WO2018025429A1 - モノヒドロペルフルオロアルカンを出発原料とするペルフルオロアルキル化合物の製造方法 - Google Patents
モノヒドロペルフルオロアルカンを出発原料とするペルフルオロアルキル化合物の製造方法 Download PDFInfo
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- WO2018025429A1 WO2018025429A1 PCT/JP2017/005726 JP2017005726W WO2018025429A1 WO 2018025429 A1 WO2018025429 A1 WO 2018025429A1 JP 2017005726 W JP2017005726 W JP 2017005726W WO 2018025429 A1 WO2018025429 A1 WO 2018025429A1
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- cyclohexanone
- piperidinone
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- NSFHTONABRSTTQ-UHFFFAOYSA-N CC(C(F)(F)F)(c1cc(Br)ccc1)O Chemical compound CC(C(F)(F)F)(c1cc(Br)ccc1)O NSFHTONABRSTTQ-UHFFFAOYSA-N 0.000 description 1
- JYAQYXOVOHJRCS-UHFFFAOYSA-N CC(c1cc(Br)ccc1)=O Chemical compound CC(c1cc(Br)ccc1)=O JYAQYXOVOHJRCS-UHFFFAOYSA-N 0.000 description 1
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
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- C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
- C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
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- C07C31/02—Monohydroxylic acyclic alcohols
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- C07C31/34—Halogenated alcohols
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- C07C33/40—Halogenated unsaturated alcohols
- C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a simple method for producing a perfluoroalkyl compound, which is an important intermediate of organic electronic materials, pharmaceuticals, agricultural chemicals, functional polymer materials, etc., using monohydroperfluoroalkane as a starting material.
- Organic compounds having a perfluoroalkyl group are important intermediates such as organic electronic materials, pharmaceuticals, agricultural chemicals, and polymer functional materials. Among them, many synthesis examples of trifluoromethyl compounds have been reported.
- a Lupert-Prakash reagent trifluoromethyltrimethylsilane, CF 3 SiMe 3
- an aldehyde Non-patent document 2, Non-patent document
- Non-Patent Document 5 Lactone (Non-Patent Document 2), Acid Halide (Non-Patent Document 2), Amide (Non-Patent Document 2, Non-Patent Document 3), Imide (Non-Patent Document 2), Aziridine (Non-Patent Document 2) Patent Literature 2), Alkyl halide (Non Patent Literature 2), Aryl halide (Non Patent Literature 2), Sulfur Compound (Non Patent Literature 2), Organometallic Compound (Non Patent Literature 2), Nitroso Compound (Non Patent Literature 2) Permitted 2), phosphorus compound (Non-patent document 2, Non-patent document 3), imine (non-patent document 3), porphyrin (
- trifluoromethane is a material that is potentially produced as a trifluoromethyl source because it is industrially produced in large quantities as a by-product of the Teflon (registered trademark) production process and is available in large quantities at a low cost. .
- Non-Patent Document 7 Non-Patent Document 8, Non-Patent Document 10, Non-Patent Document 11, Non-Patent Document 12, Non-Patent Document 13, Non-Patent Document 14, Patent Document 3, Patent 4), ketone (Non-patent document 7, Non-patent document 9, Non-patent document 11, Non-patent document 13, Non-patent document 14, Non-patent document 15, Patent document 1, Patent document 2, Patent document 4), Ester (Non-patent document 7, Non-patent document 13, Patent document 4), Acid halide (Non-patent document 7, Non-patent document 13), Boron compound (Non-patent document 7, Patent document 4), Silicon compound (Non-patent document 7) , Patent Document 4), elemental sulfur (Non-Patent Document 7, Patent Document 4), disulfide (Non-Patent Document 14), epoxide (Non-Patent Document 13), carbon dioxide (Non-Patent Document 13, Patent Document 4), elemental sulfur (Non-Patent Document 7, Patent Document 4), dis
- An object of the present invention is to provide a simple method for producing a perfluoroalkyl compound, which is an important intermediate for organic electronic materials, pharmaceuticals, agricultural chemicals, functional polymer materials, etc., using monohydroperfluoroalkane as a starting material. .
- the present inventors use trifluoromethane, which is inexpensive and available in large quantities, as a trifluoromethyl source, and uses an inexpensive and highly versatile base in place of a conventional expensive base to activate trifluoromethane.
- the goal was to develop a method to induce fluoromethyl compounds, and as a result of intensive research, we found a method that can activate trifluoromethane using potassium hydroxide as a cheap and versatile base, The reaction was successful in producing a trifluoromethyl compound with high selectivity and high yield.
- the present inventors have found that the present invention can be applied to pentafluoroethane in addition to the above-described trifluoromethane, and further found to be applicable to R F H (monohydroperfluoroalkane) represented by the general formula [3]. The present invention has been reached.
- the present invention provides the following aspects.
- R 1 and R 2 each independently have a hydrogen atom, a straight chain having 1 to 2 carbon atoms, a straight chain having 3 to 10 carbon atoms, a branched or cyclic structure, and may have a substituent.
- R 1 and R 2 may be combined to form a ring.
- an ammonium group which may have an unsubstituted or alkyl group having 1 to 10 carbon atoms as a substituent, which may be a single substance or a mixture of plural substances, and x is M It corresponds to the oxidation number of the substance represented by]
- M (OH) x represented by the general formula [2] is tetramethylammonium hydroxide or a hydrate thereof.
- a simple perfluoroalkyl compound which is an important intermediate for organic electronic materials, pharmaceuticals, agricultural chemicals, and functional polymer materials, starting from monohydroperfluoroalkanes typified by trifluoromethane and pentafluoroethane, can be used. It has become possible to provide a manufacturing method. Among monohydroperfluoroalkanes, particularly trifluoromethane is a gas with a high output and a high global warming effect, and therefore, its processing method and disposal method are listed as problems. In the present invention, it is possible to provide a treatment method as well as an effective utilization method of trifluoromethane having a high global warming effect. Therefore, it is possible to make a practical contribution in terms of economy and environment.
- a carbonyl compound represented by the general formula [1] is used as a starting material, particularly trifluoromethane produced in large quantities industrially.
- Carbonyl compound represented by the general formula [1] is not particularly limited, and examples of the substituent represented by R 1 and R 2 include a straight or carbon atom having 1 to 2 carbon atoms in addition to a hydrogen atom.
- benzophenone, acetophenone, undecan-2-one, 4′-methoxyacetophenone, 3′-methoxyacetophenone, 2′-methoxyacetophenone, 4′-dimethylaminoacetophenone, 4′-acetamidoacetophenone, 4′-fluoro Examples include acetophenone, 4′-chloroacetophenone, 3′-bromoacetophenone, pivalaldehyde, benzaldehyde, acetaldehyde, formaldehyde and the like.
- R 1 and R 2 may be combined to form an aliphatic ring or a heterocyclic ring having 3 to 26 carbon atoms, particularly 3 to 10 carbon atoms.
- the carbon atom constituting the aliphatic ring or heterocyclic ring there is a group containing an atom other than a hydrogen atom as a substituent, for example, nitrogen, oxygen, silicon, phosphorus, sulfur, fluorine, chlorine, bromine, iodine or the like.
- the hydroxide represented by the general formula [2] in the present invention is not particularly limited, and the substance represented by M is mainly Group I, Group II, Group III, Group IV, Group V, Group VI. Group VII, Group VIII, Group IX, Group X, Group XI, Group XII, and Group XIII metal or an ammonium hydroxide which may have an unsubstituted or alkyl group having 1 to 10 carbon atoms as a substituent Specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, oxyhydroxide Iron, copper hydroxide, zinc hydroxide, aluminum hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrahydroxide
- the four alkyl groups on the nitrogen atom forming the ammonium salt may all be the same, all may be different, or 1 to 4 of the alkyl groups may be substituted with hydrogen.
- Anhydrate or hydrate (monohydrate to hydrate 20) can be used.
- the hydroxide represented by the general formula [2] is preferably a combination of a monovalent cation and one hydroxide ion, more preferably sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or its Hydrate (especially pentahydrate).
- the monohydroperfluoroalkane represented by the general formula [3] in the present invention is not particularly limited, and the substance represented by R F is a straight chain having 1 to 2 carbon atoms or 3 to 26 carbon atoms, particularly 3 to 10 carbon atoms.
- An alkyl group that may have a linear, branched, or cyclic structure, and represents a perfluoroalkyl group in which all of the hydrogen on the carbon is substituted with fluorine, specifically, a trifluoromethyl group, a pentafluoroethyl group, a hepta.
- Fluoropropyl, heptafluoroisopropyl, pentafluorocyclopropyl, nonafluorobutyl, nonafluoroisobutyl, nonafluorotertiary butyl, heptafluorocyclobutyl, undecafluoropentyl, nonafluorocyclopentyl, tri Decafluorohexyl group, undecafluorocyclohexyl Group, pentadecafluoroheptyl group, tridecafluorocycloheptyl group, heptadecafluorooctyl group, pentadecacyclooctyl group, nonadecafluorononyl group, hepadecafluorocyclononyl group, henicosafluorodecenyl group, Nonadecafluorocyclodecenyl group and the like are represented.
- Perfluoroalkyl alcohol represented by the general formula [4] Perfluoroalkyl alcohol of the formula [4] in the present invention, each with R 1, the same substituents as R 2 R 1, R 2 in the general formula [1] is the corresponding perfluoroalkyl alcohol.
- the reaction temperature can be -40 ° C to 200 ° C, preferably 0 ° C to 60 ° C.
- the reaction time can be 1 hour to 100 hours, preferably 3 hours to 6 hours.
- the amount of monohydroperfluoroalkane used is about 0.1 to 100 molar equivalents, preferably 1 to 10 molar equivalents, relative to the carbonyl compound represented by the general formula [1] used in the present invention. .
- the reaction pressure is the atmospheric pressure (1.0 ⁇ 10 ⁇ 7 MPa to 0.09 MPa), normal pressure (about 0.1 MPa) or pressurized state (0.11 to 4.87 MPa).
- it is preferably 1.0 ⁇ 10 ⁇ 7 MPa to 0.11 MPa, more preferably 0.01 MPa to 0.11 MPa.
- the pressure is preferably 0.09 ⁇ 10 ⁇ 7 MPa to 4.87 MPa, more preferably 0.2 MPa to 1 MPa.
- the method for introducing monohydroperfluoroalkane will be described when the monohydroperfluoroalkane is trifluoromethane, but other monohydroperfluoroalkanes that are in the gas state at the standard state are also used for the reaction. can do.
- the inside of the reaction vessel Prior to use in the reaction, the inside of the reaction vessel is evacuated, and then trifluoromethane is introduced and the inside of the reaction vessel may be in a trifluoromethane atmosphere, but the inside of the reaction vessel is replaced with an inert gas such as nitrogen, helium or argon. After that, trifluoromethane may be introduced to carry out the reaction in the state of a mixed gas of trifluoromethane with an inert gas.
- trifluoromethane may be introduced directly from a cylinder or cylinder equipped with a pressure reducing valve into a reactor through a pipe, or a sampling bag filled with trifluoromethane in advance or introduced from a rubber balloon into the reactor.
- a method of introducing a rubber balloon into the reactor is preferable, but industrially, it is more preferable to introduce trifluoromethane into the reactor using a pipe.
- the method of contacting trifluoromethane with the reaction solution includes a method of contacting and mixing at the gas-liquid interface, or a method of liquefying trifluoromethane using a condenser and mixing it with the reaction solution, but contact mixing at the gas-liquid interface. The method of making it preferable is.
- Monohydroperfluoroalkane that is liquid or solid at room temperature can be used in the reaction by the same introduction method as that for normal liquid or solid materials.
- the carbonyl compound represented by the general formula [1] may be removed by performing a purification operation such as distillation before being used in the reaction, but it is mixed in an industrially available state. Impurities are not particularly problematic in carrying out the production method and can be used as they are.
- the substance represented by M is mainly Group I, Group II, Group III, Group IV, Group V, Group VI, Group VIII, Group IX, IX.
- Group, X, XI, XII and XIII metals or ammonium hydroxides which may have a substituent, specifically lithium hydroxide, sodium hydroxide, potassium hydroxide, water Rubidium oxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide, iron (III) oxyhydroxide, copper (I) hydroxide, copper (II) hydroxide, Zinc hydroxide, aluminum hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetohydroxide Examples include butyl ammonium, tetrapentyl ammonium
- the amount of the hydroxide represented by the general formula [2] is about 0.1 to 100 molar equivalents, preferably 1 to 20 molar equivalents with respect to the monohydroperfluoroalkane. If hydroxide is assumed to be adsorbed even when it is hydrated or anhydrous, it can be removed by drying before use in the reaction, etc. It is preferable to add a dehydrating agent such as molecular sieves to the reaction system, but it is not always necessary to completely remove it. Even if it is a hydrate having a hydration number of 5 or less, or an hydrate, it is not more than 5% by weight, preferably 1%, based on the amount of water mixed in an industrially available state, ie, hydroxide.
- Moisture of not more than wt%, more preferably not more than 0.1 wt% can be used as it is without any particular problem in carrying out the production method.
- the hydroxide can be used in the form of flakes, granules, and powders, but is preferably in the form of powders, and a method in which the granules are pulverized before use in the reaction is more preferred.
- an aprotic polar solvent can be used as the solvent. Specifically, acetonitrile, propionitrile, phenylacetonitrile, isobutyronitrile, benzonitrile, dimethylformamide, dimethylacetamide, methylformamide, formamide, N-methylpyrrolidone, N , N-dimethylimidazolidinone, hexamethylphosphoric triamide, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, 1,2-epoxyethane, diglyme, triglyme, tetraglyme, dimethyl sulfoxide, sulfolane and the like can be used, but dimethyl sulfoxide and sulfolane are preferred, and these are combined.
- aprotic polar solvent can be used in combination with a nonpolar solvent such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like.
- the amount of the solvent is about 1 to 100 parts by weight, preferably 1 to 10 parts by weight with respect to 1 part by weight of the carbonyl compound represented by the general formula [1].
- the solvent to be used may be dehydrated before use in the reaction, or a dehydrating agent such as molecular sieves may be added during the reaction, but the water does not necessarily need to be completely removed.
- the amount of water that is normally mixed in an industrially available state that is, 5% by weight or less, preferably less than 1% by weight, and more preferably 0.1% by weight or less based on the solvent, Can be used as it is.
- a perfluoroalkyl alcohol represented by the general formula [4] can be obtained by performing a purification treatment based on a normal organic chemical treatment method.
- the compound was identified by 1 H nuclear magnetic resonance spectrum analysis (NMR), 19 F NMR, and mass spectrum analysis (GS-MS).
- Ph represents a phenyl group
- DMSO represents dimethyl sulfoxide
- rt represents room temperature
- 6h represents a reaction time of 6 hours.
- benzophenone (1a) was added to a 20 mL two-necked flask containing potassium hydroxide (pulverized in a mortar in an argon glove box, 1.12 g, 20 mmol) and dimethyl sulfoxide (undried product, 5 mL). 1 mmol) was added followed by a balloon with an excess of trifluoromethane. After stirring at room temperature for 6 hours, the reaction was stopped by neutralizing potassium hydroxide with 4N hydrochloric acid in an ice bath.
- Example 1 When potassium hydroxide in Example 1 was changed to sodium hydroxide, the reaction temperature was 40 ° C., and the others were reacted under the same conditions, the target product 2a was obtained in a yield of 54% (based on raw material ketone).
- Example 1 When potassium hydroxide in Example 1 was changed to tetramethylammonium hydroxide pentahydrate, molecular sieves 4A was added, and the others were reacted under the same conditions, the target product 2a was obtained in a yield of 61% (raw material ketone). Standard).
- Example 1 The solvent in Example 1 was changed to N, N-dimethylformamide (DMF) (non-dehydrated product, 10 mL), the reaction temperature was 40 ° C., and the reaction was carried out under the same conditions. (Based on raw material ketone).
- DMF N-dimethylformamide
- Example 1 The solvent in Example 1 was changed to N-methylpyrrolidone (NMP) (non-dehydrated product, 10 mL), the reaction temperature was set to 40 ° C., and the reaction was performed under the same conditions. As a result, 47% of the target product 2a (raw material ketone) Standard).
- NMP N-methylpyrrolidone
- Non-Patent Document 9 Under the conditions described in Non-Patent Document 9, the above reaction was examined under the same conditions except that the reaction time was extended from 5 hours to 12 hours, and the target product 2a was obtained in a yield of 62% (based on the raw material ketone). .
- Example 1 When benzophenone (1a) in Example 1 was changed to 4'-methoxyacetophenone (1 g) and the reaction was carried out under the same conditions, 2 g of the desired product was obtained in a yield of 76% (based on raw material ketone).
- 1-methyl-1-trifluoromethyl-1- (4'-acetamidophenyl) methyl alcohol represented by the structural formula 2k is a novel compound synthesized for the first time by the method of the present invention.
- Example 1 When benzophenone (1a) in Example 1 was changed to 4'-fluoroacetophenone (1 l) and the reaction was carried out under the same conditions, 2l of the desired product was obtained in 44% yield (based on raw material ketone).
- Example 1 When benzophenone (1a) in Example 1 was changed to 4'-chloroacetophenone (1 m) and the reaction was carried out under the same conditions, the target product 2m was obtained in 39% yield (based on raw material ketone).
- Example 1 When benzophenone (1a) in Example 1 was changed to 3'-bromoacetophenone (1n) and the reaction was carried out under the same conditions, the target product 2n was obtained in 39% yield (based on raw material ketone).
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Abstract
Description
一般式[1]:
で示されるカルボニル化合物と、一般式[2]:
M(OH)x [2]
[式中、Mは元素周期律表におけるI族、II族、III族、IV族、V族、VI族、VII族、VIII族、IX族、X族、XI族、XII族、及びXIII族に属する金属あるいは無置換若しくは炭素数1から10のアルキル基を置換基として有しても良いアンモニウムであり、それらは単独であっても、複数の物質の混合物であっても良く、xはMであらわされる物質の酸化数に一致する]
で示される水酸化物、及び一般式[3]:
RFH [3]
[式中、RFは炭素数1~2の直鎖あるいは炭素数3~10の直鎖、分岐あるいは環状構造を有することもあるアルキル基であり、炭素上の水素が全てフッ素で置換されたペルフルオロアルキル基を表す]
で示されるモノヒドロペルフルオロアルカンを有機溶媒中で反応させることを特徴とする、一般式[4]:
一般式[3]で示されるRFHがトリフルオロメタンであることを特徴とする、(1)に記載の方法。
一般式[3]で示されるRFHがペンタフルオロエタンであることを特徴とする、(1)に記載の方法。
一般式[2]で示されるM(OH)xが水酸化カリウムであることを特徴とする、(1)に記載の方法。
一般式[2]で示されるM(OH)xが水酸化ナトリウムであることを特徴とする、(1)に記載の方法。
一般式[2]で示されるM(OH)xが水酸化テトラメチルアンモニウムまたはその水和物であることを特徴とする、(1)に記載の方法。
一般式[2]で示されるM(OH)xが、粉末状で反応系に添加されることを特徴とする、(1)~(6)のいずれかに記載の方法。
有機溶媒がジメチルスルホキシド、ジメチルホルムアミド、N-メチルピロリドン、テトラヒドロフラン、ジグライム、アセトニトリル、又はこれらの組み合わせであることを特徴とする、(1)~(7)のいずれかに記載の製造方法。
モノヒドロペルフルオロアルカンが気体の状態で反応液と接触することを特徴とする、(1)~(8)のいずれかに記載の製造方法。
モノヒドロペルフルオロアルカンを液体あるいは固体の状態で反応液と混合させることを特徴とする、(1)~(8)のいずれかに記載の製造方法。
本発明の方法は、実験的に見出されたものであり、本発明者らのこれまでの検討によれば、一般式[2]で示される水酸化物が、一般式[3]で示されるモノヒドロペルフルオロアルカンから水素原子(プロトン)を引き抜き、その結果生じたペルフルオロアルキルアニオンが一般式[1]で示されるカルボニル化合物のカルボニル基の炭素に求核的に攻撃し、カルボニル基が水酸基となり、一般式[4]で示されるペルフルオロアルキルアルコールが形成されるものと考えられる。先行技術においては、モノヒドロペルフルオロアルカンから水素原子(プロトン)を引き抜く過程が特殊な強塩基を用いなければ起こらないと考えられていたので、一般式[2]で示される水酸化物を使用することにより、本発明の方法が実施できることは驚くべきことであった。
本発明の一般式[1]で示されるカルボニル化合物は、特に限定されず、R1、R2で表される置換基としては、水素原子の他に、炭素数1~2の直鎖あるいは炭素数3~26、特に炭素数3~10の直鎖、分岐あるいは環状構造を有することもあるアルキル基、アリール基、ヘテロアリール基、アラルキル基、アルケニル基またはアルキニル基をあらわし、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、フェニル基、ナフチル基、アントラニル基、ナフタセニル基、ペンタセニル基、ヘキサセニル基、コロニル基、ピロリル基、フリル基、チエニル基、ピリジル基、ピリミジル基、ピラジル基、ピリダジル基、ピラゾリル基、イミダゾリル基、オキサゾリル基、チアゾリル基、インドリル基、ベンゾフリル基、ベンゾチエニル基、キノリル基、イソキノリル基、キノキサリル基、フタラジル基、キナゾリル基、ナフチリジル基、シンノリル基、ベンゾイミダゾリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、ベンジル基、フェネチル基、ビニル基、アリル基、プレニル基、プロパギル基などであり、それらの炭素原子上には水素原子以外の原子、例えば窒素、酸素、ケイ素、リン、硫黄、フッ素、塩素、臭素、ヨウ素等が置換された状態でも良く、また、水素原子以外の置換基、例えば、アルキル基、アリール基、ヘテロアリール基、アラルキル基、アルケニル基、アルキニル基、ヒドロキシ基、ヒドロペルオキシ基、ジオキシ基、カルボキシル基、チオカルボキシ基、ジチオカルボキシ基、カルボニル基、チオカルボニル基、オキシカルボニル基、ハロホルミル基、カルバモイル基、メトキシ基、エトキシ基等のアルコキシ基、ジメチルアミノ基、アセトアミノ基(AcHN-)等のアミノ基、イミノ基、ヒドラジノ基、トリフルオロメチル基、ジフルオロメチル基、トリクロロメチル等のハロゲン置換アルキル基、スルファニル基、アルキルスルフィニル基、アルキルスルホニル基、スルホ基、スルフィノ基、シアノ基、イソシアノ基、シアナト基、イソシアナト基、チオシアナト基、イソチオシアナト基、ニトロ基、ニトロソ基、ジアゾ基、アジド基、アミジノ基、ホルミル基、チオホルミル基等が置換された状態でもよい。具体的には、ベンゾフェノン、アセトフェノン、ウンデカン-2-オン、4’-メトキシアセトフェノン、3’-メトキシアセトフェノン、2’-メトキシアセトフェノン、4’-ジメチルアミノアセトフェノン、4’-アセトアミドアセトフェノン、4’-フルオロアセトフェノン、4’-クロロアセトフェノン、3’-ブロモアセトフェノン、ピバルアルデヒド、ベンズアルデヒド、アセトアルデヒド、ホルムアルデヒドなどが挙げられる。
(ジシクロノニルアミノ)シクロヘキサノン、4-(シクロデシルアミノ)シクロヘキサノン、4-(ジフェニルアミノ)シクロヘキサノン、4-(ジナフチルアミノ)シクロヘキサノン、4-(ジアントラニルアミノ)シクロヘキサノン、4-(ジナフタセニルアミノ)シクロヘキサノン、4-(ジペンタセニルアミノ)シクロヘキサノン、4-(ジヘキサセニルアミノ)シクロヘキサノン、4-(ジコロニルアミノ)シクロヘキサノン、4-(ジピロリルアミノ)シクロヘキサノン、4-(ジフリルアミノ)シクロヘキサノン、4-(ジチエニルアミノ)シクロヘキサノン、4-(ジピリジルアミノ)シクロヘキサノン、4-(ジピリミジルアミノ)シクロヘキサノン、4-(ジピラジルアミノ)シクロヘキサノン、4-(ジピリダジルアミノ)シクロヘキサノン、4-(ジピラゾリルアミノ)シクロヘキサノン、4-(ジイミダゾリルアミノ)シクロヘキサノン、4-(ジオキサゾリルアミノ)シクロヘキサノン、4-(ジチアゾリルアミノ)シクロヘキサノン、4-(ジインドリルアミノ)シクロヘキサノン、4-(ジベンゾフリルアミノ)シクロヘキサノン、4-(ジベンゾチエニルアミノ)シクロヘキサノン、4-(ジキノリルアミノ)シクロヘキサノン、4-(ジイソキノリルアミノ)シクロヘキサノン、4-(ジキノキサリルアミノ)シクロヘキサノン、4-(ジフタラジルアミノ)シクロヘキサノン、4-(ジキナゾリルアミノ)シクロヘキサノン、4-(ジナフチリジルアミノ)シクロヘキサノン、4-(ジシンノリルアミノ)シクロヘキサノン、4-(ジベンゾイミダゾリルアミノ)シクロヘキサノン、4-(ジベンゾオキサゾリルアミノ)シクロヘキサノン、4-(ジベンゾチアゾリルアミノ)シクロヘキサノン、4-(ジベンジルアミノ)シクロヘキサノン、4-(ジフェネチルアミノ)シクロヘキサノン、4-(ジビニルアミノ)シクロヘキサノン、4-(ジアリルアミノ)シクロヘキサノン、4-(ジプレニルアミノ)シクロヘキサノン、4-(ジプロパギルアミノ)シクロヘキサノン、4-ヒドロキシシクロヘキサノン、4-(メトキシ)シクロヘキサノン、4-(エトキシ)シクロヘキサノン、4-(プロポキシ)シクロヘキサノン、4-(イソプロポキシ)シクロヘキサノン、4-(ブトキシ)シクロヘキサノン、4-(イソブトキシ)シクロヘキサノン、4-(ターシャリーブトキシ)シクロヘキサノン、4-(ペンチルオキシ)シクロヘキサノン、4-(ヘキシルオキシ)シクロヘキサノン、4-(ヘプチルオキシ)シクロヘキサノン、4-(オクチルオキシ)シクロヘキサノン、4-(ノニルオキシ)シクロヘキサノン、4-(デシルオキシ)シクロヘキサノン、4-(シクロプロポキシ)シクロヘキサノン、4-(シクロブトキシ)シクロヘキサノン、4-(シクロペンチルオキシ)シクロヘキサノン、4-(シクロヘキシルオキシ)シクロヘキサノン、4-(シクロヘプチルオキシ)シクロヘキサノン、4-(シクロオクチルオキシ)シクロヘキサノン、4-(シクロノニルオキシ)シクロヘキサノン、4-(シクロデシルオキシ)シクロヘキサノン、4-(フェノキシ)シクロヘキサノン、4-(ナフトキシ)シクロヘキサノン、4-(アントラセニルオキシ)シクロヘキサノン、4-(ナフタセニルオキシ)シクロヘキサノン、4-(ペンタセニルオキシ)シクロヘキサノン、4-(ヘキサセニルオキシ)シクロヘキサノン、4-(コロニルオキシ)シクロヘキサノン、4-(ピロリルオキシ)シクロヘキサノン、4-(フリルオキシ)シクロヘキサノン、4-(チエニルオキシ)シクロヘキサノン、4-(ピリジルオキシ)シクロヘキサノン、4-(ピリミジルオキシ)シクロヘキサノン、4-(ピラジルオキシ)シクロヘキサノン、4-(ピリダジルオキシ)シクロヘキサノン、4-(ピラゾリルオキシ)シクロヘキサノン、4-(イミダゾリルオキシ)シクロヘキサノン、4-(オキサゾリルオキシ)シクロヘキサノン、4-(チアゾリルオキシ)シクロヘキサノン、4-(インドリルオキシ)シクロヘキサノン、4-(ベンゾフリルオキシ)シクロヘキサノン、4-(ベンゾチエニルオキシ)シクロヘキサノン、4-(キノリルオキシ)シクロヘキサノン、4-(イソキノリルオキシ)シクロヘキサノン、4-(キノキサリルオキシ)シクロヘキサノン、4-(フタラジルオキシ)シクロヘキサノン、4-(キナゾリルオキシ)シクロヘキサノン、4-(ナフチリジルオキシ)シクロヘキサノン、4-(シンノリルオキシ)シクロヘキサノン、4-(ベンゾイミダゾリルオキシ)シクロヘキサノン、4-(ベンゾオキサゾリルオキシ)シクロヘキサノン、4-(ベンゾチアゾリルオキシ)シクロヘキサノン、4-(ベンジルオキシ)シクロヘキサノン、4-(フェネチルオキシ)シクロヘキサノン、4-(ビニルオキシ)シクロヘキサノン、4-(アリルオキシ)シクロヘキサノン、4-(プレニルオキシ)シクロヘキサノン、4-(プロパギルオキシ)シクロヘキサノン、4-メルカプトシクロヘキサノン、4-(メチルチオ)シクロヘキサノン、4-(エチルチオ)シクロヘキサノン、4-(プロピルチオ)シクロヘキサノン、4-(イソプロピルチオ)シクロヘキサノン、4-(ブチルチオ)シクロヘキサノン、4-(イソブチルチオ)シクロヘキサノン、4-(ターシャリーブチルチオ)シクロヘキサノン、4-(ペンチルチオ)シクロヘキサノン、4-(ヘキシルチオ)シクロヘキサノン、4-(ヘプチルチオ)シクロヘキサノン、4-(オクチルチオ)シクロヘキサノン、4-(ノニルチオ)シクロヘキサノン、4-(デシルチオ)シクロヘキサノン、4-(シクロプロピルチオ)シクロヘキサノン、4-(シクロブチルチオ)シクロヘキサノン、4-(シクロペンチルチオ)シクロヘキサノン、4-(シクロヘキシルチオ)シクロヘキサノン、4-(シクロヘプチルチオ)シクロヘキサノン、4-(シクロオクチルチオ)シクロヘキサノン、4-(シクロノニルチオ)シクロヘキサノン、4-(シクロデシルチオ)シクロヘキサノン、4-(フェニルチオ)シクロヘキサノン、4-(ナフチルチオ)シクロヘキサノン、4-(アントラニルチオ)シクロヘキサノン、4-(ナフタセニルチオ)シクロヘキサノン、4-(ペンタセニルチオ)シクロヘキサノン、4-(ヘキサセニルチオ)シクロヘキサノン、4-(コロニルチオ)シクロヘキサノン、4-(ピロリルチオ)シクロヘキサノン、4-(フリルチオ)シクロヘキサノン、4-(チエニルチオ)シクロヘキサノン、4-(ピリジルチオ)シクロヘキサノン、4-(ピリミジルチオ)シクロヘキサノン、4-(ピラジルチオ)シクロヘキサノン、4-(ピリダジルチオ)シクロヘキサノン、4-(ピラゾリルチオ)シクロヘキサノン、4-(イミダゾリルチオ)シクロヘキサノン、4-(オキサゾリルチオ)シクロヘキサノン、4-(チアゾリルチオ)シクロヘキサノン、4-(インドリルチオ)シクロヘキサノン、4-(ベンゾフリルチオ)シクロヘキサノン、4-(ベンゾチエニルチオ)シクロヘキサノン、4-(キノリルチオ)シクロヘキサノン、4-(イソキノリルチオ)シクロヘキサノン、4-(キノキサリルチオ)シクロヘキサノン、4-(フタラジルチオ)シクロヘキサノン、4-(キナゾリルチオ)シクロヘキサノン、4-(ナフチリジルチオ)シクロヘキサノン、4-(シンノリルチオ)シクロヘキサノン、4-(ベンゾイミダゾリルチオ)シクロヘキサノン、4-(ベンゾオキサゾリルチオ)シクロヘキサノン、4-(ベンゾチアゾリルチオ)シクロヘキサノン、4-(ベンジルチオ)シクロヘキサノン、4-(フェネチルチオ)シクロヘキサノン、4-(ビニルチオ)シクロヘキサノン、4-(アリルチオ)シクロヘキサノン、4-(プレニルチオ)シクロヘキサノン、4-(プロパギルチオ)シクロヘキサノン、4-フルオロシクロヘキサノン、4-クロロシクロヘキサノン、4-ブロモシクロヘキサノン、4-ヨードシクロヘキサノン、などが挙げられる。
本発明における一般式[2]で表される水酸化物は、特に限定されず、Mで表される物質としては、主にI族、II族、III族、IV族、V族、VI族、VII族、VIII族、IX族、X族、XI族、XII族、及びXIII族の金属あるいは無置換若しくは炭素数1から10のアルキル基を置換基として有しても良いアンモニウムの水酸化物をあらわし、具体的には水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、水酸化ベリリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム、オキシ水酸化鉄、水酸化銅、水酸化亜鉛、水酸化アルミニウム、水酸化アンモニウム、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム、水酸化テトラペンチルアンモニウム、水酸化テトラヘキシルアンモニウム、水酸化テトラヘプチルアンモニウム、水酸化テトラオクチルアンモニウム、水酸化テトラノニルアンモニウム、水酸化テトラデシルアンモニウムなどである。なお、アンモニウム塩を形成している窒素原子上の4つのアルキル基は全て同じであっても良く、全てが異なっていても良く、あるいはアルキル基の1~4つが水素で置換されていても良く、無水物あるいは水和物(1水和物から20水和物)が使用できる。一般式[2]で表される水酸化物は、好ましくは1価の陽イオンと1個の水酸化物イオンの組み合わせ、より好ましくは水酸化ナトリウム、水酸化カリウム、水酸化テトラメチルアンモニウムまたはその水和物(特に、5水和物)である。
本発明における一般式[3]で示されるモノヒドロペルフルオロアルカンは、特に限定されず、RFで表される物質としては炭素数1~2の直鎖あるいは3~26、特に炭素数3~10の直鎖、分岐あるいは環状構造を有することもあるアルキル基であり、炭素上の水素が全てフッ素で置換されたペルフルオロアルキル基を表し、具体的にはトリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、ヘプタフルオロイソプロピル基、ペンタフルオロシクロプロピル基、ノナフルオロブチル基、ノナフルオロイソブチル基、ノナフルオロターシャリーブチル基、ヘプタフルオロシクロブチル基、ウンデカフルオロペンチル基、ノナフルオロシクロペンチル基、トリデカフルオロヘキシル基、ウンデカフルオロシクロヘキシル基、ペンタデカフルオロヘプチル基、トリデカフルオロシクロヘプチル基、ヘプタデカフルオロオクチル基、ペンタデカシクロオクチル基、ノナデカフルオロノニル基、ヘプタデカフルオロシクロノニル基、ヘンイコサフルオロデセニル基、ノナデカフルオロシクロデセニル基などを表す。安価で大量に入手できる点から、一般式[3]で示されるモノヒドロペルフルオロアルカンとしては、好ましくはトリフルオロメタン、ペンタフルオロエタンであり、より好ましくはトリフルオロメタンである。
本発明における一般式[4]で示されるペルフルオロアルキルアルコールは、それぞれ一般式[1]のR1、R2と同じ置換基R1、R2を持つ、対応するペルフルオロアルキルアルコールである。
次に、本発明における反応方法について詳細に説明する。
1H NMR (400 MHz, CDCl3) δ: 2.86 (s, 1H), 7.35-7.37 (m, 6H), 7.48 (d, J = 4.8 Hz, 4H).
19F NMR (376 MHz, CDCl3) δ: 87.5 (s, 3F).
GC-MS m/z (%): 252 (M+, 10), 183 (100), 105 (94), 77 (50).
1H NMR (400 MHz, CDCl3) δ: 1.79 (d, J = 0.8 Hz, 3H), 2.40 (s, 1H), 7.35-7.43 (m, 3H), 7.58 (d, J = 7.6 Hz, 2H).
19F NMR (376 MHz, CDCl3) δ: 80.7 (s, 3F).
GC-MS m/z (%): 121 (100), 105 (33), 77 (74), 69 (22), 51 (17).
1H NMR (400 MHz, CDCl3) δ: 0.88 (t, J = 6.8 Hz, 3H), 1.27-1.31 (m, 12H), 1.34 (s, 1H), 1.38-1.49 (m, 2H), 1.62-1.67 (m, 2H), 1.81 (s, 1H).
19F NMR (376 MHz, CDCl3) δ: 78.6 (s, 3F).
GC-MS m/z (%): 171 (15), 112 (25), 97 (39), 83 (80), 70 (100), 56 (85).
1H NMR (400 MHz, CDCl3) δ: 1.54-1.78 (m, 11H).
19F NMR (376 MHz, CDCl3) δ: 76.7 (s, 3F).
GC-MS m/z (%): 99 (100), 81 (87), 55 (30).
1H NMR (400 MHz, CDCl3) δ: 2.85 (s, 1H), 7.32-7.37 (m, 6H), 7.55 (d, J = 6.8 Hz, 4H).
19F NMR (376 MHz, CDCl3) δ: 45.3 (s, 2F), 84.7 (s, 3F).
GC-MS m/z (%): 183 (63), 105 (100), 77 (53), 51 (17).
1H NMR (400 MHz, CDCl3) δ: 1.82 (s, 3H), 2.39 (s, 1H), 7.36-7.42 (m, 3H), 7.56 (d, J = 7.6 Hz, 2H).
19F NMR (376 MHz, CDCl3) δ: 38.7 (d, J = 277 Hz, 1F), 40.2 (d, J = 277 Hz, 1F), 83.8 (s, 3F).
GC-MS m/z (%): 240 (M+, 8), 121 (100), 86 (24), 84 (36).
1H NMR (400 MHz, アセトン-d6) δ: 1.76 (s, 3H), 2.09(s,3H), 5.49(s, 1H), 7.57 (d, J = 9.0 Hz, 2H), 7.67 (d, J = 9.0 Hz, 2H), 9.23(s, 1H).
19F NMR (376 MHz, アセトン-d6) δ: 83.1 (s, 3F).
GC-MS m/z (%): 247 (M+, 2), 178 (48), 136 (100), 120 (13), 94 (69), 77(14), 69 (5), 65 (25).
Claims (10)
- 一般式[1]:
で示されるカルボニル化合物と、一般式[2]:
M(OH)x [2]
[式中、Mは元素周期律表におけるI族、II族、III族、IV族、V族、VI族、VII族、VIII族、IX族、X族、XI族、XII族、及びXIII族に属する金属あるいは無置換若しくは炭素数1から10のアルキル基を置換基として有しても良いアンモニウムであり、それらは単独であっても、複数の物質の混合物であっても良く、xはMであらわされる物質の酸化数に一致する]
で示される水酸化物、及び一般式[3]:
RFH [3]
[式中、RFは炭素数1~2の直鎖あるいは炭素数3~10の直鎖、分岐あるいは環状構造を有することもあるアルキル基であり、炭素上の水素が全てフッ素で置換されたペルフルオロアルキル基を表す]
で示されるモノヒドロペルフルオロアルカンを有機溶媒中で反応させることを特徴とする、一般式[4]:
で示されるペルフルオロアルキル基を有するアルコールの製造方法。 - 一般式[3]で示されるRFHがトリフルオロメタンであることを特徴とする、請求項1に記載の方法。
- 一般式[3]で示されるRFHがペンタフルオロエタンであることを特徴とする、請求項1に記載の方法。
- 一般式[2]で示されるM(OH)xが水酸化カリウムであることを特徴とする、請求項1に記載の方法。
- 一般式[2]で示されるM(OH)xが水酸化ナトリウムであることを特徴とする、請求項1に記載の方法。
- 一般式[2]で示されるM(OH)xが水酸化テトラメチルアンモニウムまたはその水和物であることを特徴とする、請求項1に記載の方法。
- 一般式[2]で示されるM(OH)xが、粉末状で反応系に添加されることを特徴とする、請求項1~6のいずれかに記載の方法。
- 有機溶媒がジメチルスルホキシド、ジメチルホルムアミド、N-メチルピロリドン、テトラヒドロフラン、ジグライム、アセトニトリル、又はこれらの組み合わせであることを特徴とする、請求項1~7のいずれかに記載の製造方法。
- モノヒドロペルフルオロアルカンが気体の状態で反応液と接触することを特徴とする、請求項1~8のいずれかに記載の製造方法。
- モノヒドロペルフルオロアルカンを液体あるいは固体の状態で反応液と混合させることを特徴とする、請求項1~8のいずれかに記載の製造方法。
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EP17836536.7A EP3495341B1 (en) | 2016-08-05 | 2017-02-16 | Preparation process of perfluoroalkyl compound with monohydroperfluoroalkane as starting material |
JP2018531732A JP6751928B2 (ja) | 2016-08-05 | 2017-02-16 | モノヒドロペルフルオロアルカンを出発原料とするペルフルオロアルキル化合物の製造方法 |
CN201780048718.XA CN109563016B (zh) | 2016-08-05 | 2017-02-16 | 以单氢全氟烷烃为起始原料的全氟烷基化合物的制造方法 |
US16/323,299 US10450253B2 (en) | 2016-08-05 | 2017-02-16 | Preparation process of perfluoroalkyl compound with monohydroperfluoroalkane as starting material |
KR1020197004329A KR20190038842A (ko) | 2016-08-05 | 2017-02-16 | 모노하이드로퍼플루오로알칸을 출발 원료로 하는 퍼플루오로알킬 화합물의 제조 방법 |
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JPWO2018025429A1 (ja) | 2019-05-30 |
EP3495341A4 (en) | 2020-04-08 |
JP6751928B2 (ja) | 2020-09-09 |
KR20190038842A (ko) | 2019-04-09 |
CN109563016A (zh) | 2019-04-02 |
EP3495341A1 (en) | 2019-06-12 |
US10450253B2 (en) | 2019-10-22 |
EP3495341B1 (en) | 2022-11-02 |
CN109563016B (zh) | 2022-05-13 |
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