二乙氨基三氟化硫
| 二乙氨基三氟化硫[1] | |||
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| IUPAC名 N,N-Diethyl-S,S,S-trifluoro-λ4-sulfanamine | |||
| 别名 | 二乙氨基三氟化硫 二乙(三氟化硫)胺 | ||
| 识别 | |||
| 缩写 | DAST | ||
| CAS号 | 38078-09-0 
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| PubChem | 123472 | ||
| ChemSpider | 110068 | ||
| SMILES |
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| InChI |
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| InChIKey | OJRFYRBETDFODT-DFZHHIFOAR | ||
| 性质 | |||
| 化学式 | C4H10F3NS | ||
| 摩尔质量 | 161.19 g·mol−1 | ||
| 外观 | 无色油状液体 | ||
| 密度 | 1.220 g/cm3 | ||
| 沸点 | 30—32 °C（86—90 °F；303—305 K）（3 mmHg） | ||
| 溶解性（水） | 反应 | ||
| 溶解性 | 和乙醇反应，可溶于乙腈 | ||
| 危险性 | |||
GHS危险性符号  
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| GHS提示词 | Danger | ||
| H-术语 | H226, H302, H312, H314, H332 | ||
| P-术语 | P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P280, P301+312, P301+330+331 | ||
| 主要危害 | 有腐蚀性，可燃，可以爆炸 | ||
| 若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。 | |||
二乙基氨基三氟化硫，简称DAST[2]是一种有机硫化合物，化学式 Et2NSF3。这种液体是一种氟化剂，用于合成有机氟化合物。二乙基氨基三氟化硫是无色的，但旧样本会呈橙色。
制备
[编辑]DAST可以由二乙基氨基三甲基硅烷和四氟化硫反应而成：[3]
- Et2NSiMe3 + SF4 → Et2NSF3 + Me3SiF
原论文使用三氯氟甲烷（氟利昂-11）作为溶剂，但这种化合物因为被蒙特利尔议定书禁用，不再作为商品化学品提供，现已使用乙醚作为替代溶剂。[4]
用处
[编辑]DAST在有机合成中用作氟化剂，可以把醇（ROH）和醛（RCHO）氟化成对应的氟代烃（RF和RCHF2）。[5]它和硫醚或亚砜反应，生成对应的α-氟代硫醚。[6][7][8]
危险和替代试剂
[编辑]DAST加热分解成极易爆炸的(NEt2)2SF2，并产生四氟化硫气体。为了尽量减少发生事故，存放DAST样本时要保持在50 °C以下。[10]双(2-甲氧乙基)氨基三氟化硫（商品名Deoxo-Fluor）和四氟硼酸二氟(吗啉基)化锍（商品名XtalFluor-M）都是衍生自DAST的试剂，但较难爆炸。[11][12]
参见
[编辑]- 石川试剂
- 氨基硫烷的氟化反应
参考资料
[编辑]- ^ A. H. Fauq, "N,N-Diethylaminosulfur Trifluoride" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York.
- ^ Middleton, William J. New fluorinating reagents. Dialkylaminosulfur fluorides. The Journal of Organic Chemistry. 1975-03-01, 40 (5): 574–578. ISSN 0022-3263. doi:10.1021/jo00893a007.
- ^ W. J. Middleton, E. M. Bingham "Diethylaminosulfur Trifluoride" Organic Syntheses, Coll. Vol. 6, p.440; Vol. 57, p.50. Online version （页面存档备份，存于互联网档案馆）
- ^ L. N. Markovskij; V. E. Pashinnik; A. V. Kirsanov. Application of Dialkylaminosulfur Trifluorides in the Synthesis of Fluoroorganic Compounds. Synthesis. 1973, 1973 (12): 787–789. doi:10.1055/s-1973-22302.
- ^ Organo-Fluorine Compounds, B. Baasner, H. Hagemann, J. C. Tatlow (Hrsg.), Houben-Weyl/Thieme, Stuttgart, 2000.
- ^ McCarthy, James R.; Peet, Norton P.; LeTourneau, Michael E.; Inbasekaran, Muthiah. (Diethylamino)sulfur trifluoride in organic synthesis. 2. The transformation of sulfoxides to .alpha.-fluoro thioethers. Journal of the American Chemical Society (American Chemical Society (ACS)). 1985, 107 (3): 735–737. ISSN 0002-7863. doi:10.1021/ja00289a053.
- ^ Wnuk, Stanislaw F.; Robins, Morris J. Antimony(III) chloride exerts potent catalysis of the conversion of sulfoxides to .alpha.-fluoro thioethers with (diethylamino)sulfur trifluoride. The Journal of Organic Chemistry (American Chemical Society (ACS)). 1990, 55 (15): 4757–4760. ISSN 0022-3263. doi:10.1021/jo00302a052.
- ^ Robins, Morris J.; Wnuk, Stanislaw F. Nucleic acid related compounds. 79. Efficient conversions of thioethers to .alpha.-fluoro thioethers with DAST or DAST/antimony(III) chloride. The Journal of Organic Chemistry (American Chemical Society (ACS)). 1993, 58 (15): 3800–3801. ISSN 0022-3263. doi:10.1021/jo00067a009.
- ^ 来源：Sigma-Aldrich Co., product no. 235253 .
- ^ Messina, P. A.; Mange, K. C.; Middleton, W. J. Aminosulfur trifluorides: relative thermal stability. Journal of Fluorine Chemistry. 1989, 42 (1): 137–143. doi:10.1016/S0022-1139(00)83974-3.
- ^ l'Heureux, A.; Beaulieu, F.; Bennett, C.; Bill, D. R.; Clayton, S.; Laflamme, F. O.; Mirmehrabi, M.; Tadayon, S.; Tovell, D.; Couturier, M. Aminodifluorosulfinium Salts: Selective Fluorination Reagents with Enhanced Thermal Stability and Ease of Handling†,‡. The Journal of Organic Chemistry. 2010, 75 (10): 3401–3411. PMC 2869536
. doi:10.1021/jo100504x.
- ^ Beaulieu, F.; Beauregard, L. P.; Courchesne, G.; Couturier, M.; Laflamme, F. O.; l’Heureux, A. Aminodifluorosulfinium Tetrafluoroborate Salts as Stable and Crystalline Deoxofluorinating Reagents. Organic Letters. 2009, 11 (21): 5050–5053. PMC 2770860 . PMID 19799406. doi:10.1021/ol902039q.
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