You could use some negated classes:
>>> import re
>>> mystring = "You said {single order='randomize'} that P.E is...Why?"
>>> if mystring.find("randomize") != -1:
... if re.search(r'{[^{}]*randomize[^{}]*}', mystring):
... print("'randomize' present within braces")
... else:
... print("'randomize' present but not within braces")
... else:
... print("'randomize' absent")
# => 'randomize' present within braces