appears around 2850 cm.-' in tigogenin derivatives and A6 compounds, but is only an inflection in most other steroidal sapogenins. This band was also assigned to the CHZ group because it decreases with increase in ring substitution. The band is almost undetectable in ketonic sapogenins. The 2860-cm.-" CH1 band almost disappears in A5 acetates, except for carbonyl compounds. I n compounds with open E and F rings, the bands in this region appear a t lower frequencies. A band near 2830 cm.-' is associated with A6 unsaturation, and is stronger in C=O compounds, but no definite assignment can be made. CONCLUSIONS
Structural features of various steroidal sapogenins can be identified from details of their C-H stretching spectra. Of the seven to nine bands observed, five can be associated with specific
I
modes of =CH, CH,, and CH, groups. All observed bands seem to show a strong dependence on the over-all structure of the molecule. Easiest to characterize are &deoxysapogenins, sapogenin acetates, Ab compounds, and open-ring compounds. I n 3-deoxysapogenins, the CH2groups absorb so much more than the CH3 groups that CHs bands a t 2950 and 2870 cm.-l are perceptible only as shoulders on the slopes of strong CH, bands. Acetylation increases the relative intensity of these
CH, bands, making them nearly equal to the CHZbands. The presence of two additional bands around 3035 and 2830 ern.'' is sufficient to characterize A5 unsaturation. In addition, A5 acetates show increased absorption around 2910 cm.-', paralleled by decreases near 2930 and 2860 cm.-' Open-ring compounds have broader and fewer bands, and those below 2880 cm.-' are shifted to lower frequencies. The 208 compounds are readily recognized by inflections around 3000 cm.-l, and in some cases also a t 2920 cm.-l The CH2 bands of 208, 2 5 acetates ~ are slightly stronger, and the CHS bands weaker than those of the corresponding 20a compounds. cis-A/B sapogenins with 2 5 ~methyl groups have a greater absorption area and broader individual bands than their trans-A/B, 2 5 counterparts. ~ N o transA/B, 2 5 compounds ~ and only one cisA/B, 2 5 ~compound were available. The cis- and trans-25~compounds were similar, suggesting that the band-broadening and increased area are mainly caused by D, L isomerism in the 25 position. ACKNOWLEDGMENT
The authors acknowledge many helpful discussions with Heino Susi of the Eastern Regional Research Laboratory. LITERATURE CITED
(1) Fox, J. J., Martin, A. E., Proc. Roy. SOC.(London )A162,419 (1937). (2) Ibid., A167, 257 (1938).
(3) Zbid., A175,208 (1940). (4) Guertin, D. L., Wiberley, S. E., Bauer, W. H., J . Am. Oil Chemists' SOC. 33, 172 (1956). (5) Jones, R. N., Herling, F., J . Org. Chem. 19, 1252 (1954). (6) Jones, R. N., Humphries, P., Packard, E., Dobriner, K., J . Am. Chem. SOC. 72,86 (1950). (7) Jones, R. N., Williams, V. Z., Whalen, H. J., Dobriner, K., Zbid., 70, 2024 (1948). (81 Miiker, R. E., Wagner, R. B., Ulshafer, P. R., Wittbecker, E. L., Goldsmith, D. P. J., Ruof, C. H., Ibid., 69, 2167 (1947). (9) Nolin, B., Jones, R. N., Can. J . Chem. 34,1382 (1956). (10) Ibid., p. 1392. (11) Nolin, B., Jones, R. N., J . A m . Chem. SOC.75,5626 (1953). (12) Pozefsky, A., Coggeshall, N. D., ANAL.CHEM. 23,1611 (1951). (13) Saier, E. L., Coggeshall, N. D., Zbid., 20, 812 (1948). (14) Saunders, R. A., Smith, D. C., J . Appl. Phys. 20, 953 (1949). (15) Tallent, W. H., Siewers, I. J., ANAL. CHEM.28,953 (1956). (16) Wall, M. E., Ezperientia 11, 340 (1955). (17) Wall, M. E. Krider, M. M., Rothman, E. S., Eddy, C. R., J . Biol. Chem. 198, 533 (1952). (18) Wall. M. E.. Serota., S.., J . Am. Chem. ' doc. 78,'1747 (1956). (19) Wall, M. E., Walens, H. A., Ibid., 77, 5661 (1955). (20) Zbid., 80, 1984 (1958). RECEIVED for review January 1, 1959. Accepted May 25, 1959. Abstracted from a thesis in chemistry submitted by Anne M. Smith in partial fulfillment of the requirements for the master of arts degree at Temple University, Philadelphia, Pa., June 1958.
X-Ray Powder Diffraction Data of Azoic Coupling Components ISIDORE SCHNOPPER, JOSEPH 0.BROUSSARD, and COSMO K. LaFORGlA U. S. Customs laboratory, New York, N. Y. ,X-ray powder diffraction data are presented for 15 organic compounds. The data permit identification of the azoic coupling components of commercially available Naphthol AS, some of its derivatives, and related compounds.
A
of coal tar products provided for under the United States Tariff Act as amended (8) N IMPORTANT CLASS
Naphthol AS 3-Hydroxy-2-naphthanilide
1542
ANALYTICAL CHEMISTRY
includes Naphthol AS, its derivatives, and related compounds (1, 3-5). These products are azoic coupling components extensively used in dyeing and printing fabrics, and thus of great commercial importance. The Tariff Act specifies that the ad valorem rate of duty applicable to importations of dutiable coal tar products shall be based upon the American selling price of any similar competitive article manufactured or produced in the United States. To that end, one function of the U. S. Customs Laboratories is to advise customs officers on the identity and comparability status of imported coal tar products. To improve this service, an effort has been directed towards an increasingly greater use of x-ray dif-
fraction as an adjunct to the conventional methods of chemical analysis. This paper is the result of a part of that effort. EXPERIMENTAL
The Naphthol AS types used for this work are commercially available and have an indicated purity of 950/, or better. Each compound was recrystallized from xylene (ACS) and the melting point determined to obtain an indication of its purity. The compounds were identified by mixed melting point determinations using identical compounds obtained from widely different sources. The recrystallized compounds were prepared for x-ray work by grinding in an automatic agate mortar for 15 minutes. The powders were then packed
Table 1.
Nomenclature, Melting Point, and Index Lines of Azoic Coupling Components
Colour Index (1956) Azoic coupling ProtoMelting C.I. Point, com o nent%o. No. C. (Unc.) 2 37505 302 248.0- 8 . 5
Pat tern
Chemical Trade 1-0. Name Name 1 3-Hydroxy-Znsphthanilide Naphthol AS 2 3-Hydroxy-2-naphthoic-unaphthalide 3 3-Hydroxy-Znaphthoic,9-naphthalide 4 3-Hydroxy-2-naphtho-4’chloro-o-toluidide 5 3-Hydroxy-4’-chloro-2naphthanilide 6 3-Hydroxy-2-naphtho-panisidide 7 3-Hydroxyd’-chlor0-2’,4’dimethoxy-2nmhthanilide 8 3-Hidroxy-2-naphtho-ophenetidide 9 3-Hydroxy-3 ‘-nitro-2naphthanilide 10 3-Hydroxy-2-nap htho-otoluidide 11 3-Hydroxy-2 ’,5 ’-dimethoxy-2-naphthanilide 12 3-Hydroxy-2-naphtho-oanisidide 13 3-Hydroxy-2-naphtho-5 Ichloro-o-toluidide 14 3-Hydroxy-Znaphtho-ptoluidide 15 3-Hydroxy-2-naphtho-5 Ichloro-o-anisidide Table It.
d, -4. 1/11 1. 3-Hydroxy-2-
naphthanilide 14.6 100 7.27 9 6.70 3 6.33 25 5.96 6.06 5.60 5.08 4.83 4.65 4.23 4.06 3.73 3.56 3.16 3.03 2 . 7 4-. .
2.61 2.43 2.29 2.09 1.92
Y3Li
8B 25 70 20 4 15 75 50 5 3B 2B 3B 2B 3B 3B
2. 3-Hydroxy-2naphthoic-anaphthalide 15.76 40 6.G 75 6.32 35 5.47 35 5.13 9 4.99 7 4.74 7 4.45 30 4.19 7 3.86 6 3.52 100
d, A.
Naphthol AS-BO
4
37560
303
217.5-18.0
Naphthol AS-SW
7
37565
313
243.5- 4.5
Naphthol AS-TR
8
37525
314
243.5- 4.5
Naphthol AS-E
10
37510
308
262.0- 3 . 0
Naphthol AS-RL
11
37535
312
229.5-30.5
Naphthol AS-ITR
12
37550
310
196.0- 7.5
Naphthol AS-PH
14
37558
557
156.5- 8.5
Naphthol AS-BS
17
37515
305
248.0- 9 . 0
Naphthol AS-D
18
37520
306
193.5- 4.0
Naphthol AS-BG
19
37545
385
185.5- 6 . 0
Naphthol AS-OL
20
37530
311
163.0- 4.5
Naphthol AS-KB
21
37526
604
243.5- 4 . 5
Naphthol AS-RT
31
37521
695
222.5- 3 . 0
Naphthol NEL
34 &/or 41
37531
559
212.5-13.0
1.81
1.76 1.71
1/11 3-Hydroxy-2naphthoic-pnaphthalide 2.96 4B 2.88 3 2.79 6B 5 2.66 2.58 2B 2.31 4B 2.24 6 2.04 2B 1.96 5B 1.89 3
d, A. 1/11 4. 3-Hydroxy-2naphtho-4’-chloroo-toluidide 2.69 4 2.52 2 2.49 2 2.44 2 2 2.35 2B 2.27 2.05 1B 2.00 3B 1.83 2 1.69 2
4 . 3-Hydroxy-2naphtho-4’-chloroo-toluidide 14.75 100 7.37 7 6.89 5 6.22 13 5.68 3 5.51 2 4.98 12 4.89 30 4.69 30 4.07 5 3.99 20 3.93 25 3.80 30 3.66 15 3.56 15 3.43 15B
5. 3-Hydroxy-4’chloro-2naphthanilide 16.35 95 9.82 4 8.75 2B 8.18 3B 6.32 40 5.75 40 5.35 12 4.90 12 4.70 60 4.57 60 4.46 9 4.14 25 3.99 11 3.95 10 3.62 30 3.55 55 3.48 100 3.30 3
d, A.
1/11
7B 6 4
2B 1B 5 7 3 1B 1B 1B 4
3. 3-Hydroxy-2naphthoic-dn aphthalid e 16.25 100 13.2 12.5 9.52 10 6.64 30 5.89 75 5.52 20 4.86 30 4.74 15 4.07 11 3.76 50 3.64 65 3.48 25 3.36 20
3
3.29 3.21 3.11
3.84 (25) 4.67 (25) 3.40 (90) 10.35 (85) 15.65 (70) 3.65
6.21 (7) 3.29 (20) 4.82 (80)
3.50 (85) 6.51 (55) 6.19 (65) (80) 3.39 6.58 (65) (60) 3.45 4.28 (85) (35)
Interplanar Spacings and Line Intensities of Azoic Coupling Components
2. 3-Hydroxy-2naphthoic-anaphthalide 3.31 85 3.13 11 3.05 2.96 2.56 2 49 2.40 2.28 2.18 2.09 1.89
1st
Interplanar Spacings d in A. and 1/11 2nd 3rd 4th Longest 3.56 4.65 (75) (70) 3.31 6.91 (85) (75) 5.89 3.64 (70) (75) 4.69 4.89 (30) (30) 16.35 3.12 (60) (95) 3.55 4.62 (35) (45) 7.74 3.37 (35) (80)
25 35 20
3.
3.34 3.24 3.17 3.13 2.86 2.76
20 7B 2 2 2 2B
3.21 3.12 3.05 2.85
10 65 12 8
d, A. 1/11 7 . 3-Hydroxy-5’chloro-2 ’,4Idimethoxy-2naphthanilide 10.85 30 9.75 8 7.74 80 7.04 10 6.79 7 6.42 30 6.00 13 8 5.68 5.33 30 5.21 7 5 02 5 4 93 6 4 81 71 4.70 81 4.53 5 6. 3-Hydroxy-24.32 8 naphtho-p4.09 9 anisidide 3.95 20 15.8 100 3.86 11 15.55 4 3 69 30 100 10 3.49 7.89 25 3.37 35 5.27 15 30 3.29 4.77 3.10 10 35 4.62 3.06 6 4.04 5B 3.00 8B 3.55 45 2.70 3 3.14 14 2.63 4B 3.09 20 2.56 4 2.96 5B 2.47 4B 2.90 4 2.42 5 2.38 3B 2.32 3B 2.23 4B 2.25 3 2.07 5B 2.17 4B 1.96 1B 2.13 5 1.92 1B 2.01 2B 2B 1.93 3 1.71 (Continued on page 1644) d, A.
5.
1/11
3-Hydroxy-4’chloro-2naphthanilide 2.78 4 2.70 3 2.64 5 2.38 3 2.32 3 2.27 6 2.23 10 2.09 7 2.05 2 2.01 5 1.90 5 1 86 3B 1 80 2B 1.66 3B
VOL. 3 1 , NO. 9, SEPTEMBER 1959
1543
Table II. d, A.
1/11 8. 3-Hydroxy-2naphtho-ophenetidide 10.35 2 9.40 100 7.62 ‘4 7.10 6 6.51 2 6.21 7 5.37 1B 4.95 5 4.67 3 4.48 3 4.35 7 4.15 6 4.06 3.84 3.56 3.44 3.28 3.09 2.95 2.81 2.69 2.34 2.26 2.19
6 25 6 2 6 4 1 1B 1 1
1B 1
9. 3-Hydroxy-3’n itro-2napht hanilide 14.1 100 7.56 1 7.02 5 6.55 2c 5.75 5.20 2 7 4.93 4.67 25 4.53 4 4.19 3 4.00 10 3.74 4 3.69 3.50 3.36 0
4 2 6
lnterplanar Spacings and Line Intensities of Azoic Coupling Components (Continued) 1/11 d, A. 1/11 d, A. 1/11 d, A. 1/11 d, A. 1/11 3-Hydroxy-3’11. 3-Hydroxy12. 3-Hydroxy-213. 3-Hydroxy-% 14. 3-Hydroxy-2-
d, A.
9.
nitro-2naphthanilide 3.29 20 3.17 7 3.06 2 2.88 2 2.64 1B 2.35 1 2.19 2 2.03 1B 2.00 2 10.
3-Hydroxy-2naphtho-otoluidide
5.26 5.10 4.82 4.35 4.14 3.92 3.86
15 7B 80 13
3.62 3.40 3.23 3.02 2.88 2.70 2.66 ~. 2.63 2.51 2.27 2.05
35 ..
~
1544
a
ANALYTICAL CHEMISTRY
2.75 2.68
6 5
2.18 2.07 2.06 2.01 1.91 1.85 1.76 1.71
8
11
70 35
90 7B 4 6 3B 3
3 3B 4B 3B
11. 3-Hydroxy2‘,5’-dimethoxy-2naphthanilide 10.35 85= 9.40 65 7.41 45 7.04 6
Probably more than one line.
2 ’,5’-dimethoxy2-naphthanilide 6.06 4 5.88 9 5.77 9 5.13 5.05 100 4.53 35 4.25 15 4.17 8 3.95 20 3.84 20 3.67 40 ~. 3.61 30 3.50 85 3.43 35 3.28 85 3.12 20
7 5 7 4B 5 2B 2B
12. 3-Hydroxy2-naphtho-oanisidide 15.65 70
naphtho-oanisidide 5.68 10 5.24 2 4.97 20 4.75 15 4.67 4 4.19 8 4.07 2 3.90 20 3.67 3.65 3.40 100 3.32 20B 3.24 3.12
2.20 2.13 2.07 2.05 1.97 1.94 1.75
9 6
2B 1B 4 2 3 2 3
naphtho-5 ’-chloroo-toluidide 3.11 12 3.03 25 2.90 3 2.79 15 2.65 4 2.59 4 2.48 4B 2.41 6B 2.35 3 2.30 4 2’20 2.08 2.03 5B 1.80 2B
‘iB
14. 3-Hydroxy-2naphtho-ptoluidide 15.75 20 10.95 100 10.52 6 7.84 2 7.27 2 6.58 60 6.24 14 5.53 25 5.20 5 4.98 55 4.79 35 4.65 9 4.29 8 4.14 30 3.93 6 3.69 45 25 3.53 3.39 65 3.34 14 ~~
13. 3-Hydroxy-2naphtho-5 ’-chloroo-toluidide 12.55 40 8.82 15 7.25 3 . ~. 6.19 65 5.55 60 15 4.75 4.38 40 4.20 25 3.97 100 3.80 25B 3.65 80 3.46 40 3.34 25 3.25 65
naphtho-ptoluidide 2.48 2.46 2 2.39 2.31 2B 2.27 2 2.20 3B 2.15 4 4B 2.07 2 1.91
15. 3-Hydroxy-2naphtho-5’-chloroo-anisidide 10.95 20 7.82 10 6.92 4 5.98 25 5.57 20 5.47 20 4.90 25 4.28 35 4.17 10B 4.03 7 3.86 100 3.74 15 6 3.63 8 3.56 3.45 85 3.24 3 3.15 8 3.08 20 3.04 9 2.91 9 2.78 4 2.73 8 12 2.64 2.59 4B 2.51 3 2.38 3 2 3.5 2 2.28 4 2.22 3 2.18 4 2.13 3 2.06 3B 2.02 0 1.79 3 i.77 4B 1.74 3 ~
3.29 3.24 3.11 3.04 2.97 2.77 2.72 2 64
2.59
15
10 4B 7 4 5 2 1
4B
in sample holders as described by iMcCreery (6) and exposed to x-radiation. The instrument used was a ru'orelco X-Ray Diffractometer (Philips Electronics, Inc.), equipped with a GeigerMuller counter and a scaler-rate meter
with an automatic strip-chart recorder. The patterns were made using nickel filtered unresolved copper K a with X (mean) = 1.5418 A. and covered a range between 2'28 and 90'28. The divergence slit used was l o ,while the
receiving slit was 0.003 or 0.006 inch. The x-ray tube and the scaler-rate meter were operated a t different settings to obtain good resolution and suitable intensity measurements. The d-spacings were calculated from VOL. 31, NO. 9, SEPTEMBER 1959
1545
the line position in degrees 28 ( 7 ) ,while the reported intensities (1/11)were obtained from the charts as peak heights above background level with the most intense line given a value of 100.
1546
ANALYTICAL CHEMISTRY
RESULTS
The azoic c o u P b 4 components COVered by this report and melting points of the recrystallized compounds are
listed in Table I, which also gives the interplanar spacings and intensities (in parentheses) corresponding to the four strongest lines and the largest spacing found in the difiractometer patterns.
Table I1 lists all the interplanar spacings with relative intensities of the compounds. The x-ray powder difiractometer tracings obtained under a given set of ex-
perimental conditions are reproduced under Figures 1 t o 15 and cover the range 2 O 2 e to 55'28; no useful data were found above this range. The inserts with the charts give the molecular and
structural formulas of the compounds and the aolventa from which the compounds were recrystallized to obtain the x-ray patterns and melting points listed in Table I. Here are also given VOL 31, NO. 9, SEPTEMBER 1959
1547
the instrumental conditions used in obtaining the patterns; these include the x-radiation and filter, the kilovoltage and current, the scaler-rate meter settings (scale factor-multiplier-time
1548
ANALYTICAL CHEMISTRY
constant), and the divergence and receiving slits. The diffractometer recordings have been included because the authors agree with Parrish (2) that a table of d-spac-
ings with corresponding intensities and such qualifying terms as broad, diffuse, doublet, etc., are not sufficient to describe the actual profile of an x-ray pattern of a compound.
DISCUSSION
The x-ray data presented identify 15 of the azoic coupling components of commercially available Naphthol AS types. This method of analysis is now a valuable procedure a t this laboratory because it is simple and leads to positive identifications. More important, x-ray analysis is of value because the commercial Naphthol AS types-which are usually impure products or mixtures of two compounds-can be analyzed directly without preliminary preparations. Polymorphism and preferred orientation, a t times, present a problem. The former leads to entirely different x-ray patterns for the same compound; and care must be taken in comparing data with those obtained from similar compounds crystallized from solvents other than those specified in this paper. The
effect of preferred orientation is to give distorted intensity measurements. This, however, may be circumvented by a more careful and detailed study of the four major index lines. X-ray diffraction lends itself perfectly t o the identification of the active components of Naphthol AS types. The technique is simple and offers unequivocal results. ACKNOWLEDGMENT
The authors acknowledge the cooperation and valuable suggestions of Edward F. Kenney, Chief Chemist, U. S. Customs Laboratory, New York, N. Y.
(2) Brindley, G. W., Norelco Reptr. 4, 71
(1957).
(3) Cady, W. H., “Tech. Manual and
Yearbook,” Am. Assoc. Textile Chemists and Colorists Vol. 34, pp. 284-6, 1958. ( 4 ) Colour Index, 2nd ed., Vol. 2, pp. 2613-28, 1956. (5) Lubs, H. A., “Chemistry of Synthetic Dyes and Pigments,” p. 184, Reinhold, New York, 1955. (6) McCreery, G. L., J . Am. Ceram. Soc. 32, 141 (1949). (7) Natl. Bur. Standards, Applied Mathematics Series 10, Tables for Conversion of X-Ray Diffraction Angles to Interplanar Spacings, U. s. Government Printing Office, Washington, D. C., 1950. (8) U. S. Import Duties (1958), Miscellaneous Series, TC 1.10: Im 7/4/1958, U. S. Government Printing Office, Washington, D. C., 1958.
LITERATURE CITED
(1) A m . Dyestuff Reptr. 46, 610 (1957).
RECEIVED for review December 15, 1958. Accepted May 6, 1959.
VOL. 31, NO. 9, SEPTEMBER 1959
1549
