CN1316423A - Liquid-phase fluorination process for chloromethyl pyridine compounds - Google Patents
Liquid-phase fluorination process for chloromethyl pyridine compounds Download PDFInfo
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Abstract
A liquid-phase fluorination process for chloromethyl pyridine compounds features that the reaction is conducted of chloromethyl pyridine compound with anhyudrous hydrogen fluoride at 100-250 deg.C and high pressure under existance of catalyst. Its resultant is an intermediate used for synthes of low-poison efficient fluoric agricultural chemical and raticide.
Description
The present invention relates to the liquid-phase fluorination process of chloromethyl pyridine compound.
One methyl fluoride pyridine, difluoromethyl pyridine and category of compound of trifluoro methylpyridine are the important intermediate that is used for synthesizing efficient, low toxicity fluoro-containing pesticide and rodenticide etc.Up to the present, synthetic method mainly contains two kinds, and a kind of is by pyridine and CF
3I etc. are through the catalyzed reaction preparation, but reaction is very difficult, and productive rate is very low.Another kind is that mainly to be generated product be 5-flumethiazine through fluoridation by chloromethylpyridine.For example with SbF
3As fluorizating agent, in the time of 80～120 ℃, feed chlorine and displace fluorion, with the reaction of 2-chloro-5-nitrapyrin, the productive rate of the 2-chloro-5-5-flumethiazine that makes is the yellow pretty tinkling of pieces of jade of 37.8%[etc., " agricultural chemicals ", 1989, (1), 1].With AlCl
3Or CrF
3As catalyzer, 350 ℃ of temperature of reaction, a step vapor phase process can prepare 2-chloro-5-5-flumethiazine, obtains but the catalyzer of this method is difficult, and temperature of reaction too high [JP62/12758,21 Jan 1987].In addition, the method for liquid-phase fluorination has begun to be applied to the fluoridation [" agricultural chemicals ", 1994, (4), 1] of o-chlorotrichlorotoluene.
The liquid-phase fluorination process that the purpose of this invention is to provide a kind of chloromethyl pyridine compound.
The invention provides a kind of liquid-phase fluorination method of chloromethyl pyridine compound.Mainly be with chloromethyl pyridine compound in the presence of catalyzer with anhydrous hydrogen fluoride generation fluoridation.Reaction generally is under high pressure to carry out.Raw material, catalyzer, anhydrous hydrogen fluoride etc. are added in the autoclave, and heated and stirred is warmed up to temperature of reaction, reacts 2-40 hour, also can prolong the reaction times.
Specifically, the present invention be 100～250 ℃, pressure be 2～15MPa and catalyzer in the presence of, general molecular formula is
Chloromethyl compound and the mol ratio of anhydrous hydrogen fluoride be 1: 2-15, recommending molar ratio is 1: 5-15; The weight ratio of catalyzer and chloromethyl compound is 1-10%, and the recommendation weight ratio is 4-6%; Fluoridation takes place 2-40 hour, recommendation response 4-20 hour, and got final product in the general 4-6 of laboratory reaction hour.Having obtained the useful molecules general formula is described as
A higher fluorine, difluoro or the category of compound of trifluoro methylpyridine of purity, m=0,1 or 2 in the formula, n=1,2 or 3, m＜n, R
1=H, HS, CH
3O, (CH
3)
2N or halogen.Described catalyzer is SbCl
5, KBF
4, CuCl
2Or FeCl
3, recommend to use iron trichloride.Increase hydrofluoric consumption and be of value to the raising productive rate.
Can be as follows after the reaction through aftertreatment: cool, the venting pressure release, byproduct hydrogen chloride and excessive hydrogen fluoride absorb with alkali such as aqueous sodium hydroxide solution.Material is with in alkali such as the aqueous sodium carbonate and behind the hydrogen fluoride, with organic solvent such as ethyl acetate extraction in the still.Dry extraction liquid filters, and extraction solvent is reclaimed in the filtrate distillation.Heat up and steam the product crude product, last rectification under vacuum can obtain highly purified fluorinated product.Excessive hydrogen fluoride recovery set can be used in the industrial production.Hydrogenchloride can be made into technical hydrochloric acid and is used.
Reacting available equation is described below for example:
The reaction conditions that above-mentioned reaction is recommended be 130～150 ℃, pressure be 2～7MPa and catalyzer in the presence of,
Obtained in 4-20 hour with the reaction under the effect of catalyzer of anhydrous hydrogen fluoride
200～240 ℃, pressure be 6～13MPa and catalyzer in the presence of,
With anhydrous hydrogen fluoride reaction 4-20 hour, obtained
Wherein m, n, catalyzer and other reaction conditions as previously mentioned.
The present invention has also studied the consumption of kind, reactant of concrete reaction conditions such as temperature, catalyzer to the influence of reaction result, respectively shown in table 1, table 2, table 3 etc.
Table 1 temperature of reaction is to result's influence
| Lot number | Raw material (gram) | Catalyzer | Reaction conditions | Content of fluoride in the crude reaction (%) | |||||||
| Temperature ℃ | Pressure MPa | Time Hrs | |||||||||
| ?0F | ?HF | ??4F | ????3F | ?2F | ?1F | ?0F | |||||
| ?09 | ?173 | ?200 | ?KBF 4 | ?130 | ?3.2 | ?6.0 | ??-- | ????0.97 | ?26.78 | ?69.27 | ?0.18 |
| ?13 | ?173 | ?200 | ?KBF 4 | ?140 | ?4.1 | ?6.0 | ??-- | ????2.13 | ?84.90 | ?11.68 | ?0.04 |
| ?16 | ?173 | ?200 | ?KBF 4 | ?150 | ?5.0 | ?6.0 | ??-- | ????3.01 | ?92.12 | ?2.79 | ?-- |
| ?06 | ?173 | ?200 | ?KBF 4 | ?180 | ?8.0 | ?6.0 | ??1.04 | ????97.37 | ?0.80 | ?0.30 | ?-- |
From table 1 09 batch, 13 batches, 16 batches relevant data as can be seen, for reaction
; adopt same catalyzer under identical reaction times condition; temperature of reaction is mainly the 1F compound in the time of 130 ℃; it is to be relatively easy to that the first step is fluoridized; when selecting 140 ℃ of reactions for use; the 1F compound begins to change into the 2F compound, and the 1F compound is converted into the 2F compound significantly when temperature of reaction is elevated to 150 ℃, has only that primary product just can be the 3F compound when temperature is elevated to 180 ℃.Same, for reaction
Also be the rising with temperature, degree of fluorination is high more.Illustrate that fluorination process is a proceed step by step, energy level distributes also apparent in view, and the activation energy of per step reaction rises step by step, and go up the 3rd fluorine is the comparison difficulty.
Table 2 anhydrous hydrogen fluoride concentration is to the influence of reaction result
| Lot number | Raw material (gram) | Catalyzer | Reaction conditions | Content of fluoride in the crude reaction (%) | |||||||
| Temperature ℃ | Pressure MPa | Time Hrs | |||||||||
| ?0F | ?HF | ?4F | ?3F | ?2F | ?1F | ?0F | |||||
| ?09-01 | ?173 | ?200 | ?KBF 4 | ?130 | ?3.2 | ?6.0 | ?-- | ?0.97 | ?26.78 | ?69.27 | ?0.18 |
| ?09-02 | ?-- | ?100 | ?-- | ?130 | ?1.8 | ?6.0 | ?-- | ?3.00 | ?33.98 | ?62.98 | ?-- |
| ?10-01 | ?173 | ?200 | ?CuCl 2 | ?130 | ?2.9 | ?6.0 | ?-- | ?0.58 | ?7.28 | ?88.53 | ?2.52 |
| ?10-02 | ?-- | ?100 | ?-- | ?130 | ?1.7 | ?6.0 | ?-- | ?2.26 | ?35.66 | ?61.94 | ?0.09 |
09-01,09-02 or 10-01,10-02 are very easy to find under identical temperature condition from table 2, adopt same catalyzer respectively, react postcooling venting pressure release in 6 hours, sampling analysis.Add anhydrous hydrogen fluoride again and continue reaction 6 hours.Increase hydrofluoric concentration as can be seen from the analytical results of front and back, the 1F compound obviously is transformed into the 2F compound in the product.But transform not exclusively, the influence that concentration is described is not as Temperature Influence.
Table 3 catalyzer is to the influence of reaction result
| Lot number | Raw material (gram) | Catalyzer | Reaction conditions | Content of fluoride in the crude reaction (%) | |||||||
| Temperature ℃ | Pressure MPa | Time Hrs | |||||||||
| ?0F | ?HF | ?4F | ?3F | ?2F | ?1F | ?0F | |||||
| ?14 | ?173 | ?200 | ?SbCl 5 | ?150 | ?4.5 | ?6.0 | ?-- | ?3.36 | ?70.46 | ?24.36 | ?-- |
| ?16 | ?173 | ?200 | ?KBF 4 | ?150 | ?5.0 | ?6.0 | ?-- | ?3.01 | ?92.12 | ?2.79 | ?-- |
| ?17 | ?173 | ?200 | ?CuCl 2 | ?150 | ?4.7 | ?6.0 | ?-- | ?15.09 | ?81.92 | ?0.26 | ?-- |
| ?11 | ?173 | ?200 | ?FeCl3 | ?150 | ?5.5 | ?6.0 | ?2.22 | ?95.02 | ?1.63 | ?0.59 | ?-- |
Fluoridation is easy to take place under the existence of catalyzer as long as have as can be seen from table 1, table 2, table 3.No matter the content of 0F compound is all very low or do not have under what condition.Illustrate that first fluorine is easy to.Find out that from the relevant data of table 3 under identical temperature condition, the catalytic activity of fluorination catalyst iron trichloride is the highest.
We adopt 2-chloro-4-nitrapyrin and 2-chloro-5-nitrapyrin to study the influence of different material to fluoridation as raw material respectively, can find that from top experimentation fluoridizing of 2-chloro-4-nitrapyrin is more much more difficult than fluoridizing of 2-chloro-5-nitrapyrin.Reach identical degree of fluorination, the fluorination reaction temperature of 2-chloro-4-nitrapyrin will exceed about more than 50 ℃, and the reaction times is also much longer.The trichloromethyl that No. 4 positions on the pyridine ring are described is fluoridized than the trichloromethyl of No. 5 positions is more difficult, and required activation energy is higher.
The present invention adopts the method for liquid-phase fluorination, filter out the catalyzer and the reaction process condition of preparation 5-flumethiazine, difluoro one chloromethylpyridine, a fluorine dichloromethyl pyridine compounds and their, easy and simple to handle, excessive capable of circulation the applying mechanically of HF in the reaction, the HCl that produces can further make industrial goods, productive rate of the present invention can reach more than 60%, than before gaseous fluoridizing method or other method breakthrough is arranged, and get ready for suitability for industrialized production.
Embodiment 1
The preparation of 2-chloro-4-one fluorine dichloromethyl pyridine
Adding content is 98% 2-chloro-4-nitrapyrin 175 grams in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer antimony pentachloride 8 grams.Heated and stirred, be warmed up to 200 ℃ after the insulation 16 hours, top pressure is 9MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate pH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid is used anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, rectification under vacuum collect 115～120 ℃/-cut 112.5 grams of 0.0985MPa, the content of product 2-chloro-4-one fluorine dichloromethyl pyridine is 98%.The reaction yield is 69.23%.
Embodiment 2
The preparation of 2-chloro-4-difluoro one chloromethylpyridine
Adding content is 98% 2-chloro-4-nitrapyrin 175 grams in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer antimony pentachloride 8 grams.Heated and stirred, be warmed up to 215 ℃ after the insulation 16 hours, top pressure is 11MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid is used anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, rectification under vacuum collect 90～95 ℃/-cut 90.5 grams of 0.0935MPa, the content of product 2-chloro-4-difluoro one chloromethylpyridine is 98%.The reaction yield is 60.33%.
Embodiment 3
The preparation of 2-chloro-4-5-flumethiazine
Adding content is 98% 2-chloro-4-nitrapyrin 175 grams in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer antimony pentachloride 8 grams.Heated and stirred, be warmed up to 230 ℃ after the insulation 16 hours, top pressure is 13MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid was with anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, and 140～145 ℃ cut 13.8 grams are collected in rectifying, and the content of product 2-chloro-4-5-flumethiazine is 98%.The reaction yield is 10.04%.
Embodiment 4
The preparation of 2-chloro-5--fluorine dichloromethyl pyridine
Adding content is 98% 2-chloro-5-nitrapyrin 175 grams in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer antimony pentachloride 8 grams.Heated and stirred, be warmed up to 130 ℃ after the insulation 4 hours, top pressure is 2.9MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid is used anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, rectification under vacuum collect 112～114 ℃/-cut 103 grams of 0.098Mpa, the content of product 2-chloro-5-one fluorine dichloromethyl pyridine is 98%.The reaction yield is 63.38%.
Embodiment 5
The preparation of 2-chloro-5-difluoro one chloromethylpyridine
Adding content is 98% 2-chloro-5-nitrapyrin 175 grams in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer anhydrous cupric chloride 8 grams.Heated and stirred, be warmed up to 140 ℃ after the insulation 4 hours, top pressure is 4.8MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid is used anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, rectification under vacuum collect 95～100 ℃/-cut 98 grams of 0.0950Mpa, the content of product 2-chloro-5-difluoro one chloromethylpyridine is 98%.The reaction yield is 65.33%.19F-NMR:-27ppm。
Embodiment 6
The preparation of 2-chloro-5-5-flumethiazine
Adding content is 98% 2-chloro-5-nitrapyrin 175 grams in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer iron trichloride 8 grams.Heated and stirred, be warmed up to 150 ℃ after the insulation 6 hours, top pressure is 6.0MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid was with anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, and 148～152 ℃ of cuts, 86.8 grams are collected in rectifying, and the content of product 2-chloro-5-5-flumethiazine is 98%.The reaction yield is 63.13%.19F-NMR:-13ppm。
Embodiment 7
The preparation of 4-5-flumethiazine
Adding content is 98% 4-nitrapyrin 150 grams in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer antimony pentachloride 8 grams.Heated and stirred, be warmed up to 200 ℃ after the insulation 6 hours, top pressure is 9MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid was with anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, cut 56.5 grams that rectification under vacuum is collected, and the content of product 4-5-flumethiazine is 98%.The reaction yield is 50.35%
Embodiment 8
The preparation of 3-5-flumethiazine
Adding content is 98% 3-nitrapyrin 200 grams in 0.5 liter of autoclave, anhydrous hydrogen fluoride 100 grams, catalyzer antimony pentachloride 8 grams.Heated and stirred, be warmed up to 150 ℃ after the insulation 6 hours, top pressure is 6.0MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid filters with anhydrous sodium sulfate drying 4 hours, and ethyl acetate is reclaimed in the filtrate distillation, and cut 78 grams are collected in rectification under vacuum, and the content of product 3-5-flumethiazine is 98%.The reaction yield is 69.51%.
Embodiment 9
The preparation of 2-sulfydryl-5-5-flumethiazine
Adding content is 2-sulfydryl-5-nitrapyrin 175 grams of 98% in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer antimony pentachloride 4 grams.Heated and stirred, be warmed up to 150 ℃ after the insulation 6 hours, top pressure is 6.0MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid was with anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, concentrates to such an extent that yellow solid 121 restrains, and the content of product 2-sulfydryl-5-5-flumethiazine is 98%.The reaction yield is 88.26%.
Embodiment 10
The preparation of 2-methoxyl group-5-5-flumethiazine
Adding content is 2-methoxyl group-5-nitrapyrin 175 grams of 98% in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer antimony pentachloride 8 grams.Heated and stirred, be warmed up to 150 ℃ after the insulation 6 hours, top pressure is 6.0MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid was with anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, and cut 81.5 grams are collected in rectification under vacuum, and the content of product 2-methoxyl group-5-5-flumethiazine is 98%.The reaction yield is 60.28%.
Embodiment 11
The preparation of 2-(N, N-dimethylamino)-5-5-flumethiazine
Adding content is 2-(N, N-dimethylamino)-5-nitrapyrin 183 grams of 98% in 0.5 liter of autoclave, anhydrous hydrogen fluoride 200 grams, catalyzer antimony pentachloride 15 grams.Heated and stirred, be warmed up to 150 ℃ after the insulation 6 hours, top pressure is 6.0MPa.Reaction finishes postcooling to room temperature.Byproduct of reaction hydrogenchloride in the still and excessive raw material hydrogen fluoride are absorbed with aqueous sodium hydroxide solution.Material N in the still
2Be pressed in 2 liters of frozen water.With 5% aqueous sodium carbonate PH=8～9 that neutralize, use the ethyl acetate extraction aqueous solution, extraction liquid was with anhydrous sodium sulfate drying 4 hours, filter, ethyl acetate is reclaimed in the filtrate distillation, and cut 98 grams are collected in rectification under vacuum, and the content of product 2-(N, N-dimethylamino)-5-5-flumethiazine is 98%.The reaction yield is 67.50%.
Claims (6)
1. the liquid-phase fluorination process of a chloromethyl pyridine compound, it is characterized in that 100～250 ℃, pressure be 2～15MPa and catalyzer in the presence of, general molecular formula is
Chloromethyl pyridine compound and the mol ratio of anhydrous hydrogen fluoride be 1: 2-15, the weight ratio of catalyzer and chloromethyl compound is 1-10%, fluoridation takes place 2-40 hour, has obtained general molecular formula and has been
A fluorine, difluoro or category of compound of trifluoro methylpyridine, m=0,1 or 2 in the formula, n=1,2 or 3, m＜n, R
1=H, HS, CH
3O, (CH
3)
2N or halogen, described catalyzer is SbCl
5, KBF
4, CuCl
2Or FeCl
3
2. the liquid-phase fluorination process of a kind of chloromethyl pyridine compound as claimed in claim 1 is characterized in that the general molecular formula of described chloromethyl pyridine compound is
, m, R in the formula
1According to claim 1.
3. the liquid-phase fluorination process of a kind of chloromethyl pyridine compound as claimed in claim 1 is characterized in that the general molecular formula of described chloromethyl pyridine compound is
M, R in the formula
1According to claim 1.
4. the liquid-phase fluorination process of a kind of chloromethyl pyridine compound as claimed in claim 2, it is characterized in that 130～150 ℃, pressure be 2～7MPa and catalyzer in the presence of,
With the mol ratio of anhydrous hydrogen fluoride be 1: 5-15, reacted m, R in the formula 4-20 hour
1, catalyzer is as described in the claim 2.
5. the liquid-phase fluorination process of a kind of chloromethyl pyridine compound as claimed in claim 3, it is characterized in that 200～240 ℃, pressure be 6～13MPa and catalyzer in the presence of,
With the mol ratio of anhydrous hydrogen fluoride be 1: 5-15, reacted m, R in the formula 4-20 hour
1, catalyzer is as described in the claim 3.
6. as the liquid-phase fluorination process of claim 1,2 or 3 described a kind of chloromethyl pyridine compounds, it is characterized in that described catalyzer is an iron trichloride.
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| CN105820112A (en) * | 2016-06-06 | 2016-08-03 | 山东福尔有限公司 | Preparation method of 2-cholrine-5-trifluoromethyl pyridine |
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