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
l Lithium Triethyllborohydride,Marek Zaidlewicz,Herbert C. Brown, Encyclopedia of Reagents for Organic Synthesis,2001
l Krishnamutthy, S. Schubert R.M Brown, H, C, J., Am Chem. Soc 1973, 95, 8486
l JACS, 1973
Chemical Name | Sodium Cyanoborohydride |
CAS Number | 25895-60-7 |
Synonym |
Sodium cyanotrihydridoborate
Sodium borocyanohydride
Sodium Cyanotrihydroborate(1-)
Sodium cyanotrihydroborate
氰基硼氢化钠 |
MDL Number | MFCD00003516 |
Beilstein Registry Number | 4152656 |
PubChem Substance ID | 87575903 |
EC Number | 247-317-2 |
Merck Number | 8606 |
Reaxys-RN | 4152656 |
Chemical Name Translation | 氰基硼氢化钠 |
LabNetwork Molecule ID | LN01305334 |
GHS Symbol
WGK Germany | 2 |
Precautionary statements | |
- 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。
- P262 Do not get in eyes, on skin, or on clothing. 不要接触眼睛,皮肤或衣服。
- 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。
- P273 Avoid release to the environment. 避免释放到环境中。
- 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。
- P284 Wear respiratory protection.? 佩戴呼吸保护装置。
- P301+P310+P330
- P301+P330+P331+P310
- P303+P361+P353
- P303+P361+P353+P310+P363
- P304+P340+P310
- P305+P351+P338
- P305+P351+P338+P310
- P335+P334
- P370+P378
- P391 Collect spillage. Hazardous to the aquatic environment 收集对水环境有危害的泄漏物。
- P402+P404
- P403+P233
- P405 Store locked up. 上锁保管。
- P501 Dispose of contents/container to..… 处理内容物/容器.....
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Hazard statements | |
- H225 Highly flammable liquid and vapour 高度易燃液体和蒸气
- H228 Flammable solid 易燃固体
- 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。
- H300 Fatal if swallowed 吞食致命
- H300+H310+H330
- H301 Toxic if swallowed 吞食有毒
- H301+H311+H331
- H310 Fatal in contact with skin 皮肤接触致命
- H311 Toxic in contact with skin 皮肤接触中毒
- H314 Causes severe skin burns and eye damage 导致严重的皮肤灼伤和眼睛损伤
- H330 Fatal if inhaled 吸入致命
- H335 May cause respiratory irritation 可能导致呼吸道刺激
- H351 Suspected of causing cancer 怀疑致癌
- H400 Verytoxictoaquaticlife 对水生生物毒性非常大。
- H410 Verytoxictoaquaticlifewithlonglastingeffects 对水生生物毒性非常大并具有长期影响。
- H411 Toxictoaquaticlifewithlonglastingeffects 对水生生物有毒性并具有长期影响。
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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 |
Signal word |
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Safety Statements | |
- S61 Avoid release to the environment. Refer to special instructions/safety data sheet 避免释放到环境中,参考特别指示/安全收据说明书;
- 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;
- 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;
- S28 After contact with skin, wash immediately with plenty of ... (to be specified by the manufacturer) 皮肤接触后,立即用大量…(由生产厂家指定)冲洗;
- 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);
- 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;
- S8 Keep container dry 保持容器干燥;
- S1 Keep locked up 上锁;
- 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”
- S16 Keep away from sources of ignition - No smoking 远离火源,禁止吸烟;
- S50 Do not mix with ... (to be specified by the manufacturer) 不要与……(由生产厂家指定)混合;
- S36/37 Wear suitable protective clothing and gloves 穿戴适当的防护服和手套;
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Packing Group | II |
UN Number |
3134 |
Risk Statements | |
|
Storage condition |
Moisture Sensitive
Store under Argon
储存温度2-8°C,充氩储存
0-10°C
储存温度2-8°C ,充氩保护。
0-10 |
Hazard Codes |
F,T+,N
F,T,N
T+,N |
Hazard Class | 4.3/6.1 |
有机合成用还原剂,醛、酮、肟、烯胺类还原,β-内酰胺还原成β-氨基酸。氨的甲基化。
{ALF} Tosylhydrazones are reduced to methylenes. The relatively slow reduction of carbonyl compounds enables the tosylhydrazone to be generated in situ: J. Am. Chem. Soc., 93, 1793 (1971); 95, 3662 (1973). For a detailed study of the mechanism of tosylhydrazone reduction, see: J. Org. Chem., 54, 4175 (1989).
{ALF} Unlike borohydride reduction of carbonyl compounds which proceeds readily at the natural pH of the solution, reduction by sodium cyanoborohydride is very slow unless the pH is reduced to 3-4. Selective reduction of iminium ions occurs, however, at pH 6-8, leading to the widespread application of the reagent in reductive aminations of carbonyl compounds: J. Am. Chem. Soc., 93, 2897 (1971); Org. Synth. Coll., 6, 499 (1988). For improved methods using combinations with Ti(IV) chloride or isopropoxide, see: Tetrahedron Lett., 31, 5547 (1990); J. Org. Chem., 55, 2552 (1990).
{ALF} Oximes are reduced to hydroxylamines, as are O-alkyloximes: Tetrahedron Lett., 2493 (1974). Reduction in the presence of TiCl3 gives primary amines, via the imine: Synth. Commun., 18, 777 (1988).
{ALF} Monograph: J. Seyden-Penne, Reductions by the Alumino- and Borohydrides In Organic Synthesis, 2nd ed., Wiley, N.Y. (1997).
{ALF} For reviews of the chemistry of sodium cyanoborohydride, see: Synthesis, 135 (1975); Org. Prep. Proced. Int., 11, 201 (1979).