2,3-環氧丁烷

2,3-環氧丁烷
	IUPAC名; 2,3-Dimethyloxirane
別名	2,3-二甲基環氧乙烷; 2-丁烯環氧化物
識別
CAS編號	3266-23-7 ; 1758-33-4（R,S） ; 21490-63-1（S,S） ; 1758-32-3（R,R）
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編號	3271
性質
化學式	C4H8O
莫耳質量	72.11 g·mol−1
外觀	無色液體
密度	0.837 g·cm−3
熔點	−85 °C（188 K）（S,S）; −80 °C（193 K）（R,S）
沸點	55—56 °C（328—329 K）; 56.5 °C（329.6 K）（S,S）; 60 °C（333 K）（R,S）; 53.5 °C（326.6 K）（746 torr，R,R）
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

2,3-環氧丁烷（英語：2,3-Epoxybutane）是化學式為CH₃CH(O)CHCH₃的環氧化合物，帶有兩個手性碳原子，其中的(2R,3S)-2,3-環氧丁烷為內消旋化合物，因此總共有三種立體異構物，它們都是無色液體。

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合成

2,3-環氧丁烷可由2-丁烯為原料進行合成，反應會生成中間體鹵代醇（英語：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脫水環化，也可以得到2,3-環氧丁烷。^[6]

性質

2,3-環氧丁烷的三元環不穩定，可以發生開環反應，如氫化生成對應的2,3-丁二醇^[7]。它和溴代甲硼烷二甲硫醚反應，可以得到3-溴-2-丁醇。^[8]在二甲基氧鎓四氟硼酸鹽催化下，二甲基亞碸可將其氧化為3-羥基-2-丁酮。^[9]

它和二氧化碳發生環加成反應，生成2,3-丁二醇-2,3-環碳酸酯，反應所用的催化劑已有較多報道，如胺基酸-碘化鉀^[10]、金屬有機框架材料^[11]等。它和二硫化碳反應，生成2,3-丁二醇-2O,3S-二硫代環碳酸酯。^[12]

2,3-環氧丁烷和五氧化二氮在二氯甲烷中反應，得到2,3-丁二醇-2,3-二硝酸酯；^[13]和四硝基甲烷反應，得到2,3-丁二醇-2-硝酸酯。^[14]它和三甲基氰矽烷發生開環反應，得到2-甲基-3-三甲基矽氧基丁腈。^[15]它和O-異丙基-O-苯基硒代磷酸反應，得到2-異丙基-4,5-二甲基-1,3,2-氧雜硒雜磷雜環戊烷-2-氧化物。^[16]

參考文獻

[1]
"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（波蘭文）. 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.

[SRC-1] [1]
"PhysProp" data were obtained from Syracuse Research Corporation of Syracuse, New York (US). Retrieved from SciFinder. [2021-07-10].

[2] [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] [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] [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.

[Ullmann-5] [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] [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] [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] [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] [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] [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] [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] [12]
Pielichowski, Jan; Czub, Piotr. Preparation of substituted 1,3-oxothiolane-2-thiones by reacting epoxides with carbon disulfide（波蘭文）. 2006. PL 191028 B1.

[13] [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] [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] [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] [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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