Having the joining process run in reverse does not quite cut it but it should be at least as involved.
Sort of like ending marriages are more complicated then beginning them.
If the Constitution can be amended, the Union itself can be liquidated, too. But civil war is not the way to do it. There should have been a legal process in 1860. The Federalist certainly speaks of war between the states as a distinct probability under the Articles of Confederation. So why not improve the Constitution yet further with an Amendment setting forth a process of whole or partial dissolution, making it possible, but a remote possibility, delayed and sublimated with a long procedure, so that the aggrieved state has time to think it over and deliberate before taking the plunge.