CN108047019A - 2,2,2- trifluoroacetophenones clean the preparation method of high conversion - Google Patents
2,2,2- trifluoroacetophenones clean the preparation method of high conversion Download PDFInfo
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
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Abstract
The invention discloses the preparation methods of 2,2,2 trifluoroacetophenones cleaning high conversion, comprise the following steps：S1, with N, O dimethyl hydroxylamine hydrochloride is raw material, is reacted with organic base, obtains free N, O dimethyl hydroxylamines；S2, trifluoroacetic anhydride and free N, O dimethyl hydroxylamine reaction generation N, three flutolanil of O dimethyl；S3, Grignard Reagent and the three flutolanil reaction of N, O dimethyl prepare trifluoroacetophenone, by the step in the N that generates, O dimethyl hydroxylamines recycle out, be applied in S2 steps, at the same by step S1, S2 and S3 using to reaction dissolvent carry out recycling and reuse.Of the present invention 2,2,2 trifluoroacetophenones clean the preparation method of high conversion, the N higher by preparing nucleophilicity, three flutolanil of O dimethyl and grignard reagent reaction, efficiently prepare 2,2,2 trifluoroacetophenones, the by-product of production simultaneously, it may be used on preparing N, three flutolanil of O dimethyl achievees the effect that recycle.
Description
Technical field
The invention belongs to the field of chemical synthesis, are specifically related to the preparation to 2,2,2- trifluoroacetophenones cleaning high conversion
Method.
Background technology
2,2,2- trifluoroacetophenones are common chemical reagent, and the common synthetic method of 2,2,2- trifluoroacetophenones has：(1)
Trifluoroacetic acid is directly reacted with the Grignard Reagent of bromobenzene, and one-step method directly synthesizes.Yield about 60%.The operation letter of this method advantage
Single, raw material is cheap.Shortcoming：Heat release is violent, and yield is low.(2) in -40 DEG C, carbon disulfide solvent, the work of lewis acid AlCl3
Under, trifluoroacetic anhydride occurs F-K reaction with phenyl ring and prepares, yield about 70%.This method advantage：One-step synthesis method.
Shortcoming：Solvent toxicity is big, and AlCl3 is difficult, the strong acid used, alkali corrosion equipment and pollution environment.(3) fluoroform gas
It reacts, prepares with benzoic ether or chlorobenzoyl chloride.Yield 70-80%.This method advantage：One-step synthesis method object.Shortcoming has
Impurity, yield be not high.
The content of the invention
The present invention provides the preparation method of 2,2,2- trifluoroacetophenones cleaning high conversion, higher by preparing nucleophilicity
Three flutolanil of N, O- dimethyl and grignard reagent reaction, efficiently prepare 2,2,2- trifluoroacetophenones, while the by-product produced, can
It is applied to and prepares N, three flutolanil of O- dimethyl achievees the effect that recycle.
The present invention is achieved by the following technical programs.
2,2,2- trifluoroacetophenones clean the preparation method of high conversion, comprise the following steps：
S1, with N, O- dimethyl hydroxylamine hydrochloride is raw material, is reacted with organic base, obtains free N, O- dimethyl hydroxylamines；
S2, trifluoroacetic anhydride and free N, O- dimethyl hydroxylamine reaction generation N, three flutolanil of O- dimethyl；
S3, Grignard Reagent and the three flutolanil reaction of N, O- dimethyl prepare trifluoroacetophenone, by the step in generate
N, O- dimethyl hydroxylamine recycle out, are applied in S2 steps, at the same by the reaction dissolvent used in step S1, S2 and S3 into
Row recycling reuses.
Preferably, for the reaction condition in the step S1 at room temperature, to add in dichloromethane, organic base, stirring is anti-
Answer 1-2h.
Preferably, the organic base in the step S1 is triethanolamine or tri-n-butylamine.
Preferably, the reaction condition in the step S2 is the insulation reaction 2-4h at 0-15 DEG C.
Preferably, the post-processing operation in the step S2 after reaction is to add in water dilution, layering, and water mutually makes
After being washed with dichloromethane, merge organic layer, organic layer is dried using water phase, anhydrous sodium sulfate, is recycled to dry.
Preferably, operation process is in the step S3, and at 0-5 DEG C, grignard reagent is instilled N, O- diformazans
In the organic solution of three flutolanil of base, 2-3h is dripped, the reaction was continued at 0-5 DEG C 1-2h, is warming up to room temperature and is carried out reaction 6-
10h。
Preferably, reacting complete last handling process in the step S3 is, adds in saturated ammonium chloride solution and is quenched, adds in
Water is diluted, and layering, water is mutually extracted using dichloromethane solution, merges organic layer, using washing, dry, recycling
It is extremely dry.
Preferably, the inventory of N in the step S1, O- dimethyl hydrochloride and organic base, according to molar ratio, N, O-
Dimethyl hydrochloride:Organic base=1:1-1.05.
Preferably, the N of the step S1, the N in O- dimethyl hydrochloride and step S2, the throwing of three flutolanil of O- dimethyl
Doses, according to molar ratio, N, O- dimethyl hydrochlorides:Three flutolanil=1 of N, O- dimethyl:1-1.05.
Preferably, the preparation method of the Grignard Reagent in the step S3 is that Mg is added in reaction vessel, uses tetrahydrochysene
Furans disperses, and instills bromobenzene, is warming up to 55-60 DEG C of insulation reaction 0.5-1h under nitrogen protection, continues to be added dropwise the four of bromobenzene
Hydrogen tetrahydrofuran solution, the reaction was continued 2-4h after dripping off；The trifluoroacetic acid amide and the inventory of Mg are, three according to molar ratio
Fluoroacetic acid amide:Mg=1:1.3-1.4.
The beneficial effects of the present invention are：
1st, necleophilic reaction activity：Aldehyde, ketone>Ester>Carboxylic acid or carboxylate.Therefore Grignard Reagent is directly reacted with trifluoroacetic acid and selected
Selecting property is bad, and generation impurity is more, and yield is not high.Preparation method of the present invention uses N, and O- dimethyl hydroxylamines are carrier,
It is reacted with grignard reagent, by improving the nucleophilicity of substrate, the progress of positive reaction can be effectively promoted, reduce the production of impurity
It is raw；For the yield of the step more than 85%, liquid phase purity is much better than the prior art more than 95%.
2nd, preparation method of the present invention, with N, O- dimethyl hydroxylamine hydrochloride is raw material, prepare to go on a tour from N, O- bis-
Methyl hydroxylamine utilizes trifluoroacetic anhydride and free N, O- dimethyl hydroxylamines reaction generation N, three flutolanil of O- dimethyl, the step
Reaction selectivity it is preferable, yield is more than 98%, and liquid phase purity is more than 96%；And three flutolanil of N, O- dimethyl and lattice
When formula reagent reacting prepares target product, the by-product of generation is N, O- dimethyl hydroxylamines, N, and O- dimethyl hydroxylamines may be used on
In the preparation of three flutolanil of N, O- dimethyl, achieve the purpose that recycle, while do not influence the preparation of target product, target production
The yield of object is more than 85%, and liquid phase purity is more than 94.5%.
3rd, in preparation method of the present invention, the organic solvents such as dichloromethane and tetrahydrofuran have been used, will have been included
After the waste liquid of these solvents is recycled afterwards, obtained dichloromethane and tetrahydrofuran solution are applied to the preparation method
In, the yield and purity of target product are not influenced, and the yield of target product is more than 85%, and liquid phase purity is more than 95%.
Description of the drawings
Fig. 1 is the reaction equation of the preparation method of 2,2,2- trifluoroacetophenones cleaning high conversion of the present invention；
Fig. 2 is the chromatograms of the 2,2,2- trifluoroacetophenones prepared by the present embodiment 1.
Specific embodiment
Be described further below technical scheme, but claimed scope be not limited to it is described.
Embodiment 1
As described in Figure 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, comprise the following steps：
S1,1mol (97.5g) N, O- dimethyl hydroxylamine hydrochloride, three ethyl alcohol of 1mol (149.1g) are added in reaction vessel
Amine, 600ml dichloromethane at room temperature, are stirred to react 1h, obtain free N, O- dimethyl hydroxylamines；
S2, at 0 DEG C, toward the free N obtained by step 2, O- dimethyl hydroxylamines are added dropwise and contain 1mol (210g) trifluoro second
The 150ml dichloromethane solutions of acid anhydrides, 1.5h are dripped, and heat preservation the reaction was continued 1.5h after reaction, it is dilute to add in 200ml water
It releases, be layered, after water is mutually washed 2 times using 300ml dichloromethane solutions, merge organic layer, organic layer is washed using 400ml water
2 times and anhydrous sodium sulfate drying, are recycled to dry at 30-35 DEG C, obtain N to be reacted, three flutolanil of O- dimethyl；
S3,15.8gMg is added in reaction vessel, is disperseed with 200ml tetrahydrofurans, instill 50g bromobenzenes (in total
104.9g), 55 DEG C of insulation reaction 0.5h are warming up under nitrogen protection, continue that the tetrahydrofuran solution of bromobenzene is added dropwise, after dripping off
The reaction was continued 2h, obtains phenyl-magnesium-bromide solution；Phenyl-magnesium-bromide solution is added drop-wise to 0.5mol (77.53g, content at 0 DEG C
95%) in the mixed solution of three flutolanil of N, O- dimethyl and 200ml tetrahydrofurans, 2h is dripped, 0 DEG C of continuation insulation reaction
1h is warming up to room temperature and carries out reaction 6h, and reaction is finished, and is added in 100 saturated ammonium chloride solutions and is quenched, and it is dilute to add in the progress of 1000ml water
Release, be layered, water mutually using 400ml dichloromethane solutions carry out extraction 2 times, merge organic layer, using 400ml water wash 2 times,
Anhydrous sodium sulfate is dried, and is recycled at 35-38 DEG C dry, obtains 2,2,2- trifluoroacetophenones.
Yield in step S2：98.5%, liquid phase purity 96.8%；
Yield in step S3：85.2%, as described in Figure 2,2 prepared, 2,2- trifluoroacetophenones, liquid phase purity
95.17%.
Embodiment 2
The preparation method of 2,2,2- trifluoroacetophenones cleaning high conversion as described in Figure 1 is characterized in that：Including following
Step：
S1,1mol (97.5g) N, O- dimethyl hydroxylamine hydrochloride is added in reaction vessel, 1.05mol (194.5g) three is just
Butylamine, 600ml dichloromethane at room temperature, are stirred to react 2h, obtain free N, O- dimethyl hydroxylamines；
S2, at 15 DEG C, toward the free N obtained by step 2, O- dimethyl hydroxylamines are added dropwise to 1.03mol (215g) trifluoro
The 150ml dichloromethane solutions of acetic anhydride, 1h are dripped, heat preservation the reaction was continued 1h, after reaction, add in the dilution of 200ml water,
Layering after water is mutually washed 2 times using 300ml dichloromethane solutions, merges organic layer, and organic layer is washed 2 times using 400ml water
And anhydrous sodium sulfate drying, it is recycled at 30-35 DEG C dry, obtains N to be reacted, three flutolanil of O- dimethyl；
S3,16.5Mg is added in reaction vessel, is disperseed with 200ml tetrahydrofurans, it is (total to instill 50g bromobenzenes
118g), 60 DEG C of insulation reaction 1h are warming up under nitrogen protection, are continued that the tetrahydrofuran solution of bromobenzene is added dropwise, are continued after dripping off
4h is reacted, obtains phenyl-magnesium-bromide solution；Phenyl-magnesium-bromide solution is added drop-wise to 0.5mol (77.53g, content at 5 DEG C
95%) in the mixed solution of three flutolanil of N, O- dimethyl and 200ml tetrahydrofurans, 3h is dripped, 5 DEG C of continuation insulation reactions
2h is warming up to room temperature and carries out reaction 10h, and reaction is finished, and is added in 100 saturated ammonium chloride solutions and is quenched, and it is dilute to add in the progress of 1000ml water
Release, be layered, water mutually using 400ml dichloromethane solutions carry out extraction 2 times, merge organic layer, using 400ml water wash 2 times,
Anhydrous sodium sulfate is dried, and is recycled at 35-38 DEG C dry, obtains 2,2,2- trifluoroacetophenones.
Yield in step S2：98.9%, liquid phase purity 97.6%；
Yield in step S3：86.5%, liquid phase purity 95.9%.
Embodiment 3
As described in Figure 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, comprise the following steps：
S1,1mol (97.5g) N, O- dimethyl hydroxylamine hydrochloride, 1.02 (152.5g) mol, tri- second are added in reaction vessel
Hydramine, 600ml dichloromethane at room temperature, are stirred to react 1h, obtain free N, O- dimethyl hydroxylamines；
S2, at 0 DEG C, toward the free N obtained by step 2, O- dimethyl hydroxylamines are added dropwise to 1.05mol (220g) trifluoro
The 150ml dichloromethane solutions of acetic anhydride, 1.5h are dripped, and heat preservation the reaction was continued 2h after reaction, it is dilute to add in 200ml water
It releases, be layered, after water is mutually washed 2 times using 300ml dichloromethane solutions, merge organic layer, organic layer is washed using 400ml water
2 times and anhydrous sodium sulfate drying, are recycled to dry at 30-35 DEG C, obtain N to be reacted, three flutolanil of O- dimethyl；
S3,17gMg is added in reaction vessel, is disperseed with 200ml tetrahydrofurans, it is (total to instill 50g bromobenzenes
112.9g), 58 DEG C of insulation reaction 0.8h are warming up under nitrogen protection, continue that the tetrahydrofuran solution of bromobenzene is added dropwise, after dripping off
The reaction was continued 3h, obtains phenyl-magnesium-bromide solution；Phenyl-magnesium-bromide solution is added drop-wise to 0.5mol (77.53g, content at 2 DEG C
95%) in the mixed solution of three flutolanil of N, O- dimethyl and 200ml tetrahydrofurans, 2.5h is dripped, 2 DEG C of continuation insulation reactions
1.5h is warming up to room temperature and carries out reaction 8h, and reaction is finished, and is added in 100 saturated ammonium chloride solutions and is quenched, and it is dilute to add in the progress of 1000ml water
Release, be layered, water mutually using 400ml dichloromethane solutions carry out extraction 2 times, merge organic layer, using 400ml water wash 2 times,
Anhydrous sodium sulfate is dried, and is recycled at 35-38 DEG C dry, obtains 2,2,2- trifluoroacetophenones.
Yield in step S2：100%, liquid phase purity 98.8%；
Yield in step S3：88.9%, liquid phase purity 96.8%.
Comparative example 1
Trifluoroacetic acid is directly reacted with the Grignard Reagent of bromobenzene, and one-step method directly synthesizes, and heat release is violent in inverse process.
Yield 61.5%, always miscellaneous≤9.7%.
Comparative example 2
In -40 DEG C, carbon disulfide solvent, in lewis acid AlCl3Under the action of, trifluoroacetic anhydride occurs to pay with phenyl ring
It is prepared by gram acylation reaction.
Yield 72.8%, always miscellaneous≤11.5%.
Comparative example 3
Fluoroform gas is reacted with benzoic ether or chlorobenzoyl chloride, is prepared.Yield 75.6%, always miscellaneous≤13.3%.
Comparative example 4
By the N of the generation in 3 step S3 of embodiment 1- embodiments, after O- dimethyl hydroxylamines are separated, step is applied to
It is operated in S2, remaining condition is consistent with step S2, S3 in embodiment 3.
Yield in step S2：98.1%, liquid phase purity 97.4%；
Yield in step S3：85.6%, liquid phase purity 95.6%.
Comparative example 5
Dichloromethane waste liquid, tetrahydrofuran waste liquid in embodiment 1- embodiments 3 is recycled, be applied to step S1,
Step S2, in step S3, remaining condition is consistent with embodiment 1.
Yield in step S2：98.8%, liquid phase purity 97.1%；
Yield in step S3：86.2%, liquid phase purity 95.5%.
Comparative example 6
By the N of the generation in 3 step S3 of embodiment 1- embodiments, after O- dimethyl hydroxylamines are separated, step is applied to
It is operated in S2；Dichloromethane waste liquid, tetrahydrofuran waste liquid in embodiment 1- embodiments 3 is recycled, obtain dichloromethane,
Tetrahydrofuran is applied in step S2, step S3, remaining condition and embodiment 1 are consistent.
Yield in step S2：98.5%, liquid phase purity 97.8%；
Yield in step S3：85.1%, liquid phase purity 94.9%.
From embodiment 1- embodiments 3 as can be seen that step S2 yield it is higher, more than 98%, liquid phase purity 96% with
On, more than 85%, liquid phase purity, compared to the product yield of comparative example 1-3, can be good at step S3 yields more than 95%
Illustrate the N prepared, three flutolanil of O- dimethyl, when nucleophilicity is very high and grignard reagent is reacted, good, the yield of selectivity
Height, while also illustrate that the yield of step S2 is higher, N, three flutolanil purity of O- dimethyl are higher.
From embodiment 3 and comparative example 4-6, it can be seen that when by-product N, the O- dimethyl hydroxylamine of production is used to prepare
Target product is yield in step S2：98.8%, liquid phase purity 97.1%；Yield in step S3：86.2%, liquid phase purity
95.5%, illustrate that by-product N, O- dimethyl hydroxylamine can be very good suitable for synthetic route of the present invention, and will not
The reduction of yield and purity is caused, can be recycled；Expense in it will produce, the dichloromethane recycled out, tetrahydrofuran
When being applied to embodiment 1, yield in step S2：98.8%, liquid phase purity 97.1%, yield in step S3：86.2%, liquid-phase pure
Degree 95.5%, dichloromethane waste liquid, the tetrahydrofuran for illustrating to recycle out can be very good to be suitable for synthesis road of the present invention
In line, and the reduction of yield and purity will not be caused, can recycled；If simultaneously using by-product N, the O- dimethyl of production
When azanol and the dichloromethane, the tetrahydrofuran that recycle out are applied to embodiment 1, yield in step S2：98.5%, liquid phase purity
Yield in 97.8%, step S3：85.1%, liquid phase purity 94.9% illustrates by-product N, O- dimethyl hydroxylamine and recycles out
Dichloromethane waste liquid, tetrahydrofuran can be very good suitable for synthetic route of the present invention, and will not cause yield and
The reduction of purity can recycle together.
The above content is combine specific/preferred embodiment further description made for the present invention, it is impossible to
Assert that the specific implementation of the present invention is confined to these explanations.Come for general technical staff of the technical field of the invention
It says, without departing from the inventive concept of the premise, some replacements or modification can also be made to the embodiment that these have been described,
And these are substituted or variant should all be considered as belonging to protection scope of the present invention.
Claims (10)
1.2,2,2- trifluoroacetophenones clean the preparation method of high conversion, it is characterised in that：Comprise the following steps：
S1, with N, O- dimethyl hydroxylamine hydrochloride is raw material, is reacted with organic base, obtains free N, O- dimethyl hydroxylamines；
S2, trifluoroacetic anhydride and free N, O- dimethyl hydroxylamine reaction generation N, three flutolanil of O- dimethyl；
S3, Grignard Reagent and the three flutolanil reaction of N, O- dimethyl prepare trifluoroacetophenone, by the step in the N, O- that generate
Dimethyl hydroxylamine recycles out, is applied in S2 steps, at the same by step S1, S2 and S3 using to reaction dissolvent returned
Receipts reuse.
2. according to claim 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, which is characterized in that institute
Reaction condition in the step S1 stated is at room temperature, addition dichloromethane, organic base is stirred to react 1-2h.
3. according to claim 1 or 22,2,2- trifluoroacetophenones clean the preparation method of high conversion, feature exists
In the organic base in the step S1 is triethanolamine or tri-n-butylamine.
4. according to claim 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, which is characterized in that institute
Reaction condition in the step S2 stated is the insulation reaction 2-4h at 0-15 DEG C.
5. according to claim 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, which is characterized in that institute
Post-processing operation in the step S2 stated after reaction is to add in water dilution, layering, after water is mutually washed using dichloromethane,
Merge organic layer, organic layer is dried using water phase, anhydrous sodium sulfate, is recycled to dry.
6. according to claim 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, which is characterized in that institute
Operation process is in the step S3 stated, and at 0-5 DEG C, grignard reagent instilled N, three flutolanil of O- dimethyl it is organic molten
In liquid, 2-3h is dripped, the reaction was continued at 0-5 DEG C 1-2h, is warming up to room temperature and is carried out reaction 6-10h.
7. according to claim 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, which is characterized in that institute
Reacting complete last handling process in the step S3 stated is, adds in saturated ammonium chloride solution and is quenched, and adds in water and is diluted, is layered,
Water is mutually extracted using dichloromethane solution, merges organic layer, using washing, it is dry, be recycled to it is dry.
8. according to claim 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, which is characterized in that institute
The inventory of N in the step S1 stated, O- dimethyl hydrochloride and organic base, according to molar ratio, N, O- dimethyl hydrochlorides:It is organic
Alkali=1:1-1.05.
9. according to claim 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, which is characterized in that institute
State the N of step S1, the N in O- dimethyl hydrochloride and step S2, the inventory of three flutolanil of O- dimethyl, according to molar ratio,
N, O- dimethyl hydrochloride:Three flutolanil=1 of N, O- dimethyl:1-1.05.
10. according to claim 12,2,2- trifluoroacetophenones clean the preparation method of high conversion, which is characterized in that
The preparation method of Grignard Reagent in the step S3 is that Mg is added in reaction vessel, is disperseed with tetrahydrofuran, is instilled
Bromobenzene is warming up to 55-60 DEG C of insulation reaction 0.5-1h under nitrogen protection, continues that the tetrahydrofuran solution of bromobenzene is added dropwise, drips off
The reaction was continued afterwards 2-4h；The trifluoroacetic acid amide and the inventory of Mg are trifluoroacetic acid amide according to molar ratio:Mg=
1:1.3-1.4。
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| CN110343134A (en) * | 2019-08-04 | 2019-10-18 | 张震 | A kind of preparation method of bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides of photoinitiator |
| CN113024390A (en) * | 2021-02-22 | 2021-06-25 | 台州臻挚生物科技有限公司 | Synthetic method of 3',5' -dichloro-2, 2, 2-trifluoro acetophenone derivative |
| CN113461503A (en) * | 2021-08-18 | 2021-10-01 | 杭州臻挚生物科技有限公司 | Preparation method of trifluoro acetophenone derivatives |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343134A (en) * | 2019-08-04 | 2019-10-18 | 张震 | A kind of preparation method of bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides of photoinitiator |
| CN110343134B (en) * | 2019-08-04 | 2022-03-15 | 张震 | Preparation method of photoinitiator bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide |
| CN113024390A (en) * | 2021-02-22 | 2021-06-25 | 台州臻挚生物科技有限公司 | Synthetic method of 3',5' -dichloro-2, 2, 2-trifluoro acetophenone derivative |
| WO2022174524A1 (en) * | 2021-02-22 | 2022-08-25 | 台州臻挚生物科技有限公司 | Method for synthesizing 3',5'-dichloro-2,2,2-trifluoroacetophenone derivative |
| CN113024390B (en) * | 2021-02-22 | 2023-12-05 | 台州臻挚生物科技有限公司 | Synthesis method of 3',5' -dichloro-2, 2-trifluoro acetophenone derivative |
| CN113461503A (en) * | 2021-08-18 | 2021-10-01 | 杭州臻挚生物科技有限公司 | Preparation method of trifluoro acetophenone derivatives |
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