JPH0377850A - Production of fluorinated nitro-or cyano-benzene - Google Patents
Production of fluorinated nitro-or cyano-benzeneInfo
- Publication number
- JPH0377850A JPH0377850A JP1211995A JP21199589A JPH0377850A JP H0377850 A JPH0377850 A JP H0377850A JP 1211995 A JP1211995 A JP 1211995A JP 21199589 A JP21199589 A JP 21199589A JP H0377850 A JPH0377850 A JP H0377850A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- nitro
- benzene
- cyano
- cyanopyridine
- 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
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000005181 nitrobenzenes Chemical class 0.000 title abstract description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 12
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 12
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 19
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 3
- QUIMTLZDMCNYGY-UHFFFAOYSA-N 2,4-dichloro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1Cl QUIMTLZDMCNYGY-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
- -1 benzonitrile Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RJXOVESYJFXCGI-UHFFFAOYSA-N 2,4-difluoro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1F RJXOVESYJFXCGI-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 2
- XNJAYQHWXYJBBD-UHFFFAOYSA-N 1,4-difluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(F)=CC=C1F XNJAYQHWXYJBBD-UHFFFAOYSA-N 0.000 description 1
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- CVICEEPAFUYBJG-UHFFFAOYSA-N 5-chloro-2,2-difluoro-1,3-benzodioxole Chemical group C1=C(Cl)C=C2OC(F)(F)OC2=C1 CVICEEPAFUYBJG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- KZLXBZDNRACERI-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC KZLXBZDNRACERI-UHFFFAOYSA-M 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は医薬、農薬などの中間体として有用な弗素化ニ
トロまたはシアノベンゼンの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a method for producing fluorinated nitro or cyanobenzene useful as an intermediate for pharmaceuticals, agricultural chemicals, etc.
「従来の技術」
従来、塩素化ニトロまたはシアノベンゼンを弗化カリウ
ムと反応させその塩素原子を弗素原子に置換させて弗素
化ニトロまたはシアノベンゼンを製造する場合、反応溶
媒としてベンゼン、トルエン、キシレン、ベンゾニトリ
ルなどの芳香族炭化水素類、ジメチルスルホキシド、ス
ルホラン、ジメチルホルムアミドなどの非プロトン性極
性溶媒を使用して反応を行なうことが知られている。"Prior Art" Conventionally, when producing fluorinated nitro or cyanobenzene by reacting chlorinated nitro or cyanobenzene with potassium fluoride and replacing the chlorine atom with a fluorine atom, benzene, toluene, xylene, It is known to carry out the reaction using aromatic hydrocarbons such as benzonitrile, aprotic polar solvents such as dimethyl sulfoxide, sulfolane, and dimethylformamide.
「発明の開示」
本発明者達は、反応溶媒としてシアノピリジンを使用し
た場合、所期の弗素化反応が良好に進み、また反応生成
物から目的物を簡便に分離できることの知見に基き、０
位または／およびｐ位に少くとも１ケの塩素原子を有す
る塩素化ニトロまたはシアノベンゼンを溶媒の存在下に
弗化カリウムと反応させ、当該塩素原子を弗素原子に置
換させて弗素化ニトロまたはシアノベンゼンを製造する
方法において、反応溶媒としてシアノピリジンを存在さ
せることにより弗素化ニトロまたはシアノベンゼンを製
造する方法を提供するに至った。"Disclosure of the Invention" The present inventors have discovered that when cyanopyridine is used as a reaction solvent, the desired fluorination reaction proceeds well, and the target product can be easily separated from the reaction product.
A chlorinated nitro or cyanobenzene having at least one chlorine atom at the position or/and p-position is reacted with potassium fluoride in the presence of a solvent, and the chlorine atom is replaced with a fluorine atom to form a fluorinated nitro or cyanobenzene. In the method for producing benzene, a method for producing fluorinated nitro or cyanobenzene has been provided by allowing cyanopyridine to be present as a reaction solvent.
本発明における原料物質としての塩素化二トロまたはシ
アノベンゼンは一般式：
Ｘ
３
（式中、Ｘはニトロ基またはシアノ基であり、Ｙ１〜Ｙ
、は水素原子、ハロゲン原子、ニトロ基またはシアノ基
であり、但しＹ、、ＹユおよびＹ。Chlorinated nitro or cyanobenzene as a raw material in the present invention has the general formula:
, is a hydrogen atom, a halogen atom, a nitro group or a cyano group, provided that Y, , Y and Y.
のうち少くとも１ケは塩素原子である）で表わされるも
のであり、またハロゲン原子は弗素原子、塩素原子、臭
素原子または沃素原子である。この塩素化ニトロまたは
シアノベンゼンの具体例としては例えば２−クロロ、４
−クロロ、２．４−ジクロロ、２．３−ジクロロ、２．
５−ジクロロ、２．６−ジクロロ、３．４−ジクロロ、
２．４．６−トリクロロ、２，３．４−１−ジクロロ、
２．４．５−１−ジクロロ、２，３．４．５−テトラク
ロロなどの各ニトロベンゼンまたは各シアンベンゼン、
４−クロロ、４．６−ジクロロまたは２，４．５− ト
リクロロの各１．３−ジニトロベンゼン、テトラクロロ
１，２．１．３または１．４−各ジシアノベンゼンなど
のジニトロまたはジシアノベンゼン、２−クロロ−４−
ニトロ、４−クロロ−２−二トロ、２−１０ロー〇−二
１・口、２．３−ジクロロ−６−二トロの各シアノベン
ゼン、２−クロロ−４−フルオロ、４−クロロニ２−フ
ルオロ、２．３．５− ） ＩＪクタロ−４−フルオロ
、２．４−ジクロロ−３−フルオロなどの各ニトロベン
ゼンなどが挙げられる。At least one of them is a chlorine atom), and the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Specific examples of this chlorinated nitro or cyanobenzene include 2-chloro, 4
-chloro, 2.4-dichloro, 2.3-dichloro, 2.
5-dichloro, 2,6-dichloro, 3,4-dichloro,
2.4.6-trichloro, 2,3.4-1-dichloro,
2.4.5-1-dichloro, each nitrobenzene or each cyanobenzene such as 2,3.4.5-tetrachloro,
dinitro or dicyanobenzenes, such as 4-chloro, 4,6-dichloro or 2,4,5-trichloro, each 1,3-dinitrobenzene, tetrachloro 1,2.1.3 or 1,4-dicyanobenzene; 2-chloro-4-
Nitro, 4-chloro-2-nitro, 2-10-21, 2,3-dichloro-6-nitro cyanobenzene, 2-chloro-4-fluoro, 4-chloro-2- Examples include nitrobenzenes such as fluoro, 2.3.5-) IJcutaro-4-fluoro, and 2.4-dichloro-3-fluoro.
本発明の反応は、通常、前記塩素化ニトロまたはシアノ
ベンゼンと弗化カリウムとをシアノピリジンの存在下に
加熱しながら撹拌させることにより行なうが、反応の際
触媒を存在させると一般に反応速度を向上させることが
できる。触媒としては例えば１８−クラウン−６、ジシ
クロへキシル−１８−クラウン−６、ジベンゾ−１８−
クラウン−６などの各エーテル、テトラデシルトリメチ
ルアンモニウムブロマイド、そのクロライド、メチルト
リオクチルアンモニウムクロライド、ベンジルトリエチ
ルアンモニウムクロライド、フェニルトリメチルアンモ
ニウムクロライド、Ｎ−（２−エチルヘキシル）−４−
（ジメチル）アミノピリジウムクロライド、トリベンジ
ルデシルアンモニウムクロライドなどの第４級アンモニ
ウム塩、テトラフェニルホスホニウムブロマイド、ヘキ
サデシルトリブチルホスホニウムアイオダイドなどのホ
スホニウム化合物が挙げられる。The reaction of the present invention is usually carried out by heating and stirring the chlorinated nitro or cyanobenzene and potassium fluoride in the presence of cyanopyridine, but the presence of a catalyst during the reaction generally improves the reaction rate. can be done. Examples of catalysts include 18-crown-6, dicyclohexyl-18-crown-6, dibenzo-18-
Ethers such as Crown-6, tetradecyltrimethylammonium bromide, its chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride, phenyltrimethylammonium chloride, N-(2-ethylhexyl)-4-
Examples include quaternary ammonium salts such as (dimethyl)aminopyridium chloride and tribenzyldecyl ammonium chloride, and phosphonium compounds such as tetraphenylphosphonium bromide and hexadecyltributylphosphonium iodide.
本発明で使用する弗化カリウムは粒子径が小さく比表面
積の高い、よく乾燥したものが高い反応活性を有するの
で好ましく、その使用量は原料物質、目的物、触媒また
は反応溶媒の種類、反応温度、反応時間などの相違によ
り異なり一概に規定できないが、原料物質の塩素化ニト
ロまたはシアンベンゼンの塩素原子１ケの反応当量当り
、１〜５当量望ましくは１〜２当量である。Potassium fluoride used in the present invention has a small particle size, a high specific surface area, and is preferably well-dried because it has high reaction activity. The amount varies depending on the reaction time and the like and cannot be absolutely defined, but it is 1 to 5 equivalents, preferably 1 to 2 equivalents, per reaction equivalent of one chlorine atom of the chlorinated nitro or cyanobenzene as the raw material.
また、本発明で使用する触媒および反応溶媒の使用量も
同様に一概に規定できないが、塩素化ニトロまたはシア
ノベンゼン１モル当り、触媒は０．０１〜０．５モル望
ましくは０．０５〜０．１モルであり、反応溶媒は０．
１〜１０モル望ましくは０．５〜３．０モルである。反
応溶媒としては２．３、または４−シアノピリジンが挙
げられるが３−シアノピリジンが好ましい。またそれら
は単独で使用してもよいが、各シアノピリジンに対して
トルエン、ベンゾニトリル、ジメチルスルホキシド、ス
ルホランなどの芳香族炭化水素類または非プロトン性極
性溶媒を混合して使用してもよい。Furthermore, although the amounts of the catalyst and reaction solvent used in the present invention cannot be specified in a general manner, the amount of the catalyst is preferably 0.01 to 0.5 mol per 1 mol of chlorinated nitro or cyanobenzene, preferably 0.05 to 0. .1 mol, and the reaction solvent was 0.1 mol.
The amount is 1 to 10 moles, preferably 0.5 to 3.0 moles. Examples of the reaction solvent include 2,3- and 4-cyanopyridine, with 3-cyanopyridine being preferred. Further, they may be used alone, but each cyanopyridine may be used in combination with an aromatic hydrocarbon such as toluene, benzonitrile, dimethyl sulfoxide, or sulfolane, or an aprotic polar solvent.
このようにして本発明の反応は行なわれるが、一般にｌ
θ℃〜還流温度で１〜２４時間、望ましくは６０℃〜還
流温度で３〜１５時間行なわれる。Although the reaction of the present invention is carried out in this manner, generally l
The reaction is carried out at θ° C. to reflux temperature for 1 to 24 hours, preferably 60° C. to reflux temperature for 3 to 15 hours.
本発明の反応では原料物質の塩素化ニトロまたはシアノ
ベンゼンについて、０位または／およびｐ位に存在する
少くとも１ケないし多くても３ケの塩素原子が全部ない
し部分的に弗素原子に置換される反応が生ずるが、この
反応以外に弗素原子を除くハロゲン原子がｍ位に存在す
る場合それらも弗素原子により置換される反応あるいは
ｏ、 ｍまたはｐ各位にニトロ基が存在する場合そのニ
トロ基が弗素原子により置換される反応も生ずることが
あるが、本発明はかかる反応をも対象とする。In the reaction of the present invention, at least one or at most three chlorine atoms present at the 0-position and/or p-position of the starting material, chlorinated nitro or cyanobenzene, are completely or partially substituted with fluorine atoms. In addition to this reaction, if a halogen atom other than a fluorine atom is present at the m position, a reaction in which it is also replaced by a fluorine atom, or a reaction in which a nitro group is present at each o, m or p position, the nitro group is replaced. Reactions in which fluorine atoms are substituted may also occur, and the present invention is also directed to such reactions.
例えば２．４−ジクロロニトロベンゼンから２−りｏロ
ー４−フルオロ、２−フルオロ−４−クロロまたは２，
４−ジフルオロ各ニトロベンゼンを生成、２．５−ジク
ロロニトロベンゼンから２−フ）Ｌｔオロー５−クロロ
又は２．５−ジフルオロ各ニトロベンゼンを生成、２，
４．５− トリクロロ−１，３−ジニトロベンゼンから
２．４−ジフルオロ−５−クロロ＝１．３−ジニトロベ
ンゼンまたは２．３．４− トリフルオロ−５−クロロ
ニトロベンゼンを生成する場合が挙げられる。その場合
目的とする反応に合致させるべく弗化カリウム、触媒の
使用量、反応条件などを適宜選択する必要がある。For example, from 2,4-dichloronitrobenzene to 2-fluoro-4-fluoro, 2-fluoro-4-chloro or 2,
4-difluoro each nitrobenzene is produced, 2.5-dichloronitrobenzene is produced from 2-F) Lt-olor 5-chloro or 2.5-difluoro nitrobenzene is produced, 2,
Examples include the case of producing 2.4-difluoro-5-chloro=1.3-dinitrobenzene or 2.3.4-trifluoro-5-chloronitrobenzene from 4.5-trichloro-1,3-dinitrobenzene. . In that case, it is necessary to appropriately select potassium fluoride, the amount of catalyst used, reaction conditions, etc. in order to match the desired reaction.
反応生成物から目的物を精製、分離する場合通常の方法
に準じて行なうが、反応生成物を鉱酸水溶液で処理する
と反応溶媒のシアノピリジンは鉱酸塩を形成して水相に
移り、更にその鉱酸塩を塩基性物質で処理するとシアノ
ピリジンを生成、再使用できる。一方目的物の弗素化ニ
トロまたはシアノベンゼンは油相に残るので、反応溶媒
と目的物とは分液により簡便に分離することができる。Purification and separation of the target product from the reaction product is carried out in accordance with the usual method, but when the reaction product is treated with an aqueous mineral acid solution, the cyanopyridine in the reaction solvent forms a mineral acid salt and transfers to the aqueous phase. When the mineral salt is treated with a basic substance, cyanopyridine is produced and can be reused. On the other hand, since the target product, fluorinated nitro or cyanobenzene, remains in the oil phase, the reaction solvent and the target product can be easily separated by liquid separation.
次に本発明の実施例を記載する。Next, examples of the present invention will be described.
「実施例」
実施例１
撹拌機、冷却器および温度計を備えた５ ０ Ｑｍｌの
四ツ目フラスコに、２．４−ジクロロニトロベンゼン９
６．０ｇ（０，５モル）、テトラフェニルホスホニウム
ブロマイド１０．５ ｇ （０，０２５モル）、３−シ
アノピリジン５０ｇおよびトルエン５ Ｑｍｌを入れ、
油浴上で窒素ガス気流下加熱撹拌しながらトルエンを留
去させて共沸脱水を行なった。"Example" Example 1 In a 50 Qml four-eye flask equipped with a stirrer, condenser and thermometer, 2,4-dichloronitrobenzene 9
6.0 g (0.5 mol), 10.5 g (0.025 mol) of tetraphenylphosphonium bromide, 50 g of 3-cyanopyridine and 5 Qml of toluene,
Azeotropic dehydration was performed by distilling toluene off while heating and stirring under a nitrogen gas stream on an oil bath.
その後、反応容器内を８０℃まで冷却し、スプレー乾燥
弗化カリウム７２．５ｇ（１，２５モル）を加え、窒素
ガス雰囲気下１７０〜１８０℃で撹拌を行ない６時間反
応を行なった。反応液をガスクロマトグラフィーで分析
したところ、原料の２，４−ジクロロニトロベンゼンの
反応率は９９％、２゜４−ジフルオロニトロベンゼンは
９３％生成していた。Thereafter, the inside of the reaction vessel was cooled to 80° C., 72.5 g (1.25 mol) of spray-dried potassium fluoride was added, and the reaction was carried out for 6 hours by stirring at 170 to 180° C. under a nitrogen gas atmosphere. Analysis of the reaction solution by gas chromatography revealed that the reaction rate of 2,4-dichloronitrobenzene as a raw material was 99% and that of 2°4-difluoronitrobenzene was 93%.
反応液を冷却し、３０％の硫酸水溶液３００ｇとベンゼ
ン２００ｇを加えた。これにより、反応で生成した塩化
カリウム、未反応弗化カリウムおよび３−シアノピリジ
ンは硫酸水溶液の層へ、反応で生成した２、４−ジフル
オロニトロベンゼンおよびその他オイル成分は有機層へ
とそれぞれ移り、さらに有機層を水洗し、ベンゼンを留
去後、残渣を減圧蒸留して２．４−ジフルオロニトロベ
ンゼン（ｂｐ、 １１０〜１１３℃／ １０ ｍｍ１１
ｇ ）の５８．０ｇ（収率７３％）を得た。The reaction solution was cooled, and 300 g of a 30% aqueous sulfuric acid solution and 200 g of benzene were added. As a result, potassium chloride produced in the reaction, unreacted potassium fluoride, and 3-cyanopyridine are transferred to the sulfuric acid aqueous solution layer, and 2,4-difluoronitrobenzene and other oil components produced in the reaction are transferred to the organic layer. After washing the organic layer with water and distilling off the benzene, the residue was distilled under reduced pressure to obtain 2,4-difluoronitrobenzene (bp, 110-113°C/10 mm11
58.0 g (yield 73%) of
実施例２
前記実施例１において、２．４−ジクロロニトロベンゼ
ンに代えて４−クロロニトロベンゼン７８．８ｇ（０，
５モル）を用い、スプレー乾燥弗化カリウム４３．５ｇ
（０，７５モル）を用いる以外は実施例１と同様に行な
い、４−フルオロニトロベンゼン５５．６ｇ（収率７８
％）を得た。Example 2 In Example 1, 78.8 g of 4-chloronitrobenzene (0,
5 mol) and 43.5 g of spray-dried potassium fluoride.
The procedure was carried out in the same manner as in Example 1 except that 4-fluoronitrobenzene (0.75 mol) was used.
%) was obtained.
実施例３
前記実施例１と同様の四ツ目フラスコを反応容器として
用い、２，４．５− ）ジクロロ−１，３−ジニトロベ
ンゼン１３．６ ｇ（０，０５モル）、スプレー乾燥弗
化カリウム２６．１ ｇ （０，４５モル）および３シ
アノピリジン５０ｇを用い、前記実施例１の場合と同様
にして１６０℃で１時間反応を行なった。Example 3 A four-eye flask similar to that in Example 1 was used as a reaction vessel, and 13.6 g (0.05 mol) of 2,4.5-)dichloro-1,3-dinitrobenzene was spray-dried and fluorinated. Using 26.1 g (0.45 mol) of potassium and 50 g of 3-cyanopyridine, a reaction was carried out at 160° C. for 1 hour in the same manner as in Example 1 above.
反応液をガスクロマトグラフィーで分析したところ、２
，４−ジフルオロ−５−クロロ−１，３−ジニトロベン
ゼンが８５．６％、２．３．４−）リフルオロ−５−ク
ロロ−ニトロベンゼンが ５．７％及びその他オイル成
分が８．７％含有していた。When the reaction solution was analyzed by gas chromatography, 2
, 85.6% of 4-difluoro-5-chloro-1,3-dinitrobenzene, 5.7% of 2.3.4-)lifluoro-5-chloro-nitrobenzene and 8.7% of other oil components. Was.
実施例４
前記実施例３において、スプレー乾燥弗化カリウム１７
．４ｇ（０，３モル）、トルエン５０ｇ、３−シアノピ
リジン７．８ｇおよび１８−クラウン−６−ニーチル６
、６ ｇ （０，０２５モル）を用い、８０℃で４時間
反応させる以外は前記実施例３と同様にして反応を行な
った。反応液には２．４−ジフルオロ−５−クロロ−１
，３−ジニトロベンゼンが２４．９％、２．３．４−１
−リフルオロ−５−クロロニトロベンゼンが１９．４％
、低沸点物が１．９％および高沸点物が４６．８％含有
されていた。Example 4 In Example 3 above, spray-dried potassium fluoride 17
．． 4 g (0.3 mol), 50 g toluene, 7.8 g 3-cyanopyridine and 18-crown-6-neethyl 6
, 6 g (0,025 mol) was used, and the reaction was carried out in the same manner as in Example 3, except that the reaction was carried out at 80° C. for 4 hours. 2,4-difluoro-5-chloro-1 was added to the reaction solution.
, 3-dinitrobenzene 24.9%, 2.3.4-1
-Refluoro-5-chloronitrobenzene 19.4%
It contained 1.9% of low boiling point substances and 46.8% of high boiling point substances.
「発明の効果」
本発明によれば塩素化ニトロまたはシアノベンゼンにつ
いて所期の弗素化反応が良好に進み、また反応生成物か
ら目的物を簡便に分離することができるので工業的実施
に有用である。"Effects of the Invention" According to the present invention, the desired fluorination reaction of chlorinated nitro or cyanobenzene proceeds well, and the target product can be easily separated from the reaction product, so it is useful for industrial implementation. be.
Claims (1)
する塩素化ニトロまたはシアノベンゼンを溶媒の存在下
に弗化カリウムと反応させ、当該塩素原子を弗素原子に
置換させて弗素化ニトロまたはシアノベンゼンを製造す
る方法において、反応溶媒としてシアノピリジンを存在
させることを特徴とする弗素化ニトロまたはシアノベン
ゼンの製造方法。A chlorinated nitro or cyanobenzene having at least one chlorine atom at the o-position and/or p-position is reacted with potassium fluoride in the presence of a solvent to replace the chlorine atom with a fluorine atom to form a fluorinated nitro or cyanobenzene. 1. A method for producing fluorinated nitro or cyanobenzene, characterized in that cyanopyridine is present as a reaction solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1211995A JPH0377850A (en) | 1989-08-17 | 1989-08-17 | Production of fluorinated nitro-or cyano-benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1211995A JPH0377850A (en) | 1989-08-17 | 1989-08-17 | Production of fluorinated nitro-or cyano-benzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0377850A true JPH0377850A (en) | 1991-04-03 |
Family
ID=16615156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1211995A Pending JPH0377850A (en) | 1989-08-17 | 1989-08-17 | Production of fluorinated nitro-or cyano-benzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0377850A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586257A (en) * | 2018-05-03 | 2018-09-28 | 浙江解氏新材料股份有限公司 | A kind of novel processing step of p-fluoronitrobenzene |
| CN112457153A (en) * | 2020-11-10 | 2021-03-09 | 杭州臻挚生物科技有限公司 | Industrial preparation method of 2,4, 5-trifluoro-phenylacetic acid |
-
1989
- 1989-08-17 JP JP1211995A patent/JPH0377850A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586257A (en) * | 2018-05-03 | 2018-09-28 | 浙江解氏新材料股份有限公司 | A kind of novel processing step of p-fluoronitrobenzene |
| CN112457153A (en) * | 2020-11-10 | 2021-03-09 | 杭州臻挚生物科技有限公司 | Industrial preparation method of 2,4, 5-trifluoro-phenylacetic acid |
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