JPH0656702A - Method for hydrogenating and reducing cyclic organic compound - Google Patents

Abstract

PURPOSE:To enable the efficient carrying out of a hydrogenating reduction of a cyclic organic compound under conditions of high safety without requiring a catalyst such as the conventional nickel by catalytically hydrogenating the cyclic organic compound with hydrogen released from a hydrogen storing alloy. CONSTITUTION:A cyclic organic compound having one or more double bonds, preferably an aromatic compound or a heterocyclic compound, especially an aromatic hydrocarbon, furan, pyrrole or pyridine is hydrogenated and reduced. In the process, a hydrogen storing alloy (e.g. CaNi5 or LaNi5) containing a compound having a hexagonal CaCu5 type crystal structure comprising M (which denotes a rare earth element or Ca element) and Ni as essential elements as a main phase is used and the cyclic organic compound is catalytically hydrogenated with hydrogen released from the alloy to reduce the one or more double bonds. After the reaction, the hydrogen gas and the reactional solution are recovered and the hydrogen storing alloy is cooled. The hydrogen is then recycled for repeated use in the next reducing reaction. Since the hydrogen storing alloy has a high catalytic ability, the cyclic organic compound can safely be reduced with a high reduction ratio even under 30kg/cm<2> or lower hydrogen gas pressure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for hydrogenating a cyclic organic compound such as an aromatic compound or a heterocyclic compound using a hydrogen storage alloy. INDUSTRIAL APPLICABILITY The method of the present invention is useful in the synthesis of chemical products used in the fields of food, medicine, agricultural chemicals and the like.

[0002]

2. Description of the Related Art Many examples of the reaction for reducing an aromatic compound or a heterocyclic compound by hydrogenation have been known for a long time. Palladium as a typical one,
There is a method of performing hydrogenation reduction in a hydrogen atmosphere using a metal catalyst such as platinum, nickel, cobalt and copper. According to this method, the operation is easier than the reaction using other reducing agents,
Moreover, since the product and the catalyst can be easily separated, there is an advantage that the reaction can be performed without polluting the reaction system. Among the metal catalysts used at this time, palladium and platinum have a relatively high activity as a catalyst and can perform the hydrogenation reaction at low temperature and low pressure, but nickel, cobalt, copper, etc. have a high activity as a catalyst. Low, often requiring reaction under high temperature, high pressure conditions. On the other hand, industrially, from the viewpoint of running cost when using this reaction,
Noble metals such as palladium and platinum can be recycled, but are expensive, and are not necessarily suitable for use on an industrial scale.

Hydrogen storage alloys, which have been recently developed and are attracting attention for their applications, are currently used in the fields of automobiles, heat pumps, indoor air-conditioning systems, and the like. The hydrogen storage alloys include, for example, LaNi ₅ , MgNi, There are many types such as TiFe, and the functions of the alloy such as hydrogen storage amount, discharge pressure, discharge temperature, etc. differ greatly depending on the constituent metals, and therefore the selection of the alloy is important for its use.

By the way, as an example of the hydrogenation reduction reaction by a hydrogen storage alloy, hydrogenation reduction of olefins, hydrogenation of carbon monoxide and synthesis of ammonia are described in "Hydrogen Storage Alloy Data Book" (published by Yono Shobo 1987). In addition, regarding the C ₁₈ alcohol formation reaction by atmospheric hydrogenolysis of methyl oleate, the Chemical Society of Japan (54th Annual Meeting of the Spring 1987
(Held annually). In addition, hydrogenation of fats and oils (JP-A-63-268799), production of sugar alcohol (Japanese Patent Application No. 2-219100), reduction of disulfide bond (Japanese Patent Application No. 2-27100).
7808) and the deprotection law (Japanese Patent Application No. 2-277809).

However, there is no report on an example in which a cyclic organic compound such as an aromatic compound or a heterocyclic compound is hydrogenated using a hydrogen storage alloy.

[0006]

DISCLOSURE OF THE INVENTION The present invention utilizes a highly reactive hydrogen storage alloy in the reduction of cyclic organic compounds such as aromatic compounds and heterocyclic compounds by catalytic hydrogenation. It is not necessary to use a catalyst at all, and a large amount of hydrogen discharged from a hydrogen storage alloy can be used at low pressure. It has a high reduction rate and can be safely and inexpensively produced by catalytic hydrogenation of aromatic compounds or heterocyclic compounds. An object of the present invention is to provide a method for hydrogenating and reducing a cyclic organic compound such as.

[0007]

According to the present invention, when a cyclic organic compound such as an aromatic compound or a heterocyclic compound is hydrogenated by a catalytic hydrogenation reaction, M (representing a rare earth element or Ca element) is used. And a hydrogen storage alloy having as a main phase a compound having a hexagonal CaCu ₅ type crystal structure in which Ni is an essential element, and catalytic hydrogenation is performed with hydrogen released from the alloy to reduce the hydrogen. To do.

The present invention will be described in detail below. The cyclic organic compound used in the present invention is preferably an aromatic compound or a heterocyclic compound having one or more double bonds,
More preferred are aromatic hydrocarbons, furan, pyrrole and pyridine. The hydrogen storage alloy used in the present invention has, as a main phase, a compound having a hexagonal CaCu ₅ type crystal structure in which M (representing a rare earth element or Ca element) and Ni are essential elements. Further, the CaCu ₅ type crystal phase contained in the hydrogen storage alloy is contained in an amount of 50% by weight or more, and the rest contains intermetallic compounds other than the main phase, impurities, additional elements, etc. as the second phase or mixed phase. Since these hydrogen storage alloys themselves have high catalytic ability for the reduction reaction, by appropriately setting the type of alloy to be used and the temperature condition for performing the reduction reaction, even under the hydrogen gas pressure condition of less than 30 kg / cm ^2. It is possible to reduce cyclic organic compounds such as aromatic compounds and heterocyclic compounds safely with a high reduction rate.

After pulverizing this hydrogen storage alloy, the alloy is occluded with hydrogen by holding it at a temperature of 0 ° C. or lower in a hydrogen atmosphere for a certain period of time. In the present invention, a reaction solution containing a cyclic organic compound such as an aromatic compound or a heterocyclic compound and the hydrogen storage alloy are placed in a reaction tank, and after degassing, the reaction solution is adjusted to an appropriate temperature condition while stirring. Of the aromatic compound and the hydrogen storage alloy is sealed in a tray column that can cool the hydrogen storage alloy by a jacket method and the reaction solution kept at an appropriate temperature condition is circulated. A cyclic organic compound such as a heterocyclic compound is hydrogenated and reduced.

After the reaction, the hydrogen gas and the reaction solution are recovered and the hydrogen storage alloy is cooled. This hydrogen storage alloy can be repeatedly used for the next reduction reaction by recycling hydrogen. Incidentally, the present invention, in the characteristics of the hydrogen storage alloy, the hydrogen gas pressure can be sufficiently hydrogenated reduction of the cyclic organic compound under the condition of less than 30 kg / cm ² , in terms of the retention safety of the manufacturing apparatus, It is advantageous. In addition, as the hydrogen storage alloy, a plating powder, a surface-treated powder, an encapsulated alloy of copper, silicon or the like, which is surface-modified for the purpose of improving corrosion resistance, thermal conductivity, etc., can be used in the present invention.

[0011]

EXAMPLES Next, the present invention will be described concretely by showing Examples. Example 1 In a dead-end type reaction vessel having a volume of 1 liter, 100 g of hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 0 ° C and vacuum degree of 750mmHg,
100 ml of cooled toluene was poured into the reaction vessel. Then, the reaction temperature was adjusted to 80 ° C. with stirring. At this time,
The hydrogen gas pressure in the reaction vessel was 20 kg / cm ² . After 2 hours, the main product in the reaction solution was collected by HPLC, and I
When confirmed by R and NMR, the desired 1-
It was confirmed that methyl-cyclohexane was produced.

Example 2 In a dead-end type reaction vessel having a volume of 1 liter, 100 g of hydrogen storage alloy LaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 4 ℃ and vacuum degree of 750mmHg,
Cooled 0.01% KOH solution of benzoic acid at a concentration of 5% by weight
100 ml was poured into the reaction vessel. Then, the reaction temperature was adjusted to 70 ° C. with stirring. At this time, the hydrogen gas pressure in the reaction vessel was 18 kg / cm ² . After 3 hours, the main product in the reaction solution was collected by HPLC and confirmed by IR and NMR. It was confirmed that the target cyclohexanecarboxylic acid was produced in a yield of 76%.

Example 3 100 g of hydrogen storage alloy LaNi _4.2 Al in which hydrogen was previously stored in a dead-end type reaction vessel having a volume of 1 liter
_{Insert 0.8} . After degassing for 5 minutes at 0 ° C. and a vacuum degree of 750 mmHg, 100 ml of a cooled 4% by weight methanol solution of 2,4-diaminotoluene was poured into the reaction vessel. Then, the reaction temperature was adjusted to 100 ° C. with stirring. At this time, the hydrogen gas pressure in the reaction vessel was 24 kg / cm ² . After 2 hours, the main product in the reaction solution was separated by HPLC and confirmed by IR and NMR. As a result, the target 1-methyl-2,4-diaminocyclohexane was produced in a yield of 68%. It was confirmed.

Example 4 In a dead-end type reaction vessel having a volume of 1 liter, 60 g of hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 0 ° C and vacuum degree of 750mmHg,
Cooled 5 wt% Naphthalene solution in ethanol
80 ml was poured into the reaction vessel. Then, the reaction temperature was adjusted to 70 ° C. with stirring. At this time, the hydrogen gas pressure in the reaction vessel was 14 kg / cm ² . After 4 hours, the main product in the reaction solution was collected by HPLC and confirmed by IR and NMR. It was confirmed that the desired tetralin was produced in a yield of 92%.

Example 5 In a dead-end type reaction vessel having a volume of 1 liter, 150 g of hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 0 ° C and vacuum degree of 750mmHg,
100 ml of a cooled 10% strength by weight solution of anthracene in cyclohexane were injected into the reaction vessel. Then, the reaction temperature was adjusted to 40 ° C. with stirring. At this time, the hydrogen gas pressure in the reaction vessel was 15 kg / cm ² . 4 hours later, HP
When the main product in the reaction solution was separated by LC and confirmed by IR and NMR, it was confirmed that the target decahydroanthracene was produced in a yield of 71%.

Example 6 In a dead-end type reaction vessel having a volume of 1 liter, 150 g of hydrogen storage alloy LaNi _{5 in} which hydrogen is stored in advance is placed. After degassing for 5 minutes at 0 ° C and vacuum degree of 750mmHg,
100 ml of a cooled 10% by weight strength solution of phenanthrin in cyclohexane was injected into the reaction vessel. Then, the reaction temperature was adjusted to 40 ° C. with stirring. At this time, the hydrogen gas pressure in the reaction vessel was 14 kg / cm ² . 4 hours later, H
The main product in the reaction solution was collected by PLC, IR, NMR
As a result, it was confirmed that the target decahydrophenanthrin was produced in a yield of 66%.

Example 7 100 g of hydrogen storage alloy LaNi _4.2 Al in which hydrogen was previously stored in a dead-end type reaction vessel having a volume of 1 liter
_{Insert 0.8} . After degassing for 5 minutes at 25 ° C. and a vacuum degree of 750 mmHg, 100 ml of cooled 1-naphthol was injected into the reaction vessel. Then, the reaction temperature was adjusted to 80 ° C. with stirring. At this time, the hydrogen gas pressure in the reaction vessel is 21 kg / c.
Although it was m ² , hydrogen was further added to 40 kg / cm ² . After 2 hours, the main product in the reaction solution was collected by HPLC, IR,
When confirmed by NMR, it was confirmed that the target 5-hydroxytetralin was produced in a yield of 81%.

Example 8 In a dead-end type reaction vessel having a capacity of 1 liter, 100 g of hydrogen storage alloy CaNi ₅ containing 100 g of hydrogen stored therein was placed. 25 ℃, vacuum degree 750mmH
After degassing with g for 5 minutes, 100 ml of cooled 2-naphthol
Was injected into the reaction vessel. Then, the reaction temperature was adjusted to 120 ° C. with stirring. At this time, the hydrogen gas pressure in the reaction vessel was 29 kg / cm ² , but hydrogen was further added to 50 kg / cm ²
And After 2 hours, the main product in the reaction solution was collected by HPLC and confirmed by IR and NMR. As a result, it was confirmed that the target 6-hydroxytetralin was produced in a yield of 74%.

Example 9 In a dead-end type reaction vessel having a volume of 1 liter, 100 g of hydrogen storage alloy LaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 4 ℃ and vacuum degree of 750mmHg,
50 ml of cooled cyclopentadiene was injected into the reaction vessel. Then, the reaction temperature was adjusted to 60 ° C. while stirring.
At this time, the hydrogen gas pressure in the reaction vessel was 9 kg / cm ² . After 2 hours, the main product in the reaction solution was separated by HPLC and confirmed by IR and NMR. It was confirmed that the target cyclopentene was produced in a yield of 55%.

Example 10 In a dead-end type reaction vessel having a volume of 1 liter, 200 g of hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 4 ° C. and a vacuum degree of 750 mmHg, 50 ml of cooled cyclooctatetraene was injected into the reaction vessel. Then, the reaction temperature was adjusted to 60 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel is 12 kg / cm ²
Met. After 4 hours, the main product in the reaction solution was separated by HPLC and confirmed by IR and NMR. It was confirmed that the target cyclooctane was produced in a yield of 66%.

Example 11 In a dead-end type reaction vessel having a volume of 1 liter, 50 g of hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 4 ℃ and vacuum degree of 750mmHg,
50 ml of cooled furan was poured into the reaction vessel. afterwards,
The reaction temperature was adjusted to 40 ° C with stirring. At this time, the hydrogen gas pressure in the reaction vessel was 5 kg / cm ² . After 1 hour, the main product in the reaction solution was collected by HPLC, and I
When confirmed by R and NMR, it was confirmed that the target tetrahydrofuran was produced in a yield of 89%.

Example 12 In a dead-end type reaction vessel having a volume of 1 liter, 100 g of hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 4 ℃ and vacuum degree of 750mmHg,
40 ml of cooled 2-methoxycarbonylfuran was poured into the reaction vessel. Then, the reaction temperature was adjusted to 40 ° C. with stirring. At this time, the hydrogen gas pressure in the reaction vessel is 9 kg
It was / cm ² . After 3 hours, the main product in the reaction solution was collected by HPLC and confirmed by IR and NMR. As a result, it was confirmed that the target 2-methoxycarbonyltetrahydrofuran was produced at a yield of 75%.

Example 13 In a dead-end type reaction vessel having a volume of 1 liter, 100 g of hydrogen storage alloy LaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 4 ℃ and vacuum degree of 750mmHg,
40 ml of cooled pyrrole was injected into the reaction vessel. Then, the reaction temperature was adjusted to 60 ° C. while stirring. At this time,
The hydrogen gas pressure in the reaction vessel was 12 kg / cm ² . After 2 hours, the main product in the reaction solution was collected by HPLC, and I
When confirmed by R and NMR, it was confirmed that the target pyrrolidine was produced in a yield of 68%.

Example 14 In a dead-end type reaction vessel having a volume of 1 liter, 200 g of hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 4 ℃ and vacuum degree of 750mmHg,
50 ml of cooled 1,2-di-ethoxycarbonylpyrrole
Was injected into the reaction vessel. Then, the reaction temperature was adjusted to 60 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel was 18 kg / cm ² . After 4 hours, the main product in the reaction solution was separated by HPLC and confirmed by IR and NMR. It was confirmed that the desired 1,2-diethoxycarbonylpyrrolidine was produced in a yield of 69%. confirmed.

Example 15 In a dead-end type reaction vessel having a volume of 1 liter, 200 g of hydrogen storage alloy LaNi _{5 in} which hydrogen was stored in advance was placed. After degassing for 5 minutes at 0 ° C and vacuum degree of 750mmHg,
100 ml of a cooled 10% strength by weight solution of pyridine in cyclohexane were injected into the reaction vessel. Then, the reaction temperature was adjusted to 80 ° C. with stirring. At this time, the hydrogen gas pressure in the reaction vessel was 29 kg / cm ² . After 6 hours, HPLC
When the main product in the reaction solution was collected by and confirmed by IR and NMR, it was confirmed that the desired piperidine was produced in a yield of 76%.

[0026]

As described above, when the hydrogen storage alloy according to the present invention is used for hydrogenation reduction of a cyclic organic compound such as an aromatic compound or a heterocyclic compound, the hydrogen storage alloy itself has a high catalytic ability. Since it does not require conventional catalysts such as nickel, it is possible to efficiently carry out hydrogenation reduction of cyclic organic compounds under conditions of high safety with a hydrogen gas pressure of less than 30 kg / cm ² , and iterative reaction. It is possible to use it. Further, the hydrogen storage alloy can store a large amount of hydrogen gas as compared with the hydrogen storage device, and can operate at a low pressure as described above. Further, when the upflow tray column as described above is used, there is an operational advantage that the load on the separation of the reaction solution and the hydrogen storage alloy can be significantly reduced.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display area C07C 5/11 13/12 9280-4H 13/18 9280-4H 13/26 9280-4H 13/48 9280-4H 13/58 9280-4H 13/60 9280-4H 37/00 39/17 9159-4H 51/36 61/08 8827-4H 209/72 211/36 9280-4H C07D 207/16 8314-4C 295/02 307 / 08 307/24 // C07B 61/00 300 (72) Inventor Shunichi Dosako 5-15-39-616 Kitaurawa, Urawa-shi, Saitama Prefecture (72) Inventor Eiki Eiki 1-6-6 Irumagawa, Sayama-shi, Saitama Prefecture −802

Claims (3)

[Claims] 1. When hydrogenating a cyclic organic compound having one or more double bonds, M (rare earth element or C
a representing the element a) and hexagonal C containing Ni as an essential element
A cyclic organic compound characterized by using a hydrogen storage alloy having a compound having an aCu ₅ type crystal structure as a main phase, and catalytically hydrogenating with hydrogen released from the alloy to reduce one or more double bonds. Hydrogenation reduction method. 2. The method for hydrogenating and reducing a cyclic organic compound according to claim 1, wherein the cyclic organic compound having one or more double bonds is an aromatic compound. 3. The method for hydrogenating and reducing a cyclic organic compound according to claim 1, wherein the cyclic organic compound having one or more double bonds is a heterocyclic compound or a derivative thereof.