JPS6019304B2 - Method for producing 5-chloromethylfurfural - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 5-chloromethylfurfural.

More specifically, the present invention is characterized by a method for producing 5-chloromethylfurfural by reacting glucose with hydrochloric acid in the presence of an organic solvent inert to the reaction, and further using a catalytic amount of a surfactant in this system. This is a method for producing 5-chloromethylfurfural.

The compound is useful as an intermediate for pharmaceuticals or agricultural chemicals, and can be converted into various furan derivatives.

Conventionally, the following method is known as a method for producing 5-chloromethylfurfural.

One is a method of treating fructose or recommended sugar with hydrochloric acid in the presence of carbon tetrachloride (J. Chem. SM., 667
, 1944). This method involves gelation during the reaction, making the operation very complicated, and the yield is as low as about 20%, so it is not a method that can be implemented industrially. According to a report on a follow-up trial of this method, a large amount of humic substances were produced, making filtering and separation after the reaction extremely difficult, and the humic substances solidified when left standing, making it impossible to extract them. It is said to be difficult. Therefore, as an industrial production method, 5-acetoxymethylfurfural is reacted with hydrochloric acid,
A method of converting an acetoxymethyl group into a chloromethyl group has been proposed (Japanese Patent Publication No. 45-3969y). However, this method starts with furfuryl alcohol, acetylates it, then formylates it to 5-acetoxymethylfurfural using the Wils-Mayer reaction, and then undergoes the aforementioned chlorination to obtain the desired product, 5-acetylfurfural. This method requires many steps to obtain chloromethylfurfural, and is not necessarily an industrially advantageous method. As a result of intensive studies on the method for producing 5-chloromethylfurfural, the present inventors surprisingly found that 5-chloromethylfurfural can be produced directly and in one step by reacting glucose with hydrochloric acid in the presence of an organic solvent. The present inventors have newly discovered that the yield of the target product can be increased by using a catalytic amount of a surfactant in this system, and after conducting various studies, they have completed the present invention. Although there is no known method for directly producing 5-chloromethylfurfural from glucose, methods for synthesizing 5-hydroxymethylfurfural include reacting it with an acid in a very dilute aqueous solution, or reacting glucose with potassium hydroxide and water. It is reported that 5-hydroxymethylfurfural can be obtained with a yield of about 30% by pretreatment with an alkali such as calcium oxide and then reacting with Hakamaic acid (JChem.Soc., 6
69, 1944).

However, as mentioned above, this method relates to the synthesis of 5-hydroxymethylfurfural, and is not a method for directly producing 5-chloromethylfurfural. Moreover, in addition to pretreating glucose with an alkali, it is necessary to perform, for example, acetylation and then chlorination in order to produce 5-chloromethylfurfural from the obtained 5-hydroxymethylfurfural. However, there is a method for obtaining the desired 5-chloromethylfurfural in one step by reacting glucose with hydrochloric acid in the presence of an organic solvent inert to the reaction, and gelation by using a catalytic amount of a surfactant in this system. , the method of high-yield reaction based on prevention of resin formation was unexpected from previous facts,
This provides an industrially extremely advantageous method.

Moreover, the glucose used in the present invention widely exists in the natural world and can be obtained industrially at low cost.

The hydrochloric acid used in carrying out the method of the present invention may be commercially available, and the amount used is not particularly limited as long as it is a stoichiometric amount or more. There is no particular advantage in using 5 moles or more relative to glucose. Organic solvents used in the reaction include organic solvents that are inert to the reaction, such as aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, and their halides, and fatty acids such as methylene chloride, chloroform, and carbon tetrachloride. Examples include group halogenated hydrocarbons.

The reaction is carried out by adding glucose in the presence of the above-mentioned organic solvent,
It is done by mixing with hydrochloric acid.

The hydrochloric acid to be used may be added in advance, or the hydrochloric acid consumed as the reaction progresses may be added gradually or intermittently to supplement it. In this case, similar results can be obtained by dissolving glucose in water and blowing hydrogen chloride into it. It is also possible to use alcohols such as methanol, ethanol, isopropanol, acetic acid, etc. in this system as a mixed solvent with water. moreover,
The present inventors have also discovered that by using a catalytic amount of a surfactant in the reaction system, the reaction can be carried out smoothly and with a good yield. That is, in the hydrochloric acid decomposition reaction in the above-mentioned hydrochloric acid-organic solvent-glucose system, when a surfactant is used as a two-layer interlayer transfer catalyst, a micelle-like system is generated, suppressing gelation and resinization of the system, and achieving the desired purpose. The production of things is promoted.

The surfactant used includes a surfactant consisting of approximately equal amounts of a sulfonate type anionic surfactant and a quaternary ammonium salt type cationic surfactant, and a sulfonate type anionic surfactant. Surfactants selected from the group consisting of: Particularly preferably, when using a surfactant consisting of approximately equal amounts of a sulfonate type anionic surfactant and a quaternary ammonium salt type cationic surfactant, the system becomes a micelle state and becomes a resin. It is also easy to process after the reaction. A preferred combination is, for example, one part of sulfonate type sodium laurylbenzenesulfonate as an anionic agent and one part of quaternary ammonium salt type cetyltrimethylammonium chloride as a cationic agent. The amount of surfactant used is 1 mole of glucose. ~life. I'm wearing desk clothes. ~Death is at stake.

There is no particular restriction on the reaction temperature, and it is preferable to flood the reaction to promote the reaction, but to suppress side reactions,
A range of 0qC or less, preferably from about 10°C to about 60'0, is suitable.

Under such conditions, the reaction is usually completed in 1 to 1q hours.

The progress of the reaction can be determined by gas chromatography or other conventional methods.

The desired 5-chloromethylfurfural is obtained with high purity from the liquid after the reaction has been completed.

If necessary, it is also possible to purify by chromatography or other conventional methods. As detailed above, 5-chloro can be obtained by the method of the present invention. The production of methylfurfuryl has become extremely advantageous industrially, and pyrethroid compounds using 5-propargylfurfuryl alcohol derived therefrom are important as excellent insecticides. Next, the method of the present invention will be explained in more detail by way of examples.

Example 1 Commercially available D-glucose (0.028 mol) was placed in a cooling tube,
The mixture was placed in a three-necked flask equipped with a fly frame, dissolved in 5 parts of water, and further mixed with 30 parts of toluene.

Thereafter, an excess molar amount of hydrogen chloride (approximately 12 hours) was added at room temperature for 30 minutes.
The mixture was injected for 5 minutes, and then heated at 45°C for 5 hours. The reaction solution containing a small amount of humic substances was diluted with a small amount of water and heated through Celite while washing with a small amount of toluene. The toluene layer was neutralized with an aqueous solution of NPHC03, dried over Na204, and concentrated to give a thick brown solution of 5-chloromethylfurfural (theoretical 4.0).
1 night). No by-products were obtained. Example 2 Commercially available D-glucose (0.028 mol), two surfactants, sodium laurylbenzenesulfonate 9
7.6 of 9 (0.00028 mol), cetyltrimethylammonium chloride 89.6 of 9 (0.00028 mol)
mol) was placed in a three-necked flask equipped with a cooling tube and a boat, 5 parts of water and 30 parts of toluene were added, and the mixture was stirred.

Thereafter, an excess molar amount of hydrogen chloride (approximately 13 hours) was blown in for 25 minutes at room temperature, and the mixture was further heated at 45° C. for 3 hours. After separating the supernatant toluene layer from the reaction solution, 30% of toluene was newly added, and after heating at 460°C for 2 hours, the upper toluene layer was separated again. This sampling and addition operation is performed 4 times in total.
Repeatedly, the total toluene solution was filtered through Ceolite, neutralized with NaHC03 aqueous solution, and Na2SQ
After drying, the mixture was concentrated to obtain a yellow-brown crude liquid product, approximately 2.4 hours of 5-chloromethylfurfural. No by-products were obtained. Example 3 Commercially available D-glucose (0.028 mol), two surfactants, sodium laurylbenzenesulfonate 97
．． Put 9 of 6 (0.00028 mol) and 9 of 89.6 (0.00028 mol) of cetyltrimethylammonium chloride into a three-necked flask equipped with a cooling tube and rope sieve, add 30' of toluene, and suspended.

Slowly drip 35% hydrochloric acid from the dropping funnel over a period of 1 hour, then slowly blow in a slightly excess amount of hydrogen chloride over a period of 3 hours while keeping the temperature at 45°C, and then add 35% hydrochloric acid for another 4 hours. After that, the reaction solution was diluted with a small amount of water, filtered through Ceolite while washing with toluene, and the toluene layer was neutralized, dried, and concentrated to obtain a crude product of about 1.9 hours. Example 4 Five volumes of commercially available D-glucose, two types of surfactants, 97.6 m9 of sodium laurylbenzenesulfonate, and 89.6 m9 of cetyltrimethylammonium chloride were placed in a similar three-necked flask, followed by five volumes of water and 30 m2 of toluene. I added it and worshiped the key.

Then, at room temperature, 2 powder molar excess of hydrogen chloride was blown into the
Furthermore, I worshiped flies for 7 hours at 50 pm. The reaction solution was diluted with a small amount of water, filtered through Ceolite while washing with toluene, and a crude product of about 1.7 hours was obtained in the same manner from the toluene layer. Example 5 A quantity of commercially available D-glucose, two surfactants, 97.6 parts of sodium laurylbenzenesulfonate, and 89.6 parts of cetyltrimethylammonium chloride were placed in a similar three-necked flask, and 5 parts of water was added. Then, 30 doses of carbon tetrachloride were added and worshiped.

Then, an excess molar amount of hydrogen chloride was blown in for 25 minutes at room temperature.
Furthermore, the lamp was held at 50℃ for 7 hours. The reaction solution, which was slightly gelled, was filtered through Ceolite while being washed with a small amount of water and carbon tetrachloride, and the lower carbon tetrachloride layer was neutralized, dried, and concentrated to give a rough solution of about 1.5 days. The product was obtained. Example 6 Five parts of commercially available D-glucose and 97.6 parts of sodium laurylbenzenesulfonate were placed in a similar three-necked flask, and 5 parts of water and 30 parts of toluene were added thereto.

Claims (1)

[Claims] 1. A method for producing 5-chloromethylfurfural, which comprises reacting glucose and hydrochloric acid in the presence of an organic solvent inert to the reaction. 2. When reacting glucose and hydrochloric acid in the presence of an organic solvent inert to the reaction, a surfactant composed of equal amounts of a sulfonate type anionic surfactant and a quaternary ammonium salt type cationic surfactant A method for producing 5-chloromethylfurfural, which comprises using a catalytic amount of a surfactant selected from the group consisting of a surfactant and a sulfonate type anionic surfactant.