JPS63287743A - Production of 2-chlorocarboxylic acid - Google Patents
Production of 2-chlorocarboxylic acidInfo
- Publication number
- JPS63287743A JPS63287743A JP62122255A JP12225587A JPS63287743A JP S63287743 A JPS63287743 A JP S63287743A JP 62122255 A JP62122255 A JP 62122255A JP 12225587 A JP12225587 A JP 12225587A JP S63287743 A JPS63287743 A JP S63287743A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- raw material
- carboxylic acid
- anhydride
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 11
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 5
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 abstract description 4
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 abstract description 3
- 235000019260 propionic acid Nutrition 0.000 abstract description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 229940005605 valeric acid Drugs 0.000 abstract description 2
- 239000004310 lactic acid Substances 0.000 abstract 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 235000014655 lactic acid Nutrition 0.000 abstract 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- RVBUZBPJAGZHSQ-UHFFFAOYSA-N 2-chlorobutanoic acid Chemical compound CCC(Cl)C(O)=O RVBUZBPJAGZHSQ-UHFFFAOYSA-N 0.000 description 1
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001385733 Aesculus indica Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVWILPZRADBDPQ-UHFFFAOYSA-N carbonochloridoyl carbonochloridate Chemical compound ClC(=O)OC(Cl)=O BVWILPZRADBDPQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は医薬又は農薬の原料として有用な２−クロルカ
ルボン酸の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing 2-chlorocarboxylic acid, which is useful as a raw material for medicines or agricultural chemicals.
例えば２−クロルゾロピオン酸はプロピオン酸系農薬の
原料として有用である。For example, 2-chlorozolopionic acid is useful as a raw material for propionic acid pesticides.
（従来技術）
一般に脂肪族カルｒン酸の・・ロケ゛ン化はきわめて緩
慢であり、通常のノ・ロダン化ではノ・ロケ゛ン原子は
カルボキシル基から遠い位置へ優先的に入りやすい。し
かし、リン、硫黄、ヨウ素等の触媒を使用すると２−位
にハロダン化することが知られている。(Prior Art) In general, aliphatic carboxylic acids undergo very slow localization, and in normal carboxylation, the location atoms tend to preferentially enter positions far from the carboxyl group. However, it is known that when a catalyst such as phosphorus, sulfur, or iodine is used, halodanization occurs at the 2-position.
又少量の酸クロライド、硫酸、クロル硫酸等を触媒とし
て使用することも知られている（Ｊ、Ｏｒｇ。It is also known to use small amounts of acid chloride, sulfuric acid, chlorosulfuric acid, etc. as catalysts (J, Org.
Ｃｈｅｍ、、 ４０ 、２９６０ 、１９７５．５ｙｎ
ｔｈｅｓｉｓ、 １９６７゜３９）。Chem, 40, 2960, 1975.5yn
thesis, 1967°39).
（発明が解決しようとする問題点）
従来法で工業的に２−クロルカルボン酸を製造する場合
２−位取外の塩素化及び高次塩素化物の生成を抑制する
触媒が要求される。(Problems to be Solved by the Invention) When 2-chlorocarboxylic acid is industrially produced by conventional methods, a catalyst is required that suppresses chlorination at the 2-position and the formation of higher-order chlorides.
その点では酸クロライド及び三塩化リンは効果的である
が、非常に反応性が強く危険なため取扱には細心の注意
が必要である。又、リン系の触媒は反応液の中に残り低
品質になる上にグラスライニング製反応缶の腐食を起し
やすい等の欠点が有る。Acid chloride and phosphorus trichloride are effective in this respect, but they are highly reactive and dangerous, so great care must be taken when handling them. In addition, phosphorus-based catalysts remain in the reaction solution, resulting in poor quality, and also have drawbacks such as being susceptible to corrosion of glass-lined reaction vessels.
本発明は上記欠点を排除し、比較的安全な触媒を用いて
高品質の２−クロルカルボン酸を経済的に製造する方法
を提供するものである。The present invention eliminates the above drawbacks and provides a method for economically producing high quality 2-chlorocarboxylic acid using a relatively safe catalyst.
（問題点を解決するための手段）
カルボン酸無水物に塩酸ガスを作用させると酸クロライ
ドとカルボン酸を生成することは公知であるが、これを
利用し、カルボン酸とその酸無水物の混合物を塩素化す
ることにより副生ずる塩酸と酸無水物が反応し、反応系
内で酸クロライドを生成するため、この酸クロライドが
触媒として作用することを見い出し本発明に至った。(Means for solving the problem) It is known that when hydrochloric acid gas acts on carboxylic acid anhydride, acid chloride and carboxylic acid are produced. The inventors have discovered that the acid chloride acts as a catalyst because the hydrochloric acid produced as a by-product reacts with the acid anhydride in the reaction system, and this acid chloride acts as a catalyst, leading to the present invention.
即ち本発明は脂肪族カルボン酸の塩素化による一般式Ｒ
ＣＨＣＯＯＨ（ここでＲはＣ１〜４の直鎖アルキルｔ
基を示す）で表わされる２−クロルカルボン酸の製造に
おいて、当該カルボン酸の酸無水物を触媒として塩素化
することを特徴とする２−クロルカルボン酸の製造法で
ある。That is, the present invention provides a compound of the general formula R by chlorinating an aliphatic carboxylic acid.
In the production of 2-chlorocarboxylic acid represented by CHCOOH (where R represents a C1-4 linear alkyl t group), 2-chlorocarboxylic acid is chlorinated using an acid anhydride of the carboxylic acid as a catalyst. This is a method for producing chlorocarboxylic acid.
本発明に使用される原料は脂肪族カルボン酸とその無水
物であり、例えばゾロピオン酸と無水プロピオン酸、ｎ
−酪酸と無水−ｎ−酪酸、吉草酸と無水吉草酸等の組合
せである。The raw materials used in the present invention are aliphatic carboxylic acids and their anhydrides, such as zolopionic acid and propionic anhydride, n
- Combinations of butyric acid and n-butyric anhydride, valeric acid and valeric anhydride, etc.
酸無水物の添加量はカルボン酸の種類により若干異るが
通常はカルボン酸１００部に対し酸無水物８〜２０部が
触媒として加えられる。酸無水物の添加量が少ないと３
−クロルカルボン酸が多くなり好ましく力い。又添加量
が多すぎても触媒の効果は変わりなく経済的に不利であ
る。The amount of acid anhydride added varies slightly depending on the type of carboxylic acid, but usually 8 to 20 parts of acid anhydride is added as a catalyst to 100 parts of carboxylic acid. If the amount of acid anhydride added is small, 3
- It is preferable that the amount of chlorocarboxylic acid is large. Moreover, even if the amount added is too large, the effect of the catalyst remains unchanged, which is economically disadvantageous.
塩素化温度はカルボン酸の種類によって異るが９０〜１
５０℃、好捷しくけ１１０〜１４０℃である。一般に温
度が低いと反応が遅く３−１又は４−クロルカルボン酸
の副生が多くなり、温度が高くなると高次塩素化物の副
生が多くなるため個々のカルボン酸について最適反応条
件が適宜選択される。The chlorination temperature varies depending on the type of carboxylic acid, but is 90 to 1
50°C, preferably 110-140°C. In general, when the temperature is low, the reaction is slow and the by-product of 3-1 or 4-chlorocarboxylic acid increases, and when the temperature is high, the by-product of higher chloride increases, so the optimal reaction conditions are selected appropriately for each carboxylic acid. be done.
上記条件でカルボン酸の転化率９９，５％以上まで塩素
化することにより反応は終了する。かくして得られた反
応液は少量の２−クロルカルボン酸クロライド及び２−
クロルカルボン酸無水物が含まれるためこれらと等モル
の水を加えて７０〜９０℃で加熱することによシ容易に
加水分解し２−クロルカルがン酸、！：ナル。The reaction is completed by chlorinating the carboxylic acid under the above conditions to a conversion rate of 99.5% or more. The reaction solution thus obtained contained a small amount of 2-chlorocarboxylic acid chloride and 2-
Because it contains chlorocarboxylic acid anhydride, it is easily hydrolyzed by adding equimolar amounts of water to these and heating at 70 to 90°C to form 2-chlorocarboxylic acid,! : Naru.
本発明においても１反応停止のタイミングを誤ると高次
塩素化物の副生が多くなるが、正常な反応では２−クロ
ルカルボン酸の選択率は９５〜９８％の範囲になる。Even in the present invention, if the timing of stopping one reaction is incorrect, higher chlorinated products will be produced as by-products, but in a normal reaction, the selectivity of 2-chlorocarboxylic acid will be in the range of 95 to 98%.
２−クロルカルボン酸の選択率が９６％以上であれば反
応液を直接工業原料として使用できる。If the selectivity of 2-chlorocarboxylic acid is 96% or more, the reaction solution can be used directly as an industrial raw material.
本発明の２−クロルカルボン酸とはＣ３〜Ｃ６の直鎖モ
ノクロルカルボン酸であって、２−クロルプロピオン酸
％２−クロル−ｎ−酪酸、２−クロル−ｎ−吉草酸、２
−クロル−ｎ−カプロン酸等である。The 2-chlorocarboxylic acid of the present invention is a C3 to C6 linear monochlorocarboxylic acid, and includes 2-chloropropionic acid% 2-chloro-n-butyric acid, 2-chloro-n-valeric acid,
-chloro-n-caproic acid and the like.
（発明の効果）
原料カルボン酸と同種の酸無水物を触媒に用いることに
より、比較的安全に、仕込んだ原料及び触媒がほとんど
２−クロルカルボン酸に転換され縮収率を向上できると
共に非常に澄明な反応液が得られるため、蒸留等の精製
を経ずに工業原料に供給できる。(Effect of the invention) By using the same type of acid anhydride as the raw material carboxylic acid as a catalyst, most of the charged raw material and catalyst can be converted into 2-chlorocarboxylic acid relatively safely, and the condensation rate can be greatly improved. Since a clear reaction solution is obtained, it can be supplied as an industrial raw material without purification such as distillation.
（実施例）
実施例−１
攪拌機、還流冷却器、温度計及び塩素ガス導入管を備え
た５１セ・ぐラブルフラスコにプロピオン酸３０００ｊ
ｊ、無水プロピオン酸５７０ｇを仕込み１１５〜１２５
℃を保ちながら塩素５４．６ Ｎｌ／Ｈｒを導入し２３
時間反応した。反応終了後、水７９ｙを滴下しながら８
０〜９０℃で３０分加水分解を行ない反応液５３７０．
！ｉ＋を得た。反応液の組成は下記の通りであった。(Example) Example-1 3000j of propionic acid was placed in a 51-cell gable flask equipped with a stirrer, a reflux condenser, a thermometer, and a chlorine gas inlet tube.
j, prepare 570 g of propionic anhydride 115-125
54.6 Nl/Hr of chlorine was introduced while maintaining the temperature at 23°C.
Time reacted. After the reaction is complete, add 8 y of water dropwise.
Hydrolysis was carried out at 0 to 90°C for 30 minutes to give a reaction solution of 5370.
! I got i+. The composition of the reaction solution was as follows.
ゾロピオン酸 ０．３％２−クロル
プロピオン酸 ９７．１％３−クロルプロピオン酸
Ｔｒａｃｅ２．２−ジクロルプロピオン酸
２．２％２．３−ジクロルプロピオン酸 Ｏ６４％実
施例−２
実施例−１と同様の反応器にｎ−酪酸２９０７ｇと無水
−ｎ−酪酸５１３ｇを仕込み、１２５〜１３５℃を保ち
ながら塩素４４ Ｎｔ／Ｈｒを導入し２００時間反応た
。反応終了後水５８ｇを滴下しながら８０〜９０℃で３
０分加水分解を行ない反応液４８５４ｇを得た。反応液
の組成は下記の通りであった。Zoropionic acid 0.3% 2-chloropropionic acid 97.1% 3-chloropropionic acid Trace2.2-dichloropropionic acid
2.2% 2.3-dichloropropionic acid O64% Example-2 2907 g of n-butyric acid and 513 g of n-butyric anhydride were charged into the same reactor as in Example-1, and chlorine was added while maintaining the temperature at 125 to 135°C. 44 Nt/Hr was introduced and the reaction was continued for 200 hours. After the reaction was completed, 58 g of water was added dropwise while heating at 80 to 90°C for 30 minutes.
Hydrolysis was carried out for 0 minutes to obtain 4854 g of a reaction solution. The composition of the reaction solution was as follows.
Claims (1)
＿〜＿４の直鎖アルキル基を示す）で表わされる２−ク
ロルカルボン酸の製造において、当該カルボン酸の酸無
水物を触媒として塩素化することを特徴とする２−クロ
ルカルボン酸の製造法。[Claims] General formula by chlorination of aliphatic carboxylic acid▲There are mathematical formulas, chemical formulas, tables, etc.▼(Here, R is C_1
A method for producing 2-chlorocarboxylic acid, which comprises chlorinating the carboxylic acid using an acid anhydride as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62122255A JPS63287743A (en) | 1987-05-19 | 1987-05-19 | Production of 2-chlorocarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62122255A JPS63287743A (en) | 1987-05-19 | 1987-05-19 | Production of 2-chlorocarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63287743A true JPS63287743A (en) | 1988-11-24 |
Family
ID=14831424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62122255A Pending JPS63287743A (en) | 1987-05-19 | 1987-05-19 | Production of 2-chlorocarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63287743A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292413A (en) * | 2021-06-08 | 2021-08-24 | 安徽星宇化工有限公司 | Preparation method of 3-chloropropionic acid |
-
1987
- 1987-05-19 JP JP62122255A patent/JPS63287743A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292413A (en) * | 2021-06-08 | 2021-08-24 | 安徽星宇化工有限公司 | Preparation method of 3-chloropropionic acid |
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