行政院國家科學委員會補助專題研究計畫
□ 成 果 報 告
■期中進度報告
合成具開口碳六十及內包氫氣、氨氣與釓離子之化學反應探討
計畫類別：■ 個別型計畫 □ 整合型計畫
計畫編號：NSC 98－2119－M－009－001－MY2
執行期間： 98 年 8 月 1 日至 100 年 7 月 31 日
計畫主持人：莊士卿
共同主持人：
計畫參與人員： 曾政國、程瑞龍、黃煒哲、羅佳伶、賴立祥、劉正揚、
林鈺偉、鄭淳安、鄧桔程、范瑞杰
成果報告類型(依經費核定清單規定繳交)：■精簡報告 □完整報告
本成果報告包括以下應繳交之附件：
□赴國外出差或研習心得報告一份
□赴大陸地區出差或研習心得報告一份
□出席國際學術會議心得報告及發表之論文各一份
□國際合作研究計畫國外研究報告書一份
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執行單位：國立交通大學應用化學系
中 華 民 國 99 年 05 月 31 日
（一） 計畫中文摘要 由於具開口碳六十之分子容器無法以傳統的電弧放電方式獲得，目前只能依賴有機合 成方式。本計劃實行的重點在於以合成方法達到含氫氣、氨氣與釓金屬離子之開口碳六十 為方向，以應用於儲氫、儲氨之分子容器及應用於內包釓金屬離子做為核磁共振顯影劑。 此計劃第一階段將探討以有機金屬催化合成反應獲得具開口之碳六十衍生物，例如以鎳金 屬催化碳六十環化反應。第二階段為探討將具有開口碳六十衍生物，以化學方法形成一個 大的開口，再置入氫氣與氨氣。 關鍵詞: 碳六十、開口碳六十、分子容器、氫氣、氨氣、金屬催化 （二） 計畫英文摘要。
Organic synthesis of open-cage fullerenes containing hydrogen, ammonia and gadolinium inside the cage is described. The desire for these endohedral open-cage fullerenes is primarily driven from their potentialities as hydrogen or ammonia-container in the frontier material field and superior magnetic resonance imaging agent in biomedical field. The availability of these compounds has yet to rely on organic synthesis because they can not be obtained from conventional electrical arc discharge method. The described approach herein starts from metal-catalyzed cycloaddition with C60. A large opening will be formed by controlled bond
scissions. The synthesized open-cage fullerenes can be molecular containers that will be inserted hydrogen or ammonia at high pressure.
Keyword: C60, open-cage fullerene, molecular container, hydrogen, ammonia, metal-catalysis
(二) 報告內容
Introduction
Fullerene materials remain one of the good candidate materials for resolving issues with energy. Fullerenes can be modified chemically to form an opening and subsequently inserted with guest molecules as hydrogen, insertion of other large guest molecules as ammonia or methane could be possible. The desire for larger opening on fullerenes remains highly demanded for study of encapsulation of larger species. In the first term of this project, we investigate metal catalyzed functionalization for derivatizing C60 for future opening on C60 through synthetic approach by
merging two chemically-opened holes.
Results and discussion
We have found a palladium-catalyzed annulation of benzamides with C60. First, we synthesized
the N-alkylated benzamides 1a–j according to conventional methods. We used
N-methylbenzamide (1a) as a standard substrate for our optimization studies. Initially, we
evaluated the reaction of C60 (36 mg, 0.050 mmol) with 1a (20 mg, 0.15 mmol) in the presence of
7 mL) at 120 °C in a sealed tube for 24 h; we obtained the desired C60-fused isoquinolinone 2a in
33% isolated yield, 45% based on recovered C60 (Table 1, entry 1). Although the formation of
this fulleroisoquinolinone was relatively efficient under these conditions, we explored reactions using other oxidizing agents and solvents in a quest for better yields. The corresponding reactions performed using the common oxidants Cu(OAc)2, CH3COOAg,1 and Ag2O,2 under the standard
conditions described above, improved the yields of 2a to 50, 45, and 38%, respectively (Table 1, entries 3–5). Next, we tested the catalytic reaction using AcOH,3 DMSO,4 CH3CN,5 and
1-chloronaphthalene as co-solvents, but the resulting transformations were relatively less efficient (entries 6–10). The reactions performed in chlorobenzene/TFA (10:1) gave 2a in 42% yield with only a trace amount of recovered C60 (entry 11). The addition of one equiv. of water deteriorated
the reaction performance (entry 12).
Table 1. Reactions of C60 with 1a Under Various Conditions
We further evaluated the catalytic scope of this system by employing a variety of substrates 1b–j (Table 2) featuring either
electron-donating and -withdrawing groups on their benzamide aryl ring. In general, substrates equipped with electron-donating groups afforded their corresponding fulleroisoquinolinones in good yields (Table 2, entries 4–7). Substrates 1e and 1f underwent regioselective C–H activations7
at their less-hindered and more-electron-rich para positions (relative to their Me substituents) to afford 2e and 2f in excellent yields of 63 and 61%,
respectively (Table 2, entries 5 and 6). Substrates bearing electron-withdrawing groups, such as the chloro and phenyl units of 1h–j, provided their products in only moderate yields (Table 2, entries 8–10). Under the standard conditions, the reactions of amides bearing N-benzyl substituents (1c, 1d, 1g, 1j) yielded debenzylated products. To overcome this problem, we
(1) (a) Shabashov, D.; Molina Maldonado, J. R.; Daugulis, O. J. Org. Chem. 2008, 73, 7818–7821. (b) Daugulis, O.; Zaitsev, V. G. Angew. Chem., Int. Ed. 2005, 44, 4046–4048.
(2) Thirunavukkarasu, V. S.; Parthasarathy, K.; Cheng, C. H. Angew.Chem. Int. Ed. 2008, 47, 9462–9465.
(3) Kalyani, D.; Deprez, N. R.; Desai, L. V.; Sanford, M. S. J. Am. Chem. Soc. 2005, 127, 7330–7331.
(4) Inamoto, K.; Saito, T.; Katsuno, M.; Sakamoto, T.; Hiroya, K. Org. Lett. 2007, 9, 2931–2934.
(5) Chen, X.; Li, J. J.; Hao, X. S.; Goodhue, C. E.; Yu, J. Q. J. Am. Chem. Soc. 2006, 128, 78–79.
entry oxidant solvents (mL) Yield (%)b
1 Oxone o-DCB/TFA (6:1) 33 (45) 2 Oxone o-DCB/DMSO(6:1) 7 (32) 3 Cu(OAc)2 o-DCB/TFA (6:1) 50 (84) 4 CH3COOAg o-DCB/TFA (6:1) 45 (85) 5 Ag2O o-DCB/TFA (6:1) 38 (53) 6 Cu(OAc)2 o-DCB/AcOH (6:1) 4 (10) 7 Cu(OAc) o-DCB/DMSO (6:1) <3 8 Cu(OAc)2 o-DCB/CH3CN (6:1) <3 9 CH3COOAg o-DCB/AcOH (6:1) 5 (12) 10 Cu(OAc)2 1-Cl-naphthalene/TFA (6:1) 14 (86) 11 Cu(OAc)2 PhCl/TFA(10:1) 42 12c Cu(OAc) 2 o-DCB/TFA (6:1) 37 (55) N H O
+ Oxidant, Solvent10% Pd(OAc)2
120 oC, 24h N O
1a
performed these experiments using only 0.2 mL of TFA, obtaining the desired products in moderate yields (Table 2, entries 3, 4, 7, and 10).
Table 2. Palladium-Catalyzed Syntheses of the Fulleroisoquinolinones 2a–j
+ NH O R2 N O R2 R1 R1 10% Pd(OAc)2 2a-j 1a-j Cu(OAc)2 ODCB/TFA (6:1) 120 oC, 24h
entry amide 1 product yield (%) recovered C60 (%) 1 NH O 2a 50 (84) 42 2 NH O 2b 72 (78) 8 3 NH O 2c 30 (39) 22 4 NH O 2d 34 (62) 44 5 NH O 2e 63 trace 6 NH O 2f 61 (84) 28 7c N H O MeO 2g 40 (76) 47 8 N H O Cl 2h 31 (56) 44 9 N H O Ph 2i 20 (48) 55 10 N H O Ph 2j 24 (41) 42
We characterized the fulleroisoquinolinones 2a–j using infrared (IR) and 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, fast atom bombardment mass spectrometry (FAB MS), and X-ray crystallography. Because each of these compounds possesses a symmetrical plane, its
13C NMR spectrum exhibits 30 sp2-hybridized carbon atoms on the C
60 cage. In their IR spectra,
C=O stretching bands appear at ca. 1650 cm–1. Figure 1 displays a 2D-HMBC spectrum of the selected compound 2f. We made partial peak assignments on the basis of one- (2D-HMQC) and three-bond (2D-HMBC) correlation spectra. For example, the sp3-hybridized carbon atoms of the C60 moiety of 2f appear as two signals at 62.60 (C1) and 79.29 (C2) ppm; C1 and C2 correlate
with the protons on C6 and C11, respectively, through three-bond couplings. Figure 2 presents the structure of compound 2d determined using X-ray diffraction analysis.
Figure 1. 2D-HMBC spectrum of compound 2f.
Figure 2. X-ray crystal structure of compound 2d.
Conclusion
we have achieved metal-catalyzed functionalization in the first step, our next goal will be extending this type of molecule toward opening. The following work is under progress using debenzylated compounds.. N H O NH+ light [4+4] N H+ N O N O and retro [2+2+2] base O2 2. H+ 1. POCl3 Cl Cl Cl Cl
