Category: 93012-36-3

Chardonnens, Louis; Wurmli, Albert published an article in 1946, the title of the article was Derivatives of fluorenone. II. 3,6-Dimethylfluorenone.Application In Synthesis of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid And the article contains the following content:

cf. C.A. 40, 1479.2. Diazotization of 4,2-Me(H2N)C6H3CO2H (I) and treatment of the solution with NH3-Cu2O gives 84% 5,5′-dimethyl-2,2′-dicarboxybiphenyl, m. 269° (all m.ps. corrected). When this is mixed with CaO and heated 2 hrs. at 350° it gives 23% 3,6-dimethylfluorenone (II), m. 118° (oxime m. 189-91°), but the product is always contaminated with a red oil which can be separated only by chromatography. It is therefore better to treat I with NaOH and MeC6H4SO2Cl to get 77% 4-methyl-2-tosylaminobenzoic acid, m. 208-9°. With PCl5 this gives the acid chloride which reacts with MePh and AlCl3. The product is saponified to give 65% 4,4′-dimethyl-2-aminobenzophenone (III), m. 119°. 4,4′-Dimethyldiphenyl sulfone is a by-product. Diazotization of III in H2SO4 gives 70% II and a little 4,4′-dimethyl-2-hydroxybenzophenone, m. 73-4°. When II is heated 6 hrs. at 175° in a sealed tube with N2H4.H2O and Na in EtOH, it gives 85% 3,6-dimethylfluorene, m. 130-1°. Direct nitration of II with H2SO4 and KNO3 gives only 3,6-dimethyl-2,7-dinitrofluorenone (IV), m. 281° (decomposition). The mononitro compound cannot be prepared in this way. 4-Methyl-5-nitro-2-chlorobenzoic acid is converted to the acid chloride which, with MePh and AlCl3, gives 69% 4,4′-dimethyl-5-nitro-2-chlorobenzophenone, m. 108.5°. This heated 8 hrs. in a sealed tube at 160-70° with alc. NH3 gives 82% 4,4′-dimethyl-2-amino-5-nitrobenzophenone, m. 162.5°. This is diazotized in H2SO4 to give 59% 3,6-dimethyl-2-nitrofluorenone (V), m. 222-4°, and some 4,4′-dimethyl-5-nitro-2-hydroxybenzophenone, m. 144°. Nitration of V gives IV. The experimental process involved the reaction of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid(cas: 93012-36-3).Application In Synthesis of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid

5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid(cas:93012-36-3) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Application In Synthesis of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

March, D. M.; Henshall, T. published an article in 1962, the title of the article was The kinetics of cyclization of some 2,2′-diphenic acids in sulfuric acid.SDS of cas: 93012-36-3 And the article contains the following content:

A spectrophotometric method of analysis was used. Simple first-order kinetics were found in each case, and also a linear dependence of log k on the Hammett acidity function. The energy and entropy parameters were found to vary in a characteristic manner. A mechanism is proposed and is discussed. The experimental process involved the reaction of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid(cas: 93012-36-3).SDS of cas: 93012-36-3

5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid(cas:93012-36-3) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. SDS of cas: 93012-36-3

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Kruber, Otto; Raeithel, Armin published an article in 1954, the title of the article was Coal-tar anthracene oil.Computed Properties of 93012-36-3 And the article contains the following content:

The following new components were found in coal tar anthracene oil: 1-methylfluorene (I), diphenylsuccindan (C.A. 4b,5,9b,10-tetrahydroindeno[2,1-a]indene) (II), 2-methylphenanthrene (III), 3,6-dimethylphenanthrene (IV), and 1,8-dimethylbiphenylene sulfide (V) of which V was unknown. I was obtained from the anthracene oil fraction, b. 316.5-18° (cf. C.A. 47, 1701d) by fractional distillation, freezing out, and Na fusion. The unreacted oil was sulfonated at room temperature with 10% by weight portions of 92% H2SO4 (2 times), 95% (4 times), and 97% (to completion). The crude crystalline sulfonic acids obtained upon cooling from sulfonation fractions 3-7 were desulfonated with 50% H2SO4. Distilling up to 115° gave a noncrystg. oil, from 115-30° an oil which partly crystallized upon cooling to give I, white needles from MeOH, m. 86-7° (identified by oxidation to 1-methylfluorenone, yellow needles from petroleum ether, m. 98-9°) and fluorenone-1-carboxylic acid, yellow needles by sublimation, m. 195-6°. II was obtained from the anthracene oil fraction, b. 333-5° (C.A. 49, 7575a). Fractions 8-14 of the yellow oil (loc. cit.) (640 g.) were treated with 50 g. of 100% H2SO4 in presence of Ac2O at 15°, the unreacted oil (485 g.) was agitated with 160 g. 100% H2SO4 for 3 h. at 70°. The sulfonic acid layer was repeatedly extracted with benzene, and the combined extract and unsulfonated oil, after washing to neutrality and evaporating the benzene, was distilled in vacuo. After separating 55 g. biphenylene sulfide crystallizing from 285 g. distillate, the remaining 181 g. oil was again treated with 150 g. 100% H2SO4 at 70-5°, the sulfonated product worked up as above gave 20.5 g. of a dark oil from which crystallized 6.6 g. of crude II (4.7 g. of white needles from EtOH, m. 104-4.5°), identified by the mixed m.p. with the synthetic product [cf. Ann. 247, 157(1888)]. The UV spectrum of II in EtOH closely resembles that of hydrindene. III was isolated from the heavy ends of the anthracene oil fraction, b. 350-70°, which was dissolved in an equal amount of PhMe. The filtrate, after evaporating the solvent, was fused with KOH to remove carbazoles, extracted with dilute acid then alkali to remove bases and phenols, resp., and treated with Na at 190-200° to remove most of the 4,5-methylene-phenanthrene. From the remaining oil a 3.5 kg. fraction, b. 350-60°, was redistilled at 30 mm. Hg in an adiabatic column of about 28 theor. plates at a reflux ratio of 30:1 to fractions of 100 g. each. The crystalline portion of fractions 11-16 was distilled over Na and recrystallized from EtOH to give 150 g. III, colorless leaflets, m. 56°, b760 354.8°. III was further purified by dissolving in a little PhMe and sulfonated at 40-5° with concentrated H2SO4, recrystallized from 33% H2SO4, and desulfonated with 33% H2SO4 at 125-30° to give III, m. 57-7.5°; picrate, orange needles, m. 120-1°. Oxidation of III gave 2-methylphenanthrenequinone (VI), orange leaflets, m. 155-6°; condensation of VI with o-C6H4(NH2)2 gave the corresponding quinoxaline, pale yellow needles, m. 196-7°. The solution obtained upon treating 2 g. VI with 10 cc. 30% H2O2 and 18 cc. of 2N NaOH at room temperature for 1.5 h., when diluted with H2O, kept overnight, and filtered gave upon acidification of the filtrate 4-methyldiphenic acid, colorless needles from very dilute EtOH, m. 246-7°. The latter can be obtained directly from III by refluxing with 30% H2O2 in AcOH for 2.5 h. and converted to 2-methylfluorenone by dry distillation over CaO. IV was obtained from the heavy ends of the anthracene oil fraction, b. 355-60°, after pretreatment as described for the preparation of III, by distilling 7 kg. in an adiabatic column of about 18 theor. plates at a reflux ratio of 20:1 at 30 mm. Hg to fractions of about 120 g. each. Fractions 6-10, upon redistillation, served as starting material for the isolation of V. The 4 penultimate fractions obtained upon redistillation of fractions 20-32 in the same column gave 45 g. IV, colorless needles, m. 141° (from EtOH), b760 363.2°; picrate, orange needles, m. 172-3°; oxidation gave 3,6-dimethylphenanthrenequinone, orange needles, m. 221-2° (from EtOH), which condensed with o-C6H4(NH2)2 to the corresponding quinoxaline, pale yellow needles, m. 266-7° (from EtOH). Heating 4 g. IV in 30 cc. of AcOH to boiling and gradually adding 24 cc. 30% H2O2 gave 2.2 g. 5,5′-dimethyldiphenic acid, pale yellow leaflets, m. 268-70° (from H2O) which upon dry distillation with CaO gave 3,6-dimethylfluorenone, orange leaflets, m. 116-17° (from petroleum ether). The filtrate obtained from the above mentioned crude starting material for V was sulfonated with 92% H2SO4 at room temperature, and the unsulfonated oil adsorbed on Al2O3 and eluted first with petroleum benzin and then with a mixture of benzene and EtOH. The colorless oily eluate, nD20 1.669, crystallized on standing V, white needles, m. 154-5° (from EtOH); picrate, yellow needles, m. 130-1°. Heating 0.2 g. V in 5 cc. of glacial AcOH with 0.5 cc. 30% H2O2 on the water bath gave 0.2 g. 1,8-dimethyldiphenylenesulfone, white needles, m. 293-4° (from EtOH or glacial AcOH), heating 10 g. 2,2′-dihydroxy-3,3′-dimethylbiphenyl with 5 g. P2S5 in an Anschütz distillation flask over 15 min. from 140 to 410° gives 0.38 g. V after recrystallizing the crude distillate from EtOH. The experimental process involved the reaction of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid(cas: 93012-36-3).Computed Properties of 93012-36-3

5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid(cas:93012-36-3) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. Computed Properties of 93012-36-3

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

On August 25, 2014, Oh, Cheon Rim; Lee, Won Jung; Kim, Yeong Seong; Lee, Min Seon; Lee, Seung Min; Jeon, Eun Ju; Choi, Don Su; Moon, Bong Seok; So, In Yeong; Lee, Jae Yeol; Ju, Seong Hu published a patent.HPLC of Formula: 93012-36-3 The title of the patent was Preparation of phenanthrene compounds as organic electroluminescence device materials. And the patent contained the following:

Disclosed are compounds I [Ar1-Ar3 are independently (un)substituted alkyl, aryl, heterocyclyl, arylamino, etc.; R1-R6 are independently H, CN, (un)substituted alkyl, alkoxy, etc.; n is 0-3; with the proviso that R1-R6 are not hydrogen at the same time; when Ar2 and Ar3 are aryl, at least one of Ar2 and Ar3 is (un)substituted anthracene, pyrene, diphenylfluorene, etc.]. Example compound II was prepared by the sequential palladium-catalyzed coupling reaction of compound III with pyren-2-ylboronic acid and diphenylamine in 25% yield for two steps. Blue electroluminescent device comprising an invention compound (light-emitting layer material) showed improvements in efficiency and life span compared to device using previously reported compound (CBP). The experimental process involved the reaction of 5,5′-Dimethyl-[1,1′-biphenyl]-2,2′-dicarboxylic acid(cas: 93012-36-3).HPLC of Formula: 93012-36-3

The Article related to phenanthrene preparation organic electroluminescence device material, Benzene, Its Derivatives, and Condensed Benzenoid Compounds: Anthracenes and Phenanthrenes and other aspects.HPLC of Formula: 93012-36-3

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics