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
a   School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China
,
Qi Zhou
a   School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China
,
Jingjing Zhao
b   Gansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin 730900, P. R. of China
,
Tianjiao Hou
c   College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China
,
Guixiang Wang
a   School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China
,
Long Zhu
a   School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China
,
Bing Li
a   School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China
,
Yu Zhang∗
a   School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China
,
Jun Luo  ∗
a   School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China
› Author AffiliationsThis work was financially supported by the National Natural Science Foundation of China (22075144).
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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2333-8774.
  • Supporting Information


Publication History

Received: 13 May 2024

Accepted after revision: 27 May 2024

Accepted Manuscript online:
27 May 2024

Article published online:
06 June 2024

© 2024. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

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  • 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.