HPTS series derivatives and synthesis method therefor

Abstract

Disclosed are HPTS series derivatives and a synthesis method thereof, belonging to the field of organic synthesis. The HPTS series derivatives are prepared by introducing alkylamine or alcohol into sulfonic acid groups of HPTS. The synthesis method comprises the following steps: subjecting HPTS and phosphorus oxychloride to heating and reflux reaction for 12 hours under catalysis of DMF to obtain a reaction product; introducing the reaction product into ice water, stirring, precipitating solid, and performing suction filtration to obtain HPTS-SO.sub.2Cl; dissolving the HPTS-SO.sub.2Cl in tetrahydrofuran to prepare solution A, and dissolving alkylamine or alcohol in tetrahydrofuran to prepare solution B; mixing the solution A with the solution B and then reacting for 24 hours at normal temperature, obtaining a product by rotary evaporation, and obtaining a pure compound after separation through columns. The derivatives have strong fat solubility, overcome the defect of a very strong water solubility.

Claims

1. A method for synthesizing a 8-hydroxy pyrene-1,3,6-sulfonate (HPTS) series derivative by introducing an alkylamine or an alcohol into sulfonic acid groups of the HPTS, comprising the following steps: (1) subjecting HPTS and phosphorus oxychloride to refluxing under catalysis of DMF to obtain a reaction product; (2) introducing the reaction product of step (1) into ice water, stirring, precipitating, and performing suction filtration to obtain HPTS-SO.sub.2Cl; (3) dissolving the HPTS-SO.sub.2Cl in tetrahydrofuran to prepare solution A, and dissolving an alkylamine or an alcohol in tetrahydrofuran to prepare solution B; and (4) mixing the solution A with the solution B and then reacting at normal temperature, obtaining a product by rotary evaporation, and obtaining a pure compound after separation through columns.

2. The method for synthesizing the HPTS series derivatives according to claim 1, wherein the molar ratio of the HPTS to the phosphorus oxychloride is 1:3-4.

3. The method for synthesizing the HPTS series derivatives according to claim 1, wherein the molar ratio of the HPTS-SO.sub.2Cl to the alkylamine or the alcohol is 1:3-4.

4. The method for synthesizing the HPTS series derivatives according to claim 3, wherein the time of the refluxing in step (1) is 12 hours; and the time of the reaction in step (4) is 24 hours.

5. A method for synthesizing a 8-hydroxy pyrene-1,3,6-sulfonate (HPTS) series derivative by introducing an alkylamine or an alcohol into sulfonic acid groups of the HPTS, comprising the following steps: (1) subjecting HPTS and phosphorus oxychloride to refluxing under catalysis of DMF to obtain a reaction product; (2) introducing the reaction product in step (1) into ice water, stirring, precipitating, and performing suction filtration to obtain HPTS-SO.sub.2Cl; (3) dissolving the HPTS-SO.sub.2Cl in an organic solvent to prepare solution A, and dissolving alkylamine or alcohol in an organic solvent to prepare solution B; and (4) mixing the solution A with the solution B and then reacting for 1 day at normal temperature, adding sodium bicarbonate as an acid binding agent, obtaining a product by rotary evaporation, and obtaining a pure compound after separation through columns.

6. The method for synthesizing the HPTS series derivatives according to claim 2, wherein the molar ratio of the HPTS-SO.sub.2Cl to the alkylamine or the alcohol is 1:3-4.

7. The method for synthesizing the HPTS series derivatives according to claim 6, wherein the time of the refluxing in step (1) is 12 hours; and the time of the reaction in step (4) is 24 hours.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic structural diagram of 8-hydroxy-1,3,6-trisulfdiethylamine (HPTS-diethyl amine) obtained in Example 1;

(2) FIG. 2 is a schematic structural diagram of 8-hydroxy-1,3,6-trisulfbutylamine (HPTS-n-butyl amine) obtained in Example 2;

(3) FIG. 3 is a schematic structural diagram of 8-hydroxy-1,3,6-trisulfonic ethyl ester (HPTS-ethyl ester) obtained in Example 3;

(4) FIG. 4 is a schematic structural diagram of 8-hydroxy-1,3,6-trisulfdipropylamine (HPTS-di-n-propylamine) obtained in Example 4;

(5) FIG. 5 is a schematic structural diagram of 8-hydroxy-1,3,6-trisulfdibutylamine (HPTS-di-n-butylamine) obtained in Example 5;

(6) FIG. 6 is a schematic structural diagram of 8-hydroxy-1,3,6-trisulfonic methyl ester (HPTS-methyl ester) obtained in Example 6; and

(7) FIG. 7 is a schematic diagram of a reaction synthesis route of HPTS series derivatives of the present invention.

DETAILED DESCRIPTION OF EMBODIMENTS

(8) The present invention will be further described below with reference to specific examples.

Example 1

(9) In this example, trisodium salt of 8-hydroxy pyrene-1,3,6-sulfonate (HPTS) is used as a precursor to synthesize 8-hydroxy-1,3,6-trisulfdiethylamine (HPTS-diethylamine), and the synthesis steps are as follows.

(10) (1) HPTS and phosphorus oxychloride are put into reaction according to 1:3 equivalent, DMF is used as catalyst, and refluxing for 12 hours.

(11) (2) The reaction product in step (1) is introduced into ice water at a slow speed and stirred, solid is precipitated, and suction filtration is performed to obtain HPTS-SO.sub.2Cl. The yield is 90%.

(12) (3) The HPTS-SO.sub.2Cl obtained in step (2) is dissolved in an appropriate amount of tetrahydrofuran (THF) to prepare solution A with a concentration of 0.3 mmol mL.sup.−1, and dimethylamine is dissolved in an appropriate amount of THF at 3 times equivalent to prepare solution B with a concentration of 0.5 mmol mL.sup.−1.

(13) (4) The solution B is added dropwise into the solution A to react for 24 hours at normal temperature, a product is obtained by rotary evaporation, and after separation on columns, a pure compound of HPTS-diethylamine can be obtained. The yield obtained in this example is 85%.

(14) FIG. 1 is a schematic structural diagram of HPTS-diethylamine obtained in this example.

(15) The purified product of HPTS-diethylamine is detected by a Brooke 400 MHz nuclear magnetic resonance spectrometer. Measured hydrogen spectrum data is as follows:

(16) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.19 (s, 1H), 9.12 (d, J=9.9 Hz, 1H), 9.02 (d, J=9.6 Hz, 1H), 8.97 (d, J=9.8 Hz, 1H), 8.78 (d, J=9.6 Hz, 1H), 8.54 (s, 1H), 3.54-3.39 (m, 12H), 1.18 (t, J=7.1 Hz, 12H), 1.08 (t, J=7.1 Hz, 6H).

Example 2

(17) In this example, trisodium salt of 8-hydroxy pyrene-1,3,6-sulfonate (HPTS) is used as a precursor to synthesize HPTS-n-butylamine and a synthesis method comprises the follows steps:

(18) (1) HPTS and phosphorus oxychloride are put into reaction according to 1:3.1 equivalent, DMF is used as catalyst, and refluxing reaction are performed for 12 hours.

(19) (2) The reaction product in step (1) is introduced into ice water at a slow speed and stirred, solid is precipitated, and suction filtration is performed to obtain HPTS-S02C1. The yield is 90%.

(20) (3) The HPTS-SO.sub.2Cl obtained in step (2) is dissolved in an appropriate amount of THF to prepare solution A with a concentration of 0.3 mmol mL.sup.−1, and n-butylamine is dissolved in an appropriate amount of THF at 3.1 times equivalent to prepare solution B with a concentration of 0.5 mmol mL.sup.−1.

(21) (4) The solution B is added dropwise into the solution A to react for 24 hours at normal temperature, a product is obtained by rotary evaporation, and after separation on columns, a pure compound of HPTS-n-butylamine can be obtained. The yield obtained in this example is 80%.

(22) FIG. 2 is a schematic structural diagram of HPTS-n-butylamine obtained in this example. The purified product of HPTS-n-butylamine is detected by a Brooke 400 MHz nuclear magnetic resonance spectrometer. Measured hydrogen spectrum data is as follows:

(23) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.29 (d, J=9.5, 7.3 Hz, 1H), δ 9.26 (d, J=9.5, 7.3 Hz, 1H), 9.20 (s, 1H), 9.13 (m, J=10.0 Hz, 4H), 8.85 (d, J=9.5 Hz, 1H), 8.46 (s, 1H), 2.63 (t, 6H), 1.54-1.30 (m, 12H), 0.89 (t, 9H).

Example 3

(24) In this example, trisodium salt of 8-hydroxy pyrene-1,3,6-sulfonate (HPTS) is used as a precursor to synthesize HPTS-ethyl ester and a synthesis method comprises the follows steps:

(25) (1) HPTS and phosphorus oxychloride are put into reaction according to 1:4 equivalent, DMF is used as catalyst, and refluxing for 12 hours.

(26) (2) The reaction product in step (1) is introduced into ice water at a slow speed and stirred, solid is precipitated, and suction filtration is performed to obtain HPTS-S02C1. The yield is 90%.

(27) (3) The HPTS-SO.sub.2Cl obtained in step (2) is dissolved in THF to prepare solution A with a concentration of 0.3 mmol mL.sup.−1, and anhydrous ethanol is dissolved in THF at 4 times equivalent to prepare solution B with a concentration of 0.5 mmol mL.sup.−1.

(28) (4) The solution B is slowly added dropwise into the solution A to react for 24 hours at normal temperature, a product is obtained by rotary evaporation, and after separation on columns, a pure compound of HPTS-ethyl ester can be obtained. The yield of the obtained HPTS-ethyl ester is 83%.

(29) FIG. 3 is a schematic structural diagram of HPTS-ethyl ester obtained in this example.

(30) The purified product of HPTS-ethyl ester is detected by a Brooke 400 MHz nuclear magnetic resonance spectrometer. Measured hydrogen spectrum data is as follows:

(31) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.29 (d, J=9.5, 7.3 Hz, 1H), δ 9.26 (d, J=9.5, 7.3 Hz, 1H), 9.20 (s, 1H), 9.13 (d, J=10.0 Hz, 1H), 8.85 (d, J=9.5 Hz, 1H), 8.46 (s, 1H), 3.94 (q, 6H), 1.54 (t, 9H).

Example 4

(32) In this example, trisodium salt of 8-hydroxy pyrene-1,3,6-sulfonate (HPTS) is used as a precursor to synthesize HPTS-di-n-propyl amine and a synthesis method comprises the follows steps:

(33) (1) HPTS and phosphorus oxychloride are put into reaction according to 1:3.1 equivalent, DMF is used as catalyst, and refluxing for 12 h.

(34) (2) The reaction product in step (1) is introduced into ice water at a slow speed and stirred, solid is precipitated, and suction filtration is performed to obtain HPTS-S02C1. The yield is 90%.

(35) (3) The HPTS-SO.sub.2Cl obtained in step (2) is dissolved in an appropriate amount of THF to prepare solution A with a concentration of 0.3 mmol mL.sup.−1, and di-n-propyl amine is dissolved in an appropriate amount of THF at 3.1 times equivalent to prepare solution B with a concentration of 0.5 mmol mL.sup.−1.

(36) (4) The solution B is slowly added dropwise into the solution A to react for 24 hours at normal temperature, a product is obtained by rotary evaporation, and after separation on columns, a pure compound of HPTS-di-n-propyl amine can be obtained. The yield obtained in this example is 75%.

(37) FIG. 4 is a schematic structural diagram of HPTS-di-n-propyl amine obtained in this example.

(38) The purified product of HPTS-di-n-propyl amine is detected by a Brooke 400 MHz nuclear magnetic resonance spectrometer. Measured hydrogen spectrum data is as follows:

(39) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.19 (s, 1H), 9.12 (d, J=9.9 Hz, 1H), 9.02 (d, J=9.6 Hz, 1H), 8.97 (d, J=9.8 Hz, 1H), 8.78 (d, J=9.6 Hz, 1H), 8.54 (s, 1H), 3.54-3.39 (m, 12H), 1.08 (m, J=7.1 Hz, 12H), 0.98 (t, J=7.1 Hz, 18H).

Example 5

(40) In this example, trisodium salt of 8-hydroxy pyrene-1,3,6-sulfonate (HPTS) is used as a precursor to prepare HPTS-dibutylamine and a preparation method comprises the follows steps:

(41) (1) HPTS and phosphorus oxychloride are put into reaction according to 1:3.1 equivalent, DMF is used as catalyst, and refluxing for 12 hours.

(42) (2) The reaction product in step (1) is introduced into ice water at a slow speed and stirred, solid is precipitated, and suction filtration is performed to obtain HPTS-S02C1. The yield is 90%.

(43) (3) The HPTS-SO.sub.2Cl obtained in step (2) is dissolved in an appropriate amount of THF to prepare solution A with a concentration of 0.3 mmol mL.sup.−1, and di-n-butylamine is dissolved in an appropriate amount of THF at 3.1 times equivalent to prepare solution B with a concentration of 0.5 mmol mL.sup.−1.

(44) (4) The solution B is slowly added dropwise into the solution A to react for 24 hours at normal temperature, a product is obtained by rotary evaporation, and after separation on columns, a pure compound of HPTS-di-n-butylamine can be obtained. The yield obtained in this example is 69%.

(45) FIG. 5 is a schematic structural diagram of HPTS-di-n-butylamine obtained in this example.

(46) The purified product of HPTS-di-n-butylamine is detected by a Brooke 400 MHz nuclear magnetic resonance spectrometer. Measured hydrogen spectrum data is as follows:

(47) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.19 (s, 1H), 9.12 (d, J=9.9 Hz, 1H), 9.02 (d, J=9.6 Hz, 1H), 8.97 (d, J=9.8 Hz, 1H), 8.78 (d, J=9.6 Hz, 1H), 8.54 (s, 1H), 3.54-3.39 (m, 12H), 1.40-1.21 (m, J=7.1 Hz, 24H), 0.98 (t, J=7.1 Hz, 18H).

Example 6

(48) In this example, trisodium salt of 8-hydroxy pyrene-1,3,6-sulfonate (HPTS) is used as a precursor to prepare HPTS-methyl ester and a preparation method comprises the follows steps:

(49) (1) HPTS and phosphorus oxychloride are put into reaction according to 1:3.1 equivalent, DMF is used as catalyst, and refluxing for 12 hours.

(50) (2) The reaction product in step (1) is introduced into ice water at a slow speed and stirred, solid is precipitated, and suction filtration is performed to obtain HPTS-S02C1. The yield is 90%.

(51) (3) The HPTS-SO.sub.2Cl obtained in step (2) is dissolved in an appropriate amount of THF to prepare solution A with a concentration of 0.3 mmol mL.sup.−1, and methanol is dissolved in an appropriate amount of THF at 3.1 times equivalent to prepare solution B with a concentration of 0.5 mmol mL.sup.−1.

(52) (4) The solution B is slowly added dropwise into the solution A to react for 24 hours at normal temperature, a product is obtained by rotary evaporation, and after separation on columns, a pure compound of HPTS-methyl ester can be obtained. The yield obtained in this example is 89%.

(53) FIG. 6 is a schematic structural diagram of HPTS-methyl ester obtained in this example.

(54) The purified product of HPTS-methyl ester is detected by a Brooke 400 MHz nuclear magnetic resonance spectrometer. Measured hydrogen spectrum data is as follows:

(55) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.29 (d, J=9.5, 7.3 Hz, 1H), δ 9.26 (d, J=9.5, 7.3 Hz, 1H), 9.20 (s, 1H), 9.13 (d, J=10.0 Hz, 1H), 8.85 (d, J=9.5 Hz, 1H), 8.46 (s, 1H), 3.94 (q, 6H), 1.54 (t, 9H).

(56) FIG. 7 is a schematic diagram of a reaction synthesis route of HPTS series derivatives of the present invention. As shown in FIG. 7, the reaction uses trisodium salt of 8-hydroxy pyrene-1,3,6-sulfonate (HPTS) as a precursor to prepare HPTS-amide or HPTS-sulfonate. Firstly, DMF is used as catalyst, HPTS is reacted with POCl.sub.3 to form HPTS-SO.sub.2C1, and then HPTS-SO.sub.2Cl is reacted with alkylamine or alcohol to form HPTS-amide or HPTS-sulfonate.

(57) What needs to be explained above is that there is no obvious difference in yields of derivatives obtained by using different synthesis routes. Main influence of different solvents in a process of preparing different derivatives lies in whether main product points are clear upon thin layer chromatography analysis, which facilitates separation through columns. Adjustment and screening can be performed according to experimental requirements.

(58) The present invention and its implementations have been schematically described above, and the description is not limited. What is shown in the accompanying drawings is only one of the embodiments of the present invention, and an actual process is not limited thereto. Therefore, if a person of ordinary skill in the art designs similar structural modes and examples without creative efforts in an enlightenment without departing from the creation purpose of the present invention, the structural modes and the examples should fall within the protection scope of the present invention.

DRAWINGS OF THE SPECIFICATION

(59) Disclosed are HPTS series derivatives and a synthesis method thereof, belonging to the field of organic synthesis. The HPTS series derivatives are prepared by introducing alkylamine or alcohol into sulfonic acid groups of HPTS. The synthesis method comprises the following steps: subjecting HPTS and phosphorus oxychloride to heating and reflux reaction for 12 hours under catalysis of DMF to obtain a reaction product; introducing the reaction product into ice water, stirring, precipitating solid, and performing suction filtration to obtain HPTS-SO.sub.2Cl; dissolving the HPTS-SO.sub.2Cl in tetrahydrofuran to prepare solution A, and dissolving alkylamine or alcohol in tetrahydrofuran to prepare solution B; mixing the solution A with the solution B and then reacting for 24 hours at normal temperature, obtaining a product by rotary evaporation, and obtaining a pure compound after separation through columns. The derivatives have strong fat solubility, overcome the defect of a very strong water solubility.