Construction of Three Novel Oxygen-Containing Cagelike Frameworks and Synthesis of their Energetic Derivatives

Huan Li; Qi Zhou; Jingjing Zhao; Tianjiao Hou; Guixiang Wang; Long Zhu; Bing Li; Yu Zhang; Jun Luo

doi:10.1055/a-2333-8774

Synlett, Table of Contents

Synlett 2024; 35(17): 1989-1996
DOI: 10.1055/a-2333-8774

letter

Energetic Molecules

Construction of Three Novel Oxygen-Containing Cagelike Frameworks and Synthesis of their Energetic Derivatives

Huan Li

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

,

Qi Zhou

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

,

Jingjing Zhao

^bGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin 730900, P. R. of China

,

Tianjiao Hou

^cCollege of Chemical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China

,

Guixiang Wang

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

,

Long Zhu

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

,

Bing Li

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

,

Yu Zhang∗

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

,

Jun Luo ∗

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

› Author Affiliations

Abstract

All articles of this category

Abstract

Organic cagelike frameworks are important and versatile skeletons for developing prospective energetic compounds because of their high intrinsic density, symmetry, stability, and derivability. Herein, we show the construction of three novel cagelike frameworks including dioxaadamantane, dioxaproadamantane, and dioxatwistane from 9-oxabicyclo[3.3.1]nonane-2,6-diene. In addition, their energetic derivatives were also prepared and characterized. Compared with our previous works, the introduction of more oxygen atoms into the framework gives the corresponding energetic derivative a better oxygen balance, significantly higher density, and detonation properties. These results imply that the oxygen-containing framework has the potential to be used for preparing new 3D energetic compounds with superior energy performance.

Key words

cagelike compounds - oxygen-containing frameworks - energetic compounds - synthesis - performance - oxidative cyclization - oxidation - nitration

Full Text

References

References and Notes

1a Fischer D, Klapötke TM, Stierstorfer J. Angew. Chem Int. Ed. 2015; 54: 10299
1b Fershtat LL, Makhova NN. ChemPlusChem 2020; 85: 13
1c Wang Y, Song S.-W, Huang C, Qi X.-J, Wang K.-C, Liu Y.-J, Zhang Q.-H. J. Mater. Chem. A 2019; 7: 19248
1d Zlotin SG, Churakov AM, Egorov MP, Fershtat LL, Klenov MS, Kuchurov IV, Makhova NN, Smirnov GA, Tomilov YV, Tartakovsky VA. Mendeleev Commun. 2021; 31: 731

2a Zhang W.-Q, Zhang J.-H, Deng M.-C, Qi X.-J, Nie F.-D, Zhang Q.-H. Nat. Commun. 2017; 8: 1
2b Zhou J, Zhang J.-L, Wang B.-Z, Qiu L.-L, Xu R.-Q, Sheremetev AB. FirePhysChem 2022; 2: 83
2c Zlotin SG, Dalinger IL, Makhova NN, Tartakovsky VA. Russ. Chem. Rev. 2020; 89: 1

3a Agrawal JP. Prog. Energy Combust. Sci. 1998; 24: 1
3b Pagoria PF, Lee GS, Mitchell AR, Schmidt RD. Thermochim. Acta 2002; 384: 187
3c Yang J.-Q, Wang G.-X, Gong X.-D, Zhang J.-G, Wang YA. ACS Omega 2018; 3: 9739
3d Zhong K, Zhang C.-Y. Chem. Eng. J. 2024; 483: 149202

4a Jones ML, Lee E. J. Energ. Mater. 1997; 15: 193
4b Tisdale JT, Hill LG, Duque AL. Powder Technol. 2022; 396: 152

5a Kumar P. Def. Technol. 2018; 14: 661
5b Venkatachalam S, Santhosh G, Ninan K. Propellants, Explos., Pyrotech. 2004; 29: 178

6a Lee JS, Hsu CK, Chang CL. Thermochim. Acta 2002; 392173
6b Ye C.-C, An Q, Zhang W.-Q, Goddard WA. J. Phys. Chem. C 2019; 123: 9231
6c Shi Y.-H, Chang Q, Song T.-S, Yin M.-L, Zhang L, Cao X.-F, Wei A.-X, Cao X. Chem. Eng. J. 2024; 479: 147394

7a Guo S.-T, Liu J, Qian W, Zhu W.-H, Zhang C.-Y. Energ. Mater. Front. 2021; 2: 292
7b Zhang C.-Y, Jiao F.-B, Li H.-Z. Cryst. Growth Des. 2018; 18: 5713
7c Muravyev NV, Meerov DB, Monogarov KA, Melnikov IN, Kosareva EK, Fershtat LL, Sheremetev AB, Dalinger IL, Fomenkov IV, Pivkina AN. Chem. Eng. J. 2021; 421: 129804

8a Song Q.-G, Zhang L, Mo Z.-Y. Chin. J. Org. Chem. 2023; 31: 286
8b Li C.-Y, Li H, Zong H.-H, Huang Y.-L, Gozin M, Sun C.-Q, Zhang L. iScience 2020; 23: 100944
8c Song Q.-G, Zhang L, Mo Z.-Y. Phys. Chem. Chem. Phys. 2022; 24: 19252

9 Zhang M.-X, Eaton PE, Gilardi R. Angew. Chem. Int. Ed. 2000; 39: 401

10a Wen L.-Y, Yu T, Lai W.-P, Shi J.-W, Liu M.-C, Liu Y.-Z, Wang B.-Z. J. Phys. Chem. Lett. 2021; 12: 11591
10b Kumari A, Chaudhary AK, Rajasekhar K. Spectrochim. Acta, Part A 2020; 241: 118597
10c Hussein AK, Zeman S, Elbeih A. Thermochim. Acta 2018; 660: 110
10d Yang L.-J, Wu J.-Y, Geng D.-S, Wang F.-P, Huang Y.-X, Chen L. Combust. Flame 2019; 202: 303

11 Sollott GP, Gilbert EE. J. Org. Chem. 1980; 45: 5405

12a Ling Y.-F, Zhang P.-P, Sun L, Lai W.-P, Luo J. Synthesis 2014; 46: 2225
12b Ling Y.-F, Ren X.-L, Lai W.-P, Luo J. Eur. J. Org. Chem. 2015; 1541
12c Zhang J, Hou T.-J, Zhang L, Luo J. Org. Lett. 2018; 20: 7172
12d Zhou Q, Cai R.-B, Li H, Liu Y.-Z, Li B, Hou T.-J, Zhu L, Wang G.-X, Zhang Y, Luo J. Org. Chem. Front. 2023; 10: 2551

13 Kotha S, Salman M, Lal S, Cheekatla SR, Ansari S. Asian J. Org. Chem. 2023; 12: e202300060

14a Zhou Q, Zhu L.-Y, Cai R.-B, Li H, Luo J. FirePhysChem 2023; 3: 11
14b Liu Y.-Z, Cai R.-B, Hou T.-J, Wang G.-X, Luo J. Chin. J. Org. Chem. 2023; 31: 325

15 CCDC 2335732, 2335726 and 2335727 contain the supplementary crystallographic data for compounds 12, 13, and 19, respectively. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures

16a Costa MB, Martins MP, Araújo HC, Resck IS. J. Brazil. Chem. Soc. 2018; 29: 74
16b Hegemann K, Fröhlich R, Haufe G. Eur. J. Org. Chem. 2004; 2181

17a Spackman MA, Jayatilaka D. CrystEngComm 2009; 11: 19
17b Johnson ER, Keinan S, Mori-Sánchez P, Contreras-García J, Cohen AJ, Yang W. J. Am. Chem. Soc. 2010; 132: 6498

18 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador PJ, Dannenberg J, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ. Gaussian 09W, Revision A.02. Gaussian, Inc; Wallingford CT: 2009

19a Lee CT, Yang W.-T, Parr RG. Phys. Rev. B 1988; 37: 785
19b Becke AD. J. Chem. Phys. 1992; 97: 9173
19c Hariharan PC, Pople JA. Theor. Chim. Acta 1973; 28: 213

20 Kamlet MJ, Jacobs SJ. J. Chem. Phys. 1968; 48: 23
21 Diols 9–11: General Procedure Diene 7 (4.9 g, 0.04 mol) and formic acid (1.9 mL, 0.05 mol) were added sequentially to a 100 mL three-neck flask. Under ice bath conditions, a 30% hydrogen peroxide aqueous solution (30 mL) was slowly added dropwise into the reaction mixture. After completion of the addition, the reaction mixture was warmed to room temperature and reacted for 30 min. Then the temperature was raised to 50 °C for reflux reaction for 48 h. The reaction mixture was adjusted to a KI/starch indicator paper with no color change by adding saturated sodium bisulfite solution. Then, it was extracted with ethyl acetate (6 × 30 mL). The organic phase was concentrated using a rotary evaporator and a pale yellow liquid was obtained. The crude product was subjected to silica gel column chromatography and eluted with petroleum ether/ethyl acetate (V/V = 1:1). This process yielded product 9 (3.3 g, 48%) as a white solid, along with the formation of product 10 (0.34 g, 5%) and product 11 (0.48 g, 7%). 2,6-Dioxaadamantane-4,8-diol (9) ¹H NMR (500 MHz, methanol-d ₄): δ = 3.96–3.82 (m, 4 H), 3.76–3.66 (m, 2 H), 2.54 (ddd, J = 13.43, 5.19, 1.48 Hz, 2 H), 1.75–1.66 (m, 2 H). ¹³C NMR (126 MHz, methanol-d ₄): δ = 71.9, 70.1, 68.3, 29.1. IR (thin film): ν = 3345, 2929, 1076, 1056, 1036, 1020, 1001, 804, 767, 754, 685, 652, 475, 430 cm^–1. Anal. Calcd for C₈H₁₂O₄: C, 55.81; H, 7.03. Found: C, 55.98; H, 7.21. 2,7-Dioxaprotoadamantane-4,10-diol (10) ¹H NMR (500 MHz, methanol-d ₄): δ = 4.49 (d, J = 5.52 Hz, 1 H), 4.09–4.04 (m, 1 H), 3.93 (dd, J = 9.18, 2.51 Hz, 1 H), 3.42–3.37 (m, 1 H), 3.02–2.96 (m, 1 H), 2.92 (d, J = 4.18 Hz, 1 H), 2.09 (td, J = 9.39, 8.98, 3.56 Hz, 2 H), 1.96–1.89 (m, 2 H). ¹³C NMR (126 MHz, methanol-d ₄): δ = 82.1, 77.2, 74.3, 71.1, 58.9, 57.9, 29.8, 26.7. IR (thin film): ν = 3378, 3304, 2986, 2940, 2900, 1042, 1023, 977, 962, 808, 784, 715, 649, 515 cm^–1. Anal. Calcd for C₈H₁₂O₄: C, 55.81; H, 7.03. Found: C, 56.03; H, 7.27. 2,7-Dioxa-twistane-4,10-diol (11) ¹H NMR (500 MHz, methanol-d ₄): δ = 4.35 (d, J = 6.83 Hz, 2 H), 4.11 (d, J = 2.25 Hz, 2 H), 3.23–3.13 (m, 2 H), 1.96–1.89 (m, 2 H), 1.82 (dd, J = 6.55, 1.67 Hz, 2 H). ¹³C NMR (126 MHz, methanol-d ₄): δ = 83.1, 73.9, 58.4, 27.0. IR (thin film): ν = 3345, 2937, 1071, 1055, 1033, 1024, 1002, 898, 810, 749, 686, 418 cm^–1. Anal. Calcd for C₈H₁₂O₄: C, 55.81; H, 7.03. Found: C, 55.94; H, 7.18. General Procedure for Nitration In a reaction flask, acetic acid (0.6 mL) and acetic anhydride (0.2 mL) were combined, and then HNO₃ (0.24 mL, 98%) was added while maintaining the reaction temperature below 5 °C (0 °C in this case). The reaction mixture was stirred for 20 min. Then, the diol (172 mg, 1 mmol) was added slowly in portions. After stirring for 4 h at room temperature, the reaction mixture was poured into a mixture of ice and water (10 mL). Ethyl acetate (10 mL) was added, and the mixture was extracted with ethyl acetate (3 × 10 mL). The organic layer was washed with brine, dried with Na₂SO₄, and filtered. The solvent was removed under vacuum, and the resulting residue was purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate (V/V = 15:1). 2,6-Dioxaadamantane-4,8-diyldinitrate (12) White solid; yield 243 mg (93%). ¹H NMR (500 MHz, chloroform-d): δ = 5.03 (d, J = 4.48 Hz, 2 H), 4.37–4.26 (m, 4 H), 2.49 (dd, J = 14.00, 5.29 Hz, 2 H), 2.01 (dd, J = 14.01, 4.29 Hz, 2 H). ¹³C NMR (126 MHz, chloroform-d): δ = 76.1, 66.6, 65.3, 29.3. IR (thin film): ν = 2982, 2896, 1630, 1307, 1274, 1247, 1064, 1034, 1009, 902, 853, 748, 719, 680, 622, 479, 448 cm^–1. Anal. Calcd for C₈H₁₀N₂O₈: C, 36.65; H, 3.84; N, 10.69. Found: C, 36.73; H, 3.91; N, 10.54. 2,7-Dioxaprotoadamantane-4,10-diyldinitrate (13) White solid; yield 233 mg (89%). ¹H NMR (500 MHz, chloroform-d): δ = 5.60 (t, J = 6.11 Hz, 1 H), 4.81 (d, J = 4.66 Hz, 1 H), 4.71 (t, J = 5.09 Hz, 1 H), 4.58 (d, J = 3.65 Hz, 1 H), 4.40 (t, J = 4.31 Hz, 1 H), 4.23 (d, J = 8.37 Hz, 1 H), 2.44 (d, J = 12.54 Hz, 1 H), 2.37 (ddd, J = 6.27, 4.22, 1.90 Hz, 2 H), 1.77 (dt, J = 12.65, 4.38 Hz, 1 H). ¹³C NMR (126 MHz, chloroform-d): δ = 80.1, 74.6, 74.4, 73.9, 72.9, 69.2, 33.8, 30.1. IR (thin film): ν = 2982, 2896, 1636, 1281, 1270, 1067, 1042, 994, 931, 842, 809, 752, 689, 639, 617, 444 cm^–1. Anal. Calcd for C₈H₁₀N₂O₈: C, 36.65; H, 3.84; N, 10.69. Found: C, 36.82; H, 3.87; N, 10.64. 2,7-Dioxatwistane-4,10-diyldinitrate (14) White solid; yield 241 mg (92%). ¹H NMR (500 MHz, chloroform-d): δ = 5.51 (q, J = 4.95 Hz, 2 H), 4.25 (t, J = 3.10 Hz, 2 H), 4.12 (t, J = 4.14 Hz, 2 H), 2.27 (t, J = 3.80 Hz, 4 H). ¹³C NMR (126 MHz, chloroform-d): δ = 75.0, 69.3, 68.0, 30.5. IR (thin film): ν = 2978, 1632, 1621, 1324, 1269, 1224, 1061, 1031, 865, 848, 828, 797, 755, 697, 613 cm^–1. Anal. Calcd for C₈H₁₀N₂O₈: C, 36.65; H, 3.84; N, 10.69. Found: C, 36.78; H, 3.95; N, 10.57. 2-Oxaadamantane-4,8-diyl dinitrate (20) White solid; yield 247 mg (95%). ¹H NMR (500 MHz, chloroform-d): δ = 5.15 (t, J = 3.71 Hz, 2 H), 4.07 (t, J = 4.31 Hz, 2 H), 2.30 (d, J = 4.83 Hz, 2 H), 2.14 (dd, J = 13.94, 3.96 Hz, 2 H), 2.09–2.02 (m, 2 H), 1.91 (d, J = 3.48 Hz, 2 H). ¹³C NMR (126 MHz, chloroform-d): δ = 79.8, 66.3, 30.9, 28.6, 24.8. IR (thin film): ν = 2964, 2949, 884, 1633, 1614, 1270, 1027, 974, 860, 842, 831, 753, 694 cm^–1. General Procedure for Oxidation In a reaction flask, 2-iodoxybenzoic acid (1.12 g, 4.0 mmol) was added to a solution of the diol (172 mg, 1 mmol) in ethyl acetate (20 mL), and the mixture was stirred magnetically at 80 °C. After 12 h of reaction, the resulting suspension was filtered through Celite and washed with ethyl acetate (20 mL). The solvent was removed under vacuum, and the resulting residue was purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate (V/V = 2:1). 2,7-Dioxaprotoadamantane-4,10-dione (16) White solid; yield 91 mg (54%). ¹H NMR (500 MHz, chloroform-d): δ = 5.01 (t, J = 3.39 Hz, 1 H), 4.73 (d, J = 6.21 Hz, 1 H), 4.46 (d, J = 8.53 Hz, 1 H), 4.40 (d, J = 3.98 Hz, 1 H), 2.90 (dd, J = 18.05, 8.54 Hz, 1 H), 2.80 (d, J = 17.96 Hz, 1 H), 2.60 (d, J = 12.98 Hz, 1 H), 2.37 (ddd, J = 13.12, 6.27, 2.85 Hz, 1 H). ¹³C NMR (126 MHz, chloroform-d): δ = 202.0, 200.8, 82.7, 81.6, 79.0, 78.3, 40.8, 40.6. IR (thin film): ν = 3303, 1738, 1713, 1233, 1102, 1068, 1036, 1024, 1004, 975, 905, 897, 822, 789, 726, 590, 637. Anal. Calcd for C₈H₈O₄: C, 57.14; H, 4.80. Found: C, 57.32; H, 4.97. 2,7-Dioxatwistane-4,10-dione (17) Light yellow oil; yield 114 mg (68%). ¹H NMR (500 MHz, chloroform-d): δ = 4.69 (dt, J = 6.00, 2.86 Hz, 2 H), 3.53 (s, 2 H), 2.35 (d, J = 3.16 Hz, 4 H). ¹³C NMR (126 MHz, chloroform-d): δ = 202.4, 84.3, 55.2, 28.2. IR (thin film): ν = 3380, 2960, 1723, 1709, 1634, 1061, 1023, 947, 923, 862, 824, 779, 586 cm^–1. Anal. Calcd for C₈H₈O₄: C, 57.14; H, 4.80. Found: C, 57.27; H, 4.95. Synthesis of Tetranitro Derivatives The ketone (168 mg, 1 mmol) was dissolved in methanol (15 mL) and treated with hydroxylamine hydrochloride (278 mg, 4 mmol) and sodium acetate (492 mg, 6.0 mmol). The resulting mixture was stirred for 12 h. Brine (5 mL) was added, and the mixture was extracted with ethyl acetate (3 × 10 mL). The combined organic phases were dried with sodium sulfate. The solvent was removed under vacuum. A mixture of the crude product, urea (360 mg, 6.0 mmol), Na₂SO₄ (5 g), and dichloromethane (20 mL) was stirred and heated to 50 °C. A solution of N₂O₅ (650 mg, 6.0 mmol) in CH₂Cl₂ (10 mL) was added dropwise over 5 min, during which time a green color initially appeared and then faded as more N₂O₅ was added. The reaction mixture was stirred for an additional 30 min and then poured into an ice-cold saturated solution of sodium bicarbonate (10 mL). The organic layer was washed with brine, dried with Na₂SO₄, and filtered. The solvent was removed under vacuum, and the resulting residue was purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate (V/V = 10:1). 4,4,10,10-Tetranitro-2,7-dioxaprotoadamantane (18) White solid; yield 154 mg (48%). ¹H NMR (500 MHz, acetone-d ₆): δ = 5.79 (d, J = 9.77 Hz, 2 H), 5.57 (d, J = 3.60 Hz, 1 H), 5.25 (t, J = 3.14 Hz, 1 H), 3.81 (dd, J = 17.58, 9.13 Hz, 1 H), 3.06 (d, J = 17.54 Hz, 1 H), 2.60 (ddd, J = 14.07, 6.55, 2.74 Hz, 1 H), 2.26 (dd, J = 14.14, 1.34 Hz, 1 H). ¹³C NMR (126 MHz, acetone-d ₆): δ = 115.4, 114.9, 78.8, 78.2, 75.5, 70.9, 36.0, 30.8. IR (thin film): ν = 1567, 1310, 1066, 1032, 835, 826, 801 cm^–1. Anal. Calcd for C₈H₈N₄O₁₀: C, 30.01; H, 2.52; N, 17.50. Found: C, 30.27; H, 2.64; N, 17.61. 4,4,10,10-Tetranitro-2,7-dioxa-twistane (19) White solid; yield 166 mg (52%). ¹H NMR (500 MHz, acetone-d ₆): δ = 5.47 (d, J = 2.95 Hz, 2 H), 4.88 (dd, J = 5.15, 3.07 Hz, 2 H), 3.66 (dd, J = 16.23, 5.14 Hz, 2 H), 3.36 (d, J = 16.23 Hz, 2 H). ¹³C NMR (126 MHz, acetone-d ₆): δ = 115.8, 73.8, 68.7, 33.5. IR (thin film): ν = 1567, 1310, 1066, 1032, 835, 826, 801 cm^–1. Anal. Calcd for C₈H₈N₄O₁₀: C, 30.01; H, 2.52; N, 17.50. Found: C, 30.19; H, 2.57; N, 17.44.

Supplementary Material

Supporting Information