溴甲烷 | 74-83-9

• 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: 溴甲烷
• 中文别名: 甲基溴；一溴甲烷
• 英文名称: methyl bromide
• 英文别名: Bromomethane
• CAS: 74-83-9
• 化学式: CH₃Br
• 分子量: 94.9388
• InChiKey: GZUXJHMPEANEGY-UHFFFAOYSA-N

物化性质

• 物理描述：
  Methyl bromide appears as colorless highly toxic volatile liquid or a gas. Boiling point 3.56°C (38.41°F). Usually odorless, but has a sweetish chloroform-like odor at high concentrations. Used as an insecticide, a rodenticide, a fumigant, a nematocide, a chemical intermediate and as a fire extinguishing agent. (EPA, 1998)
• 颜色/状态：
  Colorless, transparent, easily liquified gas or volatile liquid
• 气味：
  Usually odorless; sweetish, chloroform-like odor at high concentrations
• 味道：
  Burning taste
• 沸点：
  3.5 °C
• 熔点：
  -93.7 °C
• 闪点：
  194 °C /Open cup vs closed cup not specified/
• 溶解度：
  In water, 15,200 mg/L at 25 °C
• 密度：
  1.6755 g/cu cm at 20 °C
• 蒸汽密度：
  3.27 at 20 °C (Air = 1)
• 蒸汽压力：
  1620 mm Hg at 25 °C
• 亨利常数：
  0.01 atm-m3/mole
• 大气OH速率常数：
  4.02e-14 cm3/molecule*sec
• 稳定性/保质期：
  1. **稳定性**：稳定。 2. **禁配物**：强氧化剂、碱金属或活性金属粉末（如镁、铝等）、二甲亚砜等。 3. **聚合危害**：不会发生聚合。 4. **分解产物**：分解会产生溴化氢。
• 自燃温度：
  537 °C
• 分解：
  Hazardous decomposition products formed under fire conditions. - Carbon oxides, Hydrogen bromide gas.
• 粘度：
  0.397 cP at 0 °C
• 腐蚀性：
  Corrosive to aluminum, magnesium & their alloys
• 燃烧热：
  -787.0 kJ/mol
• 汽化热：
  23.26 kJ/mol at 25 °C
• 表面张力：
  24.5 dynes/cm = 0.0245 N/m at 15 °C
• 电离电位：
  10.54 eV
• 气味阈值：
  In mg/cu m: odor low 80; odor high 4,000
• 折光率：
  Index of refraction: 1.4218 at 20 °C/D
• 相对蒸发率：
  Greater than 1 (butyl acetate= 1)
• 保留指数：
  402.4;421;410.1;414;415;414;419.9;420

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  2
• 可旋转键数：
  0
• 环数：
  0.0
• 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

甲基溴会迅速且广泛地代谢成甲醇（最终转化为二氧化碳）和溴化物。

Methyl bromide is rapidly and extensively metabolized to methanol (ultimately to CO2) and bromide.

来源:Hazardous Substances Data Bank (HSDB)

代谢

在人体红细胞体外实验中，甲基溴被消耗，可能是形成了谷胱甘肽结合物。该反应涉及一种代谢甲基卤素的谷胱甘肽S-转移酶酶。这种酶在鼠、大鼠、牛、羊、猪或恒河猴的红细胞中尚未发现。该酶仅存在于部分人群：在调查的45人中，只有27人与甲基溴发生谷胱甘肽结合。结合者的红细胞中的酶与其他谷胱甘肽S-转移酶在底物特异性、亲和色谱和抑制特性方面有所不同；它已被命名为谷胱甘肽S-转移酶θ。

In human erythrocytes in vitro, methyl bromide is consumed, probably with formation of a glutathione conjugate. The reaction involves a glutathione S-transferase enzyme that metabolized methyl halides. This enzyme has not been found in erythrocytes of mouse, rat, cattle, sheep, pig or rhesus monkey. The enzyme is present only in part of the human population: among 45 people investigated, only 27 conjugated glutathione with methyl bromide. The enzyme is erythrocytes of conjugators is different from other glutathione S-transferases with respect to substrate specificity, affinity chromatography, and inhibition characteristics; it has been designated as glutathione S-transferase theta.

来源:Hazardous Substances Data Bank (HSDB)

代谢

溴甲烷的初步代谢主要是通过亲核取代反应去除溴离子。当攻击物种是水时，生成物是甲醇和溴离子。溴甲烷也可以与有机硫醇（R-SH）反应，产生S-甲基衍生物。这已经在暴露于溴甲烷的小鼠血红蛋白中形成S-甲基半胱氨酸衍生物中得到证实。甲醇或S-甲基衍生物的进一步代谢然后导致二氧化碳的形成。

Bromomethane undergoes initial metabolism primarily by nucleophilic displacement of the bromide ion. When the attacking species is water, the products are methanol and bromide ion. Bromomethane may also react with organic thiols (R-SH) to yield S-methyl derivatives. This has been shown to result in formation of S-methylcysteine derivatives in hemoglobin of mice exposed to bromomethane. Further metabolism of methanol or S-methyl derivatives then leads to the formation of carbon dioxide.

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

甲基溴是一种无色气体。甲基溴最普遍的用途是作为土壤熏蒸剂。它也用于作物收获后的处理和结构熏蒸。据报道，结构非食品处理（如住宅建筑）已不再进行。它还用于合成许多药物和精细化学品，用作甲基化剂或格氏试剂，甲基镁溴。人体研究：甲基溴可以引起严重的刺激和腐蚀性皮肤损伤，水疱和类二度烧伤的水泡。特别是，如果气体或液体被困在手套、靴子或其他衣服中，可能会发生严重伤害。人类因吸入甲基溴而发生过多死亡。过度暴露可能导致中枢神经系统抑制和呼吸衰竭而死亡。此外，吸入高浓度的甲基溴可能会导致直接肺部损伤，导致化学性肺炎和水肿，这也可能是致命的。其次，吸入暴露可能会损害中枢和周围神经系统。在肺部损伤不是致命的情况下，死亡可能是由抽搐或昏迷引起的。在没有死亡的情况下，中枢和周围神经系统的损伤可能会持续，前者为有机脑综合征，后者为重度暴露的周围神经病。中枢和周围神经系统的损伤更常见于急性或高水平慢性暴露，而不是急性暴露。较少见的是，急性过度暴露于甲基溴可能会导致肾脏和肝脏后遗症。人类经验表明，急性致命中毒可由暴露于低至1164至1552 mg/m³的蒸气水平引起，有害效应可能在388 mg/m³或更高时发生。据报道，在约136 mg/m³的浓度下，两周（每天8小时）的暴露会导致全身中毒。症状的严重程度通常会随着暴露水平的提高而增加，并可能因暴露情况和个体敏感性而有所不同。在亚致命中毒病例中，暴露和症状发作之间有一个2至48小时（通常为4至6小时）的潜伏期。人淋巴细胞培养暴露于4.3%甲基溴100秒，姐妹染色单体交换的频率从10.0增加到16.8%。与没有甲基溴暴露史的个人相比，暴露工人的样本显示出喉咽细胞微核的增加和淋巴细胞性嘌呤-鸟嘌呤磷酸核糖基转移酶（hprt）基因突变的增加。动物研究：在室温下将兔眼暴露于纯甲基溴蒸气一分半钟，立即失去表面光泽，几小时后失去角膜上皮，结膜和眼睑明显水肿。一天后，角膜基质呈蓝色，极度肿胀，几乎不透明，但五天内角膜开始清晰。给予兔溴甲烷20-120 mg/kg后，毒性反应包括肢体麻痹、停止饮水、减少尿量。>50 mg/kg的剂量急剧增加了血溴水平并减少了血小板、血清素和水含量。将小鼠暴露于0、0.87、1.72、2.20、2.70、3.50、3.82、4.70、5.77或5.93 mg/L。暴露于3.50 mg/L或更高浓度的动物表现出肾脏病变。暴露于2.20或2.70 mg/L的动物显示肺和肝重量减少。暴露于4.70 mg/L的动物出现肝脏病变。暴露于5.77 mg/L的动物发展为运动协调能力下降。通过灌胃给予大鼠25和50 mg/kg bw甲基溴20、60、90和120天，导致前胃溃疡和上皮增生，但没有证据表明恶性肿瘤。在其他实验中，高剂量雄性与对照组相比，垂体腺瘤的发生率显著增加。在雌性中，没有观察到与治疗相关的肿瘤发生率增加。在大鼠中没有观察到母体毒性、胎儿毒性或发育毒性的临床证据。受精的兔子暴露于70 ppm甲基溴，因过度死亡和神经毒性而终止，表现为一周治疗后出现的抽搐和后肢无力。对照组和20 ppm暴露组的兔子在妊娠第30天被牺牲。20 ppm组没有发现胎儿毒性或发育毒性。在雄性小鼠吸入(14)C甲基溴后，观察到肝和脾DNA鸟嘌呤-N-7的烷基化。在缺乏代谢激活的情况下，以0.02-0.2%的浓度测试时，甲基溴对鼠伤寒沙门氏菌TA100具有诱变性。一种商业甲基溴在没有代谢激活的情况下对鼠伤寒沙门氏菌TA1535和TA100（但不对TA1538或TA98）和大肠杆菌WP2 hcr具有诱变性。吸入甲基溴6小时/天，5天/周，2周后，在大鼠和小鼠的骨髓细胞和小鼠的外周血细胞中诱导了微核。生态毒性研究：甲基溴对鲤鱼最显著的影响是损伤鳃上皮，表明细胞膜的烷基化。按说明使用时，对蜜蜂无害。

IDENTIFICATION AND USE: Methyl bromide is a colorless gas. Methyl bromide's most prevalent use pattern is as a soil fumigant. It is also used as a post harvest treatment of commodities and structural fumigation. Structural non-food treatments (such as residential buildings) are reportedly no longer performed. It is also used in synthesis of many pharmaceuticals and fine chemicals, either as a methylating agent or as the Grignard reagent, methylmagnesium bromide. HUMAN STUDIES: Methyl bromide can cause severe irritation and corrosive skin injury, blisters and vesicles resembling second-degree burns. In particular, severe injury may occur if gas or liquid is trapped in gloves, boots or other clothing. A number of fatalities have occurred in humans from inhalation of methyl bromide. Overwhelming exposure may cause death from CNS depression and respiratory failure. In addition, inhalation exposure to high levels of methyl bromide may cause direct damage to lungs resulting in chemical pneumonia and edema that also may be fatal. Secondarily, inhalation exposure may damage the central and peripheral nervous system. In cases where damage to the lung is not fatal, death may result from convulsions or coma. Where death has not resulted, CNS and PNS damage may persist, the former as organic brain syndrome and the latter as a peripheral neuropathy in cases of heavy exposure. CNS and PNS damage results more commonly from episodic or high level chronic rather than acute exposure. More rarely, renal and hepatic sequelae may ensue from acute overexposure to methyl bromide. Human experience indicates that acute fatal intoxication can result from exposures to vapor levels as low as 1164 to 1552 mg/cu m, and harmful effects can occur at 388 mg/cu m or more. Systemic poisoning has been reported to occur from a two week exposure (8 hr/day) at about 136 mg/cu m. Symptoms generally increase in severity with increasing levels of exposure and may vary somewhat according to exposure circumstances and individual susceptibility. In sublethal poisoning cases a latency period of 2 to 48 hr (usually about 4 to 6 hr) occurs between exposure and onset of symptoms. Exposure of human lymphocyte cultures to 4.3% methyl bromide for 100 sec increased the frequency of sister chromatid exchanges from 10.0 to 16.8%. Compared to individuals with no history of methyl bromide exposure, samples from exposed workers showed an increased incidence of micronuclei in oropharyngeal cells, and an increased frequency of hypoxanthine-guanine phosphoribosyl transferase gene (hprt) mutations in lymphocyte. ANIMAL STUDIES: Experimental exposure of a rabbit's eye to pure methyl bromide gas at room temperature for one and one half minutes caused immediate loss of surface luster, followed in several hours by loss of corneal epithelium, and much edema of the conjunctivae and lids. A day later the corneal stroma was bluish, much swollen, and nearly opaque, but within five days the cornea started to clear. Toxic responses in rabbits administered bromomethane sc at 20-120 mg/kg included limb paralysis, cessation of drinking, reduced urine excretion. Levels >50 mg/kg sharply increased the blood bromide level and reduced platelets, serotonin, and water content. Mice were exposed to 0, 0.87, 1.72, 2.20, 2.70, 3.50, 3.82, 4.70, 5.77, or 5.93 mg/L. Animals exposed to 3.50 mg/L or more exhibited kidney lesions. Animals with exposure to 2.20 or 2.70 mg/L showed decreased lung and liver weight. Liver lesions appeared in animals exposed to 4.70 mg/L. Animals exposed to 5.77 mg/L developed decreased motor coordination. Oral administration of 25 and 50 mg/kg bw methyl bromide by gavage for periods of 20, 60, 90 and 120 days, caused ulceration and epithelial hyperplasia of the forestomach in rats without evidence of malignancy. In other experiment, the incidence of adenomas of the pituitary gland was significantly increased in high-dose males compared with controls. In females, no increase in the incidence of tumors related to treatment was observed. No clinical evidence of maternal toxicity, fetoxicity or developmental toxicity was observed in rats. Inseminated rabbits exposed to 70 ppm methyl bromide were terminated due to excessive mortality and neurotoxicity characterized by convulsions and paresis in the hind limbs seen after one week of treatment. Control and 20 ppm exposed rabbits were sacrificed on gestation day 30. No fetoxicity nor developmental toxicity was noted in the 20 ppm group. Alkylation of guanine-N-7 in DNA of liver and spleen was observed after treatment of male mice with (14)C methyl bromide by inhalation. Methyl bromide was mutagenic to Salmonella typhimurium TA100 when tested at concn of 0.02-0.2% in desiccators in absence of metabolic activation. A commercial methyl bromide was mutagenic to Salmonella typhimurium TA1535 and TA100 (but not to TA1538 or TA98) and to Escherchia coli WP2 hcr in the absence of metabolic activation. Micronuclei were induced in bone marrow cells of rats and mice and in peripheral blood cells of mice exposed to methyl bromide by inhalation for 6 hr/day, 5 days/wk for 2 wk. ECOTOXICITY STUDIES: Morphological damage to the gill epithelium, indicative of alkylation of cell membranes, was the most pronounced effect of methyl bromide in carp. Not hazardous to bees when used as described.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

有机溴化物化合物，如溴甲烷，是强烈的烷基化剂。因此，它们能够轻易地修改自由的硫醇（半胱氨酸）和蛋白质表面的蛋氨酸残基，从而导致酶、转运蛋白或膜功能的破坏。溴离子（由体内溴甲烷代谢产生）已知会影响中枢神经系统，导致一种称为溴中毒的状况。这被认为是溴离子在神经递质和转运系统的反应中替代氯离子的结果，从而影响许多突触过程。（L626, L627, T104）。然而，溴甲烷的确切毒性机制目前尚不确定，尽管其烷基化性质以及通过代谢转化形成的反应中间体仍然是吸引人的假设。

Organobromide compounds such as bromomethane are strong alkylating agents. Consequently they can readily modify free thiols (cysteines) and methionine residues of the surfaces of proteins leading to the disruption of enzyme, transporter or membrane functions. The bromide ion (which is produced from bromomethane metabolism in the body) is known to affect the central nervous system, causing a condition called bromism. This is believed to be a result of bromide ions substituting for chloride ions in the in actions of neurotransmitters and transport systems, thus affecting numerous synaptic processes. (L626, L627, T104). However, the exact mechanism of toxicity for methyl bromide is currently uncertain, although its alkylating property as well as the reactive intermediates formed through metabolic transformation remain attractive hypotheses.

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

评估：对于溴甲烷对人类致癌性的证据不足。对于溴甲烷在实验动物中的致癌性证据有限。总体评估：溴甲烷的致癌性在人类中无法分类（第3组）。

Evaluation: There is inadequate evidence in humans for the carcinogenicity of methyl bromide. There is limited evidence in experimental animals for the carcinogenicity of methyl bromide. Overall evaluation: Methyl bromide is not classifiable as to its carcinogenicity in humans (Group 3).

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

A4；不可归类为人类致癌物。

A4; Not classifiable as a human carcinogen.

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：甲基溴

IARC Carcinogenic Agent:Methyl bromide

来源:International Agency for Research on Cancer (IARC)

吸收、分配和排泄

甲基溴在大鼠、比格犬和人类通过吸入暴露时会被迅速吸收。认为大鼠通过吸入暴露吸收甲基溴的效率比人类更高，在约180 ppm的剂量下吸收了50%。在这一物种中，发现吸收与空气浓度成正比，直到大约300 ppm。在大鼠口服给药后，吸收也迅速而广泛（97%）。在口服或腹腔注射（ip）给药后，甲基溴也会被迅速吸收并分布到各种组织中。

Methyl bromide was rapidly absorbed when rats, beagles, and humans were exposed by inhalation. Rats are believed to be more efficient than humans at absorbing methyl bromide by inhalation exposure, absorbing 50% of the dosage up to approximately 180 ppm. Also in this species, absorption was found to be directly proportional to air concentrations up to about 300 ppm. Absorption also was rapid and extensive (97%) in rats after oral administration (ibid.). After oral or intraperitoneal (ip) administration, methyl bromide also was rapidly absorbed and distributed to various tissues.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

一旦经口服或腹腔注射吸收后，甲基溴在大鼠体内分布到脂肪、肺、肝脏、肾上腺和肾脏，在大脑中含量较少。随后，甲基溴迅速且广泛地代谢为甲醇（最终转化为二氧化碳）和溴化物。经口服或吸入暴露后，大鼠在65至72小时内排除了剂量的85%。大部分放射性碳标记的剂量（30-50%）以呼出的二氧化碳形式回收，4-20%以原始化合物形式呼出，16-40%在尿液中回收，一小部分在粪便中找到。由于给药后第一天胆汁中发现了46%的放射性活性，表明存在广泛的肠肝循环。

Once absorbed after oral or ip administration, methyl bromide is distributed in rats to fat, lung, liver, adrenals, and kidney, with less found in the brain. Thereupon, methyl bromide is rapidly and extensively metabolized to methanol (ultimately to CO2) and bromide. After oral or inhalation exposure, 85% of the dose was eliminated in rats within 65 to 72 hours. Most of the (14)C-radiolabeled dose (30-50%) was recovered as expired CO2, 4-20% as expired parent compound, 16-40% was recovered in the urine, and a small percentage was found in the feces. Extensive enterohepatic circulation was indicated since 46% of the radioactivity was found in bile within the first day after dosing.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在雄性Fischer 344大鼠通过鼻孔吸入50、300、5700或10400纳米摩尔（1.6至310 ppm）的14C甲基溴/升空气6小时后，研究了甲基溴的吸收和14C的排泄途径。在最高浓度下，甲基溴的分数吸收下降，吸入的甲基溴中有37%和27%被吸收，而在较低水平时为48%。在暴露于50或300纳米摩尔/升后，总吸附的甲基溴量为9或40微摩尔/千克体重。呼出的14CO2是排泄的主要途径，从1.2到110微摩尔（吸收量的50%）被呼出，并可以用两个组成部分的负指数函数描述；85%的半衰期为4小时，其余15%的半衰期为17小时。

Uptake of methyl bromide and pathways for excretion of (14)C were investigated in male Fischer 344 rats after nose only inhalation of 50, 300, 5700, or 10,400 nmoles (1.6 to 310 ppm) of (14)C methyl bromide/l of air for 6 hr. Fractional uptake of methyl bromide decreased at the highest concentrations, with 37 and 27% of the inhaled methyl bromide absorbed, compared to 48% at the lower levels. Total methyl bromide adsorbed was 9 or 40 umol/kg body wt after exposure to 50 or 300 nmol/L, respectively. Exhaled (14)CO2 was the dominant route of excretion, with from 1.2 to 110 umol (50% of amount absorbed) exhaled, and was described by a two component negative exponential function; 85% was exhaled with a half-life of 4 hr, & the remaining 15% was exhaled with a half-life of 17 hr.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

Fischer 344雄性大鼠仅通过鼻子暴露于337 nmol (14)C甲基溴/升空气（9.0 ppm，25摄氏度，620 torr）的蒸汽浓度中6小时。在暴露后长达65小时内收集尿液、粪便、呼出空气和组织。以(14)CO2形式排出(14)C是主要的排泄途径，约47%（3900 nmol/大鼠）的总吸收(14)C甲基溴通过此途径排出。暴露后立即在组织中广泛分布放射性，(14)C浓度（以nmol等效物/克为单位）最高的是：肺（250）、肾上腺（240）、肾脏（180）、肝脏（130）和鼻甲（110）。

Male Fischer 344 rats were exposed nose only to a vapor concentration of 337 nmol (14)C methyl bromide/L air (9.0 ppm, 25 degrees C, 620 torr) for 6 hr. Urine, feces expired air, and tissues were collected for up to 65 hr after exposure. Elimination of (14)C as (14)CO2 was the major route of excretion with about 47% (3900 nmol/rat) of the total (14)C methyl bromide absorbed excreted by this route. Radioactivity was widely distributed in tissues immediately following exposure /with highest (14)C concentrations (in nmol equivalent/g) of: lung (250), adrenal (240), kidney (180), liver (130), and nasal turbinates (110)/.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  2.3
• 安全说明：
  S15,S16,S24,S26,S27,S36/37,S36/39,S38,S45,S59,S61,S7
• 危险品运输编号：
  UN 1062 2.3
• WGK Germany：
  3
• 海关编码：
  2903399020
• 危险类别：
  2.3
• 危险品标志：
  T
• 危险类别码：
  R36/37/38,R68,R59,R48/20,R50,R23/25
• RTECS号：
  PA4900000
• 包装等级：
  O52
• 储存条件：
  储存注意事项：应将储存于阴凉、通风的有毒气体专用库房中，并远离火种、热源，确保库温不超过30℃。需保持容器密封，并与氧化剂、活性金属粉末及食用化学品分开存放，切忌混储。使用防爆型照明和通风设施，并禁止使用易产生火花的机械设备和工具。储存区应配备泄漏应急处理设备。

SDS

第一部分：化学品名称

制备方法与用途

制备方法

该物质可作为粮食、木材、仓库杀虫及烟草等土壤消毒的材料，也可用作制药中间体和灭火剂。

合成制备方法

1. 溴化钠法：将甲醇与硫酸加入溴化钠中，在60℃条件下反应。生成的溴甲烷气体经冷凝后进入碱洗塔（50%氢氧化钠）进行脱酸处理，随后通过硫酸干燥塔脱水，并进一步精馏制得纯品。
2. 氢溴酸法：直接用甲醇与氢溴酸进行反应制取。
3. 溴素法：在水存在的情况下，利用硫、溴和甲醇进行反应。

用途简介

暂无具体内容。

用途

该物质主要用于粮食、木材、仓库杀虫及烟草等土壤消毒，也可用作制药中间体和灭火剂。

上下游信息

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  ——	bromocarbene	17141-28-5	CHBr	92.9229

反应信息

• 作为反应物：
  描述：

  溴甲烷 在 sodium amalgam 、 乙酸甲酯 作用下， 生成 甲基汞
  参考文献：
  名称：

  Melnikow, Zhurnal Obshchei Khimii, 1946, vol. 16, p. 2065,2067

  摘要：

  DOI：
• 作为产物：
  描述：

  磷酸三甲酯 在 三溴化硼 作用下， 以 chloroform-d1 为溶剂， 反应 24.0h， 生成 溴甲烷
  参考文献：
  名称：

  Catalytic cleavage of phosphate ester bonds by boron chelates

  摘要：

  揭示了具有一般公式L{YXm}n的新化合物，其中X选自第13族元素，Y是卤素，L是含有至少一个与第13族元素接触的结合原子的螯合配体，所述原子选自C、N、O和S组成的组，m和n是至少为1的整数。 L可以是席夫碱型配体，如salen配体。本发明的组合物可以是双齿、四齿或更多齿的。这些组合物可以用于磷酸酯或醚的去烷基化。优点是，本发明的方法可以具有催化性。

  公开号：

  US07166591B1
• 作为试剂：
  描述：

  dimethyldibromosilane 在 溴甲烷 作用下， 以 neat (no solvent) 为溶剂， 生成 三甲基溴硅烷
  参考文献：
  名称：

  The Vapor Phase Alkylation and Hydrogenation of Chlorosilanes

  摘要：

  DOI：

  10.1021/ja01225a045

文献信息

• 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물
  申请人：Aekyung Chemical Co., Ltd. 애경화학 주식회사(119980027256) Corp. No ▼ 110111-0293011BRN ▼113-81-08840

  公开号：KR101567837B1

  公开（公告）日：2015-11-11

  본 발명은 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물에 관한 것으로, UV 광원에 대한 장파장 흡수율이 높아 내부 경화에 우수한 반응성을 보이며, 광감도 특성이 우수하여 반응 전환율이 높아 반응성 액정 조성물 및 감광성 조성물에서 상용성이 우수한 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물에 관한 것이다.본 발명의 플루오렌구조를 갖는 신규한 광개시제 하기 [일반식]으로 표시되는 것을 특징으로 한다.[일반식] 상기 [일반식]에서 R1, R2는 서로 독립적으로 수소(이때, R1 및 R2가모두 수소는 아니다.), 하기 [화학식 1] 내지 [화학식 9]으로 표시되는 광개시 그룹중에서 어느 하나 선택되며, R3, R4 는 서로 독립적으로 수소, 불소, 탄소수가 1-6인 직쇄형 또는 분지형의 알킬이다.

  本发明涉及具有芴结构的新型光引发剂及包含其的反应性液晶组合物和感光性组合物，其对紫外光源的长波长吸收率高，表现出优异的内部硬化反应性，光敏特性优越，反应转化率高，具有优异的商业性能的具有芴结构的新型光引发剂及包含其的反应性液晶组合物和感光性组合物。本发明的具有芴结构的新型光引发剂具有以下特征[一般式]。在上述[一般式]中，R1，R2独立地表示氢（此时，R1和R2并非都是氢。），选择自[化学式1]至[化学式9]中的光引发基团之一，R3，R4独立地表示氢，氟，1-6个碳原子的直链或支链烷基。
• 一种高纯度3-（2,2,2-三甲基肼）丙酸甲酯盐原料药中间体制备方法
  申请人：东力（南通）化工有限公司

  公开号：CN109369446A

  公开（公告）日：2019-02-22

  一种高纯度3‑(2，2，2‑三甲基肼)丙酸甲酯盐原料药中间体制备方法，它是一种米屈肼和氮丙啶类抗癌药物的重要医药中间体，常规方法是使1，1‑二甲基肼与丙烯酸甲酯反应并真空蒸馏后再与甲基化反应得到目标产物，这种反应所得到的中间体含有铵盐相关杂质导致最终原料药杂质种类和含量超出欧洲药典杂质限制范围，纯化工艺复杂化。本发明提供了制备这两种化合物的高效的改良方法，不仅获得高纯度产品而且提高了产品的产率，降低成本，实现了商业大规模生产。
• Synthesis of (E)- and (Z)-pulvinones
  作者：Alexander C. Campbell、Maurice S. Maidment、John H. Pick、Donald F. M. Stevenson

  DOI：10.1039/p19850001567

  日期：——

  one of which involves a novel Wittig reaction. For the first time, members of the E-series, including the parent (E)-pulvinone, are reported and the structural elucidation of the geometric isomers is described. A method for quantitatively converting (E)-pulvinones into (Z)-pulvinones is presented, together with a technique for differentiating between the isomers.

  已经开发出两种新的途径获得pulvinones，其中一种涉及新颖的Wittig反应。首次报道了E系列的成员，包括母体（E）-普尔维酮，并描述了几何异构体的结构。提出了一种将（E）-普尔维酮定量转化为（Z）-普尔维酮的方法，以及区分异构体的技术。
• PREPARATION METHOD FOR RIVASTIGMINE, INTERMEDIATES THEREOF, AND PREPARATION METHOD FOR SAID INTERMEDIATES
  申请人：Zhang Fuli

  公开号：US20140073809A1

  公开（公告）日：2014-03-13

  The present invention provides the preparation method for (S)-3-(1-(dimethylamino)ethyl)phenyl ethyl(methyl)carbamate (formula X compound), the preparation methods for its intermediates (S)-1-(3-methoxyphenyl)-N,N-dimethyl-N—((S)-1-phenylethyl)ethanaminium (formula VI compound), (S)-1-(3-hydroxyphenyl)-N,N-dimethyl-N—((S)-1-phenylethyl)ethanaminium (formula VIII compound) and (S)-1-(3-(ethyl(methyl)carbamoyloxy)phenyl)-N,N-dimethyl-N—((S)-1-phenylethyl)ethanaminium (formula IX compound), as well as the method for using above mentioned formula IX compound to prepare rivastigmine which can be used for the treatment of Alzheimer's disease. The preparation method for rivastigmine has a reasonable synthetic design with convenient source of raw materials and high total yield, and the product resulted has high chemical and optical purity, which makes it easy for large-scale. industrial production.

  本发明提供了(S)-3-(1-(二甲基氨基)乙基)苯基乙基(甲基)氨基甲酸酯（化合物X的结构）的制备方法，以及其中间体(S)-1-(3-甲氧基苯基)-N,N-二甲基-N-((S)-1-苯乙基)乙胺盐（化合物VI的结构）、(S)-1-(3-羟基苯基)-N,N-二甲基-N-((S)-1-苯乙基)乙胺盐（化合物VIII的结构）和(S)-1-(3-(乙基(甲基)氨基甲酰氧基)苯基)-N,N-二甲基-N-((S)-1-苯乙基)乙胺盐（化合物IX的结构）的制备方法，以及利用上述化合物IX制备利伐替林的方法，利伐替林可用于治疗阿尔茨海默病。利伐替林的制备方法具有合理的合成设计，原料来源便利，总产率高，所得产品具有高化学和光学纯度，便于大规模工业生产。
• A General and Efficient Approach to Aryl Thiols: CuI-Catalyzed Coupling of Aryl Iodides with Sulfur and Subsequent Reduction
  作者：Yongwen Jiang、Yuxia Qin、Siwei Xie、Xiaojing Zhang、Jinhua Dong、Dawei Ma

  DOI：10.1021/ol902186d

  日期：2009.11.19

  A CuI-catalyzed coupling reaction of aryl iodides and sulfur powder takes place in the presence of K2CO3 at 90 °C. The coupling mixture is directly treated with NaBH4 or triphenylphosphine to afford aryl thiols in good to excellent yields. A wide range of substituted aryl thiols that bear methoxy, hydroxyl, carboxylate, amido, keto, bromo, and fluoro groups can be assembled through this procedure.

  CuI催化的芳基碘化物和硫粉的偶联反应在90°C的K 2 CO 3存在下进行。偶联混合物直接用NaBH 4或三苯基膦处理，以良好或优异的收率得到芳基硫醇。可以通过该程序组装具有甲氧基，羟基，羧酸酯基，酰胺基，酮基，溴基和氟基的各种各样的取代的芳基硫醇。

表征谱图