(E)-1,4-diacetoxy-2-methyl-2-butene | 59054-99-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (E)-1,4-diacetoxy-2-methyl-2-butene
• 英文别名: 2-methyl-but-2-ene-1,4-diol diacetate；4-Acetoxy-2-methylbut-2-enyl acetate；(E)-1,4-diacetoxy-2-methylbut-2-ene；1,4-diacetoxy-2-methyl-2-butene；1,4-diacetoxy-2-methyl-but-2-ene；1,4-Diacetoxy-2-methyl-but-2-en；2-Methyl-2-butene-1,4-diyl diacetate；[(E)-4-acetyloxy-3-methylbut-2-enyl] acetate
• CAS: 59054-99-8
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: LJPNEMAMFITRSO-QPJJXVBHSA-N

物化性质

• 保留指数：
  1301

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-1,4-diacetoxy-2-methyl-2-butene 在 selenium(IV) oxide 、 乙酸酐 、 溶剂黄146 作用下， 生成 3,4-Diacetoxy-2-methylenbutanal
  参考文献：
  名称：

  Synthesis and stereochemistry of (E,E)-1,4-diacetoxy-2-methyl-1,3-butadiene and related compounds

  摘要：

  DOI：

  10.1021/jo00877a024
• 作为产物：
  描述：

  天然橡胶 生成 (E)-1,4-diacetoxy-2-methyl-2-butene
  参考文献：
  名称：

  Baltes,H. et al., Chemische Berichte, 1978, vol. 111, p. 1294 - 1314

  摘要：

  DOI：

文献信息

• Ubiquinone and related compounds. XXXI. Synthesis of urinary metabolites of ubiquinone, phylloquinone, .ALPHA.-tocopherol and their related compounds.
  作者：MASAZUMI WATANABE、KAYOKO OKAMOTO、ISUKE IMADA、HIROSHI MORIMOTO

  DOI：10.1248/cpb.26.774

  日期：——

  Metabolites (XVIIa, b, c) of ubiquinone, phylloquinone and α-tocopherol, and their 2', 3'-dihydro (XXa, b, c), dicarboxy (XVIa, b, XXIIIa, b, c, XXIVa, b and XXVa, b) and 3'-demethyl (XXIa, b) derivatives were synthesized. During the synthetic studies of these compounds, we found that cis-4-acetoxy-1-bromo-2-methyl-2-butene (cis-III) was more reactive to nucleophiles than the corresponding trans isomer. γ-Vinyl-γ-butyrolactone (XII), which was a useful starting material for the synthesis of XXIa, b, was synthesized in one step from 1, 3-butadiene. The 3'-methyl group of XVIIa, b was not essential for the membrane-stabilizing activity in the rat-liver lysosome. Introduction of a carboxyl but not a carboxyl ester group into XVIIa, b resulted in a loss of the stabilizing activity.

  合成了泛醌、叶醌和α-生育酚的代谢物（XVIIa, b, c）及其2', 3'-二氢（XXa, b, c）、二羧基（XVIa, b, XXIIIa, b, c, XXIVa, b 和 XXVa, b）和3'-去甲基（XXIa, b）衍生物。在这些化合物的合成研究过程中，我们发现顺-4-乙氧基-1-溴-2-甲基-2-丁烯（cis-III）对核苷酸反应性比相应的反异构体更强。γ-乙烯基-γ-丁内酯（XII）作为合成XXIa, b的有用起始材料，可以一步从1, 3-丁二烯合成。XVIIa, b的3'-甲基基团对大鼠肝脏溶酶体的膜稳定活性并不是必需的。将羧基引入XVIIa, b，而不是羧酸酯基团，会导致稳定活性的丧失。
• Diacetoxylation of conjugated dienes with thallium(III) acetate in acetic acid
  作者：Sakae Uemura、Haruo Miyoshi、Akira Tabata、Masaya Okano

  DOI：10.1016/s0040-4020(01)92012-5

  日期：1981.1

  The reaction of conjugated dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,5-dimethyl-2,4-hexadiene, 1,3-cyclopentadiene, and 1,3-cyclohexadiene, with thallium(III)acetate in acetic acid at 10–65° for 0.5–15 hr affords an isomeric mixture of the corresponding diacetoxyalkenes (1,2- and 1,4-addition products) in 10–92% yields. The 1,2-addition products are predominantly formed

  共轭二烯如1,3-丁二烯，异戊二烯，2,3-二甲基-1,3-丁二烯，2,5-二甲基-2,4-己二烯，1,3-环戊二烯和1,3-的反应环己二烯与乙酸th（III）在乙酸中于10–65°混合0.5–15小时，可以以10–92％的收率得到相应的二乙酰氧基烯烃（1,2-和1,4-加成产物）的异构体混合物。除1,3-环戊二烯外，在所有检查的情况下，主要形成1,2-加成产物。假定反应通过乙酰氧基化和脱盐步骤进行，后面的步骤伴随和/或随后是乙酰氧基的攻击。在线性末端二烯和环状二烯的情况下，proposed部分的初始进攻被认为主要发生在C-1和C-2碳原子上。
• Isoprenoid biosynthesis in Escherichia coli via the methylerythritol phosphate pathway: enzymatic conversion of methylerythritol cyclodiphosphate into a phosphorylated derivative of (E)-2-methylbut-2-ene-1,4-diol
  作者：Myriam Seemann、Narciso Campos、Manuel Rodriguez-Concepción、Ester Ibañez、Tore Duvold、Denis Tritsch、Albert Boronat、Michel Rohmer

  DOI：10.1016/s0040-4039(02)00003-5

  日期：2002.2

  tol 2,4-cyclodiphosphate (1) into a phosphorylated derivative of (E)-2-methylbut-2-ene-1,4-diol (6), which most probably represents a novel intermediate in the methylerythritol phosphate pathway for isoprenoid biosynthesis. The free diol 6 was accumulated by phosphatase treatment of the crude enzyme preparation and was identified by comparison with a synthetic reference.

  从A粗无细胞系统大肠埃希氏杆菌菌株过表达含有三个基因簇yfgA，yfgB和gcpE转换的2- Ç甲基d赤藓糖醇2,4-环（1）到的磷酸化衍生物（É） -2-甲基丁-2-烯-1,4-二醇（6），最有可能代表用于异戊二烯生物合成的甲基赤藓糖醇磷酸途径中的新型中间体。通过粗酶制剂的磷酸酶处理来积累游离二醇6，并通过与合成参考物进行比较来鉴定。
• Preparation of 3-alkyl-4-hydroxy-2-butenyl acetate through highly regioselective lipase-catalyzed hydrolysis of corresponding diacetates
  作者：Toshiyuki Itoh、Ayako Uzu、Naoki Kanda、Yumiko Takagi

  DOI：10.1016/0040-4039(95)02111-6

  日期：1996.1

  Highly regioselective hydrolysis of diacetate of (E)-2-substituted-2-butene-1,4-diol has been demonstrated. Lipase AL (Meito) was chosen from among commercial enzymes as the one most able to preferentially hydrolyze the acetyl group at 1-position giving monoacetate.

  已经证明了（E）-2-取代的-2-丁烯-1，4-二醇的二乙酸酯的高度区域选择性水解。脂酶AL（Meito）是从商业酶中选择的，是最能优先水解1位乙酰基以获得单乙酸酯的酶。
• Remarkable acceleration of a lipase-catalyzed reaction by a thiacrown ether additive: buffer-free highly regioselective partial hydrolysis of 4-acetoxy-2-methylbut-2-enyl acetate
  作者：Toshiyuki Itoh、Koichi Mitsukura、Kunihiro Kaihatsu、Hiroki Hamada、Yumiko Takagi、Hiroshi Tsukube

  DOI：10.1039/a702894f

  日期：——

  The reaction efficiency of the lipase-catalyzed partial hydrolysis of 4-acetoxy-2-methylbut-2-enyl acetate is greatly enhanced by the presence of 5 mol% of a thiacrown ether, particularly remarkable improvement being observed in CRL- and PCL-catalyzed reactions. 4-Hydroxy-2-methylbut-2-enyl acetate has thus been simply prepared by buffer-free lipase-catalyzed hydrolysis.

  脂肪酶催化部分反应效率 水解 4-乙酰氧基-2-甲基丁-2-烯基乙酸酯的存在大大增强了 5摩尔％硫杂冠醚的改善特别显着 在 CRL 和 PCL 催化反应中观察到。 因此，4-羟基-2-甲基丁-2-烯基乙酸酯可通过以下简单方法制备： 无缓冲液脂肪酶催化的水解。