JPH04224579A - Alpha-quinacuridone derivative and preparation thereof - Google Patents
Alpha-quinacuridone derivative and preparation thereofInfo
- Publication number
- JPH04224579A JPH04224579A JP3089276A JP8927691A JPH04224579A JP H04224579 A JPH04224579 A JP H04224579A JP 3089276 A JP3089276 A JP 3089276A JP 8927691 A JP8927691 A JP 8927691A JP H04224579 A JPH04224579 A JP H04224579A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- ring
- compound
- general formula
- derivative
- 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims abstract description 4
- 125000006091 1,3-dioxolane group Chemical group 0.000 claims abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- -1 m-nitrobenzenesulfonic acid alkali metal salt Chemical class 0.000 claims abstract 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- SNDAOXYSCAWUFQ-UHFFFAOYSA-N 5,6,12,13-tetrahydroquinolino[2,3-b]acridine-7,14-dione Chemical class N1C2=CC=CC=C2C(=O)C2=C1CC(C(=O)C1=CC=CC=C1N1)=C1C2 SNDAOXYSCAWUFQ-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical group C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims 1
- QZXFDVKEMLWZNW-UHFFFAOYSA-N cyclohexa-1,4-diene-1,4-dicarboxylic acid Chemical class OC(=O)C1=CCC(C(O)=O)=CC1 QZXFDVKEMLWZNW-UHFFFAOYSA-N 0.000 claims 1
- 239000000049 pigment Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical group C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LEWZOBYWGWKNCK-UHFFFAOYSA-N 2,3-dihydro-1h-inden-5-amine Chemical group NC1=CC=C2CCCC2=C1 LEWZOBYWGWKNCK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 1
- XGNXYCFREOZBOL-UHFFFAOYSA-N 1,3-benzodioxol-5-amine Chemical compound NC1=CC=C2OCOC2=C1 XGNXYCFREOZBOL-UHFFFAOYSA-N 0.000 description 1
- XHYQPEXIKXAQQU-UHFFFAOYSA-N 2,5-diaminocyclohexa-1,4-diene-1,4-dicarboxylic acid Chemical class NC1=C(C(O)=O)CC(N)=C(C(O)=O)C1 XHYQPEXIKXAQQU-UHFFFAOYSA-N 0.000 description 1
- YEIYQKSCDPOVNO-UHFFFAOYSA-N 5,8,9,12-tetrahydroquinolino[2,3-b]acridine-7,14-dione Chemical class N1C2=CC=CC=C2C(=O)C(C=C2N3)=C1C=C2C(=O)C1=C3C=CCC1 YEIYQKSCDPOVNO-UHFFFAOYSA-N 0.000 description 1
- CFRFHWQYWJMEJN-UHFFFAOYSA-N 9h-fluoren-2-amine Chemical compound C1=CC=C2C3=CC=C(N)C=C3CC2=C1 CFRFHWQYWJMEJN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PSLUFJFHTBIXMW-WYEYVKMPSA-N [(3r,4ar,5s,6s,6as,10s,10ar,10bs)-3-ethenyl-10,10b-dihydroxy-3,4a,7,7,10a-pentamethyl-1-oxo-6-(2-pyridin-2-ylethylcarbamoyloxy)-5,6,6a,8,9,10-hexahydro-2h-benzo[f]chromen-5-yl] acetate Chemical compound O([C@@H]1[C@@H]([C@]2(O[C@](C)(CC(=O)[C@]2(O)[C@@]2(C)[C@@H](O)CCC(C)(C)[C@@H]21)C=C)C)OC(=O)C)C(=O)NCCC1=CC=CC=N1 PSLUFJFHTBIXMW-WYEYVKMPSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0027—Crystal modifications; Special X-ray patterns of quinacridones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B48/00—Quinacridones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は、優れた赤色系の色相及
び鮮明度を有する顔料として有用な新規なアルファ型キ
ナクリドン誘導体及びその製造方法に関する。
【０００２】
【従来の技術】米国特許２８２１５２９号、同２８２１
５４１号、同３２８７４５７号及びドイツ特許１２５３
７０５号各明細書には、一般式（ＶＩ）のアルファ型キ
ナクリドン誘導体が次の方法で製造されることが開示さ
れている。
【０００３】
【化７】
（式中、Ｒ′は塩素原子、メチル基又は縮合しているベ
ンゼン環を表す）
【０００４】この一般式（ＶＩ）のアルファ型キナクリ
ドン誘導体は、米国特許２８４４４８５号及び２８４４
５８１号各明細書によれば、キシレン又はジメチルホル
ムアミド等の溶媒を使用して、ベータ型、ガンマ型、デ
ルタ型の結晶状態の異なる化合物に転換され、これらの
形態はＸ線回折により特定された。しかしながら、これ
らの誘導体は商業的には充分に望ましくないものであっ
た。
【０００５】
【発明が解決しようとする課題】本発明は、優れた赤色
系の色相と鮮明度を有する新規なアルファ型キナクリド
ン系顔料を提供するものである。
【０００６】
【課題を解決するための手段】本発明は、１又は２個の
環が縮合した一般式（Ｉ）のアルファ型キナクリドン誘
導体である。
【０００７】
【化８】
（式中、Ａ環はシクロペンタン環、１，３−ジオキソラ
ン環、インダン環又はＮ−アルキルインドリン環を表す
）
【０００８】Ａ環がシクロペンタン環の化合物はとくに
好ましい。インドリン環のＮ−置換基のアルキル基は、
メチル、エチル等があげられ、とくにエチルが好ましい
。
【０００９】一般式（Ｉ）のキナクリドン誘導体は、つ
ぎの反応式に示す方法により製造される。
【００１０】
【化９】
【００１１】上記、各反応を反応工程別に詳細に説明す
る。第一工程では、一般式 （ＩＩ） のジアルキル１
，４−ジシクロヘキサンジオン−２，５−ジカルボキシ
レートを窒素気流下でトルエン又はキシレンを溶媒とし
て使用し、トリフルオロ酢酸を触媒として使用し、一般
式（ＩＩＩ） の芳香族アミン誘導体と反応させ、一般
式（ＩＶ）のジアルキル２，５−ジアミノ−３，６−ジ
ヒドロテレフタレート誘導体を製造する。
【００１２】このとき使用する一般式（ＩＩＩ） の芳
香族アミン誘導体は、５−アミノインダン、３，４−（
メチレンジオキシ）アニリン、２−アミノフルオレン、
又は３−アミノ−９−アルキルカルバゾールである。
【００１３】第二工程では、一般式（ＩＶ）の化合物を
。高沸点（２５０°〜２５７℃）のビフェニル２３．５
％とジフェニルエーテル７６．５％の混合溶液からなる
公知のＤｏｗｔｈｅｒｍ Ａを溶媒として使用し、窒素
気流下で加熱反応させ、一般式（Ｖ） の６，１３−ジ
ヒドロキナクリドン誘導体を得る。好ましくは２５０〜
２５７℃で反応させる。
【００１４】第三工程では、一般式（Ｖ）の６，１３−
ジヒドロキナクリドン誘導体を、エタノール、水及び水
酸化ナトリウム溶液とメタ−ニトロベンゼンスルホン酸
アルカリ金属（例えばナトリウム塩）を使用して酸化し
、一般式（Ｉ）のアルファ型キナクリドン系誘導体を製
造する。
【００１５】
【実施例】以下の実施例により、本発明をより詳細に説
明する。実施例中で部は重量部を意味する。
【００１６】実施例１（第一工程）
【化１０】
【００１７】５００ｍｌの３口の円底フラスコに温度計
、還流冷却器及びディーンスターク噴流管を装着し、ト
ルエン１５０部を加え、窒素ガスを通過させながらジエ
チル１，４−ジシクロヘキサンジオン−２，５−ジカル
ボキシレート２５．６部（０．１ｍｏｌ ）を反応槽に
加えた後、加熱し溶解した。継続して５−アミノインダ
ン２８部を加えて溶解し、触媒としてトリフルオロ酢酸
０．５部を加えた後、加熱還流させた。このとき生成す
る水はディーンスターク噴流管を使用して除去した。２
時間後に窒素ガスを通過させながら反応物を徐々に冷却
し、メチルアルコール２００部を加えた後ろ過し、目的
の化合物４５部（９２．６％）を得た。
【００１８】１Ｈ−ＮＭＲ：δ（ＣＤＣｌ３ ）、７．
０１（ｍ，６Ｈ）、４．１０（ｑ，４Ｈ）、３．４０（
ｓ，４Ｈ）、２．２６（ｔ，８Ｈ）、２．１８（ｍ，４
Ｈ）、１．２３（ｔ，６Ｈ）
【００１９】実施例２〜４
実施例１の方法に準じて表１の一般式（ＩＶ）に含まれ
る化合物を製造した。
【００２０】
【表１】
【００２１】実施例５（第二工程）
【化１１】
【００２２】５００ｍｌの３口の円底フラスコに、還流
冷却器を装着し、実施例１で得た化合物４５部を加え、
窒素ガスを通過させながら高沸点のビフェニルとジフェ
ニルエーテル混合溶液２７０部を加えた後、２５０〜２
５５℃で加熱した。同温度で１．５〜２時間撹拌した後
、反応物を窒素ガスを通過させながら冷却した。これに
エタノール２００部を加えた後ろ過し、目的の化合物２
８．５部（７８％）を得た。
【００２３】１Ｈ−ＮＭＲ：δ（ＣＦ３ ＣＯ２ Ｄ）
．７８．１（ｓ，４Ｈ）、５．６９（ｓ，４Ｈ）、３．
６６（ｍ，２Ｈ）、３．２０（ｍ，６Ｈ）、２．３１（
ｍ，４Ｈ）
【００２４】実施例６〜８
実施例５の方法に準じて表２の一般式（Ｖ） に含まれ
る化合物を製造した。
【００２５】
【表２】
【００２６】実施例９（第三工程）
【化１２】
【００２７】５００ｍｌの３口の円底フラスコに還流冷
却器を装着し、実施例５で得た化合物１０部を加え、エ
タノール２００ｍｌと水２５ｍｌに水酸化ナトリウム４
部を溶解した溶液を加えた後、室温で２０分間撹拌した
。これにメタ−ニトロベンゼンスルホン酸ナトリウム塩
２０部を粉末状態で加えた後、加熱還流した。反応時間
は３時間を要した。反応物を３時間後冷却しながら水２
００部を加え、数分撹拌後ろ過し、明赤色を帯びた目的
の化合物９．５部（９５％）を得た。またこの化合物の
Ｘ線粉末回折法によるデータは表３のとおりである。
【００２８】
【表３】
【００２９】実施例１０〜１２
実施例９の方法に準じて表４の一般式（Ｉ）に含まれる
化合物を製造した。またこれらの化合物のＸ線粉末回折
法によるデータは表５〜表７のとおりである。
【００３０】
【表４】
【００３１】
【表５】
【００３２】
【表６】
【００３３】
【表７】
【００３４】
【発明の効果】本発明のアルファ型キナクリドン誘導体
（Ｉ）は、優れた赤色系の色相及び鮮明度を有する顔料
としては有用である。Description: [0001] The present invention relates to a novel alpha-type quinacridone derivative useful as a pigment having excellent red hue and sharpness, and a method for producing the same. [Prior Art] US Pat. Nos. 2,821,529 and 2,821
No. 541, No. 3287457 and German Patent No. 1253
Each specification of No. 705 discloses that the alpha-type quinacridone derivative of general formula (VI) is produced by the following method. ##STR7## (In the formula, R' represents a chlorine atom, a methyl group, or a fused benzene ring.) This alpha-type quinacridone derivative of general formula (VI) is disclosed in US Pat. No. 2,844,485 and 2844
According to the specifications of No. 581, it was converted into compounds with different crystal states of beta type, gamma type, and delta type using a solvent such as xylene or dimethylformamide, and these forms were identified by X-ray diffraction. . However, these derivatives have been highly undesirable commercially. OBJECTS OF THE INVENTION The present invention provides a novel alpha-quinacridone pigment having excellent red hue and sharpness. [0006] The present invention is an alpha-type quinacridone derivative of the general formula (I) in which one or two rings are condensed. [0007] (In the formula, ring A represents a cyclopentane ring, 1,3-dioxolane ring, indane ring or N-alkylindoline ring) Compounds in which ring A is a cyclopentane ring are particularly preferred. . The alkyl group of the N-substituent of the indoline ring is
Examples include methyl and ethyl, with ethyl being particularly preferred. The quinacridone derivative of general formula (I) is produced by the method shown in the following reaction formula. ##STR9## Each of the above reactions will be explained in detail for each reaction step. In the first step, dialkyl 1 of general formula (II)
, 4-dicyclohexanedione-2,5-dicarboxylate is reacted with an aromatic amine derivative of general formula (III) under a nitrogen stream using toluene or xylene as a solvent and trifluoroacetic acid as a catalyst. , a dialkyl 2,5-diamino-3,6-dihydroterephthalate derivative of general formula (IV) is prepared. The aromatic amine derivative of general formula (III) used at this time is 5-aminoindan, 3,4-(
methylenedioxy)aniline, 2-aminofluorene,
or 3-amino-9-alkylcarbazole. In the second step, a compound of general formula (IV) is prepared. Biphenyl 23.5 with high boiling point (250° to 257°C)
Dowtherm A, which is a mixture of 76.5% and 76.5% of diphenyl ether, is used as a solvent, and the reaction is carried out by heating under a nitrogen stream to obtain a 6,13-dihydroquinacridone derivative of the general formula (V). Preferably 250~
React at 257°C. In the third step, 6,13- of general formula (V)
A dihydroquinacridone derivative is oxidized using ethanol, water, a sodium hydroxide solution, and an alkali metal meta-nitrobenzenesulfonate (eg, sodium salt) to produce an alpha-quinacridone derivative of general formula (I). EXAMPLES The present invention will be explained in more detail with the following examples. In the examples, parts mean parts by weight. Example 1 (first step) [Chemical formula 10] A 500 ml three-neck round bottom flask was equipped with a thermometer, a reflux condenser and a Dean-Stark jet tube, 150 parts of toluene was added, and nitrogen gas was added. 25.6 parts (0.1 mol) of diethyl 1,4-dicyclohexanedione-2,5-dicarboxylate was added to the reaction tank while passing through the reactor, and then heated and dissolved. Continuously, 28 parts of 5-aminoindan was added and dissolved, and after adding 0.5 part of trifluoroacetic acid as a catalyst, the mixture was heated to reflux. The water produced at this time was removed using a Dean-Stark jet tube. 2
After a period of time, the reaction mixture was gradually cooled while passing nitrogen gas, 200 parts of methyl alcohol was added, and the mixture was filtered to obtain 45 parts (92.6%) of the target compound. 1H-NMR: δ(CDCl3), 7.
01 (m, 6H), 4.10 (q, 4H), 3.40 (
s, 4H), 2.26 (t, 8H), 2.18 (m, 4
H), 1.23(t,6H) Examples 2 to 4 Compounds included in the general formula (IV) in Table 1 were produced according to the method of Example 1. [Table 1] Example 5 (Second Step) [Chemical Formula 11] A 500 ml three-neck round bottom flask was equipped with a reflux condenser, and the compound 45 obtained in Example 1 was prepared. add part,
After adding 270 parts of a high boiling point mixed solution of biphenyl and diphenyl ether while passing nitrogen gas,
Heated at 55°C. After stirring at the same temperature for 1.5-2 hours, the reaction mixture was cooled while passing nitrogen gas through it. After adding 200 parts of ethanol to this, it was filtered to obtain the desired compound 2.
8.5 parts (78%) were obtained. 1H-NMR: δ(CF3 CO2 D)
．． 78.1 (s, 4H), 5.69 (s, 4H), 3.
66 (m, 2H), 3.20 (m, 6H), 2.31 (
m, 4H) Examples 6 to 8 Compounds included in the general formula (V) in Table 2 were produced according to the method of Example 5. [Table 2] Example 9 (Third step) [Chemical formula 12] A 500 ml three-neck round bottom flask was equipped with a reflux condenser, and 10 parts of the compound obtained in Example 5 was added. Add 4 ml of sodium hydroxide to 200 ml of ethanol and 25 ml of water.
After adding a solution in which 1 part was dissolved, the mixture was stirred at room temperature for 20 minutes. After adding 20 parts of meta-nitrobenzenesulfonic acid sodium salt in powder form to the mixture, the mixture was heated under reflux. The reaction time required 3 hours. After 3 hours, the reaction mixture was cooled with 2 ml of water.
00 parts were added, stirred for several minutes, and filtered to obtain 9.5 parts (95%) of the target compound with a bright red color. Further, data of this compound obtained by X-ray powder diffraction method are shown in Table 3. [0028] [Table 3] [0029] Examples 10 to 12 Compounds included in the general formula (I) in Table 4 were produced according to the method of Example 9. Moreover, the data of these compounds by X-ray powder diffraction method are as shown in Tables 5 to 7. [Table 4] [Table 5] [Table 5] [Table 6] [Table 7] [Effects of the Invention] The alpha-type quinacridone derivative (I) of the present invention has excellent It is useful as a pigment having a red hue and sharpness.
Claims (4)
キナクリドン誘導体。 【化１】 （式中、Ａ環はシクロペンタン環、１，３−ジオキソラ
ン環、インダン環又はＮ−アルキルインドリン環を表す
）1. An alpha-type quinacridone derivative represented by general formula (I). [Formula 1] (wherein, ring A represents a cyclopentane ring, 1,3-dioxolane ring, indane ring or N-alkylindoline ring)
ジシクロヘキサンジオン−２，５−ジカルボキシレート
と一般式（ＩＩＩ） の芳香族アミン誘導体とを反応さ
せて、一般式（ＩＶ）のジアルキル２，５−ジアミノ−
３，６−ジヒドロテレフタレート誘導体を製造する第一
工程と、【化２】 （式中、Ｒは低級アルキル基を表す） 【化３】 （式中、Ａ環はシクロペンタン環、１，３−ジオキソラ
ン環、インダン環又はＮ−アルキルインドリン環を表す
） 【化４】 （式中、Ｒ及びＡ環は前述と同じ） 一般式（ＩＶ）の化合物を加熱反応させて一般式（Ｖ）
の６，１３−ジヒドロキナクリドン誘導体を製造する
第二工程と、 【化５】 （式中、Ａ環は前述と同じ） 一般式 （Ｖ）の化合物をメタ−ニトロベンゼンスルホ
ン酸アルカリ金属塩と反応させて、一般式（Ｉ） のア
ルファ型キナクリドリン誘導体を製造する第三工程、と
からなるキナクリドン誘導体の製造方法。 【化６】 （式中、Ａ環は前述と同じ）Claim 2: Dialkyl 1,4- of general formula (II)
Dicyclohexanedione-2,5-dicarboxylate and the aromatic amine derivative of general formula (III) are reacted to form a dialkyl 2,5-diamino-
The first step of producing a 3,6-dihydroterephthalate derivative, dioxolane ring, indane ring or N-alkylindoline ring) [Formula 4] (In the formula, R and A rings are the same as above) A compound of general formula (IV) is heated and reacted to form general formula (V)
A second step of producing a 6,13-dihydroquinacridone derivative of formula (V) (in which ring A is the same as above) is reacted with an alkali metal salt of meta-nitrobenzenesulfonic acid. and a third step of producing an alpha-type quinacridine derivative of general formula (I). [Chemical formula 6] (In the formula, ring A is the same as above)
触媒として用いる請求項２の製造方法。3. The production method according to claim 2, wherein trifluoroacetic acid is used as a catalyst in the first step.
して用いる請求項２の製造方法。4. The production method according to claim 2, wherein Dowram A is used as a solvent in the second step.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900015291A KR930010503B1 (en) | 1990-09-26 | 1990-09-26 | New alpha-tape quinacridone derivatives and preparation thereof |
| KR15291/1990 | 1990-09-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04224579A true JPH04224579A (en) | 1992-08-13 |
| JPH0647590B2 JPH0647590B2 (en) | 1994-06-22 |
Family
ID=19304016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3089276A Expired - Lifetime JPH0647590B2 (en) | 1990-09-26 | 1991-03-29 | Alpha-type quinacridone derivative and method for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH0647590B2 (en) |
| KR (1) | KR930010503B1 (en) |
| CH (1) | CH682077A5 (en) |
| DE (1) | DE4119100C2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003062237A1 (en) * | 2002-01-18 | 2003-07-31 | Hirose Engineering Co., Ltd. | White light emitting compound, white light emission illuminator, and white light emission organic el device |
| CN107057054A (en) * | 2016-12-14 | 2017-08-18 | 江苏丽王科技股份有限公司 | One class quinacridone polyether derivative and its preparation method and application |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3055365B2 (en) * | 1993-06-30 | 2000-06-26 | 東洋インキ製造株式会社 | Process for producing dialkyl 2,5-di (arylamino) -3,6-dihydroterephthalate and process for producing quinacridone using the same as an intermediate |
| US5868828A (en) * | 1998-05-20 | 1999-02-09 | Bayer Corporation | Heterocyclic-substituted quinacridone pigments |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2821529A (en) * | 1955-07-22 | 1958-01-28 | Du Pont | Process for the preparation of linear quinacridones |
| US2844485A (en) * | 1955-07-22 | 1958-07-22 | Du Pont | Organic pigments |
| US2821541A (en) * | 1955-07-22 | 1958-01-28 | Du Pont | Production of dialkyl 2, 5-diarylamino-3, 6-dihydroterephthalates |
| US2844581A (en) * | 1957-11-22 | 1958-07-22 | Du Pont | Organic pigments |
| US3287457A (en) * | 1964-01-10 | 1966-11-22 | Du Pont | Process for manufacturing beta phase quinacridone |
| DE2148866C3 (en) * | 1971-09-30 | 1974-05-30 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Quinacridone pigment mixtures and processes for their preparation |
-
1990
- 1990-09-26 KR KR1019900015291A patent/KR930010503B1/en not_active IP Right Cessation
-
1991
- 1991-01-22 CH CH193/91A patent/CH682077A5/de not_active IP Right Cessation
- 1991-03-29 JP JP3089276A patent/JPH0647590B2/en not_active Expired - Lifetime
- 1991-06-10 DE DE4119100A patent/DE4119100C2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003062237A1 (en) * | 2002-01-18 | 2003-07-31 | Hirose Engineering Co., Ltd. | White light emitting compound, white light emission illuminator, and white light emission organic el device |
| CN107057054A (en) * | 2016-12-14 | 2017-08-18 | 江苏丽王科技股份有限公司 | One class quinacridone polyether derivative and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| KR930010503B1 (en) | 1993-10-25 |
| JPH0647590B2 (en) | 1994-06-22 |
| DE4119100A1 (en) | 1992-04-02 |
| CH682077A5 (en) | 1993-07-15 |
| DE4119100C2 (en) | 1996-12-19 |
| KR920006447A (en) | 1992-04-27 |
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