Lithium aluminium hydride 氢化锂铝

规格: 1.0 M solution in THF , SpcSeal
CAS: 16853-85-3
产品编号: H98239
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,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 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
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  • 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
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  • 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;
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      • 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)
          Restrict 危险品
        • 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 H98239 Lithium aluminium hydride
氢化锂铝

          化学属性

          Melting Point125
          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
          Density0.885
          Mol. FormulaLiAlH4
          Mol. Weight37.95
          RedoxReduction
          pH:A

          *以上化合物性质及应用等信息仅供参考