Lithium bis(trimethylsilyl)amide 双(三甲基硅基)氨基锂

规格: 1.0 M solution in THF, SpcSeal
CAS: 4039-32-1
产品编号: H12010
MDL: MFCD00008261
品牌: INFI

背景介绍

双(三甲基硅基)氨基锂(LiHMDS)又叫六甲基二硅基氨基锂。可用于制备低配位数的金属配合物，因为配体的位阻很大。在有机合成或药物合成中，双(三甲基硅基)氨基锂通常用作非亲核性强碱，与其他大位阻有机强碱，如二异丙基氨基锂，双三甲基硅基氨基钾，双三甲基硅基氨基钠等等相比，作用类似，但碱性更强，在某些反应中有其独特的地方，有其他有机碱不具备的优势。

合成工艺

一种是在惰性气体保护下，采用正丁基锂或氢化锂或氨基锂夺取六甲基二硅胺烷的质子，利用无水无氧的有机溶剂做反应溶剂，低温反应。另一种方式是采用金属锂和六甲基二硅胺烷高温反应，同时使用三氯化铁作为催化剂，反应完全后，再用四氢呋喃溶剂溶解，制得六甲基二硅烷胺锂四氢呋喃溶液。还有一种是惰性气体保护下，向反应容器中加入金属锂、异戊二烯、六甲基二硅氮烷和四氢呋喃，经一步合成反应得到最终产品。

应用实例

1.文章报道利用LiHMDS和三氟甲磺酸酐一步法将酰胺脱氢转化为烯酰胺，其中LiHMDS和磺酸酐添加顺序至关重要，需要先添加LiHMDS，否则产率由92%下降至52%。反应机理利用氘代实验证明，首先三氟甲磺酸酐将酰胺活化从而使N的α-氢酸化，之后发生去质子化和消除得到烯酰胺产物[1]。

 

  

图片来源于期刊：Journal of the American Chemical Society, 2021, 143, 10524-10529.


2.环状聚合物具有独特的物理化学和生物特性，但是合成具有很大的挑战性。该文章研发出利用LiHMDS促进环膨胀聚合的简单途径，从N-烷基-N羧酸酐(NNCA)合成具有生物活性的大环[2]。

图片来源于期刊：Journal of the American Chemical Society 2021, 143, 3697-3702.


参考文献：

[1] Journal of the American Chemical Society, 2021, 143, 10524-10529.

[2] Journal of the American Chemical Society 2021, 143, 3697-3702.


Chemical NameLithium bis(trimethylsilyl)amide
CAS Number4039-32-1
EC Number223-725-6
Beilstein Registry Number3567910
MDL NumberMFCD00008261
Synonym (LiN(SiMe3)2) Li bis(TMS)A Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal lithium bis(trimethylsilyl)amide {} {LY} Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal {} {} {LY} Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal {} {} {} {LY} Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal {} {} {} {} {} {} {} {} {LY} Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal {} {} {} {} {} {LY} Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal {} {} {} {} {} {} {LY} Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal {} {} {} {} {} {} {} {LY} Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal {} {} {} {} {} {} {} {} {LY} Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal {} {} {} {} {} {} {} {} {} {LY} Lithium bis(trimethylsilyl)amine,1.0M solution in THF,Safeseal {} {} {} {} {} {} {} {} {} {} {LY} Lithium bis(trimethylsilyl)amine,1
PubChem Substance ID2733832
Reaxys-RN8136861
Chemical Name Translation双(三甲基硅基)氨基锂
InChIKeyYNESATAKKCNGOF-UHFFFAOYSA-N
LabNetwork Molecule IDLN00162852
InChIInChI=1S/C6H18NSi2.Li/c1-8(2,3)7-9(4,5)6;/h1-6H3;/q-1;+1
Canonical SMILESC[Si]([N-][Si](C)(C)C)(C)C.[Li+]
GHS Symbol
Signal word Danger
WGK Germany3
Safety Statements
  • S16 Keep away from sources of ignition - No smoking 远离火源，禁止吸烟；
  • S20 When using do not eat or drink 使用时，不得进食，饮水；
  • 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；
  • S25 Avoid contact with eyes 避免眼睛接触；
  • 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；
  • S29 Do not empty into drains 不要排入下水道；
  • S30 Never add water to this product 切勿将水加入该产品中；
  • S33 Take precautionary measures against static discharges 对静电采取预防措施；
  • 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）；
  • S57 Use appropriate containment to avoid environmental contamination 使用适当容器避免环境污染；
  • 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；
  • S7/8 Keep container tightly closed and dry 保存在严格密闭容器中，保持干燥；
  • S8 Keep container dry 保持容器干燥；
  • S9 Keep container in a well-ventilated place 保持容器在通风良好的场所；
    Risk Statements
    • R11 Highly flammable 非常易燃
    • R14 Reacts violently with water 遇水会猛烈反应
    • 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
    • R34 Causes burns 会导致灼伤
    • R35 Causes severe burns 会导致严重灼伤
    • 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
    • R51/53
    • R62 Possible risk of impaired fertility 有削弱生殖能力的危险
    • R63 Possible risk of harm to the unborn child 可能危害未出生婴儿
    • 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
      • P201 Obtain special instructions before use. 使用前获取专门指示。
      • 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。
      • 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。
      • 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。
      • P264+P265
      • 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。
      • P301+P312
      • P301+P317
      • P301+P330+P331
      • P302+P352
      • P302+P361+P354
      • P303+P361+P353
      • P304+P312
      • P304+P340
      • P304+P340+P310
      • P305+P351
      • P305+P351+P338
      • P305+P354+P338
      • P308+P311
      • P310 Immediately call a POISON CENTER or doctor/physician. 立即呼救解毒中心或医生/医师。
      • P312 Call a POISON CENTER or doctor/physician if you feel unwell. 如果你感觉不适，呼叫解毒中心或医生/医师。
      • P316
      • P317
      • P321 Specific treatment (see … on this label). 具体治疗（见本标签上的）。
      • P322 Specific measures (see …on this label). 具体治疗（见本标签上的）。
      • P330 Rinse mouth. 漱口
      • P362+P364
      • P363 Wash contaminated clothing before reuse. 被污染的衣服洗净后方可重新使用。
      • P370+P378
      • P403+P233
      • P403+P235
      • P405 Store locked up. 上锁保管。
      • P501 Dispose of contents/container to..… 处理内容物/容器.....
        Hazard statements
        • H225 Highly flammable liquid and vapour 高度易燃液体和蒸气
        • H228 Flammable solid 易燃固体
        • H302 Harmful if swallowed 吞食有害
        • H304 May be fatal if swallowed and enters airways 吞食和进入呼吸道可能致命
        • H312 Harmful in contact with skin 皮肤接触有害
        • H314 Causes severe skin burns and eye damage 导致严重的皮肤灼伤和眼睛损伤
        • H318 Causes serious eye damage 严重伤害眼睛
        • H332 Harmful if inhaled 吸入有害
        • H335 May cause respiratory irritation 可能导致呼吸道刺激
        • H336 May cause drowsiness or dizziness 肯能导致嗜睡或头晕
        • H351 Suspected of causing cancer 怀疑致癌
        • H361 Suspected of damaging fertility or the unborn child 怀疑对生育能力或未出生婴儿造成伤害
        • 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
        • H411 Toxictoaquaticlifewithlonglastingeffects 对水生生物有毒性并具有长期影响。
        • H412 Harmfutoaquaticlifewithlonglastingeffects 对水生生物有害并具有长期影响。
          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 Faceshields, full-face respirator (US), Gloves, Goggles, multi-purpose combination respirator cartridge (US) Faceshields, full-face respirator (US), Gloves, Goggles, multi-purpose combination respirator cartridge (US), type ABEK (EN14387) respirator filter
          Packing GroupII
          UN Number 2924 UN2924
          Storage condition 2-8°C, sealed storage, away from moisture {LY} 2-8°C, sealed storage, away from moisture below 5° C {} {LY} 2-8°C, sealed storage, away from moisture {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage, away from moisture {} {} {} {} {} {} {} {} {} {} {} {} {} {LY} 2-8°C, sealed storage
          Hazard Codes 3 F,C
          Hazard Class3/8
          Restrict -
        • ⑴.也称二(三甲基硅基)氨基锂。熔点71～72℃。沸点114～116℃(133.322Pa)。自燃，惰气保护下密封贮运。对空气与水敏感。以硅氨在乙醚中与金属锂反应而得。
        • ⑵.用于醛醇缩合，是常用的有机碱。例如形成乙炔化锂，或者制备烯醇锂盐。
        • ⑶. 双(三甲基硅基)氨基锂可用于制备低配位数的配合物，因为配体(TMS)2N-的位阻很大。这样的例子有M[N(TMS)2]3（M = Sc, Ti, V, Fe ；TMS = (CH3)3Si)）。与三甲基氯硅烷反应产生三(三甲基硅基)胺，其中氮的配位数为3，空间构
        • 非亲核性强碱，可用于形成烯醇的反应，烯醇酯立体专一克莱森重排反应，将醛转化为硅亚胺的反应，生成缩水甘油酸酯的反应，β内酰胺的反应，芳基烷基醚的选择性断裂反应。
        • {ALF} Supplied in septum cap bottle.
        • {ALF} Versatile non-nucleophilic strong base. For examples of use in the lithiation of ethyl acetate, see: Org. Synth. Coll., 6, 598 (1988), and in the stereospecific Wadsworth-Emmons synthesis of fluoroalkenes from (E)- and (Z)-fluorovinyl sulfones: Org. Synth. Coll., 9, 442 (1998).
          • 4039-32-1 H12010 Lithium bis(trimethylsilyl)amide 双(三甲基硅基)氨基锂

          化学属性

          Mol. FormulaC6H18LiNSi2
          Mol. Weight 167.33
          Density0.87
          Boiling Point55 - 56 °C
          Flash Point-17 °C - (闭杯)
          TSCAYes
          Melting Point70 - 76 °C
          Solubility水解
          Refractive indexn20/D 1.425(lit.)
          Stability对空气和湿度敏感
          Danger-Level甲类
          pH-:-
          Redox-

          *以上化合物性质及应用等信息仅供参考