1-(o-tolyl)azepane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(o-tolyl)azepane
• 英文别名: 1-(2-Methylphenyl)azepane
• 化学式: C₁₃H₁₉N
• 分子量: 189.301
• InChiKey: AONGHEXDIMKNKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis(methoxycarbonyl)(phenyliodinio)methanide 、 1-(o-tolyl)azepane 在 calcium hydride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.02h， 以53%的产率得到dimethyl 4-methyl-6,7,8,9,10,10a-hexahydro-11H-azepino[1,2-a]indole-11,11-dicarboxylate
  参考文献：
  名称：

  碘鎓叶立德直接环化芳基叔胺

  摘要：

  本文描述的是简单的叔芳基胺与碘鎓碘化物的直接环化反应，可导致广泛的N杂环。与已知的碘鎓碘化物的反应性完全不同，本文报道的发现是碘鎓碘化物能够裂解C（sp 3）-H键并接受叔芳基胺的两个氢原子，从而诱导了新的环化过程。无需过渡金属催化剂即可进行这种转化，从而无需对胺进行预改性或使用其他引发剂/氧化剂。

  DOI：

  10.1002/anie.201800389
• 作为产物：
  描述：

  环己亚胺 、 2-氯甲苯 在 [IPr*·H][Pd(η3-cin)Cl₂] 、 potassium tert-butylate 作用下， 反应 2.0h， 以99%的产率得到1-(o-tolyl)azepane
  参考文献：
  名称：

  Palladate Precatalysts for the Formation of C–N and C–C Bonds

  摘要：

  A series of imidazolium-based palladate precatalysts has been synthesized and the catalytic activity of these air- and moisture-stable complexes evaluated as a function of the nature of the imidazolium counterion. These precatalysts can be converted under catalytic conditions to Pd-NHC species capable of enabling the Buchwald-Hartwig aryl amination and the alpha-arylation of ketones. Both reactions can be carried out efficiently under very mild operating conditions. The effectiveness of the protocol was tested on functionality-laden substrates.

  DOI：

  10.1021/acs.organomet.9b00326

文献信息

• C(sp³)–H dehydrogenation and C(sp²)–H alkoxy carbonylation of inactivated cyclic amines towards functionalized N-heterocycles
  作者：Yan He、Fang Wang、Xinying Zhang、Xuesen Fan

  DOI：10.1039/c6cc10227a

  日期：——

  A novel and efficient synthesis of tetrahydropyridine-, dihydropyrrole-, and tetrahydroazepine-3-carboxylates via cascade reactions of cyclic amines with CO and alcohols is presented. To our knowledge, this should be the first example in which functionalized N-heterocycles were prepared through Pd-catalyzed C(sp3)-H dehydrogenation and C(sp2)-H carbonylation of cyclic amines.

  通过环胺与CO和醇的级联反应，提出了一种新颖而有效的四氢吡啶-，二氢吡咯-和四氢氮杂-3-羧酸酯的合成方法。据我们所知，这应该是第一个通过钯催化环胺的C（sp 3）-H脱氢和C（sp 2）-H羰基化制备N杂环的例子。
• Direct α-Alkenylation of Cyclic Amines with Maleimides through Fe(III)-Catalyzed C(sp³)–H/C(sp²)–H Cross Dehydrogenative Coupling
  作者：Fang Wang、Qianting Zhou、Xinying Zhang、Xuesen Fan

  DOI：10.1021/acs.joc.1c01198

  日期：2021.9.3

  a novel and efficient α-C(sp3)–H alkenylation of cyclic amines with maleimides. Mechanistically, this C(sp3)–H/C(sp2)–H cross dehydrogenative coupling (CDC) reaction involves a cascade procedure including oxidative α-amino radical formation from the cyclic amine substrate and nucleophilic addition of the in situ formed α-amino radical onto the electron-deficient carbon–carbon double bond of maleimide

  本文提出了一种新颖且有效的 α-C(sp 3 )-H 环胺与马来酰亚胺的烯基化。从机制上讲，这个 C(sp 3 )–H/C(sp 2)–H 交叉脱氢偶联 (CDC) 反应涉及一个级联过程，包括从环胺底物形成氧化性 α-氨基自由基和原位形成的 α-氨基自由基亲核加成到马来酰亚胺的缺电子碳-碳双键上其次是氧化和β-消除。值得注意的是，这种直接的 α-功能化为传统的离子反应模式提供了一种有效的替代方法，其中形成亚胺或亚胺中间体与除缺电子的那些之外的富电子偶联伙伴反应。总的来说，该方法具有易得且结构多样的底物、绿色经济的催化剂、独特的反应途径、温和的反应条件、高效率和优异的原子经济性等特点。3 )–H 活化和功能化。
• SMALL MOLECULE INHIBITORS OF THE NUCLEAR TRANSLOCATION OF ANDROGEN RECEPTOR FOR THE TREATMENT OF CASTRATION-RESISTANT PROSTATE CANCER
  申请人：University of Pittsburgh - Of the Commonwealth System of Higher Education

  公开号：US20160257657A1

  公开（公告）日：2016-09-08

  A compound, or a pharmaceutically acceptable salt or ester thereof, according to formula I: R 20 —(Z) b —(Y) c —(R 21 ) a —(X) d —R 22 —R 23 wherein R 20 is aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, aryloxy, a thio-containing group, or a seleno-containing group; Z is alkanediyl, substituted alkanediyl, cycloalkanediyl, or substituted cycloalkanediyl; Y is S, O, S(═O), —S(═O)(═O)—, or NR 10 , wherein R 10 is H or alkyl; R 21 is alkanediyl, substituted alkanediyl, cycloalkanediyl, substituted cycloalkanediyl alkadienyl, substituted alkadienyl, alkatrienyl, substituted alkatrienyl; X is —C(═O)—, —S(═O)(═O)—, or —N(H)C(═O)—; R 22 includes at least one divalent amino radical; R 23 is aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, aryloxy, a thio-containing group, or a seleno-containing group; a, b, c, and d independently are 0 or 1.

  根据公式I，化合物或其药学上可接受的盐或酯，其中R20为芳基，取代芳基，杂环芳基，取代杂环芳基，杂环烷基，取代杂环烷基，烷氧基，芳基氧基，含硫基或含硒基；Z为烷二基，取代烷二基，环烷二基或取代环烷二基；Y为S，O，S(═O)，—S(═O)(═O)—或NR10，其中R10为H或烷基；R21为烷二基，取代烷二基，环烷二基，取代环烷二基，烯丙基，取代烯丙基，烯三基或取代烯三基；X为—C(═O)—，—S(═O)(═O)—或—N(H)C(═O)—；R22至少包括一个二价氨基基团；R23为芳基，取代芳基，杂环芳基，取代杂环芳基，杂环烷基，取代杂环烷基，烷氧基，芳基氧基，含硫基或含硒基；a、b、c和d独立地为0或1。
• COMPOUNDS FOR TREATING PROSTATE CANCER
  申请人：UNIVERSITY OF PITTSBURGH - OF THE COMMONWEALTH SYSTEM OF HIGHER EDUCATION

  公开号：US20160264540A1

  公开（公告）日：2016-09-15

  A compound, or a pharmaceutically acceptable salt or ester thereof, having a formula I of: R 20 —(Z) b —(Y) c —(R 21 ) a —X—R 22 -R 23 wherein R20 is an aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, aryloxy, a silyl-containing group, a boryl-containing group, a phosphine-containing group, amino, a thio-containing group, a seleno-containing group, halide, or a nitro-containing group; Z is alkanediyl, substituted alkanediyl, cycloalkanediyl, or substituted cycloalkanediyl; Y is S, O, or NR 10 , wherein R 10 is H or alkyl; R 21 is alkanediyl, substituted alkanediyl, cycloalkanediyl, substituted cycloalkanediyl, alkadienyl, substituted alkadienyl, alkatrienyl, substituted alkatrienyl; X is —C(=0)- or —S(=0)(=0)-; R 22 is a moiety that includes at least one divalent amino radical; R 23 is an aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, aryloxy, a silyl-containing group, a boryl-containing group, a phosphine-containing group, amino, a thio-containing group, a seleno-containing group, halide, or a nitro-containing group; a is 0 or 1; b is 0 or 1; and c is 0 or 1; provided that if X is —C(=0)- then Y is not S.

  化合物，或其药学上可接受的盐或酯，其具有公式I：R20—(Z)b—(Y)c—(R21)a—X—R22-R23，其中R20是芳基，取代芳基，杂环芳基，取代杂环芳基，杂环烷基，取代杂环烷基，烷氧基，芳氧基，含硅基团，含硼基团，含膦基团，氨基，含硫基团，含硒基团，卤素或含硝基团；Z是烷二基，取代烷二基，环烷二基或取代环烷二基；Y是S，O或NR10，其中R10是H或烷基；R21是烷二基，取代烷二基，环烷二基，取代环烷二基，烯二基，取代烯二基，烯三基，取代烯三基；X是—C（=0）-或—S（=0）（=0）-；R22是至少包含一个双价氨基基团的基团；R23是芳基，取代芳基，杂环芳基，取代杂环芳基，杂环烷基，取代杂环烷基，烷氧基，芳氧基，含硅基团，含硼基团，含膦基团，氨基，含硫基团，含硒基团，卤素或含硝基团；a为0或1；b为0或1；c为0或1；但如果X是—C（=0）-，则Y不是S。
• Oil extended rubber and rubber composition
  申请人：JSR Corporation

  公开号：EP0992537A1

  公开（公告）日：2000-04-12

  An oil extended rubber comprising 100 parts by weight of (A) an amino group-containing copolymer rubber of a conjugated diolefin and an aromatic vinyl compound which contains bonded amino groups in the amount of 0.0025-0.20 mmol/g polymer, and 10-100 parts by weight of (B) an extensible oil. Carbon black, silica, a mixture of carbon black and silica, or a carbon-silica dual-phase-filler can be homogeneously dispersed in the oil extended rubber. Vulcanized products obtained by vulcanizing the rubber exhibits well-balanced improved properties such as wet skid properties, low hysteresis loss properties, abrasion resistance, and breaking strength, and are useful as a tread material for low fuel consumption tires, large tires, and high performance tires.

  一种油延橡胶，由 100 重量份的(A)共轭二烯烃和芳香族乙烯基化合物的含氨基的共聚橡胶和 10-100 重量份的(B)延展性油组成，(A)共轭二烯烃和芳香族乙烯基化合物的含氨基的共聚橡胶含有键合氨基的量为 0.0025-0.20 mmol/g，(B)延展性油含有键合氨基的量为 0.0025-0.20 mmol/g。碳黑、白炭黑、碳黑和白炭黑混合物或碳硅双相填料可均匀地分散在延展性油橡胶中。通过硫化橡胶得到的硫化产品具有均衡的改良特性，如湿滑特性、低滞后损失特性、耐磨性和断裂强度，可用作低油耗轮胎、大型轮胎和高性能轮胎的胎面材料。