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利用苯甲醛醯氨基甲苯磺醯腙來合成吲哚基吲哚-3-酮衍生物

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(1)Department of Chemistry. National Taiwan Normal University Master’s Thesis. -3Synthesis of indolyl indol-3-ones from acylamino benzaldehyde tosyl hydrazones. KU, Shyue-Herng. Advisor. 109 August 2020. 8.

(2)

(3) …………………………………………………………………………………..ⅲ ……………………………………...……………….……………………...ⅴ Abstract……………………………………………..………………………….…….ⅶ. -3-. ………………………………………………………………………………1 1-1. (indole). 1-2. ..……………………………………2. (indole). 1-3. …………………………………………..…8. (disubstituted-indole). ……………………....11. …………………………………………………………………….......13. 3-1. 4a. 3-2. 4a. ………………………………...14 5a. …..…………20. 3-3. ……………..………………………………………………29. 3-3. ………..……………………………...…………………………31. ………………………………………………32 …………………………………………………………………34 ……………………………………………………………………...…36 ……………………………………………………………………...…38 ……………………………………………………………………...…55 X-ray. (Single-Crystal X-ray Diffraction) ………………......123 i.

(4) ii.

(5) Dr. Kavala. Dr. Naidu. Dr. Suresh. Suchitra. Prakash. iii. Sarath. Jivan. Palla.

(6) iv.

(7) (N-(. )-N-(2 – ((2-. ). ). ). ). -3-. (carbene) -3-. 3,322-. -3-. v.

(8) vi.

(9) Abstract This thesis is divided in two chapters. The first chapter dealt with preface of the thesis which includes the introduction to indole and bis-indole derivatives and literature survey on the synthesis and properties of bis-indole derivatives. In addition, a short introduction on tosyl hydrazone derivatives and their reactions. Further, we then disclosed the aim and research goals at the end of the first chapter. The second chapter focused on the sodium hydride ( NaH ) mediated reaction of tosylhydrazone(N-(alkyl)-N-(2-((2-tosylhydrazono) methyl) phenyl)benzamide) in dry THF to produce indolylindolin-3-one derivatives. This reaction may be involving the generation of diazo intermediate from the tosylhydrazone by the loss of tosylate in the presence of base. Then the diazo intermediate lose nitrogen to generate carbene, which insert to carbonyl carbon of amide to indole oxide, which subsequently produce indolylindolin-3-one derivative and 3,3'-biindole derivative. Although the same products were reported in the literature, most of them were prepared by using 2-substituted indole derivatives as substrate. Here , for the first time, we utilized 2-acylaminobenzaldehyde tosylhydrazones for the construction of indolylindolin-3-one derivatives and also it is revealed that the insertion of carbene to amidic carbonyl group has been observed herein for the first time.. vii.

(10) viii.

(11) 2,2-. -3-. [1]. -32,2(. ). reactions). (Annulation -3-. (Fischer indolization)/ 1.1. -3-. (Claisen rearrangement reaction). [2]. (amino imides). [(Ph3P)AuCl] (8 mol%) AgOTf (8 mol%). C5H11. OH. N3. O C5H11. (85 equiv). N H. CHCl3, 55℃ 1h, 87% Claisen rearrangement. AuL - N2. Nucleophilic trapping. AuL. N. 1.1. C5H11. O N H. C5H11. (Claisen rearrangement reaction). 1.

(12) 1-1. (indole) C2-C3. N1. C2. [3]. C3. (MoO5•HMPA),. -. (Bis(acetylacetonato)oxovanadium),. dimethyl dioxirane),. (singlet oxygen),. (m-. CPBA) 1960. (oxodiperoxo molybdenum. complexes) C2-C3. [4]. 1985. Sakamoto. (MoO5•HMPA) 1989. 1.2 2-. (2-phenylindole). Speier [5]. 2-. 1.3. Sakamoto, 1985. Ph N H. MoO5 • HMPA CH2Cl2. O Ph N H Ph. 56%. 1.2. 2-. 2. N H.

(13) Speier, 1989. O. VO(acac)2, O2, CH3CN, reflux. Me N H. Me N H Me. 47%. 1.3. N H. 2-. (Zimenez) (oxodiperoxomolybdenum oxidants with trialkylphosphine oxide ligands). (Electrophilic Aromatic Substitution,. EAS) (. 1.4. 1.5. ). (Zimenez). alkyl). EAS [3]. (. 1.6. N-. N-. (N-. (N-acyl). ). (iminium ion). Jimenez, 2004 MoO5•Et3PO•MeOH,. O. MeOH/CH2Cl2(1:1), 0 ℃. Me N Me. Me N Me Me. 90%. NMe. 1.4. MoO5•Et3PO•MeOH,. O. MeOH/CH2Cl2(1:1), 0 ℃. Ph N Me. Ph N Me Ph. 54%. 1.5. N-. EAS. 3. NMe.

(14) Ph. O. MoO5•Et3PO•MeOH, MeOH/CH2Cl2(1:1), 0 ℃. N Ac. N Ac. 52%. 1.6. OH Me. N-. (iminium intermediate) 1.7. (acyl group) (dimerization). Ph. Ph. O. [O]. N Me Ph. N Me. N Me. 1.7. 4. O Ph N Me Ph. NMe.

(15) 2017. ， Zhao. 2-. (gold/copper-co-catalyzed). TBHP) (intermolecular. nucleophilic addition). (intramolecular. cyclization/oxidative cross-dehydrogenative coupling) [1]. CuO ( 10 mol %) X-PhosAuCl (1.5 mol % ) NaBArF4 (3 mol % ). R2 R1 N H. O. R. 1.8:. 2017. OH. N R. DCE, 80 ℃, 15~30 min. 2,2-. N. R2 R1. -3-. Zhou 2-. R. 2. OR. R1. (RuCl3•3H2O) 2-. (oxidative. dearomatization). -3-. (indolin-3[6]. ones). O R3. N R2. R1. R1. RuCl3·3H2O (5.0 mol%) NaIO4 (1.0 eq) CH3CN, 70℃. R3. N. R1 N. R2 R3. 1.9:. -35. R2.

(16) 2017. Xie. (hydrazine). (allyloxyketone). (Fischer indolization. 3-. (Claisen rearrangement). 2,2-. -3-. [7]. NHNH2. +. indolization. O. O. O. Fischer. [3,3] Claissen. N H R. N H. R. O. R. 1.10: 2012. (isatogen). Ramana [8]. (indole). 0.2. (InCl3) N-. hydroxyindolin-3-one derivative). -3-. 1.5. N-. (InCl3). (toluene). 2,2-. -3-. (2,2-disubstituted indolin-3-one derivative) O. O N R3. N R2 OH. N O. R3 R1. InCl3 (0.2 equiv) acetonitrile, 25℃ 4 -8 h. +. 6. O. InCl3 (1.5 equiv) toiuene, 80℃ 8 -12 h. N R1. 1.11:. R2. R3. N H. 1 N R. R2.

(17) 2019. He. 1.12. (Ru(bpy)3Cl2•6H2O). [9]. (photooxidation step). (wheat germ lipase ,WGL)) (asymmetric alkylation). 2-. (2-arylindoles). 2,2-. -3-. WGL (visible light) (Ru(bpy)3Cl2•6H2O). WGL R2. R1. R2 N H. 1.12:. +. WGL (0.16 mol%) Ru(bpy)3Cl2•6H2O (2 mol%). O R3. R4. 32 W CFL, DMF, O2, RT. R1. N H. N H R3. R4 O. (photobiocatalytic concurrent reaction). 7. O. O N H minor product.

(18) 1-2. (indole) (indole). (Isatin). (oxindole). Adolf von Baeyer. 1866. 19 20. 30 (alkaloid). (Tryptophan). (Plant hormone). (Pyrrole) 1.1. N H 1.1. 8.

(19) [10]. 1.2. CO2H NH2. NH2. N H. N H. tryptamine. tryptophan. NH2. HO. NHAc. MeO. N H. N H. serotonin. melatonin. 1.2: (Tryptophan) (tryptamine-indole) (serotonin) (melationin). (Aspergillus fumigatus) (prenylated indole alkaloids). 1.3. (antibacterial activity). 9. [10].

(20) O N. H. OR. HN O. O. N H. O. R=CH3, H. 1.3:. marine fungus）. (Famitinib) (multi-targeted receptor tyrosine kinase inhibitor). [10]. N. O N F N H. O. N H. 1.4:. (Famitinib). 10. 1.4.

(21) 1-3. (disubstituted-indole) 2,2-. -3-. (2,2-Disubstituted indolin-3-one). 1.5 (brevianamide). 2,2-. A (Austamide A). aristotelone. A (duocarmycin A). B–D. (cephalinones B–D)、peronatins A and B (isatisine A). A. O (notoamides O). O O H. 2,2-. O. N N. O. Austamide O. OMe H N. N H. Brevianamide. CO2Me. O. MeO2C Me HN. O. OMe N O. O. HN O. O. HO HO. OMe. N H. OMe. OH. O. O N. NH O. N. HN O. O. Notoamide O. Isatisine A. 1.5:. O. Duocarmycin A. Cephalinone. HO. NH N. N H. O. N H. HO. 2,2-. -3-. 11.

(22) DNA. 12.

(23) 2 (2-(acyl(prop-2-yn-1yl)amino)benzaldehyde tosyl hydrazones) (1,3-dipolar cyclization). [11]. (pyrazole) (carbene reaction). (carbene intermediate) (alkyne) (carbonyl group). 2,2indolin-3-one). -3-. (2,2-Disubstituted. 1.6 N O. Ts N. NH H. N. H NaH. carbene reaction. N. N. and. O N. O. N. 1.6:. 13.

(24) 3 3-1. 4a 1,3(1,3-dipolar cyclization). (pyrazole). 3-1. 3-2. 5. (NaH). N. Ts NH H. N N Base. 1,3-dipolar cyclization. H. N O. N NH. N. N CH3. O. O. CH3. CH3. 3-1:. N. Ts NH H. dry THF, r.t,6 h Ar. N O. NaH (5 equiv.). CH3. +. N O 12%. Ts. Ts. N NH. CH3 N. +. CH3 5%. 45%. 3-2:. (Nheterocyclic compound) 14. CH3 N HC C CH2.

(25) 3. 3-1. N. R1 N. H N. O S. O H R3. O. R2 3. 3-1. 3. 3a (0.5 mmol) (NaH). 5. (THF). 2 50℃. 5 intermediate). (diazo. (dimerization). 3-2. (indole) 46%. 1. H-NMR. 13. C-NMR. 4a. HRMS. 1-methyl-2-(1-methyl-2-phenyl-1H-indol-3-yl)-2-phenylindolin-3-one (4a) 13%. 1,1'-dimethyl-2,2'-diphenyl-1H,1'H-3,3'-biindole (5a)， 4a X-ray. 5a。 3-2. 3. 15. 3-.

(26) N O. N. Ts NH H. N O. N N. NaH (2 equiv.) dry THF, r.t,5 h Ar. N. dimerization. H N. 4a, 46% + N. O. 0.5 mmol 3a. N. 5a, 13%. 3-3:. 3-2. 4a. 4a. 16. 5a. X-ray.

(27) 3-3. 5a. X-ray. 4a 3-1. 17.

(28) 3-1 N. H N. 4a. O S. N. N. O H. NaH. N. O. +. THF, r.t, 5 h N. N. 4a. 5a. O. 3a Entrya. Yield (%)b. NaH (equiv.) 4a. 5a. 1. 1. 78%. 8%. 2. 1.5. 86%. 6%. 3. 2. 46%. 13%. 4. 2.5. 62%. 20%. 5. 3. 42%. 16%. 6. 3.5. 28%. 8%. aReaction. conditions: 3a (0.5 mmol), dry THF (5 mL), r.t., under Ar. After the starting material disappeared, MeOH was added and then the solution was stirred for 5 minutes. bYields were determined by 1H NMR spectrum with CH Br as internal standard. 2 2. 3a (0.5 mmol). 5. 0.1M. 5. (NaH) 2.5. 46%. 4a. (NaH). 13% 4a. 4 1.5 4a. 86% 18. 5a. Entry 3 Entry. 4a. 5. 2. Entry.

(29) 3-2. N. H N. 4a. O S NaH. N. O. THF, Temp, time (h). O 3a Temp (℃). Entrya. N. N. O H. +. N. N. 4a. 5a. Time (h). Yield (%)b. 4a. 5a. 1. 30. 5. 74%. 7%. 2. 50. 3. 89%. 4%. 3. 70. 3. 70%. 7%. aReaction. conditions: 3a (0.5 mmol), NaH (1.5 equiv.), dry THF (5 mL), under Ar. After the starting material disappeared, MeOH was added and then the solution was stirred for 5 minutes. bYields were determined by 1H NMR spectrum with CH Br as internal standard. 2 2. 3-1. 3a. 0.5 mmol. 5. 1.5. 30℃. 74%. 4a. 50℃ 5a. 7%. 3. Entry 1 89%. Entry 2 70%. 5a. 70℃ 4a. 7%. 5a. 5. 4a 3. Entry 3 4a. 3a. 0.5 mmol. 5 3 5 19. 3a. 4%.

(30) 3-2. 4a. 5a. R1. 3. 1.5 R1. 3-3 N. 3. Ts NH H. R1. 3-3. NaH. N. O. THF, 50 ℃, Time (h). O. N. N. R1. +. N. R1. R1. N. R1. 3 Starting material. Entrya. 5. 4 (major product). Yield (%)b. Time (h). Product. 4. N. Ts NH H. 1. 5. N O. 3a. 89%. 4a. N N. O. 3 N 5a. 4%. N. N Br. Ts NH H. 2. N 3b. O. Br. 70%. 4b. N N. O. Br. 3 N Br. Br N. 20. 5b. tracec.

(31) Starting material. Entrya. Yield (%)b. Time (h). Product. 4. N Cl. Ts NH H. 3. 5. N 3c. O. Cl. N. 60%. 4c. N. Cl. O. 3 N Cl. Cl. 5c. 8%. N. N MeO. Ts NH H. 4. N 3d. O. MeO. N. 66%. 4d. N. OMe. O. 2 N 5d. MeO. 12%. OMe N. N O 5d. Ts NH H. O. O. O 3e. 30%. 4e. N. O. N. N. O. O O. N. O. O O. 2.5. O. 5e N. 21. tracec.

(32) Starting material. Entrya. Yield (%)b. Time (h). Product. 4. N O 6. Ts NH H. O. 5. N. O O. O. 3f. N. 90%. 4f. N. O. O O. 2 N. O O. O N. 5f. tracec. O. aReaction. conditions: 3a (0.5 mmol), NaH (1.5 equiv.), dry THF (5 mL), under Ar. After the starting material disappeared, MeOH was added and then the solution was stirred for 5 minutes. bYields were determined by 1H NMR spectrum with CH Br as internal standard. 2 2 cCould not be isolated in pure form. dStarting material is insoluble.. R1. (H). 89%. 4a. R1 (4-OMe) 4b-4d. 60-70%. Entry 1 (4-Br). (4-Cl). 2-3 R1. (Dimethoxy) 4e. Entry 5. R1. Entry 2-4. (methylenedioxy) 4f. 90%. 22. 2. 30%.

(33) R2. 3-4. N. 3. Ts NH. R2. N H. NaH. N. R2. O. +. THF, 50 ℃, Time (h). O. N. R2. N. N. R2. R2. 3. Entrya. 5. 4 (major product). Starting material. Yield (%)b. Time (h). Product. 4. N. Ts NH. N. H. 1. 5. O. 3a. 89%. 4a. N N. O. 3 N 5a. 4%. N. N. Ts NH. N. H. 2. 3g. N. F O. F. O. 4g. 72%. N. F. 2.5 F. N 5g N. 23. F. 14%.

(34) Entrya. Starting material. Time (h). Product. Yield (%)b 4. N. Ts NH. N. H. 3. Cl O. 3h. N. Cl. O. 5. 60%. 4h. N. Cl 2.5. N. Cl. 5h. Cl. N. N. Ts NH. N. H. 4. Br O. 3i. N. Br. O. 11%. 99%. 4i. N. Br 1. Br. N 5i. N. 24. Br. tracec.

(35) Starting material. Entrya. Yield (%)b. Time (h). Product. 4. N. Ts NH. N OMe. H. 5. 5. O. 3j. N. MeO. 4j. 90%. N. O OMe. 3 N. MeO. 5j OMe. N. N. Ts NH H. 6d. N. N O. S O. 3k S. S. tracec. 12%. 4k. N. 2.5 N S S. 5k. tracec. N. aReaction. conditions: 3a (0.5 mmol), NaH (1.5 equiv.), dry THF (5 mL), under Ar. After the starting material disappeared, MeOH was added and then the solution was stirred for 5 minutes. bYields were determined by 1H NMR spectrum with CH Br as internal standard. 2 2 cCould not be isolated in pure form. dStarting material decomposed.. R2. Entry 2-3. (4-F). 2.5. 4g-4h. R2. (4-Br). R2. 60-72%. (4-OMe) 4i-j. 5. (4-Cl). (thiophene) 25. 90-99%. 1-3 Entry 4-.

(36) (decomposed) 4k. 2.5. 12%. Entry 6 R3. 3-5 N. N. 3. Ts NH. R3 N. H R3. NaH. O. THF, 50 ℃, Time (h). O. +. N. N R3. 4 (major product). 5. R3. 3. Entrya. R3 N. Starting material. Yield (%)b. Time (h). Product. 4 N. Ts NH H. 1. 5. N O. 3a. 89%. 4a. N N. O. 3 N 5a. 4%. N. N. Ts NH H. 2. N O. 3l. 98%. 4l. N O. N. 3 N 5l tracec N. 26.

(37) Entrya. Starting material. Yield (%)b. Time (h). Product. 4. N. Ts NH H. 3. 5. N O. 3m. 4m. 37%. N N. O. 3. N 5m. 19%. N. N. Ts NH H. 4. N O. 3n. 60%. 4n. N O. N. 1. N 5n N. 27. tracec.

(38) Entrya. Starting material. Yield (%)b. Time (h). Product. 4. 5. Cl. N. Ts NH N H. 5. 3o. O. N. 43%. 4o. N. O Cl Cl. 3 Cl. N 5o. 24%. N. Cl. aReaction. conditions: 3a (0.5 mmol), NaH (1.5 equiv.), dry THF (5 mL), under Ar. After the starting material disappeared, MeOH was added and then the solution was stirred for 5 minutes. bYields were determined by 1H NMR spectrum with CH Br as internal standard. 2 2 cCould not be isolated in pure form.. 3-5. (N-methyl) R3 4l. 98%. (allylic) Entry 3. Entry 2 5m. Entry 4-5. R3. chlorobenzyl). (benzyl). (ethyl) R3 19%. (34n-. 28.

(39) 4o. R3. 43-60% 5o. 3-. (3-chlorobenzyl). 24%. Entry 5. 3-3 3-4. 3. Ⅰ Ⅱ. Ⅱ. Ⅲ. Ⅲ. (amidic carbonyl). (biradical intermediate)Ⅳ. Ⅴ. Ⅴ. Ⅵ 1-. 2-. -2-. 1H-. 1H-. Ⅵ. (1-methyl-2-phenyl-1H-indole) Ⅴ. -3-. 4. 3,3'-. 2,25. 29. 1-. -.

(40) N. H N. Ts. N N. Ts. N N. NaH. NaH. -H2. N. -Ts. N. O. O. N O. (Ⅰ). 3. (Ⅱ). -N2. H. H. H. H. H. O. O. OH N. O. (Ⅴ). (Ⅵ). N. N. N. (Ⅳ). (Ⅲ). N. A.. H O. N. O. O. N. N. N. N. (Ⅴ). N. 4 B.. N. N. N. O. H N. OH N. N. (Ⅴ) 5. 3-4. 4 30. 5.

(41) 3-3. 2,2-. -3-. 3,3'-. 1(1-methyl-2-phenyl-1H-indole). 12,2-. -2-. -2-. 1H-. 1H-3-. 3,3'-. 3-. 2,2-. -3-. 2,2-. -3-. 31.

(42) 4 4-1 1.. (Nuclear Magnetic Resonance Spectroscopy ) ( NMR ). Bruker Avance 400 MHz. (tetramethylsilane, TMS) d6). Bruker Avance III HD 400 MHz. (CDCl3). (chemical shift). (DMSO1. ppm. H-NMR δ= 0. 7.26 ppm. 1. H-NMR. (singlet) (quartet). d. (splitting pattern) (doublet). m. (multiplet). doublet). t. (triplet). s q. dd(doublet of doublet). (coupling constant). J. td(triplet of Hz. (. ). 13. C-NMR. (CDCl3) δ= 77.23ppm 2.. (Thin Layer Chromotography,. TLC). Merck. Silica gel 60 F254. 3.. (Column Chromotography). Merk Silica gel 60 F. 230-400 mesh ATSM. (flash column. chromotography). (eluent). 32.

(43) 4.. (Mass Spectroscopy Spectroscopy. MS). (Low Resolution Mass. LRMS). Finnigan TSQ. 700 EI, LCQ advantage ESI spectrometer (m/z) 5.. X-ray. Nonius Kappa CCD. Bruker Kappa APEX II. 6. (ether) alumina column). 7.. (CH2Cl2). (melting point, m.p.). (active ACS. Mel-Temp. 33.

(44) 4-2. CH3NH2. +. H. R1. 2. HCl / NaHCO3 (aq). Br. H. R1 N H. 5 eq. 10 mmol. (10 mmol) mmol. O. 1. 5 mol% Cu powder water, 100℃, air. O. 1. 50. 40%. 0.5 mmol. 100℃. 50. TLC. 6M HCl. TLC. 1 O O H. R1. H. R1 N. Cl. N H. R2. CH2Cl2, rt, overnight. O. 1.5 eq. 1. 1 (6 mmol) (6 mmol) 1.5. 1 eq pyridine 10 mol% DMAP. O. 4-. 2. 100. 25 (0.6 mmol). 10. (9 mmol). TLC. 3M HCl. 2. 34. R2.

(45) O. N. O H N NH2 S O. H. R1 N. O S. O H. R1 N. MeOH, 60℃. O. H N. O. R2. R2 1.2 eq. 2. 2 (5 mmol) (6 mmol). 3. 50. 20. 60℃. 1.2. TLC. 3. N. H N. O S. R1. R2. N. O H. R1. 1.5 eq NaH. N. O. R2. THF, 50℃, 3h. O. R2. N. R1. R2. 4 (major product). 3. (1.5 mmol) 3 (1 mmol). 25. 5. 3. 7. 50℃. TLC 5. 4. R1. + R1. N. N. 5. 35. R2.

(46) 5 1. Li, Y-J.; Yan, N.; Liu, C-H.; Yu, Y. and Zhao, Y-L. Org. Lett. 2017, 19, 1160−1163. 2. Wetzel, A.; Gagosz, F. Angew. Chem. Int. Ed. 2011, 50, 7354 –7358. 3. Altinis Kiraz, C. I.; Emge, T. J.; Jimenez, L. S., J. Org. Chem. 2004, 69, 2200–2202. 4. Karadeolian, A.; Kerr, M. A. J. Org. Chem. 2010, 75, 6830–6841. 5. Balogh-Hergovich, E.; Speier, G. J. Mol. Catal. 1989, 57, L9–L12. 6. Zhou, X-Y.; Chen, X.; Wangb L-G.; Yanga, D.; Li, J-H. Synlett 2018, 28, 835–839. 7. Xia, Z.; Hu, J.; Gao, Y-Q.; Yao Q.; Xie, W., Chem. Commun. 2017, 53, 7485—7488. 8. Kumar, C. V. S.; Puranik,V. G. ; Ramana,C. V. Chem. Eur. J. 2012, 18, 9601 – 9611. 9. Ding, X.; Dong, C-L.; Guan, Z.; He, Y-H. Angew. Chem. Int. Ed. 2019, 58, 118 –124. 10. Kaushik, N. K.; Kaushik, N.; Attri, P.; Kumar ,N.; Kim,C. H.; Verma, A. K.; Choi, E. H. Molecules. 2013, 18, 6620-6662. 11. Raihan, M. J.; Kavalar, V.; Kuo, C.-W.; Raju, B. R.; Yao, C.-F., Green Chem. 2010, 12, 10901096.. 36.

(47) 37.

(48) 6 (E)-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide (3a). White solid, m.p.: 203-205℃. 1H-NMR (400 MHz, H O N CDCl3) δH (ppm): 10.22 (br, 1H), 8.06 (s, 1H), 7.77-7.80 N S O H. (m, 3H), 7.18-7.22 (m, 4H),7.11 (d, J = 7.4 Hz, 2H), 6.956.99 (m, 3H), 3.33 (s, 3H), 2.38 (s, 3H) ;13C-NMR (100 N MHz, CDCl3) δC (ppm): O 171.65, 143.61, 142.87, 141.97, 135.97,134.89, 130.76, 130.54, 129.87, 129.47, 128.56, 128.10, 127.95, 127.85, 127.10, 38.87, 21.53; HRMS (ESI) calcd For C22H22N3O3S (M+) 408.1382, found 408.1382.. (E)-N-(4-bromo-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide (3b). H White solid, m.p.: 213-215℃. 1H-NMR (400 MHz, O N N S CDCl3) δH (ppm): 9.88 (br, 1H), 7.92 (s, 1H),7.90 (d, J = O Br H 2.1 Hz, 1H), 7.78 (d, J = 8.3 Hz, 2H), 7.32 (dd, J = N 8.4,2.1 Hz, 2H), 7.24 (d, J = 0.2 Hz, 1H), 7.19 (t, J = 7.3 O Hz, 1H), 6.99-7.09 (m, 4H), 6.85 (d, J = 8.4 Hz, 1H), 3.30 (s, 3H), 2.40 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 171.49, 144.01, 141.88, 140.25, 133.65, 134.57, 133.76, 132.18, 130.21, 130.13, 129.93, 129.66, 128.05, 127.92, 127.87, 122.03, 38.80, 21.58; HRMS (ESI) calcd For C22H21N3O3SBr (M+) 486.0487, found 486.0490.. 38.

(49) (E)-N-(4-chloro-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide (3c). N. H N O H. Cl. O S. White solid, m.p.: 204-206℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 9.98 (br, 1H), 7.94 (s, 1H), 7.77 (d, J = 8.3 Hz, 2H), 7.75 (d, J = 2.3 Hz, 1H), 7.24 (s, 1H), 7.08-. N. 7.20 (m, 4H), 6.99-7.03 (m, 2H), 6.92 (d, J = 8.4 Hz, O 1H), 3.30 (s, 3H), 2.40 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 171.61, 143.97, 141.32, 140.34, 135.71, 134.58, 134.13, 131.99, 130.79, 130.18, 129.87, 129.63, 128.04, 127.86, 126.85, 38.84, 21.57; HRMS (ESI) calcd. For C22H21N3O3SCl (M+) 442.0992, found 442.0989.. (E)-N-(4-methoxy-2-((2-tosylhydrazineylidene)methyl)phenyl)-Nmethylbenzamide (3d). White solid, m.p.: 210-212℃. 1H-NMR (400 MHz, H O N N S CDCl3) δH (ppm): 10.26 (br, 1H), 8.02 (s, 1H), 7.76 O O H (d, J = 8.2 Hz, 2H), 7.08-7.25 (m, 6H), 6.96-7.00 (m, N 2H), 6.88 (d, J = 8.7 Hz, 1H), 6.73 (dd, J = 8.7,2.9 Hz, O 1H), 3.75 (s, 3H), 3.29 (s, 3H), 2.39 (s, 3H) ;13CNMR (100 MHz, CDCl3) δC (ppm): 171.89, 158.77, 143.61, 142.03, 136.10, 135.96, 135.07, 131.53, 129.71, 129.60, 129.46, 127.85, 117.58, 110.10, 55.54, 39.08, 21.54; HRMS (ESI) calcd. For C23H24N3O4S (M+) 438.1488, found 438.1486.. 39.

(50) (E)-N-(4,5-dimethoxy-2-((2-tosylhydrazineylidene)methyl)phenyl)-Nmethylbenzamide (3e). N. H N O H. O. O S. White solid, m.p.: 235-237℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 10.07 (br, 1H), 8.01 (s, 1H), 7.78 (d, J = 8.2 Hz, 2H), 7.11-7.22 (m, 6H), 6.97-7.01 (m,. 2H), 6.41 (s, 1H), 3.85 (s, 3H), 3.71 (s, 3H), 3.31 (s, 3H), 2.39 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC O (ppm): 171.81, 151.10, 148.66, 143.59, 142.58, 136.77, 135.98, 135.08, 129.84, 129.42, 127.85, 127.72, 123.14, 110.83, 107.59, 56.10, 56.07, 39.13, 21.54; HRMS (ESI) calcd. For C24H26N3O5S (M+) 468.1593, found 468.1597. O. N. (E)-N-methyl-N-(6-((2-tosylhydrazineylidene)methyl)benzo[d][1,3]dioxol-5yl)benzamide (3f). White solid, m.p.: 237-239℃. 1H-NMR (400 MHz, H O DMSO-d6) δH (ppm): 11.43 (br, 1H), 7.85 (s, 1H), N N S 7.71 (d, J = 8.1 Hz, 2H), 7.39 (d, J = 8.1 Hz, 2H), O O H 7.01-7.17 (m, 6H), 6.90 (s, 1H), 6.03 (d, 2H), 3.19 O N (s, 3H), 2.36 (s, 3H) ;13C-NMR (100 MHz, DMSOd6) δC (ppm): 170.30, 149.69, 147.36, 143.58, O 143.00, 138.54, 136.67, 136.51, 130.14, 129.59, 128.01, 127.64, 124.93, 109.83, 103.98, 102.71, 38.22, 21.45; HRMS (ESI) calcd. For C23H22N3O5S (M+) 452.1280, found 452.1281.. 40.

(51) (E)-4-fluoro-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide (3g). N. H N O H. O S. White solid, m.p.: 187-189℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 10.30 (br, 1H), 8.02 (s, 1H), 7.80 (dd, J = 7.6,1.6 Hz, 1H), 7.77 (d, J = 8.2 Hz, 2H), 7.20-7.28 (m,. 4H), 7.08-7.12 (m, 2H), 7.04 (dd, J = 2.8 Hz, 1H), 6.57 (t, J = 8.6 Hz, 2H), 3.34 (s, 3H), 2.39 (s, 3H) ;13C-NMR O (100 MHz, CDCl3) δC (ppm): 170.62, 164.33, 161.83, F 143.83, 142.65, 141.77, 135.81, 130.91, 130.53, 130.37, 130.28, 129.47, 128.27, 127.77, 127.23, 114.94, 114.72, 38.89, 21.46; HRMS (ESI) calcd. For C22H21N3O3SF (M+) 426.1288, found 426.1288. N. (E)-4-chloro-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide (3h). White solid, m.p.: 210-211℃. 1H-NMR (400 MHz, H O N N S CDCl3) δH (ppm): 9.71 (br, 1H), 7.96 (s, 1H), 7.79 (d, J = O 1.7 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.24 (d, J = 8.1 Hz, H 3H), 7.00-7.03 (m, 3H), 6.88 (d, J = 8.4 Hz, 2H), 3.34 (s, N 3H), 2.40 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC O (ppm): 170.50, 144.00, 142.54, 141.89, 135.95, 135.69, Cl 133.47, 131.05, 130.47, 129.60, 129.38, 128.49, 128.39, 128.05, 127.86, 127.59, 38.77, 21.59. ; HRMS (ESI) calcd. For C22H21N3O3SCl (M+) 442.0992, found 442.0990.. 41.

(52) (E)-4-bromo-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide (3i) N. H N O H. O S. White solid, m.p.: 163-165℃. 1H-NMR (400 MHz, DMSO-d6) δH (ppm): 11.60 (br, 1H), 7.95 (s, 1H), 7.72 (d, J = 8.1 Hz, 3H), 7.53 (d, J = 7.7 Hz, 1H), 7.37 (d, J = 8.1 Hz,. 2H), 7.30-7.32 (m, 2H), 7.22-7.26 (m, 1H), 7.16 (d, J = 8.4 O Hz, 2H), 6.97 (d, J = 8.4 Hz, 2H), 3.22 (s, 3H), 2.35 (s, Br 3H) ;13C-NMR (100 MHz, DMSO-d6) δC (ppm): 168.61, 143.40, 142.76, 142.38, 136.07, 135.31, 130.85, 130.45, 130.18, 129.70, 129.49, 128.12, 127.23, 126.77, 122.61, 17.57, 21.05; HRMS (ESI) calcd. For C22H21N3O3SBr (M+) 486.0487, found 486.0490. N. (E)-4-methoxy-N-methyl-N-(2-((2tosylhydrazineylidene)methyl)phenyl)benzamide (3j). White solid, m.p.: 193-195℃. 1H-NMR (400 MHz, CDCl3) H O N N S δH (ppm): 10.41 (br, 1H), 8.05 (s, 1H), 7.80-7.85 (m, 3H), O H 7.23 (d, J = 8.2 Hz, 3H), 7.21 (d, J = 4.0 Hz, 1H), 7.1 (d, J = N 8.6 Hz, 2H), 6.95-6.97 (m, 1H), 6.49 (d, J = 8.6 Hz, 2H), O 3.69 (s, 3H), 3.29 (s, 3H), 2.39 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 171.29, 160.80, 143.62, 143.44, OMe 141.95, 136.07, 130.82, 130.43, 130.30, 129.47, 128.44, 127.92, 127.81, 127.07, 126.71, 113.17, 55.10, 39.26, 21.54; HRMS (ESI) calcd. For C23H24N3O4S (M+) 438.1488, found 438.1488.. 42.

(53) (E)-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)thiophene-2carboxamide (3k). N. H N O H. O S. White solid, m.p.: 193-195℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 9.85 (br, 1H), 8.02-8.04(m, 2H), 7.827.84 (m, 2H), 7.43-7.45 (m,2H), 7.19-7.26 (m, 4H),. 6.67-6.69 (m, 1H), 6.60 (d, J = 3.3 Hz, 1H), 3.27 (s, 3H), 2.39 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): S O 126.91, 143.69, 142.24, 141.59, 136.74, 135.90, 132.56, 131.90, 131.41, 131.36, 129.51, 129.31, 129.02, 127.86, 127.37, 126.98, 39.39, 21.57; HRMS (ESI) calcd. For C20H20N3O3S2 (M+) 414.0946, found 414.0947. N. (E)-N-ethyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide (3l). White solid, m.p.: 183-185℃. 1H-NMR (400 MHz, H O N CDCl3) δH (ppm): 9.70 (br, 1H), 8.01 (s, 1H), 7.77N S 7.81 (m, 3H), 7.17-7.24 (m, 4H), 7.08-7.14 (m, 3H), O H 6.93-6.98 (m, 3H), 4.10-4.19 (m, 1H), 3.42-3.51 (m, N 1H), 2.39 (s, 3H), 1.13 (t, 3H) ;13C-NMR (100 MHz, O CDCl3) δC (ppm): 171.00, 143.64, 142.25, 141.04, 135.95, 135.31, 130.98, 130.50, 129.73, 129.65, 129.48, 128.04, 127.93, 127.87, 127.76, 127.10, 45.71, 21.54, 12.15; HRMS (ESI) calcd. For C23H24N3O3S (M+) 422.1538, found 422.1538.. 43.

(54) (E)-N-allyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide (3m). White solid, m.p.: 186-188℃. 1H-NMR (400 MHz, N. H N O H. O S. CDCl3) δH (ppm): 10.36 (br, 1H), 8.07 (s, 1H), 7.757.80 (m, 3H), 7.17-7.20 (m,4H), 7.11-7.13 (m, 3H), 6.91-6.95 (m,3H), 5.82-5.92 (m,1H), 5.05 (d, J = 10.1. Hz, 1H), 4.99 (d, J = 17.1 Hz, 1H), 4.64 (dd, J = 14.4,6.1 Hz,1H), 3.99 (dd, J = 14.4,7.2 Hz, 1H), 2.37 O (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 171.15, 143.43, 142.42, 140.87, 135.94, 134.95, 131.22, 130.93, 130.33, 129.74, 129.47, 129.35, 128.07, 127.85, 127.75, 127.69, 126.91, 119.64, 53.58, 21.43; HRMS (ESI) calcd. For C24H24N3O3S (M+) 434.1539, found 434.1538. N. (E)-N-benzyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide (3n). White solid, m.p.: 166-168℃. 1H-NMR (400 MHz, H O N CDCl3) δH (ppm): 9.08 (br, 1H), 7.77 (d, J = 8.3 Hz, N S O 2H), 7.66-7.72 (m, 2H), 7.22 (d, J = 8.1 Hz, 2H), 7.09H 7.18 (m, 10H), 6.93-6.97 (m, 2H), 6.75 (d, J = 7.2 Hz, N 1H), 5.18 (d, J = 13.9 Hz, 1H), 4.65 (d, J = 14.0 Hz, O 1H), 2.38 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 143.83, 142.50, 140.98, 135.85, 135.71,135.06, 130.91, 130.51, 129.82, 129.53, 129.44, 129.23, 128.50, 128.13, 127.93, 127.78, 127.14, 54.12, 21.54; HRMS (ESI) calcd. For C28H26N3O3S (M+) 484.1695,found 484.1693.. 44.

(55) (E)-N-(3-chlorobenzyl)-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide (3o). N. H N. White solid, m.p.: 138-140℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 9.32 (br, 1H), 7.82 (s, 1H), 7.79 (d, J = 8.2 Hz, 2H), 7.71-7.73 (m, 1H), 7.23 (d, J = 8.2 Hz, 2H),. O S. O H. 7.05- 7.18 (m, 9H), 6.95-6.98 (m, 2H), 6.69 (d, J = 7.7 Hz, 1H), 5.29 (d, J = 14.2 Hz, 1H), 4.40 (d, J = 14.2 Hz, 1H), O 2.37 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 207.0, 171.3, 143.9, 142.4, 140.7, 138.0, 135.7, 134.9, 134.8, 134.2, 130.6, 130.5, 130.0, 129.9, 129.8, 129.6, 129.3, 128.3, 128.1, 128.0, 127.9, 127.8, 127.7, 127.4, 53.4, 30.9, 21.5; HRMS (ESI) calcd. For C28H25N3O3SCl (M+) 518.1305, found 518.1304. N. Cl. 1-methyl-2-(1-methyl-2-phenyl-1H-indol-3-yl)-2-phenylindolin-3-one (4a). Yellow solid, m.p.: 244-246℃. 1H-NMR (400 MHz, N CDCl3) δH (ppm): 7.36-7.40 (m, 2H), 7.32 (d, J = 8.3 Hz, 1H), 7.23-7.26 (m, 5H), 7.16-7.20 (m, 5H), 7.1 (d, J = 7.3 O Hz, 1H), 6.86-6.92 (m, 2H), 6.79 (d, J = 7.6 Hz, 1H), 6.62 N (d, J = 8.2 Hz, 1H), 6.50- 6.56 (m, 2H), 3.44 (s, 3H), 2.77 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 200.0, 159.4, 140.0, 138.5, 137.1, 136.8, 131.4, 131.3, 130.7, 128.2, 127.7, 127.5, 126.9, 125.1, 121.9, 121.5, 119.5, 119.4, 116.4, 109.8, 109.4, 107.7, 30.5, 29.6; HRMS (EI) calcd. For C30H24N2O (M+) 428.1888, found 428.1888.. 45.

(56) 5-bromo-2-(5-bromo-1-methyl-2-phenyl-1H-indol-3-yl)-1-methyl-2phenylindolin-3-one (4b). N Br. O. Yellow solid, m.p.: 271-273℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 7.45 (d, J = 2.1 Hz, 1H), 7.43 (d, J = 2.1 Hz, 1H), 7.28-7.33 (m, 5H), 7.27 (d, J = 1.7 Hz,. 1H), 7.25 (d, J = 2.0 Hz, 1H), 7.17-7.19 (m, 2H), 7.12 (d, J = 2.1 Hz, 1H), 6.91-6.95 (m, 1H), 6.73 (d, J = 7.6 N Br Hz, 1H), 6.60 (d, J = 1.8 Hz, 1H), 6.45 (d, J = 8.7 Hz, 1H), 3.42 (s, 3H), 2.76 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 198.4, 158.0, 141.1, 139.5, 137.3, 135.4, 131.3, 130.6, 129.0, 128.7, 128.2, 127.9, 127.4, 127.0, 124.5, 124.0, 121.0, 113.0, 110.9, 109.5, 109.4, 108.5, 76.4, 30.7, 29.8; HRMS (ESI) calcd. For C30H23N2OBr2 (M+) 585.0184, found 585.0177.. 5-chloro-2-(5-chloro-1-methyl-2-phenyl-1H-indol-3-yl)-1-methyl-2phenylindolin-3-one (4c). Yellow solid, m.p.: 265-267℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 7.26-7.33 (m, 7H), 7.23 (d, J = 8.8 N Hz, 2H), 7.18 (d, J = 7.4 Hz, 1H), 7.11-7.14 (m, 1H), O Cl 6.99 (d, J = 2.2 Hz, 1H), 6.93 (t, J = 7.3 Hz, 1H), 6.74 (d, J = 7.6 Hz, 1H), 6.51 (d, J = 8.7 Hz, 1H), 6.47 (d, N Cl J = 1.8 Hz, 1H), 3.43 (s, 3H), 2.76 (s,3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 198.7, 157.8, 141.2, 137.3, 136.9, 135.1, 131.3, 130.7, 130.6, 128.6, 128.4, 128.2, 127.9, 127.0, 125.3, 124.3, 122.0, 121.7, 121.0, 120.4, 110.5, 109.5, 108.9, 30.7, 29.8; HRMS (ESI) calcd. For C30H23N2OCl2 (M+) 497.1186, found 497.1187.. 46.

(57) 5-methoxy-2-(5-methoxy-1-methyl-2-phenyl-1H-indol-3-yl)-1-methyl-2phenylindolin-3-one (4d). N MeO. O. Yellow solid, m.p.: 208-210℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 7.26-7.27 (m, 4H), 7.167.22 (m, 3H), 7.09 (dd, J = 8.9,2.7 Hz, 1H), 6.90. (t, J = 7.4 Hz, 1H), 6.80-6.83 (m, 1H), 6.74 (d, J = 7.5 Hz, 1H), 6.54-6.56 (m, 2H), 5.98 (d, J = 2.4 N OMe Hz, 1H), 3.66 (s, 3H), 3.45 (s, 3H), 3.41 (s, 3H), 2.78 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 200.1, 155.8, 153.5, 151.6, 140.2, 138.7, 132.0, 131.6, 131.3, 130.8, 128.1, 127.9, 127.6, 127.5, 126.8, 119.4, 111.9, 110.0, 109.7, 109.1, 105.6, 103.5, 55.9, 55.4, 30.6, 30.0; HRMS (ESI) calcd. For C32H29N2O3 (M+) 489.2178, found 489.2179.. 2-(5,6-dimethoxy-1-methyl-2-phenyl-1H-indol-3-yl)-5,6-dimethoxy-1-methyl-2phenylindolin-3-one (4e). Yellow solid, m.p.: 243-245℃. 1H-NMR (400 O N MHz, DMSO-d6) δH (ppm): 7.22-7.29 (m, 6H), 7.17-7.22 (m, 2H), 7.03 (s, 1H), 6.92 (m , 1H), 6.81 O O (m, 1H), 6.42 (s, 1H), 6.37 (s, 1H), 5.78 (s, 1H), N 3.90 (s, 3H), 3.79 (s, 3H), 3.58 (s, 3H), 3.38 (s, O 3H), 3.26 (s, 3H), 2.82 (s, 3H) ;13C-NMR (100 O MHz, DMSO-d6) δC (ppm): 196.5, 158.7, 157.2, 146.3, 143.8, 142.0, 139.0, 137.9, 131.3, 131.0, 130.8, 127.9, 127.7, 127.2, 127.1, 126.6, 119.6, 109.7, 109.0, 105.2, 103.3, 94.0, 91.5, 75.7, 56.02, 55.97, 55.8, 55.2, 30.6, 29.7; HRMS (ESI) calcd. For C34H33N2O5 (M+) 549.2386, found 549.2389.. 47.

(58) 5,5'-dimethyl-6,6'-diphenyl-5,6-dihydro-5'H,7H-[6,7'-bi[1,3]dioxolo[4,5-f]indol]7-one (4f). O O. N O. Yellow solid, m.p.: 280-282℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 7.21-7.26 (m, 7H), 7.12-7.14 (m, 1H), 7.04-7.08 (m, 1H), 6.90 (d, J = 7.6 Hz, 1H), 6.75. (s, 1H), 6.57 (s, 1H), 6.07 (s, 1H), 5.98 (s, 1H), 5.97 (d, J = 1.1 Hz, 1H), 5.91 (d, J = 1.0 Hz, 1H), 5.86 (s, N O 2H), 3.35 (s, 3H), 2.59 (s, 3H) ;13C-NMR (100 MHz, O DMSO-d6) δC (ppm): 197.8, 159.1, 156.8, 144.5, 142.3,140.5, 138.5, 138.2, 132.2, 131.9, 131.5, 130.7, 128.8, 128.0, 127.8, 127.4, 126.7, 121.1, 120.0, 109.7, 102.6, 101.6, 100.8, 100.5, 90.2, 88.9, 30.8, 29.9; HRMS (ESI) calcd. For C32H25N2O5 (M+) 517.1763, found 517.1763.. 2-(4-fluorophenyl)-2-(2-(4-fluorophenyl)-1-methyl-1H-indol-3-yl)-1methylindolin-3-one (4g). Yellow solid, m.p.: 232-234℃. 1H-NMR (400 MHz, N CDCl3) δH (ppm): 7.40-7.45 (m, 2H), 7.33 (d, J = 8.2 F Hz, 2H), 7.20 (t, J = 7.9 Hz, 2H), 7.09 (d, J = 7.7 Hz, O 1H), 6.89-7.01 (m, 4H), 6.66-6.70 (m, 1H), 6.62 (d, J = F N 8.3 Hz, 1H), 6.58 (d, J = 7.4 Hz, 2H), 6.50-6.55 (m, 1H), 3.44 (s, 3H), 2.84 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 199.8, 163.9, 163.8, 161.5, 161.4, 159.4, 138.9, 137.5, 136.7, 134.03, 134.00, 133.3, 133.2, 132.63, 132.55, 127.3, 127.09, 127.06, 125.1, 121.8,121.5, 119.7, 119.4, 116.8, 115.0, 114.8, 113.9, 113.7, 110.3, 109.6, 107.7, 75.6, 30.5, 29.7; HRMS (ESI) calcd. For C30H23N2OF2 (M+) 465.1788, found 465.1782.. 48.

(59) 2-(4-chlorophenyl)-2-(2-(4-chlorophenyl)-1-methyl-1H-indol-3-yl)-1methylindolin-3-one (4h). N Cl O. Yellow solid, m.p.: 284-286℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 7.42-7.46 (m, 1H), 7.33 (d, J = 8.2 Hz, 1H), 7.19-7.27 (m, 6H), 7.15 (dd, J = 8.2,2.0 Hz,. 1H), 7.08 (d, J = 7.4 Hz, 1H), 6.90-6.94 (m, 1H), N 6.80 (dd, J = 8.1,2.1 Hz, 1H), 6.58-6.63 (m, 4H), 3.45 (s, 3H), 2.83 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 199.5, 159.5, 138.7, 137.6, 136.83, 136.75, 134.7, 133.8, 132.7, 132.1, 129.5, 128.0, 127.3, 127.0, 125.2, 121.9, 121.5, 119.8, 119.4, 116.9, 110.1, 109.6, 107.8, 75.7, 30.6, 29.7; HRMS (EI) calcd. For C30H22Cl2N2O (M+) 496.1110, found 496.1110. Cl. 2-(4-bromophenyl)-2-(2-(4-bromophenyl)-1-methyl-1H-indol-3-yl)-1methylindolin-3-one (4i). Yellow solid, m.p.: 252-254℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 7.44-7.46 (m, 1H), 7.41-7.42 (m, N Br 1H), 7.39 (d, J = 8.6 Hz, 3H),7.33 (d, J =8.3 Hz, 2H) O 7.18-7.22 (m, 1H), 7.08 (d, J = 8.2 Hz, 1H), 7.07 (d, Br J = 8.0 Hz, 1H), 6.90- 6.96 (m, 2H), 6.59-6.63 (m, N 3H), 6.55 (dd, J = 8.2,2.0 Hz, 1H), 3.44 (s, 3H), 2.82 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 199.4, 159.5, 138.7, 137.6, 137.4, 136.7, 132.9, 132.3, 130.9, 130.0, 129.9, 127.2, 125.2, 123.1, 122.1, 121.9, 121.5, 119.9, 119.4, 116.9, 110.0, 109.6, 107.8, 75.8, 30.6, 29.7; HRMS (ESI) calcd. For C30H23N2OBr2 (M+) 585.0172, found 585.0177.. 49.

(60) 2-(4-methoxyphenyl)-2-(2-(4-methoxyphenyl)-1-methyl-1H-indol-3-yl)-1methylindolin-3-one (4j).. N OMe. Yellow solid, m.p.: 227-229℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 7.38 (t, J = 7.7 Hz, 2H), 7.30 (d, J = 8.2 Hz, 2H), 7.17 (t, J = 7.6 Hz, 1H),. O. 7.11 (d, J = 8.1 Hz, 2H), 6.89 (t, J = 7.6 Hz, 1H), MeO 6.80 (dd, J = 8.3,2.6 Hz, 3H), 6.65 (d, J = 8.0 Hz, N 2H), 6.58 (d, J = 8.3 Hz, 1H), 6.51 (t, J = 7.3 Hz, 1H), 6.35 (dd, J = 8.4, 2.5 Hz, 1H), 3.78 (s, 3H), 3.75 (s, 3H), 3.45 (s, 3H), 2.81(s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 200.4, 159.5, 159.3, 159.2, 139.9, 137.0, 136.7, 132.6, 132.1, 130.4, 127.6, 125.2, 123.4, 121.7, 121.3, 119.6, 119.3, 116.1, 113.4, 112.1, 110.3, 109.3, 107.5, 75.7,30.4, 29.6; HRMS (EI) calcd. For C32H28N2O3 (M+) 488.2102, found 488.2102.. 1-methyl-2-(1-methyl-2-(thiophen-2-yl)-1H-indol-3-yl)-2-(thiophen-2-yl)indolin3-one (4k). Yellow solid, m.p.: 223-225℃. 1H-NMR (400 MHz, CDCl3) N S δH (ppm): 7.39-7.43 (m, 1H), 7.27-7.33 (m, 2H), 7.19-7.23 (m, 3H), 7.09-7.10 (m, 1H), 6.92-6.96 (m, 2H), 6.73-6.75 (m, O 2H), 6.69 (d, J = 8.2 Hz, 1H), 6.63 (d, J = 8.3 Hz, 1H), 6.59 N S (t, 7.4 Hz, 1H), 3.50 (s, 3H), 2.94 (s, 3H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 199.1, 159.5, 142.7, 137.3, 138.1, 132.0, 131.5, 130.6, 128.3, 127.5, 127.2, 126.9, 126.2, 125.4, 124.8, 122.3, 121.3, 119.9, 118.9, 117.0, 112.5, 109.6, 108.2, 73.8, 30.5, 30.1; HRMS (ESI) calcd. For C26H21N2OS (M+) 441.1093, found 441.1095.. 50.

(61) 1-ethyl-2-(1-ethyl-2-phenyl-1H-indol-3-yl)-2-phenylindolin-3-one (4l). Yellow liquid, 1H-NMR (400 MHz, DMSO-d6) δH (ppm): N O. 7.44-7.51 (m, 2H), 7.26 (m, 7H), 7.08-7.13 (m, 2H), 6.967.01 (m, 3H), 6.79 (t, J = 7.6 Hz, 1H), 6.69 (d, J = 8.3 Hz, 1H), 6.53-6.57 (m, 2H), 3.88 (q, J = 7.1 Hz, 2H), 3.56 (m,. 1H), 3.05 (m, 1H), 1.03 (t, J = 7.0 Hz, 3H), 0.48 (t, J = 7.0 N Hz, 3H) ;13C-NMR (100 MHz, DMSO-d6) δC (ppm): 198.6, 157.6, 138.7, 138.6, 137.3, 135.3, 131.0, 130.8, 130.0, 129.3, 128.6, 128.2, 127.6, 127.4, 126.9, 126.8, 126.0 124.3, 121.3, 121.1, 119.0, 118.3, 116.1, 110.1, 109.7, 108.4, 75.4, 14.9, 12.4; HRMS (ESI) calcd. For C32H29N2O (M+) 457.2283, found 457.2280.. 1-allyl-2-(1-allyl-2-phenyl-1H-indol-3-yl)-2-phenylindolin-3-one (4m). Yellow liquid. 1H-NMR (400 MHz, DMSO-d6) δH (ppm): 7.39-7.48 (m, 3H), 7.24-7.28 (m, 7H), 7.08-7.13 (m, 3H), N 6.99 (d, J = 7.3 Hz, 1H), 6.93 (s, 2H), 6.81 (t, J = 7.4 Hz, 1H), 6.71 (d, J = 8.2 Hz, 1H), 6.59 (t, J = 7.2 Hz, 1H), 6.50 O (d, J = 7.8 Hz, 1H), 5.72-5.79 (m, 1H), 4.96- 5.03 (m, 2H), N 4.80-4.87 (m, 2H), 4.67 (d, J = 16.8 Hz, 1H), 4.47 (br, 2H), 4.17 (dd, J = 15.9,6.0 Hz, 1H), 3.59-3.62 (m, 1H) ;13CNMR (100 MHz, DMSO-d6) δC (ppm): 198.4, 158.0, 139.1, 138.5, 135.8, 133.2, 130.8, 130.7, 130.3, 128.7, 128.3, 127.8., 127.3, 126.8, 124.2, 121.0, 118.5, 117.7, 115.9, 110.6, 109.9, 109.0, 75.6, 46.3, 45.4; HRMS (ESI) calcd. For C34H29N2O (M+) 481.2280, found 481.2281.. 51.

(62) 1-benzyl-2-(1-benzyl-2-phenyl-1H-indol-3-yl)-2-phenylindolin-3-one (4n). Yellow solid, m.p.: 111-113℃. 1H-NMR (400 MHz, CDCl3) δH (ppm): 7.52 (br, 1H), 7.30-7.34 (m, 2H), 7.197.21 (m, 6H), 7.15-7.16 (m, 4H), 7.05-7.10 (m, 3H), 6.997.02 (m, 2H), 6.86-6.90 (m, 1H), 6.79-6.84 (m, 4H), 6.75 (d,. N. J = 7.3 Hz, 2H), 6.58 (t, J = 7.4 Hz, 1H), 6.52 (d, J = 8.3 Hz, 1H), 5.04-5.14 (m, 2H), 4.71 (d, J = 16.4 Hz, 1H), 4.36 (d, J N = 16.8 Hz, 1H) ;13C-NMR (100 MHz, CDCl3) δC (ppm): 199.1, 158.8, 138.5, 138.0, 137.8, 137.0, 136.6, 131.4, 131.3, 130.8, 129.0, 128.6, 128.4, 128.1, 127.8, 127.7, 127.5, 127.4, 127.1, 126.8, 126.2, 125.2, 122.1, 121.9, 119.8, 119.5, 117.0, 110.8, 110.4, 108.8, 48.7, 47.3; HRMS (EI) calcd. For C42H32N2O (M+) 580.2514, found 580.2514. O. 1-(3-chlorobenzyl)-2-(1-(3-chlorobenzyl)-2-phenyl-1H-indol-3-yl)-2phenylindolin-3-one (4o). Yellow solid, m.p.: 108-110℃. 1H-NMR (400 MHz, CDCl3) Cl δH (ppm): 7.51 (br, 1H), 7.35 (td, J = 3.3 Hz, 1H), 7.21-7.24 (m, 3H), 7.17-7.19 (m, 3H), 7.15 (d, J = 1.0 Hz, 1H), 7.107.13 (m, 2H), 6.96- 7.01 (m, 2H), 6.89-6.94 (m, 4H), 6.80 (d, N J = 8.1 Hz, 2H), 6.60-6.67 (m, 3H), 6.51 (s, 1H), 6.46 (d, J = 8.3 Hz, 1H), 4.95-5.06 (m, 2H), 4.65 (d, J = 16.6 Hz, 1H), O 4.22 (d, J = 15.6 Hz, 1H) ;13C-NMR (100 MHz, CDCl3) δC N (ppm): 199.0, 158.5, 140.0, 139.8, 139.5, 138.2, 137.2, 136.6, 134.4, 133.9, 131.5, 131.0, 130.4, 130.0, 129.2, 129.1, 128.6, 127.9, 127.8, 127.5, 127.4, 127.3, 127.2, 126.9, 126.5, Cl 126.4, 125.3, 124.3, 122.3, 122.2, 120.1, 119.4, 117.4, 110.8, 110.2, 108.5, 47.9, 46.9; HRMS (ESI) calcd. For C42H31N2OCl2 (M+) 649.1808, found 649.1813.. 52.

(63) 1,1'-dimethyl-2,2'-diphenyl-1H,1'H-3,3'-biindole (5a). White solid, m.p.: 282-284℃. 1H-NMR (400 MHz, N. CDCl3) δH (ppm): 7.56 (d, J = 7.8 Hz, 1H), 7.39-7.41 (m, 1H), 7.29 (td, J =8.0 Hz, 1H), 7.09-7.14 (m, 2H), 7.03 (t, J = 7.5 Hz, 2H), 6.69 (d, J = 7.2 Hz, 2H), 3.60 (s, 3H) ;13C-. NMR (100 MHz, CDCl3) δC (ppm): 138.9, 137.6, 132.1, 130.2, 129.1, 127.8, 126.6, 121.5, 120.8, 119.3, 109.3, 107.4, 31.1; HRMS (EI) calcd. For C30H24N2 (M+) 421.1940, found 421.1940. N. 1,1'-diallyl-2,2'-diphenyl-1H,1'H-3,3'-biindole (5m). White solid, m.p.: 173-175℃. 1H-NMR (400 MHz, DMSO-d6) δH (ppm): 7.41 (d, J = 8.2 Hz, 1H), 7.25 (d, J = 7.8 Hz, 1H), 7.16-7.21 (m, 2H), 7.11-7.14 (m, 2H), 7.00 N (t, J = 7.4 Hz, 1H), 6.84 (d, J = 7.1 Hz, 2H), 5.86-5.95 (m, 1H), 5.07 (d, J = 11.5 Hz, 1H), 4.69-4.75 (m, 1H), 4.604.64 (m, 2H) ;13C-NMR (100 MHz, DMSO-d6) δC (ppm): N 138.5, 136.5, 134.4, 131.5, 129.4, 128.5, 127.8, 127.3, 121.5, 119.5, 119.4, 115.4, 110.5, 107.0, 45.7; HRMS (ESI) calcd. For C34H29N2 (M+) 465.2324, found 465.2331.. 53.

(64) 1,1'-bis(3-chlorobenzyl)-2,2'-diphenyl-1H,1'H-3,3'-biindole (5o). White solid, m.p.: 239-241℃. 1H-NMR (400 MHz, Cl. DMSO-d6) δH (ppm): 7.68-7.70 (m, 1H), 7.19-7.23 (m, 3H), 7.17-7.18 (m ,2H), 7.06-7.09 (m, 2H), 7.00-7.01 (m, 2H), 6.92 (br, 1H), 6.80 (d, J = 6.1 Hz, 1H), 6.61 (d, J = 7.1 Hz,. N. N. 2H), 5.18-5.28 (m, 2H) ;13C-NMR (100 MHz, DMSO-d6) δC (ppm): 140.6, 139.1, 136.9, 134.7, 131.5, 129.9, 129.8, 129.5, 127.9, 127.3, 127.1, 126.0, 124.0, 122.1, 120.8, 120.0, 110.2, 108.3, 47.1; HRMS (ESI) calcd. For C42H31N2Cl2 (M+) 633.1857, found 633.1864.. Cl. 54.

(65) 1. H-NMR. 13. C-NMR.

(66)

(67) C D P NAME 20200423-3F E PNO 5 PROCNO 1. 2.3 01. 3.32 1. .0652 . 056 . 4 . 31 . 666 .260 .2201 .1 .1 21 .1 30 .1 6 .1361 .11 5 .0 1 6. 5 6. 6 6. 6 3 6. 4 0. 10.21. (E)-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide. F2 - A D. P 20200423 17.30. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 113.31 D 69.333 DE 10.06 E 297.7 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300092 MH D EM B 0 LB 0H GB 0 PC 1.00. 3. 2 3.000. 4 0. 5. 2.. 4.0 0 2. 36 2. 10. 6 1.012 2.. 10 0. 4. 11. 1.

(68) 21.53. 38.87. 77.32 77.00 76.68. 143.61 142.87 141.97 135.97 134.89 130.76 130.54 129.87 129.47 128.56 128.10 127.95 127.85 127.10. 171.65. (E)-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide C D P NAME 20200423-3F E PNO 6 PROCNO 1 F2 - A D. P 20200423 17.33. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 332 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 298.6 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127713 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(69) C D P NAME 20200529-3F E PNO 7 PROCNO 1. 2.402. 1 3.2. . 1 0 . 6 . 44 . 5 . 650 .32 .3246 .30 .3036 .2422 .2034 .1 55 .16 0 .0 06 .0 24 .031 .0131 6. 3 6. 615 6. 405. .. 3. (E)-N-(4-bromo-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide. F2 - A D. P 20200530 1.32. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 293.8 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300094 MH D EM B 0 LB 0H GB 0 PC 1.00. 4. 3. 2 3.000. 5. 2. 5. 6 1. 64 1. 6 0. 5 1.02 1.01 3. 20 0. 1. 10 0. 45. 11. 1.

(70) 21.58. 38.80. 77.32 77.00 76.68. 144.03 141.88 140.25 135.65 134.57 133.76 132.18 130.21 130.13 129.93 129.66 128.05 127.92 127.87 122.03. 171.49. (E)-N-(4-bromo-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide C D P NAME 20200529-3F E PNO 3 PROCNO 1 F2 - A D. P 20200530 9.21. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 15737 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 298.1 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127699 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(71) C D P NAME 20200609-3F E PNO 3 PROCNO 1. 2.402. 3.3052. . 3 5 . 44 . 63 . 526 . 46 .23 2 .1 .1 03 .15 0 .152 .0 42 .0 5 .02 .00 0 6. 6 6. 5 6. 320 6. 10. .. 1. (E)-N-(4-chloro-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide. F2 - A D. P 20200609 17.01. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 296.2 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300090 MH D EM B 0 LB 0H GB 0 PC 1.00. 4. 3. 2 3.000. 5. 2. 34. 6 1.00 2. 5 1.05 1. 54 1. 1 1. 2 0. 43. 3. 10. 0.. 11. 1.

(72) 21.57. 38.84. 77.32 77.00 76.68. 143.97 141.32 140.34 135.71 134.58 134.13 131.99 130.79 130.18 129.87 129.63 128.04 127.86 126.85. 171.61. (E)-N-(4-chloro-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide C D P NAME 20200609-3F E PNO 4 PROCNO 1 F2 - A D. P 20200611 17.38. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 1941 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 297.7 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127700 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(73) C D P NAME 20200422-3F E PNO 4 PROCNO 1. 2.3 6. 5 3.2. 3. 52. .01 3 . 3 . 532 .2521 .2153 .1 4 .1623 .143 .1253 .1025 .0 43 6. 60 6. 6 6. 5 5 6. 16 6. 6 6. 4 3 6. 411 6. 266 6. 1 3. 10.25 5. (E)-N-(4-methoxy-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide. F2 - A D. P 20200422 17.00. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 297.5 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300090 MH D EM B 0 LB 0H GB 0 PC 1.00. 3. 2 3.001. 4 2. 50. 5. 2.. 0. 1.. 5.5 1. 1 0. 6 0. 62. 6 1 0. 10 0. 1. 11. 1.

(74) 21.54. 39.08. 55.54. 77.32 77.00 76.68. 143.61 142.03 136.10 135.96 135.07 131.53 129.71 129.60 129.46 127.85 117.58 110.10. 158.77. 171.89. (E)-N-(4-methoxy-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide C D P NAME 20200422-3F E PNO 5 PROCNO 1 F2 - A D. P 20200422 17.10. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 517 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 298.7 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127705 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(75) 4. C D P NAME 20200428-3F E PNO 1 PROCNO 1. 2.3. 3.30 4. 3. 461 3. 060. .0142 . 2 . 6 6 .2163 .1 .1626 .143 .12 .10 3 .0103 6. 13 6. 1 6.4064. 10.06 2. (E)-N-(4,5-dimethoxy-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide. F2 - A D. P 20200428 17.08. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 297.7 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300083 MH D EM B 0 LB 0H GB 0 PC 1.00. 2 3.000. 3 2. 12. 4 3 4. 5. 2. 2.. 0. 24. 5. 1 1. 04. 6 0. 2.03. 10. 0.. 11. 1.

(76) 21.54. 39.13. 56.10 56.07. 77.32 77.00 76.68. 151.10 148.66 143.59 142.58 136.77 135.98 135.08 129.84 129.42 127.85 127.72 123.14 110.83 107.59. 171.81. (E)-N-(4,5-dimethoxy-2-((2-tosylhydrazineylidene)methyl)phenyl)-N-methylbenzamide. C D P NAME 20200428-3F E PNO 2 PROCNO 1 F2 - A D. P 20200428 17.12. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 681 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 298.7 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127707 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(77) C D P NAME 20200514-3F E PNO 3 PROCNO 1. 2.5000 2.3636. 3.1 5. . 535 . 164 .6 62 .3 2 .3 0 .1665 .14 6 .101 .0 3 .0611 .042 .0234 .0111 6. 6 6.043 6.0152. 11.4336. (E)-N-methyl-N-(6-((2-tosylhydrazineylidene)methyl)benzo[d][1,3]dioxol-5-yl)benzamide. F2 - A D. P 20200514 16.51. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN DM O N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 113.31 D 69.333 DE 10.06 E 296.0 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300032 MH D EM B 0 LB 0H GB 0 PC 1.00. 4. 3. 2 3.000. 5. 2.6 3. 6 1. 22. 10 1.034 1. 52 2.060 1.041 4.661 0. 60. 0. 51. 11. 1.

(78) 20.97. 40.15 39.94 39.73 39.52 39.31 37.74. 149.21 146.88 143.37 142.52 138.06 136.19 136.03 129.65 129.11 127.53 127.16 124.45 109.35 103.50 102.23. 169.82. (E)-N-methyl-N-(6-((2-tosylhydrazineylidene)methyl)benzo[d][1,3]dioxol-5-yl)benzamide C D P NAME 20200511-3F E PNO 5 PROCNO 1 F2 - A D. P 20200514 16.53. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN DM O N 2966 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 296.2 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6128181 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(79) C D P NAME 20190812-3F E PNO 1 PROCNO 1. 2.3 0. 3.345. 10.302 .0203 . 150 . 112 . 63 . 21 . . 5 1 .2 25 .2 5 .25 .2454 .23 .2342 .2135 .2026 .116 .1035 .0 51 .0 65 .0 1 .04 2 .0462 .02 5 .02 6 6.5 3 6.5 22 6.5506. (E)-4-fluoro-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide. F2 - A D. P 20190812 18.36. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 63.58 D 69.333 DE 10.06 E 296.1 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300077 MH D EM B 0 LB 0H GB 0 PC 1.00. 4. 3. 2 3.000. 5. 2. 46. 1. 6. 4.160 2.02 1.050. 6 0. 6 0. 5 2.050. 10 0. 4. 11. 1.

(80) 21.46. 38.89. 77.32 77.00 76.68. 170.62 164.33 161.84 143.83 142.65 141.77 135.81 130.91 130.53 130.37 130.28 129.48 128.27 127.77 127.23 114.94 114.72. (E)-4-fluoro-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide C D P NAME 20190812-3F E PNO 2 PROCNO 1 F2 - A D. P 20190812 18.41. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 163 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 297.2 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127746 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(81) C D P NAME 20200521-3F E PNO 2 PROCNO 1. 2.4045. 3.33. . 645 . 14 . 0 . 33 . 52 .24 6 .22 4 .0311 .02 0 .0206 .00 4 6. 6 6. 41 6. 30. . 0 5. (E)-4-chloro-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide. F2 - A D. P 20200521 18.21. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 8 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 297.8 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300092 MH D EM B 0 LB 0H GB 0 PC 1.00. 4. 3. 2 3.000. 5. 2. 20. 3.300 2. 5 1.. 6 0. 0 2. 1. 10 0. 14. 11. 1.

(82) 21.59. 38.77. 77.32 77.00 76.68. 144.00 142.54 141.89 135.95 135.69 133.47 131.05 130.47 129.60 129.38 128.49 128.39 128.05 127.86 127.59. 170.50. (E)-4-chloro-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide C D P NAME 20200522-4F E PNO 3 PROCNO 1 F2 - A D. P 20200522 19.06. INS R M PROBHD 5 BBO BB-1H P LPROG 30 D 32768 SOL EN CDC 3 NS 3745 DS 0 S H 24038.461 H FIDRES 0.733596 H AQ 0.6815744 RG 32768 D 20.800 DE 6.50 E 296.9 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== N C1 13C P1 10.00 PL1 3.80 B SFO1 100.6233325 MH ======== CHANNEL 2 ======== CPDPRG 2 16 N C2 1H PCPD2 90.00 PL2 10.20 B PL12 26.00 B PL13 29.00 B SFO2 400.1316005 MH F2 - P SI 32768 SF 100.6127710 MH D EM SSB 0 LB 1.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(83) C D P NAME 20200611-3F E PNO 2 PROCNO 1. 2.5000 2.353. 3.21. . 502 . 2 5 . 0 2 .53 .51 .3 3 .3635 .3210 .30 3 .2 62 .256 .2505 .23 2 .2240 .2165 .1655 .1446 6. 40 6. 631. 11.5 2. (E)-4-bromo-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide. F2 - A D. P 20200611 17.09. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN DM O N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 99.72 D 69.333 DE 10.06 E 296.0 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300032 MH D EM B 0 LB 0H GB 0 PC 1.00. 5. 4. 3. 2 3.000. 6. 2. 61. 10 1.023 2.26 1.003 2.200 1. 2 0. 43 1. 3 1. 14. 0.. 11. 1.

(84) 40.15 39.94 39.73 39.52 39.31 39.10 38.89 37.57 21.05. 143.40 142.76 142.38 136.07 135.31 130.85 130.45 130.18 129.70 129.49 128.12 127.23 126.77 122.61. 168.61. (E)-4-bromo-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide C D P NAME 20200611-3F E PNO 3 PROCNO 1 F2 - A D. P 20200611 17.15. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN DM O N 405 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 297.2 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6128174 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(85) 3. 0. C D P NAME 20200521-3F E PNO 1 PROCNO 1. 3.2. 2.3. 3.6 00. .053 . 454 . 40 . 2 . 1 6 . .2430 .2225 .2134 .2035 .1024 .0 10 6. 2 6. 6 6. 526 6.5031 6.4 16. 10.405. (E)-4-methoxy-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide. F2 - A D. P 20200521 16.44. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 8 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 113.31 D 69.333 DE 10.06 E 297.1 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300089 MH D EM B 0 LB 0H GB 0 PC 1.00. 3. 2 3.000. 4 3.001. 5. 2. 43. 1.. 3. 25 1. 0 0. 45. 6 1.005 2. 6. 10 0. 0. 11. 1.

(86) 21.54. 39.26. 55.10. 77.32 77.00 76.68. 160.80 143.62 143.44 141.95 136.07 130.82 130.43 130.30 129.47 128.44 127.92 127.81 127.07 126.71 113.17. 171.29. (E)-4-methoxy-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide C D P NAME 20200521-4F E PNO 2 PROCNO 1 F2 - A D. P 20200521 18.05. INS R M PROBHD 5 BBO BB-1H P LPROG 30 D 32768 SOL EN CDC 3 NS 714 DS 0 S H 24038.461 H FIDRES 0.733596 H AQ 0.6815744 RG 812.7 D 20.800 DE 6.50 E 295.1 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== N C1 13C P1 10.00 PL1 3.80 B SFO1 100.6233325 MH ======== CHANNEL 2 ======== CPDPRG 2 16 N C2 1H PCPD2 90.00 PL2 10.20 B PL12 26.00 B PL13 29.00 B SFO2 400.1316005 MH F2 - P SI 32768 SF 100.6127735 MH D EM SSB 0 LB 1.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(87) 2.3 25. 3.26 5. . 4 2 .03 6 .02 2 .0160 . 3 . 335 . 20 . 16 .450 .444 .43 .4340 .42 4 .2610 .2552 .23 .2343 .2264 .222 .215 .206 .2054 .1 4 6.6 33 6.6 31 6.6 13 6.60 6 6.6003. (E)-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)thiophene-2-carboxamide C D P NAME 20200507-3F E PNO 2 PROCNO 1 F2 - A D. P 20200507 18.21. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 298.7 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300092 MH D EM B 0 LB 0H GB 0 PC 1.00. 3. 2 3.000. 4 2. 5. 2.. 1. 30. 2.031 3. 01. 6 2.001 1. 1. 10 0. 4. 11. 1.

(88) 21.57. 39.39. 77.32 77.00 76.68. 162.91 143.69 142.24 141.59 136.74 135.90 132.56 131.90 131.41 131.36 129.51 129.31 129.02 127.86 127.37 126.98. (E)-N-methyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)thiophene-2-carboxamide C D P NAME 20200507-3F E PNO 3 PROCNO 1 F2 - A D. P 20200507 18.27. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 478 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 299.6 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127704 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(89) 1.14 6 1.12 1.1120. 4.1 2 4.1 11 4.153 4.13 3 4.11 4.1020 3.506 3.4 3.4 10 3.454 3.43 3 3.41 4 2.3 02. .0135 . 0 . 15 . 0 .236 .2162 .2012 .1 1 .1 23 .13 2 .120 .0 6 .0 5 6. 64 6. 5 3 6. 4 5 6. 405 6. 260. .6 14. (E)-N-ethyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide C D P NAME 20200608-3F E PNO 2 PROCNO 1 F2 - A D. P 20200608 16.08. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 296.6 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300092 MH D EM B 0 LB 0H GB 0 PC 1.00. 1 2. 41. 2 3.000. 3 6. 4. 0.. 5. 0. 46. 3. 2. 54 2. 30. 6 1.00 2. 32. 10 0. 03. 11.

(90) 12.15. 21.54. 45.71. 77.32 77.00 76.68. 143.64 142.25 141.04 135.95 135.31 130.98 130.50 129.73 129.65 129.48 128.04 127.93 127.87 127.76 127.10. 171.00. (E)-N-ethyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide C D P NAME 20200608-3F E PNO 3 PROCNO 1 F2 - A D. P 20200609 16.49. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 1318 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 296.0 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127701 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(91) (E)-N-allyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide 10.355 .06 4 . 2 . 5 . 1 . 36 . 6 . 4 1 .1 64 .1 4 .1 65 .16 6 .1261 .113 .105 6. 4 6 6. 302 6. 102 5. 1 0 5. 013 5. 2 5. 4 5. 5 5. 5 3 5. 503 5. 422 5. 33 5. 1 1 5.0601 5.034 5.0143 4. 14 4.6 0 4.655 4.634 4.61 4.01 4.000 3. 2 3. 64 2.3 2. C D P NAME 20190510-3F E PNO 3 PROCNO 1 F2 - A D. P 20190510 21.21. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 8 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 51.8 D 69.333 DE 10.06 E 297.8 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300093 MH D EM B 0 LB 0H GB 0 PC 1.00. 3. 2 3.000. 0.. 4 0. 26. 5 1. 26. 0. 2. 6. 32 2. 6. 6 0. 36 2. 54. 10 0. 05. 11. 1.

(92) C D P NAME 20190513-3F E PNO 3 PROCNO 1. 21.43. 53.58. 77.32 77.20 77.00 76.68. 171.15 143.43 142.42 140.87 135.94 134.95 131.22 130.93 130.33 129.74 129.47 129.35 128.07 127.85 127.75 127.69 126.91 119.64. (E)-N-allyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide. F2 - A D. P 20190513 18.11. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 102 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 299.4 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127801 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210 200 190 180 170 160 150 140 130 120 110 100. 90. 80. 70. 60. 50. 40. 30. 20. 10. 0.

(93) C D P NAME 20200424-3F E PNO 7 PROCNO 1. 2.3 56. .0 45 . 0 . 563 . 242 . 1 . 134 . 053 . 014 .6622 .230 .2106 .1 0 .1 35 .1 16 .1621 .154 .1416 .12 1 .10 .0 3 6. 6 3 6. 4 3 6. 2 5 6. 60 6. 42 5.1 60 5.1612 4.6 14 4.6365. (E)-N-benzyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide. F2 - A D. P 20200424 17.21. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 297.3 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300096 MH D EM B 0 LB 0H GB 0 PC 1.00. 3. 2 3.000. 4 0. 25. 5 1.006. 11. 44 1. 0. 1. 6. 3.. 10 0. 22. 11. 1.

(94) 21.54. 54.12. 77.32 77.00 76.68. 143.83 142.50 140.98 135.85 135.71 135.06 130.91 130.51 129.82 129.53 129.44 129.23 128.50 128.13 127.93 127.78 127.14. (E)-N-benzyl-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide C D P NAME 20200424-3F E PNO 8 PROCNO 1 F2 - A D. P 20200424 17.43. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 403 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 298.2 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127699 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 1 0. 210. 200. 190. 180. 130. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(95) C D P NAME 20200529-4F E PNO 5 PROCNO 1. 2.3655. .315 . 162 . 3 . . 263 . 233 . 0 0 .23 4 .21 .1 2 .1633 .156 .1412 .136 .1312 .1123 .0 32 .06 5 .04 5 6. 46 6. 656 6. 461 6. 010 6.6 1 5.30 5 5.2 31 4.416 4.3 13. (E)-N-(3-chlorobenzyl)-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide. F2 - A D. P 20200530 0.08. INS R M PROBHD 5 BBO BB-1H P LPROG 30 D 32768 SOL EN CDC 3 NS 16 DS 0 S H 7246.377 H FIDRES 0.221142 H AQ 2.2609921 RG 181 D 69.000 DE 6.50 E 299.4 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== N C1 1H P1 15.00 PL1 11.10 B SFO1 400.1324008 MH F2 - P SI 16384 SF 400.1300110 MH D EM SSB 0 LB 0H GB 0 PC 1.00. 3. 2 3.000. 4 0. 1. 5 0. 36. 2.23 . 0 1. 0. 23. 6 2. 01 0. 6. 10. 0.. 11. 1.

(96) 21.52. 30.90. 53.43. 77.32 77.00 76.68. 171.25 143.94 142.38 140.65 137.96 135.63 134.85 134.78 134.21 130.64 130.52 129.98 129.93 129.76 129.61 129.34 128.27 128.07 127.98 127.95 127.82 127.72 127.44. 207.03. (E)-N-(3-chlorobenzyl)-N-(2-((2-tosylhydrazineylidene)methyl)phenyl)benzamide C D P NAME 20200529-4F E PNO 3 PROCNO 1 F2 - A D. P 20200529 23.51. INS R M PROBHD 5 BBO BB-1H P LPROG 30 D 32768 SOL EN CDC 3 NS 13548 DS 0 S H 24038.461 H FIDRES 0.733596 H AQ 0.6815744 RG 3649.1 D 20.800 DE 6.50 E 300.5 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== N C1 13C P1 10.00 PL1 3.80 B SFO1 100.6233325 MH ======== CHANNEL 2 ======== CPDPRG 2 16 N C2 1H PCPD2 90.00 PL2 10.20 B PL12 26.00 B PL13 29.00 B SFO2 400.1316005 MH F2 - P SI 32768 SF 100.6127700 MH D EM SSB 0 LB 1.00 H GB 0 PC 1.00. 1 0. 210. 200. 190. 130. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(97) 1-methyl-2-(1-methyl-2-phenyl-1H-indol-3-yl)-2-phenylindolin-3-one .4041 .400 .3 62 .3 32 .3 03 .3656 .3624 .3260 .3053 .2 43 .25 1 .250 .245 .2314 .1 0 .1 43 .1 20 .1 2 .1 23 .1 .1 44 .1 16 .1645 .1610 .1566 .153 .1122 .0 3 6. 15 6. 122 6. 5 6. 42 6. 63 6. 5 5 6. 566 6. 02 6. 3 6.630 6.6102 6.55 0 6.5361 6.51 5 6.4 1 3.43 2. 666. C D P NAME 20200508-3F E PNO 6 PROCNO 1 F2 - A D. P 20200508 22.58. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 144.49 D 69.333 DE 10.06 E 298.7 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300154 MH D EM B 0 LB 0H GB 0 PC 1.00. 5. 4. 3. 2 4. 6. 2.. 10. 6.5. 3.000. 11. .0. 1.6 1.413 4.431 3.065 1.00 2.005 0. 1 0. 3 2.011. .5. 1.

(98) C D P NAME 20200508-3F E PNO 7 PROCNO 1. 30.52 29.61. 159.38 139.97 138.46 137.11 136.82 131.41 131.34 130.67 128.23 127.68 127.54 126.89 125.14 121.89 121.50 119.50 119.40 116.37 109.75 109.37 107.70 77.32 77.00 76.68. 200.03. 1-methyl-2-(1-methyl-2-phenyl-1H-indol-3-yl)-2-phenylindolin-3-one. F2 - A D. P 20200508 23.06. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 999 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 299.8 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127719 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(99) 2. 620. 3.4212. .44 .4444 .42 2 .422 .3306 .3164 .2 1 .2 46 .2 6 .2 35 .2 15 .26 2 .2500 .2451 .1 42 .1 3 .1 25 .123 .11 6 6. 4 6 6. 2 0 6. 261 6. 105 6. 0 1 6. 414 6. 223 6.6051 6.6006 6.4 6.45. 5-bromo-2-(5-bromo-1-methyl-2-phenyl-1H-indol-3-yl)-1-methyl-2-phenylindolin-3-one C D P NAME 20200611-3F E PNO 9 PROCNO 1 F2 - A D. P 20200611 22.28. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 298.4 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300109 MH D EM B 0 LB 0H GB 0 PC 1.00. 6. 5. 4. 3. 2 3.000. 10. 6.5. 2. 6. 11. .0. 1.354 4. 05 1.024 0. 0 2.0 4 0. 50 1.003 0. 0 0. 56 0. 6. .5. 1.

(100) C D P NAME 20200611-3F E PNO 10 PROCNO 1. 30.68 29.84. 158.00 141.10 139.48 137.28 135.38 131.33 130.62 129.02 128.65 128.23 127.89 127.36 127.04 124.54 124.02 120.98 112.95 110.92 109.48 109.39 108.46 77.32 77.00 76.68 76.43. 198.44. 5-bromo-2-(5-bromo-1-methyl-2-phenyl-1H-indol-3-yl)-1-methyl-2-phenylindolin-3-one. F2 - A D. P 20200611 22.35. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 14684 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 299.5 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127706 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(101) C D P NAME 20200505-3F E PNO 4 PROCNO 1. 2. 613. 3.4250. .3323 .326 .3105 .3053 .2 12 .2 6 .2565 .23 5 .21 6 .1 22 .1 3 .13 .1350 .11 1 .1134 6. 45 6. 1 6. 50 6. 31 6. 142 6. 542 6. 353 6.51 4 6.4 56 6.46 6.4641. 5-chloro-2-(5-chloro-1-methyl-2-phenyl-1H-indol-3-yl)-1-methyl-2-phenylindolin-3-one. F2 - A D. P 20200505 18.02. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 298.0 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300111 MH D EM B 0 LB 0H GB 0 PC 1.00. 5. 4. 3. 2 3.000. 6. 3. 10. 2.. 11. .0. 10. 61 1. 31 1.000 1. 61. .5. 1.

(102) C D P NAME 20200505-3F E PNO 5 PROCNO 1. 30.70 29.84. 157.75 141.24 137.36 136.92 135.14 131.32 130.72 130.60 128.63 128.37 128.21 127.87 127.03 125.27 124.27 121.98 121.71 120.96 120.36 110.47 109.50 108.91 77.32 77.00 76.68. 198.69. 5-chloro-2-(5-chloro-1-methyl-2-phenyl-1H-indol-3-yl)-1-methyl-2-phenylindolin-3-one. F2 - A D. P 20200505 18.06. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 431 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 298.9 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127706 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(103) 01. C D P NAME 20200508-3F E PNO 3 PROCNO 1. 2.. .2652 .25 5 .2551 .2202 .1 0 .1 16 .1 1 .1 50 .163 .1604 .15 0 .106 .1003 .0 4 .0 1 6. 156 6. 6 6. 6 6. 2 6. 21 6. 05 6. 6. 4 6. 2 6.55 6.54 0 6.541 6.53 2 5. 40 5. 0 3.65 1 3.4451 3.40 3. 5-methoxy-2-(5-methoxy-1-methyl-2-phenyl-1H-indol-3-yl)-1-methyl-2-phenylindolin-3-one. F2 - A D. P 20200508 22.11. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 113.31 D 69.333 DE 10.06 E 298.5 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300116 MH D EM B 0 LB 0H GB 0 PC 1.00. .0 6.. 4. 3. 2 3.000. 5. 2. 2 3.024 3.01. 6 5. 10. 0.. 11. .2. 4.44 3.16 1.024 0. 1.004 0. 2 2.004. .4. 1.

(104) C D P NAME 20200508-3F E PNO 4 PROCNO 1. 30.62 30.00. 55.88 55.36. 155.77 153.49 151.57 140.21 138.74 132.04 131.57 131.33 130.78 128.05 127.93 127.59 127.49 126.81 119.44 111.88 109.96 109.68 109.10 105.64 103.49 77.32 77.00 76.68. 200.10. 5-methoxy-2-(5-methoxy-1-methyl-2-phenyl-1H-indol-3-yl)-1-methyl-2-phenylindolin-3-one. F2 - A D. P 20200508 22.17. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 821 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 299.5 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127705 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(105) C D P NAME 20200617-3F E PNO 1 PROCNO 1. 2.5000. 2. 1 5. 3. 54 3. 36 3.5 21 3.3 14 3.25 3. .2 33 .263 .256 .2234 .20 3 .1 3 .1 0 .1431 .030 6. 245 6. 061 6.421 6.36 3 5. 6. 2-(5,6-dimethoxy-1-methyl-2-phenyl-1H-indol-3-yl)-5,6-dimethoxy-1-methyl-2-phenylindolin-3-one. F2 - A D. P 20200617 16.51. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN DM O N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 177.16 D 69.333 DE 10.06 E 294.4 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300032 MH D EM B 0 LB 0H GB 0 PC 1.00. 6.5. 4. 3 3.000. 5. 3.032 3.123 3.004 3.054 3.10. 6 6. 10. 0.. 11. .0. 5. 66 1.322 1.01 1.0 2 1.014 0. 4 1.. .5. 2. 1.

(106) C D P NAME 20200617-3F E PNO 2 PROCNO 1. 39.73 39.52 39.31 30.60 29.74. 56.02 55.97 55.83 55.15. 75.68. 158.71 157.17 146.32 143.80 141.98 139.01 137.86 131.33 130.98 130.81 127.91 127.71 127.21 127.11 126.63 119.61 109.73 109.00 105.21 103.29 93.98 91.49. 196.48. 2-(5,6-dimethoxy-1-methyl-2-phenyl-1H-indol-3-yl)-5,6-dimethoxy-1-methyl-2-phenylindolin-3-one. F2 - A D. P 20200618 23.34. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN DM O N 4522 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 300.0 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6128183 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

(107) 4. C D P NAME 20200518-3F E PNO 4 PROCNO 1. 2.5. 3.346. .242 .22 .21 .20 6 .1362 .1322 .12 3 .11 2 .0 0 .0 0 .05 1 .0452 .035 6. 111 6. 22 6. 513 6.5 05 6.06 6 5. 16 5. 0 5. 6 1 5. 0 0 5. 054 5. 55. 5,5'-dimethyl-6,6'-diphenyl-5,6-dihydro-5'H,7H-[6,7'-bi[1,3]dioxolo[4,5-f]indol]-7-one. F2 - A D. P 20200518 17.28. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 16 D 0 H 7211.539 H FIDRE 0.220079 H AQ 2.2719147 RG 198.09 D 69.333 DE 10.06 E 298.4 K D1 2.00000000 D0 1 ======== CHANNEL 1 ======== FO1 400.1324008 MH N C1 1H P1 15.00 PL 1 11.39999962 F2 - P I 16384 F 400.1300100 MH D EM B 0 LB 0H GB 0 PC 1.00. 6. 5. 4. 3. 2 2. 6. 10. 6.5. 3.000. 11. .0. .40 1.035 1.052 0. 5 0. 5 0. 02 0. 65 2.011 1.001 2.023. .5. 1.

(108) C D P NAME 20200518-3F E PNO 5 PROCNO 1. 30.82 29.90. 159.10 156.84 144.48 142.34 140.50 138.50 138.16 132.16 131.93 131.45 130.73 128.75 128.01 127.76 127.44 126.72 121.13 111.96 109.65 102.56 101.60 100.83 100.45 90.18 88.88 77.32 77.00 76.68. 197.81. 5,5'-dimethyl-6,6'-diphenyl-5,6-dihydro-5'H,7H-[6,7'-bi[1,3]dioxolo[4,5-f]indol]-7-one. F2 - A D. P 20200524 16.36. IN R M PROBHD 5 PABBO BB/ P LPROG 30 D 32768 OL EN CDC 3 N 9789 D 0 H 24038.461 H FIDRE 0.733596 H AQ 0.6815744 RG 198.09 D 20.800 DE 6.50 E 297.2 K D1 2.00000000 D11 0.03000000 D0 1 ======== CHANNEL 1 ======== FO1 100.6228298 MH N C1 13C P1 10.00 PL 1 49.50000000 ======== CHANNEL 2 ======== FO2 400.1316005 MH N C2 1H CPDPRG 2 16 PCPD2 90.00 PL 2 12.50000000 PL 12 0.34722000 PL 13 0.28125000 F2 - P I 32768 F 100.6127705 MH D EM B 0 LB 2.00 H GB 0 PC 1.00. 210. 200. 190. 180. 170. 160. 150. 140. 130. 120. 110. 100. 90. 80. 70. 60. 50. 40. 30. 20.

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