performance spiro-fuelSupporting Materials for ... · Scheme S1 Results of the blank test with pure...
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Supporting Materials for Photoinduced cycloaddition of biomass derivatives to high- performance spiro-fuel Junjian Xie 1 , Lun Pan 1 , Genkuo Nie, Jiawei Xie, Yakun Liu, Chi Ma, Xiangwen Zhang, Ji-Jun Zou* Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China Corresponding author. Tel and fax: 86-22-27892340. E-mail: [email protected] (J.-J. Zou) 1 These authors contributed equally (J. Xie and L. Pan) Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2019
Transcript of performance spiro-fuelSupporting Materials for ... · Scheme S1 Results of the blank test with pure...
Supporting Materials for
Photoinduced cycloaddition of biomass derivatives to high-
performance spiro-fuel
Junjian Xie1, Lun Pan1, Genkuo Nie, Jiawei Xie, Yakun Liu, Chi Ma, Xiangwen Zhang, Ji-Jun Zou*
Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical
Engineering and Technology, Tianjin University, Collaborative Innovative Center of Chemical
Science and Engineering (Tianjin), Tianjin 300072, China
Corresponding author. Tel and fax: 86-22-27892340. E-mail: [email protected] (J.-J. Zou)1These authors contributed equally (J. Xie and L. Pan)
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2019
Scheme S1 Results of the blank test with pure β-pinene.
Conversion: 4.8 %
OH
O2 / hvOH
+
Figure S1 Mass spectrum of oxidation products of β-pinene.
(Text File) Component at scan 1666 (14.823 min) [Model = +79u] in e:\a\\\xjj\181212\180513yifuertongpaixi.cdf30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160
0
50
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3839
41
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43
44 51 5355
56 59 61 6365
67
6971 73 75
77
78
79
8183 85 87 89
91
92
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95 98 105
108
117
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123 133 137 141 152
(Text File) Component at scan 1537 (14.181 min) [Model = +92u] in e:\a\\\xjj\181212\180513yifuertongpaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270
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109119
123 128
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151 257
Figure S2 Mass spectrum of isophorone self-adduct.
(Text File) Component at scan 1506 (12.185 min) [Model = +139u] in E:\A\\\XJJ\170304\HV24H170302 .D\DATA.MS20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
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2941
45
55
6169
7179
82
91 95109
121
139
143 151 159 165 173 180 187 201 219 233 244 261 276
O
O
OH
OH
Figure S3 1H and 13C NMR spectra of isophorone self-adduct (One of the isomers obtained by
multiple recrystallization with CH2Cl2).
Figure S4 Mass spectrum of isophorone photoisomerized product.
(Text File) Component at scan 572 (6.543 min) [Model = +82u] in E:\A\\\XJJ\170304\HV24H170302 .D\DATA.MS20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150
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27 2938
39
40
41
42 5153
54
55
5663 65
67
68 77 79
81
82
83
84 91 93
95
110 123
138
Figure S5 Mass spectrum of isophorone and β-pinene co-adduct.
(Text File) Component at scan 3384 (23.415 min) [Model = +69u] in e:\a\\\xjj\181212\180513yifuertongpaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
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45
53
55
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5965
67
69
77
79
81
8391
96
107
123
135145
152
159
163177
191205
213
231241
245256
259274
O
O
Figure S6 1H and 13C NMR spectra of isophorone and β-pinene co-adduct.
Figure S7 GC spectra of isophorone and β-pinene reaction solution.
Figure S8 Mass spectra of isophorone and n-hexene co-adduct.
(Text File) Component at scan 3174 (19.367 min) [Model = +82u, -41u] in e:\a\\\xjj\190706\190626yifuertongzhengjixi.cdf40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230
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45 59 62
69
72 75 86 91 9497
103
111
113 117 121 125 131 135
139
153165
176 180 189 193 204
207
222
Figure S9 GC spectra of isophorone and n-hexene reaction solution.
O
Figure S10 Mass spectra of isophorone and α-pinene co-adduct.
(Text File) Component at scan 3706 (22.027 min) [Model = +122u] in e:\a\\\xjj\190706\190629yifuertong-alfapaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
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41
53
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57
69
71
79 83
91
95
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105119
122
135 151157
166
178
185
191 203
217 225231 241
255
259
274
Figure S11 GC spectra of isophorone and α-pinene reaction solution.
Figure S12 Mass spectra of isophorone and camphene co-adduct.
(Text File) Component at scan 4785 (27.420 min) [Model = +94u, -93u] in e:\a\\\xjj\190706\190627yifuertongkanxi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
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4355
57 61
67
6977
79
87
91
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136139
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152 163 175 189 198 205 213219
227 233 241 259
274
O
O
Figure S13 GC spectra of isophorone and camphene reaction solution.
Figure S14 Mass spectra of isophorone and cinene co-adduct.
(Text File) Component at scan 4141 (24.202 min) [Model = +93u] in e:\a\\\xjj\190706\190630yifuertong-ningmengxi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
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43 5355
57 65
6979
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107 121134
139
147 157 166 175 189 195 203 217231
241 259 274
(Text File) Component at scan 4573 (26.361 min) [Model = +132u, -134u] in e:\a\\\xjj\190706\190630yifuertong-ningmengxi.cdf40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280
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44 61 8796
103118 126
132
147153
163 171179 191
203 209214
227 232 237
241
259
270274
O
Isomer 2
O
Isomer 1
Figure S15 GC spectra of isophorone and cinene reaction solution.
Figure S16 Mass spectra of isophorone and 2-methoxy-4-vinylphenol co-adduct.
(Text File) Component at scan 5704 (32.014 min) [Model = +150u] in e:\a\\\xjj\190706\190701yifuertong-2jiayangjiyixijibenfefn.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
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41 45 55 59 65 69 77 82 91 95107
117 123 131
135
139 145
150
159 169 177 185 191 199 213 231 241 255 273288
Figure S17 Mass spectra of 2-methoxy-4-vinylphenol self-adduct.
(Text File) Component at scan 7336 (40.176 min) [Model = TIC] in e:\a\\\xjj\190706\190701yifuertong-2jiayangjiyixijibenfefn.cdf50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310
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55 65 77 105 115 127134
137145
151
161
176210
239
253
259269
285
300
O
OH
OCH3
HO
H3CO
OH
OCH3
Figure S18 GC spectra of isophorone and 2-methoxy-4-vinylphenol reaction solution.
Figure S19 Mass spectra of 2-cyclopentenone and β-pinene co-adduct.
(Text File) Component at scan 3906 (23.023 min) [Model = +55u] in e:\a\\\xjj\190706\190623huanwuxitong-betapaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230
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9597
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138 142
146
157
162
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190203 218
Figure S20 Mass spectra of 2-cyclopentenone self-adduct.
(Text File) Component at scan 3113 (19.060 min) [Model = +82u, -96u] in e:\a\\\xjj\190706\190623huanwuxitong-betapaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320
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39
42
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68
79
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95
104
107 122 136149
164
312
O
O
O
Figure S21 GC spectra of 2-cyclopentenone and β-pinene reaction solution.
Figure S22 Mass spectra of 3-methyl-2-cyclopenten-1-one and β-pinene co-adduct.
(Text File) Component at scan 3639 (21.693 min) [Model = +105u] in e:\a\\\xjj\190706\190625jiajihuanwuxitong-betapaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240
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4355
57 6067
69 79
8287
91
93
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120133
147 153 163 171 176 189199 204 217 232
Figure S23 GC spectra of 3-methyl-2-cyclopenten-1-one and β-pinene reaction solution.
O
Figure S24 Mass spectra of carvone and β-pinene co-adduct.
(Text File) Component at scan 4824 (27.617 min) [Model = +69u, -41u] in e:\a\\\xjj\190706\190626xiangqintong-betapaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
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40 4553
62
69
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7982
86 90
93
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118
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133 147
163
174 189 203 218225
230 239
243
246 253 271286
Figure S25 GC spectra of carvone and β-pinene reaction solution.
Figure S26 Mass spectra of coumarin and β-pinene co-adduct.
(Text File) Component at scan 6004 (33.514 min) [Model = +93u] in e:\a\\\xjj\190706\190703xiangdousu-betapaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290
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4355 69
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107 118
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136
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152 158 165 171 178 184 197 211 239 282
Figure S27 Mass spectra of coumarin self-adduct.
(Text File) Component at scan 7240 (39.697 min) [Model = +146u] in e:\a\\\xjj\190706\190703xiangdousu-betapaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
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39 5163
77 82
90
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123 132
146
178 292
O
O O
O
O
O
O
Figure S28 GC spectra of coumarin and β-pinene reaction solution.
Figure S29 Mass spectra of cinnamic aldehyde and β-pinene co-adduct.
(Text File) Component at scan 4863 (27.812 min) [Model = +93u] in e:\a\\\xjj\190706\190702rouguiquan-betapaixi.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280
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43 5569 80
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107 115121
128133
136
141 149 154 169 177 183 195 207 212 224 239 253 268
Figure S30 GC spectra of cinnamic aldehyde and β-pinene reaction solution.
O
Figure S31 Mass spectra of isophorone and 2-methylfuran co-adduct.
(Text File) Com p onent a t sc a n 1118 (10.842 m in) [Mod el = +122u] in E:\ A\ \ \ XJJ\ 171116\ 171017IPMFDA-HV.D\ DATA.MS20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230
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65 6974
7783
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130135 145
149
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177 187 192
205220
Figure S32 GC spectra of isophorone and 2-methylfuran reaction solution.
Figure S33 Mass spectra of isophorone and 2,5-dimethylfuran co-adduct.
(Text File) Component at scan 2535 (15.541 min) [Model = +81u] in E:\A\\\XJJ\XIE190426\190419YIFUERTONG25ERJIAJIFUNAN.D\DATA.MS10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240
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43
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5367
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109121 127
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149 159 177 186 191 201 219 234
O
O
O
O
Figure S34 GC spectra of isophorone and 2,5-dimethylfuran reaction solution.
Figure S35 Mass spectrum of the obtained spiro-fuel derived from isophorone and β-pinene.
(Text File) Component at scan 3755 (25.768 min) [Model = +109u] in e:\a\\\xjj\181212\180830yifuertongpaixi-nabh4-hdo-pdc-hzsm5.cdf30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270
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128137 150
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203
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Figure S36. GC spectra of the HDO solution and obtained spiro-fuel after vacuum distillation.
Figure S37. 1H and 13C NMR spectra of the obtained spiro-fuel derived from isophorone and β-
pinene.
Figure S38. 1H and 13C NMR spectra of the obtained fuel derived from isophorone self-adduct.
Figure S39 Mass spectrum of the obtained fuel derived from isophorone self-adduct.
(Text File) Component at scan 2322 (17.118 min) [Model = +109u, -124u] in E:\A\\\XJJ\170718\HDO.D\DATA.MS20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260
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9397
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Table S1 Properties of some reported biofuels.
Feedstock Main component structureDensity/kg·
m-3 (20°C)
Freezing
point/°CReference
Biobutanol 0.78 -78 Energy Environ. Sci., 2010, 3, 352.
- -49.7Furfural and methyl
isobutyl ketone - -74.9ChemSusChem, 2013, 6, 1149.
Diacetone alcohol +
0.83 -56.7 Green Chem., 2016, 18, 5751.
0.804 < -60.02-Methylfuran and
cyclohexanone0.825 -26.4
Chem. Eng. Sci., 2015, 138, 239.
Aromatic oxygenates and
furfural alcohols0.804 < -80 Fuel Process. Technol., 2017, 163, 45.
0.815 -24.6
0.822 -21.7
0.819 -14.3
Cyclic ketones and furanic
aldehydes
0.826 -9.5
Fuel Process. Technol., 2016, 148, 361.
Cyclopentanone and
butanal
+0.82 -94.0 Ind. Eng. Chem. Res., 2015, 54, 11825.
Mesityl oxide and 2-
methylfuran0.82 -56 ~ -54 Sci. Rep., 2016, 6, 32379.
0.81 -255-Hydroxymethyl-
furfural and ketones0.81 -46
ChemSusChem, 2017, 10, 711.
Isophorone 0.858 -51.0 Sci. Rep., 2017, 7, 6111.
0.867 -38.0
Cyclic ketones
0.887 1.2
Green Chem., 2015, 17, 4473.
0.870 -76
Cyclic ketones
0.893 -51
Chem. Commun., 2017, 53, 10303.
Cyclopentanone 0.91 - AIChE J., 2016, 62, 2754.
Pinenes
+
0.938 < -30 Energy Fuels, 2010, 24, 267.
Phenols and benzyl ether
or benzyl alcohol0.959 -15 Chem. Eng. Sci., 2017, 158, 64.
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