CN105669704B - Tetrathiafulvalene class compound and its synthetic method - Google Patents
Tetrathiafulvalene class compound and its synthetic method Download PDFInfo
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- CN105669704B CN105669704B CN201610009678.5A CN201610009678A CN105669704B CN 105669704 B CN105669704 B CN 105669704B CN 201610009678 A CN201610009678 A CN 201610009678A CN 105669704 B CN105669704 B CN 105669704B
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- pyrroles
- bis
- pyrazine
- sulphur
- diketone
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- -1 Tetrathiafulvalene class compound Chemical class 0.000 title claims abstract description 55
- 238000010189 synthetic method Methods 0.000 title claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005864 Sulphur Substances 0.000 claims abstract description 34
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 21
- 150000003233 pyrroles Chemical class 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 14
- USDIRSJFHPHMAS-UHFFFAOYSA-N ClC1=NC=C(C=2C1=NC=CN=2)F Chemical compound ClC1=NC=C(C=2C1=NC=CN=2)F USDIRSJFHPHMAS-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical class ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical class OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000007832 Na2SO4 Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 4
- SPSSDDOTEZKOOV-UHFFFAOYSA-N 2,3-dichloroquinoxaline Chemical class C1=CC=C2N=C(Cl)C(Cl)=NC2=C1 SPSSDDOTEZKOOV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims 1
- 150000002518 isoindoles Chemical class 0.000 abstract description 8
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical class ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 abstract description 5
- 125000005594 diketone group Chemical group 0.000 abstract 2
- 239000002245 particle Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 6
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical class CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 150000003613 toluenes Chemical class 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical class SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 150000004075 acetic anhydrides Chemical class 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OIIOPWHTJZYKIL-PMACEKPBSA-N (5S)-5-[[[5-[2-chloro-3-[2-chloro-3-[6-methoxy-5-[[[(2S)-5-oxopyrrolidin-2-yl]methylamino]methyl]pyrazin-2-yl]phenyl]phenyl]-3-methoxypyrazin-2-yl]methylamino]methyl]pyrrolidin-2-one Chemical compound C1(=C(N=C(C2=C(C(C3=CC=CC(=C3Cl)C3=NC(OC)=C(N=C3)CNC[C@H]3NC(=O)CC3)=CC=C2)Cl)C=N1)OC)CNC[C@H]1NC(=O)CC1 OIIOPWHTJZYKIL-PMACEKPBSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- MLCNOCRGSBCAGH-UHFFFAOYSA-N 2,3-dichloropyrazine Chemical compound ClC1=NC=CN=C1Cl MLCNOCRGSBCAGH-UHFFFAOYSA-N 0.000 description 1
- KJEGBYNZDMZMLK-UHFFFAOYSA-N 5-(3,4-dichlorocyclohexyl)-2H-pyrrole Chemical class ClC1CC(CCC1Cl)C1=NCC=C1 KJEGBYNZDMZMLK-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- ICXXXLGATNSZAV-UHFFFAOYSA-N butylazanium;chloride Chemical compound [Cl-].CCCC[NH3+] ICXXXLGATNSZAV-UHFFFAOYSA-N 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- KCDFUWGGOXQNPN-UHFFFAOYSA-N n-(furan-2-ylmethyl)-2,1,3-benzothiadiazole-4-sulfonamide Chemical compound C=1C=CC2=NSN=C2C=1S(=O)(=O)NCC1=CC=CO1 KCDFUWGGOXQNPN-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention discloses tetrathiafulvalene class compound and its synthetic method, comprises the following steps：(1) 4,5 2 chloro-phthalic anhydrides are synthesized；(2) diketone of 5,6 dichloro, 2 cyclohexyl iso-indoles 1,3 is synthesized；(3) diketone of 5,6 dibenzyl methyl mercapto, 2 cyclohexyl iso-indoles 1,3 is synthesized；(4) 6 cyclohexyl 5H [1,3] double sulphur [4,5 f] iso-indoles 2,5,7 (6H) triketones are synthesized；(5) 6,6 ' dicyclohexyl 5H, 5 ' H [2,2 ' the different sub- indyl of double [1,3] two sulphur [4,5 f]] 5,5 ', 7,7 ' (6H, 6H ') tetrone is synthesized.
Description
Technical field
The present invention relates to the preparation of OFET materials.More particularly, to a kind of tetrathiafulvalene class compound and its synthesis
Method.
Background technology
In organic charge material for transfer and organic free radical salt, tetrathiafulvalene (tetrathiafulvalene, TTF)
And its derivative has been widely applied in organic semiconductor and superconductor as a kind of electron donor.TTF derivatives
Organic semiconductor layer is used as in OFET devices, there are some superior performances：1. compound is easily prepared and purified and repaiied
Decorations.2. dissolubility is preferable in common solvent, solution processing film technique can be suitably used for.3. there are very strong π-π heaps in the solid state
Product and the interaction of S ... S-phase simultaneously have planar molecule conformation.4.TTF has good electron donation, its HOMO energy level and conventional gold
It is close to belong to electrode work content, is easy to electric charge to be injected into emission layer from metal electrode.
The content of the invention
It is an object of the present invention to provide a kind of tetrathiafulvalene class compound and its synthetic method.
To reach above-mentioned purpose, the present invention uses following technical proposals：Tetrathiafulvalene class compound, as shown in formula (I)：
X is C or N, Y are cyclohexyl or normal-butyl.
The synthetic method of tetrathiafulvalene class compound, comprises the following steps：
(1) chloro-phthalic anhydrides of 4,5- bis- are synthesized；
(2) the chloro- 2- cyclohexyl iso-indoles -1,3- diketone of 5,6- bis- is synthesized；
(3) 5,6- dibenzyl methyl mercapto -2- cyclohexyl iso-indoles -1,3- diketone is synthesized；
(4) 6- cyclohexyl -5H- [1,3] double sulphur [4,5-f] iso-indoles -2,5,7 (6H)-triketone is synthesized；
(5) 6,6 '-dicyclohexyl -5H, 5 ' H- [2,2 '-bis- the different sub- indyls of [1,3] two sulphur [4,5-f]] -5,5 ' is synthesized,
7,7 ' (6H, 6H ') tetrone.
The synthetic method of above-mentioned tetrathiafulvalene class compound, in step (1)：Added in 25mL single port bottles
The 4.2mmol chloro-o-phthalic acids of 4,5- bis- and 2mL acetic anhydrides, is heated to reflux 2h, cooling, has solid precipitation, solid is filtered
Obtain white solid 0.79g, the chloro-phthalic anhydrides of as 4,5- bis-；In step (2)：Added in 100mL single port bottles
The 3.6mmol chloro-phthalic anhydrides of 4,5- bis-, 5.4mmol cyclohexylamine or n-butylamine and 10mL propionic acid, protected in nitrogen
Under, 140 DEG C are heated to reflux 3h, are evaporated under reduced pressure and remove propionic acid, and it is chloro- 2- cyclohexyl iso-indoles -1 of 5,6- bis- that column chromatography, which obtains product,
3- diketone or the chloro- 2- normal-butyls iso-indoles -1,3- diketone of 5,6- bis-.
The synthetic method of above-mentioned tetrathiafulvalene class compound, in step (3)：Added in 50mL there-necked flasks
6.56mmol NaH and 5mL dry DMFs, are stirred under nitrogen protection, add 6.56mmol benzyl mercaptans, until after solution clarification
Add the 2.85mmol chloro- 2- cyclohexyl iso-indoles -1,3- diketone of 5,6- bis- or the chloro- 2- normal-butyls iso-indoles -1,3- of 5,6- bis-
Diketone, it is stirred overnight, TLC display reactions are complete, and reaction solution is poured into water, there is solid precipitation, by solid filtering CH2Cl2/
CH3OH is recrystallized, obtain product be 5,6- dibenzyls methyl mercapto -2- cyclohexyl iso-indoles -1,3- diketone or 5,6- dibenzyl methyl mercapto -
2- normal-butyl iso-indoles -1,3- diketone.
The synthetic method of above-mentioned tetrathiafulvalene class compound, in step (4)：Added in 100mL single port bottles
1.7mmol 5,6- dibenzyl methyl mercapto -2- cyclohexyl iso-indoles -1,3- diketone or the different Yin of 5,6- dibenzyl methyl mercapto -2- normal-butyls
Diindyl -1,3- diketone, 13.5mmol AlCl3With 40mL dry toluenes, the lower stirring at normal temperature 2h of nitrogen protection；Add 3.38mmol carbonyls
Base diimidazole, it is complete to be heated to 100 DEG C of reaction 10h, TLC display reactions；Be spin-dried for reaction solution, dissolved with dichloromethane, then with steam
Distilled water and saturation NaCl solution are respectively washed three times, anhydrous Na2SO4Dry, filter, solvent is removed in rotation, and pillar layer separation obtains product and is
Synthesize 6- cyclohexyl -5H- [1,3] double sulphur [4,5-f] iso-indoles -2,5,7 (6H)-triketone or 6- normal-butyls -5H- [1,3] double sulphur
[4,5-f] iso-indoles -2,5,7 (6H)-triketone.
The synthetic method of above-mentioned tetrathiafulvalene class compound, in step (5)：Under nitrogen protection, in 50mL single port bottles
Middle addition 0.25mmol 6- cyclohexyl -5H- [1,3] double sulphur [4,5-f] iso-indoles -2,5,7 (6H)-triketone or 6- normal-butyls -
5H- [1,3] double sulphur [4,5-f] iso-indoles -2,5,7 (6H)-triketones, 6mL dry toluenes and 3mL triethyl phosphites, is heated to
130 DEG C of backflow 12h, cooling, there is red solid precipitation, filter 6,6 '-dicyclohexyl -5H, 5 ' H- [2,2 '-bis- [1,3] two sulphur
[4,5-f] different sub- indyl] -5,5 ', 7,7 ' (6H, 6H ') tetrone or 6,6 '-di-n-butyl -5H, 5 ' H- [2,2 '-bis- [1,3]
The different sub- indyl of two sulphur [4,5-f]] -5,5 ', 7,7 ' (6H, 6H ') tetrone.
The synthetic method of tetrathiafulvalene class compound, comprises the following steps：
(1) 5,6- dichloro neighbour's pyrazinedicarboxylicacids are synthesized；
(2) 2,3- dichloro neighbour's pyrazinedicarboxylicacid acid anhydrides are synthesized；
(3) chloro- 6- cyclohexyl -5H- pyrroles [3,4-b] pyrazine -5,7 (the 6H)-diketone of 2,3- bis- or bis- chloro- 6- of 2,3- are synthesized
Normal-butyl -5H- pyrroles [3,4-b] pyrazine -5,7 (6H)-diketone；
(4) sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5,7 (the 6H)-triketones of 6- cyclohexyl -5H- [1,3] two or 6- are synthesized
Normal-butyl -5H- [1,3] two sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5,7 (6H)-triketone；
(5) 6,6 '-dicyclohexyl -5H, 5 ' H- [sub- pyrazine of 2,2 '-bis- [1,3] two sulphur [4,5-b] pyrroles [3,4-e] is synthesized
Base] -5,5 ' 7,7 ' (6H, 6 ' H)-tetrones or 6,6 '-di-n-butyl -5H, 5 ' H- [2,2 '-bis- [1,3] two sulphur [4,5-b] pyrroles
[3,4-e] sub- pyrazinyl] -5,5 ' 7,7 ' (6H, 6 ' H)-tetrones.
The synthetic method of above-mentioned tetrathiafulvalene class compound, in step (1)：160ml is added in 500ml there-necked flasks
Distilled water, it is heated to seething with excitement, adds 10mmol 2,3- dichloro-quinoxalines, then 67mmol KMnO are added portionwise4, keep 95 DEG C of left sides
Right reaction 8h, is filtered off except MnO2, by MnO2Boiled, refiltered again with 50ml distilled water, is repeated 3 times, collect filtrate, added
6.6ml concentrated hydrochloric acids, filtrate is evaporated, and is fully dried；Again with acetone extract three times, merge acetone, be spin-dried for khaki solid i.e.
For 5,6- dichloro neighbour's pyrazinedicarboxylicacids；In step (2)：13mmol thionyl chlorides and 3mmol 5,6- are added in 25ml single port bottles
Dichloro neighbour's pyrazinedicarboxylicacid, 3h is heated to reflux, vacuum rotation removes thionyl chloride, adds 3ml dichloromethane, then is spin-dried for, so repeatedly
Three times, solid is drying to obtain 2,3- dichloro neighbour's pyrazinedicarboxylicacid acid anhydrides；In step (3)：Under nitrogen protection, in 25ml single port bottles
Add 2.8mmol 2,3- dichloro neighbour's pyrazinedicarboxylicacids acid anhydride, 4.8mmol amine hydrochlorates and 5ml acetic anhydride, in 120 DEG C of reactions
1.5h, TLC display reaction are complete, and reaction solution is poured into water, and has solid precipitation, filter, solid pillar layer separation is obtained into white production
Thing be chloro- 6- cyclohexyl -5H- pyrroles [3,4-b] pyrazine -5,7 (the 6H)-diketone of 2,3- bis- or the chloro- 6- normal-butyls of 2,3- bis- -
5H- pyrroles [3,4-b] pyrazine -5,7 (6H)-diketone.
The synthetic method of above-mentioned tetrathiafulvalene class compound, in step (4)：2mmol2 is added in 100ml single port bottles,
Chloro- 6- cyclohexyl -5H- pyrroles [3,4-b] pyrazine -5,7 (the 6H)-diketone of 3- bis- or the chloro- 6- normal-butyls -5H- pyrroles of 2,3- bis- [3,
4-b] pyrazine -5,7 (6H)-diketone, 8mmol thiocarbamides and 30ml absolute ethyl alcohols, 2.5h is heated to reflux, is spin-dried for ethanol, adds 40ml
3mol/L NaOH solution, 2h is stirred at room temperature, adds watery hydrochloric acid and adjust pH to have solid precipitation to acidity, filter to obtain yellow solid；Will
Yellow solid is put into 50ml there-necked flasks, is added the anhydrous THF dissolvings of 30ml, under nitrogen protection, is added 1.3 times of solid masses
Triphosgene, be stirred overnight；Solvent is spin-dried for, dissolved with dichloromethane, distilled water and saturation NaCl solution wash twice, anhydrous
Na2SO4Dry, filter, be spin-dried for solvent, pillar layer separation obtains product.
The synthetic method of above-mentioned tetrathiafulvalene class compound, in step (5)：Added in 50ml single port bottles
Sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5,7 (the 6H)-triketones of 0.4mmol6- cyclohexyl -5H- [1,3] two or 6- normal-butyls -
5H- [1,3] two sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5,7 (6H)-triketones, 2ml triethyl phosphites, in 95 DEG C of heating
4h, cooling, there is red solid precipitation, filters, obtains 6,6 '-dicyclohexyl -5H, 5 ' H- [2,2 '-bis- [1,3] two sulphur [4,5-b] pyrroles
Cough up [3,4-e] sub- pyrazinyl] -5,5 ' 7,7 ' (6H, 6 ' H)-tetrones or 6,6 '-di-n-butyl -5H, 5 ' H- [2,2 '-bis- [1,3]
Two sulphur [4,5-b] pyrroles [3,4-e] sub- pyrazinyl] -5,5 ' 7,7 ' (6H, 6 ' H)-tetrones.
Beneficial effects of the present invention are as follows：
Synthetic route is easy and effective, and for raw material to be commercialized cheap product, synthesis cost is low, and products collection efficiency is high, and the method is also
With universality, it can be used for the synthesis of other classes TTF analog derivatives.
5,6- bis- chloro- 2- cyclohexyl iso-indoles -1,3- diketone are linear big pi-conjugated molecule, have rigid planar structure,
It is expected to turn into high mobility OFET materials.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1-1 compounds 137a synthetic route (137b synthetic route is similar to 137a)；
Fig. 1-2 compounds 138a synthetic route (138b synthetic route is similar to 138a)；
Fig. 2-1 to Fig. 2-4 is compound 137a scanning electron microscope (SEM) photograph；
Fig. 3-1 to Fig. 3-3 is compound 137a atomic force microscopy diagram；
Fig. 4 is compound 137a in drain-source voltage VDSTransport property during=- 100V.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
First, tetrathiafulvalene class compound 137a synthetic method (137b synthetic method is similar with 137a)
The present embodiment tetrathiafulvalene class compound 137a synthetic route is as Figure 1-1：It is diacid with dichlorobenzene
Compound 139 heats for raw material in acetic acid anhydride solution obtains anhydride compound 140,140 and cyclohexylamine reaction generation dicarbapentaborane acyl
Group with imine moiety 141a, then carried out substitution reaction with 141a in DMF solution with benzyl mercaptan and obtain compound 142a, then by carbonyl
Diimidazole nucleophilic displacement of fluorine generates important object precursor 143a.Finally in the presence of triethyl phosphite, returned in toluene solution
Stream obtains target compound 137a.Specifically comprise the following steps：
(1) synthesis of compound 140
The chloro-o-phthalic acids 139 (1.0g, 4.2mmol) of 4,5- bis-, 2ml acetic anhydrides, heating are added in 25ml single port bottles
Flow back 2h, cooling, has solid precipitation, solid is filtered to obtain into white solid 0.79g, yield 86%.m.p.186.9-188.2℃.
(2) compound 141a-b synthesis
The chloro-phthalic anhydrides of 4,5- bis- (0.78g, 3.6mmol), cyclohexylamine or normal-butyl are added in 100ml single port bottles
Amine (5.4mmol), 10ml propionic acid, under nitrogen protection, 140 DEG C are heated to reflux 3h.It is evaporated under reduced pressure and removes propionic acid, column chromatography must produces
Thing.
5,6- bis- chloro- 2- cyclohexyl iso-indoles -1,3- diketone (141a), yield 90%.1H NMR(CDCl3,600MHz)δ:
7.89 (d, J=3.6Hz, 2H), 4.09 (tt, J=12.6,3.6Hz, 1H), 2.17 (qd, J=12.6,3.6Hz, 2H), 1.87
(d, J=13.2Hz, 2H), 1.71 (t, J=12.0Hz, 3H), 1.37 (qd, J=13.2,6.6Hz, 2H), 1.27 (ddt, J=
16.2,13.2,6.6Hz,1H).
5,6- bis- chloro- 2- normal-butyls iso-indoles -1,3- diketone (141b), yield 88%.1H NMR(CDCl3,600MHz)δ:
7.91 (d, J=3.6Hz, 2H), 3.68 (t, J=7.2Hz, 2H), 1.69-1.61 (m, 2H), 1.39-1.31 (m, 2H), 0.94
(t, J=7.2Hz, 3H)
(3) compound 142a-b synthesis
NaH (0.157g, 6.56mmol) and 5ml dry DMFs are added in 50ml there-necked flasks, is stirred under nitrogen protection, then
Benzyl mercaptan (0.81g, 6.56mmol) is added, until 141a (2.85mmol) or 141b (2.85mmol) is added after solution clarification,
It is stirred overnight, TLC display reactions are complete, and reaction solution is poured into water, there is solid precipitation, by solid filtering CH2Cl2/CH3OH
Recrystallization, obtains product.
5,6- dibenzyl methyl mercapto -2- cyclohexyl iso-indoles -1,3- diketone (142a), yield 70%.1H NMR(CDCl3,
600MHz)δ:7.60 (s, 2H), 7.36 (d, J=7.2Hz, 4H), 7.32 (t, J=7.8Hz, 4H), 7.28 (d, J=7.2Hz,
2H), 4.24 (s, 4H), 4.04 (ddd, J=12.0,7.8,3.6Hz, 1H), 2.15 (tt, J=12.6,6.6Hz, 2H), 1.85
(d, J=13.2Hz, 2H), 1.70 (d, J=9.0Hz, 3H), 1.35 (dd, J=26.4,13.2Hz, 2H), 1.29 (s, 1H)
5,6- dibenzyl methyl mercapto -2- normal-butyl iso-indoles -1,3- diketone (142b), yield 67%.1H NMR(CDCl3,
600MHz)δ:7.62 (s, 2H), 7.36 (d, J=7.3Hz, 4H), 7.32 (t, J=7.4Hz, 4H), 7.28 (d, J=7.2Hz,
2H), 4.24 (s, 4H), 3.63 (t, J=7.3Hz, 2H), 1.66-1.59 (m, 2H), 1.34 (dd, J=15.1,7.5Hz, 2H),
0.94 (t, J=7.4Hz, 3H)
(4) compound 143a-b synthesis
Material 142a (1.7mmol) or 142b (1.7mmol), AlCl are added in 100ml single port bottles3(1.8g,
13.5mmol) and 40ml dry toluenes, nitrogen protect lower stirring at normal temperature 2h.Carbonyl dimidazoles (0.54g, 3.38mmol) are added,
It is complete to be heated to 100 DEG C of reaction 10h, TLC display reactions.Be spin-dried for reaction solution, dissolved with q. s. methylene chloride, then with distilled water and
Saturation NaCl solution is respectively washed three times, anhydrous Na2SO4Dry, filter, solvent is removed in rotation, and pillar layer separation obtains product.
6- cyclohexyl -5H- [1,3] double sulphur [4,5-f] iso-indoles -2,5,7 (6H)-triketones (143a), yield 28%.
m.p.176.6-180.1℃；1H NMR(CDCl3,600MHz)δ:7.95-7.91(m,2H),4.15-4.07(m,1H),2.19
(qd, J=12.6,3.0Hz, 2H), 1.88 (d, J=13.2Hz, 2H), 1.77-1.67 (m, 3H), 1.37 (q, J=13.2Hz,
2H),1.32-1.22(m,1H).IR(KBr,cm-1):2939,1725 (ν C=O), 1695,1672,1599,1391,1367,
1089,890,859,744,597.
6- normal-butyls -5H- [1,3] double sulphur [4,5-f] iso-indoles -2,5,7 (6H)-triketones (143b), yield 30%.
m.p.184.0-186.2℃；1H NMR(CDCl3,600MHz)δ:7.96 (s, 2H), 3.70 (t, J=7.2Hz, 2H), 1.66
(dd, J=15.0,7.8Hz, 2H), 1.37 (dd, J=15.0,7.8Hz, 2H), 0.95 (t, J=7.2Hz, 3H) .IR (KBr,
cm-1):2947,2864,2354,2327,1731(νC=O),1694,1662,1602,1429,1169,1061,923,861,
740.
(5) compound 137a-b synthesis
Under nitrogen protection, 143a (0.25mmol) or 143b (0.25mmol), 6ml dry toluenes are added in 50ml single port bottles
With 3ml triethyl phosphites, 130 DEG C of backflow 12h are heated to.Cooling, there is red solid precipitation, filters to obtain required object.
6,6 '-dicyclohexyl -5H, 5 ' H- [2,2 '-bis- the different sub- indyls of [1,3] two sulphur [4,5-f]] -5,5 ', 7,7 '
(6H, 6H ') tetrone (137a), yield 70%.330 DEG C of m.p ＞；IR(KBr,cm-1):3082,2944,2853,1764(νC=C),
1697(νC=O),1590,1391,1093,1020,764,743,630；Elemental analysis calcd. (%) for
C30H26N2O4S4:C,59.38；H,4.32；N,4.62；S,21.14；O,10.55；Found:C,59.33；H,4.12；N,4.66；
S,20.94；O,10.95.
6,6 '-di-n-butyl -5H, 5 ' H- [2,2 '-bis- the different sub- indyls of [1,3] two sulphur [4,5-f]] -5,5 ', 7,7 '
(6H, 6H ') tetrone (HY0422) 137b, yield 75%.330 DEG C of m.p ＞；IR(KBr,cm-1):3077,2954,2870,1767
(νC=C),1705(νC=O),1591,1395,1057,914,742,595；Elemental analysis calcd. (%) for
C26H22N2O4S4:C,56.29；H,4.00；N,5.05；S,23.12；O,11.54；Found:C,56.43；H,4.11；N,5.14；
S,23.01；O,11.31.
2nd, compound 137a property representation
Preliminary observation has been carried out to compound 137a appearance shape, then its mobility and on-off ratio surveyed
It is fixed.
2.1 compound 137a scanning electron microscope (SEM) photograph
At 300 DEG C, observed by SEM (scanning electron microscope, SEM)
Compound 137a particle morphology is as shown in Fig. 2-1 to Fig. 2-4.The particle diameter of its particle is about in 500-1000nm or so, shape
Rule【The particle diameter of 137b particle is about in 600-1100nm】.
2.2 compound 137a atomic force microscopy diagram
The surface microscopic topographic (as shown in Fig. 3-1 to Fig. 3-3) of material can be observed by AFM, while
The height of sample particle can be measured, by calculating, its height is about 16nm【The height of 137b particle is about
20nm】。
2.3 compound 137a transport property
The transport property of device based on compound 137a is as shown in figure 4, its highest mobility is 0.11cm2/ Vs,
On-off ratio is 103, while threshold voltage is -38V【The transport property of 137b device：Highest mobility is 0.10cm2/ Vs,
On-off ratio is 103, while threshold voltage is -37V】.Because source and drain electrode current increases with the increase of negative-gate voltage, so
This is a kind of OFET materials of p-type.
3rd, tetrathiafulvalene class compound 138a synthetic method (138b synthetic method is similar with 138a) the present embodiment
Tetrathiafulvalene class compound 138a synthetic route is as shown in Figure 1-2：It is raw material with o-phenylenediamine 131, by dehydrating condensation,
Chloro, oxidation reaction obtain dichloro- pyrazine diacid compound 144, and then dehydration forms acid anhydrides 145, chemical combination in thionyl chloride
Thing 145 in acetic anhydride with cyclohexylamine 120 DEG C reaction generation dicarbonyl imides compound 146a, 146a pass through it is anti-with thiocarbamide
Ying Hou, compound 147a is obtained under NaOH and watery hydrochloric acid effect successively, then carry out reaction in THF with triphosgene and form chemical combination
Thing 148a, finally obtain target compound 138a under triethyl phosphite effect.Specifically comprise the following steps：
(1) synthesis of 5,6- dichloros neighbour pyrazinedicarboxylicacid 144
160ml distilled water is added in 500ml there-necked flasks, is heated to seething with excitement, 2,3- of addition dichloro-quinoxalines 133 (2.0g,
10mmol), then it is added portionwise KMnO4(10.6g, 67mmol), 95 DEG C or so reaction 8h are kept, are filtered off except MnO2, by MnO2With
50ml distilled water boils again, refilters, and is repeated 3 times, and collects filtrate, adds 6.6ml concentrated hydrochloric acids, filtrate is evaporated, fully dry
It is dry.Again with acetone extract three times, merge acetone, be spin-dried for obtaining khaki solid 0.7g, yield 41%, direct plunge into next step.
(2) synthesis of 2,3- dichloros neighbour pyrazinedicarboxylicacid acid anhydride 145
1ml thionyl chlorides (13mmol) are added in 25ml single port bottles) and 5,6- dichloro neighbours pyrazinedicarboxylicacid 144 (0.5g,
3mmol), 3h is heated to reflux, vacuum rotation removes thionyl chloride, adds 3ml dichloromethane, then is spin-dried for, so repeatedly for three times, by solid
Dry, direct plunge into next step.
(3) compound 146a-b synthesis
Under nitrogen protection, 2,3- dichloro neighbour's pyrazinedicarboxylicacid acid anhydrides 145 (2.8mmol), cyclohexylamine are added in 25ml single port bottles
Hydrochloride (4.8mmol) or n-butylamine hydrochloride (4.8mmol), and 5ml acetic anhydride, 1.5h is reacted at 120 DEG C, TLC is shown
Reaction is complete, and reaction solution is poured into water, and has solid precipitation, filters, solid pillar layer separation is obtained into white product.
2,3- bis- chloro- 6- cyclohexyl -5H- pyrroles [3,4-b] pyrazine -5,7 (6H)-diketone 146a, yield 67%.1H NMR
(CDCl3,600MHz)δ:4.23 (tt, J=12.6,3.6Hz, 1H), 2.20 (qd, J=12.6,3.6Hz, 2H), 1.90 (d, J
=13.8Hz, 2H), 1.77 (d, J=11.4Hz, 2H), 1.72 (d, J=12.6Hz, 1H), 1.39 (dt, J=16.2,
10.2Hz,2H),1.34-1.23(m,1H).
2,3- bis- chloro- 6- normal-butyls -5H- pyrroles [3,4-b] pyrazine -5,7 (6H)-diketone 146b, yield 70%.1H NMR
(CDCl3,600MHz)δ:3.81 (t, J=7.2Hz, 2H), 1.73-1.66 (m, 2H), 1.42-1.33 (m, 2H), 0.96 (t, J
=7.2Hz, 3H)
(4) compound 148a-b synthesis
Material 146a (or 146b) (2mmol), thiocarbamide (8mmol) and 30ml absolute ethyl alcohols are added in 100ml single port bottles, is added
Heat backflow 2.5h, is spin-dried for ethanol, adds 40ml 3mol/L NaOH solution, 2h is stirred at room temperature, and adds watery hydrochloric acid and adjusts pH to acid
Property, there is solid precipitation, filter to obtain yellow solid 147a (147b).Solid is put into 50ml there-necked flasks, adds the anhydrous THF of 30ml
Dissolving, under nitrogen protection, triphosgene (for 1.3 times of solid) is added, is stirred overnight.Solvent is spin-dried for, it is molten with dichloromethane
Solution, distilled water and saturation NaCl solution wash twice, anhydrous Na2SO4Dry, filter, be spin-dried for solvent, pillar layer separation obtains product.
6- cyclohexyl -5H- [1,3] two sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5,7 (6H)-triketone 148a, yield
25%.1H NMR(CDCl3,600MHz)δ:4.29-4.22 (m, 1H), 2.22 (qd, J=12.6,3.6Hz, 2H), 1.91 (d, J
=13.8Hz, 2H), 1.79 (d, J=11.4Hz, 2H), 1.73 (d, J=11.4Hz, 1H), 1.44-1.34 (m, 2H), 1.34-
1.27(m,1H)；EI-MS:Calcd.for C13H11N3O3S2:321,found:321([M]+)；IR(KBr,cm-1):2940,
2853,1780(νC=O),1727,1392,1369,1149,1089。
6- normal-butyls -5H- [1,3] two sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5,7 (6H)-triketone 148b, yield
20%.1H NMR(CDCl3,600MHz)δ:3.82 (t, J=7.2Hz, 2H), 1.72 (dd, J=8.4,7.2Hz, 2H), 1.39
(dd, J=15.0,7.2Hz, 2H), 0.97 (td, J=7.2,1.8Hz, 3H)；ESI-MS:Calcd.for C11H9N3O3S2:
295,found:296([M+H]+)；IR(KBr,cm-1):2943,2850,1778(νC=O),1690,1600,1429,1081,
920,852,730。
(5) compound 138a-b synthesis
Material 148a (or 148b) (0.4mmol) is added in 50ml single port bottles, 2ml triethyl phosphites, is added at 95 DEG C
Hot 4h, cooling, there is red solid precipitation, filters, obtains target compound.
6,6 '-dicyclohexyl -5H, 5 ' H- [the sub- pyrazinyl of 2,2 '-bis- [1,3] two sulphur [4,5-b] pyrroles [3,4-e]] -5,
5 ' 7,7 ' (6H, 6 ' H)-tetrone 138a, yield 50%.330 DEG C of m.p ＞；IR(KBr,cm-1):2918,2848,1780(νC=C),
1726(νC=O),1495,1391,1366,1293,1206,1096,740,595；Elemental analysis calcd. (%)
for C26H22N6O4S4:C,51.13；H,3.63；N,13.76；S,21.00；O,10.48；Found:C,51.31；H,3.51；N,
13.83；S,21.21；O,10.14.
6,6 '-di-n-butyl -5H, 5 ' H- [the sub- pyrazinyl of 2,2 '-bis- [1,3] two sulphur [4,5-b] pyrroles [3,4-e]] -5,
5 ' 7,7 ' (6H, 6 ' H)-tetrone 138b, yield 52%.330 DEG C of m.p ＞；IR(KBr,cm-1):2958,2930,2865,1788
(νC=C),1726(νC=O),1403,1210,1157,1071,764,741,599；Elemental analysis calcd.
(%) for C22H18N6O4S4:C,47.30；H,3.25；N,15.04；S,22.96；O,11.46；Found:C,47.41；H,
3.48；N,15.13；S,22.79；O,11.19.
4th, 138a and 138b property representation (test condition and method are identical with 137a)
The particle diameter of 138a particle is about in 700-1000nm, the height about 18nm of 138a particle；138a device
Transport property：Highest mobility is 0.12cm2/ Vs, on-off ratio 103, while threshold voltage is -39V.138b particle
Particle diameter about in 800-1000nm, the height about 20nm of 138b particle；The transport property of 138b device：Highest migrates
Rate is 0.10cm2/ Vs, on-off ratio 103, while threshold voltage is -36V.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (1)
1. the synthetic method of tetrathiafulvalene class compound, it is characterised in that compound of the synthesis as shown in formula (I)：
X is N, and Y is cyclohexyl or normal-butyl；
Specifically comprise the following steps：
(1) 5,6- dichloro neighbour's pyrazinedicarboxylicacids are synthesized；
160mL distilled water is added in 500mL there-necked flasks, is heated to seething with excitement, adds 10mmol 2,3- dichloro-quinoxalines, then divide
Criticize and add 67mmol KMnO4, 95 DEG C or so reaction 8h are kept, are filtered off except MnO2, by MnO2Boiled again with 50mL distilled water,
Refilter, be repeated 3 times, collect filtrate, add 6.6mL concentrated hydrochloric acids, filtrate is evaporated, fully dry；Again with acetone extract three times,
Merge acetone, be spin-dried for khaki solid is 5,6- dichloro neighbour's pyrazinedicarboxylicacids；
(2) 2,3- dichloro neighbour's pyrazinedicarboxylicacid acid anhydrides are synthesized；
13mmol thionyl chlorides and 3mmol 5,6- dichloro neighbour's pyrazinedicarboxylicacid are added in 25mL single port bottles, is heated to reflux 3h, very
Thionyl chloride is removed in sky rotation, adds 3mL dichloromethane, then is spin-dried for, and so repeatedly for three times, solid is drying to obtain into 2,3- dichloro neighbour's pyrroles
Piperazine dicarboxylic acid anhydride；
(3) chloro- 6- cyclohexyl -5H- pyrroles [3,4-b] pyrazine -5,7 (the 6H)-diketone of 2,3- bis- or the positive fourths of chloro- 6- of 2,3- bis- are synthesized
Base -5H- pyrroles [3,4-b] pyrazine -5,7 (6H)-diketone；
Under nitrogen protection, 2.8mmol 2,3- dichloro neighbour's pyrazinedicarboxylicacids acid anhydride, 4.8mmol amine hydrochlorates are added in 25mL single port bottles
With 5mL acetic anhydride, 1.5h is reacted at 120 DEG C, TLC display reactions are complete, and reaction solution is poured into water, and has solid precipitation, filter, will
It is chloro- 6- cyclohexyl -5H- pyrroles [3,4-b] pyrazine -5,7 (the 6H)-diketone of 2,3- bis- that solid pillar layer separation, which obtains white product,
Or chloro- 6- normal-butyls -5H- pyrroles [3,4-b] pyrazine -5,7 (the 6H)-diketone of 2,3- bis-；
(4) sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5,7 (the 6H)-triketones of 6- cyclohexyl -5H- [1,3] two or the positive fourths of 6- are synthesized
Base -5H- [1,3] two sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5,7 (6H)-triketone；
Added in 100mL single port bottles chloro- 6- cyclohexyl -5H- pyrroles [3,4-b] pyrazine -5,7 (the 6H)-diketone of 2mmol2,3- bis- or
2,3- bis- chloro- 6- normal-butyls -5H- pyrroles [3,4-b] pyrazine -5,7 (6H)-diketone, 8mmol thiocarbamides and 30mL absolute ethyl alcohols, add
Heat backflow 2.5h, is spin-dried for ethanol, adds 40mL 3mol/L NaOH solution, 2h is stirred at room temperature, and adds watery hydrochloric acid and adjusts pH to acid
Property, there is solid precipitation, filter to obtain yellow solid；Yellow solid is put into 50mL there-necked flasks, adds the anhydrous THF dissolvings of 30mL,
Under nitrogen protection, 1.3 times of triphosgene of solid masses is added, is stirred overnight；Solvent is spin-dried for, dissolved with dichloromethane,
Distilled water and saturation NaCl solution wash twice, anhydrous Na2SO4Dry, filter, be spin-dried for solvent, pillar layer separation obtains product；
(5) synthesize 6,6 '-dicyclohexyl -5H, 5 ' H- [the sub- pyrazinyl of 2,2 '-bis- [1,3] two sulphur [4,5-b] pyrroles [3,4-e]] -
5,5 ' 7,7 ' (6H, 6 ' H)-tetrones or 6,6 '-di-n-butyl -5H, 5 ' H- [2,2 '-bis- [1,3] two sulphur [4,5-b] pyrroles [3,4-
E] sub- pyrazinyl] -5,5 ' 7,7 ' (6H, 6 ' H)-tetrones；
Sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5 of 0.4mmol6- cyclohexyl -5H- [1,3] two are added in 50mL single port bottles,
7 (6H)-triketones or 6- normal-butyls -5H- [1,3] two sulphur [4,5-b] pyrroles [3,4-e] pyrazine -2,5,7 (6H)-triketones, 2mL are sub-
Triethyl phosphate, 4h are heated at 95 DEG C, cooling, there is red solid precipitation, filters, obtains 6,6 '-dicyclohexyl -5H, 5 ' H- [2,
The sub- pyrazinyl of 2 '-bis- [1,3] two sulphur [4,5-b] pyrroles [3,4-e]] -5,5 ' 7,7 ' (6H, 6 ' H)-tetrones or 6,6 '-two positive fourths
Base -5H, 5 ' H- [the sub- pyrazinyl of 2,2 '-bis- [1,3] two sulphur [4,5-b] pyrroles [3,4-e]] -5,5 ' 7,7 ' (6H, 6 ' H)-tetrones.
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