JPS62255454A - Production of 2-(4,4'-bis(dimethylamino)-benzohydryl)-5-dimethylaminobenz-oic acid - Google Patents
Production of 2-(4,4'-bis(dimethylamino)-benzohydryl)-5-dimethylaminobenz-oic acidInfo
- Publication number
- JPS62255454A JPS62255454A JP61097376A JP9737686A JPS62255454A JP S62255454 A JPS62255454 A JP S62255454A JP 61097376 A JP61097376 A JP 61097376A JP 9737686 A JP9737686 A JP 9737686A JP S62255454 A JPS62255454 A JP S62255454A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- bis
- benzohydryl
- dimethylamino
- average particle
- 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.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 title claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- NEGFNJRAUMCZMY-UHFFFAOYSA-N 3-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC(C(O)=O)=C1 NEGFNJRAUMCZMY-UHFFFAOYSA-N 0.000 claims abstract 4
- MABRBBOPUASAAI-UHFFFAOYSA-N bis(4-aminophenyl)methanol Chemical compound C1=CC(N)=CC=C1C(O)C1=CC=C(N)C=C1 MABRBBOPUASAAI-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 2
- 150000005215 alkyl ethers Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- -1 polyoxyethylene Polymers 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- WFZCOHPBVCLBQE-UHFFFAOYSA-N 1-(4-aminophenyl)-1-(4-amino-2,3,5-trimethylphenyl)ethanol Chemical compound CC1=C(N)C(C)=CC(C(C)(O)C=2C=CC(N)=CC=2)=C1C WFZCOHPBVCLBQE-UHFFFAOYSA-N 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000000049 pigment Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 5
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RGEMJCLUPGZKTQ-WAUHAFJUSA-N (3s,8r,9s,10r,13s,14s)-3-[2-(dimethylamino)ethoxy]-10,13-dimethyl-1,2,3,4,7,8,9,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-17-one Chemical compound C([C@@H]12)C[C@]3(C)C(=O)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OCCN(C)C)C1 RGEMJCLUPGZKTQ-WAUHAFJUSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005406 washing Methods 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
２−（”４．４１−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と略
称する）は、感圧複写紙、感熱記録紙等の記録材料用色
素として広く一般に用いられている３、３−ビス（４−
ジメチルアミノフェニル）−６−シメチルアミノフタリ
ド（以下ｃｖＬと略称する）の中間体として極めて重要
な化合物である。本発明は、その改良された製造法に関
するものである。Detailed Description of the Invention [Industrial Field of Application] 2-("4.41-bis(dimethylamino)-benzohydryl]-5-dimethylaminobenzoic acid (hereinafter abbreviated as LC) is used for pressure-sensitive copying paper. , 3,3-bis(4-
It is an extremely important compound as an intermediate of dimethylaminophenyl)-6-dimethylaminophthalide (hereinafter abbreviated as cvL). The present invention relates to an improved method of manufacturing the same.
〔従来の技術と発明が解決しようとする問題点〕従来か
らＬＣの合成法としては、コージメチルアミノ安息香酸
（以下ＤＡ ＢＡと略称する）とテトラメチル４，４１
−ジアミノベンズヒドロール（以下ＭＨと略称する）と
を硫酸水溶液中で反応させる方法（米国特許第５８４２
１０５号）、及びＤＡＢＡの硫酸水溶液中にＭＨの硫酸
水溶液を滴下する方法（ドイツ公開第２１５６４８号）
があるが、いずれの方法も反応中での分解副生成物が多
く、収率及び品質は極めて低い。一般にＬＣを酸化して
合成されるＣｖＴＪの収率と品質は、ＬＣの品質に大き
く左右されることが知られておシ、通常酸化する前ＫＬ
Ｃを単離、精製することがおこなわれる。例えば、芳香
族炭化水素、又は水下混合性アルカンとの混合物を用い
て処理する方法（特開昭５３−１１５７４０）があるが
、溶剤の回収が煩雑であシ、処理中にＩ、Ｏの損失が大
きい等の欠点がある。本発明は、これら欠点を改良し高
品質のＬＣを高収率で合成する製造法を提供するもので
ある。[Prior art and problems to be solved by the invention] Conventionally, as a method for synthesizing LC, kodimethylaminobenzoic acid (hereinafter abbreviated as DA BA) and tetramethyl 4,41
- A method of reacting diaminobenzhydrol (hereinafter abbreviated as MH) in an aqueous sulfuric acid solution (US Pat. No. 5842)
105), and a method of dropping a sulfuric acid aqueous solution of MH into a sulfuric acid aqueous solution of DABA (German Publication No. 215648).
However, both methods produce many decomposition by-products during the reaction, and the yield and quality are extremely low. It is known that the yield and quality of CvTJ, which is generally synthesized by oxidizing LC, is greatly affected by the quality of LC.
C is isolated and purified. For example, there is a method of treatment using aromatic hydrocarbons or mixtures with water-miscible alkanes (Japanese Unexamined Patent Publication No. 53-115740), but the recovery of the solvent is complicated and I and O are removed during the treatment. It has drawbacks such as large losses. The present invention aims to improve these drawbacks and provide a manufacturing method for synthesizing high-quality LC in high yield.
本発明者等は、従来の合成法の欠点を改良すべく鋭意研
究した結果、本発明の改良された製造法によシ極めて高
品質のＴＪＣが高収率で得られることを見い出した。す
なわちＤＡＥＡを含むＰＨＨＩ３．５−３．０の鉱酸水
溶液中にＭＨを加えることを特徴とするＬＣの製造法で
ある。ここで使用される鉱酸としては、塩酸及び硫酸が
挙げられる。又ＤＡＢＡの平均粒子径としては３０ミク
ロン以下がよく、ＭＨの平均粒子径としては５０ミクロ
ン以下がよい。反応温度は５０−１００℃が好ましく、
ＭＨはできるだけゆつくシと加えるのが有利である。又
反応混合物を均一に分散させるため界面活性剤、例えば
ポリオキシエチレンアルキルエーテル等の添加は効果的
である。As a result of intensive research aimed at improving the drawbacks of conventional synthesis methods, the present inventors have discovered that extremely high quality TJC can be obtained in high yield by the improved production method of the present invention. That is, the method for producing LC is characterized in that MH is added to an aqueous mineral acid solution containing DAEA and having a PHHI of 3.5 to 3.0. Mineral acids used here include hydrochloric acid and sulfuric acid. Further, the average particle diameter of DABA is preferably 30 microns or less, and the average particle diameter of MH is preferably 50 microns or less. The reaction temperature is preferably 50-100°C,
It is advantageous to add MH as slowly as possible. Additionally, it is effective to add a surfactant such as polyoxyethylene alkyl ether to uniformly disperse the reaction mixture.
本発明の改良された製造法が従来の欠点をなくし、高品
質のＬＣを高収率で得る上において極めて優れているこ
とを以下に説明する。すなわち本発明は、鉱酸水溶液、
好ましくは硫酸水溶液のＰＨＨＩ３５−３．０、好まし
くは２．０−３．０において最適反応条件となシ、反応
は非常に促進され分解副生成物も少い。このＰＨ価にお
いて生成するＩ、Ｃは余シ溶解せず、ＤＡＢＡ及びＭＥ
ｔはよく溶解する。このなめ加えられたＭＨは、速やか
に溶解しＤＡＥＡと反応する。又反応溶液中に懸濁して
いるＤＡＥＡは、反応によシ生成したＩ、Ｏの析出に伴
って速やかに溶解し反応液のｐｉはほぼ一定に保たれる
。この結果ＬＣが円滑に生成され高収率で目的物が得ら
れる。又上記ＰＨにおいては、 ＤＡＢＡ及びＭＥｔ中
の不純物や反応中の分解副生成物がよく溶解するため反
応後析出したＬＣｔ−５５過、水洗するのみではとんど
完全にこれらを除去することができ高品質のＬＣがえら
れる。It will be explained below that the improved manufacturing method of the present invention eliminates the conventional drawbacks and is extremely superior in obtaining high quality LC in high yield. That is, the present invention provides a mineral acid aqueous solution,
The optimum reaction conditions are preferably a PHHI of 35-3.0, preferably 2.0-3.0 of the sulfuric acid aqueous solution, the reaction is very accelerated and there are few decomposition by-products. I and C produced at this pH value do not dissolve, and DABA and ME
t dissolves well. This added MH quickly dissolves and reacts with DAEA. Furthermore, DAEA suspended in the reaction solution is rapidly dissolved as I and O produced by the reaction are precipitated, and the pi of the reaction solution is kept almost constant. As a result, LC is smoothly generated and the target product can be obtained in high yield. Furthermore, at the above pH, impurities in DABA and MEt and decomposition by-products during the reaction dissolve well, so they cannot be completely removed by simply filtering through LCt-55 and washing with water, which precipitate after the reaction. High quality LC can be obtained.
次に実施例を挙げて具体的に説明する０〔実施例〕
実施例 １゜
ＤＡＢＡ １７７ ｙ （平均粒子径３０ミクロン以下
で純粋なりＡＥＡ １７３ｇを含む）を４．９％（以下
重量部）硫酸水溶液５００ｇ１Ｉｃ加え、次いでスコア
ロールナ１００（花王アトラス社製）１Ｆを添加し、攪
拌下ＩＣ７０℃でＭＨ２Ｂ４ｇ（平均粒子径５０ミクロ
ン以下で純粋なＭＨ２７０９を含む）と水５００ゴの混
合物を１０時間で加えた。反応終了後反応物を濾過し、
濾過残渣を中性まで水洗し乾燥粗生成物３９１ ｇ（理
論量の９２％のＬＣを含む）を得た。Next, examples will be specifically explained.0 [Example] Example 1゜DABA 177y (pure with an average particle size of 30 microns or less and containing 173 g of AEA) was added to 4.9% (hereinafter parts by weight) sulfuric acid. Add 500g of an aqueous solution, then add 1F of Scorerolna 100 (manufactured by Kao Atlas Co., Ltd.), and add a mixture of 4g of MH2B (contains pure MH2709 with an average particle size of 50 microns or less) and 500g of water at IC 70°C under stirring for 10 hours. added. After the reaction is completed, the reaction product is filtered,
The filter residue was washed with water to neutrality to obtain 391 g of dry crude product (containing 92% of the theoretical amount of LC).
実施例 ２゜
ＭＨ２８４ｆ（平均粒子径５０ミクロン以下で純粋なＭ
Ｈ２７０ｆを含む）を、Ｍｕ３１ｏｇ（平均粒子径１０
ミクロン以下で純粋なＭＨ２７０ｆを含む）に代える以
外は、実施例１と全く同様の操作をおこない乾燥粗生成
物３ｓ７Ｆ（理論量の９０％のＩ、Ｃを含む）を得た。Example 2゜MH284f (pure M with an average particle size of 50 microns or less)
H270f), Mu31og (average particle size 10
A dry crude product 3s7F (containing 90% of the theoretical amount of I and C) was obtained by carrying out exactly the same operation as in Example 1, except for replacing with MH270f (containing 90% of the theoretical amount of I and C).
実施例 ３゜ のＬＣを含む）を得た。Example 3゜ (containing LC) was obtained.
実施例 ４゜
実施例１の硫酸水溶液の代シに９．８％硫酸水溶液む）
を得た。Example 4゜9.8% sulfuric acid aqueous solution was used instead of the sulfuric acid aqueous solution of Example 1)
I got it.
実施例 ５゜
１ａａＭｔの割合で１０時間かけて空気を導入した。反
応終了後反応物を濾過し、濾過残渣を中性迄水洗して乾
燥粗生成物４ｏ６ｐ（理論量の９４％のＣＶＬを含む）
を得た。このものは極めて高い品質のＣＶＬであった。Example 5 Air was introduced at a rate of 1 aaMt over 10 hours. After the completion of the reaction, the reaction product was filtered, and the filter residue was washed with water until neutral to give a dry crude product 4o6p (containing 94% of the theoretical amount of CVL).
I got it. This was CVL of extremely high quality.
Claims (4)
−３．０の鉱酸水溶液中にテトラメチル−４，４＾１−
ジアミノベンズヒドロールを加えることを特徴とする２
−〔４，４＾１−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の製造法。(1) PH value 1.5 containing m-dimethylaminobenzoic acid
-Tetramethyl-4,4^1- in mineral acid aqueous solution of -3.0
2 characterized by adding diaminobenzhydrol
- [4,4^1-bis(dimethylamino)-benzohydryl]-5-dimethylaminobenzoic acid production method.
求の範囲第１項に記載の２−〔４，４＾１−ビス（ジメ
チルアミノ）−ベンゾヒドリル〕−５−ジメチルアミノ
安息香酸の製造法。(2) Production of 2-[4,4^1-bis(dimethylamino)-benzohydryl]-5-dimethylaminobenzoic acid according to claim 1, characterized in that sulfuric acid is used as the mineral acid. Law.
ミクロン以下とする特許請求の範囲第２項に記載の２−
〔４，４＾１−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の製造法。(3) The average particle diameter of m-dimethylaminobenzoic acid is 30
2- as set forth in claim 2, which is less than microns;
A method for producing [4,4^1-bis(dimethylamino)-benzohydryl]-5-dimethylaminobenzoic acid.
ロールの平均粒子径を５０ミクロン以下とする特許請求
の範囲第２項又は第３項に記載の２−〔４，４＾１−ビ
ス（ジメチルアミノ）ベンゾヒドリル〕−５−ジメチル
アミノ安息香酸の製造法。(4) 2-[4,4^1-bis according to claim 2 or 3, wherein the average particle diameter of tetramethyl-4,4^1-diaminobenzhydrol is 50 microns or less A method for producing (dimethylamino)benzohydryl]-5-dimethylaminobenzoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61097376A JPS62255454A (en) | 1986-04-25 | 1986-04-25 | Production of 2-(4,4'-bis(dimethylamino)-benzohydryl)-5-dimethylaminobenz-oic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61097376A JPS62255454A (en) | 1986-04-25 | 1986-04-25 | Production of 2-(4,4'-bis(dimethylamino)-benzohydryl)-5-dimethylaminobenz-oic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62255454A true JPS62255454A (en) | 1987-11-07 |
| JPH0333150B2 JPH0333150B2 (en) | 1991-05-16 |
Family
ID=14190793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61097376A Granted JPS62255454A (en) | 1986-04-25 | 1986-04-25 | Production of 2-(4,4'-bis(dimethylamino)-benzohydryl)-5-dimethylaminobenz-oic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62255454A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0373151A2 (en) * | 1987-05-18 | 1990-06-13 | Yamada Chemical Co., Ltd. | Process for producing 2-(4,4'-bis-(dimethylamino)-benzhydryl)-5-dimethyl-aminobenzoic acid |
-
1986
- 1986-04-25 JP JP61097376A patent/JPS62255454A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0373151A2 (en) * | 1987-05-18 | 1990-06-13 | Yamada Chemical Co., Ltd. | Process for producing 2-(4,4'-bis-(dimethylamino)-benzhydryl)-5-dimethyl-aminobenzoic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0333150B2 (en) | 1991-05-16 |
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