JPH0940615A - Dipropargyl carbonates and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound by using only a propargyl alcohol and carbon dioxide as raw materials, having a simply symmetric basic structure, useful as a carbonylating agent for a medicine and an agrochemical. SOLUTION: This compound of formula I (R<1> and R<2> are each H, an alkyl or an aryl) is obtained by reacting (A) a propargyl alcohol of formula II (R<3> is H, an alkyl or an aryl) (e.g. propargyl alcohol, etc.) with (B) carbon dioxide in the presence of (C) an inorganic base (preferably potassium carbonate, potassium phosphate or cesium fluoride) or (D) an organic base [preferably a diamine such as 1,8-diazabicyclo[5.4.0]-7-undecene, etc.] and (E) a crown ether (e.g. dibenzo-18-crown-6-ether, etc.) at a temperature equal to or higher than a room temperature and <=150 deg.C under pressure equal to or higher than normal pressure and <=50kg/cm<2> . The molar ratio of the component C and the component D to the component A is preferably 0.2-10.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to dipropargyl carbonates and a method for producing the same, more specifically,
The present invention relates to a dipropargyl carbonate which can be used as a carbonylating agent or a carboxylating agent for producing various carbonyl compounds for pharmaceuticals and agricultural chemicals, particularly as a novel monomer for producing polycarbonate in the resin field, and a method for producing the same.

[0002]

2. Description of the Related Art As a method for producing carbonic acid diester,
The phosgene method, the carbonylation method using carbon monoxide, and the transesterification method using other carbonic acid diesters are well known. However, with respect to the method using carbon dioxide as a carbonyl source, there have been very few examples so far in comparison with the above-mentioned various production methods. As a method using such carbon dioxide, an example of reacting a carbonate salt formed from an aliphatic alcohol and a base with an aliphatic halide (for example, JP-A-57-58645, JP-A-5-117222, US Pat. Patent No. 5302717
However, such a method has a problem that not only an alcohol but also a halide is required, and at the same time, an equivalent amount of a hydrogen halide salt is by-produced. Also,
As a method for industrially carrying out the above reaction, a method of carrying out the reaction using only alcohol and carbon dioxide as raw materials (for example, JP-B-56-40707 and JP-B-5-49658).
However, the reaction conditions of these methods are strict and the alcohols that can be used are limited to specific alcohols. In recent years, from the viewpoint of constructing a reaction system of only alcohol and carbon dioxide, a method using propargyl alcohol as a reaction system other than the above systems has been proposed. As such, for example, Japanese Patent Publication No. 2-36565 discloses a method of reacting propargyl alcohol with carbon dioxide in the presence of a ruthenium catalyst to produce a carbonic acid ester having a keto group and a propargyl group. Fair 4
Japanese Patent Laid-Open No. 19220 discloses a method for producing a carbonic acid ester having a keto group by reacting propargyl alcohol and an aliphatic alcohol with carbon dioxide in the presence of a ruthenium catalyst, but all of these methods produce The carbonic acid ester has an asymmetric structure, and its selectivity is extremely low.

[0003]

The present invention has been made under such circumstances. That is, the present invention provides a novel method for easily producing dipropargyl carbonates using only propargyl alcohol and carbon dioxide as raw materials, and a novel dipropargyl having a symmetrical basic structure by the method. The purpose is to obtain carbonate.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that propargyl alcohols easily react with carbon dioxide in the presence of an inorganic base or an organic base to form a carbonate. The present invention has been completed by finding out that the present invention can be realized. That is, the present invention provides (1) the general formula

[0005]

Embedded image (R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group)

Dipropargyl carbonates represented by: and (2) the general formula R ³ -C≡CCH ₂ OH (II) (R ³ represents a hydrogen atom, an alkyl group or an aryl group)
And a method for producing dipropargyl carbonates, which comprises reacting propargyl alcohols represented by and carbon dioxide in the presence of an inorganic base or an organic base.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the method for producing dipropargyl carbonates of the present invention, propargyl alcohols used as a raw material preferably include those represented by the general formula (II). In the general formula (II), as the alkyl group represented by R ³ , for example, those having 1 to 6 carbon atoms can be used, and as the aryl group, for example, phenyl group, p-methylphenyl group and the like can be mentioned. Various substituted phenyl groups and the like can be used. Specifically, propargyl alcohols such as propargyl alcohol and 2-butyn-1-ol can be used. The above-mentioned propargyl alcohols can be used alone,
It is also possible to use two or more types in combination.

In the production method of the present invention, the above-mentioned propargyl alcohols are reacted with carbon dioxide in the presence of an inorganic base or an organic base. As an inorganic base that can be used here, CO ₂ is used. Preferable examples include alkali metal carbonates, alkali metal phosphates, alkali metal fluorides, etc., because they can be activated. Specifically, potassium carbonate, sodium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, potassium phosphate,
Sodium phosphate, lithium phosphate, cesium phosphate,
Potassium fluoride, sodium fluoride, cesium fluoride and the like are used, but potassium carbonate, potassium phosphate or cesium fluoride is particularly preferably used. Preferred examples of the organic base include amidines. Specifically, 1,8-diazabicyclo [5.4.0] -7-undecene is preferably used. In the present invention, the inorganic bases may be used alone or in combination of two or more.

Further, in the above-mentioned production method, the presence of crown ethers during the reaction is preferable from the viewpoint of enhancing the reactivity and accelerating the reaction. Examples of such crown ethers include dibenzo-18-crown-6-ether, benzo-18-crown-6-ether, 18-crown-6-ether and benzo-12.
-Crown-4-ether, Benzo-15-crown-
5-ether, dibenzo-24-crown-8-ether and the like can be used.

In the production method of the present invention, the amount of each of the propargyl alcohol, the inorganic base or the organic base, and the crown ether used in the reaction can be appropriately determined according to the purpose. Or organic base / propargyl alcohol (molar ratio)
0.2 to 10, preferably 1 to 5, particularly preferably 2, and the inorganic base or organic base / crown ether (molar ratio) is 1 to 25, preferably 3 to 15, and particularly preferably 10 Can be determined to be
When the above inorganic base or organic base / propargyl alcohol (molar ratio) is less than 0.2, the reaction progresses extremely slowly, and when it exceeds 10, the amount of solvent needs to be increased and it may not be practically preferable. Further, when the inorganic base or organic base / crown ether (molar ratio) is less than 1, the amount of ether used increases, which is not preferable in practical use.
If it exceeds, the solubility of the inorganic base may be deteriorated and the effect may not be seen. For these reasons, the use amount determined according to each of the above-mentioned preferable ranges is practical, and even better results are obtained.

In the present invention, the reaction solvent used in the above reaction is not particularly limited, and any solvent can be used as long as it can dissolve carbon dioxide, but a polar aproton is used from the viewpoint of promoting dissolution of an inorganic base. A solvent is preferably used. Specifically, dimethylacetamide (DMA
c), tetrahydrofuran (THF), dimethylformamide (DMF), N-methylpyrrolidone (NMP),
Acetonitrile, hexamethylphosphoric triamide (HMPA) and the like can be used. Of these, dimethylacetamide (DMAc) is particularly preferably used in the present invention.

In the method for producing dipropargyl carbonates of the present invention, the above propargyl alcohols are reacted with carbon dioxide in the presence of an inorganic base or an organic base, and optionally the above crown ethers, reaction solvent and the like. In this reaction, the reaction temperature is preferably room temperature or higher and 150 ° C. or lower. If the temperature is lower than room temperature, the progress of the reaction is extremely slow, and if it exceeds 150 ° C., the amount of by-products increases, and the yield of the desired product may decrease. For this reason, in the present invention, the reaction temperature is 80 to 120 ° C., particularly 80 to 100 ° C.
It is preferably within the range. The reaction pressure is preferably not less than atmospheric pressure and not more than 50 kg / cm ² . 5
If it exceeds 0 kg / cm ² , the yield of the desired product may decrease. For these reasons, in the present invention, the reaction pressure is preferably in the range of atmospheric pressure to 10 kg / cm ² . Further, the above reaction is preferably carried out for a reaction time within the range of 5 to 45 hours. If the reaction time deviates from the above range, the yield of the desired product may decrease. The dipropargyl carbonates obtained by the above production method have the general formula

[0013]

Embedded image (R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group)

It is represented by The above general formula (I)
In the above, examples of the alkyl group represented by each of R ¹ and R ² include those having 1 to 6 carbon atoms, and examples of the aryl group include various substituted phenyl groups such as phenyl group and p-methylphenyl group. Can be mentioned. The dipropargyl carbonates represented by the above general formula (I) are preferably those in which R ¹ and R ² are the same group, and as such, for example, R ¹ and R ² are both hydrogen atoms. One example is dipropargyl carbonate.

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 4 mmol of potassium carbonate was placed in a 50 ml two-necked eggplant-shaped flask, the inside was replaced with carbon dioxide, 2.5 mmol of propargyl alcohol and 4 ml of dimethylacetamide as a solvent were added, and at 80 ° C. under carbon dioxide flow. The reaction was carried out for 45 hours. Then, after allowing the reaction solution to cool to room temperature, it was transferred to a separating funnel and ether 20
20 ml of 1N hydrochloric acid was added to the mixture to separate the layers, and the ether layer was taken out. The ether layer was dehydrated with anhydrous magnesium sulfate, the ether was distilled off with an evaporator, and then analyzed by gas chromatography to find that dipropargyl carbonate was produced in a 12% yield (based on raw material propargyl alcohol). IR, ¹ H-NMR, ¹³ C-of this dipropargyl carbonate
The results of measuring each spectrum of NMR are shown below. Spectral data for dipropargyl carbonate

[0016]

Embedded image

Example 2 0.5 mmol of potassium carbonate was placed in a 50 ml autoclave made of stainless steel, the inside was replaced with carbon dioxide, 2.3 mmol of propargyl alcohol and 4 ml of dimethylacetamide as a solvent were added, and carbon dioxide 5 kg / The reaction was carried out at 100 ° C. for 5 hours under cm ² . When the reaction liquid after the reaction was treated and analyzed in the same manner as in Example 1, dipropargyl carbonate was produced in a yield of 14% (based on raw material propargyl alcohol).

Example 3 A reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 120 ° C. and the reaction time was 5 hours, and the same treatment and analysis were conducted. It was produced on the basis of alcohol).

Example 4 Example 1 except that 0.4 mmol of dibenzo-18-crown-6-ether was added and the reaction time was 5 hours.
When reacted in the same manner as above, treated and analyzed in the same manner, dipropargyl carbonate was produced in a yield of 9% (based on raw material propargyl alcohol).

Example 5 The reaction was carried out in the same manner as in Example 1 except that potassium phosphate was used instead of potassium carbonate and the reaction time was 5 hours, and the same treatment and analysis were conducted. As a result, dipropargyl carbonate was found to be 7%. Yield (based on raw material propargyl alcohol)
Was generated by

Example 6 Reaction was carried out in the same manner as in Example 5 except that 0.17 mmol of dibenzo-18-crown-6-ether was added, and the same treatment and analysis were conducted. As a result, 14% yield of dipropargyl carbonate was obtained. (Raw propargyl alcohol standard)
Was generated by

Example 7 A reaction was conducted in the same manner as in Example 1 except that cesium fluoride was used in place of potassium carbonate, and the same treatment and analysis were carried out. ) Was generated in.

Example 8 Instead of potassium carbonate, 1,8-diazabicyclo [5.
4.0] -7-undecene was used and the reaction was carried out in the same manner as in Example 1 except that the reaction time was 5 hours, and the same treatment and analysis were conducted.
% Yield (based on raw material propargyl alcohol).

Comparative Example 1 The reaction was conducted in the same manner as in Example 1 except that potassium carbonate was not added and the reaction time was changed to 5 hours, and the same treatment and analysis were carried out. No product was detected. It was Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that magnesium carbonate was used instead of potassium carbonate and the reaction time was changed to 5 hours, and the same treatment and analysis were conducted, but no product was detected. It was

Comparative Example 3 The reaction was carried out in the same manner as in Example 1 except that zinc carbonate was used instead of potassium carbonate and the reaction time was changed to 5 hours, and the same treatment and analysis were conducted. Not detected. Comparative Example 4 The reaction was conducted in the same manner as in Example 1 except that triethylamine was used instead of potassium carbonate and the reaction time was changed to 5 hours, and the same treatment and analysis were conducted, but no product was detected at all. .

Comparative Example 5 The reaction, reaction and analysis were conducted in the same manner as in Example 1 except that methanol was used instead of propargyl alcohol and the reaction time was 5 hours. It was not detected at all. Comparative Example 6 The reaction was carried out in the same manner as in Example 1 except that allyl alcohol was used instead of propargyl alcohol and the reaction time was 5 hours, and the same treatment and analysis were conducted, and the corresponding carbonic acid diester was detected at all. Was not done.

[0027]

By the production method of the present invention, novel dipropargyl carbonates having a symmetrical basic structure can be easily obtained using only propargyl alcohols and carbon dioxide as raw materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 68/04 9546-4H C07C 68/04 A // C07B 61/00 300 C07B 61/00 300

Claims (10)

[Claims] 1. A compound of the general formula (R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group), and dipropargyl carbonates. 2. The dipropargyl carbonate according to claim ¹ , wherein in the general formula (I), R ¹ and R ² are the same group. 3. The general formula R ³ —C≡CCH ₂ OH (II) (R ³ represents a hydrogen atom, an alkyl group or an aryl group)
A method for producing dipropargyl carbonates, which comprises reacting propargyl alcohols represented by the above with carbon dioxide in the presence of an inorganic base or an organic base. 4. The method for producing dipropargyl carbonates according to claim 3, wherein the inorganic base is at least one selected from alkali metal carbonates, alkali metal phosphates and alkali metal fluorides. 5. The method for producing dipropargyl carbonates according to claim 3, wherein the inorganic base is potassium carbonate, potassium phosphate or cesium fluoride. 6. The method for producing dipropargyl carbonates according to claim 3, wherein the organic base is an amidine. 7. The method for producing dipropargyl carbonates according to claim 3, wherein the molar ratio of the inorganic base or organic base to the propargyl alcohol is 0.2 to 10. 8. The method for producing dipropargyl carbonates according to claim 3, wherein the reaction is carried out in the presence of crown ethers. 9. The method for producing dipropargyl carbonates according to claim 3, wherein the reaction temperature is room temperature or higher and 150 ° C. or lower. 10. The reaction pressure is 50 kg / cm or more at atmospheric pressure or more.
^{It is 2} or less, The manufacturing method of the dipropargyl carbonates in any one of Claims 3-9.