US3178441A - Pyridyl-pyrazolidine 3-ones - Google Patents
Pyridyl-pyrazolidine 3-ones Download PDFInfo
- Publication number
- US3178441A US3178441A US243598A US24359862A US3178441A US 3178441 A US3178441 A US 3178441A US 243598 A US243598 A US 243598A US 24359862 A US24359862 A US 24359862A US 3178441 A US3178441 A US 3178441A
- Authority
- US
- United States
- Prior art keywords
- phenyl
- general formula
- pyridyl
- pyrazolidone
- pyrazolidine
- 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
- -1 PYRAZOLIDIN-3-ONE COMPOUND Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- KKLMJYDGZSAIQX-UHFFFAOYSA-N 2-(n-hydroxyanilino)acetic acid Chemical compound OC(=O)CN(O)C1=CC=CC=C1 KKLMJYDGZSAIQX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- ABZPCWYIRGIXJP-UHFFFAOYSA-N ethyl 3-pyridin-4-ylprop-2-enoate Chemical compound CCOC(=O)C=CC1=CC=NC=C1 ABZPCWYIRGIXJP-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- NVXLIZQNSVLKPO-UHFFFAOYSA-N Glucosereductone Chemical compound O=CC(O)C=O NVXLIZQNSVLKPO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004285 Potassium sulphite Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229960005219 gentisic acid Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- HAYWTXQRYXYRAF-UHFFFAOYSA-N hydron;pyrazolidin-3-one;chloride Chemical compound Cl.O=C1CCNN1 HAYWTXQRYXYRAF-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- KRTLKPFLTASKCG-UHFFFAOYSA-N pyridin-4-ylhydrazine Chemical compound NNC1=CC=NC=C1 KRTLKPFLTASKCG-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000010792 warming Methods 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/30—Developers
- G03C5/3028—Heterocyclic compounds
- G03C5/3035—Heterocyclic compounds containing a diazole ring
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
Definitions
- R R and R are the same or different and are hydrogen atoms or hydrocarbon groups.
- the compound l-phenyl- 3-pyrazolidone has received widespread commercial use, for which purpose it is customarily employed in association with another photographic developing substance with which it exhibits a superadditive effect.
- it may be used in association with hydroquinone, hydroxyphenyl glycine, gentisic acid, ascorbic acid, reductone and other substances.
- 3-pyrazolidone derivatives as defined below are extremely useful developing agents latl high vpI-l values and have a substantially greater solu- 1 ity.
- R may be, for example, furyl, thienyl, pyrryl, indolyl, pyridyl, thiazolyl, piperidyl, morpholinyl, pyrrolidinyl or benziminazolyl.
- R may be, for example, a phenyl group or an alkyl-, alkoxy-, halogenor other substituted phenyl group, or any of the heterocycles referred to above.
- R -CH CH--COOR (IV) where R is a hydrocarbon group and the other symbols have the meanings hereinbefore assigned.
- R with an orthophenylene diamine.
- the new developing substances of the present inven-' tion may be used in the same manner as 1-phenyl-3- pyrazolidone, but at pH values above 9.5, in association with hydroquinone, hydroxyphenyl glycine, or any other known developing agent with which the new compounds exert a superadditive effect.
- EXAMPLE 3 l-phenyl-5-4'-pyridylpyrazolidind-one
- the method of Example 1 was used with ethyl 3-4- pyridylacrylate.
- the pyrazolidin-3-one formed colourless plates, M. Pt. 161-162, by crystallisation from a mixture of ethanol and water.
- EXAMPLE 4 1 -p-chlr0pIze1zyI-5 -3 '-pyridylpyrazolidin-3-0ne
- EXAMPLE 5 1,5-bis-4-pyridylpyraz0lidin-3-0ne
- a solution of sodium (3.2 g.) in ethanol 100 ml.) was refluxed for 16 hours with 4-hydrazinopyridine (11.5 g.) and ethyl 3-4-pyridylacrylate (18.7 g.).
- the residue obtained after evaporation of the solvent under reduced pressure was refluxed with concentrated hydrochloric acid (80 ml.) for 2 /2 hours.
- the cooled solution was filtered, and the filtrate treated with crystalline sodium acetate (100 g.).
- EXAMPLE 8 5 -2-bcnzim inazolyl-I -phenyl pyraz0lidin-3-0r1e A mixture of 3-oxo-1-phenylpyrazolidine-S-carboxylic acid (5.0 g.), o-phenylene-diamine (2.62 g.), and 4 N hydrochloric acid (25 ml.) was refluxed for 2 hours.
- the solution was filtered hot (charcoal), and the cooled filtrate was neutralised with aqueous ammonia.
- EXAMPLE 9 5-2-benzimidaz0lyl-1-p-tolylpyraz0lidin-3-0ne hydrochloride A mixture of 3-oxo-1-p-tolylpyrazolidine-S-carboxylic acid (3.32 g.), o-phenylene diamine (1.63 g.), and 4 N hydrochloric acid (16 ml.) was refluxed for 2 hours. The crystalline solid which separated was collected after cooling the mixture, and was crystallised from dilute hydrochloric acid, to give the pyrazolidin-3-one hydrochloride a cream-coloured prisms, M. Pt. 265-267 (decomp).
- EXAMPLE 10 The following is a suitable developer composition according to the invention:
- R is selected from the group consisting of 2- pyridyl, 3-pyridyl and 4-pyridyl and R is selected from the class consisting of phenyl, halophen'yl and tolyl.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
United States Patent 3,178,441 PYRlDYL-PYRAZOLIDINE 3-0NES Geoffrey Ernest Ficken, Ilford, Essex, England, assignor to Ilford Limited, Ilford, Essex, England, a British company No Drawing. Filed Dec. 10, 1962, Ser. No. 243,598 Claims priority, application Great Britain, Dec. 19, 1961, 45,466/ 61 6 Claims. (Cl. 260-295) This invention relates to a new class of photographic developing substance and to the use thereof in the development of silver halide photographic emulsion layers.
In specification No. 542,502 there is described a process for the development of reducible silver salt images in photographic materials which comprises treating the materials with an aqueous solution containing a 3- pyrazolidone of the general Formula I:
where R R and R are the same or different and are hydrogen atoms or hydrocarbon groups.
Of the foregoing compounds, the compound l-phenyl- 3-pyrazolidone has received widespread commercial use, for which purpose it is customarily employed in association with another photographic developing substance with which it exhibits a superadditive effect. Thus it may be used in association with hydroquinone, hydroxyphenyl glycine, gentisic acid, ascorbic acid, reductone and other substances.
Subsequently it was shown that similar, though not necessarily identical, developing characteristics were possessed by corresponding compounds in which the one or both of the hydrogen atoms shown in the 4 and 5 positions of the compounds of the foregoing formula were replaced by substituent groups such as hydrocarbon residues. p
A difficulty which has been experienced with the compound 1-phenyl -3-pyrazolidone lies in its limited solubility in alkaline media.
. It has now been found that 3-pyrazolidone derivatives as defined below are extremely useful developing agents latl high vpI-l values and have a substantially greater solu- 1 ity.
According to a first feature of the present invention there are provided 3-pyrazolidone derivatives of the general Formula II:
Rt-OH NH Rn (II) wherein R is a heterocyclic substituent and R is an aryl, substituted aryl or heterocyclic group.
In the foregoing formula R may be, for example, furyl, thienyl, pyrryl, indolyl, pyridyl, thiazolyl, piperidyl, morpholinyl, pyrrolidinyl or benziminazolyl. R may be, for example, a phenyl group or an alkyl-, alkoxy-, halogenor other substituted phenyl group, or any of the heterocycles referred to above.
These compounds are not effective photographic developing agents for silver halide emulsions at pH values below about 9.5. At pH values above that level they show a very strong superadditive effect with such auxiliary developing substances as hydroquinone, and they have the especial merit of having a high solubility in highly alkaline solutions.
3,178,441 Patented Apr. 13, 1965 ice Processes for the production of the S-pyrazolidone types of developer compound are described, for example, in specifications Nos. 542,502, 703,669 and 728,368. Of the various known methods, those of specifications Nos. 703,669 and 728,368 can most readily be adapted to the production of compounds according to the present invention, and according to further features of the present invention, therefore, compounds of general Formula II are prepared by:
(a) Reacting a hydrazine of the general Formula III:
R NH.NH (III) with an ester of the general Formula IV:
R -CH=CH--COOR (IV) where R is a hydrocarbon group and the other symbols have the meanings hereinbefore assigned.
(b) Reacting a hydrazine of the general Formula III with an amide of the general Formula V:
(c) Reacting a hydrazine of the general Formula III with a compound of the general Formula VI:
R CH-: CHCN (VI) and subjecting the resulting 3-imino pyrazolidone to hydrolysis.
(d) For the production of compounds of general Formula II where R is a benziminazole residue reacting a compound of the general Formula VII:
R: with an orthophenylene diamine.
The new developing substances of the present inven-' tion may be used in the same manner as 1-phenyl-3- pyrazolidone, but at pH values above 9.5, in association with hydroquinone, hydroxyphenyl glycine, or any other known developing agent with which the new compounds exert a superadditive effect.
The following examples will serve to illustrate the invention:
(VII) EXAMPLE 1 1-phenyl-5-2'-pyridylpyraz0lidin-3-0ne l-phenyl-5-3-pyridylpyraz0lidin-3-one This was prepared by the method of Example 1, but using ethyl 3-3'-pyridylacrylate. The pyrazolidin-El-one formed colourless plates, M. Pt. 127-128", by crystallisation from ethyl acetate.
EXAMPLE 3 l-phenyl-5-4'-pyridylpyrazolidind-one The method of Example 1 was used with ethyl 3-4- pyridylacrylate. The pyrazolidin-3-one formed colourless plates, M. Pt. 161-162, by crystallisation from a mixture of ethanol and water.
EXAMPLE 4 1 -p-chlr0pIze1zyI-5 -3 '-pyridylpyrazolidin-3-0ne EXAMPLE 5 1,5-bis-4-pyridylpyraz0lidin-3-0ne A solution of sodium (3.2 g.) in ethanol 100 ml.) was refluxed for 16 hours with 4-hydrazinopyridine (11.5 g.) and ethyl 3-4-pyridylacrylate (18.7 g.). The residue obtained after evaporation of the solvent under reduced pressure was refluxed with concentrated hydrochloric acid (80 ml.) for 2 /2 hours. The cooled solution was filtered, and the filtrate treated with crystalline sodium acetate (100 g.). The solid which separated was collected, washed thoroughly with cold water, and purified by dissolving in dilute hydrochloric acid and reprecipitating with aqueous ammonia. The pyrazolidin-B-one formed off-white crystals, M. Pt. 329-331 (decomp.).
EXAMPLE 6 5-2'-furyl-1-phenylpyrazolidin-S-one A solution of sodium (2.0 g.) in ethanol (70 ml.) was refluxed for 25 hours with henylhydrazine (6.5 ml.) and 3-2'-furylacrylamide (8.95 g.). The solvent was removed under reduced pressure, and a solution of the residue in water (70 ml.) was acidified with acetic acid. The tar which separated initially slowly gave a solid, which was collected and crystallised from a mixture of benzene and light petroleum. The pyrazolidin-3-one formed colourless plates, M. Pt. 88-89".
EXAMPLE 7 1-phenyl-5-2'-thienylpyraz0lidin-3-0ne Phenylhydrazine (16 ml.) and 3-2'-thienylacrylonitrile (22 g.) were refluxed for 16 hours in ethanol (65 ml.) containing sodium (0.65 g.), and the solid which separated on cooling was filtered off and dried. This crude 3- imino-1-phenyl-5-2'-thienylpyrazolidine, M. Pt. 174-179, was refluxed for 16 hours with a mixture of concentrated hydrochloric acid (5.5 ml.) and water (50 ml.), and the resulting aqueous solution was decanted from the sticky solid which had separated. This solid was dissolved by warming in 2 N sodium carbonate solution (50 ml.) and the solution was filtered hot (charcoal). Acidification of the filtrate caused the separation of a solid, which was crystallised from aqueous ethanol to yield the pyrazo- 1idin-3-or1e as cream-coloured needles, M. Pt. 148-151".
EXAMPLE 8 5 -2-bcnzim inazolyl-I -phenyl pyraz0lidin-3-0r1e A mixture of 3-oxo-1-phenylpyrazolidine-S-carboxylic acid (5.0 g.), o-phenylene-diamine (2.62 g.), and 4 N hydrochloric acid (25 ml.) was refluxed for 2 hours.
The solution was filtered hot (charcoal), and the cooled filtrate was neutralised with aqueous ammonia. The
solid which separated was collected and crystallised from methanol to yield the pyraZolidin-3-one as colourless plates, M. Pt. 271-273" (decomp.).
EXAMPLE 9 5-2-benzimidaz0lyl-1-p-tolylpyraz0lidin-3-0ne hydrochloride A mixture of 3-oxo-1-p-tolylpyrazolidine-S-carboxylic acid (3.32 g.), o-phenylene diamine (1.63 g.), and 4 N hydrochloric acid (16 ml.) was refluxed for 2 hours. The crystalline solid which separated was collected after cooling the mixture, and was crystallised from dilute hydrochloric acid, to give the pyrazolidin-3-one hydrochloride a cream-coloured prisms, M. Pt. 265-267 (decomp).
EXAMPLE 10 The following is a suitable developer composition according to the invention:
G. Sodium sulphite (anhydrous) 24 Potassium sulphite (anhydrous) 20 Potassium canbonate (anhydrous) 10 Hydroquinone 1 1 1-phenyl-5-2-pyridylpyrazolidin-3-one 0.275 Sodium hydroxide 3.6 Potassium bromide 4 S-mercaptol-phenyltetrazole 0.01
Water to make 1 litre.
I claim: 1. A pyrazo1idin-3-one compound of the formula:
1I2C-C=O Rl- H 1111-1 where R is selected from the group consisting of 2- pyridyl, 3-pyridyl and 4-pyridyl and R is selected from the class consisting of phenyl, halophen'yl and tolyl.
1-p1enyl-5-2-pyridylpyrazolidin-3-one. 1-phenyl-5-3'-pyridylpyraZolidin-3-one.
. l-phenyl- 5-4'-pyridylpyrazolidin-3-one.
1-p-chlorophenyl-5-3-pyridylpyrazolidin-3-one.
. 1,5-bis-4-pyridylpyrazolidin-3-one.
P MA References Cited by the Examiner UNITED STATES PATENTS OTHER REFERENCES Bernthsen et al.: Organic Chemistry, 1931 Ed., pp. 567-571 (Blackie).
Sidgwick: Organic Chemistry of Nitrogen, 1937 Ed., pp. 521-7.
WALTER A. MODANCE, Primary Examiner. D. MCCUTCHEN, JOHN RANDOLPH, Examiners.
Claims (1)
1. A PYRAZOLIDIN-3-ONE COMPOUND OF THE FORMULA:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB45465/61A GB985653A (en) | 1961-12-19 | 1961-12-19 | Pyrazolidone derivatives |
| GB45466/61A GB997033A (en) | 1961-12-19 | 1961-12-19 | Pyrazolidinone derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3178441A true US3178441A (en) | 1965-04-13 |
Family
ID=26265596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US243598A Expired - Lifetime US3178441A (en) | 1961-12-19 | 1962-12-10 | Pyridyl-pyrazolidine 3-ones |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3178441A (en) |
| DE (1) | DE1445931A1 (en) |
| GB (2) | GB985653A (en) |
| NL (1) | NL286908A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4074051A (en) * | 1971-12-08 | 1978-02-14 | Minnesota Mining And Manufacturing Company | 3-Pyrazolidinone derivatives |
| US4095024A (en) * | 1975-01-31 | 1978-06-13 | Imperial Chemical Industries Limited | Process for the manufacture of 1-aryl-3-carboxypyrazolid-5-ones |
| US4550119A (en) * | 1983-05-23 | 1985-10-29 | Warner-Lambert Company | 2,4-Dihydro-5-[(substituted)phenyl]-4,4-disubstituted-3H-pyrazol-3-ones |
| US4551538A (en) * | 1984-12-20 | 1985-11-05 | American Home Products Corporation | Phenylpyrazolidine acetic acid derivatives |
| US5089515A (en) * | 1986-11-20 | 1992-02-18 | Mitsubishi Kasei Corporation | Lipid-peroxide formation inhibiting composition and novel compounds useful therefor |
| CN101333191B (en) * | 2008-07-25 | 2013-04-03 | 浙江师范大学 | Method for preparing 2,5-disubstituted pyrazoline-3-ketone derivates |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2833779A (en) * | 1956-10-29 | 1958-05-06 | American Cyanamid Co | Substituted pyrazoles |
| US2981623A (en) * | 1954-03-15 | 1961-04-25 | Agfa Ag | Photographic developers |
| US3010827A (en) * | 1956-12-22 | 1961-11-28 | Agfa Ag | Photographic developer |
| US3041343A (en) * | 1959-10-14 | 1962-06-26 | Sandoz Ltd | 4-(thienyl-2'')-and 4-(pyridyl-3'')-5-aminopyrazoles |
-
0
- NL NL286908D patent/NL286908A/xx unknown
-
1961
- 1961-12-19 GB GB45465/61A patent/GB985653A/en not_active Expired
- 1961-12-19 GB GB45466/61A patent/GB997033A/en not_active Expired
-
1962
- 1962-12-10 US US243598A patent/US3178441A/en not_active Expired - Lifetime
- 1962-12-17 DE DE19621445931 patent/DE1445931A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2981623A (en) * | 1954-03-15 | 1961-04-25 | Agfa Ag | Photographic developers |
| US2833779A (en) * | 1956-10-29 | 1958-05-06 | American Cyanamid Co | Substituted pyrazoles |
| US3010827A (en) * | 1956-12-22 | 1961-11-28 | Agfa Ag | Photographic developer |
| US3041343A (en) * | 1959-10-14 | 1962-06-26 | Sandoz Ltd | 4-(thienyl-2'')-and 4-(pyridyl-3'')-5-aminopyrazoles |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4074051A (en) * | 1971-12-08 | 1978-02-14 | Minnesota Mining And Manufacturing Company | 3-Pyrazolidinone derivatives |
| US4095024A (en) * | 1975-01-31 | 1978-06-13 | Imperial Chemical Industries Limited | Process for the manufacture of 1-aryl-3-carboxypyrazolid-5-ones |
| US4550119A (en) * | 1983-05-23 | 1985-10-29 | Warner-Lambert Company | 2,4-Dihydro-5-[(substituted)phenyl]-4,4-disubstituted-3H-pyrazol-3-ones |
| US4551538A (en) * | 1984-12-20 | 1985-11-05 | American Home Products Corporation | Phenylpyrazolidine acetic acid derivatives |
| US5089515A (en) * | 1986-11-20 | 1992-02-18 | Mitsubishi Kasei Corporation | Lipid-peroxide formation inhibiting composition and novel compounds useful therefor |
| CN101333191B (en) * | 2008-07-25 | 2013-04-03 | 浙江师范大学 | Method for preparing 2,5-disubstituted pyrazoline-3-ketone derivates |
Also Published As
| Publication number | Publication date |
|---|---|
| GB997033A (en) | 1965-06-30 |
| DE1445931A1 (en) | 1969-02-13 |
| NL286908A (en) | |
| GB985653A (en) | 1965-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE812874C (en) | Process for the production of color photographic images | |
| NO174420B (en) | Analogous Procedure for Preparation of Therapeutically Active Pyridine-2,4- and 2,5-Dicarboxylic Acids | |
| US3178441A (en) | Pyridyl-pyrazolidine 3-ones | |
| US3152136A (en) | Dinitroaroyl-nu-pyridyl amides | |
| Katritzky | 33. The structure and reactivity of 2-aminopyridine 1-oxide | |
| SU991945A3 (en) | Process for preparing derivatives of mercaptoimidazole or their salts | |
| US3892740A (en) | Process for the production of carboxamides of oxo-1,2-benzothiazine-1,1-dioxides | |
| US2748125A (en) | 1-substituted-4-sulfamylpiperazine and method of preparing the same | |
| US2401522A (en) | Aromatic carboxylic acid amides and a process for their manufacture | |
| IE880350L (en) | Pyridine-2,4- and -2,5-dicarboxylic acid derivatives,¹process for their preparation, the use thereof and¹medicaments based on these compounds | |
| US3060177A (en) | O-(aminoalkyl)oxime derivatives of heterocyclic aldehydes and ketones | |
| US3072649A (en) | S-tmalkoxycinnamamide derivatives | |
| US3759911A (en) | Triazine derivatives | |
| US2776979A (en) | 1-nitroso-2-imidazolidone and process | |
| US3337551A (en) | Heterocyclic amides of 2, 6-dioxo-4-piperidineacetic acid | |
| US3272828A (en) | 5-nitro-2-furoylamidoximes | |
| US3700677A (en) | Certain thiazole-5-carboxylates | |
| US2524802A (en) | Hydroxybenzenesulfonamidopyridazines and preparation of same | |
| US3272833A (en) | Certain substituted 5-nitro-2-furylamidoximes | |
| US3073819A (en) | Hydrazine derivatives | |
| US1994170A (en) | Compound of the distyryl pyridinium salt series and its production | |
| SU436495A3 (en) | Method for producing benzodiazepine derivatives | |
| US2784195A (en) | Quaternary ammonium salts of nu-phenyl-nu-picolyl-dialkylaminoalkylamines | |
| US2436685A (en) | Substituted piperazines | |
| US2372690A (en) | Intermediates for the production of vitamin b6 and processes of preparing the same |