butyl 4-chloroacetoacetate | 85525-26-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: butyl 4-chloroacetoacetate
• 英文别名: Butyl 4-chloro-3-oxobutanoate
• CAS: 85525-26-4
• 化学式: C₈H₁₃ClO₃
• 分子量: 192.642
• InChiKey: KARCVSXXFQZRRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  butyl 4-chloroacetoacetate 生成 (S)-4-Chloro-3-hydroxy-butyric acid butyl ester
  参考文献：
  名称：

  SIH C. J.; ZHOU BING-NAN; GOPALAN ARAVAMUDAN S.; SHIEH WOAN-RU; CHEN CHIN+, ANN. N. Y. ACAD. SCI., 434,(1986) 186-193

  摘要：

  DOI：

文献信息

• Control of Enantioselectivity in the Bakers' Yeast Reduction of β-Keto Ester Derivatives in the Presence of a Sulfur Compound
  作者：Ryuuichirou Hayakawa、Kazumi Nozawa、Makoto Shimizu、Tamotsu Fujisawa

  DOI：10.1016/s0040-4039(97)10490-7

  日期：1998.1

  Improvement of the enantioselectivity and enhancement of the reactivity were achieved in the bakers' yeast reduction of the β-keto ester derivatives by the addition of a sulfur compound. © 1997 Elsevier Science Ltd. All rights reserved.

  通过添加硫化合物，在面包师的酵母还原β-酮酯衍生物中，实现了对映选择性的提高和反应性的提高。©1997 Elsevier ScienceLtd。保留所有权利。
• The bakers' yeast reductions of α- and β-keto ester derivatives in the presence of a sulfur compound
  作者：Ryuuichirou Hayakawa、Kazumi Nozawa、Kimihiko Kimura、Makoto Shimizu

  DOI：10.1016/s0040-4020(99)00373-7

  日期：1999.6

  enhancement of the reactivity were achieved in the bakers' yeast reduction of the α- and β-keto ester derivatives by the addition of a sulfur compound. High enantioselectivity in the bakers' yeast reduction of keto esters was accomplished by using combination of an addition of a sulfur compound with an appropriate selection of the alcohol part of the ester.

  通过添加硫化合物，在面包师的酵母还原α-和β-酮酯衍生物中，实现了对映选择性的提高和反应性的提高。在面包酵母还原酮酯的对映体选择性高，通过使用加硫化合物与酯的醇部分的适当选择的组合来实现。
• T-butyl (R)-(-)-4-cyano-3-hydroxybutyrate and process for preparing the
  申请人：Takasago International Corporation

  公开号：US05430171A1

  公开（公告）日：1995-07-04

  T-butyl (R)-(-)-4-cyano-3-hydroxybutyrate having an optical purity of 99%ee or higher and a process for producing the same are disclosed, the process comprising cyanogenation of a t-butyl (S)-(-)-4-halogeno-3-hydroxybutyrate obtained by enantioselective hydrogenation of a t-butyl 4-halogenoacetoacetate. Recrystallization of the resulting crude product gives the optically active compound with high optical purity.

  本发明公开了具有99%ee或更高的光学纯度的T-叔丁基（R）-（-）-4-氰基-3-羟基丁酸酯，以及制备该化合物的方法，该方法包括通过对通过对T-叔丁基4-卤代乙酰乙酸酯进行对映选择性氢化得到的T-叔丁基（S）-（-）-4-卤代-3-羟基丁酸酯进行氰化反应。通过对得到的粗品进行重结晶可以得到具有高光学纯度的对映活性化合物。
• Process for preparing L-carnitine and chemical intermediates employed
  申请人：Sigma-Tau Industrie Pharmaceutiche Riunite S.p.A.

  公开号：US04710468A1

  公开（公告）日：1987-12-01

  A process for preparing L-carnitine which comprises exposing .gamma.-substituted acetoacetic acid esters or amides to the fermentative enzymatic action of a microorganism which elaborates L-.beta.-hydroxyacyl CoA dehydrogenase [EC 1.1.1.35] , recovering the resulting, optically active corresponding .gamma.-substituted-.beta.-hydroxybutyric acid derivative and converting said derivative to L-carnitine. An improvement in the process is also disclosed which comprises reacting a 4-chloro-3(R)-hydroxybutyrate with sodium iodide or bromide to produce the corresponding 4-iodo- or 4-bromo-3(R)-hydroxybutyrate, converting the 4-iodo- or 4-bromo-3(R)-hydroxybutyrate to the trimethylamino-3(R)-hydroxybutyrate salt, then converting the trimethylamino-3(R)-hydroxybutyrate salt into L-carnitine. Novel chemical intermediates prepared in the processes are also disclosed.

  一种制备L-肉碱的方法，包括将.gamma.-取代乙酰乙酸酯或酰胺暴露于微生物的发酵酶作用下，该微生物制造L-.beta.-羟基酰基辅酶A脱氢酶[EC 1.1.1.35]，回收所得的光学活性对应的.gamma.-取代-.beta.-羟基丁酸衍生物，并将该衍生物转化为L-肉碱。还公开了一种改进方法，包括将4-氯-3(R)-羟基丁酸与碘化钠或溴化钠反应，以产生相应的4-碘或4-溴-3(R)-羟基丁酸盐，将4-碘或4-溴-3(R)-羟基丁酸盐转化为三甲基氨基-3(R)-羟基丁酸盐，然后将三甲基氨基-3(R)-羟基丁酸盐转化为L-肉碱。还公开了在该过程中制备的新型化学中间体。
• Process for preparing carnitine
  申请人：Takasago International Corporation

  公开号：EP0339764A1

  公开（公告）日：1989-11-02

  A process for preparing carnitine comprising asymmetrically hydrogenating a γ-halogeno-β-­keto ester represented by formula (I): wherein X represents a chlorine atom or a bromine atom; and R represents a lower alkyl group, in the presence of a ruthenium-optically active phosphine complex represented by formula (II), (III) or (IV): Ru₂Cl₄(L)₂(C₂H₅)₃N      (II) Ru(OCOR²)₂(L)      (IV) RuX₂(L)      (V) wherein L represents 2,2′-bis(di-p-R¹-phenylphosphino)-­1,1′-binaphthyl of formula (III): wherein R¹ represents a hydrogen atom, a methyl group, or a t-butyl group; R² represents a lower alkyl group or a trifluoromethyl group; and X is as defined above, as a catalyst at a temperature of from 70 to 150°C to obtain an optically active alcohol represented by formula (VI): wherein X and R are as defined above, and then reacting the optically active alcohol as obtained with trimethylamine without isolation.

  一种制备肉碱的工艺，包括不对称氢化式 (I) 所代表的 γ-卤代-β-酮酯： 其中 X 代表氯原子或溴原子；R 代表低级烷基、 在式 (II)、(III) 或 (IV) 所代表的钌-光活性膦络合物存在下： Ru₂Cl₄(L)₂(C₂H₅)₃N (II) Ru(OCOR²)₂(L) (IV) RuX₂(L) (V) 其中 L 代表式 (III) 的 2,2′-双(二-p-R¹-苯基膦)-1,1′-联萘： 其中 R¹ 代表氢原子、甲基或叔丁基； R² 代表低级烷基或三氟甲基；X 如上定义、 作为催化剂，在 70 至 150°C 的温度下，得到由式 (VI) 代表的光学活性醇： 其中 X 和 R 如上文所定义，然后将得到的光学活性醇与三甲胺进行反应而不进行分离。