二乙氨基三氟化硫
外观
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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 ![]() | ||
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![]() ![]() ![]() | |||
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样本時要保持在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,但較難爆炸。[11][12]
参见
[编辑]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.