1H, 2apos; synthesis method of H-perfluoroether fluorine-containing cooling liquid

Abstract

The invention relates to a synthesis method of a 1H, 2 'H-perfluoroether fluorine-containing cooling liquid, and discloses a method for preparing a compound shown in a formula 2 from a compound shown in a formula 1. # imgabs0 #, and the method is high in yield, simple in route, simple and convenient to operate and small in danger coefficient.

Description

Technical Field

[0001] The invention belongs to the technical field of fluorine chemical synthesis and relates to the preparation of fluorine-containing compounds. Background Art

[0002] Data centers are strategic resources and new infrastructure that support the development of modern economy and society. They are used to collect, store, process and distribute large amounts of data. With the gradual development of high-density business applications such as artificial intelligence, virtual reality, and smart cities, the amount of computing and complexity that data centers need to cope with are growing rapidly, which requires continuous improvement in CPU power. The great increase in CPU power also brings about a continuous improvement in the heat release effect. For information and communication equipment, operating temperature is an important factor that seriously affects the stability of its working performance. Therefore, the heat generated by the CPU during operation must be promptly and effectively discharged through the coolant.

[0003] Fluorine-containing coolants are very chemically inert and are not easy to react with other substances. They also have properties such as low freezing point and low dielectric constant, making them very suitable as special coolants for data centers. 1H, 2'H-perfluoroethyl ether fluorine-containing coolants were first designed and synthesized by patent US3987111. They are prepared by the addition reaction of trifluoroethanol and tetrafluoroethylene, followed by selective fluorination of fluorine gas. Highly dangerous tetrafluoroethylene and fluorine gas raw materials are used in the synthesis process. Summary of the invention

[0004] The purpose of the present invention is to provide a method for synthesizing 1H,2'H-perfluoroethyl ether fluorine-containing coolant. To this end, the present invention provides a method for preparing a compound shown in Formula 2 from a compound shown in Formula 1, which has high yield, simple route, simple operation and low risk factor.

[0005] The present invention provides a method for preparing a compound shown in Formula 2 from a compound shown in Formula 1, comprising the following steps: subjecting the compound shown in Formula 1 to a hydrolysis reaction, and then to a decarboxylation reaction to obtain a compound shown in Formula 2,

[0006]

[0007] In one embodiment, the hydrolysis reaction comprises the following steps: in a solvent, in the presence of a base, the compound represented by Formula 1 is subjected to a hydrolysis reaction.

[0008] The conditions and operation of the hydrolysis reaction can be conventional conditions and operation of such reactions in the art, and the present invention particularly prefers the following conditions and operation:

[0009] In a certain embodiment, in the hydrolysis reaction, the solvent is selected from one or more of propylene glycol, butanediol, hexanediol, acetonitrile, adiponitrile, ethylene glycol, tetraethylene glycol dimethyl ether and water; preferably, it is a mixed solvent of ethylene glycol and water.

[0010] In one embodiment, in the hydrolysis reaction, the base is selected from one or more of potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium hydroxide, sodium hydroxide, cesium hydroxide, potassium phosphate, sodium phosphate, lithium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate and dilithium hydrogen phosphate; preferably potassium hydroxide, potassium carbonate or potassium phosphate.

[0011] In a certain embodiment, in the hydrolysis reaction, the molar volume ratio of the compound represented by Formula 1 to the solvent is (10-200):27 mol / L; preferably (25-75):27 mol / L; more preferably 50:27 mol / L.

[0012] In one embodiment, in the hydrolysis reaction, the molar ratio of the compound represented by Formula 1 to the base is 0.5:(1.0-10.0); preferably 0.5:(1.0-3.0); more preferably 0.5:2.23 to 0.5:2.65.

[0013] In a certain embodiment, the progress of the hydrolysis reaction can be monitored according to conventional detection methods in the art (such as TLC, HPLC or GC), and the disappearance of the compound represented by Formula 1 is generally taken as the end point of the reaction; preferably, the hydrolysis reaction time is 1-10 hours; more preferably, the hydrolysis reaction time is 1-5 hours (such as 3-5 hours).

[0014] In one embodiment, the reaction temperature of the hydrolysis reaction is 30-150°C; preferably 50-100°C; more preferably 75°C to 80°C.

[0015] In a certain embodiment, the hydrolysis reaction is performed by first adding a solvent and a base, then adding the compound represented by Formula 1, and heating after the addition. More preferably, the hydrolysis reaction satisfies one or more of the following conditions:

[0016] a) before adding the compound represented by formula 1, controlling the temperature of the reaction system to -10-100°C, preferably 0-30°C (e.g. 30°C);

[0017] b) During the addition of the compound of Formula 1, the temperature of the reaction system is controlled to be 0-90° C., preferably 30° C. to 60° C.;

[0018] c) adding the compound of Formula 1 while stirring;

[0019] d) the heating is to 60-100° C. (e.g. 75° C. to 80° C.);

[0020] e) The reaction progress after heating can be monitored by conventional detection methods in the art (such as TLC, HPLC or GC), and the disappearance of the compound represented by Formula 1 is generally taken as the end point of the reaction; preferably, the hydrolysis reaction time is 3 hours.

[0021] In one embodiment, the product of the hydrolysis reaction is directly used for the decarboxylation reaction without post-treatment.

[0022] The conditions and operation of the decarboxylation reaction can be conventional conditions and operation of such reactions in the art, and the present invention particularly prefers the following conditions and operation:

[0023] In a certain embodiment, the decarboxylation reaction comprises the following method 1, method 2 or method 3:

[0024] Method 1 comprises the following steps: in a solvent, in the presence of a base;

[0025] Method 2 comprises the following steps: in a solvent, under heating conditions;

[0026] Method three comprises the following steps: heating in a solvent in the presence of a base.

[0027] In one embodiment, in the decarboxylation reaction methods 1 to 3, the solvent is independently selected from one or more of ethylene glycol, water, glycerol, butylene glycol, hexylene glycol, tetraethylene glycol dimethyl ether, acetonitrile and adiponitrile; preferably, it is a mixed solvent of ethylene glycol and water. The amount of the solvent used can be the conventional amount used in this type of decarboxylation reaction in the art.

[0028] In one embodiment, in the method 1 and the method 3 of the decarboxylation reaction, the base is selected from one or more of potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide, cesium hydroxide, potassium phosphate, sodium phosphate, lithium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate and dilithium hydrogen phosphate; preferably potassium hydroxide, potassium carbonate or potassium phosphate. The amount of the base used can be the conventional amount used in this field for such decarboxylation reactions.

[0029] In a certain embodiment, in the methods 1 to 3 of the decarboxylation reaction, the progress of the decarboxylation reaction can be monitored according to conventional detection methods in the art (such as TLC, HPLC or GC), and the end point of the reaction is generally when the compound represented by Formula 2 is no longer generated; preferably, the time of the decarboxylation reaction is 3-10 hours; more preferably, the time of the decarboxylation reaction is 3-5 hours.

[0030] In one embodiment, in the decarboxylation reaction methods 1 to 3, the reaction product is collected while the decarboxylation reaction is taking place, and the collection time is 3-10 hours; more preferably, the collection time is 3-5 hours.

[0031] In one embodiment, in the method three of the decarboxylation reaction, the reaction temperature of the decarboxylation reaction is 150-250°C; preferably 190°C-210°C.

[0032] In a certain embodiment, in the method for preparing a compound represented by Formula 2 from a compound represented by Formula 1, the reagents involved in the hydrolysis reaction and the decarboxylation reaction are composed of the compound represented by Formula 1 and a base, and the base is potassium hydroxide, potassium carbonate or potassium phosphate.

[0033] In a certain scheme, the method for preparing a compound shown in Formula 2 from a compound shown in Formula 1 comprises the following steps: adding alkali, water and ethylene glycol to a reactor at 15 to 25°C (e.g., 25°C), and when the system temperature drops to 0-30°C (e.g., 30°C), adding the compound shown in Formula 1, controlling the temperature of the reaction system to be less than 60°C during the addition process, heating the temperature to 60-100°C (e.g., 75°C-80°C) after the addition, and then heating the temperature to 150-250°C (e.g., 190°C-210°C) to react to obtain the compound shown in Formula 2;

[0034] Alternatively, a base, water and ethylene glycol are added to a reactor at 15 to 25° C. (e.g., 25° C.), and the compound of formula 1 is added under vigorous stirring. During the addition process, the temperature of the reaction system is controlled to be less than 60° C., and after the addition, the temperature is raised to 60-100° C. (e.g., 75° C.-80° C.) for reaction, and then the temperature is raised to 150-250° C. (e.g., 190° C.-210° C.) to react to obtain the compound of formula 2;

[0035] Preferably, the method for preparing the compound represented by Formula 2 from the compound represented by Formula 1 satisfies one or more of the following conditions:

[0036] a) the molar volume ratio of the compound represented by formula 1 to the water is 50:12 mol / L;

[0037] b) the molar volume ratio of the compound represented by formula 1 to the ethylene glycol is 50:15 mol / L;

[0038] c) the alkali is potassium hydroxide, potassium carbonate or potassium phosphate;

[0039] d) The molar ratio of the compound represented by formula 1 to the base is 0.5:2.23 to 0.5:2.65.

[0040] The present invention also provides a compound represented by formula 1-1:

[0041]

[0042] Wherein, the M is K, Na, Li or Cs.

[0043] In one embodiment, the compound represented by Formula 1-1 is a compound represented by Formula 1-2:

[0044]

[0045] The present invention also provides a method for preparing a carboxylate salt of Formula 1-1 by hydrolyzing the compound of Formula 1:

[0046]

[0047] The conditions of the hydrolysis reaction are as described in any one of the present invention.

[0048] The present invention also provides a method for preparing a compound shown in Formula 2 by decarboxylating a carboxylate shown in Formula 1-1:

[0049]

[0050] The conditions for the decarboxylation reaction are as described in any one of the present invention.

[0051] Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0052] The positive and progressive effects of the present invention are: the method for preparing 1H, 2'H-perfluoroethyl ether of the present invention has high yield, simple route, simple operation and low risk factor. DETAILED DESCRIPTION

[0053] The present invention is further described below in conjunction with specific implementation methods, aiming to illustrate the technical solutions involved in the present invention, reveal the best implementation cases of the present invention, and enable those skilled in the art to understand and implement the present invention. However, it should be understood that the present invention is not limited to the disclosed embodiments, and based on the enlightenment of the present invention, any obvious changes or substitutions should also be considered to fall within the scope of protection of the present invention:

[0054] The reagents used in the following examples are all commercially available, and some reagent information is as follows:

[0055]

[0056] Synthesis route:

[0057]

[0058] Example 1 Synthesis of 1H, 2'H-perfluoroethyl ether fluorinated coolant:

[0059] At 25°C, potassium hydroxide (125g, 5.3eq), water (120mL), and ethylene glycol (150mL) were added to the reaction flask. When the system temperature dropped to 30°C, the compound shown in Formula 1 (160g, 0.5mol) was added in batches. The internal temperature was controlled to be less than 60°C during the addition process. After the addition, the oil bath was 75°C and the reaction was continued for 3 hours to obtain a carboxylate intermediate. Subsequently, a distillation device was set up on the reaction flask, and the oil bath was 190°C for decarboxylation reaction for 5 hours, and the colorless transparent product compound shown in Formula 2 (100g, yield 91.7%, purity 92%) was collected at the same time.

[0060] 19 FNMR (376MHz, CDCl 3 )δppm-82.3(m,3F),-88.1(m,2F),-135.6(m,2F),-143.3(m,1F).

[0061] 1 HNMR (400MHz, CDCl 3 )δppm6.15(m,2H).

[0062] Example 2 Synthesis of 1H, 2'H-perfluoroethyl ether fluorine-containing coolant:

[0063] At 25°C, potassium carbonate (731.4 g, 5.3 eq), water (240 mL), and ethylene glycol (300 mL) were added, and under vigorous stirring, the compound shown in Formula 1 (320 g, 1.0 mol) was added in batches, and the internal temperature was controlled to be less than 60°C during the addition process. After the addition, the oil bath was 80°C and the reaction was continued for 5 hours to obtain a carboxylate intermediate. Subsequently, a distillation device was set up on the reaction bottle, and the oil bath was 210°C for decarboxylation reaction for 5 hours, and the colorless transparent product compound shown in Formula 2 (202 g, yield 92.6%, purity 92%) was collected at the same time.

[0064] 19 F NMR (376 MHz, CDCl 3 )δppm-82.3(m,3F),-88.1(m,2F),-135.6(m,2F),-143.3(m,1F)

[0065] 1 H NMR (400 MHz, CDCl 3 )δppm6.15(m,2H).

[0066] Example 3 Synthesis of 1H, 2'H-perfluoroethyl ether fluorinated coolant:

[0067] At 25°C, potassium phosphate (561.8 g, 5.3 eq), water (120 mL), and ethylene glycol (150 mL) were added to the reaction flask. When the system temperature dropped to 30°C, the compound shown in Formula 1 (160 g, 0.5 mol) was added in batches. The internal temperature was controlled to be less than 60°C during the addition process. After the addition, the oil bath was 75°C and the reaction was continued for 3 hours to obtain a carboxylate intermediate. Subsequently, a distillation device was set up on the reaction flask, and the oil bath was 190°C for decarboxylation reaction for 5 hours, and the colorless transparent product compound shown in Formula 2 (102 g, yield 93.5%, purity 92%) was collected at the same time.

[0068] 19 F NMR (376 MHz, CDCl 3 )δppm-82.3(m,3F),-88.1(m,2F),-135.6(m,2F),-143.3(m,1F).

[0069] 1 H NMR (400 MHz, CDCl 3 )δppm6.15(m,2H).

Claims

1. A method for preparing a compound of formula 2 from a compound of formula 1, comprising the following steps: subjecting the compound of formula 1 to a hydrolysis reaction, and then to a decarboxylation reaction to obtain a compound of formula 2, 2. The method for preparing a compound represented by formula 2 from a compound represented by formula 1 according to claim 1, characterized in that: The method satisfies one or both of the following conditions: a) the hydrolysis reaction comprises the following steps: in a solvent, in the presence of a base, the compound represented by formula 1 is subjected to a hydrolysis reaction; b) the decarboxylation reaction comprises the following steps: carrying out in a solvent in the presence of a base; carrying out in a solvent under heating conditions; or carrying out in a solvent in the presence of a base under heating.

3. The method for preparing a compound represented by formula 2 from a compound represented by formula 1 according to claim 2, characterized in that: The method satisfies one or more of the following conditions: a) In the hydrolysis reaction, the solvent is selected from glycerol, butanediol, hexanediol, acetonitrile, One or more of adiponitrile, ethylene glycol, tetraethylene glycol dimethyl ether and water; b) in the hydrolysis reaction, the base is selected from one or more of potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium hydroxide, sodium hydroxide, cesium hydroxide, potassium phosphate, sodium phosphate, lithium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate and dilithium hydrogen phosphate; c) in the hydrolysis reaction, the molar volume ratio of the compound represented by Formula 1 to the solvent is (10-200): 27 mol / L; d) In the hydrolysis reaction, the molar ratio of the compound represented by Formula 1 to the base is 0.5: (1.0-10.0)； e) the time of the hydrolysis reaction is 1-10 hours; f) the reaction temperature of the hydrolysis reaction is 30-150° C.; g) The operation of the hydrolysis reaction is to first add a solvent and a base, and then add the compound represented by formula 1, After adding, heat up; h) the product of the hydrolysis reaction is directly used for decarboxylation reaction without post-treatment; i) in the decarboxylation reaction, the solvent is independently selected from one or more of ethylene glycol, water, glycerol, butylene glycol, hexylene glycol, tetraethylene glycol dimethyl ether, acetonitrile and adiponitrile; j) when the decarboxylation reaction is carried out in the presence of a base, the base is selected from potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, cesium carbonate, lithium hydroxide, One or more of sodium hydroxide, cesium hydroxide, potassium phosphate, sodium phosphate, lithium phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate and dilithium hydrogen phosphate; k) during the decarboxylation reaction, the reaction product is collected during the decarboxylation reaction, and the collection time is 3-10 hours; 1) When the decarboxylation reaction is carried out by heating, the reaction temperature of the decarboxylation reaction is 150-250°C.

4. The method for preparing a compound represented by formula 2 from a compound represented by formula 1 according to claim 3, characterized in that: The method satisfies one or more of the following conditions: a) in the hydrolysis reaction, the solvent is a mixed solvent of ethylene glycol and water; b) in the hydrolysis reaction, the base is potassium hydroxide, potassium carbonate or potassium phosphate; c) In the hydrolysis reaction, the molar volume ratio of the compound represented by Formula 1 to the solvent is (25-75):27 mol / L; (e.g., 50:27 mol / L); d) In the hydrolysis reaction, the molar ratio of the compound represented by Formula 1 to the base is 0.5: (1.0-3.0); (e.g. 0.5:2.23 to 0.5:2.65); e) the hydrolysis reaction time is 1-5 hours (e.g. 3-5 hours); f) the reaction temperature of the hydrolysis reaction is 50-100° C. (e.g., 75° C. to 80° C.); g) In the hydrolysis reaction, before adding the compound represented by Formula 1, the temperature of the reaction system is controlled to be -10-100°C; h) During the hydrolysis reaction, the temperature of the reaction system is controlled to be 0-90° C. during the addition of the compound represented by Formula 1; i) in the hydrolysis reaction, the compound represented by Formula 1 is added while stirring; j) In the hydrolysis reaction, the temperature is raised to 60-100° C.; k) in the decarboxylation reaction, the solvent is a mixed solvent of ethylene glycol and water; 1) when the decarboxylation reaction is carried out in the presence of a base, the base is potassium hydroxide, potassium carbonate or potassium phosphate; m) in the decarboxylation reaction, the reaction product is collected during the decarboxylation reaction, and the collection time is 3-5 hours; n) When the decarboxylation reaction is carried out by heating, the reaction temperature of the decarboxylation reaction is 190°C-210°C.

5. The method for preparing a compound represented by formula 2 from a compound represented by formula 1 according to claim 4, characterized in that: The method satisfies one or more of the following conditions: a) In the hydrolysis reaction, before adding the compound represented by Formula 1, the temperature of the reaction system is controlled to be 0-30° C. (e.g., 30° C.); b) During the hydrolysis reaction, the temperature of the reaction system is controlled to be between 30° C. and 60° C. during the addition of the compound represented by Formula 1; c) during the hydrolysis reaction, the temperature is raised to 75° C. to 80° C.; d) the reagents participating in the hydrolysis reaction and the decarboxylation reaction are composed of the compound shown in Formula 1 and a base, The base is potassium hydroxide, potassium carbonate or potassium phosphate.

6. The method for preparing a compound of formula 2 from a compound of formula 1 according to claim 1, comprising the following steps: At 15 to 25° C. (e.g., 25° C.), add alkali, water and ethylene glycol into a reactor, and when the system temperature drops to 0-30° C. (e.g., 30° C.), add the compound of formula 1, control the temperature of the reaction system to be less than 60° C. during the addition process, raise the temperature to 60-100° C. (e.g., 75° C.-80° C.) after the addition, and then raise the temperature to 150-250° C. (e.g., 190° C.-210° C.) to react to obtain the compound of formula 2; Alternatively, alkali, water and ethylene glycol are added to a reactor at 15 to 25°C (e.g., 25°C), and the compound shown in Formula 1 is added under vigorous stirring. During the addition, the temperature of the reaction system is controlled to be less than 60°C. After the addition, the temperature is raised to 60-100°C (e.g., 75°C-80°C) for reaction, and then the temperature is raised to 150-250°C (e.g., 190°C-210°C) for reaction to obtain the compound shown in Formula 2.

7. The method for preparing a compound represented by Formula 2 from a compound represented by Formula 1 according to claim 6, which satisfies one or more of the following conditions: a) the molar volume ratio of the compound represented by formula 1 to the water is 50:12 mol / L; b) the molar volume ratio of the compound represented by formula 1 to the ethylene glycol is 50:15 mol / L; c) the alkali is potassium hydroxide, potassium carbonate or potassium phosphate; d) The molar ratio of the compound represented by formula 1 to the base is 0.5:2.23 to 0.5:2.

65.

8. A compound represented by formula 1-1: in, The M is K, Na, Li or Cs.

9. The compound represented by formula 1-1 according to claim 8 is a compound represented by formula 1-2:

10. A method for preparing a compound represented by formula 1-1, comprising the following steps: The compound represented by Formula 1 is subjected to hydrolysis reaction to obtain the compound represented by Formula 1-1. Wherein, the M is K, Na, Li or Cs; and the conditions of the hydrolysis reaction are as described in any one of claims 1 to 5.

11. A method for preparing the compound of formula 2, comprising the following steps: The carboxylate salt of Formula 1-1 is subjected to a decarboxylation reaction to prepare a compound of Formula 2. Wherein, the M is K, Na, Li or Cs; and the conditions of the decarboxylation reaction are as described in any one of claims 1 to 4.

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