JPH03130280A - Production of 4-aryloxy-1,3-bonzodioxole - Google Patents

Abstract

PURPOSE:To inexpensively obtain the title compound useful as an intermediate of compound for photograph in reduced process numbers and high yield by reacting a carboxylic acid with a phosphorus halide and then reacting the product with a specific compound. CONSTITUTION:A carboxylic acid expressed by the formula R<4>CO2H (R<4> is 6-10C aryl or 1-10C alkyl) is reacted with a compound expressed by the formula PXn (X is Cl or Br; (n) is 3 or 5) pref. in an aprotic solvent such as methylene chloride at 20-90 deg.C for 10 min to 2hr and the resultant reaction mixture is reacted with a compound expressed by formula I (R<1> to R<2> are H, 6-10C aromatic or 1-6C aliphatic or R<1> may be combined with R<2> and in this case, sum of carbon number of R<1> and R<2> is 1-12; R<3> is amino, 1-20C alkyl, amino or alkoxy; R<5> is benzyl), preferably at 0-90 deg.C for 20min to 3hr to provide the objective compound expressed by formula Il.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides 4-aryloxy-
The present invention relates to a method for producing 1,3-benzodioxoles.

(Prior Art and Problems to be Solved by the Invention) 3-aryloxycatechols are compounds useful as intermediates for photographic compounds. For example, this photographic use is described in JP-A-61-53643 and JP-A-63-136046. Furthermore, 3-aryloxycatechols are compounds that are expected to be used as intermediates for preservatives, rust preventives, preservatives, pharmaceuticals, dyes, and the like.

Compounds described in JP-A-63-17850 and JP-A-63-136046 are known as synthetic intermediates for 3-aryloxycatechols.

However, the compounds described in these patents had drawbacks such as a large number of reaction steps from the raw material heronitrobenzene to the aryloxycatechol (and a low total synthesis yield). When used as an intermediate, purity is a particular issue because the application is involved in the color development mechanism, and therefore each reaction raw material must be of high purity from the synthesis stage.However, it is difficult to use high purity raw materials. This requirement leads to an increase in industrial production costs, and from this point of view, there is a need to develop a method for producing vines that is fully economical.Therefore, the present invention provides a method for manufacturing vines with a small number of steps, high yield, and low cost. An object of the present invention is to provide a method for producing aryloxycatechols that can yield the desired product.

(Means for Solving the Problems) The present inventors have conducted research to overcome the drawbacks of the above-mentioned conventional methods and to develop a method for synthesizing 3-aryloxycatechols in a high yield and at low cost with a small number of steps. As a result of repeated efforts, it has been found that the above-mentioned problems can be solved by a method using a reaction mixture as a raw material and via a compound represented by formula (I) described below.

The object of the present invention is to react a carboxylic acid represented by formula (II) with a compound represented by formula (II+), and then react the resulting reaction mixture with a compound represented by formula (1). 4- represented by formula (I)
This was achieved by a method for producing benzodioxoles, which is characterized by obtaining aryloxy-1,3-benzodioxoles.

Formula (I) (wherein, R' R2 represents a hydrogen atom, an aromatic group having 6 to 10 carbon atoms, or an aliphatic group having 1 to 6 carbon atoms. Also, R1
and R2 may be bonded together, in which case the sum of the carbon numbers of R1 and R2 is 1 to 12.

R3 represents an amino group, an alkylamino group having 1 to 20 carbon atoms, or an alkoxy group. R4 has 6 to 10 carbon atoms
represents an aryl group or an alkyl group having 1 to 10 carbon atoms. R5 represents a benzyl group. ) Formula (II) R' Co, H (R' has the same meaning as formula (I)) Formula (III) Pxn (X is Cβ or B) Formula (IV) r represents, n is 3 or 5 (In the formula, R' R2, R'', and R' have the same meanings as in formula (I).) The present invention will be explained in detail below.

When R1 or R2 represents an aromatic group in formula (I), a typical example is a phenyl group, and specific examples of phenyl groups connected to each other include (in addition, R6 represents a hydrogen atom or a substituent). Further, when R1 or R2 represents an aliphatic group, typical examples include methyl, ethyl, propyl, isopropyl, butyl or cyclohexyl, and R'
Examples of when and R2 are linked to form a ring include: Among these, preferred substituents are those shown in Table 1.

Of these in Table 1, particularly preferred are No. 1, 2.3 and 8.

When R3 represents an alkylamino group in formula (I), specific examples include methylamino, ethylamino, propylamino, butylamino, hexylamino, decylamino, icosylamino, isopropylamino, isobutylamino, 5ec-butylamino, t -butylamino,
Examples include dimethylamino, methylethylamino, and diethylamino. When R3 represents an alkoxy group, specifically methoxy, ethoxy, propyloxy, butoxy,
Examples include hexyloxy, decyloxy, icosyloxy, isopropyloxy, inbutyloxy, 58C-butyloxy, and t-butyloxy. Among these, preferred substituents have 2 to 7 carbon atoms, and particularly preferred are propylamino and propyloxy groups.

When R4 represents an aryl group in formula (I), typical examples include phenyl, l-naphthyl, 4-cyanophenyl, 4-chlorophenyl, and pentafluorophenyl. When R4 represents an alkyl group, representative examples include methyl, propyl, butyl, hexyl, decyl, isopropyl, 1-butyl, trifluoromethyl, heptafluoropropyl or undecafluoropentyl. Among these, a perfluoroaryl group or a perfluoroalkyl group is preferred, and a perfluoroalkyl group is particularly preferred. Furthermore, the substituent R4 may be further substituted with an octoday group, an alkoxy group, an aryloxy group, a sulfonamide group, a carbamoyl group, a hydroxyl group, etc.
, in which case the number of carbon atoms in R4 may exceed 10.

Examples of R6 include a hydrogen atom, an octoday group, a cyano group, a nitro group, an alkoxy group, a carbamoyl group, a sulfamoyl group, and an alkylamino group. Preferred R6 is a hydrogen atom.

Specific examples of the compound represented by formula (I) are shown below. However, the present invention is not limited to these.

In formula (III), X represents a chlorine atom or a bromine atom, and n represents 3 or 5. Preferably PCO2
or P B r x, particularly preferably PC
It is.

The compound of the present invention represented by the above formula (I) is produced by the synthetic process shown in Scheme 1 below.

Scheme 1 (In scheme 1, Y in formula (Vl) is a halogen atom (
For example, chlorine, bromine, iodine) and the formula (IV) ~
The meanings of R' and R"R3R'R' in (Vl) are the same as those shown in formula (I).) Next, Scheme 1 will be explained in detail.

First, the compound represented by the formula (I) is obtained by combining the compound represented by the formula (V) and the compound represented by the formula (VT) with the formula (
It can be synthesized via a compound represented by IV).

A compound represented by formula (IV) can be obtained by reacting a metal salt of a compound represented by formula (V) with a compound represented by formula (Vl). The metal salt of the compound represented by formula (V) is preferably an alkali metal salt, such as potassium salt or sodium salt. As the reaction solvent, aprotic solvents are preferred, such as anisole, xylene,
Bromobenzene, diglyme, dimethylformamide,
Dimethylacetamide and the like are used. The reaction temperature is 8
A temperature range of 0°C to 180°C, more preferably a range of 120°C to 180°C, is suitable for obtaining the desired product in a short time.

The compound represented by formula (I) is obtained by reacting the carboxylic acid represented by formula (H) with the compound represented by formula (III''), and the resulting reaction mixture is purified and separated without purification or separation. It is obtained by reacting a carboxylic acid represented by formula (II) with a compound of formula (I).
As the reaction solvent for the compound represented by II), an aprotic solvent is used, and halogenated solvents (methylene chloride,
(chloroform, dichloroethane, etc.), ethyl acetate, acetonitrile, tetrahydrofuran, etc. are used, and dimethylformamide, dimethylacetamide, etc. are sometimes added as a co-solvent.

The reaction temperature varies depending on the type of carboxylic acid of formula (II), but is carried out between -50°C and 150°C, preferably between -20°C and 100°C, particularly preferably between 20°C and 100°C.
The temperature is 90°C. The reaction time is preferably 5 minutes to 3 hours, more preferably 10 minutes to 2 hours. The optimum time is determined by detecting the disappearance of the raw material (II) by thin layer chromatography or liquid chromatography, and when this raw material is about 90 to
You can choose the time when it disappears 100%. Alternatively, the time change in the amount of the reaction product may be tracked by gas chromatography, and the time at which the amount reaches its maximum may be determined as the optimum time.

Carboxylic acid represented by formula (II) and formula (III)
The molar ratio of the compound represented by is from n:1 to 1:n
The ratio is preferably between nil and 1:2. Here, n has the same meaning as in formula (III).

A reaction product of the thus obtained carboxylic acid represented by formula (II) and a compound represented by formula (III) (
This reactant (hereinafter referred to as A) is reacted with a compound represented by formula (IV). The reaction mixture contains a reactive derivative corresponding to the starting carboxylic acid, such as an acid halide,
Contains active esters, etc. In the reaction between A and the compound represented by the formula (EV), the compound represented by the formula (IV) may be added to the reactant A as it is or after being dissolved in a solvent to form eA. Alternatively, A may be added to a solution in which the compound represented by formula (IV) is dissolved or suspended in a solvent. Examples of the solvent used here include the solvents described in the reaction of the carboxylic acid represented by formula (II) and the compound represented by formula (III). The reaction temperature is between -50°C and 150°C, preferably between -20°C and 10°C.
0°C, more preferably between 0°C and 90°C. The reaction time is preferably 109 to 6 hours, more preferably 20 minutes to 3 hours. The optimum time can be determined by tracking raw material loss and/or product build-up.

The amount of reactant A used is preferably between 1:5 and 5:1, expressed as a molar ratio of the acid halide corresponding to the carboxylic acid represented by formula (II) and the compound represented by formula (IV). is between 1:2 and 2.5:1, particularly preferably between 1:1.2 and 2:l.

Further, in the reaction between the compound represented by formula (IV) and A, a base may or may not be added, but it is preferable to add a base. Examples of bases include tertiary amines such as triethylamine and N-methylmorpholine, pyridine, lutidine, and 4-
In addition to pyridines such as dimethylaminopyridine, imidazole and the like are used. Among these, preferred bases are pyridine and imidazole.

In the present invention, the target compound corresponding to formula (I) can also be obtained by using the following compounds as the compound of formula (IV).

(Effects of the Invention) The method of the present invention provides an inexpensive and high-yield method for synthesizing 4-aryloxy-1,3-penzodioxoles. This 4-aryloxy-1,3-benzodioxole is a photographic compound 3-
It is an important compound as a synthetic intermediate for aryloxycatechols, and is industrially useful because it allows 3-aryloxycatechols to be synthesized in a small number of steps, in high yield, and at low cost by using the synthetic route via this synthesis method. It has extremely good effects.

(Example) Next, the present invention will be explained in more detail based on an example.
The present invention is not limited to these.

(P and Q are both optionally substituted phenyl groups or hydrogen atoms, and neither is a hydrogen atom.

RI R2, R3, and R5 have the same meanings as in formula (IV). ) Example 1 Synthesis of Exemplified Compound (I)-(1) (B) Heptafluorobutyric acid (2,57 g) and phosphorus trichloride (1,
65g) in acetonitrile (20TIll)
The reaction was carried out at ℃ for 30 minutes. The liquid A is (B) (6,18
g) and pyridine (1,98 g) in acetonitrile (20
TnR) suspension and allowed to react for 1 hour. Thereafter, ethyl acetate (30 Tnf) was added, and the mixture was washed with IN hydrochloric acid, water, and brine. The organic layer was dried over sodium sulfate, concentrated, and the residue was subjected to silica gel column chromatography (ethyl acetate-hexane 1:3). 7.0g of Exemplified Compound (1)-(1) as amorphous
(86% yield).

') INMR (CDCfiS) δ value (TMS standard)
0.95 (3H), 1.55 (2H), 3.35
(2H), 5.25(2)1), 6.05(ill
), 7.10 (1111,7,20(l)l),
7.30~7.60(15+1>, 7.80(01
1゜8.20(IH), 8.75(11() I)l
)m, IR(KBr)y 1220°1500,
1550.1600.1620.1740. :140
0 cm-'Also, even if diphenyl methyl ether or triphenyl methyl ether is used instead of the benzyl ether (B) as a raw material in this example, (I
)-(1) is obtained.

Example 2 Synthesis of exemplified compound (1)-(l l) (C) Synthesis was carried out in the same manner as in Example 1 except that 6.17 g of (C) was used in place of (B) in compound 1. Ta. As a result, 6.84 g (84% yield) of (1)-(11) was obtained as amorphous.

'HNMRCCDCI2s) δ value (TMS standard)
1.0 (3H).

1.75 (2H), 4.20 (2H), 5.25 (
21(), 7.25-7.65(17H), 7.
75 (LH), 8.20 (IH), 8.80 (
1) 1) ppm.

IR(KBr)y 1210.1550.160
0.1720.1740°3410 cm-' Example 3 Synthesis of Exemplified Compound (I)-(1) (1,79 g) was dissolved in acetonitrile (20d) at 50°C.
The mixture was allowed to react for 30 minutes. The liquid A is (B) (6.18g
) and imidazole (2.04 g) (7) ethyl acetate (2
0d) It was added to the suspension and allowed to react for 1 hour. Thereafter, the same treatment as in Example 1 was performed to obtain 7.73 g (95% yield) of (I)-(1) as amorphous.

Heptafluorobutyric acid (2,78 g) and Li80 trichloride Compound (I)-(1) (74,9 g) was dissolved in dimethylacetamide (100 TI1 g), 10% Pd/C (3,7 g) in ethyl acetate (200 d). Hydrogen pressure in the presence of 20kg/
Err? , and reacted at 85°C for 2 hours. Thereafter, the reaction solution was cooled to room temperature, filtered through Celite, and concentrated to obtain compound (■) as a dimethylacetamide solution. To this solution was added a solution of Compound (■) (28.6 g) in ethyl acetate (50 ml) under water cooling, and the mixture was allowed to react for 1 hour, and then further diluted with ethyl acetate (300 ml).

This solution was washed with water (200ml x 3 times), the organic layer was concentrated and the resulting crude crystals were washed with acetonitrile (250ml).
Compound (IX) was recrystallized from 61.5
g (obtained from compound (I)-(1) in 83% yield (decomposed at 270°C).

Compound (IX) (40.0g), Compound (X) (58
,0g) and triphenylphosphine (26,0g)
was reacted with tetrahydrofuran (800 ml) for 5 hours under medium rapid flow. Then water (about 2ρ), ethyl acetate (about 2j2
) and extracted twice, washed three times with 10% aqueous sodium bicarbonate solution, washed with 10% aqueous hydrochloric acid solution, and neutralized by washing with water. The ethyl acetate layer was thoroughly dried over anhydrous sodium sulfate, and the ethyl acetate was distilled off under reduced pressure. The residue was crystallized from acetonitrile (150m)-hexane (35m) to give 13.0g of compound (XI) (melting point 136-1
38°C) was obtained. This compound (Kari) was obtained by patent application in 1981-819.
No. 62, No. 62-117635, No. 62-26584
5, No. 63-51283, and No. 63-110050.

(Application example 2) Exemplary compound (1) - From (1), a cyan coupler intermediate (■) was obtained.Then, the reaction solution was washed with water (30 mf),
Hexane (50 Tnlll>) was added to the organic layer, and the precipitated crystals were collected by filtration to obtain 14.9 g of crude crystals of compound (Xll). These crystals were dissolved in dimethylacetamide (2
0ml) and 10% Pd dissolved in ethyl acetate (40ml)
-Hydrogen pressure 25 kg/ctrr in the presence of C (0.84 g)
After reacting at 85°C for 1 hour, ethyl acetate was distilled off under reduced pressure to obtain compound (■) as a dimethylacetamide solution. This compound can be further reacted with compounds (■) and (X) using the method shown in Application Example 1 to lead to cyan coupler (Xl).

Claims (1)

[Claims] (1) By reacting a carboxylic acid represented by formula (II) with a compound represented by formula (III) and then reacting the resulting reaction mixture with a compound represented by formula (IV), 4-aryloxy-1 represented by
, 3-benzodioxole. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 represent a hydrogen atom, an aromatic group having 6 to 10 carbon atoms, or an aliphatic group having 1 to 6 carbon atoms. .R again
^1 and R^2 may be bonded together, and in that case, the sum of the carbon numbers of R^1 and R^2 is 1 to 12. R^3 represents an amino group, an alkylamino group having 1 to 20 carbon atoms, or an alkoxy group. R^4 is carbon number 6~
10 represents an aryl group or an alkyl group having 1 to 10 carbon atoms. R^5 represents a benzyl group. ) Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^4 is synonymous with formula (I).) Formula (III) PX_n (X represents Cl or Br, n is 3 or 5) ) Formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, R^3, R^5 are formula (I)
is synonymous with )