tert-butyl 3-oxooctadecanoate | 98926-85-3

• 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-oxooctadecanoate
• 英文别名: β-ketooctadecanoic acid t-butyl ester；3-oxooctadecanoic acid t-butyl ester
• CAS: 98926-85-3
• 化学式: C₂₂H₄₂O₃
• 分子量: 354.574
• InChiKey: GYLQPFTTYYUWRS-UHFFFAOYSA-N

物化性质

• 沸点：
  366.6±10.0 °C(Predicted)
• 密度：
  0.903±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.3
• 重原子数：
  25
• 可旋转键数：
  18
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 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-oxooctadecanoate 在 [(S)-2,2'-双(二苯基磷)-1,1'-联萘]二氯化钌(II) 氢气 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， -48.0 ℃ 、6.86 MPa 条件下， 反应 78.5h， 生成 (2R,3R)-tert-butyl 3-hydroxy-2-tetradecyloctadecanoate
  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：

  乙酰乙酸叔丁酯 、 十四烷基碘化物 在 sodium hydride 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.17h， 以78%的产率得到tert-butyl 3-oxooctadecanoate
  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

文献信息

• Fatty acid derivatives and process of producing them
  申请人：Yamanouchi Pharmaceutical Co., Ltd.

  公开号：US04629736A1

  公开（公告）日：1986-12-16

  Fatty acid derivatives represented by the general formula ##STR1## and salts thereof. The compounds of this invention have excellent fibrinolytic action and a highly improved solubility.

  通式##STR1##代表的脂肪酸衍生物及其盐。本发明的化合物具有出色的纤溶作用和高度改善的溶解性。
• N-acyl peptide, processes for their preparation and pharmaceutical
  申请人：Fujisawa Pharmaceutical Co., Ltd.

  公开号：US04643990A1

  公开（公告）日：1987-02-17

  N-acylpeptides are disclosed of the formula: ##STR1## wherein R.sup.1 is alkanoyloxy or alkenoyloxy; R.sup.2 is alkyl or alkenyl; R.sup.3 and R.sup.4 are each lower alkyl, hydroxy(lower)alkyl, ar(lower)alkyl, esterified carboxy(lower)alkyl, carboxy(lower)alkyl, protected amino(lower)alkyl or amino(lower)alkyl; R.sup.5 is hydrogen, hydroxy(lower)alkyl, protected amino(lower)alkyl, amino(lower)alkyl, carboxy(lower)alkyl or esterified carboxy(lower)alkyl; R.sup.6 is carboxy, esterified carboxy or sulfo(lower)alkyl; A.sup.1, A.sup.2 and A.sup.3 are each bond or lower alkylene; and m and n are each an integer of 0 or 1; or its pharmaceutically acceptable salt. These compounds have anti-complementary activity and fibrinolytic activity, and are useful as therapeutic agents for immune-complex diseases or autoimmune diseases such as nephritis, rheumatic diseases, systemic lupus erythematosus, etc. and thrombosis such as cerebral apoplexy, coronary insufficiency, pulmonary embolism, etc.

  本发明揭示了以下式子的N-酰基肽：##STR1## 其中R.sup.1是脂肪酰氧基或烯酰氧基；R.sup.2是烷基或烯基；R.sup.3和R.sup.4分别是低烷基，羟基（低）烷基，芳基（低）烷基，酯化的羧基（低）烷基，羧基（低）烷基，保护的氨基（低）烷基或氨基（低）烷基；R.sup.5是氢，羟基（低）烷基，保护的氨基（低）烷基，氨基（低）烷基，羧基（低）烷基或酯化的羧基（低）烷基；R.sup.6是羧基，酯化的羧基或磺酸（低）烷基；A.sup.1，A.sup.2和A.sup.3分别是键或低烷基；m和n分别是0或1的整数；或其药学上可接受的盐。这些化合物具有抗补体活性和纤溶活性，并可用作免疫复合物疾病或自身免疫疾病（如肾炎，风湿病，系统性红斑狼疮等）以及血栓形成（如脑卒中，冠状动脉不足，肺栓塞等）的治疗剂。
• N-acyl peptide, processes for their preparation and pharmaceutical compostions thereof
  申请人：FUJISAWA PHARMACEUTICAL CO., LTD.

  公开号：EP0085255A2

  公开（公告）日：1983-08-10

  Compounds of the formula: wherein R1 is hydrogen, alkanoyloxy or alkenoyloxy; R2 is alkyl or alkenyl; R3 and R4 are each hydrogen, lower alkyl, hydroxy(lower)alkyl, ar(lower) alkyl, esterified carboxy(lower)alkyl, carboxy-(lower)alkyl, protected amino(lower)alkyl or amino(lower)alkyl; R5 is hydrogen, hydroxy(lower)alkyl, protected amino-(lower)alkyl, amino(lower)alkyl, carboxy(lower)alkyl or esterified carboxy(lower)alkyl; R6 is carboxy, esterifed carboxy or sulfo(lower)alkyl; A1, A2 and A3 are each bond or lower alkylene; and m and n are each an integer of 0 or 1; and their pharmaceutically- acceptable salts have anti-complementary activity and fibrinolytic activity, and are useful as therapeutic agents for immunecomplex diseases or autoimmune diseases such as nephritis, rheumatic diseases, systemic lupus erythematosus, etc. and thrombosis such as cerebral apoplexy, coronary insufficiency, pulmonary embolism.

  式中的化合物： 式中 R1 是氢、烷酰氧基或烯酰氧基； R2 是烷基或烯基 R3 和 R4 分别是氢、低级烷基、羟基（低级）烷基、芳基（低级）烷基、酯化羧基（低 级）烷基、羧基（低级）烷基、受保护氨基（低级）烷基或氨基（低级）烷基； R5 是氢、羟基（低级）烷基、受保护氨基（低级）烷基、氨基（低级）烷基、羧基（低级）烷基或酯化羧基（低级）烷基； R6 是羧基、酯化羧基或磺基（低级）烷基； A1、A2 和 A3 分别为键或低级亚烷基；以及 m 和 n 分别为 0 或 1 的整数；它们的药学上可接受的盐具有抗补体活性和纤维蛋白溶解活性，可用作肾炎、风湿病、系统性红斑狼疮等免疫复合物疾病或自身免疫性疾病以及脑栓塞、冠状动脉供血不足、肺栓塞等血栓形成的治疗剂。
• Fatty acid derivatives and processes of producing them
  申请人：YAMANOUCHI PHARMACEUTICAL CO. LTD.

  公开号：EP0136879A2

  公开（公告）日：1985-04-10

  Water soluble fibrinolytic fatty acid derivatives of formula (I), and salts thereof in which R' represents an alkanoylamino group the carbon chain of which may be interrupted by at least one oxygen atom, an alkanoyloxy group the carbon chain of which is interrupted by at least one oxygen atom, an alkoxyimino group, or a group shown by the formula R3-(NH-Y-CO)m-Z-(wherein R3 represents an alkanoyl group or a C1-C5 alkylsulfonyl group; Y represents an alkylene group; m represents 1 or 2; and Z represents an oxygen atom or an imino group); R2 represents an alkyl group, an alkylaminocarbonyl group the carbon chain of which may be interrupted by at least one oxygen atom, or an alkoxyaminocarbonyl group the carbon chain of which is interrupted by at least one oxygen atom; represents a single bond or a double bond; a is zero when is a double bond and 1 when is a single bond; b is 0 or 1; c is 0 or 1; n represents an integer of 1 to 3; and A and B are the same or different amino acid residues. Various processes for the production of these compounds are as described.

  式(I)的水溶性纤溶脂肪酸衍生物及其盐类 其中 R'代表碳链可能被至少一个氧原子打断的烷酰氨基、碳链被至少一个氧原子打断的烷酰氧基、烷氧基亚氨基或式 R3-(NH-Y-CO)m-Z-（其中 R3 代表烷酰基或 C1-C5 烷基磺酰基；Y 代表亚烷基；m 代表 1 或 2；Z 代表氧原子或亚氨基）； R2 代表烷基、烷基氨基羰基（其碳链可被至少一个氧原子打断）或烷氧基氨基羰基（其碳链被至少一个氧原子打断）； 代表单键或双键； 当为双键时，a 为 0，当为单键时，a 为 1； b 为 0 或 1； c 为 0 或 1； n 代表 1 至 3 的整数；以及 A 和 B 是相同或不同的氨基酸残基。 生产这些化合物的各种工艺如上所述。
• Bianchi, Giorgio; Grugni, Mario, Gazzetta Chimica Italiana, 1985, vol. 115, # 11, p. 633 - 636
  作者：Bianchi, Giorgio、Grugni, Mario

  DOI：——

  日期：——