WO2021244624A1 - 一类杂环基取代苝酰胺化合物及其应用 - Google Patents

一类杂环基取代苝酰胺化合物及其应用 Download PDF

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WO2021244624A1
WO2021244624A1 PCT/CN2021/098218 CN2021098218W WO2021244624A1 WO 2021244624 A1 WO2021244624 A1 WO 2021244624A1 CN 2021098218 W CN2021098218 W CN 2021098218W WO 2021244624 A1 WO2021244624 A1 WO 2021244624A1
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substituted
aliphatic heterocyclic
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金朝阳
郭海腾
白文
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北京文海阳工贸有限责任公司
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    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

Definitions

  • the invention relates to a class of heterocyclic group substituted perylene amide compounds and applications thereof.
  • the Chinese patent discloses a class of chemical infrared radiation agents based on a heterocyclic compound substituted for a perylene skeleton fluorescent dye.
  • the disclosed compound is a compound formed by the reaction of a heterocyclic compound morpholine with a polyhalogenated perylene amide.
  • the morpholine group is a strong electron-donating group, once the halogen is substituted into any one of positions 1, 6, 7, and 12 of the perylene, the electron cloud density of the perylene ring will increase, and the steric hindrance will be greater. It becomes more difficult to enter the next morpholine group.
  • the synthetic products are mostly a mixture of various substitutions and multiple isomers, which contain incomplete substitutions, and there are halogens at any position of 1, 6, 7, and 12. Group of compounds. It is very difficult to separate such mixtures, and compounds containing incompletely substituted halogens are unstable in subsequent chemiluminescence reactions containing peroxidants and are prone to quenching. Therefore, it is necessary to improve these compounds.
  • the purpose of the present invention is to provide a stable near-infrared fluorescent compound, and on this basis, to provide a component that outputs near-infrared fluorescence.
  • R represents a substituted or unsubstituted alkyl or aryl group
  • Ar represents substituted or unsubstituted phenyl
  • X, Y and Z are selected from aliphatic heterocyclic groups, halogens, hydrogen and aryl ether groups, and at least one substituent is the aliphatic heterocyclic group, and the aliphatic heterocyclic group is connected to the aliphatic heterocyclic group through an NC bond Perylene skeleton.
  • R can be a C4-C18 straight-chain alkyl or ether-substituted straight-chain alkyl, or a phenyl or alkyl-substituted phenyl, preferably a C4-C18 straight-chain alkyl, ten Octaalkyl or 2,6-diisopropylphenyl.
  • Ar is preferably a phenyl group or a C1-C8 alkyl-substituted phenyl group.
  • the aliphatic heterocyclic group may be morpholinyl or tetrahydropyrrolyl;
  • the halogen is preferably bromine or chlorine
  • the aryl ether group is preferably a phenoxy group.
  • One substituent is the aliphatic heterocyclic group, and the other two substituents are both halogen, aryl ether or hydrogen;
  • one substituent is morpholinyl and the other two substituents are both chlorine; b) one substituent is morpholinyl and the other two substituents are both hydrogen; c) one substituent is morpholinyl, The other two substituents are both phenoxy; d) One substituent is tetrahydropyrrolyl, and the other two substituents are both chlorine;
  • the three substituents are respectively the aliphatic heterocyclic group, halogen and aryl ether group;
  • the three substituents are respectively morpholinyl, chlorine and phenoxy;
  • the compound provided by the present invention is preferably any one of the following:
  • the electron donating ability of phenoxy group is smaller than that of N-heterocyclic compound, and the nucleophilic ability of aliphatic N-heterocyclic compound such as morpholine is very strong, it is connected first It is a preferred solution to insert a heterocyclic group after the phenoxy group.
  • the halogenated group on the phenol-substituted perylene can be prepared by existing methods, such as: firstly, the halogen-substituted perylene diimide reacts with ArOH to obtain the ArO-substituted perylene diimide, and the perylenes with different substitution conditions are separated.
  • Diimide then connect the aliphatic N-heterocyclic group, specifically, morpholine or tetrahydropyrrole can be used to react with the halogen on the perylene diimide substituted by ArO- in different situations.
  • the compound of the present invention is compounded with bisoxalate, hydrogen peroxide and a solvent to obtain a component that outputs near-infrared fluorescence, wherein the concentration of the compound is 0.0001-0.01 mol/L.
  • the component that outputs near-infrared fluorescence further includes a catalyst
  • the molar ratio of the bisoxalate to the compound is 10-1000:1;
  • the hydrogen peroxide accounts for 0.1% to 5% of the total mass of the component that outputs near-infrared fluorescence;
  • the bisoxalate may be bis(2,4,5-trichloro-6-carbonylpentyloxyphenyl) bisoxalate;
  • the solvent can be phthalate, benzoate, etc.
  • the catalyst may be sodium salicylate.
  • the characterization data shows that the structure of the obtained compound is correct.
  • the mixed solvent is the mobile phase purification product, and 195 mg of the dark green solid product is obtained as the compound represented by formula I-5: 1-phenoxy-7-morpholinyl-N,N'-bis(2,6-diisopropyl) (Phenyl)-3,4,9,10-perylene diimide, or its isomers (shown in formula I-5'): 1-phenoxy-6-morpholinyl-N,N'- Bis(2,6-diisopropylphenyl)-3,4,9,10-perylene diimide. )
  • the following references to the compound represented by formula I-5 all mean that it may also contain its isomers (compound represented by formula I-5').
  • CN200510059303.1 describes a known method of refluxing excess morpholine and chlorinated perylene diimide to obtain morpholino substituted perylene diimide compounds.
  • Take 5g of orange-yellow-orange N,N'-bis(2,6-diisopropylphenyl) 1,6,7,12 tetrachloroperylene diimide raw material, 200ml of morpholine and 18g of anhydrous potassium carbonate and reflux After reacting for 48 hours, the reaction was terminated with 3000 ml of 10% dilute hydrochloric acid, the precipitate was filtered, washed and dried with water, and the solid was passed through a silica gel column using a mixed solvent of ethyl acetate: petroleum ether 1:3 as the mobile phase to purify the product to obtain a dark green solid
  • the product 2.2g was developed by TLC to show a mixture of many spots close together. It contains a mixture of perylene diimides with multiple substitutions
  • Formula I-1 (or may contain isomer I-1'): Formula I-2 (or may contain isomer I-2'); Formula I-3; Formula I-4 (or may contain isomer I-4'); Formula I-5 (or may contain isomer I-5'); Formula I-6; Comparative A; Comparative B.
  • the perylene amide compound connected to the phenyl ether group of the present invention shifts the fluorescence wavelength to the near-infrared band above 730 nm when the N-aliphatic heterocyclic ring also exists on the perylene structure, and shields the general perylene amide access to the phenyl ether group. After showing the nature of red fluorescence around 600nm.
  • At least one heterocyclic group and at least one aryl ether group are inserted into the four substitution positions of 1,6,7,12 of perylene diimide, although the introduction of aryl ether group usually makes the perylene diimide
  • the imine compound presents a red fluorescence wavelength of about 600nm, but by inserting an aryl ether group and a heterocyclic group into the perylene skeleton at the same time, the fluorescence wavelength of the obtained compound is still affected by the heterocyclic group and presents a near infrared above 700nm The fluorescence characteristics.
  • the simultaneous introduction of the aryl ether group and the heterocyclic group stabilizes the halogen in the remaining positions on the perylene skeleton, making the compound stable in the chemiluminescence reaction containing hydrogen peroxide.
  • the quantum yield of fluorescent dyes is increased, and the intensity of near-infrared fluorescence is increased.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

式Ⅰ所示的苝二酰亚胺化合物及其作为近红外荧光染料的应用，式I 其中，R表示取代或未取代的烷基或芳基；Ar表示取代或未取代的苯基；X、Y和Z选自脂肪族杂环基团、卤素、氢和芳醚基，且至少一个取代基为脂肪族杂环基团，脂肪族杂环基团通过N-C键连接于苝骨架上。该化合物荧光染料量子产率提高，近红外荧光强度增加，且在含有过氧化氢的化学发光反应中稳定。

Description

一类杂环基取代苝酰胺化合物及其应用 技术领域
本发明涉及一类杂环基取代苝酰胺化合物及其应用。
背景技术
中国专利(200510059303.1)公开了一类以杂环化合物取代苝骨架的荧光染料为基础的化学红外辐射剂，公开的化合物是通过杂环化合物吗啉与多卤代苝酰胺反应生成化合物。实践中由于吗啉基团是强给电子基团，一旦取代卤素接入苝的1、6、7、12任意一个位置后使苝环的电子云密度升高，位阻较大，进一步的接入下一个吗啉基团就变得比较困难，合成产物多是各种取代情况和多种异构体的混合物，其中含有未完全取代在1、6、7、12任意位置上还留有卤素基团的化合物。这类混合物分离非常困难，而含有未完全取代的卤素的化合物在后续的含有过氧化剂的化学发光反应中不稳定，易发生淬灭，因此需要对该类化合物进行改进。
发明内容
本发明的目的是提供一种稳定的近红外荧光化合物，并以此为基础提供一种输出近红外荧光的组份。
本发明所提供的化合物的结构式如式Ⅰ：
Figure PCTCN2021098218-appb-000001
式Ⅰ中，R表示取代或未取代的烷基或芳基；
Ar表示取代或未取代的苯基；
X、Y和Z选自脂肪族杂环基团、卤素、氢和芳醚基，且至少一个取 代基为所述脂肪族杂环基团，所述脂肪族杂环基团通过N-C键连接于苝骨架上。
具体地，式Ⅰ中，R可为C4～C18的直链烷基或醚基取代的直链烷基，或苯基或烷基取代的苯基，优选C4～C18的直链烷基、十八烷基或2,6-二异丙基苯基。
具体地，式Ⅰ中，Ar优选为苯基或C1～C8的烷基取代的苯基。
具体地，所述脂肪族杂环基团可为吗啉基或四氢吡咯基；
所述卤素优选为溴或氯；
所述芳醚基优选为苯氧基。
具体地，式Ⅰ中，X、Y和Z的取代情况如下1)或2)：
1)一个取代基为所述脂肪族杂环基团，另两个取代基均为卤素、芳醚基或氢；
优选：a)一个取代基为吗啉基，另两个取代基均为氯；b)一个取代基为吗啉基，另两个取代基均为氢；c)一个取代基为吗啉基，另两个取代基均为苯氧基；d)一个取代基为四氢吡咯基，另两个取代基均为氯；
2)三个取代基分别为所述脂肪族杂环基团、卤素和芳醚基；
优选：三个取代基分别为吗啉基、氯和苯氧基；
本发明提供的化合物优选为下述任一种：
Figure PCTCN2021098218-appb-000002
Figure PCTCN2021098218-appb-000003
Figure PCTCN2021098218-appb-000004
Figure PCTCN2021098218-appb-000005
获得本发明提供的化合物的合成设计思路上，由于苯氧基的给电子能力比N-杂环化合物要小，而且吗啉等脂肪族N-杂环化合物的亲核能力很强，所以先连接苯氧基后再接入杂环基团是优选的方案。苯酚取代苝上的卤代基团可通过现有方法制备得到，如：首先卤素取代的苝酰二亚胺与ArOH反应得到ArO-取代的苝酰二亚胺，并分离得到不同取代情况的苝酰二亚胺；然后再连接脂肪族N-杂环基团，具体可采用吗啉或四氢吡咯与ArO-取代的不同情况的苝酰二亚胺上的卤素反应。
本发明化合物与双草酸酯、过氧化氢和溶剂复配得到输出近红外荧光的组份，其中，所述化合物的浓度为0.0001～0.01mol/L。
所述输出近红外荧光的组份还包括催化剂；
所述双草酸酯与所述化合物的摩尔比为10～1000:1；
所述过氧化氢占所述输出近红外荧光的组份总质量的0.1％～5％；
其中，所述双草酸酯可为双(2,4,5-三氯-6-羰戊氧基苯基)双草酸酯；
所述溶剂可为邻苯二甲酸酯、苯甲酸酯类等；
所述催化剂可为水杨酸钠。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1、中间体的制备
反应方程式如下所示：
Figure PCTCN2021098218-appb-000006
取橙黄色的N,N’-二(2,6-二异丙基苯基)四氯苝酰二亚胺原料20g(23.6mmol)，加入苯酚40g(425mmol)，无水碳酸钾20g(140mmol)在200ml NMP中70℃反应。以TLC检测，生成一苯氧基取代产物、二苯氧基取代产物、三苯氧基取代产物的混合物。通过硅胶柱色谱分离产品，使用乙酸乙酯：正己烷＝1:10的混合溶剂为流动相，分离分别得到1-苯氧基-6,7,12三氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺6.2g(中间体1)、1，7-二苯氧基-6,12-二氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺4.6g(中间体2)、1,6,7-三苯氧基-12-氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺3.2g(中间体3)。三个产物都为红色固体。
实施例2、式Ⅰ-1-5所示化合物的制备
1、式Ⅰ-1(式Ⅰ-1’)所示化合物的制备：
反应方程式如下所示：
Figure PCTCN2021098218-appb-000007
中间体1：(1-苯氧基-6,7,12-三氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺)1g与20ml的吗啉、无水碳酸钾2.3g回流反应4小时，以100倍量10％稀盐酸终止反应，过滤析出物，水洗干燥后固体通过硅胶柱，使用乙酸乙酯：正己烷＝1：10的混合溶剂为流动相纯化产品，得到墨绿色固体产物395mg为式Ⅰ-1所示化合物：1-苯氧基-6，12-二氯-7-吗啉基-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺，或其异构体(式Ⅰ-1’所示)：1-苯氧基6-吗啉基-7,12二氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺的混合物。以下涉及式I-1所示化合物时均表示同时可能含有其异构体(式I-1’所示化合物)。
1H NMR(400MHz,CDCl 3,25℃,TMS)：δ8.72(s,1H),8.60(s,1H),8.44(s,1H),8.40(s,1H),7.53～7.48(m,2H),7.35(d,J＝8.0Hz,4H),7.25(d,2H,J＝8.0Hz),7.10(t,1H,J＝8.0Hz),6.89(d,2H,J＝8.0Hz),4.17～4.11(m,3H),3.95(d,1H,J＝7.2Hz),3.75(d,1H,J＝11.2Hz),3.43(t,1H,J＝10.8Hz),3.22(t,1H,J＝10.8Hz),2.81～2.72(m,4H),2.24(d,J＝12.8Hz,1H),1.22～1.81(m,24H)ppm.
MS(Maldi-TOF):理论值C 58H 51Cl 2N 3O 6[M +]955.32,测量值955.3.
由表征数据可知所得化合物结构正确。
2、式Ⅰ-2(式I-2’)所示化合物的制备
中间体2(1，7-二苯氧基-6,12-二氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺)1g与20ml的吗啉、无水碳酸钾2.3g回流反应4小 时，以100倍量10％稀盐酸终止反应，过滤析出物，水洗干燥后固体通过硅胶柱，使用乙酸乙酯:正己烷＝1:10的混合溶剂为流动相纯化产品，得到墨绿色固体产物式Ⅰ-2所示化合物：1，6-二苯氧基-7-吗啉基-12-氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺，或其异构体(式I-2’所示)1，7-二苯氧基-6-吗啉基-12-氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺)110mg。
下涉及式I-2所示化合物时均表示同时可能含有其异构体(式I-2’所示化合物)。
1H NMR(400MHz,CDCl 3,25℃,TMS)δ8.75(s,1H),8.59(s,1H),8.44(s,1H),8.38(s,1H),7.54～7.45(m,3H),7.39～7.33(m,4H),7.29～7.26(m,5H),7.14～7.08(m,1),6.92(d,2H,J＝8.0Hz),4.19～4.14(m,3H),4.00～3.98(m,1H),3.81～3.78(m,1H),3.49～3.44(m,1H),3.31～3.19(m,1H),2.81～2.73(m,4H),2.36～2.23(m,1H),1.25～1.16(m,24H)ppm.
MS(Maldi-TOF):理论值C 64H 56ClN 3O 7[M +]1013.38,测量值1013.2.
由核磁表征数据与质谱给出的分子量结合分析可知所得化合物结构正确。
3、式Ⅰ-3所示化合物的制备
中间体3(1,6,7-三苯氧基-12-氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺)1g与20ml的吗啉、无水碳酸钾2.3g回流反应8小时，以100倍量10％稀盐酸终止反应，水洗过滤析出物，干燥后固体通过硅胶柱，使用乙酸乙酯:正己烷＝1:5的混合溶剂为流动相纯化产品，得到墨绿色固体产物式Ⅰ-3所示化合物：1,7,12-三苯氧基-6-吗啉基-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺60mg。
核磁数据： 1H NMR(500MHz,CDCl 3,25℃,TMS)δ8.36(s,1H),8.34(s,1H),8.29(s,1H),8.10(s,1H),7.46～7.43(m,2H),7.31～7.29(m,4H),7.28～7.22(m,6H),7.11～7.03(m,3H),7.00(d,2H,J＝7.5Hz),6.92(d,2H,J＝7.5Hz),6.88(d,2H,J＝7.5Hz),4.17～4.07(m,3H),3.97(t,1H,J＝8.5Hz),3.79(d,1H,J＝10.5Hz),3.48(t,1H,J＝9Hz),3.24(t,1H,J＝10Hz),2.80～2.67(m,4H),2.36(d,1H,J＝12Hz),1.19～1.13(m,24H)ppm.
MS(Maldi-TOF):理论值C 70H 61N 3O 8[M +]1071.45,测量值1071.5.
由核磁表征数据与质谱给出的分子量结合分析可知所得化合物结构正 确。
4、式Ⅰ-4(式Ⅰ-4’)所示化合物的制备
中间体1(一苯氧基取代的苝二酰亚胺)1g与20ml的四氢吡咯回流反应4小时，以100倍量10％稀盐酸终止反应，过滤析出物，干燥后固体通过硅胶柱，使用乙酸乙酯:正己烷＝1:10的混合溶剂为流动相纯化产品，得到墨绿色固体产物92mg为式Ⅰ-4所示化合物：1-苯氧基-6-氯-7-四氢吡咯基-12-氯，-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺，或与其异构体(式Ⅰ-4’)：1-苯氧基6-四氢吡咯基-7,12二氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺的混合物。以下涉及式I-4所示化合物时均表示同时可能含有其异构体(式I-4’所示化合物)。
1H NMR(400MHz,CDCl 3,25℃,TMS)δ8.77(s,1H),8.60(s,1H),8.55(s,1H),8.32(s,1H),7.55(m,2H),7.40(m,4H),7.18(t,J＝8.0Hz),7.02(t,J＝8.0Hz),6.68(d,J＝8.0Hz),4.11(m,2H),3.04(m,1H),2.87(m,4H),2.38(m,3H),1.71(m,2H),1.26(m,24H)ppm.13C NMR(400MHz,CDCl 3)δ168.75,163.71,163.40,163.33,163.07,154.38,148.62,147.35,145.73,145.63,145.53,134.89,133.12,132.54,132.42,131.70,130.62,130.54,130.41,129.68,128.44,127.72,124.98,124.18,124.12,124.07,123.88,123.35,123.09,122.80,122.58,122.30,121.78,121.04,119.76,119.32,117.16,108.80,53.21,50.35,29.25,26.43,25.48,24.23,24.15,24.02ppm.
MS(Maldi-TOF):理论值C 58H 51Cl 2N 3O 5[M +]939.32,测量值939.3.
由核磁表征数据与质谱给出的分子量结合分析可知所得化合物结构正确。
5、式Ⅰ-5(I-5’)所示化合物的制备
取棕红色的N,N’-二(2,6-二异丙基苯基)1，7-二溴苝酰二亚胺10g(11.5mmol)，加入苯酚20g(212.51mmol)，无水碳酸钾9.77g(70.70mmol)在100ml NMP中70℃反应。以TLC检测，生成一苯氧基取代产物、二苯氧基取代产物、的混合物。通过硅胶柱色谱分离产品，使用乙酸乙酯：正己烷＝1：10的混合溶剂为流动相，分离第一流份得到1-苯氧基-7溴-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺4.3g鲜红色固体(中间体4)。
1H NMR(400MHz,CDCl 3,25℃,TMS)δ9.74(d,1H,J＝8.4Hz),9.54(d, 1H,J＝8.0Hz),9.10(s,1H),8.81(dd,2H,J1＝8.4Hz,J2＝3.2Hz),8.45(s,1H),7.56～7.48(m,4H),7.39(t,4H,J＝7.2Hz),7.31(t,1H,J＝7.6Hz),7.23(d,2H,J＝8.4Hz),2.82～2.75(m,4H),1.24～1.19(m,24)ppm.
Figure PCTCN2021098218-appb-000008
中间体4(1-苯氧基-7-溴-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺)1g与20ml的吗啉、无水碳酸钾2.3g回流反应4小时，以100倍量10％稀盐酸终止反应，过滤析出物，水洗干燥后固体通过硅胶柱，使用乙酸乙酯:正己烷＝1:10的混合溶剂为流动相纯化产品，得到墨绿色固体产物195mg为式Ⅰ-5所示化合物：1-苯氧基-7-吗啉基-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺，或其异构体(式I-5’所示):1-苯氧基-6-吗啉基-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺。)以下涉及式I-5所示化合物时均表示同时可能含有其异构体(式I-5’所示化合物)。
6、式Ⅰ-6所示化合物的制备
取橙红色的N,N’-双(十八烷基)-四氯苝酰二亚胺原料24.3g(23.6mmol)，加入对叔丁基苯酚64g(425mmol)，无水碳酸钾20g(140mmol)在200ml NMP中95℃反应。以TLC检测可以看到：1，6，7，12位一至四取代的对叔丁基苯氧基取代产物的四个紫红色顺序展开点。适当提高温度，以TCL监测使反应向三取代、四取代产物过渡，降温冷却后以稀盐酸和水洗产物，干燥后的固体使用乙酸乙酯：正己烷＝1:6的混合溶剂为流动相，硅胶柱分离其中1,6,7-三对叔丁基苯氧基-12-氯-N,N'-双(十八烷基)-3,4,9,10-苝二酰亚胺馏分，得紫红色固体产物3.5g。
1,6,7-三对叔丁基苯氧基-12-氯-N,N'-双(十八烷基)-3,4,9,10-苝二酰亚胺1g与100ml的吗啉、无水碳酸钾12g回流反应22小时，以100倍量10％稀 盐酸终止反应，水洗过滤析出物，干燥后固体通过硅胶柱，使用乙酸乙酯:正己烷＝1:6的混合溶剂为流动相纯化产品，得到墨绿色固体产物式Ⅰ-6所示化合物：1,6,7-三对叔丁基苯氧基-12-吗啉基-N,N'-双(十八烷基)-3,4,9,10-苝二酰亚胺75mg。
核磁数据： 1H NMR(400MHz,CDCl3):δ8.28(s,1H),8.26(s,2H),8.07(s,1H),7.23～7.19(m,6H),6.82(d,4H,J＝8.8Hz),6.75(d,2H,J＝8.8Hz),4.14～4.06(m,6H),4.00～3.92(m,2H),3.68(d,1H,J＝12Hz),3.39(t,1H,J＝8.4Hz),3.06(t,1H,J＝10Hz),2.25(d,1H,J＝8.0Hz),1.73～1.64(m,4H),1.39～1.33(m,4H),1.29～1.28(m,27H),1.26～1.23(m,56H),0.87(t,6H,J＝6.4Hz)ppm.
7、对比物A的制备
CN200510059303.1描述已知方法过量的吗啉与氯代的苝二酰亚胺回流可以获得吗啉基取代的苝二酰亚胺化合物。取橙黄橙色的N,N’-二(2,6-二异丙基苯基)1，6，7，12四氯苝酰二亚胺原料5g与200ml的吗啉、无水碳酸钾18g回流反应48小时，以3000毫升10％稀盐酸终止反应，过滤析出物，水洗干燥后固体通过硅胶柱使用乙酸乙酯:石油醚＝1:3的混合溶剂为流动相纯化产品，得到黑墨绿色固体产物2.2g经TLC展开可见多点靠近的混合物。其包含吗啉基多种取代情况的苝二酰亚胺的混合物。
对比物A：以乙酸乙酯:正己烷＝1:5的混合溶剂为流动相以硅胶柱分离上述混合物，取TLC显示的自上向下的第二点相同的留份得产物660mg为对比物B，氢谱核磁证实为1，7-二吗啉基-6,12-二氯-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺，结构式如式A所示。
Figure PCTCN2021098218-appb-000009
1H NMR(400MHz,CDCl 3,25℃,TMS)δ8.59(s,2H),8.55(s,2H),7.55(t,2H,J＝8Hz),7.39(d,4H,J＝7.6Hz),4.22～4.12(m,4H),4.08～4.05(m,2H),3.99～3.95(m,2H),3.70～3.67(m,2H),3.48～3.43(m,2H),3.00～2.95(m,2H), 2.89～2.74(m,4H),2.43～2.39(m,2H),1.26～1.19(m,24H)ppm.
MS(Maldi-TOF):理论值C56H54Cl2N4O6[M+]948.34,测量值948.3.
8、对比物B的制备
按文献：Org.Chem.Front.,2018,5,1825E ffi cient catalytic vicinal diamination of arylene diimides将双(2,6-二异丙基苯基)苝酰二亚胺1.00g(1.41mmol)，吗啉15.00g(172.17mmol)和1ml去离子水放入100ml圆底烧瓶中，在将溴化铜314.20mg(1.41mmol)和碳酸铯1.38g(4.22mmol)加入其中，将反应在大气条件下加热搅拌回流24h。冷却至室温后加入二氯甲烷和去离子水萃取分液，取二氯甲烷层无水硫酸钠干燥过滤然后旋干通过柱色谱分离技术石油醚:乙酸乙酯20:1分离得到蓝色化合物为对比物B：1，6-二吗啉基-N,N'-双(2,6-二异丙基苯基)-3,4,9,10-苝二酰亚胺，结构式如式B所示。
Figure PCTCN2021098218-appb-000010
1H NMR(400MHz,CDCl 3,25℃,TMS)δ10.00(d,2H,J＝8.0Hz),8.72(d,2H,J＝8.4Hz),8.50(s,2H),7.54(t,2H,J＝8.4Hz),7.39(d,4H,J＝8Hz),4.04～3.96(m,8H),3.41(d,4H,J＝12Hz),3.24～3.18(m,4H),2.86～2.75(m,4H),1.24～1.22(m,24)ppm.
MS(Maldi-TOF):理论值C 56H 56N 4O 6[M +]880.42,测量值880.4.
实施例3、
以上实施例2中合成得到的化合物：
式Ⅰ-1(或可能含有异构体Ⅰ-1’)：式Ⅰ-2(或可能含有异构体Ⅰ-2’)；式Ⅰ-3；式Ⅰ-4(或可能含有异构体Ⅰ-4’)；式Ⅰ-5(或可能含有异构体Ⅰ-5’)；式Ⅰ-6；对比物A；对比物B。
分别各取上述苝基染料30mg与2g双(2,4,5-三氯-6-羰戊氧基苯基)草酸酯加入苯甲酸乙酯至20ml在具塞锥形瓶内以氩气保护，超声波下溶解。其中对比物B为蓝色溶液，其它7瓶呈墨绿色溶液，备用。
以160ml邻苯二甲酸二甲酯和40ml无水叔丁醇的混合物，其中溶解了4g 85％过氧化氢和20mg水扬酸钠。该溶液构成了200ml活化剂。
准备日本日立F-7000荧光光谱仪；测试狭缝10nm，扫描波长范围600～800nm。
逐一取以各苝基染料配制的双草酸酯溶液6ml分别加具塞塑料聚乙烯试管中，再加入3ml活化剂，摇动后插入仪器测光仓，读出各试管种初始反应时近红外荧光波长峰值。收集数据填入下表1。
表1 各化合物的最大吸收波长
Figure PCTCN2021098218-appb-000011
本发明接入苯醚基的苝酰胺化合物，在苝结构上同时存在N-脂肪族杂环的情况下，使荧光波长移动到了730nm以上的近红外波段，遮蔽了一般苝酰胺接入苯醚基后呈600nm左右红色荧光的性质。
实施例4、
逐一取实施例3中以各苝基染料配制的双草酸酯溶液6ml分别加入10ml玻璃安瓶中并封口，每种样品封两个安瓶，共8组16个安瓶。将其中一组8支安瓶放入65℃烘箱老化100小时，另一组8支常温放置100小时。老化样品冷却至常温25℃后，分别取0.5ml老化与常温两组各苝基染料配制的双草酸酯溶液加入5ml平底旋塞瓶中，再加入0.6ml激活液，旋紧瓶塞，激烈摇动使其混合同时计时，摇动开始后的第十秒将瓶子放在FZ-A型辐照计传感器窗口上面，读数并记录第20秒、15分钟、60分钟的数据入下表2。
表2 储存温度对不同取代基苝酰胺染料的近红外荧光强度的影响
Figure PCTCN2021098218-appb-000012
(单位：uW/cm 2)
由表2中的数据可以看出，式Ⅰ-1-式Ⅰ-6所示化合物含有苯醚基和脂肪族N杂环取代的苝酰亚胺与对比物B则只含有脂肪族N杂环，其老化稳定性都能够得到保证，但对比物B的近红外荧光强度较低；而对比物A则含氯元素和吗啉基，在高温老化后其溶液与过氧化氢反应时稳定性大大降低，出现了严重的衰减。
工业应用
本发明通过在苝酰二亚胺的1,6,7,12四个取代位接入至少一个杂环基团和至少一个芳醚基团，虽然芳醚基团的引入通常会使苝酰二亚胺类化合物呈现600nm左右的红色荧光波长，但是通过在苝骨架同时接入芳醚基团与杂环基团，所得化合物的荧光波长则还是受杂环基团的影响呈现700nm以上的近红外的荧光特性。另外，芳醚基团与杂环基团的同时引入对苝骨架上剩余位置的卤素起到了稳定作用，使得该化合物在含有过氧化氢的化学发光反应中变得稳定，同时由于引入芳醚基团后荧光染料量子产率提高，近红外荧光强度得以增加。

Claims (10)

  1. 式Ⅰ所示化合物，
    Figure PCTCN2021098218-appb-100001
    式Ⅰ中，R表示取代或未取代的烷基或芳基；
    Ar表示取代或未取代的苯基；
    X、Y和Z选自脂肪族杂环基团、卤素、氢和芳醚基，且至少一个取代基为所述脂肪族杂环基团，所述脂肪族杂环基团通过N-C键连接于苝骨架上。
  2. 根据权利要求1所述的化合物，其特征在于：式Ⅰ中，R为C4～C18的直链烷基或醚基取代的直链烷基，或苯基或烷基取代的苯基。
  3. 根据权利要求1或2所述的化合物，其特征在于：式Ⅰ中，Ar为苯基或C1～C8的烷基取代的苯基。
  4. 根据权利要求1-3中任一项所述的化合物，其特征在于：所述脂肪族杂环基团为吗啉基或四氢吡咯基；
    所述卤素为溴或氯；
    所述芳醚基为苯氧基。
  5. 根据权利要求1-4中任一项所述的化合物，其特征在于：式Ⅰ中，X、Y和Z的取代如下1)或2)：
    1)一个取代基为所述脂肪族杂环基团，另两个取代基均为卤素、芳醚基或氢；
    2)三个取代基分别为所述脂肪族杂环基团、卤素和芳醚基。
  6. 根据权利要求5所述的化合物，其特征在于：式Ⅰ中，X、Y和Z的取代如下A)-E)中任一种：
    A)一个取代基为吗啉基，另两个取代基均为氯；
    B)一个取代基为吗啉基，另两个取代基均为氢；
    C)一个取代基为吗啉基，另两个取代基均为苯氧基；
    D)一个取代基为四氢吡咯基，另两个取代基均为氯；
    E)三个取代基分别为吗啉基、氯和苯氧基。
  7. 一种近红外荧光染料，为权利要求1-6中任一项所述化合物。
  8. 一种输出近红外荧光的组份，其活性成分为权利要求1-6中任一项所述化合物。
  9. 根据权利要求8所述的输出近红外荧光的组份，其特征在于：所述输出近红外荧光的组份由双草酸酯、过氧化氢、溶剂和所述化合物制成。
  10. 根据权利要求9所述的输出近红外荧光的组份，其特征在于：所述输出近红外荧光的组份中，所述化合物的浓度为0.0001～0.01mol/L。
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