JP2932330B2 - Method for hydrogenating and reducing nitrogen-containing compounds - Google Patents

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 and reducing a nitrogen-containing 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 Nitro groups (-NO ₂ ) and nitrile groups (-
CN), nitroso group (-NO), alkydoxime (RC
As a reaction for reducing a compound containing a nitrogen atom such as H = NOH) or ketoxime (R′RC = NOH) by hydrogenation, a method using various metal catalysts in a hydrogen atmosphere is known. The catalyst used in this reaction includes palladium, platinum, nickel, cobalt, copper and the like.
Of these, palladium and platinum have relatively high activity as catalysts and can perform hydrogenation even at low temperature and low pressure, but nickel, cobalt, copper, etc. have low activity as catalysts and high temperature and high pressure conditions. The following reaction is required.
Precious metals such as palladium and platinum are renewable, but expensive and not always suitable for use on an industrial scale.

[0003] Recently developed hydrogen storage alloys, which have attracted attention for their applications, are currently used in the fields of automobiles, heat pumps, and indoor cooling and heating systems. Examples of hydrogen storage alloys include LaNi ₅ and MgNi. , TiFe, etc., 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, in using the alloy, it is important to select the alloy.

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,
Atmospheric pressure hydrogenolysis of methyl oleate to form C ₁₈ alcohols is described in The Chemical Society of Japan (The 54th Annual Meeting of the Society, 1987)
Year). Also, 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.
No. 277808), and the Deprotection Law (Japanese Patent Application No. 2-277809) are also reported.

However, there is no report on the case where a nitrogen-containing compound is hydrogenated and reduced using a hydrogen storage alloy.

[0006]

SUMMARY OF THE INVENTION The present invention utilizes a highly reactive hydrogen storage alloy in reducing a nitrogen-containing compound by catalytic hydrogenation, so that it is not necessary to use a conventional catalyst at all. An object of the present invention is to provide a method for safely and inexpensively hydrogenating a nitrogen-containing compound by catalytic hydrogenation at a high reduction rate, in which a large amount of hydrogen discharged from a hydrogen storage alloy can be used at a low pressure.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a method for hydrogenating a compound containing a nitrogen atom such as a nitro group, a nitrile group, a nitroso group, an aldoxime, and a ketoxime by catalytic hydrogenation. Or a Ca element) and a hydrogen storage alloy having a main phase of a compound having a hexagonal CaCu _5- type crystal structure with Ni as an essential element, and performing catalytic hydrogenation with hydrogen released from the alloy, It is characterized by reduction.

Hereinafter, the present invention will be described in detail. The hydrogen storage alloy used in the present invention is a hexagonal Ca containing M (representing a rare earth element or Ca element) and Ni as essential elements.
The main phase is a compound having a Cu ₅ type crystal structure. Specific examples include CaNi ₅ , LaNi ₅ , LaNi _4.2 Al _0.8 .
The CaCu _5- type crystal phase contained in the hydrogen storage alloy is 5
0% by weight or more, the balance being an intermetallic compound other than the main phase,
Impurities, additional elements, and the like exist as a second phase or a mixed phase.

Since these hydrogen storage alloys themselves have a high catalytic activity for the reduction reaction, depending on the type of alloy used and the setting of the reduction reaction temperature of the reaction solution, 20 kg / cm ² is required.
It is possible to safely and safely hydrogenate nitrogen-containing compounds at a high reduction rate under conditions of a hydrogen gas pressure of less than. After the hydrogen storage alloy is pulverized, hydrogen is stored in the alloy at a temperature of 0 ° C. or lower in a hydrogen atmosphere for a certain period of time to absorb hydrogen.

In the present invention, the reaction solution and the hydrogen storage alloy preliminarily storing hydrogen are put into a reaction tank, and after deaeration, the reaction solution is maintained at a constant temperature while stirring, or
The hydrogen storage alloy can be maintained at a constant temperature by a jacket type.The hydrogen storage alloy is sealed in a tray column, and the nitrogen-containing compound is circulated by circulating a reaction solution maintained at a constant temperature. 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. Note that, in the present invention, due to the characteristics of the hydrogen storage alloy, it is possible to sufficiently perform the hydrogenation reduction of the nitrogen-containing compound under the condition that the hydrogen gas pressure is less than 20 kg / cm ² , which is advantageous in terms of maintenance and safety of the manufacturing apparatus. It is. As the hydrogen storage alloy, a plating powder, a surface treatment powder, and an encapsulated alloy of copper, silicon, or the like, which are surface-modified for the purpose of improving corrosion resistance and thermal conductivity, can be used in the present invention.

[0012]

The present invention will be specifically described below with reference to examples. Example 1 A dead end type reaction vessel having a capacity of 1 liter was charged with 100 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance. Then, the mixture was degassed at 0 ° C. and a degree of vacuum of 750 mmHg for 3 minutes, and 300 ml of a cooled 0.5 wt% ethanol solution of 1-nitro-2-phenylcyclohexane was poured 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 3.8 kg / cm ² . After 4 hours, the main fraction in the reaction solution was separated by high performance liquid chromatography and analyzed, and it was confirmed that 1-amino-2-phenylcyclohexane was produced in a yield of 80%. Confirmation of the product was performed by NMR.

[0013] already containing hydrogen storage alloy LaNi ₅ 50g of which were pre-storing hydrogen in a dead-end type reaction vessel of Example 2 1 liter.
Then, it was degassed at 0 ° C. and a vacuum of 750 mmHg for 5 minutes, and cooled
200 ml of a 1.0% by weight concentration of 2-nitroacetophenone in ethyl acetate 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 2.3 kg / cm ² . After 4 hours, a main fraction in the reaction solution was separated by high performance liquid chromatography and analyzed, and it was confirmed that 2-aminoacetophenone was produced in a yield of 95%. Confirmation of the product was performed by NMR.

Example 3 A dead-end type reaction vessel having a capacity of 1 liter was charged with 100 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance. Then, the mixture was degassed for 4 minutes at 0 ° C. and a degree of vacuum of 750 mmHg, and cooled to a 0.5% by weight aqueous solution of 4-nitrophenol.
200 ml 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 14.0 kg / cm ² . Four hours later, the main fraction in the reaction solution was separated and analyzed by high performance liquid chromatography, and it was confirmed that 4-aminocyclohexanol was produced in a yield of 81%. Confirmation of the product was performed by NMR.

Example 4 A dead end type reaction vessel having a capacity of 1 liter was charged with 100 g of a hydrogen storage alloy LaNi _4.2 Al _{0.8 in} which hydrogen had been previously stored. Then, the mixture was degassed at 25 ° C. and a vacuum of 750 mmHg for 2 minutes, and 100 ml of a cooled 2.0% by weight 2-nitrocinnamic acid ethanol solution was poured 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 4.2 kg / cm ² . Six hours later, a major fraction in the reaction solution was separated and analyzed by high performance liquid chromatography, and it was confirmed that 2-aminocinnamic acid was produced in a yield of 65%. Confirmation of the product was performed by NMR.

Example 5 A dead end type reaction vessel having a capacity of 1 liter was charged with 100 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance. Then, the mixture was degassed at 0 ° C. and a degree of vacuum of 750 mmHg for 5 minutes, and 200 ml of a cooled 0.5% by weight 4-nitrodibenzothiophene ethanol solution 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 4.2 kg / cm ² . Five hours later, the main fraction in the reaction solution was separated and analyzed by high performance liquid chromatography, and it was confirmed that 4-aminodibenzothiophene was produced in a yield of 68%. Confirmation of the product was performed by NMR.

[0017] dead-end type reaction vessel of Example 6 1 liter, previously, were placed the hydrogen storage alloy LaNi ₅ of 100g obtained by storing hydrogen. Then, the mixture was degassed at 0 ° C. and a degree of vacuum of 750 mmHg for 2 minutes, and 200 ml of a cooled 1.0% by weight methanol solution of 2-chloronitrobenzene 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 container was 9.8 kg / cm ² . After 4 hours, the main fraction in the reaction solution was separated and analyzed by high performance liquid chromatography, and it was confirmed that 2-aminochlorobenzene was produced in a yield of 92%. Confirmation of the product was performed by NMR.

Example 7 A dead-end type reaction vessel having a capacity of 1 liter was previously charged with 100 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen was stored. Then, the mixture was degassed at 0 ° C. and a degree of vacuum of 750 mmHg for 2 minutes, and 200 ml of a 1.0% by weight ethanol solution of 4-nitrobenzaldehyde was poured 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 3.9 kg / cm ² . Three hours later, the main fraction in the reaction solution was separated and analyzed by high performance liquid chromatography, and it was confirmed that 4-hydroxyaminobenzaldehyde was produced with a yield of 87%. Confirmation of the product was performed by NMR.

Example 8 A dead end type reaction vessel having a capacity of 1 liter was charged with 100 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance. Then, the mixture was degassed at 0 ° C. and a degree of vacuum of 750 mmHg for 2 minutes, and 200 ml of a cooled aqueous solution of 4-nitromethyl-3-cyclohexene-1-carboxylic acid having a concentration of 0.5% by weight was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 50 ° C. while stirring. At this time, the hydrogen gas pressure in the reaction vessel was 5.3 kg / cm ² . Five hours later, the main fraction in the reaction solution was separated and analyzed by high performance liquid chromatography, and it was confirmed that 4-aminomethylcyclohexanecarboxylic acid was produced in a yield of 80%. Confirmation of the product was performed by NMR.

Example 9 A 1-liter dead-end type reaction vessel was charged with 40 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance. Then, the mixture was degassed at 0 ° C. and a degree of vacuum of 750 mmHg for 2 minutes, and 200 ml of a cooled 0.5% by weight 2-methyl-3-nitrobutyronitrile methanol solution was injected into the reaction vessel. Thereafter, the reaction temperature was adjusted to 25 ° C. while stirring. At this time, the hydrogen gas pressure in the container was 1.8 kg / cm ² . 3
After a lapse of time, a major fraction in the reaction solution was separated and analyzed by high performance liquid chromatography, and it was confirmed that 3-amino-2-methylbutyronitrile was produced in a yield of 68%. Confirmation of the product was performed by NMR.

Example 10 A dead end type reaction vessel having a capacity of 1 liter was charged with 50 g of a hydrogen storage alloy LaNi _{5 in} which hydrogen was stored in advance. Then, the mixture was degassed for 2 minutes at 0 ° C. and a degree of vacuum of 750 mmHg, and 200 ml of a cooled 0.5% by weight 2,5-diamino-4-nitrosoimidazole aqueous solution 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 container was 2.2 kg / cm ² . 2
After a period of time, the main fractions in the reaction solution were separated and analyzed by high performance liquid chromatography, and the yield was 89%.
It was confirmed that 5-triaminoimidazole was produced. Confirmation of the product was performed by NMR.

Example 11 A dead end type reaction vessel having a capacity of 1 liter was charged with 150 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance. Then, the mixture was degassed at 0 ° C. and a degree of vacuum of 750 mmHg for 2 minutes, and 100 ml of a cooled 0.5% by weight 1,3,5-tricyanopentane aqueous solution was poured into the reaction vessel. Thereafter, the reaction temperature was adjusted to 75 ° C. while stirring. At this time, the hydrogen gas pressure in the container was 18.9 kg / cm ² . After 3 hours, the main fractions in the reaction solution were separated and analyzed by high performance liquid chromatography, and as a result, 4-aminomethyl-1,7 was obtained in a yield of 79%.
-It was confirmed that diaminoheptane was produced. Confirmation of the product was performed by NMR.

Example 12 A dead end type reaction vessel having a capacity of 1 liter was charged with 80 g of a hydrogen storage alloy LaNi _4.2 Al _{0.8 in} which hydrogen had been stored in advance. Then, it was degassed at 0 ° C. and a degree of vacuum of 750 mmHg for 2 minutes, and cooled to a concentration of 1.0% by weight of 4- (1-cyano-1-).
Phenyl) -methylenyl-1-hydroxyimino-2,
100 ml of a methanol solution of 5-cyclohexadiene was injected into the reaction vessel. Thereafter, the reaction temperature was raised to 40 while stirring.
Adjusted to ° C. At this time, the hydrogen gas pressure in the reaction vessel was 3.0k
g / cm ² . After 4 hours, the main fractions in the reaction solution were separated and analyzed by high performance liquid chromatography,
It was confirmed that 4-aminodiphenylacetonitrile was produced at a% yield. Confirmation of the product was performed by NMR.

Example 13 A dead end type reaction vessel having a capacity of 1 liter was charged with 80 g of a hydrogen storage alloy CaNi _{5 in} which hydrogen was stored in advance. Then, the mixture was degassed at 0 ° C and a degree of vacuum of 750 mmHg for 5 minutes, and cooled to a concentration of 1.0% by weight of 5-amino-4-chloro-3-.
150 ml of an ethanol solution of hydrazinopyridazine was injected into the reaction vessel. Thereafter, the reaction temperature was raised to 40 ° C while stirring.
Was adjusted. At this time, the hydrogen gas pressure in the reaction vessel was 3.1 kg /
It was cm ^2. After 6 hours, the catalyst was removed from the reaction solution, and the mixture was concentrated under reduced pressure. The residue was subjected to high performance liquid chromatography to collect a main fraction, and a 69% yield of 3,5-diamino-4-chloropyridazine was obtained. Was generated. Confirmation of the product was performed by NMR.

[0025]

As described above, when hydrogen reduction of a nitrogen-containing compound is performed using a hydrogen storage alloy according to the present invention, the hydrogen storage alloy itself has a high catalytic ability, and therefore, a conventional catalyst such as nickel is used. It is possible to efficiently perform the hydrogenation reduction of the nitrogen-containing compound under a highly safe condition at a hydrogen gas pressure of less than 20 kg / cm ² without need, and it is possible to repeatedly perform the reaction.

The hydrogen storage alloy can store a larger amount of hydrogen gas than an industrial hydrogen storage device, can operate at a low pressure as described above, and is much cheaper than conventional catalysts such as Pd and Pt. is there. Further, 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. Also, depending on the reactants, the hydrogen pressure during the reaction,
By controlling the temperature and the like, selective reduction with other hydrogenation sites such as an aldehyde group and a carbon-carbon multiple bond is possible.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 209/32 C07C 209/38 209/38 209/40 209/40 209/42 209/42 209/48 209/48 211/13 211/13 211/39 211/39 211/53 211/53 213/02 213/02 215/44 215/44 221/00 221/00 225/22 225/22 229/44 229/44 229/48 229 / 48 239/08 239/08 255/24 255/24 C07D 333/76 C07D 333/76 C07B 61/00 300 // C07B 61/00 300 B01J 23/74 321 (72) Inventor Shunichi Dosako Urawa-shi, Saitama Kazu Kitaura 5-15-39-616 (72) Inventor Eiji Eiji 1-6-802 Irumagawa, Sayama City, Saitama Prefecture (56) References JP-A-6-87796 (JP, A) JP-A-6-72968 (JP, A) JP-A-4-157473 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07B 31/00 B01J 23/755 B01J 23/78 C07B 43/02 C07B 43 / 04 C07C 209/32 C07C 209/38 C07C 209/40 C07C 209/42 C07C 209/48 C07C 211/13 C07C 211/39 C07C 211/53 C07C 213/02 C07C 215/44 C07C 221/00 C07C 225/22 C07C 229/44 C07C 229 / 48 C07C 239/48 C07C 255/24 C07D 333/76 C07B 61/00 300

Claims (7)

(57) [Claims] 1. When hydrogenating a compound containing a nitrogen atom, M (representing a rare earth element or Ca element) and Ni
Nitrogen-containing compound characterized by being reduced by catalytic hydrogenation with hydrogen released from the alloy using a hydrogen storage alloy having a main phase of a compound having a hexagonal CaCu ₅ type crystal structure having as essential elements Hydrogenation reduction method. 2. The method according to claim 1, wherein the compound R
A method for hydrogenating and reducing a nitrogen-containing compound, which comprises obtaining a compound R-NH ₂ (R represents an organic atomic group) using -NO ₂ (R represents an organic atomic group) as a starting material. 3. The method according to claim 1, wherein the compound R
-NO ₂ (R represents an organic atomic group) Compound R-NHOH (R represents an organic atomic group) hydrogenation reduction method of a nitrogen-containing compound, characterized in that to obtain a starting material. 4. The method according to claim 1, wherein the compound R
-CN (R represents an organic atomic group) hydrogenation reduction method of a nitrogen-containing compound, characterized in that to obtain the compound as the starting material R-CH ₂ NH ₂ (R represents an organic atomic group). 5. The method of claim 1, wherein the compound R
-CH = NOH (R represents an organic atomic group) hydrogenation reduction method of a nitrogen-containing compound, characterized in that to obtain the compound as the starting material R-CH ₂ NH ₂ (R represents an organic atomic group). 6. The compound R according to claim 1,
A method for hydrogenating and reducing a nitrogen-containing compound, comprising obtaining a compound R-NH ₂ (R represents an organic atomic group) using -NO (R represents an organic atomic group) as a starting material. 7. The method of claim 1 wherein the compound R
-NHNH ₂ (R represents an organic atomic group) hydrogenation reduction method of a nitrogen-containing compound, characterized in that to obtain the compound R-NH ₂ (R represents an organic atomic group) as starting materials.