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use Data::Dumper;
use Tie::Autotie 'Tie::IxHash';
...
$Menu_Multi_Hash{'L1A'}{'Second'}{'Third1'} = '/path/to/exe';

print Dumper(\%Menu_Multi_Hash);

$VAR1 = {
          'L1A' => {
...
                                 }
                   }
        };