CN103864686A - Microwave atmospheric pressure synthesis method for naphthalene imide quaternary ammonium salt - Google Patents
Microwave atmospheric pressure synthesis method for naphthalene imide quaternary ammonium salt Download PDFInfo
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Abstract
The invention discloses a microwave atmospheric pressure synthesis method for a naphthalene imide quaternary ammonium salt. The method is characterized by comprising the following step: by taking 4-Br-1,8-anhydride naphthalene as a raw material, reacting by three steps of amination, amidation and side-chain quaternization by adopting a microwave atmospheric pressure synthesis method, so as to obtain the water-soluble naphthalene imide quaternary ammonium salt. A solvent selected in each step is a polar molecule, microwave radiation is applied in a pulse mode, proper radiation power, pulse width and duty ratio are controlled, and the heat effect and non-heat effect of the microwave are reasonably utilized. The method disclosed by the invention has the advantages that a lot of solvents are not needed, operation is simple, the reaction rate of each step is improved by over 10 times in comparison with that of a conventional method, and the defects of the prior art that reaction time is long, operation is fussy, pollution to environment is caused by a lot of solvents, and the like are solved. Meanwhile, the product is easy to purify, and the productive rate of each step is improved. Therefore, the synthesis method provided by the invention is an efficient, energy-saving, green and environment-friendly synthesis method.
Description
Technical field
The invention belongs to a kind of naphthalimide fluorescent compound preparation field, particularly a kind of microwave atmospheric synthesizing method of naphthalimide quaternary ammonium salt.
Background technology
Naphthalimide fluorescent compound has a naphthalene ring that planarity is very strong, exists large " a suction-supplied for electronic conjugated system " in molecular structure, makes it have higher fluorescence intensity and quantum yield.This compounds, with its unique character, has obtained research widely.Such fluorescent chemicals lovely luster, fluorescence is strong, has been widely used as at present fluorescence dye and white dyes.Research in recent years shows, this compounds is also often used as the fields such as Electrophotosensitivmaterial material, liquid crystal material, laser, fluorescent probe, DNA intercalator.
But the naphthalimide material of most of bibliographical informations is water-soluble all poor, range of application is restricted, and necessary chemically modified can improve that it is water-soluble.Be seen at present the two kinds of modification approach that mainly contain of report: on naphthalene nucleus parent, introduce the hydrophilic radicals such as sulfonic group, or introduce quaternary ammonium salt structure (Zhang Yuehua at the side chain of naphthalene nucleus, Zhang Qiping, the .1 such as Lei Wu, synthetic, the sign of 8-naphthalimide fluorescent monomer and photoluminescent property [J]. Speciality Petrochemicals, 2008,25 (5): 60-6; Zhang Qiping, Zhang Yuehua, yellow lead etc. water miscible 1, synthetic and the sign [J] of 8-naphthalimide fluorescent monomer. chemical reagent, 2007,29 (2): 78-80), by contrast, latter reaction's condition is relatively simple, but still has the drawback such as long reaction time, complex operation.
Summary of the invention
Object of the present invention is exactly the defect that is to overcome above-mentioned conventional heating synthetic method, develop a kind of simple to operate, solvent load is few, speed of response is fast, convenient post-treatment, productive rate are high, the microwave atmospheric synthesizing method of the naphthalimide quaternary ammonium salt of environmental protection.
For solving the problems of the technologies described above, the present invention is achieved by the following technical programs:
A microwave atmospheric synthesizing method for the naphthalimide quaternary ammonium salt being represented by general formula I V,
It is characterized in that, comprise the steps:
(1) get the chemical compounds I 4-Br-1 that mol ratio is 1:2～3.5,8-naphthalene acid anhydride and N methyl piperazine are in single port flask, and ethylene glycol monomethyl ether makees solvent, are placed in microwave reaction instrument, load onto reflux, after microwave pulse radioreaction 40～80min, in reaction solution, add Glacial acetic acid, freezing and crystallizing, after thawing, filter, collect solid product, with alcohol washing, vacuum-drying, obtain compound ii.
(2) by the compound ii obtaining, thanomin, the ratio taking mole proportioning as 1:2～4 and lower alcohol are disposable adds in single port flask, be placed in microwave reaction instrument, load onto reflux, after microwave pulse radioreaction 10～50min, by in mixed solution impouring distilled water, leave standstill solid is separated out completely, suction filtration, vacuum-drying solid obtains compound III.
(3) get ratio taking mol ratio as 1:2～4 of compound III, halohydrocarbon and polar solvent in single port flask, be placed in microwave reaction instrument, load onto reflux, microwave radiation reaction 30～60min; Underpressure distillation reaction product is removed solvent, then uses acetone recrystallization, and vacuum-drying, obtains object product compounds Ⅳ; Described halohydrocarbon is halogenated alkane, haloolefin or halogenated aryl hydrocarbon, and wherein halogen is chlorine, bromine or iodine, and described polar solvent is DMF(dimethyl formamide), DMA(N,N-DIMETHYLACETAMIDE), one in methyl alcohol, ethanol and second eyeball.
According to the microwave atmospheric synthesizing method of naphthalimide quaternary ammonium salt of the present invention, it is characterized in that, microwave radiation in described step (1), (2) and (3) all applies with pulse mode, and in pulse protocol, microwave power, pulse width and dutycycle are controlled: for step (1), preferred microwave power, pulse width and dutycycle are respectively 390～680W, 40～70s and 6～12:1; For step (2), preferred microwave power, pulse width and dutycycle are respectively 250～530W, 30～50s and 3～6:1; For step (3), preferred microwave power, pulse width and dutycycle 250～450W, 50～70s and 6～12:1 respectively; But be not limited to these numerical value.
According to the microwave atmospheric synthesizing method of naphthalimide quaternary ammonium salt of the present invention, the alcohol in described step (1) in alcohol washing is dehydrated alcohol or anhydrous methanol.
According to the microwave atmospheric synthesizing method of naphthalimide quaternary ammonium salt of the present invention, in described step (2) lower alcohol be in ethanol, methyl alcohol and propyl alcohol wherein one or more.
Compared with prior art, the beneficial effect of the inventive method is:
1. in the inventive method, reactant and selected solvent are all polar molecules, and the easy microwave energy absorbing of polar molecule heats up rapidly reaction, and speed of reaction is significantly accelerated.These polar molecule charge distribution imbalances, specific inductivity is large, and easily microwave energy absorbing and produce obvious transient dipole moment and change, causes material molecule internal friction heat-dissipating, causes temperature of charge to raise and the quickening of speed of reaction.In addition, microwave vibrations frequency and molecular rotation frequency approach, and microwave action is after polar molecule, and the microwave energy that molecule stores and the mean kinetic energy of molecule exchange, and have reduced activation energy, have changed reaction kinetics.The existence meeting of microwave simultaneously causes orientation effect to molecular motion, and effective collision frequency is increased, and reaction is more prone to carry out.In the inventive method, each step speed of reaction has all improved more than 10 times compared with ordinary method;
2. the deep understanding of the inventive method based on to microwave action mechanism, microwave radiation applies with pulse mode, by the adjustment to microwave irradiation power and radiated time, control microwave radiation and radiation amount, improve microwave utilising efficiency, take full advantage of the energy, also avoided due to long-time continuous radiation, make too high the produced unsafe condition of system temperature, ensure to react and effectively steadily carry out;
3. the inventive method solvent load is few, and easy purification of products respectively walks reaction yield and all increases;
4. simple to operate, the environmental protection of the inventive method, do not produce secondary pollution.
Brief description of the drawings
Fig. 1 is the reaction equation of the microwave atmospheric synthesizing method of naphthalimide quaternary ammonium salt of the present invention (compounds Ⅳ);
Fig. 2 is the molecular structural formula of Compound I-IV of relating to of the each step of microwave atmospheric synthesizing method of naphthalimide quaternary ammonium salt of the present invention.
Fig. 3 is the molecular structural formula of object product naphthalimide quaternary ammonium salt IV-1, IV-2 in embodiment of the present invention 1-6.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in detail, but do not limit the protection domain of the inventive method.
The following examples 1-6 all carries out microwave normal pressure synthesis naphthalimide quaternary ammonium salt of the present invention (compounds Ⅳ) according to the reaction equation of Fig. 1, and detailed content is as follows:;
Embodiment 1
(1) compound ii is synthetic: in 100mL flask, add successively 0.01mol4-bromo-1,8-naphthalene acid anhydride, 0.03mol N methyl piperazine and 10mL ethylene glycol monomethyl ether, be placed in microwave reaction instrument, microwave pulse radioreaction under 530W power, pulse width is 65s, and dutycycle is 12:1, radioreaction 65min, utilize TLC method monitoring reaction end (developping agent: methylene dichloride: methyl alcohol: triethylamine=18:8:0.5), until R
fbe that 0.54 raw material point disappears.In mixed solution, add 40mL Glacial acetic acid, freezing and crystallizing, filters after thawing, and collects solid, uses 20mL absolute ethanol washing 2～3 times, 40 DEG C/-0.1Mpa vacuum-drying solid, obtains dark yellow solid, productive rate 97.6%.
IR(KBr, ν/cm
-1): 1465.26,1399.37(-CH
3formation vibration); 1339.99,1350.91(C-N stretching vibration), 2687.92, the flexible frequency multiplication of 2607.71(C-N); The C-Br stretching vibration peak at 556.85 places disappears simultaneously.
1H?NMR（DMSO-d
6，400MHz，δ/10
-6）：2.950（s，3H，-CH
3）；3.346（s，4H，N(CH
2CH
2)
2N-CH
3）；3.597（s，4H，N(CH
2CH
2)
2N-CH
3）；7.486（d，J=8.4Hz，1H，ArH）；7.898（t，J=7.6Hz，1H，ArH）；8.461（d，J=8.4Hz，1H，ArH）；8.545（t，J=6.8Hz，2H，ArH）。
(2) compound III is synthetic: 0.005mol compound ii, 0.015mol thanomin and 10mL ethanol are disposable to add in 100mL flask, be placed in microwave reaction instrument, microwave pulse radioreaction under 390W power, pulse width is 40s, dutycycle is 3:1, radioreaction 25min.By in mixed solution impouring 250mL distilled water, leave standstill solid is separated out completely, suction filtration, dry 8～12h at 50 DEG C, and then obtain yellow-green colour solid, productive rate 81.9% in 60 DEG C/-0.1Mpa vacuum-drying.
IR(KBr, ν/cm
-1): 3513.27(-OH stretching vibration); 1288.86,1235.71(naphthalene nucleus α position C-N stretching vibration); 785.90(C-N formation vibration).
1H?NMR（DMSO-d
6，400MHz，δ/10
-6）：2.312（s，3H，-CH
3）；2.648（s，4H，N(CH
2CH
2)
2N-CH
3）；3.237（s，4H，N(CH
2CH
2)
2N-CH
3）；3.608（t，J=6.4Hz，2H，NCH
2CH
2OH）；4.144（t，J=6.4Hz，2H，NCH
2CH
2OH）；7.341（d，J=8.4Hz，1H，ArH）；7.813（t，J=8.0Hz，1H，ArH）；8.390（d，J=8.0Hz，1H，ArH）；8.428（d，J=8.4Hz，1H，ArH）；8.467（d，J=7.6Hz，1H，ArH）。
(3) compounds Ⅳ-1(4-(N '-methyl isophthalic acid-piperazinyl)-N-hydroxyethyl-1,8-naphthalene n-butyl bromide quaternary ammonium salt, molecular structural formula is shown in Fig. 3) synthetic: get 0.005mol compound III, 0.020mol1-n-butyl bromide and 5mL DMF in 100mL flask, be placed in microwave instrument, impulse radiation reaction under 390W power, pulse width is 65s, and dutycycle is 12:1, radioreaction 54min.Solvent is removed in underpressure distillation, uses 40mL washing with acetone solid 6～7 times at every turn, and 40 DEG C of vacuum-dryings, obtain glassy yellow solid, productive rate 99.2%.
IR(KBr, ν/cm
-1): the formation vibration of 1401.77(C-H); 704.46(-CH
2rocking vibration).
1H?NMR（DMSO-d
6，δ/10
-6）：3.232（s，3H，-N
+CH
3）；1.768（m，2H，-CH
2CH
2CH
3）；1.388（q，J=7.2Hz，2H，-CH
2CH
2CH
3）；0.991（t，J=7.2Hz，3H，-CH
2CH
2CH
3）；3.785（s，4H，-N(CH
2CH
2)）；3.603（s，4H，-N
+(CH
2CH
2)）；3.613（s，2H，-NCH
2CH
2OH）；4.149（t，J=6.4Hz，2H，-NCH
2CH
2OH）；7.504（d，J=8.4Hz，1H，ArH）；7.865（t，J=8.0Hz，1H，ArH）；8.479（d，J=8.0Hz，1H，ArH）；8.512（d，J=2.0Hz，1H，ArH）；8.530（d，J=7.2Hz，1H，ArH）。
C is pressed in ultimate analysis
23h
30o
3n
3br(Mr=475.9) meter, theoretical value: C, 58.05; H, 6.36; N, 8.83, measured value: C, 58.29; H, 6.28; N, 8.78.
Comparative example
Comparative example is for adopting conventional heating method synthetic compound IV-1, IV-2, concrete operation step is pressed document (Zhang Yuehua, Zhang Qiping, Lei Wu, waits .1, synthetic, the sign of 8-naphthalimide fluorescent monomer and photoluminescent property [J]. Speciality Petrochemicals, 2008,25 (5): 60-6) implement, the raw material dosage of each step reaction is identical with microwave method (embodiment 1 and embodiment 5), and concrete implementation step is as follows:
(a) compound ii is synthetic: get 0.01mol4-bromo-1,8-naphthalic anhydride, in 100mL there-necked flask, adds 40mL ethylene glycol monomethyl ether, and oil bath reflux is dissolved it completely.The mixed solution that slowly drips 0.03mol N methyl piperazine and 10mL ethylene glycol monomethyl ether, about 0.5h drips off, back flow reaction 10h～11h.Solvent is removed in underpressure distillation, adds 50mL Glacial acetic acid and freezes crystalline substance in refrigerator and cooled, and aftertreatment is with step (1) in microwave method embodiment 1.
(b) compound III is synthetic: get 0.005mol compound ii in 100mL there-necked flask, add 40mL dehydrated alcohol, oil bath heating, is warming up to 80 DEG C, slowly drips the mixed solution of 0.015mol thanomin and 10mL ethanol, and about 0.5h drips off, back flow reaction 6h.About 30mL ethanol is removed in underpressure distillation, and by surplus solution impouring 300mL distilled water, aftertreatment is with step (2) in microwave method embodiment 1.
(c) compounds Ⅳ is synthetic: get compound 0.005mol III in 100mL there-necked flask, add 30mL DMF, oil bath heating for dissolving, after raw material dissolves completely, start to drip and the mixed solution of microwave method (embodiment 1 and embodiment 5) the identical halohydrocarbon of dosage and 10mL DMF, stirring and refluxing is reacted 8h～10h.Solvent is removed in underpressure distillation, uses 40mL washing with acetone solid 9～10 times at every turn, and 40 DEG C of vacuum-dryings, obtain compounds Ⅳ.Wherein synthetic compound IV-1, halohydrocarbon is selected n-butyl bromide; When synthetic compound IV-2, halohydrocarbon is selected propenyl chloride.
Table 1 has been listed the result contrast of microwave non-pressure process and conventional heating method.Wherein microwave non-pressure process data are obtained by step (3) in embodiment 1 and embodiment 5.
The contrast of table 1 microwave non-pressure process and conventional heating method
Embodiment 2
(1) compound ii is synthetic: reaction conditions is with the step in embodiment 1 (1), difference is that impulse radiation power is 450W, and the radioreaction time is 70min, and post-treating method is with the step in embodiment 1 (1), obtain dark yellow solid, productive rate is 92.5%.
(2) compound III is synthetic: reaction conditions is with the step in embodiment 1 (2), and difference is that lower alcohol is methyl alcohol, and impulse radiation power is 250W, and post-treating method, with the step in embodiment 1 (2), obtains yellow-green colour solid, and productive rate is 75.7%.
(3) compounds Ⅳ-1 is synthetic: reaction conditions is with the step in embodiment 1 (3), and difference is that impulse radiation power is 450W, and post-treating method, with the step in embodiment 1 (3), obtains glassy yellow solid, productive rate 98.3%.
Embodiment 3
(1) compound ii is synthetic: reaction conditions is with the step in embodiment 1 (1), difference is that impulse radiation power is 600W, and the radioreaction time is 55min, and post-treating method is with the step in embodiment 1 (1), obtain dark yellow solid, productive rate is 93.3%.
(2) compound III is synthetic: reaction conditions is with the step in embodiment 1 (2), difference is that impulse radiation power is 530W, and the radioreaction time is 12min, and post-treating method is with the step in embodiment 1 (2), obtain yellow-green colour solid, productive rate is 76.4%.
(3) compounds Ⅳ-1 is synthetic: reaction conditions is with the step in embodiment 1 (3), difference is that mole proportioning of raw material is 1:2(compound III: 0.005mol, 1-n-butyl bromide: 0.010mol), post-treating method is with the step in embodiment 1 (3), obtain glassy yellow solid, productive rate 80.8%.
Embodiment 4
(1) compound ii is synthetic: in 100mL flask, add successively 0.01mol4-bromo-1,8-naphthalene acid anhydride, 0.03mol N methyl piperazine and 5mL ethylene glycol monomethyl ether, be placed in microwave reaction instrument, impulse radiation reaction under 530W power, pulse width is 45s, dutycycle is 8:1, and the radioreaction time is 45min.Post-treating method, with the step in embodiment 1 (1), obtains dark yellow solid, productive rate 82.4%.
(2) compound III is synthetic: reaction conditions is with the step in embodiment 1 (2), difference is that mole proportioning of raw material is 1:4(compound ii: 0.005mol, thanomin: 0.020mol), post-treating method is with the step in embodiment 1 (2), obtain yellow-green colour solid, productive rate is 77.0%.
(3) compounds Ⅳ-2(4-(N '-methyl isophthalic acid-piperazinyl)-N-hydroxyethyl-1,8-naphthalene allyl chlorine quaternary ammonium salt, molecular structural formula is shown in Fig. 3) synthetic: get 0.005mol compound III, 0.0175mol propenyl chloride and 5mL DMF in 100mL flask, be placed in microwave instrument, impulse radiation reaction under 320W power, pulse width is 65s, and dutycycle is 12:1, radioreaction 43min.Solvent is removed in underpressure distillation, filters, and uses 40mL washing with acetone solid 6～7 times at every turn, and 40 DEG C of vacuum-dryings, obtain yellow-green colour solid, productive rate 87.9%.
IR(KBr, ν/cm
-1): 3073(CH=CH
2c-H stretching vibration) 1613.79(allyl group C=C stretching vibration); 997.73,924.41(CH=CH
2c-H flexural vibration).
1H?NMR（DMSO-d
6，400MHz，δ/10
-6）：3.220（s，3H，-N
+CH
3）；4.279（d，J=6.8Hz，2H，CH
2CH=CH
2）；6.133～6.198（m，1H，CH
2CH=CH
2）；5.733（m，2H，CH
2CH=CH
2）；3.778（s，4H，-N(CH
2CH
2)）；3.607（s，4H，-N
+(CH
2CH
2)）；3.623（s，2H，-NCH
2CH
2OH）；4.149（t，J=6.4Hz，2H，-NCH
2CH
2OH）；7.505（d，J=8.0Hz，1H，ArH）；7.868（t，J=8.0Hz，1H，ArH）；8.473～8.528（m，3H，ArH）。
C is pressed in ultimate analysis
22h
26o
3n
3cl(Mr=415.5) meter, theoretical value: C, 63.59; H, 6.31; N, 10.11, measured value: C, 63.88; H, 6.26; N, 10.20.
Embodiment 5
(1) compound ii is synthetic: in 100mL flask, add successively 0.01mol4-bromo-1,8-naphthalene acid anhydride, 0.03mol N methyl piperazine and 7mL ethylene glycol monomethyl ether, be placed in microwave reaction instrument, impulse radiation reaction under 530W power, pulse width is 55s, dutycycle is 10:1, and the radioreaction time is 60min.Post-treating method, with the step in embodiment 1 (1), obtains dark yellow solid, productive rate 92.4%.
(2) compound III is synthetic: reaction conditions is with the step in embodiment 1 (2), and difference is to be 40min the radioreaction time, and post-treating method, with the step in embodiment 1 (2), obtains yellow-green colour solid, and productive rate is 72.5%.
(3) compounds Ⅳ-2 is synthetic: reaction conditions is with the step in embodiment 4 (3), and difference is that polar solvent is second eyeball, and the radioreaction time is 54min, and post-treating method, with the step in embodiment 4 (3), obtains yellow-green colour solid, productive rate 93.5%.
Embodiment 6
(1) compound ii is synthetic: in 100mL flask, add successively 0.01mol4-bromo-1,8-naphthalene acid anhydride, 0.02mol N methyl piperazine and 5mL ethylene glycol monomethyl ether, be placed in microwave reaction instrument, impulse radiation reaction under 530W power, pulse width is 45s, dutycycle is 8:1, and the radioreaction time is 78min.Post-treating method, with the step in embodiment 1 (1), obtains dark yellow solid, and productive rate is 84.8%.
(2) 0.01mol compound ii, 0.03mol thanomin and 10mL ethanol are disposable adds in 100mL flask, be placed in microwave instrument, and impulse radiation reaction under 390W power, pulse width is 40s, dutycycle is 3:1, radioreaction 40min.Post-treating method, with the step in embodiment 1 (2), obtains yellow-green colour solid, and productive rate is 75.3%.
(3) compounds Ⅳ-2 is synthetic: reaction conditions is with the step in embodiment 4 (3), and difference is that impulse radiation power is 390W, and post-treating method, with the step in embodiment 4 (3), obtains yellow-green colour solid, productive rate 77.8%.
Claims (4)
1. a microwave atmospheric synthesizing method for the naphthalimide quaternary ammonium salt being represented by general formula I V,
It is characterized in that, comprise the steps:
1) get the chemical compounds I 4-bromo-1 that mol ratio is 1:2～3.5,8-naphthalene acid anhydride and N methyl piperazine are in single port flask, and ethylene glycol monomethyl ether is made solvent, are placed in microwave reaction instrument, load onto reflux, after microwave pulse radioreaction 40～80min, in reaction solution, add Glacial acetic acid, freezing and crystallizing, after thawing, filter, collect solid product, with alcohol washing, vacuum-drying, obtain compound ii;
2) by the compound ii obtaining, thanomin, the ratio taking mol ratio as 1:2～4 and lower alcohol are added in single port flask, be placed in microwave reaction instrument, load onto reflux, after microwave pulse radioreaction 10～50min, by in mixed solution impouring distilled water, leave standstill solid is separated out completely, suction filtration, vacuum-drying solid obtains compound III;
3) get ratio taking mol ratio as 1:2～4 of compound III, halohydrocarbon and polar solvent in single port flask, be placed in microwave reaction instrument, load onto reflux, microwave radiation reaction 30～60min; Underpressure distillation reaction product is removed solvent, then uses acetone recrystallization, and vacuum-drying, obtains object product compounds Ⅳ;
In described step 3), halohydrocarbon is halogenated alkane, haloolefin or halogenated aryl hydrocarbon, and halogen is chlorine, bromine or iodine; Described polar solvent be in dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl alcohol, ethanol and second eyeball wherein one or more.
2. microwave atmospheric synthesizing method according to claim 1, it is characterized in that described step 1), 2) and 3) in microwave pulse radiation in pulse protocol, microwave power, pulse width and dutycycle are controlled: microwave power, pulse width and the dutycycle of step 1) are respectively 390～680W, 40～70s and 6～12:1; Step 2) microwave power, pulse width and dutycycle be respectively 250～530W, 30～50s and 3～6:1; Microwave power, pulse width and the dutycycle of step 3) 250～450W, 50～70s and 6～12:1 respectively.
3. microwave atmospheric synthesizing method according to claim 1, is characterized in that, the alcohol in described step 1) in alcohol washing is dehydrated alcohol or anhydrous methanol.
4. microwave atmospheric synthesizing method according to claim 1, is characterized in that described step 2) in lower alcohol be one or more in ethanol, methyl alcohol and propyl alcohol.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005044309A1 (en) * | 2003-11-05 | 2005-05-19 | Photobiomed Corporation | Bonding tissues and cross-linking proteins with naphthalimide compounds |
| CN101381168A (en) * | 2008-07-04 | 2009-03-11 | 南通大学 | Fluorescence labeling acrylic acid-sodium acrylic sulphonate co-polymer water treatment agent and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005044309A1 (en) * | 2003-11-05 | 2005-05-19 | Photobiomed Corporation | Bonding tissues and cross-linking proteins with naphthalimide compounds |
| CN101381168A (en) * | 2008-07-04 | 2009-03-11 | 南通大学 | Fluorescence labeling acrylic acid-sodium acrylic sulphonate co-polymer water treatment agent and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张其平，等: "水溶性的1 , 8-萘酰亚胺类荧光单体的合成与表征", 《化学试剂》, vol. 29, no. 2, 28 February 2007 (2007-02-28), pages 78 - 80 * |
| 张跃华，等: "1,8-萘酰亚胺荧光单体的合成、表征与荧光性质", 《精细石油化工》, vol. 25, no. 5, 30 September 2008 (2008-09-30), pages 60 - 64 * |
| 张跃华，等: "１，８萘酰亚胺荧光单体的合成及光谱的量子化学研究", 《发光学报》, vol. 32, no. 5, 31 May 2011 (2011-05-31), pages 505 - 513 * |
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