JPS6052152B2 - Process for producing polyalkyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound polyalkyl-2-(2,4
-Dihydroxyphenyl)- -Relating to a method for producing hydrocoxychroman.

More specifically, polyalkyl 2-(2,4-
The present invention relates to a method for producing (dihydroxyphenyl)-7-hydroxychroman. When the novel compound of the present invention, polyalkyl-2-(2,4-dihydroxyphenyl)-hydrocoxychroman, is thermally decomposed, it can easily be converted into the general formula [■]''゜゛゛C et al. In the formula, R', R' and R'' each have an alkyl group having 1 to 3 carbon atoms, and R' is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

) Polyalkyl-J me[hydroxy-4H-
Chromene is obtained. This polyalkyl-J-hydroxy-chromene can be used as an intermediate in the production of agricultural chemicals such as insecticides, herbicides, and bactericides, medicines, fragrances, and compounding agents for polyolefin thermoplastic resins. For example, if O-ethyl-S-ethyl-0-(2,4,4-trimethyl-1,4-benzopyran-J main) phosphorothioate is produced using this, a novel product that exhibits excellent insecticidal effects against diamondback moths, etc. It is an insecticide. In addition, the general formula [
2,4,4-trialkyl-J-hydroxy-4H-chromene or 2,3,4,4-tetraalkyl-J-hydroxy-4H-chromene, which is expressed by can do. In addition, the compound represented by the general formula [] is
For example, it shows superior herbicidal activity against paddy field weeds and upland weeds compared to other compounds with 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 have produced the polyalkyl-2-(2,4-dihydroxyphenyl)-J-hydroxychroman with good yield, which has the above-mentioned usefulness! As a result of studies on methods for producing resorcinol, it was discovered that the above object could be achieved by reacting resorcinol with a specific unsaturated aliphatic ketone in the presence of an acidic catalyst, leading to the present invention.

That is, the present invention relates to resorcinol and general formula ・[1]
(In the formula, R1, R2 and R4 each represent an arbitrary alkyl group having 1 to 3 carbon atoms, and R3 represents a hydrogen atom or an arbitrary alkyl group having 1 to 3 carbon atoms.

) is characterized by condensing an unsaturated aliphatic ketone represented by the formula [] (in the formula, R
1, R2R3 and R4 are the same as above.

) is a method for producing polyalkyl-2-(2,4-dihydroxyphenyl)-J-hydroxychroman. As the raw material resorcin, any resorcin obtained by any method can be used.

The raw material unsaturated aliphatic ketone is an unsaturated aliphatic ketone represented by the above general formula [1], and specifically tantyl oxide, 5-methyl-4-hepten-3-one, 6-methyl-5-nonene-4 -one, 5-ethyl-4-methyl-4-hepten-3-one, 2,5,6-trimethyl-4-hepten-3-one, 5-ethyl-2,4,6-trimethyl-4-hepten-3-one, 5-ethyl 4-
Examples include hepten-3-one, 6-n-propyl-5-nonen-4-one, and the like.

Among these unsaturated aliphatic ketones, tantyl oxide is preferably used. In addition, in the method of the present invention, since the reaction is carried out under dehydration conditions, the general formula [1
] Instead of an unsaturated aliphatic ketone represented by It is also possible to use a tertiary alcohol represented by ) 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-methylheptane-3-
one, 6-hydroxy-6-methylnonan-4-one,
5-ethyl-5-hydroxy-4-methylheptane-3
-one, 5-hydroxy-2,5,6-trimethylheptan-3-one, 5-ethyl-5-hydroxy-2,4
, 6-trimethylheptan-3-one, and the like. In the production method of the present invention, the proportion of unsaturated aliphatic ketone used is usually in the range of 0.2 to 10 mol, preferably 0.3 mol, per 1 mol of resorcinol.

Specifically, the acidic catalyst used during the condensation reaction is:
Inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, polyphosphoric acid, organic acids such as benzenesulfonic acid, toluenesulfonic acid, etc.; silica, silica/alumina, silica magnesia, silica/titania, alumina/titania, Examples include solid acid catalysts such as cation exchange resins.

Among these acidic catalysts, it is preferable to use Bränsted acids or cation exchange resins. In the method of the present invention, resorcin and the general formula [1]
Polyalkyl-2-(2,4-dihydroxyphenyl) represented by the general formula [] is obtained by condensing an unsaturated aliphatic ketone represented by the following in the presence of an acidic catalyst.
−J me[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. in particular,
Aromatic hydrocarbons such as benzene, toluene, xylene, hexane, heptane, cyclohexane, ligroin,
Examples include aliphatic hydrocarbons such as kerosene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, and dichloroethane, and nitrobenzene. When these solvents are used, the proportion is usually 0.5 to 20 times, preferably 1 to 10 times the weight of resorcinol. The temperature during the condensation reaction is usually in the range of 20 to 150°C, preferably 40 to 130°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 3 CJI1f, preferably 2 to 2 CJI1f. The condensation reaction proceeds by contacting a mixture of resorcinol, an unsaturated aliphatic ketone, an acidic catalyst, and optionally a solvent with stirring, resulting in the formation of a new compound and by-products represented by the general formula [formerly do. After removing the solvent and unreacted raw materials from the mixture after completion of the reaction, the new compound represented by the above 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 a polyalkyl-2-(2,4-dihydroxyphenyl)-
JMe[Hydroxychroman.

Specifically, 2,4,4-trimethyl-2-(2,4-
dihydroxyphenyl)-J
n-propyl-3-ethyl-2-(2,4-dihydroxyphenyl)-J[hydroxychroman, 2,4-diethyl-4-methyl-2-(2,4-dihydroxyphenyl)-J] [Hydroxychroman, 2,4-di-n-propyl-methyl-2-(2,4-dihydroxyphenyl)
-J■■■ is 2,4,4-trimethyl-2-(2,4
-dihydroxyphenyl)-J[hydroxychroman] is particularly preferred.

The compound represented by the general formula [] of the present invention is a new compound, and its structure was determined by elemental analysis, mass spectrum, infrared absorption spectrum, and 1MH nuclear magnetic resonance spectrum.

Generally, the ratio of the constituent elements (empirical formula) is determined by elemental analysis of the compound of the present invention, and the molecular weight is determined from the mass number m/e (M) of the parent peak in the mass spectrum (MS). In addition, in the infrared spectrum (IR) of the compound of the present invention, 35
(1) Sharp absorption due to non-associative phenonor hydroxyl group was observed near o-1, and at 3700 to 3000 cm
A wide range of absorption based on associative phenolic hydroxyl groups is observed near -1. Furthermore, the structure of the compound of the present invention is 1MH
It can also be confirmed by nuclear magnetic resonance spectrum (NMR). For example, a compound represented by the general formula [formerly 2, 4,
In the case of 4-trimethyl-2-(2,4-dihydroxyphenyl)-J[hydroxychroman, the structural formula [
] The signals based on protons 1 and 6 of the phenolic hydroxyl group are 8.15δ (Singlet) and 8.15δ (Singlet), respectively.
18δ (Singlet) and 8.45δ (Singlet)
let), and the signals based on protons 1, 4541 and 9 bonded on the benzene ring are respectively 6.15δ (DOllbleOfdOuble) in the above symbol order.
t. ．． Jf. ．． k=7CpS. ．． J,,8=3CpS)
, 6.30δ(DOLlblet..Jgl,=3Cp
S), 6.35δ(DoubleL.Jhl,=7CP
S), 6.40δ (Singlet), 6.95δ (D
Oublet. ．． Jj,. h=7cps) and 7.0
0δ (DOublet..Jk..f=7CPS), and the signals based on protons 4 and 6 at position 3 are respectively 1.85δ (DOllblet..Jd..e
= 13cps) and 2.95δ (Doublet..
Je. ．． d = 13 cps), and the signal based on the three equivalent protons 6 of the methyl group at the 2-position was 1.65
Found in δ (Singlet), 3 of the 4-position methyl group
The signal based on equivalent protons 5 is 1.20δ(
Singlet), and the 3-methyl group at the 4-position
The signal based on equivalent protons 5 is 0.80δ(
Singlet).

From this nuclear magnetic resonance spectrum, this compound has the above structural formula [] 2,4,4-trimethyl-2-(2,4-
The product was confirmed to be dihydroxyphenyl-J-hydroxychroman. Also, R1, R2, R3 and R4
When is another alkyl group, the structure was similarly confirmed from the 1H nuclear magnetic resonance spectrum. Polyalkyl-2-(2,4
-Dihydroxyphenyl)-J-hydroxychromene is decomposed under heating to obtain a polyalkyl-J-hydroxychromene represented by the general formula [], and at the same time, resorcin is produced.

The format of this thermal decomposition reaction can be selected as appropriate.
For example, pyrolysis is performed using a closed type pyrolysis reactor, or pyrolysis is performed under reduced pressure while feeding the pyrolysis raw material to a pyrolysis device, and the pyrolysis product is expressed by the general formula [ ]. Examples include a method of recovering the compound and resorcinol by distillation. The reaction temperature for thermal decomposition is usually in the range of 170 to 400°C, preferably 200 to 320°C. The time required for the thermal decomposition reaction varies depending on the reaction temperature and type of thermal decomposition, but is suitably about 0.1 to 5 hours. When carrying out this method, the raw material compound 7 represented by the general formula After removing the
If necessary, it may be subjected to a thermal decomposition reaction with unreacted resorcin and/or the compound represented by the general formula [] removed. After the thermal decomposition reaction is completed, the mixture is subjected to distillation, extraction, crystallization, etc. to obtain the compound represented by the general formula []. Next, the present invention will be specifically explained using examples.

Example 1 110 g (1 mol) of resorcinol and 49 g (a) of tantyl oxide. 5mol) to 200wLL with water cooling pipe
The mixture was placed in a round bottom flask, and 10 g of Upper Risto 15 was added thereto, followed by stirring at 85 to 90° C. for 1 C@ under an argon atmosphere.

The resorcin conversion rate was measured by gas chromatography and was found to be 50%. After cooling the reaction mixture, 200 ml of ether was added, and the upper list 15 of the catalyst was filtered off. After removing unreacted resorcinol by flushing the Oki solution with water, it was dried with MgSO4, and ether and unreacted tantyl oxide were distilled off using an evaporator. When 100 ml of toluene was added to the obtained concentrate and heated to 100° C., a solid was precipitated. After cooling, it was filtered, washed with hot toluene, and then dried under reduced pressure to obtain 52 g of white powder with a melting point of 235 to 237°C. This compound was found to be 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-J me[hydroxy It turned out to be chroman (yield 35%).
Elemental analysis value C: 72.03%, H: 6.65%,
Calculated value as C: 21.34% Cl8H2OO, C: 71.98%, H: 6.71%,
C: 21.31% mass spectrum m/e: 300, 28 degrees 257, 175, 163, 15
1. Infrared absorption spectrum (KBrdisk) 3510
C! TL-1 (non-associative 0H..sharp) 3600
~3000 cm-1 (Associative 0H..br0ad) Example 2 200 with Dean-Stark condenser
110 g (1 mole) of resorcin, 69 g (0.7 mole) of tantyl oxide, and 1.1 g of concentrated sulfuric acid in an mt flask.
(0.01 mol) was added.

After replacing the inside of the lasco with argon, the temperature is 80-85%.
The mixture was stirred for 5 hours at a pressure of 30 to 40 mHg (resorcin conversion rate 45%). During this process, the water azeotroped with the tantyl oxide was collected by a Dean-Stark condenser, and the tantyl oxide was refluxed into the flask. After cooling, 200 ml of ether was added and then washed with water. The ether layer was treated in the same manner as in Example 1 to obtain 62 g (yield: 41%) of 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-J-hydroxychroman. jExample 3
In Example 2, 81 g (0.7 mol) of 4-hydroxy-4-methylpentan-2-one was used instead of tantyl oxide and reacted for 1 hour, resulting in 2,4,4-trimethyl-2-(2,4 -JJq droxyphenyl)-
J me[hydroxychroman was obtained in a yield of 35% (resorcin conversion rate 41%).

Claims (1)

[Claims] 1. Resorcinol and the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R
^1, R^2 and R^4 each have 1 to 3 carbon atoms
represents any alkyl group, and R^3 represents a hydrogen atom or any alkyl group having 1 to 3 carbon atoms. ) is characterized by condensing an unsaturated aliphatic ketone in the presence of an acidic catalyst [II] ▲ Formula,
There are chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2R^3 and R^4 are the same as above.) Polyalkyl-2-(2,4-dihydroxyphenyl)-7 - A method for producing hydroxychroman. 2. The method according to claim 1, wherein the acidic catalyst is a plain steady acid or a cation exchange resin. 3. The method according to claim 1 or 2, wherein the condensation reaction is carried out at a temperature of 40 to 130°C. 4 0 unsaturated aliphatic ketones per mole of resorcinol
．． The method according to any one of claims 1 to 3, wherein the reaction is carried out in a range of 4 to 3 moles.