葡萄糖苷酶）的排泄。在基线后，四名工人在他们所有的尿样中都有临床上升高的NAG。与基线相比，九名工人的NAG排泄量增加了超过25%。当空气暴露产物大于700毫克/分钟/立方米或排泄超过1.5毫克3CNAC/天时，可以区分出异常高的每日NAG排泄。这些数据表明空气暴露与内部暴露之间存在正相关关系，工人可能存在亚临床的肾毒性效应。在随后的研究中，使用这些相同的尿样，这些尿样在连续五个6到8小时的时间间隔内收集并冷冻保存了4年，作者分析了样品中的白蛋白和视黄醇结合蛋白（RBP）。在第二个到第五个收集间隔期间，尿中白蛋白和RBP的排泄相对于基线期在肌酐校正后没有显著增加。在每个间隔内，白蛋白和RBP的排泄与彼此和3CNAC浓度显著相关。九名受试者的NAG排泄略有增加。当3CNAC排泄数据被二分类为排泄少于和超过1.5毫克/天的受试者，这对应于低和高DCP暴露时，低暴露组的尿NAG和RBP排泄显著低于高暴露组。尿白蛋白排泄在两组中相似。尿中RBP和白蛋白在基线期的排泄与24小时累积排泄的这些蛋白质相关性最好，如逻辑回归分析所示。下午班次的NAG排泄与24小时累积NAG排泄相关性最好。第二天早晨的尿3CNAC排泄与其24小时累积排泄相关性最好。结论是，在农药施用者使用的条件下，DCP对肾脏的影响很小。

In /a/ personal air monitoring study of 15 applicators of dichloropropene (DCP), excretion of the DCP metabolite, 3CNAC, and excretion of the renal tubular enzyme, NAG [N-acetyl glucosaminidase], were studied. Four workers had clinically elevated NAG in all of their urine collections after baseline. Nine workers showed greater than 25% increases in NAG excretion when compared to baseline. Dichloropropene air exposure products of >700 mg/min/cu m or excretion of >1.5 mg 3CNAC/day distinguished abnormally high daily excretion of NAG. These data indicate a positive relationship between air exposure and internal exposure and a possible subclinical nephrotoxic effect in workers. In a subsequent study using these same urine samples collected during five consecutive 6- to 8-hour intervals and stored frozen for 4 years, /the authors/ analyzed the samples for albumin and retinal binding protein (RBP). Urinary excretion of albumin and RBP during the second through fifth collection intervals was not significantly increased relative to the baseline period after correction for creatinine. Within each interval, excretion of albumin and RBP was significantly correlated with each other and the 3CNAC concentrations. NAG excretion was slightly increased in nine subjects. When the 3CNAC excretion data were dichotomized into subjects excreting less than and more than 1.5 mg/day, which corresponded to low and high DCP exposures, urinary excretion of NAG and RBP was significantly lower in the low exposure than in the high exposure group. Urinary albumin excretion was similar in both groups. Urinary excretion of RBP and albumin during the baseline period correlated best with 24 hours cumulative excretion of these proteins as indicated by logistic regression analysis. Excretion of NAG during the afternoon shift correlated best with 24-hour cumulative NAG excretion. Urinary 3CNAC excretion during the next morning correlated best with its 24-hour cumulative excretion. The conclusion made was that under the conditions used by pesticide applicators, DCP has only a slight effect on the kidney.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 职业暴露等级：
  B
• 职业暴露限值：
  TWA: 1 ppm (5 mg/m3) [skin]
• TSCA：
  Yes
• 危险等级：
  3
• 危险品标志：
  T
• 安全说明：
  S36/37,S45,S60,S61
• 危险类别码：
  R20/21,R36/37/38,R43,R10,R50/53,R25
• WGK Germany：
  3
• 海关编码：
  2903199000
• 危险品运输编号：
  UN 1992 3/PG 3
• 危险类别：
  3
• RTECS号：
  UC8310000
• 包装等级：
  II
• 储存条件：
  储存注意事项： - 储存于阴凉、通风的库房。 - 远离火种、热源，库温不宜超过37℃。 - 包装要求密封，避免与空气接触。 - 应与氧化剂和酸类分开存放，切忌混储。 - 使用防爆型照明和通风设施。 - 禁止使用易产生火花的机械设备和工具。 - 储区应备有泄漏应急处理设备和合适的收容材料。

SDS

国标编号:	33528
ＣＡＳ:	542-75-6
中文名称:	1，3-二氯丙烯
英文名称:	1，3-dichloropropene；1,3-dichloropropylene
别 名:	3-氯丙烯基氯
分子式:	C 3 H 4 Cl 2 ；ClCHCHCH 2 Cl
分子量:	111.00
熔 点:	-84℃ 沸点：108℃
密 度:	相对密度(水=1)1.22；
蒸汽压:	35℃
溶解性:	不溶于水，溶于乙醇、乙醚、苯等多数有机溶剂
稳定性:	稳定
外观与性状:	无色液体，有灯似氯仿的气味
危险标记:	7(易燃液体)
用 途:	用于有机合成和用作防霉剂

2.对环境的影响:

一、健康危害

侵入途径：吸入、食入、经皮吸收。 健康危害：吸入、口服或经皮肤吸收对几何有害。对眼睛、皮肤、粘膜和呼吸道有强烈的刺激作用；吸入后可因喉、支气管的痉挛、水肿、炎症，化学性肺炎、肺水肿而致死。中毒症状有烧灼感、咳嗽、喘息、喉炎、气短、头痛、恶心和呕吐。

二、毒理学资料及环境行为

急性毒性：LD50470～710mg/kg(大鼠经口)；504mg/kg(兔经皮)；LC504650mg/m3，2小时(小鼠吸入) 亚急性和慢性毒性：大鼠吸入50ppm，6小时/天，12周，肝肾肿大，动物存活。 致突变性：微生物致突变：鼠伤鼠寒沙门氏菌100µg/皿。姊妹染色单体交换：仓鼠卵巢900nmol/L。

危险特性：易燃，其蒸气与空气可形成爆炸性混合物。遇明火、高热能引起燃烧爆炸。与氧化剂能发生强烈反应。 燃烧(分解)产物：一氧化碳、二氧化碳、氯化氢、光气。

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3.现场应急监测方法:

便携式气相色谱法

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4.实验室监测方法:

监测方法	来源	类别
吹扫捕集-气相色谱法	中国环境监测总站	水质
气相色谱法	《固体废弃物试验与分析评价手册》中国环境监测总站等译	固体废弃物
色谱-质谱法	《水和废水标准检验法》第20版(美)	水质
色谱/质谱法	美国EPA524.2方法	水质

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5.环境标准:

前苏联 车间空气中有害物质的最高容许浓度 5mg/m3前苏联(1975)水体中有害物质最高允许浓度 0.4mg/L

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6.应急处理处置方法:

一、泄漏应急处理

迅速撤离泄漏污染区人员至安全区，并进行隔离，严格限制出入。切断火源。建议应急处理人员戴自给正压式呼吸器，穿消防防护服。尽可能切断泄漏源，防止进入下水道、排洪沟等限制性空间。小量泄漏：用砂土或其它不燃材料吸附或吸收。也可以用不燃性分散剂制成的乳液刷洗，洗液稀释后放入废水系统。大量泄漏：构筑围堤或挖坑收容；用泡沫覆盖，降低蒸气灾害。用防爆泵转移至槽车或专用收集器内，回收或运至废物处理场所处置。

二、防护措施

呼吸系统防护：可能接触其蒸气时，应该佩戴自吸过滤式防毒面具(全面罩)。紧急事态抢救或撤离时，建议佩戴自给式呼吸器。 眼睛防护：呼吸系统防护中已作防护。 身体防护：穿胶布防毒衣。 手防护：戴橡胶手套。 其它：工作现场禁止吸烟、进食和饮水。工作毕，淋浴更衣。注意个人清洁卫生。

三、急救措施

皮肤接触：立即脱去被污染的衣着，用大量流动清水冲洗，至少15分钟。就医。 眼睛接触：立即提起眼睑，用大量流动清水或生理盐水彻底冲洗至少15分钟。就医。 吸入：迅速脱离现场至空气新鲜处。保持呼吸道通畅。如呼吸困难，给输氧。如呼吸停止，立即进行人工呼吸。就医。 食入：误服者用水漱口，给饮牛奶或蛋清。就医。

灭火方法：喷水冷却容器，可能的话将容器从火场移至空旷处。。灭火剂：泡沫、二氧化碳、干粉、砂土。

制备方法与用途

用途

1,3-二氯丙烯为无色有甜味的挥发性液体，不纯时呈白色或琥珀色。它可用作有机合成中间体，并作为除草剂野燕畏和土壤熏蒸剂滴滴混剂中的成分。

化学性质

本品为无色有甜味的挥发性液体，在不纯时可呈白色或琥珀色，沸点97～112℃，折射率n_D 1.4720，相对密度1.198，冰点23℃，在水中的溶解度为0.1 g/100 g水，可与甲酚、丙酮、苯、四氯化碳和正庚烷相溶。本品主要由顺式和反式1,3-二氯丙烯混合而成，它们的物性如下：顺式1,3-二氯丙烯，沸点104.3℃，折射率n_D 1.469，相对密度1.224；反式1,3-二氯丙烯，沸点112℃，折射率n_D 1.475，相对密度1.217。

生产方法

由丙烯与氯气反应制得。该反应在500～550℃进行，通过分离即可得到产物。在丙烯高温氯化制环氧氯丙烷过程中，副反应生成的混合物中含有3-氯丙烯、1,3-二氯丙烯和1,2-二氯丙烷。在分离这些物质时，在塔顶可得1,3-二氯丙烯，在塔釜则得到滴滴混剂，其中二氯丙烷和二氯丙烯含量达80%以上。每生产1吨环氧氯丙烷，可副产滴滴混剂230kg。

用途

1,3-二氯丙烯可用于合成杀虫剂、除草剂等，并且可用作滴滴混剂的成分，具有强力杀线虫作用。一般使用的混合物为50%～60%的1,3-二氯丙烯、25%的1,2-二氯丙烷和其他氯化物，形成的液体为有刺激性氯臭味的黄褐色液体，并且具有腐蚀性和易吸水的特点。

生产方法

其制备方法是在500～550℃条件下用丙烯和氯气反应，然后进行分离。在丙烯氯化制备环氧氯丙烷时，副产物包括3-氯丙烯、1,3-二氯丙烯和1,2-二氯丙烷，这些物质同样可以通过分离得到。

类别

农药

毒性分级

高毒

急性毒性

• 大鼠 LD50: 470毫克/公斤
• 小鼠 LD50: 640毫克/公斤

可燃性危险特性

遇明火、高温或氧化剂时较易燃烧，燃烧会产生有毒氯化物烟雾。受热分解会释放有毒光气。

储运特性

库房应保持通风低温干燥，并与氧化剂分开存放，不宜久储以防聚合。

灭火剂

干粉、干砂、二氧化碳、泡沫及1211灭火剂。

职业标准

TWA 5毫克/立方米

反应信息

• 作为反应物：
  描述：

  1,3-二氯丙烯 在 氢气 作用下， 60.0 ℃ 、3.0 MPa 条件下， 生成 1,3-二氯丙烷
  参考文献：
  名称：

  1,3-二氯丙醇生产1,3-丙二醇的方法及系统

  摘要：

  本发明公开了一种1,3‑二氯丙醇生产1,3‑丙二醇的方法及系统。所述方法包括：将1,3‑二氯丙醇连续输入设置有脱水催化剂的反应装置进行脱水反应，制得1,3‑二氯丙烯；将所述1,3‑二氯丙烯和氢气连续输入设置有加氢催化剂的反应装置中进行加氢反应，制得1,3‑二氯丙烷；以及，使包含所述1,3‑二氯丙烷、水解剂和溶剂的混合反应体系进行水解反应，制得1,3‑丙二醇。本发明以廉价的甘油氯化法制备环氧氯丙烷的中间产物1,3‑二氯丙醇为原料，通过脱水‑加氢‑水解3步制得重要的化工原料1,3‑丙二醇，为甘油制1,3‑丙二醇提供了一条新途径，且该路线条件温和，成本低廉，具有环环保与经济等优势。

  公开号：

  CN112479811A
• 作为产物：
  描述：

  1,3-二氯丙醇 生成 1,3-二氯丙烯
  参考文献：
  名称：

  1,3-二氯丙醇生产1,3-丙二醇的方法及系统

  摘要：

  本发明公开了一种1,3‑二氯丙醇生产1,3‑丙二醇的方法及系统。所述方法包括：将1,3‑二氯丙醇连续输入设置有脱水催化剂的反应装置进行脱水反应，制得1,3‑二氯丙烯；将所述1,3‑二氯丙烯和氢气连续输入设置有加氢催化剂的反应装置中进行加氢反应，制得1,3‑二氯丙烷；以及，使包含所述1,3‑二氯丙烷、水解剂和溶剂的混合反应体系进行水解反应，制得1,3‑丙二醇。本发明以廉价的甘油氯化法制备环氧氯丙烷的中间产物1,3‑二氯丙醇为原料，通过脱水‑加氢‑水解3步制得重要的化工原料1,3‑丙二醇，为甘油制1,3‑丙二醇提供了一条新途径，且该路线条件温和，成本低廉，具有环环保与经济等优势。

  公开号：

  CN112479811A
• 作为试剂：
  描述：

  、 碘 、 、 2-(4-溴苯基)-1,3-二氧戊环 、 、 氯化锂 、 顺式-1,3-二氯丙烯 在 氯化亚铜 氮 、 1,3-二氯丙烯 、 氯化铵 、 四氢呋喃 、 盐酸 、 乙醚 、 水 、 碳酸氢钠 、 氯化钠 、 magnesium sulfate 、 florisil 、 petroleum ether 作用下， 以 四氢呋喃 为溶剂， 反应 18.33h， 生成 4(Z-3-chloroallyl)benzaldehyde
  参考文献：
  名称：

  Pesticides

  摘要：

  化合物式I的化合物##STR1##其中，D代表氢或氰基; X代表卤素; A代表烷基（通常是C.sub.1-C.sub.6烷基）; n为0至4; RCOO.代表酸RCO.sub.2 H的残基，该酸或其酯化衍生物与.alpha.-氰基-3-苯氧基苯甲醇或其酯化衍生物反应，产生具有杀虫性能的.alpha.-氰基-3-苯氧基苯甲酸酯。

  公开号：

  US04847438A1

文献信息

• [EN] CONJUGATES FOR TREATING DISEASES<br/>[FR] CONJUGUÉS POUR LE TRAITEMENT DE MALADIES
  申请人：ENDOCYTE INC

  公开号：WO2016148674A1

  公开（公告）日：2016-09-22

  The present disclosure relates to pyrrolobenzodiazepine (PBD) prodrugs and conjugates thereof. The present disclosure also relates to pharmaceutical compositions of the conjugates described herein, methods of making and methods of using the same.

  本公开涉及吡咯苯并二氮杂环（PBD）前药及其结合物。本公开还涉及所述结合物的药物组合物，制备方法和使用方法。
• [EN] PYRAZOLE COMPOUNDS AND USE THEREOF IN NOXIOUS ARTHROPOD PESTS CONTROLLING COMPOSITION<br/>[FR] COMPOSES DERIVES DU PYRAZOLE ET LEUR UTILISATION DANS UNE COMPOSITION DE LUTTE CONTRE LES ARTHROPODES NUISIBLES
  申请人：SUMITOMO CHEMICAL CO

  公开号：WO2005075433A1

  公开（公告）日：2005-08-18

  The present invention provides a pyrazole compound of formula (a): ;a noxious arthropod pests controlling composition containing the compound shown by the formula (a) as an active ingredient; and a method for controlling noxious arthropod pests comprising applying an effective amount of the compound shown by the formula (a).

  本发明提供了一种式（a）的吡唑化合物；一种含有所述式（a）化合物作为活性成分的有害节肢动物害虫控制组合物；以及一种控制有害节肢动物害虫的方法，包括施用所述式（a）化合物的有效量。
• A Mild and Convenient Barbier-Type Allylation of Aldehydes to Homoallylic Alcohols via Iodide Ion Promoted Stannylation of Allylic Bromides and Chlorides with Tin(II) Chloride
  作者：Toshiro Imai、Shinya Nishida

  DOI：10.1055/s-1993-25871

  日期：——

  Barbier-type allylation of aldehydes with allylic bromides and tin(II) chloride dihydrate is largely accelerated by adding stoichiometric or substoichiometric amounts of sodium iodide. This method has some merits such as lower temperature, shorter reaction time and/or more choices of solvents for the reaction. Moreover, the activation by the iodide ion enables the use of relatively unreactive allylic chlorides of various structural types (e.g., 3-chloro-2-chloromethylpropene as an isobutene dianion equivalent) and, thus, expands synthetic applicability of this reaction. The major role of the iodide salt is attributed to the in situ generation of the corresponding allylic iodide.

  巴比尔型醛与烯丙基溴和二水合氯化亚锡的偶联反应通过添加化学计量或亚化学计量的碘化钠，得到了显著的加速。这种方法具有一些优点，如较低的反应温度、更短的反应时间以及/或更多选择性的溶剂使用。此外，碘离子引发的活化使得可以利用相对不活泼的各种结构类型的烯丙基氯化物（例如，作为异丁烯二负离子等价物的3-氯-2-氯甲基丙烯），从而扩大了这一反应的合成应用范围。碘盐的主要作用归因于其在位生成相应的烯丙基碘化物。
• A simple, stereoselective, room-temperature synthesis of cis vinyloxiranes and trans 1-phenyl-1,3-butadiene
  作者：Jacques Auge、Serge David

  DOI：10.1016/s0040-4039(00)88249-0

  日期：1983.1

  The organotin reagent from 1-chloro-3-iodoprop-1-ene and SnCl2 in dimethylformamide reacted with aldehydes by ite chlorine-substituted carbon atom. Treatment with NaOMe then gave vinyloxiranes with good stereo-selectivity. benzaldehyde and 1-bromo-3-iodoprop-1-ene in the presence of two equivalents of SnCl2 gave exclusively -1-phenyl-1,3-butadiene.

  1-氯-3-碘丙-1-烯和SnCl 2在二甲基甲酰胺中的有机锡试剂通过氯取代的碳原子与醛反应。然后用NaOMe处理得到具有良好立体选择性的乙烯基环氧乙烷。在两当量的SnCl 2存在下，苯甲醛和1-溴-3-碘丙-1-烯仅产生-1-苯基-1,3-丁二烯。
• SYNTHESIS OF β, γ-UNSATURATE CARBOXYLIC ACID DERIVATIVES BY THE NOVEL Ni (CO)₄-INDUCED RING-OPENING CARBONYLATION REACTION OF 1,1-DIBROMO-2-CHLOROCYCLOPROPANES
  作者：Toshikazu Hirao、Shinichiro Nagata、Toshio Agawa

  DOI：10.1246/cl.1985.1625

  日期：1985.11.5

  1,1-Dibromo-2-chlorocyclopropanes underwent the Ni (CO)4-induced ring-opening carbonylation reaction with alcohol or amine giving the β, γ,-unsaturated carboxylic acid and dicarboxylic acid derivatives. Use of N,N-dimethyltrimethylsilylamine as an initial nucleophile in the presence of benzaldehyde led to a dienecarboxamide presumably via codensation of the nickel enolate intermediate.

  1,1-二溴-2-氯环丙烷与醇或胺发生Ni (CO) 4 诱导的开环羰基化反应，得到β, γ,-不饱和羧酸和二羧酸衍生物。在苯甲醛存在下使用 N,N-二甲基三甲基甲硅烷基胺作为初始亲核试剂可能通过烯醇镍中间体的共聚作用产生二烯甲酰胺。

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