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CY 205 Synthetic Dyes Class Notes-Part-4 Synthesis of Various Dyes PDF
CY 205 Synthetic Dyes Class Notes-Part-4 Synthesis of Various Dyes PDF
CY 205 Synthetic Dyes Class Notes-Part-4 Synthesis of Various Dyes PDF
~:1.~-tL;;
51 -
·-·.. ': . "J\J_;/ ·
u c· w ~·;~, ~ J
NHCH 2 S03H
I
/"--ocH·3 II
NHCH2S03H
I
/"--CH
I II R
. !~..:
-
b",,.'J 'l'-jbiw
·:u ~ !·~d;dqs•
,rq ucJ
-
: ~ -= ~ .s.o
i-J '"; .,-:j[J!tf; .:.. _,
N
#C~CL ,'~; J 1Jfl
~\
NM N MC'. l
I
' t/ vt
fit ' peMe... . ~,.. .4i)
• }. •.. ~~"'.;:-·J •· ~;--
· - .. - , .. 0
e ~
~
1'.'
~ -~-· ,-::.~ rJ
?i •. .;_ -·
\t . .,. , :: ,- ; . '
. :• . ·.:i ..,.__,J d·
., T -:::7 I· . .\ :;_
-
(
/
l\\\ Examples of secondary and tertiary amines use? as coupling
.~ N-~·N--a
· f ··,
... c : ..
:: ..;t \
.components are as follows.
-y ~ - - ' I H
.· N
N= -
0/ \. YN=N0 1
'
/"'-.
- c.~~~: .f. .!~.· ·:· .....d.... · !J~ Jf.~jt}1 0 .e-:. - - I II
'/
J .... : · ·
or.::.~.. :;•
. ~ouplin~ with J>~_!l_C!.l~ ~e ;;~ ~suaH~ carried out u_nder alkaline N(CH8) 2
I
cond1t10ns while the' •cpupnng Wlf~ 18.mmes are earned out under NH
l I
slightly acidic conditioq~· /"'-
,... ~ ., - /"'-.
~1;., ". c /Jhe ..~\eqt-rpn,:~r1ithc\r,a;vicing.- .gr~J.!.PS r. such as nitro in o- and
.
Hydroxy derivatives
O:S.i..!L'· N + ·.d I - .Li·'"''
"•_ '",·O®J?J
"1 . ,-~
;i I rlq n,.,. L
.( ·~'!.--1 - '"'· ni:· ,~ ..,'' J--,,,.;.j-
"° _ ,,,,<
•
3
lo ?.'.:ii.:l 2;;_ -ND; - 4A1;;: 1i:.,i'.:.>f,-:>1 Jmiq 1.;o:; ,i_!L;r·r · Phenol couples under alkaline conditions principally in the
, ' ...r···r~·...'<."'./
"!·,: ·. .- , ..~A';"'
., ""_,,.
.. ' .·._·. .. ,·1q•JO~' • rir
. . ,,.,.-.,.--...._ ,, - -""' ·1'-.· ""
• ~1,"'
. ~ .rJ 4-position. In resorcinol, coupling takes place in the 4-position and
b~ .~l>';I -:+ 1·:·~;; It ' ~ :. O~Nb-"'-~ 3Y ' ,,~:"-N::;::N-'
.a,.. )-OCHs then according to the pH at which the coupling is done, e,g., pH
~di '/6· w.c::,.),~/G·• ;: .. 1 ·) tJ2 ~me;.:-:::,,- l~1;q1u. l' . ""'-== 5- 8, position 2 ; pH > 8, position 6. .Resorcinol couples princi-
pally in the 4-position.
_.,Erlq0·1.o·, ., ~ ';·i8'nisole; ~02 ·::; ocH mum• ·nin o; t.·1~1
-no-::'.l::No;r. '; 0q .. ~~2~,·t:t·<' w ::il:.nrn '.)it1:aNOr;. j -'. ! , ·_ rl OH
~;:m ~·ii!~ i: .; ·1 <- .:r1 ~ ,i·;;rb:im :: dT .,.HX -,;; [iO <;Ai! 2· I
OH OH
Couphng Com1J:>onents : ·: v;rJk/t < OCH8 (2) alk I -(2) acid I COOH
Benzent;,_ der1vat:ives 0 ·n
/"'-./ ~/"'-.!!:., /"'-/
I II · I II I
Amines . Primai:j aromatic amines are useful as coupling
components. Some import-ant examples ~e· as follows;
:
~
; ) 11 • -1
,.....,,__.... t"'
'"' • -
jl ~ ' T..--
'/talk
phenol
'/"
t
resorcinol
(l)alkQH '/ talk
11
OH NH 2
Naphtholdisulphonic acids 2)alk I I 1) acid
H08S OH . ~ /""-/'.!
OH I II II
I I I H0 3S-\./'-../-S0 8 H
/'-.. /''~ / "'-/'"
I II 11
Hacid
HO.S-~) 1
Lso H
1
' /""-/
Other examples are as follows :
1-naphthol -3)lisulphonk epsilo n acid
acid
OH NH 2
Ho,s + HOas-1''-}~) acid I I
2) alk /""-/"'-~
1) acid
·
. ' , /,_OH
t l / '- .;r~ II ,-NH2 '!II I 11 I
/'-.. ,., '-OH
I 11 I . I II I 2) alk ("-/ '/"-/
HOis-,./""-/-S01H H03S - '/""-/
OH
I
R acid G acid
J acid
S01 H
S acid
Synthetic Dyes .Azo Dyes
120 121
V (b) Methyl red. It may be obtained by the coupling o!- Procedure. Sulphanilic acid is diazotised with sodium nitrite
diazotised anthranilic acid with dimethylaniline. and hydrochloric acid at :i-8°C. Now · the diazotised sulphanilic
acid is run into a solution of ~-naphthol having caustic soda, soda
~/COOR _ ash and common salt at 8°C. After stirring the contents for 2 hours,
the temperature is rais.ed from 8 to l6°C. The pH of the solution
<=>-N=N.Cl + <=>-NMe 2 ---+ rises from 9 1 to 9·4 which is lowered by acidilying with HCl. The
salted dye is filtered and dried.
_ / COOR _ Orange II is used widely for dyeing wool, cotton fibres, silk,
/-"' / -"'- paper and leather.
,_/-N=N-,_/-NMe2
V (e) Orange IV. It is obtained by coupling diazotised sul-
phanilic ac.id with diphenylamine in alkaline solutiion. But diphenyla-
It is not used as a dye but is used as an indicator in acid-alkali mine is insoluble in water. Therefore, it is to be emulsified in water
titrations. before coupling is carried out.
+
\ . / (c) Orange I. (rr.-naphthol Orange). It is
coupling oa-naphthol with diazotised sulphanilic acid.
obtained by
H03 S-r
,,-
'-NH 2
"'--- /
----=----
NaNO.
o-s·c
HCI
H0 3 S~
'---/
-
/-,
-N2Cl
sulphaoilic acid
r--\. . ~
Na0 3S-'\.___.#'-N=N-Cl +'\_,,_/-OH - - -
NaOH
! /-"--NH-/-, _
, __"""
/ /
I '-- = /
j
t
"'-=/
diphenyl amine in
alkaline medium
Orange I is used widely for dyeing wool and cotton fibres. It is an acid azo dye. It is mainly used for dyeing wool and 1:!
\ / (d) Orange II. (~-naphthol orange). It is obtained by coup- cotton fabrics. Ia acid medium, it possesses limited fastness.
ling ~-naphthol with diazotised sulphanilic acid.
V (f) Fast red A. It was the first red azo dye and is still
,,- NaN0 2 + HCI /- important due to its cheapness and adequacy for many purposes. It
H 0 S-'
a "'-=/
"--NH 2 - - - - - - H O S -
.. Q.5oc a "'-='/-N Cl 2
is obtained by the condensation of diazotised naphthoic acid (1-
naphthylamine-4-sulphonic acid) with ~-naphthol.
sulphanilic acid
J /"'-/'-OH OH
\,\A.('A \ ,.,
t;;ce?Y"''-.
'.u-.O-~
I I
j "'-/"'-/
11 l
Na0 3S-<-->-N=N-Cl <=-> --
~ ~-naphthol
OH
I
in NaOH.
\
,/ __"' / +,
/ __
-"' /
HO
Nao S_/-'-N-N_/-,
~ "'-=/ - '--=/ Na03 S-<-->-N=N-<-->
01aoge II
'-"""
/
, __
/-='--
/ ,/='--
Fast Red A
__ /
124 Synthetic Dyes 125
Azo Dyes
\.....--- (g) Ponceau '2R'. It is obtained by coupling diazotised
.m-xylidene with the R acid (2-naphtbol -3, 6-disulphonic acid). ·
/-,-NH-/-,
+<=>
OH"'- / S0 3Na ""=/ "'-=/
H 3 C-<==)-N=N-CJ
--" / - " " ----+
+-----------
-HCI <=>-N
\-
2
Cl
HO "'-
[=/ "'-=/ "'-=/
H C-/ =-"'-
- /SOaNa H0 3S
8
, __ /-N=N-/--'\. metanil yellow
"'-cH __/
)-=/ It is used for dyeing silk and cotton fibres.
8 ' "
~ (i) Oran~e G. It is obtained by coupling diazotised aniline with
ponceau '2R' ""S0 Na3
the G-acid (2·naphthol-6, 8-disulphonic acid).
It is favourable scarlet dye. It has good fastness to light and HO
-washing.
\..._/ rh)
.
Metanil yellow. The starting compound for this acid
--
/-
"\
-" .
/-N=N-Cl
"/'--,/
+"'-
azo dye is nitrobenzene. It is sulphanated followed by reduction
with iron and sulphuric acid when metanilic acid is produced. This
acid is now diazotised and then coupled with diphenylamine when
--
,__
Na0 S - / = " '
3 /
---~
HO
/-,
"'-
Oleum
(25%S03) / ' - ,
/-N02 - - -0-
Pe+H2S04
-N0 2 -----+ /'
-,/-NH, , __/'- --s-,"--
--
>=<
/ --"'- N-N-/' '
=
' Ni trobenzene
Jl0-115
H0 3S
c ""=/
/
.
H03 S
"'-=
/ __/
Na0 3
Metanilic acid
I
I HCI
I NaN0 orange G
" S03 Na
1
i 0-5°Cl (j) Naphthol blue black 6B. (amino black 1 OB). It is
! obtained by coupling H-acid (l-amino-8-naphthol-3, 6-disulphonic
~- acid) with one molecule of diazotised p-nitroaniline in an acid ·
medium followed by coupling of the product with one molecule of
benzene diazonium chloride in an alkaline medium.
OH Na
I I -
/'"'-/' /= "'- acid
I II I + ClN -,_/'-N0
2 2 ---+
/ "-/"'- /'~
HO~ S~H
:126 Synthetic Dyes _Azo Dyes 127
0
N ao NH-NoH , -----" '/ } S03Na
-~ ""-/ ~/""- / =
I II I 3 --
· 2 + O= C
._ __ _ ___ _ J I r- --~---- .
--
/"\./"' / "- N 5 C:! O :
HOaS S0 3H a-
b all of p-h ydr;iz1no- I1 '--- - -- _..,)
1 H? N
naphthol blue black 6B
enzene sulphon1c HO- C= O
0 1o x ys ucc in1c
It is an important acid dye which is generally used for dyeing ac i d
a c id
-wool for black shades of moderate fastness.
V (k) Chro111e blue black R. lt is prepared by coupling
-diazotised 1-amino-2-naphthol -4-sulphonic acid with ~-naphthol. l-3"20
/OH OH"'
+ <--) O= C--N~~
~-
Na03S-( - -) -N=N-Cl -----+
, __
/ -=-""-
/ , __
/ =- ""-
/
1'•03S
0
--
N,-NJ
I
/-, / OH
/ - ""' / -, 1l
"\,_/ ,_/ O=C i ~
N-()-
chrome blue black R I
0
Na03S \ -- SO N •
N=N-CH I\) ' I 3 a
(1) Carbolan dyes. The main drawback of the above des-
·cribed dyes is that they are readily washed away with water.
This drawback bas been overcome by another group of acid azo HO-C=O
" c.f"
I
dyes called carbolan dyes; the general formula of these dyes is
·depicted as follows : ·
/ = ""' OH NHCOCH3 1l
R - , /-N=N
-
I I
""-/I ""'/'
II I
NaQ3S-o~ Ho-ri -N~-o~ N=N-C
'
I
N ~
S03 Na
"~
c
N
butter yellow
\ ._ ______ _, p-Hydraz1no- I or
COOCzli s p-dimethylaminoazobenzcne
COOCzH5 b•nzen• sulphon1c
I N. co 3
.
acid
It is used for colouring butter, oils and margarine.
Ditlhy l ox;ile-;;,c.t•t• f 2 CycliS> li on
O=C-N
I I-"\ o~ · S03H i)NaOH
ii)HCI
O=C-N
I
CHz
\
N
-0- S03N• -CzH50H V (b) Chrysodine G (2, 4-diaminoazobenzene). It is obtained
by coupling m-diphenylenediamine
chloride.
with benzene diazonium
"/
CHz N -
y c
I
H 2N"'-- _ H 2N"'--
.0
Na03S
.
(
-
~ HO-C-N-o~
N-N-C
H
1l
'-c<i'
I
N -
S03N
~.
oldest dyes which is a mixture of mainly two compounds, I and II .
This mixture is obtained by the action of HN02 on excess of
m-phenylenediamine i.e., by the diazotisation and coupling by
m-phenylenediamine
COONa
Tar 1r :a.zinc /=, /=, /=, /=,
,_/-N2c1+,_/-NH2 - ,_/-N=N-,_/-NH2
It is mainly used for dyeing wool fabrics yellow with moderate
H,N/ H2N/ H2N/ H2N/
fastness and silk fibres with poor fastness. monoazo compound, I
2. ~ a~s. These dyes have - NH2 or - NR1
group as the auxocfirome. The chromophoric system is present as /=, /~"'- /=, /=~
a cation. Only few basic azo dyes are known. These dyes are not ' /-N 2C1+2' /-NH 2 - '-
11 -N=N-, /--NH 1
much used and they are, therefore, not of much significance indus· ClN /- H N/- ,- HaN/-
2 2
trially. N
__.£ome of the basic azo dyes are described as follows :
V (a) Aniline yeD.low. It is the simplest and the first azo dye
that was made. It is obtained by coupling diazo tised aniline with
II
,_="'-
N-/ /-NH:i
H 2N/
aniline. bisazo compound, II
/=,. /="'- /="'- . /="'- It is a brown dye.
' /-]lil 2t::l + '-
- /-NH
-
2 -+ ' - /-N=N-, / -NH2'
-aniline yellow - tannin mordant.
3. D" to
(p-amino azobenzene)
earlier arc used to dye the proteinous fibres (e.g., wool, silk and
A$ this dye is acid-sensitive, it is. not of much significance leather) dircctlJ b•t taey need mordant for dyeing cellulo11ic fibres
130 Synthetic Dyes Azo Dyes
. 131
(e.g,, cotton, linen, paper, etc.,). However, certain azo dyes are
known which could dye directly the cellulosic fibres without a
mordant. Such azo dyes are called direct or substantive azo dyes. Congo red is used as an indi~ator in acid-alkali titrations •
.Congo paper is used for testing acidity of the solution.
Some important direct azo dyes are described as follows :
@ (a) Congo red. It is a simple benzidine bisazo-dye stuff. It (b) Direct deep black. It is trisazo dye and is obtained by
is obtained by coupling tetrazotised (bis-diazotised) benzidine with following series of coupling reactions in a particular order. First
two molecules of naphthionic acid. The blue dye so obtained is of all, the bis-diazotised benzidine is coupled with one mole of
converted into its red disodium salt during its salting out with H-acid {I-amino -8-naphthol -3, 6-disulphonic acid) in acid medium
sodium chloride. to yield a product, I. Then this product, I, is coupled with one
NH2 NH 2 molecule of benzene diazonium chloride in alkaline medium to yield
the product II. Finally, the product, II, is coupled with m-pheny-
I I
r
f"'"'/
11 'I
"- / ' /
~ClN 2 -( =
'-"'
)-<= _,f'
)-N2Cl+ "'"'/'
I II
"'-/ ' /
I
fonediamine to yield direct deep black.
NH2 0H
I I l I
S0 3H S0 3 H
t
I -
CIN2-<- )-,_/-N2Cl
/ ='\.
+ /I/"'/' I
' /"'-/"' 11
H
NH 2 / =, / =, NH 2 - HOsS SOa
/ "'/ "'-/
I N=N-,
-
/-"'-
-
/-N=N I
' "'"'/' l acid
' /'"'I
i 11
S0 3 H (blue)
I
, I/ ,/
S0 3 H
11 I
CIN2-,
/ ="'
_
/ -"'-N=N I 2 I
/-,_/ "'/"'/'
NH OH
- . I 11 I
HCllNaCI
disodium salt (I) HOsS /'/"'/"' SOaH
The red salt is very sensitive to acids, the colour turns from /="', , -/="' NH 2 OH /-"'
red to deep blue in the presence of strong mineral acids and dull ClN2-" , ..,-N=N I I N=N:-' /
purple by organic acids. The change in colour from red to blue in ,_, _, "'/"-/'/ -
the presence of inorganic acids may be explained due to the occur- I II I
rence of resonance as follows :
(II)NaOaS
/'/"'/"-S0 Na
Ee /= "- /="' Ee
NH2 NH 2 1
N=N- I - /-N=N I /="' I
/ ' / '/ H ,_/ ' - H ' / ' / "'-
H2N-, ""
_, II
! 11 I I II I "'NH2 t
' /"-/ , / ,/
19 t 81 /="' /="' /="' NH2 OH
H 11N-" I I N=N.C H
S03
~
/ ='
t
/='
SO a
~ "-, /-N=N-, / - , /-N=N
NH2
- - '/"'/'/
I II l
1 1
/ ' /' /
NH 2
II N-N-
H ,_/ ,_/ H
'- '-N-N
NH 2
\I
' /' /' direct deep black
Na0 3S /'/"'/"' S01 Na
I 11 I I 11 I
' /'/ ' / '/
I I It is the most widely used black dye.
8S0 3 8S0 3
blue colour in acidic solution. (c) Benzopurpurin. It is obtained by coupling bis-diazotised.
o-toluidin e with two molecules of naphthionic acid.
132 Synthetic Dyes
Azo Dyes 133
N& / =' / =' N~
I "N=N- ' - ' -N=N I (iii ) The J-acid required for step (ii) is prepared from tobias
/ ""-/' /
I 11 I H C
3
)-/ '-(' CHa ""-/I ""-/'
II I
.acid in the following manner :
' / ""-/
I
'-/"
I
S03 Na
I OH
S0 3 H
I NH 2
S0 3Na S0 9Na /"/'\./ NHa ; (NH4)2SOa /"/'/ sulphonation
-I II I ------~ I II I -----+
It is interesting to note that this dye exhibits similar colour
changes. However, it is less sensitive towards acids. It is also a.
'\./""-/
sodium salt of
under pressure
'./"'-/
tobias acid
larged used dye for pink on cotton and scarlet on wool. 2-napbthol-1-sulphonic
acid
(d) Rosantlirene 0. The preparation of this dye involves
the following steps ; SOaH
i!H03 S I NH 2 H08S NH 2
(i) First of all J-acid is condensed with m-nitrobenzoyl "'-/ " / ' / heat with ""-/"/'\./ aq.NaOH
chloride in the presence of sodium acetate to yield a product which I II I ----+ I II I ----~
is then reduced with iron and dilute hydrochloric acid to yield the- ' / "'-/ dil. a.so, '/"'-/ under prcssulO
at 190-200•
product I. I I _
S08 H S08H
(ii ) The product on coupling with benzene-diazonium chloride: Na08S - NH1 H08S NH 8
yields rosantbrene 0.
"'-/""-/' / H2SO, "/""-/ ' /
I II I ---+ I 11 I
Na0 3S NH 2 _ / N02
" /""-/'-/ '/""-/ ' / "'-/
{i) c1oc_/ - "'- I I
I II I ONa OH
' /""-/ '-/ J-acid
I
OH
---------+
(ii) Fe'-HCI The J-acid as well as its N-phenyl and N-methyl derivatives
J-acid are important intermediates of direct dyes for cellulosic fibres.
NH 3 (e) Procion dyes. The direct azo dyes described above
_/ C 6 HsN,Cl have been found to attach themselves to the fibres by hydrogen
NaOaS NH.OC-/ - "'- -----+ bonds. However, certain direct azo dyes are known which are
" / "/' / ,_/ - water soluble and get attached to the fibres through chloro-1, 3, S-
\ II I triazine molecule. Such dyes are called procion dyes. An example
of these dyes is given as follows :
' /""-/
I
OH
(I)
N~~ /N~
""-/ " / ' NH.OC-/ - ,
I II ( ""-= /
C,H5N =N /~/"/
---
OH
rosanthrene 0