JPS6313973B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to resorcinol derivatives, more specifically, the general formula () (In the formula, R represents a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 3 carbon atoms.) The present invention relates to a resorcinol derivative, which is a novel compound not described in any literature. In the substituent R in the above general formula (), examples of the linear alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-dodecyl,
Examples of the alkenyl group having 2 to 3 carbon atoms include n-eicosyl and the like, and examples of the alkenyl group having 2 to 3 carbon atoms include vinyl, allyl, and 1-propenyl. Furthermore, the present invention relates to a method for producing a resorcinol derivative represented by the general formula (), and more specifically, 4,6-di-t-butylresorcinol and the general formula () RX () (wherein R is as defined above). The present invention relates to a method for producing a resorcinol derivative represented by the general formula (), which comprises reacting a halide represented by the formula (having the same meaning, X represents a halogen atom) in an alkaline aqueous solution. 4,6-di-t-butylresorcinol used in the present invention is a known compound and can be easily obtained from resorcinol in high yield by a common butylation method. In addition, examples of halides represented by the general formula () include methyl bromide, methyl iodide,
Ethyl bromide, ethyl iodide, n-propyl chloride,
n-propyl bromide, n-propyl iodide, n-bromide
- straight chain alkyl halides such as butyl, n-butyl iodide, n-dodecyl chloride, n-dodecyl bromide, n-eicosyl chloride, n-eicosyl bromide,
Vinyl chloride, allyl chloride, allyl bromide, 1-chloride
Examples include halogenated alkenyl such as propenyl and 1-propenyl bromide. Conventionally, the most common method for alkylation, alkenylation, or aralkylation of aromatic compounds is to react with alkyl halides, alkenyl halides, or aralkyl halides in the presence of a Friedel-Crafts type catalyst. Ta.
However, when the present inventors applied this method, 4,6
- When attempting to alkylate, alkenylate, or aralkylate the 2-position of di-t-butylresorcinol, a debutylation reaction occurs, resulting in the desired 2-alkyl-4,6-di-t-butylresorcinol, 2-alkenyl-4,6-di-t-
Butylresorcinol or 2-aralkyl-
It was extremely difficult to obtain 4,6-di-t-butylresorcinol. For these reasons, the present inventors have conducted various studies on methods that can solve these problems and industrially advantageously produce the compound of general formula ().
When 4,6-di-t-butylresorcinol is alkylated, alkenylated, or aralkylated using a halide represented by the general formula () in an alkaline aqueous solution, the debutylation reaction is suppressed and the target product is not obtained. They have found that it can be obtained efficiently, leading to the completion of the present invention. It is also true that by carrying out the above reaction in an alkaline aqueous solution, the compound of general formula () itself can be converted or isomerized, and especially in the case of alkenylating agents, attack from carbon atoms forming double bonds can be prevented. This is a notable feature of the inventive method. As the alkali species used in the present invention, one or more species selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferably used, and the amount used is usually 4,6-di-t-butylresorcinol. Although the amount is 1 mole or more, it is practically desirable that the amount is in the range of 1.05 to 5 moles. The concentration of the alkaline aqueous solution is not particularly limited, but is preferably 10 to 20% by weight. In this reaction, it is desirable to use a solvent that is inert to the reaction system and immiscible with water, if necessary, from the viewpoint of improving the yield. Examples of the solvent include benzene, toluene, xylene, ethylbenzene, ligroin, n-hexane, cyclohexane, decahydronaphthalene, ethyl ether,
Examples include aromatic hydrocarbons such as isopropyl ether, aliphatic hydrocarbons, and ethers. There is no particular restriction on the amount of such a solvent used, but from the viewpoint of reducing the reaction rate and volumetric efficiency due to the use of an excessive amount, it is recommended that the amount is not more than 5 times the weight of 4,6-di-t-butylresorcinol. preferable. The amount of the halide represented by the general formula () to be used is theoretically 1 mole times that of 4,6-di-t-butylresorcinol, but it is usually in a small excess, preferably 1.05 to 1.5 Molar times are used. The reaction temperature and reaction time depend on the activity of the compound of general formula () and other conditions, but
Generally, the reaction temperature is 40 to 90°C and the reaction time is 30 minutes to 24 hours. Generally, the longer the chain of the compound of general formula (), the longer the reaction time tends to be. The novel compound () of the present invention is synthesized by the above reaction, but the target product can be separated and recovered from the reaction solution by separating the reaction solution into an organic layer and an aqueous layer according to a conventional method. This is carried out by a method such as isolation from a layer by a general method such as recrystallization. The novel compound of the present invention thus obtained ()
is also extremely useful as a raw material for easily obtaining the 2-substituted product of resorcinol in good yield, which is a useful raw material for producing pharmaceuticals and agrochemicals, dyes and pigments, stabilizers, etc. That is, as a method for obtaining a 2-substituted product of resorcinol, for example, a method using 1,3-cyclohexanedione as an intermediate from resorcinol ("Tetrahedron", Vol. 29, 3857-
9) etc. are known, but by debutylating the compound () of the present invention, it can be easily and with high yield,
Moreover, the 2-substituted resorcinol can be obtained very easily without the need for pressurization as in the above method. Next, the present invention will be explained with reference to Examples. Example 1 22.2 g of 4,6-di-t-butylresorcinol, 66.7 g of a 12% by weight aqueous sodium hydroxide solution and 50 g of toluene are placed in a 200 ml four-neck flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel. Prepare
The mixture was heated to 70°C and stirred. Next, add 15.6g of methyl iodide.
It was added dropwise over 60 minutes, and after being kept at the same temperature for 2 hours, the reaction solution was neutralized with hydrochloric acid, left to stand, and separated into an aqueous layer and an organic layer. The aqueous layer was extracted with ethyl ether, and the ether layer was combined with the organic layer. After distilling off the solvent from this organic layer, it was recrystallized from ligroin to obtain 16.7 g of white crystals of 2-methyl-4,6-di-t-butylresorcinol (mp, 117-119°C). rate
70.7%). The elemental analysis values, mass analysis values, and NMR spectrum of this product were as follows. Elemental analysis value C(%) H(%) O(%) Theoretical value 76.2 10.2 13.5 (as C ₁₅ H ₂₄ O ₂ ) Analysis value 76.2 10.6 13.2 Mass analysis value M ⁺ =236 NMR (CDCl ₃ , internal standard TMS, δppm, 60MHz) 7.02 (S, 1H, 5- H ) 4.65 (broad S, 2H, 1-0 H &3- OH ) 2.03 (S, 3H, 2- _CH3 ) 1.33 (S, 18H, -C H ₃ of t-butyl) Examples 2 to 5 According to the method of Example 1, each compound of the present invention was produced under the reaction conditions shown in Table 1. The physical properties of the product are shown in Table 1. In addition, the substituent R in the table is the substituent R of the following structural formula.
This corresponds to

[Table] The NMR data of each target compound obtained in the above examples is shown below. Example ₂ (CDCl3, internal standard TMS, δppm, 60MHz) 7.02 (S, 1H, 5- H ) 4.73 (broad S, 2H, 1- OH & 3- OH ) 2.60 (q, 2H, 2- CH _{2- CH3} ) 1.36 (s, 18H, _-CH3 of t-butyl) 1.16 (t, 3H, ₂ -CH2- _CH3 ) Example ₃ (CDCl3, internal standard TMS, δppm, 90MHz) 7.06 (s, 1H, 5- H ) 4.79 (broad S, 2H, 1- OH & 3- OH ) 2.61 (t, 2H, 2- _{CH2 - CH2CH3} ) 1.67(m, 2H, 2 _{-CH2- CH2} - _CH3 ) 1.41 (s, 18H, _-CH3 of t-butyl) 1.06 (t, 3H, ₂ -CH2CH2 _{- CH3} ) Example ₄ (CCl4, Internal standard TMS, δppm, 90MHz) 7.00 (s, 1H, 5- H ) 5.95 (complex m, 1H, 2-CH ₂ -CH =
CHaHb) 5.22 (m, 1H, -CH ₂ -CH=C Ha Hb) 5.09 (m, 1H, -CH ₂ -CH=CHa Hb ) 4.75 (broad S, 2H, 1- OH & 3- OH ) 3.44 (m, 2H, 2-C H ₂ -CH=CHaHb) 1.40 (s, 18H, -C H ₃ of t-butyl) Example 5 (CDCl ₃ , internal standard TMS, δppm, 90MHz) 7.07 (s, 1H , 5- H ) 4.75 (broad S, 2H, 1- OH & 3- OH ) 2.60 (t, 2H, 2-CH2-( _CH2 ) ₁₀ - _CH3 ) 1.41(s, _20H , 2- CH ₂ −(CH ₂ ) ₁₀ −CH ₃ ) 1.30 (s, 18H, −CH ₃ of t-butyl) 0.90 (t, 3H, 2−(CH ₂ )11−CH ₃ ) Comparative example 1 Stirring aluminum chloride 6.7 in a 100 ml four-necked flask equipped with a reflux condenser, thermometer and dropping funnel.
g and 20.0 g of nitrobenzene were charged and maintained at 20°C. Then 11.1 g of 4,6-di-t-butylresorcinol was dissolved in 11.1 g of nitrobenzene.
g was added dropwise over 30 minutes, and the mixture was stirred at the same temperature for 2 hours. Thereafter, dilute hydrochloric acid and chloroform were added, and the mixture was allowed to stand and separated into an aqueous layer and an oil layer. The aqueous layer was extracted with methyl isobutyl ketone, the extracted oil layer was added to the previous oil layer, and this oil layer was analyzed by gas chromatography, which revealed that 8.0 g of 4,6-di-t-butylresorcinol, 2.2 g of 4-t-butylresorcinol
g, resorcinol 0.06 g, and the desired 2-methyl-4,6-di-t-butylresorcinol was not observed. Application example 1 100ml with stirrer, reflux condenser and thermometer
30.0 g of nitrobenzene, 2-methyl-4,6-di-t-butylresorcinol in a four-necked flask.
23.6g and 0.12g of concentrated sulfuric acid were charged, the temperature was raised to 200°C, and the temperature was maintained for 1 hour. During this time, the gas generated was introduced into a gas absorption tube and absorbed into concentrated sulfuric acid.
Thereafter, nitrobenzene was distilled off under reduced pressure to obtain 9.9 g of 2-methylresorcinol (138° C./10 mmHg) (yield 79.8%).

Claims (1)

[Claims] 1. General formula (In the formula, R represents a linear alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 3 carbon atoms.) A resorcinol derivative represented by the following formula. 2 4,6-di-t-butylresorcinol and a halide represented by the general formula RX (wherein R represents a linear alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 3 carbon atoms), General formula characterized by reaction in aqueous alkaline solution (In the formula, R has the same meaning as above.) A method for producing a resorcinol derivative represented by the following. 3. The method according to claim 2, wherein the alkali in the aqueous alkali solution is one or more selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide.