Category: 89642-49-9

Application of 89642-49-9, These common heterocyclic compound, 89642-49-9, name is 4-Bromo-3-nitrobenzonitrile, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

General Procedure for Silyl Acetylenes (61 b,e,f). Cul (2 mol %) was added to a stirred mixture of an aryl halide 60, (trimethylsilyl)acetylene (min. 1.3 equiv), and PdCl2(PPh3)2 (2 mol %) in triethylamine. See . The mixture was heated at 60 C until the reaction was complete (ca. 3 h). Salts were filtered off and washed with EtOAc. Combined filtrates were evaporated under reduced pressure, and the residue was purified by column chromatography eluding with hexane/EtOAc. The recovered material was recrystallized as necessary. 3-nitro-4-[2-(trimethylsilyl)ethynyl]benzonitrile (61 b) was prepared from aryl bromide 60b as an off-white solid (1.61 g, 66%): mp 81-82 C (toluene/hexane); 1H NMR delta 8.69 (d, J = 1.6 Hz, 1H), 8.20 (dd, J = 8.0 and 1.6 Hz, 1H), 7.94 (d, J = 8.2 Hz, 1H), 0.27 (s, 9H); HPLC (Method B) tR 8.39 min (100 area % at 254 nm). Anal. (C12H12N2O2Si) C, H, N. A second general method is depicted in Scheme 2 immediately hereinabove and comprises the cycloaddition of cyanophenylacetylenes 51 and benzaldehyde chlorooximes 52 in the presence of bis(tributyltin) oxide, see Moriya, O., et al., J. Chem. Soc., Perkin Trans., 1, 413-417 (1994); Moriya, O., et al., J. Chem. Soc., Chem. Commun., 17-18 (1991), or triethylamine, see Thomsen, l., et al., Acta Chem. Scand. (B), 319-313 (1988), in nonpolar solvents to give isoxazole dinitriles 53a-h,k-s and bromonitrile 53i. The latter was treated with copper(I) cyanide to give dinitrile 53j. See Friedman. L., et al., J. Org. Chem., 26, 2522-2524 (1961). This method also afforded alternate routes to dinitriles 50a,b,g, k prepared by the first method as provided in Scheme 1. The phenylacetylene synthons 51a-g were prepared as shown in Scheme 3 below. Starting materials 60a,e,g were commercially available. Nitration of 60a gave 60b. See Borsche, W., L., et al., Chem. Ber., 49, 2222-2243 (1916). The latter was reduced to aniline 56, see Blanksma, J. J., et al., Recl. Trav. Chim. Pays-Bas, 66, 365-373 (1947), which underwent diazotization followed by treatment with copper(l) chloride to give chlorobenzene 60c. Triflate 60d was prepared by treatment of 4-bromo-3-hydroxybenzonitrile with triflic anhydride. The preparation of aryl iodide 60f began with the known transformation of aldehyde 57 to iodo derivative 58. See Lulinski, P., et al., Bull. Chem. Soc. Jpn., 73(4), 951-956 (2000). Treatment of 58 with hydroxylamine hydrochloride gave aldoxime 59, which was dehydrated to give nitrile 60f using acetic anhydride. The aryl halides or triflates 60a-g were treated with (trimethylsilyl)acetylene, see Roesch. K. R., et al., J. Org. Chem., 66, 412-420 (2001), or with 2-methyl-3-butyn-2-ol, see Bleicher, L. S., et al., J. Org. Chem., 63, 1109-1118 (1998), to give intermediates 61a-f or 62a-f, respectively, of which 61a,d and 62a have been reported previously. See Dirk. S. M., et al., Tetrahedron, 59(3), 287-293 (2003); Bleicher, L. S., et al., J. Org. Chem., 63, 1109-1118 (1998). The acetylenes 51 (of which 51a,e were known previously), see Blackburn, B. K., et al., J. Med. Chem., 40(5), 717-729 (1997); Dulog, L., et al., Liebigs Ann. Chem., 9, 1663-1671 (1995), were obtained by the treatment of intermediates 61 or 62 with cesium carbonate in acetonitrile or sodium hydride in toluene, respectively. See Bleicher, L. S., et al., J. Org. Chem., 63, 1109-1118 (1998). The use of cesium carbonate in acetonitrile was introduced for the deprotection of intermediates 61 after the treatment of compound 61b with potassium carbonate in methanol, see Blackburn, B. K., et al., J. Med. Chem., 40(5), 717-729 (1997), failed to give product 51b. The pathway using 2-methyl-3-butyn-2-ol provided more economical preparations of all phenylacetylenes 51 except nitro analog 51b. ; Reagents and conditions: (a) fuming HNO3, H2SO4; (b) Fe, AcOH, EtOH; (c) NaNO2, aq. HCl, then CuCl; (d) NalO4, l2, AcOH, AC2O, H2SO4; (e) NH2OH HCl, Py, EtOH (f) Ac2O; (g) TMSA, Pd2Cl2(PPh3)2, Cul, Et3N; (h) TMSA, PPh3, Pd(PPh3)4, Cul, piperidine; (j) 2-methyl-3-butyn-2-ol, Pd2Cl2(PPh3)2, Cul, Et3N; (k) 2-methyl-3-butyn-2-ol, 10% Pd/C, PPh3, Cul, aq. K2CO3/DME; (I) Cs2CO3, aq. CH3CN or MeOH; (m) NaH, toluene.

Statistics shows that 4-Bromo-3-nitrobenzonitrile is playing an increasingly important role. we look forward to future research findings about 89642-49-9.

Synthetic Route of 89642-49-9, A common heterocyclic compound, 89642-49-9, name is 4-Bromo-3-nitrobenzonitrile, molecular formula is C7H3BrN2O2, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

3.48. Compound 49: (lR,2R)-N-(6-(5-cyano-2-ethylphenylamino)-l-methyl-lH-imidazo[4,5- 3.48.1. Step i : 3-Nitro-4-vinyl-benzonitrile A mixture of 4-bromo-3-nitro-benzonitrile (1.0 eq, 1.0 g), potassium vinyl trifluoroborate (1.5 eq, 0.89 g), PdCl2(dppf).DCM (0.05 eq, 201 mg), K2C03 (3.0 eq, 1.82 g) in THF/water (10: 1; 20 mL) is heated at 80 C. After 1 h, the resulting mixture is diluted with DCM and aq. sat. NaHCOs, passed through a phase separator and concentrated. The residue is used as such in the next step.

The synthetic route of 89642-49-9 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; GALAPAGOS NV; MENET, Christel, Jeanne, Marie; MAMMOLITI, Oscar; QUINTON, Evelyne; JOANNESSE, Caroline, Martine, Andree-Marie; DE BLIECK, Ann; BLANC, Javier; (263 pag.)WO2017/12647; (2017); A1;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Application of 89642-49-9, These common heterocyclic compound, 89642-49-9, name is 4-Bromo-3-nitrobenzonitrile, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

15.18 g (52.85 mmol) of 9-phenyl-9H-carbazole-3-yl-boronic acid, 10 g (44.04 mmol) of 4-bromo-3-nitrobenzonitrile, and 0.05 percent by weight (wt %) of a palladium catalyst were dissolved in 25 ml of toluene, 25 ml of 2 molar (M) potassium carbonate was added thereto, and the resulting reaction solution was stirred for 24 hours. After completing the reaction, the resulting reaction solution was extracted using chloroform to remove a solvent therefrom. Then, the resulting solid product was dried. 3 equivalents of triphenylphosphine were added thereto, and the mixture was stirred in dichlorobenzene for 12 hours at a temperature of 160 C. After completing the reaction, 100 ml of methanol was slowly added to the mixture, to thereby filter the resulting reaction solution. The filtered crude product obtained therefrom was dried and purified by column chromatography with a mixture of dichloromethane and hexane as an eluent, thereby obtaining 4.87 g (yield: 31%) of Intermediate 4. The structure of the synthesized compound was identified using a MALDI-TOF mass spectrometer. (0347) MALDI-TOF (calculated: 357.1 g/mol, measured: [M+H]+=358 g/mol)

Statistics shows that 4-Bromo-3-nitrobenzonitrile is playing an increasingly important role. we look forward to future research findings about 89642-49-9.

Reference:
Patent; SAMSUNG ELECTRONICS CO., LTD.; SAMSUNG SDI CO., LTD.; Jeon, Soonok; Numata, Masaki; Lee, Saeyoun; Miyazaki, Hiroshi; Son, Jhunmo; Sim, Myungsun; Lee, Namheon; Ihn, Sooghang; (116 pag.)US10510966; (2019); B2;,
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts