JPS6334873B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention discloses novel compounds such as polyalkyl-5-chromenes such as 2,2,4-trialkyl-5-hydroxy-2H-chromene and 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene.
Regarding hydroxy-2H-chromene and its production method. In more detail, 2,2, Polyalkyl-5 such as 4-trialkyl-5-hydroxy-2H-chromene and 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene
-Relating to hydroxy-2H-chromene and its production method. As a result of research on chromene-based compounds, the present inventors found that 2,2,4-trialkyl-5-hydroxy-2H-chromene and 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene We have discovered that this is a new compound and has various useful properties, and have arrived at the present invention. Furthermore, we investigated a method for producing this new compound and found that 2,2,4-trialkyl-7-hydroxy-4H- It has been discovered that chromene or 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene can be obtained in good yield, and the present invention has been achieved. That is, the present invention is based on the general formula [] (In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a C 1 to 3 alkyl group.
represents an alkyl group, and R ³ and R ⁴ each represent an alkyl group having 1 to 3 carbon atoms. 2,2,4-trialkyl-5-hydroxy-2H-chromene or 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene) represented by ] (In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a C 1 to 3 alkyl group.
represents an alkyl group, and R ³ and R ⁴ each represent an alkyl group having 1 to 3 carbon atoms. ) A general formula characterized by reacting an unsaturated aliphatic ketone represented by ) in the presence of a basic catalyst [] (In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a C 1 to 3 alkyl group.
represents an alkyl group, and R ³ and R ⁴ each represent an alkyl group having 1 to 3 carbon atoms. ) A method for producing 2,2,4-trialkyl-5-hydroxy-2H-chromene or 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene represented by the following formula is defined as a production method invention. 2,2,4-trialkyl-7-hydroxy-5-hydroxy-2H, a novel compound of the present invention
-Chromene or 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene is an antibacterial agent,
It is used as a bactericidal agent, and can also be used as an intermediate in the production of agricultural chemicals, medicines, fragrances, compounding agents for thermoplastic resins such as polyolefins, and as a monomer component of polymers. For example, 2,2,4-trialkyl-5-hydroxy-2H-chromene or 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene, which is a novel compound of the present invention, is It has an excellent preventive effect against mildew and can be used as an antibacterial or fungicidal agent. Further, the following general formula obtained by reacting the compound of the present invention with O-alkyl-S-alkyl chloride phosphorothioate or dithioate (In the formula, R ¹ , R ² , R ³ and R ⁴ have the above-mentioned meanings. ^{R 5} and R ⁶ are lower alkyl groups, and X represents an oxygen atom or a sulfur atom.) is effective as an insecticide and acaricide for controlling insects such as the Japanese spider mite, the Japanese armyworm, the diamondback moth, and the false red spider mite. Furthermore, since the novel compound of the present invention exhibits cationic polymerizability, homopolymers and copolymers with aliphatic olefins or aromatic olefins can be obtained from this compound. 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 having a similar softening point, and therefore have the advantage of improved workability. The novel compound of the present invention is 2,2,4-trialkyl-5-hydroxy-2H-chromene or 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene represented by the general formula []. It is. In the general formula [], R ¹ is a methyl group, ethyl group, propyl group, or isopropyl group, and R ² is a hydrogen atom, a methyl group, an ethyl group,
It is a propyl group or an isopropyl group, and R ³ and R ⁴ are each a methyl group, an ethyl group, a propyl group or an isopropyl group. 2,2,4-trialkyl- represented by the above general formula []
Specifically, 5-hydroxy-2H-chromene is 2,2,4-trimethyl-5-hydroxy-
2H-chromene, 2,2,4-triethyl-5-
Hydroxy-2H-chromene, 2,2,4-tri-n-propyl-5-hydroxy-2H-chromene, 2,2,4-triisopropyl-5-hydroxy-2H-chromene, 2,4-diethyl-2 ―
Methyl-5-hydroxy-2H-chromene, 2,
Examples include 4-di-n-propyl-2-methyl-5-hydroxy-2H-chromene and 2,4-diisopropyl-2-methyl-5-hydroxy-2H-chromene. In addition, specifically as the 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene represented by the general formula [], 2,2,3,4-tetramethyl-5-
Hydroxy-2H-chromene, 2,2,3,4-
Tetraethyl-5-hydroxy-2H-chromene,
2,2,3,4-tetra-n-propyl-5-hydroxy-2H-chromene, 2,2,3,4-tetraisopropyl-5-hydroxy-2H-chromene, 2,2,4-triethyl-3 -Methyl-5
Examples include -hydroxy-2H-chromene and 2,4-diisopropyl-2-ethyl-3-methyl-5-hydroxy-2H-chromene.
Among these compounds represented by the above general formula [], 2,2,4-trimethyl-5-
Hydroxy-2H-chromene is preferred. The compound represented by the above general formula [] of the present invention is a new compound, and its structure can be determined by elemental analysis, mass spectrum, infrared absorption spectrum, ¹ H
This was done by nuclear magnetic resonance spectroscopy. Generally, the ratio of constituent elements (empirical formula) is determined by elemental analysis of the compound of the present invention, and mass spectrum (MS) is obtained.
The molecular weight was determined from the mass number m/e (M ⁺ ) of the parent peak. In addition, in the infrared absorption spectrum (IR) of the compound of the present invention ^, broad and strong stretching vibrations based on phenolic hydroxyl groups are observed around 3600 to 3000 cm ^-1 , and carbon and
C═C stretching vibrations based on carbon unsaturated bonds are observed. The structure of the compound of the present invention is also determined by ¹ H nuclear magnetic resonance spectroscopy. For example, if R ¹ , R ³ and R ⁴ in the general formula [] are all methyl groups and R ² is a hydrogen atom, the structural formula [] The signal of the methyl proton at the 2nd position is 1.37δ
(singlet, 6H), a methyl proton signal at position 4 was observed at 2.20δ (singlet, 3H),
The signal of the proton at position 3 is 5.33δ (singlet,
1H), and a phenolic hydroxyl proton signal was observed at 5.73δ (singlet, 1H),
In addition, the signals of the protons bonded to the benzene ring are each 6.25δ (doublet, 1H, J=9
Hz), 6.48δ (doublet, 1H, J=9Hz), 6.91δ
(triplet, 1H, J=9Hz). In the formula [], when R ¹ , R ² , R ³ and R ⁴ were other substituents, the structure was similarly confirmed from the ¹ H nuclear magnetic resonance spectrum. Next, the method of manufacturing the compound of the present invention will be explained. First, the raw materials for its production will be explained. As the raw material resorcin, any resorcin obtained by any manufacturing method can be used regardless of its purity. The raw material unsaturated aliphatic ketone has the above general formula []
It is an α,β-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-hepten-3-one, 2,5,6-trimethyl-4
-Hepten-3-one, 5-ethyl-2,4,6
Examples include -trimethyl-4-hepten-3-one, 5-ethyl-4-hepten-3-one, and 6-n-propyl-5-nonen-4-one. In addition, in the method of the present invention, the reaction is carried out under dehydration conditions, so instead of the α,β-unsaturated ketone represented by the general formula , for example, the general formula [] It is also possible to use a tertiary alcohol represented by the formula (wherein R ¹ , R ² , R ³ and R ⁴ are the same as in the general formula []) as a raw material. Specifically, the tertiary alcohols represented by the general formula [] include 4-hydroxy-4-methylpentan-2-one, 5-hydroxy-5-methylheptan-3-one, and 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-
Examples include trimethylheptan-3-one. In the method of the present invention, the proportion of these α,β-unsaturated aliphatic ketones to be used is generally 0.5 to 5 mol, preferably 0.8 to 3 mol, per 1 mol of resorcinol. Basic catalysts used in condensation reactions include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium oxide, sodium oxide, potassium oxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, and hydrogen carbonate. Sodium, potassium bicarbonate, lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide , methyllithium, ethyllithium,
Propyllithium, butyllithium, lithium acetate, sodium acetate, sodium propionate,
Basic alkali metal compounds such as sodium butyrate and potassium acetate; Basic alkaline earth metal compounds such as magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide; Trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, pyrrolidine, piperidine, piperazine, pyridine, picoline, lutidine, quinoline, triethylenediamine, 1,8
-Diazabicyclo[5,4,0]undecene-7
and quaternary ammonium hydroxides such as tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide. Among these basic catalysts, it is particularly preferable to use basic alkaline earth metal compounds. The usage ratio of these basic alkaline earth metal compounds is usually 0.001 to 0.3 mol per 1 mol of resorcinol.
Preferably it is in the range of 0.01 to 0.1 mole. When the above-exemplified basic alkali metal compound is used as a basic catalyst, the production rate of the by-product compound represented by the general formula [] will increase (Examples 4 to 6).
reference). In the production method of the present invention, the 2,2,4-trialkyl represented by the general formula [] is produced by condensing resorcin and an unsaturated aliphatic ketone represented by the general formula [] in the presence of a basic catalyst. -5-hydroxy-2H-chromene or 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene is obtained. At this time, as a by-product, the general formula [] (In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a C 1 to 3 alkyl group.
represents an alkyl group, and R ³ and R ⁴ each represent an alkyl group having 1 to 3 carbon atoms. ) 2,2,4-trialkyl-7-hydroxy-2H-chromene or 2,2,3,4-tetraalkyl-7-hydroxy-2H-chromene is produced. The condensation reaction can be carried out in the presence of a solvent or in the absence of a solvent. Specific examples of reaction solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and kerosene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, and dichloroethane; Examples include ethers such as anisole and diethylene glycol dimethyl ether, and nitro compounds such as nitrobenzene. The ratio of these reaction solvents to resorcinol is usually 1 to 1.
It is in the range of 10 times the weight. Also, the temperature during the condensation reaction is usually 50 to 250℃.
℃, preferably in the range of 100 to 180℃. The time required for the condensation reaction varies depending on the reaction temperature and other conditions, but is usually 0.5 to 20 hours.
Preferably it is in the range of 1 to 15 hours. This condensation reaction easily proceeds by bringing a mixture consisting of resorcinol, the unsaturated aliphatic ketone, a basic catalyst and, if necessary, a solvent into contact under the above conditions with stirring. The reaction method may be a closed system, but water produced by the reaction may be co-used with an α,β-unsaturated ketone represented by the general formula [], a tertiary alcohol represented by the general formula [], or a solvent. It is also possible to adopt a method of successively distilling it out of the system by boiling. As mentioned above, through this condensation reaction, a new compound represented by the general formula [] and the general formula []
A compound represented by is produced. After distilling and recovering the solvent and raw materials from the mixture after the completion of the reaction, operations such as extraction, distillation, and crystallization are performed according to conventional methods to obtain the new compound represented by the above general formula [] and the above general formula. Compounds represented by formula [] can be separated. The ratio of both compounds produced as a result of the condensation reaction is the ratio of the compounds represented by the general formula [] to 1 mole of the compound represented by the general formula [].
The amount of the compound represented by is usually in the range of 0.3 to 10 moles. Next, the present invention will be specifically explained using examples. Example 1 Stirring blade, Dean-Stark condenser,
In a 300 ml flask equipped with a thermometer, add 110 g (1 mole) of resorcin and 118 g of mesityl oxide.
(1.2 mol) and 6.3 g (0.02 mol) _of Ba(OH) 2.8H ₂ O were added. After purging the inside of the flask with argon, it was stirred at a temperature of 150 to 170°C and a pressure of 165 to 180 mmHg. During this time, water azeotroped with mesityl oxide was collected in a Dean-Stark condenser, and mesityl oxide was refluxed into the flask. After 5 hours, the conversion rate of resorcin was measured by gas chromatography and found to be 80%. After cooling, 10%
20 g of sulfuric acid was added and the precipitate was separated. 100 ml of toluene was added to the liquid, and unreacted resorcin was removed by washing with water, followed by drying with Na ₂ SO ₄ and concentration. The concentrate was then rectified using a 20-stage old-shot distillation column, and a fraction with a boiling point of 139-140°C/7.0 mmHg was collected. This fraction was recrystallized from hexane-toluene to obtain 70 g of colorless granular crystals with a melting point of 113-114°C. From the analytical values described below and the results of the ¹ H nuclear magnetic resonance spectrum mentioned above, this crystal is 2, 2, 4
-trimethyl-5-hydroxy-2H-chromene. (Yield 37%). Elemental analysis value C: 75.70%, H: 7.37%, O: 16.87% Calculated value as C ₁₂ H ₁₄ O ₂ C: 75.76%, H: 7.42%, O: 16.82% Mass spectrum (m/e) 190, 175, 87.5 Infrared absorption spectrum (KBr, disk) 3350cm ^-1 (OH), 1648cm ^-1 (C=C), 1609
cm ^-1 (benzene ring) In the above rectification, the boiling point is 139-140℃/
A fraction of 2.3 mmHg was collected and recrystallized from toluene, yielding 38 g of a by-product in the form of colorless flaky crystals with a melting point of 132-133°C. The following analytical values revealed that this crystal was 2,2,4-trimethyl-7-hydroxy-2H-chromene (yield:
20%). Elemental analysis value C: 75.68%, H: 7.41%, O: 16.83% Calculated value as C ₁₂ H ₁₄ O ₂ C: 75.76%, H: 7.42%, O: 16.82% Mass spectrum (m/e) 190, 175 Infrared absorption spectrum (KBr, disk) 3350cm ^-1 (OH), 1645cm ^-1 (C=C), 1615
cm ^-1 (benzene ring) ¹ H nuclear magnetic resonance spectrum (in CDCl ₃ , TMS
standard)

[Table] Examples 2 to 7 The reaction was carried out in the same manner as in Example 1, except that the compounds shown in Table 2 were used in place of Ba(OH) _{2.8H 2} O. The results are shown in Table 2.

[Table] Example 8 In Example 1, 4-hydroxy-methylpentan-2-one was used instead of mesityl oxide.
The reaction was carried out in the same manner as in Example 1 except that 139 g (1.2 mol) was used. As a result, 2,2,4-trimethyl-5-hydroxy-2H-chromene and 2,2,4-trimethyl-7-hydroxy-2H
-Chromene was obtained in yields of 29% and 11%, respectively (resorcin conversion rate 52%). Example 9 The reaction was carried out in the same manner as in Example 1 except that 5-methyl-4-hepten-3-one was used instead of mesityl oxide.
4-diethyl-2-methyl-5-hydroxy-
2H-chromene was obtained in a yield of 34%. ^1H nuclear magnetic resonance spectrum of this compound (in CDCl ₃ ,
TMS standards) were as follows. δ0.78(t, 3H, J=7Hz,), 1.00(t,
3H, J=7Hz,), 1.36(s, 3H,),
1.3~1.7 (m, 2H, ), 2.15 (q, 2H, J=
7Hz, ), 5.30 (s, 1H, ), 5.70 (s,
1H, ), 6.27 (d, 1H, J=8Hz, ),
6.51 (d, 1H, J=8Hz,) 6.98 (t, 1H,
J=8Hz,) Example 10 The reaction was carried out in the same manner as in Example 1 except that 6-methyl-5-nonen-4-one was used instead of mesityl oxide.
2,4-di-n-propyl-2-methyl-5-hydroxy-2H-chromene was obtained in a yield of 29%.
The ¹ H nuclear magnetic resonance spectrum (CDCl ₃ , TMS standard) of this compound was as follows. δ0.95 (t, 6H, J=8Hz,), 1.3~1.9 (m,
6H, ), 1.35 (s, 3H, ), 2.20 (t,
2H, J=8Hz,), 5.33(s, 1H,),
5.73 (s, 1H,), 6.25 (d, 1H, J=9
Hz, ), 6.49 (d, 1H, J=9Hz, ),
6.91) (t, 1H, J=9Hz,) Example 11 In Example 1, 5-ethyl-4-methyl-4-hepetene-3 was used instead of mesityl oxide.
When the reaction was carried out in the same manner as in Example 1 except for using -one, 2,2,4-triethyl-3-methyl-5-hydroxy-2H-chromene was obtained in a yield of 32%.
Obtained with. The ¹ H nuclear magnetic resonance spectrum (in CDCl ₃ , TMS standard) of this compound was as follows. δ0.85(t, 6H, J=6Hz,), 1.05(t,
3H, J=7Hz, ), 1.3~1.8(m, 4H,
), 1.70 (s, 3H, ) 2.25 (q, 2H, J=
7Hz, ), 5.80 (s, 1H, ), 6.22 (d,
1H, J=9Hz, ), 6.50 (d, 1H, J=9
Hz, ), 6.90 (t, 1H, J=9Hz,) Test Example 1 Dewny Midlew of Disease
Preventive effect against 2,2,4-trimethyl-5-hydroxy-2H-chromene as an active ingredient in cotyledon stage cucumber (variety: Sagami Hanshiro) grown in a nursery box.
Wettable powder containing % by weight is diluted with water to adjust the active ingredient concentration.
The concentration was 1000ppm and it was evenly distributed. After 5 hours, pre-cultured cucumber and disease fungus (Pseudoperonospora cubensis) were inoculated on both sides of the leaves. When seedlings were grown in a greenhouse for 8 days and then observed, the diseased leaf rate was 2.0%. On the other hand, 2, 2,
In place of 4-trimethyl-5-hydroxy-2H-chromene, the known substance 2,2,4-trimethyl-
When 7-hydroxy-2H-chromene was similarly applied, the rate of diseased leaves was 100%. The same applies to other compounds of the present invention.
Similar results were obtained when testing at a concentration of 1000 ppm to investigate the preventive effect against succulent lily and disease. Test Example 2 (Insecticide derived from the compound of the present invention) An organic phosphate ester prepared as an emulsion was diluted with water to a predetermined concentration, cabbage leaves were immersed in it for 10 seconds, and after air-drying it was poured into a 60 ml vinyl chloride cup. Get in,
I released the 3rd instar larvae of Spodoptera japonica there. After treatment, the plants were placed in a constant temperature room at 25°C for 48 hours, and the number of live and dead insects was determined to determine the mortality rate. The test was conducted three times per section, and 30 animals were tested. The results are shown in the table below.

[Table] The test compounds in the table are as follows. Reference example (synthesis of compound 1, compound 2) 2,2,4-trimethyl-5-hydroxy-
2H-chromene 9.5g (0.05mol) and DBU7.6g
(0.05 mol) was dissolved in 80 ml of benzene, and O-
10.2 g (0.05 mol) of methyl-Sn-propyl chloride phosphorodithioate was added, and the mixture was stirred and reacted at 40 to 50°C for 3 hours. After the reaction, the mixture was allowed to cool, and the reaction mixture was washed successively with water, 5% caustic soda, and water, and the benzene layer was separated and dried over anhydrous sodium sulfate. After concentrating the benzene, it was subjected to vacuum distillation to obtain compound 1, O-methyl-S-n-propyl-O-(2,2,4-trimethyl-1 ,4
15.0 g (yield: 83.8%) of -benzopyran-5-yl) phosphorodithioate (refractive index n ²⁰ _D =1.5734) was obtained. Compound 2 was obtained by reacting in the same manner as above using O-methyl-S-sec-butyl chloride phosphorothioate.

Claims (1)

[Claims] 1. General formula [] (In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a C 1 to 3 alkyl group.
represents an alkyl group, and R ³ and R ⁴ each represent an alkyl group having 1 to 3 carbon atoms. ) 2,2,4-trialkyl-5-hydroxy-2H-chromene or 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene. 2 The compound represented by the general formula [] is 2,2,
The compound according to claim 1, which is 4-trimethyl-5-hydroxy-2H-chromene. 3 Resorcinol and general formula [] (In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a C 1 to 3 alkyl group.
represents an alkyl group, and R ³ and R ⁴ each represent an alkyl group having 1 to 3 carbon atoms. ) A general formula characterized by reacting an unsaturated aliphatic ketone represented by ) in the presence of a basic catalyst [] (In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or a C 1 to 3 alkyl group.
represents an alkyl group, and R ³ and R ⁴ each represent an alkyl group having 1 to 3 carbon atoms. 2,2,4-trialkyl-5-hydroxy-2H-chromene or 2,2,3,4-tetraalkyl-5-hydroxy-2H-chromene) represented by ). 4. The method according to claim 3, wherein the basic catalyst is a basic alkaline earth metal compound. 5. The method according to claim 3, wherein the basic catalyst is used in a proportion of 0.01 to 0.1 mol per 1 mol of resorcinol. 6. The method according to claim 3, wherein the proportion of the unsaturated aliphatic ketone used is in the range of 0.8 to 3 moles per mole of resorcinol. 7. The method according to claim 3, wherein the reaction is carried out at a temperature of 100 to 180°C.