Hein, D. W.; Pierce, Elliot S. published an article in 1955, the title of the article was New pigments from 3,3′-dichloro- and 3,3′-dimethoxy-4,4′-diaminostilbene.Computed Properties of 38939-88-7 And the article contains the following content:
Two new pigment intermediates, [4,3-H2N(CL)C6H3CH:]2 (I) and [4,3-H2N(MeO)C6H3CH:]2 (II), and from them, by diazotizing and coupling with variously substituted acetoacetanilides, 1-phenyl-3-methyl-5-pyrazolone (III), and 3-hydroxy-2-naphthoic acid arylides, a number of new pigments have been prepared The new pigments show bathochromic color shifts as expected when compared with the corresponding pigments from [4,3-H2NCl)C6H3]2 (IV). The differences in the visual light absorption curves are rationalized. 2,5,4-H2N(Cl)(O2N)C6H2Me deaminated by a standard method yielded 65% 3,4-Cl(O2N)C6H3Me (V), yellow oil, b3 108°, m. 22.5°, nD26 1.5617, nD68.5 1.5426. A slow stream of O passed with high speed stirring into 5 cc. Me2CO in 200 cc. 33% KOH in MeOH containing 5 g. V during 2 hrs. with cooling and then 3 hrs. without cooling, the mixture poured into 2 l. H2O and filtered, and the filter residue washed with H2O and EtOH, dried (4.2 g.), and recrystallized from 250 cc. glacial AcOH gave [3,4-Cl(O2N)C6H3CH:]2 (VI), uniform yellow needles, m. 284-5°. In a similar run carried out at room temperature only a red solid was produced; a similar run drowned after 1 hr. stirring at 3° contained considerable [3,4-Cl(O2N)C6H3CH2]2 (VII). V (5.0 g.) stirred with 100 cc. 33% KOH in MeOH at 0° the mixture warmed slowly, the red color discharged with 30% H2O2, the solution warmed on the steam bath, treated portion wise with H2O2 until no further color was formed, diluted with 5 volumes H2O and filtered, and the filter residue washed with H2O and Et2O, dried (1.0 g.), and recrystallized from 100 cc. glacial AcOH gave VI, long yellow needles, m. 285-6°; in runs with 3, 10, and 30% H2O2 the yields varied from 0 to 56% and the product always contained some VII. Several low melting batches of VI boiled with EtOAc and filtered, and the filtrate cooled gave VII, crystals, mainly rhombs, m. 178-80°, contaminated with traces of needles. VI (31.5 g.), 126 g. 70-2% NaSH, and 1600 cc. 95% EtOH refluxed 4 hrs. with stirring and poured into 6 l. H2O, the solid precipitate filtered, washed with H2O, dried (16.8 g.), and recrystallized from 1300 cc. absolute EtOH gave 7.5 g. I, very light tan leaflets, m. 200-1°. I in EtOH saturated with HCl gave I.2HCl, needles, m. 276-7°. I.2HCl (5.28 g.), 12 cc. 5N HCl, and 45 cc. H20 diazotized at 5° with 30 cc. N NaNO2, the solution stirred 20 min., treated with H2NSO3H, and filtered cold with Super-cel, the filtrate buffered with 13.5 cc. 2N NaOAc and added dropwise with stirring to 3.9 g. AcCH2CONHPh (VIII) slurried in slightly acidic medium (by precipitation of a solution in 6 cc. 5N NaOH and 40 cc. H2O with glacial AcOH), the mixture stirred 2 hrs. without cooling and 1 hr. at 85-90°, and filtered hot, and the solid washed with H2O and dried gave 4.7 g. orange-yellow pigment with a red-brown mass tone and orange yellow tint tone. Similarly were prepared pigments with I from the following coupling components (coupling component, % yield, mass tone, and tint tone given): III, 98, bright red, yellow-red; o-AcCH2CONHC6H4Me (IX), 94, red-brown, orange-yellow; 1-C10H7NHCOCH2Ac, 84, red-brown, orange-yellow; o-AcCH2CONHC6H4OMe (X), 76, red-brown, orange-yellow; acetoacetcresidide, 122, orange-brown, orange; acetoacetpseudocumidide, 89, yellow-brown, orange-yellow; 2,4-acetoacetoxylide, 93, red-brown, orange-yellow; benzoylacetanilide, 85, orange-brown, orange-yellow; p-O2NC6H4NHCOCH2Ac, 89, dull red, light dull red; o-ClC6H4NHCOCH2Ac, 105, red-brown, orange-yellow; 3-hydroxy-2-naphthanilide, 127, blue-black, blue-gray; 3-hydroxy-2-naphtho-o-phenetidide (XI), 92, red-black, lavender; yields in excess of 100% were due to the presence of excess coupling component, precipitated by the acid coupling conditions, and not washed out by the hot H2O; the excess coupler was extracted with hot EtOH; the mass tones and tint tones are those of the crude pigment; the yields of the pigments were essentially quant. after hot EtOH extraction 3,4-MeO(O2N)C6H3Me (XII) (2 g.) added at 10° to 100 cc. 33% KOH in MeOH, the mixture bubbled 2 hrs. with rapid stirring with O, diluted with 500 cc. H2O, and filtered, and the filter residue washed with H2O and a small amount MeOH and recrystallized several times from glacial AcOH gave [3,4-MeO(O2N)C6H3CH:]2 (XIII), m. 195-6.5°. XII (8 g.) stirred 6 hrs. in a similar run gave 5.7 g. XIII, m. 194-6°; if O was introduced at the same time as the Me2CO solution of XII a higher melting product, m. 190-240°, was obtained which was not further characterized. XIII (5 g.) and 15 g. Na2S.H2O in 200 cc. EtOH refluxed 4 hrs., cooled, poured onto ice, and filtered, and the filter residue washed and dried gave 4 g. II, light yellow-tan flakes, m. 148-50°. II (1.35 g.) in 100 cc. H2O and 10 cc. N HCl heated with stirring until dissolved, the solution cooled to 10°, treated with 11 cc. N NaNO2, stirred 1 hr., and treated with a small amount H2NSO3H, and the bisdiazonium solution coupled in the usual manner with III gave a red-black pigment, 94%, with a dull red-brown tint tone. XI gave similarly 116% blue-black pigment with a red-blue tint tone. A fairly rapid stream of O passed into 200 cc. 33% KOH in MeOH with high speed stirring, the mixture treated with stirring and O addition during 20 min. with 5 g. 2,4-Cl(O2N)C6H3Me in 30 cc. warm absolute EtOH, the purple color discharged, the mixture poured into 3 l. H2O and filtered, the solid washed with H2O and 95% EtOH, and dried, and the yellow crystalline solid (4.5 g.) recrystallized from 25 cc. PhNO2 gave 2.2 g. [2,4-Cl(O2N)C6H3CH:] (XIV), long yellow needles, m. 294-6°. XIV (57 g.) and 220 g. 70-2% NaSH in 2850 cc. 95% EtOH refluxed 3 hrs. with stirring and drowned in 10 l. H2O gave in the usual manner 37.0 g. [2,4-Cl(H2N)C6H3CH:]2 (XV), yellow needles, m. 180-5°; XV.2HCl, decomposed at 286°. XV.2HCl (1.76 g.) slurried with 100 cc. H2O and 4 cc. 5N HCl, cooled to 0°, treated with 10 cc. N aqueous NaNO2, stirred 15 min., treated with H2NSO3H, and filtered cold with Supercel and the solution coupled with various coupling components gave pigments (coupler, % yield, mass tone, and tint tone of pigment given): III, 93, bright-red, orange; VIII, 88, orange-brown, orange-yellow; XII, 94, orange-brown, orange-yellow; XIII, 86, red-brown, orange-yellow; XI, 113, red-black, violet. (p-H2NC6H4CH:)2 (1.05 g.) in hot 6 cc. 5N HCl and 50 cc. H2O cooled to 5° and diazotized in the usual manner, and the solution coupled with III gave 97% pigment with a bright-red mass tone and a yellow-red tint tone. Similar coupling with XII gave a yellow brown pigment, 91%, with a yellow-orange tint tone. The experimental process involved the reaction of 2-Chloro-4-methyl-1-nitrobenzene(cas: 38939-88-7).Computed Properties of 38939-88-7
2-Chloro-4-methyl-1-nitrobenzene(cas:38939-88-7) 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 38939-88-7
Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics