CN105833791A - Surfactant containing o-nitrobenzyl ester photodegradation group, and preparation method thereof - Google Patents
Surfactant containing o-nitrobenzyl ester photodegradation group, and preparation method thereof Download PDFInfo
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- PZBLYVXIESQISD-UHFFFAOYSA-N [O-][N+](c1cc(C(Cl)=O)ccc1CBr)=O Chemical compound [O-][N+](c1cc(C(Cl)=O)ccc1CBr)=O PZBLYVXIESQISD-UHFFFAOYSA-N 0.000 description 1
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- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
Abstract
The invention discloses a novel photodegradation surfactant and preparation thereof, belonging to the field of surfactants. The novel photodegradation surfactant is synthesized through the following three reaction steps: (1) with diethylene triamine pentacetic acid as a raw material and acetic anhydride as a dehydrating agent, carrying out dehydration under the catalysis of pyridine so as to produce diethylene triamine pentacetic dianhydride; (2) with an o-nitrobenzyl bromide derivative as a raw material, carrying out acylating chlorination on the derivative and then reacting an acylating chlorination product with secondary amine so as to obtain an intermediate, i.e., para-position double-long-chain carbomite o-nitrobenzyl bromide; and (3) subjecting double-long-chain benzyl bromide in the intermediate and middle carboxyl groups of diethylene triamine pentacetic dianhydride to nucleophilic substitution under the catalysis of a catalyst in a solvent so as to obtain surfactant molecules containing o-nitrobenzyl ester light-operated groups. According to the invention, four terminal carboxyl groups are protected by ingeniously utilization of dehydration of diethylene triamine pentacetic acid into anhydride, the middle carboxyl groups are selectively utilized and form ester under the catalysis of organic base DBU, so the o-nitrobenzyl ester photodegradation surfactant is prepared. Compared with traditional methods, the method provided by the invention has the advantages that reaction flow is shortened and efficiency is greatly improved.
Description
Technical field
The present invention relates to a kind of Novel light-operated surface active molecules and preparation method thereof, be specifically related to adjacent nitrobenzyl
Ester is light degradation group, and with the double long-chain of secondary amine as hydrophobic group, diethylene triamine pentacetic acid (DTPA) is the new of hydrophilic group
Surface active molecules and the new method of synthesis, belong to surfactant field.
Background technology
Environmental response amphiphile, amphiphilic molecule assembly receives much concern because of its potential application in terms of drug controllable release,
Photoresponse is the most external controlled and without internal specific chemical change.Pharmaceutical pack being rolled in carrier, vein is noted
Inject blood circulation, external ultraviolet or near infrared light to stimulate, it is achieved the controllable release of medicine, thus effectively
Reduce drug loss and the toxic and side effects to human body, improve bioavailability.
Adjacent p-Nitrobenzyl has the special construction of two-photon effect, and under near infrared light, ester bond can rupture, and reaches
To drug controllable release effect, the near-infrared controllable release about adjacent p-Nitrobenzyl causes researcher to pay close attention in recent years.
Wherein, Jiang Jinqiang et al. devises the block copolymer with o-nitro benzyl alcohol as hydrophobic side, and esterification introduces ester
Base, wraps up dewatering medicament Nile red, 365nm or 700nm light irradiates 25min medicine and discharges completely
(Macromolecules 2006,39,4633-4640)；Minhyuck Kang and Bongjin Moon et al.
Introducing in the middle of the molecule of design with adjacent p-Nitrobenzyl for bridge, acyl chlorides and benzylalcohol react introducing ester group, and 350nm is purple
Outer light irradiates 2h neighbour's p-Nitrobenzyl system and substantially ruptures (Macromolecules 2009,42,455-458)；Dong
Build and bright et al. introduce adjacent p-Nitrobenzyl group by benzyl bromine affine replacement, and reduce vesicle particle diameter by polycondensation, carry
High the stability of dispenser carrier (Langmuir 2012,28,1733-1737).But traditional adjacent nitrobenzyl
Ester introducing method, often with o-nitro benzyl alcohol for substrate by with anhydride, acyl chlorides, active Esterification reaction, draw
Enter required photoresponse ester group.There is certain structural limitation in this kind of method, phenyl ring often only at structure end, one
Denier relates to phenyl ring and enters in the middle of structure, requires higher to the carboxylic acid reactive of esterification, is restricted.
Diethylene triamine pentacetic acid (DTPA) and gadolinium complexation can use as nuclear magnetism contrast agent, surface active molecules in the present invention
Introduce diethylene triamine pentacetic acid (DTPA) and will can be used as functional magnetic resonance contrast agent as hydrophilic group.Diethylenetriamine five
Acetic acid has five carboxyls, reaction to generally require a carboxyl, therefore needs remaining four carboxy protective to get up,
To more single-minded structure.The carboxyl of traditional diethylene triamine pentacetic acid (DTPA) typically introduces the tert-butyl group in building-up process
Alcohol becomes ester to protect, but building-up process complex steps, and the response time is longer, and inefficient and carboxyl selects
Property protection be also a difficult point.Arano etc. are with diethylenetriamine as raw material, at synthesis diethylene triamine pentacetic acid (DTPA)
During protect carboxyl by bromo-acetic acid tert-butyl, stay next terminal carboxyl group (J.Med.Chem.1996,39,
3451.).Giordano etc. first protect end group amine with diethylenetriamine for initial feed equally, are finally synthesizing and stay
There is the diethylenetriamine derivant (Synthesis 2004,1835.) of middle carboxyl.Davies etc. are with 2,2'-bis-
Chlorine diethylamide hydrochlorate is raw material, protects two end carboxyl during synthesis diethylene triamine pentacetic acid (DTPA) derivant
Leave middle carboxyl (J.Pept.Sci.2002,8,663.).
Summary of the invention
It is an object of the invention to propose one utilizes organic base DBU with benzyl br-derivatives and diethylenetriamine five
The double acid anhydride of acetic acid is the synthetic method that Material synthesis contains the surfactant of adjacent p-Nitrobenzyl photosensitive group.The method
Inversely wanting to examine, utilize the middle carboxyl that diethylene triamine pentacetic acid (DTPA) acid anhydride activated carboxyl is remaining cleverly, having synthesized can
Degraded surfactant.
The present invention provides a kind of surfactant containing adjacent p-Nitrobenzyl photosensitive group, and general structure I is as follows:
Wherein, m and n is separately selected from 6,8,10,12 or 14.M with n can be identical, it is possible to
To differ；Preferably m=n.
The present invention reoffers a kind of novel light degradation light-operated surfactant molecule of surfactant o p-Nitrobenzyl
Preparation method:
By double for diethylene triamine pentacetic acid (DTPA) acid anhydrides in single port flask, add anhydrous solvent and be heated to 60～70 DEG C of dissolvings,
It is cooled to room temperature, double long-chain bromo derivatives that dropping is dissolved in anhydrous solvent；With urging of being dissolved in anhydrous solvent
Agent DBU, under nitrogen protection, 30～80 DEG C of reaction 1h, in reactant liquor, add suitable quantity of water, produce milky white
Color liquid, centrifugal, obtain subsoil yellow solid, column chromatography for separation, what eluant was dichloromethane with methanol is mixed
Close liquid, obtain adjacent p-Nitrobenzyl light-operated surface active molecules bright yellow solid；
Described pair of long-chain bromo derivative structure such as formula II:
Wherein, m and n is separately selected from 6,8,10,12 or 14.M with n can be identical, it is possible to
To differ；Preferably m=n.
The double acid anhydride of diethylene triamine pentacetic acid (DTPA): double long-chain bromo derivatives: catalyst DBU: water mol ratio is 1:
0.8-1.2:0.8-1.2:40-60；
The double acid anhydride of diethylene triamine pentacetic acid (DTPA): solvent molar ratio is: 1:250-350.
Further, in technique scheme, described in double long-chain bromo derivatives of being dissolved in anhydrous solvent
Double long-chain bromo derivatives and anhydrous solvent mol ratio are 1:50-60；The described catalyst being dissolved in anhydrous solvent
In DBU, catalyst DBU and anhydrous solvent mol ratio are 1:50-60.
Further, in technique scheme, described anhydrous solvent is selected from DMSO or DMF.
Further, in technique scheme, the preparation method of described pair of long-chain bromo derivative intermediate is:
Take adjacent nitrobenzyl br-derivatives in there-necked flask, drip thionyl chloride, remove after back flow reaction 2～5h
Excess thionyl chloride.The appropriate double long-chain secondary amine of dropping and appropriate potassium carbonate, 30～60 DEG C of reaction 12h, stop anti-
Should, adding appropriate amount of deionized water, separatory, organic layer anhydrous sodium sulfate is dried overnight, and eluant is dichloromethane
Alkane and the mixed liquor of methanol, column chromatography for separation, obtain benzyl br-derivatives pale yellow oily liquid body.
Double long-chain secondary amine structure such as general formula III:
Wherein, m and n is separately selected from 6,8,10,12 or 14.M with n can be identical, it is possible to
To differ；Preferably m=n.
Adjacent nitrobenzyl br-derivatives: thionyl chloride: double long-chain secondary amine: potassium carbonate mol ratio is: 1:60-80:
0.8-1.2:0.8-1.2.
Further, in technique scheme, described adjacent nitrobenzyl br-derivatives is selected from 4-bromomethyl-3-nitre
Yl benzoic acid or 4-bromomethyl-3-nitrobenzene-sulfonic acid.
Further, in technique scheme, eluant used by the double long-chain bromo derivative intermediate of synthesis is
Dichloromethane and the volume ratio (20～40) of methanol: the mixed liquor of 1；
Eluant used by the adjacent light-operated surface active molecules of p-Nitrobenzyl of synthesis is the volume ratio of dichloromethane and methanol
For (10～20): the mixed liquor of 1.
Further, in technique scheme, the double acid anhydride (DTPAA) of described diethylene triamine pentacetic acid (DTPA)
Preparation method is:
Being put in by diethylene triamine pentacetic acid (DTPA) in single port flask, be sequentially added into acetic anhydride, pyridine, under nitrogen protection
It is warmed up to 60～70 DEG C, reacts 20～24h.React complete sucking filtration, obtain the double acid anhydride white of diethylene triamine pentacetic acid (DTPA) solid
Body powder.
The chemical reactive synthesis formula of surface active molecules of the present invention is as follows:
Wherein, m and n is separately selected from 6,8,10,12 or 14.M with n can be identical, it is possible to
To differ；Preferably m=n.
The ingenious part of this synthesis mechanism is to utilize the method being dehydrated into acid anhydride activated carboxyl by diethylenetriamine five
The carboxy protective at acetic acid two ends, at organic base DBU (1,8-diazabicylo 11 carbon-7-alkene) high selectivity
The carboxyl making intermediate rest under catalytic action reacts with benzyl halogen.The follow-up acid that can also recycle two ends
Acid anhydride carries out next step reaction, the most not only adds reaction selectivity but also improve the reactivity of two end carboxyl, and one
Lift two to obtain.
Invention beneficial effect
The present invention utilizes the characteristic of organic base DBU efficient catalytic nucleophilic substitution reaction, has been catalyzed diethyl dexterously
In the double acid anhydride of alkene pentaacetic acid, the most inactive carboxyl reacts generation degradable surface activity with benzyl br-derivatives
Agent, not only protects terminal carboxyl group but also improve reaction selectivity, kills two birds with one stone.
(1) present invention utilizes diethylene triamine pentacetic acid (DTPA) self to be dehydrated into acid anhydride dexterously, has both served carboxyl and has protected
The effect protected the most optionally provides the carboxyl needed for a reaction.
(2) present invention is with the double acid anhydride of diethylene triamine pentacetic acid (DTPA) as raw material, shortens routine normal-butyl greatly
The complex reaction flow process of carboxyl protected during synthesis diethylene triamine pentacetic acid (DTPA) by alcohol, improves efficiency.
(3) present invention utilizes the high catalytic reaction activity of organic base DBU, and benzyl bromine sets out to become with carboxylic acid reaction
Ester, homogeneous reaction, it is provided that a kind of new esterification response path.
Accompanying drawing explanation
Fig. 1 is surface active molecules (4-diethylene triamine pentacetic acid (DTPA) the ester group)-3-nitro of embodiment 1 preparation
The mass spectrum of-N, N-dioctyl Benzoylamide；
Fig. 2 is surface active molecules (4-diethylene triamine pentacetic acid (DTPA) the ester group)-3-nitro of embodiment 1 preparation
-N, N-dioctyl Benzoylamide1H NMR schemes.
Detailed description of the invention
Below in conjunction with embodiment, the method for the present invention is described further, but is not limitation of the invention.
Embodiment 1 light degradation surfactant (4-diethylene triamine pentacetic acid (DTPA) ester group)-3-nitro-N, N-bis-is pungent
The synthesis of yl-benzamide:
(1) synthesis diethylene triamine pentacetic acid (DTPA) acid anhydride
Weigh in 3.98g (0.01mol) diethylene triamine pentacetic acid (DTPA) and 100mL single port flask, be sequentially added into
4mL acetic anhydride and 5mL pyridine, be warmed up to 65 DEG C under nitrogen protection, react 24h.React complete sucking filtration,
Obtain white solid powder.Fusing point: 178 DEG C-184 DEG C
(2) synthesis N, N-dioctyl Benzoylamide bromo derivative intermediate
Take 1g (0.004mol) 4-bromomethyl-3-nitrobenzoic acid in 100mL there-necked flask, magnetic agitation
Under, dripping 10mL thionyl chloride, back flow reaction 3h, react complete, rotation is evaporated off excess thionyl chloride.
In there-necked flask, drip 0.96g (0.004mol) two 1-Aminooctane, drip complete, add 0.5g (0.004mol)
Potassium carbonate, 40 DEG C of reaction 12h, stopped reaction, add appropriate amount of deionized water, separatory, the anhydrous sulfur of organic layer
Acid sodium is dried, and chromatographic column separation eluant is the mixed liquor that volume ratio is 40:1 of dichloromethane and methanol,
Pale yellow oily liquid body.Productivity 76.0%.
(3) synthesis (4-diethylene triamine pentacetic acid (DTPA) ester group)-3-nitro-N, N-dioctyl Benzoylamide
Take the double acid anhydride of 0.22g (0.0006mol) diethylene triamine pentacetic acid (DTPA) in 100mL single port flask, add
10mL dry DMF is heated to 60 DEG C of dissolvings, is cooled to room temperature, and the bromo that first dropping is dissolved in DMF produces
Thing, then drip the DBU that 0.1g is dissolved in DMF, under nitrogen protection, 50 DEG C of reaction 1h, in reactant liquor
Add suitable quantity of water, produce milky white liquid, centrifugal, obtain subsoil yellow solid, column chromatography for separation, eluant
It is the mixture of 10:1 for dichloromethane and methanol volume ratio, obtains bright yellow solid (4-diethylenetriamine five second
Perester radical)-3-nitro-N, N-dioctyl Benzoylamide.Productivity 18.2%.
Fig. 1 is surface active molecules (4-diethylene triamine pentacetic acid (DTPA) the ester group)-3-nitro of embodiment 1 preparation
The mass spectrum of-N, N-dioctyl Benzoylamide；
MS:m/z[M-H]-794.50,[M/2-H]-396.88,[M+H]+796.45,[M+Na]+818.45
Fig. 2 is surface active molecules (4-diethylene triamine pentacetic acid (DTPA) the ester group)-3-nitro of embodiment 1 preparation
-N, N-dioctyl Benzoylamide1H NMR schemes.
1H NMR(400MHz,CD2Cl2,CD3OD):δin ppm 0.90-0.84(m,6H,2×CH3-CH2-)；
1.37-1.13(m,24H,2×-(CH2)6-CH3)；2.21-1.53(m,8H,2×-N-CH2-CH2-N-)；3.33(s,
14H,5×-N-CH2-COO-,2×-CO-N-CH2-CH2-)；5.50-5.54(s,2H,-O-CH2-C6H6-)；
7.68(d,1H,-C6H6-)；7.95(d,1H,-C6H6-)；8.09(s,1H,-C6H6-)
Embodiment 2 light degradation surfactant (4-diethylene triamine pentacetic acid (DTPA) ester group)-3-nitro-N, N-didecyl
The synthesis of yl-benzamide:
(1) synthesis diethylene triamine pentacetic acid (DTPA) acid anhydride
With embodiment 1
(2) synthesis N, N-didecyl Benzoylamide bromo derivative intermediate
Take in 1g (0.004mol) 4-bromomethyl-3-nitrobenzoic acid and 100mL there-necked flask, magnetic agitation
Under, dripping 10mL thionyl chloride, back flow reaction 4h, react complete, rotation is evaporated off excess thionyl chloride.
In there-necked flask, drip 1.19g (0.004mol) two n-Decylamine, drip complete, add 0.5g (0.004mol)
Potassium carbonate, 50 DEG C of reaction 15h, stopped reaction, add appropriate amount of deionized water, separatory, the anhydrous sulfur of organic layer
Acid sodium is dried, and chromatographic column separation eluant is the mixed liquor that volume ratio is 40:1 of dichloromethane and methanol,
Pale yellow oily liquid body.Productivity 62.1%.
(3) synthesis (4-diethylene triamine pentacetic acid (DTPA) ester group)-3-nitro-N, N-didecyl Benzoylamide
Take the double acid anhydride of 0.22g (0.0006mol) diethylene triamine pentacetic acid (DTPA) in 100mL single port flask, add
10mL dry DMF is heated to 70 DEG C of dissolvings, is cooled to room temperature, and the bromo that first dropping is dissolved in DMF spreads out
Biology, then drip the DBU that 0.1g is dissolved in DMF, under nitrogen protection, 60 DEG C of reaction 3h, toward reactant liquor
Middle addition suitable quantity of water, produces milky white liquid, centrifugal, obtains subsoil yellow solid, chromatographic column separation eluant
For the mixed liquor that volume ratio is 10:1 of dichloromethane Yu methanol, cross post and separate, obtain bright yellow solid (4-bis-
Ethylene pentaacetic acid ester group)-3-nitro-N, N-didecyl Benzoylamide.Productivity 18.6%.
Embodiment 3 light degradation surface active molecules (4-diethylene triamine pentacetic acid (DTPA) ester group)-3-nitro-N, N-bis-
The synthesis of lauryl amine yl-benzamide:
(1) synthesis diethylene triamine pentacetic acid (DTPA) acid anhydride
With embodiment 1
(2) synthetic bromide is for derivatives intermediates
Take in 1g (0.004mol) 4-bromomethyl-3-nitrobenzoic acid and 100mL there-necked flask, magnetic agitation
Under, dripping 10mL thionyl chloride, back flow reaction 3h, react complete, rotation is evaporated off excess thionyl chloride.
In there-necked flask, drip 1.47g (0.004mol) double lauryl amine, drip complete, add 0.5g (0.004mol)
Potassium carbonate, 40 DEG C of reaction 12h, stopped reaction, add appropriate amount of deionized water, separatory, the anhydrous sulfur of organic layer
Acid sodium is dried, and chromatographic column separation eluant is the mixed liquor that volume ratio is 40:1 of dichloromethane and methanol,
Pale yellow oily liquid body.Productivity 46.5%.
(3) the double lauryl amine yl-benzamide of synthesis (4-diethylene triamine pentacetic acid (DTPA) ester group)-3-nitro-N, N-
Take the double acid anhydride of 0.22g (0.0006mol) diethylene triamine pentacetic acid (DTPA) in 100mL single port flask, add
10mL dry DMF is heated to 70 DEG C of dissolvings, is cooled to room temperature, the bromination product that dropping is dissolved in DMF.
Drip complete, then drip the DBU that 0.1g is dissolved in DMF, under nitrogen protection, 50 DEG C of reaction 1.5h, past
Reactant liquor adds suitable quantity of water, produces milky white liquid, centrifugal, obtain subsoil yellow solid, chromatographic column separates
Eluant is the mixed liquor that volume ratio is 10:1 of dichloromethane and methanol, crosses post and separates, obtains bright yellow solid
The double lauryl amine yl-benzamide of (4-diethylene triamine pentacetic acid (DTPA) ester group)-3-nitro-N, N-.Productivity 18.4%.
Claims (10)
1. the surfactant containing adjacent p-Nitrobenzyl light degradation group, structure such as formula I,
Wherein, m and n is separately selected from 6,8,10,12 or 14.
2. the preparation method of the surfactant containing adjacent p-Nitrobenzyl light degradation group, it is characterised in that:
Anhydrous solvent is joined in the double acid anhydride of diethylene triamine pentacetic acid (DTPA) and be heated to 60～70 DEG C of dissolvings, be cooled to room
Temperature, double long-chain bromo derivatives that dropping is dissolved in anhydrous solvent；The catalyst that dropping is dissolved in anhydrous solvent
DBU, under nitrogen protection, 30～80 DEG C of reaction 1-2h, in reactant liquor, add suitable quantity of water, produce milky liquid
Body, centrifugal, obtain subsoil yellow solid, column chromatography for separation, eluant is the mixed liquor of dichloromethane and methanol,
Obtain adjacent p-Nitrobenzyl light-operated surface active molecules bright yellow solid；
Described pair of long-chain bromo derivative structure such as formula II:
Wherein, m and n is separately selected from 6,8,10,12 or 14.
Preparation method the most according to claim 2, it is characterised in that: the double acid anhydride of diethylene triamine pentacetic acid (DTPA):
Double long-chain bromo derivatives: catalyst DBU: water mol ratio is 1:0.8-1.2:0.8-1.2:40-60.
Preparation method the most according to claim 2, it is characterised in that: the double acid anhydride of diethylene triamine pentacetic acid (DTPA):
Anhydrous solvent mol ratio is 1:250-350.
Preparation method the most according to claim 2, it is characterised in that: described anhydrous solvent is selected from DMSO
Or DMF.
Preparation method the most according to claim 2, it is characterised in that in described pair of long-chain bromo derivative
The preparation method of mesosome is:
In adjacent nitrobenzyl br-derivatives, drip thionyl chloride, after back flow reaction 2～5h, remove excess thionyl chloride；
The appropriate double long-chain secondary amine of dropping and appropriate potassium carbonate, 30～60 DEG C of reaction 10-14h stopped reaction, add and go in right amount
Ionized water, separatory, organic layer anhydrous sodium sulfate is dried overnight, and eluant is the mixing of dichloromethane and methanol
Liquid, column chromatography for separation, obtain benzyl br-derivatives pale yellow oily liquid body；
Double long-chain secondary amine structure such as general formula III:
Wherein, m and n is separately selected from 6,8,10,12 or 14.
7. according to the preparation method described in claim 6, it is characterised in that: adjacent nitrobenzyl br-derivatives: two
Chlorine sulfoxide: double long-chain secondary amine: potassium carbonate mol ratio is 1:60-80:0.8-1.2:0.8-1.2.
Method the most according to claim 6, it is characterised in that: described adjacent nitrobenzyl br-derivatives is selected from
4-bromomethyl-3-nitrobenzoic acid or 4-bromomethyl-3-nitrobenzene-sulfonic acid.
Preparation method the most according to claim 6, it is characterised in that:
Eluant used by the double long-chain bromo derivative intermediate of synthesis is the volume ratio of dichloromethane and methanol
(20～40): the mixed liquor of 1.
Preparation method the most according to claim 2, it is characterised in that: the adjacent light-operated table of p-Nitrobenzyl of synthesis
Eluant used by the bioactive molecule of face is dichloromethane and the volume ratio of methanol is (10～20): the mixed liquor of 1.
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| CN109336952A (en) * | 2018-10-26 | 2019-02-15 | 大连理工大学 | It is a kind of it is novel can light-operated release nuclear-magnetism radiography lipid and preparation method thereof |
| CN110003031A (en) * | 2019-04-28 | 2019-07-12 | 大连理工大学 | A kind of amphipathic molecule and its synthetic method containing adjacent nitro benzyl ester light degradation group |
| CN110075306A (en) * | 2019-04-28 | 2019-08-02 | 大连理工大学 | The preparation method of a kind of light-operated visual pharmaceutical carrier of near-infrared |
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| CN110003031A (en) * | 2019-04-28 | 2019-07-12 | 大连理工大学 | A kind of amphipathic molecule and its synthetic method containing adjacent nitro benzyl ester light degradation group |
| CN110075306A (en) * | 2019-04-28 | 2019-08-02 | 大连理工大学 | The preparation method of a kind of light-operated visual pharmaceutical carrier of near-infrared |
| WO2020220963A1 (en) * | 2019-04-28 | 2020-11-05 | 大连理工大学 | Amphiphilic molecule containing o-nitrobenzyl ester-based photodegradable group, and synthesis method therefor |
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