Samarium(II) iodide 二碘化钐(II)

规格: 99%, dispersion in THF
CAS: 32248-43-4
产品编号: H26805
MDL: MFCD00058873
品牌: INFI

单电子转移试剂-二碘化钐

在1980年二碘化钐被法国化学家Kagan首次作为还原剂引入有机合成，还原烷基碘化物、溴化物和磺酸盐；随后Inanaga和Molander又进一步在这类反应中添加六甲磷酰三胺(HMPA)，能够显著提高反应的还原速率和产率；之后二碘化钐作为偶联剂和还原剂得到广泛应用，高效促进反应的化学选择性和非对映选择性，在实验研发和工业应用中都发挥着重要作用。

 

 

二碘化钐特点

·二碘化钐是一种单电子转移试剂

·二碘化钐对氧气敏感，需在惰性气体中保存

·二碘化钐在四氢呋喃溶液中呈深蓝色，活性最佳

·加入不同添加剂(HMPA、H2O、MeOH)，二碘化钐表现出不同的还原能力

·二碘化钐反应条件温和，在低温或室温下进行反应

 ·可以通过添加物调控二碘化钐的立体选择性，得到单一构型产物

二碘化钐介导的典型反应

Barbier反应

二碘化钐作为优良的均相还原剂，能介导一级、二级、烯丙基、苄基卤代物与醛酮发生反应，并且除了传统的分子间Barbier反应，还可以促进分子内的Barbier反应，高效合成环状化合物并具有较高的立体选择性。

 

Reformatsky-Aldol反应

Reformatsky反应是构建大碳环和大环内酯的重要方法，通常认为二碘化钐通过烯醇钐的中间体促进分子间和分子内的Reformatsky反应，并且具有极高的立体选择性。与常用的锌粉相比二碘化钐活性更高，对于大位阻或惰性酮也可顺利进行反应。

 

Radical-Alkene/Alkyne反应

有机卤化物或磺酸酯通过二碘化钐进行单电子还原生成自由基中间体，与α,β-不饱和酯、酰胺和内酯等自由基接受体发生加成反应。二碘化钐是剧毒三丁基锡氢的良好替代品用于引发自由基合环反应，并且使碳中心形成碳负离子加速环化反应，减少产生二次还原副产物。

 

Pinacol反应

醛酮通过二碘化钐介导进行单电子还原可形成羰基阴离子自由基，在氧原子和三价钐的作用下发生Pinacol反应，除此之外，亚胺也可以通过类似的反应得到邻二胺基化合物。分子内的Pinacol反应还可以控制立体选择性，有利于得到顺式二醇产物。

 

Fragmentation反应

二碘化钐可以促进环丙烷和环丁烷的裂解，是构建复杂环体系的重要手段之一；也可以促进杂环中杂原子之间的单键断裂，例如异噁唑和异噻唑中的N-O和N-S键断裂。

 

以上图片均来自下方参考文献

参考文献：

[1]Chem. Rev. 2004, 104, 3371−3403

[2] Angew. Chem. Int. Ed. 2009, 48, 7140 – 7165

[3] Chem. Rev. 2014, 114, 5959−6039

研峰科技二碘化钐

 

产品名称：Samarium(II) Iodide

产品CAS：32248-43-4

产品编号：H26805（99%, dispersion in THF）

                  H50977（0.1 M solution in THF）


 

产品名称：Samarium(II) Iodide

产品CAS：32248-43-4

产品编号：H26805（99%, dispersion in THF）

                  H50977（0.1 M solution in THF）

 

 

 

 

 

 

Chemical NameSamarium(II) Iodide
MDL NumberMFCD00058873
PubChem Substance ID24861467
CAS Number32248-43-4
Merck Number8349
EC Number203-726-8
Synonym Samarium diiodide {LY} Samarium diiodide {} {LY} Samarium diiodide {} {} {LY} Samarium diiodide {} {} {} {LY} Samarium diiodide {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {} {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {LY} Samarium diiodide {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {LY} Samar
Chemical Name Translation碘化钐
LabNetwork Molecule IDLN01295309
Canonical SMILESI[Sm]I
GHS Symbol
WGK Germany3
Personal Protective Equipment Eyeshields, Faceshields, full-face respirator (US), Gloves, multi-purpose combination respirator cartridge (US), type ABEK (EN14387) respirator filter Eyeshields, Gloves, type N95 (US), type P1 (EN143) respirator filter
UN Number UN3271 2056
Signal word {} {} {TCI} Danger
Precautionary statements
  • P362 Take off contaminated clothing and wash before reuse. 脱掉污染的衣服，清洗后方可重新使用
  • P271 Use only outdoors or in a well-ventilated area.? 只能在室外或通风良好的地方使用。
  • P280 Wear protective gloves/protective clothing/eye protection/face protection. 戴防护手套/防护服/眼睛的保护物/面部保护物。
  • P332+P313
  • P501 Dispose of contents/container to..… 处理内容物/容器.....
  • P210 Keep away from heat/sparks/open flames/hot surfaces. — No smoking. 远离热源/火花/明火/热的表面。——禁止吸烟。
  • P301+P312+P330
  • P337+P313
  • P403+P233
  • P264 Wash hands thoroughly after handling. 处理后要彻底洗净双手。
  • P303+P361+P353
  • P302+P352+P332+P313+P362+P364
  • P240 Ground/bond container and receiving equipment. 与地面接触/连接集装箱和接受设备。
  • P370+P378
  • P304+P340
  • P270 Do not eat, drink or smoke when using this product. 使用本产品时不要吃东西，喝水或吸烟。
  • P241 Use explosion-proof electrical/ventilating/lighting/…/equipment. 使用防爆电气/通风/照明/ .../设备。
  • P260 Do not breathe dust/fume/gas/mist/vapours/spray. 不要吸入粉尘/烟/气体/烟雾/蒸汽/喷雾。
  • P304+P340+P312
  • P305+P351+P338+P337+P313
  • P308+P311
  • P309+P311
  • P305+P351+P338
  • P403+P235
  • P241+P242+P243
  • P405 Store locked up. 上锁保管。
  • P233 Keep container tightly closed. ?保持容器密闭。
  • P261 Avoid breathing dust/fume/gas/mist/vapours/spray. 避免吸入粉尘/烟/气体/烟雾/蒸汽/喷雾。
  • P281 Use personal protective equipment as required. 使用所需的个人防护装备。
    Hazard statements
    • H225 Highly flammable liquid and vapour 高度易燃液体和蒸气
    • H373 May causes damage to organs through prolonged or repeated exposure 长期或频繁接触可能会损伤器官
    • H351 Suspected of causing cancer 怀疑致癌
    • H335 May cause respiratory irritation 可能导致呼吸道刺激
    • H319 Causes serious eye irritation 严重刺激眼睛
      Safety Statements
      • S26 In case of contact with eyes, rinse immediately with plenty of water and seek medical advice 眼睛接触后，立即用大量水冲洗并征求医生意见；
      • S45 In case of accident or if you feel unwell seek medical advice immediately (show the label where possible) 发生事故时或感觉不适时，立即求医（可能时出示标签）；
      • S20 When using do not eat or drink 使用时，不得进食，饮水；
      • S7/8 Keep container tightly closed and dry 保存在严格密闭容器中，保持干燥；
      • S16 Keep away from sources of ignition - No smoking 远离火源，禁止吸烟；
      • S33 Take precautionary measures against static discharges 对静电采取预防措施；
      • S30 Never add water to this product 切勿将水加入该产品中；
      • S29 Do not empty into drains 不要排入下水道；
      • S43 In case of fire use ... (indicate in the space the precise type of fire-fighting equipment. If water increases the risk add -?Never use water) 着火时使用（指明具体的消防器材种类，如果用水增加危险，注明“禁止用水”
      • S60 This material and its container must be disposed of as hazardous waste 该物质及其容器必须作为危险废物处置；
      • S36/37/39 Wear suitable protective clothing, gloves and eye/face protection 穿戴适当的防护服、手套和眼睛/面保护；
      • S9 Keep container in a well-ventilated place 保持容器在通风良好的场所；
      • S36/37 Wear suitable protective clothing and gloves 穿戴适当的防护服和手套；
        Risk Statements
        • R11 Highly flammable 非常易燃
        • R19 May form explosive peroxides 可能生成易爆的过氧化物质
        • R36/37 Irritating to eyes and respiratory system 对眼睛和呼吸系统有刺激性
        • R40 Limited evidence of a carcinogenic effect 有限证据表明其致癌作用
        • R14/15 Reacts violently with water, liberating extremely flammable gases 遇水剧烈反应，释放出高度可燃气体
        • R34 Causes burns 会导致灼伤
          Storage condition 2-8°C, sealed storage, away from moisture {LY} 2-8°C, sealed storage, away from moisture Air & Moisture Sensitive {} {LY} 2-8°C, sealed storage, away from moisture {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {}
          Packing GroupII
          Hazard Codes F,Xn F,Xi
          Hazard Class3
          Restrict 危险品
        • ⑴.常温常压下为蓝色至深蓝色液体，具有特殊气味。在极性有机溶剂中有一定的溶解度，通常在THF，HMPA中使用。刺激皮肤和粘膜。
        • ⑵. 遇水分解生成碱式碘化钐和氢气。有强还原性。具有较强的吸湿性，对氧气特别敏感，需要在惰性气体保护下制备和使用。一般保存于约0.1mol/L的四氢呋喃溶液中。
        • ⑶. 碘化钐(SmI2)是有机合成中一个具有广泛用途的试剂。它参与的主要反应包括：自由基环化反应；羰基-烯烃偶联反应；频哪偶联反应；羟醛缩合反应；Barbier反应；Reformatsky反应等。
        • ①. SmI2最基本
        • {SA}
        • 1. Synthesis , 1309, (2007)
        • {SA}
        • Merck 14 ,8349
        • {uni_hamburg} Short: II/25A
        • Title: Structure Data Of Free Polyatomic Molecules: Inorganic Molecules
        • Author: Graner, G.; Hirota, E.; Iijima, T.; Kuchitsu, K.; Ramsay, D.A.; Vogt, J.; Vogt, N.
        • Editor: Kuchitsu, K.
        • Source: Landolt-Börnstein, New Series
        • Volume: II/25A
        • Year: 1998
        • Keyword: Free Polyatomic Molecules; Inorganic Molecules; Molecules
        • ISBN: 3-540-61713-2
        • ISBN: 978-3-540-61713-6
        • Internet Resource: DOI:10.1007/b59072
        • RefComment: VII, 359 pages. Hardcover
        • Abstract: Volume II/25 is a supplemented and revised edition of the preceding volumes II/7, II/15, II/21 and II/23 containing up to date information on inorganic and organic polyatomic molecules. All experimental methods for the determination of quantitative structural data of free molecules have been considered: microwave, infrared, Raman, electronic and photoelectron spectroscopy as well as electron diffraction. The data obtained by these methods have been critically evaluated and compiled. They are presented separately for each molecule, together with a schematic figure of the structure and the original literature.
        • {uni_hamburg} Short: III/7a
        • Title: Crystal Structure Data of Inorganic Compounds: Key Elements: F, Cl , Br, I ( VII th Main Group) . Halides and Complex Halides
        • Author: Pies, W.; Weiss, A.
        • Editor: Hellwege, K.-H.; Hellwege, A.M.
        • Source: Landolt-Börnstein, New Series
        • Volume: III/7a
        • Page: 1-647
        • Year: 1973
        • ISBN: 3-540-06166-5
        • ISBN: 978-3-540-06166-3
        • Internet Resource: DOI:10.1007/b19972
        • RefComment: 1 fig., XXXII, Hardcover
        • Abstract: Volume III/7 contains structure data on those compounds which contain at least one of the elements F, Cl, Br, I, O, N, and P and cannot be called "organic". The structure data of the remaining inorganic compounds and the elements are dealt with in volumes III/6 and III/14, while the organic compounds are treated in volumes III/5 and III/10. The systematic arrange-ment is bas
          • 32248-43-4 H26805 Samarium(II) iodide 二碘化钐(II)

          化学属性

          Mol. FormulaI2Sm
          Mol. Weight404.17
          Density0.922
          TSCANo
          Appearance liq. stabilized with Sm pwdr.
          Stabilityair sensitive, moisture sensitive
          Melting Point526 ±3 °C
          Danger-Level-
          pH-:-
          Redox-

          *以上化合物性质及应用等信息仅供参考