* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Stage #1: With oxygen; ozone In dichloromethane at -78℃; for 0.583333 h; Stage #2: With dimethylsulfide In dichloromethane at -78 - 20℃; for 4 h; Stage #3: With water; potassium carbonate In methanol at 55℃; for 1 h;
A stirred solution of Part B compound (1.94 g, 9.19 mmol) in CH2Cl2 (100 ML) protected from atmospheric moisture by a calcium chloride drying tube was cooled to -78° C. and a 3percent O3/O2 gas mixture is bubbled through the solution until a blue color persists (~35 min).The solution was purged with nitrogen gas and then dimethylsulfide (5 ML) was added and the reaction allowed to warm to room temperature.After 4 h, the solution was evaporated and the residue redissolved in MeOH (8 ML) to which was added water (8 ML) and potassium carbonate (1.1 g, 80 mmol).The mixture was heated to 55° C. under argon for 1 h and then cooled, neutralized with 1 M potassium hydrogen sulfate to PH 7 and extracted twice with CH2Cl2.The organic extracts were combined, dried (MgSO4) and evaporated.Purification by flash chromatography provided the title compound as a light yellow crystalline solid, 1.47 g (80percent yield). LC/MS gave the correct molecular ion [(M+H)+=201] for the desired compound.
Reference：
[1] Patent: US2003/225091, 2003, A1, . Location in patent: Page 29
[2] Chemical and Pharmaceutical Bulletin, 1993, vol. 41, # 6, p. 1166 - 1168
[3] Chemical and Pharmaceutical Bulletin, 1993, vol. 41, # 6, p. 1166 - 1168
6
[ 50-00-0 ]
[ 95-56-7 ]
[ 1829-34-1 ]
Yield
Reaction Conditions
Operation in experiment
100%
With triethylamine; magnesium chloride In acetonitrile for 3 h; Heating / reflux
To a solution of 2-bromophenol (3.17 g, 18.3 mmol) in acetonitrile (85 ml.) was added magnesium chloride (2.62 g, 27.5 mmol), paraformaldehyde (3.7 g, 0.13 mmol) and Et3N (6.4 ml, 46 mmol). The reaction was heated at reflux for 3h, allowed to cool, diluted with 1 N HCI (100 ml_, and extracted with ethyl acetate. The organic layer was washed with aqueous sodium chloride, dried (MgSO4), and concentrated to afford the title compound (3.74 g, 100percent): MS (ES) m/e 202.1 (M + H)+. This was used without further purification.
96%
With triethylamine; magnesium chloride In tetrahydrofuran for 1.5 h;
2-Bromoρhenol (97 g, 0.56 mol), THF (1.0 L), and paraformaldehyde, prilled (84.0 g, 2.80 mol) were charged to a 5 L 3-neck round-bottom flask. Triethylamine (TEA) (400 mL) EPO <DP n="153"/>was added, followed by MgCl2 (200 g, 2.10 mmol) added portionwise over a 90 minutes, while stirring with an overhead stirrer. The reaction was white, cloudy, and viscous, and turned bright yellow on addition of the MgCl2. The reaction was allowed to stir overnight under a nitrogen atmosphere. The reaction was neutralized causiously with phosphoric acid (300 mL) and brine (500 mL) diluted with ethyl acetate (500 mL). The organic layer was separated and washed with water (500 mL X 3) and brine (500 mL), and dried over Na2SO4. The solvents were evaporated and the residue was dissolved in ethyl acetate. The solution was filtered through 6 x 4 inch a silica gel plug with ethyl acetate (1.5 L) as eluant. The solution was concentrated to give crude 3-bromo-2-hydroxy-benzaldehyde. (107g, 96percent). 1H NMR (400 MHz, DMSO) δ ppm 11.28 (s, IH), 10.06 (s, IH), 7.89 (dd, IH, J= 1.6, 7.8 Hz), 7.78 (dd, IH, J= 1.6, 7.4 Hz), 7.02 (t, IH, J= 7.8 Hz).
95%
With triethylamine; magnesium chloride In acetonitrileReflux
In a manner analogous to that of the literature (Hofslokken et al. Acta. Chemica Scand. 1999, 55, 258), a stirred suspension of 2-bromophenol (76-0, 3.5 g, 20 mmol), and paraformaldehyde (8.1 g, 270 mmol) in 100 mL of dry acetonitrile at room temperature was treated with MgCl2 (2.85 g, 30 mmol) and triethylamine (TEA, 10.45 ml, 75 mmol). The mixture was stirred vigorously at reflux O/N. After this period of time, the mixture was cooled to room temperature, then 30 mL of 5percent HCl was added and the product extracted with Et2O to give 4.0 g (95percent) of 76-1. TLC (hexanes/dichloromethane, 3:1): Rf=0.3; detection: CMA and UV
52%
With triethylamine; magnesium chloride In acetonitrile at 20℃; Heating / reflux
To a stirred suspension of 2-bromophenol (100-0, 3.5 g, 20 mmol) and paraformaldehyde (8.1 g, 270 mmol) in 100 mL of dry acetonitrile at room temperature was added MgCl2 (2.85 g, 30 mmol) and triethylamine (10.45 mL, 75 mmol). The reaction was stirred vigorously at reflux overnight. The mixture was cooled down to room temperature, then 30 mL of 5percent HCl added and the product extracted with Et2O to give 4 g (95percent) of 100-1.E. Standard Procedure for the Synthesis of Tethers T100a and T100b Construction of the individual stereoisomers proceeded from 3-bromo-2-hydroxy-benzaldehyde (100-2, Hofslokken et al. Acta. Chemica Scand. 1999, 53, 258) and toluene-4-sulfonic acid 2-hydroxy-but-3-enyl ester (100-4, Buono et al. Eur. J. Org. Chem. 1999, 1671) using a key ring closing metathesis step (Grubbs, R. J. Org. Chem. 1998, 63, 864-866; Gross, J. Tetrahedron Letters, 2003, 44, 8563-8565; Hoveyda, A. J. Am. Chem. Soc. 1998, 120, 2343-2351) as illustrated for the (R)-isomer Boc-T100a.1H NMR (300 MHz, DMSO-d6): δ 1.16 (s, 9H), 1.5-1.8 (m, 3H), 1.9-2.1 (m, 1H), 2.4-2.6 (m, 2H), 2.6-3.0 (m, 4H), 3.6 (tdd, 2H, 29.7, 11.3, 5.6 Hz), 3.9-4.1 (m, 1H), 4.8 (t, 1H, J=5.7 Hz), 6.8-6.9 (m, 1H), 6.9-7.0 (m, 1H), 6.8-6.9 (m, 2H)13C NMR (75 MHz, DMSO-d6): δ 23.6, 23.8, 26.5, 28.2, 29.6, 63.5, 76.2, 77.2, 119.2, 121.5, 127.1, 127.2, 128.8, 152.1, 155.5.The (S)-isomer, T100b, can be synthesized similarly.An alternative synthetic scheme as illustrated can also be utilized that relies on an enzymatic resolution step to provide Cbz-T100a in 15-20percent overall yield.
30 g
Stage #1: With triethylamine; magnesium chloride In tetrahydrofuran for 0.5 h; Stage #2: for 16 h; Reflux
14.5 g of anhydrous magnesium chloride was dispersed in 250 ml of anhydrous tetrahydrofuran.7.5 g of paraformaldehyde and 21 ml of triethylamine were added, and the reaction was stirred for 30 minutes.17.5 g of o-bromophenol was added, and after the addition, the mixture was stirred and heated to reflux for 16 hours.After cooling to room temperature, 500 ml of dilute hydrochloric acid was added and extracted with ethyl acetate.The organic phase was dried over anhydrous sodium sulfate, filtered and evaporated.Separation and purification on a silica gel column gave 30 g of yellow oil.
Reference：
[1] Patent: WO2007/118130, 2007, A2, . Location in patent: Page/Page column 28
[2] Organic and Biomolecular Chemistry, 2016, vol. 14, # 30, p. 7268 - 7274
[3] Patent: WO2006/86609, 2006, A2, . Location in patent: Page/Page column 151-152
[4] Bioorganic and Medicinal Chemistry Letters, 2006, vol. 16, # 12, p. 3197 - 3200
[5] Patent: US9181298, 2015, B2, . Location in patent: Page/Page column 33; Sheet 18
[6] Patent: US2018/110824, 2018, A1, . Location in patent: Paragraph 0481; 0482; 0483
[7] Journal of Medicinal Chemistry, 2001, vol. 44, # 17, p. 2753 - 2771
[8] Organic Syntheses, 2005, vol. 82, p. 64 - 68
[9] Tuberculosis, 2018, vol. 108, p. 96 - 98
[10] Journal of Medicinal Chemistry, 2011, vol. 54, # 19, p. 6724 - 6733
[11] Journal of Medicinal Chemistry, 2014, vol. 57, # 24, p. 10424 - 10442
[12] Dyes and Pigments, 2017, vol. 136, p. 292 - 301
[13] Tetrahedron Letters, 2010, vol. 51, # 46, p. 6018 - 6021
[14] Patent: US2008/194672, 2008, A1, . Location in patent: Page/Page column 37-39
[15] Journal of Medicinal Chemistry, 2011, vol. 54, # 24, p. 8305 - 8320
[16] Organic Letters, 2015, vol. 17, # 23, p. 5824 - 5827
[17] Helvetica Chimica Acta, 2009, vol. 92, # 11, p. 2313 - 2329
[18] Tetrahedron Asymmetry, 2004, vol. 15, # 8, p. 1343 - 1354
[19] Tetrahedron Letters, 2005, vol. 46, # 19, p. 3357 - 3358
[20] Tetrahedron Letters, 2005, vol. 46, # 32, p. 5285 - 5287
[21] Bioorganic and Medicinal Chemistry Letters, 2006, vol. 16, # 14, p. 3829 - 3832
[22] Tetrahedron, 2007, vol. 63, # 40, p. 9997 - 10002
[23] Patent: WO2009/80725, 2009, A1, . Location in patent: Page/Page column 81-82
[24] Patent: WO2010/42475, 2010, A1, . Location in patent: Page/Page column 88
[25] Patent: US2010/174065, 2010, A1, . Location in patent: Page/Page column 38
[26] Patent: US2011/269738, 2011, A1, . Location in patent: Page/Page column 40-41
[27] Patent: WO2011/134280, 2011, A1, . Location in patent: Page/Page column 82; 83
[28] Journal of the American Chemical Society, 2013, vol. 135, # 19, p. 7102 - 7105
[29] European Journal of Organic Chemistry, 2014, vol. 2014, # 27, p. 6077 - 6083
[30] Patent: CN108164564, 2018, A, . Location in patent: Paragraph 0072; 0076; 0077; 0078
[31] Patent: WO2009/158467, 2009, A2, . Location in patent: Page/Page column 85
[32] Patent: WO2003/104227, 2003, A1, . Location in patent: Page 62
[33] Chirality, 2018,
7
[ 95-56-7 ]
[ 1829-34-1 ]
Reference：
[1] Journal of Medicinal Chemistry, 2002, vol. 45, # 17, p. 3573 - 3575
[2] Chemical and Pharmaceutical Bulletin, 1993, vol. 41, # 6, p. 1166 - 1168
[3] Chemical and Pharmaceutical Bulletin, 1993, vol. 41, # 6, p. 1166 - 1168
[4] Chemical and Pharmaceutical Bulletin, 1993, vol. 41, # 6, p. 1166 - 1168
[5] Patent: US5965741, 1999, A,
8
[ 444095-29-8 ]
[ 1829-34-1 ]
Reference：
[1] Synthesis, 2006, # 10, p. 1578 - 1589
9
[ 90-02-8 ]
[ 1829-34-1 ]
Reference：
[1] Organic and Biomolecular Chemistry, 2013, vol. 11, # 31, p. 5147 - 5155
Reference：
[1] Journal of Medicinal Chemistry, 2002, vol. 45, # 17, p. 3573 - 3575
14
[ 38770-76-2 ]
[ 1829-34-1 ]
Reference：
[1] Chemical and Pharmaceutical Bulletin, 1993, vol. 41, # 6, p. 1166 - 1168
[2] Chemical and Pharmaceutical Bulletin, 1993, vol. 41, # 6, p. 1166 - 1168
[3] Chemical and Pharmaceutical Bulletin, 1993, vol. 41, # 6, p. 1166 - 1168
15
[ 152211-65-9 ]
[ 1829-34-1 ]
Reference：
[1] Chemical and Pharmaceutical Bulletin, 1993, vol. 41, # 6, p. 1166 - 1168
16
[ 67-66-3 ]
[ 95-56-7 ]
[ 1829-34-1 ]
[ 2973-78-6 ]
Reference：
[1] Journal of the Indian Chemical Society, 1932, vol. 9, p. 173,177
[2] Journal of the Indian Chemical Society, 1932, vol. 9, p. 173,177
Reference：
[1] Proceedings of the Iowa Academy of Science, 1945, vol. 52, p. 191,195
24
[ 68448-62-4 ]
[ 1829-34-1 ]
Reference：
[1] Chemische Berichte, 1909, vol. 42, p. 3701
25
[ 67-66-3 ]
[ 95-56-7 ]
[ 1829-34-1 ]
[ 2973-78-6 ]
Reference：
[1] Journal of the Chemical Society, 1929, p. 1641
26
[ 75-25-2 ]
[ 95-56-7 ]
[ 1829-34-1 ]
[ 2973-78-6 ]
Reference：
[1] Journal of the Chemical Society, 1929, p. 1641
27
[ 67-66-3 ]
[ 95-56-7 ]
[ 1829-34-1 ]
[ 2973-78-6 ]
Reference：
[1] Journal of the Indian Chemical Society, 1932, vol. 9, p. 173,177
[2] Journal of the Indian Chemical Society, 1932, vol. 9, p. 173,177
28
[ 67-66-3 ]
[ 95-56-7 ]
[ 1829-34-1 ]
[ 2973-78-6 ]
Reference：
[1] Journal of the Chemical Society, 1929, p. 1641
29
[ 75-25-2 ]
[ 95-56-7 ]
[ 1829-34-1 ]
[ 2973-78-6 ]
Reference：
[1] Journal of the Chemical Society, 1929, p. 1641
30
[ 1829-34-1 ]
[ 74-88-4 ]
[ 88275-87-0 ]
Yield
Reaction Conditions
Operation in experiment
99%
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 18 h;
K2C03 (13.51 g, 97.75 mmol) and CH3I (2.43 mL, 39.1 mmol) were added to a sol. of 3-bromo-2-hydroxybenzaldehyde (6.55 g, 32.58 mmol) in DMF (164 mL). The r.m. was stirred at r.t. for 18 h. The mixture was poured into a 1 N HCl sol. and the aq. layer was extracted with EtOAc. The o.l. was separated, dried (MgS04), filtered and concentrated in vacuo. Yield: 7 g of intermediate 25 (99percent yield) as a brown-orange oil.
94%
Stage #1: With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 18 h; Stage #2: With hydrogenchloride In water; N,N-dimethyl-formamide
To a solution of 3-bromo-2-hydroxy- benzaldehyde (2.72 g, 13.53 mmol) in DMF (70 mL) were added potassium carbonate (5.61 g, 40.59 mmol) and iodomethane (1.01 ml_, 16.24 mmol). The reaction mixture was stirred at RT. After 18 h, the mixture was acidified with cooling using 1 M HCI (aq), extracted with EtOAc. The organic extract was dried (Na2S04), filtered and concentrated in vacuo to afford the title compound as an oil (2.73 g, 94percent). NMR (300 MHz, CDCI3): δ 10.36 (s, 1 H), 7.85-7.79 (m, 2H), 7.15 (dt, J = 7.7and 0.7 Hz, 1 H), 4.00 (s, 3H).
93%
With potassium carbonate In acetone at 60℃; for 2 h;
3-Bromo-2-hydroxybenzaldehyde (5.0 g, 24.87 mmol) was dissolved in acetone (200 ml) and treated with iodomethane (5.3 g, 37.34 mmol) and potassium carbonate (5.2 g, 37.63 mmol). The mixture was heated to 60° C for 2 hr then cooled to room temperature and filtered. The filtrate was concentrated to dryness and re-dissolved in ethyl acetate. The solution was washed with saturated aqueous sodium bicarbonate and dried over MgSO4. After concentration, the residue was passed through a layer of silica gel, which was eluted with 50percent ethyl acetate in hexanes. The eluent was concentrated to give 2.0 g (93percent) of 3-bromo-2- methoxybenzaldehyde as a colorless syrup. MS 215.0 (M+H); HPLC rt = 13.8 min [a].
88%
With tetra(n-butyl)ammonium hydroxide; sodium hydroxide In dichloromethane; water at 20℃; for 16 h;
Bu4NOH (40 wtpercent in H2O; 11.1 mL, 16.9 mmol), NaOH (1.15 g, 28.8 mmol), and MeI (2.64 mL, 42.4 mmol) were added to a solution of 3-bromosalicylaldehyde (10) (1.70 g, 8.46 mmol) in CH2Cl2 (60 mL) and water (60 mL). The mixture was vigorously stirred at r.t. for 16 h under air. The layers were separated, the aqueous layer was extracted with CH2Cl2, the combined organic layers were dried (Na2SO4), and the solvent was evaporated. Purification of the residue by flash chromatography (silica gel, isohexane-EtOAc, 15:1) provided methyl ether 11 as a colorless solid; yield : 1.60 g (7.44 mmol, 88percent); mp 30-32 °C. IR (ATR): 3339, 3068, 3012, 2954, 2889, 2826, 2750, 2057, 1679, 1654, 1584, 1447, 1418, 1387, 1233, 1165, 1115, 1069, 986, 851, 801, 779, 747, 699 cm-1. 1H NMR (500 MHz, CDCl3): δ = 3.99 (s, 3 H), 7.14 (td, J = 7.8, 0.7 Hz, 1H), 7.80-7.82 (m, 2 H), 10.36 (d, J = 0.7 Hz, 1H). 13C NMR and DEPT (125 MHz, CDCl3): δ = 63.51 (CH3), 118.20 (C), 125.78 (CH), 127.87 (CH), 130.95 (C), 139.50 (CH), 160.13 (C), 189.14 (CHO). MS (EI): m/z (percent) = 216 (68), 214 (67, [M+]), 198 (95), 196 (81), 185 (25), 184 (23), 183 (17), 182 (23), 170 (38), 168 (24), 145 (35), 143 (35), 119 (35), 92 (43), 77 (78), 63 (100), 50 (34), 38 (18). Anal. Calcd for C8H7BrO2: C, 44.68; H, 3.28. Found: C, 44.87; H, 3.17.
Reference：
[1] Patent: WO2013/10904, 2013, A1, . Location in patent: Page/Page column 65
[2] Journal of Medicinal Chemistry, 2002, vol. 45, # 17, p. 3573 - 3575
[3] Patent: WO2011/33265, 2011, A1, . Location in patent: Page/Page column 93-94
[4] Patent: WO2009/76602, 2009, A1, . Location in patent: Page/Page column 161-162
[5] Synthesis (Germany), 2018, vol. 50, # 13, p. 2516 - 2522
[6] Patent: US2006/154915, 2006, A1, . Location in patent: Page/Page column 31
[7] Patent: US2011/269738, 2011, A1, . Location in patent: Page/Page column 41
[8] Patent: WO2011/134280, 2011, A1, . Location in patent: Page/Page column 83
[9] European Journal of Organic Chemistry, 2016, vol. 2016, # 22, p. 3679 - 3683
31
[ 1829-34-1 ]
[ 33491-30-4 ]
Yield
Reaction Conditions
Operation in experiment
26%
With ethyl (triphenylphosphoranylidene)acetate In 1-methyl-pyrrolidin-2-one at 210℃; for 3 h;
To a solution of 3-bromo-2-hydroxybenzaldehyde (402 mg, 2.0 mmol) in NMP (5 ml.) was added carbethoxymethylene triphenylphosphorane (765 mg, 2.2 mmol). The reaction was heated at 210 0C for 3h, then was cooled to RT and partitioned between water and ethyl acetate. The layers were separated and the organic layer was dried over MgSO4. Purification by flash chromatography on silica gel (2:1 hexanes/ethyl acetate) <n="30"/>yielded the title compound (1 16 mg, 26percent) as a light beige solid: MS (ES) m/e 227.0 (M + H)+.
With potassium carbonate; In N,N-dimethyl-formamide; at 60℃;Inert atmosphere;
General procedure: To a solution of 3-bromo-2-hydroxybenzaldehyde 2 (300 mg,1.5 mmol) and isobutyl bromide (0.8 ml, 7.4 mmol) in DMF was added K2CO3 (1.7 g, 12.0 mmol). Themixture was heated to 60 C under N2 in oil bath and stirred for 10 h. 1 M aq. HCl and EtOAc were addedto the resulting mixture. The organic phase was separated and the aqueous phase was extracted withEtOAc. The combined organic phase was washed with brine, dried over Na2SO4, filtered, and evaporated.The residue was purified by column chromatography on silica gel (EtOAc : hexane = 1 : 5) to afford3-bromo-2-isobutoxybenzaldehyde 3a (329.4 mg, 86%).
99%
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 18h;
K2C03 (13.51 g, 97.75 mmol) and CH3I (2.43 mL, 39.1 mmol) were added to a sol. of 3-bromo-2-hydroxybenzaldehyde (6.55 g, 32.58 mmol) in DMF (164 mL). The r.m. was stirred at r.t. for 18 h. The mixture was poured into a 1 N HCl sol. and the aq. layer was extracted with EtOAc. The o.l. was separated, dried (MgS04), filtered and concentrated in vacuo. Yield: 7 g of intermediate 25 (99% yield) as a brown-orange oil.
94%
To a solution of 3-bromo-2-hydroxy- benzaldehyde (2.72 g, 13.53 mmol) in DMF (70 mL) were added potassium carbonate (5.61 g, 40.59 mmol) and iodomethane (1.01 ml_, 16.24 mmol). The reaction mixture was stirred at RT. After 18 h, the mixture was acidified with cooling using 1 M HCI (aq), extracted with EtOAc. The organic extract was dried (Na2S04), filtered and concentrated in vacuo to afford the title compound as an oil (2.73 g, 94%). NMR (300 MHz, CDCI3): delta 10.36 (s, 1 H), 7.85-7.79 (m, 2H), 7.15 (dt, J = 7.7and 0.7 Hz, 1 H), 4.00 (s, 3H).
93%
With potassium carbonate; In acetone; at 60℃; for 2h;
3-Bromo-2-hydroxybenzaldehyde (5.0 g, 24.87 mmol) was dissolved in acetone (200 ml) and treated with iodomethane (5.3 g, 37.34 mmol) and potassium carbonate (5.2 g, 37.63 mmol). The mixture was heated to 60 C for 2 hr then cooled to room temperature and filtered. The filtrate was concentrated to dryness and re-dissolved in ethyl acetate. The solution was washed with saturated aqueous sodium bicarbonate and dried over MgSO4. After concentration, the residue was passed through a layer of silica gel, which was eluted with 50% ethyl acetate in hexanes. The eluent was concentrated to give 2.0 g (93%) of 3-bromo-2- methoxybenzaldehyde as a colorless syrup. MS 215.0 (M+H); HPLC rt = 13.8 min [a].
88%
With tetra(n-butyl)ammonium hydroxide; sodium hydroxide; In dichloromethane; water; at 20℃; for 16h;
Bu4NOH (40 wt% in H2O; 11.1 mL, 16.9 mmol), NaOH (1.15 g, 28.8 mmol), and MeI (2.64 mL, 42.4 mmol) were added to a solution of 3-bromosalicylaldehyde (10) (1.70 g, 8.46 mmol) in CH2Cl2 (60 mL) and water (60 mL). The mixture was vigorously stirred at r.t. for 16 h under air. The layers were separated, the aqueous layer was extracted with CH2Cl2, the combined organic layers were dried (Na2SO4), and the solvent was evaporated. Purification of the residue by flash chromatography (silica gel, isohexane-EtOAc, 15:1) provided methyl ether 11 as a colorless solid; yield : 1.60 g (7.44 mmol, 88%); mp 30-32 C. IR (ATR): 3339, 3068, 3012, 2954, 2889, 2826, 2750, 2057, 1679, 1654, 1584, 1447, 1418, 1387, 1233, 1165, 1115, 1069, 986, 851, 801, 779, 747, 699 cm-1. 1H NMR (500 MHz, CDCl3): delta = 3.99 (s, 3 H), 7.14 (td, J = 7.8, 0.7 Hz, 1H), 7.80-7.82 (m, 2 H), 10.36 (d, J = 0.7 Hz, 1H). 13C NMR and DEPT (125 MHz, CDCl3): delta = 63.51 (CH3), 118.20 (C), 125.78 (CH), 127.87 (CH), 130.95 (C), 139.50 (CH), 160.13 (C), 189.14 (CHO). MS (EI): m/z (%) = 216 (68), 214 (67, [M+]), 198 (95), 196 (81), 185 (25), 184 (23), 183 (17), 182 (23), 170 (38), 168 (24), 145 (35), 143 (35), 119 (35), 92 (43), 77 (78), 63 (100), 50 (34), 38 (18). Anal. Calcd for C8H7BrO2: C, 44.68; H, 3.28. Found: C, 44.87; H, 3.17.
With potassium carbonate; In N,N-dimethyl-formamide; for 18h;
Example 16 4-Aminomethyl-cyclohexanecarboxylic acid {1-[3-(3-amino-1H-indazol-6-yl)-2-hydroxy-phenyl]-2-phenyl-ethyl}-amide 16A. 3-Bromo-2-methoxy-benzaldehyde: (WO 2004/050637 and Duffy, K. J. et al., J. Med. Chem., 2002, 45(17), 3573) To a clear, colorless solution of 2-bromophenol (2.0 g, 11.56 mmol) in CH3CN (25.7 mL) was added anhydrous MgCl2 (4.40 g, 46.2 mmol) followed by Et3N (12.1 mL, 86.7 mmol). After 5 min., paraformaldehyde (2.77 g, 92.5 mmol) was added and the reaction was heated to a gentle reflux. After 1.5 h, the yellow suspension was cooled to rt and poured into a mixture of Et2O (400 mL)/5% citric acid (500 mL). Manual stirring gave two layers. The layers were separated and the organic layer was washed with water, brine, dried over Na2SO4, filtered and concentrated to give 2.12 g of a clear, orange-yellow liquid which solidified upon standing. To a solution of the above solid in DMF (58 mL) was added Mel (0.86 mL, 13.9 mmol) and K2CO3 (4.80 g, 34.7 mmol). After 18 h, the reaction was filtered, the filtrate was poured into water (250 mL), and compound 16A was extracted with CH2Cl2. The organic layer was washed with brine, dried over MgSO4, filtered and concentrated to give a clear, light-brown liquid. Column chromatography on silica gel (gradient elution 0-20% EtOAc/Hex) gave 1.58 g (64%) of the aldehyde as a clear, colorless liquid. 1H NMR (500 MHz, CDCl3) delta: 10.35 (d, J=1.0 Hz, 1H), 7.80 (dd, J=7.7, 1.6 Hz, 1H), 7.79 (dd, J=7.7, 1.6 Hz, 1H), 7.13 (t, J=7.7 Hz, 1H), 3.98 (s, 3H).
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃;
DESCRIPTION FOR D993-bromo-2-(methyloxy)benzaldehyde (D99)To a 500 mL two-neck round flask charged with 3-bromo-2-hydroxybenzaldehyde (D98) (13 g, 64.7 mmol) was added DMF (300 mL). Then K2CO3 (17.88 g, 129 mmol) was added, followed with methyl iodide (18.36 g, 129 mmol) at room temperature. The resulted mixture was stirred at room temperature. The mixture was stirred at room temperature overnight. The mixture was filtered through celite and washed with EtOAc. The resulted filtration was concentrated under reduced pressure. The residue was dissolved in EtOAc (250 mL), and washed with water (100 mL), 1N HCl (100 mL×2) and brine (100 mL×2). The organic layers was dried with sodium sulphate and concentrated. The residue was purified with ISCO column chromatography to afford 3-bromo-2-(methyloxy)benzaldehyde (D99) (4.05 g) as pale yellow oil. MS (ES): C8H7BrO2 requires 213.9. found 215.0 (M+H+).
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃;
To a 500 mL two-neck round flask charged with 3-bromo-2-hydroxybenzaldehyde (D98) (13 g, 64.7 mmol) was added DMF (300 mL). Then K2C03 (17.88 g, 129 mmol) was added, followed with methyl iodide (18.36 g, 129 mmol) at roomtemperature. The resulted mixture was stirred at room temperature. The mixture was stirred at room temperature overnight. The mixture was filtered through celite and washed with EtOAc. The resulted filtration was concentrated under reduced pressure. The residue was dissolved in EtOAc (250 mL), and washed with water (100 mL), 1 N HCI (100 mL X 2) and brine (100 mL X 2). The organic layers was dried with sodium sulphate and concentrated. The residue was purified with ISCO columnchromatography to afford 3-bromo-2-(methyloxy)benzaldehyde (D99) (4.05 g) as pale yellow oil. MS (ES): C8H7Br02 requires 213.9; found 215.0 (M+H+)
With ethyl (triphenylphosphoranylidene)acetate; In 1-methyl-pyrrolidin-2-one; at 210℃; for 3h;
To a solution of 3-bromo-2-hydroxybenzaldehyde (402 mg, 2.0 mmol) in NMP (5 ml.) was added carbethoxymethylene triphenylphosphorane (765 mg, 2.2 mmol). The reaction was heated at 210 0C for 3h, then was cooled to RT and partitioned between water and ethyl acetate. The layers were separated and the organic layer was dried over MgSO4. Purification by flash chromatography on silica gel (2:1 hexanes/ethyl acetate) <n="30"/>yielded the title compound (1 16 mg, 26%) as a light beige solid: MS (ES) m/e 227.0 (M + H)+.
13.5 g (40.3 mmol) 3-Brom-2-hydroxybenzaldehyd (Beispiel 28A, Gehalt 62 %) werden zusammen mit 9.18 g (84.62 mmol) Chloressigsaeuremethylester, 1.49 g (4. [03 MMOL)] Tetra-n-butylammoniumiodid und 22. [28 G] (161.18 mmol) Kalium- carbonat fuer 6 h auf [130C] erhitzt. Nach Abkuehlung [AUF RT] werden 100 mL Wasser und 100 mL THF sowie 13.57 g (241.77 mmol) Kaliumhydroxid zugegeben und ueber Nacht bei RT geruehrt. Das Solvens wird unter reduziertem Druck entfernt, der Rueckstand in 400 mL Wasser aufgenommen und viermal mit insgesamt 400 mL Diethylether gewaschen. Unter Eiskuehlung wird mit konzentrierter Salzsaeure auf pH 0 gestellt und fuenfmal mit insgesamt 700 mL Essigsaeureethylester extrahiert. Die organische Phase wird mit 100 mL gesaettigter Natriumchlorid-Loesung gewaschen und anschliessend ueber Magnesiumsulfat getrocknet. Das Rohprodukt wird im Hoch- vakuum von Loesungsmittelresten vollstaendig befreit und mit 80 mL Diethylether ver- ruehrt. Das Produkt wird abfiltriert und mit wenig eiskaltem Diethylether nachge- waschen. Es werden 4.8 g [(47] % d. Th. ) der Titelverbindung isoliert. [H-NMR] (200 MHz, DMSO-d6) : [8] = 13.5 (br. s, 1H), 7.86-7. 72 (m, 2H), 7.79 (s, [1H),] 7.31 (t, [1H).] MS (DCI/NH3) : m/z = 258 [(M+NH4)]
In methanol; i-pentylacetate; dichloromethane; water;
EXAMPLE 16 Preparation of 8-Bromo-3-(N-methylcyclopropyl-N-n-propylamino)chroman Commercially available 3-bromosalicylaldehyde (0.5 g; 2.5 mmol), <strong>[6287-40-7]di-n-butylammonium chloride</strong> (0.2 g; 1.2 mmol) and 2-nitroethanol (0.36 g; 4.0 mmol) were refluxed for 8 hours in i-pentylacetate with a Dean-Stark apparatus under nitrogen atmosphere. The solvent was evaporated and the product was dissolved in dichloromethane (15 ml) and cyanoborohydride (0.5 g; 8.1 mmol) in methanol (15 ml) was added. The mixture was stirred for 30 minutes at room temperature. Water was added and the mixture extracted with dichloromethane. The phase were separated and the organic layer was dried (MgSO4). The solvent was evaporated yielding 400 mg (63%) of 8-bromo-3-nitrochroman as an oil.
With caesium carbonate In water; N,N-dimethyl-formamide
3.A A.
A. 2-Acetyl-7-bromo benzo[b]furan A mixture of 5.0 g (24.9 mmol) of 3-bromo-salicylaldehyde, 3.0 g (32.3 mmol, 2.6 mL) of chloroacetone and 12 g (37.2 mmol) of Cs2CO3 in 30 mL of dry DMF was heated to 60° C. overnight. After cooling at room temperature, water (100 mL) was added and the mixture was extracted with ethyl acetate. The organic layer was dried over MgSO4 and the solvents were removed under reduced pressure. The crude product was directly recrystallized from hexane to afford 2-acetyl-7-bromo benzo[b]furan as a pale orange crystal.
With potassium acetate; at 170℃; for 6h;Schlenk technique; Inert atmosphere;
(2) Weigh 6.37g BA (31.69mmol),1.85 g of potassium acetate (18.85 mmol) in a SCHLENK reaction tube,Under a N2 atmosphere, 26 mL of acetic anhydride was added. The reaction was stirred at 170 C for 6 h.After the reaction is completed, it is cooled to room temperature and diluted with water.Slowly add sodium carbonate aqueous solution under stirring until the solution is neutral.The neutralized liquid is extracted with dichloromethane, and all the organic phases are combined.It was dried over anhydrous sodium sulfate, and the solvent was evaporated from vacuo. Separated and purified by silica gel column chromatography.The mobile phase was petroleum ether / ethyl acetate = 10/1.Finally, Br-C8 was obtained as a white solid, 5.08 g, yield 72.4%.
Stage #1: trimethylsulfoxonium iodide With sodium hydride In dimethyl sulfoxide for 1h;
Stage #2: 2-hydroxy-3-bromobenzaldehyde In dimethyl sulfoxide for 48h;
142.1 Synthesis of 7-bromo-2,3-dihydrobenzofuran-3-ol
To a solution of trimethylsulfoxonium iodide (16.7 g) in dimethylsufoxide (75 ml), sodium hydride (3.19 g) was added, and the resultant mixture was stirred for 1 hour. A solution of 2,3-dihydroxybenzaldehyde (10 g) in dimethylsufoxide (75 ml) was added thereto and the resultant mixture was stirred for 2 days. To the resultant reaction solution, saturated ammonium chloride aqueous solution was added, and extracted with ethyl acetate. The resultant organic phase was washed with a saturated saline, dried over anhydrous sodium sulfate, and filtered. From the reaction mixture, the solvent was distilled off under reduced pressure, followed by purifying the resultant residue by silica gel column chromatography (eluate; n-hexane:ethyl acetate=100:0 to 80:20), and from the resultant, the solvent was distilled off under reduced pressure to obtain the subject compound (4.2 g) as yellow solid.; According to the method of (Example 138) , from 3-bromo-2-hydroxybenzaldehyde (3.0 g), the subject compound (2.5 g) was obtained as yellow oil.
The Schiff base ligand L was prepared by the condensationof 3-bromosalicylaldehyde (1.0 mmol, 201 mg) with N-cyclohexylpropane-1,3-diamine (1.0 mmol, 156 mg) in methanol (20 cm3) at room temperature. Yield: 91%. Anal. Calcd. for C16H23BrN2O (FW 339.3): C, 56.6; H, 6.8; N, 8.3.Found: C, 56.8; H, 6.9; N, 8.2%.
83%
for 1h;Reflux;
Hot methanol solutions of 3-bromosalicylaldehyde and N-cyclohexylpropane-1,3-diamine (1:1, v/v) were stirred under reflux for 1 h, and cooled to room temperature. The yellow precipitate was collected by filtration and dried in vacuo. Yield: 83%. Anal. Calcd. for C16H23BrN2O (%): C, 56.6; H, 6.8; N,8.3. Found (%): C, 56.4; H, 6.9; N, 8.2.
General procedure: The ligands L1 and L2 were prepared in over 90% yields by condensation reactions of 3-bromosalicylaldehyde with N,N-dimethylethylenediamine and N-ethylethylenediamine, respectively, in methanol. All other chemicals were commercially available and used as received.
[VO(N'-(3-bromo-2-hydroxybenzylidene)-2-chlorobenzohydrazide(-2H))(benzohydroxamic acid(-H))][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
53%
In methanol at 20℃; Darkness;
Synthesis of I
3-Bromosalicylaldehyde (1.0 mmol, 201 mg), 2-chlorobenzohydrazide (1.0 mmol, 171 mg) and benzohydroxamic acid (1.0 mmol, 137 mg) were dissolved in methanol (20 mL) and stirred at room temperature for 10 min. Then, 20 mL methanolic solution containing [VO(Acac)2] (1.0 mmol, 265 mg) was added dropwise to the solution. The mixture was further stirred at room temperature for 10 min to give a deep brown solution. The solution was filtered to obtain clear filtrate, which was kept still at dark to slow evaporation. A few days later, well-shaped brown single crystals of the complex were formed and separated by filtration. The product was washed three times with cold methanol and dried in air. The yield was 53%. UV-Vis (acetonitrile; λmax (logε)): 240 (5.19); 269 (4.14); 341 (3.75); 455 (3.64) nm. IR (KBr; ν, cm-1) 3534 m, 3135 w, 1609 v.s, 1554 m, 1517 w, 1468 m, 1401 s, 1346 s, 1266 m, 1235 w, 1162 w, 1118 m, 1039 w, 965 m, 910 w, 825 m, 776 w, 739 w, 696 m, 579 s, 450 w. For C21H14N3O5ClBrV (I) anal. calcd., %: C, 45.47; H, 2.54; N, 7.58. Found, %: C, 45.32; H, 2.63; N, 7.50.
N’-(3-bromo-2-hydroxybenzylidene)-2-fluorobenzohydrazide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
96%
In methanol; at 20℃; for 0.5h;
General procedure: 5-Bromosalicylaldehyde or 3-bromosalicylaldehyde(1.0 mmol, 0.20 g) and 2-fluorobenzohydrazide (1.0mmol, 0.15 g) were dissolved in methanol (30 mL) withstirring. The mixture was stirred for about 30 min at roomtemperature to give clear solution. The solvent was evaporatedto give colorless crystalline products. For H2L1:Yield, 93%. Analysis: Found: C 49.73%, H 3.12%, N8.40%. Calculated for C14H10BrFN2O2: C 49.88%, H2.99%, N 8.31%. For H2L1: Yield, 96%. Analysis: Found:C 49.68%, H 3.04%, N 8.43%. Calculated for C14H10BrFN2O2: C 49.88%, H 2.99%, N 8.31%.
5-(3-bromo-2-hydroxybenzylidene)-2-thioxoimidazolidin-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
50%
With sodium acetate In acetic acid for 12h; Reflux;
General synthesis procedure A
General procedure: A mixture of compound 20, aldehyde (0.5 mmol, 1 equiv 20), compound 21 (1.2 equiv), and NaOAc (3 equiv) in glacial AcOH (4 mL) was stirred at reflux (12 h) until no starting material remained, assessed by TLC (SiO2, hexane/ethyl acetate, 1:1, v/v). The reaction mixture was cooled down to room temperature, followed by the addition of iced water. The resulting precipitate was filtered and washed successively with water and Et2O (10 mL). The product was subjected to column purification (hexane/ethyl acetate, 0/35%).
With N,N,N',N'-tetramethylguanidine; In chloroform; at 20℃; for 3h;Sealed tube;
0.20 mmol of compound 5,0.24 mmol of compound 2f,0.02 mmol TMG and 2.0 mL chloroform were added to the sealed tube, The reaction at room temperature for 3h.After removing the solvent,The residue was purified by silica gel column chromatography to give the product 6f,The yield is 75%.
N'-(3-bromo-2-hydroxybenzylidene)-2-chlorobenzohydrazide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
In methanol for 2h; Reflux;
0.201 g (1.0 mmol) of 3-bromosalicylaldehyde in 20 mL methanol was added to 20 mL of 0.170 g (1.0 mmol) of 2-chlorobenzohydrazide. The solution mixture was refluxed with vigorous stirring for 2 h. The solvent was then evaporated and allowed to cool to room temperature. The white precipitate was filtered and washed with methanol and dried in air. The yield was 86%. For C14H10N2O2ClBr anal. calcd., %: C, 47.55; H, 2.85; N, 7.92. Found, %: C, 47.32; H, 2.96; N, 8.04. IR (KBr; νmax, cm-1): 3441 w ν(OH), 1659 s ν(C=O), 1591 w ν(C=N), 1545 m ν(Ar-O), 1296 m ν(C-O). 1HNMR (DMSO-d6; δ, ppm): 6.95 (t., 1H, ArH), 7.39-7.72 (m., 6H, ArH), 8.69 (s., 1H, CH=N), 10.27 (s.,1H, NH), 12.31 (s., 1H, OH). 13C NMR (DMSO-d6; δ,ppm): 111.9, 120.3, 121.8, 127.3, 129.2, 130.5, 131.7, 133.0, 133.9, 134.3, 135.7, 147.2, 159.2, 164.5.
With caesium carbonate In N,N-dimethyl-formamide at 60℃; Inert atmosphere;
19.19a Step 19a: Preparation of (1-(7-bromobenzofuran-2-yl)ethan-1-one) (Compound 0802-58):
3-Bromo-2-hydroxybenzaldehyde (0801-58) (2.39 g, 11.9 mmol, 1.0 eq.)And bromoacetone 1.63g, 11.9mmol, 1.0 equivalent)Soluble in N,N-dimethylformamide (20 mL),Then cesium carbonate (5.82 g, 17.85 mmol, 1.2 eq.) was added.Replace the air in the reaction system three times with nitrogen,It was then reacted at 60 ° C overnight.The reaction solution was diluted with water (50 mL).Then extracted with ethyl acetate (30 mL×3).The extract was dried over anhydrous sodium sulfate and concentrated.Then purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10:1)The white solid product 1-(7-bromobenzofuran-2-yl)ethan-1-one was obtained(1.37 g, yield: 40%).
38%
With caesium carbonate In N,N-dimethyl-formamide at 0 - 60℃; for 9h;
4.1.1 General procedures for the synthesis of compounds 10, 12 and 14
General procedure: To a stirred solution of started materials 9, 11 or 13 (20mmol, 1.0 equiv) in DMF (40mL) was added Cs2CO3 (30mmol, 1.5 equiv). Then bromoacetone (26mmol, 1.3 equiv) was added dropwise under an ice bath over a period of 60min. The mixture was stirred and heated at 60°C for 8h. After cooling to room temperature, the aqueous layer was extracted with ethyl acetate (3×150mL), and the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (PE/EtOAc=10:1) to afford intermediates 10, 12 and 14. 4.1.1.1 1-(7-bromobenzofuran-2-yl) ethan-1-one (10) (0014) White solid; yield: 38%. 1H NMR (600MHz, CDCl3) δ 7.65 (t, J=7.1Hz, 2H), 7.55 (s, 1H), 7.21 (t, J=7.8Hz, 1H), 2.66 (s, 3H). ESI-HRMS [M+H]+ calcd for C10H8BrO2+ 238.9702, found 238.9705.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 75℃; for 1h;Inert atmosphere;
Synthesis of 3-phenyl salicylaldehyde:The 50 mL reaction flask was evacuated to nitrogen.After replacing nitrogen three times, 10 mmol of 3-bromo salicylaldehyde was added under nitrogen protection.11 mmol of phenylboronic acid, 10 mmol of potassium carbonate, 20 mL of a mixed solvent of tetrahydrofuran and water (V tetrahydrofuran: V water = 5:1), 0.1 mmol of tetrakis(triphenylphosphine)palladium,After magnetic stirring at 75 C for 1 h, the product is separated, purified and dried.get3-phenyl salicylaldehyde.
3-Bromosalicylaldehyde (0.200 g, 1 mmol) and 3-hydroxylbenzohydrazide (0.150 g,1 mmol) were stirred in methanol (30 mL) for 30 min. Then, ethyl maltol (0.140 g,1 mmol) and VOSO4 (0.163 g, 1 mmol) dissolved in methanol (30 mL) were added to the above solution. The mixture was further stirred for 30 min to give a deep brown solution. Single crystals were obtained by slow evaporation of the solution in air.Yield: 65%. IR data (cm-1): 3449 (OH), 1601 (CN), 949 (VO). UV-Vis data (MeOH, lambdamax, nm): 273, 325, 401. Anal. calc. for C21H16BrN2O7V: C, 46.8; H, 3.0; N, 5.2. Found: C,46.6; H, 3.1; N, 5.3%. 1H NMR (300 MHz, DMSO-d6) delta 9.72 (s, 1 H, OH), 9.24 (s, 1 H,CHN), 8.51 (d, 1 H, L'H), 7.88 (m, 2 H, ArH), 7.28 (m, 3 H, ArH), 7.02 (d, 1 H, ArH), 6.95(m, 1 H, ArH), 6.74 (d, 1 H, L'H), 3.03 (q, 2 H, CH2), 1.35 (t, 3 H, CH3).
2-([2,2':6',2''-terpyridin]-4'-yl)-6-bromophenol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92.3%
With ammonium hydroxide; potassium hydroxide In ethanol at 40℃; for 24h; Cooling with ice;
1-2 Example 1: Preparation of ligand H-Lc
Add 2-acetylpyridine (2.24mL, 20mmol) and 3-bromosalicylic aldehyde (2.01g, 10mmol) into a 100mL round-bottomed flask, measure 50mL of ethanol into the round-bottomed flask, shake well, and then measure 0.75 mL ammonia water with a concentration of 25% (the added ammonia water is about 10mmol) is added to it, 0.14g potassium hydroxide is weighed and carefully added to the round bottom flask (after the potassium hydroxide is dissolved and stirred evenly, the pH value of the system is between 12-13 ), put the magnets in, install the reflux reaction device, and react for 24 hours in a water bath at 40°C (the solution was light brown at first, and a light yellow solid was produced as the reaction progressed).After the reaction, the round-bottomed flask was removed, and the solvent in the flask was evaporated by half, and then suction filtered, the filter cake was collected, washed with ethanol, and dried.A light yellow powdery solid was obtained.The yield was 92.3% (3.72 g, calculated on the basis of 3-bromosalicylic aldehyde).
92.3%
With ammonium hydroxide; potassium hydroxide In ethanol at 40℃; for 24h;
1; 2 Example 1: Preparation of ligand H-Lc
2-Acetylpyridine (2.24 mL, 20 mmol) and 3-bromosalicylic aldehyde (2.01 g, 10 mmol) were added to a 100 mL round-bottomed flask,Measure 50mL of ethanol and add it to the round-bottomed flask, shake it up, and then measure 0.75mL of 25% ammonia water (about 10mmol of ammonia added) into it,Weigh 0.14 g of potassium hydroxide and carefully add it to the round-bottomed flask (the pH of the system is between 12 and 13 after the potassium hydroxide is dissolved and stirred evenly),After the magnetron was put in and the reflux reaction device was installed, the reaction was carried out in a water bath at 40° C. for 24 hours (the solution was light brown at first, and a light yellow solid was produced as the reaction progressed).After the reaction was completed, the round-bottomed flask was removed, and rotary evaporation was performed to evaporate half of the solvent in the flask. Then, suction filtration was performed to collect the filter cake, washed with ethanol, and dried to obtain a light yellow powdery solid. The yield was 92.3% (3.72 g based on 3-bromosalicylaldehyde).
2. 5. Synthesis of Complex 3
3-Bromosalicylaldehyde (0.10 mmol, 20 mg), N-isopropylethane-1,2-diamine (0.10 mmol, 10 mg) and coppernitrate trihydrate (0.10 mmol, 24 mg) were mixed in methanol(15 mL) to give a clear blue solution. Block blue singlecrystals of the complex, suitable for X-ray diffraction, weregrown from the solution upon slowly evaporation within 7 days. The crystals were isolated by filtration. Yield 27%.Anal. calc. for C24H34Br2CuN6O8: C, 38.03; H, 4.52; N,11.09; found: C, 38.22; H, 4.61; N, 10.93%. IR data (cm-1):2971, 2937, 1619, 1590, 1530, 1443, 1413, 1382, 1323, 1230,1177, 1146, 1070, 1033, 905, 846, 753, 654, 632, 546, 461.UV-Vis data (MeOH, λmax, nm): 220, 250, 265, 373.
2. 3. Synthesis of Complex 1
3-Bromosalicylaldehyde (0.10 mmol, 20 mg), N-isopropylethane-1,2-diamine (0.10 mmol, 10 mg), and copperbromide (0.10 mmol, 22 mg) were mixed in methanol(15 mL) to give a clear blue solution. Block blue singlecrystals of the complex, suitable for X-ray diffraction,were grown from the solution upon slowly evaporationwithin 6 days. The crystals were isolated by filtration.Yield 32%. Anal. calc. for C24H34Br4CuN4O2: C, 36.32; H,4.32; N, 7.06; found: C, 36.13; H, 4.41; N, 9.91%. IR data(cm-1): 2971, 2933, 2816, 2782, 1618, 1592, 1530, 1438,1391, 1329, 1228, 1186, 1132, 1073, 1035, 905, 843, 738,671, 612, 550. UV-Vis data (MeOH, λmax, nm): 222, 247,267, 372.
2. 2. Synthesis of HL
3-Bromosalicylaldehyde (1.0 mmol, 0.20 g) andN-isopropylethane-1,2-diamine (1.0 mmol, 0.10 g) weremixed and stirred in methanol (30 mL). The mixture wasrefluxed for 30 min, and with the solvent removed by distillation.The solid product was recrystallized from methanolto give yellow product. Yield 87%. Anal. calc. for C12H-17BrN2O: C, 50.54; H, 6.01; N, 9.82; found: C, 50.38; H,6.12; N, 9.73%. IR data (cm-1): 1634, 1468, 1381, 1242,1098, 928, 915, 457. UV-Vis data (MeOH, λmax, nm): 230,275, 332, 417.
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