CN101973949A - Method for preparing 2,4,6-tri(amino caproyl)-1,3,5-triazine - Google Patents

Abstract

The invention discloses a method for preparing an organic ternary polycarboxylic acid dustless antirust additive 2,4,6-tri(amino caproyl)-1,3,5-triazine by adopting a one-pot method, which comprises the following steps of: ring-opening caprolactam with alkali to generate carboxylate of aminocaproic acid first; then performing a substitution reaction by the carboxylate of aminocaproic acid and cyanuric chloride; and finally, acidizing with hydrochloric acid to prepare derivatives of organic ternary polycarboxylic acid. The preparation method is free from a toxic organic solvent and employs common water as a solvent for reaction. The preparation method ha the advantages of simple process operation, low production cost and low environmental pollution and is more suitable for large scale industrial production.

Description

Preparation method of 2,4,6-tris(aminocaproic acid group)-1,3,5-triazine

This invention is funded by Tianjin Normal University Development Fund (52X09042). the

technical field

The invention belongs to the technical field of organic synthesis and relates to a preparation method of 2,4,6-tris(aminocaproyl)-1,3,5-triazine. the

Background technique

2,4,6-tris(aminocaproic acid)-1,3,5-triazine is a very important water-based rust inhibitor. It has superior performance, mainly including: it can be used to protect various metals from rusting, and it works better with Irgamet 42; excellent hard water stability; extremely low foaming tendency, good air release; its triethanolamine Sodium salt will not affect the performance of extreme pressure antiwear agent; it can replace sodium nitrite when used in conjunction with AMINE O, and the anti-rust effect of adding 0.5% is equivalent to adding 6% sodium nitrite; there is no tendency to form nitrosamines; Chlorine-free and extremely low toxicity. In conclusion, 2,4,6-tris(aminocaproic acid)-1,3,5-triazine is a class of superior performance, green and environment-friendly ashless rust inhibitor suitable for all water-based lubrication and cleaning systems. the

So far, we have not found any literature reports on the synthesis method of 2,4,6-tris(aminocaproyl)-1,3,5-triazine. Almost 90% of the world's 2,4,6-tris(aminocaproyl)-1,3,5-triazine comes from the same manufacturer - Ciba Specialty Chemicals, and Ciba Specialty Chemicals is about The synthesis technique of this compound is kept secret. the

Contents of the invention

The purpose of the present invention is to break through the technical barriers of 2,4,6-tris(aminocaproic acid)-1,3,5-triazine, and provide a kind of 2,4,6-tris(aminocaproic acid)- Process for the preparation of 1,3,5-triazines. the

The inventor surprisingly found in the test: with caprolactam, cyanuric chloride, sodium hydroxide, hydrochloric acid as the main raw materials, common tap water is used as the solvent in the reaction, the toxic organic solvent is cut off, and the temperature is controlled at 25-80°C 2,4,6-tri(aminocaproic acid group)-1,3,5-tri Zinc. The inventor provides following technical scheme for this reason:

A preparation method of organic ternary polycarboxylic acid derivatives is characterized in that, in a polar solvent, the caprolactam is first hydrolyzed with an alkali to generate a carboxylate of aminocaproic acid, and then the carboxylate of aminocaproic acid is combined with the trimerized The substitution reaction of cyanogen chloride occurs, and finally the method of acid precipitation is used to prepare the organic trivalent polycarboxylic acid derivative. That is, in a polar solvent, the "one-pot method" is used to first open the ring of caprolactam (I) with an alkali to generate carboxylate (II) of aminocaproic acid, and then undergo a substitution reaction with cyanuric chloride (III), Finally, acidify and precipitate with hydrochloric acid;

The polar solvent of the present invention is water. Described alkali is sodium hydroxide. Wherein sodium hydroxide: caprolactam: cyanuric chloride: the molar ratio of hydrochloric acid is 3-6: 3: 0.8-1: 3-9; The reaction temperature of caprolactam hydrolysis is 25-70 ℃, and the reaction time is 30-60 minutes; The temperature for the substitution reaction between acid carboxylate and cyanuric chloride is 25-80°C, and the reaction time is 60-180 minutes; the reaction temperature for acid precipitation is 25-50°C, and the reaction time is 30-180 minutes. the

The preparation of 2,4,6-tris(aminocaproyl)-1,3,5-triazine in the present invention mainly adopts TLC to monitor the reaction process, and uses ethanol as a developing agent. the

2,4,6-tris(aminocaproic acid)-1,3,5-triazine compounds are as follows:

The advantages and characteristics of the preparation method of 2,4,6-tris(aminocaproyl)-1,3,5-triazine disclosed by the present invention are:

(1) The reaction operation is simple and easy, and the reaction conditions are mild. the

(2) The solvent used is water, which is cheap and easy to obtain and is friendly to the environment, and is not easy to cause environmental pollution. the

(3) The time required for the reaction is short, the yield is high, and the product obtained has high purity and superior performance. the

(4) The organic ternary polycarboxylic acid ashless rust inhibitor prepared by the present invention can be applied to all water-based lubrication and cleaning systems. The production cost is low, the profit margin is large, and it is more suitable for large-scale industrial production. the

Detailed ways

The present invention will be further described below in conjunction with the examples, the examples are only for explanatory purposes, and are not meant to limit the scope of the present invention in any way. the

All raw materials are purchased from chemical reagent companies at home and abroad, and are used directly without further purification. The melting point of the product was measured on a melting point apparatus of X ₄ Micro; ¹ H NMR was measured on an instrument of Bruker Avance 300 in deuterated DMSO; the infrared spectrum was measured by the method of KBr pellets , measured on a Jasco FT/IR-620v infrared spectrometer. The data obtained from the above tests are compared with the actual values of the standard samples.

Example 1

Add sodium hydroxide (32.8g, 0.82mol), caprolactam (92.6g, 0.82mol) and 400mL water respectively in a 1000mL three-neck round bottom flask equipped with a magnet, reflux condenser and thermometer, start stirring and control the temperature at 60 °C for 30 minutes. After the reaction, cyanuric chloride (50.4 g, 0.27 mol) was added, the temperature was raised to 70° C., and maintained for 120 minutes, during which the reaction progress was monitored by TLC, and ethanol was used as a developing solvent. Cool down to 30°C, add concentrated hydrochloric acid (82g, 0.82mol) with a concentration of 36.5%, precipitate a wet cake-like white solid, stir for 30 minutes, filter with suction, and dry at 80°C to obtain 54 grams of product, yield 88.7%. mp181-183°C. IR: v=3300, 2942, 2364, 1710, 1567, 1413, 1344, 1257, 1186, 843, 785, 742cm ^-1 . ¹ H NMR (DMSO, 300MHz): δ=1.25(t, J=6.9Hz, 6H), 1.37-1.60(m, 12H), 2.14-2.28(m, 12H), 6.20-6.69(t, J=6.3Hz, 3H). Anal. Calcd for C ₂₁ H ₃₆ N ₆ O ₆ : C, 53.83; H, 7.74; N, 17.94. Found: C, 53.91; H, 7.64; N, 17.93.

Example 2

Add sodium hydroxide (43.7g, 1.1mol), caprolactam (92.6g, 0.82mol) and 400mL water respectively in a 1000mL three-neck round bottom flask equipped with a magnet, reflux condenser and thermometer, start stirring and control the temperature at 70 °C for 40 minutes. After the reaction, cyanuric chloride (50.4 g, 0.27 mol) was added, the temperature was raised to 75° C., and maintained for 100 minutes, during which the reaction progress was monitored by TLC, and ethanol was used as a developing solvent. Cool down to 35°C, add concentrated hydrochloric acid (164g, 1.64mol) with a concentration of 36.5%, precipitate a wet cake-like white solid, stir for 50 minutes, filter with suction, and dry at 80°C to obtain 54 g of the product with a yield of 88.4%. mp181-183°C. IR: v=3300, 2942, 2364, 1710, 1567, 1413, 1344, 1257, 1186, 843, 785, 742cm ^-1 . ¹ H NMR (DMSO, 300MHz): δ=1.25(t, J=6.9Hz, 6H), 1.37-1.60(m, 12H), 2.14-2.28(m, 12H), 6.20-6.69(t, J=6.3Hz, 3H). Anal. Calcd for C ₂₁ H ₃₆ N ₆ O ₆ : C, 53.83; H, 7.74; N, 17.94. Found: C, 53.91; H, 7.64; N, 17.93.

Example 3

Add sodium hydroxide (54.6g, 1.37mol), caprolactam (92.6g, 0.82mol) and 400mL water respectively into a 1000mL three-neck round bottom flask equipped with a magnet, reflux condenser and thermometer, start stirring and control the temperature at 65 °C for 30 minutes. After the reaction, cyanuric chloride (50.4 g, 0.27 mol) was added, the temperature was raised to 75° C., and maintained for 90 minutes, during which the reaction progress was monitored by TLC, and ethanol was used as a developing solvent. Cool down to 40°C, add concentrated hydrochloric acid (219g, 2.19mol) with a concentration of 36.5%, precipitate a wet cake-like white solid, stir for 60 minutes, filter with suction, and dry at 80°C to obtain 53 g of the product, with a yield of 87%. mp181-183°C.IR: v=3300, 2942, 2364, 1710, 1567, 1413, 1344, 1257, 1186, 843, 785, 742cm ^-1 . ¹ H NMR (DMSO, 300MHz): δ=1.25(t, J=6.9Hz, 6H), 1.37-1.60(m, 12H), 2.14-2.28(m, 12H), 6.20-6.69(t, J=6.3Hz, 3H). Anal. Calcd for C ₂₁ H ₃₆ N ₆ O ₆ : C, 53.83; H, 7.74; N, 17.94. Found: C, 53.91; H, 7.64; N, 17.93.

Example 4

Add sodium hydroxide (54g, 1.35mol), caprolactam (114.13g, 1.01mol), and 400mL water respectively into a 1000mL three-necked round-bottom flask equipped with a magnet, reflux condenser and thermometer, start stirring and control the temperature at 70°C React for 35 minutes. After the reaction, cyanuric chloride (50.4 g, 0.27 mol) was added, the temperature was raised to 70° C., and maintained for 120 minutes, during which the reaction progress was monitored by TLC, and ethanol was used as a developing solvent. Cool down to 40°C, add concentrated hydrochloric acid (304g, 3.04mol) with a concentration of 36.5%, precipitate a wet cake-like white solid, stir for 70 minutes, filter with suction, and dry at 80°C to obtain 51.78 g of product, yield 85%. mp181-183°C. IR: v=3300, 2942, 2364, 1710, 1567, 1413, 1344, 1257, 1186, 843, 785, 742cm ^-1 . ¹ H NMR (DMSO, 300MHz): δ=1.25(t, J=6.9Hz, 6H), 1.37-1.60(m, 12H), 2.14-2.28(m, 12H), 6.20-6.69(t, J=6.3Hz, 3H). Anal. Calcd for C ₂₁ H ₃₆ N ₆ O ₆ : C, 53.83; H, 7.74; N, 17.94. Found: C, 53.91; H, 7.64; N, 17.93.

Example 5

Add sodium hydroxide (37.8g, 0.945mol), caprolactam (91.53g, 0.81mol) and 400mL water respectively in a 1000mL three-necked round bottom flask equipped with a magnet, reflux condenser and thermometer, start stirring and control the temperature at 70 °C for 35 minutes. After the reaction, cyanuric chloride (50.4 g, 0.27 mol) was added, the temperature was raised to 70° C., and maintained for 120 minutes, during which the reaction progress was monitored by TLC, and ethanol was used as a developing solvent. Cool down to 40°C, add concentrated hydrochloric acid (162g, 1.62mol) with a concentration of 36.5%, precipitate a wet cake-like white solid, stir for 160 minutes, filter with suction, and dry at 80°C to obtain 51.66 g of the product, with a yield of 84%. mp181-183°C. IR: v=3300, 2942, 2364, 1710, 1567, 1413, 1344, 1257, 1186, 843, 785, 742cm ^-1 . ¹ H NMR (DMSO, 300MHz): δ=1.25(t, J=6.9Hz, 6H), 1.37-1.60(m, 12H), 2.14-2.28(m, 12H), 6.20-6.69(t, J=6.3Hz, 3H). Anal. Calcd for C ₂₁ H ₃₆ N ₆ O ₆ : C, 53.83; H, 7.74; N, 17.94. Found: C, 53.91; H, 7.64; N, 17.93.

After the preferred embodiment described in detail, those skilled in the art can clearly understand that various changes and modifications can be carried out without departing from the scope and spirit of the above-mentioned patent application. Any simple modifications, equivalent changes and modifications all belong to the scope of the technical solution of the present invention. And the present invention is not limited by the example implementations in the specification. the

Claims (5)

1. one kind 2,4,6-three (hexosamine base)-1,3, the preparation method of 5-triazine is characterized in that in polar solvent, adopt " one kettle way ", make the carboxylate salt (II) of hexanolactam (I) open loop generation hexosamine earlier with alkali, and then substitution reaction takes place, separate out with hcl acidifying at last with cyanuric chloride (III);

2. the described preparation method of claim 1, wherein said polar solvent is a water.

3. the described preparation method of claim 1, wherein said alkali is sodium hydroxide.

4. the described preparation method of claim 1, wherein sodium hydroxide: hexanolactam: cyanuric chloride: the mol ratio of hydrochloric acid is 3-6: 3: 0.8-1: 3-9; The temperature of reaction 25-70 of hexanolactam hydrolysis ℃, reaction times 30-60 minute; The temperature of the carboxylate salt of hexosamine and cyanuric chloride generation substitution reaction is 25-80 ℃, reaction times 60-180 minute; The temperature of reaction of acid out is 25-50 ℃, and the reaction times is 30-180 minute.

5. preparation method as claimed in claim 4, wherein sodium hydroxide: hexanolactam: cyanuric chloride: the mol ratio of hydrochloric acid is 3.5: 3: 1: 3-9.