Bis(cyclopentadienyl)zirconium chloride hydride 氢氯二茂锆

规格: 95%
CAS: 37342-97-5
产品编号: H63619
MDL: MFCD02089401
品牌: INFI

简介

氢化锂, 氢化铝锂,硼氢化钠,三乙基硼氢化锂(Super Hydride)/钠/钾 ,三仲丁基硼氢化锂( L-Selectride)/钠/钾(K-Selectride),Lithium Trisiamylborohydride (LiBSia3H) 60217-34-7, 三叔丁氧基氢化铝锂,77299-63-9 Lithium diisobutyl-tert-butoxyaluminum hydride solution,Diisobutylaluminum hydride, DIBAL,硼烷四氢呋喃,氨基硼烷等,  金属氢化物,作为还原剂和负氢离子的来源,广泛用于无机和有机合成中,以及作为储氢材料应用到日常生产生活中。金属氢化物还原剂,可以还原取代卤代物到烷烃,醛酮环氧亚胺等到醇或胺,羧酸衍生物如酯,腈及其他衍生物到特别是某些烃基取代的金属化合物,具有反应条件温和,副反应少以及产率高的优点,体现出较好的化学选择性和立体 选择性。在复杂的天然产物,药物分子的合成中,较之其他还原法显示出更多的优点。

应用举例

1. 还原卤代物等到相应的烷烃(反应式A,B),并且氘代实验表明,该还原反应经过明确的SN2取代机理(反应式B)。另外,OTs,OMs等取代基也能被还原。

2. 还原环氧到醇,在如下例中,三乙基硼氢化锂比的四氢铝锂的选择性要高很多。


3. 选择性还原醛酮到相应的醇。在α-环己酮的还原中,以很高的选择性的得到顺势的产品(反应式D);并且在醛和酮同时存在的情况下,可以优先还原醛到相应的一级醇(反应式E)。其中,Lithium trisiamylborohydride (LiBSia3H)表现出更好的选择性,以其他取代的环己酮为例,各氢化物还原总结如表一。

4. 选择性的还原羧酸及其衍生物。可以在有其他可被还原的基团存在下,选择性的还原酯基。

5.其他用途。氢化物也可以转移负氢离子到其他的过度金属有机化合物上,形成新的M-H化合物,选择性的脱除甲基。

参考文献

Lithium Triethyllborohydride,Marek Zaidlewicz,Herbert C. Brown, Encyclopedia of Reagents for Organic Synthesis,2001

Krishnamutthy, S. Schubert R.M Brown, H, C, J., Am Chem. Soc 1973, 95, 8486

JACS, 1973

Chemical NameBis(Cyclopentadienyl)Zirconium Chloride Hydride
Synonym Bis(cyclopentadienyl)chlorohydrozirconium {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {} { {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {} {} {} {} {} {} {} {} { {} {} {} {} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {} {} {} {} {} {} {} {} {} {} {} {} { {} {} {} {} {} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium {}
PubChem Substance ID87577928
EC Number253-479-5
Merck Number8396
Chemical Name Translation氢氯二茂锆
InChIKeyUVWUHPCWBZSERX-UHFFFAOYSA-M
MDL NumberMFCD02089401
CAS Number37342-97-5
Canonical SMILES[][Zr]([H])(Cl)[].c1cccc1.c2cccc2
GHS Symbol
WGK Germany3
Precautionary statements
  • P422 Store contents under… 存储目录在…之下。
  • P310 Immediately call a POISON CENTER or doctor/physician. 立即呼救解毒中心或医生/医师。
  • P231+P232
  • 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。
  • P305+P351+P338
  • 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。
  • P223 Keep away from any possible contact with water, because of violent reaction and possible flash fire. 远离任何与水接触的可能,因为会剧烈反应可能产生闪火。
  • P501 Dispose of contents/container to..… 处理内容物/容器.....
  • 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。
  • P305+P351+P338+P310
  • P264 Wash hands thoroughly after handling. 处理后要彻底洗净双手。
  • P301+P330+P331+P310
  • P303+P361+P353
  • P370+P378
  • 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。
  • P304+P340+P310
  • P301+P330+P331
  • P402+P404
  • P303+P361+P353+P310+P363
    Hazard statements
    • H314 Causes severe skin burns and eye damage 导致严重的皮肤灼伤和眼睛损伤
    • H261 In contact with water releases flammable gas 与水接触时释放可燃气体。
      Signal word
      Personal Protective Equipment Eyeshields, Faceshields, full-face particle respirator type N100 (US), Gloves, respirator cartridge type N100 (US), type P1 (EN143) respirator filter, type P3 (EN 143) respirator cartridges
      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;
      • S27 Take off immediately all contaminated clothing 立即脱掉全部污染的衣服;
      • 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;
      • S16 Keep away from sources of ignition - No smoking 远离火源,禁止吸烟;
      • 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);
      • S33 Take precautionary measures against static discharges 对静电采取预防措施;
      • 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;
        Packing GroupII
        UN Number 3131
        Risk Statements
        • R11 Highly flammable 非常易燃
        • R15 Contact with water liberates extremely flammable gases 遇水会释放出极端易燃的气体
        • R34 Causes burns 会导致灼伤
          Storage condition 2-8°C, protect from light, stored under nitrogen {LY} 2-8°C, protect from light, stored under nitrogen Light, Air & Moisture Sensitive {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen {} {} {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C
          Hazard Codes F,C
          Hazard Class4.3/8
          Restrict -
        • 转化氨基化合物生成醛类化合物;石蜡和炔烃的功能化试剂。
        • {ALF} Reagent for selective reduction of secondary carboxamides to imines, a transformation otherwise difficult to achieve since imines are normally more easily reduced than amides: J. Org. Chem., 61, 4115 (1996); tertiary amides can also be reduced to aldehydes at room temperature: J. Am. Chem. Soc., 122, 11995 (2000). Reduction of phosphine oxides and phosphine sulfides to phosphines under mild conditions has also been reported: Tetrahedron Lett., 38, 5997 (1997).
        • {ALF} Catalyzes the hydroboration of alkynes with Pinacolborane, L17558, to form alkenylboronates with high regio- and stereoselectivity: Organometallics, 14, 3127 (1995). Alkenes are similarly converted to alkylboronates: J. Am. Chem. Soc., 118, 909 (1996).
        • {ALF} Reaction with alkenes (hydrozirconation) results in zirconocene alkyl chlorides: Tetrahedron Lett., 28, 3895 (1987). Useful products are obtained by reaction of these with various electrophiles. With O-(mesitylsulfonyl)hydroxylamine, primary amines are obtained, with generally good yields and regioselectivity: J. Org. Chem., 60, 1912 (1995).
        • {ALF} For a brief feature on the reagent, see: Synlett, 1179 (1999); review of synthetic applications of organozirconocene compounds: Tetrahedron, 52, 12853 (1996)
        • {ALD} Merck: 14,8396
        • 37342-97-5 H63619 Bis(cyclopentadienyl)zirconium chloride hydride
氢氯二茂锆

          化学属性

          TSCANo
          Mol. FormulaC10H11ClZr
          Mol. Weight257.87
          Appearance off-white pwdr.
          Stabilitylight sensitive, moisture sensitive
          Melting Point300°C
          Boiling Point41.5°C at 760 mmHg
          Danger-Level-
          pH-:-
          Redox-

          *以上化合物性质及应用等信息仅供参考