Gemini nicotinate quaternary ammonium salt and method for making same

Abstract

The invention relates to a gemini nicotinic acid ester quaternary ammonium salt, namely a bromide bi-N-alkyl nicotinic acid athylene glycol / diethylene glycol / triethylene glycol, the preparation method of which is given as follows: (1) the nicotinic acid and the thionyl chloride are added in a reaction bottle in a molar ratio of the nicotinic acid to the thionyl chloride ranging from 1:3 to 1:6; after the reaction between the nicotinic acid and the thionyl chloride lasts for 2 to 4 hours, the nicotinic acid acyl chloride which is in a white needle-shaped crystal is obtained; (2) the nicotinic acid acyl chloride is dissolved in the dried chloroform and then the alcohol with a molar ratio to the nicotinic acid of 1:2 is dropped slowly in the mixtures of the nicotinic acid acyl chloride; the alcohols can be ethylene glycol, diethylene glycol or teg; the alcohols are dissolved by adding a proper amount of water and the nicotinates which are the products of the alcoholysis are subject to the pumping filtration and drying; (3) the nicotinate and the alkyl bromide are added in the reaction bottle in a molar ratio of the nicotinate to the alkyl bromide ranging from 1:2 to 1:6; the number of the carbon atoms of the alkyl bromide is 8, 10, 12, 14 or 16; the anhydrous acetonitrile is used as the solvent and the mixtures in the reaction bottle are heated and refluxed for 30 to 40 hours; after the mixtures are subject to the washing and pumping filtration, the products, gemini nicotinic acid ester quaternary ammonium salts, are obtained. The gemini nicotinic acid ester quaternary ammonium salt has very high surface activity and very strong bactericidal performances and corrosion inhibition, the preparation method of the invention is simple, convenient and feasible, is easy to be operated, delivers high yield and causes no environmental contaminations.

Description

technical field

[0001] The invention relates to a gemininic acid ester quaternary ammonium salt and a preparation method thereof. Background technique

[0002] Surfactants have become indispensable chemicals in the national economy and human daily life. It is widely used in the fields of energy mining, metal processing, textile, daily chemical industry, food and pharmaceuticals. In 1935, Domagk discovered that cationic surfactants have bactericidal ability, the representatives of which are quaternary ammonium salt-type surfactants, in addition to pyridinium salts, imidazoline salts, and isoquinoline salts. Gemini quaternary ammonium compounds are characterized by their low toxicity, high efficiency, broad-spectrum antibacterial properties and extensive biological activity (Nagamune H et al.Evaluation of the Cytotoxic Effects of Bis-quaternary Ammonium Antimicrobial Reagents on HumanCells[J].Toxicology in Vitro, 2000, 14: 139-147), has been widely used in medicine, food, co...

Examples

Embodiment 1

[0033] Preparation of brominated di-N-alkylnicotinic acid ethylene glycol / diethylene glycol / triethylene glycol ester (EQn-m-n)

[0034] Synthesis of EQ16-2-16

[0035] Add nicotinic acid and thionyl chloride at a molar ratio of 1:5 into the reaction flask, stir and reflux, and NaOH solution absorbs the tail gas. After reacting for 4 hours, it was cooled, and the excess thionyl chloride was spin-dried under reduced pressure to obtain white needle-like crystals. Using dry chloroform as a solvent, slowly drop triethylene glycol with a molar ratio of 1:2 to nicotinic acid, NaOH solution to absorb tail gas, and reflux for 10 h. After cooling, the solvent was spin-dried, and an appropriate amount of water was added to dissolve it, and saturated Na 2 CO 3 Adjust the pH of the aqueous solution to be weakly alkaline, separate the organic phase, extract the aqueous phase with ethyl acetate 2-3 times, combine the organic phases, spin dry and pass through the column with ethyl acetate,...

Embodiment 2

[0044] Structural Characterization of Brominated Di-N-Alkyl Nicotinic Acid Ethylene Glycol / Diethylene Glycol / Triethylene Glycol Ester (EQn-m-n)

[0045] Structural characterization of EQ16-0-16

[0046]

[0047] Referring to Fig. 1, Fig. 1 is the hydrogen spectrogram of EQ16-0-16, according to the spectrogram the chemical shift and related parameters of EQ16-0-16 are listed in the following table 1:

[0048] Table 1EQ16-0-16 1 HNMR parameters

[0049] absorption peak

δ(ppm)

number of small peaks

Peak area

ratio of hydrogen atoms

1

2

3

4

5

6

7

8

9

10.34

9.70

9.05

8.35

5.22

4.84

2.07

1.21-1.1.38

0.88

S

D.

D.

Q

T

S

m

m

T

1.005

1.007

1.004

1.000

2.007

2.012

1.992

26.598

3.085

1

1

1

1

...

Embodiment 3

[0067] Study on Surface Activity of Brominated Di-N-Alkyl Nicotinic Acid Ethylene Glycol / Diethylene Glycol / Triethylene Glycol Ester (EQn-m-n)

[0068] The surfactant to be measured is prepared into a series of aqueous solutions of a certain concentration with twice distilled water, and the surface tension of the aqueous surfactant solution is measured by the suspension ring method at 20°C. The measurement results are shown in Figure 4 and Table 4.

[0069] It can be seen from Figure 4 that with the addition of this series of surfactants, the surface tension of water drops sharply, and the concentration increases, the surface tension decreases slowly, and finally tends to be stable. The alkyl chain grows and the surface activity increases.

[0070] Table 4 cmc, γ of several surfactants cmc and C 20

[0071] substances

cmc (mmol / l)

gamma cmc (mN / m)

C 20 (mmol / l)

EQ08-0-08

3.65

50.5

3.022

[0072] EQ10-0...

technical field

[0001] The invention relates to a gemininic acid ester quaternary ammonium salt and a preparation method thereof. Background technique

[0002] Surfactants have become indispensable chemicals in the national economy and human daily life. It is widely used in the fields of energy mining, metal processing, textile, daily chemical industry, food and pharmaceuticals. In 1935, Domagk discovered that cationic surfactants have bactericidal ability, the representatives of which are quaternary ammonium salt-type surfactants, in addition to pyridinium salts, imidazoline salts, and isoquinoline salts. Gemini quaternary ammonium compounds are characterized by their low toxicity, high efficiency, broad-spectrum antibacterial properties and extensive biological activity (Nagamune H et al.Evaluation of the Cytotoxic Effects of Bis-quaternary Ammonium Antimicrobial Reagents on HumanCells[J].Toxicology in Vitro, 2000, 14: 139-147), has been widely used in medicine, food, co...

Examples

Embodiment 1

[0033] Preparation of brominated di-N-alkylnicotinic acid ethylene glycol / diethylene glycol / triethylene glycol ester (EQn-m-n)

[0034] Synthesis of EQ16-2-16

[0035] Add nicotinic acid and thionyl chloride at a molar ratio of 1:5 into the reaction flask, stir and reflux, and NaOH solution absorbs the tail gas. After reacting for 4 hours, it was cooled, and the excess thionyl chloride was spin-dried under reduced pressure to obtain white needle-like crystals. Using dry chloroform as a solvent, slowly drop triethylene glycol with a molar ratio of 1:2 to nicotinic acid, NaOH solution to absorb tail gas, and reflux for 10 h. After cooling, the solvent was spin-dried, and an appropriate amount of water was added to dissolve it, and saturated Na 2 CO 3 Adjust the pH of the aqueous solution to be weakly alkaline, separate the organic phase, extract the aqueous phase with ethyl acetate 2-3 times, combine the organic phases, spin dry and pass through the column with ethyl acetate,...

Embodiment 2

[0044] Structural Characterization of Brominated Di-N-Alkyl Nicotinic Acid Ethylene Glycol / Diethylene Glycol / Triethylene Glycol Ester (EQn-m-n)

[0045] Structural characterization of EQ16-0-16

[0046]

[0047] Referring to Fig. 1, Fig. 1 is the hydrogen spectrogram of EQ16-0-16, according to the spectrogram the chemical shift and related parameters of EQ16-0-16 are listed in the following table 1:

[0048] Table 1EQ16-0-16 1 HNMR parameters

[0049] absorption peak

δ(ppm)

number of small peaks

Peak area

ratio of hydrogen atoms

1

2

3

4

5

6

7

8

9

10.34

9.70

9.05

8.35

5.22

4.84

2.07

1.21-1.1.38

0.88

S

D.

D.

Q

T

S

m

m

T

1.005

1.007

1.004

1.000

2.007

2.012

1.992

26.598

3.085

1

1

1

1

...

Embodiment 3

[0067] Study on Surface Activity of Brominated Di-N-Alkyl Nicotinic Acid Ethylene Glycol / Diethylene Glycol / Triethylene Glycol Ester (EQn-m-n)

[0068] The surfactant to be measured is prepared into a series of aqueous solutions of a certain concentration with twice distilled water, and the surface tension of the aqueous surfactant solution is measured by the suspension ring method at 20°C. The measurement results are shown in Figure 4 and Table 4.

[0069] It can be seen from Figure 4 that with the addition of this series of surfactants, the surface tension of water drops sharply, and the concentration increases, the surface tension decreases slowly, and finally tends to be stable. The alkyl chain grows and the surface activity increases.

[0070] Table 4 cmc, γ of several surfactants cmc and C 20

[0071] substances

cmc (mmol / l)

gamma cmc (mN / m)

C 20 (mmol / l)

EQ08-0-08

3.65

50.5

3.022

[0072] EQ10-0...

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