CN103193587B - Synthetic method of tetrafluoro adamantane - Google Patents
Synthetic method of tetrafluoro adamantane Download PDFInfo
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- CN103193587B CN103193587B CN201310129601.8A CN201310129601A CN103193587B CN 103193587 B CN103193587 B CN 103193587B CN 201310129601 A CN201310129601 A CN 201310129601A CN 103193587 B CN103193587 B CN 103193587B
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Abstract
The invention provides a synthetic method of tetrafluoro adamantane. The method is green and environment-friendly, simple to operate, high in yield and high in purity. The synthetic method concretely comprises the steps of adding Slectrfluor(1-chloromethyl-4-florine-1,4-diazotize bicycle [2.2.2] octane-bi(fluoroboric acid)salt) and a catalyst to adamantane, wherein the solvent is a mixed solution of methanol and water, reacting at 10-50 DEG C, and synthetizing 1,3,5,7-tetrafluoro adamantane by one step. Compared with the prior art, the synthetic method has the significant advantages that (1) the fuorinated reagent used by the method is a novel solid fuorinated reagent, and is convenient to store and use, and free of poison and pollution; (2) tetrafluoro adamantane derivant is synthetized by one step; the synthetic step is short; and the yield is 72%; and (3) the synthetic method is mild in reaction condition, free of high temperature and high pressure, free of a corrosion-resistant reaction container, and free of a special reaction container.
Description
Technical field
The present invention relates to a kind of synthetic method of tetrafluoro adamantane derivative, be specifically related to the synthetic method of 1,3,5,7-tetrafluoro adamantane.
Background technology
Diamantane is a kind of saturated caged alkane, is made up of ten carbon atoms and 16 hydrogen atoms, and its basic framework is similar to an adamantine lattice element.In its molecular weight ranges, diamantane is closest to spherical hydrocarbon molecules in known molecular, and its rigidity ring system and symmetrical structure determine it and have unique physical features and chemical property.The chemically reactive of diamantane is slightly lower than benzene, and at typical condition and nitric acid, chromic acid, the reagent such as potassium permanganate are not had an effect, but can replace under certain catalysts influence, oxidation, the reactions such as rearrangement.4 bridgehead positions (1,3,5,7) as diamantane can pass through substitution reaction (halogenation, nitrated, sulfonation, alkylation etc.) and form numerous adamantane derivative.Diamantane and derivative of many uses, in various fields widespread uses such as biological medicine, functional polymer, lubricating oil, catalyzer, tensio-active agent, sensitive materials, agricultural chemicals, be called as fine chemical material of new generation.This year, the state such as American-European, Japan and Korea S dropped into the research of a large amount of funds in synthesis containing adamantyl functional polymer field.Research shows: main chain or the side chain of adamantane framework being introduced the functional high-polymer polymkeric substance such as polycarbonate, polymeric amide, polysulfones, polyethers, urethane and polyimide, can significantly improve the thermostability of polymkeric substance, chemical stability, optical stability, dielectric properties and mechanical property.Therefore the synthesis preparation of adamantane derivative is more and more subject to a concern interest of numerous scientific workers.
1,3,5,7-tetrafluoro adamantane is important adamantane derivative, and four stable C-F keys can make four end of the bridge carbon more stable, thus becomes the important intermediate of synthesis bridge carbon derivative.At present, 1,3,5,7-tetrafluoro adamantane uses NEt
3-5HF, is obtained by electrochemical method synthesis, this method complex process, extremely strong to the dependency of laboratory apparatus, expensive reagents and being not easy to obtain, operational difficulty, by product is many, and synthetic product is for singly to fluoridize, twoly fluoridize, borontrifluoride and tetrafluorizated mixture, productive rate is up to 60%, and productive rate is lower.( Journal of Organic Chemistry. 2008, 73, 4186–4189)。Also have report to be through tetrahydroxy adamantane and be obtained by reacting tetrafluoro adamantane with fluorination reagent, this method productive rate higher (reaching 95%), but tetrahydroxy adamantane is expensive, synthesis difficulty, actual application value is not high.（ J. Am. Chem. Soc. 2002, 124, 7728-7736）
Summary of the invention
The object of the invention is to the shortcoming overcoming prior art, the synthetic method of a kind of tetrafluoro adamantane derivative that a kind of raw material is easy to get, experimental technique simple, experiment condition is easy to realization, products therefrom yield is high is provided.
The object of the invention is to be achieved through the following technical solutions:
The synthetic method of tetrafluoro adamantane, comprises the steps:
Selectfluor (two (Tetrafluoroboric acid) salt of 1-chloromethyl-4-fluoro-Isosorbide-5-Nitrae-diazotization two ring [2.2.2] octane) is added, catalyzer in diamantane, solvent is the mixing solutions of first alcohol and water, reacts, one-step synthesis 1 at 10 ~ 50 DEG C, 3,5,7-tetrafluoro adamantane.
Wherein, in solvent, the ratio of first alcohol and water counts 1:1 ~ 10:1 by volume; The mol ratio of diamantane and Selectfluor is 1:4 ~ 1:10; The mol ratio of diamantane and catalyzer is 100:5 ~ 100:10; Reaction times is 12 ~ 24 hours; Catalyzer selects aluminum chloride, aluminum bromide, iron(ic) chloride, cuprous iodide, elemental iodine or palladium.
Compared with prior art, its remarkable advantage: the fluorination reagent that (1) the present invention uses is novel solid fluorinated reagent, is convenient to store, uses, nontoxic pollution-free in the present invention; (2) one-step synthesis tetrafluoro adamantane derivative, synthesis step is short, productive rate 72%; (3) reaction conditions is gentle, and without the need to high temperature, high pressure, without the need to corrosion-resistant reaction vessel, without the need to special reaction instrument.
Embodiment
Embodiment 1
Take 10mmol diamantane, Selectfluor 40mmol, iodine 0.1mmol is in there-necked flask, and solvent is methyl alcohol: water=1:1, react 12 hours at 10 DEG C, reaction terminates the extraction of rear chloroform/water, evaporates under organic phase vacuum, obtain white solid, yield 82%, purity 90%.
Embodiment 2
Take 10mmol diamantane, Selectfluor 100mmolg, iodine 1mmol is in there-necked flask, and solvent is methyl alcohol: water=10:1, react 24 hours at 50 DEG C, reaction terminates the extraction of rear chloroform/water, evaporates under organic phase vacuum, obtain white solid, yield 72%, purity 95%.
Embodiment 3
Take 10mmol diamantane, Selectfluor 60mmol, palladium 1mmol are in there-necked flask, and solvent is methyl alcohol: water=9:1, react 24 hours at 25 DEG C, reaction terminates the extraction of rear chloroform/water, evaporates under organic phase vacuum, obtain white solid, yield 82%, purity 97%.
Embodiment 4
Take 10mmol diamantane, Selectfluor 60mmol, palladium 0.1mmol are in there-necked flask, and solvent is methyl alcohol: water=9:1, react 18 hours at 45 DEG C, reaction terminates the extraction of rear chloroform/water, evaporates under organic phase vacuum, obtain white solid, yield 82%, purity 99%.
Embodiment 5
Take 10mmol diamantane, Selectfluor 100mmol, cuprous iodide 1mmol is in there-necked flask, and solvent is methyl alcohol: water=9:1, react 12 hours at 45 DEG C, reaction terminates the extraction of rear chloroform/water, evaporates under organic phase vacuum, obtain white solid, yield 72%, purity 91%.
Embodiment 6
Take 10mmol diamantane, Selectfluor 80mmol, aluminum chloride 1mmol is in there-necked flask, and solvent is methyl alcohol: water=9:1, react 12 hours at 50 DEG C, reaction terminates the extraction of rear chloroform/water, evaporates under organic phase vacuum, obtain white solid, yield 82%, purity 93%.
Embodiment 7
Take 10mmol diamantane, Selectfluor 100mmol, aluminum bromide 1mmol is in there-necked flask, and solvent is methyl alcohol: water=9:1, react 12 hours at 25 DEG C, reaction terminates the extraction of rear chloroform/water, evaporates under organic phase vacuum, obtain white solid, yield 72%, purity 97%.
Embodiment 8
Take 10mmol diamantane, Selectfluor 100mmol, iron(ic) chloride 1mmol is in there-necked flask, and solvent is methyl alcohol: water=9:1, react 24 hours at 25 DEG C, reaction terminates the extraction of rear chloroform/water, evaporates under organic phase vacuum, obtain white solid, yield 82%, purity 97%.
Claims (4)
- The synthetic method of 1.1,3,5,7-tetrafluoro adamantane, is characterized in that comprising the following steps:In diamantane, add Selectfluor, catalyzer, solvent is the mixing solutions of first alcohol and water, reacts, one-step synthesis 1,3,5,7-tetrafluoro adamantane at 10 ~ 50 DEG C; Described catalyzer selects aluminum chloride, aluminum bromide, iron(ic) chloride, cuprous iodide, elemental iodine or palladium.
- 2. the synthetic method of 1,3,5,7-tetrafluoro adamantane according to claim 1, is characterized in that, in solvent, the ratio of first alcohol and water counts 1:1 ~ 10:1 by volume.
- 3. the synthetic method of 1,3,5,7-tetrafluoro adamantane according to claim 1, is characterized in that, the mol ratio of diamantane and Selectfluor is 1:4 ~ 1:10; The mol ratio of diamantane and catalyzer is 100:5 ~ 100:10.
- 4. the synthetic method of 1,3,5,7-tetrafluoro adamantane according to claim 1, is characterized in that, the reaction times is 12 ~ 24 hours.
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| CN103193587B true CN103193587B (en) | 2015-04-22 |
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| GB9907214D0 (en) * | 1999-03-30 | 1999-05-26 | F2 Chemicals Ltd | Preparation of selectively fluorinated organic compounds |
| GB0001093D0 (en) * | 2000-01-19 | 2000-03-08 | F2 Chemicals Ltd | Selective nitrogen functionalisation of organic compounds |
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