Sodium bis(trimethylsilyl)amide 双(三甲基硅基)氨基钠

规格: 2.0 M solution in THF, SpcSeal
CAS: 1070-89-9
产品编号: H12013
MDL: MFCD00009835
品牌: INFI

产品介绍

双(三甲基硅基)氨基钠(NaHMDS)是一种强碱，它的优势在于可以是固体试剂，且溶于广泛的非质子性溶剂中，如：四氢呋喃，乙醚，苯或甲苯中，有非常强的碱性但亲核性差，这是由于分子内具有两个体积庞大且有亲脂性的三甲基硅基(TMS)影响了它参与亲核取代反应。常用于反应中的去质子化或作为碱性反应中的催化剂，例如可以将酮和酯去质子化得到其烯醇衍生物、还可以与卤代烷烃反应得到胺的衍生物。

合成工艺

该产品与双(三甲基硅基)氨基锂生产工艺类似。有一种是由氢化钠或氨基钠与六甲基二硅氮烷在甲苯中回流反应。还有由金属钠和六甲基二硅氮烷在具有共轭不饱和键的电子载体苯乙烯存在下，在1,4-二氧六环溶剂中回流反应，得到双(三甲基硅基)氨基钠。

应用实例

1. 文章发展一种利用碱金属催化醛与甲苯的一锅法氨基苄基化反应。首先双(三甲基硅基)氨基与碳酸铯原位生产N-三甲基硅基醛亚胺，然后与甲苯衍生物发生苄基化反应，反应效率高且多种官能团耐受性好[1]。

图片来源于期刊：Organic Letters. 2019, 21, 8514-8518

2. 文章中的底物利用双(三甲基硅基)氨基钠烯醇化在不同溶剂溶剂和底物间表现出不同的选择性，只有在四氢呋喃中表现出很好的立体选择性，文献中利用密度泛函理论计算对反应进行了详细的研究[2]。

图片来源于期刊：Journal of the American Chemical Society. 2021, 143, 17452-17464

参考文献：

[1] Organic Letters. 2019, 21, 8514-8518

[2]Journal of the American Chemical Society. 2021, 143, 17452-17464


Chemical NameSodium bis(trimethylsilyl)amide, 95+%, pure
Synonym HEXAM HMN NA SALT HMN-Na 溶液 六甲基二硅氮烷 钠盐 溶液 N-SODIUMHEXAMETHYLDISILAZANE N-Sodiohe N-Sodiohexamethyldisilazane N-Sodiumhexamethyldisilazane N-lithiohexamethyldisilazane NAHMDS Natrium-bis-(trimethylsilyl)-amid Natriumbis-(t SOD SODIU SODIUM BIS(TRIMETHYLSILYL)AMIDE SOL., ~0 .6 M IN TOLUENE SODIUM BIS(TRIMETHYLSILYL)AMIDE, ~1 M IN THF Sodium bis(trimethylsilyl)amide Sodium bis(trimethylsilyl)amide (95%) {} {} {} {} {} {} {} {} {} {} {} {} { {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} { {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {} {
MDL NumberMFCD00009835
CAS Number1070-89-9
EC Number213-983-8
Beilstein Registry Number3629917
PubChem Substance ID2724254
Reaxys-RN3629917
Chemical Name Translation双(三甲基硅基)氨基钠
InChIKeyWRIKHQLVHPKCJU-UHFFFAOYSA-N
InChIInChI=1S/C6H18NSi2.Na/c1-8(2,3)7-9(4,5)6;/h1-6H3;/q-1;+1
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；
  • 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；
  • 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）；
  • 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；
  • S8 Keep container dry 保持容器干燥；
    Risk Statements
    • R11 Highly flammable 非常易燃
    • R14 Reacts violently with water 遇水会猛烈反应
    • 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
    • R19 May form explosive peroxides 可能生成易爆的过氧化物质
    • R34 Causes burns 会导致灼伤
    • 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
    • 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
      • 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。
      • P233 Keep container tightly closed. ?保持容器密闭。
      • 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。
      • P241+P242+P243
      • 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
      • P301+P330+P331+P310
      • P302+P352
      • P302+P361+P354
      • P303+P361+P353
      • P303+P361+P353+P310+P363
      • P304+P312
      • P304+P340
      • P304+P340+P310
      • P305+P351+P338
      • P305+P351+P338+P310
      • 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。
      • P403+P233
      • 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
        • 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
        • 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
        • 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), type ABEK (EN14387) respirator filter
          Packing GroupII
          UN Number 2924 UN2924 UN3096
          Storage condition Moisture Sensitive 易吸潮，密封保存。充入惰性气体，密闭保存。 Air & Moisture Sensitive 充氩保存 2-8°C
          Hazard Codes 3 F,C
          Hazard Class3/8
          Restrict -
        • ⑴. 常温下为微黄色至浅灰色结晶粉末，一般溶于四氢呋喃溶液中。
        • ⑵. 与铑(I)催化共同作用可显著加快苯乙炔的聚合反应。
        • ⑶.又称双(三甲基癸基)氨化钠
        • Significantly accelerated the polymerization of pheneylacetylene in conjunction with rhodium (I) catalysis
        • {ALF} Sufficiently nucleophilic to act as a protected form of ammonia in the synthesis of primary amines from halides and tosylates: Chem. Ber., 117, 1250 (1984).
        • {ALF} Useful sterically hindered base (NaHMDS) for, e.g. generation of enolates, Wittig reagents or carbenes.
        • {ALF} In the Wittig reaction, gives Li salt-free product distribution patterns, with selective (Z)-alkene formation: Chem. Ber., 109, 1694 (1976); Tetrahedron Lett., 30, 2173 (1989). For formation of anions of benzylic phosphonates and subsequent ɑɑ-difluorination, see N-Fluorobenzenesulfonimide, L13955.
        • {ALF} Used as a base for the preparation of ester enolates: J. Am. Chem. Soc., 93, 4945 (1971). Has been found to be superior to LDA for preparation of (Z)-enolates of ketones under thermodynamic control: Tetrahedron Lett., 30, 2779 (1989).
        • {uni_hamburg} Short: EINECS
        • {ALD} Beilstein: 4,IV,4014
        • {uni_hamburg} Short: III/35F
        • {ALF} Found to give better yields than LiHMDS or KHMDS for the carbenoid reactions with Dibromomethane, A10456: Synthesis, 201 (1972); Angew. Chem. Int. Ed., 11, 326 (1972).
          • 1070-89-9 H12013 Sodium bis(trimethylsilyl)amide 双(三甲基硅基)氨基钠

          化学属性

          Melting PointNo Data Available
          SolubilitySoluble in hexane, toluene, ether
          TSCAYes
          Flash Point-17°(1°F)
          Stability易吸潮
          Boiling Point
          Density0.9197
          Mol. FormulaC6H18NNaSi2
          Mol. Weight183.37
          Danger-Level-
          pH-:-
          Redox-

          *以上化合物性质及应用等信息仅供参考