Photochemical Degradation of the Strictosamide†

doi:10.7503/cjcu20131255

Abstract

Abstract:

Photochemical reaction in the water solution of stictosamide was studied by HPLC and LC-MS. And the main degradation product, (3S)-pumiloside, was isolated and identified by ¹H NMR, ¹³C NMR, HRMS and optical rotation. The fragmentation patterns of (3S)-pumiloside and other intermediates were analysed by LC-MS. And then the mechanism of the strictosamide transformation into (3S)-pumiloside by light with O₂ was also analysed. To improve the productivity of (3S)-pumiloside, the sunlight was replaced by light of fluorescent lamps. The productivity of (3S)-pumiloside was improved to 56% using light of fluorescent lamps and adding O₂ into the stictosamide solution for accelerating degradation. This discovery shows a new green way to make the (3S)-pumiloside, and provided references for the structure transformation of similar compounds. This also gave the evidence that the strictosamide need to be stored against light.

Key words: Stictosamide, (3S)-Pumiloside, Photochemical degradation, Oxidization

CLC Number:

O621.3

TrendMD:

LIU Wenjun, LI Zhaoliang, MENG Zhaoqing, SUN Lin, YANG Biao, ZHANG Shan, CHENG Ningbo, DING Gang, WANG Zhenzhong, XIAO Wei. Photochemical Degradation of the Strictosamide^†[J]. Chem. J. Chinese Universities, 2014, 35(8): 1710.

Figures/Tables 6

References 21

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Condition	0 d	7 d(dark)	7 d(Sun light)
Without sterilization	100.00^*
With N₂(sterilization)	100.01	99.61	94.39
With air(sterilization)	99.63	99.58	60.81
With O₂(sterilization)	99.46	98.92	42.08

Condition	0 d	7 d(dark)	7 d(Sun light)
Without sterilization	100.00^*
With N₂(sterilization)	100.01	99.61	94.39
With air(sterilization)	99.63	99.58	60.81
With O₂(sterilization)	99.46	98.92	42.08

Peak number	T_R/min	Molecular formula	Molecular weight	Molecular ions, m/z		MS² ions, m/z (-)
Peak number	T_R/min	Molecular formula	Molecular weight	(+)		(-)
1	7.55	C₂₆H₃₀N₂O₁₀	530.19	513.18[M+H-H₂O]⁺ 531.19[M+H]⁺ 1061.38[2M+H]⁺	511.17[M-H-H₂O]^- 529.18[M-H]^- 1059.37[2M-H]^-	511.16, 367.13, 349.11, 331.10, 297.08, 279.07
2	9.80	C₂₆H₂₈N₂O₉	512.18	513.18[M+H]⁺ 1025.37[2M+H]⁺	511.17[M-H]^- 1023.35[2M-H]^-	349.11, 331.10, 279.07
3	6.80	C₂₆H₃₀N₂O₁₀	530.19	513.18[M+H-H₂O]⁺ 531.19[M+H]⁺ 1061.38[2M+H]⁺	511.17[M-H-H₂O]^- 529.18[M-H]^- 1041.36[2M-H-H₂O]^-	511.17, 349.11, 331.10, 297.08,279.07
4	16.31	C₂₆H₃₀N₂O₁₀	530.19	513.18[M+H-H₂O]⁺ 531.19[M+H]⁺ 1043.37[2M+H-H₂O]⁺	511.17[M-H-H₂O]^- 529.18[M-H]^- 1041.36[2M-H-H₂O]^-	511.17, 349.12, 331.10, 279.07

Peak number	T_R/min	Molecular formula	Molecular weight	Molecular ions, m/z		MS² ions, m/z (-)
Peak number	T_R/min	Molecular formula	Molecular weight	(+)		(-)
1	7.55	C₂₆H₃₀N₂O₁₀	530.19	513.18[M+H-H₂O]⁺ 531.19[M+H]⁺ 1061.38[2M+H]⁺	511.17[M-H-H₂O]^- 529.18[M-H]^- 1059.37[2M-H]^-	511.16, 367.13, 349.11, 331.10, 297.08, 279.07
2	9.80	C₂₆H₂₈N₂O₉	512.18	513.18[M+H]⁺ 1025.37[2M+H]⁺	511.17[M-H]^- 1023.35[2M-H]^-	349.11, 331.10, 279.07
3	6.80	C₂₆H₃₀N₂O₁₀	530.19	513.18[M+H-H₂O]⁺ 531.19[M+H]⁺ 1061.38[2M+H]⁺	511.17[M-H-H₂O]^- 529.18[M-H]^- 1041.36[2M-H-H₂O]^-	511.17, 349.11, 331.10, 297.08,279.07
4	16.31	C₂₆H₃₀N₂O₁₀	530.19	513.18[M+H-H₂O]⁺ 531.19[M+H]⁺ 1043.37[2M+H-H₂O]⁺	511.17[M-H-H₂O]^- 529.18[M-H]^- 1041.36[2M-H-H₂O]^-	511.17, 349.12, 331.10, 279.07