N-(2-methylpropylidene)-2-propenyl-1-amine | 254428-45-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-(2-methylpropylidene)-2-propenyl-1-amine
• 英文别名: N-Allyl-N-isobutylideneamine；N-Allylisobutylideneamine；allyl-isobutyliden-amine；Isobutyraldehyd-allylamin；Allyl-isobutyliden-amin；isobutylidene-allylamine
• CAS: 254428-45-0
• 化学式: C₇H₁₃N
• 分子量: 111.187
• InChiKey: RUNIKZPZJNFNCX-SOFGYWHQSA-N

物化性质

• 沸点：
  117 °C(Press: 767 Torr)
• 密度：
  0.7880 g/cm3(Temp: 0 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  8.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  N-(2-methylpropylidene)-2-propenyl-1-amine 在 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 7.5h， 生成 N-(2-Methyl-1-propen-1-yl)-N-2-propen-1-ylcyclohexanemethanamine
  参考文献：
  名称：

  Lewis acid-promoted 3-aza-Cope rearrangement of N-alkyl-N-allyl enamines

  摘要：

  The 3-aza-Cope rearrangement of the N-alkyl-N-allylenamines derived from isobutyraldehyde, which proceeds thermally at 250-degrees-C, has been accelerated by a variety of electrophilic reagents to give gamma,delta-unsaturated imines. Protic acids, such as HCl (0.5 equiv), and the Lewis acidic reagents TiCl4 (0.1-0.2 equiv), Et2O.BF3 (0.5 equiv), and AlMe3 (1.0 equiv) produced complete [3,3] rearrangement of substrates at 111-degrees-C. By increasing the Lewis acidity of the aluminum reagents, this transformation was achieved at 50-degrees-C with ClAlMe2, Cl2AlMe, and methylaluminum bis(2,6-diphenylphenoxide). Reaction conditions were studied initially by GLC analysis of the N-isobutyl derivative. These optimum conditions were then used to obtain isolated yields of 59-99% for rearrangement and in situ LiAlH4 reduction of the analogous N-methylcyclohexyl substrate to the corresponding delta,epsilon-unsaturated amine. Substrates derived from 2-phenylpropanal, n-butanal, cyclohexanone, and cyclopentanone were used to examine the general effectiveness of HCl, TiCl4, and AlMe3 as reagents for acceleration of the [3,3] rearrangement. The most versatile and efficient reagent for promoting this reaction, AlMe3, produced overall yields of 83-96% for the two-step rearrangement and reduction of these substrates.

  DOI：

  10.1021/jo00028a016
• 作为产物：
  描述：

  异丁醛 、 丙烯胺 在 4 A molecular sieve 作用下， 以 乙醚 为溶剂， 以75%的产率得到N-(2-methylpropylidene)-2-propenyl-1-amine
  参考文献：
  名称：

  Lewis acid-promoted 3-aza-Cope rearrangement of N-alkyl-N-allyl enamines

  摘要：

  The 3-aza-Cope rearrangement of the N-alkyl-N-allylenamines derived from isobutyraldehyde, which proceeds thermally at 250-degrees-C, has been accelerated by a variety of electrophilic reagents to give gamma,delta-unsaturated imines. Protic acids, such as HCl (0.5 equiv), and the Lewis acidic reagents TiCl4 (0.1-0.2 equiv), Et2O.BF3 (0.5 equiv), and AlMe3 (1.0 equiv) produced complete [3,3] rearrangement of substrates at 111-degrees-C. By increasing the Lewis acidity of the aluminum reagents, this transformation was achieved at 50-degrees-C with ClAlMe2, Cl2AlMe, and methylaluminum bis(2,6-diphenylphenoxide). Reaction conditions were studied initially by GLC analysis of the N-isobutyl derivative. These optimum conditions were then used to obtain isolated yields of 59-99% for rearrangement and in situ LiAlH4 reduction of the analogous N-methylcyclohexyl substrate to the corresponding delta,epsilon-unsaturated amine. Substrates derived from 2-phenylpropanal, n-butanal, cyclohexanone, and cyclopentanone were used to examine the general effectiveness of HCl, TiCl4, and AlMe3 as reagents for acceleration of the [3,3] rearrangement. The most versatile and efficient reagent for promoting this reaction, AlMe3, produced overall yields of 83-96% for the two-step rearrangement and reduction of these substrates.

  DOI：

  10.1021/jo00028a016

文献信息

• Substituted 11-aminoundecanols
  申请人：Ciba-Geigy Corporation

  公开号：US04332969A1

  公开（公告）日：1982-06-01

  Novel substituted 11-aminoundecanols of the formula ##STR1## and a process for their preparation are described; in the formula, R.sub.1 and R.sub.3 independently of one another are hydrogen or alkyl having 1-8 C atoms and R.sub.2 and R.sub.4 independently of one another are alkyl having 1-8 C atoms, or R.sub.1 and R.sub.2 and/or R.sub.3 and R.sub.4 together with the bonding C atom form a cycloaliphatic ring having 4-8 C atoms, and R.sub.5 and R.sub.6 independently of one another are hydrogen or alkyl having 1-4 C atoms. The compounds of the formula I are valuable active compounds for combating plant pests.

  描述了一种新颖的替代品，其为式##STR1##的11-氨基十一醇，以及其制备方法；在该式中，R.sub.1和R.sub.3彼此独立地是氢或具有1-8个碳原子的烷基，R.sub.2和R.sub.4彼此独立地是具有1-8个碳原子的烷基，或者R.sub.1和R.sub.2和/或R.sub.3和R.sub.4与连接碳原子一起形成具有4-8个碳原子的环脂环，R.sub.5和R.sub.6彼此独立地是氢或具有1-4个碳原子的烷基。式I的化合物是用于对抗植物害虫的有价值的活性化合物。
• 1-Aza-1,5,9-cyclododecatrienes
  申请人：Ciba-Geigy Corporation

  公开号：US04213901A1

  公开（公告）日：1980-07-22

  Compounds of the formula ##STR1## and a process for their preparation by reacting azabutadienes with dienes, especially 1,3-butadiene, in the presence of catalysts are described. In the formula I, R.sub.1 and R.sub.3 independently of one another are hydrogen or alkyl having 1-8 C atoms and R.sub.2 and R.sub.4 independently of one another are alkyl having 1-8 C atoms, or R.sub.1 and R.sub.2 and/or R.sub.3 and R.sub.4 together with the bonding C atom form a cycloaliphatic ring having 4-8 C atoms, and R.sub.5 and R.sub.6 independently of one another are hydrogen or alkyl having 1-4 C atoms. The compounds of the formula I are valuable intermediates for the preparation of active compounds for combating plant pests.

  描述了公式##STR1##的化合物及其制备方法，方法是通过在催化剂存在下将氮丁二烯与二烯反应，特别是1,3-丁二烯。在公式I中，R.sub.1和R.sub.3彼此独立地是氢或具有1-8个碳原子的烷基，R.sub.2和R.sub.4彼此独立地是具有1-8个碳原子的烷基，或者R.sub.1和R.sub.2和/或R.sub.3和R.sub.4与连接的碳原子一起形成具有4-8个碳原子的环脂环，R.sub.5和R.sub.6彼此独立地是氢或具有1-4个碳原子的烷基。公式I的化合物是用于制备用于对抗植物害虫的活性化合物的有价值的中间体。
• Substituted 11-amino-undeca-4,8-dienal and 11-amino-undecanal
  申请人：Ciba-Geigy Corporation

  公开号：US04277621A1

  公开（公告）日：1981-07-07

  Novel substituted 11-amino-undeca-4,8-dienal and 11-amino-undecanal aldehyde-derivatives of the formulae Ia ##STR1## in which R.sub.1 to R.sub.6, Y and m are as defined in patent claim 1, and processes for their preparation are described. The compounds of the formulae Ia and Ib can be catalytically hydrogenated to novel 1,11-diaminoundecanes, which, in turn, can be used, for example, for the preparation of polycondensation products, in particular transparent polyamides, or as curing agents for epoxide resins.

  小说中替代11-氨基十一烯醛和11-氨基十一醛的衍生物的化学式Ia ##STR1##其中R.sub.1到R.sub.6、Y和m的定义如专利权要求1中所定义，并描述了它们的制备过程。化学式Ia和Ib的化合物可以通过催化氢化制备新型1,11-二氨基十一烷，进而可以用于制备聚酰胺等聚合产物，特别是透明聚酰胺，或用作环氧树脂的固化剂。
• Synthesis of 3,3-Difluoroazetidines
  作者：Norbert De Kimpe、Willem Van Brabandt

  DOI：10.1055/s-2006-948186

  日期：2006.8

  A high-yield synthesis of 3,3-difluoroazetidines was developed by a monochlorohydroalane reduction of 3,3-difluoroazetidin-2-ones. The latter compounds were conveniently synthesized by a Reformatsky-type reaction of aldimines with ethyl bromo­difluoroacetate.

  通过对 3,3-二氟氮杂环丁-2-酮进行单氯氢醛还原，开发出了一种高产率合成 3,3-二氟氮杂环丁的方法。后一种化合物是通过醛亚胺与溴二氟乙酸乙酯的 Reformatsky 型反应方便地合成的。
• 2-Aza-1,3-dienes
  申请人：Ciba-Geigy Corporation

  公开号：US04289905A1

  公开（公告）日：1981-09-15

  There are described compounds of the formula ##STR1## wherein R.sub.1 and R.sub.2 independently of one another represent alkyl having 1-8 C atoms, or together with the bond C atom they represent a cycloaliphatic ring having 4-8 C atoms, and R.sub.3 represents ethyl; or wherein R.sub.1 represents alkyl having 1-8 C atoms, R.sub.2 represents hydrogen, or alkyl having 1-8 C atoms, and R.sub.3 represents tertiary alkyl having 4-8 C atoms. The compounds of the formula I can be produced in a simple manner, in good to very good yields, by isomerisation of suitably substituted allylamines in an inert organic solvent and in the presence of a catalyst. The compounds of the formula I constitute valuable intermediates for producing active substances for combating plant pests.

  描述了化合物的公式为##STR1##其中R.sub.1和R.sub.2分别独立地表示具有1-8个C原子的烷基，或者与C原子的键结合形成具有4-8个C原子的环脂肪环，R.sub.3表示乙基; 或者其中R.sub.1表示具有1-8个C原子的烷基，R.sub.2表示氢，或者具有1-8个C原子的烷基，R.sub.3表示具有4-8个C原子的三级烷基。公式I的化合物可以通过在惰性有机溶剂中和催化剂的存在下适当取代的烯丙胺异构化而简单地制备，并且收率良好至非常好。公式I的化合物是生产用于对抗植物害虫的活性物质的有价值的中间体。