JP3023809B2 - Method for hydrogenating and reducing cyclic organic compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for hydrogenating and reducing 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 for synthesizing chemical products used in the fields of food, medicine, agrochemicals and the like.

[0002]

2. Description of the Related Art Many examples of reactions 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 under a hydrogen atmosphere using a metal catalyst such as platinum, nickel, cobalt, or copper. According to this method, the operation is simpler than the reaction using another reducing agent,
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 relatively high catalytic activities and can perform hydrogenation even at low temperatures and low pressures, but nickel, cobalt, copper, etc. have catalytic activities. Low and often require high temperature and high pressure reactions. On the other hand, industrially, from the viewpoint of running cost when using this reaction,
Precious metals, such as palladium and platinum, are renewable but expensive, and are not always suitable for use on an industrial scale.

[0003] Hydrogen storage alloys that have been recently developed and are attracting attention for their use are currently used in the fields of automobiles, heat pumps, and indoor cooling and heating systems. Examples of hydrogen storage alloys include LaNi ₅ , MgNi, There are many types such as TiFe, and the functions of the alloy such as hydrogen storage amount, discharge pressure and discharge temperature vary greatly depending on the constituent metals thereof. Therefore, selection of the alloy is important for its use.

As an example of the hydrogenation reduction reaction using a hydrogen storage alloy, hydrogen reduction of olefins, hydrogenation of carbon monoxide and synthesis of ammonia are described in “Hydrogen Storage Alloy Data Book” (published by Yono Shobo 1987). Further, regarding the _C18 alcohol formation reaction by atmospheric pressure hydrogenolysis of methyl oleate, see The Chemical Society of Japan (54th Annual Spring Meeting 1987).
Year). Further, hydrogenation of fats and oils (Japanese Patent Application Laid-Open No. 63-268799), production of sugar alcohols (Japanese Patent Application No. 2-219100), reduction of disulfide bonds (Japanese Patent Application No. 2-27
No. 7808) and the Deprotection Law (Japanese Patent Application No. 2-277809) have also been reported.

However, there is no report on the case where a cyclic organic compound such as an aromatic compound or a heterocyclic compound is hydrogenated and reduced using a hydrogen storage alloy.

[0006]

SUMMARY OF THE INVENTION The present invention uses a highly reactive hydrogen storage alloy in the reduction of a cyclic organic compound such as an aromatic compound or a heterocyclic compound by catalytic hydrogenation. There is no need to use a catalyst, and a large amount of hydrogen discharged from a hydrogen storage alloy can be used at low pressure. Aromatic compounds and heterocyclic compounds can be safely and inexpensively produced at a high reduction rate by catalytic hydrogenation. It is an object of the present invention to provide a method for hydrogenating and reducing a cyclic organic compound such as described above.

[0007]

According to the present invention, when hydrogenation is performed on a cyclic organic compound such as an aromatic compound or a heterocyclic compound by catalytic hydrogenation, M (representing a rare earth element or Ca element) is obtained. And using a hydrogen storage alloy having a hexagonal CaCu ₅ type crystal structure having Ni as an essential element as a main phase, performing catalytic hydrogenation with hydrogen released from the alloy, and reducing the hydrogen. I do.

Hereinafter, the present invention will be described in detail. 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 main phase of the hydrogen storage alloy used in the present invention is a compound having a hexagonal CaCu ₅ type crystal structure containing M (representing a rare earth element or Ca element) and Ni as essential elements. In addition, 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 balance includes intermetallic compounds other than the main phase, impurities, additional elements, and the like as a second phase or a mixed phase. These hydrogen storage alloys has a high catalytic activity to itself reduction reaction, by appropriately setting the temperature conditions for the reducing reaction with the type of alloy used, be hydrogen gas pressure condition of less than 30kg / cm ² It is possible to safely reduce a cyclic organic compound such as an aromatic compound or a heterocyclic compound at a high reduction rate.

After this hydrogen storage alloy is pulverized, hydrogen is stored in the alloy at a temperature of 0 ° C. or lower under a hydrogen atmosphere for a certain period of time to absorb hydrogen. In the present invention, a reaction solution containing a cyclic organic compound such as an aromatic compound or a heterocyclic compound and the above-mentioned hydrogen storage alloy are put into a reaction vessel, and after degassing, the reaction solution is adjusted to an appropriate temperature condition while stirring. Or by enclosing the hydrogen storage alloy in a tray type column in which the hydrogen storage alloy can be cooled by a jacket type, and circulating the reaction solution maintained at an appropriate temperature condition, thereby obtaining an aromatic compound or the like. Hydrogenate a cyclic organic compound such as a heterocyclic compound.

After the reaction, the hydrogen gas and the reaction liquid 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. The present invention, the nature of the hydrogen storage alloy, the hydrogen gas pressure is capable of performing sufficiently hydride reducing cyclic organic compounds under conditions of less than 30kg / cm ^2, on the holding security of the production apparatus, It is advantageous. Further, as the hydrogen storage alloy, a plating powder, a surface treatment powder, an encapsulated alloy of copper, silicon, or the like, which is surface-modified for the purpose of improving corrosion resistance, thermal conductivity, and the like, can also be used in the present invention.

[0011]

Next, the present invention will be described in detail with reference to examples. Example 1 A dead-end type reaction vessel having a capacity of 1 liter is charged with 100 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen is stored in advance. After degassing at 0 ° C and vacuum of 750mmHg for 5 minutes,
100 ml of cooled toluene was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 80 ° C. while stirring. At this time,
The hydrogen gas pressure in the reaction vessel was 20 kg / cm ² . Two hours later, the main product in the reaction solution was separated by HPLC, and I
When confirmed by R and NMR, the desired 1- was obtained in a yield of 88%.
It was confirmed that methyl-cyclohexane was produced.

Example 2 A dead end type reaction vessel having a capacity of 1 liter is charged with 100 g of a hydrogen storage alloy LaNi _{5 in} which hydrogen is stored in advance. After degassing at 4 ° C and a vacuum of 750mmHg for 5 minutes,
Cooled 5% by weight solution of benzoic acid in 0.01M KOH
100 ml was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 70 ° C. while 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 separated by HPLC and confirmed by IR and NMR. As a result, it was confirmed that the desired 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 capacity of 1 liter.
_{Insert 0.8} . After degassing at 0 ° C. and a degree of vacuum of 750 mmHg for 5 minutes, 100 ml of a cooled 4% by weight methanol solution of 2,4-diaminotoluene was poured into the reaction vessel. Thereafter, the reaction temperature was adjusted to 100 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel was 24 kg / cm ² . Two hours later, 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 A dead end type reaction vessel having a capacity of 1 liter is charged with 60 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen is stored in advance. After degassing at 0 ° C and vacuum of 750mmHg for 5 minutes,
Cooled 5% by weight solution of naphthalene in ethanol
80 ml was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 70 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel was 14 kg / cm ² . Four hours later, the main product in the reaction solution was separated by HPLC and confirmed by IR and NMR. As a result, it was confirmed that the desired tetralin was produced in a yield of 92%.

EXAMPLE 5 A dead end type reaction vessel having a capacity of 1 liter is charged with 150 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen has been stored in advance. After degassing at 0 ° C and vacuum of 750mmHg for 5 minutes,
100 ml of a cooled 10% by weight solution of anthracene in cyclohexane was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 40 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel was 15 kg / cm ² . 4 hours later, HP
The main product in the reaction solution was separated by LC and confirmed by IR and NMR. As a result, it was confirmed that the target decahydroanthracene was produced in a yield of 71%.

Example 6 A dead end type reaction vessel having a capacity of 1 liter is charged with 150 g of a hydrogen storage alloy LaNi _{5 in} which hydrogen is stored in advance. After degassing at 0 ° C and vacuum of 750mmHg for 5 minutes,
100 ml of a cooled 10% strength by weight solution of phenanthrin in cyclohexane was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 40 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel was 14 kg / cm ² . After 4 hours, H
The main product in the reaction solution was separated by PLC, and IR and 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 capacity of 1 liter.
_{Insert 0.8} . After degassing at 25 ° C. and a degree of vacuum of 750 mmHg for 5 minutes, 100 ml of cooled 1-naphthol was poured into the reaction vessel. Thereafter, the reaction temperature was adjusted to 80 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel was 21 kg / c
m ² , but hydrogen was further added to 40 kg / cm ² . After 2 hours, the main product in the reaction solution was separated by HPLC, and IR,
When confirmed by NMR, it was confirmed that the desired 5-hydroxytetralin was produced in a yield of 81%.

Example 8 A dead-end type reaction vessel having a capacity of 1 liter is charged with 100 g of hydrogen storage alloy CaNi _{5 in} which 100 g of hydrogen in which hydrogen is stored in advance is stored. 25 ° C, 750mmH vacuum
g for 5 minutes, and then cooled to 100 ml of 2-naphthol
Was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 120 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel, 29 kg / cm ² and was the but further 50 kg / cm ² hydrogen was
And Two hours later, the main product in the reaction solution was separated by HPLC and confirmed by IR and NMR. As a result, it was confirmed that the desired 6-hydroxytetralin was produced in a yield of 74%.

Example 9 A dead-end type reaction vessel having a capacity of 1 liter is charged with 100 g of hydrogen storage alloy LaNi _{5 in} which hydrogen has been stored in advance. After degassing at 4 ° C and a vacuum of 750mmHg for 5 minutes,
50 ml of cooled cyclopentadiene was injected into the reaction vessel. Thereafter, 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 . Two hours later, the main product in the reaction solution was separated by HPLC and confirmed by IR and NMR. As a result, it was confirmed that the desired cyclopentene was produced in a yield of 55%.

Example 10 A dead end type reaction vessel having a capacity of 1 liter is charged with 200 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen is stored in advance. After degassing at 4 ° C. and a degree of vacuum of 750 mmHg for 5 minutes, 50 ml of cooled cyclooctatetraene was injected into the reaction vessel. Thereafter, 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
Met. After 4 hours, the main product in the reaction solution was separated by HPLC and confirmed by IR and NMR. As a result, it was confirmed that the desired cyclooctane was produced in a yield of 66%.

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

Example 12 A dead-end type reaction vessel having a capacity of 1 liter is charged with 100 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen has been stored in advance. After degassing at 4 ° C and a vacuum of 750mmHg for 5 minutes,
40 ml of cooled 2-methoxycarbonylfuran was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 40 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel was 9 kg
/ cm ² . Three hours later, the main product in the reaction solution was separated by HPLC and confirmed by IR and NMR. As a result, it was confirmed that the desired 2-methoxycarbonyltetrahydrofuran was produced in a yield of 75%.

Example 13 A dead end type reaction vessel having a capacity of 1 liter is charged with 100 g of a hydrogen storage alloy LaNi _{5 in} which hydrogen is stored in advance. After degassing at 4 ° C and a vacuum of 750mmHg for 5 minutes,
40 ml of cooled pyrrole were poured into the reaction vessel. Thereafter, 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 . Two hours later, the main product in the reaction solution was separated by HPLC, and I
When confirmed by R and NMR, it was confirmed that the desired pyrrolidine was produced in a yield of 68%.

EXAMPLE 14 A dead-end type reaction vessel having a capacity of 1 liter is charged with 200 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen is stored in advance. After degassing at 4 ° C and a vacuum of 750mmHg for 5 minutes,
50 ml of cooled 1,2-di-ethoxycarbonylpyrrole
Was injected into the reaction vessel. Thereafter, 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 . Four hours later, 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 A dead-end type reaction vessel having a capacity of 1 liter is charged with 200 g of a hydrogen storage alloy LaNi _{5 in} which hydrogen has been stored in advance. After degassing at 0 ° C and vacuum of 750mmHg for 5 minutes,
100 ml of a cooled 10% by weight solution of pyridine in cyclohexane was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 80 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel was 29 kg / cm ² . After 6 hours, HPLC
The main product in the reaction solution was fractionated by and analyzed by IR and NMR. As a result, it was confirmed that the desired piperidine was produced in a yield of 76%.

[0026]

As described above, when hydrogen reduction of a cyclic organic compound such as an aromatic compound or a heterocyclic compound is performed by using a hydrogen storage alloy according to the present invention, the hydrogen storage alloy itself has a high catalytic ability. without requiring a catalyst such as conventional nickel because they have, in a high less than ² safety hydrogen gas pressure 30kg / cm conditions, efficiently it is possible to carry out the hydrogenation reduction of cyclic organic compounds, repeated reaction It is possible to provide. Further, the hydrogen storage alloy can store a larger amount of hydrogen gas than the hydrogen storage device, and can operate at a low pressure as described above. Furthermore, the use of the upflow tray column as described above has an operational advantage that the load on the separation of the reaction solution and the hydrogen storage alloy can be greatly reduced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07C 5/11 C07C 5/11 13/12 13/12 13/18 13/18 13/26 13/26 13/48 13/48 13/58 13/58 13/60 13/60 37/00 37/00 39/17 39/17 51/36 51/36 61/08 61/08 209/72 209/72 211/36 211/36 C07D 207 / 16 C07D 207/16 295/02 295/02 307/08 307/08 307/24 307/24 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Shunichi Dosako Kitaurawa, Urawa City, Saitama Prefecture 5-15-39-616 (72) Inventor Eiji Deke 1-6-802 Irumagawa, Sayama-shi, Saitama (56) References JP-A-6-16580 (JP, A) JP-A-2-263900 (JP) , A) JP-A-2-269797 (JP, A) JP-A-2-77496 (JP, A) JP-A-63-268799 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C07B 35/02 C07C 5/05 C07C 5/10 C07C 51/36 C07C 209/72

Claims (3)

(57) [Claims] (1) When hydrogenating and reducing a cyclic organic compound having one or more double bonds, M (rare earth element or C
a) and hexagonal C with Ni as an essential element
a cyclic organic compound comprising using a hydrogen storage alloy having a compound having a crystal structure of aCu ₅ type 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 according to claim 1, wherein the cyclic organic compound having one or more double bonds is an aromatic compound. 3. The method for hydrogenating 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.