Hensel, Hans R. published the artcile< New tricyclic metal complex dyes>, Quality Control of 112-63-0, the main research area is .
Diazotized aromatic amines coupled with β-substituted acroleins yielded the corresponding ArN:NCH(CHO)2 (I) which condensed with o-aminophenols, o-aminonaphthols, and 8-aminoquinolines yielded mono- and dianils, and with carboxylic acid hydrazides the corresponding dihydrazones; these formed tricyclic metal complexes with Cr, Co, Ni, Cu, or Zn. The azo dyes obtained by coupling 2-C10H7NHNHCOR with diazotized o-aminophenols or o-aminobenzoic acids also yielded deeply colored metal complexes, p-ClC6H4NH2 (128 g.) in 2.5 l. H2O and 250 cc. 35% HCl diazotized during 1 hr. at 5° with 70 g. NaNO2 in H2O, treated with 140 g. Et2NCH:CHCHO (II) in 250 cc. H2O, and stirred 1 hr. at 10° and 4 hrs. at room temperature yielded 208 g. p-ClC6H4N: NCH(CHO)2, light yellow prisms, m. 157-9° (AcOH). Similarly were prepared the following I (Ar, appearance, m.p., and % yield given): o-ClC6H4, sulfur-yellow leaflets, 107-9°, 100; 2,5-Cl2C6H3, golden yellow prisms, 201°, 95; 2,4,5-Cl3C6H2, golden yellow prisms, 166°, 85; p-O2NC6H4, dark brown, 204°, 92; m-O2NC6H4, yellow-brown prisms, 199°, 78; 2,4-MeO(O2N)C6H3 (III), brown plates (pleochroic from light to dark yellow), 210-11°, 90; 4,2-Cl(MeO)C6H3, golden yellow prisms (pleochroic from yellow to brown), 195-7°, 97; p-AcNHC6H4, red-brown, 206°, 74; m-AcNHC6H4, red-brown prisms, 260° (decomposition), 35; 2,4,6-Br(O2N)2C6H2, red-brown leaflets, 169-71°, 80; 4,2-Cl(O2N)C6H3, dark yellow prisms, 185-7°, 90; 4,3-Me(O2N)C6H3, brown prisms (pleochroic from yellow to red-brown), 179-82°, 60; p-H2NSO2C6H4, light yellow, above 360°, 88; 4,2,5-H2NSO2(MeO)2C6H2, dark yellow leaflets, 212° (decomposition), 95; 4,2,5-EtSO2(MeO)2C6H2, yellow prisms (pleochroic from light to dark yellow), 247-8°, 95; 2,4-MeO(H2NSO2)C6H3, yellow leaflets, >360°, 95; p-(hexamethyleniminosulfonyl)phenyl, yellow prisms, 173°, 60; p-H2NC6H4SO2C6H4, yellow leaflets, 176-8°, 88; o-HO2CC6H4, light yellow prisms, 228°, 95; 3,5,2-Cl2(HO2C)C6H2, yellow prisms, 170° (decomposition), 65; p-HO2CC6H4, yellow prisms, 260° (decomposition), 74; p-EtO2CC6H4, golden yellow prisms, 156-8°, 97; o-MeO2CC6H4, light yellow prisms, 121-2°, 90; 2,4-HO2C(O2N)C6H3 (IV), dark yellow prisms, 257°(decomposition) (AcOH-HCONMe2), 78: 2,4-HO2C(F3C)C6H3, yellow prisms, 239° (decomposition), 98; p-PhN:NC6H4, yellow-brown prisms, 214° (AcOH-HCONMe2), 98; 5-carboxy-1,3,4-triazol-2-yl, pale yellow prisms, >360°, 80. 4-(Phenylazo)-1-phenylpyrazole (25 g.), m. 126°, obtained by heating equimolar amounts PhN:NCH(CHO)2 (V) and PhNHNH2 in AcOH-EtOH, hydrogenated in 500 cc. dioxane over 20 g. Raney Ni yielded 13 g. 4-amino-1-phenylpyrazole, needles, m. 101° (H2O). 2-Amino-5-(phenylazo)pyrimidine (100 g.), m. 210°, obtained from V with H2NC(:NH)NH2.H2CO3 in 6% NaOEt-EtOH, hydrogenated 4 hrs. at room temperature in 3 l. H2O over 30 g. Raney Ni yielded 52 g. 2,5-diaminopyrimidine, prisms, m. 206° (PrOH). II (63 g.) in 500 cc. dry C6H6 treated dropwise at 15° with 80 g. Br, and stirred 12 hrs. at room temperature yielded 86 g. Et2NCH:CBrCHO, m. 77-8°. V (9 g.) and 19 g. 3,4-H2N(HO)C6H3SO2NH2 (VI) in 200 cc. HCONMe2 treated at 60-70° with 13 g. CuSO4.5H2O in H2O, stirred 1 hr. at 50-70°, diluted with 200 cc. H2O, and cooled yielded 27 g. VII (M = Cu, X = H). p-ClC6H4N:NCH(CHO)2 (11 g.) and 19 g. VI in 300 cc. warm HCONMe2 with 12 g. Ni(OAc)2 in H2O gave 29 g. brown-red VII (M = Ni, X = Cl). III (10 g.) and 7.6 g. 2,5-H2N(O2N)C6H3OH in 500 cc. HCONMe2 treated at 50° with 12 g. crystalline CrCl3, heated 10 hrs. at 120-30°, and diluted with H2O yielded 17 g. black VIII.H2O (M = Cr, Y = O), green in HCONMe2 and (HOCH2CH2)2O. IV (11 g.) and 7.7 g. VI in 250 cc. HCONMe2 with 10 g. CuSO4.5H2O in H2O gave, during 0.5 hr. at 100° 18 g. VIII (M = Cu, Y = COO), brown-red precipitate 2,4-Cl2C6H3N:-NCH(CHO)2 (5.0 g.) and 5.7 g. 8-aminoquinoline in 150 cc. HCONMe2 treated at 60° with 5 g. CuSO4 in H2O and heated 1 hr. at 60-80° yielded 10 g. IX (Ar = 2,4-Cl2C6H3, X = HSO4), metallic prisms; orange-red in HCONMe2. p-ClC6H4N:NCH(CHO)2 (11 g.) and 16 g. 8-aminoquinaldine in 250 cc. HCONMe2 treated at 60-80° with 12 g. Co(OAc)2 in H2O and stirred 2 hrs. on the water bath yielded 22 g. X (Y = Cl). V (9 g.)and 14g. BzNHNH2 in 400 cc. hot PrOH stirred 0.5 hr. at 80° with 13 g. Ni(OAc)2 in H2O yielded 22 g. XI (R = Ph, X = H), deep wine-red prisms (strongly pleochroic from orange to red). p-ClC6H4N:NCH(CHO)2 (10.5 g.), 14 g. isonicotinic hydrazide, and 13 g. Ni(OAc)2 in 500 cc. 80% PrOH yielded 20 g. XI (R = 4-pyridyl, X = Cl), brown-red leaflets (strongly pleochroic from orange to red). 2,6-HOC10H6SO2NH2 (2 moles), 380 g. Na2S2O5, and 3 l. 25% NH4OH heated 8 hrs. in an autoclave at 150°, the resulting 2,6-H2NC10H6SO2NH2 (444 g.) dissolved in 3.5 l. hot H2O and 400 cc. HCl, filtered, treated with 1500 g. NaCl and 380 cc. HCl, diazotized at 10° with 640 cc. 23% aqueous NaNO2, added to 1400 g. crystalline SnCl2 in 5 l. H2O, and stirried overnight yielded 492 g. 2,6-H2NNHC10H6SO2NH2.HCl (XII), m. 224°. XII heated 2 hrs. in excess HCONH2 at 100-10° yielded the N’-CHO derivative, m. 260°. Similarly was prepared with AcNH2 the N’-Ac derivative, decompose from 170°. 2,5-H2N(O2N)C6H3CO2H (XIII) (83 g.) in 2 l. H2O and 20 g. NaOH added simultaneously with 150 cc. 23% aqueous NaNO2 to 2 l. iced H2O and 180 cc. HCl, stirred 4 hrs. at 5°, filtered, treated during 1 hr. with 110 g. 2-C10H7NHNHAc (XIV) in 1 l. HCONMe2, and stirred 4 hrs. at 10° yielded 196 g. dark red 1,2-[2,4-O2N(HO2C)C6H3N:N]C10H6NHNHAc (XV). XV and an equivalent amount CrCl3 in HCONMe2 heated 1 hr. at 130° and buffered with 50% AcONa gave the green XVI.3H2O. XIII (33 g.) diazotized and coupled overnight at room temperature with 70 g. 2,6-AcNHNHC10H6SO2NH2 in 400 cc. HCONMe2 gave 95 g. red 1,2,6-[2,4 – HO2C(O2N)C6H3N:N] (AcNHNH)C10H2SO2NH2. 3,4,6-H2N(HO)(O2N)C6H2SO2Me (23 g.) in 100 cc. AcOH and 50 cc. HCl diazotized and coupled with 25 g. XIV gave 39 g. red 1,2- [2,4,5-HO(O2N)(MeO2S)C6H2N: N] C10H6NHNHAc (XVII). XVII (10 g.) and 10 g. CrCl3 in 150 cc. HCONMe2 and 10 cc. 50% aqueous AcONa heated 0.5 hr. at 120° and diluted with H2O yielded 12 g. green Cr complex dye. 2,6-H2NC10H6SO3H (45 g.) diazotized and reduced with 100 g. crystalline SnCl2 in 50 cc. HCl and 1 l. H2O, and the resulting 2,6-H2NNHC10H6SO3H (100%), dissolved in 160 cc. 5% aqueous NaOH, diluted with H2O to 3 l., treated during 0.5 hr. at 50° with 80 cc. Ac2O and then at 10-15° with diazotized 13 g. 2,5-H2N(O2N)C6H3OH, and kept 1-2 days at 20° yielded 83 g. red 1,2,6-[2,4-HO(O2N)C6H3N:N](AcNHNH)C10H5SO3H.2H2O, which yielded with Cu salts in HCONMe2 a blue, with Zn salts a blue-green, and with Cr salts in (HOCH2CH2)2O a green complex.
Chemische Berichte published new progress about Dyes. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Quality Control of 112-63-0.
Referemce:
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