. 2016 Feb 18;21(2):227. doi: 10.3390/molecules21020227

Table 2.

The HPLC-MSⁿ data and compound names of the 20 peaks.

Peak No.	t_R (min)	[M − H]⁻ [M + H]⁺	Negative Mode	Positive Mode	Identification
F1	10.228	499.3346 501.3562	MS¹: 499.3346 [M – H]⁻ MS²: 499.3346→481.3221 [M – 18(H₂O) − H]⁻, 467.3075 [M − 32(2CH₄) − H]⁻, 437.2931 [M − 62(CH₄ + HCOOH) − H]⁻, 419.2964 [M − 80(CH₄ + HCOOH + H₂O) − H]⁻, 325.2526 [M − 174(H₂O + side chainon D ring) − H]⁻ MS³: 419.2964→403.2698 [M − 80(H₂O + CH₄ + HCOOH) − 16(CH₄) − H]⁻	MS¹: 501.3562 [M + H]⁺, 483.3447 [M − 18(H₂O) + H]⁺, 465.3384 [M − 36(2H₂O) + H]⁺ MS²: 501.3562→483.3460 [M − 18(H₂O) + H]⁺, 465.3330 [M − 36(2H₂O) + H]⁺ MS³: 483.3460→465.3324 [M − 18(H₂O) − 18(H₂O) + H]⁺, 447.3232 [M − 18(H₂O) − 36(2H₂O) + H]⁺, 419.3319 [M − 18(H₂O) − 64(H₂O + HCOOH) + H]⁺, 327.2338 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺, 309.2208 [M − 18(H₂O) − 174(H₂O + side chain on D ring) + H]⁺, 465.3324→447.3118 [M − 36(2H₂O) − 18(H₂O) + H]⁺, 309.2139 [M − 36(2H₂O) − 156(side chain on D ring) + H]⁺, 291.2027 [M − 36(2H₂O) − 174(H₂O + side chain on D ring) + H]⁺	29-Hydroxy-dehydrotumulosic acid [32]
F2	12.637	513.3213 515.3352	MS¹: 513.3213 [M − H]⁻ MS²: 513.3213→481.3303 [M − 32(2CH₄) − H]⁻ MS³: 481.3303→466.3146 [M − 32(2CH₄) − 15(CH₃) − H]⁻	MS¹: 515.3352 [M + H]⁺, 497.3238 [M − 18(H₂O) + H]⁺ MS²: 515.3352→497.3235 [M − 18(H₂O) +H]⁺, 461.3047 [M − 54(3H₂O) + H]⁺, 433.3021 [M − 82(2H₂O + HCOOH) + H]⁺, 341.2130 [M − 174(H₂O + side chain on D ring) + H]⁺ MS³: 497.3238→341.2081 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺, 323.1985 [M − 18(H₂O) − 174(H₂O + side chain on D ring) + H]⁺	5α, 8α-Peroxy-dehydrotumulosic acid [5]
F3	13.665	497.3254 499.3394	MS¹: 497.3254 [M − H]⁻ MS²: 497.3254→479.3096 [M − 18(H₂O) − H]⁻, 435.3142 [M − 64(H₂O + HCOOH) − H]⁻, 419.2947 [M − 78(2CH₄ + HCOOH) − H]⁻, 401.2782 [M − 96(2CH₄ + H₂O + HCOOH) − H]⁻ MS³: 419.2947→403.2698 [M − 78(2CH₄ + HCOOH) − 16(CH₄) − H]⁻	MS¹: 499.3494 [M + H]⁺, 481.3307 [M − 18(H₂O) + H]⁺, 463.3196 [M − 36(2H₂O) + H]⁺, 346.3312 [M − 153(CH₃ + RDA fragmentation of B ring) + H]⁺ MS²: 499.3394→481.3306 [M − 18(H₂O) + H]⁺, 463.3205 [M − 36(2H₂O) + H]⁺ MS³: 481.3306→463.3220 [M − 18(H₂O) − 18(H₂O) + H]⁺, 445.3217 [M − 18(H₂O) − 36(2H₂O) + H]⁺, 417.3181 [M − 18(H₂O) − 64(H₂O + HCOOH) + H]⁺, 325.2182 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺ or [M − 18(H₂O) − 156(H₂O + RDA fragmentation of B ring) + H]⁺, 307.2059 [M − 18(H₂O) − 174(H₂O + side chain on D ring) + H]⁺, 463.3205→445.3125 [M − 36(2H₂O) − 18(H₂O) + H]⁺, 417.3209 [M − 36(2H₂O) − 46(HCOOH) + H]⁺, 307.1993 [M − 36(2H₂O) − 156(side chain on D ring) + H]⁺	6α-Hydroxy-polyporenic acid C [33]
F4	19.150	497.3287 499.3436	MS¹: 497.3287 [M − H]⁻ MS²: 497.3287→467.3141 [M − 30(2CH₃) − H]⁻ MS³: 467.3141→421.3067 [M − 30(2CH₃) − 46 (HCOOH) − H]⁻, 389.2857 [M − 30(2CH₃) − 78 (2CH₄ + HCOOH) − H]⁻	MS¹: 499.3436 [M + H]⁺, 521.3314 [M + Na]⁺, 481.3343 [M − 18(H₂O) + H]⁺ MS²: 499.3436→481.3343 [M − 18(H₂O) + H]⁺, 469.3290 [M − 30(2CH₃) + H]⁺, 451.3264 [M − 48(2CH₃ + H₂O) + H]⁺, 330.6835 [M − 68(2CH₃ + RDA fragmentation of B ring) + H]⁺, 327.1625 [M − 172(side chain on D ring) + H]⁺, 325.2160 [M − 174(2H₂O + RDA fragmentation of B ring) + H]⁺, 297.1598 [M − 202(2CH₃ + side chain on D ring) + H]⁺, 279.1605 [M − 220(2H₂O + HCOOH + RDA fragmentation of B ring) + H]⁺ MS³: 481.3433→463.3205 [M − 18(H₂O) − 18(H₂O) + H] ⁺, 451.3202 [M − 18(H₂O) − 30(2CH₃) + H]⁺, 325.2160 [M − 18(H₂O) − 156(H₂O + RDA fragmentation of B ring) + H]⁺, 295.2101 [M − 18(H₂O) − 186(2CH₃ + H₂O + RDA fragmentation of B ring) + H]⁺, 451.3264→295.2045 [M − 48(2CH₃ + H₂O) − 156(H₂O + RDA fragmentation of B ring) + H]⁺	3-oxo-16α,25-dihydroxylanosta-7,9(11),24(31)-trien-21-oic acid
F5	23.845	469.3329 471.3508	MS¹: 469.3329 [M − H]⁻ MS²: 469.3329→425.3429 [M − 44(CO₂) − H]⁻ MS³: 425.3429→409.3112 [M − 44(CO₂) − 16(CH₄) − H]⁻	MS¹: 471.3508 [M + H]⁺, 509.3063 [M + K]⁺, 493.3397 [M + Na]⁺, 453.3371 [M − 18(H₂O) + H]⁺, 435.3267 [M − 36(2H₂O) + H]⁺ MS²: 471.3508→453.3350 [M − 18(H₂O) + H]⁺ MS³: 453.3350→435.3268 [M − 18(H₂O) − 18(H₂O) + H]⁺, 311.2349 [M − 18(H₂O) − 142(side chain on D ring) + H]⁺, 293.2289 [M − 18(H₂O) − 160(H₂O + side chain on D ring) + H]⁺, 311.2349→293.2229 [M − 18(H₂O) − 142(side chain on D ring) − 18(H₂O) + H]⁺, 278.2023 [M − 18(H₂O) − 142(side chain on D ring) − 33(H₂O + CH₃) + H]⁺	3β,16α-Dihydroxy-lanosta-7,9(11),24-trien-21-oic acid [34]
F6	28.422	541.3569 543.3700	MS¹: 541.3569 [M − H]⁻, 481.3308 [M − 60(CH₃COOH) − H]⁻, 384.9361 [M − 156(side chain on D ring) − H]⁻ MS²: 541.3569→481.3293 [M − 60(CH₃COOH) − H]⁻	MS¹: 543.3700 [M + H]⁺, 525.3596 [M − 18(H₂O) + H]⁺, 507.3346 [M − 36(2H₂O) + H]⁺, 465.3378 [M − 78(H₂O + CH₃COOH) + H]⁺, 447.3277 [M − 96(2H₂O + CH₃COOH) + H]⁺, 361.6931 [M − 182(RDA fragmentation of B ring) + H]⁺ MS²: 543.3700→525.3521 [M − 18(H₂O) + H]⁺, 507.3462 [M − 36(2H₂O) + H]⁺, 465.3363 [M − 78(H₂O + CH₃COOH) + H]⁺, 447.3277 [M − 96(2H₂O + CH₃COOH) + H]⁺, 369.2441 [M − 174(H₂O + side chain on D ring) + H]⁺, 361.6931 [M − 182(RDA fragmentation of B ring) + H]⁺, 291.2117 [M − 18(H₂O) − 234(H₂O + side chain on D ring + CH₃COOH) + H]⁺ MS³: 465.3378→447.3228 [M − 78(H₂O + CH₃COOH) − 18(H₂O) + H]⁺, 429.3027 [M − 78(H₂O + CH₃COOH) − 36(2H₂O) + H]⁺, 419.3290 [M − 78(H₂O + CH₃COOH) − 46(HCOOH) + H]⁺, 309.2194 [M − 78(H₂O + CH₃COOH) − 156(side chain on D ring) + H]⁺, 291.2111 [M − 78(H₂O + CH₃COOH) − 174(H₂O + side chain on D ring) + H]⁺, 447.3277→291.2103 [M − 96(2H₂O+CH₃COOH) − 156(side chain on D ring) + H]⁺	6α-Hydroxy-dehydropachymic acid [34]
F7	29.043	483.2973 485.3333	MS¹: 483.2973 [M − H]⁻ MS²: 483.2973→465.2966 [M − 18(H₂O) − H]⁻	MS¹: 485.3332 [M + H]⁺, 507.3094 [M + Na]⁺, 467.3190 [M − 18(H₂O) + H]⁺, 449.3071 [M − 36(2H₂O) + H]⁺, 328.9961 [M − 156(H₂O + RDA fragmentation of B ring) + H]⁺, 326.0151 [M − 158(CH₄ + side chain on D ring) + H]⁺, 311.1511 [M − 174(2CH₄ + side chain on D ring) + H]⁺ or [M − 174(2H₂O + RDA fragmentation of B ring) + H]⁺ MS²: 485.3333→467.3242 [M − 18(H₂O) + H] ⁺, 449.3070 [M − 36(2H₂O) + H]⁺, 325.2146 [M − 160(H₂O + side chain on D ring) + H]⁺ MS³: 467.3242→449.3048 [M − 18(H₂O) − 18(H₂O) + H]⁺, 431.2976 [M − 18(H₂O) − 36(2H₂O) + H]⁺, 325.2218 [M − 18(H₂O) − 142(side chain on D ring) + H]⁺, 449.3070→ 431.3046 [M − 36(2H₂O) − 18(H₂O) + H]⁺, 307.2038 [M − 36(H₂O) − 142(side chain on D ring) + H]⁺	3-oxo-6,16α-dihydroxylanosta-7,9(11),24(31)-trien-21-oic acid [35]
F8	32.068	483.3425 485.3602	MS¹: 483.3425 [M − H]⁻, 295.2370 [M − 188(2CH₄ + side chain on D ring) − H]⁻ MS²: 483.3425→465.2955 [M − 18(H₂O) − H]⁻, 437.3440 [M − 46(HCOOH) − H]⁻, 311.1998 [M − 172(CH₄+side chain on D ring) − H]⁻, 295.2036 [M − 188(2CH₄ + side chain on D ring) − H]⁻	MS¹: 485.3602 [M + H]⁺, 523.3198 [M + K]⁺, 507.3451 [M + Na]⁺, 467.3518 [M − 18(H₂O) + H]⁺, 449.3387 [M − 36(2H₂O) + H]⁺, 439.3618 [M − 46(HCOOH) + H]⁺, 311.1665 [M − 174(H₂O + side chain on D ring) + H]⁺ MS²: 485.3602→467.3512 [M − 18(H₂O) + H]⁺, 449.3496 [M − 36(2H₂O) + H]⁺, 311.2428 [M − 174(H₂O + side chain on D ring) + H]⁺ MS³: 467.3512→449.3409 [M − 18(H₂O) − 18(H₂O) + H]⁺, 431.2786 [M − 18(H₂O) − 36(2H₂O) + H]^+, 327.2293 [M − 18(H₂O) − 140(RDA fragmentation of B ring) + H]⁺, 311.2351 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺, 293.2248 [M − 18(H₂O) − 174(H₂O + side chain on D ring) + H]⁺, 311.2428→293.2308 [M − 174(H₂O + side chain on D ring) − 18(H₂O) + H]⁺, 281.6503 [M − 174(H₂O + side chain on D ring) − 30(2CH₃) + H]⁺	Dehydrotumulosic acid [32]
F9	37.338	497.3263 499.3444	MS¹: 497.3263 [M − H]⁻, 479.3193 [M − 18(H₂O) − H]⁻, 452.9247 [M − 45(3CH₃) − H]⁻, 248.9602 [M − 248 (4CH₄ + HCOOH + RDA fragmentation of B ring) − H]⁻ MS²: 497.3263→479.3161 [M − 18(H₂O) − H]⁻, 452.9247 [M − 45(3CH₃) − H]⁻, 249.9602 [M − 248(4CH₄ + HCOOH + RDA fragmentation of B ring) − H]⁻	MS¹: 521.3305 [M + Na]⁺, 499.3444 [M + H]⁺, 481.3334 [M − 18(H₂O) + H]⁺, 463.3219 [M − 36(2H₂O) + H]⁺, 405.2614 [M − 93(2CH₃ + H₂O + HCOOH) + H]⁺, 310.1678 [M − 189(CH₃ + H₂O + side chain on D ring) + H]⁺, 279.1589 [M − 220(2H₂O + HCOOH + RDA fragmentation of B ring) + H]⁺ MS²: 499.3444→481.3324 [M − 18(H₂O) + H]⁺, 463.3205 [M − 36(2H₂O) + H]⁺, 325.2130 [M − 174(H₂O + side chain on D ring) + H]⁺ or [M − 174(2H₂O + RDA fragmentation of B ring) + H]⁺ MS³: 481.3324→463.3215 [M − 18(H₂O) − 18(H₂O) + H]⁺, 445.3115 [M − 18(H₂O) − 36(2H₂O) + H]⁺, 325.2132 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺ or [M − 174(2H₂O + RDA fragmentation of B ring) + H]⁺, 463.3205→445.3046 [M − 36(2H₂O) − 18(H₂O) + H]⁺, 417.3143 [M − 36(2H₂O) − 46(HCOOH) + H]⁺, 307.2058 [M − 36(2H₂O) − 156(side chain on D ring) + H]⁺	Unknown
F10	38.513	485.3269 487.3491	MS¹: 485.3269 [M − H]⁻, 469.3311 [M − 16(CH₄) − H]⁻, 248.9582 [M − 236(CH₄ + 2H₂O + HCOOH + RDA fragmentation of B ring) − H]⁻ MS²: 485.3269→441.3391 [M − 44(CO₂) − H]⁻, 423.3255 [M − 62(CH₄ + HCOOH) − H]⁻, 248.9582 [M − 236(CH₄ + 2H₂O + HCOOH + RDA fragmentation of B ring − H)]⁻	MS¹: 509.3283 [M + Na]⁺, 487.3491 [M + H]⁺, 469.3318 [M − 18(H₂O) + H]⁺, 451.3180 [M − 36(2H₂O) + H]⁺, 433.3214 [M − 54(3H₂O) + H]⁺, 405.2659 [M − 82(2H₂O + HCOOH) + H]⁺, 348.9844 [M − 138(RDA fragmentation of B ring) + H]⁺, 327.0051 [M − 18(H₂O) − 142(side chain on D ring) + H]⁺, 313.1531 [M − 174(2H₂O + RDA fragmentation of B ring) + H]⁺, 312.1531 [M − 18(H₂O) − 15(CH₃) − 142(side chain on D ring) + H]⁺ MS²: 487.3491→469.3290 [M − 18(H₂O) + H]⁺, 451.3169 [M − 36(2H₂O) + H]⁺	3-oxo-6,16α-Dihydroxytra-metenolic acid [36]
F11	44.363	−−−−−	−−−−−−	−−−−−−
F12	45.727	481.3333 483.3448	MS¹: 481.3333 [M − H]⁻ MS²: 481.3333→437.3338 [M − 44(CO₂) − H]⁻, 435.3259 [M − 46(HCOOH) − H]⁻, 403.2999 [M − 78(2CH₄ + HCOOH) − H]⁻, 311.2015 [M − 170(2CH₄ + RDA fragmentation of B ring) − H]⁻ MS³: 311.2015→293.2008 [M − 170(2CH₄ + RDA fragmentation of B ring) − 18(H₂O) − H]⁻	MS¹: 483.3463 [M + H]⁺, 505.3322 [M + Na]⁺, 465.3360 [M − 18(H₂O) + H]⁺, 437.3412 [M − 46(HCOOH) + H]⁺, 327.0080 [M − 156(side chain on D ring) + H]⁺ or [M − 156(H₂O + RDA fragmentation of B ring) + H]⁺ MS²: 483.3448→465.3357 [M − 18(H₂O) + H]⁺, 447.2191 [M − 36(2H₂O) + H]⁺, 309.2130 [M − 174(H₂O + side chain on D ring) + H]⁺ MS³: 465.3357→447.3255 [M − 18(H₂O) − 18(H₂O) + H]⁺, 419.3318 [M − 18(H₂O) − 46(HCOOH) + H]⁺, 309.2194 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺	Polyporenic acid C [32]
F13	49.785	483.3478 485.3613	MS¹: 483.3425 [M − H]⁻, 295.2370 [M − 188(2CH₄ + side chain on D ring) − H]⁻ MS²: 483.3425→465.2955 [M − 18(H₂O) − H]⁻, 437.3440 [M − 46(HCOOH) − H]⁻, 311.1998 [M − 172(CH₄ + side chain on D ring) − H]⁻, 295.2036 [M − 188(2CH₄ + side chain on D ring) − H]⁻	MS¹: 485.3602 [M + H]⁺, 523.3198 [M + K]⁺, 507.3451 [M + Na]⁺, 467.3518 [M − 18(H₂O) + H]⁺, 449.3387 [M − 36(2H₂O) + H]⁺, 439.3618 [M − 46(HCOOH) + H]⁺, 311.1665 [M − 174(H₂O+side chain on D ring) + H]⁺ MS²: 485.3602→467.3512 [M − 18(H₂O) + H]⁺, 449.3496 [M − 36(2H₂O) + H]⁺, 311.2428 [M − 174(H₂O + side chain on D ring) + H]⁺ MS³: 467.3512→449.3409 [M − 18(H₂O) − 18(H₂O) + H]⁺, 431.2786 [M − 18(H₂O) − 36(2H₂O) + H]⁺, 327.2293 [M − 18(H₂O) − 140(RDA fragmentation of B ring) + H]⁺, 311.2351 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺, 293.2248 [M − 18(H₂O) − 174(H₂O + side chain on D ring) + H]⁺, 311.2428→293.2308 [M − 174(H₂O + side chain on D ring) − 18(H₂O) + H]⁺, 281.6503 [M − 174(H₂O + side chain on D ring) − 30(2CH₃) + H]⁺	3-epi-Dehydrotumulosic acid [36]
F14	62.492	511.3436 513.3544	MS¹: 511.3433 [M − H]⁻ MS²: 511.3436→467.3499 [M − 44(CO₂) − H]⁻, 451.3122 [M − 60(CH₃COOH) − H]⁻, 355.2211 [M − 156(2H₂O + CO₂ + CH₄ + CH₃COOH) − H]⁻ MS³: 467.3499→451.3222 [M − 44(CO₂) − 16(CH₄) − H]⁻	MS¹: 513.3544 [M + H]⁺, 495.3478 [M − 18(H₂O) + H]⁺, 477.3357 [M − 36(2H₂O) + H]⁺, 435.3200 [M − 18(H₂O) − 60(CH₃COOH) + H]⁺, 337.6933 [M − 176(2H₂O + RDA fragmentation of B ring) + H]⁺ MS²: 513.3544→495.3446 [M − 18(H₂O) + H]⁺, 477.3298 [M − 36(2H₂O) + H]⁺, 435.3185 [M − 78(H₂O + CH₃COOH) + H]⁺, 353.2502 [M − 160(H₂O + side chain on D ring) + H]⁺ MS³: 495.3446→435.3266 [M − 18(H₂O) − 60(CH₃COOH) + H]⁺, 353.2445 [M − 18(H₂O) − 142(side chain on D ring) + H]⁺, 293.2276 [M − 18(H₂O) − 202(CH₃COOH + side chain on D ring) + H]⁺, 435.3185→293.2244 [M − 78(H₂O + CH₃COOH) − 142(side chain on D ring) + H]⁺	3β-Hydroxy-16α-acetoxylanosta-7,9(11),24-trien-21-oic acid [36]
F15	63.130	525.3603 527.3735	MS¹: 525.3581 [M − H]⁻ MS²: 525.3603→509.3196 [M − 16(CH₄) − H]⁻, 465.3379 [M − 60(CH₃COOH) − H]⁻, 447.3200 [M − 78(H₂O + CH₃COOH) − H]⁻, 432.3020 [M − 93(CH₃ + H₂O + CH₃COOH) − H]⁻	MS¹: 527.3735 [M + H]⁺, 549.3522 [M + Na]⁺, 509.3624 [M − 18(H₂O) + H]⁺, 481.3769 [M − 46(HCOOH) + H]⁺, 467.3539 [M − 60(CH₃COOH) + H]⁺, 449.3400 [M − 78(H₂O + CH₃COOH) + H]⁺ MS²: 527.3735→509.3624 [M − 18(H₂O) + H]⁺, 449.3465 [M − 78(H₂O + CH₃COOH) + H]⁺ MS³: 509.3624→491.3414 [M − 18(H₂O) − 18(H₂O) + H]⁺, 449.3399 [M − 18(H₂O) − 60(CH₃COOH) + H]⁺, 353.2453 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺, 293.2240 [M − 18 (H₂O) − 216(CH₃COOH + side chain on D ring) + H]⁺, 449.3465→293.2249 [M − 78(H₂O + CH₃COOH) − 156(side chain on D ring) + H]⁺	Dehydropachymic acid [32]
F16	65.458	513.3579 515.3762	MS¹: 513.3580 [M − H]⁻, 487.3071 [M − 36(2H₂O) − H]⁻ MS²: 513.3579→467.3514 [M − 46(HCOOH) − H]⁻, 453.3324 [M − 60(CH₃COOH) − H]⁻, 451.3184 [M − 46(HCOOH) − 16(CH₄) − H]⁻ MS³: 451.3184→391.3126 [M − 46(HCOOH) − 16(CH₄) − 60(CH₃COOH) − H]⁻	MS¹: 515.3761 [M + H]⁺, 497.3646 [M − 18(H₂O) + H]⁺, 479.3530 [M − 36(2H₂O) + H]⁺, 471.3044 [M − 44(CO₂) + H]⁺, 455.3505 [M − 60(CH₃COOH) + H], 437.3442 [M − 18(H₂O) − 60(CH₃COOH) + H]⁺, 419.3207 [M − 60(CH₃COOH) − 36(2H₂O) + H]⁺ MS²: 515.3762→497.3629 [M − 18(H₂O) + H]⁺, 479.3437 [M − 36(2H₂O) + H]⁺, 437.3399 [M − 78(H₂O + CH₃COOH) + H]⁺ MS³: 497.3626→437.3391 [M − 18(H₂O) − 60(CH₃COOH) + H]⁺, 419.3360 [M − 18(H₂O) − 78(H₂O + CH₃COOH) + H]⁺, 355.2645 [M − 18(H₂O) − 142(side chain on D ring) + H]⁺, 295.2417 [M − 18(H₂O) − 202(CH₃COOH + side chain on D ring) + H]⁺, 437.3391→419.3295 [M − 78(H₂O + CH₃COOH) − 18(H₂O) + H]⁺, 391.3359 [M − 78(H₂O + CH₃COOH) − 46(HCOOH) + H], 295.2419 [M − 78(H₂O + CH₃COOH) − 142(side chain on D ring) + H]⁺	3-O-Acetyl-16α-hydroxydehydrotra-metenolic acid [37]
F17	67.750	525.3584 527.3719	MS¹: 525.3581 [M − H]⁻ MS²: 525.3603→509.3196 [M − H − 16(CH₄)]⁻, 465.3379 [M − 60(CH₃COOH) − H]⁻, 447.3200 [M − H − 78(H₂O + CH₃COOH)]⁻, 432.3020 [M − 93(CH₃ + H₂O + CH₃COOH) − H]⁻	MS¹: 527.3735 [M + H]⁺, 549.3522 [M + Na]⁺, 509.3624 [M − 18(H₂O) + H]⁺, 481.3769 [M − 46(HCOOH) + H]⁺, 467.3539 [M − 60(CH₃COOH) + H]⁺, 449.3400 [M − 78(H₂O + CH₃COOH) + H]⁺ MS²: 527.3735→509.3624 [M − 18(H₂O) + H]⁺, 449.3465 [M − 78(H₂O + CH₃COOH) + H]⁺ MS³: 509.3624→491.3414 [M − 18(H₂O) − 18(H₂O) + H]⁺, 449.3399 [M − 18(H₂O) − 60(CH₃COOH) + H]⁺, 353.2453 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺, 293.2240 [M − 18(H₂O) − 216(CH₃COOH + side chain on D ring) + H]⁺, 449.3465→293.2249 [M − 78(H₂O + CH₃COOH) − 156(side chain on D ring) + H]⁺	3-epi-Dehydro-pachymic acid [37]
F18	76.858	587.3756 589.3883	MS¹: 587.3756 [M − H]⁻ MS²: 587.3756→465.3296 [M − 122(HCO−Ar−OH) − H]⁻	MS¹: 589.3883 [M + H]⁺, 611.3583 [M + Na]⁺, 571.3853 [M − 18(H₂O) + H]⁺, 449.3413 [M − 18(H₂O) − 122(HCO−Ar−OH) + H]⁺, 430.9047 [M − 36(2H₂O) − 122(HCO−Ar−OH) + H]⁺, 406.2653 [M − 15(CH₃) − 46(HCOOH) − 122(HCO−Ar−OH) + H]⁺ MS²: 589.3883→571.3813 [M − 18(H₂O) + H]⁺ MS³: 571.3813→449.3361 [M − 18(H₂O) − 122(HCO−Ar−OH) + H]⁺, 415.2603 [M − 18(H₂O) − 156(side chain on D ring) + H], 403.0557 [M − 18(H₂O) − 168(HCOOH+HCO−Ar−OH) + H]⁺, 293.2261 [M − 18(H₂O) − 278(HCO−Ar−OH+ side chain on D ring) + H]⁺, 449.3413→419.0319 [M − 18(H₂O) − 122(HCO−Ar−OH) − 30(2CH₃) + H]⁺, 293.2260 [M − 18(H₂O) − 122(HCO−Ar−OH) − 156(side chain on D ring) + H]⁺	3β-p-Hydroxybenzoyl-dehydrotumulosic acid [4]
F19	78.300	467.3152 469.3617	MS¹: 467.3152 [M − H]⁻, 439.3557 [M − 28(CO) − H]⁻ MS²: 467.3152→451.3368 [M − 16(CH₄) − H]⁻, 421.3552 [M − 46(HCOOH) − H]⁻, 292.9842 [M − 174(H₂O + side chain on D ring) − H]⁻	MS¹: 469.3617 [M + H]⁺, 451.3574 [M − 18(H₂O) + H]⁺ MS²: 469.3617→451.3574 [M − 18(H₂O) + H]⁺, 433.3207 [M − 36(2H₂O) + H]⁺, 423.3302 [M − 46 (HCOOH) + H]⁺, 328.9961 [M − 140(RDA fragmentation of B ring) + H]⁺, 313.2356 [M − 156(side chain on D ring) + H]⁺ MS³: 451.3574→433.3207 [M − 18(H₂O) − 18(H₂O) + H]⁺, 311.2370 [M − 18(H₂O) − 140(RDA fragmentation of B ring) + H]⁺, 295.2413 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺	Dehydroeburicoic acid [35]
a1	26.285	471.3478 473.3639	MS¹: 471.3478 [M − H]⁻ MS²: 471.3478→409.3100 [M − 62(CH₄ + HCOOH) − H]⁻	MS¹: 473.3639 [M + H]⁺, 495.3469 [M + Na]⁺, 511.3243 [M + K]⁺, 457.3665 [M − 16(CH₄) + H]⁺, 455.3527 [M − 18(H₂O) + H]⁺, 437.3413 [M − 36(2H₂O) + H]⁺, 429.2905 [M − 44(CO₂) + H]⁺, 317.6939 [M − 156(CH₄ + RDA fragmentation of B ring) + H]⁺ MS²: 473.3639→455.3515 [M − 18(H₂O) + H]⁺, 437.3438 [M − 36(2H₂O) + H]⁺ MS³: 455.3508→437.3415 [M − 18(H₂O) − 18(H₂O) + H]⁺, 313.2512 [M − 18(H₂O) − 142(side chain on D ring) + H]⁺, 295.2432 [M − 18(H₂O) − 160(H₂O + side chain on D ring) + H]⁺, 437.3415→419.3394 [M − 36(2H₂O) − 18(H₂O) + H]⁺, 295.2422 [M − 36(2H₂O) − 142(side chain on D ring) + H]⁺	16α-Hydroxy-trametenolic acid [34]
a2	35.110	485.3641 487.3779	MS¹: 485.3641 [M − H]⁻ MS²: 485.3641→437.3421 [M − 48(3CH₄) − H]⁻, 423.3261 [M − 62(CH₄ + HCOOH) − H]⁻ MS³: 423.3261→407.3050 [M − 62(CH₄ + HCOOH) − 6(CH₄) − H]⁻	MS¹: 487.3779 [M + H]⁺, 525.3343 [M + K]⁺, 509.3610 [M + Na]⁺, 469.3686 [M − 18(H₂O) + H]⁺, 451.3542 [M − 36(2H₂O) + H]⁺ MS²: 487.3779→469.3669 [M − 18(H₂O) + H]⁺, 451.3542 [M − 36(2H₂O) + H]⁺ MS³: 469.3669→451.3509 [M − 18(H₂O) − 18(H₂O) + H]⁺, 313.2502 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺, 295.2419 [M − 18(H₂O) − 174(H₂O+side chain on D ring) + H]⁺, 451.3542→433.3188 [M − 36(2H₂O) − 18(H₂O) + H]⁺, 309.2200 [M − 36(2H₂O) − 142(side chain on D ring) + H]⁺, 295.2425 [M − 36(2H₂O) − 156(H₂O + side chain on D ring) + H]⁺	Tumulosic acid [32]
a3	48.572	483.3478 485.3613	MS¹: 483.3478 [M − H]⁻ MS²: 483.3478→437.3382 [M − 46(HCOOH) − H]⁻, 421.3146 [M − 62(CH₄ + HCOOH) −H]⁻, 405.3155 [M − 78(2CH₄ + HCOOH) − H]⁻, 389.2812 [M − 94(3CH₄ + HCOOH) − H]⁻, 369.2392 [M − 114(2CH₄ + 2H₂O + HCOOH) − H]⁻, 295.1952 [M − 188(2CH₄ + side chain on D ring) − H]	MS¹: 485.3613 [M + H]⁺, 507.3456 [M + Na]⁺, 467.3515 [M − 18(H₂O) + H]⁺, 449.3399 [M − 36(2H₂O) + H]⁺, 311.1682 [M − 174(H₂O + side chain on D ring) + H]⁺ or [M − 174(2H₂O+RDA fragmentation of B ring) + H]⁺, 301.1401 [M − 184(HCOOH+RDA fragmentation of B ring) + H]⁺ MS²: 485.3613→467.3506 [M − 18(H₂O) + H]⁺, 449.3390 [M − 36(2H₂O) + H]⁺, 311.2428 [M − 174(H₂O + side chain on D ring) + H]⁺ MS³: 467.3506→449.3399 [M − 18(H₂O) − 18(H₂O) + H]⁺, 431.3310 [M − 18(H₂O) − 36(2H₂O) + H]⁺, 421.3452 [M − 18(H₂O) − 46(HCOOH) + H]⁺, 311.2353 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺, 293.2247 [M − 18(H₂O) − 174(H₂O + side chain on D ring) + H]⁺, 449.3390→431.3378 [M − 36(2H₂O) − 18(H₂O) + H]⁺, 403.3292 [M − 36(2H₂O) − 46(HCOOH) + H]⁺, 293.2258 [M − 36(2H₂O) − 156(side chain on D ring) + H]⁺, 311.2428→293.2250 [M − 174(H₂O + side chain on D ring) − 18(H₂O) + H]⁺	Unknown
a4	70.508	527.3730 529.3897	MS¹: 527.3730 [M − H]⁻ MS²: 527.3730→481.3658 [M − 46(HCOOH) − H]⁻, 465.3329 [M − 62(CH₄ + HCOOH) − H]⁻, 431.2794 [M − 96(2H₂O + CH₃COOH) − H]⁻, 405.3045 [M − 122(CH₃COOH + HCOOH + CH₄) − H]⁻ MS³: 465.3329→405.3168 [M − 62(CH₄ + HCOOH) − 60(CH₃COOH) − H]⁻	MS¹: 567.3456 [M + K]⁺, 551.3703 [M + Na]⁺, 529.3897 [M + H]⁺, 511.3759 [M − 18(H₂O) + H]⁺, 493.3662 [M − 36(2H₂O) + H]⁺, 469.3707 [M − 60(CH₃COOH) + H]⁺, 451.3572 [M − 78(H₂O + CH₃COOH) + H]⁺ MS²: 529.3897→511.3764 [M − 18(H₂O) + H]⁺, 451.3559 [M − 78(H₂O + CH₃COOH) + H]⁺ MS³: 511.3764→451.3555 [M − 18(H₂O) − 60(CH₃COOH) + H]⁺, 433.3480 [M − 18(H₂O) − 78(H₂O + CH₃COOH) + H]⁺, 355.2589 [M − 18(H₂O) − 156(side chain on D ring) + H]⁺, 295.2407 [M − 18(H₂O) − 216(CH₃COOH + side chain on D ring) + H]⁺, 451.3559→433.3485 [M − 78(H₂O + CH₃COOH) − 18(H₂O) + H]⁺, 405.3540 [M − 78(H₂O + CH₃COOH) − 46(HCOOH) + H]⁺, 295.2412 [M − 78(H₂O + CH₃COOH) − 156(side chain on D ring) + H]⁺, 295.2407→280.2181 [M − 78(H₂O + CH₃COOH) − 156(side chain on D ring) − 15(CH₃) + H]⁺	Pachymic acid [32]