CN105001189B - There is aliphatic carboxylic acid molecule of near-infrared response and preparation method thereof - Google Patents
There is aliphatic carboxylic acid molecule of near-infrared response and preparation method thereof Download PDFInfo
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- CN105001189B CN105001189B CN201510342412.8A CN201510342412A CN105001189B CN 105001189 B CN105001189 B CN 105001189B CN 201510342412 A CN201510342412 A CN 201510342412A CN 105001189 B CN105001189 B CN 105001189B
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
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Abstract
The present invention relates to the preparation of Photosensitive aliphatic carboxylic acid molecule, be particularly related to a kind of aliphatic carboxylic acid molecule with near-infrared response and preparation method thereof, using bromo-7 Hydroxycoumarins of 4-methylol-6-as near infrared light response unit, synthesize to prepare the aliphatic acid that contains near infrared light degradable unit by simple unit, the method synthesis technique is simple, strong operability, cost preparation that can be lower has the Photosensitive carboxylic acid molecules of different structure. The target product purity obtaining is higher, can realize more than 98% purity by simple crystallization.
Description
Technical field
The present invention relates to the preparation of Photosensitive aliphatic carboxylic acid molecule, particularly a kind of aliphatic carboxylic acid with near-infrared response dividesSon and preparation method thereof.
Background technology
The preparation that contains photosensitive unit molecule all has emphatically in the Design & preparation of molecular switch, intelligent medicine carrying and new materialThe using value of wanting. People are attempting various photoresponses unit to be incorporated into the organic of different structure by dissimilar chemical bondIn molecule, build the reaction member with photoresponse ability.
Along with the development of light-sensitive material and people are to photochemical further investigation, it is found that original light-sensitive compound, especiallyIt is the demand that light degradable organic molecule cannot meet the clinical and field of medicaments day by day increasing. Traditional light degradable officialCan roll into a ball response region and focus mostly in ultra-violet (UV) band (280-380nm), but the light of ultraviolet band is because wavelength is short, easily by live body groupHydrone scattering in knitting is fallen, and wearing in tissue is deeply limited. And ultraviolet light biological tissue is also had stronger lethal, nothingMethod is effectively applied to biological and medical field.
Summary of the invention
The present invention is directed to deficiency of the prior art, the lethal large and tissue of live body is worn dark short etc. scarce in order to overcome current ultraviolet lightFall into, development and Design of the present invention has been synthesized the aliphatic carboxylic acid molecule that a class contains near infrared light degradable unit in aliphatic chain, makes upThe application limitation of ultraviolet photosensitive unit.
Technical scheme of the present invention is:
An aliphatic carboxylic acid molecule with near-infrared response, the general formula of described carboxylic acid molecules is:
Wherein, the integer that n is 3-18.
Preferably, described aliphatic carboxylic acid molecule carries out light degradation in the wavelength 780-820nm of near infrared region.
Preferably, described aliphatic carboxylic acid molecule can carry out light degradation in the wavelength 808nm of near infrared region.
Another object of the present invention is the preparation method of the openly above-mentioned aliphatic carboxylic acid molecule with near-infrared response, comprisesBe prepared as follows process:
Wherein, the integer that n is 3-15;
Step 1: taking 4-bromine resorcinol 1 as initiation material, react and obtain with 4-chloroacetyl acetacetic ester in methanesulfonic acid solutionThe bromo-umbelliferone 2 of 4-chloromethyl 6-;
Step 2: the bromo-umbelliferone 2 of 4-chloromethyl 6-obtaining taking step 1 is intermediate, first at 1,8-diazabicyloUnder the catalysis of 11 carbon-7-alkene, carry out esterification with the dicarboxylic acids list tert-butyl ester, then under Anhydrous potassium carbonate catalysis to contain different carbon formerThe positive structure brominated alkanes of subnumber carries out etherification reaction, obtains the carboxylic acid tert-butyl ester 3 that contains near infrared light degradable unit;
Step 3: by the tert-butyl ester excision on carboxylic acid, obtain the carboxylic acid molecules 4 that contains cumarin unit under the existence of trifluoroacetic acid.
Wherein, specifically comprise the steps:
In the methanesulfonic acid solution that step 1:4-bromine resorcinol is dissolved in, be mixed with the solution that molar concentration is 100mmol/L, stirUnder add the 4-chloroacetyl acetacetic ester reaction of isopyknic 140mmol/L, under nitrogen protection, stir 24 hours in 25 DEG C,By in the frozen water of 5 times of liquor capacities of slow reactant liquor impouring, suction filtration, filter cake makes to be washed with water to no acidic, and vacuum drying obtainsObtain bromo-7 Hydroxycoumarins 2 of 4-chloromethyl-6-;
Step 2: by etc. bromo-7 Hydroxycoumarins 2 of 4-chloromethyl-6-of quality, the succinic acid list tert-butyl ester and 1,8-diazabicylo11 carbon-7-alkene is dispersed in toluene, and it is 15% dispersion soln that preparation obtains mass volume ratio; Under nitrogen protection, reflux 2 hours;Be chilled to room temperature, rotary evaporation is removed toluene, and residue is dissolved in acetone, adds and bromo-7 Hydroxycoumarins 2 of 4-chloromethyl-6-etc.The positive structure brominated alkanes of mass ratio and the Anhydrous potassium carbonate of 5 times of mass ratios, under nitrogen protection, lucifuge refluxes 6 hours; FilteringInsoluble matter, filtrate is spin-dried for, and is again dissolved in ether, after diatomite filtration, adds 10% aqueous citric acid solution extraction, organic phase withAnhydrous sodium sulfate drying, obtains yellow solid carboxylic acid tert-butyl ester 3;
Step 3: the product that step 2 is obtained is dissolved in the mixed solvent of equal-volume carrene and trifluoroacetic acid, described is mixedThe mass volume ratio of bonding solvent is 10%, stirs 2 hours at 25 DEG C, and reaction finishes rear rotary evaporation and removes organic solvent,Residue crystallization in 5mL ether-n-hexane mixed solvent, obtains yellow crystals carboxylic acid molecules 4.
The invention has the beneficial effects as follows:
1, bromo-7 Hydroxycoumarins of aliphatic carboxylic acid molecule 4-methylol-6-disclosed by the invention are as near infrared light response unit, can be closelyInfrared light, according to lower light degradation, has good optical Response.
2, preparation method's synthesis technique disclosed by the invention is simple, strong operability, and cost preparation that can be lower has different structurePhotosensitive carboxylic acid molecules.
3, preparation method disclosed by the invention react the intermediate of generation can be not purified, in the end a step recrystallization can obtain pureSpend higher target product. The target product purity obtaining is higher, can realize more than 98% purity by simple crystallization.
Brief description of the drawings
The mass spectrogram of the photolysis debris 1a that accompanying drawing 1 is the specific embodiment of the invention;
The mass spectrogram of the photolysis debris 2a that accompanying drawing 2 is the specific embodiment of the invention;
The mass spectrogram of the photolysis debris 3a that accompanying drawing 3 is the specific embodiment of the invention;
The mass spectrogram of the photolysis debris 4a that accompanying drawing 3 is the specific embodiment of the invention;
The mass spectrogram of the photolysis debris 5a that accompanying drawing 3 is the specific embodiment of the invention.
Detailed description of the invention
The specific embodiment of the present invention is as follows:
A kind of preparation method of the aliphatic carboxylic acid molecule with near-infrared response:
Step 1:2g4-bromine resorcinol is dissolved in methanesulfonic acid and is mixed with the solution that molar concentration is 100mmol/L, under stirring, addsEnter the 4-chloroacetyl acetacetic ester of equal-volume 140mmol/L, in 25 DEG C of stirrings 24 hours, reactant liquor is slow under nitrogen protectionIn slow impouring 300mL water, suction filtration, filter cake uses 100mL water washing, vacuum drying;
Step 2: by bromo-2g4-chloromethyl-6-7 Hydroxycoumarins, the 2g succinic acid list tert-butyl ester and 2g1,8-diazabicylo tenOne carbon-7-alkene is dispersed in 100mL toluene, refluxes 2 hours under nitrogen protection; Be chilled to room temperature, rotary evaporation is removed toluene,Residue is dissolved in 50mL acetone, adds the positive structure brominated alkanes of 10g Anhydrous potassium carbonate and 2g, and under nitrogen protection, lucifuge is returnedFlow 6 hours; Filtering insoluble matter, filtrate is spin-dried for, and is again dissolved in 60mL ether, after diatomite filtration, adds 10% lemonAqueous acid extraction, organic phase, with anhydrous sodium sulfate drying, obtains yellow solid carboxylic acid tert-butyl ester 3;
Step 3: the product that step 2 is obtained is dissolved in the mixed solvent of 10mL carrene and 10mL trifluoroacetic acid,At 25 DEG C, stir 2 hours, reaction finishes rear rotary evaporation and removes organic solvent, and residue mixes molten at 5mL ether-n-hexaneCrystallization in agent, obtains yellow crystals carboxylic acid molecules 4.
Wherein, positive structure brominated alkanes is the positive structure brominated alkanes that contains even carbon atomic carbon 4-12.
Prepare the aliphatic carboxylic acid molecule with near-infrared response according to above method:
Nuclear magnetic data:1H-NMR(CDCl3,400MHz):δ＝0.92(s,CH3,3H),1.26-1.34(m,CH2,2H)1.50-1.53 (m,CH2,2H),1.86-1.88(m,CH2,2H),2.78-2.81(m,OCH2,4H),4.06-4.09(m,CH2O,2H),5.27-5.30(m,ArCH2O,2H),6.36(m,ArH,1H),6.83(m,ArH,1H),7.66-7.67(m,ArH,1H).
Mass spectrometric data: ESIMScalcdforC18H19BrO7,426.03；found427.03(M+H+),428.03(M+2H+),429.03(M+H+),430.03(M+2H+).
Nuclear magnetic data:1H-NMR(CDCl3,400MHz):δ＝0.92(s,CH3,3H),1.26-1.34(m,CH2,4H)1.50-1.53(m,CH2,2H),1.86-1.88(m,CH2,2H),2.78-2.81(m,OCH2,4H),4.06-4.09(m,CH2O,2H),5.27-5.30(m,ArCH2O,2H),6.36(m,ArH,1H),6.83(m,ArH,1H),7.66-7.67(m,ArH,1H).
Mass spectrometric data: ESIMScalcdforC20H23BrO7,454.06；found455.07(M+H+),456.08(M+2H+),457.07(M+H+),458.07(M+2H+).
Nuclear magnetic data:1H-NMR(CDCl3,400MHz):δ＝0.92(s,CH3,3H),1.26-1.34(m,CH2,8H)1.50-1.53(m,CH2,2H),1.86-1.88(m,CH2,2H),2.78-2.81(m,OCH2,4H),4.06-4.09(m,CH2O,2H),5.27-5.30(m,ArCH2O,2H),6.36(m,ArH,1H),6.83(m,ArH,1H),7.66-7.67(m,ArH,1H).
Mass spectrometric data: ESIMScalcdforC22H27BrO7,482.09；found483.09(M+H+),484.08(M+2H+),485.09(M+H+),486.08(M+2H+).
Nuclear magnetic data:1H-NMR(CDCl3,400MHz):δ＝0.92(s,CH3,3H),1.26-1.34(m,CH2,12H)1.50-1.53(m,CH2,2H),1.86-1.88(m,CH2,2H),2.78-2.81(m,OCH2,4H),4.06-4.09(m,CH2O,2H),5.27-5.30(m,ArCH2O,2H),6.37(m,ArH,1H),6.82(m,ArH,1H),7.66-7.67(m,ArH,1H).
Mass spectrometric data: ESIMScalcdforC24H31BrO7,510.13；found511.13(M+H+),533.12(M+Na+).
Nuclear magnetic data:1H-NMR(CDCl3,400MHz):δ＝0.92(s,CH3,3H),1.26-1.34(m,CH2,16H)1.50-1.53(m,CH2,2H),1.86-1.88(m,CH2,2H),2.78-2.81(m,OCH2,4H),4.01-4.08(m,CH2O,2H),5.27-5.30(m,ArCH2O,2H),6.34-6.37(m,ArH,1H),6.83-6.872(m,ArH,1H),7.66-7.67(m,ArH,1H).
Mass spectrometric data: ESIMScalcdforC26H35BrO7,538.16；found539.29(M+H+),540.25(M+2H+),541.16(M+H+),542.16(M+2H+).
All target product structures and purity are determined by proton nmr spectra and the electron spray mass spectrum that dissociates.
Nuclear-magnetism model is BrukerAMX400Spectrometer (400MHz), and mass spectrum model is Agilent6510Q-TOF.
Near-infrared light source is the continuous emission mode near-infrared laser of 808nm, and photodissociation condition is laser intensity 1W. Irradiation time is15 minutes. 10mg compound 4 is dissolved in 200 μ L methyl alcohol, near infrared light according under 15 minutes, through the electron spray mass spectrum that dissociatesAnalyze, the photodissociation of molecule can be detected.
1.n＝41a.n＝4
2.n＝62a.n＝6
3.n＝83a.n＝8
4.n＝104a.n＝10
5.n＝125a.n＝12
The fracture mode of table 1 near-infrared response carboxylic acid under near-infrared laser irradiates
| Photolysis debris | Calculated mass | Actual measurement quality | Fragment existence form |
| 1a | 326.02 | 327.02，329.02 | M+H+ |
| 2a | 354.05 | 377.16 | M+Na+ |
| 3a | 382.08 | 417.23，419.21 | M-H++K+ |
| 4a | 411.11 | 433.24 | M+Na+ |
| 5a | 438.14 | 461.25 | M+Na+ |
The mass spectrogram of photolysis debris is shown in shown in accompanying drawing 1-5, has more than verified that the light under near infrared light shines falls by light degradable carboxylic acidSolution behavior, has proved the optical Response that it is good.
Claims (5)
1. an aliphatic carboxylic acid molecule with near-infrared response, is characterized in that, the general formula of described aliphatic carboxylic acid molecule is:
Wherein, the integer that n is 3-18.
2. the aliphatic carboxylic acid molecule with near-infrared response according to claim 1, is characterized in that, described aliphatic carboxylic acid molecule carries out light degradation in the wavelength 780-820nm of near infrared region.
3. the aliphatic carboxylic acid molecule with near-infrared response according to claim 2, is characterized in that, described aliphatic carboxylic acid molecule carries out light degradation in the wavelength 808nm of near infrared region.
4. a preparation method for the aliphatic carboxylic acid molecule with near-infrared response described in claim 1-3 any one, is characterized in that, comprises the process of being prepared as follows:
Wherein, the integer that n is 3-15;
Step 1: taking 4-bromine resorcinol 1 as initiation material, react with 4-chloroacetyl acetacetic ester in methanesulfonic acid solution and obtain the bromo-umbelliferone 2 of 4-chloromethyl 6-;
Step 2: the bromo-umbelliferone 2 of 4-chloromethyl 6-obtaining taking step 1 is intermediate, first 1, under the catalysis of 8-diazabicylo 11 carbon-7-alkene, carry out after esterification with the succinic acid list tert-butyl ester, under Anhydrous potassium carbonate catalysis, carry out etherification reaction from the positive structure brominated alkanes that contains different carbon atoms again, obtain the carboxylic acid tert-butyl ester 3 that contains near infrared light degradable unit;
Step 3: by the tert-butyl ester excision on carboxylic acid, obtain the carboxylic acid molecules 4 that contains cumarin unit under the existence of trifluoroacetic acid.
5. the preparation method of the aliphatic carboxylic acid molecule with near-infrared response according to claim 4, is characterized in that, specifically comprises the steps:
In the methanesulfonic acid solution that step 1:4-bromine resorcinol is dissolved in, be mixed with the solution that molar concentration is 100mmol/L, under stirring, add the 4-chloroacetyl acetacetic ester reaction of isopyknic 140mmol/L, under nitrogen protection, stir 24 hours in 25 DEG C, by in the frozen water of 5 times of liquor capacities of slow reactant liquor impouring, suction filtration, filter cake makes to be washed with water to no acidic, and vacuum drying obtains bromo-7 Hydroxycoumarins 2 of 4-chloromethyl-6-;
Step 2: by etc. bromo-7 Hydroxycoumarins 2 of 4-chloromethyl-6-of quality, the succinic acid list tert-butyl ester and 1,8-diazabicylo 11 carbon-7-alkene is dispersed in toluene, it is 15% dispersion soln that preparation obtains mass volume ratio; Under nitrogen protection, reflux 2 hours; Be chilled to room temperature, rotary evaporation is removed toluene, and residue is dissolved in acetone, adds and the positive structure brominated alkanes of bromo-7 Hydroxycoumarin 2 mass ratios such as grade of 4-chloromethyl-6-and the Anhydrous potassium carbonate of 5 times of mass ratios, and under nitrogen protection, lucifuge refluxes 6 hours; Filtering insoluble matter, filtrate is spin-dried for, and is again dissolved in ether, after diatomite filtration, adds 10% aqueous citric acid solution extraction, and organic phase, with anhydrous sodium sulfate drying, obtains yellow solid carboxylic acid tert-butyl ester 3;
Step 3: the product that step 2 is obtained is dissolved in the mixed solvent of equal-volume carrene and trifluoroacetic acid, the mass volume ratio of described mixed solvent is 10%, at 25 DEG C, stir 2 hours, reaction finishes rear rotary evaporation and removes organic solvent, residue crystallization in 5mL ether-n-hexane mixed solvent, obtains yellow crystals carboxylic acid molecules 4.
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