JPH01226862A - Production of n,n-dialkylhydrazines - Google Patents

Abstract

PURPOSE:To industrially obtain the title compound useful as an antioxidant for photographic developer in good selectively and yield, by reacting hydrazine or monoalkylhydrazines with an alkylating agent at a specific pH. CONSTITUTION:Hydrazine or monoalkylhydrazines are reacted with an alkylating agent (e.g., acrylic acid, acrylamide or propanesultone) to provide the N,N-dialkylhydrazines expressed by the formula (R1 and R2 are alkyl). The above-mentioned reaction is carried out preferably at 7.5-9.5pH and normally in the presence of a base such as NaOH or KOH. The control of alkylation reaction and suppression of decomposition of the alkylating agent are made possible by controlling pH in reaction according to the above- mentioned method.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to N, which is useful as an antioxidant for photographic developers, etc.
The present invention relates to a method for producing N-dialkylhydrazines.

(Prior art) A method for synthesizing N,N-dialkylhydrazines by alkylating hydrazine or monoalkylhydrazines is described in the Journal of the American Chemical Society (Jour, Eighter, C
hew, Soc,, ) 36. 1747 (
1914), Journal of Organic Chemistry (Jour, Org, Chew,), 25
．． 44 (1960), Oil Chemistry 24, : Jl (19
There is a method reported in 75) etc.

(Problem to be solved by the invention) However, all of these methods have poor selectivity as a method for dialkylating or monoalkylating the raw material hydrazine or monoalkyl hydrazine with an alkylating agent, and they do not produce by-products or inorganic salts. is produced in large quantities. Therefore, when used as an antioxidant in photographic developers, particularly high purity is required, but in order to isolate and purify the target N,N-dialkylhydrazines, raw materials such as hydrazines and inorganic salts, and It requires quite complicated operations such as removal of by-products, and when potassium carbonate or sodium carbonate is used as a base, foaming occurs due to the generation of carbon dioxide, making it unsuitable for industrial large-scale synthesis.

Therefore, the purpose of the present invention is to provide a production method that is excellent in selective alkylation, easy to isolate and purify, and suitable for large-scale synthesis in the synthesis of N,N-dialkylhydrazines by alkylation reaction of hydrazine or monoalkylhydrazines. The purpose is to provide a method.

(Means for Solving the Problems) As a result of extensive research, the present inventors have found that the alkylation reaction of hydrazine or monoalkylhydrazines can be carried out at pH 10,
5 or less, N,N-
We have found that it is possible to obtain dialkylhydrazines.

That is, in the present invention, when reacting hydrazine or monoalkylhydrazines with an alkylating agent, the reaction is carried out at a pH of 1.
The present invention provides a method for producing N,N-dialkylhydrazines represented by formula (I) (wherein R and R2 represent an alkyl group), which is carried out at a concentration of 0.5 or less.

The hydrazine or monoalkyl hydrazine used in the present invention may be commercially available or available, or if necessary, published in the Journal of Organic Chemistry (Jo
rn, Org, Chew, ) 25.44 (19
60), Journal of the American Chemical Society (Jour, Amer, Chew
.

Soc, ) 72.2762 (1950), Organic Inthesis (Org, 5ynth,) II
, 395 (1943), Organic Science, 208 (1943), Journal of the American Chemical Society (Jour
, Amer, Chew, Soc, ) 43.2
597 (1921), Journal of the American Chemical Society (Jour, Ame
r, Chew.

Soc, ) 44.2556 (1922), etc., and can be synthesized and used. These hydrazines may form inorganic salts such as hydrochloric acid, sulfuric acid, etc. or organic salts such as p-toluenesulfonic acid, methanesulfonic acid, etc. 0 The reaction pH during synthesis is 10.5
In order to control the following, it is preferable to use salts.

In the method of the present invention, the hydrazine or monoalkylhydrazine is reacted with an alkylating agent. This reaction can be expressed, for example, by the following formula. In addition, when R3 is a hydrogen atom, the reaction of the following formula is repeated using the reaction product (IV) as a raw material.

In the above formula, R3 represents a hydrogen atom or an alkyl group, and R4 represents an alkyl group which may have an a substituent. X is a halogen atom (chlorine, bromine, etc.), 0SO2R5
A group (R5 represents, for example, phenyl, tolyl, methyl, etc.).

Here, H2NNHR3 may be free or may form a salt with each of the above-mentioned dilute acids.

In addition, as alkylating agents, the above-mentioned α- and β-unsaturated compounds (e.g., acrylic acid, acrylic esters,
Acrylamide, acrylonitrile, etc.) or sultones (eg, propane sultone, butane sultone, etc.) can also be used. The amount used is usually 0.7 to 1.5 equivalents, preferably 0.8 to 1.1 equivalents of the alkylating agent relative to the hydrazine in the case of monoalkylation (in the case of the above formula (formerly, when R3 is an alkyl group)). equivalent, and in case of dialkylation (
When R3 is a hydrogen atom in the above formula (II)) is usually 1.5
-2.5 equivalents, preferably 1.7-2.1 equivalents.

In the present invention, the alkylation reaction is carried out at a pH of 10.5 or less, preferably 7.5 or more and 9.5 or less.The reaction solvent is usually water, alcohol, or other solvents depending on the solubility of the raw materials. Solvents such as dimethylformamide: dioxane, acetonitrile, dimethyl sulfoxide may also be used.

The reaction of the present invention is usually carried out in the presence of a base, and preferred examples of such bases include sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide. You can also use things.

The reaction temperature is usually in the range of -20°C to 100″C,
Preferably, the temperature is in the range of room temperature to 60°C.

The N,N-dialkylhydrazines obtained by the method of the present invention are represented by formula (I).

Next, R1 and R2 in formula (1) will be described in detail.

The alkyl group represented by R1 and R2 is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (
Examples of A-isomers include methyl group, ethyl group, propyl group,
isopropyl group, n-butyl group, n-hexyl group, cyclohexyl group, etc.), and may also have an l substituent. Examples of the l substituent include halogen atoms (e.g. chlorine,
bromine), hydroxyl group, carboxyl group, sulfo group,
Amino groups (e.g. unsubstituted amino, diethylamino, anilino), alkoxy groups (e.g. methoxy, ethoxy),
Amide groups (e.g. acetylamino, benzoylamino)
, sulfonamide groups (e.g. methanesulfonamide, benzenesulfonamide), aryl groups (e.g. phenyl, tolyl, 4-carboxyphenyl), heterocyclic groups (e.g. 4-pyridyl, l-pyrazolyl, l-piperidino)
, an aryloxy group (eg, phenoxy), an alkylthio group (eg, methylthio, ethylthio), an arylthio group (eg, buenylthio), a cyano group, a nitro group, and the like.

Specific examples of N,N-dialkylhydrazines represented by formula (I) that can be synthesized by the method of the present invention are shown below, but the invention is not limited thereto.

(I-1) CH3 (I-2) CH2C00H (I-3) CH2COOH (I-4) 2H5 3H7 (I-6) C2H4C00N a (I-7) C2H4S03Na CH2C00H (I-9) CH2CH2S03Na (I-10) C3H6SO3NA (I -11) C3H6S03NA (I -12) CH2COOH (I -13) H3 (I -14) CH2COOH CH2CH20H (I -17) C2H40CH3 (I -18) CH2COOH (I -19) H3 (I -20) H3 (I -20) ) HCOOH 4H9 (I-21) CHOCH3 (I-22) CHCOO) (C2Hs (Effect of the invention) Conventional methods for synthesizing N,N-dialkylhydrazines all involve adjusting the pH during the reaction to a high pH (approximately pH11
However, in the synthesis method of the present invention, by controlling the pH during the reaction to the conventional pH of 10.5 or lower, This makes it possible to control the alkylation reaction and suppress the decomposition of the alkylating agent, making it possible to dramatically improve the yield of the target compound.

Therefore, according to the present invention, N,N-dialkylhydrazines can be produced with good yield and selectivity by alkylating hydrazines.

Further, according to the method of the present invention, it is easy to isolate and purify the target N,N-dialkylhydrazines, and it is suitable as a method to be carried out technically.

(Examples) Next, the present invention will be explained in more detail based on Examples.

Example 1 Synthesis of Compound I-3 5.06 kg (38.9 mol) of hydrazine sulfate was added to 1 mol of water.
09. Sodium chloroacetate was dissolved in 9.34 g of sodium chloroacetate under stirring.
kg (77.8 mol) were added. An aqueous solution containing 6.1 kg (152.5 mol) of caustic soda dissolved in 8 pieces of wood was gradually added dropwise to this aqueous solution. During this time, the pH of the reaction solution was approximately 9.
．． The reaction temperature was maintained in the range of 30 to 60°C. After the addition is complete, cool to 25°C and add 6.5 ml (7 ml) of concentrated hydrochloric acid.
5.8 mol) was added (pH at this time was 2.2 L), and the precipitated white solid was filtered off under reduced pressure. By washing this solid with water and then hot water, 3.85 kg of compound I-3 was obtained.
(yield: 66.8%, purity: 99%). Melting point 166-1
67°C (decomposition), elemental analysis (C4H8N204) CHN Actual value 32.44 5°44 18.92 Calculated value 32.64 5.18 18.74 The above except that the pH of the reaction solution was set to 10.8 The reaction was carried out in exactly the same manner as above, and washing with water and hot water was carried out in the same manner.
1.27 kg of compound ¥5I-3 was obtained, with a purity of 95%.

Example 2 Synthesis of Compound I-7 13 g (0.1 mol) of hydrazine sulfate and 43.5 g (0.2 mol) of sodium bromoethylsulfonate were added to 8 g (0.2 mol) of water.
16 g of caustic soda dissolved in 0 ml and stirred at 25°C.
An aqueous solution of (0.4 mol) dissolved in 20 ml of water was gradually added dropwise. During this time, the pH of the reaction solution was maintained at about 9.5, and the reaction temperature was maintained at 35-60°C. After the dropwise addition was completed, the reaction was further reacted for 1 hour, and then the reaction solution was cooled to 25°C, 60 ml of concentrated hydrochloric acid was added, and the precipitated solid was filtered off. The filtrate was concentrated under reduced pressure, and the residue was passed through a 5 ephadex column with water. This aqueous solution was concentrated under reduced pressure to obtain 17.8 g of compound I-7 (yield 61%, purity 98%).
Obtained. Melting point 208-212℃ elemental analysis (C4HION
2 Na 2°632) CHN Actual value 16.44 3.45 9.59 Calculated value 16.21 3.23 9.40 Example 3 Synthesis of compound I-8 Methylhydrazine sulfate 14.4 g (0.1 mol ) was dissolved in 8 od of water and added with stirring 23 oz of sodium chloroacetate.
3 g (0.2 mol) were added. An aqueous solution prepared by dissolving 16 g (0.4 mol) of caustic soda in 20 ml of water was gradually added dropwise to this aqueous solution. During this time, the pH of the reaction solution was maintained at about 9.0, and the reaction temperature was maintained in the range of 30 to 60°C. After the addition was completed, the mixture was cooled to 25° C., 20 ml of concentrated hydrochloric acid was added, and the precipitated white solid was filtered off under reduced pressure. This filtrate was heated under reduced pressure to
After C, ethanol was added to the residue to obtain a white solid. Recrystallization from ethanol yielded 7, Ig of compound I-8 (yield: 6
8%) was obtained. Melting point 153-154°C Elemental analysis (C3H8N20°) CHN Actual value 34.60 7.75 26.91 Calculated value 34.35 7.66 26.89 Example 4 Synthesis of compound l-16 Methylhydrazine sulfate 14.4g ( 0.1 mol) was dissolved in 80 ml of water, and while stirring, 17.1 g (0.1 mol) of benzyl bromide dissolved in 40 methanol was added. Add this solution to a pH of about 9 and a reaction temperature of 30 to 30.
While maintaining the temperature at 40°C, 12 g (0.3 mol) of caustic soda dissolved in 15 d of water was slowly added dropwise. After the dropwise addition was completed, the reaction was continued for an additional hour, and then the reaction solution was distilled off under reduced pressure using an evaporator. The remaining residue was transferred to a silica gel column (solvent;
When purified using CHCl3/MeOH=lO/l), the desired compound l-16 was obtained as an oil.
7 g (yield 51%) was obtained.

Elemental analysis (C8H1□N2) CHN Actual value 70.54 8.88 20.57 Calculated value 70.73 8.69 20.72 Patent applicant Fuji Photo Film Co., Ltd. Agent Patent attorney Ii 1) Toshizo.

Claims (1)

[Claims] There is a formula (I) that is characterized in that when reacting hydrazine or monoalkylhydrazines with an alkylating agent, the reaction is carried out at a pH of 10.5 or lower. There are mathematical formulas, chemical formulas, tables, etc. A method for producing N,N-dialkylhydrazines represented by the formula (wherein R_1 and R_2 represent an alkyl group).