JPH0234333B2 - GANMAAKURORUASETOSAKUSANKURORAIDONOSEIZOHOHO - Google Patents
GANMAAKURORUASETOSAKUSANKURORAIDONOSEIZOHOHOInfo
- Publication number
- JPH0234333B2 JPH0234333B2 JP13477283A JP13477283A JPH0234333B2 JP H0234333 B2 JPH0234333 B2 JP H0234333B2 JP 13477283 A JP13477283 A JP 13477283A JP 13477283 A JP13477283 A JP 13477283A JP H0234333 B2 JPH0234333 B2 JP H0234333B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- chlorine
- diketene
- reactor
- acid chloride
- 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 - Lifetime
Links
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims description 9
- WSHVQVCBPLNREW-UHFFFAOYSA-N 4-chloro-3-oxobutanoyl chloride Chemical compound ClCC(=O)CC(Cl)=O WSHVQVCBPLNREW-UHFFFAOYSA-N 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HFLMYYLFSNEOOT-UHFFFAOYSA-N methyl 4-chloro-3-oxobutanoate Chemical compound COC(=O)CC(=O)CCl HFLMYYLFSNEOOT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- WNVYZJSJUQUVSZ-UHFFFAOYSA-N 2-chloro-3-oxobutanoyl chloride Chemical compound CC(=O)C(Cl)C(Cl)=O WNVYZJSJUQUVSZ-UHFFFAOYSA-N 0.000 description 1
- CJLSDBRIXZFCKV-UHFFFAOYSA-N 4-chloro-3-oxo-n-phenylbutanamide Chemical compound ClCC(=O)CC(=O)NC1=CC=CC=C1 CJLSDBRIXZFCKV-UHFFFAOYSA-N 0.000 description 1
- VCPNLOMAQUZMBY-UHFFFAOYSA-N 4-chloro-3-oxobutanamide Chemical compound NC(=O)CC(=O)CCl VCPNLOMAQUZMBY-UHFFFAOYSA-N 0.000 description 1
- UCTNTYHJFWMUBD-UHFFFAOYSA-N 4-chloro-3-oxobutanoic acid Chemical compound OC(=O)CC(=O)CCl UCTNTYHJFWMUBD-UHFFFAOYSA-N 0.000 description 1
- QZPDQRZWZYIBMY-UHFFFAOYSA-N 4-chloro-3-oxobutanoic acid hydrochloride Chemical compound Cl.OC(=O)CC(=O)CCl QZPDQRZWZYIBMY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
γ−クロルアセト酢酸クロライドは赤色顔料で
あるキナクリドンの中間体或は医薬原料その他合
成原料として有用なものである。しかして、該ク
ロライドの製造法としては有機溶媒中にジケテン
及び塩素を導入して両者を反応させるバツチ方式
が一般的である。DETAILED DESCRIPTION OF THE INVENTION γ-Chloroacetoacetic acid chloride is useful as an intermediate for quinacridone, which is a red pigment, or as a raw material for pharmaceuticals and other synthetic raw materials. The common method for producing chloride is a batch method in which diketene and chlorine are introduced into an organic solvent and the two are reacted.
しかしながら本発明者等が確認したところによ
ると、該クロライドの生成反応は反応熱の高い発
熱反応にもかかわらず、該反応の反応は比較的低
温が要求されるが、上記バツチ方式では伝熱面積
が充分にとれないために、冷凍負荷を工業的に実
用的な範囲に止めようとすると必然的に反応時間
が長くなる傾向があり、この様な長時間の反応を
実施すると、目的物以外にα−クロルアセト酢酸
クロライド、高次塩素化物等の副生物の生成が避
けがたいことが明らかとなつた。かかる対策とし
て、濡壁塔式反応器や流通管式反応器を用いて、
該反応を実施することが提案されてるが、前者で
は目的物の収率が精々89％程度であり工業的規模
での実施に当つては更に収率向上の必要があるこ
と、後者では反応装置が複雑であるので工業的実
施は実用面のトラブルが予想される難点がある。 However, as confirmed by the present inventors, although the chloride production reaction is an exothermic reaction with a high heat of reaction, the reaction requires a relatively low temperature. If you try to keep the refrigeration load within an industrially practical range, the reaction time inevitably tends to become longer. It has become clear that the production of by-products such as α-chloroacetoacetic acid chloride and higher chlorinated products is unavoidable. As a countermeasure against this, using a wet wall tower reactor or a flow tube reactor,
It has been proposed to carry out this reaction, but in the former, the yield of the target product is at most about 89%, and it is necessary to further improve the yield when implementing it on an industrial scale, and in the latter, the reaction equipment is Since the method is complicated, it is difficult to implement it industrially because practical problems can be expected.
しかるに、本発明者等はかかる問題を解決する
ために、鋭意研究を重ねた結果、回転薄膜式反応
器内でジケテンと塩素とを反応させる時には、α
−クロルアセト酢酸クロライドや高次塩素化物等
の副生が非常に少なく品質の優れたγ−クロルア
セト酢酸クロライドが35％以上の高収率で得られ
ること、更に反応時の除熱が容易であり、そのた
め反応の管理が容易であること等の新規な事実を
見出し本発明を完成するに至つた。 However, in order to solve this problem, the present inventors have conducted intensive research and found that when diketene and chlorine are reacted in a rotating thin film reactor, α
- γ-chloroacetoacetic acid chloride of excellent quality with very little by-products such as chloroacetoacetic acid chloride and higher chlorinated products can be obtained at a high yield of 35% or more, and furthermore, heat removal during the reaction is easy, Therefore, we discovered new facts such as ease of reaction control and completed the present invention.
本発明における回転薄膜式反応器とは、管状の
反応器内に回転羽根を挿入したもので、器内に導
入された反応原料は羽根の回転力によつて管壁に
薄膜を形成し、管壁にそつて回転しながら流下す
る間に反応が進行する反応器であつて任意の形
状、様式のものを使用出来る。通常管状反応器の
上部からジケテン及び塩素を導入して反応させれ
ば良い。反応器は１器のみでなく、複数個併列に
使用することも可能である。 The rotary thin film reactor used in the present invention is a tubular reactor in which rotating blades are inserted, and the reaction raw materials introduced into the vessel form a thin film on the tube wall due to the rotational force of the blades. A reactor in which the reaction proceeds while flowing down while rotating along the wall, and can be of any shape or style. Usually, diketene and chlorine may be introduced from the upper part of a tubular reactor and reacted. Not only one reactor but also a plurality of reactors can be used in parallel.
供給するジケテン及び塩素は通常はジケテン、
塩素に不活性な溶媒例えばジクロルメタン、ジク
ロルエタン、ジクロルプロパン、四塩化炭素、ク
ロロホルム、液体二酸化硫黄等に溶解して使用さ
れる。溶解する場合、塩素、ジケテンの濃度が小
さい程副生物の生成は少ないが、反応終了後の溶
剤回収の点でその濃度は１〜25重量％好ましくは
10〜20重量％にするのが適当である。上記原料の
供給量は塩素／ジケテンの割合が0.95〜1.10（モ
ル比）になる様に調整するのが望ましい。反応温
度は−30℃〜＋20℃と広範囲の温度が選ばれるが
好ましくは−20℃〜０℃である。 The diketene and chlorine supplied are usually diketene,
It is used after being dissolved in a solvent inert to chlorine, such as dichloromethane, dichloroethane, dichloropropane, carbon tetrachloride, chloroform, liquid sulfur dioxide, etc. When dissolving, the lower the concentration of chlorine and diketene, the less by-products are produced, but from the viewpoint of solvent recovery after the reaction, the concentration is preferably 1 to 25% by weight.
A suitable content is 10 to 20% by weight. It is desirable to adjust the supply amount of the above-mentioned raw materials so that the ratio of chlorine to diketene is 0.95 to 1.10 (molar ratio). The reaction temperature is selected from a wide range of -30°C to +20°C, but preferably -20°C to 0°C.
又、回転羽根の回転数はその形状により一概に
は規定出来ないが、通常400rpm以上が必要であ
る。更に原料の器内滞留時間は0.1〜30分好まし
くは１〜15分程度の範囲から選択される。 Further, although the rotational speed of the rotating blade cannot be unconditionally determined depending on its shape, it is usually required to be 400 rpm or more. Further, the residence time of the raw material in the container is selected from a range of about 0.1 to 30 minutes, preferably about 1 to 15 minutes.
かくして反応を行うと反応器底より目的とする
γ−クロルアセト酢酸クロライドが得られるが、
このものは非常に不安定であるので０℃以下の冷
却下に捕集することが望ましく、又その保存にも
注意する必要がある。そのためなるべく早くα−
クロルアセト酢酸クロライドにアルコール、フエ
ノール、アミン、アリニン等を反応させて比較的
安定なγ−クロルアセト酢酸エステル、γ−クロ
ルアセト酢酸アミド、γ−クロルアセト酢酸アニ
リド等に変化させることが有利である。その後常
圧又は減圧下に蒸留を行つて溶媒を回収する。 When the reaction is carried out in this way, the desired γ-chloroacetoacetic acid chloride is obtained from the bottom of the reactor, but
Since this substance is very unstable, it is desirable to collect it while cooling it to below 0°C, and care must also be taken in its storage. Therefore, α− as soon as possible
It is advantageous to react chloroacetoacetic acid chloride with alcohol, phenol, amine, alinine, etc. to convert it into relatively stable γ-chloroacetoacetate, γ-chloroacetoacetamide, γ-chloroacetoacetanilide, etc. Thereafter, the solvent is recovered by distillation under normal pressure or reduced pressure.
次に実例を挙げて本発明の方法を更に詳しく説
明する。 Next, the method of the present invention will be explained in more detail by giving examples.
実施例 １
内径80mm、高さ120mmの回転薄膜式反応器のジ
ヤケツトを溶媒で−13.0℃以下に冷却し、回転羽
根を1000rpmの割合で回転させながら、約70mlの
ジクロルエタンを滴下し管壁に回転状の薄膜を形
成させた。次に−20℃に冷却した10％塩素含有の
ジクロルエタン溶液及び11％ジケテン含有のジク
ロルエタン溶液をそれぞれ44ml／分の割合で連続
的に供給した。この時の内温は９℃であつた。Example 1 The jacket of a rotating thin film reactor with an inner diameter of 80 mm and a height of 120 mm was cooled to below -13.0°C with a solvent, and while rotating the rotary blades at a rate of 1000 rpm, about 70 ml of dichloroethane was dropped onto the tube wall. A thin film was formed. Next, a 10% chlorine-containing dichloroethane solution and a 11% diketene-containing dichloroethane solution cooled to -20°C were each continuously fed at a rate of 44 ml/min. The internal temperature at this time was 9°C.
底部から流出したγ−クロルアセト酢酸クロラ
イドを−10〜−20℃の冷却下に捕集した。 γ-Chloroacetoacetic acid chloride flowing out from the bottom was collected under cooling at -10 to -20°C.
かくして得られたγ−クロルアセト酢酸クロラ
イド反応液に−５〜０℃の温度にメチルアルコー
ルを滴下しγ−クロルアセト酢酸メチル反応液を
得た。次いで該液から減圧室温下に塩酸を追出
し、更に50℃に加温減圧下にジクロルエタンを蒸
留留出させた。粗γ−クロルアセト酢酸メチルの
ガスクロ分析を行つたところ、γ−クロルアセト
酢酸メチルの収率は95％であつた。 Methyl alcohol was added dropwise to the thus obtained γ-chloroacetoacetate chloride reaction solution at a temperature of -5 to 0°C to obtain a γ-chloroacetoacetate methyl reaction solution. Next, hydrochloric acid was removed from the liquid under reduced pressure at room temperature, and dichloroethane was distilled off under reduced pressure while heating to 50°C. Gas chromatography analysis of the crude methyl γ-chloroacetoacetate revealed that the yield of methyl γ-chloroacetoacetate was 95%.
実施例 ２
冷媒の温度を０℃にして実施例１を準じてγ−
クロルアセト酢酸クロライドおよびそのメチルエ
ステルの合成を行つた。その結果収率は95％であ
つた。Example 2 γ-
Chloracetoacetic acid chloride and its methyl ester were synthesized. As a result, the yield was 95%.
Claims (1)
応させることを特徴とするγ−クロルアセト酢酸
クロライドの製造方法。1. A method for producing γ-chloroacetoacetic acid chloride, which comprises reacting diketene and chlorine in a rotating thin film reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13477283A JPH0234333B2 (en) | 1983-07-22 | 1983-07-22 | GANMAAKURORUASETOSAKUSANKURORAIDONOSEIZOHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13477283A JPH0234333B2 (en) | 1983-07-22 | 1983-07-22 | GANMAAKURORUASETOSAKUSANKURORAIDONOSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6025951A JPS6025951A (en) | 1985-02-08 |
| JPH0234333B2 true JPH0234333B2 (en) | 1990-08-02 |
Family
ID=15136201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13477283A Expired - Lifetime JPH0234333B2 (en) | 1983-07-22 | 1983-07-22 | GANMAAKURORUASETOSAKUSANKURORAIDONOSEIZOHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0234333B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62136994A (en) * | 1985-12-11 | 1987-06-19 | Hitachi Ltd | Encoder circuit |
| EP2518043A1 (en) | 2011-04-29 | 2012-10-31 | Lonza Ltd. | Process for the production of 4-chloroacetyl chloride, 4-chloroacetic acid esters, amides and imides |
-
1983
- 1983-07-22 JP JP13477283A patent/JPH0234333B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6025951A (en) | 1985-02-08 |
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