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The Journal of Organic Chemistry
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20.7+. HRMS: ESI+ [M+H]+ Calcd. for C9H13NCl: 170.0737. Found: 170.0733. 4-chloro-3-methyl-
N,N-dimethylaniline. Obtained as a yellow oil (8 mg, 7%). TLC 10% ethyl acetate–hexanes, Rf =
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0.54 (UV, KMnO4). H NMR (400 MHz, CDCl3) δ: 7.16 (d, J = 8.8 Hz, 1H), 6.58 (d, J = 3.0 Hz,
1H), 6.50 (dd, J1 = 8.8, J2 = 3.1 Hz, 1H), 2.91 (s, 6H), 2.33 (s, 3H). 13C NMR (101 MHz, CDCl3) δ:
149.5, 136.2, 129.3, 122.1, 115.0, 111.6, 40.9, 20.7. HRMS: ESI+ [M+H]+ Calcd. for C9H13NCl:
170.0737. Found: 170.0733.
6-chloro-3-methoxy-N,N-dimethylaniline (3j). Obtained as a yellow oil (isolated as a mix of
regioisomers, 4.9:1 (6-Cl:4-Cl), asterisk denotes minor peaks, 55 mg, 43%). TLC 10% ethyl
acetate–hexanes, Rf = 0.46 (UV, KMnO4). 1H NMR (400 MHz, CDCl3) δ: 7.24 (d, J = 8.7 Hz, 1H),
7.17* (t, J = 8.2 Hz, 1H), 6.74* (dd, J1 = 8.2, J2 = 1.3 Hz, 1H), 6.65* (dd, J1 = 8.3, J2 = 1.3 Hz, 1H),
6.62 (d, J = 2.9 Hz, 1H), 6.49 (dd, J1 = 8.7 Hz, J2 = 2.9 Hz, 1H), 3.90* (s, 1H), 3.79 (s, 3H), 2.81*
(s, 1H), 2.80 (s, 6H). 13C NMR (101 MHz, CDCl3) δ: 159.1, 156.2*, 152.1*, 151.4, 131.0, 127.1*,
119.8, 116.5*, 112.4* 107.5, 107.0, 106.3*, 56.4*, 55.6, 44.1*, 43.8. HRMS: ESI+ [M+H]+ Calcd.
for C9H13ONCl: 186.0686. Found: 186.0683.
2-chloro-6-methyl-N,N-dimethylaniline (3k). Obtained as a yellow oil (isolated as mixture of
regioisomers, 1.3:1 (6-Cl:4-Cl), asterisk denotes minor peaks, 23 mg, 19%). TLC 10% ethyl
acetate–hexanes, Rf = 0.89 (UV, KMnO4). 1H NMR (400 MHz, CDCl3) δ: 7.17 (d, J = 6.8 Hz, 1H),
7.13* (d, J = 2.0 Hz, 1H), 7.10* (dd, J1 = 8.4, J2 = 2.0 Hz, 1H), 7.03 (d, J = 8.4 Hz, 1H), 6.96 (t, J
= 7.2 Hz, 1H), 6.93* (d, J = 8.4 Hz, 1H), 2.70 (s, 6H), 2.67* (s, 6H), 2.34 (s, 3H), 2.30* (s, 3H). 13C
NMR (101 MHz, CDCl3) δ 152.7*, 151.3, 134.0, 132.1, 131.2*, 130.8, 127.4*, 126.4*, 126.2,
122.5*, 119.6, 118.3*, 44.3*, 44.2, 18.4*, 18.3. HRMS: ESI+ [M+H]+ Calcd. for C9H13NCl:
170.0737. Found: 170.0727.
2-chloro-N-butyl-N-dimethylaniline (3l). Obtained as a yellow oil (isolated as a mix of
regioisomers, 2.9:1 (6-Cl:2-Cl), asterisk denotes minor peaks, 77 mg, 55%). TLC 10% ethyl
acetate–hexanes, Rf = 0.70 (UV, KMnO4). 1H NMR (400 MHz, CDCl3) δ 7.37 (dd, J1 = 7.9 Hz, J2
= 1.6 Hz, 1H), 7.22 (td, J1 = 7.7 Hz, J2 = 1.6 Hz, 1H), 7.17* (d, J = 9.1 Hz, 2H), 7.09 (dd, J1 = 8.1
Hz, J2 = 1.5 Hz, 1H), 6.96 (td, J1 = 7.6 Hz, J2 = 1.6 Hz, 1H), 6.61* (d, J = 9.1 Hz, 2H), 3.33 – 3.27*
(m, 2H), 3.07 – 3.00 (m, 2H), 2.92* (s, 3H), 2.80 (s, 3H), 1.62 – 1.51* (m, 2H), 1.62 – 1.51 (m,
2H),1.41 – 1.28* (m, 2H), 1.41 – 1.28 (m, 2H), 0.95* (m, 3H), 0.95 (m, 3H). 13C NMR (101 MHz,
CDCl3) δ 150.2, 148.0*, 130.7, 129.0, 129.0*, 127.3, 123.2*, 121.3, 120.6*, 113.2*, 55.8, 52.7*,
40.9, 38.6*, 29.5, 28.8*, 20.5*, 20.4, 14.2, 14.1*. HRMS: ESI+ [M+H]+ Calcd. for C11H17NCl:
198.1050. Found: 198.1040.
2-chloro-N-isopentyl-N-dimethylaniline (3m). Obtained as a yellow oil (isolated as a mix of
regioisomers, 2.8:1 (6-Cl:2-Cl), asterisk denotes minor peaks, 89 mg, 59%). TLC 10% ethyl
acetate–hexanes, Rf = 0.75 (UV, KMnO4). 1H NMR (400 MHz, CDCl3) δ 7.35 (dd, J1 = 7.9 Hz, J2
= 1.6 Hz, 1H), 7.22 – 7.17 (m, 1H), 7.15* (d, J = 9.1 Hz, 2H), 7.07 (dd, J1 = 8.1 Hz, J2 = 1.5 Hz,
1H), 6.93 (td, J1 = 7.6 Hz, J2 = 1.6 Hz, 1H), 6.59* (d, J = 9.1 Hz, 2H), 3.32 – 3.26* (m, 2H), 3.05 –
2.99 (m, 2H), 2.89* (s, 3H), 2.77 (s, 3H), 1.62 – 1.52* (m, 1H), 1.62 – 1.52 (m, 1H), 1.50 – 1.39*
(m, 2H), 1.50 – 1.39 (m, 2H), 0.94* (d, J = 6.6 Hz, 6H), 0.90 (d, J = 6.5 Hz, 6H). 13C NMR (101
MHz, CDCl3) δ 150.2, 147.9*, 130.7, 129.0, 129.0*, 127.3, 123.2, 121.3, 120.6*, 113.3*, 54.4,
51.2*, 41.0, 38.4*, 36.2, 35.0*, 26.4, 26.3*, 22.9, 22.8*. HRMS: ESI+ [M+H]+ Calcd. for C12H19NCl:
212.1206. Found: 212.1196.
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2-chloro-N-cyclohexyl-N-dimethylaniline (3n). Obtained as a yellow oil (isolated as a mix of
regioisomers, 4.9:1 (6-Cl:2-Cl), asterisk denotes minor peaks, 103 mg, 65%). TLC 10% ethyl
acetate–hexanes, Rf = 0.82 (UV, KMnO4). 1H NMR (600 MHz, CDCl3) δ 7.35 (dd, J1 = 7.9 Hz, J2
= 1.6 Hz, 1H), 7.19 – 7.16 (m, 1H), 7.15* (d, J = 9.0 Hz, 2H), 7.07 (dd, J1 = 8.1 Hz, J2 = 1.5 Hz,
1H), 6.91 (td, J1 = 7.6 Hz, J2 = 1.6 Hz, 1H), 6.68* (d, J = 9.1 Hz, 2H), 3.52 – 3.46* (m, 1H), 3.14
(m, 1H), 2.74* (s, 3H), 2.71 (s, 3H), 1.84 (m, 1H), 1.87 – 1.73 (m, 3H), 1.69* (m, 1H), 1.65 – 1.58*
(m, 3H), 1.45 (m, 3H), 1.39 – 1.30* (m, 3H), 1.29 – 1.20 (m, 3H), 1.11* (m, 3H). 13C NMR (101
MHz, CDCl3) δ 150.0, 148.8*, 130.7, 129.4, 129.2*, 128.9*, 127.0, 123.0, 122.7, 114.3*, 61.6,
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