The Journal of Organic Chemistry
Article
130.9 Hz), 128.9, 128.6, 128.4 (d, J = 12.8 Hz), 124.1, 123.9, 123.7,
123.3, 122.5, 121.0, 116.4, 108.6, 99.8, 79.2, 30.6. 31P NMR (121
MHz, chloroform-d) δ 24.37. HR-MS (ESI) m/z: [M + H]+ Calcd for
C30H24N3OP 474.1730; Found 474.1727.
(d, J = 3.4 Hz, 4H). 13C{1H} NMR (75 MHz, chloroform-d) δ 150.9
(d, J = 3.0 Hz), 147.8 (d, J = 19.7 Hz), 143.9 (d, J = 16.8 Hz), 135.6,
132.2, 131.7, 128.7, 128.5, 128.4, 128,4, 127.9 (d, J = 10.9 Hz), 125.1,
124.5 (d, J = 135.3 Hz), 123.0, 122.2, 111.7 (d, J = 12.6 Hz), 108.6
(d, J = 16.3 Hz), 101.6, 94.7, 86.7. 31P NMR (121 MHz, chloroform-
d) δ 24.53. HR-MS (ESI) m/z: [M + H]+ Calcd for C29H22N2O5P
509.1261; Found 509.1264.
Compound 1n. P,P-Diphenyl-N′-((2-(phenylethynyl)benzofuran-
3-yl)methylene)phosphinic hydrazide. Yield: 71% (0.89 mmol, 408
mg). Rf = 0.31 (cyclohexane/EA, 3:7). Aspect: Yellow solid.1H NMR
(300 MHz, chloroform-d) δ 8.88 (s, 1H), 8.35 (s, 1H), 7.92 (dd, J =
12.1, 7.5 Hz, 4H), 7.69−7.57 (m, 2H), 7.50 (t, J = 7.2 Hz, 2H), 7.45−
7.29 (m, 8H), 7.24 (s, 2H), 7.06−6.88 (m, 1H). 13C{1H} NMR (75
MHz, chloroform-d) δ 154.5, 139.5 (d, J = 18.1 Hz), 138.9, 132.5 (d,
J = 9.7 Hz), 132.2 (d, J = 2.6 Hz), 131.8, 130.5 (d, J = 133.8 Hz),
129.4, 128.7, 128.7, 128.5, 126.2, 124.4, 123.5 (d, J = 16.3 Hz), 121.8,
121.4, 110.6, 99.9, 78.4. 31P NMR (121 MHz, chloroform-d) δ 24.98.
HR-MS (ESI) m/z: [M + H]+ Calcd for C29H21N2O2P 461.1413;
Found 461.1409.
Compound 1t. P,P-Bis(4-fluorophenyl)-N′-(2-(phenylethynyl)-
benzylidene)phosphinic hydrazide. Yield: 67% (1 mmol, 460 mg).
1
Rf = 0.53 (cyclohexane/EA, 3:7). Aspect: Beige solid. H NMR (400
MHz, chloroform-d) δ 8.44 (s, 1H), 7.86 (dddd, J = 11.3, 8.4, 5.1, 2.3
Hz, 4H), 7.70 (dd, J = 7.7, 1.7 Hz, 1H), 7.61 (d, J = 18.3 Hz, 1H),
7.54−7.49 (m, 2H), 7.46 (dd, J = 7.6, 1.6 Hz, 1H), 7.34−7.26 (m,
3H), 7.26−7.20 (m, 2H), 7.11 (td, J = 8.8, 2.5 Hz, 4H). 13C{1H}
NMR (101 MHz, chloroform-d) δ 165.5 (dd, J = 254.0, 3.4 Hz),
144.5 (d, J = 16.4 Hz), 135.1, 135.0 (dd, J = 11.3, 8.9 Hz), 132.5,
131.7, 129.3, 128.8, 128.6, 128.6, 127.0 (dd, J = 134.0, 3.4 Hz), 125.3,
122.9, 122.6, 116.1 (dd, J = 21.5, 14.2 Hz), 94.9, 86.5. 31P NMR (162
MHz, chloroform-d) δ 22.39. 19F NMR (376 MHz, Chloroform-d) δ
−105.97. HR-MS (ESI) m/z: [M + H]+ Calcd for C27H20F2N2OP
457.1276; Found 457.1271.
Compound 1u. P,P-Bis(4-chlorophenyl)-N′-(2-(phenylethynyl)-
benzylidene)phosphinic hydrazide. Yield: 80% (0.54 mmol, 266
mg). Rf = 0.15 (cyclohexane/EA, 3:7). Aspect: White solid. 1H NMR
(400 MHz, chloroform-d) δ 8.59 (d, J = 17.9 Hz, 1H), 8.58 (s, 1H),
7.75 (dd, J = 11.9, 8.4 Hz, 4H), 7.67 (d, J = 7.5 Hz, 1H), 7.58−7.51
(m, 2H), 7.49−7.43 (m, 1H), 7.36 (dd, J = 8.4, 2.5 Hz, 4H), 7.32−
7.16 (m, 5H). 13C{1H} NMR (101 MHz, chloroform-d) δ 144.8 (d, J
= 17.1 Hz), 139.0 (d, J = 3.5 Hz), 135.2, 133.7 (d, J = 10.8 Hz),
132.4, 131.7, 129.6 (d, J = 131.9 Hz), 129.1, 129.0 (d, J = 13.7 Hz),
128.7, 128.6, 128.5, 125.1, 123.0, 122.5, 94.9, 86.6. 31P NMR (162
MHz, chloroform-d) δ 23.41. HR-MS (ESI) m/z: [M + H]+ Calcd for
C27H20Cl2N2OP 489.0685; Found 489.0686.
Compound 1o. P,P-Diphenyl-N′-((2-(phenylethynyl)quinolin-3-
yl)methylene)phosphinic hydrazide. Yield: 76% (0.76 mmol, 241
mg). Rf = 0.48 (cyclohexane/EA, 3:7). Aspect: White solid. 1H NMR
(400 MHz, Chloroform-d) δ 8.73 (d, J = 20.6 Hz, 1H), 8.70 (s, 1H),
8.40 (s, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.95−7.86 (m, 4H), 7.69 (dd, J
= 8.3, 1.3 Hz, 2H), 7.65−7.57 (m, 2H), 7.50 (ddd, J = 7.6, 6.4, 1.4
Hz, 2H), 7.42 (qd, J = 8.2, 7.3, 2.2 Hz, 5H), 7.36−7.31 (m, 1H),
7.29−7.24 (m, 2H).13C{1H} NMR (101 MHz, chloroform-d) δ 147.6,
142.1 (d, J = 16.9 Hz), 141.6, 132.6, 132.5, 132.5 (d, J = 9.9 Hz),
132.3 (d, J = 2.7 Hz), 131.0 (d, J = 130.1 Hz), 130.7, 129.5, 128.8,
128.6 (d, J = 13.0 Hz), 128.5, 128.5, 128.3, 127.6, 127.1, 121.8, 94.9,
86.4. 31P NMR (162 MHz, chloroform-d) δ 24.1. HR-MS (ESI) m/z:
[M + H]+ Calcd for C30H23N3OP 472.1573; Found 472.1572.
Compound 1p. N′-(2-(Phenylethynyl)benzylidene)-P,P-di-p-tolyl-
phosphinic hydrazide. Yield: 58% (1.41 mmol, 634 mg). Rf = 0.43
1
(cyclohexane/EA, 3:7). Aspect: White solid. H NMR (400 MHz,
chloroform-d) δ 8.48 (s, 1H), 7.78 (m, 6H), 7.55 (dd, J = 7.2, 2.0 Hz,
2H), 7.46 (d, J = 7.2 Hz, 1H), 7.29 (d, J = 6.1 Hz, 3H), 7.27−7.17
(m, 6H), 2.37 (s, 6H).13C{1H} NMR (101 MHz, chloroform-d) δ
143.5 (d, J = 16.3 Hz), 142.6 (d, J = 2.8 Hz), 135.6, 132.4 (d, J = 10.3
Hz), 132.3, 131.7, 129.3 (d, J = 13.4 Hz), 128.8, 128.6, 128.5, 128.5,
128.2 (d, J = 131.8 Hz), 125.3, 123.0, 122.3, 94.7, 86.7, 21.7. 31P
NMR (162 MHz, chloroform-d) δ 24.5. HR-MS (ESI) m/z: [M +
H]+ Calcd for C29H25N2OP 449.1777; Found 449.1772.
Compound 1q. N′-(2-(Phenylethynyl)benzylidene)-P,P-di-o-tolyl-
phosphinic hydrazide. Yield: 83% (2 mmol, 899 mg). Rf = 0.63
(cyclohexane/EA, 3:7). Aspect: White solid.1H NMR (400 MHz,
chloroform-d) δ 8.58 (s, 1H), 8.45 (d, J = 20.4 Hz, 1H), 7.78−7.65
(m, 3H), 7.60−7.54 (m, 2H), 7.48 (dd, J = 7.6, 1.5 Hz, 1H), 7.40 (tt,
J = 7.5, 1.5 Hz, 2H), 7.23 (dddd, J = 18.9, 11.5, 9.7, 4.3 Hz, 9H), 2.50
(d, J = 1.3 Hz, 6H). 13C{1H} NMR (101 MHz, chloroform-d) δ 142.7
(d, J = 9.9 Hz), 142.6 (d, J = 16.6 Hz), 135.9, 133.5 (d, J = 11.3 Hz),
132.4, 132.2 (d, J = 2.7 Hz), 131.8, 131.6 (d, J = 12.0 Hz), 130.2 (d, J
= 124.4 Hz), 128.6, 128.5, 128.5, 128.4, 125.6 (d, J = 13.2 Hz), 125.1,
123.0, 122.3, 94.8, 86.7, 21.8 (d, J = 4.1 Hz). 31P NMR (121 MHz,
chloroform-d) δ 29.60. HR-MS (ESI) m/z: [M + H]+ Calcd for
C29H25N2OP 449.1777; Found 449.1774.
Compound 1r. N′-(2-(Phenylethynyl)benzylidene)-P,P-bis(3,4,5-
trimethoxyphenyl)phosphinic hydrazide. Yield: 73% (0.44 mmol, 267
mg). Rf = 0.13 (cyclohexane/EA, 3:7). Aspect: Yellow solid. 1H NMR
(300 MHz, chloroform-d) δ 8.65 (s, 1H), 8.49 (d, J = 16.5 Hz, 1H),
7.83 (d, J = 6.3 Hz, 1H), 7.61−7.43 (m, 3H), 7.30−7.04 (m, 9H),
3.86 (s, 6H), 3.75 (s, 12H). 13C{1H} NMR (75 MHz, chloroform-d)
δ 153.2 (d, J = 18.8 Hz), 144.1 (d, J = 16.3 Hz), 141.3, 135.4, 132.4,
131.6, 129.0, 128.5 (d, J = 12.3 Hz), 128.4, 125.7 (d, J = 131.5 Hz),
124.8, 122.8, 122.3, 109.3, 109.2, 94.9, 86.5, 60.9, 56.3. 31P NMR
(121 MHz, chloroform-d) δ 25.69. HR-MS (ESI) m/z: [M + H]+
Calcd for C33H34N2O7P 601.2098; Found 601.2083.
Compound 1v. Ethyl (E)-phenyl(2-(2-(phenylethynyl)-
benzylidene)hydrazineyl)phosphinate. Yield: 44% (0.51 mmol, 200
1
mg). Rf = 0.51 (cyclohexane/EA, 3:7). Aspect: Beige solid. H NMR
(300 MHz, chloroform-d) δ 8.48 (s, 1H), 8.28 (d, J = 23.7 Hz, 1H),
8.03−7.90 (m, 3H), 7.63−7.55 (m, 2H), 7.51 (dd, J = 6.8, 1.8 Hz,
2H), 7.47−7.39 (m, 2H), 7.36−7.27 (m, 5H), 4.34−4.19 (m, 2H),
1.39 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (75 MHz, chloroform-d) δ
143.1 (d, J = 17.5 Hz), 135.6, 132.4, 132.2 (d, J = 3.0 Hz), 131.8 (d, J
= 9.7 Hz), 131.8, 131.0, 128.9, 128.7, 128.6, 128.5, 128.4 (d, J = 14.9
Hz), 124.9, 123.0, 122.5, 95.1, 86.5, 61.5 (d, J = 6.6 Hz), 16.5 (d, J =
6.6 Hz). 31P NMR (162 MHz, chloroform-d) δ 17.89. HR-MS (ESI)
m/z: [M + H]+ Calcd for C23H22N2O2P 389.1413; Found 389.1413.
Compound 1w. N′-(2-((4-Cyanophenyl)ethynyl)benzylidene)-
P,P-diphenylphosphinic hydrazide. Yield: 76% (0.89 mmol, 395
1
mg). Rf = 0.29 (cyclohexane/EA, 3:7). Aspect: Beige solid. H NMR
(300 MHz, chloroform-d) δ 8.68 (d, J = 18.4 Hz, 1H), 8.58 (s, 1H),
7.90−7.81 (m, 4H), 7.77−7.71 (m, 1H), 7.63 (d, J = 8.3 Hz, 2H),
7.56−7.49 (m, 2H), 7.43 (m, 7H), 7.28−7.21 (m, 2H). 13C{1H}
NMR (75 MHz, Chloroform-d) δ 143.5 (d, J = 16.7 Hz), 136.1,
132.4, 132.4, 132.4 (d, J = 2.7 Hz), 132.3, 132.2 (d, J = 12.1 Hz),
131.2 (d, J = 128.6 Hz), 129.3, 128.9, 128.5, 127.9, 125.2, 121.2,
118.6, 111.6, 93.1, 91.0. 31P NMR (121 MHz, chloroform-d) δ 25.59.
HR-MS (ESI) m/z: [M + H]+ Calcd for C28H21N3OP 446.1417;
Found 446.1416.
Compound 1x. N′-(2-((3-Nitrophenyl)ethynyl)benzylidene)-P,P-
diphenylphosphinic hydrazide. Yield: 85% (0.88 mmol, 409 mg). Rf =
0.77 (EA). Aspect: Beige solid. 1H NMR (300 MHz, chloroform-d) δ
8.53 (s, 1H), 8.33 (s, 1H), 8.22 (d, J = 18.8 Hz, 1H), 8.12 (d, J = 8.3
Hz, 1H), 7.88 (dd, J = 12.4, 6.9 Hz, 5H), 7.80−7.72 (m, 1H), 7.56−
7.36 (m, 8H), 7.30−7.21 (m, 2H). 13C{1H} NMR (75 MHz,
chloroform-d) δ 148.1, 143.5 (d, J = 16.3 Hz), 137.7, 135.9, 132.6,
132.4 (d, J = 9.9 Hz), 132.3, 131.1 (d, J = 129.4 Hz), 129.5, 129.3,
129.0, 128.6 (d, J = 13.0 Hz), 126.3, 125.4, 124.8, 123.2, 121.2, 92.1,
89.2. 31P NMR (121 MHz, chloroform-d) δ 24.41. HR-MS (ESI) m/
z: [M + H]+ Calcd for C27H21FN3O3P 466.1315; Found 466.1310.
Compound 1y. N′-(5-Fluoro-2-(3-methoxyprop-1-yn-1-yl)-
benzylidene)-P,P-diphenylphosphinic hydrazide. Yield: 91% (1.9
Compound 1s. P,P-Bis(benzo[d][1,3]dioxol-5-yl)-N′-(2-
(phenylethynyl)benzylidene)phosphinic hydrazide. Yield: 67% (0.79
mmol, 400 mg). Rf = 0.57 (cyclohexane/EA, 3:7). Aspect: White
1
solid. H NMR (300 MHz, chloroform-d) δ 8.42 (s, 1H), 7.90−7.72
(m, 1H), 7.61−7.53 (m, 2H), 7.49 (d, J = 8.5 Hz, 2H), 7.45 (d, J =
8.1 Hz, 1H), 7.39−7.23 (m, 8H), 6.88 (dd, J = 7.9, 2.3 Hz, 2H), 6.00
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J. Org. Chem. 2021, 86, 3758−3767