香旱芹酮肟 | 26127-86-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: 香旱芹酮肟
• 英文名称: (4R)-(-)-carvoxime
• 英文别名: (-)-carvone oxime；oxime (4R)-4-isopropenyl-1-methylcyclohex-1-en-6-one；(R)-2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-one oxime；L-Carvoxim；(-)-Carvon-oxim；l-Carvonoxim；N-[(5R)-2-Methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-ylidene]hydroxylamine；N-[(5R)-2-methyl-5-prop-1-en-2-ylcyclohex-2-en-1-ylidene]hydroxylamine
• CAS: 26127-86-6
• 化学式: C₁₀H₁₅NO
• 分子量: 165.235
• InChiKey: JOAADLZWSUDMHZ-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  香旱芹酮肟 在 水 、 N,N,N,N-tetraethylammonium tetrafluoroborate 作用下， 以 1,2-二氯乙烷 为溶剂， 以70 %的产率得到(R)-Carvone
  参考文献：
  名称：

  通过电氧化脱肟从肟生成羰基化合物

  摘要：

  开发了一种电化学方案，用于从肟生成具有优异官能团相容性的羰基化合物。机理实验研究支持这样的观点，即可能涉及肟的电氧化途径，其中水可以充当氧亲核试剂和最终羰基化合物的氧源。

  DOI：

  10.1021/acs.joc.3c02631
• 作为产物：
  描述：

  (R)-Carvone 在 吡啶 、 盐酸羟胺 作用下， 以 乙醇 为溶剂， 以98%的产率得到香旱芹酮肟
  参考文献：
  名称：

  具有抗菌活性的含氮单萜类化合物的合成。

  摘要：

  将贝克曼重排结合到本研究中导致形成源自天然化合物的含氮萜类衍生物。起始的单萜和获得的衍生物都经过估计其抗菌潜力。在本研究中，金黄色葡萄球菌对所检查的化合物最敏感。在金黄色葡萄球菌上进行的最小抑菌浓度（MIC）实验表明，在所测试的衍生物和起始原料中，（-）-薄荷酮肟（-）-8和（+）-聚醚酮肟（+）-13具有最佳的抗菌活性。化合物。它们的MIC90值为100 µg / mL。还评估了获得的衍生物对细菌脲酶的抑制活性。在测试的化合物中，发现了三种活性抑制剂-肟14和内酰胺（-）-15和16限制了巴斯德曲霉脲酶的活性，Ki值分别为174.3 µM，43.0 µM和4.6 µM。据我们所知，衍生物16是迄今为止描述的最活跃的抗脲水解内酰胺。

  DOI：

  10.1080/14786419.2018.1548456

文献信息

• The biotransformation of carvoxime and dihydrocarvoxime with cell suspension cultures of Nicotiana tabacum
  作者：Takayuki Suga、Toshifumi Hirata、Masayuki Futatsugi

  DOI：10.1016/s0031-9422(00)80453-7

  日期：1984.5

  Abstract In newly initiated cell suspension cultures of Nicotiana tabacum , (4 R )-(−) and (4 S )(+)-carvoximes and (1 S ,4 R )(+)-dihydrocarvoxime were hydrolysed to the corresponding ketones and then the resultant ketones were reduced to the corresponding alcohols.

  摘要 在烟草新开始的细胞悬浮培养中，(4 R )-(-) 和(4 S )(+)-香芹酮肟和(1 S ,4 R )(+)-二氢香芹酮肟被水解成相应的酮，然后生成的酮被还原为相应的醇。
• Selective one-pot carvone oxime hydrogenation over titania supported gold catalyst as a novel approach for dihydrocarvone synthesis
  作者：Yu. S. Demidova、E.V. Suslov、O.A. Simakova、K.P. Volcho、N.F. Salakhutdinov、I.L. Simakova、D. Yu. Murzin

  DOI：10.1016/j.molcata.2016.04.013

  日期：2016.8

  for the first time that dihydrocarvone can be selectively produced by gold-catalyzed one-pot transformation of carvone oxime. This reaction was carried out at 100 °C under hydrogen pressure of 9 bar over 1.9 wt.% Au/TiO2 catalyst using methanol as a solvent. Dihydrocarvone synthesis was shown to occur via carvone formation with the subsequent hydrogenation of its conjugated C C double bond. Application

  摘要 首次表明金催化香芹酮肟一锅转化可选择性制备二氢香芹酮。该反应在 100 °C 和 9 bar 的氢气压力下在 1.9 wt.% Au/TiO2 催化剂上使用甲醇作为溶剂进行。二氢香芹酮的合成显示通过香芹酮的形成以及随后其共轭的CC双键的氢化而发生。首次报道了Au/TiO2催化剂在烯烃CC官能团的脱肟和选择性加氢中的应用。这些步骤的组合优化了从香芹酮肟生产二氢香芹酮的合成方法，香芹酮肟是从柠檬烯合成香芹酮的关键中间体。尽管反应速率比香芹酮低，在香芹酮肟氢化的情况下，观察到对反式二氢香芹酮的立体选择性显着增加。反式和顺式二氢香芹酮的比例接近 4.0，而香芹酮加氢的比例为 1.8。
• ——
  作者：V. D. Kolesnik

  DOI：10.1023/a:1023902621846

  日期：——

  The reaction of dibenzylphosphine oxide with O-methyloximes of some alpha,beta-unsaturated ketones results in the phosphorylation at the P-carbon atom to form methoxyiminophosphine oxides, whereas the reaction of dibenzylphosphine oxide with O-methyloximes of alpha,beta-unsaturated aldehydes affords aminodihydrophosphole oxides.
• Synthesis of New 1-Adamantanecarboxylic Acid Derivatives
  作者：E. A. Dikusar1'、N. G. Kozlov、V. I. Potkin、A. P. Yuvchenko、N. V. Kovganko

  DOI：10.1023/b:rujo.0000034968.28257.e9

  日期：2004.3

  Reactions of 1-adamantanecarbonyl chloride with functionally substituted alcohols, phenols, amines, thiols, and ketone oximes gave hitherto unknown 1-adamantanecarboxylic acid esters, amides, and thio esters, including those containing a peroxide group.
• Regiospecificity and isotope effects associated with the methyl-methylene eliminations in the enzyme-catalyzed biosynthesis of (R)- and (S)-limonene
  作者：Hyung Jung Pyun、Robert M. Coates、Kurt C. Wagschal、Paul McGeady、Rodney B. Croteau

  DOI：10.1021/jo00067a037

  日期：1993.7

  [8-H-3]-, [8,8,9,9-H-2(4)]-, and [1-H-3,8,9-H-2(6)] geranyl diphosphates (1-t, 1-d4, and 1-d6,t) were synthesized and used as substrates for several monoterpene cyclases to determine the regiospecificity and isotope effects attending the terminating proton transfers in the enzyme-catalyzed biosynthesis of (R)- and (S)-limonene. Degradation of enantiomeric [H-3]limonenes produced by cyclization Of 1-t with the (+)- and (-)-pinene cyclases (synthases) from Salvia officinalis demonstrated that the eliminations occur at both the cis- (55-65%) and trans-methyl (45-35%) groups. In contrast, the terminating eliminations in the formation of (+)- and (-)-limonene catalyzed by limonene cyclasses from Citrus sinensis and Perilla frutescens, respectively, were shown by degradation to occur exclusively (greater-than-or-equal-to 97-98%) at the cis terminal methyl group. The intramolecular isotope effects for the methyl-methylene elimination in limonene biosynthesis catalyzed by (+)- and (-)-pinene cyclases from S. officinalis were found to be k(H)/k(D) = 2.3 +/- 0.2 and 5.9 +/- 0.5, respectively, by GC/MS determinations of [H-2]-limonene derived from enzymatic cyclizations of 1-d4. Similar experiments with (-)-limonene cyclase from Mentha spicata resulted in k(H)/k(D) = 4.0 +/- 0.4. Incubations of 1-d6,t with pinene and bornyl PP cyclases from S. officinalis exhibited significant remote isotope effects (k(H)/k(D) = 1.16-1.27) on the total rate of monoterpene formation which suggest that the initial cyclization step of the enzyme-bound linalyl diphosphate intermediate is an important component of the overall rate of the enzymatic reactions. The isotope effects on the partitioning of the alpha-terpinyl carbocation intermediate between bicyclization and elimination to limonene were determined from the effects of deuterium substitution on the product ratios derived from enzymatic cyclization of 1-d6,t. The small size of these product isotope effects (k(H)/k(D)) = 1.2-1.7) is attributed to a conformational inversion of the alpha-terpinyl ion to a half-chair conformer prior to proton elimination to limonene, thereby rendering the bicyclizations relatively immune to the intrinsic deuterium isotope effect. The regiospecific proton transfers from the cis terminal methyl group effected by the limonene cyclases from Citrus and Perilla are attributed to the minimization of charge separation in the transition state.