JPH0234328B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for regioselectively producing β-isopropylnaphthalene by isopropylating naphthalene over a solid or supported perfluorinated sulfonic acid catalyst. Regarding. The production of β-naphthol by the Hock process requires β-isopropylnaphthalene, which is oxidized to α-hydroxyperoxypropyl-2-naphthalene and then treated with acid to effect transfer-cleavage. β-naphthol and acetone are obtained. The production of β-isopropylnaphthalene in solution is usually carried out by Friedel-Crafts type alkylation using Lewis acid halide catalysts such as aluminum chloride or solid catalysts such as phosphoric acid supported catalysts or aluminosilicates. It is done by reaction. In any of these reactions, a mixture of α-isopropylnaphthalene and β-isopropylnaphthalene is usually obtained, which must be further separated and/or isomerized. Furthermore, aluminum chloride and similar Friedel-Crafts catalysts form highly colored complex salts with the reaction products, which ultimately have to be decomposed, resulting in catalyst losses and increased costs. From the results of research on the Friedel-Crafts isopropylation of naphthalene in solution, α-
and β-products [“Friedel-Crafts and Related Reactions”, GAOlha, Volume 11, Chapter XIV, Wiley
Published by Interscience Publishers, 1964; and H.
E. Nursten and AT Peters, Journal of the
Chemical Society (London), 129 (1950), GA
Olah and JAOlah, Journal of the
See American Chemical Society 98 , 1839 (1976)]. Haworth, Letsky and Marvin, Price and Ciskowsky, The Reaction of 2-Propanol with Naphthalene in the Presence of Boron Trifluoride as a Catalyst, Journal of the American Chemical Society,
60, 2499), they reported that pure β-isopropylnaphthalene was obtained by reacting isopropyl bromide and naphthalene in the presence of aluminum chloride (Journal of
(See Chemical Society, 1932, p. 1790). However, U.S. Pat. No. 2,776,322 discloses that in these reactions and the related isopropylation using propene in the presence of an aluminum chloride catalyst, a mixture of α- and β-isomers is obtained. , it is stated that these need to be separated by careful and highly efficient fractional distillation or crystallization. If the naphthalene is then alkylated according to the Friedel-Crafts method with propene using a H ₃ PO ₄ BF ₃ catalyst, a mixture consisting of 70% α-isopropylnaphthalene and 30% β-isopropylnaphthalene is obtained. [Friedman and Nelson, Journal of
Organic Chemistry, 34 3211 (1969)]. More recently, the results of reaction mechanism studies of reactions carried out with aluminum trichloride in dilute CS ₂ or CH ₃ NO ₂ solutions over short periods of time and at very low conversions have shown that the kinetic conditions It has been shown that under thermodynamic conditions the α-isomer tends to form, and under thermodynamic conditions the β-isomer tends to form.
The solution isomerization thermodynamic equilibrium of isopropylnaphthalene using _AlCl3 as a catalyst has also been studied [Olah, Journal of the American Chemical
Society, Vol. 98, 1839 (1976)]. However, no practical method for selectively producing β-isopropylnaphthalene has been achieved so far. For example, US Pat. No. 2,776,332 states that the isopropylnaphthalene obtained by the Friedel-Crafts reaction is a mixture of α- and β-isomers, which must be separated by highly efficient distillation or crystallization. Something is clearly stated.
U.S. Pat. No. 3,458,587 discloses catalytic liquid phase alkylation of naphthalene with propene over solid phosphoric acid to obtain a mixture of α- and β-isopropylnaphthalene, which is then used in a separate operation with anhydrous hydrogen fluoride. isomerization to obtain the desired β-isomer in high proportions. Also,
No. 3,504,045 describes the Friedel-Crafts alkylation of naphthalene to obtain a mixture of α- and β-isomers. The content of the β-isomer is increased by treating the alkylate with H ₃ PO ₃ on a solid support at elevated temperatures. The composition ratio of the product at 350°C is 13% α-isopropylnaphthalene and 52.5% β-isopropylnaphthalene, and also contains 16% naphthalene and 18% high molecular weight polymeric compounds. US Pat. No. 3,504,046 describes the alkylation of naphthalene using a H ₃ PO ₄ catalyst supported on a solid support, similar to that described above. At 350° C. and 800 psig propene pressure, a mixture consisting of 16% naphthalene, 17% α-isopropylnaphthalene and 34.8% β-isopropylnaphthalene is obtained. The prior art for the alkylation of naphthalene can be found in recent US Pat. No. 4,026,959 (1977).
It is summarized and describes a method for the isomerization of isopropylnaphthalene. however,
``There is no process by which isopropylnaphthalene can be produced in high yield and with high β-isomer content and which uses the catalyst economically by direct alkylation of naphthalene with propylene.'' As far as we know, this
This is true regardless of the catalyst used. Therefore, there is a need for a process for obtaining β-isopropylnaphthalene in high yield and purity from naphthalene and propene (as well as other alkylating agents).The present invention provides such a process. The present invention provides a method for producing β-naphthol by isopropylating naphthalene over a solid or carrier-supported perfluorinated sulfonic acid catalyst without purification, separation or subsequent isomerization. The present invention relates to a process for selectively producing β-isopropylnaphthalene with suitably high isomeric purity (90-98%). Friedel-Crafts alkylation in solution using a catalyst such as aluminum chloride usually produces a highly colored complex salt (red oil).
, which necessitates the use of large amounts (molar excess) of catalyst, which is largely
It is bound as a counterion in carbocation complex salts. These complex salts must eventually decompose, resulting in the loss of anhydrous chloride catalyst. When using solid or supported perfluorinated sulfonic acid catalysts according to the invention, no complex salts are formed and therefore no special treatment of the reaction mixture is required. While the conventionally used solid acid catalysts are insufficient to regioselectively produce β-isopropylnaphthalene, the use of solid perfluorinated sulfonic acid catalysts
- Regioselective production of isopropylnaphthalene is possible and the advantages mentioned above are obtained. According to the invention, naphthalene and a suitable alkylating agent, such as 2-halopropane, propane,
- Propanol, β-isopropylnaphthalene can be produced in high purity (90 to 98%). The reaction is carried out in a solution consisting of a high-boiling solvent such as delicane or in a gas phase, using a perfluorinated sulfonic acid catalyst, preferably a carbon number of 6 to 18 high molecular weight perfluorinated alkanesulfonic acids or commercially available Nafion K
The reaction is carried out over a perfluorinated sulfonic acid ion-membrane resin in the acid form, such as an ion-membrane resin (a product of DuPont). This perfluorinated resin sulfonic acid is about 0.01 to 5 mg per gram of catalyst.
It consists of a fluorinated polymer having an equivalent amount of sulfonic acid groups. This polymer catalyst has the following formula: or (In the formula, the ratio of x and y is about 2 to 50, and m is 1
or 2). This polymeric structure is commercially available under the name Nafyon resin. The polymer catalyst having the above structure can be produced by various methods. For example US Patent No. 3282875
The method described in No. 3882093 and the specification of No. 3882093 is
It consists of polymerizing the corresponding perfluorinated vinyl compound. The polymer catalyst is disclosed in U.S. Pat.
It can also be produced by copolymerizing the corresponding perfluorinated vinyl ether with perfluoroethylene and/or perfluoro-α-olefin according to the method of No. 4,041,090.
Although the specific fluorinated repeating units mentioned above are not limited, perfluorinated units are preferred. The isopropylation of naphthalene using said solid catalyst to produce 90-98% β-isopropylnaphthalene is usually carried out at 150-250°C, preferably
It is carried out at a temperature of 170-220° C. and under atmospheric pressure or slightly above atmospheric pressure (up to about 10 atmospheres). Table 1 shows the high selectivity for the β-position in the isopropylation of naphthalene according to specific examples of the invention. According to another aspect of the invention, by using the solid catalyst it is also possible to trans-alkylate naphthalene with propylated aromatic compounds. That is, when naphthalene is reacted with isopropylbenzene, isopropyltoluene or a mixture of di- and polyisopropylnaphthalene, β-isopropylnaphthalene is selectively obtained in high yield. According to yet another aspect of the invention, α- and β
- any mixture of isopropylnaphthalene,
Using a solid catalyst, 150-250℃, preferably 170℃
Processing at temperatures of ˜220° C. and in the same manner as in the absence of the naphthalene reactant provides a method for conversion to essentially pure β-isopropylnaphthalene. Examples of the present invention are shown below. Example 1 10g perfluorodecanesulfonic acid
C ₁₀ F ₂₁ SO ₃ H was deposited onto 75 g of chromosorb from vacuum distillation. 5g of this catalyst
The liquid phase was charged to the alkylation reactor along with 0.1 mol of naphthalene dissolved in 150 ml of delicane. To this solution at a temperature close to its boiling point (190℃),
Propylene was introduced at a flow rate of 0.8/min for 1 hour under stirring. The solution was then stirred for an additional hour at the same temperature as above. After cooling, the catalyst was separated and the solution was distilled under vacuum. The yield of isopropylnaphthalene thus obtained was 68%, and its composition was 92%.
% was the β-isomer and 8% was the α-isomer (analyzed by gas-liquid chromatography). Example 2 The same reaction as in Example 1 was carried out, except that 2-bromopropane was used as the alkylating agent.
The yield of isopropylnaphthalene was 38%, and its composition was 88% β- and 12% β-isopropylnaphthalene. Example 3 The same reaction as in Example 1 was carried out except that perfluorodecanesulfonic acid was used as the catalyst component and isopropyl chloroformate was used as the alkylating agent. The yield of isopropylnaphthalene was 43%, and its composition was 92% β- and 8% α-isopropylnaphthalene. Example 4 The same reaction as Example 1 was carried out except that cumene was used to transalkylate naphthalene to isopropylnaphthalene. The yield of isopropylnaphthalene is 34% and its composition is 89
% was β- and 11% was α-isopropylnaphthalene. Example 5 50 g of commercially available Nafyon K resin (potassium salt of ion-membrane material from Dupont) was refluxed in 250 ml of deionized water for 2 hours. After that, add 20 ml of resin.
Treated with ~25% nitric acid for 5 hours at room temperature. After evaporation, the nitric acid treatment was repeated three times. Finally, the resin was washed with deionized water until neutral and dried under heating at 105° C. for 24 hours. After charging 5 g of Nafion-H perfluorinated resin sulfonic acid catalyst to the liquid phase alkylation apparatus,
Isopropylation of naphthalene was carried out in the same manner as in Example 1. The yield of isopropylnaphthalene is
73%, and its composition is 95% β- and 5% α-
It was an isomer. Example 6 The same reaction as in Example 4 was carried out, except that 2-chloropropane was used as the alkylating agent and the naphthalene/2-chloropropane ratio was 1:0.8. Yield of isopropylnaphthalene is 54%
Its composition was 98% β- and 2% α-isopropylnaphthalene. Example 7 The same reaction as in Example 4 was carried out except that naphthalene and cumene were reacted at a molar ratio of 1:0.8 for 4 hours. The yield of the obtained isopropylnaphthalene was 37%, and its composition was 92% β-isomer, 8
% was the α-isomer. Example 8 The same reaction as in Example 7 was carried out except that naphthalene and p-cymene were reacted. The yield of isopropylnaphthalene is 51% and its composition is 93
% was the β-isomer and 7% was the α-isomer. Example 9 Commercial isopropylnaphthalene isomer mixture 20 consisting of 57% α-isomer and 43% β-isomer
was heated under the conditions of Example 5 over 5 g of Nafyon-H catalyst in 200 ml of decalin solution at 190 DEG C. for 2 hours. A product consisting of 98% β- and 2% α-isopropylnaphthalene was obtained. Example 10 2 g in a fixed bed contact reactor with a size of 170 x 12 mm
of activated Nafion-H catalyst was charged. Commercially available isopropylnaphthalene mixture (57% α-, 43%
is the β-isomer) using a continuous flow sulfur injection pump,
A constant flow rate of 0.06 ml/min was passed into a reaction chamber electrically heated to about 220°C and into which dry nitrogen was introduced at a flow rate of 8 ml/min. The composition of the isomerized isomerized isopropylnaphthalene taken at intervals was 92% β- and 8% α-isomer. Example 11 A fixed bed catalytic reactor similar to that used in Example 10 was charged with 2.2 g of activated naphion-H catalyst as in Example 5, and a
-Used in gas phase alkylation of chloropropane.
In a contact reactor maintained at 220% by electrical heating,
naphthalene and 2-chloropropane in carbon tetrachloride or cyclohexane at a constant flow rate of 0.15 ml/min and in carbon tetrachloride or cyclohexane.
Delivered as a 10% solution. The products exiting the reactor can be separated directly by fractional distillation without washing or other treatments and analyzed by gas-liquid chromatography. The yield of isopropylnaphthalene is 34% and its composition is 93
% was the β-isomer and 7% was the α-isomer. Example 12 The same reaction as Example 11 was carried out, except that 2-bromopropane was used as the alkylating agent.
The yield of isopropylnaphthalene was 30%, and its composition was 92% β- and 8% α-isomer. Example 13 The same reaction as Example 11 was carried out except that propane was used as the alkylating agent. The yield of isopropylnaphthalene is 37% and its composition is 90
% was the β-isomer and 10% was the α-isomer. Example 14 The same reaction as Example 11 was carried out except that 2-propanol was used as the alkylating agent. The yield of isopropylnaphthalene was 39%, and its composition was 92% β- and 8% α-isomer. Example 15 To transalkylate naphthalene
- The same reaction as in Example 11 was carried out except that cymene was used. Isopropylnaphthalene yield is 21
%, and its composition was 90% β- and 10% α-isopropylnaphthalene. [Table] [Table]

Claims (1)

[Claims] 1. A method characterized by reacting naphthalene and an alkylating agent over a solid perfluorinated sulfonic acid catalyst or a solid perfluorinated sulfonic acid catalyst supported on a carrier.
A method for selectively producing β-isopropylnaphthalene. 2. The method of claim 1, wherein the catalyst is a perfluorinated resin sulfonic acid. 3. The method of claim 1, wherein the catalyst is a _C4 to _C18 perfluorinated alkanesulfonic acid deposited on a support. 4. The method according to claim 1, wherein the isopropylation is carried out in a liquid phase. 5. The method according to claim 1, wherein the isopropylation is carried out in the gas phase. 6. The isopropylation of naphthalene over said catalyst is carried out by transalkylation using an isopropylated aromatic compound as an alkylating agent.
A method according to claim 1. 7. The method of claim 6, wherein the isopropylated aromatic compound is a mixture of isopropylbenzene, isopropyltoluene, diisopropyl or polyisopropylnaphthalene. 8. The isopropylnaphthalene mixture is converted into substantially pure β-isopropylnaphthalene by contacting the mixture of α- and β-isopropylnaphthalene with a solid or supported solid perfluorinated sulfonic acid catalyst. Method of converting to isopropylnaphthalene.