[CONTRIBUTION No. 132 FROM
THE
JACKSON LABORATORY, E. I. DU POXTDE NEMOURS BVD COMP‘WYI
“KAPHTHANIL” COUPLING COMPONENTS : RELATIONSHIP BETWEEK CHEMICAL STRUCTURE AND CELLULOSE SUBSTANTIVITY LOUIS SPIEGLER Received M a r c h 9, 1965 INTRODUCTION
This paper deals with studies on the relationship between cotton substantivity and the aryl amides of 3-hydroxy-2-naphthoic acid and other aromatic o-hydroxycarboxylic acids which are known in the trade as “Naphtol”, “Naphthol”, “Brenthol”, or “Naphthanil” coupling components. Insoluble azo dyes are generated from these components in the fibers by impregnating or adsorbing a caustic soda solution of these almost colorless phenolic compounds on cotton, followed by treatment with diazo compounds. In most applications, the affinity of the sodium salts of the aryl-amides for the cellulose fiber is a significant and controlling property. To meet requirements for various uses in the trade, arylamide products varying from low to high substantivities have been developed. For dyeing purposes, particularly in machine dyeing, and where a high fastness to rubbing is required in the final color, a highly substantive arylamide is needed; and for printing purposes, where the component is padded, a low substantivity is preferred so that soaping will readily remove the undeveloped component and leave B clear, white pattern (1-3). All of the mylamides in commercial use display some degree of affinity for cotton; but there are wide variations in the substantivity ( % exhaustion from dye bath solution) which range from 10 to about 75%. These variations in affinity appear to be dependent, to some extent, on the chemical constitution of the arylamide. The structural features of the arylamides and their influence on cotton substantivity have, therefore, been subject to considerable investigation. It is obvious that the more clearly the relation between constitution and substantivity is understood, the more easily can products be prepared possessing certain and definite properties. The substantivity of many arylamides has been determined by gravimetric methods either directly by nitrogen analysis of the impregnated cotton, or indirectly by acid precipitation of the residual arylamide left in the bath after exposure to the cotton fiber (1,4-9). More recently methods have been described for colorimetric determination, by either ultraviolet light on the residual arylamide left in the bath, or visual light on water-soluble colors formed by coupling with diazo components (10-12). The subject arylamides have been classed generically with direct cotton dyes which are positively absorbed by cellulose, even though they do not generally possess that elongated structure which characterizes most of the known direct cotton dyes.1 Certain of the arylamides possess considerable substantivity and 1 Types of molecule substantive t o cellulose which are derived from benzidine, disnisidine, p , p’-diaminostilbene, lI4-diaminonaphthalene, etc. 1292
1293
NAPHTHAh-IL C O U P L I N G COMPONENTS
their absorption on cotton follows a course similar to a quickly diffusing dye (13, 14). In the arylamides of the o-hydroxycarboxylic acid series, as with most of the direct cotton dyes, (a) The presence of the acid amide group, -CONHenhances substantivity (15-18). Further, it is known that beta-naphthol is considerably less substantive than the anilide of 3-hydroxy-2-naphthoic acid (4,19), and that methylation of the -CONHgroup to -CO-Nin the latter diminishes or destroys sub-
I
CH3 stantivity (3, 16) ; (b) Substantivity is affected or modified by the introduction of substituent groups into the arylamine radical (3) and generally speaking, (if the same acid is considered), the substantivity increases with the molecular weight (20). For example, anthracene derivatives are more substantive than analogous naphthalene products (1). Increased cotton affinity is obtained from the introduction of known substantivity-conferring groups which are generally associated with the direct cotton dyes, namely: 1. The further extended conjugations (“bridges”) (3) such as,
CHI 0
OCHa
-HNO--C>~H- H N e C O - - C > . SUBSTAFTIVITY-CONFERRIXG G R O W S
Elect ron-donating
Hvdronen-donatinz
-0
I
H -N=N--
H-O-
. -”*
. .
-N-c-
1
.
H
-N-C-N-
I OI!
-KHR
H
Ar-NH
I
H -S-
I1
O
I
H
1294
L. SPIEGLER
2. Groups which carry lone pairs of electrons, capable of acting as eIectron donors, and those which carry hydrogen atoms capable of co-ordinating, i.e. accepting, electrons from an external source (forming a hydrogen bond with another group) as shown on page 1293 (21). However, not only the nature of the group, but the position of the substituent appears to display an important influence on substantivity (3, 22), and small changes in substituents may alter entirely the substantivity relations (19,23-25). a 0
0.a
b
1 ,
9$
0.6
,el 0
5 -2 0.3 !bJ 0
icL
w
e
-at
2
0.2
Q ,
0.D
22 -f
0.0 0.0
$:
4
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
A R Y L A M ~ D EINIITIhLLY PRESENT iR1 S ~ L U T I B N (SMILITER)
FIG.1. EFFECT OF 30% ETHYL ALCOHQLON SUBSTANTIVIT~. Absorption of “Kaphthol”
AS-DB,
on cotton at 25-30’ in (I)HzO, NaQH; and (11) HzQ, C2H,QH, NaOH. a
Substantivity calculated as % exhaustion
[:(loo)]*
where y = arylamide removed and absorbed by cotton
from solution (g./liter) and x = arylamide initially present in solution @./liter).
HYDROGEN BOND THEORY
(21, 26)
The above mentioned hydrogen bond linkage of cellulose with hydroxyl groups with direct dyes containing substantive amide groups has been visualized (27) as: iCellulose
.. .. ..
H-0
O -C-N-
H
1295
N A P H T H A S I L COUPLIXG CONPONESTG
1.6
1.5 1.4
-
I
1
I
I
I
I
I
I
I
I
-
1.2 0.90.7 1.3
1.1
1.0
0.0
Q6
-
0.4 0.5
0.2-
0.3
0.I
-
A 30% C2H50H I
I
1.0
2.0
I
I
3.0
ARYLAMIDE INITIALLY
I
I
4.0 5.0 6.0 PRESENT IN SOLUTION
FIG.2 . EFFECT O F 307, ETHYL ALCOHOLO S AS-LB.
ZO 8.0 (GM./LITER)
SrBSTA4STITITY. $bsorption Of
“Saphtol”
H on c o t t o n a t 25-30” in (I) HZO, NaOH; and (11)HzO, CaHcOH, NaOH
For the subject arylamides, hydrogen bonding of the possible amide forms u-ith the hydroxyl groups of cellulose as follows, has been suggested (28). Rj-.C--l\‘-.
/I
I
R2
.. .. . .
O
-2
R1-C-
S-RZ
H
H-0-Cellulose
0
I
H
H
1
* * 0-Cellulose
This coiiception of cotton substantivity, which postulates that coordinated hydrogen furnishes the link between cellulose and direct cotton dyea, is in good agreement with experimental facts, as follows : 1. The hydroxyl groups of the cellulose appear to be involved in the bonding since esterification of the cellulose inhibits its capacity for absorbing direct dyes ;
1296
L. SPIEGLER
axoH co - o c o - g
OH C0NH-O- CO
FIGURE 3 S C A L E MODELS OF ISOMERIC ARYLAMIDES SHOWING LINEAR AND ANGULAR CONFIGURATIONS 2 . In a selected direct dye (29), the heat of dyeing (energy release) for each substantive group fixed has been shom-n to be about 7 kilocalories, 1s-hich is the order of energy to be expected for hydrogen bond formation (30).
NAPHTHANIL COUPLING COXPONENTS
1297
3. Scale models of subst,antive dyes have been found to fit well alongside of models of the cellulose chain. The substantive dye models display long chainlike structures, while nonsubstantive dyes have shorter, and less linear structures. Deviations from linear configuration in a dye molecule decrease its substantivity for cellulose. See planar diagram, p. 1298.
ARYLAMIDE INI‘BIALLY P ESENT IN SOLUBlON ( GWW./LlTEWb FIG.4.EFFECTS OF LINEAR AND AXGULAR COXFIGURATIONS ON SUBSTANTIVITY. Absorption of (I) “Naphthol” AS-BO, and (11) “Naphthol” AS-SW on cotton a t 28-30’ (4).
% ’ Exhaustion: (I), 21-26; (II),41-50. 4. It has been further observed that more stable fixations occur when the dye molecule not only forms, like cellulose, a straight linear chain, but when the aromatic nuclei are capable of assuming a coplanar arrangement, and when two or more substantive groups (or substa?tivating links) of the dye are situated alternately a t a distance of 10.3 to 10.8A units or multiples thereof, corresponding to the periodicity of the cellobiose units which make up the cellulose chain.
1298
L. S P I E G L E R
Our studies, described below, further exemplify the above relationship between substantivity and spacial arrangement, and extend the evidence advanced for cotton substantivity of azo colors to colorless “Kaphthanil” coupling components. Planar Section of Cellulose Chain CH2 OH
OH OH
I
I
\
/o-cH\
/CH-o-CH
\
/CH-o-CH
1
OH OH .
I
/o-cH\
CH-CH
I
CHzOH
1
\
0-CH
/CH-o-CH
I
CHIOH
!
\
C H-0 -C H
/
CH-CH
I
/
\
I
OH OH .
i
EXPERIMENTAL PREPARATIOS O F ARYLAMIDES
The arylamides, further discussed below, which were not commercially available and whose cotton substantivity had not been adequately recorded in the literature, were prepared by the generally known procedure of condensing amines, or their hydrochlorides with 3-hydroxy-2-naphthoic acid in inert solvents with dehydrating agents such as phosphorus trichloride, or phosphorus oxychloride (31). The N-(3-hydroxy-2-naphthoyl)-N’-benzoyl m-phenylenediamine [Figs. 3 (Bottom, right), 61 was obtained by catalytic hydrogenationof N-(3-hydroxy-2-naphthoyl)-nz-nitroaniline (Kaphthanil BS) t o N-(3-hydroxy-2-naphthoyl) -m-phenylenediamine followed by condensation of the latter with benzoyl chloride. The condensation products obtained were purified and freed from unreacted initial components by (a) solution in alcoholic caustic soda and reprecipitation with mineral acids, (b) extraction with mild alkalis such as sodium bicarbonate, and/or (c) recrystallization from organic solvents (32). The 2- (3- and 4-) aminobenzoylthiophenes used for the preparation of the arylamides shown in Figs. 3 (Center), 5 were obtained by condensation of the corresponding nitrobenzoyl chlorides Kith thiophene in carbon disulfide (33, 34), and subsequent reduction of t h e 2- (3- and 4-) nitrobenzoylthiophenes in alcoholic solution t o amines with iron and acetic acid. N-Benzoyl-p-phenylenediamine,and P’;-p-anisoyl-p- and m-phenylenediamine for the arylamides shown in Figures 3 , 6 , and 7 were obtained in a similar manner, by reduction of condensation products from m- and p-nitroanilines with benzoyl and anisoyl chlorides (35-37). Similarly N-monothenoyl-p-phenylenediamine for the arylamide shown in Fig. 19 was produced from thiophene-2-carbonyl chloride and p-nitroaniline (38) The 4-arninobenzophenone employed for the arylamide in Fig. 17 was purchased from Dow Chemical Co. I
1299
N A P H T H S N I L C O U P L I N G COMPOKENTS
Mesidine (39) (2,4,6-trimethylaniline), used for the preparation of the arylamide shown in Fig. 15, was obtained b y catalytic hydrogenation with nickel in methanol from nitromesitylene which was purchased from the Eastman Kodak Co.
FIG.5 . EFFECTS O F LINEaR AND AXGULAR CONFIGURATIONS O N SUBSTAXTIVITY.Absorption of (I) N-(3-hydroxy-2-naphthoyl)-2-(4-aminobenzoyl)thiopheneand (11) X- (3hydroxy-2-naphthoyl) -2-(3-aminobenzoyl)thiopheneon cotton at 25-30". 70Exhaustion
I
I1
29-35
L@-"()mU 0
14-16
Purified pseudocumidine (40) (2,4,5-trimethylaniline) was separated from crude material purchased from the National Aniline Co. by fractional distillation and subsequent crystallization of distilled fractions.
1300
L. SPIECTLER
Yb FIG.6. EFFECTS OF LINDAR AND ANQULAR COGFIGURATIONS o s SUBSTANTIYITY. Absorption of (I) N-(3-hydroxy-2-naphthoyl)-Pi'-benzoyl-p-phenylenediamine and (11) N-(3hydroxy-2-naphthoyl) -N'-benzoyl-m-phenylenediamine on cotton at 25-30". % Exhaustion
21-34
2,6-Dimethoxyaniline (41) was prepared from 2-aminoresoroinol (purchased from the Eastman Kodak Go.) by methylation with dimethyl sulfate in acetic anhydride and subsequent deacetylation of the dimethoxyacetanilide.
NAPHTHSXIL COCPLING COMPONENTS
1301
0-
2
bfl
rn -1
P
1.2
0
m
1.1
Q:
w
-I-
1.0
+ 5 0.9
-
0.8
5
O.?
0 ;P
Q
J Q 0.6 w
0.5 LL
0.4
0
aJ
> 0.3 0
3 0.2 ig:
g
-
0.I
5J 0 >. (L
I.O 2 .o 3.0 4.0 5.0 7.0 ARYLAMIDE IMlTlALLY PRESENT IN SOLUTION 4 OM./ LITER)
4
FIG.7 . EFFXCTS O F LINEAR AKD ANGULAR CONFIUURATIONS ox SUBSTANTIVITY. Absorption of (I) S-(3-hydroxy-Z-naphthoyl)-nT'-p-anisoyl-p-phenylenediamine and (11) Tu'(3-hydroxy-2-naphthoyl)-~"-p-anisoyl-nt-phenylenediamine on cotton at 25-30'. % Exhaustion
43-64
I1
14-24
1302
L. SPIEGLER
IA I .3
1.2
z 0 g
1.1
3-
G '*O z 0.9
"5 0.8
a
U O
> w 0.7 0-
I-
=:
OL
0.6
w 30.5
5
5J -5 0.4
: 0.3 4
0.2 0.1
0 1.0 2 .o 5.0 6.0 A R Y L A M IDE INITIALLY FRESENT IN SOLUklBN(@MILITER) FIG.8. EFFBCTS OF LINEARAND AXGULAR CONFIGURATIOSG ON SUBSTANTIVITY. Absorption of (I) Di-(3-hydroxy-2-naphthoyl)-p-phenylenediamineand (PI) Di-(3-hydroxy-2naphthoy1)-m-toluylenediamineon cotton at 26-30" (4). %
Exhaustion -.__
I
45-47
""""3 HO
I1
23-26
NAPHTHAKIL COUPLING COMPONESTS
1305
SCBSTASTIVITY VALUES
In Figures 4, 8, 10, 13, and 18 are plotted absorption values of a number of arylamides on cotton at 25-30", where the yarn-to-liquor ratio \vas 1:20, which have been reported by Scheel (4). Other arylamide values shorn-n ~vherethe ratio of yarn-to-liquor v a s 1:30, were obtained by a modification of the gravimetric method described by Bhat. et al. (1) and
FGURE 9
SCALE MODELS SHOWlNG SLIGHTLY ANNULAR CONFIGURATION FROM
- NH-GO-NH-
BRIDGE, AND MORE LINEAR
CONFIGURATION F R O M
Rloualim (42). No ethyl aIcohol. however, v a s used t o increase the solubility of the arylaniide, eince as observed by Bhat, and further illustrated in Figures 1 and 2, the presence of alcohol in the alkaline arylamide solution decreases the cotton affinity of the arylamide considerably. The arylamide (2 g.j under examination as pasted wtih 30 ml. of distilled water containing 1.6 g . of caustic soda, then diluted with 170 ml. of i\-ater and warmed t o 50" toeffect solution. After cooling t o 25-30". the mixture was clarified by filtration through a Filter-
1304
>o
-5%
v
-
L. SPIEGLER
1.5-
-
1.4
1.3 -
I-
-.I \
1 0
u
-
1.2 1.1
2
,o
1.0-
20
0.9-
I-
v,
I 0.8
-
O
0.7-
D
.
w 0.6
>
0 2
0.5-
W
w
-c9
0.4-
c
0.3L
I
I
I
I
I
4D 5.0 3.0 2 .o A R Y L A M I D E INITIALLY PRESENT IN S O l - U l l ~ ( G M J L l T E R ) I .o
FIG.10 Cel mat, and the clear filtrate was diluted to 200-ml. volume XT-ith mater. From this solution, other solutions of approximately 0.1, 0.25, 0.50, 0.7'5, and lYc concentrations were prepared by pipetting 4.5,11.25, 22.5, 33.75, and 45 ml. of the filtrate folloxved by dilution of these
1305
NAPHTRASIL COUPLIKG COMPONENTS
portions with water t o 45 ml. total volume. Cotton yarn skeins,? each weighing 1.500 g. were then impregnated a t the various concentrations for 30 minutes, while stirring a t 5minute intervals to assure complete saturation. The skeins were then removed, Ivhile squeezing excess liquor from them a i t h a glass rod. Then 25-ml. samples of the residual solution mere diluted t o 175 ml. Tvith water, and the residual arylamide assayed by precipitation with excess concentrated h) drochloric acid. The precipitated arylamide n-as collected on a tared Gooch crucible, aashed Tyith x a t e r . and dried a t 100" t o constant n-eight. The initial concentration of the arylamide solutions before treatment v i t h the cotton skeins was also determined by precipitation with acid. The arylamide absorbed (expressed in g./liter) was then calculated by difference. USE O F SCSLE MODELS
Scale models of the arylamides were constructed from Fisher-Taylor-Hirschfelder Atom Rlodels. Based on electron diffraction studies, the linear scale of one cni. in the model is
FIG.10. EFFECTS O F LIYE4R A \ D - 4 X G U L A R C O X F I G U R A 4 T I O S SAND N O T - C O P L A T A R EFFECT A -CH2BRIDGEO N S~BSTASTIVITY. Absorption of di-(3-hydroxy-2-naphthoyl) derivatives of (I) 4,4'-diaminodiphenylmethane,(11) 4,4'-diaminostilbene, (111) 4,4'diaminodiphenyl urea, (IV) 4,4'-diaminoazobenzene, and (V) benzidine on cotton a t OF
25-30" (4).
yo Exhaustion
I
I1
24
-H.U/j
NH--
80
!\/CH=CH I11
IV
--HK
YH-
55
66
70
Bleached cotton yarn, boiled in Turkey Red Oil (5 g./liter), washed thoroughly with water, and dried a t 105'.
( T O P VIEW)
FIGURE I I SCALE MODEL OF DI[2: 3 HYDROXYNAPHTHOYL]
4 4' DIAMINO DIPHENYL METHANE SHOWING ANGULAR CONFIGURATION AND NON-COPLANAR EFFECT OF - C H a -
BRIDGE
FIGURE 12
SCALE MODELS OF DI (213 HYDROXYNAPHTHOYL) DERIVATIVES OF (LEFT) ORTHODICHLOROBENZIDINE
, AND (RIGHT) m-DICHLOROBENZIDINE 1306
FIG.13. COPLANaR
COSBIGURATIOSS :
EFFECTS OF
S U B S T I T U T I O N S WHICH
DISTORT c0-
Absorption of di- (3-hydroxy-2-naphthoyl) derivatives of (I) o-dichlorobenzidine, (11) m-dichlorobenaidine, (111)o-tolidine, and (IT)m-tolidine on cotton a t 25-30°(4). PLASSRITY.
[C 3 - ] * Oi
I
c1
% Exhaustion
82
-.Hc1>-DXH-
c1 c1
38
-.HCT>-c7>.,.C1 C H,
111
57
-
IV
29
1308
L. SPIEGLER
equal t o one Angstrom unit in the natural atom (43). I t was then easy to examine in detail the spacial characteristics of the subject compounds. i.e., linearity, planarity, distances betneen substantive groups. etc., and to determine how readily the models would fit alongside a model of the cellulose chain, and t o relate these configurations TTith observed substantivity values. Scale models of isonieric pairs of 3-hydroxy-2-naphtho~laniides of (a) alpha- and betanaphthylamines, (b) 2- (3- and 4) aminobenzoylthiophenes, and (c) S-benzoyl-m- and p-
i:,.
FIGURE 14
SCALE MODELS SHOWING EFFECT OF DI-ORTHO SUBSTITUTIONS TO -GO"-
GROUP UPON
COPLANAR CONFIGURATIONS phenylenediamines are illustrated In Figure 3. The marked difference in configuration betneeii isomers is readily apparent, i.e., the beta-naphthamide is more linear than the alpha isomer; the 4-aminobenzoylthiophene derivative niore linear than the 3-amino isomer; and the benzoyl-p-phenylenediaminederivative is linear, hile the benzoyl-m-phenylenediamine derivative is definitely angular in shape. Figures 4 to 8 inclusive, showing the absorption of isomeric pairs of the subject arylamides"on cotton, establish the relationship between a straight linear structure and cotton
1309
N A P H T H A N I L COUPLIKG COMPONENTS
substantivity. Arylamides with linear configurations are considerably more substantive than isomers which are angular.
ARYLAMIDE INITIALLY PRESENT IN SOLUTION (GWLITER)
FIG.1s. EFFECTS O F S L V B S T I T U T I O N DI-ortho T O -CON%GROUPO S S U B S T A N T I V I T Y . Absorption of 3-hydroxy-2-naphthoyI derivatives of (I) mesidine, (11) pseudocumidene, and (111) 2,B-dimethoxyaniline on cotton at 25-30”. -5% Exhaustion 0
I
I1
20-28
I11
0
CHI0 In Figure 9, scale models of di-(3-hydroxy-2-naphthoyl) derivatives of (a) 1,4’-diaminodiphenyl urea, (b) 4,4’-diaminostilbene, and (e) benzidine are illustrated. The slightly and the more linear conangular configuration from the urea bridge, -XH-CO-XH--,
a
figurations from the stilbene, -
-,
-CH=CH-
c>
-,
and the diphenyl,
bridges are readily apparent. In Figure 10, the cotton ab-
1310
L. SPIEGLER
sorption of these arylamides is shown. As might be expected (from their knoivn effects in azo dyes), the t x o latter more linear configurations (Plots I1 and V) display noticeably greater exhaustion characteristics than the more angular urea configuration (Plot 111). d model of di-(3-hgdroxy-2-naphthoyl~ -4,4'-diaminodiphenylmethane is shoyxn in Figure 11, Tvhich demonstrates the angular configuration, and the non-coplaner effect resulting bridge. I t is knoan in azo colors that deviation from the straight from a methane, -CHL-, linear structure of benzidine derivatives, as in colors derived from p-diaminodiphenylmethane, results in a reduction in cotton substantivity. This is again apparent in the arylamide series as is illustrated in Figure 10 (Plot I). The effects of various substitutions or modifications which distort coplanar configurations and affect substantivity are further illustrated a s follom: (Figures 12-li), 1. Figvre 19 shows models of di-(3-hydroxy-2-naphthoyl)derivatives of (a) o-dichlorobenzidine and (b) m-dichlorobenzidine. The tn o chloro groups, when present ortho t o the
FIGURE 16 SCALE MODELS FOR (LEFT) N-2 13 HYDROXY NAPHTHOYL-2(4 AMINO BENZOYL) THIOPHENE
-
AND (RIGHT) N 2 :3 HYDROXYNAPHTHOYL -4- AM INOBENZOPHENONE
diphenyl linkage distort the coplanar configuration of the molecule. Such substitutions, as demonstrated in Figure 13, result in products with reduced substantivity. c1 I
c1 2 . The effects of di-ortho substitutions t o the carbonamide, -CO-SH--, group are shonn in Figures 14 and 15. The 2,6-dimethyl- and 2,H-dimethoxy- anilides display no affinity for cotton (zero substantivity). The scale models shoir that these amide molecules are not flat, i.e., the configurations are not coplanar. Honever, a polymethyl substituted anilide in which one of the ortho positions is left open. as in the 2.4.5-trimethyl anilide, is found t o be substantive, and its scale model shows a coplanar configuration. 3 . Scale niodels and absorption values for (a) N-(3-hydroxy-2-naphthoyl) -2-(&aminobenzoyl)thiophene, and (b: ?;-(3-hydroxy-2-naphtho~-1)-4-aminobenzopheiioneare shoa-n in Figures 16 and 1;. The benzoylthiophene derivative is more substantive and the molecule is flatter than the benzophenone derivative. The absorption on cotton for a number of arg lamides which are predominately linear and
1311
NL4PHTHANIL COUPLING COMPONENTS
z 0
ARYL FIG.17. EFFECTS O F COPLAXAR ASD NON-COPLANAR CONFIGURATIONS ON SUBSTANTIVITY. Absorption of (I) N-(3-hydroxy-2-naphthoyl)-2-(4-aminobenzoyl)thiopheneand (11) P\'-(3-hydroxy-2-naphthoyl)-4-aminobenzophenone on cotton at 25-30'. % Exhaustion
34
I
C O O "
c o N ~ c o ~ I1
17
coplanar in configuration, and which contain a plurality of substantivity-conferring groups are shown in Figures 18 t o 20. For the pairs of substantive links examined:
-CONHand -CONHand -KHand maximum cotton fixation is observed when
-COXH-
Fig.18;
\S/
Fig. 19;
-CONH-
Fig.20;
these groups are situated lOA units apart.
FIG..18. EFFECTS OF INTERATOMIC DISTANCES BETWEEN PAIRSOF SUBSTANTIYE GROUPS. Absorption of di-(3-hydroxy-2-naphthogl)derivatives of (I) p-phenylenediamine, (11) 1,5-naphthalenediarnine,(111) 2,6-naphthalenediamine,and (IV) 1,6-naphthalenediarnine on cotton at 25-30’ (4).
[c():-],
FROU SCALE MODELS
Of
% Exhaustion
I
Interatomic distances between -CONH- and CONH-
1
tic--+I
45
7.5
60
10.0
56
11 .o
68
10.0
-”
NH-
I1
03
-HN
I11 -HN IV
-HN 1312
1313
NAPHTHANIL COCPLING COMPONENTS
FIQ.19. EFFECTSOF INTBRATOMIC DISTANCES BETWEEN PAIRS OF SUBSTANTIVE GROUPS. -IS'-monothenoyl-p-phenylenediamine and Absorption of (I) N- (3-hydroxy-2-naphthoyl) (11) h--(3-hydroxy-2-naphthoyl) -2-(4-aniinobenzoyl)thiopheneon cotton at 25-30". Interatomic distance between
-CONH-
and
-
IJ S
%Exhaustion
I1
A
4
O
H
I
-+I
65
10.3
34
7.0
1314
L. SPIEGLER
m 2 c
3
DALLY PRESENT
IN SBLU?
FIG.20. EFFECTSOF INT~RATOMIC DISTANCES BETWEEN PAIRS OF SUBSTANTIVE GROUPS. Absorption of (I) ‘ T a p h t o l ” AS-LB and (11)‘Waphthol” AS-SG (Brenthol GB) on cotton a t 25-30”, Intcratomic distance between
%Exhaustion
Q
Interatomic distances
(A)
‘N’and H [
-1
-03“+-
k.
22-28
7.3
62-70
10.0’
N A P H T H A N I L COUPLING C O V P O N E N T S
1315
Acknowledgements. The author expresses appreciation to D. E. Kvalnes for his invaluable suggestions and contributions, and thanks to C. E. Sparks, L. E. Schniepp, J. H. Trepagnier, M. E. Friedrich, C. W. Croco, and V. Weinmayr, members of the Jackson Laboratory Research Staff, for their assistance in the synthesis of some of the arylamides used in this investigation. SUMMARY
Measurements from scale models of “Kaphthanil” Coupling Components, and their substantivity values exemplify relationships between substantivity and spacial arrangement as follows : (a) Products with linear configuration are more substantive than angular types. (b) Products which are flat, or coplanar have better affinity for cotton than analogous or isomeric products which are non-coplanar. (c) Substitutions or modifications which disrupt or disturb the coplanar configuration of the parent nucleus result in a reduction of substantivity. (d) Maximum h a t i o n to cotton occurs in compounds n-hich are predominately linear and coplanar in configuration, and which contain a plurality of substantive groups, which are situated lOA units, or multiples thereof, apart corresponding to the periodicity of the cellulose units which make up the cellulose chain. These relationships are similar to those observed for direct cotton dyes and are in agreement with the conception that coordinated hydrogen furnishes the link between cellulose and the direct dye or the coupling component. WILMINGTON 99, DELAWARE REFERENCES BHAT,FORSTER, AND VENHATARAMAN, J . SOC.Dyers Colourists, 66, 166 (1940). HASSMAN, Testil-Rundschau., 3, 433 (1948); Dyer, 101, 206 [1949). ADAMS,J. SOC.Dyers Colourists, 67, 223 (1951). SCHEEL, Inaugural Dissertation, University of Frankfurt (1927). RATH, J . SOC.Dyers Colourists, 44, 10 (1928). CHRIST,Melliand Textilber., 11, 447 (1930). JDZJGYICH AND KIMOVEC, Melliand Tertilber., 15, 171 (1934). (8) MEHTAAND T H O S ~ RJ ,. Soc. Dyers Colourists, 66, 160 (1940). Ber., 73, 701 (1940). (9) R.4m AND BURKHARDT, (10) CROPPER AND GILES, J . SOC.Dyers Colourists, 60, 279 (1944). (11) GILES, J . SOC. Dyers Colourists, 60, 280 (1944). Dyers Colourists, 61, 47 (1943). (12) GILES, J. SOC. AXD MORTON, J . SOC. Dyers Colourists, 66, 146 (1940). (13) BOULTON (14) MEYER,Monatsh., 22, 791 (1901). (15) MEYERAND MARK,Der A u f b a u der Hochpolumeren Organischen Naturstoffe, Leipzig, 1930, p. 127; MEYER,Natural and Synthetic H i g h Polymers, 2nd Ed., N. Y., Interscience, 1950, p. 332. (16) KRZIKALLA AND EISERT,J . prakt. Chem., [X.F.]143, 50 (1938). (17) VOROSWCOV LYD BABISCHEV, J. A p p l . Chem. (U.S.S.R.), 11, 1486 (1938) [Chem. Abstr., 33, 5841 (1939)l. (18) RODD,DATIDSON, AND STOCKS, Ann. Repts. SOC.Chem. Ind. ( L o n d o n ) on Prog. Appl. Chem., 21, 106 (1936). (19) RUGCLI,J. SOC. Dyers Colourists Jubilee I s s u e , 60, 77 (1934). (1) (2) (3) (4) (5) (6) (7)
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