Supporting Information for
Synthesis of
2,6,8,12-Tetraacetyl-2,4,6,8,10,12-hexaazaiso
wurtzitane (TAIW) from
2,6,8,12-Tetraacetyl-4,10-dibenzyl-2,4,6,8,10,
12-hexaazaisowurtzitane (TADBIW) by
Catalytic Hydrogenolysis Using a Continuous
Flow Process
Kai Dong,a Cheng H. Sun,*a Jian W. Song,b Gai X. Wei,b and Si P. Pang*a
a
School of Materials Science & Engineering, Beijing Institute of Technology, 5 South
Zhongguancun Street, Haidian District, Beijing 100081, P. R. China
b
Qingyang Chemical Industry Corporation, Liaoyang, Liaoning, 111002, P. R. China
* TEL.: (+)86 010-68918049. Fax: (+)86 010-68918049. E-mail: [email protected];
* TEL.: (+)86 010-68913038. Fax: (+)86 010-68913038. E-mail: [email protected].
Contents:
I. The photo of the H-Cube ProTM
II. The front view of the H-Cube ProTM
III. The schematic design of the H-Cube ProTM
IV. HPLC and HPLC-MS method for analysis of the liquid products
V. Selectivity calculation of the liquid product
VI. MS identification and quantitative analysis method of TAMBIW
I. The photo of the H-Cube ProTM
Figure S1. The H-Cube ProTM
II. The front view of the H-Cube ProTM
Figure S2. Front view of the H-Cube ProTM
1. Sample inlet line
2. Inlet pressure sensor
3. Inlet valve
4. Gas/liquid mixer
5. Bubble detector
6. Loop module attachment before CatCart
7. CatCart column heater/cooler unit
8. Loop module attachment after CatCart
9. System pressure sensor
10. Back pressure sensor
11. Hydrogenated product collector
12. Front cover
III. The schematic design of the H-Cube ProTM
Figure S3. Schematic design of the H-Cube ProTM
IV. HPLC and HPLC-MS method for analysis of the liquid products
Column: Eclipse XDB C18
Solvent A: Water
Solvent B: Methanol
Sample injection: 5ul
Wavelength: 230nm
Flow rate, Solvent Percentage and retention time
HPLC
HPLC-MS
TADBIW
1ml/min, 70%B, 5.35min
0.4ml/min, 70%B, 13.15min
TAMBIW
1ml/min, 70%B, 2.7min
0.4ml/min, 70%B, 6.7min
TAIW
0.4ml/min, 25%B, 6.38min
0.4ml/min, 25%B, 6.38min
acetic acid
0.4ml/min, 25%B, 7.1min
0.4ml/min, 25%B, 7.1min
MS Conditions:
Ion polarity: Negative; Ion source Type: ESI; Dry temp: 250°C; Nebulizer: 35 psig;
Dry gas: 12 mL/min;. Capillary voltage: 4000V; Frag: 70.
V. Selectivity calculation of the liquid product
TADBIW and TAIW were dissolved in acetonitrile and water, then they were examined by HPLC
using the same analysis conditions with that of the reaction products. The purities of TADBIW and
TAIW were established as 98% and 96% respectively using the area normalization method. The
selectivity of TAIW was calculated as follows.
S(TAIW)=C(TAIW)*P(TAIW)*516/[ Creact.(TADBIW)*336*P(TADBIW)]
S(TAIW): Selectivity of TAIW
P(TAIW): Purity of TAIW
Creact.(TADBIW): Measured reacted concentration of TADBIW
P(TADBIW): Purity of TADBIW
VI. MS identification and quantitative analysis method of TAMBIW
Figure S5. MS sprcturm of TAMBIW
Although ref. 1 has reported the synthesis of TAMBIW as the final product of TADBIW
hydrogenolysis in acetic acid, this work has revealed that TAMBIW is an intermediate of
TADBIW hydrogenolysis to prepare TAIW. Unfortunately, we were unable to isolate TAMBIW
from the mixture. Considering the difficulty of TAMBIW isolation, a method to estimate the
response factor of TAMBIW was used as follows.
The response factor of TADBIW and TAIW were identified as 1:0.85 by HPLC analysis using the
method of analyzing TADBIW and TAMBIW (i.e. 70% methanol, 1ml/min, 6min). Given that
TAMBIW was more structurally similar to TADBIW shown by TLC and HPLC results, a
deduction was made that the response factor of TADBIW:TAMBIW was 1:0.95, which was used
for quantitative analysis of TAMBIW.
Reference:
(1) Ou, Y. X.; Xu, Y. J.; Chen, J. T.; Chen, B. R. Zheng, F. P.; Jia, H. C.; Wang, C. Chem. J. Chin.
U. 1999, 20, 561-564.
Note:
Figure S1-S3 here were taken from the H-Cube ProTM manual.