JPH02196743A - Production of homoallyl alcohols - Google Patents

Abstract

PURPOSE:To obtain the subject compounds which are a raw material for perfumes, medicines, agricultural chemicals, etc., in high selectivity by bringing a specific compound obtained from olefins and formaldehyde as raw materials into contact with gamma-alumina under specific conditions and carrying out reaction while distilling away the resultant product. CONSTITUTION:A compound expressed by formula I (R<1> to R<6> are same or different and H, alkyl or alkenyl which may be substituted by hydroxyl or alkoxyl group; X and Y are same or different H, alkyl or alkenyl) as a raw material is brought into contact with gamma-alumina in the liquid phase at a temperature within the range of 130-250 deg.C, preferably 150-210 deg.C normally under a pressure within the range of about 0.01-20kg/cm<2>. Reaction is then carried out while distilling away the resultant objective compounds expressed by formula II (either of A<1> and A3 is H and the other, together with A<2>, forms single bond) and a compound expressed by formula III to afford the objective compounds. Furthermore, the compound expressed by formula I is obtained by reacting the compound expressed by formula IV with formaldehyde.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to the general formula (in which one of AI and A3 represents a hydrogen atom, and the other together with A! forms a single bond). Table t)
L, R1, R1,, R3, R4, R5 and R& are the same or different and each represents an alkyl group or alkenyl group which may be substituted with a hydrogen atom, a hydroxyl group or an alkoxyl group, and Y is a hydrogen atom or an alkyl group. or representing an alkenyl group).

The homoallyl alcohols represented by the general formula (R) produced by the method of the present invention are useful as raw materials for producing fragrances, medicines, agricultural chemicals, and the like.

[Conventional technology]

Conventionally, with regard to the production method of homoallylic alcohols represented by the general formula (1), 3-methyl-1,3-butanediol is dehydrated under heating conditions in the presence of phosphoric acid or iodine. 3-buten-1-ol was obtained with a yield of 35% and isoprene with a yield of 30-35%.
[Bulletin de Société Quimique de France (Bullet
inde Ia 5ociete Chi+wi
que de France), 1964, pp. 800-804], and Nef tekh
Imiya Engineering, 1,104~? (1963),
Similarly, 3-methyl-3-buten-1-ol is converted to 3-methyl-2-buten-1-ol by catalytic dehydration of 3-methyl-1,3-butanediol using alumina, silica alumina, or calcium phosphate as a catalyst. It has been reported that a maximum yield of 50% was obtained in total.

[Problem to be solved by the invention]

The above conventional methods have various problems in industrial implementation. That is, when trying to increase the conversion rate of 3-methyl-1,3-butanediol to an industrially satisfactory value, the by-product of isoprene is unavoidable, and the resulting 3-methyl-3
- If the yield of buten-1-ol is low, and if phosphoric acid is used as a catalyst, the equipment is made of a material that has sufficiently high corrosion resistance since phosphoric acid has the property of corroding metals easily. This requires a large amount of equipment, which requires a large amount of equipment. Furthermore, when using iodine as a catalyst, it is not only disadvantageous in that iodine is expensive, but also because iodine is volatile, it is easy for iodine to be mixed into the product. A disadvantage is that it requires the removal of iodine, which complicates the manufacturing process. Also Naft
ekhiniya-3-2 magnetic 1,104~7 (196
The method shown in 3) has the disadvantage that, if the selectivity is to be maintained, the amount of the compound represented by the general formula ([) produced per hour (STY) per unit volume of catalyst is low.

Therefore, an object of the present invention is to provide an industrially advantageous method for producing homoallylic alcohols represented by the general formula (1) with high selectivity, using a high catalyst, and a high production amount per hour, and at low cost. There is a particular thing.

[Means to solve the problem]

According to the present invention, the above object is achieved by formula (II) (wherein R1, R2, R3, R4, R5 and R6 are the same or different, each substituted with a hydrogen atom or a hydroxyl group or an alkoxyl group) X and Y are the same or different and each represents a hydrogen atom, an alkyl group or an alkenyl group) in a liquid phase at a temperature within the range of 130 to 250°C to T - General formula (1) produced by contact with alumina
) Homoallylic alcohols represented by the general formula (II
I) This is achieved by carrying out the reaction while distilling off the compound represented by X-011(III) (wherein X is as defined above).

By using the method of the present invention, homoallyl alcohols represented by the general formula (1) can be produced with high selectivity and a high production amount per catalyst/hour. Furthermore, high catalytic activity can be maintained over a long period of time, and homoallyl alcohols represented by the general formula (1) can be economically produced at low cost.

R'SR",R',R', R in the above general formula
'sR', detailing X and Y* R' SR
``As described above, R3, R4, R5 and Rh are the same or different and each represents an alkyl group or an alkenyl group which may be substituted with a hydrogen atom, a hydroxyl group or an alkoxyl group, where the alkyl group is a methyl group, Examples include ethyl group, propyl group, isopropyl group, butyl group, etc. This alkyl group may be substituted with a hydroxyl group or an alkoxyl group such as methoxy group, ethoxy group, propoxy group, isopropoxy group, or butoxy group. Examples of alkyl groups substituted with hydroxyl groups include hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group, and examples of alkyl groups substituted with alkoxyl groups include methoxymethyl group and ethoxy group. Examples include methyl group, 1-methoxyethyl group, 2-methoxyethyl group, etc.Alkenyl groups include vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl!, 2-butenyl group, 3 -butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, etc. X and Y are the same or different as described above, respectively, a hydrogen atom,
Represents an alkyl group or an alkenyl group, where the alkyl group includes, for example, a methyl group, an ethyl group, a propyl group,
Examples include isopropyl group, butyl group, pentyl group, isopentyl group, tert-pentyl group, and examples of alkenyl group include vinyl group, allyl group, 1-propenyl group, isopropenyl group, l-butenyl group, and 2-butenyl group. , 3-butenyl group, 3-methyl-2-butenyl group, 3
-Methyl-3-butenyl group and the like.

In the present invention, the reaction can be carried out in the liquid phase in a continuous or batchwise manner.

In the T-alumina used in the method of the present invention, the larger the pore volume, the higher the reaction rate, and the smaller the pore volume, the higher the selectivity to homoallylic alcohols represented by the general formula (1). Due to the tendency, 16 to 33
Preferably, the pore volume of the pores having a pore diameter within the range of 0 angstroms is within the range of 0.1 to 1.0 cc/g.

In the present invention, it is possible to use industrially produced T-alumina of normal purity, for example, about 10% by weight or less of water, about 1% by weight or less of silica, and about 1% by weight or less of oxidation. Iron, up to about 1% by weight of alkali metal oxides, about 1
Alkaline earth metal oxides up to about 0.5% by weight
It is acceptable to use T-alumina containing the following sulfates, but from the viewpoint of sufficiently increasing the reaction rate, the content of alkali metal oxides and alkaline earth metal oxides in alumina is 0. The amount of T-alumina used, which is preferably .3% by weight or less, is usually about 2% by weight per hour of the compound represented by the general formula (n).
Preferably, the amount is between about 5 and 30% by weight, particularly between about 5 and 30% by weight.

There is no particular restriction on the form of T-alumina used in the method of the present invention, and powders, pellets, extruded products, etc. are used.

In the method of the present invention, an organic solvent having a boiling point higher than that of the homoallylic alcohol represented by the general formula (1) and the compound represented by the general formula (III) and which does not adversely affect the reaction is used. reactions can be carried out. Specific examples of organic solvents include high-boiling hydrocarbons such as liquid paraffin and squalane; polyether polyols such as oligomers or polymers such as ethylene glycol, propylene glycol, and 1,4-butanediol;
The compound represented by the general formula (n) can also serve as an organic solvent.

The reaction according to the invention is carried out at a temperature within the range 130-250°C, preferably at a temperature within the range 150-210'C. If the reaction is carried out at a temperature lower than 130°C, it will be impossible to increase the reaction rate sufficiently;
Further, when the reaction is carried out at a temperature higher than 250°C, the loss of the homoallyl alcohol represented by the general formula (I) due to thermal decomposition is significant. In addition, the reaction temperature is 130 to 25, taking into account the boiling points of the compound represented by general formula (II) and the homoallyl alcohol represented by general formula (1).
It is carried out under normal pressure, reduced pressure or increased pressure to achieve the desired temperature within the range of 0°C, but it is usually about 0.01 to 20k.
g/cl” (absolute pressure),
It is preferably carried out at a pressure within the range of about 0.05 to 10 kg/cm'' (absolute pressure).

In the method of the present invention, the addition rate of the compound represented by the general formula (II) and the withdrawal rate of the distillate containing the homoallyl alcohol represented by the general formula (1) and the compound represented by the general formula (III) are controlled. It is preferable to appropriately adjust the amount of liquid in the reaction zone in which T-alumina is present to be constant. Normally, in the case of a reaction using a solid catalyst such as γ-alumina, a decrease in catalyst activity is observed due to by-produced tar-like substances, but in the method of the present invention, the decrease in catalyst activity is extremely small, and the catalyst is stable for a long time. Reactions can be carried out.

General formula (I) produced by reaction according to the method of the invention
The homoallylic alcohols represented by can be separated and obtained from the distillate from the resulting reaction system by a conventional separation operation, for example, a distillation operation.

The compound represented by the general formula (■) used in the method of the present invention is an olefin represented by the general formula (IV) (wherein R1, R2, R3, R4 and R5 are as defined above) and formaldehyde. 1,3-dioxanes represented by the general formula (V) (wherein R1 to R% are as defined above) obtained by reacting them in the presence of an acid catalyst or at the same time, in the presence of an acid catalyst. It can be obtained by hydrolysis or alcoholysis in the presence of Furthermore, this compound has the general formula (V) (wherein Rl,..., R4 are as defined above)
General formula (■) (in the formula, R'-R' is as defined above) or general formula (■) (in the formula, Rf-R' is as defined above) can also be easily obtained by a method such as hydrogenation of a ketoalcohol represented by (as defined above).

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 3-Methyl was placed in a 300 tal glass autoclave equipped with a McMahon packed column with an inner diameter of 10 m and a length of 150 mm, which was connected to a thermometer, a stirrer, a feeder, and a distillate outlet, a reflux condenser, and a dry ice/acetone trap at the top. -1,3-butanediol 300g and powdered γ
-Alumina (Alumina Catalyst N-61 manufactured by JGC Chemical Co., Ltd.)
Pore volume in pores with pore diameter within the range of 16-330 angstroms: 0.33 cc
/g), and the internal atmosphere was replaced with nitrogen gas. Heat the suspension under normal pressure while stirring until the internal temperature reaches 18.
When the temperature reached 8°C, 3-methyl-1,3-butanediol was started to be fed at a rate of 180 g/hour, and at the same time, the distillation port was opened to start collecting the distillate. Note that the amount of suspension in the autoclave was maintained at a constant amount by adjusting the amount of heat of the heater. Also, the internal temperature during this time was 188
It was ℃.

The supply of 3-methyl-1,3-butanediol and the collection of distillate were started, and within 5 hours, 900 g of distillate was obtained. As a result of analyzing the distillate by gas chromatography, it was found that 61% of unreacted 3-methyl-1,3-butanediol was present in the distillate.
．． It was found that 2 g of 3-methyl-1,3-butanediol remained (conversion rate of 93.2%), and that 590.3 g of 3-methyl-3-buten-1-ol was produced. (Selectivity to 3-methyl-3-buten-1-ol: 85.1 mol%, production amount per catalyst/hour: 1.9
7g/g-hr)eThe water contained in the distillate is 145
．． It was 2g.

Example 2 In Example 1, the 3-
900 g of distillate was obtained by carrying out the same operation except that 300 g of liquid paraffin was used instead of 300 g of methyl-1,3-butanediol. The remaining amount of unreacted 3-methyl-1,3-butanediol in the distillate was 173.7 g (conversion rate of 3-methyl-1,3-butanediol: 80.7%), and 3 -The distilled amount of methyl-3-buten-1-ol was 514.7 g (3-methyl-3-buten-1-ol).
Selectivity to -buten-1-ol: 85.7 mol%, production amount per catalyst/hour = 1-72 g/g-hr), and distilled amount of water was 125.7 g. .

Examples 3 to 15 In Example 1, 1,3-glycols having the substituents shown in Table 1 in the general formula (n) were replaced with 3-methyl-1,
Instead of 3-butanediol, add 3 in advance in the autoclave.
By carrying out the same operation except that 00 g was prepared and fed at the feeding rate shown in Table 1, and the reaction temperature and reaction pressure shown in Table 1 were adopted, homogeneous products represented by the corresponding general formula (1) were obtained. Allyl alcohols were obtained.

These results are shown in Table 1.

Examples 16 to 19 with blank spaces below The results shown in the table were obtained.

The following margins are Examples 20 to 22 By performing the same operations as in Example 1 except that the powdered alumina with a particle size of 150 mesh or more shown in Table 3 was used, the results are shown in Table 3.
Below is a margin Example 23 The procedure was the same as in Example 1 except that pelletized γ-alumina (alumina catalyst NN-611-N5φ×5mad manufactured by JGC Chemical Co., Ltd.) was used instead of powdered T-alumina. By doing this, 900 g of distillate was obtained. The remaining amount of unreacted 3-methyl-1,3-butanediol in the distillate was 117 g (conversion rate of 3-methyl-1,3-butanediol: 87.0%), and 3-methyl-1,3-butanediol remained in the distillate.
The distilled amount of 3-buten-1-ol was 519.3 g (3-buten-1-ol).
Selectivity to methyl-3-buten-1-ol: 80.
2 mol%, catalyst/time production 1.73 g/g-
hr), and the amount of water distilled out was 135.5 g.

Example 24 A long-term reaction was carried out under the same reaction conditions as in Example 1. During that time, sampling was performed for 5 hours every 24 hours to check the reaction results. The results are shown in Table 4.

1-6 25-30 49-54 73-78 97-102 121-126 145-150 169-174 193-198 217-222 241-246 265-270 289-294 188±2 188±1 188±2 188 ±2 188±1 188±2 188±2 188±2 188±1 188±2 188±2 188±1 188±2 93.8 92.6 93.5 91.9 92.3 93.2 92.5 93.4 91.8 92.9 93.6 93.0 93.7 84.8 87.0 85.2 86.0 84.2 83.0 84.1 83.2 83.7 85.1 82. 5 83.3 83.6 1.98 2.00 1.98 1.96 1.93 1.92 1.93 1.93 1.91 1.96 1.92 1.92 1.95 [Effect of the invention According to the present invention, as is clear from the above examples, the homoallyl alcohol represented by the general formula (1) can be produced with high selectivity and a high production amount per catalyst/hour.

Claims (1)

[Claims] General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1, R^2, R^3, R^4, R^5 and R
^6 are the same or different and each represents a hydrogen atom, an alkyl group or an alkenyl group which may be substituted with a hydroxyl group or an alkoxyl group, and X and Y are the same or different and each represents a hydrogen atom, an alkyl group or an alkenyl group) The general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, one of A^1 and A^3 represents a hydrogen atom, and the other together with A^2 forms a single bond. It represents R^1, R^2, R^3, R^4, R^5, R
^6 and Y are as defined above) Homoallylic alcohols represented by the general formula (III) X-OH(III) (wherein X is as defined above) are distilled. 1. A method for producing homoallylic alcohols, characterized by carrying out the reaction while