methyl 2-<(3-methylacetonyl)thio>acetate | 61363-63-1

• 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: methyl 2-<(3-methylacetonyl)thio>acetate
• 英文别名: methyl 2-(2-oxobutylthio)acetate；Methyl-2-(3-methyl-acetonylthio)-acetat；Methyl [(2-oxobutyl)sulfanyl]acetate；methyl 2-(2-oxobutylsulfanyl)acetate
• CAS: 61363-63-1
• 化学式: C₇H₁₂O₃S
• 分子量: 176.236
• InChiKey: LSVOGJNOXYTIKJ-UHFFFAOYSA-N

物化性质

• 沸点：
  137-140 °C(Press: 13 Torr)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  68.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 2-<(3-methylacetonyl)thio>acetate 在 咪唑 、 氢氧化钾 、 sodium tetrahydroborate 、 copper(l) iodide 、 四(三苯基膦)钯 、 N,N-二甲基乙醇胺 、 cerium(III) chloride 、 bis(triphenylphosphine) palladium (Il) acetate 、 碘 、 sodium hydride 、 二乙胺 、 正丁胺 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 169.67h， 生成 (R)-6-{(1R,3aR,7aR)-4-[(S)-5-(tert-Butyl-dimethyl-silanyloxy)-4-methyl-5,6-dihydro-2H-thiopyran-3-ylethynyl]-7a-methyl-2,3,3a,6,7,7a-hexahydro-1H-inden-1-yl}-2-methyl-heptan-2-ol
  参考文献：
  名称：

  Studies of vitamin D (calciferol) and its analogs. 42. 3-Deoxy-3-thia-1.alpha.,25-dihydroxyvitamin D3 and its 1.beta.-epimer: synthesis and biological evaluation

  摘要：

  The syntheses of 3-deoxy-3-thia-1-alpha,25-dihydroxyvitamin D3 (5a) and its 1-beta-epimer 5b have been achieved starting from CD-fragment 10 and the enantiomerically pure A-rings 11a and 11b prepared from thia 1,3-diketone 13. For the preparation of 11a and 11b, the thia diketone 13 was converted in two steps to the trimethylsilyl enynone 18. In the most effective route, the latter was asymmetrically reduced using (R)- or (S)-oxazaborolidine 24 and 25 and catecholborane to afford 19a (87% ee) and 19b (85% ee), respectively. Final enrichment to 11a and 11b was achieved via their crystalline carbamates 23a and 22b and then hydrolysis to the enantiomerically pure enynols 12a and 12b and silylated to the desired 11a and 11b. The absolute configuration at C-1 of the A-ring was examined in detail through four empirical correlation methods. The elution order of carbamates 22 and 23 by HPLC correlates with Pirkle's empirical rules. The specific rotations of enynols (-)-12a and (+)-12b correlate with Mills' rules for absolute configurations of chiral cyclohexenols. The enantiomeric sense of asymmetric reduction using the (R)- or (S)-oxazaborolidines and a complementary asymmetric reduction using LiAlH4 and N-methylephedrine was exactly that predicted. The C-1 absolute configuration of (S,S)-carbamate 22b was in fact fully confirmed by a single-crystal X-ray crystallographic study. Hence, the four empirically derived methods for establishing absolute configuration of the various enynols were mutually consistent. The analogues 5a and 5b were submitted for biological evaluation of their relative ability, in relation to the reference 1-alpha,25-dihydroxyvitamin D3 (3, 1-alpha,25-(OH)2-D3), to stimulate intestinal calcium absorption (ICA) and bone calcium mobilization (BCM) under in vivo conditions. Analogue 5a was 20% and <10% while analogue 5b was <20% and <10% as active as a 100 pmol dose of 1-alpha,25-(OH)2-D3 for ICA and BCM, respectively. In addition, 5a and 5b were 14.5 +/- 5.7% and 1.23 +/- 0.38%, respectively, as effective as 1-alpha,25-(OH)2-D3 in binding, under in vitro conditions, to a chick intestinal nuclear receptor.

  DOI：

  10.1021/jo00040a025
• 作为产物：
  描述：

  methyl 2-(2-hydroxybutylthio)acetate 在 三乙胺 作用下， 以 水 、 二甲基亚砜 为溶剂， 生成 methyl 2-<(3-methylacetonyl)thio>acetate
  参考文献：
  名称：

  EP1211249

  摘要：

  公开号：

文献信息

• Reaction of mixed carboxylic anhydrides with grignard reagents
  作者：T. Terasawa、T. Okada

  DOI：10.1016/0040-4020(77)80298-6

  日期：1977.1

  The low-temperature Grignard reaction of mixed carboxylic anhydrides derived from acid chlorides and o-anisic acid to the general synthesis of keto esters is demonstrated for compounds 1–6, although, some limitations on substrate and Grignard reagent species are also encountered; attempts in the oxa series 2 are unsuccessful, and reaction with ω-phenylpropyl Grignard species for 1 and 4 shows a drastic

  对于化合物1-6，已证明了酰氯和邻茴香酸的混合羧酸酐的低温格氏反应与酮酯的一般合成，尽管在底物和格氏试剂种类上也遇到了一些限制。在氧杂一系列尝试2是不成功的，并与ω苯丙基格利雅物种反应1只4示出了在酮酯为产率的急剧下降米甲氧基类似物。异常行为可能与特定类型的金属配位配合物的另一种类型有关，该配合物包括正确位于基质或试剂中的醚氧原子
• Novel thiazine derivatives
  申请人：SANTEN PHARMACEUTICAL CO.,LTD.

  公开号：US20040097496A1

  公开（公告）日：2004-05-20

  A compound having 3-oxo-3,4-dihydro-2H-1,4-thiazine 4-tetrahydropyrazine as a main skeleton. The compound is a chymase inhibitor and is represented by the following formula [I] and salts thereof: 1 In the formula [I], X is S; R 1 and R 2 are H, alkyl, cycloalkyl or aryl; R 3 and R 4 are H, alkyl, cycloalkyl, aryl or an aromatic heterocycle; R 5 is H, alkyl, cycloalkyl, aryl or -A 3 -A 4 -R 7 ; R 6 is H, alkyl, cycloalkyl, hydroxy, alkoxy, aryl, aryloxy or an aromatic heterocycle; R 7 is H, alkyl, hydroxy, alkoxy, aryl, aryloxy, amino, alkylamino, arylamino, an aromatic heterocycle or a nonaromatic heterocycle; A 1 is alkylene; A 2 is carbonyl or sulfonyl; A 3 is alkylene; A 4 is carbonyl or oxalyl; and n is 0 or 1.

  化合物具有3-氧代-3,4-二氢-2H-1,4-噻嗪-4-四氢吡嗪作为主要骨架。该化合物是一种Chymase抑制剂，由以下公式[I]及其盐所表示：1在公式[I]中，X为S；R1和R2为H，烷基，环烷基或芳基；R3和R4为H，烷基，环烷基，芳基或芳香族杂环；R5为H，烷基，环烷基，芳基或-A3-A4-R7；R6为H，烷基，环烷基，羟基，烷氧基，芳基，芳氧基或芳香族杂环；R7为H，烷基，羟基，烷氧基，芳基，芳氧基，氨基，烷基氨基，芳基氨基，芳香族杂环或非芳香族杂环；A1为烷基；A2为羰基或磺酰基；A3为烷基；A4为羰基或草酰基；n为0或1。
• Oxa- and thia-steroids
  申请人：Shionogi & Co., Ltd.

  公开号：US04083852A1

  公开（公告）日：1978-04-11

  16-Oxa- and 16-thia-D-homo-estrogen derivatives useful as postcoital oral contraceptives which are produced by total synthesis from 1-vinyltetralin-1-ols or their thiuronium derivatives on reactions with 4-substituted tetrahydropyran- or tetrahydrothiopyran-3,5-diones, and subsequent appropriate modifications.

  16-Oxa-和16-thia-D-homo-雌激素衍生物是一种有用的事后口服避孕药，它们是通过从1-乙烯基四氢萘酚或其硫脲衍生物开始的全合成反应中，与4-取代四氢吡喃-或四氢噻吩-3,5-二酮反应，然后进行适当的修饰而产生的。
• Novel type of oxa- and thia-steroids
  申请人：Shionogi & Co., Ltd.

  公开号：US04130565A1

  公开（公告）日：1978-12-19

  16-Oxa- and 16-thia-D-homo-estrogen derivatives useful as postcoital oral contraceptives which are produced by total synthesis from 1-vinyltetralin-1-ols or their thiuronium derivatives on reactions with 4-substituted tetrahydropyran- or tetrahydrothiopyran-3,5-diones, and subsequent appropriate modifications.

  16-氧-和16-硫-D-同型雌激素衍生物，可用作事后口服避孕药，这些衍生物通过从1-乙烯基四氢萘-1-醇或其硫脲衍生物开始的全合成反应中，与4-取代的四氢吡喃-或四氢噻吩-3,5-二酮反应，随后进行适当的修饰而制得。
• Thiazine derivatives
  申请人：Nishimura Kazuo

  公开号：US06960575B2

  公开（公告）日：2005-11-01

  A compound having 3-oxo-3, 4-dihydro-2H-1, 4-thiazine 4-tetrahydropyrazine as a main skeleton. The compound is a chymase inhibitor and is represented by the following formula [I] and salts thereof: In the formula [I], X is S; R 1 and R 2 are H, alkyl, cycloalkyl or aryl; R 3 and R 4 are H, alkyl, cycloalkyl, aryl or an aromatic heterocycle; R 5 is H, alkyl, cycloalkyl, aryl or -A 3 -A 4 -R 7 ; R 6 is H, alkyl, cycloalkyl, hydroxy, alkoxy, aryl, aryloxy or an aromatic heterocycle; R 7 is H, alkyl, hydroxy, alkoxy, aryl, aryloxy, amino, alkylamino, arylamino, an aromatic heterocycle or a nonaromatic heterocycle; A 1 is alkylene; A 2 is carbonyl or sulfonyl; A 3 is alkylene; A 4 is carbonyl or oxalyl; and n is 0 or 1.

  一种具有3-氧代-3，4-二氢-2H-1，4-噻嗪-4-四氢吡嗪为主要骨架的化合物。该化合物是一种胰蛋白酶酶抑制剂，其化学式[I]及其盐如下所示：在公式[I]中，X为S；R1和R2为H，烷基，环烷基或芳基；R3和R4为H，烷基，环烷基，芳基或芳香族杂环；R5为H，烷基，环烷基，芳基或-A3-A4-R7；R6为H，烷基，环烷基，羟基，烷氧基，芳基，芳氧基或芳香族杂环；R7为H，烷基，羟基，烷氧基，芳基，芳氧基，氨基，烷基氨基，芳基氨基，芳香族杂环或非芳香族杂环；A1为烷基；A2为羰基或磺酰基；A3为烷基；A4为羰基或草酰基；n为0或1。