簡(jian)介
氫化鋰, 氫化鋁鋰,硼氫化鈉,三乙基硼氫化鋰(Super Hydride)/鈉/鉀 ,三仲丁基硼氫化鋰( L-Selectride)/鈉/鉀(K-Selectride),Lithium Trisiamylborohydride (LiBSia3H) 60217-34-7, 三叔丁氧基氫化鋁鋰,77299-63-9 Lithium diisobutyl-tert-butoxyaluminum hydride solution,Diisobutylaluminum hydride, DIBAL,硼烷四氫呋喃,氨基硼烷等, 金屬氫化物,作為還原劑和負氫離子的來源,廣泛用于無機和有機合成中,以及作為儲氫材料應用到日常生產生活中。金屬氫化物還原劑,可以還原取代鹵代物到烷烴,醛酮環氧亞胺等到醇或胺,羧酸衍生物如酯,腈及其他衍生物到特別是某些烴基取代的金屬化合物,具有反應條件溫和,副反應少以及產率高的優點,體現出較好的化學選擇性和立體 選擇性。在復雜的天然產物,藥物分子的合成中,較之其他還原法顯示出更多的優點。
應用舉(ju)例(li)
1. 還(huan)原鹵代(dai)物等(deng)到相應的烷烴(反應式A,B),并(bing)且氘代(dai)實(shi)驗表明,該還(huan)原反應經過明確的SN2取代(dai)機理(反應式B)。另外,OTs,OMs等(deng)取代(dai)基也能被還(huan)原。
2. 還原(yuan)環(huan)氧到醇,在(zai)如下(xia)例中,三乙基硼氫化(hua)鋰比的四氫鋁鋰的選擇性要高很多。
3. 選擇性還原醛酮(tong)(tong)到相應(ying)的(de)(de)醇。在α-環(huan)(huan)己酮(tong)(tong)的(de)(de)還原中,以很高(gao)的(de)(de)選擇性的(de)(de)得到順勢的(de)(de)產(chan)品(反應(ying)式D);并(bing)且在醛和酮(tong)(tong)同時存在的(de)(de)情況(kuang)下,可以優先(xian)還原醛到相應(ying)的(de)(de)一級(ji)醇(反應(ying)式E)。其(qi)中,Lithium trisiamylborohydride (LiBSia3H)表現(xian)出更好的(de)(de)選擇性,以其(qi)他(ta)取代的(de)(de)環(huan)(huan)己酮(tong)(tong)為例(li),各氫化物還原總結如表一。
4. 選(xuan)擇性(xing)(xing)的還原羧酸及其衍生物。可以在(zai)有其他(ta)可被還原的基(ji)團(tuan)存在(zai)下,選(xuan)擇性(xing)(xing)的還原酯基(ji)。
5.其他用途(tu)。氫化物(wu)也(ye)可以轉(zhuan)移(yi)負氫離子到其他的(de)過度(du)金屬(shu)有機(ji)化合物(wu)上,形成新的(de)M-H化合物(wu),選擇(ze)性的(de)脫除甲基。
參考文(wen)獻
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 | Bis(Cyclopentadienyl)Zirconium Chloride Hydride |
Synonym |
Bis(cyclopentadienyl)chlorohydrozirconium
{LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {}
{} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {} {} {} {} {
{} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {} {} {} {} {} {} {} {
{} {} {} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {} {} {} {} {} {} {} {} {
{} {} {} {} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohydrozirconium
{} {} {} {} {} {} {} {} {} {} {} {} {LY} Bis(cyclopentadienyl)chlorohy |
PubChem Substance ID | 87577928 |
EC Number | 253-479-5 |
Merck Number | 8396 |
Chemical Name Translation | 氫氯二茂鋯 |
InChIKey | UVWUHPCWBZSERX-UHFFFAOYSA-M |
MDL Number | MFCD02089401 |
CAS Number | 37342-97-5 |
Canonical SMILES | [][Zr]([H])(Cl)[].c1cccc1.c2cccc2 |
WGK Germany | 3 |
GHS Symbol
Precautionary statements | |
- P422 Store contents under… 存儲目錄在…之下。
- P310 Immediately call a POISON CENTER or doctor/physician. 立即呼救解毒中心或醫生/醫師。
- P231+P232
- P280 Wear protective gloves/protective clothing/eye protection/face protection. 戴防護手套/防護服/眼睛的保護物/面部保護物。
- P305+P351+P338
- P271 Use only outdoors or in a well-ventilated area.? 只能在室外或通風良好的地方使用。
- P223 Keep away from any possible contact with water, because of violent reaction and possible flash fire. 遠離任何與水接觸的可能,因為會劇烈反應可能產生閃火。
- P501 Dispose of contents/container to..… 處理內容物/容器.....
- P260 Do not breathe dust/fume/gas/mist/vapours/spray. 不要吸入粉塵/煙/氣體/煙霧/蒸汽/噴霧。
- P305+P351+P338+P310
- P264 Wash hands thoroughly after handling. 處理后要徹底洗凈雙手。
- P301+P330+P331+P310
- P303+P361+P353
- P370+P378
- P270 Do not eat, drink or smoke when using this product. 使用本產品時不要吃東西,喝水或吸煙。
- P304+P340+P310
- P301+P330+P331
- P402+P404
- P303+P361+P353+P310+P363
|
Hazard statements | |
- H314 Causes severe skin burns and eye damage 導致嚴重的皮膚灼傷和眼睛損傷
- H261 In contact with water releases flammable gas 與水接觸時釋放可燃氣體。
|
Signal word |
|
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 |
Safety Statements | |
- S26 In case of contact with eyes, rinse immediately with plenty of water and seek medical advice 眼睛接觸后,立即用大量水沖洗并征求醫生意見;
- S27 Take off immediately all contaminated clothing 立即脫掉全部污染的衣服;
- S36/37/39 Wear suitable protective clothing, gloves and eye/face protection 穿戴適當的防護服、手套和眼睛/面保護;
- S16 Keep away from sources of ignition - No smoking 遠離火源,禁止吸煙;
- S45 In case of accident or if you feel unwell seek medical advice immediately (show the label where possible) 發生事故時或感覺不適時,立即求醫(可能時出示標簽);
- S33 Take precautionary measures against static discharges 對靜電采取預防措施;
- 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) 著火時使用(指明具體的消防器材種類,如果用水增加危險,注明“禁止用水”
- S60 This material and its container must be disposed of as hazardous waste 該物質及其容器必須作為危險廢物處置;
|
Packing Group | II |
UN Number |
3131 |
Risk Statements | |
- R11 Highly flammable 非常易燃
- R15 Contact with water liberates extremely flammable gases 遇水會釋放出極端易燃的氣體
- R34 Causes burns 會導致灼傷
|
Storage condition |
2-8°C, protect from light, stored under nitrogen
{LY} 2-8°C, protect from light, stored under nitrogen
Light, Air & Moisture Sensitive
{} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, protect from light, stored under nitrogen
{} {} {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C |
Hazard Codes |
F,C |
Hazard Class | 4.3/8 |
Restrict |
- |
轉化氨基化合物生成醛類化合物;石蠟和炔烴的功能化試劑。
{ALF} Reagent for selective reduction of secondary carboxamides to imines, a transformation otherwise difficult to achieve since imines are normally more easily reduced than amides: J. Org. Chem., 61, 4115 (1996); tertiary amides can also be reduced to aldehydes at room temperature: J. Am. Chem. Soc., 122, 11995 (2000). Reduction of phosphine oxides and phosphine sulfides to phosphines under mild conditions has also been reported: Tetrahedron Lett., 38, 5997 (1997).
{ALF} Catalyzes the hydroboration of alkynes with Pinacolborane, L17558, to form alkenylboronates with high regio- and stereoselectivity: Organometallics, 14, 3127 (1995). Alkenes are similarly converted to alkylboronates: J. Am. Chem. Soc., 118, 909 (1996).
{ALF} Reaction with alkenes (hydrozirconation) results in zirconocene alkyl chlorides: Tetrahedron Lett., 28, 3895 (1987). Useful products are obtained by reaction of these with various electrophiles. With O-(mesitylsulfonyl)hydroxylamine, primary amines are obtained, with generally good yields and regioselectivity: J. Org. Chem., 60, 1912 (1995).
{ALF} For a brief feature on the reagent, see: Synlett, 1179 (1999); review of synthetic applications of organozirconocene compounds: Tetrahedron, 52, 12853 (1996)
{ALD} Merck: 14,8396