CN107043397A - 亚磷酸取代苝酰亚胺化合物及其合成方法 - Google Patents
亚磷酸取代苝酰亚胺化合物及其合成方法 Download PDFInfo
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- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical class C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 6
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- 150000002460 imidazoles Chemical class 0.000 claims description 3
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- 229910019142 PO4 Inorganic materials 0.000 claims description 2
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- 239000010452 phosphate Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 3
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- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OGSPWJRAVKPPFI-UHFFFAOYSA-N Alendronic Acid Chemical compound NCCCC(O)(P(O)(O)=O)P(O)(O)=O OGSPWJRAVKPPFI-UHFFFAOYSA-N 0.000 description 1
- 101100189168 Capsicum frutescens PAMT gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 241000736199 Paeonia Species 0.000 description 1
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- 229960004343 alendronic acid Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
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- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
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Abstract
本发明涉及一种亚磷酸取代苝酰亚胺化合物及其合成方法，其结构式为：分子式为：C28H22(CH2)nN2O18P4。本发明的苝酰亚胺化合物具有稳定的阴离子，能够进一步提高水溶性；该方法采用的合成反应原料价格低，副反应少，溶剂低毒，操作非常简易，产率达60～70%，适合大规模生产。
Description
技术领域
本发明涉及的一种亚磷酸取代苝酰亚胺化合物及其合成方法。
背景技术
苝酰亚胺化合物刚性共轭面大，具有较高的电子亲和能和电荷传导能力；摩尔吸光系数ε和荧光量子产率Φ较高，光谱可调性较大，具有丰富的颜色变化；光稳定性和热稳定性较高，是一种很好的n型材料。因此除了在传统的染（颜）料行业中继续发挥作用外，还被广泛应用于有机光导材料、有机电致发光材料、液晶显示材料、激光染料、化学发光色素、染料敏化太阳能电池和分子开关等领域。但由于大多数苝化合物在水中的溶解性不高，很大程度上阻碍了这类化合物的进一步应用，尤其是在生物医药领域。
发明内容
本发明目的之一在于克服上述现有技术存在的苝酰亚胺化合物溶解性不高的问题，提供一种亚磷酸取代苝酰亚胺化合物。
本发明的目的之二在于提供该化合物的合成方法。
本发明通过合理的设计，使苝酰亚胺化合物具有稳定的阴离子，能够进一步提高溶解性，该制备方法操作简易，产率高。具体反应机理为：
为达到上述目的，本发明采用如下技术方案：
一种亚磷酸取代苝酰亚胺化合物，其特征在于该化合物的结构式为：
其中n=1~4。
一种制备上述的亚磷酸取代苝酰亚胺化合物的方法，其特征在于该方法的具体步骤为：在惰性气体保护下，将3,4,9,10-苝四羧酸二酐和含氮磷酸盐类化合物按1：（2~3）的摩尔比溶于咪唑中，回流反应10~16h，得到深红色溶液；冷却至室温后，有深红色沉淀析出，将产物溶解在热水中，除去不溶性杂质，调节滤液pH=2~4,得到红色沉淀，离心、水洗、乙醇，得到粗产物；将该粗产物溶解在水中，调节pH为10~12，去除不溶固体，再调节pH=2~4，离心、水洗、乙醇、干燥，得到红色产物，即为亚磷酸取代苝酰亚胺化合物。
本发明具有如下显而易见的突出性特点和显著性优点：本发明的亚磷酸取代基的苝酰亚胺化合物在溶液中能够产生稳定的阴离子，进一步提高在水中的溶解度。磷酸取代基的生物相容性好，使得这种化合物能够在生物化学领域和药物缓释等方面有潜在的应用。该方法采用的合成反应原料价格低，副反应少，溶剂低毒，操作非常简易，产率达60～70%，适合大规模生产。
附图说明
图1为本发明实施例制备的亚磷酸取代基的苝酰亚胺化合物（n=2）的核磁共振谱，图中，横坐标为化学位移（δ）,单位为ppm，纵坐标为峰的强度。
图2为本发明实施例制备的亚磷酸取代基的苝酰亚胺化合物（n=2）的红外光谱（IR）图。
具体实施方式：
以下结合附图对本发明的实施例作详细地说明。
实施例1（n=2）：
(1).首先称取3,4,9,10-苝四羧酸二酐（PTCDA, 400mg，1.0mmol）、三水合阿仑磷酸单钠盐（820mg, 2.5mmol）、咪唑（9g）于100mL单口圆底烧瓶中，在N2保护下搅拌、加热到110-130°C，回流反应10-12h，得到深红色溶液。
(2).将上述反应后的溶液冷却至室温后，向反应器中加入100mL热水 ，产物溶解在热水中，减压抽滤，除去不溶性杂质。深红色溶液用2.0M HCl酸化至大约pH=3,得到红色沉淀，离心、水洗、乙醇各洗涤三次，得到红色固体。80°C真空干燥12h，得到粗产物。
(3).将粗产物溶解在50mL水中，用2.0M KOH溶液调节pH约为10，此时产物基本全部溶解。离心去除微量不溶固体。再将深红色溶液用2.0M HCl酸化至大约pH=3,离心、水洗、乙醇洗三次。80°C真空干燥12h。重复KOH溶解，HCl酸化操作2-3次，完全去除杂质，得到红色产物PAMT（528.35mg,产率63%）。
紫外可见吸收光谱数据（H2O）:λmax/nm(ε/M-1cm-1)=533(5.8ⅹ104)，498（4.4ⅹ104）,465(1.9ⅹ104)。
荧光发射光谱数据（H2O，激发波长500nm，狭缝宽度3nm，3nm，低灵敏度）：
λmax/nm：554，595。
溶解度：2.35g/1mL H2O
采用Bruker AC-300 核磁共振仪对上述亚磷酸取代基的苝酰亚胺化合物进行测定，TMS 为内标，氘代D2O和30%氘代NaOD为溶剂，化学位移以ppm 为单位，如图1中所示的亚磷酸取代基的苝酰亚胺化合物的核磁共振氢谱谱图。8.22和8.00ppm的峰归属于苝环上的8个H，两者相互影响，因此存在裂分。4.08ppm的峰归属于c处的H，因为离苯环较近，因而化学位移偏高。2.07和1.87 ppm的峰归属于d、e两处亚甲基上的H，由于两者化学环境相近，峰形有一点重合。
采用红外光谱采用KBr压片法，美国尼高力公司AVATAR370型红外光谱仪对上述亚磷酸取代基的苝酰亚胺化合物进行测定，图2为由实施例制备亚磷酸取代基的苝酰亚胺化合物的红外光谱（IR）图，图中，横坐标为波数（wavenumber），单位为cm-1，纵坐标为透射率(Transmittance%)，3434归属于酰胺N-H伸缩振动，2955为饱和C-H伸缩振动，1695,1646是酰亚胺特征峰, 1586为苝环C=C伸缩振动,1445,1348归属于C-N伸缩振动, 1248,1172,1074,935为羧酸中C-O伸缩振动, 806,745,656,515为C-H非平面摇摆。
本实施例合成的亚磷酸取代基的苝酰亚胺化合物可用于金属离子浓度的测定和骨质疏松症的机理研究。
Claims (2)
1.一种亚磷酸取代苝酰亚胺化合物，其特征在于该化合物的结构式为：
其中n=1~4。
2.一种制备根据权利要求1所述的亚磷酸取代苝酰亚胺化合物的方法，其特征在于该方法的具体步骤为：在惰性气体保护下，将3,4,9,10-苝四羧酸二酐和含氮磷酸盐类化合物按1：（2~3）的摩尔比溶于咪唑中，回流反应10~16h，得到深红色溶液；冷却至室温后，有深红色沉淀析出，将产物溶解在热水中，除去不溶性杂质，调节滤液pH=2~4,得到红色沉淀，离心、水洗、乙醇，得到粗产物；将该粗产物溶解在水中，调节pH为10~12，去除不溶固体，再调节pH=2~4，离心、水洗、乙醇、干燥，得到红色产物，即为亚磷酸取代苝酰亚胺化合物。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111777761A (zh) * | 2020-06-03 | 2020-10-16 | 北京大学深圳研究生院 | 含膦苝二酰亚胺界面材料及其合成方法和太阳能电池 |
| CN112791747A (zh) * | 2021-01-05 | 2021-05-14 | 黑龙江大学 | 一种超薄二维磷酸调控的金属酞菁/苝酰亚胺复合光催化剂的制备方法及应用 |
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| SERGIO BROCHSZTAIN ET AL.,: ""Characterization of self-assembled thin films of zirconium phosphonate/aromatic diimides"", 《THIN SOLID FILMS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777761A (zh) * | 2020-06-03 | 2020-10-16 | 北京大学深圳研究生院 | 含膦苝二酰亚胺界面材料及其合成方法和太阳能电池 |
| CN112791747A (zh) * | 2021-01-05 | 2021-05-14 | 黑龙江大学 | 一种超薄二维磷酸调控的金属酞菁/苝酰亚胺复合光催化剂的制备方法及应用 |
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