匹贝卡 | 2522-81-8

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 匹贝卡
• 英文名称: 2-oxo-2-phenylethyl pivalate
• 英文别名: Pibecarb；phenacyl 2,2-dimethylpropanoate
• CAS: 2522-81-8
• 化学式: C₁₃H₁₆O₃
• mdl: MFCD00868933
• 分子量: 220.268
• InChiKey: OTIZTAXUFMCICV-UHFFFAOYSA-N

物化性质

• 熔点：
  62.5°C
• 沸点：
  321.2°C (rough estimate)
• 密度：
  1.1101 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.384
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2915900090

反应信息

• 作为反应物：
  描述：

  匹贝卡 在 Eaton’s reagent 、 palladium 10% on activated carbon 、 水 、 氢气 、 sodium methylate 、 magnesium 、 potassium hydroxide 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 生成 4-(3,4-二氯苯基)-1-四氢萘酮
  参考文献：
  名称：

  α,α-二芳基乙二醇作为合成 1,1-二芳基乙烯和 α,α-二芳基乙醛的重要前体

  摘要：

  为了组装生物学上重要的分子中存在的二芳基次甲基单元，我们开发了一种新的基于 Weinreb 酰胺 (WA) 的结构单元，该结构单元源自乙醇酸。该构件中存在的 WA 官能团允许以受控方式顺序添加各种芳基溴化镁试剂，从而能够组装二芳基次甲基单元。开发的合成路线可以轻松获得重要的二芳基乙烯和 α,α-二芳基乙二醇。合成的α,α-二芳基乙二醇为合成重要的对称和不对称α,α-二芳基乙醛作为有价值的中间体铺平了道路。

  DOI：

  10.1002/ejoc.201700467
• 作为产物：
  描述：

  特戊酸氯甲酯 在 sodium iodide 、 lithium chloride 、 锌 作用下， 以 丙酮 为溶剂， 反应 4.58h， 生成 匹贝卡
  参考文献：
  名称：

  Preparation and reactivity of highly functionalized organometallics at the .alpha. position of oxygen or nitrogen

  摘要：

  Alpha-Halogenoalkyl carboxylates (FG-R1CH(X)(OCOR2); FG = COOR, CN, SR; X = I, Br) were readily prepared by the addition of an acid chloride or bromide (R2COX; X = Br or Cl) to an aldehyde (FG-RCHO) in the presence of a catalytic amount of ZnCl2. They insert efficiently zinc dust in THF-DMSO (X = Br, 8-10-degrees-C, 6-10 h) affording the corresponding zinc organometallics at the a position to oxygen FG-RCH(ZnBr)(OAc). After the addition of the THF-soluble copper salt CuCN.2LiCl, the corresponding copper reagents FG-RCH(Cu(CN)ZnBr)(OAc) are formed and reacted with various classes of electrophiles such as acid chlorides, aldehydes, enones, allylic and alkynyl halides, activated alkynes, nitro olefins and alkylidenemalonates providing polyfunctional molecules in excellent yields. Similarly, zinc organometallics at the a position to the nitrogen of cyclic imides were prepared by the zinc insertion to cyclic alpha-chloromethyl (or alpha-chloroethyl) imides. After their transmetalation to the corresponding copper organometallic ((R1CO)2NCH(R)(Cu(CN)ZnCl); R = Me or H), they were reacted with allylic and alkynyl halides and ethyl propiolate affording polyfunctional imides. The reaction of cyclic N-(chloromethyl)imides with aldehydes in the presence of chromium(II) chloride in THF furnishes protected amino alcohols in 36-95% yield.

  DOI：

  10.1021/jo00055a010

文献信息

• Cost-Benefit Analysis of a Haemophilus Influenzae Type B Meningitis Prevention Programme in The Philippines
  作者：M. Rhona Limcangco、Carol L. Armour、Eugene G. Salole、Susan J. Taylor

  DOI：10.2165/00019053-200119040-00006

  日期：——

  Background: Haemophilus influenzae type b (Hib) meningitis is associated with high mortality and serious sequelae in children under 5 years of age. Vaccines which can prevent this infection are available. Objective: To evaluate the costs and benefits of a 3-dose immunisation schedule in Manila, Philippines. Perspective: Government and societal perspectives. Design and participants: A cost-benefit analysis based on a birth cohort of 100 000 children. The state of health of the cohort with and without a Hib immunisation programme was modelled over a 5-year period. A survey of medical records of patients with Hib in Manila provided data on the extent and cost of sequelae following infection. Intervention: A 3-dose Hib vaccination programme given at ages 2, 3 and 4 months. Results: The model predicted that vaccinating children against Hib meningitis would prevent 553 cases per year in a birth cohort of 100 000, at a cost of 56 200 Philippine pesos (PHP) [$US1605; 1998 exchange rate] per case (base case assumptions of 90% vaccine efficacy rate, 95 per 100 000 Hib incidence rate, 85% vaccination coverage). Results from the cost-benefit analyses indicated that the saving to the government would be around PHP39 million ($US1.11 million), and the saving to society would be PHP255 million ($US7.28 million). Conclusion: There would be a positive economic benefit for the Philippine government and for the Filipino society if a Hib vaccination programme was introduced in Manila.

  背景：B 型流感嗜血杆菌（Hib）脑膜炎在 5 岁以下儿童中关联高死亡率和严重后遗症。存在可预防这种感染的疫苗。目标：在菲律宾马尼拉评估三剂接种计划的代价和收益。视角：政府和社会视角。设计和参与者：基于 100，000 名儿童的出生队列进行成本-效益分析。该队列的健康状况在有和没有 Hib 免疫计划的情况下模拟了 5 年的健康状况。一项针对马尼拉 Hib 感染患者的病历调查提供了关于感染后后遗症的严重程度和成本的数据。干预：在 2、3 和 4 个月龄时给予 3 剂 Hib 疫苗接种计划。结果：该模型预测，在 100，000 名出生队列中，预防儿童 Hib 脑膜炎每年将预防 553 例，每例成本为 56，200 菲律宾比索（PHP）[1998 年汇率下为 1，605 美元;基础假设为 90% 疫苗有效率，95/100，000 Hib 发病率，85% 疫苗接种率]。成本-效益分析的结果表明，政府的节约约为 3900 万 PHP（111 万美元），社会的节约约为 25500 万 PHP（728 万美元）。结论：如果在马尼拉引入 Hib 疫苗接种计划，菲律宾政府和菲律宾社会将获得正面的经济收益。
• A Convenient and Versatile Method for the Preparation of α-Hydroxymethyl Ketone Derivatives from the Corresponding Allyl Silyl Ethers or Allyl Carboxylates
  作者：Yung-Son Hon、Ying-Chieh Wong、Kuo-Jui Wu

  DOI：10.1002/jccs.200800134

  日期：2008.8

  The ozonolysis of 1-substituted allyl silyl ethers or 1-substituted allyl carboxylates followed by treatment with bases gave the corresponding α-silyloxymethyl- or a-acyloxymethyl-ketones in good yields. It is proposed to proceed via the corresponding α-silyloxy- or α-acyloxyaldehydes intermediates followed by 1,4-group migration. The results of theoretical calculations are applicable to explain the

  1-取代的烯丙基甲硅烷基醚或1-取代的烯丙基羧酸盐随后用碱处理得到相应的α-甲硅烷氧基甲基-或α-酰氧基甲基-酮，产率良好。建议通过相应的 α-甲硅烷氧基或 α-酰氧基醛中间体进行，然后进行 1,4-基团迁移。理论计算结果适用于解释实验结果。
• Palladium-Catalyzed Chemo- and Enantioselective C−O Bond Cleavage of α-Acyloxy Ketones by Hydrogenolysis
  作者：Jianzhong Chen、Zhenfeng Zhang、Delong Liu、Wanbin Zhang

  DOI：10.1002/anie.201603590

  日期：2016.7.11

  A chemoselective C−O bond cleavage of the ester alkyl side‐chain of α‐acyloxy ketones was realized for the first time by a highly efficient palladium‐catalyzed hydrogenolysis (S/C=6000, the highest catalytic efficiency by far). Furthermore, a kinetic resolution of α‐acyloxy ketones was first developed by enantioselective hydrogenolysis with good yields and up to 99 % ee.

  通过高效钯催化的氢解反应（S / C = 6000，迄今为止最高的催化效率），首次实现了α-酰氧基酮的酯烷基侧链的化学选择性C-O键断裂。此外，首先通过对映选择性氢解反应开发了α-酰氧基酮的动力学拆分方法，该方法具有良好的收率和高达99％ee的收率。
• Synergistic Interplay of a Non-Heme Iron Catalyst and Amino Acid Coligands in H₂O₂Activation for Asymmetric Epoxidation of α-Alkyl-Substituted Styrenes
  作者：Olaf Cussó、Xavi Ribas、Julio Lloret-Fillol、Miquel Costas

  DOI：10.1002/anie.201410557

  日期：2015.2.23

  Highly enantioselective epoxidation of α‐substituted styrenes with aqueous H2O2 is described by using a chiral iron complex as the catalyst and N‐protected amino acids (AAs) as coligands. The amino acids synergistically cooperate with the iron center in promoting an efficient activation of H2O2 to catalyze epoxidation of this challenging class of substrates with good yields and stereoselectivities

  通过使用手性铁络合物作为催化剂，使用N-保护的氨基酸（AAs）作为大分子配体，描述了使用水为H 2 O 2的α-取代的苯乙烯的高度对映选择性环氧化。氨基酸与铁中心协同作用，以促进H 2 O 2的有效活化，从而在较短的反应时间内以良好的收率和立体选择性（高达97％ee）催化这种具有挑战性的底物的环氧化 。
• Synthetic applications of the amine-base treatment in the ozonolysis of substituted-allyl silyl ethers or -allyl esters via a novel ene–diol type rearrangement
  作者：Yung-Son Hon、Ying-Chieh Wong

  DOI：10.1016/j.tetlet.2004.12.135

  日期：2005.2

  The ozonolysis of substituted-allyl silyl ethers or -allyl esters followed by treatment with bases gave the corresponding α-silyloxy ketones or α-acyloxy ketones in good yields. The reaction is proposed to proceed via a novel ene–diol rearrangement of the corresponding α-silyloxy aldehydes or α-acyloxy aldehydes intermediates.

  取代的烯丙基甲硅烷基醚或烯丙基酯的臭氧分解，然后用碱处理，以良好的收率得到相应的α-甲硅烷氧基酮或α-酰氧基酮。该反应被建议通过相应的α-甲硅烷氧基醛或α-酰氧基醛中间体的新型烯-二醇重排进行。