Note: Descriptions are shown in the official language in which they were submitted.
- 1 -
3-14176/=/ZF0/B
This Appllcation is a Divisional Application from
Application 440,255, filed November 2nd, 1983.
The present invention relates to novel bisimides which
can be used in compositions of ma~ter wh;ch crosslink
under the action of light in ~he presence of sensi~isers.
German Offenlegungsschrif~ 2,626,769 and European Patent
Application Publ;cation No. 3,552 d;sclose photocross-
linking polymers having imidyl side groups, in particular
dimethylmaleiimidyl and certain tricyclic imidyl ~roups.
Ho~ever, in some instances their light-sensitivity still
leaves something to be desired.
The invention prov;des novel bisimides of the formula II
R~ ~CO~ ~CO~ ,R
!I N-R4-N l! (TI)
R' C0 C0 ~'
in ~h;ch R and R' together are tetramPthylene which is
unsubstituted or substituted by a methyl group, R4 is
-CmH2m- ~ith m = 1 to 20, -(CH2)XQ(CH2) ,-,
-(CH )2NH(CH2)2NH(CH2)2 ' CH2 Z CH2 ' P
unsubst;tuted or substituted by one or two chlorine atoms
or one or two methyl groups, naphthylene, or a group of
the formula
O _ . ~,_ . ,_ ~, ._,
o~ ~-X~ or X /--CH2-~\ X
~ _ . . _ . , _ " . _ .
Q is -S-, -O- or -NH-, x and x', independently of each
other, are each a number from 2 to 4, Z is phenylene or
C4 6-cycloalkylene, and X is a direct bond, -O-, -S-,
-SO -, -CH2- or -C(CH3)2
The bisimides are suitable in compositions of matter which
crosslink under the act;on of light ;n the presence of
sensitisers and which conta;n
h) an aliphatically unsaturated polycondensation product
which can cantain structural elements of the formula I
1 1 (I)
CH-CI--CO-Y'
R'
and
B) the bisim;de of formula Iio
R and R in formula I are each C1 4-alkyl or together
te~ramethylene, which is unsubstituted or substituted by
15 a methyl group.
R1 is hydrogen or methyl, Y and Y' are each -OH- or
together -O-, and the proportion of bisim;de of the
formula II is 0.1 to 75% by weight, preferably 1 to
25% by weiqht, based on polymer A).
20 R, R' alkyl groups can be strai~ht-chain or branched.
Examples of such groups are methyl, ethyl, n-propyl,
isopropyl, n-butyl and sec.-butyl. A preferred alkyl
group has 1 or 2 carbon atoms and is in particular methyl.
In formula II R and R' together are preferabLy tetra-
methylene, 3- or 4-methyltetramethylene.
An R4 -CmH2~- can be a straight-cha;n or branched
radical, for example methylene, ethylene~ 1,2- or 1~3-propyl-
ener tetramethylene, 1,1,3,3-tetramethylbutylene, penta-
methylene~ hexamethylene, heptamethylene, octamethylene~nonamethylene, decamethylene, undecame~hylene~ trideca-
methylene, tetradecamethylene, hexadecamethylene, heptadeca-
methylene, octadecamethylene or eicosyleneO Preferr~d
10 ~CmH2m- radicals are straight-chain with m = 2-10. An R4
-CH2-Z-CH2- group can be, for example, a 1,3- or 1,4-
phenyLene group or a 1,2-cyclobutylene, 1,3-cyclopentylene
or 1,3-cyclohexylene group. Z is preferably 1~3- or 1,4-
phenylene or 1,3~ or 1,4-cyclohexylene.
A phenylene R4 ~hich is unsubstituted or subst;tuted
by one or two chlorine atoms or one or two methyl groups can be,
for example, the 1,3- or 1,4-phenylene, o- or m-toluylene, 4,5-
dimethyl-1,2-phenylene or 3-chloro-1~4-phenylene group. An
R4 group ~ -X-~ . or ~X i'-C~2~ ~ ;s in
o a ~ 9 _ ~
~o particular the radical of 4,4'-diaminodiphenylmethane, 4,4'-
diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide or 4,4'-
diaminodicyclohexylmethane. R4 is preferably straight-
chain -CmHzm- with m = 2-10, -(C~2)2~(CH2~2 with Q
-S-, -0- or in particular -NH-, -CH2-~-CH2- with Z = 1,3- or
25 1,4-phenylene or 1,3- or 1~4-cyclohexylene; or the radical of
4~4'-diaminodiphenylmethane, 4,4B-diaminodiphenyl ether or
4,4'-diaminodiphenyl sulfide, or 193- or 1~4-phenylene.
g~
-- 4 --
The poLymers to be used according to the invention
preferably have an average molecular ~eight of 1,000 to
1,000,000 and very particularly from 1~000 to 350,000. The
average molecular ieight of the polymers can be determined by
methods known per se, for example by means of light-scatter-
ing, vapour pressure osmometry or ultracentrifugation~
Examples of suitable unsaturated polycondensation
products are unsaturated polyamides, polyes~ers~ polyester
amides and polyurethanes.
~0 Polycondensation products ~hich are preferably used
contain recurring structural elements of the formulae IV to X
-NH-CO-R5-C=C~-R~-CO-NH-~ - (IV) ,
-R8-co-NH-R9-cH=c~-Rlo-NH-co- ( V )
R~
-O-CO-R5-C=CH-R -CO-O-R - (VI3 ,
-co-o-cH2~cH=cH-cH2-o-co-R8- (VII) ,
(VIII) ,
-c~-o-cH-cH2-o-co-R
CH
CH~
-NH-C0-0-CH2-CH=CH-CH2-0-C0-NH-R - (IX) or
-O-CO-~H-R 2-CH=CH-R -NH-CO-O-R - tX)
and can also conta;n corresponding saturated recurring struc-
tural elements which are obtained by partial addition of
anhydrides of the formula XI
R~ /CO~ t X I
Il O
onto the C=C double bonds of the starting polymers with
structural elements of the formulae IV to X and possible
hydrolysis of the anhydride groups, ~here R, R' and R1 are
as defined under the formula I, R5 and R6, independently of
each other, are each a d;rect bond or -CH2-, or one of R5
and R6 is a direct bond and the other is -CH=CH- or
~ CHz ~ , R7 is the radical of an aromatic diamine~
in particular 1,3- or 1,4-phenylene, the radical of 454'-di-
am;nodiphenylmethane or 4,4'-diaminodiphenyl ether, or the
radical of an aliphatic diamine having 1-16 carbon atoms, in
particular -CoH2o- with o = 2 7, R8 is the radical of an
aromatic dicarboxylic acid, in particular the radical of
terephthal;c acid or isophthalic acid, or the radical of an
aliphatic dicarboxylic acid which can have C=C double bonds
and has at least 6 carbon atoms, in particular -tCH2)p-
~ith p = 4-12 and especially 4-8, R9 and R1U, independently
of each other~ are aliphatic radicals which are substituted
or unsubstituted andlor have C-C double bonds and have a
totaL of 4-12 carbon atoms in the main chains~ R11 is a
ben2ene radical, -CH2--\ X, 2 or CqH2q~ ~ith q = 2-10~ in
particular Z-4, and R12 and R13, independently of each
other, are each -tCH2)r- ~ith r = 1-5.
In the formulae IV and YI, R5 and 26 preferably
each are a direct bond and R1 is methyl or in particular
hydrogen, or R1 is hydrogen and R5 and R6 each are -CH2 .
It is very particularly preferable that, in the formulae IY
and YI~ R~ is hydrogen and R5 and R~ are each a direct
bond.
Sa;d polymers can be homopolymers or copolymers, for
example copolyesters of H0-R11-OH diols and mixtures of
unsaturated and saturated d;carboxyl;c ac;ds~ such as mix-
tures of maleic anhydride and terephthalic acid or deriva-
tives thereof.
Preferred polyesters consist of recurring structural
elements of the formula VIa
-0-C0-CH=CH-C0-0-R11- (VIa~
~ith or ~ithout recurring structural elemen~s of the formula
VIb and/or Ia
CO-O-R
tVIb)
and/or
O-CO-C ~ CH-CO-O-R
R-C- C-R' ~Ia)
OC\o/co
in which R and R' together are tetramethylene or, especially,
/ X 2
are each methyl, and R11 is a -CH2-`~ /. group, in
particular -CH~ \-CH2- , or -CH2~s- uith s = 2-12, in
particular 2-4. The proportion of structural elements of
the formula Ia can amount to 95X, in particular 30 to 85%,
of the total number of recurring structural elements of the
polyester. Preferred polyesters consist of structural ele-
ments of the formula VIa ~ith or without structural elements
of the formula VIb.
Polyamides which are used very particularly prefer-
ably consist of recurring structural elements of the formu~a
Va
~L
-- 7
~3 Ql
-R8-CO-~IH-C-CH -CH=CH-(C~ ~ CH=CH-CHC CH i~H CO
Q4 Q~
with or ~ithout recurring structural elem2nts of the formulae
Ib, Ic and/or Id
Q3 Ql
-R8-CO-NH-C-CH2-C'~CH-(CH ~CH=CH-CH C CEI NH tIb)
\0/
Q3 Ql
R8 CO NH-C-CH2-CH=CH- (CH2~HffH-CH -C-CH -NE~-CO- t I c )
Q3 R-C--C-R' Q
OC CO
\0/
and/or
Q3 Ql
-R8-CO-NH-C-CH2-f~CH-(CH2~C~CH-CH -C-CH -NH-CO- (Id~
Q4 R-C--C-R~ R-CI-R ' Q2
OC~o~CO OC~ /CO
in ~hich R and R' together are tetramethylene or, especialLy,
are each methyL, Q1 is C1_12-alkYl, q2 is hydrogen or
C1_12-alkyl, Q3 is C1_12-alkyl~ cycloalkyl having 4-12
ring carbon atoms~ aralkyl having 7 or 8 carbon atoms, or
phenyl, and Q4 is hydrogen, c1_12-alkYl~ cycloalkyl having
4-12 ring carbon atoms, aralkyl having 7 or 8 carbon atoms,
or phenyl, or Q1 and 42 and/or Q3 and Q4 together are
alkylene hav;ng 3-11 carbon atoms, and R8 is the radical of
terephthalic acid, isophthalic acid and/or of a saturated
aliphat;c dicarboxylic acid having 6-12 carbon atoms. The
proportion of structural elements of the formulae Ib, Ic and/
or Id can amount to 95%~ in particular 20-90%~ of ~he total
number of recurring structural elements of the poLyamiden
.
s
8 -
Preferably, Q1 ;s C1_5-alkyl and ~2 is hydrogen or
C1_5-alkyl, Of Q7 and Q2 together are alkylene having
4-7 carbon atoms~ Q3 is C1_7-alkyl, Cs_8 cyc~oa y
phenyl, in particular C1_5-alkyl or phenyl, an~ Q4 is
hydrogen or C1_5-alkyl, in particular hydrogen or methyl.
Particularly preferably~ Q1 is methyl or ethyl, Q2
is hydrogen, methyl or ethyl, Q3 is C1_5-alkyl or phenyl,
Q4 is hydrogen or methyl and R8 is the radical of tere-
phthal;c acid, ;sophthalic ac;d and/or a saturated aliphatic
dicarboxylic acid having 6-10 carbon atons.
Very particularly preferred polymers consist of recur-
ring structural elements of the formula Va with or without re-
curr;ng structural elements of the formulae Ib, Xc and/or Id
in which R and R' together are tetramethylene or ;n particular
are each methyl, Q1 and Q2 are each methyl, Q3 is isopropyl~
Q4 ;s hydro~en, and R8 is the radical of terephthalic acid,
isophthalic ac;d and/or adipic acid, espec;aLLy those wherein
q1 and Q2 are each methyl, Q3 is ;sopropyl, Q4 ;s hydro-
gen, and R8 is the radical of terephthalic acid and/or the
rad;cal of ad;pic ac;d, where the proportion of structural
elements of the formulae Ib, Ic and/or Id can amount to 40-
85~, based on the d;am;ne components of the polyamide. Th~
most preferred polyamides consist solely of recurring struc-
tural elements of the formula ~a in which ~1 to Q4 and R8
are as preferred above.
Aliphatically unsa~urated polycondensation products
wh;ch incorporate recurring structural elements of the
formula I are novel and are likewise part of the subject-
matter of the present invention, what ~as said above also
applying to preferred definitions of R1, R, R'~ Y and Y'
and to preferred unsaturated polycondensat;on products wh;ch
have partly been modified uith -C-C0-Y groupsO Polymers
-e-c o-Y ~
having structural elements of the formula X can be obtained
by reacting aliphatically unsaturated polycondensat;on pro-
ducts ~;th a compound of the ~ormula XI under free-radical
conditions or under the action of l;gh~, and if desired
hydrolys;ng the anhydride groups. The reaction is advantage-
ously carried out in an inert gas atmosphere, for example
under nitrogen~ and in the presence of an inert organic sol-
vent and of a sens;t;ser of the type described below.
Examples of su;table solvents are alipha~ic, cycloaliphatic
or aromatic hydrocarbons wh;ch can be halogenated, such as
pentane, hexane, heptane, cyclohexane~ benzene, toluene,
chlorobenzene~ dichlorobenzenes, cyclic or aLiphatic amides, such
as N methylpyrrol;done~ N-ethyl-2-pyrrolidone, N-methyl-~-
caprolactam, N,N d;methylformamide, N,N-dimethy~acetamide or
N,N-d;ethylacetamide, aliphatic or cyclic ketones, such as
acetone, meth~l e~hyl ketone, cyclohexanone or cyclopen-
tanone, and alcohols~ such as methanol, ethanol or 2-
methoxyethanol. It is also possible to use mixtures of said
soL~ents~ The preferred solvent is N,N-dimethylformamide.
2' The compounds of the formula XI and the polymers
having structural elements of the formulae IV to X are kno~n
or can be prepared by methods known per se. Compounds of the
formula II can be obta;ned in a manner known per se by
reacting a compound of the formula X~ with H2N-R4-NHz
diam;nes and cyclising the amide acids formed as intermedi-
ates. The compounds of the formula II in ~hich R and R' to-
gether are a tetramethylene which is unsubstituted or sub-
stituted by a methyl group, and R4 is as defined above, are
novel and a further part of the subject-matter of the present
invention, ~hat ~as said abo~e also applying to preferred
definitions of R4, and R and R' preferably together being
tetramethylene. The unsaturated diamines required for pre-
par;ng polymers having recurring structural elements of thP
formula V can be obtained by, for example, directly reducing
oximes of the ~ormula XII
- 10 -
Q3 Ql
H 2'~-C-CH-CH=CH- (CE~2) 2-CH=CH CH2-C-CH=!~~ ~ X I I )
Q4 Q.,
to the correspond;ng diamines, or first dehydrating the
oximes to the corresponding nitriles and reducing the nit-
riles to the diamines~ The oximes of the formula XII are
known or can be prepared by the process described in European
Paten~ Application Publication No 11,599.
The compositions of matter can contain~ in
addition to the sensitisers, customary additives, such
as further crossLinking agents. Possible add;t;onal
crosslinking agents are in particular diamines, for
1~ example those of the type described in German Offenlegungs-
schrift 2f657~104. Suitable sensitisers are in particular
triplet sensitisers on whose application the reaction takes
place by triplet energy transfer from the excited sensitiser
to the groundstate compounds of the for0ula II, for example
ketones, for example acetophenone, benzophenone, acetone~
methyL ethyl ketone, methyl isobutyl ketone, Michlerls
ketone, 1 a2~di ben~ilbenzen~ 1,4-diacetylbenzene, 4~cyano-
benzophenone~ thioxanthone, anthraquinone, 1,2- and 1,4-
naphthoqu;none, 2-methyLanthraquinone, benzanthrone, v;ol-
2Q anthrone, p,p~-tetramethyLdiaminobenzophenone, or chloroanil~
anthracene, chrysene, or nitro compounds, such as nitro-
benzene, p-dinitrobenzene, 1- or 2 nitronaphthalene, 2-nitro-
fluorene, 5-nitroacenaphthene, nitroaniline~ 2-chloro-4~
nitroaniline or 2,6-dichloro-~-nitroani~ine~ ThP sensiti;ers
Z5 used can also be free-radical initiators, such as azoisobutyro-
n;trile, or peroxides, for example dibenzoyl pero~ide~ The
sensitisers which are preferably used are unsubstituted thio-
xanthone or substituted thioxanthones, for exa~ple those of
the type described in German Offenlegungsschriften 3~018,891
and 3,117,568 and European Patent Application Publication
Nou 33~720a
s
UV l;ght is preferably used for irrabia~ing ~he
crossl;nking reactions as well as the possible preceding
react;on of the polymers with the anhydrides of the formula
XI. Examples of suitable light sources are xenon lamps,
carbon arcs, mercury lamps and metal halide/mercury lamps.
The compos;tions of matter are suitable, for
example, for preparing solvent-resis~an-t coatings on
various substrates, in particular metals, such as
aluminium, copper and steel, or plastics, for example
~^ polyesters, cellulose acetate and the l;ke, or for
preparing offset printing plates, for preparing photooffset-
resists, or for unconventional photography~ for e~ample for
preparing, by means of photocrosslinking, photographic images
~hich can be coloured ~ith cationic dyes. They are prefer-
ably used for preparing printing plates or as photoresistmaterials for manufacturing printed circuits by methods known
per se. In the latter application, that face of the conductor
board which has been provided ~ith the Light-sensitive layer
is exposed through a photomask incorporating the circuit
diagram and is then developed, whereupon the unexposed areas
of the layer are removed by means of developing liquid~
Compositions of matter in ~hich the polymer has structural
elements of the formula I are systems which can be developed
under aqueous or aqueous-alkaline conditions, ~hich can be
an ecological advantage over cereain develop;ng baths based
on organic solvents. Systems of th;s type can also be
coLoured ~ith cationic dyes. The support materiaLs can be
coated with light-sensitive compositions of matter by tech-
niques ~hich are customary per se, for example by dipping,
spraying, whirLer-coating~ cascade-coating~ knife-coating,
curtain-coating or roller-coating.
- 12 -
The compositions of matter are d;stinguished ;n
particular by a high degree of light-sensitivity. The
crosslinked produc~s ~hich can be obtained therefrom
are highly soLvent-resistant, for example in isopropanol,
and h;ghly abras;on-resistant and firmly adhere to var;ous
support materials, in particular metals~
Examples 1-5 An amount of dimethylmale;c anhydride as
specified in Table I, below~ and 0.25 9 of thioxanthone in
80 ml of DMF are added dropwise at 2ûC under nitrogen and
with irrad;ation in the course of 2 hours to a solution of
5.0 9 of a polyamide of adipic acid and 2~2-dimethyL~11-iso-
propyl-1,11-diaminoundeca-4,8-diene (DUD~ in 70 mL of N,N-
dimethyLformamide (DMF) in a UV reactor (a flask which has
been equipped with a 1ZS-W Philips HPK dip lamp~. Irradia-
tion of the solution ;s then continued for a further 20hours, and the solution is concentrated to a third of its
volume The polymer is precipitated by pouring the solution
into 2 litres of diethyl etheru The analytical data of the
polymers obtained have been compiled in Table I~
The polyamide used can be prepared as follows:
62.8 g of 2,2-dimethyl~ isopropyl-1,11-diamino-
undeca-4,8-diene, 36.4 9 of adipic acid, 0.25 ml of a 10X
aqueou~ NH4H2P02 solution and 0.5 g of di-tert~ Dutyl-
p-cresol are condensed for 90 minutes in a nitrogen atmos-
phere in an autoclave, ehen for 4 hours in a nitrogen s~ream
in an open polycondensation vessel and finally for 1 hour
under h;gh vacuum. All polycondensation steps are carried
out at 250C. Elemental analysis of the polyamide obtained:
calculated C 72.88X H 10.57X N 7.73X
found C 70.20X H 10.47% N 7.45%.
Terminal group content: -COOH 0~16 mEq/g; -NH2 0.04 mEq~g~
Glass transition tempera~ure (Tg~ detsrmined in a differen-
~ 13 -
tial scanning calorimeter3 = 45C; redu~ed v;sCoSitY ~ red. ~
0.70 dl/g (measured as an 0.5% solution in m-cresol at 25C~.
The diamine used can be prepared as foLlows:
100 ml of glacial acetic acid are added with stirring
to 80 9 (0.3 mole) of 2,2-dimethyl-11-isopropyl-11-amino-
undeca~4,8-dienaloxime. HCl gas is then passed in until
saturation is reached, and 30~6 9 (0.3 mol~) of acetic
anhydride are added dropw;se in ~he course of 15 minutes.
The reaction ~ixture is then refluxed for 4 hours, the glacial
acetic acid is distilled off, and the residue is dissolved in
water~ After the solution has been rendere~ basic using
sodium hydroxide solution, the organic phase which separa~es
out is taken up in toluene and distilled, affording 68.5 9
(0.276 mole) of 1,1~dimethyl~10-isopropyl-10-aminodeca 3,7-
dienonitr;le, which corresponds to a yield of 92% of theory;boiling point 94C:3 Pa.
23 9 ~1 mole) of sodium are added to 150 ml of tolu-
ene, and the mixture is heated until the sodium melts. The
heating is then re~oved, and the mixture is stirred until the
sod;um ;s in the form of a fine grey dispersion. A solution
of 53 9 (0.214 molel of 1,1-dimethyL-10-isopropyl-1û-amino-
deca 3,7-dienonitrile in 100 ml of isopropanol is then added
dropwise to this mixtureO which is then refluxed for 3 hours.
200 ~l of water are added, and the organic phase is separated
ff. The solvent is distilled off to gi~e 44 9 (0.175 mole)
of 2,2-dimethyl~ isopropyl-1,11-diaminoundeca-4,8-diene~
which ~orresponds to a yield of 81.5X of theory; boiling
po;nt 86C/1 Pa; n2D0 = 1.4810.
- 14 -
_ ~
O L C) t~l U~ 1~ O r~
u 11 ^ .
~ ~ ~ ~ I~ ~ I~ r~
~ O`' ~
1~1~ _.
_ a~
f~ ~ I~ ~ O` 0
~0 ~ 1~
~J M r~ E
O O O O
C~ O u~
1:~ Z # ~ U;
O.. _____ ' _._ _ `O
L V~ 00 0 0 00
Q ~:t O 0~ t~ N I I
I ~!
~ O~ C~ 0 0 a~ .~
C._.... _ . . _ O
r~ O u O O O
C~ 0 1~ 0 0 r-
L~ ~ . . . . .
~ ~0 ~ ~ ~ `O
E _ `~ Q `O `O
:~
_ ~ C
O ~ ._
Q. _ O` `O 0` 0 r_
1~) ~J ~ L
L _ O O O O O E
,_.. _ .. _ .___ O
~ ru
O ~ ~ ~ ~
.- ~0 ~U
V) ~ ~
C ~ O `O ~ O _ C
~ U~ U~ 01) O` O ~.
J C Q U~
cn ~ v
3J ~ ~ ~
C
. .__ - __ E O
U
.- a~ c u~ ~ ~ ~ # C
~ ~ ," o ~ e ~ ~ u~ O o , _
O -- -~ C ~ O O ~ O f ~ D
~0 ~ O-- u~`O " ~ ~ C ::1
J E ~ ~ '7 0 ~ ~ ~:n ~ ~ O O
c ~ Cl a~ ~~ ~ _
O r L ,~ _ ~ ~) I~ O~
e ~ ~ ~ ~ I~ o ,~ ~ ~ -- a~
>~ ~ . . . . . o ..
E r ~ O ~ ~ 1 ~ U) L
., c cn~ C a,
~ , , ~ ~
_.___ ~ C
tL~ . O
~ J O U
Q
r o
O r~ Z ~ Ul~ ~
~ 1~1
_a ~ O~S g of a polyamide fro~ 2,2-dimethyl~
isopropyl-1,11-diaminoundeca-4,8-diene and adipic acid ~pre-
pared analogously to the method described in Examples 1-5,
Tg = 58C, ~ red = 0.65 dl/g~ 5X solution in m-cresol at
25C~, 50 ng of one of the following bis;mides:
A) m;xture of N,N'-hexamethylenebis-(3-methyl-3,4~5,6 tetra-
hydrophthalimide) and N,N'-hexamethylenebis-t4-methyl-3,4,5,6-
tetrahydrophthalimide~ (ratio abo~t 15:85% by ~e;ght),
~) N,N'-hexamethylenebis-3~4,5~S-tetrahydrophthal~mide
and 27.5 mg of ethyl thioxanthone-7-methyl-3-carboxyl3te are
dissolved in 11 9 of chloroform. The resulting solution is
appl;ed to a copper conductor board by means of a 50 ~m
doctor and is dr;ed at ~0C in the course of 3 minutes. The
coating is then exposed through a Stouffer step wedge t21
step sensitivity guide) to the light of a 5,ûO0-W high pres-
sure burner a distance of 70 cm anay. The unexposed areas
are dissolved out by ~ashing in chloroform (30 seconds). The
results are g;ven in Table III, below.
Table III
Durat;on of Final wedge step depicted
exposure to light _
(seconds) A B
_ (~xample 14) (Example 15)
none
none 3
120 _ ~
- 16-
The novel bisinides A) and B~ wsed in Examples 6 and
7 above can be prepared as follows:
a) 23.2 9 (0~2 mole) of 1~6 diaminohexane and 66.4 9
(0.4 mole) of a mixture of about 15X by ~eight of 3-methyl-
1-cyclohexene 1,2~dicarboxylic anhydride and about 85Z by
weight of 4-methyl-1-cyclohexene-1~2-djcarboxylic anhydride
are dissolved in 350 ml of toluene. The water formed is
separated off under reflux in the course of 24 hours. 300 ml
of toluene are then distilled off, the crystals formed are
filtered off and washed with cyclohexane~ and the crude pro-
duct is recrystallised from methanol, a,fording 35 9 (42.5%
of theory) of a mixture of about 15X by ~eight of N~N'-nexa-
methylenebis-~3-methyl-3,4,5~6-tetrahydrophthalimide) and
about 85X by ~eight of N,N'-hexamethylenebis-~4-methyl-
3,4,5,6-tetrahydrophthalimide). Melting point 93-95C.
Elemental analysis:
calculated C 69.88 H 7.82 N 6.79X
found C 70.0 H 7 o8 N 6.7%.
Thin layer chromatogram with toluene/ethanol in a ratio by
volume of 80:20 as solvent: 1 main spot.
b) 23.2 9 (0.2 mole) of 1,6-diaminohexane and 60.8 9
(0.4 mole~ of 1-cyclohexene-1,2-dicarboxyLic anhydride are
dissolved in 350 ml of toluene, and the water formed is
separated off under reflux in the course of 20 hours. 300 ml
of toluene are then distilled off, and the precipitated pro-
duct is filtered off~ ~ashed with toluene/cyclohexane and re-
crystallised from 600 ml of methanol. The resulting ~hite
crystalline product is dried at 60C in vacuo in the course
of 24 hours~ affording 50 9 (64.1X of theory) of N,N'-hexa-
methylenebis-3,4,5~6-tetrahydro?hthdlim;de; melting point
123-124C.
Elemental analysis:
calculated C ~8.73X H 7.34X N 7~4%
found C 68.9X H 7~4% N 7~4X~
Thin layer chromatogram ~ith toluene/ethanol tratio by volume
80:20) as solvent: 1 spot.
