Лако-красочные материалы — производство

When dyes are exposed to daylight or sunlight, they undergo a change and are discolored and bleached. The rate of this fading varies greatly with different dyes and with different depths of color. Thus, some dyes are extensively faded by exposure to sunlight for 1 day, or even for a few hours. Others show a definite fading only after several days or weeks, or even after many months. Such dyes are said to have widely different light fastness.

The rapid growth of the synthetic dye industry made it necessary, at an early stage, to classify dyes according to their degree of light fastness. To this end, each individual manufacturer set Up his own classification by comparing his dyes with standards arranged in order of increasing light fastness. The standards used were entirely arbitrary, and there was no relation between the standards of one manufacturer and those of another. A common basis was arived at only after the formation, in 1911, of the Deutsche Echtheitskommission. A series of eight standard degrees of light fastness was set up, the first degree representing the lowest, and the eighth, the highest light fastness.

As a result of this effort, comparison standards for cotton and wool were distributed for the first time in 1914 and 1916. Then, after a long interval and contrary to the original decision, 5-degree standards were put out between 1926 and 1928 for unweighted silk, weighted silk, viscose rayon, and acetate silk. With these standards, it was possible for the first time to classify dyes in fastness groups according to a uniform system.

However, serious defects were soon apparent even in this system. After the six standard scales were prepared, requiring 33 dyes, the process of arriving at a reliable estimation of the degree of light fastness was very complicated and difficult because of the variations in color in the standards. Also, there was the difficulty that there was no uni­formity of gradation in the standard dyeings with different textile fibers, and so the lastness ratings with different textiles were not comparable. This defect was especially troublesome with the artificial silks, particu­larly the mixed-fiber fabrics. From the fastness tables put out by the dye manufacturers, it was quite impossible for the dyers to select dyes of equal light fastness for use with mixed-fiber fabrics. Some remedy had to be worked out.

The I. G. Farbenindustrie worked for many years in an attempt to develop better standards for the different textile fibers, but these efforts did not achieve the desired improved standardization. During the course of this work, however, it became increasingly evident that other factors, in addition to exposure to light, had a significant effect on dye bleaching. Among these other factors were temperature, light intensity, and espe­cially humidity and nature of the substrate. Thus, the fading of dyes on cotton and artificial silks was greatly affected by humidity, being much more rapid in moist air than in a dry atmosphere.’Wool dyes, on the other hand, showed a much smaller dependence on humidity, as shown by extensive tests in which cotton and wool dyes were given identical exposures under the varying climatic conditions prevailing in some eighteen locations around the world.

These data led to the evolution of eight new dyeing standards for wool. Attempts were made to circumvent the troubles due to variations In tint and to limit the standards to a single constant tint. Gray would have been the best color to use for this purpose, because it would be the easiest to compare with all the different colors. Unfortunately, how­ever, there were not enough gray dyes available for the purpose. The situation was much better with blue dyes, and it was possible, by care­ful selection of dyes and depths of coloring, to arrive at a set of eight standards making up an approximately geometric series with respect to fight fastness. Within this series, then, each step requires about twice the exposure of the preceding step to produce the same degree of fading. It must be emphasized that the light fastness ratings 1 to 8 do not give a direct measure of the actual fastnesses. An idea of the magnitude of this progression is best afforded by a practical example. If Standard 1 shows definite fading after 2 days’ exposure, the other standards will require approximately the following exposure times:

Standard……………………………………. 1 2 3 4 5 6 7 8

Exposure, days……………………………. 2 4 8 16 32 64 128 256

Since these values vary, depending on the brightness of the daylight and the hours of sunshine, they must be regarded as approximate, average values.

The figures given above show clearly that groups 1 to 3 correspond to a very low light fastness, group 4 to medium, and group 5 to higher fastness. The groups from 6 on withstand rapidly increasing exposure times, and group 8 can be regarded as being outstandingly fast. These dyes in group 8 fulfill the very highest requirements, particularly since most textile fibers themselves are badly damaged or even completely destroyed on such long exposures. The light fastness ratings from 1 to 4 are given in whole numbers and those above 4 are expressed, if neces­sary, in half steps.

These new standards were accepted by the German Echtheitskom — mission and were published for the first time in the 6th edition of Ver fahren, Normen und Typen.[79] In the meantime, the series has been still further improved, and in the 8th edition, the present official standards were set up as follows:

Fastness rating 1………………………… 0.8% Brilliant wool blue FFR extra

2 1-0% Brilliant wool blue FFB

3 1.2%.. Brilliant indocyanine 6B

4 1.2%.. Supramine blue EG

5 1.0%.. Cyananthrol RX

6 3.0%.. Alizarin direct blue 3 GL

7 3.0%.. Indigosol 06 В

8 3.0%.. Indigosol blue AGG

Although the dyeing procedure was accurately described, it was still difficult for the outsider to dye up his own set of these blue stand­ards. Hence, in order to eliminate all sources of error, the standards have been supplied free of charge by the German Echtheitkommission and by German and Swiss dye manufacturers.

The introduction of these standards simplified matters a great deal. By their use, it became possible to compare dyes of any depth or tint and, of special importance, on all the various fibers. Thus, this set of blue standards has become an absolute standard for the determination of light fastness and it has become possible to assign a numerical value for light fastness to every dye used in practice.

The actual determination of light fastness is very simple. The dyed material to be tested and the blue standard are half covered with card­board and exposed together to daylight. The samples are exposed at least 2 cm. behind ultraviolet-transmitting glass in well-ventilated frames set at a 45-degree angle facing the south. When a distinct fading is ob­served in the test sample, a narrow strip of the exposed portion of the sample and of the standard is covered with cardboard, and exposure is continued until a definite change is again observed. A second strip is then covered and the exposure continued. The method must be changed somewhat if several dyed samples, differing in light fastness, are to be compared with the blue standards. In this case, exposure is continued, without regard for the fading of the samples being tested, until standard 4 shows a definite fading. Then a strip of the standards and test samples is covered, and exposure continued until standard 6 is observed to fade. A second strip is then covered, and exposure continued until standard 7 shows a distinct change. In this way, three fading strips are formed across the standards and the test samples. The fastness of a sample is then easily determined by locating the standard corresponding in degree of fading, and the fastness rating is then the number of the corresponding standard. The ratings can also be expressed in words as follows: 1, small; 3, moderate; 5, good; 6, very good; 7, excellent; 8, outstanding.

A simple and usable method has thus been found for determining the light fastness of dyed materials. There was still a need for a standard method for the evaluation of dyes. As is well known, a dye fades more rapidly in light tints than in the deeper tints, and different fastness rat­ings are obtained for one and the same dye depending on the depth of tint.

As a first step, it was necessary to establish exactly the depth of tint upon which the fastness of a dye was to be based. To this end, so-called auxiliary standards were set up, these being standardized dyeings, of equal depth of tint, in the most important colors: yellow, orange, red, violet, blue, green, brown, and gray. Marine blue and black were ex­ceptions, these colors being based on more saturated shades corre­sponding to their use in practice.

A second important point involves a consideration of the textile fiber used. A direct dye on cotton, for example, exhibits a different degree of light fastness from the same dye on glossy viscose or on matte artificial silk. Still greater differences are found between weighted and unweighted silks, the former giving a lower degree of light fastness. It was necessary, therefore, to set up auxiliary standards using the more important fibers such as cotton, artificial silk, acetate silk, weighted natural silk, unweighted natural silk, and wool. These auxiliary standards can be ordered from the German or Swiss Echtheitkommission or from dye manufacturers.

These auxiliary standards are consistent in depth of tint for all colors

and all fibers, and bence the light fastness ratings for all dyes on all the fibers can be compared directly.

Marine blue and black are handled separately as already pointed out. Because they use a different strength for the auxiliary standards, marine blues can be compared directly only with themselves, and a black with blacks.

Fig. 57. Step exposure.

This is still not the complete picture. It is desired to give the dyers information about the fastness properties of light and dark tints, as well as of the middle tones. To this end, it was arranged that dyes should be evaluated in three depths of tint, having the relationship to the auxiliary standard of 1/3, 1, and 2. That is to say, the light tints were prepared using one-third, and the dark tints with twice, the amount of dye required to produce the depth of tint in the standard. In special cases, deviations from this rule were necessary, as with light rose or gray tones where one-sixth or one-ninth tints may be evaluated, or with saturated browns where four — or sixfold depths of tint may be used. The ratios use, d must always be specified. With marine blues, a double tint, and with black, a deep black, are measured.

Because of the varying strengths of dyes, these one-third and double tints are not of equal depth and hence are not comparable with each other. Comparable fastness ratings are usually signified by printing in bold face type.

This new method is the basis for determining the light fastness ratings by German and Swiss manufacturers. Tables are given, listing three ratings for all dyes on all the textile fibers with which they are used.

This system for evaluating dyes meets all the requirements of the dye­ing trade. Each dyer is now able to select, from the tables, dyes which will be equal in light fastness for use with mixed fibers, and at the safne time, have information about their behavior in light and dark tints.

Similar efforts are being made in England and America. Indepen-

Compound

1. 6-Chloro-2-amlnoplienol-4-sulfonic acid

2. 3f4-Diehloroanlline-6-sulfonic acid

(No. 12, Table IV)

3. 2,4,5-Trichloroaniline

4. 4r5-Dichk>FO-2-aiiiinophenol

5. 4,5-Dichloro-2-anisidine

6. в-СЫого-4-aminoresorcinol dimethyl ether

7. Naphthol AS ITR

B. p-Phenylenediamine (paramine brown)

(No. I, Table IV, and No. 5, Table VII)

9. 3,4-Dichloro-6-nitroaniIine (No. 7, Table IV)

10. 4’Chloro-2-nitroaniline (fast red 3 CL base)

11. Lithol fast yellow CC

12. p-Dichlorobenzene

Compound

13. 4,e-Dichloro-2*aminophenol (No. 23t

Table VUI)

14. 4-CMoro-2-aminophenal

15. 4 Chloro-2-aminophenol-6-sulfonic acid

16. 4-Chloro-2*aminophenol-5-sulfonic acid

17. e-Nitro-4-chk>ro-2-aminophenol

18. 4-Chloro2-anisidine (chioranisidine P, fast

red R base)

19. Dichlorodianisidine

20. 2t5-Dichloro-/>-phenylenediamine

21. 6-Nitro-4-chloro-3-anisidine

22. 2,5-Diamino-4chloroanisole

23. 2>5-Dichloroaniline (fast scarlet CC base)

24. 2,5-Dichloroaniline-4-sulfonic acid

a
сі p. 62
so.4H SO3H
SO3H SO3H

Compound

1. o-Chlorometanilic acid

2. o-Aminoplienol-p-sulfonic acid

3. o-Anisidine-p-suifonic acid (No. 9, Table Ш)

4. o-Aminodiphenylether-p-sulfonic acid

5. Aniline-2t5-disdfonic acid

6. o-Nitroaniline-p-sulfonic acid

7. 2,6-Diaminophenol-4-sulfonic acid (No. 12, Table VIII)

Compound

8. 6-Nitro-2-aminophenoI-4-sulfonic acid (nitro acid I)

(No. II. Table VIII)

9. 2.6-Dinitroaniline-4-sulfonic acid

10. 2,6-Dinitroaniiine

11. 2.e-Dinitrodiphenylamine-4,3′-disulfonic acid

12. Tetrazo compound of No. 7

1 OCH, (7fH* НгКЧ^1

ci

Compound

1. o-Chloroaniline (fast yellow G base)

2. 2jChloroaniline 4*sulfonic acid (No. 10, Table VII)

3. o-Nitroaniline (fast orange GR base) (No. 1, Table VII)

4. o-Dianistdine, л

5. 4-Nitro-2-anisid! ne (fast scarlet R base) (No. 4, Table V)

6. 0‘Anisidine (fast red BB base)

7. 5 Nitro-2-anlsidine (fast red В base)

8. 2,5-Diaminoanisole

9. o-Anisidine-p-sulfonlc acid (No. 3, Table II)

■S

NOa

2 оснз J^jNOa

SCHa J^jNH2

ЯП. ШС. Н.Л.

Compound

10. Guaiacol

11. VantUin

12. 2-Anisidine-4-dtethylsu]famide (fast red ITR base)

13. o^Phenetidine

14. oAminodiphenyl ether

15. o Aminophenol (No. 16. Table VIII)

16. 5-Nitro-2-aminophenol (No. 17, Table VIII)

17. Aniline o-sulfonic acid (No. 6, Table VIII)

18. 8-Hydroxyquinoline

Compound

1. p-Phenylenediamine (paramine brown) (No. 8,

Table 1, and No. 5, Table Vll)

2. Chloro-p-phenylenediamine (No. 9, Table VI)

3. p-Aminophenyloxamic acid

4. p-Nitroaniline (fast red GG base) (No. 4, Table Vll)

5. 2-Chloro-4- nitroaniline

6. ^e-Dichloro^-nitroaniline

7. 3.4-Dichlorо-в-nitroaniline (No. 9, Table 1)

8. 4 • N itro-e-chloro-2-am inopheno!

9. 2-Chloro-4-anisidine (fast red R base)

10. 5-Nitro-2-chloro-4-anisidine

11. 3,4-Dichloroaniline

12. 3,4-Dichloraaniline-e-sulfon»c acid (No. 2. Table 1)

13. 4-Anisidine-3-su]fonic acid

14. p-Ani$idine

15. 3-Nitro*4-anisidine (fast Bordeaux GP base)

16. 4-‘Anisidine-2-sulfonic acid

17. 4-Aminodiphenylether-3-sulfonic acid

18. 4-Acetamino-2-aminophenol-e-sulfonic acid

Compound

19. p-Aminophenol (No. 22, Table VIII)

20. 6-Nitro-4^acetamino-2»aniinophenQl

21. p-Nitrophenol (No. 15. Table УШ)

22. 4»Acetamino-2-aminophenol (No. 14. Table V)

23. Monomethyl-p-aminophenol

24. p-Aminophenol-o-sulfonic acid

25. 4-Nitro-2-aminophenol-6-su]fonic acid (nitro acid III)

26. p-Nitroaniline-o-sulfonic acid

27. p-Phenylenediaminesulfonic acid

28. Benzoyl-p-phenylenediamfnesulfonic acid

29. 4-Chloroaniline*2-sulfonic acid

30. 4-Chloroaniline-3-sulfonic acid

31. p*Chloroaniline

32. 4-Aminodiphenylamine-2-sulfonic acid

33. 4r4′-Diaminodiphenylurea*3,3′.disulfonic acid

34. Nitrophenylenediamine (No. 6. Table Vll)

35. 4>Aminodiphenylether>2*sulfonic add

Ho3S|

N—- ( )NOj

SOsH

ГJ ■N“"

NHg

HOaS

Compound

1. Chloro-m-phenylenediamine

2. Chloro-m-phenylenediaminesulfonic acid

3. 6-Chloro-3-nitroaniline

4. 4-Nitro-2-anisidine (fast scarlet R base)

(No. 5, Table 111)

5. 2,4-DiaminoaniSole

6. 2,4-Dinitroaniline

7. p-Aminoazimide of J acid

8. m-Phenylenediaminesulfonic acid

9. 2,4- Dinitrochlorobenzene

10. Hexanitrodiphenylamine

Compound

11. 2,4-Dinitro-4′-hydroxydiphenylamine

12. 4,6-Diacetamino-2-aminophenol

13. 2,4-Diaminophenol

14. 4-Acetamino-2-aminophenol (No. 22,

Table IV)

15. 4*Nitro-2-aminophenol

16. 2,4-Dinitrophenol

17. Picric acid (No. 8, Table VIII)

18. Picramic acid (No. 9, Table VIII)

19. 4-Nitro-e-acetamino-2-aminophenol

20. 4-Nitro-6-chloro-2*aminophenol

hnos + no2

Compound

1. m-Phenylenediamine

2. Diphenyl*m-phenylenediamine

3. m-Nitroaniline (fast orange R base)

4. m-Aminophenylglycine

5. 3-Chloro-6-nitroaniline-4-sulfonic acid

6. 3-Chloro-6-nitroaniline (same as No. 14)

7. 3-Chloroaniline-4.suIfonic acid

8. 4-Nitro-3-chloroaniline

9. Chloro-p-phenylenediamine (No. 2. Table IV)

10. m*Chloroaniline (fast orange GC base)

11. 3-Chlofoaniline-6-sulfonic acid

12. 2-Chloro-4-dimethylaminobenzaldehyde

13. 4,e~Dianillnometanilic acid

Compound

14. Same as No. 6

15. 2,4-DichloroanUine (No. 7, Table VII)

16. m-Aminopbenol

17. Metanilic acid (No. 5, Table VIII)

18. Dialkylmetanilic acid (No. 30, ТаЫе VII)

19. Dialkyl-m-aminophenol (No. 31, Table VII)

20. Nitrosodialkyl*m-aminophenol

21. Benzidine-2,2’-disulfonic acid

22. Benzidine

23. Benzidine-3-sulfonic acid

24. Benzidine-3,3’-disulfonic acid

25. Benzidineoxamic acid

І

Compound

1. 0‘Nitroaniline (fast orange GR base) (No. 34 Table III)

2. Acetanilide (antifebrin)

3. p-Aminoacetanilide

4. p-Nitroanil’sne (fast red GG base) (No. 4. Table IV)

5. p-Phenylenediamine (paramine brown) (No. 8, Table I.

and No. 1. Table IV)

6. Nitro-p-phenylenediamine (No. 34. Table IV)

7. 2,4~Dichloroaniline (No. 15. Table VI)

8. 2,4,6-Trichloroaniline

9. Aniline^^d’tsulfonic acid

10. 2jChloroanil! ne*4-sulfon>c acid (No. 2, Table III)

11. Sulfanilic acid

12. 2j&‘DtchIoroaniIine*4«suIfontc acid

Principal Use Azo dyes (lake, ice colors) Antipyretic Azo dyes Azo dyes Oxidation dye, fur dyeing Oxidation dye* fur dyeing Azo dyes Azo dyes Azo dyes Azo dyes Azo dyes, azines. acid anthraquinone dyes Azo dyes Azo dyes

13. 2,6-DichIoroantline

(continued in Table Vllb)

Principal Use

Mulbple Tartrazine Azo dyes Tartrazine

Azo dyes, pharmaceutical Azo dyes Indigo Azo dyes

Photography (sensitizers) Photography (sensitizers).

quinophthalone dyes Azo dyes

Pharmaceutical (sulfanilamide) Pharmaceutical

nh2

Compound

25. Phenylglycine

26. Acetoacetanilide

27. p-Nitrosodimethylaniline

28. fbAminodimethylaniline

29. p-Aminodimethylanilinemercaptan

30. Dimethyhnetanilicacid (No. 18,Table VI)

31. Dimethyl-m-aminophenol (No. 19, Table 6)

32. Monomethylaniline 1

33. Dimethylaniline J

34. p-Dimethylaminobenzaldehyde

35. 4,4′-Tetramethyldiaminophenylmethane (methane base)

36. 4,4′-Tetramethyldiaminobenznydral (Michler hydrol)

37. 4.4’*Tetramethyldianiinobenzophenone (Michler ketone) 36. Diethylaniline 1

39. Monoethylaniline J

40. Monoethytp-phenylenediamine

Compound

41. Benzvlaniline (No. ll, Table IX)

42. Et hy Ibenzylanili ne

43. EthyJbenzylanilinesulfonic acid

44. Dibenzylaniline

45. Ethylhydroxyethylaniline

46. Hydroxyethylaniline

47. Dihydroxyethylaniline

48. Diphenylaminemonosulfonic acid

49. Diphenylamine

50. p-Aminodipbenylamine (diphenyl black base,

vari amine blue RT base)

51. Ouinone

52. Hydroquinone

53. Aminohydroquinonedimethyl ether

54. 5-Nitro-2-aminohydroquinonedimethyl ether

55. 5-Benzoylamino-2-aminohydroquinone dimethyl ether

(fast blue RR base)

Compound

1. Phenol-m-sulfonic acid

2. Resorcinol

3. m-Hydroxydiphenylamine

4. Resorcylic acid

5. Metanilic acid (No. 17. Table VI)

6. Aniline-o-sulfonic acid (No. 17, Table III)

7. 2-Aminophenol-4,6-disulfonic acid

8. Picric acid (No. 17, Table V)

9. Picramic acid (No. 18, Table V)

Ш. Phenol-p-sulfonic acid

11. 6-Nitro-2-aiuinophenoI-4-.sulfonic acid. (nitroacidl) (No. 8, Table II)

12. 2,6-Di;iiiiinopheroI-4-sulfonic acid

(No. 7» Table 11)

13. oNitroplienol

14. o-Aniinophenol-p-sulfonic acid

15. p-NitrophenoI (No. 21, Table IV)

16. o-Aminophenol (No. 15, Table III)

17. 5-Nitro-2-aminophenol (No. 16, Table III)

Compound

18. Phenol

19. p-Phenetidine

20. Phenacetin

21. o-Chlorophenol

22. p-Aminophenol (No. 19, Table IV)

23. 4,6-Dichloro-2-aminophenol (No. 13, Table I)

24. p-Chlorophenol

25. 2,4-Dichiorophenol

26. Chloranil

27. p-Nitrosophenol

28. p-Aminosalicylic acid

29. Salicylic acid

30. p-Chloro-o-aminosalicylic acid

31. Same as No. 22

32. Carbazoleindophenol

33. Sulfosalicylic acid

34. p-Sulfo-o-aminosalicylic acid

Principal Use

Disinfectant, azo dyes, triphenylmethanes, sulfur dyes Azo dyes Antipyrectic Azo dyes

Photography (developer), sulfur dyes, fur dyeing Azo dyes (chrome)

Azo dyes, anthraquinone dyes Disinfectant

Sulfur dyes, vat dyes (helindone), oxazines Indophenols. sulfur dyes Azo dyes (chrome)

Azo dyes, triphenylmethanes, anthraquinone dyes, pharmaceutical Azo dyes (chrome)

Vat dye (hydrone blue)

Azo dyes

Azo dyes (chrome)

сн2а CH3

Compound

1. Benzyl alcohol

2. Benzaldehyde (oil of bitter almond)

3. o-Nitrobenzaldehyde

4. m-Nitrobenzoyl chloride

5. m-Nitrobenzaldehyde

6. m-Aminobenzaldehyde

7. o-Nitrocinnaniic acid

8. Benzotricliloride

9. Benzoyl chloride

10. m-Hydroxybenzaldehyde

11. Benzylaniline (No. 4lf ТаЫе VII)

12. Benzamide

13. Cinnamaldehyde

14. Phenylacetyl chloride

15. o-ToluenesuIfamide Ів. p-Toiuenesulfamide

17. Nitro-p-phenylenediamine

18. p-Chlorobenzoic acid

Principal Use Perfume

Perfume» triphenyhuethanes, acridines Indigo

Azo dyes (rosanthrene), pharmaceutical

Triphenylmethanes

Triphenylme thanes

Indigo

Triphenylmethanes

Multiple

Triphenylmethanes

Triphenylmethanes

Anthraquinone vat dyes

Perfume

Ciba lake red В

Saccharin

Disinfectant

Azo dyes

Triphenylmethanes

Compound

19. 2,4-DichIorobenzoyI chloride

20. 4t6-Dichloro-3-iiminoben/.(>i( acid

21. Benzaldehyde-o-sulfonic acid

22. o-Chlorobenzaldehydc

23. o-Chlorobenzoic acid

24. 6-Chioro-3-aiuinobenzoic acid

25. 6-ChIoro-2-toIuidine-4-siiIfi>nic acid

26. o-Chlorobenzoyl chloride

27. 6-ChIoro-3-toIuidine-4-suIfonic acid 28 6-Cldoro-3-toluidine

29. 2-Toluidine-4-sulfonic acid

30. 2-Amino-4-cresol

31. Benzaldehyde2t4disuIfonic acid

32. 2.6-Toluylenediamine-4-sulfonic acid

33. p-Cresol

Principal Use Azo dyes (anthosines) Azo dyes Triphenylmethanes Triphenylmethanes Anthraqninone-acridones Azo dyes Azo dyes Azo dyes* vat dyes Azo dyes (lake) Azo dyes Azo dyes Rhodamines Triphenylmethanes Azo dyes Disinfectant, a/о dyes Azo dyes (lake) Azo dyes

<34. p-Sulfoanthranilic acid

35. o-Tolidine-m-disulfonic acid

COOH CHO

Compound

36. Benzidine-3,3′-dicarboxylic acid

37. 6-Chloro-2-toluidine (fast scarlet TR base)

38. 2,6-Dichlorobenzaldehyde

39. 2-ChJoro-6-nitrobenzaldehyde

40. Same as No. 3

41. 4-CUoro-2-toluidine (fast red KB base)

42. 4-Chloro-2-toluidine-5-sulfonic acid

43. 4-Chloroanthranilic acid

44. o-Tolidine

45. Diacetoacet-o-tolidide (naphthol AS G)

46. 2-Toluidine-5-suIfonic acid

47. Monomethyl-o-toliiidine

48. 5»Anilino-2-aniino-3-mercaptotoluene

49. o-Toluidine

50. 3*Cliloro(bromo)-2-toluidine-5-sulfonic acid

51. >3-Chloro(bromo)-2-toIuidine

52. 6-Nitro-2rt<iluidine

53. 5-Nitro-2-toluidine (fast red RL base)

54. 4-Nitro-2-toluidine (fast scarlet C base)

55. 5-ChIoro-2-tbluidine (fast red TR base)

Azo dyes Azo dyes (ice colors) Triphenylmethanes Halogenated indigo Azo dyes (ice colors* hike) Azo dyes (lake) Azo dyes Azo dyes (subst.) Azo dyes (ice colors) Azo dyes Di — and triphenylmethanes* thiazines Sulfur dyes Multiple Azo dyes (tartrazine) Azo dyes Azo dyes Azo dyes (ice colors) Azo dyes (ice colors), thioindigo dyes Azo dyes (ice colors) Azo dyes

56. 3-Nitro-2-toluidine

Compound

57. m-Tohiylenediamine

58. m-Toluylenediaminesulfonic acid

59. 2-ChIoro-4-toIuidine-5-sulfonic acid

60. Trinitrotoluene

61. 2-Chloro-4-toIuidine

62. 5-Nitro-2-chb>ro-4-toluidine

63. 2j6-D»cIiloro-4-toluidine

64. 4-Toluidine-2-sulfontc acid

65. 4-Nitrotaluene-2-sulfonic acid

66. pTp/-Dianiinostilbenedisutfonic acid

67. 4-Toluidine-3-sulfonic acid

68. 2-Nitro-4-toluidine

69. p-Toluidine

70. 3-Nitro-4-toluidine (fast red C base)

71. 3-ChIoro-4-toluidine

72. Cresidine

73. m-Toluidine

74. Dimcthyl-m-toluidine

75. Ethylbenzyl-m-toluidine

76. Etliylbenzyl-m-t61uidinesulfonic 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

Stilbene dyes (subst.)

Azo dyes (subst.)

Azo dyes Azo dyes Multipe

Azo dyes (lake, ice colors)

Azo dyes

Azo dyes (middle comp.)

Azo dyes

Triphenylmethanes

Triphenylmethanes

Triphenylmethanes

Compound

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

2. l-Diazo-2-naphthol-4-sulfonic acid (cf. No. 29, Table XII)

3. 2.4-Dinitro-l-naphthol-7-sulfonic acid (naphthol yellow S)

4. l-Hydroxy-2-naphthoic acid

5. Ethyl-o-naphthylamine

6. о-Naphthol (No. 1, Table XI)

7. 2.4-Dinitro-l-napbthol (Martius yellow)

8. 4-Benzoyl-I-naphtho!

9. o*Naphthylamine

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

Compound

11. l-Amino-Snaphthol-7-sulfonic acid (M acid) (No. 4, Table XI)

12. Phenyl-o-napnthylamine

13. I-Naphthylamine-4-sulfonic acid (naphthionic acid)

14. l-Naphthol-4-sulfonic acid (Nevile-Winther acid)

15. l-Naphthylamine-4,e-disulfonic acid (Dahl acid)

16. l-Naphthylamine-4t7-disulfonicacid (Dahlacid)

17. 1,5-Dinitronaphthalene

18. 15-Diaminonaphthalene

19. 13-Dinitronapnthalene

20. Perimidine

21. l-Amino-8-naphthol3-su]f<Muc acid (No. 14, Table XI)

22.
Naphthazarin

Compound

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

2. l-Naphthylaniine-5-sulfonic acid

3. l*Naphtbylaniine-5+7-disulfonic acid (No. 10,

ТаЫе X)

4. l-Amino-5-naphthol-7-sulfonic acid (M acid)

No. П, Table X)

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

6. l-Naphtliol-4,8-disulfonic acid (Schoellkopf

acid)

7. l-NaphtIiylmiiine-8-suIfonic acid (peri acid)

8. I-Phenylnaphthylamine«8-sulfonic acid

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

10. l-Amino-5-naphthol

11. l-Amino-8-naphthol-4-su]fonic acid (S acid)

12. 18-Dihydroxynaphthalene-4-sulfonic acid

13. l-Amino-8naphthol

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

Table X)

15. I-Aniino-8-naplithol-5,7-disulfonic acid

16. 2-AininonaphlIialene-4.8-disulfonic acid (C

acid)

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

acid. Chicago acid )

18. I-NaplitIiylainine-4,6,8-trisulfonic acid

19. I-Amino-&iiaphthol-41.6-di. suIfonic acid (K

acid)

20. l-Benzoyliiinino-8 napIithob4,e-disu]fonic acid

(Anthosine acid)

21. I-Naphthylaniine-3,8-disulfonic acid

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

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

24. I-Naphthol-5-sulfomc acid

25. 1,5-Diliydroxynaphthalene

26. l-Naphthol-3f6-disulfonic acid (Rudolf Giircke

acid)

27. l-Naphthol-3,63-trisu]fonic acid

28. l,8*Dihydroxynaphthalene*3,e-disulfonic acid

(chromotropic acid)

29. l-Naphthylamine-3,e-disulfonic acid (Freund

acid)

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

acid)

31. p-Aminophenyl-l42-naphthotriazole-4,8-disu]fonic

acid)

32. l-Naplithylamine-3.6,8-trisu]fonic acid (Koch

acid)

35. AcetonyTl,8-naphthylenediamine-3,e-disulfonic acid

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

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

acid

36. Naphthalene-2t7-disulfonic acid

37. 15-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-3t7-disulfonic acid

43. 2,7-Dihydroxynaplithalene

44. 2-Naphthylaniine-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-Naphthylaniine-7-sulfonic acid (Cleve acid)

50. 4-Acctamino-I-naphthylamine-6-sulfonic acid

51. l-Amino-7-naphthol

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

Compound

1. 2-Naphthylamine-l-sulfonic acid

2. 2-Naphthylaniine-5t7-disulfonic acid

3. 2-Amino-5-naplitliol-7-sulfonic acid (Jacid)

4. 2-Naphthol-8-sulfonic acid (crocein acid)

5. 2-Naphthoie^disulfonic acid (C salt)

6. 2>8-Dihydroxynaphthalene-6-snlfonic acid

7. 2-Aniino-8-naphtliol-6-sulfonic acid (Camma acid)

8. 2-Naphthylamine-6,8-disulfonlc acid (amino-G salt)

9. 2-Naplithol-3,6t8-trisulfonic acid

10. 2-Naphthylamine-3,6t8- trisulfonic acid

11. 2-Amino-8-naphthol-3t6-disulfonic acid

(Gamnia-disulfonic acid)

12. 2-Naphthol-6-sulfonic acid (Schaeffer acid)

13. 2-Naphthol-3t6-disulfonic acid (R salt)

14. 2-Naphthylamine-3.6-disnlfonic acid (aniino-R salt)

15. 2-Amino-3-naphthQl-6-sulfonic acid

16. 2>6-Dihydroxynaphthalene

17. 0-Naphthol

18. 2-Niiplithyiamine-6-sulfonic acid (Bronner acid)

19. I-Aniino-2-mcthoxynaphthalene-6-siilfonic acid

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

Principal Use Azodyes (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, tripbenylmetbanes Azo dyes Azo dyes Azo dyes Azo dyes* tripbenylmetbanes. oxazines Azo dyes Azo dyes Lake (as Fe salt) Photography (developer), oxazines

21. I-Amino-2-naphth<^-6-sulfonic acid (Eikonogen)

Compound

22. /9-Naphthol methyl ether

23. l-Amino-2-naphthol methyl ether

24. 2-Naphthylamine-5-sulfon»c add

25. 2-Naphthylamine*1,5-disulfonic acid

26. 2-Ainino-5-naphthoH,7-disulfonie acid

(J disulfonic acid)

27. 2-Hydroxy -3-naphthoic acid

28. l-Nitroso-2-naphthol

29. I-Aniino-2-naphthci-4-$ulfonic acid

(cf. No. 2» Table X)

30. ^Naphthoquinones ulfonic acid

31. 2-Naphthylainine-7-sulfonic acid (No. 44, Table XI)

32. 2-PhenyIaniino-5-naphthol-7-$uIfonic acid

(phenyl-J acid)

33. 2-Hydroxy-3-naphthanilide (naphtholAS)

34. Ethyi-S-naphthylamine

35. PhenyI-/3-naphthylamine

36. ^-Naphthylamine

37. 2-Naphthylamine-8-sulfonic acid (Badische acid)

38. 2-Phenylaniino-8-naphthoI-e-sulfonic acid

(phenyl-gamma acid)

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

Phenyl mustard oil

TABLE Xlllb. Derivatives of 2-Amino-5-naphthol-7-sulfonic Acid (J Acid) (continued from Table XHIa)

Compounds 14 to 2-3 are all used as end or middle components
for substantive cotton dyes.

Compounds I to 3 are used as end or middle components
for substantive cotton dyes.

Compound

1. Dibenzopyrenequinone (indanthrene

golden yelow GK) (No. 5, Table XVI)

2. о-Naphthohydroquinone monomethyl ether

3. 2,3-Dichloro-o-naphthoquinone

4. 5-Aminoacetylanthranilic acid

5. a-Naphthoquinone

6. 5-Nitroanthranilic acid

7. 5-Sulfoanthraniiic acid

8. 2t4-Dihydroxyquin61ine

9. 5-Chloroanthranilic acid

Compound

10. Phthalic anhydride

11. Anthranilic acid

12. o-Carboxyphenyltliioglycolic acid

13. 3-Hydroxythionaphthene

14. Methyl anthranilate

15. Phenylglycine-o-carboxylic acid

16. TetracMorophthalic anhydride

17. m-Aiuinobenzoic acid

Compound

1. Benzanthrone

2. fcz-I-Chlorobenzantlirone

3. Isodibenzanthrone (indanthrene vi<jlet R)

4. Dibenzantlirone (indanthrene dark Ыие BO)

5. Dibenzopyreneqninone (indanthrene golden

yellow GK) (No. 1> Table XV)

6. 1,4,5,8-Tetraaiiiinoantliraquinone

7. Anthracene Ыие SWX (alizarin cyanine S)

Compound

8. Anthracene blue WR (alizarin cyanine)

9. Anthracene blue GG

10. Indanthrene yellow 3 GF

11. 1,5-Diaminoanthraquinone

12. Anthraquinone blue SR

13. 13-Dianiinoanthraquinone

14. Indanthrene yellow GK

Principal Use Mordant dye Mordant dye Vat dye Vat dyes, acid wool dyes Acid word dye Vat dyes* acid wool dyes Vat dye Vat dye

15. Algol brilliant red 2 В

Compound Principal Use

1. 2‘Chloroanthraquinone Vat dyes

2. 2-Aminoanthraquinone Vat dyes

3. l,3-Dibromo-2«aminoanthraquinone Vat dyes

4. Algol orange Vat dye

5. 2,6-Diaminoanthraauinone Vat dyes

6. Benzanthronequinoline Vat dyes

6

Erweco alizarin acid Ыие R

Compound

7. 1,2.6-Trihydroxyanlhraquinone (flavopurpurln)

8. 1+2,4,53,8-Hexahydroxyanthraquinone

(alizarin brilliant cyanine RJ

9. 1,2,7-Trihydroxyanthraquinone (anthrapurpurin)

10. Erweco alizarin acid Ыие R

X. Anthraquinoneacridone (No. 4, Table XIX, and No. 9, Tahle XXI)

2. Alizarin astrd В

3. Alizarin geranol В

4. 4-Broino-I-acetylmethylaminoanthraquinone

5. Alizarin rubinol R

6. Alizarin irisol R

7. o-Anthrol

ComfHHtnd

8. Anthraquinooe violet

9. 1,5-Dichloroanthraquinone

10. Indanthrene brilliant violet BBK

11. Alizarin sapliird В

12. Alizarin saphirol SE

13. I 8-Dihydroxynnthraquinone (chrysazin)

14. l,4t8-Trihydroxy«nthruquinone

C’ompmmd

1. Helindone yellow RW

2. Algol grey В

3. Indantlirene olive R

4. Anthraquinoneacridone (No. 1, Table XVIII,

and No. 9» Table XXI)

5. o-Aminoanthraquinone (fast red AL base)

6. Anthrapyridone

7. Helindone brown

Compound

8. l-Aminoanthraquinone-2-sulfonic acid

9. 4- Bronio — l-aminoanthraquinone — 2- sulfonic acid

10. Alizarin риге Ыие В

11. 2t4*Dibromo-I*aminoanthraquinone

12. Alizarin sapbirol A

13. Algol yellow WG

14. 1,4-Diaminoanthraquinone

15. Indanthrene red 5 GK

Compound

1. It2-Dihydroxyantliraquinone-3-sulfonic acid (alizarin S)

2. Alizarin viridine FF

3. 1,2,53-Tetrahydroxyanthraquinone (alizarin Bordeaux R)

4. Alizarin brilliant cyanine GC

5. l,2-Dihydroxyanthraquinone-5-sulfonic acid (Erweco acid

alizarin red)

6. 1,2,5-Trihydroxyanthraquinone (alizarin brilliant Bordeaux R)

7. I,2,4r5,8-Pentahydroxyanthraquinone (alizarin cyanine R)

8. 1,4-Dihydroxyanthraquinone (quinizarin)

Compound

9. I,2-Dihydroxyanthra<iuinone (alizarin)

10. 1,2,4-Trihydroxyanthraquinone (purpurin)

11. Alizarin heliotrope

12. 4-Aniino-I,2-dihydroxyanthraquinone (alizarin garnet)

13. Alizarin green S

14. 3-Nitro-I^-dihydroxyanthraquinone (alizarin Mange A)

15. 3-Ainino-I,2-dihydroxyanthraquinone (alizarin maroon)

16. Alizarin Ыие S

Compound

X. Pyranthrone (indanthrene golden orange G)

2. l-Chloroanthraquinone*2-carboxy lie acid

3. Dimethybrneso-benzodianthrone

4. аЙо-meso-Naphthodianthrone

5. meso-Anthradianthrone

6. Cyananthrol

Compound

7. Anthraflavone G

8. Anthraquinonethioxanthone

9. Anthraquinoneacridone (No. 1, Table XVUI

and No. 4, Table XIX)

10. Same as No. 2

11. 1-Aminoanthraquinone-2-carboxylic add

[1]Frdl., 7, 90 (1902-1904) (Note).

[2] Witt, Ber., 48, 750 (1915).

[3] Kofler, “M ikroskopische Methoden zur Identifizierung organischer Substanzen,” Supplement to 2. Ver. deut. Chem., No. 36 (1940).

[4]See, for example, Fierz-David, Helv. Chim. Acta, 10, 219 (1927).

[5] See, for example, Fierz-David, Helv. Chim. Acta, 10, 200 (1927).

[6] Concerning the mononitration of 2-methylanthraquinone, see p. 227, as well as Locher and Fierz, Helix Chim. Acta, 10, 642 (1927).

[7]Hefti, Helv. Chim. Acta, 14, 1404 (1931).

[8] M.,L., and B., Ger. Pat. 75,288 (1894) [Frdl, 3, 260 (1890-1894)1.

[9] C. Kranzlein, Aluminiumchlorid in der organischen Chemie. 2nd ed., Verlag Chemie, Berlin, 1935.

[10] See Fierz-Davia, Kiinstliche organische Farbstoffe, Hauptwerk. Springer, Berlin, 1926, p. 538 ff.

[11] Soc. Chim. Usines Rhone, Ger. Pat. 98,433 (1898) [Frdl, 5, 41 (1897-1900)1.

[12] Cf. the preparation of o-chlorotoluene from p-toluenesulfonic acid according to Badische A. und S. F., Ger. Pat. 294,638 (1916) [Frdl., 12, 908 (1914-1916): C. A., 11, 2582 (1917)]. See also, p. 163.

[13] For the construction of industrial equipment, see, for example, Ullmann, Enzyklopadie der technischen Chemie. 2nd ed., Vol. 1, Urban und Schwarzen — berg, Berlin, 1928, pp. 465 and 467.

[14] See, for example, I. G., Ger. Pat. 436,820 [Frdl., 15, 391 (1928)1.

[15] Hale and Britton, Ind. Eng. Chem., 20, 114 (1928).

[16]« Chem. Fab. Griesheim, Ger. Pat. 97,013 (1896) [Frdl., 5, 47 (1897-1900)].

[17] Badische A. und S. F., Ger. Pat. 289,111 (1915) [Frdl., 12, 308 (1914-1916); C. A., 10, 2529 (1916)1.

27 C. Curtis Dissertation, Zurich-Weida, 1929. This also gives the preparation of 1-anthraquinoneoxainic acid and of indanthrene red 5 GK.

[18] See page 115.

31 Carter, Z. ges. Schliess — u. Sprengstoffw., 8, 205, 251 (1913).

[19] O. Wyler, Helo. Chim. Acta, IS, 23 (1932).

[20] Obermiller, Ger. Pat. 281,176 (1914) [Frdl., 12, 125 (1914-1916); C. A., 9,

1830 (1915)1.

37 Fierz, Schlittler, and Waldmann, Helv. Chim. Acta, 12, 663 (1929).

38 I. G., Fr. Pat. 734,616 (1932) [C. A., 27, 1002 (1933)1.

39 W. Stockar, Dissertation, Eidg. Techn. Hochschule, Zurich, 1942.

[25] Huber, Dissertation, Zurich, 1931.

[26] Lunge and Berl, Chemisch-techmsche Untersuchungsmethoden. 6th ed., Vol. IV, Springer, Berlin, 1910-1911, p. 625.

[27] See, for example, Heumann, Die AniUnfarben und ihre Fabrikation, Vieweg, Braunschweig, 1888-1903.

[28] E. Ziegler, Dissertation, Zurich, 1928. See also Fierz-David and Blangey, Kunstliche organische Farbstoffe, Erganzungsband, Springer, Berlin, 1935, p. 58.

[29] Fierz and Stamm, Helv. Chim. Acta, 25, 364 (1942).

[30]Kempf and Moehrke, Ger. Pat. 256,034 (1913) [Frdl.. 11, 193 (1912-1914);

CA„ 7, 2096 (1913)1.

[31] M., L., and B., Ger. Pat. 263,382 (1913), 265,195 (1913), 265,196 (1913), 270,401 (.1914) [Frdl., 11, 257 ff. (1912-1914); C. A., 8, 257, 429, 2261 (1914)1. R. Lesser, Ger. Pat. 236,074 (1911) [Frdl., 10, 282 (1910-1912); C. A., 6, 2007 (1912)].

[32]Badische A. und S. F. (Julius and Miinch), Ger. Pat. 167,012 (1905) [Frdl., 8, 752 (1905-1907)1.

[33] Hofmann, Ger. Pat. 65,131 (1892) [Frdl., 3, 826 (1890-1894)1.

[34] Schultze, Ger. Pat., 85,493 (1896) [Frdl., 4, 145 (1894-1897)1.

[35] Badische A. und S. F., Ger. Pat. 294,638 (1916) [Frdl, 12, 908 (1914—1916);

C. A., II, 2582 (1917)1.

[36] Badische A. und S. F. Ger. Pat. 160,536 (1905), 157,325 (1904), 156,440 (1904) [Frdl., 8, 656-7 (1905-1907)1.

[37] Bayer & Co., Cer. Pat. 109,102 (1899) [Frdl., 5, 164 (1897-1900)1. Badisclie A. und S. F., Ger. Pat. 115,335 (1900), 117,471 (1900), and 126,136 (1901), [Frdl, 6, 187-190 (1900-1902)1.

[38] Badische A. und S. F., Ger. Pat. 121,683 (1901) and 122,570 (1901) [Frdl., 6, 192-194 (1900-1902)1.

[39] I. G. (Limpach and Hager), Ger. Pat. 550,707 (1930) [Frdl., 19, 1899 (1934); C. A., 26, 4962 (1932)]. Helv. Chim. Acta, 29, 1756 Г1946).

[40] Witt, Ber., 48, 743 (1915).

[41] The Calico Printers Assoc, and E. Fourneaux, Ger. Pat. 204,702 (1909) [Frdl., 9, 408 (1908-1910); C. A., 3, 958 (1909)1

[42] The solution can also be heated under reflux.

[43] — Naphthylamine-8-sulfonic acid can be converted into the diazonium com­

pound by treatment with nitrous acid (sodium nitrite) in mineral acid solution at

[45] O. Kruber, Ber., 64, 84 (1931). Pier and Schoenemann (I. G.), Ger. Pat. 639,240 (1936) [C. A., 31, 1590 (1937)1 and 640,580 (1937) [C. A., 31, 5543 (1937)1.

T1 Vollmann, Becker, Corell, and Streeck, Ann., 531, 1-159 (1937).

[47] Kranzlein, Z. angew. Chem., 51, 373 (1938).

[48] For example, 30 grams of the crude material is dissolved in 240 grams of con­centrated sulfuric acid at a temperature not to exceed 35°, and 135 grams of 62.5 per cent (50° Be) sulfuric acid is added. The nearly colorless crystals of the amine sulfate are filtered off on a sintered glass funnel, washed with 82-83 per cent sulfuric acid, and then converted to the free base by stirring with water. 77 Kriinzlein, Nawiasky, Corell, Kunz, and Schiitz (Badische A. und S. F.), Ger. Pat. 421,206 [Frdf., 14, 1495 (1921-1925)1.

[49] Secondary amine.

[50] Kalle & Co., Ger. Pat. 175,593 (1906) and 176,618 (1906) [Frdl., 8, 648, 651

(1905-1907); C. A., 1, 1202, 1208 (1907)1.

[51] Cf. Laska, Zitscher, Christ, and Petzold (I. G.), Ger. Pat. 508,585 (1930) [Frdl.,

17, 967 (1932); CA., 25, 599 (1931)1.

[52] See Geigy, Ger. Pat. 224,024 and 224,025 (1910) [Frdl., 10, 844-845 (1910- 1912); C. A., 4, 3304 (1910)1.

MCf. Agfa, Ger. Pat. 131,860 I Frdl, 6, 872 (1900-1902)].

[54] Volume per cent: 1 liter contains 200 grams of 100 per cent sodium nitrite.

[55] Ger. Pat. Applic. F 28,279 (1910) [Frdl., 10, 946 (1910-1912)].

[56] The benzo light dyes have more recently been sold under the name, Sirius ‘Light, t It is essential to determine the purity of the starting materials. Anilinedisulfonic acid andmaphthylaminesulfonic acid are analyzed by titration with nitrite, phenyl-J acid by titration with diazobenzene (see Analytical Section, pages 386-390).

I It is possible, with suitable precautions, to achieve good results without using alcohol. The a-naphthylamine is dissolved in a boiling mixture of 28 cc. 2 N hydrochloric acid and 100 cc. water, and the solution is filtered if necessary and allowed to cool to about 50°. Before the hydrochloric acid begins to crystallize out, the solution is poured rapidly into the diazo solution containing ice, and then a solution of 7 grams of crystalline sodium acetate in 20 cc. water is added slowly.

[57] Contrary to the general impression, phenol does not couple readily with diazo compounds. Diazo ethers are frequently formed and the reaction is mistaken for true coupling. The procedure given here, in which the acid diazo solution is mixed with the phenol (or cresol) and the mixture treated with soda without sodium hydroxide, gives the azo dye in much better yield.

[58] See, however, Schmidt and Hagenbocker, Ber., 54, 2201 (1921).

[59] Kern, Dissertation, Zurich, 1921; Geigy, Ger. Pat. 278,613 (1914) [Frdl 12 323 (1914-1916); C. A., 9, 1847 (1915)1.

[60] This auramine process is ascribed to Feer in the patent literature. The actual discoverer, however, was Sandmeyer. Feer, Ger. Pat. 53,614 (1890) [Frdl., 2, 60 (1887-1890)1.

[61] In many plants, saltpeter is preferred over chlorate since it attacks iron less readily and is reduced directly to ammonia in the process. Chlorate, however, gives a more clear-cut reaction.

[62] du Pont, Ger. Pat. 656,944 (1938) [Frdl., 24, 868; C. A., 32, 4176 (1938)1.

98 Pope and Scottish Dyes, Ltd., Ger. Pat. 382,178 (1923) [Frdl., 14, 871 (1921- 1925)1.

(1910) [Frdi., 9, 1197 (1908-1910); C. A., 5, 592 (1911)].

[65] Hefti, Helv. Chim. Acta, 14, 1404 (1931). Schmidt (Bayer), Ger. Pat. 225,232

[66] Badische A. und S. F., Ger. Pat. 56,273 (1891) [Frdl., 3, 281 (1890-1894)1.

[67] Badische A. und S. F., Ger. Pat. 127,178 (1901) [Frdl., 6, 538 (1900-1902)1.

[68] Sandmeyer, Z. Farben — u. Textilchem., No. 7, p. 129 (1903). Also, Helv. Chim. Acta, 2, 234 (1919).

[69] H. de Diesbach and E. von der Weid, Helv. Chim. Acta, 10, 886 (1927).

[70] Linstead, Ber., 72, 93 (1939).

[71] This involves a relatively large amount of hand work and as a result the opera­tion of filter presses is more costly than that of suction filters or centrifuges. The latter are preferred, therefore, if the properties of the precipitate permit their use. 104 See, for example, Ullmann, Enzyklopadie der technischen Chemie. 2nd ed., Vol. 5, Urban und Schwarzenberg, Berlin, 1928, p. 358 ff.

[72] The inlet tubes on filter presses, as well as the stopcocks on dye vats, are almost always made from the best bronze.

1 An alloy of equal parts of tin and lead has practically no expansion on heating.

[73] See Knecht and Hibbert, New Reduction Methods in Volumetric Analysis. 2nd ed., Longmans, Green, London, 1928.

[74] Fierz-David, /. Soc. Dyers Colourists, 45, 133 (1929).

[75] Ruggli and Jensen, HeIv. Chim. Acta, 18, 624 (1935). See also Zechmeister

ana Cholnoky, Die chromatographische Adsorptionsmethode. 2nd ed., Springer,

Wien, 1938.

[76] Frische, Ann., 224, 141 (1884).

[77] Kranzlein, Werden, Sein, und Vergehen der kiinsllichen organischen Farhstoffe, Ferdinand Enke, Stuttgart, 1935.

[78] By Dr. Heinrich Ris.

[79] Verfahren, Typen, und Normen fur die Prufung und Beurteilung der Echtheit — seigenschaften, Verlag Chemie, Berlin, 1939. This also gives the procedures for determining other fastness ratings, such as fastness to washing, chlorine, alkali, and acid.