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12 protocols using 4 bromoaniline

1

Synthesis of Brominated Aniline Compounds

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4-Bromoaniline, purity 98%, was obtained from Aldrich (Poole, UK) and was used as received. Bromobenzene, purity 99%, was also obtained from Aldrich. Solvents for HPLC were of high purity HPLC grade and were obtained from Fisher Scientific UK Ltd. (Loughborough, UK).
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2

Synthesis and Characterization of Novel Compounds

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4-Bromobenzyl bromide, 4-bromoaniline, 4-pyridylboronic acid, 1,3-dichlorobenzene, p-tolylmagnesium bromide, n-butyllithium and N-bromosuccinimide were purchased from Aldrich and used as received. Benzoyl peroxide was purchased from Acros and used as received. Compounds 3 [18 (link)], [5][OTf]2 [19 (link)–20 (link)] and 6 [21 (link)] were prepared using literature methods. Solvents were dried using an Innovative Technologies solvent purification system. Thin-layer chromatography (TLC) was performed using Teledyne Silica gel 60 F254 plates and viewed under UV light. Column chromatography was performed using Silicycle ultra-pure silica gel (230–400 mesh). The solvents were dried and distilled prior to use. NMR spectra were recorded on a Bruker Avance III console equipped with an 11.7 T magnet (e.g., 500 MHz for 1H). Samples were locked to the deuterated solvent and all chemical shifts reported in ppm referenced to tetramethylsilane. Mass spectra were recorded on a Waters Xevo G2-XS instrument. Solutions with concentrations of 0.001 molar were prepared in methanol and injected for analysis at a rate of 5 µL/min using a syringe pump.
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3

Synthesis and Characterization of Organometallic Complexes

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Tetrabutylammonium tetrachlorooxorhenate(V), 4-Chloroaniline, 4-Bromoaniline, 4-Methylaniline, 4-isopropylaniline, aniline, 4-Methylcatechol, and 1,2-dihydroxybenzene were purchased from Sigma-Aldrich. Acetonitrile (HPLC grade) and triethylamine were purchased from Fisher Scientific. Nitrogen used as nebulizing and drying gas was generated by MS-NGM 11 (Bruker Daltonics, Bremen, Germany) nitrogen generator.
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4

Functionalization of Carbon Nonwoven

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The prewetted carbon nonwoven (10 × 10 mm2) was placed in a round-bottom flask and treated with 25 mL of 1 M HCl, and then the mixture was heated to 80 °C. After reaching the required temperature, isoamyl nitrite (0.7 mL, 5 mmol) and 4-bromoaniline (0.86 g, 5 mmol) (Sigma-Aldrich, Poznan, Poland) were added to the mixture. The reaction was carried out at 80 °C for 18 h. Finally, the nonwoven fabric was washed with DMF (3 × 5 mL) and DCM (3 × 5 mL).
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5

Metal-Organic Complexation and Biomolecular Interactions

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All reagents and
solvents used in this synthesis were commercially available. Reagent-grade
chemicals were used in this experiment. Hence, no further purification
was needed. Salicylaldehyde, 5-bromo Salicylaldehyde, 4-bromo aniline,
ctDNA, HSA, EB, and DAPI were obtained from Sigma-Aldrich Chemicals.
CuCl2, ZnCl2, and triethyl amine (Et3N) were purchased from Merck. Elemental analyses were performed using
a PerkinElmer 240C elemental analyzer. Electronic absorption spectral
data were collected by using a PerkinElmer UV–vis Lambda 365
spectrophotometer at room temperature. The concentration of ctDNA
per nucleotide was determined by absorption spectroscopy using a molar
extinction coefficient (€) 6600 (M–1 cm–1) at 260 nm. ctDNA interaction studies were performed
in a citrate-phosphate (CP) buffer of 10 mM [Na+] at pH
7.40 containing 0.5 mM Na2HPO4, and HSA interaction
studies were performed in Tris buffer.
Caution! Mercury salts are extremely toxic, so proper caution should be taken
before use.
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6

Synthesis and Characterization of Benzothiazole Derivatives

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All reagents, catalysts,
and chemicals utilized in the study were of analytical quality and
supplied by commercial providers. The chemicals used in this study
were sourced from various suppliers. 2-Aminobenzothiazole (Sigma-Aldrich,
99%), sulfapyridine (NENTECH, U.K., 99%), sulfaguanidine (Tokyo Chemical
Industry, Japan, 98%), piperazine (Central Dreug House, India, 99%),
benzylamine (Loba Chemi, India, 99%), cyclohexylamine (Sigma-Aldrich,
99%), 3,4 dimethylaniline (GCC, U.K., 98%), 4-chloroaniline (Sigma-Aldrich,
98%), 4-bromoaniline (Sigma-Aldrich, 90%), 4-fluoroaniline (Sigma-Aldrich,
99%), 4-nitroaniline (Janssen, Belgium, 98%), diethylamine (GCC, U.K.,
98%), m-toluidine (Sigma-Aldrich, 99%), morpholine
(Tokyo Chemical Industry, Japan, 99%), dimethylformamide (DMF) (Carlo
Erba, France, 99.9%), acetone (Carlo Erba, France, 99%), triethylamine
(TEA) (TEDIA, 99%), ethanol (Carlo Erba, France, 98%), n-hexane (Carlo Erba, France, 95%), sodium bicarbonate (NaHCO3) (GCC, U.K., 99.5%), sodium hydroxide (NaOH) (GCC, U.K.,
99.5%), chloroform (Carlo Erba, France, 99.9%), and dimethyl sulfoxide
(DMSO) (Carlo Erba, France, 99%) and monochloroacetyl chloride (α
Chemika, India) were used.
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7

Synthesis and Characterization of Copper Complexes

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For the synthesis and characterization the following commercial chemicals were used: 4-Bromoaniline (CAS: 106-40-1, 97%, Sigma Aldrich), Cu(NO3)2·3H2O (CAS: 10031-43-3, 98%, Sigma Aldrich), N,N-Dimethylethylenediamine (CAS: 108-00-9, 95%, Sigma Aldrich), 9H-Carbazole (CAS: 86-74-8, >95%, Sigma Aldrich), Copper(I) iodine (CAS: 7681-65-4 99%, Riedel-de Haen), N,N′-Dimethylformamid, (CAS: 68-12-2, 99%, Fischer Scientific). Solvents and stock chemicals were used with purities exceeding 98%.
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8

Synthesis of Substituted Anilines

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4-Bromoaniline (97%) and 3-bromoaniline (97%)
were purchased from Sigma-Aldrich. Ferrous sulfate (FeSO4·7H2O) and potassium permanganate (KMnO4) were purchased from Central Drug House (CDH) and used as received.
The solvents dimethylformamide (DMF) [high-performance liquid chromatography
(HPLC) grade] and TEA were purchased from CDH. TEA was dried in our
laboratory. PA was purchased from Thomas Baker (Chemicals). Tetrakis(triphenylphosphine)palladium(0)
(Pd(PPh3)4) (99%) and copper iodide (CuI) were
purchased from Sigma-Aldrich and were used as received.
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9

Synthesis and Characterization of Sulfanilamide Derivatives

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All of the reagents and
chemicals were of analytical grade and purchased from commercial suppliers.
Sulfapyridine (NENTECH, U.K., 99%), sulfaguanidine (Tokyo Chemical
Industry, Japan, 98%), cyanuric chloride (Acros Organics, China, 99%),
aniline (GCC, U.K., 99.5%), benzylamine (LobaChemi, India, 99%), cyclopropylamine
(Sigma-Aldrich, 98%), cyclohexyl amine (Sigma-Aldrich, 99%), diethylamine
(GCC, U.K., 98%), m-toluidine (Sigma-Aldrich, 99%),
3,4-dimethylaniline (GCC, U.K., 98%), 4-chloroaniline (Sigma-Aldrich,
98%), 4-bromoaniline (Sigma-Aldrich, 90%), 4-fluoroaniline (Sigma-Aldrich,
99%), 4-nitroaniline (Janssen, Belgium, 98%), morpholine (Tokyo Chemical
Industry, Japan, 99%), acetone (Carlo Erba, France, 99%), ethanol
(Carlo Erba, France, 98%), dimethylformamide (DMF) (Carlo Erba, France,
99.9%), n-hexane (Carlo Erba, France, 95%), sodium
bicarbonate (NaHCO3) (GCC, U.K., 99.5%), sodium hydroxide
(NaOH) (GCC, U.K., 99.5%), triethylamine (TEA) (TEDIA, 99%), chloroform
(Carlo Erba, France, 99.9%) and dimethyl sulfoxide (DMSO) (Carlo Erba,
France, 99%).
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10

Synthesis and Characterization of Metal Complexes

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1,10‐phenanthroline (Sigma Aldrich, 97 %), 2–2’‐bipyridine (Alfa Aesar, 99 %), 4,7‐dimethyl‐1,10‐phenanthroline (Sigma Aldrich), 1,10‐phenanthroline‐5‐amine (Sigma Aldrich, 97 %), 4‐bromoaniline (Sigma Aldrich, 99 %), NaNO2 (Merck, 99.9 %), K3Fe(CN)6 (Sigma Aldrich, 99.98 %) and Cu(OTf)2 (Alfa Aesar, ≥99 %) were used as received. Electrolyte solutions were prepared with HClO4 (Merck suprapur, 70 %), HCl (Merck, 37 %), Na2HPO4 (Merck, 99.9 %), NaH2PO4 (Merck, 99.9 %), NaCl (Merck, 99.9 %) and were prepared with MilliQ water (>18.2 MΩ cm resistivity). Argon and oxygen (5.0) were purchased from Linde Gas.
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