CN105837505A - Water or oil soluble controllable fluorescent monomer for copolymerization and preparation method thereof - Google Patents

Water or oil soluble controllable fluorescent monomer for copolymerization and preparation method thereof Download PDF

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CN105837505A
CN105837505A CN201610277836.5A CN201610277836A CN105837505A CN 105837505 A CN105837505 A CN 105837505A CN 201610277836 A CN201610277836 A CN 201610277836A CN 105837505 A CN105837505 A CN 105837505A
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bromo
naphthalimide
fluorescent monomer
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于静
沈卫平
姜开元
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University of Shanghai for Science and Technology
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
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Abstract

The invention relates to a fluorescent functional monomer for copolymerization and a preparation method thereof .The structural formula of the compound can be found in specification, the compound has excellent fluorescence response performance, and multiple types of functionalized polymers and oligomer are configured through controllable polymerization .A high-sensitivity fluorescent tracing detection technology is utilized, and wide application prospect is achieved in the fields of biological macromolecular separation and identification, biosensors, medical diagnosis, drug tracing, targeted drug release, a tracing corrosion inhibition and antisludging agent in an industrial cooled and recycled water treatment system; the synthesis route is efficient and simple, raw materials are easy to obtain, and significant application and popularization value is achieved on the aspect of purification treatment.

Description

For the water of combined polymerization or oil-soluble controllable fluorescent monomer and preparation method thereof
Technical field
The present invention relates to a kind of fluorescent functional monomer and preparation method thereof, a kind of copolymerizable fluorescent functional list Body and preparation method thereof.
Background technology
Detection technique of fluorescence has the sensitivity of height and the widest responding range, is widely used to analysisization The various aspects such as, biochemistry and cell biology.In actual applications, small molecule fluorescent compound has its limitation used Property: first, when forming homogeneous system during small molecule fluorescent compound is dissolved into solution to be measured, system to be measured may be produced dirt Dye, can not use it for anything else again;Second, after small molecule fluorescent compound is dissolved in investigation system, it is difficult to extract and separate, not there is repetition Usability repeatedly;3rd, the water-insoluble and toxic and side effect of some small molecule fluorescent compounds so that it is life science, doctor Application in etc. field is restricted;4th, small molecule fluorescent compound is difficult to make optical instrument, it is difficult to make itself and light Instrument combines, and realizes Aulomatizeted Detect and is restricted.Fluorescent polymer is that small molecule fluorescent compound is introduced polymer side Chain, the end of the chain or by fluorescent functional monomer polymerization preparation.Since the 1960's, the most document report, it grinds Study carefully research fields such as relating to material science, life science, medical science and chemistry.Some have good mechanical performance, easy film forming and Fluorescent polymer easy to process receives publicity in material science research field;And some have the fluorescence polymerization of good aqueous solubility Thing is more paid close attention in the research field such as life science and medical science.Fluorescent polymer in use, is possible not only to gram Take small molecule fluorescent compound limitation on using, but also there is some self advantage.
1,8-naphthalimide is a kind of application fluorescent chromophore widely, and it has good heat endurance and light is steady Qualitative, and it also has big Stokes (stokes) displacement, and high fluorescence quantum yield, fluorescence emission wavelengths is moderate Advantages such as (about 520 nm).Naphthalimide fluorescent probe is usually by 1,8-naphthalene acid anhydride and various primary amine class substance reaction systems For forming.The fluorescence intensity of 1,8 naphthalene acid anhydrides itself is the most weak, almost without fluorescence, if modifying confession on 4 of naphthalene nucleus The group (such as amino) of electronics the most just can go into strong confession-electrophilic system, and the electronics in this system is easy to be swashed by light There is transition after Faing, produce strong fluorescence.
Styrene monomer has the addition polymerization performance of brilliance, and it is not only by polymerisation in bulk, suspension polymerisation, polymerisation in solution, breast Radical polymerization or the anionic polymerisations such as liquid polymerization, form the homopolymers of changeable material property, and can be formed block copolymer, Functional copolymer, single dispersing type copolymer, water solubility copolymer etc., be preferable copolymerization module.
Summary of the invention
An object of the present invention is to overcome problems of the prior art, it is provided that a class may be used for combined polymerization Water or the controlled fluorescent monomer compound of oil-soluble.
The two of the purpose of the present invention are to provide the preparation method of such water or oil-soluble compounds.
For achieving the above object, the reaction mechanism that the present invention uses is:
According to above-mentioned mechanism, the present invention adopts the following technical scheme that
A kind of polymerisable water or the controlled fluorescent monomer of oil-soluble, it is characterised in that the structural formula of this monomer is:
Wherein R is C4～C18Direct-connected or branched alkyl, different octyloxy propyl group, P-TOLUENE SULFO ACID 99's base ,-THP trtrahydropyranyl ,-N, N-bis- Ethylaminoethyl ,-N, N-Dibutylaminoethyl, chloroethyl ,-(2,2,6,6-tetramethyl-tetrahydropyridine) base ,-morpholine second Base.
A kind of method preparing above-mentioned polymerisable water or the controlled fluorescent monomer of oil-soluble, it is characterised in that the method Concretely comprise the following steps:
A. bromo-for 4-1,8-naphthalic anhydride and primary amine compound are dissolved in absolute ethyl alcohol or ice by the mol ratio of 1:1 ~ 1:1.4 In acetic acid, back flow reaction to reaction completely, after reaction terminates, filters while hot, and filtrate, under 4 DEG C of states, separates out crude product crystal, Suction filtration, is washed with deionized and is vacuum dried, and the separated purifying of crude product obtains naphthalimide intermediate, and its structural formula is:, the structural formula of described primary amine compound is: RNH2；
B. under inert gas shielding, by step a gained intermediate naphthalimide and 4-aminostyryl rubbing by 1:1 ~ 1:1.3 Your ratio dissolves in glycol monoethyl ether or DMF, adds Anhydrous potassium carbonate, and its addition is 4-aminobenzene The 18% ~ 30% of ethene charged material weight, back flow reaction to reaction completely, after reaction terminates, is cooled to room temperature, is poured into by reactant liquor In ionized water, regulation pH value of solution to 6 ~ 8, suction filtration, be washed with deionized, filter cake be vacuum dried, crude product is separated to be purified Polymerisable water or the controlled fluorescent monomer of oil-soluble.
The novelty of the present invention is to be designed, hydrophilic or lipophilic group and naphthalimide fluorescence by the structure of rationality Chromophore and styrene co-monomer are organically incorporated in a molecule.Conventional naphthalimide type fluorescent monomer concentrates on Use quaternary ammoniated method, vinyl is introduced fluorescent monomer molecule, so brings two shortcomings: one is molecular band positive charge shadow Ringing combined polymerization performance, two is quaternary ammonium salts derivative facile hydrolysis, causes fluorophor to be lost.And advantages of the present invention overcomes just Two above shortcoming
The present invention utilizes having the naphthalimide fluorescent chromophore of excellent fluorescence quantum efficiency and having the benzene of good copolymerization performance Ethene functional group is organically incorporated in a molecule, and by regulation oil-soluble or water soluble group, it is thus achieved that water/oil-soluble can The copolymerization fluorescent monomer of control.This fluorescent monomer has excellent fluorescence response performance, and constructs several functions by controllable polymerization Property polymer and oligomer.Use high-sensitive fluorescent tracing detection technique, at separation of biopolymer and identification, bio-sensing Device, medical diagnosis, pharmaceutical indications, targeting drug release, and the spike corrosion inhibiting and descaling agent in industry cooling circulating water processing system Have a wide range of applications in field.Its synthetic route is efficiently simple, and raw material is easy to get, and purification process conveniently has important pushing away Wide using value.
Accompanying drawing explanation
Fig. 1 compound I-XIII absorption spectrum in chloroform solvent.
Fig. 2 compound I-VII emission spectrum in chloroform solvent.
Fig. 3 compound VIII-XIII emission spectrum in chloroform solvent.
Detailed description of the invention
Embodiment one: the preparation of fluorescent monomer I:
Fluorescent monomer I
(1) synthesis of 4-bromo-N-normal-butyl-1,8-naphthalimide；
Weigh 4-bromo-1,8-naphthalic anhydride 5.54g (0.02mol) in 250ml three-necked bottle, add the glacial acetic acid of 150ml, Under the protection of argon gas, then it is slowly added dropwise the acetum containing n-butylamine 2.14ml (0.022mol) with constant pressure funnel 10ml.Make reaction system be slowly heated after dropping and be warmed up to reflux temperature, keep 6 ~ 7h, and be tracked prison by TLC method Survey to determine reaction process.Reaction is filtered after terminating while hot, and filtrate separates out crude product crystal, suction filtration under 4 DEG C of states, and filter cake is washed To neutral, vacuum drying, crude product column chromatography purifies (eluant ethyl acetate: petroleum ether=1:4) and is just obtaining the bromo-N-of 4- Butyl-1,8-naphthalimide intermediate 5.03g, productivity is 76.0%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.86(d,1H,J=7.5Hz),8.52(d,1H,J=7.5Hz),8.32(d, 1H,J=7.0Hz),8.21(d,1H,J=7.0Hz),7.98(t,1H,J=7.5Hz),3.14(t,2H,J=7.1Hz),1.56(m, 2H),1.31(m,2H),0.9(t,3H,=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.3,137.9,132.2, 128.7,126.4,125.5,124.2,125.1,40.1,29.5,19.8,13.8.
(2) synthesis of fluorescent monomer I:
Taking intermediate 4-bromo-N-normal-butyl-1,8-naphthalimide 3g (0.009mol) is placed in the three-necked bottle flask of 100ml, point Not Jia Ru Anhydrous potassium carbonate 0.33g (0.0024mol) and the glycol monoethyl ether of 50ml, and be slowly added dropwise under the protection of argon gas 4-aminostyryl 1.1g (0.009mol), keeps reaction temperature at about 140 DEG C, keeps 8h, be tracked monitoring by TLC method To determine reaction process.After question response terminates, it is cooled to room temperature, reactant liquor is poured in the deionized water of 100ml, with 10% Hydrochloric acid solution regulation solution PH makes it be neutrality, and suction filtration is washed with deionized, and filter cake is vacuum dried, crude product column chromatography Method purifies (eluant ethyl acetate: petroleum ether=1:6) and obtains solid I 2.71g, and productivity is 81.5%.The nuclear-magnetism hydrogen of fluorescent monomer I Spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.34(d,1H),8.24(d,1H,J= 7.5Hz),7.98(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.63 (s,1H),5.18(s1H),5.61(s,1H),4.0(s,1H(N-H)),3.14(t,2H,J=7.1Hz),1.31~1.56(m, 4H),0.9(t,3H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.3,151.6,141.6,137.8, 137.2,127.4,126.4,125.9,124.2,116.3,114.3,111.4,40.1,29.5,13.8
Embodiment two: the preparation of fluorescent monomer II
Fluorescent monomer II
(1) 4-bromo-N-n-octylcyclam, the synthesis of 8-naphthalimide:
Replace n-butylamine anti-with 4-bromo-1,8-naphthalic anhydride 5.54g (0.02mol) with n-octyl amine 3.64ml (0.022mol) Should.By the operation of (1) in embodiment one, gained intermediate 4-bromo-N-n-octylcyclam, 8-naphthalimide 7.12g, productivity is 92%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.86(d,1H,J=7.5Hz),8.52(d,1H,J=7.5Hz),8.32(d, 1H,J=7.0Hz),8.21(d,1H,J=7.0Hz),7.98(t,1H,J=7.5Hz),3.14(t,2H,J=7.1Hz),1.67~ 1.31(m,12H),0.88(t,3H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.3,137.9,132.2, 128.7,125.5,124.2,125.1,40.4,31.9,30.2,26.7,29.3,22.7,14.1
(2) synthesis of fluorescent monomer II:
With 4-bromo-N-n-octylcyclam, 8-naphthalimide 3.48g(0.009mol) replace 4-bromo-N-normal-butyl-1,8-naphthoyl sub- Amine.By the operation of (2) in embodiment one, finally obtain yellow solid II 3.16g, productivity 82.5%.The core of fluorescent monomer II Magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.34(s,1H),8.24(d,1H,J= 7.5Hz),7.98(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.63 (s,1H),5.18(s,1H),5.61(s,1H),4.0(s,1H(N-H)),3.14(t,2H,J=7.1Hz),1.31~1.67(m, 12H),0.88(t,3H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.3,151.6,141.6,137.8, 137.2,127.4,125.9,124.2,116.3,114.3,111.4,40.1,31.9,30.2,29.3,26.7,22.7,14.1
Embodiment three: the preparation of fluorescent monomer III
Fluorescent monomer III
(1) synthesis of 4-bromo-N-dodecyl-1,8-naphthalimide:
Replace n-butylamine anti-with 4-bromo-1,8-naphthalic anhydride 5.54g (0.02mol) with n-dodecylamine 4.07g (0.022mol) Should.By the operation of (1) in embodiment one, gained intermediate 4-bromo-N-dodecyl-1,8-naphthalimide 8.194g, productivity It is 85.1%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.41(d,1H,J=7.5Hz),8.34(s,1H),8.26(d,1H,J= 7.5Hz),7.98(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),3.28(t,2H,J=7.1Hz),1.31~1.68(m, 20H),0.88(t,3H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.1,151.7,141.6,136.8, 137.2,128.4,125.9,124.2,116.3,114.3,111.4,40.1,31.9,30.2,29.6,29.3,26.7,22.7, 14.1.
(2) synthesis of fluorescent monomer III:
Replace 4-bromo-N-normal-butyl-1,8-naphthoyl sub-with 4-bromo-N-dodecyl-1,8-naphthalimide 3.42g (0.009mol) Amine.By the operation of (2) in embodiment one, finally obtain faint yellow solid III 3.512g, productivity 81%.The core of fluorescent monomer III Magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.38(d,1H,J=7.5Hz),8.35(d,1H),8.24(d,1H,J= 7.5Hz)7.78(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.63(s,1H),5.18(s,1H), 5.61(s,1H),4.1(s,1H(N-H)),3.14(t,2H,J=7.1Hz),1.31~1.67(m,20H),0.88(t,3H,J= 7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.1,151.3,141.6,137.8,137.2,127.4,125.9, 124.2,116.3,114.3,111.4,40.4,31.9,30.2,29.3,26.7,22.7,14.1
Embodiment four: the preparation of fluorescent monomer IV
Fluorescent monomer IV
(1) synthesis of 4-bromo-N-n-octadecane base-1,8-naphthalimide:
N-butylamine and 4-bromo-1,8-naphthalic anhydride 5.54g (0.02mol) is replaced with octadecyl amine 5.925g (0.022mol) Reaction.By the operation of (1) in embodiment one, gained intermediate 4-bromo-N-n-octadecane base-1,8-naphthalimide 8.64g, productivity It is 82%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.41(d,1H,J=7.5Hz),8.34(s,1H),8.26(d,1H,J= 7.5Hz),7.98(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),3.14(t,2H,J=7.1Hz),1.31~1.69(m, 32H),0.88(t,3H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.5,151.7,140.9,136.1, 137.8,128.4,125.9,124.2,116.3,114.3,111.4,40.1,31.9,30.2,29.6,29.3,27.8,26.9, 26.7,25.5,22.7,14.1,13.9
(2) synthesis of fluorescent monomer IV:
4-bromo-N-normal-butyl-1,8-naphthoyl is replaced with 4-bromo-N-octadecyl-1,8-naphthalimide 4.176g (0.009mol) Imines.By the operation of (2) in embodiment one, finally obtain faint yellow solid IV 4.33g, productivity 85%.The core of fluorescent monomer IV Magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.40(d,1H ,J=7.5Hz),8.35(s,1H),8.21(d,1H ,J= 7.5Hz),7.98(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.61 (s,1H),5.18(s,1H),5.61(s,1H),4.1(s,1H(N-H)),3.14(t,2H,J=7.1Hz),1.30~1.68(m, 32H),0.85(t,3H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.1,151.3,141.6,137.8, 137.2,127.4,125.9,124.2,116.3,114.3,111.4,40.4,33.2,31.9,30.2,29.1,27.5,26.7, 22.7,13.9
Embodiment five: the preparation of fluorescent monomer V
Fluorescent monomer V
(1) synthesis of the bromo-N-of 4-different octyloxy propyl group-1,8-naphthalimide:
N-butylamine and 4-bromo-1,8-naphthalic anhydride 5.54g is replaced with different octyloxypropylamine 4.114g (0.022mol) (0.02mol) reaction.By the operation of (1) in embodiment one, the bromo-N-of gained intermediate 4-different octyloxy propyl group-1,8-naphthoyl is sub- Amine 7.49g, productivity is 84.2%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.41(d,1H,J=7.5Hz),8.34(s,1H),8.26(d,1H,J= 7.5Hz),7.98(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),4.12(t,2H,J=7.1Hz),3.46(m,2H), 3.37(m,2H),1.77~1.25(m,11H),0.9(t,6H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ= 159.1,151.9,140.9,136.1,137.8,128.4,125.9,124.2,116.3,114.3,111.4,40.1, 30.2, 29.6,29.1,27.8,26.9,26.1,25.5,23.0,14.1,11.9
(2) synthesis of fluorescent monomer V:
4-bromo-N-normal-butyl-1,8-is replaced with the bromo-N-of 4-different octyloxy propyl group-1,8-naphthalimide 3.438g (0.009mol) Naphthalimide.By the operation of (2) in embodiment one, finally obtain pale yellow solid V 3.78g, productivity 87%.Fluorescent monomer V's Nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.37(d,1H,J=7.5Hz),8.33(s,1H),8.21(d,1H,J= 7.5Hz),7.98(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.61 (s,1H),5.18(s,1H),5.60(s,1H(,3.21~4.12(m,7H),3.14(t,2H,J=7.1Hz),1.33~1.80(m, 11H),0.9(t,6H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.1,151.3,141.6,137.8, 137.2,127.4,125.9,124.2,116.3,114.3,111.4,66.2,40.7,39,2,30.9,29.6,27.5,27.1, 23.8,14.1,11.9
Embodiment six: the preparation of fluorescent monomer VI
Fluorescent monomer VI
(1) synthesis of the bromo-N-of 4-(9-heptadecyl)-1,8-naphthalimide:
Replace n-butylamine anti-with 4-bromo-1,8-naphthalic anhydride 5.54g (0.02mol) with 9-heptadecyl-amine 5.61g (0.022mol) Should.By the operation of (1) in embodiment one, the bromo-N-of gained intermediate 4-(9-heptadecyl)-1,8-naphthalimide 8.34g, productivity It is 81.3%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.32(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),3.58(m,1H),1.29~1.55(m,28H),0.88 (t,6H).13C-NMR(125MHz,CDCl3,ppm)δ=159.0,153.9,142.9,136.1,136.8,128.4,125.6, 124.2,116.3,114.3,111.4,40.1,31.3,30.2,29.6,29.1,27.8,26.9,26.1,25.5,23.0, 15.2,14.0,11.7
(2) synthesis of fluorescent monomer VI:
4-bromo-N-normal-butyl-1,8-naphthalene is replaced with the bromo-N-of 4-(9-heptadecyl)-1,8-naphthalimide 4.05g (0.009mol) Acid imide.By the operation of (2) in embodiment one, finally obtain field gray solid VI 3.979g, productivity 80.1%.Fluorescent monomer VI Nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.37(d,1H,J=7.5Hz),8.33(s,1H),8.21(d,1H,J= 7.5Hz),7.96(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.61 (s,1H),5.18(s,1H),5.60(s,1H),4.0(s,1H(N-H)),3.58(m,1H),1.31~1.55(m,28H),0.88 (t,6H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.1,151.3,141.6,137.8,137.2,127.4, 125.9,124.2,116.3,114.3,111.4,66.2,53.4,32.5,2,31.9,29.3,22.7,14.1,13.9
Embodiment seven: the preparation of fluorescent monomer VII
Fluorescent monomer VII
(1) synthesis of 4-bromo-N-P-TOLUENE SULFO ACID 99 sodium-1,8-naphthalimide:
N-butylamine and 4-bromo-1,8-naphthalic anhydride 5.54g is replaced with sodium sulfanilate 4.264g (0.022mol) (0.02mol) reaction.By the operation of (1) in embodiment one, obtain intermediate 4-bromo-N-P-TOLUENE SULFO ACID 99 sodium-1,8-naphthalimide 7.86g, productivity is 87%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.32(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),7.56(d,4H(Phen-H),J=7.5Hz).13C- NMR(125MHz,CDCl3,ppm)δ=159.3,154.9,142.9,136.1,136.8,132.6,129.8,128.4,125.6, 124.2,116.3,114.3,111.4
(2) synthesis of fluorescent monomer VII:
With 4-bromo-N-benzene sulfonic acid sodium salt-1,8-naphthalimide 3.51g(0.009mol) replace 4-bromo-N-normal-butyl-1,8-naphthoyl sub- Amine.By the operation of (2) in embodiment one, finally obtain faint yellow solid VII 3.80g, productivity 86%.The core of fluorescent monomer VII Magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.38(d,1H,J=7.5Hz),8.35(d,1H),8.24(d,1H,J= 7.5Hz),8.09(d,2H,J=7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),7.55(d,4H (Phen-H),J=7.5Hz),7.42(d,2H,J=7.5Hz),6.63(s,1H),5.18(s,1H),5.61(s,1H),4.1(s, 1H(N-H)).13C-NMR(125MHz,CDCl3,ppm)δ=158.6,151.6,145.4,141.6,137.2,127.4,125.9, 124.2,121.7,116.3,114.3,111.4
Embodiment eight: the preparation of fluorescent monomer VIII
Fluorescent monomer VIII
(1) synthesis of the bromo-N-of 4-(4-oxinane)-1,8-naphthalimide:
N-butylamine and 4-bromo-1,8-naphthalic anhydride 5.54g is replaced with 4-amino tetrahydro pyran 2.18g (0.022mol) (0.02mol) reaction.By the operation of (1) in embodiment three, obtain the bromo-N-of intermediate 4-(4-oxinane)-1,8-naphthalimide 6.85g, productivity is 86%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.32(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),3.70(m,1H),3.65~1.74(m,8H).13C- NMR(125MHz,CDCl3,ppm)δ=159.3,154.9,142.9,136.1,136.8,132.6,129.8,128.4,125.6, 124.2,116.3,114.3,111.4
(2) synthesis of fluorescent monomer VIII:
With 4-bromo-N-amino tetrahydro pyran-1,8-naphthalimide 2.664g(0.009mol) replace 4-bromo-N-normal-butyl-1,8- Naphthalimide.By the operation of (2) in embodiment one, finally obtain faint yellow solid VIII 3.03g, productivity 84.5%.Fluorescence list The nucleus magnetic hydrogen spectrum of body VIII, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.38(d,1H,J=7.5Hz),8.35(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.63 (s,1H),5.18(s1H),5.61(s,1H),4.1(s,1H(N-H)),3.70(m,1H),3.65~1.74(m,8H).13C-NMR (125MHz,CDCl3,ppm)δ=158.6,151.6,145.4,141.6,137.2,127.4,125.9,124.2,121.7, 116.3,114.3,111.4,65.2,48.0,34.1
Embodiment nine: the preparation of fluorescent monomer IX
Fluorescent monomer IX
(1) synthesis of the bromo-N-of 4-(2-N, N-diethylamino ethyl)-1,8-naphthalimide:
N-butylamine and 4-bromo-1,8-naphthalic anhydride 5.54g is replaced with 2-N, N-diethyl ethylenediamine 2.5g (0.022mol) (0.02mol) reaction.By the operation of (1) in embodiment one, obtain the bromo-N-of intermediate 4-(2-N, N-diethylamino ethyl)-1, 8-naphthalimide 7.02g, productivity is 85%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.32(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),3.29(t,2H,J=7.1Hz),2.57(t,2H), 1.02~2.46(t,8H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.3,154.9,142.9,136.1, 136.8,132.6,129.8,128.4,125.6,124.2,116.3,114.3,111.450.2,49.6,38.4,13.3
(2) synthesis of fluorescent monomer IX:
The bromo-N-of 4-is replaced with the bromo-N-of 4-(2-N, N-diethylamino ethyl)-1,8-naphthalimide 2.799g (0.009mol) Normal-butyl-1,8-naphthalimide.By the operation of (2) in embodiment one, finally obtain faint yellow solid IX 3.345g, productivity 90.1%.The nucleus magnetic hydrogen spectrum of fluorescent monomer IX, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.38(d,1H,J=7.5Hz),8.35(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.63 (s,1H),5.18(s,1H),5.61(s,1H),4.1(s,1H(N-H)),3.29(t,2H,J=7.1Hz),2.57(t,2H,J= 7.1Hz),1.02~2.46(t,8H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.3,151.6,145.4, 141.6,137.2,127.4,125.9,124.2,121.7,116.3,114.3,111.4,50.2,49.6,38.4,13.3
Embodiment ten: the preparation of fluorescent monomer X
Fluorescent monomer X
(1) synthesis of the bromo-N-of 4-(2-N, N-Dibutylaminoethyl)-1,8-naphthalimide:
N-butylamine and 4-bromo-1,8-naphthalic anhydride is replaced with 2-N, N-dibutylamino ethamine 3.74g (0.022mol) 5.54g (0.02mol) reacts.By the operation of (1) in embodiment one, obtain the bromo-N-of intermediate 4-(2-N, N-dibutylamino second Base)-1,8-naphthalimide 7.01g, productivity is 81.5%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.32(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),3.29(t,2H,J=7.1Hz),2.57(t,2H), 1.02~2.46(t,12H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.1,154.8,142.9,136.1, 136.8,132.6,129.8,128.4,125.6,124.2,116.3,114.3,111.450.2,56.6,50.2,39.0, 30.5,20.4,13.8
(2) synthesis of fluorescent monomer X:
With the bromo-N-of 4-(2-N, N-Dibutylaminoethyl)-1,8-naphthalimide 3.30g(0.009mol) just replacing the bromo-N-of 4- Butyl-1,8-naphthalimide.By the operation of (2) in embodiment one, finally obtain faint yellow solid X 3.67g, productivity 87%.Glimmering The nucleus magnetic hydrogen spectrum of light monomer X, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.38(,1HJ=7.5Hz),8.35(s,1H),8.24(d,1HJ=7.5Hz), 7.97(t,1H,J=7.5Hz),7.78(d,1HJ=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.63(s,1H), 5.18(s,1H),5.61(s,1H),4.1(s,1H(N-H)),3.29(t,2H,J=7.1Hz),3.01(t,4H,J=7.1Hz), 2.57(t,2H,J=7.1Hz),1.31~1.36(t,8H,J=7.1Hz),0.9(t,4H,J=7.1Hz).13C-NMR(125MHz, CDCl3,ppm)δ=159.3,151.6,145.4,141.6,137.2,127.4,125.9,124.2,121.7,116.3, 114.3,111.4,56.6,50.2,39.0,30.5,20.4,13.8
Embodiment 11: the preparation of fluorescent monomer XI
Fluorescent monomer XI
(1) synthesis of 4-bromo-N-chloroethyl-1,8-naphthalimide:
Replace n-butylamine anti-with 4-bromo-1,8-naphthalic anhydride 5.54g (0.02mol) with chlorethamin 1.694g (0.022mol) Should.By the operation of (1) in embodiment one, obtaining intermediate 4-bromo-N-chloroethyl-1,8-naphthalimide 5.59g, productivity is 83%.In Mesosome nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.32(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),3.19(t,2H,J=7.1Hz),2.26(t,2H,J= 7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.1,154.8,142.9,136.1,136.8,132.6,129.8, 128.4,125.6,124.2,116.3,114.3,111.450.2,56.6,50.2, 13.8
(2) synthesis of fluorescent monomer XI:
With 4-bromo-N-chloroethyl-1,8-naphthalimide 2.466g(0.009mol) replace 4-bromo-N-normal-butyl-1,8-naphthoyl sub- Amine.By the operation of (2) in embodiment one, finally obtain yellow solid XI 2.876g, productivity 85%.The nuclear-magnetism hydrogen of fluorescent monomer XI Spectrum, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.40(d,1H,J=7.5Hz),8.37(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.76(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.63 (s,1H),5.18(s1H),5.61(s,1H),4.1(s,1H(N-H)),3.68(t,2H,J=7.1Hz),3.48(t,2H,J= 7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.3,151.6,145.4,141.6,137.2,127.4,125.9, 124.2,121.7,116.3,114.3,111.4,49.5,41.5
Embodiment 12: the preparation of fluorescent monomer XII
Fluorescent monomer XII
(1) synthesis of the bromo-N-of 4-[4-(2,2,6,6-tetramethyl-tetrahydropyridine) base]-1,8-naphthalimide:
N-butylamine and 4-bromo-1,8-naphthalene two is replaced with 2,2,6,6-tetramethyl-4-amino tetrahydropyridine 3.388g (0.022mol) Formic anhydride 5.54g (0.02mol) reacts.By the operation of (1) in embodiment one, obtain the bromo-N-of intermediate 4-[4-(2,2,6,6-tetra- Methyl-tetrahydro pyridine) base]-1,8-naphthalimide 7.61g, productivity is 84%.Intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data are such as Under:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.32(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),3.60(m,1H),3.2(s,1H(N-H),1.80(t, 4H,J=7.5Hz),1.36(s,12H)..13C-NMR(125MHz,CDCl3,ppm)δ=159.1,154.8,142.9,136.1, 136.8,132.6,129.8,128.4,125.6,124.2,116.3,114.3,111.4, 63.3,53.8,44.6,39.0, 33.6,29,25.1
(2) synthesis of fluorescent monomer XII:
With the bromo-N-of 4-[4-(2,2,6,6-tetramethyl-tetrahydropyridine) base]-1,8-naphthalimide 3.159g(0.009mol) generation For 4-bromo-N-normal-butyl-1,8-naphthalimide.By the operation of (2) in embodiment one, finally obtain yellow solid XII3.445 G, productivity 84.5%.The nucleus magnetic hydrogen spectrum of fluorescent monomer XII, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.40(d,1H,J=7.5Hz),8.37(s,1H),8.24(d,1H ,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.76(d,1H,J=7.5Hz),7.55(d,4H(Phen-H),J=7.5Hz),6.63 (s,1H),5.18(s,1H),5.61(s,1H),4.1(s,1H(N-H)),3.60(m,1H),3.2(s,1H(N-H),1.80(t, 4H,J=7.1Hz),1.36(s,12H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.0,151.6,145.4, 141.6,137.2,127.4,125.9,124.2,121.7,116.3,114.3,111.4,63.3,53.8,44.6,39.0, 33.6,29,25.1
Embodiment 13: the preparation of fluorescent monomer XIII
Fluorescent monomer XIII
(1) synthesis of the bromo-N-of 4-(2-morpholine ethyl)-1,8-naphthalimide:
N-butylamine and 4-bromo-1,8-naphthalic anhydride 5.54g is replaced with 2-morpholine ethylenediamine 2.816g (0.022mol) (0.02mol) reaction.The bromo-N-of intermediate 4-(2-morpholine ethyl)-1,8-naphthalimide 6.67g, productivity is 86%.By embodiment The operation of (1) in one, obtains intermediate nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon modal data as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.39(d,1H,J=7.5Hz),8.32(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.78(d,1H,J=7.5Hz),3.29(t,2H,J=7.1Hz),3.65(t,4H,J= 7.1Hz),2.57(t,2H,J=7.1Hz),2.36(t,4H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.1, 154.8,142.9,136.1,136.8,132.6,129.8,128.4,125.6,124.2,116.3,114.3,111.4,63.3, 55.8,50.2, 39.0,38.7,27.0,23.1
(2) synthesis of glimmering photo polymerization monomer XIII:
With the bromo-N-of 4-(2-morpholine ethyl)-1,8-naphthalimide 2.925g(0.009mol) replace 4-bromo-N-normal-butyl-1,8- Naphthalimide.By the operation of (2) in embodiment one, finally obtain faint yellow solid XIII 3.132 g, productivity 81.5%.Fluorescence The polymerization nucleus magnetic hydrogen spectrum of monomer XIII, nuclear-magnetism carbon modal data are as follows:
1H-NMR(500MHz,CDCl3,ppm)δ=8.40(d,1H,J=7.5Hz),8.37(s,1H),8.24(d,1H,J= 7.5Hz),7.97(t,1H,J=7.5Hz),7.76(d,1H,J=7.5Hz),7.56(d,4H(Phen-H),J=7.5Hz),6.63 (s,1H),5.18(s,1H),5.61(s,1H),4.1(s,1H(N-H)),3.29(t,2H,J=7.1Hz),3.65(t,4H,J= 7.1Hz),2.57(t,2H,J=7.1Hz),2.36(t,4H,J=7.1Hz).13C-NMR(125MHz,CDCl3,ppm)δ=159.3, 152.6,145.4,141.6,137.2,127.4,125.9,124.2,121.7,116.3,114.3,111.4,55.8,50.2, 39.0,38.7,27.0,23.1
Analyzing from performance test, naphthalimide analog derivative has certain photoelectric properties, sees Fig. 1-3.

Claims (2)

1. a polymerisable water or the controlled fluorescent monomer of oil-soluble, it is characterised in that the structural formula of this monomer is:
Wherein R is C4～C18Direct-connected or branched alkyl, different octyloxy propyl group, P-TOLUENE SULFO ACID 99's base ,-THP trtrahydropyranyl ,-N, N-bis- Ethylaminoethyl ,-N, N-Dibutylaminoethyl, chloroethyl ,-(2,2,6,6-tetramethyl-tetrahydropyridine) base ,-morpholine second Base.
2. preparing polymerisable water according to claim 1 or a method for the controlled fluorescent monomer of oil-soluble, it is special Levy and be concretely comprising the following steps of the method:
A. bromo-for 4-1,8-naphthalic anhydride and primary amine compound are dissolved in absolute ethyl alcohol or ice by the mol ratio of 1:1 ~ 1:1.4 In acetic acid, back flow reaction to reaction completely, after reaction terminates, filters while hot, and filtrate, under 4 DEG C of states, separates out crude product crystal, Suction filtration, is washed with deionized and is vacuum dried, and the separated purifying of crude product obtains naphthalimide intermediate, and its structural formula is:, the structural formula of described primary amine compound is: RNH2；
B. under inert gas shielding, by step a gained intermediate naphthalimide and 4-aminostyryl rubbing by 1:1 ~ 1:1.3 Your ratio dissolves in glycol monoethyl ether or DMF, adds Anhydrous potassium carbonate, and its addition is 4-aminobenzene The 18% ~ 30% of ethene charged material weight, back flow reaction to reaction completely, after reaction terminates, is cooled to room temperature, is poured into by reactant liquor In ionized water, regulation pH value of solution to 6 ~ 8, suction filtration, be washed with deionized, filter cake be vacuum dried, crude product is separated to be purified Polymerisable water or the controlled fluorescent monomer of oil-soluble.
CN201610277836.5A 2016-05-01 2016-05-01 Water or oil soluble controllable fluorescent monomer for copolymerization and preparation method thereof Pending CN105837505A (en)

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CN107793401A (en) * 2017-11-11 2018-03-13 福建医科大学 Ag in one kind identification K562+Naphthoyl imide compounds fluorescence probe and preparation method thereof
CN109324025A (en) * 2018-09-30 2019-02-12 毅康科技有限公司 A kind of monitoring method of circulation sewerage disposing chemical content
CN109324025B (en) * 2018-09-30 2021-07-27 毅康科技有限公司 Method for monitoring water treatment agent content in circulating water system
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CN110283270A (en) * 2019-06-28 2019-09-27 北京科技大学 A kind of preparation of the fluorescent polymer containing naphthalimide and rhodamine and application method

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