DE1944054A1 - 3-Pyrazolidinone derivatives, process for their preparation and their use - Google Patents

Description

MINNESOTA MINING AJTD MANTJPACTIJRINa COMPANY Saint Paul, Minnesota, V, St.A ₀

^N 3-Pyrazolidinone derivatives, process for their preparation and their use ^M

Priorities: 30 »August 1968, Great Britain, Nos. 41637/68, 41638/68 and 41639/68 ₀

The present invention relates to 3-tyrazolidinone derivatives, processes for their preparation and also the use of these derivatives all developers for photographic silver halide emulsions »

The production of Furthermore relates to the invention ^ -. fyrazolidiniiain-Zwischen products for use in the preparation of 3 - fyrazolidinone

from

Derivatives and also / ungoritttLgJhn organieolura compounds, which as Intermediates in the manufacture of both 3-tyrazolidinones and 3-pyrazolidinibines are valuable «

1-Jfhenyl-3-pyrazolidinone is inherently a good developer, however, it becomes noticeably better when it is used in conjunction with gr <x »

009821/1952

Eat quantities of other cheaper developers such as hydroquinone because the two developers together are far more effective are than could be expected from a simple addition of their properties. This seems to be all because t-phenyl « -3 ~ pyrazolidinone is used over and over and over again ultimately only exhausted as soon as all other chemicals in the developer have also been exhausted »

Although 1 ~ phenyl-3-pyrazolidinone is an excellent developer is, nevertheless, its use indicates a number of cells in the Prejd. · euf. One of them is the instability in alkaline solutions with a pH value above 9. This means that it does not have a is a very suitable developer in highly active liquid developers. Another disadvantage is its relatively low solubility in developer solutions, which pretty much limit the concentration in which the concentrated developer solutions are sold will. Usually, consumers prefer to purchase a concentrated solution that is easily accessible to the right amount by diluting rather than with a solid which has to be dissolved

So far, every attempt is made to improve stability or solubility by ^ -pyrazolidinone developers at the expense of an or several of the developer's desired properties, such as » development activity.

So it let a keel to the present invention is to provide developers ^ $ desirable that developers own shadow be8its @ a ₉ AEIE bo well as those of 1-- ₌ Hi © ßyl »3 gyrazolidi

009821/1962

are non or only slightly worse, but one is a lot have better stability in strongly alkaline solutions and / or are more soluble in developer solutions «.

According to the invention, S-vryrazolidinone compounds of the general formula are created:

N CH ₂ C CO

1 y I.

^R H ₂ C .NH

in which R and R are each independently hydrogen, a Alkyl, substituted alkyl, cycloalkyl, arallcyl or aryl radical, where the alkyl group of the alkyl, cycloalkyl, substituted alkyl or aralkyl radical represented by K or R contains 1-6 carbon atoms, or in the optionally

R and R together form a carbocyeli or including

of the nitrogen atom form a heterocyclic king and R for an aryl or substituted arylrea ".

These 3-pyrazolidinone compounds make good developers for photographic silver halide emulstones and are considerably more soluble and / or more stable in strongly alkaline solutions as i-irhenyl-3-pyrazolidinone.

While the compounds of the invention are themselves developers, they are preferably used with one or more other developers, such as hydroquinone, because - similar to 1-irhenyl-3-pyrazolidinone - such a combination has an

009821/1962

signed developer who reuses several times before it is exhausted. fcine other very useful intwieklerkombiriation, which is particularly useful for the Development of color photographic material is suitable, is a compound according to the invention together with Ν, Ν'-diethyl <p ~ phe <nylenediamine or another color developer.

Suitable rings formed by the vest R and R together with the nitrogen atom are the morpholine or the piperidine ring.

When R and R represent substituted alkyl radicals, are suitable O substituents the hydroxy or the tertiary amino group, because these groups give the compounds increased solubility in water or other developer solvents such as alcohols

2
When R represents a substituted aryl radical, suitable substituents are, for example, alkyl and alkoxy radicals or halogen atoms.

The 3-tyrazolidinone compounds according to the invention can according to a number of different processes can be produced "

One of these manufacturing methods is to implement a üsters of the general formula

^ ¹ ***** "W (tu", __ "_ fill ΡΠΠΤΤ ^

λ ^ * W VrUn KiIA V / UVJXl

H-

in which R and R ^{% have} the meanings given above and R is a

009821/1882

Means hydrogen atom or an alkyl radical, with a substituted hydrazine of the general formula

R ² NIPNH ₂

in the H has the meaning given above “The turnover can by heating a mixture of the two reactants in solution.

Another method provides for the hydrolysis of 3 ~ i * yrazolidiniminen before, for example by boiling the imines in solution in an aqueous weakly-acidic solvent _o Therefore, present invention provides in a further aspect, 3-fyrazolidinimin-Zwiechenprodukte before, which have the general formula:

NU

in which H and B are each independently hydrogen, one Alkyl, substituted alkyl, cycloalkyl, aralkyl or aryl radical, where the alkyl group of the alkyl, substituted alkyl, cyoloalkyl or aralkyl radical represented by B or H contains 1-6 carbon atoms, or in the optionally

H and R together a carbocyclic or with inclusion

of the nitrogen atoms form a heterocyclic ring and B stands for an aryl or substituted aryl radical «

The 5-fyrazolidinone compounds according to the invention can furthermore be prepared by reacting an unsaturated organic compound of the

009821/1962

general formula

λ /

13 in which K, R and R have the meanings given above, with

a substituted hydrazine, such as ifhenylhydrazine, of the general formula

R ² HH-HH ₂

in the & has the meaning given above. The implementation can by heating the reaction partners together in solution.

Apart from the fact that the 3-jyrazolidinone compounds according to the invention can be prepared from these unsaturated organic compounds, the 3-pyrazolidinine intermediates described above can also be prepared by reacting one of these unsaturated organic compounds containing an aainomethylene ur group Compounds With a Substituted Hydrazine, such as Phenylhydr & - zin, the general formula

B ² HH-MH ₂

In which H has the meanings given above, are prepared. San can do this, for example, by cooking the Reaction partner In solution in a solvent such as ethanol, carry out,

The invention relates in yet another aspect to the preparation of these unsaturated organic compounds. Therefore, in this regard, the present invention envisages a process for the preparation of the unsaturated organic group-containing compounds of the ^invention. ° γ »θ1 before

GH ₂

in which P and P each independently represent a hydrogen atom or an alkyl, substituted alkyl, cycloalkyl ore Aralkyl radical or in which optionally P and P together form a carbocyclic ring or, with the inclusion of the nitrogen atom, a heterocyclic ring and JC stands for an electron-withdrawing group, with the characteristic that one an amine of the general formula under alkaline conditions

y -_— NH P ¹ ,

in which P and P have the above meanings, with formaldehyde and with one, one active methylene group in the vicinity of one Carboxyl group-containing compound of the general formula

I CH ₂ COOH,

in which X has the above meaning, implements "

However, although not proven, it is believed that this process proceeds at least in part via an intermediate stage in which a bis-aminomethane compound is formed, which then with the Association of general terms.

JL '- (JiL-J GOUH

reacted. In any case, the unsaturated organic terminal compound can be obtained by reacting a bis-aminomethane compound and a compound old of the general formula

X CH ₂ COOH ^:

getting produced. Therefore, another feature of the present invention is a method for producing these unsaturated ones organic compounds containing an aainomethylene group

0Q9821 / 1Ö62

with the general formula

in which P, P and X have the above meanings, with the indicative Feature that you can have a bis-aminomethane compound the general formula

• CHp "

with a compound with an activated methylene group in Position adjacent to a carboxyl group with the general form!

χ CH ₂ COOH

in which X has the above meaning, mixed.

As already mentioned above, these unsaturated compounds are nützlieh as intermediates for the preparation of the above-described 3- ± ^/ yrazolidinon "compounds and 3 ~ Pyrazolidinimin compounds, in which case P and P may represent the same as R and B best.

The Heat X must have an electron-attracting effect. Suitable Groups are therefore, for example, those of the formulas

-GOOH, -GOOP ² and -GN,

009821/1912

'-: sr *

in which F represents an alkyl, aryl or aralkyl radical.

It is possible to produce these unsaturated compounds Either use formaldehyde as such, or nan can use it for ■ Reaction chemicals in the form of a normaldehyde-releasing compound, such as faraformaldehyde.

The preparation of these unsaturated compounds is preferably carried out in an aqueous reaction medium.

One can use the unsaturated compounds in the case that X is a Represents carboxyl group in such corresponding compounds

2 convert, in which X represents an ester group -COOP, and by treating the unsaturated compound in which X the Represents carboxyl group with an alcohol in the presence of a strong acid such as sulfuric acid.

The invention is now illustrated by the following examples explained in more detail.

Examples 1-10 illustrate the production of unsaturated organic intermediates

Example 1. 2-Diaethylaainomethaory acid.

Il

(CU ₃ ) gN • CH ₂ C-OOOH

150 ml of a 40% strength iomaldehyde solution were added while stirring. Solution of 218 g of a 26% dimethylamine solution, 104 g ae £ 250 ml of water. During the addition and afterwards

009821/1952

The heating temperature was kept at 20 ° C for two hours. The solution was then heated to dea for two hours Steam bath and removed the water under decreased pressure. Man obtained a pale yellow syrup, which was then further dried by azeotropic distillation using JJenzol.

The product was recrystallized from acetone and gave colorless crystals which were dried for four days under vacuum over phosphorus pentoxide. Yield: 92 g or 71%. Analysis: ^G $ ^a - \ f ^S0 2 calculated * H 10.85 / 6

found: N $ 10.70.

Example 2,

2-piperidinoethyl acrylonitrile. CH ₂ OA

f% ti > « . / ItT ___ η ent

V / ^ H

CH ₂ UH ₂ OE ₂ .

75 al of a 40 £ strength rorealdehydlöeung were xugefügt in water! Ears at 15 ⁰ O "iner solution of A3 & CyaneseigeMur 'and 85 S piperidine. The solution was stirred for an hour at home temperature and then boiled under the river. After cooling, I separated the Heaktlonegeaiach into two layers. The upper layer was separated and distilled. A colorless "Ol was obtained, bp 117-118 ⁰ C at 0.5" at%. Analysis: C ₉ H ₁₄ M ₃ Versöhnett C ^ 6 71.96, H 9, K Wt I8,65 t?

found s C 71.6 ^, H 10 _t 4 ^ "H

Example 3.

001121/1612

GH ₂

75 β of a 4O £ formaldehyde solution were added with stirring 15 ° C of a solution of 43 β uyanacetic acid and 173 β of a 2656 igen Dimethylamine solution in 250 ml of water was added While cooling, the solution was refluxed for an hour Upon cooling, the reaction mixture separated into two layers. The top layer was separated and distilled. 2-Dimethylaminomethylacrylonitrile (boiling point 40-45 ° C./0.5 mm Hg) and a higher boiling by-product,

Analysis: CgH ₁ ^ ₂ '' calculated: C 65 _g 45 # »K 9» 15 $, N 25.45 #

found »065.196, H 8.85ε, 25.3 *.

Example 4. 2 - methylaminomethyl-acrylate ethyl ester _g

(CH ₃ ) gN • CH ₂ .C-CDOC ₂ H ₅

60 ml of a 40 ^ ~ strength Poraaldehydlöeung were added to a solution under Kühren at 15 ⁰ C aalonsäureftthyleeter potassium of 34 g and 40 al of a 26) Uigen solution of diethylamine in 100 al of water added The solution was stirred at Hauuteaperatur a at and e, and then Boiled under reflux for one hour, after cooling the solution was extracted with ether and the ether evaporated as remaining yellow oil gave a clear oil of bp 84 ° C. at 20 mm Hg _{0 after distillation}

Analysis: ^G e ^H i5 ^N0 2 ^s calculated! ^G 61,1 # »H 9 _f G2j6, N 8,

found: C 6O _s 7 # ₅ H 10.15? ί, W 8 _P

9 8 21/19 5 2

Example 5.

2- dimethylaminomethyl-acrylate ethyl ester.

) οΝ ·

JH ₂ -C ⁰ Go ₂ H ₅

A solution of 35 g of the 2-dimethylaminomethacrylic acid prepared in Example 1 in 350 ml of ethanol and 60 ml of concentrated sulfuric acid was boiled under reflux for three hours. The solution was concentrated to half its volume and poured into 1 l of water. The aqueous solution was neutralized by addition of solid sodium carbonate and extracted with ether "After evaporation of the ethereal solution gave a pale brown oil, which is now yielded Hg after distillation as a colorless oil, bp. 84 ⁰ C at 20. Ee was identical to the product of. Example 4 °

Example 6.

2-dimethylaminomethacrylic acid.

162 ml of a 37 ^ aqueous solution of formaldehyde was added slowly with stirring at 15 ⁰ C a solution of 104 g of malonic acid and 350 ml of a 26 # ~ aqueous dimethylamine in 150 ml of water. Carbon dioxide evolved at a rate that depends on the rate at which iOrmaldehyde was added. The Keaktionsgemisch was stirred for 15 minutes at 15 ⁰ G and then heated for one hour on the steam bath to complete the decarboxylation. Evaporation under reduced pressure gave a yellow syrup which was further dried by azeotropic distillation with ioluene. A pale brown residue was obtained which was recrystallized from acetone and dried in a vacuum over phosphorus pentoxide.

009821/1 9S2

loose cubes of pp. 115-117 ⁰ C. Yield: 107 g or 86 #. Analysis: CgH ₁₁ NO ₂ : calculated: υ 55.8 $, H 8.65b, N 10,

found: C 54.256, H $ 8.5, «10,

Example 7 »

2-diethyl ainomethacrylic acid.

(C ₂ Hc) 2 «. CH ₂ . C. O ¹ OOH

Ih ₂

To 24 g of bis- (diethylamino) methane maxi added 5.2 g of malonic acid in aliquots, cooled with ice and stirred with hand. A vigorous reaction took place and the mixture became viscous. After excess bis- (diethylamino ) methane and diethylamine, the syrup obtained was recrystallized several times from acetone. Colorless crystals of 2-i) ethylaminomethacrylic acid from ¥ p were obtained. 121-123 ⁰ C. Yield: 5.9 g or

Analysis »C ^^ MOgt calculated: 0 61.156, H 9.654, N 8.9 3 &

found: 0 58.4%, H 10.2 *, Μ 7.69 *.

Other 2-aainomethaoryli acids were made by similar procedures manufactured. The properties of the products obtained are given in Table I below, the Aino group Q the bed Q in the general formula

QCH ₂ UCOOH

* is equivalent to"

009821 / 19S2

Table I.

Pp ₀
in
⁰ O analysis H N calculated (£) H N Crime
stali
shape recrystalline
lized out Aaino 145-
151 found (#) 7.7 15.4 Q 7.0 13.9 dice Acetone/
Methanol »Ethyl
amino 137-
146 Ü 7.4 11.4 47.5 7.9 12.1 rfürfel Acetone/
Methanol Dimethyl
amine 115-
117 45.4 8.5 1ü, 7 52.2 8.6 10.8 dice acetone Diethyl
amine © 121-
123 50.7 10 ₉ 2 9.6 55.8 9.6 8.9 plates
• acetone Dieyclo-
hexyl
aain 147-
148 55.2 10.0 5.0 61.1 10.3 5.3 plates Acetοα 1 pipe
ridino 144-
145 58.4 8.9 8.1 72.4 8.9 8.3 plates acetone 1-iior-
pholino 114-
115 72.6 7.6 8.2 63.9 7.6 8.2 plates acetone 63.3 56.1 55.1

Example 8 _a

2-dimethylaminoethyl-acryl8äureäthyle8ter ₀ 161 577 al a & -i en aqueous formaldehyde solution were added at 15 ⁰ C a solution of 132 g Malonsäuremonoäthylester and 350 ml of a 26 # aqueous dimethylamine in 150 ml of water langaaa. The mixture was stirred for 30 minutes at 15 ⁰ C, slowly at 40 erhitst ⁰ O and stirred an additional 30 minutes. The decarboxylation began at 26 ⁰ C. After cooling, the organic material deposited as a colorless oil was extracted three times with 250 ml of ether each time. The essential extract was dried over anhydrous sodium sulfate and steamed

00SS21 / 1862

print a. The fiüekstand. proved to be a mixture because of the appearance of two carbonyl bands (1740 cm and 1720 cm "*) in infrared spectra. The mixture was distilled in vacuo. 50 g (325t) of a-dimethylaminomethyl-acrylic acid ethyl ether at boiling point 34 ° C. were obtained at 0.7 mn Hg ( "Ι _{Λ Λ} _ 1722 ca" ¹⁾ and 87 g ( "1,3-bis ~ (dimethylamino) propan-2 * carboxylate from 58 ⁰ C at 0.8 mm Hg (V _cMQ 1740 cm " ¹ ).

Analysis for S-dimethylaminomethyl-acrylic acid ethyl esteri C ₈ H ₁₅ NO ₂ J calculated: G 61.1 #, H 9.63ε, S 8.95t

found: G 60.6 ^, H 10.1 ^, 'H 8.8 £ _O

Analysis for 1,5-bis- (dimethylamine) -propane-2 '«CRrboxylic acid ethyl ester S calculated: 0 59.49t, H 10.9 ^, K 13.85ε

found s C 58.6 *, H 11.5 #, N 12.3 *.

In this way, other 2-alkylaminomethyl acrylic acid esters became the properties of which are given in Table IX below are given, in which Q and Q the entC ^. ^ existing groups in the following general formula

QCH ₂ GCOOi /

Represent CH _2.

009821/1962

f 16! table II

C ₂ H ₅ Kp ₀
in
⁰ C pressure
in
mm Hg analysis U N calculated (#) H N Methylamines » CH, 106 2.0 found (#) 10.5 8.9 C. 9.2 9.8 Dimethylamino ^O 2 ^H 5 77 20.0 C. 8.9 9.6 58.7 9.2 9.8 Dimethylamine CH ₅ 84 20.0 56.8 10.1 8.9 58.7 9.6 8.9 Diethylaaino C ₂ H ₅ 94 15.0 57.9 9.6 7.5 61.1 10.0 8.2 Diethylamino 'GH ₅ 56 2.0 60.6 9.9 7.7 63.1 10 _s 3 7.6 1-piperidino C ₂ H ₅ 80 2.0 59.0 8.8 7.3 64.8 9.3 7.6 1-piperidino i-Ο, Ε, 117 15.0 64.0 9.6 7.0 65.5 9.7 7.1 1-piperidine © HC ₄ H ₉ 94 1.0 62.8 10.1 5.9 66.9 10.0 6.2 1-piperidino ⁰ A 102 1.0 65.9 10.3 5.4 68.2 10.3 6.2 1-morpholines 94 1.0 66.6 8.8 7.1 69.3 8.6 7.0 67.5 60.3 60.3

■ Example 9.

2-Diaetbylaainoaethy! Acrylonitrile »

162 37 £ al aqueous formaldehyde were "slowly added to a solution of 85 g Cyanessigeäure and 350 ml of 26 ^ aqueous sodium dimethylamine, The solution was stirred during the addition at 15 ⁰ C and then for another 30 minutes at 40 ⁰ C. The COg evolution

started at 31 ⁰ G. The speed of development increased with the increase in temperature. The solution was then extracted three times with 250 bX ether each time. After drying over anhydrous Na-

009821 / 1Ü2

trum sulfate, the solvent was evaporated. To give an oil whose infrared spectrum of two nitrile bands (2240 cm ~ 2220 cm) and thus the presence of two compounds showed * Distillation of the mixture gave 25 g ( »2YF>) 2-Dimethylaminomethylacrylnitril, bp ₀ 43 ⁰ C at 1.0 mm Hg and 43 g ( »319t) of 1,3-bis- (Dimethylamine) propan-2 ~ nitrile, bp. 57 ⁰ C at 0.8 mm

Analysis for 2-dimethylaminomethylacrylonitrile; C ₆ H ₁₀ NgS calculated C 65.4 * »H 9.2 *, N 25, -

Found: C 65.2 *, H 9.2 *, N. 25.4 * ° Analysis for 1,3-bis (dimethylamine) propane-2-nitrile:

CgH ₁₇ NX calculated: C 61.9 *, H 11.0 *, N 27.1 * found: C 62.3 *, H 10.8 *, N 27.1 * o

In the same way, other 2-alkylaminomethylacrylonitriles were prepared, the properties of which are listed in Table III below, the amino group Q corresponding to the keet Q in the general formula QCH ₂ CCN.

CH ₂

Table III

Kp.
Xn
⁰ C pressure
in
mm Hg analysis H N calculated (*) H N Dimethylamino 56 10.0 found (*) 9.2 25.4 C. 9.2 25.4 Diethy1amino 40 1.0 C. 10.4 20.3 65.4 10.2 20.3 1-piperidino 117 0.5 65.2 9.8 18.6 69.5 9.4 18.7 69.1 71.9 71.6

009821/1952

Example 10.

2 ~ Dimethylamlnomethyl> acrylic acid ethyl ether » A solution of 129 g of ^ -dimethylaminomethacrylic acid in 105 ml of 90% sulfuric acid and 500 ml of ethanol was heated under reflux for three hours. After concentrating to half volume the restlich® mixture was poured into 1 1 water, added 212 g of anhydrous sodium carbonate au and the solution was left when she was neutral stand _t three hours the aqueous solution "was extracted three times with 250 like that. Ether, dried the extract over anhydrous sodium sulfate and evaporated it under normal pressure. The lingering © pale yellow oil was distilled under reduced pressure and provides © 86 g ( "5556) 2-i) imethylaainometliyl ~ ~ acrylaäureäthyl ester, bp. 84 ⁰ C at 20 mm Hg"

Analysis: OgH ^ NOg * calculated: £ 61.1, £ 9.69, N $ 8.9

found: C 60.7 #, H 10.1 #, K 8,

Examples 1.1 to 13 below illustrate the preparation the 3-iYra3olidinimiri ~ intermediates ο

Example 11.
4 "3i ^> iperidlnoaethyl ^ 1" phenylpyrazolidln ~ 3 "iMi.n _c

HH

Adds 17 g of 1-piperidolnometharyl nitrile and 10.8 g of phenylhydrazine to a solution of latriuiiäthylat (2j3.g sodium) in

009821 / ie§2

200 ml of ethanol and the resulting solution is heated under reflux for two hours. During the reaction, a solid precipitate is formed. 50 ml of 2N hydrochloric acid are added and the solution is evaporated to dryness. The solid residue is extracted with dry ethanol. The end product crystallizes from ethanol in colorless leaflets (pp. 186 "167 ⁰ G),

Analysis: ^c i5 ^H 22 ^H 4 ⁱ calculated: C 69.7 $, H 8.6 $, N 21.7 $

found: 0 69.6 $, H 8.8 $, K 21 _? 6 $ "

Example 12 "4-Morpholinonethyl- 1- # Ii enylpyrazolidin-3-imine"

² \

) NH

54 g of I-aorpholinomethylacrylonitrile and 37 g of hydrazine are heated with a solution of sodium ethylate (7-5 g of sodium) in 250 ml of ethanol for two hours under reflux. A solid product forms during the reaction. 160 ml of 2N hydrochloric acid are added and the solution is evaporated to dryness. The solid residue is extracted with dry ethanol, the product crystallizes from ethanol in colorless leaflets (melting point 204-205 ⁰ ), analysis: G ₁₄ H ₁₉ N ₅ O ₀ ; calculated: G 64.613t, H 7.76? C, N 21.52 *

found s 0 $ 64.68, H $ 7.6, H-

Example 13.

4-Pimethylaminomethyl-1-phenylp yragQlldin ~ 3-J

009821 / 13B2

NH

11.0 g of 2-dimethylaminomethylacrylonitrile are added all at once to a solution of 10.8 g of phenylhydrazine and sodium ethylate (2.3 g of sodium) in 100 ml of ethanol. The product was rapidly oxidized to a deep red substance in an alkaline solution? contact with oxygen was avoided by vigorously boiling the solution for 90 minutes under the flow of water. After cooling, the sodium ethylate was neutralized with 50 ml of 2N sulfuric acid and the mixture was extracted three times with 100 ml of chloroform each time. After evaporation of the solvent a brown solid _(17? 8 g), which was recrystallized from 300 ml of petroleum ether (b.p. 80-100 ₀ ⁰ C) was obtained. 16.4 g (* 75 $) of colorless flakes were obtained from Pp. 117-118 ⁰ C.

Analysis: C ₁₂ H ₁₈ H ₄ S calculated: C 66, Oj6, H 8.3j6, K 25 _}

found: C 65.8? t _f H 8.2fi _t H 25 _f

You prepared according to these examples ^ -Pyrazolidiniain-Yerbindungen are useful as intermediates in the preparation of the 3-pyrazolidinone compounds of the invention

The following Examples 14-19 illustrate the preparation of the 3 * pyraolidinone compounds according to the invention.

0Ö982T / 19B2

A solution of ^ -Morpholinometbyl-i-phenyXpyrazolidin-3 ~ irain (29 g) was refluxed for four hours in 120 ml of 2N hydrochloric acid, then cooled? Neutralized with sodium hydroxide and extracted with chloroform, the chloroflorine extract was dried and evaporated to dryness. The residue was recrystallized from Patrol ether (bp. 100-120 ⁰ O) and gave colorless leaflets, mp. 143-144 ⁰ C.

Analysis: G ₁₄ H ₁₉ N ₅ O ₂ : calculated: G 64.35 #, H 7.33? 6, N i6 _t 08 #

found: C 64.5 #, H 7.4 #, N 16

Example 15 «

4 ~ Morpholinoethyl ^ 1-phenylpyrazolidin »3-one.

A solution of 5.4 g of phenylhydrazine and matrix ethylate (1.15 pounds of halide) in 100 ml of ethanol was added to 10 g of ethyl i-morpholinomethyl acrylate, and the mixture was heated under reflux for 30 minutes. During this time, the sodium salt of Product. The oil suspension was cooled and 25 ml of 2N hydrochloric acid were added. The solution was evaporated to dryness and the sticky residue was extracted with chloroform, the Chloroforalö8ung evaporated to dryness and a brown residue, which was recrystallized from tetroläther (bp _{0100 to 120} ⁰ C), colorless platelets were obtained from received Pp, 143 -144 ⁰ G, The product was identical to that from Example Ho

009821/1952

Example 16

GH, H

ClU C - 'CO

I ₀

H ₂ C _x »Η

15 »7 g of 2-dimethylaminomethyl-acrylic acid ethyl ester were at once a boiling mixture of 10.8 g phenylhydrazine and sodium! sopropylate (2.3 g sodium) in 100 ml xsopropanol added, violent foaming occurred. The product was rapidly oxidized by air in an alkaline solution and gave a deep red substance. In order to avoid contact with air, the solution was added briskly refluxed during the subsequent heating. After 10 minutes of boiling, the solution became in a with The bottle, closed with an oil stopper, was quickly cooled to 0 ° G λ 125 ml of 2N sulfuric acid were added and the mixture was extracted three times with 250 ml of ether each time. The essential extract was made discarded and the aqueous solution with approximately 125 ml of 2N sodium hydroxide solution adjusted to pH θ. The three-time extraction of the aqueous mixture with 100 ml of chloroform each time gave a pale yellow extract, which after evaporation of the chloroform produced 18.5 g of an oil »

On cooling, the crystallized 01 "body to a buff solid, which was umkristnllisiert from 450 ml of petroleum ether (bp. 60-80 ⁰ C)" was obtained 12.4 · g (■ # 57) 4-Diraethylarainomethyl-1-phe ~ nylpyrazolidin -3-on (pp. 118 * 119 ⁰ C) as colorless needles,

009821/1952

Analysis: C ₁₂ H ₁₇ K ₅ O; calculated: G 65.7 #, H 7.896, H 19.1 lbs

found: G 66.5 #, H 7.8 #, N 19.2 #.

The mono-oxalate salt was prepared by mixing the tyrazolidinone with oxalic acid in an acetone solution. A white solid was obtained which was recrystallized from ethanol. They achieved a 73 # owned yield of 4-dimethylaminomethyl-i-phenylpyrazolidin-3-one-mono-oxalate salt (Pp _0128-129 ⁰ C) as colorless crystals.

Analysis: G ₁₄ H ₁₉ N ₅ O ₅ ! calculated: G 54 ·, 5 #, H 6.2 #, N 13,

found: C 54.5 / », H 6.1ji, N 13

Example 17 »

4-Bimethylaninomethyl- »1 -phenylpyraaolidin ~ 3-one» 20.2 g of ethyl 1,3-bie- (DiBiethyla «ino) propane-2-carbonate were given nan at once to a boiling mixture of 10.8 g phenylhy drazin and Satriuaisopropylat (2.3 g sodium) in isopropanol »

The solution was boiled under fiüekflux for 50 minutes and gave nti'-h Work-up in a similar manner as described in "ia i" i, ö $ i®l 16 Way 13.6 g (62 #) of a product identified by infrared spectrua

as 4-DiiBethylaminonethyl ~ 1-phenylpyrazolidin-3-one (pp. 117-118 ⁰ C) was identified.

Example 18. 4- Eimethylaminomethyl-1-p ~ chlorophenylpyrazolidin-3-one »

τ -f °

oil
009821/1852

14.5 g of p-chlorophenylhydrazine were added to a solution of sodium isopropoxide (2.3 g of sodium) in 200 ml of dry isopropanol _9, the solution was heated under reflux and 15.7 g of ethyl 2-bimethylaminomethyl-aerylate were added all at once After boiling for 20 minutes, the solution was cooled to ⁰ ° C. in a blown bottle, 125 ml of 2N sulfuric acid were added and the mixture was extracted three times with 250 ml of ether each time. The ethereal extract was discarded and the aqueous solution was adjusted to pH 3 with approximately 125 ml of 2N sodium hydroxide solution. Extraction of the aqueous ttomisehs with chloroform yielded a pale yellow extract, which after evaporation of the chloroform gave a buff-colored solid which after recrystallization from carbon tetrachloride (mp. 107 ⁰ C) 9 i ( »$ 35) 4-Dimethylaminoiaethyl-1-p 'chlorphenylpyra ~ Bolidin-3-one as colorless needles yielded _o Analyzes C ₁₂ H ^ gClN-Os calculated: C 56.856, H 6, 4 ^ 1 N

found j C 57.156, H 6.4 #, N

Example 19.

4-piperidinomethyl-1-pfaenylpyragolidin-3-one. CH ₂ - CH "

OH ₂ ^X S- - GH ₂ CH 00

CHn P ^^ 2 * v

19 »7 g 2-piperidinomethyl ~ acryl8äureäthylester was added in one portion to a boiling mixture of 10.8 g Fhenylhydrazin and ftatriun · ieopropylat (2.3 g of sodium) in 100 ml. Iaopropanol _r where vigorous foaming occurred. The solution was briskly refluxed

0 09821 / 19S2

<· 25 - ·

boils to avoid contact of the reaction mixture with air. After boiling for one hour, the solution was quickly cooled and neutralized with 50 ml of 2N sulfuric acid * The mixture was extracted three times with 100 ml of chloroform each time and the chloroform solution was evaporated to dryness. The buff-colored plague obtained was recrystallized from tetrolether. 18.7 g ( "72%) of colorless Blättchen.vom Pp 134-135 ⁰ C _0. Analysis: O ₁₅ H ₂₁ N ₅ O: Calculated: 69.5% G, H 8.2%, N 16, 3%

found: C 69.5%, H 8.2%, N 16.3%.

The "3-pyrazolidinone compounds prepared according to Examples 14 to 19 are excellent. winder, as shown in Examples 20 to 22 below.

Example 20.

4-Horpholinonethyl-1-phenylpyrftzolidin-3-one (OL's photographic developer was tested in the following solution, designated as Solution "A" 4-MorpholnOBethyl-1-plienylpyrazolidine «3-O] i ......... 2.61 g

Sodium sulfite 72.0 g Sodium carbonate 48.0 g Potassium bromide · .. ·· ... · 4.0 g Hydro t hi non ·. ..ο. 8.8 g

"IBT" -Ver2Ögei ^ r 10.0 αϊ

Water ad 1000.0 al

A different solution, referred to as solution ¹¹ B ", was identical to solution" A *, with the exception that 0.22 g of 1-lrhenylpyrazolidin-3-one instead of A-liorpholinomethyl'-i-phenylpyrazolidine ^ 'On ver . " applies «· The solution" B "became the standard for comparison purposes

009821/1952

used

The following results were obtained when the two solutions were used to develop a commercially available high-speed fine-grain medical X-ray film

Developer-
solution veil
(Jiasis +
Emulsion) Helative
Sensation
opportunity contrast D max Development
time at 21.1
⁰ C (minutes) A. 0.19 1.97 1.89 3.12 5 B. 0.19 1.90 2.06 3.1 " 5

Example 21.

4-Korpholinomethyl-1-phenylpyraolidin-3-one was tested for its oxidation resistance in the same formulation as solution "A ** in Example 20. A control solution, designated as solution" C ", was previously solution ⁿ B ⁿ identical with the exception that it contained 0.22 g of 4-tetethyl-1-phenylpyrazolidin-3-one instead of 1-phenylpyrazolidin-3-one because the former compound is more stable than the latter.

Heathen solutions were made in developing a photographic one Films examined when they were freshly made and then again after oxygen had been bubbled through at a rate of 2.5 liters per minute for six hours.

The following results were found

009 8 21/1852

Initial investigation

intwiekler-
Solution Sea eggs
(Base +
Emulsion) Relative
Sensation
opportunity contrast D max Developments
time at 21.1
⁰ C (minutes) A. 0.19 1.87 2.04 3.03 5 C. 0.18 1.86 2.04 3 * 02 5

Naofa of oxidation

intwiekler-
solution veil
(Base +
Emulsion) Relative
Sensation »
opportunity contrast D ma * *
jünt wi ekl-
time at 21.1
⁰ C (minutes) A. 0.13 1.45 1.45 3.05 5 C. 0.13 1.36 1.05 2.26 5

Example 22. ^

4 * BiBethylaminoaethyl ~ 1-phenylpyrazolidin-3-one was tested as a photographic developer in a solution, designated as solution "D", of the same composition as solution "A * of Example 20, with the exception that dl · solution" D * * Contained 2.19 g of 4-BiimthylaBinomethyl-1-pnn9rlpyraxolidin-3 * one instead of 4-Morpholinoethyl-1-phenylpyrazolldin-3 ~ one. This Ent "wieklerlösung ^w D ^lf was" comparing it solution "B" of Example 20 in the development of a photographic Silberhalogenidemulsionsfilas. The following results were obtained:

009821/1952

developer
solution veil
(Base +
Emulsion) Relative
Sensation
opportunity contrast D max Development
time at 21.1
⁰ O (minutes) D. 0.15 1.76 2.09 2.90 5 B. 0.16 1.76 2.05 2.91 5

It can be seen from the results of Examples 20 to 22 that the compounds according to the invention have similar and sometimes better developer properties when compared with previous developers, such as 1-phenyl-3-pyrazolidinone and 4-methyl-1-phenylpyrazoli- din-3 ~ on, to be compared,, however, the connections are after of the invention when stored in the form of strongly alkaline solutions more stable · Furthermore, the compounds according to the invention are much more soluble at room temperature than 1-phenyl-3 ~ pyrazolidinone and ^ methyl-i-phenylpyrazolidin-O-one, so in one Developer solution of the composition described in Example 20 the solubilities of i-phenyl-3-pyrazolidinone and 4-kothyl-1-phenylpyrazolidine-Of 11.0 g / 1 and 5.5 gA, respectively, while the compounds according to the invention are 4-methylaminomethyl-i-phenylpyrasolldin-3-one and 4 -MorphQlinoaethyl-1-phenylpyraaolidin-3-one have solubility of 32.0 g / l or 24.0 g / l.

Claims

Ό09821 / 19Ε2

Claims (1)

Έ ate η ta λ would speak ^ -Pyrazolidinone compounds of the general formula GH «Ü GC IT in which E and H each independently of one another - hydrogen, one Alkyl, substituted alkyl, cycloalkyl, aralkyl or aryl radical, where the alkyl group of the alkyl, substituted alkyl, cycloalkyl or aralicyl radical represented by Ii or fi contains 1-6 carbon atoms, or in the optionally R and B together form a carbocyclic ring or, with the inclusion of the nitrogen atom, a heterocyclic ring and H represents represents an aryl or substituted aryl radical. 2 * · Compounds according to claim 1, characterized in that R and H together with the nitrogen atom form a morpholine or piperidine ring. 3 · Compounds according to claim 1, characterized in that R and / or R represent alkyl radicals substituted by a hydroxy or tertiary amino group. Α » Compounds according to one or more of the preceding claims, characterized in that H is an aryl radical substituted by an alkyl or alkoxy group or an ualogen atom, % A-Morpholinomethyl-i-phenylpyrazolldin-J-onc. 009821/1952 6. 4-Binie tiiylaminoraethyl-l-phenylpyrazolidin-'J-one » 7 ο acid oxalic acid salt of 4-dimethylaiainomethyl-l-phenyl - pyrazolian-3-one, 8 ο 4-dimethylaminomethyl-l ~ p-chlorophenylpyrazolidin-3-ono 9e. 4-piperidinomethyl-1-phenylpyrazolidin-3-one, 10. Process for the preparation of the compounds according to the claims 1 to 9t characterized by that one has an unsaturated, an aminomethylene group Compound of the general formula / C. in which R and R have the meanings given in claim 1 and R represents a hydrogen atom or an alkyl group, with a substituted hydrazine of the general formula R ² NH'MH ₂ 2
in which R has the meanings given in claim 1. H ₀ Process for the preparation of the compounds according to Claims 1 to 9, characterized in that an unsaturated organic compound of the general formula having an amino-ethylene group is used CH; f with a substituted hydrazine of the general formula 009821/1952 ³¹ - 1844Ü54 1 2 where in the two formulas R, R and R those specified in claim 1 Have meanings, in solution ^ converts and the received Hydrolyzed compound, 12 · Method according to claims IO to 11, characterized marked that the reactants are heated together in solution « 15 * The method according to claim 12, characterized in that that one used ethanol as a solvent 14 «Process for the preparation of the compounds according to the claims 1 to 9t characterized by that one has a 3 ~ pyrazolidinimine of the general formula N CH ₅ -C -C "NH ² II H ₂ C NH R ² in which R, R and R have the meanings given in claim 1 have, hydrolyzed, 15 · The method according to claim 14, characterized in that the 3-pyrazolidine imines in solution in an aqueous weakly acidic solution boils. 16. The method according to claim 14 or 15, characterized in that 4-piperidinomethyl-l-phenylpyrazolidine-3-yniine is hydrolyzed _o 009821/1952 17o method according to claim 14 or · 15 »thereby ge indicates that 4 ~ morpholinoniethyl-l-phenyl pyrazolidine-3-imine hydrolyzed. 18 ", method according to claim 14 or 15" thereby ge indicates that 4 * - DiiHethylaminomethyl «-lphenylpyrazolidin-> 3-imine hydrolyzed " 19ο Process for the preparation of the compounds according to Claims 1 to 3 »characterized in that ψ that one has an ester of the general formula IL COOR ⁵ 1 3 in which R and R have the meanings given in claim 1 and R have the meanings given in claim 10 _e with a substituted hydrazine of the general formula R ² HH * HH ₂ in which R has the meanings given in claim 1. 2Oo method according to claim 19 »characterized in that that a mixture of the two reactants is heated in solution. 0 09821/1952 ~ ³⁵ ~ 1944ÜÖ4 21o Process for the preparation of the compounds according to the claims 1 to 9 and in particular the method according to the claims 11 to 13, characterized in that an amine of the general formula is used under alkaline conditions - p ¹ '. in which P and P are each independently a hydrogen atom or an alkyl, substituted alkyl, cycloalkyl or aralkyl radical, or in which, if appropriate, P and P together a carbocyclic or with inclusion of nitrogen atoms form a heterocyclic ring, with formaldehyde and with one, an activated methylene group in the neighboring position to a carboxyl group-containing compound of the general formula X CH ₂ COOH in which X is an electron-withdrawing group to a compound of the general formula converts, in which P and P have the above meanings, this Compound with a substituted hydrazine of the general formula in which R has the meaning given in claim 1, and the reaction product is optionally hydrolyzed ₀ 0 0 9821/1952 22 β method according to claim 21 ', characterized draws that formaldehyde is in the form of paraformaldehyde used. 23 · Method according to claim 21, characterized draws that one is a bis-aminomethane compound of general formula in which P and P have the meanings given in claim 21, with a compound having an activated methylene group in Position adjacent to a carboxyl group with the general formula X ———— CHp COOH in which X has the meaning given in claim 21, mixed. 24 · The method according to any one of claims 21 to 23, d a through marked that one connections ο used, in which X is the groups -COCH, -COOP or -CN and P mean an alkyl, aryl or aralkyl group. 25 «The method according to any one of claims 21 to 24, characterized in that connections used in which P and P are alkyl, substituted alkyl, Cycloalkyl or aralkyl radicals mean, where the alkyl group Contains 1 to 6 carbon atoms. 009821/1952 26o The method according to any one of claims 21 to 25, characterized in that the implementation in is carried out in an aqueous reaction medium. 27 β method according to claims 21 "to 26, characterized denoted that one is a compound of the general formula ^ CH in which P and P have the meaning given in claim 21, 2 2 with an alcohol of the general formula P - OH, where P is the has the meanings given in claim 24, treated in the presence of a strong acid. 28ο The method according to claim 27, characterized in that the treatment is carried out with sulfuric acid . 29- Use of the compounds according to claims 1 to 28 in photographic silver halide emulsion developer solutions 30. Use according to claim 29, characterized in that one or more other developers are also used will. 31 ο Use according to claims 29 or 30 together with hydroquinone or N, H ⁱ -diethyl-p-phenylene ~ diamine (, 009821/1952