(but-3-enyloxy)chloroacetic acid methyl ester | 135718-80-8

• 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: (but-3-enyloxy)chloroacetic acid methyl ester
• 英文别名: O-(but-3-enyl)-α-chloroglycolic acid methyl ester；methyl O-(3-butenyl)-α-chloroglycolate；Methyl 2-(3-buten-1-oxy)-2-chloroacetate；Methyl 2-but-3-enoxy-2-chloroacetate
• CAS: 135718-80-8
• 化学式: C₇H₁₁ClO₃
• 分子量: 178.616
• InChiKey: FNFNLNCGXTWBRH-UHFFFAOYSA-N

物化性质

• 沸点：
  232.2±30.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (but-3-enyloxy)chloroacetic acid methyl ester 在 copper(l) chloride 2,2'-联吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以84%的产率得到methyl 3-chloromethyl-2-tetrahydrofurancarboxylate
  参考文献：
  名称：

  铜催化甘氨酸和乙醇酸衍生物的氯转移环化

  摘要：

  在催化量的氯化亚铜和2,2'-联吡啶的存在下，氯甘氨酸和氯乙醇酸衍生物可在原子转移过程中平稳环化，分别生成官能化的脯氨酸酯和2-四氢呋喃羧酸酯。

  DOI：

  10.1016/0040-4039(91)80706-c
• 作为产物：
  描述：

  Methyl 2-(3-buten-1-oxy)-2-acetoxyacetate 在 盐酸 、 乙酰氯 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以100%的产率得到(but-3-enyloxy)chloroacetic acid methyl ester
  参考文献：
  名称：

  酶解拆分顺式-3-氯甲基-2-四氢呋喃甲酸甲酯

  摘要：

  通过酶催化水解在中性条件下的动力学拆分成功地应用于外消旋顺式-3-氯甲基-2-四氢呋喃甲酸甲酯（1）。用酰基转移酶-I（E = 51）和α-胰凝乳蛋白酶（E = 28）可获得最高的选择性。在两种情况下回收的光学活性甲酯均为（+）-（2 S，3 R）-1。在反应条件下，水解产物自发地环化成双环内酯（-）3a R，6a R）-9，其在一次重结晶后对映体纯。（-）- 9的X射线晶体结构分析 允许确定其绝对配置

  DOI：

  10.1016/s0957-4166(00)86087-5

文献信息

• Resolution of methyl cis-3-chloromethyl-2-tetrahydrofurancarboxylate via enzymatic hydrolysis
  作者：Jan H. Udding、Jan Fraanje、Kees Goubitz、Henk Hiemstra、W.Nico Speckamp、Bernard Kaptein、Hans E. Schoemaker、Johan Kamphuis

  DOI：10.1016/s0957-4166(00)86087-5

  日期：1993.3

  Kinetic resolution via enzyme catalyzed hydrolysis under neutral conditions was successfully applied to racemic methyl cis-3-chloromethyl-2-tetrahydrofurancarboxylate (1). The highest selectivities were attained with the enzymes acylase-I(E = 51) and α-chymotrypsin (E = 28). The optically active methyl ester recovered in both cases was (+)-(2S,3R)-1. The hydrolysis product spontaneously cyclized under

  通过酶催化水解在中性条件下的动力学拆分成功地应用于外消旋顺式-3-氯甲基-2-四氢呋喃甲酸甲酯（1）。用酰基转移酶-I（E = 51）和α-胰凝乳蛋白酶（E = 28）可获得最高的选择性。在两种情况下回收的光学活性甲酯均为（+）-（2 S，3 R）-1。在反应条件下，水解产物自发地环化成双环内酯（-）3a R，6a R）-9，其在一次重结晶后对映体纯。（-）- 9的X射线晶体结构分析 允许确定其绝对配置
• Xanthate Transfer Cyclization of Glycolic Acid-Derived Radicals. Synthesis of Five- to Eight-Membered Ring Ethers
  作者：Jan H. Udding、J. P. M. Giesselink、Henk Hiemstra、W. Nico Speckamp

  DOI：10.1021/jo00101a027

  日期：1994.11

  A novel method for the preparation of functionalized five- to eight-membered ring ethers is described. This method involves the xanthate transfer radical cyclization of 2-(alken-1-oxy)-2-[(ethoxythio-carbonyl)sulfanyl]acetic acid methyl esters 6 to give good yields of xanthate-substituted five- to eight-membered ethers 7 and/or 8, depending on the length of the carbon chain. These cyclic ethers are usually obtained as mixtures of diastereomers. The cyclizations are performed at 150-160 degrees C in tert-butylbenzene with di-tert-butyl peroxide as the initiator. This group-transfer radical cyclization was successfully applied in a total synthesis of lauthisan (44). The use of benzoyl xanthate (56) as a catalyst allows a visible light-induced xanthate transfer cyclization to a tetrahydrofuran in high yield.
• Udding, Jan H.; Hiemstra, Henk; Speckamp, W. Nico, Journal of the Chemical Society. Perkin transactions II, 1992, # 9, p. 1529 - 1530
  作者：Udding, Jan H.、Hiemstra, Henk、Speckamp, W. Nico

  DOI：——

  日期：——
• Transition Metal-Catalyzed, Chlorine-Transfer Radical Cyclizations of 2-(3-Alken-1-oxy)-2-Chloroacetates. Formal Total Synthesis of Avenaciolide and Isoavenaciolide
  作者：Jan H. Udding、Kees C. J. M. Tuijp、Marco N. A. van Zanden、Henk Hiemstra、W. Nico Speckamp

  DOI：10.1021/jo00087a011

  日期：1994.4

  A novel method for the synthesis of functionalized tetrahydrofurans is described. This method involves the treatment of 2-(3-alken-1-oxy)-2-chloroacetates 1 with a catalytic amount of Cu(bpy)Cl in refluxing 1,2-dichloroethane to give good yields of 3-(1-chloroalkyl)-2-tetrahydrofuran carboxylic esters 2. The stereochemical course of the radical cyclizations shows a-preference for the formation of 2,3-cis-substituted tetrahydrofurans in all cases. This selectivity is exploited in the formation of bicyclic lactones which form spontaneously upon ester hydrolysis. As an application of this methodology a formal total synthesis of avenaciolide (28) and isoavenaciolide (29) is described.
• Copper catalyzed chlorine transfer cyclizations of glycine and glycolic acid derivatives
  作者：Jan H. Udding、Henk Hiemstra、Marco N.A. van Zanden、W.Nico Speckamp

  DOI：10.1016/0040-4039(91)80706-c

  日期：1991.6

  Chloroglycine and chloroglycolic acid derivatives smoothly cyclize in the presence of a catalytic amount of cuprous chloride and 2,2′-bipyridine to produce functionalized proline and 2-tetrahydrofurancarboxylic esters, respectively, in an atom transfer process.

  在催化量的氯化亚铜和2,2'-联吡啶的存在下，氯甘氨酸和氯乙醇酸衍生物可在原子转移过程中平稳环化，分别生成官能化的脯氨酸酯和2-四氢呋喃羧酸酯。