Fundamental processes of dye chemistry. 1949

434 TABLE VIII. Derivatives of Benzenesulfonic Acid and of Phenol 435

			o	Redn.
			S|8a
SO3H Oleum	H		4
			SOaH	^
p.^J^-r^		Oleum p. 143	r^,
HOaStv^SOaH l^^	SO3H	•	-—^— U-

HO

Compound				Principal Use	Compound		Principal	Use
1. Phenol-m-sulfonic acid				Azo dyes	18.	Phenol	Disinfectant, azo dyes, triphenylmethanes,
2.	Resorcinol			Eosins, azo dyes, nitroso dyes, oxazines	19. p-Phenetidine		sulfur dyes
3.	m-Hydroxydiphenylamine			Triphenylmethanes, rhodamines, oxazines			Azo dyes
4.	Resorcylic acid			Azo dyes	20.	Phenacetin	Antipyrectic
5.	Metanilic acid	(No. 17, Table	VI)	Azo dyes	21.	o-Chlorophenol	Azo dyes
6.	Aniline-o-sulfonic acid (No. 17, Table III)			Azo dyes	22.	p-Aminophenol (No. 19, Table IV)	Photography (developer), sulfur dyes,
7. 2-Aminophenol-4,6-disulfonic acid				Azo dyes (chrome)	23. 4,6-Dichloro-2-aminophenol (No. 13, Table I)		fur dyeing
8.	Picric acid (No. 17, Table V)			Nitro dye, explosive			Azo dyes (chrome)
9.	Picramic acid (No. 18, Table		V)	Azo dyes (chrome)	24.	p-Chlorophenol	Azo dyes, anthraquinone dyes
10. Phenol-p-sulfonic acid				Azo dyes	25.	2,4-Dichlorophenol	Disinfectant
11. 6-Nitro-2-aminophenol-4-sulfonic acid				Azo dyes (chrome)	26.	Chloranil	Sulfur dyes, vat dyes (helindone), oxazines
	(nitroacidl) (No. 8, Table		II)		27.	p-Nitrosophenol	Indophenols, sulfur dyes
12. 2,6-Diaminophepol-4-sulfonic acid				Azo dyes (chrome)	28.	p-Aminosalicylic acid	Azo dyes (chrome)
	(No. 7, Table II)			Sulfur dyes	29.	Salicylic acid	Azo dyes, triphenylmethanes, anthraquinone
13.	o-Nitrophenol				30.	p-Chloro-o-aminosalicylic acid	dyes,	pharmaceutical
14. o-Aminophenol-p-sulfonic acid				Azo dyes (chrome)			Azo dyes (chrome)
15. p-Nitrophenol		(No. 21, Table	IV)	Sulfur dyes	31.	Same as No. 22
16. o-Aminophenol		(No. 15, Table III)		Azo dyes (chrome), fur dyeing	32.	Carbazoleindophenol	Vat dye (hydrone blue)
17. 5-Nitro-2-aminophenol (No. 16, Table III)				Azo dyes (chrome)	33.	Sulfosalicylic acid	Azo dyes
					34.	p-Sulfo-o-aminosalicylic acid	Azo dyes (chrome)

436	TABLE IXa.
CH2C1	CH3

NH

Compound		Principal Use
1.	Benzyl alcohol	Perfume
2.	Benzaldehyde (oil of bitter almond)	Perfume, triphenylmethanes, acridines
3.	o-Nitrobenzaldehyde	Indigo
4.	m-Nitrobenzoyl chloride	Azo dyes (rosanthrene), pharmaceutical
5.	m-Nitrobenzaldehyde	Triphenylmethanes
6.	m-Aminobenzaldehyde	Triphenylmethanes
7.	o-Nitrocinnamic acid	Indigo
8.	Benzotrichloride	Triphenylmethanes
9.	Benzoyl chloride	Multiple
10.	m-Hydroxybenzaldehyde	Triphenylmethanes
11.	Benzylaniline (No. 41, Table VII)	Triphenylmethanes
12.	Benzamide	Anthraquinone vat dyes
13.	Cinnamaldehyde	Perfume
14.	Phenylacetyl chloride	Ciba lake red B
15.	o-Toluenesulfamide	Saccharin
16.	p-Toluenesulf amide	Disinfectant
17.	Nitro-p-phenylenediamine	Azo dyes
18. p-Chlorobenzoic acid		Triphenylmethanes

Derivatives of Toluene

437

Cl

Compound

19.2,4-Dichlorobenzoyl chloride

20.4,6-Dichloro-3-aminoben/oic acid

21.Benzaldehyde-o-siilfonic acid

22.o-Chlorobenzaldehyde

23.o-Chlorobenzoic acid

24.6-Chloro-3-aminobenzoie acid

25.6-ChIoro-2-toluidine-4-sulfonic acid

26.o-Chlorobenzoyl chloride

27.6-Chloro-3-toluidine-4-sulfonic acid

286-Chloro-3-toluidine

29.2-Toluidine-4-sulfonic acid

30.2-Amino-4-cresol

31.Benzaldehyde-2,4-disulfonic acid

32.2,6-Toluylenediamine-4-sulfonic acid

33.p-Cresol

34.p-Sulfoanthranilic acid

35.o-Tolidine-m-disulfonic acid

Principal Use

Azo dyes (anthosines) Azo dyes Triphenylmethanes Triphenylmethanes Anthraquinone-acridones Azo dyes

Azo dyes

Azo dyes, vat dyes Azo dyes (lake) Azo dyes

Azo dyes

Rhod amines Triphenylmethanes Azo dyes Disinfectant, azo dyes Azo dyes (lake)

Azo dyes

438	TABLE 1Kb.

COOH

NH2

NHCOCHa Isaponificatton

CH3

NH2

i Cl fx^|NHCOCH3 I H03sL J

JCH3

NHCOCH2COCH8

Compourui		Principal Use
36.	Benzidine-3,3'-dicarboxylic acid	Azo dyes
37.	6-Chloro-2-toluidine (fast scarlet TR base)	Azo dyes (ice colors)
38.	2,6-Dichlorobenzaldehyde	Triphenylmethanes
39.	2-Chloro-6-nitrobenzaldehyde	Halogenated indigo
40.	Same as No. 3
41.	4-Chloro-2-toluidine (fast red KB base)	Azo dyes (ice colors, lake)
42.	4-Chloro-2-toluidine-5-sulfonic acid	Azo dyes (lake)
43. 4-Chloroanthranilic acid		Azo dyes
44.	o-Tolidine	Azo dyes (subst.)
45. Diacetoacet-o-tolidide (naphthol AS G)		Azo dyes (ice colors)
46.	2-Toluidine-5-sulfonic acid	Azo dyes
47.	Monomethyl-o-toluidine	Diand triphenylmethanes, thiazines
48.	5-Anilino-2-amino-3-mercaptotoluene	Sulfur dyes
49.	o-Toluidine	Multiple
50.	3-Chloro(bromo)-2-toluidine-5-sulfonic acid	Azo dyes (tartrazine)
51.	3-Chloro (bromo)-2-toluidine	Azo dyes
52.	6-Nitro-2-toluidine	Azo dyes
53. 5-Nitro-2-toluidine (fast red RL base)		Azo dyes (ice colors)
54. 4-Nitro-2-toluidine (fast scarlet G base)		Azo dyes (ice colors), thioindigo dyes
55. 5-Chloro-2-toluidine (fast red TR base)		Azo dyes (ice colors)
56. 3-Nitro-2-toluidine		Azo dyes

Derivatives of Toluene (continued from Table IXa)	439
CH3	CH3

N(CH3)2

Compound

57.m-Toluylenediamine

58.m-Toluylenediaminesulfonic acid

59.2-Chloro-4-toluidine-5-sulfonic acid

60.Trinitrotoluene

61.2-Chloro-4-toluidine

62.5-Nitro-2-chloro-4-toluidine

63.2,6-Dichloro-4-toluidine

64.4-Toluidine-2-sulfonic acid

65.4-Nitrotoluene-2-sulfonic acid

66.p.p'-Diaminostilbenedisulfonic acid

67.4-Toluidine-3-sulfonic acid

68.2-Nitro-4-toluidine

69.p-Toluidine

70.3-Nitro-4-toluidine (fast red G base)

71.3-Chloro-4-toluidine

72.Cresidine

73.m-Toluidine

74.Dimethyl-m-toluidine

75.Ethylbenzyl-m-toluidinc

76.Ethylbenzyl-m-toluidinesulfonic acid

Principal Use

Azo dyes, acridines, azines, sulfur dyes Azo dyes

Azo dyes (lake) Explosive

Azo dyes (lake) Azo dyes (lake) Azo dyes

Azo dyes Stilbenedyes (subst.) Azo dyes (subst.) Azo dyes

Azo dyes Multiple

Azo dyes (lake, ice colors) Azo dyes

Azo dyes (middle comp.) Azo dyes Triphenylmethanes Triphenylmethanes Triphenylmethanes

440

TABLE X.

Derivatives of a-Nitronaphthalene

441

rNjn.2

CO

H03S

HO3S

Compound

1.l-Naphthylamine-2,4-disulfonic acid

2.l-Diazo-2-naphthol-4-sulfonic acid (of. No. 29, TableXII)

3.2,4-Dinitro-l-naphthol-7-sulfonic acid (naphthol yellow S)

4.l-Hydroxy-2-naphthoic acid

5.Ethyl-a-naphthylamine

6.a-Naphthol (No. 1, Table XI)

7.2,4-Dinitro-l-naphthol (Martius yellow)

8.4-Benzoyl-l-naphthol

9.a-Naphthylamine

10.l-Naphthylaimne-5,7-disulfonic acid (No. 3, Table XI)

Principal Use

Azo dyes

Azo dyes (chrome) Wool and lake dye Triphenylmethanes Triphenylmethanes

Azo dyes, triphenylmethanes, indophenols, indigoids

Nitro dye

Azo dyes (ice colors)

Azo dyes (ice colors), azines, oxazines, vat dyes, and others

Azo dyes

p. 175

1 111

•8§	f NH2

1 OO

N02

\* NH2

00

NH2

S03H

SO3H

Compound			Principal Use
11.	l-Amino-5-naphthol-7-sulfonic acid	(M acid) (No. 4, Table XI)	Azo dyes (esp. subst.)
12.	Phenyl-a-naphthylamine		Triphenylmethanes
13.	l-Naphthylamine-4-sulfonic acid (naphthionic acid)		Azo dyes
14.	l-Naphthol-4-sulfonic acid (Nevile-Winther acid)		Azo dyes
15.	l-Naphthylamine-4,6-disulfonic acid (Dahl acid)		Azo dyes
16.	l-Naphthylamine-4,7-disulfonic acid (Dahl acid)		Azo dyes
17.	1,5-Dinitronaphthalene		Sulfur dyes
18.	1,5-Diaminonaphthalene		Azo dyes (subst.)
19.	1,8-Dinitronaphthalene		Sulfur dyes
20.	Perimidine		Azo dyes, indigoids
21.	l-Amino-8-naphthol-5-sulfonic acid	(No.14, Table XI)	Azo dyes
22. Naphthazarin			Mordant dye

442

TABLE XI.

Derivatives of Naphthalene-a- and 0-sulfonic Acids

443

SO3H

SOgH

I(and isomers)

|S03H

HO3S

x	S°3H		COSO3H
TO	Ger. Pat. 170477
		HO3S	NH2
HO3S	Frdl. 8:700		(See page 445 /or Compounds and Principal Uses)

TABLE XI. Derivatives of Naphthalene-a- and /?-sulfonic Acids

445

Compound

1.o-Naphthol (No. 6, Table X)

2.l-Naphthylamine-5-sulfonic acid

3.l-Naphthylamine-5,7-disulfonic acid (No. 10, Table X)

4.l-Amino-5-naphthol-7-sulfonic acid (M acid) No. 11, Table X)

5.l-Naphthylamine-4,8-disulfonic acid (S acid)

6.l-Naphthol-4,8-disulfonic acid (Schoellkopf acid)

7.l-Naphthylamine-8-sulfonic acid (peri acid)

8.l-Phenylnaphthylamine-8-sulfonic acid

9.l-Amino-8-naphthol-7-sulfonic acid

10.l-Amino-5-naphthol

11.l-Amino-8-naphthol-4-sulfonic acid (S acid)

12.l,8-Dihydroxynaphthalene-4-sulfonic acid

13.l-Amino-8-naphthol

14.l-Amino-8-naphthol-5-sulfonic acid (No. 21, Table X)

15.l-Amino-8-naphthol-5,7-disulfonic acid

16.2-Aminonaphthalene-4,8-disulfonic acid (C acid)

17.l-Amino-8-naphthol-2,4-disulfonic acid (SS acid, Chicago acid )

18.l-Naphthylamine-4,6,8-trisulfonic acid

19.l-Amino-8-naphthol-4,6-disulfonic acid (K acid)

20.l-Benzoylixmino-8-naphthol-4,6-disulfonic acid (Anthosine acid)

21.l-Naphthylamine-3,8-disulfonic acid

22.l-Naphthol-3,8-disulfonic acid (Epsilon acid)

23.l,3-Dianilinonaphthalene-8-sulfonic acid

24.l-Naphthol-5-sulfonic acid

25.1,5-Dihydroxynaphthalene

26.l-Naphthol-3,6-disulfonic acid (Rudolf Gurcke acid)

27.l-Naphthol-3,6,8-trisulfonic acid

28.l,8-Dihydroxynaphthalene-3,6-disulfonic acid (chromotropic acid)

29.l-Naphthylamine-3,6-disulfonic acid (Freund acid)

30.l-Amino-8-naphthol-3,6-disulfonic acid (H acid)

31.p-Aminophenyl-1,2-naphthotriazole-4,8-disulfonic acid)

32.l-Naphthylamine-3,6,8-trisulfonic acid (Koch acid)

35.Acetonyl-1,8-naphthylenediamine-3,6-disulfonic acid

34.l,8-Naphthylenediamine-3,6-disulfonic acid

35.Acetonyl-1,8-naphthylenediamine-3,6-disulfonic acid

36.Naphthalene-2,7-disulfonic acid

37.l,5-Diaminonaphthalene-3,7-disulfonic acid

38.2-Naphthol-7-sulfonic acid (F acid)

39.2-Naphthol-3,7-disulfonic acid

40.2-Naphthylamine-3,7-disulfonic acid

41.l-Naphthylamine-3,7-disulfonic acid

42.l-Naphthol-3,7-disulfonic acid

43.2,7-Dihydroxynaphthalene

44.2-Naphthylamine-7-sulfonic acid (No. 31, Table XII)

45.l-Naphthylamine-6-sulfonic acid (Cleve acid)

46.4-Acetamino-l-naphthylamine»7-sulfonic acid

47.l-Amino-6-naphthol

48.Diisopropylnaphthalenesulfonic acid (Nekal)

49.l-Naphthylamine-7-sulfonic acid (Cleve acid)

50.4-Acetamino-l-naphthylamine-6-sulfonic acid

51.l-Amino-7-naphthol

52.l,5-Diaminonaphthalene-3-sulfonic acid

Principal Use

Azo dyes

Azo dyes, triphenyhnethanes Azo dyes

Azo dyes (subst.)

Azo dyes

Azo dyes

Azo dyes

Azo dyes, sulfur dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes (subst.)

Azo dyes

Azo dyes

Azo dyes (lake)

Azo dyes Azo dyes

Azines (wool fast blue) Azo dyes (lake)

Azo dyes (chrome) Azo dyes

Azo dyes

Azo dyes (chrome)

Azo dyes

Azo dyes

Azo dyes (lake)

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Naphthalene green

Azo dyes (subst.)

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

A/o dyes, oxazines

Azo dyes

Azo dyes Azo dyes Azo dyes

Emulsifying and wetting agent Azo dyes

Azo dyes Azo dyes Azo dyes

446	TABLE XII.

C1S03H P-199

bUsJ

CO

Compound

1.2-Naphthylamine-l-sulfonic acid

2.2-Naphthylamine-5,7-disulfonic acid

3.2-Amino-5-naphthol-7-sulfonic acid (J acid)

4.2-Naphthol-8-sulfonic acid (crocein acid)

5.2-Naphthol-6,8-disulfonic acid (G salt)

6.2,8-Dihydroxynaphthalene-6-sulfonic acid

7.2-Amino-8-naphthol-6-sulfonic acid (Gamma acid)

8.2-Naphthylamine-6,8-disulfonic acid (amino-G salt)

9.2-Naphthol-3,6,8-trisulfonic acid

10.2-Naphthylamine-3,6,8-trisulfonic acid

11.2-Amino-8-naphthol-3,6-disulfonic acid

(Gamma-disulfonic acid)

12.2-Naphthol-6-sulfonic acid (Schaeffer acid)

13.2-Naphthol-3,6-disulfonic acid (R salt)

14.2-Naphthylamine-3,6-disulfonic acid (amino-R salt)

15.2-Amino-3-naphthol-6-sulfonic acid

16.2,6-Dihydroxynaphthalene

17.0-Naphthol

18.2-Naphthylamine-6-sulfonic acid (Bronner acid)

19.l-Amino-2-methoxynaphthalene-6-sulfonic acid

20.l-Nitroso-2-naphthol-6-sulfonic acid

21.l-Amino-2-naphthol-6-sulfonic acid (Eikonogen)

Principal l/se

Azo dyes (lake)

Azo dyes

Azo dyes (subst.)

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes, triphenylmethanes Azo dyes

Azo dyes Azo dyes

Azo dyes, triphenylmethanes, oxazines Azo dyes

Azo dyes

Lake (asFesalt)

Photography (developer), oxazines

Derivatives of /?-Naphthol	447

Compound

22./3-Naphthol methyl ether

23.l-Amino-2-naphthol methyl ether

24.2-Naphthylamine-5-sulfonic acid

25.2-Naphthylamine-l,5-disulfonic acid

26.2-Amino-5-naphthol-l,7-disulfonic acid (J disulfonic acid)

27.2-Hydroxy-3-naphthoic acid

28.l-Nitroso-2-naphthol

29.l-Amino-2-naphthol-4-sulfonic acid

(cf. No. 2, Table X)

30./3-Naphthoquinonesulfonic acid

31.2-Naphthylamine-7-suIfonic acid (No. 44, Table XI)

32.2-Phenylamino-5-naphthol-7-sulfonic acid

(phenyl-J acid)

33.2-Hydroxy-3-naphthanilide (naphthol AS)

34.Ethyl-fl-naphthylamine

35.Phenyl-/3-naphthylamine

36.0-Naphthylamine

37.2-Naphthylamine-8-sulfonic acid (Badische acid)

38.2-Phenylamino-8-naphthol-6-suIfonic acid (phenyl-gamma acid)

39.l-Nitroso-2-hydroxy-3-naphthoic acid

'CO—NH—^ \

^Q,

OH

'COOH

NHC0H5

Principal £/«?

Perfume

Azo dyes

Azo dyes

Azo dyes

Azo dyes

Azo dyes (lake)

Lake, steam green (Fe salt)

Azo dyes (chrome), oxazines

Oxazines, sulfur dyes

Azo dyes

Azo dyes (subst.)

Azo dyes (pigment and ice colors)

Azines

Azines

Azo dyes, triphenylmethanes, vat dyes

Azo dyes (lake)

Azo dyes

Lake (as Fesalt)

448	TABLE Xllla.	Derivatives of 2-Amino-5-naphthol-7-8ulfonic Acid (J Acid)	449

OH	Ger. Pat 136614
	Frdl. 7:443

2,4-Dinitrochlorobenzene

H03Scofx^rx^T—-N—( \NH-CHO

1 Lr

OH	Ger. Pat. 240827
^>v	Frdl. 10:193

NH2

HO3SGO"			OH	Ger. Pat. 170045
				Frdl. 8:174
		OH
OH	Ger. Pat. 254510		Ger. Pat 165102
	Frdl. 11:224		Frdl. 8:693

Compounds 1 to 13 are all used as end or middle components for substantive cotton dyes.

(continued in Table Xlllb)

450	TABLE Xlllb. Derivatives of 2-Amino-5-naphthol-7-sulfonic Acid	TABLE XIV. Derivatives of 2-Naphthylamine-5,7-disulfonic Acid	451
	(J Acid) (continued from Table XIHa)

HOaS 22 1	J	1 IOW311	llW3k JI 1
^S^~S	\x^	\X^sx^	^sx^^x,
OH	S03H	OH	OH
	Ger. Pat. 236594		Acetoacetic	CH2-C-CH8
	Frdl. 10:904
			ester	OC
HOaSr 21	-NH-CO-NH/ VNH-COCHa		HOaS	—N
\x
OH	Ger. Pat. 148505		OH	Ger. Pat 138902
	Frdl. 7:438			Frdl. 7:445

Compounds 14 to 23 are all used as end or middle components for substantive cotton dyes.

NH'

H03S

f^N^^VN - \ /

SO3H N=N

NH2

		S03H
		Ger. Pat. 146375
		Frdl. 7:435
	NH2
OH	°	OH	N==N
Ger. Pat	167139		Ger. Pat. 214658
Frdl. 8:177			Frdl. 9:401
	Compounds 1 to 3	are used as en^l or middle components
	for	substantive cotton dyes.

452	Other Derivatives of Naphthalene	453
	TABLE XV.

CeHsCOCl + AlCls

ceo	CCC
| I*	il
ceo	ceo-
^co,
See Table XVI	See Table XVII

,CO

Indanthrene golden yellow GK
		NHCOCH
		0COOH
Compound		Principal l/se
1. Dibenzopyrenequinone (indanthrene		Vat dye
	golden yelow GK) (No. 5, Table XVI)
2.	a-Naphthohydroquinone monomethyl ether	Azo dyes, indigoids
3.	2,3-Dichloro-a-naphthoquinone	Vat dyes
4.	5-Aminoacetylanthranilic acid	Azo dyes, acridones
5.	a-Naphthoquinone	Vat dyes
6.	5-Nitroanthranilic acid	Azo dyes
7.	5-Sulfoanthranilic acid	Azo dyes
8.	2,4-Dihydroxyquinoline	Azo dyes (lake)
9.	5-Chloroanthranilic acid	Azo dyes, acridones

Compound

10.Phthalic anhydride

11.Anthranilic acid

12.o-Carboxyphenylthioglycolic acid

13.3-Hydroxythionaphthene

14.Methyl anthranilate

15.Phenylglycine-o-carboxylic acid

16.Tetrachlorophthalic anhydride

17.m-Aminobenzoic acid

Dilute acid.

JCOOH

-CH2-COOH

Principal C7se

Phthaleins, anthraquinone, sulfur dyes, softeners, resins

Azo dyes, acridones Thioindigos Thioindigos Perfume, azo dyes Indigo

Phthaleins Azo dyes