CN104073017B - Organic dye sensitized dose, preparation method and the application in photoelectric conversion - Google Patents
Organic dye sensitized dose, preparation method and the application in photoelectric conversion Download PDFInfo
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- CN104073017B CN104073017B CN201410122668.3A CN201410122668A CN104073017B CN 104073017 B CN104073017 B CN 104073017B CN 201410122668 A CN201410122668 A CN 201410122668A CN 104073017 B CN104073017 B CN 104073017B
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- 206010070834 Sensitisation Diseases 0.000 claims abstract description 5
- 230000008313 sensitization Effects 0.000 claims abstract description 5
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- -1 cyano Chemical group 0.000 claims description 37
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 claims description 32
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- LWLSVNFEVKJDBZ-UHFFFAOYSA-N N-[4-(trifluoromethoxy)phenyl]-4-[[3-[5-(trifluoromethyl)pyridin-2-yl]oxyphenyl]methyl]piperidine-1-carboxamide Chemical compound FC(OC1=CC=C(C=C1)NC(=O)N1CCC(CC1)CC1=CC(=CC=C1)OC1=NC=C(C=C1)C(F)(F)F)(F)F LWLSVNFEVKJDBZ-UHFFFAOYSA-N 0.000 claims description 21
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- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 claims description 19
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- 229940126142 compound 16 Drugs 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
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- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 claims description 13
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 6
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 claims description 6
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- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 6
- 125000003282 alkyl amino group Chemical group 0.000 claims 1
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Classifications
-
- 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
-
- 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
- C09B17/00—Azine dyes
- C09B17/04—Azine dyes of the naphthalene series
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/148—Stilbene dyes containing the moiety -C6H5-CH=CH-C6H5
-
- 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
- C09B57/001—Pyrene 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/004—Diketopyrrolopyrrole dyes
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Abstract
The invention discloses organic dye sensitized dose a kind of, preparation method and the applications in its photoelectric conversion.The present invention provides organic dye sensitized dose of one kind, and general formula is shown in formula I；Wherein, A is short of electricity subelement, is electron acceptor；D is electron rich unit, is electron donor；N is electron neutral organic structure ele, does not have apparent push-and-pull electronic capability；π is the unit of connection conjugated structure；Ar is the conjugation assembly of two or more being conjugated in aromatic ring chromophore units either these structural units；B is to refer to mutually to be bonded with the nanometer micropore surface of dye sensitization battery light electricity anode, thus the structural unit that will contaminate the electron-transport that quick agent molecule excites after visible and ultraviolet light and go out to be formed electric current；N is 1,2,3,4,5 or 6.
Description
Technical field
The present invention relates to organic dye sensitized dose, preparation method and the applications in photoelectric conversion.
Background technique
The potential collision hazard of the energy and ecological environment it is continuous deteriorate so that new energy of the exploitation including solar energy including with can
The renewable sources of energy become a key subjects in worldwide, and what all life were all based on solar energy on the earth (passes through algae
The photosynthesis of class plant is realized), electric energy is that safely and effectively energy form (passes through the widely used one kind of current human society
Various power stations, battery and electric appliance are realized), photovoltaic energy conversion and energy storing technology are that the energy with essence meaning solves
Scheme.Currently, most important part is still to carry out around crystalline silicon in photovoltaic cell technical research and Materials, silicon substrate
The solar battery of material requires material purity high, equipment and cost of manufacture valuableness；It is used in its complete set of equipments manufacturing process
The factors such as material and the environmental pollution of manufacturing process bring, old equipment and component recovery processing are this kind of battery apparatus after supervention
The main bottleneck of exhibition.In order to adapt to solar battery high efficiency, low cost, large-scale production and the actual needs used, greatly
Power develops amorphous silicon, cadmium telluride, copper and indium gallium tin, organic semiconductor thin-film battery and dye-sensitized solar cells and is researching and developing
Major domain and direction.Dye-sensitized solar cells (B.O ' Regan, M.Nature, 1991,353,737-740)
Manufacture craft is relatively easy, manufacturing process energy consumption is few, and equipment requirement is easier to reach；Its main material cost is cheap,
(having the photoelectric conversion ability to work under room light and low light condition) good to various intensitv light adaptability, portable removable
Segment market product orientation advantage in terms of dynamic electric appliance and rechargable power supplies, is likely to become the master of a kind of following solar battery
The property led product.Light-sensitive coloring agent is an important component of dye-sensitized solar cells, light of the dyestuff performance for battery
Photoelectric transformation efficiency is most important, at present using it is more be ruthenium complex light-sensitive coloring agent N719(M.et al
J.Am.Chem.Soc.1993,115,6382-6390).It is various in order to find efficient light-sensitive coloring agent of the substitution containing noble ruthenium
The organic photosensitive agent dye molecule of various kinds be synthesized (P.Bauerle, et al Angew.Chem.Int.Ed.2009,
48,2474-2499).It by design and rational to organic dye sensitized agent molecule structure and rationally cuts out, different conjugation is selected to tie
The fragrant chromophore (Ar) of structure, conjugated structure connection unit and electron rich unit (electron donor, D), short of electricity subelement (electronics by
Body, A), or neutral organic structure ele (neutral body, N) constructs dye-sensitized molecules, is expected to rationally to change the vertical of molecule
Body structure reduces the nonplanarity for contaminating quick agent molecule, to reduce dyestuff in TiO2The pi-pi accumulation on surface acts on；It can prepare
What is needed has the organic dye molecule of wider absorption spectrum, stronger photoelectric current, so that enough adjusting electronics are logical in transmission
Locomotivity in road improves the photoelectric conversion efficiency of device.Chinese patent CN102816132A and CN102532032A are disclosed
Two class novel organic dye sensitizers, enrich organic dye sensitized dose of type, embody organic dyestuff structure and be imbued with change
Change and the excellent feature of photoelectric conversion performance.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome existing organic dye sensitized dose of light, heat and chemical stability
The defects of poor and provide organic dye sensitized dose a kind of, preparation method and the application in photoelectric conversion.Of the invention is organic
Dye sensitizing agent has good light, heat, chemical stability, can be used as photosensitive in commercialization dye-sensitized solar cells product
Agent uses.
The present invention provides organic dye sensitized dose of one kind, and general formula is shown in formula I: where A(Acceptor) it is short of electricity
Subelement is electron acceptor；D(Donor it is) electron rich unit, is electron donor；It N(Neutral) is the organic knot of electron neutral
Structure unit does not have apparent push-and-pull electronic capability；π (conjugated link) is the unit of connection conjugated structure；Ar is
The conjugation assembly of two or more being conjugated in aromatic ring chromophore units either these structural units；B
(Binding Group) is to refer to mutually to be bonded with the nanometer micropore surface of dye sensitization battery light electricity anode, so that quick dose will be contaminated
The electron-transport that molecule excites after visible and ultraviolet light goes out to form the structural unit of electric current；N be 1,2,3,4,5 or
6；
In the present invention, the A(Acceptor) preferably following any structure substituent group form:
Wherein, R1、R2、R3、R6、R7、R44、R47And R48It is independent to select hydrogen, C1-4Alkyl (preferably methyl), C1-4's
Alkoxy (preferably methoxyl group), C5-10Aryl (preferably phenyl), trifluoromethyl replace C5-10Aryl (preferably trifluoromethyl
One or more of substituted phenyl) and trifluoromethyl；R4And R5It is independently selected from hydrogen, C1-4Alkyl (preferably first
Base), C1-4One or more of alkoxy (preferably methoxyl group), halogen (preferably F), cyano, formoxyl and trifluoromethyl；
R8、R9、R10、R11、R12、R13、R14、R45And R46Independent is C5-10Alkyl (preferably).
In the present invention, the A(Acceptor) further preferably following any structure substituent group form:
In the present invention, the A(Acceptor) any substituent group still further preferably as follows:
In the present invention, any substituent group A still further preferably as follows:
In the present invention, the D(Donor) preferably following any structure substituent group form:
Wherein, R15Selected from hydrogen, C1-4Alkyl, C1-10Alkoxy (preferably methoxyl group or) andOne or more of, wherein n is the integer of 1-10；R16Selected from C1-4Alkyl (preferably methyl) and C6-10's
One or two of aryl (preferably phenyl)；R17、R18、R19And R20It is independently selected from hydrogen, C1-6Alkyl (preferably), C1-6Alkoxy (preferably methoxyl group or) and C1-6Alkoxy replace phenyl (preferablyOrOne or more of)；R21And R22It is independently selected from hydrogen, C1-4Alkyl (preferably methyl, second
Base, propyl, isopropyl or tert-butyl), C6-10Aryl (preferably phenyl), C1-4Alkoxy (preferably methoxyl group, ethyoxyl, third
Oxygroup, isopropoxy or tert-butoxy) and C1-4Alkyl amino (preferably methylamino, ethylamino- or Propylamino) in one or
It is multiple；R23、R24、R25、R26And R27It is independently selected from hydrogen, C1-4Alkyl and C1-4One or more of alkoxy.
In the present invention, the D(Donor) further preferably following any structure substituent group form:
In the present invention, the D(Donor) any substituent group still further preferably as follows:
In the present invention, the D(Donor) any substituent group still further preferably as follows:
In the present invention, the D(Donor) any substituent group still further preferably as follows:
In the present invention, the N(Neutral) any substituent group preferably as follows:
C1-20Linear or branched alkyl group (preferably
Or), the C that is replaced by one or more halogens1-4The alkyl (C preferably replaced by one or more fluorine atoms1-4
Alkyl, further preferablyC1-6Alkyl amino (preferably
), C1-6Sodium alkyl sulfonate (preferably),(preferably),(preferablyWherein m is the integer (preferably 1,2 of 1-10
Or 3),
WithWherein R28For C1-20
Linear or branched alkyl group.
In the present invention, the N(Neutral) any substituent group further preferably as follows:
In the present invention, the substituent group form of the preferably following any structure of the π (conjugated link):
C5-10Aryl,
Wherein, R29And R30One or more be independently selected from hydrogen, phenyl, furyl, pyrrole radicals and thienyl
It is a；R31、R32And R33It is independently selected from hydrogen, C1-10Linear or branched alkyl group (preferably methyl, ethyl, propyl, butyl, penta
Base or hexyl), C1-10Straight or branched alkoxyl (preferably), thienyl and by C1-6Alkyl-substituted thiophene
One or more of pheno base；R34、R35、R36、R37、R38And R39It is independently selected from hydrogen, C1-10Linear or branched alkyl group
And C1-10One or more of straight or branched alkoxyl.
In the present invention, the substituent group form of the further preferably following any structure of the π (conjugated link):
In the present invention, any substituent group π (conjugated link) still further preferably as follows:
In the present invention, any substituent group π still further preferably as follows:
In the present invention, any substituent group π still further preferably as follows:
In the present invention, the substituent group form of the preferably following any structure of the Ar:
In the present invention, any substituent group Ar further preferably as follows:
In the present invention, the substituent group Ar still further preferably as follows:
In the present invention, the B(Binding Group) preferably following any structure substituent group form:
Wherein, R40And R41It is independently selected from hydrogen, carboxyl, hydroxyl, C2-6Alkynyl (preferably acetenyl) and C1-4Carboxylic
Base is (preferablyOne or more of)；R42Selected from carboxyl,Cyano, C6-10Aryl (preferably benzene
Base), the C that is replaced by one or more cyano6-10Aryl (phenyl preferably replaced by one or more cyano) and by one
Or the C that multiple carboxyls replace6-10One or more of aryl (phenyl preferably replaced by one or more carboxyls)；R43For
C1~C9Straight chain or branched paraffin.
Heretofore described B(binding group) further preferred any substituent group as follows:
In the present invention, the B(binding group) any substituent group still further preferably as follows:
Heretofore described B(binding group) substituent group still further preferably as follows:
In the present invention, the Ar can be by any key to close with the B(binding group) or the π
The mode of reason is attached；Described D, the A or the N and π can be attached by any key with reasonable manner.
It is described organic dye sensitized dose as shown in general formula I in the present invention, preferably there is the chemical combination of following any general formula
Object:
Wherein π1、π2Definition define identical, π with above-mentioned π1With π2It can be the same or different.
It is described organic dye sensitized dose as shown in general formula I in the present invention, further preferably following any compound:
Heretofore described organic dye sensitized dose can be with known compound according to the difference of specific molecular structure
Initial feed prepares described accordingly organic dye sensitized dose in conjunction with the conventional reaction method and reaction condition of this field
In particular compound.
The present invention also provides the preparation method of the terthienyl general formula compound 1 when Ar is thienyl, π is thienyl,
Itself the following steps are included: in organic solvent, by compound 2 withCondensation reaction is carried out, compound 1 is obtained；
Wherein, the definition of A, B and D are same as above.
The method of prepare compound 1 can be using the conventional method and condition of such condensation reaction in this field, the present invention
In particularly preferably following reaction method and condition:
It can be carried out under gas shield in the method for prepare compound 1, when the method for prepare compound 1 can be in gas
Protection is lower when carrying out, one of the preferred nitrogen of gas, argon gas, helium and neon described in " under the gas shield " or
It is a variety of.
In the method for prepare compound 1, the preferred carboxylic acids organic solvent of the organic solvent, the carboxylic acids has
The preferred acetic acid of solvent.
In the method for prepare compound 1, the compound 2 and the mass volume ratio of the organic solvent are preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
It is described in the method for prepare compound 1With the molar ratio preferably 1~5 of the compound 2.
In the method for prepare compound 1, preferably 0~150 DEG C of the temperature of the condensation reaction, further preferred 100
DEG C~150 DEG C.
In the method for prepare compound 1, the process of the condensation reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, generally with describedIt is reaction end when disappearance, the reaction time is excellent
It selects 1 hour~24 hours, further preferred 1 hour~10 hours.
In the method for prepare compound 1, the condensation reaction preferably existing for the ammonium acetate under the conditions of carry out, it is described
Ammonium acetate and the compoundMolar ratio preferably 1~5.
Following post-processing step is preferably included in the method for prepare compound 1: after reaction, crude product is obtained by filtration,
Pillar layer separation obtains product after purification, the method and condition of pillar layer separation can using in this field the generic operation it is normal
Advise method and condition.
In the method for the prepare compound, the compound 2 can using method (1) method (2) or
Method (3) preparation:
Method (1) preferably includes following steps: in a solvent, under the conditions of alkali and catalyst are existing, by compound 3 and changing
It closes object 4 and carries out Suzuki coupling reaction, obtain the compound 2；
Method (2) preferably includes following steps: in a solvent, under the conditions of alkali and catalyst are existing, by compound 8 and changing
It closes object 9 and carries out Suzuki coupling reaction, obtain the compound 2；
Method (3) preferably includes following steps: in organic solvent, compound 11 and acid being carried out oxidation reaction
Close object 2；
Wherein, the definition of A and D is same as above.
The method (1) of prepare compound 2 can be using the conventional method and item of such Suzuki coupling reaction in this field
Part, particularly preferably following reaction method and condition in the present invention:
The method (1) of prepare compound 2 can carry out under gas shield, when the method (1) of prepare compound 2 is in gas
Protection is lower when carrying out, one of the preferred nitrogen of gas, argon gas, helium and neon described in " under the gas shield " or
It is a variety of.
In the method (1) of prepare compound 2, the preferred ether solvent of the solvent and/or water, the ether solvent
It is preferred that tetrahydrofuran；When using the mixed solvent of ether solvent and water, the volume ratio of the ether solvent and water preferably 1
~10, further preferred 1~5.
In the method (1) of prepare compound 2, the compound 4 and the mass volume ratio of the solvent are preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
In the method (1) of prepare compound 2, the preferred inorganic base of the alkali, the preferred potassium carbonate of the inorganic base.
In the method (1) of prepare compound 2, the molar ratio preferably 1~5 of the alkali and the compound 4.
In the method (1) of prepare compound 2, the catalyst preferably four triphenyl phosphorus palladiums.
In the method (1) of prepare compound 2, the molar ratio of the catalyst and the compound 4 is preferred
0.01~1, further preferred 0.01~0.1.
In the method (1) of prepare compound 2, the molar ratio preferably 1 of the compound 3 and the compound 4
~5.
In the method (1) of prepare compound 2, preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, into one
Preferably 40 DEG C~90 DEG C of step.
In the method (1) of prepare compound 2, the process of the Suzuki coupling reaction can be using in this field
Routine monitoring method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 4,
Reaction time preferably 1 hour~24 hours, further preferred 1 hour~10 hours.
Following post-processing step is preferably included in the method (1) of prepare compound 2: after reaction, removing solvent, column color
Isolated product after purification is composed, the method and condition of pillar layer separation can be using the routine side of the generic operation in this field
Method and condition.
In the method for the prepare compound 1, following steps are preferably included: in organic solvent, by compound 5
Substitution reaction is carried out with N- bromo-succinimide (NBS), obtains the compound 4；
Wherein, the definition of A, B and D are same as above.
The method of prepare compound 4 can be using the conventional method and condition of such substitution reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound 4, the organic solvent preferred amide class solvent, the amide solvent is excellent
Select N,N-dimethylformamide (DMF)；
In the method for prepare compound 4, the compound 5 and the mass volume ratio of the organic solvent are preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 4, the molar ratio of the N- bromo-succinimide and the compound 5
It is preferred that 1~3.
In the method for prepare compound 4, preferably 0~100 DEG C of the temperature of the substitution reaction, further preferred 0 DEG C
~40 DEG C.
In the method for prepare compound 4, the process of the substitution reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 5, the reaction time
It is preferred that 1 hour~48 hours, further preferred 1 hour~24 hours.
The method of prepare compound 4 preferably existing for the radical initiator under the conditions of carry out, the free radical causes
The preferred benzoyl peroxide of agent or azodiisobutyronitrile.
The method of prepare compound 4 preferably includes following post-processing step: after reaction, adds water quenching reaction, filters,
Obtain compound 4.
In the method for the prepare compound 1, preferably include following steps: in a solvent, alkali and catalyst are deposited
Under the conditions, compound 6 and compound B-11 are subjected to Suzuki coupling reaction, obtain the compound 5；
Wherein, the definition of A, B and D are same as above.
The method of prepare compound 5 can use the conventional method and condition of such Suzuki coupling reaction in this field,
Particularly preferred following reaction method and condition in the present invention:
The method of prepare compound 5 can carry out under gas shield, when the method for prepare compound 5 is under gas shield
When progress, one of the preferred nitrogen of gas, argon gas, helium and neon or a variety of described in " under the gas shield ".
In the method for prepare compound 5, the preferred ether solvent of the solvent and/or water, the ether solvent is excellent
Select tetrahydrofuran；When using the mixed solvent of ether solvent and water, the volume ratio of the ether solvent and water preferably 1~
10, further preferred 1~5.
In the method for prepare compound 5, the preferred 1mg/mL of mass volume ratio of the compound 6 and the solvent
~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 5, the preferred inorganic base of the alkali, the preferred potassium carbonate of the inorganic base.
In the method for prepare compound 5, the molar ratio preferably 1~5 of the alkali and the compound 6.
In the method for prepare compound 5, the catalyst preferably four triphenyl phosphorus palladiums.
In the method for prepare compound 5, the molar ratio preferably 0.01 of the catalyst and the compound 6~
1, further preferred 0.01~0.1.
In the method for prepare compound 5, the molar ratio preferably 1 of the compound 6 and the compound B-11~
5。
It is preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, further excellent in the method for prepare compound 5
Select 40 DEG C~90 DEG C.
In the method for prepare compound 5, the process of the Suzuki coupling reaction can be using normal in this field
Rule monitoring method (such as TLC, HPLC or NMR) are monitored, as reaction end when generally being disappeared using the compound 6, instead
Preferably 1 hour~24 hours, further preferred 1 hour~10 hours between seasonable.
Following post-processing step is preferably included in the method for prepare compound 5: after reaction, removing solvent, column chromatography
The method and condition of isolated product after purification, pillar layer separation can be using the conventional method of the generic operation in this field
And condition.
In the method for the prepare compound 1, following steps are preferably included: in organic solvent, alkali and catalyst
Under the conditions of existing, compound 7 and duplex pinacol borate (CAS:73183-34-3) are subjected to nucleophilic substitution, obtained
The compound 6；
Wherein, A is defined as above described.
The method of prepare compound 6 can be using the conventional method and condition of such nucleophilic substitution in this field, this
Particularly preferred following reaction method and condition in invention:
In the method for prepare compound 6, the preferred ether solvent of the organic solvent, the ether solvent preferably 1,
4- dioxane (dioxanes)；
In the method for prepare compound 6, the compound 7 and the mass volume ratio of the organic solvent are preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 6, the molar ratio of the duplex pinacol borate and the compound 7
It is preferred that 1~3.
In the method for prepare compound 6, the preferred inorganic base of the alkali；The preferred potassium acetate of the inorganic base.
In the method for prepare compound 6, the molar ratio preferably 1~5 of the alkali and the compound 7.
In the method for prepare compound 6, the catalyst preferably [1,1'- bis- (diphenylphosphine) ferrocene] dichloride
Palladium (Pd (dppf) Cl2).
In the method for prepare compound 6, the molar ratio preferably 0.01 of the catalyst and the compound 7~
1, further preferred 0.01~0.1.
In the method for prepare compound 6, preferably 0~150 DEG C of the temperature of the nucleophilic substitution, further preferably
50 DEG C~100 DEG C.
In the method for prepare compound 6, the process of the nucleophilic substitution can be using the routine in this field
Monitoring method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 7, reaction
Time preferably 1 hour~24 hours.
Following post-processing step is preferably included in the method for prepare compound 6: after reaction, removing solvent, column chromatography
The method and condition of isolated product after purification, pillar layer separation can be using the conventional method of the generic operation in this field
And condition.
In the method for the prepare compound 1, preferably include following steps: in a solvent, alkali and catalyst are deposited
Under the conditions, compound 8 and 2- bromothiophene are subjected to Suzuki coupling reaction, obtain the compound 7；
Wherein, the definition of A is same as above.
The method of prepare compound 7 can use the conventional method and condition of such Suzuki coupling reaction in this field,
Particularly preferred following reaction method and condition in the present invention:
The method of prepare compound 7 can carry out under gas shield, when the method for prepare compound 7 is under gas shield
When progress, one of the preferred nitrogen of gas, argon gas, helium and neon described in " under the gas shield " or
It is a variety of.
In the method for prepare compound 7, the preferred ether solvent of the solvent and/or water, the ether solvent is excellent
Select tetrahydrofuran；When using the mixed solvent of ether solvent and water, the volume ratio of the ether solvent and water selects 1~
10, further preferred 1~5.
In the method for prepare compound 7, the preferred 1mg/mL of mass volume ratio of the compound 8 and the solvent
~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 7, the preferred inorganic base of the alkali, the preferred potassium carbonate of the inorganic base.
In the method for prepare compound 7, the molar ratio preferably 1~5 of the alkali and the compound 8.
In the method for prepare compound 7, the catalyst preferably four triphenyl phosphorus palladiums.
In the method for prepare compound 7, the molar ratio preferably 0.01 of the catalyst and the compound 8~
1, further preferred 0.01~0.1.
In the method for prepare compound 7, the molar ratio preferably 1 of the compound 8 and the 2- bromothiophene~
5。
It is preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, further excellent in the method for prepare compound 7
Select 40 DEG C~90 DEG C.
In the method for prepare compound 7, the process of the Suzuki coupling reaction can be using normal in this field
Rule monitoring method (such as TLC, HPLC or NMR) are monitored, and are reaction when generally being disappeared with the compound 2- bromothiophene
Terminal, the reaction time preferably 1 hour~24 hours, further preferred 1 hour~10 hours.
Following post-processing step is preferably included in the method for prepare compound 7: after reaction, removing solvent, column chromatography
The method and condition of isolated product after purification, pillar layer separation can be using the conventional method of the generic operation in this field
And condition.
The method (2) of prepare compound 2 can be using the conventional method and item of such Suzuki coupling reaction in this field
Part, particularly preferably following reaction method and condition in the present invention:
The method (2) of prepare compound 2 can carry out under gas shield, when the method (2) of the prepare compound 2
When being carried out under gas shield, one of the preferred nitrogen of the gas, argon gas, helium and neon or a variety of.
In the method (2) of prepare compound 2, the preferred ether solvent of the solvent and/or water, the ether solvent
It is preferred that tetrahydrofuran；When using the mixed solvent of ether solvent and water, the volume ratio of the ether solvent and water preferably 1
~10, further preferred 1~5.
In the method (2) of prepare compound 2, the compound 9 and the mass volume ratio of the solvent are preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
In the method (2) of prepare compound 2, the preferred inorganic base of the alkali, the preferred potassium carbonate of the inorganic base.
In the method (2) of prepare compound 2, the molar ratio preferably 1~5 of the alkali and the compound 9.
In the method (2) of prepare compound 2, the catalyst preferably four triphenyl phosphorus palladiums.
In the method (2) of prepare compound 2, the molar ratio of the catalyst and the compound 9 is preferred
0.01~1, further preferred 0.01~0.1.
In the method (2) of prepare compound 2, the molar ratio preferably 1 of the compound 8 and the compound 9
~5.
In the method (2) of prepare compound 2, preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, into one
Preferably 40 DEG C~90 DEG C of step.
In the method (2) of prepare compound 2, the process of the Suzuki coupling reaction can be using in this field
Routine monitoring method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 9,
Reaction time preferably 1 hour~24 hours, further preferred 1 hour~10 hours.
Following post-processing step is preferably included in the method (2) of prepare compound 2: after reaction, removing solvent, column color
Isolated product after purification is composed, the method and condition of pillar layer separation can be using the routine side of the generic operation in this field
Method and condition.
In the method for the prepare compound 1, preferably include following steps: in a solvent, alkali and catalyst exist
Under conditions of, by compound Q ' and the progress Suzuki coupling reaction of compound 3, obtain the compound 9；
Wherein, D is defined as above described.
The method of prepare compound 9 can use the conventional method and condition of such Suzuki coupling reaction in this field,
Particularly preferred following reaction method and condition in the present invention:
The method of prepare compound 9 can carry out under gas shield, when the method for prepare compound 9 is under gas shield
When progress, one of the preferred nitrogen of gas, argon gas, helium and neon or a variety of described in " under the gas shield ".
In the method for prepare compound 9, the preferred ether solvent of the solvent and/or water, the ether solvent is excellent
Select tetrahydrofuran；When using the mixed solvent of ether solvent and water, the volume ratio of the ether solvent and water preferably 1~
10, further preferred 1~5.
In the method for prepare compound 9, the compound Q ' the preferred 1mg/ of mass volume ratio with the solvent
ML~100mg/mL, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 9, the preferred inorganic base of the alkali, the preferred potassium carbonate of the inorganic base.
In the method for prepare compound 9, the alkali and the compound Q ' molar ratio preferably 1~5.
In the method for prepare compound 9, the catalyst preferably four triphenyl phosphorus palladiums.
In the method for prepare compound 9, the catalyst and the compound Q ' molar ratio preferably 0.01
~1, further preferred 0.01~0.1.
In the method for prepare compound 9, the compound 3 and the compound Q ' molar ratio preferably 1~
5。
It is preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, further excellent in the method for prepare compound 9
Select 40 DEG C~90 DEG C.
In the method for prepare compound 9, the process of the Suzuki coupling reaction can be using normal in this field
Rule monitoring method (such as TLC, HPLC or NMR) are monitored, as reaction end when generally being disappeared using the compound 3, instead
Preferably 1 hour~24 hours, further preferred 1 hour~10 hours between seasonable.
Following post-processing step is preferably included in the method for prepare compound 9: after reaction, removing solvent, column chromatography
The method and condition of isolated product after purification, pillar layer separation can be using the conventional method of the generic operation in this field
And condition.
In the method for the prepare compound 1, following steps are preferably included: in organic solvent, by compound
P ' and N- bromo-succinimide (NBS) carry out substitution reaction, obtain the compound Q '；
The method of prepare compound Q ' can be using the conventional method and condition of such substitution reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound Q ', the organic solvent preferred amide class solvent, the amide solvent
It is preferred that N,N-dimethylformamide (DMF)；
In the method for prepare compound Q ', the compound P ' and the mass volume ratio of the organic solvent are preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound Q ', the molar ratio of the N- bromo-succinimide and the compound P '
Value preferably 1~3.
In the method for prepare compound Q ', preferably 0~100 DEG C of the temperature of the substitution reaction, further preferred 0 DEG C
~40 DEG C.
In the method for prepare compound Q ', the process of the substitution reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 11, the reaction time
It is preferred that 1 hour~48 hours, further preferred 1 hour~24 hours.
The method of prepare compound Q ' preferably existing for the radical initiator under the conditions of carry out, the free radical causes
The preferred benzoyl peroxide of agent or azodiisobutyronitrile.
The method of prepare compound Q ' preferably includes following post-processing step: after reaction, adding water quenching reaction, mistake
Filter, obtains compound Q '.
In the method for the prepare compound 1, preferably include following steps: in a solvent, alkali and catalyst are deposited
Under the conditions, compound 10 and compound B-11 are subjected to Suzuki coupling reaction, obtain the compound P '；
The method of prepare compound P ' can use the conventional method and condition of such Suzuki coupling reaction in this field,
Particularly preferred following reaction method and condition in the present invention:
The method of prepare compound P ' can carry out under gas shield, when the method for prepare compound P ' is in gas shield
When lower progress, one of the preferred nitrogen of gas, argon gas, helium and neon or more described in " under the gas shield "
Kind.
In the method for prepare compound P ', the preferred ether solvent of the solvent and/or water, the ether solvent is excellent
Select tetrahydrofuran；When using the mixed solvent of ether solvent and water, the volume ratio of the ether solvent and water preferably 1~
10, further preferred 1~5.
In the method for prepare compound P ', the preferred 1mg/ of mass volume ratio of the compound 10 and the solvent
ML~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound P ', the preferred inorganic base of the alkali, the preferred potassium carbonate of the inorganic base.
In the method for prepare compound P ', the molar ratio preferably 1~5 of the alkali and the compound 10.
In the method for prepare compound P ', the catalyst preferably four triphenyl phosphorus palladiums.
In the method for prepare compound P ', the molar ratio preferably 0.01 of the catalyst and the compound 10
~1, further preferred 0.01~0.1.
In the method for prepare compound P ', the molar ratio preferably 1 of the compound B-11 and the compound 10
~5.
In the method for prepare compound P ', preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, further
It is preferred that 40 DEG C~90 DEG C.
In the method for prepare compound P ', the process of the Suzuki coupling reaction can be using normal in this field
Rule monitoring method (such as TLC, HPLC or NMR) are monitored, as reaction end when generally being disappeared using the compound B-11, instead
Preferably 1 hour~24 hours, further preferred 1 hour~10 hours between seasonable.
Following post-processing step is preferably included in the method for prepare compound P ': after reaction, removing solvent, column chromatography
The method and condition of isolated product after purification, pillar layer separation can be using the conventional method of the generic operation in this field
And condition.
The method (3) of prepare compound 2 can be using the conventional method and condition of such oxidation reaction in this field, this hair
Particularly preferred following reaction method and condition in bright:
In the method (3) of prepare compound 2, the preferred halogenated hydrocarbon solvent of the solvent, the halogenated hydrocarbon is molten
The preferred chlorinated hydrocarbon solvent of agent, the preferred methylene chloride of the chlorinated hydrocarbon solvent.
In the method (3) of prepare compound 2, the compound 11 and the mass volume ratio of the solvent are preferred
1mg/mL~100mg/L, further preferred 10mg/mL~50mg/L.
In the method (3) of prepare compound 2, the preferred inorganic acid of acid, the preferred hydrochloric acid of the inorganic acid；It is described
Hydrochloric acid mass percentage concentration preferably 10%~37%, the mass percentage concentration refers to that the quality of hydrogen chloride accounts for the total matter of hydrochloric acid
The percentage of amount.
In the method (3) of prepare compound 2, the molar ratio preferably 1~5 of the acid and the compound 11.
In the method (3) of prepare compound 2, preferably 0~100 DEG C of the temperature of the oxidation reaction, further preferred 0
DEG C~40 DEG C.
In the method (3) of prepare compound 2, the process of the oxidation reaction can be using the conventional prison in this field
Survey method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 11, when reaction
Between preferably 1 hour~24 hours.
Following post-processing step is preferably included in the method (3) of prepare compound 2: after reaction, it is left to adjust pH to 7
The right side, extraction obtain crude product and are used directly for reacting in next step.It adjusts pH and preferably uses inorganic base, the inorganic base is excellent
Select sodium bicarbonate.The method and condition of extraction can using the conventional method and condition of the generic operation in this field, extraction it is molten
The preferred halogenated hydrocarbon solvent of agent, the preferred chlorinated hydrocarbon solvent of the halogenated hydrocarbon solvent, the chlorinated hydrocarbon solvent are preferred
Methylene chloride.
In the method for the prepare compound 1, preferably uses method 1. or 2. method prepares the chemical combination
Object 11:
Method is 1.: in a solvent, under the conditions of catalyst is existing, compound 12 and compound 13 being carried out Suzuki coupling
Reaction obtains the compound 11；
Method is 2.: in a solvent, alkali and catalyst it is existing under the conditions of, compound 17 and compound 3 are subjected to Suzuki
Coupling reaction obtains the compound 11；
Wherein, the definition of A and D is same as above.
The method of prepare compound 11 1. can be using the conventional method and item of such Suzuki coupling reaction in this field
Part, particularly preferably following reaction method and condition in the present invention:
1. the method for prepare compound 11 can carry out under gas shield, when the method for prepare compound 11 is 1. in gas
Protection is lower when carrying out, one of the preferred nitrogen of gas, argon gas, helium and neon described in " under the gas shield " or
It is a variety of.
Prepare compound 11 method 1. in, the solvent preferred amide class solvent, the amide solvent is excellent
Select N,N-dimethylformamide and/or N.N- dimethyl acetamide.
Prepare compound 11 method 1. in, the compound 12 and the mass volume ratio of the solvent are preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
Prepare compound 11 method 1. in, the catalyst preferably four triphenyl phosphorus palladiums.
Prepare compound 11 method 1. in, the molar ratio of the catalyst and the compound 12 is preferred
0.01~1, further preferred 0.01~0.1.
Prepare compound 11 method 1. in, the molar ratio of the compound 13 and the compound 12 is preferred
1~5.
Prepare compound 11 method 1. in, preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, into one
Preferably 40 DEG C~90 DEG C of step.
Prepare compound 11 method 1. in, the process of the Suzuki coupling reaction can be using in this field
Routine monitoring method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 12,
Reaction time preferably 1 hour~24 hours.
1. preferably include following post-processing step in the method for prepare compound 11: after reaction, extraction removes solvent
Crude product is obtained, crude product pillar layer separation obtains product after purification.The method and condition of pillar layer separation can be using this
The conventional method and condition of the generic operation in field；The method and condition of extraction can be using the routine of the generic operation in this field
Method and condition, the preferred esters solvent of the solvent of extraction, the esters solvent ethyl acetate.
In the method for the prepare compound 1, preferably include following steps: in organic solvent, free radical draws
Under the conditions of sending out existing for agent, compound 14 and tributyltin chloride are subjected to substitution reaction, obtain the compound 13；
The method of prepare compound 13 can be using the conventional method and condition of such substitution reaction in this field, the present invention
In particularly preferably following reaction method and condition:
The method of prepare compound 13 can carry out under gas shield, when the method for prepare compound 13 can be in gas
When being carried out under protection, the preferred ether solvent of the organic solvent, the preferred tetrahydrofuran of the ether solvent (THF)；
In the method for prepare compound 13, the compound 14 and the mass volume ratio of the organic solvent are preferred
1mg/mL~100mg/mL, further preferred 1mg/mL~20mg/mL.
In the method for prepare compound 13, the molar ratio of the tributyltin chloride and the compound 14 is excellent
Select 1~3.
In the method for prepare compound 13, the preferred isopropylmagnesium chloride of the radical initiator.
In the method for prepare compound 13, the molar ratio of the radical initiator and the compound 14 is preferred
1~3.
In the method for prepare compound 13, preferably 0~100 DEG C of the temperature of the substitution reaction, further preferred 0 DEG C
~40 DEG C.
In the method for prepare compound 13, the process of the substitution reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, generally using the compound R ' disappear when as reaction end, the reaction time
It is preferred that 1 hour~48 hours, further preferred 1 hour~24 hours.
The method of prepare compound 13 preferably includes following post-processing step: after reaction, quenching reaction, extraction obtains
To compound 13, can be directly used for reacting in next step.The preferred aqueous ammonium chloride solution of reagent used by being quenched.The extraction can
With the preferred esters solvent of solvent used using the conventional method of the generic operation in this field, the extraction, the esters
Solvent ethyl acetate.
The method of prepare compound 13 preferably includes following steps: under gas shield, by being added drop-wise to of radical initiator
It closes in the solution that object 14 and organic solvent are formed, reaction a period of time (preferably 1 hour~3 hours), then by tributyltin chloride
It is added drop-wise in reaction system, carries out substitution reaction and obtain the compound 13.It is described by being added drop-wise to of radical initiator
Preferably -10 DEG C~0 DEG C of temperature in the solution that object 14 and organic solvent are formed is closed, it is described to be added drop-wise to tributyltin chloride instead
Answer preferably -10 DEG C~0 DEG C of temperature in system.
In the method for the prepare compound 1, following steps are preferably included: in organic solvent, existing for acid
Under the conditions of, compound 15 and carbonyl-protection base (preferably ethylene glycol) are subjected to condensation reaction, obtain the compound 14；
The method of prepare compound 14 can be using the conventional method and condition of such condensation reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound 14, the solvent preferred aromatic hydrocarbons class solvent, the aromatic hydrocarbon solvent is preferred
Toluene.
In the method for prepare compound 14, the preferred 1mg/ of mass volume ratio of the compound 15 and the solvent
ML~100mg/mL, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 14, the preferred organic acid of acid, the preferred p-methyl benzenesulfonic acid of the organic acid.
In the method for prepare compound 14, the molar ratio preferably 0.01 of the described acid and the compound 15~
0.1。
In the method for prepare compound 14, the hydroxy protecting agent preferred diol class compound, the glycol
The preferred ethylene glycol of class compound.
In the method for prepare compound 14, the molar ratio of the hydroxy protecting agent and the compound 15 is excellent
Select 1~5.
In the method for prepare compound 14, preferably 0~150 DEG C of the temperature of the condensation reaction, further preferred 80
DEG C~120 DEG C.
In the method for prepare compound 14, the process of the condensation reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 15, the reaction time
It is preferred that 1 hour~24 hours.
Following post-processing step is preferably included in the method for prepare compound 14: after reaction, alkali cleaning to pH7 or so,
Solvent is removed, pillar layer separation obtains product after purification.The preferred inorganic base of the alkali, the preferred bicarbonate of the inorganic base
Sodium.The method and condition of pillar layer separation can be using the conventional method and condition of the generic operation in this field.
In the method 1 of the prepare compound 1, preferably include following steps: in a solvent, alkali and catalyst are deposited
Under the conditions, compound 3 and compound 16 are subjected to Suzuki coupling reaction, obtain the compound 15；
Wherein, D is defined as above described.
The method of prepare compound 15 can use the conventional method and condition of such Suzuki coupling reaction in this field,
Particularly preferred following reaction method and condition in the present invention:
The method of prepare compound 15 can carry out under gas shield, when the method for prepare compound 15 is in gas shield
When lower progress, one of the preferred nitrogen of gas, argon gas, helium and neon or more described in " under the gas shield "
Kind.
In the method for prepare compound 15, the preferred ether solvent of the solvent and/or water, the ether solvent is excellent
Select tetrahydrofuran；When using the mixed solvent of ether solvent and water, the volume ratio of the ether solvent and water preferably 1~
10, further preferred 1~5.
In the method for prepare compound 15, the preferred 1mg/ of mass volume ratio of the compound 16 and the solvent
ML~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 15, the preferred inorganic base of the alkali, the preferred potassium carbonate of the inorganic base.
In the method for prepare compound 15, the molar ratio preferably 1~5 of the alkali and the compound 16.
In the method for prepare compound 15, the catalyst preferably four triphenyl phosphorus palladiums.
In the method for prepare compound 15, the molar ratio preferably 0.01 of the catalyst and the compound 16
~1, further preferred 0.01~0.1.
In the method for prepare compound 15, the molar ratio preferably 1 of the compound 3 and the compound 16~
5。
In the method for prepare compound 15, preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, further
It is preferred that 40 DEG C~90 DEG C.
In the method for prepare compound 15, the process of the Suzuki coupling reaction can be using normal in this field
Rule monitoring method (such as TLC, HPLC or NMR) are monitored, as reaction end when generally being disappeared using the compound 16, instead
Preferably 1 hour~24 hours, further preferred 1 hour~10 hours between seasonable.
The method of prepare compound 15 preferably includes following post-processing step: after reaction, removing solvent, column chromatography
The method and condition of isolated product after purification, pillar layer separation can be using the conventional method of the generic operation in this field
And condition.
In the method for the prepare compound 1, following steps are preferably included: in organic solvent, by compound
B1 and N- N-iodosuccinimide (NIS) carry out substitution reaction, obtain the compound 16；
The method of prepare compound 16 can be using the conventional method and condition of such substitution reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound 16, the organic solvent preferred amide class solvent, the amide solvent
It is preferred that N,N-dimethylformamide (DMF)；
In the method for prepare compound 16, the mass volume ratio of the compound B-11 and the organic solvent is preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 16, the molar ratio of the N- N-iodosuccinimide and the compound B-11
Value preferably 1~3.
In the method for prepare compound 16, preferably 0~100 DEG C of the temperature of the substitution reaction, further preferred 0 DEG C
~40 DEG C.
In the method for prepare compound 16, the process of the substitution reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 5, the reaction time
It is preferred that 1 hour~48 hours, further preferred 1 hour~24 hours.
The method of prepare compound 16 preferably includes following post-processing step: after reaction, adding water quenching reaction, mistake
Filter, obtains compound 16.
The method of prepare compound 11 2. can be using the conventional method and item of such Suzuki coupling reaction in this field
Part, particularly preferably following reaction method and condition in the present invention:
Prepare compound 11 method 2. in, the preferred nitrogen of gas described in " under the gas shield ", argon gas,
One of helium and neon are a variety of.
Prepare compound 11 method 2. in, the preferred ether solvent of the solvent and/or water, the ether solvent
It is preferred that tetrahydrofuran；When using the mixed solvent of ether solvent and water, the volume ratio of the ether solvent and water preferably 1
~10, further preferred 1~5.
Prepare compound 11 method 2. in, the compound 17 and the mass volume ratio of the solvent are preferred
1mg/mL~100mg/mL, further preferred 1mg/mL~20mg/L.
Prepare compound 11 method 2. in, the preferred inorganic base of the alkali, the preferred potassium carbonate of the inorganic base.
Prepare compound 11 method 2. in, the molar ratio preferably 1~5 of the alkali and the compound 17.
Prepare compound 11 method 2. in, the catalyst preferably four triphenyl phosphorus palladiums.
Prepare compound 11 method 2. in, the molar ratio of the catalyst and the compound 17 is preferred
0.01~1, further preferred 0.01~0.1.
Prepare compound 11 method 2. in, the molar ratio preferably 1 of the compound 3 and the compound 17
~5.
Prepare compound 11 method 2. in, preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, into one
Preferably 40 DEG C~90 DEG C of step.
Prepare compound 11 method 2. in, the process of the Suzuki coupling reaction can be using in this field
Routine monitoring method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 3,
Reaction time preferably 1 hour~24 hours, further preferred 1 hour~10 hours.
Following post-processing step is 2. preferably included in the method for prepare compound 11: after reaction, removing solvent, column color
Isolated product after purification is composed, the method and condition of pillar layer separation can be using the routine side of the generic operation in this field
Method and condition.
In the method 1 of the prepare compound 1, following steps are preferably included: in organic solvent, by compound
18 carry out substitution reaction with N- bromo-succinimide (NBS), obtain the compound 17；
The method of prepare compound 17 can be using the conventional method and condition of such substitution reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound 17, the organic solvent preferred amide class solvent, the amide solvent
It is preferred that N,N-dimethylformamide (DMF)；
In the method for prepare compound 17, the compound 18 and the mass volume ratio of the organic solvent are preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 17, the molar ratio of the N- bromo-succinimide and the compound 18
Value preferably 1~3.
In the method for prepare compound 17, preferably 0~100 DEG C of the temperature of the substitution reaction, further preferred 0 DEG C
~40 DEG C.
In the method for prepare compound 17, the process of the substitution reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 18, the reaction time
It is preferred that 1 hour~48 hours, further preferred 1 hour~24 hours.
The method of prepare compound 17 preferably existing for the radical initiator under the conditions of carry out, the free radical causes
The preferred benzoyl peroxide of agent or azodiisobutyronitrile.
The method of prepare compound 17 preferably includes following post-processing step: after reaction, adding water quenching reaction, mistake
Filter, obtains compound 17.
In the method for the prepare compound 1, the compound 18 can be prepared using method I or method II,
Method I its preferably include following steps: in a solvent, under the conditions of catalyst is existing, by compound S ' and chemical combination
Object 12 carries out Suzuki coupling reaction, obtains the compound 18；
Method II: in organic solvent, under the conditions of catalyst is existing, compound 19 and compound V ' are subjected to Suzuki
Coupling reaction obtains the compound 18；
The method I of prepare compound 18 can be carried out under gas shield, when the method I of prepare compound 18 is protected in gas
When being carried out under shield, one of the preferred nitrogen of gas, argon gas, helium and neon or more described in " under the gas shield "
Kind.
In the method I of prepare compound 18, the solvent preferred aromatic hydrocarbons class solvent, the aromatic hydrocarbon solvent is preferred
Toluene.
In the method I of prepare compound 18, the compound 12 and the mass volume ratio of the solvent are preferred
1mg/mL~100mg/mL, further preferred 1mg/mL~20mg/mL.
In the method I of prepare compound 18, the catalyst preferably four triphenyl phosphorus palladiums.
In the method I of prepare compound 18, the molar ratio of the catalyst and the compound 12 is preferred
0.01~1, further preferred 0.01~0.1.
In the method I of prepare compound 18, the molar ratio preferably 1 of the compound S ' and the compound 12
~5.
In the method I of prepare compound 18, preferably 0~150 DEG C of the temperature of the Suzuki coupling reaction, further
It is preferred that 80 DEG C~150 DEG C.
In the method I of prepare compound 18, the process of the Suzuki coupling reaction can be using in this field
Routine monitoring method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 12,
Reaction time preferably 1 hour~24 hours.
Following post-processing step is preferably included in the method I of prepare compound 18: after reaction, removing solvent, column color
Isolated product after purification is composed, the method and condition of pillar layer separation can be using the routine side of the generic operation in this field
Method and condition.
The method II of prepare compound 18 can be carried out under gas shield, when the method II of prepare compound 18 is in gas
Protection is lower when carrying out, one of the preferred nitrogen of gas, argon gas, helium and neon described in " under the gas shield " or
It is a variety of.
In the method II of prepare compound 18, the organic solvent preferred aromatic hydrocarbons class solvent, the aromatic hydrocarbons are molten
The preferred toluene of agent.
In the method II of prepare compound 18, the compound 19 and the mass volume ratio of the solvent are preferred
1mg/mL~100mg/mL, further preferred 1mg/mL~20mg/mL.
In the method II of prepare compound 18, the catalyst preferably four triphenyl phosphorus palladiums.
In the method II of prepare compound 18, the molar ratio of the catalyst and the compound 19 is preferred
0.01~1, further preferred 0.01~0.1.
In the method II of prepare compound 18, the molar ratio of the compound V ' and the compound 19 are preferred
1~5.
In the method II of prepare compound 18, preferably 0~150 DEG C of the temperature of the Suzuki coupling reaction.
In the method II of prepare compound 18, the process of the Suzuki coupling reaction can be using in this field
Routine monitoring method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 12,
Reaction time preferably 1 hour~24 hours.
Following post-processing step is preferably included in the method II of prepare compound 18: after reaction, removing solvent, column color
Isolated product after purification is composed, the method and condition of pillar layer separation can be using the routine side of the generic operation in this field
Method and condition.
In the prepare compound 1, following steps are preferably included: in organic solvent, radical initiator
Under the conditions of existing, by compound R ' and tributyltin chloride progress substitution reaction, obtain the compound S '；
The method of prepare compound S ' can be using the conventional method and condition of such substitution reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound S ', the preferred ether solvent of the organic solvent, the ether solvent is preferred
Tetrahydrofuran (THF)；
In the method for prepare compound S ', the compound R ' it is preferred with the mass volume ratio of the organic solvent
1mg/mL~100mg/mL, further preferred 1mg/mL~20mg/mL.
In the method for prepare compound S ', the tributyltin chloride and the compound R ' molar ratio it is excellent
Select 1~3.
In the method for prepare compound S ', the preferred isopropylmagnesium chloride of the radical initiator.
In the method for prepare compound S ', the radical initiator and the compound R ' molar ratio it is preferred
1~3.
In the method for prepare compound S ', preferably 0~100 DEG C of the temperature of the substitution reaction, further preferred 0 DEG C
~40 DEG C.
In the method for prepare compound S ', the process of the substitution reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, generally using the compound R ' disappear when as reaction end, the reaction time
It is preferred that 1 hour~48 hours, further preferred 1 hour~24 hours.
The method of prepare compound S ' preferably includes following post-processing step: after reaction, quenching reaction, extraction obtains
To compound S ', can be directly used for reacting in next step.The preferred aqueous ammonium chloride solution of reagent used by being quenched.The extraction can
With the preferred esters solvent of solvent used using the conventional method of the generic operation in this field, the extraction, the esters
Solvent ethyl acetate.
The method of prepare compound S ' preferably includes following steps: under gas shield, by being added drop-wise to of radical initiator
It closes in the solution that object R ' and organic solvent are formed, reaction a period of time (preferably 1 hour~3 hours), then by tributyltin chloride
It is added drop-wise in reaction system, carries out substitution reaction and obtain the compound S '.It is described by being added drop-wise to of radical initiator
Preferably -10 DEG C~0 DEG C of temperature in the solution that object R ' and organic solvent are formed is closed, it is described to be added drop-wise to tributyltin chloride instead
Answer preferably -10 DEG C~0 DEG C of temperature in system.
In the method for the prepare compound 1, following steps are preferably included: under the conditions of acid is existing, by chemical combination
Object B1 and carbonyl-protection base (preferably ethylene glycol) carry out condensation reaction, obtain the compound R '；
The method of prepare compound R ' can be using the conventional method and condition of such condensation reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound R ', the preferred organic acid of acid, the preferred p-methyl benzenesulfonic acid of the organic acid.
In the method for prepare compound R ', the molar ratio preferably 0.01 of the described acid and the compound B-11~
0.1。
In the method for prepare compound R ', the hydroxy protecting agent preferred diol class compound, the glycol
The preferred ethylene glycol of class compound.
In the method for prepare compound R ', the molar ratio of the hydroxy protecting agent and the compound B-11 is excellent
Select 1~5.
In the method for prepare compound R ', preferably 0~150 DEG C of the temperature of the condensation reaction, further preferred 80
DEG C~120 DEG C.
In the method for prepare compound R ', the process of the condensation reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 17, the reaction time
It is preferred that 1 hour~24 hours.
The method of the prepare compound R ' can carry out in organic solvent, when the condensation reaction is organic
When being carried out in solvent, the solvent preferred aromatic hydrocarbons class solvent, the preferred toluene of the aromatic hydrocarbon solvent.When the condensation is anti-
When should carry out in organic solvent, the preferred 1mg/mL of mass volume ratio of the compound B-11 and the organic solvent~
100mg/mL, further preferred 1mg/mL~20mg/L.
Following post-processing step is preferably included in the method for prepare compound R ': after reaction, alkali cleaning to pH7 or so,
Solvent is removed, pillar layer separation obtains product after purification.The preferred inorganic base of the alkali, the preferred carbonic acid of the inorganic base
Hydrogen sodium.The method and condition of pillar layer separation can be using the conventional method and condition of the generic operation in this field.
In the method 2 of the prepare compound 1, preferably include following steps: in organic solvent, free radical draws
Under the conditions of sending out existing for agent, compound U ' and tributyltin chloride are subjected to substitution reaction, obtain the compound V '；
The method of prepare compound V ' can be using the conventional method and condition of such substitution reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound V ', the preferred ether solvent of the organic solvent, the ether solvent is preferred
Tetrahydrofuran (THF)；
In the method for prepare compound V ', the compound U ' and the mass volume ratio of the organic solvent are preferred
1mg/mL~100mg/mL, further preferred 1mg/mL~20mg/mL.
In the method for prepare compound V ', the molar ratio of the tributyltin chloride and the compound U ' is excellent
Select 1~3.
In the method for prepare compound V ', the preferred isopropylmagnesium chloride of the radical initiator.
In the method for prepare compound V ', the molar ratio of the radical initiator and the compound U ' is preferred
1~3.
In the method for prepare compound V ', preferably 0~100 DEG C of the temperature of the substitution reaction, further preferred 0 DEG C
~40 DEG C.
In the method for prepare compound V ', the process of the substitution reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound U ', the reaction time
It is preferred that 1 hour~48 hours, further preferred 1 hour~24 hours.
The method of prepare compound V ' preferably includes following post-processing step: after reaction, quenching reaction, extraction obtains
To compound V ', can be directly used for reacting in next step.The preferred aqueous ammonium chloride solution of reagent used by being quenched.The extraction can
With the preferred esters solvent of solvent used using the conventional method of the generic operation in this field, the extraction, the esters
Solvent ethyl acetate.
The method of prepare compound V ' preferably includes following steps: under gas shield, by being added drop-wise to of radical initiator
It closes in the solution that object U ' and organic solvent are formed, reaction a period of time (preferably 1 hour~3 hours), then by tributyltin chloride
It is added drop-wise in reaction system, carries out substitution reaction and obtain the compound V '.It is described by being added drop-wise to of radical initiator
Preferably -10 DEG C~0 DEG C of temperature in the solution that object U ' and organic solvent are formed is closed, it is described to be added drop-wise to tributyltin chloride instead
Answer preferably -10 DEG C~0 DEG C of temperature in system.
In the method for the prepare compound 1, following steps are preferably included: under the conditions of acid is existing, by chemical combination
Object T ' and carbonyl-protection base (preferably ethylene glycol) carry out condensation reaction, obtain the compound U '；
The method of prepare compound U ' can be using the conventional method and condition of such condensation reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound U ', the preferred organic acid of acid, the preferred p-methyl benzenesulfonic acid of the organic acid.
In the method for prepare compound U ', the molar ratio preferably 0.01 of the described acid and the compound T '~
0.1。
In the method for prepare compound U ', the hydroxy protecting agent preferred diol class compound, the glycol
The preferred ethylene glycol of class compound.
In the method for prepare compound U ', the molar ratio of the hydroxy protecting agent and the compound T ' is excellent
Select 1~5.
In the method for prepare compound U ', preferably 0~150 DEG C of the temperature of the condensation reaction, further preferred 80
DEG C~120 DEG C.
In the method for prepare compound U ', the process of the condensation reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound T ', the reaction time
It is preferred that 1 hour~24 hours.
The method of the prepare compound U ' can carry out in organic solvent, when the condensation reaction is organic
When being carried out in solvent, the solvent preferred aromatic hydrocarbons class solvent, the preferred toluene of the aromatic hydrocarbon solvent.When the condensation is anti-
When should carry out in organic solvent, the preferred 1mg/mL of mass volume ratio of the compound T ' and the organic solvent~
100mg/mL, further preferred 1mg/mL~20mg/L.
Following post-processing step is preferably included in the method for prepare compound U ': after reaction, alkali cleaning to pH7 or so,
Solvent is removed, pillar layer separation obtains product after purification.The preferred inorganic base of the alkali, the preferred carbonic acid of the inorganic base
Hydrogen sodium.The method and condition of pillar layer separation can be using the conventional method and condition of the generic operation in this field.
In the method for the prepare compound 1, following steps are preferably included: in organic solvent, by compound
057-1 and N- bromo-succinimide (NBS) carry out substitution reaction, obtain the compound T '；
The method of prepare compound T ' can be using the conventional method and condition of such substitution reaction in this field, the present invention
In particularly preferably following reaction method and condition:
In the method for prepare compound T ', the organic solvent preferred amide class solvent, the amide solvent
It is preferred that N,N-dimethylformamide (DMF)；
In the method for prepare compound T ', the mass volume ratio of the compound 057-1 and the organic solvent
It is preferred that 1mg/mL~100mg/L, further preferred 1mg/mL~50mg/L.
In the method for prepare compound T ', the N- bromo-succinimide rubs with the compound 057-1's
That ratio preferably 1~3.
In the method for prepare compound T ', preferably 0~100 DEG C of the temperature of the substitution reaction, further preferred 0 DEG C
~40 DEG C.
In the method for prepare compound T ', the process of the substitution reaction can be using the routine monitoring in this field
Method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using the compound 057-1, reaction
Time preferably 1 hour~48 hours, further preferred 1 hour~24 hours.
The method of prepare compound T ' preferably includes following post-processing step: after reaction, adding water quenching reaction, mistake
Filter, obtains compound T '.
The method of prepare compound T ' preferably includes following steps: N- bromo-succinimide and organic solvent are formed
Solution is added drop-wise in the solution that compound 057-1 and organic solvent are formed, and is carried out substitution reaction and is obtained compound T '.Described
Preferably -10 DEG C~10 DEG C of the temperature of " solution that compound 057-1 and organic solvent are formed ".
In the method for the prepare compound 1, preferably include following steps: in a solvent, alkali and catalyst are deposited
Under the conditions, compound 20 and compound A1 are subjected to Suzuki coupling reaction, obtain the compound 057-1；
The method of prepare compound 057-1 can be using the conventional method and item of such Suzuki coupling reaction in this field
Part, particularly preferably following reaction method and condition in the present invention:
In the method for prepare compound 057-1, the preferred nitrogen of gas, argon described in " under the gas shield "
One of gas, helium and neon are a variety of.
In the method for prepare compound 057-1, the preferred ether solvent of the solvent and/or water, the ethers is molten
The preferred tetrahydrofuran of agent；When using the mixed solvent of ether solvent and water, the volume ratio of the ether solvent and water is excellent
Select 1~10, further preferred 1~5.
In the method for prepare compound 057-1, the compound 20 and the mass volume ratio of the solvent are preferred
1mg/mL~100mg/L, further preferred 1mg/mL~20mg/L.
In the method for prepare compound 057-1, the preferred inorganic base of the alkali, the preferred potassium carbonate of the inorganic base.
In the method for prepare compound 057-1, the molar ratio preferably 1~5 of the alkali and the compound 20.
In the method for prepare compound 057-1, the catalyst preferably four triphenyl phosphorus palladiums.
In the method for prepare compound 057-1, the molar ratio of the catalyst and the compound A1 is preferred
0.01~1, further preferred 0.01~0.2.
In the method for prepare compound 057-1, the molar ratio of the compound 20 and the compound A1 is excellent
Select 1~5.
In the method for prepare compound 057-1, preferably 0~100 DEG C of the temperature of the Suzuki coupling reaction, into one
Preferably 40 DEG C~90 DEG C of step.
In the method for prepare compound 057-1, the process of the Suzuki coupling reaction can be using in this field
Routine monitoring method (such as TLC, HPLC or NMR) be monitored, when generally being disappeared with the compound A1 eventually for reaction
Point, the reaction time preferably 1 hour~24 hours.
Following post-processing step is preferably included in the method for prepare compound 057-1: after reaction, removing solvent, column
Chromatographic isolation obtains product after purification, and the method and condition of pillar layer separation can be using the routine of the generic operation in this field
Method and condition.
The method of prepare compound 1 preferably uses route one, route two, route three, route four or route five:
Route one:
Route two
Route three
Route four
Route five
The present invention also provides compound 1, compound 2, compound 3, compound 4, compound 5, compounds 6, compound
7, compound 8, compound 9, compound 10, compound 11, compound 12, compound 13, compound 14, compound 15, chemical combination
Object 16, compound 17, compound 18, compound 19, compound B-11, compound P ', compound Q ', compound R ', compound S ',
Compound T ', compound U ', compound V ', compound A1 or compound 057-1,
Wherein, the definition of A, B, D are same as above.
The present invention also provides organic dye sensitized dose of the salt, the preferred institute of organic dye sensitized dose of salt
Organic dye sensitized dose of the alkali metal salt or organic dye sensitized dose of the ammonium salt stated.
The present invention also provides described organic dye sensitized doses 1 or its salt as light-sensitive coloring agent in photoelectric conversion technique
Purposes.The preferred organic film solar cell technology in the photoelectric conversion technique field, dye sensitized nano crystal body sun electricity
Pool technology or organic photoelectric hydrogen production by water decomposition technology etc., further preferred dye sensitized nano crystal body solar cell technology.
Heretofore described organic dye sensitized dose 1 or its salt can be used as pure as a kind of novel photosensitizer
Organic dyestuff photosensitizer replace precious metals complex photosensitizer reported in the literature, the production of this kind of battery can be effectively reduced
Cost.
Dye sensitized nano crystal salar battery of the present invention includes photo cathode, and the photo cathode has porous
Nano-oxide film, the porous nano oxide membranous layer adsorb or are impregnated with described organic dye sensitized dose, this
A little novel organic dye sensitizers can be used as photosensitizer and replace precious metals complex photosensitizer reported in the literature, can be effectively
Reduce the cost of manufacture of this kind of battery.The porous nano sull is one of titanium oxide, zinc oxide, tin oxide
Or it is a variety of.
In the present invention, the absorption or dipping are the following steps are included: first quick by heretofore described organic dyestuff
It is 10 that agent, which is dissolved in organic solvent and is configured to concentration,-8The solution of~10M, the nanoporous oxidation for then sintering being annealed later
Object film is immersed in the solution, and soaking time is one minute to 36 hours, and the photo cathode through being sensitized can be obtained.It is described to have
The preferred halogenated hydrocarbon solvent of solvent, alcohols solvent, ether solvent, amide solvent, nitrile solvents, aromatic hydrocarbon solvent and halogenated
One of aromatic hydrocarbon solvent is a variety of.The preferred chlorinated hydrocarbon solvent of the halogenated hydrocarbon solvent；The chlorinated hydrocarbon is molten
One of the preferred methylene chloride of agent, chloroform, carbon tetrachloride, dichloroethanes and trichloroethanes are a variety of.The alcohols solvent
It is preferred that C1-8Alcoholic solvent；The C1-8One of the preferred methanol of alcoholic solvent, ethyl alcohol, propyl alcohol, isopropanol and butanol or more
Kind.One of the preferred tetrahydrofuran of the ether solvent, ether, methyltetrahydrofuran, methyl tertiary butyl ether(MTBE) and isopropyl ether
Or it is a variety of.The preferred acetonitrile of the nitrile solvents.The preferred N,N-dimethylformamide of the amide solvent.The aromatic hydrocarbons
One of the preferred benzene of class solvent, dimethylbenzene, t-butyltoluene are a variety of.The preferred chlorinated aromatic hydrocarbons of halogenated aryl hydrocarbon class solvent
Class solvent；The preferred chlorobenzene of chlorinated aromatic hydrocarbons class solvent.
The present invention also provides a kind of dye sensitized nano crystal body solar batteries, mainly by following components group
At transparent base layer 1, conductive layer 2, light absorbing layer 3, electrolyte layer 4 and to electrode layer 5；Wherein, light absorbing layer 3 is by semiconductor
Nanoparticle 6 and dye coating 7 are constituted.The dye coating 7 is as the organic dye sensitized dose of structure of the invention as shown in general formula 1
At.
In the present invention, the preferred substrate of glass of transparent base layer 1 or plastics；The preferably poly- terephthaldehyde of the plastics
Sour glycol ester, polyethylene naphthalate, polycarbonate, polypropylene, poly- propionamide, tri acetyl cellulose and polyether sulfone
One of or it is a variety of.
In the present invention, the conductive layer 2 is preferably by tin indium oxide, fluorine oxide tin, ZnO-Ga2O3、ZnO-Al2O3, tinbase
Any one composition in oxide, antimony tin and zinc oxide.
In the present invention, the light absorbing layer 3 is preferably made of semiconductor nano-particles layers 6 and dye coating 7；It is preferred that institute
The semiconductor nano-particles layers 6 stated are connect with conductive layer 2, and dye coating 7 is connect with electrolyte layer 4.
In the present invention, the semi-conductor nano particles preferred Si, Ti0 of the semiconductor nano-particles layers 62,SnO2,ZnO,
WO3,Nb205Or TiSrO3, it is preferable that 0nm < semi-conductor nano particles average grain diameter < 50nm.
In the present invention, the electrolyte layer 4 is preferably by iodine/salt compounded of iodine electrolyte, ionic liquid, organic hole transport material
Any one in (bis- (N, N- di-p-methoxy the aniline) -9,9- spiro-bisfluorenes of such as 2,2-7,7- tetra-) and inorganic hole transporter
Or a variety of compositions.
In the present invention, it is described to electrode 5 preferably by Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C or conduction
Any one or more in polymer forms；The conducting polymer preferred polyaniline, polythiophene, gathers to benzene second polypyrrole
One of alkynes and polyethers are a variety of.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably
Example.
The reagents and materials used in the present invention are commercially available.
Room temperature in the present invention refers to that environment temperature is 10 DEG C~30 DEG C.
The positive effect of the present invention is that:
1, include conjugation aromatic ring chromophore units either these knots in organic dye sensitized agent molecule of the invention
The conjugation assembly of two or more in structure unit, the aromatic ring directly link two or more electron donors, electricity
Sub- receptor or electron neutral organic structure ele；The especially introducing of electron acceptor and electron neutral organic structure ele, it is rich
The rich regulating measure and ability that spectral range and intramolecular electronic behavior are inhaled to molecular structure, molecule.
2, of the invention organic dye sensitized dose, pass through one or more comprising conjugation aromatic ring in molecule
Bindinggroup comes and dye sensitization battery light electricity anode (TiO2, ZnO etc.) and the nanometer micropore surface of material is mutually bonded, thus
The electron-transport that quick agent molecule excites after visible and ultraviolet light will be contaminated to go out to form electric current.
3, organic dye sensitized agent molecule provided by the invention, synthesizing selected structural unit is general aromatic conjugated structure
Chromophore (Ar), by the matched conjugation electron rich unit (electron donor, D) of selection, short of electricity subelement (electron acceptor, A), or
Person's electron neutral organic structure ele (neutral body, N) is linked through conjugation, is built conjugation aromatic ring chromophore highly branched chain and is spread out
Biochemical new dye sensitizer.The stereochemical structure of gained molecule is changed, and improves the nonplanarity for contaminating quick agent molecule, is reduced
Dyestuff is in TiO2The pi-pi accumulation on surface acts on；By being given to conjugation aromatic ring chromophore, conjugated structure unit and electronics
Body, receptor and neutral body are cut out, and gained dye sensitizing agent has wider absorption spectrum, stronger photoelectric current, can pass through
Molecular structure rationally cuts out the locomotivity for reaching and adjusting electronics in transmission channel, improves the photoelectric conversion efficiency of device.It should
Class dye molecule has the advantages that good light, heat, chemical stability, raw material is easy to get, synthesis facilitates, molecular diversity, gained
The photoelectric conversion efficiency of dye-sensitized solar cells reaches 80% or more of N719 dyestuff, can be used as commercialization dye sensitization too
Organic photosensitive agent in positive battery product uses.
5, the invention discloses one kind conjugation organic dye sensitized dose of aromatic ring chromophore highly branched chain derivatization, its salt and
The intermediate of such organic dyestuff compound, especially a kind of band terthienyl conjugation aromatic rings cellular construction intermediate, it is each
Kind synthetic method and rationally organic dye sensitized dose or its salt of derivative gained, their preparation method are led with them in photoelectric conversion
The application in domain can replace the precious metals complex photosensitizer reported in document or patent, can be effectively reduced the system of this kind of battery
Make cost.This hair agents useful for same and raw material are commercially available, and raw material sources are convenient；Selected synthetic method is general organo units
Reaction, practical process of preparing and purifying is simple, suitable for laboratory preparation and industrialized production.
Detailed description of the invention
Fig. 1 is the dye sensitized nano crystal body sun electricity of organic dye sensitized dose of I preparation of the invention in effect example 1
The structural schematic diagram in pond, wherein 1 is transparent substrates；2 be conductive layer；3 be light absorbing layer；4 be electrolyte layer；5 is to electrode layers.
Fig. 2 is the compound of the present invention CGTD-DSSC-025, CGTD-DSSC-029, CGTD-DSSC-031, CGTD-
DSSC-036、CGTD-DSSC-039、CGTD-DSSC-055、CGTD-DSSC-064、CGTD-DSSC-066、CGTD-DSSC-
The short circuit current (Isc) of 069 and N719 and the relational graph of current potential (Voc), wherein 6 be the short circuit current of CGTD-DSSC-025
(Isc) with the relational graph of current potential (Voc), 7 for CGTD-DSSC-029 short circuit current (Isc) and current potential (Voc) relational graph, 8
It is the short circuit current of CGTD-DSSC-036 for the short circuit current (Isc) of CGTD-DSSC-031 and the relational graph of current potential (Voc), 9
(Isc) with the relational graph of current potential (Voc), 10 for CGTD-DSSC-039 short circuit current (Isc) and current potential (Voc) relational graph,
11 be the short circuit current (Isc) of CGTD-DSSC-055 and the relational graph of current potential (Voc), and 12 is electric for the short circuit of CGTD-DSSC-064
The relational graph of (Isc) and current potential (Voc) are flowed, 13 be the short circuit current (Isc) of CGTD-DSSC-066 and the relationship of current potential (Voc)
Figure, 14 be the short circuit current (Isc) of CGTD-DSSC-069 and the relational graph of current potential (Voc), and 15 be the short circuit current of N719
(Isc) with the relational graph of current potential (Voc).
Fig. 3 is the compound of the present invention CGTD-DSSC-029, CGTD-DSSC-031, CGTD-DSSC-036, CGTD-
The UV, visible light of DSSC-039, CGTD-DSSC-055, CGTD-DSSC-064, CGTD-DSSC-066, CGTD-DSSC-069 are inhaled
Spectrum spectrogram is received, 7 be the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-029, and 8 be the UV, visible light of CGTD-DSSC-031
Absorption spectrum spectrogram, 9 be the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-036, and 10 can for the ultraviolet of CGTD-DSSC-039
See absorption spectrum spectrogram, 11 be the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-055, and 12 be the purple of CGTD-DSSC-064
Outer visible absorption spectra spectrogram, 13 be CGTD-DSSC-066, and 14 be the ultraviolet-visible absorption spectroscopy spectrogram of CGTD-DSSC-069.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Embodiment 1:
1) synthesis of intermediate A 1: under the conditions of being protected from light, N- bromo-succinimide (1.60 grams, 9 mMs) is added to
Dissolved in 80 milliliters of n,N-Dimethylformamide solution of 3- formylthien (1.0 grams, 9 mMs), react at room temperature 2 days, it
100 milliliters of water are added afterwards, and (100 milliliters, 3 times) are extracted with ethyl acetate, organic layer concentration, silica gel crosses column (petroleum ether: second
Acetoacetic ester=50:1) obtain 1.9 g of compound A1, yield 78.5%.1H-NMR (400MHz, DMSO-d6) δ: 7.476 (s, 1H),
9.722 (s, 1H).ESI-MS[M+H]+:267.8。
2) synthesis of intermediate B 1: in 100 milliliters of flasks be added compound A1(538 milligrams, 2 mMs), thiophene -2- boron
Sour (256 milligrams, 2 mMs), tetra-triphenylphosphine palladium (232 milligrams, 0.2 mM) and tetrahydrofuran: 24 milli of water (5:1)
It rises.Under the conditions of nitrogen protection, mixture reacts 8 hours at 70 DEG C, and after being cooled to room temperature, concentration removes solvent, silica gel column layer
Analysis (petroleum ether: ethyl acetate=50:1) obtains 174 milligrams of compound B-11s, yield 31.8%.ESI-MS[M+H]+:272.7。
3) synthesis of intermediate C: compound 3- hexyl thiophene (842 milligrams, 5 mMs) are added in 50 milliliters of flasks, N-
Chlorosuccinimide (668 milligrams, 5 mMs) and 20 milliliters of n,N-Dimethylformamide.Under the conditions of nitrogen protection, mix
Object is closed after room temperature reaction 16 hours, 20 milliliters of water are added in reaction solution, are extracted with ethyl acetate (20 milliliters, three times), it is organic
Layer concentration removes solvent and obtains 0.98 g of compound C, LC-MS purity: 89.02%, yield 97.0%.ESI-MS[M+H]+:
202.2。
4) compound C(909 milligrams, 4.5 mMs the synthesis of intermediate D1: is added in 50 milliliters of flasks), N- bromine is added
For succimide (800 milligrams, 4.5 mMs), room temperature reaction overnight, is added 20 milliliters of water, uses ethyl acetate in reaction solution
It extracts (20 milliliters, three times), organic layer concentration removes solvent and obtains 1.2 g of compound D1, LC-MS purity: 100%, yield
85.4%。ESI-MS[M+H]+: 281.9.
5) compound D1(702 milligrams, 2.5 mMs the synthesis of intermediate E: is added in 25 milliliters of three-necked flasks), -78
N-BuLi (1.5 milliliters, 3.75 mMs) are added dropwise under the conditions of DEG C, are reacted 1 hour under the conditions of -78 DEG C, isopropyl fundamental frequency are added where
Alcohol borate (744 milligrams, 4 mMs).Under the conditions of nitrogen protection, mixture reacts 16 hours, and saturated ammonium chloride water is added
Solution quenching reaction, methylene chloride extract (20 milliliters, three times), and silica gel chromatograph post separation (petroleum ether) obtains after concentration removes solvent
To 450 milligrams of compound E, yield 54.8%.1H-NMR (400MHz, CDCl3) δ: 0.821 (t, 3H), 1.237 (m, 6H), 1.255
(s, 12H), 1.501 (m, 2H), 2.481 (t, 2H), 7.260 (s, 1H), ESI-MS [M+H]+: 356.2.
6) synthesis of intermediate G: in 100 milliliters of flasks be added F(1.67 grams of compound, 6 mMs), tributyl tin thiophene
(2.24 grams, 6 mMs), tetra-triphenylphosphine palladium (0.694 gram, 0.6 mM) and 50 milliliters of tetrahydrofuran.In nitrogen protection
Under the conditions of, mixture 66 degrees Celsius react 16 hours, after being cooled to room temperature, concentration remove solvent, silica gel cross column (petroleum ether:
Ethyl acetate=6:1) obtain 1.5 g of compound G, LC-MS purity: 98.48%, yield 89%.1H-NMR(400MHz,DMSO-d6)
δ:3.197(s,3H),3.378(s,3H),7.120(t,1H),7.185(d,1H),7.540(d,2H),7.601(d,1H),
7.625(d,1H),ESI-MS(M+H+):282.0.
7) under the conditions of being protected from light, NBS (2 grams, 11.18 mMs) synthesis of intermediate H: is added to 60 milliliters of compound G
The DMF(N of (3 grams, 10.65 mMs), dinethylformamide) in solution, stirred under nitrogen atmosphere is overnight, in reaction system
50 milliliters of water of middle addition, solid be precipitated, filtering arrive 2.5g intermediate H, LC-MS purity: 95.77%, yield 65.4%.1H-NMR
(400MHz,DMSO-d6)δ:3.207(s,3H),3.400(s,3H),7.016(d,1H),7.250(d,1H),7.570(m,
4H),.ESI-MS(M+H+): 361.9.
Embodiment 2:
1) synthesis of intermediate compound I: 1,1,7,7- tetramethyl julolidine is added in 25 milliliters of flasks, and (91.6 milligrams, 0.4 in the least
Mole), N- bromo-succinimide (71.2 grams, 0.4 mM) and 12 milliliters of methylene chloride.Under the conditions of nitrogen protection,
12 milliliters of water are added after room temperature reaction 16 hours in mixture, and methylene chloride extracts (15 milliliters, 3 times) concentrations removing solvents and obtains
To 105 milligrams of compound I, LC-MS purity: 100%, yield 85.1%.1H-NMR (400MHz, DMSO-d6) δ: 1.254 (s,
12H), 1.733 (t, 4H), 3.121 (t, 4H), 7.083 (s, 2H), ESI-MS (M+H+):310.0。
2) compound I(92.4 milligrams, 0.3 mM the synthesis of intermediate J: is added in 50 milliliters of flasks), duplex frequency is where
Alcohol borate (152 milligrams, 0.6 mM), potassium acetate (88.3 milligrams, 0.9 mM), [1,1'- bis- (diphenylphosphines) two cyclopentadienyl
Iron] palladium chloride (Pd (dppf) Cl2) (24 milligrams, 0.03 mM) and 20 milliliters of dioxanes.Under the conditions of nitrogen protection,
Mixture reacts 16 hours at 85 DEG C, and silica gel chromatograph post separation (petroleum ether) obtains 75 milligrams of compound J after concentration removes solvent,
LC-MS purity: 100%, yield 70.4%.1H-NMR(400MHz,DMSO-d6) δ: 1.231 (s, 24H), 1.662 (t, 4H),
3.129 (t, 4H), 7.429 (s, 2H), ESI-MS [M+H]+: 356.2.
3) synthesis of intermediate L: in 50 milliliters of flasks, being added compound K (1.07 grams, 3 mMs), compound duplex frequency
Any alcohol borate (1.52 grams, 6 mMs), potassium acetate (0.882 gram, 9 mMs), [1,1'- bis- (diphenylphosphine) ferrocene]
Palladium chloride (Pd (dppf) Cl2) (219 milligrams, 0.3 mM) and 20 milliliters of dioxanes, be heated to 90 degrees Celsius it is stirred
Night, concentration remove solvent, and silica gel crosses column (petroleum ether: ethyl acetate=100:1) and obtains 1.0 g of compound L, LC-MS purity:
98.6%, yield 82.3%.1H-NMR (400MHz, CDCl3) δ: 1.306 (s, 12H), 7.550 (m, 1H), 7.886 (d, 2H),
7.944 (d, 1H), 8.025 (d, 2H), 8.280 (s, 1H).ESI-MS[M+H]+: 406.1.
4) synthesis of intermediate N1: by compound M (364 milligrams, 1.0 mMs), 20 milliliters of tetrahydrofuran are added to 50
In milliliter three-necked flask, n-BuLi (0.48 milliliter, 1.2 mMs) is added dropwise under subzero 78 degrees Celsius, at this temperature instead
After answering 1 hour, it is added dropwise tributyltin chloride (390 milligrams, 1.2 mMs), room temperature reaction 16 is slowly warming up to after being added dropwise
Hour, 20 milliliters of water are added, is extracted with ethyl acetate (20 milliliters, 3 times), organic layer concentration, silica gel crosses column (petroleum ether: acetic acid
Ethyl ester=50:1) 380 milligrams of compound Ns 1 are obtained, LC-MS purity: 98.47%, yield 66.2%.1H-NMR (400MHz, DMSO-
d6) δ: 0.862 (t, 9H), 1.152 (t, 6H), 1.335 (m, 6H), 1.651 (m, 6H), 7.302 (d, 1H), 7.750 (d, 1H),
7.982 (d, 1H), 8.340 (m, 2H).ESI-MS[M+H]+:576.2。
5) compound O(298 milligrams, 2 mMs the synthesis of intermediate P: is added in 100 milliliters of flasks), 4- hexyloxy bromine
Benzene (1.28 grams, 5 mMs), sodium tert-butoxide (576 milligrams, 6 mMs), bis- (dibenzalacetone) palladiums (91.5 milligrams, 0.1
MM), tributyl phosphorus tetrafluoroborate (116 milligrams, 0.4 mM) and 50 milliliters of toluene, under the conditions of nitrogen protection
100 DEG C of 16 hours reaction hours, silica gel chromatograph post separation (petroleum ether: ethyl acetate=100:1) obtains after concentration removes solvent
800 milligrams of compound P, yield 79.8%.1H-NMR (400MHz, CDCl3) δ: 0.878 (t, 6H), 1.309 (m, 8H), 1.406
(m, 4H), 1.670 (m, 4H), 3.912 (t, 4H) 6.861 (m, 4H), 6.949 (m, 5H), 7.262 (m, 2H), 7.671 (d,
1H), 7.783 (d, 1H), ESI-MS [M+H]+: 501.1.
6) compound P(204 milligrams, 0.4 mM the synthesis of intermediate Q: is added in 25 milliliters of three-necked flasks), -78
N-BuLi (0.24 milliliter, 0.6 mM) is added dropwise under the conditions of DEG C, is reacted 1 hour under the conditions of -78 DEG C, isopropyl fundamental frequency is added where
Alcohol borate (120 milligrams, 0.64 mM).Under the conditions of nitrogen protection, mixture reacts 16 hours, and saturated ammonium chloride is added
Aqueous solution quenching reaction, methylene chloride extract (20 milliliters, three times), concentration remove solvent after silica gel chromatograph post separation (petroleum ether:
Ethyl acetate=30:1) obtain 100 milligrams of compound Qs, yield 40%.ESI-MS[M+H]+: 628.2.
7) synthesis of intermediate R: by bromo- 9, the 9- dimethyl -9-(H of 2-)-fluorenes (3.30 grams, 12 mMs), aniline (440
Milligram, 4.73 mMs), tris(dibenzylideneacetone) dipalladium (180 milligrams, 0.2 mM), tri-tert-butylphosphine borofluoride
(232 milligrams, 0.8 mM), sodium tert-butoxide (1.3 grams, 13.5 mMs) and 20 milliliters of toluene are under nitrogen atmosphere in 100 DEG C
Reaction 4 hours.Filtrate is concentrated in filtering, and residue obtains 2.0 grams of whites with silica gel column purification (petroleum ether: ethyl acetate=100:1)
Solid chemical compound R, yield 89%.ESI-MS[M+H]+: 478.
8) synthesis of intermediate S: into 50 milliliters of dichloromethane solutions dissolved with R (954 milligrams, 2.0 mMs) in 0 DEG C
Under N- bromo-succinimide (NBS) (340 milligrams, 1.91 mMs) be slowly added dropwise be dissolved in the solution of 30 milliliters of methylene chloride,
It adds within 30 minutes, finishes, the reaction was continued 30 minutes in 0 DEG C.Evaporating solvent under reduced pressure, the purifying of residue silica gel column chromatography (eluant, eluent:
Petroleum ether), obtain 1.02 grams of compound as white solid S, yield 96%.ESI-MS[M+H]+: 478.
9) synthesis of intermediate T: to S(973 milligrams of compound, 1.75 mMs) to be dissolved in 20 milliliters of dry tetrahydrofurans molten
The lithium hexane solution (1.3 milliliters, 2.1 mMs) of 1.6M is added dropwise in liquid in -78 DEG C, finishes, is maintained at -78 DEG C anti-
It answers 1 hour, 2- isopropyl -4,4-5,5- tetramethyl -1,3,2- dioxo borine (558 milligrams, 3 mMs), reaction solution is added
Room temperature is warmed naturally to, reaction 16 hours is stirred at room temperature.20 milliliters of saturated aqueous ammonium chlorides, acetic acid are added into reaction solution
Ethyl ester extraction, separates organic layer, is spin-dried for, and silica gel column chromatography purifies (petroleum ether: ethyl acetate=40:1), and it is solid to obtain 630 milligrams of whites
Body compound T, yield: 60%.1H-NMR(400MHz,CDCl3):δ7.69(d,J=8.0Hz,2H),7.64(d,J=8.0Hz,
2H), 7.59 (d, J=8.0Hz, 2H), 7.38 (d, J=8.0Hz, 2H), 7.30~7.33 (m, 2H), 7.24~7.28 (m, 4H),
7.15(d,J=8.0Hz,2H),7.09(d,J=8.0Hz,2H),1.40(s,12H),1.35(s,12H)。
10) it the synthesis of intermediate V: in 50 milliliters of flasks, is added compound U (1.15 grams, 3 mMs), compound duplex
Pinacol borate (1.52 grams, 6 mMs), potassium acetate (0.882 gram, 9 mMs), 1,1'- bis- Diphenyl phosphino ferrocenes two
Palladium chloride (219 milligrams, 0.3 mM) and 20 milliliters of dioxanes, are heated to 90 degrees Celsius and are stirred overnight, and concentration removes molten
Agent, silica gel cross column (petroleum ether: ethyl acetate=100:1) and obtain 1.0 g of compound V, yield 77.3%.ESI-MS[M+H]+:
431.3。
11) it the synthesis of intermediate X: in 50 milliliters of flasks, is added compound W (1.57 grams, 3 mMs), compound duplex
Pinacol borate (1.52 grams, 6 mMs), potassium acetate (0.882 gram, 9 mMs), 1,1'- bis- Diphenyl phosphino ferrocenes two
Palladium chloride (219 milligrams, 0.3 mM) and 20 milliliters of dioxanes, are heated to 95 degrees Celsius and are stirred overnight, and concentration removes molten
Agent, silica gel cross column (petroleum ether: ethyl acetate=150:1) and obtain 1.1 g of compound V, yield 64.1%.ESI-MS[M+H]+:
571.6。
Embodiment 3:
1) synthesis of intermediate Y: thieno [3,2-b] thiophene (140 milligrams, 1 mM) are added in 25 milliliters of flasks, N-
Bromo-succinimide (480 grams, 0.9 mM) and 12 milliliters of methylene chloride.Under the conditions of nitrogen protection, mixture is in room
After temperature reaction 16 hours, 12 milliliters of water are added, methylene chloride extracts (15 milliliters, 3 times) concentrations removing solvents and obtains intermediate
Y180 milligrams.Yield 82.1%.ESI-MS(M+H+):219.8。
2) compound Y(175.2 milligrams, 0.8 mM the synthesis of intermediate Z: is added in 50 milliliters of flasks), compound 3
(182.4 milligrams, 0.96 mM), potassium carbonate (331 milligrams, 2.4 mMs), four triphenyl phosphorus palladiums (92.6 milligrams, 0.08 milli
Mole), 20 milliliters of tetrahydrofuran and 6 milliliters of water.Under the conditions of nitrogen protection, mixture reacts 16 hours at 68 DEG C, concentration
Silica gel chromatograph post separation (petroleum ether) obtains Z170 milligrams of intermediate after removing solvent.Yield 74.8%.1H-NMR(400MHz,
DMSO-d6)δ:7.196(d,1H),7.338(d,1H),7.507(s,1H),7.563(d,2H),7.643(d,2H),ESI-MS
(M+H+):284.3
3) intermediate A ' synthesis: in 100 milliliters of flasks be added 4- trifluoromethylbenzene boronic acid (570 milligrams, 3 mMs),
2,3- dibromo thiophenes (657 milligrams, 3 mMs), potassium carbonate (1.24 grams, 9 mMs), tetra-triphenylphosphine palladium (347 milligrams, 0.3
MM) and 25 milliliters of tetrahydrofuran, 8 milliliters of water.Under the conditions of nitrogen protection, mixture reacts 16 hours at 68 DEG C
Afterwards, after cooling room temperature, concentration removes solvent, silica gel chromatograph post separation (petrol ether/ethyl acetate=20/1) obtain intermediate A '
700 milligrams.Yield 62.7%.ESI-MS(M+H+):372.0。
4) intermediate B ' synthesis: in 25 milliliters of flasks be added compound A'(297.6 milligrams, 0.8 mM), N- bromo
Succimide (142.4 milligrams, 0.8 mM) and 25 milliliters of n,N-Dimethylformamide.Under the conditions of nitrogen protection, mix
After conjunction object reacts 8 hours under the conditions of 50 DEG C, 25 milliliters of water, white solid intermediate B ' 340 to compound 8 of filtering are added
Milligram.Yield 94.2%.ESI-MS(M+H+):451.9.
5) synthesis of intermediate C': in 50 milliliters of flasks be added the bromo- 5- trifluoromethyl thiophene of compound 2- (462 milligrams, 2
MM), compound 2- thienyl boric acid (307.2 milligrams, 2.4 mMs), potassium carbonate (0.828 gram, 6 mMs), four triphens
Base phosphorus palladium (232 milligrams, 0.2 mM), 21 milliliters of tetrahydrofuran and 7 milliliters of water.Under the conditions of nitrogen protection, mixture exists
68 DEG C are reacted 6 hours, and silica gel chromatograph post separation (petroleum ether) obtains C'400 milligrams of intermediate after concentration removes solvent.Yield
85.5%。ESI-MS(M+H+):233.9。
6) compound C'(398 milligrams, 1.7 mMs the synthesis of intermediate D': is added in 25 milliliters of flasks), N- bromo fourth
Imidodicarbonic diamide (302 milligrams, 1.7 mMs) and 25 milliliters of n,N-Dimethylformamide.Under the conditions of nitrogen protection, mixture
It is reacted overnight under the conditions of 30 DEG C, 25 milliliters of water, D'340 milligrams of white solid intermediate to compound 4 of filtering is added.It produces
Rate 63.9%.ESI-MS(M+H+):311.9。
7) intermediate E ' synthesis: in 50 milliliters of flasks be added compound 5- methyl -2,1,3- diazosulfide (901 milli
Gram, 6 mMs), hydrogen bromide (40%, 15 milliliters) is added dropwise bromine (1 milliliter, 1 milliliter of hydrogen bromide dissolution), mixes after being heated to 120 degree
It closes object to react under 120 degrees celsius overnight, after being cooled to room temperature, 15 milliliters of bisulfite saturated aqueous solution of sodium additions are removed
Excessive bromine is removed, yellow solid is obtained by filtration, ethyl alcohol recrystallization obtains intermediate E ' 1.3 gram.Yield 70.3%.ESI-MS(M+H+):308.8。
8) E'(1.3 grams of compound, 4.2 mMs the synthesis of intermediate F': is added in 50 milliliters of flasks), N- bromo fourth two
Acid imide (0.75 gram, 4.2 mMs), benzoyl peroxide (50.8 milligrams, 0.21 mM), 20 milliliters of carbon tetrachloride, in nitrogen
Under the conditions of gas shielded, mixture heating reflux reaction is stayed overnight, and is filtered to remove solid, is used ethyl alcohol recrystallization after filtrate concentration, obtain
F'0.92 grams of intermediate, yield 56.6%.ESI-MS(M+H+):387.2。
9) compound F'(851 milligrams, 2.2 mMs the synthesis of intermediate G': is added in 50 milliliters of flasks), calcium carbonate
(1.1 grams, 11 mMs) and 25 milliliters of dioxanes, 20 milliliters of water is heated to 100 degree of reactions overnight, after being cooled to room temperature, mistake
Calcium carbonate is filtered out, filtrate is concentrated to get G'0.62 grams of intermediate.Yield 84.5%.ESI-MS(M+H+):324.2。
10) compound G'(620 milligrams, 1.9 mMs the synthesis of intermediate H': is added in 100 milliliters of flasks), titanium dioxide
Manganese (1.33 grams, 15.2 mMs) and 30 milliliters of dioxanes, react 1 hour after being heated to 100 degree, after being cooled to room temperature, mistake
Unreacted manganese dioxide is filtered out, filtrate is concentrated to get H'400 milligrams of intermediate.Yield 64.5%.ESI-MS(M+H+):
321.8。
11) intermediate compound I ' synthesis: in 25 milliliters of flasks be added compound H'(200 milligrams, 0.62 mM), tri- fourth of 2-
Base tinbase thiophene (293 grams, 0.78 mM), four triphenyl phosphorus palladiums (72 milligrams, 0.062 mM) and 15 milliliters of toluene,
It is reacted after being heated to 95 degrees Celsius overnight, after being cooled to room temperature, concentration removes toluene, silica gel chromatograph post separation (petroleum ether: acetic acid
Ethyl ester=50:1) obtain intermediate compound I ' 65 milligram.Yield 33.3%.ESI-MS(M+H+):325.9。
12) synthesis of intermediate J': cyclopenta bithiophene (178.3 milligrams, 1 mM) are added in 25 milliliters of flasks, just
Hexyl bromide (363 milligrams, 2.2 mMs), potassium iodide (8.3 milligrams, 0.05 mM), is stirred at room temperature by 6 milliliters of dimethyl sulfoxide
After ten minutes, potassium hydroxide (224 milligrams, 4 mMs) are added.Under the conditions of nitrogen protection, mixture is small in 20 DEG C of reactions 16
When, add water quenching reaction and extract (15 milliliters, three times) with ether, is concentrated to get crude product, silica gel chromatograph post separation (petroleum
Ether) obtain J'300 milligrams of intermediate.Yield 86.7%.ESI-MS(M+H+):346.1。
13) compound J'(173.3 milligrams, 0.5 mM the synthesis of intermediate K': is added in 25 milliliters of three-necked flasks),
10 milliliters of tetrahydrofuran, n-BuLi (2.5M, 0.24 milliliter, 0.6 mM) is added dropwise under subzero 78 degrees celsius, is added dropwise
After, react 1 hour at a temperature of this, be added dropwise under the conditions of subzero 78 degree tributyltin chloride (195.3 milligrams, 0.6 mmoles
You), under the conditions of nitrogen protection, mixture is slowly being warming up to room temperature and is reacting overnight, adds water quenching reaction and separates
It is several layers of to having, K'230 milligrams of intermediate are concentrated to get, yield 72.3%.ESI-MS(M+H+):636.2。
14) synthesis of intermediate L'
Cyclopenta bithiophene (178.3 milligrams, 1 mM) are added in 25 milliliters of flasks, and bromoethane (240 milligrams, 2.2 millis
Mole), potassium iodide (8.3 milligrams, 0.05 mM), is stirred at room temperature after ten minutes, hydroxide is added by 8 milliliters of dimethyl sulfoxide
Potassium (224 milligrams, 4 mMs).Under the conditions of nitrogen protection, mixture reacts 17 hours at 20 DEG C, and water quenching reaction is added to be used in combination
Ether extracts (15 milliliters, three times), is concentrated to get crude product, and silica gel chromatograph post separation (petroleum ether) obtains intermediate L'200 milli
Gram.Yield 85.5%.ESI-MS(M+H+):234.1。
15) synthesis of intermediate M'
Compound L ' (550 milligrams, 2.35 mMs) are added in 25 milliliters of three-necked flasks, 15 milliliters of tetrahydrofuran, zero
N-BuLi (2.5M, 1.13 milliliters, 2.82 mMs) is added dropwise under lower 78 degrees celsius, it is anti-at a temperature of this after being added dropwise
It answers 1 hour, tributyltin chloride (880 milligrams, 2.7 mMs) is added dropwise under the conditions of subzero 78 degree, under the conditions of nitrogen protection,
Mixture is slowly being warming up to room temperature and is reacting overnight, add water quenching reaction and it is isolated have several layers of, be concentrated to get 1.02
Gram intermediate M', yield 82.9%.ESI-MS(M+H+):524.2。
16) synthesis of intermediate N':
By B(450 milligrams of compound, 1.67 mMs), N- bromo-succinimide (578 milligrams, 3.34 mMs) is molten
In chloroform (30 milliliters), acetic acid (10 milliliters) are added dropwise under ice-water bath, drop finishes, and reacts ambient temperature overnight, and reaction solution is used respectively
Water (30 milliliters, three times), saturated sodium bicarbonate (20 milliliters), sodium thiosulfate (20 milliliters) are washed, and organic layer concentration silica gel crosses column
(petroleum ether: ethyl acetate=100:1) obtains 588 milligrams of intermediate N', LC-MS purity: 99%, yield 88%.ESI-MS[M+H
]+: 398.9.
17) synthesis of intermediate O':
By N'(100 milligrams of intermediate, 0.25 mM), 4- isopropoxy phenyl boric acid (55 milligrams, 0.3 mM), carbon
Sour potassium (86 milligrams, 0.63 mM) is dissolved in the in the mixed solvent for filling tetrahydrofuran (10 milliliters) and water (2 milliliters), and nitrogen is protected
Tetra-triphenylphosphine palladium (29 milligrams, 0.025 mM) are added under the conditions of shield, solution is stayed overnight in 70 DEG C of reactions, after being cooled to room temperature
Organic layer is separated, is concentrated to get crude product, silica gel crosses column (petroleum ether: ethyl acetate=10:1) and obtains 64 milligrams of intermediates O', LC-
MS purity: 96%, yield 38%, ESI-MS [M+H+2]+: 409.0.
18) B " synthesis of intermediate:
By compound 055-1 (200 milligrams, 0.279 mM), ethylene glycol (86.5 milligrams, 1.39 mMs), to toluene
Sulfonic acid (4.8 milligrams, 0.028 mM) is added in the flask for filling 20 milliliters of toluene, in 130 degrees Celsius of lower water segregators point
Water is stirred at reflux reaction 8 hours, and sodium bicarbonate aqueous solution is added after being cooled to room temperature, adjusts pH value and is greater than 8, ethyl acetate extraction
Concentration is taken, silica gel crosses column (petroleum ether: ethyl acetate=20:1) and obtains 200 milligrams of compound B ".Yield 94.3%.ESI-MS(M+H+)=760.2
19) C " synthesis of intermediate:
Under the conditions of ice-water bath, isopropylmagnesium chloride (1M, 0.4 milliliter, 0.4 mM) is added dropwise to and fills B " (200 millis
Gram, 0.263 mM), in the flask of 10 milliliters of tetrahydrofurans, under the conditions of nitrogen protection, reacted 1 hour at 0 degree Celsius, by three
Dibutyl tin oxide (130 milligrams, 0.4 mM) is added dropwise in flask, and heating is anti-overnight naturally after reacting 1 hour under 0 degree Celsius
It answers, aqueous ammonium chloride solution is added and is quenched, ethyl acetate extraction is concentrated to get product and is directly used in reacts in next step.Obtain 350 millis
G of compound C ", TLC purity 60%, yield 78.4%.
Embodiment 4:
1) synthesis of intermediate P'
Compound B-11 (273 milligrams, 1 mM) are added in 50 milliliters of flasks, and the chloro- 5 boric acid thiophene of 2- (162 milligrams, 1 milli
Mole), potassium carbonate (414 milligrams, 3 mMs), tetra-triphenylphosphine palladium (115.8 milligrams, 0.1 mM) and 20 milliliters of tetrahydro furans
It mutters 4 milliliters of water, is reacted overnight after 65 degree under nitrogen protection, concentration removes solvent, silica gel chromatograph post separation (stone after being cooled to room temperature
Oily ether: ethyl acetate=20:1) obtain P'280 milligrams of intermediate.Yield 90.3%.ESI-MS(M+H+):310.9。
2) synthesis of intermediate Q'
Compound P'(155 milligrams, 0.5 mM is added in 50 milliliters of flasks), N- bromo-succinimide (89 milligrams,
0.5 mM), 20 milliliters of n,N-Dimethylformamide, 25 degrees Celsius of reactions overnight, add elutriation to go out solid, centre are obtained by filtration
Q'175 milligrams of body, yield 89.9%.ESI-MS(M+H+):388.8。
3) synthesis of intermediate R':
It is added in a flask equipped with water segregator: compound B-11 (580 milligrams), ethylene glycol (2 milliliters), toluene (30
Milliliter), p-methyl benzenesulfonic acid (20 milligrams).Reaction solution is heated to reflux point water and stays overnight.It is cooled to room temperature, ethyl acetate dilution is added,
Saturated sodium bicarbonate aqueous solution, saturated common salt water washing are successively used, anhydrous sodium sulfate is dry.Revolving removes solvent, and crude product is used
Silica gel column chromatography (petrol ether/ethyl acetate=20:1) purifying obtains R'(480 milligrams of grease intermediate), yield 71%.1H-
NMR(400MHz,CDCl3)δ:7.35(dd,J=1.1Hz,5.4Hz,1H),7.21(dd,J=0.9Hz,3.5Hz,1H),7.18,
(s,1H),7.07(dd,J=3.7Hz,5.6Hz,1H),5.82(s,1H),4.14(m,2H),4.00(m,2H)。
4) synthesis of intermediate S'
Under nitrogen protection, compound R ' (160 milligrams) are dissolved in tetrahydrofuran (6 milliliters), are cooled to 0 DEG C, stir lower be added dropwise
Isopropylmagnesium chloride (1M tetrahydrofuran solution, 1 milliliter).Stirring 1 hour is added tributyltin chloride (0.32 milliliter), room temperature
The reaction was continued 1 hour.Saturated aqueous ammonium chloride is added to be quenched, ethyl acetate extraction, saturated common salt water washing, anhydrous sodium sulfate
It is dry.Revolving removes solvent, and crude product silica gel column chromatography (petrol ether/ethyl acetate=20:1) purifying obtains among grease
S'(200 milligrams of body), yield 75%.1H-NMR(400MHz,CDCl3)δ:7.32(dd,J=1.2Hz,5.4Hz,1H),7.26,(s,
1H),7.22(dd,J=1.0Hz,3.4Hz,1H),7.06(dd,J=3.6Hz,5.4Hz,1H),5.93(s,1H),4.15(m,
2H), 4.07 (m, 2H), 1.6 (m, 6H), 1.3 (m, 6H), 1.1 (m, 6H), 0.91 (m, 9H).
5) synthesis of intermediate T'
Compound 057-1(900 milligrams, 3.26 mMs is added in 50 milliliters of flasks) 20 milliliters of N, N- dimethyl formyl
20 milliliters of n,N-Dimethylformamide of N- bromo-succinimide (580 milligrams, 3.26 mMs) are slowly added dropwise under ice bath for amine
Solution after being slowly raised to room temperature, is stirred to react overnight, elutriation is added to go out T'800 milligrams of intermediate.Yield 69.1%.1H-NMR
(400MHz,CDCl3):6.961(d,1H),7.000(d,1H),7.163(t,1H),7.308(d,1H),7.501(m,2H),
10.073(s,1H).ESI-MS(M+H+):354.9。
6) synthesis of intermediate U'
It is added in a flask equipped with water segregator: T'(400 milligrams of compound), ethylene glycol (2 milliliters), toluene (30
Milliliter), p-methyl benzenesulfonic acid (20 milligrams).Reaction solution is heated to reflux point water and stays overnight.It is cooled to room temperature, ethyl acetate dilution is added,
Saturated sodium bicarbonate aqueous solution, saturated common salt water washing are successively used, anhydrous sodium sulfate is dry.Revolving removes solvent, and crude product is used
Silica gel column chromatography (petrol ether/ethyl acetate=20:1) purifying obtains U'(334 milligrams of grease intermediate), yield 71%.
7) synthesis of intermediate V'
Under nitrogen protection, U'(334 milligrams of compound) tetrahydrofuran (8 milliliters) are dissolved in, it is cooled to 0 DEG C, stirs lower be added dropwise
Isopropylmagnesium chloride (1M tetrahydrofuran solution, 1.7 milliliters).Stirring 1 hour is added tributyltin chloride (0.54 milliliter), room
The reaction was continued 1 hour for temperature.Saturated aqueous ammonium chloride is added to be quenched, ethyl acetate extraction, saturated common salt water washing, anhydrous slufuric acid
Sodium is dry.Revolving removes solvent, and crude product silica gel column chromatography (petrol ether/ethyl acetate=20:1) purifying obtains in grease
V'(420 milligrams of mesosome), yield 82%.1H-NMR(400MHz,CDCl3)δ:7.34(dd,J=1.0Hz,5.3Hz,1H),7.29
(d,J=3.1Hz,1H),7.28(s,1H),7.27(dd,J=1.0Hz,5.4Hz,1H),7.07(dd,J=3.3Hz,5.4Hz,
1H), 7.06 (d, J=3.1Hz, 1H), 5.89 (s, 1H), 4.20 (m, 2H), 4.03 (m, 2H), 1.57 (m, 6H), 1.35 (m,
6H),1.12(m,6H),0.96(t,J=7.2Hz,9H)。
8) synthesis of intermediate W'
By compound 3 bromo thiophene, simultaneously [3,2-b] thiophene (500 milligrams, 2.3 mMs) is dissolved in tetrahydrofuran (5 milliliters)
In, n-BuLi (1.76 milliliters, 4.6 mMs) are added dropwise under the conditions of -78 DEG C, are reacted 20 minutes under the conditions of -78 DEG C, N is added,
N- dimethyl acetamide (0.35 milliliter, 4.6 mMs).Under the conditions of nitrogen protection, mixture reacts 2 hours, and saturation is added
Aqueous ammonium chloride solution quenching reaction, ethyl acetate extract (20 milliliters, three times), and concentration removes silica gel chromatograph post separation after solvent
(petroleum ether: methylene chloride=1:2) obtains 200 milligrams of compound W ', LC-MS purity: 100%, yield 52%.1H-NMR
(400MHz,CDCl3)δ:7.256-7.270(d,1H),7.621-7.634(d,1H),7.876(s,1H),9.099(s,1H)。
9) intermediate X ' synthesis
250 milligrams of W' are dissolved in 10 ml methanols, 0 DEG C is cooled under stirring.280 milligrams of sodium borohydrides are added, react
30 minutes.Revolving removes most of methanol, is diluted with water.Ethyl acetate extraction, anhydrous sodium sulfate is dry, obtains after removing solvent
White solid intermediate X ' (250 milligrams), yield 99%.1H-NMR(400MHz,CDCl3)δ:7.36(d,J=5.3Hz,1H),
7.24(d,J=5.3Hz,1H),7.20(s,1H),4.87(s,2H)。
10) synthesis of intermediate Y'
By X'(200 milligrams), NBS(500 milligrams) it is dissolved in 15 milliliters of tetrahydrofurans, it is stirred at room temperature 3 hours.Add water quenching
It goes out, ethyl acetate extraction, anhydrous sodium sulfate drying.Revolving removes solvent, and crude product silica gel column chromatography purifies (petroleum ether: acetic acid
Ethyl ester=1:2) obtain Y'(120 milligrams of white solid intermediate), yield 31%.1H-NMR(400MHz,CDCl3)δ:7.29(s,
1H),4.86(d,J=6.3Hz,2H),1.95(t,J=6.2Hz,1H)。
11) synthesis of intermediate Z'
By Y'(120 milligrams), PDC(280 milligrams) it is dissolved in 10 milliliters of methylene chloride, it is stirred at room temperature 3 hours.Diatom is added
Soil is vigorously stirred lower addition ether.Filtering, solid are washed with ethyl acetate, and merging filtrate revolving obtains green admittedly after removing solvent
Z'(110 milligrams of body intermediate), yield 92%.1H-NMR(400MHz,CDCl3) δ: 10.03 (s, 1H) 7.40 (s, 1H).
Embodiment 5:
1) synthesis of compound 020-1: by intermediate H (1.39 grams, 3.8 mMs), intermediate V (2 grams, 4.56 mmoles
You), potassium carbonate (1.6 grams, 0.4 mole) be added to 250 milliliters of there-necked flasks for filling 100 milliliters of tetrahydrofurans and 30 milliliters of water
In, tetra-triphenylphosphine palladium (0.448 gram, 0.4 mM) is added under the conditions of nitrogen protection, solution reacted under 68 degrees Celsius
Night separates organic layer after being cooled to room temperature, is concentrated to get crude product, and silica gel crosses column (petroleum ether: ethyl acetate=6:1) and obtains 0.7 gram
Compound 020-1, LC-MS purity: 100%, yield 38%.1H-NMR(400MHz,DMSO-d6)δ:3.227(s,3H),3.399
(s, 3H), 3.748 (s, 6H), 6.770 (d, 2H), 6.935 (d, 4H), 7.051 (d, 4H), 7.130 (d, 1H), 7.309 (d,
1H), 7.463 (d, 2H), 7.532 (m, 2H), 7.610 (d, 1H).ESI-MS[M+H]+: 584.2.
2) synthesis of compound 020-2: under nitrogen protection, by 020-1(66 milligrams of compound, 0.113 mM), in
L(50.3 milligrams of mesosome, 0.125 mM), cesium carbonate (74 milligrams, 0.22 mM), two tri-tert phosphorus palladiums (10 milligrams,
0.011 mM) and (80 milliliters) of toluene mix and be stirred to react under 110 degree 2 hours.After being cooled to room temperature, concentration is removed
Remove solvent, silica gel column chromatography (petroleum ether: ethyl acetate=2:1) obtains 70 milligrams of compound 020-2, LC-MS purity: 98.6%,
Yield 74.8%.1H-NMR(400MHz,DMSO-d6)δ:3.292(s,3H),3.434(s,3H),3.755(s,6H),6.790
(d, 2H), 6.937 (d, 4H), 7.049 (d, 4H), 7.205 (d, 1H), 7.342 (d, 1H), 7.488 (d, 2H), 7.729 (d,
1H), 7.832 (m, 3H), 7.898 (d, 1H), 8.011 (d, 2H), 8.228 (d, 2H), 8.432 (d, 2H) .ESI-MS [M+H]+:
828.2。
3) compound 020-3 is synthesized: under subzero 78 degrees celsius, by the diisopropyl aluminum hydride of 1M (2.5 milliliters, 2.5
MM) be added to 020-2(414 milligrams of compound, 0.5 mM) tetrahydrofuran (20 milliliters) solution in, slowly heat up
Overnight to room temperature reaction, methylene chloride (10 milliliters), water (15 milliliters) are added in reaction solution, separate organic layer, concentration removes molten
Agent, silica gel column chromatography (petroleum ether: ethyl acetate=5:1) obtain 250 milligrams of compound 020-3, LCMS purity: 99.2%, yield
65.1%。1H-NMR (400MHz, DMSO-d6) 3.752 (s, 6H), 6.776 (d, 2H), 6.872 (s, 1H), 6.927 (d, 4H),
7.059 (d, 4H), 7.400 (s, 1H), 7.514 (d, 2H), 7.776 (m, 2H), 7.935 (m, 3H), 8.244 (m, 3H), 8.402
(d, 2H), 10.240 (s, 1H).ESI-MS[M+H]+: 769.2.
4) synthesis of CGTD-DSSC-020: under nitrogen protection, by 020-3(192 milligrams of above compound, 0.25 mmoles
You), cyanoacetic acid (42.5 milligrams, 0.5 mM), ammonium acetate (38.5 milligrams, 0.5 mM) and (5 milliliters) of acetic acid are mixed
Merging is stirred to react 5 hours under 125 degrees Celsius.There is solid precipitation after being cooled to room temperature, 104 milligrams of compounds are obtained by filtration
CGTD-DSSC-020, LC-MS purity: 100%, yield 50%.1H-NMR(400MHz,DMSO-d6)3.750(s,6H),6.776
(d,2H),6.872(s,1H),6.928(d,4H),7.058(d,4H),7.104(d,1H),7.401(s,1H),7.504(d,
2H),7.766(m,2H),7.939(m,3H),8.242(m,3H),8.405(d,2H),12.560(s,1H).ESI-MS[M+H
]+: 836.2.
Embodiment 6:
1) compound L (202 milligrams, 0.5 mM), A1(135 the synthesis of compound 021-1: are added in 50 milliliters of flasks
Milligram, 0.5 mM), tetra-triphenylphosphine palladium (58 milligrams, 0.05 mM), potassium carbonate (208 milligrams, 1.5 mMs) and
15 milliliters and 8 milliliters of water of tetrahydrofuran.Under the conditions of nitrogen protection, mixture reacts 2 hours at 68 degrees Celsius, is cooled to room temperature
Afterwards, concentration removes solvent, and silica gel crosses column (petroleum ether: ethyl acetate=10:1) and obtains 150 milligrams of compound 021-1, yield
64.1%。1H-NMR(400MHz,DMSO-d6) δ: 7.632 (s, 1H), 7.830 (m, 3H), 8.242 (d, 2H), 8.438 (s, 2H),
9.762 (s, 1H).ESI-MS[M+H]+: 468.0.
2) compound 021-2(135.4 milligrams, 0.2 mM the synthesis of compound 021-3: is added in 50 milliliters of flasks),
021-1(93.6 milligrams of compound, 0.2 mM), tetra-triphenylphosphine palladium (25 milligrams, 0.02 mM) and toluene milliliter.
Under the conditions of nitrogen protection, mixture reacts 3 hours at 90 degrees Celsius, and after being cooled to room temperature, concentration removes solvent, and silica gel crosses column
(petroleum ether: ethyl acetate=5:1) obtains 120 milligrams of compound 021-3, LC-MS purity: 100%, yield 77.5%.1H-NMR
(400MHz, DMSO-d6) 3.795 (s, 6H), 6.791 (d, 2H), 6.971 (d, 4H), 7.089 (d, 4H), 7.347 (d, 1H),
7.473 (m, 3H), 7.654 (s, 1H), 7.843 (m, 3H), 8.261 (d, 2H), 8.453 (d, 2H), 9.898 (s, 1H).ESI-
MS[M+H]+: 775.2.
3) synthesis of CGTD-DSSC-021: under nitrogen protection, by 021-3(120 milligrams of above compound, 0.155 in the least
Mole), cyanoacetic acid (26.4 milligrams, 0.0.31 mMs), ammonium acetate (23.9 milligrams, 0.31 mM) and acetic acid (5
Milliliter) it mixes and is stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, 76 milligrams of changes are obtained by filtration
Close object CGTD-DSSC-021.LC-MS purity: 100%, yield 58.3%.1H-NMR(400MHz,DMSO-d6)3.748(s,6H),
6.730 (d, 2H), 6.824 (d, 4H), 7.035 (d, 4H), 7.289 (d, 1H), 7.330 (d, 1H), 7.445 (d, 2H), 7.644
(d, 2H), 7.763 (d, 1H), 7.981 (s, 2H), 8.212 (d, 2H), 8.389 (d, 2H), 13.920 (s, 1H) .ESI-MS [M+
H]+: 842.2.
Embodiment 7:
1) synthesis of compound 022-1: in 50 milliliters of flasks be added compound 021-2(203 milligram, 0.3 mM), change
Close object A1(81 milligrams, 0.3 mM), tetra-triphenylphosphine palladium (35 milligrams, 0.03 mM) and 20 milliliters of toluene.In nitrogen
Under protective condition, mixture reacts 16 hours at 90 degrees Celsius, and after being cooled to room temperature, concentration removes solvent, and silica gel crosses column (petroleum
Ether: ethyl acetate=20:1) obtain 90 milligrams of compound 022-1, yield 52.2%.1H-NMR(400MHz,DMSO-d6)δ:3.753
(s, 6H), 6.762 (d, 2H), 6.937 (d, 4H), 7.079 (d, 4H), 7.432 (d, 2H), 7.546 (m, 4H), 9.955 (s,
1H),.ESI-MS[M+H]+: 577.1.
2) compound 022-1(90 milligrams, 0.156 mM the synthesis of compound 022-2: is added in 25 milliliters of flasks),
Compound L (70 milligrams, 0.172 mM), tetra-triphenylphosphine palladium (18.2 milligrams, 0.016 mM), potassium carbonate (65 milligrams,
0.47 mM) and 10 milliliters and 5 milliliters of water of tetrahydrofuran.Under the conditions of nitrogen protection, mixture reacts 3 at 68 degrees Celsius
Hour, after being cooled to room temperature, organic layer is separated, concentration removes solvent, and silica gel column chromatography (petroleum ether: ethyl acetate=10:1) obtains
To 65 milligrams of compound 022-2, LC-MS purity: 100%, yield 54.2%.1H-NMR(400MHz,DMSO-d6)3.798(s,
6H), 6.793 (d, 2H), 6.974 (d, 4H), 7.092 (d, 4H), 7.347 (d, 1H), 7.473 (m, 3H), 7.654 (s, 1H),
7.843 (m, 3H), 8.263 (d, 2H), 8.455 (d, 2H), 9.958 (s, 1H).ESI-MS[M+H]+: 775.2.
3) synthesis of CGTD-DSSC-022: under nitrogen protection, by 022-2(65 milligrams of above compound, 0.084 mmoles
You), cyanoacetic acid (28 milligrams, 0.34 mM), ammonium acetate (25 milligrams, 0.34 mM) and (5 milliliters) of acetic acid mixing
And it is stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, 36 milligrams of compound CGTD- are obtained by filtration
DSSC-022, LC-MS purity: 100%, yield 50.9%.1H-NMR (400MHz, DMSO-d6) 3.762 (s, 6H), 6.762 (d,
2H),6.846(d,4H),7.072(d,4H),7.297(s,1H),7.480(m,3H),7.805(m,3H),8.172(m,3H),
8.265(s,1H),8.395(d,2H),13.820(s,1H)。ESI-MS[M+H]+: 842.2.
Embodiment 8 and embodiment 9:
1) synthesis of compound 024-2: by compound X (102.8 milligrams, 0.18 mM), compound 024-1 (100 millis
Gram, 0.18 mM), potassium carbonate (75 milligrams, 0.54 mole) be added to 50 millis for filling 15 milliliters of tetrahydrofurans and 6 milliliters of water
It rises in there-necked flask, tetra-triphenylphosphine palladium (21 milligrams, 0.018 mM) is added under the conditions of nitrogen protection, solution is at 68 degrees Celsius
Lower reaction overnight, separates organic layer after being cooled to room temperature, is concentrated to get crude product, silica gel crosses column (petroleum ether: ethyl acetate=5:1)
Obtain 100 milligrams of compound 024-2, LC-MS purity: 100%, yield 60.3%.1H-NMR(400MHz,DMSO-d6)0.881
(t, 6H), 1.313 (m, 8H), 1.412 (m, 4H), 1.700 (m, 4H), 3.935 (t, 4H), 6.746 (d, 2H), 6.916 (d,
4H), 7.041 (d, 4H), 7.439 (d, 2H), 7.508 (d, 2H), 7.608 (m, 2H), 7.745 (d, 1H), 7.795 (s, 1H),
7.918(d,1H),8.348(m,2H),10.063(s,1H)。ESI-MS[M+H]+: 920.2.
2) synthesis of compound CGTD-DSSC-024: under nitrogen protection, by above-mentioned 024-2(30 milligrams of compound,
0.033 mM), 024-3(13.3 milligrams of compound, 0.13 mM), ammonium acetate (10 milligrams, 0.13 mM), and
(5 milliliters) of acetic acid mix and are stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration 25
Milligram compound CGTD-DSSC-024, LC-MS purity: 100%, yield 69.2%.1H-NMR (400MHz, DMSO-d6)0.882
(t, 6H), 1.306 (m, 8H), 1.401 (m, 4H), 1.700 (m, 4H), 3.926 (t, 4H), 4.679 (s, 2H) 6.726 (d,
2H), 6.898 (d, 4H), 7.016 (d, 4H), 7.300 (d, 1H), 7.442 (m, 4H), 7.575 (d, 1H), 7.686 (s, 1H),
7.843(d,1H),8.276(d,1H),13.818(s,1H).ESI-MS[M+H]+: 1093.2.
3) synthesis of compound CGTD-DSSC-025: under nitrogen protection, by above-mentioned compound 024-2(55.3 milli
Gram, 0.06 mM), cyanoacetic acid (20.4 milligrams, 0.24 mM), ammonium acetate (18.5 milligrams, 0.24 mM), and
(5 milliliters) of acetic acid mix and are stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration 50
Milligram compound CGTD-DSSC-025, LC-MS purity: 100%, yield 84.3%.1H-NMR(400MHz,DMSO-d6)0.868
(t, 6H), 1.276 (m, 8H), 1.408 (m, 4H), 1.702 (m, 4H), 3.942 (t, 4H), 6.760 (d, 2H), 6.919 (d,
4H), 7.066 (d, 4H), 7.382 (d, 1H), 7.515 (m, 4H), 7.763 (d, 1H), 7.795 (s, 1H), 8.177 (d, 1H),
8.269(d,1H),8.394(m,2H),13.925(s,1H)。ESI-MS[M+H]+: 987.2.
Embodiment 10:
1) synthesis of compound 026-2: by compound X (45.7 milligrams, 0.08 mM), compound 026-1 (51.2 millis
Gram, 0.08 mM), 33 milligrams of potassium carbonate, 0.24 mole) be added to 50 millis for filling 15 milliliters of tetrahydrofurans and 6 milliliters of water
It rises in there-necked flask, tetra-triphenylphosphine palladium (9.3 milligrams, 0.008 mM) is added under the conditions of nitrogen protection, solution is at 68 degrees Celsius
Lower reaction overnight, separates organic layer after being cooled to room temperature, is concentrated to get crude product, silica gel crosses column (petroleum ether: ethyl acetate=5:1)
Obtain 45 milligrams of compound 026-2, LC-MS purity: 100%, yield 56.3%.1H-NMR(400MHz,DMSO-d6)0.870(t,
3H),0.931(t,6H),1.246(m,6H),1.365(m,8H),1.466(m,4H),1.654(m,2H),1.735(m,4H),
2.664 (t, 2H), 3.973 (t, 4H), 6.825 (d, 2H), 6.929 (d, 4H), 7.077 (d, 4H), 7.412 (s, 1H), 7.506
(d, 2H), 7.637 (d, 1H), 7.771 (d, 1H), 7.844 (s, 1H), 7.949 (s, 1H), 8.300 (s, 1H), 8.383 (d,
2H),9.834(s,1H)。ESI-MS[M+H]+: 1004.3.
2) synthesis of compound CGTD-DSSC-026: under nitrogen protection, by above-mentioned 026-2(40 milligrams of compound,
0.04 mM), cyanoacetic acid (13.5 milligrams, 0.16 mM), ammonium acetate (12.3 milligrams, 0.16 mM), Yi Jiyi
(5 milliliters) of acid mix and are stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, 25 millis are obtained by filtration
G of compound CGTD-DSSC-026, LC-MS purity: 100%, yield 58.3%.1H-NMR(400MHz,DMSO-d6)0.766(t,
3H),0.798(t,6H),1.227(m,8H),1.314(m,8H),1.404(m,4H),1.560(m,2H),1.691(m,4H),
3.916 (t, 4H), 6.745 (d, 2H), 6.903 (d, 4H), 7.024 (d, 4H), 7.382 (d, 1H), 7.461 (m, 4H), 7.754
(m,2H),7.900(d,1H),8.184(s,1H),8.333(m,2H),13.925(s,1H)。ESI-MS[M+H]+: 1071.3.
Embodiment 11:
1) synthesis of compound 027-1: compound N 1(200 milligrams is added in 100 milliliters of three-necked flasks, 0.34 mmoles
You), 1(130 milligram of intermediate B, 0.48 mM), tetra-triphenylphosphine palladium (60 milligrams, 0.05 mM) and toluene 10 in the least
It rises.Under the conditions of nitrogen protection, mixture reacts 16 hours at 100 DEG C.Concentration removes solvent, and silica gel crosses column (petroleum ether: acetic acid
Ethyl ester=10:1) obtain 120 milligrams of compound 027-1, yield 73%.1H-NMR(400MHz,CDCl3)δ:10.10(s,1H),
8.28 (s, 1H), 7.96 (d, J=8.3Hz, 1H), 7.69 (s, 1H), 7.60~7.62 (m, 2H), 7.53 (dd, J=5.2,
1.2Hz, 1H), 7.35 (dd, J=3.6,1.2Hz, 1H), 7.25 (d, J=3.6Hz, 2H), 7.17~7.19 (m, 1H).
2) synthesis of compound 027-2: N- bromo-succinimide (41 milligrams, 2.3 mMs) is added to compound
In n,N-Dimethylformamide (8 milliliters) solution of 027-1 (95 milligrams, 2.0 mMs), stirred under nitrogen atmosphere, which stays overnight, to be had
Solid is precipitated, filtering, and solid vacuum drying obtains 85 milligrams of yellow solid product compound 027-2, yield 76%.ESI-MS[M+
H]+: 557.
3) synthesis of compound 027-3: to T(30 milligrams of compound, 0.05 mM), 027-2(30 milligrams of compound,
0.05 mM), tetra-triphenylphosphine palladium (24 milligrams, 0.02 mM), sodium carbonate (20 milligrams, 0.2 mM) and 6 milliliter four
In the mixture of hydrogen furans, 1 milliliter of water is added, reaction mixture reacts 16 hours at 65 DEG C.Evaporating solvent under reduced pressure, residual silicon
Gel column chromatography eluting (petroleum ether: ethyl acetate=15:1), obtains 30 milligrams of dark red solid compound 027-3, yield: 63%.1H-
NMR(400MHz,CDCl3): δ 10.20 (s, 1H), 8.29 (s, 1H), 7.96 (d, J=8.0Hz, 2H), 7.60~7.68 (m,
7H), 7.52 (d, J=8.0Hz, 2H), 7.40 (d, J=8.0Hz, 2H), 7.27~7.35 (m, 9H), 7.21 (d, J=8.4Hz,
2H),7.14(dd,J=8.4,1.6Hz,2H),1.43(s,12H)。
4) synthesis of compound CGTD-DSSC-027: under nitrogen protection, by 027-3(30 milligrams of compound, 0.03 in the least
Mole), cyanoacetic acid (10 milligrams, 0.12 mM), ammonium acetate (5 milligrams, 0.07 mM) and (5 milliliters) of acetic acid are mixed
Merging is stirred to react 6 hours at 125 DEG C.Evaporating solvent under reduced pressure acetic acid, residue silica gel column chromatography (methylene chloride: methanol=
20:1) obtain 12 milligrams of bright black solid chemical compound CGTD-DSSC-027, LC-MS purity: 100%, yield: 40%.1H-NMR
(400MHz,DMSO-d6): δ 8.14~8.24(m, 3H), 7.99~8.05 (m, 1H), 7.65~7.72 (m, 5H), 7.41~
7.49 (m, 6H), 7.18~7.28 (m, 8H), 6.98~7.05 (m, 4H), 1.31 (s, 12H).
Embodiment 12:
1) synthesis of compound 028-2: by compound T (51.2 milligrams, 0.08 mM), compound 028-1 (48.2 millis
Gram, 0.08 mM), 33 milligrams of potassium carbonate, 0.24 mole) be added to 50 millis for filling 15 milliliters of tetrahydrofurans and 6 milliliters of water
It rises in there-necked flask, tetra-triphenylphosphine palladium (9.3 milligrams, 0.008 mM) is added under the conditions of nitrogen protection, solution is at 68 degrees Celsius
Lower reaction overnight, separates organic layer after being cooled to room temperature, is concentrated to get crude product, silica gel crosses column (petroleum ether: ethyl acetate=5:1)
Obtain 60 milligrams of compound 028-2, LC-MS purity: 100%, yield 72.3%.ESI-MS[M+H]+: 1036.28.
2) synthesis of compound CGTD-DSSC-028: under nitrogen protection, by above-mentioned 028-2(52 milligrams of compound,
0.05 mM), cyanoacetic acid (17 milligrams, 0.2 mM), ammonium acetate (15.4 milligrams, 0.2 mM) and acetic acid (5
Milliliter) it mixes and is stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, 32 milligrams of changes are obtained by filtration
Object CGTD-DSSC-028 is closed, LC-MS purity: 100%, yield 57.9%.1H-NMR(400MHz,DMSO-d6)0.784(t,3H),
1.176 (m, 8H), 1.355 (s, 12H), 1.589 (m, 12H), 7.049 (m, 4H), 7.263 (m, 6H), 7.504 (m, 4H),
7.604 (m, 2H), 7.729 (m, 5H), 7.832 (s, 1H), 7.904 (d, 1H), 8.196 (d, 1H), 8.33O (s, 2H),
13.925(s,1H)。ESI-MS[M+H]+: 1071.3.
Embodiment 13:
1) synthesis of compound 029-2: under nitrogen protection, by compound B-11 (41 milligrams, 0.15 mM), compound
029-1(61 milligrams, 0.17 mM), potassium carbonate (62 milligrams, 0.45 mM), four triphenyl phosphorus palladiums (18 milligrams, 0.015
MM) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature, concentration
Solvent is removed, silica gel column chromatography (petroleum ether: ethyl acetate=100:1) obtains 40 milligrams of compound 029-2, LC-MS purity
99.6%, yield 63.5%.ESI-MS[M+H]+: 420.8.
2) synthesis of compound 029-3: by compound 029-2 (50 milligrams, 0.12 mM), NBS (28 milligrams, 0.15
MM) be added to and fill in 10 milliliters of DMF50 milliliters of round-bottomed flask bottles, it is reacted overnight at 32 DEG C, adds water quenching reaction, have
Solid is precipitated, and suction filtration is dried to obtain 30 milligrams of compound 029-3, LC-MS purity 98.7%, yield 50.8%.1H-NMR
(400MHz,CDCl3)δ:7.091-7.136(m,2H),7.219(d,1H),7.329(d,1H),7.585(s,1H),7.636-
7.705(m,4H)。
3) synthesis of compound 029-4: under nitrogen protection, by 029-3(30 milligrams of compound, 0.06 mM), change
Close object V(32 milligrams, 0.072 mM), potassium carbonate (24 milligrams, 0.18 mM), four triphenyl phosphorus palladiums (7 milligrams, 0.006
MM) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature, concentration
Solvent is removed, silica gel column chromatography (petroleum ether: ethyl acetate=40:1) obtains 40 milligrams of compound 029-4, LC-MS purity
99.3%, yield 90%.ESI-MS[M+H]+: 726.2.
4) synthesis of compound GTD-DSSC-029: under nitrogen protection, by 029-4(40 milligrams of compound, 0.06 mmoles
You), cyanoacetic acid (20 milligrams, 0.24 mM), ammonium acetate (19 milligrams, 0.24 mM) and (5 milliliters) of acetic acid mixing
And it is stirred to react at 125 DEG C 5 hours.There is solid precipitation after being cooled to room temperature, filters, filter cake column chromatography for separation (methylene chloride:
Methanol=40:1) obtain 25 milligrams of compound GTD-DSSC-029, LC-MS purity 100%, yield 58.1%.1H-NMR(400MHz,
DMSO-d6)3.747(s,6H),6.753(d,2H),6.924(d,4H),7.050(d,4H),7.216(d,1H),7.049-
7.477(m,4H),7.680-7.739(m,3H),7.880(d,2H),7.969(s,1H),8.123(s,1H).ESI-MS[M+H
]+: 791.7.
Embodiment 14:
1) synthesis of compound 030-2: by intermediate T (59.5 milligrams, 0.1 mM), compound 030-1 (66 milligrams,
0.11 mM), cesium carbonate (99 milligrams, 0.3 mM), bis- (dibenzalacetone) palladiums (7.5 milligrams, 0.005 mM),
Tributyl phosphorus tetrafluoroborate (9.6 milligrams, 0.02 mM) is added in the there-necked flask for filling 15 milliliters of dioxanes, and nitrogen is protected
Under the conditions of shield, solution reacts overnight under 109 degrees Celsius, is cooled to after room temperature and is concentrated to get crude product, silica gel cross column (petroleum ether:
Ethyl acetate=5:1) obtain 40 milligrams of compound 030-2, LC-MS purity: 100%, yield 39.2%.ESI-MS[M+H]+:
1036.28。
2) synthesis of compound CGTD-DSSC-030: under nitrogen protection, by above-mentioned 030-2(40 milligrams of compound,
0.038 mM), cyanoacetic acid (13 milligrams, 0.15 mM), ammonium acetate (11.8 milligrams, 0.15 mM) and acetic acid
(5 milliliters) mix and are stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration 32 milligrams
Compound CGTD-DSSC-030, LC-MS purity: 100%, yield 57.9%.1H-NMR (400MHz, DMSO-d6): 0.787 (t,
3H), 1.176 (m, 6H), 1.334 (s, 12H), 1.542 (m, 2H), 2.602 (t, 2H), 7.014 (d, 2H), 7.038 (d, 2H),
7.095(s,1H),7.254(m,8H),7.378(d,1H),7.485(d,2H),7.632(d,2H),7.698(m,4H),7.800
(d,1H),8.042(s,1H),8.176(s,1H),8.222(m,2H),13.925(s,1H).ESI-MS[M+H]+: 1071.3.
Embodiment 15:
1) synthesis of compound 031-1: under nitrogen protection, by 029-3(50 milligrams of compound, 0.1 mM), chemical combination
X(62 milligrams of object, 0.11 mM), potassium carbonate (40 milligrams, 0.3 mM), four triphenyl phosphorus palladiums (12 milligrams, 0.01 mmoles
You) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 68 DEG C 8 hours.After being cooled to room temperature, concentration is removed
Solvent, silica gel column chromatography (petroleum ether: ethyl acetate=50:1) obtain 56 milligrams of compound 031-1, LC-MS purity 98.1%, produce
Rate 65.1%.ESI-MS[M+H]+: 867.4.
2) synthesis of compound CGTD-DSSC-031: under nitrogen protection, by 031-1(56 milligrams of compound, 0.06 in the least
Mole), cyanoacetic acid (20 milligrams, 0.24 mM), ammonium acetate (19 milligrams, 0.24 mM) and acetic acid (10 milliliters)
It mixes and is stirred to react at 125 DEG C 5 hours.There is solid precipitation after being cooled to room temperature, filters, filter cake column chromatography for separation (dichloro
Methane: methanol=40:1) obtain 27 milligrams of compound CGTD-DSSC-031, LC-MS purity 100%, yield 45%.1H-NMR
(400MHz,DMSO-d6)0.878(t,6H),1.257-1.317(m,8H),1.405(t,4H),1.658-1.728(m,4H),
3.921(t,4H),6.741(d,2H),6.896(d,4H),7.016(d,4H),7.217(d,1H),7.403-7.469(m,
4H),7.684-7.741(m,3H),7.886(d,2H),7.974(s,1H),8.120(s,1H).ESI-MS[M+H]+: 931.2.
Embodiment 16:
1) synthesis of compound 032-2: under nitrogen protection, by compound 032-1 (100 milligrams, 0.23 mM), change
It closes object B1 (71 milligrams, 0.25 mM), potassium carbonate (96 milligrams, 0.69 mM), and four triphenyl phosphorus palladiums (27 milligrams, 0.023
MM) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature, concentration
Solvent is removed, silica gel column chromatography (petroleum ether: ethyl acetate=100:1) obtains 44 milligrams of compound 032-2, LC-MS purity
100%, yield 40%.ESI-MS[M+H]+: 494.1.
2) synthesis of compound 032-3: by compound 032-2 (44 milligrams, 0.09 mM), NBS (17 milligrams, 0.095
MM) be added to and fill in 10 milliliters of DMF25 milliliters of round-bottomed flask bottles, it is reacted overnight at 27 DEG C, adds water quenching reaction, have
Solid is precipitated, and silica gel column chromatography (petroleum ether: ethyl acetate=30:1) obtains 40 milligrams of compound 032-3, LC-MS purity 83%,
Yield 78%.ESI-MS[M+H]+: 572.9.
3) synthesis of compound 032-4: under nitrogen protection, by 032-3(40 milligrams of compound, 0.07 mM), change
Close object X(40 milligrams, 0.07 mM), potassium carbonate (30 milligrams, 0.21 mM), four triphenyl phosphorus palladiums (9 milligrams, 0.007 milli
Mole) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature, concentration is removed
Solvent is removed, silica gel column chromatography (petroleum ether: ethyl acetate=40:1) obtains 40 milligrams of compound 032-4, LC-MS purity 100%, produces
Rate 61%.ESI-MS[M+H]+: 936.35.
4) synthesis of compound CGTD-DSSC-032: under nitrogen protection, by 032-4(40 milligrams of compound, 0.043 in the least
Mole), cyanoacetic acid (15 milligrams, 0.17 mM), ammonium acetate (13 milligrams, 0.17 mM) and (5 milliliters) of acetic acid are mixed
Merging is stirred to react 5 hours at 125 DEG C.There is solid precipitation after being cooled to room temperature, filters, filter cake column chromatography for separation (dichloromethane
Alkane: methanol=40:1) obtain 25 milligrams of compound CGTD-DSSC-032, LC-MS purity 100%, yield 58.1%.1H-NMR
(400MHz,DMSO-d6)0.853-0.899(t,9H),1.232-1.411(m,18H),1.665-1.733(m,4H),1.797-
1.852(m,2H),3.097-3.133(t,2H),3.918-3.950(t,4H),6.751-6.772(d,2H),6.870-6.923
(d,4H),7.031-7.053(d,4H),7.226-7.236(d,1H),7.411-7.444(q,2H),7.483-7.505(d,
2H),7.664-7.673(d,2H),7.712-7.733(d,2H),7.981(s,1H),8.064-8.107(t,2H),8.240
(s,1H)。ESI-MS[M+H]+: 1003.35.
Embodiment 17:
1) synthesis of compound 034-3: by compound 034-1 (48.3 milligrams, 0.07 mM), compound 034-2 (28
Milligram, 0.0.077 mMs), potassium carbonate (29 milligrams, 0.21 mM), tetra-triphenylphosphine palladium (8.2 milligrams, 0.007 mmoles
You) it is added in the flask for filling 15 milliliters of tetrahydrofurans and 6 milliliters of water, under the conditions of nitrogen protection, solution is under 69 degrees Celsius
Reaction overnight, is concentrated to get crude product after being cooled to room temperature, silica gel crosses column (petroleum ether: ethyl acetate=10:1) and obtains 30 milligrams of changes
Object 034-3 is closed, LC-MS purity: 100%, yield 51.1%.ESI-MS[M+H]+: 838.2.
2) synthesis of compound CGTD-DSSC-034: under nitrogen protection, by above-mentioned 034-3(25 milligrams of compound,
0.03 mM), cyanoacetic acid (10.2 milligrams, 0.12 mM), ammonium acetate (9.2 milligrams, 0.12 mM) and acetic acid
(5 milliliters) mix and are stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration 18 milligrams
Compound CGTD-DSSC-034, LC-MS purity: 100%, yield 66.7%.1H-NMR (400MHz, DMSO-d6): 0.878 (t,
6H),1.309(m,8H),1.395(m,4H),1.696(m,4H),3.923(t,4H),6.904(d,4H),6.982(m,5H),
7.265(s,1H),7.534(m,2H),7.750(m,3H),7.829(d,1H),8.933(d,2H),8.068(s,1H),8.258
(s,1H),13.925(s,1H)。ESI-MS[M+H]+: 904.2.
Embodiment 18:
1) synthesis of compound 035-1: under nitrogen protection, by 029-3(50 milligrams of compound, 0.10 mM), change
Close object Q(75 milligrams, 0.12 mM), potassium carbonate (40 milligrams, 0.30 mM), four triphenyl phosphorus palladiums (12 milligrams, 0.01 milli
Mole) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 68 DEG C 8 hours.After being cooled to room temperature, concentration is removed
Solvent is removed, silica gel column chromatography (petroleum ether: ethyl acetate=50:1) obtains 55 milligrams of compound 035-1, LC-MS purity 98.5%,
Yield 59.7%.ESI-MS[M+H]+: 923.4.
2) synthesis of compound CGTD-DSSC-035: under nitrogen protection, by 035-1(55 milligrams of compound, 0.06 in the least
Mole), cyanoacetic acid (20 milligrams, 0.24 mM), ammonium acetate (19 milligrams, 0.24 mM) and acetic acid (15 milliliters)
It mixes and is stirred to react at 125 DEG C 5 hours.There is solid precipitation after being cooled to room temperature, filters, filter cake column chromatography for separation (dichloro
Methane: methanol=40:1) obtain 25 milligrams of compound CGTD-DSSC-035, LC-MS purity 100%, yield 42.3%.1H-NMR
(400MHz,DMSO-d6)0.881(t,6H),1.232-1.319(m,8H),1.407(t,4H),1.659-1.711(m,4H),
3.915(t,4H),6.873(d,5H),6.969(d,4H),7.179(d,1H),7.266(d,1H),7.435-7.467(m,
2H),7.519(s,1H),7.677-7.743(m,4H),7.887(d,2H),7.983(s,1H),8.095(s,1H)。ESI-MS
[M+H]+: 987.2.
Embodiment 19:
1) synthesis of compound 036-2: under nitrogen protection, by compound 036-1 (193 milligrams, 0.46 mM), change
It closes object B1 (125 milligrams, 0.46 mM), potassium carbonate (190 milligrams, 1.38 mMs), four triphenyl phosphorus palladiums (55 milligrams,
0.046 mM) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature,
Concentration removes solvent, and it is pure that silica gel column chromatography (petroleum ether: ethyl acetate=100:1) obtains 150 milligrams of compounds 036-2, LC-MS
Degree 100%, yield 67%.ESI-MS[M+H]+: 487.98.
2) synthesis of compound 036-3: by compound 036-2 (75 milligrams, 0.15 mM), NBS (30 milligrams, 0.17
MM) be added to and fill in 10 milliliters of DMF25 milliliters of round-bottomed flask bottles, it is reacted overnight at 27 DEG C, adds water quenching reaction, have
Solid is precipitated, and silica gel column chromatography (petroleum ether: ethyl acetate=30:1) obtains 75 milligrams of compound 036-3, LC-MS purity 100%,
Yield 86%.ESI-MS[M+H]+: 567.89.
3) synthesis of compound 036-4: under nitrogen protection, by X(89 milligrams of compound, 0.132 mM), compound
036-3(75 milligrams, 0.132 mM), potassium carbonate (55 milligrams, 0.4 mM), four triphenyl phosphorus palladiums (15 milligrams, 0.0132
MM) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature, concentration
Solvent is removed, silica gel column chromatography (petroleum ether: ethyl acetate=200:3) obtains 86 milligrams of compound 036-4, LC-MS purity
100%, yield 70%.ESI-MS[M+H]+: 931.26.
4) synthesis of compound CGTD-DSSC-036: under nitrogen protection, by 036-4(86 milligrams of compound, 0.09 in the least
Mole), cyanoacetic acid (32 milligrams, 0.37 mM), ammonium acetate (29 milligrams, 0.37 mM) and acetic acid (10 milliliters)
It mixes and is stirred to react at 125 DEG C 5 hours.There is solid precipitation after being cooled to room temperature, filters, filter cake column chromatography for separation (dichloro
Methane: methanol=40:1) obtain 50 milligrams of compound CGTD-DSSC-036, LC-MS purity 100%, yield 56.2%.1H-NMR
(400MHz,DMSO-d6)0.852-0.898(t,6H),1.232-1.430(m,12H),1.665-1.717(m,4H),3.919-
3.951(t,4H),6.751-6.773(d,2H),6.871(s,1H),6.903-6.925(d,2H),7.035-7.057(d,
4H),7.265-7.272(d,2H),7.459-7.475(d,1H),7.490-7.512(d,2H),7.917-7.937(d,1H),
8.014(s,1H),8.130-8.154(d,2H),8.189(s,1H)。ESI-MS[M+H]+: 998.27.
Embodiment 20:
1) synthesis of compound CGTD-DSSC-018: under nitrogen protection, by 018-1(50 milligrams of compound, 0.066 in the least
Mole), cyanoacetic acid (11.4 milligrams, 0.132 mM), ammonium acetate (10.3 milligrams, 0.132 mM) and acetic acid (5
Milliliter) it mixes and is stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, 20 milligrams of changes are obtained by filtration
Object CGTD-DSSC-018 is closed, LC-MS purity: 100%, yield 35%.1H-NMR(400MHz,DMSO-d6): 3.758 (s, 6H),
6.722(d,2H),6.873(s,1H),6.944(d,4H),7.105(d,4H),7.210(d,2H),7.683(d,1H),7.795
(d,2H),7.948(s,2H),8.063(d,2H),8.305(d,2H),13.925(s,1H)。ESI-MS[M+H]+: 816.2.
2) synthesis of compound CGTD-DSSC-019: under nitrogen protection, by 018-1(30 milligrams of compound, 0.04 in the least
Mole), 019-1(20 milligrams of compound, 0.05 mM), ammonium acetate (3 milligrams, 0.04 mM) and acetic acid (5 milliliters)
It mixes and is stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, 13 milligrams of compounds are obtained by filtration
CGTD-DSSC-019, LC-MS purity: 100%.Yield 29%.1H-NMR(400MHz,DMSO-d6):0.855(t,3H),1.296
(m,10H),1.591(t,2H),3.758(s,6H),3.973(t,2H),4.180(s,2H),6.722(d,2H),6.878(s,
1H),6.949(d,4H),7.102(d,4H),7.206(d,2H),7.780(d,2H),7.949(s,2H),8.068(d,2H),
8.308(d,2H),13.930(s,1H)。ESI-MS[M+H]+: 1132.2.
Embodiment 21:
1) compound B-11 (96 milligrams, 0.35 mM), chemical combination the synthesis of compound 023-1: are added in 25 milliliters of flasks
N(201 milligrams of object, 0.35 mM), tetra-triphenylphosphine palladium (40.5 milligrams, 0.035 mM) and 10 milliliters of toluene.In nitrogen
Under the conditions of gas shielded, mixture reacts 6 hours at 90 degrees Celsius, and after being cooled to room temperature, concentration removes solvent, silica gel column chromatography
(petroleum ether: ethyl acetate=6:1) obtains 130 milligrams of compound 023-1, yield 77.9%.1H-NMR(400MHz,DMSO-d6)
6.872(s,1H),7.274(t,1H),7.620(d,1H),7.654(d,1H),7.816(s,1H),7.876(d,1H),7.945
(d,1H),8.361(m,2H),10.012(s,1H)。ESI-MS[M+H]+: 478.0.
2) synthesis of compound 023-2: under the conditions of being protected from light, by N- bromo-succinimide (NBS) (48 milligrams, 0.27
MM) to be added to 30 milliliters of n,N-Dimethylformamide dissolved with compound 023-1 (129 milligrams, 0.27 mM) molten
It in liquid, is stirred overnight at room temperature, reaction solution is poured into 30 milliliters of ice water and is stirred 30 minutes, 100 milligrams of compounds are obtained by filtration
023-2, yield 66.7%.1H-NMR(400MHz,DMSO-d6)7.318(t,1H),7.432(d,1H),7.546(d,1H),
7.798(s,1H),7.854(d,1H),8.184(s,1H),8.298(m,2H),10.005(s,1H)。ESI-MS[M+H]+:
478.0。
3) synthesis of compound 023-3: by compound 023-2 (100 milligrams, 0.18 mM), compound V (77.6 grams,
0.18 mM), 75 milligrams of potassium carbonate, 0.54 mole) be added to 50 milliliter three for filling 15 milliliters of tetrahydrofurans and 6 milliliters of water
In mouth bottle, tetra-triphenylphosphine palladium (21 milligrams, 0.018 mM) are added under the conditions of nitrogen protection, solution is anti-under 68 degrees Celsius
It should stay overnight, separate organic layer after being cooled to room temperature, be concentrated to get crude product, silica gel is crossed column (petroleum ether: ethyl acetate=5:1) and obtained
100 milligrams of compound 023-3, LC-MS purity: 100%, yield 71.1%.1H-NMR(400MHz,DMSO-d6)3.758(s,6H),
6.748(d,2H),7.945(d,4H),7.076(d,4H),7.347(d,2H),7.498(m,4H),7.735(d,1H),7.919
(d,1H),8.248(s,1H),8.328(d,2H),10.015(s,1H)。ESI-MS[M+H]+: 780.2.
4) synthesis of compound CGTD-DSSC-023: under nitrogen protection, by above-mentioned 023-3(60 milligrams of compound,
0.077 mM), cyanoacetic acid (26.2 milligrams, 0.308 mM), ammonium acetate (23.7 milligrams, 0.308 mM), and
(5 milliliters) of acetic acid mix and are stirred to react under 125 degrees Celsius 5 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration 35
Milligram compound CGTD-DSSC-023, LC-MS purity: 100%, yield 53.7%.1H-NMR(400MHz,DMSO-d6)3.755
(s,6H),6.747(d,2H),7.940(d,4H),7.072(d,4H),7.344(d,2H),7.497(m,4H),7.732(d,
1H),7.917(d,1H),8.121(s,1H),8.247(s,1H),8.341(d,2H),13.810(s,1H)。ESI-MS[M+H
]+: 848.1.
Embodiment 22:
1) synthesis of compound 039-02: under nitrogen protection, by compound 039-01 (137 milligrams, 0.4 mM),
Compound B-11 (120 milligrams, 0.44 mM), potassium carbonate (166 milligrams, 1.2 mMs), four triphenyl phosphorus palladiums (46 milligrams,
0.04 mM) and tetrahydrofuran: (16 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature,
Concentration removes solvent, and it is pure that silica gel column chromatography (petroleum ether: ethyl acetate=100:1) obtains 113 milligrams of compounds 039-02, LC-MS
Degree 88%, yield 70%.ESI-MS[M+H]+: 408.07.
2) synthesis of compound 039-03: by compound 039-02 (113 milligrams, 0.28 mM), NBS (55 milligrams,
0.3 mM) it is added to and fills in 10 milliliters of DMF25 milliliters of round-bottomed flask bottles, it is reacted overnight at 27 DEG C, water quenching is added to go out instead
It answers, has solid precipitation, it is pure that silica gel column chromatography (petroleum ether: ethyl acetate=30:1) obtains 45 milligrams of compounds 039-03, LC-MS
Degree 85%, yield 33%.ESI-MS[M+H]+: 487.98.
3) synthesis of compound 039-04: under nitrogen protection, by X(59 milligrams of compound, 0.09 mM), compound
039-03(45 milligrams, 0.09 mM), potassium carbonate (40 milligrams, 0.27 mole), four triphenyl phosphorus palladiums (10 milligrams, 0.009 milli
Mole) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature, concentration is removed
Solvent is removed, silica gel column chromatography (petroleum ether: ethyl acetate=200:3) obtains 50 milligrams of compound 039-04, LC-MS purity 100%,
Yield 67%.ESI-MS[M+H]+: 851.35.
6) synthesis of compound CGTD-DSSC-039: under nitrogen protection, by 039-04(50 milligrams of compound, 0.06 in the least
Mole), cyanoacetic acid (20 milligrams, 0.24 mM), ammonium acetate (19 milligrams, 0.24 mM) and (5 milliliters) of acetic acid are mixed
Merging is stirred to react 5 hours at 125 DEG C.There is solid precipitation after being cooled to room temperature, filters, filter cake column chromatography for separation (dichloromethane
Alkane: methanol=30:1) obtain 30 milligrams of compound CGTD-DSSC-039, LC-MS purity 100%, yield 54.5%.1H-NMR
(400MHz,DMSO-d6)0.865-0.898(t,6H),1.301-1.322(m,17H),1.396-1.431(m,4H),1.666-
1.752(m,4H),3.921-3.952(t,4H),6.753-6.775(d,2H),6.871(s,1H),6.906-6.928(t,
4H),7.038-7.060(d,4H),7.247-7.256(d,1H),7.391-7.400(d,1H),7.442-7.462(d,3H),
7.493-7.512(d,2H),7.619-7.640(d,2H),7.967(s,1H),8.133(s,1H)。ESI-MS[M+H]+:
918.36。
Embodiment 23
1) synthesis of compound 045-02: under nitrogen protection, by compound 045-01 (103 milligrams, 0.26 mM),
Compound B-11 (70 milligrams, 0.26 mM), potassium carbonate (110 milligrams, 0.78 mM), four triphenyl phosphorus palladiums (30 milligrams,
0.026 mM) and tetrahydrofuran: (16 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature,
Concentration removes solvent, and silica gel column chromatography (petroleum ether: methylene chloride=1:1) obtains 53 milligrams of compound 045-02, LC-MS purity
97%, yield 43%.ESI-MS[M+H]+: 478.
2) synthesis of compound 045-03: by compound 045-02 (53 milligrams, 0.11 mM), NBS (21 milligrams,
0.12 mM) it is added to and fills in 10 milliliters of DMF25 milliliters of round-bottomed flask bottles, it is reacted overnight at 27 DEG C, water quenching is added to go out instead
It answers, there is solid precipitation, silica gel column chromatography (petroleum ether: methylene chloride=1:1) obtains 53 milligrams of compound 045-03, LC-MS purity
86%, yield 86.8%.ESI-MS[M+H]+: 556.
3) synthesis of compound 045-04: under nitrogen protection, by X(68 milligrams of compound, 0.114 mM), chemical combination
045-03(53 milligrams of object, 0.09 mM), potassium carbonate (40 milligrams, 0.28 mole), four triphenyl phosphorus palladiums (10 milligrams, 0.009
MM) and tetrahydrofuran: (12 milliliters) of water mix and are stirred to react at 70 DEG C 8 hours.After being cooled to room temperature, concentration
Solvent is removed, silica gel column chromatography (petroleum ether: methylene chloride=1:1) obtains 58 milligrams of compound 045-04, LC-MS purity 100%,
Yield 66.7%.ESI-MS[M+H]+: 921.28.
4) synthesis of compound CGTD-DSSC-045: under nitrogen protection, by 045-04(58 milligrams of compound, 0.06 in the least
Mole), cyanoacetic acid (22 milligrams, 0.25 mM), ammonium acetate (19 milligrams, 0.25 mM) and (6 milliliters) of acetic acid are mixed
Merging is stirred to react 5 hours at 125 DEG C.There is solid precipitation after being cooled to room temperature, filters, filter cake column chromatography for separation (dichloromethane
Alkane: methanol=30:1) obtain 30 milligrams of compound CGTD-DSSC-045, LC-MS purity 100%, yield 49%.1H-NMR
(400MHz,DMSO-d6)0.865-0.880(t,6H),1.295-1.511(m,12H),1.677-1.758(m,4H),3.800-
3.889(t,4H),4.460-4.479(t,4H),6.694-6.711(d,2H),6.769-6.870(d,4H),6.947-6.964
(d,4H),7.116(s,1H),7.328(s,1H),7.379-7.394(d,2H),7.610-7.623(d,2H),7.758-
7.781(d,2H),7.889(s,1H),8.088(s,1H).ESI-MS[M+H]+: 988.29.
Embodiment 24:
1) synthesis of compound 046-2
By compound 046-1 (83.6 milligrams, 0.13 mM), X (89.2 milligrams, 0.156 mM), potassium carbonate (54
Milligram, 0.39 mM), tetra-triphenylphosphine palladium (15 milligrams, 0.013 mM) is added to and fills 15 milliliters of tetrahydrofurans and 6
In the flask of milliliter water, under the conditions of nitrogen protection, solution reacts overnight under 69 degrees Celsius, is concentrated to get slightly after being cooled to room temperature
Product, silica gel cross column (petroleum ether: ethyl acetate=5:1) and obtain 67 milligrams of compound 046-2.Yield 51.1%.ESI-MS(M+H+)
1007.3。
2) synthesis of CGTD-DSSC-046
Under nitrogen protection, by the 046-2(50.4 milligram of above compound, 0.05 mM), cyanoacetic acid (17 millis
Gram, 0.2 mM), ammonium acetate (15.4 milligrams, 0.2 mM) and (8 milliliters) of acetic acid are mixed and are stirred under 125 degrees Celsius
Mix reaction 5 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-04630 milligrams of products C.Yield 56.1%.
1H-NMR(400MHz,DMSO-d6):0.877(t,6H),1.298(m,8H),1.393(m,4H),1.693(m,4H),3.920
(t,4H),6.746(d,2H),6.882(d,4H),7.001(d,4H),7.225(d,1H),7.412(d,1H),7.515(m,
6H),7.608(s,1H),7.712(m,4H),8.020(s,1H),8.133(s,1H),13.925(s,1H).ESI-MS(M+H+)
1075.3。
Embodiment 25
1) synthesis of compound 047-2
By compound 047-1 (66 milligrams, 0.13 mM), X (74 milligrams, 0.13 mM), potassium carbonate (54 milligrams,
0.39 mM), tetra-triphenylphosphine palladium (15 milligrams, 0.013 mM) is added to and fills 15 milliliters of tetrahydrofurans and 6 milliliters of water
Flask in, under the conditions of nitrogen protection, solution reacts 7 hours under 68 degrees Celsius, is concentrated to get crude product, silicon after being cooled to room temperature
Glue crosses column (petroleum ether: ethyl acetate=20:1) and obtains 72 milligrams of compound 047-2.Yield 63.7%.ESI-MS(M+H+)=
870.2。
2) synthesis of CGTD-DSSC-047
Under nitrogen protection, by the 047-2(43.5 milligram of above compound, 0.05 mM), cyanoacetic acid (17 millis
Gram, 0.2 mM), ammonium acetate (15.4 milligrams, 0.2 mM) and (8 milliliters) of acetic acid are mixed and are stirred under 125 degrees Celsius
Mix reaction 6 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration 34 milligrams of product.Yield 72.6%.1H-NMR
(400MHz,DMSO-d6):0.878(t,6H),1.310(m,8H),1.408(m,4H),1.696(m,4H),3.924(t,4H),
6.730(d,2H),6.889(d,4H),7.012(d,4H),7.242(d,1H),7.400(d,1H),7.422(d,1H),7.490
(m,4H),7.690(d,1H),7.962(s,1H),8.142(s,1H),13.925(s,1H).ESI-MS(M+H+)937.2。
Embodiment 26:
1) synthesis of compound 048-2
By compound 048-1 (106.8 milligrams, 0.2 mM), 4- trifluoromethylbenzene boronic acid (57 milligrams, 0.3 mmoles
You), potassium carbonate (83 milligrams, 0.6 mM), tetra-triphenylphosphine palladium (24 milligrams, 0.02 mM) be added to and fill 15 milliliters
In the flask of tetrahydrofuran and 6 milliliters of water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is cooled to room temperature
After be concentrated to get crude product, silica gel crosses column (petroleum ether: ethyl acetate=30:1) and obtains 84 milligrams of compound 048-2.Yield 70.0%.
ESI-MS(M+H+)=600.2。
2) synthesis of compound 048-3
By compound 048-2 (84 milligrams, 0.14 mM), and N- bromo-succinimide (28 milligrams, 0.154 mmoles
You), it is added in the flask for filling 15 milliliters of n,N-Dimethylformamide, overnight, 15 milliliters of water are added in reaction under room temperature,
95 milligrams of 048-3 are obtained by filtration in solid.Yield 99.5%.ESI-MS(M+H+)=678.1。
3) synthesis of compound 048-4
By compound 048-3 (95 milligrams, 0.14 mM), X (96 milligrams, 0.168 mM), potassium carbonate (58 milligrams,
0.42 mM), tetra-triphenylphosphine palladium (16 milligrams, 0.014 mM) is added to and fills 10 milliliters of tetrahydrofurans and 4 milliliters of water
Flask in, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated to get crude product, silicon after being cooled to room temperature
Glue crosses column (petroleum ether: ethyl acetate=15:1) and obtains 50 milligrams of compound 048-4.Yield 51.2%.ESI-MS(M+H+)=
1043.5。
4) synthesis of CGTD-DSSC-048
Under nitrogen protection, by the 048-4(50 milligram of above compound, 0.047 mM), cyanoacetic acid (15.1 millis
Gram, 0.192 mM), ammonium acetate (16.3 milligrams, 0.192 mM) and (8 milliliters) of acetic acid mixing and at 125 degrees Celsius
Under be stirred to react 6 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-04830 milligrams of products C.Yield
57.5%。1H-NMR(400MHz,DMSO-d6):0.733(t,6H),0.859(t,6H),0.918(m,4H),1.099(m,
12H),1.315(m,8H),1.387(m,4H),1.673(m,4H),1.856(m,4H),3.919(t,4H),6.750(d,2H),
6.876(d,4H),6.980(d,4H),7.389(s,1H),7443(m3H),7.855(d,4H),8.274(d,2H),13.916
(s,1H).ESI-MS(M+H+)1110.5。
Embodiment 27:
1) synthesis of compound 049-2
By compound 049-1 (65 milligrams, 0.2 mM), 029-1 (85 milligrams, 0.24 mM), potassium carbonate (83 millis
Gram, 0.6 mM), tetra-triphenylphosphine palladium (24 milligrams, 0.02 mM) is added to and fills 15 milliliters of tetrahydrofurans and 6 milliliters
In the flask of water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated to get crude product after being cooled to room temperature,
Silica gel crosses column (petroleum ether: ethyl acetate=30:1) and obtains 48 milligrams of compound 049-2.Yield 50.8%.ESI-MS(M+H+)=
473.0.
2) synthesis of compound 049-3
By compound 049-2 (47.2 milligrams, 0.1 mM), and N- bromo-succinimide (19.6 milligrams, 0.11 mmoles
You), it is added in the flask for filling 15 milliliters of n,N-Dimethylformamide, is reacted overnight under the conditions of 50 DEG C, 15 milliliters of water are added,
28 milligrams of 049-3 are obtained by filtration in solid.Yield 50.8%.ESI-MS(M+H+)=550.9.
3) synthesis of compound 049-4
By compound 049-3 (28 milligrams, 0.0508 mM), X35 milligrams, 0.0609 mM), potassium carbonate (21 millis
Gram, 0.152 mM), tetra-triphenylphosphine palladium (5.8 milligrams, 0.0051 mM) is added to and fills 10 milliliters of tetrahydrofurans and 4
In the flask of milliliter water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated to get after being cooled to room temperature
Crude product, silica gel cross column (petroleum ether: ethyl acetate=10:1) and obtain 28 milligrams of compound 049-4.Yield 60.2%.ESI-MS(M+H+)=916.3.
4) synthesis of CGTD-DSSC-049
Under nitrogen protection, by the 049-4(27.6 milligram of above compound, 0.03 mM), cyanoacetic acid (9.24 millis
Gram, 0.12 mM), ammonium acetate (10.3 milligrams, 0.12 mM) and (8 milliliters) of acetic acid mixing and under 125 degrees Celsius
It is stirred to react 6 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-04914 milligrams of products C.Yield
50.0%。1H-NMR(400MHz,DMSO-d6):0.880(t,6H),1.311(m,8H),1.392(m,4H),1.698(m,4H),
3.921(t,4H),6.749(d,2H),6.884(d,4H),7.021(d,4H),7.261(d,1H),7.403(d,1H),7.467
(d,2H),7.713(m,3H),7.866(d,2H),8.026(d,1H),8.251(s,1H),8.382(s,1H),13.928(s,
1H).ESI-MS(M+H+)983.3.
Embodiment 28:
1) synthesis of compound 050-1
By compound 048-1 (128 milligrams, 0.24 mM), X (164 milligrams, 0.288 mM), potassium carbonate (99.4
Milligram, 0.72 mM), tetra-triphenylphosphine palladium (28 milligrams, 0.024 mM) is added to and fills 15 milliliters of tetrahydrofurans and 6
In the flask of milliliter water, under the conditions of nitrogen protection, solution reacts 15 hours under 68 degrees Celsius, is concentrated to get after being cooled to room temperature
Crude product, silica gel cross column (petroleum ether: ethyl acetate=50:1) and obtain 134 milligrams of compound 050-1.Yield 62.0%.ESI-MS(M+
H+)=900.4。
2) synthesis of compound 050-2
By compound 050-1 (134 milligrams, 0.149 mM), (31.8 milligrams, 0.179 in the least for N- bromo-succinimide
Mole), it is added in the flask for filling 15 milliliters of n,N-Dimethylformamide, reaction overnight, is added 20 milliliters under room temperature
120 milligrams of 050-2 are obtained by filtration in water, solid.Yield 82.3%.ESI-MS(M+H+)=979.4。
3) synthesis of compound 050-3
By compound 050-2 (118 milligrams, 0.12 mM), and 4- trifluoromethylbenzene boronic acid (34.2 milligrams, 0.18 mmoles
You), potassium carbonate (50 milligrams, 0.36 mM), tetra-triphenylphosphine palladium (14 milligrams, 0.012 mM) be added to and fill 10 millis
In the flask for rising tetrahydrofuran and 4 milliliters of water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is cooled to room
Crude product is concentrated to get after temperature, silica gel crosses column (petroleum ether: ethyl acetate=10:1) and obtains 80 milligrams of compound 050-3.Yield
63.9%。ESI-MS(M+H+)=1043.5。
4) synthesis of CGTD-DSSC-050
Under nitrogen protection, by the 050-3(50 milligram of above compound, 0.047 mM), cyanoacetic acid (15.1 millis
Gram, 0.192 mM), ammonium acetate (16.3 milligrams, 0.192 mM) and (8 milliliters) of acetic acid mixing and at 125 degrees Celsius
Under be stirred to react 6 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-05035 milligrams of products C.Yield
67%。1H-NMR(400MHz,DMSO-d6):0.751(t,6H),0.876(t,6H),0.893(m,4H),1.099(m,12H),
1.315(m,8H),1.387(m,4H),1.673(m,4H),1.856(m,4H),3.919(t,4H),6.750(d,2H),6.899
(d,4H),7.002(d,4H),7.389(s,1H),7443(m3H),7.855(d,4H),8.275(d,2H),13.918(s,
1H).ESI-MS(M+H+)1110.5。
Embodiment 29 and embodiment 30:
) compound 051-2 synthesis
By compound M ' (575 milligrams, 1.1 mMs), the bromo- 3- formylthien of 2,5- bis- (327 milligrams, 1.21 mmoles
You), tetra-triphenylphosphine palladium (127 milligrams, 0.11 mM) is added in the flask for filling 20 milliliters of dry toluenes, nitrogen protection
Under the conditions of, solution reacts 16 hours under 95 degrees Celsius, is concentrated to get crude product after being cooled to room temperature, silica gel crosses column (petroleum ether: second
Acetoacetic ester=20:1) obtain 350 milligrams of compound 051-2.Yield 75.2%.ESI-MS(M+H+)=423.9。
2) synthesis of compound 051-3
By compound 051-2 (153 milligrams, 0.362 mM), 029-1 (153.6 milligrams, 0.434 mM), carbonic acid
Potassium (150 milligrams, 1.08 mMs), tetra-triphenylphosphine palladium (42 milligrams, 0.036 mM) are added to and fill 20 milliliters of tetrahydro furans
It mutters in the flask of 8 milliliters of water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated after being cooled to room temperature
Crude product is obtained, silica gel crosses column (petroleum ether: ethyl acetate=30:1) and obtains 120 milligrams of compound 051-3.Yield 58.0%.ESI-
MS(M+H+)=570.2
3) synthesis of compound 051-4
By compound 051-3 (120 milligrams, 0.21 mM), and N- bromo-succinimide (45 milligrams, 0.253 mmoles
You), it is added in the flask for filling 15 milliliters of n,N-Dimethylformamide, overnight, 15 milliliters of water are added in reaction under room temperature,
Ether extracts (25 milliliters, 3 times) merging organic phases, and anhydrous magnesium sulfate dry filter is concentrated to get crude product, and silica gel crosses column (stone
Oily ether: ethyl acetate=50:1) obtain 100 milligrams of compound 051-4.Yield 73.3%.ESI-MS(M+H+)=649.9。
4) synthesis of compound 051-5
By compound 051-4 (100 milligrams, 0.154 mM), X (97 milligrams, 0.17 mM), potassium carbonate (64 millis
Gram, 0.462 mM), tetra-triphenylphosphine palladium (18 milligrams, 0.016 mM) be added to fill 15 milliliters of tetrahydrofurans and 6 milli
In the flask for rising water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated to get slightly after being cooled to room temperature
Product, silica gel cross column (petroleum ether: ethyl acetate=10:1) and obtain 120 milligrams of compound 051-5.Yield 76.8%.ESI-MS(M+H+)=1013.3。
5) synthesis of CGTD-DSSC-051
Under nitrogen protection, by the 051-5(50 milligram of above compound, 0.05 mM), cyanoacetic acid (17 milligrams,
0.2 mM), ammonium acetate (15 milligrams, 0.2 mM) and (8 milliliters) of acetic acid mixing are simultaneously stirred anti-under 125 degrees Celsius
It answers 6 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-05128 milligrams of products C.Yield 55.6%.1H-
NMR(400MHz,DMSO-d6):0.594(t,6H),0.881(t,6H),1.236(m,8H),1.393(m,4H),1.698(t,
4H),1.856(m,4H),3.927(t,4H),6.757(d,2H),6.886(d,4H),6.988(d,4H),7.366(d,2H),
7.456(m3H),7.765(m,3H),7.900(d,2H),7.989(s,1H),8.218(s,1H),13.946(s,1H).ESI-
MS(M+H+)1080.3。
6) synthesis of CGTD-DSSC-052
Under nitrogen protection, by the 051-5(56 milligram of above compound, 0.055 mM), rhodanine acetic acid (15.7
Milligram, 0.083 mM), ammonium acetate (17 milligrams, 0.0.22 mMs) and (8 milliliters) of acetic acid mixing and it is Celsius 125
It is stirred to react under degree 6 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-05234 milligrams of products C.Yield
52.05%。1H-NMR(400MHz,DMSO-d6):0.576(t,6H),0.881(t,6H),1.230(m,4H),1.322(m,
8H),1.416(m,4H),1.764(m,4H),3.924t,4H),4.452(s,2H),6.764(d,2H),6.903(d,4H),
6.978(d,4H),7.401(m,3H),7.468(d2H),7.554(d,1H),7.735(m,3H),7.787(s,1H),7.895
(d,2H),13.938(s,1H).ESI-MS(M+H+)1186.3。
Embodiment 31 and embodiment 32
1) synthesis of compound 053-2
By compound 053-1 (153 milligrams, 0.362 mM), 029-1 (153.6 milligrams, 0.434 mM), carbonic acid
Potassium (150 milligrams, 1.08 mMs), tetra-triphenylphosphine palladium (42 milligrams, 0.036 mM) are added to and fill 20 milliliters of tetrahydro furans
It mutters in the flask of 8 milliliters of water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated after being cooled to room temperature
Crude product is obtained, silica gel crosses column (petroleum ether: ethyl acetate=30:1) and obtains 120 milligrams of compound 053-2.Yield 58.2%.ESI-
MS(M+H+)=570.0。
2) synthesis of compound 053-3
By compound 053-2 (120 milligrams, 0.21 mM), and N- bromo-succinimide (45 milligrams, 0.253 mmoles
You), it is added in the flask for filling 20 milliliters of n,N-Dimethylformamide, overnight, 20 milliliters of water are added in reaction under room temperature,
100 milligrams of 053-3 are obtained by filtration in solid.Yield 73.3%.ESI-MS(M+H+)=650.0。
3) synthesis of compound 053-4
By compound 053-3 (100 milligrams, 0.154 mM), X (97 milligrams, 0.170 mM), potassium carbonate (64 millis
Gram, 0.462 mM), tetra-triphenylphosphine palladium (18 milligrams, 0.0154 mM) is added to and fills 10 milliliters of tetrahydrofurans and 4
In the flask of milliliter water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated to get after being cooled to room temperature
Crude product, silica gel cross column (petroleum ether: ethyl acetate=20:1) and obtain 120 milligrams of compound 053-4.Yield 76.8%.ESI-MS(M+
H+)=1013.3。
4) synthesis of CGTD-DSSC-053
Under nitrogen protection, by the 053-4(60 milligram of above compound, 0.059 mM), cyanoacetic acid (20.1 millis
Gram, 0.237 mM), ammonium acetate (18.2 milligrams, 0.237 mM) and (8 milliliters) of acetic acid mixing and at 125 degrees Celsius
Under be stirred to react 8 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-05335 milligrams of products C.Yield
52.1%。1H-NMR(400MHz,DMSO-d6):0.595(t,6H),0.882(t,6H),1.355(m,8H),1.410(m,4H),
1.678 (m, 4H), 1.910 (m, 4H), 3.578 (t, 4H), 3.915 (t, 4H), 6.735 (d, 2H), 6.870 (d, 4H), 6.946
(d,4H),7.325(s,1H),7420(m4H),7.654(d,1H),7.823(d,1H),8.039(s,1H)8.171(s,1H),
8.251(m,2H),13.926(s,1H).ESI-MS(M+H+)1137.3。
5) synthesis of CGTD-DSSC-054
Under nitrogen protection, by the 053-4(60 milligram of above compound, 0.059 mM), rhodanine acetic acid (13.5
Milligram, 0.708 mM), ammonium acetate (18.2 milligrams, 0.237 mM) and (10 milliliters) of acetic acid are mixed and are taken the photograph 125
It is stirred under family name's degree anti-15 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-05440 milligrams of products C.It produces
Rate 54.5%.ESI-MS(M+H+)1243.3。
Embodiment 33:
1) synthesis of compound 055-1
By compound X (114.2 milligrams, 0.20 mM), N'(79.8 milligrams, 0.20 mM), potassium carbonate (82.8 millis
Gram, 0.6 mM), tetra-triphenylphosphine palladium (23.2 milligrams, 0.02 mM) be added to fill 20 milliliters of tetrahydrofurans and 8 milli
In the flask for rising water, under the conditions of nitrogen protection, solution reacts 8 hours under 65 degrees Celsius, is concentrated to get slightly after being cooled to room temperature
Product, silica gel cross column (petroleum ether: ethyl acetate=40:1) and obtain 75 milligrams of compound 055-1.Yield 52.3%.ESI-MS(M+H+)
=717.2。
2) synthesis of compound 055-2
By compound 055-1 (71.6 milligrams, 0.1 mM), 061-4 (72.6 milligrams, 0.1 mM), potassium carbonate
(41.4 milligrams, 0.3 mM), tetra-triphenylphosphine palladium (11.6 milligrams, 0.01 mM) are added to and fill 10 milliliters of tetrahydro furans
It mutters in the flask of 3 milliliters of water, under the conditions of nitrogen protection, solution reacts 16 hours under 68 degrees Celsius, is cooled to dense after room temperature
Contracting obtains crude product, and silica gel crosses column (petroleum ether: ethyl acetate=10:1) and obtains 92 milligrams of compound 055-2.Yield 74.4%.ESI-
MS(M+H+)=1236.6。
3) synthesis of CGTD-DSSC-055
Under nitrogen protection, by the 055-2(61.8 milligram of above compound, 0.05 mM), cyanoacetic acid (17 millis
Gram, 0.20 mM), piperidines (17 milligrams, 0.20 mM) and (8 milliliters) of tetrahydrofuran mixing and under 70 degrees Celsius
It is stirred to react 48 hours.It is cooled to the crude product that obtains being concentrated after room temperature, silica gel crosses 35 milli of column (methylene chloride: methanol=20:1)
Gram CGTD-DSSC-055.Yield 53.7%.1H-NMR(400MHz,DMSO-d6):0.751(t,6H),0.866(t,6H),
1.135 (m, 12H), 1.335 (m, 8H), 1.412 (m, 4H), 1.701 (m, 4H), 1.987 (m, 4H), 3.736 (t, 4H),
3.925 (t, 4H), 6.750 (d, 2H), 6.888 (d, 4H), 7.003 (d, 4H), 7.235 (m, 1H), 7394 (s, 1H), 7.435
(d,2H),7.724(d,2H),7.783(d,2H),7.923(m,8H)8.132(s,1H),8.222(s,2H),13.946(s,
1H).ESI-MS(M+H+)1137.3
Embodiment 34
1) synthesis of compound 056-1
By compound 061-4 (72.6 milligrams, 0.1 mM), B1 (27.3 milligrams, 0.1 mM), potassium carbonate (41.4
Milligram, 0.3 mM), tetra-triphenylphosphine palladium (11.6 milligrams, 0.01 mM) is added to and fills 15 milliliters of tetrahydrofurans and 6
In the flask of milliliter water, under the conditions of nitrogen protection, solution reacts 8 hours under 65 degrees Celsius, is concentrated to get after being cooled to room temperature
Crude product, silica gel cross column (petroleum ether: ethyl acetate=10:1) and obtain 65 milligrams of compound 056-1.Yield 81.9%.ESI-MS(M+H+)=792.3。
2) synthesis of CGTD-DSSC-056
Under nitrogen protection, by the 056-1(36.3 milligram of above compound, 0.05 mM), cyanoacetic acid (17 millis
Gram, 0.20 mM), piperidines (17 milligrams, 0.20 mM) and (8 milliliters) of tetrahydrofuran mixing and under 70 degrees Celsius
It is stirred to react 48 hours.It is cooled to the crude product that obtains being concentrated after room temperature, silica gel crosses 25 milli of column (methylene chloride: methanol=20:1)
Gram CGTD-DSSC-056.Yield 58.1%.1H-NMR(400MHz,DMSO-d6):0.752(t,6H),1.136(m,12H),
1.442 (m, 4H), 3.751 (t, 4H), 7.242 (br, 2H), 7.793 (d, 5H), 7.942 (m, 9H), 8.251 (s, 1H),
13.946(s,1H).ESI-MS(M+H+)859.3。
Embodiment 35:
1) synthesis of compound 057-1
By compound A1 (486 milligrams, 1.8 mMs), 2- thienyl boric acid (576 milligrams, 4.5 mMs), potassium carbonate
(1.24 grams, 9 mMs), tetra-triphenylphosphine palladium (417 milligrams, 0.36 mM) are added to and fill 30 milliliters of tetrahydrofurans and 12
In the flask of milliliter water, under the conditions of nitrogen protection, solution reacts 16 hours under 65 degrees Celsius, is concentrated to get after being cooled to room temperature
Crude product, silica gel cross column (petroleum ether: ethyl acetate=10:1) and obtain 420 milligrams of compound 057-1.Yield 84.5%.ESI-MS(M+
H+)=276.
2) synthesis of CGTD-DSSC-057
Under nitrogen protection, by the 057-1(55.2 milligram of above compound, 0.2 mM), cyanoacetic acid (68 milligrams,
0.8 mM), ammonium acetate (61.6 milligrams, 0.8 mM) and (8 milliliters) of acetic acid are mixed and are stirred under 125 degrees Celsius
Reaction 16 hours.Solid is precipitated after being cooled to room temperature, and 36 milligrams of CGTD-DSSC-057 are obtained by filtration.Yield 52.5%.1H-NMR
(400MHz,DMSO-d6):7.167(t,1H),7.313(t,1H),7.419(m,2H),7.663(d,1H),7.905(d,1H),
8.017(s,1H),8.230(s,1H),14.031(s,1H).ESI-MS(M+H+)343.0。
Embodiment 36
1) synthesis of compound 058-1
Compound 057-1 (166 milligrams, 0.6 mM) is added to the burning for filling 30 milliliters of n,N-Dimethylformamide
In bottle, N- bromo-succinimide (225 milligrams, 1.26 mMs) are added at room temperature, solution reacts 16 hours at room temperature, adds
Enter 30 milliliters of water, solid is precipitated, filtering to 245 milligrams of 058-1.Yield 94.04%.ESI-MS(M+H+)=433.8。
2) synthesis of CGTD-DSSC-058
Under nitrogen protection, by the 058-1(43.4 milligram of above compound, 0.1 mM), cyanoacetic acid (34 milligrams,
0.4 mM), ammonium acetate (30.8 milligrams, 0.4 mM) and (8 milliliters) of acetic acid are mixed and are stirred under 125 degrees Celsius
Reaction 16 hours.Solid is precipitated after being cooled to room temperature, and 30 milligrams of CGTD-DSSC-058 are obtained by filtration.Yield 59.9%.1H-NMR
(400MHz,DMSO-d6):7.257(d,1H),7.302(d,2H),7.449(d,1H),7.946(s,1H),8.128(s,1H),
14.090(s,1H).ESI-MS(M+H+)500.8。
Embodiment 37
1) synthesis of compound 059-1
By compound 058-1 (65.1 milligrams, 0.15 mM), 4- amyl phenyl boric acid (86.4 milligrams, 0.45 mM),
Potassium carbonate (103.5 milligrams, 0.75 mM), tetra-triphenylphosphine palladium (34.7 milligrams, 0.03 mM), which are added to, fills 20 millis
In the flask for rising tetrahydrofuran and 8 milliliters of water, under the conditions of nitrogen protection, solution reacts 12 hours under 65 degrees Celsius, is cooled to
Crude product is concentrated to get after room temperature, silica gel crosses column (petroleum ether: ethyl acetate=40:1) and obtains 45 milligrams of compound 059-1.Yield
52.7%。ESI-MS(M+H+)=568.2.
2) synthesis of CGTD-DSSC-059
Under nitrogen protection, by the 059-1(45 milligram of above compound, 0.08 mM), cyanoacetic acid (27.2 millis
Gram, 0.32 mM), ammonium acetate (24.6 milligrams, 0.32 mM) and (8 milliliters) of acetic acid mixing and under 125 degrees Celsius
It is stirred to react 16 hours.Solid is precipitated after being cooled to room temperature, and 30 milligrams of CGTD-DSSC-059 are obtained by filtration.Yield 58.9%.1H-
NMR(400MHz,DMSO-d6):0.866(t,6H),1.295(m,8H),1.579(m,4H),2.589(t,4H),7.255(m,
4H),7.377(d,2H),7.495(d,1H),7.606(m,5H),7.994(s,1H),8.256(s,1H),14.033(s,1H)
.ESI-MS(M+H+)635.2。
Embodiment 38
1) synthesis of compound 060-1
By compound 058-1 (65.1 milligrams, 0.15 mM), X (214 milligrams, 0.375 mM), potassium carbonate
(103.5 milligrams, 0.75 mM), tetra-triphenylphosphine palladium (34.7 milligrams, 0.03 mM) are added to and fill 20 milliliters of tetrahydros
In the flask of furans and 8 milliliters of water, under the conditions of nitrogen protection, solution reacts 12 hours under 65 degrees Celsius, after being cooled to room temperature
It is concentrated to get crude product, silica gel crosses column (petroleum ether: ethyl acetate=40:1) and obtains 120 milligrams of compound 060-1.Yield 68.8%.
ESI-MS(M+H+)=1162.5.
2) synthesis of CGTD-DSSC-060
Under nitrogen protection, by the 060-1(58.2 milligram of above compound, 0.05 mM), cyanoacetic acid (17 millis
Gram, 0.2 mM), ammonium acetate (15.4 milligrams, 0.2 mM) and (8 milliliters) of acetic acid are mixed and are stirred under 125 degrees Celsius
Mix reaction 5 hours.Solid is precipitated after being cooled to room temperature, and 40 milligrams of CGTD-DSSC-060 are obtained by filtration.Yield 65.0%.1H-NMR
(400MHz,DMSO-d6):0.864(t,12H),1.322(m,16H)m,1.412(m,8H),1.718(m,8H),3.936(t,
8H),6.748(m,4H),6.926(m,8H),7.051(m,8H),7.263(d,1H),7.346(d,2H),7.458(d,1H),
7.492(m,4H),7.931(s,1H),8.153(s,1H),13.936(s,1H).ESI-MS(M+H+)1229.5。
Embodiment 39
1) synthesis of compound 061-1:
It will be slowly warmed up dissolved with the 2- methyl 2- butanol solution (20 milliliters) of sodium tert-butoxide (3.84 grams, 4.0 mMs)
50 DEG C, 4- bromobenzylcyanide (3.6 grams, 20.0 mMs) are added portionwise at this temperature, temperature is risen to 90 DEG C after adding, then
It will be slowly added drop-wise to dissolved with 2- methyl -2- butanol (20 milliliters) solution of diisopropyl ester amber acid (2.02 grams, 10.0 mMs)
In reaction solution, after 3 hours add, reaction solution reacts overnight at this temperature, and reaction solution is then cooled to 50 DEG C, is slowly dripped
Enter the aqueous solution containing acetic acid, reaction solution filtering, filter cake water and methanol are washed to obtain 2.86 grams of red solid 061-1.Yield
64%。
2) synthesis of compound 061-2:
By 061-1(1 grams of compound, 2.2 mMs) it is dissolved in n,N-Dimethylformamide (30 milliliters), then by 1- bromine
Hexane (1.44 grams, 8.8 mMs), cesium carbonate (2.15 grams, 6.6 mMs) are added in solution, and reaction solution is reacted at 40 DEG C
Overnight.Reaction solution filtering is added 200 milliliters of methylene chloride toward filtrate, is washed with water (50 milliliters, 3 times), organic layer concentration, silica gel
It crosses column (petroleum ether: ethyl acetate=10:1) and obtains 554 milligrams of compound 061-2. yields 40.1%.ESI-MS[M+H]+:
615.2。
3) synthesis of compound 061-3:
By 061-2(554 milligrams of compound, 0.9 mM), 4- trifluoromethylbenzene boronic acid (171 milligrams, 0.9 mM),
It (310 milligrams, 2.25 mMs) of potassium carbonate plus is added in the mixed solution of tetrahydrofuran (15 milliliters) and water (3 milliliters), nitrogen
Tetra-triphenylphosphine palladium (0.1 gram, 0.09 mM) is added under the conditions of gas shielded, solution reacts 3 hours at 45 DEG C, is cooled to room temperature
After separate organic layer, be concentrated to get crude product, silica gel crosses column (petroleum ether: ethyl acetate=10:1) and obtains 286 milligrams of compound 061-
3, LC-MS purity: 100%, yield 47%.1H-NMR(400MHz,CDCl3)δ:0.857(m,6H),1.213(m,12H),1.572
(m,4H),3.758(m,4H),7.512(t,1H),7.683(m,4H),7.705(s,3H),7.755(s,1H),7.784(d,
2H),7.532(m,1H),7.911(d,2H)。
4) synthesis of compound 061-4:
By compound 061-3 (286 milligrams, 0.42 mM), and duplex pinacol borate (267 milligrams, 1.05 mmoles
You), potassium acetate (123 milligrams, 1.26 mMs) is dissolved in Isosorbide-5-Nitrae-dioxane (20 milliliters), is added 1,1'- under nitrogen protection
Double Diphenyl phosphino ferrocene palladium chlorides (31 milligrams, 0.042 mM) are heated to 90 DEG C overnight, and concentration removes solvent, silica gel
It crosses column (petroleum ether: methylene chloride=10:1-1:1) and obtains 168 milligrams of compound 061-4, yield 53.8%.1H-NMR(400MHz,
CDCl3)δ:0.808-0.838(m,6H),1.241(S,12H),1.261(S,12H),1.646(S,4H),3.751-3.789
(m,4H),7.747-7.802(m,8H),7.933-7.979(m,4H)。
5) synthesis of compound 061-5:
By 061-4(118 milligrams of compound, 0.16 mM), O'(64 milligrams of compound, 0.16 mM), potassium carbonate
(55 milligrams, 0.4 mM) are dissolved in the in the mixed solvent for filling tetrahydrofuran (20 milliliters) and water (5 milliliters), nitrogen protection item
Tetra-triphenylphosphine palladium (18 milligrams, 0.01 mM) are added under part, solution 70 DEG C of reactions overnight, being cooled to after room temperature to separate has
Machine layer, is concentrated to get crude product, and silica gel crosses column (petroleum ether: ethyl acetate=3:1), and to obtain 46 milligrams of compounds 061-5, LC-MS pure
Degree: 100%, yield 38%.1H-NMR(400MHz,CDCl3)δ:0.851-0.818(m,6H),1.159(m,6H),1.254(m,
12H),1.650(m,4H),3.796-3.825(m,4H),4.582(s,1H),6.735-6.758(d,2H),7.206-7.215
(d,1H),7.308-7.317(d,1H),7.518-7.540(d,2H),7.749-7.787(m,8H),7.827(s,1H),
7.905-7.963(m,4H),10.229(s,1H).
6) synthesis of compound CGTD-DSSC-061:
By 061-5(46 milligrams of compound, 0.05 mM), cyanoacetic acid (42 milligrams, 0.5 mM), pyridine (0.1
Milliliter) it is dissolved in the in the mixed solvent of tetrahydrofuran (3 milliliters) and acetonitrile (3 milliliters), it is refluxed overnight under nitrogen protection, mistake after cooling
Filter, filtrate concentration, silica gel cross column (methylene chloride: methanol=100:1) and obtain 13 milligrams of compound CGTD-DSSC-061.LC-MS
Purity: 100%, yield 27%.1H-NMR(400MHz,DMSO)δ:0.773-0.741(t,6H),1.118-1.129(m,10H),
1.224(s,6H),1.269-1.284(d,6H),3.698-3.709(m,4H),4.596-4.625(m,1H),6.874-6.896
(d,2H),7.179(s,1H),7.389-7.396(d,1H),7.477-7.498(d,2H),7.614-7.634(d,2H),
7.705-7.726(d,2H),7.762-7.826(m,6H),7.847-7.867(d,2H),8.113-8.160(d,2H)。
Embodiment 40
1) synthesis of compound 062-1:
By compound 2,4- dimethoxy benzene bromine (5g, 23 mMs) is dissolved in 50 milliliters of methylene chloride, under ice-water bath
Boron tribromide (20 milliliters) is slowly instilled in solution, drop finishes, and reaction is stirred overnight at room temperature, by reaction solution methanol (50 millis
Rise) it is quenched under ice-water bath, the solution concentration silica gel after being quenched crosses column (methylene chloride: methanol=50:1-20:1) and obtains 2.4 grams
Compound 062-1, LC-MS purity: 94%, yield 55%.ESI-MS[M+H]+: 190.1.
2) synthesis of compound 062-2:
By 061-1(1.97 grams of compound, 10.4 mMs) it is dissolved in acetonitrile (150 milliliters), then by 1- iodohexane
(4.42 grams, 20.8 mMs), cesium carbonate (6.78 grams, 20.8 mMs) are added in solution, and under nitrogen protection, reaction solution exists
90 DEG C are stirred overnight.Reaction solution filtering is added 100 milliliters of methylene chloride toward filtrate, (50 milliliters, 3 times) is washed with water, organic layer is dense
Contracting, silica gel cross column (petroleum ether: ethyl acetate=50:1) and obtain 2.8 g of compound 062-2. yields 76%.1H-NMR(400MHz,
CDCl3)δ:0.888-0.926(t,6H),1.312-1.358(m,8H),1.427-1.511(m,4H),1.742-1.840(m,
4H),3.893-3.926(t,2H),3.960-3.993(t,2H),6.348-6.376(dd,1H),6.459-6.466(d,1H),
7.358-7.380(d,1H)。
3) synthesis of compound 062-3:
By 062-2(2.8 grams of compound, 7.9 mMs), 4- nitrobenzene boronic acid (1.97 grams, 11.8 mMs), potassium fluoride
(1.37 grams, 23.7 mMs) are added to glycol dimethyl ether (20 milliliters), toluene (2 milliliters), ethyl alcohol (12 milliliters) and water (6
Milliliter) mixed solution in, under the conditions of nitrogen protection be added tetra-triphenylphosphine palladium (912 milligrams, 0.79 mM), solution exists
110 DEG C are stirred to react 5h, separate organic layer after being cooled to room temperature, are concentrated to get crude product, silica gel cross column (petroleum ether: ethyl acetate=
20:1-20:1) obtain 2.1 g of compound 062-3, LC-MS purity: 95%, yield 67%.1H-NMR(400MHz,CDCl3)δ:
0.782-0.860(tt,6H),1.182-1.290(m,10H),1.374-1.426(m,2H),1.637-1.752(tt,4H),
3.877-3.944(m,4H),6.484-6.506(d,2H),7.177-7.197(t,1H),7.599-7.621(d,2H),
8.131-8.153(d,2H)。
4) synthesis of compound 062-4:
By 062-3(1.5 grams of compound, 3.76 mMs), zinc powder (2.44 grams, 37.6 mMs), ammonium chloride (3.0 grams,
37.6 mMs) it is added in the mixed solution of acetone (30 milliliters) and water (6 milliliters), under the conditions of nitrogen protection, solution is 60
DEG C it is stirred to react 1h, is filtered after being cooled to room temperature, filtrate is concentrated to get crude product, and silica gel crosses column (petroleum ether: methylene chloride=1:1)
Obtain 1.38 g of compound 062-4, LC-MS purity: 92%, yield 86%.ESI-MS[M+H+2]+: 370.3.
5) synthesis of compound 062-5:
By 062-4(1.0 grams of compound, 2.7 mMs) it is added to the mixed of 9% sulfuric acid (15 milliliters) and acetonitrile (15 milliliters)
It closes in solution, under ice-water bath, the sodium nitrite (560 milligrams, 8.1 mMs) for being dissolved in water (3 milliliters) is added drop-wise in solution, drip
Finish, stir 30 minutes, the potassium iodide (4.48 grams, 27 mMs) for being dissolved in water (5 milliliters) is added in reaction solution, drop finishes, molten
35 DEG C of liquid are stirred overnight.After being cooled to room temperature, reaction solution is quenched with saturated sodium thiosulfate solution (20 milliliters), uses unsaturated carbonate
Potassium solution neutralizes, and is extracted with dichloromethane (20 milliliters, three times), and extract liquor is concentrated to get crude product, silica gel mistake with water (20 milliliters)
Column (petroleum ether: methylene chloride=10:1-1:1) obtains 860 milligrams of compound 062-5, LC-MS purity: 95%, yield 66%.1H-
NMR(400MHz,CDCl3)δ:0.861-0.929(m,6H),1.272-1.290(m,4H),1.326-1.393(m,6H),
1.452-1.488(tt,2H),1.688-1.808(tt,4H),3.907-3.989(tt,4H),6.508-6.528(m,2H),
7.167-7.190(d,2H),7.246-7.266(d,2H),7.661-7.682(d,2H)。
6) synthesis of compound 062-6:
By 062-5(753 milligrams of compound, 1.56 mMs), 4- bromaniline (90 milligrams, 0.52 mM), iodate it is sub-
Copper (30 milligrams, 0.156 mM), 1.10- phenanthroline (28 milligrams, 0.156 mM), sodium tert-butoxide (270 milligrams, 2.8 millis
Mole) be added in toluene (5 milliliters), under the conditions of nitrogen protection, solution is stirred to react 1h at 125 DEG C, is cooled to mistake after room temperature
Filter, filtrate are concentrated to get crude product, and silica gel crosses column (petroleum ether: methylene chloride=1:1) and obtains 380 milligrams of compounds 062-6, LC-MS
Purity: 96%, yield 83%.1H-NMR(400MHz,CDCl3)δ:0.850-0.931(t,12H),1.285-1.303(m,8H),
1.339-1.375(m,12H),1.403-1.494(m,4H),1.723-1.813(m,8H),3.935-3.997(m,8H),
6.525-6.540(m,4H),7.028-7.049(d,2H),7.097-7.118(d,4H),7.233-7.254(d,3H),
7.315-7.336(d,2H),7.423-7.443(d,3H)。
7) synthesis of compound 062-7:
By 062-6(380 milligrams of compound, 0.4 mM) it is dissolved in tetrahydrofuran (5 milliliters), it is dripped under the conditions of -78 DEG C
Add n-BuLi (0.64 milliliter, 1.6 mMs), reacted 30 minutes under the conditions of -78 DEG C, isopropyl pinacol borate is added
(298 milligrams, 1.6 mMs).Under the conditions of nitrogen protection, mixture reacts 16 hours, and saturated aqueous ammonium chloride is added and quenches
It goes out reaction, methylene chloride extracts (20 milliliters, three times), and concentration removes silica gel chromatograph post separation (petroleum ether: methylene chloride after solvent
=5:1-1:2) obtain 159 milligrams of compound 062-7, LC-MS purity: 100%, yield 40%.1H-NMR(400MHz,CDCl3)δ:
0.848-0.932(t,12H),1.285-1.303(m,8H),1.334(s,12H),1.348-1.441(m,12H),1.459-
1.491(m,4H),1.724-1.815(m,8H),3.935-3.999(m,8H),6.527-6.538(m,4H),7.120-7.153
(m,6H),7.246(s,1H),7.269(s,1H),7.426-7.448(d,4H),7.664-7.685(d,2H)。
8) synthesis of compound 062-8:
By 062-7(110 milligrams of compound, 0.12 mM), compound 029-3 (50 milligrams, 0.1 mM), carbonic acid
Potassium (41 milligrams, 0.3 mM) is dissolved in the in the mixed solvent for filling tetrahydrofuran (9 milliliters) and water (3 milliliters), nitrogen protection item
Tetra-triphenylphosphine palladium (11 milligrams, 0.01 mM) are added under part, solution 80 DEG C of reactions overnight, being cooled to after room temperature to separate has
Machine layer, is concentrated to get crude product, and silica gel crosses column (petroleum ether: ethyl acetate=3:1), and to obtain 78 milligrams of compounds 062-8, LC-MS pure
Degree: 100%, yield 64%.1H-NMR(400MHz,CDCl3)δ:0.859-0.935(m,12H),1.299-1.317(m,8H),
1.344-1.370(m,8H),1.401-1.518(m,8H),1.739-1.821(m,8H),3.951-4.006(m,8H),
6.539-6.552(m,4H),7.169-7.190(d,2H),7.220-7.230(d,2H),7.279-7.301(m,5H),
7.330-7.340(d,2H),7.464-7.501(m,6H),7.610(s,1H),7.637-7.712(dd,4H),10.185(s,
1H).
9) synthesis of compound CGTD-DSSC-062:
By 062-8(78 milligrams of compound, 0.064 mM), cyanoacetic acid (22 milligrams, 0.256 mM), ammonium acetate
(20 milligrams, 0.256 mM) are dissolved in acetic acid (4 milliliters), and under nitrogen protection, reaction solution reacts 4 hours at 125 DEG C, cold
But it filters afterwards, filtrate concentration, silica gel crosses column (methylene chloride: methanol=100:1) and obtains 52 milligrams of compound CGTD-DSSC-062.
LC-MS purity: 100%, yield 63%.1H-NMR(400MHz,DMSO)δ:0.774-0.914(m,12H),1.201-1.268(m,
12H),1.331-1.377(m,8H),1.398-1.465(m,4H),1.603-1.747(m,8H),3.941-4.019(m,8H),
6.554-6.609(m,4H),7.035-7.091(m,6H),7.197-7.225(d,2H),7.260-7.271(d,2H),
7.395-7.451(m,6H),7.555-7.584(d,2H),7.631-7.644(d,2H),7.715-7.743(d,2H),
7.867-7.893(d,2H),8.021(s,1H),8.1809(s,1H)。
Embodiment 41
1) synthesis of compound 031-3
By compound 031-2 (450 milligrams, 1.16 mMs), X (660 milligrams, 1.16 mMs), potassium carbonate (320 millis
Gram, 2.32 mMs), tetra-triphenylphosphine palladium (67 milligrams, 0.06 mM) be added to fill 80 milliliters of tetrahydrofurans and 20 milli
In the flask for rising water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated to get slightly after being cooled to room temperature
Product, silica gel cross column (petroleum ether: ethyl acetate=10:1) and obtain 100 milligrams of compound 031-3.Yield 80%.ESI-MS(M+H+)=
754.2。
2) synthesis of compound 063-1
By compound 031-3 (100 milligrams, 0.14 mM), to trifluoromethylbenzene boronic acid (26 milligrams, 0.14 mmoles
You), tris(dibenzylideneacetone) dipalladium (6 milligrams, 0.07 mM), tri-tert-butylphosphine borofluoride (8 milligrams, 0.28 mmoles
You), cesium carbonate (130 milligrams, 0.4 mM) is added in the flask for filling 15 milliliters of dioxane, nitrogen protection condition
Under, 120 degrees Celsius are reacted 3 hours, are concentrated to get crude product after being cooled to room temperature, silica gel crosses column (petroleum ether: ethyl acetate=10:1)
Obtain 85 milligrams of compound 063-1.Yield 74%.ESI-MS(M+H+)=720.3。
3) synthesis of CGTD-DSSC-063
Under nitrogen protection, by the 063-1(85 milligram of above compound, 0.1 mM), cyanoacetic acid (34 milligrams,
0.4 mM), ammonium acetate (31.2 milligrams, 0.4 mM) and (5 milliliters) of acetic acid are mixed and are stirred under 125 degrees Celsius
Reaction 6 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-06328 milligrams of products C.Yield 30.0%.
1H-NMR(400MHz,DMSO-d6):0.884(t,6H),1.315(m,8H),1.414(m,4H),1.702(m,4H),3.937
(t,4H),6.751(d,2H),6.907(d,4H),7.041(d,4H),7.161(t,1H),7.301(d,1H),7.417(s,
1H),7.520(m,3H),7.646(d,1H),7.985(s,1H),8.210(s,1H).ESI-MS(M+H+)=787.3。
Embodiment 42
1) synthesis of compound 064-2:
By 064-1(700 milligrams of compound, 1.6 mMs), 4- trifluoromethylbenzene boronic acid (365 milligrams, 1.92 mmoles
You), potassium carbonate (552 milligrams, 4.0 mMs) be added in the mixed solution of tetrahydrofuran (20 milliliters) and water (4 milliliters), nitrogen
Tetra-triphenylphosphine palladium (185 milligrams, 0.16 mM) are added under the conditions of gas shielded, solution is stirred to react 2 days at 50 DEG C, is cooled to
Organic layer is separated after room temperature, is concentrated to get crude product, and silica gel crosses column (petroleum ether: ethyl acetate=20:1-20:1) and obtains 270 milligrams
Compound 064-2, LC-MS purity: 98%, yield 32%.ESI-MS[M+H+1]+: 507.0.
2) synthesis of compound 064-3:
By 064-2(270 milligrams of compound, 0.53 mM), 2- thienyl boric acid (81 milligrams, 0.63 mM), carbonic acid
Potassium (183 milligrams, 1.325 mMs) is added in the mixed solution of tetrahydrofuran (20 milliliters) and water (4 milliliters), nitrogen protection
Under the conditions of be added tetra-triphenylphosphine palladium (61 milligrams, 0.053 mM), solution be stirred to react at 70 DEG C overnight, be cooled to room temperature
After separate organic layer, be concentrated to get crude product, silica gel crosses column (petroleum ether: methylene chloride=2:1) and obtains 210 milligrams of compound 064-
3, LC-MS purity: 100%, yield 32%.ESI-MS[M+H+1]+: 509.2.
3) synthesis of compound 064-4:
By 064-3(180 milligrams of compound, 0.35 mM), N- bromo-succinimide (75 milligrams, 0.42 mM)
It is dissolved in chloroform (15 milliliters), acetic acid (3 milliliters) is added dropwise under ice-water bath, drop finishes, and reaction is stirred at room temperature 6 hours, instead
Answer liquid that water (30 milliliters, three times), saturated sodium bicarbonate (20 milliliters), sodium thiosulfate (20 milliliters) is used to wash respectively, organic layer is dense
Contracting silica gel crosses column (petroleum ether: methylene chloride=5:1) and obtains 205 milligrams of compound 064-4, LC-MS purity: 99%, yield 98%.1H-NMR(400MHz,CDCl3)δ:7.077-7.087(d,2H),7.244-7.289(m,3H),7.342-7.360(m,3H),
7.468-7.488(m,2H),7.548-7.558(d,1H),7.637-7.661(m,2H),7.690-7.711(d,2H),
7.770-7.789(d,1H),7.877-7.897(d,2H),8.098-8.117(d,1H)。
4) synthesis of compound 064-5:
By 064-4(50 milligrams of compound, 0.085 mM), compound C " (100 milligrams, 0.103 mM) is dissolved in N,
In N- dimethyl acetamide (3 milliliters), tetra-triphenylphosphine palladium (9.8 milligrams, 0.0085 mM) are added under the conditions of nitrogen protection,
Solution reacts overnight at 70 DEG C, and after being cooled to room temperature, solution is dissolved in ethyl acetate (30 milliliters), water (10 milliliters, three times)
It washes, organic layer is concentrated to get crude product, and silica gel crosses column (petroleum ether: ethyl acetate=1；25) 38 milligrams of compounds 064-5, LC- are obtained
MS purity: 94%, yield 39%.1H-NMR(400MHz,CDCl3)δ:0.829-0.861(t,6H),1.256-1.309(m,8H),
1.379-1.416(m,4H),1.693-1.730(m,4H),3.856-3.858(t,4H),4.029(m,2H),4.174(m,
2H),5.930(s,1H),6.758-6.791(m,4H),63845-6.865(d,2H),7.090(S,1H),7.239-7.253
(m,3H),7.338-7.355(m,6H),7.507-7.527(m,4H),7.694-7.736(m,4H),7.769-7.793(m,
2H),7.895-7.915(d,2H),8.129-8.150(d,2H)。
5) synthesis of compound 064-6:
By 064-5(38 milligrams of compound, 0.032 mM) it is dissolved in methylene chloride (5 milliliters), it is added dropwise under ice-water bath dense
Hydrochloric acid (1 milliliter), drop finish, and solution reacts overnight at room temperature.Reaction solution is adjusted to neutrality with saturated sodium bicarbonate solution, uses dichloro
(20 milliliters) of methane extractions, extract liquor are washed with water (10 milliliters, three times), and organic layer is concentrated to get 52 milligrams of crude Compound 064-
6, it is directly used in and reacts in next step.LC-MS purity: 90%, yield 140%.1H-NMR(400MHz,CDCl3)δ:0.782-0.857
(m,6H),1.257-1.3092(m,8H),1.335-1.418(m,4H),1.694-1.7302(m,4H),3.881(m,4H),
6.775-6.793(d,4H),6.997(m,4H),7.201-7.229(m,6H),7.334-7.380(m,5H),7.502-7.522
(m,2H),7.573(s,1H),7.690-7.722(m,4H),7.760-7.790(m,4H),7.760-7.791(m,2H),
7.884-7.905(d,2H),8.130-8.150(d,1H),10.120(s,1H)。
6) synthesis of compound CGTD-DSSC-064:
By 064-6(52 milligrams of compound, 0.045 mM), cyanoacetic acid (19 milligrams, 0.225 mM), ammonium acetate
(17 milligrams, 0.225 mM) are dissolved in acetic acid (4 milliliters), and under nitrogen protection, reaction solution reacts 5 hours at 125 DEG C, cold
But it filters afterwards, filtrate concentration, silica gel crosses column (methylene chloride: methanol=50:1) and obtains 19 milligrams of compound CGTD-DSSC-062.
LC-MS purity: 100%, yield 34%.1H-NMR(400MHz,DMSO)δ:0.921(m,6H),1.278-1.482(m,12H),
1.745-1.787(m,4H),3.994(m,4H),6.805-6.830(d,2H),6.930-6.996(m,4H),7.038-7.094
(m,4H),7.301-7.553(m,10H),7.755(m,2H),7.840-7.863(m,2H),7.971-8.097(m,5H),
8.310(s,1H),8.467-8.487(d,1H)。
Embodiment 43
1) synthesis of compound 065-2
By compound 065-1 (500 milligrams, 1.38 mMs), and N- bromo-succinimide (245.4 milligrams, 1.38 mmoles
You), it is added in the flask for filling 15 milliliters of n,N-Dimethylformamide, reacts 1 hour under room temperature, be added 60 milliliters
400 milligrams of 065-2 are obtained by filtration in water, solid.Yield 65.7%.ESI-MS(M+H+)=441.1。
2) synthesis of compound 065-3
By compound 065-2 (400 milligrams, 0.9 mM), tributyl (4- trifluoromethyl-phenyl) tin (475 milligrams,
1.1 mMs), tetra-triphenylphosphine palladium (55 milligrams, 0.05 mM) is added in the flask for filling 50 milliliters of toluene solutions,
Under nitrogen protection, 100 degrees Celsius of reactions overnight, are concentrated to get crude product after being cooled to room temperature, silica gel is crossed column (petroleum ether=100%) and obtained
To 410 milligrams of compound 065-3.Yield 89%.ESI-MS(M+H+)=507.2。
3) synthesis of compound 065-4
By compound 065-3 (410 milligrams, 0.81 mM), and N- bromo-succinimide (145 milligrams, 0.81 mmoles
You), it is added in the flask for filling 10 milliliters of n,N-Dimethylformamide, reacts 2 hours under room temperature, be added 60 milliliters
270 milligrams of 065-4 are obtained by filtration in water, solid.Yield 57%.ESI-MS(M+H+)=585.1。
4) synthesis of compound 065-5
By compound 065-4 (270 milligrams, 0.46 mM), and tributyl (2- thienyl) tin (258 milligrams, 0.69 mmoles
You), tetra-triphenylphosphine palladium (30 milligrams, 0.03 mM) is added in the flask for filling 15 milliliters of toluene solutions, is protected in nitrogen
Under shield, 100 degrees Celsius of reactions overnight, are concentrated to get crude product after being cooled to room temperature, silica gel crosses column (petroleum ether=100%) and obtains 240
Milligram compound 065-5.Yield 89%.ESI-MS(M+H+)=589.2。
5) synthesis of compound 065-6
By compound 065-5 (220 milligrams, 0.37 mM), and N- bromo-succinimide (80 milligrams, 0.45 mmoles
You), it is added in the flask for filling 10 milliliters of n,N-Dimethylformamide, reacts 1 hour under room temperature, be added 60 milliliters
240 milligrams of 065-6 are obtained by filtration in water, solid.Yield 90%.ESI-MS(M+H+)=667.1。
6) synthesis of compound 065-7
By compound 065-6 (72 milligrams, 0.11 mM), 055-1b (100 milligrams, 0.11 mM), four triphenyls
Phosphine palladium (10 milligrams, 0.01 mM) is added in the flask for filling 5 milliliters of n,N-Dimethylformamide, under nitrogen protection,
70 degrees Celsius of reactions overnight, are added 25 milliliters of water after being cooled to room temperature, add ethyl acetate extraction (20 milliliters of x3), organic phase
(20 milliliters of x2) is washed with saturated salt solution, anhydrous sodium sulfate dries, filters, and filtrate is concentrated to get crude product, and silica gel crosses column (petroleum
Ether: ethyl acetate=10:1) obtain 50 milligrams of compound 065-7.Yield 37%.ESI-MS(M+H+)=1268.4。
7) synthesis of compound 065-8
By compound 065-7 (72 milligrams, 0.04 mM), it is added to and fills 10 milliliters of methylene chloride and 1 milliliter of dense salt
It in the flask of sour mixed solution, reacts 3 hours under room temperature, 30 milliliters of water is added, add methylene chloride and extract (20 milliliters
X3), (20 milliliters of x2) is washed with water in organic phase, and anhydrous sodium sulfate dries, filters, and filtrate is concentrated to get 47 milligrams of compound 065-8.
Yield 98%.ESI-MS(M+H+)=1224.4。
8) synthesis of CGTD-DSSC-065
Under nitrogen protection, by the 065-8(40 milligram of above compound, 0.032 mM), cyanoacetic acid (11 milligrams,
0.13 mM), ammonium acetate (10 milligrams, 0.13 mM) and (5 milliliters) of acetic acid are mixed and are stirred under 125 degrees Celsius
Reaction 12 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-0655 milligrams of products C.Yield 12%.1H-
NMR(400MHz,DMSO-d6):0.853(m,12H),1.236(m,20H),1.320(m,8H),1.421(m,4H),1.752
(m,4H),3.882(t,4H),6.742(d,2H),6.915(d,4H),7.051(d,4H),7.308(d,1H),7.351(d,
1H),7.407(d,1H),7.482(d,1H),7.510(m,3H),7.732(m,4H),7.808(s,1H),7.887(d,2H),
7.983 (s, 1H), 8.188 (s, 1H) .ESI-MS (M+H+)1291.4。
Embodiment 44
1) synthesis of compound 066-1
By compound Z ' (110 milligrams, 0.337 mM), 029-1 (119 milligrams, 0.337 mM), potassium carbonate (139
Milligram, 1.01 mMs), tetra-triphenylphosphine palladium (39 milligrams, 0.034 mM) is added to and fills 20 milliliters of tetrahydrofurans and 6
In the flask of milliliter water, under the conditions of nitrogen protection, solution reacts 16 hours at 60 c, is concentrated to get after being cooled to room temperature
Crude product, silica gel cross column (petroleum ether: ethyl acetate=20:1) and obtain 58 milligrams of compound 066-1.Yield 36.4%.ESI-MS(M+H+)
=474.7。
2) synthesis of compound 066-2
By compound 066-1 (58 milligrams, 0.123 mM), X (77 milligrams, 0.135 mM), potassium carbonate (51 millis
Gram, 0.369 mM), tetra-triphenylphosphine palladium (13.9 milligrams, 0.012 mM) is added to and fills 10 milliliters of tetrahydrofurans and 2
In the flask of milliliter water, under the conditions of nitrogen protection, solution reacts 16 hours under 65 degrees Celsius, is concentrated to get after being cooled to room temperature
Crude product, silica gel cross column (petroleum ether: ethyl acetate=10:1) and obtain 70 milligrams of compound 066-2, yield 68.1%.ESI-MS(M+H+)
=838.3.
3) synthesis of CGTD-DSSC-066
Under nitrogen protection, by the 066-2(70 milligram of above compound, 0.083 mM), cyanoacetic acid (28.4 millis
Gram, 0.334 mM), ammonium acetate (25.7 milligrams, 0.334 mM) and (10 milliliters) of acetic acid mixing and it is Celsius 125
It is stirred to react under degree 5 hours.Solid is precipitated after being cooled to room temperature, and 40 milligrams of CGTD-DSSC-066 are obtained by filtration.Yield
53.25%。1H-NMR(400MHz,DMSO-d6):0.879(t,6H),1.310(m,8H),1.409(m,4H),1.698(m,
4H),3.932(t,4H),6.745(d,2H),6.902(d,4H),7.031(d,4H),7.442(d,1H),7.524(d,2H),
7.809(m,3H),7.886(d,1H),7.945(d,2H),8.393(s,1H),13.936(s,1H).ESI-MS(M+H+)
905.3。
Embodiment 45
1) synthesis of compound 067-2
By compound 067-1 (230 milligrams, 1.1 mMs), 2- thienyl boric acid (164 milligrams, 1.28 mMs), carbonic acid
Potassium (300 milligrams, 2.2 mMs), tetra-triphenylphosphine palladium (20 milligrams, 0.02 mM) are added to and fill 50 milliliters of tetrahydrofurans
In the flask of 10 milliliters of water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated after being cooled to room temperature
Crude product is obtained, silica gel crosses column (petroleum ether: ethyl acetate=20:1) and obtains 200 milligrams of compound 067-2.Yield 85%.ESI-MS
(M+H+)=219.0。
2) synthesis of compound 067-3
By compound 067-2 (200 milligrams, 0.92 mM), N- bromo-succinimide (178 milligrams, 1 mM),
It is added in the flask for filling 10 milliliters of acetic acid and 10 milliliters of chloroform mixed solutions, reacts 2 hours under room temperature, be added
60 milliliters of water add methylene chloride extraction (20 milliliters of x3), and organic phase is washed with water (20 milliliters of x2), and anhydrous sodium sulfate is dry,
Filtering, filtrate are concentrated to get 245 milligrams of compound 067-3.Yield 90%.ESI-MS(M+H+)=296.9。
3) synthesis of compound 067-4
By compound 067-3 (120 milligrams, 0.82 mM), S'(200 milligrams, 0.82 mM), tetra-triphenylphosphine palladium
(20 milligrams, 0.02 mM) are added in the flask for filling 10 milliliters of n,N-Dimethylformamide solution, under nitrogen protection,
Overnight, after being cooled to room temperature, 40 milliliters of water are added in 70 degrees Celsius of reactions, add ethyl acetate extraction (20 milliliters of x3), organic
(20 milliliters of x2) mutually is washed with saturated common salt, anhydrous sodium sulfate dries, filters, and filtrate is concentrated to get crude product, and silica gel crosses column (petroleum
Ether: ethyl acetate=20:1) obtain 100 milligrams of compound 067-4.Yield 56%.ESI-MS(M+H+)=455.0。
4) synthesis of compound 067-5
By compound 067-4 (100 milligrams, 0.22 mM), and N- bromo-succinimide (43 milligrams, 0.24 mmoles
You), it is added in the flask for filling 8 milliliters of n,N-Dimethylformamide, reacts 8 hours under room temperature, 50 milliliters of water are added,
118 milligrams of 067-5 are obtained by filtration in solid.Yield 100%.ESI-MS(M+H+)=532.9。
5) synthesis of compound 067-6
By compound 067-5 (118 milligrams, 0.22 mM), it is added to and fills 10 milliliters of methylene chloride and 1 milliliter of dense salt
It in the flask of sour mixed solution, reacts 8 hours under room temperature, 30 milliliters of water is added, add methylene chloride and extract (20 milliliters
X3), (20 milliliters of x2) is washed with water in organic phase, and anhydrous sodium sulfate dries, filters, and filtrate is concentrated to get 107 milligrams of compound 067-
6.Yield 99%.ESI-MS(M+H+)=490.5。
6) synthesis of compound 067-7
By compound 067-6 (107 milligrams, 0.22 mM), X (151 milligrams, 0.26 mM), potassium carbonate (61 millis
Gram, 0.44 mM), tetra-triphenylphosphine palladium (20 milligrams, 0.02 mM) be added to fill 50 milliliters of tetrahydrofurans and 10 milli
In the flask for rising water, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated to get slightly after being cooled to room temperature
Product, silica gel cross column (petroleum ether: ethyl acetate=10:1) and obtain 150 milligrams of compound 067-7.Yield 80%.ESI-MS(M+H+)=
854.2。
7) synthesis of CGTD-DSSC-067
Under nitrogen protection, by the 063-7(150 milligram of above compound, 0.175 mM), cyanoacetic acid (60 millis
Gram, 0.7 mM), ammonium acetate (54 milligrams, 0.7 mM) and (5 milliliters) of acetic acid are mixed and are stirred under 125 degrees Celsius
Reaction 8 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-06770 milligrams of products C.Yield 50.0%.
1H-NMR(400MHz,DMSO-d6):0.881(t,6H),1.309(m,8H),1.408(m,4H),1.697(m,4H),3.923
(t,4H),6.736(d,2H),6.905(d,4H),7.003(d,4H),7.21(s,1H),7.444(m,4H),7.667(s,
1H),7.950(m,2H),8.118(m,3H).ESI-MS(M+H+)=921.2。
Embodiment 46
1) synthesis of compound 068-2
By compound 068-1 (184 milligrams, 0.42 mM), S'(220 milligrams, 0.42 mM), tetra-triphenylphosphine palladium
(30 milligrams, 0.03 mM) are added in the flask for filling 10 milliliters of n,N-Dimethylformamide solution, under nitrogen protection,
Overnight, after being cooled to room temperature, 40 milliliters of water are added in 70 degrees Celsius of reactions, add ethyl acetate extraction (20 milliliters of x3), organic
(20 milliliters of x2) mutually is washed with saturated common salt, anhydrous sodium sulfate dries, filters, and filtrate is concentrated to get crude product, and silica gel crosses column (petroleum
Ether: ethyl acetate=10:1) obtain 170 milligrams of compound 068-2.Yield 68%.ESI-MS(M+H+)=599.0.
2) synthesis of compound 068-3
By compound 068-2 (170 milligrams, 0.28 mM), and N- bromo-succinimide (60 milligrams, 0.34 mmoles
You), it is added in the flask for filling 5 milliliters of n,N-Dimethylformamide, reacts 2 hours under room temperature, 50 milliliters of water are added,
150 milligrams of 068-3 are obtained by filtration in solid.Yield 78%.ESI-MS(M+H+)=676.9。
3) synthesis of compound 068-4
By compound 068-3 (150 milligrams, 0.22 mM), it is added to and fills 10 milliliters of methylene chloride and 1 milliliter of dense salt
It in the flask of sour mixed solution, reacts 8 hours under room temperature, 30 milliliters of water is added, add methylene chloride and extract (20 milliliters
X3), (20 milliliters of x2) is washed with water in organic phase, and anhydrous sodium sulfate dries, filters, and filtrate is concentrated to get 140 milligrams of compound 068-
4.Yield 98%.ESI-MS(M+H+)=632.9。
4) synthesis of compound 068-5
By compound 068-4 (40 milligrams, 0.22 mM), X (126 milligrams, 0.22 mM), potassium carbonate (61 milligrams,
0.44 mM), tetra-triphenylphosphine palladium (30 milligrams, 0.03 mM) is added to and fills 50 milliliters of tetrahydrofurans and 10 milliliters of water
Flask in, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated to get crude product, silicon after being cooled to room temperature
Glue crosses column (petroleum ether: methylene chloride=1:2) and obtains 50 milligrams of compound 068-5.Yield 23%.ESI-MS(M+H+)=998.3。
5) synthesis of CGTD-DSSC-068
Under nitrogen protection, by the 068-5(50 milligram of above compound, 0.05 mM), cyanoacetic acid (17 milligrams,
0.2 mM), ammonium acetate (15.4 milligrams, 0.2 mM) and (5 milliliters) of acetic acid are mixed and are stirred under 125 degrees Celsius
Reaction 8 hours.There is solid precipitation after being cooled to room temperature, is obtained by filtration GTD-DSSC-06826 milligrams of products C.Yield 48.7%.
1H-NMR(400MHz,DMSO-d6):0.889(t,6H),1.312(m,8H),1.417(m,4H),1.706(m,4H),3.930
(t,4H),6.740(d,2H),6.890(d,4H),7.025(d,4H),7.185(s,1H),7.391(s,1H),7.437(m,
3H), 7.845 (m, 3H), 7.971 (s, 1H), 8.131 (m, 5H) .ESI-MS (M+H+)=1065.3。
Embodiment 47
1) synthesis of compound 031-3
By compound Q ' (450 milligrams, 1.16 mMs), X (660 milligrams, 1.16 mMs), potassium carbonate (320 milligrams,
2.32 mMs), tetra-triphenylphosphine palladium (67 milligrams, 0.06 mM) is added to and fills 80 milliliters of tetrahydrofurans and 20 milliliters of water
Flask in, under the conditions of nitrogen protection, solution reacts 8 hours under 68 degrees Celsius, is concentrated to get crude product, silicon after being cooled to room temperature
Glue crosses column (petroleum ether: ethyl acetate=10:1) and obtains 100 milligrams of compound 031-3.Yield 80%.ESI-MS(M+H+)=
754.2。
2) synthesis of compound 031-4
By compound 031-3 (50 milligrams, 0.07 mM), to trifluoromethylbenzene boronic acid (20 milligrams, 0.1 mM),
Palladium acetate (3 milligrams, 0.01 mM), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (10 milligrams, 0.02 mM),
Cesium hydroxide (20 milligrams, 0.12 mM), is added in the flask for filling 8 milliliters of n-butanols and 2 milliliters of water mixed solutions, nitrogen
Under the conditions of gas shielded, reacts at room temperature 12 hours, be concentrated to get crude product, silica gel crosses column (petroleum ether: ethyl acetate=6:1) and obtains 20
Milligram compound 031-4.Yield 40%.ESI-MS(M+H+)=864.2。
3) synthesis of compound CGTD-DSSC-031
Under nitrogen protection, by 031-4(56 milligrams of compound, 0.06 mM), and cyanoacetic acid (20 milligrams, 0.24 milli
Mole), ammonium acetate (19 milligrams, 0.24 mM) and (10 milliliters) of acetic acid are mixed and are stirred to react at 125 DEG C 5 hours.
There is solid precipitation after being cooled to room temperature, filter, filter cake column chromatography for separation (methylene chloride: methanol=40:1) obtains 27 milligrams of chemical combination
Object CGTD-DSSC-031, LC-MS purity 100%, yield 45%.1H-NMR(400MHz,DMSO-d6)0.878(t,6H),
1.257-1.317(m,8H),1.405(t,4H),1.658-1.728(m,4H),3.921(t,4H),6.741(d,2H),6.896
(d,4H),7.016(d,4H),7.217(d,1H),7.403-7.469(m,4H),7.684-7.741(m,3H),7.886(d,
2H),7.974(s,1H),8.120(s,1H).ESI-MS[M+H]+: 931.2.
Embodiment 48
1) synthesis of intermediate 069-2
069-1(2.47 grams of compound, 10 mMs is added in 50 milliliters of three-necked flasks), 2-(tributyl tin) thiophene
(3.73 grams, 10 mMs), tetra-triphenylphosphine palladium (231 milligrams, 2 mMs) and 20 milliliters of toluene return for 130 degree under nitrogen protection
Overnight, concentration removes solvent after being cooled to room temperature, and silica gel chromatograph post separation (petroleum ether) obtains intermediate 069-22.47 for stream reaction
Gram.Yield 98.8%, purity 99.5%.1H-NMR(400MHz,DMSO-d6):7.917(m,1H),7.569(m,1H),7.284
(t,1H)。
2) synthesis of intermediate 069-3
069-2(2.00 grams of compound, 8 mMs is added in 50 milliliters of single-necked flasks), N- bromo-succinimide (2.28
Gram, 12.8 mMs) and 32 milliliters of n,N-Dimethylformamide, 25 degree of reactions overnight, be poured into 150 milliliters of ice water, stir
It mixes half an hour, filters, washing three times, is dried to obtain 069-32.23 grams of intermediate.Yield 84.8%, purity 98.5%.1H-NMR
(400MHz,DMSO-d6):7.404(m,2H).
3) synthesis of intermediate 069-4
Compound 069-3(75 milligrams, 0.228 mM is added in 5 milliliters of single-necked flasks), compound S ' (120 milligrams,
0.228 mM), tetra-triphenylphosphine palladium (15 milligrams, 0.023 mM) and 3 milliliters of toluene, 130 degree of reflux under nitrogen protection
Reaction overnight, is cooled to concentration after room temperature and removes solvent, during silica gel chromatograph post separation (petroleum ether: ethyl acetate=25:1) obtains
069-480 milligrams of mesosome.Yield 72.1%, purity 96.5%.1H-NMR(400MHz,DMSO-d6):7.714(m,1H),7.551
(m,2H),7.473(s,1H),7.351(t,1H),7.189(m,1H),5.834(s,1H),4.103(m,2H),3.967(m,
2H).
4) synthesis of compound 069-5
Compound 069-4(80 milligrams, 0.159 mM is added in 5 milliliters of single-necked flasks), N- bromo-succinimide
(29 milligrams, 0.159 mM) and 2 milliliters of n,N-Dimethylformamide, 25 degree of reactions overnight, are poured into 10 milliliters of ice water
In, it stirs half an hour, filtering, washing three times, is dried to obtain 069-559 milligrams of product Intermediate.Yield 63.4%.1H-NMR
(400MHz,DMSO-d6):7.574(s,2H),7.481(s,1H),7.323(d,1H),7.189(d,1H),5.813(s,1H),
4.116(t,2H),3.970(t,2H).
5) synthesis of compound 069-6
Hydrochloric acid (1M, 1 milliliter, 1.0 mMs) is added to 15 milliliters for filling 069-5 (56.5 milligrams, 0.1 mM)
It in methylene chloride, reacts 16 hours at room temperature, methylene chloride extraction is concentrated to get 52 milligrams of compound 069-6.Yield 99.8%.
ESI-MS(M+H+)=520.9.
6) synthesis of compound 069-7
By compound 069-6 (52 milligrams, 0.1 mM), X (57 milligrams, 0.1 mM), potassium carbonate (41.4 milligrams,
0.3 mM), tetra-triphenylphosphine palladium (11.6 milligrams, 0.01 mM) is added to and fills 10 milliliters of tetrahydrofurans and 2 milliliters of water
Flask in, under the conditions of nitrogen protection, solution reacts 16 hours under 65 degrees Celsius, be concentrated to get crude product after being cooled to room temperature,
Silica gel crosses column (petroleum ether: ethyl acetate=25:1) and obtains 60 milligrams of compound 069-7.Yield 68.2%.ESI-MS(M+H+)=
886.2。
7) synthesis of CGTD-DSSC-069
Under nitrogen protection, by the 069-7(26.6 milligram of above compound, 0.03 mM), cyanoacetic acid (10.2 millis
Gram, 0.12 mM), ammonium acetate (9.24 milligrams, 0.12 mM) and (6 milliliters) of acetic acid mixing and under 125 degrees Celsius
It is stirred to react 5 hours.Solid is precipitated after being cooled to room temperature, and 20 milligrams of CGTD-DSSC-069 are obtained by filtration.Yield 69.94%.1H-
NMR(400MHz,DMSO-d6):0.880(t,6H),1.312(m,8H),1.409(m,4H),1.698(m,4H),3.928(t,
4H),6.737(d,2H),6.891(d,4H),7.015(d,4H),7.226(d,1H),7.416(d,1H),7.494(m,3H),
7.567(d,1H),8.005(s,1H),8.104(s,1H),13.886(s,1H).ESI-MS(M+H+)953.3。
Embodiment 49
1) synthesis of 038-2
Under nitrogen protection, by 038-1(90 milligrams of compound, 0.19 mM), X(132 milligrams, 0.23 mM),
Potassium carbonate (79 milligrams, 0.57 mM), four triphenyl phosphorus palladiums (23 milligrams, 0.02 mM) and tetrahydrofuran: water (15
Milliliter) it mixes and is stirred to react at 68 DEG C 8 hours.After being cooled to room temperature, concentration removing solvent, silica gel column chromatography (petroleum ether:
Ethyl acetate=100:1) obtain 24 milligrams of 038-2, yield 14.9%.ESI-MS(M+H+):826.2。
2) synthesis of CGTD-DSSC-038
Under nitrogen protection, by 038-2(24 milligrams of compound, 0.03 mM), and cyanoacetic acid (13 milligrams, 0.15 milli
Mole), ammonium acetate (12 milligrams, 0.15 mM) and (10 milliliters) of acetic acid are mixed and are stirred to react at 125 DEG C 5 hours.
There is solid precipitation after being cooled to room temperature, filters, filter cake column chromatography for separation (methylene chloride: methanol=30:1) obtains 10 milligrams of product,
Yield 38.4%.1H-NMR(400MHz,DMSO-d6)0.885(s,6H),1.236-1.410(m,12H),1.703(s,4H),
3.802(s,3H),3.937(s,4H),6.765(d,2H),6.876-6.927(m,4H),6.993-7.037(m,6H),7.246
(s,1H),7.366(s,1H),7.432(d,2H),7.498(d,2H),7.641(d,2H),7.949(s,1H),8.144(s,
1H).ESI-MS(M+H+):893.2。
Effect example 1
The dye sensitized nano crystal body solar battery of organic dye sensitized dose of application of the invention is organic by having adsorbed
The nanocrystal light anode of dye sensitizing agent, electrolyte and to electrode composition, preparation and performance characterization are as follows:
In the present invention dye sensitized nano crystal body solar battery the preparation method is as follows:
The preparation of transparent substrates (1) and conductive layer (2) the following steps are included:
1) electro-conductive glass pre-processes: taking a small amount of glass cleaner in water, is cleaned by ultrasonic 5 minutes.Again by electro-conductive glass
It is placed in secondary water, is cleaned by ultrasonic 5 minutes.Electro-conductive glass is again placed in dehydrated alcohol and is cleaned by ultrasonic 5 minutes.Hair dryer is certainly
Right wind 3 minutes.Finally, with high-purity CO2Solid-liquid mixing aeroge pistol alignment electro-conductive glass conducting surface pass through by
Layer cleaning 2 minutes.
The preparation of light absorbing layer (3) the following steps are included:
2) TiO2The preparation of slurry: using commercialized P25 powder as raw material, by grinding repeatedly under different conditions,
The methods of stirring and ultrasound reach control TiO2The purpose of granular size of slurry, the uniformity and solid content.According to this preparation side
The feed ratio of method, primary experiment can prepare 20 grams -30 grams of nano-crystalline layers TiO2Slurry.The specific method is as follows:
A. 6 grams of TiO is taken2Powder and the mixing of 1 milliliter of acetic acid, grind 5 minutes；
B. slowly 1 milliliter of water, grinding 1 minute are repeated 5 times；
C. it is slowly added into 1 milliliter of ethyl alcohol, grinds 1 minute, is repeated 15 times；
D. it is slowly added into 2.5 milliliters of ethyl alcohol, grinds 1 minute, is repeated 6 times；
E. TiO is shifted with 100 milliliters of ethyl alcohol slowly2Slurry is to a beaker；
F. with stirrer stirring (300rpm) 1 minute, interval is 2 minutes ultrasonic, is then stirred for (300rpm) 1 minute；
G. 20 grams of terpinols are slowly added into；
H. stirring (300rpm) 1 minute, interval ultrasound 2 minutes, then proceedes to stirring (300rpm) 1 minute；
I. it is slowly added into 3 grams: 30 grams ethyl cellulose (1.5 grams of ECl and 1.5 gram of EC2) ethanol solution (10%)
J. stirring (300rpm) 1 minute, interval ultrasound 2 minutes, then proceedes to stirring (300rpm) 1 minute；
K. 10 steps are repeated three times；
L. rotary evaporation slowly removes ethyl alcohol under 35 degree；
M. it is ground 30 minutes with agate mortar.
3) preparation of light-sensitive coloring agent solution:
A. suitable solvent is selected.
B. the dye solution of a certain concentration (such as 0.3mM or 0.5mM) is prepared, ultrasound is completely dissolved dyestuff.
C. with 0.22 μm of micropore filtering film filter dyes solution.
D. filtered dye solution dyestuff is placed in impregnate in bottle.
E. dye solution is being sealed and is being saved under darkroom.
The preparation of electrolyte layer (4) the following steps are included:
4) it the preparation of high-efficiency electrolytic solution: (volume ratio: 1/1) is prepared with absolutely dry acetonitrile and valeronitrile and contains 1.0M
DMII, 50mM LiI, 30mM I2, the solution of the GuNCS of 0.5M tert .-butylpyridine and 0.1M.
Preparation to electrode layer (5) the following steps are included:
5) to electrode: the electro-conductive glass that sputtering method has been plated is cleaned by ultrasonic 10 minutes, then respectively with steaming with 1N dilute hydrochloric acid
Distilled water and dehydrated alcohol are cleaned by ultrasonic 5 minutes, are placed in 120 degree of baking oven lower dryings 30 minutes, cooling is placed in spare in drying box.
6) battery composition and test: by TiO2Nano-electrode is soaked in containing organic dye sensitized dose of solution of the invention
The middle some time, dye composition is made to be adsorbed in TiO2On the nano particle of electrode, TiO is then taken out2Electrode, slightly with solvent
After rinsing and drying, covers to electrode (5) and seal.Later, electrolyte (4) are injected, then by inlet seal, can be completed
Effect area is 0.24cm2Dye-sensitized solar cells.By resulting dye-sensitized solar cells AM1.5 illumination
Under, test its short circuit current (Jsc), open-circuit voltage (Voc), fill factor (FF), photoelectric conversion efficiency (η).
7) comparative example: dye-sensitized solar cells is made in the same manner described above, specific battery structure is shown in Fig. 1.
Battery data test uses U.S. NEWPORT ORIEL solar simulator and Keithley KEITHLEY data collector,
Under the standard light irradiation of AM1.5, short circuit current (Jsc), the open-circuit voltage (Voc), fill factor (FF), light of difference test dye
Photoelectric transformation efficiency (η), test result representative data are shown in Table 1 and Fig. 2.Representative organic dye sensitized agent molecule it is ultraviolet-can
See that absorption spectrum spectrogram is shown in Fig. 3.
8) photoelectric conversion performance measurement result: conjugation aromatic ring chromophore highly branched chain derivatization organic dyestuff of the invention
Sensitizer, the photoelectric conversion efficiency of dye-sensitized solar cells reach the 80% of current the recognized standard dyestuff N719 efficiency.
The representative dyestuff that the N719 and embodiment 1-49 that table 1 is commercialized are obtained is for dye-sensitized nano solar battery
Performance data comparison
| Dyes | Voc/V | Jsc/mA cm2 | FF/% | Effi./% |
| CGTD-DSSC-025 | 0.67 | 15.15 | 63.63 | 6.44 |
| CGTD-DSSC-029 | 0.70 | 14.85 | 63.04 | 6.58 |
| CGTD-DSSC-031 | 0.71 | 15.51 | 65.15 | 7.17 |
| CGTD-DSSC-036 | 0.74 | 11.96 | 65.80 | 5.81 |
| CGTD-DSSC-039 | 0.69 | 14.83 | 64.45 | 6.64 |
| CGTD-DSSC-55 | 0.69 | 15.85 | 67.78 | 7.41 |
| CGTD-DSSC-64 | 0.68 | 16.69 | 68.09 | 7.60 |
| CGTD-DSSC-66 | 0.57 | 14.64 | 65.30 | 5.46 |
| CGTD-DSSC-69 | 0.65 | 15.02 | 62.71 | 6.11 |
| N719 | 0.70 | 18.76 | 65.80 | 8.62 |
Claims (14)
1. organic dye sensitized dose a kind of, it is characterised in that: its general formula is shown in formula I；Wherein, A is short of electricity subelement, is electronics
Receptor；D is electron rich unit, is electron donor；B is mutually to be bonded with the nanometer micropore surface of dye sensitization battery light electricity anode,
To which the electron-transport that quick agent molecule excites after visible and ultraviolet light will be contaminated go out to be formed the structural unit of electric current；
The A is the substituent group form of following any structure:
Wherein, R1、R2、R3、R6、R7、R44、R47And R48It is independent to select hydrogen, C1-4Alkyl, C1-4Alkoxy, C5-10Virtue
The C that base, trifluoromethyl replace5-10Aryl and one or more of trifluoromethyl；R4And R5Be independently selected from halogen,
One or more of cyano, formoxyl and trifluoromethyl；R8、R9、R10、R11、R12、R13、R14、R45And R46It is independent to be
C5-10Alkyl；
The D is the substituent group form of following any structure:
Wherein, R15Selected from hydrogen, C1-4Alkyl and C1-10One or more of alkoxy；R16Selected from C1-4Alkyl and C6-10
One or two of aryl；R17、R18、R19And R20It is independently selected from hydrogen, C1-6Alkyl, C1-6Alkoxy and C1-6
One or more of the phenyl that replaces of alkoxy；R21And R22It is independently selected from hydrogen, C1-4Alkyl, C6-10Aryl,
C1-4Alkoxy and C1-4One or more of alkyl amino；R23、R24、R25、R26And R27Be independently selected from hydrogen,
C1-4Alkyl and C1-4One or more of alkoxy；
The B is the substituent group form of following any structure:
Wherein, R40And R41It is independently selected from hydrogen, carboxyl, hydroxyl and C2-6One or more of alkynyl；R42Selected from carboxylic
Base,Cyano, C6-10Aryl, the C that is replaced by one or more cyano6-10Aryl and by one or more carboxylics
The C that base replaces6-10One or more of aryl；R43For C1~C9Straight chain or branched paraffin.
2. organic dye sensitized dose as described in claim 1, it is characterised in that: the R1、R2、R3、R6Or R7Described in
C1-4Alkyl be methyl；
And/or the R1、R2、R3、R6、R7、R44、R47And R48Described in C1-4Alkoxy be methoxyl group；
And/or the R1、R2、R3、R6、R7、R44、R47And R48Described in C5-10Aryl be phenyl；
And/or the R1、R2、R3、R6、R7、R44、R47And R48Described in trifluoromethyl replace C5-10Aryl be trifluoro
Aminomethyl phenyl；
And/or the R4Or R5Described in halogen be F；
And/or the R8、R9、R10、R11、R12、R13、R14、R45And R46Described in C5-10Alkyl be
And/or the R40And R41Being independently selected from carboxyl described in carboxyl is C1-4Carboxyl.
3. organic dye sensitized dose as described in claim 1, it is characterised in that: the A is the substitution of following any structure
Base form:
4. organic dye sensitized dose as claimed in claim 3, it is characterised in that: any substitution that the A is as follows
Base:
5. organic dye sensitized dose as described in claim 1, it is characterised in that: the R15Described in C1-10Alkoxy
For methoxyl group or
And/or the R16Described in C1-4Alkyl be methyl；
And/or the R16Described in C6-10Aryl be phenyl；
And/or the R17、R18、R19Or R20Described in C1-6Alkyl be
And/or the R17、R18、R19Or R20Described in C1-6Alkoxy be methoxyl group or
And/or the R17、R18、R19Or R20Described in C1-6Alkoxy replace phenyl be
And/or the R21Or R22Described in C1-4Alkyl be methyl, ethyl, propyl, isopropyl or tert-butyl；
And/or the R21Or R22Described in C6-10Aryl be phenyl；
And/or the R21Or R22Described in C1-4Alkoxy be methoxyl group, ethyoxyl, propoxyl group, isopropoxy or uncle
Butoxy；
And/or the R21Or R22Described in C1-4Alkyl amino be methylamino, ethylamino- or Propylamino.
6. organic dye sensitized dose as claimed in claim 5, it is characterised in that: the D is the substitution of following any structure
Base form:
7. organic dye sensitized dose as claimed in claim 6, it is characterised in that: the D is as follows any substituent group:
8. organic dye sensitized dose as described in claim 1, it is characterised in that: the R40Or R41Described in C2-6Alkynes
Base is acetenyl；
And/or the R40Or R41Described in C1-4Carboxyl be
And/or the R42Described in C6-10Aryl be phenyl；
And/or the R42Described in the C replaced by one or more cyano6-10Aryl be by one or more cyano
Substituted phenyl；
And/or the R42Described in the C replaced by one or more carboxyls6-10Aryl be by one or more carboxyls
Substituted phenyl.
9. organic dye sensitized dose as claimed in claim 8, it is characterised in that: any substitution that the B is as follows
Base:
10. organic dye sensitized dose a kind of, it is characterised in that: be following any compound:
11. as claim 1~10 described in any item organic dye sensitized dose or its salt as light-sensitive coloring agent in photoelectric conversion
Purposes in technology.
12. such as the preparation method of claim 1~10 described in any item organic dye sensitized dose or its salt, it is characterised in that:
The preparation method of terthienyl general formula compound 1 comprising following steps: under gas shield, in organic solvent, by compound
2 withCondensation reaction is carried out, compound 1 is obtained；
Wherein, the definition of A is as described in any one of Claims 1 to 5；The definition of B is as described in claim 1,10 or 11 any one；
The definition of D is as described in claim 1,6,7,8 or 9 any one.
13. the preparation method of organic dye sensitized dose as claimed in claim 12 or its salt, it is characterised in that: terthienyl is logical
The preparation method of formula compound 1 comprising following route:
Route one, the following steps are included:
Step 1: in a solvent, under the conditions of alkali and catalyst are existing, it is anti-that compound 8 and 2- bromothiophene being subjected to Suzuki coupling
It answers, obtains the compound 7；
Step 2: in organic solvent, under the conditions of alkali and catalyst are existing, compound 7 and duplex pinacol borate being subjected to parent
Core substitution reaction obtains the compound 6；
Step 3: in a solvent, under the conditions of alkali and catalyst are existing, it is anti-that compound 6 and compound B-11 being subjected to Suzuki coupling
It answers, obtains the compound 5；
Step 4: in organic solvent, compound 5 and N- bromo-succinimide being subjected to substitution reaction, obtain the chemical combination
Object 4；
Step 5: in a solvent, under the conditions of alkali and catalyst are existing, it is anti-that compound 3 and compound 4 being subjected to Suzuki coupling
It answers, obtains the compound 2；
Step 6: in organic solvent, by compound 2 withCondensation reaction is carried out, compound 1 is obtained；
Route two the following steps are included:
Step 1: in a solvent, under the conditions of alkali and catalyst are existing, compound 10 and compound B-11 being subjected to Suzuki coupling
Reaction obtains the compound P '；
Step 2: in organic solvent, compound P ' and N- bromo-succinimide being subjected to substitution reaction, obtain the change
Close object Q '；
Step 3: in a solvent, under the conditions of alkali and catalyst are existing, by compound Q ' to carry out Suzuki coupling with compound 3 anti-
It answers, obtains the compound 9；
Step 4: in a solvent, under the conditions of alkali and catalyst are existing, it is anti-that compound 8 and compound 9 being subjected to Suzuki coupling
It answers, obtains the compound 2；
Step 5: in organic solvent, by compound 2 withCondensation reaction is carried out, compound 1 is obtained；
Route three the following steps are included:
Step 1: in organic solvent, compound B-11 and N- N-iodosuccinimide being subjected to substitution reaction, obtain the change
Close object 16；
Step 2: in a solvent, under the conditions of alkali and catalyst are existing, it is anti-that compound 3 and compound 16 being subjected to Suzuki coupling
It answers, obtains the compound 15；
Step 3: in organic solvent, under the conditions of acid is existing, compound 15 and carbonyl-protection base being subjected to condensation reaction, obtained
The compound 14；
Step 4: in organic solvent, under the conditions of radical initiator is existing, compound 14 and tributyltin chloride being carried out
Substitution reaction obtains the compound 13；
Step 5: in a solvent, under the conditions of catalyst is existing, compound 12 and compound 13 are subjected to Suzuki coupling reaction,
Obtain the compound 11；
Step 6: in organic solvent, compound 11 and acid being subjected to oxidation reaction and obtain compound 2；
Step 7: in organic solvent, by compound 2 withCondensation reaction is carried out, compound 1 is obtained；
Route four the following steps are included:
Step 1: under the conditions of acid is existing, compound B-11 and carbonyl-protection base being subjected to condensation reaction, obtain the compound
R '；
Step 2: in organic solvent, under the conditions of radical initiator is existing, by compound R it ' is carried out with tributyltin chloride
Substitution reaction obtains the compound S '；
Step 3: in a solvent, under the conditions of catalyst is existing, compound S ' and compound 12 are subjected to Suzuki coupling reaction,
Obtain the compound 18；
Step 4: in organic solvent, compound 18 and N- bromo-succinimide being subjected to substitution reaction, obtain the change
Close object 17；
Step 5: in a solvent, under the conditions of alkali and catalyst are existing, it is anti-that compound 17 and compound 3 being subjected to Suzuki coupling
It answers, obtains the compound 11；
Step 6: in organic solvent, compound 11 and acid being subjected to oxidation reaction and obtain compound 2；
Step 7: in organic solvent, by compound 2 withCondensation reaction is carried out, compound 1 is obtained；
Route five the following steps are included:
Step 1: in a solvent, under the conditions of alkali and catalyst are existing, compound 20 and compound A1 being subjected to Suzuki coupling
Reaction obtains the compound 057-1；
Step 2: in organic solvent, compound 057-1 and N- bromo-succinimide being subjected to substitution reaction, obtained described
Compound T '；
Step 3: under the conditions of acid is existing, compound T ' and carbonyl-protection base being subjected to condensation reaction, obtain the compound
U '；
Step 4: in organic solvent, under the conditions of radical initiator is existing, compound U ' and tributyltin chloride being carried out
Substitution reaction obtains the compound V '；
Step 5: in organic solvent, under the conditions of catalyst is existing, compound 19 and compound V ' being subjected to Suzuki coupling
Reaction obtains the compound 18；
Step 6: in organic solvent, compound 18 and N- bromo-succinimide being subjected to substitution reaction, obtain the change
Close object 17；
Step 7: in a solvent, under the conditions of alkali and catalyst are existing, it is anti-that compound 17 and compound 3 being subjected to Suzuki coupling
It answers, obtains the compound 11；
Step 8: in organic solvent, compound 11 and acid being subjected to oxidation reaction and obtain compound 2；
Step 9: in organic solvent, by compound 2 withCondensation reaction is carried out, compound 1 is obtained；
14. compound 2
Wherein, the definition of A is as described in any one of Claims 1 to 4；Any one of the definition of D such as claim 1,5,6 or 7 institute
It states.
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| KR101699155B1 (en) * | 2015-03-16 | 2017-01-24 | 부산대학교 산학협력단 | New terthiophen compound and use thereof |
| KR102123902B1 (en) * | 2018-08-07 | 2020-06-17 | 전북대학교산학협력단 | Benzothiadiazole compound and perovskite solar cell comprising the same |
| CN110759899B (en) * | 2019-06-28 | 2020-09-25 | 杭州职业技术学院 | High-rigidity quinoxaline dye sensitizer and preparation method and application thereof |
| CN110845489A (en) * | 2019-11-13 | 2020-02-28 | 南京邮电大学 | Asymmetric V-type organic dye sensitizer and preparation method and application thereof |
| CN113896724B (en) * | 2021-10-09 | 2023-11-24 | 吉林大学 | Organic red light micromolecule based on benzothiadiazole-pyrene imidazole and application thereof in preparation of undoped organic electroluminescent device |
| CN114014837A (en) * | 2021-10-29 | 2022-02-08 | 南京碳硅人工智能生物医药技术研究院有限公司 | Design and synthesis of novel probe for visually monitoring viscosity fluctuation of living cells |
| CN115160348B (en) * | 2022-07-06 | 2024-06-21 | 中山大学 | Method for directly borating aromatic C-H bond without metal catalysis under illumination |
| CN116217559B (en) * | 2022-12-29 | 2024-04-02 | 浙江工业大学 | Carbazole compound with antenna and preparation method and application thereof |
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| CN101602759A (en) * | 2009-07-07 | 2009-12-16 | 武汉大学 | Pyrrole group-containing compound and its production and use |
| TW201114844A (en) * | 2009-06-19 | 2011-05-01 | Dongjin Semichem Co Ltd | Novel organic dye and preparation thereof |
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| EP2752935A4 (en) * | 2011-08-25 | 2015-10-28 | Nat Inst For Materials Science | Dye-sensitized solar cell and sensitizing dye |
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