JPS63111192A - Production of fluorobenzene - Google Patents
Production of fluorobenzeneInfo
- Publication number
- JPS63111192A JPS63111192A JP61256882A JP25688286A JPS63111192A JP S63111192 A JPS63111192 A JP S63111192A JP 61256882 A JP61256882 A JP 61256882A JP 25688286 A JP25688286 A JP 25688286A JP S63111192 A JPS63111192 A JP S63111192A
- Authority
- JP
- Japan
- Prior art keywords
- anode
- benzene
- fluorobenzene
- electrode
- rhodium
- 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.)
- Pending
Links
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 5
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 12
- 238000003682 fluorination reaction Methods 0.000 claims description 8
- -1 nitrile compound Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 5
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 abstract description 3
- 150000004767 nitrides Chemical class 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ベンゼンの電解フツ素化方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for electrolytic fluorination of benzene.
従来、ベンゼンを電解フッ素化する方法として、Ｉｚｖ
、 ＡｌａＬｄ−Ｎａｕｋ Ｓ ＳＳＲＳｅｒ 、
Ｋｈｉｍ（、１１３０（１９７２）、が挙ケラれる。こ
の方法では、電解溶媒としてアセトニトリルを用い、支
持価およびフッ素源として（０２Ｈ５）４ＮＦ ・３Ｈ
Ｆを用い２．４■の一定電位（対カロメル電極）で白金
陽極を用いて行っている。Conventionally, as a method for electrolytic fluorination of benzene, Izv
, AlaLd-Nauk S SSRSer ,
Khim (, 1130 (1972)). In this method, acetonitrile is used as the electrolytic solvent, and (02H5)4NF 3H is used as the supporting value and fluorine source.
The test was carried out using a platinum anode at a constant potential of 2.4 µm (vs. calomel electrode).
白金陽極に水溶液環境では安定であるが、酸性条件下で
有機物が存在した場合、異常消耗を起こすことが知られ
ている（電気化学協会筒５１回大会予稿集Ｅ２Ｒ２．１
９８４）。上記従来技術の電解フッ素化を本発明者らが
試みたところ、同じ様に陽極異常消耗が認められ、この
技術を工業的に応用することは困難であることが判明し
た。Although the platinum anode is stable in an aqueous environment, it is known to cause abnormal consumption if organic substances are present under acidic conditions (Electrochemical Society of Japan's 51st Annual Conference Proceedings E2R2.1)
984). When the present inventors attempted electrolytic fluorination using the above-mentioned conventional technique, abnormal anode consumption was similarly observed, and it was found that it was difficult to apply this technique industrially.
本発明者らは、上記の様な従来方法が持つ欠点を克服し
、陽極異常消耗を引き起こさずにベンゼンの電解フッ素
化を行う方法を開発すぺ〈種々の電極材料について鋭意
研究を重ねた結果、陽極材料としてロジウムもしくはロ
ジウム合金が、特異的に消耗が少ないことを見い出し、
この知見に基づいて本発明を完成するに至った。The present inventors have developed a method for electrolytic fluorination of benzene without causing abnormal consumption of the anode by overcoming the drawbacks of the conventional methods as described above. discovered that rhodium or rhodium alloys have uniquely low wear and tear as anode materials.
Based on this knowledge, we have completed the present invention.
〔問題点を解決するための手段および作用〕本発明は、
ベンゼンを、ニトリル系化合物を溶媒として、支持塩に
一般式 ＢＩ Ｈ２Ｂ３〜１”ｘＨＦ （式中Ｒ”ｌ
１２Ｒ Ｒ”ｌ Ｒ’はアルキル基であり、互いに同
一もしくは異ってもよい。Ｘは１以上１０以下である。[Means and effects for solving the problems] The present invention has the following features:
Using benzene and a nitrile compound as a solvent, the supporting salt has the general formula BI H2B3~1"xHF (in the formula R"l
12R R"l R' is an alkyl group and may be the same or different from each other. X is 1 or more and 10 or less.
）で表わされるフッ化テトラアルキルアンモニウム−フ
ツ化水素を用い、ロジウムもしくはロジウムを８０％以
上含む合金よシなる陽極を用いて電解フッ素化すること
を特徴とするフルオロベンゼンの製法である。This is a method for producing fluorobenzene, which is characterized by electrolytic fluorination using a tetraalkylammonium fluoride-hydrogen fluoride represented by the following formula, using an anode made of rhodium or an alloy containing 80% or more of rhodium.
本発明において、使用する溶媒はニトリル系化合物であ
る。この中でも、アセトニトリル、プロピオニトリル、
ｎ−ブチロニトリル、インブチロニトリルが好ましい。In the present invention, the solvent used is a nitrile compound. Among these, acetonitrile, propionitrile,
Preferred are n-butyronitrile and inbutyronitrile.
本発明において支持塩は、一般式Ｒ”Ｒ２Ｒ’Ｒ’ＮＦ
−ｘＨＦ（式中Ｒ１，Ｒ”、 Ｒｓ、 Ｒ４はアルキル
基であり、互いに同一もしくは異ってもよい。Ｘは１以
上１０以下である。）で表わされるフッ化テトラアルキ
ルアンモニウム−フツ化水素である。アルキル基の種類
は反応に大きな影響を及ぼさ々いが、Ｒ’、 Ｒ”、
Ｒ”。In the present invention, the supporting salt has the general formula R"R2R'R'NF
Tetraalkylammonium fluoride-hydrogen fluoride represented by -xHF (in the formula, R1, R", Rs, and R4 are alkyl groups, and may be the same or different from each other. The type of alkyl group has a great influence on the reaction, but R', R'',
R”.
Ｒ４がエチル基、ｎ−プロピル基、イソプロピル基、ｎ
−ブチル基、イソブチル基、ｔａｒｔ−ブチル基である
ものが入手しやすいので好ましい。またＸの値１ｌ−１
：１以上１０以下であるが、好ましくは１以上３．５以
下である。支持塩濃度は５Ｗ％以上５０Ｗ％以下が目的
物の選択率、電流効率の点で好ましい。R4 is an ethyl group, n-propyl group, isopropyl group, n
-butyl group, isobutyl group, and tart-butyl group are preferred because they are easily available. Also, the value of X is 1l-1
: 1 or more and 10 or less, preferably 1 or more and 3.5 or less. The supporting salt concentration is preferably 5 W% or more and 50 W% or less in terms of selectivity of the target product and current efficiency.
本発明において陽極はロジウムもしくはロジウムを８０
％以上含む合金よシなる。該陽極は、少なくともその表
面がロジウムもしくはロジウムを８０％以上含む合金で
あればよい。合金中のロジウム以外の成分は、ルテニウ
ム、ノラジウム、イリジウム、白金が好ましい。後述す
る実施例から明らかな様に、該陽極は特異的に消耗が少
ない。In the present invention, the anode is rhodium or rhodium 80
% or more. The anode may be made of rhodium or an alloy containing 80% or more of rhodium at least on its surface. Components other than rhodium in the alloy are preferably ruthenium, noradium, iridium, and platinum. As is clear from the examples described below, the anode has a uniquely low wear rate.
本発明において、ベンゼン濃度は０．５Ｗ％以上５０Ｗ
％以下であることが好ましい。In the present invention, the benzene concentration is 0.5W% or more and 50W
% or less.
本発明において電解は定電流電解あるいは定電位電解い
ずれの方法でも行うことが可能である。In the present invention, electrolysis can be carried out by either constant current electrolysis or constant potential electrolysis.
本発明では、フルオロベンゼンを製造するに際し陽極の
消耗が極めて少ない点で工業的に実施する場合極めて有
利な方法である。The present invention is an extremely advantageous method when carried out industrially in that the consumption of the anode is extremely small when producing fluorobenzene.
実施例１
５０１ｄのテフロン製電解槽にプロピオニトリル２３９
、 （ｎ−０４Ｈｏ）４ＮＦ・３ＨＦ ７ ｆ、ベン
ぜン５Ｆを仕込んだ。陽極としてチタン板上にロジウム
をメッキしたものを用い、陰極としてチタンラス電極を
用い、電流密度ｘＯＡ／ｄｍ”（通電面積１５ｃ！ｎ２
）電気ｆｌ ６＝５７ Ａｈｒでモノフルオロペンぜン
を得た。なお所定の電気量の約％の電流を流した時点で
電解液を、新しく調整した液（液組成は上記と同じ）に
更新した。Example 1 Propionitrile 239 in a 501d Teflon electrolytic cell
, (n-04Ho)4NF.3HF 7f and benzene 5F were charged. A titanium plate plated with rhodium was used as the anode, a titanium lath electrode was used as the cathode, and the current density x OA/dm" (current carrying area 15c!n2
) Monofluoropenzene was obtained with electricity fl 6=57 Ahr. The electrolytic solution was replaced with a newly prepared solution (liquid composition was the same as above) when a current of approximately % of the predetermined amount of electricity was passed.
陽極の消耗はＱ、Ｑ７６ ｆｆ／Ａｈであった。The consumption of the anode was Q, Q76 ff/Ah.
実施例２
陽極としてチタン板上に８０％のロジウムと２０％の白
金の合金をメッキした電極を用いた以外は実施例１と同
様な条件、同様な操作で電解フッ素化を行いモノフルオ
ロベンゼンを得た。結果を表に示した。Example 2 Monofluorobenzene was electrolytically fluorinated under the same conditions and operations as in Example 1, except that an electrode made of a titanium plate plated with an alloy of 80% rhodium and 20% platinum was used as an anode. Obtained. The results are shown in the table.
実施例３
溶媒としてアセトニトリル２３２、支持塩として（０２
Ｈ５）４ＮＦ・２．３ＨＦ７Ｆを用いた以外は実施例１
と同様々条件、同様な操作で電解フッ素化を行いモノフ
ルオロベンゼンを得た。結果を表に示した。Example 3 Acetonitrile 232 as a solvent, (02
H5) Example 1 except that 4NF/2.3HF7F was used
Monofluorobenzene was obtained by electrolytic fluorination using the same conditions and operations as above. The results are shown in the table.
比較例１〜５
表に示した電極を用いその他は実施例１と同様な条件、
同様な操作で電解フッ素化を行い表に示した消耗結果を
得た。Comparative Examples 1 to 5 The electrodes shown in the table were used and the other conditions were the same as in Example 1.
Electrolytic fluorination was carried out in a similar manner and the consumption results shown in the table were obtained.
表table
Claims (1)
一般式Ｒ＾１Ｒ＾２Ｒ＾３Ｒ＾４ＮＦ・ｘＨＦ（式中Ｒ
＾１、Ｒ＾２、Ｒ＾３、Ｒ＾４はアルキル基であり、互
いに同一もしくは異つてもよい。ｘは１以上１０以下で
ある。）で表わされるフツ化テトラアルキルアンモニウ
ム−フツ化水素を用い、ロジウムもしくはロジウムを８
０％以上含む合金よりなる陽極を用いて電解フッ素化す
ることを特徴とするフルオロベンゼンの製法Using benzene and a nitrile compound as a solvent, the general formula R^1R^2R^3R^4NF xHF (in the formula R
^1, R^2, R^3, and R^4 are alkyl groups, and may be the same or different from each other. x is 1 or more and 10 or less. ) using tetraalkylammonium fluoride-hydrogen fluoride, rhodium or rhodium 8
A method for producing fluorobenzene characterized by electrolytic fluorination using an anode made of an alloy containing 0% or more
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61256882A JPS63111192A (en) | 1986-10-30 | 1986-10-30 | Production of fluorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61256882A JPS63111192A (en) | 1986-10-30 | 1986-10-30 | Production of fluorobenzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63111192A true JPS63111192A (en) | 1988-05-16 |
Family
ID=17298721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61256882A Pending JPS63111192A (en) | 1986-10-30 | 1986-10-30 | Production of fluorobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63111192A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3696156A1 (en) | 2019-02-15 | 2020-08-19 | Fujian Yongjing Technology Co., Ltd. | New process for the manufacture of fluoroaryl compounds and derivatives |
-
1986
- 1986-10-30 JP JP61256882A patent/JPS63111192A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3696156A1 (en) | 2019-02-15 | 2020-08-19 | Fujian Yongjing Technology Co., Ltd. | New process for the manufacture of fluoroaryl compounds and derivatives |
| US11420917B2 (en) | 2019-02-15 | 2022-08-23 | Fujian Yongjing Technology Co., Ltd. | Process for the manufacture of fluoroaryl compounds and derivatives |
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