CN104370937B - The synthetic method and purposes of a kind of containing oxygen group elements and five condensed ring conjugated molecules and its derivative - Google Patents
The synthetic method and purposes of a kind of containing oxygen group elements and five condensed ring conjugated molecules and its derivative Download PDFInfo
- Publication number
- CN104370937B CN104370937B CN201310362715.7A CN201310362715A CN104370937B CN 104370937 B CN104370937 B CN 104370937B CN 201310362715 A CN201310362715 A CN 201310362715A CN 104370937 B CN104370937 B CN 104370937B
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- CN
- China
- Prior art keywords
- thiophene
- sulfidomethyls
- furans
- added
- selenophen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 241001597008 Nomeidae Species 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 210
- 229930192474 thiophene Natural products 0.000 claims description 108
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 102
- -1 methoxyl group Chemical group 0.000 claims description 80
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 70
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 43
- 150000002240 furans Chemical class 0.000 claims description 38
- 238000010992 reflux Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 22
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000284 extract Substances 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- 238000007792 addition Methods 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 229960000583 acetic acid Drugs 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 11
- 230000000630 rising effect Effects 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 230000004224 protection Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
- WAQFYSJKIRRXLP-UHFFFAOYSA-N 2,4-dibromothiophene Chemical compound BrC1=CSC(Br)=C1 WAQFYSJKIRRXLP-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 claims description 3
- QZVHYFUVMQIGGM-UHFFFAOYSA-N 2-Hexylthiophene Chemical class CCCCCCC1=CC=CS1 QZVHYFUVMQIGGM-UHFFFAOYSA-N 0.000 claims description 3
- MNDZHERKKXUTOE-UHFFFAOYSA-N 2-butylthiophene Chemical class CCCCC1=CC=CS1 MNDZHERKKXUTOE-UHFFFAOYSA-N 0.000 claims description 3
- GOTHKCARNFTUSW-UHFFFAOYSA-N 2-decylthiophene Chemical class CCCCCCCCCCC1=CC=CS1 GOTHKCARNFTUSW-UHFFFAOYSA-N 0.000 claims description 3
- JCCCMAAJYSNBPR-UHFFFAOYSA-N 2-ethylthiophene Chemical class CCC1=CC=CS1 JCCCMAAJYSNBPR-UHFFFAOYSA-N 0.000 claims description 3
- GIFWAJGKWIDXMY-UHFFFAOYSA-N 2-octylthiophene Chemical class CCCCCCCCC1=CC=CS1 GIFWAJGKWIDXMY-UHFFFAOYSA-N 0.000 claims description 3
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- NDJKXXJCMXVBJW-UHFFFAOYSA-N Heptadecane Natural products CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 3
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- OTIVLGJBKUFOEX-UHFFFAOYSA-N n-tetradecoxyaniline Chemical compound CCCCCCCCCCCCCCONC1=CC=CC=C1 OTIVLGJBKUFOEX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229940038384 octadecane Drugs 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- DFLKSYRDWXWBBL-UHFFFAOYSA-N thiophen-3-ylmethanethiol Chemical compound SCC=1C=CSC=1 DFLKSYRDWXWBBL-UHFFFAOYSA-N 0.000 claims description 3
- 150000003577 thiophenes Chemical class 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- ZBZNCJRCPCNHQL-UHFFFAOYSA-N 2,4-dibromofuran Chemical class BrC1=COC(Br)=C1 ZBZNCJRCPCNHQL-UHFFFAOYSA-N 0.000 claims description 2
- GNOLAERWALKOOH-UHFFFAOYSA-N 2,4-dibromoselenophene Chemical compound BrC1=C[se]C(Br)=C1 GNOLAERWALKOOH-UHFFFAOYSA-N 0.000 claims description 2
- FGGZOCMVJAJPMH-UHFFFAOYSA-N 2-heptylthiophene Chemical compound CCCCCCCC1=CC=CS1 FGGZOCMVJAJPMH-UHFFFAOYSA-N 0.000 claims description 2
- BPNQMPWZDNUCPT-UHFFFAOYSA-N 2-octadecylthiophene Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CS1 BPNQMPWZDNUCPT-UHFFFAOYSA-N 0.000 claims description 2
- KACFQILXXNJKSZ-UHFFFAOYSA-N OBO.C=1C=COC=1 Chemical class OBO.C=1C=COC=1 KACFQILXXNJKSZ-UHFFFAOYSA-N 0.000 claims description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 229910052798 chalcogen Inorganic materials 0.000 claims 1
- 150000001787 chalcogens Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 claims 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims 1
- 235000019345 sodium thiosulphate Nutrition 0.000 claims 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 7
- 230000005669 field effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OBHWOLDGXCOBAK-UHFFFAOYSA-N [F].CS(O)(=O)=O Chemical compound [F].CS(O)(=O)=O OBHWOLDGXCOBAK-UHFFFAOYSA-N 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- NJPMFDNZCLKTHE-UHFFFAOYSA-N 2-dodecylthiophene Chemical class CCCCCCCCCCCCC1=CC=CS1 NJPMFDNZCLKTHE-UHFFFAOYSA-N 0.000 description 2
- CHXZRHMQQRUVHF-UHFFFAOYSA-N 2-hex-5-en-1,3-diynyl-5-prop-1-ynylthiophene Chemical compound CC#CC1=CC=C(C#CC#CC=C)S1 CHXZRHMQQRUVHF-UHFFFAOYSA-N 0.000 description 2
- KBZSJFOSBGKXIY-UHFFFAOYSA-N 4-bromo-2-hexylthiophene Chemical class CCCCCCC1=CC(Br)=CS1 KBZSJFOSBGKXIY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UZILCZKGXMQEQR-UHFFFAOYSA-N decyl-Benzene Chemical compound CCCCCCCCCCC1=CC=CC=C1 UZILCZKGXMQEQR-UHFFFAOYSA-N 0.000 description 2
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 0 *(C=C1)c2c1[s]c-1c2*c2c-1[s]c1c2*C=C1 Chemical compound *(C=C1)c2c1[s]c-1c2*c2c-1[s]c1c2*C=C1 0.000 description 1
- RXEIUHSMORSJCK-UHFFFAOYSA-N 2-methylselenophene Chemical compound CC1=CC=C[se]1 RXEIUHSMORSJCK-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- QKUKRVOSJTZJDI-UHFFFAOYSA-N C(CCC)OCCCCCCOOOCCCCC Chemical compound C(CCC)OCCCCCCOOOCCCCC QKUKRVOSJTZJDI-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MEWQFMZMPMAMTG-UHFFFAOYSA-N [O].CCCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCCC MEWQFMZMPMAMTG-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QVJBJBWGSWLPQL-UHFFFAOYSA-N furan-3-ylmethanethiol Chemical class SCC=1C=COC=1 QVJBJBWGSWLPQL-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IIYFAKIEWZDVMP-UHFFFAOYSA-N linear paraffin C13 Natural products CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- GCZQHDFWKVMZOE-UHFFFAOYSA-N thiophen-2-ylmethanethiol Chemical compound SCC1=CC=CS1 GCZQHDFWKVMZOE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
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Abstract
The present invention relates to the preparation method and use of a kind of containing oxygen group elements and five condensed ring conjugated molecules and its derivative, wherein oxygen-containing race's element and five condensed ring conjugated molecule structures be：Described containing oxygen group elements and five condensed ring conjugated molecule derivant structures are：
Description
Technical field
The present invention relates to the synthetic method of a kind of containing oxygen group elements and five condensed ring conjugated molecules and its derivative, Yi Jihan
Oxygen group elements and five condensed ring conjugated molecules and its derivative purposes.
Background technology
Field-effect transistor was used widely as most important unit component in microelectronics, in 1986
(Tsumura, the A. such as Tsumura, A；Koezuka, H.；Ando, T.Appl.Phys.Lett, 1986,49,1210) report one
New field-effect transistor --- the organic field effect tube (OFET) of kind, subsequent organic field effect tube prepare work by its
The advantages that skill is simple, cost is low, in light weight and pliability is good and in smart card, electronic trademark, Electronic Paper, memory, sensing
Device and Active Matrix Display etc. are all many widely used to have obtained the numerous studies of numerous researchers.
In the organic semiconducting materials used in organic field effect tube, although pentacene good film-forming property, mobility are high,
But its stability is poor, visible region is absorbed by force, so as to limit its development in field of display.Chemistry institute of Chinese Academy of Sciences Liu Yun
Uncommon researcher, primary track this academician synthesized using thiophene as construction unit and five thiophene, its semiconducting behavior is preferable, with pentacene
Compared to there is higher stability, but its synthesis step is more complicated.The present invention is devised a kind of synthesis including simultaneously five thiophene
A variety of condensed ring conjugated molecules and its derivative containing oxygen group elements method.These condensed ring conjugated molecules are respectively provided with larger be total to
Yoke structure, higher carrier mobility, it is a kind of good organic semiconducting materials, can be applied to organic effect crystal
The donor material of pipe and organic solar batteries.
The content of the invention
In view of this, the invention discloses the synthesis of a kind of containing oxygen group elements and five condensed ring conjugated molecules and its derivative
Method, a series of this condensed ring conjugated molecule can use wet processing in ito glass or silicon chip, ceramic substrate surface on, through appropriate
Heating anneal processing, the transparent membrane of high-sequential, while big pi-conjugated structure can be formed, be advantageous to carrier transport.
Therefore, there can be important application value in the field such as OTFT and organic solar batteries.
To achieve these goals, the present invention has synthesized following compound：
A kind of containing oxygen group elements and five condensed ring conjugated molecules, its structure are as follows：
X is O, S, Se, and its counter structure is as follows：
A kind of containing oxygen group elements and five condensed ring conjugated molecule derivatives, its structure are as follows：
X is 0, S, Se, and its counter structure is as follows：
Wherein, R is to include：Alkyl, including methyl, ethyl, propyl group, isopropyl, butyl, amyl group, hexyl, heptyl, octyl group,
Nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl and ten
At least one of eight alkyl；Alkoxy, including methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan
Base, octyloxy, nonyl epoxide, decyloxy, hendecane epoxide, dodecyloxy, tridecane epoxide, tetradecyloxyaniline, pentadecane oxygen
At least one of base, hexadecane epoxide, heptadecane epoxide and octadecane epoxide；Aryl, including phenyl, naphthyl, tolyl, second
Base phenyl, propyl group phenyl, butyl phenyl, amyl group phenyl, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl benzene
Base, undecyl phenyl, dodecylphenyl, tridecyl phenyl, myristyl phenyl, pentadecylphenyl, cetyl
At least one in phenyl, heptadecyl phenyl and octadecylphenyl；Thienyl, including thiophene, 1,4-Dithiapentalene, 5- thiophene
Thiophene, 5- ethylthiophenes, 5- propyl group thiophene, 5- isopropyls thiophene, 5- butyl thiophenes, 5- amylic thiophenes, 5- hexyl thiophenes, 5- heptan
Base thiophene, 5- octyl thiophenes, 5- nonyls thiophene, 5- decylthiophenes, 5- undecyls thiophene, 5- dodecylthiophenes, 5- 13
Alkylthrophene, 5- myristyls thiophene, 5- pentadecyls thiophene, 5- cetyls thiophene, 5- heptadecyls thiophene, 5- octadecanes
At least one in base thiophene.
3rd, a kind of to prepare containing oxygen group elements and five condensed ring conjugated molecules methods, its reaction scheme is as follows：
Methods described comprises the following steps：
(1) at -78 DEG C, take 3- bromines furans or 3 bromo thiophene or 1 part of 3- bromines selenophen to be added in anhydrous THF, add dropwise
Enter 1 part of n-BuLi, moved on at room temperature after stirring 0.5~3h.1~2.0 part of dimethyl disulfide is added in said mixture,
10~24h is stirred, is quenched with saturated ammonium chloride, dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained 3- sulfidomethyls furans or 3- sulphur first
Base thiophene or 3- sulfidomethyl selenophens；
(2) at 0 DEG C, 3- sulfidomethyls furans or 3- sulfidomethyls thiophene or 1 part of 3- sulfidomethyls selenophen is taken to be added to dichloromethane
In alkane, 1 part of bromine will be added, stir 2.5~5.0h, add saturation NaHSO3Or hypo solution, extract organic
Mutually and drying is spin-dried for, and is crossed post and is obtained the bromo- 3- sulfidomethyls furans of 2- or the bromo- 3- sulfidomethyls thiophene of 2- or the bromo- 3- sulfidomethyls selenophens of 2-；
(3) the bromo- 3- sulfidomethyls furans of 2- or the bromo- 3- sulfidomethyls thiophene of 2- or the bromo- 3- sulfidomethyls selenophens 2.2~3.0 of 2- are taken
Part is added in THF, in N2Or Pd (the PPh of the lower addition 2~10% of Ar protections3)4, it is heated to reflux 24-48h.Screw out THF, extraction
Obtain organic phase and drying is spin-dried for, cross post and obtain 2,5- (2- (3- sulfidomethyls) furans) furans or 2,5- (2- (3- sulfidomethyls) thiophene)
Thiophene or 2,5- (2- (3- sulfidomethyls) selenophen) selenophen；
(4) 1 part of 2,5- (2- (3- sulfidomethyls) furans) furans or 2,5- (2- (3- sulfidomethyls) thiophene) thiophene or 2,5- are taken
(2- (3- sulfidomethyls) selenophen) selenophen is added in glacial acetic acid, and 25~40% H is slowly added in said mixture2O22.2~
4.0 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, 3~5 parts of trifluoromethanesulfonic acid is added in the mixture, in room temperature
24~36h of lower stirring, reaction product is poured into the mixed liquor of water and pyridine and is heated to reflux 0.5~1.0h, is filtered and is used dichloro
Methane wash product, distil target product containing oxygen group elements and five condensed ring conjugated molecules.
It should be noted that the ratio of the water and pyridine is 8: 1.
A kind of to prepare containing oxygen group elements and five condensed ring conjugated molecule derivatives synthetic methods, its reaction scheme is as follows：
Wherein, comprise the following steps：
(1)N2Or under Ar protections, 2,4- dibrom furans or 2,4- dibromo thiophene or 2,4- dibromo selenophen are added in anhydrous THF
At 1 part, -78 DEG C plus 1 part of n-BuLi reacts 1.0~2.0h, then adds 1~2 part of 12~24h of RI backflows to obtain 2-R base -4- bromine furans
Or 2-R base -4- bromothiophenes or 2-R base -4- bromine selenophens；
(2) at -78 DEG C, 2-R bases -4- bromines furans or 2-R base -4- bromothiophenes or the 1 part of addition of 2-R base -4- bromines selenophen are taken
Into anhydrous THF, 1 part of n-BuLi is added dropwise, is moved on at room temperature after stirring 0.5~3h.In said mixture add 1~
2.0 parts of dimethyl disulfide, 10~24h is stirred, is quenched with saturated ammonium chloride, dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained
2-R bases -4- sulfidomethyls furans or 2-R bases -4- sulfidomethyls thiophene or 2-R base -4- sulfidomethyl selenophens；
(3) at 0 DEG C, 2-R bases -4- sulfidomethyls furans or 2-R bases -4- sulfidomethyls thiophene or 2-R base -4- sulfidomethyl selenium are taken
1 part of fen is added in dichloromethane, and adds 1 part of bromine, stirs 2.5~5.0h, adds saturation NaHSO3Or thiosulfuric acid
Sodium solution, extract organic phase and drying be spin-dried for, cross post obtain the bromo- 5-R bases -3- sulfidomethyls furans of 2- or the bromo- 5-R bases -3- of 2-
Sulfidomethyl thiophene or the bromo- 5-R bases -3- sulfidomethyl selenophens of 2-；
(4) the bromo- 5-R bases -3- sulfidomethyls furans of 2- or the bromo- 5-R bases -3- sulfidomethyls thiophene of 2- or the bromo- 5-R bases -3- of 2- are taken
1 part of sulfidomethyl selenophen, the furan boronic acids of 2,5- bis- or 2,5- Dithiophene boric acid or 2.2~3.0 parts of bis- selenophen boric acid of 2,5- are added to
In THF, in N2Or Pd (the PPh of the lower addition 2~10% of Ar protections3)4, it is heated to reflux 24~48h.THF is screwed out, extracts organic
Mutually and drying is spin-dried for, and is crossed post and is obtained 2,5- (2- (5-R base -3- sulfidomethyls) furans) furans or 2,5- (2- (5-R base -3- sulphur first
Base) thiophene) thiophene or 2,5- (2- (5-R base -3- sulfidomethyls) selenophen) selenophen)；
(5) 1 part of 2,5- (2- (5-R base -3- sulfidomethyls) furans) furans or 2,5- (2- (5-R base -3- sulfidomethyls) thiophene are taken
Fen) thiophene or 2,5- (2- (5-R base -3- sulfidomethyls) selenophen) selenophen be added in glacial acetic acid, in said mixture slowly plus
Enter 25~40% H2O22.2~4 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, adds 3~5 parts in the mixture
Trifluoromethanesulfonic acid, 24~36h is stirred at room temperature, reaction product is poured into the mixed liquor of water and pyridine and is heated to reflux 0.5~
1.0h, filter and use dichloromethane wash products, distil target product containing oxygen group elements and five condensed ring conjugated molecules derivative
Thing.
It should be noted that the ratio of the water and pyridine is 8: 1.
It should be noted that its step (3) includes with the R bases described in (4)：Alkyl, including methyl, ethyl, propyl group,
Isopropyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, the tetradecane
At least one of base, pentadecyl, cetyl, heptadecyl and octadecyl；Alkoxy, including methoxyl group, second
Epoxide, propoxyl group, butoxy, amoxy, hexyloxy, epoxide in heptan, octyloxy, nonyl epoxide, decyloxy, hendecane epoxide, 12
In alkoxy, tridecane epoxide, tetradecyloxyaniline, pentadecane epoxide, hexadecane epoxide, heptadecane epoxide and octadecane epoxide
It is at least one；Aryl, including phenyl, naphthyl, tolyl, ethylphenyl, propyl group phenyl, butyl phenyl, amyl group phenyl, oneself
Base phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, undecyl phenyl, dodecylphenyl, tridecyl
In phenyl, myristyl phenyl, pentadecylphenyl, cetyl phenyl, heptadecyl phenyl and octadecylphenyl
It is at least one；Thienyl, including 5- thiophene thiophene, 5- ethylthiophenes, 5- propyl group thiophene, 5- isopropyls thiophene, 5- butyl
Thiophene, 5- amylic thiophenes, 5- hexyl thiophenes, 5- heptyl thiophene, 5- octyl thiophenes, 5- nonyls thiophene, 5- decylthiophenes, 5- 11
Alkylthrophene, 5- dodecylthiophenes, 5- tridecyls thiophene, 5- myristyls thiophene, 5- pentadecyls thiophene, 5- hexadecanes
At least one in base thiophene, 5- heptadecyls thiophene, 5- octadecyl thiophene.
A kind of containing oxygen group elements and five condensed ring conjugated molecules and its derivant material can be applied to OLED, polycrystalline organic thin film
The donor material of body pipe p-type material and organic solar batteries.
Beneficial effect of the present invention is：
1st, synthesis step is simple, and yield is higher；
2nd, dissolubility is good, dissolves in a variety of Conventional solvents (dichloromethane, chloroform, tetrahydrofuran, DMF, DMSO etc.)；
3rd, higher carrier mobility.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but should not be construed as limiting the invention.
It should be noted that following embodiments 1~3 are containing oxygen group elements and five condensed ring conjugated molecules, embodiment 4~7
It is containing oxygen group elements and five condensed ring conjugated molecule derivatives.
Example 1
Preparation：
At -78 DEG C, take 1 part of 3- bromines furans to be added in anhydrous THF, 1 part of BuLi is added dropwise, after stirring 0.5~3h
Move on at room temperature.1~2.0 part of dimethyl disulfide is added in said mixture, 10~24h is stirred, uses saturated ammonium chloride
It is quenched, dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained 3- sulfidomethyl furans.
At 0 DEG C, take 1 part of 3- sulfidomethyls furans to be added in dichloromethane, will add 1 part of bromine, stirring 2.5~
5.0h, add saturation NaHSO3Or hypo solution, extract organic phase and drying be spin-dried for, cross post obtain the bromo- 3- sulphur of 2-
Methylfuran
2.2~3.0 parts of the bromo- 3- sulfidomethyls furans of 2- is taken to be added in THF, in N2Or the lower addition 2~10% of Ar protections
Pd(PPh3)4, it is heated to reflux 24~48h.Screw out THF, extract organic phase and drying be spin-dried for, cross post obtain 2,5- (2- (3- sulphur
Methyl) furans) furans.
1 part of 2,5- (2- (3- sulfidomethyls) furans) furans is taken to be added in glacial acetic acid, be slowly added in said mixture
25~40% H2O22.2~4 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, in the mixture the three of 3~5 parts of addition
Fluorine methanesulfonic acid, stirs 24-36h at room temperature, reaction product is poured into the mixed liquor of water and pyridine and is heated to reflux 0.5~
1.0h, filter and with dichloromethane wash products, distil to obtain target product.It should be noted that water: pyridine=8: 1.Nuclear-magnetism is total to
Shake result：1H NMR(CDCl3, 400MHz), δ (ppm)：7.38 (d, 2H), 6.30 (d, 2H).
Example 2
Preparation：
At -78 DEG C, take 1 part of 3 bromo thiophene to be added in anhydrous THF, 1 part of BuLi is added dropwise, after stirring 0.5~3h
Move on at room temperature.1~2.0 part of dimethyl disulfide is added in said mixture, 10~24h is stirred, uses saturated ammonium chloride
It is quenched, dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained 3- sulfidomethyl thiophene.
At 0 DEG C, take 1 part of 3- sulfidomethyls thiophene to be added in dichloromethane, will add 1 part of bromine, stirring 2.5~
5.0h, add saturation NaHSO3Or hypo solution, extract organic phase and drying be spin-dried for, cross post obtain the bromo- 3- sulphur of 2-
Methylthiophene.
2.2~3.0 parts of the bromo- 3- sulfidomethyls thiophene of 2- is taken to be added in THF, in N2Or the lower addition 2~10% of Ar protections
Pd(PPh3)4, it is heated to reflux 24~48h.Screw out THF, extract organic phase and drying be spin-dried for, cross post obtain 2,5- (2- (3- sulphur
Methyl) thiophene) thiophene.
1 part of 2,5- (2- (3- sulfidomethyls) thiophene) thiophene is taken to be added in glacial acetic acid, be slowly added in said mixture
25~40% H2O22.2~4 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, in the mixture the three of 3~5 parts of addition
Fluorine methanesulfonic acid, 24~36h is stirred at room temperature, reaction product is poured into the mixed liquor of water and pyridine and is heated to reflux 0.5~
1.0h, filter and with dichloromethane wash products, distil to obtain target product.It should be noted that water: pyridine=8: 1.Nuclear-magnetism is total to
Shake result：1H NMR(CDCl3, 400MHz), δ (ppm)：7.20 (d, 2H), 6.96 (d, 2H).
Example 3
Preparation：
At -78 DEG C, 1 part of 3- bromines selenophen is added in anhydrous THF, and 1 part of BuLi is added dropwise, and is moved after stirring 0.5~3h
To at room temperature.1~2.0 part of dimethyl disulfide is added in said mixture, 10~24h is stirred, is quenched with saturated ammonium chloride
Go out, dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained 3- sulfidomethyl thiophene.
At 0 DEG C, 1 part of 3- sulfidomethyls selenophen is added in dichloromethane, will add 1 part of bromine, and stirring 2.5~
5.0h, add saturation NaHSO3Or hypo solution, extract organic phase and drying be spin-dried for, cross post obtain the bromo- 3- sulphur of 2-
Methyl selenophen.
2.2~3.0 parts of the bromo- 3- sulfidomethyls selenophens of 2- are taken to be added in THF, in N2Or the lower Pd for adding 2-10% of Ar protections
(PPh3) 4, it is heated to reflux 24~48h.Screw out THF, extract organic phase and drying be spin-dried for, cross post obtain 2,5- (2- (3- sulphur first
Base) selenophen) selenophen.
1 part of 2,5- (2- (3- sulfidomethyls) selenophen) selenophen is taken to be added in glacial acetic acid, be slowly added in said mixture
25~40% H2O22.2~4 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, in the mixture the three of 3~5 parts of addition
Fluorine methanesulfonic acid, 24-36h is stirred at room temperature, reaction product is poured into the mixed liquor of water and pyridine and is heated to reflux 0.5~
1.0h, filter and with dichloromethane wash products, distil to obtain target product.It should be noted that water: pyridine=8: 1.Nuclear-magnetism is total to
Shake result：1H NMR(CDCl3, 400MHz), δ (ppm)：6.60 (d, 2H), 5.20 (d, 2H).
Example 4
Preparation：
In N2Or under Ar protections, in anhydrous THF plus at 1 part, -78 DEG C of 2,4- dibromo thiophenes plus 1 part of n-BuLi reacts 1.0
~2.0h, then add 1~2 part of C6H13I backflows 12-24h obtains 2- hexyl -4- bromothiophenes.
At -78 DEG C, take 1 part of 2- hexyl -4- bromothiophenes to be added in anhydrous THF, 1 part of n-BuLi is added dropwise, stir
Moved on at room temperature after 0.5~3h.1~2.0 part of dimethyl disulfide is added in said mixture, stirs 10~24h, with full
It is quenched with ammonium chloride, dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained 2- hexyl -4- sulfidomethyl thiophene.
At 0 DEG C, take 1 part of 2- hexyl -4- sulfidomethyls thiophene to be added in dichloromethane, 1 part of bromine, stirring will be added
2.5~5.0h, add saturation NaHSO3Or hypo solution, extract organic phase and drying are spin-dried for, crossing post, to obtain 2- bromo-
5- hexyl -3- sulfidomethyl thiophene.
1 part of the bromo- 5- hexyls -3- sulfidomethyls thiophene of 2-, 2,5- Dithiophene boric acid 2.2-3.0 parts is taken to be added in THF, in N2
Or the lower Pd (PPh for adding 2-10% of Ar protections3)4, it is heated to reflux 24~48h.THF is screwed out, extracts to obtain organic phase and dry rotation
It is dry, cross post and obtain 2,5- (2- (5- hexyl -3- sulfidomethyls) thiophene) thiophene.
Take 1 part of 2,5- (2- (5- hexyl -3- sulfidomethyls) thiophene) thiophene to be added in glacial acetic acid, delay in said mixture
The H of slow addition 25~40%2O22.2~4 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, adds 3-5 in the mixture
The trifluoromethanesulfonic acid of part, 24~36h is stirred at room temperature, reaction product is poured into the mixed liquor of water and pyridine and is heated to reflux
0.5~1.0h, filter and with dichloromethane wash products, distil to obtain target product.It should be noted that water: pyridine=8: 1.Core
Magnetic resonance results：1H NMR(CDCl3, 400MHz), δ (ppm)：6.60 (d, 2H), 2.72 (m, 4H), 1.59 (m, 4H), 1.31
(m, 4H), 1.29 (m, 8H), 0.88 (m, 6H).
Example 5
Preparation：
In N2Or under Ar protections, in anhydrous THF plus at 1 part, -78 DEG C of 2,4- dibromo thiophenes plus 1 part of n-BuLi reacts 1.0
~2.0h, then add 1-2 parts C6H1312~24h of I backflows obtains the bromo- 2- of 4- (2- (5- hexyls) thiophene) thiophene.
At -78 DEG C, take the bromo- 2- of 4- (2- (5- hexyls) thiophene) 1 part of thiophene to be added in anhydrous THF, be added dropwise 1 part
BuLi, moved on at room temperature after stirring 0.5~3h.1~2.0 part of dimethyl disulfide, stirring 10 are added in said mixture
~24h, is quenched with saturated ammonium chloride, and dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained 2- (2- (5- hexyls) thiophene) -4- sulphur first
Base thiophene.
At 0 DEG C, take 2- (2- (5- hexyls) thiophene) 1 part of -4- sulfidomethyls thiophene to be added in dichloromethane, 1 will be added
The bromine of part, 2.5~5.0h is stirred, add saturation NaHSO3Or hypo solution, extract organic phase and drying be spin-dried for,
Cross post and obtain the bromo- 5- of 2- (2- (5- hexyls) thiophene) -3- sulfidomethyl thiophene.
The bromo- 5- of 2- (2- (5- hexyls) thiophene) 1 part of -3- sulfidomethyls thiophene, 2.2~3.0 parts of 2,5- Dithiophenes boric acid is taken to add
Enter into THF, in N2Or Pd (the PPh of the lower addition 2~10% of Ar protections3)4, it is heated to reflux 24~48h.THF is screwed out, is extracted
Organic phase and drying be spin-dried for, cross post obtain 2,5- (2- (5- hexyls) thiophene -3- sulfidomethyls) thiophene) thiophene.
Taking 1 part of 2,5- (2- (5- hexyls) thiophene -3- sulfidomethyls) thiophene) thiophene is added in glacial acetic acid, in above-mentioned mixing
25~40% H is slowly added in thing2O22.2~4 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, adds in the mixture
Enter 3~5 parts of trifluoromethanesulfonic acid, stir 24~36h at room temperature, reaction product is poured into the mixed liquor of water and pyridine and heated
Flow back 0.5~1.0h, filters and with dichloromethane wash products, distil to obtain target product.It should be noted that water: pyridine=8:
1.Nuclear magnetic resonance result：1H NMR(CDCl3, 400MHz), δ (ppm)：7.49 (d, 2H), 7.25 (d, 2H), 6.83 (d, 2H),
2.77 (m, 4H), 1.59 (m, 4H), 1.31 (m, 4H), 1.29 (m, 8H), 0.88 (m, 6H).
Example 6
Preparation：
In N2Or under Ar protections, in anhydrous THF plus at 1 part, -78 DEG C of 2,4- dibromo thiophenes plus 1 part of n-BuLi reacts 1.0
~2.0h, then add 1-2 parts C6H1312~24h of I backflows obtains the bromo- 2- of 4- (2- (5- hexyls) benzene) thiophene.
At -78 DEG C, take the bromo- 2- of 4- (2- (5- hexyls) benzene) 1 part of thiophene to be added in anhydrous THF, be added dropwise 1 part
BuLi, moved on at room temperature after stirring 0.5~3h.1~2.0 part of dimethyl disulfide, stirring 10 are added in said mixture
~24h, is quenched with saturated ammonium chloride, and dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained 2- (2- (5- hexyls) benzene) -4- sulfidomethyls
Thiophene.
At 0 DEG C, take 2- (2- (5- hexyls) benzene) 1 part of -4- sulfidomethyls thiophene to be added in dichloromethane, 1 part will be added
Bromine, stir 2.5~5.0h, add saturation NaHSO3Or hypo solution, extract organic phase and drying be spin-dried for, mistake
Post obtains the bromo- 5- of 2- (2- (5- hexyls) benzene) -3- sulfidomethyl thiophene.
Take the bromo- 5- of 2- (2- (5- hexyls) benzene) 1 part of -3- sulfidomethyls thiophene, 2,5- Dithiophenes boric acid, 2.2~3.0 parts of additions
Into THF, in N2Or Pd (the PPh of the lower addition 2~10% of Ar protections3)4, it is heated to reflux 24~48h.THF is screwed out, extracting to have
Machine phase and drying be spin-dried for, cross post obtain 2,5- (2- (5- hexyls) benzene -3- sulfidomethyls) thiophene) thiophene.
Taking 1 part of 2,5- (2- (5- hexyls) benzene -3- sulfidomethyls) thiophene) thiophene is added in glacial acetic acid, in said mixture
In be slowly added to 25~40% H2O22.2~4 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, adds in the mixture
3~5 parts of trifluoromethanesulfonic acid, 24~36h is stirred at room temperature, reaction product is poured into the mixed liquor of water and pyridine and heated back
0.5~1.0h is flowed, is filtered and with dichloromethane wash products, distil to obtain target product.It should be noted that water: pyridine=8: 1.
Nuclear magnetic resonance result:1H NMR(CDCl3, 400MHz), δ (ppm)：7.74 (d, 4H), 7.35 (d, 4H), 7.25 (d, 2H), 2.62
(m, 4H), 1.59 (m, 4H), 1.31 (m, 4H), 1.29 (m, 8H), 0.88 (m, 6H).
Example 7
Preparation：
Take 3 parts of n-hexyl alcohols, add 3 parts of Na, add 1 part of 2,4- dibromo thiophene, 0.5 part of CuO, it is stirred at reflux 3.0~
10.0h, obtain the bromo- 4- hexyloxies thiophene of 2-.
At -78 DEG C, take 1 part of the bromo- 4- hexyloxies thiophene of 2- to be added in anhydrous THF, 1 part of BuLi is added dropwise, stir
Moved on at room temperature after 0.5~3h.1~2.0 part of dimethyl disulfide is added in said mixture, stirs 10~24h, with full
It is quenched with ammonium chloride, dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained 2- hexyloxy -4- sulfidomethyl thiophene.
At 0 DEG C, take 1 part of 2- hexyloxy -4- sulfidomethyls thiophene to be added in dichloromethane, 1 part of bromine will be added, stirred
2.5~5.0h is mixed, adds saturation NaHSO3Or hypo solution, extract organic phase and drying be spin-dried for, cross post obtain 2-
Bromo- 5- hexyloxies -3- sulfidomethyl thiophene.
1 part of the bromo- 5- hexyloxies -3- sulfidomethyls thiophene of 2-, 2.2~3.0 parts of 2,5- Dithiophenes boric acid is taken to be added in THF,
In N2Or Pd (the PPh of the lower addition 2~10% of Ar protections3)4, it is heated to reflux 24~48h.THF is screwed out, extracts organic phase and to do
It is dry to be spin-dried for, cross post and obtain 2,5- (2- (5- hexyloxy -3- sulfidomethyls) thiophene) thiophene.
1 part of 2,5- (2- (5- hexyloxy -3- sulfidomethyls) thiophene) thiophene is taken to be added in glacial acetic acid, in said mixture
It is slowly added to 25~40% H2O22.2~4 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, adds 3- in the mixture
5 parts of trifluoromethanesulfonic acid, 24~36h is stirred at room temperature, reaction product is poured into the mixed liquor of water and pyridine and is heated to reflux
0.5~1.0h, filter and with dichloromethane wash products, distil to obtain target product.It should be noted that water: pyridine=8: 1.Core
Magnetic resonance results：1H NMR(CDCl3, 400 MHz), δ (ppm)：6.02 (d, 2H), 4.06 (m, 4H), 1.76 (m, 4H), 1.43
(m, 4H), 1.31 (m, 4H), 1.29 (m, 4H), 0.88 (m, 6H).
For those skilled in the art, technical scheme that can be as described above and design, make other each
Kind is corresponding to be changed and deforms, and all these change and deformed the protection model that should all belong to the claims in the present invention
Within enclosing.
Claims (4)
1. a kind of prepare containing oxygen group elements and five condensed ring conjugated molecules methods, it is characterised in that described containing oxygen group elements
And five condensed ring conjugated molecule structure it is as follows：
X is O, S, Se, and its counter structure is as follows：
Methods described comprises the following steps：
(1) at -78 DEG C, take 3- bromines furans or 3 bromo thiophene or 1 part of 3- bromines selenophen to be added in anhydrous THF, be added dropwise 1 part
BuLi, moved on at room temperature after stirring 0.5~3h；1~2.0 part of dimethyl disulfide, stirring 10 are added in said mixture
~24h, is quenched with saturated ammonium chloride, and dichloromethane extraction, drying is spin-dried for, and is crossed post and is obtained 3- sulfidomethyls furans or 3- sulfidomethyl thiophene
Or 3- sulfidomethyl selenophens；
(2) at 0 DEG C, 3- sulfidomethyls furans or 3- sulfidomethyls thiophene or 1 part of 3- sulfidomethyls selenophen is taken to be added in dichloromethane,
1 part of bromine will be added, stir 2.5~5.0h, add saturation NaHSO3Or hypo solution, extract organic phase and to do
It is dry to be spin-dried for, cross post and obtain the bromo- 3- sulfidomethyls furans of 2- or the bromo- 3- sulfidomethyls thiophene of 2- or the bromo- 3- sulfidomethyls selenophens of 2-；
(3) the bromo- 3- sulfidomethyls furans of 2- or the bromo- 3- sulfidomethyls thiophene of 2- or 2.2~3.0 parts of the bromo- 3- sulfidomethyls selenophens of 2- is taken to add
Enter into THF, in N2Or Pd (the PPh of the lower addition 2~10% of Ar protections3)4, it is heated to reflux 24-48h；THF is screwed out, extracting to have
Machine phase and drying be spin-dried for, cross post obtain 2,5- (2- (3- sulfidomethyls) furans) furans or 2,5- (2- (3- sulfidomethyls) thiophene) thiophene
Or 2,5- (2- (3- sulfidomethyls) selenophen) selenophen；
(4) 1 part of 2,5- (2- (3- sulfidomethyls) furans) furans or 2,5- (2- (3- sulfidomethyls) thiophene) thiophene or 2,5- (2- are taken
(3- sulfidomethyls) selenophen) selenophen is added in glacial acetic acid, 25~40% H is slowly added in said mixture2O22.2~4.0
Part, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, adds 3~5 parts of trifluoromethanesulfonic acid in the mixture, stir at room temperature
24~36h is mixed, reaction product is poured into the mixed liquor of water and pyridine and is heated to reflux 0.5~1.0h, filters and uses dichloromethane
Wash products, distil target product containing oxygen group elements and five condensed ring conjugated molecules.
2. according to claim 1 containing oxygen group elements and five condensed ring conjugated molecule preparation methods, it is characterised in that described
The ratio of water and pyridine is 8: 1.
3. a kind of prepare containing oxygen group elements and five condensed ring conjugated molecule derivatives methods, it is characterised in that described to contain chalcogen
Element and five condensed ring conjugated molecule derivant structures it is as follows：
X is O, S, Se, and its counter structure is as follows：
Wherein, R is：Alkyl or alkoxy, aryl, at least one of thienyl；Wherein, alkyl be methyl, it is ethyl, propyl group, different
Propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl,
At least one of pentadecyl, cetyl, heptadecyl and octadecyl；Alkoxy is methoxyl group, ethyoxyl, the third oxygen
Base, butoxy, amoxy, hexyloxy, epoxide in heptan, octyloxy, nonyl epoxide, decyloxy, hendecane epoxide, dodecyloxy, ten
At least one of tri-alkoxy, tetradecyloxyaniline, pentadecane epoxide, hexadecane epoxide, heptadecane epoxide and octadecane epoxide；
Aryl be phenyl, naphthyl, tolyl, ethylphenyl, propyl group phenyl, butyl phenyl, amyl group phenyl, hexyl phenyl, heptyl phenyl,
Octyl phenyl, nonyl phenyl, decyl phenyl, undecyl phenyl, dodecylphenyl, tridecyl phenyl, Tetradecylbenzene
At least one in base, pentadecylphenyl, cetyl phenyl, heptadecyl phenyl and octadecylphenyl；Thienyl
For 1,4-Dithiapentalene, 5- thiophene thiophene, 5- ethylthiophenes, 5- propyl group thiophene, 5- isopropyls thiophene, 5- butyl thiophenes, 5- amyl group thiophenes
Fen, 5- hexyl thiophenes, 5- heptyl thiophene, 5- octyl thiophenes, 5- nonyls thiophene, 5- decylthiophenes, 5- undecyls thiophene, 5- ten
Dialkylthiophene, 5- tridecyls thiophene, 5- myristyls thiophene, 5- pentadecyls thiophene, 5- cetyls thiophene, 5- 17
At least one in alkylthrophene, 5- octadecyl thiophene；
Methods described comprises the following steps：
(1)N2Or under Ar protections, 2,4- dibrom furans or 2,4- dibromo thiophene or 1 part of 2,4- dibromo selenophen are added in anhydrous THF ,-
At 78 DEG C plus 1 part of BuLi reacts 1.0~2.0h, then adds 1~2 part of 12~24h of RI backflows to obtain 2-R bases -4- bromines furans or 2-R
Base -4- bromothiophenes or 2-R base -4- bromine selenophens；
(2) at -78 DEG C, 2-R bases -4- bromines furans or 2-R base -4- bromothiophenes or 1 part of 2-R base -4- bromines selenophen is taken to be added to nothing
In water THF, 1 part of BuLi is added dropwise, is moved on at room temperature after stirring 0.5~3h；1~2.0 part is added in said mixture
Dimethyl disulfide, stir 10~24h, be quenched with saturated ammonium chloride, dichloromethane extraction, drying be spin-dried for, cross post obtain 2-R bases-
4- sulfidomethyls furans or 2-R bases -4- sulfidomethyls thiophene or 2-R base -4- sulfidomethyl selenophens；
(3) at 0 DEG C, 2-R bases -4- sulfidomethyls furans or 2-R bases -4- sulfidomethyls thiophene or 2-R base -4- sulfidomethyls selenophen 1 are taken
Part is added in dichloromethane, and adds 1 part of bromine, stirs 2.5~5.0h, adds saturation NaHSO3Or sodium thiosulfate is molten
Liquid, extract organic phase and drying be spin-dried for, cross post obtain the bromo- 5-R bases -3- sulfidomethyls furans of 2- or the bromo- 5-R bases -3- sulphur first of 2-
Base thiophene or the bromo- 5-R bases -3- sulfidomethyl selenophens of 2-；
(4) the bromo- 5-R bases -3- sulfidomethyls furans of 2- or the bromo- 5-R bases -3- sulfidomethyls thiophene of 2- or the bromo- 5-R bases -3- sulphur first of 2- are taken
1 part of base selenophen, the furan boronic acids of 2,5- bis- or 2,5- Dithiophene boric acid or 2.2~3.0 parts of bis- selenophen boric acid of 2,5- are added to THF
In, in N2Or Pd (the PPh of the lower addition 2~10% of Ar protections3)4, it is heated to reflux 24~48h；Screw out THF, extract organic phase simultaneously
Drying is spin-dried for, and is crossed post and is obtained 2,5- (2- (5-R base -3- sulfidomethyls) furans) furans or 2,5- (2- (5-R base -3- sulfidomethyls) thiophene
Fen) thiophene or 2,5- (2- (5-R base -3- sulfidomethyls) selenophen) selenophen)；
(5) 1 part of 2,5- (2- (5-R base -3- sulfidomethyls) furans) furans or 2,5- (2- (5-R base -3- sulfidomethyls) thiophene) thiophene are taken
Fen or 2,5- (2- (5-R base -3- sulfidomethyls) selenophen) selenophen are added in glacial acetic acid, it is slowly added to 25 in said mixture~
40% H2O22.2~4 parts, 20~36h of temperature rising reflux, it is spin-dried for obtaining mixture, adds 3~5 parts of fluoroform in the mixture
Sulfonic acid, 24~36h is stirred at room temperature, reaction product is poured into the mixed liquor of water and pyridine and is heated to reflux 0.5~1.0h, mistake
Filter and use dichloromethane wash products, distil target product containing oxygen group elements and five condensed ring conjugated molecule derivatives.
4. according to claim 3 containing oxygen group elements and five condensed ring conjugated molecule derivative preparation methods, its feature exist
In the ratio of the water and pyridine is 8: 1.
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