Compound as well as synthesis thereof and method for synthesizing double-UPy substituted compound by using same

Abstract

The invention discloses a compound which is 2[2-(1-ethanethiol)] urea-4 [1H]-pyrimidone. The invention also discloses a synthesis method of the compound, which comprises the steps: enabling cystamine dihydrochloride to react with activated ureido pyrimidine S1 to obtain a 2-urea-4[1H]-pyrimidine disubstituted sulfur-sulfur compound S2; and reducing the sulfur-sulfur compound S2 by using DTT (Dithiothreitol) to obtain the compound. The invention also discloses a method for synthesizing a double-UPy substituted compound by using the compound disclosed by the invention. According to the method, the compound has a free radical thiol-alkynyl click chemical reaction with an alkane alkynyl-terminated compound CHR to obtain the double-UPy substituted compound. According to the method disclosed by the invention, the thiol-alkynyl click chemical reaction is utilized to synthesize the double-UPy substituted compound for the first time; raw materials are easy to obtain, the application range is wide, the separation yield is high, and the synthesis method is scientific and reasonable; therefore a general method is provided for synthesizing the double-UPy substituted compound.

Description

technical field

[0001] The invention relates to a compound, its synthesis and a method for synthesizing a double UPy substituted compound, belonging to the field of organic synthesis. Background technique

[0002] The self-complementary quadruple hydrogen bond functional group 2-urea-4[1H]-pyrimidinone (UPy) has been widely developed since Meijer's invention due to its strong complexation and directionality. UPy-based supramolecular polymers have achieved many satisfactory results in the construction of functional materials. The double UPy substituted compounds are the basis for the formation of supramolecular polymers.

[0003] At present, the synthesis of double-UPy substituted compounds mainly uses the reaction of diamino compounds with activated ureidopyrimidinone compounds, or the reaction of isocytosine with diisocyanates. However, diamino compounds are not easy to synthesize, and it is often necessary to reduce the azide or nitro group under harsh conditions; at the...

Examples

Embodiment 1

[0039] 1) Dissolve 224mg, 1mmol of cystamine dihydrochloride in 5-50mL of anhydrous dichloromethane, add compound S1 (456-912mg, 1.5-3mmol), stir at room temperature for 5-15h, wash with brine three times , the collected organic phase was spin-dried, and separated by column chromatography to obtain compound S2.

[0040] 2) Dissolve compound S2 (100 mg, 0.16 mmol) in 15-100 mL of anhydrous dichloromethane, add 37-248 mg (0.24-1.6 mmol) of 1,4-dithiothreitol, and add a catalytic amount of 1,8 - Diazabicyclo[5.4.0]undec-7-ene (DBU) was refluxed for 0.25-3 hours, washed with water, the organic phase was collected, and spin-dried to obtain the product S3.

[0041]

Embodiment 2

[0043] Take 7 mg of propynyl alcohol and 398 mg of compound S, add the initiator DMPA (2-16 mg), dissolve and mix with 1.2 mL of 1,2-dichloroethane, and then carry out the light reaction. After 2 hours of light, the reaction is complete, and the organic solvent is spin-dried in vacuum for 1, 2-dichloroethane, compound 1a was obtained by column chromatography. Isolated yield 97%. The NMR data of the compound 1a are as follows: 1 H NMR (CDCl 3 ,400MHz,ppm): δ13.17-13.09 (m, 2H), 11.99-11.95 (m, 2H), 10.43 (s, 2H), 5.84 (s, 2H), 3.86-3.40 (m, 6H), 2.97 -2.78 (m, 7H), 2.31 (s, 2H), 1.71-1.52 (m, 8H), 1.32-1.20 (m, 8H), 1.21-0.84 (m, 12H).

[0044]

Embodiment 3

[0046] 1) Synthesis of propynyl pyrenecarboxylate: 1-pyrenecarboxylic acid (372mg, 1.5mmol), propynyl alcohol (265-530mg, 2.25-4.5mmol), and potassium carbonate (1-10g, 7.5-75mmol) were added After reacting in 10-60mL N,N-dimethylformamide solvent at 80°C for 5-12h, add a large amount of ethyl acetate and wash with water, collect the organic phase, spin dry, and obtain 391mg of the product by column chromatography. The NMR data of this compound are expressed as follows: 1 H NMR (CDCl 3 ,400MHz,ppm):δ9.32(d,J=9.2Hz,1H),8.71(d,J=8.4Hz,1H),8.30(q,3H),8.22(t,2H),8.12(q, 2H), 5.12(d, J=2.4Hz, 2H), 2.59(t, 1H).

[0047]2) Take 15 mg of propynyl pyrenecarboxylate and 398 mg of compound S in 1), add the initiator DMPA (2-16 mg), dissolve and mix with 1.2 mL of 1,2-dichloroethane, then carry out light reaction, and react after 2 hours of light After completion, the organic solvent 1,2-dichloroethane was spin-dried in vacuum, and compound 1b was obtained by column chromatography. Is...

technical field

[0001] The invention relates to a compound, its synthesis and a method for synthesizing a double UPy substituted compound, belonging to the field of organic synthesis. Background technique

[0002] The self-complementary quadruple hydrogen bond functional group 2-urea-4[1H]-pyrimidinone (UPy) has been widely developed since Meijer's invention due to its strong complexation and directionality. UPy-based supramolecular polymers have achieved many satisfactory results in the construction of functional materials. The double UPy substituted compounds are the basis for the formation of supramolecular polymers.

[0003] At present, the synthesis of double-UPy substituted compounds mainly uses the reaction of diamino compounds with activated ureidopyrimidinone compounds, or the reaction of isocytosine with diisocyanates. However, diamino compounds are not easy to synthesize, and it is often necessary to reduce the azide or nitro group under harsh conditions; at the...

Examples

Embodiment 1

[0039] 1) Dissolve 224mg, 1mmol of cystamine dihydrochloride in 5-50mL of anhydrous dichloromethane, add compound S1 (456-912mg, 1.5-3mmol), stir at room temperature for 5-15h, wash with brine three times , the collected organic phase was spin-dried, and separated by column chromatography to obtain compound S2.

[0040] 2) Dissolve compound S2 (100 mg, 0.16 mmol) in 15-100 mL of anhydrous dichloromethane, add 37-248 mg (0.24-1.6 mmol) of 1,4-dithiothreitol, and add a catalytic amount of 1,8 - Diazabicyclo[5.4.0]undec-7-ene (DBU) was refluxed for 0.25-3 hours, washed with water, the organic phase was collected, and spin-dried to obtain the product S3.

[0041]

Embodiment 2

[0043] Take 7 mg of propynyl alcohol and 398 mg of compound S, add the initiator DMPA (2-16 mg), dissolve and mix with 1.2 mL of 1,2-dichloroethane, and then carry out the light reaction. After 2 hours of light, the reaction is complete, and the organic solvent is spin-dried in vacuum for 1, 2-dichloroethane, compound 1a was obtained by column chromatography. Isolated yield 97%. The NMR data of the compound 1a are as follows: 1 H NMR (CDCl 3 ,400MHz,ppm): δ13.17-13.09 (m, 2H), 11.99-11.95 (m, 2H), 10.43 (s, 2H), 5.84 (s, 2H), 3.86-3.40 (m, 6H), 2.97 -2.78 (m, 7H), 2.31 (s, 2H), 1.71-1.52 (m, 8H), 1.32-1.20 (m, 8H), 1.21-0.84 (m, 12H).

[0044]

Embodiment 3

[0046] 1) Synthesis of propynyl pyrenecarboxylate: 1-pyrenecarboxylic acid (372mg, 1.5mmol), propynyl alcohol (265-530mg, 2.25-4.5mmol), and potassium carbonate (1-10g, 7.5-75mmol) were added After reacting in 10-60mL N,N-dimethylformamide solvent at 80°C for 5-12h, add a large amount of ethyl acetate and wash with water, collect the organic phase, spin dry, and obtain 391mg of the product by column chromatography. The NMR data of this compound are expressed as follows: 1 H NMR (CDCl 3 ,400MHz,ppm):δ9.32(d,J=9.2Hz,1H),8.71(d,J=8.4Hz,1H),8.30(q,3H),8.22(t,2H),8.12(q, 2H), 5.12(d, J=2.4Hz, 2H), 2.59(t, 1H).

[0047]2) Take 15 mg of propynyl pyrenecarboxylate and 398 mg of compound S in 1), add the initiator DMPA (2-16 mg), dissolve and mix with 1.2 mL of 1,2-dichloroethane, then carry out light reaction, and react after 2 hours of light After completion, the organic solvent 1,2-dichloroethane was spin-dried in vacuum, and compound 1b was obtained by column chromatography. Is...

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