反式-3-苯基-12-取代环十二酮的合成及晶体结构

doi:10.7503/cjcu20160717

摘要/Abstract

摘要：

以环十二酮为原料, 经2-碘酰基苯甲酸(IBX)氧化制备2-环十二烯酮, 在醋酸钯和三苯基磷催化下, 2-环十二烯酮与苯硼酸反应制得3-苯基环十二酮. 经3-苯基环十二酮与不同试剂发生区域选择性反应制备了一系列新的3-苯基-12-取代环十二酮衍生物, 采用核磁共振波谱(NMR)和液相色谱-高分辨质谱(HRMS)表征了其结构. 在溶液中结晶, 获得了4个代表性化合物的单晶并进行X射线衍射分析, 结果表明, 3-苯基-12-取代环十二酮晶体中的十二元环仍采取[3333]-2-酮构象, 2个取代基为反式构型, 取代基存在2种情形: 2个取代基在同一条边上, 苯基位于与羰基间隔1个亚甲基的β-角碳反向位, 而另1个取代基位于与羰基另一侧相邻的α-角碳顺向位; 或2个取代基在2条边上, 苯基位于与羰基间隔1个亚甲基另一条边的β-边碳外向位, 而另1个取代基位于与羰基另一侧相邻并在同一条边的α-边碳外向位, 量子力学计算结果与晶体衍射分析结果一致.

关键词: 3-苯基环十二酮, 3-苯基-12-取代环十二酮, [3333]-2-酮构象, 构象分析

Abstract:

2-Cyclododecenone was prepared via oxidation of cyclododecanone with o-iodylbenzoic acid(IBX), then 3-phenyl cyclododecanone was synthesized by 2-cyclododecenone and phenyl boronic acid under catalysis of palladium acetate. A series of 3-phenyl-12-substitutedcyclododecanone was regioselectively prepared by the reaction of 3-phenylcyclododecanone with different reagents, and their structures were characterized by ¹H NMR, ¹³C NMR and HR-MS. The crystals for four compounds were obtained in the solution and X-ray diffraction analyses were carried out. The results showed that [3333]-2-one conformation was took by the cyclododecanone ring of 3-phenyl-12-substituted cyclododecanone with trans-configuration of two substituted groups. One case was that the two substituted groups were at the same side, phenyl was at β-corner-anti position of the carbon atom in one side of carbonyl, and the other groups were at α-corner-syn position of the carbon atom in the other side of carbonyl in their crystals. The other case was that the two substituted groups were at the different sides, both phenyl and the other groups were at side-exo position of the carbon atoms in two sides of carbonyl in their crystals. The results of quantum mechanics calculation were consistent with those of X-ray diffraction.

Key words: 3-Phenylcyclododecanone, 3-Phenyl-12-substitutedcyclododecanone, [3333]-2-One conformation, Conformation analysis

中图分类号:

O626

TrendMD:

杨明艳, 张莉, 王道全, 王明安. 反式-3-苯基-12-取代环十二酮的合成及晶体结构. 高等学校化学学报, 2017, 38(3): 403.

YANG Mingyan, ZHANG Li, WANG Daoquan, WANG Ming an. Synthesis and Crystal Structure of Trans-3-phenyl-12-substituted Cyclododecanone^†. Chem. J. Chinese Universities, 2017, 38(3): 403.

图/表 10

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Compd.	Appearance	m. p./℃	Yield(%)	HRMS(ESI), m/z (cacld.) [M+H]⁺
3a	White solid	128—130	59	337.1162(337.1158)
3b	White solid	138—140	67	385.1024(385.1023)
3c	White solid	76—78	37	273.2210(273.2213)
3d	White solid	49—51	24	315.2679(315.2682)
3e	White solid	119—121	71	349.2517(349.2526)
3f	White solid	115—117	52	363.2310(363.2319)
3g	White solid	106—108	37	289.2157(289.2162)
3h	White solid	89—91	59	399.1988(399.1988)
4	White solid	93—95	7	463.0528(463.0531)

Compd.	Appearance	m. p./℃	Yield(%)	HRMS(ESI), m/z (cacld.) [M+H]⁺
3a	White solid	128—130	59	337.1162(337.1158)
3b	White solid	138—140	67	385.1024(385.1023)
3c	White solid	76—78	37	273.2210(273.2213)
3d	White solid	49—51	24	315.2679(315.2682)
3e	White solid	119—121	71	349.2517(349.2526)
3f	White solid	115—117	52	363.2310(363.2319)
3g	White solid	106—108	37	289.2157(289.2162)
3h	White solid	89—91	59	399.1988(399.1988)
4	White solid	93—95	7	463.0528(463.0531)

Compd.	¹H NMR(300 MHz, CDCl₃), δ	¹³C NMR(75 MHz, CDCl₃), δ
3a	7.38—7.20(m, 5H), 4.59(dd, 1H,J=12.2, 3.6 Hz), 3.34—3.26(m, 1H), 3.08(dd, 1H, J=14.4, 3.1 Hz), 2.94(dd, 1H, J=12.2, 14.4 Hz), 2.51—2.42(m, 1H), 2.00—1.93(m, 1H), 1.63—1.08(m, 14H)	203.8, 143.8, 128.5, 127.4, 126.5, 48.9, 43.9, 39.1, 33.1, 30.9, 24.7, 24.4, 24.2, 23.6, 22.3, 21.9
3b	7.35—7.19(m, 5H), 4.99(dd, 1H, J=11.3, 3.6 Hz), 3.31(dd, 1H, J=13.5, 2.9 Hz), 3.17—3.12(m, 1H), 2.70—2.59(m, 2H), 2.01—1.92(m, 1H), 1.60—1.12(m, 14H)	204.4, 143.7, 128.6, 127.4, 126.6, 45.9, 40.3, 34.9, 30.8, 25.9, 25.84, 25.81, 23.6, 23.0, 22.8, 22.2
3c	7.30—7.18(m, 5H), 3.61—3.55(m, 1H), 3.33(dd, J=12.7, 8.5 Hz, 1H), 2.86—2.82(m, 1H), 2.37(dd, J=12.7, 2.2 Hz, 1H), 1.81—1.07(m, 16H), 1.06(d, J=5.1 Hz, 3H)	213.4, 145.3, 128.4, 127.6, 126.0, 46.3, 43.9, 38.6, 32.4, 30.8, 26.6, 26.3, 23.9, 28.2, 21.5, 21.2, 15.3
3d	7.31—7.18(m, 5H), 3.60—3.56(m, 1H), 3.36(dd, J=12.8, 8.6 Hz, 1H), 2.72—2.66(m, 1H), 2.38(dd, J=12.8, 2.2 Hz, 1H), 1.79—1.64(m, 4H), 1.35—1.18(m, 16H), 0.86(t, J=5.3 Hz, 3H)	213.2, 145.4, 128.4, 127.6, 126.0, 52.2, 45.2, 38.5, 32.4, 29.9, 29.8, 29.2, 26.5, 24.0, 22.9, 21.8
3e	7.29—7.12(m, 10H), 3.62—3.56(m, 1H), 3.31(dd, 1H, J=17.4, 11.3 Hz), 3.06—2.96(m, 2H), 2.67—2.61(m, 1H), 2.19(dd, 1H, J=17.4, 2.8 Hz), 1.84—1.26(m, 16H)	212.2, 145.0, 140.2, 128.8, 128.3, 128.2, 127.4, 126.0, 125.9, 53.9, 45.1, 37.9, 36.0, 32.2, 28.8, 26.5, 26.4, 23.8, 22.7, 21.7, 20.7
3f	7.89(d, J=7.2 Hz, 2H), 7.59—7.52(m, 1H), 7.47—7.41(m, 2H), 7.29—7.13(m, 5H), 4.67(dd, 1H, J=9.8, 3.3 Hz), 3.41—3.35(m, 1H), 2.99(dd, 1H, J=16.0, 10.5 Hz), 2.75(dd, 1H, J=16.0, 3.2 Hz), 2.37—2.34(m, 1H), 1.86—1.15(m, 15H)	205.7, 196.4, 145.1, 136.3, 133.4, 128.8, 128.4, 128.3, 127.3, 126.1, 62.5, 47.48, 40.3, 32.6, 27.8, 26.22, 25.9, 24.8, 23.7, 23.5, 23.0
3g	7.33—7.22(m, 5H), 4.01(dd, J=6.7, 2.9 Hz, 1H), 3.37(s, 3H), 3.23—3.14(m, 1H), 2.53(dd, J=16.6, 3.1 Hz, 1H), 2.03—1.20(m, 16H)	209.2, 144.5, 128.2, 127.5, 126.1, 86.6, 57.6, 42.4, 38.0, 30.9, 28.5, 26.0, 25.7, 22.4, 22.3, 20.4, 19.3
3h	7.76—7.21(m, 10H), 4.51(dd, J=9.3, 2.2 Hz, 1H), 3.35—3.26(m, 2H), 3.00—2.94(m, 1H), 2.14—1.14(m, 16H)	201.9, 143.2, 135.9, 134.3, 129.3, 129.0, 128.6, 127.4, 126.7, 126.3, 72.3, 50.5, 38.8, 30.9, 25.7, 25.6, 24.3, 23.0, 22.9, 22.2
4	8.06—7.96(m, 2H), 7.58—7.39(m, 2H), 5.77—5.71(m, 1H), 5.01(d, J=10.9 Hz,1H), 3.20—3.12(m, 1H), 2.62—2.52(m, 1H), 1.88—1.26(m, 16H)	204.1, 164.0, 134.6, 133.2, 131.6, 129.8, 129.7, 127.9, 73.8, 37.9, 31.7, 28.6, 25.3, 25.2, 24.3, 24.0, 23.2, 22.0, 19.8

Compd.	¹H NMR(300 MHz, CDCl₃), δ	¹³C NMR(75 MHz, CDCl₃), δ
3a	7.38—7.20(m, 5H), 4.59(dd, 1H,J=12.2, 3.6 Hz), 3.34—3.26(m, 1H), 3.08(dd, 1H, J=14.4, 3.1 Hz), 2.94(dd, 1H, J=12.2, 14.4 Hz), 2.51—2.42(m, 1H), 2.00—1.93(m, 1H), 1.63—1.08(m, 14H)	203.8, 143.8, 128.5, 127.4, 126.5, 48.9, 43.9, 39.1, 33.1, 30.9, 24.7, 24.4, 24.2, 23.6, 22.3, 21.9
3b	7.35—7.19(m, 5H), 4.99(dd, 1H, J=11.3, 3.6 Hz), 3.31(dd, 1H, J=13.5, 2.9 Hz), 3.17—3.12(m, 1H), 2.70—2.59(m, 2H), 2.01—1.92(m, 1H), 1.60—1.12(m, 14H)	204.4, 143.7, 128.6, 127.4, 126.6, 45.9, 40.3, 34.9, 30.8, 25.9, 25.84, 25.81, 23.6, 23.0, 22.8, 22.2
3c	7.30—7.18(m, 5H), 3.61—3.55(m, 1H), 3.33(dd, J=12.7, 8.5 Hz, 1H), 2.86—2.82(m, 1H), 2.37(dd, J=12.7, 2.2 Hz, 1H), 1.81—1.07(m, 16H), 1.06(d, J=5.1 Hz, 3H)	213.4, 145.3, 128.4, 127.6, 126.0, 46.3, 43.9, 38.6, 32.4, 30.8, 26.6, 26.3, 23.9, 28.2, 21.5, 21.2, 15.3
3d	7.31—7.18(m, 5H), 3.60—3.56(m, 1H), 3.36(dd, J=12.8, 8.6 Hz, 1H), 2.72—2.66(m, 1H), 2.38(dd, J=12.8, 2.2 Hz, 1H), 1.79—1.64(m, 4H), 1.35—1.18(m, 16H), 0.86(t, J=5.3 Hz, 3H)	213.2, 145.4, 128.4, 127.6, 126.0, 52.2, 45.2, 38.5, 32.4, 29.9, 29.8, 29.2, 26.5, 24.0, 22.9, 21.8
3e	7.29—7.12(m, 10H), 3.62—3.56(m, 1H), 3.31(dd, 1H, J=17.4, 11.3 Hz), 3.06—2.96(m, 2H), 2.67—2.61(m, 1H), 2.19(dd, 1H, J=17.4, 2.8 Hz), 1.84—1.26(m, 16H)	212.2, 145.0, 140.2, 128.8, 128.3, 128.2, 127.4, 126.0, 125.9, 53.9, 45.1, 37.9, 36.0, 32.2, 28.8, 26.5, 26.4, 23.8, 22.7, 21.7, 20.7
3f	7.89(d, J=7.2 Hz, 2H), 7.59—7.52(m, 1H), 7.47—7.41(m, 2H), 7.29—7.13(m, 5H), 4.67(dd, 1H, J=9.8, 3.3 Hz), 3.41—3.35(m, 1H), 2.99(dd, 1H, J=16.0, 10.5 Hz), 2.75(dd, 1H, J=16.0, 3.2 Hz), 2.37—2.34(m, 1H), 1.86—1.15(m, 15H)	205.7, 196.4, 145.1, 136.3, 133.4, 128.8, 128.4, 128.3, 127.3, 126.1, 62.5, 47.48, 40.3, 32.6, 27.8, 26.22, 25.9, 24.8, 23.7, 23.5, 23.0
3g	7.33—7.22(m, 5H), 4.01(dd, J=6.7, 2.9 Hz, 1H), 3.37(s, 3H), 3.23—3.14(m, 1H), 2.53(dd, J=16.6, 3.1 Hz, 1H), 2.03—1.20(m, 16H)	209.2, 144.5, 128.2, 127.5, 126.1, 86.6, 57.6, 42.4, 38.0, 30.9, 28.5, 26.0, 25.7, 22.4, 22.3, 20.4, 19.3
3h	7.76—7.21(m, 10H), 4.51(dd, J=9.3, 2.2 Hz, 1H), 3.35—3.26(m, 2H), 3.00—2.94(m, 1H), 2.14—1.14(m, 16H)	201.9, 143.2, 135.9, 134.3, 129.3, 129.0, 128.6, 127.4, 126.7, 126.3, 72.3, 50.5, 38.8, 30.9, 25.7, 25.6, 24.3, 23.0, 22.9, 22.2
4	8.06—7.96(m, 2H), 7.58—7.39(m, 2H), 5.77—5.71(m, 1H), 5.01(d, J=10.9 Hz,1H), 3.20—3.12(m, 1H), 2.62—2.52(m, 1H), 1.88—1.26(m, 16H)	204.1, 164.0, 134.6, 133.2, 131.6, 129.8, 129.7, 127.9, 73.8, 37.9, 31.7, 28.6, 25.3, 25.2, 24.3, 24.0, 23.2, 22.0, 19.8

Compd.	3d	3e	3g	3h
Crystal size/mm³	0.70×0.05×0.04	0.50×0.30×0.08	0.40×0.25×0.07	0.30×0.08×0.05
Empirical formula	C₂₂H₃₄O	C₂₅H₃₂O	C₁₉H₂₈O₂	C₂₄H₃₀SO₃
Formula weight	314.49	348.51	288.41	398.54
Temperature/K	102.1	98.7	104.4	104.5
Crystal system	Momoclinic	Momoclinic	Orthorhombic	Momoclinic
Space group	P2/n	C2/n	Pbca	P2₁/c
a/nm	1.5910(6)	2.34299(4)	1.24310(8)	1.38599(4)
b/nm	0.5535(2)	0.562885(9)	1.07820(5)	1.50455(5)
c/nm	2.3010(8)	3.03128(5)	2.4889(3)	0.99769(3)
α/(°)	90.00	90.00	90.00	90.00
β/(°)	108.65(4)	101.0795(16)	90.00	98.324(3)
γ/(°)	90.00	90.00	90.00	90.00
Volume/nm³	1.9197(12)	3.92324(11)	3.3359(5)	2.05857(11)
Z	4	8	8	4
ρ_calc./(g·cm^-3)	1.088	1.180	1.149	1.286
μ/mm^-1	0.064	0.0525	0.072	0.180
F(000)	696	1520	1264	856
2θ/(°)	6.96—52	5.94—142.44	6.54—52	6.06—52
Index range	-15≤h≤19	-22≤h≤28	-13≤h≤15	-17≤h≤17
	-4≤k≤6	-6≤ k≤6	-13≤k≤10	-18≤k≤18
	-28≤l≤23	-37≤l≤36	-25≤l≤30	-11≤l≤12
Reflections collected	7913	5892	10243	9231
Independent reflections R(int)	3768(0.1258)	6094(0.0000)	3288(0.0381)	4038(0.0254)
Data/restraints/parameters	3768/0/209	6094/0/236	3288/0/191	4038/16/253
GOF	0.969	1.084	1.058	1.046
Final R indices[I>2σ(I)]	R₁=0.0872,	R₁=0.0464,	R₁=0.0479,	R₁=0.0554,
	wR₂=0.1386	wR₂=0.1242	wR₂=0.0933	wR₂=0.1244
R index(all data)	R₁=0.2043,	R₁=0.0496,	R₁=0.0660,	R₁=0.0668,
	wR₂=0.1979	wR₂=0.1264	wR₂=0.1016	wR₂=0.1311
Largest diff. peak and hole/(e·nm^-3)	239, -271	248, -214	198, -198	116, -436
Completeness	0.998	0.992	0.999	0.998