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2,3-环氧丁烷

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2,3-环氧丁烷
IUPAC名
2,3-Dimethyloxirane
别名 2,3-二甲基环氧乙烷
2-丁烯环氧化物
识别
CAS号 3266-23-7  checkY
1758-33-4（R,S）  checkY
21490-63-1（S,S）  checkY
1758-32-3（R,R）  checkY
PubChem 18632
92162
30664
6432237
SMILES
 
  • CC1C(O1)C
InChI
 
  • 1S/C4H8O/c1-3-4(2)5-3/h3-4H,1-2H3
InChIKey PQXKWPLDPFFDJP-UHFFFAOYSA-N
UN编号 3271
性质
化学式 C4H8O
摩尔质量 72.11 g·mol−1
外观 无色液体
密度 0.837 g·cm−3
熔点 −85 °C（188 K）（S,S）[1]
−80 °C（193 K）（R,S）[1]
沸点 55—56 °C（328—329 K）[2]
56.5 °C（329.6 K）（S,S）[1]
60 °C（333 K）（R,S）[3]
53.5 °C（326.6 K）（746 torr，R,R）[4]
若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

2,3-环氧丁烷（英語：2,3-Epoxybutane）是化学式为CH3CH(O)CHCH3的环氧化合物，带有两个手性碳原子，其中的(2R,3S)-2,3-环氧丁烷为内消旋化合物，因此总共有三种立体异构体，它们都是无色液体。

合成

2,3-环氧丁烷可由2-丁烯为原料进行合成，反应会生成中间体卤代醇（英语：Halohydrin）[5]：

CH3CH=CHCH3 + HOCl → CH3CH(OH)CH(Cl)CH3
CH3CH(OH)CH(Cl)CH3 → CH3CH(O)CHCH3 + HCl

2,3-丁二醇在偶氮二甲酸二乙酯和三苯基膦的存在下脱水环化，也可以得到2,3-环氧丁烷。[6]

性质

2,3-环氧丁烷的三元环不稳定，可以发生开环反应，如氢化生成对应的2,3-丁二醇[7]。它和溴代甲硼烷二甲硫醚反应，可以得到3-溴-2-丁醇。[8]在二甲基氧鎓四氟硼酸盐催化下，二甲基亚砜可将其氧化为3-羟基-2-丁酮。[9]

它和二氧化碳发生环加成反应，生成2,3-丁二醇-2,3-环碳酸酯，反应所用的催化剂已有较多报道，如氨基酸-碘化钾[10]、金属有机框架材料[11]等。它和二硫化碳反应，生成2,3-丁二醇-2O,3S-二硫代环碳酸酯。[12]

2,3-环氧丁烷和二氧化碳的环加成反应。
2,3-环氧丁烷和二硫化碳的环加成反应。

2,3-环氧丁烷和五氧化二氮在二氯甲烷中反应，得到2,3-丁二醇-2,3-二硝酸酯；[13]和四硝基甲烷反应，得到2,3-丁二醇-2-硝酸酯。[14]它和三甲基氰硅烷发生开环反应，得到2-甲基-3-三甲基硅氧基丁腈。[15]它和O-异丙基-O-苯基硒代磷酸反应，得到2-异丙基-4,5-二甲基-1,3,2-氧杂硒杂磷杂环戊烷-2-氧化物。[16]

参考文献

  1. ^ 1.0 1.1 1.2 "PhysProp" data were obtained from Syracuse Research Corporation of Syracuse, New York (US). Retrieved from SciFinder. [2021-07-10].
  2. ^ Cottle, D. L.; Powell, Leo S. The Reaction of 2,3-Epoxybutane with the Grignard Reagent. Journal of the American Chemical Society. 2002, 58 (11): 2267–2272. ISSN 0002-7863. doi:10.1021/ja01302a052. 
  3. ^ Farberov, M. I.; Bondarenko, A. V.; Obukhov, V. M.; Stepanova, I. P.; Srednev, S. S.; Vasil'eva, I. A. Epoxidation of 2-butene by organic hydroperoxides and syntheses based on 2-butene oxide. II. Syntheses based on 2-butene oxide（俄文）. Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation), 1984. 57 (11): 2581-2584. ISSN: 0044-4618. CODEN: ZPKHAB.
  4. ^ Leroux, P. J.; Lucas, H. J. L(-)-2-Butanol from D(-)-2,3-Butanediol. Journal of the American Chemical Society. 2002, 73 (1): 41–42. ISSN 0002-7863. doi:10.1021/ja01145a015. 
  5. ^ Heinz Gräfje, Wolfgang Körnig, Hans-Martin Weitz, Wolfgang Reiß, Guido Steffan, Herbert Diehl, Horst Bosche, Kurt Schneider and Heinz Kieczka "Butanediols, Butenediol, and Butynediol" in Ullmann's Encyclopedia of Industrial Chemistry, 2000, Wiley-VCH, Weinheim. doi:10.1002/14356007.a04_455
  6. ^ Castro, Bertrand R. Replacement of Alcoholic Hydroxyl Groups by Halogens and Other Nucleophiles via Oxyphosphonium Intermediates: 18. 2005. doi:10.1002/0471264180.or029.01. 
  7. ^ Nugent, William A. Desymmetrization of Meso Epoxides with Halides: A New Catalytic Reaction Based on Mechanistic Insight. Journal of the American Chemical Society. 1998, 120: 7139–7140. doi:10.1021/JA981031L. 
  8. ^ Brown, Herbert C.; Roy, Chandra Deo. Dibromoborane-Dimethyl Sulfide and Monobromoborane-Dimethyl Sulfide as Superior Reagents for the Opening of Oxiranes to Bromohydrins. Molecules Online. 1998, 2 (8): 114–120. ISSN 1433-1373. doi:10.1007/s007830050066. 
  9. ^ Tsuji, Tadakazu. Acid-Catalyzed Oxidation of Oxiranes with Dimethyl Sulfoxide Giving α-Hydroxy Ketones. Bulletin of the Chemical Society of Japan. 1989, 62 (2): 645–647. ISSN 0009-2673. doi:10.1246/bcsj.62.645. 
  10. ^ Yang, Zifeng; Sun, Jian; Cheng, Weiguo; Wang, Jinquan; Li, Qian; Zhang, Suojiang. Biocompatible and recyclable amino acid binary catalyst for efficient chemical fixation of CO2. Catalysis Communications. 2014, 44: 6–9. ISSN 1566-7367. doi:10.1016/j.catcom.2013.07.025. 
  11. ^ Parmar, Bhavesh; Patel, Parth; Pillai, Renjith S.; Kureshy, Rukhsana I.; Khan, Noor-ul H.; Suresh, Eringathodi. Efficient catalytic conversion of terminal/internal epoxides to cyclic carbonates by porous Co(ii) MOF under ambient conditions: structure–property correlation and computational studies. Journal of Materials Chemistry A. 2019, 7 (6): 2884–2894. ISSN 2050-7488. doi:10.1039/C8TA10631B. 
  12. ^ Pielichowski, Jan; Czub, Piotr. Preparation of substituted 1,3-oxothiolane-2-thiones by reacting epoxides with carbon disulfide（波兰文）. 2006. PL 191028 B1.
  13. ^ Golding, P.; W Millar, R; C Paul, N; H Richards (deceased), D. Nitration by oxides of nitrogen, part 1: preparation of nitrate esters by reaction of strained-ring oxygen heterocycles with dinitrogen pentoxide. Tetrahedron Letters. 1988, 29 (22): 2731–2734. ISSN 0040-4039. doi:10.1016/0040-4039(88)85272-9. 
  14. ^ Volkova, Yuliya A.; Ivanova, Olga A.; Budynina, Ekaterina M.; Averina, Elena B.; Kuznetsova, Tamara S.; Zefirov, Nikolai S. Tetranitromethane as an efficient reagent for the conversion of epoxides into β-hydroxy nitrates. Tetrahedron Letters. 2008, 49 (24): 3935–3938. ISSN 0040-4039. doi:10.1016/j.tetlet.2008.04.050. 
  15. ^ Lidy, Werner; Sundermeyer, Wolfgang. Cleavage reactions of trimethylsilyl cyanide with epoxides, carboxylic acid chlorides, chlorocarbonate esters, and sulfenyl chlorides（德文）. Tetrahedron Letters, 1973. 9 (17): 1449-1450. ISSN: 0040-4039. CODEN: TELEAY.
  16. ^ Arbuzov, B. A.; Nuretdinova, O. N. Reactions of diaryl thio- and selenophosphoric acids with oxetanes（俄文）. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1983. 3. 675-677. ISSN: 0002-3353. CODEN: IASKA6.
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