JPH05262689A - Production of aldehyde derivative - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a production intermediate for an oxime derivative having excellent herbicidal activity in high yield and selectivity by reacting a phenolic compound with formaldehyde in the presence of a specific catalyst. CONSTITUTION:The objective 0-hydroxybenzaldehyde of formula II is produced by reacting a phenolic compound of formula I (X and Y are H, halogen, CF3 or 1-5C alkyl) [e.g. 3-(2-chloro-4-trifluoromethylphenoxy)phenol] with formaldehyde in the presence of a catalyst consisting of a tin compound containing an alkali metal and an alcoholate preferably at 110-170 deg. deg.C. The above catalyst is preferably an alcoholate, etc., containing alkali metal atom as well as tin atom and produced by the direct reaction of stannic chloride (SnCl4) with >=4 equivalent of an alkali metal alcoholate such as sodium ethoxide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing an aldehyde derivative. More specifically, the present invention is an important intermediate in the production of oxime derivatives having excellent herbicidal activity against broadleaf and / or fineleaf weeds.

[0002]

2. Description of the Related Art Conventionally, there have been the following methods for forming aldehydes by formylating phenols. (I) Guttermann method; a method for producing aldehydes by reacting phenols with hydrogen cyanide or by reacting cyanic zinc with hydrogen chloride using aluminum chloride or zinc chloride as a catalyst (Org. React.,
9:37, 1957). (Ii) Gattermann-Koch method; a method for producing aldehydes by reacting carbon monoxide and hydrogen chloride in the presence of aluminum chloride and copper chloride (J. Amer. Chem. Soc., Vol. 91,
4606, 1969). (Iii) A method using formyl fluoride and boron trifluoride (J. Amer. Chem. Soc., Vol. 82, page 2380, 1960). (Iv) Method using dichloromethyl alkyl ether or orthoformate; Method for reacting dichloromethyl alkyl ether or orthoformate in the presence of titanium tetrachloride or aluminum chloride, and then hydrolyzing to produce aldehydes (Chem ．Ber., Volume 93,
88 pages, 1960). (V) Vilsmeier reaction; a method for producing an aldehyde by reacting a compound obtained by reacting phosphorus oxychloride or thionyl chloride with an N-substituted formamide (Org
． Synth., Vol. 3, p. 98, 1955). (Vi) Reimer-Tiemann reaction; a method for producing aldehydes by reacting chloroform, bromoform, trichloroacetic acid, etc. in the presence of alkali (Ber., Vol. 9, 423).
P., 1876). (Vii) Duff reaction; a method of producing aldehydes by reacting hexamethylenetetramine in the presence of glycerin borate or acetic acid or trifluoroacetic acid (J.
Chem. Soc., P. 276, 1945). (Viii) A catalytic method using formalin; for example, a tin chloride compound (J.C.S. Per Rin I1862 (1
980)), titanium or zirconium compounds (JP-A-58)
-72536, JP-A-59-73537) and the like are known.

However, the methods (i), (ii), (i
In v) and (vi), toxic raw materials are used, which is not industrially advantageous. Also, the method (iii
In () and (iv), the raw material is expensive, and this cannot be said to be an industrially suitable method. Furthermore, in the method (v), a highly corrosive raw material must be used, and in this case, the apparatus is industrially expensive.

On the other hand, these methods are represented by the following formula (I)

[0005]

[Chemical 3]

[Wherein X and Y are the same or different and each represents a hydrogen atom, a halogen atom, —CF ₃ or a carbon number 1
~ 5 alkyl groups. ] When used for a phenol compound represented by the following formula (II)

[0007]

[Chemical 4]

[Where X and Y are as defined in formula (I). ] The compound represented by the formula [1] cannot be obtained at all or can be obtained only in an extremely low yield. In addition, structural isomers other than the target compound of formula (II), such as the following formula (III
)

[0009]

[Chemical 5]

[In the formula, X and Y have the same definitions as in formula (I). ] Are often generated, and are therefore inappropriate in many cases.

[0011]

OBJECTS OF THE INVENTION Therefore, the inventors of the present invention investigated the production method of o-hydroxybenzaldehyde represented by the above formula (II) with high yield and selectivity, and as a result, the conventional production method was found. In comparison with the above, a new method for obtaining a desired o-hydroxybenzaldehyde derivative in a high yield was found, and the present invention was completed.

[0012]

That is, the present invention is represented by the following formula (I)

[0013]

[Chemical 6]

[Wherein X and Y are the same or different and each represents a hydrogen atom, a halogen atom, -CF ₃ or a carbon atom number 1
~ 5 alkyl groups. ] The phenol compound represented by the formula and formaldehyde are reacted in the presence of a tin compound containing an alkali metal and an alcoholate, the following formula (II):

[0015]

[Chemical 7]

[Where X and Y are as defined in formula (I). ] It is a manufacturing method of o-hydroxy benzaldehyde represented by these.

The present invention will be described in detail below.

In the present invention, the phenol compound represented by the above formula (I) and formaldehyde such as paraformaldehyde or free formaldehyde are present in the presence of a tin compound containing an alkali metal and an alcoholate as catalyst components, and more preferably. Is a method of reacting in the presence of a base which is a catalyst promoter.

The formula (I) and the formula (I
Regarding X and Y in the compound of I), X and Y
Are the same or different and are hydrogen atom, halogen atom, -C
F ₃ or an alkyl group having 1 to 5 carbon atoms.

The halogen atom is, for example, fluorine, chlorine or bromine. The alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples thereof include methyl, ethyl, n-propyl, iso-propyl, n-butyl,
sec-butyl, iso-butyl, t-butyl, n-pentyl and the like.

In the above formula (I), a small number of X and Y
At least one is a halogen atom, -CF ₃Or carbon number 1
Is preferably an alkyl group of 5 to 5 and X is -CF.₃
It is particularly preferable that Y is a halogen atom.

The formaldehyde compounds used in the present invention are free formaldehyde and paraformaldehyde, the molar ratio of formaldehyde to the phenolic compound of formula (I) being generally from 2 to 6: 1 and preferably from 3 to 5 :. The range is 1.

The catalyst used to carry out the process of the present invention is a tin compound containing an alkali metal and an alcoholate. Examples of the alkali metal include sodium and potassium. On the other hand, as alcoholate, methyl, ethyl, n-
Propyl, iso-propyl, n-butyl, t-butyl, iso-butyl, sec-butyl, amyl and other aliphatic alcohols having 1 to 10 carbon atoms, cyclohexyl, cyclopentyl and other aliphatic alcohols having 1 to 10 carbon atoms Alternatively, there may be mentioned those comprising residues of phenols, etc., having 6 to 12 carbon atoms such as phenol, substituted phenols, naphthols and the like. One or more of these may be mixed and contained. In addition to the above-mentioned alkali metal and alcoholate groups, other ligands that do not affect the reaction may be contained as a part in the tin compound. Examples of such a ligand include β-diketones such as halogen acetylacetonate such as chlorine and bromine, 0-formylphenols such as 8-hydroxyquinoline and salicylaldehyde, and the like. It does not matter even if the tin compound itself is partially oxidized and associated to form a polymer.

In the catalyst composition of the present invention, it is necessary for the target formylation reaction to be carried out in good yield with the inclusion of an alkali metal such as sodium or potassium in a certain range with respect to tin. is there. The atomic ratio of alkali metal to tin in this catalyst composition is in the range of 0.01 to 2, preferably 0.1 to 1.5. If the amount of alkali metal is less than this range, the effect is weak and a sufficient yield cannot be obtained. Further, when the atomic ratio exceeds 2, the catalyst component becomes non-uniform and the yield is lowered. On the other hand, the alkoxy group is tin
One or more atoms and a maximum coordination number of 6 may be contained. The alkoxy group in this tin compound is the other alcohol or phenol component contained in the system during the reaction,
Alternatively, it is presumed that it undergoes a ligand exchange reaction with another component having a coordinating force, and is considered to have an important role also as a ligand on the gaff catalyst metal.

As the alkoxy compound of tin, a compound represented by the general formula S
n (OR)₂Or Sn (OR) _Four[Wherein R is lower
It is an alkyl group. ] Is known
[Reference Chem. Ber., 2560 (1963), J. Inorg. nucl. C
hem., 29 393 (1967), J. Chem. Soc., 4775 (195
7)]. However, these alkoxides, especially primary alcohols
Alkoxides are non-volatile and strongly associate or polymerize.
And is easily oxidized by oxygen in the air.
Satisfactory yield cannot be obtained when used as a catalyst for the reaction
In many cases. On the other hand, for example, tin tetrachloride SnCl_FourWhen
Direct reaction with more than 4 equivalents of alkali metal alcoholate
can get. Alco containing both alkali metal and tin metal atoms
A catalyst for this reaction, which is a so-called double alkoxide
Targeting formylation with good yield
The product can be obtained. As a double alkoxide
Is NaSn (OR)₉The composition of is described in the literature
(J. Chem. Soc., −)
It is also soluble in the reaction solvent of the present invention such as ren and has a favorable touch.
It can be given as an example of the medium. Other double arco
NaSn (OR) as the oxidant_FiveOr Na₂Sn
(OR)₆It is considered that the composition such as
When prepared with excess alkali metal alkoxide
If it is considered that they are a mixed composition of them,
Any of these can be cited as an example of a suitable catalyst. That
As mentioned above, part of the alkoxy group is inactive in the reaction.
Compounds that are replaced by other active ligands also act as catalysts for this reaction
Can be used.

The amount of the above-mentioned catalyst used may be a so-called catalytic amount with respect to the starting phenol of the formula (I), but is usually in the range of 0.01 to 0.2 equivalent, preferably 0.02 to 0.1 equivalent. is there. When the amount is less than the above range, the reaction rate is slow, and therefore it takes a long time to complete the reaction, which is not preferable, and when the amount exceeds the above range, the target product may be taken into the catalyst to impair the yield, which is not preferable. It is also uneconomical.

To further accelerate the reaction, catalyst promoters may be added to the reaction system. Examples of such an accelerator include tertiary amines. In addition to aliphatic and alicyclic tertiary amines, preferably pyridine, γ-picoline, β
-Aromatic amines such as picoline or quinoline and isoquinoline. A sufficient accelerating effect can be obtained by allowing them to be present in the reaction system in the same small amount as the catalyst. Therefore, the amount of these promoters used is such that
On the other hand, the amount is 0.01 mol or more, preferably 0.02 mol or more, and there is no particular upper limit. Not preferable.

In the present invention, the reaction temperature is 90 to 200.
C., preferably 110 to 170.degree. When the reaction temperature is lower than 90 ° C, the reaction is delayed and it takes a long time to complete the reaction, which is not preferable. On the other hand, when the temperature exceeds 200 ° C., side reactions are likely to occur, which may lead to a decrease in yield.

The present invention can be carried out under atmospheric pressure (open system) or under pressure (closed system). This choice is
It can be determined by the reaction temperature and the boiling point of the solvent used. Solvents that can be used here include aromatic carbon such as benzene, toluene, xylene, chlorobenzene, trimethylbenzene, tetralin, decalin and anisole, or an aliphatic hydrocarbon which is inert to the catalyst component,
There are ether etc. Therefore, for example, this reaction is
When it is carried out in a suitable temperature range of 30 ° C., it can be carried out simply in an open system in a solvent such as toluene, xylene or chlorobenzene.

[0030]

According to the method of the present invention, it becomes possible to obtain the target compound in a further step and in an excellent yield. Further, the catalyst tin compound used in the present invention is inexpensive and can be easily prepared, and further, formaldehyde which is a reaction raw material, a small amount of a base such as pyridine which is a catalyst accelerator,
This method is inexpensive, including the reaction solvent, and is an extremely advantageous method from an industrial and economic standpoint.

[0031]

EXAMPLES The present invention will be described in detail below with reference to examples.

[0032]

Example 1 (1) Preparation of catalyst 765 g of a 20% solution of commercially available sodium ethoxide was placed in a 1-liter flask, and stannic chloride Sn was added thereto with stirring.
130 g of Cl _{4 are} added dropwise. After the dropping, the mixture is heated under reflux on an oil bath for 2 hours. The resulting NaCl-based precipitate was filtered,
Concentrate the filtrate. To the concentrated residue, 400 ml of toluene was added, stirred well, and filtered again to remove the precipitate. Toluene was evaporated from the filtrate to dryness to obtain 114 g of an alkoxide catalyst containing 2 atoms of sodium and tin. A part of this solid was taken and the atomic ratio of Na / Sn was determined by ICP emission spectrometry, resulting in 0.50.

(2) Formylation reaction In a 100 ml three-necked flask, 45 m of xylene was used as a solvent.
1 g of 3- (2-chloro-4-trifluoromethylphenoxy) phenol (4.5 g), paraformaldehyde (1.5 g), γ-picoline (250 μl), and the catalyst (330 mg) prepared above were charged in an oil bath at 110 ° C to 120 ° C. The mixture was stirred in the temperature range of ° C for 3 hours. 0.3 g of paraformaldehyde was added every 30 minutes in 3 steps. After completion of the reaction, the solvent such as xylene was removed under reduced pressure, and the residue was separated and purified by silica gel column chromatography. As a result, 2-hydroxy-4- (2-chloro-4-
3.24 g (yield 66%) was obtained as a mixture of trifluoromethylphenoxy) benzaldehyde and 2-hydroxy-6- (2-chloro-4-trifluoromethylphenoxy) benzaldehyde. By proton NMR and HPLC, the production ratio of the former, which was the object, to the latter, which was its isomer, was 9.5.

[0034]

Example 2 (1) Preparation of catalyst 200 ml of isopropanol was placed in a 500 ml flask, and then 17.2 g of sodium metal was placed therein and heated.
Prepare a solution of sodium isopropoxide. Then, 43.2 g of stannic chloride was added dropwise thereto, and after the addition, another 2
Heat to reflux for hours. The formed precipitate of potassium chloride is filtered off, the filtrate is concentrated, and the residue is extracted with 100 ml of toluene. The extract was evaporated to dryness to obtain isopropoxide containing sodium and tin as a white solid. The atomic ratio of Na and Sn contained in this solid was 0.42 as a result of measurement by ICP emission spectrometry.

(2) Formylation reaction Instead of the catalyst of Example 1, 400 mg of isopropoxide containing sodium and tin was used as a catalyst to carry out the reaction under the same conditions. As a result, 2-hydroxy-4- (2-chloro-4-trifluoromethylphenoxy) benzaldehyde and 2-hydroxy-6- (2-chloro-4-trifluoromethylphenoxy) benzaldehyde were added to 6.7: 1. 3.21 g of formyl compound (yield 62%)
To give 3- (2-chloro-4-trifluoromethylphenoxy) phenol 0.32 g (conversion rate 93%)
Was recovered.

[0036]

Examples 3 to 11 (1) Preparation of catalyst In the same manner as in Example 1, double ethoxide with various ratios of sodium and tin was prepared from stannic chloride and a 20% solution of sodium ethoxide. Table 1 shows the weight of the solvent used in the formylation reaction and the atomic ratio of sodium to tin in the catalyst.

(2) Formylation reaction Using the catalyst prepared in the preceding paragraph, 100
3. 45 ml of xylene as a solvent in a ml flask.
5 g of 3- (2-chloro-4-trifluoromethylphenoxy) phenol, 250 μl of γ-picoline and paraformaldehyde were 1.5 g at the start of the reaction and then 30 g.
0.3 g was added every minute three times. Keep the oil bath temperature at 130 ° C, the reaction system temperature is 110-120 ° C,
The reaction time is 3 hours. The treatment after the reaction was performed in the same manner as in Example 1. The results are shown in Table 1.

[0038]

[Table 1]

[0039]

Examples 12 and 13 (1) Preparation of catalyst 7.2 g of metallic potassium was added to 100 ml of ethanol to prepare an ethanol solution of potassium ethoxide, and 10.7 g of stannic chloride SnCl ₄ was appropriately added thereto. To do. After completion of the dropwise addition, the mixture is heated under reflux for 2 hours, and the formed KCl precipitate is filtered off. Alcohol was evaporated from the filtrate in substantially the same manner as in Example 1, toluene extraction was performed, and toluene was evaporated to dryness from the extract to prepare double ethoxide of potassium and tin.

Similarly, 7.2 g of potassium and 100 μm
A double isopropoxide of potassium and tin is prepared from 1 of isopropanol.

(2) Formylation reaction Using the double alkoxide of potassium and tin prepared above, a formylation reaction under atmospheric pressure was carried out in the same manner as in Examples 4 to 10, and the results are shown in Table 2.

[0042]

[Table 2]

[0043]

Example 14 In a 100 ml autoclave, 330 mg of the same catalyst used in Example 10 and xylene 4 as a solvent were used.
4.5 g of raw material 3- (2-chloro-4-trifluoromethylphenoxy) phenol, 250 μl of γ-picoline, and 1.8 g of paraformaldehyde were added together with 5 ml, and 1
The reaction was carried out at 40 ° C for 1 hour. After completion of the reaction, xylene was distilled off under reduced pressure and the residue was separated and purified by silica gel column chromatography. As a result, the yield of the formylation reaction was 35%, the conversion rate was 73%, and the production ratio of the target product and the isomer was 8.8.

[0044]

Comparative Example 1 (1) Preparation of Catalyst Sn (OEt) ₄ Tin tetraethoxide Sn (OEt) ₄ was prepared according to the method described in the literature (J. Chem. Soc., P. 4775, 1957) and further depressurized. Distilled under. (Boiling point 55-60% 0.
5 mmHg) (2) Formylation reaction Using 330 mg of the above catalyst, 4.5 g of 3- (2-chloro-4-trifluoromethylphenoxy) phenol, 1.8 g of paraformaldehyde, 250 μ of γ-picoline
l, 110-120 using 45 ml of xylene as a solvent
The reaction was carried out at ℃ for 4 hours. After the completion of the reaction, the same treatment as in the previous example was conducted, resulting in a yield of the formylation product of 12% (0.59
g), raw material conversion rate 49%, target 2-hydroxy-4- (2-chloro-4-trifluoromethylphenoxy) benzaldehyde in the formylation product and isomer 2-hydroxy-6- (2-chloro) The production ratio with -4-trifluoromethylphenoxy) benzaldehyde was 12.5.

[0045]

Comparative Example 2 (1) Preparation of Catalyst According to the method described in the literature (J. Inorg. Nucl. Chem., 29
Vol. 393, 1967) Tin (II) ethoxide Sn (OEt) ₂ was prepared from stannous chloride Sncl ₂ and ethanol in the presence of triethylamine.

(2) Formylation reaction In the same manner as in Comparative Example 1, 210 mg of tin diethoxide prepared above was used in place of tin tetraethoxide to carry out the reaction under the same conditions. As a result, the yield of formylation reaction is 29%.
(1.44 g), the raw material conversion rate was 81%, and the production ratio of the target product and the isomer was 9.5.

[0047]

Examples 15 to 19 In a 100 ml flask, 300 mg of double ethoxide having a Na / Sn ratio of 0.51 used in Example 5 was used as a catalyst, and the starting material 3- (2-chloro-4) was used.
-Trifluoromethylphenoxy) phenol 4.5
g, 1.8 g of paraformaldehyde, and the base and solvent shown in Table 2 were reacted at a reaction temperature of 115 to 120 ° C. for 3 hours. As a result, the yield of the formylation reaction, the conversion rate of the starting materials, the desired product 2-hydroxy-4- (2-chloro-4-trifluorophenoxy) benzaldehyde and the isomer 2-hydroxy-6- (2 The ratio of chloro to 4-chloro-4-trifluoromethylphenoxy) benzal is shown in Table 3.

[0048]

[Table 3]

Claims (1)

[Claims] 1. The following formula (I): [Here, X and Y are the same or different and each is a hydrogen atom, a halogen atom, —CF ₃ or an alkyl group having 1 to 5 carbon atoms. ] The phenol compound represented by the formula and formaldehyde are reacted in the presence of a tin compound containing an alkali metal and an alcoholate, and the following formula (II): [Where X and Y are as defined in formula (I). ] The manufacturing method of o-hydroxy benzaldehyde represented by these.