CN104254538A - 萘并双噻二唑衍生物 - Google Patents
萘并双噻二唑衍生物 Download PDFInfo
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- CN104254538A CN104254538A CN201380021148.7A CN201380021148A CN104254538A CN 104254538 A CN104254538 A CN 104254538A CN 201380021148 A CN201380021148 A CN 201380021148A CN 104254538 A CN104254538 A CN 104254538A
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- naphtho
- thiadiazoles
- acid ester
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- boric acid
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- 150000004867 thiadiazoles Chemical class 0.000 claims description 38
- 239000004327 boric acid Substances 0.000 claims description 27
- -1 triol boric acid ester Chemical class 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 10
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical compound FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 claims description 10
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 5
- 125000005621 boronate group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical group FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract 2
- 125000005620 boronic acid group Chemical group 0.000 abstract 2
- 150000003839 salts Chemical group 0.000 abstract 2
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 abstract 1
- 150000001639 boron compounds Chemical class 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 150000002605 large molecules Chemical class 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 9
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical compound C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000950 dibromo group Chemical group Br* 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 1
- LTPQFVPQTZSJGS-UHFFFAOYSA-N 1$l^{4},3,5$l^{4},7-tetrathia-2,4,6,8-tetrazacycloocta-1,4,5,8-tetraene Chemical compound [N]1S[N]S[N]S[N]S1 LTPQFVPQTZSJGS-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- WYBQOWXCLDXZNR-UHFFFAOYSA-N 2-(1,3,2-benzodioxaborol-2-yl)-1,3,2-benzodioxaborole Chemical compound O1C2=CC=CC=C2OB1B1OC2=CC=CC=C2O1 WYBQOWXCLDXZNR-UHFFFAOYSA-N 0.000 description 1
- MDNDJMCSXOXBFZ-UHFFFAOYSA-N 2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5,5-dimethyl-1,3,2-dioxaborinane Chemical compound O1CC(C)(C)COB1B1OCC(C)(C)CO1 MDNDJMCSXOXBFZ-UHFFFAOYSA-N 0.000 description 1
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- UEBSWKNVDRJVHN-UHFFFAOYSA-N 4,4,6-trimethyl-2-(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)-1,3,2-dioxaborinane Chemical compound O1C(C)CC(C)(C)OB1B1OC(C)(C)CC(C)O1 UEBSWKNVDRJVHN-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- JAZCEXBNIYKZDI-UHFFFAOYSA-N [Ir+] Chemical compound [Ir+] JAZCEXBNIYKZDI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- TWEILHAJXWAJIW-UHFFFAOYSA-N benzo[e][1,2,3]benzothiadiazole Chemical class C1=CC2=CC=CC=C2C2=C1SN=N2 TWEILHAJXWAJIW-UHFFFAOYSA-N 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/025—Silicon compounds without C-silicon linkages
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- 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
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
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- 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
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- 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
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- Spectroscopy & Molecular Physics (AREA)
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- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
萘并双噻二唑衍生物以式(1)表示。式1中，Z表示氢、硼酸基、硼酸酯基、三氟硼酸盐基、或三醇硼酸酯盐基，至少一个是硼酸基、硼酸酯基、三氟硼酸盐基、或三醇硼酸酯盐基。萘并双噻二唑衍生物是有机硼化合物，能够经铃木宫浦偶合法等转化成经常使用的化合物，能够用作复杂化合物的前体。所以，能够以萘并双噻二唑衍生物为基础来实现对各种有机半导体材料等有用的低分子化合物和/或高分子化合物的研究、开发和实用化。
Description
技术领域
本发明涉及萘并双噻二唑衍生物。
背景技术
各种有机半导体材料的研究、开发、实用化发展起来，具有萘并双噻二唑骨架的有机半导体材料被视作是有希望的。非专利文献1中，公开了一种具有萘并双噻二唑骨架的有机半导体材料及其合成方法。
现有技术文献
非专利文献
非专利文献1：Ming Wang,Xiaowen Hu,Peng Liu,Wei Li,Xiong Gong,Fei Huang,andYong Cao；“Donor-Acceptor Conjugated Polymer Based onNaphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole for High Performance Polymer Solar cells”；J.Am.Chem.Soc.,133,9638-9641,(2011).
发明内容
发明要解决的技术问题
非专利文献1中，将萘并双噻二唑溴化，用过渡金属催化剂使该溴化物与具有有机锡等有机金属的噻吩环等杂芳环或芳环键合，获得可以用作有机半导体材料的高分子化合物。然而，该方法中，根据结合的杂芳环或芳环而有时不能导入有机金属，另外，有机锡等有毒性，因此难以工业上使用，由此存在缺乏通用性的问题。
本发明是鉴于上述事项完成的，其目的在于，提供能够向各种具有萘并双噻二唑骨架的有机半导体材料开展、通用性优良的萘并双噻二唑衍生物。
解决技术问题的手段
本发明涉及的萘并双噻二唑衍生物的特征在于，以式1表示，
(式1中，Z表示氢、硼酸基、硼酸酯基、三氟硼酸盐基或三醇硼酸酯盐基，至少一个是硼酸基、硼酸酯基、三氟硼酸盐基或三醇硼酸酯盐基。)
另外，优选所述Z以式11～式19中的任一个表示。
(式12中，R表示烷基。)
发明的效果
本发明所涉及的萘并双噻二唑衍生物具有硼酸基、硼酸酯基、三氟硼酸盐基或三醇硼酸酯盐基。就硼酸基、硼酸酯基、三氟硼酸盐基或三醇硼酸酯盐基而言，能够经铃木宫浦偶合等偶合反应转化成经常使用的化合物，能够用作复杂化合物的前体，通用性强。所以，能够以萘并双噻二唑衍生物为基础来实现具有对各种有机半导体材料等有用的萘并双噻二唑骨架的低分子化合物和/或高分子化合物的研究、开发和实用化。
具体实施方式
(萘并双噻二唑衍生物)
本实施例所涉及的萘并双噻二唑衍生物以式1表示。
上述式1中，Z表示氢、硼酸基、硼酸酯基、三氟硼酸盐基或三醇硼酸酯盐基，至少一个是硼酸基、硼酸酯基、三氟硼酸盐基或三醇硼酸酯盐基。对硼酸基、硼酸酯基、三氟硼酸盐基或三醇硼酸酯盐基没有特别限定，作为例子，可以举出式11～19表示的官能团。应予说明，式12中，R表示烷基。
萘并双噻二唑衍生物是有机硼化合物，能够经铃木宫浦偶合等偶合反应转化成经常使用的化合物，能够用作复杂化合物的前体。
因此，能够使萘并双噻二唑衍生物与具有供体性官能团和/或受体性官能团、噻吩环等π共轭电子结构等的卤化物进行反应，从而容易地进行具有萘并双噻二唑骨架的低分子化合物和/或高分子化合物等的合成。
所以，能够以萘并双噻二唑衍生物为基础来实现具有对各种有机半导体材料等有用的萘并双噻二唑骨架的低分子化合物和/或高分子化合物的研究、开发和实用化。另外，萘并双噻二唑衍生物在水和/或空气中比较稳定，操作性也优良。
(萘并双噻二唑衍生物的合成方法)
对于上述本实施方式涉及的萘并双噻二唑衍生物的合成方法没有特别限制，能够组合公知的合成方法合成。作为一例，可以按如下方式合成。
使萘并双噻二唑衍生物(萘并[1,2-c:5,6-c']双[1,2,5]噻二唑)与二硼酸酯进行反应。将位于萘并双噻二唑的4位和9位的碳与氢的键切断，在相同位置键合硼酸酯基，得到式1表示的萘并双噻二唑衍生物。
作为使用的二硼酸酯，没有特别限制，例如可以举出双联硼酸频那醇酯(bis(pinacolato)diboron)和/或双联硼酸新戊二醇酯(bis(neopentyl glycolato)diboron)、双联(2-甲基-2,4-戊二醇)硼酸酯(bis(hexylene glycolato)diboron)、双联邻苯二酚硼酸酯(bis(catecholato)diboron)等二硼酸酯。
另外，宜添加CH活化催化剂使其反应。从而易于切断萘并双噻二唑的4位和9位的碳与氢的键。由此，促进脱离了氢的碳与硼酸酯基键合。作为CH活化催化剂，只要能够切断碳-氢键，就没有限制，例如可以举出钯、铱、钌等过渡金属或含有它们的催化剂。应予说明，将铱或含有铱的催化剂用作CH活化催化剂的情况下，宜也添加为配位体的化合物。
另外，具有硼酸的萘并双噻二唑衍生物能够通过将具有上述硼酸酯的萘并双噻二唑衍生物脱酯化而得到。
而且，具有三氟硼酸盐基和/或三醇硼酸酯盐基的萘并双噻二唑衍生物是利用具有硼酸或硼酸酯的萘并双噻二唑衍生物、采用例如Potassium Organotrifluoroborates:NewPerspectives in Organic Synthesis；Sylvain Darses and Jean-Pierre Genet,Chem.Rev.,108,288-325(2008)和/或Cyclic Triolborates:Air-and Water-Stable Ate Complexes of OrganoboronicAcids；Yasunori Yamamoto,Miho Takizawa,Xiao-Qiang Yu,Norio Miyaura,Angewandte ChemieInternational Edition,47,928-931(2007)中公开的方法得到的。
另外，能够使二溴萘并双噻二唑(4,9-二溴萘并[1,2-c:5,6-c']双[1,2,5]噻二唑)与二硼酸酯进行反应来合成具有硼酸酯基的双萘并双噻二唑衍生物。
应予说明，萘并双噻二唑衍生物(萘并[1,2-c:5,6-c']双[1,2,5]噻二唑)和/或二溴萘并双噻二唑(4,9-二溴萘并[1,2-c:5,6-c’]双[1,2,5]噻二唑)是采用Sulfur Nitride in Organic Chemistry.Part 19.Selective Formation of Benzo-and Benzobis[1,2,5]thiadiazole Skeleton in the Reaction ofTetrasulfur Tetranitride with Naphthalenols and Related Compounds；Shuntaro MATAKA,Kazufumi TAKAHASHI,Youji IKEZAKI,Taizo Hatta,Akiyoshi TORII,and Masashi TASHIRO；Bull.Chem.Soc.Jpn,64,68-73(1991)中公开的方法得到的。
实施例
下面，基于实施例对萘并双噻二唑衍生物及其合成方法进行详述，但本发明不限定于此。
(萘并[1,2-c:5,6-c']双[1,2,5]噻二唑-4,9双(硼酸频哪醇酯)(以下为化合物1)的合成)
氮气氛围下，在三口烧瓶中放入作为溶剂的环己烷20mL、作为CH活化催化剂的双(1,5-环辛二烯)二-μ-甲氧基二铱(Ⅰ)(33mg，0.05mmol)、作为CH活化催化剂的配位体的4,4’-二叔丁基-2.2’-联吡啶化合物(27mg，0.1mmol)，在遮光下回流搅拌约1小时。
接着，加入联硼酸频那醇酯(283mg，1.1mmol)，进一步回流30分钟。
其后，加入萘并[1,2-c:5,6-c']双[1,2,5]噻二唑(122mg，0.5mmol)，使其回流搅拌12小时。
冷却至室温后，除去环己烷，用氯仿将粗精制物再结晶，由此得到为乳白色针状结晶的化合物1(174mg，70％)。
将上述反应式示于下面。
另外，将得到的化合物1的测定结果示于下面。
1H-NMR(400MHz,CDCl3，ppm)δ1.50(s,24H,CH3)，9.52(s,2H,ArH)
(4,9-双(噻吩-2-基)-萘并[1,2-c:5,6-c']双[1,2,5]噻二唑(以下为化合物2)的合成)
氮气氛围下，在三口烧瓶中加入化合物1(99.2mg，0.2mmol)、2-溴噻吩(72.7mg，0.44mmol)、Pd(PPh3)4(4.8mg，0.004mmol)、碳酸钾(1.11g，8mmol)、蒸馏水(4ml)、甲苯(10ml)，回流搅拌12小时。
将反应溶液冷却至室温，注入水，滤出析出的固体。用氯仿将得到的固体再结晶，由此得到为红色固体的化合物2(67mg，82％)。
上述反应式用下式表示。
另外，将得到的化合物2的测定结果示于下面。
1H-NMR(400MHz,CDCl3，ppm)δ7.29(d,2H,ArH),7.55(d,2H,ArH),8.33(d,2H,ArH),8.99(s,2H)
(4,9-二溴萘并[1,2-c:5,6-c']双[1,2,5]噻二唑(以下为化合物3)的合成)
在反应容器中加入化合物1(49.6mg，0.1mmol)、溴化铜(Ⅱ)(134mg，0.6mmol)、甲醇(4ml)、蒸馏水(2ml)、NMP(12ml)并使其回流。冷却后，滤出析出的固体，用盐酸、水、甲醇洗涤，由此得到化合物3(3mg，70％)。
将上述反应式示于下面。
另外，将得到的化合物3的测定结果示于下面。
1H-NMR(400MHz,CDCl3，ppm)δ9.14(s,2H,ArH)
(聚{萘并[1,2-c:5,6-c']双[1,2,5]噻二唑-4,9-二基-交替-(3’4”-二(2-癸基十四烷基)-2,2’；5’,2”；5”,2”’-四联噻吩-5,5”’-二基)}(化合物4)的合成)
氮气氛围下，在反应用管形瓶中放入化合物1(24.8mg，0.05mmol)、化合物A(58.1mg，0.05mmol)、Pd(PPh3)2Cl2(1.7mg，0.0025mmol)、2M的K2CO3水溶液(1.6ml)、甲苯(2.4ml)以及1滴季铵氯化物(Aliquat)336，并密封。
将其安置在微波合成装置中，使其在180℃下反应2小时。其后，将反应液注入到大过量的甲醇中，并搅拌。
用索克斯累特提取用过滤器滤出沉淀物，利用甲醇和氯仿，通过索克斯累特提取除去在这些溶剂中可溶的成分。
进一步用氯苯将过滤器残留进行索克斯累特提取，将得到的溶液注入到大过量的甲醇中。
滤出沉淀物，由此得到为深绿色固体的化合物4(27mg，43％)。
将上述反应式示于下面。
另外，将得到的化合物4的测定结果示于下面。
1H-NMR(400MHz，CDCl3，ppm)δ9.0付近(br，2H，ArH)，δ7～8付近(br，6H，ArH)，δ2.5付近(br，4H)，δ0.8～2付近(br，94H)
应予说明，本发明能够不脱离本发明的范围地实现各种实施方式和变形。另外，上述实施方式是说明本发明用的，不限定本发明的范围。
本申请基于在2012年4月26日申请的日本国专利申请2012-101625号。将日本国专利申请2012-101625号的说明书、专利权利要求的范围全部作为参照援引至本说明书中。
产业上的利用
如以上说明地，萘并双噻二唑衍生物能够经铃木宫浦偶合等偶合反应转化成经常使用的化合物，能够用作复杂化合物的前体，通用性优良。所以，能够以萘并双噻二唑衍生物为基础，期待具有对各种有机半导体材料等有用的萘并双噻二唑骨架的低分子化合物和/或高分子化合物的研究、开发和实用化。
Claims (2)
1.一种萘并双噻二唑衍生物，其特征在于，以式1表示，
式1中，Z表示氢、硼酸基、硼酸酯基、三氟硼酸盐基或三醇硼酸酯盐基，至少一个是硼酸基、硼酸酯基、三氟硼酸盐基或三醇硼酸酯盐基。
2.根据权利要求1所述的萘并双噻二唑衍生物，其特征在于，所述Z以式11～式19中的任一个表示，
式12中，R表示烷基。
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| PCT/JP2013/055129 WO2013161377A1 (ja) | 2012-04-26 | 2013-02-27 | ナフトビスチアジアゾール誘導体 |
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| CN112930351B (zh) * | 2018-10-30 | 2024-04-26 | 国立大学法人大阪大学 | 化合物及其制造方法以及使用了该化合物的有机半导体材料 |
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