4,5-dihydro-3H-dinaphtho<2,1-c:1',2'-e>thiepin | 154801-71-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并硫平类
• 英文名称: 4,5-dihydro-3H-dinaphtho<2,1-c:1',2'-e>thiepin
• 英文别名: (+/-)-4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]thiepine；dinaphtho<2,1-c:1',2'-d>thiepin；3,5-Dihydrodinaphtho[2,1-c:1,2-e]thiepine；13-thiapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene
• CAS: 154801-71-5；154801-72-6；169557-40-8
• 化学式: C₂₂H₁₆S
• 分子量: 312.435
• InChiKey: OGYUAGGBMMVBML-UHFFFAOYSA-N

物化性质

• 沸点：
  571.1±39.0 °C(Predicted)
• 密度：
  1.242±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4,5-dihydro-3H-dinaphtho<2,1-c:1',2'-e>thiepin 以 四氢呋喃 、 甲醇 、 水 、 苯 为溶剂， 反应 36.17h， 生成 2-<(N,N-dimethylamino)methyl>-2'-<(methylthio)methyl>-1,1'-binaphthyl
  参考文献：
  名称：

  Nucleophilic Attack on 4,5-Dihydro-4-alkyl-3H-dinaphtho[2,1-c:1',2'-e]thiepinium Salts. A Convenient Approach to New 2,2'-Bidentate 1,1'-Binaphthalene Ligands with Sulfur Donor Atoms

  摘要：

  The title dihydrothiepinium salts 6 react with a wide range of N-, S-, Se-, O-, and C-nucleophiles to afford dihydrothiepin 5 and/or the corresponding bidentate ligands 7. The dual course of the reaction can be controlled by a judicious choice of the substrate counterion. In most instances, an iodide counterion aids formation of dihydrothiepins 5, whereas perchlorate, tetraphenyl borate, or tetrafluoroborate counterions favor formation of bidentate ligands 7. An explanation based on a competition between the counterion and the external nucleophile is provided. Dihydrothiepinium salts 6 are easily accessible from dibromide (R,S)-4 via dihydrothiepin (R,S)-5. Individual enantiomers (R)- and (S)-5 have been obtained by resolution on a preparative triacetylcellulose (TAC) column and assigned absolute configuration on the basis of CD spectra and chemical correlation.

  DOI：

  10.1021/jo00085a021
• 作为产物：
  描述：

  4,5-dihydro-4-methyl-3H-dinaphtho<2,1-c:1',2'-e>thiepinium iodide 在 sodium acetate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 96.0h， 以53%的产率得到4,5-dihydro-3H-dinaphtho<2,1-c:1',2'-e>thiepin
  参考文献：
  名称：

  Nucleophilic Attack on 4,5-Dihydro-4-alkyl-3H-dinaphtho[2,1-c:1',2'-e]thiepinium Salts. A Convenient Approach to New 2,2'-Bidentate 1,1'-Binaphthalene Ligands with Sulfur Donor Atoms

  摘要：

  The title dihydrothiepinium salts 6 react with a wide range of N-, S-, Se-, O-, and C-nucleophiles to afford dihydrothiepin 5 and/or the corresponding bidentate ligands 7. The dual course of the reaction can be controlled by a judicious choice of the substrate counterion. In most instances, an iodide counterion aids formation of dihydrothiepins 5, whereas perchlorate, tetraphenyl borate, or tetrafluoroborate counterions favor formation of bidentate ligands 7. An explanation based on a competition between the counterion and the external nucleophile is provided. Dihydrothiepinium salts 6 are easily accessible from dibromide (R,S)-4 via dihydrothiepin (R,S)-5. Individual enantiomers (R)- and (S)-5 have been obtained by resolution on a preparative triacetylcellulose (TAC) column and assigned absolute configuration on the basis of CD spectra and chemical correlation.

  DOI：

  10.1021/jo00085a021

文献信息

• Reductive ring opening of dihydrodibenzothiepine and dihydrodinaphtho-oxepine and -thiepine
  作者：Francisco Foubelo、Benjamín Moreno、Tatiana Soler、Miguel Yus

  DOI：10.1016/j.tet.2005.07.042

  日期：2005.9

  hydrolysis, to unsymmetrically 2,2′-disubstituted binaphthyls 9 and 12, respectively. When the lithiation is performed with an excess of lithium in the presence of a catalytic amount of DTBB (10% molar), a double reductive cleavage takes place to give the dianionic intermediate VII, which by reaction with different electrophiles [H2O, Me2CO, Et2CO, (CH2)4CO, (CH2)5CO], followed by hydrolysis with water, yields

  在-78°C下，4,4'-二叔丁基联苯（DTBB）催化的二氢二苯并噻吩平（1）的锂化反应30分钟，然后与羰基化合物[ t BuCHO，Ph（CH 2）2 CHO，PhCHO，在相同温度下的（n -C 5 H 11）2 CO，（CH 2）5 CO，（CH 2）7 CO，（-）-薄荷酮]在用3 M盐酸水解后会生成硫烷基醇2。如果在添加羰基化合物作为第一亲电子试剂后[Me 2 CO，（CH 2）5CO，（-）-薄荷酮]，使生成的II型二价阴离子在室温下反应30分钟，进行第二次锂化反应，生成III型中间体，该中间体通过与第二个亲电试剂[Me 2 CO ，Et 2 CO，（CH 2）5 CO，ClCO 2 Et]，水解后得到苯基4的双官能团。硫烷醇2c在酸性条件下的环化反应产生八元含硫杂环3。二氢二萘并异庚烷7和10的锂化在−78°C的条件下用2.2当量的萘二甲酸锂在THF中反应，然后与不同的亲电试剂[H
• Synthesis and structural characterization of dithiacyclophanes derived from biaryldithiols
  作者：Upul K. Bandarage、Lyall R. Hanton、Robin A.J. Smith

  DOI：10.1016/0040-4020(94)00951-p

  日期：1995.1

  1′-binaphthalene-2,2′-bis(methylenethiol) with 2,2′-bis(bromomethyl)-1,1′-binaphthalene gave a mixture including dinaphtho[2,1-c:1′,2′-d]thiepin and the racemic diastereoisomer of 11,13,26,28-tetrahydrotetranaphtho[2,1-c:1′,2′-e:2″,1″-j:1‴,2‴-l][1,8]dithiacyclotetradecin.

  已经研究了二溴化物与联苯-2,2'-二硫醇和1,1'-联萘-2,2'-二硫醇反应生成二噻唑烷的反应的相对效率，这是手性联芳基二硫醇的潜在途径。可拆分的二溴化物2,2'-双（溴甲基）-1,1'-联萘与1,1'-联萘-2,2'-二硫醇的反应得到了二硫代环庚烷的非对映异构体混合物。1,1'-联萘-2,2'-双（亚甲基硫醇）与2,2'-双（溴甲基）-1,1'-联萘的反应生成的混合物包括萘甲酚[2,1-c：1'， 2'-d] thiepin和11,13,26,28-四氢四萘并[2,1-c：1'，2'-e：2“，1” -j：1‴，2‴-l的外消旋非对映异构体] [1,8]二硫代环十四烷。
• Preparation, characterisation and slow quantitative dissociation of a novel asymmetric N-unsubstituted dialkylsulfimide
  作者：Anthony D. M. Curtis、Christopher A. Ramsden、Muhammad R. Raza、Ray McCague

  DOI：10.1039/a808356h

  日期：——

  (±)-S-Imino-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-e]thiepine, a novel asymmetric N-unsubstituted sulfimide, undergoes slow, quantitative N–S bond cleavage in CDCl3 solution at 20 oC with a half-life of 20 h.

  (±)-S-氨基-4,5-二氢-3H-二萘并[2,1-c:1′,2′-e]硫杂卓是一种新型不对称 N-未取代亚硫酰亚胺，在 20 oC 时于 CDCl3 溶液中发生缓慢、定量的 N-S 键裂解，半衰期为 20 h。
• Reductive opening of 2,7-dihydrodinaphthoxepine and thiepine: easy regioselective preparation of 2,2′-difunctionalised binaphthyls
  作者：Francisco Foubelo、Benjamín Moreno、Miguel Yus

  DOI：10.1016/j.tetlet.2004.10.041

  日期：2004.11

  electrophiles [H2O, Me2CO, Et2CO, (CH2)4CO, (CH2)5CO], followed by hydrolysis with water, yields symmetrically 2,2′-disubstituted binaphthyls 7. In the case of starting from (R)-5a, the reductive opening by treatment with 2.2 equiv of lithium naphthalenide followed by reaction with H2O or (CH2)5CO as electrophiles and final hydrolysis, leads to enantiomerically pure compounds (R)-6aa and (R)-6af, respectively.

  在-78°C下用2.2当量萘基锂在THF中的2,7-二氢二萘并杂庚烷（5）锂化生成双阴离子中间体8，该中间体通过与不同的亲电试剂[H 2 O，D 2 O，t BuCHO，Me 2 CO ，在同一温度下，Et 2 CO，（CH 2）4 CO，（CH 2）5 CO]，然后水解，导致不对称的2,2'-双取代联萘6。当锂化是4,4'-二-催化量的存在下与过量的锂进行叔-丁基联苯（DTBB，10 mol％），进行两次还原裂解，得到双阴离子中间体9，该中间体通过与不同的亲电试剂[H 2 O，Me 2 CO，Et 2 CO，（CH 2）4 CO，（CH 2）5 CO]，然后用水水解，对称地生成2,2'-di取代的双萘基7。在从（R）-5a开始的情况下，通过用2.2当量的萘二甲酸锂处理然后与H 2 O或（CH 2）5反应来进行还原性打开。CO作为亲电子试剂并最终水解，分别产生对映体纯的化合物（R）-6aa和（R）-6af。
• Stara Irena G., Star Ivo, Tich Milo, Zavada Jii, Fiedler Pavel, J. Org. Chem, 59 (1994) N 6, S 1326-1332
  作者：Stara Irena G., Star Ivo, Tich Milo, Zavada Jii, Fiedler Pavel

  DOI：——

  日期：——