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my %resulting_vendors;
my %vendors = %{ $xmldoc->{Catalog}{Vendors}{Vendor} };
...
    $resulting_vendors{$vendors{$vendor2}{vendorUniqueKey}}=$vendor2;
}
print Data::Dumper->Dump( [\%resulting_vendors], [qw(resulting_vendors
+)] );

my %vendors = %{ $xmldoc->{Catalog}{Vendors}{Vendor} };