3-环氧乙烷基7-氧杂二环[4.1.0]庚烷的均聚物 | 106-87-6

• 物质功能分类: 化学试剂 - 有机试剂 - 双环化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 中文名称: 3-环氧乙烷基7-氧杂二环[4.1.0]庚烷的均聚物
• 中文别名: 4-乙烯基-1-环己烯二环氧化物,异构体混合物；1-乙烯氧基-3,4-环氧环己烷；3-环氧乙基-7-氧杂二环[4,1,0]庚烷；二氧化乙烯基环己烯；3-环氧乙烷基7-氧杂二环[4.1.0]庚烷；4-乙烯基-1-环己烯二环氧化物；乙烯基环己烯-二环氧化物
• 英文名称: 4-vinylcyclohexene dioxide
• 英文别名: 4-vinylcyclohexene diepoxide；4-Vinyl-1-cyclohexene diepoxide；VCD；3-epoxyethyl-7-oxabicyclo[4.1.0]heptane；3-(oxiran-2-yl)-7-oxabicyclo[4.1.0]heptane
• CAS: 106-87-6；25086-25-3
• 化学式: C₈H₁₂O₂
• mdl: MFCD00022354
• 分子量: 140.182
• InChiKey: OECTYKWYRCHAKR-UHFFFAOYSA-N

物化性质

• 熔点：
  -55°C
• 沸点：
  230-232 °C(lit.)
• 密度：
  1.094 g/mL at 25 °C(lit.)
• 闪点：
  225 °F
• 物理描述：
  1-vinyl-3-cyclohexene dioxide is a clear colorless liquid. Sets to glass at -67°F. Faint olefinic odor. (NTP, 1992)
• 颜色/状态：
  COLORLESS LIQUID
• 溶解度：
  Solubility in water, g/100ml at 20 °C: 18.3
• 蒸汽密度：
  4.07 (NTP, 1992) (Relative to Air)
• 蒸汽压力：
  LESS THAN 0.1 MM HG @ 20 °C
• 稳定性/保质期：
  SLOWLY HYDROLYZED IN WATER
• 自燃温度：
  393 °C
• 粘度：
  7.77 CP @ 20 °C
• 折光率：
  INDEX OF REFRACTION: 1.4787 @ 20 °C

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.1
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

代谢

体外研究中，使用兔肝微粒体制备物进行的研究表明，4-乙烯基-1-环己烯二环氧可以代谢为单环氧单醇、1,2-羟基-4-乙烯基环己烷氧化物和4-(1',2'-二羟基乙基)-1-环己烷氧化物。这些产物的形成是由环氧水解酶催化的。与谷胱甘肽的结合是4-乙烯基-1-环己烯代谢的另一条途径。有报道称，给予小鼠500毫克/千克4-乙烯基-1-环己烯二环氧的腹腔注射后，小鼠肝脏中的还原型谷胱甘肽含量降低。

In vitro studies with rabbit liver microsomal preparations showed that 4-vinyl-1-cyclohexene diepoxide can be metabolized to monoepoxymonoglycols, 1,2-hydroxy-4-vinylcyclohexane oxide, and 4-(1',2'-dihydroxyethyl)-1-cyclohexane oxide. Formation of these products is catalyzed by epoxide hydrolase. Conjugation with glutathione is another pathway for metabolism of 4-vinyl-1- cyclohexene. Depletion of reduced glutathione /was reported/ in the liver of mice given ip injections of 500 mg/kg 4-vinyl-1-cyclohexene diepoxide.

来源:Hazardous Substances Data Bank (HSDB)

代谢

致癌性研究表明，长期给予4-乙烯基环己烯会在B6C3F1小鼠中诱导卵巢肿瘤，但在F-344大鼠中不会。这是因为4-乙烯基环己烯的有毒代谢物，4-乙烯基环己烯-1,2-环氧化物，在给予4-乙烯基环己烯处理的小鼠中的血液水平显著高于大鼠。这种种间差异在4-乙烯基环己烯的环氧化速率中也有所体现，由肝微粒体（雌性小鼠高于雌性大鼠）代谢4-乙烯基环己烯的速率。本研究评估了从人肝中获得的微粒体将4-乙烯基环己烯代谢为环氧化物的能力，因为人类在某些职业环境中会暴露于4-乙烯基环己烯。人肝微粒体从4-乙烯基环己烯（1 mM）产生4-乙烯基环己烯-1,2-环氧化物和4-乙烯基环己烯-7,8-环氧化物对于微粒体蛋白浓度（0.25-1.0 mg/ml）和孵化时间（5-20分钟）呈线性关系。4-乙烯基环己烯-1,2-环氧化物是主要的代谢物，而4-乙烯基环己烯-7,8-环氧化物的形成速率大约低6倍，在某些情况下低于检测限。从男性和女性人体中获得的肝微粒体在4-乙烯基环己烯环氧化速率方面没有显著差异。女性人肝微粒体形成4-乙烯基环己烯-1,2-环氧化物的速率为0.71 + 或 - 0.35 nmol/mg微粒体蛋白/分钟（n = 4）。这比雌性小鼠和雌性大鼠肝微粒体形成4-乙烯基环己烯-1,2-环氧化物的速率分别低13倍和2倍。

Carcinogenicity studies have shown that chronic administration of 4-vinylcyclohexene will induce ovarian tumors in B6C3F1 mice but not F-344 rats. This occurs because the blood level of the ovotoxic 4-vinylcyclohexene metabolite, 4-vinylcyclohexene-1,2-epoxide, is dramatically higher in 4-vinylcyclohexene treated female mice compared with rats. This species difference in 4-vinylcyclohexene epoxidation is also reflected in the rate of 4-vinylcyclohexene metabolism by hepatic microsomes (female mouse greater than female rat). The present study assessed the ability of microsomes obtained from human liver to metabolize 4-vinylcyclohexene to epoxides since humans are exposed to 4-vinylcyclohexene in certain occupational settings. The production of 4-vinylcyclohexene-1,2-epoxide and 4-vinylcyclohexene-7,8-epoxide from 4-vinylcyclohexene (1 mM) by human hepatic microsomes was linear with respect to microsomal protein concentration (0.25-1.0 mg/ml) and incubation time (5-20 min). 4-Vinylcyclohexene-1,2-epoxide was the major metabolite, while the rate 4-vinylcyclohexene-7,8-epoxide formation was about 6 fold lower and in some cases was below the limit of detection. There was no dramatic difference in the rate of 4-vinylcyclohexene epoxidation by hepatic microsomes obtained from male and female humans. The rate of 4-vinylcyclohexene-1,2-epoxide formation by female human hepatic microsomes was 0.71 + or - 0.35 nmol/mg microsomal protein/min (n = 4). This is 13 and 2 fold lower than the rate of 4-vinylcyclohexene-1,2-epoxide formation by female mouse and rat hepatic microsomes, respectively.

来源:Hazardous Substances Data Bank (HSDB)

代谢

4-乙烯基环己烯是橡胶工业中人类暴露的一种化学物质。美国国家毒理学计划（NTP）进行的慢性致癌性生物测试显示，口服4-乙烯基环己烯会在小鼠的卵巢中诱导肿瘤，但在大鼠的卵巢中则不会。测试的假设是，4-乙烯基环己烯毒性的物种和器官特异性是由于雌性大鼠和小鼠之间4-乙烯基环己烯处置的差异。因此，研究了雌性B6C3F1小鼠和Fischer 344大鼠口服单剂400 mg/kg (14)C 4-乙烯基环己烯的处置情况。小鼠在24小时内排除了超过95%的剂量，而大鼠需要48小时才能排除超过95%的剂量。放射性(14)C 4-乙烯基环己烯的主要排泄途径是在尿液中（50-60%）和呼出气体中（30-40%）。没有证据表明两个物种的卵巢保留了4-乙烯基环己烯作为母化合物或作为放射性等价物。在大鼠和小鼠之间，4-乙烯基环己烯给药（800 mg/kg，ip）后0.5至6小时内血液中出现的一种单环氧化物的差异非常显著。4-乙烯基环己烯-1,2-环氧化物在小鼠血液中的含量最高，在2小时时为41 nmol/ml。在大鼠中，4-乙烯基环己烯-1,2-环氧化物的血液浓度在所有检测时间点都小于2.5 nmol/ml。4-乙烯基环己烯-7,8-环氧化物在两个物种的血液中均未达到检测水平。这些发现得到了肝脏微粒体对4-乙烯基环己烯环氧化作用的体外研究的支持。4-乙烯基环己烯（1 mM）环氧化为4-乙烯基环己烯-1,2-环氧化物的速率在小鼠肝脏微粒体中比大鼠肝脏微粒体高6.5倍。肝脏形成环氧化物的速率的物种差异可能是物种对4-乙烯基环己烯诱导卵巢肿瘤易感性差异的一个重要因素。

4-Vinylcyclohexene is a chemical to which humans are exposed in the rubber industry. A chronic carcinogenicity bioassay conducted by the NTP showed that oral administration of 4-vinylcyclohexene induced tumors in the ovaries of mice but not in those of rats. The hypothesis tested was that the species and organ specificity of 4-vinylcyclohexene toxicity was due to differences in the disposition of 4-vinylcyclohexene between the female rat and mouse. Therefore, the disposition of a single oral dose of 400 mg/kg (14)C 4-vinylcyclohexene was studied in female B6C3F1 mice and Fischer 344 rats. Mice eliminated greater than 95% of the dose in 24 hr, whereas rats required 48 hr to eliminate greater than 95% of the dose. The major routes of excretion of (14)C 4-vinylcyclohexene derived radioactivity were in the urine (50-60%) and expired air (30-40%). No evidence was obtained to indicate that the ovaries of either species retained 4-vinylcyclohexene as a parent cmpd or as radioactive equivalents. A dramatic difference was observed between the rat and mouse in the appearance of a monoepoxide of 4-vinylcyclohexene in blood from 0.5 to 6 hr after 4-vinylcyclohexene administration (800 mg/kg, ip). 4-Vinylcyclohexene-1,2-epoxide was present in the blood of mice with the highest concentration at 2 hr (41 nmol/ml). The blood concentration of 4-vinylcyclohexene-1,2-epoxide in rats was less than 2.5 nmol/ml at all times examined. 4-Vinylcyclohexene-7,8-epoxide was not present in the blood of either species at the level of detection. These findings were supported by in vitro studies of 4-vinylcyclohexene epoxidation by liver microsomes. The rate of epoxidation of 4-vinylcyclohexene (1 mM) to 4-vinylcyclohexene-1,2-epoxide was 6.5 fold greater in mouse liver microsomes than that in rat liver microsomes. The species difference in the rate of epoxide formation by the liver may be an important factor in the species difference in susceptibility to 4-vinylcyclohexene induced ovarian tumors.

来源:Hazardous Substances Data Bank (HSDB)

代谢

VCH-环氧是一种已知的人体代谢物，来源于环氧-4-乙烯基环己烯和1,2-环氧-4-乙烯基环己烷。

VCH-diepoxide is a known human metabolite of Epoxy-4-vinylcyclohexene and 1,2-Epoxy-4-vinylcyclohexane.

来源:NORMAN Suspect List Exchange

毒理性

• 致癌性证据

评估：对于4-乙烯基环己烯二环氧化的致癌性，人类中的证据不足。在实验动物中，对于4-乙烯基环己烯二环氧化的致癌性有足够的证据。总体评估：4-乙烯基环己烯二环氧化可能对人类具有致癌性（2B组）。

Evaluation: There is inadequate evidence in humans for the carcinogenicity of 4-vinylcyclohexene diepoxide. There is sufficient evidence in experimental animals for the carcinogenicity of 4-vinylcyclohexene diepoxide. Overall evaluation: 4-Vinylcyclohexene diepoxide is possibly carcinogenic to humans (Group 2B).

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)

毒理性

• 致癌性证据

4-乙烯基-1-环己烯二环氧物：合理预期为人类致癌物。

4-Vinyl-1-cyclohexene Diepoxide: reasonably anticipated to be 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：4-乙烯基环己烯二环氧物

IARC Carcinogenic Agent:4-Vinylcyclohexene diepoxide

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：2B组：可能对人类致癌

IARC Carcinogenic Classes:Group 2B: Possibly carcinogenic to humans

来源:International Agency for Research on Cancer (IARC)

吸收、分配和排泄

4-乙烯基-1-环己烯二环氧物可以通过皮肤、口服或吸入的方式被啮齿类动物吸收。... 大鼠和小鼠分别接受了0.1毫升和0.01毫升的剂量混合物，其中含有500毫克/毫升（200单位/毫升）的[乙基-(14)C] 4-乙烯基-1-环己烯二环氧物丙酮溶液。初步结果显示，在大鼠和小鼠的皮肤上施用的剂量中，有30%在24小时内被吸收；在施用部位只有1%-3%的剂量残留在皮肤上。到24小时时，吸收剂量的70%-80%已经从体内排出，几乎全部通过尿液排出。体内的放射性物质分布在内多个组织中，但没有一个组织含有超过1%的施用剂量。然而，在大鼠的组织中，肝脏、肌肉和脂肪组织分别含有0.5%-1.6%的吸收剂量，在小鼠的组织中则含有1.2%-2.9%的吸收剂量。在大鼠中，组织与血液的比例从0.3到1.5不等，在小鼠中从0.8到2.8不等。

4-Vinyl-1-cyclohexene diepoxide is absorbed by rodents exposed dermally orally, or by inhalation. ... Rats and mice received 0.1 ml and 0.01 ml, respectively, of dose mixtures containing 500 mg/ml (200 uc/ml) [ethylene-(14)C] 4-vinyl-1-cyclohexene diepoxide in acetone. The preliminary results indicate that 30% of the dose applied to the skin is absorbed over a 24 hr period for both rats and mice; only 1%-3% of the dose remained on the skin at the site of application. By 24 hr, 70%-80% of the absorbed dose had been eliminated from the body, virtually all in the urine. The radioactivity remaining in the body was distributed over a number of tissues, with no tissue containing more than 1% of the applied dose. The liver, muscle, and adipose tissue, however, contained 0.5%-1.6% and 1.2%-2.9% of the absorbed dose in rat and mouse tissue, respectively. Tissue to blood ratios ranged from 0.3 to 1.5 in rats and from 0.8 to 2.8 in mice.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 职业暴露等级：
  A
• 职业暴露限值：
  TWA: 10 ppm (60 mg/m3) [skin]
• 危险等级：
  6.1(b)
• 危险品标志：
  T
• 安全说明：
  S23,S24,S45
• 危险类别码：
  R23/24/25
• WGK Germany：
  1
• 危险品运输编号：
  UN 2810 6.1/PG 3
• RTECS号：
  RN8640000
• 海关编码：
  2932999099
• 包装等级：
  III
• 危险类别：
  6.1(b)
• 危险性防范说明：
  P261,P280,P301+P310,P311
• 危险性描述：
  H301,H311,H331,H351

制备方法与用途

乙烯基环己烯二氧化物（VCD）作为一种卵巢毒素，可用于研究其毒性机制。具体来说，它被用于探讨VCD对卵巢滤泡及上皮细胞分化的影响。

类别 有毒物质

毒性分级 中毒

急性毒性

• 口服：大鼠 LD50 为 2130 毫克/公斤
• 吸入：大鼠 LC50 为 800 ppm（4 小时）

刺激数据

• 皮肤接触：兔，500 毫克，重度刺激

爆炸物危险特性 聚合放热；密闭容器中可能发生爆炸

可燃性危险特性 易燃；燃烧时释放出刺激性烟雾

储运特性 低温库房储存、通风、干燥环境

灭火剂 水、二氧化碳、泡沫、干粉

职业标准 时间加权平均容许浓度（TWA）：60 毫克/立方米 短时间暴露极限值（STEL）：90 毫克/立方米

反应信息

• 作为反应物：
  描述：

  3-环氧乙烷基7-氧杂二环[4.1.0]庚烷的均聚物 在 硫酸 作用下， 以 水 、 丙酮 为溶剂， 生成 4-(1,2-dihydroxyethyl)cyclohexane-1,2-diol
  参考文献：
  名称：

  Phosphorus compound

  摘要：

  本发明的含磷化合物由以下式(I)、(II)或(III)表示：其中Z1、Z2和Z3分别表示可能具有取代基团的环烷烃、环烯烃、多环脂肪烃或芳香烃环；R表示卤素原子、羟基、羧基、卤代羧基（卤甲酰基）、烷基、烷氧基、烯基或芳基；A表示对应于烷烃的多价基团；Y1、Y2和Y3分别表示—O—、—S—或—NR1—，其中R1表示氢原子或烷基；k为0至6的整数；m为0至2的整数；n为不少于1的整数；q为0至5的整数；r为0或1；S为1至4的整数。这种含磷化合物具有优异的耐热性，可用作阻燃剂、增塑剂或稳定剂。

  公开号：

  US20030109736A1
• 作为产物：
  描述：

  4-乙烯基-1-环己烯 在 硫酰氟 、 双氧水 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 1.0h， 以81%的产率得到3-环氧乙烷基7-氧杂二环[4.1.0]庚烷的均聚物
  参考文献：
  名称：

  SO 2 F 2介导的烯烃与过氧化氢的环氧化。

  摘要：

  已开发出一种廉价，温和且高效的环氧化方案，包括在室温下将SO2F2气体鼓泡到烯烃，30％过氧化氢水溶液和4 N碳酸钾水溶液在1,4-二恶烷中的溶液中1h相应的环氧化物的收率好至极好。新型的SO2F2 / H2O2 / K2CO3环氧化系统适用于各种烯属底物，包括富电子和电子不足的底物。

  DOI：

  10.1021/acs.joc.9b01784

文献信息

• Designing the synthesis of catalytically active Ti-β by using various new templates in the presence of fluoride anion
  作者：Manickam Sasidharan、Asim Bhaumik

  DOI：10.1039/c1cp21013k

  日期：——

  Crystallization of large-pore Ti-β by using a variety of diquaternary ammonium derivatives of dibromoalkane and amines such as triethylamine, 1,4-diazabicyclo[2,2,2]octane (DABCO), and quinuclidine as structure-directing agents (SDA) is described. The size of hydrophobic bridging alkyl-chain length of the template [R3N+–(CH2)x–N+R3](OH−)2 directs the final crystalline product: Ti-β, Ti-ZSM-12, Ti-nonasil or Ti-ZSM-5, as x gradually changes from 6 to 1, in the fluoride medium under hydrothermal conditions. A dense phase such as Ti-nonasil (clathrasil type) is crystallized as the size of hydrophobic bridging alkyl-chain length decreases. The use of F− anions as a mineralizer and Ti4+ as a heteroatom in the synthesis gel also influences the selectivity of final crystalline product. The phase purity and incorporation of Ti4+ into the lattice of β (BEA) and ZSM-12 frameworks are confirmed using XRD, UV-visible, FT-IR, 29Si NMR spectroscopes, elemental analysis (ICP), surface area measurements and catalytic test reactions. The morphology of Ti-β samples is dependent on the nature of the structure-directing agent as revealed by the scanning electron microscopic (SEM) observations. The catalytic activity in the epoxidation of 4-vinyl-1-cyclohexene is increased with the amount of tetrahedral Ti4+ atoms in the framework. The new templates can be effectively used for preparation of catalytically active Ti-β with the minimum number of framework defect sites.

  使用多种二溴烷烃和胺类（如三乙胺、1,4-二氮杂双环[2,2,2]辛烷（DABCO）及奎宁环）的双四级铵衍生物作为结构导向剂（SDA），可以在氟化物介质中通过水热条件下的晶化过程，合成大孔Ti-β。模板中的疏水性桥连烷基链的长度[R₃N⁺–(CH₂)ₓ–N⁺R₃](OH⁻)₂决定了最终晶体的种类：随x从6逐渐变为1，依次形成Ti-β、Ti-ZSM-12、Ti-nonasil或Ti-ZSM-5。随着疏水性桥连烷基链长度的减小，结晶出了如Ti-nonasil（笼型）的致密相。在合成凝胶中，使用F⁻作为矿化剂和Ti⁴⁺作为杂原子也会影响最终晶体的选择性。通过XRD、UV-可见光、FT-IR、²⁹Si NMR光谱、元素分析（ICP）、比表面积测量及催化测试反应，确认了相纯度和Ti⁴⁺在β（BEA）及ZSM-12框架中的掺入。扫描电子显微镜（SEM）观察显示，Ti-β样品的形貌取决于结构导向剂的性质。在4-乙烯基-1-环己烯的环氧化反应中，随着框架中四面体Ti⁴⁺原子数量的增加，催化活性也增强。新的模板能有效用于制备具有最低框架缺陷位的催化活性Ti-β。
• AROMATIC AMINE COMPOUND, CURING AGENT FOR EPOXY COMPOUND, CURABLE COMPOSITION, CURED PRODUCT, METHOD FOR PRODUCING CURED PRODUCT, AND METHOD FOR PRODUCING AROMATIC AMINE COMPOUND
  申请人：TOKYO OHKA KOGYO CO., LTD.

  公开号：US20210130284A1

  公开（公告）日：2021-05-06

  An aromatic amine compound capable of satisfactorily forming a cured product having exceptional alkali resistance by reaction with an epoxy compound; a curing agent for an epoxy compound, the curing agent including the aromatic amine compound; a curable composition including the curing agent for an epoxy compound; a cured product of the curable composition; a method for producing the cured product; and a method for producing the abovementioned aromatic amine compound. The aromatic amine compound has a structure such that a specific position in a central skeleton comprising a fused ring such as a fluorene ring is substituted with a side-chain group including two aromatic groups linked by a flexible bond such as an amide bond, at least one amino group is bonded to the end of the side-chain group, and the structure has no hydroxyl groups.

  一种芳香胺化合物，通过与环氧化合物反应能够满意地形成具有异常碱性抗性的固化产品；一种环氧化合物的固化剂，该固化剂包括芳香胺化合物；一种包括环氧化合物的固化剂的可固化组合物；可固化组合物的固化产品；生产所述固化产品的方法；以及生产上述芳香胺化合物的方法。该芳香胺化合物具有这样的结构，即中心骨架中的特定位置包括类似于芴环的融合环，该位置被取代为包括通过柔性键（如酰胺键）连接的两个芳香基的侧链基团，至少一个氨基固定在侧链基团的末端，并且该结构不含羟基。
• [EN] PROCESS FOR THE MANUFACTURING OF A POLYMER WITH URETHANE GROUPS<br/>[FR] PROCÉDÉ DE FABRICATION D'UN POLYMÈRE AYANT DES GROUPES URÉTHANNE
  申请人：BASF SE

  公开号：WO2019034473A1

  公开（公告）日：2019-02-21

  Process for the manufacturing of a polymer with urethane groups, wherein in a first alternative a compound A) with at least two five-membered cyclic monothiocarbonate groups and a compound B) with at least two amino groups, selected from primary or secondary amino groups and optionally a compound C) with at least one functional group that reacts with a group -SH are reacted or wherein in a second alternative a compound A) with at least two five-membered cyclic monothiocarbonate groups or a mixture of a compound A) with a compound A1)with one five-membered cyclic monothiocarbonate group and a compound B) with at least two amino groups, selected from primary or secondary amino groups or a compound B1) with one amino group selected from primary or secondary amino groups or mixtures of compounds B) and B1) and a compound C) with at least two functional groups that react with a group -SH or in case of a carbon-carbon triple bond as functional group that react with a group -SH, a compound C) with at least one carbon-carbon triple bond. are reacted.

  制造含有尿烷基团的聚合物的过程，其中，在第一种替代方案中，至少具有两个五元环状单硫代碳酸酯基团的化合物A)与至少具有两个氨基的化合物B)反应，这些氨基选自伯氨基或仲氨基，以及可选的至少含有一个与-SH基团反应的功能性基团的化合物C)；或者在第二种替代方案中，至少具有两个五元环状单硫代碳酸酯基团的化合物A)或化合物A)与具有一个五元环状单硫代碳酸酯基团的化合物A1)的混合物与至少具有两个氨基的化合物B)反应，这些氨基选自伯氨基或仲氨基，或具有一个氨基的化合物B1)，该氨基选自伯氨基或仲氨基，或化合物B)和B1)的混合物，以及至少具有两个与-SH基团反应的功能性基团的化合物C)，或当功能性基团为碳-碳三键时，至少具有一个碳-碳三键的化合物C)。
• Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
  申请人：Starnes Herbert William

  公开号：US20050049307A1

  公开（公告）日：2005-03-03

  Organic thiol compounds based on pentaerythritol and dipentaerythritol are described herein. More specifically, the compounds of the present invention are mixed esters of pentaerythritol and dipentaerythritol having at least one sulfhydryl group and preferably a plurality of sulfhydryl groups as well as at least one non-thiol-containing group. The organic thiol compounds are utilized to plasticize and/or heat stabilize halogen-containing polymer compositions especially poly(vinyl chloride) compositions. The compositions are substantially free or free of metal-based stabilizers, Lewis acids and terpenes. The compounds of the present invention are ideally utilized in polymers normally susceptible to deterioration and color change which can occur during processing of the polymer or exposure of the polymer to certain environments and surprisingly also serve as excellent plasticizers.

  本文描述了基于对羟基甲苯和二对羟基甲苯的有机硫醇化合物。更具体地说，本发明的化合物是对羟基甲苯和二对羟基甲苯的混合酯，具有至少一个巯基和最好是多个巯基，以及至少一个非巯基含有基团。这些有机硫醇化合物被用于增塑和/或热稳定含卤素聚合物组合物，特别是聚氯乙烯组合物。这些组合物基本上不含或不含金属基稳定剂、路易斯酸和萜类物质。本发明的化合物在通常容易恶化和变色的聚合物中得到理想应用，这种恶化和变色可能发生在聚合物加工过程中或聚合物暴露于某些环境中，并且令人惊讶地还可作为优秀的增塑剂。
• Covalent Heterogenization of a Discrete Mn(II) Bis-Phen Complex by a Metal-Template/Metal-Exchange Method:  An Epoxidation Catalyst with Enhanced Reactivity
  作者：Tracy J. Terry、T. Daniel P. Stack

  DOI：10.1021/ja0742030

  日期：2008.4.1

  along with the epoxidation reactivity once reloaded with manganese. Comparisons of this imprinted material with material synthesized by random grafting of the ligand show that the template method creates more reproducible, solution-like bis-1,10-phenanthroline coordination at a variety of ligand loadings. Olefin epoxidation with peracetic acid shows the imprinted manganese catalysts have improved product

  由于位点隔离可能带来的好处，例如增加催化剂稳定性、催化剂回收和产品分离，将分散的环氧化催化剂固定在固体载体上引起了相当大的关注。本文报道了一种合成金属模板/金属交换方法，可将共价连接的双-1,10-菲咯啉配位环境印记到高表面积介孔 SBA-15 二氧化硅上，并在重新加载锰后具有环氧化反应性。这种印迹材料与通过配体随机接枝合成的材料的比较表明，模板方法在各种配体负载下产生了更具重现性的、类似溶液的双 1,10-菲咯啉配位。烯烃与过乙酸的环氧化表明，印迹锰催化剂对环氧化物的产物选择性有所提高，底物范围更大，氧化剂的使用更有效，并且比其均相或接枝类似物具有更高的反应性，而不受配体负载的影响。然而，随机接枝的锰催化剂显示出随着配体负载而变化的反应性，而均相类似物降解三取代的烯烃并从顺式烯烃产生反式环氧化物产物。模板化催化剂的有效回收行为也是可能的。显示反应性随配体负载而变化，而均相类似物降解三取代

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