CA1108626A - 3- and 4-azidophthalic acid derivatives - Google Patents
3- and 4-azidophthalic acid derivativesInfo
- Publication number
- CA1108626A CA1108626A CA313,228A CA313228A CA1108626A CA 1108626 A CA1108626 A CA 1108626A CA 313228 A CA313228 A CA 313228A CA 1108626 A CA1108626 A CA 1108626A
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
- B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
- B29C65/483—Reactive adhesives, e.g. chemically curing adhesives
- B29C65/4845—Radiation curing adhesives, e.g. UV light curing adhesives
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/008—Azides
- G03F7/012—Macromolecular azides; Macromolecular additives, e.g. binders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
Abstract
Abstract of the Disclosure The compounds according to the invention have the formulae Ia or Ib or (Ia) (Ib) in which Y is a divalent organic radical and Z is -NH2, -NH-alkyl having 1-4 C atoms, -OH, -COOH, -COCl, O-CO-CH=CH2, , -COO-CH=CH2 or -O-CH=CH2.
These novel 3- or 4-azidophthalic acid derivatives may be used for the preparation of photo-crosslinkable polymers. Compared to corresponding photosensitive polymers of the prior art, these novel polymers have the advantages that they are even more photosensitive and that they also absorb in the long wavelength UV region (at wavelengths greater than 320 nm).
These novel 3- or 4-azidophthalic acid derivatives may be used for the preparation of photo-crosslinkable polymers. Compared to corresponding photosensitive polymers of the prior art, these novel polymers have the advantages that they are even more photosensitive and that they also absorb in the long wavelength UV region (at wavelengths greater than 320 nm).
Description
``"`` - 1~8626 .
The present invention relates to novel 3- or 4-azidophthalic acid derivatives and to processes for their preparation. The 3- and 4-azidophthalic acid deriva-tives according to the invention can be used to produce photocurable polymers.
The literature discloses that polymers having azido side groups can be photo-crosslinked and are suitable for photo-mechanical applications [cf., for example, British Patent Specification 843,541, U.S. Patent Specific-ation 3,002,003, Journal of Appl. Poly. Sci., 7, 273-279 (1963) and Japanese Laid-Open Specification i4/238431.
These prior-art polymers have disadvantages inasmuch as they absorb predominantly in the short wavelength W reg-ion and are therefore unsuitable, or rather unsuitable, for numerous applications, especially in the field of micro-electronics, which demand highly photosensitive sub-stances which absorb in the longer wavelength W region.
It was therefore the object of the invention to provide novel substances which are suitable for the pre-paration of polymers which have increased photosensitivity and absorb in the longer wavelength W region (above 320 nm ) .
The novel 3- and 4-azidophthalic acid derivatives have the formula Ia or Ib .
.~ ~
.. ... . ...
.. , ~ .. . .
~, .:. ~: ~ : . -. ~
- ; ' ~ . - :, '' ' ' . :
~ ~" CONH-Y-Z ~ CO~
N ~ OOH N3 ~ N-Y-Z
(Ia) (Ib) in which Y is an alkyene group having.2-18 C atoms, which is unsubstituted or is substituted by one or two phenyl groups, cycloalkyl groups having 5-8 C atoms or aralkyl groups having 7 or 8 C atoms, or is phenylene, naphthylene, blphenylene, cyclohexylene, dicyclohexylmethane or ~ X ~ , which Y groups are unsubstituted or are substituted, per ring, by one halogen atom, one alkyl group having 1-4 C atoms, one cycloalkyl group having 5-7 C atoms or one aralkyl group having 7 or 8 C atoms, X is -O-, -S-, -SO2-, -CH2-, -ÇH-, -g- or -CO- and Z 1~ -NH2, -NH-alkyl having 1-4 C atoms, -OH, -COOH, -COCl, -O-CO-CH=CH2, -O-CO-g=CH2, -COO-CH=CH2 or -O-CH=C~2.
Alkylene groups Y may be stralght-chain or branched.
Preferred substituted alkylene groups Y are those which are substituted by one or two phenyl groups or ~y one or two cycloalkyl or aralkyl groups according to the defini-tion glven, such as the cyclohexyl or benzyl group.
Examples of such alkylene groups Y are the 1,2-ethylene, 1,3- or 1,2-propylene, 1,4- or 1,3-butylene, pentamethylene, hexamethylene,.2-methyl-4-dimethylhexa-methylene,.2-dimethyl-4-methylhexamethylene, l,10-dicyclo-hexyl- or.l,10-dicyclooctyl-decamethylene, l,10-diisopropyl-decamethylene, l,l,10,10-tetramethyldecamethylene, 1,10-diethyl-l,10-dimethyldecamethylene, octamethylene, deca-methylene, dodecamethylene and l-ethyl-10,10-dimethylundeca-: . ~ , ... ... . . .
. .
: ~ . . :
., . ~ . . - - .
methylene. Unsubstituted straight-chain or branched alkyl-ene groups, especially those having 2-16 C atoms, are preferred.
Phenylene, naphthylene, diphenylene, cyclohexylene or dicyclohexylmethane groups Y, or ~ ~
groups Y, can be substituted, by halogen atoms, such as fluorine, chlorine or bromine, alkyl groups having 1-4 C atoms, especially methyl or ethyl, cycloalkyl groups having 5-7 C atoms, especially cyclopentyl and cyclohexyl, or aralkyl groups having 7 or 8 C atoms, such as benzyl or ~-phenylethyl. The said groups can have several substituents of the type mentioned on each ring, but advantageously are substitued by only one of the said groups per ring, especially by chlorine or bromlne, methyl or ethyl.
Preferably, however, phenylene, naphthylene, cyclo-hexylene, biphenylene, dicyclohexylmethane and ~ X ~ groups Y are unsubstltuted, and advanta-geously X is -O-, -SO2- or -CH2. Cyclohexylene, naphthylene and in particular phenylene groups are particularly preferred.
The N3 group is preferably joined to the benzene ring in the ortho-position to the carboxyl or carboxamide group or to a carbonyl group.
Preferred compounds are those of the formula Ia, and especlally those of the ~ormula Ib, ln which Y is unsubsti-tuted straight-chain or branched alkylene and Z is as defined under formula Ia or Ib, but in particular compounds of the formula Ia, and especially compounds of the formula Ib, in which Y is unsubstituted alkylene having 2-18, especially 2-16, C atoms, cyclohe~ylene, naphthylene or phenylene and Z is -NH2, -COOH, -COCl, -OH, -O-CO-CH=CH2 or -O-CO-C,=CH2 Particularly preferred products according to the invention are compounds of the formula VII
: . . . . . . .
.. . . .
. . : ~ . - . . , -,: , ~:. ; . . : :, ; ~' .
~ 86~6 . ~ CO ~N CH2 CH2 - OH (VII~, 3 . - .
preferably N~ hydroxyethyl)-3-azidophthalimide, and compounds of the formula VIII
.
~ N-- ~CH2)f CO.OH (VIII), in which f is from 1 to 5, preferably 5, the preferred compound being 6-(3-azidophthalimidyl)-caproic acid, and compounds of the formula IX
~ CO ~ ~ ~H2 (IX), preferably 4-(3-azidophthalimidyl)-aniline, and compounds of the formula X
N3 N - CH2.CH2 - O.CO - CH = CH2 (X) and compounds of the formula XI
~ ~ - CH2CH2 - O.CO - C = CH2 (XI).
; N3 CH3 The compounds of the formula Ib can be prepared in a particularly advantageous manner by reacting a com--- 5 --pound of the formula II
Q ~ ~N Y Z' (II) in which Y is defined as under formula Ib, Z' is a group corresponding to Z but is not -COCl and Q is a halogen atom, such as chlorine, bromine or fluorine, or is the nitro group, in an inert organic solvent, at a temperature between about 0C and 120C, preferably between about 50C
and 90C, with an azide of the formula III
Mn+ (N3 )n (III) in which n is 1 or 2 and M is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation, and if desired converting the resulting compound of the formula Ib, in which Z is -COOH, to the corresponding acid chloride by treatment with a suitable chlorinating agent, such as thionyl chloride, oxalyl chloride or phosgene.
The literature [Tetrahedron Letters, 12, 1305-1309 (1966)] discloses that 3-nitrophthalic anhydride can be converted to 3-azidophthalic anhydride by means of sodium azide in the presence of an inert organic solvent at a temperature of 110C. However, 4-nitrophthalic an-hydride and 3-chlorophthalic anhydride cannot be converted to the corresponding azide by this method. It is therefore surprising that, according to the invention, both the 3-nitro- and 4-nitro-phthalimides of the formula II, and the corresponding 3- and 4-halogen compounds, can be converted to the corresponding azides and the reaction can furthermore in most cases be carried out at substantially lower temperatures, with good to very good yields. A
prior expensive separation of the starting materials into the 3- and 4-isomers is therefore not necessary in the pro-cess according to the invention.
Preferably, Q is the nitro group. A quater-.
. ~
-` ` 11Ç18626 .
nary ammonium cation M is, for example, a tetraalkylammon-ium cation or benzyltrialkylammonium cation, with each alkyl moiety having 1-12 and especially 1-4 C atoms, especially the tetramethylammonium cation and the trimethyl benzylammonium cation.
Examples of suitable alkali metal azides and alkaline earth metal azides are lithium, sodium, potass-ium, calcium, magnesium and barium azide. Alkali metal azides, above all sodium azide, are preferred.
The azide is advantageously employed in excess, for ex-ample in a molar excess of about 5-50% and preferably of about 10-30%.
Examples of suitable inert organic solvents are polar solvents, for instance lower aliphatic alcohols,for example those having not more than`6 C atoms,such as methanol, ethanol, propanol, isopropanol, butanols and pentanols, dibenzyl ethers and dialkyl ethers with each alkyl moi-ety having 1-4 C atoms, such as diethyl ether, di-n-propyl ether and di-isopropyl ether, cyclic ethers, such as tetrahydrofuran, tetrahydropyran and dioxan~ and diethylene glycol dialkyl ethers and triethylene glycol dialkyl ethers with each alkyl moiety having 1-4 C atoms, such as diethylene glycol diethyl ether and di-n-butyl ether, and triethylene glycol dimethyl ether It is advantageous to use aprotic polar solvents, such as aliphatic and aromatic nitriles, such as alkylnitriles having 2-5 C atoms in the alkyl moiety, for example acetonitrile, propionitrile and butyronitrile, or benzonitrile, cyclic amides, such as N-methyl-2-pyrroli-done, N-acetyl-2-pyrrolidone and N-methyl--caprolactam, N,N-dialkylamides of aliphatic monocarboxylic acids having 1-3 C atoms in the acid moiety, such as N,N-dimethylform-amide, N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxyacetamide, dialkylsulphoxides, such as dimethylsulphoxide and diethylsulphoxide, hexamethylphos-phoric acid triamide (hexametapol), and tetrahydrothio-phene dioxide (sulpholan). Preferred solvents are .;
.
, dialkylsulphoxides, especially dimethylsulphoxide.
Compounds of the formula Ia and Ib, in which Z ~
-OCH=CH2, can also be prepared by a modified method which comprises reacting a compound of the formula IV
3~~ ~ \ (I~) with an amine of the formula V
H2N-Y-Z~ (V) to give a compound of the formula VI
~ O-NH-Y-Z (VI), - N3 ~ COOH
in which formulae Y is as defined under formula Ia or Ib r and Z" is -NH2, -NH-alkyl having 1-4 C atoms,.-OH, -COOH, -O-CO-CH=CH2, -0-CO-C=CH2 or -COO-CH=CH2, thereafter, if appropriate, cyclising the compound of the formula VI and, if desired, converting compounds of the formula Ib, in which Z is -COOH, to the corresponding acid chloride by treatment with a chlorinating agent.
The reaction of the anhydride of the formula IV
with the amine of the formula V is advantageously carried out in an organic medium, at temperatures between about 0C and 120C, depending on the nature of the reactants.
Advantageously, the anhydride of the formula IV is employed in stoichiometric amount, or in slight excess over the amine of the formula V, for example in an excess of up to about 20 mol ~.
Examples of suitable organic solvents are aprotic solvents of the abovementioned type, as well as non-halogenated and halogenated aliphatic or aromatic hydro-carbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, 1,2-dichloroethane, benzene, toluene and chlorobenzene, and aliphatic and cycloaliphatic ketones, such as acetone,-methyl ethyl ketone, cyclopentanone and cyclohexanone.
The cyclisation of the compounds of the formula VI
can be carried out in a manner known per se, by chemical means, i.e. with addition of dehydrating agents known per se. Depending on the nature of the reactants, the re-action conditions and the solvent employed, the cyclisa-tion can, especially at elevated temperatures, also be carried out without adding a dehydrating agent, the water formed advantageously being removed azeotropically.
However, in general the cyclisation is carried out at temperatures between about 40 and 120C, preferably at 70-90C, in the presence of dehydrating agents and in the presence or absence of an aprotic organic solvent.
Suitable dehydrating agents are, in particular, anydrides of aliphatic monocarboxylic acids, having 2-5 C atoms, which are unsubstituted or substituted by halogen atoms or alkyl groups, such as acetic anhydride, propionic an-hydride, butyric anhydride, valeric anhydride, trichloro-acetic anhydride and trimethylacetic anhydride. The preferred dehydrating agent is acetic anhydride.
Compounds of the formula Ia or Ib, in which Z is -O-CO-CH=CH2 or -0-CO-C=CH2, can also be obtained by re-: CH3 acting a compound of the formula Ia or Ib, in which Z is -OH, with corresponding unsaturated acids, acid chlorides or esters. Finally, compqunds of the formula Ia or Ib, in which Z is -COOCH=CH2, can also be obtained by re-acting compounds of the formula Ia or Ib, in which Z is -COOH, with corresponding alcohols or esters in the pres-ence of acids or bases.
The starting materials of the formulae II to V are known or can be prepared by methods known per se. Com-pounds of the formula II can, for example, be obtained in ~ ..... , . .. . . . . .. .. .. .. .. . . _ .. , . =, .. . . .. . ....... . .. ... . . .. .
_ g _ a manner known per se, by reacting 3- or 4-nitrophthalic anhydride or the corresponding halogen compounds with amines HN-Y-Z' and then cyclising the resulting amido-carboxylic acids The azidophthalic anhydrides of the formula IV are described in U.S. Patent Specification 3,002,003.
After the reaction has ended, the compounds o~
the formula Ia or Ib can be purified and isolated in the conventional manner, for example by concentrating the re-action solution or suspension in vacuo and washing the reaction product with wa-ter. The compounds of the formula Ia and Ib are in general obtained in the form of crystals.
The compounds of the formula Ib are valuable intermediates for the preparation of photo-crosslinkable polymers. Such polymers can be prepared by methods of synthesis, known per se, for the preparation of macro-molecules having photoactive side groups. In prin-ciple, two methods can be employed;
1. Introduction of the azidophthalimidyl groups into an existing polymer chain containing corresponding functional groups, and
The present invention relates to novel 3- or 4-azidophthalic acid derivatives and to processes for their preparation. The 3- and 4-azidophthalic acid deriva-tives according to the invention can be used to produce photocurable polymers.
The literature discloses that polymers having azido side groups can be photo-crosslinked and are suitable for photo-mechanical applications [cf., for example, British Patent Specification 843,541, U.S. Patent Specific-ation 3,002,003, Journal of Appl. Poly. Sci., 7, 273-279 (1963) and Japanese Laid-Open Specification i4/238431.
These prior-art polymers have disadvantages inasmuch as they absorb predominantly in the short wavelength W reg-ion and are therefore unsuitable, or rather unsuitable, for numerous applications, especially in the field of micro-electronics, which demand highly photosensitive sub-stances which absorb in the longer wavelength W region.
It was therefore the object of the invention to provide novel substances which are suitable for the pre-paration of polymers which have increased photosensitivity and absorb in the longer wavelength W region (above 320 nm ) .
The novel 3- and 4-azidophthalic acid derivatives have the formula Ia or Ib .
.~ ~
.. ... . ...
.. , ~ .. . .
~, .:. ~: ~ : . -. ~
- ; ' ~ . - :, '' ' ' . :
~ ~" CONH-Y-Z ~ CO~
N ~ OOH N3 ~ N-Y-Z
(Ia) (Ib) in which Y is an alkyene group having.2-18 C atoms, which is unsubstituted or is substituted by one or two phenyl groups, cycloalkyl groups having 5-8 C atoms or aralkyl groups having 7 or 8 C atoms, or is phenylene, naphthylene, blphenylene, cyclohexylene, dicyclohexylmethane or ~ X ~ , which Y groups are unsubstituted or are substituted, per ring, by one halogen atom, one alkyl group having 1-4 C atoms, one cycloalkyl group having 5-7 C atoms or one aralkyl group having 7 or 8 C atoms, X is -O-, -S-, -SO2-, -CH2-, -ÇH-, -g- or -CO- and Z 1~ -NH2, -NH-alkyl having 1-4 C atoms, -OH, -COOH, -COCl, -O-CO-CH=CH2, -O-CO-g=CH2, -COO-CH=CH2 or -O-CH=C~2.
Alkylene groups Y may be stralght-chain or branched.
Preferred substituted alkylene groups Y are those which are substituted by one or two phenyl groups or ~y one or two cycloalkyl or aralkyl groups according to the defini-tion glven, such as the cyclohexyl or benzyl group.
Examples of such alkylene groups Y are the 1,2-ethylene, 1,3- or 1,2-propylene, 1,4- or 1,3-butylene, pentamethylene, hexamethylene,.2-methyl-4-dimethylhexa-methylene,.2-dimethyl-4-methylhexamethylene, l,10-dicyclo-hexyl- or.l,10-dicyclooctyl-decamethylene, l,10-diisopropyl-decamethylene, l,l,10,10-tetramethyldecamethylene, 1,10-diethyl-l,10-dimethyldecamethylene, octamethylene, deca-methylene, dodecamethylene and l-ethyl-10,10-dimethylundeca-: . ~ , ... ... . . .
. .
: ~ . . :
., . ~ . . - - .
methylene. Unsubstituted straight-chain or branched alkyl-ene groups, especially those having 2-16 C atoms, are preferred.
Phenylene, naphthylene, diphenylene, cyclohexylene or dicyclohexylmethane groups Y, or ~ ~
groups Y, can be substituted, by halogen atoms, such as fluorine, chlorine or bromine, alkyl groups having 1-4 C atoms, especially methyl or ethyl, cycloalkyl groups having 5-7 C atoms, especially cyclopentyl and cyclohexyl, or aralkyl groups having 7 or 8 C atoms, such as benzyl or ~-phenylethyl. The said groups can have several substituents of the type mentioned on each ring, but advantageously are substitued by only one of the said groups per ring, especially by chlorine or bromlne, methyl or ethyl.
Preferably, however, phenylene, naphthylene, cyclo-hexylene, biphenylene, dicyclohexylmethane and ~ X ~ groups Y are unsubstltuted, and advanta-geously X is -O-, -SO2- or -CH2. Cyclohexylene, naphthylene and in particular phenylene groups are particularly preferred.
The N3 group is preferably joined to the benzene ring in the ortho-position to the carboxyl or carboxamide group or to a carbonyl group.
Preferred compounds are those of the formula Ia, and especlally those of the ~ormula Ib, ln which Y is unsubsti-tuted straight-chain or branched alkylene and Z is as defined under formula Ia or Ib, but in particular compounds of the formula Ia, and especially compounds of the formula Ib, in which Y is unsubstituted alkylene having 2-18, especially 2-16, C atoms, cyclohe~ylene, naphthylene or phenylene and Z is -NH2, -COOH, -COCl, -OH, -O-CO-CH=CH2 or -O-CO-C,=CH2 Particularly preferred products according to the invention are compounds of the formula VII
: . . . . . . .
.. . . .
. . : ~ . - . . , -,: , ~:. ; . . : :, ; ~' .
~ 86~6 . ~ CO ~N CH2 CH2 - OH (VII~, 3 . - .
preferably N~ hydroxyethyl)-3-azidophthalimide, and compounds of the formula VIII
.
~ N-- ~CH2)f CO.OH (VIII), in which f is from 1 to 5, preferably 5, the preferred compound being 6-(3-azidophthalimidyl)-caproic acid, and compounds of the formula IX
~ CO ~ ~ ~H2 (IX), preferably 4-(3-azidophthalimidyl)-aniline, and compounds of the formula X
N3 N - CH2.CH2 - O.CO - CH = CH2 (X) and compounds of the formula XI
~ ~ - CH2CH2 - O.CO - C = CH2 (XI).
; N3 CH3 The compounds of the formula Ib can be prepared in a particularly advantageous manner by reacting a com--- 5 --pound of the formula II
Q ~ ~N Y Z' (II) in which Y is defined as under formula Ib, Z' is a group corresponding to Z but is not -COCl and Q is a halogen atom, such as chlorine, bromine or fluorine, or is the nitro group, in an inert organic solvent, at a temperature between about 0C and 120C, preferably between about 50C
and 90C, with an azide of the formula III
Mn+ (N3 )n (III) in which n is 1 or 2 and M is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation, and if desired converting the resulting compound of the formula Ib, in which Z is -COOH, to the corresponding acid chloride by treatment with a suitable chlorinating agent, such as thionyl chloride, oxalyl chloride or phosgene.
The literature [Tetrahedron Letters, 12, 1305-1309 (1966)] discloses that 3-nitrophthalic anhydride can be converted to 3-azidophthalic anhydride by means of sodium azide in the presence of an inert organic solvent at a temperature of 110C. However, 4-nitrophthalic an-hydride and 3-chlorophthalic anhydride cannot be converted to the corresponding azide by this method. It is therefore surprising that, according to the invention, both the 3-nitro- and 4-nitro-phthalimides of the formula II, and the corresponding 3- and 4-halogen compounds, can be converted to the corresponding azides and the reaction can furthermore in most cases be carried out at substantially lower temperatures, with good to very good yields. A
prior expensive separation of the starting materials into the 3- and 4-isomers is therefore not necessary in the pro-cess according to the invention.
Preferably, Q is the nitro group. A quater-.
. ~
-` ` 11Ç18626 .
nary ammonium cation M is, for example, a tetraalkylammon-ium cation or benzyltrialkylammonium cation, with each alkyl moiety having 1-12 and especially 1-4 C atoms, especially the tetramethylammonium cation and the trimethyl benzylammonium cation.
Examples of suitable alkali metal azides and alkaline earth metal azides are lithium, sodium, potass-ium, calcium, magnesium and barium azide. Alkali metal azides, above all sodium azide, are preferred.
The azide is advantageously employed in excess, for ex-ample in a molar excess of about 5-50% and preferably of about 10-30%.
Examples of suitable inert organic solvents are polar solvents, for instance lower aliphatic alcohols,for example those having not more than`6 C atoms,such as methanol, ethanol, propanol, isopropanol, butanols and pentanols, dibenzyl ethers and dialkyl ethers with each alkyl moi-ety having 1-4 C atoms, such as diethyl ether, di-n-propyl ether and di-isopropyl ether, cyclic ethers, such as tetrahydrofuran, tetrahydropyran and dioxan~ and diethylene glycol dialkyl ethers and triethylene glycol dialkyl ethers with each alkyl moiety having 1-4 C atoms, such as diethylene glycol diethyl ether and di-n-butyl ether, and triethylene glycol dimethyl ether It is advantageous to use aprotic polar solvents, such as aliphatic and aromatic nitriles, such as alkylnitriles having 2-5 C atoms in the alkyl moiety, for example acetonitrile, propionitrile and butyronitrile, or benzonitrile, cyclic amides, such as N-methyl-2-pyrroli-done, N-acetyl-2-pyrrolidone and N-methyl--caprolactam, N,N-dialkylamides of aliphatic monocarboxylic acids having 1-3 C atoms in the acid moiety, such as N,N-dimethylform-amide, N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxyacetamide, dialkylsulphoxides, such as dimethylsulphoxide and diethylsulphoxide, hexamethylphos-phoric acid triamide (hexametapol), and tetrahydrothio-phene dioxide (sulpholan). Preferred solvents are .;
.
, dialkylsulphoxides, especially dimethylsulphoxide.
Compounds of the formula Ia and Ib, in which Z ~
-OCH=CH2, can also be prepared by a modified method which comprises reacting a compound of the formula IV
3~~ ~ \ (I~) with an amine of the formula V
H2N-Y-Z~ (V) to give a compound of the formula VI
~ O-NH-Y-Z (VI), - N3 ~ COOH
in which formulae Y is as defined under formula Ia or Ib r and Z" is -NH2, -NH-alkyl having 1-4 C atoms,.-OH, -COOH, -O-CO-CH=CH2, -0-CO-C=CH2 or -COO-CH=CH2, thereafter, if appropriate, cyclising the compound of the formula VI and, if desired, converting compounds of the formula Ib, in which Z is -COOH, to the corresponding acid chloride by treatment with a chlorinating agent.
The reaction of the anhydride of the formula IV
with the amine of the formula V is advantageously carried out in an organic medium, at temperatures between about 0C and 120C, depending on the nature of the reactants.
Advantageously, the anhydride of the formula IV is employed in stoichiometric amount, or in slight excess over the amine of the formula V, for example in an excess of up to about 20 mol ~.
Examples of suitable organic solvents are aprotic solvents of the abovementioned type, as well as non-halogenated and halogenated aliphatic or aromatic hydro-carbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, 1,2-dichloroethane, benzene, toluene and chlorobenzene, and aliphatic and cycloaliphatic ketones, such as acetone,-methyl ethyl ketone, cyclopentanone and cyclohexanone.
The cyclisation of the compounds of the formula VI
can be carried out in a manner known per se, by chemical means, i.e. with addition of dehydrating agents known per se. Depending on the nature of the reactants, the re-action conditions and the solvent employed, the cyclisa-tion can, especially at elevated temperatures, also be carried out without adding a dehydrating agent, the water formed advantageously being removed azeotropically.
However, in general the cyclisation is carried out at temperatures between about 40 and 120C, preferably at 70-90C, in the presence of dehydrating agents and in the presence or absence of an aprotic organic solvent.
Suitable dehydrating agents are, in particular, anydrides of aliphatic monocarboxylic acids, having 2-5 C atoms, which are unsubstituted or substituted by halogen atoms or alkyl groups, such as acetic anhydride, propionic an-hydride, butyric anhydride, valeric anhydride, trichloro-acetic anhydride and trimethylacetic anhydride. The preferred dehydrating agent is acetic anhydride.
Compounds of the formula Ia or Ib, in which Z is -O-CO-CH=CH2 or -0-CO-C=CH2, can also be obtained by re-: CH3 acting a compound of the formula Ia or Ib, in which Z is -OH, with corresponding unsaturated acids, acid chlorides or esters. Finally, compqunds of the formula Ia or Ib, in which Z is -COOCH=CH2, can also be obtained by re-acting compounds of the formula Ia or Ib, in which Z is -COOH, with corresponding alcohols or esters in the pres-ence of acids or bases.
The starting materials of the formulae II to V are known or can be prepared by methods known per se. Com-pounds of the formula II can, for example, be obtained in ~ ..... , . .. . . . . .. .. .. .. .. . . _ .. , . =, .. . . .. . ....... . .. ... . . .. .
_ g _ a manner known per se, by reacting 3- or 4-nitrophthalic anhydride or the corresponding halogen compounds with amines HN-Y-Z' and then cyclising the resulting amido-carboxylic acids The azidophthalic anhydrides of the formula IV are described in U.S. Patent Specification 3,002,003.
After the reaction has ended, the compounds o~
the formula Ia or Ib can be purified and isolated in the conventional manner, for example by concentrating the re-action solution or suspension in vacuo and washing the reaction product with wa-ter. The compounds of the formula Ia and Ib are in general obtained in the form of crystals.
The compounds of the formula Ib are valuable intermediates for the preparation of photo-crosslinkable polymers. Such polymers can be prepared by methods of synthesis, known per se, for the preparation of macro-molecules having photoactive side groups. In prin-ciple, two methods can be employed;
1. Introduction of the azidophthalimidyl groups into an existing polymer chain containing corresponding functional groups, and
2. Synthesis of a polymer chain from monomers which already contain the photosensitive azidophthalimidyl group, the polymer chain being synthesisable by polymer-isation or polyaddition.
Examples of suitable compounds for process 1) are those of the formula Ib in which Z is -OH, -COOH, -COCl, -NH2 or -NH-alkyl having 1-4 C atoms, such compounds being reacted, for example, with polymers having recurring structural units of the formulae ÇH - CO ~ ~H2 CH2 / \
~H - CO ~ . H - OH, R - C - COO(CH2 ~ CH CH2 or CH2 / \
O(CH2 ~ CH 2 (where R is hydrogen or methyl - : .... - . ~ ~
: ~ . - ~. :. . .......... ..
..
~8626 and y is 1 or 2).
Suitable compounds for process 2) are, in parti-cular, those of the formula Ib in which Z is -O-COCH=CH2, -O-COC=CH2, -COOCH=CH2 or -OCH=CH2, such-compounds being polymerised, by themselves or together with other ethylen-ically unsaturated monomers, for example vinyl chloride, vinylidene chloride, acrylic acid, acrylonitrile, alkyl acrylates and alkyl methacrylates, styrene, ethylene, pro-pylene, isoprene, chloroprene, 1,4-butadiene, vinyl ace-tate, vinyl propionate, maleic acid, fumaric acid or maleic anhydride.
The polymers thus obtained, having azidophthalimidyl side groups, can be photo-crosslinked, especially with UV
light, and are suitable for photomechanical applications, for example for the manufacture of printing plates for the offset printing process, for the manufacture of photo-offset lacquers, for unconventional photography, for example for the production of so-called vesicular images, or for colouring polymer images, which after exposure and development are not easily visible, by means of suitable dyes, for example oil-soluble dyes, or, if the polymer con-tains acid groups, for example carboxylic acid or sulphonic acid groups, with cationic dyes, The polymers accord-ing to the invention are used in particular as so-called photo-resists for the manufacture of printed circuits by methods known per se. In these, the side of the con-ductive plate provided with the photosensitive layer is exposed through a negative transparency carrying the con-ductor image and is then developed, after which the unex-posed areas of the layer are removed with developer fluid.
Exposure can be effected by means of sunlight, carbon arcs or xenon lamps, but is advantageously carried out with high pressure mercury lamps.
.
... . . .
. - . ~ ~ . .
. ~ .
~ ~ -~i86Z6 Example 1 N-C
A mixture of 17.9 g (o.076 mol) of N-(~hydroxy-ethyl)-3-nitrophthalmide and 5,11 g (0.078 mol) of sodium azide in 70 ml of dimethylsulphoxide is stirred at 50C
for 12 hours. The solution is evaporated in vacuo and the residue is stirred with 200 ml of ice-water. The crystals which have precipitated are filtered off with suction, washed with 20 ml of water and dried for 24 hours at 80C/100 mm Hg, 17 g (97% of theory) of N-(~-hydroxyethyl)-3-azidophthalimide are obtained; melting point 141C (with decomposition). IR spectrum (CH2C12):
1775 cm 1 and 1720 cm 1 (C0-N-C0); 2120 cm 1 (N3).
N-(~-Hydroxyethyl-3-nitrophthalimide, used in the above example, can be prepared as follows: a mixture of 19.3 g (0.1 mol) of 3-nitrophthalic anhydride, 6.7 g (0.1 mol) of ethanolamine, 50 ml of N,N-dimethylformamide (DMF) and 30 ml of toluene is boiled, the water formed in the course of the reaction being removed azeotropically.
The reaction mixture is then evaporated to dryness. The residue is dissolved in 200 ml of methylene chloride and the solution is extracted by shaking with 100 ml of satura-ted sodium chloride solution. The methylene chloride solution is then dried with anhydrous sodium sulphate and evaporated, 18 g (76% of theory) of N-(~-hydroxy-ethyl)-3-nitrophthalimide are obtained as an oily residue, which crystallises in a short time; melting point 93C.
IR spectrum (CH2C12): 1790 cm 1 and 1730 cm 1 (C0-N-C0);
1550 cm 1 and 1370 cm 1 (C02).
Exam~e 2 31,85 g (0.135 mol) of a mixture of N-(~-hydroxy-ethyl)-3- and -4-nitrophthalimide are heated with 9.62 g (0,148 mol) of sodium azide in 360 ml of dimethylsulphox-., . ;, .: . .. . ~: ..
~8626 ide for 18 hours at 80C. The solution is then con-centrated in vacuo at 80C and the residue is stirred with 250 ml of water. The resulting suspension is filtered with suction, the filter residue is résuspended in 100 ml -;
of water and this suspension is stirred for 18 hours.
After filtering the suspension with suction, and drying the filter residue at 70C/100 mm Hg, 24,5 g (78.6% of theory) of a mixture of N-(~-hydroxyethyl)-3- and -4-azido-phthalimide are obtained; melting point 102C (with decomposition). IR spectrum (CHzCl2): 1785 cm 1 and 1725 cm 1 (C0-N-C0); 2125 cm 1 (N3).
The mixture of N-(~-hydroxyethyl)-3- and -4-nitrophthalimide can be prepared as follows: 38.6 g (0.2 mol) of a mixture of 3- and 4-nitrophthalic anhydride, 13.4 g (0.22 mol) of ethanolamine, 100 ml of N,N-dimethyl-formamide and 60 ml of toluene are refluxed, the water formed in the course of the reaction being removed azeo-tropically. The reaction mixture is then evaporated to dryness in vacuo. The oily residue is dissolved in 200 ml of methylene chloride and the solution is twice extracted by shaking with saturated sodium chloride solu-tion. The methylene chloride solution is dried with anhydrous sodium sulphate and evaporated to dryness.
The oily residue crystallises on stirring with 500 ml of diethyl ether. After filtering the resulting yellow crystalline suspension with suction, and drying the filter residue at 40C/100 mm Hg, 31.6 g (67% of theory) of a mixture of N-(~-hydroxyethyl)-3- and -4-nitrophthalimide are obtained; melting point 80-95C. IR spectrum (dioxan): 1780 cm 1 and 1720 cm 1 (C0-N-C0); 1550 cm 1 and 1340 cm 1 (N02).
Example 3 630 g (3.26 mols) of an isomer mixture of 3-and 4-nitrophthalic anhydride are dissolved in 1,632 mols of N,N-dimethylformamide, and 218 g (3.57 mols) of ethanolamine and 980 ml of toluene are added. The reaction mixture is refluxed, the water - .
.. ..
il~8626 formed in the course of the reaction being distilled off azeotropically. The reaction mixture is then evapora-ted in vacuo at 90C. 7,000 ml of dimethylsulphoxide and 263 g (4.04 mols) of sodium azide are added to the oily residue. The reaction mixture is-then heated for 20 hours at 80C, after which it is concentrated in vacuo at 90-100C, and the residue is stirred with 5,500 ml of water. The resulting yellow suspension is filtered with suction and the filter residue is dried in vacuo at 60C over solid sodium hydroxide, 647 g (85.5% of theory) of an isomer mixture of N-(~-hydroxyethyl)-~- and -4-nitrophthalimide are obtained; mèlting point 90-105C
~with decomposition). IR spectrum (CH2C12) 1780 cm 1 and 1720 cm 1 (CO-N-CO); 2125 cm 1 (N3).
Example 4 A mixture of 2.9 g (0.01 mol) of 4-(3-nitrophthal-imidyl)-cyclohexanol and 0.9 g (0.013 mol) of sodium azide in 20 ml of dimethylsulphoxide is stirred for 6 hours at 80C and then evaporated in vacuo at the same temperature.
e residue is diluted with 20 ml of water. The pro-duct which has separated out is filtered off with suction, washed with 5 ml of water and dried for 24 hours at 80C
in a drying cabinet. 2.6 g (91% of theory) of 4-(3-azidophthalimidyl)-cyclohexanol are obtained; melting point 155C (with decomposition). IR spectrum (KBr):
1775 cm 1 and 1710 cm 1 (CO-N-CO); 2130 cm 1 (N3).
The starting material used in the above example can be prepared as follows: A mixture of 29.4 g (0.25 mol) of 4-aminocyclohexanol, 43.9 g (0.227 mol) of 3-nitro-phthalic anhydride, 120 ml of N,N-dimethylformamide and 75 ml of toluene is heated to the boil, with azeotropic removal of the water formed during the reaction, and is finally evaporated. The oily residue is dissolved in 1,000 ml of methylene chloride and the solution is extract-ed with four times 40.0 ml of 5% aqueous NaOH
solution. The methylene chloride solution is dried with anhydrous sodium sulphate and evaporated. The :: . : , . ........................ . . , "
., . , ~ , ;, ~ :: - .~ i . ..
~1~f3626 oily residue is dissolved in 280 ml of hot methanol.
On cooling, 16 g (22% of theory) of 4-(3-nitrophthal-imidyl)-cyclohexanol crystallise out; melting point 215C.
IR spectrum (CH2C12): 1790 cm 1 and 1730 cm 1 (CO-N-CO);
1550 cm 1 and 1370 cm 1 (N02), Example 5 A mixture of 55 g (0.193 mol) of 4-(3-nitrophthal-imidyl)-phenol and 13.8 g (0.212 mol) of sodium azide in 380 ml of dimethylsulphoxide is heated for 6 hours at 50C.
The reaction mixture is evaporated in vacuo at 80C and the residue is stirred with 1,000 ml of water for 18 hours, After filtering the resulting suspension, and drying the filter residue in a drying cabinet at 60C over phosphorus pentoxide, 56 6 g (95% of theory) of 4-(3-azidophthalim-idyl)-phenol are obtained; melting point 165C (with decomposition). IR spectrum (KBr): 1780 and 1715 cm 1 (CO-N-CO); 2140 cm 1 (N3).
The starting material used in the above example can be prepared as follows: 34.3 g (0.31 mol) of 4-aminophenol and 59.9 g (0.31 mol) of 3-nitrophthalic anhydride in 600 ml of acetic acid are refluxed for - 6'''hours and the mixture is then stirred into 3,000 ml of water. The product which has pre-cipitated is washed with water and dried ~or Z4 hours at 70C/30 mm Hg. 69 g (78% of theory) of 4-(3-nitro-phthalimidyl)-phenol are obtained; melting point 202C.
IR spectrum (KBr): 1785 cm 1 and 1725 cm 1 (CO-N-CO);
1550 and 1350 cm 1 (N02).
Example 6 13.5 g (0.047 mol) of 4-(3-nitrophthalimidyl)-aniline and 3.4 g (0.051 mol) of sodium azide in 120 ml of dimethylsulphoxide are heated for 18 hours at 80C.
The reaction mixture is then concentrated in vacuo at 80C
and diluted with 100 ml of water, the mixture is filtered with suction and the filter residue is washed with 20 ml of water and dried for 24 hours in a drying cabine-t at 80C/100 mm Hg. 13.1 g (100% of theory) of 4-(3-azido-.. ...
...
: ~ . ..
~ 86Z6 phthalimidyl)-aniline are obtained; melting point 176C
(with decomposition). IR spectrum (KBr): 1780 and 1725 cm 1 (C0-N-C0); 2130 cm ~ (N3).
4-(3-Nitrophthalimidyl)-aniline, used in the above example, can be prepared as follows: .4~.3 ~ (0.25 mol) of 3-nitrophthalic anhydride and 37.5 g (0.25 mol) of 4-aminoacetanilide in 500 ml of acetic acid are refluxed for 8~hours and are then cooled.
The crystals which have separated out are filtered off with suction, washed with 150 ml of ethanol and dried for 24 hours at 80C/~0 mm Hg. 65 g (8~/~ of theory) of 4-(3-nitrophthalimidyl)-acetanilide are obtained; melt-ing point 255C. 65 g (0.2 mol) of 4-(3-nitrophthal-imidyl)-acetanilide are heated with a mixture of 400 ml of dioxan and 200 ml of concentrated hydrochloric acid for 3 hours at 90C and the whole is then left to stand for 24 hours at 25C. The crystals which have sep-arated out are filtered off with suction and washed with 100 ml of methanol 45 g (70% of theory) of crude 4-(3-nitrophthalimidyl)-aniline hydrochloride are obtained.
45 g (0,14 mol) of this hydrochloride are mixed with 100 ml of water and 200 ml of a saturated sodium bicarbonate solution are added dropwise at 5C. After one hour, the resulting fine precipitate is filtered off with suction, washed three times with 50 ml of water and dried for 24 hours at 25C/1 mm Hg. 21 g (54/0 of theory) of 4-(3-nitrophthalimidyl)-aniline are obtained; melting point 177C. IR spectrum (KBr): 1790 and 1725 cm 1 (C0-N-C0); 1540 and 1360 cm 1 (N02).
ExamPle ?
1.4 ml (0.01 mol) of triethylamine, followed by 0.72 g (0.011 mol) of sodium azide, are added to a mixture of 3.12 g (0.01 mol) of 4-(3-nitrophthalimidyl)-benzoic acid and 20 ml of dimethylsulphoxide. The reaction ~ mixture is heated for 6 hours at 50C and is then evapora-ted in vacuo at 80C; the residue is s~irred with 70 ml ; - of water and the resulting solution is then brought to .
~9 ~8626 pH 1 with hydrochloric acid. The product which has precipitated is filtered off with suction, washed with 5 ml of methanol and dried for 24 hours in a drying cabinet at 80C/100 mm Hg. 2.47 g (80% of theory) of 4-(3-azidophthalimidyl)-benzoic acid are obtained;
melting point 300C (with decomposition). IR spec-trum (KBr): 1790 and 1740 cm 1 (C0-N-C0); 2150 cm 1 (N3).
The starting material used in the above example can be prepared as follows: 57.9 g (0.3 mol) of 3-nitrophthalic anhydride and 41.1 g ~0.3 mol) of 4-amino-benzoic acid in 600 ml of acetic acid are refluxed for 6 hours and the mixture is then stirred into 1,000 ml of 50% aqueous ethanol. The yellow product which has precipitated is filtered off with suction, washed with water and dried at 80C/30 mm Hg for 24 hours.
82 g (88% of theory) of 4-(3-nitrophthalimidyl)-benzoic acid are obtained; melting point > 300C.
IR spectrum (KBr): 1790 and 1740 cm 1 (C0-N-C0);
1550 and 1370 cm 1 (N02).
Example 8 2.58 ml (0.018 mol) of triethylamine, followed by 1,3 g (0.0198 mol) of sodium azide, are added to a mix-ture of 5.7 g (0.018 mol) of 6-(3-nitrophthalimidyl)-caproic acid in 35 ml of dimethylsulphoxide. The reaction mixture is heated for 6 hours at 50C and is then concentrated in vacuo, diluted with 100 ml of water and acidified with 4 ml of concentrated hydrochloric acid.
The resulting suspension of the reaction product is stirred for 18 hours and filtered with suction, and the filter residue is washed with 20 ml of water and dried for 24 hours at 60C/.100. mm Hg, over phosphorus pentoxide.
5.1 g (94% of theory) of 6-(3-azidophthalimidyl)-caproic ~cid are obtained; melting point 87-90C (with decomposi-tion). IR spectrum (CH2C12): 1780 and 1725 cm 1 (C0-N-C0); 2130 cm 1 (N~).
The starting material used in the above example can be prepared as follows: 3.86 g (0.02 mol) of 3-, .; , .. ~ ~..,:, .. .
.
~386Z6 .
nitrophthalic anhydride and 2.9 g (0.022 mol) of 6-amino-caproic acid are heated under reflux for 8 hours and then evaporated. The solid residue is stirred with water, fi-ltered off with suction and dried for 24 hours at 80C.
5.7 g (93% of theory) of 6-(3-nitrophthalimi~yl)-caproic acid are obtained; melting point 148-150C. IR
spectrum (CH~C12): 1790 and 1725 cm 1 (CO-N-CO); 1550 and 1370 cm (N02)~
Example 9 A solution of 3.78 g (0.02 mol) of 3-azidophthalic anhydride in 50 ml of dioxan is mixed with a solution of 2.74 g (0.02 mol) of p-aminobenzoic acid in 50 ml of dioxan and the mixture is left to stand for 3 hours.
5 ml of acetic anhydride are then added and the reaction mixture is heated for 1 hour at 85C. After con-centrating to dryness, the residue is mixed with water and the resulting crystals are filtered off with suction.
4.8 g (78% of theory) of 4-(3-azidophthalimidyl)-benzoic acid are obtained; melting point 300C (with decompos-ition).
Example 10 N3 ~ ,N-(CH2)2-O-co-c~l=cH
In a 500 ml sulphonation flask equipped with a 50 ml dropping funnel with pressure equaliser, a high-efficiency condenser with drying tube, and a thermometer, 23.1 g (0.1 mol) of the mixtuPe of N-(~-hydroxyethyl)-3-and -4-azidophthalimide obtained according to Example 2 and 10.1 g (0,1 mol) of triethylamine (dried over NaOH) are dissolved in 250 ml of dry methylene chloride and the solution is cooled to 0C, the operations being carried out under a nitrogen atmosphere. 9.05g (0.1 mol)of acryloyl chloride are added dropwise to this solution at a rate such that the temperature does not exceed 10G. After ~862~
the reaction has ended 9 the reaction mixture is stirred until it has come to room temperature (20-25C). The triethylamine hydrochloride which has precipitated during the reaction is separated from the remainder of the reac-tion solution by filtration. The methyIene chloride extract is washed neutral with water, dried with Na sul-phate and then concentrated in vacuo, without heating.
25.9 g (90.7% of theory) of a mixture of N-(~-acryloyloxy-ethyl)-3- and -4-azidophthalimide are obtained, NMR spec-trum: H2C=CH- 5.7-6,3 (3H) ppm; ~internal standard TMS=O), Example 11 In an apparatus of the type described in Example 10, 23.2 g (0.1 mol) of a mixture of N-(~-hydroxyethyl)-3-and -4-azidophthalimide and 10.1 g (0.1 mol) of triethyl-amine (dried over NaOH) are dissolved in 250 ml of dry methylene chloride and the solution is cooled to 0C, the operations being carried out under a nitrogen atmosphere.
10,45 g (0.1 mol) of methacryloyl chloride are added drop-wise to this solution at a rate such that the temperature does not exceed 10C. After the reaction has ended, the reaction mixture is stirred until it has come to room tem-perature. The triethylamine hydrochloride which has precipitated during the reaction is separated from the remainder of the reaction solution by filtration. The methylene chloride extract is washed neutral with water, dried with Na sulphate and concentrated in vacuo, without heating. 27.65 g (92.2% of theory) of a mixture of N-(~-methacryloyloxyethyl)-3- and -4-azidophthalimide are obtained. NMR spectrum: H2C=C- 6.1 (lH) and 5.6 (lH) ' CH3 ppm; internal standard TMS = O.
Example 12 15.0 g (0.05 mol) of the 6-(3-azidophthalimidyl)-caproic acid obtained according to Example 8 are dissolved in 327 g (2.75 mols) of thionyl chloride, and the solution is warmed to 80C, the operations being carried out under yellow light. At 80C, 0.5 ml of N,N-dimethylforma-.
.~ . .. .
-- 19 -- ' mide is added to the clear solution obtained. Thereaction mixture is stirred for 15 minutes at 80C and is then cooled to room temperaturé. This produces a beige-coloured suspension, which is filtered with suction, under N2. The crude product is recrystallised from 250 ml of dry ligroin. 12.5 g (75.4% of theory) of 6-(3-azidophthalimidyl)-caproyl chloride are obtained;
melting point 68-69C, Elementary analysis;
calculated C 52.43% H 4.09% N~17.47% Cl 11. 06%
found C 52.61% H 4.13% N 17.27% Cl 9.04%
Example 13 N3 0 ~ CH (CH2)8 C CH2H
A mixture of 20.9 g (0.05 mol) of` N-(l-ethyl-10,10-dimethyl-11-hydroxyundecyl)-3-nitrophthalimide and
Examples of suitable compounds for process 1) are those of the formula Ib in which Z is -OH, -COOH, -COCl, -NH2 or -NH-alkyl having 1-4 C atoms, such compounds being reacted, for example, with polymers having recurring structural units of the formulae ÇH - CO ~ ~H2 CH2 / \
~H - CO ~ . H - OH, R - C - COO(CH2 ~ CH CH2 or CH2 / \
O(CH2 ~ CH 2 (where R is hydrogen or methyl - : .... - . ~ ~
: ~ . - ~. :. . .......... ..
..
~8626 and y is 1 or 2).
Suitable compounds for process 2) are, in parti-cular, those of the formula Ib in which Z is -O-COCH=CH2, -O-COC=CH2, -COOCH=CH2 or -OCH=CH2, such-compounds being polymerised, by themselves or together with other ethylen-ically unsaturated monomers, for example vinyl chloride, vinylidene chloride, acrylic acid, acrylonitrile, alkyl acrylates and alkyl methacrylates, styrene, ethylene, pro-pylene, isoprene, chloroprene, 1,4-butadiene, vinyl ace-tate, vinyl propionate, maleic acid, fumaric acid or maleic anhydride.
The polymers thus obtained, having azidophthalimidyl side groups, can be photo-crosslinked, especially with UV
light, and are suitable for photomechanical applications, for example for the manufacture of printing plates for the offset printing process, for the manufacture of photo-offset lacquers, for unconventional photography, for example for the production of so-called vesicular images, or for colouring polymer images, which after exposure and development are not easily visible, by means of suitable dyes, for example oil-soluble dyes, or, if the polymer con-tains acid groups, for example carboxylic acid or sulphonic acid groups, with cationic dyes, The polymers accord-ing to the invention are used in particular as so-called photo-resists for the manufacture of printed circuits by methods known per se. In these, the side of the con-ductive plate provided with the photosensitive layer is exposed through a negative transparency carrying the con-ductor image and is then developed, after which the unex-posed areas of the layer are removed with developer fluid.
Exposure can be effected by means of sunlight, carbon arcs or xenon lamps, but is advantageously carried out with high pressure mercury lamps.
.
... . . .
. - . ~ ~ . .
. ~ .
~ ~ -~i86Z6 Example 1 N-C
A mixture of 17.9 g (o.076 mol) of N-(~hydroxy-ethyl)-3-nitrophthalmide and 5,11 g (0.078 mol) of sodium azide in 70 ml of dimethylsulphoxide is stirred at 50C
for 12 hours. The solution is evaporated in vacuo and the residue is stirred with 200 ml of ice-water. The crystals which have precipitated are filtered off with suction, washed with 20 ml of water and dried for 24 hours at 80C/100 mm Hg, 17 g (97% of theory) of N-(~-hydroxyethyl)-3-azidophthalimide are obtained; melting point 141C (with decomposition). IR spectrum (CH2C12):
1775 cm 1 and 1720 cm 1 (C0-N-C0); 2120 cm 1 (N3).
N-(~-Hydroxyethyl-3-nitrophthalimide, used in the above example, can be prepared as follows: a mixture of 19.3 g (0.1 mol) of 3-nitrophthalic anhydride, 6.7 g (0.1 mol) of ethanolamine, 50 ml of N,N-dimethylformamide (DMF) and 30 ml of toluene is boiled, the water formed in the course of the reaction being removed azeotropically.
The reaction mixture is then evaporated to dryness. The residue is dissolved in 200 ml of methylene chloride and the solution is extracted by shaking with 100 ml of satura-ted sodium chloride solution. The methylene chloride solution is then dried with anhydrous sodium sulphate and evaporated, 18 g (76% of theory) of N-(~-hydroxy-ethyl)-3-nitrophthalimide are obtained as an oily residue, which crystallises in a short time; melting point 93C.
IR spectrum (CH2C12): 1790 cm 1 and 1730 cm 1 (C0-N-C0);
1550 cm 1 and 1370 cm 1 (C02).
Exam~e 2 31,85 g (0.135 mol) of a mixture of N-(~-hydroxy-ethyl)-3- and -4-nitrophthalimide are heated with 9.62 g (0,148 mol) of sodium azide in 360 ml of dimethylsulphox-., . ;, .: . .. . ~: ..
~8626 ide for 18 hours at 80C. The solution is then con-centrated in vacuo at 80C and the residue is stirred with 250 ml of water. The resulting suspension is filtered with suction, the filter residue is résuspended in 100 ml -;
of water and this suspension is stirred for 18 hours.
After filtering the suspension with suction, and drying the filter residue at 70C/100 mm Hg, 24,5 g (78.6% of theory) of a mixture of N-(~-hydroxyethyl)-3- and -4-azido-phthalimide are obtained; melting point 102C (with decomposition). IR spectrum (CHzCl2): 1785 cm 1 and 1725 cm 1 (C0-N-C0); 2125 cm 1 (N3).
The mixture of N-(~-hydroxyethyl)-3- and -4-nitrophthalimide can be prepared as follows: 38.6 g (0.2 mol) of a mixture of 3- and 4-nitrophthalic anhydride, 13.4 g (0.22 mol) of ethanolamine, 100 ml of N,N-dimethyl-formamide and 60 ml of toluene are refluxed, the water formed in the course of the reaction being removed azeo-tropically. The reaction mixture is then evaporated to dryness in vacuo. The oily residue is dissolved in 200 ml of methylene chloride and the solution is twice extracted by shaking with saturated sodium chloride solu-tion. The methylene chloride solution is dried with anhydrous sodium sulphate and evaporated to dryness.
The oily residue crystallises on stirring with 500 ml of diethyl ether. After filtering the resulting yellow crystalline suspension with suction, and drying the filter residue at 40C/100 mm Hg, 31.6 g (67% of theory) of a mixture of N-(~-hydroxyethyl)-3- and -4-nitrophthalimide are obtained; melting point 80-95C. IR spectrum (dioxan): 1780 cm 1 and 1720 cm 1 (C0-N-C0); 1550 cm 1 and 1340 cm 1 (N02).
Example 3 630 g (3.26 mols) of an isomer mixture of 3-and 4-nitrophthalic anhydride are dissolved in 1,632 mols of N,N-dimethylformamide, and 218 g (3.57 mols) of ethanolamine and 980 ml of toluene are added. The reaction mixture is refluxed, the water - .
.. ..
il~8626 formed in the course of the reaction being distilled off azeotropically. The reaction mixture is then evapora-ted in vacuo at 90C. 7,000 ml of dimethylsulphoxide and 263 g (4.04 mols) of sodium azide are added to the oily residue. The reaction mixture is-then heated for 20 hours at 80C, after which it is concentrated in vacuo at 90-100C, and the residue is stirred with 5,500 ml of water. The resulting yellow suspension is filtered with suction and the filter residue is dried in vacuo at 60C over solid sodium hydroxide, 647 g (85.5% of theory) of an isomer mixture of N-(~-hydroxyethyl)-~- and -4-nitrophthalimide are obtained; mèlting point 90-105C
~with decomposition). IR spectrum (CH2C12) 1780 cm 1 and 1720 cm 1 (CO-N-CO); 2125 cm 1 (N3).
Example 4 A mixture of 2.9 g (0.01 mol) of 4-(3-nitrophthal-imidyl)-cyclohexanol and 0.9 g (0.013 mol) of sodium azide in 20 ml of dimethylsulphoxide is stirred for 6 hours at 80C and then evaporated in vacuo at the same temperature.
e residue is diluted with 20 ml of water. The pro-duct which has separated out is filtered off with suction, washed with 5 ml of water and dried for 24 hours at 80C
in a drying cabinet. 2.6 g (91% of theory) of 4-(3-azidophthalimidyl)-cyclohexanol are obtained; melting point 155C (with decomposition). IR spectrum (KBr):
1775 cm 1 and 1710 cm 1 (CO-N-CO); 2130 cm 1 (N3).
The starting material used in the above example can be prepared as follows: A mixture of 29.4 g (0.25 mol) of 4-aminocyclohexanol, 43.9 g (0.227 mol) of 3-nitro-phthalic anhydride, 120 ml of N,N-dimethylformamide and 75 ml of toluene is heated to the boil, with azeotropic removal of the water formed during the reaction, and is finally evaporated. The oily residue is dissolved in 1,000 ml of methylene chloride and the solution is extract-ed with four times 40.0 ml of 5% aqueous NaOH
solution. The methylene chloride solution is dried with anhydrous sodium sulphate and evaporated. The :: . : , . ........................ . . , "
., . , ~ , ;, ~ :: - .~ i . ..
~1~f3626 oily residue is dissolved in 280 ml of hot methanol.
On cooling, 16 g (22% of theory) of 4-(3-nitrophthal-imidyl)-cyclohexanol crystallise out; melting point 215C.
IR spectrum (CH2C12): 1790 cm 1 and 1730 cm 1 (CO-N-CO);
1550 cm 1 and 1370 cm 1 (N02), Example 5 A mixture of 55 g (0.193 mol) of 4-(3-nitrophthal-imidyl)-phenol and 13.8 g (0.212 mol) of sodium azide in 380 ml of dimethylsulphoxide is heated for 6 hours at 50C.
The reaction mixture is evaporated in vacuo at 80C and the residue is stirred with 1,000 ml of water for 18 hours, After filtering the resulting suspension, and drying the filter residue in a drying cabinet at 60C over phosphorus pentoxide, 56 6 g (95% of theory) of 4-(3-azidophthalim-idyl)-phenol are obtained; melting point 165C (with decomposition). IR spectrum (KBr): 1780 and 1715 cm 1 (CO-N-CO); 2140 cm 1 (N3).
The starting material used in the above example can be prepared as follows: 34.3 g (0.31 mol) of 4-aminophenol and 59.9 g (0.31 mol) of 3-nitrophthalic anhydride in 600 ml of acetic acid are refluxed for - 6'''hours and the mixture is then stirred into 3,000 ml of water. The product which has pre-cipitated is washed with water and dried ~or Z4 hours at 70C/30 mm Hg. 69 g (78% of theory) of 4-(3-nitro-phthalimidyl)-phenol are obtained; melting point 202C.
IR spectrum (KBr): 1785 cm 1 and 1725 cm 1 (CO-N-CO);
1550 and 1350 cm 1 (N02).
Example 6 13.5 g (0.047 mol) of 4-(3-nitrophthalimidyl)-aniline and 3.4 g (0.051 mol) of sodium azide in 120 ml of dimethylsulphoxide are heated for 18 hours at 80C.
The reaction mixture is then concentrated in vacuo at 80C
and diluted with 100 ml of water, the mixture is filtered with suction and the filter residue is washed with 20 ml of water and dried for 24 hours in a drying cabine-t at 80C/100 mm Hg. 13.1 g (100% of theory) of 4-(3-azido-.. ...
...
: ~ . ..
~ 86Z6 phthalimidyl)-aniline are obtained; melting point 176C
(with decomposition). IR spectrum (KBr): 1780 and 1725 cm 1 (C0-N-C0); 2130 cm ~ (N3).
4-(3-Nitrophthalimidyl)-aniline, used in the above example, can be prepared as follows: .4~.3 ~ (0.25 mol) of 3-nitrophthalic anhydride and 37.5 g (0.25 mol) of 4-aminoacetanilide in 500 ml of acetic acid are refluxed for 8~hours and are then cooled.
The crystals which have separated out are filtered off with suction, washed with 150 ml of ethanol and dried for 24 hours at 80C/~0 mm Hg. 65 g (8~/~ of theory) of 4-(3-nitrophthalimidyl)-acetanilide are obtained; melt-ing point 255C. 65 g (0.2 mol) of 4-(3-nitrophthal-imidyl)-acetanilide are heated with a mixture of 400 ml of dioxan and 200 ml of concentrated hydrochloric acid for 3 hours at 90C and the whole is then left to stand for 24 hours at 25C. The crystals which have sep-arated out are filtered off with suction and washed with 100 ml of methanol 45 g (70% of theory) of crude 4-(3-nitrophthalimidyl)-aniline hydrochloride are obtained.
45 g (0,14 mol) of this hydrochloride are mixed with 100 ml of water and 200 ml of a saturated sodium bicarbonate solution are added dropwise at 5C. After one hour, the resulting fine precipitate is filtered off with suction, washed three times with 50 ml of water and dried for 24 hours at 25C/1 mm Hg. 21 g (54/0 of theory) of 4-(3-nitrophthalimidyl)-aniline are obtained; melting point 177C. IR spectrum (KBr): 1790 and 1725 cm 1 (C0-N-C0); 1540 and 1360 cm 1 (N02).
ExamPle ?
1.4 ml (0.01 mol) of triethylamine, followed by 0.72 g (0.011 mol) of sodium azide, are added to a mixture of 3.12 g (0.01 mol) of 4-(3-nitrophthalimidyl)-benzoic acid and 20 ml of dimethylsulphoxide. The reaction ~ mixture is heated for 6 hours at 50C and is then evapora-ted in vacuo at 80C; the residue is s~irred with 70 ml ; - of water and the resulting solution is then brought to .
~9 ~8626 pH 1 with hydrochloric acid. The product which has precipitated is filtered off with suction, washed with 5 ml of methanol and dried for 24 hours in a drying cabinet at 80C/100 mm Hg. 2.47 g (80% of theory) of 4-(3-azidophthalimidyl)-benzoic acid are obtained;
melting point 300C (with decomposition). IR spec-trum (KBr): 1790 and 1740 cm 1 (C0-N-C0); 2150 cm 1 (N3).
The starting material used in the above example can be prepared as follows: 57.9 g (0.3 mol) of 3-nitrophthalic anhydride and 41.1 g ~0.3 mol) of 4-amino-benzoic acid in 600 ml of acetic acid are refluxed for 6 hours and the mixture is then stirred into 1,000 ml of 50% aqueous ethanol. The yellow product which has precipitated is filtered off with suction, washed with water and dried at 80C/30 mm Hg for 24 hours.
82 g (88% of theory) of 4-(3-nitrophthalimidyl)-benzoic acid are obtained; melting point > 300C.
IR spectrum (KBr): 1790 and 1740 cm 1 (C0-N-C0);
1550 and 1370 cm 1 (N02).
Example 8 2.58 ml (0.018 mol) of triethylamine, followed by 1,3 g (0.0198 mol) of sodium azide, are added to a mix-ture of 5.7 g (0.018 mol) of 6-(3-nitrophthalimidyl)-caproic acid in 35 ml of dimethylsulphoxide. The reaction mixture is heated for 6 hours at 50C and is then concentrated in vacuo, diluted with 100 ml of water and acidified with 4 ml of concentrated hydrochloric acid.
The resulting suspension of the reaction product is stirred for 18 hours and filtered with suction, and the filter residue is washed with 20 ml of water and dried for 24 hours at 60C/.100. mm Hg, over phosphorus pentoxide.
5.1 g (94% of theory) of 6-(3-azidophthalimidyl)-caproic ~cid are obtained; melting point 87-90C (with decomposi-tion). IR spectrum (CH2C12): 1780 and 1725 cm 1 (C0-N-C0); 2130 cm 1 (N~).
The starting material used in the above example can be prepared as follows: 3.86 g (0.02 mol) of 3-, .; , .. ~ ~..,:, .. .
.
~386Z6 .
nitrophthalic anhydride and 2.9 g (0.022 mol) of 6-amino-caproic acid are heated under reflux for 8 hours and then evaporated. The solid residue is stirred with water, fi-ltered off with suction and dried for 24 hours at 80C.
5.7 g (93% of theory) of 6-(3-nitrophthalimi~yl)-caproic acid are obtained; melting point 148-150C. IR
spectrum (CH~C12): 1790 and 1725 cm 1 (CO-N-CO); 1550 and 1370 cm (N02)~
Example 9 A solution of 3.78 g (0.02 mol) of 3-azidophthalic anhydride in 50 ml of dioxan is mixed with a solution of 2.74 g (0.02 mol) of p-aminobenzoic acid in 50 ml of dioxan and the mixture is left to stand for 3 hours.
5 ml of acetic anhydride are then added and the reaction mixture is heated for 1 hour at 85C. After con-centrating to dryness, the residue is mixed with water and the resulting crystals are filtered off with suction.
4.8 g (78% of theory) of 4-(3-azidophthalimidyl)-benzoic acid are obtained; melting point 300C (with decompos-ition).
Example 10 N3 ~ ,N-(CH2)2-O-co-c~l=cH
In a 500 ml sulphonation flask equipped with a 50 ml dropping funnel with pressure equaliser, a high-efficiency condenser with drying tube, and a thermometer, 23.1 g (0.1 mol) of the mixtuPe of N-(~-hydroxyethyl)-3-and -4-azidophthalimide obtained according to Example 2 and 10.1 g (0,1 mol) of triethylamine (dried over NaOH) are dissolved in 250 ml of dry methylene chloride and the solution is cooled to 0C, the operations being carried out under a nitrogen atmosphere. 9.05g (0.1 mol)of acryloyl chloride are added dropwise to this solution at a rate such that the temperature does not exceed 10G. After ~862~
the reaction has ended 9 the reaction mixture is stirred until it has come to room temperature (20-25C). The triethylamine hydrochloride which has precipitated during the reaction is separated from the remainder of the reac-tion solution by filtration. The methyIene chloride extract is washed neutral with water, dried with Na sul-phate and then concentrated in vacuo, without heating.
25.9 g (90.7% of theory) of a mixture of N-(~-acryloyloxy-ethyl)-3- and -4-azidophthalimide are obtained, NMR spec-trum: H2C=CH- 5.7-6,3 (3H) ppm; ~internal standard TMS=O), Example 11 In an apparatus of the type described in Example 10, 23.2 g (0.1 mol) of a mixture of N-(~-hydroxyethyl)-3-and -4-azidophthalimide and 10.1 g (0.1 mol) of triethyl-amine (dried over NaOH) are dissolved in 250 ml of dry methylene chloride and the solution is cooled to 0C, the operations being carried out under a nitrogen atmosphere.
10,45 g (0.1 mol) of methacryloyl chloride are added drop-wise to this solution at a rate such that the temperature does not exceed 10C. After the reaction has ended, the reaction mixture is stirred until it has come to room tem-perature. The triethylamine hydrochloride which has precipitated during the reaction is separated from the remainder of the reaction solution by filtration. The methylene chloride extract is washed neutral with water, dried with Na sulphate and concentrated in vacuo, without heating. 27.65 g (92.2% of theory) of a mixture of N-(~-methacryloyloxyethyl)-3- and -4-azidophthalimide are obtained. NMR spectrum: H2C=C- 6.1 (lH) and 5.6 (lH) ' CH3 ppm; internal standard TMS = O.
Example 12 15.0 g (0.05 mol) of the 6-(3-azidophthalimidyl)-caproic acid obtained according to Example 8 are dissolved in 327 g (2.75 mols) of thionyl chloride, and the solution is warmed to 80C, the operations being carried out under yellow light. At 80C, 0.5 ml of N,N-dimethylforma-.
.~ . .. .
-- 19 -- ' mide is added to the clear solution obtained. Thereaction mixture is stirred for 15 minutes at 80C and is then cooled to room temperaturé. This produces a beige-coloured suspension, which is filtered with suction, under N2. The crude product is recrystallised from 250 ml of dry ligroin. 12.5 g (75.4% of theory) of 6-(3-azidophthalimidyl)-caproyl chloride are obtained;
melting point 68-69C, Elementary analysis;
calculated C 52.43% H 4.09% N~17.47% Cl 11. 06%
found C 52.61% H 4.13% N 17.27% Cl 9.04%
Example 13 N3 0 ~ CH (CH2)8 C CH2H
A mixture of 20.9 g (0.05 mol) of` N-(l-ethyl-10,10-dimethyl-11-hydroxyundecyl)-3-nitrophthalimide and
3.55 g (0.055 mol) of sodium azide in 100 ml o~ dimethyl-sulphoxide is stirred for 24 hours at 80C. The solu-tion is evaporated in vacuo and the residue is diluted with 300 ml of water. The resulting emulsion is ex-tracted with twice 100 ml of diethyl ether. The ether extracts are first dried with anhydrous sodium sul-phate, and then evaporated. 14.7 g (71% of theory) of N-(l-ethyl-10,10-dimethyl-11-hydroxyundecyl)-3-azidophth-alimide are obtained in the form of a viscous oil which cannot be distilled.
IR spectrum (CHC13): 1780 and 1725 cm 1 (C0-N-C0); 2130 cm 1 (N3).
The starting material used in the above example can be prepared as follows: A mixture of 9.6 g (0.05 mol) of 3-nitrophthalic anhydride, 12.9 g (0.055 mol) of l-ethyl-10,10-dimethyl-11-hydroxy-1-aminoundecane, 150 ml of toluene and 250 ml of dimethylformamide is heated to ..
- . ,, 1~8626 the boil, the water formed being removed azeotropically.
The reaction mixture is then evaporated to dryness.
The residue is dissolved in 150 ml of methylene chloride and the solution is extracted with three times 50 ml of 10% sodium carbonate solution. The methylene chloride solution is then dried over anhydrous sodium sulphate and evaporated. 20.9 g (about 100% of theory) of N-(l-ethyl-10,10-dimethyl~ hydroxyundecyl)-3-nitro-phthalimide are obtained in the form of a viscous oil which gradually crystallises after standing for several weeks; melting point 66-68C.
Example 14 A mixture of 2.4 g (0.007 mol) of 1-(3~nitro-phthalimidyl)-7-hydroxynaphthalene and 0.52 g (0.008 mol) of sodium azide in 14 ml of dimethylsulphoxide is stirred for 24 hours al 80C. 100 ml of water are added to the solution. The crystals which have precipitated are filtered off with suction, washed with water and dried at 80C/100 mm Hg. 1.7 g (73.6% of theory) of 1-(3-azidophthalimidyl)-7-hydroxynaphthalene are obtained;
melting point 154C (with decomposition). IR spectrum (KBr): 1775 and 1720 cm 1 (C0-N-C0); 2130 cm 1 (N3).
The starting material used in the above example can be prepared as follows: A mixture of 1.93 g (0.01 mol) of 3-nitrophthalic anhydride, 1.59 g (0.01 mol) of l-amino-7-naphthol and 30 ml of acetic acid is re~luxed for 17 hours. The resulting suspension is stirred with 300 ml of water, t~en filtered and the ~lter residue is then washed with water and dried. 2.9g of cr~de product are obtained and are extracted with chloroform. The chloroform extract is stirred with 4 g of silica gel, filtered with suction whilst hot, and evaporated to dryness. 2.4 g (72% of theory) of ~ nitrophthalimidyl)-7-hydroxynaphthalene are obtained;
melting point 136-7C.
Example 15 120.0 g of a mixture of N-(~-methacryloyloxyethyl)-3- and -4-azidophthalimide and 1.20 g of azoisobutyronit-.
.. . ..
- . . . . : ., . -.; , . , . - .,., . .:
... .
~8626 rile are dissolved in 545 ml of tetrahydrofuran, under yellow light, in a 1 litre reaction vessel equipped with a jacket, stirrer, high-efficiency condenser and thermo-meter This solution is polymerised for 8 hours at 70C, with stirring and under a nitrogen atmosphere.
After the reaction has ended, the reaction mixture is cooled to room temperature (20-25C) and the polymer is precipitated by dripping the reaction solution into 4 litres of n-hexane. 113 8 g (94,8% of theory) of a pale yellowish polymer are obtained; intrinsic viscosity ^~= 0.22 dl/g (c = 0.5% by weight in N,N-dimethylformamide at 25C).
To produce photosensitive plates, for example for the manufacture of printed circuits, a copper-laminated epoxy plate is coated with a 5% solution of the above polymer in N,N-dimethylformamide (DMF), using a production technique known per se [cf. Bogenschutz in "Fotolacktechnik" ("Photo-lacquer Technology"), Eugen G.
Lenze-Verlag, DT 7968 Saulgau (1975)]~ in such a way that after drying at 40C a film about 5~ thick is formed.
If this plate is now exposed to W light (~ greater than 320 nm) through a line negative for one minute, the non-crosslinked parts then developed in tetrahydrofuran, and the unprotected copper surface etched away, the circuit corresponding to the line negative is obtained.
Example 16 105.0 g of a mixture of N-(~-methacryloyloxy ethyl)-3- and -4-aæidophthalimide, 15.0 g of ethyl acryl-ate and 1.20 g of azoisobutyronitrile are dissolved in 545 ml of tetrahydrofuran, under yellow light, in an apparatus of the type described in Example 15. This solution is polymerised for 8 hours at 70C, with stir-ring and under a nitrogen atmosphere. After the reac-tion has ehded~ the reaction mixture is cooled to room temperature and the polymer obtained is precipitated by dripping the reaction solution into 4 litres of n-hexane.
113.8 g (94.8% of theory) of a pale yellowish polymer are : . , ~ i, .
-, ' ' . ' -~ '. ' . ' ' ' ' ` ,.
obtained; intrinsic viscosity ~1= 0.28 dl/g (c = 0.5% by weight in DMF at 25C).
Example 17 2.5 g of N-(~-hydroxyethyl)-3-azidophthalimide, 5 0 g of a copolymer of methyl vinyl ether and maleic anhydride (GANTREZ 119; anhydride content 0.64 mol per 100 g Polymer; ~= 5.76 cP; a commercial product from General Aniline ~ Film Corp.), i.e. a polymer having recurring structural units of the formula ~CH3 _ -CH2 - CH - CH --CH - -, O=C~C=O
and 0.1 ml of concentrated sulphuric acid are dissolved in 77 ml of tetrahydrofuran in a 250 ml round-bottomed flask equipped with a high-efficiency condenser and a drying tube. After heating up the reaction mixture, the latter is kept under reflux for 48 hours, with stirring. When the reaction solution has cooled, the polymer obtained is precipitated by dripping the reaction solution into 500 ml of diethyl ether. 6.8 g (91%
of theory) of a pale yellow polymer, containing 33.5%
by weight of azide, are obtained.
Example 18 2.5 g of N-(w-carboxypentyl~-3-azidophthalimide, 2.5 g of a styrene/glycidyl methacrylate copolymer (molar ratio 1:1, molecular weight 25,000, i.e. a copolymer having recurring structural units of the formula CH3 ~
~H2 ~ CH2 - C ~o _ L ~ O - O - CH2- CH - CH~ ~
.. . ~. , . . :
. ..
,, . , ... ~ , ;~ , . :~ ,- . . . :
~ . - , ,- - .
~D86Z6 and 0.03 g of tetramethylammonium chloride are dissolved in 45 ml of cyclohexanone in an apparatus of the type des-cribed in Example 17. After heating up the reaction mixture, the latter is stirred for 1 3/4 hours at 110C.
After the mixture has cooled, the polymer is precipitated by dripping the reaction solution into 300 ml of n-hexane
IR spectrum (CHC13): 1780 and 1725 cm 1 (C0-N-C0); 2130 cm 1 (N3).
The starting material used in the above example can be prepared as follows: A mixture of 9.6 g (0.05 mol) of 3-nitrophthalic anhydride, 12.9 g (0.055 mol) of l-ethyl-10,10-dimethyl-11-hydroxy-1-aminoundecane, 150 ml of toluene and 250 ml of dimethylformamide is heated to ..
- . ,, 1~8626 the boil, the water formed being removed azeotropically.
The reaction mixture is then evaporated to dryness.
The residue is dissolved in 150 ml of methylene chloride and the solution is extracted with three times 50 ml of 10% sodium carbonate solution. The methylene chloride solution is then dried over anhydrous sodium sulphate and evaporated. 20.9 g (about 100% of theory) of N-(l-ethyl-10,10-dimethyl~ hydroxyundecyl)-3-nitro-phthalimide are obtained in the form of a viscous oil which gradually crystallises after standing for several weeks; melting point 66-68C.
Example 14 A mixture of 2.4 g (0.007 mol) of 1-(3~nitro-phthalimidyl)-7-hydroxynaphthalene and 0.52 g (0.008 mol) of sodium azide in 14 ml of dimethylsulphoxide is stirred for 24 hours al 80C. 100 ml of water are added to the solution. The crystals which have precipitated are filtered off with suction, washed with water and dried at 80C/100 mm Hg. 1.7 g (73.6% of theory) of 1-(3-azidophthalimidyl)-7-hydroxynaphthalene are obtained;
melting point 154C (with decomposition). IR spectrum (KBr): 1775 and 1720 cm 1 (C0-N-C0); 2130 cm 1 (N3).
The starting material used in the above example can be prepared as follows: A mixture of 1.93 g (0.01 mol) of 3-nitrophthalic anhydride, 1.59 g (0.01 mol) of l-amino-7-naphthol and 30 ml of acetic acid is re~luxed for 17 hours. The resulting suspension is stirred with 300 ml of water, t~en filtered and the ~lter residue is then washed with water and dried. 2.9g of cr~de product are obtained and are extracted with chloroform. The chloroform extract is stirred with 4 g of silica gel, filtered with suction whilst hot, and evaporated to dryness. 2.4 g (72% of theory) of ~ nitrophthalimidyl)-7-hydroxynaphthalene are obtained;
melting point 136-7C.
Example 15 120.0 g of a mixture of N-(~-methacryloyloxyethyl)-3- and -4-azidophthalimide and 1.20 g of azoisobutyronit-.
.. . ..
- . . . . : ., . -.; , . , . - .,., . .:
... .
~8626 rile are dissolved in 545 ml of tetrahydrofuran, under yellow light, in a 1 litre reaction vessel equipped with a jacket, stirrer, high-efficiency condenser and thermo-meter This solution is polymerised for 8 hours at 70C, with stirring and under a nitrogen atmosphere.
After the reaction has ended, the reaction mixture is cooled to room temperature (20-25C) and the polymer is precipitated by dripping the reaction solution into 4 litres of n-hexane. 113 8 g (94,8% of theory) of a pale yellowish polymer are obtained; intrinsic viscosity ^~= 0.22 dl/g (c = 0.5% by weight in N,N-dimethylformamide at 25C).
To produce photosensitive plates, for example for the manufacture of printed circuits, a copper-laminated epoxy plate is coated with a 5% solution of the above polymer in N,N-dimethylformamide (DMF), using a production technique known per se [cf. Bogenschutz in "Fotolacktechnik" ("Photo-lacquer Technology"), Eugen G.
Lenze-Verlag, DT 7968 Saulgau (1975)]~ in such a way that after drying at 40C a film about 5~ thick is formed.
If this plate is now exposed to W light (~ greater than 320 nm) through a line negative for one minute, the non-crosslinked parts then developed in tetrahydrofuran, and the unprotected copper surface etched away, the circuit corresponding to the line negative is obtained.
Example 16 105.0 g of a mixture of N-(~-methacryloyloxy ethyl)-3- and -4-aæidophthalimide, 15.0 g of ethyl acryl-ate and 1.20 g of azoisobutyronitrile are dissolved in 545 ml of tetrahydrofuran, under yellow light, in an apparatus of the type described in Example 15. This solution is polymerised for 8 hours at 70C, with stir-ring and under a nitrogen atmosphere. After the reac-tion has ehded~ the reaction mixture is cooled to room temperature and the polymer obtained is precipitated by dripping the reaction solution into 4 litres of n-hexane.
113.8 g (94.8% of theory) of a pale yellowish polymer are : . , ~ i, .
-, ' ' . ' -~ '. ' . ' ' ' ' ` ,.
obtained; intrinsic viscosity ~1= 0.28 dl/g (c = 0.5% by weight in DMF at 25C).
Example 17 2.5 g of N-(~-hydroxyethyl)-3-azidophthalimide, 5 0 g of a copolymer of methyl vinyl ether and maleic anhydride (GANTREZ 119; anhydride content 0.64 mol per 100 g Polymer; ~= 5.76 cP; a commercial product from General Aniline ~ Film Corp.), i.e. a polymer having recurring structural units of the formula ~CH3 _ -CH2 - CH - CH --CH - -, O=C~C=O
and 0.1 ml of concentrated sulphuric acid are dissolved in 77 ml of tetrahydrofuran in a 250 ml round-bottomed flask equipped with a high-efficiency condenser and a drying tube. After heating up the reaction mixture, the latter is kept under reflux for 48 hours, with stirring. When the reaction solution has cooled, the polymer obtained is precipitated by dripping the reaction solution into 500 ml of diethyl ether. 6.8 g (91%
of theory) of a pale yellow polymer, containing 33.5%
by weight of azide, are obtained.
Example 18 2.5 g of N-(w-carboxypentyl~-3-azidophthalimide, 2.5 g of a styrene/glycidyl methacrylate copolymer (molar ratio 1:1, molecular weight 25,000, i.e. a copolymer having recurring structural units of the formula CH3 ~
~H2 ~ CH2 - C ~o _ L ~ O - O - CH2- CH - CH~ ~
.. . ~. , . . :
. ..
,, . , ... ~ , ;~ , . :~ ,- . . . :
~ . - , ,- - .
~D86Z6 and 0.03 g of tetramethylammonium chloride are dissolved in 45 ml of cyclohexanone in an apparatus of the type des-cribed in Example 17. After heating up the reaction mixture, the latter is stirred for 1 3/4 hours at 110C.
After the mixture has cooled, the polymer is precipitated by dripping the reaction solution into 300 ml of n-hexane
4.49 g (89.9% of theory) of a pale yellow polymer, con-taining 50% by weight of azide, are obtained Example 19 0 7 g of N-(4-carboxyphenyl)-3-azidophthalimide, 1 4 g of a methyl methacrylate/glycidyl methacrylate copolymer having recurring structural units of the formula . 3 CH3 ~H2 ' C - - CH2--C --- ' _ C0 - 0 - CH3C0 - 0 - CH2 - CH ~CH2 . '' _ ' ' .
(molar ratio 1:1, molecular weight 25,000) and 0 005 g of tetramethylammonium chloride are dissolved in 25 ml of cyclohexanone in an apparatus of the type described in Example 17 After heating up,the reaction mixture is stirred for 2 hours at 110C. The poly-mer is precipitated by dripping the reaction solution, when it has cooled, into 150 ml of n-hexane 1 96 g (93 3% of theory) of a pale yellow polymer, containing 33 5% by weight of azide, are obtained Example 20 Following a method analogous to that described in Examples 15 and 16, a mixture of N-(~-methacryloyloxy-ethyl)-3- and -4-azidophthalimide and acrylic acid, in a weight ratio of 1:4, is polymerised for 20 hours at 60C
in the presence of 0 5% by weight of azoisobutyronitrile, based on the weight of the monomers The polymer ob-tained is precipitated by dripping the reaction solution into diethyl ether A pale yellowish polymer is obtained; intrinsic viscosity .~= 0.23 dl/g (c = 0.5% by .
~862ti weight in DMF at 25C).
The polymers obtained according to Examplesl6-20 can be used for the manufacture of printed circuits by the method described.
Example 21 The polymer obtained according to Example 20 is tested in a photographic layer material. First a coat-ing solution of the following composition is prepared:
gelatin 2 g/m2 polymer according to Example 20 ~ g/m2 wetting agent (polyethylene oxide 20% by weight, based stearate) on the weight of the polymer photosensitiser (2-p-methoxy- 4% by weight, based benzyl-6'- and -7'-sulphoquin- on the weight of the oxaline) polymer hardener (2-hydroxy-6-amino-s- 8% by weight, based triazine-4-N-methylmorpholinium on the weight of the tetrafluoborate) gelatin This coating solution is coated onto a transparent carrier, i.e. a polyester film. After the gelatin has hardened, the film is exposed through a screen negative (step wedge with 12 steps) for 15 seconds, using a 400 watt high pressure lamp, The unexposed portions are washed out in water at 20C in the course of 20 seconds, The crosslinked polymer is dyedj or rendered visible, with a cationic dye, for example the dye of the formula ~3 ~ N ^~ /C2H5 ~ Cl .
used as an aqueous solution; all 12 steps of the step wedge are reproduced.
Example 22 10.42 g (0.035 mol) of N-(~-methacryloyloxyethyl)-3-azidophthalimide and 2.32 g (0.023 mol) of ethyl acryl-ate are dissolved in 50 ml of tetrahydrofuran and the - . , . - .
~: ~ - ' ,. , :
. . ~
' ~,. .' .'' ' 8 ~ ~6 ~ 25 -solution is warmed to 70C under nitrogen, the operations being carried out under yellow light. 0.127 g of azo-isobutyronitrile is dissolved in 7 ml of tetrahydrofuran and introduced into the monomer solution from a dropping funnel flushed with nitrogen. The reaction mixture is stirred for a further 7 hours at 70C and is then cooled to room temperature, filtered and precipitated in 1 litre of diethyl ether. The pale yellowish sus-pension is filtered with suction, and the product obtained is dried in vacuo at 30C. Yield: 11.85 g = 93% of theory; 11 8yo by weight N; intrinsic viscosity ~0.18 dl/g (c = O.5% by weight in DMF at 25C).
A copper-coated plate (about 5 x 10 cm) is coated on a commercial centrifuge with a 10% solution of the above polymer in DMF (viscosity about 1 Pa.s). The copper plate provided with the photolacquer is then dried in a circulating air oven at 6QC. Thereafter the coated plate is exposed for various periods of time, through a 21 step film negative original (a so-called "21-step sensitivity guide"), to a 400 watt mercury high-pressure lamp in front of which is a Pyrex glass filter, the distance from lamp to plate being 60 cm. The exposed plate is developed in l,l,l-trichloroethane and etched in FeC13 solution. To determine the photosensi-tivity, the last step of the original visible after etching is record-ed in each case.
Exposure time Ste~
1 minute 0 3 minutes 0-1 6 minutes 4 Comparative example: Using the method described in Example 15, N-(~~hydroxyethyl)-3-azidophthalimide is react-ed with a maleic anhydride polymer ("GantrezAN"~ a commercial product from GAF) to give a polymer having recurring structural units of the formula .... ..
.... ,. - ..
.. ., :
. -. ~ . .
_ 26 -~ -~H CH ---- C -COOH CO-O-(CH2 ~ N`Co ~ ~ ; (A) The same maleic anhydride polymer is reacted analogously with mono-~-hydroxyethyl 3-azidophthalate to give a polymer having recurring structural~units of the formula ._ _IH -- ~H ~
L ( H2~ ~oc~ J
~3 If polymers (A) and (B) are irradiated with W ~
light of wavelengths greater than 320 nm, polymer (A) exhibits a photosensitivity which is 5-10 times higher : than that of polymer (B), - - . ., . - . . . : . - : . - .
(molar ratio 1:1, molecular weight 25,000) and 0 005 g of tetramethylammonium chloride are dissolved in 25 ml of cyclohexanone in an apparatus of the type described in Example 17 After heating up,the reaction mixture is stirred for 2 hours at 110C. The poly-mer is precipitated by dripping the reaction solution, when it has cooled, into 150 ml of n-hexane 1 96 g (93 3% of theory) of a pale yellow polymer, containing 33 5% by weight of azide, are obtained Example 20 Following a method analogous to that described in Examples 15 and 16, a mixture of N-(~-methacryloyloxy-ethyl)-3- and -4-azidophthalimide and acrylic acid, in a weight ratio of 1:4, is polymerised for 20 hours at 60C
in the presence of 0 5% by weight of azoisobutyronitrile, based on the weight of the monomers The polymer ob-tained is precipitated by dripping the reaction solution into diethyl ether A pale yellowish polymer is obtained; intrinsic viscosity .~= 0.23 dl/g (c = 0.5% by .
~862ti weight in DMF at 25C).
The polymers obtained according to Examplesl6-20 can be used for the manufacture of printed circuits by the method described.
Example 21 The polymer obtained according to Example 20 is tested in a photographic layer material. First a coat-ing solution of the following composition is prepared:
gelatin 2 g/m2 polymer according to Example 20 ~ g/m2 wetting agent (polyethylene oxide 20% by weight, based stearate) on the weight of the polymer photosensitiser (2-p-methoxy- 4% by weight, based benzyl-6'- and -7'-sulphoquin- on the weight of the oxaline) polymer hardener (2-hydroxy-6-amino-s- 8% by weight, based triazine-4-N-methylmorpholinium on the weight of the tetrafluoborate) gelatin This coating solution is coated onto a transparent carrier, i.e. a polyester film. After the gelatin has hardened, the film is exposed through a screen negative (step wedge with 12 steps) for 15 seconds, using a 400 watt high pressure lamp, The unexposed portions are washed out in water at 20C in the course of 20 seconds, The crosslinked polymer is dyedj or rendered visible, with a cationic dye, for example the dye of the formula ~3 ~ N ^~ /C2H5 ~ Cl .
used as an aqueous solution; all 12 steps of the step wedge are reproduced.
Example 22 10.42 g (0.035 mol) of N-(~-methacryloyloxyethyl)-3-azidophthalimide and 2.32 g (0.023 mol) of ethyl acryl-ate are dissolved in 50 ml of tetrahydrofuran and the - . , . - .
~: ~ - ' ,. , :
. . ~
' ~,. .' .'' ' 8 ~ ~6 ~ 25 -solution is warmed to 70C under nitrogen, the operations being carried out under yellow light. 0.127 g of azo-isobutyronitrile is dissolved in 7 ml of tetrahydrofuran and introduced into the monomer solution from a dropping funnel flushed with nitrogen. The reaction mixture is stirred for a further 7 hours at 70C and is then cooled to room temperature, filtered and precipitated in 1 litre of diethyl ether. The pale yellowish sus-pension is filtered with suction, and the product obtained is dried in vacuo at 30C. Yield: 11.85 g = 93% of theory; 11 8yo by weight N; intrinsic viscosity ~0.18 dl/g (c = O.5% by weight in DMF at 25C).
A copper-coated plate (about 5 x 10 cm) is coated on a commercial centrifuge with a 10% solution of the above polymer in DMF (viscosity about 1 Pa.s). The copper plate provided with the photolacquer is then dried in a circulating air oven at 6QC. Thereafter the coated plate is exposed for various periods of time, through a 21 step film negative original (a so-called "21-step sensitivity guide"), to a 400 watt mercury high-pressure lamp in front of which is a Pyrex glass filter, the distance from lamp to plate being 60 cm. The exposed plate is developed in l,l,l-trichloroethane and etched in FeC13 solution. To determine the photosensi-tivity, the last step of the original visible after etching is record-ed in each case.
Exposure time Ste~
1 minute 0 3 minutes 0-1 6 minutes 4 Comparative example: Using the method described in Example 15, N-(~~hydroxyethyl)-3-azidophthalimide is react-ed with a maleic anhydride polymer ("GantrezAN"~ a commercial product from GAF) to give a polymer having recurring structural units of the formula .... ..
.... ,. - ..
.. ., :
. -. ~ . .
_ 26 -~ -~H CH ---- C -COOH CO-O-(CH2 ~ N`Co ~ ~ ; (A) The same maleic anhydride polymer is reacted analogously with mono-~-hydroxyethyl 3-azidophthalate to give a polymer having recurring structural~units of the formula ._ _IH -- ~H ~
L ( H2~ ~oc~ J
~3 If polymers (A) and (B) are irradiated with W ~
light of wavelengths greater than 320 nm, polymer (A) exhibits a photosensitivity which is 5-10 times higher : than that of polymer (B), - - . ., . - . . . : . - : . - .
Claims (12)
1. A compound of the formula Ia or Ib or (Ia) (Ib) in which Y is an alkylene group, having 2-18 C atoms, which is unsubstituted or is substituted by one or two phenyl groups, cycloalkyl groups having 5-8 C atoms or aralkyl groups having 7 or 8 C atoms, or is phenylene, naphthylene, biphenylene, cyclohexylene, dicyclohexylmethane or , which are unsubstituted or are substituted, per ring, by one halogen atom, one alkyl group having 1-4 C atoms, one cycloalkyl group having 5-7 C atoms or one aralkyl group having 7 or 8 C atoms, X is -O-, -S-, -SO2-, -CH2-, , or -CO- and Z is -NH2, -NH-alkyl having 1-4 C atoms, -OH, -COOH, -COCl, -O-CO-CH=CH2, , -COO-CH=CH2 or -O-CH=CH2.
2. A compound of the formula Ia or Ib according to claim 1, in which the N3 group is joined to the benzene ring in the otho-position to the carboxyl or carboxamide group, or to a carbonyl group.
3. A compound of the formula Ia or Ib according to claim 1, in which Y is unsubstituted alkylene having 2-18 C atoms, cyclohexylene, naphthylene or phenylene and Z is -NH2, -COOH, -COCl, -OH, -O-CO-CH=CH2 or .
4. A compound according to claim 1, of the formula VII
(VII).
(VII).
5. A compound according to claim 1, of the formula VIII
(VIII), in which f is from 1 to 5.
(VIII), in which f is from 1 to 5.
6. A compound according to claim 1, of the formula IX
(IX).
(IX).
7. A compound according to claim 1, of the formula X
(X).
(X).
8. A compound according to claim 1, of the formula XI
(XI).
(XI).
9. A process for the prepartion of a compound of the formula Ib according to claim 1, which comprises reacting a compound of the formula II
(II) in which Y is defined as under formula Ib, Z' is a group corresponding to Z but is not -COCl and Q is a halogen atom, or is the nitro group, in an inert organic solvent, at a temperature between about 0°C and 120°C, with an azide of the formula III
Mn+ (N3-)n (III) in which n is 1 or 2 and M is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation, and if desired converting the resulting compound of the formula Ib, in which Z is -COOH, to the corresponding acid chloride by treatment with a chlorinating agent or of a compound of the formula Ia or Ib according to claim 1, in which Z is not -OCH=CH2, which process comprises reacting a compound of the formula IV
(IV) with an amine of the formula V
H2N-Y-Z" (V) to give a compound of the formula VI
(VI), in which formulae Y is as defined under formula Ia or Ib and Z" is -NH2, -NH-alkyl having 1-4 C atoms, -OH, -COOH, -O-CO-CH=CH2, or -COO-CH=CH2, thereafter, if appropriate, cyclising the compound of the formula VI and, if desired, converting a resulting compound of the formula Ib, in which Z is -COOH, to the corresponding acid chlor-ide by treatment with a chlorinating agent.
(II) in which Y is defined as under formula Ib, Z' is a group corresponding to Z but is not -COCl and Q is a halogen atom, or is the nitro group, in an inert organic solvent, at a temperature between about 0°C and 120°C, with an azide of the formula III
Mn+ (N3-)n (III) in which n is 1 or 2 and M is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation, and if desired converting the resulting compound of the formula Ib, in which Z is -COOH, to the corresponding acid chloride by treatment with a chlorinating agent or of a compound of the formula Ia or Ib according to claim 1, in which Z is not -OCH=CH2, which process comprises reacting a compound of the formula IV
(IV) with an amine of the formula V
H2N-Y-Z" (V) to give a compound of the formula VI
(VI), in which formulae Y is as defined under formula Ia or Ib and Z" is -NH2, -NH-alkyl having 1-4 C atoms, -OH, -COOH, -O-CO-CH=CH2, or -COO-CH=CH2, thereafter, if appropriate, cyclising the compound of the formula VI and, if desired, converting a resulting compound of the formula Ib, in which Z is -COOH, to the corresponding acid chlor-ide by treatment with a chlorinating agent.
10. A process according to claim 9, wherein a compound of the formula II, in which Q is the nitro group, is used.
11. A process according to claim 9, wherein an alkali metal azide, especially sodium azide, is used as the azide of the formula III.
12. A process according to claim 9, wherein the re-action is carried out at a temperature between about 50 and 90°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH12577/77 | 1977-10-14 | ||
| CH1257777 | 1977-10-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1108626A true CA1108626A (en) | 1981-09-08 |
Family
ID=4384342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA313,228A Expired CA1108626A (en) | 1977-10-14 | 1978-10-12 | 3- and 4-azidophthalic acid derivatives |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4250096A (en) |
| EP (1) | EP0002181B1 (en) |
| JP (1) | JPS5463040A (en) |
| CA (1) | CA1108626A (en) |
| DE (1) | DE2860863D1 (en) |
| ES (1) | ES474173A1 (en) |
| IT (1) | IT1099730B (en) |
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|---|---|---|---|---|
| US4459414A (en) * | 1981-04-08 | 1984-07-10 | Ciba-Geigy Corporation | Tetrasubstituted phthalic acid derivatives, and a process for their preparation |
| US4467100A (en) * | 1981-05-26 | 1984-08-21 | Lord Corporation | Epoxy resin compositions cured with imide-amine at ambient temperatures to afford products having useful properties at high temperatures |
| US5521014A (en) | 1981-11-13 | 1996-05-28 | The Boeing Company | Extended multidimensional ether or ester oligomers |
| US5512676A (en) | 1987-09-03 | 1996-04-30 | The Boeing Company | Extended amideimide hub for multidimensional oligomers |
| US5693741A (en) | 1988-03-15 | 1997-12-02 | The Boeing Company | Liquid molding compounds |
| US5714566A (en) | 1981-11-13 | 1998-02-03 | The Boeing Company | Method for making multiple chemically functional oligomers |
| US5516876A (en) | 1983-09-27 | 1996-05-14 | The Boeing Company | Polyimide oligomers and blends |
| US5210213A (en) | 1983-06-17 | 1993-05-11 | The Boeing Company | Dimensional, crosslinkable oligomers |
| US5705598A (en) | 1985-04-23 | 1998-01-06 | The Boeing Company | Polyester sulfone oligomers and blends |
| US5969079A (en) | 1985-09-05 | 1999-10-19 | The Boeing Company | Oligomers with multiple chemically functional end caps |
| US4515964A (en) * | 1982-01-07 | 1985-05-07 | Ppg Industries, Inc. | Polyhalophthalimidoalkyl-functional carbonates |
| US4666958A (en) * | 1982-01-07 | 1987-05-19 | Ppg Industries, Inc. | Polymeric compositions containing polyhalophthalimidoalkyl-functional carbonates |
| US4414396A (en) * | 1982-01-07 | 1983-11-08 | Ppg Industries, Inc. | Polyhalophthalimidoalkyl-functional carbonates and haloformates |
| US5120819A (en) * | 1984-09-18 | 1992-06-09 | Boeing Company | High performance heterocycles |
| US5082905A (en) * | 1984-09-18 | 1992-01-21 | The Boeing Company | Blended heterocycles |
| US4868270A (en) * | 1986-08-04 | 1989-09-19 | The Boeing Company | Heterocycle sulfone oligomers and blends |
| US5618907A (en) | 1985-04-23 | 1997-04-08 | The Boeing Company | Thallium catalyzed multidimensional ester oligomers |
| US5817744A (en) | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
| JPH04182466A (en) * | 1990-11-19 | 1992-06-30 | Mitsubishi Gas Chem Co Inc | Production of bistrimellitic imides |
| US6017661A (en) | 1994-11-09 | 2000-01-25 | Kimberly-Clark Corporation | Temporary marking using photoerasable colorants |
| CA2120838A1 (en) | 1993-08-05 | 1995-02-06 | Ronald Sinclair Nohr | Solid colored composition mutable by ultraviolet radiation |
| US5645964A (en) | 1993-08-05 | 1997-07-08 | Kimberly-Clark Corporation | Digital information recording media and method of using same |
| US5773182A (en) | 1993-08-05 | 1998-06-30 | Kimberly-Clark Worldwide, Inc. | Method of light stabilizing a colorant |
| US5700850A (en) | 1993-08-05 | 1997-12-23 | Kimberly-Clark Worldwide | Colorant compositions and colorant stabilizers |
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| US6211383B1 (en) | 1993-08-05 | 2001-04-03 | Kimberly-Clark Worldwide, Inc. | Nohr-McDonald elimination reaction |
| US5721287A (en) | 1993-08-05 | 1998-02-24 | Kimberly-Clark Worldwide, Inc. | Method of mutating a colorant by irradiation |
| US5865471A (en) | 1993-08-05 | 1999-02-02 | Kimberly-Clark Worldwide, Inc. | Photo-erasable data processing forms |
| US5643356A (en) | 1993-08-05 | 1997-07-01 | Kimberly-Clark Corporation | Ink for ink jet printers |
| US5733693A (en) | 1993-08-05 | 1998-03-31 | Kimberly-Clark Worldwide, Inc. | Method for improving the readability of data processing forms |
| US6017471A (en) | 1993-08-05 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Colorants and colorant modifiers |
| US5739175A (en) | 1995-06-05 | 1998-04-14 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer |
| US6242057B1 (en) | 1994-06-30 | 2001-06-05 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition and applications therefor |
| US5685754A (en) * | 1994-06-30 | 1997-11-11 | Kimberly-Clark Corporation | Method of generating a reactive species and polymer coating applications therefor |
| US6071979A (en) | 1994-06-30 | 2000-06-06 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition method of generating a reactive species and applications therefor |
| US6008268A (en) | 1994-10-21 | 1999-12-28 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition, method of generating a reactive species, and applications therefor |
| US5747550A (en) | 1995-06-05 | 1998-05-05 | Kimberly-Clark Worldwide, Inc. | Method of generating a reactive species and polymerizing an unsaturated polymerizable material |
| US5798015A (en) | 1995-06-05 | 1998-08-25 | Kimberly-Clark Worldwide, Inc. | Method of laminating a structure with adhesive containing a photoreactor composition |
| US5849411A (en) | 1995-06-05 | 1998-12-15 | Kimberly-Clark Worldwide, Inc. | Polymer film, nonwoven web and fibers containing a photoreactor composition |
| US5786132A (en) | 1995-06-05 | 1998-07-28 | Kimberly-Clark Corporation | Pre-dyes, mutable dye compositions, and methods of developing a color |
| US5811199A (en) | 1995-06-05 | 1998-09-22 | Kimberly-Clark Worldwide, Inc. | Adhesive compositions containing a photoreactor composition |
| DE69609967T2 (en) | 1995-06-05 | 2001-04-12 | Kimberly Clark Co | DYE PRECURSORS AND COMPOSITIONS CONTAINING THEM |
| CA2221565A1 (en) | 1995-06-28 | 1997-01-16 | Kimberly-Clark Worldwide, Inc. | Novel colorants and colorant modifiers |
| EP0854896B1 (en) | 1995-11-28 | 2002-04-03 | Kimberly-Clark Worldwide, Inc. | Light-stabilized dyestuff compositions |
| US6099628A (en) | 1996-03-29 | 2000-08-08 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5855655A (en) | 1996-03-29 | 1999-01-05 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5782963A (en) | 1996-03-29 | 1998-07-21 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US5891229A (en) | 1996-03-29 | 1999-04-06 | Kimberly-Clark Worldwide, Inc. | Colorant stabilizers |
| US6524379B2 (en) | 1997-08-15 | 2003-02-25 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
| JP2002517540A (en) | 1998-06-03 | 2002-06-18 | キンバリー クラーク ワールドワイド インコーポレイテッド | Neo nanoplast and microemulsion technology for ink and ink jet printing |
| BR9906513A (en) | 1998-06-03 | 2001-10-30 | Kimberly Clark Co | New photoinitiators and applications for the same |
| US6228157B1 (en) | 1998-07-20 | 2001-05-08 | Ronald S. Nohr | Ink jet ink compositions |
| DE69930948T2 (en) | 1998-09-28 | 2006-09-07 | Kimberly-Clark Worldwide, Inc., Neenah | CHELATE WITH CHINOIDS GROUPS AS PHOTOINITIATORS |
| DE60002294T2 (en) | 1999-01-19 | 2003-10-30 | Kimberly Clark Co | DYES, COLOR STABILIZERS, INK COMPOSITIONS AND METHOD FOR THE PRODUCTION THEREOF |
| US6331056B1 (en) | 1999-02-25 | 2001-12-18 | Kimberly-Clark Worldwide, Inc. | Printing apparatus and applications therefor |
| US6294698B1 (en) | 1999-04-16 | 2001-09-25 | Kimberly-Clark Worldwide, Inc. | Photoinitiators and applications therefor |
| US6368395B1 (en) | 1999-05-24 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Subphthalocyanine colorants, ink compositions, and method of making the same |
| MXPA02012011A (en) | 2000-06-19 | 2003-04-22 | Kimberly Clark Co | Novel photoinitiators and applications therefor. |
| FR2831534B1 (en) * | 2001-10-29 | 2004-01-30 | Oreal | PHOTOACTIVABLE COMPOSITION AND USES |
| CN105985770A (en) * | 2015-02-09 | 2016-10-05 | 苏州罗兰生物科技有限公司 | Preparation method and application of hydrogen sulfide fluorescent probe |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB678599A (en) | 1949-10-10 | 1952-09-03 | Kalle & Co Ag | Improvements relating to the production of colloid photo-images for use in photomechanical printing |
| BE549814A (en) | 1955-07-29 | |||
| BE595534A (en) * | 1959-10-02 | |||
| FR1289450A (en) | 1960-11-07 | 1962-04-06 | Kodak Pathe | New thermographic reproduction process |
| DE2000623C3 (en) * | 1970-01-08 | 1979-06-28 | Agfa-Gevaert Ag, 5090 Leverkusen | Photographic process for the production of images |
| FR2076639A5 (en) * | 1970-01-21 | 1971-10-15 | Inst Francais Du Petrole | |
| US3878224A (en) * | 1970-12-23 | 1975-04-15 | Mitsubishi Chem Ind | N-substituted-{66 {40 -tetrahydrophthalimides |
-
1978
- 1978-10-05 US US05/948,857 patent/US4250096A/en not_active Expired - Lifetime
- 1978-10-06 EP EP78101082A patent/EP0002181B1/en not_active Expired
- 1978-10-06 DE DE7878101082T patent/DE2860863D1/en not_active Expired
- 1978-10-12 CA CA313,228A patent/CA1108626A/en not_active Expired
- 1978-10-13 IT IT7828768A patent/IT1099730B/en active
- 1978-10-13 ES ES474173A patent/ES474173A1/en not_active Expired
- 1978-10-14 JP JP12676278A patent/JPS5463040A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ES474173A1 (en) | 1979-09-01 |
| EP0002181A2 (en) | 1979-06-13 |
| IT7828768A0 (en) | 1978-10-13 |
| IT1099730B (en) | 1985-09-28 |
| EP0002181A3 (en) | 1979-07-11 |
| US4250096A (en) | 1981-02-10 |
| DE2860863D1 (en) | 1981-10-29 |
| EP0002181B1 (en) | 1981-07-22 |
| JPS5463040A (en) | 1979-05-21 |
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