CN100349869C - Cyanine dye containing end alkynyl radical and its synthesis process - Google Patents
Cyanine dye containing end alkynyl radical and its synthesis process Download PDFInfo
- Publication number
- CN100349869C CN100349869C CNB2004100893563A CN200410089356A CN100349869C CN 100349869 C CN100349869 C CN 100349869C CN B2004100893563 A CNB2004100893563 A CN B2004100893563A CN 200410089356 A CN200410089356 A CN 200410089356A CN 100349869 C CN100349869 C CN 100349869C
- Authority
- CN
- China
- Prior art keywords
- compound
- cyanine dyes
- sulfonic acid
- formula
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Indole Compounds (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
The present invention discloses cyanine dye containing end alkynyl radicals and a synthesis process thereof. The present invention introduces end alkynyl radicals into an aromatic rings. In this way, obtained cyanine dye can be directly used as dye with an active radical group for application to a bioluminescence mark, and can also be used as a useful intermediate body for satisfying different needs. The structure of the cyanine dye is shown in the following formula I or II: Ar1 and Ar2 are the aromatic rings; X1 and X2 are selected from one of O, S, Se, * and CH=CH; Y<-> is Cl<->, Br<->, I<->, ClO4<->, PF6<->, p-CH3C6H4SO3<->, or R1OSO3<->; n is from 0 to 5; R1 and R2 are selected from one of substituents represented by-(CH2)mCH2L, wherein m is from 0 to 30; L is hydrogen, a sulfonic acid radical, a hydroxyl radical, a halogen, an alkoxyl radical, or an alkyl radical with the aromatic rings; R3 is zero, a carboxyl radical, the sulfonic acid radical, the halogen, or a saturated or unsaturated alkyl radical of C1 to C20; R4 is the hydrogen, the alkoxyl radical, an amino radical, or a substitute amino radical.
Description
Technical field
The present invention relates to a kind of cyanine dyes and synthetic method thereof, specifically, relate to the cyanine dyes and the synthetic method thereof that have the Terminal Acetylenes base on a kind of aromatic ring.
Background technology
Cyanine dyes at first was synthesized by Greville Williams in 1856, was used as textile dyestuff at first, but cyanine dyes is not widely used in dope dyeing to the less stable of light and soda acid.1875, Vogel found that cyanine dyes has special light sensitive characteristic, thereby begins to be used for sensitive materials.In the process in more than 100 year after this, the most important purposes of cyanine dyes is as the spectral sensitizer in the silver halide photographic emulsions, is used to enlarge the sensitive volume of silver halide grains and improves light sensitivity.
Cyanine dyes has that molar extinction coefficient is very high (can to reach 10
5M
-1Cm
-1), stability compares better, the reflectivity height, solvability is good, thermal conductivity is little, can spin-coating, easily form state of aggregation, maximum absorption wavelength can be in whole visible spectrum range characteristics such as tuning range is big.In nearest nearly decades, cyanine dyes also has increasing function and purposes except as textile dyestuff and the sensitive materials in other field.Cyanine dyes has been widely used in aspects such as bioluminescence check and analysis, electrofax material, optical nonlinearity material, infrared laser dye, optical disc recording medium and organic solar battery material now, and wide development and application prospect are arranged.
The general general structure of polymethin cyanine dyestuff is as follows:
This shows that cyanine dyes is the conjugated system that is formed by carbochain two nitrogen-atoms of connection, one of them nitrogen-atoms has positive charge.Normal with various end groups that contain the heterocycle of nitrogen-atoms as conjugated chain such as pyridine, quinoline, indoles, thiazole, pyrroles in cyanine dyes, the big π that has formed the cyanine dyes molecule with the methine chain advises system altogether, determined the scope of the main absorption band of dyestuff, the system of gripping altogether is big more, and the maximum absorption wavelength of dye molecule is long more.In general, 2 methynes of every increase can make the maximum absorption wavelength red shift 100nm of dye molecule on the conjugated chain, but the methine chain is long more, and the stability of dyestuff is poor more.Heterocycle in the cyanine dyes has certain influence to the absorbing wavelength and the stability of dyestuff.In addition, substituting group in the cyanine dyes and negatively charged ion also have very big influence to the performances such as solvability of dyestuff.
In actual application, need carry out different modifications to cyanine dyes according to the difference of Application Areas, introduce various active groups.For example, as the sensitizing agent of dye sensitization nano titania porous-film solar cell, need in cyanine dyes, introduce the group that carboxyl or sulfonic group etc. can be adsorbed on titanium dioxide surface; As the biological test material, need in cyanine dyes, introduce the group that succimide or maleimide etc. can react with sulfydryl in the organism or amino etc.
Because cyanine dyes structure special and to the unstable of alkali makes and introduces relatively difficulty of active group that in cyanine dyes the scope of introducing active group also has been subjected to certain restriction.The multiterminal alkynyl then is a kind of more active group, can a lot of reactions take place with other functional group under the comparatively gentle situation of condition, thereby introduces the range of application that terminal alkynyl can effectively be widened cyanine dyes in cyanine dyes.The cyanine dyes that has terminal alkynyl on the aromatic nucleus not only can directly be applied in the biological fluorescent labelling as a kind of dyestuff that has active group, can also introduce various active groups as a kind of very useful as intermediates, to satisfy different needs.
Summary of the invention
One of the object of the invention is, discloses the cyanine dyes that has the Terminal Acetylenes base on a kind of aromatic ring;
Two of the object of the invention is, the synthetic method of above-mentioned cyanine dyes is provided.
Have the cyanine dyes of Terminal Acetylenes base on the said aromatic ring of the present invention, its general structure is as follows:
In the formula: Ar
1, Ar
2Be aromatic nucleus; X
1, X
2Be selected from O, S, Se,
With a kind of among the CH=CH; Y
-Be Cl
-, Br
-, I
-, ClO
4 -, PF
6 -, p-CH
3C
6H
4-SO
3 -Or R
1OSO
3 -N is 0～5; R
1, R
2Be selected from: by-(CH
2)
mCH
2A kind of in the represented substituting group of L, wherein: m is 0～30, and L is hydrogen, sulfonic group, carboxyl, hydroxyl, halogen, alkoxyl group or the alkyl that contains aromatic ring; R
3Be nothing, carboxyl, sulfonic group, halogen or C
1～C
20Saturated or unsaturated alkyl; R
4Be hydrogen, alkoxyl group, amino or substituted-amino.
For the represented compound of formula (I): preferred Ar
1, Ar
2Be the aromatic nucleus of forming by six carbon at least, more preferably phenyl ring or naphthalene nucleus; Preferred X
1And X
2For O, S or
Preferred n is 1,2 or 3; Preferred Y
-Be I
-, ClO
4 -, PF
6 -, p-CH
3C
6H
4-SO
3 -Or R
1OSO
3 -, preferred Y
-Be I
-, ClO
4 -, PF
6 -Preferred R
1And R
2Be respectively C
1～C
20Alkyl, propyloic, cyanoethyl, sulfonic acid ethyl, sulfonic acid propyl group or sulfonic acid butyl, preferred R
1And R
2Be respectively methyl, ethyl, butyl, sulfonic acid ethyl, sulfonic acid propyl group or sulfonic acid butyl; Preferred R
3Be nothing, carboxyl, sulfonic group, chlorine, bromine or C
1～C
6Alkyl, preferred R
3Be nothing, carboxyl, sulfonic group, chlorine, bromine, methyl or ethynyl.
For the represented compound of formula (II): preferred Ar
1Be the aromatic nucleus of forming by six carbon at least, more preferably phenyl ring or naphthalene nucleus; Preferred X
1For O, S or
Preferred n is 1,2 or 3, and preferred n is 1 or 2; Preferred Y
-Be I
-, ClO
4 -, PF
6 -, p-CH
3C
6H
4-SO
3 -Or R
1OSO
3 -, preferred Y
-Be I
-, ClO
4 -, PF
6 -Preferred R
1Be C
1～C
20Alkyl, propyloic, cyanoethyl, sulfonic acid ethyl, sulfonic acid propyl group or sulfonic acid butyl, preferred R
1Be methyl, ethyl, butyl, sulfonic acid ethyl, sulfonic acid propyl group or sulfonic acid butyl; Preferred R
4Be hydrogen, C
1～C
20Alkoxyl group or by-(CH
2)
KCOOH ,-(CH
2)
KCN, C
1～C
6The amino that alkyl or phenyl replaces, wherein K=1～6; Preferred R
4Be methoxyl group, oxyethyl group, dimethylamino, diethylin, dibutylamino, N-methyl-N-ethylamino, dicarboxyl ethylamino, dicyanoethyl amino or diphenyl amino.
Can adopt a kind of among following method A, B or the C for the cyanine dyes shown in the formula (I) synthetic:
Method A:
Method B:
Method C:
The key step of method A, B or C is, compound III (or VI) and compound IV (V or VII) are mixed according to mol ratio at 1: 1, add aceticanhydride as solvent, reaction mixture 0～150 ℃ the reaction 5 minutes to 72 hours after, pour in the water then, stirring is until separating out solid, after filtration, purifying is target compound.
The method D that can adopt for the represented cyanine dyes of formula (II) synthesizes:
Method D:
The key step of method D is compound III and compound VIII to be mixed at 1: 1 adding organic solvent stirring and dissolving according to mol ratio, add proper catalyst then, after 5 minutes to 72 hours, steaming desolventizes 0～150 ℃ of reaction, and residue is target compound through purification.
Wherein: used solvent is alcohol compound or aceticanhydride, and said alcohol compound includes, but is not limited to: methyl alcohol, ethanol, Virahol, propyl carbinol etc.; Catalyzer is Louis (lewis) alkali that contains N, and it includes, but is not limited to: triethylamine, diethylamine, piperidines etc., and the preferred solvent of institute is methyl alcohol or ethanol; Catalyzer is a piperidines.
Related Ar among reaction equation A, B, C, the D
1, Ar
2, X
1, X
2, Y
-, n, R
1, R
2, R
3And R
4All described identical with preamble.
To the represented cyanine dyes of formula (I), work as Ar
1And Ar
2Identical, R
1And R
2Identical, X
1And X
2Identical, R
3During for ethynyl, this cyanine dyes is the symmetrical cyanine dyes that the aromatic ring two ends all have alkynyl, its synthetic method any in can adopting method A, B or C, also can adopt method E:
Method E:
The key step of method E is, compound VI I and Compound I X were mixed in 2: 1 in molar ratio, adds the aceticanhydride stirring and dissolving,, pours in the water after 5 minutes to 72 hours 0～150 ℃ of reaction, stirs until separating out solid, after filtration, purifying promptly gets target compound.
To the represented cyanine dyes of formula (I), work as Ar
1And Ar
2Identical, R
1And R
2Identical, X
1And X
2Identical, R
3Be ethynyl, n is 1 o'clock, and this cyanine dyes is the three methine cyanine dyes that the aromatic ring two ends all have alkynyl, its synthetic method any in can adopting method A, B, C or E, also can adopt method F:
Method F:
The key step of method F is, compound VI I and triethyl orthoformate were mixed in 2: 1 in molar ratio, adds the pyridine stirring and dissolving, and reflux is poured in the water after 1 hour to 72 hours, stirs until separating out solid, after filtration, purifying promptly gets target compound.
In method A～F, compound IV can be synthesized with reference to CN1312249A institute reported method, compound V can be with reference to US5,929,227 or EP1209205 institute reported method synthesize, compound VI can be with reference to Soobshch Akad.Nauk.Gruz.SSR, 1968,50 (1), 77～82 reported method are synthetic, compound III adopts method as follows to synthesize, and other raw material all adopts the commercially available prod.
The synthetic route of compound III:
Wherein, X is chlorine, bromine or iodine, and L is trimethyl silicon based or 2-hydroxyl-2-propyl group.
The concrete steps of synthetic compound III are:
(1) with Compound I X and compounds X (trimethyl silicane ethyl-acetylene or 2-methyl-3-butyne-2-alcohol) 1～10: 1 mixing in molar ratio, add toluene, tetrahydrofuran (THF), N, dinethylformamide, triethylamine or the dissolving of Diisopropylamine stirring solvent, add triphenyl phosphorus chlorination handle, cuprous iodide and triethylamine as catalyzer after removing the oxygen in the reaction vessel, under protection of inert gas, in room temperature to 140 ℃ reaction after 10 minutes to 72 hours, steaming desolventizes, and residue obtains compounds X I through purification;
(2) compounds X I and yellow soda ash, salt of wormwood, sodium hydroxide or potassium hydroxide in molar ratio 0.1～10: 1 mixes, add organic solvents such as toluene, methyl alcohol, ethanol or Virahol, under protection of inert gas,, slough blocking group and obtain compounds X II room temperature to 110 ℃ reaction 10 minutes to 48 hours;
(3) with compounds X II and compound VIII 1～10: 1 mixing in molar ratio, add toluene, methyl alcohol, ethanol, Virahol or propyl carbinol equal solvent stirring and dissolving, back flow reaction obtains compound III after 30 minutes to 72 hours under protection of inert gas.
Embodiment
The present invention is further elaborated below by embodiment, and its purpose is better to understand content of the present invention.Therefore, the cited case should not be considered as limiting the scope of the invention.In addition, the compound that does not provide concrete synthetic method in an embodiment is that the synthetic method that provides by previously described existing document or supplier is synthetic.
Embodiment 1
Synthesizing of cyanine dyes [compound (I-1)]:
(1) 1,1,2-trimethylammonium-7-(3-methyl-3-hydroxyl-ethyl acetylene base)-1H-benzo [e] indoles (XI-1) synthetic:
In the single port flask of 250ml, add 6.5g 1; 1; 2-trimethylammonium-7-bromo-1H-benzo [e] indoles, 2.86ml2-methyl-3-butyne-2-alcohol, 100ml exsiccant triethylamine, 0.015g triphenyl phosphorus, 0.05g cuprous iodide and 0.07g two (triphenylphosphine) palladium chloride, stirring and refluxing 12h under argon shield.After reaction finished, the triethylamine that removes in the reaction system was steamed in rotation.The solid that obtains is dissolved in methylene dichloride, washes with water, use anhydrous magnesium sulfate drying, use methylene dichloride: ethyl acetate=10: 1 obtains 4.7g compounds X I-1, yield 72% for developping agent carries out column chromatography for separation.
(2) 1,1,2-trimethylammonium-7-ethynyl-1H-benzo [e] indoles (XII-1) synthetic:
3g compounds X I-1 is dissolved in the 50ml Virahol, adds 2.1g potassium hydroxide again, back flow reaction 6h under argon shield.After reaction finished, rotation was steamed and is removed Virahol, adds methylene dichloride, after washing with water, uses anhydrous magnesium sulfate drying, carries out column chromatography with methylene dichloride as eluent, obtains 1.6g compounds X II-1, yield 67%.
(3) 1,1,2,3-tetramethyl--7-ethynyl-1H-benzo [e] indoles salt compounded of iodine (III-1) synthetic:
1g compounds X II-1 and 10ml methyl iodide reflux 6h, after the cooling,,, obtain 1.2g compound III-1, yield 76% with the ether washing solid filtering.
(4) compound (I-1) is synthetic:
0.58g compound III-1,0.4g compound IV-1 and 10ml diacetyl oxide are added in the 25ml there-necked flask, at 100 ℃ of reacting by heating 1h.After the cooling, reaction mixture is under agitation poured in the water, the product of separating out is filtered, obtain 0.77g cyanine dyes I-1 with ethyl alcohol recrystallization, yield is 83%.
1H-NMR(DMSO-d
6)：8.5(t，1H)，8.23(m，3H)，8.08(d，2H)，8.03(d，2H)，7.76(m，2H)，7.62(m，2H)，7.46(t，1H)，6.53(d，1H)，6.48(d，1H)，4.29(s，1H)，4.25(d，2H)，3.7(s，3H)，1.95(d，12H)，1.34(t，3H)。
Embodiment 2
Synthesizing of cyanine dyes [compound (II-1)]
(1) 2,3,3-trimethylammonium-5-(trimethyl silicon based ethynyl)-3H-benzazolyl compounds (XI-2) synthetic:
With 2,2,3-trimethylammonium-5-bromo-3H-indoles and trimethyl silicane ethyl-acetylene react according to the method for embodiment 1, obtain compounds X I-2.
(2) 2,3,3-trimethylammonium-5-ethynyl-3H-indole compound (XII-2) synthetic:
2.5g compounds X I-2 is dissolved in the 30ml methyl alcohol, adds 0.7g salt of wormwood, at room temperature stir 2h, steaming desolventizes, add the 50ml methylene dichloride,, use anhydrous sodium sulfate drying with the sodium hydrogen carbonate solution washing, carry out column chromatography with methylene dichloride as eluent, obtain product 1.7g, yield 91%.
(4) 1-butyl-2,3,3-trimethylammonium-5-ethynyl-3H-indoles salt compounded of iodine (III-2) synthetic:
1.8g compounds X II-2,3.6g butyl iodide and 30ml acetonitrile reflux 20h, after the cooling, add ether sedimentation and go out solid, filter, with the ether washing, obtain 1.9g compound III-2, yield 53%.
(5) compound (II-1) is synthetic:
0.5g compound III-2 and 0.23g compound VIII-1 are dissolved in the 30ml ethanol reflux 2h.After reaction finished, the cooling standing over night was filtered the solid of separating out.Get 0.7g cyanine dyes II-1, yield 66% for several times with recrystallizing methanol.
1H-NMR(DMSO-d
6)：δ8.33(d，1H)，8.16(d，1H)，8.07(m，1H)，7.70(t，1H)，7.58(d，2H)，7.51(d，1H)，7.34(d，1H)；7.21(m，1H)，6.80(d，2H)，4.30(s，1H)，4.25(t，2H)，1.8(m，4H)，3.05(s，6H)，2.00(s，6H)，1.2(t，3H)。
Embodiment 3
Synthesizing of cyanine dyes [compound (I-2)]:
0.56g compound III-2 and 0.77g compound V-1 are joined in the 50ml flask, add the 10ml acetic anhydride, reflux 2h.The reaction postcooling is poured in the water, stirs 3h.Cross filter solid, get 0.42g cyanine dyes I-2, yield 62% for several times with recrystallizing methanol.
1H-NMR(DMSO-d
6)：8.5(t，1H)，8.34(d，1H)，8.27(d，1H)，8.2(d，1H)，8.15(m，2H)，8.1(d，1H)，7.8(d，1H)，7.62(m，2H)，6.75(t，1H)，6.5(m，2H)，4.25(t，2H)，4.2(t，2H)，2.6(d，2H)，2.1(s，6H)，1.9(s，6H)，1.8(m，4H)，1.45(m，2H)，0.9(d，3H)。
Embodiment 4
Synthesizing of cyanine dyes [compound (I-3)]
(1) 1,1,3-trimethylammonium-2-formyl radical methylene radical-7-ethynyl-1H-benzo [e] indoles (VI-1) synthetic:
From 1,1,3-trimethylammonium-2-carboxaldehyde radicals methylene radical-7-bromo-1H-benzo [e] indoles begins, according to embodiment 1 He
The method of embodiment 4 is reacted, and obtains compound VI-1.
(2) compound (I-3) is synthetic:
0.6g compound VI-1 and 0.34g compound VI I-1 are joined in the 50ml there-necked flask, add the 10ml acetic anhydride, reflux 2h.The reaction postcooling is poured in the water, stirs 3h.Cross filter solid, get 0.8g cyanine dyes I-3, yield 67.8% for several times with recrystallizing methanol.
1H-NMR(DMSO-d
6)：8.45(t，1H)，8.31(d，1H)，8.24(d，1H)，8.2(d，1H)，8.15(m，2H)，8.1(d，1H)，7.8(d，1H)，7.50(t，1H)，6.5(m，2H)，4.25(t，2H)，3.8(t，3H)，2.6(d，2H)，2.1(s，6H)，1.9(s，6H)，1.8(m，4H)。
Embodiment 5
Synthesizing of cyanine dyes [compound (I-4)]:
0.43g compound III-2 and 0.15g Compound I X are joined in the 50ml flask, add 10ml acetic anhydride, 5ml acetic acid and 0.2g sodium-acetate again, be heated to reaction 2h at 100 ℃.Reaction finishes postcooling, pours in the water, stirs 3h.Cross filter solid, get 0.2g cyanine dyes I-4, yield 53.0% for several times with recrystallizing methanol.
1H-NMR(DMSO-d
6)：8.33(d，2H)，8.16(d，2H)，8.03(s，2H)，7.62(m，2H)，7.46(t，1H)，6.70(t，1H)，6.43(d，2H)，6.48(d，2H)，4.29(s，2H)，4.25(t，4H)，1.95(s，12H)，1.8(m，8H)，1.2(t，6H)。
Embodiment 6
Synthesizing of cyanine dyes [compound (I-5)]:
1g compound III-1 and 0.2g Compound I-5 are dissolved in the 30ml pyridine reflux 6 hours.Reaction solution poured in the water stirred 3 hours, filter the solid of separating out, be dissolved in the ethanol of reflux, add the 3.2g sodium perchlorate, continue to reflux 1 hour, cooled and filtered obtains 1.3g cyanine dyes I-5, yield 77%.
1H-NMR(DMSO-d
6)：8.23(d，2H)，8.08(d，2H)，8.03(d，2H)，7.76(s，2H)，7.62(m，2H)，7.46(t，1H)，6.53(d，2H)，6.48(d，2H)，4.29(s，2H)，3.7(s，6H)，1.95(s，12H)。
Embodiment 7
Synthesizing of hemicyanine dye [compound (II-2)]:
In 30ml ethanol, add 1.2g compound III-1 and 0.84g compound VIII-2, reflux 2h.After reaction finished, standing over night was filtered the solid of separating out, and uses recrystallizing methanol, gets 1.5g cyanine dyes II-2, yield 75%.
1H-NMR(DMSO-d
6)：8.50(d，1H)，8.35(d，1H)，8.22(d，1H)，8.13(m，3H)，7.96(d，1H)，7.63(t，1H)，7.35(d，1H)，6.92(d，2H)，4.32(s，1H)，3.70(s，3H)，3.75(m，4H)；3.2(s，6H)，2.55(m，4H)。
Embodiment 8～12
According to the method for embodiment 1 to embodiment 7, can synthesize following compound:
Claims (12)
1, have the cyanine dyes of Terminal Acetylenes base on a kind of aromatic ring, its general structure is as follows:
In the formula: Ar
1, Ar
2Be aromatic nucleus; X
1, X
2Be selected from O, S, Se,
With a kind of among the CH=CH; Y
-Be Cl
-, Br
-, I
-, ClO
4 -, PF
6 -, p-CH
3C
6H
4-SO
3 -Or R
1OSO
3 -N is 0～5;
R
1, R
2Be selected from: by-(CH
2)
mCH
2A kind of in the represented substituting group of L, wherein: m is 0～30, and L is hydrogen, sulfonic group, carboxyl, hydroxyl or halogen;
R
3Be H, carboxyl, sulfonic group, halogen or C
1～C
20Alkyl or ethynyl;
R
4Be H, amino, or by-(CH
2)
KCOOH ,-(CH
2)
KCN, C
1～C
6The amino that alkyl or phenyl replaces, wherein K=1～6.
2, cyanine dyes as claimed in claim 1 is characterized in that, said cyanine dyes is the compound shown in the formula (I), wherein: Ar
1, Ar
2Be the aromatic nucleus of forming by six carbon at least; X
1And X
2For O, S or
N is 1,2 or 3; Y
-Be I
-, ClO
4 -, PF
6 -, p-CH
3C
6H
4-SO
3 -Or R
1OSO
3 -R
1And R
2Be respectively C
1～C
20Alkyl, propyloic, sulfonic acid ethyl, sulfonic acid propyl group or sulfonic acid butyl; R
3Be H, carboxyl, sulfonic group, chlorine, bromine or C
1～C
6Alkyl or ethynyl.
3, cyanine dyes as claimed in claim 2 is characterized in that, wherein Ar
1, Ar
2Be phenyl ring or naphthalene nucleus; Y-is I
-, ClO
4 -, PF
6 -R
1And R
2Be respectively methyl, ethyl, butyl, sulfonic acid ethyl, sulfonic acid propyl group or sulfonic acid butyl; R
3Be H, carboxyl, sulfonic group, chlorine, bromine, methyl or ethynyl.
4, cyanine dyes as claimed in claim 3 is characterized in that, said cyanine dyes is a compound shown in formula I-1, formula I-2, formula I-3, formula I-4 or the formula I-5
5, cyanine dyes as claimed in claim 1 is characterized in that, said cyanine dyes is the compound shown in the formula (II), wherein: Ar
1Be the aromatic nucleus of forming by six carbon at least; X
1For O, S or
N is 1,2 or 3; Y
-Be I
-, ClO
4 -, PF
6 -, p-CH
3C
6H
4-SO
3 -Or R
1OSO
3 -R
1Be C
1～C
20Alkyl, propyloic, sulfonic acid ethyl, sulfonic acid propyl group or sulfonic acid butyl; R
4Be H, or by-(CH
2)
KCOOH ,-(CH
2)
KCN, C
1～C
6The amino that alkyl or phenyl replaces, wherein K=1～6.
6, cyanine dyes as claimed in claim 5 is characterized in that, wherein Ar
1Be phenyl ring or naphthalene nucleus; N is 1 or 2; Y
-Be I
-, ClO
4 -, PF
6 -R
1Be methyl, ethyl, butyl, sulfonic acid ethyl, sulfonic acid propyl group or sulfonic acid butyl; R
4Be dimethylamino, diethylin, dibutylamino, N-methyl-N-ethylamino, dicarboxyl ethylamino, dicyanoethyl amino or diphenyl amino.
7, cyanine dyes as claimed in claim 6 is characterized in that, described cyanine dyes is a compound shown in formula II-1 or the formula II-2
8, synthetic shown in any described formula (I) in the claim 1～4 method of cyanine dyes, it is characterized in that described synthetic method adopts a kind of among following method A, B or the C:
Method A:
Method B:
Method C:
Its key step is: respectively compound (III) is mixed according to mol ratio with compound (VII) with compound (V) or compound (VI) with compound (IV) or compound (III) at 1: 1, add aceticanhydride as solvent, reaction mixture 0～150 ℃ the reaction 5 minutes to 72 hours after, pour in the water then, stirring is until separating out solid, after filtration, purifying is target compound.
9, synthetic as any described symmetry and R in the claim 1～4
3Method for the cyanine dyes of ethynyl, it is characterized in that, the key step of described synthetic method is: compound (VII) and Compound I X were mixed in 2: 1 in molar ratio, add the aceticanhydride stirring and dissolving,, pour in the water after 5 minutes to 72 hours 0～150 ℃ of reaction, stir until separating out solid, after filtration, purification promptly gets target compound
10, synthetic as any described symmetry in the claim 1～3, and R
3Method for the cyanine dyes of ethynyl, n=1, it is characterized in that, the key step of described synthetic method is: compound (VII) and triethyl orthoformate were mixed in 2: 1 in molar ratio, add the pyridine stirring and dissolving, after the reflux 1 hour to 72 hours, pour in the water, stir until separating out solid, after filtration, purification promptly gets target compound
The method of 11, synthesizing cyanine dyes shown in claim 1,5,6 or 7 described formulas (II), it is characterized in that, the key step of described synthetic method is: compound (III) and compound (VIII) are mixed according to mol ratio at 1: 1, add the organic solvent stirring and dissolving, add proper catalyst then, 0～150 ℃ of reaction 5 minutes to 72 hours, steaming desolventized, and residue is target compound through purification;
Wherein: used solvent is alcohol compound or aceticanhydride; Catalyzer is the Lewis base that contains N,
12, preparation method as claimed in claim 11 is characterized in that, wherein said solvent is methyl alcohol or ethanol; Catalyzer is a piperidines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100893563A CN100349869C (en) | 2004-12-10 | 2004-12-10 | Cyanine dye containing end alkynyl radical and its synthesis process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100893563A CN100349869C (en) | 2004-12-10 | 2004-12-10 | Cyanine dye containing end alkynyl radical and its synthesis process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1637077A CN1637077A (en) | 2005-07-13 |
| CN100349869C true CN100349869C (en) | 2007-11-21 |
Family
ID=34847572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100893563A Expired - Fee Related CN100349869C (en) | 2004-12-10 | 2004-12-10 | Cyanine dye containing end alkynyl radical and its synthesis process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100349869C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555246B (en) * | 2008-04-11 | 2012-05-30 | 大连理工大学 | Halogen-containing asymmetry phthalocyanines compound, preparation method and application thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723874B (en) | 2008-10-31 | 2013-09-11 | 深圳迈瑞生物医疗电子股份有限公司 | Cyanine compound and application thereof in dyeing biological samples |
| CN101750476B (en) | 2008-12-08 | 2015-06-03 | 深圳迈瑞生物医疗电子股份有限公司 | Blood analysis reagent and use method thereof |
| CN102115456B (en) | 2009-12-30 | 2014-08-20 | 深圳迈瑞生物医疗电子股份有限公司 | Cyanine compound, composition containing same and application in cell detection thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000075237A2 (en) * | 1999-06-09 | 2000-12-14 | Carnegie Mellon University | pH SENSITIVE CYANINE DYES AS REACTIVE FLUORESCENT REAGENTS |
| JP2001192579A (en) * | 2000-01-11 | 2001-07-17 | ▲らい▲とく▼科技股▲ふん▼有限公司 | Asymmetrical trimethine cyanine dye for high capacity optical recording medium |
| CN1312249A (en) * | 2001-03-07 | 2001-09-12 | 华东理工大学 | Preparation of asymmetric cyanine dyes for DVD-R CD |
| US6667087B2 (en) * | 2001-11-30 | 2003-12-23 | Cmc Magnetics Corporation | Optical information recording medium |
| EP1394219A1 (en) * | 1999-06-09 | 2004-03-03 | Carnegie-Mellon University | PH sensitive cyanine dyes as reactive fluorescent reagents |
-
2004
- 2004-12-10 CN CNB2004100893563A patent/CN100349869C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000075237A2 (en) * | 1999-06-09 | 2000-12-14 | Carnegie Mellon University | pH SENSITIVE CYANINE DYES AS REACTIVE FLUORESCENT REAGENTS |
| EP1394219A1 (en) * | 1999-06-09 | 2004-03-03 | Carnegie-Mellon University | PH sensitive cyanine dyes as reactive fluorescent reagents |
| JP2001192579A (en) * | 2000-01-11 | 2001-07-17 | ▲らい▲とく▼科技股▲ふん▼有限公司 | Asymmetrical trimethine cyanine dye for high capacity optical recording medium |
| CN1312249A (en) * | 2001-03-07 | 2001-09-12 | 华东理工大学 | Preparation of asymmetric cyanine dyes for DVD-R CD |
| US6667087B2 (en) * | 2001-11-30 | 2003-12-23 | Cmc Magnetics Corporation | Optical information recording medium |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555246B (en) * | 2008-04-11 | 2012-05-30 | 大连理工大学 | Halogen-containing asymmetry phthalocyanines compound, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1637077A (en) | 2005-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1239503C (en) | Liquid crystalline-3, 4:9, 10-perylenetetracarboxylic acid diimides | |
| CN1213998C (en) | Processes and intermediates useful to make antifolates | |
| CN1186795A (en) | Method for preparing aromatic compounds | |
| CN1153175A (en) | Photo-cross-linkable optically active compounds | |
| CN1789224A (en) | Preparation method of 2.3-difluoro-5-bromophenol | |
| CN100349869C (en) | Cyanine dye containing end alkynyl radical and its synthesis process | |
| JP2013173726A (en) | Coumarin derivative | |
| CN1049232C (en) | Fluorescent dye with double chromogens and preparing process thereof | |
| CN1827574A (en) | Chemical synthesis process for hypericin and derivatives thereof | |
| CN101029179A (en) | Solid-phase synthesis of asymmetric indocyanine dyes | |
| CN1259319C (en) | Dimer dye of sanjie-chuanjing in use for DVD-R atn high speed, and synthesis method | |
| CN1215025C (en) | spirans and the use thereof | |
| CN1410422A (en) | Benzfuran compound | |
| CN1869129A (en) | Cyanine dye containing coumarin | |
| CN1255404C (en) | Process for preparing substd. imidazopyridine compound | |
| CN1740171A (en) | Second order non-linear optical chromophore containing indolyl radical and its prepn and application | |
| CN1765900A (en) | Spiro oxazone derivative containing naphthalimide unit | |
| CN100335454C (en) | Dphenylacetylene derivative and its preparation method and uses | |
| CN1047862A (en) | The preparation method of N-(3-(((aryl) amino) alkylsulfonyl)-1H-1,2,4-triazole-5-yl) amine | |
| CN103427046A (en) | Organic semiconductor composition | |
| JP7297066B2 (en) | Fluorescent compound, its production method and its use | |
| RU2425047C9 (en) | Method of producing substituted 4-hydroxy-3-oxo-3,4-dihydro-2h-1,4-benzoxazine-6,7-dicarbonitriles based on 4-bromo-5-nitrophthalonitrile | |
| CN1465578A (en) | Indolinospirobenzoxazine compound, and synthesis method and use thereof | |
| CN1869021A (en) | Preparation method of tegaserod | |
| CN101735637B (en) | Cyanine dye having azulene structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071121 Termination date: 20121210 |