JP2011042626A - Method for producing perfluoroorganic substance - Google Patents
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Abstract
Description
本発明は、ペルフルオロ有機基を含有する有機化合物(ペルフルオロ有機物)の製造方法に関する。ペルフルオロ有機物は化学品、医農薬、樹脂等の中間体として有用な化合物である。特に置換可能な官能基が結合した炭化水素部位を有するペルフルオロ有機物は機能性材料を製造するためのモノマー成分として有用な化合物である。 The present invention relates to a method for producing an organic compound (perfluoro organic substance) containing a perfluoro organic group. Perfluoro organic substances are useful compounds as intermediates for chemicals, medical pesticides, resins and the like. In particular, a perfluoro organic substance having a hydrocarbon moiety to which a substitutable functional group is bonded is a useful compound as a monomer component for producing a functional material.
ペルフルオロ有機基を有機化合物に導入する手法としては、ラジカル開始剤存在下、ペルフルオロ有機ハロゲン化物とオレフィン化合物を反応させる手法が知られている。(特許文献1、非特許文献1参照)
しかし、これらの手法ではヨウ素や臭素などのハロゲン付加体で得られるため、さらに脱ハロゲン化の工程が必要となる。
As a technique for introducing a perfluoro organic group into an organic compound, a technique of reacting a perfluoro organic halide with an olefin compound in the presence of a radical initiator is known. (See Patent Document 1 and Non-Patent Document 1)
However, since these methods can be obtained with a halogen adduct such as iodine or bromine, a further dehalogenation step is required.
脱ハロゲン化としては、水素化アルミニウムリチウム、水素化トリブチルスズ、パラジウム(0)などの還元剤を用いる手法、またはニッケルやパラジウム等の金属触媒による接触水素化還元などが知られている。(非特許文献2参照)
また、合成中間体としてハロゲン付加体を経ない手法も報告されているが、純粋な一工程とはいえないし、やはり水素化トリブチルスズ等の還元剤が必須である。(非特許文献3、4参照)
As the dehalogenation, a method using a reducing agent such as lithium aluminum hydride, tributyltin hydride, palladium (0), or catalytic hydrogenation reduction using a metal catalyst such as nickel or palladium is known. (See Non-Patent Document 2)
In addition, although a method without a halogen adduct has been reported as a synthetic intermediate, it is not a pure one step, and a reducing agent such as tributyltin hydride is essential. (See Non-Patent Documents 3 and 4)
しかし、還元剤として用いられる水素化アルミニウムリチウムや水素化トリブチルスズは危険性や毒性が非常に高く、工業化にあたっては設備費も増大するなどの不利がある。さらに反応の際に生じるアルミニウム化合物やスズ化合物を廃棄する際には環境面および安全面に対して十分な注意が必要となる。
また、接触水素化還元ではニッケルやパラジウムなどの高価な貴金属触媒を使用するため、工業化する場合には触媒の回収が必要になるという欠点もある。
However, lithium aluminum hydride and tributyltin hydride used as a reducing agent are extremely dangerous and toxic and have disadvantages such as increased equipment costs for industrialization. Furthermore, when disposing of aluminum compounds and tin compounds generated during the reaction, sufficient attention must be paid to the environment and safety.
In addition, since catalytic hydrogenation reduction uses an expensive noble metal catalyst such as nickel or palladium, there is also a disadvantage that the catalyst must be recovered when industrialized.
本発明はラジカル開始剤存在下、ペルフルオロ有機ハロゲン化物とオレフィン化合物を反応させ、還元剤や金属触媒を用いる還元反応を用いることなく、一工程で、ペルフルオロ有機物を製造する方法を提供する。 The present invention provides a method for producing a perfluoro organic compound in one step without reacting a perfluoro organic halide with an olefin compound in the presence of a radical initiator and using a reduction reaction using a reducing agent or a metal catalyst.
本発明者らは、ペルフルオロ有機ハロゲン化物とオレフィン化合物を反応させる際に、通常は触媒量で用いるラジカル開始剤を1モル当量以上で反応させることにより、驚くべきことに一工程でペルフルオロ有機物が製造できることを見出し、本発明を完成させた。 When the present inventors react a perfluoro organic halide with an olefin compound, a perfluoro organic compound is surprisingly produced in one step by reacting a radical initiator usually used in a catalytic amount with 1 molar equivalent or more. We have found that this is possible, and have completed the present invention.
すなわち、本発明は、一般式(1)
Rf−X (1)
[式中Rfはペルフルオロ有機基を表し、Xはヨウ素または臭素を表す。]で表わされるペルペルフルオロ有機ハロゲン化物と、一般式(2)
Rf-X (1)
[Wherein Rf represents a perfluoro organic group, and X represents iodine or bromine. A perperfluoro organic halide represented by the general formula (2)
本発明によれば化学品、機能性材料、医農薬、樹脂等として有用なペルフルオロ有機物が、還元剤や触媒を使用せずに、わずか一工程で効率的に得られる。本発明の方法は製造工程が簡略化できる方法であり、更に毒性の高い還元剤や、高価な貴金属触媒を使用しないことから、工業的プロセスとして非常に有用な方法である。 According to the present invention, perfluoro organic substances useful as chemical products, functional materials, medical pesticides, resins, and the like can be efficiently obtained in just one step without using a reducing agent or a catalyst. The method of the present invention is a method that can simplify the production process, and is very useful as an industrial process because it does not use a highly toxic reducing agent or an expensive noble metal catalyst.
次に、本発明について更に詳しく説明する。
なお本明細書においては、式(1)で表わされる化合物を、化合物(1)と記す。他の式で表わされる化合物においても同様に記す。
Next, the present invention will be described in more detail.
In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
化合物(1)におけるRfはペルフルオロ有機基である。ここで有機基とは、C−H部分を必須とする基をいう。有機基としては、飽和炭化水素基、エーテル性酸素原子含有飽和炭化水素基が好ましい。 Rf in the compound (1) is a perfluoro organic group. Here, the organic group refers to a group in which a C—H moiety is essential. The organic group is preferably a saturated hydrocarbon group or an etheric oxygen atom-containing saturated hydrocarbon group.
Rfの炭素数は1〜150が好ましく、特に1〜50が好ましく、4〜16が最も好ましい。
Rfの構造は直鎖構造であっても、分岐構造であっても、環構造であっても、または部分的に環構造を有する構造であってもよく、化合物(1)の入手のしやすさの点から直鎖構造、または分岐構造であるのが好ましい。
Rf has preferably 1 to 150 carbon atoms, particularly preferably 1 to 50, and most preferably 4 to 16 carbon atoms.
The structure of Rf may be a linear structure, a branched structure, a ring structure, or a structure having a partial ring structure, and the compound (1) is easily available. From this point, a linear structure or a branched structure is preferable.
Rfの具体例としては次の例が挙げられる。
化合物(2)は分子内にヒドロキシル基、エーテル基、カルボキシル基、エステル基等の含酸素基、アミノ基等の含窒素基、メルカプト基、スルフィド基等の含硫黄基、ホスフィン基、ホスフィンオキシド基等の含リン基、またはフェニル基等の置換基を有していてもよい。 The compound (2) has a hydroxyl group, an ether group, a carboxyl group, an ester group or other oxygen-containing group in the molecule, an amino group or other nitrogen-containing group, a mercapto group or a sulfur-containing group such as a sulfide group, a phosphine group or a phosphine oxide group. And may have a substituent such as a phenyl group.
これらの代表的なオレフィン化合物として、例えば、エチレン、プロピレン、1−ブテン、2−ブテン、イソブテン、1−ペンテン、1−ヘキセン、2−エチル−1−ブテン、1−ヘプテン、1−オクテン、1−ノネン、1−デセン、シクロヘキセン、シクロオクテン、ノルボルネン等の脂肪族モノオレフィン類、スチレン、アリルベンゼン、4−フェニル−1−ブテン等の芳香族モノオレフィン類、ブタジエン、1,5−ヘキサジエン、1,7−オクタジエン等のジオレフィン類、アリルアルコール、2−ブテノール、3−ブテノール、3−ヘキセノール、4−ヘキセノール、5−ヘキセノール、7−オクテノール、10−ウンデセノール等の不飽和アルコール類、アリルエチルエーテル、ジアリルエーテル等の不飽和エーテル類、3−ブテン酸、5−ヘキセン酸、7−オクテン酸、10−ウンデセン酸等の不飽和カルボン酸、3−ブテン酸メチル、3−ブテン酸エチル、5−ヘキセン酸メチル、10−ウンデセン酸メチル等の不飽和カルボン酸エステル類、アリルアセテート、3−ブテニルアセテート等のカルボン酸不飽和アルコールエステル類、アリルアミン、ジアリルアミン、トリアリルアミン、3−ブテニルアミン、5−ヘキセニルアミン等の不飽和アミン類、アリルメルカプタン、3−ブテニルメルカプタン、5−ヘキセニルメルカプタン等の不飽和メルカプタン類、アリルスルフィド等の不飽和スルフィド類、アリルジメチルホスフィン、アリルジフェニルホスフィン等の不飽和ホスフィン類、アリルジフェニルホスフィンオキシド等の不飽和ホスフィンオキシド類等が挙げられる。
これらのオレフィン化合物の使用量は、通常、Rf−Xに対して0.1〜5モル当量、好ましくは0.2〜0.5モル当量である。
Examples of these representative olefin compounds include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 2-ethyl-1-butene, 1-heptene, 1-octene, 1 -Aliphatic monoolefins such as nonene, 1-decene, cyclohexene, cyclooctene, norbornene, aromatic monoolefins such as styrene, allylbenzene, 4-phenyl-1-butene, butadiene, 1,5-hexadiene, 1 , 7-octadiene and other diolefins, allyl alcohol, 2-butenol, 3-butenol, 3-hexenol, 4-hexenol, 5-hexenol, 7-octenol, unsaturated alcohols such as 10-undecenol, allyl ethyl ether , Unsaturated ethers such as diallyl ether, 3-butyl Acid, 5-hexenoic acid, 7-octenoic acid, unsaturated carboxylic acid such as 10-undecenoic acid, methyl 3-butenoate, ethyl 3-butenoate, methyl 5-hexenoate, methyl 10-undecenoate, etc. Saturated carboxylic acid esters, carboxylic acid unsaturated alcohol esters such as allyl acetate and 3-butenyl acetate, unsaturated amines such as allylamine, diallylamine, triallylamine, 3-butenylamine and 5-hexenylamine, allyl mercaptan, 3 -Unsaturated mercaptans such as butenyl mercaptan and 5-hexenyl mercaptan; unsaturated sulfides such as allyl sulfide; unsaturated phosphines such as allyldimethylphosphine and allyldiphenylphosphine; unsaturated phosphine oxides such as allyldiphenylphosphine oxide And the like.
The amount of these olefin compounds used is usually 0.1 to 5 molar equivalents, preferably 0.2 to 0.5 molar equivalents relative to Rf-X.
本発明において使用されるラジカル開始剤としては、ラジカルを発生させるものであれば特に制限されない。代表的なラジカル開始剤としては、例えば、アゾビスイソブチロニトリル、ジメチル−2,2’−アゾビスイソブチレート、2,2’−アゾビス(4−メト
キシ−2,4−ジメチルバレロニトリル)、等のアゾ化合物、過酸化ベンゾイル、ジtert−ブチルパーオキシド等のパーオキシド化合物、トリメチルボラン、トリエチルボラン等のトリアルキルボラン等が挙げられるが、トリアルキルボランが好ましい。
The radical initiator used in the present invention is not particularly limited as long as it generates radicals. Typical radical initiators include, for example, azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile). An azo compound such as benzoyl peroxide, a peroxide compound such as ditert-butyl peroxide, and a trialkylborane such as trimethylborane and triethylborane are preferable, and a trialkylborane is preferable.
トリアルキルボランの具体例としては、トリメチルボラン、トリエチルボラン、トリ(n−プロピル)ボラン、トリ(iso−プロピル)ボラン、トリ(n−ブチル)ボラン、トリ(sec−ブチル)ボラン、トリ(iso−ブチル)ボラン、トリ(tert−ブチル)ボラン、トリ(1−メチルブチル)ボラン、トリ(2−メチルブチル)ボラン、トリ(neo−ペンチル)ボラン、トリ(1,2−ジメチルプロピル)ボラン、トリ(1−エチルプロピル)ボラン、トリ(n−ヘキシル)ボラン、トリ(シクロヘキシル)ボランなどが挙げられる。この中では、工業的な入手容易性の点から、トリエチルボランが好ましい。 Specific examples of the trialkylborane include trimethylborane, triethylborane, tri (n-propyl) borane, tri (iso-propyl) borane, tri (n-butyl) borane, tri (sec-butyl) borane, and tri (iso). -Butyl) borane, tri (tert-butyl) borane, tri (1-methylbutyl) borane, tri (2-methylbutyl) borane, tri (neo-pentyl) borane, tri (1,2-dimethylpropyl) borane, tri ( 1-ethylpropyl) borane, tri (n-hexyl) borane, tri (cyclohexyl) borane and the like. Of these, triethylborane is preferred from the viewpoint of industrial availability.
ラジカル開始剤の使用量はRf−Xに対して1モル当量以上であれば特に制限されないが、好ましくはRf−Xに対して1〜10モル当量、より好ましくは1〜5モル当量である。 Although there will be no restriction | limiting in particular if the usage-amount of a radical initiator is 1 molar equivalent or more with respect to Rf-X, Preferably it is 1-10 molar equivalent with respect to Rf-X, More preferably, it is 1-5 molar equivalent.
反応は、無溶媒で実施しても、溶媒の存在下に実施してもよい。溶媒を用いる場合は、該反応において不活性な溶媒の1種または2種以上を用いうる。溶媒としては、シクロヘキサン、イソオクタン、n−ヘキサン等の炭化水素系溶媒、ジクロロメタン、ジクロロエタン、四塩化炭素、クロロホルム等のハロゲン化炭化水素系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル−tert−ブチルエーテル、エチレングリコールジメチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、アセトニトリル等のニトリル系溶媒が用いられる。また用いる溶媒の量に特に制限はない。 The reaction may be carried out without a solvent or in the presence of a solvent. When using a solvent, 1 type (s) or 2 or more types of the solvent inactive in this reaction can be used. Solvents include hydrocarbon solvents such as cyclohexane, isooctane and n-hexane, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, carbon tetrachloride and chloroform, diethyl ether, diisopropyl ether, methyl-tert-butyl ether, and ethylene glycol. Ether solvents such as dimethyl ether, tetrahydrofuran and dioxane, and nitrile solvents such as acetonitrile are used. There is no particular limitation on the amount of solvent used.
反応の圧力は、減圧下、大気圧下、または加圧下のいずれであってもよい。
反応時間、反応温度にも何ら制限はない。いずれも化合物(1)、化合物(2)の構造により適宜変更しうるが、30分〜72時間が好ましい。また反応温度も化合物(1)、化合物(2)の構造により適宜変更しうるが、0℃〜200℃が好ましい。
以下に、本発明を、実施例を用いて更に詳細に説明するが、これらの実施例は本発明の概要を示すもので、本発明はこれらの実施例に限定されるものではない。
The pressure of the reaction may be any of reduced pressure, atmospheric pressure, or increased pressure.
There is no limitation on reaction time and reaction temperature. Any of these can be appropriately changed depending on the structures of the compound (1) and the compound (2), but is preferably 30 minutes to 72 hours. Moreover, although reaction temperature can be suitably changed with the structure of a compound (1) and a compound (2), 0 to 200 degreeC is preferable.
The present invention will be described in more detail with reference to the following examples. However, these examples show the outline of the present invention, and the present invention is not limited to these examples.
3‐ブテン1‐オール(71.7 mg, 0.99 mmol)とペルフルオロ-2,5,8-トリオキサドデシルブロミド (1.1 g, 1.8 mmol)をヘキサン-イソオクタン(1:1)混合溶液(10 mL)に溶解させた。75℃に昇温し、攪拌しながら1.0 Mトリエチルボランヘキサン溶液(2.5 mL, 2.5 mmol)を加え、更に75℃で攪拌した。15時間後、溶液を室温にし、溶媒を濃縮した。得られた残査をシリカゲルカラムクロマトグラフィーで精製(n-ヘキサン→n-ヘキサン:酢酸エチル=4:1)することにより、目的物である1H,1H,2H,2H,3H,3H,4H,4H-ペルフルオロ-6,9,12-トリオキサヘキサデカン-1-オール(264 mg, 45%)が得られた。
1H NMR (CDCl3, 600 MHz;内部標準TMS δ ppm) δ 1.25 (brs, 1H), 1.61-1.67 (m, 4H), 2.09-2.18 (m, 2H), 3.64-3.68 (m, 2H)
3-Buten-1-ol (71.7 mg, 0.99 mmol) and perfluoro-2,5,8-trioxadodecyl bromide (1.1 g, 1.8 mmol) dissolved in hexane-isooctane (1: 1) mixed solution (10 mL) I let you. The temperature was raised to 75 ° C., 1.0 M triethylborane hexane solution (2.5 mL, 2.5 mmol) was added with stirring, and the mixture was further stirred at 75 ° C. After 15 hours, the solution was brought to room temperature and the solvent was concentrated. By purifying the obtained residue by silica gel column chromatography (n-hexane → n-hexane: ethyl acetate = 4: 1), the target products 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H-perfluoro-6,9,12-trioxahexadecan-1-ol (264 mg, 45%) was obtained.
1 H NMR (CDCl 3 , 600 MHz; internal standard TMS δ ppm) δ 1.25 (brs, 1H), 1.61-1.67 (m, 4H), 2.09-2.18 (m, 2H), 3.64-3.68 (m, 2H)
3‐ブテン1‐オール(73.6 mg, 1.02 mmol)とペルフルオロオクチルブロミド (1.2 g, 2.3 mmol)をヘキサン-イソオクタン(1:1)混合溶液(10 mL)に溶解させた。75℃に昇温し、攪拌しながら1.0 Mトリエチルボランヘキサン溶液(2.5 mL, 2.5 mmol)を加え、更に75℃で攪拌した。15時間後、溶液を室温にし、溶媒を濃縮した。得られた残査をシリカゲルカラムクロマトグラフィーで精製(n-ヘキサン→n-ヘキサン:酢酸エチル=4:1)することにより、目的物である1H,1H,2H,2H,3H,3H,4H,4H-ペルフルオロドデカン-1-オール(246 mg, 48%)が得られた。
1H NMR (CDCl3, 600 MHz;内部標準TMS δ ppm)δ 1.26 (brs, 1H), 1.62-1.70 (m, 2H), 1.70-1.76 (m, 2H), 2.05-2.16 (m, 2H), 3.70 (t, J = 6.2 Hz, 2H).
3-Buten-1-ol (73.6 mg, 1.02 mmol) and perfluorooctyl bromide (1.2 g, 2.3 mmol) were dissolved in a hexane-isooctane (1: 1) mixed solution (10 mL). The temperature was raised to 75 ° C., 1.0 M triethylborane hexane solution (2.5 mL, 2.5 mmol) was added with stirring, and the mixture was further stirred at 75 ° C. After 15 hours, the solution was brought to room temperature and the solvent was concentrated. By purifying the obtained residue by silica gel column chromatography (n-hexane → n-hexane: ethyl acetate = 4: 1), the target products 1H, 1H, 2H, 2H, 3H, 3H, 4H, 4H-perfluorododecan-1-ol (246 mg, 48%) was obtained.
1 H NMR (CDCl 3 , 600 MHz; internal standard TMS δ ppm) δ 1.26 (brs, 1H), 1.62-1.70 (m, 2H), 1.70-1.76 (m, 2H), 2.05-2.16 (m, 2H) , 3.70 (t, J = 6.2 Hz, 2H).
本発明は、ペルフルオロ有機物の製造方法を提供するものであり、ペルフルオロ有機物は化学品、医農薬、樹脂等の中間体として有用な化合物である。特に、置換可能な官能基が結合した炭化水素部位を有するペルフルオロ有機物は、機能性材料を製造するためのモノマー成分として有用な化合物である。 The present invention provides a method for producing a perfluoro organic substance, and the perfluoro organic substance is a compound useful as an intermediate for chemicals, medical pesticides, resins and the like. In particular, a perfluoro organic substance having a hydrocarbon moiety to which a functional group capable of substitution is bonded is a useful compound as a monomer component for producing a functional material.
Claims (3)
Rf−X (1)
[式中Rfはペルフルオロ有機基を表し、Xはヨウ素または臭素を表す。]で表わされるペルフルオロ有機ハロゲン化物と、一般式(2)
Rf-X (1)
[Wherein Rf represents a perfluoro organic group, and X represents iodine or bromine. ] Perfluoro organic halide represented by the general formula (2)
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JPS5411284B2 (en) * | 1972-11-04 | 1979-05-14 | ||
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JPH11180914A (en) * | 1997-10-14 | 1999-07-06 | Bayer Ag | Production of pentafluoropentanol |
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