DE1695585C - Process for the preparation of 3,3 dialkyldiazacyclopropanes - Google Patents

Description

The invention relates to an improved process for the preparation of 3,3-dialkyldiazacyclopropanes which as a starting material for the production of hydrazine hydrate, hydrazine salts and other hydrazine derivatives are usable.

So far, 3,3-dialkyldiazacyclopropanes are in general by introducing chlorine gas into an aqueous or organic solution of ammonia and ketone has been manufactured. For example, when methyl ethyl ketone is used as a ketone, the reaction can be carried out print out by the following formula:

4NH _a + Cl ₂ + CH ₃ COC ₂ H ₅
CH ₃ NH

- »C; j + 2NH ₄ CH-H ₂ O

C ₂ H ₅ NH

In such a conventional method, however, there is a risk of explosion by the direct Contact of the ammonia with the chlorine gas, and furthermore the ketone used can by oxidation with Chlorine gas can be decomposed, reducing both the yield of the desired product and the usability of ketone are reduced.

Further, a method for producing 3,3-Dialkyldiazacyclopropanderivaten by reacting liquid ammonia, ketone and chlorine using low temperatures from -50 ⁰ C is known. Since the reaction of ammonia, ketone and chlorine to produce dialkyldiazacyclopropane is known to be a strongly exothermic reaction, considerable difficulties arise in keeping the temperature of the reaction system at -50 ° C., so that such a process cannot be considered as a technically useful process .
Also could from the fact that the manufacture

ίο of dialkyldiazacyclopropane from ketone, ammonia and chlorine or chloramine and on the other hand the formation of chloramine from ammonia and chlorine or Hypochlorite are known and are made up of the reaction of chloramine with ammonia and strong alkali Forms hydrazine, not to be inferred from the teaching according to the invention, within a process for Production of certain 3,3-dialkyldiazacycloproparii: To use hypochlorite in place of chlorine or chloramine and an ammonium salt of a strong acid Use to stop the formation of hydrazine.

The invention is based on the task of creating a safe one while avoiding the previous disadvantages technically favorable process for the production of

To create 3,3-dialkyldiazacyclopropanes, which is free from the risk of explosion and which are used in ^ em Ketones effective without decomposition and / or condensation with easily accessible hypochlorite as a source of chlorine with selective formation of the desired pro-

products are implemented in high yields and high concentrations.

The invention relates to a method for production of 3,3-dialkyldiazacyclopropanes of the general formula

35 R ₁ .

R,

, NH

NH

in which R ₁ and R _{2 are} alkyl groups with 1 to 4 carbon atoms and the total number of carbon atoms of the radicals R ₁ and R _{2 is} in the range from 2 to 5, by reaction of ammonia, chlorine and ketone, the ketone in an amount of more than 0.9 mol per mol of chlorine is used, which is characterized in that an inorganic hypochlorite is used as the chlorine source and the reaction is carried out with the addition of an ammonium salt of an inorganic acid at a pH of the reaction system of 10 to 13.

If calcium hypochlorite is used, the method associated with the process according to the invention is used Response essentially expressed by the following equation:

R ₁ .

R ₁

4 NH ₃ + 2 CO + Ca (OCl) ₂ - 2; C NH

NH

r- CaCl ₂ + _{4H 2} O

wherein R ₁ and R _{1 are} alkyl groups having 1 to 4 carbon atoms and the total number of carbon atoms of the radicals R ₁ and R _{2 is} in the range from 2 to 5.

According to the invention, various salts of hypochlorous acid can be used as the hypochlorite be, for example calcium hypochlorite, sodium hypochlorite, Potassium hypochlorite. The preferred examples are chlorinated lime and sodium hypochlorite. The hypochlorite can be used in the form of a powder, an aqueous solution and an aqueous suspension will. Since the hypochlorite is used as a source of chlorine, the invention can reduce the risk of Explosion and decomposition of the starting ketone

switched off by chlorine gas and also the production of 3,3-dialkyldiazacyclopropane economical be made.

Examples of the ketones used according to the invention are acetone, methyl ethyl ketone, diethyl ketone, Methyl isopropyl ketone, methyl isobutyl ketone. The ketone is used in an amount greater than 0.9 mole, preferably 1.2 to 4.0 moles per mole of available chlorine in the starting hypochlorite.

The ammonia is used in the form of ammonia water and ammonia gas and in general in an amount of 3 to 20 moles, preferably 4 to 10 moles, per mole of available chlorine in the Starting hypochlorite applied.

other heavy metals in the hypochlorite used, which hindered the reaction becomes, in a manner known per se, a sticky substance, such as gelatin, glue, starch or carboxymethyl cellulose, added to the reaction system.

The following examples serve to illustrate the invention.

B e i s ρ i e 1 I

Ζ ··, a mixture of 486 g of 28 weight percent ammonia water, 116 g of acetone and 53 g of ammonium chloride were under violent in 30 minutes

When the method according to the invention is carried out, 444 g of an aqueous suspension of! 18.4 g

rens it is important to carry out the reaction with the addition of an ammonium salt "in an inorganic acid, while the pH of the reaction system is maintained between 10 and 13, whereby the desired 3,3-DialkyIdiazacyclopropanes selectively in high yield. If the reaction is carried out without adding the salt, it increases the pH of the reaction system due to the formation of a strongly alkaline intermediate product, such as calcium hydroxide, to more than 13, so that predominantly hydrazones or azines are produced which are partially decomposed with the hypochlorite used during the reaction and thus the yield of the desired product be bleach powder (Chlorinated lime) was added, which contained 60 percent by weight of available chlorine suspended in water. At the beginning of the reaction, the pH of the reaction mixture was 11.3. The temperature of the The system was kept at 30 ° C. by water cooling during the addition. After that, the system Heated to about 4OC for 1 hour, leaving 67 g of 3,3-DimethyIdiazacyclopropane in the form of a solution were obtained. After the reaction, the pH of the reaction mixture was 10.7. The yield, calculated as hydrazine hydrate, was 93 mole percent based on the available chlorine that was used in the Bleach powder used as a starting material was included, and the concentration of the product in

considerably decrease. If jeJorh the reaction after 30 of the solution was 4.65 weight percent, the inventive method calculates u ter addition of the hydrazine hydrate. The boiling point of the 3,3-di-

methyldiazacyclopropane was 106 ^ / 760 mm Hg. For comparison, the reaction was in the same Carried out as in Example 1, with the difference that no ammonium chloride was added.

Ammonium salt is carried out, the strongly alkaline intermediate is immediately with the Ammonium salts are neutralized to prevent the undesired rise in pH of the reaction system, and the pH becomes in the range from 10 to 13, which makes it possible to selectively use the 3,3-dialkyldiazacyclopropanes in high Produce yield The ammonium salts preferably used according to the invention are ammonium chloride, Ammonium nitrate, ammonium sulfate and ammonium phosphate, with ammonium chloride being most preferred. The preferred amount of the The ammonium salt varies over a wide range. However, it is used in an amount sufficient to de the pH of the reaction system during the entire period. Response to 10 to 13, preferably to 10.5 to 12.

The process of the invention can be carried out in batches. There was no formation of j.S-dimethyldiazacyclopropane observed, but one obtained acetonazine.

Example 2

To a mixture of 2190 g of 28 weight percent ammonia water, 576 g of methyl ethyl ketone and 214 g of ammonium chloride, 10 ml of 5 weight percent gelatin and 444 g of bleach powder containing 64 weight percent of available chlorine were added in 30 minutes with vigorous stirring. At the beginning of the reaction, the pH of the reaction mixture was 11.4. The reaction temperature of the system slowly increased, but increased during the addition

or run continuously. According to a 50 kept 20 to 25 ° C. Thereafter, the mixture was preferred procedure for carrying out the inventions for 2 hours at about 4O ⁰ C heated, whereby 330 g

3-methyl-3-ethyldiazacyclopropane were obtained. After the reaction, the pH of the reaction mixture was 10.8. The yield calculated as Hydrazine hydrate, was 96 mole percent based on the available available contained in the bleach powder used Chlorine, and the concentration of the product in the resulting solution was 5.78 percent by weight, calculated as hydrazine hydrate. The boiling

diazacyclopropane is obtained in the form of a solution. 60 point of the obtained S-methyl-S-äthyldiazacyclopro-General, the product in the resulting pan is at 32 ° C / 17 mm Hg.
Solution in a concentration of 4 to 10 percent by weight, calculated as hydrazine hydrate, and from 10 to

According to the method, hypochlorite is added with stirring at a temperature below 40 ° C, preferably 10 to 35 ° C, in the form of powder, solution or suspension to a mixed solution of ammonia water, ketone and ammonium salt of an inorganic acid preferably continued until 8O ⁰ C 40 to 8O ⁰ C, about 0.5 to 4 hours. The desired 3,3-dialkyl

30 weight percent, calculated as hydrazine hydrate, based on the weight of that contained in the solution Water.

Before the reaction, if necessary, i. H. fill's impurities, such as iron or

Example 3

To a mixture of 60 g ammonia water of 28 weight percent, 66 g ammonium sulfate, 144 g Methyl ethyl ketone and 100 ml of water were in

30 minutes with vigorous stirring at 25 to 30 ° C 85 g of ammonia gas and 592 g of sodium hypochlorite solution added containing 12 weight percent available chlorine. At the beginning of the reaction was the pH of the reaction mixture at 11.5. The system was then heated to 45 ° C for 2 hours, whereby 75.7 g of 3-methyl-3-ethyldiazacyclopropane were obtained in the form of a solution. After the reaction The pH of the reaction mixture was 10.9. The yield calculated as hydrazine hydrate was 88 mole percent based on the chlorine available in the sodium hypochlorite solution and the concentration of the product in the resulting solution was 4.35 percent by weight calculated as hydrazine hydrate. The boiling point of the 3-methyl-3-ethyldiazacyclopropane obtained is 32 ° C./17 mm Hg.

Example 4

To a mixture of 46 g of 28 weight percent ammonia water, 26 g of methyl isopropyl ketone and 12 g of ammonium nitrate became 17 g of bleach powder in 20 minutes with vigorous stirring at 20 to 25 ° C was added containing 10.65 grams of available chlorine. At the beginning of the reaction, the pH of the reaction mixture was 11.2. After that, the system was 1 hour heated to 40 ° C. for a long time, and 3-methyl-3-isopropyldiazacyclopropane solution was obtained. After the reaction, the pH of the reaction mixture was 10.5. the Yield, calculated as hydrazine hydrate, was 86 mol percent based on that in the one used Available chlorine contained in bleach powder. The boiling point of the obtained S-methyl-S-isopropyldiazacyclopropane is at 67 ° C / 50 mm Hg.

Claims (1)

Claim: Process for the preparation of 3,3-dialkydiazacyclopropanes the general formula: R ,. NH R., NH ir. R ₁ and R _{2 are} alkyl groups with 1 to 4 carbon atoms and the total number of carbon atoms of the radicals R ₁ and R _{2 is} in the range from 2 to 5, by reaction of ammonia, chlorine and ketone, the ketone in an amount of more than 0.9 mol per mole of chlorine is used, as it is indicated that an inorganic hypochlorite is used as the source of chlorine and the reaction is carried out with the addition of an ammonium salt of an inorganic acid at a pH of the reaction system of 10 to 13.