SYNTHESIS OF TRIFLUOROACETYL IODIDE (TFAI) FROM TRIFLUOROACETYL CHLORIDE (TFAC) AND HYDROGEN IODIDE (HI) IN A LIQUID PHASE REACTION

Abstract

The present disclosure provides a process for making trifluoroacetyl iodide (TFAI) in a liquid phase reaction. Specifically, the present disclosure provides a liquid phase reaction of trifluoroacetyl chloride (TFAC) and hydrogen iodide (HI), with or without a catalyst, to form trifluoroacetyl iodide (TFAI). The reaction may be performed at ambient or elevated temperatures.

Claims

1. A process for producing trifluoroacetyl iodide (TFAI) in a liquid phase reaction, the process comprising: providing trifluoroacetyl chloride, hydrogen iodide, and an optional catalyst; reacting the trifluoroacetyl chloride and hydrogen iodide to provide trifluoroacetyl iodide.

2. The process of claim 1, wherein in the providing step, the mole ratio of the trifluoroacetyl chloride to the hydrogen iodide is from about 1:10 to about 10:1.

3. The process of claim 1, wherein in the providing step, a weight ratio of the catalyst to the trifluoroacetyl chloride may be from about 0.001:1 to about 0.5:1.

4. The process of claim 1, wherein the catalyst is selected from the group consisting of silicon carbide, activated carbon, carbon molecular sieves, and combinations thereof.

5. The process of claim 1, wherein in the reacting step, the trifluoroacetyl chloride, the hydrogen iodide, and the optional catalyst are at a temperature from 0° C. to 200° C.

6. A process for producing trifluoroacetyl iodide (TFAI) in a liquid phase reaction, the process comprising: mixing trifluoroacetyl chloride, hydrogen iodide, and an optional catalyst; and heating the trifluoroacetyl chloride, hydrogen iodide, and an optional catalyst to produce trifluoroacetyl iodide and hydrogen chloride.

7. The process of claim 6, further including separating the trifluoroacetyl iodide from the hydrogen chloride, trifluoroacetyl chloride, and hydrogen iodide.

8. The process of claim 6, wherein the process is a continuous process.

9. The process of claim 6, wherein the process is a batch process.

10. The process of claim 6, wherein the catalyst is selected from the group consisting of silicon carbide, activated carbon, carbon molecular sieves, and combinations thereof.

11. The process of claim 6, wherein in the reacting step, the trifluoroacetyl chloride, the hydrogen iodide, and the optional catalyst are at a temperature from 0° C. to 200° C.

12. The process of claim 6, wherein in the reacting step, the trifluoroacetyl chloride, the hydrogen iodide, and the optional catalyst are at a pressure of 5 psig to 500 psig.

Description

DESCRIPTION OF THE DRAWINGS

[0017] FIG. 1 corresponds to Example 1 and shows reactor pressure versus time for the liquid phase synthesis of trifluoroacetyl iodide (TFAI) at ambient temperature.

[0018] FIG. 2 corresponds to Example 2 and shows conversion of TFAC and selectivity for TFAI versus reaction time at ambient temperature.

[0019] FIG. 3 corresponds to Example 3 and shows conversion of TFAC and selectivity for TFAI versus reaction time at ambient temperature.

[0020] FIG. 4 corresponds to Example 4 and shows conversion of TFAC and selectivity for TFAI versus reaction time at 90° C.

[0021] FIG. 5 corresponds to Example 5 and shows conversion of TFAC and selectivity for TFAI versus reaction time at 90° C.

[0022] FIG. 6 corresponds to Example 6 and shows conversion of TFAC and selectivity for TFAI versus reaction time at 60° C.

[0023] FIG. 7 corresponds to Example 7 and shows conversion of TFAC and selectivity for TFAI versus reaction time at 60° C.

[0024] FIG. 8 corresponds to Example 8 and shows conversion of TFAC and selectivity for TFAI versus reaction time at 60° C.

[0025] FIG. 9 corresponds to Example 9 and shows conversion of TFAC and selectivity for TFAI versus reaction time at 120° C.

[0026] FIG. 10 corresponds to Example 10 and shows conversion of TFAC and selectivity for both TFAI and CF.sub.3I versus reaction time at 120° C.

[0027] FIG. 11 corresponds to Example 11 and shows conversion of TFAC and selectivity for TFAI versus reaction time at 60° C. in the presence of a catalyst.

[0028] FIG. 12 corresponds to Example 12 and shows conversion of TFAC and selectivity for TFAI versus reaction time at 60° C. in the presence of a catalyst.

[0029] FIG. 13 corresponds to Example 13 and shows conversion of TFAC and selectivity for TFAI versus reaction time at 90° C. in the presence of a catalyst.

DETAILED DESCRIPTION

[0030] The present disclosure provides a liquid phase process for producing trifluoroacetyl iodide (TFAI) via the reaction shown below in Equation 1.

CF.sub.3COCl+HI.fwdarw.CF.sub.3COI+HCl  Equation 1:

[0031] The liquid phase process can be conducted in a liquid phase reactor with or without agitation. Preferably, the reactor is equipped with an agitator, and the reactor may be formed in whole or in part of materials including Hastelloy C 276, Inconel 600, Inconel 625, Monel 400, SS316, SS316L, PFA lined, PTFE lined, glass lined etc.

[0032] The reaction can be run under conditions effective to form trifluoroacetyl iodide (TFAI) but not CF.sub.3I to avoid the difficulties arising from the separation of trifluoroacetyl chloride (TFAC) from CF.sub.3I.

[0033] The reaction temperatures may be as low as about 0° C., about 25° C., about 35° C., about 40° C., about 50° C., or as high as about 60° C., about 90° C., about 120° C., about 150° C., or about 200° C., or within any range defined between any two of the foregoing values.

[0034] The pressure may be as low as about 5 psig, about 25 psig, about 50 psig, about 100 psig, about 150 psig, about 200 psig, about 250 psig, or as high as about 300 psig, about 350 psig, about 400 psig, about 450 psig, about 500 psig, or within any range defined between any two of the foregoing values.

[0035] The TFAC:HI (trifluoroacetyl chloride:hydrogen iodide) ratio may be as low as about 1:10, about 2:1, about 3:1, about 4:1, or as high as about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, or about 10:1, or within any range defined between any two of the foregoing values. Preferably, the TFAC:HI ratio is from 1:2 to 2:1, such as 1:1, 1:1.5, 1:1.9, 1.1:1, 1.5:1, 1.9:1, for example. More preferably, the TFAC/HI ratio is from 1:1 to 2:1.

[0036] A catalyst may be added to the reaction. The catalyst may be silicon carbide, activated carbon, carbon molecular sieves, or combinations thereof. The weight ratio of the catalyst to TFAC may be as low as about 0.001:1, about 0.01:1, about 0.02:1, about 0.03:1, about 0.04:1, or as high as about 0.05:1, about 0.06:1, about 0.07:1, about 0.08:1, about 0.09:1, about 0.1:1, about 0.2:1, about 0.5:1, or within any range defined between any two of the foregoing values.

[0037] The residence time may be as low as about 0.1 hour, about 0.5 hour, about 1 hour, about 5 hours, about 10 hours, about 15 hours, or as high as about 20 hours, about 30 hours, about 40 hours, about 50 hours, or within any range defined between any two of the foregoing values.

[0038] The reaction can be carried out in a batch-wise or continuous mode. Preferably, the reaction is carried out in a continuous mode.

[0039] The reactor may be equipped with a distillation column to remove low boiling by-products, such as HCl. As reaction progresses, the TFAI concentration rises in the reactor and a liquid stream can be drawn continuously or intermittently for product separation. The isolated TFAI can be sent to a storage tank for the use in next step reaction as raw material to make CF.sub.3I, while the separated TFAC and/or HI can be recycled back to the reactor.

EXAMPLES

[0040] In the following examples, the manufacture of TFAI from TFAC and HI in a liquid phase process is demonstrated.

Example 1

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at Ambient Temperature

[0041] At ambient temperature, 19.94 grams of HI and 22.97 grams of TFAC (TFAC/HI molar ratio of 1.11:1.00) were charged into a 100 mL 316L reactor equipped with a pressure gauge without agitation. The cylinder pressure was monitored to track the progress of the reaction with the pressure profile as shown in FIG. 1. After 5.3 hours, the reactor pressure was stabilized at 168 psig. After 17.5 hours, the reactor was drained, and the liquid sample was analyzed by gas chromatography (GC). The results show 76.04% conversion of TFAC, and 99.99% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 2

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at Ambient Temperature

[0042] At ambient temperature, 19.48 grams of HI and 21.21 grams of TFAC (TFAC/HI molar ratio of 1.05:1.00) were charged into a 100 mL 316L reactor equipped with a pressure gauge without agitation. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity as shown in FIG. 2. The results show that, during the first 12 hours, TFAC conversion was increased with increasing reaction time, reaching about 85.4% after 14 hours. Near 100% selectivity for TFAI was observed throughout the entire run. No CF.sub.3I formation was observed.

Example 3

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at Ambient Temperature

[0043] At ambient temperature, 47.71 grams of HI and 70.30 grams of TFAC (TFAC/HI molar ratio of 1.42:1.00) were charged into a 300 mL Teflon-lined PARR reactor equipped with an agitator. The reactor was agitated during the test period. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity as shown in FIG. 3. After 14 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed 65-66% conversion of TFAC and >99.9% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 4

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at 90° C.

[0044] A 300 mL Teflon-lined PARR reactor equipped with an agitator was charged with 64.33 grams of TFAC. The reactor was agitated and heated to 70° C., then 56.67 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.10:1.00). The reactor temperature controller was set at 90° C., with peak temperature of 98° C. observed due to exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity as shown in FIG. 4. After 4 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed about 84% conversion of TFAC and >99.9% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 5

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at 90° C.

[0045] A 300 mL Teflon-lined PARR reactor equipped with an agitator was charged with 65.49 grams of TFAC. The reactor was agitated and heated to 70° C., then 51.08 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.24:1.00). The reactor temperature controller was set at 90° C., with peak temperature of 97.7° C. observed due to the exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity as shown in FIG. 5. After 6 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed 77-78% conversion of TFAC and >99.9% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 6

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at 60° C.

[0046] A 300 mL Teflon-lined PARR reactor with agitator was charged with 70.63 grams of TFAC. The reactor was agitated and heated to 35° C., then 61.34 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.11:1.00). The reactor temperature controller was set at 60° C., with peak temperature of 61.5° C. observed due to the exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity as shown in FIG. 6. After 6 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed roughly 85% conversion of TFAC and >99.9% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 7

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at 60° C.

[0047] A 300 mL Teflon-lined PARR reactor equipped with an agitator was charged with 74.18 grams of TFAC. The reactor was agitated and heated to 35° C., then 42.58 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.68:1.00). The reactor temperature controller was set at 60° C., with peak temperature of 65° C. observed due to the exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity as shown in FIG. 7. After 10.5 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis from the final liquid sample showed roughly 60% conversion of TFAC and near 100% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 8

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at 60° C.

[0048] A 300 mL Teflon-lined PARR reactor equipped with an agitator was charged with 75.10 grams of TFAC. The reactor was agitated and heated to 35° C., then 38.77 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.87:1.00). The reactor temperature controller was set at 60° C., with peak temperature of 66.3° C. observed due to exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity shown in FIG. 8. After 6 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed 51-52% conversion of TFAC and near 100% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 9

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at 120° C.

[0049] A 300 mL Teflon-lined PARR reactor equipped with an agitator was charged with 65.60 grams of TFAC. The reactor was agitated and heated to 85° C., then 56.12 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.13:1.00). The reactor temperature controller was set at 120° C., with peak temperature of 121.3° C. observed due to the exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity as shown in FIG. 9. After 5 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed 80-81% conversion of TFAC, 99.79% selectivity for TFAI, and 0.10% selectivity for CF.sub.3I.

Example 10

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at 120° C.

[0050] A 300 mL Teflon-lined PARR reactor equipped with an agitator was charged with 61.08 grams of TFAC. The reactor was agitated and heated to 85° C., then 40.99 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.44:1.00). The reactor temperature controller was set at 120° C., with peak temperature of 120.9° C. observed due to the exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity as shown in FIG. 10. After 3 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed 72-73% conversion of TFAC, 99.82% selectivity for TFAI, and 0.13% selectivity for CF.sub.3I.

Example 11

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) with Catalyst

[0051] 1.13 grams of silicon carbide (SiC) catalyst and 71.44 grams of TFAC were charged into a 300 mL Teflon-lined PARR reactor equipped with an agitator. The weight ratio of the catalyst to the TFAC was 0.016:1.00. The reactor was agitated and heated to 35° C., then 65.39 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.05:1.00). The reactor temperature controller was set at 60° C., with peak temperature of 60.2° C. observed due to the exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity shown in FIG. 11. After 5 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed 85-86% conversion of TFAC and 99.9% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 12

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) with Catalyst

[0052] 1.09 grams of silicon carbide (SiC) catalyst, and 74.95 grams of TFAC were charged into a 300 mL Teflon-lined PARR reactor equipped with an agitator. The weight ratio of the catalyst to the TFAC was 0.014:1.00. The reactor was agitated and heated to 35° C., then 53.80 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.35:1.00). The reactor temperature controller was set at 60° C., with peak temperature of 60.9° C. observed due to the exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity shown in FIG. 12. After 5 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed 72-73% conversion of TFAC and >99.9% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 13

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) with Catalyst

[0053] 1.10 grams of silicon carbide (SiC) catalyst, and 76.26 grams of TFAC were charged into a 300 mL Teflon-lined PARR reactor equipped with an agitator. The weight ratio of the catalyst to the TFAC was 0.014:1.00. The reactor was agitated and heated to 75° C., then 57.12 grams of HI was charged into the reactor (TFAC/HI molar ratio of 1.29:1.00). The reactor temperature controller was set at 90° C., with peak temperature of 107.3° C. observed due to exothermic reaction. Periodically, a small amount of liquid sample was drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity shown in FIG. 13. After 6 hours, the reactor was drained, and the liquid samples were analyzed by GC. The analysis of the final liquid sample showed 74-75% conversion of TFAC and >99.9% selectivity for TFAI. No CF.sub.3I formation was observed.

Example 14

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI)

[0054] Hydrogen iodide (172.7 grams) and 20.0 grams of TFAC (TFAC/HI molar ratio of 1.0:9.0) are charged into a 100 mL 316L reactor equipped with a pressure gauge without agitation. Periodically, a small amount of liquid sample is drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity. After a time, the reactor is drained, and the liquid samples are analyzed by GC.

Example 15

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI)

[0055] Hydrogen iodide (20.0 grams) and 165.6 grams of TFAC (TFAC/HI molar ratio of 8.0:1.0) are charged into a 100 mL 316L reactor equipped with a pressure gauge without agitation. Periodically, a small amount of liquid sample is drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity. After a time, the reactor is drained, and the liquid samples are analyzed by GC.

Example 16

Liquid Phase Synthesis of Trifluoroacetyl Iodide (TFAI) at 200° C.

[0056] A 300 mL Teflon-lined PARR reactor equipped with an agitator is charged with 61.08 grams of TFAC. The reactor is agitated and heated up to 180° C., then 40.99 grams of HI is charged into the reactor (TFAC/HI molar ratio of 1.44:1.00). The reactor temperature controller is set at 200° C. Periodically, a small amount of liquid sample is drained and analyzed by gas chromatography (GC) to track the progress of the reaction with the TFAC conversion and TFAI selectivity. After a time, the reactor is drained, and the liquid samples are analyzed by GC.

[0057] It should be understood that the foregoing description is only illustrative of the present disclosure. Various alternatives and modifications can be devised by those skilled in the art without departing from the disclosure. Accordingly, the present disclosure is intended to embrace all such alternatives, modifications and variances that fall within the scope of the appended claims.

Aspects

[0058] Aspect 1 is a process for producing trifluoroacetyl iodide (TFAI), the process comprising: providing trifluoroacetyl chloride, hydrogen iodide, and an optional catalyst; and reacting the trifluoroacetyl chloride and hydrogen iodide to provide trifluoroacetyl iodide.

[0059] Aspect 2 is the process of Aspect 1, wherein in the providing step, the mole ratio of the trifluoroacetyl chloride to the hydrogen iodide is from about 1:10 to about 10:1.

[0060] Aspect 3 is the process of either of Aspect 1 or Aspect 2, wherein in the providing step, a weight ratio of the catalyst to the trifluoroacetyl chloride is from about 0.001:1 to about 0.5:1.

[0061] Aspect 4 is the process of any one of Aspects 1-3, wherein the catalyst is selected from the group consisting of silicon carbide, activated carbon, carbon molecular sieves, and combinations thereof.

[0062] Aspect 5 is the process of any one of Aspects 1-4, wherein in the reacting step, the trifluoroacetyl chloride, the hydrogen iodide, and the optional catalyst are at a temperature from 0° C. to 200° C.

[0063] Aspect 6 is a process for producing trifluoroacetyl iodide (TFAI), the process comprising: mixing trifluoroacetyl chloride, hydrogen iodide, and an optional catalyst; and heating the trifluoroacetyl chloride, hydrogen iodide, and an optional catalyst to produce trifluoroacetyl iodide and hydrogen chloride.

[0064] Aspect 7 is the process of Aspect 6, further including separating the trifluoroacetyl iodide from the hydrogen chloride, trifluoroacetyl chloride, and hydrogen iodide.

[0065] Aspect 8 is the process of either of Aspect 6 or Aspect 7, wherein the process is a continuous process.

[0066] Aspect 9 is the process of either of Aspect 6 or Aspect 7, wherein the process is a batch process.

[0067] Aspect 10 is the process of any one of Aspects 6-9, wherein the catalyst is selected from the group consisting of silicon carbide, activated carbon, carbon molecular sieves, and combinations thereof.

[0068] Aspect 11 is the process of any one of Aspects 6-10, wherein in the reacting step, the trifluoroacetyl chloride, the hydrogen iodide, and the optional catalyst are at a temperature from 0° C. to 200° C.

[0069] Aspect 12 is the process of any one of Aspects 6-11, wherein in the reacting step, the trifluoroacetyl chloride, the hydrogen iodide, and the optional catalyst are at a pressure of 5 psig to 500 psig.