3.2.4. Hydroxybenzophenones

Maclurin 3-C-hexoside derivates (Figure 9) were identified by their molecular formula and characteristic fragment at *m*/*z* 303 due to retro Diels–Alder cleavage of hexoside. Thus, peak 10 ([M−H]<sup>−</sup> = 423.0943, C19 H19 O11) was identified as maclurin 3-C-hexoside. Peak 14 ([M−H]<sup>−</sup> = 575.1047, C26 H23 O15) had main fragments at *m*/*z* 423 (loss of galloyl) and 303, so it was identified as maclurin 3-C-(2-O-galloyl)-hexoside. Peak 18 ([M−H]<sup>−</sup> = 737.1588, C32 H33 O20) showed a main MS2 fragment at *m*/*z* 575 due to a loss of hexoside, and MS3 fragments at *m*/*z* 423 and 303 as the previous peak, so it was identified as maclurin 3-C-(2-O-hexosyl-galloyl)-hexoside. Peak 26 ([M−H]<sup>−</sup> = 727.1166, C33 H27 O19), identified as maclurin 3-C-(2,3-di-O-galloyl)-hexoside, had an MS2 fragment at *m*/*z* 575 due to the loss of one galloyl, and main MS3 fragments at *m*/*z* 485 (cleavage of hexoside) and 405 (loss of O-galloyl). Peak 34 ([M−H]<sup>−</sup> = 543.1149, C26 H23 O13) had a main fragment at *m*/*z* 285 due to the loss of water of a fragment at *m*/*z* 303, coincident with reports for maclurin-3-C-(p-hydroxybenzoyl)-hexoside [19,48].

Peak 25 ([M−H]<sup>−</sup> = 559.1101, C26 H23 O14) was identified as iriflophenone 3-C-(2-O-galloyl)- hexoside, due to its MS2 fragment at *m*/*z* 407 ([M−H−152]<sup>−</sup>, loss of galloyl) and MS3 fragment at *m*/*z* 287 (hexoside cleavage). Peak 36 ([M−H]<sup>−</sup> = 711.1216, C33 H27 O18) had an MS2 fragment at *m*/*z* 559 due to a loss of a galloyl, and an MS3 fragment at 387 (loss of O-galloyl), so it was assigned to iriflophenone 3-C-(2,3-di-O-galloyl)-hexoside [49].


**Figure 9.** Structure and fragments of hydroxybenzophenones a Positions of substituents may vary among the hexoside ring.
