(S)-(+)-1-(1-萘基)异硫氰酸乙酯 | 131074-55-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: (S)-(+)-1-(1-萘基)异硫氰酸乙酯
• 中文别名: (S)-(+)-1-(1-萘基)乙基硫代异氰酸酯
• 英文名称: (S)-1-(1-naphthyl)ethyl isothiocyanate
• 英文别名: (S)-(+)-1-(1-Naphthyl)ethyl isothiocyanate；1-[(1S)-1-isothiocyanatoethyl]naphthalene
• CAS: 131074-55-0
• 化学式: C₁₃H₁₁NS
• 分子量: 213.303
• InChiKey: PGJWLIIUEIYCSF-JTQLQIEISA-N

物化性质

• 沸点：
  354.4±11.0 °C(Predicted)
• 密度：
  1,154 g/cm3
• 稳定性/保质期：
  如果按照规格使用和储存，则不会分解，未有已知危险反应。应避免与氧化物、水分等接触。

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  44.4
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险等级：
  6.1
• 安全说明：
  S26,S36/37/39
• 危险类别码：
  R20/21/22,R36/37/38
• 海关编码：
  2930909090
• 包装等级：
  III
• 危险类别：
  6.1
• 危险品运输编号：
  UN 2810

反应信息

• 作为反应物：
  描述：

  (S)-(+)-1-(1-萘基)异硫氰酸乙酯 在 2-氯-1,3-二甲基氯化咪唑啉 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 40.0h， 生成 (4S,5S)-4,5-diphenyl-1-ethoxycarbonyl-2-[(S)-1-(1-naphthyl)ethylimino]imidazolidine
  参考文献：
  名称：

  Modified Guanidines as Potential Chiral Superbases. 2. Preparation of 1,3-Unsubstituted and 1-Substituted 2-Iminoimidazolidine Derivatives and a Related Guanidine by the 2-Chloro-1,3-dimethylimidazolinium Chloride-Induced Cyclization of Thioureas

  摘要：

  Simple preparation methods for modified guanidines were explored for new chiral superbases, Thus, (4S,5S)-4,5-diphenyl- and diastereomeric cyclohexane-fused 2-iminoimidazolidines were prepared from (1S,2S)-1,2-diphenylethylenediamine and (1R,2R)- or (1S,2S)-1,2-diaminocyclohexanes through cyclization of protected thiourea intermediates with 2-chloro-1,3-dimethylimidazolinium chloride (DMC) as a key reaction. In the (4S,SS)-4,5-diphenyl series 1-methyl-2-iminoimidazolidines and 2-diethylaminoimidazoline were also prepared as related guanidines.

  DOI：

  10.1021/jo000745n
• 作为产物：
  描述：

  (S)-(-)-1-(1-萘基)乙胺 在 2-氯-1,3-二甲基氯化咪唑啉 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (S)-(+)-1-(1-萘基)异硫氰酸乙酯
  参考文献：
  名称：

  Modified Guanidines as Potential Chiral Superbases. 2. Preparation of 1,3-Unsubstituted and 1-Substituted 2-Iminoimidazolidine Derivatives and a Related Guanidine by the 2-Chloro-1,3-dimethylimidazolinium Chloride-Induced Cyclization of Thioureas

  摘要：

  Simple preparation methods for modified guanidines were explored for new chiral superbases, Thus, (4S,5S)-4,5-diphenyl- and diastereomeric cyclohexane-fused 2-iminoimidazolidines were prepared from (1S,2S)-1,2-diphenylethylenediamine and (1R,2R)- or (1S,2S)-1,2-diaminocyclohexanes through cyclization of protected thiourea intermediates with 2-chloro-1,3-dimethylimidazolinium chloride (DMC) as a key reaction. In the (4S,SS)-4,5-diphenyl series 1-methyl-2-iminoimidazolidines and 2-diethylaminoimidazoline were also prepared as related guanidines.

  DOI：

  10.1021/jo000745n

文献信息

• The thiocarbonyl ‘S’ is softer than thiolate ‘S’: A catalyst-free one-pot synthesis of isothiocyanates in water
  作者：Latonglila Jamir、Abdur Rezzak Ali、Harisadhan Ghosh、Francis A. S. Chipem、Bhisma K. Patel

  DOI：10.1039/b923336a

  日期：——

  Treatment of the preformed or the in situ generated aryl/alkyl dithiocarbamates triethylammonium salt (ArNHCSS−.Et3NH+) with methyl acrylate in an aqueous medium gave solely arylisothiocyanate (ArNCS), whereas the in situ generated aryl dithiocarbamic acid (ArNHCSS−.H+) yielded exclusively the thia-Michael adduct (ArNHCSSCH2CH2COOMe). This differential reactivity can be explained by two alternative mechanisms which is dependent both on the nature of the counter cation and on the pH of the reaction medium. Irrespective of the counter cations, the thiocarbonyl sulfur (=S) atom, having large orbital-coefficient, is softer compared to the thiol/thiolate sulfur (-SH/S−) in a dithiocarbamate salt and the former adds to the Michael acceptor by a 1,4-addition.

  在水中介质中，用甲基丙烯酸处理预制的或原位生成的芳基/烷基二硫代氨基甲酸盐三乙基铵盐（ArNHCSS−.Et3NH+）仅得到芳基异硫氰酸酯（ArNCS），而原位生成的芳基二硫代氨基甲酸（ArNHCSS−.H+）仅生成硫代迈克尔加合物（ArNHCSSCH2CH2COOMe）。这种差异性反应活性可以通过两种替代机制来解释，这取决于反荷离子的性质和反应介质的pH值。不管反荷离子如何，与二硫代氨基甲酸盐中的硫醇/硫醇盐硫（−SH/S−）相比，硫羰基硫（=S）原子具有较大的轨道系数，更为柔软，前者通过1,4-加成与迈克尔受体加合。
• The effect of chiral <i>N</i>-substituents with methyl or trifluoromethyl groups on the catalytic performance of mono- and bifunctional thioureas
  作者：Josué Vazquez-Chavez、Socorro Luna-Morales、Diego A. Cruz-Aguilar、Howard Díaz-Salazar、Wilmer E. Vallejo Narváez、Rodrigo S. Silva-Gutiérrez、Simón Hernández-Ortega、Tomás Rocha-Rinza、Marcos Hernández-Rodríguez

  DOI：10.1039/c9ob01893j

  日期：——

  thiourea organocatalysts that incorporate a chiral group which includes a trifluoromethyl moiety and contrasted their performance with non-fluorinated analogs. The comparison between such systems allows the direct study of the NH acidity of a thiourea bonded to an aliphatic substituent. In principle, –CF3 systems feature an enhanced hydrogen bond (HB) donor capacity that is undoubtedly beneficial for

  我们评估了含有手性基团（包括三氟甲基部分）的硫脲有机催化剂，并将其性能与非氟化类似物进行了对比。这些系统之间的比较允许直接研究与脂族取代基键合的硫脲的NH酸度。原则上，–CF 3系统具有增强的氢键（HB）供体容量，这无疑有利于应用于Baylis-Hillman反应的HB催化。我们发现，像Schreiner的硫脲一样，在两个氮原子上都被该基团取代的硫脲可加速该反应。另一方面，我们在双功能催化剂（硫脲-伯胺）促进的反应中观察到了不同的行为。在异丁醛向亚苄基丙酮酸甲酯的迈克尔加成反应中，–CF 3含催化剂的性能优于–CH 3体系，而将共轭物添加至N-苯基马来酰亚胺则表现出相反的行为。过渡态的理论计算表明，氟化和非氟化化合物中的苯乙基与亲电试剂具有不同种类的相互作用。这些相互作用导致亲电试剂的不同排列，从而导致催化剂的选择性。因此，不能一概而论，在所有情况下，NH的酸度都与催化剂的性能有关，特别是
• Chiral thiourea compounds and process for enantioselective reduction of ketones
  申请人：Li Derun

  公开号：US20090253919A1

  公开（公告）日：2009-10-08

  Chiral thioureas are effective catalysts for the borane reduction of prochiral ketones to optically active alcohols. A prochiral ketone may be reduced to an optically active alcohol in the presence of a substantially sub-stoichiometric amount of chiral thiourea. The asymmetric thiourea compound of the present invention may be produced according to a production method described herein.

  手性硫脲是对丙酮进行硼氢化还原生成光学活性醇的有效催化剂。在存在明显亚化学计量量手性硫脲的情况下，可以将一个丙酮还原为光学活性醇。本发明的不对称硫脲化合物可以根据本文描述的生产方法制备。
• Catalytic asymmetric hydrosilylation of acetophenone with new chiral thiourea ligands containing the (S)-α-phenylethyl group
  作者：Ericka Santacruz、Gabriela Huelgas、Sandra K. Angulo、Virginia M. Mastranzo、Simón Hernández-Ortega、Judit A. Aviña、Eusebio Juaristi、Cecilia Anaya de Parrodi、Patrick J. Walsh

  DOI：10.1016/j.tetasy.2009.11.027

  日期：2009.12

  New chiral thioureas 1–8 containing 1,2-ethylendiamine or trans-1,2-diaminocyclohexane as the carbon skeleton, and containing an (S)-α-phenylethyl group have been prepared (79–98% yield). Thioureas 1–8 were used as ligands for the zinc-based catalyzed asymmetric hydrosilylation of acetophenone with polymethylhydrosiloxane (PMHS). The best result was achieved with monothiourea 1 (up to 75% ee), in toluene

  制备了一种新的手性硫脲1-8，它含有1,2-乙基己二胺或反式1,2-二氨基环己烷作为碳骨架，并含有（S）-α-苯乙基（收率79-98％）。硫脲1-8被用作苯乙酮与聚甲基氢硅氧烷（PMHS）的锌基催化不对称氢化硅烷化的配体。用单硫脲1（最高75％ee），甲苯和5 mol％的催化剂负载量可获得最佳结果。
• Crystallographic, 1H NMR and CD studies of sterically strained thiourea anion receptors possessing two stereogenic centres
  作者：Haslin Dato Paduka Ali、Susan J. Quinn、Thomas McCabe、Paul E. Kruger、Thorfinnur Gunnlaugsson

  DOI：10.1039/b819638a

  日期：——

  three chiral bis-naphthalene thiourea receptors (1–3) derived from (R)-(+)-1-(1-naphthyl)ethylamine and (S)-(−)-1-(1-naphthyl)ethylamine are reported along with spectroscopic studies to screen their potential as anion receptors/sensors. Their solid state structures were analysed by X-ray crystallography and their ability to bind anions such as acetate and phosphate in DMSO solution investigated by 1H

  三种衍生自手性的双萘硫脲受体（1-3）的合成和结构表征（R）-（+）-1-（1-萘基）乙胺 和 （S）-（-）-1-（1-萘基）乙胺与光谱研究一起被报道以筛选其作为阴离子受体/传感器的潜力。通过X射线晶体学分析它们的固态结构，并通过1 H NMR，吸收，荧光和圆二色谱法研究它们在DMSO溶液中与阴离子如乙酸根和磷酸根结合的能力。