(Z)-Deoxybenzoin enolate | 30498-85-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (Z)-Deoxybenzoin enolate
• 英文别名: (Z)-1,2-diphenylethenol
• CAS: 30498-85-2
• 化学式: C₁₄H₁₂O
• 分子量: 196.249
• InChiKey: BTYKKTHKEGJHPO-KAMYIIQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-Deoxybenzoin enolate 在 (+)-tetrahydro-9,9-dimethyl-4H-4a,7-methanooxazirino<3,2-i><2,1>benzisothiazole 3,3-dioxide 、 双(三甲基硅烷基)氨基钾 作用下， 生成 (S)-(+)-安息香 、 (R)-(-)-安息香
  参考文献：
  名称：

  Chemistry of oxaziridines. 18. Synthesis and enantioselective oxidations of the [(8,8-dihalocamphoryl)sulfonyl]oxaziridines

  摘要：

  The synthesis and enantioselective oxidations of [(8,8-dihalocamphoryl)sulfonyl]oxaziridines [8,8-dichloro-1,7,7-trimethyl-2'-(phenylsulfonyl)spiro[bicyclo[2.2.1]heptane-2,3'-oxazinidine]] 13 are reported. These reagents are prepared in two steps from the (camphorylsulfonyl)imine 4 by treatment of the corresponding azaenolate with electrophilic halogen sources followed by biphasic oxidation of the resulting dihalo imine 6-9 with m-CPBA/K2CO3. Of these oxaziridines the dichloro reagent 13b, available on a multigram scale, affords the highest enantioselectivities for the asymmetric oxidation of sulfides to sulfoxides (42-74%) and for the hydroxylation of enolates (often better than 95% ee). In general the molecular recognition is predicted and explained in terms of minimization of nonbonded steric interactions the transition states. For the asymmetric oxidation of sulfides to sulfoxides, secondary electronic factors related to the polarity of the sulfide and oxaziridine also play a role. Definitive evidence for chelation of the metal enolate with the C-X bond in 13 is not found. The molecular recognition is interpreted in terms of the higher reactivity of the reagents and an active-site structure which is sterically complementary with the enolate. For the asymmetric hydroxylation of the Z- and E-enolates of propiophenone (16a), the Z-enolate exhibits much higher stereoselectivity than the E-enolate: >95% vs 22% ee.

  DOI：

  10.1021/jo00052a050
• 作为产物：
  描述：

  苯乙醛 、 水 生成 (Z)-Deoxybenzoin enolate
  参考文献：
  名称：

  KATRITZKY, ALAN R.;LUXEM, FRANZ J.;SISKIN, MICHAEL, ENERGY AND FUELS , 4,(1990) N, C. 514-517

  摘要：

  DOI：

文献信息

• METHOD FOR PRODUCING A CROSS-COUPLING PRODUCT OF A BENZENOID DIAZONIUM SALT
  申请人：Boege Nicolas

  公开号：US20130053598A1

  公开（公告）日：2013-02-28

  The invention relates to a method for producing a cross-coupling product of a benzenoid dizonium salt according to the general formula (I), wherein the groups R 1 , R 2 , R 3 , R 4 , and R 5 represent hydrogen, halogen, an alkyl, alkenyl, aryl, alkoxy, aryloxy, nitro, cyano, hydroxy, acetyl, and/or diazo groups independently of each, and X represents BF 4 , Cl, F, SO 3 CH 3 , CO 2 CH 3 , PF 6 , ClO 2 CH 3 , or CIO 4 , comprising the following steps: (a) providing a benzenoid amide, which with the exception of the diazo function has the same substituents R 1 , R 2 , R 3 , R 4 , and R 5 as the benzenoid diazonium salt of the general formula (I), and hydrolytically cleaving the amide to form an amine or providing a corresponding amine, (b) diazotizing the amine thus obtained or provided with a nitrite, and (c) subsequently reacting the benzenoid diazonium salt with a coupling partner in the presence of a catalyst to form a cross-coupling product, wherein the coupling parter is represented by the general formula (II), R 6 , R 7 , and R 8 are the same or different and represent hydrogen, carboxyalkyl groups, carboxyaryl groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, wherein the groups can each contain Si, N, S, O, and or halogen atoms, or R 6 and R 7 with the double bound form an aromatic ring, which can be provided with R 8 and one to four further substituents, independently of each other, selected from the group comprising a straight-chain or branched (C 1 -C 6 ) alkyl group, a (C 3 -C 7 ) cycloalkyl group, a straight-chain or branched (C 1 -C 6 ) alkenyl group, a straight-chain or branched (C 1 -C 6 ) alkyoxy group, halogen, the hydroxy group, an amino, di(C 1 -C 6 ) alkylamino, nitro, acetyl, cyan, benzyl, 4-methoxybenzyl, 4-nitrobenzyl, phenyl, and 4-methoxyphenyl group and represents Y=H, —B(OR) 2 , —SnR 3 , —ZnR, —SiR 3 , or Mg (halogen), and wherein at least the steps (b) and (c) are performed without intermediate isolation of an intermediate product. According to said method, cross-couplings can be performed more simply and with improved yield without the hydroxyl group in aromatic reactants containing hydroxyl groups having to be provided with a protective group.

  该发明涉及一种根据通式(I)制备苯并重氮盐的交叉偶联产物的方法，其中基团R1、R2、R3、R4和R5代表氢、卤素、烷基、烯基、芳基、烷氧基、芳氧基、硝基、氰基、羟基、乙酰基和/或重氮基，X代表BF4、Cl、F、SO3CH3、CO2CH3、PF6、ClO2CH3或CIO4，包括以下步骤：(a)提供苯并酰胺，除了重氮功能外，具有通式(I)中苯并重氮盐相同的取代基R1、R2、R3、R4和R5，并水解裂解酰胺形成胺或提供相应的胺，(b)用亚硝酸盐重氮得到或提供的胺，(c)随后在催化剂存在下将苯并重氮盐与偶联配体反应形成交叉偶联产物，其中偶联配体由通式(II)表示，R6、R7和R8相同或不同，代表氢、羧基烷基、羧基芳基、烷基、芳基、烷氧基、芳氧基，其中基团可以包含Si、N、S、O和/或卤素原子，或R6和R7与双键形成芳香环，可提供R8和一个到四个进一步取代基，独立于彼此，选自包括直链或支链(C1-C6)烷基、(C3-C7)环烷基、直链或支链(C1-C6)烯基、直链或支链(C1-C6)烷氧基、卤素、羟基、氨基、二(C1-C6)烷基氨基、硝基、乙酰基、氰基、苄基、4-甲氧基苄基、4-硝基苄基、苯基和4-甲氧基苯基，表示Y=H、—B(OR)2、—SnR3、—ZnR、—SiR3或Mg(卤素)，至少步骤(b)和(c)在不中间分离中间产物的情况下执行。根据该方法，可以更简单地进行交叉偶联，并且在含有羟基的芳香反应物中无需提供保护基即可获得改进的产率。
• PROCESS FOR PREPARING TAPINAROF
  申请人：Dermavant Sciences GmbH

  公开号：US20190144367A1

  公开（公告）日：2019-05-16

  The present invention provides processes for the preparation of 3, 5-Dihydroxy-4-isopropyl-trans-stilbene or a salt or solvate thereof and novel intermediates used therein. In some embodiments the 3, 5-Dihydroxy-4-isopropyl-trans-stilbene is prepared from (E)-2-chloro-2-isopropyl-5-styrylcyclohexane-1,3-dione. Also disclosed are crystal forms of 3, 5-Dihydroxy-4-isopropyl-trans-stilbene or a salt or solvate thereof and pharmaceutical compositions comprising same.

  本发明提供了制备3,5-二羟基-4-异丙基-反-芪或其盐或溶剂化物的方法以及在其中使用的新颖中间体。在某些实施例中，3,5-二羟基-4-异丙基-反-芪是从(E)-2-氯-2-异丙基-5-苯乙烯基环己烷-1,3-二酮制备的。还公开了3,5-二羟基-4-异丙基-反-芪或其盐或溶剂化物的晶体形式以及包含相同的药物组合物。
• Light-Emitting Biomarker
  申请人：Renard Pierre-Yves

  公开号：US20090041669A1

  公开（公告）日：2009-02-12

  The invention concerns novel 1,2-dioxetane derivatives of general formula (I) as defined in the description, capable of emitting a detectable luminescent signal, their use in a method for detecting and/or quantizing a physical, chemical or biological, in particular enzymatic, phenomenon, as well as a kit for implementing said method.

  这项发明涉及一种新颖的1,2-二氧杂环戊烷衍生物，其一般式（I）如描述中所定义，能够发出可检测的发光信号，其用于检测和/或定量化物理、化学或生物学，特别是酶促现象的方法，以及用于实施该方法的试剂盒。
• [EN] METHODS OF ARENE ALKENYLATION<br/>[FR] PROCÉDÉS D'ALCÉNYLATION D'ARÈNE
  申请人：UNIV VIRGINIA PATENT FOUNDATION

  公开号：WO2021236764A1

  公开（公告）日：2021-11-25

  The present disclosure provides for a rhodium-catalyzed oxidative arene alkenylation from arenes and styrenes to prepare stilbene and stilbene derivatives. For example, the present disclosure provides for method of making arenes or substituted arenes, in particular stilbene and stilbene derivatives, from a reaction of an optionally substituted arene and/or optionally substituted styrene. The reaction includes a Rh catalyst or Rh pre-catalyst material and an oxidant, where the Rh catalyst or Rh catalyst formed Rh pre-catalyst material selectively functionalizes CH bond on the arene compound (e.g., benzene or substituted benzene).

  本公开提供了一种从芳烃和苯乙烯进行的铑催化氧化芳烯烯化反应，以制备联苯和联苯衍生物。例如，本公开提供了一种制备芳烃或取代芳烃的方法，特别是联苯和联苯衍生物，通过对可选取代的芳烃和/或可选取代的苯乙烯进行反应。该反应包括Rh催化剂或Rh前驱体材料和氧化剂，其中Rh催化剂或形成的Rh前驱体材料选择性地对芳烃化合物（例如苯或取代苯）上的CH键进行官能化。
• Sun protection compositions comprising semi-crystalline polymers and hollow latex particles
  申请人：Candau Didier

  公开号：US20090041691A1

  公开（公告）日：2009-02-12

  Topically applicable cosmetic/dermatological UV protection compositions having enhanced SPF contain at least one organic UV screening agent and/or at least one inorganic screening agent, such compositions also containing at least the following constituents (A) and (B): A) a semi-crystalline polymer which is solid at ambient temperature and has a melting point of greater than or equal to 30° C., containing a) a polymeric backbone and b) at least one crystallizable organic side chain and/or one crystallizable organic block forming part of the backbone of this said polymer, said polymer having a number-average molecular mass Mn of greater than or equal to 1,000, and B) hollow latex particles having a particle size ranging from 150 to 380 nm, formulated into a topically applicable, physiologically acceptable medium therefor.

  具有增强SPF的适用于化妆品/皮肤科的防紫外线保护组合物至少包含一种有机紫外线过滤剂和/或至少一种无机过滤剂，此类组合物还至少包含以下成分（A）和（B）： A）半结晶聚合物，室温下为固体，熔点大于或等于30°C，包含a）聚合骨架和b）至少一种可结晶有机侧链和/或作为该聚合物骨架一部分的可结晶有机块，该聚合物具有大于或等于1,000的数均分子质量Mn，以及 B）中空乳胶颗粒，粒径范围为150至380纳米，配制成适用于局部使用的、生理上可接受的介质。