JPS625421B2 - - Google Patents
Info
- Publication number
- JPS625421B2 JPS625421B2 JP15683779A JP15683779A JPS625421B2 JP S625421 B2 JPS625421 B2 JP S625421B2 JP 15683779 A JP15683779 A JP 15683779A JP 15683779 A JP15683779 A JP 15683779A JP S625421 B2 JPS625421 B2 JP S625421B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrobenzonitrile
- fluoride
- fluorobenzonitrile
- reaction
- chloro
- 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.)
- Expired
Links
- SWBDKCMOLSUXRH-UHFFFAOYSA-N 2-nitrobenzonitrile Chemical class [O-][N+](=O)C1=CC=CC=C1C#N SWBDKCMOLSUXRH-UHFFFAOYSA-N 0.000 claims description 15
- GDHXJNRAJRCGMX-UHFFFAOYSA-N 2-fluorobenzonitrile Chemical class FC1=CC=CC=C1C#N GDHXJNRAJRCGMX-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- 235000003270 potassium fluoride Nutrition 0.000 description 12
- 239000011698 potassium fluoride Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 8
- ZHLCARBDIRRRHD-UHFFFAOYSA-N 2-chloro-6-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1C#N ZHLCARBDIRRRHD-UHFFFAOYSA-N 0.000 description 7
- XPTAYRHLHAFUOS-UHFFFAOYSA-N 2-chloro-6-fluorobenzonitrile Chemical compound FC1=CC=CC(Cl)=C1C#N XPTAYRHLHAFUOS-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 239000012025 fluorinating agent Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229940096017 silver fluoride Drugs 0.000 description 4
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 4
- -1 2,3 -dibromo-6-nitrobenzonitrile Chemical compound 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RDFDRMZYAXQLRT-UHFFFAOYSA-N 2,3-dichloro-6-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1C#N RDFDRMZYAXQLRT-UHFFFAOYSA-N 0.000 description 2
- QAWCUFOFDZAVNA-UHFFFAOYSA-N 2-bromo-6-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC(Br)=C1C#N QAWCUFOFDZAVNA-UHFFFAOYSA-N 0.000 description 2
- OFOAJCHZFBHSCB-UHFFFAOYSA-N 2-iodo-6-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC(I)=C1C#N OFOAJCHZFBHSCB-UHFFFAOYSA-N 0.000 description 2
- OZKOAADVLVCNFO-UHFFFAOYSA-N 4-chloro-2-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC(Cl)=CC=C1C#N OZKOAADVLVCNFO-UHFFFAOYSA-N 0.000 description 2
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- PISOOQLALMAJRE-UHFFFAOYSA-N 2,3-dichloro-6-fluorobenzonitrile Chemical compound FC1=CC=C(Cl)C(Cl)=C1C#N PISOOQLALMAJRE-UHFFFAOYSA-N 0.000 description 1
- KDKBYOPMHBZSKW-UHFFFAOYSA-N 2,4-dichloro-6-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(Cl)=C1C#N KDKBYOPMHBZSKW-UHFFFAOYSA-N 0.000 description 1
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 1
- BNBRIFIJRKJGEI-UHFFFAOYSA-N 2,6-difluorobenzonitrile Chemical compound FC1=CC=CC(F)=C1C#N BNBRIFIJRKJGEI-UHFFFAOYSA-N 0.000 description 1
- JHFVJZYSOSQUDW-UHFFFAOYSA-N 2-bromo-4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(Br)=C1 JHFVJZYSOSQUDW-UHFFFAOYSA-N 0.000 description 1
- IELGUZKHALDFOO-UHFFFAOYSA-N 2-bromo-6-fluorobenzonitrile Chemical compound FC1=CC=CC(Br)=C1C#N IELGUZKHALDFOO-UHFFFAOYSA-N 0.000 description 1
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 1
- UXBIHGQYRYAMFN-UHFFFAOYSA-N 2-fluoro-4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(F)=C1 UXBIHGQYRYAMFN-UHFFFAOYSA-N 0.000 description 1
- FAACTMVXBNSPJA-UHFFFAOYSA-N 2-fluoro-6-iodobenzonitrile Chemical compound FC1=CC=CC(I)=C1C#N FAACTMVXBNSPJA-UHFFFAOYSA-N 0.000 description 1
- DOHMTOMVCPKOEE-UHFFFAOYSA-N 2-fluoro-6-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC(F)=C1C#N DOHMTOMVCPKOEE-UHFFFAOYSA-N 0.000 description 1
- CDNHWNSAPDNORO-UHFFFAOYSA-N 2-iodo-4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(I)=C1 CDNHWNSAPDNORO-UHFFFAOYSA-N 0.000 description 1
- RNDBDEZITHKFEU-UHFFFAOYSA-N 3-bromo-4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1Br RNDBDEZITHKFEU-UHFFFAOYSA-N 0.000 description 1
- RUSAWEHOGCWOPG-UHFFFAOYSA-N 3-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC(C#N)=C1 RUSAWEHOGCWOPG-UHFFFAOYSA-N 0.000 description 1
- IOBYLOUUUJPZEO-UHFFFAOYSA-N 4-bromo-2-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC(Br)=CC=C1C#N IOBYLOUUUJPZEO-UHFFFAOYSA-N 0.000 description 1
- JRDMGVGCATYZPW-UHFFFAOYSA-N 4-chloro-2-fluorobenzonitrile Chemical compound FC1=CC(Cl)=CC=C1C#N JRDMGVGCATYZPW-UHFFFAOYSA-N 0.000 description 1
- LCNNOEPOXHHUQG-UHFFFAOYSA-N 5-bromo-2-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1C#N LCNNOEPOXHHUQG-UHFFFAOYSA-N 0.000 description 1
- HPWJUEZFOUOUEO-UHFFFAOYSA-N 5-chloro-2-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1C#N HPWJUEZFOUOUEO-UHFFFAOYSA-N 0.000 description 1
- LHKYUZREPLVVKN-UHFFFAOYSA-N 6-chloro-6-fluorocyclohexa-2,4-diene-1-carbonitrile Chemical compound FC1(Cl)C=CC=CC1C#N LHKYUZREPLVVKN-UHFFFAOYSA-N 0.000 description 1
- 229910021593 Copper(I) fluoride Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は一般式（）で表わされるニトロベン
ゾニトリル誘導体を、周期律表第族の元素のフ
ツ化物と非プロトン性極性溶媒中で反応させるこ
とを特徴とする一般式（）で表わされるフルオ
ロペンゾニトリル誘導体の製造方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized in that a nitrobenzonitrile derivative represented by the general formula () is reacted with a fluoride of an element in Group 1 of the periodic table in an aprotic polar solvent. The present invention relates to a method for producing a fluoropenzonitrile derivative represented by ().
一般式（）
一般式（）
（式中、ＸはCl，Br，Ｉ，Ｆのハロゲン原
子、ｎは０〜４を表わす。）
フルオロベンゾニトリル誘導体は、農薬及び農
薬中間体として有用な物質であるが、現在まで工
業的に安価に製造する方法は無い。 General formula () General formula () (In the formula, X represents a halogen atom of Cl, Br, I, or F, and n represents 0 to 4.) Fluorobenzonitrile derivatives are useful substances as agricultural chemicals and agricultural chemical intermediates, but until now they have not been used industrially. There is no way to manufacture it cheaply.
本発明者は原料的に安価に得られるハロゲノニ
トロベンゼン誘導体のハロゲン基をシアノ基に置
換することで容易に得られるニトロベンゾニトリ
ル誘導体を、非プロトン性極性溶媒中で周期律表
第族の元素のフツ化物からなるフツ素化剤と反
応させることにより温和な条件でニトロ基をフル
オロ基に置換し、好収率でフルオロベンゾニトリ
ル誘導体を得ることが出来ることを見出した。従
来芳香族ニトロ基をフルオロ基に変える方法とし
ては、ニトロ基を還元してアミノ基とし、シーマ
ン反応でフルオロ基を導入する方法が一般的であ
つた。しかし、この方法では反応工程が長く、総
収率が低いこと、又、廃水や廃棄物の量が多いこ
とが欠点であつた。又、本発明方法は、ハロゲン
交換反応（例えば、２，６−ジクロルベンゾニト
リルより、フツ化カリウムを用いて２−クロル−
６−フルオロベンゾニトリルを合成する方法）に
よるフルオロベンゾニトリル誘導体の製造方法と
比較して、温和な条件で生成物が得られること、
原料と生成物の物性が著しく異なるため、反応後
の生成物の分離精製が容易になることからも工業
的に有利な製造方法であることを見い出し、本発
明を完成するに至つたものである。 The present inventor developed a nitrobenzonitrile derivative, which can be easily obtained by substituting a cyano group for the halogen group of a halogenonitrobenzene derivative, which can be obtained at low cost as a raw material, in an aprotic polar solvent. It has been found that fluorobenzonitrile derivatives can be obtained in good yield by substituting nitro groups with fluoro groups under mild conditions by reacting with a fluorinating agent consisting of a fluoride. Conventionally, a common method for converting an aromatic nitro group into a fluoro group is to reduce the nitro group to an amino group, and then introduce a fluoro group by a Siemann reaction. However, this method has drawbacks such as long reaction steps, low total yield, and large amounts of waste water and waste. The method of the present invention also includes a halogen exchange reaction (for example, converting 2,6-dichlorobenzonitrile to 2-chlorobenzonitrile using potassium fluoride).
6-Fluorobenzonitrile (method for synthesizing 6-fluorobenzonitrile), the product can be obtained under mild conditions compared to the method for producing fluorobenzonitrile derivatives;
Since the physical properties of the raw materials and the products are significantly different, the inventors discovered that this is an industrially advantageous production method because it facilitates the separation and purification of the products after the reaction, leading to the completion of the present invention. .
本発明で使用されるニトロベンゾニトリル誘導
体としては、２−ニトロベンゾニトリル、３−ニ
トロベンゾニトリル、４−ニトロベンゾニトリ
ル、２−クロル−６−ニトロベンゾニトリル、２
−クロル−４−ニトロベンゾニトリル、３−クロ
ル−６−ニトロベンゾニトリル、４−クロル−６
−ニトロベンゾニトリル、２，３−ジクロル−６
−ニトロベンゾニトリル、２，４−ジクロル−６
−ニトロベンゾニトリル、２−ブロモ−６−ニト
ロベンゾニトリル、２−ブロモ−４−ニトロベン
ゾニトリル、３−ブロモ−６−ニトロベンゾニト
リル、４−ブロモ−６−ニトロベンゾニトリル、
３−ブロモ−４−ニトロベンゾニトリル、２，３
−ジブロモ−６−ニトロベンゾニトリル、２，４
−ジブロモ−６−ニトロベンゾニトリル、２−ヨ
ード−６−ニトロベンゾニトリル、２−ヨード−
４−ニトロベンゾニトリル、２−フルオロ−６−
ニトロベンゾニトリル、２−フルオロ−４−ニト
ロベンゾニトリル、等、ベンゼン環にシアノ基と
ニトロ基を持つ化合物で好ましくはシアノ基のオ
ルソ位又はパラ位にニトロ基を持つものが使用さ
れる。 The nitrobenzonitrile derivatives used in the present invention include 2-nitrobenzonitrile, 3-nitrobenzonitrile, 4-nitrobenzonitrile, 2-chloro-6-nitrobenzonitrile, 2-nitrobenzonitrile,
-Chlor-4-nitrobenzonitrile, 3-chloro-6-nitrobenzonitrile, 4-chloro-6
-Nitrobenzonitrile, 2,3-dichloro-6
-Nitrobenzonitrile, 2,4-dichloro-6
-Nitrobenzonitrile, 2-bromo-6-nitrobenzonitrile, 2-bromo-4-nitrobenzonitrile, 3-bromo-6-nitrobenzonitrile, 4-bromo-6-nitrobenzonitrile,
3-Bromo-4-nitrobenzonitrile, 2,3
-dibromo-6-nitrobenzonitrile, 2,4
-dibromo-6-nitrobenzonitrile, 2-iodo-6-nitrobenzonitrile, 2-iodo-
4-nitrobenzonitrile, 2-fluoro-6-
Compounds having a cyano group and a nitro group on the benzene ring, such as nitrobenzonitrile and 2-fluoro-4-nitrobenzonitrile, preferably have a nitro group at the ortho or para position of the cyano group.
フツ素化剤として使用するフツ化物としては、
周期律表第族の元素のフツ化物、例えばフツ化
セシウム、フツ化ルビジウム、フツ化カリウム、
フツ化ナトリウム、フツ化リチウム、フツ化第一
銀、フツ化第二銀、フツ化第一銅、フツ化第二銅
が用いられる。フツ化セシウム、フツ化ルビジウ
ムは反応は充分進行するが高価である。又、フツ
化ナトリウム、フツ化リチウムでは反応の進行は
他のものに比べ遅い。実用的には、工業的に安価
に入手出来るフツ化カリウムが特に好ましい。
又、高価ではあるが、本反応において主反応の選
択率が良く、反応後常法により容易に回収出来る
フツ化第一銀も有用なフツ素化剤として使用され
る。フツ素化剤の使用量は、使用するニトロベン
ゾニトリル誘導体に対して、0.5〜5.0倍モルが好
ましく、特に1.0〜3.0倍モルが適当である。 Fluorides used as fluorinating agents include:
Fluorides of elements in group of the periodic table, such as cesium fluoride, rubidium fluoride, potassium fluoride,
Sodium fluoride, lithium fluoride, silver fluoride, silver fluoride, cuprous fluoride, and cupric fluoride are used. Although the reaction of cesium fluoride and rubidium fluoride proceeds satisfactorily, they are expensive. In addition, the reaction progresses slower with sodium fluoride and lithium fluoride than with others. Practically speaking, potassium fluoride, which is industrially available at low cost, is particularly preferred.
Although expensive, silver fluoride, which has a good selectivity for the main reaction in this reaction and can be easily recovered by conventional methods after the reaction, is also used as a useful fluorinating agent. The amount of the fluorinating agent to be used is preferably 0.5 to 5.0 times, more preferably 1.0 to 3.0 times, by mole, relative to the nitrobenzonitrile derivative used.
非プロトン性極性溶媒としては、Ｎ，Ｎ−ジメ
チルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミ
ド、ジメチルスルホキシド、ジメチルスルホン、
テトラメチレンスルホン、アセトアミド、ヘキサ
メチルホスホルアミド、Ｎ−メチルピロリドン、
Ｎ，N′−ジメチルイミダゾリドン等が使用され
る。その使用量は、原料として使用するニトロベ
ンゾニトリル誘導体1.0重量部に対して0.5〜10.0
重量部が好ましく、特に1.0〜5.0重量部が適当で
ある。 Examples of the aprotic polar solvent include N,N-dimethylformamide, N,N-diethylformamide, dimethylsulfoxide, dimethylsulfone,
Tetramethylene sulfone, acetamide, hexamethylphosphoramide, N-methylpyrrolidone,
N,N'-dimethylimidazolidone and the like are used. The amount used is 0.5 to 10.0 parts by weight of the nitrobenzonitrile derivative used as a raw material.
Parts by weight are preferred, particularly 1.0 to 5.0 parts by weight.
反応温度及び反応時間は使用する溶剤の種類や
使用量により異なるが、反応温度は一般的には50
℃〜200℃が良く、好ましくは100℃〜140℃が適
当である。反応時間は0.5〜20.0時間が適当であ
る。 The reaction temperature and reaction time vary depending on the type and amount of solvent used, but the reaction temperature is generally 50°C.
The temperature range is preferably from 100°C to 200°C, preferably from 100°C to 140°C. A suitable reaction time is 0.5 to 20.0 hours.
反応終了後、無機物を別し、液を減圧下蒸
留することにより、目的とするフルオロベンゾニ
トリル誘導体を未反応のニトロベンゾニトリル誘
導体より容易に分離することが出来る。 After the reaction is completed, the inorganic substances are separated and the liquid is distilled under reduced pressure, whereby the desired fluorobenzonitrile derivative can be easily separated from the unreacted nitrobenzonitrile derivative.
又、使用した溶剤及び未反応のニトロベンゾニ
トリル誘導体は回収し再使用することが可能であ
る。 Further, the used solvent and unreacted nitrobenzonitrile derivative can be recovered and reused.
以下実施例によつて本発明をさらに詳しく説明
するが、本発明はこれらに限定されるものではな
い。 The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.
実施例 １
２−クロル−６−ニトロベンゾニトリル18.2
ｇ、フツ化カリウム7.0ｇにジメチルスルホキシ
ド60.0ｇを加え、反応温度120℃で６時間反応さ
せた。反応終了後無機物を別した後、液中の
生成物をガスクロマトグラフイにより定量し、収
率70.3％で２−クロル−６−フルオロベンゾニト
リルを得た。Example 1 2-chloro-6-nitrobenzonitrile 18.2
60.0 g of dimethyl sulfoxide was added to 7.0 g of potassium fluoride, and the mixture was reacted at a reaction temperature of 120° C. for 6 hours. After the completion of the reaction, the inorganic substances were separated, and the product in the liquid was quantified by gas chromatography to obtain 2-chloro-6-fluorobenzonitrile in a yield of 70.3%.
実施例 ２
２−クロル−６−ニトロベンゾニトリル18.2
ｇ、フツ化セシウム18.2ｇにジメチルスルホキシ
ド60.0ｇを加え、反応温度120℃で２時間反応さ
せた。実施例１と同様の方法で後処理を行い、収
率89.7％で２−クロル−フルオロベンゾニトリル
を得た。Example 2 2-chloro-6-nitrobenzonitrile 18.2
60.0 g of dimethyl sulfoxide was added to 18.2 g of cesium fluoride, and the mixture was reacted at a reaction temperature of 120° C. for 2 hours. Post-treatment was performed in the same manner as in Example 1 to obtain 2-chloro-fluorobenzonitrile in a yield of 89.7%.
実施例 ３
２−クロル−６−ニトロベンゾニトリル18.2
ｇ、フツ化第一銀30.8ｇ、にジメチルスルホキシ
ド60.0ｇを加え、反応温度120℃で６時間反応さ
せた。実施例１と同様の方法で後処理を行い、収
率85.2％で２−クロル−６−フルオロベンゾニト
リルを得た。Example 3 2-chloro-6-nitrobenzonitrile 18.2
60.0 g of dimethyl sulfoxide was added to 30.8 g of silver fluoride, and the mixture was reacted at a reaction temperature of 120° C. for 6 hours. Post-treatment was performed in the same manner as in Example 1 to obtain 2-chloro-6-fluorobenzonitrile in a yield of 85.2%.
実施例 ４
２−クロル−６−ニトロベンゾニトリル18.2
ｇ、フツ化ナトリウム5.0ｇにジメチルスルホキ
シド60.0ｇを加え、反応温度160℃で６時間反応
させた。実施例１と同様の方法で後処理を行い、
収率37.4％で２−クロル−６−フルオロベンゾニ
トリルを得た。Example 4 2-chloro-6-nitrobenzonitrile 18.2
60.0 g of dimethyl sulfoxide was added to 5.0 g of sodium fluoride, and the mixture was reacted at a reaction temperature of 160° C. for 6 hours. Post-processing was performed in the same manner as in Example 1,
2-chloro-6-fluorobenzonitrile was obtained with a yield of 37.4%.
実施例 ５
２−クロル−６−ニトロベンゾニトリル18.2
ｇ、フツ化カリウム7.0ｇにＮ，Ｎ−ジメチルホ
ルムアミド60.0ｇを加え反応温度120℃で６時間
反応させた。実施例１と同様の方法で後処理を行
い、収率63.6％で２−クロル−６−フルオロベン
ゾニトリルを得た。Example 5 2-chloro-6-nitrobenzonitrile 18.2
60.0 g of N,N-dimethylformamide was added to 7.0 g of potassium fluoride and reacted at a reaction temperature of 120° C. for 6 hours. Post-treatment was performed in the same manner as in Example 1 to obtain 2-chloro-6-fluorobenzonitrile in a yield of 63.6%.
実施例 ６
２−クロル−６−ニトロベンゾニトリル18.2
ｇ、フツ化カリウム7.0ｇにＮ−メチルピロリド
ン60.0ｇを加え、反応温度120℃で12時間反応さ
せた。実施例１と同様の方法で後処理を行い、収
率52.5％で２−クロル−６−フルオロベンゾニト
リルを得た。Example 6 2-chloro-6-nitrobenzonitrile 18.2
60.0 g of N-methylpyrrolidone was added to 7.0 g of potassium fluoride and reacted at a reaction temperature of 120° C. for 12 hours. Post-treatment was performed in the same manner as in Example 1 to obtain 2-chloro-6-fluorobenzonitrile in a yield of 52.5%.
実施例 ７
２−ニトロベンゾニトリル14.8ｇ、フツ化カリ
ウム7.0ｇにジメチルスルホキシド60.0ｇを加
え、反応温度120℃で６時間反応させた。実施例
１と同様の方法で後処理を行い、収率66.2％で２
−フルオロベンゾニトリルを得た。Example 7 60.0 g of dimethyl sulfoxide was added to 14.8 g of 2-nitrobenzonitrile and 7.0 g of potassium fluoride, and the mixture was reacted at a reaction temperature of 120° C. for 6 hours. Post-treatment was carried out in the same manner as in Example 1, and 2 was obtained with a yield of 66.2%.
-Fluorobenzonitrile was obtained.
実施例 ８
４−ニトロベンゾニトリル14.8ｇ、フツ化カリ
ウム7.0ｇにジメチルスルホキシド60.0ｇを加
え、反応温度140℃で６時間反応させた。実施例
１と同様の方法で後処理を行い、収率45.2％で４
−フルオロベンゾニトリルを得た。Example 8 60.0 g of dimethyl sulfoxide was added to 14.8 g of 4-nitrobenzonitrile and 7.0 g of potassium fluoride, and the mixture was reacted at a reaction temperature of 140° C. for 6 hours. Post-treatment was carried out in the same manner as in Example 1, and 4 was obtained with a yield of 45.2%.
-Fluorobenzonitrile was obtained.
実施例 ９
４−クロル−６−ニトロベンゾニトリル18.2
ｇ、フツ化カリウム7.0ｇにジメチルスルホキシ
ド60.0ｇを加え、反応温度120℃で６時間反応さ
せた。実施例１と同様の方法で後処理を行い、収
率69.2％で４−クロル−６−フルオロベンゾニト
リルを得た。Example 9 4-chloro-6-nitrobenzonitrile 18.2
60.0 g of dimethyl sulfoxide was added to 7.0 g of potassium fluoride, and the mixture was reacted at a reaction temperature of 120° C. for 6 hours. Post-treatment was performed in the same manner as in Example 1 to obtain 4-chloro-6-fluorobenzonitrile in a yield of 69.2%.
実施例 10
２，３−ジクロル−６−ニトロベンゾニトリル
21.7ｇ、フツ化カリウム7.0ｇにジメチルスルホ
キシド60.0ｇを加え反応温度120℃で６時間反応
させた。実施例１と同様の方法で後処理を行い、
収率72.0％で２，３−ジクロル−６−フルオロベ
ンゾニトリルを得た。Example 10 2,3-dichloro-6-nitrobenzonitrile
60.0 g of dimethyl sulfoxide was added to 21.7 g of potassium fluoride and 7.0 g of potassium fluoride, and the mixture was reacted at a reaction temperature of 120° C. for 6 hours. Post-processing was performed in the same manner as in Example 1,
2,3-dichloro-6-fluorobenzonitrile was obtained with a yield of 72.0%.
実施例 11
２−ブロモ−６−ニトロベンゾニトリル22.7
ｇ、フツ化カリウム7.0ｇにジメチルスルホキシ
ド60.0ｇを加え、反応温度120℃で６時間反応さ
せた。実施例１と同様の方法で後処理を行い収率
68.7％で２−ブロモ−６−フルオロベンゾニトリ
ルを得た。Example 11 2-bromo-6-nitrobenzonitrile 22.7
60.0 g of dimethyl sulfoxide was added to 7.0 g of potassium fluoride, and the mixture was reacted at a reaction temperature of 120° C. for 6 hours. Post-treatment was performed in the same manner as in Example 1, and the yield was
2-bromo-6-fluorobenzonitrile was obtained at 68.7%.
実施例 12
フツ化セシウム18.2ｇの代りにフツ化ルビジウ
ム12.6ｇを用いた以外は実施例２と同様にして反
応及び後処理を行い、収率78.3％で２−クロル−
６−フルオロベンゾニトリルを得た。Example 12 The reaction and post-treatment were carried out in the same manner as in Example 2 except that 12.6 g of rubidium fluoride was used instead of 18.2 g of cesium fluoride, and 2-chloro-
6-fluorobenzonitrile was obtained.
実施例 13
２−ニトロベンゾニトリル14.8ｇの代りに２，
３，４−トリクロル−６−ニトロベンゾニトリル
25.2ｇを用いた以外は実施例７と同様にして反応
及び後処理を行い、収率73.5％で２，３，４−ト
リクロル−６−フルオロベンゾニトリルを得た。Example 13 2, instead of 14.8 g of 2-nitrobenzonitrile
3,4-trichloro-6-nitrobenzonitrile
The reaction and post-treatment were carried out in the same manner as in Example 7, except that 25.2 g was used, and 2,3,4-trichloro-6-fluorobenzonitrile was obtained in a yield of 73.5%.
実施例 14
２−ニトロベンゾニトリル14.8ｇの代りに２−
ヨード−６−ニトロベンゾニトリル27.4ｇを用い
た以外は実施例７と同様にして反応及び後処理を
行い、収率68.3％で２−ヨード−６−フルオロベ
ンゾニトリルを得た。Example 14 Instead of 14.8 g of 2-nitrobenzonitrile, 2-
The reaction and post-treatment were carried out in the same manner as in Example 7, except that 27.4 g of iodo-6-nitrobenzonitrile was used, and 2-iodo-6-fluorobenzonitrile was obtained in a yield of 68.3%.
実施例 15
２−ニトロベンゾニトリル14.8ｇの代りに２−
フルオロ−６−ニトロベンゾニトリル16.6ｇを用
いた以外は実施例７と同様にして反応及び後処理
を行い、収率65.4％で、２，６−ジフルオロベン
ゾニトリルを得た。Example 15 Instead of 14.8 g of 2-nitrobenzonitrile, 2-
The reaction and post-treatment were carried out in the same manner as in Example 7, except that 16.6 g of fluoro-6-nitrobenzonitrile was used, and 2,6-difluorobenzonitrile was obtained with a yield of 65.4%.
Claims (1)
リル誘導体を、周期律表第族の元素のフツ化物
と、非プロトン性極性溶媒中で反応させることを
特徴とする、一般式（）で表わされるフルオロ
ベンゾニトリル誘導体の製造方法。 一般式（） 一般式（） （式中、ＸはCl，Br，Ｉ，Ｆのハロゲン原
子、ｎは０〜４を表わす）[Scope of Claims] 1. A nitrobenzonitrile derivative represented by the general formula () is reacted with a fluoride of an element in Group 1 of the periodic table in an aprotic polar solvent. ) A method for producing a fluorobenzonitrile derivative represented by General formula () General formula () (In the formula, X represents a halogen atom of Cl, Br, I, F, and n represents 0 to 4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15683779A JPS5679660A (en) | 1979-12-05 | 1979-12-05 | Preparation of fluorobenzonitrile derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15683779A JPS5679660A (en) | 1979-12-05 | 1979-12-05 | Preparation of fluorobenzonitrile derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5679660A JPS5679660A (en) | 1981-06-30 |
| JPS625421B2 true JPS625421B2 (en) | 1987-02-04 |
Family
ID=15636443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15683779A Granted JPS5679660A (en) | 1979-12-05 | 1979-12-05 | Preparation of fluorobenzonitrile derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5679660A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5838248A (en) * | 1981-08-31 | 1983-03-05 | Ishihara Sangyo Kaisha Ltd | 3-chloro-2,6-difluorobenzonitrile |
| SE0403003D0 (en) * | 2004-12-09 | 2004-12-09 | Astrazeneca Ab | Chemical compound 1 |
-
1979
- 1979-12-05 JP JP15683779A patent/JPS5679660A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5679660A (en) | 1981-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH01301636A (en) | Production of 1,2,2,2-tetrafluoroethyl difluoromethyl ether | |
| JPS63502181A (en) | Method for producing fluoroaromatic compounds in potassium fluoride dispersion | |
| JPS625421B2 (en) | ||
| US4849552A (en) | Preparation of fluoroaromatic compounds in dispersion of potassium fluoride | |
| JPH024580B2 (en) | ||
| JPS5824430B2 (en) | Method for producing fluorobenzonitrile | |
| JPH07145111A (en) | Preparation of polyfluorinated nitrobenzene | |
| JPH0149137B2 (en) | ||
| JPH072751A (en) | 2,3-difluoro-6-nitrobenzonitrile, 2-chloro-5,6- difluorobenzonitrile (2,3-difluoro-6-chlorobenzonitrile), their production and method of using them to produce 2,3,6-trifluorobenzoic acid | |
| JP3806962B2 (en) | Method for producing 3,5-bis (trifluoromethyl) bromobenzene | |
| JPH0616613A (en) | 2-chloro-4,5-difluorobenzonitrile and its preparation | |
| JPS6335548A (en) | Production of triarylamine | |
| JPH04224535A (en) | Production of 1,3,5-trifluorobenzene | |
| JPS6350339B2 (en) | ||
| JPS6147830B2 (en) | ||
| US5489715A (en) | Process for preparing 4,5-difluorobenzaldehydes | |
| JPH0229667B2 (en) | ||
| US4952719A (en) | Process for the preparation of halo aromatic compounds | |
| JPH0648991A (en) | Production of chlorinated and brominated benzene compounds by selective nucleophilic fluorination and denitration | |
| JPH037662B2 (en) | ||
| JPH0830065B2 (en) | Method for producing fluoro-lower 0-diaminobenzo-1,4-dioxenes | |
| JP4651003B2 (en) | Method for producing fluorinated aniline | |
| JPS60228436A (en) | Fluorination of aromatic compound | |
| JP2779527B2 (en) | Method for producing 4-chloro-2-fluoronitrobenzene | |
| JP2000212104A (en) | Production of bis (trifluoromethyl)monobromobenzene |