瞬烯

瞬烯
	IUPAC名; Tricyclo[3.3.2.02,8]deca-3,6,9-triene; 三环[3.3.2.02,8]-3,6,9-癸三烯
英文名	Bullvalene
别名	Bullvalen
识别
CAS号	1005-51-2
PubChem	136796
ChemSpider	120549
SMILES	C\2=C\C/1\C=C/C3C(\C=C\1)C/23;
InChI	1/C10H10/c1-4-8-9-5-2-7(1)3-6-10(8)9/h1-10H;
InChIKey	UKFBVTJTKMSPMI-UHFFFAOYAK
性质
化学式	C10H10
摩尔质量	130.19 g·mol⁻¹
熔点	96 °C
沸点	400 °C分解
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

瞬烯（化学式：C₁₀H₁₀）是一个碳氢化合物。瞬烯是流变分子之一，其分子内所有的碳碳键不断地发生Cope重排，从而存在多个价互变异构体。^[1]

瞬烯最早在1963年由G. Schröder通过光解环辛四烯二聚体而得，同时生成副产物苯。^[2]

高温时，快速的分子内重排与结构对称性，使瞬烯所有碳原子和氢原子在核磁共振实验中呈现等价。重排可能产物多达10!/3 = 1,209,600个 (未计算对映异构体)，下图仅列出其中的五个。

瞬烯在室温下的质子NMR谱有一个宽峰，表明可以分辨出分子中不同的氢原子。在二硫化碳做为溶剂、温度120.3 °C时，瞬烯的¹H NMR谱只存在4.237 ppm一个尖锐的吸收峰，说明分子重排速度大于¹H核磁共振的弛豫时间，无法被分辨出来。 ^[3] 变温¹³C NMR实验与变温魔角固体核磁共振(¹³C CP-MS NMR)实验中亦可观察到快速的平衡反应。^[4] Martin由变温核磁共振实验得到瞬烯结构变化所需要的活化能为11.8 kcal/mol。^[5] Patel等人于2020年发表的研究工作中通过理论计算发现瞬烯衍生物的构型重排时所需要的活化能约为14 kcal/mol。^[6]

参考文献

^ Ault, Addison. The Bullvalene Story. The Conception of Bullvalene, a Molecule That Has No Permanent Structure. Journal of Chemical Education. 2001-07, 78 (7): 924. doi:10.1021/ed078p924.
^ Schröder, Gerhard. Preparation and Properties of Tricyclo[3,3,2,04,6]deca-2,7,9-triene (Bullvalene). Angewandte Chemie International Edition in English. 1963-08, 2 (8): 481–482. doi:10.1002/anie.196304814.
^ Oth, Jean F. M.; Müllen, Klaus; Gilles, Jean-Marie; Schröder, Gerhard. Comparison of 13C‐ and 1H‐Magnetic Resonance Spectroscopy as Techniques for the Quantitative Investigation of Dynamic Processes. The cope rearrangement in bullvalene. Helvetica Chimica Acta. 1974-07-17, 57 (5): 1415–1433. doi:10.1002/hlca.19740570518.
^ Meier, B. H.; Earl, William L. Fluxional behavior in the solid state: bullvalene. Journal of the American Chemical Society. 1985-09, 107 (19): 5553–5555. doi:10.1021/ja00305a054.
^ Saunders, Martin. Measurement of the rate of rearrangement of bullvalene. Tetrahedron Letters. 1963-01, 4 (25): 1699–1702. doi:10.1016/S0040-4039(01)90897-4.
^ Patel, Harshal D.; Tran, Thanh-Huyen; Sumby, Christopher J.; Pašteka, Lukáš F.; Fallon, Thomas. Boronate Ester Bullvalenes. Journal of the American Chemical Society. 2020-02-11, 142 (8): 3680–3685. doi:10.1021/jacs.9b12930.

[1] Ault, Addison. The Bullvalene Story. The Conception of Bullvalene, a Molecule That Has No Permanent Structure. Journal of Chemical Education. 2001-07, 78 (7): 924. doi:10.1021/ed078p924.

[2] Schröder, Gerhard. Preparation and Properties of Tricyclo[3,3,2,04,6]deca-2,7,9-triene (Bullvalene). Angewandte Chemie International Edition in English. 1963-08, 2 (8): 481–482. doi:10.1002/anie.196304814.

[3] Oth, Jean F. M.; Müllen, Klaus; Gilles, Jean-Marie; Schröder, Gerhard. Comparison of 13C‐ and 1H‐Magnetic Resonance Spectroscopy as Techniques for the Quantitative Investigation of Dynamic Processes. The cope rearrangement in bullvalene. Helvetica Chimica Acta. 1974-07-17, 57 (5): 1415–1433. doi:10.1002/hlca.19740570518.

[4] Meier, B. H.; Earl, William L. Fluxional behavior in the solid state: bullvalene. Journal of the American Chemical Society. 1985-09, 107 (19): 5553–5555. doi:10.1021/ja00305a054.

[5] Saunders, Martin. Measurement of the rate of rearrangement of bullvalene. Tetrahedron Letters. 1963-01, 4 (25): 1699–1702. doi:10.1016/S0040-4039(01)90897-4.

[6] Patel, Harshal D.; Tran, Thanh-Huyen; Sumby, Christopher J.; Pašteka, Lukáš F.; Fallon, Thomas. Boronate Ester Bullvalenes. Journal of the American Chemical Society. 2020-02-11, 142 (8): 3680–3685. doi:10.1021/jacs.9b12930.

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