3,5-双[(1S)-1-乙氧基乙基]-1,2,4-三唑-4-胺 | 652538-45-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 3,5-双[(1S)-1-乙氧基乙基]-1,2,4-三唑-4-胺
• 英文名称: 3,5-bis[(1S)-1-ethoxyethyl]-4H-1,2,4-triazol-4-amine
• 英文别名: (S,S)-4-amino-3,5-bis(1-ethoxyethyl)-1,2,4-triazole；3,5-bis[(1S)-1-ethoxyethyl]-1,2,4-triazol-4-amine
• CAS: 652538-45-9
• 化学式: C₁₀H₂₀N₄O₂
• 分子量: 228.294
• InChiKey: FVENUMQIFTUKLW-YUMQZZPRSA-N

物化性质

• 沸点：
  365.8±52.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  75.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,5-双[(1S)-1-乙氧基乙基]-1,2,4-三唑-4-胺 、 乙二醛-1,1-二甲基乙缩醛溶液 在 对甲苯磺酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 3.0h， 以95%的产率得到N-[(1E)-2,2-dimethoxyethylidene]-3,5-bis[(1S)-1-ethoxyethyl]-4H-1,2,4-triazol-4-amine
  参考文献：
  名称：

  Synthesis of chiral primary amines: diastereoselective alkylation of N-[(1E)-alkylidene]-3,5-bis[(1S)-1-methoxyethyl]-4H-1,2,4-triazol-4-amines and N4–Nexocyclic bond cleavage in the resulting 1,2,4-triazol-4-alkylamines

  摘要：

  Enantiomerically pure 3,5-bis[(1S)-1-methoxyethyl]-4H-1,2,4-triazol-4-amine 14a and 3,5-bis[(1S)-1-ethoxyethyl]-4H-1,2,4-triazol-4-amine 14b were used as chiral auxiliaries to obtain enantiomerically enriched alpha-aminoacetals, primary alkyl and arylalkyl amines (ee ranging from 40% to 90%). The different stages of the process were imine formation from the corresponding aldehydes, diastereoselective addition of a Grignard reagent, quaternization of the triazole auxiliary and cleavage of the N-4-N-exocylic bond by LiBH4. The mechanism of the cleavage of the N-4-N-exocyclic bond is supported by the use of deuterated metal hydride. The absolute configurations of the new stereogenic centres were established by X-ray analyses of the enantiomerically pure stereomers isolated by semi-preparative liquid chromatography on a chiral support. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.12.015
• 作为产物：
  描述：

  (S,S)-4-amino-3,5-bis(1-hydroxyethyl)-1,2,4-triazole 、 对甲苯磺酸乙酯 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以70%的产率得到3,5-双[(1S)-1-乙氧基乙基]-1,2,4-三唑-4-胺
  参考文献：
  名称：

  Synthesis of chiral primary amines: diastereoselective alkylation of N-[(1E)-alkylidene]-3,5-bis[(1S)-1-methoxyethyl]-4H-1,2,4-triazol-4-amines and N4–Nexocyclic bond cleavage in the resulting 1,2,4-triazol-4-alkylamines

  摘要：

  Enantiomerically pure 3,5-bis[(1S)-1-methoxyethyl]-4H-1,2,4-triazol-4-amine 14a and 3,5-bis[(1S)-1-ethoxyethyl]-4H-1,2,4-triazol-4-amine 14b were used as chiral auxiliaries to obtain enantiomerically enriched alpha-aminoacetals, primary alkyl and arylalkyl amines (ee ranging from 40% to 90%). The different stages of the process were imine formation from the corresponding aldehydes, diastereoselective addition of a Grignard reagent, quaternization of the triazole auxiliary and cleavage of the N-4-N-exocylic bond by LiBH4. The mechanism of the cleavage of the N-4-N-exocyclic bond is supported by the use of deuterated metal hydride. The absolute configurations of the new stereogenic centres were established by X-ray analyses of the enantiomerically pure stereomers isolated by semi-preparative liquid chromatography on a chiral support. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.12.015

文献信息

• [EN] PROCESS FOR THE PREPARATION OF PRIMARY AMINES<br/>[FR] PROCEDE DE PREPARATION D'AMINES PRIMAIRES
  申请人：CLARIANT FRANCE SA

  公开号：WO2004013081A1

  公开（公告）日：2004-02-12

  Process for the preparation of primary amines of formula (I): on enclosed where R3 represents an alkyl, cycloalkyl or aralkyl group, by reaction of a triazolium salt of formula (II): (formula see on enclosed paper version) where R1 and R2 represent hydrogen or an alkyl, aralkyl or aryl group, R4 represents an alkyl or aralkyl group or a residue of an organic polymer functionalized by an alkylating group, and A- represents a halogen, alkylsulphonate, arylsulphonate, alkyl sulphate, hydrogensulphate, hemisulphate, perchlorate or hydroxide, with a hydride, in order to obtain an amine of formula (I), which is isolated, if desired, and intermediates.

  制备式(I)的主要胺的过程：通过将式(II)的三唑盐与氢化物反应（式子见附上的纸张版本），其中R1和R2代表氢或烷基、芳基烷基或芳基，R4代表烷基或芳基烷基或被烷基化基团功能化的有机聚合物残基，A-代表卤素、烷基磺酸盐、芳基磺酸盐、烷基硫酸盐、氢硫酸盐、半硫酸盐、高氯酸盐或氢氧化物，其中R3代表烷基、环烷基或芳基烷基。最终得到式(I)的胺，可隔离，如果需要，还有中间体。
• Process for the preparation of primary amines
  申请人：Serradeil Albalat Muriel

  公开号：US20050240059A1

  公开（公告）日：2005-10-27

  Process for the preparation of primary amines of formula (I): where R3 represents an alkyl, cycloalkyl or aralkyl group, by reaction of a triazolium salt of formula (II): where R1 and R2 represent hydrogen or an alkyl, aralkyl or aryl group, R4 represents an alkyl or aralkyl group or a residue of an organic polymer functionalized by an alkylating group, and A − represents a halogen, alkylsulphonate, arylsulphonate, alkyl sulphate, hydrogensulphate, hemisulphate, perchlorate or hydroxide, with a hydride, in order to obtain an amine of formula (I), which is isolated, if desired, and intermediates.

  制备式（I）的初级胺的过程：其中R3代表烷基，环烷基或芳基烷基团，通过式（II）的三唑盐的反应获得，其中R1和R2代表氢或烷基，芳基烷基或芳基团，R4代表烷基或芳基烷基团或被烷基化基团功能化的有机聚合物残基，A-代表卤素，烷基磺酸盐，芳基磺酸盐，烷基硫酸盐，氢硫酸盐，半硫酸盐，高氯酸盐或氢氧化物，与氢化物反应，以获得式（I）的胺，如果需要，则分离中间体。
• PROCESS FOR THE PREPARATION OF PRIMARY AMINES
  申请人：Clariant (France)

  公开号：EP1527041A1

  公开（公告）日：2005-05-04
• US7220883B2
  申请人：——

  公开号：US7220883B2

  公开（公告）日：2007-05-22