tert-butyl 3-oxotetradecanoate | 627535-28-8

• 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: tert-butyl 3-oxotetradecanoate
• CAS: 627535-28-8
• 化学式: C₁₈H₃₄O₃
• 分子量: 298.466
• InChiKey: TXDCVRFKTNHJMZ-UHFFFAOYSA-N

物化性质

• 沸点：
  319.7±10.0 °C(Predicted)
• 密度：
  0.914±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  21
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  tert-butyl 3-oxotetradecanoate 在 [(S)-2,2'-双(二苯基磷)-1,1'-联萘]二氯化钌(II) 氢气 作用下， 以 甲醇 为溶剂， 反应 72.0h， 以96%的产率得到(R)-3-羟基十四烷酸叔丁酯
  参考文献：
  名称：

  Efficient Syntheses of a Series of Trehalose Dimycolate (TDM)/Trehalose Dicorynomycolate (TDCM) Analogues and Their Interleukin-6 Level Enhancement Activity in Mice Sera

  摘要：

  We found an IL-6 level-enhancing compound during our synthetic study of trehalose-6,6'-dimycolate (1, TDM, formerly called cord factor) analogues. TDM is a glycolipid distributed in the cell wall of Mycobacterium tuberculosis and shows significant antitumor activity based on an immunoadjuvant activity. However, due to its significant toxicity, TDM is not yet applicable for practical use. In 1993, Datta and Takayama reported the purification of trehalose-6,6'-dicorynomycolate (2c, TDCM) from Corynebacterium spp. We have previously reported the synthesis of four diastereomeric TDCMs and showed that the synthetic (2R,3R,2'R,3'R)-TDCM (2c, hereafter abbreviated RRRR-TDCM-C-14) is identical to natural TDCM; we also demonstrated that 2c and SSSS-TDCM-C-14 (3c) showed significant antitumor activity as well as inhibitory activity in experimental lung metastasis based on the immunoadjuvant activity. Furthermore, we found that the significant lethal toxicity in mice by TDM (1) was no longer observed with the shorter-chain analogues of TDCMs. Therefore, we have elucidated that the 2,3-antistereochemistry (RR or SS) of the fatty acid residue is promising for biological activities. The chain length of the fatty acid residue should also be important for the biological activity, and thus, we designed a general synthetic procedure for trehalose diesters with 2,3-antistereochemistry and a series of chain lengths by using Noyori's asymmetric reduction of beta,beta-ketoesters followed by antiselective alkylation according to Frater to give beta,beta-hydroxy alcohols as the key steps. Thus, we prepared trehalose diesters (TDCM) 2a-d, 3a-d, and 4a-d as well as monoesters (TMCM) 5a-d and 6a-d. Immunological activities of TDCMs and TMCMs were evaluated by determining IL-6 level enhancement in mouse serum, and we found that RRRR-TDCM-C-14 (2c) and RRSS-TDCM-C-14 (4c) showed significant IL-6 level enhancement activities.

  DOI：

  10.1021/jo062018j
• 作为产物：
  描述：

  月桂酸 在 氯化亚砜 、 calcium hydroxide 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 、 甲苯 为溶剂， 反应 26.5h， 生成 tert-butyl 3-oxotetradecanoate
  参考文献：
  名称：

  一种长链烷基-β-酮酸酯类化合物的合成方法

  摘要：

  本发明公开了一种长链烷基‑β‑酮酸酯类化合物的合成方法，以长链脂肪酸、乙酰乙酸酯类化合物为原料，以有机溶剂为反应介质，加入缚酸剂，进行酰氯化反应后，再进行烷基‑β‑酮酸式分解反应，最后与脂肪醇进行酯化反应，制得长链烷基‑β‑酮酸酯类化合物。本发明的合成方法操作安全简单，无需使用昂贵且危险的试剂，具有生产工艺条件温和，原料廉价易得，转化率高，对底物适应性广等诸多优点，适于大规模工业化生产，可广泛应用于医药、有机合成领域。

  公开号：

  CN116120173A

文献信息

• Synthesis of Alkynes from Vinyl Triflates Using Tetrabutylammonium Fluoride
  作者：Masaru Okutani、Yuji Mori

  DOI：10.1248/cpb.c15-00146

  日期：——

  A convenient method for the preparation of alkynes and alkynyl esters from ketones and beta-keto esters is described which involves the formation of vinyl triflates, followed by elimination with tetrabutylammonium fluoride trihydrate, to give alkynes. Unlike established elimination methods, the method requires neither a strong base nor anhydrous conditions.

  描述了一种由酮和β-酮​​酯制备炔烃和炔基酯的方便方法，该方法包括形成乙烯基三氟甲磺酸酯，然后用四丁基氟化铵三水合物消除，得到炔烃。与已建立的消除方法不同，该方法既不需要强碱也不需要无水条件。
• Chemoselective, Regioselective, and <i>E</i>/<i>Z</i>-Diastereoselective Synthesis of 2-Alkylidenetetrahydrofurans by Sequential Reactions of Ambident Dianions and Monoanions
  作者：Peter Langer、Esen Bellur

  DOI：10.1021/jo034966f

  日期：2003.12.1

  A number of novel beta-ketoesters were prepared by regioselective alkylation reactions of simple beta-ketoester dianions. The cyclization of the dianions of these 1,3-dicarbonyl derivatives with 1-bromo-2-chloroethane afforded a variety of 2-alkylidenetetrahydrofurans with very good regioselectivity and E/Z-diastereoselectivity. These products were deprotonated to give novel ambident carbanions. The

  通过简单的β-酮酯二价基团的区域选择性烷基化反应制备了许多新颖的β-酮酯。这些1-，3-二羰基衍生物的二价阴离子与1-溴-2-氯乙烷的环化反应提供了具有非常好的区域选择性和E / Z-非对映选择性的各种2-亚烷基四氢呋喃。这些产品被去质子化，以产生新颖的碳负离子。这些碳负离子用卤代烷进行的烷基化反应具有非常好的区域选择性和E / Z-非对映选择性，并可以方便地合成许多新的2-亚烷基四氢呋喃。
• Efficient Syntheses of a Series of Trehalose Dimycolate (TDM)/Trehalose Dicorynomycolate (TDCM) Analogues and Their Interleukin-6 Level Enhancement Activity in Mice Sera
  作者：Mugio Nishizawa、Hirofumi Yamamoto、Hiroshi Imagawa、Véronique Barbier-Chassefière、Emmanuel Petit、Ichiro Azuma、Dulce Papy-Garcia

  DOI：10.1021/jo062018j

  日期：2007.3.1

  We found an IL-6 level-enhancing compound during our synthetic study of trehalose-6,6'-dimycolate (1, TDM, formerly called cord factor) analogues. TDM is a glycolipid distributed in the cell wall of Mycobacterium tuberculosis and shows significant antitumor activity based on an immunoadjuvant activity. However, due to its significant toxicity, TDM is not yet applicable for practical use. In 1993, Datta and Takayama reported the purification of trehalose-6,6'-dicorynomycolate (2c, TDCM) from Corynebacterium spp. We have previously reported the synthesis of four diastereomeric TDCMs and showed that the synthetic (2R,3R,2'R,3'R)-TDCM (2c, hereafter abbreviated RRRR-TDCM-C-14) is identical to natural TDCM; we also demonstrated that 2c and SSSS-TDCM-C-14 (3c) showed significant antitumor activity as well as inhibitory activity in experimental lung metastasis based on the immunoadjuvant activity. Furthermore, we found that the significant lethal toxicity in mice by TDM (1) was no longer observed with the shorter-chain analogues of TDCMs. Therefore, we have elucidated that the 2,3-antistereochemistry (RR or SS) of the fatty acid residue is promising for biological activities. The chain length of the fatty acid residue should also be important for the biological activity, and thus, we designed a general synthetic procedure for trehalose diesters with 2,3-antistereochemistry and a series of chain lengths by using Noyori's asymmetric reduction of beta,beta-ketoesters followed by antiselective alkylation according to Frater to give beta,beta-hydroxy alcohols as the key steps. Thus, we prepared trehalose diesters (TDCM) 2a-d, 3a-d, and 4a-d as well as monoesters (TMCM) 5a-d and 6a-d. Immunological activities of TDCMs and TMCMs were evaluated by determining IL-6 level enhancement in mouse serum, and we found that RRRR-TDCM-C-14 (2c) and RRSS-TDCM-C-14 (4c) showed significant IL-6 level enhancement activities.
• 一种长链烷基-β-酮酸酯类化合物的合成方法
  申请人：金浦新材料股份有限公司

  公开号：CN116120173A

  公开（公告）日：2023-05-16

  本发明公开了一种长链烷基‑β‑酮酸酯类化合物的合成方法，以长链脂肪酸、乙酰乙酸酯类化合物为原料，以有机溶剂为反应介质，加入缚酸剂，进行酰氯化反应后，再进行烷基‑β‑酮酸式分解反应，最后与脂肪醇进行酯化反应，制得长链烷基‑β‑酮酸酯类化合物。本发明的合成方法操作安全简单，无需使用昂贵且危险的试剂，具有生产工艺条件温和，原料廉价易得，转化率高，对底物适应性广等诸多优点，适于大规模工业化生产，可广泛应用于医药、有机合成领域。