CN103073566A - Phenylboronic acid organic gel compound - Google Patents
Phenylboronic acid organic gel compound Download PDFInfo
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- CN103073566A CN103073566A CN2012103750890A CN201210375089A CN103073566A CN 103073566 A CN103073566 A CN 103073566A CN 2012103750890 A CN2012103750890 A CN 2012103750890A CN 201210375089 A CN201210375089 A CN 201210375089A CN 103073566 A CN103073566 A CN 103073566A
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Abstract
The invention discloses a 3-(3-chloro-4-ethoxy carbonyl-2-butene amino) phenylboronic acid shown as a formula (1) as below, and application of the compound as a gel to preparation of a glucose sensitive organic gel.
Description
(1) technical field
The present invention relates to a kind of preparation of synthetic and gel of phenylo boric acid class organogel compound, belong to technical field of chemistry.
(2) background technology
Regular Insulin self-adjustable control delivery systme is to significant (the Zhao Y. N. of the treatment of insulin-dependent diabetes mellitus, Trewyn B. G., Slowing I. I., Lin V. S. Y. J. Am. Chem. Soc., 2009,131,8398-8400.), burst size by glucose concentration signal and automatic continuous control Regular Insulin in the feedback body, thereby the misery (Siegel R. A., Gu Y. D., the Lei M. that make the diabetic subject break away from long term injections Regular Insulin to bring, Baldi A., Nuxoll E. E., Ziaie B. J. Control. Release, 2010,141,303-313; Ravaine V., Ancla C., Catargi B. J. Control. Release, 2008,132,2-11.).But, can realize that Regular Insulin raises and glucose-sensitive and the rapid response type Regular Insulin control release vehicle material of synchronization control release with blood sugar concentration, fails to be developed well always.The present invention is based on the novel glucose-sensitive material of Low Molecular-Weight Gel system probe one class, intend being used for the control release of glucose molecule sensor or Regular Insulin.The present invention mainly is that the organic micromolecule gel factor that a class contains glucose-sensitive phenylo boric acid group has been synthesized in design, this gel has been realized glucose-sensitive, the glucose-sensitive material that this class is novel, aspect the intelligence transmission that realizes Regular Insulin with significant.
(3) summary of the invention
The present invention relates to a kind of preparation of synthetic and gel of phenylo boric acid class organogel compound.
The invention provides a kind of phenylo boric acid class organogel compound, structure as the formula (1):
The compound title is 3-(3-chloro-4-ethoxycarbonyl-2-butylene is amino) phenylo boric acid
The present invention also provides the preparation method of described 3-(3-chloro-4-ethoxycarbonyl-2-butylene is amino) phenylo boric acid as the formula (1), and described method is:
(1) with 3-amino-benzene boric acid, the neopentyl glycol shown in the formula (4), in chloroform solvent, mix, stirring reaction 1.5-5 h under the room temperature, gained reaction solution a aftertreatment makes compound (C as the formula (3)
11H
16BNO
2, 3-amino-benzene boric acid DOPCP); The ratio of the amount of substance of the 3-amino-benzene boric acid shown in the described formula (4), neopentyl glycol is 1.0:0.8～1.5;
(2) as the formula (3) compound is dissolved in the dichloromethane solvent, adds 2-chloroacetyl acetacetic ester, triethylamine again, and heating reflux reaction 15-30 h reacts complete rear gained reaction solution b aftertreatment and makes as the formula (2) compound (C
17H
23BClNO
4); The ratio of the amount of substance of described compound, 2-chloroacetyl acetacetic ester, triethylamine as the formula (3) is 1:1.0～1.8:0.95 ~ 1.9;
(3) as the formula (2) compound is in isopropanol solvent, after adding diethanolamine stirring reaction 0.5-2.0 h under the 0-10 ℃ of temperature, again at room temperature reaction 2.0-8.0 h, react complete rear suction filtration, filter cake is dissolved in behind the ether at the 0-10 ℃ of lower sulfuric acid that adds, adjust pH is that the preferred adjust pH of 1.0 ~ 3.0(is 2.0), behind the stirring reaction 0.5 ~ 1 hour, leave standstill separatory, get organic phase and steam to desolventize and make described 3-(3-chloro-4-ethoxycarbonyl-2-butylene is amino) phenylo boric acid as the formula (1); The ratio of the amount of substance of described compound, diethanolamine as the formula (2) is 1.0:0.6～1.5.
The reaction formula of described reaction is as follows:
In the described step (1), described reaction solution a post-treating method is: reaction solution a washes with water, gets organic phase and filters after with anhydrous sodium sulfate drying, and filtrate steaming removal solvent makes compound as the formula (3).
In the described step (2), described reaction solution b post-treating method is: reaction solution b steams and desolventizes methylene dichloride, and the residuum ethyl acetate extraction is got organic layer saturated common salt water washing, steam after the organic phase drying and desolventize, must make as the formula (2) compound with the Virahol recrystallization.
In the described step (1), the volumetric usage of described chloroform solvent is counted 14 ~ 35mL/g with the quality of the 3-amino-benzene boric acid shown in the formula (4) usually.
In the described step (2), the volumetric usage of described dichloromethane solvent is counted 10 ~ 15mL/g with the quality of the compound shown in the formula (3) usually.
In the described step (3), the volumetric usage of described isopropanol solvent is counted 10 ~ 20mL/g with the quality of the compound shown in the formula (2) usually.
In the described step (3), the volumetric usage of said ether is counted 5 ~ 10mL/g with the quality of the compound shown in the formula (2) usually.
3-(3-chloro-4-ethoxycarbonyl-2-butylene is amino) phenylo boric acid as the formula (1) of the present invention can be used the organogel for preparing glucose-sensitive as gelifying agent.
Concrete, the method of described application is: 3-(3-chloro-4-ethoxycarbonyl-2-butylene is amino) phenylo boric acid is as the formula (1) added in the organic solvent, heated sealed to 60 ℃ fully dissolving, then leave standstill and be cooled to room temperature, make the organogel of concentration 20 ~ 100mg/mL, described organic solvent is hexanaphthene, toluene, dimethylbenzene, methylene dichloride, chloroform, tetracol phenixin equal solvent.
The compound that the present invention relates to (1) prepares gel as gelifying agent and has advantages of glucose-sensitive.Compound (1) is the good gelifying agent of a class, it is in hexanaphthene, toluene, dimethylbenzene, methylene dichloride, chloroform, tetracol phenixin equal solvent, be self-assembled into three-dimensional net structure by the intermolecular non covalent bond reactive force of gelator such as Van der Waals force, hydrogen bond, π-reactive forces such as π stack, solvent molecule is lost flowability and form gel, as shown in Figure 1.This gel has advantages of glucose-sensitive, because the phenylo boric acid group that contains in compound (1) molecular structure is that a class is to the group of glucose-sensitive, when adding glucose molecule in the organogel, the phenylo boric acid group just generates mixture with glucose molecule, as shown in Figure 2, this mixture has destroyed the interaction force between gelator, further destroyed the three-dimensional net structure of gel, so that the gelator that dissociates is dissolved in organic solvent, causing gel conversion is that colloidal sol is realized the sensitivity response to glucose molecule, as shown in Figure 3.
(4) description of drawings
Fig. 1. the gel of compound (1) in toluene.
Fig. 2. phenylo boric acid group and glucose molecule form the process of mixture.
Fig. 3. the variation of the time that responds fully with the increase organogel of glucose concn.
(5) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
The concrete synthetic example of compound (1) such as embodiment 1-embodiment 5
Embodiment 1
Add 30 mL chloroforms, 3-amino-benzene boric acid (1.37 g, 10 mmol) in the 100mL round-bottomed flask, neopentyl glycol (1.04 g, 10 mmol) stirs 3 h under the room temperature.Reaction solution is isolated organic phase with 200 mL washing 2 times, and with filtering behind the anhydrous sodium sulfate drying, organic phase is revolved and steamed to get compound (3) (C
11H
16BNO
2, 3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl) benzenamine), yield 99%.Get this compound (3) (7.0 g, 34 mmol), 2-chloroacetyl acetacetic ester (6 mL, 43 mmol), join in the 100 mL methylene dichloride, add triethylamine (7 mL), heating reflux reaction 24 h.React and revolve steaming vibrating dichloromethane after complete, ethyl acetate extraction, organic phase is used the saturated common salt water washing three times again, and organic phase gets compound (2) (C with the Virahol recrystallization after revolving steaming
17H
23BClNO
4, ethyl 2-chloro-3-(3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl) phenylamino) but-2-enoate), yield 51%.Compound (2) (4.0 g, 12 mmol) is joined in the 50 mL Virahols, in 0
oAfter adding diethanolamine (1.26 g, 12 mmol) stirring reaction 1h under the C, at room temperature react again 5h.React complete rear suction filtration and get solid, join in the round-bottomed flask after it is dissolved in the 30mL ether, in 0
oAdd aqueous sulfuric acid (pH=2.0) stirring reaction of 15 mL under the C after half an hour, separatory is got organic phase and is revolved and steam to get final product compound (1) (C
12H
15BClNO
4, 3-(3-chloro-4-ethoxycarbonyl-2-butylene is amino) phenylo boric acid), yield 70%.White powder; Mp 170.7-171.6 ° C;
1H NMR (300 MHz, CDCl
3): δ 10.80 (s, 1H), 7.99 (t, J=22.8 Hz, 1H), 7.874 (m, 1H), (7.496 m, 1H), 7.231 (m, 1H), 4.252 (m, 2H), (2.40 s, 2H), 2.20 (s, 3H), 1.357 (t, 3H);
13C NMR (75 MHz, CDCl
3): δ 167.09 (s), 156.71,138.49,132.25,131.27,128.82 128.64,128.306,92.42,61.04,18.06,14.14; HRMS (EI, 70 eV): 284.0854 (M+H)
+, C
12H
15BClNO
4Requires 283.0783; FTIR (KBr): 3456.49,2365.92,1641.61,1435.65,1374.36,1255.30,1016.27,759.77 cm
-1.
Embodiment 2
In the 100mL round-bottomed flask, add 35 mL chloroforms, 3-amino-benzene boric acid (1.37 g, 10 mmol), neopentyl glycol (1.25 g, 12 mmol), stir 4 h under the room temperature.Reaction solution is isolated organic phase with 200 mL washing 2 times, and with filtering behind the anhydrous sodium sulfate drying, organic phase is revolved and steamed to get compound (3), yield 99%.Get this compound (3) (7.0 g, 34 mmol), 2-chloroacetyl acetacetic ester (4.7 mL, 34 mmol), join in the 75 mL methylene dichloride, add again triethylamine (4.5 mL), heating reflux reaction 15 h.React and revolve steaming vibrating dichloromethane after complete, ethyl acetate extraction, organic phase is used the saturated common salt water washing three times again, and organic phase gets compound (2), yield 47% with the Virahol recrystallization after revolving steaming.Compound (2) (4.0 g, 12 mmol) is joined in the 40 mL Virahols, in 5
oAfter adding diethanolamine (7.2 mmol) stirring reaction 1.5 h under the C, at room temperature react again 6.0 h.React complete rear suction filtration and get solid, react complete rear suction filtration and get solid, join in the round-bottomed flask after it is dissolved in the 20mL ether, in 0
oAdd aqueous sulfuric acid (pH=2.0) stirring reaction of 15 mL under the C after half an hour, separatory is got organic phase and is revolved and steam to get final product compound (1), yield 58%.
Embodiment 3
In the 100mL round-bottomed flask, add 40 mL chloroforms, 3-amino-benzene boric acid (1.37 g, 10 mmol), neopentyl glycol (1.56 g, 15 mmol), stir 2 h under the room temperature.Reaction solution is isolated organic phase with 220 mL washing 2 times, and with filtering behind the anhydrous sodium sulfate drying, organic phase is revolved and steamed to get compound (3), yield 98%.Get this compound (3) (7.0 g, 34 mmol), 2-chloroacetyl acetacetic ester (62 mmol) joins in the 100 mL methylene dichloride, adds triethylamine (9 mL), heating reflux reaction 30 h again.React and revolve steaming vibrating dichloromethane after complete, ethyl acetate extraction, organic phase is used the saturated common salt water washing three times again, and organic phase gets compound (2), yield 60% with the Virahol recrystallization after revolving steaming.Compound (2) (4.0 g, 12 mmol) is joined in the 60 mL Virahols, in 0
oAfter adding diethanolamine (18 mmol) stirring reaction 2.0 h under the C, at room temperature react again 8.0 h.React complete rear suction filtration and get solid, join in the round-bottomed flask after it is dissolved in the 40mL ether, in 0
oAdd aqueous sulfuric acid (pH=2.0) stirring reaction of 15 mL under the C after half an hour, separatory is got organic phase and is revolved and steam to get final product compound (1), yield 75%.
Embodiment 4
In the 100mL round-bottomed flask, add 20 mL chloroforms, 3-amino-benzene boric acid (1.37 g, 10 mmol), neopentyl glycol (0.83 g, 8 mmol), stir 5 h under the room temperature.Reaction solution is isolated organic phase with 150 mL washing 2 times, and with filtering behind the anhydrous sodium sulfate drying, organic phase is revolved and steamed to get compound (3), yield 95%.Get this compound (3) (7.0 g, 34 mmol), 2-chloroacetyl acetacetic ester (50 mmol) joins in the 100 mL methylene dichloride, adds triethylamine (7 mL), heating reflux reaction 25 h again.React and revolve steaming vibrating dichloromethane after complete, ethyl acetate extraction, organic phase is used the saturated common salt water washing three times again, and organic phase gets compound (2), yield 57% with the Virahol recrystallization after revolving steaming.Compound (2) (4.0 g, 12 mmol) is joined in the 50 mL Virahols, in 10
oAfter adding diethanolamine (1.26 g, 12 mmol) stirring reaction 1h under the C, again at room temperature reaction 5h.React complete rear suction filtration and get solid, join in the round-bottomed flask after it is dissolved in the 30mL ether, in 0
oAdd aqueous sulfuric acid (pH=2.0) stirring reaction of 15 mL under the C after half an hour, separatory is got organic phase and is revolved and steam to get final product compound (1), yield 65%.
Embodiment 5
In the 100mL round-bottomed flask, add 45 mL chloroforms, 3-amino-benzene boric acid (1.37 g, 10 mmol), neopentyl glycol (1.35 g, 13 mmol), stir 1.5 h under the room temperature.Reaction solution is isolated organic phase with 200 mL washing 2 times, and with filtering behind the anhydrous sodium sulfate drying, organic phase is revolved and steamed to get compound (3), yield 98%.Get this compound (3) (7.0 g, 34 mmol), 2-chloroacetyl acetacetic ester (35 mmol), join in the 70 mL methylene dichloride, add again triethylamine (5 mL), heating reflux reaction 15 h.React and revolve steaming vibrating dichloromethane after complete, ethyl acetate extraction, organic phase is used the saturated common salt water washing three times again, and organic phase gets compound (2), yield 50% with the Virahol recrystallization after revolving steaming.Compound (2) (4.0 g, 12 mmol) is joined in the 50 mL Virahols, in 0
oAfter adding diethanolamine (1.26 g, 12 mmol) stirring reaction 1h under the C, at room temperature react again 5h.React complete rear suction filtration and get solid, join in the round-bottomed flask after it is dissolved in the 30mL ether, in 0
oAdd aqueous sulfuric acid (pH=2.0) stirring reaction of 15 mL under the C after half an hour, separatory is got organic phase and is revolved and steam to get final product compound (1), yield 70%.
The specific solution of compound (1) gel such as embodiment 6-embodiment 11
Embodiment 6
25 mg are joined in the 1.0 mL hexanaphthenes by the gelifying agent of embodiment 1 method preparation, be sealed in and be heated to 60 in the ampoule
oC dissolves gelator fully, then leaves standstill and is cooled to room temperature, can obtain the organogel that concentration is 25 mg/mL.
Embodiment 7
20 mg are joined in the 1.0 mL tetracol phenixin by the gelifying agent of embodiment 2 methods preparation, be sealed in and be heated to 60 in the ampoule
oC dissolves gelator fully, then leaves standstill and is cooled to room temperature, can obtain the organogel that concentration is 20 mg/mL.
Embodiment 8
30 mg are joined in the 1.0 mL toluene by the gelifying agent of embodiment 3 methods preparation, be sealed in and be heated to 35 in the ampoule
oC dissolves gelator fully, then leaves standstill and is cooled to room temperature, can obtain the organogel that concentration is 30 mg/mL, and the gained gel photograph as shown in Figure 1.
Embodiment 9
50 mg are joined in the 1.0 mL dimethylbenzene by the gelifying agent of embodiment 4 methods preparation, be sealed in and be heated to 60 in the ampoule
oC dissolves gelator fully, then leaves standstill and is cooled to room temperature, can obtain the organogel that concentration is 50 mg/mL.
100 mg are joined in the 1.0 mL methylene dichloride by the gelifying agent of embodiment 5 methods preparation, be sealed in and be heated to 60 in the ampoule
oC dissolves gelator fully, then leaves standstill and is cooled to room temperature, can obtain the organogel that concentration is 100 mg/mL.
Embodiment 11
100 mg are joined in the 1.0 mL chloroforms by the gelifying agent of embodiment 1 method preparation, be sealed in and be heated to 60 in the ampoule
oC dissolves gelator fully, then leaves standstill and is cooled to room temperature, can obtain the organogel that concentration is 100 mg/mL.
Embodiment 12
50 mg are joined in the 1.0 mL toluene by the gelifying agent of embodiment 3 methods preparations, and being prepared into concentration according to the method for embodiment 8 is 50 mg/mL organogels, prepares altogether 9 organogel samples, then adding respectively 1.0 mL concentration is 0,1,3,5,10,20,30,40, the D/W of 50 mg/mL, record gel conversion are the time of colloidal sol to be the time of response.As shown in Figure 3, when adding the blank aqueous solution, gel conversion is that the time of colloidal sol is 48h.And along with the increase of D/W concentration, the gel time of response shortens gradually, and when the D/W concentration that adds increases to 50 mg/mL, the time of response shortens to 8h, and above result shows that this gel has glucose-sensitive.
Claims (6)
1. 3-(3-chloro-4-ethoxycarbonyl-2-butylene amino) phenylo boric acid as the formula (1)
2. the preparation method of 3-(3-chloro-4-ethoxycarbonyl-2-butylene amino) phenylo boric acid as the formula (1) as claimed in claim 1 is characterized in that described method is:
(2) as the formula (3) compound is dissolved in the dichloromethane solvent, adds 2-chloroacetyl acetacetic ester, triethylamine again, and heating reflux reaction 15-30 h reacts complete rear gained reaction solution b aftertreatment and makes as the formula (2) compound; The ratio of the amount of substance of described compound, 2-chloroacetyl acetacetic ester, triethylamine as the formula (3) is 1:1.0～1.8:0.95 ~ 1.9;
(3) as the formula (2) compound is in isopropanol solvent, after adding diethanolamine stirring reaction 0.5-2.0 h under the 0-10 ℃ of temperature, again at room temperature reaction 2.0-8.0 h, react complete rear suction filtration, filter cake is dissolved in behind the ether at the 0-10 ℃ of lower sulfuric acid that adds, and adjust pH is 1.0 ~ 3.0, and stirring reaction is after 0.5 ~ 1 hour, leave standstill separatory, get organic phase and steam to desolventize and make described 3-(3-chloro-4-ethoxycarbonyl-2-butylene is amino) phenylo boric acid as the formula (1); The ratio of the amount of substance of described compound, diethanolamine as the formula (2) is 1.0:0.6～1.5.
3. method as claimed in claim 2, it is characterized in that in the described step (1), described reaction solution a post-treating method is: reaction solution a washes with water, gets organic phase and filters after with anhydrous sodium sulfate drying, and filtrate steaming removal solvent makes compound as the formula (3).
4. method as claimed in claim 2, it is characterized in that in the described step (2), described reaction solution b post-treating method is: reaction solution b steams and desolventizes methylene dichloride, the residuum ethyl acetate extraction, get organic layer saturated common salt water washing, steam after dry and desolventize, must make as the formula (2) compound with the Virahol recrystallization.
5. 3-(3-chloro-4-ethoxycarbonyl-2-butylene is amino) phenylo boric acid as the formula (1) claimed in claim 1 prepares the application of the organogel of glucose-sensitive as gelifying agent.
6. application as claimed in claim 5, the method that it is characterized in that described application is: 3-(3-chloro-4-ethoxycarbonyl-2-butylene is amino) phenylo boric acid is as the formula (1) added in the organic solvent, heated sealed to 60 ℃ fully dissolving, then leave standstill and be cooled to room temperature, make the organogel of concentration 20 ~ 100mg/mL.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103467502A (en) * | 2013-08-19 | 2013-12-25 | 温州大学 | Phenylboronic acid organogel compound |
| CN109897148A (en) * | 2019-02-26 | 2019-06-18 | 西安交通大学 | Renewable polyureas-urethane of dynamic covalent cross-linking based on stable boric acid ester bond and its preparation and application |
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| CN101273961A (en) * | 2007-03-30 | 2008-10-01 | 中国人民解放军总医院 | Glucose-sensitive hydrogels |
| US20090191642A1 (en) * | 2008-01-29 | 2009-07-30 | University Of South Carolina | Compositions, Systems, and Methods for Continuous Glucose Monitoring |
| WO2010041037A2 (en) * | 2008-10-10 | 2010-04-15 | The University Of Bath | Materials and methods for resolving polyhydric species by electrophoresis |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467502A (en) * | 2013-08-19 | 2013-12-25 | 温州大学 | Phenylboronic acid organogel compound |
| CN103467502B (en) * | 2013-08-19 | 2015-12-02 | 温州大学 | One class Phenylboronic acid organic gel compound |
| CN109897148A (en) * | 2019-02-26 | 2019-06-18 | 西安交通大学 | Renewable polyureas-urethane of dynamic covalent cross-linking based on stable boric acid ester bond and its preparation and application |
| CN109897148B (en) * | 2019-02-26 | 2020-10-27 | 西安交通大学 | Stable borate ester bond based dynamically covalently crosslinked renewable polyurea-urethanes and their preparation and use |
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