CN105601608B - Coumarin derivative and its production and use - Google Patents

Coumarin derivative and its production and use Download PDF

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Publication number
CN105601608B
CN105601608B CN201510725292.XA CN201510725292A CN105601608B CN 105601608 B CN105601608 B CN 105601608B CN 201510725292 A CN201510725292 A CN 201510725292A CN 105601608 B CN105601608 B CN 105601608B
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formula
compound
straight
coumarin derivative
independently selected
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CN105601608A (en
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王利民
吴洵燊
杨阳
吴生英
王峰
王桂峰
田禾
王振炎
陈立荣
黄卓
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LILY GROUP CO Ltd
East China University of Science and Technology
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LILY GROUP CO Ltd
East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/02—Coumarine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0065—Preparation of organic pigments of organic pigments with only non-macromolecular compounds

Abstract

The present invention relates to a kind of coumarin derivative and application thereof.Described coumarin derivative is compound shown in formula I.Application of the compound as organic pigment shown in formula I.The present invention has not only expanded the application field of the coumarin derivative with big pi-conjugated system, and prepares such coumarin derivative for commercialization and lay a good foundation.In formula I, R1~R7It is respectively and independently selected from：Hydrogen, halogen, C1~C4Straight or branched alkyl, fluorine-containing C1~C4Straight or branched alkyl, hydroxyl, C1~C3Straight or branched alkoxyl, trifluoromethanesulfonic acid base or C6~C10It is a kind of in aromatic ring yl；Or, R1,R4,R5,R6And R7It is respectively and independently selected from：Hydrogen or C1~C3It is a kind of in straight or branched alkyl, R2And R3The phenyl for being combined as divalence.

Description

Coumarin derivative and its production and use
Technical field
The present invention relates to a kind of coumarin derivative and its production and use.
Background technology
Into 21 century, with the fast development of functional material and biomedicine etc., the perfume (or spice) with big pi-conjugated system Beans chlorins compound is widely used.
2007, kelly et al. synthesized compound shown in formula A by multistep reaction (12 step), and the compound can be controlled Treatment trauma medicine (Kelly, T.R.Org.Lett.2007,9,3255-3257).
2014, Gryko groups synthesized a kind of cumarin of π-π systems (chemical combination shown in formula B using Scholl reactions Thing), find its fluorescence quantum yield to be better than traditional umbelliferone (Gryko, D.T.Phys.Chem.Chem.Phys.2014,16,18268-18275).Hereafter, the group reports a kind of cumarin simultaneously again The compound (compound shown in formula C) of six ring structures of Coumarins, its have strong fluorescence property (Gryko, D.T.Chem.Commun.,2014,50,9105-9108)。
To sum up, the existing coumarin derivative with big pi-conjugated system is used as fluorescent material and medicine, and its synthesis is more Difficult (not being that step is tediously long, be exactly that raw material is rare).
The content of the invention
The present inventor has designed and synthesized the novel coumarin derivative with big π systems of structure, sends out simultaneously Existing its can be used as organic pigment, and easily prepared (synthesis step is succinct and raw material is easy to get).
It is an advantage of the invention to provide a kind of novel coumarin derivative of structure.
Coumarin derivative of the present invention is compound shown in formula I：
In formula I, R1~R7It is respectively and independently selected from：Hydrogen (H), halogen (F, Cl, Br or I), C1~C4Straight or branched alkyl, Fluorine-containing C1~C4Straight or branched alkyl, hydroxyl (- OH), C1~C3Straight or branched alkoxyl, trifluoromethanesulfonic acid base (- OTf) Or C6~C10It is a kind of in aromatic ring yl；Or,
R1,R4,R5,R6And R7It is respectively and independently selected from：Hydrogen (H) or C1~C3It is a kind of in straight or branched alkyl, R2And R3Group Be combined into divalence phenyl (Curve mark is substitution position, and it is relation " simultaneously " with parent benzene).
A kind of it is another object of the present invention to provide method of compound shown in formula I.
Methods described comprises the following steps：
(1) as shown in formula II shown in preparation of compounds of formula III the step of compound；With
(2) compound shown in compound and a of the formula IV or b of formula IV is reacted as shown in formula III, be made object (one of) step Suddenly；
Or,
(1) as shown in formula V shown in preparation of compounds of formula VI the step of compound；
(2) shown in formula VI shown in preparation of compounds of formula VII the step of compound；
(3) shown in formula VII shown in preparation of compounds of formula VIII the step of compound；
(4) shown in formula VIII shown in preparation of compounds of formula Ⅸ the step of compound；And
(5) compound shown in compound shown in formula Ⅸ and a of the formula IV or b of formula IV is reacted, the step of object (two) is made；
A further object of the invention is, discloses a kind of purposes of compound shown in formula I.
That is, application of the compound as organic pigment shown in formula I, in other words, compound is preparing organic pigment shown in formula I In application.
Meaning of the present invention is, has not only expanded the application field of the coumarin derivative with big pi-conjugated system, and And prepare such coumarin derivative for commercialization and lay a good foundation.
Embodiment
In a preferable technical scheme of the invention, R1~R7It is respectively and independently selected from：H, halogen (F, Cl, Br or I), C1 ~C4Straight or branched alkyl, fluorine-containing C1~C4Straight or branched alkyl ,-OH, C1~C3Straight or branched alkoxyl ,-OTf or It is a kind of in phenyl or naphthyl.
Further preferred technical scheme is：R1,R2And R3It is respectively and independently selected from：H, halogen (F, Cl, Br or I), C1~C4 Straight or branched alkyl ,-OH, C1~C3It is a kind of in straight or branched alkoxyl ,-OTf or phenyl or naphthyl；
R4,R5,R6And R7It is respectively and independently selected from：H, halogen (F, Cl, Br or I), C1~C4Straight or branched alkyl, it is fluorine-containing C1~C4Straight or branched alkyl or C1~C3It is a kind of in straight or branched alkoxyl.
Technical scheme still more preferably is：R1,R2And R3It is respectively and independently selected from：H, halogen (F, Cl, Br or I), first It is a kind of in base, normal-butyl ,-OH, methoxyl group ,-OTf or phenyl or naphthyl；
R4,R5,R6And R7It is respectively and independently selected from：H, halogen (F, Cl, Br or I), methyl, the tert-butyl group, trifluoromethyl or methoxy It is a kind of in base.
In presently preferred technical scheme, coumarin derivative of the present invention is chemical combination shown in the A of formula I Thing：
In the A of formula I, R1,R4,R5,R6And R7It is respectively and independently selected from：It is a kind of in hydrogen (H) or methyl.
The method of compound, specifically comprises the following steps shown in formula I provided by the invention：
(1) under the conditions of with the presence of acetic anhydride and sodium acetate and 150 DEG C, compound is in aprotic organic solvent shown in formula II In, kept for about six hours in 150 DEG C of states, obtain compound shown in formula III；
(2) under the conditions of with the presence of inert gas and copper trifluoromethanesulfcomposite and 100 DEG C, compound and formula as shown in formula III Compound shown in the IV a or b of formula IV reacts (about 24 hours) in aprotic organic solvent, obtain object (one of).
Or,
(1) under the conditions of with the presence of NaH and 0 DEG C, compound and CH as shown in formula V3I reacts, and obtains chemical combination shown in formula VI Thing；
(2) under the conditions of with the presence of n-BuLi and -78 DEG C, compound is reacted with DMF in THF as shown in formula VI, is obtained To compound shown in formula VII；
(3) there is excessive AlCl3In the presence of and room temperature condition under, compound is in halogenated alkyl solvent shown in formula VII, anhydrous The state of anaerobic keeps at least 8h, obtains compound shown in formula VIII；
(4) under the conditions of with the presence of acetic anhydride and sodium acetate and 150 DEG C, compound is in aprotic organic solvent shown in formula VIII In, kept for about six hours in 150 DEG C of states, obtain compound shown in formula Ⅸ；And
(5) under the conditions of with the presence of inert gas and copper trifluoromethanesulfcomposite and 100 DEG C, compound and formula as shown in formula Ⅸ Compound shown in the IV a or b of formula IV reacts (about 24 hours) in aprotic organic solvent, obtains object (two).
Below by embodiment, the present invention will be further described, and its purpose, which is only that, is best understood from present disclosure. The cited case does not limit the scope of the invention.
Embodiment 1
Salicylide (compound ii -1,10mmol, 1equiv) and sodium acetate (15mmol, 1.5equiv) are placed in 100mL In round-bottomed flask, while 30mLN is added, dinethylformamide (DMF), add acetic anhydride (12mmol, 1.2equiv), add Hot to 150 DEG C are reacted 6 hours.After reaction terminates, room temperature is cooled to, 50mL frozen water is added and reaction is quenched, with 100mL ethyl acetate Three times, organic phase anhydrous sodium sulfate drying, filtering is spin-dried for pillar layer separation purification (PE for extraction:EA=5:1 (v/v), similarly hereinafter) Obtain compound III -1.
In N2Under protection, diaryl group iodized salt (1.5mmol, 3.0equiv) is sequentially added in 25mL Schlenk bottles, is changed Compound III -1 (0.5mmol, 1.0equiv), Cu (OTf)2(0.05mmol, 18mg), it is steamed to add 2mL weights with syringe DMF, react 24 hours at 100 DEG C.After reaction terminates, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE/EA= 15/1 (v/v)) obtain yellow solid (chemical compounds I -1), M.p.:155-157 DEG C, yield 90%.
1H NMR(400MHz,CDCl3):δ 7.79 (d, J=7.6Hz, 1H), 7.72 (d, J=7.6Hz, 1H), 7.47- 7.54 (m, 2H), 7.43 (d, J=7.2Hz, 1H), 7.37 (t, J=7.6Hz, 1H), 7.12 (d, J=8.0Hz, 1H), 6.73 (s,1H)；
13C NMR(100MHz,CDCl3):δ162.9,150.8,150.5,143.1,138.0,134.6,133.2, 132.4,128.3,125.2,122.2,120.9,116.9,114.8,108.9；
HRMS (ESI) theoretical value (calculated for)：C15H9O2[M+H]+221.0603 experiment value (found)： 221.0605。
Embodiment 2
Divided by the alternate embodiment of compound ii -2 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -2), M.p.:174-176 DEG C, yield 60%.
1H NMR(400MHz,CDCl3):δ 8.15 (d, J=7.6Hz, 1H), 7.82 (d, J=7.6Hz, 1H), 7.56 (td, J=7.6,0.8Hz, 1H), 7.43 (dd, J=7.6,1.2Hz, 1H), 7.39 (d, J=8.8Hz, 1H), 7.07 (d, J= 8.8Hz,1H),6.76(s,1H)；
13C NMR(100MHz,CDCl3)δ162.3,149.7,149.2,141.7,134.3,134.3,134.0,132.7, 128.8,125.2,124.7,124.5,122.1,116.2,109.5；
HRMS(ESI)calculated for C15H8ClO2[M+H]+255.0213,found 255.0199。
Embodiment 3
Divided by the alternate embodiment of compound ii -3 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -3), M.p.:174-176 DEG C, yield 61%.
1H NMR(400MHz,CDCl3):δ 7.72 (d, J=7.2Hz, 1H), 7.69 (d, J=7.6Hz, 1H), 7.48 (td, J=7.6,1.2Hz, 1H), 7.33 (td, J=7.6,0.8Hz, 1H), 7.19 (d, J=7.6Hz, 1H), 6.95 (d, J= 8.0Hz,1H),6.60(s,1H),2.56(s,3H)；
13C NMR(100MHz,CDCl3)δ163.0,150.2,149.0,143.7,135.4,135.2,134.6,132.3, 129.9,127.6,125.0,124.0,120.5,114.6,108.2,18.9；
HRMS(ESI)calculated for C16H11O2[M+H]+235.0759,found 235.0753。
Embodiment 4
Divided by the alternate embodiment of compound ii -4 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -4), M.p.:174-176 DEG C, yield 55%.
1H NMR(400MHz,CDCl3) δ 7.83 (t, J=6.4Hz, 2H), 7.54 (t, J=8.0Hz, 1H), 7.41 (td, J =7.6,0.8Hz, 1H), 7.18 (t, J=8.8Hz, 1H), 7.10 (dd, J=9.2,2.8Hz, 1H), 6.79 (s, 1H)；
13C NMR(100MHz,CDCl3)δ162.6,155.1,152.6,150.1(d,JC-F=2.6Hz), 146.9 (d, JC-F=1.9Hz), 140.4,134.0,132.8,128.5,125.2,124.9 (d, JC-F=3.1Hz), 122.6 (d, JC-F= 17.6Hz),122.1(d,JC-F=8.3Hz), 121.0 (d, JC-F=24.2Hz), 116.6 (d, JC-F=7.1Hz), 109.8；
19F NMR(376MHz,CDCl3)δ-121.46(s,1F)；
HRMS(ESI)calculated for C15H8FO2[M+H]+239.0508,found 239.0516。
Embodiment 5
Divided by the alternate embodiment of compound ii -5 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -5), M.p.:252-254 DEG C, yield 56%.
1H NMR(400MHz,CDCl3) δ 7.76 (d, J=7.6Hz, 1H), 7.68 (d, J=7.6Hz, 1H), 7.49 (td, J =0.8,7.6Hz, 1H), 7.35 (td, J=0.8,7.6Hz, 1H), 7.25 (s, 1H), 6.91 (s, 1H), 6.65 (s, 1H), 2.50(s,3H)；
13C NMR(100MHz,CDCl3)δ163.2,150.77,150.4,144.7,143.2,137.8,135.1, 132.2,128.2,125.2,122.1,118.7,118.1,114.9,107.8,22.6；
HRMS(ESI)calculated for C16H11O2[M+H]+235.0759,found 235.0757。
Embodiment 6
Divided by the alternate embodiment of compound ii -6 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -6), M.p.:171-175 DEG C, yield 57%.
1H NMR(400MHz,CDCl3):δ 7.80 (d, J=7.6Hz, 1H), 7.76 (d, J=7.6Hz, 1H), 7.61- 7.64 (m, 3H), 7.37-7.54 (m, 5H), 7.29 (d, J=0.4Hz, 1H), 6.71 (s, 1H)；
13C NMR(100MHz,CDCl3)δ163.0,151.0,150.3,147.5,143.0,140.5,138.3,135.1, 132.4,129.1,128.5,128.4,127.5,125.3,122.3,120.0,116.4,113.5,108.6；
HRMS(ESI)calculated for C21H12O2[M+H]+297.0916,found 297.0915。
Embodiment 7
Divided by the alternate embodiment of compound ii -7 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -7), M.p.:202-205 DEG C, yield 57%.
1H NMR(400MHz,CDCl3):δ 7.78 (d, J=7.6Hz, 1H), 7.67 (d, J=7.6Hz, 1H), 7.52 (td, J=0.8,7.6Hz, 1H), 7.32-7.38 (m, 2H), 7.22 (dd, J=8.0,11.2Hz, 1H), 6.74 (s, 1H)；
13C NMR(100MHz,CDCl3) δ 161.3,150.2 (d, J=1.9Hz), 149.4,146.8,142.5,138.7 (d, J=13.4Hz), 134.6,133.3 (d, J=12.7Hz), 132.7,128.0,125.4,123.0 (d, J=3.1Hz), 122.0,119.4 (d, J=19.1Hz), 117.1 (d, J=6.2Hz), 109.4；
19F NMR(376MHz,CDCl3)δ-134.53(s,1F)；
HRMS(ESI)calculated for C15H7FO2[M+H]+239.0508,found 239.0516。
Embodiment 8
Beta naphthal (compound V -1,10mmol, 1equiv) is dissolved in 30mL tetrahydrofurans, by reaction solution ice water cooling But to 0 DEG C, NaH (20mmol, 2equiv) is added, after stirring 5 minutes, adds CH3I (12mmol, 1.2equiv), reacts in room After the lower reaction of temperature two hours, add frozen water and reaction is quenched, extracted 3 times with 100mL ethyl acetate, it is organic with saturated common salt water washing Xiang Hou, with anhydrous sodium sulfate drying, filtering is spin-dried for, silica gel post separation (PE:EA=10:1) compound VI -1 (95%), is obtained；
Compound VI -1 (5mmol, 1equiv) being dissolved in the THF of 20mL dryings, the protection reacted in nitrogen cools to - 78 DEG C, n-BuLi (15mmol, 3equiv) is squeezed into, reacts and is warming up to 0 DEG C after being stirred one hour in the environment of -78 DEG C, slowly Slowly dry DMF (10mmol, 2equiv) is squeezed into, then reaction is stirred at room temperature overnight, and adds water quenching to go out after reaction, is used 100mL dichloromethane extracts 3 times, with saturation experiments water washing organic phase, is spin-dried for after adding anhydrous sodium sulfate drying, silicagel column point From (PE:EA=10:1) compound VII -1 (60%), is obtained；
Compound VII -1 (2mmol, 1equiv) is dissolved in 20mL dichloromethane, adds excessive AlCl3, in anhydrous nothing The state of oxygen keeps 8h, adds water quenching to go out and reacts and extracted with dichloromethane, is spin-dried for after drying, silica gel post separation (PE:EA=8: 1) compound VIII -1 (99%), is obtained；
Compound VIII -1 (2mmol, 1equiv) and sodium acetate (3mmol, 1.5equiv) are placed in 50mL round-bottomed flasks, 15mL DMF is added simultaneously, adds acetic anhydride (2.4mmol, 1.2equiv), is heated to 150 DEG C and is reacted 6 hours, is cooled to Room temperature, add 50mL frozen water and reaction is quenched, with the extraction of 100mL ethyl acetate three times, organic phase anhydrous sodium sulfate drying, filtering It is spin-dried for pillar layer separation purification (PE:EA=5:1) compound Ⅸ -1 is obtained；
In N2Under protection, diaryl group iodized salt (1.5mmol, 3.0equiv) is sequentially added in 25mL Schlenk bottles, is changed Compound Ⅸ -1 (0.5mmol, 1.0equiv), Cu (OTf)2(0.05mmol, 18mg), it is steamed to add 2mL weights with syringe DMF, react 24 hours at 100 DEG C.After reaction terminates, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE/EA= 15/1) yellow solid (chemical compounds I A-1), M.p. are obtained:245-247 DEG C, yield 70%.
1H NMR(400MHz,CDCl3):δ 8.28 (d, J=8.0Hz, 1H), 8.01 (d, J=7.6Hz, 1H), 7.85 (d, J =7.2Hz, 1H), 7.75 (d, J=7.2Hz, 1H), 7.46-7.58 (m, 3H), 7.41 (s, 1H), 7.34 (t, J=7.6Hz, 1H),6.70(s,1H)；
13C NMR(100MHz,CDCl3)δ162.4,150.0,147.2,143.7,137.4,134.7,133.7,132.4, 129.7,127.5,127.3,126.6,126.5,124.9,124.1,124.0,120.6,111.8,109.8；
HRMS(ESI)calculated for C19H10O2[M+H]+271.0759,found 271.0756。
Embodiment 9
Divided by the alternate embodiment of compound ii -8 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -8), M.p.:248-250 DEG C, yield 53%.
1H NMR(400MHz,CDCl3):δ 8.32 (d, J=7.6Hz, 1H), 7.83 (d, J=7.2Hz, 1H), 7.56- 7.61 (m, 2H), 7.44 (td, J=7.6,0.8Hz, 1H), 7.02 (d, J=8.8Hz, 1H), 6.77 (s, 1H)；
13C NMR(100MHz,CDCl3):δ162.2,149.8,149.6,142.3,137.0,136.4,134.5, 132.5,128.9,125.2,124.2,122.6,116.4,111.9,109.3；
HRMS(ESI)calculated for C15H8BrO2[M+H]+298.9708,found 298.9700。
Embodiment 10
Divided by the alternate embodiment of compound ii -10 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -9), M.p.:275-278 DEG C, yield 50%.
1H NMR(400MHz,DMSO-d6):δ 10.62 (s, 1H), 8.05 (d, J=7.6Hz, 1H), 7.92 (d, J= 7.2Hz, 1H), 7.58 (td, J=7.6,1.2Hz, 1H), 7.46 (td, J=7.6,0.8Hz, 1H), 7.16 (d, J=1.2Hz, 1H), 6.90 (s, 1H), 6.61 (d, J=1.6Hz, 1H)；
13C NMR(100MHz,DMSO-d6):δ163.6,162.5,151.6,149.9,142.1,138.3,135.2, 132.2,128.5,125.6,122.6,112.5,106.7,105.5,100.2；
HRMS(ESI)calculated for C15H8O3[M+H]+237.0552,found 237.0543。
Embodiment 11
Divided by the alternate embodiment of compound ii -11 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -10), M.p.:181-184 DEG C, yield 53%.
1H NMR(400MHz,CDCl3):δ 7.79 (d, J=7.2Hz, 1H), 7.70 (d, J=7.6Hz, 1H), 7.51 (td, J=7.6,1.2Hz, 1H), 7.38 (td, J=7.6,1.2Hz, 1H), 7.05 (d, J=1.6Hz, 1H), 6.62 (d, J= 1.6Hz,1H),6.61(s,1H),3.92(s,3H)；
13C NMR(100MHz,CDCl3):δ165.3,163.4,151.9,150.5,142.7,138.5,135.7, 132.1,128.5,125.0,122.2,114.5,105.8,105.7,98.6,56.2；
HRMS(ESI)calculated for C16H10O3[M+H]+251.0708,found 251.0706。
Embodiment 12
Divided by the alternate embodiment of compound ii -12 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -11), M.p.:117-121 DEG C, yield 50%.
1H NMR(400MHz,CDCl3):δ 7.71 (d, J=7.6Hz, 1H), 7.62 (d, J=7.6Hz, 1H), 7.47 (t, J =7.6Hz, 1H), 7.34 (t, J=7.6Hz, 1H), 6.96 (d, J=1.2Hz, 1H), 6.53 (d, J=1.2Hz, 1H), 6.50 (s, 1H), 4.02 (t, J=6.4Hz, 2H), 1.86-1.78 (m, 2H), 1.59-1.48 (m, 2H), 1.01 (t, J=7.6Hz, 3H)；
13C NMR(100MHz,CDCl3):δ164.8,163.5,151.9,150.5,142.8,138.5,135.7, 132.0,128.4,125.0,122.2,114.3,106.2,105.6,99.1,68.8,31.1,19.2,13.9；
HRMS(ESI)calculated for C19H16O3[M+H]+293.1178,found 293.1179。
Embodiment 13
Divided by the alternate embodiment of compound ii -13 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -13), M.p.:167-169 DEG C, yield 70%.
1H NMR(400MHz,CDCl3):δ 7.85 (d, J=7.2Hz, 1H), 7.77 (d, J=7.6Hz, 1H), 7.58 (td, J=0.8,7.6Hz, 1H), 7.47 (td, J=1.2,7.6Hz, 1H), 7.37 (d, J=1.6Hz, 1H), 7.07 (d, J= 1.6Hz,1H),6.80(s,1H)；
13C NMR(100MHz,CDCl3):δ161.5,152.5,150.6,149.5,141.5,139.4,134.9, 132.9,129.6,125.5,122.9,120.4,117.1,111.0,110.0,108.5；
19F NMR(376MHz,CDCl3)δ-72.47(s,1F)；
HRMS(ESI)calculated for C16H7F3O5S[M+H]+369.0045,found 369.0032。
Embodiment 14
Divided by the alternate embodiment of compound ii -14 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -13), M.p.:240-242 DEG C, yield 60%.
1H NMR(400MHz,CDCl3):δ 7.82 (d, J=7.6Hz, 1H), 7.71 (d, J=7.6Hz, 1H), 7.55 (td, J=1.2,7.6Hz, 1H), 7.45-7.40 (m, 2H), 7.15 (d, J=1.2Hz, 1H), 6.73 (s, 1H)；
13C NMR(100MHz,CDCl3):δ162.1,150.7,149.8,142.1,139.0,138.8,134.9, 132.6,129.0,125.4,122.5,119.4,117.8,115.0,108.9；
HRMS(ESI)calculated for C15H8ClO2[M+H]+255.0213,found 255.0211。
Embodiment 15
Divided by the alternate embodiment of compound ii -15 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -14), M.p.:132-135 DEG C, yield 91%.
1H NMR(400MHz,CDCl3):δ 7.76 (d, J=7.6Hz, 1H), 7.64 (d, J=7.6Hz, 1H), 7.48 (td, J=7.6,1.2Hz, 1H), 7.34 (d, J=8.0Hz, 1H), 7.30 (td, J=7.6,1.2Hz, 1H), 6.96 (d, J= 7.6Hz,1H),6.74(s,1H),4.00(s,3H)；
13C NMR(100MHz,CDCl3):δ162.2,150.7,146.8,143.4,140.6,134.6,132.5, 129.7,127.2,125.2,122.2,121.5,117.3,114.7,108.8,56.7；
HRMS(ESI)calculated for C16H10O3[M+H]+251.0708,found 251.0704。
Embodiment 16
Divided by the alternate embodiment of compound ii -16 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -15), M.p.:179-182 DEG C, yield 73%.
1H NMR(400MHz,CDCl3):δ 7.82 (d, J=7.6Hz, 1H), 7.76-7.71 (m, 3H), 7.61 (d, J= 7.6Hz,1H),7.55-7.47(m,4H),7.43-7.36(m,2H),6.78(s,1H)；
13C NMR(100MHz,CDCl3):δ162.7,150.7,148.0,142.8,137.1,135.0,134.8, 133.7,132.4,129.2,128.7,128.2,128.1,125.1,122.1,121.3,117.2,108.8；
HRMS(ESI)calculated for C21H12O2[M+H]+297.0916,found 297.0916。
Embodiment 17
Divided by the alternate embodiment of compound ii -17 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -16), M.p.:205-208 DEG C, yield 86%.
1H NMR(400MHz,CDCl3):δ 7.80 (d, J=7.6Hz, 1H), 7.71 (d, J=7.6Hz, 1H), 7.49- 7.56(m,2H),7.35-7.42(m,2H),6.76(s,1H)；
13C NMR(100MHz,CDCl3):δ161.6,150.2,146.8,142.4,136.5,134.4,133.2, 132.7,128.5,125.4,122.3,122.0,119.3,117.4,109.4；
HRMS(ESI)calculated for C15H17ClO2[M+H]+255.0213,found 255.0209。
Embodiment 18
Divided by the alternate embodiment of compound ii -18 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -17), M.p.:216-218 DEG C, yield 98%.
1H NMR(400MHz,CDCl3):δ 7.80 (d, J=7.2Hz, 1H), 7.71 (d, J=7.6Hz, 1H), 7.66 (d, J =7.6Hz, 1H), 7.53 (td, J=0.8,7.6Hz, 1H), 7.40 (td, J=0.8,7.6Hz, 1H), 7.31 (d, J= 7.6Hz,1H),6.74(s,1H)；
13C NMR(100MHz,CDCl3):δ161.7,150.3,148.1,142.4,137.2,136.1,134.2, 132.7,128.6,125.3,122.3,122.0,117.8,109.4,107.4；
HRMS(ESI)calculated for C15H7BrO2[M+H]+298.9708,found 298.9715。
Embodiment 19
Divided by the alternate embodiment of compound ii -19 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -18), M.p.:245-248 DEG C, yield 19%.
1H NMR(400MHz,CDCl3):δ 8.15 (d, J=7.6Hz, 1H), 7.84 (d, J=7.6Hz, 1H), 7.59 (t, J =7.6Hz, 1H), 7.48-7.43 (m, 2H), 6.82 (s, 1H)；
13C NMR(100MHz,CDCl3):δ161.1,149.7,145.6,141.2,134.1,133.5,133.1, 133.0,129.0,125.3,124.7,124.5,122.9,120.3,110.0；
HRMS(ESI)calculated for C15H6Cl2O2[M+H]+288.9823,found 288.9826。
Embodiment 20
Divided by the alternate embodiment of compound ii -19 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -19), M.p.:256-259 DEG C, yield 14%.
1H NMR(400MHz,CDCl3):δ 8.30 (d, J=7.6Hz, 1H), 7.84 (d, J=7.6Hz, 1H), 7.80 (s, 1H), 7.60 (td, J=1.2,7.6Hz, 1H), 7.47 (td, J=0.8,7.6Hz, 1H), 6.79 (s, 1H)；
13C NMR(100MHz,CDCl3):δ161.1,149.5,147.3,141.7,139.0,135.7,134.1, 132.8,129.1,125.3,124.2,123.1,112.0,109.7,108.4；
HRMS(ESI)calculated for C15H6Br2O2[M+H]+376.8813,found 376.8803。
Embodiment 21
Divided by the alternate embodiment of compound ii -20 1 outside compound ii -1, other conditions and step are same as Example 1, Obtain yellow solid (chemical compounds I -20), M.p.:200-203 DEG C, yield 82%.
1H NMR(400MHz,CDCl3):δ 7.93 (d, J=8.0Hz, 2H), 7.87 (d, J=7.6Hz, 1H), 7.81 (d, J =7.6Hz, 1H), 7.69 (d, J=8.0Hz, 1H), 7.58-7.48 (m, 6H), 7.42 (t, J=7.6Hz, 2H), 6.79 (s, 1H)；
13C NMR(100MHz,CDCl3):δ162.7,150.7,148.8,143.0,137.5,135.7,134.9, 133.8,132.7,132.5,132.0,128.8,128.4,128.3,128.2,127.9,126.3,126.0,125.7, 125.3,125.3,122.2,121.2,116.8,109.2；
HRMS(ESI)calculated for C25H14O2[M+H]+347.1072,found 347.1074。
Embodiment 22
Divided by diaryl group iodized salt (Ph in diaryl group iodized salt (compound a) alternate embodiment 1 of chlorine2IOTf) outside, it is other Condition is same as Example 1 with step, obtains yellow solid (chemical compounds I -21), M.p.:256-259 DEG C, yield 72%.
1H NMR(400MHz,CDCl3):δ 7.73 (d, J=8.0Hz, 1H), 7.70 (d, J=1.6Hz, 1H), 7.53 (t, J =7.6Hz, 1H), 7.44 (d, J=7.2Hz, 1H), 7.36 (dd, J=8.0,2.0Hz, 1H), 7.18 (d, J=8.0Hz, 1H), 6.74(s,1H)；
13C NMR(100MHz,CDCl3):δ162.5,150.8,149.2,144.7,138.7,136.8,133.3, 132.9,128.3,126.0,122.9,121.2,117.2,115.5,109.4；
HRMS(ESI)calculated for C15H8ClO2[M+H]+255.0213,found 255.0220。
Embodiment 23
Divided by the diaryl group iodized salt of bromine (diaryl group iodized salt (Ph in compound b) alternate embodiments 12IOTf) outside, it is other Condition is same as Example 1 with step, obtains yellow solid (chemical compounds I -22), M.p.:245-248 DEG C, yield 58%.
1H NMR(400MHz,CDCl3):δ 7.91 (d, J=2.0Hz, 1H), 7.69 (d, J=8.0Hz, 1H), 7.53- 7.56 (m, 2H), 7.46 (d, J=7.2Hz, 1H), 7.19 (d, J=8.4Hz, 1H), 6.79 (s, 1H)；
13C NMR(100MHz,CDCl3):δ162.6,150.9,149.5,144.9,136.9,133.5,131.3, 127.2,126.3,125.9,121.2,117.3,115.6,109.6；
HRMS(ESI)calculated for C15H8BrO2[M+H]+298.9708,found 298.9700。
Embodiment 24
Divided by the diaryl group iodized salt of fluorine (diaryl group iodized salt (Ph in compound c) alternate embodiments 12IOTf) outside, it is other Condition is same as Example 1 with step, obtains yellow solid (chemical compounds I -23), M.p.:218-220 DEG C, yield 65%.
1H NMR(400MHz,CDCl3):δ 7.80 (dd, J=8.4,5.2Hz, 1H), 7.54 (t, J=7.6Hz, 1H), 7.42-7.47 (m, 2H), 7.19 (d, J=8.4Hz, 1H), 7.08 (td, J=8.4,2.4Hz, 1H), 6.74 (s, 1H)；
13C NMR(100MHz,CDCl3):δ167.0,164.5,162.6,150.7,149.3,145.7,136.8, 133.3,130.5,126.7(d,JC-F=9.9Hz), 121.6,117.2,115.5,115.2 (d, JC-F=44.9Hz), 110.3 (d,JC-F=24.2Hz), 108.8；19F NMR(376MHz,CDCl3)δ105.73(s,1H)；
HRMS(ESI)calculated for C15H8FO2[M+H]+239.0508,found 239.0500。
Embodiment 25
Divided by the diaryl group iodized salt of the tert-butyl group (diaryl group iodized salt (Ph in compound d) alternate embodiments 12IOTf) outside, Other conditions are same as Example 1 with step, obtain yellow solid (chemical compounds I -24), M.p.:188-191 DEG C, yield 88%.
1H NMR(400MHz,CDCl3):δ 7.74 (d, J=1.6Hz, 1H), 7.69 (d, J=8.0Hz, 1H), 7.49- 7.42 (m, 2H), 7.39 (dd, J=8.0,2.0Hz, 1H), 7.08 (d, J=8.0Hz, 1H), 6.65 (s, 1H), 1.41 (s, 9H)；
13C NMR(100MHz,CDCl3):δ163.0,156.6,150.7,150.4,143.2,138.3,133.0, 132.0,125.5,124.9,121.3,119.4,116.7,114.6,108.2,35.5,31.3；
HRMS(ESI)calculated for C19H7O2[M+H]+277.1229,found 277.1225。
Embodiment 26
Divided by the diaryl group iodized salt of methoxyl group (diaryl group iodized salt (Ph in compound e) alternate embodiments 12IOTf) outside, Other conditions are same as Example 1 with step, obtain yellow solid (chemical compounds I -25), M.p.:156-158 DEG C, yield 95%.
1H NMR(400MHz,CDCl3):δ 7.64 (d, J=8.4Hz, 1H), 7.45 (t, J=7.6Hz, 1H), 7.36 (d, J =7.6Hz, 1H), 7.18 (d, J=2.4Hz, 1H), 7.09 (d, J=8.0Hz, 1H), 6.82 (dd, J=2.4,8.4Hz, 1H), 6.54(s,1H),3.92(s,1H)；
13C NMR(100MHz,CDCl3):δ163.5,163.1,150.5,150.0,145.3,137.6,132.8, 126.9,126.4,121.8,116.7,114.9,113.2,108.6,106.9,55.8；
HRMS(ESI)calculated for C16H10O3[M+H]+251.0708,found 251.0711。
Embodiment 27
Divided by the diaryl group iodized salt of methyl (diaryl group iodized salt (Ph in compound f) alternate embodiments 12IOTf) outside, its Its condition is same as Example 1 with step, obtains yellow solid (chemical compounds I -26), M.p.:163-165 DEG C, yield 87%.
1H NMR(400MHz,CDCl3):δ 7.62 (d, J=7.6Hz, 1H), 7.50 (s, 1H), 7.46 (t, J=7.6Hz, 1H), 7.37 (d, J=7.6Hz, 1H), 7.15 (d, J=7.6Hz, 1H), 7.08 (d, J=8.4Hz, 1H), 6.63 (s, 1H), 2.47(s,3H)；
13C NMR(100MHz,CDCl3):δ163.0,150.7,150.4,143.4,143.3,138.0,133.0, 132.0,129.0,125.0,123.1,121.2,116.7,114.6,108.1,22.1；
HRMS(ESI)calculated for C16H11O2[M+H]+235.0759,found 235.0754。
Embodiment 28
Divided by diaryl group iodized salt (diaryl group iodized salt (the Ph in compound g) alternate embodiments 1 of a methyl2IOTf) outside, its Its condition is same as Example 1 with step, obtains yellow solid (chemical compounds I -27), M.p.:208-211 DEG C, yield 90%.
1H NMR(400MHz,CDCl3):δ 7.55 (d, J=8.0Hz, 1H), 7.53 (s, 1H), 7.44 (t, J=7.6Hz, 1H), 7.34 (d, J=7.6Hz, 1H), 7.28 (d, J=8.0Hz, 1H), 7.05 (d, J=8.4Hz, 1H), 6.63 (s, 1H), 2.43(s,3H)；
13C NMR(100MHz,CDCl3):δ163.0,150.7,150.6,140.5,138.5,138.1,134.8, 133.1,133.0,125.8,121.9,120.8,116.5,114.3,108.5,21.5；
HRMS(ESI)calculated for C16H11O2[M+H]+235.0759,found 235.0763。
Embodiment 29
Divided by the diaryl group iodized salt of trifluoromethyl (diaryl group iodized salt (Ph in compound h) alternate embodiments 12IOTf) Outside, other conditions are same as Example 1 with step, obtain yellow solid (chemical compounds I -28), M.p.:257-260 DEG C, yield 88%.
1H NMR(400MHz,CDCl3):δ 7.99 (s, 1H), 7.95 (d, J=8.0Hz, 1H), 7.67 (dd, J=0.4, 8.0Hz, 1H), 7.61-7.53 (m, 2H), 7.22 (dd, J=0.8,8.0Hz, 1H), 6.87 (s, 1H)；
13C NMR(100MHz,CDCl3):δ162.5,151.1,149.2,143.8,137.9,136.9,134.4, (133.9,130.8,125.6,125.5,121.3,119.3 q, J=5.0Hz), 117.7,115.8,111.0；
19F NMR(376MHz,CDCl3)δ-63.21(s,1H)；
HRMS(ESI)calculated for C16H7F3O2[M+H]+289.0476,found 289.0467。
Pigment compounds performance test
Embodiment 30
By taking chemical compounds I -9 as an example, following pigment performance test is carried out
1) pH value determines：Take minority specioz I -9 to be configured to 10% suspension, acutely rock, its pH value is surveyed with pH meter For 6.8, in neutrality.
2) hydrotrope determines：50mg chemical compounds I -9 are taken, are dissolved in 100mL water, heating is boiled 5 minutes, is cooled down, and filtering, is taken 10ml filtrates are evaporated, and obtain 0.5mg solid, and thus its water solubles content is 5%.
3) 105 DEG C of volatile matters：Take 50mg chemical compounds Is -9 to be placed in evaporating dish, be heated to 105 DEG C, its quality is claimed after cooling For 49.8mg, then its volatile matter at 105 DEG C accounts for 0.4%.
4) water resistance：Take 50mg chemical compounds Is -9 to be placed in water, filtered after heating, see filtrate still into water white transparency, then its is resistance to Water excellent performance.
4) acid resistance：Take 50mg chemical compounds Is -9 to be placed in 1mol/L sulfuric acid, filtered after being heated to 50 DEG C, obtain yellow and consolidate Body 49mg, illustrate that acid resistance is excellent.
5) alkali resistance：Take 50mg chemical compounds Is -9 to be placed in 1mol/L sodium hydroxide solution, filtered after being heated to 50 DEG C, Yellow solid 48mg is obtained, illustrates that alkali resistance is excellent.
The performance of other compounds is shown in Table 1.
Embodiment 31
By taking chemical compounds I -28 as an example, tested as follows
Standard chalk 2g is respectively weighed on two blocks of sheet glass respectively, then weigh respectively chemical compounds I in 50mg embodiments 29- 28 mill base and the mill base of 50mgC.I. pigment Yellow 12s 9, are fully mixed well with inking knife, scrape sample.Aberration is carried out with colour photometer, by surveying Color result is visible, Δ C>0, illustrate that the compound of chemical compounds I -28 is more bright-coloured than the coloured light of C.I. pigment Yellow 12 9.The property of other compounds 1 can be shown in Table.
Table 1
Continued 1
From embodiment 30 and 31, compound provided by the invention can be used as (yellow) organic pigment.

Claims (8)

1. a kind of coumarin derivative, described coumarin derivative is compound shown in Formulas I：
In Formulas I, R1~R7It is respectively and independently selected from：Hydrogen, halogen, C1~C4Straight or branched alkyl, fluorine-containing C1~C4Straight chain or branch Alkyl group, hydroxyl, C1~C3Straight or branched alkoxyl, trifluoromethanesulfonic acid base or C6~C10It is a kind of in aromatic ring yl；
Or,
R1, R4, R5, R6And R7It is respectively and independently selected from：Hydrogen or C1~C3It is a kind of in straight or branched alkyl, R2And R3Be combined asCurve mark is substitution position, and it is relation " simultaneously " with parent benzene.
2. coumarin derivative as claimed in claim 1, it is characterised in that wherein, R1~R7It is respectively and independently selected from：H, halogen, C1 ~C4Straight or branched alkyl, fluorine-containing C1~C4Straight or branched alkyl, hydroxyl, C1~C3Straight or branched alkoxyl, trifluoro Methanesulfonic acid base, it is a kind of in phenyl or naphthyl.
3. coumarin derivative as claimed in claim 2, it is characterised in that wherein, R1, R2And R3It is respectively and independently selected from：H, halogen Element, C1~C4Straight or branched alkyl, hydroxyl, C1~C3Straight or branched alkoxyl, in trifluoromethanesulfonic acid base or phenyl or naphthyl It is a kind of；
R4, R5, R6And R7It is respectively and independently selected from：H, halogen, C1~C4Straight or branched alkyl, fluorine-containing C1~C4Straight or branched Alkyl or C1~C3It is a kind of in straight or branched alkoxyl.
4. coumarin derivative as claimed in claim 3, it is characterised in that wherein, R1, R2And R3It is respectively and independently selected from：H, halogen Element, methyl, normal-butyl, hydroxyl, methoxyl group are a kind of in trifluoromethanesulfonic acid base or phenyl or naphthyl；
R4, R5, R6And R7It is respectively and independently selected from：It is a kind of in H, halogen, methyl, the tert-butyl group, trifluoromethyl or methoxyl group.
5. coumarin derivative as claimed in claim 1, it is characterised in that described coumarin derivative is chemical combination shown in Formulas I A Thing：
In Formulas I A, R1, R4, R5, R6And R7It is respectively and independently selected from：It is a kind of in hydrogen or methyl.
A kind of 6. method for preparing the coumarin derivative as described in any one in Claims 1 to 5, it is characterised in that described Method comprises the following steps：
(1) as shown in Formula II shown in preparation of compounds of formula III the step of compound；With
(2) the step of compound is with one of the reaction of compound shown in formula IV a or formula IV b, obtained object as shown in formula III；
Or,
(1) as shown in Formula V shown in preparation of compounds of formula VI the step of compound；
(2) shown in preparation of compounds of formula VII shown in Formula IV the step of compound；
(3) shown in preparation of compounds of formula VIII shown in Formula VII the step of compound；
(4) shown in preparation of compounds of formula IX shown in Formula VIII the step of compound；And
(5) compound shown in compound shown in Formula IX and formula IV a or formula IV b is reacted, the step of the two of object are made；
Wherein, R1~R7Implication it is identical with described in any one in Claims 1 to 5；Described " one of object " is Formulas I institute Show compound, described " two of object " are compound shown in Formulas I A.
7. method as claimed in claim 6, it is characterised in that methods described comprises the following steps：
(1) under the conditions of with the presence of acetic anhydride and sodium acetate and 150 DEG C, compound shown in Formula II in aprotic organic solvent, Kept for six hours in 150 DEG C of states, obtain compound shown in formula III；
(2) under the conditions of with the presence of inert gas and copper trifluoromethanesulfcomposite and 100 DEG C, compound and formula IV a as shown in formula III Or compound shown in formula IV b is reacted in aprotic organic solvent, obtains one of object；
Or,
(1) under the conditions of with the presence of NaH and 0 DEG C, compound and CH as shown in Formula V3I reacts, and obtains compound shown in Formula IV；
(2) under the conditions of with the presence of n-BuLi and -78 DEG C, compound is reacted with DMF in THF as shown in Formula IV, obtains formula Compound shown in VII；
(3) there is excessive AlCl3In the presence of and room temperature condition under, compound shown in Formula VII is in halogenated alkyl solvent, in anhydrous and oxygen-free State keep at least 8h, obtain compound shown in Formula VIII；
(4) under the conditions of with the presence of acetic anhydride and sodium acetate and 150 DEG C, compound is in aprotic organic solvent shown in Formula VIII In, kept for six hours in 150 DEG C of states, obtain compound shown in Formula IX；And
(5) under the conditions of with the presence of inert gas and copper trifluoromethanesulfcomposite and 100 DEG C, as shown in Formula IX compound and formula IV a or Compound shown in formula IV b is reacted in aprotic organic solvent, obtains the two of object；
Described " one of object " is compound shown in Formulas I, and described " two of object " are compound shown in Formulas I A.
8. application of the coumarin derivative as organic pigment as described in any one in Claims 1 to 5.
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