High Regioselective Aminobromination of β-Nitrostyrene Derivatives with 1,3-Dibromo-5,5-dimethyl Hydantoin†

doi:10.7503/cjcu20141110

Abstract

Abstract:

A new protocol for the high regioselective aminobromination of β-nitrostyrene derivatives with 1,3-dibromo-5,5-dimethyl hydantoin(DBDMH) as nitrogen/bromine sources was developed. Two kinds of β-nitrostyrene derivatives got different reaction results under different reaction conditions. For the β-nitrostyrene derivatives, this protocol offered vicinal haloamine products in good to excellent yields(up to 97%) at room temperature in CH₃CN catalyzed by Na₂CO₃. For the β-methyl-β-nitrostyrene, the good to excellent yields(up to 95%)were also achieved refluxed in CH₃CN catalyzed by KOH. The strong electron-donating substituents(e.g., CH₃O) on the 4-position of benzene ring could deactivated the reaction activity of β-nitrostyrenederi-vetives with DBDMH. However, the vicinal haloamines were also afforded as the sole addition product. Whereas strong electron-withdrawing substituent(e.g., NO₂) could activated reaction activity remarkably and the vicinal haloamines were afforded as the sole addition product, too. The result revealed that the addition reaction has a nucleophilic addition feature. The aminobromination of 20 examples of β-nitrostyrenes were investigated in this work and the structure of all products were confirmed by the corresponding ¹H NMR, ¹³C NMR spectra and HRMS(ESI). A possible mechanism involving a nucleophilic conjugate addition was proposed.

Key words: Aminobromination, β-Nitrostyrene, High regioselective, 1,3-Dibromo-5, 5-dimethyl hydantoin

CLC Number:

O626.3

TrendMD:

LIU Yali, LIU De’e, DU Manfei, CAO Chenxi, CHEN Zhanguo. High Regioselective Aminobromination of β-Nitrostyrene Derivatives with 1,3-Dibromo-5,5-dimethyl Hydantoin^†[J]. Chem. J. Chinese Universities, 2015, 36(6): 1117.

Figures/Tables 8

References 37

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Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃
1a	55.1—56.3(55—56^[21])	11a	145—146(128—131^[31])
2a	100.1—102.1(102—102.5^[22])	12a	61.5—61.7(60—61 ^[32])
3a	84.4—86.0(85.5—87.5^[23])	13a	54.0—54.4(55^[33])
4a	120.2—120.6(125.5—126.5^[24])	14a	42.0—42.3(43—44.5^[34])
5a	98—99(98—99^[25])	15a	96.4—97.3(96—97^[25])
6a	98.6—99.1(101—102.5^[26])	16a	64.0—65.1(66^[35])
7a	108.5—110.4(112—113^[27])	17a	88.6—89.9(86—87^[36])
8a	149.3—150.6(151—153^[28])	18a	89.3—91.3(93—95^[35])
9a	201.2—203.1(203—204^[29])	19a	113.8—114.1(114—115^[37])
10a	123.1—124.3(124.5—126^[30])	20a	56.1—56.3(55—55.5^[35])

Compd.	m.p.(ref.)/℃	Compd.	m.p.(ref.)/℃
1a	55.1—56.3(55—56^[21])	11a	145—146(128—131^[31])
2a	100.1—102.1(102—102.5^[22])	12a	61.5—61.7(60—61 ^[32])
3a	84.4—86.0(85.5—87.5^[23])	13a	54.0—54.4(55^[33])
4a	120.2—120.6(125.5—126.5^[24])	14a	42.0—42.3(43—44.5^[34])
5a	98—99(98—99^[25])	15a	96.4—97.3(96—97^[25])
6a	98.6—99.1(101—102.5^[26])	16a	64.0—65.1(66^[35])
7a	108.5—110.4(112—113^[27])	17a	88.6—89.9(86—87^[36])
8a	149.3—150.6(151—153^[28])	18a	89.3—91.3(93—95^[35])
9a	201.2—203.1(203—204^[29])	19a	113.8—114.1(114—115^[37])
10a	123.1—124.3(124.5—126^[30])	20a	56.1—56.3(55—55.5^[35])

Compd.	Appearance	Yield^*(%)	m. p./℃	HRMS [M+Na]⁺(calcd.), m/z
1b	White solid	94	167—169	457.9151(457.9150)
2b	White solid	89	147—149	471.9295(471.9307)
3b	White solid	85	142—144	487.9246(487.9256)
4b	White solid	45	169—171	547.9466(547.9467)
5b	Pale yellow solid	65	200—202	595.8471(595.8466)
6b	Pale yellow solid	95	166.8—169.0	475.9046(475.9056)
7b	White solid	95	180—182	491.8763(491.8760)
8b	White solid	94	155—157	535.8259(535.8255)
9b	White solid	97	185—187	502.8991(502.9001)
10b	White solid	96	164—165	502.8988(502.9001)
11b	White solid	90	164—165	507.9308(507.9307)
12b	White solid	90	164.4—166.7	392.0214(392.0222)
13b	White solid	78	166.1—168.1	406.0374(406.0378)
14b	White solid	76	168.7—170.4	422.0327(422.0328)
15b	Yellow solid	84	156.1—157.5	531.9513(531.9518)
16b	Pale yellow solid	95	164.8—165.7	410.0123(410.0128)
17b	Yellow solid	94	199.5—201.4	425.9826(425.9832)
18b	White solid	94	177.1—178.9	471.9302(471.9307)
19b	White solid	95	148.6—149.9	437.0077(437.0073)
20b	White solid	93	175.5—176.3	437.0067(437.0073)

Compd.	Appearance	Yield^*(%)	m. p./℃	HRMS [M+Na]⁺(calcd.), m/z
1b	White solid	94	167—169	457.9151(457.9150)
2b	White solid	89	147—149	471.9295(471.9307)
3b	White solid	85	142—144	487.9246(487.9256)
4b	White solid	45	169—171	547.9466(547.9467)
5b	Pale yellow solid	65	200—202	595.8471(595.8466)
6b	Pale yellow solid	95	166.8—169.0	475.9046(475.9056)
7b	White solid	95	180—182	491.8763(491.8760)
8b	White solid	94	155—157	535.8259(535.8255)
9b	White solid	97	185—187	502.8991(502.9001)
10b	White solid	96	164—165	502.8988(502.9001)
11b	White solid	90	164—165	507.9308(507.9307)
12b	White solid	90	164.4—166.7	392.0214(392.0222)
13b	White solid	78	166.1—168.1	406.0374(406.0378)
14b	White solid	76	168.7—170.4	422.0327(422.0328)
15b	Yellow solid	84	156.1—157.5	531.9513(531.9518)
16b	Pale yellow solid	95	164.8—165.7	410.0123(410.0128)
17b	Yellow solid	94	199.5—201.4	425.9826(425.9832)
18b	White solid	94	177.1—178.9	471.9302(471.9307)
19b	White solid	95	148.6—149.9	437.0077(437.0073)
20b	White solid	93	175.5—176.3	437.0067(437.0073)

Compd.	¹H NMR(300 MHz, CDCl₃), δ	¹³C NMR(75 MHz, CDCl₃), δ
1b	7.74(dd, J=7.7, 1.5 Hz, 2H, ArH), 7.45—7.33(m, 3H, ArH), 6.80(s, 1H, NH), 6.46(s, 1H ,CH), 1.49(s, 3H ,CH₃), 1.43(s, 3H, CH₃)	176.12, 154.95, 131.95, 130.55, 129.97, 128.60, 89.90, 66.11, 58.56, 25.19, 24.88
2b	7.62(d, J=8.2 Hz, 2H, ArH), 7.17(d, J=8.1 Hz, 2H, ArH), 6.94(s, 1H , NH), 6.42(s, 1H, CH), 2.34(s, 3H, ArCH₃), 1.48(s, 3H , CH₃), 1.42(s, 3H, CH₃)	176.15, 155.01, 140.06, 130.45, 129.24, 128.87, 90.18, 65.96, 58.48, 25.11, 24.79, 21.20
3b	7.70(d, J=8.9 Hz, 2H, ArH), 6.88(d, J=8.9 Hz, 2H , ArH), 6.60(s, 1H, NH), 6.42(s, 1H, CH), 3.81(s, 3H, OCH₃), 1.49(s, 3H, CH₃), 1.43(s, 3H, CH₃)	176.07, 160.67, 154.90, 132.30, 123.62, 113.84, 90.55, 65.86, 58.47, 55.26, 25.20, 24.89
4b	7.07(s, 2H, ArH), 6.50(s, 1H, NH), 6.41(s, 1H, CH), 3.86(d, J=7.2 Hz, 9H, 3OCH₃), 1.45(s, 3H, CH₃)	176.14, 154.72, 152.89, 139.31, 126.70, 108.54, 90.31, 66.42, 60.84, 58.43, 56.35, 25.24, 24.94
5b	8.06(s, 1H, ArH), 7.04(s, 1H, NH), 6.76(s, 1H, NH), 6.74(s, 1H, CH), 3.91(s, 3H, OCH₃), 3.88(s, 3H, OCH₃), 1.47(s, 3H, CH₃), 1.39(s, 3H, CH₃)	175.98, 154.58, 150.33, 147.37, 122.62,116.50, 115.21, 114.83, 90.34, 63.98, 58.43, 56.09, 56.08, 25.16, 24.84
6b	7.79(d, J=3.7 Hz, 2H, ArH), 7.07(d, J=17.3 Hz, 2H ,ArH), 6.45(s, 1H, NH), 6.31(s, 1H, CH), 1.49(s, 3H, CH₃), 1.42(s, 3H, CH₃)	176.07, 154.87, 131.95, 130.56, 129.95, 128.58, 89.89, 66.12, 58.53, 25.20, 24.90
7b	7.72(d, J=8.4 Hz, 2H, ArH), 7.36(d, J=8.5 Hz, 2H, ArH), 6.52(s, 1H, NH), 6.41(s, 1H, CH), 1.46(d, J=22.2 Hz, 6H, 2CH₃)	175.93, 154.58, 136.28, 132.13, 130.28, 128.83, 89.45, 65.52, 58.61, 25.20, 24.92
8b	7.65(d, J=8.5 Hz, 2H, ArH), 7.52(d, J=8.5 Hz, 2H, ArH), 6.68(s, 1H, NH), 6.39(s, 1H, CH), 1.49(s, 3H, CH₃), 1.43(s, 3H, CH₃)	175.96, 154.69, 132.34, 131.81, 130.83, 124.62, 89.33, 65.60, 58.63, 25.17, 24.89
9b	8.25(d, J=8.9 Hz, 2H, ArH), 7.98(d, J=8.8 Hz, 2H, ArH), 6.51(s, 1H, NH), 5.94(s, 1H, CH), 1.51(s, 3H, CH₃), 1.45(s, 3H, CH₃)	175.70, 153.89, 148.63, 138.55, 131.81, 123.60 88.24, 65.14, 58.77, 25.24, 25.02
10b	8.75(d, J=1.5 Hz, 1H , ArH), 8.30(d, J=9.6 Hz, 1H, ArH), 8.14(d, J=7.9 Hz, 1H, ArH), 7.62(t, J=8.1 Hz, 1H, ArH), 6.69(s, 1H, NH), 6.50(s, 1H, CH), 1.52(s, 3H, CH₃), 1.47(s, 3H, CH₃)	175.96, 154.36, 148.03, 136.72, 133.66, 129.60, 126.00, 124.89, 88.53, 65.19, 58.87, 25.12, 24.92
11b	8.55(d, J=7.5 Hz, 1H, ArH), 7.99(d, J=8.6 Hz, 1H, ArH), 7.89(dd, J=14.0, 8.1 Hz, 2H, ArH), 7.53(dd, J=22.9, 15.0, 7.4 Hz, 3H, ArH), 7.22(s, 1H, NH), 6.17(s, 1H,CH), 1.42(s, 3H, CH₃), 1.27(s, 3H, CH₃)	175.84, 154.48, 133.87, 131.42, 130.59, 129.53, 128.57, 127.57, 126.50, 125.94, 124.43, 121.60, 89.73, 60.01, 58.47, 25.20, 24.79
12b	7.77(dd, J=7.3, 2.1 Hz, 2H, ArH), 7.45—7.34(m, 3H, ArH), 6.69(s, 1H, NH), 6.20(s, 1H, CH), 2.59(s, 3H, CH₃), 1.39(d, J=3.5 Hz, 6H, 2×CH₃)	176.99, 155.15, 132.96, 130.74, 129.54, 128.68, 95.75, 63.97, 58.35, 29.12, 24.93, 24.72
13b	7.65(d, J=8.2 Hz, 2H, ArH), 7.20(d, J=8.0 Hz, 2H, ArH), 6.51(s, 1H, NH), 6.17(s, 1H, CH), 2.59(s, 3H, CH₃), 2.37(ArCH₃), 1.38(d, J=6.2 Hz, 6H, 2×CH₃)	176.84, 139.39, 130.54, 129.96, 129.16, 96.02, 63.77, 58.31, 29.11, 24.98, 24.80
14b	7.71(d, J=8.8 Hz, 2H, ArH), 6.91(d, J=8.9 Hz, 2H, ArH), 6.48(s, 1H, NH), 6.15(s, 1H, CH), 3.82(s, 3H, OCH₃), 2.58(s,3H, CH₃), 1.38(d, J=4.5 Hz, 6H, 2×CH₃)	176.87, 160.38, 155.06, 132.31, 124.80, 113.98, 96.33, 63.55, 58.32, 55.29, 29.04, 24.90
15b	7.91(s, 1H, ArH), 7.06(s, 1H, ArH), 6.76(s, 1H, NH), 6.65(s, 1H, CH), 3.88(s, 3H, OCH₃), 3.87(s, 3H, OCH₃), 2.57(s, 3H, CH₃), 1.44(s, 3H, CH₃), 1.39(s, 2×CH₃)	176.87, 155.10, 150.08, 147.91, 123.87, 116.58, 115.49, 114.50, 97.83, 61.54, 58.45, 56.06, 31.20, 24.97
16b	7.67(d, J=8.5 Hz, 2H, ArH), 7.54(d, J=8.3 Hz, 2H, ArH), 6.51(s, 1H, NH), 6.16(s, 1H, CH), 2.57(s, 3H, CH₃), 1.39(d, J=6.4 Hz, 6H, 2×CH₃)	176.80, 154.84, 132.51, 132.30, 131.95, 124.15, 95.43, 63.37, 58.44, 29.10, 24.98, 24.83
17b	7.73(d, J=8.5 Hz, 2H, ArH), 7.38(d, J=8.5 Hz, 2H, ArH), 6.53—6.43(m, 1H, NH), 6.17(s, 1H, CH), 2.57(s, 3H, CH₃), 1.39(d, J=4.1 Hz, 6H, 2×CH₃)	176.79, 154.84, 135.85, 132.24, 131.37, 128.95, 95.53, 63.29, 58.43, 29.10, 24.89
18b	7.67(d, J=7.1 Hz, 2H, ArH), 7.54(d, J=5.5 Hz, 2H, ArH), 6.63(d, J=19.0 Hz, 1H, NH), 6.16(s, 1H, CH), 2.58(s, 3H, CH₃), 1.40(d, J=2.8 Hz, 6H, 2×CH₃)	176.83, 154.86, 132.49, 132.29, 131.94, 124.14, 95.45, 63.37, 58.43, 29.11, 24.96, 24.80
19b	8.26(d, J=8.8 Hz, 2H, ArH), 8.01(d, J=8.8 Hz, 2H, ArH), 6.51(s, 1H, NH), 6.30(s, 1H, CH), 2.59(s, 3H, CH₃), 1.42(d, J=7.1 Hz, 6H, 2×CH₃)	176.73, 154.57, 148.50, 139.71, 131.95,131.36, 128.87, 123.79, 94.87, 62.98, 58.62, 29.33, 24.98, 24.85
20b	8.74(s, 1H, ArH), 8.30(d, J=8.3 Hz, 1H, ArH), 8.17(d, J=7.8 Hz, 1H, ArH), 7.65(t, J=8.0 Hz, 1H, ArH), 6.85(s, 1H, NH), 6.31(s,1H, CH), 2.60(s, 3H, CH₃), 1.44(s, 6H, 2×CH₃)	176.82, 154.81, 148.20, 136.88, 134.72, 129.87, 125.89, 124.58, 95.18, 62.94, 58.71, 29.22, 25.08, 24.86