肼,[(2,3-二氢-1,4-苯并二噁英-2-基)甲基]-,盐酸(1:1) | 169566-78-3

• 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
• 中文名称: 肼,[(2,3-二氢-1,4-苯并二噁英-2-基)甲基]-,盐酸(1:1)
• 英文名称: rac-4-isopropyl-4-methyl-2-phenyl-1,3-oxazol-5(4H)-one
• 英文别名: 4-isopropyl-4-methyl-2-phenyl-1,3-oxazol-5(4H)-one；rac-4-isopropyl-4-methyl-2-phenyloxazol-5(4H)-one；4-isopropyl-4-methyl-2-phenyloxazol-5(4H)-one；4-isopropyl-4-methyl-2-phenyl-4H-oxazol-5-one；4-Methyl-2-phenyl-4-propan-2-yl-1,3-oxazol-5-one
• CAS: 169566-78-3
• 化学式: C₁₃H₁₅NO₂
• 分子量: 217.268
• InChiKey: CJJMGKMMPVGELA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  肼,[(2,3-二氢-1,4-苯并二噁英-2-基)甲基]-,盐酸(1:1) 在 sodium tetrahydroborate 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 N-(1-(4-chlorophenyl)-1-hydroxy-2,3-dimethylbutan-2-yl)benzamide
  参考文献：
  名称：

  N-1-Alkyl-2-oxo-2-aryl amides as novel antagonists of the TRPA1 receptor

  摘要：

  A series of potent antagonists of the ion channel transient receptor potential A1 (TRPA1) was developed by modifying lead structure 16 that was discovered by high-throughput screening. Based on lead compound 16, a SAR was established, showing a narrow region at the nitro-aromatic R-1 moiety and at the warhead, while the R-2 side had a much wider scope including ureas and carbamates. Compound 16 inhibits Ca2+-activated TRPA1 currents reversibly in whole cell patch clamp experiments, indicating that under in vivo conditions, it does not react covalently, despite its potentially electrophilic ketone. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2012.07.032
• 作为产物：
  描述：

  N-苯甲酰-N-缬氨酸 在 sodium hydride 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 肼,[(2,3-二氢-1,4-苯并二噁英-2-基)甲基]-,盐酸(1:1)
  参考文献：
  名称：

  重新研究4-单取代的2-苯基恶唑-5（4 H）-ones（'azlactones'）的α-烷基化：普遍进入高度官能化的α，α-二取代的α-氨基酸†

  摘要：

  4-单取代的2-苯基恶唑-5（4 H）-ones（= 4-单取代的2-苯基-氮杂内酯）rac - 2至4,4-二取代的2-的α-烷基化的新颖，更可靠，更通用的反应条件发现苯恶唑-5（4 H）-one rac - 1（方案2）。因此，以中等到良好的总收率（40-90％，见表）制备了一系列高度功能化的rac - 1。lac内酯rac - 1是合成光学纯α，α-二取代（R）和（S）的理想前体。）-α-氨基酸。

  DOI：

  10.1002/hlca.19940770520

文献信息

• <scp>L</scp>-Phenylalanine Cyclohexylamide: A simple and convenient auxiliary for the synthesis of optically pure α,α-disubstituted (<i>R</i>)- and (<i>S</i>)-amino acids
  作者：Daniel Obrecht、Udo Bohdal、Clemens Broger、Daniel Bur、Christian Lehmann、Ruth Ruffieux、Peter Schönholzer、Clive Spiegler、Klaus Müller

  DOI：10.1002/hlca.19950780305

  日期：1995.5.10

  synthesis of a series of optically pure α,α-disubstituted (R)- and (S)-amino acids of type 1, such as (R)- and (S)-2-methyl-phenylalanine (1a), (R)- and (S)-2-methyl-2-phenylglycine (1b), and (R)- and (S)-2-methylvaline (1c; Scheme 3). These amino acids were efficiently transformed into the suitably protected and activated amino acid building blocks (R)- and (S)-12b and (R)- and (S)-12c (Scheme 4) which are

  这项工作描述了L-苯丙氨酸环己基酰胺（5C），其为简单的，价格便宜，且功能强大的手性助剂为一系列光学纯α，α-二取代的（的合成- [R ）-和（小号）型的α-氨基酸1，这样如（R）-和（S）-2-甲基-苯丙氨酸（1a），（R）-和（S）-2-甲基-2-苯甘氨酸（1b）以及（R）-和（S）-2 -甲基缬氨酸（1c；方案3）。这些氨基酸被有效地转化为适当保护和活化的氨基酸构件（R）和（S）-12b以及（R）-和（S）-12c（方案4），它们已经准备好通过溶液或固相技术掺入肽中。基于属于非对映异构体肽系列6和7的6b，6c和7a的晶体结构，确定该系列的每个成员的绝对构型。对于6b和7a分别观察到II'和I型的β-转角几何形状，而6c以扩展构象结晶。讨论了侧链变化对这些三酰胺的构象和晶体堆积的影响。
• Steric and electronic substituent effects in hydrolysis and aminolysis of 4-alkyl-4-methyl-2-aryl-4,5-dihydro-1,3-oxazol-5-ones
  作者：Miloš Sedlák、Roman Keder、Pavel Skála、Jiří Hanusek

  DOI：10.1002/poc.928

  日期：2005.8

  derivatives undergo nucleophilic attack by water at the carbonyl carbon atom at the 5-position of the 1,3-oxazol-5-one ring to the extents of ca 70% and 60%, respectively. Another reaction path consists in nucleophilic attack by water at the 2-position of the 1,3-oxazol-5-one ring. The reaction kinetics of aminolyses of substituted 4-isopropyl-4-methyl-2-phenyl-1,3-oxazol-5(4H)-ones (1a, 1b, 1f) giving

  酸催化的取代的4-烷基-4-甲基-2-甲基-2-芳基-4,5-二氢-1,3-恶唑-5-酮水解为相应的2-烷基-2-苯甲酰基氨基丙酸的动力学和机理被研究了。在1,3-恶唑-5-环的4位上的酸催化水解与烷基取代的速率常数的塔夫脱相关性是非线性的。在哈米特（Hammett）相关性中，ρ的值随着烷基取代基的空间需求的增加而降低。对于4-异丙基和叔丁基衍生物，ρ分别为-0.63和-0.32。质子化的4-异丙基和叔丁基衍生物受到水在1,3-恶唑-5-酮环的5位羰基碳原子上的亲核攻击，其程度分别约为70％和60％。另一反应途径是在1，3-恶唑-5-酮环的2-位被水进行亲核攻击。取代的4-异丙基-4-甲基-2-甲基-2-苯基-1,3-恶唑-5（4 H）-ones（1a，1b，1f）的氨解反应动力学，得到取代的N- 1,2-二甲基-在丙胺水溶液中研究了1-[（丙基氨基）羰基]-丙基}苯甲酰胺（3a，3b，
• Process for the preparation of amides
  申请人：Ihara Chemical Industry Co., Ltd.

  公开号：US06504046B1

  公开（公告）日：2003-01-07

  A process for producing an amide compound of the following formula by reacting a nitrile compound of the formula with an acid to obtain an oxazolinone compound of the formula and reacting the oxazolinone compound with a carboxy compound of the formula in the presence of a base.

  通过将公式为nitrile的化合物与酸反应以获得公式为oxazolinone的化合物，然后在碱存在下将oxazolinone化合物与公式为carboxy的化合物反应，从而制备以下公式的酰胺化合物的方法。
• PROCESS FOR THE PREPARATION OF AMIDES
  申请人：IHARA CHEMICAL INDUSTRY CO., LTD.

  公开号：EP1092705A1

  公开（公告）日：2001-04-18

  The present invention aims at providing important intermediates used in production of a phenylalkanoic acid amide compound showing an excellent fungicidal effect; and novel and simple processes for producing such an intermediate or a raw material compound used in production of the intermediate. The present invention relates to a process for producing an amide compound represented by the following general formula [wherein R is an alkyl group, a cycloalkyl group, a haloalkyl group, an aryl group, a substituted aryl group, an arylalkyl group, a substituted arylalkyl group, an (aryl)(alkoxy)alkyl group or a (substituted aryl)(alkoxy)alkyl group; R1 and R2 are each independently an alkyl group, a cycloalkyl group, a haloalkyl group, an arylalkyl group, a substituted arylalkyl group, an aryl group, a substituted aryl group or a hydrogen atom, and may bond with each other to form a ring together with the carbon atom with which they bond; and R3 is an alkyl group, a cycloalkyl group, a haloalkyl group, an arylalkyl group, a substituted arylalkyl group, an aryl group, a substituted aryl group or a hydrogen atom], which process comprises reacting a nitrile compound represented by the following general formula (wherein R, R1 and R2 each have the same definition as given above) with an acid to give rise to intramolecular ring closure to obtain an oxazolinone compound represented by the following general formula (wherein R, R1 and R2 each have the same definition as given above), and reacting the oxazolinone compound with a carboxy compound represented by the following general formula (wherein Y is a hydrogen atom, a carboxyl group or a salt of the carboxyl group; and R3 has the same definition as given above) in the presence of a base.

  本发明旨在提供用于生产具有优异杀菌效果的苯烷酸酰胺化合物的重要中间体；以及生产这种中间体或用于生产这种中间体的原料化合物的新颖而简单的工艺。 本发明涉及一种生产由以下通式表示的酰胺化合物的工艺 [其中 R 是烷基、环烷基、卤代烷基、芳基、取代的芳基、芳烷基、取代的芳烷基、 （芳基）（烷氧基）烷基或（取代的芳基）（烷氧基）烷基；R1 和 R2 各自独立地为烷基、环烷基、卤代烷基、芳烷基、取代芳烷基、芳基、取代芳基或氢原子，并可相互键合，与键合的碳原子一起形成环；和 R3 是烷基、环烷基、卤代烷基、芳烷基、取代芳烷基、芳基、取代芳基或氢原子]，该工艺包括使以下通式表示的腈化合物反应 (其中 R、R1 和 R2 的定义同上）与酸反应，产生分子内环闭合，得到下式通式所代表的噁唑啉酮化合物 (其中 R、R1 和 R2 的定义同上），并将该噁唑啉酮化合物与下式通式所代表的羧基化合物反应 (其中 Y 为氢原子、羧基或羧基盐；R3 的定义与上述相同）在碱存在下反应。
• BEMP-Promoted C(4)-Alkylation of 4-Alkyloxazol-5(4H)-ones: A Rapid and Efficient Route to α,α-Dialkyl-α-amino Acids
  作者：Byeong-Seon Jeong、Yeon-Ju Lee、Jeyoung Seo、Dong-Guk Kim、Hyeung-geun Park

  DOI：10.1055/s-0032-1317801

  日期：——

  Rapid and efficient C(4)-alkylation of 4-alkyloxazol-5(4H)-ones has been achieved by the utilization of BEMP as base. 4,4-Dialkyloxazol-5(4H)-ones, which can easily be hydrolyzed into free alpha,alpha-dialkyl-alpha-amino acids, were obtained in high yields (up to 99%) within a few minutes (1-18 min). BEMP, a sterically hindered strong base with low nucleophilicity facilitated the desired reaction, while decreasing the rate of side reactions such as O-alkylation, C(2)-alkylation and the breakage of oxazolone.