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1、?()(*+,?I?1,5-?-1,4-?-3-?(?)? ? ? !“?#$%?$ ?$#,-?-?AB?CDEF GHIJ$GK%?LM?N 1,5-?-1,4-?-3-?O“P?QR89:;.101.2.1 =?.101.2.2 =?.101.2.3 ?=. 111.3 1,5-?-1,4-?-3-?$.111.4 1,5-?-1,4-?-3-?Oh?,j?-? h)?DEF15 miny?;?NaBH4EF10 min?y?CH2Cl2?b?V+,?96%?=? DBU? -10oC ,- 1 h +,? 90%?$?1 mLj./01nCDk%,-?j 1H NMR(400 MHz,
2、 CDCl3): ?: 1.48-2.75(m, 11H), 2.32(s, 3H, CH3), 2.37(s, 3H, CH3), 3.73(t, 1H), 3.88(t, 1H), 3.15(dd, 1H, J=12 Hz, 4 Hz), 7.07-7.21(m, 8H, Ph-H); m/z(ESI): 361M+1+. 2e: ,-./0 123 114-116 oC; 1H NMR(400 MHz, CDCl3): ?: 1.47-2.76(m, 11H), 3.15(dd, 1 H, J=12 Hz, 4 Hz), 3.76(s, 3H, OCH3), 3.90(t, 2H), 7
3、.18-7.30(m, 9H, Ph-H); m/z (ESI): 363M+1+.2f: ,-./0 123 144-146 oC; 1H NMR(400 MHz, CDCl3): ?: 1.48-2.77(m, 11H), 3.17(dd, 1H, J=12 Hz, 4 Hz), 2.28(s, 3H, CH3), 3.69-3.95(m, 2H), 7.00-7.30(m, 9H, Ph-H); Anal. Calcd for C24H26O2: C 83.24, H 7.51; found C 83.36, H 7.36.2g: ,-./0 123 200-202 oC; 1H NMR
4、(400 MHz, CDCl3): ?: 1.46-2.76(m, 11H), 3.18(dd, 1 H, J=12 Hz, 4 Hz), 3.77(t, 1H), 3.97(t, 1H), 7.18-7.29(m, 9H, Ph-H); m/z (ESI): 368M+1+. 2h: ,-./0 123 120-122 oC; 1H NMR(400 MHz, CDCl3): ?: 1.47-2.78(m, 11H), 3.19(dd, 1 H, J=12 Hz, 4 Hz), 3.77(t, 1H), 3.94(t, 1H), 7.18-7.28(m, 9H, Ph-H); m/z (ESI
5、): 368M+1+.2.1.2 ?1?Q$?“P?O 1,5-?-1,4-?-3-?,-C?DE1G?18HIJ$?U?V?$A B?$l?F?,-?4?CD$? ,-/, 1:1.2 ?2a ? 97%(Entry 2)K?N?M“P?=?G:x? 2a ?HId?efgh(69 mg?1 mmol)?bc5CDEFX,-?:;K,-?“?V?j? 1H NMR(DMSO): : 3.31-3.34(d, J=14.2Hz, 2H, COCH2), 3.34-3.39(d, J=14.2Hz, 2H, COCH2), 3.53-3.86(m, 2H, 2PhCH), 7.13-7.45(m
6、, 8H, Ph-H), 10.62(s, 1H, N-H); m/z (ESI): 492M-1+; 13C NMR (DMSO), 27.4, 33.9, 43.5, 44.1, 52.7,63.9, 121.2, 131.5, 131.9, 141.0, 154.8, 170.0, 170.1 ppm.3f: ,-./012: 186-188oC; 1H NMR(DMSO): : 3.31-3.34(d, J=10.5Hz, 2H, COCH 2), 3.42-3.45(d, J=10.0Hz, 2H, COCH2), 3.54-3.58(t, J=14.0Hz, 1H, PhCH ),
7、 3.86-3.89(t, J=12.5Hz, 1H, PhCH ), 7.19-7.45(m, 8H, Ph-H), 7.62(s, 1H, N-H); m/z(ESI): 493 M+; 13C NMR(100 MHz, DMSO): 27.2, 33.9, 43.6, 44.4, 52.6, 64.1, 121.8, 128.8, 130.9, 132.7, 143.6, 154.6, 169.0, 170.1 ppm.3g: ,-./012: 212-214 oC; 1H NMR(DMSO): : 3.24-3.31(m, 4H, 2COCH 2), 3.89-3.93(t, J=13
8、.6Hz, 2H, PhCH), 4.03-4.06(t, J=17.5Hz, 2H, PhCH), 7.18-7.45(m, 8H, Ph-H), 10.66(s, 1H, N-H); m/z (ESI): 404M+1+; 13C NMR(100 MHz, DMSO): 22.0, 36.6, 44.8, 45.6, 53.0, 55.9, 127.9,128.5, 129.2, 129.5, 134.0, 157.2, 168.3, 168.7 ppm.3h: ,-./012: 236-238oC;1H NMR(DMSO): : 3.22-3.23(d, J=4.84Hz, 2H, CO
9、CH 2), 3.31-3.33(d, J=9.12Hz, 2H,COCH2), 3.84-3.88(dd, J=13.2, 3.48 Hz, 1H, PhCH), 3.97-4.00(dd, J=13.2, 3.72 Hz, 1H, PhCH), 7.19-7.61(m, 6H, Ph-H), 10.71(s, 1H, N-H); m/z (ESI): 473 M+; 13C NMR(100 MHz, DMSO): 26.8, 33.6, 44.0, 45.4, 58.3, 65.0, 124.8, 126.9, 128.3, 129.6, 132.5, 178.6, 209.7 ppm.
10、3i: ,-./0 12: 196-198 oC; 1H NMR(DMSO): : 3.38-3.54(m, 4H, 2COCH2), 3.56-4.04(m, 2H, 2PhCH), 7.08-7.25(m, 8H, Ph-H), 7.69(s, 1H, N-H); m/z(ESI): 402M-1+; 13C NMR(100 MHz, DMSO): ?2227.2, 33.9, 43.6, 44.4, 52.4, 64.1, 125.8, 128.2, 129.8, 143.3, 154.3, 168.9, 170.0 ppm.2.2.2 ?K?7 3 89?5CDEFXB?$l?F?,-
11、?HIflK 1,5-?-1,4-?-3-?OB?$lx? 1:0.15 ?5 30oC ,- 6 h?3a ? 43%(Entry 2)?K?4?f, 40oC 50oC ?3a ? 52%(Entry 5) 73%(Entry 6)? 3? 3- ! ! ! !-6,10-?“?“?“?“?-2-#!#!#!#!-?4.5?-1,4,8-$? Table 3The effect of reaction conditions on one-pot synthesis of 3-aza-6,10-diphenyl-2-oxa-spiro4.5decane-1,4,8-trione under
12、ultrasound irradiation*EntryAmount of NaOH, mmolFrequency, kHzTemperature, oCIsolated yield, %10.1025302220.1525304330.3025306840.5025506150.1525405260.1525507370.1540506980.3025509190.30-reflux36* Substrate: 1,5-diphenyl-1,4-pentadien-3-one, 1mmol; CH 3OH, 2 mL; dimethyl malonate, 1mmol; hydroxylam
13、ine hydrochloride, 1mmol. Reaction time: addition: 2 h, cyclocondensation: 4 h. Q$DE1CD$?,-?HI5 50oC ? 25 kHz $?CDEF?3a ? 73%(Entry 6)? 40 kHz CDEF?3a ? 69%(Entry 7)?N$?CDEF?gn?,-? 1DECDEF? Q$11P?CDEF?5?st?G?stXnd?qr 6 h +, 3a ? 36%(Entry 9)KCDEF?O,-?a?f?K?J?,-?Ust?1,5-?-1,4-?-3-?(1 mmol)?B? 2 ?#$%?
14、k?!“?$?- ?l?-KCDkOp?;?$m?mn?op?q?:;,-?,-2 h?,-5?Ha?f?(200-300?)B“?Vj$?+,? m.p. 176-177oC; 1H NMR(CDCl 3, 400 MHz): : 2.95(dd, 1H, J=6.6, 16.7Hz, 4-H), 3.66(dd, 1H, J=12.6, 16.5Hz, 4-H), 5.24(dd, 1H, J=6.8, 12.3Hz, 5-H), 6.41(dd, 1H, J=10.7, 15.3Hz, =CH), 6.78(d, 1H, J=15.8, =CH), 6.78-7.43(m, 17H, P
