United S ta tes P a tent C ?

tic e
3 , 1 1 9 , 8 1 1
P a tented J a n. 2 8 , 1 9 64
1
3 , 1 1 9 , 8 1 1
DYES FER QOLUR P HQTGGRAP HY
P a u l Dr ey tns s , B a s el , S w itz er l a nd, a s s ig no r to
C ib a S ta tes Lim ited, New Yo r k , FLY.
No Dr a w ing . Fil ed S ep t. 7 , 1 9 60 , S er . No . 5 4, 3 8 1
C l a im s p r io r ity , a p p l ic a tio n S w itz er l a nd S ep t. 9 , B 5 9
7 C l a im s . ( C l . 2 60 1 7 9 )
The p r es ent inv entio n p r o v ides dy es f o r the s il v er dy e
b l ea c h p r o c es s a s w el l a s p ho to g r a p hic m a ter ia l c o n
ta ining s u c h dy es f o r the s il v er dy e b l ea c h p r o c es s a nd
c o l o r p ho to g r a p hs p r o du c ed ther ef r o m .
I t is k no w n tha t it is p o s s ib l e to p r o du c e w ith the a id
o f the s il v er dy e b l ea c h p r o c es s , w hic h is b a s ed o n the r e
m o v a l o f dy es c o r r es p o nding to the im a g e, m o no c hr o m e
o r p o l y c hr o m e p ho to g r a p hic r ec o r ds . I n the s il v er dy e
b l ea c h p r o c es s the im a g e is ? r s t f o r m ed b y a k no w n p ho
to g r a p hic m etho d b y ex p o s u r e a nd dev el o p m ent a s a s il
v er im a g e in a p ho to s ens itiv e l a y er ho m o g eneo u s l y dy ed
w ith a dy e. The dy e p r es ent in the l a y er is then r em o v ed
in a s il v er dy e b l ea c h b a th in ea c h im a g e a r ea p r o p o r
tio na l to the a m o u nt o f im a g e s il v er p r es ent in it. The
s il v er is then r em o v ed, w her eu p o n a dy e im a g e o p p o s ite
to the o r ig ina l s il v er im a g e is o b ta ined. As w ith the
k no w n m u l ti- p a c k m a ter ia l s w hic h a r e p r o c es s ed a c c o r d
ing to the c o l o r c o u p l ing dev el o p m ent ther e is u s ed a l s o
in the s il v er dy e b l ea c h p r o c es s f o r the p r o du c tio n o f p o l y
c hr o m e p ho to g r ' ip hs a dv a nta g eo u s l y a m u l ti- l a y er m a te
r ia l c o m p r is ing in g ener a l thr ee s ep a r a te c o m p o nent dy e
l a y er s Who s e s ens itiv ity is r es tr ic ted to the a s s o c ia ted
s p ec tr a l a r ea s . Fo r ex a m p l e, in a p r ef er a b l y u s ed m u l ti
l a y er c o m b ina tio n the b a s e is c o a ted, o ne u p o n a no ther ,
w ith a ? r s t l a y er s ens itiz ed to r ed c o nta ining a b l u is h
g r een ( c y a n) dy e, a s ec o nd l a y er s ens itiz ed to g r een c o n
ta ining a p u r p l e ( m a g enta ) dy e, a thir d y el l o w ? l ter l a y
er f o r el im ina ting a ny s ho r t- w a v e r a y s tha t a r e a dis tu r b
ing f a c to r in v iew o f the inher ent s ens itiv ity o f tr e tw o
u nder l y ing l a y er s , a nd a s the to p m o s t l a y er a no n- s ens i
tiz ed, tha t is to s a y b l u e- s ens itiv e, l a y er c o nta ining a y el
l o w dy e.
The dy es u s ed in p ho to g r a p hic m a ter ia l to b e p r o c es s ed
b y the s il v er dy e b l ea c h p r o c es s m u s t s a tis f y a n ex tr em e
l y v a r ied r a ng e o f r eq u ir em ents . Ap a r t f r o m ha v ing to
b e ea s y to b l ea c h o u t, a s is needed f o r the s il v er dy e b l ea c h
p r o c es s , s u c h dy es m u s t b e r ea dil y s o l u b l e in Wa ter ; they
m u s t no t tend to dif f u s e in g el a tine o r o ther ? l m - f o r m ing
c o l l o ids ; a nd they m u s t no t ha v e a n a dv er s e ef f ec t o n
the p ho to g r a p hic er o p er ties o f the s il v er ha l ide em u l s io n
in w hic h they a r e inc o r p o r a ted. They m u s t b e f a s t to
l ig ht a nd p o s s es s p u r e tints .
in the s il v er dy e b l ea c h p r o c es s inc r ea s ed p ho to s ens i
tiv ity in the indiv idu a l l a y er s is o f s p ec ia l im p o r ta nc e b e
c a u s e the p ho to s ens itiv e s il v er ha l ide l a y er c o nta ins a dy e
a l r ea dy a t the ex p o s u r e s ta g e w hic h dy e a b s o r b s the a v a il
a b l e ex p o s u r e l ig it a nd ther eb y dim inis hes the p ho to
s ens itiv ity o f the l a y er . The s ens itiz ing o f s u c h dy ed l a y
er s is f u r ther r ender ed v er y di? ic u l t b y the f a c t tha t the
hither to k no w n dy es u s ed f o r s ens itiz ing the l a y er ha v e
a s tr o ng des ens itiz ing a c tio n o n the em u l s io n o v er a nd
a b o v e the a f o r em entio ned a c tio n o f the a b s o r p tio n w hic h
dec r ea s es the p ho to s ens itiv ity .
The p r es ent inv entio n p r o v ides new dy es w hic h a r e
p a r tic u l a r l y s u ita b l e f o r the a f o r em entio ned p u r p o s e a nd
1 0
2 5
3 5
60
2
c o r r es p o nd to the g ener a l f o r m u l a
( 1 ) X
w her ein D a nd E r ep r es ent a l ip ha tic r a dic a l s w hic h to
g ether c o nta in a t l ea s t 5 c a r b o n a to m s ; X a nd Y ea c h r ep
r es ent a hy dr o g en a to m o r a m o no v a l ent s u b s titu ent o r ,
w hen X a nd Y a r e v ic ina l , they m a y c o ns titu te the c o m
p l em ent r eq u ir ed to f o r m a f u r ther r ing , a nd L a nd M
ea c h r ep r es ent a r a dic a l o f a n a m ino hy dr o x y na p htha
l ene- s u l f o nic a c id b o u nd to the a z o l ink a g e in v ic ina l p o
s itio n to the hy dr o x y l g r o u p .
The dy es o i the Fo r m u l a 1 c a n b e p r ep a r ed b y c o u
p l ing in a k no w n m a nner a n a m ino hy dr o x y na p htha l ene
s u l t o nic a c id w ith a tetr a z o c o m p o u nd o f a dia m ine o f
the f o r m u l a
in w hic h D, E, X a nd Y ha v e the a b o v e m ea ning s .
The dia m ines o f the Fo r m u l a 2 a r e l ik ew is e a v a il a b l e
b y k no w n m etho ds , b y c o ndens ing a n a r o m a tic a m ine o f
the f o r m u l a
( 3 ) X
H2 N< ~
Y
in a n a c id m ediu m w ith a n a l ip ha tic k eto ne c o nta ining
a t l ea s t 6 c a r b o n a to m s .
P a r tic u l a r l y s u ita b l e a m ines o f the Fo r m u l a 3 a r e
a m ino b enz ene a nd a m ino b enz enes s u b s titu ted b y ha l o g en
a to m s s u c h a s c hl o r ine, b y a l k y l g r o u p s s u c h a s m ethy l
o r ethy l , o r b y a l k o x y g r o u p s s u c h a s m etho x y o r etho x y ,
f o r ex a m p l e l - a m ino - B - c hl o r o b enz ene, 1 - a m ino - 2 - m ethy l
o r - 2 - ethy l b enz ene, 1 - a m ino - 2 : 5 - o r ~ 2 2 6- dim etl 1 y l b enz ene
o r 1 - a m ino - 2 - m etho x y - b enz ene. As a n a m ine o f the
Fo r m u l a 3 w ho s e s u b s titu ents X a nd Y a r e v ic ina l a nd
f o r m the c o m p l em ent to a f u r ther r ing ther e m a y b e m en
tio ned l - a m ino na p htha l ene.
The a l ip ha tic k eto nes to b e c o ndens ed w ith s u c h a m ines
c o nta in a t l ea s t 6 c a r b o n a to m s , a nd, a dv a nta g eo u s l y , in
a dditio n to the o x y g en a to m o f the k eto g r o u p o nl y c a r
b o n a nd hy dr o g en a to m s . They c o r r es p o nd, f o r ex a m p l e,
to the f o r m u l a
C O
in w hic h in a nd n a r e w ho l e nu m b er s , the s u m ( m - I - n)
b eing a t l ea s t 5 . The a l ip ha tic r a dic a l s D a nd E m a y b e
b r a nc hed o r p r ef er a b l y u nb r a nc hed
H]
a nd a dv a nta g eo u s l y a t l ea s t o ne o f them c o nta ins m o r e
3 , 1 1 9 , 8 1 1
4
tha n 5 , f o r ex a m p l e 6 to 2 0 , c a r b o n a to m s . S u ita b l e w her ein the tw o Z s ha v e the a b o v e m ea ning ; U r ep r es ents
k eto nes o f the Fo r m u l a 4 a r e f o r ex a m p l e a C O- o r S O2 g r o u p , a nd R1 a n u ns u b s titu ted o r
Methy 1 _ n_ a m y 1 k em ne s u b s titu ted b enz ene r a dic a l . The b enz ene r a dic a l m a y c o n
Methy ] _ _ n_ hex y l k eto ne ta m , f o r ex a m p l e, a s f u r ther s u b s titu ent a n a l k y l _ g r o u p
Methy p m hep ty l k eto ne 5 s u c h a s m ethy l o r a ha l o g en a to m s u c h a s c hl o r ine, o r
Methy l _ n_ no ny l k eto ne a n a c ety l a m l no g r o u p , a nd 1 f des ir ed it m a y c o nta in tw o
o r thr ee s u b s titu ents s o tha t it c o r r es p o nds , f o r ex a m p l e,
Ethy l - n- b u ty l k eto ne
Diis o b u ty l k eto ne to the f o r m u l a
Di- ( n- hep ty l )- k eto ne 1 O ( 3 ) Y Y
Whil e the k no w n c o ndens a tio n p r o du c ts o f a r o m a tic ~ V
a m ines a r e r el a tiv el y ea s y to is o l a te in the f o r m o f c r y s
ta l l ines s u b s ta nc es w ith a c eto ne, b enz y m ethy l k eto ne o r the V V
l ik e, c o ndens a tio n p r o du c ts w ith hig her a l ip ha tic k eto nes in w hic h 2 to 5 Vs r ep r es ent hy dr o g en a to m s , 0 to 2 Vs
ha v e v er y l ittl e c r y s ta l l iz a tio n tendenc y . Ac c o r ding l y , 1 5 m ethy l g r o u p s , 0 o r 1 V r ep r es ents a c hl o r ine a to m a nd
the c o ndens a tio n p r o du c ts o f the Fo r m u l a 2 m u s t b e 0 o r 1 V a n a c ety l a r nino g r o u p .
is o l a ted f r o m the c o ndens a tio n m ix tu r es either b y f r a c - The f o r m u l a e o f the p r ef er r ed dy es c a n b e w o r k ed o u t
tio na l dis til l a tio n o r p r ef er a b l y b y tr ea ting the c r u de c o n- w itho u t di? ic u l ty f r o m the a b o v e s p ec i? c a tio ns a nd f o r
dens a tio n m ix tu r e w ith a n a c y l a ting a g ent s u c h, f o r ex - m u l a e o f the inter m edia tes . I n this c o nnec tio n s p ec ia l
a m p l e, a s a c etic a nhy dr ide o r nitr o b enz o y l c hl o r ide, 2 0 m entio n is m a de o nl y o f the dy es o f the f o r m u l a
( 9 )
Ac y l - HN 0 1 1 X X no NI I - Aey l
1 a l l I
N=N- N=N
z _ s 0 3 1 1 Y Y 1 1 0 3 S " 2
w her eu p o n the r ea dil y c r y s ta l l iz ing a c y l a ted der iv a tiv es in w hic h D, E, X, Y a nd Z ha v e the a b o v e m ea ning s a nd
0 f the f o r m u l a the a c y l g r o u p s a r e p r ef er a b l y m a de u p o f a C O- o r
( 5 ) X X S 2 O b r idg e a nd a r a dic a l o f the Fo r m u l a 8 .
The new dy es o f the Fo r m u l a 1 a r e p a r tic u l a r l y s u ita b l e
_ NH. Ac y 1 f o r inc o r p o r a tio n in s il v er ha l ide em u l s io ns f o r the p r o
3 5 du c tio n o f c o l o r p ho to g r a p hs b y the s o - c a l l ed s il v er dy e
Y Y b l ea c h p r o c es s , b ec a u s e they s a tis f y ex tens iv el y the nu
m er o u s r eq u ir em ents m entio ned b el o w w hic h a r is e in s a id
p r o c es s , na m el y :
They m u s t b e c o m p a tib l e w ith the s il v er ha l ide em u l
s io n, m o r e es p ec ia l l y w ith a n o p tic a l l y s ens itiz ed s il v er
b l ea c ha b l e w itho u t l ea v ing c o l o r ed r a dic a l s . They m u s t
b e f a s t to l ig ht, m o r e es p ec ia l l y in the c a s e o f r ec o r ds
v iew ed b y inc ident l ig ht, a nd their a b s o r p tio n m u s t s a tis f y
c er ta in s p ec tr a l c o nditio ns .
45 I n g ener a l , thes e dy es a r e p u r p l e dy es o f a p a r tic u l a r l y
p u r e tint. I ns o f a r a s they tend to diif u s e they c a n b e
m a de s ta b l e to dif f u s io n w ith b a s ic p r ec ip ita ting a g ents
s u c h, f o r ex a m p l e, a s a b ig u a nide. B y s u ita b l y s el ec ting
the c o m p o nents the deg r ee o f dif f u s io n c a n b e v a r ied.
5 0 When the r a dic a l s D a nd E in the dia m ines a r e inc r ea s ed,
the r es u l ting dy es a r e m o r e s ta b l e to dif f u s io n. Ho w ev er ,
the nec es s a r y s iz e o f D a nd E dep ends a l s o o n the c o ntr i
b u tio n w hic h the c o u p l ing c o m p o nent m a k es to the dif
f u s io n s ta b il ity ; it s u f ? c es ther ef o r e to u s e a dia m ine
w ith r el a tiv el y s m a l l D a nd E r a dic a l s to r ender the
( 6) HO I I TH' AC W dis a z o dy e f r o m 2 m o l s o f a c o u p l ing c o m p o nent o f l a r g e
m o l ec u l a r s iz e, o r o ne w hic h im p a r ts to the dy e a ? inity
f o r the b a s e, s ta b l e to dif f u s io n.
The dy es , m o r e es p ec ia l l y tho s e o f the Fo r m u l a 9
a r e o b ta ined f r o m w hic h the p u r e dia m ines a r e o b ta ined
b y hy dr o l y s is , p r ef er a b l y in a n a c id m ediu m . The a c id
s o l u tio ns o b ta ined b y hy dr o l y s ing the a c y l a ted a m ines c a n 40
b e u s ed a s they a r e f o r the tetr a z o tiz a tio n a nd dy e
c o u p l ing o r , a l ter na tiv el y , the b a s e c a n ? r s t b e l ib er a ted
f r o m the hy dr o l y s is s o l u tio n.
The a m ino hy dr o x y na p htha l enes u l f o nic a c ids to b e
c o u p l ed w ith the tetr a z o c o m p o u nds o f the dia m ines o f
the Fo r m u l a 2 m a y c o nta in o ne o r tw o s u l f o nic a c id
g r o u p s a nd a p r im a r y o r s u b s titu ted a m ino g r o u p , f o r
ex a m p l e a p heny l a m ino g r o u p o r p r ef er a b l y a n a c y l a m ino
g r o u p . I n g ener a l it is o f a dv a nta g e to c o u p l e the tetr a z o
c o m p o u nds o n b o th s ides w ith the identic a l a m ino hy dr o x y
na p htha l enes u l f o nic a c id.
P a r tic u l a r l y v a l u a b l e dy es a r e o b ta ined b y c o u p l ing a
tetr a z o c o m p o u nd w ith a 1 - a c y l a m ino - 8 - hy dr o x y
na p htha l ene- 3 : 6- o r - 4: 6- dis u l f o nic a c id ( a c y l - H a c id o r
a c y l - K a c id) w hic h c o r r es p o nd to the f o r m u l a 5 5
H0 3 5 Z 60 a r e p a r tic u l a r l y dis ting u is hed b y the f a c t tha t they a r e
I r ea dil y c o m p a tib l e w ith s il v er ha l ide em u l s io ns , m o r e
Z es p ec ia l l y w ith o p tic a l l y s ens itiz ed s il v er ha l ide em u l s io ns ,
in w hic h o ne Z r ep r es ents a hy dr o g en a to m a nd the o ther tha t is to s a y tha t they ha v e a r el a tiv el y m ino r des ens itiz ~
Z a s u l f o nic a c id g r o u p . The a c y l r a dic a l l ink ed to the ing ef f ec t.
a m ino g r o u p is p r ef er a b l y der iv ed f r o m a b enz enes u l f o nic 65 The dy es o f the inv entio n c a n b e a p p l ied in a g el a tine
a c id o r a b enz enec a r b o x y l ic a c id. I n this c a s e the c o m - s il v er ha l ide em u l s io n o r to g ether w ith a s il v er ha l ide
p o u nds to b e u s ed a s c o u p l ing c o m p o nents c o r r es p o nd to em u l s io n in a no ther c o l l o id; they c a n a l s o b e inc o r p o r a ted
the f o r m u l a in dr o p l ets o f a hig h- b o il ing c r y s ta l l o id m a ter ia l o r in a
( 7 ) HO NH_ _ U_ R1 s p ec ia l c o l l o id l a y er s u p er im p o s ed u p o n the s il v er ha l ide
7 0 l a y er ; they m a y b e no n- dif f u s ing a s s u c h o r they m a y
ha v e b een r eneder ed no n- dif f u s ing b y s u ita b l e a dditiv es .
Ho w ev er , a s is des ir a b l e f o r c er ta in dy e tr a ns f er p r o c es s es ,
Ho g s _ _ Z they m a y b e c a p a b l e o f dil f u s io n. The dy es o f the in
v entio n c a n b e c a s t in s ing l e l a y er s o r in m u l ti- l a y er m a
Z 7 5 ter ia l s o r in m u l ti- p a c k em u l s io ns . They a r e s u ita b l e f o r
3 , 1 1 9 , 8 1 1
' p r o du c ing r ec o r ds to b e v iew ed b y tr a ns m itted o r inc ident
l ig ht.
I n c o nc l u s io n it m a y b e s ta ted tha t the dy es a r e a l s o
s u ita b l e f o r o ther tha n p ho to g r a p hic p u r p o s es . They c a n
b e u s ed f o r dy eing a w ide v a r iety o f m a ter ia l s , f o r ex
a m p l e ? b er s o f v eg eta b l e, a nim a l , o r s y nthetic o r ig in,
s u c h a s c o tto n, w o o l , s il k o r p o l y a m idic ? b er s .
Unl es s o ther w is e indic a ted, p a r ts a nd p er c enta g es in
the f o l l o w ing ex a m p l es a r e b y w eig ht.
Ex a m p l e 1
1 8 3 p a r ts o f the dia m ine o f the f o r m u l a
( 1 0 ) H3 0 0 Ha
C E3 |
H2 N< , > ~ ( ! J - < > - NH2
( ( L H2 ) r ( l _ ' } 1 1 3
a r e tetr a z o tiz ed in the u s u a l m a nner in a hy dr o c hl o r ic
a c id s o l u tio n w ith 7 0 p a r ts o f s o diu m nitr ite a nd c o u p l ed
w ith 48 0 p a r ts o f 1 - ( 3 - a c ety l a m ino b enz o y l a m ino )- 8 - hy
dr o x y na p htha l ene- 3 z - dis u l f o nic a c id in a s o l u tio n a l k a
l iniz ed w ith s o diu m c a r b o na te. The p u r p l e dy e is ? l ter ed
o f f a nd f r eed f r o m s a l t in the u s u a l m a nner . I n the f o r m
o f the f r ee a c id it c o r r es p o nds to the f o r m u l a
( 1 1 )
@Mr @
C 1 1 3
I t is v er y r ea dil y s o l u b l e in w a ter , do es no t dif f u s e in
g el a tine, ha s a hig h b r il l ia nc e, it is r ea dil y c o m p a tib l e
w ith s il v er ha l ide em u l s io ns , a nd c a n b e b l ea c hed p u r e
w hite.
The dia m ine o f the Fo r m u l a 1 0 u s ed a s s ta r ting m a te
r ia l c a n b e p r ep a r ed a s f o l l o w s :
A s o l u tio n o f 1 2 8 p a r ts o f 1 - a m ino - 2 - m ethy l b enz ene
in 1 2 0 p a r ts b y v o l u m e o f hy dr o c hl o r ic a c id o f 3 0 %
s tr eng th is tr ea ted w ith 5 4 p a r ts o f m ethy l l - n- no ny l k eto ne,
a nd the tem p er a tu r e is r a is ed w ithin 4 ho u r s w ith s tir
r ing f r o m 60 to 1 1 0 C . The Who l e is then dis til l ed Whil e
r a is ing the tem p er a tu r e to 1 40 C . , w her eu p o n a n a q u eo u s
l a y er a nd a n o il y l a y er s ep a r a te in the r ec eiv er . The
o il is is o l a ted a nd r etu r ned to the r ea c tio n v es s el . The
s o l idi? ed m ix tu r e is then hea ted u nder r e? u x f o r a b o u t 8 '
ho u r s a t 1 40 C . , ta k en u p in w a ter , r ender ed s tr o ng l y
a l k a l ine w ith s o diu m hy dr o x ide s o l u tio n, a nd the s ep
a r a ted o il is s u b j ec ted to s tea m dis til l a tio n to r ec o v er
the ex c es s l s a m ino - Z - m ethy l b enz ene. The o il y r es idu e
r em a ining in the dis til l a tio n v es s el is dis s o l v ed in b enz ene,
dr ied o v er c a l c iu m c hl o r ide, f r eed f r o m b enz ene a nd
s tir r ed w ith a c etic a nhy dr ide. When the m ix tu r e is l ef t
to its el f , the a c ety l c o m p o u nd c r y s ta l l iz es o u t; a f ter ha v
ing b een r ec r y s ta l l iz ed f r o m a c eto ne it m el ts a t 1 7 0 C .
A m ix tu r e o f 2 2 5 p a r ts o f the a c ety l c o m p o u nd, 2 0 0 0
p a r ts b y v o l u m e o f a q u eo u s etha no l o f 5 0 % s tr eng th a nd
5 0 1 0 p a r ts b y v o l u m e o f hy dr o c hl o r ic a c id o f 3 0 % s tr eng th
is r e? u x ed f o r 8 ho u r s , w her eu p o n the a l c o ho l is dis til l ed
o f f . The s o l u tio n c o nta ins the hy dr o c hl o r ide o f the di
H3 0
1
C l - S O2 I | \ I H OH
( 3 H3
1 1 0 3 s
a m ine o f the Fo r m u l a 1 0 a nd c a n b e u s ed a s it is f o r the
p r ep a r a tio n o f the tetr a z o c o m p o u nd. The dia m ine it
s el f c a n b e is o l a ted f r o m this s o l u tio n w ith s o diu m hy
dr o x ide; o n r ec r y s ta l l iz a tio n f r o m p etr o l eu m o ther it
f o r m s c o l o r l es s c r y s ta l s m el ting a t 5 5 C .
H H3 9 ( I ) H3
' l
( C H2 ) s C Hs
C Ha
( 1 Ha i I
I 6
Ex a m p l e 2
The f o l l o w ing dis a z o dy es a r e p r ep a r ed v 8 . 5 des c r ib ed in
Ex a m p l e 1 b y c o u p l ing o n b o th s ides the tetr a z o c o m
p o u nds o f the u nder m entio - ned dia m ines w ith 1 - ( 3 - a c ety l
5 a m ino - b enz o y l a m ino ) - 8 - hy dr o x y na p htha l ene- 3 : 6- dis u 1
io nic a c id. Fo r this p u r p o s e ther e a r e u s ed the dia m ines
o f the f o r m u l a
( 1 2 )
1 0
E3 0 ( I DHE
I
w her ein R r ep r es ents the f o l l o w ing a to m ic g r o u p ing s :
The r es u l ting p u r p l e dy es ha v e the s a m e v a l u a b l e p r o p
er ties a s tho s e m entio ned in c o nnec tio n w ith the dy e o f
the Fo r m u l a 1 1 .
The dia m ines o f the Fo r m u l a 1 2 c a n b e p r ep a r ed a s
des c r ib ed in Ex a m p l e 1 a nd a r e a dv a nta g eo u s l y p u r i? ed
v ia the a c ety l c o m p o u nd a s des c r ib ed in Ex a m p l e 1 .
3 5
4O
l - a m ino - Z - m ethy l b o nz ene m el ting p o int
c o ndens ed w ith a c ety l c o m
p o u nd, C .
n- a m y l m ethy l k eto ne _ _ _ _ _ _ _ _ _ _ _ _ _ . 2 0 7
n- hex y l m ethy l k eto ne _ _ _ _ _ _ _ _ _ _ _ _ _ . 1 9 7
( c ) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . n- hep ty l m ethy l k eto ne _ _ _ _ _ _ _ _ _ _ _ _ _ 1 7 8
Ex a m p l e 3
1 8 p a r ts o f the 2 : 2 - di; ( 3 - m ethy l - 4' - ia m ino p heny l )- n
u ndec a ne o f the Fo r m u l a 1 0 o r the c o r r es p o nding q u a n
tity o f 2 : 2 - di- ( 4 - a m ino p heny l )- n- u ndec a ne a r e tetr a z o
tiz ed in a n a q u eo u s hy dr o c hl o r ic a c id s o l u tio n a nd c o u
p l ed in a s o l u tio n, a l l na l iniz ed w ith s o diu m c a r b o na te,
With 5 2 p a r ts o f 1 - ( 4 - c hl o r o - 2 : 5 ' ~ dim ethy l p heny l - s u l f o
ny l a m ino ) - 8 - hy dr o x y na p htha l ene- 3 : 6- dis u l f o nic a c id.
The dy e f o r m ed is is o l a ted, a nd p u r i? ed b y b eing dis
s o l v ed in w a ter a nd p r ec ip ita ted a g a in w ith s o diu m c hl o
r ide; it is o b ta ined f r ee f r o m s a l t b y b eing dis s o l v ed in
w a ter , p r ec ip ita ted w ith s o diu m a c eta te a nd w a s hed o u t
w ith etha no l . I n the f o r m o f its f r ee a c id it c o r r es p o nds
to the f o r m u l a
( 1 3 )
5 5
60
l
( C H2 )8 0 H3 Ho 3 s S 0 3 1 1
I t is r ea dil y s o l u b l e in w a ter a nd is o f a p u r e p u r p l e
tint. When inc o r p o r a ted in a g el a tine l a y er it do es no t
dif f u s e into a n a dj a c ent l a y er a nd c a n b e b l ea c hed in
the p r es enc e o f a s il v er im a g e w itho u t f o r m ing u ndes ir a b l e
7 5 c o l o r ed dec o m p o s itio n p r o du c ts .
3 , 1 1 9 , 8 1 1
8
Ex a m p l e 4 v io l et im p u r ities b y r ep ea ted r ep r ec ip ita tio n. I t dy es g el
a tine a p u r e b l u is h g r een tint. As the y el l o w dy e f o r the
no n- s ens itiz ed s il v er b r o m ide em u l s io n ther e m a y b e u s ed,
f o r ex a m p l e, the dy e o b ta ined in the f o l l o w ing m a nner :
1 7 5 p a r ts o f l - a m ino b enz ene- 3 - s u l f o nic a c id a r e dia z o
A c el l u l o s e a c eta te ? l m is c o a ted w ith the f o l l o w ing
l a y er s in the u nder m entio ned o r der o f s u c c es s io n:
( 1 ) A s il v er b r o m ide em u l s io n s ens itiz ed to r ed w hic h
c o nta ins the c y a n dy es tu ? ? o f the f o r m u l a
HOz S - S Oz H Ho g s - S O: ; H
O- C Ha
( 2 ) A s il v er b r o m ide em u l s io n s ens itiz ed to g r een ~ A n . . l . s
w hic h c s m ta ins the P u r p l e dy es tu ? o f the Fo r m u l a 1 1 de- 3 3 5 1 1 1 5 1 5 1 ? $ 3 3 3 1 ? l ? dl z g ih i f ie
s c nb ed m th? a b o v e Ex a m p l e 1 . . f o r m ed is s a l ted o u t, ? l ter ed o tt' , dis s o l v ed in w a ter a nd
( 3 ) A y el o w ? itf z r l a y ? f o r m ed . b y c o l l o l q a l s il v er . 2 0 tr ea ted a t r o o m tem p er a tu r e w ith p ho s g ene w hil e k eep
_ ( 4) A no n- s ens 1 t1 2 c d s il v er b r o m ide em u l s io n c o nta m - ing the r ea c tio n s o l u tio n a t a neu tr a l r ea c tio n b y a dding
m g a y c no w a z o dy e . . s o diu m c a r b o na te. On c o m p l etio n o f the p ho s g ena tio n
The ? l m p r o du c ed a s des c nb ed a b o v e is P r o c es s ed b y the r ea c tio n m ix tu r e is a l l o w ed to tu r n a c idic , the dy e
the u s u a l m etho ds o f the s il v er dy e b l ea c h p r o c es s . I ts w hic h ha s s ep a r a ted in b r o w n ? o c k s is ? l ter ed o f f a nd
p ho to s ens itiv ity in a l l its dy ed l a y er s is s u f f ic ient f o r the 2 5 tho r o u g hl y Wa s hed w ith Wa ter _ The r es idu e is dig es ted
u s u a l l ig hting c o nditio ns . 1 6. m a ter ia l is ex p o s ? d? f o r w ith s g diu m c a r b o na te s o l u tio n o f 2 % s tr eng th, w her e
ex a m p l e u nder , a c o l o r ed p o s m v e m a s ter da v el o p ed , m a u p o n a s m a l l a m o u nt o f dy e p r es ent, w hic h dif f u s es s l ig ht
m eto l hy dr o q m no ne dev el o p er ? x ed a nd b l ea c hed 1 1 1 . a l y in g el a tine, p a s s es into s o l u tio n, w her ea s o w ing to the
dy e b l ea c h b a th. p r ep a r ed f r o m hy dr o c hl o nc a w ! ? u ? - s a l ting ~ o u t ef f ec t o f s o diu m c a r b o na te the m a in p r o du c t
u r ea a nd P hena z m e' Af ter r em o v a l o f the ex c es s s l l v er m 3 0 do es no t dis s o l v e. The r es idu e is dr ied; it f o r m s a b r o w n
a Fa r m er s r edu c er a r ec o r d in na tu r a l c o l o r s is o b ta ined. . . . . . t
I t is o f a dv a nta g e to s u b j ec t the r ec o r d a f ter the l a s t w a ter ig tl g il io tl ? g g 1 S r ea dl l y S o l u b l e I n Wa ter Wu h a p u r e y el '
b a th a nd b ef o r e dr y ing , f o r 3 m inu tes to a tr ea tm ent in a Wha t is C l a im ed is _
. . f P t .
s o diu m c a r b o na te s o l u tio n o f 1 % s tr eng . h a nd th- n to a 1 . A dis a z o dy es tu ? , o f the f o r m u l a
45 in w hic h - U is a m em b er s el ec ted f r o m the g r o u p c o n
s is ting o f C O a nd - S O2 , a t l ea s t tw o a nd a t m o s t
? v e V1 s a nd a t l ea s t tw o a nd a t m o s t ? v e V2 s a r e H,
0 to tw o V1 s a nd O to tw o Vz s a r e - - - C H3 , 0 to o ne V1
a nd O to o ne V2 a r e C l , 0 to o ne V1 , a nd 0 to o ne V2 a r e
5 0 C H3 C ONH, a nd m a nd 1 1 ea c h s ta nds f o r a w ho l e nu m
b er , the s u m ( m +n) b eing a t l ea s t 5 .
2 . A dis a z o dy es tu f f w hic h c o r r es p o nds to the f o r m u l a
The a z o dy e o f the Fo r m u l a 1 4 c a n b e p r ep a r ed a s
f o l l o w s :
1 9 8 p a r ts o f l - a m ino - Z : 5 - dim etho Xy - 4- nitr o b enz ene
a r e dia z o tiz ed in a hy dr o c hl o r ic a c id s u s p ens io n a nd the
dia z o c o m p o u nd is c o u p l ed w ith 3 61 p a r ts o f l - a c ety l
a m ino - S - hy dr o x y na p htha l ene - 3 : 6 - dis u l f o nic a c id. The
r es u l ting nitr o m o no a z o dy e is r edu c ed in a n a l k a l ine m e
V1 "7 1 V2 V2
V1 - 0 O- NI I 0 1 1 1 1 3 C OH: HO I - I NOC - V:
1 ( l m |
V1 V1 N=N T N: - V2 V1
1 1 0 3 8 S O3 H ( C H2 ) DC H3 HOg S S O3 H
tdiu m w ith s o diu m s u l ? de to f o r m the a m ino m o no a z o dy e in w hic h 2 to 5 V1 s a nd 2 to 5 V2 s r ep r es ent hy dr o g en
w hic h is p u r i? ed b y r ep r ec ip ita tio n, then dia z o tiz ed, a nd a to m s , 0 to 2 V1 s a nd O to 2 Vz s m ethy l g r o u p s , 0 to 1
the dia z o c o m p o u nd is c o u p l ed in a m ix tu r e o f p y r idine V1 a nd 0 to 1 V2 r ep r es ent a c hl o r ine a to m , O to 1 V1
a nd a q u eo u s a m m o nia w ith 5 42 p a r ts o f 1 - ( 4- b enz o y l - 5 a nd 0 to 1 V2 a n a c ety l a m ino g r o u p , a nd p s ta nds f o r a
a m ino - b enz o y l a m ino ) - 8 - hy dr o x y na p htha l ene- 3 : 6- di- w ho l e nu m b er o f a t l ea s t 5 a nd a t the m o s t 8 .
s u l f o nic a c id, The r es u l ting dis a z o dy e is f r eed f r o m 3 . The dis a z o dy es tu f f o f the f o r m u l a
J 1 3 C - C O- NH NH- C OC H3
GOO- EN o n m e c m 1 1 0 HNOC
l l ( 3 H3 I
1 1 0 3 8 S O3 H ( C H2 )B C H3 HOa S - S Oa H
3 , 1 1 9 , 8 1 1
0 4. The dis a z o dy es tu l ' f o f the f o r m u l a
H3 0 ' C H3
5 . The dis a z o dy s s tu f f o f the f o r m u l a
1 1 3 0 - 0 0 - 1 : r | m _ 0 o 0 H3
O0 OHN 0 H H3 0 C H3 HO HNO 0 _ < >
] ( [ 1 1 1 3 I l
: N < l : _ < > - - N=N
I I O3 S ~ S O3 H ( C H2 ) 4C H3 H0 3 5 - S O: 4H
6. The dis a z o dy es tu f f o f the f o r m u l a
H3 O C OI TI ] EI I \ | I HC 0 0 H3
0 OI ' I N 0 1 1 H3 O C H3 1 - 1 0 LI N- 0 0 _ < >
| | ( 3 1 1 3 | I |
no a s - S Oa H ( 0 H2 ) 5 0 H3 H0 3 s - - s o n
7 . The dis a z o dy es tu l f o f the f o r m u l a
H3 0 _ 0 0 - 1 TI H 1 . 1 1 0 0 0 0 I I :
I
O- o O- HN OH H3 O C H3 HO HN- Oc - O
l I ( I J Hs | I |
N=N - < f @ =N
Ref er enc es C ited in the ? l e o f this p a tent
UNI TED S TATES P ATENTS
1 , 8 5 6, 2 1 7 K a l is c hc her et a l _ _ _ _ _ _ _ _ _ Ma y 3 , 1 9 3 2
2 , 2 8 6, 8 3 7 S ey m o u r et a 1 . _ _ _ _ _ _ _ _ _ J u ne 1 6, 1 9 42
FOREI GN P ATENTS
8 9 , 5 5 7 S w itz er l a nd _ _ v _ _ _ _ , _ _ _ _ _ _ J u ne 1 , 1 9 2 1