JPS59204154A - Acetal derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R1 and R2 are lower alkyl or R1 and R2 link at the terminals thereof to form alkylene; R3 is H or lower acyl). EXAMPLE:3-Amino-4-fluor-benzaldehyde ethylene acetal. USE:Useful as a synthetic intermediate for aldehyde compounds which are synthetic raw materials for insecticides and acaricides. PREPARATION:A nitrobenzene derivative of formula II is catalytically reduced in the presence of a catalyst, e.g. palladium-carbon or platinum dioxide, in a solvent, e.g. methanol or ethanol, at 10-30 deg.C to give the aimed compound of formula I (R3 is H).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound of the general formula (I) [wherein R1 and R2 both represent a lower alkyl group, or Ro and R2 are bonded at the terminals and represent an alkylene group; Represents a hydrogen atom or a lower acyl group. ] and its production method.

represents a nyl group or l-propynyl group.

Melon represents a group represented by the general formula % (where X represents a chlorine atom or a bromine atom). ] It has been discovered that the novel ester compound shown below has excellent insecticidal and acaricidal activity.

As a result of various studies on the method of synthesizing the alcohol component of the ester compound represented by the above general formula 1), the present inventors found that the acetal derivative represented by the above general formula (I) and the general formula @) [In the formula, R4 has the same meaning as above.

] The bromobenzene derivative represented by the formula 1) is reacted with a base in the presence of a base or a copper compound, and then deacylated if necessary and then deacetalized to produce an ester compound represented by the above general formula 1). General formula serving as a raw material for synthesis [wherein R4 has the same meaning as above. It was discovered that the aldehyde compound represented by the formula (I) can be obtained efficiently, and the acetal derivative represented by the general formula (I) was found to be an important intermediate thereof, leading to the completion of the present invention.

That is, the present invention provides an acetal derivative represented by the general formula (I) and a method for producing the same, [wherein 几□ and R
2 has the same meaning as above. ] General formula (■') obtained by catalytically reducing the nitrobenzene derivative represented by [In the formula, R1 and R2 have the same meanings as above. ] A method for producing an acetal derivative represented by the general formula (I#) by further reacting the acetal derivative with a lower carboxylic acid anhydride or a lower carboxylic acid halide [wherein R1 and R2 have the same meanings as above] However, it currently represents a lower acyl group. ] The present invention provides a method for producing an acetal derivative represented by the following.

The present invention will be explained in detail below.

In the acetal derivative represented by the general formula (I), the substituents R1 and R2 include a lower alkyl group such as a methyl group, an ethyl group, and an n-propyl group; For example, it represents a group.

In the method for producing the acetal derivative of the present invention represented by the general formula (I), the catalyst for catalytic reduction of the nitrobenzene derivative represented by the general formula (V) is palladium-
A common catalyst used to reduce an aromatic nitro compound to an aniline derivative, typified by carbon and platinum dioxide, is used, and the amount used is 0. .01-10 mol%,
Preferably, the range is from o to 5 mol%.

Further, examples of the solvent used in this catalytic reduction reaction include alcoholic solvents such as methanol and ethanol, and inert solvents such as acetic acid.

The pressure of the hydrogen gas used is in the range of 1 to 10 atm, preferably 1 to 8 atm, and the reaction temperature is in the range of 0°C to the boiling point of the solvent used, preferably 1O to ao'c.

After the catalytic reduction reaction as described above, the desired general formula (1') is obtained by removing the catalyst and distilling off the solvent.
An acetal derivative represented by can be obtained. At this time, it is desirable to dry the reaction solvent in advance before distilling off the solvent.

The acetal derivative represented by the general formula (I') thus obtained is reacted with a lower carboxylic acid anhydride or a lower carboxylic acid chloride in the presence of a deoxidizing agent such as pyridine or triethylamine. Through the acylation reaction, an acetal derivative represented by the general formula (I#) can be obtained.

The nitrobenzene derivative represented by the general formula (V) related to the present invention is prepared by adding ethylene glycol, methyl orthoformate, orthoformic acid to 4-fluoro-3-nitrobenzaldehyde in the presence of p-)luenesulfonic acid or sulfuric acid. It can be easily obtained by a normal acetalization reaction by reacting ethyl or the like.

The present invention will be explained in more detail below with reference to Examples and Reference Examples, but the present invention is of course not limited to these.

Example 1 4-Fluoro-8-nitrobenzaldehyde ethylene acetal 3. Of was dissolved in 100 tttt of ethyl acetate, 100 tttt of platinum dioxide was added thereto, and a catalytic reduction reaction was carried out at room temperature for 8 hours while introducing hydrogen gas under normal pressure.

At this point, no early hydrogen gas absorption was observed.
Further, as a result of analysis of the reaction product by gas chromatography, no starting material compound remained.

Next, the reaction solution was filtered through Celite, and the resulting filtrate was dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 2.5y of extremely pure 3-amino-4-fluorobenzaldehyde ethylene acecool.

Yield 97% m, p 48-49.5°C Example 2 4-fluoro-3-nitrobenzaldehyde ethylene acetal 8.0 flz99.5% ethanol 100 m
200 mg of 5% palladium-carbon was added thereto, and a reduction reaction was carried out at room temperature for 8 hours while introducing hydrogen gas under normal pressure.

Next, 200q of 5% palladium-carbon was further added to the reaction solution, and the mixture was contacted for 1 hour under the same conditions to carry out a simple reaction.

At this point, no absorption of deuterium gas was observed.
Further, as a result of analysis of the reaction product by gas chromatography, no starting material compound remained.

Next, the reaction solution was filtered through Celite, and the obtained P solution was
After concentrating to 0-, it was poured into a 50 M1 saturated aqueous sodium hydrogen carbonate solution and extracted with ether.

The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain a product of 2.71 as a residue.

The product was dried in pyridine for 20 minutes. 2.g/ of acetic anhydride under water cooling. Of was added dropwise while stirring. After dripping,
After continuing to stir at room temperature for an additional 8 hours, the reaction solution was poured into ice cubes.
and extracted with ether.

The organic layer was washed with water and an aqueous copper sulfate solution to remove pyridine, and then washed twice with a saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off to yield 2.6 g as a residue. I got something.

The product was then purified by silica gel column chromatography (eluent: chloroform) to obtain 1.90 y of pure 3-acetamino-4-fluorobenzaldehyde ethylene acetal.

Yield 59% m, p 58.2°C Reference Example 1 4-Fluoro-3-acetaminobenzaldehyde ethylene acetal 0.5.2y1 Potassium carbonate 0.421
．． Cuprous chloride 0.07f and hyfromobenzene 8.62
Put g into the reactor and reduce the internal temperature to 140-150° under nitrogen flow.
The mixture was stirred at C for 13 hours.

After the reaction solution was allowed to cool, it was filtered through Celite, and the resulting filtrate solution was extracted twice with ether. The extract was washed once with a saturated aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain a product of 0.951 as a residue.

The product was then treated with 20 mL of IN-sodium hydroxide solution.
After stirring at room temperature for 2 hours, 20 ml of 10% sulfuric acid was gradually added dropwise to this while cooling, and after the dropwise addition, the mixture was stirred for 2 hours.The reaction solution was extracted twice with ether. The extract was washed with a saturated aqueous sodium bicarbonate solution, then dried over anhydrous magnesium sulfate, and the ether was distilled off.

The obtained residue was purified by silica gel column chromatography (eluent: methylene chloride) to obtain pure 3-anilino-4-fluorobenzaldehyde.

Yield 81% m, p 115-117°C Reference Example 2 3-amino-4-fluorobenzaldehyde ethylene acetal 0.80f, potassium carbonate 0.2'lf/, cuprous chloride 0.05F and bromobenzene t, Place the aoy into a reaction container and maintain the internal temperature to 180-140°C under a nitrogen stream.
The mixture was stirred for 10 hours.

After cooling the reaction solution, 10 g of 10% hydrochloric acid was added to it.
The mixture was stirred at 50° C. for 2 hours, and then the reaction solution was filtered through celite, the filtrate was neutralized with sodium hydroxide, and extracted twice with ether.

The extract was washed once with a saturated aqueous sodium bicarbonate solution,
After drying over anhydrous magnesium sulfate, the solvent was distilled off.

The resulting residue was subjected to silica gel column chromatography (
Eluent: methylene chloride) to obtain 0.141 of pure 3-anilino-4-fluorobenzaldehyde.

Yield 33% Reference Example 3 4-fluoro-8-nitrobenzaldehyde 10//,
After dissolving 5.5y of ethylene glycol and 100 f/If of P-1 toluene sulfonic acid in 50 ml of toluene, azeotropic dehydration was carried out while adding 100 ml of toluene dropwise under heating and reflux to obtain an approximately 100 dilute toluene solution containing water. /2
It took time to distill it out.

The content liquid was analyzed by gas chromatography, and the conversion rate of the raw material was 98%.

After the reaction solution was allowed to cool, it was diluted with a saturated aqueous sodium hydrogen carbonate solution and separated.

The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 12.8y of 4-fluoro-3-nitro-benzaldehyde ethylene acecure as a pale yellow oil. (Yield: 97.6
%).

The product was fairly pure from its gas chromatogram and NM,a spectrum.

nD 1.508O NMR data (0DCd3.TMS) 6.80-7.80 (m, 8H) 5.70 (8, LH) 8.90-4.10 (m, 4fl[) Procedural amendment (
Portrait)? f5y) 1 Indication of the case Showa S: What year Patent application No. 79 and No. 01 2, Title of the invention Aceter, I/Induction related and 0 0 separation law 3 Person making the amendment Relationship with the case Patent applicant 5-15 Kitahama, Higashi-ku, Osaka (209) Representative of Sumitomo Chemical Co., Ltd. -t 77 Mail: 4, Agent 5-15 Kitahama, Higashi-ku, Osaka, Japan Full text of specification to be amended, content of amendment Procedures for amendment Written by Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office, June 3, 1982 (1) Indication of the case 1982 Patent Application No. 75808 (2) Name of the invention Acetal derivatives and their manufacturing process 8, Person making the amendment Relationship to the incident Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative Hijikata
Take 4, Agent address: 5-15 Kitahama, Higashi-ku, Osaka City, Detailed explanation of the invention in the specification subject to amendment, column 6, Contents of amendment (1) June 13, 1981: Procedural amendment ( In the fifth line from the bottom of page 13, the word "solution" is corrected to "aqueous solution."

(2) From the bottom of page 18, in the third line, the word "sulfuric acid" is corrected to "hydrochloric acid." (3) From the bottom of page 14, in the bottom line of page 16, the word "sodium hydroxide" is corrected. Correct it to "aqueous sodium hydroxide solution."

(4) Add the following after the bottom line of page 16.

[Example 3 2.43 y of 4-fluoro-3-nitrobenzaldehyde diethyl acecure was dissolved in ethyl acetate lO(l me), 100 my of platinum dioxide was added thereto, and the mixture was heated to room temperature while introducing hydrogen gas under normal pressure. A catalytic reduction reaction was carried out for 6 hours.

Even at this point, no absorption of hydrogen gas was observed.
Further, as a result of analysis of the reaction product by gas chromatography, no starting material compound remained. Next, the reaction solution was filtered through Serai II, and the obtained solution F was dried over anhydrous magnesium sulfate, the solvent was distilled off, and almost pure 3-amino-
4-fluorobenzaldehyde diethyl acetal 1.
Got 50p.

Yield 70% nD23,01.5620 Reference Example 4 4-Fluoro-3-nitrobenzaldehyde 5, Oy was dissolved in ethyl orthoformate I B, L P, p-)
100~ of luenesulfonic acid was added, and the mixture was left to stand at room temperature for 5 hours. When the content liquid was analyzed by gas chromatography, the conversion rate of the raw material was 95%.

Then, after distilling off excess ethyl orthformate, vacuum distillation was performed to obtain 5.52 g of 4-fluoro-8-nitrobenzaldehyde diethyl acetal as a pale yellow oily substance.

The compound was nearly pure from its gas chromatogram and NMR spectrum. Yield 76% NMR data (CDC#a, TMS, δ value) 7.
l O ~ 8.80 (m, BH) 5.50 (S, L
H) Weight: 3.55 (g, 4H) 1.20 (t, 6H) Reference example 5 4-fluoro-3-acetaminobenzaldehyde diethylacecool 1.0y, potassium carbonate 0.7:dy,
Cuprous chloride 0. l B y and bromobenzene6.
45y was placed in a reaction container and the internal temperature was raised to 140-1.
The mixture was stirred at 50°C for 15 hours.

After the reaction solution was allowed to cool, it was filtered and the reactor was washed with ether. The obtained P solution was washed once with a saturated aqueous sodium bicarbonate solution, dried over anhydrous sulfuric acid, and then the solvent was distilled off to obtain a 1.98y product as a residual liquid.

Next, 2 Q rne of an IN-sulfur hydroxide aqueous solution was added to the product, and the mixture was stirred at room temperature for 2 to 2 hours.

The reaction solution was extracted twice with ether, the extract was washed with a saturated sodium bicarbonate aqueous solution, and then dried over anhydrous magnesium sulfate, and the ether was distilled off.

The resulting residual liquid was subjected to silica gel column chromatography (
Eluent: methylene chloride) to give 0.49y of pure 8-anilino-4-fluorobenzaldehyde.

Yield 65%

Claims (1)

[Claims] [In the formula, both R and R2 represent a lower alkyl group, or R1 and R2 are bonded at the terminals to represent an alkylene group, and R3 represents a hydrogen atom or a lower acyl group. ] Acetal derivative shown. (2) General formula [wherein R1 and R2 both represent a lower alkyl group, or R1 and R2 are bonded at the terminals to represent an alkylene group. ] A general formula characterized by catalytically reducing a nitrobenzene derivative represented by the formula [wherein the pore and R2 have the same meanings as above. ] A method for producing an acetal derivative shown in (8) General formula [wherein R1 and R2 both represent a lower alkyl group, or R1 and R2 are bonded at the terminals to represent an alkylene group. ] The nitrobenzene derivative shown above is catalytically reduced to obtain a general formula: [wherein R1 and R2 have the same meanings as above.] ] A general formula characterized by reacting an acetal derivative represented by a lower carboxylic acid anhydride or a lower carboxylic acid/monide [wherein, 几 and R2 represent the same meanings as above, and are now lower acyl groups] represents. ] A method for producing an acetal derivative.