1,2-二溴-4-(1,2-二溴乙基)环己烷 | 3322-93-8

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 环烃
• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 中文名称: 1,2-二溴-4-(1,2-二溴乙基)环己烷
• 中文别名: 1,2-二溴-4-(1,2-二溴乙基)-环己烷
• 英文名称: 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane
• 英文别名: BCH
• CAS: 3322-93-8
• 化学式: C₈H₁₂Br₄
• 分子量: 427.799
• InChiKey: PQRRSJBLKOPVJV-UHFFFAOYSA-N

物化性质

• 熔点：
  72-73℃ (ethyl ether )
• 沸点：
  308.26°C (rough estimate)
• 密度：
  23800 g/cm3
• 溶解度：
  氯仿（微溶）、乙酸乙酯（微溶）、甲醇（微溶）
• 物理描述：
  1-(1,2-dibromoethyl)-3,4-dibromocyclohexane is a white crystalline powder. Ester-like odor. (NTP, 1992)
• 颜色/状态：
  White solid
• 气味：
  Ester-like odor
• 蒸汽压力：
  1.05X10-4 mm Hg at 25 °C (est)
• 分解：
  When heated to decomposition it emits toxic vapors of bromide.

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

含溴阻燃剂TBECH被用作添加剂，以延迟点火并抑制建筑材料和消费品中的火灾。人类暴露的趋势尚不清楚，尽管人们可能会通过室内尘埃和空气接触到TBECH。在鸟类和鱼类中，有证据表明TBECH可能会干扰内分泌和生殖参数。体外研究表明TBECH是一种雄激素受体激动剂。在这项研究中，大鼠通过饮食暴露于0、10、50、250、1250或5000毫克/千克技术TBECH，持续28天，在雄性中分别对应于0、0.9、4.2、21.3、98.0或328.9毫克TBECH/千克体重/天，在雌性中分别对应于0、0.8、3.9、19.4、91.7或321.4毫克TBECH/千克体重/天。在血清、肝脏和脂肪中检测到alpha-和beta- TBECH的剂量依赖性增加。

The brominated flame retardant TBECH is used as an additive to delay ignition and inhibit fires in construction materials and consumer goods. Trends in human exposure are not clear, although humans may be exposed to TBECH via indoor dust and air. In birds and fish there is some evidence of disruption in endocrine and reproductive parameters due to TBECH. In vitro studies indicate that TBECH is an androgen receptor agonist. In this study rats were exposed to 0, 10, 50, 250, 1250 or 5000 mg/kg technical TBECH for 28 days in diet, corresponding to 0, 0.9, 4.2, 21.3, 98.0 or 328.9 mg TBECH/kg bw/d in males and 0, 0.8, 3.9, 19.4, 91.7 or 321.4 mg TBECH/kg bw/d in females. Dose-dependent increases in alpha- and beta- TBECH were detected in serum, liver and adipose. ...

来源:Hazardous Substances Data Bank (HSDB)

代谢

斑马鱼（Danio rerio）被喂食含有11种结构多样的溴化阻燃剂（BFRs）混合物的饮食，浓度为1或100纳米摩尔/克，持续多达42天，之后是14天的消除期。... 在鱼体内鉴定出四种BFR代谢物：2,2',3,4',5',6-六溴二苯醚（BDE 149）、2,2',4,4',5,6'-六溴二苯醚（BDE 154）、2,4,6-三溴苯甲醚和1,2,4,5-六溴苯。这些代谢物在14天的消除期后仍然存在于斑马鱼体内。斑马鱼体内的BFR浓度与它们的辛醇-水分配系数（KOW）的对数值之间没有发现相关性。通常，全溴化和羟基化化合物表现出较低的生物累积倾向。然而，观察到的BFR代谢物在鱼体内的积累表明，低浓度的BFR并不能单独提供一个可靠的指示，表明该BFR具有低风险。

Zebrafish (Danio rerio) were fed a diet containing a mixture of 11 structurally diverse brominated flame retardants (BFRs) at nominal concentrations of either 1 or 100 nmol/g for up to 42 days, followed by an elimination period of 14 days. ... Four BFR metabolites were identified in the fish: 2,2',3,4',5',6-Hexabromodiphenyl ether (BDE 149), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE 154), 2,4,6-tribromoanisole, and 1,2,4,5-hexabromobenzene. These metabolites were still present in the zebrafish after the 14-d elimination period. No relationship between the BFR concentrations in the zebrafish and their log octanol-water partition coefficient (KOW) values was found. Generally, low tendencies to bioaccumulate were observed for perbrominated and hydroxylated compounds. The observed accumulation of BFR metabolites in fish, however, shows that low concentration of a BFR does not provide, in isolation, a sound indication that the BFR poses low risks.

来源:Hazardous Substances Data Bank (HSDB)

代谢

1,2-二溴-4-(1,2-二溴乙基)环己烷(TBECH或DBE-DBCH)的技术混合物和纯beta-TBECH异构体被用于体外人肝微粒体(HLM)生物转化。在60分钟的孵化后，使用超高效液相色谱-Q-Exactive Orbitrap质谱在TBECH混合物和beta-TBECH的微粒体分析中鉴定出5种潜在的TBECH代谢物。这些包括单羟基和二羟基TBECH以及单羟基和二羟基TriBECH以及alpha-氧化代谢物溴-(1,2-二溴环己基)-乙酸。我们的结果表明，TBECH可能通过细胞色素P450催化的羟基化、脱溴和alpha-氧化在肝脏中发生生物转化。动力学研究表明，单羟基-TBECH、二羟基-TBECH和单羟基-TriBECH的形成最好符合米氏-门顿酶动力学模型。在TBECH混合物中，这些代谢物的估计Vmax值(最大代谢速率)分别为11.8 +/- 4、0.6 +/- 0.1和10.1 +/- 0.8 pmol/min/mg蛋白质，在beta-TBECH中分别为4992 +/- 1340、14.1 +/- 4.9和66.1 +/- 7.3 pmol/min/mg蛋白质。这表明单羟基-TBECH是通过体外HLM-based assay的TBECH的主要代谢物。TBECH混合物的估计体外内在清除率(Clint)比纯beta-TBECH慢(P < 0.05)。虽然单羟基-TBECH的形成可能降低生物累积潜力并提供监测TBECH暴露的有用生物标志物，但需要进一步的研究来完全理解已鉴定代谢物的水平和毒理学影响。

The technical mixture of 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH or DBE-DBCH) and the pure beta-TBECH isomer were subjected to in vitro biotransformation by human liver microsomes (HLM). After 60 min of incubation, 5 potential metabolites of TBECH were identified in microsomal assays of both the TBECH mixture and beta-TBECH using ultraperformance liquid chromatography-Q-Exactive Orbitrap mass spectrometry. These include mono- and dihydroxylated TBECH and mono- and dihydroxylated TriBECH as well as an alpha-oxidation metabolite bromo-(1,2-dibromocyclohexyl)-acetic acid. Our results indicate potential hepatic biotransformation of TBECH via cyctochrome P450-catalyzed hydroxylation, debromination, and alpha-oxidation. Kinetic studies revealed that the formation of monohydroxy-TBECH, dihydroxy-TBECH, and monohydroxy-TriBECH were best fitted to a Michaelis-Menten enzyme kinetic model. Respective estimated Vmax values (maximum metabolic rate) for these metabolites were 11.8 +/- 4, 0.6 +/- 0.1, and 10.1 +/- 0.8 pmol/min/mg protein in TBECH mixture and 4992 +/- 1340, 14.1 +/- 4.9, and 66.1 +/- 7.3 pmol/min/mg protein in beta-TBECH. This indicates monohydroxy-TBECH as the major metabolite of TBECH by in vitro HLM-based assay. The estimated in vitro intrinsic clearance (Clint) of TBECH mixture was slower (P < 0.05) than that of pure beta-TBECH. While the formation of monohydroxy-TBECH may reduce the bioaccumulation potential and provide a useful biomarker for monitoring TBECH exposure, further studies are required to fully understand the levels and toxicological implications of the identified metabolites.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

鉴定和使用：1,2-二溴-4-(1,2-二溴乙基)环己烷（BCH）是一种白色粉末。它被用作阻燃添加剂（聚苯乙烯、聚氨酯、聚氯乙烯）。人类研究：BCH是人类雄激素受体（AR）的激动剂。带有AR突变的细胞更容易受到雄激素内分泌干扰物的影响。结合理论建模与体外配体结合和受体激活实验表明，BCH能够结合并激活人类AR，表明它是一种潜在的内分泌干扰物。动物研究：在鸟类和鱼类中，有一些证据表明BCH会干扰内分泌和生殖参数。体外研究表明，BCH是雄激素受体的激动剂。雄性大鼠通过饮食暴露于0、0.9、4.2、21.3、98.0或328.9 mg BCH/kg体重/天，雌性大鼠暴露于0、0.8、3.9、19.4、91.7或321.4 mg BCH/kg体重/天，持续28天。观察到一些激素干扰的证据，包括雄性血清睾酮水平的改变和雌性血清T3和T4水平的改变。BCH激活了鸡LMH细胞系中的AR。进一步的定量逆转录聚合酶链反应（qRT-PCR）分析显示，BCH与甲状腺受体和雌激素受体相互作用并改变了它们的表达。此外，qRT-PCR分析显示，BCH改变了参与炎症、凋亡、增殖、DNA甲基化和药物代谢途径的基因的转录模式。在四种沙门氏菌鼠伤寒菌株（TA98、TA100、TA1535和TA1537）存在和不存在代谢激活的情况下进行测试时，BCH在致突变性实验中呈阴性。生态毒性研究：繁殖期间的笼养美洲红隼（Falco sparverius）通过饮食暴露于环境相关浓度的beTA-BCH。蛋产量和生育能力的降低导致孵化成功率下降。beTA-BCH暴露的鸟类的雄性依赖行为也显著增加。在斑马雀胚胎中，对不同发育阶段的组织样本进行分析表明，alpha-/beTA-BCH被迅速代谢，因此不太可能对斑马雀胚胎或后代的发育产生任何直接、长期的影响。

IDENTIFICATION AND USE: 1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (BCH) is a white powder. It is used as a fire-retardant additive (polystyrene, polyurethane, polyvinyl chloride). HUMAN STUDIES: BCH is an agonist to human androgen receptor (AR). Cells with AR mutations were more susceptible to androgenic endocrine disrupters. Combining theoretical modeling with in vitro ligand-binding and receptor-activation assays demonstrated that BCH binds to and activates the human AR, indicating that it is a potential endocrine disruptor. ANIMAL STUDIES: In birds and fish there is some evidence of disruption in endocrine and reproductive parameters due to BCH. In vitro studies indicate that BCH is an androgen receptor agonist. Rats were exposed to 0, 0.9, 4.2, 21.3, 98.0 or 328.9 mg BCH/kg bw/d in males and 0, 0.8, 3.9, 19.4, 91.7 or 321.4 mg BCH/kg bw/d in females for 28 days in diet. Some evidence of hormone disruption was observed, including changes in serum testosterone levels in males and changes in serum T3 and T4 levels in females. BCH activated AR in chicken LMH cell line. Further quantitative reverse-transcriptase polymerase chain reaction (qRT-PCR) analysis showed that BCH interacted with and altered the expression of both thyroid receptors and estrogen receptors. In addition, the qRT-PCR analysis showed that BCH altered the transcription pattern of genes involved in inflammatory, apoptotic, proliferative, DNA methylation, and drug-metabolizing pathways. BCH was negative in mutagenicity assay when tested in four Salmonella typhimurium strains (TA98, TA100, TA1535, and TA1537) in the presence and absence of metabolic activation. ECOTOXICITY STUDIES: Captive American kestrels (Falco sparverius) were exposed via diet during reproduction to an environmentally relevant concentration of beta- BCH. Reductions in egg production and fertility resulted in decreased hatchling success. Androgen-dependent behaviors were also significantly increased in beta-BCH-exposed birds. In zebra finch embryos, analysis of tissue samples at various developmental stages suggests that alpha-/beta-BCH was metabolized rapidly, and thus was unlikely to cause any direct, long-term effects on the development of zebra finch embryos or offspring.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 相互作用

内分泌干扰化合物可以干扰雄激素受体（AR）信号传导并破坏类固醇生成，导致生殖失败。溴化阻燃剂（BFR）1,2-二溴-4-(1,2-二溴乙基)环己烷（TBECH）是人类、鸡和斑马鱼AR的激动剂。最近，另一组替代BFRs，即烯丙基2,4,6-三溴苯基醚（ATE）和2,3-二溴丙基2,4,6-三溴苯基醚（DPTE）及其代谢物2-溴烯丙基2,4,6-三溴苯基醚（BATE）被识别为强效的人类AR拮抗剂。这些替代BFRs存在于环境中。本研究的目的是确定在环境相关浓度下，AR激动剂和AR拮抗剂混合暴露的影响。体外报告荧光素酶分析显示，当AR拮抗剂的浓度高于TBECH时，能够抑制TBECH介导的AR活性。这些AR拮抗剂还促进了AR的核转位。在非肿瘤性人前列腺上皮细胞RWPE1中的体外基因表达分析显示，TBECH诱导了AR靶基因，而DPTE则抑制了这些基因。进一步分析类固醇生成基因显示，TBECH上调了大多数基因，而DPTE则下调了相同的基因。结果表明，当TBECH和DPTE同时存在时，它们将相互拮抗，从而减少它们各自的影响。

Endocrine disrupting compounds can interfere with androgen receptor (AR) signaling and disrupt steroidogenesis leading to reproductive failure. The brominated flame-retardant (BFR) 1, 2-dibromo-4-(1, 2-dibromoethyl) cyclohexane (TBECH), is an agonist to human, chicken and zebrafish AR. Recently another group of alternative BFRs, allyl 2, 4, 6-tribromophenyl ether (ATE), and 2, 3-dibromopropyl 2, 4, 6-tribromophenyl ether (DPTE) along with its metabolite 2-bromoallyl 2, 4, 6-tribromophenyl ether (BATE) were identified as potent human AR antagonists. These alternative BFRs are present in the environment. The aim of the present study was to determine the effect of mixed exposures to the AR agonist and the AR antagonists at environmentally relevant concentrations. In vitro reporter luciferase assay showed that the AR antagonists, when present at concentration higher than TBECH, were able to inhibit TBECH-mediated AR activity. These AR antagonists also promoted AR nuclear translocation. In vitro gene expression analysis in the non-tumorigenic human prostate epithelial cell RWPE1 showed that TBECH induced AR target genes whereas DPTE repressed these genes. Further analysis of steroidogenic genes showed that TBECH up-regulated most of the genes while DPTE down-regulated the same genes. The results indicate that when TBECH and DPTE are present together they will antagonize each other, thereby reducing their individual effects.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 紧急急救：确保已经进行了充分的中和。如果患者停止呼吸，请开始人工呼吸，最好使用需求阀复苏器、袋阀面罩装置或口袋面罩，按训练操作。如有必要，执行心肺复苏。立即用缓慢流动的水冲洗受污染的眼睛。不要催吐。如果发生呕吐，让患者前倾或将其置于左侧（如果可能的话，头部向下）以保持呼吸道畅通，防止吸入。保持患者安静，维持正常体温。寻求医疗帮助。 /溴素、甲基溴和相关化合物/

/SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Bromine, methyl bromide, and related compounds/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 基本治疗：建立专利气道（如有必要，使用口咽或鼻咽气道）。如有必要，进行吸痰。观察呼吸不足的迹象，如有必要，协助通气。通过非循环呼吸面罩以10至15升/分钟的速度给予氧气。监测肺水肿，如有必要，进行治疗...。监测休克，如有必要，进行治疗...。预期癫痫发作，如有必要，进行治疗...。对于眼睛污染，立即用水冲洗眼睛。在运输过程中，用0.9%的生理盐水（NS）持续冲洗每只眼睛...。不要使用催吐剂。对于摄入，如果患者能够吞咽、有强烈的干呕反射且不流口水，则用水冲洗口腔，并给予5毫升/千克，最多200毫升的水进行稀释。给予活性炭...。在去污后，用干燥的无菌敷料覆盖皮肤烧伤...。/溴素、甲基溴和相关化合物/

/SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . Cover skin burns with dry sterile dressings after decontamination ... . /Bromine, methyl bromide, and related compounds/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 高级治疗：对于无意识、严重肺水肿或严重呼吸困难的病人，考虑进行口咽或鼻咽气管插管以控制气道。使用气囊面罩装置的正压通气技术可能有益。考虑使用药物治疗肺水肿……。对于严重的支气管痉挛，考虑给予β激动剂，如沙丁胺醇……。监测心率和必要时治疗心律失常……。开始静脉输注5%葡萄糖（D5W）/SRP: "保持开放"，最低流量/。如果出现低血容量的迹象，使用0.9%盐水（NS）或乳酸林格液（LR）。对于伴有低血容量迹象的低血压，谨慎给予液体。如果病人在正常液体容量下出现低血压，考虑使用血管加压药。注意观察液体过载的迹象……。用地西泮或劳拉西泮治疗癫痫……。使用丙美卡因氢氯化物协助眼部冲洗……。/溴素、甲基溴和相关化合物/

/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasm ... . Monitor cardiac rhythm and treat arrhythmias if necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Consider vasopressors if patient is hypotensive with a normal fluid volume. Watch for signs of fluid overload ... . Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Bromine, methyl bromide, and related compounds/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

立体异构体组成的研究：1,2,5,6,9,10-六溴环十二烷（HBCD）和1,2-二溴-4-(1,2-二溴乙基)环己烷（TBECH）在2005年至2015年间，从南海的两类海洋哺乳动物——江豚（Neophocaena phocaenoides）和印度太平洋驼背海豚（Sousa chinensis）的脂肪组织中进行了调查。江豚样本（n = 59）和海豚样本（n = 32）中的sigma-HBCD浓度范围分别为97.2至6,260 ng/g脂质重量（lw）和447至45,800 ng/g lw，而sigma-TBECH的浓度则普遍低约两个数量级。在过去的十年里，海豚脂肪中的SHBCD含量呈显著上升趋势。对映体剖面显示alpha-HBCD的绝对优势（大多数>90%），而四种TBECH对映体在样本中的比例相似。在大多数脂肪样本中发现了alpha-、beta-和gamma-HBCD的(-)-对映体的偏好性富集。有趣的是，江豚的体长与alpha-HBCD的对映体比例呈显著负相关。alpha-、gamma-和sigma-TBECH的对映体对也观察到了显著的消旋偏差。这是首次报告环境中存在TBECH对映体。估计的危险商数表明，由于HBCD暴露，海豚可能面临潜在风险。

Stereoisomeric compositions of 1,2,5,6,9,10-hexabromocyclododecane (HBCD) and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) were investigated in the blubber of two species of marine mammals, finless porpoises (Neophocaena phocaenoides) and Indo-Pacific humpback dolphins (Sousa chinensis), from the South China Sea between 2005 and 2015. The concentrations of sigma-HBCD in samples of porpoise (n = 59) and dolphin (n = 32) ranged from 97.2 to 6,260 ng/g lipid weight (lw) and from 447 to 45,800 ng/g lw, respectively, while those of sigma-TBECH were both roughly 2 orders of magnitude lower. A significant increasing trend of SHBCD was found in dolphin blubber over the past decade. The diastereomeric profiles exhibited an absolute predominance of alpha-HBCD (mostly >90%), while the proportions of four TBECH diastereomers in the samples appeared similar. A preferential enrichment of the (-)-enantiomers of alpha-, beta-, and gamma-HBCD was found in most blubber samples. Interestingly, the body lengths of porpoises showed a significant negative correlation with the enantiomer fractions of alpha-HBCD. Significant racemic deviations were also observed for alpha-, gamma-, and sigma-TBECH enantiomeric pairs. This is the first report of the presence of TBECH enantiomers in the environment. The estimated hazard quotient indicates that there is a potential risk to dolphins due to HBCD exposure.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

技术 1,2-二溴-4-(1,2-二溴乙基)环己烷或四溴乙基环己烷（TBECH）主要用作聚苯乙烯泡沫中的添加剂阻燃剂，包含两种对映异构体，alpha-和beta-，以等摩尔量存在。在超过125°C的温度下，可能会异构成另外两种同分异构体，sigma-和gamma-。最近在环境中检测到TBECH，以及研究表明这些异构体具有雄激素作用，促使我们研究其中一种异构体，beta-，在受控实验室环境中的毒物动力学和生化效应。将幼年棕鳟（Salmo trutta）暴露于三种不同剂量的beta异构体（低、中、高）通过食物，随后是一段时间内它们暴露于未加固的食物。第四组鱼在整个实验期间暴露于未加固的食物。在第0、7、14、21、35、49、56、63、77、91、105和133天，每组处理八条鱼被安乐死，并收集肝脏、血浆、下颌（即甲状腺组织）和性腺，保留剩余组织（'整鱼'）。在整鱼和肝脏中测量beta异构体含量，而雌二醇（E2）、11-酮睾酮（11-KT）和睾酮（T）在血浆中测量。基于肝脏和性腺体指数，在任何处理组的鱼中都没有观察到对肝脏或性腺发育的明显影响。beta异构体在所有处理组的鱼中的生物累积相似，稳态发生在摄取阶段结束之前。从鱼中去除beta异构体遵循一级动力学，并且处理组之间的排泄半衰期（t(1/2)）没有统计学上的显著差异：22.5 +/- 10.4（低）、13.5 +/- 5.9（中）和13.8 +/- 2.2（高）天。稳态生物放大因子在所有处理组的鱼中远小于1。在复合肝脏或整鱼提取物中没有检测到脱溴代谢物，并且没有证据表明beta异构体在体内异构化为其他同分异构体。虽然偶尔会出现处理组之间循环血浆E2、T和11-KT水平的差异，但没有明确的时效趋势或剂量反应。

Technical 1,2-dibromo-4-(1,2 dibromoethyl)cyclohexane or tetrabromoethylcyclohexane (TBECH) used primarily as an additive flame retardant in polystyrene foams, contains two diastereoisomers, alpha- and beta- present in equimolar amounts. At temperatures in excess of 125 °C, isomerization to two other isoforms, sigma- and gamma- is possible. The recent detection of TBECH in the environment and studies suggesting that isomers are androgenic prompted us to examine the toxicokinetics and biochemical effects of one of the isomers, beta-, in a controlled laboratory environment. Juvenile brown trout (Salmo trutta) were exposed to three different amounts of the beta-isomer (low, medium and high) via the food followed by a period in which they were exposed to unfortified food. A fourth group of fish was exposed to unfortified food for the duration of the experiment. On days 0, 7, 14, 21, 35, 49, 56, 63, 77, 91, 105, and 133, eight fish from each treatment group were euthanized and liver, plasma, lower jaw (i.e., thyroid tissue) and gonad were collected and the remaining tissue ('whole-fish') was retained. beta-Isomer content was measured in whole-fish and in liver while estradiol (E2), 11-ketotestosterone (11-KT) and testosterone (T) were measured in plasma. Based on liver and gonad somatic indices, no apparent effects on liver or gonad development in fish from any of the treatment groups were observed. The bioaccumulation of beta-isomer was similar in fish from all treatment groups with steady-state occurring before the end of the uptake phase. Depuration of the beta-isomer from fish obeyed first order kinetics and there were no statistically significant differences in the depuration half life (t(1/2)) among the treatment groups: 22.5 +/- 10.4 (low), 13.5 +/- 5.9 (med) and 13.8 +/- 2.2 (high) days. Steady-state biomagnification factors were much smaller than 1 for fish in all treatment groups. Debrominated metabolites were not detected in composite liver or whole-fish extracts and there was no evidence of isomerization of the beta-isomer to other isoforms in vivo. While there were occasional differences among treatment groups in circulating plasma E2, T and 11-KT levels there was no clear, temporal trend or dose-response.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

斑马鱼（Danio rerio）被喂食含有11种结构多样的溴化阻燃剂（BFRs）混合物的饮食，名义浓度分别为1或100纳米摩尔/克，持续最多42天，随后是14天的消除期。在暴露和消除阶段，通过测量雄性鱼体内五种BFRs的浓度，计算了它们的摄取率和消除常数。观察到摄取效率最高的是2,4,4'-三溴二苯醚（BDE 28）和1,2-二溴-4-(1,2-二溴乙基)环己烷（TBECH），而最低的是十溴二苯醚（BDE 209）。TBECH和2,4,6-三溴苯酚的估计半衰期较短（小于2天）。在鱼体内鉴定出四种BFR代谢物：2,2',3,4',5',6-六溴二苯醚（BDE 149），2,2',4,4',5,6'-六溴二苯醚（BDE 154），2,4,6-三溴苯甲醚和1,2,4,5-六溴苯。这些代谢物在14天的消除期后仍然存在于斑马鱼体内。斑马鱼体内的BFR浓度与它们的辛醇-水分配系数（KOW）的对数值之间没有发现相关性。一般来说，全溴化和羟基化化合物表现出较低的生物累积倾向。然而，在鱼体内观察到BFR代谢物的积累表明，低浓度的BFR本身并不能提供该BFR具有低风险的可靠指示。

Zebrafish (Danio rerio) were fed a diet containing a mixture of 11 structurally diverse brominated flame retardants (BFRs) at nominal concentrations of either 1 or 100 nmol/g for up to 42 days, followed by an elimination period of 14 days. Uptake rates and elimination constants for five of the BFRs were calculated from measurements of their concentrations in the male fish during the exposure and elimination phases. Observed uptake efficiencies were highest for 2,4,4'-tribromodiphenyl ether (BDE 28) and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) and were lowest for decabromodiphenyl ether (BDE 209). Estimated half-lives for TBECH and 2,4,6-tribromophenol were short (<2 days). Four BFR metabolites were identified in the fish: 2,2',3,4',5',6-Hexabromodiphenyl ether (BDE 149), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE 154), 2,4,6-tribromoanisole, and 1,2,4,5-hexabromobenzene. These metabolites were still present in the zebrafish after the 14-d elimination period. No relationship between the BFR concentrations in the zebrafish and their log octanol-water partition coefficient (KOW) values was found. Generally, low tendencies to bioaccumulate were observed for perbrominated and hydroxylated compounds. The observed accumulation of BFR metabolites in fish, however, shows that low concentration of a BFR does not provide, in isolation, a sound indication that the BFR poses low risks.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 海关编码：
  2903890090

反应信息

• 作为反应物：
  描述：

  1,2-二溴-4-(1,2-二溴乙基)环己烷 在 poly(styrylmethylthiol) 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 4.0h， 以62%的产率得到4-乙烯基-1-环己烯
  参考文献：
  名称：

  Poly(styrylmethylthiol) as an efficient debrominating reagent of 1,2-dibromides

  摘要：

  DOI：

  10.1016/s0040-4039(00)94312-0
• 作为产物：
  描述：

  4-乙烯基-1-环己烯 在 四丁基溴化铵 、 溴 作用下， 以 1,2-二氯乙烷 为溶剂， 以97.2 %的产率得到1,2-二溴-4-(1,2-二溴乙基)环己烷
  参考文献：
  名称：

  一种提高催化溴化加成反应立体选择性的方法

  摘要：

  一种提高催化溴化加成反应立体选择性的方法，包括以下步骤：(1)将反应原料与催化剂溶于溶剂中，缓慢滴加溴素，进行溴化加成反应；(2)溴素滴加完毕，缓慢进行升温，进行中温阶段的溴化加成反应；(3)向步骤(2)中所得到的混合物中加入亚硫酸钠水溶液以除去过量的溴素，然后再加入氢氧化钠水溶液调pH至中性；(4)将上述步骤(3)中所得到的混合料液进行静置分层，去掉水层后得含溶剂的混合溶液；(5)除去溶剂，最后得目标产品。本发明提供的溴化加成方法，在实现双键加成高效立体选择性的同时，有效节约了原料成本，极大减少了三废产生。

  公开号：

  CN115677458A

文献信息

• Thermoplastic resin composition and elastomer composition
  申请人：——

  公开号：US20040106732A1

  公开（公告）日：2004-06-03

  Provided are a thermoplastic resin composition which is excellent in oil resistance, heat resistance, weatherability, impact resistance, transparency, and moldability, and which can be produced economically, an elastomer composition with low hardness and high tensile strength which is excellent in oil resistance and compression set, and a molded object produced by molding the thermoplastic resin composition or elastomer composition. The composition is produced by compounding a thermoplastic resin or an elastomer with a block copolymer having at least one methacrylic ester polymer block and at least one acrylic ester polymer block. Also provided are a process for producing a methacrylic ester-acrylic ester-methacrylic ester block copolymer which requires hardly any purification, which is excellent in heat resistance and weatherability, and in which the molecular weight and the molecular-weight distribution are controlled, and a methacrylic ester-acrylic ester-methacrylic ester block copolymer produced by the process.

  提供了一种热塑性树脂组合物，具有优异的耐油性、耐热性、耐候性、抗冲击性、透明度和成型性，且可经济生产；一种低硬度、高拉伸强度的弹性体组合物，具有优异的耐油性和压缩回弹性；以及由该热塑性树脂组合物或弹性体组合物成型而成的成型物。该组合物通过将热塑性树脂或弹性体与至少具有一个甲基丙烯酸酯聚合物块和至少一个丙烯酸酯聚合物块的嵌段共聚物混合制备而成。 同时提供了一种制备甲基丙烯酸酯-丙烯酸酯-甲基丙烯酸酯嵌段共聚物的方法，该方法几乎不需要纯化，具有优异的耐热性和耐候性，并且分子量和分子量分布可控；以及由该方法制备的甲基丙烯酸酯-丙烯酸酯-甲基丙烯酸酯嵌段共聚物。
• Block copolymer
  申请人：——

  公开号：US20040236020A1

  公开（公告）日：2004-11-25

  Provided are a block copolymer including a polymer block containing acrylonitrile or methacrylonitrile as a principal constituent, which is excellent in heat resistance, weatherability, oil resistance, flame retardancy, and low-temperature resistance and which can be economically produced; and a thermoplastic resin composition and an elastomer composition each containing the block copolymer. The block copolymer is produced by reversible addition-fragmentation chain transfer polymerization in the presence of a thiocarbonylthio group-containing compound.

  提供的是一种块状嵌段共聚物，包括一个聚合物块，其中含有丙烯腈或甲基丙烯腈作为主要成分，该共聚物在耐热性、耐候性、耐油性、阻燃性和低温性方面表现出色，并且可以经济地生产；以及分别含有该块状嵌段共聚物的热塑性树脂组合物和弹性体组合物。该块状嵌段共聚物是在含有硫代氨基甲酸酯化合物的情况下通过可逆加成-断裂链转移聚合制备的。
• Flame retardant polymer compositions
  申请人：OCCIDENTAL CHEMICAL CORPORATION

  公开号：EP0063855A1

  公开（公告）日：1982-11-03

  Polyolefins, such as polyethylene and polypropylene, are rendered flame retardant by incorporating therein a combination of (1) a Diels-Alder adduct of a chlorinated cyclopentadiene and a polyunsaturated cycloaliphatic compound and (2) a ring-brominated aromatic compound.

  聚烯烃（如聚乙烯和聚丙烯）通过加入以下两种物质的组合而具有阻燃性能：(1) 氯化环戊二烯和多不饱和环脂族化合物的 Diels-Alder 加合物；(2) 环溴芳烃化合物。
• Modified cyanate ester group curable resin composition, and varnish, prepreg, metal clad laminated board, film, printed circuit board, and multilayered circuit board using the same
  申请人：Hitachi Chemical Company, Ltd.

  公开号：EP0889096A2

  公开（公告）日：1999-01-07

  A modified cyanate ester group curable resin composition, and varnishes, prepregs, laminated boards adhered with metal foil, films, printed circuit boards, and multilayered circuit boards using the same, comprising: (A) a cyanate ester group compound expressed by chemical formula (1), (where, R1 is ―CH2 ―, and respective of and R2 and R3 is any one of hydrogen or methyl group, and the both can be the same or different from each other, (B) a monovalent phenolic group compound expressed by chemical formula (2), or formula (3),    where R4 and R5 is any one of hydrogen atom or low alkyl group having 1 to 4 carbon atoms, and the both can be the same or different from each other,    n is a positive integer of 1 or 2.    (where, R6 is -CH3, -CH2CH3,    or (C) a polyphenylene ether resin, (D) a flame retardant not reactive with the cyanate ester group compound, and (E) a metal group reaction catalyst.

  一种改性氰酸酯类可固化树脂组合物，以及使用该组合物的清漆、预浸料、粘有金属箔的层压板、薄膜、印刷电路板和多层电路板，包括 (A) 由化学式（1）表示的氰酸酯基化合物、 (其中，R1 为 -CH2 -、 和 R2 及 R3 分别为氢或甲基中的任一个，两者可以相同或不同、 (B) 由化学式(2)或式(3)表示的一价酚基化合物、 其中 R4 和 R5 是氢原子或具有 1 至 4 个碳原子的低级烷基中的任一个，两者可以相同或不同、 n 是 1 或 2 的正整数。 (其中，R6 是-CH3、- 、 或 (C) 聚苯醚树脂、 (D) 不与氰酸酯基化合物反应的阻燃剂，以及 (E) 金属基反应催化剂。
• Stabilized flame retardant additives and their use
  申请人：ALBEMARLE CORPORATION

  公开号：EP1092748A1

  公开（公告）日：2001-04-18

  Flame retardant additive compositions having enhanced thermal stability are described. They comprise a blend formed from (A) at least one organic bromine flame retardant selected from (i) a flame retardant compound having a plurality of bromine atoms directly bonded to a cycloaliphatic ring, (ii) the bis(2,3-dibromopropyl ether) of tetrabromobisphenol-A, and (iii) the bis(2,3-dibromopropyl ether) of tetrabromobisphenol-S, (B) an alkyltin mercaptoalkanoate, and (C) a zeolite adjuvant. The proportions are 0.01-0.08 part by weight of (B) per part by weight of (A), and 0.01-0.35 part by weight of (C) per part by weight of (A). Thermoplastic polymer compositions in which these additive compositions are employed possess enhanced properties.

  所述阻燃添加剂组合物具有更高的热稳定性。它们包括由以下物质形成的混合物：(A) 至少一种有机溴阻燃剂，选自 (i) 具有多个溴原子直接键合到环脂族环上的阻燃化合物，(ii) 四溴双酚-A 双（2,3-二溴丙基醚），以及 (iii) 具有多个溴原子直接键合到环脂族环上的阻燃化合物、(ii) 四溴双酚-A 的双(2,3-二溴丙基)醚，和 (iii) 四溴双酚-S 的双(2,3-二溴丙基)醚， (B) 烷基锡巯基烷酸酯，和 (C) 沸石佐剂。其中(B)与(A)的比例为 0.01-0.08 重量份，(C)与(A)的比例为 0.01-0.35 重量份。使用了这些添加剂组合物的热塑性聚合物组合物具有更好的性能。