JPH02255674A - 4-aryloxy-1,3-benzodioxoles and production thereof - Google Patents

Abstract

PURPOSE:To simply obtain the title partially new compound useful as an intermediate of compound for photography by acylating a 4-aryloxy-1,3-benzodioxole containing amino group at the 5position of aryl ring. CONSTITUTION:A compound shown by formula I (R<1> and R<2> are H, aromatic or aliphatic or R<1> and R<2> are bonded) R<3> is amino, alkylamino or alkoxy; R<4> is aryl, arylamino, alkyl, alkoxy, etc.; R<5> is H or substituent group) is acylated to give a 4-aryloxy-1,3-benzodioxole shown by formula II. A compound shown by formula III [R<11> and R<12> are phenyl or (CH2)n (n is 4 or 5); R<13> is alkylamino, etc.; R<14> is heptafluoropropyl, phenyl, etc.] among the compound shown by formula I is new. The formed compound shown by formula II is used as an intermediate to give a 3-aryloxycatechol as an intermediate of a compound for photography by a few processes in high yield and inexpensively.

Description

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

(Prior Art) 3-Aryloxycatechols are compounds useful as intermediates for photographic compounds.
It is described in No. 046. Furthermore, 3-aryloxycatechols are compounds that are expected to be used as intermediates for preservatives, rust preventives, preservatives, pharmaceuticals, dyes, and the like.

(Problems to be Solved by the Invention) 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 the drawback that the number of reaction steps from the raw material heronitrobenzene to the aryloxycatechol was large and the overall synthesis yield was low. Therefore, it has been desired to develop a synthetic intermediate that can synthesize aryloxycatechols at low cost with a small number of steps and high yield.

(Means for Solving the Problems) The present inventors have conducted repeated research to develop intermediates that can synthesize 3-aryloxycatechols in a small number of steps, in high yields, and at low cost. It has been found that the above problems can be solved by using the compound represented by formula (I).

The object of the present invention has been achieved with 4-aryloxy-1,3-benzodioxoles represented by the following formula (I).

Formula (I) (wherein R1 and R12 represent a hydrogen atom, an aromatic group having 6 to 10 carbon atoms, or an aliphatic group having 1 to 6 carbon atoms, and 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 or an alkoxy group having 1 to 20 carbon atoms, R4 represents an amino group having 6 to 10 carbon atoms,
Aryl group, arylamino group or aryloxy group or having 1 to 10 carbon atoms.

The present invention will be described in detail below.

When R1 or R2 represents an aromatic group in formula (I), a typical example is a phenyl group, and Table 1 shows examples when phenyl groups are linked together. Further, when R1 or R2 represents an aliphatic group, typical examples include methyl, ethyl, propyl, isopropyl, butyl or cyclohexyl.
As an example when R1 and R2 are connected to form a ring.

can be mentioned. Among these, preferred substituents are those shown in Table 1.

Among these, No. 1.2.3 and No. 8 are particularly preferred.

When R3 represents an alkylamino group in formula (I), specific examples include methylamino, ethylamino, propylamino, butylamino, hexylamino, decylamino, icosylamino, isopropylamino, isobutyloxy, 5ec-butylamino, t -butylamino,
Examples include dimethylamino, methylethylamino, and diethylamino. When R:l represents an alkoxy group, specific examples thereof include methoxy, ethoxy, pro-ruoxy, butoxy, hexyloxy, decyloxy, icosyloxy, iso-pro-ruoxy, isobutyloxy, 5ec-butyloxy and t-butyloxy. Among these, preferred substituents are those having 2 to 4 carbon atoms, and particularly preferred are pro-, ruamino, and propyloxy groups.

When R4 represents an aryl group in formula (I), typical examples include phenyl, 1-naphthyl, 4-diaphenyl, and 4-chlorophenyl. When R4 represents an arylamino group, typical examples include anilino, -naphthylamino, 4-cyanophenylamino, 4-chlorophenylamino or 3-chloro-4-cyanoanilino. When R4 represents an aryloxy group, a typical example is a phenoxy group. When R4 represents an alkyl group, representative examples include methyl, propyl, butyl, hexyl, decyl, isopropyl, or hebutafluoropropyl. When R4 represents an alkylamino group, representative examples include methylamino, propylamino, hexylamino, decylamino, isopro-ruamino, t-butylamino or cyclohexylamino. When R4 represents an alkoxy group, representative examples include methoxy, propyloxy, hexyloxy, decyloxy, isopropyloxy, t-butyloxy, and cyclohexyloxy. Among these, preferable substituted 3R' are an aryl group, an arylamino group, an alkyl group, and an alkylamino group. Particularly preferred substituents R4 are an arylamino group and an alkyl group.

Furthermore, the substituent R4 may be further substituted with a hexagroup, an alkoxy group, an aryloxy group, a sulfonamide group, a carbamoyl group, an amino group, a hydroxyl group, a carboxyl group, a sulfonic acid group, etc. In that case, the number of carbon atoms in R4 is may exceed 10.

Examples of R5 include a hydrogen atom, a heguchi group, a cyano group, a nitro group, an alkoxy group, a carbamoyl group, a sulfamoyl group, and an alkylamino group. Preferred Rs is a hydrogen atom.

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

The 4-aryloxy-1,3-benzodioxoles represented by formula (I) are preferably 4-aryloxy-1°3-benzodioxoles represented by formula (IA) Scheme 1 (wherein R", R" is a phenyl group or -(CH2)n
- group (n represents 4 or 5), R'' represents a lower alkylamino group, lower alkoxy group, R represents a hebutafluoropropyl group, 4-cyanophenylamino group, or phenyl group, R "represents a hydrogen atom." The compound of the present invention represented by the above formula (I) is produced by the synthetic process shown in Scheme 1 below.

(In scheme 1, Y in formula (m) represents a halogen atom (e.g., chlorine, bromine, iodine), and formula (■) ~ (rV
The meanings of R', R'', R', and R'- in ) 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) can be synthesized from the compound represented by the formula (n) and the compound represented by t(III) via the compound represented by the formula (IT).

The compound represented by formula (17) is obtained by reacting the metal salt of the compound represented by formula (II) with the compound represented by formula (III).As the metal salt of the compound represented by formula (II), Salts of alkali metals are preferred, such as potassium salts and sodium salts.As the reaction solvent, aprotic solvents are preferred.Anisole, xylene, bromobenzene, diglyme, dimethylformamide, dimethylacetamide, etc. are used.The reaction temperature is 80°C. to 180°C, more preferably 120°C.
A temperature range of 180°C to 180°C is suitable for obtaining the desired product in a short time.

A compound represented by formula (I) can be obtained by representing formula (IV). Here, R4 has the same meaning as defined in formula (I). The compound represented by X can also be obtained by reacting with a compound represented by formula (IV) or by reacting with R'-Co2H in the presence of a condensing agent such as dicyclohexylcarbodiimide, phosphorus trichloride, phosphorus oxychloride, etc. be able to. Here, R4 has the same meaning as defined in formula (1).

As the reaction solvent, an aprotic solvent is used, such as halogenated solvents (methylene chloride, chloroform, dichloroethane, etc.), ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, dimethylacetamide, etc. Although the reaction temperature varies depending on the method of introducing the R'-C- group, it is preferably carried out between 10°C and 100°C.

When synthesizing the compound represented by formula (1), Formula 1 is used in a molar ratio of 0.5 to 5 times, preferably 0.9 to 2 times to obtain the compound represented by formula (I). can.

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

(P and Q are both optionally substituted phenyl groups or hydrogen atoms, and neither is a hydrogen atom,
R', R'', R'', and R' have the same meanings as in formula (IV). ) (Effect of the invention) By using the 4-aryloxy-1,3-benzodioxole of the present invention, 3-
Aryloxy-catechols can be synthesized,
(2) It is especially valuable as a key intermediate for functional cyan couplers useful in color photographic materials.

Further, according to the method of the present invention, 4-aryloxy-1,3-benzodioxoles that exhibit the above-mentioned excellent effects can be synthesized economically and in high yield.

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

Example 1 Synthesis of Exemplified Compound (I)-(1) (A) Compound A (1.24 g) and hebutafluorobutanoic anhydride (0.74 nl) were dissolved in acetonitrile (lOTnii).
) The reaction was carried out under live reflux for 2 hours. After distilling off the acetonitrile under reduced pressure, the exemplified compound (I) was purified using a silica gel column (eluent: ethyl acetate-hexane 1:3).
1.34 g (82% yield) of -(1) was obtained as amorphous.

"IINMR (CDCJL s) 8 values (7MS standard) 0.95 (3H), 1.55 (2) 1), 3
15 (2H), 5.25 (2H), 6.05 (IH
), 7.10 (IH), 7.20 (IH), 7.
30-7.60 (15N), 7.80 (18).

8.20 (IH), 8.75 (IH) ppm,
IR(KBr)y 1220゜1500, 155
0.1600.1620.1740.3400 cta
-'Also, even if a diphenyl methyl ether or a triphenyl methyl ether is used instead of the benzyl ether of (A) as a raw material in this example, (I) -(
A compound corresponding to 1) is obtained.

Example 2 Synthesis of Exemplified Compound (I)-(11) (C) Compound (C) (1.24 g) and hebutafluorobutanoic anhydride (0.74 d) were reacted under live reflux in acetonitrile (10%) for 2 hours. After cooling the reaction solution to room temperature, ethyl acetate (20 ml?) was added and washed with saturated sodium hydrogen carbonate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the obtained oil was purified using a silica gel column (eluent: ethyl acetate-hexane=4) to obtain exemplified compound (I)-(11). ) was obtained as an amorphous product in an amount of 1.14 g (70% yield).

'IINMR (CDC statement,) δ value (7MS standard)
1.0 (3H).

1.75 (211), 4.20 (2H), 5.25
(2H), 7.25-7.65 (178), 7.
75 (ill), 8.20 (IH), 8.80
(IH) PI) Otori.

IR(KBr)y 1210.1550.1600
．． 1720.1740°3410 cm-' Example 3 Synthesis of Exemplary Compounds (1) to (12) (C) Compound (c) (1,24 g) and benzoyl chloride (
0.26) and imidazole (0.17 g) were reacted in acetonitrile at room temperature for 4 hours and then left to stand for 2 nights. The precipitated crystals were collected by filtration and washed with ethyl acetate and hexane to obtain 1.26 g of exemplified compound (I)-(12) (
92% yield) was obtained. Melting point 167°C Example 4 Synthesis of exemplified compound (I)-(13) (211), 5.10 (211), 6.10 (IH
), 7.20-7.65 (2211).

7.75 (IH) ppm, IR (neat) y
1310.1530.16:10°1720, 224
0. 3380 cm-'(C)
(D) Compound (C) (1,24g) and compound (D) (o,5
3g), Imidazo-J Shiku0. t4g) was refluxed for 3 hours in acetonitrile (10ml). Ethyl acetate (20ml)
After diluting with water, the mixture was washed with 1N hydrochloric acid and a saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over anhydrous sodium sulfate and then concentrated under pressure. The residue was purified with a silica gel column (eluent: ethyl acetate-hexane 1:4) to obtain 0.72 g of exemplified compound (I)-(13) as an oil (
47% yield) was obtained. 'HNMR (CDCRi) δ
Value (7MS standard) 0.95 (3H), 1.70 (2
H), 4.20 (211), 4.50 (Application example 1) Exemplary compound (1) Synthesis of cyan coupler (IX) from (1) (W) C3H.

Compound (1)-(1) (74.9 g) was dissolved in dimethylacetamide (roomed) and ethyl acetate (10% in 200 ml).
Hydrogen pressure in the presence of %Pd/C (3.7 g) 20 kg
/C, the reaction was carried out at 85°C for 2 hours. Thereafter, the reaction solution was cooled to room temperature, filtered through Celite, and concentrated to obtain compound (V) as a dimethylacetamide solution. Add compound (■) (28,'6g) to this solution under water cooling.
) in ethyl acetate (50T11) was added and reacted for 1 hour, followed by further addition of ethyl acetate (300Tn[!>) for dilution.

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

Compound (■) (40,0g), Compound (■) (58,0
g) and triphenylphosphine (26.0 g) were reacted under live reflux of tetrahydrofuran (800-) for 5 hours. The water was removed (approximately 21%), ethyl acetate (approximately 2Li) was added, extracted twice, washed three times with a 10% aqueous sodium bicarbonate solution, washed with a 10% aqueous hydrochloric acid solution, and neutralized by washing with water.

The ethyl acetate layer was thoroughly dried with anhydrous sodium sulfate.

Ethyl acetate was distilled off under reduced pressure. Compound (IK) was obtained in 13. by crystallizing the residue from acetonitrile (150TrIll)-hexane (35m). Og (melting point 13
6-138°C) was obtained. This compound (IX) was obtained by patent application in 1982.
-819°62, 62-117635, 62-
No. 265845, No. 63-51283, No. 63-11
It is a useful compound having the performance as described in No. 0050.

(Application example 2) From exemplified compound (I)-(1), cyan coupler intermediate ('/)(V) Compound (I)-(1) (15 g) was mixed with ethyl acetate (30 m
After dissolving 1) in acetonitrile (30d), concentrated hydrochloric acid (Iordj) was added and the mixture was refluxed for 1 hour.

Thereafter, the reaction solution was washed with water (30 ml), hexane (50 ml) was added to the organic layer, and the precipitated crystals were collected by filtration to obtain 14.9 g of crude crystals of compound (X). (20T11) and 10% Pd-C (0,8
After reacting for 1 hour at 85°C under a hydrogen pressure of 25 kg/crn' in the presence of 4 g), compound (V) was obtained as a dimethylacetamide solution by distilling off ethyl acetate under reduced pressure. This compound can be further reacted with compound (1, (W)) using the method shown in Application Example 1 to lead to cyan coupler (IK).

Claims (2)

[Claims] (1) Production of benzodioxoles characterized by acylating a compound represented by formula (IV) to obtain 4-aryloxy-1,3-benzodioxoles represented by formula (I) below. Method. 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 aryl group, arylamino group or aryloxy group, or an alkyl group, alkylamino group or alkoxy group having 1 to 10 carbon atoms. R^5 represents a hydrogen atom or a substituent. ) 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 ) (2) 4-aryloxy- represented by formula (IA)
1,3-benzodioxoles. Formula (IA) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1^1 and R^1^2 are phenyl groups or -
(CH_2)_n- group (n represents 4 or 5), R^1^3 represents a lower alkylamino group or lower alkoxy group, R^1^4 represents a heptafluoropropyl group, 4
-represents a cyanophenylamino group or a phenyl group, R
^1^5 indicates a hydrogen atom. )