The Journal of Organic Chemistry
Article
20.9, 20.6, 20.5. HRMS (ESI) m/z: [M + H]+ calcd for C33H27N2O3
499.2016; found 499.2020.
CH3CN at 20 °C for 48 h under an air atmosphere. After the
completeness of the reaction, the solvent was removed, and the crude
product was carried out by chromatography (silica gel, petroleum:-
EtOAc = 10:1) to afford 4f as a white solid (430 mg, 30%).
(1-Phenyl-1H-pyrazole-3,4,5-triyl)tris(m-tolylmethanone)
(3g). Purified by column chromatography (silica gel, petroleum:-
1
EtOAc = 8:1), white solid (85 mg, 51%), mp 150.2−152.1 °C. H
(1-(p-Tolyl)-1H-pyrazole-3,4-diyl)bis(phenylmethanone)
NMR (400 MHz, CDCl3) δ 7.97 (d, J = 7.6 Hz, 1H), 7.87 (s, 1H),
7.53−7.46 (m, 4H), 7.42−7.36 (m, 6H), 7.34−7.38 (m, 2H), 7.25−
7.14 (m, 3H), 2.36 (s, 3H), 2.22 (s, 3H), 2.21 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3) δ 189.5, 187.3, 186.7, 150.0, 141.4, 138.8, 138.6,
138.1, 138.1, 137.9, 136.4, 136.3, 135.0, 134.2, 133.7, 130.6, 129.9,
129.3, 129.0, 128.6, 128.2, 127.8, 126.9, 126.8, 126.2, 124.5, 21.3,
21.0, 21.0. HRMS (ESI) m/z: [M + H]+ calcd for C33H27N2O3
499.2016; found 499.2010.
(4a). Purified by column chromatography (silica gel, petroleum:-
1
EtOAc = 8:1), white solid (98 mg, 80%), mp 99.3−101.0 °C. H
NMR (400 MHz, CDCl3) δ 8.30 (s, 1H), 8.14−7.99 (m, 2H), 7.89−
7.76 (m, 2H), 7.67 (d, J = 8.4 Hz, 2H), 7.60−7.48 (m, 2H), 7.48−
7.35 (m, 4H), 7.31 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3) δ 189.2, 188.1, 151.2, 138.3, 138.2, 136.7, 136.7,
133.2, 132.9, 130.2, 130.2, 130.1, 129.1, 128.5, 128.3, 125.0, 119.9,
21.0. HRMS (ESI) m/z: [M + H]+ calcd for C24H19N2O2 367.1441;
found 367.1438.
(1-Phenyl-1H-pyrazole-3,4,5-triyl)tris(p-tolylmethanone)
(3h). Purified by column chromatography (silica gel, petroleum:-
(1-(2-Fluorophenyl)-1H-pyrazole-3, 4-diyl)bis-
(phenylmethanone) (4b). Purified by column chromatography
(silica gel, petroleum:EtOAc = 8:1), white solid (76 mg, 62%), mp
1
EtOAc = 8:1), white solid (85 mg, 51%), mp 203.2−204.9 °C. H
NMR (400 MHz, CDCl3) δ 8.11 (d, J = 8.0 Hz, 2H), 7.61 (d, J = 8.0
Hz, 2H), 7.57 (d, J = 8.0 Hz, 2H), 7.53−7.47 (m, 2H), 7.39−7.35 (m,
3H), 7.26−7.23 (m, 2H), 7.10 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 8.0
Hz, 2H), 2.41 (s, 3H), 2.33 (s, 3H), 2.32 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3) δ 189.2, 186.4, 186.4, 149.9, 145.6, 144.3, 143.9,
141.3, 138.9, 135.4, 133.9, 133.8, 130.7, 129.8, 129.4, 129.3, 129.2,
129.1, 129.0, 129.0, 126.7, 124.4, 21.8, 21.8, 21.7. HRMS (ESI) m/z:
[M + H]+ calcd for C33H27N2O3 499.2016; found 499.2021.
(1-(4-Methoxyphenyl)-1H-pyrazole-3,4,5-triyl)tris-
(phenylmethanone) (3i). Purified by column chromatography
(silica gel, petroleum:EtOAc = 6:1), white solid (104 mg, 64%),
mp 119.3−121.0 °C. 1H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 7.2
Hz, 2H), 7.69−7.61 (m, 4H), 7.57 (t, J = 7.4 Hz, 1H), 7.50−7.40 (m,
6H), 7.31−7.28 (m, 2H), 7.27−7.24 (m, 2H), 6.89 (d, J = 9.2 Hz,
2H), 3.79 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 189.5, 186.8,
186.7, 160.0, 149.5, 141.3, 137.8, 136.3, 136.3, 134.3, 133.7, 133.0,
131.8, 130.5, 129.5, 128.9, 128.6, 128.3, 126.5, 125.9, 114.4, 55.5.
HRMS (ESI) m/z: [M + H]+ calcd for C31H23N2O4 487.1652; found
487.1645.
1
118.3−119.5 °C. H NMR (400 MHz, CDCl3) δ 8.41 (s, 1H), 8.08
(d, J = 7.2 Hz, 2H), 7.98 (t, J = 7.4 Hz, 1H), 7.84 (d, J = 7.2 Hz, 2H),
7.65−7.52 (m, 2H), 7.49−7.36 (m, 5H), 7.34−7.25 (m, 2H).
13C{1H} NMR (100 MHz, CDCl3) δ 188.8, 188.2, 154.0 (d, J = 250.3
Hz), 151.5, 138.2, 136.7, 134.3 (d, J = 10.4 Hz), 133.5, 133.1, 130.4,
129.6 (d, J = 7.9 Hz), 129.2, 128.6, 128.5, 127.3 (d, J = 9.5 Hz), 125.4
(d, J = 3.8 Hz), 125.0, 124.9, 117.2 (d, J = 20.2 Hz). HRMS (ESI) m/
z: [M + H]+ calcd for C23H16FN2O2 371.1190; found 371.1183.
(1-(3-Fluorophenyl)-1H-pyrazole-3, 4-diyl)bis-
(phenylmethanone) (4c). Purified by column chromatography
(silica gel, petroleum:EtOAc = 8:1), white solid (79 mg, 64%), mp
1
105.6−107.1 °C. H NMR (400 MHz, DMSO-d6) δ 9.24 (s, 1H),
8.02 (d, J = 7.6 Hz, 2H), 7.97−7.85 (m, 4H), 7.73−7.66 (m, 2H),
7.64−7.50 (m, 5H), 7.31 (t, J = 8.2 Hz, 1H). 13C{1H} NMR (100
MHz, DMSO-d6) δ 193.4, 193.1, 167.7 (d, J = 244.4 Hz), 156.6,
145.3 (d, J = 10.6 Hz), 142.5, 141.3, 139.1, 138.5, 136.8 (d, J = 9.7
Hz), 135.0, 134.4, 134.0 (d, J = 3.5 Hz), 129.2, 120.9, 119.9 (d, J =
21.0 Hz), 112.5 (d, J = 26.3 Hz), 112.3 (d, J = 3.5 Hz). HRMS (ESI)
m/z: [M + H]+ calcd for C23H16FN2O2 371.1190; found 371.1192.
(1-(4-Fluorophenyl)-1H-pyrazole-3, 4-diyl)bis-
(phenylmethanone) (4d). Purified by column chromatography
(silica gel, petroleum:EtOAc = 8:1), a white solid (80 mg, 65%), mp
92.3−94.1 °C. 1H NMR (400 MHz, CDCl3) δ 8.29 (s, 1H), 8.06 (d, J
= 7.2 Hz, 2H), 7.81 (m, 4H), 7.64−7.48 (m, 2H), 7.46−7.32 (m,
4H), 7.30−6.98 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3) δ 189.0,
188.0, 162.1 (d, J = 248.6 Hz), 151.6, 138.1, 136.6, 135.3 (d, J = 2.8
Hz), 133.4, 133.0, 130.2, 129.1, 128.5, 128.4, 125.3, 121.9 (d, J = 8.5
Hz), 116.7 (d, J = 23.3 Hz). HRMS (ESI) m/z: [M + H]+ calcd for
C23H16FN2O2 371.1190; found 371.1196.
(1-Phenyl-1H-pyrazole-3,4,5-triyl)tris(naphthalen-2-ylme-
thanone) (3j). Purified by column chromatography (silica gel,
petroleum:EtOAc = 8:1), light pink solid (51 mg, 25%), mp 183.9−
185.8 °C. 1H NMR (400 MHz, CDCl3) δ 8.87 (s, 1H), 8.25 (s, 1H),
8.13 (d, J = 9.2 Hz, 2H), 7.94 (d, J = 8.0 Hz, 1H), 7.85 (t, J = 8.2 Hz,
2H), 7.78−7.70 (m, 4H), 7.69−7.65 (m, 2H), 7.62−7.58 (m, 5H),
7.56−7.50 (m, 3H), 7.46−7.35 (m, 5H). 13C{1H} NMR (100 MHz,
CDCl3) δ 189.6, 186.9, 186.7, 150.3, 141.6, 139.0, 136.2, 135.9, 135.7,
135.5, 133.9, 133.8, 133.3, 133.0, 132.5, 132.3, 132.2, 131.4, 130.1,
129.8, 129.6, 129.5, 129.4, 129.3, 129.0, 128.9, 128.6, 128.5, 128.4,
127.9, 127.8, 127.3, 127.2, 126.8, 126.7, 125.5, 124.6, 124.2, 123.9.
HRMS (ESI) m/z: [M + H]+ calcd for C42H27N2O3 607.2016; found
607.2013.
(1-(4-Fluorophenyl)-1H-pyrazole-3,4,5-triyl)tris-
(phenylmethanone) (3k). Purified by column chromatography
(silica gel, petroleum:EtOAc = 8:1), white solid (88 mg, 56%), mp
163.9−164.8 °C. 1H NMR (400 MHz, CDCl3) δ 8.17 (d, J = 6.0 Hz,
2H), 7.66−7.57 (m, 5H), 7.50−7.45 (m, 6H), 7.35−7.26 (m, 4H),
7.14−7.06 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3) δ 189.4,
186.6, 186.4, 162.6 (d, J = 250.2 Hz), 149.8, 141.3, 137.7, 136.2,
136.1, 134.9 (d, J = 3.1 Hz), 134.5, 133.5, 133.2, 130.5, 129.5, 128.9,
128.7, 128.4, 126.9, 126.6 (d, J = 8.9 Hz), 116.4 (d, J = 23.2 Hz).
HRMS (ESI) m/z: [M + H]+ calcd for C30H20FN2O3 475.1452;
found 475.1460.
(1-(4-Chlorophenyl)-1H-pyrazole-3, 4-diyl)bis-
(phenylmethanone) (4e). Purified by column chromatography
(silica gel, petroleum:EtOAc = 10:1), white solid (93 mg,72%), mp
1
105.6−106.8 °C. H NMR (400 MHz, CDCl3) δ 8.32 (s, 1H), 8.06
(d, J = 7.6 Hz, 2H), 7.80 (d, J = 7.6 Hz, 2H), 7.74 (d, J = 8.4 Hz, 2H),
7.59−7.45 (m, 5H), 7.44−7.38 (m, 3H). 13C{1H} NMR (100 MHz,
CDCl3) δ 188.9, 187.8, 151.6, 138.0, 137.5, 136.5, 133.9, 133.4, 133.0,
130.2, 130.0, 129.9, 129.0, 128.5, 128.3, 125.4, 121.0. HRMS (ESI)
m/z: [M + H]+ calcd for C23H16ClN2O2 387.0895; found 387.0901.
(1-(4-Bromophenyl)-1H-pyrazole-3, 4-diyl)bis-
(phenylmethanone) (4f). Purified by column chromatography
(silica gel, petroleum:EtOAc = 10:1), white solid (143 mg, 79% for 1
mmol scale reaction; 430 mg, 30% for 10 mmol scale reaction), mp
1
Typical Procedure for Synthesis of Product 4. A mixture of
sulfur ylide (1.0 mmol, 2.0 equiv), aryl diazonium tetrafluoroborate
(0.5 mmol, 1.0 equiv), and NaOH (1.5 mmol, 3.0 equiv) was stirred
in 10 mL of CH3CN at 20 °C for 48 h under an air atmosphere. After
the completeness of the reaction, the solvent was removed, and the
crude product was carried out by chromatography to afford 4a−4q as
desired products.
115.6−117.0 °C. H NMR (400 MHz, CDCl3) δ 8.32 (s, 1H), 8.06
(d, J = 7.2 Hz, 2H), 7.80 (d, J = 7.2 Hz, 2H), 7.71−7.62 (m, 4H),
7.60−7.56 (m, 1H), 7.55−7.51 (m, 1H), 7.44 (t, J = 7.6 Hz, 2H),
7.39 (t, J = 7.6 Hz, 2H). 13C{1H} NMR (100 MHz, CDCl3) δ 188.9,
187.8, 151.7, 138.0, 138.0, 136.5, 133.4, 133.0, 132.8, 130.2, 129.9,
129.0, 128.5, 128.3, 125.4, 121.7, 121.3. HRMS (ESI) m/z: [M + H]+
calcd for C23H16BrN2O2 431.0390; found 431.0397.
Typical procedure for scale-up synthesis of product 4f. A mixture of
2-(dimethyl-l4-sulfanylidene)-1-phenylethan-1-one (10 mmol, 2.0
equiv), 4-bromobenzenediazonium tetrafluoroborate (5 mmol, 1.0
equiv), and NaOH (15 mmol, 3.0 equiv) were stirred in 80 mL of
4-(3,4-Dibenzoyl-1H-pyrazol-1-yl)benzonitrile (4g). Purified
by column chromatography (silica gel, petroleum:EtOAc = 8:1),
white solid (88 mg, 70%), mp 118.9−120.5 °C. 1H NMR (400 MHz,
CDCl3) δ 8.41 (s, 1H), 8.06 (d, J = 7.6 Hz, 2H), 7.95 (d, J = 8.4 Hz,
9003
J. Org. Chem. 2021, 86, 8997−9006