JPS5824552A - Preparation of quaternary hydrazinium chloride - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a synthetic raw material of a surface active agent, adhesive and amineimide compound, and pesticide, etc., easily, in high yield and purity, by reacting a tertiary amine with the reaction mixture of ammonia water and sodium hypochlorite. CONSTITUTION:The reaction mixture of ammonia water and sodium hypochlorite is obtained by adding sodium hypochlorite to ammonia water while cooling the system to 0 deg.C or below. The reaction mixture is made to react with a tertiary amine (e.g. trimethylamine, N,N,N'N'-tetra-methylethylenediamine, N-methylmorpholine, triethylenediamine, etc.) at -10-+20 deg.C to obtain the objective compound. The reaction is carried out by adding the reaction mixture dropwise to the tertiary amine (or its aqueous solution). The amount of the tertiary amine is nearly equimolar to the chloroamine contained in the reaction mixture, or 0,9-1.1 times mole of the chloroamine.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing quaternary and doph-Vnium chlorides.

Quaternary and dolarenium clophytes, especially thoria and kylhydrazinium clophytes, are surfactants.

It is an important compound as a raw material for the synthesis of A-min-imi Y compounds used in adhesives, efstomers, polymerization agents, etc., and as an agricultural chemical. In addition to these uses, there are other uses similar to those of quaternary ammonium, such as sterilizing-1 disinfectants, antistatic agents, and softeners.

However, an industrial manufacturing method for tri-kylhydrinium chloride has not yet been established, and its use remains extremely limited.

Conventionally, several methods are known for producing quaternary human fucinium, especially trialkyl human fucinium crophyte. For example, 1) a method of quaternizing hydrazine or asymmetric dialkyl hydrofuzine with an alkyl chlorophyte, 2) a method of metathesizing the corresponding triple-kyl hydrofusinium bromide or iodide with silver chloride, 3) a method of metathesizing the corresponding triple-kylhydrofusinium bromide with silver chloride, 3) a method of metathesizing the corresponding triple-kylhydrofusinium bromide with silver chloride 4 methods of neutralizing the hydroxide obtained by the reaction of hydrazinium hafide and silver oxide with hydrochloric acid; 4) Neutralizing the chloramine gas obtained by the gas phase reaction of ammonia and chlorine with excess liquid tertiary amine or A method of reacting while blowing into a solution of a tertiary amine dissolved in an inert solvent, or 6) an alcohol ~ solution Ki! of a tertiary amine and ammonia. A known method is to react while blowing chlorine gas diluted with raw gas.

However, in the method of 1), when alkyl iodide, bromide, )V rate, etc. are used as reagents, tria-ki/&/hydrazinium can be obtained almost quantitatively; When clophyte is used, a large amount of trialkylhydrotuzine is produced as a by-product. Further, both the double decomposition method (2) and the neutralization method (3) cannot be said to be industrially advantageous methods in that they use silver compounds. In addition, the method of 4) in which the chloramine paste obtained by the reaction of ammonia gas and chlorine gas is reacted with a tertiary amine has a high yield of chloroamine paste, but requires the use of an excess of amine. ,
It is difficult to remove ammonium chloride produced by the reaction between ammonia gas and chlorine gas, and as a result, the flow rate of chlorine gas cannot be increased, making it unsuitable for mass production. Also,
As an improved method for this reaction, a tertiary amine and ammonia are dissolved in isopropyl γμ co-μ! A method has been proposed in which circular ring gas is injected diluted with nitrogen gas. However, with this method, it is necessary to use approximately twice the amount of tertiary amine as compared to chlorine gas, and the flow rate of chlorine gas cannot be increased, so it cannot be said to be an excellent method from an industrial perspective. .

The present inventors investigated an industrially advantageous method for producing quaternary human fusinium chloride, and used a reaction mixture of aqueous ammonia and an aqueous solution of sodium hypochlorite to neutralize, extract, Surprisingly, it was found that when reacted with a tertiary amine in an aqueous medium without taking any purification measures such as isolation, quaternary and dophnium chlorides were produced in high yield. Surprisingly, the conventional method using chloroamine gas
Whereas a large excess of tertiary amine was required relative to chloroamine, in the reaction using the above reaction mixture in an aqueous solvent, the chloroamine present in the reaction mixture was It has been discovered that the desired product can be obtained in high yield simply by using an amine. Conventionally, methods have been known in which ammonia water and sodium hypochlorite aqueous solution are reacted to form an aqueous solution containing chloroamines or a concentrated solution thereof, and chloroamines are extracted from the solution with a solvent such as ether. The chloroamine thus isolated is an extremely unstable compound and cannot be said to be suitable as an industrial raw material. In addition, the above chloroamine-containing aqueous solution can be used directly and with doralin derivatives, such as non-targeted sia μ
Although it has been used in conjunction with the Kir C Dorazine O combination, there is no example of it being used in the quaternary H2T MTA YO combination.

The present inventors conducted further intensive studies based on the knowledge such as ζO, and as a result, completed the present invention.

That is, the present invention combines aqueous ammonia and submerged chloric acid (ψ)
Quaternary hydrogenium by reacting the OK reaction mixture with tertiary amine? Retwee you: It's a decision.

The ammonium chloride water used in the present invention and the following N loading acid>l? ^
0Ilt, a mixture can be obtained by adding sodium chloride to aqueous ammonia while cooling it to a temperature above -0°C; Ryu^ is usually dripped in its aqueous solution. Such an aqueous solution includes a thorium chlorate aqueous solution (usually containing about 10% excess hydroxide) obtained by passing chlorine into an aqueous hydroxide solution.
And - may be. Excess amount of ammonia water, for example, 1 of the theoretical amount! ~ 6 times 7μ is lost. The mixture obtained in this manner is an aqueous solution containing chloroamine and an equivalent amount of sodium hydroxide.
The aqueous solution is then subjected to reaction with a tertiary amine.

Tertiary amines that can be quaternized in the present invention include, for example, chain or cyclic aliphatic tertiary amines.

Idiomatic examples include trimethylamine, triethylamine, tripropylamine, y-methyamine, and sF-methypropamine.

V methyl to 2v Lua abuse, dimethy〃octy~amine, y
Objects such as methiμVriphekivI&/amine, Vethy〃methyμamine are hybrid OriJ fat * amines =, 9 For example, N, N, N', N'-teshitsumechiμena,
Ren V amine, N, N, N', N'-tetramethylene and trimethylene rare amine, N, N, N', N'-
Aliphatic V such as tetramethylene and hequinamethylenediamine
Amines, N-methylmorpholine, N-methy-piperi V
and cyclic cyamines such as triethylenediamine and N,N'-dimethylbibewodine.

The above-mentioned tertiary amine can be subjected to the reaction as it is or after purification with a salt of an inorganic acid such as camphoric acid or sulfuric acid.

Further, these tertiary amines or their derivatives are used either directly or usually as an aqueous solution. If the amine is insoluble or sparingly soluble in water, use the amine or replace some of the water with, for example, meth! No~,
Alcohols such as ethanol may also be added.

The reaction between the reaction mixture of aqueous ammonia and sodium hypochlorite and the tertiary amine is usually -10~! The reaction is carried out at 0°C, preferably while maintaining the reaction temperature at about -5 to 10°C. In this case, the tertiary amine is present in an approximately equimolar amount, or approximately 0%, relative to the chloroamine contained in the reaction mixture of aqueous ammonia and sodium hypochlorite.
．． It is best to use 9 to 1.1 times the amount. The reaction can be carried out by dropping a reaction mixture of aqueous ammonia and sodium hypochlorite onto a tertiary amine (usually in water), or vice versa. A method of dropping it into the reaction mixture with sodium hypochlorite may also be used. The reaction usually completes in 10 minutes to 2.3 hours, and after the reaction is completed, it is neutralized using a commonly used mineral acid such as caustic soda ft hydrochloric acid present in the system. After the water has been evaporated, the target product, quaternary human fusinium clophyte, is obtained using an organic solvent such as ethanol, n-globanol, in-propanol, n-butano-fi/chloroform, etc. Extract. In addition to the method of neutralizing after the reaction, an acid is added in advance to a mineral acid salt of a tertiary amine or an aqueous amine solution, and this is neutralized with a reaction mixture of aqueous ammonia and sodium hypochlorite. It can also be reacted.

According to the method of the present invention, the nitrogen atom is quaternized and quaternary human fusinium clophyte can be obtained in extremely high yield and purity. In particular, the yield of amine paste is extremely high.Moreover, this reaction is easy to handle as it is a reaction in an aqueous solvent, there is no need to use excess raw materials, and there are few by-products, making it difficult to use complicated manufacturing equipment. This method is industrially extremely advantageous as it does not require

If necessary, the object of the present invention can be prepared by a method commonly used for purification of quaternary salts, such as ethanol.

It can be purified by a recrystallization method using a mixed solvent of an alcohol such as Dega Panol and ED.

In addition, in the method of the present invention, when cyamine is used as the tertiary amine, the target product in which two nitrogen atoms are usually quaternized is obtained. (R represents a lower alkyl group which is the same but may be substituted with hydroxy or lower 1-coIfV)
When using a pipefuzine derivative represented by, for example, a diamine such as N, "-dimethy-pipevodine, N, N'-diethypibewodine," the target product is a compound in which only one of the two nitrogen atoms is selectively conjugated. Quaternized compounds are obtained, and these compounds are new compounds, which can be produced by conventional methods, but can be obtained in good yield according to the method of the present invention.In this case, excess glue proamine Good results can be obtained by using

The object of the present invention can be used as a raw material for the synthesis of amine imide compounds used in surfactants, adhesives, efstomers, and polymerization catalysts for urethane and epoxy resins, and is itself useful as a pesticide and fungicide. .

The present invention will be explained below with reference to Examples.

Example 1 One of two reactors connected to each other with stirring steel
One 30% methylamine aqueous solution (65 ft) was added to 100 m of 6% ammonia water, and each was cooled with ice/food. Next, 200 wt of a 1.7 mol/1 sodium hypochlorite aqueous solution (a solution obtained by reacting chlorine and a sodium hydroxide aqueous solution, in which sodium hydroxide was used in an excess of 10≦the theoretical amount) was added. The mixture was added dropwise to aqueous ammonia while stirring for 30 minutes while maintaining the temperature at t-5 to O'CK, and stirring was continued for an additional KIO minutes to obtain a reaction mixture containing chloroamine. The reaction mixture thus obtained was added to an aqueous trimethylamine solution at a temperature of 0.
The mixture was added dropwise over 30 minutes while maintaining the temperature not to exceed 0.degree. C., and the reaction was continued for an additional 10 minutes. After the reaction, 2N hydrochloric acid 185
Sodium hydroxide present in the reaction solution was neutralized using wIt. The entire amount was evaporated to dryness under reduced pressure, and extracted using 99.5% ethanol/%'500f. When the ethanol extract was concentrated and ether was added to the concentrated solution, crystals were precipitated. When this crystal was taken out in a furnace and vacuum dried in a desiccator, 31
．． 5f white crystals of ON,N,N-trimethylhydophyltrimethylhydrochloride were obtained, yield 84%, melting point 24
f) °C (decomposition) The spectrum of just one of this is 3!00
．． 3100 cn and 1630 cn, showing the absorption based on the K amino group.

Elemental analysis value C3Hll N2 CHN as C1
C1 Calculated value (equity) 32.58 10.03 25.3
2 32.05 Actual value (A) 32.34 10.
16 25.20 32.30 Example 2 Example IKjiI - The same procedure as in Example 1 was carried out except that the order of addition was reversed and the aqueous trimethylamine solution was added dropwise to the reaction mixture containing chloroamine.
32. ．． Obtain crystals of 31ON,N,N-trimethylhydrazinium cloide. Yield 86% Melting point 240℃ (
Decomposition] Elemental analysis value C3Hll NJ! CHN as C1
C1 Calculated value (correction 32.58 10.03 25.32 3
2.05 Estimated value (%) 32.28 10.13 2
5.27 32.40 Example 3 A reaction mixture containing chloroamine was obtained in the same manner as described in Example IKU. To this reaction mixture, a trimethylamine aqueous solution and 2N citric acid 161j were added with deionized water.
OV, the aqueous solution was added dropwise over 30 minutes so that the temperature did not exceed 0°C, and stirring was continued for an additional 16 minutes. Next, the reaction solution was evaporated to dryness under reduced pressure to produce
[Extracted with t99.5 Whisper Etano-w60 Of. The extract was concentrated, and ether was added to the concentrated solution to precipitate crystals.

Dry this crystal in several rooms, 3421 ON, N, NCHN.
C1- Calculated value (2) 32.68 1G, 03 26.32
32.05 dormitory measurements ■ 32.33 10.18 25.
Example 4 160% of 26% ammonia water was charged into a reactor equipped with a stirrer and cooled with dry ice/acetone. To this cold ammonia water 1. ymol/Jf of a subM sodium chloride aqueous solution (400°C) was added dropwise with stirring while maintaining the internal temperature at t-10 to -6°C to obtain a reaction mixture containing chloro and amine. Then to this reaction temperature) 9 ethylamine 68.8
An aqueous solution of f with 3 fistfuls of 2N hydrochloric acid sgK* was heated to a temperature of O.
Add dropwise over 20 minutes while stirring so as not to exceed C and continue to react for 20 minutes. The reaction solution was evaporated to dryness under reduced pressure, and after death, the hydrazinium salt was extracted using 99.5% ethanol (~700ml). After concentrating the ethanol extract, ether was added to the concentrated solution to precipitate crystals. Nine.

The obtained crystals were dried for 88.3 fON, N, N
-Lxflv HiY'l Gini T Mukp Phyto was obtained.

Yield 85% Melting point 175-178℃ Elemental analysis value c6 H17N2 CI CHN C1 Calculated value (Feed 47.21 11.22 1g, IIS
23. 22 actual measurement value (4) 47.15 11.57
18.13 23.59 Example 6 Reaction 11 equipped with a stirrer! 6% ammonia water 200g
/ and cooled with dry ice/methanol μ. To this cold ammonia water, 600 sJ of a 1.7 mol/l aqueous sodium hypochlorite solution was added dropwise over 40 minutes while stirring to maintain the temperature at -10 to -6°C to obtain a reaction mixture containing chloroamine. This reaction mixture was then charged with N,
An aqueous solution of 75.8f of N-dimethyethanol-amine in deionized water was added dropwise over 50 minutes to react while keeping the temperature at 0°C.9. After the reaction was completed, the sodium hydroxide in the system was neutralized with 93.8f of 36% hydrochloric acid.

The reaction solution was evaporated to dryness under reduced pressure, and nine human fusinium salts were extracted using 99.5% ethanol. Concentrate the extract and add methylene acetate to precipitate crystals.
4Jf of white N,Np methyl-N-(!- and dodakiVethy~) hydrazinium cloide was obtained. Yield 88% Melting point 160'C (decomposition) Elemental analysis value C, H13N, OHN as 20C1
C1 Calculated value 6Q 34. HI 9.32 19.92
215.21 guest measurement value 114 34.26 9.53 1
9.79 25.30 1 Drying Example 6 180mg of 26% ammonia water in a reactor equipped with a stirrer
Prepare and cool with dry ice/acetone. Add 400 d of a 1.7 mol/71 sodium hypochlorite aqueous solution to this cold ammonia water while stirring, and bring the internal temperature to -6 to 0°C.
The reaction mixture was added dropwise over 60 minutes while maintaining the temperature to obtain a reaction mixture containing chloroamine. Next, an aqueous solution of 68.8 f of N-methymophorin dissolved in 370 d of 2N hydrochloric acid was added dropwise to the reaction mixture over 40 minutes with stirring so that the temperature did not exceed 16° C. for reaction. After the reaction solution was evaporated to dryness under reduced pressure, extraction was performed with 99.6% ethanol.
The extract was concentrated and ether was added to precipitate white crystals. This product was dried several times to obtain 94.31 ON-amino-N-methylsulfolinium clofide. Yield 91% Melting point 233℃ (decomposition) Elemental analysis value H13
CHN 'C1 calculated value as N, 20C1 (plow 39.35 g, 59 18.36 2
3.23 fresh measurement value eg3 39.26 8.73 18.
0! ! 23.11 Example 7 A reactor equipped with a stirrer was charged with 200 g of 26% ammonia water and cooled with dry ice/acetone. To this cold ammonia water, add 1.7 mo1. /jl of sodium hypochlorite aqueous solution with stirring at a temperature of 1-10 to -6°C.
The reaction mixture was added dropwise over 30 minutes while maintaining the temperature to obtain a reaction mixture containing crotamine.

Subsequently, N, N, N', N'-tetmethylethyl V:/diamine 41L4F was diluted with deionized water for 1!0OW.
While stirring, the dK aqueous solution was added dropwise over 40 minutes to react while maintaining the internal temperature at -6 to 0°C. After the reaction is completed, 36%
Neutralize the sodium hydroxide in the system with woodcutter rawwast.
The reaction solution was evaporated to dryness under reduced pressure, and the human fusinium produced in 99.5% ethanol was extracted with O2. Concentrate the extract and add the concentrate to precipitate the crystals.

The crystals are taken in a furnace and dried to produce 'rs, tt deliquescent N.
, N'-8'7t/-N.

M,N',N'-tetramethylethylenedianium V chloride was obtained. Yield 84% Melting point 211-
! 13℃ to%00 engineering Ribet, w is 3ffi00.3100
Absorption based on amino groups is shown at ゜1g30-. Also,
NMR Nuvector (in heavy water) Fia, 65 (Methi*).

t34 (methylene) shows absorption at 4.80 with an intensity ratio of 3:1:1.

Elemental analysis i [c3 H1ON2 CHN as C1
C1 Calculated value (6) 32.88 9.20 25.56 3
2.35 dormitory measurements (4) 32.62 9.28 25.
38 32.40 Example 8 A reactor equipped with a stirrer was charged with 200 g of 25% ammonia water and cooled with Dobuy ice/acetone. Add 1.7 mol/j of hypochlorous acid F to this cold ammonia water.
While stirring 500 g of aqueous solution, the temperature was adjusted to -10 to -6℃.
The solution was added dropwise over an hour while maintaining the temperature. To this reaction mixture containing chloroamine, 48.5f of N,N'-dimethybipefudine and 8ft of 36% 9B of saline were mixed, and an aqueous solution of 300wtK with deionized water was added while stirring so that the temperature did not exceed 5°C. The mixture was added dropwise over 1 hour to react. The reaction solution was evaporated to dryness under reduced pressure, and the produced hydrazinium salt was extracted using 600 m/m of 99.5% ethanol.
After concentrating the extract, ether was added to precipitate crystals. The crystals were collected in an oven and dried to obtain deliquescent crystals of 109.7 f. Yield 78% Melting point 168-170℃ and (D40 (DNMR spec) #(DMSO-(16)
is shown in Figure 1. That is, 2.66, a, 1~a
, 3°a, 5. It exhibits absorption at an intensity ratio of 3:4:3:4:20 in a, 7 to a, s, s, s ppm. Also, Engineering R Nuvecto is 1 32 Go, 3100.16! Shows absorption based on Ots K amino groups. From this, the obtained %0 is N.

N'-dimethyμ-bibella sl: It was confirmed that only one of the 10t nitrogen atoms was quaternized N-amino-N,N'-dimethy-bibetziniu^crophyte.

Elemental analysis value C6H16'N3 G as C1
E(N C1 Calculated value m 43.60 9.74 25.36 21
．． 40 dormitory measurements (A) 43.58 9.96 26.2
9 21.62 Dormitory Example 9 Equipped with a stirrer, charge 80% of ammonia water into a reactor, cool with dry ice/acetone, and add 7 mol/l of sodium hypochlorite aqueous solution 20012 into the cold ammonia water. While stirring, the mixture was added dropwise over 30 minutes while maintaining the temperature at -6 to 0°C to obtain a reaction mixture containing chloroamine. Immediately after dropping, add triethylenediamine 19. Add an aqueous solution of Of in 185 d of 2N hydrochloric acid dropwise over 20 minutes while stirring so that the internal temperature does not exceed 6°C to react. After evaporating the reaction solution to dryness under reduced pressure,
The produced human fusinium salt was extracted using 99.5% ethanol/I1500m. The extract was concentrated and ede/%/l was added to precipitate crystals. This ton was dried to yield 51.7 f of deliquescent N-aminotriethylene diammonium cloide. Yield: 93% Melting point: 220℃ (decomposition) NMR spectrum fi of this product
/CDMSO-d6) is shown in Figure 2. That is, 1
9~a, 2.3.3~! , 6, L31) shows absorption at pm with an intensity ratio of 3:3:1. In addition, the engineering R spectrum shows absorption based on amino groups at 3150.3050°1620 exi''. From this, it was confirmed that only the l side of the two nitrogen atoms of triethylenediamine was a quaternized humanfusinium salt.

Elemental analysis value C6H14N3 CHN as C1
C1 Calculated value (to) 44.04 8.62 25.68 21
．． 66 unexpected value (equity) 43.85 8.85 25.4
0 21.82

[Brief explanation of the drawing]

Figure 1 shows NMR spectra of the nine target compounds obtained in Example 8)
FIG. 2 shows the NMR spectrum of the target product obtained in Example 9. Procedural amendment (voluntary) 1. Description of the case 1982 Patent Application No. 122868 2 Title of the invention Process for producing quaternary hydrazinium chloride 3 Relationship with the person making the amendment TIda Patent application Daisaku Place 2-27 Doshomachi, Higashi-ku, Osaka Address name (
293) Take ITI Pharmaceutical Industry Co., Ltd. Representative i,,/
, - Kurabayashi Ikushibu 4, Agent Address: 1-17-85, 2-Sanhonmachi, Yodoyo-ku, Osaka City
No. 6, as per the supplementary appendix of the amendment, ``Figure 1'' is corrected as ``Figure 2,'' and ``Figure 2'' is corrected as ``Figure 1.''

Claims (1)

[Claims] A method for producing quaternary and dophnium chloride, which comprises reacting a tertiary amine with a reaction mixture of aqueous ammonia and sodium hypochlorite.