JPS625419B2 - - Google Patents
Info
- Publication number
- JPS625419B2 JPS625419B2 JP9676579A JP9676579A JPS625419B2 JP S625419 B2 JPS625419 B2 JP S625419B2 JP 9676579 A JP9676579 A JP 9676579A JP 9676579 A JP9676579 A JP 9676579A JP S625419 B2 JPS625419 B2 JP S625419B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- nitrobenzonitrile
- chloro
- halide
- alkaline earth
- 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
- -1 lithium halide Chemical class 0.000 claims description 22
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 45
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 29
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 26
- ZHLCARBDIRRRHD-UHFFFAOYSA-N 2-chloro-6-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1C#N ZHLCARBDIRRRHD-UHFFFAOYSA-N 0.000 description 24
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 10
- 239000001110 calcium chloride Substances 0.000 description 10
- 229910001628 calcium chloride Inorganic materials 0.000 description 10
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- SWBDKCMOLSUXRH-UHFFFAOYSA-N 2-nitrobenzonitrile Chemical class [O-][N+](=O)C1=CC=CC=C1C#N SWBDKCMOLSUXRH-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
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OHDYZVVLNPXKDX-UHFFFAOYSA-N 2,3-dichlorobenzonitrile Chemical compound ClC1=CC=CC(C#N)=C1Cl OHDYZVVLNPXKDX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000003839 salts Chemical class 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
- IOBYLOUUUJPZEO-UHFFFAOYSA-N 4-bromo-2-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC(Br)=CC=C1C#N IOBYLOUUUJPZEO-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
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001631 strontium chloride Inorganic materials 0.000 description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- QTUXEYXZJLVGOA-UHFFFAOYSA-N 2,3,6-trichlorobenzonitrile Chemical compound ClC1=CC=C(Cl)C(C#N)=C1Cl QTUXEYXZJLVGOA-UHFFFAOYSA-N 0.000 description 1
- IAQRNDXVYOQXLS-UHFFFAOYSA-N 2,3-dibromobenzonitrile Chemical compound BrC1=CC=CC(C#N)=C1Br IAQRNDXVYOQXLS-UHFFFAOYSA-N 0.000 description 1
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 description 1
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical class NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 1
- NVPXACXEVCJWCF-UHFFFAOYSA-N 2-bromo-6-chlorobenzonitrile Chemical compound ClC1=CC=CC(Br)=C1C#N NVPXACXEVCJWCF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 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
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VIJUZNJJLALGNJ-UHFFFAOYSA-N n,n-dimethylbutanamide Chemical compound CCCC(=O)N(C)C VIJUZNJJLALGNJ-UHFFFAOYSA-N 0.000 description 1
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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（）
（式中、Ｘはハロゲン原子を表わし、ｎは１又
は２を表わす）
で示される化合物を非プロトン性極性溶媒中でア
ルカリ土類金属のハロゲン化物、又はこれとハロ
ゲン化リチウムとの混合物、又はアルカリ土類金
属のハロゲン化物と無水ハロゲン化アルミニウム
との混合物、又はこれに更にハロゲン化リチウム
を含む混合物（ここで、ハロゲン化リチウムと無
水ハロゲン化アルミニウムのハロゲンはアルカリ
土類金属のハロゲン化物のハロゲンと同種のもの
である。）と反応させることを特徴とする一般式
（）
（式中、Ｘ，X′はハロゲン原子を表わし、ｎ
は１又は２を表わす）
で示される２−ハロゲノ−ベンゾニトリル誘導体
の製造法に関するものである。[Detailed Description of the Invention] The present invention relates to the general formula () (In the formula, X represents a halogen atom and n represents 1 or 2) in an aprotic polar solvent, an alkaline earth metal halide, or a mixture of this and lithium halide, or A mixture of an alkaline earth metal halide and anhydrous aluminum halide, or a mixture further containing lithium halide (here, the halogen of lithium halide and anhydrous aluminum halide is the halogen of the alkaline earth metal halide) The general formula () is characterized by reacting with (In the formula, X and X' represent halogen atoms, and n
represents 1 or 2) The present invention relates to a method for producing a 2-halogeno-benzonitrile derivative represented by
一般式（）で示される２−ハロゲノ−ベンゾ
ニトリル誘導体は農薬として、また種々の有用な
物質の中間体として知られており、例えば２，６
−ジクロロベンゾニトリルは優れた除草剤として
知られている。 2-halogeno-benzonitrile derivatives represented by the general formula () are known as agricultural chemicals and intermediates for various useful substances, such as 2,6
-Dichlorobenzonitrile is known as an excellent herbicide.
従来、一般式（）で示される２−ニトロベン
ゾニトリル誘導体から一般式（）で示される２
−ハロゲノ−ベンゾニトリル誘導体を製造する方
法としては、ニトロ基を還元して２−アミノベン
ゾニトリル誘導体とし、サンドマイヤー反応によ
り２−ハロゲノ−ベンゾニトリル誘導体を製造す
る方法が最も一般的である。しかし、この方法は
還元、ジアゾ化、ハロゲン置換といつた煩雑な工
程を要し、廃水、廃棄物が多量に排出され、工業
的に有利な方法ではない。 Conventionally, from the 2-nitrobenzonitrile derivative represented by the general formula () to the 2-nitrobenzonitrile derivative represented by the general formula (),
The most common method for producing a -halogeno-benzonitrile derivative is to reduce the nitro group to produce a 2-aminobenzonitrile derivative, and then use the Sandmeyer reaction to produce the 2-halogeno-benzonitrile derivative. However, this method requires complicated steps such as reduction, diazotization, and halogen substitution, and a large amount of waste water and waste is discharged, so it is not an industrially advantageous method.
そこで本発明者は、２−ハロゲノ−ベンゾニト
リル誘導体の製造法について鋭意検討した結果、
驚くべきことに、２−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、アルカリ土類金
属のハロゲン化物又はこれとハロゲン化リチウム
との混合物と反応させるだけで２−ハロゲノ−ベ
ンゾニトリル誘導体を製造できることを見出し、
更に無水ハロゲン化アルミニウムを共存させるこ
とにより収率が著しく向上することを見出し本発
明を完成するに至つた。無水塩化アルミニウムを
共存させると収率が著しく向上する理由は明らか
でないが、反応系においては複塩を形成しその結
果反応が穏やかに進行するためと思われる。 Therefore, as a result of intensive study on the method for producing 2-halogeno-benzonitrile derivatives, the present inventor found that
Surprisingly, 2-halogeno-benzonitrile derivatives can be produced simply by reacting 2-nitrobenzonitrile derivatives with alkaline earth metal halides or their mixtures with lithium halides in an aprotic polar solvent. Find out what you can do,
Furthermore, the present inventors have discovered that the yield can be significantly improved by coexisting anhydrous aluminum halide, leading to the completion of the present invention. The reason why the yield is significantly improved when anhydrous aluminum chloride is present is not clear, but it is thought to be because a double salt is formed in the reaction system, and as a result, the reaction proceeds slowly.
本発明の方法は従来法に比べ原料が安価であ
り、反応工程が少なく、しかも廃水、廃棄物の量
も極めて少ないので目的物を安価に製造すること
ができる。 Compared to conventional methods, the method of the present invention uses less expensive raw materials, fewer reaction steps, and extremely less amount of waste water and waste, making it possible to produce the desired product at low cost.
本発明において使用されるアルカリ土類金属の
ハロゲン化物は、通常一種が使用されるが、同種
のハロゲン原子を有するアルカリ土類金属のハロ
ゲン化物であれば二種以上を混合して使用するこ
ともできる。又、アルカリ土類金属のハロゲン化
物のハロゲンと同種のハロゲン原子を有するハロ
ゲン化リチウムをアルカリ土類金属のハロゲン化
物と併用してもよい。含水塩を使用するとニトリ
ル基の加水分解反応が起こるので、無水塩を使用
することが望ましい。 Generally, one type of alkaline earth metal halide is used in the present invention, but a mixture of two or more alkaline earth metal halides having the same type of halogen atom may also be used. can. Further, a lithium halide having the same type of halogen atom as the halogen of the alkaline earth metal halide may be used in combination with the alkaline earth metal halide. It is preferable to use an anhydrous salt since the use of a hydrated salt causes a hydrolysis reaction of the nitrile group.
また、アルカリ土類金属のハロゲン化物と無水
ハロゲン化アルミニウムの混合物を用いる場合、
アルカリ土類金属のハロゲン化物自体を用いても
よいが、反応系においてアルカリ土類金属のハロ
ゲン化物に転換しうるアルカリ土類金属化合物、
例えばアルカリ土類金属の炭酸塩等も使用するこ
とができる。又、無水ハロゲン化アルミニウムを
併用する場合も、同様にアルカリ土類金属のハロ
ゲ化物とハロゲン化リチウム、又は反応系におい
てハロゲン化リチウムとなりうる炭酸リチウム等
のリチウム化合物を併用してもよい。アルカリ土
類金属のハロゲン化物の使用量は特に限定されな
いが、一般式（）で示される化合物に対して好
ましくは0.01〜10モル倍、特に好ましくは0.1〜
３モル倍である。ハロゲン化リチウムの使用量
は、一般式（）で示される化合物に対して０〜
５モル倍が好ましい。アルカリ土類金属のハロゲ
ン化物と無水ハロゲン化アルミニウムの混合物を
使用する場合、無水ハロゲン化アルミニウムの使
用量はアルカリ土類金属１原子に対してアルミニ
ウムが0.001〜５原子となる様な割合が好まし
く、アルカリ土類金属１原子に対してアルミニウ
ムが0.05〜３原子となる割合で用いるのが特に好
ましい。 In addition, when using a mixture of an alkaline earth metal halide and anhydrous aluminum halide,
Alkaline earth metal halides themselves may be used, but alkaline earth metal compounds that can be converted into alkaline earth metal halides in the reaction system,
For example, carbonates of alkaline earth metals can also be used. Furthermore, when anhydrous aluminum halide is used in combination, an alkaline earth metal halide and lithium halide, or a lithium compound such as lithium carbonate that can become lithium halide in the reaction system may be used in combination. The amount of alkaline earth metal halide used is not particularly limited, but is preferably 0.01 to 10 times the amount of the compound represented by the general formula (), particularly preferably 0.1 to 10 times the amount by mole.
It is 3 times the mole. The amount of lithium halide used is 0 to 0 for the compound represented by the general formula ().
5 mole times is preferable. When using a mixture of an alkaline earth metal halide and anhydrous aluminum halide, the amount of anhydrous aluminum halide used is preferably such that the ratio of aluminum to 1 atom of alkaline earth metal is 0.001 to 5 atoms, It is particularly preferable to use aluminum in a ratio of 0.05 to 3 atoms per one atom of alkaline earth metal.
本発明で用いる式（）の化合物としては、２
−クロロ−６−ニトロベンゾニトリル、４−クロ
ロ−２−ニトロベンゾニトリル、５−クロロ−２
−ニトロベンゾニトリル、２，３−ジクロロ−６
−ニトロベンゾニトリル、４−ブロモ−２−ニト
ロベンゾニトリル等が挙げられる。 The compound of formula () used in the present invention includes 2
-chloro-6-nitrobenzonitrile, 4-chloro-2-nitrobenzonitrile, 5-chloro-2
-Nitrobenzonitrile, 2,3-dichloro-6
-nitrobenzonitrile, 4-bromo-2-nitrobenzonitrile, and the like.
本発明で用いるアルカリ土類金属のハロゲン化
物としては、カルシウム、マグネシウム、ストロ
ンチウムのフツ化物、塩化物、臭化物、ヨウ化物
等が挙げられる。 Examples of the alkaline earth metal halides used in the present invention include fluorides, chlorides, bromides, and iodides of calcium, magnesium, and strontium.
又、無水ハロゲン化アルミニウムとしては、無
水塩化アルミニウム、無水臭化アルミニウム等が
挙げられる。ハロゲン化リチウムとしては、フツ
化リチウム、塩化リチウム、臭化リチウム、ヨウ
化リチウムが挙げられる。 Further, examples of the anhydrous aluminum halide include anhydrous aluminum chloride, anhydrous aluminum bromide, and the like. Examples of lithium halides include lithium fluoride, lithium chloride, lithium bromide, and lithium iodide.
本発明で使用される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
メチルアセトアミド、Ｎ，Ｎ−ジメチルプロピオ
ンアミド、Ｎ，Ｎ−ジメチルブチルアミド、Ｎ−
メチルピロリドン、Ｎ，N′−ジメチルイミダゾ
リドン、ジメチルスルホキシド、ヘキサメチルホ
スホルアミドなどが挙げられ、その使用量は特に
制限がないが、通常は一般式（）で示される化
合物に対して0.5〜10重量倍程度用いるのが適当
である。 The aprotic polar solvents used in the present invention include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N-
Examples include methylpyrrolidone, N,N'-dimethylimidazolidone, dimethyl sulfoxide, hexamethylphosphoramide, etc. The amount used is not particularly limited, but it is usually 0.5 to 0.5 to the compound represented by the general formula (). It is appropriate to use about 10 times the weight.
反応温度は120〜250℃が好ましく、特に150〜
200℃が好ましい。反応時間は反応温度により異
なるので特に限定されないが、通常0.5〜20時間
が適当である。 The reaction temperature is preferably 120~250℃, especially 150~250℃.
200°C is preferred. The reaction time is not particularly limited as it varies depending on the reaction temperature, but 0.5 to 20 hours is usually appropriate.
また本発明の方法は空気雰囲気下で行つてもよ
いが、窒素ガスの様な不活性ガス雰囲気下で行つ
てもよい。 Further, the method of the present invention may be carried out under an air atmosphere, but may also be carried out under an inert gas atmosphere such as nitrogen gas.
本発明の方法により得られる一般式（）で示
される化合物は、反応終了後無機物を過し液
の溶媒を留去するか、液に水、アルコール等を
加えて希釈し析出した結晶を別することにより
容易に単離することができる。 The compound represented by the general formula () obtained by the method of the present invention can be obtained by filtering the inorganic matter and distilling off the solvent of the liquid after the reaction is completed, or by diluting the liquid by adding water, alcohol, etc., and separating the precipitated crystals. It can be easily isolated by
この化合物は蒸留、昇華あるいは適当な溶媒、
例えばアセトン、アルコール、エーテル、酢酸エ
チル、ベンゼン、ヘキサン等を用いて再結晶する
ことにより更に精製できる。 This compound can be prepared by distillation, sublimation or by using a suitable solvent.
For example, it can be further purified by recrystallization using acetone, alcohol, ether, ethyl acetate, benzene, hexane, etc.
以下、本発明を実施例を挙げて説明するが、実
施例中「部」とあるのは「重量部」を示す。 The present invention will be described below with reference to Examples, where "parts" in the Examples indicate "parts by weight."
実施例 １
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化カルシウム5.55部、Ｎ，Ｎ−ジメチルホ
ルムアミド30部を155〜156℃にて６時間加熱還流
させた。反応液を冷却し、ジクロロエタン150部
を加えて過し、液をガスクロマトグラフイー
で分析したところ、２，６−ジクロロベンゾニト
リル2.64部、２−クロロ−６−ニトロベンゾニト
リル4.51部を含有していた。Example 1 2-chloro-6-nitrobenzonitrile 9.13
1 part, 5.55 parts of calcium chloride, and 30 parts of N,N-dimethylformamide were heated under reflux at 155 to 156°C for 6 hours. The reaction solution was cooled, filtered with 150 parts of dichloroethane, and analyzed by gas chromatography to find that it contained 2.64 parts of 2,6-dichlorobenzonitrile and 4.51 parts of 2-chloro-6-nitrobenzonitrile. Ta.
実施例 ２
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化カルシウム3.89部、Ｎ−メチル−２−ピ
ロリドン30部を反応温度160℃で６時間反応させ
た。反応液を実施例１と同様に処理したものをガ
スクロマトグラフイーで分析したところ、２，６
−ジクロロベンゾニトリル3.98部、２−クロロ−
６−ニトロベンゾニトリル0.13部を含有してい
た。Example 2 2-chloro-6-nitrobenzonitrile 9.13
1, 3.89 parts of calcium chloride, and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 160° C. for 6 hours. When the reaction solution was treated in the same manner as in Example 1 and analyzed by gas chromatography, it was found that 2,6
-3.98 parts of dichlorobenzonitrile, 2-chloro-
It contained 0.13 parts of 6-nitrobenzonitrile.
実施例 ３
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化マグネシウム3.33部、Ｎ−メチル−２−
ピロリドン30部を反応温度180℃で６時間反応さ
せた。反応液を実施例１と同様に処理したものを
ガスクロマトグラフイーで分析したところ、２，
６−ジクロロベンゾニトリル3.7部、２−クロロ
−６−ニトロベンゾニトリル0.74部を含有してい
た。Example 3 2-chloro-6-nitrobenzonitrile 9.13
parts, magnesium chloride 3.33 parts, N-methyl-2-
30 parts of pyrrolidone was reacted at a reaction temperature of 180°C for 6 hours. When the reaction solution was treated in the same manner as in Example 1 and analyzed by gas chromatography, 2,
It contained 3.7 parts of 6-dichlorobenzonitrile and 0.74 parts of 2-chloro-6-nitrobenzonitrile.
実施例 ４
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化ストロンチウム7.93部、Ｎ−メチル−２
−ピロリドン30部を反応温度180℃で６時間反応
させた。反応液を実施例１と同様に処理したもの
をガスクロマトグラフイーで分析したところ、
２，６−ジクロロベンゾニトリル3.81部、２−ク
ロロ−６−ニトロベンゾニトリル0.03部を含有し
ていた。Example 4 2-chloro-6-nitrobenzonitrile 9.13
parts, strontium chloride 7.93 parts, N-methyl-2
- 30 parts of pyrrolidone was reacted at a reaction temperature of 180°C for 6 hours. The reaction solution was treated in the same manner as in Example 1 and analyzed by gas chromatography.
It contained 3.81 parts of 2,6-dichlorobenzonitrile and 0.03 parts of 2-chloro-6-nitrobenzonitrile.
実施例 ５
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化カルシウム1.94部、塩化マグネシウム
1.67部、Ｎ−メチル−２−ピロリドン30部を反応
温度180℃で５時間反応させた。Example 5 2-chloro-6-nitrobenzonitrile 9.13
parts, calcium chloride 1.94 parts, magnesium chloride
1.67 parts of N-methyl-2-pyrrolidone and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 180°C for 5 hours.
反応液を実施例１と同様に処理したものをガス
クロマトグラフイーで分析したところ、2.6−ジ
クロロベンゾニトリル4.07部、２−クロロ−６−
ニトロベンゾニトリル0.04部を含有していた。 When the reaction solution was treated in the same manner as in Example 1 and analyzed by gas chromatography, it was found that 4.07 parts of 2.6-dichlorobenzonitrile, 2-chloro-6-
Contained 0.04 part of nitrobenzonitrile.
実施例 ６
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化マグネシウム2.38部、塩化リチウム0.42
部、Ｎ−メチル−２−ピロリドン30部を反応温度
180℃で６時間反応させた。反応液を実施例１と
同様に処理したものをガスクロマトグラフイーで
分析したところ、２，６−ジクロロベンゾニトリ
ル3.91部、２−クロロ−６−ニトロベンゾニトリ
ル0.23部を含有していた。Example 6 2-chloro-6-nitrobenzonitrile 9.13
parts, magnesium chloride 2.38 parts, lithium chloride 0.42 parts
part, 30 parts of N-methyl-2-pyrrolidone at the reaction temperature
The reaction was carried out at 180°C for 6 hours. A reaction solution treated in the same manner as in Example 1 was analyzed by gas chromatography and found to contain 3.91 parts of 2,6-dichlorobenzonitrile and 0.23 parts of 2-chloro-6-nitrobenzonitrile.
実施例 ７
２−クロロ−６−ニトロベンゾニトリル9.13
部、臭化マグネシウム9.21部、Ｎ−メチル−２−
ピロリドン30部を反応温度190℃で８時間反応さ
せた。反応液を冷却後過し、液を水300部中
に放出して析出した結晶を過、水洗、乾燥後、
エタノールから再結晶して融点143〜144℃の２−
ブロモ−６−クロロベンゾニトリル3.0部を得
た。Example 7 2-chloro-6-nitrobenzonitrile 9.13
parts, magnesium bromide 9.21 parts, N-methyl-2-
30 parts of pyrrolidone was reacted at a reaction temperature of 190°C for 8 hours. The reaction solution was cooled and filtered, and the solution was poured into 300 parts of water. The precipitated crystals were filtered, washed with water, and dried.
Recrystallized from ethanol to obtain 2-
3.0 parts of bromo-6-chlorobenzonitrile were obtained.
実施例 ８
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化カルシウム2.78部、無水塩化アルミニウ
ム2.22部、Ｎ−メチル−２−ピロリドン30部を反
応温度170℃で10時間反応させた。反応液を実施
例７と同様に処理して融点145〜146℃の２，６−
ジクロロベンゾニトリル7.49部を得た。Example 8 2-chloro-6-nitrobenzonitrile 9.13
2.78 parts of calcium chloride, 2.22 parts of anhydrous aluminum chloride, and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 170° C. for 10 hours. The reaction solution was treated in the same manner as in Example 7 to obtain 2,6-
7.49 parts of dichlorobenzonitrile were obtained.
実施例 ９
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化マグネシウム2.38部、無水塩化アルミニ
ウム2.22部、Ｎ−メチル−２−ピロリドン30部を
反応温度200℃で６時間反応させた。反応液を実
施例１と同様に処理したものをガスクロマトグラ
フイーで分析したところ、２，６−ジクロロベン
ゾニトリル6.62部、２−クロロ−６−ニトロベン
ゾニトリル0.11部を含有していた。Example 9 2-chloro-6-nitrobenzonitrile 9.13
2.38 parts of magnesium chloride, 2.22 parts of anhydrous aluminum chloride, and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 200° C. for 6 hours. A reaction solution treated in the same manner as in Example 1 was analyzed by gas chromatography and found to contain 6.62 parts of 2,6-dichlorobenzonitrile and 0.11 parts of 2-chloro-6-nitrobenzonitrile.
実施例 10
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化ストロンチウム3.96部、無水塩化アルミ
ニウム2.22部、Ｎ−メチル−２−ピロリドン30部
を反応温度180℃で８時間反応させた。反応液を
実施例１と同様に処理したものをガスクロマトグ
ラフイーで分析したところ、２，６−ジクロロベ
ンゾニトリル5.89部、２−クロロ−６−ニトロベ
ンゾニトリル1.54部を含有していた。Example 10 2-chloro-6-nitrobenzonitrile 9.13
3.96 parts of strontium chloride, 2.22 parts of anhydrous aluminum chloride, and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 180° C. for 8 hours. A reaction solution treated in the same manner as in Example 1 was analyzed by gas chromatography and found to contain 5.89 parts of 2,6-dichlorobenzonitrile and 1.54 parts of 2-chloro-6-nitrobenzonitrile.
実施例 11
２−クロロ−６−ニトロベンゾニトリル9.13
部、炭酸カルシウム2.5部、無水塩化アルミニウ
ム2.22部、Ｎ−メチル−２−ピロリドン30部を加
熱すると、約65℃で急激な発泡が起こる。発泡が
治まつた後、反応温度180℃で６時間反応させ
た。反応液を実施例１と同様に処理したものをガ
スクロマトグラフイーで分析したところ、２，６
−ジクロロベンゾニトリル4.48部、２−クロロ−
６−ニトロベンゾニトリル3.0部を含有してい
た。Example 11 2-chloro-6-nitrobenzonitrile 9.13
When 2.5 parts of calcium carbonate, 2.22 parts of anhydrous aluminum chloride, and 30 parts of N-methyl-2-pyrrolidone are heated, rapid foaming occurs at about 65°C. After the foaming subsided, the reaction was carried out at a reaction temperature of 180° C. for 6 hours. When the reaction solution was treated in the same manner as in Example 1 and analyzed by gas chromatography, it was found that 2,6
-4.48 parts of dichlorobenzonitrile, 2-chloro-
It contained 3.0 parts of 6-nitrobenzonitrile.
実施例 12
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化カルシウム1.39部、塩化マグネシウム
1.19部、無水塩化アルミニウム2.22部、Ｎ−メチ
ル−２−ピロリドン30部を反応温度180℃で６時
間反応させた。反応液を実施例１と同様に処理し
たものをガスクロマトグラフイーで分析したとこ
ろ、２，６−ジクロロベンゾニトリル5.7部、２
−クロロ−６−ニトロベンゾニトリル2.15部を含
有していた。Example 12 2-chloro-6-nitrobenzonitrile 9.13
parts, calcium chloride 1.39 parts, magnesium chloride
1.19 parts of anhydrous aluminum chloride, 2.22 parts of anhydrous aluminum chloride, and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 180°C for 6 hours. When the reaction solution was treated in the same manner as in Example 1 and analyzed by gas chromatography, it was found that 5.7 parts of 2,6-dichlorobenzonitrile, 2
-chloro-6-nitrobenzonitrile 2.15 parts.
実施例 13
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化カルシウム0.56部、塩化リチウム0.42
部、無水塩化アルミニウム2.22部、Ｎ−メチル−
２−ピロリドン30部を反応温度180℃で６時間反
応させた。反応液を実施例１と同様に処理したも
のをガスクロマトグラフイーで分析したところ、
２，６−ジクロロベンゾニトリル7.18部、２−ク
ロロ−６−ニトロベンゾニトリル0.2部を含有し
ていた。Example 13 2-chloro-6-nitrobenzonitrile 9.13
parts, calcium chloride 0.56 parts, lithium chloride 0.42 parts
parts, anhydrous aluminum chloride 2.22 parts, N-methyl-
30 parts of 2-pyrrolidone was reacted at a reaction temperature of 180°C for 6 hours. The reaction solution was treated in the same manner as in Example 1 and analyzed by gas chromatography.
It contained 7.18 parts of 2,6-dichlorobenzonitrile and 0.2 parts of 2-chloro-6-nitrobenzonitrile.
実施例 14
２−クロロ−６−ニトロベンゾニトリル9.13
部、塩化カルシウム2.0部、塩化マグネシウム
0.67部、塩化リチウム0.42部、無水塩化アルミニ
ウム2.22部、Ｎ−メチル−２−ピロリドン30部を
反応温度170℃で６時間反応させた。反応液を実
施例１と同様に処理したものをガスクロマトグラ
フイーで分析したところ、２，６−ジクロロベン
ゾニトリル5.88部、２−クロロ−６−ニトロベン
ゾニトリル2.23部を含有していた。Example 14 2-chloro-6-nitrobenzonitrile 9.13
part, calcium chloride 2.0 parts, magnesium chloride
0.67 parts of lithium chloride, 2.22 parts of anhydrous aluminum chloride, and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 170° C. for 6 hours. A reaction solution treated in the same manner as in Example 1 was analyzed by gas chromatography and found to contain 5.88 parts of 2,6-dichlorobenzonitrile and 2.23 parts of 2-chloro-6-nitrobenzonitrile.
実施例 15
４−クロロ−２−ニトロベンゾニトリル9.13
部、塩化カルシウム2.78部、無水塩化アルミニウ
ム2.22部、Ｎ−メチル−２−ピロリドン30部を反
応温度180℃で６時間反応させた。反応液を冷却
後過し、液を水300部中に放出し、析出した
結晶を別して水洗、乾燥後、ｎ−ヘキサンから
再結晶して融点60〜61℃の２，４−ジクロロベン
ゾニトリル7.64部を得た。Example 15 4-chloro-2-nitrobenzonitrile 9.13
1, 2.78 parts of calcium chloride, 2.22 parts of anhydrous aluminum chloride, and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 180° C. for 6 hours. The reaction solution was cooled and filtered, and the solution was discharged into 300 parts of water. The precipitated crystals were separated, washed with water, dried, and recrystallized from n-hexane to obtain 2,4-dichlorobenzonitrile with a melting point of 60-61°C 7.64 I got the department.
実施例 16
５−クロロ−２−ニトロベンゾニトリル9.13
部、塩化カルシウム2.78部、無水塩化アルミニウ
ム2.22部、Ｎ−メチル−２−ピロリドン30部を反
応温度200℃で８時間反応させた。反応液を実施
例15と同様に処理して融点128〜129℃の２，５−
ジクロロベンゾニトリル7.38部を得た。Example 16 5-chloro-2-nitrobenzonitrile 9.13
1, 2.78 parts of calcium chloride, 2.22 parts of anhydrous aluminum chloride, and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 200° C. for 8 hours. The reaction solution was treated in the same manner as in Example 15 to obtain 2,5-
7.38 parts of dichlorobenzonitrile were obtained.
実施例 17
２，３−ジクロロ−６−ニトロベンゾニトリル
10.85部、塩化カルシウム2.78部、無水塩化アル
ミニウム2.22部、Ｎ−メチル−２−ピロリドン30
部を反応温度180℃で２時間反応させた。反応液
を実施例７と同様に処理して融点122〜123℃の
２，３，６−トリクロロベンゾニトリル9.13部を
得た。Example 17 2,3-dichloro-6-nitrobenzonitrile
10.85 parts, calcium chloride 2.78 parts, anhydrous aluminum chloride 2.22 parts, N-methyl-2-pyrrolidone 30
A portion was reacted at a reaction temperature of 180°C for 2 hours. The reaction solution was treated in the same manner as in Example 7 to obtain 9.13 parts of 2,3,6-trichlorobenzonitrile having a melting point of 122-123°C.
実施例 18
４−ブロモ−２−ニトロベンゾニトリル11.35
部、臭化マグネシウム4.6部、無水臭化アルミニ
ウム4.45部、Ｎ−メチル−２−ピロリドン30部を
反応温度190℃で６時間反応させた。反応液を実
施例７と同様に処理して融点91〜92℃の２，４−
ジブロモベンゾニトリル3.6部を得た。Example 18 4-bromo-2-nitrobenzonitrile 11.35
1, 4.6 parts of magnesium bromide, 4.45 parts of anhydrous aluminum bromide, and 30 parts of N-methyl-2-pyrrolidone were reacted at a reaction temperature of 190° C. for 6 hours. The reaction solution was treated in the same manner as in Example 7 to obtain 2,4-
3.6 parts of dibromobenzonitrile were obtained.
Claims (1)
は２を表わす） で示される化合物を非プロトン性極性溶媒中でア
ルカリ土類金属のハロゲン化物、又はこれとハロ
ゲン化リチウムとの混合物、又はアルカリ土類金
属のハロゲン化物と無水ハロゲン化アルミニウム
との混合物、又はこれに更にハロゲン化リチウム
を含む混合物（ここで、ハロゲン化リチウムと無
水ハロゲン化アルミニウムのハロゲンはアルカリ
土類金属のハロゲン化物のハロゲンと同種のもの
である。）と反応させることを特徴とする。 一般式（） （式中、Ｘ，X′はハロゲン原子を表わし、ｎ
は１又は２を表わす） で示される２−ハロゲノ−ベンゾニトリル誘導体
の製造法。[Claims] 1 General formula () (In the formula, X represents a halogen atom and n represents 1 or 2) in an aprotic polar solvent, an alkaline earth metal halide, or a mixture of this and lithium halide, or A mixture of an alkaline earth metal halide and anhydrous aluminum halide, or a mixture further containing lithium halide (here, the halogen of lithium halide and anhydrous aluminum halide is the halogen of the alkaline earth metal halide) ). General formula () (In the formula, X and X' represent halogen atoms, and n
represents 1 or 2) A method for producing a 2-halogeno-benzonitrile derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9676579A JPS5620560A (en) | 1979-07-31 | 1979-07-31 | Production of 2-halogenobenzonitrile derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9676579A JPS5620560A (en) | 1979-07-31 | 1979-07-31 | Production of 2-halogenobenzonitrile derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5620560A JPS5620560A (en) | 1981-02-26 |
| JPS625419B2 true JPS625419B2 (en) | 1987-02-04 |
Family
ID=14173722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9676579A Granted JPS5620560A (en) | 1979-07-31 | 1979-07-31 | Production of 2-halogenobenzonitrile derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5620560A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58114096A (en) * | 1981-12-28 | 1983-07-07 | カシオ計算機株式会社 | Electronic musical instrument |
| CN116003294A (en) * | 2022-12-30 | 2023-04-25 | 常州大学 | New synthesis method of medical intermediate 2-bromo-6-chlorobenzonitrile |
-
1979
- 1979-07-31 JP JP9676579A patent/JPS5620560A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5620560A (en) | 1981-02-26 |
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