CN102492306A - Boron-dipyrromethene dye containing sulfur and halogen, and preparation method thereof - Google Patents
Boron-dipyrromethene dye containing sulfur and halogen, and preparation method thereof Download PDFInfo
- Publication number
- CN102492306A CN102492306A CN201110427596XA CN201110427596A CN102492306A CN 102492306 A CN102492306 A CN 102492306A CN 201110427596X A CN201110427596X A CN 201110427596XA CN 201110427596 A CN201110427596 A CN 201110427596A CN 102492306 A CN102492306 A CN 102492306A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- pyrroles
- reaction
- fluorine boron
- bearing
- 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.)
- Pending
Links
Abstract
The invention relates to a boron-dipyrromethene dye containing sulfur and halogen, and a preparation method thereof. The invention belongs to the field of organic chemical engineering and fine chemical engineering. The dye is characterized in that sulfur-containing boron-dipyrromethene is adopted as a raw material; NCS, NBS, and NIS are used for respectively carrying out a chlorination reaction, a bromination reaction, and an iodination reaction; under a temperature of -78 to 100 DEG C, a molar ratio of sulfur-containing boron-dipyrromethene to a halogenation reagent is 1:2-30, and a reaction is carried out for 1-100h; hydrogen in sulfur-containing boron-dipyrromethene is respectively substituted by chlorine, bromine and iodine, such that sulfur-containing boron-dipyrromethene dyes containing different halogens can be obtained with a good effect. According to the invention, the preparation method is simple, and a yield is high. Halogen is introduced into sulfur-containing boron-dipyrromethene, such that the optical property of the sulfur-containing boron-dipyrromethene can be regulated, and red shifts occur to the absorbed and emitted spectrum. The halogenated sulfur-containing boron-dipyrromethene can subject to various coupling reactions, such that a good platform is provided for the developments of boron-dipyrromethene derivatives in future.
Description
Technical field
The present invention relates to fluorine boron two pyrroles's dye well its preparation methods of one type of sulfur-bearing and halogen, this molecule comprises: sulfur-bearing chloro fluorine boron two pyrroles, sulfur-bearing bromo fluorine boron two pyrroles, sulfur-bearing iodo fluorine boron two pyrroles, it belongs to organic chemical industry and field of fine chemical.
Background technology
Fluorine boron two pyroles dyestuffs are one type of dye matrix commonly used, and its structural formula is following.
It is a compound very important in the organic dye; Because the π-pi-conjugated system in its molecular structure makes it have good fluorescence property and photoelectric properties, for example; High-fluorescence quantum yield; High molar extinction coefficient, preferable light stability or the like makes its verivate at bioprobe, solar cell, laser field bigger development arranged.This type dyestuff has especially become one of current research focus in the bioprobe field.At present existing be reported in fluorine boron two pyrroles and go up and introduce halogen and carry out linked reaction (J.Am.Chem.Soc.2011,133,8606-8616; The Journal of Organic Chemistry, 2011,76,8466-8471), but subject matter is halogenated fluorine boron two azole cpds complex manufacturing technology, yield is not high, synthetic relatively difficulty.The present invention is raw material (its preparation technology sees bibliographical information Tetrahedron 62 (2006) 5084-5091) with sulfur-bearing fluorine boron two pyrroles of easy acquisition, its respectively with NCS, NBS, NIS reaction, can the efficient production sulfur-bearing and fluorine boron two pyrroles of halogen.Fluorine boron two pyrroles's dyestuffs of sulfur-bearing and halogen do not appear in the newspapers at present; On sulfur-bearing fluorine boron two pyrroles, introduce halogen; Can regulate and control sulfur-bearing fluorine boron two pyrroles' light property; It is absorbed and emmission spectrum generation red shift, and halo sulfur-bearing fluorine boron two pyrroles can carry out multiple linked reaction, for fluorine boron two pyrrole derivative of developing excellent property from now on provide a platform preferably.
Summary of the invention
The present invention seeks on sulfur-bearing fluorine boron two pyrroles's dye matrix, to introduce different halogens; Can obtain to contain sulfur-bearing fluorine boron two pyrroles's dyestuffs of different halogens; The simple yield of this method preparation technology is high; Optimizing the manufacture craft of this compounds, thus the easier fluorine boron two pyrroles's dyestuffs that obtain sulfur-bearing and halogen.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: fluorine boron two pyrroles's dyestuffs of one type of sulfur-bearing and halogen, and fluorine boron two pyrroles's dyestuffs of its sulfur-bearing and halogen comprise a kind of in the following chemical molecular general structure; Specific as follows:
Wherein A is sulfur-bearing fluorine boron two pyrroles of containing 4 chlorine, and B is sulfur-bearing fluorine boron two pyrroles of containing 6 chlorine, and C is sulfur-bearing fluorine boron two pyrroles of containing 4 bromines, and D is sulfur-bearing fluorine boron two pyrroles of containing 6 bromines, and E is sulfur-bearing fluorine boron two pyrroles of containing 2 iodine.In formula A, B, C, D, E,
(1) R=C
1～C
20Straight or branched or naphthenic hydrocarbon
Or
(2)
n
2＝1～20
Or
(3)
n
3＝1～20
Or
(4)
n
4＝1～20
Or
(5)
n
5＝1～20
Or
(6)
n
6＝1～20
Or
(7)
n
7＝1～20
Or
(8)
n
8＝1～20
Or
(9)
n
9＝1～20
Or
(10)
m
10＝1～20?n
10＝1～20
Or
(11)
n
11＝1～20
Or
(12)
m
12＝1～20?n
12＝1～20
The preparation method of fluorine boron two pyrroles's dyestuffs of above-mentioned one type of sulfur-bearing and halogen is following:
(1) being raw material with sulfur-bearing fluorine boron two pyrroles, is halogenating agent with NCS, and their mol ratio is 1: 4～20; At organic solvent DMSO 99.8MIN., THF, toluene, 1; 4-dioxane, chloroform, N react in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone ,-78 ℃～50 ℃; React 1～50h, obtain containing sulfur-bearing fluorine boron two pyrroles of 4 chlorine through column chromatography separation method.
(2) being raw material with sulfur-bearing fluorine boron two pyrroles, is halogenating agent with NCS, and their mol ratio is 1: 21～30; At organic solvent DMSO 99.8MIN., THF, toluene, 1; 4-dioxane, chloroform, N react in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone, 51 ℃～100 ℃; React 51～100h, obtain containing sulfur-bearing fluorine boron two pyrroles of 6 chlorine through column chromatography separation method.
(3) being raw material with sulfur-bearing fluorine boron two pyrroles, is halogenating agent with NBS, and their mol ratio is 1: 4～20; At organic solvent DMSO 99.8MIN., THF, toluene, 1; 4-dioxane, chloroform, N react in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone ,-50 ℃～50 ℃; React 1～50h, obtain containing sulfur-bearing fluorine boron two pyrroles of 4 bromines through column chromatography separation method.
(4) being raw material with sulfur-bearing fluorine boron two pyrroles, is halogenating agent with NBS, and their mol ratio is 1: 21～30; At organic solvent DMSO 99.8MIN., THF, toluene, 1; 4-dioxane, chloroform, N react in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone, 51 ℃～100 ℃; React 51～90h, obtain containing sulfur-bearing fluorine boron two pyrroles of 6 bromines through column chromatography separation method.
(5) being raw material with sulfur-bearing fluorine boron two pyrroles, is halogenating agent with NIS, and their mol ratio is 1: 2～20; At organic solvent DMSO 99.8MIN., THF, toluene, 1; 4-dioxane, chloroform, N react in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone ,-50 ℃～85 ℃; React 1～75h, obtain containing sulfur-bearing fluorine boron two pyrroles of 2 iodine through column chromatography separation method.
Above-mentioned DMSO 99.8MIN., THF, toluene, 1,4-dioxane, chloroform, N, dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone of with an organic solvent being selected from.
The invention has the beneficial effects as follows: preparing simple sulfur-bearing fluorine boron two pyrroles with the yield high technology is raw material; Utilize NCS, NBS, NIS to carry out chloro, bromo and iodide reaction respectively; Can obtain fluorine boron two pyrroles's dyestuffs of sulfur-bearing and halogen easily, the simple yield of this method preparation technology is high, on sulfur-bearing fluorine boron two pyrroles, introduces halogen; Can regulate and control sulfur-bearing fluorine boron two pyrroles' light property; It is absorbed and emmission spectrum generation red shift, and halo sulfur-bearing fluorine boron two pyrroles can carry out multiple linked reaction, for fluorine boron two pyrrole derivative of developing excellent property from now on provide a platform preferably.
Embodiment
Embodiment 1
Under 0 ℃, 0.252g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml THF, add 0.798g NCS, reaction 35h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 72%.
Embodiment 2
Under 55 ℃, 0.252g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml DMSO 99.8MIN., add 3.32g NCS, reaction 65h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 78%.
Embodiment 3
Under 0 ℃, 0.252g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml chloroform, add 1.78gNBS, reaction 45h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 78%.
Embodiment 4
Under 60 ℃, 0.252g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml THF, add 4.6g NBS, reaction 65h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 88%.
Embodiment 5
Under-25 ℃, 0.252g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml ethanol, add 1.125g NIS, reaction 65h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 68%.
Embodiment 6
Under 40 ℃, 0.322g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml toluene, add 1.59g NCS, reaction 46h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains pink solid, yield: 75%.
Embodiment 7.
Under 70 ℃, 0.322g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml chlorobenzene, add 3.99g NCS, reaction 75h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 80%.
Embodiment 8
Under-20 ℃, 0.322g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml toluene, add 2.13g NBS, reaction 26h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 85%.
Embodiment 9.
Under 70 ℃, 0.322g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml N-Methyl pyrrolidone, add 4.62g NBS, reaction 75h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains pink solid, yield: 81%.
Embodiment 10
Under-30 ℃, 0.322g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml THF, add 1.8g NIS, reaction 56h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 75%.
Embodiment 11
Under-78 ℃, 0.32g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 2.3g NCS, reaction 45h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 72%.
Embodiment 12
Under 78 ℃, 0.32g sulfur-bearing fluorine boron two pyrroles are dissolved in the 40ml toluene, add 3.72gNCS, reaction 88h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 82%.
Embodiment 13
Under-48 ℃, 0.32g sulfur-bearing fluorine boron two pyrroles are dissolved in the 40ml ethanol, add 2.84g NBS, reaction 42h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains pink solid, yield: 62%.
Embodiment 14
Under 68 ℃, 0.32g sulfur-bearing fluorine boron two pyrroles are dissolved in the 40ml DMSO 99.8MIN., add 4.62gNBS, reaction 72h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains pink solid, yield: 72%.
Embodiment 15
Under 68 ℃, 0.32g sulfur-bearing fluorine boron two pyrroles are dissolved in the 40ml chlorobenzene, add 1.84g NIS, reaction 32h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 76%.
Embodiment 16
Under-30 ℃, 0.263g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 1.32g NCS, reaction 48h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains sorrel solid, yield: 66%.
Embodiment 17
Under 73 ℃, 0.263g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml N-Methyl pyrrolidone, add 3.72g NCS, reaction 70h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 74%.
Embodiment 18
Under-10 ℃, 0.263g sulfur-bearing fluorine boron two pyrroles are dissolved in the 25ml ethanol, add 2.16gNBS, reaction 38h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains pink solid, yield: 86%.
Embodiment 19
Under 62 ℃, 0.263g sulfur-bearing fluorine boron two pyrroles are dissolved in the 25mlN-SL 1332, add 4.9gNBS, reaction 78h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 79%.
Embodiment 20
Under-36 ℃, 0.263g sulfur-bearing fluorine boron two pyrroles are dissolved in 30mlN, in the dinethylformamide, add 2gNIS, reaction 48h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 76%.
Embodiment 21
Under-30 ℃, 0.264g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 1.08g NCS, reaction 40h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 70%.
Embodiment 22
Under 65 ℃, 0.264g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml chlorobenzene, add 3.8gNCS, reaction 73h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 75%.
Embodiment 23
Under-25 ℃, 0.264g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 2.1g NBS, reaction 30h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 72%.
Embodiment 24
Under 63 ℃, 0.264g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 4.8gNBS, reaction 63h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 80%.
Embodiment 25.
Under 30 ℃, 0.264g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml toluene, add 1.8gNIS, reaction 30h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 76%.
Embodiment 26
Under-50 ℃, 0.262g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml ethanol, add 1.59g NCS, reaction 46h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 67%.
Embodiment 27
Under 65 ℃, 0.262g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml chlorobenzene, add 3.7g NCS, reaction 76h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 74%.
Embodiment 28
Under 50 ℃, 0.262g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml ethanol, add 2.82g NBS, reaction 46h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 70%.
Embodiment 29
Under 75 ℃, 0.262g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml ethanol, add 4.32g NBS, reaction 86h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 76%.
Embodiment 30
Under-20 ℃, 0.262g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml THF, add 1.57g NIS, reaction 56h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 67%.
Embodiment 31
Under-54 ℃, 0.314g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 1.33g NCS, reaction 46h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 72%.
Embodiment 32
Under 54 ℃, 0.314g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 3.7g NCS, reaction 84h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 70%.
Embodiment 33
Under-50 ℃, 0.314g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 1.78g NBS, reaction 46h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 82%.
Embodiment 34
Under 74 ℃, 0.314g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml chlorobenzene, add 4.6g NBS, reaction 75h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 79%.
Embodiment 35
Under 34 ℃, 0.314g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 1.83gNIS, reaction 56h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 70%.
Embodiment 36
Under-65 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 1.33gNCS, reaction 45h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 77%.
Embodiment 37
Under 65 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 3.63g NCS, reaction 75h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 72%.
Embodiment 38
Under-45 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 32ml THF, add 2.33gNBS, reaction 45h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 67%.
Embodiment 39
Under 75 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml toluene, add 4.63g NBS, reaction 72h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 70%.
Embodiment 40
Under 5 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 1.8g NIS, reaction 45h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 70%.
Embodiment 41
Under-35 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 1.32gNCS, reaction 25h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 77%.
Embodiment 42
Under 75 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml chlorobenzene, add 3.75g NCS, reaction 75h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 78%.
Embodiment 43
Under-25 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 2.82gNBS, reaction 35h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 81%.
Embodiment 44
Under 75 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml chlorobenzene, add 4.6gNBS, reaction 70h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 71%.
Embodiment 45
Under-15 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 2gNIS, reaction 55h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 73%.
Embodiment 46
Under-70 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 40ml THF, add 1.32gNCS, reaction 40h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 67%.
Embodiment 47
Under 70 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml chlorobenzene, add 3.72g NCS, reaction 74h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 75%.
Embodiment 48.
Under-40 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 40ml THF, add 2.14gNBS, reaction 40h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains pink solid, yield: 70%.
Embodiment 49
Under 70 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 4.62g NBS, reaction 70h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 78%.
Embodiment 50
Under 70 ℃, 0.315g sulfur-bearing fluorine boron two pyrroles are dissolved in the 40ml chlorobenzene, add 2gNIS, reaction 40h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 70%.
Embodiment 51
Under 0 ℃, 0.281g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml THF, add 1gNCS, reaction 33h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 70%.
Embodiment 52
Under 85 ℃, 0.281g sulfur-bearing fluorine boron two pyrroles are dissolved in 20ml N, in the dinethylformamide, add 3.7g NCS, reaction 86h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 82%.
Embodiment 53
Under 25 ℃, 0.281g sulfur-bearing fluorine boron two pyrroles are dissolved in the 20ml chloroform, add 2.13g NBS, reaction 40h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 85%.
Embodiment 54
Under 85 ℃, 0.281g sulfur-bearing fluorine boron two pyrroles are dissolved in 20ml 1, in the 4-dioxane, add 4.5g NBS, reaction 83h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 70%.
Embodiment 55
Under 80 ℃, 0.281g sulfur-bearing fluorine boron two pyrroles are dissolved in 20ml 1, in the 4-dioxane, add 1.5gNIS, reaction 60h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 80%.
Embodiment 56
Under-34 ℃, 0.309g sulfur-bearing fluorine boron two pyrroles are dissolved in the 40ml THF, add 1.56g NCS, reaction 38h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 84%.
Embodiment 57
Under 64 ℃, 0.309g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 3.32g NCS, reaction 73h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 80%.
Embodiment 58
Under-14 ℃, 0.309g sulfur-bearing fluorine boron two pyrroles are dissolved in the 40ml ethanol, add 1.76g NBS, reaction 28h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 79%.
Embodiment 59
Under 74 ℃, 0.309g sulfur-bearing fluorine boron two pyrroles are dissolved in 40ml 1, in the 4-dioxane, add 3.98g NBS, reaction 78h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 74%.
Embodiment 60
Under 34 ℃, 0.309g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml chloroform, add 1.86g NIS, reaction 58h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 76%.
Embodiment 61
Under-50 ℃, 0.282g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml chloroform, add 1.55g NCS, reaction 36h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains pink solid, yield: 66%.
Embodiment 62
Under 65 ℃, 0.282g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 3.4g NCS, reaction 76h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 76%.
Embodiment 63
Under-28 ℃, 0.282g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 2.84g NBS, reaction 16h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 72%.
Embodiment 64
Under 70 ℃, 0.282g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml toluene, add 5gNBS, reaction 66h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 76%.
Embodiment 65
Under 0 ℃, 0.282g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml chloroform, add 1.75g NIS, reaction 46h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 72%.
Embodiment 66
Under 0 ℃, 0.31g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml ethanol, add 1.6gNCS, reaction 35h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 75%.
Embodiment 67
Under 70 ℃, 0.31g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml chlorobenzene, add 3.4g NCS, reaction 78h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 75%.
Embodiment 68
Under 0 ℃, 0.31g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml THF, add 2.13g NBS, reaction 48h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains orange solid, yield: 72%.
Embodiment 69
Under 75 ℃, 0.31g sulfur-bearing fluorine boron two pyrroles are dissolved in 30ml 1, in the 4-dioxane, add 4.6g NBS, reaction 88h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains dark red solid, yield: 71%.
Embodiment 70
Under 80 ℃, 0.31g sulfur-bearing fluorine boron two pyrroles are dissolved in the 30ml DMSO 99.8MIN., add 2.2gNIS, reaction 70h, reaction is revolved dried solvent after finishing, and the column chromatography chromatogram separation obtains red solid, yield: 78%.
Claims (7)
1. fluorine boron two pyrroles's dyestuffs of one type of sulfur-bearing and halogen, the fluorine boron two pyrroles's dyestuffs that it is characterized in that this sulfur-bearing and halogen comprise a kind of in the following chemical molecular general structure; Specific as follows:
In formula A, B, C, D, E,
(1) R=C
1～C
20Straight or branched or naphthenic hydrocarbon
Or
(2)
n
2＝1～20
Or
(3)
n
3＝1～20
Or
(4)
n
4＝1～20
Or
(5)
n
5＝1～20
Or
(6)
n
6＝1～20
Or
(7)
n
7＝1～20
Or
(8)
n
8＝1～20
Or
(9)
n
9＝1～20
Or
(10)
m
10＝1～20?n
10＝1～20
Or
(11)
n
11＝1～20
Or
(12)
m
12＝1～20?n
12＝1～20
2. the preparation method of fluorine boron two pyrroles's dyestuffs of described sulfur-bearing of claim 1 and halogen is characterized in that, is raw material with sulfur-bearing fluorine boron two pyrroles, is halogenating agent with NCS, and their mol ratio is 1: 4～20; At organic solvent DMSO 99.8MIN., THF, toluene, 1; 4-dioxane, chloroform, N; React in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone;-78 ℃～50 ℃, react 1～50h, obtain containing sulfur-bearing fluorine boron two pyrroles of 4 chlorine through column chromatography separation method.
3. the preparation method of fluorine boron two pyrroles's dyestuffs of described sulfur-bearing of claim 1 and halogen is characterized in that, is raw material with sulfur-bearing fluorine boron two pyrroles; With NCS is halogenating agent; Their mol ratio is 1: 21～30, at organic solvent DMSO 99.8MIN., THF, toluene, 1,4-dioxane, chloroform, N; React in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone; 51 ℃～100 ℃, react 51～100h, obtain containing sulfur-bearing fluorine boron two pyrroles of 6 chlorine through column chromatography separation method.
4. the preparation method of fluorine boron two pyrroles's dyestuffs of described sulfur-bearing of claim 1 and halogen is characterized in that, is raw material with sulfur-bearing fluorine boron two pyrroles; With NBS is halogenating agent; Their mol ratio is 1: 4～20, at organic solvent DMSO 99.8MIN., THF, toluene, 1,4-dioxane, chloroform, N; React in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone;-50 ℃～50 ℃, react 1～50h, obtain containing sulfur-bearing fluorine boron two pyrroles of 4 bromines through column chromatography separation method.
5. the preparation method of fluorine boron two pyrroles's dyestuffs of described sulfur-bearing of claim 1 and halogen is characterized in that, is raw material with sulfur-bearing fluorine boron two pyrroles; With NBS is halogenating agent; Their mol ratio is 1: 21～30, at organic solvent DMSO 99.8MIN., THF, toluene, 1,4-dioxane, chloroform, N; React in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone; 51 ℃～100 ℃, react 51～90h, obtain containing sulfur-bearing fluorine boron two pyrroles of 6 bromines through column chromatography separation method.
6. the preparation method of fluorine boron two pyrroles's dyestuffs of described sulfur-bearing of claim 1 and halogen is characterized in that, is raw material with sulfur-bearing fluorine boron two pyrroles; With NIS is halogenating agent; Their mol ratio is 1: 2～20, at organic solvent DMSO 99.8MIN., THF, toluene, 1,4-dioxane, chloroform, N; React in dinethylformamide, ethanol, chlorobenzene or the N-Methyl pyrrolidone;-50 ℃～85 ℃, react 1～75h, obtain containing sulfur-bearing fluorine boron two pyrroles of 2 iodine through column chromatography separation method.
7. according to the arbitrary described preparation method of claim 2-6; It is characterized in that: described organic solvent is selected from DMSO 99.8MIN., THF, toluene, 1; 4-dioxane, chloroform, N, dinethylformamide, ethanol, chlorobenzene or N-Methyl pyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110427596XA CN102492306A (en) | 2011-12-19 | 2011-12-19 | Boron-dipyrromethene dye containing sulfur and halogen, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110427596XA CN102492306A (en) | 2011-12-19 | 2011-12-19 | Boron-dipyrromethene dye containing sulfur and halogen, and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102492306A true CN102492306A (en) | 2012-06-13 |
Family
ID=46184170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110427596XA Pending CN102492306A (en) | 2011-12-19 | 2011-12-19 | Boron-dipyrromethene dye containing sulfur and halogen, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102492306A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478706A (en) * | 2016-10-12 | 2017-03-08 | 郑州大学 | Replace Two-photon fluorescent dye and its synthetic method of two pyrroles of fluorine boron and hexichol amido fluorenes based on phenyl |
| CN106632435A (en) * | 2016-10-12 | 2017-05-10 | 郑州大学 | Two-photon fluorescent dye based on phenyl-substituted boron-dipyrromethene and diphenyl indenofluorene and synthetic method thereof |
| KR20180026340A (en) * | 2016-09-02 | 2018-03-12 | 주식회사 엘지화학 | Compound and color conversion film comprising the same |
| CN109234759A (en) * | 2018-11-02 | 2019-01-18 | 陕西师范大学 | A kind of synthetic method being commercialized BODIPY |
| WO2022189648A1 (en) * | 2021-03-11 | 2022-09-15 | Cambridge Display Technology Ltd. | Polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005139371A (en) * | 2003-11-10 | 2005-06-02 | Japan Science & Technology Agency | Ion-sensitive dye and ion sensor using the same |
| CN101302353A (en) * | 2008-07-02 | 2008-11-12 | 大连理工大学 | Long wavelength boron dipyrromethene dye and preparation thereof |
| CN101424641A (en) * | 2008-11-01 | 2009-05-06 | 山西大同大学 | Strong acid type ph fluorescent probe based on fluoro-boron fluorescent dye |
| CN101565554A (en) * | 2009-05-24 | 2009-10-28 | 大连理工大学 | Strong-fluorescence boron dipyrromethene dye containing carbazole structure |
-
2011
- 2011-12-19 CN CN201110427596XA patent/CN102492306A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005139371A (en) * | 2003-11-10 | 2005-06-02 | Japan Science & Technology Agency | Ion-sensitive dye and ion sensor using the same |
| CN101302353A (en) * | 2008-07-02 | 2008-11-12 | 大连理工大学 | Long wavelength boron dipyrromethene dye and preparation thereof |
| CN101424641A (en) * | 2008-11-01 | 2009-05-06 | 山西大同大学 | Strong acid type ph fluorescent probe based on fluoro-boron fluorescent dye |
| CN101565554A (en) * | 2009-05-24 | 2009-10-28 | 大连理工大学 | Strong-fluorescence boron dipyrromethene dye containing carbazole structure |
Non-Patent Citations (3)
| Title |
|---|
| THIRUMANI VENKATESHWAR GOUD等: "Synthesis of 8-heteroatom-substituted 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene dyes (BODIPY)", 《TETRAHEDRON》 * |
| THIRUMANI VENKATESHWAR GOUD等: "Synthesis of 8-heteroatom-substituted 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene dyes (BODIPY)", 《TETRAHEDRON》, vol. 62, no. 21, 17 April 2006 (2006-04-17), pages 5084 - 5091 * |
| VELLANKI LAKSHMI等: "Synthesis of Sterically Crowded Polyarylated Boron-Dipyrromethenes", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180026340A (en) * | 2016-09-02 | 2018-03-12 | 주식회사 엘지화학 | Compound and color conversion film comprising the same |
| CN109563107A (en) * | 2016-09-02 | 2019-04-02 | 株式会社Lg化学 | Compound and color conversion coatings film comprising it |
| JP2019532912A (en) * | 2016-09-02 | 2019-11-14 | エルジー・ケム・リミテッド | Compound and color conversion film containing the same |
| KR102148067B1 (en) * | 2016-09-02 | 2020-08-26 | 주식회사 엘지화학 | Compound and color conversion film comprising the same |
| CN109563107B (en) * | 2016-09-02 | 2022-02-22 | 株式会社Lg化学 | Compound and color conversion film comprising same |
| US11479566B1 (en) | 2016-09-02 | 2022-10-25 | Lg Chem, Ltd. | Compound and color conversion film comprising same |
| CN106478706A (en) * | 2016-10-12 | 2017-03-08 | 郑州大学 | Replace Two-photon fluorescent dye and its synthetic method of two pyrroles of fluorine boron and hexichol amido fluorenes based on phenyl |
| CN106632435A (en) * | 2016-10-12 | 2017-05-10 | 郑州大学 | Two-photon fluorescent dye based on phenyl-substituted boron-dipyrromethene and diphenyl indenofluorene and synthetic method thereof |
| CN106478706B (en) * | 2016-10-12 | 2018-03-23 | 郑州大学 | Two-photon fluorescent dye and its synthetic method based on the pyrroles of phenyl substitution fluorine boron two and hexichol amido fluorenes |
| CN106632435B (en) * | 2016-10-12 | 2018-06-29 | 郑州大学 | Two-photon fluorescent dye and its synthetic method based on two pyrroles of phenyl substitution fluorine boron and hexichol amido indenofluorene |
| CN109234759A (en) * | 2018-11-02 | 2019-01-18 | 陕西师范大学 | A kind of synthetic method being commercialized BODIPY |
| WO2022189648A1 (en) * | 2021-03-11 | 2022-09-15 | Cambridge Display Technology Ltd. | Polymer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020052194A1 (en) | Fused ring benzothiadiazole-based non-fullerene acceptor material, preparation method therefor and use thereof | |
| CN102492306A (en) | Boron-dipyrromethene dye containing sulfur and halogen, and preparation method thereof | |
| Ball et al. | Chiral conjugated corrals | |
| Lakshmi et al. | Functionalized boron-dipyrromethenes and their applications | |
| Wang et al. | Regioselective 2, 6-dihalogenation of BODIPYs in 1, 1, 1, 3, 3, 3-hexafluoro-2-propanol and preparation of novel meso-alkyl polymeric BODIPY dyes | |
| Zhang et al. | A highly strained all‐phenylene conjoined bismacrocycle | |
| Zhang et al. | A new organic far-red mechanofluorochromic compound derived from cyano-substituted diarylethene | |
| Wang et al. | Novel hydroxyl-substituted perylene-3, 4, 9, 10-tetracarboxylic acid diimides for selective recognition of fluoride | |
| Liao et al. | Synthesis, optical and electrochemical properties of novel meso-triphenylamine-BODIPY dyes with aromatic moieties at 3, 5-positions | |
| Li et al. | Synthesis of B← N embedded indacenodithiophene chromophores and effects of bromine atoms on photophysical properties and energy levels | |
| Sun et al. | Probing the effect of acceptor engineering in benzothiadiazole-based DAD-typed hole-transporting materials for perovskite solar cells | |
| Ozser et al. | Novel derivatives of regioisomerically pure 1, 7-disubstituted perylene diimide dyes bearing phenoxy and pyrrolidinyl substituents: Synthesis, photophysical, thermal, and structural properties | |
| CN106348993A (en) | Annihilation agent applied to triplet-triplet annihilation up-conversion system, and preparation and application methods thereof | |
| Goeb et al. | Synthesis of novel tetrachromophoric cascade-type Bodipy dyes | |
| CN114014873B (en) | C2 v-based symmetrical aza-condensed ring compound and preparation method and application thereof | |
| Fujita et al. | A Series of Soluble Planar Oligorylenes up to Hexarylene | |
| Takahashi et al. | Synthesis of lipophilic bisanthracene fluorophores: versatile building blocks toward the synthesis of new light-harvesting dendrimers | |
| CN106478704A (en) | A kind of Two-photon fluorescent dye and its synthetic method for replacing two pyrroles of fluorine boron and hexichol amido fluorenes based on 4 cyano-phenyls | |
| Chevalier et al. | Rapid Synthesis of Unsymmetrical Sulforhodamines Through Nucleophilic Amination of a Monobrominated Sulfoxanthene Dye | |
| CN113292585B (en) | BODIPY-benzothiadiazole-porphyrin-carbazole quaternary system linear compound and preparation method thereof | |
| CN113773328B (en) | Fluorenyl carbazole macrocyclic compound and preparation method and application thereof | |
| Zhao et al. | Synthesis of fluorene-based di-BODIPY dyes containing different aromatic linkers and their properties | |
| CN108250790B (en) | Organic dye with near-infrared absorption based on alkynyl triphenylamine and perylene diimide, and preparation method and application thereof | |
| Liu et al. | TPA-active D–π–D fluorophores with rigid, planar cores from phenylene to indenofluorene and indolocarbazole | |
| CN109134515A (en) | Six dimmer compound of imidodicarbonic diamide and preparation method, composition and organic solar batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120613 |