JPH02127475A - Production of benzoindolenine cyanine dyestuff - Google Patents
Production of benzoindolenine cyanine dyestuffInfo
- Publication number
- JPH02127475A JPH02127475A JP28050688A JP28050688A JPH02127475A JP H02127475 A JPH02127475 A JP H02127475A JP 28050688 A JP28050688 A JP 28050688A JP 28050688 A JP28050688 A JP 28050688A JP H02127475 A JPH02127475 A JP H02127475A
- Authority
- JP
- Japan
- Prior art keywords
- ion
- formula
- parts
- group
- compound
- 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
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000975 dye Substances 0.000 title abstract description 21
- -1 halogen ion Chemical class 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 3
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract description 39
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 abstract description 7
- 239000001632 sodium acetate Substances 0.000 abstract description 7
- 235000017281 sodium acetate Nutrition 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract description 3
- 239000003086 colorant Substances 0.000 abstract 1
- 150000002367 halogens Chemical class 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 150000003839 salts Chemical group 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 238000001226 reprecipitation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MNRRNPKQXGBGBH-UHFFFAOYSA-N 2,3,3-trimethylbenzo[g]indole Chemical compound C1=CC=C2C(N=C(C3(C)C)C)=C3C=CC2=C1 MNRRNPKQXGBGBH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 125000005041 acyloxyalkyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical group N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000006351 ethylthiomethyl group Chemical group [H]C([H])([H])C([H])([H])SC([H])([H])* 0.000 description 1
- WFSXUTWNNVIIIG-ZPUQHVIOSA-N glutaconaldehyde Chemical compound O\C=C\C=C\C=O WFSXUTWNNVIIIG-ZPUQHVIOSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004372 methylthioethyl group Chemical group [H]C([H])([H])SC([H])([H])C([H])([H])* 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- IJNJLGFTSIAHEA-UHFFFAOYSA-N prop-2-ynal Chemical compound O=CC#C IJNJLGFTSIAHEA-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
- C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は染料、顔料、フィルター用着色材料および記録
媒体として有用なベンゾインドレニン系シアニン色素の
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing benzoindolenine cyanine dyes useful as dyes, pigments, coloring materials for filters, and recording media.
（従来の技術〕
従来のベンゾインドレニン系シアニン色素の合成は、例
えば米国特許第２，８９５，９５５号に記載されている
ように、４，５−ベンゾインドレニンの四級塩と酢酸ナ
トリウムと塩酸グルタコンアルデヒドシアニルの混合物
に沸騰した無水酢酸を添加するといった非常に危険を伴
なう方法であり、商業規模での製造が困難であった。ま
た該方法を６．７−ベンゾインドレニン系シアニン色素
の合成反応に応用しても、副生成物が多く高純度品を得
ることはできなかった。(Prior Art) Conventional benzindolenine cyanine dyes are synthesized by combining a quaternary salt of 4,5-benzoindolenine with sodium acetate, as described in, for example, U.S. Pat. No. 2,895,955. This method involved adding boiling acetic anhydride to a mixture of glutaconaldehyde cyanyl hydrochloride, making it difficult to produce on a commercial scale. Even when applied to the synthesis reaction of cyanine dyes, it was not possible to obtain highly pure products due to the large amount of by-products.
本発明の目的は、染料、顔料、フィルター用着色材料お
よび記録媒体として有用なベンゾインドレニン系シアニ
ン色素の商業規模の製造方法を提供することにあり、か
つ副生成物の生成を抑制することの可能な製造方法を提
供することにある。An object of the present invention is to provide a commercial-scale production method for benzoindolenine cyanine dyes useful as dyes, pigments, coloring materials for filters, and recording media, and to suppress the production of by-products. The purpose is to provide a possible manufacturing method.
本発明は、式（Ｔ）
［式（１）中、Ｒは未置換または置換アルキル基を表わ
し、ｘｅはアリールスルホン酸イオン、アルキルスルホ
ン酸イオン、アルコキシスルホン酸イオン、ハロゲンイ
オンを表わす］で示される６、７−ベンゾインドレニン
系シアニン色素の合成に際して、式（ＩＮ）
［式（ＩＩ）中、Ｒは未置換または置換アルキル基を表
わし、ｘｏはアリールスルホン酸イオン、アルキルスル
ホン酸イオン、アルコキシスルホン酸イオン、ハロゲン
イオンを表わす］で示される化合物と塩基とカルボン酸
無水物を含む溶液に、式［式（Ｉ［Ｉ）中、ＹｅハＣＨ
３ＣＯ０ｅマタハハロケンイオンを表わす］で示される
化合物を１００℃から反応溶媒の還流温度の範囲で加え
ることを特徴とするベンゾインドレニン系シアニン色素
の製造方法である。The present invention is represented by the formula (T) [in formula (1), R represents an unsubstituted or substituted alkyl group, and xe represents an arylsulfonate ion, an alkylsulfonate ion, an alkoxysulfonate ion, or a halogen ion]. When synthesizing a 6,7-benzoindolenine cyanine dye, formula (IN) [In formula (II), R represents an unsubstituted or substituted alkyl group, and xo represents an arylsulfonate ion, an alkylsulfonate ion, an alkoxy sulfonic acid ion, halogen ion], a base, and a carboxylic acid anhydride.
This is a method for producing a benzindolenine cyanine dye, which is characterized in that a compound represented by 3CO0e (representing matahahalokene ion) is added at a temperature ranging from 100° C. to the reflux temperature of the reaction solvent.
式（Ｉ）、（ｎ）中のＲの未置換または置換アルキル基
としては、例えば、メチル基、エチル基、プロピル基、
ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オク
チル基、ノニル基、デシル基などのアルキル基、メトキ
シメチル基、エトキシメチル基、プロポキシメチル基、
メトキシエチル基、メトキシブチル基などのアルコキシ
アルキル基、メチルチオメチル基、エチルチオメチル基
、メチルチオエチル基などのアルキルチオアルキル基、
メチルカルボニルオキシメチル基、エチルカルボニルオ
キシメチル基、メチルカルボニルオキシエチル基などの
アルカノイルオキシアルキル基、メ］・キシカルボニル
メチル基、エトキシカルボニルメチル基、ブトキシカル
ボニルメチル基、メトキシカルボニルエチル基などのア
ルコキシカルボニルアルキル基、ベンジル基、フェニル
エチル基などのアラルキル基、アリル基、クロチル基な
どのアルケニル基などが挙げられる。Examples of the unsubstituted or substituted alkyl group for R in formulas (I) and (n) include methyl group, ethyl group, propyl group,
Alkyl groups such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group,
Alkoxyalkyl groups such as methoxyethyl group and methoxybutyl group; alkylthioalkyl groups such as methylthiomethyl group, ethylthiomethyl group and methylthioethyl group;
Alkanoyloxyalkyl groups such as methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, methylcarbonyloxyethyl group, alkoxycarbonyl group such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, methoxycarbonylethyl group Examples include aralkyl groups such as alkyl groups, benzyl groups and phenylethyl groups, and alkenyl groups such as allyl groups and crotyl groups.
式（Ｉ）、（ＩＩ）中のＸ１９としては、ｐ−トルエン
スルホン酸イオン、ベンゼンスルホン酸イオンなどのア
リールスルホン酸イオン、メチルスルホン酸イオン、エ
チルスルホン酸イオン、プロピルスルホン酸イオンなど
のアルキルスルホン酸イオン、メトキシスルホン酸イオ
ン、エトキシスルホン酸イオンなどのアルコキシスルホ
ン酸イオン、Ｆｅ、 Ｃ１”、 Ｂｒｅ、ＩＯなどのハ
ロゲンイオンなどが挙げられる。X19 in formulas (I) and (II) is an arylsulfonate ion such as p-toluenesulfonate ion or benzenesulfonate ion, or an alkylsulfone such as methylsulfonate ion, ethylsulfonate ion, propylsulfonate ion, etc. Examples include acid ions, alkoxysulfonate ions such as methoxysulfonate ions and ethoxysulfonate ions, and halogen ions such as Fe, C1'', Bre, and IO.
カルボン酸無水物としては、無水酢酸、無水プロピオン
酸などが挙げられ、好ましくは無水酢酸である。カルボ
ン酸としては、酢酸、プロピオン酸などが挙げられる。Examples of the carboxylic anhydride include acetic anhydride and propionic anhydride, with acetic anhydride being preferred. Examples of carboxylic acids include acetic acid and propionic acid.
塩基としては、酢酸ナトリウム、酢酸カリウム、酢酸マ
グネシウムなどの塩が挙げられる。Examples of the base include salts such as sodium acetate, potassium acetate, and magnesium acetate.
反応で使用される化合物（ＩＩＩ）の量は、化合物（ｎ
）に対して、０．３〜０．７モル当量、好ましくは０．
４５〜０．５５モル当量である。塩基の使用量は化合物
（ＩＩ）に対して０．５〜２．０モル当量であり、好ま
しくは、０．８〜１．２モル当量である。化合物（ＩＩ
りの添加は１００℃から反応溶媒の還流温度の範囲で行
ない、反応温度はｉｏｏ℃から反応溶媒の還流温度の範
囲である。反応時間は必要に応じて調整される。また化
合物（ＩＩ）は２，３．３−トリメチル−６，７−ベン
ゾインドレニンとＲＸ（式中のＲｌＸは式（ｎ）中のＲ
，Ｘと同一の意味を表わす）で示される化合物を加熱下
、反応させて得ることができる。また、化合物（ｍ）は
、プロパギルアルコールを酸化したプロピオールアルデ
ヒドとアニリンと酸を反応させて得ることができる。The amount of compound (III) used in the reaction is
), 0.3 to 0.7 molar equivalent, preferably 0.
45 to 0.55 molar equivalent. The amount of the base used is 0.5 to 2.0 molar equivalents, preferably 0.8 to 1.2 molar equivalents, relative to compound (II). Compound (II
The addition is carried out at a temperature ranging from 100° C. to the reflux temperature of the reaction solvent, and the reaction temperature ranges from 100° C. to the reflux temperature of the reaction solvent. The reaction time is adjusted as necessary. Moreover, compound (II) is 2,3,3-trimethyl-6,7-benzoindolenine and RX (RlX in the formula is R in the formula (n)
, (same meaning as X) under heating. Compound (m) can also be obtained by reacting propiolaldehyde obtained by oxidizing propargyl alcohol with aniline and an acid.
以下、実施例により、さらに詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
（実施例１）
下記ベンズインドレニン四級塩（Ｉｌ−１）２６５部と
酢酸ナトリウム５３部と無水酢酸２３００部を含む溶液
を還流冷却器を備えたフラスコ中に入れ、１００℃に加
熱した後、酢酸マロンアルデヒドシアニル９１部と無水
酢酸５５０部よりなる溶液を１００℃で加え、さらに
１００℃で２０分間攪拌した後、Ｎａ１２２０部を含む
水２００００部中に排出した。静置後、タール状沈降物
を分取し水洗した。このタール状沈降物をアセトン８０
００部に溶解し、Ｎａ１２２０部を加えた。−夜静置後
、不溶物を除去し、溶媒を留去した。得られた残清なア
セトンに溶解した後、ヘキサンを加えて結晶を析出させ
る再沈法により精製し、 １８５部（収率９０％）の下
記シアニン色素（Ｉ−１）を得た。(Example 1) A solution containing 265 parts of the following benzindolenine quaternary salt (Il-1), 53 parts of sodium acetate, and 2300 parts of acetic anhydride was placed in a flask equipped with a reflux condenser, and heated to 100°C. , a solution consisting of 91 parts of cyanyl malonaldehyde acetate and 550 parts of acetic anhydride was added at 100°C, and then
After stirring at 100° C. for 20 minutes, the mixture was discharged into 20,000 parts of water containing 1,220 parts of Na. After standing still, the tar-like precipitate was collected and washed with water. This tar-like precipitate was washed with 80% acetone.
00 parts, and 1220 parts of Na was added. - After standing overnight, insoluble matter was removed and the solvent was distilled off. The resulting residue was dissolved in acetone and purified by a reprecipitation method in which hexane was added to precipitate crystals to obtain 185 parts (yield 90%) of the following cyanine dye (I-1).
（ＩＩ−１）
（Ｉ
（実施例２）
下記ベンズインドレニン四級塩（ＩＩ−２） ２７４
部と酢酸ナトリウム５３部と無水酢酸２３００部を含む
溶液を還流冷却器を備えたフラスコ中に入れ、１００℃
に加熱した後、酢酸マロンアルデヒドシアニル９１部と
無水酢酸５５０部よりなる溶液を１００℃で加え、さら
に １００℃で２５分間攪拌した後、Ｎａ１２２０部を
含む水２００００部中に排出した。静置後、タール状沈
降物を分取し水洗した。このタール状沈降物をアセトン
８０００部に溶解し、ＮａＩ２２０部を加えた。−夜静
置後、不溶物を除去し、溶媒を留去した。得られた残渣
をアセトンに溶解した後、ヘキサンを加えて結晶を析出
させる再沈法により精製し、 ２００部（収率８５％）
の下記シアニン色素（Ｉ−２）を得た。(II-1) (I (Example 2) The following benzindolenine quaternary salt (II-2) 274
A solution containing 53 parts of sodium acetate and 2300 parts of acetic anhydride was placed in a flask equipped with a reflux condenser and heated to 100°C.
After heating to 200° C., a solution consisting of 91 parts of cyanyl malonaldehyde acetate and 550 parts of acetic anhydride was added at 100°C, and after further stirring at 100°C for 25 minutes, the mixture was discharged into 20,000 parts of water containing 1220 parts of Na. After standing still, the tar-like precipitate was collected and washed with water. This tar-like precipitate was dissolved in 8000 parts of acetone, and 220 parts of NaI was added. - After standing overnight, insoluble matter was removed and the solvent was distilled off. After dissolving the obtained residue in acetone, it was purified by a reprecipitation method in which hexane was added to precipitate crystals, and 200 parts (yield 85%) were obtained.
The following cyanine dye (I-2) was obtained.
（ＩＩ−２）
（実施例３）
下記ベンズインドレニン四級塩（ｎ −３） １９７
部と酢酸カリウム６３部と無水酢酸２３００部を含む溶
液を還流冷却器を備えたフラスコ中に入れ、１００℃に
加熱した後、塩酸マロンアルデヒドシアニル８４部と無
水酢酸５５０部よりなる溶液を１００℃で加え、ざらに
１００℃で２０分間攪拌した後、水２００００部中に排
出した。静置後、タール状沈降物を分取し水洗した。こ
のタール状沈降物をアセトンに溶解した後、ヘキサンを
加えて結晶を析出させる再沈法により精製し、 １５９
部（収率８１％）の下記シアニン色素（１−３）を得た
。(II-2) (Example 3) The following benzindolenine quaternary salt (n-3) 197
A solution containing 63 parts of potassium acetate and 2300 parts of acetic anhydride was placed in a flask equipped with a reflux condenser and heated to 100°C. The mixture was added at 100°C, stirred roughly for 20 minutes at 100°C, and then discharged into 20,000 parts of water. After standing still, the tar-like precipitate was collected and washed with water. After dissolving this tar-like precipitate in acetone, it was purified by a reprecipitation method in which hexane was added to precipitate crystals, and 159
(yield: 81%) of the following cyanine dye (1-3) was obtained.
（実施例４〜１２） 式 式（ＩＩＩ） 中の ｙｆ９、 塩基、 溶媒、 反応条件、 収率を第１表に示 す。(Examples 4 to 12) formula Formula (III) In yf9, base, solvent, reaction conditions, The yield is shown in Table 1. vinegar.
本発明の製造方法では、高純度のシアニン色素を高収率
で得ることができた。しかし、化合物（Ｉ［Ｉ）の添加
を、比較的低温で行なうとシアニン生成反応が不十分と
なり、副生成物が多く、高純度のシアニン色素を得るこ
とができなくなる。以下にその例を比較例として示す。In the production method of the present invention, a highly pure cyanine dye could be obtained in high yield. However, when compound (I[I) is added at a relatively low temperature, the cyanine production reaction becomes insufficient, many by-products are produced, and a highly pure cyanine dye cannot be obtained. An example is shown below as a comparative example.
（比較例１）
ベンズインドレニン四級塩（ＩＩ−１） ２６５部と
酢酸ナトリウム５３部と酢酸マロンアルデヒドシアニル
９１部と無水酢酸２８５０部よりなる溶液を室温から徐
々に加熱して１００℃に昇温し、さらに１００℃で２０
分間攪拌した後、ＮａＩ２２０部を含む水２００００部
中に排出した。静置後、タール状沈降物を分取し水洗し
た。このタール状沈降物をアセトン８０００部に溶解し
、ＮａＩ２２０部を加えた。−夜静置後、不溶物を除去
し、溶媒を留去した。得られた残漬をアセトンに溶解し
た後、ヘキサンを加えて結晶を析出させる再沈法により
積製し、 １１０部の結晶を得た。しかしこの結晶中の
シアニン色素（Ｉ−１）の含有率は１１％であった。(Comparative Example 1) A solution consisting of 265 parts of benzindolenine quaternary salt (II-1), 53 parts of sodium acetate, 91 parts of malonaldehyde cyanyl acetate, and 2850 parts of acetic anhydride was gradually heated from room temperature to 100°C. Raise the temperature and further increase the temperature to 100℃ for 20
After stirring for a minute, it was poured into 20,000 parts of water containing 220 parts of NaI. After standing still, the tar-like precipitate was collected and washed with water. This tar-like precipitate was dissolved in 8000 parts of acetone, and 220 parts of NaI was added. - After standing overnight, insoluble matter was removed and the solvent was distilled off. After dissolving the obtained residue in acetone, hexane was added to precipitate the solution by reprecipitation to obtain 110 parts of crystals. However, the content of cyanine dye (I-1) in this crystal was 11%.
（比較例２）
ベンズインドレニン四級塩（ＩＴ−１）２６５部と酢酸
ナトリウム５３部と無水酢酸２３００部を含む溶液を６
０℃に加熱した。そこへ酢酸マロンアルデヒドシアニル
９１部と無水酢酸５５０部よりなる溶液を６０℃で加え
、さらに１００℃に昇温し、 １００℃で２０分間攪拌
した後、Ｎａ１２２０部を含む水２００００部中に排出
した。静置後、タール状沈降物を分取し水洗した。この
タール状沈降物をアセトン８０００部に溶解し、ＮａＩ
２２Ｑ部を加えた。−夜静置後、不溶物を除去し、溶媒
を留去した。得られた残漬をアセトンに溶解した後、ヘ
キサンを加えて結晶を析出させる再沈法により精製し、
１２４部の結晶を得た。しかしこの結晶中のシアニン
色素（１−１）の含有率は３２％であフた。(Comparative Example 2) A solution containing 265 parts of benzindolenine quaternary salt (IT-1), 53 parts of sodium acetate, and 2300 parts of acetic anhydride was
Heated to 0°C. A solution consisting of 91 parts of cyanyl malonaldehyde acetate and 550 parts of acetic anhydride was added thereto at 60°C, the temperature was further raised to 100°C, and after stirring at 100°C for 20 minutes, it was discharged into 20,000 parts of water containing 1,220 parts of Na. did. After standing still, the tar-like precipitate was collected and washed with water. This tar-like precipitate was dissolved in 8000 parts of acetone, and NaI
Added 22Q parts. - After standing overnight, insoluble matter was removed and the solvent was distilled off. After dissolving the obtained residue in acetone, it is purified by a reprecipitation method in which hexane is added to precipitate crystals.
124 parts of crystals were obtained. However, the content of cyanine dye (1-1) in this crystal remained at 32%.
本発明により、ベンゾインドレニン系シアニン色素合成
において、従来法である沸騰した無水酢酸の添加といっ
た危険な操作を行なうことなく、安全かつ工業的に存利
な製造方法を提供することが可能となった。さらに、本
発明の製造方法によれば、高純度、高収率で目的とする
色素を得られるようになった。The present invention makes it possible to provide a safe and industrially viable production method for benzindolenine cyanine dye synthesis without the need for dangerous operations such as adding boiling acetic anhydride, which is the conventional method. Ta. Furthermore, according to the production method of the present invention, it has become possible to obtain the desired dye with high purity and high yield.
Claims (1)
わし、Ｘ＾■はアリールスルホン酸イオン、アルキルス
ルホン酸イオン、アルコキシスルホン酸イオン、ハロゲ
ンイオンを表わす］で示される６、７−ベンゾインドレ
ニン系シアニン色素の合成に際して、式（II） ▲数式、化学式、表等があります▼（II） ［式（II）中、Ｒは未置換または置換アルキル基を表わ
し、Ｘ＾■はアリールスルホン酸イオン、アルキルスル
ホン酸イオン、アルコキシスルホン酸イオン、ハロゲン
イオンを表わす］で示される化合物と塩基とカルボン酸
無水物を含む溶液に、式（III） ▲数式、化学式、表等があります▼（III） ［式（III）中、Ｙ＾■はＣＨ＿３ＣＯＯ＾■またはハ
ロゲンイオンを表わす］で示される化合物を１００℃か
ら反応溶媒の還流温度の範囲で加えることを特徴とする
ベンゾインドレニン系シアニン色素の製造方法。 ２、塩基がカルボン酸ナトリウムまたはカルボン酸カリ
ウムであることを特徴とする請求項１記載のシアニン色
素の製造方法。[Claims] 1. Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In formula (I), R represents an unsubstituted or substituted alkyl group, and X^■ is arylsulfonic acid. ion, alkylsulfonate ion, alkoxysulfonate ion, halogen ion], formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II ) [In formula (II), R represents an unsubstituted or substituted alkyl group, and X represents an arylsulfonate ion, an alkylsulfonate ion, an alkoxysulfonate ion, or a halogen ion] and a base; In a solution containing a carboxylic acid anhydride, a compound represented by formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [In formula (III), Y^■ represents CH_3COO^■ or a halogen ion] 1. A method for producing a benzoindolenine cyanine dye, which comprises adding the above at a temperature ranging from 100° C. to the reflux temperature of a reaction solvent. 2. The method for producing a cyanine dye according to claim 1, wherein the base is sodium carboxylate or potassium carboxylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28050688A JPH0791477B2 (en) | 1988-11-08 | 1988-11-08 | Method for producing benzoindolenine cyanine dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28050688A JPH0791477B2 (en) | 1988-11-08 | 1988-11-08 | Method for producing benzoindolenine cyanine dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02127475A true JPH02127475A (en) | 1990-05-16 |
| JPH0791477B2 JPH0791477B2 (en) | 1995-10-04 |
Family
ID=17626043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28050688A Expired - Lifetime JPH0791477B2 (en) | 1988-11-08 | 1988-11-08 | Method for producing benzoindolenine cyanine dye |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791477B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000064989A1 (en) * | 1999-04-27 | 2000-11-02 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Cyanine dye |
| WO2001062853A1 (en) * | 2000-02-23 | 2001-08-30 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Cyanine dyes |
| JP2009234148A (en) * | 2008-03-28 | 2009-10-15 | Sugino Oshibana Kenkyusho:Kk | Dried flower picture and its manufacturing method |
-
1988
- 1988-11-08 JP JP28050688A patent/JPH0791477B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000064989A1 (en) * | 1999-04-27 | 2000-11-02 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Cyanine dye |
| WO2001062853A1 (en) * | 2000-02-23 | 2001-08-30 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Cyanine dyes |
| JP2009234148A (en) * | 2008-03-28 | 2009-10-15 | Sugino Oshibana Kenkyusho:Kk | Dried flower picture and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0791477B2 (en) | 1995-10-04 |
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