2-(dichloromethylidene)-1,1,3,3-tetramethylindan | 242149-78-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 2-(dichloromethylidene)-1,1,3,3-tetramethylindan
• 英文别名: 2-(Dichloromethylidene)-1,1,3,3-tetramethylindene；2-(dichloromethylidene)-1,1,3,3-tetramethylindene
• CAS: 242149-78-6
• 化学式: C₁₄H₁₆Cl₂
• 分子量: 255.187
• InChiKey: SOIGLZBFGWNCPV-UHFFFAOYSA-N

物化性质

• 熔点：
  119-121 °C(Solv: ethanol (64-17-5))
• 沸点：
  305.1±27.0 °C(Predicted)
• 密度：
  1.124±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-(dichloromethylidene)-1,1,3,3-tetramethylindan 在 叔丁基氯化镁 、 甲基锂 作用下， 以 四氢呋喃 、 乙醚 、 全氘代环己烷 为溶剂， 反应 120.0h， 生成 2-(3-phenyl-2-propyn-1-ylidene)-1,1,3,3-tetramethylindan
  参考文献：
  名称：

  Carbenoid 链反应：在未活化的 1-Chloro-1-烯烃上被有机锂化合物取代†

  摘要：

  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

  DOI：

  10.1021/ja0649116
• 作为产物：
  描述：

  1,1,3,3-tetramethylindan-2-thione 在 sodium hydroxide 、 苄基三乙基氯化铵 作用下， 以 solid 为溶剂， 反应 0.25h， 生成 2-(dichloromethylidene)-1,1,3,3-tetramethylindan
  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

文献信息

• Ring expansion and vinylic nucleophilic substitution competing for (tert-alkyl)2CC(Li)–Cl in carbenoid chain processes
  作者：Rudolf Knorr、Thomas Menke、Karsten-Olaf Hennig、Johannes Freudenreich、Petra Böhrer、Bernhard Schubert

  DOI：10.1016/j.tet.2014.03.004

  日期：2014.4

  (tert-alkyl)2CC(Li)–Cl as transient intermediates. The chains are longer and the overall reactions much slower in tert-butyl methyl ether (t-BuOMe) than in THF as the solvent. In competition with the fast SNV step of these Cl,Li-carbenoids, the Fritsch–Buttenberg–Wiechell (FBW) ring expansion in t-BuOMe (but less so in THF) generates short-lived cyclohexyne species, which are trapped by the accompanying

  乙烯基亲核取代（S Ñ V）未活化的，环状的α的反应，α-dichloroalkenes [（叔烷基）2 ç的CCl 2 ]与芳基锂（RLi的），得到（叔烷基）2 Ç C（Cl）的-R是被认为是类胡萝卜素链反应，涉及不饱和Cl，Li-类胡萝卜素（叔烷基）2 C C（Li）–Cl作为过渡中间体。与作为溶剂的THF相比，叔丁基甲基醚（t -BuOMe）中的链更长，总反应慢得多。与快速的S N竞争这些Cl，Li类胡萝卜素的V阶跃，在t -BuOMe中的Fritsch–Buttenberg–Wiechell（FBW）环膨胀（但在THF中则较少）产生了短寿命的环己炔物种，这些环己炔物种被伴随的RLi物种捕获以产生氯环己烯衍生物[（叔烷基）–（Cl）C C（R）–（叔烷基）]作为FBW链产物。
• Carbenoid-mediated nucleophilic “hydrolysis” of 2-(dichloromethylidene)-1,1,3,3-tetramethylindane with DMSO participation, affording access to one-sidedly overcrowded ketone and bromoalkene descendants^§
  作者：Rudolf Knorr、Thomas Menke、Johannes Freudenreich、Claudio Pires

  DOI：10.3762/bjoc.10.28

  日期：——

  2-(Dichloromethylidene)-1,1,3,3-tetramethylindane was “hydrolyzed” by solid KOH in DMSO as the solvent at ≥100 °C through an initial chlorine particle transfer to give a Cl,K-carbenoid. This short-lived intermediate disclosed its occurrence through a reversible proton transfer which competed with an oxygen transfer from DMSO that created dimethyl sulfide. The presumably resultant transitory ketene incorporated KOH to afford the potassium salt of 1,1,3,3-tetramethylindan-2-carboxylic acid (the product of a formal hydrolysis). The lithium salt of this key acid is able to acylate aryllithium compounds, furnishing one-sidedly overcrowded ketones along with the corresponding tertiary alcohols. The latter side-products (ca. 10%) were formed against a substantially increasing repulsive resistance, as testified through the diminished rotational mobility of their aryl groups. As a less troublesome further side-product, the dianion of the above key acid was recognized through carboxylation which afforded 1,1,3,3-tetramethylindan-2,2-dicarboxylic acid. Brominative deoxygenation of the ketones furnished two one-sidedly overcrowded bromoalkenes. Some presently relevant properties of the above Cl,K-carbenoid are provided in Supporting Information File 1.

  2-(二氯甲基亚甲基)-1,1,3,3-四甲基茚烷在DMSO作为溶剂的固体KOH存在下，通过最初的氯粒子转移反应形成了Cl,K-卡宾中间体，反应温度≥100°C。这种短暂的中间体通过可逆的质子转移来表明其存在，该过程与DMSO中的氧转移竞争，产生了二甲基硫。推测所得的短暂的酮烯通过与KOH结合形成了1,1,3,3-四甲基茚烷-2-羧酸钾盐（一种形式的水解产物）。该关键酸的锂盐能够酰化芳基锂化合物，产生单面过度拥挤的酮和相应的三级醇。后者是副产物（约10%），与它们的芳基基团的旋转自由度减小相应地形成。作为一个不太麻烦的进一步副产物，上述关键酸的二阴离子通过羧化反应被识别出来，形成了1,1,3,3-四甲基茚烷-2,2-二羧酸。酮的溴化脱氧反应生成了两个单面过度拥挤的溴代烯烃。有关上述Cl,K-卡宾中间体的一些相关性质在支持信息文件1中提供。
• Pseudomonomolecular, Ionic sp²-Stereoinversion Mechanism of 1-Aryl-1-alkenyllithiums
  作者：Rudolf Knorr、Thomas Menke、Claudia Behringer、Kathrin Ferchland、Johann Mehlstäubl、Ernst Lattke

  DOI：10.1021/om4000852

  日期：2013.8.12

  The trans/cis stereoinversion of the trigonal carbanion centers C-alpha in a series of monomeric 2-(alpha-aryl-alpha-lithiomethylidene)-1,1,3,3-tetramethylindanes (known to be trisolvated at Li) is rapid on the NMR time scales (400 and 100.6 MHz) in THF solution. The far-reaching redistribution of electric charge in the ground-state molecules caused by lithiation (formal replacement of alpha-H by alpha-Li) is illustrated through NMR shifts, Delta delta. The transition states for stereoinversion are significantly more polar and charge-delocalized than the ground states (Hammett rho = +5.2), pointing to a mechanism that involves heterolysis of the C-Li bond via a solvent-separated ion pair (SSIP). This requires immobilization of only one additional (the fourth) THF molecule at Li+, which accounts for part of the apparent activation entropies of ca. -23 cal mol(-1) K-1 and constitutes a kinetic privilege of THF depending on microsolvation at Li. Thus, the sp(2)-stereoinversion process is "catalyzed" by the solvent THF; its mechanism is monomolecular with respect to the ground-state species because the pseudo-first-order rate constants, measured through NMR line shape analyses, are independent of the concentrations (inclusive of decomposition) of the dissolved species (hence no associations and no dissociation to give free carbanion intermediates). In the deduced pseudomonomolecular mechanism (bimolecular through solvent participation), the angular C-alpha of the SSIP undergoes rehybridization (approximately in-plane inversion) through a close-to-linear transition state; this motion occurs with a concomitant "conducted tour" migration of Li(THF)(4) and is unimpaired by additional ortho-methylations at alpha-aryl. The synthetic route started with preparations of three alpha-chloro congeners through the carbenoid chain reaction, followed by vinylic substitution of alpha-Cl by alpha-SnMe3 (most efficient in THF despite steric congestion). The final Sn/Li interchange reaction afforded the new 1-aryl-1-alkenyllithium samples, initially uncontaminated by free Li+.
• Carbenoid Chain Reactions through Proton, Deuteron, or Bromine Transfer from Unactivated 1-Bromo-1-alkenes to Organolithium Compounds
  作者：Rudolf Knorr、Claudio Pires、Johannes Freudenreich

  DOI：10.1021/jo070623w

  日期：2007.8.1

  The deceptively simple vinylic substitution reactions Alk(2)CCABr + RLi -> Alk(2)CCAR + LiBr (A = H, D, or Br) occur via an alkylidenecarbenoid chain mechanism (three steps) without transition metal catalysis. 2-(Bromomethylidene)-1,1,3,3-tetramethylindan (Alk(2)CCH-Br, 2a) is deprotonated (step 1) by phenyllithium (PhLi) to give the Br,Li-alkylidenecarbenoid Alk(2)CCLi-Br (3). In the ensuing chain cycle, 3 and PhLi (step 2) form the observable alkenyllithium intermediate Alk(2)CCLiPh that characterizes the carbenoid mechanism in Et2O and is able to propagate the chain (step 3) through deprotonation of 2a, furnishing carbenoid 3 and the product Alk(2)CCHPh. The related 2-(dibromomethylidene)-1,1,3,3-tetramethylindan (Alk(2)CCBr(2), 2c) and methyllithium (MeLi) generate carbenoid 3 (step 1), which incorporates MeLi (step 2) to give Alk(2)CCLiCH(3), which reacts with 2c by bromine transfer producing Alk(2)CCBrCH(3) and carbenoid 3 (step 3). PhCCLi cannot carry out step 1, but MeLi can initiate (step 1) the carbenoid chain cycle (steps 2 and 3) of 2c with PhCCLi leading to Alk(2)CCBrCC-Ph. Reagent 2a may perform both proton and bromine transfer toward Alk(2)CCLiCH(3), feeding two coupled carbenoid chain processes in a ratio that depends on the solvent and on a primary kinetic H/D isotope effect.
• 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