JP2871919B2 - N-[(halogenopyridyl) methyl] aminoacetonitrile and process for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound,
Further, N-[(halogenopyridyl) methyl] ethylenediamine, which is an intermediate for pesticides, is useful as a precursor.
The present invention relates to [(halogenopyridyl) methyl] aminoacetonitrile, a method for producing the same, and a method for producing the N-[(halogenopyridyl) methyl] ethylenediamine from N-[(halogenopyridyl) methyl] aminoacetonitrile.

[0002]

2. Description of the Related Art Conventionally, N-[(halogenopyridyl) methyl] ethylenediamines (3), which are intermediates for agricultural chemicals, are methylhalogenopyridines (4) as shown in the following formula. Is converted to chloromethylhalogenopyridines (5) and then reacted with ethylenediamine.

[0003]

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However, since chloromethylhalogenopyridines (5) are decomposed by contact with oxygen in the air, storage stability is impaired, and skin irritation is immediately caused by contact with a small amount of vapor, causing immediate skin damage. There is a problem that it is so expensive that it is easily caused and that handling is not easy.

Also, halogenomethylhalogenopyridines
The yield when synthesizing N-[(halogenopyridyl) methyl] ethylenediamine (3) from (5) is 86% (when X = Cl), which is not sufficiently satisfactory.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the problem in producing N-[(halogenopyridyl) methyl] ethylenediamine by the conventional method as described above, and has been made by the general formula (I). 1):

[0007]

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(Wherein X represents a halogen atom) N-[(halogenopyridyl) methyl] aminoacetonitrile represented by the general formula (2):

[0009]

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Wherein X represents a halogen atom, wherein aminomethylhalogenopyridines are reacted with glycolonitrile.
A compound represented by the general formula (1) is reduced by reducing the compound represented by the general formula (1):

[0011]

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(Wherein X represents a halogen atom) The present invention relates to a method for producing N-[(halogenopyridyl) methyl] ethylenediamine represented by the formula:

[0013]

EXAMPLES The general formula (1) of the present invention:

[0014]

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X in the compound represented by the formula is Cl,
A methylaminoacetonitrile group, which is a halogen atom such as Br and bonds to the pyridine ring, may be bonded to any of the 3-, 4-, 5-, and 6-positions of the pyridine ring.

Specific examples of the compound represented by the general formula (1) include N-[(2-chloro-5-pyridyl) methyl] aminoacetonitrile and N-[(2-chloro-3-pyridyl) methyl ] Aminoacetonitrile, N
-[(2-chloro-4-pyridyl) methyl] aminoacetonitrile, N-[(2-chloro-6-pyridyl) methyl] aminoacetonitrile, N-[(2-bromo-5-
Pyridyl) methyl] aminoacetonitrile, N-[(2
-Bromo-3-pyridyl) methyl] aminoacetonitrile and the like, but are not limited thereto.

The compound represented by the above general formula (1) is inactive against oxygen, so that it has good storage stability, and furthermore, it does not easily cause skin damage even upon contact, and is easy to handle. Compound. Further, this compound is a compound having the property that N-[(halogenopyridyl) methyl] ethylenediamine can be produced in a high yield if reduced.

The compound represented by the general formula (1) is, for example, a compound represented by the general formula (2):

[0019]

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(Wherein X represents a halogen atom such as Cl or Br), and is produced by reacting aminomethylhalogenopyridines and glycolonitrile (HOCH ₂ CN).

[0021]

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The reaction conditions for producing the compound represented by the general formula (1) from the compound represented by the general formula (2) and glycolonitrile are as follows based on 1 mol of the compound represented by the general formula (2). The use of glycolonitrile at a ratio of 1.0 to 1.2 moles, preferably 1.0 to 1.1 moles, from the viewpoint that the compound represented by the general formula (1) can be obtained in high yield by suppressing side reactions. preferable.

The method of mixing the compound represented by the general formula (2) with glycolonitrile is not particularly limited. It is preferable from the viewpoint of suppressing the reaction between them.

It is preferable to use a solvent when mixing the compound represented by the general formula (2) with glycolonitrile from the viewpoint that the reaction proceeds efficiently. In this case, the amount of the compound represented by the general formula (2) ) Is preferably 0.1 to 10 times by weight, more preferably 0.5 to 2 times by weight, based on the total amount of the compound represented by the formula (1) and glycolonitrile.

Specific examples of the solvent include water; alcohols such as methanol and ethanol; ethers such as ethyl ether, tetrahydrofuran and dioxane; aromatic and alicyclic hydrocarbons such as toluene, xylene and hexane.

In a preferred embodiment of the reaction between the compound represented by the general formula (2) and glycolonitrile, a mixture of the solvent and the compound represented by the general formula (2) is heated to 10 to 50 ° C., preferably 20 to 30 ° C. While maintaining the temperature at about 0 ° C., glycolonitrile was added dropwise thereto in about 0.5 to 5 hours.
This is a method of stirring at 10 to 50 ° C. for 1 to 5 hours, and the reaction rate at this stage is almost the same as that of the compound represented by the general formula (2).
100%.

When water is used as the solvent, the reaction solution after the completion of the reaction is treated with an organic solvent such as toluene, xylene, or the like.
Extract with hydrocarbons such as hexane, remove the aqueous layer by operations such as liquid separation, and evaporate the solvent from the resulting organic layer.
Preferably, by distillation under reduced pressure, N-[(halogenopyridyl) methyl] aminoacetonitrile represented by the general formula (1) can be obtained in a yield of about 95% or more.

The N-[(halogenopyridyl) methyl] aminoacetonitrile represented by the general formula (1) thus obtained has a purity of 98% or more and contains almost no unreacted substances. It can be used in the next step without the need.

Specific examples of the compound represented by the general formula (2) include, for example, 2-chloro-5-aminomethylpyridine, 2-chloro-3-aminomethylpyridine,
Chloro-4-aminomethylpyridine, 2-chloro-6-
Examples thereof include aminomethylpyridine, 2-bromo-5-aminomethylpyridine, and 2-bromo-3-aminomethylpyridine. These compounds are obtained by catalytically reducing the corresponding cyanohalogenopyridines using a hydrogenation catalyst. Can be obtained more easily.

In the present invention, the compound represented by the general formula (1) is a compound represented by the general formula (3):

[0031]

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(Wherein X is the same as described above). It is used for the production of N-[(halogenopyridyl) methyl] ethylenediamine represented by the formula:

The compound represented by the general formula (3) can be produced by reducing the compound represented by the general formula (1). As a typical method of this reduction, a general formula (1)
Is catalytically reduced using a hydrogenation catalyst such as Raney cobalt or Raney nickel.

The amount of the catalyst used in this case is determined by the general formula (1)
Is preferably from 10 to 50% by weight based on the compound represented by the formula, since the reaction is completed in a short time.
More preferably, it is% by weight.

The above-mentioned catalytic reduction is preferably carried out in an organic solvent such as dioxane, methanol or toluene, from the viewpoint that the reaction proceeds gently to suppress side reactions, and is preferably carried out in the presence of ammonia. It is preferable in terms of suppressing side reactions such as a dimerization reaction of a product and decomposition of a nitrile group.

The amount of the solvent used in the catalytic reduction is preferably 1 to 10 times by weight of the compound represented by the general formula (1) to enhance the stirring efficiency and improve the contact between the catalyst and the substrate. And more preferably 2 to 5 times by weight. The amount of ammonia is preferably 0.1 to 5 times the weight of the compound represented by the general formula (1) from the viewpoint of effectively suppressing the side reaction and the economical efficiency.
More preferably, it is 1 to 3 times by weight.

The reaction temperature and the reaction pressure at the time of performing the above-mentioned catalytic reduction are each 50 to 50 in consideration of the reaction rate and the like.
The reaction temperature is preferably about 100 ° C. and about 10 to 70 kg / cm ^2, and the reaction time when the reduction is performed under such reaction conditions is usually about 1 to 5 hours.

After completion of the reaction, a simple operation such as distillation is carried out after filtering off the catalyst, and N-[(halogenopyridyl) methyl] ethylenediamine represented by the general formula (3) can be obtained with high purity. . The yield from the compound represented by the general formula (1) is as high as about 90% or more.

Next, the present invention will be described based on examples.

Example 1 Preparation of N-[(2-chloro-5-pyridyl) methyl] aminoacetonitrile 150 g (1.053 mol) of 2-chloro-5-aminomethylpyridine, 150 ml of water were placed in a 500 ml four-necked flask.
g, 82.5 g of 72.5% glycolonitrile aqueous solution
(1.105 mol) was dropped at 15-20 ° C for 40 minutes, then 40 ° C
For 3 hours. Thereafter, 300 g of toluene was added for extraction, followed by washing with 150 g of water, and the obtained organic layer was concentrated under reduced pressure to give N-[(2-chloro-5-
Pyridyl) methyl] aminoacetonitrile 98.1% (filler; Capsule Pack C-18 SG120 (Shiseido Co., Ltd.)
, A column temperature of 30 ° C., an eluent; 1% acetic acid aqueous solution: acetonitrile (95: 5), a detector; liquid chromatography using UV 268 nm) to obtain 192.7 g of a concentrated residue. The yield of N-[(2-chloro-5-pyridyl) methyl] aminoacetonitrile was 98.9% and the unreacted material content was 0.1%.

Results of identification of N-[(2-chloro-5-pyridyl) methyl] aminoacetonitrile NMR analysis (solvent CDCl ₃ ): δ ppm 1.82 (s, 1H), 3.61 (s, 2H), 3.95 (s, 2H) ), 7.20-7.48 (m, 1
H), 7.60-7.87 (m, 1H), 8.35-8.48 (d, 1H) MS (m / e): 182 Example 2 Production of N-[(2-chloro-5-pyridyl) methyl] ethylenediamine N- [(2-chloro-5-pyridyl) methyl] aminoacetonitrile 9.1 g (0.05 mol), dioxane 200 g,
13 g of ammonia and 1.8 g of Raney cobalt were charged into a 500 ml electromagnetic stirring autoclave, and hydrogen was introduced thereinto at 80 ° C.
After raising the temperature and pressure to 40 kg / cm ² , catalytic reduction was performed while introducing hydrogen as needed to maintain the temperature and pressure. Hydrogen absorption was completed 2 hours and 20 minutes after the start of hydrogen introduction. After completion of the reaction, the catalyst was removed by filtration, and 9.9 g of a concentrated residue obtained by distilling off ammonia and dioxane was subjected to an absolute calibration curve method using liquid chromatography to determine the yield.
[(2-Chloro-5-pyridyl) methyl] ethylenediamine was obtained in a yield of 93.0%. The residue was distilled to obtain 8.1 g of N-[(2-chloro-5-pyridyl) methyl] ethylenediamine as a fraction having a boiling point of 134 to 138 DEG C./1.5 mmHg.
I got

[0042]

According to the present invention, N- represented by the general formula (1)
[(Halogenopyridyl) methyl] aminoacetonitrile is a compound having low skin irritation and good storage stability as compared with an intermediate of a conventional method, and can be obtained in high yield.

Further, N- represented by the general formula (1)
[(Halogenopyridyl) methyl] aminoacetonitrile is catalytically reduced using a hydrogenation catalyst to give N- (halogenopyridyl) methylethylenediamine represented by the general formula (3), which is useful as an agricultural chemical intermediate, by a conventional method. It can be produced with a higher yield than that of.

────────────────────────────────────────────────── (5) References JP-A-63-10762 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07D 213/61 CA (STN) REGISTRY (STN) )

Claims (5)

(57) [Claims] [Claim 1] General formula (1): (Wherein, X represents a halogen atom) N-[(halogenopyridyl) methyl] aminoacetonitrile represented by the following formula: 2. A compound represented by the general formula (1):
The N-[(halogenopyridyl) methyl] aminoacetonitrile according to claim 1, which is [(2-chloro-5-pyridyl) methyl] aminoacetonitrile. 3. The general formula (2): (Wherein X represents a halogen atom). A method for producing a compound according to claim 1, wherein an aminomethylhalogenopyridine represented by the following formula is reacted with glycolonitrile. 4. The compound of claim 1 which is reduced to form a compound of the general formula
(3): (Wherein X represents a halogen atom) A method for producing N-[(halogenopyridyl) methyl] ethylenediamine represented by the following formula: 5. The method according to claim 4, wherein the reduction is a catalytic reduction in the presence of a hydrogenation catalyst.