三聚丙烯 | 115-07-1

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 无环烃
• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 中文名称: 三聚丙烯
• 中文别名: 甲基乙烯；丙烯；1-丙烯；丙烯(化学级)；丙烯(合成级)
• 英文名称: propene
• 英文别名: 1-propene；propylene；prop-1-ene
• CAS: 115-07-1；13987-01-4
• 化学式: C₃H₆
• 分子量: 42.0806
• InChiKey: QQONPFPTGQHPMA-UHFFFAOYSA-N

物化性质

• 熔点：
  −185 °C(lit.)
• 沸点：
  −47.7 °C(lit.)
• 密度：
  1.49
• 蒸气密度：
  1.48 (vs air)
• 闪点：
  -108 °C
• 介电常数：
  1.9（20℃）
• LogP：
  1.77 at 20℃
• 物理描述：
  Propylene is a colorless gas with a faint petroleum like odor. It is shipped as a liquefied gas under its own vapor pressure. For transportation it may be stenched. Contact with the liquid can cause frostbite. It is easily ignited. The vapors are heavier than air. Any leak can either be liquid or vapor. It can asphyxiate by the displacement of air. Under prolonged exposure to fire or intense heat the containers may rupture violently and rocket. It is used to make other chemicals. Can cause explosion.
• 颜色/状态：
  Colorless gas
• 气味：
  Practically odorless; aromatic
• 溶解度：
  In water, 200 mg/L at 25 °C
• 蒸汽密度：
  1.46 (Air = 1.0) at 0 °C
• 蒸汽压力：
  8.69X10+3 mm Hg at 25 °C /Extrapolated/
• 亨利常数：
  0.20 atm-m3/mole
• 大气OH速率常数：
  2.63e-11 cm3/molecule*sec
• 稳定性/保质期：
  Stable under recommended storage conditions.
• 自燃温度：
  851 °F (455 °C)
• 粘度：
  83.4 micropoises at 16.7 °C
• 燃烧热：
  -19,692 Btu/lb = -10,940 cal/g = -458.04X10+5 J/kg
• 汽化热：
  18.42 kJ/mol at BP
• 聚合：
  A mixture under confinement in a glass pressure bottle at 20 °C polymerized explosively, the polymerization probably being initiated by access of light through the clear glass container. Such alkene-sulfur dioxide co-polymerizations will not occur above a ceiling temperature, different for each alkene.
• 气味阈值：
  ... between 39.6 and 116.27 mg/cu m.
• 保留指数：
  294;283;290;294;289;286;294;295;295;295;295;298;288;290;290;283;290;290;290;283;310;290

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

...暴露于6 ppm丙烯6小时导致大鼠每克血液中产生160纳克环氧丙烷...600 ppm丙烯8小时导致每克血液中产生740纳克环氧丙烷。两种暴露浓度均降低了鼻腔和肝脏细胞色素P450的水平（程度不同）。

...Exposure to 6 ppm propylene for 6 hours produced 160 ng propylene oxide per gram of blood in rats... 600 ppm propylene for 8 hours produced 740 ng propylene oxide per gram of blood. Both exposure concentrations reduced nasal and liver cytochrome P450 levels (to differing degrees).

来源:Hazardous Substances Data Bank (HSDB)

代谢

环氧丙烷是在丙烯代谢的第一步产生的。当使用H2O中的反式-1-氘代丙烯或D2O中的丙烯（pH 7.4，4°C）时，通过包括细胞色素P450还原酶的重构细胞色素P450LM2系统进行的环氧化反应伴随着从水相中的共轭、立体特异性（相对于烷基组的反式）氢/氘交换。在将丙烯与来自雄性Wistar大鼠（对照和苯巴比妥预处理动物）和雄性NMRI/HAN小鼠（对照、苯巴比妥和苯并[a]芘预处理动物）的肝微粒体以及NADPH再生系统一起孵化（37°C，pH 7.4）后，发现了丙烯环氧烷的两种对映异构体。在含有三氯丙烯环氧烷的孵化中，环氧水解酶活性被抑制。在用大鼠肝微粒体的孵化中，形成了大约30%的R-对映体和大约70%的S-对映体，而在用小鼠微粒体的孵化中，两种对映异构体的量几乎相等：R，42-55%；S，45-58%，具体取决于预处理情况。

Propylene oxide is produced during the first step of propylene metabolism. Epoxidation by a reconstituted cytochrome P450LM2 system including cytochrome P450 reductase proceeded with a concomitant, stereospecific (trans to the alkyl group) hydrogen/deuterium exchange from the aqueous phase when trans-1-deuterio-propylene in H2O or propylene in D2O (pH 7.4, 4 °C) was used. Both enantiomers of propylene oxide were found after incubation (37 °C, pH 7.4) of propylene with an NADPH-regenerating system and microsomes prepared from livers of male Wistar rats (control and phenobarbital-pretreated animals) and male NMRI/HAN mice (control, phenobarbital- and benzo[a]pyrene-pretreated animals). Epoxide hydrolase activity was inhibited in those incubates which contained trichloropropylene oxide. In incubations with liver microsomes of rats, about 30% of R- and about 70% of S-enantiomer were formed, whereas with mouse microsomes the amounts of the two enantiomers were nearly equal: R, 42-55%; S, 45-58%, depending on the pretreatment.

来源:Hazardous Substances Data Bank (HSDB)

代谢

DNA中鸟嘌呤N7位的烷基化在暴露于大气丙烯或统一标记的(14)C-丙烯的雄性CBA小鼠中进行了研究。丙烯代谢的速率计算出的丙烯浓度与加合物的水平相关（丙烯氧化物0.88 mmol/kg bw）。在封闭式暴露室中暴露于107 MBq统一标记的(14)C-丙烯（18.1 MBq/mmol丙烯）7小时后，立即处死小鼠并测量2-羟基丙烯-DNA加合物。测得的值为：肝脏，3000 pmol/g DNA；肾脏，3000 pmol/g DNA；脾脏，2000 pmol/g DNA。

Alkylation of DNA at the N7 position of guanine was investigated in male CBA mice exposed to atmospheric propylene or uniformly labelled (14)C-propylene. The adduct levels were related to the concentration of propylene oxide (0.88 mmol/kg bw), calculated from the rate of propylene metabolism. Immediately after exposure to 107 MBq uniformly labelled (14)C-propylene (18.1 MBq/mmol propylene) for 7 hr in a closed exposure chamber, in which the atmospheric concentration-time course was measured after injection of a single dose into the chamber atmosphere, the mice were killed and 2-hydroxypropyl-DNA adducts were measured. The values were: liver, 3000 pmol/g DNA; kidney, 3000 pmol/g DNA; and spleen, 2000 pmol/g DNA.

来源:Hazardous Substances Data Bank (HSDB)

代谢

... 暴露于6 ppm丙烯6小时，在大鼠血液中产生了每克血液160纳克环氧丙烷... 600 ppm丙烯8小时产生了每克血液740纳克环氧丙烷。两种暴露浓度都降低了鼻腔和肝脏细胞色素P450的水平（程度不同）。

... Exposure to 6 ppm propylene for 6 hours produced 160 ng propylene oxide per gram of blood in rats... 600 ppm propylene for 8 hours produced 740 ng propylene oxide per gram of blood. Both exposure concentrations reduced nasal and liver cytochrome P450 levels (to differing degrees).

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别和使用：丙烯是一种无色气体。它用于制造异丙醇、聚丙烯、合成甘油、丙烯腈、环氧丙烷、庚烯、异丙苯、聚合物汽油、丙烯酸、乙烯基树脂、氧化学品。它也用作气溶胶推进剂和组分。以前在牙科手术中用作临时麻醉剂。人体研究：根据有限的人体研究，丙烯在气态时对皮肤或眼睛没有刺激性。然而，如果液态的这种化学物质接触到皮肤或眼睛，可能会导致组织冻结、严重冷烧伤和/或冻伤。动物研究：在为期14周的重复剂量吸入毒性研究中，啮齿类动物在丙烯浓度高达10,000 ppm的情况下未观察到不良反应。此外，在丙烯浓度高达10,000 ppm的情况下，对大鼠或小鼠进行长达103周的暴露，没有致癌性的证据。在雄性大鼠暴露于5,000和10,000 ppm丙烯和雌性大鼠暴露于10,000 ppm丙烯103周后，鼻腔炎症是观察到的唯一毒性迹象。当大鼠在14周内暴露于相似浓度时，这些效果并未观察到。在Ames试验中，一种单一的细菌菌株在代谢激活的条件下观察到了致突变活性。在预产期前一天（第6-19天）将怀孕的Wistar大鼠暴露于丙烯，所有测试浓度高达10,000 ppm均未引起母体毒性、胎儿毒性或发育毒性。

IDENTIFICATION AND USE: Propylene is a colorless gas. It is used in manufacture of isopropyl alcohol, polypropylene, synthetic glycerol, acrylonitrile, propylene oxide, heptene, cumene, polymer gasoline, acrylic acid, vinyl resins, oxo chemicals. It is also used as aerosol propellant and component. Formerly used in dental surgery as temporary anesthetic. HUMAN STUDIES: In the gaseous state propylene is not irritating to the skin or eyes based on limited human studies. However, should skin or eye contact occur to this chemical in its liquid state, tissue freezing, severe cold burn, and/or frostbite may result. ANIMAL STUDIES: No adverse effects were observed in repeated dose inhalation toxicity studies in rodents at concentrations up to 10,000 ppm propylene, for 14 weeks. Furthermore, there was no evidence of carcinogenicity in rats or mice exposed to propylene concentrations as high as 10,000 ppm for up to 103 weeks. Inflammation of the nasal cavity was the only indication of toxicity observed following exposure of male rats to 5,000 and 10,000 ppm propylene and female rats exposed to 10,000 propylene for 103 weeks. These effects were not observed when rats were exposed to similar concentrations for 14 weeks. Mutagenic activity was observed in a single bacterial strain in the Ames assay in the presence of metabolic activation. Inhalation exposure of pregnant Wistar rats to propylene from implantation to one day prior to the expected day of parturition (days 6-19 p.c.) elicited no maternal toxicity, prenatal or developmental toxicity, or teratogenicity at all tested concentrations up to 10,000 ppm.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

评估：对于丙烯的人类致癌性证据不足。对于实验动物的丙烯致癌性证据不足。总体评估：丙烯对人类的致癌性无法分类（第3组）。

Evaluation: There is inadequate evidence in humans for the carcinogenicity of propylene. There is inadequate evidence in experimental animals for the carcinogenicity of propylene. Overall evaluation: Propylene is not classifiable as to its carcinogenicity to 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：丙烯

IARC Carcinogenic Agent:Propylene

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

积累是不太可能的，因为从体内快速移除。... 丙烷和体内生物介质之间的直接化学反应也不太可能。未改变的形态通过肺部快速消除。

Accumulation is /unlikely/ because of rapid removal from the body. ... A direct chemical interaction between propylene and biological media of the body is /also/ unlikely. Elimination occurs rapidly in an unaltered form through the lungs.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

丙烯吸入的药代动力学已经在雄性Sprague-Dawley大鼠和CBA小鼠在封闭暴露室中进行研究，其中在向室内空气中注入单剂量后，测量了大气浓度-时间过程。研究发现大鼠体内丙烯的吸收较低。由于吸收导致的清除，反映了丙烯从大气中转移到生物体中的速率，对于一只体重250克的大鼠，清除率为19毫升/分钟。这个值仅代表肺泡通气量（117毫升/分钟）的16%。吸入肺部的丙烯大部分又被呼出，没有进入血液成为全身可利用的物质。同一大鼠体内丙烯的最大积累，以整体动物：空气的热力学分配系数（Keq=Conc.animal/Conc.air）来衡量，仅为1.6。在浓度低于50 ppm[86 mg/m³]时，稳态下整体动物：空气中的浓度比甚至更小（0.7），这是由于代谢消除。在这些浓度下，发现了第一级动力学，并且相对于大气中的浓度，由于代谢导致的清除率在250克大鼠中计算为11毫升/分钟。因此，在稳态下，大约58%全身可利用的丙烯通过代谢消除，42%以未改变的物质通过呼出消除。对于小鼠尚未发布相应的数据。在大鼠和小鼠中，丙烯的代谢速率显示出饱和动力学，最大代谢速率（Vmax）分别为0.17 umol/(min x 250 g bw)[1.7 mg/(hr x kg bw)]和8 mg/(hr x kg bw)，Vmax/2的大气浓度分别为260 ppm（447 mg/m³）和800 ppm（1376 mg/m³）。

The pharmacokinetics of inhaled propylene have been investigated in male Sprague- Dawley rats and CBA mice in closed exposure chambers, in which the atmospheric concentration-time course was measured after injection of a single dose into the chamber atmosphere. The uptake of propylene into the body of rats has been found to be low. Clearance due to uptake, reflecting the rate of transfer of propylene from the atmosphere into the organism, was 19 mL/min for one rat weighing 250 g. This value represents only 16% of the alveolar ventilation (117 mL/min). Most propylene inhaled into the lungs is exhaled again and does not reach the blood to become systemically available. Maximal accumulation of propylene in the same rat, determined as the thermodynamic partition coefficient for whole body:air (Keq=Conc.animal/Conc.air), was only 1.6. At concentrations below 50 ppm [86 mg/cu m], the concentration ratio at steady-state whole body:air was even smaller (0.7), owing to metabolic elimination. At these concentrations, first-order kinetics were found, and clearance due to metabolism in relation to the concentration in the atmosphere was calculated to be 11 mL/min for a 250-g rat. Thus, at steady state, about 58% of systemically available propylene is eliminated metabolically and 42% is eliminated by exhalation as the unchanged substance. No corresponding data have been published for mice. In rats and mice, the rate of propylene metabolism showed saturation kinetics, with maximal metabolic rates (Vmax) of 0.17 umol/(min x 250 g bw) [1.7 mg/(hr x kg bw)] and 8 mg/(hr xkg bw) and atmospheric concentrations at Vmax/2 of 260 ppm (447 mg/cu m) and 800 ppm (1376 mg/cu m), respectively.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在雄性Sprague-Dawley大鼠中，当大气中浓度超过50 ppm [86 mg/m3]时，丙烯的吸收变得越来越饱和...

In male Sprague-Dawley rats, propylene /absorption/ becomes increasingly saturated at concentrations above 50 ppm [86 mg/m3] in the atmosphere...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

丙烯表现出米氏-门顿饱和动力学特征。

Propylene exhibits saturation kinetics according to Michaelis-Menten.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

一个针对吸入丙烷气体（PE）的小鼠、大鼠和人类的生理毒物动力学（PT）模型被开发出来。模拟代谢主要发生在肝脏（90%）和丰富血流的组织群（10%）。组织：空气的分配系数是通过使用小鼠、大鼠和人类的组织在体外确定的。大多数组织的分配系数约为0.5。只有脂肪组织的值高出10倍。人类的血液：空气分配系数为0.44，约为啮齿动物的的一半。PE在生物体中的积聚非常有限。对于B6C3F1雄性小鼠和Fischer 344/N雄性大鼠，通过气体摄取实验获得了PE代谢的参数。小鼠和大鼠的最大代谢速率（V(maxmo)）分别为110 umol/hr/kg和50.4 umol/hr/kg。小鼠在大气PE浓度为270 ppm时达到V(maxmo)/2，大鼠在400 ppm时达到。用二乙基二硫代氨基甲酸钠预处理动物几乎完全抑制了两种动物PE的代谢。在一项初步的毒物动力学研究中，一名志愿者在持续接触5和25 ppm PE的环境中分别暴露了最多4.5小时，以获取人类PE代谢的数据。使用PT模型计算了稳态下PE的血液浓度。在25 ppm时，血液值在物种之间是相当的，小鼠、大鼠和人类分别为0.19、0.32和0.34 umol/L。然而，相应的PE代谢速率差异很大，小鼠、大鼠和人类分别为8.3、2.1和0.29 umol/hr/kg。对于人类重复暴露于空气中25 ppm PE的情况（每天8小时，每周5天），模拟了静脉血中PE的浓度。预测表明，PE被消除得如此之快，以至于它不能在生物体中积聚。对于低暴露浓度，显而易见的是，通过吸入进入血液的速度受到通过肺部的血流量和通过代谢器官的血流量限制。

A physiological toxicokinetic (PT) model was developed for inhaled propylene gas (PE) in mouse, rat, and human. Metabolism was simulated to occur in the liver (90%) and in the richly perfused tissue group (10%). The partition coefficients tissue:air were determined in vitro using tissues of mice, rats, and humans. Most of the tissues have partition coefficients of around 0.5. Only adipose tissue displays a 10 times higher value. The partition coefficient blood:air in human is 0.44, about half of that in rodents. PE can accumulate in the organism only barely. For male B6C3F1 mice and male Fischer 344/N rats, parameters of PE metabolism were obtained from gas uptake experiments. Maximum rates of metabolism (V(maxmo)) were 110 umol/hr/kg in mice and 50.4 umol/hr/kg in rats. V(maxmo)/2 was reached in mice at 270 ppm and in rats at 400 ppm of atmospheric PE. Pretreatment of the animals with sodium diethyldithiocarbamate resulted in an almost complete inhibition of PE metabolism in both species. Preliminary toxicokinetic data on PE metabolism in humans were obtained in one volunteer who was exposed up to 4.5 hr to constant concentrations of 5 and 25 ppm PE. The PT model was used to calculate PE blood concentrations at steady state. At 25 ppm, the blood values were comparable across species, with 0.19, 0.32, and 0.34 umol/L for mouse, rat, and human, respectively. However, the corresponding rates of PE metabolism differed dramatically, being 8.3, 2.1, and 0.29 umol/hr/kg in mouse, rat, and human. For a repeated human exposure to 25 ppm PE in air (8 hr/day, 5 days/wk), PE concentrations in venous blood were simulated. The prediction demonstrates that PE is eliminated so rapidly that it cannot accumulate in the organism. For low exposure concentrations, it became obvious that the rate of uptake into blood by inhalation is limited by the blood flow through the lung and the rate of metabolism is limited by the blood flow through the metabolizing organs.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  2.1
• 危险品标志：
  F+
• 安全说明：
  S16,S33,S9
• 危险类别码：
  R12
• WGK Germany：
  -
• 海关编码：
  2901220000
• RTECS号：
  UC6740000
• 危险类别：
  2.1
• 危险品运输编号：
  UN 1077 2.1

制备方法与用途

丙烯是一种重要的化工原料，具有多种用途和生产方法。以下是关于丙烯的详细信息：

化学性质

• 分子式: CH2=CHCH3
• 分子量: 42.08
• 物理性质:
  • 常温常压下为无色可燃性气体。
  • 略有烃类特有的气味。
  • 可溶于乙醇和乙醚，微溶于水。

主要用途

1. 有机合成原料

   • 丙烯气相氧化得到的丙烯醛用于生产丙烯酸、烯丙醇、甘油醛等。
   • 丙烯氨氧化得到的丙烯腈是合成纤维、合成橡胶和塑料的重要原料。
   • 丙烯氯化得到的氯丙烯可进一步制得多种化学品，如烯丙醇、丙烯二氯丙醇、氯丙腈等。

2. 生产重要产品

   • 制备异丙醇：用于生产丙酮、异丙胺及异丙酯。
   • 丙烯二聚得到乙烯、三聚得到千烯、聚合得到聚丙烯，丙烯四聚得到的十二碳烯是表面活性剂的中间体。

生产方法

1. 炼厂催化裂化气精馏法

   • 经蒸馏除去C2和C4馏分，得到丙烯、丙烷馏分。
   • 再经精馏得纯度较高的丙烯。

2. 石油烃类高温裂解

   • 是乙烯生产的联产品之一。
   • 石油热解气体中含有一定量的丙烯。

3. 丙烷脱氢法

   • 催化剂为氧化铬-氧化铝，反应温度635℃，丙烷转化率54%，丙烯选择性76%，回收率93%（分子比）。

安全与防护

• 急性毒性:

  • 大鼠吸入TCL0: 5000 PPM/6小时/2年。

• 爆炸物危险特性: 与空气混合明火、受热可爆。

• 可燃性危险特性: 明火、受热可燃; 燃烧产生刺激烟雾。

• 储运特性:

  • 库房通风低温干燥;
  • 轻装轻卸;
  • 与氧气、空气等助燃气体钢瓶分开存放。

• 灭火剂:

  • 雾状水、二氧化碳、泡沫。

职业标准

• TWA: 17500 毫克/立方米

综上所述，丙烯是一种广泛应用的化工原料，在生产过程中需要严格的安全防护措施。

反应信息

• 作为反应物：
  描述：

  三聚丙烯 在 氢气 作用下， -62.1~174.9 ℃ 、66.66 kPa 条件下， 生成 异丙基自由基
  参考文献：
  名称：

  Kinetic Isotope Effects in the H+C₃H₆→C₃H₇Reaction

  摘要：

  通过脉冲辐射解离-共振吸收技术，在200–500 K的温度范围内测定了H和D原子与丙烯-d0和-d6的加成反应的绝对速率常数。所得的速率常数可以用以下阿伦尼乌斯方程很好地表示：k(H+C3H6)=(3.00±0.38)exp[−(1612±66)⁄RT]，k(H+C3D6)=(2.55±0.57)exp[−(1509±128)⁄RT]，k(D+C3H6)=(1.99±0.05)exp[−(1550±15)⁄RT]，和k(D+C3D6)=(2.20±0.27)exp[−(1587±67)⁄RT]，单位为10−11 cm3 molecule−1 s−1。活化能的单位是cal mol−1。几乎没有可归因于C3H6和C3D6之间差异的同位素效应被观察到。这与之前在H和D原子与同位素乙烯加成速率常数中观察到的动能同位素效应相似。上述反应的理论速率常数是通过常规的活化复合物理论，使用从头算方法绘制的势能面计算的；然而，由于C3H6和C3D6之间的差异，实验和理论之间无法就同位素效应达成一致。这也与H+C2H4→C2H5反应中发现的同位素效应相似。

  DOI：

  10.1246/bcsj.55.3720
• 作为产物：
  描述：

  沙林 以 异辛烷 、 十二烷 为溶剂， 生成 三聚丙烯
  参考文献：
  名称：

  Measurement of gas phase reactions using automated headspace gaschromatography

  摘要：

  DOI：

  10.1007/bf00811273
• 作为试剂：
  描述：

  氯化苦 在 air 、 三聚丙烯 、 二氧化氮 作用下， 生成 光气
  参考文献：
  名称：

  通过向丙烯/NO/空气/光辐照系统中添加氯化苦（三氯硝基甲烷）来增强臭氧的形成

  摘要：

  氯化苦在空气中在 1 个大气压下的光解是在 6 立方米的光化学反应室中进行的，该反应室结合了氙弧灯和耐热玻璃过滤器作为光源。光气作为主要产品之一获得，收率一致。没有观察到亚硝酰氯，这支持光解的 C-N 断裂机制。在达到臭氧浓度最大值后，将氯化苦加入丙烯/NO/空气/光辐照系统时，光化学臭氧的形成得到增强。然而，在所采用的条件下，氯化苦的臭氧形成因子估计为每摩尔分解的氯化苦形成 0.25 摩尔的臭氧。这意味着 Cl 原子本身有助于破坏臭氧，而不是在实验条件下形成臭氧。氯化苦释放的 NO2 是臭氧增强的来源。如果氯化苦作为土壤熏蒸剂的用量增加，会导致土壤中臭氧浓度升高。...

  DOI：

  10.1246/bcsj.72.1497

文献信息

• Fe and Co Complexes of Rigidly Planar Phosphino-Quinoline-Pyridine Ligands for Catalytic Hydrosilylation and Dehydrogenative Silylation
  作者：Debashis Basu、Ryan Gilbert-Wilson、Danielle L. Gray、Thomas B. Rauchfuss、Aswini K. Dash

  DOI：10.1021/acs.organomet.8b00416

  日期：2018.8.27

  of simple and complex 1-alkenes with a variety of hydrosilanes. Catalysts derived from MesNQpy exhibited low activity. Fe-RPQpy derived catalysts favor hydrosilylation, whereas Co-RPQpy based catalysts favor dehydrogenative silylation. Catalysts derived from CoX2(iPrPQpy) convert hydrosilanes and ethylene to vinylsilanes. Related experiments were conducted on propylene to give propenylsilanes.

  制备了一种新的刚性平面PNN配体平台的Co和Fe二卤化物配合物，并将其作为烯烃氢化硅烷化的预催化剂。将Thummel的8-溴-2-（吡啶-2'-基）喹啉锂化，然后用（i- Pr）2 PCl和（C 6 F 5）2 PCl处理，得到膦-喹啉-吡啶配体，缩写为R PQpy对于R ＝i- Pr和C 6 F 5。这些配体与铁和钴的二氯化物和二溴化物形成1：1加合物。FeBr 2（iPr PQpy），FeBr 2（ArFPQpy），CoCl 2（iPr PQpy），CoBr 2（iPr PQpy）和CoCl 2（ArF PQpy）证实这些配合物的M–P–C–C–N–C–C–N部分在0.078范围内为平面不同于前几代的PNN配合物，其平面度偏差约为0.35。键距和磁性表明Fe络合物为高自旋，而钴络合物为高自旋或参与自旋平衡。还研究了R PQpy配体的NNN类似物，其中膦基被异丁烯酮取代。FeBr 2（Mes
• Asymmetric Markovnikov Hydroaminocarbonylation of Alkenes Enabled by Palladium-Monodentate Phosphoramidite Catalysis
  作者：Ya-Hong Yao、Hui-Yi Yang、Ming Chen、Fei Wu、Xing-Xing Xu、Zheng-Hui Guan

  DOI：10.1021/jacs.0c11249

  日期：2021.1.13

  n of alkenes with anilines has been developed for the atom-economical synthesis of 2-substituted propanamides bearing an α-stereocenter. A novel phosphoramidite ligand L16 was discovered which exhibited very high reactivity and selectivity in the reaction. This asymmetric Markovnikov hydroaminocarbonylation employs readily available starting materials and tolerates a wide range of functional groups

  已经开发了钯催化的烯烃与苯胺的不对称马尔科夫尼科夫氢氨基羰基化反应，用于原子经济合成带有 α-立体中心的 2-取代丙酰胺。发现了一种新的亚磷酰胺配体 L16，它在反应中表现出非常高的反应性和选择性。这种不对称 Markovnikov 氢氨基羰基化使用容易获得的起始材料并耐受范围广泛的官能团，从而为在环境条件下区域选择性和对映选择性合成 2-取代丙酰胺提供了一种简便而直接的方法。机理研究表明，该反应通过钯氢化物途径进行。
• On the mechanism and synthetic applications of the thermal and alkaline degradation of c-18 castor oil
  作者：S. Ranganathan、Raaj Kumar、V. Maniktala

  DOI：10.1016/s0040-4020(01)99322-6

  日期：1984.1

  c-8 via unique sequence involving a primary reaction which is associated with three different types of redox systems as well as with uncoupled oxidation, the overall change amounting to a milieu of hydride transfer, π -migration, retro-Michael, retro-aldol, Meerwein-Pondorff-Verley as well as Cannizzaro type of reactions. These findings which constitute the core of the present work, are of significance

  由π蓖麻油片段的C-18骨架，热至C-11 + C-7 2 S +π 2 S +Ò 2s过程，并通过独特的顺序将热碱转化为c-10 + c-8，该过程涉及与三种不同类型的氧化还原系统以及未偶联的氧化有关的主要反应，总体变化相当于氢化物转移的环境π -迁移，迈克·怀特（Michael），怀特·阿尔多（Retro-aldol），Meerwein-Pondorff-Verley以及Cannizzaro型反应。这些发现构成了本研究的核心，不仅对于了解蓖麻油的两个最重要的反应具有重要意义，而且在利用这些知识来引导和优化所需产品方面也具有重要意义。此外，它们为机械有机化学增加了一个独特的方面。蓖麻油C-18→C-11 + C-7变化的协调性质的令人信服的证据是，将12-羟基十八烷基9-壬酸甲酯干净地转化为新型有用的烯丙基酯，十一碳烯酸9,10-讨人喜欢。对不同的α-取代的γδ-不饱和醇进行的模型研究表明，π2个S
• [EN] PROCESSES FOR SYNTHESIS OF 1,3,3,3-TETRAFLUOROPROPENE AND 2,3,3,3-TETRAFLUOROPROPENE<br/>[FR] PROCEDES POUR LA SYNTHESE DE 1,3,3,3-TETRAFLUOROPROPENE ET DE 2,3,3,3-TETRAFLUOROPROPENE
  申请人：HONEYWELL INT INC

  公开号：WO2005108334A1

  公开（公告）日：2005-11-17

  Disclosed in one embodiment is a process for the synthesis of 1,3,3,3-tetrafluoropropene that comprises (a) reacting a compound of formula (I) X1X2 with a compound of formula (II) CF3CH=CH2 to produce a reaction product comprising a compound of formula (III) CF3CHX1CH2X2, wherein X1 and X2 are each independently selected from the group consisting of hydrogen, chlorine, bromine and iodine, provided that X1 and X2 are not both hydrogen; (b) when X2 in formula (III) is not fluorine, fluorinating the compound of formula (III) to produce a reaction product comprising a compound of formula (III) wherein X1 is as described above and X2 is fluorine; and (c) exposing said compound of formula (III) to reaction conditions effective to convert said compound to 1,3,3,3,-tetrafluoropropene. In another embodiment, the process comprises (a) reacting chlorine with a compound of formula (I) CH3CH=CH2 to produce a reaction product comprising a compound of formula (II) CCI3CHC1CH2C1; (b) fluorinating the compound of formula (II) to produce a reaction product comprising a compound of formula (III) CF3CHC1CH2F; and (c) exposing said compound of said formula (III) to reaction conditions effective to convert said compound to 1,3,3,3-tetrafluoropropene.

  一个实施例中披露了一种合成1,3,3,3-四氟丙烯的方法，包括：(a)将式(I) X1X2化合物与式(II) CF3CH=CH2化合物反应，生成包含式(III) CF3CHX1CH2X2化合物的反应产物，其中X1和X2分别独立地选自氢、氯、溴和碘组成的群，前提是X1和X2不同时为氢；(b)当式(III)中的X2不是氟时，对式(III)化合物进行氟化，生成包含式(III)化合物的反应产物，其中X1如上所述，X2为氟；以及(c)将所述式(III)化合物暴露于有效的反应条件，将所述化合物转化为1,3,3,3-四氟丙烯。在另一个实施例中，该方法包括：(a)将氯与式(I) CH3CH=CH2化合物反应，生成包含式(II) CCI3CHC1CH2C1化合物的反应产物；(b)对式(II)化合物进行氟化，生成包含式(III) CF3CHC1CH2F化合物的反应产物；以及(c)将所述式(III)化合物暴露于有效的反应条件，将所述化合物转化为1,3,3,3-四氟丙烯。
• Chemical conversions using sheet silicates: novel intermolecular dehydrations of alcohols to ethers and polymers
  作者：James A. Ballantine、Mary Davies、Howard Purnell、Mongkon Rayanakorn、John M. Thomas、Kevin J. Williams

  DOI：10.1039/c39810000427

  日期：——

  Aliphatic primary alcohols, when intercalated in certain ion-exchanged montmorillonites, react preferentially via an intermolecular nucleophilic displacement of water to give high yields of di-(alk-1-yl) ethers, rather than the competitive intramolecular dehydration to alkenes; an essentially similar process yields polymeric material, poly(phenylenemethylene), from benzyl alcohol, but aliphatic secondary

  当插入某些离子交换的蒙脱石中时，脂肪族伯醇优先通过分子间亲核取代水反应以产生高产率的二-（烷基-1-基）醚，而不是竞争性的分子内脱水生成烯烃。基本上类似的方法由苯甲醇产生聚合材料，聚苯撑亚甲基，而脂族仲和叔醇则几乎仅产生烯烃。

表征谱图