JPH0676360B2 - Synthesis of 4-alkoxy- and 4-aryloxy-3-acylaminophenyl carbonates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides 4-alkoxy- and 4-aryloxy-3-acylaminophenyl carbonates (or 4
-Alkoxy-, and 4-aryloxy-5-acylaminophenyl carbonates), especially the aforementioned 3-acylaminophenyl carbonates useful as intermediates for 2-equivalent cyan couplers for color photography Relating to the synthesis method of.

BACKGROUND OF THE INVENTION In recent years, it has been found that a dye formed by a 2,5-diacylaminophenol-based cyan color coupler is excellent in color recovery upon color development and is also excellent in wet heat fastness (for example, JP-A-53-53). 110530, 55-163537, 56-29235, 56-5
5945, 59-31953, 59-31954, U.S. Pat. No. 4,12
No. 4,396, No. 4,341,864, etc.), and the dye produced by the 2-phenylureido-5-acylaminophenol-based cyan color coupler is extremely excellent in color reversion property at the time of color development, spectral absorption characteristics, and wet heat fastness. It was discovered. (For example, US Pat. Nos. 4,333,999 and 4,427,7
67, JP-A-57-204543, 57-204544, 57-20454
Therefore, 4-alkoxy-, and 4-aryloxy-5-acylaminophenyl carbonates are noteworthy compounds as synthetic intermediates for these couplers. By the way, photographic couplers are roughly classified according to the hue of the color forming dye, and from the stoichiometry, 4
It is roughly classified into two types, an equivalent coupler and a two equivalent coupler. A 4-equivalent coupler produces 1 mole of dye by consuming 4 moles of silver halide, whereas a 2-equivalent coupler has a leaving group at the coupling position of the coupler, and 1 mole of 2 moles of silver halide is used per mole of silver halide. It is known to be an advantageous coupler from the standpoint of silver saving because it produces a dye. Thus, with the recent increase in the sensitivity of color negative films, high-speed 2-equivalent couplers in which a leaving group is introduced at the coupling position are often used. , And development of a simple synthetic method for 4-aryloxy-3-acylaminophenyl carbonates has been desired. Thus, it is important as a synthetic intermediate for cyan color couplers in photographic chemistry.
The synthesis method of -alkoxy- and 4-aryloxy-3-acylaminophenyl carbonates is described in JP-B-59-451.
No. 42 discloses a method shown by the following route.

However, in the alkylation reaction of the hydroxyl group in the step of synthesizing the compound [b] from the compound [a] in the above reaction formula, the nucleophilicity of the hydroxyl group is increased by the hydrogen bond between the nitro group existing at the ortho position of the hydroxyl group and the hydroxyl group. The reactivity is poor because it is greatly reduced, and the reaction point is activated by an electron-withdrawing group, etc., but it reacts with a so-called active halogen compound, but the reaction point is not particularly activated. If
The yield of the desired product is very low, and the synthetic method by the above route is not universally applicable.

As a result of various studies conducted by the present inventors to overcome the drawbacks of the above synthetic method, the reactivity of the hydroxyl group was increased by previously converting the nitro group of the compound represented by the general formula [I] into an acylamino group. We succeeded in obtaining the expected product with a high yield of 90% or more.

[Object of the Invention] Therefore, an object of the present invention is 4-alkoxy- and 4-aryloxy, which are versatile in simple operation and can be synthesized in a high yield without any side reaction. It is to provide a method for synthesizing 3-acylaminophenyl carbonates.

[Structure of the Invention] The above-mentioned object is to synthesize a compound represented by the general formula [II] by reducing the nitro group of the compound represented by the general formula [I] and further acylating the compound, and then converting the hydroxyl group into an alkyl group. Can be converted to the general formula [II
I]] 4-alkoxy- and 4-aryloxy-3-acylaminophenyl carbonates, which are characterized by synthesizing 4-alkoxy- and 4-aryloxy-3-acylaminophenyl carbonates Achieved by a synthetic method of a class.

[However, in the general formulas [I] to [III], R ₁ , R ₂ , and R ₃ represent a substituted or unsubstituted alkyl group or an aryl group. The reaction method of the synthetic method of the present invention is shown in more detail below.

Here, R ₁ , R ₂ and R ₃ in the general formulas [I] to [III] represent an alkyl group or an aryl group, and R ₂ is an alkyl group having 1 to 20 carbon atoms as an alkyl group, It may have a group, and a group represented by the following general formula [IV] is preferable.

[However in this general formula, Y is -O -, - S -, - SO 2 - a, R
₄ is an alkylene group having 1 to 20 carbon atoms (methylene, 1,1-ethylene, 1,1-propylene, 1,3-propylene, 2-methyl-1,1-propylene, 1,1-pentylene, 1,1 -Heptylene, 1,1-nonylene, 1,1-undecylene, 1,1-tridecylene, 1,1-pentadecylene, etc.), R ₅ is a halogen atom (chlorine atom, fluorine atom, etc.), a hydroxy group, and a carbon number of 1 to 1. 20 alkyl groups (eg methyl, ethyl, te
rt-butyl group, tert-pentyl group, cyclopentyl group,
tert-octyl group, pentadecyl group, etc., alkoxy group (methoxy group, ethoxy group, isopropoxy group, butoxy group, hexyloxy group, dodecyloxy group, etc.), alkylsulfonamide group (methanesulfonamide group, ethanesulfonamide group) , Butanesulfonamide group, octylsulfonamide group, hexadecylsulfonamide group, etc., arylsulfonamide group (benzenesulfonamide group, m-chlorobenzenesulfonamide group, toluenesulfonamide group, p-methoxybenzenesulfonamide group, p -Dodecyloxybenzenesulfonamide group, etc.), alkylsulfamoyl group (butylsulfamoyl group, tert-butylsulfamoyl group, dodecylsulfamoyl group, etc.), arylsulfamoyl group (benzenesulfamoyl group, To Enns sulfamoyl group and a dodecyloxy benzene sulfamoyl group), an alkylsulfonyl group (methanesulfonyl group, a butanesulfonyl group), an arylsulfonyl group (benzenesulfonyl group,
Examples thereof include p-benzyloxyphenylsulfonyl group, p-hydroxyphenylsulfonyl group and the like) and alkoxycarbonyl groups (ethoxycarbonyl group, butoxycarbonyl group, hexadecyloxycarbonyl group and the like). l
Represents an integer of 1 to 4, preferably 1 or 2. When l is 2 or more, R ₅ may be the same or different. In the present invention, when R ₂ in the general formula [I] is an aryl group, it is preferably a phenyl group, and the phenyl group may be substituted with R _{5 represented} by the general formula [VI]. .

R ₁ and R ₃ represent an alkyl group (for example, an alkyl group having 1 to 20 carbon atoms or an alkenyl group) or an aryl group (for example, an aralkyl group or an aralkenyl group, an aryl group having 6 to 12 carbon atoms). Here, the alkyl group, alkenyl group, aralkyl group, aralkenyl group, and aryl group represented by R ₁ and R ₃ are halogen atom (fluorine, chlorine, iodine, bromine), nitro group, cyano group, hydroxyl group, alkoxy group, It may be substituted with an alkylthio group, an arylthio group, an acyloxy group, an acylamino group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group or a sulfo group. Also R ₁
The alkyl group, alkenyl group, aralkyl group and aralkenyl group represented by R ₃ may be linear or branched.

[Step] The acylaminophenol derivative represented by the general formula [II] is synthesized from the orthonitrophenol derivative represented by the general formula [I] by reducing the nitro group to an amino group and then reacting with R ₂ COX. To be achieved. The reduction of a nitro group to an amino group can be easily carried out by a conventional method for reducing an aromatic nitro compound.However, the post-treatment is easy in the case of the catalytic reduction method, and a side reaction does not occur and the yield is good. It is preferable in that the intended product can be obtained. The amino compound obtained here can be used in the next reaction without particular purification.

The reaction between the amino compound and R ₂ COX is such that when X is a halogen atom,
It can be smoothly carried out by a method of coexisting a tertiary amine in an aprotic solvent or a shotten-Baumann method. When X is OH, the reaction can be carried out by heating the mixture of both to a high temperature and removing the produced water by azeotropic distillation, or by allowing a dehydrating agent to coexist. In particular, carbodiimides are used as a dehydrating agent. When used, the target product can be obtained in high yield.

When X is an alkoxy group, the desired product can be obtained by heating the mixture of both to a high temperature and distilling off the produced alcohol, but when the amino compound is converted to an alkali amide with a strong base, the reaction occurs under mild conditions. And the yield is good.

When X is an acyloxy group, the desired product can be obtained by heating a mixture of the two, but the addition of a small amount of pyridine, sulfuric acid or the like accelerates the reaction and improves the yield.

[Step] The acylaminophenol derivative represented by the general formula [II] can be easily alkylated or arylated by the method described in detail below, and the 4-alkoxy- and 4-aryloxy represented by the general formula [III] can be obtained. It is possible to obtain -3-acylaminophenyl carbonates in high yield.

The alkylation reaction proceeds in good yield under the alkylation conditions generally performed with phenols.

Among them, alkylation under basic conditions is preferable, for example, alkylation with an alkyl halide and potassium carbonate in acetone; alkylation with a dialkylsulfuric acid or an alkyl-p-toluenesulfonic acid ester in an alcoholic sodium hydroxide solution. The reaction proceeds under conditions such as sodium alkoxide or sodium hydride and alkyl iodide, alkyl bromide, alkyl chloride, or alkylation using alkyl-p-toluenesulfonic acid ester. In either case, the alkylating agent is used in the range of about 1 to 10 equivalents, preferably 1 to 2 equivalents, relative to the acylaminophenol derivative. The alkali is used in the range of 1 to 100 equivalents, particularly preferably 1 to 10 equivalents based on the acylaminophenol derivative. The reaction temperature is suitably in the range of about 0 ° C to 100 ° C for about 0.5 to 40 hours. In some cases, the alkylation can be carried out under a condition using a Lewis acid, and the alkylation can be carried out with a diazoalkane and a Lewis acid. In addition, addition reaction to olefin and acetylene compounds proceeds smoothly, and corresponding alkyl and alkenyl ethers can be obtained. Addition to ordinary olefin compounds can be carried out in the presence of an acid catalyst such as sulfuric acid, hydrochloric acid or boron trifluoride, and to olefin compounds having an electron withdrawing group such as halogen, alkoxycarbonyl, nitro or cyano. The addition can be performed by coexisting with a base or by using an acylaminophenol derivative as an alkali salt. In addition, the alkali salt of acylaminophenol easily adds to an acetylene compound to give an alkenyl ether.

The arylation reaction is known as the ullmann reaction Cu, Cu ⁺ , Cu
It is achieved by performing a substitution reaction with an aryl halide in the presence of a metal represented by ⁺⁺ or a metal ion. Further, when the halogen atom is activated by the electron-withdrawing group on the aromatic ring, the metal or the metal ion does not necessarily need to coexist, and the reaction proceeds under milder conditions.

Specific examples of 4-alkoxy- and 4-aryloxy-5-acylaminophenyl carbonates synthesized by the method of the present invention are listed below, but the invention is not limited thereto.

In the above exemplified compounds, Me represents CH ₃ and Et represents C ₂ H ₅ .

The 4-alkoxy- and 4-aryloxy-3-acylaminophenols synthesized by the present invention are useful cyan by diverting the method shown in the following reference example (disclosed in Japanese Patent Publication No. 59-45142). Can be guided to a coupler.

(Synthesis scheme 1) Compound 1: Z = CH ₂ CO ₂ Me Compound 3: Z = CF ₂ CHFCF ₃ [Example] The following is an example relating to the synthesis method of the present invention, which is one example of the present invention. It is not limited.

Example 1 (Synthesis of Compound 1) 5.0 g of compound [a] was dissolved in 50 ml of methanol, 1.0 g of Raney nickel was added, and catalytic hydrogenation was carried out at room temperature and atmospheric pressure. After the reaction was completed, the catalyst was separated and the solvent was distilled off under reduced pressure.
The residue was washed with a mixed solvent of ethyl acetate-n-hexane,
3.7 g (yield 85%) of crude crystals of compound [d] were obtained. This product was dissolved in 40 ml of ethyl acetate, 2.5 g of N, N-dimethylaniline was added, and a solution of 7.6 g of α-2- (2,4-di-t-acylphenoxy) hexanoyl chloride in ethyl acetate (20 ml) was added. 50 ml of ethyl acetate was added to the reaction solution which was slowly added dropwise at room temperature and stirred for 5 hours, washed with water and concentrated under reduced pressure. The residue was recrystallized with a mixed solvent of ethyl acetate-n-hexane to give compound [e] of 7.1 g ( Yield 71%) was obtained. mp.108 ~ 11
0 ℃ Dissolve this in 100 ml of acetone and potassium carbonate 2.
1 g and 3.1 g of methyl bromoacetate were added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the insoluble material was removed and the mixture was concentrated under reduced pressure.
Ethyl acetate was added to the residue, washed with water and concentrated under reduced pressure to obtain 7.3 g (90%) of Compound 1 as an oil. Structure is NM
It was identified by R, IR, and MASS.

Example 2 (Synthesis of Compound 2) 5.3 g of compound [e] was mixed with 600 mg of potassium hydroxide in alcohol 3
It was dissolved in a 0 ml solution, and then the solvent was distilled off under reduced pressure. DMF (50 ml) and 2,4-dinitrochlorobenzene (2.4 g) were added to the residue.
The mixture was heated and stirred at 0 ° C for 3 hours. Crystals were precipitated when 300 ml of water was added. Crystals were collected and recrystallized from a mixed solvent of ethyl acetate-n-hexane to obtain 6.8 g of Compound 2. (Yield 94
%). The structure was identified by NMR, IR and MASS.

Example 3 (Synthesis of Compound 3) 5.3 g of the compound [e] was dissolved in 100 ml of dimethylformamide, 11.1 g of triethylamine was added, and a solution of 1.7 g of hexafluoropropylene in dimethylformamide (20 ml) was added dropwise under ice cooling. Stir for 1 hour. The reaction solution was poured into ice water 1 and the precipitated crystals were collected. The crystals were recrystallized from a mixed solvent of ethyl acetate-n-hexane to give compound 3
Was obtained in an amount of 6.2 g. (Yield 91%). Structures are NMR, IR, and M
It was identified by ASS.

The 4-alkoxy- and 4-aryloxy-3-acylaminophenol derivatives obtained by the present invention are represented by the following general formulas [V] to [VII] according to the synthetic method disclosed in JP-B-59-45142. A 2-phenylureido-5-acylaminophenol cyan coupler can be easily synthesized by synthesizing a compound and further condensing the compound [VII] with carbamic acid esters in acetonitrile.

[However, in general formulas [V] to [VII], R ₂ and R ₃ have the same meanings as R ₂ and R ₃ described above] Reference Example (Synthesis of Compound 21) (Synthesis Scheme 2) Compound 1 and 20.6 g were dissolved in methanol 200 ml, an aqueous solution of sodium hydroxide 2.7 g (20 ml) was added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the mixture was acidified with hydrochloric acid and extracted with ethyl acetate. After washing with water and concentration under reduced pressure, methanol 100 ml, concentrated sulfuric acid 1-
Two drops were added and the mixture was heated under reflux for 4 hours. After completion of the reaction, the mixture was concentrated under reduced pressure, and the residue was recrystallized from n-hexane to give compound [f].
15.5 g (yield 86%) was obtained. mp.128 ℃ -130 ℃.

5.3 g of compound [f] was dissolved in 30 ml of chloroform, 1.1 ml of concentrated nitric acid (d = 1.38) was slowly added dropwise under ice cooling, and the mixture was stirred for 30 minutes as it was. After completion of the reaction, the product was washed with water and concentrated under reduced pressure to obtain 5.0 g (yield 87%) of the compound [g] as an oil. This product was dissolved in 150 ml of methanol and catalytically reduced using a palladium catalyst with a carbon support at room temperature and atmospheric pressure.

After the theoretical amount of hydrogen was consumed, the catalyst was separated and concentrated under reduced pressure, 30 ml of acetonitrile, 20 mg of imidazole were added to the residue.
Phenyl 3-cyano-4-chlorophenylcarbamate
2.0 g was added and the mixture was heated under reflux for 2 hours. Cool the reaction,
The precipitated crystals were collected and recrystallized from acetonitrile to obtain Compound 21 (3.4 g, yield 53%). mp.143 ~ 145
° C. The structure was identified by NMR, IR and MASS.

[Effect of the Invention] In the method for synthesizing 4-alkoxy- and 4-aryloxy-3- (or -5) acylaminophenyl carbonates, the conventional synthetic method has poor reactivity and extremely high yield. Not only is it low in general versatility, but by using the synthesis method of the present invention, the reactivity is increased and there is no side reaction, and therefore, it is possible to obtain a high yield and versatility. It is a simple and easy synthetic method.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07C 255/13 309/75 311/49 317/18

Claims (1)

[Claims] 1. A compound represented by the general formula [II] by reducing the nitro group of the compound represented by the general formula [I] and further acylating the compound.
4-alkoxy- and 4-aryloxy-3 represented by the general formula [III] by synthesizing a compound represented by
-A method for synthesizing 4-alkoxy- and 4-aryloxy-3-acylaminophenyl carbonates, which comprises synthesizing an acylaminophenyl carbonate. [However, in the general formulas [I] to [III], R ₁ , R ₂ , and R ₃ represent a substituted or unsubstituted alkyl group or an aryl group. ]