JPH02268135A - Preparation of chlorinated benzoic acids - Google Patents
Preparation of chlorinated benzoic acidsInfo
- Publication number
- JPH02268135A JPH02268135A JP8982189A JP8982189A JPH02268135A JP H02268135 A JPH02268135 A JP H02268135A JP 8982189 A JP8982189 A JP 8982189A JP 8982189 A JP8982189 A JP 8982189A JP H02268135 A JPH02268135 A JP H02268135A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- benzoic acids
- acid
- liquid phase
- solvent
- 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
- 150000001559 benzoic acids Chemical class 0.000 title claims description 17
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- -1 chloroformyl Chemical group 0.000 claims abstract description 4
- 125000004438 haloalkoxy group Chemical group 0.000 claims abstract description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract 3
- 239000000460 chlorine Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000005711 Benzoic acid Substances 0.000 abstract description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical group O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000012188 paraffin wax Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VCDHXXPXZNMKSL-UHFFFAOYSA-N 2-chloro-4,5-difluoro-3-nitrobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(F)C([N+]([O-])=O)=C1Cl VCDHXXPXZNMKSL-UHFFFAOYSA-N 0.000 description 2
- VPHHJAOJUJHJKD-UHFFFAOYSA-N 3,4-dichlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(Cl)=C1 VPHHJAOJUJHJKD-UHFFFAOYSA-N 0.000 description 2
- DFXQXFGFOLXAPO-UHFFFAOYSA-N 96-99-1 Chemical compound OC(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 DFXQXFGFOLXAPO-UHFFFAOYSA-N 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- LPDOHCZLFZKSLU-UHFFFAOYSA-N 2,3-dichloro-4,5-difluorobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(F)C(Cl)=C1Cl LPDOHCZLFZKSLU-UHFFFAOYSA-N 0.000 description 1
- DGCBGBZYTNTZJH-UHFFFAOYSA-N 2-bromo-4,5-difluorobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(F)C=C1Br DGCBGBZYTNTZJH-UHFFFAOYSA-N 0.000 description 1
- ICXSHFWYCHJILC-UHFFFAOYSA-N 2-fluoro-5-nitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC=C1F ICXSHFWYCHJILC-UHFFFAOYSA-N 0.000 description 1
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 description 1
- QKFNYXRBTKWJQW-UHFFFAOYSA-N 3,4-dichloro-5-nitro-benzoic acid Chemical compound OC(=O)C1=CC(Cl)=C(Cl)C([N+]([O-])=O)=C1 QKFNYXRBTKWJQW-UHFFFAOYSA-N 0.000 description 1
- PCTFIHOVQYYAMH-UHFFFAOYSA-N 3,5-dinitro-4-chlorobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1 PCTFIHOVQYYAMH-UHFFFAOYSA-N 0.000 description 1
- KBESHLYCSZINAJ-UHFFFAOYSA-N 3-chloro-2,4,5-trifluorobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(F)C(Cl)=C1F KBESHLYCSZINAJ-UHFFFAOYSA-N 0.000 description 1
- FSXCNZDIJKLGGU-UHFFFAOYSA-N 3-chloro-4-fluoro-5-nitrobenzoic acid Chemical compound OC(=O)C1=CC(Cl)=C(F)C([N+]([O-])=O)=C1 FSXCNZDIJKLGGU-UHFFFAOYSA-N 0.000 description 1
- VIPUIECMSDQUIK-UHFFFAOYSA-N 3-fluoro-5-nitrobenzoic acid Chemical compound OC(=O)C1=CC(F)=CC([N+]([O-])=O)=C1 VIPUIECMSDQUIK-UHFFFAOYSA-N 0.000 description 1
- DQCNIBCDZAAPPQ-UHFFFAOYSA-N 4-fluoro-3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=C(F)C([N+]([O-])=O)=C1 DQCNIBCDZAAPPQ-UHFFFAOYSA-N 0.000 description 1
- BOJWTAQWPVBIPG-UHFFFAOYSA-N 4-fluoro-3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C([N+]([O-])=O)=C1 BOJWTAQWPVBIPG-UHFFFAOYSA-N 0.000 description 1
- 208000018380 Chemical injury Diseases 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、ニトロ化安息香酸類から塩素化安息香酸類を
得る方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for obtaining chlorinated benzoic acids from nitrated benzoic acids.
２．４−ジクロロ−５−フルオロ−３−二トロ安息香酸
のごときニトロ化安息香酸類から２゜３．４−トリクロ
ロ−５−フルオロ安息香酸のごとき塩素化安息香酸類を
得る方法には、下記反応式で表わされるサンドマイヤー
反応を用ν八る方法が知られている。 （特開昭６３−
８８１５７号等）
しかしながら、中間生成物のジアゾニウム塩は毒性が極
めて高く、取扱作業者に対する薬傷力τ問題であり、又
、ジアゾニウム塩は不安定で、室温で簡単に分解し、好
収率で目的化合物を得ることができない。さらに、前記
反応は工程数が多く、各工程とも容積効率が低く、又多
量の酸性廃液が生成し、取扱いが不便である等、従来法
にはいくつかの欠点が存在している。The method for obtaining chlorinated benzoic acids such as 2.3.4-trichloro-5-fluorobenzoic acid from nitrated benzoic acids such as 2.4-dichloro-5-fluoro-3-nitrobenzoic acid involves the following reaction. A method using the Sandmeyer reaction expressed by the formula ν8 is known. (Unexamined Japanese Patent Publication 1986-
88157, etc.) However, the diazonium salt as an intermediate product is extremely toxic and poses a problem of chemical injury τ to workers who handle it, and diazonium salt is unstable and easily decomposes at room temperature, resulting in a good yield. Unable to obtain target compound. Furthermore, the conventional method has several drawbacks, such as the number of steps involved in the reaction, low volumetric efficiency in each step, and the production of a large amount of acidic waste liquid, which is inconvenient to handle.
また、ハロゲン化ニトロベンゼン類と塩素化剤との反応
によりハロゲン化クロロベンゼン類を得る方法が知られ
ている。（特開昭６０−２４６３２７号等） しかしな
がら、安息香酸類の反応については知られていない。こ
のようなニトロ化安息香酸類の高温での脱ニトロ塩素化
反応は脱炭酸反応等の副反応が予想さ九実施は困難であ
ると考えられていた。Furthermore, a method for obtaining halogenated chlorobenzenes by reacting halogenated nitrobenzenes with a chlorinating agent is known. (JP-A No. 60-246327, etc.) However, the reaction of benzoic acids is not known. It was thought that such a denitrochlorination reaction of nitrated benzoic acids at high temperatures would be difficult to carry out because side reactions such as decarboxylation reactions were expected.
本発明者らは、工業的に有利に、塩素化安息香酸類を得
る方法を見いだすべぐ、鋭意検討を重ねた結果、驚くべ
きことにニトロ化安息香酸と塩素化剤との反応により高
収率で塩素化安息香酸が得られることを見いだした。こ
こに作業環境上問題がないとともに、工程数を大幅に短
縮できる優れた方法を完成し、提案するに至った。すな
わち、本発明は、下記−形式（Ｉ）で表わされるニトロ
化安息香酸類のニトロ基を塩素化剤により塩素置換せし
め下記−形式（ＩＩ）で表わされる塩素化安息香酸類を
得ることを特徴とする塩素化安息香酸類の製造方法に関
するものである。The present inventors have conducted intensive studies to find an industrially advantageous method for obtaining chlorinated benzoic acids, and have surprisingly found that a high yield can be obtained by the reaction of nitrated benzoic acid with a chlorinating agent. It was discovered that chlorinated benzoic acid could be obtained by We have now completed and proposed an excellent method that does not pose problems in the working environment and can significantly shorten the number of steps. That is, the present invention is characterized in that the nitro group of a nitrated benzoic acid represented by the following formula (I) is substituted with chlorine using a chlorinating agent to obtain a chlorinated benzoic acid represented by the following formula (II). The present invention relates to a method for producing chlorinated benzoic acids.
（式中、ＸはそれぞれＣ１，Ｅｒ、 またはＦ、Ｒは
ハロゲン、ハロゲノアルキル、ハロゲノアルコキシ、ク
ロロホルミル、ＮＯ２，ＣＮ、 又はＨを示す。ｍは
１または２、ｎは０または１から４−ｍの整数を示す。(In the formula, X is C1, Er, or F, R respectively represents halogen, halogenoalkyl, halogenoalkoxy, chloroformyl, NO2, CN, or H. m is 1 or 2, and n is 0 or 1 to 4- Indicates an integer of m.
）
本発明におけるニトロ化安息香酸類は、前記−形式（Ｉ
）で表わさね、少なくとも１個のニトロ基および少なく
とも１個のＣユ、Ｂｒ、Ｆ等のハロゲン原子を同時に有
する化合物である。) The nitrated benzoic acids in the present invention have the above-mentioned form (I
) is a compound having at least one nitro group and at least one halogen atom such as C, Br, F, etc.
一方、得られる塩素化安息香酸類は、前記−形式（ＩＴ
）で表わされる。−形式（Ｉ）及び（ＩＩ）におけるＸ
はそれぞれＣ１，Ｂｒ、 またはＦ、 Ｒはハロゲ
ン、ハロゲノアルキル、ハロゲノアルコキシ、クロロホ
ルミル、 ＮＯ２，ＣＮ、 又はＨを示す。ｍは１
または２、ｎは０または１から４−ｍの整数を示す。On the other hand, the obtained chlorinated benzoic acids are of the above-mentioned format (IT
). - X in forms (I) and (II)
represents C1, Br, or F, R represents halogen, halogenoalkyl, halogenoalkoxy, chloroformyl, NO2, CN, or H, respectively. m is 1
or 2, n represents an integer from 0 or 1 to 4-m.
前記−形式（１）で示されるニトロ化安息香酸類の具体
例としては４−クロロ−３−二トロ安息香酸、３，４−
ジクロロ−５−ニトロ安息香酸、３． ４． ５−トリ
クロロ−２−ニトロ安息香酸、２，４−ジクロロ−５゛
−ニトロ安息香酸、２． ４． ５−トリクロロ−３−
ニトロ安息香酸、４−クロロ−３，５−ジニトロ安息香
酸、４−フルオロ−３−ニトロ安息香酸、３−クロロ−
４−フルオロ−５−二トロ安息香酸、３゜４．５−トリ
フルオロ−２−二トロ安息香酸、２．４−ジフルオロ−
５−ニトロ安息香酸、２゜４．５−トリフルオロ−３−
ニトロ安息香酸、４−フルオロ−３，５−ジニトロ安息
香酸、２゜４−ジクロロ−５−フルオロ−３−ニトロ安
息香酸、２−クロロ−４，５−ジフルオロ−３−二トロ
安息香酸、２−ブロモ−４，５−ジフルオロ安息香酸、
２−プロぞ−４−クロロ−５−フルオロ安息香酸、３．
４． ６−１−リフルオロ−５−ニトロフタル酸等の
安息香酸類があげられる。Specific examples of the nitrated benzoic acids represented by the above-mentioned format (1) include 4-chloro-3-nitrobenzoic acid, 3,4-
Dichloro-5-nitrobenzoic acid, 3. 4. 5-trichloro-2-nitrobenzoic acid, 2,4-dichloro-5'-nitrobenzoic acid, 2. 4. 5-trichloro-3-
Nitrobenzoic acid, 4-chloro-3,5-dinitrobenzoic acid, 4-fluoro-3-nitrobenzoic acid, 3-chloro-
4-Fluoro-5-nitrobenzoic acid, 3゜4.5-trifluoro-2-nitrobenzoic acid, 2.4-difluoro-
5-Nitrobenzoic acid, 2°4.5-trifluoro-3-
Nitrobenzoic acid, 4-fluoro-3,5-dinitrobenzoic acid, 2゜4-dichloro-5-fluoro-3-nitrobenzoic acid, 2-chloro-4,5-difluoro-3-nitrobenzoic acid, 2 -bromo-4,5-difluorobenzoic acid,
2-prozo-4-chloro-5-fluorobenzoic acid, 3.
4. Examples include benzoic acids such as 6-1-lifluoro-5-nitrophthalic acid.
ニトロ基の塩素置換反応は、液相又気相流通系で行ない
、液相系では、溶媒存在下でも無溶媒でもよく、溶媒を
用゛いる場合には、塩素化パラフィン、クロルトリフル
オロエチレン低重合体、テトラブロモエタン等のハロゲ
ン系溶媒が好ましい。塩素化剤の使用量は、ニトロ化安
息香酸類の置換すべきニトロ基が塩素に置換するために
必要な反応理論量の０．２〜１０倍、好ましくは １．
０〜５倍が適当である。反応温度は１５０〜３５０ ’
Ｃ，反応圧力は常圧〜１００ｋｇ／ｃｍ２ 反応時間は
２〜３０時間が適当である。The chlorine substitution reaction of the nitro group is carried out in a liquid phase or gas phase flow system. In the liquid phase system, it may be in the presence of a solvent or without a solvent. If a solvent is used, chlorinated paraffin, chlorotrifluoroethylene, Preferred are polymers and halogenated solvents such as tetrabromoethane. The amount of the chlorinating agent to be used is 0.2 to 10 times the theoretical reaction amount necessary for replacing the nitro group of the nitrated benzoic acids with chlorine, preferably 1.
0 to 5 times is appropriate. Reaction temperature is 150-350'
C. Suitable reaction pressure is normal pressure to 100 kg/cm2 and reaction time is 2 to 30 hours.
本発明に従えば、医農薬中間体の原料として有用な３−
クロロ−２，４，５−トリフルオロ安息香酸の塩素化安
息香酸類を工業的に有利に得ることができる。以下、本
発明の実施例について、さらに具体的に説明する。According to the present invention, 3-
Chlorinated benzoic acids such as chloro-2,4,5-trifluorobenzoic acid can be advantageously obtained industrially. Examples of the present invention will be described in more detail below.
実施例１
リフラックスコンデンサーおよび塩素導入管を取り付け
た２００ｍ１のガラス製反応器に４−クロロ−３−二ト
ロ安息香酸を１００ｇ（０，５０ｍｏｌ ）を仕込み２
００°Ｃ″″Ｃ激しく攪拌しながら塩素ガスを７．０ｇ
／ｈｒで１５時間導入した。Example 1 100 g (0.50 mol) of 4-chloro-3-nitrobenzoic acid was charged into a 200 ml glass reactor equipped with a reflux condenser and a chlorine introduction tube.
00°C''''C Add 7.0g of chlorine gas while stirring vigorously.
/hr for 15 hours.
反応液の分析を行なったところ原籍の反応率は８５％、
３．４−ジクロロ安息香酸への選択率は９１％であった
。生成物を水洗し、四塩化炭素で再結晶し３，４−ジク
ロロ安息香酸５３．４ｇを得た。Analysis of the reaction solution revealed that the original reaction rate was 85%.
The selectivity to 3,4-dichlorobenzoic acid was 91%. The product was washed with water and recrystallized with carbon tetrachloride to obtain 53.4 g of 3,4-dichlorobenzoic acid.
実施例２
実施ｇ４１と同様の反応装置を用い、３−クロロ−４−
フルオロ−５−二トロ安息香酸を１００ｇ仕込み、激し
く撹拌しながら１９０″Ｃで塩素ガスを導入した。１３
時間後反応液の分析を行なったところ原籍の反応率は８
９％、３．５−ジクロロ−４−フルオロ安息香酸への選
択率は９３％であった。Example 2 Using the same reaction apparatus as Example g41, 3-chloro-4-
100g of fluoro-5-nitrobenzoic acid was charged, and chlorine gas was introduced at 190"C with vigorous stirring.13
When the reaction solution was analyzed after a period of time, the original reaction rate was 8.
The selectivity to 9%, 3.5-dichloro-4-fluorobenzoic acid was 93%.
実施例３
出発物質を２． ４． ５−トリフルオロ−３−二トロ
安息香酸に変えた以外は実施例１と同様の条件で塩素ガ
スを導入し、１０時間塩素化反応を行なった。反応後、
生成物を分析したところ、原籍の反応率８６％、２．
４． ５−トリフルオロ−３−クロロ安息香酸への選択
率は８２％であった。Example 3 The starting materials were 2. 4. Chlorine gas was introduced under the same conditions as in Example 1 except that 5-trifluoro-3-nitrobenzoic acid was used, and the chlorination reaction was carried out for 10 hours. After the reaction,
Analysis of the product revealed that the original reaction rate was 86%; 2.
4. The selectivity to 5-trifluoro-3-chlorobenzoic acid was 82%.
実施例４
実施例１と同様の反応装置を用い、２．４−ジクロロ−
５−フルオロ−３−二トロ安息香酸を１００ｇ仕込み、
１８０℃で激しく撹拌しながら塩素ガスを１７時間導入
した。反応後、生成物を分析したところ、ＷＪ４の反応
率９５％、２． ３． ４−トリクロ安息香酸フルオロ
安患香酸への選択−率は８８％であった。Example 4 Using the same reaction apparatus as in Example 1, 2,4-dichloro-
Prepare 100g of 5-fluoro-3-nitrobenzoic acid,
Chlorine gas was introduced for 17 hours at 180° C. with vigorous stirring. After the reaction, the product was analyzed and the reaction rate of WJ4 was 95%.2. 3. The selectivity of 4-triclobenzoic acid to fluorobenzoic acid was 88%.
実、施例５
リフラックスコンデンサーおよび塩素導入管を取り付け
た１００ｍ１ガラス製反応器に２−クロロ−４，５−ジ
フルオロ−３−二トロ安息香酸５０ｇを仕込み、激しく
攪拌しながら１８０°Ｃで２０時間塩素ガスを導入した
。反応後、生成物を分析したところ、原籍の反応率８４
％、２，３−ジクロロ−４，５−ジフルオロ安息香酸へ
の選択率は８０％であった。Example 5 50 g of 2-chloro-4,5-difluoro-3-nitrobenzoic acid was charged into a 100 ml glass reactor equipped with a reflux condenser and a chlorine introduction tube, and heated at 180°C for 20 minutes with vigorous stirring. Chlorine gas was introduced for an hour. After the reaction, the product was analyzed and the original reaction rate was 84.
%, the selectivity to 2,3-dichloro-4,5-difluorobenzoic acid was 80%.
［発明の効果］
本発明方法は、従来法に比べ、反応の容積動車が高く、
−段で目的化合物を得ることができる。[Effect of the invention] Compared to the conventional method, the method of the present invention has a higher volumetric displacement of the reaction.
- The target compound can be obtained in step -.
しかも収率の高い優れた方法である。Moreover, it is an excellent method with high yield.
Claims (1)
類のニトロ基を塩素化剤により塩素置換せしめ、下記一
般式（II）で表わされる塩素化安息香酸類を得ることを
特徴とする塩素化安息香酸類の製造方法。 ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） （式中、ＸはそれぞれＣｌ、Ｂｒ、またはＦ、Ｒはハロ
ゲン、ハロゲノアルキル、ハロゲノアルコキシ、クロロ
ホルミル、ＮＯ＿２、ＣＮ、又はＨを示す。ｍは１また
は２、ｎは０または１から４−ｍの整数を示す。）[Claims] 1. The nitro group of nitrated benzoic acids represented by the following general formula (I) is replaced with chlorine using a chlorinating agent to obtain chlorinated benzoic acids represented by the following general formula (II). Characteristic method for producing chlorinated benzoic acids. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formulas, X is Cl, Br, or F, respectively, and R is halogen, halogenoalkyl, halogenoalkoxy, Chloroformyl, NO_2, CN, or H. m is 1 or 2, n is 0 or an integer from 1 to 4-m.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8982189A JPH02268135A (en) | 1989-04-11 | 1989-04-11 | Preparation of chlorinated benzoic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8982189A JPH02268135A (en) | 1989-04-11 | 1989-04-11 | Preparation of chlorinated benzoic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02268135A true JPH02268135A (en) | 1990-11-01 |
Family
ID=13981421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8982189A Pending JPH02268135A (en) | 1989-04-11 | 1989-04-11 | Preparation of chlorinated benzoic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02268135A (en) |
-
1989
- 1989-04-11 JP JP8982189A patent/JPH02268135A/en active Pending
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