JPS6113713B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyalkyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman. More specifically, polyalkyl-2-(2,4-dihydroxyphenyl) is useful as a manufacturing intermediate for agricultural chemicals, medicines, resin compounding agents, etc., or as a manufacturing intermediate for monomer components of copolymers for resin modification. The present invention relates to a method for producing enyl)-7-hydroxychroman. Polyalkyl-2- which is a compound of the present invention
When (2,4-dihydroxyphenyl)-7-hydroxychroman is thermally decomposed, the general formula [] (In the formula, R ¹ , R ² and R ⁴ each have an arbitrary alkyl group having 1 to 3 carbon atoms, and R ³ is a hydrogen atom or an arbitrary alkyl group having 1 to 2 carbon atoms.) Polyalkyl-7-hydroxy-4H-chromene is obtained. This polyalkyl-7-hydroxy-4H-chromene is an insecticide,
It can be used as an intermediate in the production of agricultural chemicals such as herbicides and fungicides, pharmaceuticals, fragrances, and formulations for thermoplastic resins such as polyolefins. For example, if O-ethyl-S-ethyl-O-(2,4,4-trimethyl-1,4-benzopyran-7-yl) phosphorothioate is produced using this, it has an excellent insecticidal effect against diamondback moths etc. This is a new insecticide that exhibits
Also, 2, 4, 4 represented by the above general formula []
-trialkyl-7-hydroxy-4H-chromene or 2,3,4,4-tetraalkyl-7-
Since hydroxy-4H-chromene exhibits antibacterial activity, it can be used as an antibacterial agent or bactericidal agent. Furthermore, the compound represented by the general formula [] exhibits superior herbicidal activity against, for example, paddy field weeds and upland weeds, compared to other compounds having similar structures. Furthermore, since the compound represented by the general formula [] has a vinyl ether type double bond, it exhibits cationic polymerizability, and a homopolymer and a copolymer with an aliphatic olefin or an aromatic olefin can be obtained. It will be done. Since these homopolymers or copolymers have phenolic hydroxyl groups, they can be used for various purposes, such as weather resistance improvers, water resistance improvers, and paint film strength improvers for various polymer coatings. Furthermore, the above-mentioned homopolymers and copolymers have a lower melt viscosity than other similar polymers with similar softening points, and therefore have the advantage of improved workability. The present inventors investigated a method for producing polyalkyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman with good yield and found that resorcinol and a specific The present invention was achieved by discovering that the above object can be achieved by reacting an aliphatic ketone or an unsaturated aliphatic ketone in the presence of a Lewis acid. That is, the present invention provides resorcinol and the general formula [] R ¹ R ² C=0 [] (wherein R ¹ and R ² each have 1 to 3 carbon atoms.
represents any alkyl group. ) Aliphatic ketone or general formula [] (In the formula, R ¹ , R ² and R ⁴ each represent an arbitrary alkyl group having 1 to 3 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.)
A general formula characterized by condensing an unsaturated aliphatic ketone (b) represented by in the presence of a Lewis acid described below [] (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.)
This is a method for producing (dihydroxyphenyl)-7-hydroxychroman. As the raw material resorcin (a), any resorcin obtained by any method can be used. Among the raw ketones, aliphatic ketones have the general formula [] R ¹ R ² C=0 [] (wherein R ¹ and R ² each have 1 to 3 carbon atoms.
represents any alkyl group. ), more specifically, in the general formula [], R ¹ and R ² are each an alkyl group having 1 to 3 carbon atoms, and at least one of R ¹ and R ² is an aliphatic ketone represented by One is a primary alkyl group. For example, acetone, methyl ethyl ketone,
Examples include methylpropylketone, diethylketone, ethylpropylketone, and dipropylketone. Among these aliphatic ketones, it is preferred to use acetone. Among raw ketones, unsaturated aliphatic ketones have the general formula [] (In the formula, R ¹ , R ² and R ⁴ each represent an arbitrary alkyl group having 1 to 3 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.)
It is an unsaturated aliphatic ketone represented by, specifically mesityl oxide, 5-methyl-4-hepten-3-one, 6-methyl-5-nonen-4-one, 5-ethyl-4-methyl -4-heptene-3
-one, 2,5,6-trimethyl-4-hepten-3-one, 5-ethyl-2,4,6-trimethyl-4-hepten-3-one, 6-n-propyl-5-nonene-4 -On, etc. can be exemplified. Among these unsaturated aliphatic ketones, it is preferred to use mesityl oxide. In addition, in the method of the present invention, since the reaction is carried out under dehydration conditions, instead of the unsaturated aliphatic ketone represented by the general formula formula〔〕 (In the formula, R ¹ , R ² , R ³ and R ⁴ are represented by the above general formula []
is the same as ) It is also possible to use a tertiary alcohol represented by the following as a raw material for production. Specifically, the tertiary alcohols represented by the general formula [] include 4-hydroxy-4-methylpentan-2-one, 5-hydroxy-5-methylheptan-3-one, 6-hydroxy-6 -Methylnonan-4-one, 5-ethyl-5-hydroxy-4-methylheptan-3-one, 5-hydroxy-2,5,6-trimethylheptan-3-one, 5-ethyl-5-hydroxy-2・4・6-
Trimethylheptan-3-one and the like can be mentioned. In the method of the present invention, the proportion of the aliphatic ketone represented by the general formula [] used is generally in the range of 0.1 to 20 mol%, preferably 0.5 to 5 mol%, based on 1 mol of resorcinol. In the production method of the present invention, the proportion of the unsaturated aliphatic ketone represented by the above general formula [] is usually 0.2 to 10 mol%, based on 1 mol of resorcinol.
Preferably it is in the range of 0.4 to 3 mol%. Specifically, Lewis acids used in condensation reactions include boron trifluoride, complexes of boron trifluoride and various compounds, and halogenated acids such as ferric chloride, ferrous chloride, and ferric bromide. Iron, antimony halides such as antimony pentafluoride, antimony pentachloride, molybdenum halides such as molybdenum pentachloride, molybdenum pentabromide, molybdenum hexachloride, tungsten hexafluoride, tungsten hexachloride, tungsten pentachloride, pentabromide. Tungsten halides such as tungsten, aluminum halides such as aluminum trichloride and aluminum tribromide, titanium halides such as titanium tetrachloride and titanium tetrabromide, tin halides such as tin tetrachloride and tin tetrabromide, etc. I can give an example. Among these Lewis acids, boron trifluoride or its complex, iron halide, antimony halide, or molybdenum halide are preferred. The proportion of these Lewis acids used is usually 0.001 to 1 mol, preferably 0.01 to 0.1 mol, per 1 mol of resorcinol.
It is in the molar range. In the method of the present invention, polyalkyl-2-(2. 4-dihydroxyphenyl)-7-hydroxychroman is formed as the main product. This condensation reaction can be carried out in the presence of a solvent or in the absence of a solvent. As the reaction solvent, a solvent inert to the condensation reaction is used. Specifically, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, cyclohexane, ligroin, and kerosene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, and dichloroethane; Examples include carbon sulfide and nitrobenzene. When using these solvents, the usage ratio is:
The amount is usually 0.5 to 20 times, preferably 1 to 10 times the weight of resorcinol. The temperature during the condensation reaction is usually 20 to 150°C, preferably
The temperature ranges from 30 to 100°C. The time required for the condensation reaction varies depending on the reaction temperature and other conditions, but is usually in the range of 0.5 to 30 hours, preferably 2 to 20 hours. The condensation reaction proceeds by bringing a mixture of resorcinol, aliphatic ketone or unsaturated aliphatic ketone, Lewis acid, and optionally a solvent into contact with each other under stirring, and the compound represented by the general formula Produced by living things. After removing the solvent and unreacted raw materials from the reaction mixture, the compound represented by the general formula [] can be separated by performing operations such as extraction and crystallization according to conventional methods. The compound obtained by the method of the present invention is polyalkyl-2-(2.4-
dihydroxyphenyl)-7-hydroxychroman. Specifically, 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman, 2,4,4-triethyl-3
-Methyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman, 2,4,4-tri-n-propyl-3-ethyl-2-(2,4-
dihydroxyphenyl)-7-hydroxychroman, 2,4-diethyl-4-methyl-2-(2.
Examples include 4-dihydroxyphenyl)-7-hydroxychroman and 2,4-di-n-propyl-4-methyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman. Among these compounds obtained by the method of the present invention,
2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman is particularly preferred. The structure of the chroman compound represented by the general formula [] of the present invention was determined by elemental analysis, mass spectrum, infrared absorption spectrum, and ¹ H nuclear magnetic resonance spectrum. Generally, the ratio of constituent elements (experimental ratio) is determined by elemental analysis of the compound of the present invention.
The molecular weight was determined from the mass number m/e (M ⁺ ) of the parent peak in the mass spectrum (MS). Additionally, the infrared spectrum (IR) of the compounds of the present invention is 3500
A sharp absorption based on non-associative phenolic hydroxyl groups is observed around cm ^-1 , and a wide absorption based on associative phenolic hydroxyl groups is observed around 3700 to 3000 cm ^-1 . Furthermore, the structure of the compound of the present invention is
It can also be confirmed by ^1H nuclear magnetic resonance spectrum (NMR). For example, the compound represented by the general formula [] is 2,4,4-trimethyl-2-(2,4
-dihydroxyphenyl)-7-hydroxychroman, the structural formula [] The signals based on the protons of the phenolic hydroxyl group are 8.15δ (singlet) and 8.18, respectively.
δ(singlet) and 8.45δ(singlet) are observed, the proton bonded on the benzene ring,
, , and the signals based on 6.15δ (double of doublet, J _f ,
k = 7cps, J _f , _g = 3cps), 6.30δ (doublet, J
_g , f = 3cps), 6.35δ (doublet, J _h , _j =
7cps), 6.40δ (singlet), 6.95δ (doublet, J
_j , _h = 7 cps) and 7.00δ (doublet, J _k , _f =
7cps), and the signals based on the 3rd proton and 1.85δ (double,
J _d , _e = 13 cps) and 2.95 δ (doublet, J _e , _d
= 13cps), and the signal based on the three equivalent protons of the methyl group at the 2nd position was 1.65δ
(singlet), and the signal based on three equivalent protons of the 4-position methyl group is 1.20δ
(singlet), and the 3-methyl group at the 4-position
The signal based on equivalent protons is 0.80δ
(singlet). From this nuclear magnetic resonance spectrum, it was confirmed that this compound was 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman having the above structural formula []. Also, R ¹ , R ² , R ³ and R ⁴
When is another alkyl group, the structure was similarly confirmed from ¹ H nuclear magnetic resonance spectra. By decomposing the polyalkyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman represented by the general formula [] obtained by the above method under heating, the polyalkyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman represented by the above general formula [] is obtained. Polyalkyl-7-hydroxy-4H-chromene is obtained and at the same time resorcin is produced. The format of this pyrolysis reaction can be selected as appropriate, for example, pyrolysis using a closed pyrolysis reactor, or pyrolysis under reduced pressure while feeding the pyrolysis raw material to a pyrolysis device. Examples include a method in which the thermal decomposition products, the compound represented by the general formula [] and resorcinol, are recovered by distillation. The reaction temperature of pyrolysis is usually
The temperature range is from 170 to 400°C, preferably from 200 to 320°C. The time required for the thermal decomposition reaction varies depending on the reaction temperature and type of thermal decomposition, but approximately 0.1 to 5 hours is appropriate. When carrying out this method, the compound represented by the general formula [] as a raw material can be isolated and subjected to a thermal decomposition reaction, and low-boiling substances such as solvents can be removed from the mixture after the condensation reaction. Thereafter, if necessary, it can be subjected to a thermal decomposition reaction with unreacted resorcin and/or the compound represented by the general formula [] removed. Distillation of the mixture after the completion of the thermal decomposition reaction,
The above general formula [] can be obtained by extraction, crystallization, etc.
A compound represented by is obtained. Next, the present invention will be specifically explained using examples. Example 1 22.0 g (0.2 mol) of resorcinol, 19.6 g (0.2 mol) of mesityl oxide, and 180 g of carbon disulfide were placed in a 500 ml four-necked flask equipped with a stirrer, condenser, and thermometer, and boron trifluoride. aetherate
1.42 g (0.01 mol) was added and refluxed for 5 hours with vigorous stirring. The reaction mixture was separated by adding 50 g each of water and methanol, and the water-methanol layer was analyzed using high-performance liquid chromatography. As a result, the conversion rate of resorcin was 89 mol%, 2.4.4-
The yield of trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman is 77 mol%.
It turns out that it is. Examples 2 to 5 The reaction was carried out in the same manner as in Example 1, except that the Lewis acids shown in Table 1 were used instead of boron trifluoride etherate. After the reaction, the rate of change in resorcin and the yield of 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman were determined in the same manner as in Example 1, and the results shown in Table 1 were obtained. Ta. Example 6 The rate of change of resorcin and 2.4.
The yields of 4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman were determined to be 90% and 49%, respectively. Examples 7 to 8 Same as Example 1 except that 23.2 g (0.4 mol) of acetone was used instead of mesityl oxide and the Lewis acid shown in Table 2 was used instead of boron trifluoride etherate. The reaction was carried out in the same manner. After the reaction, the rate of change in resorcin and the yield of 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman were determined in the same manner as in Example 1, and the results in Table 2 were obtained. Ta.

【table】

[Table] Reference example 2,2,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman 6.0
g (20 mmol) was placed in a 50 ml round bottom flask equipped with a distillation column, thermal decomposition was performed under conditions of a heating temperature of 200 to 310°C and a pressure of 10 mmHg, and the distillate was collected. 50 ml of 1% sodium bicarbonate solution and 100 ml of toluene were added to the distillate to dissolve it, and then oil and water were separated. The toluene layer was washed three times with 50 ml of water, dried over sodium sulfate, and then the toluene was distilled off. The residue was recrystallized with 10 ml of ligroin (yield: 3.0 g). The colorless prismatic crystals thus obtained were found to be 2,4,4 ^- trimethyl-7-
It was found to be hydroxy-4H-chromene (yield 79%).

Claims (1)

[Claims] 1. Resorcin (a) and general formula [] (In the formula, R ¹ , R ² and R ⁴ each represent an arbitrary alkyl group having 1 to 3 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.)
An unsaturated aliphatic ketone represented by is selected from the group of boron trifluoride or its complexes, iron halides, antimony halides, molybdenum halides, tungsten halides, aluminum halides, titanium halides and tin halides. General formula characterized by condensation in the presence of a Lewis acid [] (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.)
A method for producing dihydroxyphenyl)-7-hydroxychroman. 2. The method according to claim 1, wherein the Lewis acid is boron trifluoride or a complex thereof, iron halide, antimony halide, or molybdenum halide. 3. The production method according to claim 1 or 2, wherein the condensation reaction is carried out at a temperature of 30 to 100°C. 4. The method according to any one of claims 1 to 3, in which 1 mole of resorcinol is reacted with an unsaturated aliphatic ketone in a range of 0.4 to 3 moles. 5 Resorcinol (a) and general formula [] R ¹ R ² C=0 [] (In the formula, R ¹ and R ² each have 1 to 3 carbon atoms
represents any alkyl group. ) is a Lewis compound selected from the group of boron trifluoride or its complexes, iron halides, antimony halides, molybdenum halides, tungsten halides, aluminum halides, titanium halides and tin halides. General formula characterized by condensation in the presence of an acid [] (In the formula, R ¹ and R ² are the same as above, R ³ represents hydrogen or an alkyl group having 1 to 2 carbon atoms, and R ⁴
is the same as R ² . ) A method for producing polyalkyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman. 6. The method according to claim 5, wherein the Lewis acid is boron trifluoride or a complex thereof, iron halide, antimony halide, or molybdenum halide. 7. The method according to claim 5 or 6, wherein the condensation reaction is carried out at a temperature of 30 to 100°C. 8. The method according to any one of claims 5 to 7, in which 1 mole of resorcinol is reacted with an unsaturated aliphatic ketone in a range of 0.4 to 3 moles.