dimethyl (4R,5R)-2-(1-bromoethyl)-2-(6-methoxynaphthalen-2-yl)-1,3-dioxolane-4,5-dicarboxylate | 281223-31-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: dimethyl (4R,5R)-2-(1-bromoethyl)-2-(6-methoxynaphthalen-2-yl)-1,3-dioxolane-4,5-dicarboxylate
• CAS: 281223-31-2
• 化学式: C₂₀H₂₁BrO₇
• 分子量: 453.287
• InChiKey: MDNOCWNFUCBFPY-YSGDOOFJSA-N

物化性质

• 沸点：
  535.6±45.0 °C(Predicted)
• 密度：
  1.436±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  dimethyl (4R,5R)-2-(1-bromoethyl)-2-(6-methoxynaphthalen-2-yl)-1,3-dioxolane-4,5-dicarboxylate 在 silver tetrafluoroborate 、 水 、 溴 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 18.75h， 生成 (2S,3R)-dimethyl 2-(((S)-2-(5-bromo-6-methoxynaphthalen-2-yl)propanoyl)oxy)-3-hydroxysuccinate
  参考文献：
  名称：

  Tartaric acid, an efficient chiral auxiliary: new asymmetric synthesis of 2-alkyl-2-arylacetic acids

  摘要：

  DOI：

  10.1021/jo00390a013
• 作为产物：
  描述：

  (4R,5R)-2-ethyl-2-(6-methoxy-2-naphthyl)-1,3-dioxolane-4,5-dicarboxylic acid dimethyl ester 以13%的产率得到
  参考文献：
  名称：

  GIORDANO, CLAUDIO;CASTALDI, GRAZIANO;UGGERI, FULVIO;CAVICCHIOLI, SILVIA

  摘要：

  DOI：

文献信息

• Enantiomerically Pure 2-Bromoalkyl Aryl Ketones
  作者：Graziano Castaldi、Claudio Giordano

  DOI：10.1055/s-1987-28166

  日期：——

  The non-conventional hydrolysis of mixtures of diastereoisomeric α-bromo acetals, available in high yields, high diastereomeric excesses, and in large amounts, allows the synthesis and the full characterization of enantiomerically pure (2S)- and (2R)-bromoalkyl aryl ketones. The developed methodology represents the first route to enantiomerically pure 2-bromoalkyl aryl ketones of (2R) and (2S) configurations.

  非传统的水解法对混合的二对映异构体α-溴醛的处理，可在高产率、高对映体过量和大量条件下实现，允许合成和全面表征对映体纯的(2S)-和(2R)-溴烷基芳基酮。所开发的方法代表了获得(2R)和(2S)构型的对映体纯2-溴烷基芳基酮的第一条途径。
• Optically active ketals, processes for their preparation and their use in the synthesis of apha-arylakanoic acids
  申请人：ZAMBON S.p.A.

  公开号：EP0158255A2

  公开（公告）日：1985-10-16

  Compounds of formula wherein Ar represents an optically substituted aryl group, R represents a C,-C4 alkyl; R, and R2, equal to or different from each other, represent hydroxy, O-M+, OR3 or N R4 R5 group, R3 represents a C,-C24 alkyl, a C3-C6 cycloalkyl, a phenyl or a benzyl; M+ represents the cation of an alkaline metal; R4 and Rs, equal to or different from each other, represent a hydrogen atom, a C1-C4 alkyl, a C5-C6 cycloalkyl, a (CH2)n-CH20H group with n=1, 2 or 3, or R4 and R5 together are a group (CH2)m with m=4 or 5, a group -CH2-CH2R6-CH2-CH2- in which R6 is an oxygen atom, an N-H or N-(C1-C4) alkyl group; X represents a chlorine, bromine or iodine atom, an hydroxy, acyloxy, alkylsulphonyloxy or arylsulphonyloxy group; the carbon atoms marked by an asterisk are both contemporaneously in the R or S configuration, are described. The preparation of the compound of formula I by ketalization or by trans-ketalization with tartaric acid derivatives and their rearrangement into alpha-arylalkanoic acids is described too.

  式中的化合物 式中 Ar 代表光学取代的芳基 R 代表 C,-C4 烷基； 代表羟基、O-M+、OR3 或 N R4 R5 基团、 R3 代表 C,-C24烷基、C3-C6 环烷基、苯基或苄基； M+ 代表碱金属的阳离子； R4和Rs，彼此相同或不同，代表氢原子、C1-C4烷基、C5-C6环烷基、n=1、2或3的(CH2)n-CH20H基团，或R4和R5一起是m=4或5的(CH2)m基团、R6为氧原子的-CH2-CH2R6-CH2-CH2-基团、N-H或N-(C1-C4)烷基； X 代表氯、溴或碘原子，羟基、酰氧基、烷基磺酰氧基或芳基磺酰氧基；用星号标出的碳原子同时处于 R 或 S 构型。 此外，还介绍了通过与酒石酸衍生物酮化或反酮化以及将其重排为α-芳基烷酸来制备式 I 化合物的方法。
• Process for the preparation of optically active alpha-arylalkanoic acids and intermediates thereof
  申请人：ZAMBON S.p.A.

  公开号：EP0158913A2

  公开（公告）日：1985-10-23

  A new enantioselective process is described for preparing optically active alpha-arylalkanoic acids by: a) halogenation on the aliphatic carbon atom alpha to the ketal group, of ketals of formula in which Ar represents an aryl, optically substituted; R represents a C1-C4 alkyl; R, and R2, represent a hydroxy, a O-M+, OR3 or NR4R5 group; the carbon atoms indicated by an asterisk both simultaneously are in (R) or (S) configuration.This reaction is diastereoselective, so that a misture of alpha-haloketals is obtained in which one of the two epimers prevails, and generally strongly prevails, over the other. b) rearrangement of the haloketals of formula in which X is CI, Br or I to alpha-arylalkanoic acids in a single stage or in two successive stages, by way of esters of formula The compounds (A) and (C) are all new compounds. The rearrengement step (b) may be performed under new, inventive conditions. The esters of formula (C) have pharmacological activity analogous to that of the corresponding alpha-arylalkanoic acids.

  介绍了一种通过以下方法制备光学活性α-芳基烷酸的对映体选择性新工艺： a) 卤化式如下的酮的脂肪族碳原子α到酮基 其中 Ar 代表被光学取代的芳基； R 代表 C1-C4 烷基； R 和 R2 代表羟基、O-M+、OR3 或 NR4R5。 基团；星号表示的碳原子同时在 该反应具有非对映选择性。 该反应具有非对映选择性，因此可以得到α-卤代金属的畸变体。 该反应具有非对映选择性，因此可以得到α-卤代缩酮的混合物。 该反应具有非对映选择性，因此在得到的α-卤代金属错置物中，两种表聚物中的一种占优势，而且通常比另一种强。 b) 式中α-卤代金属的重排 式中 X 为 CI、Br 或 I 的卤代烃与 α-芳基烷酸在一个阶段或连续两个阶段的重排，通过式中的酯 化合物(A)和(C)均为新化合物。重整步骤 (b) 可在新的创造性条件下进行。 式（C）的酯类具有类似于相应α-芳基烷酸的药理活性。
• Process for the preparation of (6-methoxy-2-naphthyl)-(1-bromoethyl)-ketone and its derivatives
  申请人：ZAMBON S.p.A.

  公开号：EP0203557A1

  公开（公告）日：1986-12-03

  A process is described for the preparation of (6-methoxy-2-naphthyl)- (1-bromoethyl)-ketone or ketals thereof (I), by selective debromination of (5-bromo-6-methoxy-2-naphthyl) -(1-bromoethyl)- ketone or ketals thereof (III) by means of a bromine acceptor in the presence of an acid and of an inert organic solvent. The bromine acceptor is preferably a phenol, a phenol ether or an aromatic ketone. The acid is preferably a hydrogen halide.

  本发明描述了一种制备 (6-甲氧基-2-萘基)-(1-溴乙基)-酮或其酮类 (I) 的工艺，其方法是在酸和惰性有机溶剂存在下，利用溴受体对 (5-溴-6-甲氧基-2-萘基)-(1-溴乙基)-酮或其酮类 (III) 进行选择性脱溴。溴受体最好是苯酚、苯酚醚或芳香族酮。酸最好是卤化氢。
• Process for preparing optically active alpha-haloalkyl-arylketones
  申请人：ZAMBON S.p.A.

  公开号：EP0217376A2

  公开（公告）日：1987-04-08

  A process is described for preparing alpha-haloalkyl-aryl-­ketones, comprising reacting a substantially anhydrous strong acid with a ketal of formula in which Ar, R, R₁, R₂ and X have the meanings given in the description.

  本发明描述了一种制备α-卤代烷基芳基酮的工艺，包括使基本无水的强酸与式 其中 Ar、R、R₁、R₂ 和 X 的含义如描述中所给。