Lithium aluminium hydride 氢化锂铝

规格: 2.5 M solution in THF, SpcSeal
CAS: 16853-85-3
产品编号: H89055
MDL: MFCD00011075
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,OTsOMs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alfa-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,选择性的脱除甲基等等。



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 NameLithium aluminium hydride
Synonym Aluminate(1-), tetrahydro-, lithium, (T-4)- Aluminum lithium hydride LAH LAH Lithium alanate LAH Lithium alanate Lithium tetrahydro LAH; Lithium tetrahydridoaluminate LITHIUM ALANATE LITHIUM ALUMINUM HYDRIDE LiAlH4 LiAlH4 Lithium alanate Lithium aluminohydride Lithium aluminum hydride (LiAlH4) Lithium aluminum tetrahydride Lithium tetrahydroaluminate Lithiumaluminiumhydrid lithium aluminium hydride lithiumaluminumhydride,ethereal lithiumtetrahydroaluminate lithiumtetrahydroaluminate(lithiumaluminiumhydride) {} {} {} {} {Chemi 四氢铝锂 四氢铝锂,四氢化铝锂,(T-4)-四氢铝酸锂 四氫化鋁鋰
MDL NumberMFCD00011075
EC Number240-877-9
PubChem Substance ID87560001
CAS Number16853-85-3
Merck Number350
Beilstein Registry Number11460447
Reaxys-RN11460447
Chemical Name Translation氢化铝锂
Wiswesser Line Notation.AL..H4.LI
LabNetwork Molecule IDLN01341120
GHS Symbol
Precautionary statements
  • 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。
  • 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。
  • P231+P232
  • 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。
  • P264 Wash hands thoroughly after handling. 处理后要彻底洗净双手。
  • 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。
  • 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。
  • P281 Use personal protective equipment as required. 使用所需的个人防护装备。
  • P284 Wear respiratory protection.? 佩戴呼吸保护装置。
  • P301+P330+P331+P310
  • P303+P361+P353+P310+P363
  • P304+P340+P310
  • P305+P351+P338
  • P305+P351+P338+P310
  • P335+P334
  • P370+P378
  • P402+P404
  • P403+P235
  • P405 Store locked up. 上锁保管。
  • P422 Store contents under… 存储目录在…之下。
  • P501 Dispose of contents/container to..… 处理内容物/容器.....
    Signal word Danger
    Hazard statements
    • H314 Causes severe skin burns and eye damage 导致严重的皮肤灼伤和眼睛损伤
    • H260 In contact with water releases flammable gases which may ignite spontaneously 与水接触时释放可燃气体,可自燃。
    • H225 Highly flammable liquid and vapour 高度易燃液体和蒸气
    • H332 Harmful if inhaled 吸入有害
    • H315 Causes skin irritation 会刺激皮肤
    • H360 May damage fertility or the unborn child 可能对生育能力或未出生婴儿造成伤害
    • H319 Causes serious eye irritation 严重刺激眼睛
    • H335 May cause respiratory irritation 可能导致呼吸道刺激
    • H304 May be fatal if swallowed and enters airways 吞食和进入呼吸道可能致命
    • H336 May cause drowsiness or dizziness 肯能导致嗜睡或头晕
    • H361d Suspected of damaging the unborn child 怀疑对未出生婴儿造成伤害
    • 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
    • H261 In contact with water releases flammable gas 与水接触时释放可燃气体。
    • H226 Flammable liquid and vapour 易燃液体和蒸气
    • H302 Harmful if swallowed 吞食有害
    • H318 Causes serious eye damage 严重伤害眼睛
    • H224 Extremely flammable liquid and vapour 极端易燃液体和蒸气
    • H351 Suspected of causing cancer 怀疑致癌
      WGK Germany1
      RTECSBD0100000
      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 Eyeshields, Faceshields, full-face respirator (US), Gloves, multi-purpose combination respirator cartridge (US), type ABEK (EN14387) respirator filter Eyeshields, Faceshields, full-face respirator (US), Gloves, multi-purpose combination respirator cartridge (US)
      Safety Statements
      • S15 Keep away from heat 远离热源;
      • S16 Keep away from sources of ignition - No smoking 远离火源,禁止吸烟;
      • S22 Do not breathe dust 不要吸入粉尘;
      • S23 Do not breathe gas/fumes/vapour/spray (appropriate wording to be specified by the manufacturer) 不要吸入气体/烟雾/蒸汽/喷雾;
      • S24/25 Avoid contact with skin and eyes 避免皮肤和眼睛接触;
      • 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;
      • S30 Never add water to this product 切勿将水加入该产品中;
      • S36/37 Wear suitable protective clothing and gloves 穿戴适当的防护服和手套;
      • 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;
      • 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”
      • 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);
      • S7/8 Keep container tightly closed and dry 保存在严格密闭容器中,保持干燥;
        Packing GroupI
        UN Number 1410 3399
        Risk Statements
        • R10 Flammable 易燃
        • R11 Highly flammable 非常易燃
        • R12 Extremely flammable 极端易燃
        • 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
        • R15 Contact with water liberates extremely flammable gases 遇水会释放出极端易燃的气体
        • R19 May form explosive peroxides 可能生成易爆的过氧化物质
        • R20 Harmful by inhalation 吸入有害
        • R22 Harmful if swallowed 吞咽有害
        • R34 Causes burns 会导致灼伤
        • R36/37 Irritating to eyes and respiratory system 对眼睛和呼吸系统有刺激性
        • R36/37/38 Irritating to eyes, respiratory system and skin 对眼睛、呼吸系统和皮肤有刺激性
        • R36/38 Irritating to eyes and skin 对眼睛和皮肤有刺激性
        • R37 Irritating to respiratory system 刺激呼吸道
        • R40 Limited evidence of a carcinogenic effect 有限证据表明其致癌作用
        • R48/20
        • R60 May impair fertility 可能降低生殖能力
        • R61 May cause harm to the unborn child 可能对未出生的婴儿导致伤害
        • R63 Possible risk of harm to the unborn child 可能危害未出生婴儿
        • R66 Repeated exposure may cause skin dryness or cracking 反复接触可能导致皮肤干燥或皴裂
        • R67 Vapours may cause drowsiness and dizziness 蒸汽可能导致嗜睡和昏厥
          Storage condition 充氩储存 储存温度2-8℃; 充氩储存 Air & Moisture Sensitive 充氩密封 2-8°C
          Hazard Codes 4.3 F+,Xn F,C,Xi,Xn,F+ F,T
          Hazard Class4.3
          Warnings 危化品目录(2015)
        • ⑴.具有高度可燃性,必须隔绝空气、湿气,并最好在氮气氛下保存。
        • ⑵. 羰基试剂。还原剂。制造其他氢化物及硅烷、硼烷等。在医药、香料、农药、染料及其他精细有机合成中用作还原剂。可将醛酮、酸、酸酐、酯、醌、酰氯等还原为醇,将腈还原为伯胺,将卤化烃还原为烃,芳香硝基化合物还原成偶氮化合物。但通常不能使碳—碳双键氢化。100份乙醚能溶本品30份,100份四氢呋喃能溶13份,100份二甲基溶纤剂能溶10份,100份二丁醚能溶2份,100份二氧六环能溶0.1份。
        • ⑶. 是有机化学中一个常用的还原试剂,能够还原多种官能
        • A powerful reagent and reducing agent.
        • {ALF} For reduction of sulfones, see Titanium(IV)­ chloride, 14713.
        • {ALF} For THF, at least 10ml solvent per gram of reagent is recommended to absorb heat of mixing.
        • {ALF} The use of water or steam baths, or of electric heating mantles is to be strongly discouraged.
        • {ALF} The reduction reaction should preferably be controlled by adjusting the rate of addition of the substrate rather than relying on external heating or cooling.
        • {uni_hamburg} Short: IV/19A1
        • {ALF} Many procedures for reactions with this reagent which have been described in the literature are potentially unsafe on anything other than a very small scale, since often no precautions are given for mixing the reagent with flammable solvents. The following suggestions are offered for laboratory scale reductions:
        • {uni_hamburg} Short: III/14a
        • {ALD} Merck: 14,349
        • {ALF} Efficient stirring is essential during mixing, reaction and workup.
        • {ALF} For phase-transfer reductions in hydrocarbon solvents, see 15-Crown-5, A12265. For formation of lithium tris(diethylamino)aluminum hydride and use in the reduction of esters or amides to aldehydes, see Diethyl­amine, A11716. For formation of a reagent for reduction of carboxylic acids to aldehydes, see 1-Methyl­piperazine, A10837.
        • {ALF} External heating or cooling, if required, should be by means of a suitable inert oil.
        • {ALF} Monograph: J. Seyden-Penne, Reductions by the Alumino- and Borohydrides In Organic Synthesis, 2nd ed., Wiley, N.Y. (1997).
        • {ALF} Mixing with a flammable solvent must always be carried out under an inert atmosphere.
        • {ALF} Reverse addition (solvent to reagent), if done rapidly, may be safer.
        • {ALF} The use of Diethoxymethane, B23134 as a reaction solvent has also been recommended.
        • {uni_hamburg} Short: III/35C4
        • 16853-85-3 H89055 Lithium aluminium hydride
氢化锂铝

          化学属性

          Mol. FormulaLiAlH4
          Mol. Weight37.95
          Melting Point125
          Density0.905
          TSCAYes
          SolubilityDecomposes in water. Soluble in ether
          Flash Point-17 ºC
          Boiling Point66
          Appearance tablets (~0.5 g each)
          Stability对空气和湿度敏感
          Mol. FormulaAlH4Li
          Mol. Weight38
          Density0.905
          Density0.885
          Mol. FormulaAlH4Li
          Mol. Weight38.00