JP2784532B2 - Method for producing 3,3-bis- (4-dimethylaminophenyl) -6-dimethylaminophthalide - Google Patents
Method for producing 3,3-bis- (4-dimethylaminophenyl) -6-dimethylaminophthalideInfo
- Publication number
- JP2784532B2 JP2784532B2 JP63198701A JP19870188A JP2784532B2 JP 2784532 B2 JP2784532 B2 JP 2784532B2 JP 63198701 A JP63198701 A JP 63198701A JP 19870188 A JP19870188 A JP 19870188A JP 2784532 B2 JP2784532 B2 JP 2784532B2
- Authority
- JP
- Japan
- Prior art keywords
- bis
- oxygen
- catalyst
- producing
- dimethylaminophthalide
- 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 - Fee Related
Links
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
Landscapes
- Furan Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 式（２）で示される3,3−ビス−（４−ジメチルアミ
ノフェニル）−６−ジメチルアミノフタリドは一般にク
リスタルバイオレットラクトン（以下CVLという）とし
て公知であり、このCVLは反応性色素として、感圧複写
紙，感熱記録紙等に広く使用されている。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] 3,3-bis- (4-dimethylaminophenyl) -6-dimethylaminophthalide represented by the formula (2) is generally crystal violet lactone (hereinafter referred to as CVL). This CVL is widely used as a reactive dye in pressure-sensitive copying paper, heat-sensitive recording paper, and the like.
（式中MeはCH3を意味する。以下同じ。） 本発明は、CVLの改良された製造法に関するものであ
る。 (In the formula, Me means CH 3 ; the same applies hereinafter.) The present invention relates to an improved method for producing CVL.
式（１）で示される２−〔4,4′−ビス−（ジメチル
アミノ）−ベンゾヒドリル〕−５−ジメチルアミノ安息
香酸（以下LCという）を酸化して式（２）で示されるCV
Lを合成する製造法は、数多く知られている。2- [4,4'-bis- (dimethylamino) -benzohydryl] -5-dimethylaminobenzoic acid (hereinafter referred to as LC) represented by the formula (1) is oxidized to obtain a CV represented by the formula (2).
Many production methods for synthesizing L are known.
しかし従来の製法は、製造工程が煩雑であったり、酸
化による分解副生成物が多く、収量よく高品質のCVLを
得ることは困難であった。 However, in the conventional production method, the production process is complicated, and there are many decomposition by-products due to oxidation, and it is difficult to obtain high-quality CVL with high yield.
例えば、LCを氷酢酸，クロロホルム等の有機溶剤中、
クロラニル及び金属錯体の存在下酸素酸化する方法（特
開昭48−25730号公報）、LCを非水溶性の炭化水素系溶
剤及び水の混合液中、過酸化水素で酸化する方法（特開
昭52−78867号公報）等は、いずれも溶剤の回収が煩雑
であり収率も低かった。またLCを鉱酸水溶液中、過酸化
鉛，過マンガン酸カリウム等で酸化する方法（米国特許
第2417897号明細書）では副反応物が多く生成し品質に
重大な欠点を及ぼした。またLCを塩基性の水溶液もしく
は水溶性有機溶剤中、過酸化水素で酸化する方法（特開
昭52−31384号公報）、LCをアルカリ金属塩水溶液中、
コバルト及び銅化合物の触媒存在下に、過酸化水素，酸
素あるいは空気で酸化する方法（特公昭59−19548号公
報）、原子量50〜56の金属化合物の触媒存在下に、過酸
化水素，酸素あるいは酸素含有ガスで酸化する方法（特
開昭58−38279号公報）等は、未反応LCがいつまでも残
存し、収量が向上しなかった。For example, LC in an organic solvent such as glacial acetic acid, chloroform,
A method of oxidizing oxygen in the presence of chloranil and a metal complex (JP-A-48-25730), and a method of oxidizing LC with hydrogen peroxide in a mixed solution of a water-insoluble hydrocarbon solvent and water (JP-A-48-25730) No. 52-78867), the recovery of the solvent was complicated and the yield was low. In the method of oxidizing LC with lead peroxide, potassium permanganate or the like in a mineral acid aqueous solution (U.S. Pat. No. 2417897), a large amount of by-products was formed, which caused a serious defect in quality. Also, a method of oxidizing LC with hydrogen peroxide in a basic aqueous solution or a water-soluble organic solvent (JP-A-52-31384),
Oxidation with hydrogen peroxide, oxygen or air in the presence of a catalyst of cobalt and copper compounds (Japanese Patent Publication No. 59-19548), hydrogen peroxide, oxygen or oxygen in the presence of a metal compound having an atomic weight of 50 to 56 In the method of oxidizing with an oxygen-containing gas (JP-A-58-38279), unreacted LC remains forever and the yield is not improved.
本発明は、上記従来技術に鑑みなされたものであり、
CVLの収量と品質の向上を可能にする、改良製造法を提
供するものである。The present invention has been made in view of the above prior art,
The purpose of the present invention is to provide an improved production method capable of improving the yield and quality of CVL.
以上のように、LCの酸化反応に金属触媒を用いること
は周知であるが、適切な触媒の選択が難しく、満足のい
く結果は得られていなかった。As described above, the use of a metal catalyst for the oxidation reaction of LC is well known, but it has been difficult to select an appropriate catalyst, and satisfactory results have not been obtained.
発明者等は、従来のLCの酸化方法の欠点を改良すべく
鋭意研究した結果、特定の金属触媒にキレート剤を添加
することにより、その触媒効果が更に強力に発現するこ
とを見い出した。得に、鉄，マンガン化合物の混合触媒
にキレート剤を添加することにより、一段とCVLの収量
と品質が向上する。The present inventors have conducted intensive studies to improve the drawbacks of the conventional LC oxidation method, and as a result, have found that the addition of a chelating agent to a specific metal catalyst exerts its catalytic effect more strongly. In particular, by adding a chelating agent to a mixed catalyst of iron and manganese compounds, the yield and quality of CVL can be further improved.
すなわち、本発明はLCをpH7.0〜14.0に調整した塩基
性水溶液中、鉄，マンガン化合物及びキレート剤の三種
類の触媒存在を必須条件に、酸化剤として過酸化水素，
酸素又は酸素含有気体を用いて酸化することを特徴とす
るCVLの改良製造法である。That is, in the present invention, in a basic aqueous solution in which the LC is adjusted to pH 7.0 to 14.0, the presence of three types of catalysts, iron, a manganese compound, and a chelating agent, is essential.
This is an improved method for producing CVL, comprising oxidizing using oxygen or an oxygen-containing gas.
本発明において、使用する触媒中、鉄化合物の具体例
としては塩化第一鉄，硫酸第一鉄，フタロシアニン鉄
等、マンガン化合物としては二酸化マンガン，塩化マン
ガン，硫酸マンガン等，キレート剤としては酒石酸，グ
ルコン酸，エチレンジアミン四酢酸等、あるいはそれら
のナトリウム，カリウム，アミン塩等の鉄，マンガンと
キレート生成可能な化合物が挙げられる。また、反応水
溶液をpH7.0〜14.0に調整するにはナトリウム，カリウ
ムの水酸化物若しくは炭酸塩又はアンモニアなどの塩基
性化合物を任意に用いることが出来る。通常、酸化反応
は50〜100℃の温度で行われ、酸化剤として過酸化水
素，酸素又は酸素含有気体を大気圧あるいは加圧下にお
いて、反応液中に導入することにより達成される。In the present invention, specific examples of iron compounds in the catalyst used include ferrous chloride, ferrous sulfate, iron phthalocyanine and the like; manganese compounds such as manganese dioxide, manganese chloride and manganese sulfate; chelating agents such as tartaric acid; Examples of such compounds include compounds capable of chelating with iron and manganese, such as gluconic acid, ethylenediaminetetraacetic acid and the like, and sodium, potassium and amine salts thereof. In order to adjust the pH of the reaction aqueous solution to 7.0 to 14.0, a basic compound such as hydroxide or carbonate of sodium or potassium, or ammonia can be optionally used. Usually, the oxidation reaction is carried out at a temperature of 50 to 100 ° C., and is achieved by introducing hydrogen peroxide, oxygen or an oxygen-containing gas as an oxidizing agent into the reaction solution at atmospheric pressure or under pressure.
次に実施例と比較例を挙げて、本発明の改良製造法に
よりCVLの収量と品質が向上することを明らかにする。Next, with reference to Examples and Comparative Examples, it is clarified that the improved production method of the present invention improves the yield and quality of CVL.
実施例１ 空気導入管付きオートクレーブに、LC41.7g,触媒（塩
化第一鉄0.1g,硫酸マンガン0.1g,エチレンジアミン四酢
酸−２ナトリウム塩0.5g），炭酸ナトリウム5.3g,水500
ccを加えた。これを90℃に加熱し、反応容器のゲージ圧
を2kg/cm2に保持しながら空気10.7を４時間で導入し
た。この反応溶液中より生成物を濾別、水で充分に水洗
し乾燥して淡黄色結晶41.3g（m.p182〜184℃）を得た。Example 1 In an autoclave equipped with an air introduction tube, 41.7 g of LC, a catalyst (0.1 g of ferrous chloride, 0.1 g of manganese sulfate, 0.5 g of disodium ethylenediaminetetraacetic acid), 5.3 g of sodium carbonate, and 500 of water
cc was added. This was heated to 90 ° C., and air 10.7 was introduced over 4 hours while maintaining the gauge pressure of the reaction vessel at 2 kg / cm 2 . The product was filtered off from the reaction solution, sufficiently washed with water and dried to obtain 41.3 g of pale yellow crystals (m.p. 182 to 184 ° C).
実施例２ 実施例１の触媒（塩化第一鉄0.1g,硫酸マンガン0.1g,
エチレンジアミン四酢酸−２ナトリウム塩0.5g）に代え
て、硫酸第一鉄0.1g,硫酸マンガン0.1g,グルコン酸ナト
リウム0.5gを使用する以外は、実施例１と同様に操作し
て淡黄褐色結晶41.1g（m.p181.5〜183.5℃）を得た。Example 2 The catalyst of Example 1 (ferrous chloride 0.1 g, manganese sulfate 0.1 g,
The procedure of Example 1 was repeated, except that ferrous sulfate (0.1 g), manganese sulfate (0.1 g), and sodium gluconate (0.5 g) were used instead of ethylenediaminetetraacetic acid disodium salt (0.5 g). 41.1 g (m.p. 181.5-183.5 ° C.) were obtained.
比較例１ 実施例１の触媒（塩化第一鉄0.1g,硫酸マンガン0.1g,
エチレンジアミン四酢酸−２ナトリウム塩0.5g）に代え
て、塩化第一鉄0.1gのみを使用する以外は、実施例１と
同様に操作したが、淡黄褐色結晶34.2g（m.p178〜180
℃）が得られたに過ぎなかった。Comparative Example 1 The catalyst of Example 1 (0.1 g of ferrous chloride, 0.1 g of manganese sulfate,
The same operation as in Example 1 was carried out except that only ferrous chloride (0.1 g) was used instead of ethylenediaminetetraacetic acid disodium (0.5 g), but pale yellow-brown crystals (34.2 g, m.p.
° C).
比較例２ 実施例１の触媒（塩化第一鉄0.1g,硫酸マンガン0.1g,
エチレンジアミン四酢酸−２ナトリウム塩0.5g）に代え
て、硫酸マンガン0.1gのみを使用する以外は、実施例１
と同様に操作したが黄褐色結晶29.8g（m.p175〜177℃）
が得られたに過ぎなかった。Comparative Example 2 The catalyst of Example 1 (ferrous chloride 0.1 g, manganese sulfate 0.1 g,
Example 1 except that only 0.1 g of manganese sulfate was used instead of 0.5 g of ethylenediaminetetraacetic acid disodium salt).
The procedure was the same as described above, but 29.8 g of yellow-brown crystals (m.p. 175-177 ° C)
Was just obtained.
比較例３ 実施例１の触媒（塩化第一鉄0.1g,硫酸マンガン0.1g,
エチレンジアミン四酢酸−２ナトリウム塩0.5g）に代え
て、塩化第一鉄0.1g,硫酸マンガン0.1gを使用する以外
は、実施例１と同様に操作したが、淡黄褐色結晶37.7g
（m.p179〜181℃）が得られたに過ぎなかった。Comparative Example 3 The catalyst of Example 1 (ferrous chloride 0.1 g, manganese sulfate 0.1 g,
The procedure of Example 1 was repeated, except that ferrous chloride (0.1 g) and manganese sulfate (0.1 g) were used instead of ethylenediaminetetraacetic acid disodium (0.5 g), but 37.7 g of pale yellowish brown crystals were used.
(M.p. 179 DEG-181 DEG C.).
以上のように、本発明は特定の触媒の混合効果に加
え、キレート剤の触媒活性化作用をCVLの製造法に応用
するものである。これにより、従来法では得られなかっ
た高品質のCVLを高収量で得ることが出来る。As described above, the present invention applies the effect of activating a chelating agent to the CVL production method in addition to the effect of mixing a specific catalyst. As a result, high-quality CVL that cannot be obtained by the conventional method can be obtained in high yield.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−184061（ＪＰ，Ａ) 特開 昭55−25496（ＪＰ，Ａ) 特開 昭50−124931（ＪＰ，Ａ) 特開 昭47−10632（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C09B 11/00 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-184061 (JP, A) JP-A-55-2496 (JP, A) JP-A-50-124931 (JP, A) JP-A 47-49 10632 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) C09B 11/00 CA (STN) REGISTRY (STN)
Claims (1)
ベンゾヒドリル〕−５−ジメチルアミノ安息香酸をpH7.
0〜14.0に調整した塩基性水溶液中、鉄，マンガン化合
物及びキレート剤の三種類の触媒存在下に、過酸化水
素，酸素又は酸素含有気体を用いて酸化することを特徴
とする で示される3,3−ビス−（４−ジメチルアミノフェニ
ル）−６−ジメチルアミノフタリドの製造法。(1) 2- [4,4'-bis- (dimethylamino)-represented by
Benzohydryl) -5-dimethylaminobenzoic acid at pH 7.
Oxidation using hydrogen peroxide, oxygen or an oxygen-containing gas in a basic aqueous solution adjusted to 0 to 14.0 in the presence of three types of catalysts, iron, manganese compounds and chelating agents A method for producing 3,3-bis- (4-dimethylaminophenyl) -6-dimethylaminophthalide represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63198701A JP2784532B2 (en) | 1988-08-08 | 1988-08-08 | Method for producing 3,3-bis- (4-dimethylaminophenyl) -6-dimethylaminophthalide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63198701A JP2784532B2 (en) | 1988-08-08 | 1988-08-08 | Method for producing 3,3-bis- (4-dimethylaminophenyl) -6-dimethylaminophthalide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0247160A JPH0247160A (en) | 1990-02-16 |
| JP2784532B2 true JP2784532B2 (en) | 1998-08-06 |
Family
ID=16395589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63198701A Expired - Fee Related JP2784532B2 (en) | 1988-08-08 | 1988-08-08 | Method for producing 3,3-bis- (4-dimethylaminophenyl) -6-dimethylaminophthalide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2784532B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930021731A (en) * | 1992-04-08 | 1993-11-22 | 랑핑어, 방에르트 | Method for preparing diarylmethane or triarylmethane dye by oxidation |
| DE59306714D1 (en) * | 1992-04-08 | 1997-07-17 | Basf Ag | Process for the preparation of di- or triarylmethane dyes by oxidation |
| DE4211782A1 (en) * | 1992-04-08 | 1993-10-14 | Basf Ag | Process for the preparation of di- or triarylmethane dyes |
-
1988
- 1988-08-08 JP JP63198701A patent/JP2784532B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0247160A (en) | 1990-02-16 |
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