JP3055262B2 - Method for producing 1,1,2,3,3,5-hexamethylindane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to 1,1,2,3,3,5
The present invention relates to a method for producing hexamethylindane (hereinafter referred to as HMI). 5-Acetyl-1,1,2,3,3,6-hexamethylindane obtained by acetylating HMI is used as a flavor for soaps and cosmetics, and HMI is an intermediate for producing the same. .

[0002]

2. Description of the Related Art Isopropenyltoluene and 2-methyl-2-butene are used as a method for producing HMI.
Method of reacting in the presence of crafts type catalyst
No. 09358), a method of reacting in the presence of a catalyst such as a mixture of sulfuric acid and phosphorus pentoxide or phosphoric acid and boron trifluoride etherate (JP-A-51-59846), decomposition or modification of cimen or isopropenyl toluene with petroleum. return C after extracting separated isoprene from C ₅ fraction obtained by the quality
Method of reacting ₅ fractions in the presence of a Friedel-Crafts type catalyst (JP-A-49-110658), 2-methyl-2-
A method is known in which a mixture of butene and 2-methyl-1-butene is reacted with P-cymene in the presence of a Friedel-Crafts type catalyst (Indian Patent No. 161104, 1985).

[0003]

However, 2-methyl-2-butene has been added to Friedel et al.
A method of producing HMI by reacting in the presence of a crafts type catalyst has a low yield and is not an economically advantageous method. Further, a phenomenon in which the catalyst sludge of aluminum hydride solidifies during the reaction and the reaction is stopped is often observed, and the reproducibility is not always sufficient.

In view of these circumstances, P-Symen and 2-
As a result of earnestly studying a method for producing HMI by reacting methyl-2-butene in the presence of anhydrous aluminum chloride and a tertiary alkyl halide with the aim of improving reproducibility and yield, a specific mixed solvent was found to be obtained. By choosing
They have found that good results can be obtained, and have completed the present invention.

[0005]

That is, the present invention provides a P-
The reaction of cymen and 2-methyl-2-butene in the presence of anhydrous aluminum chloride and a tertiary alkyl halide to produce 1,1,2,3,3,5-hexamethylindane at 25 ° C. An aliphatic hydrocarbon or a chlorinated aliphatic hydrocarbon having a solubility coefficient of 9.3 or less, and 25 ° C.
Characterized in that a mixed solvent with a chlorinated hydrocarbon having a solubility coefficient of at least 9.5 is used.
This is a method for producing 5-hexamethylindane.

The tertiary alkyl halide used in the present invention is tert-butyl chloride, tert-amyl chloride, t-butyl bromide or 2-chloro-2,4,4.
4-trimethylpentane and the like. These tertiary alkyl halides are used in an amount of about 1.0 to 1.5 equivalents, preferably about 1.1 to 1.5 equivalents to 2-methyl-2-butene.
1.2 equivalents are used.

The anhydrous aluminum halide of the catalyst used in the present invention includes aluminum trichloride or aluminum tribromide. The amount of these catalysts used is 2
It is usually in the range of 1 to 20 mol%, preferably 5 to 15 mol%, based on -methyl-2-butene.

[0008] The amount of p-cymene used in the present invention is 2-
It is usually in the range of 1 to 5 mol, preferably 1.2 to 3 mol, based on methyl-2-butene. There is no problem if the amount of p-cymene is used more than this range, but the effect corresponding thereto cannot be obtained. On the other hand, when the amount of p-cymene is less than this range, the HMI yield decreases.

The solubility coefficient of the solvent at 25 ° C. (referred to as SP) is defined by the following equation. SP = [(d / M) (△ H-1.987T)] ^1/2 where d is specific gravity (g / cc) at 25 ° C., M is molecular weight, and ΔH is evaporation at 25 ° C. Heat (cal / g), T =
298.2K.

As an aliphatic hydrocarbon or a chlorinated aliphatic hydrocarbon having an SP value of 9.3 or less (referred to as a poor solvent),
n-pentane (SP = 7.0), cyclohexane (SP = 8.2),
n-hexane (SP = 7.4), n-heptane (SP = 7.2), n
Octane (SP = 7.6) and 2,2,4-trimethylpentane (SP = 6.8), tetrachloroethylene (SP = 9.3),
1,1,2-trichloroethylene (SP = 9.2), chloroform (SP = 9.2), tr-1,2-dichloroethylene (SP =
9.0), 1,2-dichloropropane (SP = 9.1), carbon tetrachloride (SP = 8.6), 1,1,1-trichloroethane (SP =
8.5), 1-chlorobutane (SP = 8.4), 1-chloropentane (SP = 8.4) and the like.

On the other hand, chlorinated hydrocarbons having a SP value of 9.5 or more (referred to as good solvents) used in combination with these are 1,2,3-trichloropropane (SP = 9.5),
1,1,2,2-tetrachloroethane (SP = 9.8), dichloromethane (SP = 9.9), 1,2-dichloroethane (SP =
9.9), 1,1,2-trichloroethane (SP = 10.1), monochlorobenzene (SP = 9.8), o-dichlorobenzene (SP = 10.1) and the like.

The mixing ratio of the poor solvent and the good solvent is not particularly limited, but the weight ratio of the good solvent / the poor solvent = 0.5 / 9.5.
To 8/2, preferably 1/9 to 6/4.

When the poor solvent alone or a mixture of the poor solvents is used, solidification of the catalyst sludge at a low temperature surely occurs, and solidification of the catalyst sludge may occur even at a reaction temperature considered as a normal safe area. On the other hand, the solidification of the catalyst sludge does not occur when using a good solvent alone or a mixture of good solvents,
The HMI yield is low and not practical. When a mixed solvent of a poor solvent and a good solvent is used, the yield is slightly lower than when only a poor solvent is used, and the yield decreases as the amount of the good solvent increases, but the temperature at which the solidification of the catalyst sludge occurs is low. Become. The reproducibility is poor when the solidification occurs around the temperature at which solidification occurs, but the reaction reproducibility is good in the higher temperature safety region, and the catalyst sludge does not solidify.

The amount of the mixed solvent used in the present invention is 2
-Methyl-2-butene is usually 100 to 20 with respect to 1 mol.
00 g, preferably in the range of 150 to 1000 g.
There is no particular problem if the solvent is used in an amount larger than this range, but the effect corresponding thereto cannot be obtained. On the other hand, if the amount of the solvent is less than this range, the yield of HMI is undesirably reduced.

If a specific reaction charging method is exemplified,
After the mixed solvent and the solution of p-cymene are charged into the reaction vessel, anhydrous aluminum halide is charged and dispersed by stirring, and then the solution of 2-methyl-2-butene and the tertiary alkyl chloride and the mixed solvent is continuously supplied. After the method of reacting, or charging a solution of p-cymene and a mixed solvent into a reaction vessel,
A part of the anhydrous aluminum halide was charged and dispersed by stirring, and then a solution of 2-methyl-2-butene and a tertiary alkyl chloride and a mixed solvent was continuously supplied, and the reaction was performed while the remaining anhydrous aluminum halide was added in portions. And the like. Especially when the reaction time is long,
The HMI yield is higher when the anhydrous aluminum halide is added in portions.

The amount of p-cymene used in the present invention is 2-
It is usually in the range of about 1-5 mol, preferably 1.2-3 mol, based on methyl-2-butene. There is no particular problem if the amount of p-cymene is used more than this range, but the effect corresponding thereto cannot be obtained. On the other hand, when the amount of p-cymene is less than this range, the HMI yield decreases.

The reaction time is not particularly limited, but is usually 1-1.
It is 5 hours, particularly preferably about 1.2 to 8 hours. The cyclized alkylation reaction of the present invention is an extremely fast reaction, and the reaction time is almost the same as the raw material supply time, which is sufficient, and the post-reaction time after the completion of the raw material supply is not particularly necessary. If the post-reaction time is too long, side reactions such as dimerization of p-cymene become prominent, so that the post-reaction should usually be completed within about 15 to 30 minutes. In this reaction, the active catalyst sludge is settled and separated by stopping the stirring. Therefore, the reaction can be stopped by stopping the stirring.

The reaction temperature is selected from the range of about -5 ° C to 30 ° C. Preferably it is in the range of 5 to 20C. It is not economical to lower the reaction temperature to −5 ° C. or lower from the viewpoint of the reaction heat removal efficiency. On the other hand, if the reaction temperature exceeds 30 ° C., side reactions increase and the HMI yield decreases.

After completion of the reaction, HMI can be purified, isolated and obtained according to a usual method such as washing, neutralization, rectification or crystallization. When the obtained HMT is acetylated according to a conventional method, it is widely used as a musk flavor.
Acetyl-1,1,3,4,4,6-hexamethylindane can be obtained.

[0020]

According to the method of the present invention, the yield is improved as compared with the conventional method, and the reaction is not stopped due to the solidification of the aluminum halide catalyst sludge during the reaction, and the reproducibility of the reaction is improved. I do.

[0021]

Hereinafter, the present invention will be described in detail with reference to Examples.
The present invention is not limited to only this embodiment. The HMI yield, p-cymene (PCM) used in the following examples
Called. ) Conversion is defined as follows. HMI yield: formed HM relative to 2-methyl-2-butene
Molar yield of I (%) PCM conversion = [(raw material PCM-residual PCM) / raw material P
CM] x 100 (%)

Example 1 500 ml equipped with a stirrer, a condenser and a dropping funnel
1.12 g of anhydrous aluminum chloride, 67.11 g of PCM, cyclohexane (SP =
8.2) Charge 30g and dichloromethane (SP = 9.9) 20g,
Stir vigorously. Then, the 2-methyl-
17.35 g of 2-butene and t-butyl chloride
15 g, cyclohexane 30 g and dichloromethane (SP = 9.
9) While maintaining 20 g of the mixed solution at 20 ° C., a drop reaction was carried out over 6.0 hours. At 2.0 hours and 4.0 hours on the way, 1.12 g of anhydrous aluminum chloride was added. Furthermore, after stirring at the same temperature for 10 minutes, the mixture was allowed to stand and tar components were separated to obtain an organic layer. The organic layer was sequentially washed with 100 g of water, 100 g of a 1% aqueous sodium hydroxide solution, and 100 g of water.

The obtained organic layer weighed 158.34 g,
When the organic layer was analyzed by gas chromatography, 28.69 g of unreacted P-cymene and HMI38.
62 g were confirmed. Therefore, 2-methyl-2- of HMI
The reaction yield based on butene was 76.5%, and the PCM conversion was 5%.
7.2%.

Example 2 The same procedure as in Example 1 was carried out except that the reaction temperature was changed to 0 ° C. As a result, the reaction yield of HMI based on 2-methyl-2-butene was 73.4%, and the PCM conversion was 53.5%.

Example 3 Instead of dichloromethane, 1,2-dichloroethane (SP =
9.9) was used in the same manner as in Example 1. Result is,
The reaction yield of HMI based on 2-methyl-2-butene is 6
7.2%, PCM conversion was 58.5%.

Examples 4 to 7 The same procedure as in Example 3 was carried out except that the reaction temperature was changed as shown in Table 1. Table 1 shows the results.

[0027]

[Table 1]

Examples 8 to 9 The same procedures as in Example 3 were carried out except that the amount of pre-loaded PCM was changed as shown in Table 2. Table 2 shows the results.

[0029]

[Table 2]

Example 10 Monochlorobenzene (SP = 9.8) instead of dichloromethane
Was performed in the same manner as in Example 1 except that was used. The result is HM
The reaction yield of I based on 2-methyl-2-butene is 74.8.
%, And the PCM conversion was 57.9%.

Example 11 The same operation as in Example 10 was carried out except that the reaction temperature was changed to 0 ° C. As a result, the reaction yield of HMI based on 2-methyl-2-butene was 75.4%, and the PCM conversion was 47.5%.

Example 12 Instead of monochlorobenzene, dichlorobenzene (SP = 1)
0.1) was performed in the same manner as in Example 11. As a result, the reaction yield of HMI based on 2-methyl-2-butene was 59.2%, and the PCM conversion was 48.4%.

Examples 13 to 16 The same procedures as in Example 1 were carried out except that the poor solvent, the good solvent and the reaction temperature were changed as shown in Table 3. Table 3 shows the results.

[0034]

[Table 3]

Comparative Example 1 The procedure of Example 1 was repeated, except that carbon tetrachloride (SP = 8.2) was used instead of dichloromethane. The result is HMI 2-
Reaction yield based on methyl-2-butene was 74.9%, PC
The M conversion was 58.0%. When the reaction was carried out at 0 ° C., the catalyst sludge solidified and was deactivated.

Comparative Example 2 500 ml equipped with a stirrer, a condenser and a dropping funnel
3.37 g of anhydrous aluminum chloride, 67.11 g of PCM, cyclohexane (SP =
8.2) 50 g was charged (the poor solvent was used alone) and stirred vigorously. Next, 17.35 g of 2-methyl-2-butene, 26.15 g of t-butyl chloride and 50 g of cyclohexane were dropped into the suspension over 1.5 hours while maintaining the temperature at 20 ° C. Post-treatment of the reaction solution was performed in the same manner as in Example 1. As a result, the reaction yield of HMI based on 2-methyl-2-butene was 77.7%, and the PCM conversion was 56.0.
%Met. When the reaction was carried out at 0 ° C., the catalyst sludge solidified and was deactivated.

Comparative Example 3 In the same manner as in Comparative Example 2, except that dichloromethane (SP = 9.9) or 1,2-dichloroethane (SP = 9.9) was used instead of cyclohexane (a good solvent was used alone), and the reaction was carried out at 20 ° C. went. As a result, the reaction yield of HMI based on 2-methyl-2-butene was 28.9% and 20.8%, respectively, and the PCM conversion was 58.6% and 55.3%, respectively.

Comparative Example 4 30 g of cyclohexane (SP = 8.2) and dichloromethane (SP = 8.2)
9.9) The procedure was as in Example 1, except that 50 g of 1,2-dichloroethane was used instead of 20 g and the reaction was carried out at -4.degree. As a result, the reaction yield of HMI based on 2-methyl-2-butene was 18.9%, and the PCM conversion was 29.0%.

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Claims (7)

(57) [Claims] 1. The reaction of P-cymene and 2-methyl-2-butene in the presence of anhydrous aluminum chloride and a tertiary alkyl halide to produce 1,1,2,3,3,5-hexamethylindane. In this case, a mixed solvent of an aliphatic hydrocarbon or a chlorinated aliphatic hydrocarbon having a solubility coefficient at 25 ° C of 9.3 or less and a chlorinated hydrocarbon having a solubility coefficient at 25 ° C of 9.5 or more is used. A process for producing 1,1,2,3,3,5-hexamethylindane, which is used. 2. The tertiary alkyl halide is tert-butyl chloride, tert-amyl chloride or 2-chloro-2,
The 1,1,2 compound according to claim 1, which is at least one compound selected from the group consisting of 4,4-trimethylpentane.
A method for producing 2,3,3,5-hexamethylindane. 3. The method for producing 1,1,2,3,3,5-hexamethylindane according to claim 1, wherein the anhydrous aluminum halide is aluminum trichloride or aluminum tribromide. 4. An aliphatic or chlorinated hydrocarbon having a solubility coefficient at 25 ° C. of 9.3 or less is n-pentane,
Cyclohexane, n-hexane, n-heptane, n-octane, 2,2,4-trimethylpentane, tetrachloroethylene, 1,1,2-trichloroethylene, chloroform, tr-1,2-dichloroethylene, 1,2-dichloropropane, The 1,1,2,3,3,5- compound according to claim 1, which is at least one compound selected from the group consisting of carbon tetrachloride, 1,1,1-trichloroethane, 1-chlorobutane and 1-chloropentane. Method for producing hexamethylindane. 5. A chlorinated hydrocarbon having a solubility coefficient at 25 ° C. of 9.5 or more is 1,2,3-trichloropropane,
The compound is at least one compound selected from the group consisting of 1,1,2,2-tetrachloroethane, dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, monochlorobenzene and o-dichlorobenzene. The method for producing 1,1,2,3,3,5-hexamethylindane according to the above. 6. A mixing ratio of a chlorinated hydrocarbon having a solubility coefficient of not less than 9.5 with respect to an aliphatic hydrocarbon or a chlorinated hydrocarbon having a solubility coefficient of not more than 9.3 at 25.degree. 2. The composition according to claim 1, wherein the ratio is /9.5 to 8/2.
A method for producing 2,3,3,5-hexamethylindane. 7. The process for producing 1,1,2,3,3,5-hexamethylindane according to claim 1, wherein the reaction temperature is -5 to + 30 ° C.