Month: November 2022

《A bicyclic pentapeptide-based highly potent and selective pan-SIRT1/2/3 inhibitor harboring Nε-thioacetyl-lysine》 was published in Bioorganic & Medicinal Chemistry in 2020. These research results belong to Li, Renwu; Yan, Lingling; Sun, Xun; Zheng, Weiping. Electric Literature of C4H7BrO2 The article mentions the following:

Past few years have seen an active pursuit of the inhibitors for the deacylation catalyzed by the seven human sirtuins (i.e. SIRT1-7) as valuable chem. biol./pharmacol. probes of this enzymic deacylation and lead compounds for developing novel therapeutics for human diseases. In the current study, we prepared eight monocyclic and one bicyclic analogs of a linear pentapeptide-based potent (sub-μM IC50’s) pan-SIRT1/2/3 inhibitor Zheng laboratory discovered recently that harbors the catalytic mechanism-based SIRT1/2/3 inhibitory warhead Nε-thioacetyl-lysine at its central position. We found that the bicyclic analog exhibited largely comparable SIRT1/2/3 inhibitory potencies to those of the parent linear pentapeptide, however, the former is proteolytically much more stable than the latter. Moreover, the bicyclic analog displayed very weak inhibition against SIRT5/6/7, was cell permeable, and exhibited an anti-proliferative effect on the human SK-MEL-2 melanoma cells. This bicyclic analog could be a lead for the future development of more potent and still selective pan-SIRT1/2/3 inhibitors whose use in studies on human sirtuin biol., pharmacol., and medicinal chem. could complement with the use of the potent inhibitors selective for a single human sirtuin. In the experimental materials used by the author, we found 4-Bromobutanoic acid(cas: 2623-87-2Electric Literature of C4H7BrO2)

4-Bromobutanoic acid(cas: 2623-87-2) belongs to carboxylic acids. The chief chemical characteristic of the carboxylic acids is their acidity. They are generally more acidic than other organic compounds containing hydroxyl groups but are generally weaker than the familiar mineral acids (e.g., hydrochloric acid, HCl, sulfuric acid, H2SO4, etc.).Electric Literature of C4H7BrO2

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary

《Cross-coupling polymerization at iodophenyl thin films prepared by spontaneous grafting of a diazonium salt》 was published in PeerJ Materials Science in 2020. These research results belong to Marshall, Nicholas; Rodriguez, Andres. Product Details of 3141-27-3 The article mentions the following:

Cross-coupling at aryl halide thin films has been well-established as a technique for the surface-initiated Kumada catalyst transfer polymerization (SI-KCTP), used to produce covalently bound conjugated polymer thin films. In this work, we report that the spontaneous grafting of 4-iodobenzenediazonium tetrafluoroborate on gold substrates creates a durable iodoarene layer which is effective as a substrate for cross-coupling reactions including SI-KCTP. Using cyclic voltammetry of a surface-coupled ferrocene terminating agent, we have measured initiator surface coverage produced by oxidative addition of Pd(t-Bu3P)2 and estimated the rate constant of the termination reaction in the SI-KCTP system with 2-chloromagnesio-5-bromothiophene and Pd(t-Bu3P)2. We used this system to prepare uniform polythiophene thin films averaging 90 nm in thickness. In addition to this study using 2,5-Dibromothiophene, there are many other studies that have used 2,5-Dibromothiophene(cas: 3141-27-3Product Details of 3141-27-3) was used in this study.

2,5-Dibromothiophene(cas: 3141-27-3) , is mainly used as pharmaceutical intermediate and synthesis intermediate. 2,5-Dibromothiophene may be used in the preparation of soluble α,ω-diformyl-a-oligothiophenes.Product Details of 3141-27-3

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary

《Tunable emission of AgIn5S8 and ZnAgIn5S8 nanocrystals: electrosynthesis, characterization and optical application》 was written by Sousa, F. L. N.; Freitas, D. V.; Silva, R. R.; Silva, S. E.; Jesus, A. C.; Mansur, H. S.; Azevedo, W. M.; Navarro, M.. Recommanded Product: 13465-09-3 And the article was included in Materials Today Chemistry in 2020. The article conveys some information:

Ternary AgIn5S8 (AIS) and quaternary ZnAgIn5S8-alloy (ZAIS) nanocrystals, stabilized by L-glutathione, were produced by a clean and eco-friendly electrochem. method, eliminating the need of reducing agents. AIS-GSH colloidal solution was obtained by constant current electrolysis (i = 30 mA) in cavity cell. S2- ions (0.051 mmol) were generated into a graphite powder macroelectrode, reacting in the intermediate compartment of the cell containing Ag+/In3+ aqueous solution at different ratios (0.5, 0.28, 0.18, and 0.14), and 0.025 mmol/L-1 glutathione (GSH). ZAIS-GSH NCs were synthesized in the same cavity cell containing the previously prepared AIS-GSH solution A paired electrolysis (i = 30 mA) was used for simultaneous production of Zn2+ and S2- (Zn0 sacrificial anode and graphite powder macroelectrode/S0 cathode). The electrochem. method promoted a high reproducibility and efficient luminescence in the preparations of NCs. The sizes of the AIS-GSH and ZAIS-GSH nanoparticles were determined by HRTM (3.4 and 4.0 nm, resp.), and quantum yields reaching 16% (AIS-GSH, Ag+/In3+ = 0.18). The spectrophotometric characterization showed that Ag+/In3+ ratio can be used for the tuning of the AIS-GSH nanoparticle emission wavelength, which is associated to electronic defects introduced in the NCs lattice. XRD/EDS anal. of ZAIS-GSH nanoparticles point out to Zn2+ ion-exchange into the AIS-GSH lattice. XPS anal. was carried out at different etching levels of the ZAIS nanocrystals surface, making possible to identify the 2p Zn doublet signal, indicating two different Zn2+ sites in the alloy structure. Time-resolved spectroscopy measurements/decay curves were carried out to evaluate the effect of silver amount on radioactive and non-radioactive terms. Addnl., the AIS-GSH and ZAIS-GSH photoluminescence and stability were used to produce the active parts of com. white LEDs, and modulate the color perception from the resp. emission bands. In the experiment, the researchers used many compounds, for example, Indium(III) bromide(cas: 13465-09-3Recommanded Product: 13465-09-3)

Indium(III) bromide(cas: 13465-09-3) is used as a catalyst to produce dithioacetals when unactivated alkynes react with thiols and fields such as optics and microelectronics that utilize semiconductor technology have wide uses for indium in high-performing solar cells.Recommanded Product: 13465-09-3

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary

《Amide derivatives of 4-azaindole: design, synthesis, and EGFR targeting anticancer agents》 was written by Venkat Swamy, Puli; Kiran Kumar, Vukoti; Radhakrishnam Raju, Ruddarraju; Venkata Reddy, Regalla; Chatterjee, Anindita; Kiran, Gangarapu; Sridhar, Gattu. Synthetic Route of C6H5Br2N And the article was included in Synthetic Communications in 2020. The article conveys some information:

A series of amide derivatives of azaindole-oxazoles (11a-11n) were designed and synthesized and their structures were confirmed by 1HNMR, 13CNMR and mass spectral anal. Further, these derivatives were screened for their anticancer activity against human cancer cell lines viz; MCF7 (breast), A549 (lung) and A375 (melanoma). In vitro anticancer activity screening indicated that most of the hybrids exhibited potent inhibitory activities in a variety of cancer cell lines. Compounds 11m (I), 11j (II), 11d, 11e, 11f, 11k, 11l and 11n (III; R= 4-OMe; 3,5-diOMe; 3,4,5-triOMe; 4-F; 4-NO2; 4-CN; resp.) each exhibited more potent activity than standard, and compounds I and II exhibited excellent activity in MCF-7 cell line with IC50 values 0.034 and 0.036μM. Moreover, all these compounds were subjected to mol. docking studies on EGFR receptor and the results indicated that two potent compounds I and II strongly bind to protein EGFR (PDB ID: 4hjo). It was found that the energy calculations were in good agreement with the observed IC50 values. The experimental part of the paper was very detailed, including the reaction process of 3,5-Dibromoaniline(cas: 626-40-4Synthetic Route of C6H5Br2N)

3,5-Dibromoaniline(cas: 626-40-4) belongs to anime. Examples of direct uses of amines and their salts are as corrosion inhibitors in boilers and in lubricating oils (morpholine), as antioxidants for rubber and roofing asphalt (diarylamines), as stabilizers for cellulose nitrate explosives (diphenylamine), as protectants against damage from gamma radiation (diarylamines), as developers in photography (aromatic diamines), as flotation agents in mining, as anticling and waterproofing agents for textiles, as fabric softeners, in paper coating, and for solubilizing herbicides.Synthetic Route of C6H5Br2N

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary

《Nickel-Catalyzed Cross-Electrophile Reductive Couplings of Neopentyl Bromides with Aryl Bromides》 was written by Biswas, Soumik; Qu, Bo; Desrosiers, Jean-Nicolas; Choi, Younggi; Haddad, Nizar; Yee, Nathan K.; Song, Jinghua J.; Senanayake, Chris H.. Name: 1-Bromo-4-(trifluoromethyl)benzene And the article was included in Journal of Organic Chemistry in 2020. The article conveys some information:

5-Cyanoimidazole was identified as an inexpensive ligand for nickel-catalyzed cross-electrophile couplings by screening a diverse set of pharmaceutical compound library. A strategic screening approach led to the discovery of this novel ligand, which was successfully applied in the preparation of various alkylated arene products with good to high yields. Furthermore, the properties of this ligand allowed expanding the scope of reductive couplings to challenging substrates, such as sterically hindered neopentyl halides, which are known to generate motifs that are prevalent in biol. active mols. The results came from multiple reactions, including the reaction of 1-Bromo-4-(trifluoromethyl)benzene(cas: 402-43-7Name: 1-Bromo-4-(trifluoromethyl)benzene)

1-Bromo-4-(trifluoromethyl)benzene(cas: 402-43-7) belongs to organobromine compounds.The reactivity of organobromine compounds resembles but is intermediate between the reactivity of organochlorine and organoiodine compounds. Dehydrobromination, Grignard reactions, reductive coupling, Wittig reaction, and several nucleophilic substitution reactions are some of the principal reactions which involve organic bromides.Name: 1-Bromo-4-(trifluoromethyl)benzene

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary

Julia, Marc; Chastrette, Francine published an article in 1962, the title of the article was 4-Substituted salicyclic acids.Product Details of 39503-58-7 And the article contains the following content:

The preparation of 4,3-HO2C(HO)C6H3(CH2)nCO2H (I) (n = 1, 2, 3) is described. m-AcOC6H4Me (600 g.) and 600 cc. powd. AlCl3 heated at 120-65° and steam distilled, and the distillate extracted with Et2O gave 470 g. 4,2-Me(HO)C6H3Ac (II), b0.6 82-4°, n2D4 1.5542; semicarbazone m. 218-20° (EtOH). II (167 g.) in 500 cc. aqueous NaOH heated 6 h. on a steam bath with 140 g. Me2SO4, treated again with 470 g. Me2SO4 and with a sufficient amount aqueous NaOH to maintain alkalinity, and extracted with Et2O yielded 180 g. 4,2-Me(MeO)C6H3Ac (III), b0.6 100-3°, m. 35-6°; semicarbazone m. 194-8°. III (192 g.) and 4.1 l. 1.4N NaOCl, 2.3-2.6N in NaOH, stirred several hrs., treated with aqueous NaHSO3, and acidified with concentrated HCl precipitated 184 g. 4,2-Me(MeO)C6H3CO2H (IV), m. 103-4° (aqueous EtOH). III (48 g.) treated with 900 cc. 1.7N NaOCl, 3.14N in NaOH, yielded 53 g. 3,5,4,2-Cl2Me(MeO)C6-H6CO2H, m. 175-6°. IV (93 g.), 900 cc. absolute MeOH, and 6 g. concentrated H2SO4 refluxed overnight, the mixture concentrated, poured onto ice, and extracted with Et2O gave 75 g. 4,2-Me(MeO)C6H3CO2Me (V), b22 142°, m. 29°, n1D8 1.5230. V (4.5 g.) in 100 cc. AcOH treated dropwise with 4.5 g. Br, the mixture stirred 3 h., kept overnight, diluted with H2O, and extracted with Et2O yielded 5.4 g. Me ester (VI) of 5,4,2-BrMe(MeO)C6H2CO2H (VII), m. 46°. VI saponified gave VII, m. 134-5°. IV (2.2 g.) in 40 cc. CCl4 refluxed and irradiated (W filament) with stirring, treated during 1 h. with 2.2 g. Br, heated 2 h., stirred 12 h., and filtered gave 2.44 g. VII, m. 135° (C6H6). VII (6.2 g.) in 90 cc. 95% EtOH and 30 g. Raney Ni-Al alloy treated dropwise with 300 cc. 10% aqueous NaOH, refluxed 1 h., and filtered, the filtrate added to 250 cc. concentrated HCl, the precipitate extracted with C6H6, and the extract evaporated yielded 3.66 g. IV, m. 102°. N-Bromosuccinimide (2.5 g.), 3.6 g. Bz2O2, 30 g. V, and 75 cc. CCl4 refluxed 3 h., cooled, filtered, and distilled gave 7 g. unchanged V and 26 g. oil, b0.03 122-42°, which, fractionally recrystallized from MeOH and petr. ether, gave 4 g. VI and 8 g. 4,2BrCH2(MeO)C6H3CO2Me (VIII), m. 51°. VIII (4 g.) and 3.2 g. (CH2)6N4 in 30 cc. CHCl3 refluxed I hr. and filtered, the residue refluxed 2 h. with 50 cc. AcOH and 50 cc. H2O, poured into H2O, and extracted with Et2O, and the extract worked up gave 1.5 g. oily 4,3-MeO2C(MeO)C6H3CHO; 2,4-dinitrophenylhydrazone m. 228-30° (C6H6). VIII (4 g.) in 100 cc. EtOH treated dropwise with stirring with 1.1 g. KCN in 50 cc. H2O, kept 4 h. at room temperature, refrigerated 14 h., diluted with saturated aqueous NaCl, and extracted with Et2O gave 1.77 g. 4,3-MeO2C(MeO)C6H3CH2CN, b0.3 149-50° m. 59-60°(EtOH). 4,2-Me(MeO)C6H3CO2H (20 g.) in 300 cc. dry CCl4 refluxed and irradiated as above with stirring, treated with a small amount powd. AlCl3 and a few cc. solution of 2.14 g. Br in 120 cc. CCl4, the mixture then treated dropwise during 17-20 h. with the remainder of the Br solution, kept overnight at room temperature, and several hrs. at 0°, and filtered yielded 15-16 g. 4,3-HO2C(MeO)C6H3CH2Br (IX), m. 124-5° (C6H6). IX (12 g.) stirred 3 h. at 0° with 110 cc. saturated HCl-MeOH, refrigerated overnight, diluted with ice, washed with Et2O, neutralized with solid NaHCO3, and extracted with Et2O gave 10 g. VIII, m. 51°. IX (500 mg.) and 500 mg. NaOAc in 5 cc. AcOH refluxed 2 h., diluted with H2O, and filtered yielded 330 mg. 4,3-HO2C(MeO)C6H3CHOAc, m. 100°. IX (5 g.) neutralized with 2N NaOH, treated gradually with 2 g. KCN, the mixture stirred 2 h. at room temperature, acidified, extracted with CHCl3, and the oily product chromatographed on silica gel yielded 64% 4,3-HO2C(MeO)C6H3CH2CN (X), m. 113-15° (C6H6-ligroine, b. 60-80°). X (1 g.) refluxed 2 h. with 10 cc. aqueous NaOH and 2 cc. EtOH, acidified, and filtered yielded 77% 4,3HO2C(MeO)C6H3CH2-CO2H (XI), m. 137.5-39° (Et2O-petr. ether). XI (1 g.), 2 cc. AcOH, and 2 cc. 48% HBr refluxed 1 h. and cooled gave 0.75 g. I (n = 1), m. 208-10° (H2O). 4,3-NC(O2N)C-6H3Me (XII) (10 g.) treated with Cl during 8.5 h. at 120-30° with irradiation with UV light, cooled, and filtered, and the residue triturated with cold EtOH gave 5 g. crude unreacted XII; the oily residue from the extract refluxed 2 h. with KOAc-AcOH, cooled, poured into H2O, extracted with Et2O, and the oily residue from the extract chromatographed on Al2O3 gave successively 10% oil, 43% unreacted XII, 5% oil, and 20% 4,3-NC(O2N)C6H3CH2OAc (XIII), m. 64-4.5°. XII (7 g.), 0.5 g. Bz2O2, and 45 cc. CCl4 refluxed 67 h. with 8 g. N-bromosuccinimide, filtered, and worked up, and the oily product (1.2 g.) refluxed 2 h. with KOAc-AcOH yielded 32% XIII, m. 64-5°. XII (25 g.) treated at 150° (later at 120-5°) with 3.3 g. Br with UV irradiation during 7 h. and extracted with Et2O, and the oily residue (32.5 g.) from the extract refluxed 2 h. with KOAc-AcOH yielded 25-30% XIII. Similarly were prepared the benzoate analog (XIV), m. 138-9.5° (C6H6), and the p-nitrobenzoate (XV) analog of XIII, m. 168.570° (CHCl3-C6H6). XIII, XIV, and XV treated overnight with an equivalent amount 50% aqueous KOH in 50-100 volume absolute EtOH at 0° yielded 80% 4,3-NC(O2N)C-6H3CH2OH, m. 78.5-80.5° (C6H6ligroine). 3,4-MeO(O2N)C-6H3Me (XVI) (1.8 g.) in 20 cc. CCl4 refluxed 4-5 h. with 4 cc. Br, bubbled with N, cooled, and filtered gave 2.1 g. 6,3,4-Br(MeO)-(O2N)C6H3Me. XVI (5 g.), 5.4 g. N-bromosuccinimide, and 0.3 g. Bz2O2 refluxed overnight in 30 cc. CCl4 (addnl. Bz2O2 was added after 4 h.) gave 58% 3,4-MeO(O2N)C6H3CH2Br (XVII), m. 97-820 (C6H6-ligroine). XVII (230 mg.), 230 mg. KOAc, and 5 cc. AcOH refluxed 1 h. yielded 175 mg. 3,4-MeO(O2N)C6-H3CH2OAc, m. 61-3° (C6-H6petr. ether). XVII (4 g.), 3.5 g. (CH2)-6N4, and 30 cc. CHCl3 refluxed 4 h., cooled, and filtered, and the residue (5.5-6.0 g.) refluxed 2 h. with 45 cc. AcOH and 45 cc. H2O, cooled, poured onto ice, and extracted with Et2O yielded 1.1-1.6 g. yellow 3,4-MeO-(O2N)C6H3CHO, m. 97-9° (EtOH); 2,4-dinitrophenylhydrazone m. 279-80° (EtOAc). X (1.05 g.) in 30 cc. Ac2O hydrogenated over 200 mg. PtO2, centrifuged, and evaporated, and the oily residue refluxed 4 h. with 2 cc. AcOH and 2 cc. 48% HBr and filtered gave 0.7 g. 4,2H2NCH2CH2(HO)C6-H3CO2H.HBr, m. 260° (absolute EtOH-Et2O). Hydrated Na2S (25.7 g.), 10.7 g. sulfur flowers, 23 g. KOH pellets, and 51 cc. H2O heated 15 min. on a water bath, added to 35 g. XVI in 260 cc. 95% EtOH, refluxed 4 h., steam distilled, and the distilled oil stirred several hrs. at 0° and filtered gave 13.6 g. 4,3-H2-N(MeO)C6H3CHO (XVIII), m. 100°; the gummy residue from the filtrate dissolved twice in saturated aqueous NaHSO3 and treated with 5N NaOH gave an addnl. 7.8 g. XVIII. XVIII (12 g.), 60 cc. AcOH, 10 cc. Ac2O, and 6 g. NaOAc refluxed 1.5 h., poured onto ice, saturated with Na2CO3, and filtered gave 15.3 g. 4,3-AcNH(MeO)C6H-3CHO (XIX), m. 142-5°. XIX (18.5 g.) in 23.5 cc. C5H5N, 10 g. CH2(CO-2H)2, and 1 cc. piperidine heated 5 h. on a water bath, cooled, poured onto 300 cc. ice and 30 cc. AcOH, and filtered yielded 75% 4,3-AcNH(MeO)C6H3CH:CHCO2H (XX), m. 213° (decomposition)(EtOH). XX (5.0 g.) in 30 cc. H2O shaken 1 h. with Na-Hg from 1.32 g. Na and 72 g. Hg, filtered, and acidified yielded 4.4 g. 4,3-AcNH(MeO)-C6H3CH2CH2CO-2H (XXI), m. 112° (H2O). XXI (6 g.) and 10 cc. solution of 8.8 g. KOH in 6.3 cc. H2O, diluted with MeOH to 25 cc., heated 1 h. on a water bath, treated with 5.5 cc. H2O, heated again 0.5 h., neutralized with HCl, and filtered gave 4.8 g. 4,3-H2N(MeO)C6H3CH2CH2CO2H (XXII), m. 98-9° (C6H6-ligroine). XXII (5 g.) neutralized with 2.7 g. Na2CO3 in 20 cc. H2O, treated with cooling with 2 g. NaNO2 in 10 cc. H2O, added with stirring and cooling to 10.5 cc. concentrated HCl and 10.5 cc. H2O at 6-8°, poured at 50-60° to a solution of CuCN from 6 g. CuSO4, 7.5 g.. KCN, and 30 cc. H2O, stirred 1 h. at 60-70°, filtered, acidified, and extracted with CHCl-3 yielded 2.9-3.15 g. 4,3-NC(MeO)C6H-3CH2CH2CO2H (XXIII), m. 159-60° (C6H6-ligroine). XXIII (0.5 g.), 1 cc. AcOH, and 1 cc. 48% HBr refluxed overnight and filtered gave 0.27 g. I (n = 2), m. 230° (decomposition) (EtOH). XVI (20 g.), 500 cc. H2O, and 45 g. KMnO4 refluxed until decolorized, treated during 6 h. at 0.5-h. intervals with 5-g. portions KMnO4, filtered hot, concentrated to 250 cc., and acidified with concentrated HCl gave 20-2 g. 3,4-MeO(O2N)C6H3CO2H (XXIV), m. 230.5°. XXIV (25 g.) and 50 cc. SOCl2 refluxed 4 h. and distilled yielded 22 g. 3,4-MeO(O2N)C6H3COCl (XXV), b1 150-60°, m. 50-5°. Mg (5.85 g.), 37 cc. absolute EtOH, and 1 cc. dry CCl4 treated with stirring with 37 cc. dry PhCl and then during 4 h. with coolingwith 26.4 cc. CH2(CO2Et)-2 and 18 cc. PhCl in 80 cc. absolute EtOH below 65°, heated slowly to 85°, kept about 2 h. at 85°, cooled to 25°, treated slowly with 32 g. XXV in 93 cc. PhCl with stirring below 35°, stirred 0.5 h. at 35°, and treated with cooling with 9.3 cc. H2SO4 > in 65 cc. H2O, the organic phase decanted, dried, and evaporated, and the residue refluxed 6 h. with 5 cc. AcOH, 6.5 cc. H2SO4, and 35 cc. H2O, cooled, and poured onto ice gave 19.5 g. 3,4-MeO(O2N)C6H3Ac (XXVI), m. 72-3° (ligroine); 15% unreacted XXV was recovered. XXVI (2 g.) in 5 cc. AcOH treated slowly with 1.64 g. Br in 5 cc. AcOH, diluted wi h H2O, and filtered yielded 2.5 g. 3,4-MeO(O2N)C6H3COCH2Br (XXVII), m. 90-1.5° (EtOH). NaH (250 mg.) and 3.1 cc. CH2(CO2Et)2 in 25 cc. HCONMe2 stirred until H evolution ceased, stirred an addnl. 0.5 h., treated with 2.74 g. XXVII in 30 cc. HCONM 2, stirred 23 h. at room temperature, evaporated in vacuo, and the residual oil triturated with a little Et2O gave 1.3 g. 3,4-MeO(O2N)C6H-3COCH2CH(CO2Et)2, m. 78-80° (EtOH), which upon acid or alk. hydrolysis gave only gummy products. EtO2CCHAcCH CO2Et (XXVIII)(15.5 g.) and 1.65 g. powd. Na in 105 cc. C6H6 refluxed 2 h., treated slowly with 15 g. 3,4-MeO(O2N)C6H3C ,Cl in 45 cc. C6H6, heated 1 h. on a water bath, kept 24 h., filtered, evaporated, the residue dissolved in 100 cc. Et2O, filtered, worked up, and the viscous oily product heated with occasional shaking on a water bath with 110 cc. 70 % H2SO4, cooled, filtered, and poured into ice gave 5.8 g. 3,4-MeO(O2N)C6H3CO-CH2CH-2CO2H (XXIX), m. 137-8.5° (H2O). XXVIII treated in the usual manner with 1 g. 3,4-MeO(O2N)C6H3COCl yielded 34% 3,4-MeO(O2N)C6H3COCAc(CO-2Me)CH2CO2Me, m. 99-100.5° (Et2O-petr. ether). XXIX (32.4 g.) in 145 cc. 2N NH4OH added at room temperature to 208 g. FeSO-4.5H2O in 340 cc. H2O, basified with 10% NH4OH, boiled a few min., filtered, concentrated to about 800 cc., adjusted with concentrated HCl to pH 6, and filtered gave 23 g. 4,3-H2N(MeO)C6-H3COCH2CH2CO2H (XXX), m. 152-3° (H2O). XXX (22.5 g.) and 10.3 g. Na2CO3 in 60 cc. H2O treated with stirring and cooling with 7.9 g. NaNO2 in 70 cc. H2O and then slowly with cold 52 cc. concentrated HCl and 52 cc. H2O below 4° added to CuCN solution from 23.4 g. CuSO4 and 29.3 g. KCN in 175 cc. H2O, heated 1 h. at 70° cooled, and acidified yielded 14.4 g. 4,3-NC(MeO)C6-H3COCH2CH2CO2H (XXXI), m. 153-4° (CHCl3). XXXI (14 g.), 104 cc. 10% aqueous NaOH, and 28 cc. 95% EtOH refluxed 2.5 h. under N, cooled, acidified with concentrated HCl, and extracted with CHCl3 yielded 10.6 g. 4,3-HO2C-(MeO)C6H3COCH2CH2CO2H (XXXII), m. 158-9.5° (CHCl3-ligroine). XXXII (10.6 g.), 60 cc.(HOCH2CH2)-2O, 8 g. KOH pellets, and 10 cc. 95% N2H4.H2O refluxed 2 h., distilled to 145-50° pot temperature, refluxed 5 h., cooled, acidified with concentrated HCl, extracted with CHCl3, and the crude oily product (6.7 g.) chromatographed on silica gel yielded 2.38 g. 4,3-HO2C(MeO)C-6H3(CH2)3CO2H (XXXIII), m. 110-12° (C6H6-ligroine). XXXIII (2.5 g.) heated 1 h. on a water bath with 5 cc. AcOH and 5 cc. 48% HBr yielded 1.1g. I(n = 3), m.205-° (H2O). XXXI (200 mg.), 0.4 cc. AcOH, and 0.4 cc. 48% HBr refluxed overnight gave 15 mg. 4,3-HO2C(HO)C6H3COCH2CH-2CO2H, m. 211-14° (H2O). The experimental process involved the reaction of Methyl 5-bromo-2-methoxy-4-methylbenzoate(cas: 39503-58-7).Product Details of 39503-58-7

Methyl 5-bromo-2-methoxy-4-methylbenzoate(cas:39503-58-7) belongs to organobromine compounds. Most organobromine compounds, like most organohalide compounds, are relatively nonpolar. Bromine is more electronegative than carbon (2.9 vs 2.5). Consequently, the carbon in a carbon–bromine bond is electrophilic, i.e. alkyl bromides are alkylating agents. Product Details of 39503-58-7

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary

Julia, Marc; Chastrette, Francine published an article in 1962, the title of the article was 4-Substituted salicyclic acids.HPLC of Formula: 90326-61-7 And the article contains the following content:

The preparation of 4,3-HO2C(HO)C6H3(CH2)nCO2H (I) (n = 1, 2, 3) is described. m-AcOC6H4Me (600 g.) and 600 cc. powd. AlCl3 heated at 120-65° and steam distilled, and the distillate extracted with Et2O gave 470 g. 4,2-Me(HO)C6H3Ac (II), b0.6 82-4°, n2D4 1.5542; semicarbazone m. 218-20° (EtOH). II (167 g.) in 500 cc. aqueous NaOH heated 6 h. on a steam bath with 140 g. Me2SO4, treated again with 470 g. Me2SO4 and with a sufficient amount aqueous NaOH to maintain alkalinity, and extracted with Et2O yielded 180 g. 4,2-Me(MeO)C6H3Ac (III), b0.6 100-3°, m. 35-6°; semicarbazone m. 194-8°. III (192 g.) and 4.1 l. 1.4N NaOCl, 2.3-2.6N in NaOH, stirred several hrs., treated with aqueous NaHSO3, and acidified with concentrated HCl precipitated 184 g. 4,2-Me(MeO)C6H3CO2H (IV), m. 103-4° (aqueous EtOH). III (48 g.) treated with 900 cc. 1.7N NaOCl, 3.14N in NaOH, yielded 53 g. 3,5,4,2-Cl2Me(MeO)C6-H6CO2H, m. 175-6°. IV (93 g.), 900 cc. absolute MeOH, and 6 g. concentrated H2SO4 refluxed overnight, the mixture concentrated, poured onto ice, and extracted with Et2O gave 75 g. 4,2-Me(MeO)C6H3CO2Me (V), b22 142°, m. 29°, n1D8 1.5230. V (4.5 g.) in 100 cc. AcOH treated dropwise with 4.5 g. Br, the mixture stirred 3 h., kept overnight, diluted with H2O, and extracted with Et2O yielded 5.4 g. Me ester (VI) of 5,4,2-BrMe(MeO)C6H2CO2H (VII), m. 46°. VI saponified gave VII, m. 134-5°. IV (2.2 g.) in 40 cc. CCl4 refluxed and irradiated (W filament) with stirring, treated during 1 h. with 2.2 g. Br, heated 2 h., stirred 12 h., and filtered gave 2.44 g. VII, m. 135° (C6H6). VII (6.2 g.) in 90 cc. 95% EtOH and 30 g. Raney Ni-Al alloy treated dropwise with 300 cc. 10% aqueous NaOH, refluxed 1 h., and filtered, the filtrate added to 250 cc. concentrated HCl, the precipitate extracted with C6H6, and the extract evaporated yielded 3.66 g. IV, m. 102°. N-Bromosuccinimide (2.5 g.), 3.6 g. Bz2O2, 30 g. V, and 75 cc. CCl4 refluxed 3 h., cooled, filtered, and distilled gave 7 g. unchanged V and 26 g. oil, b0.03 122-42°, which, fractionally recrystallized from MeOH and petr. ether, gave 4 g. VI and 8 g. 4,2BrCH2(MeO)C6H3CO2Me (VIII), m. 51°. VIII (4 g.) and 3.2 g. (CH2)6N4 in 30 cc. CHCl3 refluxed I hr. and filtered, the residue refluxed 2 h. with 50 cc. AcOH and 50 cc. H2O, poured into H2O, and extracted with Et2O, and the extract worked up gave 1.5 g. oily 4,3-MeO2C(MeO)C6H3CHO; 2,4-dinitrophenylhydrazone m. 228-30° (C6H6). VIII (4 g.) in 100 cc. EtOH treated dropwise with stirring with 1.1 g. KCN in 50 cc. H2O, kept 4 h. at room temperature, refrigerated 14 h., diluted with saturated aqueous NaCl, and extracted with Et2O gave 1.77 g. 4,3-MeO2C(MeO)C6H3CH2CN, b0.3 149-50° m. 59-60°(EtOH). 4,2-Me(MeO)C6H3CO2H (20 g.) in 300 cc. dry CCl4 refluxed and irradiated as above with stirring, treated with a small amount powd. AlCl3 and a few cc. solution of 2.14 g. Br in 120 cc. CCl4, the mixture then treated dropwise during 17-20 h. with the remainder of the Br solution, kept overnight at room temperature, and several hrs. at 0°, and filtered yielded 15-16 g. 4,3-HO2C(MeO)C6H3CH2Br (IX), m. 124-5° (C6H6). IX (12 g.) stirred 3 h. at 0° with 110 cc. saturated HCl-MeOH, refrigerated overnight, diluted with ice, washed with Et2O, neutralized with solid NaHCO3, and extracted with Et2O gave 10 g. VIII, m. 51°. IX (500 mg.) and 500 mg. NaOAc in 5 cc. AcOH refluxed 2 h., diluted with H2O, and filtered yielded 330 mg. 4,3-HO2C(MeO)C6H3CHOAc, m. 100°. IX (5 g.) neutralized with 2N NaOH, treated gradually with 2 g. KCN, the mixture stirred 2 h. at room temperature, acidified, extracted with CHCl3, and the oily product chromatographed on silica gel yielded 64% 4,3-HO2C(MeO)C6H3CH2CN (X), m. 113-15° (C6H6-ligroine, b. 60-80°). X (1 g.) refluxed 2 h. with 10 cc. aqueous NaOH and 2 cc. EtOH, acidified, and filtered yielded 77% 4,3HO2C(MeO)C6H3CH2-CO2H (XI), m. 137.5-39° (Et2O-petr. ether). XI (1 g.), 2 cc. AcOH, and 2 cc. 48% HBr refluxed 1 h. and cooled gave 0.75 g. I (n = 1), m. 208-10° (H2O). 4,3-NC(O2N)C-6H3Me (XII) (10 g.) treated with Cl during 8.5 h. at 120-30° with irradiation with UV light, cooled, and filtered, and the residue triturated with cold EtOH gave 5 g. crude unreacted XII; the oily residue from the extract refluxed 2 h. with KOAc-AcOH, cooled, poured into H2O, extracted with Et2O, and the oily residue from the extract chromatographed on Al2O3 gave successively 10% oil, 43% unreacted XII, 5% oil, and 20% 4,3-NC(O2N)C6H3CH2OAc (XIII), m. 64-4.5°. XII (7 g.), 0.5 g. Bz2O2, and 45 cc. CCl4 refluxed 67 h. with 8 g. N-bromosuccinimide, filtered, and worked up, and the oily product (1.2 g.) refluxed 2 h. with KOAc-AcOH yielded 32% XIII, m. 64-5°. XII (25 g.) treated at 150° (later at 120-5°) with 3.3 g. Br with UV irradiation during 7 h. and extracted with Et2O, and the oily residue (32.5 g.) from the extract refluxed 2 h. with KOAc-AcOH yielded 25-30% XIII. Similarly were prepared the benzoate analog (XIV), m. 138-9.5° (C6H6), and the p-nitrobenzoate (XV) analog of XIII, m. 168.570° (CHCl3-C6H6). XIII, XIV, and XV treated overnight with an equivalent amount 50% aqueous KOH in 50-100 volume absolute EtOH at 0° yielded 80% 4,3-NC(O2N)C-6H3CH2OH, m. 78.5-80.5° (C6H6ligroine). 3,4-MeO(O2N)C-6H3Me (XVI) (1.8 g.) in 20 cc. CCl4 refluxed 4-5 h. with 4 cc. Br, bubbled with N, cooled, and filtered gave 2.1 g. 6,3,4-Br(MeO)-(O2N)C6H3Me. XVI (5 g.), 5.4 g. N-bromosuccinimide, and 0.3 g. Bz2O2 refluxed overnight in 30 cc. CCl4 (addnl. Bz2O2 was added after 4 h.) gave 58% 3,4-MeO(O2N)C6H3CH2Br (XVII), m. 97-820 (C6H6-ligroine). XVII (230 mg.), 230 mg. KOAc, and 5 cc. AcOH refluxed 1 h. yielded 175 mg. 3,4-MeO(O2N)C6-H3CH2OAc, m. 61-3° (C6-H6petr. ether). XVII (4 g.), 3.5 g. (CH2)-6N4, and 30 cc. CHCl3 refluxed 4 h., cooled, and filtered, and the residue (5.5-6.0 g.) refluxed 2 h. with 45 cc. AcOH and 45 cc. H2O, cooled, poured onto ice, and extracted with Et2O yielded 1.1-1.6 g. yellow 3,4-MeO-(O2N)C6H3CHO, m. 97-9° (EtOH); 2,4-dinitrophenylhydrazone m. 279-80° (EtOAc). X (1.05 g.) in 30 cc. Ac2O hydrogenated over 200 mg. PtO2, centrifuged, and evaporated, and the oily residue refluxed 4 h. with 2 cc. AcOH and 2 cc. 48% HBr and filtered gave 0.7 g. 4,2H2NCH2CH2(HO)C6-H3CO2H.HBr, m. 260° (absolute EtOH-Et2O). Hydrated Na2S (25.7 g.), 10.7 g. sulfur flowers, 23 g. KOH pellets, and 51 cc. H2O heated 15 min. on a water bath, added to 35 g. XVI in 260 cc. 95% EtOH, refluxed 4 h., steam distilled, and the distilled oil stirred several hrs. at 0° and filtered gave 13.6 g. 4,3-H2-N(MeO)C6H3CHO (XVIII), m. 100°; the gummy residue from the filtrate dissolved twice in saturated aqueous NaHSO3 and treated with 5N NaOH gave an addnl. 7.8 g. XVIII. XVIII (12 g.), 60 cc. AcOH, 10 cc. Ac2O, and 6 g. NaOAc refluxed 1.5 h., poured onto ice, saturated with Na2CO3, and filtered gave 15.3 g. 4,3-AcNH(MeO)C6H-3CHO (XIX), m. 142-5°. XIX (18.5 g.) in 23.5 cc. C5H5N, 10 g. CH2(CO-2H)2, and 1 cc. piperidine heated 5 h. on a water bath, cooled, poured onto 300 cc. ice and 30 cc. AcOH, and filtered yielded 75% 4,3-AcNH(MeO)C6H3CH:CHCO2H (XX), m. 213° (decomposition)(EtOH). XX (5.0 g.) in 30 cc. H2O shaken 1 h. with Na-Hg from 1.32 g. Na and 72 g. Hg, filtered, and acidified yielded 4.4 g. 4,3-AcNH(MeO)-C6H3CH2CH2CO-2H (XXI), m. 112° (H2O). XXI (6 g.) and 10 cc. solution of 8.8 g. KOH in 6.3 cc. H2O, diluted with MeOH to 25 cc., heated 1 h. on a water bath, treated with 5.5 cc. H2O, heated again 0.5 h., neutralized with HCl, and filtered gave 4.8 g. 4,3-H2N(MeO)C6H3CH2CH2CO2H (XXII), m. 98-9° (C6H6-ligroine). XXII (5 g.) neutralized with 2.7 g. Na2CO3 in 20 cc. H2O, treated with cooling with 2 g. NaNO2 in 10 cc. H2O, added with stirring and cooling to 10.5 cc. concentrated HCl and 10.5 cc. H2O at 6-8°, poured at 50-60° to a solution of CuCN from 6 g. CuSO4, 7.5 g.. KCN, and 30 cc. H2O, stirred 1 h. at 60-70°, filtered, acidified, and extracted with CHCl-3 yielded 2.9-3.15 g. 4,3-NC(MeO)C6H-3CH2CH2CO2H (XXIII), m. 159-60° (C6H6-ligroine). XXIII (0.5 g.), 1 cc. AcOH, and 1 cc. 48% HBr refluxed overnight and filtered gave 0.27 g. I (n = 2), m. 230° (decomposition) (EtOH). XVI (20 g.), 500 cc. H2O, and 45 g. KMnO4 refluxed until decolorized, treated during 6 h. at 0.5-h. intervals with 5-g. portions KMnO4, filtered hot, concentrated to 250 cc., and acidified with concentrated HCl gave 20-2 g. 3,4-MeO(O2N)C6H3CO2H (XXIV), m. 230.5°. XXIV (25 g.) and 50 cc. SOCl2 refluxed 4 h. and distilled yielded 22 g. 3,4-MeO(O2N)C6H3COCl (XXV), b1 150-60°, m. 50-5°. Mg (5.85 g.), 37 cc. absolute EtOH, and 1 cc. dry CCl4 treated with stirring with 37 cc. dry PhCl and then during 4 h. with coolingwith 26.4 cc. CH2(CO2Et)-2 and 18 cc. PhCl in 80 cc. absolute EtOH below 65°, heated slowly to 85°, kept about 2 h. at 85°, cooled to 25°, treated slowly with 32 g. XXV in 93 cc. PhCl with stirring below 35°, stirred 0.5 h. at 35°, and treated with cooling with 9.3 cc. H2SO4 > in 65 cc. H2O, the organic phase decanted, dried, and evaporated, and the residue refluxed 6 h. with 5 cc. AcOH, 6.5 cc. H2SO4, and 35 cc. H2O, cooled, and poured onto ice gave 19.5 g. 3,4-MeO(O2N)C6H3Ac (XXVI), m. 72-3° (ligroine); 15% unreacted XXV was recovered. XXVI (2 g.) in 5 cc. AcOH treated slowly with 1.64 g. Br in 5 cc. AcOH, diluted wi h H2O, and filtered yielded 2.5 g. 3,4-MeO(O2N)C6H3COCH2Br (XXVII), m. 90-1.5° (EtOH). NaH (250 mg.) and 3.1 cc. CH2(CO2Et)2 in 25 cc. HCONMe2 stirred until H evolution ceased, stirred an addnl. 0.5 h., treated with 2.74 g. XXVII in 30 cc. HCONM 2, stirred 23 h. at room temperature, evaporated in vacuo, and the residual oil triturated with a little Et2O gave 1.3 g. 3,4-MeO(O2N)C6H-3COCH2CH(CO2Et)2, m. 78-80° (EtOH), which upon acid or alk. hydrolysis gave only gummy products. EtO2CCHAcCH CO2Et (XXVIII)(15.5 g.) and 1.65 g. powd. Na in 105 cc. C6H6 refluxed 2 h., treated slowly with 15 g. 3,4-MeO(O2N)C6H3C ,Cl in 45 cc. C6H6, heated 1 h. on a water bath, kept 24 h., filtered, evaporated, the residue dissolved in 100 cc. Et2O, filtered, worked up, and the viscous oily product heated with occasional shaking on a water bath with 110 cc. 70 % H2SO4, cooled, filtered, and poured into ice gave 5.8 g. 3,4-MeO(O2N)C6H3CO-CH2CH-2CO2H (XXIX), m. 137-8.5° (H2O). XXVIII treated in the usual manner with 1 g. 3,4-MeO(O2N)C6H3COCl yielded 34% 3,4-MeO(O2N)C6H3COCAc(CO-2Me)CH2CO2Me, m. 99-100.5° (Et2O-petr. ether). XXIX (32.4 g.) in 145 cc. 2N NH4OH added at room temperature to 208 g. FeSO-4.5H2O in 340 cc. H2O, basified with 10% NH4OH, boiled a few min., filtered, concentrated to about 800 cc., adjusted with concentrated HCl to pH 6, and filtered gave 23 g. 4,3-H2N(MeO)C6-H3COCH2CH2CO2H (XXX), m. 152-3° (H2O). XXX (22.5 g.) and 10.3 g. Na2CO3 in 60 cc. H2O treated with stirring and cooling with 7.9 g. NaNO2 in 70 cc. H2O and then slowly with cold 52 cc. concentrated HCl and 52 cc. H2O below 4° added to CuCN solution from 23.4 g. CuSO4 and 29.3 g. KCN in 175 cc. H2O, heated 1 h. at 70° cooled, and acidified yielded 14.4 g. 4,3-NC(MeO)C6-H3COCH2CH2CO2H (XXXI), m. 153-4° (CHCl3). XXXI (14 g.), 104 cc. 10% aqueous NaOH, and 28 cc. 95% EtOH refluxed 2.5 h. under N, cooled, acidified with concentrated HCl, and extracted with CHCl3 yielded 10.6 g. 4,3-HO2C-(MeO)C6H3COCH2CH2CO2H (XXXII), m. 158-9.5° (CHCl3-ligroine). XXXII (10.6 g.), 60 cc.(HOCH2CH2)-2O, 8 g. KOH pellets, and 10 cc. 95% N2H4.H2O refluxed 2 h., distilled to 145-50° pot temperature, refluxed 5 h., cooled, acidified with concentrated HCl, extracted with CHCl3, and the crude oily product (6.7 g.) chromatographed on silica gel yielded 2.38 g. 4,3-HO2C(MeO)C-6H3(CH2)3CO2H (XXXIII), m. 110-12° (C6H6-ligroine). XXXIII (2.5 g.) heated 1 h. on a water bath with 5 cc. AcOH and 5 cc. 48% HBr yielded 1.1g. I(n = 3), m.205-° (H2O). XXXI (200 mg.), 0.4 cc. AcOH, and 0.4 cc. 48% HBr refluxed overnight gave 15 mg. 4,3-HO2C(HO)C6H3COCH2CH-2CO2H, m. 211-14° (H2O). The experimental process involved the reaction of 5-Bromo-2-methoxy-4-methylbenzoic acid(cas: 90326-61-7).HPLC of Formula: 90326-61-7

5-Bromo-2-methoxy-4-methylbenzoic acid(cas:90326-61-7) belongs to organobromine compounds. Most organobromine compounds, like most organohalide compounds, are relatively nonpolar. Bromine is more electronegative than carbon (2.9 vs 2.5). Consequently, the carbon in a carbon–bromine bond is electrophilic, i.e. alkyl bromides are alkylating agents. HPLC of Formula: 90326-61-7

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary

Kolsaker, Per; Bailey, Philip S.; Dobinson, Frank; Kumar, Baldev published an article in 1964, the title of the article was Ozonation of 9,10-dihaloanthracenes.Product Details of 41819-13-0 And the article contains the following content:

Ozonation of 9,10-dibromoanthracene gave anthraquinone, 1,4-dibromo-2,3-naphthalenedicarboxylic acid, and 3,6-dibromo-1,2,4,5-benzenetetracarboxylic acid (dibromopyromellitic acid). Approx. 2 moles mol. oxygen was evolved per mole of anthraquinone produced when 2 equivalents or less of ozone was used. Bromine was also a product and reacted with ozone when more than 2 equivalents was employed. There is a definite, though not so great as originally reported, solvent effect involving the competition between atom and bond attack of ozone. Similar results were obtained with 9,10-dichloroanthracene, except that there was little, if any, solvent effect. Mechanisms are discussed. The experimental process involved the reaction of 3,6-Dibromobenzene-1,2,4,5-tetracarboxylic acid(cas: 41819-13-0).Product Details of 41819-13-0

3,6-Dibromobenzene-1,2,4,5-tetracarboxylic acid(cas:41819-13-0) belongs to organobromine compounds. Most organobromine compounds, like most organohalide compounds, are relatively nonpolar. Bromine is more electronegative than carbon (2.9 vs 2.5). Consequently, the carbon in a carbon–bromine bond is electrophilic, i.e. alkyl bromides are alkylating agents. Product Details of 41819-13-0

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary

Philippi, Ernst; Seka, Reinhard; Robinson, Lilly published an article in 1922, the title of the article was Mellitic acid, pyromellitic acid and their formation upon the oxidation of coal. IV. Synthesis of substituted pyromellitic acids.Product Details of 41819-13-0 And the article contains the following content:

Nitration of 1,4,2,5-C6H2Me2Et2 gave a poor yield of 1,4-dinitro-2,5-dimethyl-3,6-diethyl- benzene, yellow, m. 100°. Nitration of 1,4,2,5-C6H2Me2EtAc with 5 parts HNO3 and subsequent oxidation at 160-70° gave a mononitro derivative of B, while if 10-12 parts HNO3 are used, a dinitro derivative is formed, yellow powder, m. 190-200° decomposition 1,4-Dibromo-2,5-dimethyl-3,6-diethylbenzene is obtained by dissolving C6H2Me2Et2 in ligroin and adding HNO3 and then S2Br2, needles, m. 81-2°. On oxidation with HNO3 at 140-60° in a sealed tube, 1,4-dibromo-2,5-dimethylbenzene-3,6-diacetic acid is formed, needles, decomposition about 180°; there also results 1,4-dibromo-2,5-dimethylbenzene-3,6 diketocarboxylic acid, needles, m. 232°; and dibromopyromellitic acid, decompose 230°. The experimental process involved the reaction of 3,6-Dibromobenzene-1,2,4,5-tetracarboxylic acid(cas: 41819-13-0).Product Details of 41819-13-0

3,6-Dibromobenzene-1,2,4,5-tetracarboxylic acid(cas:41819-13-0) belongs to organobromine compounds. Most organobromine compounds, like most organohalide compounds, are relatively nonpolar. Bromine is more electronegative than carbon (2.9 vs 2.5). Consequently, the carbon in a carbon–bromine bond is electrophilic, i.e. alkyl bromides are alkylating agents. Product Details of 41819-13-0

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary

von Walther, R. F.; Zipper, W. published an article in 1915, the title of the article was p-Chloro- and p-bromo-m-cresols. I.Recommanded Product: 39503-58-7 And the article contains the following content:

Halogenated cresols have powerful antiseptic properties; p-chloro-m-cresol surpasses all other analogous phenol derivatives in this respect and therefore derivatives of this substance are of special interest. While the chlorination of o- and p-cresol with the formation of monosubstitution products proceeds with comparative case (cf. Ber. 16, 1598), m-cresol shows a great tendency to take up 2 atoms of Cl and it is only by protecting the OH group or observing special precautions as to temperature and dilution that the formation of dichloro-m-cresol can be avoided. By chlorinating m-HOC6H4Me (a) in glacial or 90% AcOH both at room temperature and at 100°, the following compounds were isolated by W. and Z.: 2,4,6-trichloro-m-cresol (b), 1-methyl-2,4,5-trichloroquinone dichloride (c), 1-chloromethyl-2,4,5-trichloroquinone dichloride (d), and 2,4,5-trichlorotoluquinone (e). (b) seps. in prisms when (a) in glacial AcOH is saturated cold with Cl; faintly yellow needles in clusters, m. 45° (cf. C. A. 6, 354; 7, 2546). When the filtrate from (b) is again saturated with Cl and allowed to stand, (d) seps.; prisms from alc., m. 117°. (e) is obtained when (a) is saturated at 100° with Cl. Some (d) seps. on cooling, which is filtered off, the solution again saturated with Cl, cooled, and diluted with H2O, when an oil seps. which deposits (e), yellow leaves from alc., m. 238° (decomposition). This m. p. is somewhat higher than that ascribed by previous investigators (cf. Ann. 168, 268; 172, 210; 237, 145) and lower than that of Michaelis (Ann. 293, 275). When (a) in the least quantity of 90% AcOH is saturated with Cl at 100°, a yellow oil and a crystalline solid sep. on cooling. The latter consists of (c), (d) and (e), which may be separated by crystallization from alc. 4,6-Dichloro-3-cresol (f), probably the dichloro-m-cresol obtained by Claus and Schweitzer (Ber. 19, 927) on chlorinating (a) hot and considered to be the 2,4-Cl2 compound, was obtained by W. and Z. from 6-chloro-3-cresol (p-chloro-m-cresol) (g), when treated in warm aqueous Na2CO3 with the calculated quantity of Cl and allowed to stand. The yellow oil which seps. on dilution with H2O is probably a mixture of mono-, di- and trichloro-m-cresols; on long standing (f) crystallines from this mixture, needles from Et2O, m. 45-6; FeCl3 gives no phenol reaction. Contrary to the finding of C. and S., neither this product nor any other dichloro-m-cresol was ever obtained by W. and Z. by the direct chlorination of (a) in AcOH. 6-Bromo-3-cresol (h) is obtained smoothly in 83% yield when (a) in CCl4 is treated slowly with the calculated amount of Br at -5° to -10°; needles from H2O or ligroin, volatile with steam, m. 62°; 100 cc. H2O dissolves 0.1713 g. at 19°. Benzoyl derivative, from BzCl in C5H5N, needles from alc., m. 83-83.5°. 6-Chloro-4-bromo-3-cresol (i) is obtained in needles when (g) in CCl4 is treated with Br in CCl4 in portions and the solvent evaporated; needles from petr. ether, m. 70-70.5°. When (g) in glacial AcOH is treated with Br until the red color persists, a brownish red oil seps., from which 6-chloro-2,4-dibromo-3-cresol (j) is extracted by 50% AcOH; needles from petr. ether, m. 70°-70.5°, b17 177°; yield, 67%. 6-Chloro-3-hydroxy-4-toluic acid (p-chloro-m-cresotinic acid) (k), previously prepared by Gattermann (Ber. 26, 1851), is obtained in 95% yield when dry Na (g) is heated at 160-75° with an excess of CO2 at high pressure for 6 hrs. The brown product is dissolved in NaOH, largely diluted, decolorized hot with SnCl2, filtered and precipitated by HCl; leaves from CHCl3, needles from alc., m. 206-7°; it is volatile with steam and sublimes readily; 100 cc. H2O dissolves 0.0120 g. at 12°. (The Na salt of (g) is much more readily decomposed than PhONa; in the presence of a trace of H2O, it chars as low as 180°.) (k) is also formed in almost quant. yield by the action of Cl (calculated amount) on m-cresotinic acid (l) in glacial AcOH. (c), (d) and (e) are also formed in small quantities, but there was no tendency to form polyhalogenated cresotinic acids when AcOH, CCl4, CHCl3, C6H6 or Me2CO were used as solvents. Alc., AcOEt, Et2O, ligroin and CS2 are not suitable mediums; H2O leads to the formation of (e). Sodium salt of (k), seps. in leaves from 96% alc.; potassium salt, needles from H2O; lithium salt, clusters of needles from alc.; ammonium salt, needles from alc.; neutral calcium and neutral barium salts, leaves from H2O; silver salt, fine needles; lead, mercury and aluminium salts, all very difficultly soluble; magnesium salt, leaves from H2O; manganese salt, bright violet needles from H2O; basic copper salt, green leaves, insoluble in H2O; bismuth salt, very difficultly soluble With FeCl3 (k) gives a violet coloration; when the chloride is in excess a brownish red precipitate seps. Hexamethylenetetramine p-chloro-m-cresotinate, (CH2)6 N4.C8H7O3Cl, prisms from alc., m. 170° (decomposition) and gives a weak blue fluorescence in aqueous NaOH; antipyrine salt, C8H7O3Cl.C11H12ON2, needles from H2O, m. 128°; quinine salt, C8H7O3Cl.C20H24O2N2, an oil from H2O, crystallizing in indefinite form; cinchonine salt, C8H7O3Cl.C19H22ON2, indefinite crystals from H2O. Methyl ester of (k), (m), leaves from MeOH, m. 55°; ethyl ester (n), faintly yellow leaves from 96% alc., m. 52-3°; propyl ester (o), prisms, m. 21°, b18 168-70°. Methyl 2-methoxy-4-methyl-5-chlorobenzoate (p), from the Na salt of (m) with EtI or from the Na salt of the (l) with Me2SO4 in NaOH solution, faintly yellow needles from MeOH, m. 53-4°, b14 160°. Methyl 2-ethoxy-4-methyl-5-chlorobenzoate b11 170°; precipitated from MeOH by H2O in faintly yellow needles, m. 54°. Methyl 2-propyloxy-4-methyl-5-chlorobenzoate, b24 188°. Methyl 2-isopropyloxy-4-methyl-5-chlorobenzoate, a highly refractive oil, b19 173°. Methyl 2-butyloxy-4-methyl-5-chlorobenzoate, faintly yellow refractive oil, b20 194°. Methyl 2-isobutyloxy-4-methyl-5-chlorobenzoate (q), refractive oil, crystallizing in prisms, b14 187°. Methyl 2-isoamyloxy-4-methyl-5-chlorobenzoate, faintly yellow refractive oil, b18 197°. 2-Methoxy-4-methyl-5-chlorobenzoic acid, obtained by saponification of (p), prisms from alc., m. 130°; sodium salt, needles; the salts of the alkali metals and the ammonium salt are soluble; calcium, barium, lead, silver, the yellow ferric and the blue copper salts are all difficultly soluble 2-Ethoxy-4-methyl-5-chlorobenzoic acid (r), needles from H2O, m. 143°, 2-propyloxy-4-methyl-5-chlorobenzoic acid, broad prisms from CCl4, m. 112° (sodium salt, needles), 2-isopropyloxy-4-methyl-5-chlorobenzoic acid, long prisms from ligroin, m. 121°, 2-butyloxy-4-methyl-5-chlorobenzoic acid, needles from ligroin, m. 96.5°, and 2-isoamyloxy-4-methyl-5-chlorobenzoic acid, leaves from ligroin, m. 94°, are all obtained by saponification of the corresponding esters. Saponification of (q) with alc. NaOH gave a mixture of 2-isobutyloxy-4-methyl-5-chlorobenzoic acid and (r), m. 117°, which could not be separated 3-Methyl-4-chlorophenyl salicylate, C6H4(OH)CO2C6H3MeCl, is formed when o-HOC6H4CO2H is heated at 135-40° with (g) in the presence of POCl3; fine needles from alc., m. 74°. 3-Methyl-4-chlorophenyl p-chloro-m-cresotinate, from (k), (g), and POCl3 at 140°, small needles from MeOH, m. 142°. Phenyl p-chloro-m-cresotinate (s), needles from MeOH, m. 88°. β-Naphthyl p-chloro-m-cresotinate, prisms from Me2CO, m. 137.5°. Saponification of these new “salols” shows a behavior similar to C6H4(OH)CO2Ph; their therapeutic application is thus possible. Acetyl-p-chloro-m-cresotinic acid, clusters of needles from CCl4, m. 146°. 5-Chloro-4-methyl-2-hydroxybenzoyl chloride (t) is easily obtained on heating (k) with SOCl2 at 80°; long needles from petr. ether, m. 48°; it cannot be distilled without decomposition Treated with PhOH, (t) gives (s). The amide of (k), leaves from alc., is formed when (t) is treated in Et2O with dry NH3; anilide, leaves from alc., m. 222°; p-phenetidide, from (t) and p-NH2C6H4OEt, leaves from 96% alc., m. 215°. 6-Bromo-3-hydroxy-4-toluic acid (p-bromo-m-cresotinic acid) (u) is obtained in theoretical yield when 106 g. Br in 300 g. CCl4 is slowly dropped into 100 g. (l) in 1 kg. CCl4 and let stand 24 hrs.; prisms from 96% alc., which give a bluish violet coloration with FeCl3 and m. 221° (not 211°, as Gattermann, Ber. 26, 1851, gave it); ammonium salt, needles from H2O; the alkali, cobalt and magnesium salts are all easily soluble while the barium, silver, mercury, lead, gold, bright yellow platinum, brownish violet ferric and yellowish green copper salts are all difficultly soluble Both (k) and (u) are more powerful antiseptics than o-HOC6H4CO2H. Methyl 2-methoxy-4-methyl-5-bromobenzoate, formed when (u) is treated with Me2SO4 and MeONa, seps. from dilute MeOH in leaves, in 45-6°; the yield is small as the chief product is methyl 2-hydroxy-4-methyl-5-bromobenzoate, needles from MeOH, m. 48°. Acetyl-p-bromo-m-cresolinic acid seps. in leaves from CHCl3, m. 155°. When (g) in 80% AcOH is treated cold with dilute HNO3, a yellow substance seps. from which 6-chloro-4-nitro-3-cresol (v) is obtained on crystallization from alc. in yellow leaves, m. 133.5°; ammonium salt, orange yellow leaves from H2O, m. 146° (decomposition); sodium salt, red needles; potassium and barium salts, red leaves; calcium salt, orange-red needles; mercury salt, brownish yellow leaves; copper salt, bright green leaves; lead salt, brick red; ferric salt, yellowish to dark brown, featherlike crystals; aluminium salt, yellow featherlike crystals; chromium salt, bright green; silver, gold, and platinum salts, yellow leaves; aniline salt, yellow leaves from alc., m. 134°; p-toluidine salt, bright yellow leaves, m. 133°; o-toluidine salt, yellow leaves, m. 132°. On evaporating the alc. mother liquors from (v), 6-chloro-2,4-dinitro-3-cresol (w) seps.; yellow leaves from ligroin, m. 69°. If heat is applied during the nitration of (g), (w) is the only product of the reaction. Ammonium salt, orange needles, m. 190-224° (decomposition); sodium salt, orange; potassium salt, orange needles; calcium salt, golden yellow scales; barium salt, microscopic orange needles; mercury salt, reddish brown needles; copper and lead salts, brown needles; ferric and aluminium salts, brown leaves; chromium salt, leaves; silver, gold and platinum salts, yellow needles; aniline, p-toluidine and o-toluidine salts, orange needles, m. 136°, 145° and 78°, resp. Reduced with H2SO3 in boiling H2O, (v) is converted into 6-chloro-4-amino-3-cresol, which seps. on cooling in leaves, m. 143°; yield, 80%. The experimental process involved the reaction of Methyl 5-bromo-2-methoxy-4-methylbenzoate(cas: 39503-58-7).Recommanded Product: 39503-58-7

Methyl 5-bromo-2-methoxy-4-methylbenzoate(cas:39503-58-7) belongs to organobromine compounds. Most organobromine compounds, like most organohalide compounds, are relatively nonpolar. Bromine is more electronegative than carbon (2.9 vs 2.5). Consequently, the carbon in a carbon–bromine bond is electrophilic, i.e. alkyl bromides are alkylating agents. Recommanded Product: 39503-58-7

Referemce:
Bromide – Wikipedia,
bromide – Wiktionary