Mild and effective synthesis of morpholinium 3-cyano-4-methyl-6-oxo-1,6- dihydropyridine-2-thiolate

Full text of DOI:10.1134/S1070428006060236

6
+257ꢀꢀ
&
20081,&$7,216ꢀ
0
LOGꢀDQGꢀ(IIHFWLYHꢀ6\QWKHVLVꢀRIꢀ0RUSKROLQLXPꢀꢀ
ꢁ
ꢂ&\DQRꢂꢃꢂPHWK\OꢂꢄꢂR[RꢂꢅꢆꢄꢂGLK\GURS\ULGLQHꢂꢇꢂWKLRODWHꢀ
9ꢈꢀ'ꢈꢀ'\DFKHQNRꢀ
7DUDVꢀ6KHYFKHQNRꢀ1DWLRQDOꢀ3HGDJRJLFDOꢀ8QLYHUVLW\ꢁꢀXOꢂꢀ2ERURQQD\Dꢀꢃꢁꢀ/XJDQVNꢁꢀꢄꢅꢆꢅꢅꢀ8NUDLQHꢀꢀ
HꢇPDLOꢈꢀGYGBOXJ#RQOLQHꢂOJꢂXDꢀ
5
HFHLYHGꢃ6HSWHPEHUꢃꢄꢅꢆꢃꢄꢂꢂꢇꢃ
'2,ꢉꢃꢋꢂꢎꢋꢋꢈꢁꢏ6ꢋꢂꢐꢂꢁꢄꢅꢂꢂꢊꢂꢊꢂꢄꢈꢊꢃ
0
RUSKROLQLXPꢃ ꢈꢉF\DQRꢉꢁꢉPHWK\OꢉꢊꢉR[RꢉꢋꢆꢊꢉGLK\ꢉ
,QꢃWKHꢃSUHVHQWꢃZRUNꢆꢃWKHꢃFRQGHQVDWLRQꢃRIꢃFRPꢉ
GURS\ULGLQHꢉꢄꢉWKLRODWHꢃꢌ,ꢍꢃZDVꢃV\QWKHVL]HGꢃSUHYLRXVO\ꢃ SRXQGVꢃ,,,ꢃDQGꢃ,,ꢃLQꢃHWKDQROꢃDWꢃURRPꢃWHPSHUDWXUHꢃLQꢃWKHꢃ
E\ꢃFRQGHQVDWLRQꢃRIꢃF\DQRWKLRDFHWDPLGHꢃꢌ,,ꢍꢃZLWKꢃHWK\Oꢃ SUHVHQFHꢃRIꢃDQꢃHTXLPRODUꢃDPRXQWꢃRIꢃPRUSKROLQHꢃZDVꢃ
ꢁ
ꢉPRUSKROLQREXWꢉꢄꢉHQRDWHꢃLQꢃHWKDQROꢃDWꢃꢄꢂƒ&ꢃLQꢃWKHꢃ VKRZQꢃIRUꢃWKHꢃILUVWꢃWLPHꢃWRꢃJLYHꢃVDOWꢃ,ꢃLQꢃTXDQWLWDWLYHꢃ
DEVHQFHꢃRIꢃDꢃFDWDO\VWꢃ>ꢋ@ꢎꢃꢊꢉ+\GUR[\ꢉꢁꢉPHWK\OꢉꢄꢉWKLꢉ
R[RꢉꢋꢆꢄꢉGLK\GURS\ULGLQHꢉꢈꢉFDUERQLWULOHꢃZDVꢃREWDLQHGꢃ
E\ꢃFRQGHQVDWLRQꢃRIꢃHWK\OꢃDFHWRDFHWDWHꢃꢌ,,,ꢍꢃZLWKꢃFRPꢉ
SRXQGꢃ,,ꢃLQꢃS\ULGLQHꢃDWꢃꢋꢊꢂƒ&ꢃLQꢃWKHꢃSUHVHQFHꢃRIꢃꢃ
ꢄꢉꢌGLHWK\ODPLQRꢍHWKDQROꢃ>ꢄ@ꢎꢃ
\LHOGꢎꢃ7KHꢃSURSRVHGꢃSURFHGXUHꢃUHTXLUHVꢃQRꢃSUHOLPLQDU\ꢃ
SUHSDUDWLRQꢃRIꢃWKHꢃFRUUHVSRQGLQJꢃHQDPLQHꢃIURPꢃHWK\Oꢃ
DFHWRDFHWDWHꢃDQGꢃKHDWLQJꢃRIꢃWKHꢃUHDFWLRQꢃPL[WXUHꢎꢃ
7KHꢃDON\ODWLRQꢃRIꢃS\ULGLQHWKLRODWHꢃ,ꢃZLWKꢃꢄꢃHTXLYꢃRIꢃ
EHQ]\OꢃFKORULGHꢃLQꢃ'0)ꢃLQꢃWKHꢃSUHVHQFHꢃRIꢃDꢃEDVHꢃJDYHꢃ
ꢀꢁꢂꢃ

0
,/'ꢃꢃ$1'ꢃꢃ())(&7,9(ꢃꢃ6<17+(6,6ꢃꢃ2)ꢃꢃ0253+2/,1,80ꢃꢃꢈꢉ&<$12ꢉꢁꢉ0(7+</ꢉꢎꢎꢎꢃ
ꢀꢁꢋꢃ
VXEVWLWXWHGꢃꢋꢆꢄꢉGLK\GURS\ULGLQꢉꢄꢉRQHꢃ,9ꢃZKLFKꢃLVꢃ VWDQGꢃIRUꢃꢄꢁꢃKꢎꢃ7KHꢃSUHFLSLWDWHꢃZDVꢃILOWHUHGꢃRIIꢆꢃZDVKHGꢃ
DꢃSURPLVLQJꢃLQWHUPHGLDWHꢃSURGXFWꢃLQꢃWKHꢃV\QWKHVLVꢃRIꢃD]Rꢃ ZLWKꢃZDWHUꢆꢃHWKDQROꢆꢃDQGꢃKH[DQHꢆꢃGULHGꢃLQꢃDLUꢆꢃDQGꢃ
G\HVꢃ>ꢈ@ꢎꢃ7UHDWPHQWꢃRIꢃVDOWꢃ,ꢃZLWKꢃꢁꢉPHWKR[\SKHQDF\Oꢃ KHDWHGꢃLQꢃꢋꢇꢃPOꢃRIꢃDFHWLFꢃDQK\GULGHꢃIRUꢃꢄꢃKꢃXQGHUꢃ
EURPLGHꢆꢃIROORZHGꢃE\ꢃKHDWLQJꢃRIꢃWKHꢃSURGXFWꢃLQꢃERLOLQJꢃ UHIOX[ꢎꢃ7KHꢃPL[WXUHꢃZDVꢃILOWHUHGꢃZKLOHꢃKRWꢃWKURXJKꢃꢃ
DFHWLFꢃDQK\GULGHꢃUHVXOWHGꢃLQꢃIRUPDWLRQꢃRIꢃVXEVWLWXWHGꢃ DꢃIROGHGꢃSDSHUꢃILOWHUꢆꢃDQGꢃWKHꢃILOWUDWHꢃZDVꢃOHIWꢃWRꢃVWDQGꢃ
WKLD]RORS\ULGLQRQHꢃ9ꢃDVꢃSRWHQWLDOꢃSHSWLGRPLPHWLFꢃ>ꢁ@ꢎꢃ IRUꢃꢁꢅꢃKꢎꢃ7KHꢃSUHFLSLWDWHꢃZDVꢃILOWHUHGꢃRIIꢃDQGꢃZDVKHGꢃ
3
$
UHVXPDEO\ꢆꢃWKHꢃUHDFWLRQꢃLQYROYHVꢃIRUPDWLRQꢃRIꢃVXOILGHꢃ ZLWKꢃGLHWK\OꢃHWKHUꢎꢃ<LHOGꢃꢄꢎꢁꢃJꢃꢌꢅꢋBꢍꢆꢃ\HOORZꢃFRWWRQꢉ
ꢃDQGꢃK\GUR[\ꢉVXEVWLWXWHGꢃWKLD]RORS\ULGLQHꢃ%ꢎꢃ
OLNHꢃPDWHULDOꢆꢃPSꢃꢄꢄꢀ±ꢄꢈꢂƒ&ꢃꢌIURPꢃ$F2+ꢍꢎꢃ,5ꢃVSHFꢉ
WUXPꢆꢃ ꢆꢃFP ꢒꢃꢄꢄꢂꢊꢃꢌ& 1ꢍꢆꢃꢋꢊꢀꢁꢃꢌ& 2ꢍꢎꢃ +ꢃ105ꢃ
VSHFWUXPꢆꢃ ꢆꢃSSPꢒꢃꢄꢎꢈꢐꢃVꢃꢌꢈ+ꢆꢃ0HꢍꢆꢃꢈꢎꢅꢀꢃVꢃꢌꢈ+ꢆꢃ0H2ꢍꢆꢃ
ꢇꢎꢀꢀꢃVꢃꢌꢋ+ꢆꢃꢄꢉ+ꢍꢆꢃꢊꢎꢅꢇꢃGꢃDQGꢃꢐꢎꢄꢁꢃGꢃꢌꢄ+ꢃHDFKꢆꢃ&+ꢆꢃꢃ
0
RUSKROLQLXPꢀ ꢁꢂF\DQRꢂꢃꢂPHWK\OꢂꢄꢂR[RꢂꢅꢆꢄꢂGLꢂ
K\GURS\ULGLQHꢂꢇꢂWKLRODWHꢀꢊ,ꢋꢈꢃ0RUSKROLQHꢆꢃꢂꢎꢅꢐꢃPOꢃ
ꢌꢋꢂꢃPPROꢍꢆꢃZDVꢃDGGHGꢃXQGHUꢃVWLUULQJꢃDWꢃꢄꢂƒ&ꢃWRꢃDꢃVXVꢉ
SHQVLRQꢃRIꢃꢋꢎꢂꢃJꢃꢌꢋꢂꢃPPROꢍꢃRIꢃF\DQRWKLRDFHWDPLGHꢃꢌ,,ꢍꢃ
LQꢃꢄꢂꢃPOꢃRIꢃHWKDQROꢎꢃ7KHꢃPL[WXUHꢃZDVꢃVWLUUHGꢃIRUꢃꢇꢃPLQꢃ
XQWLOꢃLWꢃEHFDPHꢃKRPRJHQHRXVꢆꢃꢋꢎꢄꢅꢃPOꢃꢌꢋꢂꢃPPROꢍꢃRIꢃ
HWK\OꢃDFHWRDFHWDWHꢃꢌ,,,ꢍꢃZDVꢃDGGHGꢆꢃDQGꢃWKHꢃPL[WXUHꢃ
-
+
ꢃ ꢃꢅꢎꢅꢄꢃ+]ꢍꢆꢃꢐꢎꢋꢐꢃVꢃꢌꢋ+ꢆꢃꢊꢉ+ꢍꢎꢃ)RXQGꢆꢃBꢒꢃ&ꢃꢊꢁꢎꢊꢅꢑꢃꢃ
ꢃꢈꢎꢀꢋꢑꢃ1ꢃꢀꢎꢄꢀꢎꢃ& + 126ꢎꢃ&DOFXODWHGꢆꢃBꢒꢃ&ꢃꢊꢁꢎꢅꢇꢑꢃ
+ꢃꢁꢎꢂꢅꢑꢃ1ꢃꢀꢎꢁꢇꢎꢃ0ꢃꢄꢀꢊꢎꢈꢁꢅꢎꢃ
7KHꢃ,5ꢃVSHFWUDꢃZHUHꢃUHFRUGHGꢃRQꢃDQꢃ,.6ꢉꢁꢂꢃVSHFꢉ
ZDVꢃVWLUUHGꢃIRUꢃꢋꢂꢃPLQꢃDQGꢃZDVꢃOHIWꢃWRꢃVWDQGꢃIRUꢃꢄꢁꢃKꢎꢃ WURSKRWRPHWHUꢃIURPꢃVDPSOHVꢃGLVSHUVHGꢃLQꢃPLQHUDOꢃRLOꢎꢃ
KHꢃSUHFLSLWDWHꢃZDVꢃILOWHUHGꢃRIIꢃDQGꢃZDVKHGꢃZLWKꢃ 7KHꢃ +ꢃ105ꢃVSHFWUDꢃZHUHꢃPHDVXUHGꢃRQꢃDꢃ9DULDQꢃ
HWKDQROꢃDQGꢃKH[DQHꢎꢃ<LHOGꢃꢄꢎꢂꢃJꢃꢌꢐꢅBꢍꢆꢃZKLWHꢃSRZGHUꢆꢃ 0HUFXU\ꢉꢁꢂꢂꢃLQVWUXPHQWꢃꢌꢁꢂꢂꢎꢈꢀꢐꢃ0+]ꢍꢃIURPꢃVROXꢉ
7
WLRQVꢃLQꢃ'062ꢉG ꢃXVLQJꢃWHWUDPHWK\OVLODQHꢃDVꢃLQWHUQDOꢃ
UHIHUHQFHꢎꢃ7KHꢃPDVVꢃVSHFWUXPꢃRIꢃVDOWꢃ,ꢃꢌꢐꢂꢃH9ꢍꢃZDVꢃ
REWDLQHGꢃRQꢃDꢃ.UDWRVꢃ06ꢉꢅꢀꢂꢃVSHFWURPHWHUꢃZLWKꢃGLUHFWꢃ
VDPSOHꢃDGPLVVLRQꢃLQWRꢃWKHꢃLRQꢃVRXUFHꢎꢃ
PSꢃꢄꢄꢁ±ꢄꢄꢊƒ&ꢑꢃSXEOLVKHGꢃGDWDꢃ>ꢋ@ꢒꢃPSꢃꢄꢄꢊ±ꢄꢄꢅƒ&ꢎꢃ
0
DVVꢃVSHFWUXPꢆꢃPꢏ]ꢃꢌ, ꢆꢃBꢍꢒꢃꢋꢊꢊꢃꢌꢐꢅꢍꢃ>0ꢃꢓꢃꢋ@ ꢃ
ꢌDQLRQLFꢃIUDJPHQWꢍꢆꢃꢋꢈꢅꢌꢁꢀꢍꢆꢃꢋꢈꢈꢃꢌꢄꢇꢍꢆꢃꢋꢄꢄꢃꢌꢋꢁꢍꢆꢃꢋꢋꢂꢃ
ꢌꢋꢇꢍꢆꢃꢋꢂꢇꢃꢌꢈꢄꢍꢆꢃꢅꢐꢃꢌꢈꢊꢍꢃ>0ꢃ±ꢃꢋ@ ꢃꢌFDWLRQLFꢃIUDJPHQWꢍꢆꢃꢅꢈꢃ
ꢌꢋꢁꢍꢆꢃꢐꢅꢃꢌꢇꢀꢍꢆꢃꢐꢂꢃꢌꢋꢋꢍꢆꢃꢊꢈꢃꢌꢋꢁꢍꢆꢃꢇꢐꢃꢌꢋꢂꢂꢍꢆꢃꢇꢋꢃꢌꢈꢈꢍꢎꢃꢃ
5()(5(1&(6ꢃ
ꢅꢂ%HQ]\OꢂꢇꢂEHQ]\OVXOIDQ\OꢂꢃꢂPHWK\OꢂꢄꢂR[Rꢂꢅꢆꢄꢂ
GLK\GURS\ULGLQHꢂꢁꢂFDUERQLWULOHꢀꢊ,9ꢋꢈꢃ6DOWꢃ,ꢆꢃꢄꢎꢇꢈꢃJꢃ
ꢋꢎꢃ'\DFKHQNRꢆꢃ9ꢎ'ꢎꢆꢃ6KDUDQLQꢆꢃ<Xꢎ$ꢎꢆꢃ6KHVWRSDORYꢆꢃ$ꢎ0ꢎꢆꢃ
ꢌꢋꢂꢃPPROꢍꢆꢃZDVꢃGLVVROYHGꢃLQꢃꢋꢇꢃPOꢃRIꢃ'0)ꢆꢃꢇꢎꢊꢃPOꢃꢃ ꢃ 5RGLQRYVND\Dꢆꢃ /ꢎ$ꢎꢆꢃ 7XURYꢆꢃ$ꢎ9ꢎꢆꢃ /LWYLQRYꢆꢃ 9ꢎ3ꢎꢆꢃ DQGꢃ
ꢌꢋꢂꢃPPROꢍꢃRIꢃꢋꢂBꢃDTXHRXVꢃSRWDVVLXPꢃK\GUR[LGHꢃDQGꢃ ꢃ 3URPRQHQNRYꢆꢃ9ꢎ.ꢎꢆꢃ=Kꢂꢀ 2EVKFKꢂꢀ .KLPꢎꢆꢃꢋꢀꢀꢂꢆꢃYROꢎꢃꢊꢂꢆꢃꢃ
ꢃ Sꢎꢃ ꢄꢈꢅꢁꢑꢃ /LWYLQRYꢆꢃ 9ꢎ3ꢎꢆꢃ 6KDUDQLQꢆꢃ <Xꢎ$ꢎꢆꢃ 3URPRQHQꢉꢃ
ꢄꢎꢈꢃPOꢃꢌꢄꢂꢃPPROꢍꢃRIꢃEHQ]\OꢃFKORULGHꢃZHUHꢃDGGHGꢃLQꢃ
ꢃ NRYꢆꢃ9ꢎ.ꢎꢆꢃ5RGLQRYVND\Dꢆꢃ/ꢎ$ꢎꢆꢃ6KHVWRSDORYꢆꢃ$ꢎ0ꢎꢆꢃDQGꢃ
VXFFHVVLRQꢃDWꢃURRPꢃWHPSHUDWXUHꢆꢃDQGꢃWKHꢃPL[WXUHꢃZDVꢃ
ꢃ 0RUWLNRYꢆꢃ9ꢎ<Xꢎꢆꢃ,]Yꢂꢀ$NDGꢂꢀ1DXNꢀ6665ꢁꢀ6HUꢂꢀ.KLPꢎꢆꢃꢋꢀꢅꢁꢆꢃ
VWLUUHGꢃIRUꢃꢈꢃKꢆꢃGLOXWHGꢃZLWKꢃDQꢃHTXDOꢃYROXPHꢃRIꢃZDWHUꢆꢃ
ꢃ Sꢎꢃꢋꢅꢊꢀꢎꢃ
DQGꢃOHIWꢃWRꢃVWDQGꢃIRUꢃꢁꢅꢃKꢎꢃ7KHꢃSUHFLSLWDWHꢃZDVꢃILOWHUHGꢃ
ꢄꢎꢃ6FKPLGWꢃ8ꢎꢃDQGꢃ.XELW]HNꢆꢃ+ꢎꢆꢃ&KHPꢂꢀ%HUꢎꢆꢃꢋꢀꢊꢂꢆꢃYROꢎꢃꢀꢈꢆꢃ
RIIꢃDQGꢃZDVKHGꢃZLWKꢃZDWHUꢆꢃHWKDQROꢆꢃDQGꢃKH[DQHꢎꢃ<LHOGꢃ
ꢃ Sꢎꢃꢋꢇꢇꢀꢎꢃ
ꢄꢎꢄꢅꢃJꢃꢌꢊꢊBꢍꢆꢃFRORUOHVVꢃQHHGOHVꢆꢃPSꢃꢐꢈ±ꢐꢁƒ&ꢃꢌIURPꢃ
ꢈꢎꢃ/HHꢆꢃ.ꢎ7ꢎꢆꢃ6RQꢆꢃ<ꢎ6ꢎꢆꢃ+DQꢆꢃ:ꢎ6ꢎꢆꢃ-RRꢆꢃ%ꢎ-ꢎꢆꢃDQGꢃ(RPꢆꢃ6ꢎ<ꢎꢆꢃ
$
F2+ꢍꢎꢃ,5ꢃVSHFWUXPꢆꢃ ꢆꢃFP ꢒꢃꢄꢄꢂꢁꢃꢌ& 1ꢍꢆꢃꢋꢊꢀꢇꢃ
ꢃ 86ꢃ3DWHQWꢃQRꢎꢃꢇꢀꢄꢀꢄꢋꢅꢆꢃꢋꢀꢀꢀꢑꢃ5HIꢂꢀ =Kꢂꢁꢀ .KLPꢎꢆꢃꢄꢂꢂꢂꢆꢃꢃ
ꢃ QRꢎꢃꢋꢀ1ꢋꢊꢂ3ꢑꢃ0KHLGOHꢆꢃ0ꢎꢆꢃ/DFURL[ꢆꢃ5ꢎꢆꢃDQGꢃ6FKHLEOLꢆꢃ3ꢎꢆꢃ
ꢃ (8ꢃ 3DWHQWꢃ QRꢎꢃ ꢅꢅꢇꢀꢀꢀꢆꢃ ꢌꢋꢀꢀꢐꢑꢃ &KHPꢂꢀ $EVWUꢎꢆꢃ ꢋꢀꢀꢀꢆꢃꢃ
ꢌ& 2ꢍꢎꢃ +ꢃ105ꢃVSHFWUXPꢆꢃ ꢆꢃSSPꢒꢃꢄꢎꢁꢈꢃVꢃꢌꢈ+ꢆꢃ0Hꢍꢆꢃ
ꢎꢁꢁꢃVꢃꢌꢄ+ꢆꢃ6&+ ꢍꢆꢃꢇꢎꢈꢅꢃVꢃꢌꢄ+ꢆꢃ1&+ ꢍꢆꢃꢊꢎꢇꢋꢃVꢃꢌꢋ+ꢆꢃꢃ
ꢁ
ꢇꢉ+ꢍꢆꢃꢐꢎꢋꢇ±ꢐꢎꢈꢊꢃPꢃꢌꢋꢂ+ꢆꢃ+ ꢍꢎꢃ)RXQGꢆꢃBꢒꢃ&ꢃꢐꢄꢎꢊꢂꢑꢃꢃ ꢃ YROꢎꢃ ꢋꢈꢂꢆꢃ QRꢎꢃ ꢅꢄꢅꢋꢁKꢑꢃ &DUOLQLꢆꢃ 5ꢎꢆꢃ %DQQLQJꢆꢃ -ꢎ+ꢎꢆꢃꢃ
+
ꢃꢇꢎꢂꢊꢑꢃ1ꢃꢐꢎꢅꢅꢎꢃ& + 126ꢎꢃ&DOFXODWHGꢆꢃBꢒꢃ&ꢃꢐꢄꢎꢅꢋꢑꢃ ꢃ 'XIIꢆꢃ -ꢎ0ꢎꢆꢃ :Xꢆꢃ %ꢎꢆꢃ DQGꢃ 0D\Rꢆꢃ -ꢎ'ꢎꢆꢃ 86ꢃ 3DWHQWꢃꢃ
ꢃ QRꢎꢃꢊꢐꢋꢈꢊꢋꢁꢆꢃꢄꢂꢂꢁꢑꢃ5HIꢂꢀ=Kꢂꢁꢀ.KLPꢎꢆꢃꢄꢂꢂꢁꢆꢃQRꢎꢃꢋꢀ1ꢋꢁꢊ3ꢑꢃ
ꢃ 6FKDHW]HUꢆꢃ-ꢎꢆꢃ6ZLVVꢃ3DWHQWꢃQRꢎꢃꢊꢅꢀꢀꢅꢂꢆꢃꢄꢂꢂꢂꢑꢃ5HIꢂꢀ =Kꢂꢁꢀ
+ꢃꢇꢎꢄꢁꢑꢃ1ꢃꢅꢎꢂꢀꢎꢃꢃ
ꢁ
ꢂꢊꢃꢂ0HWKR[\SKHQ\OꢋꢂꢌꢂPHWK\OꢂꢍꢂR[Rꢂꢃꢆꢍꢂ
GLK\GURWKLD]ROR>ꢁꢆꢇꢂD@S\ULGLQHꢂꢎꢂFDUERQLWULOHꢀ ꢊ9ꢋꢈꢃꢃ
ꢃPL[WXUHꢃRIꢃꢄꢎꢇꢈꢃJꢃꢌꢋꢂꢃPPROꢍꢃRIꢃFRPSRXQGꢃ,ꢃDQGꢃ
ꢄꢎꢄꢀꢃJꢃꢌꢋꢂꢃPPROꢍꢃRIꢃꢁꢉPHWKR[\SKHQDF\OꢃEURPLGHꢃLQꢃꢃ
ꢀ
.KLPꢎꢆꢃꢄꢂꢂꢂꢆꢃQRꢎꢃꢋꢀ1ꢋꢇꢂ3ꢎꢃ
ꢁ
ꢎꢃ'UDJRYLFKꢆꢃ3ꢎ6ꢎꢆꢃ3ULQVꢆꢃ7ꢎ-ꢎꢆꢃ=KRXꢆꢃ5ꢎꢆꢃ-RKQVRQꢆꢃ7ꢎ2ꢎꢆꢃ
$
ꢃ %URZQꢆꢃ (ꢎ/ꢎꢆꢃ 0DOGRQDGRꢆꢃ )ꢎ&ꢎꢆꢃ )XKUPDQꢆꢃ 6ꢎ$ꢎꢆꢃ =DOꢉꢃ
ꢃ PDQꢆꢃ /ꢎ6ꢎꢆꢃ 3DWLFNꢆꢃ $ꢎ.ꢎꢆꢃ 0DWWKHZVꢆꢃ 'ꢎ$ꢎꢆꢃ +RXꢆꢃ ;ꢎꢆꢃ
ꢋꢇꢃPOꢃRIꢃ'0)ꢃZDVꢃVWLUUHGꢃIRUꢃꢄꢃKꢃDWꢃꢄꢂƒ&ꢎꢃ,WꢃZDVꢃWKHQꢃ ꢃ 0HDGRUꢆꢃ-ꢎ:ꢎꢆꢃ)HUUHꢆꢃ5ꢎ$ꢎꢆꢃDQGꢃ:RUODQGꢆꢃ6ꢎ7ꢎꢆꢃ%LRRUJꢂꢀ
GLOXWHGꢃZLWKꢃDQꢃHTXDOꢃYROXPHꢃRIꢃZDWHUꢃDQGꢃZDVꢃOHIWꢃWRꢃ ꢀ 0HGꢂꢀ&KHPꢂꢀ/HWWꢎꢆꢃꢄꢂꢂꢄꢆꢃYROꢎꢃꢋꢄꢆꢃSꢎꢃꢐꢈꢈꢎꢃ
5
866,$1ꢃꢃ-2851$/ꢃꢃ2)ꢃꢃ25*$1,&ꢃꢃ&+(0,675<ꢃꢃꢃ9ROꢎꢃꢃꢁꢄꢃꢃꢃ1Rꢎꢃꢃꢊꢃꢃꢃꢄꢂꢂꢊꢃ