cascade annulations of benzimidates with alkenes …s1 synthesis of polydisubstituted 3-aminoindenes...
TRANSCRIPT
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Synthesis of polydisubstituted 3-aminoindenes via rhodium-catalysed [3 + 2] cascade annulations of benzimidates with alkenes
Binjie Wu, Zi Yang, Hong Zhang, Lianhui wang, and Xiuling Cui*
Engineering Research Center of Molecular Medicine of Ministry of Education, Key Laboratory of
Fujian Molecular Medicine, Key Laboratory of Xiamen Marine and Gene Drugs, School of
Biomedical Sciences, Huaqiao University, Xiamen 361021, P. R. China, *e-mail: [email protected]
Contents
1.General Information.......................................................................................................................22.Typical procedure for synthesis of 3a............................................................................................23.Conversion of 3a ...........................................................................................................................24.Characterization data of the products ............................................................................................35.X-ray Crystallographic data of 3a................................................................................................126.Reference .....................................................................................................................................197.NMR Spectra of the Products ......................................................................................................208.HRMS spectra of the intermediate E ...........................................................................................44
Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2019
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1. General Information
Unless otherwise stated, all commercial materials and solvents were used directly
without further purification. Commercially available chemicals were obtained from
Energy Chemical, TCI, Alfa Aesar, J&K. Melting points were determined in open
glass capillaries and were uncorrected. 1H NMR spectra were recorded on 400 MHz
spectrometers, and 13C NMR spectra were recorded on a 100 MHz spectrometer.
High-resolution mass spectra (HRMS) were equipped with an ESI source and a TOF
detector. Column chromatography was performed on silica gel (70-230 mesh ASTM)
using the reported eluents. Thin-layer chromatography (TLC) was carried out on 4×15
cm plates with a layer thickness of 0.2 mm (silica gel 60 F254). Benzimidates[1] and
α,β-unsaturated ketones[2] were synthesized according to the previously reported
procedure.
2. Typical procedure for synthesis of 3a
R1NH
OR2
R4
R3R3
NH2
R4+ R1
[Cp*Rh(MeCN)3](SbF6)2 (5 mol%)1-Ada-CO2H (1 equiv)
DCE, 120℃
1 2 336h, air
To a test tube equipped with magnetic stir bar, alkene (2, 0.40 mmol),
[Cp*Rh(MeCN)3](SbF6)2 (0.01 mmol, 8.3 mg), 1-Ada-CO2H (0.2 mmol, 36.0 mg),
DCE (2ml) and benzimidate (1, 0.20 mmol) were added sequentially under air
atmosphere. The reaction mixture was stirred at 120°C for 36 h. After cooled to room
temperature, Na2CO3 (0.2 mmol, 21.2mg) was added. The resulting mixture was
stirred at room temperature for another 1 h. After removal of the solvent under
reduced pressure, purification was performed by flash column chromatography on
silica gel with petroleum ether/ethyl acetate (gradient mixture ratio from 5:1 to 2:1) as
eluent to afford the desired product 3.
3. Conversion of 3aNH2
O
PhPh
PhNHNH2·HCl+NN Ph
Ph
Ph
EtOH
100℃
3a 4, 95%
12 h
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To a test tube equipped with magnetic stir bar, 3a (0.1 mmol), phenylhydrazine
hydrochloride (0.3 mmol) and dry ethanol (1 ml) were added sequentially under air
atmosphere. The reaction mixture was stirred at 100°C for 12 h and cooled to room
temperature. After evaporation of solvent, the residue was dissolved in ethyl acetate,
and the organic layer was washed subsequently with H2O and then dried with
anhydrous MgSO4. After concentration under reduced pressure, the residue was
purified by column chromatography on silica gel to afford the product 4 in 95%
yield.[3]
4. Characterization data of the products
3-Amino-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3a)
NH2
O
yellow solid, 88% yield, mp: 209-210°C. 1H NMR (400 MHz, DMSO) δ 8.71 (s, 2H),
8.07-8.01 (m, 1H), 7.44-7.34 (m, 4H), 7.28-7.17 (m, 3H), 7.17-7.07 (m, 1H), 6.99-
6.89 (m, 3H), 6.81-6.73 (m, 2H), 5.28(s, 1H). 13C NMR (100 MHz, DMSO) δ 191.3,
161.9, 150.6, 142.8, 142.3, 136.6, 130.8, 129.4, 128.3, 128.0, 127.6, 127.4, 127.2,
126.2, 125.1, 122.0, 110.8, 52.7. HRMS (ESI) Calcd for C22H17NO [M+H]+ 312.1383;
found 312.1386.
3-Amino-6-chloro-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3b)
NH2
OCl
yellow solid, 77% yield, mp: 207-208°C. 1H NMR (400 MHz, DMSO) δ 8.71 (s, 2H),
8.07 (d, J = 8.2 Hz, 1H), 7.52-7.46 (m, 1H), 7.42-7.35 (m, 2H), 7.29-7.17 (m, 3H),
7.11 (d, J = 1.9 Hz, 1H), 7.02-6.92 (m, 3H), 6.84-6.76 (m, 2H), 5.31 (s,1H). 13C NMR
(100 MHz, DMSO) δ 191.4, 160.6, 152.4, 142.6, 141.5, 135.6, 135.4, 129.6, 128.5,
128.0, 127.8, 127.6, 127.2, 126.5, 125.0, 123.7, 110.8, 52.5. HRMS (ESI) Calcd for
C22H16ClNO [M+H]+ 346.0993; found 346.0994.
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3-Amino-6-bromo-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3c)
NH2
OBr
yellow solid, 87% yield, mp: 189-190°C. 1H NMR (400 MHz, DMSO) δ 8.70 (s, 2H),
8.00 (d, J = 8.2 Hz, 1H), 7.66-7.59 (m, 1H), 7.41-7.36 (m, 2H), 7.28-7.18 (m, 4H),
7.02-6.92 (m, 3H), 6.85-6.78 (m, 2H), 5.31 (s,1H). 13C NMR (100 MHz, DMSO) δ
191.4, 160.7, 152.6, 142.6, 141.4, 135.9, 130.6, 129.6, 128.5, 128.0, 127.9, 127.6,
127.2, 126.6, 124.1, 124.0, 110.7, 52.5. HRMS (ESI) Calcd for C22H16BrNO [M+H]+
390.0488; found 390.0488.
3-Amino-6-methyl-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3d)
NH2
O
yellow solid, 88% yield, mp: 211-212°C. 1H NMR (400 MHz, DMSO) δ 8.69 (s, 2H),
7.91 (d, J = 7.8 Hz, 1H), 7.39-7.33 (m, 2H), 7.26-7.17 (m, 4H), 6.99-6.89 (m, 4H),
6.80-6.73 (m, 2H), 5.21 (s,1H), 2.28 (s, 3H). 13C NMR (100 MHz, DMSO) δ 191.0,
162.2, 151.0, 142.9, 142.5, 140.9, 134.0, 129.3, 128.4, 128.3, 127.9, 127.6, 127.2,
126.2, 125.5, 121.8, 110.5, 52.5, 21.8. HRMS (ESI) Calcd for C23H19NO [M+H]+
326.1539; found 326.1540.
3-Amino-6-methoxy-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3e)
NH2
OMeO
yellow solid, 68% yield, mp: 177-178°C. 1H NMR (400 MHz, DMSO) δ 8.68 (s, 2H),
7.96 (d, J = 8.6 Hz, 1H), 7.40-7.27 (m, 2H), 7.26-7.15 (m, 3H), 7.02-6.89 (m, 4H),
6.79-6.73 (m, 2H), 6.62 (d, J = 2.3 Hz, 1H), 5.20 (s,1H), 3.70 (s, 3H). 13C NMR (100
MHz, DMSO) δ 190.4, 162.3, 162.1, 153.1, 143.0, 142.6, 129.2, 129.1, 128.3, 127.9,
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127.6, 127.2, 126.2, 123.4, 113.8, 110.3, 110.2, 55.9, 52.5. HRMS (ESI) Calcd for
C23H19NO2 [M+H]+ 342.1489; found 342.1490.
3-Amino-5-methyl-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3f)
NH2
O
yellow solid, 76% yield, mp: 198-199°C. 1H NMR (400 MHz, DMSO) δ 8.68 (s, 2H),
7.86 (s, 1H), 7.40-7.35 (m, 2H), 7.27-7.17 (m, 4H), 7.01-6.88 (m, 4H), 6.79-6.71 (m,
2H), 5.21 (s, 1H). 13C NMR (100 MHz, DMSO) δ 191.2, 162.1, 148.0, 142.8, 142.5,
136.8, 136.7, 131.7, 129.4, 128.3, 127.9, 127.5, 127.2, 126.2, 124.8, 122.2, 111.2,
52.3, 21.5. HRMS (ESI) Calcd for C23H19NO [M+H]+ 326.1539; found 326.1539.
3-Amino-5-methoxy-1-phenyl-1H-inden-2-yl)(phenyl)methanone (3g)
NH2
O
MeO
yellow solid, 57% yield, mp: 213-214°C. 1H NMR (400 MHz, DMSO) δ 8.66 (s, 2H),
7.70 (d, J = 2.0 Hz, 1H), 7.39-7.35 (m, 2H), 7.27-7.17 (m, 3H), 7.00-6.88 (m, 5H),
6.77-6.71 (m, 2H), 5.19 (s, 1H), 3.81 (s, 3H). 13C NMR (100 MHz, DMSO) δ 191.2,
161.9, 159.3, 143.0, 142.8, 142.5, 137.8, 129.4, 128.3, 127.9, 127.5, 127.3, 126.1,
125.8, 117.9, 111.8, 106.3, 55.9, 52.0. HRMS (ESI) Calcd for C23H19NO2 [M+H]+
342.1489; found 342.1489.
3-Amino-1-(4-fluorophenyl)-1H-inden-2-yl)(phenyl)methanone (3h)
NH2
O
F
yellow solid, 85% yield, mp: 205-206°C. 1H NMR (400 MHz, DMSO) δ 8.73 (s, 2H),
8.09-8.01 (m, 1H), 7.45-7.36 (m, 4H), 7.29-7.19 (m, 3H), 7.15-7.06 (m, 1H), 6.77 (d,
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J = 7.14 Hz, 4H), 5.29 (s,1H). 13C NMR (100 MHz, DMSO) δ 191.4, 161.9, 160.8 (d,
JCF= 241.6 Hz),150.5, 142.8, 138.3 (d, JCF= 3.0 Hz), 136.5, 130.9, 129.5, 129.3 (d,
JCF= 8.0 Hz), 128.0, 127.6, 127.2, 125.1, 122.1, 115.0 (d, JCF= 21.3 Hz), 110.8, 51.8.
19F NMR (376 MHz, DMSO) δ -117.25. HRMS (ESI) Calcd for C22H16FNO [M+H]+
330.1289; found 330.1290.
3-Amino-1-(4-chlorophenyl)-1H-inden-2-yl)(phenyl)methanone (3i)
NH2
O
Cl
yellow solid, 75% yield, mp: 235-236°C. 1H NMR (400 MHz, DMSO) δ 8.72 (s, 2H),
8.09-8.00 (m, 1H), 7.46-7.36 (m, 4H), 7.32-7.18 (m, 3H), 7.15-7.07 (m, 1H), 7.06-
6.97 (m, 2H), 6.81-6.74 (m, 2H), 5.31 (s, 1H). 13C NMR (100 MHz, DMSO) δ 191.2,
162.0, 150.2, 142.7, 141.4, 136.5, 131.0, 130.6, 129.5, 129.4, 128.3, 128.1, 127.6,
127.2, 125.1, 122.1, 110.5, 51.9. HRMS (ESI) Calcd for C22H16ClNO [M+H]+
346.0993; found 346.0994.
3-Amino-1-(4-nitrophenyl)-1H-inden-2-yl)(phenyl)methanone (3j)
NH2
O
NO2
yellow solid, 76% yield, mp: 93-94°C. 1H NMR (400 MHz, DMSO) δ 8.79 (s, 2H),
8.13-8.06 (m, 1H), 7.88-7.80 (m, 2H), 7.48-7.35 (m, 4H), 7.28-7.18 (m, 3H), 7.12 (d,
J = 7.4 Hz, 1H), 7.08-6.98 (m, 2H), 5.48 (s, 1H). 13C NMR (100 MHz, DMSO) δ
191.1, 162.1, 151.1, 149.4, 146.0, 142.6, 136.7, 131.2, 129.6, 128.9, 128.2, 128.0,
127.1, 125.2, 123.6, 122.4, 110.3, 52.1. HRMS (ESI) Calcd for C22H16N2O3 [M+H]+
357.1234; found 357.1236.
3-Amino-1-(p-tolyl)-1H-inden-2-yl)(phenyl)methanone (3k)
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NH2
O
yellow solid, 74% yield, mp: 219-220°C. 1H NMR (400 MHz, DMSO) δ 8.68 (s, 2H),
8.06-7.96 (m, 1H), 7.46-7.33 (m, 4H), 7.31-7.17 (m, 3H), 7.14-7.06 (m, 1H), 6.78 (d,
J = 8.32 Hz, 2H), 6.71-6.61 (m, 2H), 5.26 (s, 1H), 2.09 (s, 3H). 13C NMR (100 MHz,
DMSO) δ 191.2, 161.9, 150.8, 142.7, 139.2, 136.5, 135.1, 130.8, 129.5, 129.0, 128.0,
127.5, 127.4, 127.3, 125.1, 121.9, 110.7, 52.3, 21.0. HRMS (ESI) Calcd for
C23H19NO [M+H]+ 326.1539; found 326.1541.
3-Amino-1-(m-tolyl)-1H-inden-2-yl)(phenyl)methanone (3l)
NH2
O
yellow solid, 81% yield, mp: 218-219°C. 1H NMR (400 MHz, DMSO) δ 8.69 (s, 2H),
8.07-8.02 (m, 1H), 7.43-7.35 (m, 4H), 7.29-7.19 (m, 3H), 7.15-7.08 (m, 1H), 6.85 (t, J
= 7.5 Hz, 1H), 6.73 (d, J = 7.5 Hz, 1H), 6.58-6.51 (m, 2H), 5.21 (s, 1H). 13C NMR
(100 MHz, DMSO) δ 191.4, 161.8, 150.6, 142.9, 142.1, 137.1, 136.7, 130.8, 129.3,
128.3, 128.2, 127.9, 127.4, 127.2, 126.9, 125.1, 124.8, 122.0, 110.9, 52.6, 21.3.
HRMS (ESI) Calcd for C23H19NO [M+H]+ 326.1539; found 326.1542.
3-Amino-1-(3-methoxyphenyl)-1H-inden-2-yl)(phenyl)methanone (3m)
NH2
O
OMe
yellow solid, 53% yield, mp: 132-133°C. 1H NMR (400 MHz, DMSO) δ 8.69 (s, 2H),
8.07-7.98 (m, 1H), 7.48-7.35 (m, 4H), 7.32-7.19 (m, 3H), 7.19-7.11 (m, 1H), 6.88 (t, J
= 7.9 Hz, 1H), 6.54-6.47 (m, 1H), 6.41-6.28 (m, 2H), 5.25 (s, 1H), 3.55 (s, 3H). 13C
NMR (100 MHz, DMSO) δ 191.3, 161.9, 159.2, 150.4, 143.9, 142.8, 136.5, 130.8,
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129.5, 129.4, 128.0, 127.5, 127.3, 125.0, 121.9, 119.6, 113.6, 111.7, 110.6, 55.2, 52.6.
HRMS (ESI) Calcd for C23H19NO2 [M+H]+ 342.1489; found 342.1492.
3-Amino-1-(3-nitrophenyl)-1H-inden-2-yl)(phenyl)methanone (3n)
NH2
O
NO2
yellow solid, 74% yield, mp: 226-227°C. 1H NMR (400 MHz, DMSO) δ 8.77 (s, 2H),
8.12-8.06 (m, 1H), 7.83-7.78 (m, 1H), 7.57-7.53 (m, 1H), 7.49-7.40 (m, 2H), 7.36-
7.31 (m, 2H), 7.28-7.11 (m, 6H), 5.47 (s, 1H). 13C NMR (100 MHz, DMSO) δ 191.3,
162.0, 149.6, 147.6, 144.9, 142.7, 136.8, 134.4, 131.2, 129.9, 129.4, 128.1, 128.0,
127.0, 125.2, 122.6, 122.3, 121.4, 110.5, 51.77. HRMS (ESI) Calcd for C22H16N2O3
[M+H]+ 357.1234; found 357.1236.
3-Amino-1-phenyl-1H-inden-2-yl)(4-fluorophenyl)methanone (3o)
NH2
O
F
yellow solid, 75% yield, mp: 218-219°C. 1H NMR (400 MHz, DMSO) δ 8.75 (s, 2H),
8.08-8.02 (m, 1H), 7.51-7.37 (m, 4H), 7.13-7.09 (m, 1H), 7.05-6.91 (m, 5H), 6.85-
6.76 (m, 2H), 5.29 (s,1H). 13C NMR (100 MHz, DMSO) δ 189.9, 162.8 (d, JCF= 245.7
Hz), 162.2, 150.6, 142.2, 139.3 (d, JCF= 3.1 Hz), 136.5, 130.9, 129.8 (d, JCF= 8.6 Hz),
128.4, 127.6, 127.5, 126.4, 125.1, 122.0, 114.8 (d, JCF= 21.3 Hz), 110.6, 52.6. 19F
NMR (376 MHz, DMSO) δ -111.98. HRMS (ESI) Calcd for C22H16FNO [M+H]+
330.1289; found 330.1288.
3-Amino-1-phenyl-1H-inden-2-yl)(4-chlorophenyl)methanone (3p)
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NH2
O
Cl
yellow solid, 82% yield, mp: 204-205°C. 1H NMR (400 MHz, DMSO) δ 8.77 (s, 2H),
8.17-7.97 (m, 1H), 7.54-7.32 (m, 4H), 7.31-7.19 (m, 2H), 7.17-7.06 (m, 1H), 7.06-
6.89(m, 3H), 6.89-6.72 (m, 2H), 5.28 (s, 1H). 13C NMR (100 MHz, DMSO) δ 189.7,
162.4, 150.6, 142.1, 141.4, 136.4, 134.1, 131.0, 129.2, 128.4, 128.0, 127.6, 127.5,
126.4, 125.1, 122.1, 110.5, 52.47. HRMS (ESI) Calcd for C22H16ClNO [M+H]+
346.0993; found 346.0993.
3-Amino-1-phenyl-1H-inden-2-yl)(p-tolyl)methanone (3q)
NH2
O
yellow solid, 67% yield, mp: 160-161°C. 1H NMR (400 MHz, DMSO) δ 8.67 (s, 2H),
8.04-7.99 (m, 1H), 7.43-7.34 (m, 4H), 7.15-7.10 (m, 1H), 7.05-6.92 (m, 5H), 6.87-
6.80 (m, 2H), 5.33 (s, 1H), 2.24 (s,3H). 13C NMR (100 MHz, DMSO) δ 190.9, 161.8,
150.5, 142.4, 139.9, 139.1, 136.6, 130.7, 128.5, 128.4, 127.6, 127.5, 127.4, 126.3,
125.0, 121.9, 110.6, 52.7, 21.4. HRMS (ESI) Calcd for C23H19NO [M+H]+ 326.1539;
found 326.1542.
3-Amino-1-phenyl-1H-inden-2-yl)(4-methoxyphenyl)methanone (3r)
NH2
O
OMe
yellow solid, 64% yield, mp: 180-181°C. 1H NMR (400 MHz, DMSO) δ 8.63 (s, 2H),
8.03-7.97 (m, 1H), 7.54-7.47 (m, 2H), 7.43-7.34 (m, 2H), 7.16-7.10 (m, 1H), 7.04-
6.91 (m, 3H), 6.91-6.85 (m, 2H), 6.79-6.73 (m, 2H), 5.38 (s, 1H), 3.72 (s, 3H). 13C
NMR (100 MHz, DMSO) δ 190.0, 161.7, 160.5, 150.4, 142.5, 136.6, 135.1, 130.6,
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129.6, 128.4, 127.5, 127.4, 126.4, 125.0, 121.8, 113.2, 110.5, 55.6, 52.8. HRMS (ESI)
Calcd for C23H19NO2 [M+H]+ 342.1489; found 342.1491.
(3-Amino-1-ethyl-1H-inden-2-yl)(phenyl)methanone (3s)NH2
O
yellow solid, 62% yield, mp: 157-158°C. 1H NMR (400 MHz, DMSO) δ 8.61 (s, 2H),
7.98 (d, J = 7.52 Hz, 1H), 7.67-7.59 (m, 2H), 7.56-7.39 (m, 6H), 4.30-4.18 (m, 1H),
1.74-1.62 (m, 1H), 1.17-1.05 (m, 1H), 0.19 (t, J = 7.44 Hz, 3H). 13C NMR (100 MHz,
DMSO) δ 190.7, 161.6, 149.4, 143.3, 137.6, 130.4, 129.9, 128.6, 127.2, 127.1, 124.2,
121.8, 108.3, 46.4, 24.0, 8.1. HRMS (ESI) Calcd for C18H17NO [M+H]+ 264.1383;
found 264.1386.
1-(3-Amino-1-phenyl-1H-inden-2-yl)ethan-1-one (3t)NH2
O
yellow solid, 56% yield, mp: 194-195°C. 1H NMR (400 MHz, DMSO) δ 8.45 (s, 2H),
7.97-7.92 (m, 1H), 7.40-7.33 (m, 2H), 7.30-7.23 (m, 2H), 7.22-7.10 (m, 4H), 4.96 (s,
1H), 1.76 (s, 3H). 13C NMR (100 MHz, DMSO) δ 193.7, 159.1, 149.8, 142.8, 136.9,
130.4, 129.1, 127.8, 127.4, 127.0, 125.1, 121.9, 111.3, 52.2, 28.7. HRMS (ESI) Calcd
for C17H15NO [M+H]+ 250.1226; found 250.1228.
3-Amino-1-phenyl-1H-inden-2-yl)(naphthalen-2-yl)methanone (3u)
NH2
O
yellow solid, 66% yield, mp: 187-188°C. 1H NMR (400 MHz, DMSO) δ 8.84 (s, 2H),
8.12-8.06 (m, 2H), 7.95-7.91 (m, 1H), 7.85-7.81 (m, 1H), 7.73 (d, J = 8.5 Hz, 1H),
7.55-7.49 (m, 3H), 7.47-7.37 (m, 2H), 7.17-7.10 (m, 1H), 6.90-6.81 (m, 5H), 5.51
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(s,1H). 13C NMR (100 MHz, DMSO) δ 190.7, 162.3, 150.7, 142.5, 139.7, 136.5,
133.5, 132.4, 130.9, 129.1, 128.4, 127.8, 127.6, 127.5, 127.4, 127.3, 127.2, 126.6,
126.3, 125.2, 125.1, 122.0, 110.9, 52.7. HRMS (ESI) Calcd for C26H19NO [M+H]+
362.1539; found 362.1538.
2-Nitro-1-phenyl-1H-inden-3-amine (3v)NH2
NO2
yellow solid, 71% yield, mp: 249-250°C. 1H NMR (400 MHz, DMSO) δ 9.38 (s, 1H),
8.99 (s, 1H), 8.21-8.14 (m, 1H), 7.53-7.45 (m, 2H), 7.30-7.24 (m, 2H), 7.23-7.17 (m,
2H), 7.16-7.09 (m, 2H), 5.14 (s, 1H). 13C NMR (100 MHz, DMSO) δ 156.1, 147.1,
140.4, 134.2, 132.6, 129.0, 128.2, 127.7, 127.2, 125.5, 123.4, 122.4, 50.6. HRMS
(ESI) Calcd for C15H12N2O2 [M+H]+ 253.0972; found 253.0976.
2,3,4-Triphenyl-2,4-dihydroindeno[1,2-c]pyrazole (4)
NN Ph
Ph
Ph
white solid, 95% yield, mp: 188-189°C. 1H NMR (400 MHz, CDCl3) δ 7.98-7.90 (m,
1H), 7.43-7.12 (m, 16H), 6.98-6.90 (m, 2H), 5.05 (s, 1H). 13C NMR (100 MHz,
CDCl3) δ 159.7, 153.4, 141.7, 140.8, 137.9, 133.6, 130.0, 129.9, 129.1, 128.9, 128.6,
128.2, 128.1, 128.0, 127.7, 127.6, 127.2, 126.9, 126.0, 125.4, 120.4, 47.8. HRMS
(ESI) Calcd for C28H20N2 [M+H]+ 385.1699; found 385.1699.
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5. X-ray Crystallographic data of 3a
X-ray molecular structure of 3a
Table 1 Crystal data and structure refinement for 3a.
Identification code 3a
Empirical formula C22H17NO
Formula weight 311.36
Temperature/K 293(2)
Crystal system orthorhombic
Space group P212121
a/Å 9.8259(6)
b/Å 12.3491(8)
c/Å 13.8190(9)
α/° 90
β/° 90
γ/° 90
Volume/Å3 1676.82(18)
Z 4
ρcalcg/cm3 1.233
μ/mm-1 0.588
F(000) 656.0
Crystal size/mm3 0.18 × 0.16 × 0.15
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Radiation CuKα (λ = 1.54184)
2Θ range for data collection/° 9.606 to 142.272
Index ranges -11 ≤ h ≤ 11, -13 ≤ k ≤ 15, -16 ≤ l ≤ 16
Reflections collected 6963
Independent reflections 3192 [Rint = 0.0307, Rsigma = 0.0408]
Data/restraints/parameters 3192/0/226
Goodness-of-fit on F2 1.043
Final R indexes [I>=2σ (I)] R1 = 0.0404, wR2 = 0.0944
Final R indexes [all data] R1 = 0.0477, wR2 = 0.1006
Largest diff. peak/hole / e Å-3 0.13/-0.12
Flack parameter -0.1(3)
Table 2 Fractional Atomic Coordinates (×104) and Equivalent Isotropic
Displacement Parameters (Å2×103) for 3a. Ueq is defined as 1/3 of of the trace of
the orthogonalised UIJtensor.
Atomx y z U(eq)
C1 -918(3) 3718(2) 3194(2) 45.6(6)
C2 -1712(3) 4333(3) 2584(2) 51.7(7)
C3 -1253(3) 5319(3) 2238(2) 55.5(7)
C4 11(3) 5709(2) 2493(2) 52.7(6)
C5 821(3) 5105(2) 3103.5(18) 42.2(6)
C6 362(3) 4109(2) 3445.4(18) 40.3(5)
C7 1430(2) 3650.4(19) 4061.0(17) 37.8(5)
C8 2501(3) 4380(2) 4130.8(18) 39.3(5)
C9 2235(3) 5359(2) 3491.4(19) 43.3(6)
S14
C10 3277(3) 5524(2) 2700(2) 49.3(7)
C11 3636(4) 4687(3) 2091(2) 64.8(8)
C12 4596(4) 4828(4) 1363(3) 85.0(12)
C13 5207(4) 5822(5) 1249(3) 92.5(15)
C14 4881(5) 6649(4) 1847(3) 93.7(15)
C15 3911(4) 6515(3) 2572(3) 71.2(10)
C16 3654(2) 4202.2(19) 4713.7(17) 39.2(5)
C17 4673(3) 5095(2) 4836.8(18) 41.3(5)
C18 5986(3) 4970(3) 4490(2) 55.6(7)
C19 6929(4) 5787(3) 4603(3) 69.3(9)
C20 6579(4) 6716(3) 5083(3) 72.4(10)
C21 5288(4) 6845(3) 5444(3) 67.4(9)
C22 4330(3) 6036(2) 5321(2) 52.7(7)
N1 1367(3) 2678.8(18) 4468.5(18) 46.8(5)
O1 3857(2) 3324.2(15) 5144.2(15) 51.6(5)
Table 3 Anisotropic Displacement Parameters (Å2×103) for 3a. The Anisotropic
displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].
Atom U11 U22 U33 U23 U13 U12
C1 42.8(14) 47.5(14) 46.4(14) -2.8(11) 1.3(11) -2.5(11)
C2 36.7(13) 67.7(17) 50.8(15) -4.9(14) -1.5(11) -0.4(13)
C3 45.8(15) 70.1(18) 50.5(15) 11.0(13) -7.2(12) 8.4(13)
C4 51.7(14) 54.3(15) 52.2(14) 14.8(13) -4.9(13) 2.1(13)
C5 41.3(14) 42.0(13) 43.2(13) 4.6(10) -0.4(10) 1.8(10)
C6 39.2(12) 41.0(12) 40.6(12) -0.3(10) 2.8(10) 2.3(10)
C7 35.9(12) 38.2(11) 39.4(12) 1.0(9) 5.6(10) 2.4(10)
C8 40.2(13) 36.8(11) 40.8(12) 6.7(10) 1.8(10) 0.5(10)
C9 44.4(14) 39.7(13) 45.9(13) 7.6(10) -5.5(11) -1.3(10)
S15
C10 42.1(13) 56.8(16) 49.1(15) 17.5(12) -10.1(11) -6.0(12)
C11 59.1(19) 78(2) 57.2(17) 7.3(16) 0.7(15) -4.3(16)
C12 68(2) 129(4) 58(2) 8(2) 3.5(18) 9(2)
C13 52(2) 159(5) 66(2) 50(3) 0.4(17) -15(3)
C14 80(3) 107(3) 94(3) 47(3) -2(2) -33(3)
C15 71(2) 68(2) 74(2) 27.0(18) -3.9(18) -20.1(17)
C16 38.9(12) 39.0(12) 39.9(12) 2.8(10) 2.8(10) 5.6(10)
C17 41.5(13) 44.3(13) 38.0(12) 5.3(10) -4.7(10) 0.2(11)
C18 49.9(16) 58.3(17) 58.6(17) -4.8(13) 7.0(13) -4.2(13)
C19 54.2(18) 78(2) 76(2) -3.7(19) 10.8(16) -16.4(17)
C20 73(2) 66(2) 78(2) -2.5(17) -3.6(19) -27.2(18)
C21 81(2) 50.0(16) 71(2) -10.5(14) -7.6(19) -4.0(16)
C22 51.4(15) 50.9(15) 55.9(16) -2.1(12) -2.6(13) 3.1(12)
N1 42.1(13) 39.9(11) 58.4(14) 12.7(10) -0.1(11) -2.4(10)
O1 45.4(10) 45.5(10) 63.8(12) 15.1(8) -8.1(9) 4.0(8)
Table 4 Bond Lengths for 3a.
Atom Atom Length/Å Atom Atom Length/Å
C1 C2 1.377(4) C10 C15 1.385(4)
C1 C6 1.392(4) C11 C12 1.390(5)
C2 C3 1.384(4) C12 C13 1.376(7)
C3 C4 1.378(4) C13 C14 1.352(7)
C4 C5 1.380(4) C14 C15 1.393(5)
C5 C6 1.393(4) C16 C17 1.499(4)
C5 C9 1.522(3) C16 O1 1.253(3)
C6 C7 1.465(3) C17 C18 1.384(4)
C7 C8 1.389(3) C17 C22 1.383(4)
S16
C7 N1 1.327(3) C18 C19 1.379(4)
C8 C9 1.521(3) C19 C20 1.369(5)
C8 C16 1.407(3) C20 C21 1.371(5)
C9 C10 1.512(4) C21 C22 1.384(4)
C10 C11 1.379(5)
Table 5 Bond Angles for 3a.
Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚
C2 C1 C6 118.2(3) C11 C10 C9 120.9(3)
C1 C2 C3 120.8(3) C11 C10 C15 118.1(3)
C4 C3 C2 120.9(3) C15 C10 C9 121.0(3)
C3 C4 C5 119.2(3) C10 C11 C12 121.4(4)
C4 C5 C6 119.9(3) C13 C12 C11 119.4(4)
C4 C5 C9 129.1(3) C14 C13 C12 120.0(4)
C6 C5 C9 111.0(2) C13 C14 C15 120.8(4)
C1 C6 C5 121.0(2) C10 C15 C14 120.3(4)
C1 C6 C7 131.2(2) C8 C16 C17 119.2(2)
C5 C6 C7 107.8(2) O1 C16 C8 122.4(2)
C8 C7 C6 109.4(2) O1 C16 C17 118.4(2)
N1 C7 C6 124.3(2) C18 C17 C16 120.1(2)
N1 C7 C8 126.3(2) C22 C17 C16 120.6(2)
C7 C8 C9 110.2(2) C22 C17 C18 119.2(3)
C7 C8 C16 123.3(2) C19 C18 C17 120.4(3)
C16 C8 C9 126.5(2) C20 C19 C18 119.9(3)
C8 C9 C5 101.4(2) C19 C20 C21 120.4(3)
C10 C9 C5 113.0(2) C20 C21 C22 120.1(3)
S17
C10 C9 C8 114.2(2) C17 C22 C21 120.0(3)
Table 6 Hydrogen Bonds for 3a.
D H A d(D-H)/Å d(H-A)/Å d(D-A)/Å D-H-A/°
N1 H1A O1 0.84(3) 2.11(3) 2.737(3) 131(3)
N1 H1B O11 0.93(3) 1.91(3) 2.811(3) 164(3)
1-1/2+X,1/2-Y,1-Z
Table 7 Torsion Angles for 3a.
A B C D Angle/˚ A B C D Angle/˚
C1 C2 C3 C4 0.2(4) C8 C16 C17 C22 66.5(3)
C1 C6 C7 C8 -176.8(3) C9 C5 C6 C1 179.1(2)
C1 C6 C7 N1 4.2(4) C9 C5 C6 C7 -0.5(3)
C2 C1 C6 C5 1.1(4) C9 C8 C16 C17 8.0(4)
C2 C1 C6 C7 -179.5(3) C9 C8 C16 O1 -172.7(2)
C2 C3 C4 C5 -0.2(5) C9 C10 C11 C12 -179.8(3)
C3 C4 C5 C6 0.7(4) C9 C10 C15 C14 179.2(3)
C3 C4 C5 C9 -179.6(3) C10 C11 C12 C13 0.3(5)
C4 C5 C6 C1 -1.1(4) C11 C10 C15 C14 -0.1(5)
C4 C5 C6 C7 179.3(2) C11 C12 C13 C14 0.5(6)
C4 C5 C9 C8 178.6(3) C12 C13 C14 C15 -1.1(7)
C4 C5 C9 C10 -58.7(4) C13 C14 C15 C10 0.9(6)
C5 C6 C7 C8 2.7(3) C15 C10 C11 C12 -0.5(5)
C5 C6 C7 N1 -176.3(2) C16 C8 C9 C5 -177.0(2)
C5 C9 C10 C11 -64.7(3) C16 C8 C9 C10 61.1(3)
S18
C5 C9 C10 C15 116.1(3) C16 C17 C18 C19 -179.9(3)
C6 C1 C2 C3 -0.6(4) C16 C17 C22 C21 178.9(3)
C6 C5 C9 C8 -1.7(3) C17 C18 C19 C20 1.8(6)
C6 C5 C9 C10 121.0(2) C18 C17 C22 C21 0.8(4)
C6 C7 C8 C9 -3.9(3) C18 C19 C20 C21 -0.8(6)
C6 C7 C8 C16 176.5(2) C19 C20 C21 C22 -0.2(6)
C7 C8 C9 C5 3.4(3) C20 C21 C22 C17 0.2(5)
C7 C8 C9 C10 -118.5(2) C22 C17 C18 C19 -1.8(5)
C7 C8 C16 C17 -172.5(2) N1 C7 C8 C9 175.1(2)
C7 C8 C16 O1 6.9(4) N1 C7 C8 C16 -4.5(4)
C8 C9 C10 C11 50.5(3) O1 C16 C17 C18 65.2(3)
C8 C9 C10 C15 -128.7(3) O1 C16 C17 C22 -112.9(3)
C8 C16 C17 C18 -115.4(3)
Table 8 Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement
Parameters (Å2×103) for 3a.
Atomx y z U(eq)
H1 -1230 3058 3431 55
H2 -2568 4083 2402 62
H3 -1805 5724 1828 67
H4 314 6372 2256 63
H9 2192 6011 3895 52
H11 3227 4013 2169 78
H12 4822 4255 957 102
H13 5846 5925 761 111
H14 5309 7315 1773 112
S19
H15 3687 7094 2973 85
H18 6233 4332 4180 67
H19 7802 5708 4353 83
H20 7219 7263 5165 87
H21 5058 7477 5771 81
H22 3454 6125 5564 63
H1A 2000(30) 2530(20) 4850(20) 44(8)
H1B 570(30) 2280(30) 4490(20) 53(8)
6. References
[1] V. Yadav and K. Babu, Eur. J. Org. Chem. 2005, 452-456.
[2] T. Lei, C. Zhou, M. Huang, L. Zhao, B. Yang, C. Ye, H. Xiao, Q. Meng, V.
Ramamurthy, C. Tung and L. Wu, Angew. Chem. Int. Ed. 2017, 56, 15407-15410.
[3] L. Calvo, A. Gonzalez-Nogal, A. Gonzalez-Ortega and M. Sanudo, Tetrahedron
Lett. 2001, 42, 8981.
S20
7. NMR Spectra of the Products1H, 13C spectra of 3a
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
1.00
2.01
2.98
1.00
2.99
3.97
0.99
1.79
5.28
6.75
6.76
6.76
6.77
6.77
6.78
6.78
6.90
6.90
6.90
6.91
6.92
6.92
6.93
6.93
6.94
6.95
6.96
6.96
6.97
6.98
6.98
7.07
7.08
7.10
7.10
7.11
7.11
7.12
7.13
7.18
7.19
7.19
7.20
7.21
7.22
7.23
7.23
7.24
7.25
7.25
7.26
7.27
7.27
7.27
7.35
7.36
7.36
7.38
7.38
7.39
7.39
7.40
7.40
7.41
7.41
7.43
7.43
8.03
8.03
8.04
8.05
8.05
8.71
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.38
39.59
39.80
40.01
40.22
40.42
40.63
52.66
110.78
121.98
125.08
126.24
127.23
127.44
127.57
127.96
128.33
129.43
130.80
136.56
142.25
142.79
150.60
161.91
191.33
NH2
O
NH2
O
S21
1H, 13C spectra of 3b
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
1.00
2.00
3.02
0.97
3.06
1.98
0.97
1.00
1.76
5.31
6.78
6.79
6.79
6.79
6.80
6.81
6.81
6.94
6.95
6.96
6.96
6.96
6.97
6.98
6.98
6.98
6.99
7.00
7.00
7.11
7.11
7.18
7.19
7.19
7.20
7.20
7.21
7.22
7.22
7.23
7.24
7.24
7.25
7.25
7.26
7.27
7.27
7.28
7.37
7.38
7.38
7.39
7.39
7.40
7.40
7.48
7.49
7.50
7.51
8.06
8.08
8.71
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.38
39.59
39.79
40.00
40.21
40.42
40.63
52.53
110.81
123.70
125.03
126.54
127.19
127.56
127.82
128.00
128.49
129.58
135.36
135.56
141.48
142.57
152.43
160.62
191.40
NH2
OCl
NH2
OCl
S22
1H, 13C spectra of 3c
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
1.00
2.00
3.04
4.00
1.98
0.98
0.99
1.90
5.31
6.79
6.79
6.80
6.80
6.81
6.81
6.95
6.96
6.96
6.97
6.97
6.98
6.98
6.99
7.00
7.19
7.20
7.21
7.22
7.23
7.24
7.24
7.25
7.25
7.37
7.37
7.38
7.38
7.39
7.39
7.62
7.62
7.64
7.64
7.99
8.01
8.70
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.39
39.60
39.81
40.01
40.22
40.43
40.64
52.53
110.69
123.97
124.12
126.55
127.18
127.57
127.93
128.00
128.50
129.59
130.62
135.92
141.44
142.56
152.61
160.67
191.42
NH2
OBr
NH2
OBr
S23
1H, 13C spectra of 3d
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
2.99
1.00
1.98
4.04
4.04
2.00
1.00
1.84
2.28
5.21
6.74
6.75
6.75
6.76
6.77
6.77
6.77
6.89
6.90
6.91
6.91
6.92
6.93
6.93
6.94
6.94
6.96
6.96
6.97
6.98
6.98
7.17
7.18
7.18
7.19
7.20
7.21
7.22
7.22
7.23
7.23
7.24
7.25
7.25
7.26
7.35
7.35
7.36
7.37
7.37
7.37
7.91
7.93
8.69
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
21.83
39.38
39.59
39.80
40.01
40.22
40.42
40.63
52.49
110.54
121.83
125.48
126.19
127.19
127.62
127.92
128.31
128.35
129.31
133.98
140.85
142.45
142.88
151.00
162.17
191.01
NH2
O
NH2
O
S24
1H, 13C spectra of 3e
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
3.03
1.00
1.01
1.98
4.07
3.01
1.95
0.94
0.96
3.70
5.20
6.61
6.62
6.74
6.75
6.76
6.76
6.77
6.77
6.78
6.90
6.91
6.91
6.91
6.92
6.93
6.94
6.94
6.95
6.95
6.96
6.97
6.98
6.98
6.99
6.99
7.01
7.01
7.17
7.17
7.18
7.19
7.19
7.20
7.21
7.21
7.22
7.22
7.23
7.24
7.34
7.34
7.35
7.35
7.36
7.36
7.95
7.97
8.45
8.91
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.37
39.58
39.79
40.00
40.21
40.41
40.62
52.54
55.89
110.15
110.25
113.84
123.38
126.23
127.17
127.59
127.91
128.32
129.11
129.22
142.55
142.99
153.10
162.13
162.28
190.38
NH2
OMeO
NH2
OMeO
S25
1H, 13C spectra of 3f
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
2.97
1.00
1.99
4.06
4.05
2.04
0.99
1.96
2.37
5.21
6.73
6.73
6.74
6.74
6.75
6.76
6.88
6.89
6.89
6.90
6.91
6.91
6.92
6.92
6.93
6.94
6.95
6.96
6.96
6.97
6.99
7.17
7.18
7.19
7.20
7.20
7.21
7.21
7.22
7.23
7.23
7.24
7.25
7.25
7.26
7.26
7.27
7.36
7.37
7.37
7.38
7.38
7.39
7.86
8.68
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
21.52
39.38
39.59
39.79
40.00
40.21
40.42
40.63
52.29
111.18
122.19
124.81
126.15
127.23
127.53
127.94
128.27
129.38
131.73
136.69
136.75
142.47
142.81
148.02
162.05
191.24
NH2
O
NH2
O
S26
1H, 13C spectra of 3g
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
3.04
1.00
1.97
5.04
3.09
2.01
1.00
1.91
3.81
5.19
6.72
6.73
6.73
6.74
6.74
6.75
6.75
6.89
6.90
6.91
6.92
6.92
6.93
6.94
6.94
6.95
6.96
6.96
6.97
6.99
7.18
7.18
7.18
7.20
7.20
7.21
7.22
7.23
7.23
7.23
7.24
7.25
7.27
7.36
7.36
7.37
7.37
7.38
7.38
7.69
7.70
8.66
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.37
39.58
39.79
40.00
40.21
40.42
40.63
51.96
55.89
106.28
111.78
117.88
125.76
126.12
127.25
127.48
127.93
128.27
129.39
137.81
142.52
142.79
142.95
159.29
161.88
191.20
NH2
O
MeO
NH2
O
MeO
S27
1H, 13C, 19F spectraspectra of 3h
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
1.00
3.96
1.00
2.98
3.93
0.97
1.99
5.29
6.74
6.76
6.78
7.08
7.09
7.10
7.11
7.11
7.20
7.21
7.21
7.22
7.23
7.24
7.25
7.25
7.26
7.26
7.27
7.28
7.28
7.29
7.37
7.37
7.39
7.39
7.39
7.40
7.41
7.41
7.42
7.42
7.44
7.44
7.45
8.01
8.02
8.03
8.04
8.05
8.06
8.07
8.73
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.37
39.58
39.79
39.99
40.20
40.41
40.62
51.78
110.77
114.89
115.10
122.06
125.05
127.15
127.55
128.01
129.27
129.35
129.45
130.90
136.51
138.32
138.35
142.80
150.46
159.57
161.85
161.97
191.35
NH2
O
F
NH2
O
F
S28
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010
f1 (ppm)
-117.28
-117.26
-117.25
-117.23
-117.21
1H, 13C spectra of 3i
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
1.00
1.98
2.00
1.03
3.07
4.05
1.02
1.93
5.31
6.76
6.76
6.77
6.78
6.78
6.79
6.99
7.00
7.00
7.01
7.02
7.02
7.08
7.09
7.10
7.11
7.11
7.21
7.21
7.22
7.23
7.24
7.25
7.26
7.26
7.27
7.27
7.28
7.29
7.30
7.30
7.30
7.38
7.39
7.39
7.40
7.40
7.41
7.41
7.42
7.42
7.43
7.44
7.45
7.45
7.46
8.02
8.03
8.03
8.04
8.05
8.05
8.07
8.72
NH2
O
F
NH2
O
Cl
S29
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.38
39.59
39.80
40.01
40.22
40.42
40.63
51.85
110.48
122.10
125.05
127.20
127.63
128.05
128.27
129.40
129.54
130.61
130.95
136.54
141.44
142.72
150.16
161.96
191.19
1H, 13C spectra of 3j
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
1.00
2.02
0.99
3.01
4.00
1.97
0.99
1.99
5.48
7.01
7.02
7.04
7.11
7.13
7.19
7.20
7.22
7.22
7.23
7.24
7.25
7.25
7.26
7.27
7.27
7.28
7.28
7.37
7.38
7.39
7.40
7.41
7.42
7.43
7.44
7.44
7.46
7.46
7.48
7.83
7.83
7.84
7.85
8.08
8.10
8.10
8.79
NH2
O
Cl
NH2
O
NO2
S30
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.38
39.59
39.80
40.01
40.22
40.42
40.63
52.12
110.28
122.35
123.56
125.15
127.11
127.97
128.15
128.90
129.59
131.15
136.72
142.62
146.04
149.35
151.13
162.13
191.13
1H, 13C spectra of 3k
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
2.97
1.00
1.99
1.97
1.05
3.02
4.22
1.07
1.96
2.08
5.26
6.66
6.66
6.67
6.68
6.77
6.79
7.08
7.09
7.09
7.10
7.10
7.10
7.20
7.20
7.21
7.22
7.22
7.23
7.24
7.24
7.24
7.25
7.25
7.25
7.26
7.26
7.27
7.28
7.29
7.29
7.29
7.35
7.35
7.37
7.37
7.38
7.38
7.39
7.40
7.40
7.41
7.41
7.42
7.43
7.43
7.43
7.44
8.00
8.01
8.01
8.02
8.03
8.68
NH2
O
NO2
NH2
O
S31
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
20.96
39.36
39.57
39.78
39.99
40.20
40.41
40.61
52.30
110.73
121.90
125.05
127.35
127.40
127.54
127.98
128.98
129.54
130.75
135.05
136.47
139.18
142.73
150.77
161.91
191.19
1H, 13C spectra of 3l
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
2.98
1.00
2.00
1.01
1.02
1.05
3.07
4.02
0.99
1.77
2.03
5.21
6.53
6.53
6.54
6.56
6.72
6.74
6.83
6.85
6.87
7.10
7.11
7.12
7.12
7.20
7.20
7.22
7.22
7.23
7.24
7.25
7.25
7.25
7.27
7.36
7.36
7.37
7.38
7.38
7.39
7.40
7.40
7.41
7.41
8.03
8.03
8.04
8.05
8.05
8.69
NH2
O
NH2
O
S32
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
21.31
39.60
39.81
40.02
40.23
40.44
52.60
110.93
121.95
124.77
125.09
126.91
127.21
127.42
127.94
128.19
128.25
129.34
130.77
136.66
137.14
142.10
142.87
150.59
161.75
191.42
1H, 13C spectra of 3m
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
2.89
1.00
1.95
0.97
0.98
1.00
3.08
3.98
0.97
1.76
3.55
5.26
6.31
6.31
6.32
6.33
6.33
6.34
6.37
6.38
6.38
6.38
6.48
6.48
6.49
6.49
6.50
6.50
6.51
6.51
6.86
6.88
6.90
7.13
7.14
7.15
7.15
7.15
7.16
7.21
7.21
7.21
7.23
7.23
7.24
7.24
7.25
7.25
7.26
7.26
7.27
7.27
7.28
7.29
7.29
7.29
7.37
7.37
7.39
7.39
7.39
7.40
7.40
7.41
7.41
7.42
7.42
7.43
7.43
8.01
8.02
8.02
8.03
8.04
8.69
NH2
O
NH2
O
OMe
S33
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.35
39.56
39.77
39.98
40.19
40.40
40.61
52.61
55.17
110.57
111.68
113.63
119.58
121.94
125.03
127.30
127.47
127.98
129.36
129.49
130.80
136.53
142.77
143.91
150.38
159.20
161.88
191.25
1H, 13C spectra of 3n
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
1.00
6.09
1.95
2.05
0.99
0.98
1.00
1.94
5.47
7.12
7.12
7.14
7.14
7.14
7.15
7.15
7.17
7.17
7.19
7.20
7.21
7.21
7.22
7.24
7.26
7.28
7.32
7.33
7.34
7.34
7.35
7.41
7.41
7.42
7.43
7.44
7.45
7.45
7.46
7.47
7.48
7.49
7.54
7.55
7.55
7.79
7.79
7.79
7.80
7.81
7.81
7.82
7.82
8.08
8.08
8.08
8.10
8.10
8.77
NH2
O
OMe
NH2
O
NO2
S34
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.38
39.59
39.80
40.01
40.22
40.43
40.64
51.77
110.48
121.37
122.32
122.59
125.23
126.97
127.97
128.07
129.42
129.89
131.19
134.43
136.77
142.74
144.92
147.59
149.57
161.98
191.29
1H, 13C, 19F spectraspectra of 3o
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.00
1.98
5.05
0.99
4.08
1.00
1.99
5.29
6.78
6.79
6.79
6.80
6.81
6.81
6.84
6.92
6.92
6.93
6.93
6.94
6.95
6.95
6.96
6.96
6.97
6.99
6.99
7.01
7.03
7.03
7.04
7.09
7.10
7.11
7.12
7.12
7.37
7.37
7.39
7.39
7.39
7.40
7.41
7.41
7.42
7.43
7.44
7.45
7.46
7.46
7.47
7.48
7.49
7.50
7.50
8.02
8.03
8.04
8.04
8.05
8.06
8.07
8.75
NH2
O
NO2
NH2
O
F
S35
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.38
39.59
39.79
40.00
40.21
40.42
40.63
52.60
110.60
114.67
114.89
122.04
125.06
126.35
127.48
127.60
128.40
129.74
129.82
130.90
136.45
139.26
139.29
142.15
150.60
161.55
162.19
163.99
189.86
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010
f1 (ppm)
-111.99
-111.98
-111.97
NH2
O
F
NH2
O
F
S36
1H, 13C spectra of 3p
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
1.00
2.00
2.97
1.05
1.98
3.98
1.01
1.84
5.28
6.79
6.80
6.80
6.81
6.82
6.86
6.93
6.94
6.94
6.95
6.96
6.96
6.97
6.97
6.98
6.99
7.00
7.01
7.02
7.10
7.11
7.12
7.12
7.24
7.24
7.26
7.38
7.39
7.40
7.40
7.42
7.43
7.44
8.03
8.04
8.04
8.05
8.05
8.06
8.07
8.77
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.38
39.59
39.80
40.01
40.22
40.43
40.64
52.47
110.54
122.10
125.07
126.39
127.51
127.61
128.00
128.42
129.23
130.99
134.06
136.35
141.43
142.11
150.62
162.41
189.65
NH2
O
Cl
NH2
O
Cl
S37
1H, 13C spectra of 3q
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
2.99
1.00
2.00
5.02
1.00
4.00
0.99
1.83
2.24
5.33
6.83
6.83
6.83
6.84
6.85
6.85
6.94
6.95
6.96
6.96
6.97
6.98
6.99
6.99
7.00
7.01
7.01
7.03
7.11
7.11
7.12
7.13
7.36
7.36
7.38
7.38
7.39
7.40
7.40
7.40
8.01
8.01
8.01
8.02
8.03
8.67
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
21.36
39.39
39.59
39.80
40.01
40.22
40.43
40.64
52.68
110.63
121.88
125.01
126.31
127.39
127.54
127.56
128.39
128.51
130.69
136.55
139.10
139.94
142.42
150.49
161.81
190.91
NH2
O
NH2
O
S38
1H, 13C spectra of 3r
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
2.94
1.00
1.97
1.96
2.98
0.97
1.99
1.95
0.97
1.75
3.72
5.38
6.74
6.75
6.76
6.77
6.77
6.78
6.86
6.87
6.87
6.88
6.88
6.89
6.89
6.93
6.93
6.94
6.94
6.95
6.96
6.96
6.97
6.97
6.99
7.00
7.01
7.01
7.03
7.03
7.03
7.11
7.12
7.13
7.13
7.14
7.14
7.14
7.15
7.36
7.36
7.37
7.38
7.38
7.39
7.40
7.40
7.40
7.42
7.42
7.49
7.49
7.50
7.51
7.52
7.52
7.98
7.99
8.00
8.00
8.01
8.02
8.63
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.38
39.59
39.80
40.01
40.21
40.42
40.63
52.77
55.56
110.50
113.24
121.79
124.96
126.35
127.37
127.54
128.44
129.57
130.59
135.12
136.59
142.46
150.40
160.51
161.68
190.03
NH2
O
OMe
NH2
O
OMe
S39
1H, 13C spectra of 3s
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
2.99
1.01
1.00
1.00
5.95
2.02
1.03
1.97
0.18
0.19
0.21
1.08
1.09
1.10
1.11
1.12
1.13
1.13
1.14
1.16
1.64
1.65
1.66
1.66
1.67
1.68
1.68
1.69
1.70
1.70
1.71
1.72
4.22
4.23
4.23
4.24
7.39
7.40
7.41
7.42
7.43
7.43
7.44
7.45
7.45
7.46
7.46
7.47
7.47
7.48
7.49
7.51
7.60
7.60
7.61
7.62
7.62
7.63
7.63
7.64
7.64
7.97
7.98
8.61
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
8.12
23.98
39.48
39.65
39.81
39.90
39.98
40.07
40.15
40.24
40.31
40.40
40.48
46.35
108.26
121.77
124.20
127.13
127.24
128.61
129.90
130.43
137.57
143.34
149.37
161.61
190.71
NH2O
NH2O
S40
1H, 13C spectra of 3t
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
2.99
1.00
4.03
2.03
2.07
1.05
1.88
1.76
4.96
7.11
7.12
7.12
7.13
7.13
7.13
7.14
7.14
7.15
7.15
7.16
7.16
7.17
7.19
7.20
7.21
7.21
7.25
7.27
7.27
7.28
7.29
7.29
7.29
7.35
7.36
7.37
7.37
7.38
7.93
7.94
7.94
7.95
7.95
7.95
8.45
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
28.71
39.60
39.81
40.02
40.23
40.44
52.21
111.25
121.85
125.11
126.95
127.39
127.75
129.12
130.43
136.89
142.75
149.84
159.12
193.69
NH2
O
NH2
O
S41
1H, 13C spectra of 3u
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
1.00
5.02
1.00
1.99
2.95
1.00
0.95
1.00
1.99
1.93
5.51
6.81
6.82
6.82
6.83
6.84
6.85
6.86
6.87
6.88
6.89
6.89
7.12
7.13
7.14
7.38
7.38
7.40
7.40
7.41
7.41
7.42
7.43
7.43
7.44
7.45
7.49
7.49
7.50
7.51
7.52
7.52
7.54
7.55
7.72
7.74
7.82
7.83
7.84
7.84
7.85
7.91
7.92
7.93
7.93
7.94
7.95
8.06
8.07
8.08
8.08
8.11
8.11
8.84
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.37
39.58
39.79
40.00
40.21
40.42
40.63
52.72
110.87
122.02
125.07
125.17
126.28
126.59
127.20
127.34
127.47
127.50
127.57
127.83
128.35
129.06
130.87
132.44
133.48
136.46
139.73
142.46
150.65
162.30
190.66
NH2
O
NH2
O
S42
1H, 13C spectra of 3v
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
1.00
1.98
2.01
2.08
2.00
1.02
0.95
0.97
5.14
7.12
7.14
7.14
7.19
7.20
7.21
7.21
7.22
7.25
7.27
7.27
7.28
7.29
7.45
7.45
7.47
7.47
7.49
7.49
7.50
7.50
7.51
7.51
7.53
8.15
8.16
8.16
8.17
8.18
8.18
8.99
9.38
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
39.39
39.59
39.80
40.01
40.22
40.43
40.64
50.62
122.42
123.37
125.50
127.17
127.66
128.22
128.95
132.63
134.21
140.38
147.08
156.11
NH2
NO2
NH2
NO2
S43
1H, 13C spectra of 4
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
f1 (ppm)
1.00
2.01
16.10
1.00
5.05
6.92
6.93
6.93
6.94
6.95
6.95
7.12
7.14
7.16
7.17
7.17
7.18
7.19
7.20
7.20
7.21
7.22
7.22
7.24
7.25
7.27
7.29
7.30
7.31
7.32
7.32
7.33
7.34
7.35
7.36
7.38
7.39
7.39
7.40
7.41
7.42
7.42
7.43
7.92
7.93
7.94
7.94
7.94
7.95
7.96
7.96
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
47.78
76.73
76.77
77.05
77.08
77.36
77.40
120.37
125.44
125.98
126.90
127.16
127.55
127.67
127.95
128.16
128.20
128.60
128.91
129.11
129.91
130.02
133.64
137.89
140.77
141.65
153.37
159.70
NN Ph
Ph
Ph
NN Ph
Ph
Ph
S44
8. HRMS spectra of the intermediate E
NH2O
PhPh
EtO
H
C24H23NO2Calcd (M + H) + 358.1802Found(M + H) + 358.1803