JPS6372661A - Production of alkylhydrazines - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material for agricultural chemicals, drugs, blowing agents, etc., by the use of inexpensive raw materials economically and in high yield, by reacting hydrazine with an olefinic hydrocarbon in the presence of an inorganic acid. CONSTITUTION:Hydrazine is reacted with an olefinic hydrocarbon shown by formula I (R<1>, R<2> and R<3> may be same or different and are H or lower alkyl) in the presence of an inorganic acid usually at about 70-150 deg.C, preferably about 90-110 deg.C to give compounds shown by formula II and formula III. A hydrohalogenic acid, sulfuric acid, alkali hydrogensulfate, etc., are used as the inorganic acid and the amount of the inorganic acid used is preferably 1-5mol based on 1mol hydrazine. Hydrazine is usually used in an aqueous solution of an inorganic acid salt of hydrazine or hydrazine hydrate. The amount of the compound shown by formula I is preferably 0.5-1.5mol based on 1mol hydrazine when the compound shown by formula II is synthesized.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel method for producing alkylhydranone.

(Prior Art) Alkylhydrazines are compounds useful as raw materials for agricultural chemicals, medicines, foaming agents, and the like.

Conventionally, there have been various methods for producing alkylhydranone, especially tert-butylhydrazine, using hydrazine as a raw material.
being developed. U.S. Pat. No. 4,248,800 discloses a method for producing tert-butylhydrazine by reacting chloramine with potassium hydroxide and tert-butylamine. However, tert-butyl 7mine is produced from tert-butyl chloride and ammonia and is expensive. Tokuko Sho 57-212
No. 67 discloses a method for producing an inorganic acid salt of lert-butylhydranone by reacting an inorganic acid salt of hydranone with tert-butyl halide. But jerk
-Butyl halide is produced from tert-butanol and hydrogen halide and is expensive. Japanese Unexamined Patent Publication 1983
-137453 discloses a method for producing tert-butylhydrazine hydrohalide by reacting hydrazine hydrohalide and tert-butanol in the presence of hydrazine dihydrohalide or hydrogen halide. is disclosed. However, tert-butyl alcohol is produced by a water utilization reaction of inbutylene and is expensive.

(Problems to be Solved by the Invention) The purpose of the present invention is to provide an economically advantageous method for producing furkylhydrazines, which uses inexpensive raw materials and can obtain furkylhydrazines in high yields. be.

(Means for Solving the Problems) The present invention provides a method of combining hydrazine with formula (1)% formula% (1) (wherein R', R2 and VB2 may be the same or different) in the presence of an inorganic acid. , each representing a hydrogen atom or a lower furkyl group). and formula (3) (in which R', R2 and R3 have the same meanings as above).

In the above, examples of lower alkyl groups include alkyl groups having 1 to 6 carbon atoms.

Although the details of the reaction mechanism in the method for producing furkylhydrazine of the present invention have not been elucidated, there is no 8! acid (this is HA
When hydranone and olefinic hydrocarbon are reacted in the presence of hydranone and olefinic hydrocarbon to produce an alkylhydranone-based salt, the reaction is presumed to proceed as follows.

However, the present invention is not limited by the speculation of the reaction mechanism described above.

The inorganic acid salts of alkylhydranones formed by the above reaction formulas (2) and (3) can be converted into the corresponding alkylhydrazines by neutralizing with an alkali such as sodium hydroxide.

The hydrazine used in the present invention is usually an aqueous solution of an inorganic acid salt of hydrazine hittride or hydranone.

The concentration of the hydrazine aqueous solution is not particularly limited, but in the case of hydrazine hydride, it is preferably about 60 to 80% by weight.
Examples of olefinic hydrocarbons in the present invention include ethylene, propylene, imbutylene, butene-1, pudene-2, and 2-methyl-butene-2.
, pentene-1, and the like. The amount of olefinic hydrocarbon used differs depending on whether the monoalkylhydracne represented by formula (2) is produced or the dialkylhydrazine represented by formula (3) is produced. When producing monoalkylhydrazine as the main objective, the amount of olefinic hydrocarbon used is usually 2 mol or less, preferably 0.5 to 1.5 mol, per 1 mol of hydrazine. On the other hand, when producing dialkylhydrazine as the main objective, the amount of olefinic hydrocarbon used is usually 2 mol or more, preferably 5 to 15 mol, per 1 mol of hydranone.
It is in the molar range.

The inorganic acid in the present invention is, for example, one or more of hydrohalic acid, sulfuric acid, alkali hydrogen sulfate, phosphoric acid, and the like. As hydrohalic acid, HCI, HBr, H
Examples include I. The amount of inorganic acid used is 1 mol or more, preferably 1 to 5 mol, per 1 mol of hydrazine.

When hydrazine is used in the form of an inorganic acid salt of hydrazine, the number of moles of the inorganic acid forming the salt and the number of moles of the inorganic acid not forming the salt per 1 mole of the inorganic acid salt of hydrazine. It is used so that the total number of moles is in the range of 1 to 5 moles. The form of the inorganic acid is not particularly limited, but it is usually used in the form of an aqueous solution and preferably has a concentration in the range of 20 to 70% by weight.

In the present invention, the order of addition of reaction raw materials is not particularly limited,
They can be added in any order. However, when producing monoalkyl hydracune, it is preferable to react the inorganic acid with the hydrazine or hydranone inorganic acid salt solution while gradually introducing the olefinic hydrocarbon. Further, when producing dialkylhydrazine, it is preferable to gradually introduce hydrazine into a solution of an inorganic acid and an olefinic hydrocarbon while causing the reaction. The reaction temperature of the present invention is usually about 7
The temperature is in the range of 0 to 150°C, preferably about 90 to 110°C. The reaction pressure of the present invention can be carried out under normal pressure, under spontaneous main pressure in a closed system, or under pressure using an inert gas or the like.

The reaction time of the present invention is related to the reaction temperature and can be determined as appropriate. For example, when the reaction temperature is 100°C, about 2 to
It is 4 hours. As the reaction solvent of the present invention, organic solvents that do not participate in the reaction, such as toluene, can also be used, but
It is usually preferred to use water. The reaction of the present invention can be carried out either batchwise or continuously.

In the present invention, after the reaction is completed, the reaction solution is cooled and made alkaline to a dog, thereby converting the produced inorganic acid salts of alkylhydranones into free flukylhydrazines. Free fulkylhydranones may react with oxygen in the air and decompose, so it is preferable to use a nitrogen atmosphere. By extracting this alkaline aqueous solution using an organic solvent such as chloroform, the alkylhydranones are transferred to the organic layer. At this time, unreacted hydrazine remains in the aqueous layer without being extracted, so by back-extracting with water the organic layer containing zero-threaded alkylhydrazines that can separate hydrazine and furkylhydrazines, monoalkylhydrazine moves to the aqueous layer, N, N'-
Since dialkylhydrazine remains in the organic layer, monoalkylhydranone and N,N'-dialkylhydrazine can be separated. High purity monofurkylhydrazine can be isolated by distilling the aqueous layer containing monoalkylhydrazine together with an alkali. In addition, by adding the same number of moles of inorganic acid to the aqueous layer containing monoalkylhydranone and concentrating it, you can obtain highly pure monoalkylhydrazine! ! 8! Acid salts can be isolated. High purity N,N'-dialkylhydrazine can be isolated by distilling the organic layer containing N,N'-dialkylhydrazine. In addition, by back-extracting the organic layer containing N,N'-dialkylhydrazine with an inorganic acid aqueous solution of the same number of moles, and concentrating the aqueous layer, highly pure N,N''-dialkylhydrazine inorganic acid salts can be obtained. Can be isolated.

In addition, in the present invention, after the completion of the reaction, if there is little unreacted hydrazine, the reaction solution is cooled and the generated crystals are
High purity inorganic acid salts of furkylhydracunes can be isolated by excessive separation and recrystallization if necessary. Alternatively, highly pure fulkylhydrazines can be isolated by adding caustic soda to the reaction solution while cooling and then distilling the solution.

(Example) Next, the present invention will be explained by giving examples. The results of the reaction are expressed as conversion rate, selectivity, and yield, which are defined as follows.

(2) Conversion rate refers to the mol% of hydrazine consumed in the reaction relative to the hydrazine used in the reaction.

(2) Selectivity (A) indicates the mol% of the monoalkylhydrazine produced relative to the hydranone consumed in the reaction.

(2) Selectivity (B) indicates the mol% of the dialkylhydrazine produced relative to the hydrazine consumed in the reaction.

Example 1 24.3 g of 30% HCl (0,
To this was added 6.25 g (0.10 mol) of 80% by weight hydranone hydra). Next, the contents were cooled to -10°C, and the contents were cooled to -10°C.
After introducing 0.10 mol), the inside of the system is made into a nitrogen gas atmosphere,
After sealing, the temperature was gradually raised to 95°C, and the reaction was carried out at the same temperature for 3 hours.

Analysis of the reaction solution revealed that tert-butylhydranone hydrochloride and N,N'-di-tcrt-butylhydranone hydrochloride were produced, with a conversion rate of 93% and a selectivity (A) of 97.
%, selectivity (B) 2% of the reaction solution was made alkaline with caustic soda and extracted with nochloromethane to remove unreacted hydrazine into the aqueous layer and tert-butylhydrazine and N,N'-not-tert-butyl Hydrazine was separated into n-layers.

The active layer was back-extracted with water, and tert-butylhydrazine was separated into water/11N,N'-di-tert-butylhydranone into an organic layer. Hydrochloric acid of the same number of moles as tert-butylhydrazine was added to the aqueous layer, concentrated under reduced pressure, and heated to 110°C.
White crystals were isolated by drying. As a result of NMR spectrum and mass spectrum measurements of this crystal, the spectrum completely matched that of the standard tert-butylhydrazine hydrochloride, confirming its identity.

N/20-K I O, reductive titration and N/10
A g N Ox droplet # early Otsume JLI+), 1l-
) - Gofutoru V Usinoso linic acid salt content was 99%.

The same molar number of hydrochloric acid aqueous solution was added to the organic layer containing N,N'-jerk-butylhydrazine for back extraction, the aqueous layer was concentrated under reduced pressure, and white crystals were isolated by drying at 110°C. The crystals were N,N'-di-tcrt-butylhydranone hydrochloride with a content of 99%.

Examples 2 to 7 Reactions were carried out in the same manner as in Example 1, except that the type and amount of inorganic acid used, the amount of isobutylene used, and the reaction temperature and reaction time were changed. The results are shown in Table 1.

Table 1 Examples 8 to 11 Inorganic acid was charged into the same equipment as in Example 1, 8.33 g (0.10 mol) of 60% by weight hydrazine hydride was added, the system was made into a nitrogen gas atmosphere, and the system was sealed. After that, gradually 9
The temperature was raised to 0'C. Add 3 olefinic hydrocarbons to this
The mixture was gradually introduced over time, and the reaction was further carried out at the same temperature for 3 hours. The results are shown in Table 2.

Table 2 Book 1 terL-butylhydrazine and monolithic book 2
3 ethyl rehydracin and hydrazine 4 hydrazine isopropylhydranone 4 isobutyfluhydranone and ethylehydranone Example 12 In the same apparatus as in Example 1, 10.5 g of hydrazine dihydrochloride was added.
(0.10 mol) and 20 g of water were charged, cooled to -10°C, and 5.6 g (0.10 mol) of isobutylene was introduced.The prefecture was made into a nitrogen atmosphere, and after being sealed, the temperature was gradually increased to 100°C.
As a result of analysis of the reaction solution obtained by raising the temperature to (
B) It was 2%.

Example 13 In the same apparatus as in Example 1, 20.9 g of 35% HCl (0
, 20 mol), and 6.25 g (0.10 mol) of 80% hydrazine hydra) was added thereto. This was cooled to -10'C and inbutylene 14. Og(0,25
mol), create a nitrogen gas atmosphere in the system, and after sealing,
The temperature was gradually raised to 100°C, and the reaction was carried out at the same temperature for 5 hours. Analysis of the reaction solution showed a conversion rate of 98% and a selectivity (A).
The selectivity (B) was 47% and the selectivity (B) was 51%.

Example 14 In the same apparatus as in Example 1, 31.3 g of 35% HCl (0
, 30 mol) was cooled to -10°C, 56.0 g (1,00 mol) of isobutylene was charged, the system was made into a nitrogen gas atmosphere, and after being sealed, the temperature was gradually raised to 90°C.

Add to this 6.25g (80% hydranone hydra) (0,
10 mol) was gradually introduced over 3 hours, and the reaction was further carried out at the same temperature for 5 hours. As a result of analysis of the reaction solution, the conversion rate was 1.
The selectivity (A) was 17%, and the selectivity (B) was 82%.

(that's all)

Claims (2)

[Claims] (1) In the presence of an inorganic acid, hydrazine and the formula (1) ▲ have mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R^1, R^2 and R^3 may be the same or different. Formula (2) is characterized by reacting olefinic hydrocarbons represented by hydrogen atoms or lower alkyl groups, respectively) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, R^ 1, R^2 and R^3 have the same meanings as above) and formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(3) (In the formula, R^1, R^2 and R^3 are A method for producing an alkylhydrazine represented by (having the same meaning as above). (2) The method according to claim 1, wherein the inorganic acid is at least one selected from the group of hydrohalic acid, sulfuric acid, alkali hydrogen sulfate, and phosphoric acid.