JPS63206491A - Production of polyfluorobenzyl alcohol - Google Patents
Production of polyfluorobenzyl alcoholInfo
- Publication number
- JPS63206491A JPS63206491A JP62039288A JP3928887A JPS63206491A JP S63206491 A JPS63206491 A JP S63206491A JP 62039288 A JP62039288 A JP 62039288A JP 3928887 A JP3928887 A JP 3928887A JP S63206491 A JPS63206491 A JP S63206491A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- manufacturing
- alcohol
- electrolytic solution
- polyfluorobenzoic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229910000497 Amalgam Inorganic materials 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- KVLBXIOFJUWSJQ-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzoic acid Chemical compound OC(=O)C1=C(F)C(F)=CC(F)=C1F KVLBXIOFJUWSJQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 claims description 20
- 239000008151 electrolyte solution Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- SFKRXQKJTIYUAG-UHFFFAOYSA-N 2,3,4,5-tetrafluorobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(F)C(F)=C1F SFKRXQKJTIYUAG-UHFFFAOYSA-N 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 229910052725 zinc Inorganic materials 0.000 abstract description 10
- 239000011701 zinc Substances 0.000 abstract description 10
- PGJYYCIOYBZTPU-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzyl alcohol Chemical compound OCC1=C(F)C(F)=C(F)C(F)=C1F PGJYYCIOYBZTPU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- -1 lithium aluminum hydride Chemical compound 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 2
- AGWVQASYTKCTCC-UHFFFAOYSA-N (2,3,5,6-tetrafluorophenyl)methanol Chemical compound OCC1=C(F)C(F)=CC(F)=C1F AGWVQASYTKCTCC-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229910000761 Aluminium amalgam Inorganic materials 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019785 NBF4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000003938 benzyl alcohols Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- WOFDVDFSGLBFAC-UHFFFAOYSA-N lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、医薬、農薬、写真薬剤をはじめとする情報記
録材料等の製造上重要な中間体である、ペンタフルオロ
ベンジルアルコール（以下ＰＦＢＡＬと略す）又は２，
３，５．６−チトラフルオロベンジルアルコール（以下
２．３．５．６−ＴＦＢＡＬと略す）などのポリフルオ
ロベンジルアルコールの新規な選択的電解還元製造法に
関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to pentafluorobenzyl alcohol (hereinafter referred to as PFBAL), which is an important intermediate in the production of information recording materials such as pharmaceuticals, agricultural chemicals, and photographic agents. omitted) or 2,
The present invention relates to a novel selective electrolytic reduction production method for polyfluorobenzyl alcohol such as 3,5.6-titrafluorobenzyl alcohol (hereinafter abbreviated as 2.3.5.6-TFBAL).
従来、ベンジルアルコール類は、一般に、安息香酸類を
試薬を用いて以下の通り還元することにより製造されて
いる。Conventionally, benzyl alcohols are generally produced by reducing benzoic acids using a reagent as described below.
しかしながら、ベンゼン核にフッ素原子が多く置換した
ポリフルオロベンジルアルコールについてはこのような
化学的還元法は工業的に成功していない。However, such a chemical reduction method has not been industrially successful for polyfluorobenzyl alcohol in which the benzene nucleus is substituted with many fluorine atoms.
即ち、例えばポリフルオロ安息香酸をリチウムアルミニ
ウムヒドリド（ＬＡＨ）で化学的に還元することも考え
られるが、この方法には１）ＬＡＨが工業的に使用する
のには高価であり、また２）無水の極性溶媒（例えばテ
トラヒドロフラン、ジオキサン）を使用しないとＬＡＨ
が水によって失活するという問題があり、更に３）原料
として、例えばペンタフルオロ安息香酸を使用した場合
、ＰＦＢＡＬと２．３．５．６−ＴＦＢＡＬとの混合物
（〜は＼“１：１）が得られるのみで、いずれか一方を
選択的に製造することがむずかしいという問題がある。That is, for example, it is possible to chemically reduce polyfluorobenzoic acid with lithium aluminum hydride (LAH), but this method requires 1) LAH is expensive for industrial use, and 2) anhydrous. If polar solvents (e.g. tetrahydrofuran, dioxane) are not used, LAH
There is a problem that 2.3.5.6-TFBAL is deactivated by water, and 3) When pentafluorobenzoic acid is used as a raw material, for example, a mixture of PFBAL and 2.3.5.6-TFBAL (~ is \"1:1) However, there is a problem in that it is difficult to selectively manufacture one of the two.
一方、ポリフルオロベンジルアルコールラミ解還元法に
より合成する方法も、例えばＦ、Ｇ、Ｄｒａｋｅｓ−ａ
＋ｉｔｈ＋ Ｊ、Ｃｈｅｍ、Ｓｏｃ、、 Ｐｅｒｋｉｎ
Ｔｒａｎｓ、１＋１９７２＋ ｐ１８４に記載されて
いるように研究されているが、この方法でＰＦＢＡＬを
選択的に製造するためには、爆発、火災等の危険がある
３０％以上の高濃度過塩素酸水溶液を使用する必要があ
り、更に水銀を陰電極に使用するため、公害規制の面で
工業化はむすかしいという問題がある。更に例えば２．
３．５．６−ＴＦＢＡＬを選択的に製造するためには、
高価な支持電解質（Ｅｔ、ＮＢＦ４）水溶液を高濃度（
０，２モル／りで使用しなければならないという問題が
ある。On the other hand, a method of synthesizing by polyfluorobenzyl alcohol laminated reduction method is also available, for example, F, G, Drakes-a
+ith+ J, Chem, Soc,, Perkin
Trans, 1+1972+ p184, but in order to selectively produce PFBAL using this method, it is necessary to use a highly concentrated perchloric acid aqueous solution of 30% or more, which poses a risk of explosion and fire. Furthermore, since mercury is used in the negative electrode, industrialization is difficult in terms of pollution control. Furthermore, for example 2.
3.5.6-To selectively produce TFBAL,
Expensive supporting electrolyte (Et, NBF4) aqueous solution at high concentration (
There is a problem in that it has to be used at 0.2 mol/liter.
従って、本発明は前記した従来技術の問題点を解決して
所望のポリフルオロベンジルアルコールを工業的に良好
な収率及び選択率で電解的に製造することができる方法
を提供することを目的とする。Therefore, it is an object of the present invention to solve the problems of the prior art described above and to provide a method capable of electrolytically producing a desired polyfluorobenzyl alcohol with industrially good yield and selectivity. do.
本発明に従えば、前記問題点は、下記一般式（Ｉ）のポ
リフルオロ安息香酸を電解還元として、下記一般式（■
）のポリフルオロベンジルアルコールを製造するに当り
、
〔上記式（Ｎ及び（Ｉ１）においてｎ及びｍはそれぞれ
独立に１〜５の整数を示し、ｍ≦ｎである〕陰電極とし
て固体金属又は固体合金を用い、電解溶液として硫酸水
性液を用いることによって解決することができる。本発
明に従えば、更に、前記硫酸水性液にオニウム塩触媒を
添加することによって、特にペンタフルオロ安息香酸か
ら２．３，５．６− ＴＦＢＡＬを高い選択性及び収率
で製造することができる。According to the present invention, the above problem can be solved by electrolytically reducing polyfluorobenzoic acid of the following general formula (I),
) In producing polyfluorobenzyl alcohol, [in the above formulas (N and (I1), n and m each independently represent an integer of 1 to 5, and m≦n]) a solid metal or solid is used as the negative electrode. This can be solved by using a sulfuric acid aqueous solution as the electrolytic solution.According to the present invention, furthermore, by adding an onium salt catalyst to the sulfuric acid aqueous solution, especially pentafluorobenzoic acid to 2. 3,5.6-TFBAL can be produced with high selectivity and yield.
（実施態様の説明）
本発明者らも、ＰＦＢＡＬあるいは２．３．５．６−
ＴＦＢＡＬなどのポリフルオロベンジルアルコールを製
造する目的でペンタフルオロ安息香酸をＬＡＮで化学的
に還元することを試みたが、この還元法ではＰＦＢＡＬ
と２．３．５．６− ＴＦＢＡＬの混合物（はぼ１：１
）が得られるのみで、いずれか一方を選択的に製造する
ことはできなかった。また、テトラフルオロベンジルア
ルコールも目的とするパラ位に水素のついた２、３．５
．６−ＴＦＢＡＬ以外にオルト位が水素置換された２、
３．４．５−ＴＦＢＡＬも副生じ、両者の分離精製も困
難であった。(Description of Embodiments) The present inventors also believe that PFBAL or 2.3.5.6-
We attempted to chemically reduce pentafluorobenzoic acid using LAN for the purpose of producing polyfluorobenzyl alcohol such as TFBAL, but this reduction method
and 2.3.5.6-TFBAL (1:1
), but it was not possible to selectively produce one of them. In addition, tetrafluorobenzyl alcohol can also be used with 2,3.5
．． 2 with hydrogen substitution at the ortho position other than 6-TFBAL,
3.4.5-TFBAL was also produced as a by-product, and separation and purification of both was difficult.
然るに本発明に従った電解法では電解の電極、電位、電
解溶液等を選択することにより、特に、好適には前記一
般式（Ｉ）におけるｎの値いが３以上のポリフルオロ安
息香酸を原料として用いる場合の反応、例えば
の反応を効果的にかつ、選択的に行うことができる。However, in the electrolytic method according to the present invention, by selecting electrodes, potentials, electrolytic solutions, etc. for electrolysis, polyfluorobenzoic acid having a value of n in the general formula (I) of 3 or more is particularly preferably used as a raw material. Reactions when used as, for example, reactions can be carried out effectively and selectively.
即ち本発明に従えば、工業的に安価で危険の少ない硫酸
水性液を電解溶液として用いるため、従来技術の如く高
濃度の過塩素酸水溶液を使用する必要がなく、また従来
法では電極に水銀（液体）を用いるため、前記したよう
な問題があるばかりでなく、ＰＦＢＡＬと２．３．５．
６−ＴＦＢＡＬの生成に選択性が乏しくＰＦＢＡＬ ／
２．３．５．６−ＴＦＢＡＬ（モル比）は０．８〜１
．２程度である。That is, according to the present invention, an industrially inexpensive and less dangerous sulfuric acid aqueous solution is used as the electrolytic solution, so there is no need to use a highly concentrated perchloric acid aqueous solution as in the prior art. (liquid), there are not only the problems mentioned above, but also PFBAL and 2.3.5.
6-TFBAL production has poor selectivity and PFBAL/
2.3.5.6-TFBAL (molar ratio) is 0.8 to 1
．． It is about 2.
これに対し本発明に従えば、例えば亜鉛アマルガム電極
、鉛アマルガム電極などの固体合金を陰電極に使用する
ので電解槽の設計製作上の利便が極めて大きく、また硫
酸濃度を約１０〜９０重量％、特に１５〜６０重量％に
することにより、ＰＦＢＡＬ ／２゜３．５．６−ＴＦ
ＢＡＬ（モル比）を６以上にすることができ、更に硫酸
濃度を下げ、極く少量のオニウム塩を触媒として加える
ことにより、例えば、ＰＦＢＡＬ／ ２．３．５．６−
ＴＦＢＡＬ（モル比）を０．１以下にすることができる
。In contrast, according to the present invention, a solid alloy such as a zinc amalgam electrode or a lead amalgam electrode is used for the negative electrode, which greatly facilitates the design and manufacture of the electrolytic cell, and the sulfuric acid concentration is approximately 10 to 90% by weight. , especially by 15-60% by weight, PFBAL /2°3.5.6-TF
BAL (molar ratio) can be increased to 6 or more, and by further lowering the sulfuric acid concentration and adding a very small amount of onium salt as a catalyst, for example, PFBAL/2.3.5.6-
TFBAL (molar ratio) can be made 0.1 or less.
すなわち、本発明によれば同一装置を用いて条件を変え
ることにより生成物の組成を、任意に調整することがで
き、工業的にも大きな装置が組めるため、工業的に非常
に有利な製法である。In other words, according to the present invention, the composition of the product can be adjusted as desired by changing the conditions using the same equipment, and a large-scale equipment can be set up, making it an industrially very advantageous manufacturing method. be.
本発明に従えば、陰電極として、亜鉛、鉛、カドミウム
、銅、アルミニウム、スズなどの固体金属又は亜鉛アマ
ルガム、鉛アマルガム、カドミウムアマルガム、銅アマ
ルガム、アルミニウムアマルガム、スズアマルガムなど
の固体合金を用い、電解溶液に硫酸水性液、例えば硫酸
濃度１〜９０重量％、好ましくは２〜７０重量％の硫酸
水性液を用い、更にオニウム塩を微量の触媒として必要
に応じ添加することにより所望のポリフルオロベンジル
アルコールを選択的に製造することができる。According to the present invention, solid metals such as zinc, lead, cadmium, copper, aluminum, tin or solid alloys such as zinc amalgam, lead amalgam, cadmium amalgam, copper amalgam, aluminum amalgam, tin amalgam are used as the negative electrode, By using a sulfuric acid aqueous solution, for example, a sulfuric acid aqueous solution with a sulfuric acid concentration of 1 to 90% by weight, preferably 2 to 70% by weight, as the electrolytic solution, and further adding a small amount of onium salt as a catalyst as necessary, the desired polyfluorobenzyl can be obtained. Alcohol can be selectively produced.
ここで使用するオニウム塩としては、一般式Ｒ４ＮＸ、
Ｒ３５Ｘ、Ｒ４ＰＸ （但し、Ｒは炭素数１〜８のアル
ハロゲンを表わす）が使用でき、例えばＥｔ４ＮＨ５Ｏ
ａ。The onium salt used here has the general formula R4NX,
R35X, R4PX (wherein R represents an alhalogen having 1 to 8 carbon atoms) can be used, for example, Et4NH5O
a.
ＢＬＩ４Ｃｌ ０４１ ＢｕｉＳＢＦｉ、 ＢｕｚＳＣ
Ｉ Ｏｈ Ｂｕ４ＰＢｒ等をあげることができる。BLI4Cl 041 BuiSBFi, BuzSC
Examples include I Oh Bu4PBr.
例えば原料としてＰＦＢＡを用いる場合、２，３，５．
６−ＴＦＢＡＬを選択的かつ経済的に製造するためには
、オニウム塩触媒の添加量は、電解溶液に対して一般に
０．０００１〜０．１モル／Ｉ！、、好ましくは約０．
００１〜０．０５モル／ｌである。For example, when using PFBA as a raw material, 2, 3, 5.
In order to selectively and economically produce 6-TFBAL, the amount of onium salt catalyst added is generally 0.0001 to 0.1 mol/I! relative to the electrolyte solution. , preferably about 0.
001 to 0.05 mol/l.
また、陰電極には亜鉛、鉛などの固体金属を使用し、電
解溶液中の硫酸濃度は通常１〜５０重量％程度、好まし
くは２〜４０重量％、さらに好ましくは３〜３０重量％
が使用される。In addition, a solid metal such as zinc or lead is used for the negative electrode, and the sulfuric acid concentration in the electrolytic solution is usually about 1 to 50% by weight, preferably 2 to 40% by weight, and more preferably 3 to 30% by weight.
is used.
一方、ＰＦＢＡＬを選択的に製造するためには亜鉛、鉛
、カドミニウム等の金属アマルガム合金（水銀量１〜２
０重量％、好ましくは２〜１５重量％）を陰電極に用い
硫酸濃度１０〜９０重景％、重量しくは１５〜７０重量
％がよく、この場合はオニウム塩を添加しない方がよい
。いずれの場合も得られるポリフルオロベンジルアルコ
ールの選択性は極めて高＜ 、ＰＦＢＡＬ ／ ２．３
．５．６−ＴＦＢＡＬのモル比を６以上または０．１以
下にすることが可能である。On the other hand, in order to selectively manufacture PFBAL, metal amalgam alloys such as zinc, lead, and cadmium (mercury content of 1 to 2
0% by weight, preferably 2 to 15% by weight) in the negative electrode, and the sulfuric acid concentration is preferably 10 to 90% by weight, preferably 15 to 70% by weight; in this case, it is better not to add an onium salt. In both cases, the selectivity of the polyfluorobenzyl alcohol obtained is extremely high < , PFBAL / 2.3
．． It is possible for the molar ratio of 5.6-TFBAL to be greater than or equal to 6 or less than or equal to 0.1.
次に、原料として２，３，５．６−テトラフルオロ安息
香酸又は２，３，４．５−テトラフルオロ安息香酸を用
いる場合には、オニウム塩の添加は必ずしも必要ではな
く、また陰電極も前記の固体金属、固体アマルガム合金
のいずれでもよい。Next, when using 2,3,5,6-tetrafluorobenzoic acid or 2,3,4,5-tetrafluorobenzoic acid as a raw material, addition of an onium salt is not necessarily necessary, and the negative electrode is also Either the solid metal or solid amalgam alloy mentioned above may be used.
また、電解溶液としての硫酸濃度も特に制限されるもの
ではなく、１〜９０重量％、好ましくは２０〜７０重量
％がよい。但し、電流効率を高めるためには、陰電極と
して亜鉛、鉛等のアマルガム合金を用い、電解溶液とし
ての硫酸濃度を２０〜５０重量％とじて、オニウム塩を
約０．００１−０．０５モル／ｌ用いることができる。Further, the concentration of sulfuric acid as an electrolytic solution is not particularly limited, and is preferably 1 to 90% by weight, preferably 20 to 70% by weight. However, in order to increase current efficiency, use an amalgam alloy such as zinc or lead as the negative electrode, keep the sulfuric acid concentration as the electrolytic solution at 20 to 50% by weight, and add about 0.001 to 0.05 mol of onium salt. /l can be used.
更に、本発明の電解溶液には、水溶性有機溶媒を含有さ
せるのが、得られるポリフルオロベンジルアルコールの
収率及び電流効率等の観点から好ましい。上記水溶性有
機溶媒の電解溶液中の濃度としては一般に５〜５０重量
％程度が好適に使用される。Furthermore, it is preferable to include a water-soluble organic solvent in the electrolyte solution of the present invention from the viewpoints of the yield of polyfluorobenzyl alcohol obtained, current efficiency, etc. The concentration of the water-soluble organic solvent in the electrolytic solution is generally about 5 to 50% by weight.
前記の水溶性有機溶媒としては、例えばメチルアルコー
ル、エチルアルコール、プロピルアルコール（ＩＩ、
、 ｉ、 ）等の炭素数１〜３の脂肪族−価アルコ
ール類；アリルアルコール、フルフリルアルコール等の
その他の一価アルコール頻；エチレングリコール、プロ
ピレングリコール（Ｉ，２＋、 ｉ、 ３−）、グ
リセリン等の炭素原子数１〜３の脂肪族多価アルコール
類；室温で液状のポリエチレングリコール；エチレング
リコールモノメチルエーテル、エチレングリコールモノ
エチルエーテル、エチレングリコールモノブチルエーテ
ル、エチレングリコールジメチルエーテル等のエチレン
グリコールと炭素原子数１〜４の脂肪族−価アルコール
とのモノまたはジエーテル化物；ジエチレングリコール
モツプチルエーテル、ジエチレングリコールモノエチル
エーテル、ジエチレングリコールモツプチルエーテル、
ジエチレングリクールジメチルエーテル、ジエチレング
リコールジエチルエーテル等のジエチレングリコールと
炭素原子数１〜４の脂肪族−価アルコールとのモノまた
はジエーテル化物；１−グリセリンモノメチルエーテル
等のグリセリンと炭素原子数１〜３の脂肪族−価アルコ
ールとのモノエーテル化物；テトラヒドロフラン、ジオ
キサン（Ｉ，３−，１，４−）ｊ並びにアセトン、アセ
トニトリル、ラクトニトリル、Ｎ、Ｎ−ジメチルホルム
アミド、ジメチルスルホオキシド、ジエチルスルホオキ
シド等のその他の水溶性有機溶媒などを挙げることがで
き、入手の容易性や経済的観点よりメチルアルコールが
特に好適に使用できる。Examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, propyl alcohol (II,
, i, ); Other monohydric alcohols such as allyl alcohol and furfuryl alcohol; ethylene glycol, propylene glycol (I, 2+, i, 3-), Aliphatic polyhydric alcohols having 1 to 3 carbon atoms such as glycerin; polyethylene glycol that is liquid at room temperature; ethylene glycol and carbon atoms such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, etc. Mono- or dietherified products with aliphatic-hydric alcohols of numbers 1 to 4; diethylene glycol motsubutyl ether, diethylene glycol monoethyl ether, diethylene glycol motsubutyl ether,
Mono- or dietherized products of diethylene glycol and aliphatic alcohols having 1 to 4 carbon atoms, such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether; 1-Glycerin and aliphatic alcohols having 1 to 3 carbon atoms, such as 1-glycerin monomethyl ether; Monoetherified products with alcohols; tetrahydrofuran, dioxane (I,3-,1,4-)j, and other aqueous solutions such as acetone, acetonitrile, lactonitrile, N,N-dimethylformamide, dimethylsulfoxide, diethylsulfoxide, etc. Among them, methyl alcohol is particularly preferably used from the viewpoint of easy availability and economical viewpoint.
電解還元の浴温、電位（あるいは、電流密度）などは操
作条件、電流効率、電極費等を考え適切に選べばよいが
、電位は飽和材コウ電極（以下、ＳＣＥと略す）に対シ
テ、−１，３０Ｖ 〜−１，６０Ｖ程度（定電位電解）
或いは電流密度０．２〜２０Ａ／ｄｍ” （定電流電解
）、浴温−１０°Ｃ〜１００°Ｃ１好ましくは０°Ｃ〜
５０°Ｃである。The electrolytic reduction bath temperature, potential (or current density), etc. can be selected appropriately considering operating conditions, current efficiency, electrode cost, etc.; -1,30V to -1,60V (constant potential electrolysis)
Or current density 0.2 to 20 A/dm" (constant current electrolysis), bath temperature -10°C to 100°C, preferably 0°C to
It is 50°C.
以下、実施例に従って本発明を更に具体的に説明するが
、本発明の技術的範囲をこれらの実施例に限定するもの
でないことはいうまでもない。The present invention will be described in more detail below with reference to Examples, but it goes without saying that the technical scope of the present invention is not limited to these Examples.
ス新ｌｌ上
ガラスフィルターの隔膜を有し、陽電極に鉛板を陰電極
に亜鉛アマルガム板（面積６．３ ｃ＋ｌｌ ）を備え
たＨ型ガラスセルの陰極室及び陽極室にそれぞれ３５重
量％の硫酸５０ＩＩ１１を電解溶液として加え、ペンタ
フルオロ安息香酸０．５３ｇ （２，５ミリモル）を
陰極液中に添加した。次に陰極電位を−１，５Ｖ（対５
ＣＥ）に設定し、室温（２３°Ｃ）で２５ｍＦの電気量
を流してペンタフルオロ安息香酸を電解還元した。35 wt. Sulfuric acid 50II11 was added as electrolyte solution and 0.53 g (2.5 mmol) of pentafluorobenzoic acid was added to the catholyte. Next, set the cathode potential to -1.5V (vs.
CE), and a current of 25 mF was applied at room temperature (23°C) to electrolytically reduce pentafluorobenzoic acid.
電解後の陰極液をエーテル抽出し、抽出液をガスクロマ
トグラフ分析した結果は以下の通りであった。The catholyte after electrolysis was extracted with ether, and the extracted liquid was analyzed by gas chromatography. The results were as follows.
ペンタフルオロ安息香酸（出発原料）の転化率：３５．
６％
ＰＰＢＡＬの収量： ０．６０４ミリモル（選択率６
７．９％電流効率１０％）
２．３．５．６−ＴＦＢＡＬの収量： ０．０９ミリモ
ルＰＦＢＡＬ／ ２，３，５．６−ＴＦＢＡＬ ：
６．７スｌｕ生え
実施例Ｉにおいて、陰電極を、鉛アマルガム電極に替え
た以外は、実施例１と同様にして、ペンタフルオロ安息
香酸を電解還元した。Conversion rate of pentafluorobenzoic acid (starting material): 35.
Yield of 6% PPBAL: 0.604 mmol (selectivity 6
7.9% current efficiency 10%) Yield of 2.3.5.6-TFBAL: 0.09 mmol PFBAL/2,3,5.6-TFBAL:
6.7 Thin Growth In Example I, pentafluorobenzoic acid was electrolytically reduced in the same manner as in Example 1, except that the negative electrode was replaced with a lead amalgam electrode.
結果は以下の通りであった。The results were as follows.
ペンタフルオロ安息香酸の転化率：４０％ＰＦＢＡＬの
収量： ０．７８１ミリモル（選択率７８．１％電流
効率１２％）
２．３，５．６− ＴＦＢＡＬの収＠ ： ０．０８ミ
リモルＰＦＢＡＬ／ ２．３，５．６−ＴＦＢＡＬ
： １０実施■ユ
実施例１で用いたと同様のＨ型ガラスセルを用い、その
陰極室に１ミリモルのテトラエチルアンモニウムパラト
ルエンスルホネートを含む５重量％硫酸５０１！！、陽
極室に５重量％硫酸５０Ｉｌｌｌ！を電解液として加え
、ペンタフルオロ安息香酸０．５３ｇ（２，５ミリモル
を陰極液中に添加した。次に陰極電位を−１，５Ｖ（対
５ＣＥ）！、：設定し、室温（２３°Ｃ）で１１．２５
ｍ Ｆの電気量を流して、ペンタフルオロ安息香酸を電
解還元した。Conversion rate of pentafluorobenzoic acid: 40% Yield of PFBAL: 0.781 mmol (selectivity 78.1% current efficiency 12%) 2.3,5.6- Yield of TFBAL @: 0.08 mmol PFBAL/2 .3,5.6-TFBAL
: 10 implementation ■ U Using the same H-type glass cell as used in Example 1, 5% by weight sulfuric acid containing 1 mmol of tetraethylammonium paratoluene sulfonate was added to the cathode chamber. ! , 50Illll of 5% by weight sulfuric acid in the anode chamber! was added as an electrolyte, and 0.53 g (2.5 mmol) of pentafluorobenzoic acid was added to the catholyte.Then, the cathode potential was set to -1.5 V (vs. 5 CE), and the temperature was increased to room temperature (23 °C ) at 11.25
An amount of electricity of m F was applied to electrolytically reduce pentafluorobenzoic acid.
電解後の陰極液をエーテル抽出し、抽出液をガスクロマ
トグラフ分析した結果は以下の通りであった。The catholyte after electrolysis was extracted with ether, and the extracted liquid was analyzed by gas chromatography. The results were as follows.
ペンタフルオロ安息香酸（出発原料）の転化率：９０６
８％
２．３．５．６−ＴＦＢＡＬの収量： １．１６１ミ
リモル（選択率５１．１％ 電流効率４１．１％）ＰＰ
ＢＡＬの収量： ０．０３１ミリモルＰＦＢＡＬ／
２，３．５．６−ＴＦＢＡＬ ：０．０２７なお、他
に、２．３，５．６−テトラフルオロ安息香酸が０．８
１４ミリモル生成した（選択率３５．９％電流効率１４
．４％）。Conversion rate of pentafluorobenzoic acid (starting material): 906
Yield of 8% 2.3.5.6-TFBAL: 1.161 mmol (selectivity 51.1% current efficiency 41.1%) PP
Yield of BAL: 0.031 mmol PFBAL/
2,3.5.6-TFBAL: 0.027 In addition, 2,3,5.6-tetrafluorobenzoic acid is 0.8
14 mmol was produced (selectivity 35.9% current efficiency 14
．． 4%).
裏庭■土
実施例３において電流密度２．４Ａ／ｄｍ”（定電流電
解）に設定し、１６．２５ｍ Ｆの電気量を流した以外
は実施例３と同様に電解還元した。Backyard Soil Electrolytic reduction was carried out in the same manner as in Example 3, except that the current density was set at 2.4 A/dm'' (constant current electrolysis) and an amount of electricity of 16.25 mF was applied.
結果は以下の通りであった。The results were as follows.
ペンタフルオロ安息香酸の転化率：８７．７％２、３．
５．６− ＴＦＢＡＩ、の収量： ０．９７５ミリモル
（選択率４４．５％ 電流効率３６％）
ＰＦＢＡＬの収量： ０．０３６ミリモルＰＦＢＡＬ
／ ２，３，５．６−ＴＦＢＡＬ ： ０．０３７
なお他に２．３，５．６−テトラフルオロ安息香酸が０
．２１５ ミリモル（選択率９．８％ 電流効率２．６
％）生成していた。Conversion rate of pentafluorobenzoic acid: 87.7% 2, 3.
5.6- Yield of TFBAI: 0.975 mmol (selectivity 44.5% current efficiency 36%) Yield of PFBAL: 0.036 mmol PFBAL
/2,3,5.6-TFBAL: 0.037
In addition, 2,3,5,6-tetrafluorobenzoic acid is 0
．． 215 mmol (selectivity 9.8% current efficiency 2.6
%) was generated.
尖詣土工
実施例３において、陰極室液を、１ミリモルのテトラア
ンモニウムパラトルエンスルホネートを含む６．２５重
量％硫酸４０ｄとメタノール１０ｄよりなる電解溶液に
替え１６．２５ｍ Ｆの電気量を流した以外は実施例３
と同様にして、ペンタフルオロ安息香酸を電解還元した
。Except for the case where the cathode chamber solution was replaced with an electrolytic solution consisting of 40 d of 6.25 wt% sulfuric acid containing 1 mmol of tetraammonium para-toluene sulfonate and 10 d of methanol in Example 3 of the chiseled earthwork, and an amount of electricity of 16.25 mF was passed. is Example 3
In the same manner as above, pentafluorobenzoic acid was electrolytically reduced.
結果は以下の通りであった。The results were as follows.
ペンタフルオロ安息香酸の転化率： ９７．２％２．３
．５．６−ＴＦＢＡＬの収量： ２．０３１ミリモル
（選択率８３．６％ 電流効率５０％）
ＰＦＢＡＬの収ｆｌｔ： ０．０４ミリモルＰＦＢＡＬ
／ ２．３．５．６−ＴＦＢＡＬ ： ０．０
２なお他に２．３，５．６−テトラフルオロ安息香酸が
０．０８１ミリモル生成していた。Conversion rate of pentafluorobenzoic acid: 97.2%2.3
．． 5.6-TFBAL yield: 2.031 mmol (selectivity 83.6% current efficiency 50%) PFBAL yield flt: 0.04 mmol PFBAL
/2.3.5.6-TFBAL: 0.0
2. In addition, 0.081 mmol of 2,3,5,6-tetrafluorobenzoic acid was produced.
ス五ｌ吐灸
実施例１で用いたと同様のＨ型ガラスセルを用い、その
陰極室に１ミリモルのテトラアンモニウムパラトルエン
スルホネートを含む５重量％硫酸５０ｉｄ、陽極室に５
重量％硫酸５０１ｄを電解液として加え、２，３，５．
６−テトラフルオロ安息香酸０．４８５ｇ （２，５ミ
リモル）を陰極液中に添加した。次に陰極電位を−１，
５Ｖ（対５ＣＥ）に設定し、室温（２３°Ｃ）で１６．
２５ｍ Ｆの電気量を流して２，３，５．６−テトラフ
ルオロ安息香酸を電解還元した。Using an H-type glass cell similar to that used in Moxibustion Example 1, the cathode chamber contained 50 id of 5 wt% sulfuric acid containing 1 mmol of tetraammonium para-toluene sulfonate, and the anode chamber contained
Add 501 d of sulfuric acid (wt%) as an electrolyte, 2, 3, 5.
0.485 g (2.5 mmol) of 6-tetrafluorobenzoic acid was added to the catholyte. Next, the cathode potential is -1,
Set to 5V (vs. 5CE) and heat at room temperature (23°C) for 16.
2,3,5,6-tetrafluorobenzoic acid was electrolytically reduced by flowing an amount of electricity of 25 mF.
電解後の陰極液をエーテルで抽出し抽出液をガスクロマ
トグラフ分析は結果は以下の通りであった。The catholyte after electrolysis was extracted with ether, and the extracted liquid was analyzed by gas chromatography, and the results were as follows.
２．３，５．６−テトラフルオロ安息香酸の転化率７８
８．０％
２．３．５．６−ＴＰＢＡＬの収量： １．８５ミリモ
ル（選択率８４．１ 電流効率４５．５％）
実施例７
実施例６において陰極に亜鉛アマルガム板を用い、陰極
液及び陽極液に２０重量％硫酸５０ＷＩｆｔを用いた以
外は、実施例６と同様にして、２，３゜５．６−テトラ
フルオロ安息香酸を電解還元した。Conversion rate of 2.3,5.6-tetrafluorobenzoic acid 78
8.0% Yield of 2.3.5.6-TPBAL: 1.85 mmol (selectivity 84.1 current efficiency 45.5%) Example 7 In Example 6, a zinc amalgam plate was used as the cathode, and the catholyte was 2,3°5,6-tetrafluorobenzoic acid was electrolytically reduced in the same manner as in Example 6, except that 20% by weight sulfuric acid (50WIft) was used as the anolyte.
結果は以下の通りであった。The results were as follows.
２．３．５．６−テトラフルオロ安息香酸の転化率：２
４％
２、３．５．６− ＴＦＢＡＬの収量： ０，４３９ミ
リモル（選択率７３．２％ 電流効率１０．８％）災脂
■工
実施例６において、原料に、２，３，４．５−テトラフ
ルオロ安息香酸を用い、１１ｍＦの電気量を流した以外
は実施例６と同様に電解還元した。2.3.5. Conversion rate of 6-tetrafluorobenzoic acid: 2
4% 2, 3.5.6- Yield of TFBAL: 0,439 mmol (selectivity 73.2%, current efficiency 10.8%) In Example 6, 2, 3, 4. Electrolytic reduction was carried out in the same manner as in Example 6, except that 5-tetrafluorobenzoic acid was used and a current of 11 mF was applied.
結果は以下の通りであった。The results were as follows.
２．３，４．５−テトラフルオロ安息香酸の転化率：
８７．４％
２．３．４．５−ＴＦＢＡＬの収量： ０．７６７ミ
リモル（選択率３５．１％ 電流効率２７．９％）災籐
皿ニ
ガラスフィルターの隔膜並びに陽極に鉛板を陰極に鉛ア
マルガム板（面積６．３ ｃｌｉｌ）を備えたＨ型ガラ
スセルの陰極及び陽極に２０％硫酸５０ｄを電解液とし
て加え、２．３，４．５−テトラフルオロ安息香酸を陰
極液中に添加した。次に陰極電位を−１，５７Ｖ （対
５ＣＥ）に設定、０〜３°Ｃで２５ｍＦの電気量を流し
て、２．３，４．５−テトラフルオロ安息香酸を電解し
た。Conversion rate of 2.3,4.5-tetrafluorobenzoic acid:
87.4% Yield of 2.3.4.5-TFBAL: 0.767 mmol (Selectivity 35.1% Current efficiency 27.9%) The diaphragm of the rattan dish glass filter and the anode and lead plate as the cathode. 50 d of 20% sulfuric acid was added as an electrolyte to the cathode and anode of an H-type glass cell equipped with a lead amalgam plate (area 6.3 cli), and 2,3,4,5-tetrafluorobenzoic acid was added to the catholyte. did. Next, the cathode potential was set to -1,57V (vs. 5CE), and 25 mF of electricity was applied at 0 to 3°C to electrolyze 2.3,4.5-tetrafluorobenzoic acid.
ガスクロマトグラフ分析の結果は以下の通りであった。The results of gas chromatography analysis were as follows.
２．３，４．５−テトラフルオロ安息香酸の転化率＝４
２％
２．３．４．５−ＴＦＢＡＬの収量： ０．７２５ミリ
モル（選択率６９％ 電流効率１１．６％）
手続補正書（自発）
昭和６２年１０月３０日
特許庁長官 小 川 邦 夫 殿
１、事件の表示
昭和６２年特許願第３９２８８号
２、発明の名称
ポリフルオロベンジルアルコールの製造方法３、補正を
する者
事件との関係 特許出願人
名称（４Ｓ’？）日本カーバイド工業株式会社４、代理
人
住所 東京都港区虎ノ門−丁目８番１ｏ号静光虎ノ門ビ
ル
５、補正の対象
明細書の「発明の詳細な説明」の欄
６、補正の内容
明細書第２２頁第１２行の後に以下の実施例を加入する
。2. Conversion rate of 3,4.5-tetrafluorobenzoic acid = 4
2% 2.3.4.5-TFBAL yield: 0.725 mmol (selectivity 69%, current efficiency 11.6%) Procedural amendment (voluntary) October 30, 1985 Director General of the Japan Patent Office Kunio Ogawa 1. Indication of the case Patent Application No. 39288 of 1988 2. Name of the invention Process for producing polyfluorobenzyl alcohol 3. Person making the amendment Relationship to the case Patent applicant name (4S'?) Nippon Carbide Industries Co., Ltd. 4. Agent address: 5, Shizukou Toranomon Building, 8-1o Toranomon-chome, Minato-ku, Tokyo; Column 6, "Detailed Description of the Invention" of the specification to be amended; Page 22, line 12 of the specification of the contents of the amendment. The following examples are added after.
「ス崖開土■
ナフィオン膜（デュポン製Ｎａｆｉｏｎ ４２３．フッ
素イオン交換膜）を介して陰陽両極室に分かれたエレク
トロセルニービー（Ｅｌｅｃｔｒｏ Ｃｅ１ｌ ＡＢ）
社製のフィルタープレス型マイクロセル（陰極室容量約
１０ｄ）に陰極に亜鉛板（有効電極面積１０ｃＪ）を、
陽極には白金−チタン板（有効電極面積１０ｃｊ）をつ
け、陰陽電解液にそれぞれ５重量％硫酸水溶液２００ｄ
を用い、陰極電解液にペンタフルオロ安息香酸２．１２
ｇｒ（Ｉ０ミリモル）を添加した。``Scrap open earth ■ Electro Cell Nevie (Electro Ce1l AB) divided into negative and positive polar chambers via Nafion membrane (DuPont Nafion 423.Fluorine ion exchange membrane)
A zinc plate (effective electrode area: 10 cJ) is installed as a cathode in a filter press type microcell (cathode chamber capacity: approximately 10 d) manufactured by
A platinum-titanium plate (effective electrode area: 10 cj) was attached to the anode, and 200 d of 5 wt% sulfuric acid aqueous solution was attached to the negative and positive electrolytes, respectively.
using 2.12 pentafluorobenzoic acid in the catholyte.
gr (I0 mmol) was added.
次に電解液をそれぞれの陰陽両極室に、０．７４１！／
ｗｉｎの流速で流して循環させ、４．８ Ａ／ｄｍ”の
電流密度に設定した。室温（２３℃）で２５０ｓＦの電
気量を流して、ペンタフルオロ安息香酸を電解還元した
。Next, add electrolyte to each yin and yang polar chamber, 0.741! /
The current density was set at 4.8 A/dm''. Pentafluorobenzoic acid was electrolytically reduced by flowing an amount of electricity of 250 sF at room temperature (23° C.).
電解後の陰極液をエーテルで抽出し、抽出液をガスクロ
マトグラフ分析したところ、以下の結果を得た。The catholyte after electrolysis was extracted with ether, and the extracted liquid was analyzed by gas chromatography, and the following results were obtained.
ペンタフルオロ安息香酸（出発原料）の転化率９８．１
％
生成２，３，５．６−テトラフルオロベンジルアルコー
ル（２，３，５，６−ＴＦＢＡＬ）の収量５．２４１ミ
リモル（選択率５３．４％、電流効率１Ｏ０５％）
生成ペンタフルオロベンジルアルコール（ＰＦＢＡＩ、
）の収量０．４１ミリモル
ＰＦＢＡＬ／２，３．５．６−ＴＦＢＡＬ：０、０８
実旌拠上土
実施例１Ｏにおいて、陰極を鉛板（有効電極面１ｆｉｌ
ＯｃＪ）に替えた以外は実施例１０と同一の装置を用い
、陰極液にテトラエチルアンモニウム・パラトルエンス
ルホネート４ミリモルを添加し、２．９Ａ／ｄがの電流
密度で１００ｓＦ電気量を流した以外は、実施例ＩＯと
同一の条件で電解還元を行った・
実施例１０と同様の操作で生成物を分析したところ、ペ
ンタフルオロ安息香酸（出発原料）の転化率は８４％、
生成２，３，５，６ＴＦＢＡＬの収量４．６２ミリモル
（選択率５５％、電流効率４３％）及びＰＦＢＡＬの収
量０．３３６ミリモルでＰＦＢＡＬ／２，３，５．６−
ＴＦＢＡＬ比は０．０７であった。１
以上Conversion rate of pentafluorobenzoic acid (starting material) 98.1
% Yield of 2,3,5,6-tetrafluorobenzyl alcohol (2,3,5,6-TFBAL) 5.241 mmol (selectivity 53.4%, current efficiency 1005%) Pentafluorobenzyl alcohol ( PFBAI,
) yield of 0.41 mmol PFBAL/2,3.5.6-TFBAL: 0,08 In Practical Top Soil Example 1O, the cathode was replaced with a lead plate (effective electrode surface 1fil
The same apparatus as in Example 10 was used, except that 4 mmol of tetraethylammonium paratoluenesulfonate was added to the catholyte, and 100 sF electricity was passed at a current density of 2.9 A/d. , electrolytic reduction was performed under the same conditions as in Example IO. When the product was analyzed in the same manner as in Example 10, the conversion rate of pentafluorobenzoic acid (starting material) was 84%,
PFBAL/2,3,5.6- with a yield of 4.62 mmol of produced 2,3,5,6 TFBAL (55% selectivity, 43% current efficiency) and a yield of 0.336 mmol of PFBAL.
TFBAL ratio was 0.07. 1 or more
Claims (1)
還元して、下記一般式（II）のポリフルオロベンジルア
ルコールを製造するに当り、 ▲数式、化学式、表等があります▼…………（ I ） ▲数式、化学式、表等があります▼…………（II） 〔上記式（ I ）及び（II）においてｎ及びｍはそれぞ
れ独立に１〜５の整数を示し、ｍ≦ｎである〕陰電極と
して固体金属又は固体合金を用い、電解溶液として硫酸
水性液を用いることを特徴とするポリフルオロベンジル
アルコールの製造方法。 ２、前記陰電極が固体金属アマルガムである特許請求の
範囲第１項記載の製造方法。 ３、前記固体金属アマルガム中の水銀量が１〜２０重量
％である特許請求の範囲第２項記載の製造方法。 ４、前記電解溶液が水溶性有機溶媒を含有している特許
請求の範囲第１項〜第３項のいずれか１項に記載の製造
方法、 ５、前記電解溶液中の水溶性有機溶媒の濃度が５〜５０
重量％である特許請求の範囲第４項記載の製造方法。 ６、前記水溶性有機溶媒がメタノールである特許請求の
範囲第４項又は第５項に記載の製造方法。 ７、前記ポリフルオロ安息香酸がペンタフルオロ安息香
酸である特許請求の範囲第１項〜第６項のいずれか１項
に記載の製造方法。 ８、前記ポリフルオロ安息香酸が２，３，５，６−テト
ラフルオロ安息香酸又は２，３，４，５−テトラフルオ
ロ安息香酸である特許請求の範囲第１項〜第６項のいず
れか１項に記載の製造方法。 ９、下記一般式（ I ）のポリフルオロ安息香酸を電解
還元して下記一般式（II）のポリフルオロベンジルアル
コールを製造するに当り、 ▲数式、化学式、表等があります▼…………（ I ） ▲数式、化学式、表等があります▼…………（II） 〔上記式（ I ）及び（II）においてｎ及びｍはそれぞ
れ独立に１〜５の整数を示し、ｍ≦ｎである〕陰電極と
して固体金属又は固体合金を用い、電解溶液としてオニ
ウム塩触媒を含む硫酸水性液を用いることを特徴とする
ポリフルオロベンジルアルコールの製造方法。 １０、前記オニウム塩触媒の添加量が、電解溶液に対し
て約０．０００１〜０．１モル／ｌである特許請求の範
囲第９項に記載の製造方法。 １１、前記電解溶液が水溶性有機溶媒を含有している特
許請求の範囲第９項又は第１０項に記載の製造方法。 １２、前記電解溶液中の水溶性有機溶媒の濃度が５〜５
０重量％である特許請求の範囲第１１項記載の製造方法
。 １３、前記水溶性有機溶媒がメタノールである特許請求
の範囲第１１項又は第１２項に記載の製造方法。 １４、前記ポリフルオロ安息香酸がペンタフルオロ安息
香酸である特許請求の範囲第９項〜第１３項のいずれか
１項に記載の製造方法。 １５、前記ポリフルオロ安息香酸が２，３，５，６−テ
トラフルオロ安息香酸又は２，３，４，５−テトラフル
オロ安息香酸である特許請求の範囲第９項〜第１３項の
いずれか１項に記載の製造方法。[Claims] 1. In producing polyfluorobenzyl alcohol of the following general formula (II) by electrolytically reducing polyfluorobenzoic acid of the following general formula (I), ▲ Numerical formulas, chemical formulas, tables, etc. There are▼…………(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼…………(II) [In the above formulas (I) and (II), n and m each independently represent an integer from 1 to 5. and m≦n] A method for producing polyfluorobenzyl alcohol, characterized in that a solid metal or solid alloy is used as a negative electrode, and a sulfuric acid aqueous solution is used as an electrolytic solution. 2. The manufacturing method according to claim 1, wherein the negative electrode is a solid metal amalgam. 3. The manufacturing method according to claim 2, wherein the amount of mercury in the solid metal amalgam is 1 to 20% by weight. 4. The manufacturing method according to any one of claims 1 to 3, wherein the electrolytic solution contains a water-soluble organic solvent; 5. The concentration of the water-soluble organic solvent in the electrolytic solution. is 5-50
5. The manufacturing method according to claim 4, wherein the amount is % by weight. 6. The manufacturing method according to claim 4 or 5, wherein the water-soluble organic solvent is methanol. 7. The manufacturing method according to any one of claims 1 to 6, wherein the polyfluorobenzoic acid is pentafluorobenzoic acid. 8. Any one of claims 1 to 6, wherein the polyfluorobenzoic acid is 2,3,5,6-tetrafluorobenzoic acid or 2,3,4,5-tetrafluorobenzoic acid. The manufacturing method described in section. 9. When producing polyfluorobenzyl alcohol of the following general formula (II) by electrolytically reducing polyfluorobenzoic acid of the following general formula (I), there are ▲mathematical formulas, chemical formulas, tables, etc.▼…………( I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼…………(II) [In the above formulas (I) and (II), n and m each independently represent an integer from 1 to 5, and m≦n. A method for producing polyfluorobenzyl alcohol, which comprises using a solid metal or solid alloy as a negative electrode and using an aqueous sulfuric acid solution containing an onium salt catalyst as an electrolytic solution. 10. The manufacturing method according to claim 9, wherein the amount of the onium salt catalyst added is about 0.0001 to 0.1 mol/l based on the electrolytic solution. 11. The manufacturing method according to claim 9 or 10, wherein the electrolytic solution contains a water-soluble organic solvent. 12. The concentration of the water-soluble organic solvent in the electrolytic solution is 5 to 5.
12. The manufacturing method according to claim 11, wherein the content is 0% by weight. 13. The manufacturing method according to claim 11 or 12, wherein the water-soluble organic solvent is methanol. 14. The manufacturing method according to any one of claims 9 to 13, wherein the polyfluorobenzoic acid is pentafluorobenzoic acid. 15. Any one of claims 9 to 13, wherein the polyfluorobenzoic acid is 2,3,5,6-tetrafluorobenzoic acid or 2,3,4,5-tetrafluorobenzoic acid. The manufacturing method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62039288A JP2632832B2 (en) | 1987-02-24 | 1987-02-24 | Method for producing polyfluorobenzyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62039288A JP2632832B2 (en) | 1987-02-24 | 1987-02-24 | Method for producing polyfluorobenzyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63206491A true JPS63206491A (en) | 1988-08-25 |
| JP2632832B2 JP2632832B2 (en) | 1997-07-23 |
Family
ID=12548968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62039288A Expired - Fee Related JP2632832B2 (en) | 1987-02-24 | 1987-02-24 | Method for producing polyfluorobenzyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2632832B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6624336B1 (en) | 1999-05-07 | 2003-09-23 | Showa Denko K.K. | Process for producing tetrafluorobenzenemethanols |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60234987A (en) * | 1984-05-09 | 1985-11-21 | Mitsui Toatsu Chem Inc | Manufacture of m-hydroxybenzyl alcohol |
-
1987
- 1987-02-24 JP JP62039288A patent/JP2632832B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60234987A (en) * | 1984-05-09 | 1985-11-21 | Mitsui Toatsu Chem Inc | Manufacture of m-hydroxybenzyl alcohol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6624336B1 (en) | 1999-05-07 | 2003-09-23 | Showa Denko K.K. | Process for producing tetrafluorobenzenemethanols |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2632832B2 (en) | 1997-07-23 |
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