Bhatt, M. V. published the artcile< Quinone studies. I. Evidence for a new type of substitution reaction of phenanthrenequinone derivatives>, Quality Control of 90940-40-2, the main research area is .
The para orientation by the carbonyl groups in the bromination of phenanthrenequinone (I) derivatives was explained on the basis of a reaction between Br atoms and an excited state resulting from the thermal excitation of the quinone and (or) from an n → π* transition of the non-bonding electrons of the oxygen atoms. A method for synthesis of 3-bromophenanthrenequinone (II) derivatives consists of irradiating with a 75 w. tungsten lamp, a mixture of 0.01 mole the quinone, 0.02 mole Br, and 100 mg. (BzO)2 in 10 ml. PhNO2, at 60 ± 10° 1-2 hrs. The residue obtained after steam distillation of the reaction mixture yielded 80-6% the bromo derivative Thus, 0.02 mole 2-nitrophenanthrenequinone (III), 0.04 mole Br, and 100 mg. (BzO)2 in 10 ml. PhNO2 was irradiated during 2 hrs., 25 ml. EtOH added to the reaction mixture, and the mixture cooled in ice to yield 80% 2-nitro-6-bromophenanthrenequinone (IV) in yellow plates, m. 318-18.5° (PhNO2); quinoxaline derivative m. 318-18.5° (xylene). Oxidation of 1 g. IV in 20 ml. AcOH with 5 ml. ∼25% H2O2 at reflux temperature 3 hrs. and purification (NaHCO3 solution) yielded light brown cubes (AcOH) of 2-nitro-5′-bromodiphenic acid (V), m. 271-2°. The structure of IV was established by degradation. A mixture of 2.0 g. IV, 4.0 g. granulated Sn, 70 ml. EtOH, 30 ml. concentrated HCl, and 30 ml. H2O was heated on a water bath 3 hrs., filtered, mixed with 100 ml. concentrated HCl, cooled in a freezing mixture, a light yellow solid separated, dissolved in H2O, and basified (NaOH), and air bubbled. Dark pink 2-amino-6-bromophenanthrenequinone (VI) formed was separated (1 g.) and crystallized, m. >360° (PhNO2); yellow quinoxaline derivative m. 360° (AcOH). A solution of 0.3 g. VI in 3 ml. concentrated H2SO4 was cooled in a freezing mixture 0.5 hr. and an aqueous solution of 3 g. NaHPO2.H2O added and kept 24 hrs. The yellow solid was separated, sublimed, and crystallized (AcOH) to yield orange yellow plates, m. 267-8°, of 3-bromophenanthrenequinone (VII). Finely powd. IV (2 g.) was added with stirring to a boiling solution containing 10 g. KMnO4 and 20 g. KOH in 200 ml. H2O and the mixture stirred another hr., cooled, diluted, and filtered. The solid was boiled with NaHSO3 solution to dissolve MnO2 and filtered and the residue of 2-nitro-6-bromofluorenone (VIII) crystallized (xylene) in yellow flakes, m. 264-5°; oxime m. 256-7° (EtOH). In connection with synthesis of VIII, 5-nitroacetylanthranilic acid (IX) was prepared in 60-6% yield by nitrating 30 g. acetylanthranilic acid with 60 ml. HNO3 (sp. gr. 1.5) at 5° during 12 hrs. and at room temperature 1.5 hrs. Nitration of tosylanthranilic acid with HNO3 (sp. gr. 1.5) gave a product, m. 209-10°, different from 5-nitrotosylanthranilic acid. A CHCl3 solution (150 ml.) of the pseudo acid chloride (X) of 2-(4-bromobenzoyl)benzoic acid obtained from 36 g. acid and 27 g. PCl5, was added to 100 ml. liquid NH3. On evaporation of NH3 and trituration of the solid with Na2CO3 solution was obtained 35 g. pseudo amide (XI), m. 210-11° (EtOH), λ (CHCl3) 2.8 and 5.83 μ (Nujol) 2.8-3, 5.83, 6.0 μ. A solution obtained by mixing 6 g. XI, 30 ml. 10% aqueous NaOH, 30 ml. EtOH, and NaOBr solution (from 1.4 ml. Br and 100 ml. ice-cold 10% NaOH solution) was stirred 5 min. at 0°, refluxed 1 hr., and cooled to 0° to give 32-55% the amine (XII), m. 111-13° (EtOH). 2-(4-Bromobenzoyl)acetanilide (XIII) was obtained by warming 0.5 hr. (water bath) a mixture of 5 g. XII, 10 ml. Ac2O, and 2-3 drops concentrated H2SO4 0.5 hr., and pouring into water. Recrystallization (EtOH) gave transparent needles, m. 143.5-4.5°. Nitration of 1.5 g. XIII with 9 ml. HNO3 (sp. gr. 1.46) below 0° 1.5 hrs. and room temperature 3 hrs. and working up yielded 750 mg. 2-(4-bromobenzoyl)-4-nitroacetanilide (XIV), yellow, m. 207-8° (EtOH). A mixture of 300 mg. XIV and 2 ml. concentrated H2SO4 was heated on a water bath 5 min. Dilution yielded 250 mg. 2-(4-bromobenzoyl)-4-nitroaniline (XV), yellow, m. 201.5-2.0° (EtOH). A slurry obtained from 200 mg. XV in 2 ml. concentrated H2SO4 and 2 ml. H2O was treated with 0.3 ml. 30% aqueous NaNO2 solution below 0° 1 hr. and at water bath temperature 1 hr. The solid formed was washed with 20% NaOH and purified by sublimation and crystallization (xylene) to yield yellow flakes, m. 256-7°, identical with VIII (ultraviolet, infrared, mixed m.p., mixed m.p. of oxime). Nitration of 0.5 g. XIII with 1 ml. HNO3 (sp. gr. 1.5) at 0° 24 hrs. yielded 0.4 g. 2-(4-bromobenzoyl)-4,6(?)-dinitroacetanilide (XVI), m. 198-9.5° (AcOH). Hydrolysis of XVI with 20 ml. HCl and 10 ml. AcOH under reflux 2 hrs. yielded 1.1 g. 2-(4-bromobenzoyl)-4,6(?)-dinitroaniline (XVII), brown, m. 220-1° (EtOAc). Cooling the reaction mixture obtained during nitration of 20 g. I with 600 ml. HNO3 (sp. gr. 1.39-1.40) at 100-25° (20 min.) gave 42% III, m. 256-8°. A mixture of 5 g. III, 4 ml. Br, and 40 ml. AcOH was heated at 140 ± 5° 2 hrs. in a closed bottle. The greenish brown solid, 77%, m. 305-7°, was separated The m.p. of this material was not depressed when mixed with IV. M.ps. of the quinoxaline derivative, 318-18.5° (xylene), and diphenic acid derivative, 271-2° (AcOH), were undepressed when mixed with corresponding derivatives from IV. Heating a mixture of 90 mg. VII, 0.5 g. KMnO4, 4 g. KOH, and 10 ml. H2O 1 hr. and treatment of the solid with NaHSO3 solution furnished 20 mg. 3-bromofluorenone (XVIII), m. 163-4° (C6H6). Boiling a mixture of 27.6 g. XII, 60 ml. concentrated HCl, and 40 ml. H2O, filtering, and cooling in a freezing mixture gave the hydrochloride. A suspension of the hydrochloride was treated with 840 mg. NaNO2 in 10 ml. at 5°, stirred 0.5 hr., kept 0.5 hr., filtered and heated 2 hrs. The yellow solid formed was extracted with 3N NaOH and filtered to yield 1.65 g. residue. Vacuum sublimation and crystallization (C6H6) yielded yellow needles of XVIII, m. 163-4°. A solution of 1.78 g. AgNO3 in 10ml. H2O was added dropwise to a mixture of 2.1 g. I, 50 ml. AcOH, 0.5 ml. Br, 5 ml. HNO3, and 5 ml. H2O and the mixture refluxed 0.25 hr. The solid was extracted with hot AcOH and cooled to give 0.5 g. red needles of 2-bromophenanthrenequinone (XIX), m. 233-4°. Similarly, a solution of 3.4 g. AgNO3 in 20 ml. H2O was added to a mixture containing 2.1 g. I, 50 ml. AcOH, 20 ml. HNO3 (sp. gr. 1.42), and 1.1 ml. Br and the mixture refluxed 0.5 hr. When worked up as before 0.6 g. 2,7-dibromophenanthrenequinone was obtained, m. 323° (AcOH). A suspension of 300 mg. powd. I in 30 ml. CCl4 and 1.2 ml. Br in 10 ml. CCl4 was mixed and cooled 40 hrs. in ice to give 300 mg. red needles, Br complex of I, m. 170-5° (shrinking at 165°).
Tetrahedron published new progress about Bromination. 90940-40-2 belongs to class chlorides-buliding-blocks, and the molecular formula is C10H9ClO2, Quality Control of 90940-40-2.
Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics