DYESFROM
Dec. 20, i9G1
5015
SUBSTITUTED a-NAPHTHOLS
which had previously been thoroughly purged with helium 119(C2Fa ), 31(C F +)> 50(CFI ) , loo(CtFt +), W C F s N ‘1, 114(C2F4;\;+), 45(CFN+) and 109 (C2FINt+). There a t the operating temperature (540”). Tne products were was a i 5 0 a small Deak a t mass 197(CaF,N1+). while the condensed in a glass trap cooled by iiquid oxygen, and after 1.25 hr. the product (3.0 cc.) was separated by V.P.C. absence of peaks a i 33 and 52 indicat‘ed that {here was no The major components were CF4 and (CF8)zN with small E-F bonding in this compound. amounts of CF3NF2, C2FGand unchanged (CFa)zNF, all Fluorino1yses.-1. When CFsN=iYCFs (0.04 mole/hr.) was allowed t o react with fluorine (0.15 mole/hr.) in the identified by infrared. 2. Next CFsCFzNFz (0.02 mole/ hr.) and helium (0.52 mole/hr.) were passed through the jet reactor, the only products formed were CF, (15 parts), pyrolyzer a t 450”. After 2 hr. the condensed product CFaNFp (1 part) and (CFa)ZNF (1 part). At 150°, 10% of the CFaS=KCPa was returned unchanged, while a t 30°, (4.0 cc.) was separated by V.P.C. T h e major products F~ as identified by infrared were CF,, CzF6, n-C,Fto, NFa, 25% did riut react. 2. Wheii Fz, X F Z C F ~ C F Z Kand nitrogen in the molar ratio 15: 1: 50 were introduced into CFDNFI, (CFI)2NF and (CF8)aN. A small amount of L was also detected. This pyrolysis was repeated the jet reactor a t 200°, only 10% of the X F ~ C F ~ C F ~ N FC3F8 underwent fiuorinolysis to give CF4 (1 part), NFa ( 2 parts), several times during which the composition of the product CF&F2KF2 ( 2 5 parts) and an unidentified compound (10 obtained gradually changed until t t remained constant as: parts). The last mentioned had a very simple infrared CF4, CzFs, C3F8, n-C,F,o, CFaCN and ( C F ~ ) J K . 3. Finally, spectrum with one absorption, a triplet, centered a t 10.65 NF2CFiCF2NF2 (0.025 mole/hr.) diluted with helium (0.60 p . 3. Fraction 2, Table V, which contained (CFa)$NF, mole/hr.) was pyrolyzed a t 255’. After 0.5 hr. the conC F E C F ~ K F CFzN=SCFa, ~, (CFa)aN, CFaIVFC2F6, NF2- densed product (1.3 cc.) was separated by V.P.C. and idenCFzCF2XF2 and CF,r’;=XC2Fa was fluorinated a t a molar , tified by infrared as CF4, C2Fe, C F ~ C F ~ N F ZCFICN, reaction ratio of 3:3 :8 a t 200’. The product contained CFIN=NCFI and unchanaed NFICFXFINFI. At 360’. CF, arid C9Fa with a little CFaNF2 as well as all of the origi- the- products were CF4, -C2F8,C3F8; nIC,F;o, (CF&N; nal materials except CF3N=SCFs and CFsN=NC2F6. C F C N and CFsN=CFz. The amounts of CF, and C2F8formed could account for the Acknowledgment.-We would like to thank Dr. two azo comrmunds that underwent fluorinoiysis, all estimated byV.P.C. Wallace S. Brey, University of Florida, for the Pyrolyses.-The pyrolyzer consisted of a 60” section of n.m.r. spe’ctrum of CF3.NFC2F6,and Dr. John Ruth, copper tuhing electrically heated for the middle 48”. Liggett and Myers Research Laboratory, Durham, 1. At first (CE’nLKF 10.024 molehr.) was mixed with helium (0.5s’moie/hr.) ‘and passed ‘through the pyrolyzer N. C., for the mass spectra given above. +
+
[COMMUNICATION
NO. 2134 PROM
THE
KODAK KESEARCH LABORATORIES, ROCHESTER 4, N. Y.]
RESEARCH LABORATOKIES, E e s r M A N
KODAKeo.
Indomiline Dyes. V.l Some Dyes Derived from Substituted a-Naphthols BY A. P. LURIE,G. H. BROWN,J. R. THIRTLE AND A. WEISSBERGER RECEIVED APRIL 25, 1981 T h e synthesis arid properties of some substituted a-naphthols and the indoaniline dyes derived from them are reported. Effects of substituents and solvents on the absorption maxima of these dyes, prepared by oxidative condensation of the anaphthol with 4-arnino-3-methyl-N,N-diethylaniline, are explained in terms of electronic and hydrogen-bonding considerations.
An increased contribution of the polarized form (Ib) to the resonance hybrid representing the indo0
R-@
(-t)N(C,H,), Ib
aniline dye (I) should cause both a bathochromic shift and an increase in the maximum extinction coefficient. This expectation is based on a study of the indoaniline dyes derived from phenols2 and from 1-hydroxy-2-naphtharnides.1~~ The effect of (1) Indoaniline Dyes. IV. C. R . Barr, G . H. Brown, J. R. Thirtle and A. Wrissberger, P h o t Sc1. and Eng., 6, 195 (1961). (2) (a) P. W. Vittum and G. H . Brown, J . A m . Chem. Soc., 68, 2235 (1946); (b) 69, 153 (1947); (c) 71, 2287 (1949). (3) (a) B. S. Portnaya, I . I. Levkoev and N. S. Spawkukotskil, Doklodr A k a d . Nauk SSSR,811, 603 (1952); (b) N.S. Spawkukotakil. I. I . Levkoev and B. S. Portnaya, i b i d . , 93, 671 (1953); (c) B. S Portnaya. N. S. Spasokukotskil, N. P. Turitsyna, T. P. Bobkova. G . I. Arbuzov and I. 1. Levkoev, J . Gen. Chem. SSSR. 86, 2532 (1956); (d) N. F. Turitsyna, B. S. Portnaya, N. S. Spasokukotskii, T. P. Bobkova, G. I. Arbuzov and I. I. Levkoev, ibid.. 26,2546 (1956).
substituents in positions other than 2 or 3 on the absorption of indoaniline dyes derived from 1naphthol is the subject of the present paper. The data obtained are summarized in Table I. Because an increase in the polarity of the solvent tends to favor the ionic form (Ib) of the dye, the bathochromic and hyperchromic effects observed in proceeding from cyclohexane t o butyl acetate to methanol were to be expected. A plot (Fig. 1) of a-constants4 against l / A m a x of the dyes derived from 6- and 7-substituted a naphthols, using para-constants and metu-constants, respectively, results in straight-line relationships. In these positions, substituents which increase the electron density on the carbonyl oxygen of the dye cause hypsochromic shifts; those which decrease the electron density result in bathochromic shifts. Thus, a methoxy group in position 6, where it can exercise resonance effects, is electron- supplying and gives a hypsochromic shift relative to the dye from a-naphthol; the same group in position 7, owing to its electron-withdrawing inductive effect, causes a bathochromic shift.& (4) L. P. Hammett. “Physical Organic Chemistry,” McGraw-Hill Book Co., Inc., New York, N. Y..1940, p. 188; H . H.Jaffe, Chrtn. Revs., 68, 191 (1953); &values were used when available. (5) It has been brought to our attention, by one of the referees, thot the absorption of substituted indigo and thioindigo dyes (61.
501G
Vol. 83
1ND0.4NILINEa
TABLE I DYESDERIVEDF R O M SUBSTITUTED a - yAPHTHOLS L
0
K
KO.
1 2 3 4 5 6 7 8
9 10 11 12 13
14 15
16
H 5-OCH3 6-OCH3 7-OCHs 8-OCH3 5-OH 6-OH 8-OH 5-h"2 6-KH2 8-NH2 5-NH CzHj 5-SHCOCHp 6-SHCOCI 13 8-SI-ICOCHs J-SHCOCsF;-??
17 18
-~ h
SHSO-(
"2
Crystallized from
114 92 135 153 143 164 191 185 152 198 120 108 19s 2%72 190 130
Ethanol Cyclohexane Ethanol Eth,triol Ethanol Ethanol Ethanol .Icet one 2-Propanol Benzenc Ethanol Ethanol Ethanol Et11n no1 Ethanol Cyclohcunnr
5 8 2 ( 1 . 1 ) [0.541 5 8 8 ( 1 . 6 ) [ ,641 576(1.3) [ ,551 5 8 7 ( 1 . 5 ) [ .58] 570 [ ,551 [,591 fj40(2.0) [ .iiO] 6 2 9 ( 1 . 3 ) i ,701
023(1.7) [O.(j2] 6 2 0 ( 1 . 8 ) [ .'if] fj23(1.6) [ .e21 f j P i ( l . 6 ) [ ,631 6 2 2 ( 1 . 6 ) [ .64] 6 2 4 ( 1 . 8 ) [ .63] 6 i 7 ( 1 . 5 ) [ .651 660 [ .67] 6 2 4 ( 1 . 3 ) [ ,721 6 1 2 ( 1 . 3 ) [ 381 6 3 0 ( i . 5 ) [ ,761 6 3 8 ( 1 . 4 ) 1 .77] 6 3 6 ( 1 . 5 ) I .A71 ti?;f1.7j[ .f'6l 655(2.1) [ ,651 650(1.31 [ .71:
Ethyl ncetote
GOO(1.8) [ .55]
616(1.9)[ .58]
G10(:?.0)! . ; 3 ]
Ethanol
629
[ ,581
646(2.1) [ .SO]
663
c
c
[ .(;l]
168 Ethanol 19 5-XO: 6 2 3 ( 2 . 2 ) [ .52] 646(2.3) [ . G 1 ] 6 1 3 ( 2 . 2 ) [ ,461 mu Ethyl acetate 20 B-K-O? 658 [ .G41 618 [ .50l 6 3 6 ( 2 . 1 ) [ ,571 21 11; Gtlinnol 5-CI 598 [ ,591 6 1 2 ( 1 . 4 ) [ ,641 636(1.5) [ .71] Etllallnl 128 22 5 9 7 ( 1 . 5 ) [ .59] BPj(l.6) [ .e51 7-CHa jSl(1.4) [ .551 182 Et i1anol j Z ( 1 . 3 ) [ .58] 592(1.5)[ .5i] 626(1.6) [ .62] 23 6,i-OCHs Cyclohexane 5 6 6 ( 1 . 0 ) [ .62] GOO(1.1) [ ,721 152 24 554(0.9) [ ,601 5,8-OCH3 Ethn 1101 110 5 7 0 ( 0 . 9 ) [ ,661 5 9 6 ( 0 . 9 ) [ .731 556 [ .601 '75 5,8-OCE13-7-CII~ Et 1lJllInl 1tG B O O ( 1 . 4 ) [ ,611 6 2 0 ( 1 . 4 ) [ .711 26 5 8 7 ( 1 . 3 ) [ ,571 5,8-C1 0 For convenience, only the non-polar structure Ta is given. The slope of the spectrophotometric curve in the region of peak absorption is given in ternis of sharpness, s. For the discussion me have considered only the sharpness on the low m v e t h e smnller will he the Slength side of the absorptiori curve as given b y s = D x ~ ~ ~ - ~ , , ~The ~ . sharper / D x ~the ~ ~curve . value. Too insoluble.
Electron-withdrawing substituents (e.g., nitro-) in position 5 give rise to bathochromic shifts. XIethoxy and chloro groups, in this position, also shift the absorption t o longer wave lengths in agreement with the fact that they can exert only inductive effects on the absorption of the dye. -1s can be expected, amido groups in position 5 cause larger bathochromic shifts the greater the inductive effect of the acyl group, as measured by the strength of the corresponding acid. The %substituents studied, with the exception of amino, affect the hue of the dye, apparently, by a withdrawal of electrons from the aromatic system as a whole. It is difficult t o understand the hypsochromic shift effected by a %amino group unless one assumes that a direct interaction between the two ?J-atoms in the peri-positions interferes with the ability of the tertiary nitrogen atom to accept the positive charge. The similarity in absorptions of the S-rnethoxy-, C,-methoxy- and 6-hydroxj.-l-naphthol dj-es is J. Formanek, 2 . angew. Chcm., 41, 1137 (1928)) has been explained in a similar manner by G. M. Wyman and W. R Brode, .I 4wt C h P m SOL , 7 8 , 1408 (1951,
readily understood in terms of resonance. The observation t h a t the S-hydroxy-1-naphthol dye absorbs a t considerably longer wave lengths can be explained by the hydrogen bonding as shown in 11. Such an interpretation is corroborated by the conip r i s o n of other 6-an?[ 8-substituents c a p n l k of
such hydrogen bonding. An amino group in p s i tion 6 causes a hypsochromic shift of 16 m p in cyclohexane, relative t o that of the unsubstituted l-naphthol dye? but the Same group in position results in a 20-mp bathochromic shift. The acet-
DYESFROM SUBSTITUTED CY-NAPHTHOLS
Dec. 20, 19G1
I i... I. 2 r
.....................
'.,
I
I, 0
tI
.ec
',...,
Methanol
\
I\\\\\ \
-----Butyl acetate Cyc Io hexane
1 'i I
I
5017 I
/
I
2.0
I
\ 0'
i
/-NHSO&CH~
5-OH
-I
J
.'I -4
I 650
500
Fig. 1.-Plot of l/Am,, ,,A,( in mp) vs. Hammett's uconstants for indoaniline dyes (I) substituted in the 6- or 7positions.
amido group in position 6 is without effect but is bathochromic by 44 m p in position 8. Analogous chelation effects have been used to explain the difference in absorptions of dyes prepared from 2acetamido- and 3-acetamidophenolZa and for the differences between dyes from 1-hydroxy-2-naphthamides derived from primary and secondary The dyes with multiple substitution on the naphthol ring show hypsochromic shifts which are considerably larger than the values calculated by the addition of shifts caused by the individual groups.2c The data seem to indicate that there is a mutual enhancement of electron density toward the aromatic system, particularly in the case of 5,8dimethoxy substitution. The data presented indicate t h a t the dominant factor controlling Xma, is the increased or decreased ability of the tertiary nitrogen atom of the p phenylenediamine moiety to accept a positive charge as shown in Ib. The effect of substituents on extinction and shape of the absorption curve is less readily explained, However, a plot of Amax US. E m a x (Fig. 2 ) reveals that where chelation effects between groups in peripositions are not possible, a nearly linear relationship exists. With the exception of 6-hydroxy, -nitro and -p-toluenesulfonamido groups, all of the 5substituted dyes give low extinction coefficients and unsharp absorption curves (see footnote b, Table I). It appears t h a t the absorption becomes broader and the extinction diminishes when additional structures contribute to the resonance hybrid representing the dye.
Experimental6 A.
Couplers.-Commercially available 1-naphthol, 5nitro-1-naphthol, 5-p-toluenesulfonamido-1-naphthol, 1,5naphthalenediol and 1,6-naphthalenediol were recrystallized t o constant m.p. prior to dye formation. (6) All melting points are uncorrected. The microanalyses were performed bv D F Ketchurn and associates Kodak Research Laboratories, Eastman Kodrk 60.
Xrnox, mp.
Fig.2.-Plot
of Xmsr vs. Em,, for a-naphthol indoaniline dyes ( I ) in butyl acetate.
The following couplers were prepared according to rnethods described in the literature and gave satisfactory elemental analyses ( $0.37, absolute): 5-meth0xy-l-naphthol,~~ m.p. 135-136 ; 8-methoxy-l-naphth01,7~ m.p. 53-54"; 8-amino-l-naphthol,8 m.p. 95-96"; 6-acetamido-l-naphth~l,~ m .p. 95-96'; 8-acetarnido-l-naphthol,10 rn .p. 174~175'; 8-p-toluenesulfonamido-l-naphth~l,11 m.p. 190-192 ; 6nitro-l-naphthol,12m.p. 178-180 . The rest of the couplers are either new compounds or were synthesized by methods superior t o those given in the literature. Infrared spectra have been obtained for all couplers and their intermediates; these spectra confirm the structural assignments. 6-Methoxy-l-naphtho1.l3-A mixture of 10 g. (0.058 mole) of 6-rneth0xy-l-naphthylamine,'~ 40 g. of sodium bisulfite and 100 mi. of water was refluxed 24 hr. and then made alkaline (caution!) with 307, aqueous sodium hydroxide solution and refluxed 24 hr. longer. The filtrate was acidified with 209" aqueous hydrochloric acid and the precipitate recrystallized from ethanol-water to give 6 g. of 6-methoxy1-naphthol, m.p. 79-80'. Anal. Calcd. for CllH1002: C, 75.8; H , 5.8. Found: C, 75.8; H , 6.1. 7-Metho~y-l-naphthol.~~-Toa solution of 12 g. (0.06 mole) of 8-acetamido-2-naphtho110 in 150 ml. of water containing 5.2 g. of sodium hydroxide there was added 13 g. (0.10 mole) of dimethyl sulfate a t 25' and the resulting mixture was stirred 4 hr. The precipitate was recrystallized from ethanol-water to give 9.7 g. of l-acetamido-imethoxynaphthalene, m.p. 166-167", litS17m.p.145". Anal. Calcd. for C13Hl3N02: C, 72.5; H, 6.1; N, 6.5. Found: C,72.3; H, 6.2; N, 6.3. (7) (a) H. E. Fierz-David, L. Blangey and W. von Krannichfeldt, Helw. Chim. Acta, 3 0 , 816 (1947); m.p. 135-136O. (b) H. Staudinger, E. Schlenker and H. Goldstein, ibid., 4, 334 (1921); m.p. 55-50', (8) F. Fichter and R. Gageur, B e y . , 39, 3331 (1900); m.p. 93-07' (9) L. Sander, ibid., 58, 824 (1025); m.p. looo. (10) L. C. Raiford and E. P. Clark, J . Am. Chem. SOG.,48, 483 (1926); m.p. 18P. (11) F. Fichter and T. Kiihnel, Ber., 42, 4748 (1909); m.p. 180°. (12) H. H. Hodgson and H. S. Turner, J . Chem. Soc., 8 (1944); m.p. 181-182°. (13) German Patent 298,098 ( 1 9 1 6 ) ; no m.p. is given for this compound. (14) A. Butenandt and G. Schramm, Ber., 68, 2083 (1935). ( 1 5 ) Prepared b y a rapid distillation of p-anisalpropionic acid, the product has a m.p. significantly different from that reported herein; A. Angeletti, GQEZ.chim. ital., 59, 851 (1929). (16) F. Kehrmann and E. F. Engelke, Be7., 42, 350 (1909). (17) W.A. Davis, Chem. Nezur, 74, 302 (I896), has an alternate syrithesis.
5018
A . P. LURIE,G. H. BROWK,J. R. TIIIRTLE AND A. WEISSBERGER
A solution of 9 g. of potassium hydroxide in 10 ml. of water was added t o a solution of 8.4 g. (0.038 mole) of 1acetamido-7-1nethoxy1iaphthalene in 60 mi. of ethanol, refluxed 12 hr. and then poured into 500 mi. of water. The precipitate was recrystallized from methanol-water to give ti g. of 7-methoxy-?-ti~phtliylai~iiie, m.p. 79.5-80", lit.'* 1n.p. 81". Five grams (0.03 mole) of 7-:netl~oxy-l-ilaphtliyl~iii~iiie was converted, as described for the 6-methoxy isomer, to 0.5 g. of 7-methoxy-1-naphthol, m.p. 104.5-105" from ethanolwater; m.p. 122--124', turning brown a t 60". Aiiul. Calcd. for Ct:HIOOZ: C, 75.8; H, 5.8. Found: C, 75.8; H, 6.0. 1,S-Naphthalenedi~l.~g-A mixture of 50 g. of l-naphthol8-sulfonic acid (Eastman Kodak Co.), 150 g. of potassium hydroxide, 150 g. of sodium hydroxide and 75 rnl. of water was fused slowly, with vigorous stirring, to 230" in a 5 liter stainless-steel beaker. The fusion was interrupted when frothing had ceased arid the melt was totally eiicrusted with black tar, The fluid mixture was poured onto a stainless-steel sheet to effect immediate solidification. The solid mass rras crushed and added piecemeal, with vigorous stirring, t o 2.R liters of water containing 700 ml. CJf concentrated hydrochloric acid and the mixture boiled for 10 itiin. and filtered hot. The cooled filtrate was extracted with ethyl ether, dried and evaporated. The residue was recrystallized from benzene-ligroin to give 4.3 g. of 1,snaphthalenediol, m.p. 142-143", lit..I9m.p. 140". Anal. Calcd. for ClQH602: C, 74.9; 11, 5.1. Found: c, 75.9; H, 5.3. 5-Amino-l-naphthol.-5-~itro-l~naphthol (19 9.) in 200 nil. of isopropyl alcohol was reduced in the presence of Kaney nickel at 50 p.s.i. hydrogen. The solution of the amine was acidified with concentrated hydrochloric acid, stripped to dryness and the resultant solid converted to the free amine with 57, aqueous sodium carbonate solution. Recrystallization from water gave 12 g. of Samino-lnaphthol, 11i.p. 192-193' dec.; lit. m.p. 170' dec.,zOa192" dec.ZOb Anal. Calcd. for CloHsPu'O: C, 75.4; H, 5.7; N,8.8. Found: C, 75.2; H, 5.8; N , 8 . 7 . 6-Amino-l-naphthol.-Cntslytic hydrogenation under the conditions just given afforded a 957, yield of 6-amino-lnaphthol, m.p. 193-195' dec. (from acetic acid), lit.*] m.p. 199.5" dec. Anal. Calcd. for C I O H ~ X O C, : 75.4; H , 5.7; N, 8.8. Found: C, 75.3; H,6.0; K,8.6. 5-Acetamido-1-naphthol.- A mixture of 3.2 g. (0.02 mole) of 5-amino-1-naphthol and 9.8 g. of acetic anhydride was shaken vigorously. During the exothermic reaction, complete solution occurred, followed immediately by solidification. The solid was recrystallized irom ethanol-ligroin t o give 1.6 g. of 5-acetarnido-1-naphthol, m.p. 172-174". Anal. Ca!cd. for C12HllN02: C, 71.6; H, 5.5; N,7.0. Found: C, 71.6; H, 5.8; X,6.9. 5-Ethylamino-l-naphthol.-Thirty grams (0.15 mole) of .i-:icet3niid~l-nap~ithol was converted t o 21 g. of bacetamido-1-methoxynaphthalene (see 1-acetamido-7-methoxyn,iphthalene), m.p. 189-190" (from ethanol-ligroin). ilnal. Calcd. for C ~ S H ~ ~ KC,O 72.5; ~: 13, 6.1; N, 6.5. Found: C, 72.6; H , 6.3; K,6.6. Twenty grams (0.09 mole) of this amide was added t o a suspension of 5.7 g. (0.15 mole) of lithium aluminum hydride in 500 mi. of ethyl ether and refluxed 3 days. After decomposition of excess lithium aluminum hydride, the mixture was extracted with 3 liters of ethyl ether which was tlien decolorizrd and dried over anhydrous magnesium sulfate. The residue, after evaporation of ethyl ether, was recrystallized from cyclohexane t o give 12 g. of Sethylimino-1-methoxynaphthalene, m.p. 74.575". (18) German Patent 477,148(1926). ( i R ) H. Erdmann, A n n . , 247, 306 (1888); an alternate method t o t h n t reported herein was used. 120) !a) H. T. Bucherer aud A. Uhlmann, J . p r a k f . Chem., 121 80, 20: (1909); (i,) h'. N. Vorozhtzov and A . A. Kulev, Bull. inst. polyr e c h . Zuanouo-Vomicsenck. 9, 87 (1928). (21) I
