高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (3): 435.doi: 10.7503/cjcu20170507
王毅1, 张苹1, 吴生秀1, 孙媛媛1, 赵彤1, 刘世熙2()
收稿日期:
2017-07-26
出版日期:
2018-03-10
发布日期:
2018-01-17
作者简介:
联系人简介: 刘世熙, 男, 博士, 副教授, 主要从事计算化学方面的研究. E-mail:基金资助:
WANG Yi1, ZHANG Ping1, WU Shengxiu1, SUN Yuanyuan1, ZHAO Tong1, LIU Shixi2,*()
Received:
2017-07-26
Online:
2018-03-10
Published:
2018-01-17
Contact:
LIU Shixi
E-mail:shxliu@ynu.edu.cn
Supported by:
摘要:
利用气相色谱-质谱法分别对含C≡≡C桥键、 CF2O桥键及双CF2O桥键的联苯类化合物进行分析, 在各个化合物的谱图中均存在显著的奇电子自由基离子峰(反偶电子规则)和双电荷碎片离子峰. 根据所得实验结果, 归纳以上化合物中奇电子离子的生成途径分别为: (1) 游离基中心诱导苄基
中图分类号:
TrendMD:
王毅, 张苹, 吴生秀, 孙媛媛, 赵彤, 刘世熙. 质谱中反偶电子规则并含双电荷离子的两类联苯化合物的裂解机理. 高等学校化学学报, 2018, 39(3): 435.
WANG Yi, ZHANG Ping, WU Shengxiu, SUN Yuanyuan, ZHAO Tong, LIU Shixi. Fragmentation Mechanism of Two Kinds of Violated Even-electron Rule Compounds with Doubly Charged Ions in Mass Spectrometry†. Chem. J. Chinese Universities, 2018, 39(3): 435.
Compound | R1 | X1 | X2 | X3 | X4 | R2 |
---|---|---|---|---|---|---|
1 | C3H7 | F | H | H | H | C2H5 |
2 | C3H7 | H | H | H | H | C4H9 |
3 | C3H7 | F | H | H | H | C3H7 |
4 | C3H7 | F | H | H | H | C4H9 |
5 | C3H7 | F | H | H | H | C5H11 |
6 | C3H7 | H | H | F | F | C2H5 |
7 | C2H5 | F | F | H | H | C3H7 |
8 | C3H7 | H | H | F | F | C4H9 |
9 | C4H9 | F | F | H | H | C3H7 |
Table 1 Structures and stereochemistry of alkyl biphenyl compounds with C≡≡C central-bridge-bond*
Compound | R1 | X1 | X2 | X3 | X4 | R2 |
---|---|---|---|---|---|---|
1 | C3H7 | F | H | H | H | C2H5 |
2 | C3H7 | H | H | H | H | C4H9 |
3 | C3H7 | F | H | H | H | C3H7 |
4 | C3H7 | F | H | H | H | C4H9 |
5 | C3H7 | F | H | H | H | C5H11 |
6 | C3H7 | H | H | F | F | C2H5 |
7 | C2H5 | F | F | H | H | C3H7 |
8 | C3H7 | H | H | F | F | C4H9 |
9 | C4H9 | F | F | H | H | C3H7 |
Fig.1 EI mass spectra of alkyl biphenyl compounds with C≡≡C central-bridge-bond for compounds 1—9(A—I) ■ Doubly charged ion; ▲ even electron ion; ● odd electron ion; * molecular ion. Insets of (D) arethe expanded EI mass spectra, showing the presence of 13C isotope for doubly charged ion.
Type of ion | Theoretical value | Measured value | 103 Error | Elemental composition |
---|---|---|---|---|
[odd] +· | 370.2091 | 370.2060 | 3.1 | C27H27F+· |
[even] + | 341.1700 | 341.1736 | 3.6 | C25H22F+ |
[even] + | 327.1544 | 327.1513 | 3.1 | C24H20F+ |
[even] + | 311.1231 | 311.1198 | 3.3 | C23H16F+ |
[odd] +· | 298.1152 | 298.1147 | 0.5 | C22H15F+· |
[odd] +· | 276.0934 | 276.0896 | 3.8 | C22 |
[even] 2+ | 185.1043 | 185.1030 | 1.3 | C27H27F2+ |
[even] 2+ | 149.0573 | 149.0568 | 0.5 | C22H15F2+ |
Table 2 Results of Q-TOF-HRMS of compound 4
Type of ion | Theoretical value | Measured value | 103 Error | Elemental composition |
---|---|---|---|---|
[odd] +· | 370.2091 | 370.2060 | 3.1 | C27H27F+· |
[even] + | 341.1700 | 341.1736 | 3.6 | C25H22F+ |
[even] + | 327.1544 | 327.1513 | 3.1 | C24H20F+ |
[even] + | 311.1231 | 311.1198 | 3.3 | C23H16F+ |
[odd] +· | 298.1152 | 298.1147 | 0.5 | C22H15F+· |
[odd] +· | 276.0934 | 276.0896 | 3.8 | C22 |
[even] 2+ | 185.1043 | 185.1030 | 1.3 | C27H27F2+ |
[even] 2+ | 149.0573 | 149.0568 | 0.5 | C22H15F2+ |
Compd. | R1 | X1 | X2 | X3 | X4 | X5 | Compd. | R1 | X1 | X2 | X3 | X4 | X5 |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1a | C2H5 | H | F | OCF2CFCF2 | F | H | 1b | CH3 | H | F | F | F | H |
2a | C3H5 | H | F | F | F | H | 2b | C2H5 | H | F | F | F | H |
3a | CH3 | H | H | OCF3 | H | H | 1c | H | H | F | F | F | H |
4a | C2H5 | H | H | OCF3 | H | H | 2c | C3H7 | H | F | F | F | H |
5a | C4H9 | H | F | F | F | H | 3c | C4H9 | H | F | F | F | H |
6a | C3H7 | H | F | F | F | H | 4c | C5H11 | H | F | F | F | H |
7a | C2H5 | H | F | F | F | H | 5c | C6H13 | H | F | F | F | H |
8a | C2H5 | CH3 | F | F | F | H | 6c | C5H11 | H | F | F | F | H |
9a | No Replace | H | F | F | F | H |
Table 3 Structures and stereochemistry of alkyl biphenyl compounds with CF2O central-bridge-bond*
Compd. | R1 | X1 | X2 | X3 | X4 | X5 | Compd. | R1 | X1 | X2 | X3 | X4 | X5 |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1a | C2H5 | H | F | OCF2CFCF2 | F | H | 1b | CH3 | H | F | F | F | H |
2a | C3H5 | H | F | F | F | H | 2b | C2H5 | H | F | F | F | H |
3a | CH3 | H | H | OCF3 | H | H | 1c | H | H | F | F | F | H |
4a | C2H5 | H | H | OCF3 | H | H | 2c | C3H7 | H | F | F | F | H |
5a | C4H9 | H | F | F | F | H | 3c | C4H9 | H | F | F | F | H |
6a | C3H7 | H | F | F | F | H | 4c | C5H11 | H | F | F | F | H |
7a | C2H5 | H | F | F | F | H | 5c | C6H13 | H | F | F | F | H |
8a | C2H5 | CH3 | F | F | F | H | 6c | C5H11 | H | F | F | F | H |
9a | No Replace | H | F | F | F | H |
Fig.2 EI mass spectra of alkyl biphenyl compounds [a] with CF2O central-bridge-bond for compounds 1a—9a(A—I) ■ Doubly charged ion; ▲ even electron ion; ● odd electron ion; * molecular ion.
Fig.3 EI mass spectra of alkyl biphenyl compounds [b] with CF2O central-bridge-bond for compounds 1b(A) and 2b(B) ■ Doubly charged ion; ▲ even electron ion; ● odd electron ion; * molecular ion.
Fig.4 EI mass spectra of alkyl biphenyl compounds [c] with CF2O central-bridge-bond for compounds 1c—6c(A—F) ■ Doubly charged ion; ▲ even electron ion; ● odd electron ion; * molecular ion. Insets of (B) is the expanded EI mass spectrum, showing the presence of 13C isotope for doubly charged ion.
Type of ion | Theoretical value | Measured value | 103 Error | Elemental composition |
---|---|---|---|---|
[odd]+· | 562.1537 | 562.1592 | 5.5 | C31H22F8O+· |
[even]+ | 519.0990 | 519.0972 | 1.8 | C28H15F8O+ |
[even]+ | 415.1480 | 415.1496 | 1.6 | C25H20 |
[odd]+· | 372.0932 | 372.0901 | 3.1 | C22H13 |
[even]+ | 371.0854 | 371.0894 | 4.0 | C22H12 |
[even] 2+ | 186.0463 | 186.0449 | 1.4 | C22H13 |
Table 4 Results of Q-TOF-HRMS of compound 2c
Type of ion | Theoretical value | Measured value | 103 Error | Elemental composition |
---|---|---|---|---|
[odd]+· | 562.1537 | 562.1592 | 5.5 | C31H22F8O+· |
[even]+ | 519.0990 | 519.0972 | 1.8 | C28H15F8O+ |
[even]+ | 415.1480 | 415.1496 | 1.6 | C25H20 |
[odd]+· | 372.0932 | 372.0901 | 3.1 | C22H13 |
[even]+ | 371.0854 | 371.0894 | 4.0 | C22H12 |
[even] 2+ | 186.0463 | 186.0449 | 1.4 | C22H13 |
Fig.5 EI mass spectra of biphenyl compounds with double CF2O central-bridge-bond for compounds 1d(A) and 2d(B) ■ Doubly charged ion; ▲ even electron ion; ● odd electron ion; * molecular ion.
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