US2772282A - 3-pyrazolidones - Google Patents

3-pyrazolidones Download PDF

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Publication number
US2772282A
US2772282A US372148A US37214853A US2772282A US 2772282 A US2772282 A US 2772282A US 372148 A US372148 A US 372148A US 37214853 A US37214853 A US 37214853A US 2772282 A US2772282 A US 2772282A
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United States
Prior art keywords
pyrazolidone
dimethyl
chloride
compounds
dialkyl
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Expired - Lifetime
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US372148A
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English (en)
Inventor
Charles F H Allen
Jr John R Byers
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE530884D priority Critical patent/BE530884A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US372148A priority patent/US2772282A/en
Priority to FR1131853D priority patent/FR1131853A/fr
Priority to GB22511/54A priority patent/GB757271A/en
Application granted granted Critical
Publication of US2772282A publication Critical patent/US2772282A/en
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D231/08—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen or sulfur atoms directly attached to ring carbon atoms

Definitions

  • the 4,4-dialkyl-3-pyrazo1idones of the invention have 01H: the general formula OH:
  • R represents an alkyl group preferably of 1 to 4 1-p acetamidopheny1-4,4diethy1-3-pyrazo1idone carbon atoms such as methyl, ethyl, n-propyl, lso-butyl;
  • aryl group of the benzene or naphthalene series OH substituted or not such as phenyl, o-tolyl, m-tolyl, p-tolyl, 0:0 p-aniinophenyl, o, 111-, p-methoxyphenyl, p-dialkylarninophenyl, o-nitrophenyl, o-brornopheny1, o-chlorophenyl, I m-nitrophenyl, m-bromophenyl, m-chlorophenyl, p-nitro- H-N 01-1 phenyl, p-benzylphenyl, p-brornophenyl, p-chlorophenyl, p-acetamidophenyl, 0-, m-, p-carboxyphenyl, p-cyanophenyl, hydroxyalkylphenyl such as p-hydroxye
  • a hydrazine such as an arylhydrazine of the benzene or naphthalene series such as phenylhydrazine, is generally reacted with approximately a molecular equivalent amount of a 3- halogen-2,2-dialkyl propionyl halide such as 3-chloro-2,2- dimethylpropionyl chloride in the presence of an acid binding agent such as sodium carbonate, sodium acetate, methyl morpholine, pyridine, quinoline, isoquinoline, dialkylanilines, such as diethylaniline, trialkylarnines such as triethylamine and N-alkylpiperidines.
  • a 3- halogen-2,2-dialkyl propionyl halide such as 3-chloro-2,2- dimethylpropionyl chloride
  • an acid binding agent such as sodium carbonate, sodium acetate, methyl morpholine, pyridine, quinoline, isoquinoline, dialkylanilines, such as dieth
  • the mentioned ingredients be combined within a rather limited range of temperature of the order of to 10 C. in order to prevent side reactions such as the formation of a S-pyrazolidone compound which materially reduces the yield of the desired product.
  • the yield of product is greatly increased by gradually warming up the reaction mixture as over a steam bath, and maintaining the temperature of the reaction mixture at about 100 C. until the reac tion is complete.
  • heating of the reaction mixture over a steam bath for about 1 to 10 hours produces the best yields.
  • one hour heating yields 40 percent and 4 hours heating yields percent of the theoretical amount of the 3-pyrazolidone compound. Longer heating can be expected to increase the yield somewhat and it is apparent that it is preferred that the heating be carried out for at least 4 to 5 hours or for an equivalent length of time if heating is conducted at a temperature differing appreciably from steam bath temperature.
  • 3-*halogen-2,2-dialkyl propionyl halides used in preparing the 4,4-dialkyl-3-pyrazolidones of the invention have the structure in which X is a halogen atom and R1 and R2 are alkyl groups and can be prepared as described by Kharasch and Brown, I. A. C. S. 62, 925929 (1940).
  • 3-chloro- 2,2-dimethylpropionyl chloride prepared by that process from sulfuryl chloride and trimethyl acetic acid had a boiling point of -86 C. at 60 mm. and the refractive index was (n l.4539).
  • a satisfactory procedure is as follows:
  • 3-chloro-Z,2'dipropylpropionylhalide can be made in a similar manner.
  • the alkyl groups in the 2-position of the propionyl halides are identical, and when these propionyl halides are reacted with the hydrazines, the resulting 3-pyrazolidone compounds contain identical alkyl groups in the 4-position (R and R2 in the above formulas).
  • the 4,4-dialkyl-3-pyrazolidones having the above formula in which R and R2 are different alkyl groups are preferably prepared by reaction of the selected arylhydrazine with propionyl halides having the above formula in which R and R2 are different alkyl groups.
  • propionyl halides can be prepared from disubstituted acetaldehydes (R1RzCHCHO) such as methylpropyl acetaldehyde by reaction with formaldehyde and alkali to obtain the corresponding hydroxymethyl disubstituted acetaldehydes (RiRzCCHO) OHZOH such as hydroxymethyl-propylmethylacetaldehyde, followed by oxidation to obtain a hydroxymethyl disuhstituted acetic acid, i. e.
  • R1RzCHCHO disubstituted acetaldehydes
  • SiRzCCHO hydroxymethyl disubstituted acetaldehydes
  • HOCE'T EHRQCOOH HOCHflIHOHQOOOH 03131 which is then treated with thionyl chloride to obtain the desired 2,2-dialkylsubstituted-3-chloropropionyl chloride such as 2,2-methylpropyl-3-chloropropionyl chloride which is then reacted with the selected hydrazine to obtain the corresponding 4,4-disubstituted-3-pyrazolidone.
  • the 1 hydroxyalkylaryl 4,4 dialkyl 3-pyrazolidone compounds having the above general formula wherein R represents a hydroxyalkylphenyl group are prepared by the reaction of acetoxyalkylphenylhydrazines with the above described 2,2 disubstituted 3 chloropropionyl halides, followed by acidic or basic hydrolysis of the resulting 1-acetoxyalkylphenyl-4,4-dia1kyl-3-pyrazolidone as described in the following examples.
  • 1-hydroxyphenyl-4,4-dialkyl-3-pyrazolidones are prepared from acyloxyphenylhydrazines such as p-acetoxyphenylhydrazine reacted with the selected 2,2-dialkyl substituted 3-chloropropionyl chloride, such as 2,2-dimethyl- S-chloropropionyl chloride in the manner of the following examples, and subsequently hydrolyzing the resultant 1-acyloxyphenyl-4,4-dialkyl-S-pyrazolidone.
  • the comparable 1-naphtho1-4,4-dialkyl-3-pyrazolidones are prepared similarly from the acetoxynaphthylhydrazines.
  • the 1-arnin0phenyl-4,4-disubstituted S-pyrazolidones can be prepared similarly by reacting the selected acylaminophenyl'hydrazine such as p-acetaminophenylhydrazine with the selected 2,2-disubstituted-3-chloropropionyl chloride, e. g, 2,2-dimethyl-3-chloropropionyl chloride, followed by saponification of the resultant amide.
  • the selected acylaminophenyl'hydrazine such as p-acetaminophenylhydrazine
  • 2,2-disubstituted-3-chloropropionyl chloride e. g, 2,2-dimethyl-3-chloropropionyl chloride
  • the 1-aminoaryl-4,4-diallcyl-3-pyrazolidone compounds can also be obtained by our process by utilizing a nitrophenyl hydrazine, such as p-nitrophenylhydrazine for reaction with the acid chloride followed by reduction of the nitro group of the resulting 1-nitroaryl-4,4-dialkyl-3- pyrazolidone.
  • a nitrophenyl hydrazine such as p-nitrophenylhydrazine
  • the 1-alky1*4,4-dialkyl-3-pyrazolidones are prepared by reaction of aikylhydrazines such as methylhydrazine or carboxymethylhydrazine, with the 3-halogen-2,2-dialkylpropionyl halides such as 3-chloro-2,2-dimethylpropionyl chloride.
  • aikylhydrazines such as methylhydrazine or carboxymethylhydrazine
  • 3-halogen-2,2-dialkylpropionyl halides such as 3-chloro-2,2-dimethylpropionyl chloride.
  • the mixture is cooled, diluted with 300 ml. of chloroform, and extracted with several portions of 5l0% aqueous sodium hydroxide. Each extract is washed twice with a little chloroform, neutralized (to pH 6, universal indicator paper) with concentrated hydrochloric acid, cooled, and filtered. The first extracts are neutralized by the pyridine hydrochloride and yield no pyrazolidone. From later portions are obtained 64 g. (74%) of crude material. Recrystallization from aqueous methanol yields 59 g. (68%); M. P. 164166 (uncon).
  • the hydrazine salts e. g., phenylhydrazine hydrochloride can also be used in the above synthesis.
  • 2-chloro-1,l-dimethylpropionyl chloride (14 g.; 0.1 mole) is dissolved in 25 ml. of pyridine which has been cooled to 5 in :an ice bath. This solution is added in four portions at 5 during 5 minutes to a slurry of 16 g. of p-tolyl-l-iydrazine hydrochloride in 15 ml. of pyridine. The mixture is heated on the steam bath until all has dissolved, and then heated for four more hours. Cold water (350 ml.) is stirred in during 15 minutes. The solution is scratched to start crystallization, cooled to 5, and filtered. There is thus obtained 12.4 g. of crude 1-p-tolyl--4,4-dimethyl-3-pyrazolidone (M. P. 143145) which is 60% of the theoretical amount of 20.4 g.
  • Purification is eiiected by dissolving in 55 ml. of absolute alcohol and treating with Norit.
  • the hot filtered solution is cooled to 5 and again filtered.
  • the crystallino product is washed well with petroleum ether to remove a yellow impurity and dried.
  • the melting range is then 148149.
  • the isomeric ortho and meta-tolyl compounds l-otolyl-4,4-dimethyl-3-pyrazo1idone M. P. 143-144 C., and 1-m-tolyl-4,4-dimethyl-3-pyrazolidlone M. P. 107 C., are prepared by the above method using the corresponding .orthoand meta-tolylhydrazines or their salts.
  • Example 3 1- (p-fi-hydroxyethylphenyl) -4,4-dimethyl- 3-pyraz0lid0ne p(B-Acetoxyethyl)phenylhydrazine hydrochloride was prepared by diazotization of 33 g. of p-(B-acetoxyethyD- aniline followed by reduction of the resulting diazonium compound with 85.5 g. stannous chloride dihydrate. The diazonium compound was extracted with ether, Washed with water, and dried over magnesium. sulfate The hydrazine HCl derivative was precipitated by bubbling I-ICl through the ether solution until no additional product separated.
  • the desired 3-pyrazolidone derivative was obtained by mixing an externally cooled solution of 1.6 g. of (pacetoxyethyl) phenylhydrazine hydrochloride in 8 ml. of dry pyridine and 1.08 g. of 3-chloro-2,2-dimethylpropionyl chloride, followed by refluxing the reaction mixture for 2 hours.
  • the resulting l-(p-fi-acetoxyethylphenyl)-4,4-dimethyl-3-pyrazolidone after further extraction and recrystallization, had a. melting point of 81.5-83.5 C.
  • arylhydrazines and alkylhydrazines useful in preparing the compounds of the invention are, for example:
  • the developing agents were also compared for their stability in developers of relatively high pH of the order of 10. This is, developer compositions of this alkalinity are well known to undergo darkening due to aerial oxidation on standing in open vessels, which shortens their life.
  • developer compositions of this alkalinity are well known to undergo darkening due to aerial oxidation on standing in open vessels, which shortens their life.
  • three developer compositions of pH 10, each containing one of the three above developing agents in addition to hydroquinone were aerated for 4 days in open vessels.
  • the two developer compositions containing the developing agents of the invention darkened measurably less than the developer composition containing l-phenyl-3-pyrazolidone.
  • a I i-pyrazolidone compound having the general formula /R2 O C-C wherein R represents a member of the class consisting of phenyl, tolyl, p-fl-hydroxyethylphenyl, and p-fi-acetoxyethylphenyl groups, and R1 and R2 each represent an alkyl group containing from 1 to 4 carbon atoms.
  • a process for preparing a 1-aryl-4,4-dialkyl-3- pyrazolidone which comprises reacting phenylhydrazine with a compound having the general formula wherein R1 and R2 represent alkyl groups each containing from 1 to 4 carbon atoms and X represents a halogen atom, at a temperature of 0 to 10 C. in the presence of an acid binding agent, heating the reaction mixture at a temperature of about 100 C. for about 1 to 10 hours.
  • R1 and R2 represent alkyl groups each containing from 1 to 4 carbon atoms and X represents a halogen atom, at a temperature of 0 to 10 C. in the presence of an acid binding agent, heating the reaction mixture at a temperature of about 100 C. for about 1 to 10 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
US372148A 1953-08-03 1953-08-03 3-pyrazolidones Expired - Lifetime US2772282A (en)

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BE530884D BE530884A (en, 2012) 1953-08-03
US372148A US2772282A (en) 1953-08-03 1953-08-03 3-pyrazolidones
FR1131853D FR1131853A (fr) 1953-08-03 1954-07-30 Nouvelles 3-pyrazolidones, procédé pour leur préparation et leurs applications
GB22511/54A GB757271A (en) 1953-08-03 1954-08-03 Improvements in photographic developing agents

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153654A (en) * 1961-05-31 1964-10-20 Ilford Ltd 3-pyrazolidinone carboxylic acid derivatives
US3166568A (en) * 1965-01-19 Therapeutic compositions containing
US3284200A (en) * 1962-06-07 1966-11-08 Ilford Ltd 3-pyrazolidone developers
US3453109A (en) * 1966-06-24 1969-07-01 Eastman Kodak Co Forming a relief by developing and hardening an exposed unhardened silver halide emulsion in the exposed areas with 3-pyrazolidones having hydroxymethyl substitution in the 4-position
US4209580A (en) * 1978-10-02 1980-06-24 Eastman Kodak Company Substituted 1-phenyl-3-pyrazolidinone electron transfer agents
US4266002A (en) * 1978-10-02 1981-05-05 Eastman Kodak Company Substituted 1-phenyl-3-pyrazolidinone electron transfer agents
US4409324A (en) * 1981-09-21 1983-10-11 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive materials
EP0428455A3 (en) * 1989-11-13 1991-07-17 Eastman Kodak Company Photographic developing solution for use with fore-hardened x-ray films
US5187050A (en) * 1986-11-07 1993-02-16 Fuji Photo Film Co., Ltd. Method for automatic processing of silver halide photographic material
US5447826A (en) * 1991-08-16 1995-09-05 Agfa-Gevaert, N.V. Photographic silver halide material
EP0843212A1 (en) * 1996-11-14 1998-05-20 Eastman Kodak Company Novel auxiliary developing agents, photographic materials incorporating them and the use thereof
US6087084A (en) * 1997-11-14 2000-07-11 Eastman Kodak Company Auxiliary developing agents, photographic materials incorporating them and the use thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2743905B1 (fr) * 1996-01-23 1999-03-05 Kodak Pathe Composition de revelateur organique-inorganique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2289367A (en) * 1940-07-10 1942-07-14 Llford Ltd Photographic developer
US2688024A (en) * 1951-10-17 1954-08-31 Ilford Ltd Production of 3-pyrazolidones
US2704762A (en) * 1952-08-25 1955-03-22 Ilford Ltd Production of 3-pyrazolidones

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2289367A (en) * 1940-07-10 1942-07-14 Llford Ltd Photographic developer
US2688024A (en) * 1951-10-17 1954-08-31 Ilford Ltd Production of 3-pyrazolidones
US2704762A (en) * 1952-08-25 1955-03-22 Ilford Ltd Production of 3-pyrazolidones

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166568A (en) * 1965-01-19 Therapeutic compositions containing
US3153654A (en) * 1961-05-31 1964-10-20 Ilford Ltd 3-pyrazolidinone carboxylic acid derivatives
US3284200A (en) * 1962-06-07 1966-11-08 Ilford Ltd 3-pyrazolidone developers
US3453109A (en) * 1966-06-24 1969-07-01 Eastman Kodak Co Forming a relief by developing and hardening an exposed unhardened silver halide emulsion in the exposed areas with 3-pyrazolidones having hydroxymethyl substitution in the 4-position
US4209580A (en) * 1978-10-02 1980-06-24 Eastman Kodak Company Substituted 1-phenyl-3-pyrazolidinone electron transfer agents
US4266002A (en) * 1978-10-02 1981-05-05 Eastman Kodak Company Substituted 1-phenyl-3-pyrazolidinone electron transfer agents
US4409324A (en) * 1981-09-21 1983-10-11 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive materials
US5187050A (en) * 1986-11-07 1993-02-16 Fuji Photo Film Co., Ltd. Method for automatic processing of silver halide photographic material
EP0428455A3 (en) * 1989-11-13 1991-07-17 Eastman Kodak Company Photographic developing solution for use with fore-hardened x-ray films
US5447826A (en) * 1991-08-16 1995-09-05 Agfa-Gevaert, N.V. Photographic silver halide material
EP0843212A1 (en) * 1996-11-14 1998-05-20 Eastman Kodak Company Novel auxiliary developing agents, photographic materials incorporating them and the use thereof
US5932399A (en) * 1996-11-14 1999-08-03 Eastman Kodak Company Auxiliary developing agents, photographic materials incorporating them and the use thereof
US5972584A (en) * 1996-11-14 1999-10-26 Eastman Kodak Company Auxiliary development agents photographic materials incorporating them and the use thereof
US6087084A (en) * 1997-11-14 2000-07-11 Eastman Kodak Company Auxiliary developing agents, photographic materials incorporating them and the use thereof

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GB757271A (en) 1956-09-19
FR1131853A (fr) 1957-02-28

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