Amides Nickel/Briphos-Catalyzed Transamidation of ...H O O M e N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and 4-methoxyaniline (49 mg, 0.4 mmol) provided 3ae (35 mg, 78 %). Yellow

S1

Supplementary Information

Nickel/Briphos-Catalyzed Transamidation of Unactivated Tertiary

Amides

Da Hyeon Yang,a Taeil Shin,b Hyunwoo Kim,b* and Sunwoo Leea*

Content

General Experimental Procedure --------------------------------------------------------- S2

Reference --------------------------------------------------------------------------------- S10

Spectral Data ----------------------------------------------------------------------------- S11

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2020

S2

General Experimental Procedure

N-methyl-N-phenylbenzamide (0.2 mmol), Primary Amine (0.4 mmol), NiCl2 (0.02 mmol), Briphos

(0.02 mmol), Mn (1.0 mmol), TMSCl (0.4 mmol) and N-Methylpyrrolidone (1 mL) was added into a

clean and dried glass vial under aerobic condition. The suspension was stirred for 12 h at 160 oC.

After cooling, the reaction mixture was diluted with 30 mL EtOAc and 30 mL water. The organic

layer was extracted and dried over anhydrous MgSO4. Evaporation of the solvent under reduced

pressure provided the crude product, which was purified by column chromatography (25% ethyl

acetate in hexane) to afford the final product.

N-phenylbenzamide (3aa)1

NH

O

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol) provided 3aa (34

mg, 87 %). White solid. Mp. 162 - 163 oC. 1H NMR (500 MHz, CDCl3) δ 7.81 – 7.76 (m, 3H), 7.58 (d,

J = 7.9 Hz, 2H), 7.48 (m, 1H), 7.44 – 7.41 (m, 2H), 7.32 – 7.29 (m, 2H), 7.09 (t, J = 7.4 Hz, 1H); 13C

NMR (126 MHz, CDCl3) δ 165.8, 137.9, 135.0, 131.8, 129.1, 128.8, 127.0, 124.6, 120.2; MS (EI) m/z:

197 (M+).

N-(p-tolyl)benzamide (3ab)2

NH

OMe

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and p-toluidine (43 mg, 0.4 mmol) provided 3ab

(35 mg, 82 %). White solid. Mp. 156 - 157 oC. 1H NMR (500 MHz, CDCl3) δ 7.88 – 7.86 (m, 2H), 7.78

(s, 1H), 7.57 – 7.52 (m, 3H), 7.51 – 7.48 (m, 2H), 7.19 (d, J = 8.0 Hz, 2H), 2.35 (s, 3H); 13C NMR (126

MHz, CDCl3) δ 165.6, 135.3, 135.1, 134.3, 131.8, 129.6, 128.8, 127.0, 120.2, 20.9; MS (EI) m/z: 211

(M+).

N-(o-tolyl)benzamide (3ac)2

NH

O

Me

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and o-toluidine (43 mg, 0.4 mmol) provided 3ac

S3

(33 mg, 77 %). White solid. Mp. 143 - 144 oC. 1H NMR (500 MHz, CDCl3) δ 7.89 (d, J = 7.9 Hz, 1H),

7.82 (d, J = 7.3 Hz, 2H), 7.61 (s, 1H), 7.50 (m, 1H), 7.45 – 7.42 (m, 2H), 7.21 (m, 1H), 7.17 (m, 1H),

7.05 (td, J = 7.5 Hz, 0.9 Hz, 1H), 2.27 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 165.4, 135.4, 134.7, 131.5,

130.3, 129.1, 128.5, 126.8, 126.6, 125.1, 122.9, 17.5; MS (EI) m/z: 211 (M+).

N-mesitylbenzamide (3ad)8

NH

OMe

Me

Me

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and 2,4,6-trimethylaniline (54 mg, 0.4 mmol)

provided 3ad (25 mg, 53 %). White solid. Mp. 204 - 205 oC. 1H NMR (500 MHz, CDCl3) δ 7.85 – 7.84

(m, 2H), 7.49 (t, J = 7.4 Hz, 1H), 7.44 – 7.41 (m, 2H), 7.25 (s, 1H), 6.87 (s, 2H), 2.23 (s, 3H), 2.17 (s,

6H); 13C NMR (126 MHz, CDCl3) δ 166.0, 137.1, 135.3, 134.6, 131.7, 131.1, 129.0, 128.7, 127.2, 20.9,

18.4; MS (EI) m/z: 239 (M+).

N-(4-Methoxyphenyl)benzamide (3ae)2

NH

OOMe

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and 4-methoxyaniline (49 mg, 0.4 mmol) provided

3ae (35 mg, 78 %). Yellow solid. Mp. 159 - 160 oC. 1H NMR (500 MHz, CDCl3) δ 7.79 – 7.78 (m, 2H),

7.72 (s, 1H), 7.47 – 7.45 (m, 3H), 7.40 (t, J = 7.5 Hz, 2H), 6.84 – 6.81 (m, 2H), 3.74 (s, 3H); 13C NMR

(126 MHz, CDCl3) δ 165.7, 156.6, 135.0, 131.7, 131.0, 128.7, 127.0, 122.1, 114.2, 55.5; MS (EI) m/z:

227 (M+).

N-(4-(methylthio)phenyl)benzamide (3af)2

NH

OSMe

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and 4-(methylthio)aniline (56 mg, 0.4 mmol)

provided 3af (38 mg, 79 %). Purple solid. Mp. 179 - 180 oC. 1H NMR (500 MHz, CDCl3) δ 7.80 – 7.78

(m, 2H), 7.75 (s, 1H), 7.52 – 7.47 (m, 3H), 7.42 (t, J = 7.5 Hz, 2H), 7.22 – 7.21 (m, 2H), 2.42 (s, 3H);

S4

13C NMR (126 MHz, CDCl3) δ 165.6, 135.5, 134.8, 134.0, 131.9, 128.8, 128.0, 127.0, 120.8, 16.7; MS

(EI) m/z: 243 (M+).

N-(4-fluorophenyl)benzamide (3ag)3

NH

OF

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and 4-fluoroaniline (44 mg, 0.4 mmol) provided

3ag (30 mg, 69 %). White solid. Mp. 185 - 186 oC. 1H NMR (500 MHz, CDCl3) δ 7.80 – 7.78 (m, 2H),

7.73 (s, 1H), 7.54 – 7.47 (m, 3H), 7.44 – 7.41 (m, 2H), 7.02 – 6.98 (m, 2H); 13C NMR (126 MHz, CDCl3)

δ 165.7, 159.5 (d, JC-F = 244.4 Hz), 134.7, 133.9 (d, JC-F = 2.5 Hz), 132.0, 128.9, 127.0, 122.0 (d, JC-F =

8.8 Hz), 115.8 (d, JC-F = 22.7 Hz); MS (EI) m/z: 215 (M+).

N-(4-(trifluoromethyl)phenyl)benzamide (3ah)7

NH

OCF3

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and 4-(trifluoromethyl)aniline (64 mg, 0.4 mmol)

provided 3ah (33 mg, 63 %). White solid. Mp. 207 - 208 oC. 1H NMR (500 MHz, DMSO-d6) δ 10.57

(s, 1H), 8.02 (d, J = 8.5 Hz, 2H), 7.97 – 7.96 (m, 2H), 7.71 (d, J = 8.6 Hz, 2H), 7.61 (t, J = 7.4 Hz, 1H),

7.56 – 7.53 (m, 2H); 13C NMR (126 MHz, DMSO-d6) δ 166.5, 143.3, 134.6, 132.4, 128.9, 128.2, 126.4

(q, JC-F = 3.8 Hz), 125.9 (q, JC-F = 219.2 Hz), 123.9 (d, JC-F = 21.4 Hz), 120.5; MS (EI) m/z: 265 (M+).

N-(pyridin-2-yl)benzamide (3ai)2

NH

O

N

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and pyridin-2-amine (38 mg, 0.4 mmol) provided

3ai (29 mg, 74 %). White solid. Mp. 83 - 84 oC. 1H NMR (500 MHz, CDCl3) δ 9.07 (s, 1H), 8.38 (d, J

= 8.4 Hz, 1H), 8.15 (s, 1H), 7.89 – 7.88 (m, 2H), 7.72 (m, 1H), 7.50 (t, J = 7.4 Hz, 1H), 7.44 – 7.41 (m,

2H), 7.01 (dd, J = 6.8 Hz, 5.3 Hz, 1H); 13C NMR (126 MHz, CDCl3) δ 165.9, 151.5, 147.0, 139.1, 134.1,

132.4, 128.8, 127.4, 119.9, 114.5; MS (EI) m/z: 198 (M+).

S5

N-(thiazol-2-yl)benzamide (3aj)4

NH

O

N

S

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and thiazol-2-amine (40 mg, 0.4 mmol) provided

3aj (29 mg, 72 %). White solid. Mp. 149 - 150 oC. 1H NMR (500 MHz, CDCl3) δ 7.97 – 7.96 (m, 2H),

7.56 (t, J = 7.5 Hz, 1H), 7.47 – 7.44 (m, 2H), 6.93 (d, J = 3.7 Hz, 1H), 6.87 (d, J = 3.6 Hz, 1H); 13C

NMR (126 MHz, CDCl3) δ 165.8, 160.4, 136.6, 132.7, 132.6, 128.8, 128.1, 113.4; MS (EI) m/z: 204 (M+).

N-(benzo[d]thiazol-2-yl)benzamide (3ak)5

NH

O

N

S

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and benzo[d]thiazol-2-amine (60 mg, 0.4 mmol)

provided 3ak (36 mg, 71 %). White solid. Mp. 187 - 188 oC. 1H NMR (500 MHz, CDCl3) δ 8.03 (dd,

J = 8.4 Hz, 1.2 Hz, 2H), 7.86 (dd, J = 7.8 Hz, 0.8 Hz, 1H), 7.56 (m, 1H), 7.43 – 7.39 (m, 2H), 7.30 (m,

1H), 7.27 – 7.20 (m, 2H); 13C NMR (126 MHz, CDCl3) δ 166.1, 160.1, 147.1, 133.1, 131.9, 131.6, 129.0,

128.1, 126.2, 124.1, 121.4, 120.4; MS (EI) m/z: 254 (M+).

N-benzylbenzamide (3al)3

NH

O

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and phenylmethanamine (43 mg, 0.4 mmol)

provided 3al (27 mg, 65 %). White oil. 1H NMR (500 MHz, CDCl3) δ 7.72 (m, 2H), 7.43 (m, 1H), 7.37

– 7.34 (m, 2H), 7.29 – 7.28 (m, 4H), 7.23 (m, 1H), 6.36 (s, 1H), 4.58 (d, J = 5.6 Hz, 2H); 13C NMR (126

MHz, CDCl3) δ 167.3, 138.1, 134.4, 131.6, 128.8, 128.6, 127.9, 127.6, 126.9, 44.2; MS (EI) m/z: 211

(M+).

N-benzhydrylbenzamide (3am)10

S6

NH

O

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and diphenylmethanamine (73 mg, 0.4 mmol)

provided 3am (24 mg, 42 %). White solid. Mp. 176 - 177 oC. 1H NMR (500 MHz, CDCl3) δ 7.74 –

7.72 (m, 2H), 7.42 (m, 1H), 7.36 – 7.32 (m, 2H), 7.28 – 7.18 (m, 10H), 6.67 (d, J = 7.5 Hz, 1H), 6.37 (d,

J = 7.8 Hz, 1H); 13C NMR (126 MHz, CDCl3) δ 166.5, 141.5, 134.2, 131.7, 128.8, 128.6, 127.6, 127.5,

127.1, 57.5; MS (EI) m/z: 287 (M+).

N-(1-phenylethyl)benzamide (3an)9

NH

O Me

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and 1-phenylethanamine (48 mg, 0.4 mmol)

provided 3an (20 mg, 45 %). White solid. Mp. 125 - 126 oC. 1H NMR (500 MHz, CDCl3) δ 7.70 – 7.68

(m, 2H), 7.41 (m, 1H), 7.34 – 7.30 (m, 4H), 7.28 – 7.25 (m, 2H), 7.20 (m, 1H), 6.39 (d, J = 6.4 Hz, 1H),

5.25 (m, 1H), 1.52 (d, J = 6.9 Hz, 3H); 13C NMR (126 MHz, CDCl3) δ 166.6, 143.1, 134.6, 131.5, 128.7,

128.6, 127.5, 126.9, 126.3, 49.2, 21.7; MS (EI) m/z: 225 (M+).

N-allylbenzamide (3ao)6

NH

O

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and prop-2-en-1-amine (23 mg, 0.4 mmol)

provided 3ao (13 mg, 39 %). White oil. 1H NMR (500 MHz, CDCl3) δ 7.72 – 7.70 (m, 2H), 7.36 (m,

1H), 7.28 – 7.25 (m, 2H), 6.93 (s, 1H), 5.79 (ddt, J = 17.1 Hz, 10.3 Hz, 5.6 Hz, 1H), 5.11 (dq, J = 17.2

Hz, 1.6 Hz, 1H), 5.02 (dq, J = 10.3 Hz, 1.3 Hz, 1H), 3.93 (tdd, J = 5.7 Hz, 1.5 Hz, 1.5 Hz, 2H); 13C NMR

(126 MHz, CDCl3) δ 167.4, 134.2, 134.0, 131.2, 128.2, 126.9, 116.1, 42.2; MS (EI) m/z: 161 (M+).

S7

N-cyclohexylbenzamide (3ap)2

NH

O

N-methyl-N-phenylbenzamide (42 mg, 0.2 mmol) and cyclohexanamine (40 mg, 0.4 mmol) provided

3ap (17 mg, 41 %). White solid. Mp. 150 - 152 oC. 1H NMR (500 MHz, CDCl3) δ 7.69 – 7.67 (m, 2H),

7.41 (m, 1H), 7.36 – 7.33 (m, 2H), 5.94 (s, 1H), 3.91 (m, 1H), 1.98 – 1.94 (m, 2H), 1.68 (dt, J = 13.9

Hz, 3.8 Hz, 2H), 1.58 (dt, J = 13 Hz, 3.8 Hz, 1H), 1.40 – 1.31 (m, 2H), 1.21 – 1.08 (m, 3H); 13C NMR

(126 MHz, CDCl3) δ 166.7, 135.0, 131.2, 128.5, 126.8, 48.7, 33.2, 25.6, 24.9; MS (EI) m/z: 203 (M+).

2-methyl-N-phenylbenzamide (3ba)1

NH

OMe

N,2-dimethyl-N-phenylbenzamide (45 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol) provided 3ba

(27 mg, 65 %). White solid. Mp. 126 - 127 oC. 1H NMR (500 MHz, CDCl3) δ 7.54 (d, J =7.6 Hz, 2H),

7.45 (s, 1H), 7.39 (d, J = 7.5 Hz, 1H), 7.30 – 7.27 (m, 3H), 7.19 – 7.15 (m, 2H), 7.08 (t, J = 7.5 Hz, 1H),

2.42 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 168.1, 138.0, 136.4, 131.3, 130.3, 129.1, 126.6, 125.9, 124.6,

119.9, 19.8; MS (EI) m/z: 211 (M+).

3-methyl-N-phenylbenzamide (3ca)14

NH

OMe

N,3-dimethyl-N-phenylbenzamide (45 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol) provided 3ca

(33 mg, 79 %). White solid. Mp. 128 - 129 oC. 1H NMR (500 MHz, CDCl3) δ 7.83 (s, 1H), 7.60 (s, 1H),

7.57 – 7.56 (m, 3H), 7.30 – 7.27 (m, 4H), 7.07 (t, J = 7.4 Hz, 1H), 2.34 (s, 3H); 13C NMR (126 MHz,

CDCl3) δ 166.0, 138.7, 138.0, 135.0, 132.6, 129.1, 128.6, 127.8, 124.5, 124.0, 120.2, 21.4; MS (EI) m/z:

211 (M+).

4-methyl-N-phenylbenzamide (3da)1

S8

O

NH

Me

N,4-dimethyl-N-phenylbenzamide (45 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol) provided 3da

(31 mg, 73 %). White solid. Mp. 145 - 146 oC. 1H NMR (500 MHz, CDCl3) δ 7.70 (d, J = 7.7 Hz, 3H),

7.57 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.6 Hz, 2H), 7.22 (d, J = 7.8 Hz, 2H), 7.08 (t, J = 7.2 Hz, 1H), 2.36

(s, 3H); 13C NMR (126 MHz, CDCl3) δ 165.6, 142.4, 138.0, 132.1, 129.4, 129.1, 127.0, 124.4, 120.1,

21.5; MS (EI) m/z: 211 (M+).

4-(tert-butyl)-N-phenylbenzamide (3ea)13

NH

O

t-Bu

4-(tert-butyl)-N-methyl-N-phenylbenzamide (53 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol)

provided 3ea (35 mg, 70 %). White solid. Mp. 125 - 126 oC. 1H NMR (500 MHz, CDCl3) δ 7.75 – 7.73

(m, 3H), 7.57 (d, J = 7.9 Hz, 2H), 7.43 (d, J = 8.3 Hz, 2H), 7.30 (t, J = 7.8 Hz, 2H), 7.08 (t, J = 7.4 Hz,

1H), 1.28 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 165.7, 155.4, 138.1, 132.1, 129.1, 126.9, 125.7, 124.4,

120.2, 35.0, 31.2; MS (EI) m/z: 253 (M+).

4-methoxy-N-phenylbenzamide (3fa)1

NH

O

MeO

4-methoxy-N-methyl-N-phenylbenzamide (48 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol)

provided 3fa (34 mg, 74 %). White solid. Mp. 168 - 170 oC. 1H NMR (500 MHz, CDCl3) δ 7.77 (d, J

= 8.1 Hz, 2H), 7.69 (s, 1H), 7.56 (d, J = 7.8 Hz, 2H), 7.29 (t, J = 7.7 Hz, 2H), 7.07 (t, J = 7.3 Hz, 1H),

6.90 (d, J = 8.6 Hz, 2H), 3.80 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 165.2, 162.5, 138.1, 129.1, 128.9,

127.1, 124.3, 120.1, 114.0, 55.5; MS (EI) m/z: 227 (M+).

N-phenyl-4-(trifluoromethyl)benzamide (3ga)12

S9

O

NH

F3C

N-methyl-N-phenyl-4-(trifluoromethyl)benzamide (56 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol)

provided 3ga (41 mg, 77 %). White solid. Mp. 207 - 208 oC. 1H NMR (500 MHz, DMSO-d6) δ 10.45

(s, 1H), 8.14 (d, J = 8.1 Hz, 2H), 7.90 (d, J = 8.2 Hz, 2H), 7.78 – 7.77 (m, 2H), 7.38 – 7.35 (m, 2H), 7.12

(t, J = 7.4 Hz, 1H); 13C NMR (126 MHz, DMSO-d6) δ 164.8, 139.3, 139.2, 131.8 (d, JC-F = 32.8 Hz),

129.1, 129.0, 125.8 (q, JC-F = 3.8 Hz), 125.5 (q, JC-F = 273.4 Hz), 124.5, 120.9; MS (EI) m/z: 265 (M+).

4-fluoro-N-phenylbenzamide (3ha)11

O

NH

F

4-fluoro-N-methyl-N-phenylbenzamide (46 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol) provided

3ha (35 mg, 82 %). White solid. Mp. 187 - 188 oC. 1H NMR (500 MHz, CDCl3) δ 7.82 (dd, J = 8.6 Hz,

5.3 Hz, 2H), 7.69 (s, 1H), 7.55 (d, J = 7.9 Hz, 2H), 7.31 (t, J = 7.9 Hz, 2H), 7.10 (t, J = 8.4 Hz, 3H); 13C

NMR (126 MHz, CDCl3) δ 165.1 (d, JC-F = 253.3 Hz), 164.9, 137.9, 131.3 (d, JC-F = 3.8 Hz), 129.6 (d,

JC-F = 8.8 Hz), 129.4, 125.0, 120.5, 116.1 (d, JC-F = 22.7 Hz); MS (EI) m/z: 215 (M+).

N-phenyl-[1,1'-biphenyl]-4-carboxamide (3ia)13

NH

O

Ph

N-methyl-N-phenyl-[1,1'-biphenyl]-4-carboxamide (57 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol)

provided 3ia (44 mg, 81 %). White solid. Mp. 227 - 228 oC. 1H NMR (500 MHz, CDCl3) δ 7.90 – 7.88

(m, 2H), 7.78 (s, 1H), 7.65 (d, J = 8.3 Hz, 2H), 7.61 – 7.56 (m, 4H), 7.43 – 7.40 (m, 2H), 7.36 – 7.31

(m, 3H), 7.10 (t, J = 7.4 Hz, 1H); 13C NMR (126 MHz, CDCl3) δ 165.4, 144.7, 139.9, 137.9, 133.6, 129.1,

129.0, 128.1, 127.6, 127.5, 127.2, 124.6, 120.2; MS (EI) m/z: 273 (M+).

N-phenyl-2-naphthamide (3ja)1

S10

NH

O

N-methyl-N-phenyl-2-naphthamide (52 mg, 0.2 mmol) and Aniline (37 mg, 0.4 mmol) provided 3ja

(34 mg, 69 %). White solid. Mp. 166 - 169 oC. 1H NMR (500 MHz, CDCl3) δ 8.32 (s, 1H), 7.90 – 7.83

(m, 5H), 7.63 (d, J = 7.8 Hz, 2H), 7.55 – 7.49 (m, 2H), 7.35 – 7.32 (m, 2H), 7.11 (t, J = 7.4 Hz, 1H); 13C

NMR (126 MHz, CDCl3) δ 165.8, 138.0, 134.9, 132.6, 132.2, 129.2, 129.0, 128.8, 127.9, 127.8, 127.5,

127.0, 124.6, 123.5, 120.2; MS (EI) m/z: 247 (M+).

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S11

N-phenylbenzamide (3aa)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.00

2.00

2.04

1.04

2.00

2.92

7.07

347.

0881

7.10

317.

2913

7.30

687.

3216

7.40

577.

4203

7.43

537.

4708

7.48

457.

5001

7.56

767.

5833

7.75

677.

7944

7.80

92

13C NMR

102030405060708090100110120130140150160170180190200f1 (ppm)

120.

2312

4.58

127.

0312

8.79

129.

1013

1.84

134.

9813

7.92

165.

79

S12

N-(p-tolyl)benzamide (3ab)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

2.00

2.10

3.00

0.70

2.00

2.35

33

7.17

827.

1943

7.47

707.

4793

7.48

257.

4934

7.49

637.

5059

7.50

887.

5099

7.52

437.

5384

7.54

117.

5437

7.55

147.

5561

7.56

067.

5679

7.57

057.

5731

7.77

837.

8649

7.86

787.

8818

7.88

39

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

20.9

2

120.

2412

6.98

128.

7712

9.60

131.

7513

4.25

135.

0813

5.33

165.

60

S13

N-(o-tolyl)benzamide (3ac)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

1.05

1.10

0.90

2.10

1.10

0.90

2.00

1.00

2.27

46

7.03

917.

0409

7.05

417.

0557

7.06

907.

0707

7.15

997.

1750

7.19

937.

2144

7.42

097.

4353

7.45

087.

4846

7.48

687.

4952

7.49

957.

5037

7.51

177.

5140

7.60

997.

8135

7.82

817.

8834

7.89

92

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

17.5

4

122.

9112

5.09

126.

5712

6.76

128.

5112

9.08

130.

2513

1.53

134.

6513

5.44

165.

36

S14

N-mesitylbenzamide (3ad)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

6.00

3.00

2.00

0.90

2.12

1.07

2.00

2.17

292.

2250

6.86

697.

2521

7.40

807.

4224

7.43

787.

4760

7.49

067.

5055

7.83

547.

8378

7.85

20

13C NMR

-100102030405060708090100110120130140150160170180190200f1 (ppm)

18.3

720

.94

127.

1612

8.72

128.

9913

1.14

131.

7013

4.61

135.

2613

7.09

166.

02

S15

N-(4-Methoxyphenyl)benzamide (3ae)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

2.00

2.05

3.00

0.80

2.00

3.73

81

6.81

256.

8194

6.82

376.

8330

6.83

736.

8442

7.38

107.

3954

7.41

097.

4477

7.45

017.

4568

7.46

227.

4671

7.47

437.

7235

7.77

677.

7912

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

55.5

0

114.

22

122.

1212

6.98

128.

7313

0.98

131.

6913

5.00

156.

61

165.

65

S16

N-(4-(methylthio)phenyl)benzamide (3af)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

2.00

2.00

3.00

0.80

2.00

2.41

86

7.20

657.

2237

7.40

127.

4156

7.43

127.

4684

7.48

327.

5049

7.52

217.

7454

7.78

117.

7836

7.79

81

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

16.6

5

120.

8012

6.98

127.

9912

8.81

131.

8913

3.98

134.

8413

5.51

165.

62

S17

N-(4-fluorophenyl)benzamide (3ag)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.00

2.00

3.00

0.80

2.00

6.98

106.

9853

6.99

466.

9987

7.01

117.

0156

7.40

837.

4226

7.42

517.

4352

7.43

827.

4768

7.49

197.

5160

7.52

557.

5297

7.53

397.

5435

7.78

307.

7858

7.80

02

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

115.

7011

5.88

122.

0112

2.08

126.

9812

8.85

131.

9813

3.84

133.

8613

4.70

158.

5616

0.50

165.

69

S18

N-(4-(trifluoromethyl)phenyl)benzamide (3ah)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

2.00

1.00

2.00

2.00

2.00

0.90

7.52

837.

5427

7.55

817.

5960

7.61

077.

6254

7.70

637.

7235

7.95

787.

9605

7.97

478.

0076

8.02

46

10.5

725

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

120.

5412

3.67

123.

7612

3.93

124.

1812

5.92

126.

3012

6.33

126.

3612

6.39

128.

2412

8.90

132.

3613

4.95

143.

29

166.

50

S19

N-(pyridin-2-yl)benzamide (3ai)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.00

2.00

1.00

1.05

2.00

1.00

0.95

0.90

6.99

457.

0053

7.00

837.

0188

7.40

817.

4228

7.43

847.

4840

7.49

877.

7210

7.87

677.

8791

7.89

36

9.07

43

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

114.

50

119.

88

127.

3512

8.84

132.

3513

4.08

139.

08

147.

0215

1.47

165.

85

S20

N-(thiazol-2-yl)benzamide (3aj)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.95

0.95

2.00

1.00

2.00

6.86

566.

8728

6.92

956.

9368

7.45

177.

4675

7.55

51

7.95

687.

9595

7.97

38

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

113.

37

128.

0612

8.75

132.

6013

2.69

136.

60

160.

41

165.

84

S21

N-(benzo[d]thiazol-2-yl)benzamide (3ak)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.00

1.00

2.00

1.00

1.00

2.00

7.19

557.

1970

7.21

187.

2128

7.23

687.

2394

7.25

107.

2535

7.26

707.

2699

7.28

477.

2875

7.30

047.

3029

7.31

467.

3171

7.39

457.

3981

7.40

957.

4108

7.42

267.

4258

7.53

787.

5402

7.54

267.

5551

7.56

767.

5700

7.57

247.

8469

7.84

827.

8622

7.86

418.

0234

8.02

598.

0403

8.04

25

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

120.

4112

1.41

124.

1012

6.19

128.

0612

9.01

131.

5713

1.92

133.

13

147.

09

160.

14

166.

08

S22

N-benzylbenzamide (3al)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.00

1.00

1.10

4.00

2.00

1.00

2.00

4.57

524.

5864

6.35

517.

2277

7.23

637.

2447

7.28

287.

2916

7.34

207.

3564

7.35

907.

3690

7.37

207.

4122

7.41

487.

4174

7.42

977.

4443

7.71

077.

7136

7.71

757.

7278

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

44.1

615

126.

9431

127.

6447

127.

9320

128.

6023

128.

7994

131.

5625

134.

3615

138.

1489

167.

3360

S23

N-benzhydrylbenzamide (3am)

1H NMR

-2-1012345678910111213f1 (ppm)

1.00

1.00

10.0

02.

001.

002.

00

6.36

156.

3771

6.66

516.

6800

7.18

127.

1843

7.18

477.

1881

7.19

317.

1984

7.20

307.

2036

7.20

517.

2082

7.20

927.

2108

7.21

277.

2148

7.21

657.

2225

7.22

577.

2414

7.24

327.

2446

7.24

897.

2566

7.25

877.

2609

7.27

027.

2734

7.27

587.

3188

7.32

047.

3220

7.32

547.

3367

7.33

907.

3492

7.35

227.

3532

7.35

597.

3987

7.40

137.

4039

7.41

227.

4162

7.42

037.

4284

7.43

107.

4335

7.71

877.

7214

7.72

557.

7356

7.73

687.

7380

7.74

19

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

57.4

5

127.

0712

7.52

127.

5712

8.63

128.

7513

1.69

134.

2314

1.45

166.

51

S24

N-(1-phenylethyl)benzamide (3an)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

1.00

0.90

1.00

2.00

4.00

1.00

2.00

1.50

831.

5221

5.22

455.

2387

5.25

325.

2676

5.28

16

6.38

206.

3947

7.26

607.

2806

7.29

707.

2986

7.30

217.

3038

7.31

277.

3135

7.31

567.

3184

7.32

097.

3339

7.38

097.

3958

7.67

867.

6814

7.69

567.

6979

13C NMR

102030405060708090100110120130140150160170180190200f1 (ppm)

21.7

3

49.2

3

126.

2612

6.94

127.

4512

8.55

128.

7413

1.47

134.

5514

3.12

166.

60

S25

N-allylbenzamide (3ao)

1H NMR

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.00

1.00

1.00

1.05

0.95

2.00

1.00

2.00

3.91

463.

9175

3.92

053.

9260

3.92

893.

9317

3.93

723.

9402

3.94

315.

0098

5.01

265.

0303

5.03

315.

1229

5.76

365.

7731

5.78

415.

7978

5.81

83

6.92

977.

2539

7.25

727.

2685

7.28

137.

2843

7.34

117.

3436

7.34

607.

3547

7.35

837.

3622

7.37

077.

3732

7.37

567.

7028

7.70

557.

7092

7.71

987.

7212

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

42.2

3

116.

10

126.

8912

8.23

131.

1913

4.01

134.

20

167.

44

S26

N-cyclohexylbenzamide (3ap)

1H NMR

-2-1012345678910111213f1 (ppm)

3.00

2.00

1.00

2.00

2.00

1.00

1.00

2.00

1.00

2.00

1.12

051.

1283

1.13

681.

1466

1.15

261.

1595

1.17

601.

1814

1.19

891.

2059

1.31

771.

3351

1.34

171.

3484

1.36

181.

3687

1.37

571.

3926

1.57

031.

5779

1.59

631.

6613

1.66

871.

6763

1.68

861.

6965

1.70

391.

9438

1.95

061.

9595

1.96

851.

9756

3.90

083.

9089

3.91

707.

3288

7.33

097.

3341

7.34

517.

3479

7.35

767.

3604

7.36

447.

3916

7.39

437.

3969

7.40

467.

4091

7.41

367.

4211

7.42

367.

6703

7.67

327.

6773

7.68

437.

6872

7.68

96

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

24.9

225

.57

33.2

3

48.7

0

126.

8312

8.50

131.

2413

5.04

166.

65

S27

2-methyl-N-phenylbenzamide (3ba)

1H NMR

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

1.00

2.32

3.00

1.00

1.00

2.00

2.42

29

7.06

127.

0761

7.09

107.

1543

7.16

937.

1947

7.26

927.

2845

7.30

327.

3844

7.39

937.

4530

7.53

247.

5476

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

19.8

3

119.

8712

4.56

125.

9012

6.60

129.

1113

0.29

131.

2713

6.43

137.

97

168.

09

S28

3-methyl-N-phenylbenzamide (3ca)

1H NMR

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

1.00

4.00

3.00

1.00

0.83

2.33

57

7.05

367.

0684

7.08

337.

2667

7.27

137.

2747

7.28

417.

2993

7.55

957.

5748

7.60

207.

8290

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

21.4

0

120.

2012

3.97

124.

5012

7.80

128.

6312

9.07

132.

5813

4.97

137.

9813

8.69

165.

99

S29

4-methyl-N-phenylbenzamide (3da)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

1.00

2.00

2.00

2.00

2.71

2.35

63

7.06

067.

0750

7.08

957.

2092

7.22

477.

2836

7.29

877.

3139

7.55

937.

5753

7.69

257.

7078

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

21.5

0

120.

1312

4.43

127.

0112

9.07

129.

4413

2.10

138.

0114

2.38

165.

64

S30

4-(tert-butyl)-N-phenylbenzamide (3ea)

1H NMR

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

9.00

1.00

2.00

2.00

2.00

2.72

1.28

40

7.06

037.

0750

7.08

997.

2826

7.29

837.

3139

7.42

257.

4391

7.56

177.

5775

7.73

047.

7467

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

31.1

634

.99

120.

1612

4.41

125.

7112

6.89

129.

0613

2.07

138.

05

155.

41

165.

73

S31

4-methoxy-N-phenylbenzamide (3fa)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

2.00

1.00

2.00

2.00

0.80

2.00

3.80

33

6.89

336.

9105

7.05

377.

0685

7.08

297.

2786

7.29

377.

3092

7.54

987.

5654

7.69

257.

7635

7.77

96

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

55.4

6

113.

9612

0.11

124.

3312

7.11

128.

8612

9.05

138.

06

162.

4616

5.19

S32

N-phenyl-4-(trifluoromethyl)benzamide (3ga)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

1.00

2.00

2.00

2.00

2.00

0.90

7.10

677.

1215

7.13

637.

3479

7.36

437.

3797

7.76

727.

7826

7.89

507.

9113

8.13

388.

1500

10.4

504

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

120.

8912

3.29

124.

4612

5.46

125.

7712

5.80

125.

8312

5.86

129.

0312

9.12

131.

6613

1.92

139.

2313

9.27

164.

82

S33

4-fluoro-N-phenylbenzamide (3ha)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

2.00

2.00

0.80

2.00

7.07

917.

0960

7.11

287.

2925

7.30

867.

3241

7.54

377.

5594

7.69

437.

8024

7.81

297.

8196

7.83

01

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

116.

0311

6.21

120.

4712

4.96

129.

3712

9.59

129.

6613

1.33

131.

3613

7.94

164.

1216

4.90

166.

13

S34

N-phenyl-[1,1'-biphenyl]-4-carboxamide (3ia)

1H NMR

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.00

3.00

2.00

4.00

2.00

0.80

2.00

7.08

727.

1020

7.11

687.

3100

7.32

647.

3416

7.35

607.

4011

7.41

667.

4314

7.56

207.

5765

7.59

297.

6090

7.64

387.

6604

7.78

207.

8790

7.89

55

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

120.

1612

4.60

127.

2312

7.47

127.

5512

8.14

128.

9712

9.14

133.

5613

7.90

139.

8514

4.71

165.

37

S35

N-phenyl-2-naphthamide (3ja)

1H NMR

-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

1.00

2.00

2.13

2.00

5.00

1.00

7.093

07.1

079

7.122

77.3

173

7.333

77.3

490

7.489

07.5

026

7.515

47.5

189

7.533

97.5

451

7.623

37.6

388

7.826

97.8

444

7.866

77.8

746

7.898

68.3

150

13C NMR

0102030405060708090100110120130140150160170180190200f1 (ppm)

120.

2212

3.52

124.

6212

6.97

127.

5112

7.83

127.

9312

8.79

128.

9712

9.15

132.

1913

2.62

134.

8713

7.97

165.

77