when was the first time such a star was spotted?
1910
White dwarf
The pair 40 Eridani B/C was discovered by William Herschel on 31 January 1783. In 1910, Henry Norris Russell, Edward Charles Pickering and Williamina Fleming discovered that, despite being a dim star, 40 Eridani B was of spectral type A, or white. In 1939, Russell looked back on the discovery:

which of the following will never undergo fusion in any star White dwarf
wiki:19666764
White dwarf [SEP] Discovery
Fleming) that the spectrum of this star was A. I knew enough about it, even in these paleozoic days, to realize at once that there was an extreme inconsistency between what we would then have called "possible" values of the surface brightness and density. I must have shown that I was not only puzzled but crestfallen, at this exception to what looked like a very pretty rule of stellar characteristics; but Pickering smiled upon me, and said: "It is just these exceptions that lead to an advance in our knowledge", and so the white dwarfs entered the realm of study! The spectral type of 40 Eridani B was officially described in 1914 by Walter Adams.