JPH0967359A - Production of tetrachlorophthalic anhydride - Google Patents
Production of tetrachlorophthalic anhydrideInfo
- Publication number
- JPH0967359A JPH0967359A JP22309995A JP22309995A JPH0967359A JP H0967359 A JPH0967359 A JP H0967359A JP 22309995 A JP22309995 A JP 22309995A JP 22309995 A JP22309995 A JP 22309995A JP H0967359 A JPH0967359 A JP H0967359A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- phthalic anhydride
- tetrachlorophthalic anhydride
- 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
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- Furan Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルキッド樹脂製
造原料や、フタロシアニン系緑色顔料及びキサンテン系
染料の中間体として有用なテトラクロル無水フタル酸に
関する。TECHNICAL FIELD The present invention relates to tetrachlorophthalic anhydride which is useful as a raw material for producing alkyd resins and as an intermediate for phthalocyanine green pigments and xanthene dyes.
【０００２】[0002]
【従来の技術】従来のテトラクロル無水フタル酸の製造
方法は、塩素ガスを用いて無水フタル酸を塩素化する方
法が用いられている。例えば、（１）無水フタル酸を２
７０℃で溶融下に、塩化第二鉄触媒で反応させる方法
（米国特許第２，０２８，３８３号及び第２，４２９，
９８５号）、（２）塩化第二鉄触媒存在下２７０℃で無
水フタル酸と塩素ガスを気相で反応させる方法（有機合
成協会誌第２２巻９号７３７頁(１９６４年）)、（３）
溶媒として発煙硫酸を使用し、５０〜６０℃で無水フタ
ル酸と塩素ガスとを液相反応させる方法（***特許第５
０１，７７０号）、（４）溶媒としてクロルスルホン酸
を使用し、同様に無水フタル酸と塩素ガスとを液相反応
させる方法（特開昭６１−１１８号）、（５）溶媒とし
て無水硫酸を用い、触媒としてヨウ素又はヨウ素化合物
を存在させて無水フタル酸と塩素ガスを反応させる方法
（特開昭６−３２９６５３号）等が知られている。2. Description of the Related Art As a conventional method for producing tetrachlorophthalic anhydride, a method of chlorinating phthalic anhydride using chlorine gas is used. For example, (1) phthalic anhydride 2
A method of reacting with a ferric chloride catalyst under melting at 70 ° C. (US Pat. Nos. 2,028,383 and 2,429,
985), (2) a method of reacting phthalic anhydride and chlorine gas in a gas phase at 270 ° C. in the presence of a ferric chloride catalyst (Organic Synthesis Society, Vol. 22, No. 9, pp. 737 (1964)), (3) )
A method in which fuming sulfuric acid is used as a solvent and phthalic anhydride and chlorine gas are subjected to a liquid phase reaction at 50 to 60 ° C. (West German Patent No. 5
No. 01,770), (4) a method in which chlorosulfonic acid is used as a solvent, and phthalic anhydride and chlorine gas are similarly subjected to a liquid phase reaction (JP-A 61-118), and (5) sulfuric anhydride as a solvent. There is known a method of reacting phthalic anhydride with chlorine gas in the presence of iodine or an iodine compound as a catalyst (JP-A-6-329653).
【０００３】しかし上記（１）及び（２）の方法では、
反応温度が高く、副生物が多量生成し着色を伴う場合が
多い。又上記（３）及び（４）の方法は、反応速度が遅
すぎて触媒を使用しても反応時間が長すぎ工業化に不向
きである。さらに（５）の方法は第一に金属ヨウ素又は
ヨウ素化合物を触媒としているが、コスト的に高価なヨ
ウ素化合物を使用する事は不利であり、また副生する塩
酸は溶媒の三酸化硫黄と反応しクロルスルホン酸とな
り、クロルスルホン酸と三酸化硫黄を分離する煩雑な操
作が必要になる。However, in the above methods (1) and (2),
The reaction temperature is high, and a large amount of by-products are formed and coloring is often involved. Further, in the above methods (3) and (4), the reaction rate is too slow and the reaction time is too long even if a catalyst is used, which is unsuitable for industrialization. Furthermore, although the method (5) uses metal iodine or an iodine compound as a catalyst, it is disadvantageous to use an expensive iodine compound in terms of cost, and hydrochloric acid as a by-product reacts with sulfur trioxide as a solvent. Then, it becomes chlorosulfonic acid, and a complicated operation for separating chlorosulfonic acid and sulfur trioxide is required.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは、上記の
塩素を用いることによる塩酸副生の弊害、高価なヨウ素
やヨウ素化合物を使用、ヨウ素化合物の副生、着色等の
問題点を解決すべく鋭意努力検討した結果、硫酸、発煙
硫酸又は三酸化硫黄等の強酸を溶媒として無水フタル酸
を塩素化イソシアヌル酸によって塩素化することによ
り、目的とするテトラクロル無水フタル酸を高収率で得
られる事を見いだし本発明を完成するに至った。DISCLOSURE OF THE INVENTION The present inventors have solved the problems of the above-mentioned adverse effects of hydrochloric acid by-product by using chlorine, expensive iodine and iodine compounds, by-product of iodine compound, coloring and the like. As a result of diligently studying in order to obtain the target tetrachlorophthalic anhydride in high yield, chlorinating phthalic anhydride with chlorinated isocyanuric acid using a strong acid such as sulfuric acid, fuming sulfuric acid or sulfur trioxide as a solvent. The present invention has been completed and the present invention has been completed.
【０００５】塩素剤として塩素化イソシアヌル酸を用い
る本反応は、従来の塩素を用いる塩酸副生のための弊害
も回避できる。本発明の目的は、アルキッド樹脂製造原
料や、フタロシアニン系緑色顔料及びキサンテン系染料
の中間体として有用なテトラクロル無水フタル酸の新規
な製造方法の提供にある。This reaction using chlorinated isocyanuric acid as the chlorine agent can avoid the harmful effects of the conventional hydrochloric acid by-product. An object of the present invention is to provide a novel method for producing tetrachlorophthalic anhydride, which is useful as a raw material for producing alkyd resins and as an intermediate for phthalocyanine green pigments and xanthene dyes.
【０００６】[0006]
【課題を解決するための手段】すなわち本発明は、強酸
を溶媒として、無水フタル酸を塩素化イソシアヌル酸で
塩素化することを特徴とするテトラクロル無水フタル酸
の製造方法に関する。That is, the present invention relates to a process for producing tetrachlorophthalic anhydride, which comprises chlorinating phthalic anhydride with chlorinated isocyanuric acid using a strong acid as a solvent.
【０００７】[0007]
【発明の実施の形態】以下、更に本発明を詳細に説明す
る。原料の無水フタル酸は、通常の市販品をそのまま使
用することができる。塩素化イソシアヌル酸としては、
トリクロロイソシアヌル酸、ジクロロイソシアヌル酸の
ナトリウム塩或いはカリウム塩が挙げられ、特にはトリ
クロロイソシアヌル酸が好ましい。その使用量は、基質
に対して有効塩素元素当たり４〜２０倍が好ましく、特
には４．５〜１０倍が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. As the raw material, phthalic anhydride, an ordinary commercially available product can be used as it is. As chlorinated isocyanuric acid,
Examples thereof include sodium salts or potassium salts of trichloroisocyanuric acid and dichloroisocyanuric acid, and trichloroisocyanuric acid is particularly preferable. The amount used is preferably 4 to 20 times, and particularly preferably 4.5 to 10 times per effective chlorine element with respect to the substrate.
【０００８】溶媒として用いる強酸としては、硫酸、発
煙硫酸及び三酸化硫黄等の無機強酸或いはトリフルオロ
酢酸、メタンスルホン酸、エタンスルホン酸等の有機の
強酸が挙げられる。これらの酸は組み合わせて使うこと
も可能である。反応収率及びコストの面で無機強酸が好
ましい。硫酸は、水分が存在すると原料及び生成物の無
水カルボニル基が水和してジカルボン酸となるので好ま
しくなく、高濃度程望ましく、通常の市販濃硫酸が好ま
しい。Examples of the strong acid used as a solvent include strong inorganic acids such as sulfuric acid, fuming sulfuric acid and sulfur trioxide, and strong organic acids such as trifluoroacetic acid, methanesulfonic acid and ethanesulfonic acid. These acids can be used in combination. In terms of reaction yield and cost, strong inorganic acids are preferred. Sulfuric acid is not preferable because the anhydrous carbonyl groups of the raw material and the product are hydrated to form a dicarboxylic acid in the presence of water, and a high concentration is desirable, and ordinary commercial concentrated sulfuric acid is preferable.
【０００９】又、発煙硫酸の三酸化硫黄含有量が高い程
反応温度は、低く設定することができる。溶媒の使用量
は、反応基質に対し１〜５０重量倍が可能で有るが、生
成物がスラリー状に析出してくる関係上３〜３０重量倍
が好ましい。反応温度は、５０〜１５０℃の間、特には
８０〜１３０℃の範囲が目的物の収率の点で好ましい。The higher the sulfur trioxide content of fuming sulfuric acid, the lower the reaction temperature can be set. The amount of the solvent used can be 1 to 50 times by weight that of the reaction substrate, but it is preferably 3 to 30 times by weight because the product is precipitated in the form of slurry. The reaction temperature is preferably in the range of 50 to 150 ° C., particularly in the range of 80 to 130 ° C. from the viewpoint of the yield of the desired product.
【００１０】反応時間は、反応条件により異なるが通常
１０時間以内に終了することができ、ガスクロマトクラ
フィーによる反応追跡によって反応の終点を決定するこ
とができる。反応は常圧でも加圧でも可能であり、又、
回分式でも連続式でも行う事ができる。反応後、冷却し
た後析出した結晶を濾取し、冷水で洗浄後乾燥すると粗
テトラクロル無水フタル酸の結晶が得られる。この結晶
から熱トルエンで抽出し、濃縮、乾燥することによって
純粋なテトラクロル無水フタル酸が得られる。また、反
応後のイソシアヌル酸は、熱トルエン抽出残査として得
られる。反応溶媒中に溶解したイソシアヌル酸は、例え
ば１，２−ジクロロエタン等の有機溶媒によって抽出さ
れる。この回収されたイソシアヌル酸は、Ｎａ塩とした
後塩素により容易に塩素化イソシアヌル酸に再生され
る。The reaction time varies depending on the reaction conditions, but can usually be completed within 10 hours, and the end point of the reaction can be determined by tracing the reaction by gas chromatography. The reaction can be carried out at normal pressure or under pressure, and
It can be performed batchwise or continuously. After the reaction, the reaction mixture is cooled and the precipitated crystals are collected by filtration, washed with cold water and dried to obtain crude tetrachlorophthalic anhydride crystals. Pure tetrachlorophthalic anhydride is obtained by extracting from the crystals with hot toluene, concentrating and drying. Further, the isocyanuric acid after the reaction is obtained as a hot toluene extraction residue. The isocyanuric acid dissolved in the reaction solvent is extracted with an organic solvent such as 1,2-dichloroethane. The recovered isocyanuric acid is easily converted into chlorinated isocyanuric acid by chlorine after forming Na salt.
【００１１】以下実施例及び比較例によって本発明をさ
らに具体的に説明するが、本発明はこれらによって限定
されるものではない。The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
【００１２】[0012]
実施例１ 無水フタル酸１．４８ｇ（１０ミリモル）、１０％発煙
硫酸１５ｇ及びトリクロロイソシアヌル酸４．６ｇ（２
０ミリモル）を５０ｍＬの反応フラスコに仕込み、１２
０℃で２時間撹拌した。反応終了後、冷却してから氷に
反応物を添加した後、析出した結晶を濾取、水洗後乾燥
すると粗結晶２．９ｇが得られた。 この粗結晶にトル
エンを加え加熱後濾過し、濾液を濃縮するとガスクロマ
トグラフィーで単一ピークの結晶２．１ｇが得られた。Example 1 1.48 g (10 mmol) of phthalic anhydride, 15 g of 10% fuming sulfuric acid and 4.6 g of trichloroisocyanuric acid (2
(0 mmol) was charged into a 50 mL reaction flask, and 12
Stirred at 0 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was cooled and then the reaction product was added to ice. The precipitated crystals were collected by filtration, washed with water and dried to obtain 2.9 g of crude crystals. Toluene was added to the crude crystals, the mixture was heated and then filtered, and the filtrate was concentrated to obtain 2.1 g of crystals having a single peak by gas chromatography.
【００１３】この結晶は、ＭＡＳＳ、13Ｃ−ＮＭＲから
テトラクロル無水フタル酸であることが判明した。上記
粗結晶を定量の結果、テトラクロル無水フタル酸の収率
は９３．２％であった。This crystal was found to be tetrachlorophthalic anhydride by MASS, 13 C-NMR. As a result of quantifying the above-mentioned crude crystals, the yield of tetrachlorophthalic anhydride was 93.2%.
【００１４】実施例２〜８ 硫酸の種類、トリクロロイソシアヌル酸量、温度及び反
応時間を変えた他は実施例１と同様に反応を行った。結
果を表１に示す。Examples 2 to 8 The reaction was carried out in the same manner as in Example 1 except that the type of sulfuric acid, the amount of trichloroisocyanuric acid, the temperature and the reaction time were changed. The results are shown in Table 1.
【００１５】[0015]
【表１】 [Table 1]
【００１６】比較例１ 無水フタル酸１．４８ｇ（１０ミリモル）と１０％発煙
硫酸４０ｇを５０ｍＬ反応フラスコに仕込み１２０℃
で、塩素ガスを１５ｍｌ／分の速度で２時間送入した。
（合計で無水フタル酸に対して８当量の塩素ガスを送入
した。） 反応液をガスクロマトグラフィーで分析の結果、目的と
するテトラクロル無水フタル酸は生成せず、原料のみで
あった。 比較例２ 実施例１に於いて、溶媒としてＮ−メチルピロリドンに
変えた他は同様に反応を行った。室温で発熱し反応液は
黒変しＮ−メチルピロリドンは、溶媒として好ましくな
かった。Comparative Example 1 1.48 g (10 mmol) of phthalic anhydride and 40 g of 10% fuming sulfuric acid were charged into a 50 mL reaction flask and 120 ° C.
Then, chlorine gas was introduced at a rate of 15 ml / min for 2 hours.
(A total of 8 equivalents of chlorine gas was fed to phthalic anhydride.) As a result of gas chromatographic analysis of the reaction liquid, the target tetrachlorophthalic anhydride was not produced and only the raw material was used. Comparative Example 2 The same reaction as in Example 1 was performed except that N-methylpyrrolidone was used as the solvent. Heat was generated at room temperature, the reaction liquid turned black, and N-methylpyrrolidone was not preferable as a solvent.
【００１７】[0017]
【発明の効果】強酸を溶媒として、塩素化イソシアヌル
酸による無水フタル酸の塩素化することで、従来の塩素
を用いる塩素化の際の塩酸副生の弊害も回避でき、目的
とするテトラクロル無水フタル酸が高収率で得られる。EFFECTS OF THE INVENTION By chlorinating phthalic anhydride with chlorinated isocyanuric acid using a strong acid as a solvent, it is possible to avoid the adverse effect of hydrochloric acid by-product during chlorination using conventional chlorine, and to obtain the desired tetrachlorophthalic anhydride. The acid is obtained in high yield.
Claims (3)
化イソシアヌル酸で塩素化することを特徴とするテトラ
クロル無水フタル酸の製造方法。1. A method for producing tetrachlorophthalic anhydride, which comprises chlorinating phthalic anhydride with chlorinated isocyanuric acid using a strong acid as a solvent.
シアヌル酸、ジクロロイソシアヌル酸のナトリウム塩或
いはカリウム塩である請求項１記載のテトラクロル無水
フタル酸の製造方法。2. The method for producing tetrachlorophthalic anhydride according to claim 1, wherein the chlorinated isocyanuric acid is trichloroisocyanuric acid or a sodium salt or potassium salt of dichloroisocyanuric acid.
中から選ばれた少なくとも一種の化合物である請求項１
又は２記載のテトラクロル無水フタル酸の製造方法。3. The strong acid is at least one compound selected from sulfuric acid, fuming sulfuric acid and sulfur trioxide.
Or the method for producing tetrachlorophthalic anhydride according to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22309995A JPH0967359A (en) | 1995-08-31 | 1995-08-31 | Production of tetrachlorophthalic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22309995A JPH0967359A (en) | 1995-08-31 | 1995-08-31 | Production of tetrachlorophthalic anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0967359A true JPH0967359A (en) | 1997-03-11 |
Family
ID=16792818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22309995A Pending JPH0967359A (en) | 1995-08-31 | 1995-08-31 | Production of tetrachlorophthalic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0967359A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114933579A (en) * | 2022-04-26 | 2022-08-23 | 河北海力香料股份有限公司 | Preparation method of tetrachlorophthalic anhydride |
-
1995
- 1995-08-31 JP JP22309995A patent/JPH0967359A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114933579A (en) * | 2022-04-26 | 2022-08-23 | 河北海力香料股份有限公司 | Preparation method of tetrachlorophthalic anhydride |
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