Code
%%// Label matrix
L = [
0 0 2 0 0;
2 2 2 1 1;
2 2 1 1 0
0 1 1 1 1]
[X_row,X_col] = find(L==1);
[Y_row,Y_col] = find(L==2);
X = [X_row X_col];
Y = [Y_row Y_col];
%%// You code works till this point to get X and Y
%%// Peform subtractions so that later on could be used to detect
%%// where Y has any index that touches X
%%// Subtract all Y from all X. This can be done by getting one
%%//of them and in this case Y into the third dimension and then subtracting
%%// from all X using bsxfun. The output would be used to index into Y.
Y_touch = abs(bsxfun(@minus,X,permute(Y,[3 2 1])));
%%// Perform similar subtractions, but this time subtracting all X from Y
%%// by putting X into the third dimension. The idea this time is to index
%%// into X.
X_touch = abs(bsxfun(@minus,Y,permute(X,[3 2 1]))); %%// for X too
%%// Find all touching indices for X, which would be [1 1] from X_touch.
%%// Thus, their row-sum would be 2, which can then detected and using `all`
%%// command. The output from that can be "squeezed" into a 2D matrix using
%%// `squeeze` command and then the touching indices would be any `ones`
%%// columnwise.
ind_X = any(squeeze(all(X_touch==1,2)),1)
%%// Similarly for Y
ind_Y = any(squeeze(all(Y_touch==1,2)),1)
%%// Get the touching locations for X and Y
touching_loc = [X(ind_X,:) ; Y(ind_Y,:)]
%%// To verify, let us make the touching indices 10
L(sub2ind(size(L),touching_loc(:,1),touching_loc(:,2)))=10
Output
L =
0 0 2 0 0
2 2 2 1 1
2 2 1 1 0
0 1 1 1 1
L =
0 0 10 0 0
2 10 10 10 1
10 10 10 10 0
0 10 10 1 1