JPH06298688A - Production of alkyl-substituted hydroquinone - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as photographic chemicals, etc., in high efficiency and yield by reacting a hydroquinone compound with a specific alpha-olefin in the presence of activated clay under specific condition. CONSTITUTION:The objective compound is produced by reacting a hydroquinone compound with a 6-30C alpha-olefin such as 1-hexene in the presence of activated clay as an acid catalyst. Water contained in the activated clay is removed before and/or during the reaction. The reaction is carried out by placing a solid basic substance such as sodium acetate and/or a solid desiccant such as molecular sieves in the reaction system and preferably using an aprotic organic solvent such as octane as a solvent for azeotropic distillation and/or for reaction.

Description

Detailed Description of the Invention

[0001]

The present invention relates to hydroquinones and α
The present invention relates to a method for producing an alkyl-substituted hydroquinone useful as a photographic chemical, a polymerization inhibitor, a stabilizer and the like at low cost and in high yield by reacting with an olefin.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an alkyl-substituted hydroquinone by reacting a hydroquinone with an α-olefin, there are a method using a catalyst and a method using an ion exchange resin instead of the catalyst. Broadly divided. The method using the above-mentioned ion exchange resin is not the optimum method from an industrial viewpoint because the reaction time is long and the reaction yield is not sufficient, and the ion exchange resin is expensive. As the above catalyst, acid activated montmorillonite, silica-alumina, synthetic zeolite, sulfuric acid, phosphoric acid,
It is known to use many acid catalysts such as zinc chloride, aluminum chloride and boron trifluoride. However, all of them had low yields and were insufficient as a production method. Among them, in the method using activated clay as an acid catalyst (Japanese Patent Publication No. 46-42890 and Japanese Patent Publication No. 51-12250), when hydroquinone and α-olefin are added all at once without a solvent, and the mixture is heated and reacted, a rapid reaction occurs. The progress of the reaction was observed, and a relatively large amount of some side reaction products were produced along with the rapid progress of the reaction. Therefore, the yield of the desired alkyl-substituted hydroquinone was not always sufficient. In addition, it has been revealed that it is difficult to control the reaction temperature and the like in large-scale production.

[0003]

The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a novel method for producing an alkyl-substituted hydroquinone with high yield. A second object of the present invention is to obtain a high yield even if the reaction temperature is low and the reaction time is short.
An object of the present invention is to provide a novel method for producing an alkyl-substituted hydroquinone that can be produced at low cost. A third object of the present invention is to provide a novel method for producing an alkyl-substituted hydroquinone which is excellent in production suitability on a large scale.

[0004]

Means for Solving the Problems The above-mentioned problems are as follows in a method for producing an alkyl-substituted hydroquinone by using activated clay with hydroquinone and an α-olefin having 6 to 30 carbon atoms as an acid catalyst. ) And (2). (1) Water contained in the activated clay is removed before and / or during the reaction. (2) A solid basic substance and / or a solid desiccant coexist in the reaction system. In addition, the reaction rate can be more effectively improved by combining the above two means (1) and (2).

In the method (1) and / or (2), at least one of the following two types of operations is
It has also become clear that it is preferable to do one. (3) An aprotic organic solvent is used as a solvent for azeotropic distillation and / or reaction. (4) At least 1 part of α-olefin is added dropwise after charging. The reaction rate can be more effectively improved by combining the two means (3) and (4).

The present invention will be described in detail below. In the present invention, the method for producing an alkyl-substituted hydroquinone using hydroquinone and an α-olefin having 6 to 30 carbon atoms as an acid catalyst using activated clay may be any known method, that is, the reaction. The method of adding reagents and catalysts necessary for the above and the order of addition can be arbitrarily determined. As a general method, hydroquinones and activated clay as an acid catalyst are mixed, and an α-olefin is heated and reacted. At this time, all the α-olefins may be mixed and then heated and reacted, or as described below, a part or all of the α-olefins may be mixed after the heating reaction is started. Further, after mixing the hydroquinone and the α-olefin, activated clay as an acid catalyst may be mixed. Further, these reactions may be carried out without a solvent, or an organic solvent may be used. The organic solvent may be an organic solvent that dissolves hydroquinones, but is preferably an aprotic organic solvent as described later.

The activated clay used in the present invention means acid treatment.
It is a white clay that has been activated to enhance its activity.
Natural clay known to have properties, commonly known as acid clay
Acid-treat similar clay with acid such as sulfuric acid
It is made from petroleum in general.
It is often used for decolorization and purification of products. Of this special clay
There are many studies on the main body, mainly montmorillon
Clay minerals such as knight, halloysite and kaolinite
It is known to be a constituent component (for example, Al ₂O₃．
4 SiO₂． nH₂O). However, recently activated clay
We also found clay that is more advantageous than acid clay as a raw material soil
Has been. Appearance is white to slightly grayish powder
It usually contains about 5 to 15% by weight of water. Active white
Soil manufacturers (eg, Japan Activated White Clay, Mizusawa Chemical, East
Various types of activated clay depending on the application
One of the features is that it is supplied at the same time and is very inexpensive.
It Specifically, Galleon Earth V₂, Galleon earth
NV, Galleon Earth SV (manufactured by Mizusawa Chemical), activated clay R
-15 (made by Japan activated clay), activated clay F-116 (Toyo
Activated clay) and the like.

Regarding the use of clay minerals such as activated clay as a catalyst in the present invention, for example, "Clay Chemistry" Vol. 28, No. 4, pp. 200 to 204 (19)
88), Applied Clay science, 2 (1987), p.
p. It is widely known as outlined in 309 to 342 and the like, and the method of using activated clay as an acid catalyst as in the present invention is also known in the above-mentioned Japanese Patent Publication No. 46-42890.

What shape is the activated clay used in the present invention?
However, it is preferably 150 mesh or more.
Above, more preferably fine powder of 200 mesh or more
The ones are good. The addition amount of activated clay in the present invention is preferably
It is more preferable that the hydroquinone used in the reaction is triple
Amounts of at least 30% by weight are suitable,
50 wt% or more is more preferable, 80 wt% or more is further
preferable. The upper limit is 250% by weight or less.
200% by weight or less is preferable, and 150% by weight or less
More preferably, 120% by weight or less is further preferable.
In addition, in the present invention, as an auxiliary catalyst other than activated clay
For example, sulfuric acid, phosphoric acid, paratoluene sulfonic acid, etc.
You may use together. Also, metal compounds such as B ₂O₃,
Al₂O₃, ZnO, ZnCl₂, CuCl₂, MgC
l₂Etc. on activated clay to improve catalytic activity
Good. Further, activated clay used in the method of the present invention is disclosed in
In accordance with the method described in Sho 63-36837.
Can be used.

The reaction temperature used in the present invention is 70 ° C. or higher 2
The temperature is preferably 00 ° C or lower, but preferably 80 ° C or higher and 1
50 ° C or lower, more preferably 80 ° C or higher and 14
0 ° C or lower, most preferable temperature is 90 ° C or higher and 130
It is below ℃. It goes without saying that this temperature refers to the internal temperature of the reaction system. In the method of the present invention, the reaction time can be variously set depending on the reaction temperature, but is preferably 30 minutes to 6 hours, more preferably 40 minutes to 4 hours, and particularly preferably 1 hour to 2 hours. The present invention is a preferred embodiment because a high reaction yield can be obtained even at a relatively low temperature of 150 ° C. or lower or a short time.

In the present invention, it is considered that suppression of by-products and improvement of reaction controllability have been achieved by means of the above (1) and / or (2). Hereinafter, the means (1) and (2) will be described.

As the means for removing water before the reaction in (1), a method of azeotropic distillation using an organic solvent can be mentioned. In addition, a method of exposing the activated clay to strong heat (about 100 ° C. or higher) under a nitrogen stream to remove water can be mentioned. In this case, if the removed activated clay is left to stand, it absorbs water. Therefore, it is preferable to do it just before use. As a means for removing water during the reaction, a method of distilling off water during the reaction by using an excess amount of α-olefin having a relatively low boiling point can be mentioned. In addition to these, the method of using the solid desiccant (2) may be used as the water removing means. In the present invention, the means for removing water by azeotropic distillation using the organic solvent before the reaction in (1) is a preferred embodiment from the viewpoint of improving the yield.

As mentioned above, the activated clay is usually 5 to 1
It is known that it exists stably in a state of containing 5% by weight of water, and it quickly returns to a stable state even when forced dehydration is performed. Activated clay that has been dried in advance when no solvent is used. It is not preferable to carry out the reaction by using from the viewpoint of reaction control.

The solid basic substance in (2) is an inorganic chemical species capable of trapping protons, such as alkali metal and alkaline earth metal acetates, carbonates and oxides.
Examples thereof include hydroxide and oxides of other metals. These solid basic substances have little or no solubility in aprotic organic solvents. Specifically, as the acetate, CH ₃ COONa, CH ₃ COOK, etc., and as the carbonate, K ₂ CO ₃ Na ₂ CO ₃ , CaCO
_As oxides such as ₃ and MgCO ₃ , MgO and CaO
Examples of hydroxides such as and BaO include NaOH, KOH and Ca (OH) ₂ . The amount of the solid basic substance added in the present invention is 2 with respect to the activated clay used in the reaction.
-60% by weight is suitable, but in terms of yield, it is preferably 5-40% by weight, more preferably 10-2.
It is in the range of 0% by weight.

The solid desiccant (2) is a substance that removes water, more specifically, a substance that physically adheres to or adsorbs on the activated clay and has a function of desorbing the water contained therein. Usually, a desiccant having a strong heat resistance, which is used as a desiccant for an organic solvent and does not release water trapped under reaction conditions of 80 ° C. or higher and 150 ° C. or lower, is preferable.
Specific examples include synthetic fluorite molecular sieves, Na ₂ SO ₄ , MgSO ₄ , and C.
Examples include aCl _{2 and the} like. Molecular sieves
Molecular sieves 3A, molecular sieves 4
A, molecular sieves 5A, molecular sieves 15A and the like are commercially available from Wako Pure Chemical Industries, Ltd. The addition amount of the solid desiccant in the present invention is appropriately in the range of 2 to 60% by weight based on the activated clay used in the reaction, but in terms of yield, it is preferably in the range of 5 to 40% by weight, and more preferably. It is in the range of 10 to 20% by weight.

In the method of the present invention, it is preferable to carry out the reaction in an aprotic organic solvent as a solvent for azeotropic distillation and / or reaction. From the viewpoint of increasing the reaction rate, a preferable aprotic organic solvent is, for example, octane.
(n-, iso-), trichloroethane, tetrachloroethane, chlorobenzene (mono-, di-), toluene, dioxane, sulfolane, decalin, methylcyclohexane, nonane, decane and the like. Organic solvents (tetrachloroethane, octane (n-, iso-), chlorobenzene (mono-, di-
-) And toluene) are preferable. These solvents may be mixed and used according to the purpose. For example, a solvent having a relatively high polarity (for example, sulfolane or dimethyl sulfoxide) may be used in combination with the nonpolar solvent to achieve both reactivity and solubility. it can. The aprotic organic solvent may be used in an amount of 0.5 to 20 times by volume, preferably 1 to 10 times by volume, more preferably 2 to 5 times by volume, based on 1 weight of the hydroquinone as a raw material.

In the method of the present invention, it is preferable that at least a part of the α-olefin is charged and then added dropwise. This is considered to prevent the starting hydroquinones and α-olefins from reacting rapidly to generate heat, making reaction control difficult and causing side reactions. Of these, the preferred method is to put the starting hydroquinones and activated clay in the solvent, azeotropically dehydrate them while heating and stirring them, and then add the entire amount of α-olefin dropwise thereto.

In the method of the present invention, the reaction may be carried out in an atmosphere of an inert gas such as nitrogen or argon in order to suppress undesired side reactions during the reaction. In the method of the present invention, it is preferable to add an auxiliary solvent (for example, toluene, hexane, ethyl acetate, etc.) after the reaction to carry out filtration of the catalyst and washing with water. The alkyl-substituted hydroquinone of the present invention is obtained by the above reaction and isolated and purified by a suitable isolation means. Examples of such means include a solvent extraction method, a recrystallization method, a filtration method, a column chromatography method, and a single layer chromatography method.

The starting hydroquinones used in the present invention are unsubstituted hydroquinones or monosubstituted hydroquinones. The alkyl-substituted hydroquinones obtained by the method of the present invention are hydroquinones substituted with at least one alkyl group alkylated by the reaction with an α-olefin.

The monosubstituted hydroquinones used in the present invention are preferably those represented by the following general formula (I).

[0021]

[Chemical 1]

(In the general formula (I), R ¹ represents an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a sulfonamide group or a ureido group.)

The alkyl group, aryl group, acylamino group, alkoxy group, alkylthio group, arylthio group and ureido group represented by R ¹ may be substituted, and examples of such a substituent include a halogen atom (for example, fluorine atom). , Chlorine, bromine), cyano group, nitro group, hydroxyl group, carboxyl group, sulfo group, alkyl group (eg, methyl, t-butyl, t-octyl, hexadecyl, 1-ethyl-1-methylpentyl, 1-hexyl- 1-methylnonyl), aryl group (for example, phenyl), alkoxy group (for example, methoxy, butoxy), aryloxy group (for example, phenoxy), alkylthio group (for example,
Methylthio, butylthio), arylthio groups (eg,
Phenylthio), alkoxycarbonyl group (eg ethoxycarbonyl), acylamino group (eg acetylamino, benzoylamino, hexadecanoylamino), sulfonamide group (eg methanesulfonamide), ureido group (eg butylureido, dodecyl) Ureido), heterocyclic thio group (for example, 1-phenyltetrazolylthio group), acyl group (for example, acetyl),
Examples thereof include a sulfonyl group (eg, benzenesulfonyl). Preferred groups that can be substituted are halogen atoms, hydroxyl groups, sulfo groups, alkyl groups, acylamino groups, and sulfonamide groups.

R ¹ is specifically a linear or branched alkyl group (preferably having a carbon number of 1 to 30, more preferably 1 to 14, for example, methyl, ethyl, i-propyl, t.
-Butyl, octyl, t-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 1-
Ethyl-1-methylpentyl, 1-hexyl-1-methylnonyl), aryl group (preferably having 6 to 3 carbon atoms)
0, for example, phenyl, halogen atom (for example, chlorine atom, fluorine atom), acylamino group (preferably having 2 to 30 carbon atoms, acetylamino, benzoylamino, hexadecanoylamino, tridecanoylamino), alkoxy group (preferably Is 1 to 30 carbon atoms, for example, methoxy, an alkylthio group (preferably 1 to 30 carbon atoms,
For example, methylthio, dodecylthio, hexadecylthio,
Octylthio), an aryloxy group (preferably having 6 to 30 carbon atoms such as phenoxy), an arylthio group (preferably having 6 to 30 carbon atoms such as phenylthio, p-).
Methoxyphenylthio), a sulfonamide group (preferably having a carbon number of 1 to 30, for example, methanesulfonamide),
Alternatively, it represents an ureido group (preferably having a carbon number of 2 to 30, such as methylureido and butylureido). R ¹ is preferably an alkyl group or an acylamino group. Specific examples of the hydroquinone represented by the general formula (I) are shown below, but the invention is not limited thereto.

[0025]

[Chemical 2]

[0026]

[Chemical 3]

[0027]

[Chemical 4]

The hydroquinones used in the present invention are preferably unsubstituted hydroquinones or monosubstituted hydroquinones in which R ¹ is an alkyl group or an acylamino group, and unsubstituted hydroquinones or R ¹ is an alkyl group. Monosubstituted hydroquinone is particularly preferred.

The α-olefin used in the present invention is
It is a general term for linear or branched alkenes having a double bond at the end. Preferably, it can be represented by the general formula (II). Formula ^{_{(II) CH 2 = CHR 2}} ( wherein, R ² is. Represents an unsubstituted alkyl group having a linear or branched with 6-20 carbon atoms) having from 6 to 20 carbon atoms of R ² in the formula
As the linear or branched unsubstituted alkyl group, for example, a hexyl group, an octyl group, a decyl group, a dodecyl group,
A tetradecyl group, a hexadecyl group, an octadecyl group etc. are mentioned.

The α-olefin used in the present invention is preferably a linear one having 6 to 22 carbon atoms, and more preferably 8 to 18 carbon atoms. For example, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-octacosene and the like can be mentioned. Since α-olefins are usually produced by polymerizing ethylene, many of them having an even number of carbon atoms are commercially available. The α-olefin may be a mixture of two or more kinds, and the mixture may be a mixture of single substances during the reaction or a mixture of α-olefin as a fraction.

In the method of the present invention, the ratio of the raw material hydroquinone and the α-olefin varies depending on the reactivity of the raw material and the intended product. In the case of using unsubstituted hydroquinone as a raw material, in order to obtain a monoalkyl compound as a main component, it is preferable to use 0.3 to 1.0 mol of α-olefin per 1 mol of hydroquinone and a dialkyl compound as a main component. In order to obtain it, it is preferable to use 2.0 to 3.0 mol of α-olefin with respect to 1 mol of hydroquinone.

When mono-substituted hydroquinone is used as a raw material, in order to obtain a monoalkylation reaction product as a main component, 1 mol of mono-substituted hydroquinone is used.
It is preferable to use 1.0 to 1.5 mol, and to obtain the dialkylated product as the main component, it is preferable to use 2.0 to 3.0 mol per 1 mol of monosubstituted hydroquinone. Further, the above polyalkyl-substituted hydroquinones can also be synthesized by appropriately changing the ratio of the starting hydroquinones to be used and the α-olefin.

Specific examples of the alkyl-substituted hydroquinones that can be produced by the method of the present invention are shown below, but the present invention is not limited thereto.

[0034]

[Chemical 5]

[0035]

[Chemical 6]

[0036]

[Chemical 7]

[0037]

[Chemical 8]

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Comparative Synthesis Example 1. Hydroquinone 55.0g (0.5mo
l), 21-tetradecene 216.0 g (1.1 mol)
And activated white clay galleon earth V ₂ (manufactured by Mizusawa Chemical) 44g
(80% by weight to HQ) was mixed and stirred, and the internal temperature was raised to 100 ° C. under a nitrogen stream to carry out a reaction for 2 hours.

Comparative Synthesis Example 2. The reaction was performed in the same manner as in Comparative Synthesis Example 1 except that 200 ml of chlorobenzene was used as the solvent.

Synthesis Example 1. The reaction was performed in the same manner as in Comparative Synthesis Example 1 except that 10 g of Na ₂ CO ₃ was mixed with and stirred with activated clay.

Synthesis Example 2. Hydroquinone 55.0g
(0.5 mol) and 44 g (80% by weight of HQ) of activated white clay galleon earth V ₂ (manufactured by Mizusawa Chemical Co., Ltd.) were mixed and stirred with 300 ml of chlorobenzene, and the internal temperature under nitrogen stream was adjusted to 1
100 ml of chlorobenzene and 5 m of water are heated up to 00 ° C.
After distilling off l, 216.0 g of 1-tetradecene
(1.1 mol) was added dropwise over 30 minutes. Then, the reaction was carried out for 2 hours.

Synthesis Example 3. Hydroquinone 55.0g
(0.5 mol), activated clay clay galleon earth V ₂ (manufactured by Mizusawa Chemical Co., Ltd.) 44 g (80 wt% vs. HQ) was added to n-octane 3
The mixture was stirred using 00 ml, heated to n-octane reflux (123 ° C) under a nitrogen stream, and n-octane 100 was added.
After distilling off 5 ml of water and 5 ml of water, 1-tetradecene 21
6.0 g (1.1 mol) was added dropwise over 30 minutes. Then, the reaction was carried out for 2 hours.

Synthesis Example 4. Hydroquinone 55.0g
(0.5 mol), 10-tetradecene 108.0 g
(0.55 mol), activated white clay galleon earth V ₂ (manufactured by Mizusawa Chemical Co., Ltd.) 44 g (80% by weight relative to HQ) and Na ₂ CO
₃ 10g is mixed and stirred, and the internal temperature is 100 ° C under nitrogen flow.
After heating up to 108.0 g of 1-tetradecene to 30
It dripped over minutes. Then, the reaction was carried out for 2 hours.

Synthesis Example 5. Hydroquinone 55.0g
(0.5 mol), activated white clay galleon earth V ₂ (manufactured by Mizusawa Chemical Co., Ltd.) 44 g (80% by weight relative to HQ), Na ₂ CO ₃
10 g and 200 ml of chlorobenzene were mixed and stirred,
After raising the internal temperature to 100 ° C. under a nitrogen stream, 216.0 g (1.1 mol) of 1-tetradecene was added dropwise over 30 minutes. Then, the reaction was carried out for 2 hours.

Synthesis Example 6. The reaction was performed in the same manner as in Synthesis Example 5 except that 10 g of Molecular Sieves 3A (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 10 g of Na ₂ CO ₃ .

Synthesis Example 7. Hydroquinone 55.0g
(0.5 mol), activated white clay galleon earth V ₂ (manufactured by Mizusawa Chemical Co., Ltd.) 44 g (80 wt% vs. HQ) g were mixed and stirred using 300 ml of chlorobenzene, and the internal temperature was raised to 100 ° C. under a nitrogen stream. Chlorobenzene 100ml and water 5
The ml was distilled off. After adding 5 g of Na ₂ CO ₃ into the reaction system, 216.0 g of 1-tetradecene (1.1 mo)
1) was added dropwise over 30 minutes. Then, the reaction was carried out for 2 hours.

In Comparative Synthesis Examples 1 and 2 and Synthesis Examples 1 to 7, after completion of the reaction, high performance liquid chromatography (HPL
The reaction mixture was analyzed using C), and the reaction yield of the target exemplary compound (HQ-1) was determined from the calibration curve. Also,
The ratio with monoalkylhydroquinone (HQ-6) was determined. The dialkyl hydroquinone obtained was treated with proton N
As a result of MR analysis, it was found to be a 70:30 (molar ratio) mixture of a 2,5-dialkyl compound and a 2,6-dialkyl compound. Table 1 shows the HPLC data on the respective synthesis examples of the exemplified compound (HQ-1).

[0048]

[Table 1]

Comparative Synthesis Example 3. Hydroquinone 55.0g
(0.5 mol), 1-octene 123.0 g (1.1
mol) and 33 g (60% by weight of HQ) of activated clay clay galleon earth V ₂ (manufactured by Mizusawa Chemical Co., Ltd.), and the mixture was heated to 1-octene reflux (123 ° C.) under a nitrogen stream and reacted for 2 hours. It was

Synthesis Example 8. After heating, 70 ml of 1-octene
The reaction was performed in the same manner as in Comparative Synthesis Example 3 except that 5 ml of water was distilled off.

Synthesis Example 9. Hydroquinone 55.0g
(0.5 mol), 1-octene 112.0 g (1.0
mol) and 33 g of activated white clay galleon earth V ₂ (manufactured by Mizusawa Chemical Co., Ltd., 60 wt% vs. HQ), and heated to 1-octene reflux (123 ° C.) under a nitrogen stream to 1-
After 50 ml of octene and 5 ml of water were distilled off, 40.0 g of 1-octene was added dropwise over 30 minutes. Then, the reaction was carried out for 2 hours.

Synthesis Example 10. Hydroquinone 55.0g
(0.5 mol), activated white clay galleon earth V ₂ (manufactured by Mizusawa Chemical Co., Ltd.) 33 g (60 wt% vs. HQ), 5 g of MgO and 200 ml of chlorobenzene were mixed and stirred, and the internal temperature was raised to 120 ° C. under a nitrogen stream. Later 1-octene 12
3.0 g (1.1 mol) was added dropwise over 30 minutes. Then, the reaction was carried out for 2 hours.

Synthesis Example 11. The reaction was performed in the same manner as in Synthesis Example 10 except that 5 g of Molecular Sieves 3A (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 5 g of MgO.

Synthesis Example 12. Na instead of 5 g of MgO
_The reaction was performed in the same manner as in Synthesis Example 10 except that 5 g of ₂ CO ₃ was used.

Synthesis Example 13. Ca instead of MgO 5g
The reaction was performed in the same manner as in Synthesis Example 10 except that 5 g of (OH) ₂ was used.

Synthesis Example 14. CH instead of MgO 5g
_The reaction was performed in the same manner as in Synthesis Example 10 except that 5 g of ₃ COONa was used.

Synthesis Example 15. After heating, chlorobenzene 10
The reaction was carried out in the same manner as in Synthesis Example 12, except that 0 ml and 5 ml of water were distilled off, and then 1-octene was added dropwise.

In Comparative Synthesis Example 3 and Synthesis Examples 8 to 15,
After completion of the reaction, the reaction mixture was analyzed using gas chromatography, and the reaction yield of the target exemplary compound (HQ-3) was determined from a calibration curve. Moreover, as a result of proton NMR analysis of the obtained dialkylhydroquinone, 2,5-
It was found to be a 75:25 (molar ratio) mixture of the dialkyl compound and the 2,6-dialkyl compound. Table 2 shows the gas chromatographic data in Comparative Synthesis Example 3 and Synthesis Examples 8 to 15 of the exemplified compound (HQ-3).

[0059]

[Table 2]

Comparative Synthesis Example 4. Methyl hydroquinone 6
2.0 g (0.5 mol), 1-octadecene 136.
When 0 g (0.54 mol) and activated clay R-15 (manufactured by Nippon Activated Clay) 12 g (20 wt% relative to HQ) were mixed and stirred, and the internal temperature was raised to 130 ° C. under a nitrogen stream,
An exothermic reaction was observed, and the temperature inside the system rose to 150 ° C.
After waiting until the system temperature finally reached 130 ° C., the reaction was carried out for 1 hour.

Comparative Synthesis Example 5. The reaction was carried out in the same manner as in Comparative Synthesis Example 4 except that 150 ml of chlorobenzene was used as the solvent, and after completion of the reaction, the reaction yield of the target product was determined by gas chromatography.

Synthesis Example 16. Methyl hydroquinone 62.
0 g (0.5 mol), activated clay R-15 (manufactured by Nippon Activated Clay) 12 g (20 wt% vs. HQ), 3 g of MgO and 150 ml of chlorobenzene were mixed and stirred, and the internal temperature was raised to 130 ° C under a nitrogen stream. And then 1-octadecene 13
6.0 g (0.54 mol) was added dropwise over 30 minutes.
Then, the reaction was carried out for 1 hour.

Synthesis Example 17. 3 g of MgO is added to Na ₂ CO ₃
The reaction was performed in the same manner as in Synthesis Example 16 except that the amount was changed to 3 g.

Synthesis Example 18. Methyl hydroquinone 62.
0 g (0.5 mol), activated clay R-15 (manufactured by Nippon Activated Clay) 12 g (20 wt% to HQ) g and 200 ml of 1-octane were mixed and stirred, and the solvent was refluxed under a nitrogen stream (12).
3 ° C), n-octane 100 ml and water 3 m
After distilling off 1 l, 136.0 g of 1-octadecene (0.
(54 mol) was added dropwise over 30 minutes. Then, the reaction was carried out for 1 hour.

Synthesis Example 19. Methyl hydroquinone 62.
0 g (0.5 mol), activated clay R-15 (manufactured by Nippon Activated Clay) 12 g (20 wt% vs. HQ), MgO 3 g and 250 g of chlorobenzene were mixed and stirred, and the internal temperature under a nitrogen stream was 130 ° C. After the temperature was raised to 100 ml and 100 ml of chlorobenzene and 3 ml of water were distilled off, 136.0 g (0.54 mol) of 1-octadecene was added dropwise over 30 minutes. Then, the reaction was carried out for 1 hour.

In Comparative Synthetic Examples 4 and 5 and Synthetic Examples 16 to 19, after completion of the reaction, the reaction mixture was analyzed by gas chromatography to obtain the desired exemplary compound (HQ-5).
The reaction yield of was determined from the calibration curve. Further, as a result of proton NMR analysis of the obtained dialkylhydroquinone,
85 of 2,5-dialkyl compound and 2,6-dialkyl compound:
It was found to be a 15 (molar ratio) mixture. As described above, Comparative Synthesis Examples 4 and 5 and Synthesis Example 16 of the exemplified compound (HQ-5)
Gas chromatographic data for ~ 19 are shown in Table 3.

[0067]

[Table 3]

Comparative Synthesis Example 6. Hydroquinone 66.0g
(0.6 mol), 1-octadecene 126.0 g
(0.5 mol) and activated clay F-116 (manufactured by Toyo Activated Clay) 7 g (-10% by weight relative to HQ) were mixed and stirred, and the internal temperature was raised to 100 ° C. under a nitrogen stream to react for 2 hours. I did.

Comparative Synthesis Example 7. The reaction was carried out in the same manner as in Comparative Synthesis Example 6 except that 200 ml of chlorobenzene was used as the solvent.

Synthesis Example 20. Hydroquinone 66.0g
(0.6 mol), activated clay F-116 (made by Toyo activated clay) 7 g (-10 wt% vs. HQ), chlorobenzene 30
0 ml was mixed and stirred, the temperature was raised to 100 ° C. under a nitrogen stream, 100 ml of chlorobenzene and 1 ml of water were distilled off, and 126.0 g (0.5 mol) of 1-octadecene was added dropwise over 30 minutes. Then, the reaction was carried out for 2 hours.

Synthesis Example 21. Hydroquinone 66.0g
(0.6 mol), activated clay F-116 (made by Toyo activated clay) 7 g (-10% by weight relative to HQ), sulfolane 200 m
1 and 100 ml of toluene were mixed and stirred, and the temperature was raised to toluene reflux (111 ° C.) under a nitrogen stream. Then, after distilling off all the toluene and 1 ml of water, 1-octadecene 12
6.0 g (0.5 mol) was added dropwise over 30 minutes. Then, the reaction was carried out for 1 hour.

Synthesis Example 22. Hydroquinone 66.0g
(0.6 mol), activated clay F-116 (made by Toyo activated clay) 7 g (-10 wt% vs. HQ), Na ₂ CO ₃ 2 g
Was stirred with 300 ml of chlorobenzene, heated to 100 ° C. under a nitrogen stream, and then 1-octadecene 1 was added.
26.0 g (0.5 mol) was added dropwise over 30 minutes.
Then, the reaction was carried out for 2 hours.

Synthesis Example 23. Increase the temperature and chlorobenzene 10
The reaction was performed in the same manner as in Synthesis Example 22 except that 1 ml of 1-octadecene was added dropwise after removing 0 ml of water and 1 ml of water.

In Comparative Synthesis Examples 6 and 7, and Synthesis Examples 20 to 23, after completion of the reaction, the reaction mixture was analyzed by gas chromatography to obtain the desired exemplary compound (HQ-7).
The reaction yield of was determined from the calibration curve. As described above, the exemplified compound (H
Table 4 shows the gas chromatographic data of Comparative Synthesis Examples 6 and 7 of Q-7) and Synthesis Examples 20 to 23.

[0075]

[Table 4]

Comparative Synthesis Example 8. Hydroquinone 55.0g
(0.5 mol), 185.2 g of 1-dodecene (1.1
mol), activated white clay galleon earth NV (manufactured by Mizusawa Chemical Co., Ltd.)
8 g (~ 15% by weight to HQ) of chlorobenzene 200 m
The mixture was stirred with 1, and the internal temperature was raised to 100 ° C. under a nitrogen stream to carry out a reaction for 2 hours.

Synthesis Example 24. Hydroquinone 55.0g
(0.5 mol), activated white clay galleon earth NV (manufactured by Mizusawa Chemical Co., Ltd.) 8 g (-15% by weight relative to HQ) and Na ₂ CO _3.
2 g was mixed and stirred with 200 ml of chlorobenzene, the internal temperature was raised to 100 ° C. under a nitrogen stream, and 185.2 g (1.1 mol) of 1-dodecene was added dropwise over 30 minutes. Then, the reaction was carried out for 2 hours.

Synthesis Example 25. Hydroquinone 55.0g
(0.5 mol), 8 g of activated white clay galeon earth NV (manufactured by Mizusawa Chemical Co., Ltd.) (to 15% by weight with respect to HQ) were mixed and stirred using 300 ml of chlorobenzene, and the internal temperature was set to 1 under a nitrogen stream.
100 ml of chlorobenzene and 2 m of water are heated to 00 ° C.
After distilling off l, 185.2 g of 1-dodecene (1.1
(mol) was added dropwise over 30 minutes. Then, the reaction was performed for 2 hours.

Synthesis Example 26. Hydroquinone 55.0g
(0.5 mol), 8 g of activated white clay galeon earth NV (manufactured by Mizusawa Chemical Co., Ltd.) (to 15% by weight with respect to HQ) were mixed and stirred using 300 ml of chlorobenzene, and the internal temperature was set to 1 under a nitrogen stream.
100 ml of chlorobenzene and 2 m of water are heated to 00 ° C.
1 was distilled off. After adding 2 g of Na ₂ CO ₃ to the reaction system, 185.2 g (1.1 mol) of 1-dodecene was added dropwise over 30 minutes. Then, the reaction was performed for 2 hours.

In Comparative Synthesis Example 8 and Synthesis Examples 24 to 26, after completion of the reaction, the reaction mixture was analyzed by gas chromatography to obtain the reaction yield of the target exemplified compound (HQ-2) from the calibration curve. It was Further, as a result of proton NMR analysis of the obtained dialkylhydroquinone, 2,
55:45 of 5-dialkyl body and 2,6-dialkyl body
It was found to be a (molar ratio) mixture. Table 5 shows the gas chromatographic data relating to Comparative Synthesis Example 8 and Synthesis Examples 24 to 26 of the exemplified compound (HQ-2).

[0081]

[Table 5]

Comparative Synthesis Example 9. Methyl hydroquinone 6
2.0 g (0.5 mol), 1-tetradecene 245.
5 g (1.25 mol) and activated clay Galleon Earth V
₂ 55 g (89 wt% vs. HQ) mixing攪samurai, the inner temperature under a nitrogen stream was heated to 110 ° C. was carried out for 2 hours. After completion of the reaction, the reaction mixture was analyzed by gas chromatography to find that the desired exemplary compound (HQ
-31) and a monoalkylated product in a 60:40 (molar ratio) mixture. The reaction mixture was purified by column chromatography to obtain the target HQ-31. Yield 124g (48%)

Synthesis Example 27. Methyl hydroquinone 62.
0 g (0.5 mol), activated clay Galleon Earth V ₂
55 g (89 wt% vs. HQ), and chlorobenzene 30
0 ml was mixed and stirred, the internal temperature was raised to 110 ° C. under a nitrogen stream, 100 ml of chlorobenzene and 5 ml of water were distilled off, and then 245.5 g of 1-tetradecene (1.25 mo)
1) was added dropwise over 30 minutes. Then, the reaction was carried out for 2 hours. After the reaction was completed, the reaction mixture was analyzed by gas chromatography to find that the target exemplified compound (HQ-3
It was found to be a 78:22 (molar ratio) mixture of 1) and the monoalkylated product. The reaction mixture was purified by column chromatography to obtain the target HQ-31. Yield 170g (65%)

Synthesis Example 28. Methyl hydroquinone 62.
0 g (0.5 mol), activated clay Galleon Earth V ₂
55 g (89% by weight relative to HQ), 10 g of Na ₂ CO ₃ and 200 ml of chlorobenzene were mixed and stirred, and the internal temperature was raised to 110 ° C. under a nitrogen stream, and then 1-tetradecene 2
45.5 g (1.25 mol) was added dropwise over 30 minutes. After reacting for 2 hours, after the reaction was completed, the reaction mixture was analyzed by gas chromatography.
Objective compound (HQ-31) and monoalkylated 7
It was found to be a 5:25 (molar ratio) mixture. The reaction mixture was purified by column chromatography to obtain the target HQ-31. Yield 162g (62%)

From Tables 1 to 5 and Reaction Examples 27 and 28, it can be seen that the reaction rate can be improved by the method of the present invention.

[0086]

According to the present invention, alkyl-substituted hydroquinones can be produced in high yield.

Claims (3)

[Claims] 1. Hydroquinones and α having 6 to 30 carbon atoms
A method for producing an alkyl-substituted hydroquinone using activated clay with an olefin as an acid catalyst, which comprises the following means (1) and / or (2). (1) Water contained in the activated clay is removed before and / or during the reaction. (2) A solid basic substance and / or a solid desiccant coexist in the reaction system. 2. The method for producing an alkyl-substituted hydroquinone according to claim 1, wherein an aprotic organic solvent is used as a solvent for azeotropic distillation and / or reaction. 3. The method for producing an alkyl-substituted hydroquinone according to claim 1, wherein at least a part of the α-olefin is charged and then added dropwise.