CN1034215C - Synthetic method for fluorine-containing Beta-diketone - Google Patents
Synthetic method for fluorine-containing Beta-diketone Download PDFInfo
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- CN1034215C CN1034215C CN92108563A CN92108563A CN1034215C CN 1034215 C CN1034215 C CN 1034215C CN 92108563 A CN92108563 A CN 92108563A CN 92108563 A CN92108563 A CN 92108563A CN 1034215 C CN1034215 C CN 1034215C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/516—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of nitrogen-containing compounds to >C = O groups
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Abstract
The present invention relates to a synthesis method for fluorine-containing beta-diketone. Under the action of sodium hydrosulfite and alkali, enol siloxane and perfluorovulcanization alkane carry out perfluoroalkylation reaction in a polar solvent and react with amine, and the obtain solution is adjusted to acidity with hydrochloric acid to carry out hydrolysis reaction continuously. Three steps of reaction are carried out in a container continuously, and an intermediate product does not need separation and purification. The method has the advantages of mild reaction condition, simple operation, high yield and low cost.
Description
The invention belongs to the synthetic method of fluorine-containing beta-diketon
Fluorine-containing beta-diketon chemically is being widely used, and it is a kind of effective extraction agent of separating rare-earth metal, also is the important intermediate of synthesizing heterocyclic compounds, and the lanthanide chelate of fluorine-containing beta-diketon also is used as
1Shift reagent in the H-NMR test.In general, the synthetic the most frequently used method of fluorine-containing beta-diketon is carried out [A.F.Cockerill, Chem.Rev. by the Claisen condensation reaction, 73,551 (1973)], but this method because some inevitably pay reaction exists, productive rate is very low, and the purifying of product is also quite difficult.
For this reason, it is easy to the present invention seeks to seek a method, the method for the synthetic fluorine-containing beta-diketon that reaction conditions gentleness and productive rate are high.
The present invention be silyl enol ether and perfluoroalkyl iodide under vat powder and alkali effect, in polar solvent, carry out the perfluoroalkylation reaction, with the amine reaction, be that 1-6 proceeds hydrolysis reaction with hydrochloric acid conditioned reaction liquid PH then again, promptly get the fluorine-containing beta-diketon of product.
Synthetic method of the present invention can be represented by following formula:
R is the straight chain of 1-10 carbonatoms or the alkyl that has side chain in the following formula, R
1, R
2, R
3Be respectively the straight chain of a phenyl or 1-4 carbonatoms or the alkyl that has side chain, R
1, R
2, R
3Can be group identical or that have nothing in common with each other, R
FBe the straight chain of 1-10 carbonatoms or the alkyl that has side chain, R
FBe R '
FAnd CF
2Sum.
Used alkali can be metal oxide in the reaction, oxyhydroxide, and carbonate, supercarbonate and phosphoric acid salt etc. are as calcium oxide, magnesium oxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonium hydroxide, salt of wormwood, yellow soda ash, saleratus, sodium bicarbonate, sodium hydrogen phosphate and Sodium phosphate dibasic etc.
The polar solvent of using in the reaction is a water, acetonitrile, propionitrile, methylene dichloride, chloroform, dimethyl formamide, N,N-DIMETHYLACETAMIDE, diethylformamide, alcohols such as methyl alcohol, ethanol, propyl alcohol etc., can adopt a kind of composition mixed solvent in water or water and other solvent, the proportioning of water and other solvent is 1-10: 10-1, solvent load are every mol silyl enol ether 50-10000 milliliters.
The amine of using in the reaction is primary amine such as n-Butyl Amine 99, normal hexyl Amine, and hexahydroaniline etc. also can be secondary amine such as diethylamine, dipropyl amine, hexahydropyridine etc.
The synthetic method of the fluorine-containing beta-diketon of the present invention comprises (1) silyl enol ether, and perfluoroalkyl iodide, vat powder and alkali carry out the perfluoroalkylation reaction in polar solvent.Temperature of reaction is 15-60 ℃, and the time is 1-10 hour, uses
19F-NMR follows the tracks of reaction, and (2) add amine, continues stirring reaction 1-10 hour, and (3) add 4N aqueous hydrochloric acid conditioned reaction liquid PH is 1-6, continues to stir 1-10 hour, and this three-step reaction carries out in container in succession, and intermediate product does not need separation and purification.The mol ratio of reactant is a silyl enol ether in reaction: perfluoroalkyl iodide: vat powder: alkali: amine=1: 1: 0.5-5: 0.5-5: 3-10.If replace amine to react with ammoniacal liquor, because of ammonium hydroxide just can be used as the alkali of using in the perfluoroalkylation reaction, therefore above-mentioned three-step reaction can be reduced to two step reactions (referring to embodiment 2).The mol ratio of each reactant is a silyl enol ether in the reaction: perfluoroalkyl iodide: vat powder: ammoniacal liquor=1: 1: 0.5-5: 3-10.After reaction finished, the reaction mixture extracted with diethyl ether was taken out solvent ether in the extraction liquid, got crude product, carried out purifying with underpressure distillation or rapid column chromatography method, promptly got the fluorine-containing beta-diketone compound of product.Productive rate is 72-93%.The physico-chemical constant of products therefrom is consistent with the bibliographical information value.
The advantage of synthetic method of the present invention is to carry out owing to being reflected under the mild conditions, and reaction preference is improved greatly, has avoided many pairs of reactions.And three steps (or the two step) reaction that comprises in the building-up process is to carry out in succession, need not carry out the separation and purification of intermediate product, not only easy to operate, also reduced the loss in the sepn process, and this just makes productive rate improve greatly.Also have present method reaction to carry out at aqueous phase, easy and simple to handle.In addition, used reagent vat powder, amine (or ammoniacal liquor), solvent etc. all are that price is cheaper, have reduced the cost of present method, so this synthetic method has an Application Prospect industrial.
The following example will help understanding of the present invention, but not limit content of the present invention.
Embodiment 1
With 0.01 mol silyl enol ether, 0.01 mol perfluoroalkyl iodide, a certain amount of vat powder, alkali and solvent join in the reaction flask successively.Stir at a certain temperature and use
19F-NMR follows the tracks of reaction, finishes until the perfluoroalkyl iodide total overall reaction, and the reaction times is 1-10 hour.In reaction system, add amine again, continue to stir 1-10 hour.With the 4N aqueous hydrochloric acid reaction solution is adjusted to acidity (PH=1-6) then, continues to stir stopped reaction 1-10 hour.Reaction mixture extracted with diethyl ether (3 * 25 milliliters), extraction liquid is used saturated sodium bicarbonate solution (1 * 30 milliliter) successively, and anhydrous magnesium sulfate drying is used in saturated nacl aqueous solution (1 * 30 milliliter) washing.After taking out the ether that desolvates, (eluent is a sherwood oil: ethyl acetate :=10: purifying crude product 1 mixed solvent) promptly gets the fluorine-containing beta-diketone compound of product with underpressure distillation or rapid column chromatography.Close the amount that kind of raw material reagent adds, temperature of reaction, time and product see Table sequence number 1-13 among the I.
Embodiment 2
With 0.01 mol silyl enol ether, 0.01 mol perfluoroalkyl iodide, a certain amount of vat powder, 25% ammoniacal liquor and solvent join in the reaction flask successively.Stir at a certain temperature, use
19F-NMR follows the tracks of reaction, finishes until the perfluoroalkyl iodide total overall reaction, and the reaction times is 1-10 hour.Reaction system is acidified to reaction system with the 4N aqueous hydrochloric acid is acid (PH=1-6), continue to stir stopped reaction 1-10 hour.Carry out aftertreatment according to embodiment 1 method, get the fluorine-containing beta-diketone compound of product.Close the amount that kind of raw material reagent adds, temperature of reaction, time and product see Table sequence number 14-18 among the I.
Table I
Continuous Table I
Claims (5)
1. the synthetic method of a fluorine-containing beta-diketon, it is characterized in that with silyl enol ether (
), perfluoroalkyl iodide (R
FI), V-Brite B and alkali carry out the perfluoroalkylation reaction in polar solvent, add the amine reaction again, and then be 1-6 with hydrochloric acid conditioned reaction liquid PH, proceed hydrolysis reaction, this three-step reaction carries out in container in succession, and intermediate product does not need separation and purification, R is the straight chain of C=1-10 or the alkyl that has side chain in the formula, R
1, R
2, R
3For the straight chain of phenyl or C=1-4 or have the alkyl of side chain, can be identical or have nothing in common with each other R
FFor the straight chain of C=1-10 or have the alkyl of side chain, R
F' be to compare R
FFew carbon fluorine chain CF
2Straight chain or have the alkyl of side chain, the mol ratio of reactant is a silyl enol ether: perfluoroalkyl iodide: V-Brite B: alkali: amine=1: 1: 0.5-5: 0.5-5: 3-10, temperature of reaction is 15-60 ℃, the reaction times is 1-10 hour.
2. by the described synthetic method of claim 1, it is characterized in that alkali is metal oxide, oxyhydroxide, carbonate, supercarbonate and phosphoric acid salt, comprise calcium oxide, magnesium oxide, oxygen potassium oxide, sodium hydroxide, calcium hydroxide, ammonium hydroxide, salt of wormwood, yellow soda ash, saleratus, sodium bicarbonate, sodium hydrogen phosphate and Sodium phosphate dibasic.
3. by the described synthetic method of claim 1, it is characterized in that polar solvent is water, acetonitrile, propionitrile, methylene dichloride, chloroform, dimethyl formamide, N,N-DIMETHYLACETAMIDE, diethylformamide, alcohols, alcohols comprises methyl alcohol, ethanol, propyl alcohol, can adopt a kind of composition mixed solvent in water or water and other solvent, the proportioning of water and other solvent is 1-10: 10-1, solvent load are every mol silyl enol ether 50-10000 milliliters.
4. by the described synthetic method of claim 1, it is characterized in that amine is primary amine or secondary amine, wherein primary amine comprises n-Butyl Amine 99, normal hexyl Amine, hexahydroaniline; Secondary amine comprises diethylamine, dipropyl amine, hexahydropyridine.
5. by the described synthetic method of claim 1, it is characterized in that the amine aqueous ammonia to replace, then the mol ratio of reactant is a silyl enol ether: perfluoroalkyl iodide: V-Brite B: ammoniacal liquor=1: 1: 0.5-5: 3-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108563A CN1034215C (en) | 1992-09-18 | 1992-09-18 | Synthetic method for fluorine-containing Beta-diketone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108563A CN1034215C (en) | 1992-09-18 | 1992-09-18 | Synthetic method for fluorine-containing Beta-diketone |
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| Publication Number | Publication Date |
|---|---|
| CN1084158A CN1084158A (en) | 1994-03-23 |
| CN1034215C true CN1034215C (en) | 1997-03-12 |
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| CN92108563A Expired - Fee Related CN1034215C (en) | 1992-09-18 | 1992-09-18 | Synthetic method for fluorine-containing Beta-diketone |
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| CN104725206A (en) * | 2013-12-18 | 2015-06-24 | 浙江化工院科技有限公司 | Trifluoroacetylacetone preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU523076A1 (en) * | 1973-07-30 | 1976-07-30 | Институт Органической Химии Ан Украинской Сср | The method of obtaining fluorinated diketones |
| US4201726A (en) * | 1977-05-17 | 1980-05-06 | Hoffmann-La Roche Inc. | Synthesis of Vitamin E |
| CN1031366A (en) * | 1987-07-18 | 1989-03-01 | 北京市化工研究院 | The manufacture method of beta-diketone compounds |
| EP0346279A1 (en) * | 1988-06-06 | 1989-12-13 | Ciba-Geigy Ag | Propane-1,3-dione derivatives and their use as stabilizing agents for chlorine-containing polymerisates |
-
1992
- 1992-09-18 CN CN92108563A patent/CN1034215C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU523076A1 (en) * | 1973-07-30 | 1976-07-30 | Институт Органической Химии Ан Украинской Сср | The method of obtaining fluorinated diketones |
| US4201726A (en) * | 1977-05-17 | 1980-05-06 | Hoffmann-La Roche Inc. | Synthesis of Vitamin E |
| CN1031366A (en) * | 1987-07-18 | 1989-03-01 | 北京市化工研究院 | The manufacture method of beta-diketone compounds |
| EP0346279A1 (en) * | 1988-06-06 | 1989-12-13 | Ciba-Geigy Ag | Propane-1,3-dione derivatives and their use as stabilizing agents for chlorine-containing polymerisates |
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| CN1084158A (en) | 1994-03-23 |
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