WO2008140159A1 - Process for preparing organic silicon monomer - Google Patents
Process for preparing organic silicon monomer Download PDFInfo
- Publication number
- WO2008140159A1 WO2008140159A1 PCT/KR2007/005056 KR2007005056W WO2008140159A1 WO 2008140159 A1 WO2008140159 A1 WO 2008140159A1 KR 2007005056 W KR2007005056 W KR 2007005056W WO 2008140159 A1 WO2008140159 A1 WO 2008140159A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction
- formula
- organic silicon
- dioxythiophene
- hours
- Prior art date
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 17
- 239000010703 silicon Substances 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 238000006114 decarboxylation reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 2
- 230000000911 decarboxylating effect Effects 0.000 claims 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 239000002210 silicon-based material Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 150000003577 thiophenes Chemical class 0.000 claims 1
- 229930192474 thiophene Natural products 0.000 abstract description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 238000010992 reflux Methods 0.000 description 16
- -1 isoprophyl Chemical group 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- RIUHHQINFXZTAF-UHFFFAOYSA-N diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate;sodium Chemical compound [Na].[Na].CCOC(=O)C=1SC(C(=O)OCC)=C(O)C=1O RIUHHQINFXZTAF-UHFFFAOYSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 4
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229940071127 thioglycolate Drugs 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 3
- VJPALIAORYSTKL-UHFFFAOYSA-N 3,4-dimethoxythiophene-2,5-dicarboxylic acid Chemical compound COC1=C(C(O)=O)SC(C(O)=O)=C1OC VJPALIAORYSTKL-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- TVCSSJHLVLMADJ-UHFFFAOYSA-N ethyl 2-(2-ethoxy-2-oxoethyl)sulfanylacetate Chemical compound CCOC(=O)CSCC(=O)OCC TVCSSJHLVLMADJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- JBOAELCPSXBGSR-UHFFFAOYSA-N 2,3-dimethoxythiophene Chemical compound COC=1C=CSC=1OC JBOAELCPSXBGSR-UHFFFAOYSA-N 0.000 description 1
- XKUDDFRZUUSBOV-UHFFFAOYSA-N 3,4-dimethoxy-2h-thiophene-2,3-dicarboxylic acid Chemical compound COC1=CSC(C(O)=O)C1(OC)C(O)=O XKUDDFRZUUSBOV-UHFFFAOYSA-N 0.000 description 1
- ZUDCKLVMBAXBIF-UHFFFAOYSA-N 3,4-dimethoxythiophene Chemical compound COC1=CSC=C1OC ZUDCKLVMBAXBIF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- SFAZXBAPWCPIER-UHFFFAOYSA-N chloro-[chloro(dimethyl)silyl]-dimethylsilane Chemical compound C[Si](C)(Cl)[Si](C)(C)Cl SFAZXBAPWCPIER-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C07F7/08—Compounds having one or more C—Si linkages
Definitions
- the present invention relates to a process for preparing a conductive high-molecular weight organic silicon monomer of Formula 1 or 2, containing thiophene as a main backbone and having a substitution of a five- or six-membered heterocyclic compound containing silicon (Si) in the 3,4 position of the thiophene ring:
- Fager et al conducted preparation of the above-mentioned thiophene in the presence of copper and chromium oxide catalysts in 1945 (E. Fager, J. Am. Chem. Soc, 67(1945), 2217-2218).
- Polythiophene has been used for various applications, for example as an antistatic agent, a substitute for a condenser electrolyte, a coating on printed circuit boards (PCBs), and a variety of electronic materials for fabrication of electro-luminescence (EL) devices.
- Polythiophene may exhibit various physical properties particularly by the introduction of substituent(s) into the 3,4-position of the thiophene ring.
- Poly(3,4-ethylenedioxythiophene) having a broad industrial applicability as stated above is prepared from a 3,4-ethylenedioxythiophene monomer unit.
- the present invention has been made in view of the above problems, and it is an object of the present invention to provide synthesis of a conductive high- molecular weight monomer, i.e. a process for preparing a novel organic silicon monomer under milder reaction conditions without use of any catalyst, via the introduction of silicon atoms having the same bond order as that of existing carbon atoms but superior reactivity into the 3,4 position of the thiophene ring.
- Technical Solution [18]
- the presenst invetion provides a process for preparing a conductive high-molecular weight organic silicon monomer, which comprises following four steps:
- Step 1 condensation of dialkyl thioglycolate and dialkyl oxalate is carried out to recover an alcohol and prepare a 5-membered ring structure.
- Step 2 an activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene produced in Step 1 is reacted with 1,2-dichlorotetraalkyldisilane to synthesize 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene having a structure in which a thiophene ring is connected to a silicon-containing hetero ring.
- Step 2-1 is a the synthesis step of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene having a structure in which a thiophene ring is connected to a silicon- containing hetero ring, from the reaction of an activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene produced in Step 1 with 1 ,3-dichloro- 1 , 1 ,3,3-tetraalkyldisiloxane.
- Step 3 is saponification of 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene using an aqueous solution of an alkali metal salt having strong basicity.
- an alkali metal salt sodium hydroxide and potassium hydroxide are used.
- the subsequent process employs various kinds of acids such as hydrochloric acid, nitric acid and sulfuric acid.
- Step 3-1 is saponification of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene using an aqueous solution of an alkali metal salt having strong basicity.
- an alkali metal salt sodium hydroxide and potassium hydroxide are used.
- the subsequent process employs various kinds of acids such as hydrochloric acid, nitric acid and sulfuric acid.
- Step 4 is decarboxylation of 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene, which is carried out under a reduced atmosphere to thereby obtain 3 ,4-tetraalkyldisilylene dioxythiophene.
- Step 4-1 is decarboxylation of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene, which is carried out under a reduced atmosphere to thereby obtain 3 ,4-tetraalkyldisiloxylene dioxythiophene.
- FIG. 1 is a block diagram illustrating a preparation process of the present invention.
- the present invention is directed to a process for preparing a conductive high- molecular weight organic silicon monomer.
- reaction is required to carry out 4 steps for preparation of the aforesaid organic silicon monomer.
- Step 1 condensation of dialkyl thioglycolate and dialkyl oxalate is carried out to recover an alcohol and prepare a 5-membered ring structure.
- a conventional process usually employs a basic catalyst, whereas the present invention primarily employs metal alkoxides such as sodium methoxide and sodium ethoxide, and potassium methoxide and potassium ethoxide.
- each R may be identical to or different from each other and represents methyl or ethyl.
- dialkyl oxalate dimethyl oxalate and diethyl oxalate are used.
- the reaction solvent preferably employs a lower aliphatic alcohol which for an alkoxide component is present, such as methanol, ethanol or the like.
- a lower aliphatic alcohol which for an alkoxide component is present, such as methanol, ethanol or the like.
- dialkyl oxalate 4.0 moles of dialkyl oxalate are used based on dialkyl thioglycolate.
- the reaction is carried out at a temperature of 60 to 12O 0 C for 4 to 12 hours.
- the resulting solid compound is washed with an extra reaction solvent to thereby remove the unreacted reactants and dried at a temperature of 60 to 7O 0 C under vacuum.
- Step 2 an activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene produced in Step 1 is reacted with 1,2-dichlorotetraalkyldisilane to synthesize 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene having a structure in which a thiophene ring is connected to a silicon-containing hetero ring.
- reaction for Step 2 may be expressed as in Reaction Scheme 2 below: [41] Reaction Scheme 2 [42]
- Step 2-1 is a the synthesis step of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene having a structure in which a thiophene ring is connected to a silicon- containing hetero ring, from the reaction of an activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene produced in Step 1 with 1 ,3-dichloro- 1 , 1 ,3,3-tetraalkyldisiloxane.
- each R is as defined above.
- a solvent having a boiling point of 60 to 100 0 C is employed.
- the solvent that can be used in the present invention may include methanol, ethanol and toluene. These solvents may be used alone or in any combination thereof.
- As a proper reaction molar ratio 0.5 to 1.5 moles of a silicon reactant are used based on the activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene. The reaction is carried out for 3 to 6 hours.
- Step 3 is saponification of 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene using an aqueous solution of an alkali metal salt having strong basicity.
- an alkali metal salt sodium hydroxide and potassium hydroxide are used.
- the subsequent process employs various kinds of acids such as hydrochloric acid, nitric acid and sulfuric acid.
- each R is as defined above.
- Step 3-1 is saponification of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene using an aqueous solution of an alkali metal salt having strong basicity.
- an alkali metal salt sodium hydroxide and potassium hydroxide are used.
- the subsequent process employs various kinds of acids such as hydrochloric acid, nitric acid and sulfuric acid.
- each R is as defined above.
- the alkali metal salt is used in a content of 3 to 10% by weight, and the acid is used in a content of 1 to 10% by weight.
- Step 4 is decarboxylation of 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene, which is carried out under a reduced atmosphere to thereby obtain 3 ,4-tetraalkyldisilylene dioxythiophene.
- reaction for Step 4 may be expressed as in Reaction Scheme 6 below: [66] [67] Reaction Scheme 6 [68]
- Step 4-1 is decarboxylation of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene, which is carried out under a reduced atmosphere to thereby obtain 3 ,4-tetraalkyldisiloxylene dioxythiophene.
- reaction for Step 4-1 may be expressed as in Reaction Scheme 7 below: [73] [74] Reaction Scheme 7 [75]
- Step 4 and Step 4-1 In order to optimize the reactions of Step 4 and Step 4-1 in the present invention, various kinds of solvents such as polyethylene glycol, dibutylphthalate, tetramethyl sulfone, and the like are used.
- the reaction vessel is maintained at a pressure of 0.2 to 0.35 mbar.
- the reaction is then carried out at a temperature of 80 to 12O 0 C for 6 to 24 hours.
- the final compound thus obtained is distilled at a pressure of 0.1 mbar.
- a IL 3-neck flask was equipped with an impeller stirrer, a reflux condenser and a dropping funnel and was then flame-dried with a nitrogen purge.
- reaction mixture was stirred at 8O 0 C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was then gradually added thereto via the dropping funnel.
- reaction mixture was extracted three times with 500 mL of chloroform and dried over magnesium sulfate, followed by removal of the solvent under vacuum.
- Example 2 [98] A IL 3-neck flask was equipped with an impeller stirrer, a reflux condenser and a dropping funnel and was then flame-dried with a nitrogen purge.
- reaction mixture was stirred at 80 0 C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was gradually added thereto via the dropping funnel.
- reaction mixture was extracted three times with 500 mL of chloroform and dried over magnesium sulfate, followed by removal of the solvent under vacuum.
- reaction mixture was stirred at 80 0 C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was gradually added thereto via the dropping funnel.
- reaction mixture was extracted three times with 150 mL of chloroform and dried over magnesium sulfate, followed by vacuum concentration of the solution to make a final volume of 250 mL.
- reaction mixture was stirred at 8O 0 C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was gradually added thereto via the dropping funnel.
- reaction mixture was extracted three times with 150 mL of chloroform and dried over magnesium sulfate, followed by vacuum concentration of the solution to make a final volume of 250 mL.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Provided is a process for preparing a conductive high-molecular weight organic silicon monomer represented by Formula 1 or 2, which contains thiophene as a main backbone and has a substitution of a five- or six-membered heterocyclic compound containing silicon (Si) in the 3,4 position of the thiophene ring:
Description
Description
PROCESS FOR PREPARING ORGANIC SILICON MONOMER
Technical Field
[1] The present invention relates to a process for preparing a conductive high-molecular weight organic silicon monomer of Formula 1 or 2, containing thiophene as a main backbone and having a substitution of a five- or six-membered heterocyclic compound containing silicon (Si) in the 3,4 position of the thiophene ring:
[2] (Formula 1)
[3]
[4] (Formula 2)
[5]
Si -Si ^
S
[6] wherein R and R are methyl and R and R are methyl, isoprophyl, or phenyl group. Background Art
[7] Even though there has yet been no report of a compound having the same chemical structure as the compound of the present invention, several researches and studies have been made on 3,4-ethylenedioxythiophene having a similar chemical structure as follows.
[8] Since the first synthesis of 3,4-dialkoxythiophene in 1910, from condensation of an thiodiacetic acid ester with an oxalic acid ester, followed by alkylation, saponification and decarboxylation, Fager et al conducted preparation of the above-mentioned thiophene in the presence of copper and chromium oxide catalysts in 1945 (E. Fager, J. Am. Chem. Soc, 67(1945), 2217-2218).
[9] In 1948, U.S. Patent No. 2,453, 103 introduced decarboxylation of
3,4-dimethoxythiophene-2,5-dicarboxylic acid at a high temperature of 18O0C using a special copper powder catalyst.
[10] In 1951, Overberger et al reported the synthesis of 3,4-dimethoxythiophene by de-
carboxylation of 3,4-dimethoxythiophene-2,5-dicarboxylic acid at a temperature of 180 to 19O0C in the presence of a copper catalyst under solvent- free conditions (C. Overberger, J. Am. Chem. Soc, 73(1951), 2956-2957).
[11] In 1996, Merz et al developed a method for synthesis of dimethoxythiophene at a temperature of 25O0C, using 3,4-dimethoxythiophene dicarboxylic acid as a starting material without any reaction solvent and metal catalyst (J. Prakt. Chem., 338, 672-674). However, production of such a compound without use of the reaction diluent under high-temperature reaction conditions suffers from disadvantages associated with various additional processes for separation and purification of a desired compound from the reaction mixtures.
[12] In 1996, Coffey et al demonstrated that upon decarboxylation of dicarboxylic acid in the presence of a metal catalyst, the optimum reaction is carried out using 0.25 equivalents of a copper catalyst based on a start material, and a reaction temperature of 180 to 2000C (Synthetic Communications, 26(11), 2205-2212).
[13] However, such temperature conditions are affected by reaction sites and facilities to be employed, and there have been also raised various problems associated with a difficulty in industrial application thereof due to a low yield of 54%.
[14] Polythiophene has been used for various applications, for example as an antistatic agent, a substitute for a condenser electrolyte, a coating on printed circuit boards (PCBs), and a variety of electronic materials for fabrication of electro-luminescence (EL) devices. Polythiophene may exhibit various physical properties particularly by the introduction of substituent(s) into the 3,4-position of the thiophene ring.
[15] Poly(3,4-ethylenedioxythiophene) having a broad industrial applicability as stated above is prepared from a 3,4-ethylenedioxythiophene monomer unit.
[16] Therefore, it is important to develop a technique for preparation of the monomer
3,4-ethylenedioxythiophene. However, most of conventional arts involve high- temperature reaction conditions with essential use of a certain catalyst and thus suffer from production of reaction by-products due to such severe reaction conditions. Disclosure of Invention Technical Problem
[17] Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide synthesis of a conductive high- molecular weight monomer, i.e. a process for preparing a novel organic silicon monomer under milder reaction conditions without use of any catalyst, via the introduction of silicon atoms having the same bond order as that of existing carbon atoms but superior reactivity into the 3,4 position of the thiophene ring. Technical Solution
[18] To accomplish the above object, the presenst invetion provides a process for preparing a conductive high-molecular weight organic silicon monomer, which comprises following four steps:
[19] As Step 1, condensation of dialkyl thioglycolate and dialkyl oxalate is carried out to recover an alcohol and prepare a 5-membered ring structure.
[20] As Step 2, an activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene produced in Step 1 is reacted with 1,2-dichlorotetraalkyldisilane to synthesize 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene having a structure in which a thiophene ring is connected to a silicon-containing hetero ring.
[21] Step 2-1 is a the synthesis step of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene having a structure in which a thiophene ring is connected to a silicon- containing hetero ring, from the reaction of an activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene produced in Step 1 with 1 ,3-dichloro- 1 , 1 ,3,3-tetraalkyldisiloxane.
[22] Step 3 is saponification of 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene using an aqueous solution of an alkali metal salt having strong basicity. As the alkali metal salt, sodium hydroxide and potassium hydroxide are used. The subsequent process employs various kinds of acids such as hydrochloric acid, nitric acid and sulfuric acid.
[23] Step 3-1 is saponification of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene using an aqueous solution of an alkali metal salt having strong basicity. As the alkali metal salt, sodium hydroxide and potassium hydroxide are used. The subsequent process employs various kinds of acids such as hydrochloric acid, nitric acid and sulfuric acid.
[24] Finally, Step 4 is decarboxylation of 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene, which is carried out under a reduced atmosphere to thereby obtain 3 ,4-tetraalkyldisilylene dioxythiophene.
[25] Step 4-1 is decarboxylation of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene, which is carried out under a reduced atmosphere to thereby obtain 3 ,4-tetraalkyldisiloxylene dioxythiophene.
Advantageous Effects
[26] The present invention provides synthesis of a conductive high-molecular weight monomer, i.e. a process for preparing a novel organic silicon monomer under milder reaction conditions without use of any catalyst, via the introduction of silicon atoms having the same bond order as that of existing carbon atoms but superior reactivity into the 3,4 position of the thiophene ring. Brief Description of the Drawings
[27] FIG. 1 is a block diagram illustrating a preparation process of the present invention.
Best Mode for Carrying Out the Invention
[28] Hereinafter, the present invention will be described in more detail with reference to one embodiment.
[29] The present invention is directed to a process for preparing a conductive high- molecular weight organic silicon monomer.
[30] For this purpose, the reaction is required to carry out 4 steps for preparation of the aforesaid organic silicon monomer.
[31] As Step 1, condensation of dialkyl thioglycolate and dialkyl oxalate is carried out to recover an alcohol and prepare a 5-membered ring structure. In this connection, a conventional process usually employs a basic catalyst, whereas the present invention primarily employs metal alkoxides such as sodium methoxide and sodium ethoxide, and potassium methoxide and potassium ethoxide.
[32] The reaction for Step 1 may be expressed as in Reaction Scheme 1 below:
[33] Reaction Scheme 1
[34]
[35] wherein each R may be identical to or different from each other and represents methyl or ethyl.
[36] Further, as the dialkyl oxalate, dimethyl oxalate and diethyl oxalate are used.
[37] For optimization of the first reaction step in the present invention, the reaction solvent preferably employs a lower aliphatic alcohol which for an alkoxide component is present, such as methanol, ethanol or the like. For a molar ratio of reactants, 0.8 to
4.0 moles of dialkyl oxalate are used based on dialkyl thioglycolate. The reaction is carried out at a temperature of 60 to 12O0C for 4 to 12 hours. [38] After the reaction was complete, the resulting solid compound is washed with an extra reaction solvent to thereby remove the unreacted reactants and dried at a temperature of 60 to 7O0C under vacuum. [39] As Step 2, an activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene
produced in Step 1 is reacted with 1,2-dichlorotetraalkyldisilane to synthesize 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene having a structure in which a thiophene ring is connected to a silicon-containing hetero ring.
[40] The reaction for Step 2 may be expressed as in Reaction Scheme 2 below: [41] Reaction Scheme 2 [42]
[43] wherein each R is as defined above.
[44] Step 2-1 is a the synthesis step of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene having a structure in which a thiophene ring is connected to a silicon- containing hetero ring, from the reaction of an activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene produced in Step 1 with 1 ,3-dichloro- 1 , 1 ,3,3-tetraalkyldisiloxane.
[45] The reaction for Step 2-1 may be expressed as in Reaction Scheme 3 below:
[46] Reaction Scheme 3
[47]
[48] wherein each R is as defined above.
[49] In order to optimize the reactions of Step 2 and Step 2- 1 , a solvent having a boiling point of 60 to 1000C is employed. [50] Examples of the solvent that can be used in the present invention may include methanol, ethanol and toluene. These solvents may be used alone or in any combination thereof. [51] As a proper reaction molar ratio, 0.5 to 1.5 moles of a silicon reactant are used
based on the activated intermediate of 2,5-dicarboalkoxy-3,4-dioxythiophene. The reaction is carried out for 3 to 6 hours. [52] Step 3 is saponification of 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene using an aqueous solution of an alkali metal salt having strong basicity. As the alkali metal salt, sodium hydroxide and potassium hydroxide are used.
The subsequent process employs various kinds of acids such as hydrochloric acid, nitric acid and sulfuric acid.
[53] The reaction for Step 3 may be expressed as in Reaction Scheme 4 below:
[54] Reaction Scheme 4
[55]
[56] wherein each R is as defined above.
[57] Step 3-1 is saponification of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene using an aqueous solution of an alkali metal salt having strong basicity. As the alkali metal salt, sodium hydroxide and potassium hydroxide are used.
The subsequent process employs various kinds of acids such as hydrochloric acid, nitric acid and sulfuric acid.
[58] The reaction for Step 3-1 may be expressed as in Reaction Scheme 5 below:
[59] Reaction Scheme 5
[60]
[61] wherein each R is as defined above.
[62] In order to optimize the reactions of Step 3 and Step 3-1, the alkali metal salt is
used in a content of 3 to 10% by weight, and the acid is used in a content of 1 to 10% by weight.
[63] The reaction is carried out at a temperature of 100 to 15O0C for 1 to 10 hours. [64] Finally, Step 4 is decarboxylation of 2,5-dicarboalkoxy-3,4-tetraalkyldisilylene dioxythiophene, which is carried out under a reduced atmosphere to thereby obtain 3 ,4-tetraalkyldisilylene dioxythiophene.
[65] The reaction for Step 4 may be expressed as in Reaction Scheme 6 below: [66] [67] Reaction Scheme 6 [68]
[69] wherein each R is as defined above. [70] [71] Step 4-1 is decarboxylation of 2,5-dicarboalkoxy-3,4-tetraalkyldisiloxylene dioxythiophene, which is carried out under a reduced atmosphere to thereby obtain 3 ,4-tetraalkyldisiloxylene dioxythiophene.
[72] The reaction for Step 4-1 may be expressed as in Reaction Scheme 7 below: [73] [74] Reaction Scheme 7 [75]
[76] wherein each R is as defined above.
[77] In order to optimize the reactions of Step 4 and Step 4-1 in the present invention,
various kinds of solvents such as polyethylene glycol, dibutylphthalate, tetramethyl sulfone, and the like are used. The reaction vessel is maintained at a pressure of 0.2 to 0.35 mbar. The reaction is then carried out at a temperature of 80 to 12O0C for 6 to 24 hours. The final compound thus obtained is distilled at a pressure of 0.1 mbar. Mode for the Invention
[78] EXAMPLES
[79] Now, the present invention will be described in more detail with reference to the following Examples. These examples are provided only for illustrating the present invention and should not be construed as limiting the scope and spirit of the present invention.
[80] Example 1
[81] A IL 3-neck flask was equipped with an impeller stirrer, a reflux condenser and a dropping funnel and was then flame-dried with a nitrogen purge.
[82] 57.7 g (0.30 mol) of a 28% sodium methoxide solution and 25 g of methanol were placed and stirred in the 3-neck flask.
[83] A mixture of 30.7 g (0.15 mol) of 98% diethyl thioglycolate and 25.18 g (0.15 mol) of diethyl oxalate was placed in the dropping funnel and was then added dropwise at a temperature of 0 to 50C over 30 min.
[84] The mixture was stirred at room temperature for 1 hour and then stirred at 6O0C under reflux for another 3 hours to complete the reaction.
[85] When it begins to form a yellow diethyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt, the solvent is refluxed by the exothermic reaction.
[86] After the reaction was complete, the reactants were cooled to room temperature and washed three times with 60 mL of methanol, followed by drying at a temperature of 60 to 7O0C under vacuum.
[87] 82 g (0.27 mol) of the thus-dried dialkyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt and 550 g of ethanol were placed in a 2L reaction vessel having a plane ground joint and equipped with an impeller stirrer, a reflux condenser, a thermometer and a dropping funnel, and 50.55 g (0.27 mol) of 1,2-dichlorotetramethyldisilane and 50 g of ethanol were placed in the dropping funnel and were then added dropwise at 5O0C.
[88] Next, the reaction mixture was stirred at 8O0C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was then gradually added thereto via the dropping funnel.
[89] The reaction mixture was extracted three times with 500 mL of chloroform and dried over magnesium sulfate, followed by removal of the solvent under vacuum.
[90] 800 mL of an aqueous potassium hydroxide (84 g, 1.50 mol) solution was added
dropwise to the thus-obtained white solids, and the mixture was stirred at 7O0C under reflux for 2 hours, such that the mixture is completely dissolved.
[91] The solution of the reaction vessel was concentrated under vacuum to a total volume of 400 mL, and then 168 mL of cone. HCl was gradually added dropwise at O0C to thereby give white solids with completion of the reaction.
[92] After stirring for another 2 hours at room temperature, the resulting 3,4-tetramethyldisilylenedioxythiophene carboxylic acid was dried under vacuum. [93] 1200 mL of tetramethylene sulfone was introduced into the flask under stirring, and 240 g (0.75 mol) of 3,4-tetramethyldisilylenedioxythiophene carboxylic acid was then added thereto. The resulting mixture was heated to 950C under pressure of 0.35 mbar over 2 hours.
[94] When the reaction was complete, the reactants were cooled to room temperature and 3,4-tetramethyldisilylenedioxythiophene was distilled under vacuum (0.3 mbar) to thereby afford 27.65 g (0.12 mol) of a desired product (yield: 80%).
[95] Table 1 [96]
[97] Example 2 [98] A IL 3-neck flask was equipped with an impeller stirrer, a reflux condenser and a dropping funnel and was then flame-dried with a nitrogen purge.
[99] 69.23 g (0.36 mol) of a 28% sodium methoxide solution and 25 g of methanol were placed and stirred in the 3-neck flask. [100] A mixture of 37.13 g (0.18 mol) of 98% diethyl thioglycolate and 26.30 g (0.18 mol) of diethyl oxalate was placed in the dropping funnel and was then added dropwise at a temperature of 0 to 50C over 30 min.
[101] The mixture was stirred at room temperature for 1 hour and then stirred at 6O0C under reflux for another 3 hours to complete the reaction. [102] When it begins to form a yellow diethyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt, the solvent is refluxed by the exothermic reaction. [103] After the reaction was complete, the reactants were cooled to room temperature and washed three times with 60 mL of methanol, followed by drying at a temperature of 60
to 700C under vacuum.
[104] 50 g (0.16 mol) of the thus-dried dialkyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt and 550 g of ethanol were placed in a 2L reaction vessel having a plane ground joint and equipped with an impeller stirrer, a reflux condenser, a thermometer and a dropping funnel, and 32.51 g (0.16 mol) of l,3-dichloro-l,l,3,3-tetramethyldisiloxane and 50 g of ethanol were placed in the dropping funnel and were then added dropwise at 500C.
[105] Next, the reaction mixture was stirred at 800C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was gradually added thereto via the dropping funnel.
[106] The reaction mixture was extracted three times with 500 mL of chloroform and dried over magnesium sulfate, followed by removal of the solvent under vacuum.
[107] 500 mL of an aqueous potassium hydroxide (50 g, 0.99 mol) solution was added dropwise to the thus-obtained white solids, and the mixture was stirred at 700C under reflux for 2 hours, such that the mixture is completely dissolved.
[108] The solution of the reaction vessel was concentrated under vacuum to a total volume of 200 mL, and then 100 mL of cone. HCl was gradually added dropwise at 00C to thereby give white solids with completion of the reaction.
[109] After stirring for another 2 hours at room temperature, the resulting
3,4-tetramethyldisilylenedioxythiophene carboxylic acid was dried under vacuum.
[110] 1200 mL of tetramethylene sulfone was introduced into the flask under stirring, and
50 g (0.15 mol) of 3,4-tetramethyldisilylenedioxythiophene carboxylic acid was then added thereto. The resulting mixture was heated to 800C under pressure of 0.2 mbar over 2 hours.
[I l l] When the reaction was complete, the reactants were cooled to room temperature and 3,4-tetramethyldisilylenedioxythiophene was distilled under vacuum (0.3 mbar) to thereby afford 28.64 g (0.12 mol) of a desired product (yield: 66%).
[112] Example 3
[113] 25 g (82.17 mmol) of diethyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt, which was synthesized and dried in the same manner as in Example 2, and 300 g of ethanol were placed in a 2L reaction vessel having a plane ground joint and equipped with an impeller stirrer, a reflux condenser, a thermometer and a dropping funnel, and 25.92 g (82.20 mmol) of l,3-dichloro-l,l,3,3-tetraisopropyldisiloxane and 35 g of ethanol were placed in the dropping funnel and were then added dropwise at 50°C.
[114] Next, the reaction mixture was stirred at 800C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was gradually added thereto via the dropping funnel.
[115] The reaction mixture was extracted three times with 150 mL of chloroform and dried over magnesium sulfate, followed by vacuum concentration of the solution to make a final volume of 250 mL.
[116] To the white solids obtained from low-temperature recrystallization of the thus- prepared solution was added dropwise 300 mL of an aqueous sodium hydroxide (30 g, 0.75 mol) solution, and the mixture was stirred at 7O0C under reflux for 2 hours, such that the mixture is completely dissolved.
[117] The solution of the reaction vessel was concentrated under vacuum to a total volume of 200 mL, and then 100 mL of cone. HCl was gradually added dropwise at O0C to thereby give white solids with completion of the reaction.
[118] After stirring for another 2 hours at room temperature, the resulting
3,4-tetraisopropyldisilylenedioxythiophene carboxylic acid was dried under vacuum.
[119] 800 mL of tetramethylene sulfone was introduced into the flask under stirring, and
34.83 g (77.98 mmol) of 3,4-tetraisopropyldisilylenedioxythiophene carboxylic acid was then added thereto. The resulting mixture was heated to 8O0C under 0.2 mbar over 2 hours.
[120] When the reaction was complete, the reactants were cooled to room temperature and extracted three times with 200 mL of chloroform. The resulting solution was concentrated under vacuum to a volume of 400 mL which was then subjected to low- temperature recrystallization to thereby afford 20.94 g (84.97 mmol) of 3,4-tetraisopropyldisilylenedioxythiophene (yield: 86%).
[121] Example 4
[122] 20 g (65.74 mmol) of diethyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt, which was synthesized and dried in the same manner as in Example 2, and 300 g of ethanol were placed in a 2L reaction vessel having a plane ground joint and equipped with an impeller stirrer, a reflux condenser, a thermometer and a dropping funnel, and 29.91 g (66.25 mmol) of l,3-dichloro-l,l,3,3-tetraphenyldisiloxane and 35 g of ethanol were placed in the dropping funnel and were then added dropwise at 5O0C.
[123] Next, the reaction mixture was stirred at 8O0C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was gradually added thereto via the dropping funnel.
[124] The reaction mixture was extracted three times with 150 mL of chloroform and dried over magnesium sulfate, followed by vacuum concentration of the solution to make a final volume of 250 mL.
[125] To clear solids obtained from low-temperature recrystallization of the thus-prepared solution was added dropwise 300 mL of an aqueous sodium hydroxide (30 g, 0.75 mol) solution, and the mixture was stirred at 7O0C under reflux for 2 hours, such that the mixture is completely dissolved.
[126] The solution of the reaction vessel was concentrated under vacuum to a total volume of 200 mL, and then 100 mL of cone. HCl was gradually added dropwise at O0C to thereby give white solids with completion of the reaction.
[127] After stirring for another 2 hours at room temperature, the resulting 3,4-tetraphenyldisilylenedioxythiophene carboxylic acid was dried under vacuum. [128] 1 L of tetramethylene sulfone was introduced into the flask under stirring, and 35.56 g (61.02 mmol) of 3,4-tetraphenyldisilylenedioxythiophene carboxylic acid was then added thereto. The resulting mixture was heated to 6O0C under pressure of 0.3 mbar over 2 hours.
[129] When the reaction was complete, the reactants were cooled to room temperature and extracted three times with 200 mL of chloroform. The resulting solution was concentrated under vacuum to a volume of 400 mL which was then subjected to low- temperature recrystallization to thereby afford 24.71 g (49.95 mmol) of 3,4-tetraphenyldisilylenedioxythiophene (yield: 71%).
[130] Table 2 [131]
Claims
[1] A process for preparing a conductive high-molecular weight organic silicon monomer, comprising: synthesizing a carboxylic acid derivative of Formula 5 or 6 from a silicon- containing compound of Formula 3 or 4 using a base; and decarboxylating the compound of Formula 5 or 6 under reduced conditions without use of a catalyst to prepare a thiophene derivative of Formula 1 or 2: (Formula 1)
(Formula 2)
(Formula 3)
(Formula 4)
(Formula 5)
(Formula 6)
[2] The process according to claim 1, wherein the organic silicon monomer has a Si- containing heterocycle which is attached to the 3,4-position of the thiophene ring. [3] The process according to claim 1, wherein the organic silicon monomer has a siloxane-containing heterocycle which is attached to the 3,4-position of the thiophene ring. [4] The process according to claim 1, wherein the decarboxylation is carried out at a pressure of 0.2 to 0.35 mbar.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2007-0045913 | 2007-05-11 | ||
| KR1020070045913A KR100885855B1 (en) | 2007-05-11 | 2007-05-11 | Manufacturing method for organic silicon monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2008140159A1 true WO2008140159A1 (en) | 2008-11-20 |
Family
ID=40002336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2007/005056 WO2008140159A1 (en) | 2007-05-11 | 2007-10-16 | Process for preparing organic silicon monomer |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100885855B1 (en) |
| WO (1) | WO2008140159A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2453103A (en) * | 1944-02-25 | 1948-11-02 | Du Pont | Decarboxylation of 3,4-dihydroxy-2,5-dicarboxythiophene |
| US20010034453A1 (en) * | 2000-04-04 | 2001-10-25 | Gunter Rauchschwalbe | Process for the preparation of dialkylthiophenes and alkylenedioxythiophenes |
| WO2003046106A1 (en) * | 2001-11-21 | 2003-06-05 | University Of Florida | Electrochromic polymers and polymer electrochromic devices |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060060776A (en) * | 2004-11-30 | 2006-06-05 | 오응주 | Method for manufacturing polythiophene derivatives soluble in organic solvents and application thereof |
-
2007
- 2007-05-11 KR KR1020070045913A patent/KR100885855B1/en active IP Right Grant
- 2007-10-16 WO PCT/KR2007/005056 patent/WO2008140159A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2453103A (en) * | 1944-02-25 | 1948-11-02 | Du Pont | Decarboxylation of 3,4-dihydroxy-2,5-dicarboxythiophene |
| US20010034453A1 (en) * | 2000-04-04 | 2001-10-25 | Gunter Rauchschwalbe | Process for the preparation of dialkylthiophenes and alkylenedioxythiophenes |
| WO2003046106A1 (en) * | 2001-11-21 | 2003-06-05 | University Of Florida | Electrochromic polymers and polymer electrochromic devices |
Non-Patent Citations (1)
| Title |
|---|
| BAEK N.S. ET AL.: "Direct synthesis and luminescent properties of new silicon-based alternating copolymers", SYNTHETIC METALS, vol. 121, no. 1-3, 2001, pages 1743 - 1744 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100885855B1 (en) | 2009-02-26 |
| KR20080099966A (en) | 2008-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1910447B1 (en) | Improved process for substituted polythiophene polymers | |
| KR20140000693A (en) | Novel spirobifluorene compounds | |
| TW200418864A (en) | Preparation of 2,2'-di(3,4-ethylenedioxythiophene)s | |
| JP2001288182A (en) | Method for producing dialkylthiophene and alkylenedioxythiophene | |
| US7202369B2 (en) | Processes for preparing of 3,4-alkylenedioxythiophenes and 3,4-dialkoxythiophenes | |
| JP2009224593A (en) | Organic conductive material for electronic device containing indolocarbazole derivative | |
| CN111285881B (en) | Thieno [3,4-b ] indole derivative and synthetic method thereof | |
| WO2008140159A1 (en) | Process for preparing organic silicon monomer | |
| US6433190B1 (en) | 3,6-Di(3′,5′-bis(fluoroalkyl) phenyl) pyromellitic dianhydride and method for the preparation thereof | |
| CN102863310B (en) | Rigid oligomer-fullerene copolymer and preparation method and application thereof | |
| CN115505100B (en) | Epoxy resin based on spirosilafluorene as framework, and preparation method and application thereof | |
| CN109422748B (en) | Method for synthesizing TNNI3K inhibitor | |
| US7141693B2 (en) | Process for producing β-oxonitrile compound or alkali metal salt thereof | |
| JP2009249355A (en) | Fluorinated fluorene derivative and method for producing the same | |
| JP2021172789A (en) | Method for producing charge-transporting polymer | |
| JPH10251401A (en) | Alkylene oxide oligomer having linear carbonate ester group and its production | |
| US11964939B2 (en) | Aromatic tetracarboxylic acid compound | |
| JP5854345B2 (en) | Method for producing dimer | |
| KR101233822B1 (en) | Polymer or derivatives with dioxidephenanthrothiadiazole thereof and photovoltaic device using the same | |
| JP2000256351A (en) | Bis(diarylamino)thiophene | |
| JP4475901B2 (en) | Method for producing 3-acetylthiophenes | |
| KR101316093B1 (en) | A preparation method of polythiopene derivatives | |
| KR20100113893A (en) | Process for the preparation of dialkoxythiophenes and alkylenedioxythiophenes | |
| JP2011144156A (en) | New terthiophene derivative and polymer thereof | |
| CN118812409A (en) | Diethylenetriamine type double Synthesis method of maleimide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07833365 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (THE COMMUNICATIONS FORMS 1205A DATED: 27/01/2010 AND 23/02/2010) |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 07833365 Country of ref document: EP Kind code of ref document: A1 |