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 Name | Lithium 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 Number | MFCD00011075 |
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| EC Number | 240-877-9 |
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| PubChem Substance ID | 87560001 |
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| CAS Number | 16853-85-3 |
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| Merck Number | 350 |
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| Beilstein Registry Number | 11460447 |
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| Reaxys-RN | 11460447 |
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| Chemical Name Translation | 氢化铝锂 |
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| Wiswesser Line Notation | .AL..H4.LI |
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| LabNetwork Molecule ID | LN01341120 |
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GHS Symbol
| Precautionary statements | |
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- 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.....
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| 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
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| WGK Germany | 1 |
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| RTECS | BD0100000 |
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| 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 | |
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- 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；
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| Packing Group | I |
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| UN Number |
1410
3399 |
| Risk Statements | |
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- 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
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| 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 Class | 4.3 |
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| 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
