A Manual for Students of Chemistry and Dyeing
By
M. Fort, M.Sc. (Leeds) Late Lecturer in Dyeing in the Bradford Technical College and L. L. Lloyd, Ph.D. (Bern) Lecturer in Organic and Technical Chemistry in the Bradford Technical College
Cambridge: at the University Press 1919
(First edition 1917, reprinted 1919)Although phenolic substances are present in coal tar, the majority of the hydroxy compounds other than phenol and cresols are prepared from the corresponding sulphonic acids or chloro derivatives by fusion with alkali.
R.SO3Na + 2NaOH = R.ONa + Na2SO3.
Phenol is usually extracted from coal tar but may be manufactured from benzene. Hydroxy compounds are sometimes obtained from corresponding amino compounds, either by diazotisation and subsequent dccomposition of the diazo compound by water, or by the reaction of sodium bisulphite upon the amine followed by treatment with caustic soda. This method is more common with the naphthalene derivatives. Oxysulphonic acids may, in some cases, be prepared by heating amines under pressure with sodium bisulphite solution.
Resorcin [] or Resorcinol (M.P. 118°C., B.P. 276,5°C.) is manufactured by heating sodium benzene disulphonate with caustic soda in cast iron vessels, fitted with a stirring gear, at 270°C., for about nine hours. The melt is dissolved in water and acidified with sulphuric acid. The resorcin is extracted with ether (Fig. IX, Appendix) and the ether distilled off. The crude resorcin may be purified by recrystallisation, quick distillation under reduced pressure, or sublimation (Fig. VII, Appendix).
Pyrogallol [] (M.P. 131 G). This compound is not obtained from coal tar. It is produced from tannin by hydrolysing to gallic acid [], the gallic acid is then heated with twice its weight of water in an autoclave from 200 to 210°C. The solution obtained of the very soluble pyrogallol is decolourised by animal charcoal and evaporated.
Since carbon dioxide is so readily split off from gallic acid, it is often better in high temperature reactions to use gallic acid in place of pyrogallol, the latter body being produced during the condensation by loss of carbon dioxide.
Naphthols C10H7OH.
α-naphthol (M.P. 94°C., B.P. 280°C.),
β-naphthol (M.P. 122°C., B.P. 286°C.).
These are white crystalline compounds, sparingly soluble in water and unlike phenol do not absorb water. They are manufactured from the corresponding sulphonic acids. Caustic soda is dissolved in water until the solution has a boiling point of about 130°C., into this solution finely powdered dried sodium naphthol sulphonate is stirred and the mixture gradually heated to about 300°C.; the reaction being carried out in an autoclave. The melt, after cooling, is acidified with hydrochloric acid and the naphthol which separates out is filter-pressed, washed and then melted.
The dioxynaphthalenes are obtained by an alkali melt of the corresponding disulphonic acids or oxysulphonic acids.
The replacement of sulphonic acid groups by oxy groups is easier in the a position and takes place at a lower temperature than in the β position. On account of this difference it is possible to obtain oxysulphonic acids by fusion processes from disulphonic acids.
Chloronaphthols may be obtained from the naphthols by chlorination in cooled acetic acid solution, by this method only homonucleal derivatives can be obtained. Other chloro-derivatives are obtained by the Gattermann or Sandmeyer reactions from the corresponding amino derivatives. Some of the chloronaphthol sulphonic acids are employed in the production of azo dyes, the introduction of chlorine tending to improve general fastness.
The Nitronaphthols may be obtained by the direct nitration vOf the naphthols, from nitrosonaphthols by oxidation, from naphthol sulphonic acids, or from nitrosonaphtholsul phonic acids. In many cases the yields are very unsatisfactory owing to the formation of tar. Chloronitronaphthalenes are converted into naphthols by digesting with strong soda carbonate solution, just as benzene derivatives are converted into phenols.
Dioxynaphthalene derivatives. Like the naphthols, the dioxynaphthalenes may be obtained by heating sulphonic acids with caustic alkali, but it has not been found possible to obtain 1.2-, 1.3-, or 1.4-dioxynaphthalene by this method.
The dioxynaphthalenes may also be obtained by heating diarnidonaphthalenes, amidonaphthols, certain amidonaphthol sulplioriic acids, or certain dioxynaphthalene sulphonic acids under pressure with dilute mineral acids. In the case of the sulphonic acid derivatives, the sulphonic acid group is eliminated by hydrolysis.
The 1.2 and the 1.4-dioxynaphthalenes are only obtained by reduction of the corresponding quinones.
The alkaline solutions of the dioxynaphthalenes absorb oxygen from the air forming dark brown or black solutions.
1.2-Dioxynaphthalene (M.P. 60°C.) is obtained by reducing β-naphthoquinone with a cold solution of sulphurous acid. It readily oxidises back to β-naphthoquinone by treatment with ferric chloride solution.
It forms scales, dissolves in alkalis forming yellow solutions which turn green on exposure to air.
1.3-Dioxynaphthalene (M.P.124°C.; diacetate, M.P. 56°C.) is obtained from l-amido-3-naphthol by boiling with dilute acid, or from many of the amido-oxynaphthol sulphonic acids, having the amido and oxy groups in the 1.3 positions to one another, by heating under pressure with water or dilute acid. It crystallises from water in scales.
1.4-Dioxynaphthalene (α-naphtho-hydro-quinone) (M.P. 176°C.; diacetate, M.P. 128°-130°C.) is obtained by reduction of α-naphthoquinone with tin and boiling hydrochloric acid.
It is readily soluble in boiling water.
1.5-Dioxynaphthalene (M.P. 265°C.; diacetate, M.P. 159°-160°C.) is obtained by caustic fusion of the corresponding naphthol sulphonic acid.
It readily oxidises in alkaline solution.
1.5-Dioxynaphthalene-2-sulphonic acid ("Cacid") is obtained together with the -4-sulphonic acid when 1.5-dioxynaphthalene is heated with sulphuric acid at 50°-60°C.
It couples in alkaline solution with diazo salts to form azo dyestuffs.
1.6-Dioxynaphthalene (M.P. 135°C.; diacetate, M.P. 73°C.) is obtained by caustic fusion at 230°-250°C. of the corresponding naphthalene disulphonic acid, or when β-naphthol-5-sulphonic acid is similarly treated.
It crystallises from benzene.
1.7-Dioxy naphthalene (M.P. 170°C.; diacetate, M.P. 108°C.) is obtained from β-naphthol-8sulphonic acid by caustic fusion.
1.7-Dioxynaphthalene3 -sulphonic acid is obtained by heating β-naphthol disulphonic acid G with caustic soda at 220°-230°C.
It is used for the production of azo dyest lifts.
1.8-Dioxy naphthalene (M.P. 140°C.; diacetate, M.P. 147°C.) is obtained from α-naphthol-8sulphonic acid by caustic fusion, or from naphthosultone by caustic fusion at 220°-230°C. Naphthosultone is obtained almost quantitatively by boiling diazotised α-naphthylamine-8-sulphonic acid with water, alcohol, or dilute sulphuric acid.
The 1.8-dioxynaphthalene. It is also obtained when 1.8-diamido-naphthalene is heated with dilute hydrochloric acid at 180°C.
It oxidises rapidly when moist on exposure to air.
l.8-Dioxynaphthalene-3-sulphonic acid is obtained by heating α-naphthol-6.8-disulphonic acid with 50 per cent, caustic soda solution at 170°-210°C.
It couples in alkaline solution with diazo salts.
1.8-Dioxynaphthalene-3.6-disulphonic acid ("Chromotropic acid" or "Chromogen I" (M.)) is obtained from Koch's α-naphthol-3.6.8-trisulphonic acid by heating with 60 per cent, caustic soda atl70 220°C.; or from l-amido-8-naphthol-3.6-disulphonic acid witH5 per cent, caustic soda solution at 265°C.; also from 8-chloro-l-naphthol-3.6-disulphonic acid by heating with 60 per cent, caustic soda solution at 220°-240°C.
Chromogen I is used as a dyestuff on wool, being absorbed from an acid bath, and on subsequent with bichromate giving a fast brown. Chromotropic acid is also largely used in the production of monoand disazo dyestuffs, having mordant dyeing properties.
2.3 -Dioxynaphthalene (M.P. 160°-161°C.) is obtained by heating 2-amido-3-naphthol-6-sulphonic acid with dilute mineral acid under pressure at 180° to 200°C., or by heating 2.3-dioxynaphthalene-6-sulphonic acid with 25 per cent, sulphuric acid to 200°C., or by fusion of β-naphthol-3.6-disulphonic acid with strong caustic soda at 280° to 300°C.
It is sparingly soluble in water.
2.3 Dioxynaphthalene-6.8-disulphonic acid is obtained by fusion of β-naphthol-3.6.8-trisulphonic acid with caustic potash.
It readily condenses to form azo compounds.
2.6 Dioxynaphthalene (M.P. 218°C.; diacetate, M.P. 175°C.) is obtained from the corresponding naphthalene disulphonic acid or the corresponding naphthol monosulphonic acid by fusion with caustic soda.
It is sparingly soluble in water.
2.7 Dioxynaphthalene (M.P. 190°C.; diacetate, M.P. 136°C.) is formed similarly to the 2.6-compound from 2.7-substituted derivatives.
It is readily soluble in hot water.
2.7-Dioxynaphthalene-3.6-disulphonic acid is obtained by sulphonation of the preceding compound with sulphuric acid at 100°C.
It couples in alkaline solution with one molecule of a diazo salt.
Amidophenols.
Ortho-amidophenol (M.P. 170°C.) prepared by the reduction of ortho-nitrophenol by means of sulphuretted hydrogen in presence of ammonia. It is a crystalline solid.
Many derivatives of ortho-nitrophenol are employed as first components in the preparation of azo and mordant azo dyestuffs.
Picramic acid. See page 26.
Para-nitro-ortho-amidophenol [-] is obtained by the partial reduction of 2.4-dinitrophenol by means of ammonia and sulphuretted hydrogen.
Ortho-nitro-ortho-amidophenol-para-sulphonic acid [-] is obtained by the nitration and partial reduction of phenol-para-sulphonic acid.
Ortho-chloro-ortho-amidophenol-para sulphonic acid [-] is made from the preceding substance
by diazotisation, halogen substitution by the Gattermann reaction, and reduction of the product.
Para-chloro-ortho-amidophenol-ortho-sulphonic acid is prepared by the action of sodium sulphite upon para-chloro-ortho-nitrophenol.
Meta-amidophenol [-] (M.P. 121°C.) may be prepared by heating 10 parts of resorcin under pressure with 20 parts of 10 per cent, aqueous ammonia, in presence of 6 parts of ammonium chloride, for twelve hours in an autoclave at 200°C. It may also be prepared by heating meta-sulphanilic acid with twice its weight of caustic soda at 280 to 290°C.
It is a colourless crystalline body, easily soluble in hot water, moderately in cold.
Dimethyl-meta-amidophenol [-] (M.P. 87°C., BP. 266°C.) may be prepared by heating dimethylmeta-sulphanilic acid with caustic alkali as above. It may also be prepared from resorcin and dimethylamine.
It is a colourless crystalline body nearly insoluble in water.
Monoethyl-meta-amidophenol [-] (M.P. 62°C.) is obtained as above from monoethyl-rneta-sulphanilic acid. The monoethyl-meta-sulphanilic acid is obtained from monoethylaniline by sulphonation with fuming sulphuric acid (30 per cent. SO3).
It is a colourless crystalline body.
Diethyl-meta-amidophenol [-] (M.P. 14°C.) is obtained similarly to the dimethyl compound. It is a crystalline solid.
Phenyl-meta-amidophenol [-] (M.P. 82°C.) or meta-oxy-diphenylamine is obtained by heating 12 parts of aniline hydrochloride with 10 parts of meta-amidophenol in an autoclave at 210° to 215°C.
It is a colourless crystalline solid, moderately soluble in boiling water.
Dimethyl-meta-amido-para-cresol [-] (M.P. 46°C.) is obtained by sulphonation of dimethylorthotoluidine with fuming sulphuric acid in the cold and decomposition of the sulphonic acid by heating with caustic soda as above. It is a crystalline powder.
Diethyl-meta-amido-para-cresol (M.P. 49°C.) is obtained as above from diethyl-orthotoluidine. It is a crystalline solid.
The meta-amido-phenols are used in the preparation of basic dyes.
Para-amidophenol [-] (M.P. 184°C.) is prepared by the electrolytic reduction of nitrobenzene in sulphuric acid solution or suspension. The compound formed is resolved on heating into para-amidophenol. It is also prepared by heating para-chloronitrobenzene under pressure with ammonia.
It crystallises in plates, aiid is readily oxidised. It is largely used in the preparation of sulphide blacks.
Amidosalicylic acid [-] is obtained by nitration of salicylic acid and reduction of the nitro compound. It is sparingly soluble in water.
Meta-nitro-para-amidophenol [-] (M.P. 148°C.) with decomposition, is obtained by hydrolysis of the acetyl derivative with dilute sulphuric acid. The acetyl para-amidophenol is nitrated with strong nitric acid.
Ortho-nitro-para-amidophenol-ortho-sulphonic acid is obtained by the nitration of paraamidophenol sulphonic acid. It is almost insoluble in cold water but forms an easily soluble diazo salt.
Amidonaphthols and their sulphonic acids.
l-Amido-2-naphthol [-] is produced by the reduction of nitroso-β-naphthol with ammonium sulphide. It is sparingly soluble in water, and is readily oxidised in alkaline solution. Ferric chloride and acid oxidising agents convert it into β-naphthoquinone.
It has been used i'or the production of oxazine dyestuffs, as a coupling agent for azo dyestuffs and also for the production of azo dyestuffs by diazotisation in neutral solution in presence of copper salts.
1-Amido-2-naphthol-4-sulphonic acid [-] is obtained by reduction of nitroso-β-naphthol with sulphurous acid. It may be diazotised in neutral solution in presence of copper salts and is used for the production of azo dyestuffs.
l-Amido-4-naphthol [-] may be prepared by reduction of nitroso-α-naphthol. Its N-acetyl derivative, obtained by acetylating the hydrochloride in presence of sodium acetate is used as a coupling agent in alkaline solution.
Several sulphonic acids of the above compound have been obtained but find little or no application in the production of dyestuffs.
l-Amido-5-naphthol [-] may be prepared from α-naphthylamine-5-sulphonic acid by heating with a 60 per cent, solution of caustic soda at 240° ta 250°C.
l-Amido-5-naphthol-2-sulphonic acid may be obtained by heating 1.5-diamido-naphthalene-2-sulphonic acid with sodium bisulphite solution followed by decomposition of the resulting body by treatment with caustic soda. It forms sparingly soluble diazo compounds.
l-Amido-5-naphthol-7-sulphonic acid [-] (M-acid) is obtained by heating 1.5-dioxy-naphthalene7-sul phonic acid with ammonium sulphite and ammonia under pressure. It is used as a coupling agent and also for diazotisation.
l-Amido-6-naphthol [-] may be obtained by reduction of 5-nitro-β-naphthol, or by heating β-naphthol with sodamide and naphthalene to 230°C. It may be diazotised and it also couples in alkaline solution with diazo salts.
l-Amido-6-naphthol-3-sulphonic acid and 1-amido-6-naphthol-4-sulphonic acid may be used for the production of azo dyestuffs.
l-Amido-7-naphthol [-] may be obtained by digesting α-naphthylamine-7-sulphonic acid with 60 per cent, caustic soda solution at 250°C. It may be diazotised and it couples in acid or alkaline solutions with diazo salts.
1-Amido-7-naphthol-3-sulphonic acid [-] (B-acid) is obtained, mixed with the 1.3.7-acid, by heating α-naphthylamine-3-7-disulphonic acid with 40 per cent, caustic soda solution at 200°C. It forms sparingly soluble diazo salts, and it couples in acid or alkaline solution with diazo salts.
l-Amido-7-naphthol-4-sulphonic acid is obtained by sulphonation of l-amido-7-naphthol with sulphuric acid below 30°C. It is similar in properties to the previous acid.
l-Amido-8-naphthol [-] may be obtained by fusion of α-naphthylamine-8-sulphonic acid with caustic soda at 230 to 240°C., or by heating 1.8-diainidonaphthalene with sodium bisulphite solution or with dilute sulphuric acid solution under pressure.
l-Amido-8-naphthol4 -sulphonic acid (S-acid) may be obtained by heating 1.8-diamido-naphthalene-4-sulphonic acid with 40 per cent, sodium bisulphite solution at 95°C., in presence of acetone, and decomposition of the product with alkali.
It is used as middle component for disazo dyes and couples in either acid or alkaline solution.
l-Amido-8-naphthol-6-sulphonic acid [-] is obtained from oc-naphthylamine-6.8-disulphonic acid by heating with 50 per cent, caustic soda under pressure at 200°C. It forms sparingly soluble diazo salts and couples in alkaline solution with diazo salts.
l-Amido-8-naphthol-3.6-disulphonic acid [-] may be obtained by heating 1.8-
diamido-naphthalene-3.6 disulphonic acid with 10 per cent, sulphuric acid at 120°C., or with 40 per cent, caustic soda solution at 200°C.
It forms soluble diazo salts, and also couples in acid or alkaline solutions with diazo salts to form azo dyes. It is largely used for the production of azo dyestuffs.
2-Amido-1-naphthol [-] may be obtained by reduction of 2-nitroso-l -naphthol. It has been used for the production of azo dyestuffs. It may be diazotised in neutral solutions in presence of copper salts to form naphthalcne-2-diazo-l-oxide
[-]
2-Amido1 -naphthol-4-sulphonic acid is obtained by reduction of nitroso-α-naphthol-4-sulphonic acid. It is diazotisable in neutral solutions giving a diazo oxide.
2-Amido-3 -naphthol [-] is obtained from the corresponding dioxy compound by heating with 30 per cent, ammonia at 140 150°C., or with ammonium sulphite solution and ammonia at 80°C. It couples in alkaline solutions with diazo salts to form diazo compounds.
2-Amido-3-naphthol-6-sulphonic acid (R-acid) [-] is obtained by heating -naphthylamine
3.6-disulphonic acid with 75 per cent, caustic soda at 230° to 250°C. It is very sparingly soluble in water.
It may be diazotised and it couples in alkaline solution with diazo salts.
2-Amido-5-naphthol [-] may be obtained by heating β-naphthylamine-5-sulphonic acid with caustic soda at 260° to 270°C.
2-Amido-5-naphthol-7-sulphonic acid (J-acid) [-] is obtained from β-naphthylamine-5.7
disulphonic acid by heating with caustic soda at 180°C., or with 50 per cent, caustic soda solution at 190°C. The β-naphthylamine-5.7-disulphonic acid is obtained by sulphonating $-naphthylaimne-5-sulphonic acid with fuming sulphuric acid (20 per cent, anhydride) below 20°C. About a 50 per cent, yield of the 5.7-disulphonic acid is obtained.
It is very important because many dyestuffs obtained from it have good cotton-dyeing properties without the use of benzidine, its homologues, or sulphur bases (e.g., Primuline etc.).
N-ethyl and N-phenyl J-acids are also of great importance in the production of azo dyestuffs.
2-Amido-5-naphthol-l.7-disulphonic acid and the 3.7-disulphonic acid are also employed in the production of azo dyestuffs.
2-Amido-7-naphthol [-] is obtained when β-naphthylamine-7-sulphonic acid is heated with a 50 per cent, solution of caustic soda at 260° to 300°C., or by boiling 2.7-diamido-naphthalene with sodium bisulphite solution followed by decomposition with caustic, or by heating 2.7-dioxynaphthalene with ammonium sulphite and ammonia under reflux condenser.
It forms diazo salts and it also couples in acid or alkaline solution with diazo salts to form azo compounds.
2-Amido-7-naphthol-3-sulphonic acid ("Facid") is obtained from 2.7-dioxynaphthalene-3-sulphonic acid by heating with ammonia ,880 sp. gr. at 120° to 150°C.
It forms sparingly soluble diazo salts and it couples in acid or alkaline solutions with diazo salts.
The 2-amido-7-naphthol-3.6-disul phonic acid forms sparingly soluble diazo salts and couples extremely slowly or not at all with diazo salts.
2-Amido-8-naphthol [-] may be obtained by heating β-naplithylamine-8-sulphonic acid with caustic soda at 260° to 270°C.
It couples in alkaline or in acetic acid solution with diazo salts to form azo compounds.
2-Amido-8-naphthol-6-sulphonic acid ("G- or 7-acid") is obtained from 2.8-dioxynaphthalcne-Gsulphonic acid by heating with "880" ammonia at 120° to 150°C., or by heating with ammonia and ammonium sulphite at 150°C.
It is largely used in the production of azo dyestuffs.
2-Amido-8-naphthol-3.6-disulphonic acid ("2R-acid") is obtained by heating β-naphthylamine3.6.8-trisulphonic acid with 80 per cent, caustic soda at 220° to 250°C.
It forms sparingly soluble diazo salts and it couples in alkaline solution with diazo salts.
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