TABLE 2

Mass spectral data of protonated mavoglurant and its metabolites

For characterization and confirmation of chemical structures of mavoglurant and its metabolites observed in plasma, urine, and feces, LC-MS, LC-MS^E, and/or LC-MS/MS in the positive ionization mode were performed on a Synapt Quadrupole-time-of-flight (QTOF) tandem mass spectrometer.

Name	LC R_t	Full-MS^a	Type of Ion	Exact Mass Difference^b	Elemental Composition	Mass Shift (Metabolite–Parent Compound)	Fragments Observed in MS/MS	Number of Exchangeable Protons^{^c}
Name	LC R_t	Full-MS^a	Type of Ion	Exact Mass Difference^b	Elemental Composition	Mass Shift (Metabolite–Parent Compound)	Fragments Observed in MS/MS	[M+H]⁺	[M+Na]⁺
	min	m/z		mDa		Da	m/z
Mavoglurant	59.6	336	[M+Na]⁺	+2.5	C₁₉H₂₃NO₃	—	264, 236, 221, 218, 208, 206, 193, 191, 178, 165, 153, 141,128, 115, 105, 91, 77	2	1
		314	[M+H]⁺	+1.4
		(296)	[M+H]⁺-H₂O	−1.2
M1 (diastereomer)	53.5	368	[M+K]⁺	+2.9	C₁₉H₂₃NO₄	+16	262, 244, 234, 219, 204, 191, 178,165, 152, 128, 115, 105, 91, 77	ND	2
		352	[M+Na]⁺	+3.8
		312	[M+H]⁺-H₂O	+0.8
		(294)	[M+H]⁺-2 H₂O	+1.3
M2 (Diastereomer)	53.1	368	[M+K]⁺	+2.6	C₁₉H₂₃NO₄	+16	262, 244, 234, 219, 204, 191, 178,165, 152, 128, 115, 105, 91, 77	ND	2
		352	[M+Na]⁺	+3.2
		312	[M+H]⁺-H₂O	+2.5
		(294)	[M+H]⁺-2 H₂O	+1.7
M3	49.2	352	[M+Na]⁺	+1	C₁₉H₂₃NO₄	+16	280, 252, 237, 222, 209, 195, 181, 171, 165, 159, 152, 145, 128, 121, 117, 115, 105, 91, 77	ND	2
		330	[M+H]⁺	+3.4
		(312)	[M+H]⁺-H₂O	+0.1
M5	46.1	512	[M+Na]⁺	+1.1	C₂₅H₃₁NO₉	+176	268, 264, 236, 221, 218, 206, 193, 191, 178, 165, 153, 141, 128, 115, 105, 91, 77	ND	4
		490	[M+H]⁺	ND
		(296)	[M+H]⁺-H₂O-Gluc	+0.9
M6	45.0	366	[M+Na]⁺	+2	C₁₉H₂₁NO₅	+30	308, 294, 280, 276, 266, 251, 248, 238, 220, 204, 191, 178, 165, 159, 152, 141, 135, 128, 115, 107, 105, 91, 77	3	2
		344	[M+H]⁺	+2.7
		(326)	[M+H]⁺-H₂O	+1.9
M7	43.1	368	[M+K]⁺	+4.1	C₁₉H₂₃NO₄	+16	312, 294, 266, 262, 237, 234, 219, 203, 191, 178, 165, 153, 141, 128, 115, 91, 77	3	2
		352	[M+Na]⁺	+3.8
		330	[M+H]⁺	+2.9
		(312)	[M+H]⁺-H₂O	+1.9
M12	62.7	366	[M+K]⁺	−0.3	C₁₉H₂₁NO₄	+14	235, 207, 192, 178, 165, 152, 129, 119, 115, 105, 91	NA	NA
		350	[M+Na]⁺	−4.4
		345	[M+NH₄]⁺	−1.9
		328	[M+H]⁺	−2.6
		310	[M+H]⁺-H₂O	−2.3
		(253)	[M+H]⁺-75	−2.7
M13	12.9	(302)	[M+H]⁺	+0.9	C₁₇H₁₉NO₄	−12	284, 266, 238, 223, 210, 198, 178, 165, 152, 133, 127, 115, 105, 77	5	ND
		284	[M+H]⁺-H₂O	+0.7
		266	[M+H]⁺-2H₂O	+0.8
M14	12.9	(352)	[M+H]⁺	−0.2	C₁₇H₂₁NO₅S	+38	334, 254, 239, 226, 211, 195, 186, 171, 165, 146, 134, 128, 121, 91, 77	4	ND
		334	[M+H]⁺-H₂O	+0.5
		254	[M+H]⁺-H₂O-SO₃	+1.5
M15	16.2	(286)	[M+H]⁺	−3.3	C₁₇H₁₉NO₃	−28	268, 252, 238, 226, 222, 200, 194, 192, 178, 165, 152, 128, 115, 105, 91, 77	4	ND
M15	16.2	268	[M+H]⁺-H₂O	−1.2	C₁₇H₁₉NO₃	−28		4	ND
M16	20.6	(272)	[M+H]⁺	+1.8	C₁₇H₂₁NO₂	−42	254, 238, 226, 224, 210, 196, 186, 171, 160, 152, 146, 128, 121, 119, 115, 105, 91, 77	4	ND
M16	20.6	254	[M+H]⁺-H₂O	−1.2	C₁₇H₂₁NO₂	−42		4	ND
M17	21.4	544	[M+Na]⁺	−3.8	C₂₅H₃₁NO₁₁	+208	310, 282, 278, 235, 223, 207, 191, 170, 115	7	6
		(522)	[M+H]⁺	+5.4
		504	[M+H]⁺-H₂O	+1.4
		486	[M+H]⁺-2H₂O	−2.5
M18	27.5	386	[M+K]⁺	+1.7	C₁₉H₂₅NO₅	+34	312, 280, 252, 237, 222, 209, 195, 181, 165, 158, 153, 145, 128, 121, 117, 115, 105, 91, 77	ND	3
		370	[M+Na]⁺	+4.8
		348	[M+H]⁺	+2.5
		(330)	[M+H]⁺-H₂O	+1.6
		312	[M+H]⁺-2H₂O	+1.8
M19	30.2	473	[M+Na]⁺	+3.7	C₂₁H₂₆N₂O₇S	+137	401, 373, 308, 276, 248, 233, 220, 203, 189, 178, 165, 152, 129, 105, 91	4	3
		(451)	[M+H]⁺	0.0
		433	[M+H]⁺-H₂O	−0.6
M20	30.2	544	[M+K]⁺	+0.3	C₂₅H₃₁NO₁₀	+192	488, 312, 284, 280, 252, 237, 225, 222, 209, 195, 129, 121, 117, 105, 91	6	5
		528	[M+Na]⁺	+2.8
		523	[M+NH₄]⁺	+3
		(506)	[M+H]⁺	+1.8
		488	[M+H]⁺-H₂O	−1.8
M21	30.2	542	[M+Na]⁺	+1.8	C₂₅H₂₉NO₁₁	+206	326, 308, 294, 276, 266, 251, 248, 233, 222, 205, 178, 167, 129,115, 88, 79	6	5
		(520)	[M+H]⁺	+3.1
		502	[M+H]⁺-H₂O	+2.7
		484	[M+H]⁺-2H₂O	+7.1
		344	[M+H]⁺-Gluc	+1.4
M22	30.8	528	[M+Na]⁺	−0.2	C₂₅H₃₁NO₁₀	+192	312, 294, 280, 266, 262, 242, 234, 219, 207, 191, 178, 165, 141, 128, 115, 105, 91, 88	ND	5
		(506)	[M+H]⁺	+5.5
		312	[M+H]⁺-H₂O-Gluc	+4.2
M23	35.2	384	[M+K]⁺	+1.7	C₁₉H₂₃NO₅	+32	328, 310, 282, 278, 250, 235, 223, 207, 202, 191, 165, 152, 128, 115, 105, 91, 79	ND	ND
		368	[M+Na]⁺	+2.4
		(346)	[M+H]⁺	ND
		328	[M+H]⁺-H₂O	+1.8
		310	[M+H]⁺-2H₂O	+0.5
M24	35.2	439	[M+K]⁺	+0.8	C₂₁H₂₄N₂O₆	+87	308, 280, 276, 248, 233, 221, 203., 191, 178, 165, 152, 129, 115, 91, 79	4	3
		423	[M+Na]⁺	+2.1
		418	[M+NH₄]⁺	+0.2
		(401)	[M+H]⁺	+1.7
		383	[M+H]⁺-H₂O	−1.5
M25	37.3	(256)	[M+H]⁺	−1.6	C₁₇H₂₁NO	−58	238, 222, 208, 193, 178, 170, 165, 153, 141, 132, 128, 115, 105, 91, 77	3	ND
M25	37.3	238	[M+H]⁺-H₂O	−0.2	C₁₇H₂₁NO	−58		3	ND
M26	37.3	410	[M+H]⁺	−2.1	C₁₉H₂₃NO₇S	+96	312, 280, 252, 237, 203, 191, 165, 149, 128	3	2
M26	37.3	(392)	[M+H]⁺-H₂O	−3.5	C₁₉H₂₃NO₇S	+96	312, 280, 252, 237, 203, 191, 165, 149, 128	3	2
M27	38.1	382	[M+Na]⁺	−2.1	C₁₉H₂₁NO₆	+46	306, 292, 277, 252, 246, 237, 231, 218, 202, 189, 178, 165, 131, 115, 77	ND	3
		360	[M+H]⁺	ND
		(324)	[M+H]⁺-2H₂O	−2
		306	[M+H]⁺-3H₂O	−2.6
M28	40.3	398	[M+Na]⁺	+0.6	C₁₉H₂₁NO₇	+62	358, 283, 265, 237, 219, 209, 191, 178, 165, 152, 144, 131, 115, 91, 85	5	4
		376	[M+H]⁺	−2.8
		(358)	[M+H]⁺-H₂O	−0.5
M29	45.6	528	[M+Na]⁺	+1.8	C₂₅H₃₁NO₁₀	+192	219, 204, 191, 178, 165, 152, 128, 115, 93, 77	ND	5
		(312)	[M+H]⁺-H₂O-Gluc	−3.8
		294	[M+H]⁺-2H₂O-Gluc	−0.7
M30	54.6	384	[M+K]⁺	+1	C₁₉H₂₃NO₅	+32	278, 253, 250, 235, 225, 207, 192, 178, 165, 129, 119, 115, 105, 91, 79	ND	3
		368	[M+Na]⁺	+1.6
		346	[M+H]⁺	+1.3
		(328)	[M+H]⁺-H₂O	+1.1
M31	55.2	396	[M+K]⁺	−3.2	C₂₀H₂₃NO₅	+44	308, 280, 276, 265, 248, 233, 221, 205, 191, 178, 165, 149, 128, 105, 115, 91	NA	NA
		380	[M+Na]⁺	−4.1
		358	[M+H]⁺	−2.3
		340	[M+H]⁺-H₂O	−2.7

LC, liquid chromatography; NA, not assessed; ND, not detected; R_t, chromatographic retention time.
↵^a Mass (m/z) used for ms/ms fragmentation are shown in parentheses.
↵^b Exact mass difference of the measured mass [M+H]⁺ to the theoretical exact mass.
↵^c Mass shift (Da) upon hydrogen–deuterium exchange.