US2484477A - Process for making color couplers - Google Patents
Process for making color couplers Download PDFInfo
- Publication number
- US2484477A US2484477A US508392A US50839243A US2484477A US 2484477 A US2484477 A US 2484477A US 508392 A US508392 A US 508392A US 50839243 A US50839243 A US 50839243A US 2484477 A US2484477 A US 2484477A
- Authority
- US
- United States
- Prior art keywords
- amino
- group
- coupler
- amines
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 16
- 150000001412 amines Chemical class 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- -1 sulfobenzoyl Chemical group 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BXDMTLVCACMNJO-UHFFFAOYSA-N 5-amino-1,3-dihydrobenzimidazole-2-thione Chemical compound NC1=CC=C2NC(S)=NC2=C1 BXDMTLVCACMNJO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical compound BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001266 acyl halides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- AYLDJQABCMPYEN-UHFFFAOYSA-N (4-azaniumylphenyl)-diethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)C1=CC=C(N)C=C1 AYLDJQABCMPYEN-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- NUMXHEUHHRTBQT-AATRIKPKSA-N 2,4-dimethoxy-1-[(e)-2-nitroethenyl]benzene Chemical compound COC1=CC=C(\C=C\[N+]([O-])=O)C(OC)=C1 NUMXHEUHHRTBQT-AATRIKPKSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- XSFKCGABINPZRK-UHFFFAOYSA-N 4-aminopyrazol-3-one Chemical class NC1=CN=NC1=O XSFKCGABINPZRK-UHFFFAOYSA-N 0.000 description 1
- XTBFKMDOQMQYPP-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C=C1 XTBFKMDOQMQYPP-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- 101100386518 Caenorhabditis elegans dbl-1 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- WSDQIHATCCOMLH-UHFFFAOYSA-N phenyl n-(3,5-dichlorophenyl)carbamate Chemical compound ClC1=CC(Cl)=CC(NC(=O)OC=2C=CC=CC=2)=C1 WSDQIHATCCOMLH-UHFFFAOYSA-N 0.000 description 1
- 235000020004 porter Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- ZDXCSDOLRSKTIP-UHFFFAOYSA-N s-(1h-benzimidazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2NC(SN)=NC2=C1 ZDXCSDOLRSKTIP-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific
Definitions
- This invention relates to particularly to a novel method of preparing couplers for color photography.
- Color forming compounds which react with the 2 development product of aromatic amino developing agents to form :coloredimages on photographic developmenthave been the subject of numerous prior-patents.
- the dyes formed in this way are insoluble in water and in the ordinary photographic developing and fixing baths,
- a coupling component or coupler Such a com- 4 pound which isempl'oyed conjunction with the developing agent 'for thesilver and which couples with the development product'of the developer during photographic development is referred to herein as a coupling component or coupler.
- the couplingportion ofthe coupler molecule usually consists of a radicalzwith a phenolichydroxyl group or a'reactivemethylene group,.and
- a further object is td provide a method for the preparation ofcouplers suitable for use in the process of Peterson U. S. 5
- Couplers containing amino groups are well known. Porter and Weissberger U. S. Patent 2,376,380, granted May 22, 1945, describes amino pyrazolones; French Patent 836,144 discloses aminophenols.
- R represents a coupler molecule and R represents a second coupler molecule or a heterocyclic system containing an NH- or SH-group.
- CouplerNH CI-I2 C6 NH- lieterocyclic.
- Type III Heterocyc1ic--NH-CHzCO-NH- coupler.
- Example -1 ---- m( 2 hydroxyphenyhcarbamylv *benzenesulfonyl chloride 'In'" -a'-2"-"liter;* 3--neekdflask;-equipped” with a thermometermndstirrer, placed 5 700' cc. of 'tlioxane "dried over anhydrous calcium chloride. In this solvent is” dissolved l g'fii grams 0.4 mole) "of "recrystallized (from .””parts' of alcohol) o-aminophenol by he'ating'to”70 C. The clear pink solution is cooled to' ""Ci and to it is added 48. grams 10.2 mole).
- the cream-colored mixture is cooled to" and V c poured in a thin stream into 1 liter of water. 15
- the mixture is filtered by suction, a 6" Biichner N I NH funnel being used.v
- Theproduct is washed on the 6,
- This solid is dissolved by heating in 600 cc. of 1 methanol.
- the amber methanol solution is i cooled to room temperature and treated with 3.0 i CH 7 grams of Darco.
- the mixture is filtered by suction through a layer of 3.0 g. otDarco on a CH2 C NH C f Biichner funnel.
- the clear amber filtrate is 0 N l 'N N Typm concentrated by suctionona steam bath. The f viscous residue pulls and dries to a brittle yellow A A solid, which may be ground.
- I such as alkylphenylenediamines and alkyltoluylenediamines.
- Example 1 p-Aminodiethylaniline sulphate grams 2.5 Sodium sulphite anhydrous do 2 Sodium carbonate anhydrous do 20 Potassium bromide do 1 Water to liters 1
- Example 2 p-Aminodiethylaniline hydrochloride grams 2 Sodium sulphite anhydrous do Sodium carbonate anhydrous do Water to liters 1
- the couplers used according to my invention may be incorporated in silver halide emulsion layers in various ways but we prefer to form a solution of the sodium salt of the coupler in alcohol and add this to the emulsion. For example, 3 grams of coupler may be dissolved or suspended in 50 cc.
- the sodium hydroxide may be added as solid or as a concentrate solution.
- the sodium salt of the coupler is thereby generated in a solution of 50 cc. of alcohol and this solution is added to 1 liter of a gelatin silver halide emulsion.
- the pH of the emulsion may then be adjusted if desired by adding a suitable acid such as acetic or sulphuric acid to neutralize all or part of the sodium hydroxide used to form the sodium salt of the coupler.
- a suitable acid such as acetic or sulphuric acid
- the coupling components may be incorporated either in gelatin or in other colloidal materials such as collodion, organic esters of cellulose or synthetic resins.
- the emulsion may be carried by a transparent medium such as glass, cellulose esters, or synthetic resin or a non-transparent reflecting medium such as paper or an opaque cellulose ester.
- the emulsion may be coated as a single layer on the support or superposed layers containing the couplers may be coated on one or both sides of the support.
- the superposed layers may be differentially sensitized for the formation of a natural color image in the well known manner.
- the method of reacting sulfobenzoyldichloride with two difierent primary amines in successive stages, at least one of which amines contains a group reactive with the oxidation products of primary aromatic amino photographic developing agents which comprises selectively reacting a cool solution of one of said amines with the carboxylic acid chloride group of said sulfobenzcyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulfonic acid amide.
- the method of reacting sulfobenzoyldichloride in successive stages, with a phenol having a primary amino group in the 2-position, and with 5-amino-2-mercaptobenzimidazole which comprises selectively reacting a cool solution of one of said amines with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulfonic acid amide.
- the method of reacting sulfobenzoyldichloride in successive stages, with a phenol having a primary amino group in the 2-position, and with 5-amino-2-mercaptobenzimidazole which comprises selectively reacting a cool solution of said phenol with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with said 5-amino- Z-mercaptobenzimidazole to produce a sulfonic acid amide.
Description
Patented Oct. 11, 1949 UNlTE D-flS T'AT PROCESS FOR MAKING coLoncoUPLnns Arnold Weissberger and Ilinari Salminen,
Rochester, N.- -Y.,'-assignors to Eastman Kodak Company, Rochester I New Jersey N Drawing.
1 This invention relates to particularly to a novel method of preparing couplers for color photography.
Color forming compounds which react with the 2 development product of aromatic amino developing agents to form :coloredimages on photographic developmenthave been the subject of numerous prior-patents. The dyes formed in this way are insoluble in water and in the ordinary photographic developing and fixing baths,
although the silver images formed simultaneously with, them during the photographic development may be removed fromthephotographic layer to leave pure dye imagesin .thelayer. Such a com- 4 pound which isempl'oyed conjunction with the developing agent 'for thesilver and which couples with the development product'of the developer during photographic development is referred to herein as a coupling component or coupler.
When these "couplingcomponents areincorpo rated in the photographic layer prior to exposure, they do notaffect theexposure and development of the layer in the usual way'but when the development is carriedout with a suitable developing agent they combine withthe oxida-;.
tion product of the developer toform a colored image in situ with'the silver image. i
The couplingportion ofthe coupler molecule usually consists of a radicalzwith a phenolichydroxyl group or a'reactivemethylene group,.and
to this portion may be attached;substituents which render the coupler suitable for use in variousprocesses, such asthose described in Mannes and Godowskyfi s; Patent 2,304,940, granted December 15, 1942, Jelleyand Vittum U. S. Pat
ent 2,322,027, grantedJune 15,1943, andQPcterson U. S. Patent 2,296,306, granted September 22, 1942; In the process of thePetersonpatent, for example, couplersare used containing irnino or mercapto groups which permit the formation vention to provide a novel method for the prep- ,9
A further object is td provide a method for the preparation ofcouplers suitable for use in the process of Peterson U. S. 5
aration of color couplers.
Patent 2,296,306. Other objects will appear from the following description of our invention.
These objects are accomplished, according to the broader aspects of our invention bynj ining two different primary or secondary amines,;=orie -5 I or both of which may be, couplers," or one of which may be a heterocycliclcompound containing a reactiveniercapto or imino group, or one of which may be a non coupling aliphatic or aromatic amine, by means of a'two-step condenphotography and activity to saidiamines. j
, N. a corporation of npplication october so, 1943, Serial No. 508,392
6 Claims. (01. 260309 I sation involving theuse of an acyl halide having replaceable halogen atoms of different re- More' specifically, our invention provides for the joining of a coupler containin an amino group, to another amine, such as a heterocyclic compound containing an amino group, by the use of bromoacetyl bromide or sulfobenzoyl dichloride as the condensing agent.
Couplers containing amino groups are well known. Porter and Weissberger U. S. Patent 2,376,380, granted May 22, 1945, describes amino pyrazolones; French Patent 836,144 discloses aminophenols.
If these or similar couplers containing amino groups are treated with suliobenzoyl dichloride (Annalen, 102, 1857, page 249) or bromoacetyl bromide (Berichte, 24, 1891, page 2219) in the presence of a base to take up the hydrogen halide which is split off, a condensation takes place, and an intermediate compound is formed which has coupling properties and contains a replaceable halogen atom., If this intermediate, which may or may not be isolated, is reacted with another amino compound, again in the presence of a base to take up the hydrogen halide, a second condensation takes place, and a compound is formed which retains its coupling properties and which possesses characteristics introduced by the second amino compound.
In-the case of bromoacetyl bromide, the reaction proceeds as follows:
where R represents a coupler molecule and R represents a second coupler molecule or a heterocyclic system containing an NH- or SH-group.
-: similar reactiontakes-place in the case of sulfobenzoyl dichloride as follows:
NH: O-ooomoomn-Umn Type I. CouplerNH CI-I2 C6 NH-=lieterocyclic.
Type II. Coupler NH CO-+- CsH iH-S2'- NH--heterocyc1ic.
Type III. Heterocyc1ic--NH-CHzCO-NH- coupler.
Type IV. HeterocyclicNHCO-CsH4SOz Couplers containing aminogroups which-may 1 be condensedwith the acyl halide are as follows,
this .list being illustrative only.
NH: HR
CH3- CH5 l I-Ieterocyclic amines containing --NH 1 or #SH o Pyrimil'jine Tetrazole Benzimidazo'le Any of the Eheterocy'clickcompounds disclosd in i Peterson *U.- S: Fatent..2 ,296, 30.6-,--when:-substituted with an -emmofrgroupiimay be employed.
The following examples illustrate the method of forming the compounds according to our invention:
Example -1.---- m( 2 hydroxyphenyhcarbamylv *benzenesulfonyl chloride 'In'" -a'-2"-"liter;* 3--neekdflask;-equipped" with a thermometermndstirrer, placed 5 700' cc. of 'tlioxane "dried over anhydrous calcium chloride. In this solvent is" dissolved l g'fii grams 0.4 mole) "of "recrystallized (from .""parts' of alcohol) o-aminophenol by he'ating'to"70 C. The clear pink solution is cooled to' ""Ci and to it is added 48. grams 10.2 mole). of m-isiil fbhenzoyldichloride with continuousls'tirring. The temperature rises to-about- 40.- and, -after a few minutes, the viscous pinlomaterial. which. has separated,- crystall-izes. After themixture has been stirred for 15 minutesyit iisi-filtered by.suction-andthe residuew of :maminophenolhydrochloride washed- -0n the filter with---1=Q0-:cctofliresh-dioxane.
I The 1 filtrate-adsediluted with 800i T00, :of ligroin enmspmew fon fislminutes. :The sulionyl chloride which sepamtes iis filterecband-Washed on the -filter with l -l'lter f ipetroleum ether. The solid produet is crystallized "'as -f a itan =s'0l i'cl from 600 --'cc. -oftetrachloroethane which has been dried by the distillation-oration? 2500? of forerun. The
mixture-"ls *filtered and the 5 product =washedon the filter with 2X50 "cc. of fresh tetrachloro- "ethanefo'llowwby 300*cci'of hexane to remove "tetrachloroethane. Thei'productis'dried at 100. "Yfe1d 43 g.'(69'% MJP: 186.
'-C-SH+ CHiCOOH NaCl In a 500 cc. 3-necked, flask, equipped with a 2' CH stirrer and a thermometer, is placed 35O cc. of r. 90% acetic acid. To the acid is added. 14.5 g. T E Y ,I T' (0.18 mole) of anhydrous sodium acetate and N N TypeIII 20.0 g. (0.12 mole) of -amino-2-mercaptobenz- 5 I I imidazole. The mixture is heated in a water I I bath to 45. Then is added 37.3 g. 0.12 mole) of 9 in 2'-hydroxyphenylcarbamylbenzenesulfonyl 'chlop y l( e c oy o y p' y -fi'r ide. The mixture is heated in the bath to 55 and ammmiy n held at 55-58 for-2 hours, during vigorous stiri ring. After one-half hour of heating, 2.0 g. (0.012 mole) more of 5-amino-2-mercaptobenzv n N imidazole is added. 5 r CHFC NHCO CH, NH
The cream-colored mixture is cooled to" and V c poured in a thin stream into 1 liter of water. 15 The mixture is filtered by suction, a 6" Biichner N I NH funnel being used.v Theproduct is washed on the 6,
funnel with 3 liters of water. Dried at 50. The
This solid is dissolved by heating in 600 cc. of 1 methanol. The amber methanol solution is i cooled to room temperature and treated with 3.0 i CH 7 grams of Darco. The mixture is filtered by suction through a layer of 3.0 g. otDarco on a CH2 C NH C f Biichner funnel. The clear amber filtrate is 0 N l 'N N Typm concentrated by suctionona steam bath. The f viscous residue pulls and dries to a brittle yellow A A solid, which may be ground. Yield, 34.5 grams H (65 l-phenyl-b l [2' (2" mercapto-4-hydro minions" Example: H a suliamyllbenzamidol-iS-pyrazo one 2-{s'-[3" -(4"'-( tertiary amy1 'shenoxaben'. zene carbamyD-benzene suliamidolvbenzamido}-4-chloro-5-methylphenol (No. 19) "is prepared by the condensation of equimoiecular EHT NHCO SOME weights of Z-(S' a minobenZamid 4-chloror-5- Q I I methylphenol and 3[4 (4"-tertiary amyl phe- If 4 Type II noxy) -benzene carbamyllbenzene sulfonyl chlo- -sn Typ'am Co s" Tide in an excess of quinoline. After the spontaneous reaction excess quinoline f quinonne i0 5-[m-(1u henyl-ls'-pyrazoloite-i-carbagl)ibenzenesulfamidol-z hydrochloride are removed by dilute hydrochlo- 4 I memp 0 mm we ric acid.
E$ mple3 h on l-phenyl-3-{3'-[3"-(4-p-tertiary amyl phe- CHn-0NHSO -CO-NH-C/ c-mn noxy benzene carbamyD-benzene sulfamidol- O L i 1 benzamido}-5-pyrazolone (No. 20) is prepared by the condensation of equimolecular weights of 1- N h phenyl 3 m amino benzoylamino 5 aparaz- $.11, r SH I Type IV olone hydrochloride and 3-[4-(4"-tertiary amyl i v phenoxy)-benzene carbamyll-benzene sulfonyl l-pheny l -iilI?(2"-mercapto4 -hydroxypyrimidyl-o")carbamyll t benzenesuliamidol-Ji-pymzolone I 7. CIHQ O (EH10 ONH A I '.;6L3[3"-(bonzoyl acetylamino)benzene mrbamyH-benzenesuliamido}-2-mercapto benzimidszole chloride in an excess of q'uinolihei Themethodj is similar to'that of Examplel' fi 'f'i Example! I do l-phenyl-3-ani1ino acetylamino-5-pyr amolone (No. 21) is prepared by'heating 1-phenyl-3 b'romoacetylaminoefi-pyrazolone in an excess ofanion N NHCO SO:NH
I p I NH Typell'.
I I 5-[3-(2-hydroxyphenylcarbam 1)-benzene sulfamidoline. Excess aniline is removed by dilute hydro- I a. zmempwbwigmml I 1 chloric acid and during the operati m11 c5 drochloride isalso remo'vedp: I other p unds listed below-are" prepared;
similarly. I I -I I 5-[3- 2-hydroxy4"-methyl-5"-ohlorophenyi carbamynenaene-suliamidol-Z-mwqapto baoziu idalole was 2-mezeapto benzimidazole 5-[m-(2-hydroxy-4-methoxyphenyl-sulfamyl)-benzamido] 2- 'mercapto benzimidazole N 00 CHz-N 20 C-SH CH E/I Type III.
y 2-mercapto benzimidazole 25 wanilinoacetylaminmi-ehloro-i-methylphenol 19. OH I I --NHCO NHSO 2-{ 3-[3-(4-(p-tert. amylphenoxwbeniene'csrb2amylgbeiizeuesulfan idolbenzamido14-ehIoro-5- ma-(z'z-h-ydmlyuhemrl' carbemyl) benzene-N-amylsulfanilide 1s.
' I hen 1-3 nlin cet 1 -5- 1 i1 5[m-(2'-hyd1oxyphen3 ;)l suliauEyD-PenzamidoI-2-mercaptol i, y a 1 yammo pyrazo o e enzimi azo e The aromatic amino developing agents used The following-compound illustrates the union 55 with the coupler compounds of our invention inoi, two coupler molecules containing-H ammo. I V cludewthe'mono diand tri-aminoaryl comgroups by our method: poundsgndztheizde zivatives formed: by substitu- OH tion in the amino group tas WBHfaSlin. the ring,
I such as alkylphenylenediamines and alkyltoluylenediamines. Thesercox npotm'ds are usually used 111. salteiiomr, suchias: the hydrochloride or the sulnhateizi which armmorej stable than t the amines themselYes.:;-= Suitable :cmnpoundseare; vdiethyl-p- 2,2"-dihydroxy-msulfobenzoyldianilide pwphenyienediaminehydrochloride,y diinethyl-phe o ow C po ds illustrate the 00111- Dhenylenediaminehydmohloridewand; dimethylbination of a coupler with a non-coupling arop mphenglenediammeesulphate;;;.Thepammuphenylenediamine hydrochloride, mono-methylmatic amine by our method: phenols and their substitution products may also 1 OH be used where the amino group is unsubstituted. I 'i All of these compounds have an unsubstituted h i ;.SO,NH amino group-which enables the oxidation prodv ueteziof the developer to eouple the colorforming oon pounds to form a dye image;
The following examples are illustrative of dem-(T-IifimkfihhyD-carfirhtl benzene sulieuilide wv opl ssolutionswhichb to develop emulsion layers containing the couplers made according to our invention.
Example 1 p-Aminodiethylaniline sulphate grams 2.5 Sodium sulphite anhydrous do 2 Sodium carbonate anhydrous do 20 Potassium bromide do 1 Water to liters 1 Example 2 p-Aminodiethylaniline hydrochloride grams 2 Sodium sulphite anhydrous do Sodium carbonate anhydrous do Water to liters 1 The couplers used according to my invention may be incorporated in silver halide emulsion layers in various ways but we prefer to form a solution of the sodium salt of the coupler in alcohol and add this to the emulsion. For example, 3 grams of coupler may be dissolved or suspended in 50 cc. of ethyl alcohol and sodium hydroxide added in the amount of 1 equivalent weights of the coupler. The sodium hydroxide may be added as solid or as a concentrate solution. The sodium salt of the coupler is thereby generated in a solution of 50 cc. of alcohol and this solution is added to 1 liter of a gelatin silver halide emulsion.
The pH of the emulsion may then be adjusted if desired by adding a suitable acid such as acetic or sulphuric acid to neutralize all or part of the sodium hydroxide used to form the sodium salt of the coupler.
The coupling components may be incorporated either in gelatin or in other colloidal materials such as collodion, organic esters of cellulose or synthetic resins. The emulsion may be carried by a transparent medium such as glass, cellulose esters, or synthetic resin or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the support or superposed layers containing the couplers may be coated on one or both sides of the support. The superposed layers may be differentially sensitized for the formation of a natural color image in the well known manner.
The examples and, compounds set forth in the present specification are illustrative only and it is to be understood that our invention is to be taken as limited only by the scope of the appended claims.
We claim:
1. The method of reacting sulfobenzoyldichloride with two difierent primary amines in successive stages, at least one of which amines contains a group reactive with the oxidation products of primary aromatic amino photographic developing agents, which comprises selectively reacting a cool solution of one of said amines with the carboxylic acid chloride group of said sulfobenzcyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulfonic acid amide.
2. The method of reacting sulfobenzoyldichloride with two different primary amines in successive stages, one of which amines contains a reactive methylene roup and the other of which amines contains a 5-membered heterocyclic group containing a mercapto group, which comprises selectively reacting a cool solution of one of said amines with the carboxylic acid chloride group of said suliobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulfonic acid amide.
3. The method of reacting sulfobenzoyldichloride in successive stages, with a l-phenyl pyrazolone having a reactive methylene group in the 4-position and having a primary amino substituent, and with 5-amino-2-mercaptobenzimidazole, which comprises selectively reacting a cool solution of one or said amines with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulionic acid amide.
4. The method of reacting sulfobenzoyldichloride in successive stages, with a l-phenyl pyrazolone having a reactive methylene group in the 4-position and having a primary amino substitu- 1 cut, and with 5-amino-2-mercaptobenzimidazole, which comprises selectively reacting a cool solution of said pyrazolone with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group,
and then heating said reaction product with said S-amino-2-mercaptobenzimidazole to produce a sulfonic acid amide.
5. The method of reacting sulfobenzoyldichloride in successive stages, with a phenol having a primary amino group in the 2-position, and with 5-amino-2-mercaptobenzimidazole, which comprises selectively reacting a cool solution of one of said amines with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with the other of said amines to produce a sulfonic acid amide.
6. The method of reacting sulfobenzoyldichloride in successive stages, with a phenol having a primary amino group in the 2-position, and with 5-amino-2-mercaptobenzimidazole, which comprises selectively reacting a cool solution of said phenol with the carboxylic acid chloride group of said sulfobenzoyldichloride to produce a carboxylic acid amide reaction product containing an unreacted sulfonyl chloride group, and then heating said reaction product with said 5-amino- Z-mercaptobenzimidazole to produce a sulfonic acid amide.
ARNOLD WEISSBERGER. ILMARI F. SALMINEN.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name I Date 1,663,474 Ackerman Mar. 20, 1928 FOREIGN PATENTS Number Country Date 503,752 Great Britain 1939
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US508392A US2484477A (en) | 1943-10-30 | 1943-10-30 | Process for making color couplers |
FR943670D FR943670A (en) | 1943-10-30 | 1946-11-26 | Improvements to chromogenic couplers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US508392A US2484477A (en) | 1943-10-30 | 1943-10-30 | Process for making color couplers |
Publications (1)
Publication Number | Publication Date |
---|---|
US2484477A true US2484477A (en) | 1949-10-11 |
Family
ID=24022580
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US508392A Expired - Lifetime US2484477A (en) | 1943-10-30 | 1943-10-30 | Process for making color couplers |
Country Status (2)
Country | Link |
---|---|
US (1) | US2484477A (en) |
FR (1) | FR943670A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2722526A (en) * | 1952-09-24 | 1955-11-01 | American Cyanamid Co | Trialkylphosphites as acid acceptors in the synthesis of amides |
US4124396A (en) * | 1977-03-03 | 1978-11-07 | Eastman Kodak Company | 2,5-Dicarbonylaminophenol dye-forming couplers |
US4299914A (en) * | 1979-05-07 | 1981-11-10 | Konishiroku Photo Industry Co., Ltd. | Method for forming a cyan dye image |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1663474A (en) * | 1926-10-06 | 1928-03-20 | Chem Ind Basel | Vat dyestuffs of the anthraquinone series containing the triazine ring and process of making same |
GB503752A (en) * | 1936-07-07 | 1939-04-11 | Kodak Ltd | Process of colour photography |
-
1943
- 1943-10-30 US US508392A patent/US2484477A/en not_active Expired - Lifetime
-
1946
- 1946-11-26 FR FR943670D patent/FR943670A/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1663474A (en) * | 1926-10-06 | 1928-03-20 | Chem Ind Basel | Vat dyestuffs of the anthraquinone series containing the triazine ring and process of making same |
GB503752A (en) * | 1936-07-07 | 1939-04-11 | Kodak Ltd | Process of colour photography |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2722526A (en) * | 1952-09-24 | 1955-11-01 | American Cyanamid Co | Trialkylphosphites as acid acceptors in the synthesis of amides |
US4124396A (en) * | 1977-03-03 | 1978-11-07 | Eastman Kodak Company | 2,5-Dicarbonylaminophenol dye-forming couplers |
US4299914A (en) * | 1979-05-07 | 1981-11-10 | Konishiroku Photo Industry Co., Ltd. | Method for forming a cyan dye image |
Also Published As
Publication number | Publication date |
---|---|
FR943670A (en) | 1949-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2772162A (en) | Diacylaminophenol couplers | |
US2592364A (en) | p-phenylenediamine developer containing alkylacylamidoethyl or alkylacylamidoethoxyring substituents | |
US3034892A (en) | Magenta-colored cyan-forming couplers | |
US4009035A (en) | Process for forming cyan dye photographic images | |
US2455169A (en) | Colored couplers | |
US2956876A (en) | Mercapto heterocyclic addenda for reversal color development | |
US3615505A (en) | Silver halide emulsion containing 2-pyrazolin-5-one color coupler | |
US2412700A (en) | Thioglycolic amides | |
US3222176A (en) | Photographic colour images from amino substituted phenols | |
US2592363A (en) | P-phenylenediamine developer containing nu-alkylacetamido ethyl substituent | |
US3677764A (en) | Silver halide emulsion containing purple coupler for color photography and process of making the same | |
US2484477A (en) | Process for making color couplers | |
JPS5816174B2 (en) | Shashin Halogen Kaginzai Ryounogen Zohou | |
US2350138A (en) | Nondiffusing acylacetyl sulphonamide coupler | |
US4146400A (en) | Color photographic material containing new 2-equivalent yellow couplers | |
US2710803A (en) | Color couplers containing hydroxyalkyl groups | |
US4281059A (en) | Photographic material | |
US2979405A (en) | Light-sensitive photographic element containing a 1-hydroxy-2-naphthoic acid anilidecolor coupler | |
US2448939A (en) | Thioglycolic amide couplers | |
US3779763A (en) | Phenol color couplers | |
US2395776A (en) | Color photography | |
US2695234A (en) | Photographic development | |
US2728660A (en) | Salicylic acid ester and amide photographic coupler compounds | |
US3543292A (en) | Photographic gelatin hardened with bis isoxazole compounds and their quaternary salts | |
US2411951A (en) | 4,4'-bis (pyrazolone) couplers for color photography |