methyl acetoacetate dithioketal | 65726-45-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl acetoacetate dithioketal
• 英文别名: 1,3-Dithiolane-2-acetic acid, 2-methyl-, methyl ester；methyl 2-(2-methyl-1,3-dithiolan-2-yl)acetate
• CAS: 65726-45-6
• 化学式: C₇H₁₂O₂S₂
• 分子量: 192.303
• InChiKey: KIOUEQHNRVBGAQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl acetoacetate dithioketal 在 sodium hydroxide 、 硫酸 作用下， 以 四氯化碳 为溶剂， 反应 8.67h， 生成 (2-Methyl-1,3-dithiolan-2-yl)essigsaeure-propylester
  参考文献：
  名称：

  Stahl, Ingfried; Schramm, Berthold; Manske, Rainer, Liebigs Annalen der Chemie, 1982, # 6, p. 1158 - 1172

  摘要：

  DOI：
• 作为产物：
  描述：

  二氯甲烷 以49%的产率得到
  参考文献：
  名称：

  TANIMOTO, SHIGEO;OIDA, TATSUO;HATANAKA, KOUHEI;OKANO, MASAYA, BULL. INST. CHEM. RES. KYOTO UNIV., 1981, 59, N 5-6, 332-336

  摘要：

  DOI：

文献信息

• Solvent Free Thioacetalization of Carbonyl Compounds Catalyzed by Cu(OTf)₂-SiO₂
  作者：R. Vijaya Anand、P. Saravanan、Vinod K. Singh

  DOI：10.1055/s-1999-2635

  日期：1999.4

  Aldehydes and ketones were thioacetalyzed using 1,2-ethanedithiol in the presence of a catalytic amount of Cu(OTf)2-SiO2 under solvent free conditions in excellent yields.

  醛和酮在无溶剂条件下，使用1,2-乙二硫醇，在催化量的Cu(OTf)2-SiO2存在下，进行了硫代乙酰化反应，产率极佳。
• Rearrangement mechanisms of 1,3-dithiolane sulfoxides.
  作者：Wha Suk Lee、Koo Lee、Kee Dal Nam、Yang Joon Kim

  DOI：10.1016/s0040-4020(01)91005-1

  日期：1991.9

  sulfide 4 gave a mixture of cis and trans monosulfoxides 5 and 6 as major and minor products, respectively, plus a small amount of disulfoxides 7. The structural assignments of cis and trans sulfoxides 5 and 6 were based on 1H NMR spectroscopy and the regiospecific deuterations of the two isomers . Under neutral conditions cis sulfoxides 5 underwent a sigmatropic rearrangement with 2-methylene hydrogens

  硫化物4的氧化分别产生作为主要产物和次要产物的顺式和反式一亚砜5和6的混合物，以及少量的二亚砜7。顺式和反式亚砜5和6的结构分配基于1 H NMR光谱和两种异构体的区域特异性氘。在中性条件下，顺式亚砜5经过2-亚甲基氢的σ重排，生成亚磺酸18，然后环化成二氢-1,4-二硫辛2。反式亚砜6重排涉及2-甲基氢经由亚磺酸19形成异构体二氢二硫辛3。在亚砜的两种反应中，亚砜4和二硫化物11也作为次要副产物形成。在酸催化剂的存在顺式亚砜5制备2在定量的产率加上少量3，而反式亚砜6，得到2作为主要产物和3作为次要。形成的机制2，3，4和11进行了讨论。
• The Reaction of 2-Ethoxy-1,3-oxathiolane with Carbonyl Compounds in the Presence of ZnCl₂or HgCl₂
  作者：Shigeo Tanimoto、Shigeo Jo、Toyonari Sugimoto、Masaya Okano

  DOI：10.1246/bcsj.54.3237

  日期：1981.10

  In the reaction of 2-ethoxy-1,3-oxathiolane with carbonyl compounds in the presence of ZnCl2 or HgCl2, it has been found that only the breaking of the endocyclic bond (C–O or C–S bond) occurs, while the breaking of the exocyclic C–O bond to give the 1,3-oxathiolan-2-ium ion is unfavorable. This behavior is different from that of 2-ethoxy-1,3-dithiolane, in which the breaking of the endocyclic C–S bond

  在 ZnCl2 或 HgCl2 存在下，2-乙氧基-1,3-氧杂硫杂环戊烷与羰基化合物反应，发现仅发生内环键（C-O 或 C-S 键）断裂，而环外 C-O 键断裂产生 1,3-oxathiolan-2-ium 离子是不利的。这种行为不同于 2-乙氧基-1,3-二硫戊环，其中环内 C-S 键通过 HgCl2 和外环 C-O 键发生断裂，通过 ZnCl2。
• Highly Efficient Dithioacetalization of Carbonyl Compounds Catalyzed with Iodine Supported on Neutral Alumina
  作者：Nabajyoti Deka、Jadab C. Sarma

  DOI：10.1246/cl.2001.794

  日期：2001.8

  Aldehydes and ketones are protected as their corresponding dithioacetals with ethane-1,2-dithiol in the presence of a catalytic amount of iodine supported on neutral alumina surface. This is a high yielding method of carbonyl group protection under mild, neutral and solvent free conditions.

  醛和酮在中性铝土表面上以乙炔-1,2-二硫醇的对应二硫缩醛形式得到保护，反应中使用了少量的碘作为催化剂。这是一种在温和、中性和无溶剂条件下高产率的羰基保护方法。
• Selective Catalytic Transesterification, Transthiolesterification, and Protection of Carbonyl Compounds over Natural Kaolinitic Clay
  作者：Datta E. Ponde、Vishnu H. Deshpande、Vivek J. Bulbule、Arumugam Sudalai、Anil S.Gajare

  DOI：10.1021/jo971404l

  日期：1998.2.1

  Transesterification and transthiolesterification of beta-keto esters with variety of alcohols and thiols and selective protection of carbonyl functions with various protecting groups catalyzed by natural kaolinitic clay are described. The clay has been found to be an efficient catalyst in transesterifying long chain alcohols, unsaturated alcohols, and phenols to give their corresponding beta-keto esters in high yields. For the first time, transthiolesterification of beta-keto esters with a variety of thiols has been achieved under catalytic conditions. Clay also catalyzes selective transesterification of beta-keto esters by primary alcohols in the presence of secondary and tertiary alcohols giving corresponding beta-keto esters. A systematic study involving the reactivity of different nucleophiles (alcohols, amines, and thiols) toward beta-keto esters is also described. Sterically hindered carbonyl groups as well as alpha,beta-unsaturated carbonyl groups underwent protection without the deconjugation of the double bond. Chemoselective protection of aldehydes in the presence of ketones has also been achieved over natural kaolinitic clay.