Synthesis and Crystal Structure of Trans-3-phenyl-12-substituted Cyclododecanone†

doi:10.7503/cjcu20160717

Abstract

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

CLC Number:

O626

TrendMD:

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

Figures/Tables 10

References 38

[1]	Zoorob H. H., Elsherbini M. S., Hamama W. S., Arkivoc,2011, 2011(i), 429—495
[2]	Zoorob H. H., Elsherbini M. S., Hamama W. S., Am. J. Org. Chem., 2012, 2, 63—68
[3]	Miura T., Yadav N. D., Iwasaki H., Ozeki M., Kojima N., Yamashita M., Org. Lett., 2012, 14, 6048—6051
[4]	Wang X. L., Zhang S., Pang Y. L., Yuan H. H., Liang X. M., Zhang J. J., Wang D. Q., Wang M. A., Dong Y. H., Eur. J. Med. Chem., 2014, 73, 286—294
[5]	Silk P. J., Ryall K., Mayo P., MaGee D. I., Leclair G., Fidgen J., Lavallee R., Price J., McConaghy J., J. Chem. Ecol., 2015, 41, 294—302
[6]	Sathesh V., Umamahesh B., Ramachandran G., Ravindaranath S. R., Sathiyanarayanan K. I., New J. Chem., 2012, 36, 2292—2301
[7]	Sathesh V., Sathiyanarayanan K. I., New J. Chem., 2016, 40, 3833—3842
[8]	Karthikeyan N. S., Gunasekar R., Sathiyanarayanan K. I., Ravindaranath R., Synthetic Communications, 2012, 42, 3429—3440
[9]	Sathesh V., Natesan S. K., Ravindaranath S. R., Periyasamy G., Sathiyanarayanan K. I., Med. Chem. Res, 2014, 23, 5086—5101
[10]	Sathishkumar M., Ramachandran G., Sathiyanarayanan K. I., RSC Adv., 2014, 4, 8498—8501
[11]	Riedel D., Wurm T., Graf K., Rudolph M., Rominger F., Hashmi A. S. K., Adv. Synth. Catal., 2015, 357, 1515—1523
[12]	Zeiler A., Rudolph M., Rominger F., Hashmi A. S. K., Chem. Eur. J., 2015, 21, 11065—11071
[13]	Skibinski M., Wang Y., Slawin A. M. Z., Lebl T., Kirsch P., O’Hagan D., Angew. Chem. Int. Ed., 2011, 50, 10581—10584
[14]	O’Hagan D., Wang Y., Skibinski M., Slawin A. M. Z., Pure Appl. Chem., 2012, 84, 1587—1595
[15]	Callejo R., Corr M. J., Yang M. Y., Wang M. A., Cordes D. B., Slawin A. M. Z., O’Hagan D., Chem. Eur. J., 2016, 22, 8317—8351
[16]	Wang D. Q., Yang X. L., Wang M. A., Liang X. M., You T. B., Acta Chim. Sinica, 2002, 60, 475—480
	(王道全, 杨晓亮, 王明安, 梁晓梅, 尤田耙化学学报, 2002, 60, 475—480)
[17]	Wang M. A., Ma Z. C., Lu H. Z., Wang D. Q., Acta Chim. Sinica, 2003, 61, 445—449
	(王明安, 马祖超, 路慧哲, 王道全化学学报, 2003, 61, 445—449)
[18]	Wang M. A., Ma Z. C., Wang D. Q., Acta Chim. Sinica, 2003, 61, 399—405
	(王明安, 马祖超, 王道全.化学学报, 2003, 61, 399—405)
[19]	Wang M. A., Zhang N., Lu H. Z., Wang D. Q., Chin. J.　Chem., 2007, 25, 1196—1201
[20]	Zhang C. Y., Chen S. C., Liu J. P., Wang D. Q., Wang M. A., Chin. J. Org. Chem, 2010, 30, 1700—1704
	(张春艳, 陈守聪, 刘吉平, 王道全, 王明安有机化学, 2010, 30, 1700—1704)
[21]	Zhang C. Y., Chen S. C., Wang D. Q., Wang M. A., Acta Chim. Sinica, 2010, 68, 989—995
	(张春艳, 陈守聪, 王道全, 王明安. 化学学报, 2010, 68, 989—995)
[22]	Wang M. A., Yan X. J., Liu J. P., Jin S. H., Li T. G., Yang X., Wang D. Q., Acta Chim. Sinica, 2007, 65, 1657—1662
	(王明安, 闫晓静, 刘建平, 金淑慧, 李太公, 杨旭, 王道全. 化学学报, 2007, 65, 1657—1662)
[23]	Chen S. C., Zhang C. Y., Zhang L., Wang D. Q., Wang M. A., Acta Chim. Sinica, 2011, 69, 1354—1360
	(陈守聪, 张春艳, 张莉, 王道全, 王明安. 化学学报, 2011, 69, 1354—1360)
[24]	Yang M. Y., Zhang X. T., Wang D. Q., Wang M. A., Chin. J. Org. Chem., 2016, 36, 399—405
	(杨明艳, 张晓腾, 王道全, 王明安. 有机化学, 2016, 36, 399—405)
[25]	Han X. Y., Wang M. A., Li T. G., Liang X. M., Dong Y. H., Chen F. H., Wang D. Q., Chin. J. Struct. Chem., 2007, 26, 625—631
[26]	Yang M. Y., Zhang L., Wang D. Q., Wang M. A., Chem. J. Chinese Universities,2015, 36(3), 489—498
	(杨明艳, 张莉, 王道全, 王明安. 高等学校化学学报,2015, 36(3), 489—498)
[27]	Yang M.Y., Synthesis and Conformational Studies of Phenylcyclododecanone Derivatives, 8-CF2 Muscone and 5-CF2 Dodecan-12-olide, China Agricultural University, Beijing, 2016
	(杨明艳. 苯基环十二酮衍生物, 8-CF2麝香酮和5-CF2十二内酯的合成及构象分析, 中国农业大学,北京, 2016)
[28]	Nicolaou K. C., Montagnon T., Baran P. S., Zhong Y. L., J. Am. Chem. Soc., 2002, 124, 2245—2258
[29]	Ruedi G., Hansen H. J., Helv. Chim. Acta, 2004, 87, 1628—1665
[30]	Scafato P., Caprioli F., Rosini C., Tetrahedron: Asymmetry, 2011, 22, 558—561
[31]	Reddy M. M., Swamy P., Naresh M., Srujana K., Durgaiah C., Rao T. V., Narender N., RSC Advances, 2015, 5, 12186—12190
[32]	Horiuchi C. A., Ji S . J., Matsushita M., Chai W.Synthesis, 2004, (2), 202—204
[33]	Dunitz J. D., Shearer H. M. M., Helv. Chim. Acta, 1960, 43, 18—35
[34]	Rawdah T. N., Tetrahedron, 1991, 47, 8579—8586
[35]	Dowd M. K., Stevens E. D., Acta Cryst., 2003, C59, o397—o399
[36]	Li P., Chem. Res. Chinese Universities, 2014, 30(6), 1032—1043
[37]	Lei X., Doubleday C. Jr., Turro N. J., Tetrahedron Lett, 1986, 27, 4671—4674
[38]	Berger S., Diehl B. W. K., Magn.Reson.Chem., 1988, 26, 327—333
	(Ed.:P, H, W, K)

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