bis-(3-methyl-[2]thienyl)-methane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: bis-(3-methyl-[2]thienyl)-methane
• 英文别名: Bis-(3-methyl-[2]thienyl)-methan；3-Methyl-2-[(3-methyl-2-thienyl)methyl]thiophene；3-methyl-2-[(3-methylthiophen-2-yl)methyl]thiophene
• 化学式: C₁₁H₁₂S₂
• 分子量: 208.348
• InChiKey: ZLJYGYFEWDYXAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  三聚甲醛 、 3-甲基噻吩 在 氢氟酸 作用下， 生成 bis-(3-methyl-[2]thienyl)-methane
  参考文献：
  名称：

  The Synthesis and Oxidation of 2,2'-Methylene-bis-(5-acetylthiophene)

  摘要：

  DOI：

  10.1021/ja01147a117

文献信息

• Method for preparing n-pyridyl-n-thenyl alkylene diamines
  申请人：ABBOTT LAB

  公开号：US02556566A1

  公开（公告）日：1951-06-12

  Diamines of the general formula (wherein R1 and R2 each represent hydrogen or an alkyl group of 1-4 carbon atoms, A represents an alkylene group of 2-11 carbon atoms, and R3 and R4 represent alkyl or aralkyl groups or may be joined to form a ring, and together contain a total of not more than 11 carbon atoms) are manufactured by treating at reaction temperatures, in the presence of a solvent which is or contains an acid-binding agent, an a -(R3,R4-aminoalkylamino)-pyridine with an a -halomethylthiophene, or an N-(a -thenyl) - N1 : N1 - R3,R4 - alkylenediamin with an a -halopyridine. The reaction is preferably carried out in an inert hydrocarbon solvent in the presence of an alkali metal amide or hydride. The products are useful as chemical intermediates, and in some cases themselves possess physiological activity, e.g. some have anti-histaminic and some local an sthetic properties. They may be converted into salts, e.g. hydrohalides, sulphates, phosphates, oxalates, succinates, fumarates, maleates, tartrates, gluconates or citrates. In examples: (1) N-(a -pyridyl)-N1 : N1-dimethyl- or -diethyl-ethylenediamine is refluxed with a -thenyl chloride in benzene in the presence of sodium hydride to produce N - (a - pyridyl) - N - (a 1 - thenyl) - N1 : N1-dimethyl- or -diethyl-ethylenediamine; (2) N - (a - pyridyl) - N1 : N1 - dimethylethylenediamine is refluxed with b -methyl-a -thenyl chloride in toluene in the presence of sodamide, yielding N - (a - pyridyl) - N - (b 1 - methyl - a 1 - thenyl) - N1 : N1 - dimethylethylenediamine; (3) N - (g - methyl - a - pyridyl) - N1 : N1 - dimethylethylenediamine is reacted as in (1) to form N - (g - methyl - a - pyridyl) - N - (a 1 - thenyl) - N1 : N1 - dimethylethylenediamine. A list of additional products is given. Specification 606,181 is referred to. a -(R3,R4-Aminoalkylamino)-pyridines are obtainable by reacting, in an inert hydrocarbon solvent in the presence of an alkali metal amide or hydride, an a -aminopyridine with an o -R3,R4-aminoalkyl halide (e.g. a -aminopyridine or its g -methyl derivative with b -dimethylaminoethyl chloride), or by reacting an a -halopyridine with an N : N-R3,R4-alkylene diamine (e.g. a -bromopyridine with N : N-dimethylethylenediamine in pyridine). N - (a - Thenyl) - N1 : N1 - R3,R4 - alkylenediamines are obtainable by reacting an a -halomethylthiophene with an N : N-R3,R4-alkylenediamine in pyridine or in an inert solvent in the presence of an alkali metal amide or hydride. b -Methyl-a -thenyl chloride is obtainable by treating b -methylthiophene with aqueous formaldehyde and hydrogen chloride. The Specification as open to inspection under Sect. 91 comprises also the manufacture of compounds of the general formula above in which A may be a hydrocarbon group other than alkylene, and R3 and R4 may be hydrogen, and the use of the following additional methods of preparation: (a) the process of Specification 673,633; (b) reaction of a dialkylamine with a compound containing chlorine, bromine, iodine or a hydroxy group in place of the group NR3R4; (c) the action of alkyl halides, sulphates or sulphonates on a compound containing NH2 in place of NR3R4 (obtainable by reduction of the appropriate compound containing a nitro or cyano group). An example of (a) is given. This subject-matter does not appear in the Specification as accepted. Reference has been directed by the Comptroller to Specification 675,266.

  通式的二胺（其中R1和R2各自代表氢或1-4个碳原子的烷基，A代表2-11个碳原子的亚烷基，R3和R4代表烷基或芳烷基，或者可以连接形成环，总共含有不超过11个碳原子）通过在反应温度下，在含有或作为酸结合剂的溶剂存在下，将α-(R3,R4-氨基烷基氨基)吡啶与α-卤甲基噻吩或N-(α-噻吩基)-N1:N1-R3,R4-亚烷基二胺与α-卤吡啶反应制备。反应优选在惰性烃溶剂中，在碱金属氨基或氢化物存在下进行。这些产品作为化学中间体有用，并且在某些情况下本身具有生理活性，例如一些具有抗组胺和局部麻醉特性。它们可以转化为盐，例如氢卤酸盐、硫酸盐、磷酸盐、草酸盐、琥珀酸盐、富马酸盐、马来酸盐、酒石酸盐、葡萄糖酸盐或柠檬酸盐。例如：(1) N-(α-吡啶基)-N1:N1-二甲基或二乙基乙二胺与α-噻吩基氯在苯中在氢化钠存在下回流，产生N-(α-吡啶基)-N-(α1-噻吩基)-N1:N1-二甲基或二乙基乙二胺；(2) N-(α-吡啶基)-N1:N1-二甲基乙二胺与β-甲基-α-噻吩基氯在甲苯中在氨基钠存在下回流，产生N-(α-吡啶基)-N-(β1-甲基-α1-噻吩基)-N1:N1-二甲基乙二胺；(3) N-(γ-甲基-α-吡啶基)-N1:N1-二甲基乙二胺如(1)所述反应，形成N-(γ-甲基-α-吡啶基)-N-(α1-噻吩基)-N1:N1-二甲基乙二胺。给出了其他产品的列表。参考了说明书606,181。α-(R3,R4-氨基烷基氨基)吡啶可以通过在惰性烃溶剂中，在碱金属氨基或氢化物存在下，将α-氨基吡啶与邻-R3,R4-氨基烷基卤化物（例如α-氨基吡啶或其γ-甲基衍生物与β-二甲氨基乙基氯）反应，或者通过将α-卤吡啶与N:N-R3,R4-亚烷基二胺（例如α-溴吡啶与N:N-二甲基乙二胺在吡啶中）反应获得。N-(α-噻吩基)-N1:N1-R3,R4-亚烷基二胺可以通过在吡啶中或在惰性溶剂中在碱金属氨基或氢化物存在下，将α-卤甲基噻吩与N:N-R3,R4-亚烷基二胺反应获得。β-甲基-α-噻吩基氯可以通过用甲醛水溶液和氢氯酸处理β-甲基噻吩获得。根据第91节，公开的说明书还包括上述通式化合物A可以是除亚烷基以外的烃基，R3和R4可以是氢的制造，以及使用以下额外的制备方法：(a) 说明书673,633的工艺；(b) 二烷基胺与含有氯、溴、碘或羟基代替NR3R4的化合物的反应；(c) 烷基卤化物、硫酸盐或磺酸盐对含有NH2代替NR3R4的化合物的反应（通过还原含有适当硝基或氰基的化合物获得）。给出了(a)的一个例子。这一主题内容在已接受的说明书中没有出现。审计长已指示参考说明书675,266。