WO2012172893A1 - ヘキサフルオロアセトンまたはその水和物の製造法 - Google Patents
ヘキサフルオロアセトンまたはその水和物の製造法 Download PDFInfo
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- WO2012172893A1 WO2012172893A1 PCT/JP2012/062021 JP2012062021W WO2012172893A1 WO 2012172893 A1 WO2012172893 A1 WO 2012172893A1 JP 2012062021 W JP2012062021 W JP 2012062021W WO 2012172893 A1 WO2012172893 A1 WO 2012172893A1
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- sulfide
- hexafluoroacetone
- hydrate
- reducing agent
- compound
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- 0 C*1(C)OO*O1 Chemical compound C*1(C)OO*O1 0.000 description 1
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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
- C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
-
- 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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
Definitions
- the present invention relates to a process for producing hexafluoroacetone or a hydrate thereof. More specifically, when the ozonide compound obtained by the ozonation of heptafluoroisobutenyl ether compound is subjected to reduction reaction in the presence of an organic sulfide compound reducing agent, hexafluoroacetone or its hydrate is produced in high yield. On how to do it.
- Hexafluoroacetone is used as a monomer for producing synthetic resins, synthetic rubbers, etc., or as an intermediate of a crosslinking agent such as bisphenol AF, or as an intermediate raw material for medicines, agricultural chemicals, etc.
- Non-patent document 1 Patent Document 1
- Patent Document 2 Patent Document 3
- Patent Document 4 Non-patent Document 4
- Patent Document 5 proposes a method for producing hexafluoroacetone or a hydrate thereof.
- Patent Document 6 describes, in production of a prostaglandin synthesis intermediate, ozonation of the butenyl group in a synthetic raw material, followed by reduction reaction in the presence of triphenylphosphine, in Examples 30 and 32. ing.
- Patent Document 7 describes in Reference Example 1 that the carbon-carbon double bond is ozonized and the obtained ozonide is subjected to a reduction reaction in the presence of dimethyl sulfide in the production of a steroid derivative.
- Patent Document 8 discloses ozonizing 4-alkyl-5-alkenylthiazole compounds and reducing the resulting ozonide compounds, such as lower alkyl disulfides, aryl phosphines, alkyl phosphines, alkyl phosphites, aryl Phosphites, alkali metal bisulfite, alkali metal pyrosulfite, alkali metal sulfite, alkali metal dithionite, thiodi lower alkyl alcohols, thiodi lower alkyl carboxylic acids, thiodialkyl nitriles, thiodiphenols It is described that the reduction reaction is carried out in the presence of thiocarbamides and the like.
- dimethyl sulfide, diethyl sulfide, dipropyl sulfide and the like are shown as examples of lower alkyl disulfides, and in Example 14 of which dimethyl sulfide is used, and when this ozonide compound reducing agent is used, (Example 14)
- the target 4-methyl-5-formylthiazole is obtained in the highest yield as compared with the case where other types of ozonide compound reducing agents are used, and diethyl sulfide and dipropyl are obtained.
- Sulfide is also considered to have the same effect as dimethyl sulfide.
- An object of the present invention is to provide hexafluoroacetone or a hydrate thereof in high yield when an ozonide compound obtained by ozonizing a heptafluoroisobutenyl ether compound is subjected to a reduction reaction in the presence of an organic sulfide compound reducing agent.
- the object of the present invention is to (Wherein R is an alkyl group having 1 to 8 carbon atoms, an aryl group or a benzyl group) 1-fluoro-4,4-bis (trifluoromethyl) -2,3,5-trioxolanyl ether represented by Achieved by a method of producing hexafluoroacetone or a hydrate thereof by reducing the compound in the presence of a dialkyl sulfide, diaryl sulfide, diaryl disulfide or diaralkyl sulfide reducing agent having an alkyl group of 3 or 4 carbon atoms. Be done.
- Patent Document 8 exemplifies lower alkyl disulfides such as dimethyl sulfide, diethyl sulfide, and dipropyl sulfide as an ozonide compound reducing agent, and in Example 14 using a dimethyl sulfide reducing agent, other types of ozonide compound reduction As described above, the objective compound is obtained in the highest yield as compared with the case where a reducing agent is used, but in the present invention where the reduction reaction product is different, dimethyl sulfide is used as an ozonide compound reducing agent. The yield of hexafluoroacetone trihydrate is not always good (Comparative Example 1 below).
- a phase transfer catalyst such as a quaternary ammonium salt
- the ozone oxidation reaction of heptafluoroisobutenyl ether compound is carried out in the absence of a solvent or after charging a raw material therein using a glass reaction vessel or the like, or in a hydrocarbon, a halogenated hydrocarbon, an ether, water, etc. It is carried out by contacting the ozone-containing oxidizing gas or air under stirring conditions at a temperature of about ⁇ 70 to 100 ° C., preferably about ⁇ 40 to 60 ° C., in the presence of a solvent.
- the concentration of ozone in oxygen gas or air is not particularly limited, but is generally about 0.1 to 1000 mg / L, preferably about 1 to 500 mg / L, and the molar ratio to the starting material is about 1 Used in proportions.
- the 1,2,4-trioxolane ring possessed by the obtained 1-fluoro-4,4-bis (trifluoromethyl) -2,3,5-trioxolanyl ether compound has extremely high activity and is reduced It is easily cleaved in the presence of a catalyst to form hexafluoroacetone and methyl fluoroformate.
- the reduction reaction of 1-fluoro-4,4-bis (trifluoromethyl) -2,3,5-trioxolanyl ether compound to hexafluoroacetone was carried out using a glass reaction vessel or the like, in which the raw material was charged. Thereafter, the reaction is carried out by reacting the specific ozonide reducing agent at a temperature of about ⁇ 60 to 30 ° C., preferably ⁇ 40 ° C. to 20 ° C., in the presence or absence of a solvent and under a nitrogen atmosphere.
- the type of solvent is not particularly limited as long as it is inert to the oxolane compound and the ozonide reducing agent, but in general, 1,1,1,3,3-pentafluorobutane (mfc 365) And other fluorinated solvents are used.
- any known ozonide can be used as long as it reductively decomposes ozonide (see Patent Document 9), for example, sulfide compounds (dimethyl sulfide, dialkyl disulfides are exemplified) And sulfur-containing compounds such as sodium thiosulfate, phosphorus-containing compounds such as triethyl phosphite, triphenyl phosphine and phosphite, and metals or metal compounds such as zinc, raney nickel and sodium borohydride.
- sulfide compounds dimethyl sulfide, dialkyl disulfides are exemplified
- sulfur-containing compounds such as sodium thiosulfate, phosphorus-containing compounds such as triethyl phosphite, triphenyl phosphine and phosphite, and metals or metal compounds such as zinc, raney nickel and sodium borohydride.
- diaralkyl sulfide is used typified, for example, In the diphenyl disulfide and the like of the melting point of 62 ° C., is used as the organic solvent solution such as toluene.
- sulfide compounds are used in a ratio of about 1 to 10 moles with respect to 1 mole of 1-fluoro-4,4-bis (trifluoromethyl) -2,3,5-trioxolanyl ether compound.
- the product gas is led to a water trap, an ice-cooled trap and a dry ice / methanol trap to collect the product, and hexafluoroacetone is mainly used in the water trap and ice-cooled trap. It is obtained as a hydrate aqueous solution.
- hexafluoroacetone is A simple and convenient method is to use acetone as a simple and convenient method, without separating acetone as it is, once introducing a decomposition gas into water to form a hydrate, and separating or analyzing it.
- the obtained hexafluoroacetone hydrate can be used as a solvent of polyester, polyamide etc. as such, but when dehydrating it, it is carried out by a method using phosphorus pentoxide, concentrated sulfuric acid, sulfuric anhydride, molecular sieve etc. (See Patent Documents 10 to 11).
- Comparative example 2 In Comparative Example 1, 150 ml of glacial acetic acid was dropped over 10 minutes instead of dropping dimethyl sulfide, and then 49.0 g (0.75 mol) of zinc pieces were added little by little while maintaining the inside of the system at about 30 ° C. As a result of stirring, it was confirmed that 68.0 g (yield 82%) of hexafluoroacetone trihydrate was obtained.
- Comparative example 3 In Comparative Example 1, 188 g (1.131 mol) of triethyl phosphite was added over 15 minutes instead of dropwise addition of dimethyl sulfide, and then stirring was performed overnight, 75.5 g of hexafluoroacetone trihydrate was collected. It was confirmed that the rate was 91%).
- Example 1 In Comparative Example 1, 44.9 g of the same molar amount (0.38 mol) of dipropyl sulfide is used instead of dimethyl sulfide, and this is dropped at a reaction temperature of 20 ° C. to carry out a reaction, 78.7 g of hexafluoroacetone trihydrate (Yield 95%) was obtained.
- Example 2 In Comparative Example 1, 55.6 g of the same molar amount (0.38 mol) of dibutyl sulfide is used instead of dimethyl sulfide, and this is dropped at a reaction temperature of 15 ° C. to carry out a reaction, 77.1 g of hexafluoroacetone trihydrate Yield 93%).
- Comparative example 4 In Comparative Example 1, 76.9 g of dihexyl sulfide of the same molar amount (0.38 mol) is used instead of dimethyl sulfide, and this is added dropwise at a reaction temperature of 30 ° C. Yield 90%).
- Example 3 In Comparative Example 1, 70.7 g of diphenyl sulfide of the same molar amount (0.38 mol) is used instead of dimethyl sulfide, and this is dropped at a reaction temperature of 30 ° C. to carry out a reaction, 80.4 g of hexafluoroacetone trihydrate Yield 97%).
- Example 4 In Comparative Example 1, in place of dimethyl sulfide, 82.9 g of the same molar amount (0.38 mol) of diphenyl disulfide (used as a solution dissolved in 110.5 g of toluene) is used, and this is reacted dropwise at a reaction temperature of 30 ° C. There were obtained 78.7 g (yield 95%) of hexafluoroacetone trihydrate.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
を経て、ヘキサフルオロアセトンまたはその水和物を製造する方法を提案している(特許文献5)。
・特許文献6には、プロスタグランジン合成中間体の製造に際し、合成原料中のブテニル基をオゾン酸化し、次いでトリフェニルホスフィンの存在下で還元反応させることが、実施例30、32に記載されている。
・特許文献7には、ステロイド誘導体の製造に際し、炭素-炭素二重結合をオゾン酸化し、得られたオゾニドをジメチルスルフィドの存在下で還元反応させることが、参考例1に記載されている。
・特許文献8には、4-アルキル-5-アルケニルチアゾール化合物をオゾン分解し、得られたオゾニド化合物を還元剤、例えば低級アルキルジスルフィド類、アリールホスフィン類、アルキルホスフィン類、アルキルホスファイト類、アリールホスファイト類、重亜硫酸アルカリ金属塩、ピロ亜硫酸アルカリ金属塩、亜硫酸アルカリ金属塩、亜二チオン酸アルカリ金属塩、チオジ低級アルキルアルコール類、チオジ低級アルキルカルボン酸類、チオジアルキルニトリル類、チオジフェノール類、チオカルボアミド類等の存在下で還元反応させることが記載されている。
ここで、低級アルキルジスルフィド類の例としてジメチルスルフィド、ジエチルスルフィド、ジプロピルスルフィド等が示されており、その実施例14ではジメチルスルフィドが用いられており、このオゾニド化合物還元剤を用いた場合には(実施例14)、他の種類のオゾニド化合物還元剤を用いた場合と比較して、最高の収率で目的物たる4-メチル-5-ホルミルチアゾールが得られており、ジエチルスルフィド、ジプロピルスルフィドもジメチルスルフィドと同効物質と考えられる。
(a) 赤外線吸収スペクトルでのオキシラン環に由来する波数1230cm-1の特性吸収
(b) 19F-NMRによるフッ素原子の結合様式
(c) 1H-NMRによる水素原子の結合様式
(d) 質量スペクトル(M/Z)=228に由来する特徴的な強いピーク
ヘプタフルオロイソブテニルメチルエーテル(純度91%)100g(0.43モル)を容量500mlの三口フラスコに仕込み、ジムロート冷却管には-20℃のブラインを流し、0℃で攪拌しながら、約125mg/L濃度のオゾンを含む酸素ガスを、5時間30分の間に約165L(オゾン量として約0.43モル)をバブリングさせた。
赤外線吸収スペクトル:1230cm-1(2,3,5-トリオキソラン)
19F-NMR(TFA,CH2Cl2):-15.3ppm(d,j=2.19Hz,1F)
+0.58ppm(dq,j=2.19,2.63Hz,3F)
+1.90ppm(q,j=2.63Hz.3F)
1H-NMR(TMS,CDCl3):3.58ppm(s,3H)
質量スペクトル(EI,M/Z):260(M+)
1-フルオロ-4,4-ビス(トリフルオロメチル)-2,3,5-トリオキソラニル・メチルエーテル(純度98%)100g(0.38モル)を容量500mlの五口フラスコに仕込み、窒素バブリングを行いながら、ジムロート冷却管には-20℃のブラインを流し、-20℃の反応温度で攪拌しながら、滴下ロートを用いてジメチルスルフィド23.4g(0.38モル)を30分間かけて滴下した。反応の結果得られたガスを氷水で0℃に冷却した水トラップで捕集し、得られた水層を19F-NMRで分析したところ、ヘキサフルオロアセトン・三水和物が73.8g(収率89%)得られていることが確認された。
比較例1において、ジメチルスルフィドを滴下する代わりに、氷酢酸150mlを10分間かけて滴下した後、系内を30℃程度に維持しながら亜鉛片49.0g(0.75モル)を少量ずつ加え、1時間攪拌したところ、ヘキサフルオロアセトン・三水和物が68.0g(収率82%)得られていることが確認された。
比較例1において、ジメチルスルフィドを滴下する代わりに、トリエチルフォスファイト188g(1.131mol)を15分間かけて加えた後、オーバーナイトで攪拌したところ、ヘキサフルオロアセトン・三水和物が75.5g(収率91%)得られていることが確認された。
比較例1において、ジメチルスルフィドの代わりに同モル量(0.38モル)のジプロピルスルフィド44.9gを用い、これを反応温度20℃で滴下して反応を行い、ヘキサフルオロアセトン・三水和物78.7g(収率95%)を得た。
比較例1において、ジメチルスルフィドの代わりに同モル量(0.38モル)のジブチルスルフィド55.6gを用い、これを反応温度15℃で滴下して反応を行い、ヘキサフルオロアセトン・三水和物77.1g(収率93%)を得た。
比較例1において、ジメチルスルフィドの代わりに同モル量(0.38モル)のジヘキシルスルフィド76.9gを用い、これを反応温度30℃で滴下して反応を行い、ヘキサフルオロアセトン・三水和物74.6g(収率90%)を得た。
比較例1において、ジメチルスルフィドの代わりに同モル量(0.38モル)のジフェニルスルフィド70.7gを用い、これを反応温度30℃で滴下して反応を行い、ヘキサフルオロアセトン・三水和物80.4g(収率97%)を得た。
比較例1において、ジメチルスルフィドの代わりに同モル量(0.38モル)のジフェニルジスルフィド82.9g(トルエン110.5gに溶解させた溶液として使用)を用い、これを反応温度30℃で滴下して反応を行い、ヘキサフルオロアセトン・三水和物78.7g(収率95%)を得た。
Claims (6)
- ジアルキルスルフィド還元剤として、ジプロピルスルフィドまたはジブチルスルフィドが用いられる請求項1記載のヘキサフルオロアセトンまたはその水和物の製造法。
- ジアリールスルフィド還元剤としてジフェニルスルフィドが、またジアリールジスルフィドとしてジフェニルジスルフィドが用いられる請求項1記載のヘキサフルオロアセトンまたはその水和物の製造法。
- オゾニド還元剤が、1-フルオロ-4,4-ビス(トリフルオロメチル)-2,3,5-トリオキソラニル・エーテル化合物1モルに対して、1~10モルの割合で用いられる請求項1記載のヘキサフルオロアセトンまたはその水和物の製造法。
- 生成したヘキサフルオロアセトンを水トラップで捕集し、ヘキサフルオロアセトン水和物水溶液を形成させる請求項1記載のヘキサフルオロアセトン水和物の製造法。
- ヘキサフルオロアセトンを水和物水溶液とした後、脱水させる請求項5記載のヘキサフルオロアセトンの製造法。
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EP12800128.6A EP2722324B1 (en) | 2011-06-17 | 2012-05-10 | Method for producing hexafluoroacetone or hydrate thereof |
US14/124,085 US8853462B2 (en) | 2011-06-17 | 2012-05-10 | Method for producing hexafluoroacetone or hydrate thereof |
JP2013520473A JP5664779B2 (ja) | 2011-06-17 | 2012-05-10 | ヘキサフルオロアセトンまたはその水和物の製造法 |
CN201280029749.8A CN103619794B (zh) | 2011-06-17 | 2012-05-10 | 六氟丙酮或其水合物的制备方法 |
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JP2011134747 | 2011-06-17 | ||
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EP (1) | EP2722324B1 (ja) |
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CN103394362A (zh) * | 2013-07-26 | 2013-11-20 | 临海市利民化工有限公司 | 一种以八氟异丁烯为原料制备六氟丙酮的催化剂、制备方法及应用 |
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CN114591158B (zh) * | 2020-12-04 | 2024-01-30 | 福建省漳平市九鼎氟化工有限公司 | 一种由全氟-2-甲基-2-戊烯制备五氟丙酰氟和六氟丙酮的方法及装置 |
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- 2012-05-10 CN CN201280029749.8A patent/CN103619794B/zh active Active
- 2012-05-10 US US14/124,085 patent/US8853462B2/en active Active
- 2012-05-10 JP JP2013520473A patent/JP5664779B2/ja active Active
- 2012-05-10 EP EP12800128.6A patent/EP2722324B1/en active Active
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CN103394362A (zh) * | 2013-07-26 | 2013-11-20 | 临海市利民化工有限公司 | 一种以八氟异丁烯为原料制备六氟丙酮的催化剂、制备方法及应用 |
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JPWO2012172893A1 (ja) | 2015-02-23 |
US20140121416A1 (en) | 2014-05-01 |
JP5664779B2 (ja) | 2015-02-04 |
EP2722324A4 (en) | 2014-11-12 |
US8853462B2 (en) | 2014-10-07 |
CN103619794A (zh) | 2014-03-05 |
EP2722324A1 (en) | 2014-04-23 |
CN103619794B (zh) | 2015-06-24 |
EP2722324B1 (en) | 2015-08-26 |
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