1,1,3,4-四甲基-2-茚酮 | 5689-12-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 中文名称: 1,1,3,4-四甲基-2-茚酮
• 英文名称: 1,1,3,3-tetramethylindane-2-one
• 英文别名: 1,1,3,3-tetramethyl-2-indanone；1,1,3,3-Tetramethyl-2-indanon；1,1,3,3-tetramethylinden-2-one
• CAS: 5689-12-3
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: KBFUPRLHCWUTGK-UHFFFAOYSA-N

物化性质

• 熔点：
  76℃ (methanol )
• 沸点：
  108-112℃ (15 Torr)
• 稳定性/保质期：
  存在于主流烟气中。

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,1,3,4-四甲基-2-茚酮 在 盐酸 、 sodium hydroxide 、 硫化氢 、 苄基三乙基氯化铵 、 原甲酸三甲酯 作用下， 以 乙醇 为溶剂， 反应 0.25h， 生成 3',3'-dichloro-1,1,3,3-tetramethylspiro
  参考文献：
  名称：

  Reactions of Thioketones with Dichlorocarbene

  摘要：

  The reactions of sterically crowded cycloalkanethiones of type 2 with CHCl3/NaOH under phase-transfer catalysis (PTC) with benzyl(triethyl)ammonium chloride (TEBA) as catalyst afforded the corresponding 'gem.-dichlorothiiranes' of type 3 in good yields (cf. Scheme 2 and Table). The desulfurization, which, in some cases, occurred spontaneously, led to (dichloromethylidene)cycloalkanes of type 4. Similar results were obtained using Seyferth's reagent in boiling benzene. In the case of 2,2,6,6-tetramethylcyclohexanethione, reaction under PTC conditions after 3 h yielded only the corresponding dichloromethylidene derivative: on the other hand, workup after 1 h gave (2,2,6,6-tetramethylcyclohexylidene)methanethione (thioketene 9; Scheme 5).

  DOI：

  10.1002/(sici)1522-2675(19990609)82:6<946::aid-hlca946>3.0.co;2-p
• 作为产物：
  描述：

  1,1,3,3-tetramethylindan-2-thione 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 97.5h， 生成 1,1,3,4-四甲基-2-茚酮
  参考文献：
  名称：

  Lewis Acid Catalyzed Reactions of Thioketones with 1,2-Epoxycyclohexane and 1,2-Epoxycyclopentane

  摘要：

  Non-enolizable thioketones and 1,2-epoxycycloalkanes undergo a Lewis acid catalyzed addition reaction to give 1.3-oxathiolanes. Appropriate reaction conditions are CH2Cl2 as the solvent, BF3. Et2O as the Lewis acid, and a temperature between -78 degrees and r.t. Under the reaction conditions, the 1,3-oxathiolanes are only moderately stable. They decompose to yield the corresponding epithiocycloalkane and ketone. In general, 1,3-dithiolanes are isolated as minor products or, after prolonged reaction, as the main product. These secondary products are formed via the Lewis acid catalyzed reaction of the intermediate epithiocycloalkane and a second molecule of the thioketone. In the reaction of thiobenzophenone and 1.2-epoxycyclohexane, trans-8,8-diphenyl-7,9-dioxabicyclo[4.3.0]nonane is formed in small amounts as an additional side product (Scheme 12). in all cases, the newly formed heterocycle and the carbocycle are trans-fused. This result is consistent with a nucleophilic ring-opening of the complexed oxirane by the thioketone via inversion of the configuration and subsequent formation of the O(1)-C(2) bond of the 13-oxathiolane (Scheme 13). The surprising formation of the fused 1,4-oxathiepan derivative 23 (Scheme 9) is in accordance with un ionic reaction mechanism (cf. Scheme 15).

  DOI：

  10.1002/(sici)1522-2675(19991215)82:12<2316::aid-hlca2316>3.0.co;2-3

文献信息

• Carbenoid Chain Reactions:  Substitutions by Organolithium Compounds at Unactivated 1-Chloro-1-alkenes
  作者：Rudolf Knorr、Claudio Pires、Claudia Behringer、Thomas Menke、Johannes Freudenreich、Eva C. Rossmann、Petra Böhrer

  DOI：10.1021/ja0649116

  日期：2006.11.1

  chain cycle consists of the following two steps: (i) A fast vinylic substitution reaction of these RLi at carbenoid 6 (step 2) with formation of the chain carrier Alk(2)C=CLi-R (8), and (ii) a rate-limiting transfer of atom A (step 3) from reagent 2 to the chain carrier 8 with formation of the product Alk(2)C=CA-R (4) and with regeneration of carbenoid 6. This chain propagation step 3 was sufficiently

  看似简单的“交叉偶联”反应 Alk(2)C=CA-Cl + RLi --> Alk(2)C=CA-R + LiCl（A = H、D 或 Cl）通过亚烷基卡宾链机制发生在没有过渡金属催化剂的情况下分三步进行。在起始步骤 1 中，空间屏蔽的 2-(氯亚甲基)-1,1,3,3-四甲基茚满 2a-c (Alk(2)C=CA-Cl) 生成 Cl,Li-亚烷基卡宾 (Alk(2) C=CLi-Cl, 6) 通过将原子 A 转移到 RLi（甲基锂、正丁基锂或芳基锂）。链循环由以下两个步骤组成：（i）这些 RLi 在类胡萝卜素 6 处的快速乙烯基取代反应（步骤 2），形成链载体 Alk(2)C=CLi-R (8)，以及 (ii) ) 原子 A (步骤 3) 从试剂 2 到链载体 8 的限速转移，形成产物 Alk(2)C=CA-R (4) 并再生类卡宾化合物 6。这个链增长步骤 3 足够慢，可以观察到 Alk(2)C=CLi-Aryl
• Thermal and Nickel-catalyzed Dimerization of Hexapentaene. Synthesis of Two [4]Radialenes with Planar, Stable Cyclobutadiene-like Geometry
  作者：Masahiko Iyoda、Masaji Oda、Yasushi Kai、Nobuko Kanehisa、Nobutami Kasai

  DOI：10.1246/cl.1990.2149

  日期：1990.12

  The thermal and nickel-catalyzed cyclodimerization of the hexapentaene produced two types of [4]radialenes. The X-ray structural analysis of the thermal dimer has shown that the molecule has a pinwheel-like structure with the exactly planar central four-membered ring.

  六戊烯的热催化和镍催化环二聚反应产生两种类型的 [4] 辐射烯。热二聚体的 X 射线结构分析表明，该分子具有风车状结构，具有精确平面的中央四元环。
• Imidazole derivatives
  申请人：Hoffmann-La Roche Inc.

  公开号：US04435406A1

  公开（公告）日：1984-03-06

  Tricyclic imidazole derivatives of the formula ##STR1## wherein R.sup.1 is 2-pyridyl optionally substituted by lower alkyl or lower alkoxy, n is the integer 0 or 1, R.sup.2 is hydrogen or lower alkyl, R.sup.3 and R.sup.4, independently, are hydrogen or lower alkyl, A is a group of the formula ##STR2## m is the integer 2 or 3, R.sup.5, R.sup.6, R.sup.7 and R.sup.8, independently, are hydrogen or lower alkyl, and R.sup.9 is hydrogen and R.sup.10 is hydrogen or lower alkyl or R.sup.9 and R.sup.10 taken together are oxo, provided that at least one of R.sup.3 and R.sup.4 is lower alkyl when A is a group of the formula --CH.dbd.CH--CH.dbd.CH-- or --(CH.sub.2).sub.4 --, and their pharmaceutically acceptable acid addition salts. The compounds of formula I inhibit gastric acid secretion and prevent the formation of gastric ulcers.

  Tricyclic imidazole derivatives of the formula ##STR1## wherein R.sup.1 is 2-pyridyl optionally substituted by lower alkyl or lower alkoxy, n is the integer 0 or 1, R.sup.2 is hydrogen or lower alkyl, R.sup.3 and R.sup.4, independently, are hydrogen or lower alkyl, A is a group of the formula ##STR2## m is the integer 2 or 3, R.sup.5, R.sup.6, R.sup.7 and R.sup.8, independently, are hydrogen or lower alkyl, and R.sup.9 is hydrogen and R.sup.10 is hydrogen or lower alkyl or R.sup.9 and R.sup.10 taken together are oxo, provided that at least one of R.sup.3 and R.sup.4 is lower alkyl when A is a group of the formula --CH.dbd.CH--CH.dbd.CH-- or --(CH.sub.2).sub.4 --, and their pharmaceutically acceptable acid addition salts. The compounds of formula I inhibit gastric acid secretion and prevent the formation of gastric ulcers.
• Nickel-Catalyzed Dimerization of [5]Cumulenes (Hexapentaenes)
  作者：Yoshiyuki Kuwatani、Gaku Yamamoto、Masaji Oda、Masahiko Iyoda

  DOI：10.1246/bcsj.78.2188

  日期：2005.12

  Tetraaryl[5]cumulenes react with low-valent nickel complexes at the second double bond to produce novel [4]radialene derivatives that are head-to-head dimers of [5]cumulenes. The head-to-head dimers are also synthesized by a stepwise route. On the other hand, the nickel-catalyzed dimerization of ‖5]cumulenes with bulky substituents produces other types of extended [4]radialenes and [5]radialenones

  四芳基[5] 枯草烯与低价镍配合物在第二个双键处反应生成新型 [4] 放射烯衍生物，它们是 [5] 枯草烯的头对头二聚体。头对头二聚体也是通过逐步途径合成的。另一方面，镍催化的具有庞大取代基的 ‖5] 枯草烯的二聚反应产生其他类型的扩展 [4] 辐射烯和 [5] 辐射烯，这取决于末端烷基取代基的庞大性。因此，四叔丁基[5]枯草烯和l,4-双(2,2,6,6-四甲基亚环己基)[3]枯草烯在中心双键反应生成相应的[4]radialene和[5]径向烯酮，而 1,4-双(2,2,5,5-四甲基环戊叉基)[3] 枯草烯及其苯并环化衍生物在第二个双键处以头对尾的方式反应，得到相应的扩展 [4 ]辐射烯。使用甲基化-脱水程序将四叔丁基[5]radialenone转化为[5]radialene。扩展的 [4]- 和 [5] 辐射烯和 [5] 辐射烯已通过光谱分析、X 射线晶体学和/或独立的化学合成进行了充分表征。已经详细研究了这些新型环外
• Alkylation of ketones by use of solid KOH in dimethyl sulfoxide
  作者：Elke Langhals、Heinz Langhals

  DOI：10.1016/s0040-4039(00)94647-1

  日期：1990.1

  A mixture of solid KOH in dimethyl sulfoxide has a strong basicity, but only a low nucleophilicity and is used for methylation of ketones. With this simple and inexpensive reagent complete methylation with yields up to 90% can be achieved.

  固体KOH与二甲亚砜的混合物具有强碱性，但亲核性较低，可用于酮的甲基化。使用这种简单且便宜的试剂，可以实现甲基化，收率高达90％。