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 | Tributyltin Hydride |
|---|
| Synonym |
Hydridotris(butyl)tin
Stannane, tributyl-
TBTHTri-n-butylstannane
TIN TRIBUTYL HYDRIDE
TRI-N-BUTYLTIN
TRI-N-BUTYLTIN HYDRIDE
TRIBUTYLSTANNANE
TRIBUTYLTINHYDRIDE,TECHNICAL
Tin, tri-n-butyl-, hydride
Tri-n-butyl tin hydride
Tri-n-butylstannane
Tri-n-butyltin
Tri-n-butyltin; Tributylstannane
Tri-n-butyltinhydride,min.95%
Tributylstannane
Tributylstannyl hydride
Tributylstannyl hydride solution
Tributyltin
Tributyltin hydride
Tributylzinnhydrid
tbth
tri-n-butylstannanehydride
tributyl-stannane
三丁基氢化锡 溶液
三正丁基氢化锡
三正丁基氢锡
氢化三丁锡 |
| CAS Number | 688-73-3 |
|---|
| EC Number | 211-704-4 |
|---|
| Beilstein Registry Number | 3587329 |
|---|
| MDL Number | MFCD00009416 |
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| PubChem Substance ID | 87577235 |
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| Reaxys-RN | 3587329 |
|---|
| Chemical Name Translation | 三正丁基氢锡 |
|---|
| Wiswesser Line Notation | 4-SN-H4&4 |
|---|
| LabNetwork Molecule ID | LN00193590 |
|---|
| Signal word |
Danger |
GHS Symbol
| WGK Germany | 3 |
|---|
| Safety Statements | |
|---|
- S16 Keep away from sources of ignition - No smoking 远离火源，禁止吸烟；
- 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；
- S33 Take precautionary measures against static discharges 对静电采取预防措施；
- S35 This material and its container must be disposed of in a safe way 该物料及其容器必须以安全方式处置；
- 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；
- 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；
- 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；
- S62 If swallowed, do not induce vomiting: seek medical advice immediately and show this container or label where possible 吞食后不要催吐：立即求医并出示该容器或标签；
|
| Risk Statements | |
|---|
- R10 Flammable 易燃
- 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
- R21 Harmful in contact with skin 与皮肤接触有害
- R25 Toxic if swallowed 吞咽有毒
- R30/38
- R36/38 Irritating to eyes and skin 对眼睛和皮肤有刺激性
- R48/23/25
- R50/53
- R65 Harmful: may cause lung damage if swallowed 若吞咽可能伤害肺部器官
- R67 Vapours may cause drowsiness and dizziness 蒸汽可能导致嗜睡和昏厥
|
| 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。
- P240 Ground/bond container and receiving equipment. 与地面接触/连接集装箱和接受设备。
- P241 Use explosion-proof electrical/ventilating/lighting/…/equipment. 使用防爆电气/通风/照明/ .../设备。
- P261 Avoid breathing dust/fume/gas/mist/vapours/spray. 避免吸入粉尘/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。
- 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。
- P301+P310
- P303+P361+P353
- P305+P351+P338
- P314 Get medical advice/attention if you feel unwell. 获取医疗咨询/就医，如果你觉得不舒服
- P332+P313
- P337+P313
- P403+P235
- P501 Dispose of contents/container to..… 处理内容物/容器.....
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| Hazard statements | |
|---|
- H315 Causes skin irritation 会刺激皮肤
- H301 Toxic if swallowed 吞食有毒
- H312 Harmful in contact with skin 皮肤接触有害
- H410 Verytoxictoaquaticlifewithlonglastingeffects 对水生生物毒性非常大并具有长期影响。
- H319 Causes serious eye irritation 严重刺激眼睛
- H372 Causes damage to organs through prolonged or repeated exposure 长期或频繁接触会损伤器官
- H226 Flammable liquid and vapour 易燃液体和蒸气
- 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
- H225 Highly flammable liquid and vapour 高度易燃液体和蒸气
- H302+H332
- H302 Harmful if swallowed 吞食有害
|
| Personal Protective Equipment |
Eyeshields, Faceshields, full-face respirator (US), Gloves, multi-purpose combination respirator cartridge (US), type ABEK (EN14387) respirator filter |
| RTECS | WH8675000 |
|---|
| Packing Group | I |
|---|
| UN Number |
1993
2929
3399 |
| Storage condition |
Air & Moisture Sensitive
2-8℃保存。
0-10°C
0-10
储存温度2-8℃; 充氩保存
2-8°C |
| Hazard Codes |
3
4.3
T,N
T,N,F |
| Hazard Class | 6.1/3 |
|---|
| Warnings |
危化品目录(2015) |
TYPE OF TEST : LCLo - Lowest published lethal concentration
ROUTE OF EXPOSURE : Inhalation
SPECIES OBSERVED : Rodent - mouse
DOSE/DURATION : 1460 mg/m3/10M
TOXIC EFFECTS :
Sense Organs and Special Senses (Eye) - lacrimation
Behavioral - convulsions or effect on seizure threshold
Lungs, Thorax, or Respiration - dyspnea
REFERENCE :
NDRC** National Defense Research Committee, Office of Scientific Research
and Development, Progress Report. Volume(issue)/page/year:
NDCrc-132,FEB1942
| Restrict |
危险品 |
广泛使用的自由基试剂，可用于还原裂解、自由基脱卤以及分子内自由基环化。
{ALF} Dialdehydes and keto aldehydes undergo free-radical intramolecular pinacol coupling to give cyclic diols: J. Am. Chem. Soc., 117, 7283 (1995); J. Org. Chem., 63, 6357 (1998).
{ALD} Merck: 14,10451
Beilstein:4(4)4312
{
{uni_hamburg} Short: III/38A
{ALF} TBTH also cleaves other C-heteroatom bonds, controlled by the stability of the resulting radical: Nitro-groups at tertiary centers are readily cleaved: Synthesis, 693 (1986). Azides are readily reduced to amines: Synlett, 342 (1991). C-S and C-Se bonds are also cleaved. J. Am. Chem. Soc., 104, 2046 (1982); 112, 4008 (1990); J. Org. Chem., 49, 5206 (1984); 54, 1234 (1989).
{uni_hamburg} Short: III/35C4
{ALF} Reducing agent and source of tributyltin radicals. Widely used for selective reduction of alkyl halides to alkanes by a radical chain mechanism. The reaction is tolerant of a wide range of functionality, including OH and NH, in contrast to polar metal hydride reagents. For reviews, see: Synthesis, 499 (1970); 665 (1987). For a brief feature on uses of this reagent in synthesis, see: Synlett, 173 (2007). For use in the synthesis of deoxy sugars via reductive rearrangement of glycosyl bromides, see: Org. Synth. Coll., 8, 583 (1993). Cyclization of the initially-formed alkyl radical to a suitably positioned double bond may occur. Formation of 5-membered rings is strongly favoured, and ring closure onto an existing ring gives the cis-fused product. See, e.g.: J. Am. Chem. Soc., 108, 5893 (1986):
{ALF} Free-radical hydrostannylation of alkenes occurs with TBTH to give alkylstannanes. The reaction is catalyzed by, e.g. Rh complexes: Chem. Lett., 881 (1988), or Pd complexes: Angew. Chem. Int. Ed., 35, 1329 (1996), and refs therein. Syn-addition to alkynes gives vinylstannanes, useful intermediates which undergo electrophilic substitution reactions with retention of configuration. Thus, iodine, NIS and NBS give vinyl halides: J. Org. Chem., 47, 404 (1982); Tetrahedron, 42, 3575 (1986), and alkyllithium compoun
