Synthetic Applications of Aryllead Triacetates
J . Org. Chem., Vol. 61, No. 17, 1996 5869
petroleum ether-CH2Cl2. The same yield was obtained fol-
lowing method C at 70 °C for 6 h. Mp 201-203 °C (EtOH).
Data for 10: Mp 158-159 °C (EtOH). IR (KBr): 1348, 1156,
710 cm-1
.
1H-NMR (CDCl3, 250 MHz) δ 7.70 (dd, 2Η, J ) 8.1
IR (KBr): 1720 cm-1
.
1H-NMR (CDCl3, 300 MHz) δ 7.94 (m,
and 1.6 Hz); 7.58 (tt, 1H, J ) 7.8 and 2.0 Hz); 7.47 (td, 2H, J
) 7.9 and 1.2 Hz); 7.14 (d, 4Η, J ) 8.8 Hz); 7.02 (d, 4Η, J )
8.5 Hz); 2.30 (s, 6H). 13C-NMR (CDCl3, 63 MHz) δ 140.6; 138.9;
137.4; 132.6; 129.9; 128.8; 128.1; 127.7; 21.0. Anal. Calcd for
C20H19NO2S: C, 71.19; H, 5.67; N, 4.15. Found: C, 71.07; H,
5.63; N, 4.04.
2H); 7.78 (m, 2H); 7.31 (s, 4H); 2.41 (s, 3H). 13C-NMR (CDCl3,
75 MHz) δ 167.4; 138.2; 134.3; 131.8; 129.8; 128.9; 126.4; 123.7;
21.2. Anal. Calcd for C15H11NO2: C, 75.93; H, 4.67; N, 5.90.
Found: C, 75.56; H, 4.94; N, 5.76.
1,1-Dioxo-2-(p-tolyl)ben zo[c]1,2-th iazol-3-on e (4). Start-
ing from sodium saccharine (100 mg, 0.49 mmol) and p-
tolyllead triacetate (255 mg, 0.54 mmol) in 1:1.5 CH2Cl2-DMF,
method A was used at 60 °C for 5 h. A yield of 129 mg (98%)
of 4 was obtained after chromatography on silica gel, eluting
with 95:5 petroleum ether-ethyl ether. Mp 198-200 °C
4-[N-(p -Tolyl)a m in o]a cet a n ilid e (11). Starting from
4-aminoacetanilide (50 mg, 0.21 mmol) and p-tolyllead triac-
etate (174 mg, 0.37 mmol) in CH2Cl2 (2 mL), method C was
followed at 25 °C for 1 h. A yield of 75 mg (97%) of 11 was
obtained after chromatography on silica gel, eluting with ethyl
ether. The same yield was obtained following method C at 70
°C for 6 h. Mp 141-143 °C (CDCl3). IR (KBr): 3320, 1650
(EtOH). IR (KBr): 1718, 1308, 1192 cm-1 1H-NMR (CDCl3,
.
300 MHz) δ 8.15 (dd, 1H, J ) 7.5 and 1.8 Hz); 7.99 (dd, 1H, J
) 7.5 and 1.8 Hz); 7.92 (td, 1H, J ) 7.5 and 1.8 Hz); 7.88 (td,
1H, J ) 7.5 and 1.8 Hz); 7.41 (d, 2H, J ) 8.1 Hz); 7.35 (d, 2H,
J ) 8.1 Hz); 2.43 (s, 3H). 13C-NMR (CDCl3, 75 MHz) δ 158.5;
140.5; 137.6; 135.0; 134.4; 130.6; 128.7; 127.2; 125.7; 125.6;
121.2; 21.4. Anal. Calcd for C14H11NO3S: C, 61.53; H, 4.05;
N, 5.12. Found: C, 61.14; H, 4.25; N, 5.07.
cm-1
.
1H-NMR (CDCl3, 250 MHz) δ 7.66 (br s, 1H); 7.34 (d,
2H, J ) 8.8 Hz); 7.06 (d, 2H, J ) 8.2 Hz); 6.95 (d, 2H, J ) 8.8
Hz); 6.94 (d, 2H, J ) 8.3 Hz); 5.63 (br s, 1H); 2.29 (s, 3H); 2.13
(s, 3H). 13C-NMR (CDCl3, 63 MHz) δ 168.5; 140.5; 140.4; 130.8;
130.4; 129.8; 121.8; 118.0; 117.7; 24.2; 20.6. Anal. Calcd for
C15H16N2O: C, 74.97; H, 6.71; N, 11.65. Found: C, 74.74; H,
6.70; N, 11.49.
5,5-Dip h en yl-3-(p -t olyl)im id a zolid in e-2,4-d ion e (5).
Starting from diphenylhydantoin (100 mg, 0.39 mmol) and
p-tolyllead triacetate (222 mg, 0.47 mmol) in 3:1 CH2Cl2-DMF,
method A was used at 80 °C for 7 h. A yield of 101 mg (75%)
of 5 was obtained after chromatography on silica gel, eluting
with CH2Cl2. Mp 202-204 °C (EtOH). IR (KBr): 3230, 1725
N
1-(p-Tolyl)su lfa n ila m id e (13). A solution of p-tolyllead
triacetate (152 mg, 0.319 mmol) and copper(II) acetate (10 mg)
in CH2Cl2 (3 mL) containing pyridine or triethylamine (1.1
equiv) was added to a suspension of sulfanilamide (50 mg, 0.29
mmol) in CH2Cl2 (5 mL) at 40 °C. The green suspension was
heated in an oil bath at 40 °C for 16 h and worked up as in
method A. The crude reaction product was purified by
cm-1 1H-NMR (CDCl3, 300 MHz) δ 7.88 (br s, 1H); 7.44-7.41
.
and 7.34-7.32 (2 m, 10H); 7.23 (s, 4H); 2.35 (s, 3H). 13C-NMR
(CDCl3, 75 MHz) δ 172.2; 155.9; 139.1; 138.4; 129.6; 128.8;
128.5; 126.8; 126.1; 69.9; 21.1. Anal. Calcd for C22H18N2O2:
C, 77.17; H, 5.30; N, 8.18. Found: C, 76.62; H, 5.19; N, 7.97.
N-P h en yl-N-(p-tolyl)a ceta m id e (6). Starting from ac-
etanilide (50 mg, 0.37 mmol), p-tolyllead triacetate (211 mg,
0.44 mmol), and NaH (17 mg of a 60% dispersion in mineral
oil, followed by 14 mg 24 h later, totaling 0.78 mmol), method
B was used for 48 h at 80 °C. A yield of 62 mg of 6 was
obtained (75%, 91% based on recovered acetanilide), after
column chromatography on silica gel, using a gradient of 98:2
chromatography on silica gel, eluting with CHCl3
, yielding 53
mg (70%) of 13. IR (NaCl): 3410, 3250, 3330, 1340, 1160 cm-1
.
1H-NMR (acetone-d6, 250 MHz) δ 7.86 (br s, 1Η); 7.73 (d, 2Η,
J ) 7.6 Hz); 7.18 (br s, 4H); 7.12 (d, 2H, J ) 7.6 Hz); 6.36 (br
s, 1Η); 2.33 (s, 3H). 13C-NMR (acetone-d6, 63 MHz) δ 149.2;
139.7; 134.1; 132.8; 130.6; 128.7; 121.3; 114.6; 20.7. Anal.
Calcd for C13H14N2O2S: C, 59.52; H, 5.38; N, 10.68. Found:
C, 59.33; H, 5.33; N, 10.49.
N-(3′-Meth oxyp h en yl)-3-oxobu ta n a m id e (14b). A solu-
tion of m-anisidine (3 g, 24.35 mmol) and 2,2,6-trimethyl-4H-
1,3-dioxin-3-one (3.63 g; 25.57 mmol) in xylene (20 mL) was
heated in an open flask at 120 °C for 1 h. The solvent was
evaporated under reduced pressure, and the crude reaction
product was purified by chromatography on silica gel, eluting
with CH2Cl2, yielding 3.63 g (72%) of anilide 14b. Mp 76-77
°C (acetone/petroleum ether). IR (KBr): 3150, 1676, 1624
hexane-CH2Cl2 to neat CH2Cl2. IR (NaCl): 1670 cm-1 1H-
.
NMR (CDCl3, 250 MHz) δ 7.26-7.14 (m, 9Η); 2.32 (br s, 3H);
2.03 (s, 3H). Anal. Calcd for C15H15NO: C, 79.97; H, 6.71; N,
6.22. Found: C, 79.52; H, 7.06; N, 6.16.
N-(p-Tolyl)a ceta m id e (7) a n d N,N-Bis(p-tolyl)a ceta -
m id e (8). Starting from acetamide (25 mg, 0.43 mmol),
p-tolyllead triacetate (221 mg, 0.47 mmol), and NaH (18 mg
of a 60% dispersion in mineral oil, 0.47 mmol), method B was
used at 80 °C for 16 h. A yield of 48 mg (76%) of 7 and 10 mg
(10%) of 8, after column chromatography on silica gel eluting
with 7:3 petroleum ether-ethyl ether was obtained.
cm-1 1H-NMR (CDCl3, 300 MHz) δ: 9.22 (br s, 1H); 7.27 (m,
.
1H); 7.18 (t, 1H, J ) 8.1 Hz); 7.03 (d, 1H, J ) 7.5 Hz); 6.66 (d,
1H, J ) 8.4 Hz); 3.75 (s, 3H); 3.54 (s, 2H); 2.26 (s, 3H) ppm.
13C-NMR (CDCl3, 75 MHz) δ: 204.2; 161.9; 159.6; 138.3; 129.2;
111.9; 109.8; 105.5; 54.8; 49.9; 30.6 ppm. Anal. Calcd for C11
-
Data for 7: Mp 129-130 °C. IR (KBr): 3260, 1672 cm-1
.
H13NO3: C, 63.75; H, 6.32; N, 6.76. Found: C, 63.84; H, 6.20;
N, 6.82.
1H-NMR (CDCl3, 250 MHz) δ 7.34 (d, 2Η, J ) 8.1 Hz); 7.18
(br s, 1H); 7.09 (d, 2H, J ) 8.1 Hz); 2.29 (s, 3H); 2.14 (s, 3H).
13C-NMR (CDCl3, 63 MHz) δ 168.2; 135.2; 135.2; 133.9; 129.5;
120.0; 24.6; 20.9. Anal. Calcd for C9H11NO: C, 72.45; H, 7.43;
N, 9.38. Found: C, 72.14; H, 7.54; N, 8.98.
2-(p -Tolyl)-N -(2′,5′-d im e t h oxyp h e n yl)-3-oxob u t a n -
a m id e (15a ) a n d 2-(p-tolyl)-N-(2′,5′-d im eth oxyp h en yl)-2-
oxoa ceta m id e (16a ). Starting from N-(2′,5′-dimethoxyphen-
yl)-3-oxobutanamide (100 mg, 0.42 mmol), p-tolyllead triace-
tate (220 mg, 0.46 mmol) in CH2Cl2 (5 mL), and sodium
hydride (18 mg of a 60% dispersion in mineral oil, 0.46 mmol),
method A was used at 90 °C for 4 h. A yield of 15 mg (11%,
22% based on recovered starting material) of 15a and 10 mg
(8%, 16% based on recovered starting material) of 16a was
obtained after column chromatography on silica gel eluting
with 9:1 petroleum ether-CH2Cl2.
Data for 8: IR (NaCl): 1671 cm-1
.
1H-NMR (CDCl3, 250
MHz) δ 7.15 (br s, 8Η); 2.35 (br s, 6H); 2.05 (s, 3H). Anal.
Calcd for C16H17NO: C, 80.30; H, 7.16; N, 5.85. Found: C,
80.38; H, 7.42; N, 5.74.
N-(p -Tolyl)b en zen esu lfon a m id e (9) a n d N,N-Bis(p -
tolyl)ben zen esu lfon a m id e (10). Starting from benzene-
sulfonamide (60 mg, 0.38 mmol), p-tolyllead triacetate (199
mg, 0.42 mmol) in 3:1 CH2Cl2-DMF, and NaH (17 mg of a
60% dispersion in mineral oil, 0.42 mmol), method A was used
at 90 °C for 5 h. A yield of 69 mg (73%) of 9 and 11 mg (9%)
of 10, after column chromatography on silica gel eluting with
1:1 CH2Cl2-hexane, was obtained.
Data for 15a : 1H-NMR (CDCl3, 250 MHz, 67% oxo tautomer,
33% enol tautomer) δ: 14.46 (s, 1H); 9.32 (br s, 1H); 7.98 (d,
1H, J ) 3.0 Hz); 7.93 (d, 1H, J ) 3.0 Hz); 7.52 (br s, 1H); 7.25-
7.15 (m, 6H); 7.11 (d, 2H, J ) 7.9 Hz); 6.71 (d, 1H, J ) 8.9
Hz); 6.60 (d, 1H, J ) 7.6 Hz); 6.49 (dd, 1H, J ) 9.0 and 3.0
Hz); 6.44 (dd, 1H, J ) 8.8 and 2.9 Hz); 4.67 (s, 1H); 3.75 (s,
3H); 3.71 (s, 3H); 3.67 (s, 3H); 3.46 (s, 3H); 2.35 (s, 3H); 2.28
(s, 3H); 2.21 (s, 3H); 1.76 (s, 3H).
Data for 9: Mp 117-119 °C (EtOH). IR (KBr): 3310, 1316,
1172, 740 cm-1 1H-NMR (CDCl3, 250 MHz) δ 7.75 (d, 2Η, J
.
) 7.2 Hz); 7.53 (tt, 1H, J ) 7.3 and 2.0 Hz); 7.43 (t, 2H, J )
7.1 Hz); 7.03 (d, 2Η, J ) 8.3 Hz); 6.95 (d, 2Η, J ) 8.4 Hz);
6.74 (br s, 1Η); 2.27 (s, 3H). 13C-NMR (CDCl3, 63 MHz) δ
139.1; 135.7; 133.6; 133.0; 130.0; 129.1; 127.3; 122.6; 22.0.
Anal. Calcd for C13H13NO2S: C, 63.13; H, 5.30; N, 5.66.
Found: C, 62.85; H, 5.25; N, 5.28.
Data for 16a : Mp 101-102 °C (acetone/petroleum ether).
IR (KBr): 3456, 3375, 1700, 1656, 1290 cm-1
.
1H-NMR
(CDCl3, 250 MHz) δ 9.48 (br s, 1H); 8.25 (d, 2H, J ) 8.2 Hz);
8.14 (d, 1H, J ) 3.0 Hz); 7.23 (d, 2H, J ) 8.2 Hz); 6.77 (d, 1H,
J ) 8.9 Hz); 6.58 (dd, 1H, J ) 8.9 and 3.0 Hz); 3.81(s, 3H);