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Improvements in and relating to polymethine dye intermediates and to the production of polymethine dyes

机译:与聚次甲基染料中间体和聚次甲基染料的生产有关的改进

摘要

556,266. Polymethine dyes and intermediates. KODAK, Ltd. Sept. 26, 1941, No. 12486. Convention date, Oct. 18, 1940. Samples furnished. [Class 2 (iii)] [Also in Group XX] A compound of the general formula of Fig. 1 where R represents an alkyl or aryl radical, RSP1/SP represents an alkyl radical, X represents an acid radical, and Z the non-metallic atoms necessary to complete a 5- or 6- membered heterocyclic nucleus is prepared by condensing a #-alkoxyacrolein acetal with a cyclammonium quaternary salt containing a methyl group in the α-position to the nitrogen atom and employing as the reaction medium substantially anhydrous acetic acid not containing more than 1 per cent. of water. From 1 ¢ to 3 molecular proportions of acrolein acetal may be used for each molecular proportion of cyclammonium quaternary salt. The cyclammonium quaternary salt may be a quinoline, benzoxazole, naphthoxazole, benzthiazole, naphthathiazole, benzselenazole, or thiazoline derivative. The reaction medium may be glacial acetic acid and the quaternary salt an iodide. 2-(4-Ethoxy- #SP1/SP:SP3/SP-butadienyl)-benzthiazoleethiodide is prepared by reacting 2-methylbenzthiazole ethiodide and #-ethoxyacrolein diethyl acetal in glacial acetic acid. 2-(4-Ethoxy-#SP1/SP:SP3/SP-butadienyl)-benzoxazole ethiodide, 2-(4-etlaoxy-#SP1/SP:SP3/SP- butadienyl)-#-naphthathiazole ethiodide, 2-(4- ethoxy-#SP1/SP:SP3/SP-butadienyl)-α-naphthoxazole ethiodide, 2-(4-ethoxy-# SP1/SP:SP3/SP-butadienyl)-#-naphthoxazole ethiodide, 2-(4-ethoxy-#SP1/SP:SP3/SP-butadienyl)-quino line ethiodide, 2-(4-ethoxy-#SP1/SP:SP3/SP-butadienyl)-benzselenazole ethiodide, 2-(4-ethoxy- #SP1/SP: SP3/SP-butadienyl). thiazoline ethiodide, 2-(4-ethoxy-#SP1/SP:SP3/SP-butadienyl). benzthiazolepheniodide, and 2-(4-ethoxy-#SP1/SP:SP3/SP- butadienyl) 3:4 - - trimethylene benzthiazolium iodide are similarly prepared. Polymethine dyes are prepared by condensing a compound of the general formula shown in Fig. 1 with a cyclammonium alkyl quarternary salt containing a methyl group in the α or y position to the nitrogen atom. Pyridine or trialkylamines dissolved in acetic anhydride may be used as condensing agents. 3 : 3SP1/SP- Diethylthiadicarbocyanine iodide is prepared by refluxing together 2 - (4 - ethoxy - # SP1/SP : SP3/SP - butadienyl) - benzthiazole ethiodide and 2 - methylbenzthiazole ethiodide in pyridine. 1SP1/SP: 3- Diethyloxa - 2SP1/SP - dicarbocyanine iodide is similarly prepared using as condensing agent acetic anhydride containing triethylamine. 1SP1/SP : 3 - - Diethylthia - 2SP1/SP dicarbocyanine iodide, 1SP1/SP : 3 - diethylthia - 4SP1/SP - dicarbocyanine iodide 3 : 3SP1/SP - diethyl - 4 : 5 benzthiadicarbocyanine iodide, 3 : 3 - diethyl - 4 5 : 4SP1/SP: 5SP1/SP - dibenzthiadicarbocyanine iodide, 1 : : 1SP1/SP - diethyl 2 : : 2SP1/SP- dicarbocyanine iodide, 3 : 3SP1/SP - diethyloxadi - carbocyanine iodide, 3 : 3SP1/SP - . diethyloxathiadicarbonyanine isodide, 1SP1/SP : 3 - diethyloxa - 4SP1/SP - dicarbocyanine iodide, 3 3SP1/SP - diethylselena - dicarbocyanine iodide, 3 : 3SP1/SP - diethylselenathiadicarbocyanine iodide, 3 : 3SP1/SP- diethyloxaselena dicarbocyanine iodide, and 3 - ethyl - 3SP1/SP - methylthiathiazolino dicarbocyanine iodide are similarly prepared. Polymethine dyes may also be prepared by condensing the compounds of the general formula of Fig. 1 with a heterocyclic compound having a methylene group adjacent to a carbonyl group. 3 - - Ethyl - 5 - [(3 - - ethyl - 2 - benzthiazolyidene) - butenylidene] - rhodanine is prepared by condensing 2 - (4 - ethoxy - #SP 1/SP : 3- butadienyl) - benzthiazole ethiodide with 3 - ethylrhodanine in the presence of triethylamine and acetic anhydride. The intermediate may also be condensed with 1 - phenyl - 3 - methyl - 5 -.pyrazolone or with 1 - ethyl - 3 - phenyl - 2 - thiohydantoin. Polymethine dyes may also be prepared by condensing the intermediates with primary or secondary aliphatic or aromatic amines. 2 - (4- Piper´dino - #SP1/SP : SP3/SP - butadienyl)- benzthiazole ethiodide is prepared by refluxing together 2 - (4 - ethoxy - #SP1/SP : 3 - butadienyl)- benzthiazole ethiodide and piperidine in ethyl alcohol. The intermediate may also be condensed with aniline. Polymethine dyes may also be obtained by condensing the intermediates with N - alkyl or N - aryl pyrroles. Such dyes may be used as light-screening substances in the preparation of photographic elements, and are bleachable in alkaline developers. (3 - - Ethyl - 2 - benzthiazole) (1 - - heptyl - 2 : 5 - dimethyl - 3 - pyrrole) - tetramethinecyanine iodide is prepared by refluxing together 2 - (4 - ethoxy - #SP1/SP : 3 - butadienyl) - benzthiazole ethiodide and 1 - heptyl - 2 : 5 - dimethylpyrrole in acetic anhydride. (3 - - Ethyl - 2 - benzoxazole) (1 - - heptyl - 2 : 5 - dimethyl - 3 pyrrole-, (3 - - ethyl - 2 - benzoxaozle) (1 - lauryl - 2 : : 5 - dimethyl 3 - - pyrrole) 3 - - ethyl - 2 - benzoxazole)- (1 - ethyl - 2 : : 5 - dimethyl - 3 - pyrrole)-, (1 - cetyl - 2 : 5 - dimethyl 3 - - pyrrole) 3 - - ethyl - 2 - benzoxazole)-, (1 ethyl - 2: 5 - dimethyl - 3 - pyrrole) - (3 - ethyl - 2 - α - naphthoxazole),- (3 - - ethyl - 2 - α - - naphthoxazole) - (1 lauryl - 2 : 5 - - dimethyl 3 - pyrrole)-, (1 - ethyl - 2 : 5 - dimethyl - 3 pyrrole) (1 - - ethyl - 2 - # - naphthoxazole)-, 1 - - ethyl - 2 5 - dimethyl - 3 pyrrole)- (1 - - ethyl 2 - quinoline)-, (3 - - ethyl - 2 - benzthia; zole)- (1 - ethyl - 2 : 5 - dimethyl - 3 pyrrole)-,. (3 - - ethyl - 2 - benzthiazole)- (2 : 5 dimethyl 1- phenyl 3 - - pyrrole)-, (1 - - ethyl - 2 : 5 - dimethyl- 3 - pyrrole) - (3 - - methyl - 2 thiazoline)-, and (3 - - ethyl - 2 - - benzselenazole) (1 - - ethyl - 2 : 5- dimethyl - 3 - pyrrole) tetramethine cyanines are similarly prepared. Samples have been furnished under Sect. 2 (5) of (a) 2SP1/SP - (4 - methoxy - #SP1/SP :SP3/SP -butadienyl)- benzoxazole ethiodide (b) 2SP1/SP - (4-piperidine - # SP1/SP: SP3/SP - butadienyl) - benzthiazole ethiodide: (c) 2SP1/SP - (4 - anilino - #SP1/SP : 3 - butadienyl) - benz - thiazole ethiodide : and (d) 2SP1/SP - (4 - dibutylamino - # SP1/SP : SP3/SP - butadienyl) - benzoxazole ethoper - chlorate. Specification 551,331 is referred to.
机译:556,266。聚次甲基染料和中间体。柯达有限公司(KODAK,Ltd。),1941年9月26日,编号12486。会议日期,1940年10月18日。提供样品。 [2(iii)类] [XX族中的化合物]图1的通式的化合物,其中R代表烷基或芳基,R 1 代表烷基,X代表酸自由基和Z是完成5或6元杂环原子核所必需的非金属原子,这是通过将#-烷氧基丙烯醛缩醛与在α位上含有甲基的环铵季铵盐缩合到氮原子上而制备的作为反应介质,基本上无水乙酸的含量不超过1%。水。 1到3分子比例的丙烯醛缩醛可用于每个分子比例的环铵季盐。环铵季盐可以是喹啉,苯并恶唑,萘并恶唑,苯并噻唑,萘并噻唑,苯并硒唑或噻唑啉衍生物。反应介质可以是冰醋酸,而季盐是碘化物。 2-(4-乙氧基-# 1 3 -丁二烯基)-苯并噻唑硫代噻吩是通过使2-甲基苯并噻唑硫代乙炔与#-乙氧基丙烯醛二乙缩醛在冰醋酸中反应制得。 2-(4-乙氧基-# 1 3 -丁二烯基)-苯并恶唑乙硫醚,2-(4-乙氧基-# 1 :< SP> 3 -丁二烯基)-#-萘噻唑乙硫醇,2-(4-乙氧基-# 1 3 -丁二烯基)-α-萘恶唑乙硫醇, 2-(4-乙氧基-# 1 3 -丁二烯基)-#-萘恶唑乙硫醚,2-(4-乙氧基-# 1 3 -丁二烯基)-喹啉乙硫键,2-(4-乙氧基-# 1 3 -丁二烯基)-苯并硒唑乙硫醚,2 -(4-乙氧基-# 1 3 -丁二烯基)。噻唑啉噻吩,2-(4-乙氧基-# 1 3 -丁二烯基)。类似地制备苯并噻唑苯碘化物和2-(4-乙氧基-# 1 3 -丁二烯基)3:4-三亚甲基苯并噻唑鎓碘化物。通过将图1所示的通式化合物与在氮原子的α或y位置含有甲基的环烷基烷基季铵盐缩合来制备聚次甲基染料。溶解在乙酸酐中的吡啶或三烷基胺可用作缩合剂。 3:3 1 -碘化二乙基噻二氧杂花青碘是通过2-(4-乙氧基-# 1 3 -丁二烯基)-苯并噻唑乙硫醚回流而制得的和2-甲基苯并噻唑硫代吡啶。 1 1 :3-二乙氧基-2 1 -二碳菁碘化物也使用含有三乙胺的乙酸酐作为缩合剂来制备。 1 1 :3--二乙基-2 1 二碳菁碘化物,1 1 :3-二乙基-4 1 -碘化二羰花青3:3 1 -二乙基-4:5碘化苯并二氰基花青,3:3-二乙基-4 5:4 1 :5 1 -碘二苯并噻二氰基花青,1::1 1 -二乙基2:::2 1 -碘化二羰花青,3:3 1 -二乙基恶二酮-碳花青碘化物3:3 1 -。 diethyloxathiadicarbonyanine isodide,1 1 :3-diethyloxa-4 1 -dicarbocyanine iodide,3 3 1 -diethylselena-dicarbocyanine iodide,3:3 <类似地制备SP> 1 -二乙基硒代二氰基花青碘化物,3:3 1 -二乙基氧杂色拉二碳菁碘化物和3-乙基-3 1 -甲基噻吩并恶唑啉基二碳菁碘化物。聚次甲基染料也可以通过将图1的通式化合物与具有与羰基相邻的亚甲基的杂环化合物缩合来制备。 3--乙基-5-[(3--乙基-2-苄硫唑基)-丁烯基]-罗丹宁是将2-(4-乙氧基-# 1 :3-丁二烯基)-苯并噻唑缩合制备的在三乙胺和乙酸酐存在下,将乙硫醇与3-乙基罗丹宁混合。中间体也可以与1-苯基-3-甲基-5-吡唑酮或1-乙基-3-苯基-2-硫代乙内酰脲缩合。聚次甲基染料也可以通过使中间体与伯或仲脂族或芳族胺缩合来制备。 2-(4-哌啶基-# 1 3 -丁二烯基)-苯并噻唑乙硫醇通过回流2-(4-乙氧基-# 1 :在乙醇中的3-丁二烯基)-苯并噻唑乙硫醚和哌啶。中间体也可以与苯胺缩合。聚次甲基染料也可以通过使中间体与N-烷基或N-芳基吡咯缩合而获得。这样的染料可以在照相材料的制备中用作遮光物质。,并且在碱性显影剂中可漂白。 (3--乙基-2-苯并噻唑)(1--庚基-2:5-二甲基-3-吡咯)-四甲基花青碘化物是通过将2-(4-乙氧基-# 1 :在乙酸酐中的3-丁二烯基)-苯并噻唑乙硫醚和1-庚基-2:5-二甲基吡咯。 (3--乙基-2-苯并恶唑)(1--庚基-2:5-二甲基-3吡咯-,(3--乙基-2-苯并恶唑)(1-月桂基-2 :: 5-二甲基3--吡咯)3--乙基-2-苯并恶唑)-(1-乙基-2::5-二甲基-3-吡咯)-,(1-十六烷基-2:5-二甲基3--吡咯)3--乙基- 2-苯并恶唑)-,(1乙基-2:5-二甲基-3-吡咯)-(3-乙基-2-α-萘并恶唑),-(3--乙基-2-α--萘并恶唑)-(1月桂基-2:5--二甲基3-吡咯)-,(1-乙基-2:5-二甲基-3吡咯)(1--乙基-2-#-萘恶唑)-,1--乙基-2 5-二甲基-3吡咯)-(1--乙基2-喹啉)-,(3--乙基-2-苯并噻唑;唑)-(1-乙基-2:5-二甲基-3吡咯)-。 (3--乙基-2-苯并噻唑)-(2:5二甲基1-苯基3--吡咯)-,(1--乙基-2:5-二甲基-3-吡咯)-(3--甲基-2类似地制备噻唑啉)-和(3--乙基-2--苯并恶唑)(1-乙基-2:5-二甲基-3-吡咯)四甲胺花青。样品已根据“节”提供。 (a)2 1 -(4-甲氧基-# 1 3 -丁二烯基)-苯并恶唑乙硫醚的2(5)(b) 2 1 -(4-哌啶-# 1 3 -丁二烯基)-苯并噻唑乙硫醚:(c)2 1 -(4-苯胺基-# 1 :3-丁二烯基)-苯并-噻唑硫代噻吩:和(d)2 1 -(4-二丁基氨基-# 1 3 -丁二烯基)-苯并恶唑乙炔-氯酸盐。参考规范551,331。

著录项

  • 公开/公告号GB556266A

    专利类型

  • 公开/公告日1943-09-28

    原文格式PDF

  • 申请/专利权人 KODAK LIMITED;

    申请/专利号GB19410012486

  • 发明设计人

    申请日1941-09-26

  • 分类号C09B23/01;C09B23/02;C09B23/10;

  • 国家 GB

  • 入库时间 2022-08-24 03:42:06

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