Name: 7310-95-4|2-Hydroxy-5-methylisophthalaldehyde|94%
Brand: Ambeed
SKU: A131296
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1
[ 91-04-3 ]
[ 127-68-4 ]
[ 7310-95-4 ]

Reference： [1]Patent: DE580981,1932,
Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 20,p. 533

2
[ 91-04-3 ]
[ 7310-95-4 ]

Yield	Reaction Conditions	Operation in experiment
92%	With dimethyl selenoxide In benzene for 2h; Heating;
90%	With manganese(IV) oxide
79%	With manganese(IV) oxide In chloroform for 8h; Heating;

76%	With manganese(IV) oxide In chloroform for 8h; Heating;
76.3%	With 2-iodoxybenzoic acid In ethyl acetate at 70℃; for 3h;	1 Synthesis of Compound 2 of Example 1 1.0 g of 5.95 mmol of compound 1 (2,6-bis(hydroxymethyl)-4-methylphenol) and 5.0 g of 17.86 mmol of2-iodobenzoic acid were placed in a round bottom flask with compounds 1 and 2 - iodoxybenzoic acid molar ratio is 1: 3, was added 20mLof ethyl acetate, 70 deg.] C the reaction was heated at reflux for 3h, cooled to room temperature, filtered, and the cake was washed with ethyl acetate 3 times, rotary evaporatedto remove the organic solvent hair After that, column chromatography was carried out with an eluent having a volume ratio of petroleum ether: ethyl acetate = 10:1 to obtain a white solid compound 2; The obtained compound 2 is 2-hydroxy-5-methylisophthalaldehyde, and the compound 2 has a structural formula of 76.3%;
76.3%	With 2-iodoxybenzoic acid In ethyl acetate for 3h; Reflux;	Synthesis of compound 1: To a solution of (2-hydroxy-5-methyl-1,3-phenylene) dimethanol (1 g, 5.95 mmol) in ethyl acetate (20 mL)was added 2-iodylbenzoic acid (5 g, 17.86mmol). Themixture solutionwas stirred under refluxing for 3 h. After filtrating the solid, the filtratewas evaporated to obtain the crude product. Then, the product was purifiedby column chromatography on silica gel to obtain the target compoundas a white solid (yield: 76.3%). 1H NMR (400MHz, CDCl3, ppm):11.47 (s, 1H), 10.23 (s, 2H), 7.78 (s, 2H), 2.40 (s, 3H).
74%	With manganese(IV) oxide In dichloromethane at 120℃; for 72h;	2,6-Diformyl-4-methylphenol was synthesized by accordingly to describe the method in Scheme S1. 2,6-Bis(hydroxymethyl)-p-cresol (1g) was dissolved in dichloromethane and stirred for 30min at 65°C, activate manganese dioxide (6g) was added. Then mixture was refluxed for 3days at 120°C, then allowed to cool to room temperature naturally. After filtration, the solvent was removed under reduced pressure, and the crude product was purified by silica column chromatography (ethyl acetate and petroleum ether as the eluent). After drying in a vacuum oven. 2,6-Diformyl-4-methylphenol was obtained as a yellow solid (0.74g, 74%). 1H NMR (CDCl3), δ: 2. 33 (s, 3H); 7. 85 (s, 2H); 10. 07 (s, 2H); 11.4 (s, 1H).
67%	With manganese(IV) oxide In chloroform for 48h; Ambient temperature; Heating;
60%	With manganese(IV) oxide In lithium hydroxide monohydrate; toluene for 120h; Reflux;
50%	With manganese(IV) oxide In chloroform for 18h; Reflux;
	at 160℃; im Kohlendioxyd-Strom;
	at 160℃;
	Multi-step reaction with 3 steps 1: sodium hydroxide / H₂O; toluene / 22 h 2: sodium dichromate, acetic acid / 0.75 h / 110 - 116 °C 3: 95 g / aq. sulfuric acid / 1 h
	Multi-step reaction with 2 steps 1: aqueous NaOH-solution; benzene 2: Oxidation zum Ester des Oxyuvitinaldehyds und Verseifen mit konz.Schwefelsaeure
	Multi-step reaction with 3 steps 1: K₂CO₃ 2: Py*HClCrO₃ 3: BBr₃
	With manganese(IV) oxide In propan-2-one
500 mg	With manganese(IV) oxide In chloroform for 18h; Reflux;	Synthesisof 2-hydroxy-5-methyl-benzene-1,3-dicarbaldehyde (2): As we learnt, p-Cresol (10 g) wasadded to a solution of NaOH (3 g) in water (20 mL). Following full development of a gold color, 37% formaldehyde (20 g) was added. The mixture was stirred for 20 min and allowed to stand overnight at the ambient temperature. The yellow granular 2,6-dimethylol-5-methylphenolproduct was collected by vacuum filtration and washed withwater-saturated sodium chloride followed by dilute HCl. In a 100 ml r.b. flask fitted with a reflux condenser, a magnetic stirrer and a dropping funnel was placed 2,6-dimethylol-5-methylphenol (1 gm). Following addition of excess MnO2, it was then refluxed in CHCl3 for 18 hours. Finally, the product 2 was purified by 60-120 silica gel by 5% ethyl acetatein pet ether. Yield of the product was 500 mg (50%).
	With manganese(IV) oxide In chloroform for 6h; Reflux;	2.3. Synthesis of 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde 2,6-Bis(hydroxymethyl)-p-cresol (13.8 g) was dissolved in 1 L of chloroform under continuous stirring at room temperature. Manganese dioxide (120 g) was added slowly to the reaction mixture under continuous stirring, and the final suspension was refluxed for 6 h. The obtained mixture was cooled to room temperature and filtered. The yellow solution was evaporated under vacuum and the obtained yellow solid was purified by sublimation. The product was characterized by FTIR spectroscopy (KBr pellets): 3028-2924 (νC-H aromatic ring), 2872 (νC-H aldehyde), 1681, 1666 (νC=O aldehyde). Anal. Calcd (C9H8O3) (%):C, 65.85; H, 4.91. Found (%): C, 64.5; H, 5.1.
	Multi-step reaction with 3 steps 1: sodium hydroxide / lithium hydroxide monohydrate / 20 h / 20 °C 2: sodium bichromate dihydrate; glacial acetic acid / 0.67 h / 110 °C 3: sulfuric acid / 1 h
	With manganese(IV) oxide In acetonitrile at 110℃; for 65h;	1.1 Preparation of 2,6-Diacetaldehyde-4-Methylphenol: 1 g of 2, 6-dimethylol p-methylphenol was placed in a round bottom flask,Dissolved with 20 mL of acetonitrile,65 oil bath stirring 30min after adding 6g activated manganese dioxide,110 high temperature stirring reflux reaction 65h,After the reaction is completed, the mixture is cooled to room temperature,Filtration to remove oxidant manganese dioxide,Collecting filtrate,The solvent was removed under reduced pressure to remove the crude product,Purification was carried out in ethanol to give a pale yellow solid.
	With manganese(IV) oxide In chloroform at 80℃; for 24h;
500 mg	With manganese(IV) oxide In chloroform for 18h; Reflux;	Synthesis of 2hydroxy-5-methyl-benzene-1,3-dicarbaldehyde(2): p-Cresol (10 g) was added to a solution of NaOH (3 g) in water(20 mL). Following full development of a gold color, 37% formaldehyde(20 g) was added. The mixture was stirred for 20 min and allowedto stand overnight at the ambient temperature. The yellowgranular 2,6-dimethylol-5-methylphenol product was collected byvacuum filtration and washed with water-saturated sodium chloridefollowed by dilute HCl. In a 100 ml r.b. flask fitted with areflux condenser, a magnetic stirrer and a dropping funnel wasplaced 2,6-dimethylol-5-methylphenol (1 gm). Following additionof excess MnO 2 , it was then refluxed in CHCl 3 for 18 h. Finally, theproduct 2 was purified by 60-120 silica gel by 5% ethyl acetate inpet ether. Yield of the product was 500 mg (50%).

Reference： [1]Syper; Mlochowski [Synthesis, 1984, vol. NO. 9, # 9, p. 747 - 752]
[2]Coman, Anca G.; Hadade, Niculina D.; Hanganu, Anamaria; Mǎdǎlan, Augustin M.; Matache, Mihaela; Paun, Anca; Popescu, Codruţa C. [Revue Roumaine de Chimie, 2020, vol. 65, # 1, p. 109 - 114] Coman, Anca G.; Paun, Anca; Popescu, Codruța C.; Hadade, Niculina D.; Hanganu, Anamaria; Mădălan, Augustin M.; Matache, Mihaela [Revue Roumaine de Chimie, 2021, vol. 65, # 1, p. 109 - 114]
[3]Xie; Zhang; Yan; Yuan [Synthetic Communications, 1994, vol. 24, # 1, p. 53 - 58]
[4]Huang, Wei; Gou, Shaohua; Hu, Dahua; Meng, Qingjing [Synthetic Communications, 2000, vol. 30, # 9, p. 1555 - 1561]
[5]Current Patent Assignee: LINGNAN NORMAL UNIVERSTITY - CN109134206, 2019, A Location in patent: Paragraph 0020; 0079; 0080; 0081
[6]Feng, Aiqing; Jia, Yongmei; Huang, Liping; Wang, Lin; Zhou, Guohua; Wang, Sheng; Liu, Peilian [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, vol. 220]
[7]Tang, Xu; Han, Juan; Wang, Yun; Bao, Xu; Ni, Liang; Wang, Lei; Li, Longhua [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2017, vol. 184, p. 177 - 183]
[8]Taniguchi, Shozo [Bulletin of the Chemical Society of Japan, 1984, vol. 57, # 9, p. 2683 - 2684]
[9]Das, Biswanath; Lee, Bao-Lin; Karlsson, Erik A.; Åkermark, Torbjörn; Shatskiy, Andrey; Demeshko, Serhiy; Liao, Rong-Zhen; Laine, Tanja M.; Haukka, Matti; Zeglio, Erica; Abdel-Magied, Ahmed F.; Siegbahn, Per E. M.; Meyer, Franc; Kärkäs, Markus D.; Johnston, Eric V.; Nordlander, Ebbe; Åkermark, Björn [Dalton Transactions, 2016, vol. 45, # 34, p. 13289 - 13293] Das, Biswanath; Lee, Bao-Lin; Karlsson, Erik A.; Åkermark, Torbjörn; Shatskiy, Andrey; Demeshko, Serhiy; Liao, Rong-Zhen; Laine, Tanja M.; Haukka, Matti; Zeglio, Erica; Abdel-Magied, Ahmed F.; Siegbahn, Per E. M.; Meyer, Franc; Kärkäs, Markus D.; Johnston, Eric V.; Nordlander, Ebbe; Åkermark, Björn [Dalton Transactions, 2016, vol. 45, # 34, p. 13289 - 13293]
[10]Goswami, Shyamaprosad; Das, Avijit Kumar; Maity, Anup Kumar; Manna, Abhishek; Aich, Krishnendu; Maity, Sibaprasad; Saha, Partha; Mandal, Tarun Kanti [Dalton Transactions, 2014, vol. 43, # 1, p. 231 - 239]
[11]Zinke; Hanus; Ziegler [Journal fur praktische Chemie (Leipzig 1954), 1939, vol. <2> 152, p. 126,135]
[12]Zinke; Hanus; Ziegler [Journal fur praktische Chemie (Leipzig 1954), 1939, vol. <2> 152, p. 126,135]
[13]Gagne, R. R.; Spiro, C. L.; Smith, T. J.; Hamann, C. A.; Thies, W. R.; Shiemke, A. K. [Journal of the American Chemical Society, 1981, vol. 103, # 14, p. 4073 - 4081]
[14]Ullmann; Brittner [Chemische Berichte, 1909, vol. 42, p. 2546]
[15]Koenig,K.E. et al. [Journal of the American Chemical Society, 1979, vol. 101, # 13, p. 3553 - 3566]
[16]Location in patent: scheme or table Liu, Hongyan; Shi, Xiaoyan; Xu, Min; Li, Zhengpeng; Huang, Liang; Bai, Decheng; Zeng, Zhengzhi [European Journal of Medicinal Chemistry, 2011, vol. 46, # 5, p. 1638 - 1647]
[17]Goswami, Shyamaprosad; Maity, Sibaprasad; Das, Avijit Kumar; Maity, Annada C.; Mandal, Tarun Kanti; Samanta, Siddhartha [Tetrahedron Letters, 2013, vol. 54, # 38, p. 5232 - 5235]
[18]Fuentealba, Pablo; Serón, Lorenzo; Sánchez, Camila; Manzur, Jorge; Paredes-Garcia, Verónica; Pizarro, Nancy; Cepeda, Marjorie; Venegas-Yazigi, Diego; Spodine, Evgenia [Journal of Coordination Chemistry, 2014, vol. 67, # 23-24, p. 3894 - 3908]
[19]Lal, Sunder; Thakur, Ramswaroop Singh [Asian Journal of Chemistry, 2016, vol. 28, # 12, p. 2596 - 2600]
[20]Current Patent Assignee: JIANGSU UNIVERSITY - CN106631730, 2017, A Location in patent: Paragraph 0031; 0033; 0035
[21]Zhang, Gaobin; Zhao, Yanfei; Peng, Bo; Li, Zheng; Xu, Chenchen; Liu, Yi; Zhang, Chengwu; Voelcker, Nicolas H.; Li, Lin; Huang, Wei [Journal of Materials Chemistry B, 2019, vol. 7, # 14, p. 2252 - 2260]
[22]Goswami, Shyamaprosad; Maity, Annada C; Maity, Sibaprasad; Mandal, Tarun Kanti; Roymahapatra, Gourisankar; kumar Das, Avijit [Journal of Molecular Structure, 2022, vol. 1264]

3
[ 3731-51-9 ]
[ 7310-95-4 ]
[ 102262-03-3 ]

Yield	Reaction Conditions	Operation in experiment
86%	In methanol at 65℃;	1 Example 1: Synthesis of Fluorescent Probe Probe 1 : 2,6-Diformyl-4-methylphenol (0.164 g, 1.0 mmol) was added sequentially to a 100 mL round bottom flask.2-aminopyridine (0.216 g, 2.0 mmol),It was then dissolved by the addition of 25 mL of methanol.In the 65 ° C oil bath,Stir and reflux for 3 to 4 hours with a magnetic stirrer.Using dichloromethane and methanol (5:1, V:V) as the developing solvent, the progress of the reaction was detected by a thin layer chromatography plate until the disappearance of the two raw materials, the stirring was stopped, the reaction system was cooled to room temperature, and suction filtration was performed.Drying the obtained solid,Probe 1 (light yellow solid powder) was obtained, 0.296 g, yield: 86%.
82.8%	In acetonitrile for 4h; Reflux;
	In ethanol

In methanol for 3h;

Reference： [1]Current Patent Assignee: SHAANXI UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN110003095, 2019, A Location in patent: Paragraph 0031; 0037; 0038
[2]Sahana, Animesh; Banerjee, Arnab; Lohar, Sisir; Sarkar, Bidisha; Mukhopadhyay, Subhra Kanti; Das, Debasis [Inorganic Chemistry, 2013, vol. 52, # 7, p. 3627 - 3633]
[3]Schindler, Siegfried; Elias, Horst; Paulus, Helmut [Zeitschrift fur Naturforschung, B: Chemical Sciences, 1990, vol. 45, # 5, p. 607 - 618]
[4]Chen, Xiaoqiang; Wang, Jingyun; Sun, Shiguo; Fan, Jiangli; Wu, Song; Liu, Jianfeng; Ma, Saijian; Zhang, Lizhu; Peng, Xiaojun [Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 1, p. 109 - 113]

4
[ 7310-95-4 ]
[ 13330-41-1 ]
[ 133592-38-8 ]

Yield	Reaction Conditions	Operation in experiment
56%	With piperidine In isopropyl alcohol Heating;
56%	With triethylamine In isopropyl alcohol for 0.25h; Reflux;	1,3,3,8 -tetramethyl-6 -formyl-spiro[indoline-2,2 -2 H - chromene] 6. General procedure: 0.82 g (0.003 mol) of 1,2,3,3-tetramethyl-3 H - indolium perchlorate 1 was added to a hot solution of 0.492 g (0.003 mol) of 2a in 15 ml of isopropyl alcohol. Then, 0.42 ml of triethylamine was carefully added dropwise. The reaction mixture was refluxed for 15 minutes. The formed precipitate was filtered offandpurifiedbycolumnchromatographyonsilicagelusing chloroform as eluent. Yield 0.531 g (55.5 %).
56%	With triethylamine In isopropyl alcohol for 0.25h; Reflux;	8-Formyl-1,3,3,6'-tetramethylspiro[indoline-2,2'-2H-chromene](1). Triethylamine (0.28 mL, one molar equivalent) wasadded dropwise under heating to a mixture of 1,2,3,3-tetramethyl-3H-indolium perchlorate (3) (0.547 g, 0.002 mol) and 2-hydroxy-3-formyl-5-methylbenzaldehyde (4a) (0.328 g, 0.002 mol)in propan-2-ol (15 mL). The reaction mixture was refl uxed for15 min, cooled, poured into water (60 mL), and extracted withbenzene. The organic layer was separated, washed with water,dried with anhydrous sodium sulfate, concentrated using a waterjet vacuum pump to 15 mL, and chromatographed on a silica gelcolumn (chloroform as the eluent). The solvent was distilled off ,and the residue was crystalized from ethanol. The yield was 0.357 g(56%), m.p. 107 C (cf. lit. data44: 105-106 C). IR, ν/cm-1:1667 (C=O); 1646, 1598 (C=C); 927 (Cspiro-O). 1H NMR,δ: 10.10 (s, 1 H, CHO); 7.43 (d, 1 H, C(7)H, J = 1.7 Hz); 7.15(td, 1 H, C(6)H, J = 7.7 Hz, J = 1.0 Hz); 7.08 (d, 1 H, C(5)H,J = 2.1 Hz); 7.04 (d, 1 H, C(4)H, J = 7.0 Hz); 6.88-6.79 (m, 2 H,C(5)H, C(4)H); 6.51 (d, 1 H, C(7)H, J = 7.7 Hz); 5.77 (d, 1 H,C(3)H, J = 10.3 Hz); 2.73 (s, 3 H, N-CH3); 2.25 (s, 3 H,C(6)-CH3); 1.31 (s, 3 H, C(3)-CH3); 1.18 (s, 3 H, C(3)-CH3). 13C NMR, δ: 189.00 (s, CHO); 155.53 (s, C(9)); 147.76(s, C(8)); 136.32 (s, C(9)); 133.45 (s, C(5)); 129.27 (s, C(10));128.78 (s, C(4)); 127.64 (s, C(6)); 127.36 (s, C(7)); 122.23(s, C(8)); 121.39 (s, C(4)); 120.34 (s, C(3)); 119.95 (s, C(6));119.51 (s, C(5)); 106.91 (s, C(7)); 105.42 (s, C(22)); 51.98 (s, C(3)); 28.93 (s, NCH3); 25.71 (s, C(3)-CH3); 20.40(s, C(3)-CH3); 20.24 (s, C(6)-CH3). 15N NMR, δ: 92.40.Found (%): C, 79.08; H, 6.59; N, 4.41. C21H21NO2. Calculated(%): C, 79.03; H, 6.63; N, 4.39.

With piperidine In isopropyl alcohol for 0.166667h; Heating;

1,3,3,6′-tetramethyl-8′-formyl-spiro[indoline-2,2-2H-chromene] SP-1 0.1 ml (0.0011 moldm-3 ) of piperidine was added dropwise with heating to a boiling solution containing 1 mmol of 1,2,3,3- tetramethyl-3H-indolium perchlorate 1, 1 mmol of 2,6-diformylphenol (R1 = CHO, R2 = CH3) 2, and 5 ml of 2-propanol. Then the reaction mixture was being boiled for 10 minutes. The resulting mixture was chromatographed on an Al2O3 column with benzene as an eluent. The residue obtained after solvent distillation was recrystallized from ethanol. IR spectrum, ν, cm- 1 : 1667 (C=O); 1646, 1598 (C=C); 927 (Cspiro). NMR 1 H (CDCl3) δ, ppm (J, Hz): 10.10 (s, 1, -), 7.43 (d, J = 1.7, 1, H-7′ ), 7.15 (td, J = 7.7, 1.0, 1, H-6), 7.08 (d, J = 2.1, 1H, H-5′ ), 7.04 (d, J = 7.0, 1H, -4), 6.87 - 6.81 (m, 2H, -5, H-4′ ), 6.51 (d, J = 7.7, 1H, -7), 5.77 (d, J = 10.4, 1, H-3′ ), 2.73 (s, 3, N-3), 2.25 (s, 3, C(6)-3), 1.31 (s, 3, C(3)-CH3), 1.18 (s, 3,C(3)-CH3). NMR 13C (CDCl3) δ, ppm: 189.00 (s, C=O), 155.53 (s), 147.76 (s), 136.32 (s), 133.45 (s), 129.27 (s), 128.78 (s), 127.64 (s), 127.36 (s), 122.23 (s), 121.39 (s), 120.34 (s), 119.95 (s), 119.51 (s), 106.91 (s), 105.42 (s, Cspiro), 51.98 (s, C(3)), 28.93 (s, N-3), 25.78 (s, C(3)-CH3), 20.40 (s, C(6)-3), 20.24 (s, C(3)-CH3). Found, %: 79.03; H 6.58; N 4.35. C21H21NO2. Calc., %: C 78.97; H 6.63; N 4.39.

Reference： [1]Luk'yanov, B. S.; Nivorozhkin, L. E.; Minkin, V. I. [Chemistry of Heterocyclic Compounds, 1993, vol. 29, # 2, p. 152 - 154][Khimiya Geterotsiklicheskikh Soedinenii, 1993, # 2, p. 176 - 179]
[2]Pugachev, Artem D.; Ozhogin, Ilya V.; Lukyanova, Maria B.; Lukyanov, Boris S.; Kozlenko, Anastasia S.; Rostovtseva, Irina A.; Makarova, Nadezhda I.; Tkachev, Valery V.; Aldoshin, Sergey M.; Metelitsa, Anatoly V. [Journal of Molecular Structure, 2021, vol. 1229]
[3]Aldoshin, S. M.; Lukyanov, B. S.; Lukyanova, M. B.; Metelitsa, A. V.; Minkin, V. I.; Mukhanov, E. L.; Ozhogin, I. V.; Pugachev, A. D.; Stankevich, N. V.; Tkachev, V. V. [Russian Chemical Bulletin, 2021, vol. 70, # 11, p. 2090 - 2099][Izv. Akad. Nauk, Ser. Khim., 2021, # 11, p. 2090 - 2099]
[4]Dunaev, A. M.; Govorov, D. N.; Kudin, L. S.; Kuzmin, N. A.; Lukyanov, B. S.; Lukyanova, M. B.; Motalov, V. B. [Thermochimica Acta, 2021, vol. 706]

5
[ 7310-95-4 ]
[ 107-15-3 ]
[ 37512-33-7 ]

Yield	Reaction Conditions	Operation in experiment
100%
78%	In ethanol at 20℃; for 24h; Inert atmosphere;
62%	In isopropanol at 20℃; for 1h;	2.4. Syntheses of [2 + 1] hemicyclic ligands with aliphatic amines General procedure: The hemicyclic ligand was obtained using the corresponding aliphatic amine. In 10 mL of 2-propanol 150 mg (0.914 mM) of 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde was dissolved with continuous stirring at room temperature. The appropriate aliphatic diamine(ethylenediamine (27 μL) (I), 1,3-diaminopropane (34 μL) (II), 1,3-diamino-2-propanol (37 mg) (III)) was added dropwise (90% of the corresponding molar relation, 0.411 mM), thus avoiding formation of the macrocyclic species, and left to react for one hour. The solutions were cooled to 5 °C, and the yellow-orange solids that precipitated were washed with 2-propanol and dried under vacuum (scheme 1).

62%	In isopropanol at 20℃; for 1h;
	With magnesium(II) nitrate; magnesium acetate tetrahydrate In methanol for 1h; Heating;
	In ethanol

Reference： [1]Srivastava, Shipra; Srivastava, Ankita; Tripathi, Namrata; Sharma [Journal of the Indian Chemical Society, 2007, vol. 84, # 6, p. 524 - 531]
[2]Chen, Xuesi; Duan, Ranlong; Hu, Chenyang; Huang, Yuezhou; Pang, Xuan; Sun, Zhiqiang; Zhou, Yanchuan [Angewandte Chemie - International Edition, 2022, vol. 61, # 20][Angew. Chem., 2022, vol. 134, # 20]
[3]Fuentealba, Pablo; Serón, Lorenzo; Sánchez, Camila; Manzur, Jorge; Paredes-Garcia, Verónica; Pizarro, Nancy; Cepeda, Marjorie; Venegas-Yazigi, Diego; Spodine, Evgenia [Journal of Coordination Chemistry, 2014, vol. 67, # 23-24, p. 3894 - 3908]
[4]Fuentealba; Paredes-Garcia; Venegas-Yazigi; Silva; Magon; Costa De Santana; Audebrand; Manzur; Spodine [RSC Advances, 2017, vol. 7, # 53, p. 33305 - 33313]
[5]Nanda, Kausik K.; Das, Ramprasad; Venkatsubramanian, Krishnan; Paul, Parimal; Nag, Kamalaksha [Journal of the Chemical Society, Dalton Transactions, 1993, # 16, p. 2515 - 2520]
[6]Current Patent Assignee: WUHAN INSTITUTE OF TECHNOLOGY - CN108030926, 2021, B Location in patent: Paragraph 0022

6
[ 7310-95-4 ]
[ 109-76-2 ]
[ 37512-34-8 ]

Yield	Reaction Conditions	Operation in experiment
100%
47%	In isopropyl alcohol at 20℃; for 1h;	2.4. Syntheses of [2 + 1] hemicyclic ligands with aliphatic amines General procedure: The hemicyclic ligand was obtained using the corresponding aliphatic amine. In 10 mL of 2-propanol 150 mg (0.914 mM) of 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde was dissolved with continuous stirring at room temperature. The appropriate aliphatic diamine(ethylenediamine (27 μL) (I), 1,3-diaminopropane (34 μL) (II), 1,3-diamino-2-propanol (37 mg) (III)) was added dropwise (90% of the corresponding molar relation, 0.411 mM), thus avoiding formation of the macrocyclic species, and left to react for one hour. The solutions were cooled to 5 °C, and the yellow-orange solids that precipitated were washed with 2-propanol and dried under vacuum (scheme 1).
	In ethanol Heating;

Reference： [1]Srivastava, Shipra; Srivastava, Ankita; Tripathi, Namrata; Sharma [Journal of the Indian Chemical Society, 2007, vol. 84, # 6, p. 524 - 531]
[2]Fuentealba, Pablo; Serón, Lorenzo; Sánchez, Camila; Manzur, Jorge; Paredes-Garcia, Verónica; Pizarro, Nancy; Cepeda, Marjorie; Venegas-Yazigi, Diego; Spodine, Evgenia [Journal of Coordination Chemistry, 2014, vol. 67, # 23-24, p. 3894 - 3908]
[3]Adhikary, Bibhutosh; Mandal, Sanat K.; Nag, Kamalaksha [Journal of the Chemical Society, Dalton Transactions, 1988, p. 935 - 942]

7
[ 110-52-1 ]
[ 7310-95-4 ]
[ 165387-55-3 ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 2h;
50%	Stage #1: 2-Hydroxy-5-methylisophthalaldehyde With potassium carbonate In N,N-dimethyl-formamide at 40 - 45℃; for 2h; Stage #2: 1,4-dibromo-butane In N,N-dimethyl-formamide for 4h;	1 4.1 g (0.025 mol) A (R is methyl) was dissolved in DMF,In the heating conditions (control temperature at 40-50 ) Was added 6.9 g (0.05 mol) of potassium carbonate and stirred for 2 h, 5.4 g (0.025 mol) of 1,4-dibromobutane was added dropwise,The reaction was stirred for 4h and the DMF was evaporated by evaporation to give a white solid, which was recrystallized from methanol and washed repeatedly with water to give product B. Yield 50%.

Reference： [1]Clark, Barry P.; Harris, John R.; Timms, Graham H.; Olkowski, Jennifer L. [Tetrahedron Letters, 1995, vol. 36, # 22, p. 3889 - 3892]
[2]Current Patent Assignee: XINXIANG UNIVERSITY - CN106749328, 2017, A Location in patent: Paragraph 0022; 0024; 0025

8
[ 106-44-5 ]
[ 100-97-0 ]
[ 7310-95-4 ]

Yield	Reaction Conditions	Operation in experiment
70%	With trifluoroacetic acid for 24h; Reflux;
68%	With trifluoroacetic acid for 24h; Heating;
64%	Stage #1: p-cresol; hexamethylenetetramine With trifluoroacetic acid at 0 - 85℃; for 20h; Inert atmosphere; Stage #2: With water monomer at 20℃;	2-hydroxy-5-methylisophthalaldehyde (4A) TFA (200ml) was placed under an argon atmosphereand cooled to 0 °C, hexamine (68.41g, 2 equiv.) and para-cresol (25.6ml, 1 equiv.) were charged inportions. The resulting bright yellow solution was heated to 85 °C for 20 hr to form a viscous orangesolution. This was cooled to RT, quenched with water (600ml) and extracted with DCM (4 x100ml). Combined organic was washed with water (2 x 100ml), dried (Mg2SO4) and stripped togive a viscous bright yellow oil (36.53g). This was purified by flash chromatography (productadhered to silica, eluting with DCM, Rf = 0.37) which yielded the title compound as an off-whitesolid (25.72g, 64%)

60.9%	In trifluoroacetic acid at 100℃; for 48h; Inert atmosphere;	2,6-diformyl-4-methylphenol was firstly synthesized according to the reported procedure [35]. Briefly, under N2 atmosphere, 4-methylphenol (10mmol) and hexamethylenetetramine (40mmol) were dissolved in TFA (15mL) and refluxed at 110°C for 48h. The mixture was cooled to room temperature, poured into 4M HCl solution (80mL), and extracted with chloroform (3×20mL). The organic layer was combined and washed with 4M HCl (80mL), water (80mL), then dried over MgSO4 and evaporated to dryness under reduced pressure, respectively. The crude product was further purified by column chromatography (silica gel, hexane/ethyl acetate=20:1 v/v). Yield: 60.9%. 1H NMR (400MHz, CDCl3), δ (ppm): 11.48 (s, 1H), 10.24 (s, 2H), 7.79 (s, 2H), 2.41 (s, 3H); 13C NMR (100MHz, CDCl3), δ (ppm): 192.22, 161.77, 137.99, 129.53, 122.92, 20.09. Then 3 was prepared by employing the similar procedure described for 2. The pure 3 was isolated as pale yellow solid by column chromatography (silica gel, hexane/dichloromethane=4:1 v/v). Yield: 8%. 1H NMR (400MHz, CDCl3), δ (ppm): 8.13 (d, J=8Hz, 4H), 7.99 (d, J=8Hz, 2H), 7.57 (t, J=8Hz, 2H), 7.46 (t, J=8Hz, 2H), 2.51 (s, 3H); 13C NMR (100MHz, CDCl3), δ (ppm): 154.25, 151.43, 132.01, 126.56, 125.35, 122.37, 121.51, 29.71, 20.53. MALDI-TOF-MS: m/z calcd for C21H14N2OS2, 374.05; found 375.12 (M+H)+. Elemental Anal: calcd for C21H14N2OS2, C 67.35%, H 3.77%, N 7.48%; found C 67.50%, H 4.63%, N 6.42%.
53%	With trifluoroacetic acid at 100℃; for 24h;
42%	Stage #1: p-cresol; hexamethylenetetramine With trifluoroacetic acid at 110℃; for 48h; Stage #2: With hydrogenchloride for 0.166667h; Further stages.;
42%	Stage #1: p-cresol; hexamethylenetetramine With trifluoroacetic acid at 130℃; for 24h; Inert atmosphere; Stage #2: With hydrogenchloride In water monomer for 0.5h;	1.1.6 2,6-diformyl-p-cresol Put a rotor in a 200 mL recovery flask,3.84 g (27.4 mmol) of hexamethylenetetramine and 1.48 mL (13.7 mmol) of p-cresol were dissolved in 24 mL of TFA and N 2 -substituted, followed by refluxing at 130 ° C. for 24 hours. After 24 hours, the reaction solution was cooled to room temperature, 80 mL of 4 M HCl was added and the mixture was stirred under aerobic conditions for 30 minutes.The solution was then transferred to a separatory funnel and extracted three times with 60 mL of CH 2 Cl 2. The extracted organic phase was washed twice with 80 mL of 4 M HCl, once with 80 mL of H 2 O,It was washed once with 50 mL of saturated brine,The organic phase was dried over Na 2 SO 4 and concentrated to give the desired yellow solid. This was subjected to silica gel column chromatography (developing solvent: hexane: CHCl 3 = 1: 1), and the fraction containing the desired product was recovered and concentrated to obtain 0.953 g of the objective pale yellow solid(5.81 mmol, Yield 42%).
41%	Stage #1: p-cresol; hexamethylenetetramine With trifluoroacetic acid at 120℃; for 20h; Schlenk technique; Inert atmosphere; Stage #2: With hydrogenchloride In water monomer for 0.166667h; Inert atmosphere;
	Stage #1: p-cresol; hexamethylenetetramine With trifluoroacetic acid Reflux; Stage #2: With hydrogenchloride In water monomer
	With trifluoroacetic acid Reflux;
	With trifluoroacetic acid
	Stage #1: p-cresol; hexamethylenetetramine With trifluoroacetic acid at 90℃; for 24h; Stage #2: With hydrogenchloride; water monomer In trifluoroacetic acid at 20℃; for 2h;	1 References (Synthesis, 1998, 1998 (07): 1029-1032.). p- Methylphenol (4.040 g, 37.3 mmol) was dissolved in 40 ml of trifluoroacetic acid, and hexamethylenetetramine (10.600 g, 75.6 mmol) was added portionwise, and stirred at 90 ° C for 24 h, the solution changed from yellow to red-brown. The reaction solution was poured into 60 ml of a 4 M HCl solution and stirred at room temperature for 2 hr. Continue to added 100 ml of 4 HCl solution, and white turbidity is formed during the addition, and the stirring becomes clarified. The resulting solution was poured into a 500 ml separatory funnel, extracted with CH 2 Cl 2 (100 ml X 3 ), and combined organic phase. Thereafter, it was washed with 4 HCl solution, H 2 O, NaCl saturated solution (100 ml X 3 ). The resulting yellow liquid was dried over anhydrous Na2SO4, and Concentrated to give a crude product as a yellow oil. Purification by silica gel column gave 2-hydroxy-5-methyl-isophthalaldehyde ( or m-benzne dicarbaldehyde) as the desired product as a yellow powder.
	With trifluoroacetic acid In water monomer Acidic conditions; Reflux;
	With trifluoroacetic acid

Reference： [1]Location in patent: experimental part Hryniewicka, Agnieszka; Morzycki, Jacek W.; Witkowski, Stanisław [Journal of Organometallic Chemistry, 2010, vol. 695, # 9, p. 1265 - 1270]
[2]Lindoy, Leonard F.; Meehan, George V.; Svenstrup, Niels [Synthesis, 1998, # 7, p. 1029 - 1032]
[3]Aspinall, Helen C.; Beckingham, Oliver; Farrar, Michael D.; Greeves, Nicholas; Thomas, Christopher D. [Tetrahedron Letters, 2011, vol. 52, # 40, p. 5120 - 5123]
[4]Zhang, Xuan; Liu, Jing-Yun [Dyes and Pigments, 2016, vol. 125, p. 80 - 88]
[5]Chen, Xuesi; Duan, Ranlong; Hu, Chenyang; Huang, Yuezhou; Pang, Xuan; Sun, Zhiqiang; Zhou, Yanchuan [Angewandte Chemie - International Edition, 2022, vol. 61, # 20][Angew. Chem., 2022, vol. 134, # 20]
[6]Chen, Xiaoqiang; Wang, Jingyun; Sun, Shiguo; Fan, Jiangli; Wu, Song; Liu, Jianfeng; Ma, Saijian; Zhang, Lizhu; Peng, Xiaojun [Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 1, p. 109 - 113]
[7]Current Patent Assignee: DOSHISHA UNIVERSITY - JP2018/135304, 2018, A Location in patent: Paragraph 0043; 0044
[8]Kremer, Alexandre B.; Osten, Kimberly M.; Yu, Insun; Ebrahimi, Tannaz; Aluthge, Dinesh C.; Mehrkhodavandi, Parisa [Inorganic Chemistry, 2016, vol. 55, # 11, p. 5365 - 5374]
[9]Location in patent: experimental part Tanaka, Koichi; Watanabe, Yuta; Kalicki, Przemyslaw; Urbanczyk-Lipkowska, Zofia [Bulletin of the Chemical Society of Japan, 2012, vol. 85, # 6, p. 727 - 729]
[10]Gupta, Abhishek Kumar; Dhir, Abhimanew; Pradeep, Chullikkattil P. [European Journal of Organic Chemistry, 2015, vol. 2015, # 1, p. 122 - 129]
[11]Arafa, Wael A.A.; Badry, Mohamed G. [Journal of Chemical Research, 2016, vol. 40, # 7, p. 385 - 392]
[12]Current Patent Assignee: ZHEJIANG UNIVERSITY - CN108676021, 2018, A Location in patent: Paragraph 0024; 0026
[13]Ozhogin, Ilya V.; Chernyavina, Valentina V.; Lukyanov, Boris S.; Malay, Vasily I.; Rostovtseva, Irina A.; Makarova, Nadezhda I.; Tkachev, Valery V.; Lukyanova, Maria B.; Metelitsa, Anatoly V.; Aldoshin, Sergey M. [Journal of Molecular Structure, 2019, vol. 1196, p. 409 - 416]
[14]Aldoshin, S. M.; Lukyanov, B. S.; Lukyanova, M. B.; Metelitsa, A. V.; Minkin, V. I.; Mukhanov, E. L.; Ozhogin, I. V.; Pugachev, A. D.; Stankevich, N. V.; Tkachev, V. V. [Russian Chemical Bulletin, 2021, vol. 70, # 11, p. 2090 - 2099][Izv. Akad. Nauk, Ser. Khim., 2021, # 11, p. 2090 - 2099]

9
[ 7310-95-4 ]
[ 20439-47-8 ]
(HOC₆H₂(CH₃)CHNC₆H₁₀NCH)3 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	In methanol; dichloromethane at 4 - 20℃; for 20h;	63 Example 63 N N H3C I'-'I CH3 "OH H Hexamer la-Me-1, 2-imine N ion tNstNit CH3 [0376] HEXAMERLA-ME. A solution of 2-hydroxy-5-methyl-1,3- benzenedicarboxaldehye (53 mg, 0.32 mmol) in dichloromethane (0.6 mL) was added to a solution of (lR, 2R)- (-)-1, 2-diaminocyclohexane (37 mg, 0.32 mmol) in dichloromethane (0.5 mL). The mixture was stirred at ambient temperature for 16 h, added dropwise to methanol (75 mL) and chilled (4°C) for 4 h. The precipitate was collected to afford 71 mg (92%) OF HEXAMER LA-ME.
80%	In methanol
	With sodium tetrahydroborate In acetonitrile for 1h;

Reference： [1]Current Patent Assignee: COVALENT PARTNERS - WO2005/30711, 2005, A2 Location in patent: Page/Page column 135
[2]Korupoju, Srinivas R.; Zacharias, Panthapally S. [Chemical Communications, 1998, # 12, p. 1267 - 1268]
[3]Ślepokura, Katarzyna; Kobyłka, Michał J.; Lis, Tadeusz; Lisowski, Jerzy; Wydra, Karol [European Journal of Inorganic Chemistry, 2020]

10
[ 91-04-3 ]
[ 127-68-4 ]
aqueous NaOH [ No CAS ]
[ 7310-95-4 ]

Reference： [1]Patent: DE580981,1932,
Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 20,p. 533

11
[ 50-00-0 ]
[ 106-44-5 ]
[ 7310-95-4 ]

Yield	Reaction Conditions	Operation in experiment
35%	With hexamethylenetetramine In acetic acid at 70 - 90℃; for 2h;
35%	Stage #1: formaldehyd; p-cresol With hexamethylenetetramine; acetic acid at 70 - 90℃; for 2h; Stage #2: With sulfuric acid for 0.5h; Reflux;	2 2.2 Synthesis of 2,6-diformyl-4-methylphenol [67] To a solution of p-cresol (10.8 g, 0.1 mol) in acetic acid (50 cm3) were added hexamethylenetetramine (28.2 g, 0.2 mol) and paraformaldehyde (30 g, 1.0 mol). The system was stirred until a light brown viscous solution was formed and then heated (70-90 °C) for 2 h. The solution was cooled to room temperature and conc. H2SO4 (10 cm3) added carefully. The resulting solution was refluxed again for 0.5 h and then on treatment with distilled water (400 cm3) resulted in the formation of a light yellow precipitate, which was stored at 4 °C overnight. The yellow product was isolated by filtration and washed with a small amount of cold CH3OH. A purer product was obtained after recrystallization from toluene. Yield: 5.7 g (35%); color: yellow; m.p: 130-134 °C (lit., 133.5 °C); 1H NMR [250 MHz, DMSO-d6, δ (ppm)]: 11.38 (s, 1H, OH), 10.19 (s, 2H, HC=O), 7.82 (s, 2H, Ar-H), 2.31 (s, 3H, CH3); 1HNMR (CDCl3, ppm): 11.39 (s, 1H, OH), 10.15 (s, 2H, HC=O), 7.70 (s, 2H, Ar-H), 2.32 (s, 3H, CH3); FT-IR (KBr, cm-1): 2869 (υC-H), 1674 (υC=O), 1211 (υC-O); Elemental Analysis, Found (Calc.)%: C9H8O3 (MW = 164.05 g.mol-1) C: 66.02 (65.85); H: 4.78 (4.91); N: 0 (0).
35%	Stage #1: formaldehyd; p-cresol With hexamethylenetetramine; acetic acid at 70 - 90℃; for 2h; Stage #2: With sulfuric acid for 0.5h; Reflux;	Synthesis of 2,6-diformyl-4-methylphenol P-cresol (10.8 g, 0.1 mol) was dissolved in acetic acid (50 cm3), and then hexamethylenetetramine (28.2 g, 0.2 mol) and paraformaldehyde (30 g, 1.0 mol) were added successively. After producing a light-brown viscous solution, heating (70-90 °C) was continued for 2 h and then conc. H2SO4 (10 cm3) was added to the cooled solution. An additional 0.5 h reflux was performed and then treated with distilled water (400 cm3) to a light-yellow precipitate, which was stored at 4 °C overnight. The yellow product was isolated by filtration and washed with a small amount of cold methanol. A purer product was obtained after recrystallization from toluene. Yield: 5.7 g (35%); color: yellow; m.p: 130-134 °C (lit., 133.5 °C) [42]; 1H NMR [250 MHz, DMSO-d6, δ (ppm)]: 11.38 (s, 1H, OH), 10.19 (s, 2H, HC=O), 7.82 (s, 2H, Ar-H), 2.31 (s, 3H, CH3); 1HNMR (CDCl3, ppm): 11.39 (s, 1H, OH), 10.15 (s, 2H, HC = O), 7.70 (s, 2H, Ar-H), 2.32 (s, 3H, CH3);FT-IR (KBr, cm-1): 2869 (υC-H), 1674 (υC=O), 1211 (υC-O); Elemental Analysis, found (Calc.) %: C9H8O3 (MW = 164.05 g mol-1) C: 66.02 (65.85); H: 4.78 (4.91); N: 0 (0).

21%	Stage #1: formaldehyd; p-cresol With hexamethylenetetramine In acetic acid at 70 - 90℃; for 2h; Stage #2: With sulfuric acid for 0.5h; Reflux;
	With hexamethylenetetramine; sulfuric acid Reflux;
	With hexamethylenetetramine; sulfuric acid; acetic acid Reflux;
	With hexamethylenetetramine; acetic acid at 70 - 80℃; for 2h;
	With hexamethylenetetramine

Reference： [1]Verani, Claudio Nazari; Rentschler, Eva; Weyhermueller, Thomas; Bill, Eckhard; Chaudhuri, Phalguni [Journal of the Chemical Society, Dalton Transactions, 2000, # 3, p. 251 - 258]
[2]Asadi, Zahra; Golchin, Maryam; Eigner, Vaclav; Dusek, Michal; Amirghofran, Zahra [Inorganica Chimica Acta, 2017, vol. 465, p. 50 - 60]
[3]Asadi, Zahra; Nasrollahi, Neda; Golchin, Maryam [Journal of the Iranian Chemical Society, 2019, vol. 16, # 11, p. 2479 - 2487]
[4]Buch, Christian D.; Mitcov, Dmitri; Piligkos, Stergios [Dalton Transactions, 2020, vol. 49, # 39, p. 13557 - 13565]
[5]Das, Kuheli; Mondal, Tapan Kumar; Garribba, Eugenio; Fondo, Matilde; Sinha, Chittaranjan; Datta, Amitabha [Inorganica Chimica Acta, 2014, vol. 413, p. 194 - 202]
[6]Das, Kuheli; Nandi, Soumendra; Mondal, Sudipa; Askun, Tulin; Cantürk, Zerrin; Celikboyun, Pinar; Massera, Chiara; Garribba, Eugenio; Datta, Amitabha; Sinha, Chittaranjan; Akitsu, Takashiro [New Journal of Chemistry, 2015, vol. 39, # 2, p. 1101 - 1114]
[7]Bhanja, Piyali; Bhunia, Kousik; Das, Sabuj K.; Pradhan, Debabrata; Kimura, Ryuto; Hijikata, Yuh; Irle, Stephan; Bhaumik, Asim [ChemSusChem, 2017, vol. 10, # 5, p. 921 - 929]
[8]Asadi, Zahra; Nasrollahi, Neda; Karbalaei-Heidari, Hamidreza; Eigner, Vaclav; Dusek, Michal; Mobaraki, Nabiallah; Pournejati, Roya [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2017, vol. 178, p. 125 - 135]

12
[ 7310-95-4 ]
[ 32047-53-3 ]
bis(iminomethyl)-2,6-bis(mercaptoisobutyl)-4-methylphenol [ No CAS ]

Reference： [1]European Journal of Inorganic Chemistry,2001,p. 751 - 754

13
[ 7310-95-4 ]
[ 20439-47-8 ]
[ 656811-79-9 ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 2-Hydroxy-5-methylisophthalaldehyde; (1R,2R)-1,2-diaminocyclohexane With lead acetate In methanol Stage #2: With sodium tetrahydroborate In methanol at 20℃; for 2h;

Reference： [1]Gao, Jian; Reibenspies, Joseph H.; Martell, Arthur E. [Angewandte Chemie - International Edition, 2003, vol. 42, # 48, p. 6008 - 6012]

14
[ 7310-95-4 ]
[ 35132-20-8 ]
[ 656811-81-3 ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: 2-Hydroxy-5-methylisophthalaldehyde; (R,R)-1,2-diphenylethylenediamine With lead acetate In methanol Stage #2: With sodium tetrahydroborate In methanol at 20℃; for 2h;

Reference： [1]Gao, Jian; Reibenspies, Joseph H.; Martell, Arthur E. [Angewandte Chemie - International Edition, 2003, vol. 42, # 48, p. 6008 - 6012]

15
[ 7310-95-4 ]
[ 563-41-7 ]
[ 300731-04-8 ]

Yield	Reaction Conditions	Operation in experiment
98%	With sodium acetate In ethanol; water at 20℃; for 0.0833333h; Sonication; Green chemistry;	General procedure for the synthesis of bis-semicarbazones (2a-f) General procedure: Ultrasound Method. A mixture of dialdehydes (1a-f) (1 mmol), semicarbazide hydrochloride (2 mmol) andsodium acetate (2.5 mmol) in aqueous ethanol (15 mL) was irradiated in the water bath of the ultrasoniccleaner at room temperature. To optimize time, the tests were implemented with several times (2, 5, 7, 10,and 15 min) and 5 min was selected as optimum time, also with increasing time from 5 to 15 min no changeswere observed in the formed products. After completion of the reaction (confirmed TLC), the obtained solidwas filtered off, washed with chilled aqueous ethanol (3x5 mL) and dried to afford the desired products (2a-f),which in all cases were essentially pure semicarbazones.2,2'-[(2-Hydroxy-5-methyl-1,3-phenylene)bis(methanylidene)]bis(hydrazine-1-carboxamide) (2a).45 Yield98%; light yellow solid; mp 197-199 oC; 1H NMR (400 MHz, DMSO): δ 10.67 (s, 1H, OH), 10.30 (s, 2H, NH), 8.11(s, 2H, CH=N), 7.48 (s, 2H, ArH), 6.43 (s, 4H, NH2), 2.24 (s, 3H, CH3). 13C NMR (100 MHz, DMSO): δ 156.6 (C=O),152.9 (ArC), 139.0 (CH=N), 129.3, 128.6, 121.0 (ArC), 20.4 (CH3). IR (KBr, cm-1): νmax 3264 (br, NH2, NH& OH),1676 (C=O) cm-1. HRMS (EI) for (M - H)+: calcd. 277.1044; found 277.1061. Anal. Calcd. for C11H14N6O3: C,47.48; H, 5.07; N, 30.20. Found: C, 47.51; H, 5.12; N, 30.16%
76.4%	With sodium carbonate In ethanol for 2h; Heating;
76%	Stage #1: semicarbazide hydrochloride In methanol for 1h; Stage #2: 2-Hydroxy-5-methylisophthalaldehyde In methanol for 6h; Reflux;	DSC 15mL methanol solution of semicarbazide hydrochloride (339 mg, 3.04mmol) is stirred with (256 mg, 3.04 mmol) for 1h. Then the suspension is filtered and added in 20 ml dry methanol solution of DFP (250 mg, 1.52 mmol) and refluxed for 6 h. Light yellow precipitate is filtered and washed with ethanol several times. Yield, 322 mg (76%). ESI-TOF(+) mass (Fig. S4): 301.1 for [DSC+Na+]. 1HNMR (600 MHz, DMSO-d6), δ (ppm): 10.67 (1H, S), 10.31 (2H, S), 8.11 (2H, S),7.48 (2H, S), 6.43 (4H, S), 2.24 (3H, S) (Fig.S2). FTIR spectrum (Fig. S6): 1689, 1654 (C=O), 1573 (CH=N).

Reference： [1]Arafa, Wael Abdelgayed Ahmed; Abdel-Magied, Ahmed Fawzy [Arkivoc, 2017, vol. 2017, # 5, p. 327 - 340]
[2]Lozan, Vasile; Lassahn, Paul-Gerhard; Zhang, Cungen; Wu, Biao; Janiak, Christoph; Rheinwald, Gerd; Lang, Heinrich [Zeitschrift fur Naturforschung, B: Chemical Sciences, 2003, vol. 58, # 12, p. 1152 - 1164]
[3]Lohar, Sisir; Sinha, Sougata; Ghosh, Subrata; Das, Debasis [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2016, vol. 155, p. 75 - 80]

16
[ 358-23-6 ]
[ 7310-95-4 ]
[ 801292-26-2 ]

Yield	Reaction Conditions	Operation in experiment
83%	Stage #1: 2-Hydroxy-5-methylisophthalaldehyde With potassium phosphate In toluene at 20℃; for 0.25h; Stage #2: trifluoromethylsulfonic anhydride In water; toluene at 0 - 20℃;

Reference： [1]Gopalsamuthiram, Vijay; Wulff, William D. [Journal of the American Chemical Society, 2004, vol. 126, # 43, p. 13936 - 13937]

17
[ 7310-95-4 ]
[ 107-21-1 ]
[ 773101-80-7 ]

Yield	Reaction Conditions	Operation in experiment
61%	With toluene-4-sulfonic acid In benzene at 20℃; for 23h; Heating / reflux;	1 Diprotected 4-methyldialdehyde phenol (1). To a 250 mL Schlenk flask with stirbar under argon 2-HYDROXY-5-METHYL-1, 3-BENZENEDICARBOXALDEHYDE (15.2 mmol, 2.5 g) was added and the flask evacuated and backfilled with argon 3 X. Anhydrous benzene (80 mL) was cannula transferred followed by stirring at ambient temperature. Next, anhydrous ethylene glycol (91.4 mmol, 5.67 g) was added via syringe under argon followed BY TSOH (0.167 mmol, 0. 032 g). The reaction vessel was fitted with a Dean- Stark trap and reflux condenser and the reaction refluxed for ca. 23 h. The reaction was diluted with ethyl acetate (300 mL) washed with 1M NaHCO3 (50 mL), H20 (50 mL), then brine (50 mL). The organic layer was separated and dried OVER NA2S04, filtered and the solvent removed by rotovaporation. Purification by silica gel chromatography (2: 1 hexane: ethyl acetate) afforded a white solid (2.34 g; 6 LAO yield).

Reference： [1]Current Patent Assignee: COVALENT PARTNERS - WO2005/30711, 2005, A2 Location in patent: Page/Page column 76

18
[ 7310-95-4 ]
[ 20439-47-8 ]
C₄₅H₅₄N₆O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	In dichloromethane at 20℃; for 16h;	53 A solution of 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehye (53 mg, 0.32 mmol) in dichloromethane (0.6 mL) was added to a solution of (1R,2R)-(-)-1,2-diaminocyclohexane (37 mg, 0.32 mmol) in dichloromethane (0.5 mL). The mixture was stirred at ambient temperature for 16 h, added dropwise to methanol (75 mL) and chilled (4[deg.] C.) for 4 h. The precipitate was collected to afford 71 mg (92%) of hexamer 1A-Me. <1>H NMR (CDCl3): [delta] 13.88 (s, 3H, OH), 8.66 (s, 3H, ArCH-N), 8.19 (s, 3H, ArCH-N), 7.52 (d, 3H, J=2 Hz, Ar H), 6.86 (d, 3H, J=2 Hz, Ar H), 3.35 (m, 6H, cyclohexane 1,2-H's), 2.03 (3, 9H, Me), 1.6-1.9 (m, 18H, cyclohexane 3,6-H2 and 4eq,5eq-H's), 1.45 (m, 6H, cyclohexane 4ax, 5ax-H's); <13>C NMR [delta] 63.67, 159.55, 156.38, 134.42, 129.75, 127.13, 119.00, 75.68, 73.62, 33.68, 33.41, 24.65, 24.57, 20.22; ESI(+) MS m/e (%) 727 M+H (100); IR 1634 cm.

Reference： [1]Current Patent Assignee: COVALENT PARTNERS - US2003/199688, 2003, A1 Location in patent: Page/Page column 44; 45

19
manganese(II) perchlorate hexahydrate [ No CAS ]
[ 4097-88-5 ]
[ 7310-95-4 ]
[ 2156-56-1 ]
{Mn₂(CH₃C₆H₂O(CHNCH₂CH₂)2NCH₃)2(CHCl₂CO₂)}⁽¹⁺⁾*ClO₄^(1-) = Mn₂(CH₃C₆H₂O(CHNCH₂CH₂)2NCH₃)2(CHCl₂COO)ClO₄ [ No CAS ]

Reference： [1]Chemistry Letters,1993,p. 1049 - 1052

20
[ 7310-95-4 ]
[ 88-44-8 ]
[ 142-71-2 ]
(N,N-(2-hydroxy-5-methyl-1,3-dibenzylidine)-bis-(4-methyl-2-sulphonate aniline))copper*tetrahydrate [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 102,p. 121 - 126

21
[ 7310-95-4 ]
[ 88-44-8 ]
[ 373-02-4 ]
(N,N-(2-hydroxy-5-methyl-1,3-dibenzylidine)-bis-(4-methyl-2-sulphonate aniline))nickel*4.5hydrate [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 102,p. 121 - 126

22
[ 7310-95-4 ]
[ 88-44-8 ]
[ 142-72-3 ]
(N,N-(2-hydroxy-5-methyl-1,3-dibenzylidine)-bis-(4-methyl-2-sulphonate aniline))magnesium*4.5H₂O [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 102,p. 121 - 126

23
[ 7310-95-4 ]
[ 88-44-8 ]
[ 638-38-0 ]
(N,N-(2-hydroxy-5-methyl-1,3-dibenzylidine)-bis-(4-methyl-2-sulphonate aniline))manganese*1.5hydrate*di-acetic acid [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 102,p. 121 - 126

24
[ 7310-95-4 ]
[ 88-44-8 ]
[ 557-34-6 ]
(N,N-(2-hydroxy-5-methyl-1,3-dibenzylidine)-bis-(4-methyl-2-sulphonate aniline))zinc*4.5hydrate [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 102,p. 121 - 126

25
[ 7310-95-4 ]
[ 88-44-8 ]
[ 71-48-7 ]
(N,N-(2-hydroxy-5-methyl-1,3-dibenzylidine)-bis-(4-methyl-2-sulphonate aniline))cobalt*4.5hydrate [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 102,p. 121 - 126

26
[ 7310-95-4 ]
[ 88-44-8 ]
iron(II) sulfate [ No CAS ]
(N,N-(2-hydroxy-5-methyl-1,3-dibenzylidine)-bis-(4-methyl-2-sulphonate aniline))iron*1.5hydrate*di-acetic acid [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 102,p. 121 - 126

27
[ 7310-95-4 ]
[ 13940-96-0 ]
[ 373-02-4 ]
[ 38399-46-1 ]
C₆H₃(OC₆H₅)(NCHC₁₀H₅OC(O)OH)(NCHC₆H₂(CH₃)OCH(O))Ni*H₂O [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 96,p. 209 - 212

28
[ 7310-95-4 ]
[ 373-02-4 ]
[ 81-16-3 ]
(alsatH)nickel*trihydrate [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 102,p. 121 - 126

29
[ 7310-95-4 ]
[ 557-34-6 ]
[ 81-16-3 ]
(alsatH)zinc*trihydrate [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1985,vol. 102,p. 121 - 126

30
[ 4461-39-6 ]
[ 7310-95-4 ]
[ 6156-78-1 ]
Mn₂O₂(N₃)2NCHC₆H₂CH₃CHN(CH₂)3NCHC₆H₂CH₃CHN(CH₂)3 [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1992,vol. 194,p. 129 - 132

31
[ 29046-78-4 ]
[ 7310-95-4 ]
[ 65423-44-1 ]
[NiCl(CH₃C₆H₂O(CHNC₆H₄P(C₆H₅)2)2H)]⁽¹⁺⁾*Cl^(1-)=[NiCl(CH₃C₆H₂(O)(CHNC₆H₄P(C₆H₅)2)2H)]Cl [ No CAS ]

Reference： [1]Inorganica Chimica Acta,2005,vol. 358,p. 3003 - 3008

32
[ 10025-74-8 ]
[ 7310-95-4 ]
[ 107-15-3 ]
[ 291290-44-3 ]

Reference： [1]Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry,2000,vol. 30,p. 1057 - 1068

33
[ 7310-95-4 ]
[ 109-76-2 ]
iron(II) chloride [ No CAS ]
C₂₄H₂₆N₄O₂^(2-)*2Cl^(1-)*2Fe⁽²⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	In methanol at 20℃; for 3h;	2 Under nitrogen atmosphere, a 50 ml round-bottom flask was loaded with 20 ml of a methanol solution containing 0.4 g of iron chloride tetrahydrate and 0.33 g of 4-methyl-2,6-diformylphenol and the solution was stirred at room temperature. Ten ml of methanol containing 0.15 g of 1,3-propanediamine was gradually added to the solution. After the above-mentioned mixture was stirred for 3 hours, red brown precipitate was produced. The precipitate was recovered by filtration and dried to obtain a multinuclear metal complex (B) (produced amount 0. 50 g: yield 85%). In the above-mentioned reaction formula the "Cl2" means two equivalents of chloride ion existed as a counter ion. Elemental analysis value (%): Calcd. for C24H26Cl2Fe2N4O2; C, 49.27; H, 4.48; N, 9.58. Found: C, 44.92; H, 4.94; N, 10.86.

Reference： [1]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - EP1988084, 2008, A1 Location in patent: Page/Page column 17

34
[ 4097-88-5 ]
[ 7310-95-4 ]
[ 7732-18-5 ]
[ 3109-63-5 ]
[ 7646-85-7 ]
Zn₂(CH₃N(CH₂CH₂NCHC₆H₂(CH₃)(O)CHNCH₂CH₂)2NCH₃)Cl⁽¹⁺⁾*PF₆^(1-)*1.7H₂O=C₂₈H₃₆N₆ClZn₂O₂PF₆*1.7H₂O [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2008,vol. 130,p. 4708 - 4724

35
manganese(II) chloride tetrahydrate [ No CAS ]
[ 4097-88-5 ]
[ 7310-95-4 ]
[ 3109-63-5 ]
[ 1021496-30-9 ]

Reference： [1]Journal of the American Chemical Society,2008,vol. 130,p. 4708 - 4724

36
[ 7310-95-4 ]
[ 136-64-1 ]
[ 1187324-92-0 ]

Reference： [1]European Journal of Medicinal Chemistry,2009,vol. 44,p. 3552 - 3559
[2]Bulletin of the Korean Chemical Society,2012,vol. 33,p. 473 - 482

37
C₆₈H₁₀₆N₈O₁₆ [ No CAS ]
[ 7310-95-4 ]
C₆₆H₈₂N₈O₁₀ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	Stage #1: C₆₈H₁₀₆N₈O₁₆ With trifluoroacetic acid In dichloromethane at 20℃; for 1h; Stage #2: With triethylamine In diethyl ether at 20℃; for 2h; Stage #3: 2-Hydroxy-5-methylisophthalaldehyde In d⁽⁴⁾-methanol at 66℃; for 22h;	1 Bridged macrocyclic module (6): To a 15 mL round bottom flask with stirbar under argon 5 (0.0107 mmol, 0.0138 g) was added. The vessel was evacuated and backfilled with argon (3X). The substrate was dissolved in dichloromethane (0.712 mL, 0.015 M). Anhydrous trifluoroacetic acid (0.356 mL) was added via syringe, the vessel sealed under argon with a glass stopper and stirred at rt for ca. 1 h. All volatiles were removed under vacuo followed by addition OF CA. 1 mL of diethyl ether. Next, anhydrous NEt3 (0.020 mL) was added via syringe under argon at rt and the mixture stirred for ca. 2 h. The resulting precipitate was washed with anhydrous diethyl ether (4 X 2 mL), followed by cannula filtration and drying in vacuo to afford a light yellow solid. In a nitrogen atmosphere glovebag, the solid was dissolved in CD30D (2 mL) and transferred to a vial containing 2-HYDROXY-5-METHYL-1, 3-benzenedicarboxaldehyde (0.0214 mmol, 0.0035 g). The reaction mixture was transferred to a J-Young tube, sealed and heated to 66 °C for 22 h. Purification by silica plug (4: 2: 0.3 chloroform : hexane: triethylamine) afforded a yellow-green solid (0. 0103 g, 84% YIELD).

Reference： [1]Current Patent Assignee: COVALENT PARTNERS - WO2005/30711, 2005, A2 Location in patent: Page/Page column 79

38
[ 7310-95-4 ]
[ 142-71-2 ]
[ 121-44-8 ]
[ 3060-50-2 ]
(CH₃CH₂)3NH⁽¹⁺⁾*Cu₂(CH₃COO)2(O)(CH₃)C₆H₂(HCNC(C₆H₅)2COO)2^(1-)=(HN(C₂H₅)3)[Cu₂(CH₃COO)2(O)(CH₃)C₆H₂(HCNC(C₆H₅)2COO)2] [ No CAS ]

Reference： [1]Inorganica Chimica Acta,2011,vol. 365,p. 96 - 102

39
[ 825-55-8 ]
[ 7310-95-4 ]
[ 1313735-45-3 ]

Yield	Reaction Conditions	Operation in experiment
44%	Stage #1: 2-phenylthiophene With n-butyllithium In tetrahydrofuran at -78℃; Stage #2: 2-Hydroxy-5-methylisophthalaldehyde In tetrahydrofuran at -78 - 25℃; for 12h; Stage #3: With manganese(IV) oxide In chloroform at 25℃; for 12h;	16 (Example 16) 40 ml of a tetrahydrofuran solution of 3.0 g of phenylthiophene was cooled to -78 °C, and 8.6 ml (2.6 M) of n-butyllithium was slowly dropped thereto, and stirred at the same temperature for 2 hours. Thereafter, 0.85 g of 2- hydroxy-5-methylisophthalaldehyde was added thereto, and stirred for 12 hours while the temperature was being slowly raised to 25 °C. After the confirmation of the degree of reaction progress by TLC, the reaction was terminated with an ammonium chloride aqueous solution, and an organic phase was extracted with ethyl acetate.[0122] After the obtained organic phase was dried with anhydrous magnesium sulfate, the organic phase was concentrated and purified by column chromatography. 10 g of manganese dioxide was added to 30 ml of a chloroform solution of the obtained intermediate compound, and the mixture was stirred at 25°C for 12 hours. After the confirmation of the degree of reaction progress by TLC, the manganese dioxide was filtered, and 1.1 g (yield: 44%) of Product 16 shown below was obtained as a white crystal by recrystallization. The structure of Product 16 was confirmed by 1HNMR. 1H-NMR (CDC13; T S) : δ 2.41 (s, 3H) , 7.37-7.46 (m, 8H) , 7.66-7.74 (m, 8H) , 11.78 (s, 1H)

Reference： [1]Current Patent Assignee: CANON INC. - WO2011/81078, 2011, A1 Location in patent: Page/Page column 34-35

40
[ 7310-95-4 ]
[ 106-50-3 ]
[ 1315483-56-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	In ethanol at 20℃; Reflux;	Synthesis of ligand LH2 2,6-Diformyl-4-methylphenol (0.1 mol) was taken in 50 ml of absolute ethanol, to which p-phenylenediamine (0.05 mol) in absolute alcohol was added dropwise with constant stirring. Further the mixture was stirred at room temperature for 30 min. The reaction mixture was refluxed on water bath temperature for 4 h. The reddish solid that formed (precursor A) was filtered off and washed with hot ethanol (m.p.: 260 °C, yield: 90%). The ethanolic solution of 2-hydrazinobenzothiazole (0.2 mol) is added slowly to the above obtained compound (0.1 mol) in 70 ml of ethanol with constant stirring. After completion of the addition the mixture was stirred at room temperature for 15 min and refluxedon water bath temperature for 4 h. Catalytical amount of acetic acid is added while refluxing. The dirty-yellow solid that formed was filtered off and washed with hot ethanol (m.p.: 340 °C, yield: 78%). The reaction pathway is given in Fig. 1.

Reference： [1]Location in patent: experimental part Kamath, Anupama; Kulkarni, Naveen V.; Netalkar, Priya P.; Revankar, Vidyanand K. [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2011, vol. 79, # 5, p. 1418 - 1424]

41
[ 7310-95-4 ]
[ 141-43-5 ]
[ 174504-82-6 ]

Yield	Reaction Conditions	Operation in experiment
89%	In methanol for 1h; Reflux;
72%	In methanol for 3h; Reflux;	2.3 Synthesis of 2,6-bis-[(2-hydroxyethylimino)methyl]-4-methylphenol (L¹) The di-aldehyde precursor (2,6-diformyl-4-methylphenol) was prepared according to the procedure published by Verani et. al. [22]. To a methanolic solution of 2,6-diformyl-4-methylphenol (0.164g, 1mmol) was added 2-aminoethanol (0.12ml, 2mmol). The reaction mixture was reuxed for 3h after solvent evaporation; an orange product was collected by ltration, washed with a minimum volume of methanol and diethyl ether. The product was purified by recrystallization from methanol [23].(Fig. 1 ) Yield: 0.18g (72%); color: orange; m.p: 145°C; 1H NMR (DMSO-d6, ppm): 14.36 (1H, s, OHa), 8.54 (2H, s, HC=N), 7.50 (2H, s, Ar-H), 4.68 (2H, s, OHb), 3.62 (8H, s, CH2), 2.23 (3H, s, CH3); FT-IR (KBr, cm-1): 3348 (υ O-H), 1635 (υ C=N), 1604 and 1450 (υ C=C), 1072 (υ C-O); Elemental Analysis, Found (Calc.)%: C13H18N2O3 (MW=250g.mol-1) C: 62.46 (62.38); H: 7.55 (7.25); N: 11.30 (11.19)
	In methanol for 1h; Reflux;	3.1 2.3.1 2,6-Bis-[(2-hydroxy ethylimino)-methyl]-4-methyl phenol (H₃bemp) The Schiff base was prepared from the single step condensation reaction of 2,6-diformyl-4-methyl phenol (1.0 g, 6.1 mmol) and 2-amino ethanol (0.74 g, 12.2 mmol) in MeOH (40 mL) under reflux for 1 h, as reported previously [18].

In acetonitrile for 4h; Reflux;

Reference： [1]Sarkar, Avijit; Ghosh, Aloke Kumar; Bertolasi, Valerio; Ray, Debashis [Dalton Transactions, 2012, vol. 41, # 6, p. 1889 - 1896]
[2]Asadi, Zahra; Golchin, Maryam; Eigner, Vaclav; Dusek, Michal; Amirghofran, Zahra [Journal of Photochemistry and Photobiology A: Chemistry, 2018, vol. 361, p. 93 - 104]
[3]Sarkar, Avijit; Bertolasi, Valerio; Ray, Debashis [Polyhedron, 2012, vol. 44, # 1, p. 113 - 123]
[4]Halder, Shibashis; Dey, Sudipto; Rizzoli, Corrado; Roy, Partha [Polyhedron, 2014, vol. 78, p. 85 - 93]

42
[ 7310-95-4 ]
[ 156-87-6 ]
[ 1356334-20-7 ]

Yield	Reaction Conditions	Operation in experiment
78%	In methanol at 28℃; for 2h;
78%	In methanol at 28℃; for 2h;	2.1 Synthesis 2.2.1 _2,6-Bis-[(3-hydroxy-propylimino)-methyl]-4-methyl-phenol (H3L) To a MeOH solution (20 mL) of 2,6-diformyl-4-methylphenol (1.0 g, 6.1 mmol), 3-amino-1-propanol (0.91 g, 12.2 mmol) was added in air at room temperature (28 °C) and stirred for 2 h to give an orange colored semi-solid product after complete evaporation of solvent in air for 12 h. The semi-solid product 2,6-bis-[(3-hydroxy-propylimino)-methyl]-4-methylphenol thus obtained was washed with water and used directly without further purification for complexation reactions. Yield: 1.32 g (78%).
78%	In methanol at 28℃; for 2h;	2.1 2.2.1 H₃bpmp ligand To a MeOH solution (20 mL) of 2,6-diformyl-4-methylphenol (1.0 g, 6.1 mmol), 3-amino-1-propanol (0.91 g, 12.2 mmol) was added in air at room temperature (28 °C) and stirred for 2 h to give an orange colored semi-solid product after complete evaporation of solvent in air for 12 h. The semi-solid product 2,6-bis-[(3-hydroxy-propylimino)-methyl]-4-methylphenol thus obtained was washed with water and used directly without further purification. Yield: 1.32 g (78%).

78%	In methanol at 28℃; for 2h;	2.2.1 H₃bpmp ligand The H3bpmp Schiff-base ligand was prepared from the single step condensation of 2,6-diformyl-4-methylphenol (1.0g, 6.1 mmol) and 3-amino-1-propanol (0.91g, 12.2mmol) in methanol (20mL) in air at room temperature (28°C), under stirring for 2h. Complete evaporation of the solvent in air over 12h yielded an orange colored semi-solid product which was used directly for the reaction without further characterization. Yield: 1.32g (78%).
78%	In methanol at 28℃; for 2h;
78%	In methanol at 28℃; for 2h;
78%	In methanol at 28℃;
	In methanol at 28℃; for 2h;
	In acetonitrile for 5h; Reflux;	2.3 Syntheses of [Cu₄(L²)₂(O)(CH₃COO)₄] (2), [Cu₅(L³)₂(OH)₂(CH₃COO)₆]·H₂O (3), [Cu₄(L⁴)₂(O)(CH₃COO)₄]·CH₃CN (4) and [Cu₄(L⁵)₂(O)(CH₃COO)₄] (5) General procedure: Complexes 2, 3, 4 and 5 were synthesized following a similar procedure. Typically, to an acetonitrile solution (10mL) of 4-methyl-2,6-diformyl (0.3mmol, 0.049g) was added respective amine (0.6mmol) (0.045g of 3-amino-1-propanol for complex 2; 0.053g of 4-amino1-butanol for complex 3; 0.062g of 5-amino-1-pentanol for 4; 0.070g of 6-amino-1-hexanol for complex 5). The mixture was stirred for 1h and after that it was refluxed for 4h. It was then cooled to room temperature. This ligand was used to synthesize copper(II) complexes without any purification or identification. Copper(II) acetate monohydrate (0.6mmol, 0.120g) was added and the solution stirred again for 45min. The mixture was then refluxed for about 1h, after which it was cooled to room temperature and filtered. The filtrate was kept at ambient temperature. Single crystals of complexes 3, 4 and 5 suitable for X-ray diffraction were grown from the filtrate upon slow evaporation within few days.
	In methanol at 28℃; for 2h;	2.2.1 The ligand H₃bpmp CH3OH solution (20mL) of prepared 22 2,6-diformyl-4-methylphenol (1.0g, 6.1mmol), 29 3-amino-1-propanol (0.91g, 12.2mmol) was added in air at room temperature (28°C) and stirred for 2h to give an orange colored gummy 30 product after complete evaporation of the reaction solvent in air for 12h. The gummy mass of H3bpmp was washed copiously with water and dried over P4O10 in a CaCl2 charged desiccator. The product was later used directly without undergoing further purification steps. Yield: 1.32g (78%).

Reference： [1]Sarkar, Avijit; Ghosh, Aloke Kumar; Bertolasi, Valerio; Ray, Debashis [Dalton Transactions, 2012, vol. 41, # 6, p. 1889 - 1896]
[2]Ghosh, Aloke Kumar; Bauzá, Antonio; Bertolasi, Valerio; Frontera, Antonio; Ray, Debashis [Polyhedron, 2013, vol. 53, p. 32 - 39]
[3]Ghosh, Aloke Kumar; Ray, Debashis [Polyhedron, 2013, vol. 52, p. 370 - 376]
[4]Ghosh, Aloke Kumar; Clérac, Rodolphe; Mathonière, Corine; Ray, Debashis [Polyhedron, 2013, vol. 54, p. 196 - 200]
[5]Ghosh, Aloke Kumar; Pait, Moumita; Shatruk, Michael; Bertolasi, Valerio; Ray, Debashis [Dalton Transactions, 2014, vol. 43, # 5, p. 1970 - 1973]
[6]Ghosh, Aloke Kumar; Pait, Moumita; Clerac, Rodolphe; Mathoniere, Corine; Bertolasi, Valerio; Bauza, Antonio; Frontera, Antonio; Pramanik, Kausikisankar; Ray, Debashis [Dalton Transactions, 2014, vol. 43, # 10, p. 4076 - 4085]
[7]Ghosh, Aloke Kumar; Singha Mahapatra, Tufan; Clérac, Rodolphe; Mathonière, Corine; Bertolasi, Valerio; Ray, Debashis [Inorganic Chemistry, 2015, vol. 54, # 11, p. 5136 - 5138]
[8]Ghosh, Aloke Kumar; Shatruk, Michael; Bertolasi, Valerio; Pramanik, Kausikisankar; Ray, Debashis [Inorganic Chemistry, 2013, vol. 52, # 24, p. 13894 - 13903]
[9]Halder, Shibashis; Dey, Sudipto; Rizzoli, Corrado; Roy, Partha [Polyhedron, 2014, vol. 78, p. 85 - 93]
[10]Das, Manisha; Ghosh, Aloke Kumar; Clérac, Rodolphe; Mathonière, Corine; Ray, Debashis [Polyhedron, 2018, vol. 146, p. 136 - 144]

43
[ 7310-95-4 ]
N<SUP>1</SUP>-(2-aminoethyl)-N<SUP>2</SUP>-(4-nitrobenzyl)ethane-1,2-diamine trihydrobromide [ No CAS ]
sodium perchlorate [ No CAS ]
[ 6018-89-9 ]
[ 1426433-67-1 ]

Yield	Reaction Conditions	Operation in experiment
40.9%	Stage #1: 2-Hydroxy-5-methylisophthalaldehyde; N<SUP>1</SUP>-(2-aminoethyl)-N<SUP>2</SUP>-(4-nitrobenzyl)ethane-1,2-diamine trihydrobromide; nickel(II) acetate tetrahydrate With sodium hydroxide In ethanol; water at 20℃; for 8h; Stage #2: sodium perchlorate In ethanol; water for 8h;	Preparation of [Ni2L1(OAc)2]ClO4 (1) To a solution of 2,6-diformyl-4-methylphenol (0.082 g, 0.5 mmol) and Ni(OAc)2 4H2O (0.249 g, 1 mmol) in anhydrous ethanol (15 mL), the mixture of N1-(2-aminoethyl)- N2-(4-nitrobenzyl) ethane-1,2-diamine hydrobromide (0.481 g, 1 mmol) and NaOH (0.120 g, 3 mmol) in 10 mL distilled water was added dropwise. The resulting solution was stirred at ambient temperature for 8 h, NaClO4 (0.141 g, 1 mmol) was added. After being stirred for further 8 h, the reaction mixture was filtered. The green block crystals suitable for the X-ray measurement were obtained by evaporation of the filtrate at room temperature for five days. Yield: 0.192 g (40.9%). Anal. Calc. for C35H45N8Ni2O9ClO4 (%): C, 44.79; H, 4.83; N, 11.94 Found: C, 44.89; H, 4.76; N, 11.89. IR(KBr, m/cm 1): 3277 m(NAH), 1643 m(C(at)N), 1094, 624 m(ClO 4 ), 1402, 1548 m(OAc ).

Reference： [1]Wang; Xiao; Mao; Zhou; Pan [Journal of Molecular Structure, 2013, vol. 1036, p. 361 - 371]

44
magnesium(II) nitrate hexahydrate [ No CAS ]
[ 7310-95-4 ]
[ 16674-78-5 ]
[ 107-15-3 ]
C₄₄H₄₈Mg₂N₁₀O₁₀⁽²⁺⁾*2NO₃^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	In methanol; for 2.5h;Reflux;	This compound has been prepared by suitable modification of the procedure reported previously by us [39]. To a boiling methanol solution (50 cm3) containing 4-methyl-2,6-diformylphenol [40] (1.64 g, 10 mmol), Mg(OAc)24H2O (1.07 g,5 mmol) and Mg(NO3)26H2O (1.28 g, 5 mmol) was added a methanol solution (30 cm3) of 1,2-diaminoethane (0.60 g, 10 mmol) over a period of 0.5 h. A yellow crystalline product began to deposit after 0.5 h. After 2 h of reflux, the precipitated magnesium(II) complex was filtered and washed with methanol and diethyl ether; yield 2.24 g (80%). Anal. Calc. for C44H56Mg2N12O20: C, 47.13; H,5.03; N, 14.98. Found: C, 47.30; H, 5.14; N, 14.84%. IR (KBr): 3420br, 1650s, 1490s, 1385s, 1240m, 1085m, 830w cm 1. 1HNMR (300 MHz, (CD3)2SO) H: 14.0 (br, 4H, N-H O), 8.47 (s, 8H, CH(at)N), 7.40 (s, 8H, Ar), 3.93 (s, 16H, CH2), 2.12 (s, 12H, CH3) ppm.

Reference： [1]Polyhedron,2013,vol. 52,p. 976 - 985

45
[ 83-07-8 ]
[ 7310-95-4 ]
[ 956474-43-4 ]

Yield	Reaction Conditions	Operation in experiment
84%	In methanol for 6h; Reflux;	2.2.1.1. Preparation of L 2, 6-diformyl-4-methyl phenol a, (1 mmol)was added to a solution of 4-aminoantipyrine (2 mmol) in hot methanol(50 mL) with a syringe. The mixture was heated to reflux for 6 h. Theresulting precipitate was purified with hot methanol. The obtainedproduct was collected and dried at room temperature.2.2.2. Synthesis of receptor LYellow, yield: 84%. Anal. Calc. for C31H30N6O3, C: 69.08, H: 5.61, N:15.72 Found: C: 68.73, H: 5.10, N: 14.92 %. FTIR (KBr, cm 1): 3421(-OH group), 1652 (C = O group), 1638 (C = N group), 1508 (phenol ring), 1293 (C-O), 1135 (-N-N). 1H NMR (d6-DMSO, 300 MHz, ppm) δ:13.85(1H, s, OH-phenolic), 9.86(2H, s, CH = N), 7.64(2H, s, ArH), 7.61(2H, s, ArH), 7.58(4H, d, ArH), 7.42(4H, d, ArH), 2.54(6H, s, N-Me),2.48(6H, s, C-Me), 2.35(3H, s, H-methyl). λmax (nm) (ε (M 1 cm 1)):254(34100), 320(34210), 370(30500) in CH3CN.
75%	In ethanol for 8h; Reflux;
	In methanol for 1h; Reflux;	Synthesis General procedure: The imine derivatives of 4-aminoantipyrine (4AAP) have been obtained by condensation in methanol solution of parent amine and appropriate aldehyde in proportions 1:1. This is the modification of the method published previously [49]. The mixture was stirred and refluxed for 1 h. Then the mixture was cooled to room temperature. After 24 h the obtained precipitate was filtered out and washed by methanol. The authenticity and purity of obtained compounds were examined by proton NMR measurements.

Reference： [1]Arabahmadi, Raziyeh [Journal of Photochemistry and Photobiology A: Chemistry, 2022, vol. 426]
[2]Lohar, Sisir; Sengupta, Archya; Chattopadhyay, Ansuman; Matalobos, Jesús Sanmartín; Das, Debasis [European Journal of Inorganic Chemistry, 2014, vol. 2014, # 33, p. 5675 - 5682]
[3]Schilf, Wojciech; Kamieński, Bohdan; Szady-Chełmieniecka, Anna; Kołodziej, Beata; Grech, Eugeniusz; Zarzeczańska, Dorota; Wcisło, Anna; Ossowski, Tadeusz [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013, vol. 109, p. 47 - 54]

46
[ 3048-01-9 ]
[ 7310-95-4 ]
[ 1443360-61-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	In acetonitrile for 4h; Reflux;	2.2 Synthesis of 4-methyl-2,6-bis(((2-tri-fluoromethyl)phenyl)methyliminomethyl)phenol(HL) The ligand HL was synthesized following a literature method with a slight modification [29,30]. 2-Trifluoromethyl-1-phenylmethanamine (0.857g, 8mmol) in 10mL of acetonitrile was added to a solution of 4-methyl-2,6-diformylphenol (0.656g, 4mmol) in 15mL of acetonitrile. The reaction mixture was refluxed for 4h. The solution was filtered, concentrated on a rotary evaporator to dryness and kept at 4°C overnight. The yellow colored solid Schiff base ligand was recrystallized from acetonitrile. (Yield=1.7g, 89%) Anal. Calc. For C25H20N2OF6: C, 62.76; H, 4.21; N, 5.86. Found: C, 62.73; H, 4.10; N, 5.92%. 1H NMR δH (300MHz, CDCl3, Me4Si): 2.31 (3H, s, Ar-CH3), 5.01 (4H, s, CH), 7.26-7.72 (10H, m, Ar-CH), 8.70 (2H, s, HC=N). HRMS: m/z (ESI) 479.09 ([HL+H]+ requires 479.1513).

Reference： [1]Jana, Mahendra Sekhar; Dey, Sudipto; Priego, José L.; Jiménez-Aparicio, Reyes; Kumar Mondal, Tapan; Roy, Partha [Polyhedron, 2013, vol. 59, p. 101 - 106]

47
[ 7310-95-4 ]
[ 6325-92-4 ]
[ 1443458-05-6 ]

Yield	Reaction Conditions	Operation in experiment
95%	In ethanol at 20 - 25℃;	2.3.1 Synthesis of ligand Ethanol solution (30 mL) containing 4-methyl-2,6-diformyl phenol (0.5 g, 3.04 mmol) was slowly added to an ethanol solution (20 mL) of 2-(benzylthio)aniline (1.31 g, 6.09 mmol). After complete addition, the reaction mixture was stirred at 25 °C for 6 h and kept at room temperature overnight. The product that formed was separated as yellowish-orange crystals, which were collected by filtration and washed with ethanol and diethyl ether. The filtrate on standing for an additional 24 h provides a second crop of product, and the combined yield was 1.61 g (95 %) or more. Anal. Calc. for C35H30N2OS2: C, 75.17; H, 5.36; N, 5.01. Found: C, 75.23; H, 5.20; N, 5.18%. UV-Vis (λmax/nm (ε/dm2mol-1), dichloromethane): 385 (12144); 260 (33211). IR (KBr, cm-1): 3343 (ν O-H), 2914 ν(C-H), 1621 and 1592 ν(C=N), 1254 ν(O-C), 744 ν(C-S). 1H NMR (400 MHz, CDCl3): 2.35 (CH3, s, 3H), 4.14 (CH2, s, 4H), 7.10-7.36 (ArH, m, 20H), 8.53 (CH=N, s, 2H), 13.65 (Ar-OH, s, 1H).

Reference： [1]Pattanayak, Poulami; Pratihar, Jahar Lal; Patra, Debprasad; Brandão, Paula; Mal, Dasarath; Felix, Vitor [Polyhedron, 2013, vol. 59, p. 23 - 28]

48
[ 7310-95-4 ]
[ 33513-42-7 ]
[ 10347-32-7 ]
[ 7646-85-7 ]
C₃₂H₄₄Cl₄N₈O₄Zn₄*2C₃H₇NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With sodium hydroxide In water at 120℃; for 90h; Sealed tube; High pressure;	General procedure: [Zn4L1Cl4]·3H2O (1): A mixture of 2,6-diformyl-4-methoxyl phenol (1.8mg, 0.01mmol), 1,3-bis[(2-aminoethyl)amino]-2-propanol (1.76mg, 0.01mmol), ZnCl2 (2.73mg, 0.02mmol) and aqueous NaOH (0.2mL 0.1mol/L, 0.02mmol) in DMF/H2O (2/1) was sealed in a small glass vial (10mL), which was heated to 120°C for 90h. After cooling to room temperature, yellowish block crystals of 1 suitable for X-ray structure determination were obtained. Yield: 2.6mg, 48%.

Reference： [1]Ding, Cai-Xia; He, Chang-Hua; Xie, Yong-Shu [Chinese Chemical Letters, 2013, vol. 24, # 6, p. 463 - 466]

49
[ 7310-95-4 ]
[ 40617-52-5 ]

Yield	Reaction Conditions	Operation in experiment
82%	With sodium hydroxide; silver(l) oxide In water at 55 - 60℃; for 0.166667h;	1.1.7 p-cresol 2,6-dicarboxylic acid Put a rotor in a 50 mL recovery flask,1.56 g of NaOH was dissolved in 13.7 mL of H 2 O,1.78 g (7.80 mmol) of Ag 2 O was added and the mixture was heated to 55 ° -60 ° C. There, 0.63 g (3.90 mmol) of 2,6-diformyl-p-cresol was added and stirring was continued until Ag 2 O was reduced to Ag. Thereafter, the mixture was further stirred for 10 minutes,The solution was filtered with hot water,When pH was lowered to 1 by adding HCl to the filtrate, a pale yellow solid precipitated.This was collected by filtration to obtain 0.56 g of the objective compound(2.86 mmol, 82%).
	With potassium hydroxide at 230℃;

Reference： [1]Current Patent Assignee: DOSHISHA UNIVERSITY - JP2018/135304, 2018, A Location in patent: Paragraph 0045; 0046
[2]Samanta, Suvendu; Das, Sudipto; Samanta, Partha Kumar; Dutta, Supriya; Biswas, Papu [RSC Advances, 2013, vol. 3, # 42, p. 19455 - 19466]

50
manganese(II) chloride tetrahydrate [ No CAS ]
[ 7310-95-4 ]
C₁₂H₂₂N₄*3ClH [ No CAS ]
sodium perchlorate [ No CAS ]
[{Mn₂(N-(2-pyridylmethyl)-N-(3-aminopropyl)-1,3-diaminopropane)Cl(H₂O)}₂(μ-Cl)₂][Mn₂(N-(2-pyridylmethyl)-N-(3-aminopropyl)-1,3-diaminopropane)(H₂O)₂](ClO₄)₆Cl₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50%	Stage #1: C₁₂H₂₂N₄*3ClH With sodium hydroxide In ethanol for 0.5h; Reflux; Stage #2: manganese(II) chloride tetrahydrate; 2-Hydroxy-5-methylisophthalaldehyde In methanol at 20℃; for 72h; Stage #3: sodium perchlorate In methanol	Preparation of [{Mn2(H2L1)Cl(H2O)}2(μ-Cl)2][Mn2(H2L1) (H2O)2](ClO4)6Cl2, 1 General procedure: L22py·3HCl (0.1 g, 0.33 mmol) and NaOH (0.04 g, 0.99 mmol) were mixed and heated under reflux for 30 min in EtOH (15 ml). The NaCl which formed upon cooling was filtered off. The filtrate was added to a mixed solution of 2,6-diformyl-4-methylphenol (0.05 g, 0.33 mmol) and MnCl2·4H2O (0.06 g, 0.33 mmol) in dry MeOH (40 ml) with continuous stirring, and the solution colour gradually changed from brown to deep green. The mixture was stirred at room temperature for 72 h, then NaClO4 (0.09 g, 0.66 mmol) was added. The solution was filtered and the filtrate was reduced to ca 10 cm3. A yellow crystalline compound was obtained by slow diffusion of Et2O vapor into this solution. Yield: 40%. Anal. Calc. for C114H140Cl12Mn6N24O34: C, 43.82; H, 4.41; N, 10.77. Found: C, 43.18; H, 4.19; N, 10.56%. IR (KBr, cm-1): 1623, (νC=N schiff base), 1558 (νC=N pyridine), 1568 (νC=C), 1081. UV (acetonitrile, nm (ε, L mol-1 cm-1)): 228 (4690), 280 (3270). Accurate mass spectrometry (ESI-MS) m/z: 697.1471 [ML+], C38H42MnN8O2 requires 697.2811; 787.1922 [M2LCl+], C38H42ClMn2N8O2 requires 787.188; 822.0983 [M2LCl2+], C38H42Cl2Mn2N8O2 requires 822.1568.

Reference： [1]Golbedaghi, Reza; Salehzadeh, Sadegh; Khavasi, Hamid Reza; Blackman, Allan G. [Polyhedron, 2014, vol. 68, p. 151 - 156]

51
nickel(II) perchlorate hexahydrate [ No CAS ]
[ 7310-95-4 ]
2,2′-4-nitrobenzoyliminodi(ethylamine) trihydrochloride [ No CAS ]
C₄₀H₃₈N₈Ni₂O₈⁽²⁺⁾*2ClO₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	Stage #1: 2,2′-4-nitrobenzoyliminodi(ethylamine) trihydrochloride With sodium hydroxide In ethanol at 20℃; Stage #2: nickel(II) perchlorate hexahydrate; 2-Hydroxy-5-methylisophthalaldehyde In ethanol Reflux;	General procedure for synthesis of pendant-armed polyamine macrocyclic dinuclear nickel(II) and copper(II) complexes General procedure: A solution of NaOH (3 mmol) in ethanol (10 mL) was added to a suspension of hydrochloride salt of the appropriate amine (L, L' or L'') (1 mmol) in ethanol (10 mL). The mixture was stirred at room temperature for few minutes and filtered. Then the precipitate was washed with ethanol (10 mL) and the combined filtrate was added dropwise to a solution of M(ClO4)2*6H2O (1.5 mmol) and 2,6-diformyl-4-methylphenol (1 mmol) in ethanol (20 mL) over a period of 30 min. The resulting solution was stirred for 4 h and refluxed for 5-7 h. The precipitate thus obtained was filtered, washed with cold ethanol, followed by diethyl ether and dried under vacuum.

Reference： [1]Arthi; Haleel; Srinivasan; Prabhu; Arulvasu; Kalilur Rahiman [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, vol. 129, p. 400 - 414]

52
copper(II) perchlorate hexahydrate [ No CAS ]
[ 7310-95-4 ]
2,2′-4-nitrobenzoyliminodi(ethylamine) trihydrochloride [ No CAS ]
C₄₀H₃₈Cu₂N₈O₈⁽²⁺⁾*2ClO₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	Stage #1: 2,2′-4-nitrobenzoyliminodi(ethylamine) trihydrochloride With sodium hydroxide In ethanol at 20℃; Stage #2: copper(II) perchlorate hexahydrate; 2-Hydroxy-5-methylisophthalaldehyde In ethanol Reflux;	General procedure for synthesis of pendant-armed polyamine macrocyclic dinuclear nickel(II) and copper(II) complexes General procedure: A solution of NaOH (3 mmol) in ethanol (10 mL) was added to a suspension of hydrochloride salt of the appropriate amine (L, L' or L'') (1 mmol) in ethanol (10 mL). The mixture was stirred at room temperature for few minutes and filtered. Then the precipitate was washed with ethanol (10 mL) and the combined filtrate was added dropwise to a solution of M(ClO4)2*6H2O (1.5 mmol) and 2,6-diformyl-4-methylphenol (1 mmol) in ethanol (20 mL) over a period of 30 min. The resulting solution was stirred for 4 h and refluxed for 5-7 h. The precipitate thus obtained was filtered, washed with cold ethanol, followed by diethyl ether and dried under vacuum.

Reference： [1]Arthi; Haleel; Srinivasan; Prabhu; Arulvasu; Kalilur Rahiman [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, vol. 129, p. 400 - 414]

53
nickel(II) perchlorate hexahydrate [ No CAS ]
[ 7310-95-4 ]
2,2'-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride [ No CAS ]
C₄₀H₃₆N₁₀Ni₂O₁₂⁽²⁺⁾*2ClO₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43%	Stage #1: 2,2'-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride With sodium hydroxide In ethanol at 20℃; Stage #2: nickel(II) perchlorate hexahydrate; 2-Hydroxy-5-methylisophthalaldehyde In ethanol Reflux;	General procedure for synthesis of pendant-armed polyamine macrocyclic dinuclear nickel(II) and copper(II) complexes General procedure: A solution of NaOH (3 mmol) in ethanol (10 mL) was added to a suspension of hydrochloride salt of the appropriate amine (L, L' or L'') (1 mmol) in ethanol (10 mL). The mixture was stirred at room temperature for few minutes and filtered. Then the precipitate was washed with ethanol (10 mL) and the combined filtrate was added dropwise to a solution of M(ClO4)2*6H2O (1.5 mmol) and 2,6-diformyl-4-methylphenol (1 mmol) in ethanol (20 mL) over a period of 30 min. The resulting solution was stirred for 4 h and refluxed for 5-7 h. The precipitate thus obtained was filtered, washed with cold ethanol, followed by diethyl ether and dried under vacuum.

Reference： [1]Arthi; Haleel; Srinivasan; Prabhu; Arulvasu; Kalilur Rahiman [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, vol. 129, p. 400 - 414]

54
copper(II) perchlorate hexahydrate [ No CAS ]
[ 7310-95-4 ]
2,2'-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride [ No CAS ]
C₄₀H₃₆Cu₂N₁₀O₁₂⁽²⁺⁾*2ClO₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
44%	Stage #1: 2,2'-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride With sodium hydroxide In ethanol at 20℃; Stage #2: copper(II) perchlorate hexahydrate; 2-Hydroxy-5-methylisophthalaldehyde In ethanol Reflux;	General procedure for synthesis of pendant-armed polyamine macrocyclic dinuclear nickel(II) and copper(II) complexes General procedure: A solution of NaOH (3 mmol) in ethanol (10 mL) was added to a suspension of hydrochloride salt of the appropriate amine (L, L' or L'') (1 mmol) in ethanol (10 mL). The mixture was stirred at room temperature for few minutes and filtered. Then the precipitate was washed with ethanol (10 mL) and the combined filtrate was added dropwise to a solution of M(ClO4)2*6H2O (1.5 mmol) and 2,6-diformyl-4-methylphenol (1 mmol) in ethanol (20 mL) over a period of 30 min. The resulting solution was stirred for 4 h and refluxed for 5-7 h. The precipitate thus obtained was filtered, washed with cold ethanol, followed by diethyl ether and dried under vacuum.

Reference： [1]Arthi; Haleel; Srinivasan; Prabhu; Arulvasu; Kalilur Rahiman [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, vol. 129, p. 400 - 414]

55
nickel(II) perchlorate hexahydrate [ No CAS ]
[ 7310-95-4 ]
2,2′-benzoyliminodi(ethylamine) trihydrochloride [ No CAS ]
C₄₀H₄₀N₆Ni₂O₄⁽²⁺⁾*2ClO₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	Stage #1: 2,2′-benzoyliminodi(ethylamine) trihydrochloride With sodium hydroxide In ethanol at 20℃; Stage #2: nickel(II) perchlorate hexahydrate; 2-Hydroxy-5-methylisophthalaldehyde In ethanol Reflux;	General procedure for synthesis of pendant-armed polyamine macrocyclic dinuclear nickel(II) and copper(II) complexes General procedure: A solution of NaOH (3 mmol) in ethanol (10 mL) was added to a suspension of hydrochloride salt of the appropriate amine (L, L' or L'') (1 mmol) in ethanol (10 mL). The mixture was stirred at room temperature for few minutes and filtered. Then the precipitate was washed with ethanol (10 mL) and the combined filtrate was added dropwise to a solution of M(ClO4)2*6H2O (1.5 mmol) and 2,6-diformyl-4-methylphenol (1 mmol) in ethanol (20 mL) over a period of 30 min. The resulting solution was stirred for 4 h and refluxed for 5-7 h. The precipitate thus obtained was filtered, washed with cold ethanol, followed by diethyl ether and dried under vacuum.

Reference： [1]Arthi; Haleel; Srinivasan; Prabhu; Arulvasu; Kalilur Rahiman [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, vol. 129, p. 400 - 414]

56
copper(II) perchlorate hexahydrate [ No CAS ]
[ 7310-95-4 ]
2,2′-benzoyliminodi(ethylamine) trihydrochloride [ No CAS ]
C₄₀H₄₀Cu₂N₆O₄⁽²⁺⁾*2ClO₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50%	Stage #1: 2,2′-benzoyliminodi(ethylamine) trihydrochloride With sodium hydroxide In ethanol at 20℃; Stage #2: copper(II) perchlorate hexahydrate; 2-Hydroxy-5-methylisophthalaldehyde In ethanol Reflux;	General procedure for synthesis of pendant-armed polyamine macrocyclic dinuclear nickel(II) and copper(II) complexes General procedure: A solution of NaOH (3 mmol) in ethanol (10 mL) was added to a suspension of hydrochloride salt of the appropriate amine (L, L' or L'') (1 mmol) in ethanol (10 mL). The mixture was stirred at room temperature for few minutes and filtered. Then the precipitate was washed with ethanol (10 mL) and the combined filtrate was added dropwise to a solution of M(ClO4)2*6H2O (1.5 mmol) and 2,6-diformyl-4-methylphenol (1 mmol) in ethanol (20 mL) over a period of 30 min. The resulting solution was stirred for 4 h and refluxed for 5-7 h. The precipitate thus obtained was filtered, washed with cold ethanol, followed by diethyl ether and dried under vacuum.

Reference： [1]Arthi; Haleel; Srinivasan; Prabhu; Arulvasu; Kalilur Rahiman [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, vol. 129, p. 400 - 414]

57
[ 7310-95-4 ]
[ 79-19-6 ]
[ 37512-36-0 ]

Yield	Reaction Conditions	Operation in experiment
96.5%	In methanol for 4h; Reflux;	2.4.1. Preparation of H₃dfmp(sbdt)₂ (I), H₃dfmp(smdt)₂ (II) and H₃dfmp(tsc)₂(III) General procedure: The ligands H3dfmp(sbdt)2 (I), H3dfmp(smdt)2 (II) and H3dfmp(tsc)2 (III) were prepared by a general procedure; the preparation of H3dfmp(sbdt)2 is described here. A solution of 2,6-diformyl-4-methylphenol (1.64 g, 10 mmol) dissolved in methanol (30 ml) was added to a solution of S-benzyldithiocarbazate (3.966 g, 20 mmol) dissolved in methanol (10 ml). The obtained reaction mixture was refluxed on a water bath for 4 h. During this period a yellow solid slowly separated out. This was filtered, washed with methanol followed by petroleum ether and dried over silica gel under vacuum.
96%	In ethanol at 60℃; for 0.5h; Sonication;	Synthesis of bis-thiosemicarbazones 3a-c; general procedure General procedure: Ultrasonic irradiation methodTo a solution of thiosemicarbazide (0.182 g, 2 mmol) in ethanol(10 mL) was added the 2,6-diformylphenol derivative 2a-c (1 mmol).The reaction mixture was irradiated with an ultrasound probe for30 min at 60 °C (the reaction was monitored by TLC). After that time,the precipitate was filtered off and dried to produce 3a-c in excellentyields without any further purification.2-Hydroxy-5-methylisophthalylidenebisthiosemicarbazide (3a):White crystals; yield 96%; m.p. 282 °C; IR nmax/cm-1 (KBr): 3422 (OH,NH2), 3250 (NH), 1617, 1598 (C=N, C=C), 1290 (C=S); 1H NMR (400MHz, DMSO-d6):11.46 (s, 2H, 2NH), 9.56 (s, 1H, OH), 8.32 (s, 2H, 2CH=N), 8.17 (s, 2H, NH2), 8.07 (s, 2H, NH2), 7.63 (s, 2H, ArH), 2.25(s, 3H, CH3) ppm; 13C NMR (100 MHz, DMSO-d6): 178.15, 157.13,141.75, 130.94, 129.42, 121.27, 20.26 ppm; HRMS (EI) calcd for [M +H]+: 309.0587; found: 309.0585; Anal. calcd for C11H14N6OS2: C, 42.56;H, 4.55; N, 27.07; found: C, 42.58; H, 4.51; N, 27.11%.
96.3%	In methanol for 4h; Reflux;

89%	In ethanol at 70℃; for 6h;	2,6-Diformyl-4-methylphenol(0.164g, 1mmol) and thiosemicarbazide (0.182g, 2mmol) were dissolved in ethanol. The mixture was refluxed for 6h at 70°C, then the solvent was removed under reduced pressure. The crude product was recrystallized with hexane to obtain yellow solid (0.276g, 89%) 1H NMR (CDCl3), δ (ppm): 11.53(s, 2H), 9.57 (s, 1H), 8.33(s, 2H), 8.14 (d, 4H), 8.19 (s, 2H), 7.65 (s, 2H), 2.33(s, 3H). C11H14ON6S2 (M=310), MS [1+Na+]: m/z=333.15.
85.57%	In ethanol at 20℃; Inert atmosphere;
70%	In methanol for 6h; Reflux;	DTSC It is synthesized by condensation between DFP with thiosemicarbazide. DFP (250 mg, 1.52 mmol) is dissolved in 20 mL dry methanol. 15 mL methanol solution of thiosemicarbazide (277 mg, 3.04 mmol) is added drop wise to the former solution under stirring condition followed by reflux for 6 h. Light yellow precipitate is obtained by filtration and washed with ethanol. Yield, 330 mg (70%). ESI-TOF(+) mass (Fig. S3): 311.07 for [DTSC+H]+. 1H NMR spectrum (500 MHz, DMSO-d6), δ(ppm): 11.5287 (1H, d, J = 29.4), 10.0442 (1H, S), 9.5621 (1H, S), 8.3236 (2H,S), 8.1852 (2H, S), 7.6448 (4H, S), 2.4962 (3H, S)(Fig. S4). FTIR spectrum (Fig. S5): 1608 (CH=N).
	With acetic acid In ethanol at 65℃; for 5h;	1.2 the 2,6-dimethyl-4-methylphenol and acetaldehyde thiosemicarbazide 0.164g 0.182g was placed in a round bottom flask, treated with 20mL anhydrous This was dissolved in ethanol, was added dropwise 2 drops of glacial acetic acid as catalyst.An oil bath of 65 deg.] C was stirred at reflux for 5h, after the completion of the reaction was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure to give the crude product was purified by recrystallization from n-hexane to give a yellow
	In ethanol; water at 20℃; for 0.0833333h; Sonication; Green chemistry;	Synthesis of derivatives 3a-f and 5a-f General procedure: A mixture of dialdehydes 1a-f (1 mmol), semicarbazide hydrochloride or thiosemicarbazide (2mmol) and sodium acetate (2 mmol, added only in case of semicarbazide hydrochloride) in aqueous ethanol (75%, 10 mL)was sonicated for 5 min. Then the solvent was evaporated under reduced pressure, and the resulting residue was redissolved in 1,4-dioxane (10 mL), followed by addition of potassium carbonate (3 mmol) and iodine (2.3equiv.) in sequence. The reaction mixture was sonicated again at 60 oC for about 10 min (monitored by TLC). After cooling to ambient temperature, 5% Na2S2O3 (30 mL) was added and the mixture was extracted with CH2Cl2/MeOH (6:4, 3x15 mL). The combined organic layer was dried over anhydrous magnesium sulfate and concentrated. Upon standing at room temperature, the corresponding bis-1,3,4-oxa(thia)diazoles were precipitated in pure form which is then washed with chilled ethanol, filtered and dried.

Reference： [1]Maurya, Mannar R.; Dhaka, Sarita; Avecilla, Fernando [Polyhedron, 2014, vol. 81, p. 154 - 167]
[2]Arafa, Wael A.A.; Badry, Mohamed G. [Journal of Chemical Research, 2016, vol. 40, # 7, p. 385 - 392]
[3]Maurya, Mannar R.; Sarkar, Bithika; Kumar, Amit; Ribeiro, Nádia; Miliute, Aistè; Pessoa, João Costa [New Journal of Chemistry, 2019, vol. 43, # 45, p. 17620 - 17635]
[4]Tang, Xu; Han, Juan; Wang, Yun; Bao, Xu; Ni, Liang; Wang, Lei; Li, Longhua [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2017, vol. 184, p. 177 - 183]
[5]Bhowmick, Rahul; Alam, Rabiul; Mistri, Tarun; Das, Kalyan Kumar; Katarkar, Atul; Chaudhuri, Keya; Ali, Mahammad [RSC Advances, 2016, vol. 6, # 14, p. 11388 - 11399]
[6]Lohar, Sisir; Sinha, Sougata; Ghosh, Subrata; Das, Debasis [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2016, vol. 155, p. 75 - 80]
[7]Current Patent Assignee: JIANGSU UNIVERSITY - CN106631730, 2017, A Location in patent: Paragraph 0032; 0034; 0036
[8]Arafa, Wael Abdelgayed Ahmed; Abdel-Magied, Ahmed Fawzy [Arkivoc, 2017, vol. 2017, # 5, p. 327 - 340]

58
manganese(II) perchlorate hexahydrate [ No CAS ]
[ 7310-95-4 ]
2,2'-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride [ No CAS ]
C₄₀H₃₆Mn₂N₁₀O₁₂⁽²⁺⁾*2ClO₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	Stage #1: 2,2'-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride With sodium hydroxide In ethanol at 20℃; Stage #2: manganese(II) perchlorate hexahydrate; 2-Hydroxy-5-methylisophthalaldehyde In ethanol at 20℃; for 9.5h; Reflux;	[Mn2L1](ClO4)2 (1) An ethanolic solution (10 mL) of NaOH (3 mmol) was added to a suspension of 2,20-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride (1 mmol) in ethanol (10 mL). The mixture was stirredat room temperature for few minutes and filtered. The precipitate obtained was washed with ethanol (2 x 10 mL) and the combined filtrate was added dropwise to an ethanolic solution (20 mL) of Mn(ClO4)2*6H2O (1.5 mmol) and 2,6-diformyl-4-methylphenol (1 mmol) over a period of 30 min. The resulting solution was then stirred for 4 h and refluxed for 5 h. The precipitate thus obtained was filtered, washed with cold ethanol, followed by diethyl ether and dried under vacuum.

Reference： [1]Arthi; Shobana; Srinivasan; Mitu; Kalilur Rahiman [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2015, vol. 143, p. 49 - 58]

59
[ 7310-95-4 ]
[ 137-07-5 ]
4-methyl-2,6-dibenzothiazolylphenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With hydrogenchloride; dihydrogen peroxide In ethanol; water at 25℃; for 0.5h;
67%	In methanol; dichloromethane at 20℃; for 3h;	Example Take 2-hydroxy-5-methyl isophthalaldehyde(100 mg, 0.6 mmol) dissolved in 8 ml of dichloromethane/methanol mixture (wherein,Dichloromethane: methanol=3:5,In terms of volume ratio).Then add o-aminothiophenol(152 mg, 1.22 mmol),Stir at room temperature for 3 hours.Filter the crude product,And purified by column chromatography,A yellow solid is obtained,Marked as M-HBT,The yield was 67% (150 mg, 0.4 mmol).
37%	In methanol; dichloromethane at 20℃; for 3h;	2.2.1. Synthesis of M-HBT 2-hydroxy-5-methylisophthalaldehyde (100 mg, 0.61 mmol)was dissolved in 8 mL DCM/MeOH (3/5, v/v). Then, o-aminothiophenol(152 mg, 1.22 mmol) was added in the stirring solution.The mixture was stirred at room temperature for 3 h. The precipitatewasfiltered and further purified by a silica gel column using PE(petroleum ether)/DCM (Dichloromethane)(5/1, v/v) as eluent.The pale yellow solid was obtained after evaporation in 37% yield(150 mg, 1.65 mmol).1H NMR (400 MHz, CDCl3) d 13.98 (s, 1H), 8.10 (d, J 8.1 Hz, 4H),7.99 (d, J 7.9 Hz, 2H), 7.61e7.51 (m, 2H), 7.51e7.41 (m, 2H), 2.51 (s,3H). 13C NMR (100 MHz, CDCl3) d 154.60e153.76 (m),152.18e151.26(m), 131.90 (s), 129.57e128.39 (m), 126.45 (s), 125.25 (s), 122.46 (s),121.48 (s), 21.05e19.86 (m). MS (m/z): calcd. for C21H15N2OS2:375.0626; found: 375.0620 [MH] .

8%	In dimethyl sulfoxide at 180℃; for 2h; Inert atmosphere;	2.2.2 2,4-Dibenzothiazolylphenol (2) General procedure: 2 was prepared as previously described with some modifications [32]. Briefly, under an N2 atmosphere, 5-formylsalicylic acid (5mmol) and 2-aminobenzenethiol (10mmol) were dissolved in DMSO (2mL) and heated at 180°C for 2h. After cooling to room temperature, the mixture was poured into water and the crude product was collected by filtration. The obtained solid product was further purified by column chromatography (silica gel, hexane/dichloromethane=1:1 v/v) to give 2 as pale yellow solid. Yield: 19.9%.
	In dimethyl sulfoxide at 180℃; for 2h;

Reference： [1]Xu, Jing; Xu, Zhenghe; Wang, Zuokai; Liu, Caiyun; Zhu, Baocun; Wang, Xiuru; Wang, Kun; Wang, Jiangting; Sang, Guoqing [Luminescence, 2018, vol. 33, # 1, p. 219 - 224]
[2]Current Patent Assignee: SHANGHAI UNIVERSITY OF ENGINEERING SCIENCES; SHANGHAI CUSTOM INDUSTRIAL GOODS AND RAW MATERIAL - CN111635376, 2020, A Location in patent: Paragraph 0025; 0026; 0027; 0028
[3]Cao, Jian; Cheng, Yuxiao; Qu, Yi; Wang, Shuxin; Zhang, Jidong [Journal of Molecular Structure, 2020, vol. 1221]
[4]Zhang, Xuan; Liu, Jing-Yun [Dyes and Pigments, 2016, vol. 125, p. 80 - 88]
[5]Zhang, Xuan; Liu, Jing-Yun; Ma, Wei-Wei; Yang, Meng-Lu [Journal of Materials Chemistry B, 2016, vol. 4, # 41, p. 6662 - 6669]

60
[ 7310-95-4 ]
[ 24878-25-9 ]
C₄₂H₃₂N₄O₄ [ No CAS ]

Reference： [1]Dalton Transactions,2015,vol. 45,p. 226 - 236

61
[ 7310-95-4 ]
[ 34124-14-6 ]
C₄₆H₄₀N₄O₂ [ No CAS ]

Reference： [1]Dalton Transactions,2015,vol. 45,p. 226 - 236

62
[ 7310-95-4 ]
[ 894493-95-9 ]
C₂₅H₄₄N₄O [ No CAS ]

Reference： [1]Inorganic Chemistry,2016,vol. 55,p. 5365 - 5374

63
[ 7310-95-4 ]
[ 894493-95-9 ]
C₂₅H₄₀N₄O [ No CAS ]

Reference： [1]Inorganic Chemistry,2016,vol. 55,p. 5365 - 5374

64
[ 7310-95-4 ]
[ 67198-21-4 ]
(±)-4-(methyl)-2,6-bis(((2-(dimethylamino)cyclohexyl)imino)methyl)phenol [ No CAS ]
C₁₇H₂₄N₂O₂ [ No CAS ]

Reference： [1]Inorganic Chemistry,2016,vol. 55,p. 5365 - 5374

65
[ 7310-95-4 ]
[ 67198-21-4 ]
C₂₅H₄₄N₄O [ No CAS ]

Reference： [1]Inorganic Chemistry,2016,vol. 55,p. 5365 - 5374

66
[ 4807-55-0 ]
[ 7310-95-4 ]
2-hydroxy-5-methyl-3-[(Z)-(3-methyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidene)methyl]benzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium methylate; acetic acid at 90℃; for 0.333333h; Microwave irradiation;	Synthesis of 17a-f: General procedure: To a 5 mL glass tube, sodium methoxide (1 mmol) was added to the mixture of 2,6-diformylphenols 15a-c (0.5 mmol) and rhodanines 9a,c (1.1 mmol) in acetic acid (2 mL). The reaction tube was placed inside the cavity of the microwave, operated at power 200-250 W. The tube was irradiated in the microwave oven for appropriate time and temperature (according to Table 3). The work-up and purification step was the same used for conventional thermal heating.

Reference： [1]Arafa, Wael A. A.; Shaker, Raafat M.; Rabeh, Saleh A. [Heterocycles, 2016, vol. 92, # 7, p. 1224 - 1243]

67
[ 7310-95-4 ]
[ 6322-59-4 ]
3-[(Z)-(3-cyclohexyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidene)methyl]-2-hydroxy-5-methylbenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium methylate; acetic acid at 90℃; for 0.333333h; Microwave irradiation;	Synthesis of 17a-f: General procedure: To a 5 mL glass tube, sodium methoxide (1 mmol) was added to the mixture of 2,6-diformylphenols 15a-c (0.5 mmol) and rhodanines 9a,c (1.1 mmol) in acetic acid (2 mL). The reaction tube was placed inside the cavity of the microwave, operated at power 200-250 W. The tube was irradiated in the microwave oven for appropriate time and temperature (according to Table 3). The work-up and purification step was the same used for conventional thermal heating.

Reference： [1]Arafa, Wael A. A.; Shaker, Raafat M.; Rabeh, Saleh A. [Heterocycles, 2016, vol. 92, # 7, p. 1224 - 1243]

68
[ 23906-13-0 ]
[ 7310-95-4 ]
4-methyl-2,6-bis[2-(4,6-dimethylpyrimidin-2-yl)hydrazono]methyl}phenol [ No CAS ]

Reference： [1]New Journal of Chemistry,2016,vol. 40,p. 5976 - 5984

69
[ 42974-19-6 ]
[ 7310-95-4 ]
2,6-di(benzofuran-2-carbohydrazono)-4-methylphenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	In methanol at 20℃; for 4h;	2.1.3. Synthesis of ligand L The hot methanolic solution (25mL) of dfp (0.164g, 1mmol) and hot methanolic solution (25mL) of benzofuran-2-carbohydrazide (0.352g, 2mmol) were mixed slowly with constant stirring. The resulting mixture was stirred at room temperature for 4h. The yellow precipitate formed was filtered off, washed with hot methanol and air dried. (M. P.: 165°C, Yield: 90%). The reaction pathway is given in Scheme 1.

Reference： [1]Kokare, Dhoolesh Gangaram; Kamat, Vinayak; Naik, Krishna; Nevrekar, Anupama; Kotian, Avinash; Revankar, Vidyanand K. [Journal of Molecular Structure, 2017, vol. 1127, p. 289 - 295]

70
[ 7310-95-4 ]
[ 115-70-8 ]
2,6-bis((1-hydroxy-2-(hydroxymethyl)butan-2-ylimino)-methyl)-4-methylphenol [ No CAS ]

Reference： [1]Inorganic Chemistry,2017,vol. 56,p. 2639 - 2652

71
[ 7310-95-4 ]
[ 35578-47-3 ]
C₃₇H₂₄Br₄N₄O [ No CAS ]

Reference： [1]New Journal of Chemistry,2018,vol. 42,p. 7884 - 7900

72
[ 7310-95-4 ]
[ 87-62-7 ]
C₂₅H₂₆N₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75.3%	With acetic acid In ethanol at 50℃; for 8h;	1 2-Hydroxy-5-methyl-isophthalaldehyde (0.990 g, 6.0 mmol) and 40 ml of absolute ethanol and 2,6-dimethylaniline (99%, 1.769 g, 14.5 mmol)were added sequentially to a 100 ml one-neck round bottom flask. The reaction was carried out at 1:2 of the raw material with a slight excess of 2,6-dimethylaniline. The reaction was carried out at 50 ° C for 8 h. A few drops of glacial acetic acid were added dropwise as a catalyst. The reaction solution was orange, and a large amount of orange powder was precipitated during the reaction. The orange powder was filtered and washed 3 times with iced anhydrous ethanol. The filtrate was concentrated by rotary evaporation and placed in a refrigerator overnight to precipitate a yellow crystal and then washed again with iced ethanol. A total of 1.6789 g of product was obtained with a yield of 75.3%.
	In ethanol

Reference： [1]Current Patent Assignee: ZHEJIANG UNIVERSITY - CN108676021, 2018, A Location in patent: Paragraph 0024; 0027
[2]Hu, Qian; Jie, Suyun; Braunstein, Pierre; Li, Bo-Geng [Journal of Organometallic Chemistry, 2019, vol. 882, p. 1 - 9]

73
[ 7310-95-4 ]
[ 1099-45-2 ]
C₁₇H₂₀O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86.4%	In dichloromethane at 20℃; for 6h;	2 Synthesis of Compound 3 of Example 2 745 mg of 4.543 mmol of the compound 2 obtained in Example 1 and 6.3 g of 18.1 mmol of ethoxycarbonylmethylenetriphenylphosphine were placed in a round bottom flask.The molar ratio of the compound 2 to the ethoxycarbonylmethylenetriphenylphosphine is 1:4, 30 mL of dichloromethane is added, and the reaction is stirred at room temperature for 6 hours; after the reaction is completed, the solvent is removed by rotary evaporation, and the volume ratio is petroleum ether. : eluent of ethyl acetate = 1.5:1 was subjected to column chromatography to give compound 3 as a white solid;The obtained Compound 3 had a structural formula of a yield of 86.4%.
86.4%	In dichloromethane at 20℃; for 6h;	Synthesis of compound 2: Compound 1 (745 mg, 4.54 mmol) andethyl 2-(triphenylphosphoranylidene) acetate (6.3 g, 18.1 mmol)were dissolved in dichloromethane (30 mL), and the mixture was stirringunder roomtemperature for 6 h. The organic solventwas removedby decompression. Then, the crude product was purified by columnchromatography on silica gel to afford the compound 2 as a white solid (yield: 86.4%). 1H NMR (400 MHz, CDCl3, ppm): 8.10-8.20 (d,2H), 7.35 (s, 2H), 6.45-6.55 (d, 2H), 4.25-4.40 (m, 4H) 2.32 (s, 1H),1.30-1.40 (t, 6H), 1.27 (s, 1H). 13C NMR (101 MHz, CDCl3, ppm):167.68, 152.01, 139.47, 130.42, 129.99, 123.01, 119.15, 60.82, 20.52,14.33.

Reference： [1]Current Patent Assignee: LINGNAN NORMAL UNIVERSTITY - CN109134206, 2019, A Location in patent: Paragraph 0020; 0083; 0084; 0085
[2]Feng, Aiqing; Jia, Yongmei; Huang, Liping; Wang, Lin; Zhou, Guohua; Wang, Sheng; Liu, Peilian [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, vol. 220]

74
[ 7310-95-4 ]
C₃₄H₄₄N₄O₄ [ No CAS ]
C₇₇H₉₂N₈O₉ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	In methanol at 60℃; for 6h;	2.3. Synthesis of L Mixture of 2-hydroxy-5-methylisophthalaldehyde (0.250 g,1.25 mmol) and L1 (0.87 g, 1.25 mmol) in methanol (10 mL) is refluxedat 60 °C for 6 h (Scheme 1). The reddish product appeared after removalof the solvent is assigned as L (1.07 g, yield: 96%). Anal. calcd (%): C,72.61; H, 7.28 and N, 8.80; found: C, 72.63; H, 7.27 and N, 8.78.QTOF-MS ES+ (Fig.S3, ESI): [M+H]+=1274.24, 1HNMR (Fig.S4,ESI) (400 MHz, DMSO-d6), Z (ppm): 13.163 (1H, s), 9.337 (1H, s),8.372-8.350 (2H, s, J=2), 8.137-7.918 (6H, m, J=8.8),7.819-7.069 (10H, m, J=4), 6.472-6.122 (4H, m, J=8.8),3.277-1.137 (23H, m, J=7.2). 13CNMR (Fig.S5, ESI) (75 MHz,CDCl3), Z (ppm): 187.18, 177.18, 164.65, 161.18, 158.64, 147.19,137.22, 136.38, 129.22, 124.67, 121.10, 120.76, 117.18, 111.10,110.40, 100.06, 40.61, 40.40, and 39.10. FTIR (cm-1) (Fig.S6, ESI): (O-H) 3381.21, (C-H, aromatic) 2968.45, 2868.15 (CH]N, iminebond) 1687.71, (C]C, stretch) 1614.42, (C]O, carbonyl) 1512.19, (CeN, stretch) 1465.90, (CeO, stretch) 1375.25, 1230.58. UV-vis.(Fig. S7a, ESI): P (nm) in MeOH/ H2O (4/1, v/v) (, M-1 cm-1),240 nm (8.5×104), 314 nm (3.84×103), 403 nm (13×102). Excitationand emission spectra (Fig.S7b and S7c, ESI, Pex = 366 nm,Pem=440 nm).

Reference： [1]Banerjee, Mahuya; Ghosh, Milan; Ta, Sabysachi; Das, Jayanta; Das, Debasis [Journal of Photochemistry and Photobiology A: Chemistry, 2019, vol. 377, p. 286 - 297]

75
manganese(II) perchlorate hexahydrate [ No CAS ]
[ 7310-95-4 ]
[ 127-09-3 ]
[ 109-76-2 ]
C₂₄H₂₆N₄O₂^(2-)*2C₂H₃O₂^(1-)*ClO₄^(1-)*Mn⁽²⁺⁾*Mn⁽³⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	Stage #1: 2-Hydroxy-5-methylisophthalaldehyde; Trimethylenediamine In methanol at 20℃; for 0.666667h; Stage #2: manganese(II) perchlorate hexahydrate With air In methanol for 0.5h; Stage #3: sodium acetate In methanol for 24h;	2.3. Synthesis of [Mn2L(OAc)2]ClO4}n (1) A solution of 2,6-diformyl-4-methylphenol (100 mg, 0.6 mmol)in methanol (15 ml) was added dropwise over a period of 10 min toa solution of 1,3-diaminopropane (45 mg, 0.6 mmol) in methanol(15 ml) and the mixture was stirred in presence of air at room temperaturefor h. To the above mixture, solid Mn(ClO4)26H2O(217 mg, 0.6 mmol) was added and stirred for another h underaerobic conditions. The reaction mixture turned from yellow tobrown. Solid CH3COONa3H2O (82 mg, 0.6 mmol) was added tothis brown reaction mixture and stirring was continued for 24 h.The complex precipitated as a microcrystalline solid was collectedby filtration, washed with cold methanol and dried under vacuum.The volume of the brown filtrate was reduced to about 10 ml on asteam bath and then it was kept at low temperature (278 K) forslow evaporation. The complex separated as a dark brown crystallinematerial was filtered off and dried in air. The combinedyield was 140 mg (64%). Anal. Calc. for C28H32N4O10ClMn2: C,46.07; H, 4.42; N, 7.68. Found: C, 46.15; H, 4.38; N, 7.76. SelectedIR data (m (cm1)): 1635 (CN), 1542 and 1412 (COO), 1084 and621 (ClO4). UV-Vis data (kmax(nm) (e (104 M1 cm1))): 373(1.20), 260 (2.15).

Reference： [1]Srivastava, Ankit Kumar; Ghosh, Sabari; Pal, Samudranil [Polyhedron, 2019, vol. 172, p. 112 - 119]

76
[ 7310-95-4 ]
[ 4488-22-6 ]
[ 6046-93-1 ]
C₅₈H₃₈N₄O₂^(2-)*2Cu⁽²⁺⁾*2C₂H₃O₂^(1-) [ No CAS ]

Reference： [1]Inorganic Chemistry,2019,vol. 58,p. 4465 - 4479

77
[ 7310-95-4 ]
[ 4488-22-6 ]
[ 5970-45-6 ]
C₆₂H₄₄N₄O₆Zn₂ [ No CAS ]

Reference： [1]Inorganic Chemistry,2019,vol. 58,p. 4465 - 4479

78
[ 7310-95-4 ]
[ 144222-34-4 ]
C₅₁H₄₈N₄O₅S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In ethanol; at 20℃; for 12h;	Protect one side,Diphenylethylenediamine (4 mmol) was dissolved in ethanol (50 mL).Phenoldialdehyde (1.8 mmol) was slowly added and reacted at room temperature for 12 h.NaBH4 (14.4 mmol) was added at 0 C, and after the addition was completed, the reaction was carried out at room temperature.TLC monitoring.After the reaction was completed, water (120 mL) was added to the mixture and extracted with CH2Cl2.The organic phase was collected, washed with brine and dried over anhydrous sodium sulfateSeparation and purification by column chromatography (petroleum ether: ethyl acetate = 4:1) to obtain ligand complex(L-1).

Reference： [1]Patent: CN109666049,2019,A .Location in patent: Paragraph 0054-0059

79
[ 580-22-3 ]
[ 7310-95-4 ]
2-hydroxy-5-methyl-3-((quinolin-2-ylimino)methyl)benzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	In acetonitrile; for 8.5h;Reflux;	<strong>[580-22-3]2-Aminoquinoline</strong> (0.072 g, 0.5 mmol) in 10 mL of acetonitrilewas added slowly to a 10mL acetonitrile solution of 4-methyl-2,6-diformylphenol (0.082 mg, 0.5 mmol). The mixture was stirred for30 min and then refluxed for 8 h. The reaction mixture was cooledto room temperature. It was then filtered to remove any suspended material. Orange color and needle shaped single crystals suitablefor X-ray diffraction analysis were obtained by slow evaporationafter a few days. The productwas collected by filtration and dried inair. Yield: 0.108 g (78%). Anal. Calc. (%) for C18H14N2O2: C, 74.48; H,4.83; N, 9.65. Found: C, 74.38; H, 4.72; N, 9.60. 1H NMR (300 MHz,DMSO-D6; d ppm, TMS): 14.28 (S, 1H, phenolic OH), 10.42 (s, 1H,CHO), 9.61 (s, 1H, imine), 8.53 (d, 1H, J 6.3 Hz, Ar), 7.81e7.68 (m,5H, Ar), 7.45 (d, J 5.88 Hz, 1H, Ar), 6.54 (m, 1H, Ar), 2.33 (s, 3H,CH3); 13C NMR (DMSO-d6, 75 MHz): 192.69, 165.68, 161.15, 158.47,147.81, 139.81, 137.62, 133.67, 130.98, 128.68, 128.44, 127.99, 127.05,125.18, 124.01, 119.03, 113.63, 20.16. ESI-MS (m/z): 291.14(HL H).

Reference： [1]Journal of Molecular Structure,2020,vol. 1201

80
[ 7310-95-4 ]
[ 3119-93-5 ]
2,2'-((2-hydroxy-5-methyl-1,3-phenylene)bis(ethene-2,1-diyl))bis(3-ethylbenzothiazole-3-ium)diiodide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: N-ethyl-2-methylbenzothiazolium iodide With pyridine In methanol at 20℃; for 0.5h; Stage #2: 2-Hydroxy-5-methylisophthalaldehyde In methanol at 60℃;

Reference： [1]Dahal, Dipendra; McDonald, Lucas; Pokhrel, Sabita; Paruchuri, Sailaja; Konopka, Michael; Pang, Yi [Chemical Communications, 2019, vol. 55, # 88, p. 13223 - 13226]

81
[ 7310-95-4 ]
2-[O-(1-ethyloxyamide)]oxime-2-naphthol [ No CAS ]
C₃₅H₃₂N₄O₇ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83.5%	In ethanol at 55℃; for 4h;	2.2. The synthesis of the sensors 2-[O-(1-Ethyloxyamide)]oxime-2-naphthol were prepared accordingto a similarmethod [3]. According to the reports in related literature,the bis(salamo)-type tetraoxime sensor H3L is obtained by reacting 2-[O-(1-ethyloxyamide)] oxime-2-naphthol with 2-dihydroxy-5-methyl-1,3-benzenedialdehyde in Scheme 1 [19]. First, an orangeyellowsolid powder of 2-hydroxy-5-methyl-1,3-benzenedialdehyde(164.16 mg, 1 mmol) which was dissolved in absolute EtOH (10 mL)and placed in a round bottom flask. After pale yellow solid powder of2-[O-(1-ethyloxyamide)]oxime-2-naphthol (492.52 mg, 2 mmol) wasdissolved in absolute EtOH (20 mL) and placed in a constant pressurepartition funnel and control the drip rate and drop it within 5-6 h.The temperature was controlled at 55 °C and kept constant, and themixed solution was then heated under reflux for 4 h, a small amount of pale-yellow precipitate was formed. The solvent was removedunder reduced pressure by a rotary evaporator to give a crude productwhich was recrystallized to give the symmetric bis(salamo)-typetetraoxime sensor H3L in EtOH and trichloromethane solvents. Yield:83.5%. M. p.: 121-122 °C. Anal. calc. for C35H32N4O7 (%): C, 67.73; H,5.20; N, 9.03. Found (%): C, 67.85; H, 5.09; N, 8.92. 1H NMR (500 MHz,CDCl3) δ 10.85 (s, 2H), 10.07 (s, 1H), 9.16 (s, 2H), 8.39 (s, 2H), 7.92 (d,J = 5.0 Hz, 2H), 7.76 (dd, J = 4.6, 5.2 Hz, 4H), 7.51 (d, J = 8.4 Hz, 2H),7.34 (d, J = 7.5 Hz, 4H), 7.19 (d, J = 9.0 Hz, 2H), 4.54 (m, 8H), 2.24 (s,3H) (Fig. S1). IR (KBr; cm-1): 3420 [v(O-H)], 2932 [v(C-H)], 1615[v(C=N)], 1360 [v(C=C)], 945 [v(Ar-O)].
83.5%	In ethanol for 4h; Reflux;

Reference： [1]Pan, Ying-Qi; Xu, Xin; Zhang, Yu; Zhang, Yang; Dong, Wen-Kui [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2020, vol. 229]
[2]Pan, Ying-Qi; Wang, Li; Yu, Meng; Zhang, Yang; Zhang, Yu [Applied Organometallic Chemistry, 2020]

82
[ 7310-95-4 ]
[ 14134-81-7 ]
C₃₅H₄₀N₂O⁽²⁺⁾*2I^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With piperidine In ethanol at 80℃; for 3h;	2.2. Synthesis of the probe DFIN 1-ethyl-2,3,3-trimethyl-3H-indol-1-ium iodide (0.22 g, 1 mmol) and2,6-diformyl-4-methyl phenol (0.08 g, 0.5 mmol) were dissolved in20.0 mL of ethanol, followed by addition of two drops of piperidine.The mixture was heated to reflux at 80 °C for 3 h. After checking theprogress of the reaction by TLC, the reaction mixture was cooled to25 °C. The precipitate formed was filtered, dried and purified by columnchromatography using petroleum ether/ethyl acetate (7:3) as eluent togive the probe DFIN as red solid.Yield: (0.23 g, 76%), M.pt: 126 °C. Elemental analysis forC35H40N2O2+: C, 83.29; H, 7.99; N, 5.55%. Found: C, 82.87; H, 7.41 N,5.12%. 1H NMR (DMSO-d6, ppm): 10.2 (s, 1 H) 8.5 (t, J=12.1 Hz, 2 H),8.3 (d, J=9.2 Hz, 2 H), 8.0 (d, J=7.6 Hz, 2 H), 7.7 (d, J=9.6 Hz, 2 H), 7.5 (s, 2 H), 7.4 (t, J=12.8 Hz, 2 H), 7.1 (d, J=8.8 Hz, 2 H), 4.6 (q,J=14.3 Hz, 4 H), 2.3 (s, 3 H), 2.1 (s, 12 H), 1.6 (t, J=8.0 Hz, 6 H). 13CNMR (DMSO-d6, ppm) 171. 9, 150.6, 143.8, 140.4, 136.7, 128.6, 127.6,125.8, 121.1, 117.9, 113.0, 111.1, 53.2, 46.0, 25.5, 22.6, 13.3. HR-MS(ESI) for C35H40N2O2+ [M]+ 504.7.2.3. Synthesis

Reference： [1]Asaithambi, Gomathi; Periasamy, Viswanathamurthi [Journal of Photochemistry and Photobiology A: Chemistry, 2020, vol. 389]

83
[ 7310-95-4 ]
[ 19353-92-5 ]
(N',N'''E,N',N'''E)-N',N'''-((2-hydroxy-5-methyl-1,3-phenylene)bis(methanylylidene))bis(4-(dimethylamino)benzohydrazide) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With trifluoroacetic acid In dimethyl sulfoxide at 20 - 100℃; for 16h;	General experimental procedure for the synthesis ofcompounds 3. General procedure: A mixture of the corresponding dialdehyde(1 eq.) and the corresponding hydrazide (2 eq.) were dissolvedin DMSO (up to a 0.1-0.01 M concentration) and a few dropsof trifluoroacetic acid were added. The reaction mixture washeated at 100°C for 4 hours and left at room temperatureovernight (12 h). To the reaction mixture water was added(90% v/v) and the resulting precipitate was filtered, washedwith water and dried to afford pure product.
81%	With trifluoroacetic acid In dimethyl sulfoxide at 20 - 100℃;	General experimental procedure for the synthesis ofcompounds 3 General procedure: A mixture of the corresponding dialdehyde(1 eq.) and the corresponding hydrazide (2 eq.) were dissolvedin DMSO (up to a 0.1-0.01 M concentration) and a few dropsof trifluoroacetic acid were added. The reaction mixture washeated at 100°C for 4 hours and left at room temperatureovernight (12 h). To the reaction mixture water was added(90% v/v) and the resulting precipitate was filtered, washedwith water and dried to afford pure product. (N',N'''E,N',N'''E)-N',N'''-((2-hydroxy-5-methyl-1,3-phenylene)bis(methanylylidene))bis(4-(dimethylamino)benzohydrazide) 3a. Yellow solid. Yield 81%(0.445 g). m.p.209-212 °C. Rf=0.29 (silica, DCM:MeOH=9:1).1HNMR (500.13 MHz, DMSO-d6): δ= 12.42 (s, 1H, -OH), 11.81(s, 2H, -NH), 8.67 (s, 2H, H5), 7.84 (d, 4H, 3J = 8.9 Hz,H7/H11), 7.50 (s, 2H, H3), 6.77 (s, 4H, 3J = 8.9 Hz, H8/H10),3.01 (s, 12H, -N(CH3)2), 2.31 (s, 3H, -CH3) ppm. 13C NMR(125.77 MHz, DMSO-d6): 162.7 (C=O), 154.4 (C-1), 152.6(C-9), 144.5 (C-5), 129.7 (C-3), 129.2 (C-7/C-11), 128.1 (C-4), 120.2 (C-2), 118.9 (C-6), 110.9 (C8/C10), 39.6 (-N(CH3)2overlapped with DMSO), 20.0 (-CH3) ppm. HRMS (APCI, +)m/z: calc. for C27H31N6O3 [M+H]+487.2458; found 487.2447

Reference： [1]Coman, Anca G.; Hadade, Niculina D.; Hanganu, Anamaria; Mǎdǎlan, Augustin M.; Matache, Mihaela; Paun, Anca; Popescu, Codruţa C. [Revue Roumaine de Chimie, 2020, vol. 65, # 1, p. 109 - 114]
[2]Coman, Anca G.; Paun, Anca; Popescu, Codruța C.; Hadade, Niculina D.; Hanganu, Anamaria; Mădălan, Augustin M.; Matache, Mihaela [Revue Roumaine de Chimie, 2021, vol. 65, # 1, p. 109 - 114]

84
[ 120-72-9 ]
[ 7310-95-4 ]
3-(di(1H-indol-3-yl)methyl)-2-hydroxy-5-methylbenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With water; β‐cyclodextrin at 60℃; for 3h; Green chemistry; chemoselective reaction;	1.2. General experimental procedure for the β-CD hydrate catalysed reactions of indoles with aldehydes General procedure: To a suspension of indole 1 (1.0 mmol), and aldehyde 2 (0.5 mmol) in water (3 mL), the β-CD hydrate (4 mol %) was added and the mixture was stirred at 60oC and the progress of the reaction was monitored with TLC. After completion of reaction, the reaction mixture was cooled to 5oC, ethyl acetate (15 mL) was added to the reaction mixture and the catalyst was separated by filtration for reuse. The residual catalyst was repeatedly washed with ethyl acetate (3×5 mL). The combined organic layer was separated and dried with anhydrous sodium sulphate. The solvent was removed under reduced pressure to furnish the crude product 3, which was further purified by filtration chromatography on a short column of silica gel using 5-15% ethyl acetate-hexane as eluent.

Reference： [1]Das, Asit Kumar; Sepay, Nayim; Nandy, Sneha; Ghatak, Avishek; Bhar, Sanjay [Tetrahedron Letters, 2020, vol. 61, # 37]

85
[ 1824-81-3 ]
[ 7310-95-4 ]
2-hydroxy-5-methyl-3-[{(6-methylpyridin-2-yl)imino}methyl]benzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With acetic acid In acetonitrile for 1h; Reflux; Inert atmosphere;	2.2. Synthesis of L 2-hydroxy-5-methylisophthalaldehyde (A) was prepared byknown literature procedure [16]. A mixture of A (0.328 g, 2.0 mmol)and 2-amino-6-methylpyridine (B) (0.216 g, 2.0 mmol) in acetonitrile(20 mL) was refluxed for 1 h under nitrogen atmosphere. Thesolution was concentrated in vacuum to get crude product at RT.The product was purified by column chromatography using solventethylacetate: hexane (2:1) and finally the yellow crystalline solidof L was isolated (Yield 75%), IR νmax (cm-1) (Fig. S1): 3404 for νmax(O-H), 2931 for aldehyde νmax (C-H); 1606 for νmax (CN)(azomethine); 1442 for νmax (C-N) (aromatic); 1675 for νmax(CO) and 1199 for νmax (C-O) (phenolate). 1H NMR (CDCl3,400 MHz) (Fig. S2): δ (ppm) 2.37 (s, 3H), 2.58 (s, 3H), 7.57(s, 1H), 7.27 (s, 1H), 7.12 (d, 1H), 7.68 (d, 1H), 7.76-7.75 (dd, 1H),9.46 (s, 1H), 10.55 (s, 1H).

Reference： [1]Jana, Abhimanyu; Aher, Abhishek; Brandao, Paula; Ali, Syed Samim; Samanta, Sandip Kumar; Mondal, Gopinath; Bera, Pradip; Santra, Ananyakumari; Manna, Sunil Kumar; Mahapatra, Ajit Kumar; Bera, Pulakesh [Polyhedron, 2020, vol. 192]

86
[ 7310-95-4 ]
[ 615-21-4 ]
C₂₃H₁₈N₆OS₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	In ethanol at 80℃; for 6h;	2.2. Synthesis As shown in Scheme 1, 2,6-diformyl-4-methylphenol was synthesizedaccording to the method in the literature with slight modification[24]. The hot ethanol solution (15 mL) of 2-hydrazinobenzothiazole (0.661 g, 0.4 mmol) was dripwised tothe ethanol solution (15 mL) of 2,6-diformyl-4methylphenol(0.328 g, 0.2 mmol), then the mixture solution was stirred andrefluxed for 6 h at 80 °C. Finally, the above steps were ended untilthe TLC plate showed a completed reaction. After cooling to roomtemperature, the solution was evaporated to 4 mL using a rotaryevaporator and recrystallized in ethanol. After vacuum drying, ayellow solid was obtained. Yield: 0.6962 g (76%). 1H NMR(600 MHz, DMSO d6) δ 12.08 (s, 3H), 11.86 - 11.38 (m, 1H), 8.49(s, 2H), 7.77 (s, 2H), 7.51 (s, 2H), 7.31 (t, J = 7.5 Hz, 2H), 7.12 (t,J = 7.7 Hz, 2H), 2.33 (s, 3H). 13C NMR (101 MHz, Benzene d6) δ 230.55, 228.15, 206.22, 203.61, 202.93, 200.57, 197.74, 165.89,165.16, 163.57, 149.81, 147.46, 144.94, 141.87, 130.80, 127.61,126.91, 125.54, 122.66, 121.68, 120.67, 119.70, 18.52. ESI-MSCalcd m/z: 459.1073, found 481.0895 [M + Na]+ (Fig. S6-S7, supplementarymaterials).
	In methanol Reflux;

Reference： [1]Chen, Lijuan; Han, Qingxin; Jiang, Huie; Li, Nihao; Li, Zhijian; Liu, Xinhua; Meng, Qingjun [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2022, vol. 268]
[2]Borah, Nilotpal; De, Sagnik; Gogoi, Abhijit; Das, Gopal [New Journal of Chemistry, 2020, vol. 44, # 43, p. 18703 - 18713]

87
[ 7310-95-4 ]
[ 3119-93-5 ]
C₂₉H₂₈N₂OS₂⁽²⁺⁾*2BF₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	Stage #1: 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehyde; 2-methyl-3-ethyl benzothiazolium iodide With piperidine In ethanol at 95℃; for 24h; Stage #2: With hydrogen tetrafluoroborate In ethanol at 20℃; for 2h;	2.1. Preparation of the probe Qcy-OH To a solution containing 183 mg (0.6 mmol) of 3ethyl2methylbenzothiazolium iodide and 0.3 mmol of the 2hydroxy5methyl1,3benzenedicarboxaldehyde in 7 mL of anhydrous ethanol, 100 lL piperidine was added and the mixture was then heatedat 95 C for 24 h. After cooling to room temperature, 100 lL HBF4was added and stirred for another 2 h. The solution was thenremoved under reduced pressure. The crude product was recrystallizedfrom acetonitrile (5 mL) to give probe Qcy-OH as orange solid(156 mg, yield 79 %), m.p.: 253-254 oC1H NMR (DMSO d6,400 MHz, ppm): d = 8.47 (d, J = 8.0 Hz, 2H), 8.43 (d, J = 15.6 Hz,2H), 8.34 (d, J = 8.4 Hz, 2H), 8.22 (s, 2H), 8.04 (d, J = 15.6 Hz, 2H),7.90 (t, J = 7.8 Hz, 2H), 7.82 (t, J = 7.6 Hz, 2H), 5.01-4.98 (m, 4H),2.45 (s, 3H), 1.51 (t, J = 7.2 Hz, 6H); 13C NMR (DMSO d6,100 MHz, ppm): d = 172.54, 160.95, 155.91, 154.31, 144.48, 143.83,141.88, 136.71, 135.73, 134.37, 131.07, 130.53, 129.93, 129.38,129.25, 128.45, 127.23, 125.43, 124.41, 123.40, 122.92, 118.98,117.632, 114.29, 113.63, 45.60, 21.13, 20.94, 15.22, 13.49; HRMSm/z calculated for C29H28N2OS22+: 483.1559, found 483.1556.

Reference： [1]He, Song; Liu, Chang; Wang, Zhiming; Wu, Jianhong; Yan, Huimin; Zeng, Xianshun; Zhao, Liancheng [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2022, vol. 278]

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CAS No. :	7310-95-4	MDL No. :	MFCD00016596
Formula :	C₉H₈O₃	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	ZBOUXALQDLLARY-UHFFFAOYSA-N
M.W :	164.16	Pubchem ID :	81744
Synonyms :

Num. heavy atoms :	12
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.11
Num. rotatable bonds :	2
Num. H-bond acceptors :	3.0
Num. H-bond donors :	1.0
Molar Refractivity :	44.21
TPSA :	54.37 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.3 cm/s

Log Po/w (iLOGP) :	0.98
Log Po/w (XLOGP3) :	1.41
Log Po/w (WLOGP) :	1.33
Log Po/w (MLOGP) :	0.47
Log Po/w (SILICOS-IT) :	2.12
Consensus Log Po/w :	1.26

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Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Log S (ESOL) :	-1.98
Solubility :	1.7 mg/ml ; 0.0104 mol/l
Class :	Very soluble
Log S (Ali) :	-2.16
Solubility :	1.15 mg/ml ; 0.00698 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.1
Solubility :	1.31 mg/ml ; 0.00798 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.0

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

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[ CAS No. 7310-95-4 ] {[proInfo.proName]}

Quality Control of [ 7310-95-4 ]

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[ 7310-95-4 ] Synthesis Path-Downstream 1~87

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[ 7310-95-4 ]