JPH04338583A - Leuco dye - Google Patents
Leuco dyeInfo
- Publication number
- JPH04338583A JPH04338583A JP3138467A JP13846791A JPH04338583A JP H04338583 A JPH04338583 A JP H04338583A JP 3138467 A JP3138467 A JP 3138467A JP 13846791 A JP13846791 A JP 13846791A JP H04338583 A JPH04338583 A JP H04338583A
- Authority
- JP
- Japan
- Prior art keywords
- group
- lower alkyl
- alkyl group
- formula
- leuco dye
- 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
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract description 27
- -1 butadiene compound Chemical class 0.000 abstract description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000000975 dye Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000005711 Benzoic acid Substances 0.000 description 7
- 235000010233 benzoic acid Nutrition 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MIKRFDVUQPMQEK-UHFFFAOYSA-N 1-methoxy-4-[1-(4-methoxyphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(OC)=CC=C1C(=CC=C)C1=CC=C(OC)C=C1 MIKRFDVUQPMQEK-UHFFFAOYSA-N 0.000 description 1
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 235000019646 color tone Nutrition 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
- Color Printing (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は新規な画像形成用ロイコ
染料に関し、特に感熱記録や感圧記録における近赤外吸
収ロイコ染料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel leuco dye for image formation, and more particularly to a near-infrared absorbing leuco dye for heat-sensitive recording and pressure-sensitive recording.
【０００２】0002
【従来技術】感圧記録や感熱記録に一般に利用されるロ
イコ染料は、トリフェニルメタン系、フルオラン系がメ
インである。しかしながらこれらの染料は色調即ち可視
領域の吸収を目的として使われるものが多く、７００〜
９００ｎｍの近赤外領域に吸収を有さないものがほとん
どである。一方、近年、半導体レーザーへの普及が広ま
るにつれ、バーコード等の記録画像をこれらを光源とし
たスキャナーで読み取る方式がＦＡ分野を中心に顕著に
なってきた。BACKGROUND OF THE INVENTION Leuco dyes commonly used for pressure-sensitive recording and heat-sensitive recording are mainly triphenylmethane-based and fluoran-based dyes. However, many of these dyes are used for the purpose of absorbing color tones, that is, in the visible region, and are
Most of them do not have absorption in the near-infrared region of 900 nm. On the other hand, in recent years, as semiconductor lasers have become more popular, methods of reading recorded images such as barcodes with scanners using these as light sources have become prominent mainly in the FA field.
【０００３】こうした事態に対応する為、近赤外領域に
吸収を有するロイコ染料として特開昭６２−２４３６５
３号、特開昭６３−３７１５８号、特開昭６１−１６５
３８０号、特開昭５９−１９９７５７号、特開平２−１
３８３６８号にみられるような、近赤外領域に吸収を有
するロイコ染料がいくつか開示されている。[0003] In order to cope with this situation, Japanese Patent Application Laid-Open No. 62-24365 has been developed as a leuco dye that absorbs in the near-infrared region.
No. 3, JP-A-63-37158, JP-A-61-165
No. 380, JP-A-59-199757, JP-A-2-1
Several leuco dyes having absorption in the near-infrared region have been disclosed, such as those found in US Pat.
【０００４】これら開示されている化合物は、近赤外領
域に吸収を有する様にする為に置換フェニル基を２つ有
するエチレン化合物やブタジエン化合物を原料として染
料を合成する必要があり、これらは工業的には特別な化
合物を原料として使うため、高価になるといった不具合
がある。[0004] In order for these disclosed compounds to have absorption in the near-infrared region, it is necessary to synthesize dyes using ethylene compounds or butadiene compounds having two substituted phenyl groups as raw materials, and these are industrially difficult to obtain. However, because it uses special compounds as raw materials, it has the disadvantage of being expensive.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、近赤外領域
に強い吸収能を有するとともに、原料として比較的工業
的に汎用なブチジエン化合物を利用し得るロイコ染料を
提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a leuco dye which has a strong absorption ability in the near-infrared region and which can use a relatively industrially-common butidiene compound as a raw material. .
【０００６】[0006]
【課題を解決するための手段】本発明によれば、下記化
１及び化２で表わされるロイコ染料が提供される。According to the present invention, leuco dyes represented by the following chemical formulas 1 and 2 are provided.
【化１】
Ｒ１，Ｒ２：低級アルキル基
Ｒ３：水素原子、低級アルキル基、低級アルコキシ基Ｘ
１：ジアルキルアミノフェニル基
Ｙ１：水素原子、低級アルキル基
Ａ：ベンゼン環、ナフタレン環[Formula 1] R1, R2: Lower alkyl group R3: Hydrogen atom, lower alkyl group, lower alkoxy group X
1: dialkylaminophenyl group Y1: hydrogen atom, lower alkyl group A: benzene ring, naphthalene ring
【化２】
Ｒ１，Ｒ２：低級アルキル基
Ｒ３：水素原子、低級アルキル基、低級アルコキシ基Ｘ
２：低級アルコキシル基で置換されていてもよいフェニ
ル基
Ｙ２：低級アルキル基、前記したＸ２
Ａ：ベンゼン環、ナフタレン環[Formula 2] R1, R2: Lower alkyl group R3: Hydrogen atom, lower alkyl group, lower alkoxy group X
2: Phenyl group optionally substituted with lower alkoxyl group Y2: Lower alkyl group, X2 described above A: Benzene ring, naphthalene ring
【００
０７】本発明の前記化１で表わされるロイコ染料は、次
の表１に示す反応式に従って容易に合成することができ
る。00
The leuco dye represented by formula 1 of the present invention can be easily synthesized according to the reaction formula shown in Table 1 below.
【表１】[Table 1]
【０００８】又、本発明の前記化２で表わされるロイコ
染料も、前記表１に示す反応式において原料のブタジエ
ン化合物に対応するブタジエン化合物（Ｘ１がＸ２、Ｙ
１がＹ２に置き換ったもの）を使用することにより、化
１で表わされるロイコ染料と同様にして、容易に合成す
ることができる。In addition, the leuco dye represented by the above formula 2 of the present invention is also a butadiene compound (X1 is X2, Y
1 is replaced with Y2), it can be easily synthesized in the same manner as the leuco dye represented by chemical formula 1.
【０００９】即ち、本発明のロイコ染料は、原料として
工業的に汎用されている置換基がＸ１，Ｙ１或いはＸ２
，Ｙ２であるブタジエン化合物を利用することができる
ため、極めて安価に製造することができる。That is, the leuco dye of the present invention has substituents commonly used industrially as raw materials such as X1, Y1 or X2.
, Y2, it can be produced at extremely low cost.
【００１０】本発明のロイコ染料は、前記反応式に従っ
て、ケトン誘導体とブタジエン化合物とを、脱水縮合剤
の存在下、脱水縮合させることにより容易に合成できる
。この場合、脱水縮合剤としては、無水酢酸、無水プロ
ピオン酸、オキシ塩化リン、硫酸、ポリリン酸等が用い
られる。The leuco dye of the present invention can be easily synthesized by dehydrating and condensing a ketone derivative and a butadiene compound in the presence of a dehydrating condensing agent according to the above reaction formula. In this case, as the dehydration condensation agent, acetic anhydride, propionic anhydride, phosphorus oxychloride, sulfuric acid, polyphosphoric acid, etc. are used.
【００１１】前記化１及び化２で表わされる本発明のロ
イコ染料において、Ｒ１，Ｒ２の具体例としては、メチ
ル基、エチル基、プロピル基、イソプロピル基、ブチル
基等の低級アルキル基が挙げられる。Ｒ３の具体例とし
ては、水素原子、メチル基、エチル基、イソプロピル基
、ブチル基等の低級アルキル基；メトキシ基、エトキシ
基、プロポキシ基、イソプロポキシ基等の低級アルコキ
シ基が挙げられる。In the leuco dyes of the present invention represented by Chemical Formulas 1 and 2, specific examples of R1 and R2 include lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, and butyl group. . Specific examples of R3 include hydrogen atoms, lower alkyl groups such as methyl, ethyl, isopropyl and butyl; lower alkoxy groups such as methoxy, ethoxy, propoxy and isopropoxy.
【００１２】前記化１で表わされる本発明のロイコ染料
において、Ｘ１の具体例としてはＰ−ジメチルアミノフ
ェニル基、Ｐ−ジエチルアミノフェニル基、Ｐ−ジプロ
ピルアミノフェニル基、Ｐ−ジブチルアミノフェニル基
等が挙げられる。更に、Ｙ１の具体例としては、水素原
子、メチル基、エチル基、プロピル基、イソプロピル基
、ブチル基等の低級アルキル基が挙げられる。In the leuco dye of the present invention represented by the above formula 1, specific examples of X1 include P-dimethylaminophenyl group, P-diethylaminophenyl group, P-dipropylaminophenyl group, P-dibutylaminophenyl group, etc. can be mentioned. Further, specific examples of Y1 include a hydrogen atom and a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
【００１３】前記化２で表わされる本発明のロイコ染料
において、Ｘ２の具体例としては４−メトキシフェニル
基、４−エトキシフェニル基、４−ブトキシフェニル基
、２，４−ジメトキシフェニル基、２，４−ジエトキシ
フェニル基、３，４−ジメトキシフェニル基、３，４−
ジエトキシフェニル基、３，４，５−トリメトキシフェ
ニル基等が挙げられる。更にＹ２の具体例としては、メ
チル基、エチル基、プロピル基、イソプロピル基、ブチ
ル基等の低級アルキル基、又は前記Ｘ２と同じ基が挙げ
られる。In the leuco dye of the present invention represented by formula 2, specific examples of X2 include 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-butoxyphenyl group, 2,4-dimethoxyphenyl group, 2, 4-diethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,4-
Examples include diethoxyphenyl group and 3,4,5-trimethoxyphenyl group. Furthermore, specific examples of Y2 include lower alkyl groups such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, or the same group as the above-mentioned X2.
【００１４】本発明の前記化１で表わされるロイコ染料
の具体例としては、次の表２に示されるものが挙げられ
るが、必ずしもこれらに限定されるものではない。Specific examples of the leuco dye represented by formula 1 of the present invention include those shown in Table 2 below, but are not necessarily limited thereto.
【００１５】[0015]
【表２−（１）】[Table 2-(1)]
【表２−（２）】[Table 2-(2)]
【００１６】本発明の前記化２で表わされるロイコ染料
の具体例としては、次の表３に示されるものが挙げられ
るが必ずしもこれらの限定されるものではない。Specific examples of the leuco dye represented by formula 2 of the present invention include those shown in Table 3 below, but are not necessarily limited to these.
【００１７】[0017]
【表３−（１）】[Table 3-(1)]
【表３−（２）】[Table 3-(2)]
【００１８】[0018]
【実施例】以下に本発明を実施例により更に詳細に説明
する。[Examples] The present invention will be explained in more detail below using examples.
【００１９】
実施例１〔表２の具体例Ｎｏ．（１）の合成〕２−（４
′−ジエチルアミノ−２′−メトキシベンゾイル）安息
香酸３．５ｇと１−（４′−ジメチルアミノフェニル）
−１，３−ブタジエン１．７ｇに無水酢酸２０ｍｌを加
え更にアセトン５０ｍｌを加え３時間還流する。冷却後
アセトンを留去し、残渣を水１００ｍｌに投入し、水酸
化ナトリウム水溶液で中和し、析出物を濾取する。次に
この析出物をメタノールで再結晶して、淡黄色の固体を
採取した。得量２．９ｇ、融点９０〜９３℃、酢酸中で
の極大吸収波長８００ｎｍであった。Example 1 [Specific example No. in Table 2] Synthesis of (1)]2-(4
3.5 g of '-diethylamino-2'-methoxybenzoyl)benzoic acid and 1-(4'-dimethylaminophenyl)
Add 20 ml of acetic anhydride to 1.7 g of -1,3-butadiene, add 50 ml of acetone, and reflux for 3 hours. After cooling, acetone is distilled off, the residue is poured into 100 ml of water, neutralized with an aqueous sodium hydroxide solution, and the precipitate is collected by filtration. Next, this precipitate was recrystallized with methanol to collect a pale yellow solid. The yield was 2.9 g, the melting point was 90-93°C, and the maximum absorption wavelength in acetic acid was 800 nm.
【００２０】
実施例２〔表２の具体例Ｎｏ．（６）の合成〕２−（４
′−ジブチルアミノ−２′−メトキシベンゾイル）安息
香酸４．０ｇと１−（４′−ジメチルアミノフェニル）
−１，３−ブタジエン１．７ｇに無水酢酸２０ｍｌを加
え、更にアセトン５０ｍｌを加え３時間還流する。冷却
後アセトンを留去し、残渣を水１５０ｍｌに投入し、水
酸化ナトリウム水溶液で中和し、析出物を濾取する。次
にこの析出物をメタノールで再結晶して淡黄色の固体を
採取した。得量３．１ｇ、融点８３〜８５℃、酢酸中で
の極大吸収波長は８００ｎｍであった。Example 2 [Specific example No. in Table 2] Synthesis of (6)]2-(4
4.0 g of '-dibutylamino-2'-methoxybenzoyl)benzoic acid and 1-(4'-dimethylaminophenyl)
Add 20 ml of acetic anhydride to 1.7 g of -1,3-butadiene, then add 50 ml of acetone and reflux for 3 hours. After cooling, acetone is distilled off, the residue is poured into 150 ml of water, neutralized with an aqueous sodium hydroxide solution, and the precipitate is collected by filtration. Next, this precipitate was recrystallized with methanol to collect a pale yellow solid. The yield was 3.1 g, the melting point was 83-85°C, and the maximum absorption wavelength in acetic acid was 800 nm.
【００２１】
実施例３〔表２の具体例Ｎｏ．（２）の合成〕２−（４
′−ジエチルアミノ−２′−メトキシベンゾイル）安息
香酸３．８ｇと２−（４′−ジメチルアミノフェニル）
−２，４−ペンタジエン１．８ｇに無水酢酸１０ｍｌを
加え、１２０℃で２時間反応させる。冷却後５％ＮａＯ
Ｈ水溶液２００ｍｌに投入、撹拌し析出物を濾取する。
次にこれをシリカゲル（ワコーゲルＣ２００）を用い、
トルエン／酢酸エチル＝６／１を展開液としてカラムク
ロマト精製を行ない、赤紫色固体を採取した。
得量１．５ｇ、このものの融点は１１０〜１１５℃、酢
酸中での極大吸収波長は８３２ｎｍであった。Example 3 [Specific example No. in Table 2] Synthesis of (2)] 2-(4
3.8 g of '-diethylamino-2'-methoxybenzoyl)benzoic acid and 2-(4'-dimethylaminophenyl)
10 ml of acetic anhydride is added to 1.8 g of -2,4-pentadiene, and the mixture is reacted at 120°C for 2 hours. 5% NaO after cooling
The mixture was poured into 200 ml of H aqueous solution, stirred, and the precipitate was collected by filtration. Next, use silica gel (Wako Gel C200) to
Column chromatography purification was performed using toluene/ethyl acetate = 6/1 as a developing solution, and a reddish-purple solid was collected. The yield was 1.5 g, the melting point of this product was 110-115°C, and the maximum absorption wavelength in acetic acid was 832 nm.
【００２２】
実施例４〔表３の具体例Ｎｏ．（１）の合成〕２−（４
′−ジエチルアミノ−２′−メトキシベンゾイル）安息
香酸６．７ｇと１，１−ビス（４′−メトキシフェニル
）−１，３−ブタジエン４．５ｇに無水酢酸５０ｍｌを
加え、１００℃で２時間反応させる。冷却後５％ＮａＯ
Ｈ水溶液３００ｍｌに投入、撹拌し析出物を濾取する。
次にこの析出物をトルエン１００ｍｌに溶解し、更に１
０％ＮａＯＨ水溶液５０ｍｌを加え、１時間加熱撹拌す
る。冷却後、有機層を分取し、無水硫酸ナトリウムで乾
燥した後、トルエンを留去してピンク色の固体を採取し
た。得量７．０ｇ、このものの融点は７５〜８０℃、酢
酸中での極大吸収波長は６３５ｎｍであった。Example 4 [Specific example No. in Table 3] Synthesis of (1)]2-(4
50 ml of acetic anhydride was added to 6.7 g of '-diethylamino-2'-methoxybenzoyl)benzoic acid and 4.5 g of 1,1-bis(4'-methoxyphenyl)-1,3-butadiene, and the mixture was reacted at 100°C for 2 hours. let 5% NaO after cooling
The mixture was poured into 300 ml of H aqueous solution, stirred, and the precipitate was collected by filtration. Next, this precipitate was dissolved in 100 ml of toluene, and
Add 50 ml of 0% NaOH aqueous solution, and heat and stir for 1 hour. After cooling, the organic layer was separated, dried over anhydrous sodium sulfate, and the toluene was distilled off to collect a pink solid. The yield was 7.0 g, the melting point of this product was 75-80°C, and the maximum absorption wavelength in acetic acid was 635 nm.
【００２３】
実施例５〔表３の具体例Ｎｏ．（３）の合成〕２−（４
′−ジエチルアミノ−２′−メトキシベンゾイル）安息
香酸６．３ｇと、１−（４′−メトキシフェニル）−１
−フェニル−１，３−ブタジエン３．７ｇに無水酢酸５
０ｍｌを加え、１００℃で１時間反応させる。
冷却後、５％ＮａＯＨ水溶液２００ｍｌに投入、撹拌し
、析出物を濾取する。次にこれをシリカゲル（ワコーゲ
ルＣ２００）を用い、トルエン／酢酸エチルに８／１の
展開液でカラムクロマト精製を行ない、黄色固体を１．
０ｇ採取した。このものの融点は６０〜６５℃、酢酸中
での極大吸収波長は６００ｎｍであった。Example 5 [Specific example No. in Table 3] Synthesis of (3)]2-(4
6.3 g of '-diethylamino-2'-methoxybenzoyl)benzoic acid and 1-(4'-methoxyphenyl)-1
- 3.7 g of phenyl-1,3-butadiene and 5 ml of acetic anhydride
Add 0 ml and react at 100°C for 1 hour. After cooling, the mixture was poured into 200 ml of 5% NaOH aqueous solution, stirred, and the precipitate was collected by filtration. Next, this was purified by column chromatography using silica gel (Wako Gel C200) with a developing solution of 8/1 in toluene/ethyl acetate to obtain a yellow solid of 1.
0g was collected. The melting point of this product was 60 to 65°C, and the maximum absorption wavelength in acetic acid was 600 nm.
【００２４】
実施例６〔表３の具体例Ｎｏ．（５）の合成〕２−（４
′−ジエチルアミノ−２′−メトキシベンゾイル）安息
香酸７．６ｇと２−（４′−メトキシフェニル）−２，
４−ペンタジエン３．４ｇと無水酢酸２０ｍｌ、更にＤ
ＭＦ１００ｍｌを加え、２時間還流する。冷却後５％Ｎ
ａＯＨ水溶液５００ｍｌに投入、撹拌し析出する粘稠物
をデカンテーションにより採取する。次に、これをシリ
カゲル（ワコーゲルＣ２００）を用い、トルエン／酢酸
エチル＝６／１の展開液でカラムクロマト精製を行ない
淡ピンク色固体２．０ｇを採取した。このものの融点は
９３〜１００℃、酢酸中での極大吸収波長は６９０ｎｍ
であった。Example 6 [Specific example No. in Table 3] Synthesis of (5)]2-(4
7.6 g of '-diethylamino-2'-methoxybenzoyl)benzoic acid and 2-(4'-methoxyphenyl)-2,
3.4 g of 4-pentadiene and 20 ml of acetic anhydride, plus D
Add 100 ml of MF and reflux for 2 hours. 5% N after cooling
Pour into 500 ml of aOH aqueous solution, stir, and collect the precipitated viscous substance by decantation. Next, this was purified by column chromatography using silica gel (Wako Gel C200) and a developing solution of toluene/ethyl acetate = 6/1, and 2.0 g of a pale pink solid was collected. The melting point of this substance is 93-100℃, and the maximum absorption wavelength in acetic acid is 690 nm.
Met.
【００２５】
実施例７〔表３の具体例Ｎｏ．（７）の合成〕２−（４
′−ジエチルアミノ−２′−メトキシベンゾイル）安息
香酸５．７ｇと１−（２′，４′−ジメトキシフェニル
）−１−フェニル−１，３−ブタジエン４．２ｇに無水
酢酸１００ｍｌを加え、９０℃で４時間反応させる。冷
却後、１０％ＮａＯＨ水溶液３００ｍｌに投入撹拌し、
析出する粘稠物をデカンテーションにより採取する。次
に、これをシリカゲル（ワコーゲルＣ−２００）を用い
トルエン／酢酸エチル＝８／１の展開液でカラムクロマ
ト精製を行ない、赤茶色の固体２．０ｇを採取した。こ
のものの融点は６０〜６５℃、酢酸中での極大吸収波長
は５８０ｎｍであった。Example 7 [Specific example No. in Table 3] Synthesis of (7)]2-(4
100 ml of acetic anhydride was added to 5.7 g of '-diethylamino-2'-methoxybenzoyl)benzoic acid and 4.2 g of 1-(2',4'-dimethoxyphenyl)-1-phenyl-1,3-butadiene, and the mixture was heated at 90°C. Let it react for 4 hours. After cooling, it was poured into 300 ml of 10% NaOH aqueous solution and stirred.
Collect the precipitated viscous material by decantation. Next, this was purified by column chromatography using silica gel (Wako Gel C-200) with a developing solution of toluene/ethyl acetate = 8/1, and 2.0 g of a reddish-brown solid was collected. The melting point of this product was 60 to 65°C, and the maximum absorption wavelength in acetic acid was 580 nm.
【００２６】[0026]
【発明の効果】本発明のロイコ染料は、近赤外領域に強
い吸収能を有するものであり、また原料化合物として工
業的に汎用なブタジエン化合物を利用できるため、工業
的に安価に製造することができる。[Effects of the Invention] The leuco dye of the present invention has a strong absorption ability in the near-infrared region, and can be produced industrially at low cost because it can use an industrially general-purpose butadiene compound as a raw material compound. Can be done.
Claims (2)
１：ジアルキルアミノフェニル基 Ｙ１：水素原子、低級アルキル基 Ａ：ベンゼン環、ナフタレン環[Claim 1] A leuco dye represented by the following chemical formula 1. [Formula 1] R1, R2: Lower alkyl group R3: Hydrogen atom, lower alkyl group, lower alkoxy group X
1: dialkylaminophenyl group Y1: hydrogen atom, lower alkyl group A: benzene ring, naphthalene ring
２：低級アルコキシル基で置換されていてもよいフェニ
ル基 Ｙ２：低級アルキル基、前記したＸ２ Ａ：ベンゼン環、ナフタレン環2. A leuco dye represented by the following chemical formula 2. [Formula 2] R1, R2: Lower alkyl group R3: Hydrogen atom, lower alkyl group, lower alkoxy group X
2: Phenyl group optionally substituted with lower alkoxyl group Y2: Lower alkyl group, X2 described above A: Benzene ring, naphthalene ring
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03138467A JP3078035B2 (en) | 1991-05-14 | 1991-05-14 | Leuco dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03138467A JP3078035B2 (en) | 1991-05-14 | 1991-05-14 | Leuco dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04338583A true JPH04338583A (en) | 1992-11-25 |
| JP3078035B2 JP3078035B2 (en) | 2000-08-21 |
Family
ID=15222728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03138467A Expired - Fee Related JP3078035B2 (en) | 1991-05-14 | 1991-05-14 | Leuco dye |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3078035B2 (en) |
-
1991
- 1991-05-14 JP JP03138467A patent/JP3078035B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3078035B2 (en) | 2000-08-21 |
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