Photochemical Reaction of Monosubstituted Aminoazidobenzoic Acid

14 Photochemical Reaction of Monosubstituted Aminoazidobenzoic Acid Derivatives in Novolak TAKAHIRO TSUNODA and TSUGUO ΥΑΜΑΟΚΑ Faculty of Engineering, Chiba University, Japan

We found that when 4.4'-diazidodiphenylamine in novolak was irradiated by UV light, novolak was insolubilized in alkali aqueous solution and colored in black1) But it is impossible to use it as photopolymer for plate-making because 4.4'-diazidodiphenylamine is very dangerous causing explosion during storage. We investigated the photosensitive azide compounds that was stable and made a deep color image by UV irradiation. We synthesized monosubstitutedamino azidobenzoic acid derivatives which made a deep color image and caused insolubilization of novolak in alk ali aqueous solution by UV irradiation. These photo sensitive azide compounds including some couplers gave more deep color image by UV irradiation. 2.4Dichloronaphthol was the most important coupler to photodecomposed monosubstitutedamino-azidobenzoic acids. The photosensitive layer ( thickness: about 3 . 7 μ ) containing 2-(p-methylphenylamino)-5-azidobenzoic acid, 2.4-dichloronaphthol and novolak had the color density 1.48 by UV irradiation. The polyaster film coated with this photocolored polymer was exposed by UV light through a negative film and then 197

UV L I G H T INDUCED REACTIONS IN P O L Y M E R S

198

washed out by d i l u t e a l k a l i move the unexposed a r e a . polyester

s o l u t i o n to

The p r o d u c e d c o l o r

f i l m may be u s e d as n e g a t i v e

intermediate salt

aqueous

or

re-

image on

positive

f i l m f o r plate-making instead of

silver

emulsion f i l m .

Experimental 1) S y n t h e s i s o f benzoic a c i d a)

2-monosubstitutedamino-azido-

derivatives

2-Monosubstituted(R)amino-5-nitrobenzoic A mixture

of

acid(I)

2-chloro-5-nitro-

b e n z o i c a c i d and amine d e r i v a t i R-NH-^^-N0

2

uOOH

ves

i n g l y c e r o l was s t i r r e d

heat adding potassium

I

After reaction, filtered

the

carbonate.

s o l u t i o n was

and a c i d i f i e d w i t h h y -

d r o c h l o r i c a c i d . The p r e c i p i t a t i o n was t h e product.

with

T a b l e 1 shows t h e r e a c t i o n

reaction

condition,

pro-

d u c t s and y i e l d . b)

2-Monosubstituted(R)amino-5-aminobenzoic

( HCl-salt

acid

)(II) A mixture

of I ,

m e t h a n o l and

h y d r o c h l o r i c a c i d was R - N H - ^ - î î H - HOI 2

COOH

refluxed

w i t h t i n powder f o r 3-5

hours

and t h e n f i l t e r e d . Prom the dified filtrate ric

acid,

with hydrochlo-

the reduced

product,

amine d e r i v a t i v e was s e p a r a t e d as h y d r o c h l o r i c salt. and c)

T a b l e 2 shows the r e a c t i o n

aci-

condition,

acid

products

yield. 2-Monosubstituted(R)amino-5-azidobenzoic

acid

(III) II

was d i a z o t i z e d w i t h n i t r o s y l s u l f u r i c a c i d

sodium n i t r i t e

i n aqueous

or

s o l u t i o n of a c e t i c a c i d

or

14. TSUNODA & YAMAOKA

hydrochloric II

Amino-azidobenzoic Acid Derivatives

199

acid. After filtration,

the d i a z o t i z e d

was a z i d o t i z e d w i t h sodium a z i d e .

The p r e c i p i t a -

t i o n was a z i d e compound I I I . R-NH--^^—Table

3 shows t h e r e a c t i o n c o n d -

ition,

COOH

products

and y i e l d .

Ill Table 1 R-

Table 2

Temp. Reac- Y i e l d M e l 'C tion % ting hour point G hrs 4

®CH3O-®

S R,-

Reac- Y i e l d M e l tion % ting lour point hrs •c

140

5

46.1

251-3

3

63.9

232-5

130

6

94.4

246.5 -7.5

4

61.9

216-7

HO

5

81.9

146-8

5

97.2

207-8

140

4

80.8

186-7

5

69.8

226-9

140

5

13.0

258-9

3

45.7

214-5

Compound

Reaction Yield Melhour(hrs) % ting Diazo Azido point •c 1

1

74.4

over 250

1

1

90.1

253-4 2 - phenylamino - 5 azidobenzoic acid

2-(p-chlorophenylamino ) - 5 - a z i d o b e n zoic acid

b 257-9 2 - ( p - m e t h y l p h e n y l amino)-5-azidobenzoic acid IIII 3 C I

CH 0-@3

1

4

46.8

1

1

56.5

156 2-(p-methoxyphenyldecom. a m i n o ) - 5 - a z i d o b e n zoic acid I H ^

U V L I G H T INDUCED REACTIONS I N P O L Y M E R S

200

162 2- (of - n a p h t h y l a m i decoml n o ) - 5 - a z i d o b e n z O ' i c acid III

51.7

2)

Novolak r e s i n

m - C r e s o l t y p e n o v o l a k , A l n o v o l 429K tferke 3)

(Chemische

A l b e r t W i e s b a d e n - B i e b r i c h t ) was u s e d .

Couplers

2 . 4 - D i c h l o r o n a p h t h o l ( m p . 107°C ) , (mp. 1 2 5 ° C ) ,

4-methoxynaphthol

l-phenyl-3-methylpyrazolone(mp. 129°C)

and 2 . 5 - d i c h l o r o a c e t a c e t a n i l i d e ( m p . 9 5 C )

were u s e d

e

as c o u p l e r t o

photodecomposed

-5-azidobenzoic 4)

Measurement o f I n f r a r e d

Infrared type 5)

spectrophotometer.

Measurement o f s p e c t r a l

Spectral non a r c

sensitivity

s e n s i t i v i t i e s were measured by Narumi RMe q u i p p e d w i t h g r a t i n g and 450W X e -

lamp.

Measurement o f o p t i c a l d e n s i t y o f c o l o r e d

Macbeth d e n s i t o m e t e r transmittance 7)

spectra

s p e c t r a were measured by H i t a c h i EPI-S2

35 monochromator 6)

2-monosubstitutedamino

acids.

Exposure

image.

was u s e d f o r measurement

of

density.

equipment

Vacume p r i n t e r e q u i p e d w i t h t e n 40W c h e m i c a l lamps ( D a i n i p p o n S c r e e n P - 1 1 3 - B ) was u s e d . The f r o m lamp t o n e g a t i v e 8)

cm.

P h o t o d e c o m p o s i t i o n and s e p a r a t i o n o f

osed

photodecomp-

products

I n 500 m l o f b e n z e n e , solved. the

f i l m was 4 . 4

distance

0.5g

o f a z i d e compound was

I n a f l a s k e q u i p p e d w i t h UV l i g h t

source,

a z i d e i n benzene was photodecomposed p a s s i n g

nitrogene

gass.

The photodecomposed p r o d u c t s

were

separated

by column chromatography w i t h developement


solvents Result


o f c h l o r o f o r m and a c e t o n e .

and

discussion

T a b l e 4 and 5 show the c o l o r o f photodecomposed zoic

acid.

and o p t i c a l

i n t a b l e 4 were p r o d u c e d by UV

a filter

a n o l s o l u t i o n of azide

paper a b s o r b e d w i t h 30% compounds.

The c o l o r s

5 were p r o d u c e d by UV i r r a d i a t i o n t o inum p l a t e o r p o l y e s t e r of mixture

o f n o v o l a k and a z i d e compounds

I

X

m

I

I

b

J

I

ni

Ι

a

τ

1

c

d

β

meth

i n table

a grained

f i l m c o a t e d w i t h 10%

alum

solution

(10:3

)

so

methylethylketone.

T a b l e 4 The c o l o r o f p h o todecomposed a z i d e s c o a t e d on f i l t e r paper w i t h o u t novolak

Compound

density

2-monosubstitutedamino-5-azidoben-*

The c o l o r s

i r r a d i a t i o n to

lved i n

201

Exposure time (min.)

1 3 5 1 3 5 1 3 5 1 3 5 1 3 5

Color

l i g h t G. l i g h t G. l i g h t G. (G: gray) l i g h t G. black black

T a b l e 5 The d e n s i t y o f photodecomposed a z i d e s c o a t e d on p o l y e s t e r f i l m w i t h novolak

Expos Color ure time (min.)

Optical density coating thickness (micron) a f t e r was* out

2

black

0.30

l i g h t G. black black

2

black

0.30


2

green black

0.32


1

black

0.36

UV L I G H T INDUCED REACTIONS IN P O L Y M E R S

202

The t r a n s m i t t a n c e

densities

were measured on p o l y e s t e r

of the c o l o r e d

image

f i l m a f t e r UV i r r a d i a t i o n

o r a f t e r i r r a d i a t i o n and washing out

i n 2% aqueous

s o l u t i o n o f sodium p h o s p h a t e . Pig.

1 shows t h e

spectral

sensitivities

of

a z i d e compounds. The mechanism o f t h e c o l o r i s not c l e a r ,

but i t

c t i o n products

is

assumed t h a t

of nitrenes

these reaction

the v a r i o u s

f r o m photodecomposed

rea azi

de compounds p r o d u c e t h e mixed c o l o r i n g m a t t e r .

300

400 III

300 III

a

300

400 I I ] C

300

b

300

400 d

400

m

e

400 Ι

ΐ

τ

ο

Figure 1. Spectral sensitivities of 2-monosubstituted-amino-5-azidobenzoic acids

In t h i s

photocolor reaction

amino-5-azidobenzoic a c i d ,

of

2-monosubstituted-

t h e i m i n o and c a r b o x i l i c

groups i n the molecules are v e r y i m p o r t a n t .

The com

pounds (IV and V) w h i c h h y d r o g e n o f t h e s e g r o u p s s u b s t i t u t e d w i t h a l k y l group are when t h e y a r e

are

very hypsochromic

photodecomposed. The r e a s o n why t h e

photodecomposed I V and V a r e h y p s o c h r o m i c may be due to

the f a c t

ture l i k e VI

t h a t t h e y c a n not have i n n e r s a l t .

struc



203

UV L I G H T INDUCED REACTIONS I N P O L Y M E R S

204

When t h e m i x t u r e

of

2-monosubstitutedamino-5-azido-

b e n z o i c a c i d and n o v o l a k was i r r a d i a t e d by UV l i g h t , p h o t o c o l o r and p h o t o c u r e o c c u r e d a t t h e same t i m e . I n this case,

i t i s considered that

quinonimine d e r i v a t -

i v e s a r e a l s o p r o d u c e d by t h e p h o t o r e a c t i o n

between

a z i d e compounds and novolakr-^

C00H

C00H

R-HH m-cresol novolak

nitrene

type

000H

RNH-^^-NH

2

quinonimine compound Pig.

2 shows t h e I n f r a r e d s p e c t r a o f 2 - p h e n y l a m i n o -

5-azidobenzoic acid I I I duct i n K B r t a b l e t

b

and t h e photodecomposed pro-

by UV i r r a d i a t i o n .

Figure 2. Infrared spectra of 2-phenylamino-5-azidobenzoic acid and the photodecomposed product

14.


TSUNODA & YAMAOKA

2-Phenylamino-5-azidobenzoic

a c i d III^

decomposed i n benzene w i t h o u t o x y g e n ,

was

205 photo-

and t h e n

the

photodecomposed p r o d u c t s were s e p a r a t e d by column chromatography. the

P i g . 3 shows the

Infrared

spectrum

photodecomposed component o b t a i n e d f r o m t h e

of

deve-

loped l a y e r of the column.

Wave ^ i a U ^ ft**""') Figure 3.

Infrared spectrum of the one component from photodecomposed 2-phenyU amino-5-azidobenzoic acid

A mixture

of

2-monosubstitutedamino-5-azidobenzoic

a c i d and c o u p l e r gave deep c o l o r image by UV i r r a d i ation.

It

seems t h a t t h e dye p r o d u c e d by c o u p l i n g

photodecomposed a z i d e w i t h c o u p l e r added t o

the

pho-

t o c o l o r of monosubstitutedamino-azidobenzoic P o r example,

the c o u p l i n g r e a c t i o n

COOH

acid. 3) i s as f o l l o w s ^ - ' ;

COOH

dye

OH

UV L I G H T INDUCED REACTIONS I N

206 The f o l l o w i n g example

i s the c o a t i n g

solution

a i n i n g a z i d e compound, n o v o l a k and c o u p l e r . rage t h i c k n e s s g i v e n are

of coating

by w e i g h t

percent.

5 32

novolak(alnovo1) coupler

4

methylcellosolve 6

59

shows the t r a n s m i t t a n c e

c o l o r images

cont

The a v e

l a y e r was 3·7ρ. A l l p a r t s

a z i d e compound

Table

POLYMERS

densities

of

the

p r o d u c e d by UV i r r a d i a t i o n t o the

coat

ing l a y e r o f the m i x t u r e

o f a z i d e compound, n o v o l a k

and c o u p l e r on p o l y e s t e r

film,

out

and t h e n by w a s h i n g

i n 2% aqueous s o l u t i o n o f sodium p h o s p h a t e .

color

image f r o m t h e m i x t u r e

ino)-5azidobenzoic

acid(III

of

The

2-(p-methylphenylam-

) and

2.4-dichloronaphth-

c o l gave the h i g h e s t

d e n s i t y 1.48

.

Conclusion 2-Monosubstitutedamino-5-azidobenzoic ivatives

acid

der

are v e r y u s e f u l f o r p h o t o c o l o r i n g m a t t e r .

The d e n s i t y o f t h e

p h o t o c o l o r image i n c r e a s e s by a d d

i n g a proper coupler to

the

a z i d e compound. I t

p o s s i b l e t o f i x the c o l o r e d image u s i n g t h e

is

photo-

polymers c o n t a i n i n g t h e s e a z i d e compounds and n o v o lak.

In future,

it

may be p o s s i b l e t o use t h i s

c o l o r f i l m f o r p l a t e making i n s t e a d o f s i l v e r emulsion

photohalide

film.

Acknowledgment The a u t h o r s

are

deeply indebted to M r . Shigeo

Maeda and M r . Susumu Suzuka i n Hodogaya C h e m i c a l I n dustry Co. f o r t h e i r various

compounds.

assistance with synthesis

of


\


Table

A \ Ε

I : C I

6 C-CH3 •H

OH

0

CI

00H

Pi]Lter R G

Pi]Lter G R

3

°d1 Pi].ter R G

1 2 3 4 5

0.42 0.58 0.58 0.65 0.62

0.59 0.75 0.80 0.95 0.88

0.63 0.63 0.56 0.63 0.62

0 . 8 8 0.57 0 . 5 4 0.89 0.81 0.55 0.52 0.90 0 . 8 6 0 . 4 9 0.48

1 2 3 4 5

0.96 0.97 1.00 1.07 1.10

1.19 1.20 1.33 1.48 1.48

0.54 0.57 0.56 0.58 0.57

0.67 0.64 0.69 0.68 0.69

1 2 d 3 4 5

0.79 0.82 0.74 0.76 0.84

1.05 1.12

1 2 3 4 5

0.61 0.60 0.62 0.65 0.60

0.90 0.89 0.92 0.91 0.88

1.05

1.17 1.18 0.56 0.51 0.59 0.58 0.55

207

0.38 0.40 0.40 0.41 0.39

0.25 0.29 0.33 0.32 0.34

0.45 0.48 0.51 0.58 0.56

0.42 0.43 0.44 0.55 0.52

NHC0CH C0CH, 2

0

Pi].ter R G

0.53 0.57 0.67 0.69 0.62

0.38 0.40 0.98 0.47 0.41

0 . 6 6 0.26 0.24 0.56 0.69 0.39 0.33 0.73 0.67 0.38 0.34

C:Coupler, A:Azide compound, E:Exposure time(min.) R:Red f i l t e r , G:Green f i l t e r

Literature cited 1) T.Tsunoa, T.Yamaoka and Y.Yamaguchi: Japanese Patent pending 2) Takahiro Tsunoda: Technical Papers of Photopolymer Conference (1973) 20 3) J.J.Sagura and J.A.Van Allan ( Kodak Co.): U.S. Pat. 3.062.650 (1962)

Photochemical Reaction of Monosubstituted Aminoazidobenzoic Acid

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