JPH0570407A - Cyclopropanecarbonylacetic acid ester - Google Patents

Abstract

PURPOSE:To provide a new cyclopropanecarbonylacetic acid ester useful as a synthetic intermediate for heterocyclic compounds, photographic couplers for forming yellow pigment, etc. CONSTITUTION:The compound of formula (R<1> is 2-4C alkyl; R<2> is 1-4C alkyl), e.g. ethyl 1-ethylcyclopropane-1-carbonylacetate. The compound can be produced by reacting a ketone compound of formula II (e.g. alpha-acetyl-gamma-butyrolactone) with a dialkyl carbonate of formula III in the presence of a base.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel cyclopropanecarbonyl acetic acid ester useful as a synthetic intermediate for heterocyclic compounds, photographic yellow dye-forming couplers and the like.

[0002]

BACKGROUND OF THE INVENTION Acyl acetates are useful as starting materials for the synthesis of heterocyclic compounds (eg 5-pyrazolone, 5-isoxazolone, pyridine). In addition, 1-methylcyclopropane-1- which is a kind of acyl acetate ester
Ethyl carbonyl acetate is used as a raw material for synthesizing 9-bromo-2,7-dimethylnona-2,6-diene, which is useful as a synthetic intermediate for terpenes and steroids.

Acyl acetates are also useful as starting materials for the synthesis of photographic yellow dye forming couplers. The skeleton of the yellow dye-forming coupler is an acylacetanilide which is usually obtained by a condensation reaction of acylacetic acid ester and aniline, and representative ones thereof are benzoylacetanilide and pivaloylacetanilide.

[0004]

As mentioned above, there are few kinds of acylacetic acid esters to be used for synthesis although they are useful synthetic raw materials. Further, the skeleton used as a photographic yellow dye-forming coupler is limited to benzoylacetanilide and pivaloylacetanilide,
In addition, the color images obtained from these couplers have poor fastness to heat, and improvements have been strongly desired.

Therefore, the first object of the present invention is to provide a novel acylacetic acid ester useful as a starting material for the synthesis of heterocyclic compounds, terpenes, steroids and the like.

A second object of the present invention is to provide acylacetic acid esters which provide novel photographic yellow dye-forming couplers.

A third object of the present invention is to provide an acylacetic acid ester which provides a novel photographic yellow dye-forming coupler which is fast in color images.

[0008]

The above object of the present invention is achieved by cyclopropane-1-carbonyl acetic acid ester represented by the following general formula (hereinafter referred to as the compound of the present invention).

[0009]

[Chemical 2] (In the formula, R ¹ represents an alkyl group having 2 to 4 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms.)

The compound of the present invention is described in detail below. As a specific example of R ^{1 in} the general formula, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, isobutyl group and 2-butyl group. R ¹ is preferably an ethyl group, an n-propyl group, an n-butyl group or an isobutyl group.

Specific examples of R ^{2 in} the general formula include methyl group, ethyl group, n-propyl group, isopropyl group and n-
There are a butyl group, an isobutyl group, a 2-butyl group, and a t-butyl group. R ² is preferably a methyl group or an ethyl group.

Of the compounds of the present invention, the following compounds are preferred. Ethyl 1-ethyl cyclopropane-1-carbonyl acetate Boiling point 134 ° C./25 mmHg Methyl 1-ethyl cyclopropane-1-carbonyl acetate 89-91 ° C./0.3 mmHg Ethyl 1-n-propyl cyclopropane-1-carbonyl acetate 136- 140 ° C./20 mmHg ethyl 1-n-butylcyclopropane-1-carbonyl acetate 124-126 ° C./1.2 mmHg ethyl 1-isobutylcyclopropane-1-carbonyl acetate 136-137 ° C./11 mmHg The compounds of the present invention are synthesized as follows. Can be combined by root.

[0013]

[Chemical 3]

Here, the ketone body a can be synthesized, for example, by the method described in the following documents. M. Julia, S. Julia, Y. Noel, Bull. Soc. Chim. Fr.,
1960, 1708 M. Asaoka, K. Miyake, H. Takei, Chem. Lett., 1975,
1149

The reaction between the ketone body a and the dialkyl carbonate b is carried out by using a base (for example, NaH, NaNH ₂ , KH, t-).
Butoxy potassium, butyl lithium, sodium ethylate, sodium methylate) in the presence of no solvent or tetrahydrofuran, dioxane, ether, benzene,
It is carried out in a solvent such as toluene, xylene or tetralin. Reaction temperature is -10 ° C to 200 ° C, preferably 25 ° C
~ 150 ° C. The base and dialkyl carbonate are preferably used in excess (for example, 2 equivalents) with respect to the ketone body.

[0016]

EXAMPLES The present invention will be described in more detail based on examples. Example 1 Synthesis of ethyl 1-ethylcyclopropane-1-carbonyl acetate 400 ml of acetone was added to 207 g of potassium carbonate, and 128 g of α-acetyl-γ-butyrolactone was added with stirring. Next, 210 g of ethyl iodide was added dropwise over 1 hour while heating under reflux, and the mixture was further heated under reflux for 3 hours. After cooling the reaction solution, inorganic salts were filtered, and the filtrate was concentrated with an evaporator. Then, by distillation under reduced pressure, α-at a boiling point of 135 ° C. to 140 ° C./30 mmHg
134 g of acetyl-α-ethyl-γ-butyrolactone
Got

To 12.9 g of sodium iodide, 50 ml of N-methylpyrrolidone was added, and α- was added with heating and stirring at 190 ° C.
134 g of acetyl-α-ethyl-γ-butyrolactone was added dropwise in about 1 hour. 71.4 g of 1-ethylcyclopropyl methyl ketone was obtained by collecting the components distilled at 130 ° C to 145 ° C. 60% sodium hydride 5
0.9 g was dispersed in 300 ml of tetrahydrofuran, and 150 g of diethyl carbonate was added with stirring. Then heat to reflux,
71.4 g of 1-ethylcyclopropyl methyl ketone was added dropwise in about 1 hour. The mixture was heated under reflux for another 2 hours, and the reaction liquid was cooled. The reaction solution was added to dilute hydrochloric acid containing ice and extracted with ethyl acetate. After distilling off ethyl acetate with an evaporator, vacuum distillation was carried out to obtain 76.2 g of desired ethyl 1-ethylcyclopropane-1-carbonyl acetate having a boiling point of 134 ° C./25 mmHg. Of the obtained compound
^{The 1} H NMR spectrum is shown below.

¹ H NMR spectrum (CDCl ₃ ) δ; 0.08 to 0.90 (m, 2H), 0.97 (t, 3H), 1.20 to 1.32
(m, 2H), 1.29 (t, 3H), 1.20 ~ 1.32 (m, 2H), 1.68 (q,
2H), 3.38 (s, 2H), 4.19 (q, 2H)

Example 2 Synthesis of ethyl 1-n-propylcyclopropane-1-carbonylacetate 384 g of α-acetyl-γ-butyrolactone was added to N, N-
It was dissolved in 1000 ml of dimethylformamide, and 144 g of 60% sodium hydride was added. Next, 620 g of n-propyl iodide was added dropwise at room temperature with stirring for about 1 hour. After stirring for 2 hours, 2 liters of water and 500 ml of ethyl acetate were added for extraction. After concentration with an evaporator, vacuum distillation is performed and α-acetyl-α with a boiling point of 139 ° C to 146 ° C / 18 mmHg.
340 g of -n-propyl-γ-butyrolactone was obtained.

50 ml of N-methylpyrrolidone was added to 30 g of sodium iodide, and 339 g of α-acetyl-α-n-propyl-γ-butyrolactone was stirred with heating at 200 ° C.
Was dropped in about 2 hours. 170 g of methyl 1-n-propylcyclopropylketone was obtained by collecting the components distilled at 147 to 162 ° C.

103 g of 60% sodium hydride was dispersed in 340 g of tetrahydrofuran, and diethyl carbonate 3 was added with stirring.
05g was added. Then, the mixture was heated under reflux, and 163 g of methyl 1-n-propylcyclopropylketone was added dropwise in about 1 hour. The mixture was heated under reflux for another 2 hours, and the reaction liquid was cooled. The reaction solution was added to dilute hydrochloric acid containing ice and extracted with ethyl acetate. After distilling off ethyl acetate with an evaporator, vacuum distillation was carried out to obtain 146 g of desired ethyl 1-n-propylcyclopropane-1-carbonylacetate having a boiling point of 136 to 140 ° C./20 mmHg. Of the obtained compound
^{The 1} H NMR spectrum is shown below.

¹ H NMR spectrum (CDCl ₃ ) δ; 0.78 to 0.90 (m, 2H), 0.90 (t, 3H), 1.20 to 1.31
(m, 2H), 1.25 (t, 3H), 1.32 ~ 1.51 (m, 2H), 1.51 ~ 1.
65 (m, 2H), 3.34 (s, 2H), 4.17 (q, 2H) Other compounds of the present invention can be synthesized by the same synthetic method.

Reference Example 1 Synthesis of 5-pyrazolone 3.7 g of ethyl 1-ethylcyclopropane-1-carbonylacetate and 2.2 g of phenylhydrazine were mixed and stirred at 120 ° C. for 1 hour. After distilling off the ethanol produced under reduced pressure and crystallizing from n-hexane, the target pale yellow crystal of 3- (1-ethylcyclopropan-1-yl) -1-phenyl-5-pyrazolone was obtained in 3. 3 g was obtained. The compound structure was confirmed by ¹ H NMR spectrum, MASS spectrum and elemental analysis.
The melting point of this compound was 77 to 78.5.

Reference Example 2 Synthesis of Yellow Dye-Forming Coupler 1 32.2 g of ethyl 1-ethylcyclopropane-1-carbonyl acetate and 12.7 g of 2-chloroaniline.
Were mixed and stirred at 140 ° C. for 3 hours. Excess ethyl
1-Ethylcyclopropane-1-carbonylacetate was distilled off under reduced pressure and then purified by column chromatography to obtain the desired oily N- (2-chlorophenyl)-(1-ethylcyclopropane-1- 24.0 g of carbonyl) acetamide was obtained. The structure of this compound was confirmed by ¹ H NMR spectrum, MASS spectrum and elemental analysis.

Reference Example 3 Synthesis of Yellow Dye-Forming Coupler 2 20.0 g ethyl 1-n-propylcyclopropane-1-carbonyl acetate and 2-chloroaniline 8.
0 g was mixed and stirred at 140 ° C. for 3 hours. The excess ethyl 1-n-propylcyclopropane-1-carbonylacetate was distilled off under reduced pressure, and the residue was purified by column chromatography to give the desired oily N 2
12.7 g of-(2-chlorophenyl)-(1-n-propylcyclopropane-1-carbonyl) acetamide
Obtained. The structure of this compound is ¹ H NMR spectrum, MA
Confirmed by SS spectrum and elemental analysis.

Reference Example 4 Synthesis of Yellow Dye-Forming Coupler 3 A synthetic scheme is shown below.

[Chemical 4]

Ethyl 1-ethylcyclopropane-1-
27.5 g of carbonyl acetate and 5-amino-2,
37.4 g of dodecyl C 4-dichlorobenzoate was mixed and stirred under reduced pressure at 140 ° C. for 4 hours. Excess ethyl 1-ethylcyclopropane-1-carbonylacetate was distilled off under reduced pressure, and then methanol was added for crystallization to obtain 43.1 g of white crystals of compound d. Compound d (41.0 g) was dissolved in methylene chloride (200 ml), and sulfuryl chloride (10.8 g) was added dropwise under ice cooling. 1 at room temperature
After stirring for an hour, methylene chloride was distilled off under reduced pressure to obtain an oily compound e. Compound e with 1-benzyl-
4-Ethoxyhydantoin 46.9g and N, N- dimethylformamide 200ml were added, and also triethylamine 16.2g was dripped in 30 minutes. After stirring for 5 hours, 500 ml of ethyl acetate and 1 liter of water were added for extraction, and the ethyl acetate solution was washed with an aqueous sodium hydroxide solution and then with dilute hydrochloric acid. After distilling off ethyl acetate with an evaporator, crystallization was carried out by adding methanol to obtain 48.9 g of a white crystal of the objective yellow dye-forming coupler f.
Obtained. The structure of this compound is ¹ H NMR spectrum, M
Confirmed by ASS spectrum and elemental analysis. The melting point of this compound was 73 to 75 ° C.

Reference Example 5 Yellow Dye Forming Coupler Y-1, Y-2, Y-3, Y-4 Derived from the Compound of the Present Invention YC Dye Forming Coupler YC Derived from Ethyl Pivaloyl Acetate -2, YC-4, the following yellow dye-forming coupler derived from ethyl 4-methoxybenzoyl acetate, and the following yellow dye-forming coupler derived from YC-1, YC-3 and ethyl 1-methylcyclopropane-1-carbonyl acetate. Using YC-5 and YC-6, the fastness of the color image was compared.

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

Yellow dye-forming coupler Y-1 was added to 17.
After weighing 0 g, 9.2 cc of tricresyl phosphate and 20 cc of ethyl acetate were added and dissolved. To 500 g of a 10% aqueous gelatin solution, 2.5 g of sodium dodecylbenzenesulfonate was added, and the entire amount of the above coupler solution was added to emulsify and disperse. A silver chlorobromide emulsion (70 mol% of silver bromide) was added to this emulsified dispersion so that the molar ratio of silver halide to coupler was 3.0. Further, a 10% gelatin aqueous solution and water were added so that the amount of the coating solution completed was 2000 cc and the gelatin concentration at the time of completion was 5%. This coating solution was coated on an undercoated triacetyl cellulose support so that the coating amount of the coupler would be 1 mmol / m ² . At this time, 1-oxy-3,5-dichloro-s as a hardener
-A gelatin protective layer with sodium triazinate was applied at the same time.

Similarly, Y-2 to Y-4 and YC-1 to
A film sample was prepared by using YC-6 and substituting it for Y-1 so as to be equimolar to Y-1. The prepared sample was prepared by first using a sensitometer (FW, manufactured by Fuji Photo Film Co., Ltd.
Gradient exposure for sensitometry was performed using an H type and a light source color temperature of 3200K). The exposure at this time is 0.1
The exposure amount was 250 CMS with an exposure time of 2 seconds. The exposed sample was processed in the following steps. The composition of each treatment liquid is shown below.

Processing step Temperature Time Color development 35 ° C. 2 minutes Bleach fixing 35 ° C. 1 minute 30 seconds Wash with water 35 ° C. 2 minutes Dry 60 ° C. 10 minutes

Color developer water 700 ml Ethylenediaminetetraacetic acid 3.0 g Triethanolamine 12.0 g Potassium bromide 1.0 g Potassium carbonate 27.0 g Sodium sulfite 0.1 g Disodium-N, N-bis (sulfonate ethyl) hydroxyl Amine 8.0 g N-ethyl-N- (β-methanesulfonamidoethyl) 1.0 g-3-Methyl-4-aminoaniline sulfate 5.0 g Water was added to 1000 ml pH (25 ° C.) 10.05

Bleach-fixing solution Water 600 ml Ammonium thiosulfate aqueous solution (700 g / l) 100 ml Ethylenediaminetetraacetic acid (III) ammonium 55 g Ethylenediaminetetraacetic acid 5 g Ammonium bromide 40 g Nitric acid (67%) 30 g Water 1000 ml pH (25 ° C.) ( With acetic acid or ammonia water) 5.8

Sensitometry was performed on each of the obtained samples after the treatment with blue light. Each sample is then
After storing for 1 month under constant temperature and humidity conditions of 70% RH, sensitometry was performed again with blue light. Initial concentration 1.0
The residual rate of the color image at was read from the sensitometric curve. The results are shown in Table 1. Here, it can be said that the larger the residual ratio of the color image is, the more excellent the fastness is.

[0038]

[Table 1]

From Table 1, the yellow dye-forming couplers derived from the compounds of the present invention show that the color fastness of the colored image is higher than that of the conventional yellow dye-forming couplers derived from ethyl pivaloyl acetate or ethyl p-methoxybenzoyl acetate. It turns out that it is excellent. Further, the yellow dye-forming coupler derived from the compound of the present invention is remarkably excellent in the fastness of the color image even when compared with the yellow dye-forming coupler derived from ethyl 1-methylcyclopropane-1-carbonyl acetate. I understand.
The structure of the acyl acetate ester used in the synthesis of the coupler in Table 1 is shown in Chemical formula 8.

[0040]

[Chemical 8]

[0041]

INDUSTRIAL APPLICABILITY The compounds of the present invention are extremely useful as synthetic intermediates for couplers which form photographic yellow dyes having high fastness. It is also useful as a synthetic intermediate for various heterocyclic compounds, terpenes, steroids and the like.

Claims (1)

[Claims] 1. A cyclopropanecarbonyl acetic acid ester represented by the following general formula. [Chemical 1] (In the formula, R ¹ represents an alkyl group having 2 to 4 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms.)