# Patent

## Title
Fungicidal substituted 2-phenyl-2,2-difluoroethylthiolcarbonates,

## Abstract

According to the procedures as described in the preceding Examples, the compounds as shown in Tables 12, 13 and 14 were obtained. __________________________________________________________________________ ##STR176## Example No.  R.sub.0 R.sub.1 R.sub.2 X        Y     n  Physical data __________________________________________________________________________ 12   H   Me PNB CONH.sub.2 PNZ   1  IR.sub.max.sup.CHCl.sbsp.3 cm.sup.-1 1770, 1690, 1520, 1400, 1345, 1105 NMR .delta. (CDCl.sub.3): 1.28(3H, d, J = 6.8Hz), 1.36(3H, d, J=7Hz), 5.22 (2H, s), 5.49 1H, d, J=13.9Hz), 8.21(4H, d, J=8.8Hz) H   Me H   CONH.sub.2 H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1665, 1590, 1487, 1280 NMR .delta. (D.sub.2 O): 1.20(3H, d, J=7.3Hz), 1.28(3H, d, J = 6.3Hz), 3.44(1H, dd, J= 2.6Hz and 6.3Hz) 13   PNZ H  PNB ##STR177## PNZ   1  IR.sub.max.sup.CHCl.sbsp.3 cm.sup.-1 : NMR .delta. (CDCl.sub.3): 1773, 1740, 1695, 1620, 1513, 1340, 1254 1.48(3H, d, J=6.2Hz), 5.22(2H, s), 5.26(2H, s), 5.46(1H, d, J = 3.9Hz), 8.21(6H, d, J=8.6Hz) H   H  H ##STR178## H     1  UV.sub.max.sup.H.sbsp.2.sup.O nm: IR.sub.max.sup.KBR cm.sup.- 1: NMR .delta. (D.sub.2 O): 298 1753, 1620, 1446, 1380 1.26(3H, d, J=6.3Hz) 14   H   Me PNB ##STR179## PNZ   1  IR.sub.max.sup.neat cm.sup.-1: NMR .delta. (CDCl.sub.3): 1765, 1700, 1620, 1520, 1347, 1210 1.27(3H, d, J=7.3Hz), 1.34(3H, d, J=6.4Hz), 5.22(2H, s), 5.48(1H, d, J = 13.9Hz), 8.40(4H, d, J=8.6Hz) H   Me H ##STR180## H     1  UV.sub.max.sup.H.sbsp.2.sup.O nm: IR.sub.max.sup.KBr cm.sup.- 1: NMR .delta. (D.sub.2 O): 296 1745, 1615, 1445, 1380 1.20(3H, d, J=7.32Hz), 1.27(3H, d, J=6.3Hz) 15   H   Me PNB COOMe    PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1760, 1730(sh), 1700, 1515, 1345, 1210 NMR .delta. (CDCl.sub.3): 1.26(3H, d, J=7Hz), 1.34(3H, d, J=6.9Hz), 3.67(3H, s), 5.22 (2H, s), 5.49(1H, d, J=13.6Hz), 8.20(4H, d, J=8.8Hz) H   Me H   COOMe    H     1  UV.sub.max.sup.H.sbsp.2.sup.O 296 IR.sub.max.sup.KBr cm.sup.-1 : 1755(sh), 1735, 1600, 1385, 1260 NMR .delta. (D.sub.2 O): 1.20(3H, d, J = 7Hz), 1.27(3H, d, J= 6Hz), 3.44(1H, dd, J = 2.3Hz and 6 Hz), 3.73(3H, s), 4.19(1H, d, J=2.3Hz) 16   PNZ H  PNB NHCONH.sub.2 PNZ   1  IR.sub.max.sup.Nujol cm.sup.-1 : 1782, 1750, 1700, 1608, 1520, 1350 NMR .delta. (DMSO-d.sub.6): 5.35(2H, s), 5.42(2H, s), 8.33(6H, d, J=8.6Hz) H   H  H   NHCONH.sub.2 H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1652, 1585, 1383 NMR .delta. (D.sub.2 O): 1.27(3H, d, J=6.3Hz), 3.18(2H, d, J = 9.2Hz) 17   PNZ H  PNB NHCONMe.sub.2 PNZ   1  IR.sub.max.sup.near cm.sup.-1 : 1780, 1742, 1692, 1636, 1520, 1255 NMR .delta. (CDCl.sub.3): 1.50(3H, d, J=6.4Hz), 2.87(6H, s), 5.26(4H, s), 8.20(6H, d J=8.6Hz) H   H  H   NHCONMe.sub.2 H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1757, 1605(sh), 1595, 1535, 1395 NMR .delta. (D.sub.2 O): 1.26(3H, d, J=6.4Hz), 2.88(6H, s), 3.67(2H, d, J=9.2Hz) 18   PNZ H  PNB NHCOOEt  PNZ   1  IR.sub.max.sup.near cm.sup.-1 : 1770, 1750, 1710, 1520, 1350, 1280 NMR .delta. (CDCl.sub.3): 1.22(3H, t, J=7Hz), 1.48(3H, d, J=6.2Hz), 5.24(4H, s), 8.20 (6H, d, J=8.6Hz) H   H  H   NHCOOEt  H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1746, 1700, 1585, 1380, 1245 NMR .delta. (D.sub.2 O): 3.17(2H, d, J=8.9Hz), 3.30(1H, dd, J=4.6Hz and 12.5Hz), 3.40 (1H, dd, J=2.6Hz, and 5.9Hz) 19   PNZ H  PNB NHCOCH.sub.3 PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1780, 1745, 1695, 1520, 1347, 1256 NMR .delta. (CDCl.sub.3): 1.48(3H, d, J=6.2Hz), 1.95(3H, s), 5.25(4H, s) H   H  H   NHCOCH.sub.3 H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1650, 1593, 1385, 1195, 1040 NMR .delta. (D.sub.2 O): 1.28(3H, d, J=6Hz), 2.03(3H, s), 3.19(2H, d, J=9.2Hz) 20   PNZ H  PNB OCONH.sub. 2 PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1783, 1740, 1705, 1525, 1348, 1260 NMR .delta. (CDCl.sub.3): 1.48(3H, d, J=6.2Hz), 5.22(4H, s), 5.46(1H, d, J=13.9Hz) H   H  H   OCONH.sub.2 H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1725, 1595, 1395, 1520, 1092 NMR .delta. (D.sub.2 O): 1.26(3H, d, J=6.3Hz), 3.40(1H, dd, J=2.6Hz and 5.9Hz), 3.57(1H, dd, J=6.9Hz, and 12.2Hz) 21   PNZ H  PNZ OCONMe.sub.2 PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1773, 1740, 1700, 1515, 1340, 1253 NMR .delta. (CDCl.sub.3): 1.49(3H, d, J=6.4Hz), 2.88 (6H, s), 5.23(4H, s), 5.46 (1H, d, J=13.6Hz), 8.20(6H, d, J=8.4Hz) H   H  H   OCONMe.sub.2 H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1755, 1690, 1592, 1385, 1193 NMR .delta. (D.sub.2 O): 1.27(3H, d, J=6.3Hz), 2.89(3H, s), 2.94(3H, s), 3.40(1H, dd, J=2.6Hz and 5.9Hz), 3.56(1H, dd, J=6.9Hz and 12.2Hz) 22   PNZ H  PNB NHPNZ    CONMe.sub.2 1  IR.sub.max.sup.CHCl.sbsp.3 cm.sup.-1 1780, 1740(sh), 1720, 1625(sh), 1610, 1514 NMR .delta. (CDCl.sub.3): 1.49(3H, d, J=6.4Hz), 2.83 (6H, s), 5.18(2H, s), 5.26 (2H, s) 23   PNZ H  PNB OCONHMe  PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1773, 1745(sh), 1702, 1520, 1343, 1260 NMR .delta. (CDCl.sub.3): 1.48(3H, d, J=6.4Hz), 2.95(3H, s), 5.25(4H, s), H   H  H   OCONHMe  H     1  UV.sub.max.sup.H.sbsp.2.sup.O 296 IR.sub.max.sup.KBr cm.sup.-1 : 1758, 1712, 1588, 1385, 1255, 1140 NMR .delta. (D.sub.2 O): 1.27(3H, d, J=6.6Hz), 2.71(3H, s), 3.41(1H, dd, J=2.6Hz and 5.9Hz), 24   PNZ H  PNB OCOOEt   PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1770, 1740, 1708, 1515, 1340 NMR .delta. (CDCl.sub.3): 1.31(3H, t, J=7Hz), 1.49(3H, d, J=6.2Hz), 4.19(2H, q, J=7Hz), 5.24(4H, s), 5.47(1H, d, J= 14.1Hz), 8.20(6H, d, J=8.6Hz) H   H  H   OCOOEt   H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1747, 1600, 1386, 1260 NMR .delta. (D.sub.2 O): 1.26(3H, d, J=6.6Hz), 1.28(3H, t, J=6.9Hz), 3.30(1H, dd, J=5.6Hz and 12.2Hz), 3.40(1H, dd J=2.6Hz and 5.9Hz) 25   PNZ H  PNB OCOCH.sub.3 PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1772, 1730, 1698, 1517, 1342, 1225 NMR .delta. (CDCl.sub.3): 1.49(3H, d, J=6.4Hz), 2.06(3H, s), 5.24(4H, s), 5.47(1H, d, J= 13.6Hz), 8.20(6H, d, J=8.4Hz) H   H  H   OCOCH.sub.3 H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1740, 1590, 1385, 1238 NMR .delta. (D.sub.2 O): 1.26(3H, d, J=6.3Hz), 2.14(3H, s) 26   PNZ H  PNB CONH.sub.2 PNZ   2  IR.sub.max.sup.Nujol cm.sup.-1 : 1790, 1746, 1708, 1660, 1600, 1510 NMR .delta. (CDCl.sub.3): 1.34(3H, d, J=6.1Hz), 5.22(2H, s), 5.30(2H, s), 8.21(6H, d, J= 8.6Hz) H   H  H   CONH.sub.2 H     2  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1660, 1585, 1387 NMR .delta. (D.sub.2 O): 1.25(3H, d, J=6.6Hz), 2.39(2H, t, J=7.7Hz), 3.27(1H, dd, J=5.2Hz and 12.5Hz), 3.38(1H, dd, J=2.6Hz and 5.9Hz) 27   H   Me PNB CONH.sub.2 PNZ   2  IR.sub.max.sup.CHCl.sbsp.3 cm.sup.-1 1700, 1770, 1520, 1347, 1102 NMR .delta. (acetone-d.sub.6): 1.27(6H, d, J= 6.2Hz), 5.25 (2H, s), 5.51(1H, d, J= 14.1Hz) H   Me H   CONH.sub.2 H     2  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1663, 1590, 1383, 1246 NMR .delta. (D.sub.2 O): 1.18(3H, d, J=7.3Hz) 1.26(3H, d, J=6.6Hz), 3.43(1H, dd, J=2.6Hz and 6.3Hz) 28   PNZ H  PNB ##STR181## PNZ   2  IR.sub.max.sup.Nujol cm.sup.-1 : NMR .delta. (DMSO-d.sub.6): 1788, 1742, 1704, 1633, 1512 .22(3H, s), 5.22(2H, s), 5.30 (2H, s), 8.21(6H, d, J=8.6Hz) H   H  H ##STR182## H     2  UV.sub.max.sup.H.sbsp.2.sup.O nm: IR.sub.max.sup.KBr cm.sup.-1 : NMR .delta. (D.sub.2 O): 299 1757, 1638, 1590, 1380, 1240  1.25(3H, d, J=6.3Hz), 2.69(3H, s), 3.38(1H, dd, J=2.6Hz and 6.3Hz) 29   PNZ H  PNB CONMe.sub.2 PNZ   2  IR.sub.max.sup.CHCl.sbsp.3 cm.sup.-1 1782, 1750, 1700, 1638, 1523 NMR .delta. (CDCl.sub.3): 1.48(3H, d, J=6.4Hz), 2.91(3H, s), 2.94(3H, s), 5.26(2H, s), 5.21(2H, s), 5.48(1H, d, J= 13.9Hz), 8.20(6H, d, J=8.6Hz) H   H  H   CONMe.sub.2 H     2  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1756, 1620, 1590, 1385, 1245 NMR .delta. (D.sub.2 O): 1.25(3H, d, J=6.3Hz) 2.90(3H, s), 3.03(3H, s) 30   PNZ H  PNB OH       PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1778, 1748, 1700, 1515, 1305, 1259 NMR .delta. (CDCl.sub.3): 1.48(3H, d, J=6.4Hz), 5.23(4H, s), 5.46(1H, d, J=13.9Hz), 8.20 (6H, d, J=8.6Hz) H   H  H   OH       H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1585, 1385, 1240 NMR .delta. (D.sub.2 O): 1.26(3H, d, J=6.3Hz), 3.18(2H, d, J=8.9Hz) 31   H   Me H   OH       CHNH  1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1742, 1698, 1582, 1380 NMR .delta. (D.sub.2 O): 1.19(3H, d, J=7.3Hz), 1.27(3H, d, J=6.3Hz), 8.05(1H, s) 32   H   Me H   OH ##STR183## 1  UV.sub.max.sup.H.sbsp.2.sup.O nm: IR.sub.max.sup.KBr cm.sup.-1 : NMR .delta. (D.sub.2 O): 298 1740, 1693, 1605, 1382 1.19(3H, d, J=6.9Hz), 1.27(3H, d. J=6.3Hz), 2.20(3H, s) 33   PNZ H  PNB SMe      PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1778, 1738, 1705, 1520, 1345, 1260 NMR .delta. (CDCl.sub.3): 1.49(3H, d, J=6.4Hz), 2.09(3H, s), 5.23(2H, s), 5.25(2H, s), 5.47(1H, d, J=13.6Hz), 8.20(6H, d, J=8.6Hz) H   H  H   SMe      H     1  UV.sub.max.sup.H.sbsp.2.sup.O 297 IR.sub.max.sup.KBr cm.sup.-1 : 1755, 1590, 1380, 1238 NMR .delta. (D.sub.2 O): 1.26(3H, d, J=6.3Hz), 2.14(3H, s), 3.17(2H, d, J=8.9Hz) 34   PNZ H  PNB SO.sub.2 Me PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1780, 1750, 1703, 1520, 1308, 1263 NMR .delta. (CDCl.sub.3): 1.49(3H, d, J=6.4Hz), 2.75(3/2H, s), 2.80(3/2H, s), 5.23(2H, s), 5.25(2H, s), 5.47(1H, d, J= 13.9Hz), 8.20(6H, d, J=8.8Hz) H   H  H   SO.sub.2 Me H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1755, 1590, 1390, 1292, 1128 NMR .delta. (D.sub.2 O): 1.26(3H, d, J=6.3Hz), 3.15(3H, s), 3.39(1H, dd, J=2.3Hz and 5.9Hz) 35   PNZ H  PNB OMe      PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1783, 1752, 1708, 1528, 1350 NMR .delta. (CDCl.sub.3): 1.49(3H, d, J=6.4Hz), 3.33(3H, s), 5.23(2H, s), 5.25(2H, s), 5.47(1H, d, J=13.9Hz), 8.20(6H, d, J=8.6Hz) H   H  H   OMe      H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1752, 1590, 1382, 1242 NMR .delta. (D.sub.2 O): 1.26(3H, d, J=6.6Hz), 3.40(3H, s) 36   H   Me PNB CN       PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 2250, 1770, 1705, 1513, 1350 NMR .delta. (CDCl.sub.3): 1.28(3H, d, J=7Hz), 1.35(3H, d, J=6Hz), 5.23(2H, s), 5.48(1H, d, J=13.9Hz), 8.21(4H, d, J= 8.1Hz) H   Me H   CN       H     1  UV.sub.max.sup.H.sbsp.2.sup.O 300 IR.sub.max.sup.KBr cm.sup.-1 : 2250, 1750, 1593, 1390 NMR .delta. (D.sub.2 O): 1.21(3H, d, J=7.3Hz), 1.29(3H, d, J=6.3Hz), 3.16(1H, dd, J=4.3Hz and 12.2Hz) 37   PNZ H  PNB CN       PNZ   1  IR.sub.max.sup.neat  cm.sup.-1 : 2245, 1778, 1745, 1700, 1519 NMR (CDCl.sub.3): 1.48(3H, d, J=6.2Hz), 5.24(4H, s), 8.18(6H, d, J=8.8Hz) H   H  H   CN       H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1585, 1383 NMR .delta. (D.sub.2 O): 1.28(3H, d, J=6.6Hz), 3.72(1H, dd, J=7.6Hz and 12.5Hz) 38   H   Me PNB OMe      PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1765, 1700, 1520, 1340 NMR .delta. (CDCl.sub.3): 1.27(3H, d, J=6.6Hz), 1.48(3H, d, J=6.2Hz), 3.33(3H, s), 5.22 (2H, s), 5.48(1H, d, J=13.6Hz), 8.20(4H, d, J=8.4Hz) H   Me H   OMe      H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1753, 1597, 1385 NMR .delta. (D.sub.2 O): 1.19(3H, d, J=7.3Hz), 1.26(3H, d, J=6.3Hz), 3.39(3H, s), 3.44(1H, dd, J=2.4Hz and 6.3Hz) 39   H   Me PNB ##STR184## PNZ   3  IR.sub.max.sup.neat cm.sup.-1 : NMR .delta. (CDCl.sub.3): 1775, 1705, 1658, 1525, 1348 .26(3H, d, J=7Hz), 1.34(3H, d, J=6.4Hz), 2.77(3H, d, J=4.8Hz), 5.20(2H, s), 5.47(1H, d, J= 13.6Hz) H   Me H ##STR185## H     3  UV.sub.max.sup.H.sbsp.2.sup.O nm IR.sub.max.sup.KBr cm.sup.-1 : NMR .delta. (D.sub.2 O): 298 1752, 1640, 1590, 1383 1.20(3H, d, J=7.3Hz), 1.27(3H, d, J=6.3Hz), 2.29(2H, t, J=7Hz), 2.71(3H, s) 40   H   Me PNB ##STR186## PNZ   4  IR.sub.max.sup.neat  cm.sup.-1 : NMR .delta. (CDCl.sub.3): 1763, 1700, 1655, 1520, 1343 .27(3H, d, J=7Hz), 1.35(3H, d, J=7Hz), 2.78(3H, d, J=4.8Hz), 5.21(2H, s), 8.21(4H, d, J= 8.8Hz) H   Me H ##STR187## H     4  UV.sub.max.sup.H.sbsp.2.sup.O nm: IR.sub.max.sup.KBr cm.sup.-1 : NMR .delta. (D.sub.2 O): 298 1752, 1640, 1590, 1385 1.22(3H, d, J=6.9Hz), 1.30(3H, d, J=6.3Hz), 2.27(2H, t, J=7Hz), 2.73(3H, s) 41   H   Me PNB COOPNB   PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1762, 1736, 1703, 1519, 1342 NMR .delta. (CDCl.sub.3): 1.26(3H, d, J=6.8Hz), 1.34(3H, d, J=6.2Hz), 5.20(4H, s), 8.19 (6H, d, J=8.8Hz) H   Me H   COOH     H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1598, 1393, 1180 NMR .delta. (D.sub.2 O): 1.22(3H, d, J=7.3Hz), 1.30(3H, d, J=6.3Hz), 3.47(1H, dd, J=2.6Hz and 6.3Hz) 42   H   Me PNB COOPNB   PNZ   2  IR.sub.max.sup.neat cm.sup.-1 : 1770, 1730, 1693, 1604, 1515 NMR .delta. (CDCl.sub.3): 1.26(3H, d, J=7.3Hz), 1.34(3H, d, J=6Hz), 5.20(4H, S), 8.18(6H, d, J=8.1Hz) H   Me H   COOH     H     2  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1755, 1608, 1570, 1400 NMR .delta. (D.sub.2 O): 1.23(3H, d, J=7.3Hz), 1.30(3H, d, J=6.6Hz) 43   H   Me PNB CHNOMe   PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1760, 1700, 1520, 1400, 1345 NMR .delta. (CDCl.sub.3): 1.27(3H, d, J=6.8Hz), 1.35(3H, d, J=5.9Hz), 5.23(2H, s), 5.49 (1H, d, J=13.9Hz), 8.20(4H, d, J=8.6Hz) H   Me H   CHNOMe   H     1  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1595, 1390 NMR .delta. (D.sub.2 O): 1.22(3H, d, J=7.3Hz), 1.29(3H, d, J=6.3Hz), 3.47(1H, dd, J= 2.6Hz and 5.9Hz), 3.85, 3.90 (3H, s) 44   H   Me PNB CHNNMe.sub.2 PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1765, 1700, 1520, 1400, 1340 NMR .delta. (CDCl.sub.3): 1.19(3H, d, J=7Hz), 1.27(3H, d, J=7Hz), 2.73(6H, s), 5.23 (2H, s), 8.21(4H, d, J=8.8Hz) H   Me H   CHNNMe.sub.2 H     1  UV.sub.max.sup.H.sbsp.2.sup.O 238, 298 IR.sub.max.sup.KBr cm.sup.-1 : 1748, 1590, 1383 NMR .delta. (D.sub.2 O): 1.22(3H, d, J=7.3Hz), 1.30(3H, d, J=6.6Hz), 2.72(6H, s), 3.47 (1H, dd, J=2.6Hz and 6.3Hz), 6.02(1H, t, J=5Hz) 45   H   Me PNB CONHNMe.sub.2 PNZ   1  IR.sub.max.sup.neat cm.sup.-1 : 1763, 1700, 1520, 1400, 1342 NMR .delta. (CDCl.sub.3): 1.28(3H, d, J=7Hz), 1.35(3H, d, J=6.4Hz), 2.49(3H, s), 2.56 (3H, s), 5.22(2H, s), 8.21(4H, d, J=8.4Hz) H   Me H   CONHNMe.sub.2 H     1  UV.sub.max.sup.H.sbsp.2.sup.O 296 IR.sub.max.sup.KBr cm.sup.-1 : 1745, 1658, 1590, 1383 NMR .delta. (D.sub.2 O): 1.22(3H, d, J=7.3Hz), 1.30(3H, d, J=6.6Hz), 2.55(6H, s) 46   H   Me PNB OH       PNZ   2  IR.sub.max.sup.neat cm.sup.-1 : 1768, 1690, 1520, 1348, 1212 NMR .delta. (CDCl.sub.3): 1.28(3H, d, J=7.3Hz), 1.35 3H, d, J=6.3Hz), 5.23(2H, s), 5.50(1H, d, J=13.9Hz) H   Me H   OH       H     2  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1750, 1588, 1383 NMR .delta. (D.sub.2 O): 1.23(3H, d, J=7.3Hz), 1.30(3H, d, J=6.3Hz), 3.47(1H, dd, J= 2.6Hz and 6.3Hz) 47   H   Me PNB OH       PNZ   3  IR.sub.max.sup.neat cm.sup. 1770, 1690, 1520, 1348, 1208 NMR .delta. (CDCl.sub.3): 1.28(3H, d, J=7Hz), 1.36(3H, d, J=6.3Hz), 5.50(1H, d, J= 13.5Hz), 7.65(2H, d, J=8.9Hz) H   Me H   OH       H     3  UV.sub.max.sup.H.sbsp.2.sup.O 298 IR.sub.max.sup.KBr cm.sup.-1 : 1752, 1595, 1388 NMR .delta. (D.sub.2 O): 1.22(3H, d, J=7.3Hz), 1.30(3H, d, J=6.3Hz) __________________________________________________________________________ __________________________________________________________________________ ##STR188## Example No.  R.sub.0 R.sub.1 R.sub.2 X     Y  n Physical data __________________________________________________________________________ 48   H Me PNB OH    PNZ 1 IR.sub.max.sup.neat cm.sup.-1 : 1760, 1685, 1512, 1340 NMR .delta. (CDCl.sub.3): 1.27 (3H, d, J=7.3Hz), 1.34 (3H, d, J=6.3 Hz), 5.24 (2H, s), 5.48 (1H, d, J=13.9Hz), 7.52 (2H, d, J=8.9Hz), 7.63 (2H d, J=8.9 Hz) H Me H  OH    H  1 UV.sub.max.sup.H.sbsp.2.sup.O nm: 298 IR.sub.max.sup.KBr cm.sup.-1 : 1752, 1598, 1395 NMR .delta. (D.sub.2 O): 1.22 (3H, d, J=7.3Hz), 1.30 (3H, d, J=6.3 Hz) 3.48 (1H, dd, J=2.6 Hz and 5.9 Hz) 49   H Me PNB ##STR189## PNZ 1 IR.sub.max.sup.neat cm.sup.-1 : NMR .delta. (CDCl.sub.3): 1768, 1705, 1660, 1524 1.27 (3H, d, J=7.3 Hz), 1.36 (3H, d, J=6.3 Hz), 2.72 (3H, d, J=4.6 Hz), 5.22 (2H, s), 5.50 (1H, d, J=13.5 Hz), 7.52 (2H, d, J=8.3 Hz), 7.66 (2H d, J=8.6 Hz) H Me H ##STR190## H  1 UV.sub.max.sup.H.sbsp.2.sup.O nm: IR.sub.max.sup.K Br cm.sup.-1 : NMR .delta. (D.sub.2 O): 298 1745, 1642, 1580, 1380 1.22 (3H, d, J=7.3 Hz), 1.31 (3H, d, J=6.3 Hz), 2.74 (3H, s) __________________________________________________________________________ ______________________________________ ##STR191## No.      R.sub.1 n       X           Y ______________________________________ 1        H      1       CONH.sub.2  H 2        Me     1       CONH.sub.2  H 3        H      1       CONHMe      H 4        Me     1       CONHMe      H 5        H      1       CONMe.sub.2 H 6        Me     1       CONMe.sub.2 H 7        H      1 ##STR192## H 8        Me     1 ##STR193## H 9        H      1 ##STR194## H 10       Me     1 ##STR195## H 11       H      1 ##STR196## H 12       Me     1 ##STR197## H 13       H      1       COOMe       H 14       Me     1       COOMe       H 15       H      1       COOEt       H 16       Me     1       COOEt       H 17       H      1       NHCONH.sub.2 H 18       Me     1       NHCONH.sub.2 H 19       H      1       NHCONHMe    H 20       Me     1       NHCONHMe    H 21       H      1       NHCONMe.sub.2 H 22       Me     1       NHCONMe.sub.2 H 23       H      1       NHAc        H 24       Me     1       NHAc        H 25       H      1       NHCOOMe     H 26       Me     1       NHCOOMe     H 27       H      1       NHCOOEt     H 28       Me     1       NHCOOEt     H 29       H      1       OAc         H 30       Me     1       OAc         H 31       H      1       OCONH.sub.2 H 32       Me     1       OCONH.sub.2 H 33       H      1       OCONHMe     H 34       Me     1       OCONHMe     H 35       H      1       OCONMe.sub.2 H 36       Me     1       OCONMe.sub.2 H 37       H      1       NHCHNH      CONMe.sub.2 38       Me     1       NHCHNH      CONMe.sub.2 39       H      1 ##STR198## CONMe.sub.2 40       Me     1 ##STR199## CONMe.sub.2 41       H      1       CONH.sub.2  CHNH 42       Me     1       CONH.sub.2  CHNH 43       H      1       CONH.sub.2 ##STR200## 44       Me     1       CONH.sub.2 ##STR201## 45       H      1       CONHMe      CHNH 46       Me     1       CONHMe      CHNH 47       H      1       CONHMe ##STR202## 48       Me     1       CONHMe ##STR203## 49       H      1       CONMe.sub.2 CHNH 50       Me     1       CONMe.sub.2 CHNH 51       H      1       CONMe.sub.2 ##STR204## 52       Me     1       CONMe.sub.2 ##STR205## 53       H      1 ##STR206## CHNH 54       Me     1 ##STR207## CHNH 55       H      1 ##STR208## ##STR209## 56       Me     1 ##STR210## ##STR211## 57       H      1       NHCONMe.sub.2 CHNH 58       Me     1       NHCONMe.sub.2 CHNH 59       H      1       NHCONMe.sub.2 ##STR212## 60       Me     1       NHCONMe.sub.2 ##STR213## 61       H      1       CONHEt      H 62       Me     1       CONHEt      H 63       H      1       CONEt.sub.2 H 64       Me     1       CONEt.sub. 2 H 65       H      1       NHCONHEt    H 66       Me     1       NHCONHEt    H 67       H      1       NHCONEt.sub.2 H 68       Me     1       NHCONEt.sub.2 H 69       H      1       OCONHEt     H 70       Me     1       OCONHEt     H 71       H      1       OCONEt.sub.2 H 72       Me     1       OCONEt.sub.2 H 73       H      1       OCOEt       H 74       Me     1       OCOEt       H 75       H      1       OCOOMe      H 76       Me     1       OCOOMe      H 77       H      1       OCOOEt      H 78       Me     1       OCOOEt      H 79       H      1       COOH        H 80       Me     1       COOH        H 81       H      2       CONH.sub.2  H 82       Me     2       CONH.sub.2  H 83       H      2       CONHMe      H 84       Me     2       CONHMe      H 85       H      2       CONMe.sub.2 H 86       Me     2       CONMe.sub.2 H 87       H      2 ##STR214## H 88       Me     2 ##STR215## H 89       H      2 ##STR216## H 90       Me     2 ##STR217## H 91       H      2       COOMe       H 92       Me     2       COOMe       H 93       H      2       COOH        H 94       Me     2       COOH        H 95       H      2       CONH.sub.2  CHNH 96       Me     2       CONH.sub. 2 CHNH 97       H      2       CONH.sub.2 ##STR218## 98       Me     2       CONH.sub.2 ##STR219## 99       H      2       CONHMe      CHNH 100      Me     2       CONHMe      CHNH 101      H      2       CONHMe ##STR220## 102      Me     2       CONHMe ##STR221## 103      H      2       CONMe.sub.2 CHNH 104      Me     2       CONMe.sub.2 CHNH 105      H      2       CONMe.sub.2 ##STR222## 106      Me     2       CONMe.sub.2 ##STR223## 107      H      3       CONH.sub.2  H 108      Me     3       CONH.sub.2  H 109      H      3       CONHMe      H 110      Me     3       CONHMe      H 111      H      3       CONMe.sub.2 H 112      Me     3       CONMe.sub.2 H 113      H      3 ##STR224## H 114      Me     3 ##STR225## H 115      H      3       COOMe       H 116      Me     3       COOMe       H 117      H      3       COOH        H 118      Me     3       COOH        H 119      H      3       CONH.sub.2  CHNH 120      Me     3       CONH.sub.2  CH NH 121      H      3       CONH.sub.2 ##STR226## 122      Me     3       CONH.sub.2 ##STR227## 123      H      3       CONHMe      CHNH 124      Me     3       CONHMe      CHNH 125      H      3       CONHMe ##STR228## 126      Me     3       CONHMe ##STR229## 127      H      3       CONMe.sub.2 CHNH 128      Me     3       CONMe.sub.2 CHNH 129      H      3       CONMe.sub.2 ##STR230## 130      Me     3       CONMe.sub.2 ##STR231## 131      H      4       CONH.sub.2  H 132      Me     4       CONH.sub.2  H 133      H      4       CONHMe      H 134      Me     4       CONHMe      H 135      H      4       CONMe.sub.2 H 136      Me     4       CONMe.sub.2 H 137      H      4       COOMe       H 138      Me     4       COOMe       H 139      H      4       COOH        H 140      Me     4       COOH        H 141      H      4 ##STR232## H 142      Me     4 ##STR233## H 143      H      4       CONH.sub.2  CHNH 144      Me     4       CONH.sub.2  CHNH 145      H      4       CONH.sub.2 ##STR234## 146      Me     4       CONH.sub.2 ##STR235## 147      H      4       CONHMe      CHNH 148      Me     4       CONHMe      CHNH 149      H      4       CONHMe ##STR236## 150      Me     4       CONHMe ##STR237## 151      H      4       CONMe.sub.2 CHNH 152      Me     4       CONMe.sub.2 CHNH 153      H      4       CONMe.sub.2 ##STR238## 154      Me     4       CONMe.sub.2 ##STR239## 155      H      1       CN          H 156      Me     1       CN          H 157      H      1       CHNOMe      H 158      Me     1       CHNOMe      H 159      H      1       CHNOEt      H 160      Me     1       CHNOEt      H 161      H      1       CHNNMe.sub.2 H 162      Me     1       CHNNMe.sub.2 H 163      H      1       CHNNEt.sub.2 H 164      Me     1       CHNNEt.sub.2 H 165      H      1 ##STR240## H 166      Me     1 ##STR241## H 167      H      1       CHNNHMe     H 168      Me     1       CHNNHMe     H 169      H      1       CONHNH.sub.2 H 170      Me     1       CONHNH.sub.2 H 171      H      1       CONHNMe.sub.2 H 172      Me     1       CONHNMe.sub.2 H 173      H      1       CONMeNMe.sub.2 H 174      Me     1       CONMeNMe.sub.2 H 175      H      1       CONHNEt.sub.2 H 176      Me     1       CONHNEt.sub.2 H 177      H      1       CONMeNEt.sub.2 H 178      Me     1       CONMeNEt.sub.2 H 179      H      1 ##STR242## H 180      Me     1 ##STR243## H 181      H      1       OH          H 182      Me     1       OH          H 183      H      1       SMe         H 184      Me     1       SMe         H 185      H      1       SEt         H 186      Me     1       SEt         H 187      H      1       S(n)Pr      H 188      Me     1       S(n)Pr      H 189      H      1       S(i)Pr      H 190      Me     1       S(i)Pr      H 191      H      1       SO.sub.2 Me H 192      Me     1       SO.sub.2 Me H 193      H      1       SO.sub.2 Et H 194      Me     1       SO.sub.2 Et H 195      H      1       SO.sub.2 (n)Pr H 196      Me     1       SO.sub.2 (n)Pr H 197      H      1       SO.sub.2 (i)Pr H 198      Me     1       SO.sub.2 (i)Pr H 199      H      1       OMe         H 200      Me     1       OMe         H 201      H      1       OEt         H 202      Me     1       OEt         H 203      H      1       O(n)Pr      H 204      Me     1       O(n)Pr      H 205      H      1       O(i)Pr      H 206      Me     1       O(i)Pr      H 207      H      1       OH          CHNH 208      Me     1       OH          CHNH 209      H      1       OH ##STR244## 210      Me     1       OH ##STR245## 211      H      1       SMe         CHNH 212      Me     1       SMe         CHNH 213      H      1       SMe ##STR246## 214      Me     1       SMe ##STR247## 215      H      1       SO.sub.2 Me CHNH 216      Me     1       SO.sub.2 Me CHNH 217      H      1       SO.sub.2 Me ##STR248## 218      Me     1       SO.sub.2 Me ##STR249## 219      H      1       OMe         CHNH 220      Me     1       OMe         CHNH 221      H      1       OMe ##STR250## 222      Me     1       OMe ##STR251## ______________________________________

## Background
## Claims

1. A compound of the formula: ##STR252## wherein R.sub.1 is a hydrogen atom or a lower alkyl group, R.sub.2 is a hydrogen atom or a conventional protecting group for a carboxyl group, R.sub.0 is a hydrogen atom or a conventional protecting group for a hydroxyl group, X is a protected or unprotected amino group, a carboxyl group, a lower alkoxycarbonyl group, an ar(lower)alkyloxycarbonyl group, a cyano group, a hydroxyl group, a lower alkyloxy group, a lower alkylthio group, a lower alkylsulfonyl group or a group of either one of the following formulas: ##STR253## wherein R.sub.3 and R.sub.4, which may be the same or different, each represent a hydrogen atom or a lower alkyl group, or they are taken together to represent an alkylene chain to form, in combination with the adjacent nitrogen atom, a 3- to 7-membered cyclic amino group, wherein Z represents --NH-- or --O-- and R.sub.5 represents an amino group, a mono(lower)alkylamino group, a di(lower)alkylamino group, a lower alkyloxy group or a lower alkyl group, ##STR254## wherein R.sub.6 represents a hydrogen atom or a lower alkyl group, wherein R.sub.7 represents a mono(lower)alkylamino group, a di(lower)alkylamino group or a lower alkyloxy group, or ##STR255## wherein R.sub.8, R.sub.9 and R.sub.10, which may be the same or different, each represent a hydrogen atom or a lower alkyl group, Y represents a hydrogen atom, a conventional protecting group for an amino group or a group of either one of the following formulas: ##STR256## wherein R.sub.11 and R.sub.12, which may be the same or different, each represents a hydrogen atom or a lower alkyl group or ##STR257## wherein R.sub.6 is as defined above and n is an integer of 1 to 6, and a pharmacologically acceptable salt thereof.

2. A compound as claimed in claim 1, wherein R.sub.0 and R.sub.2 each are a hydrogen atom and X is an amino group, a carboxyl group, a lower alkoxycarbonyl group, an ar(lower)alkyloxycarbonyl group, a cyano group, a hydroxyl group, a lower alkyloxy group, a lower alkylthio group, a lower alkylsulfonyl group or a group of either one of the following formulas: ##STR258## wherein R.sub.3 and R.sub.4 are as defined in claim 1, wherein Z and R.sub.5 are as defined in claim 1, ##STR259## wherein R.sub.6 is as defined in claim 1, wherein R.sub.7 is as defined in claim 1, or ##STR260## wherein R.sub.8, R.sub.9 and R.sub.10 are as defined in claim 1, and Y is a hydrogen atom or a group of either one of the following formulas: ##STR261## wherein R.sub.11 and R.sub.12 are as defined in claim 1, or ##STR262## wherein R.sub.6 is as defined in claim 1.

3. A compound as claimed in claim 1, wherein R.sub.0 and R.sub.2 each are a hydrogen atom, X is a carboxyl group, a lower alkoxycarbonyl group, a cyano group, a hydroxyl group, a lower alkyloxy group or a group of either one of the following formulas: ##STR263## wherein R.sub.3 and R.sub.4 are as defined in claim 1, wherein R.sub.7 is as defined in claim 1, or ##STR264## wherein R.sub.8, R.sub.9 and R.sub.10 are as defomed om claim 1, and Y is a hydrogen atom.

4. A compound as claimed in claim 3, wherein X is a group of the formula: ##STR265## wherein R.sub.3a and R.sub.4a each represent a hydrogen atom or a methyl group.

5. A compound as claimed in claim 3, wherein X is a hydroxyl group or a lower alkyloxy group.

6. A compound as claimed in any one of claims 1 to 5, wherein R.sub.1 is a methyl group.

7. A compound as claimed in claim 6, which has a (5S)-configuration.

8. A compound as claimed in claim 7, which has a (4R,5S,6S,8R)-configuration.

9. A compound as claimed in claim 3, wherein R.sub.1 is a hydrogen atom.

10. A compound as claimed in claim 9, which has a (5R)-configuration.

11. A compound as claimed in claim 10, which has a (5R,6S,8R)-configuration.

12. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'R,4'S)-3-[(2-dimethylaminocarbonylmethyl-pyrrolidin)-4-ylth io]-4-methyl-6-(1-hydroxyethyl)-1-azabicyclo[3.2.0]-hept-2-en-7-one-2-carbo xylic acid, or a salt thereof.

13. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'R,4'S)-3-[(2-methylaminocarbonylmethylpyrrolidin)-4-ylthio] -4-methyl-6-(1-hydroxyethyl)-1-azabicyclo[3.2.0]-hept-2-en-7-one-2-carboxyl ic acid, or a salt thereof.

14. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'R,4'S)-3-[(2-carbamoylmethylpyrrolidin)-4-ylthio]-b 4-methyl-6-(1-hydroxyethyl)-1-azabicyclo[3.2.0]-hept-2-en-7-one-2-carboxyl ic acid, or a salt thereof.

15. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'R,4'S)-3-[(2-(2-dimethylaminocarbonylethyl)-pyrrolidin)-4-y lthio]-4-methyl-6-(1-hydroxyethyl)-1-azabicyclo[3.2.0]-hept-2-en-7-one-2-ca rboxylic acid, or a salt thereof.

16. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'R,4'S)-3-[(2-(2-methylaminocarbonylethyl)-pyrrolidin)-4-ylt hio]-4-methyl-6-(1-hydroxyethyl)-1-azabicyclo[3.2.0]-hept-2-en-7-one-2-carb oxylic acid, or a salt thereof.

17. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'R,4'S)-3-[(2-(2-carbamoylethyl)pyrrolidin)-4-ylthio]-4-meth yl-6-(1-hydroxyethyl)-1-azabicyclo[3.2.0]-hept-2-en-7-one-2-carboxylic acid, or a salt thereof.

18. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'S,4'S)-3-[(2-hydroxymethylpyrrolidin)-4-ylthio]-4-methyl-6- (1-hydroxyethyl)-1-azabicyclo[3.2.0]-hept-2-en-7-one-2-carboxylic acid, or a salt thereof.

19. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'S,4'S)-3-[2-methoxymethylpyrrolidin)-4-ylthio]-4-methyl-6-( 1-hydroxyethyl)-1-azabicyclo[3.2.0]-hept-2-en-7-one-2-carboxylic acid, or a salt thereof.

20. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'R,4'S)-3-[(2-(2-carboxyethyl)pyrrolidin)-4-ylthio]-4-methyl -6-(1-hydroxyethyl)-1-azabicyclo-[3.2.0]-hept-2-en-7-one-2-carboxylic acid, or a salt thereof.

21. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'R,4'S)-3-[(2-methoxycarbonylmethylpyrrolidin)-4-ylthio]-4-m ethyl-6-(1-hydroxyethyl)-1-azabicyclo[3.2.0]-hept-2-en-7-one-2-carboxylic acid, or a salt thereof.

22. A compound as claimed in claim 1, which is (4R,5S,6S,8R,2'R,4'S)-3-[(2-(2-N,N-dimethylhydrazonoethyl)pyrrolidin)-4-yl thio]-4-methyl-6-(1-hydroxyethyl)1-azabicyclo[3.2.0]-hept-2-en-7-one-2-carb oxylic acid, or a salt thereof.

23. A pharmaceutical composition for antimicrobial use which comprises as an active ingredient a pharmaceutically effective amount of a compound according to claim 1, and at least one pharmaceutically acceptable inert carrier or diluent.

24. A pharmaceutical composition for antimicrobial which comprises as an active ingredient a pharmaceutically effective amount of a compounding according to claim 2, and at least one pharmaceutically acceptable carrier or diluent.

25. A method for treating an infectious disease caused by bacteria, which comprises administering an effective amount of a compound according to claim I as an antimicrobial agent to a patient suffering from said disease caused by bacteria.

26. A compounding according to claim 1, which is represented by the formula: ##STR266##

27. A compound according to claim 1, which is represented by the formula: ##STR267##

28. A compound according to claim 1, which is represented by the formula: ##STR268##

29. A compound according to claim 1, which is represented by the formula: ##STR269##