KR20220168271A - Novel preparing method for regioselective 1,5-dimethyltetrazole - Google Patents
Novel preparing method for regioselective 1,5-dimethyltetrazole Download PDFInfo
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- HWHNFJYQDMSYAF-UHFFFAOYSA-N 1,5-dimethyltetrazole Chemical compound CC1=NN=NN1C HWHNFJYQDMSYAF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 17
- -1 chlorosilane compound Chemical class 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 12
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- UBXSSBYAEBFCRS-UHFFFAOYSA-N triazido(chloro)silane Chemical compound [N-]=[N+]=N[Si](Cl)(N=[N+]=[N-])N=[N+]=[N-] UBXSSBYAEBFCRS-UHFFFAOYSA-N 0.000 claims description 6
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- PKMGIQQHPJFMIA-UHFFFAOYSA-N azido(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)N=[N+]=[N-] PKMGIQQHPJFMIA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- TZLVRPLSVNESQC-UHFFFAOYSA-N potassium azide Chemical compound [K+].[N-]=[N+]=[N-] TZLVRPLSVNESQC-UHFFFAOYSA-N 0.000 claims description 3
- SZJFGTWFLXTOHF-UHFFFAOYSA-N silicon tetraazide Chemical compound [N-]=[N+]=N[Si](N=[N+]=[N-])(N=[N+]=[N-])N=[N+]=[N-] SZJFGTWFLXTOHF-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001540 azides Chemical class 0.000 claims description 2
- QDDNUCYMNPKKGC-UHFFFAOYSA-N diazido(dichloro)silane Chemical compound [N-]=[N+]=N[Si](Cl)(Cl)N=[N+]=[N-] QDDNUCYMNPKKGC-UHFFFAOYSA-N 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- 239000010887 waste solvent Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- HVRBCXZGTURXBT-UHFFFAOYSA-N 2,5-dimethyltetrazole Chemical compound CC=1N=NN(C)N=1 HVRBCXZGTURXBT-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007069 methylation reaction Methods 0.000 description 6
- WACDNDXNBSEKRZ-UHFFFAOYSA-N 2-tert-butyl-5-methyltetrazole Chemical compound CC=1N=NN(C(C)(C)C)N=1 WACDNDXNBSEKRZ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000011987 methylation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000008431 aliphatic amides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- IJIBRSFAXRFPPN-UHFFFAOYSA-N 5-bromo-2-methoxybenzaldehyde Chemical compound COC1=CC=C(Br)C=C1C=O IJIBRSFAXRFPPN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008430 aromatic amides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- BICAGYDGRXJYGD-UHFFFAOYSA-N hydrobromide;hydrochloride Chemical compound Cl.Br BICAGYDGRXJYGD-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
본 발명은 위치 선택적인 1,5-디메틸테트라졸의 신규 제조방법 등에 관한 것이다. The present invention relates to a novel method for preparing regioselective 1,5-dimethyltetrazole and the like.
반도체 공정에서 테트라졸(tetrazole) 유도체들은 분자내에 질소 함유량이 높아서 메탈 세정에 탁월한 효과를 발휘한다. 대표적인 예로 5-아미노테트라졸(5-aminotetrazole, 5-ATZ)와 5-메틸테트라졸(5-methyltetrazole, 5-MTZ)가 있다. 5-ATZ는 구리(Cu) 식각액의 핵심 첨가제로서 오랫동안 사용되었으나, 세정 후에 얼룩이 남는 단점이 있다. In the semiconductor process, tetrazole derivatives have a high nitrogen content in the molecule, so they have an excellent effect in metal cleaning. Representative examples include 5-aminotetrazole (5-ATZ) and 5-methyltetrazole (5-MTZ). 5-ATZ has been used as a key additive for copper (Cu) etchants for a long time, but it has a disadvantage of leaving stains after cleaning.
5-ATZ의 단점을 보완하기 위해서 5-MTZ가 사용되었고, 5-MTZ는 은(Ag)의 과식각을 막아 좁은 화소 전극(Pixel)의 배선을 형성할 수 있어 미세한 패턴의 제조를 용이하게 할 수 있으며, 식각속도를 조절하여 공정상 컨트롤을 용이하게 할 수 있는 효과가 있으며, 잔사 및 재흡착이 발생하지 않으며, 경시 안정성이 우수한 장점이 있다. 하지만 최근 세정시 5-MTZ가 반도체 미세공정에서 결함이 발생되어 불량률이 증가하여 점점 사용하지 않는 추세이다.5-MTZ is used to compensate for the disadvantages of 5-ATZ, and 5-MTZ prevents over-etching of silver (Ag) to form narrow pixel electrode wiring, facilitating the manufacture of fine patterns. It has an effect of facilitating process control by adjusting the etching rate, no residue and re-adsorption, and excellent stability over time. However, in recent years, 5-MTZ has been increasingly discontinued due to an increase in the defect rate due to the occurrence of defects in semiconductor microprocessing during cleaning.
식각조성의 다음세대에 대한 연구가 활발히 진행되고 있으며, US 9,394,616은 식각액으로 1,5-디메틸테트라졸을 보고한 바 있다. 본 발명의 대상인 1,5-디메틸테트라졸은 차세대 식각액으로서 하나의 대안이 될 것으로 기대된다.Research on the next generation of etching compositions is being actively conducted, and US 9,394,616 has reported 1,5-dimethyltetrazole as an etching solution. 1,5-dimethyltetrazole, which is the subject of the present invention, is expected to be an alternative as a next-generation etchant.
1,5-디메틸테트라졸의 제조방법은 Mendeleev Communications (1995), (1), 10-11., Journal of Heterocyclic Chemistry (2015), 52(5), 1483-1487., Chemical Communications (Cambridge, United Kingdom) (2015), 51(99), 17627-17629. 등에 개시되어 있다.The preparation method of 1,5-dimethyltetrazole is Mendeleev Communications (1995), (1), 10-11., Journal of Heterocyclic Chemistry (2015), 52(5), 1483-1487., Chemical Communications (Cambridge, United Kingdom) (2015), 51(99), 17627-17629. etc. are disclosed.
선행문헌에 따르면, 하기 반응식 1에 도시한 바와 같이, 1,5-디메틸테트라졸은 먼저 5-메틸테트라졸을 합성한 후, 메틸화 시약을 사용하여 메틸레이션을 하는 방법으로 주로 제조한다.According to the prior literature, as shown in Scheme 1 below, 1,5-dimethyltetrazole is mainly prepared by first synthesizing 5-methyltetrazole and then performing methylation using a methylation reagent.
[반응식 1][Scheme 1]
상업적으로 대량생산 가능한 5-메틸테트라졸(3)의 제조방법으로는 샤플리스(Sharpless)의 제조방법(J. Org. Chem. 2001, 66, 7945-7950)이 주로 사용되고 있다. 아세토니트릴(acetonitrile)을 출발물질로 하여 소듐아자이드와 염화아연 또는 염화브롬화물을 사용하여 고온 고압에서 5-메틸테트라졸을 생산한다. 상온, 상압조건(25℃, 1기압)에서는 반응시간이 훨씬 길어져서 공정시간이 증가하는 단점이 있다. As a method for producing 5-methyltetrazole (3) that can be commercially mass-produced, the Sharpless method (J. Org. Chem. 2001, 66, 7945-7950) is mainly used. 5-methyltetrazole is produced at high temperature and high pressure using acetonitrile as a starting material and sodium azide and zinc chloride or bromide chloride. At room temperature and normal pressure conditions (25° C., 1 atm), the reaction time is much longer, which increases the process time.
한편, 5-메틸테트라졸의 메틸화반응을 살펴보면, 상기 보고된 문헌(Journal of Heterocyclic Chemistry (2015), 52(5), 1483-1487.)은 메틸화 반응시약으로 디메틸카보네이트(dimethylcarbonate)를 사용하였으며, 이 때 컬럼수율은 67%이고, 이성질체인 2,5-디메틸테트라졸이 함께 수득된다. 또 다른 문헌(Chemical Communications (Cambridge, United Kingdom) (2015), 51(99), 17627-17629.)은 메틸화 반응시약으로 메틸아이오다이드(methyliodide)를 사용하였으며, 이 때 컬럼수율은 62%이고, 이성질체인 2,5-디메틸테트라졸이 함께 수득된다. 즉, 이전에 보고된 방법은 이성질체를 제거해야 하는 불편함이 있으며, 반응 수율도 좋지 못하다는 단점이 있다.On the other hand, looking at the methylation reaction of 5-methyltetrazole, the reported literature (Journal of Heterocyclic Chemistry (2015), 52(5), 1483-1487.) used dimethylcarbonate as a methylation reaction reagent, At this time, the column yield was 67%, and 2,5-dimethyltetrazole, an isomer, was obtained together. Another literature (Chemical Communications (Cambridge, United Kingdom) (2015), 51(99), 17627-17629.) used methyliodide as a methylation reaction reagent, and the column yield was 62%. , the isomer 2,5-dimethyltetrazole is obtained together. That is, the previously reported method has the disadvantage of having to remove isomers, and the reaction yield is also poor.
1,5-디메틸테트라졸의 또 다른 제조방법으로는 하기 반응식 2에 도시한 바와 같이, 5-메틸테트라졸을 출발물질로 사용하고, t-부틸알코올과 황산을 이용해 2번 위치에 t-부틸기를 도입한 후, 입체선택성을 이용하여 1번 위치에 메틸화를 한 후, t-부틸기를 제거하는 방법이다. 하지만 이 방법은 고온의 반응조건을 요구하고, 소모성 도입과 제거반응이 있어 상업적 생산에는 다소 무리가 있다.As another method for preparing 1,5-dimethyltetrazole, as shown in Scheme 2 below, 5-methyltetrazole is used as a starting material and t-butyl alcohol and sulfuric acid are used to form t-butyl at position 2. This is a method in which a group is introduced, methylation is performed at position 1 using stereoselectivity, and then the t-butyl group is removed. However, this method requires high-temperature reaction conditions and has consumptive introduction and elimination reactions, making it somewhat unreasonable for commercial production.
[반응식 2][Scheme 2]
이외에도 아세톤을 출발물질로 하여 하이드록실 아민을 이용해서 옥심을 합성한 후, 이탈기를 보호한 다음 소듐아자이드와 트리메틸실릴 트리플루오로메탄설포네이트를 이용해서 1,5-디메틸테트라졸을 합성하는 방법 (Bulletin of the Chemical Society of Japan (1985), 58(8), 2419-20.)이 있으나, 이는 반응공정이 매우 길고 수율이 낮아서 경제성이 떨어진다는 단점이 있다.In addition, after synthesizing an oxime using hydroxyl amine using acetone as a starting material, protecting the leaving group, and then synthesizing 1,5-dimethyltetrazole using sodium azide and trimethylsilyl trifluoromethanesulfonate (Bulletin of the Chemical Society of Japan (1985), 58(8), 2419-20.), but this has the disadvantage that the reaction process is very long and the yield is low, resulting in poor economic efficiency.
따라서, 본 발명자는 제조공정과 제조시간을 줄여 보다 경제적으로 1,5-디메틸테트라졸을 제조하는 방안을 연구하여 본 발명을 완성하였다.Therefore, the present inventors completed the present invention by studying a method of manufacturing 1,5-dimethyltetrazole more economically by reducing the manufacturing process and manufacturing time.
본 발명이 이루고자 하는 기술적 과제는 1,5-디메틸테트라졸의 제조방법을 제공하는 것이다.A technical problem to be achieved by the present invention is to provide a method for producing 1,5-dimethyltetrazole.
그러나 본 발명이 이루고자 하는 기술적 과제는 이상에서 언급한 과제에 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당해 기술분야의 통상의 기술자에게 명확하게 이해될 수 있을 것이다.However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.
상기 과제를 해결하기 위하여, 본 발명은 하기 단계를 포함하는 1,5-디메틸테트라졸의제조방법을 제공한다.In order to solve the above problems, the present invention provides a method for preparing 1,5-dimethyltetrazole comprising the following steps.
(1) N-메틸아세트아마이드(N-methylacetamide)를 클로로실란 화합물 및 아자이드 화합물과 반응시키는 단계; 및(1) reacting N-methylacetamide with a chlorosilane compound and an azide compound; and
(2) 상기 반응의 생성물을 결정화하는 단계.(2) crystallizing the product of the reaction.
본 발명의 일 구현예로서, 상기 (2) 단계에서 결정화 용매는 자체적으로 수소결합을 형성하지 않는 것일 수 있다.As an embodiment of the present invention, the crystallization solvent in step (2) may not form a hydrogen bond with itself.
본 발명의 다른 구현예로서, 상기 클로로실란 화합물은 트리메틸실란, 테트라클로로실란, 디클로로디아지도실란, 트리아지도클로로실란, 및 트리클로로아지도실란으로 이루어진 군으로부터 선택되는 어느 하나 이상일 수 있다.As another embodiment of the present invention, the chlorosilane compound may be at least one selected from the group consisting of trimethylsilane, tetrachlorosilane, dichlorodiadosilane, triazidochlorosilane, and trichloroazidosilane.
본 발명의 다른 구현예로서, 상기 아자이드 화합물은 소듐아자이드, 칼륨아자이드, 트리부틸아자이드, 및 테트라아지도실란으로 이루어진 군으로부터 선택되는 어느 하나 이상일 수 있다.As another embodiment of the present invention, the azide compound may be at least one selected from the group consisting of sodium azide, potassium azide, tributyl azide, and tetraazidosilane.
본 발명의 또 다른 구현예로서, 상기 결정화 용매는 노말헥산, 사이클로헥산, 노말헵탄, 노말펜탄, 디에틸에테르, 이소프로필에테르, 메틸 t-부틸에테르, 에틸아세테이트, 메틸아세테이트, 이소프로필아세테이트 및 이들의 혼합물로 이루어진 군으로부터 선택되는 어느 하나 이상일 수 있다.As another embodiment of the present invention, the crystallization solvent is normal hexane, cyclohexane, normal heptane, normal pentane, diethyl ether, isopropyl ether, methyl t-butyl ether, ethyl acetate, methyl acetate, isopropyl acetate and these It may be any one or more selected from the group consisting of a mixture of.
본 발명의 또 다른 구현예로서, 상기 결정화 용매는 끓는점이 65 내지 100℃인 것일 수 있으며, 바람직하게는 헵탄 또는 이소프로필에테르일 수 있다.As another embodiment of the present invention, the crystallization solvent may have a boiling point of 65 to 100° C., and may preferably be heptane or isopropyl ether.
본 발명의 다른 구현예로서, 상기 (1) 단계에서, N-메틸아세트아마이드, 클로로실란 화합물, 및 아자이드 화합물의 몰비는 1 : 1 : 1 내지 1 : 1 : 10인 것일 수 있으며, 바람직하게는 1 : 1 : 2 내지 1 : 1 : 3일 수 있다.As another embodiment of the present invention, in step (1), the molar ratio of N-methylacetamide, the chlorosilane compound, and the azide compound may be 1:1:1 to 1:1:10, preferably may be 1:1:2 to 1:1:3.
본 발명의 다른 구현예로서, 상기 (1) 단계의 용매는 아세토니트릴, 테트라하이드로퓨란, 디메틸포름아마이드, 디메틸설폭사이드, 디메틸아세트아마이드, 아세톤, N-메틸피롤리돈, 및 이들의 혼합물로 이루어진 군으로부터 선택되는 어느 하나 이상일 수 있다.As another embodiment of the present invention, the solvent in step (1) is composed of acetonitrile, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, acetone, N-methylpyrrolidone, and mixtures thereof. It may be any one or more selected from the group.
본 발명의 다른 구현예로서, 상기 (1) 단계는, 상기 N-메틸아세트아마이드, 클로로실란 화합물, 및 아자이드 화합물을 첨가한 후 4 내지 6 시간동안 환류교반하는 것일 수 있으며, 바람직하게는 5 시간동안 환류교반하는 것일 수 있다.As another embodiment of the present invention, in step (1), after adding the N-methylacetamide, the chlorosilane compound, and the azide compound, reflux stirring may be performed for 4 to 6 hours, preferably 5 It may be reflux stirring for a period of time.
본 발명의 다른 구현예로서, 상기 (1) 단계 이후 (2) 단계 이전에, 하기의 단계를 추가적으로 포함하는 것일 수 있다.As another embodiment of the present invention, after step (1) and before step (2), the following steps may be additionally included.
(a) 냉각 후 메탄올을 적가하는 단계;(a) adding methanol dropwise after cooling;
(b) 메틸렌클로라이드를 첨가한 후 셀라이트를 통해 여과하는 단계; 및(b) filtering through celite after adding methylene chloride; and
(c) 용매를 감압농축하는 단계.(c) concentrating the solvent under reduced pressure.
본 발명은 N-메틸아세트아마이드, 클로로실란 화합물 및 아자이드 화합물을 이용한 1,5-디메틸테트라졸 제조방법에 관한 것으로서, 5-메틸테트라졸 중간체를 거치지 않아 공정이 간단하고, 불필요한 폐수와 폐용매가 발생하지 않으며, 수소결합을 형성하지 않는 결정화 용매를 사용하여 건조 및 정제공정 등이 단순하여 제조원가를 크게 절감할 수 있고, 반응시간이 짧고 반응조건이 비교적 온화하여 고압반응기와 같은 고가의 제조설비를 필요로 하지 않아, 높은 수율 및 순도의 1,5-디메틸테트라졸을 효율적으로 제조할 수 있다.The present invention relates to a method for producing 1,5-dimethyltetrazole using N-methylacetamide, a chlorosilane compound, and an azide compound, and the process is simple because it does not go through a 5-methyltetrazole intermediate, and unnecessary wastewater and waste solvent are eliminated. does not occur, and by using a crystallization solvent that does not form a hydrogen bond, the drying and purification processes are simple, so the manufacturing cost can be greatly reduced, and the reaction time is short and the reaction conditions are relatively mild, requiring expensive manufacturing equipment such as a high-pressure reactor. , it is possible to efficiently produce 1,5-dimethyltetrazole in high yield and purity.
도 1은 1,5-디메틸테트라졸의 1H NMR 결과를 나타낸 것이다.
도 2는 2,5-디메틸테트라졸의 1H NMR 결과를 나타낸 것이다.
도 3은 1,5-디메틸테트라졸 : 2,5-디메틸테트라졸을 3 : 1 비율로 분석한 1H NMR 결과를 나타낸 것이다.
도 4는 2-(t-부틸)-5-메틸테트라졸의 1H NMR 결과를 나타낸 것이다.1 shows the 1 H NMR results of 1,5-dimethyltetrazole.
Figure 2 shows the 1 H NMR results of 2,5-dimethyltetrazole.
3 shows 1 H NMR results obtained by analyzing 1,5-dimethyltetrazole:2,5-dimethyltetrazole at a ratio of 3:1.
4 shows the 1 H NMR results of 2-(t-butyl)-5-methyltetrazole.
본 발명을 좀 더 구체적으로 설명하기 전에, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정되어서는 아니되며, 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Before describing the present invention in more detail, the terms or words used in this specification and claims should not be limited to their usual or dictionary meanings, and the concept of terms is appropriately used to describe the invention in the best way. It should be interpreted as a meaning and concept consistent with the technical spirit of the present invention based on the principle that it can be defined in the following way.
본 발명은 지방족 아마이드(aliphatic amides)에 클로로실란(chlorosilane) 화합물과 아자이드(azide) 화합물을 이용하여 위치선택적으로 1,5-디메틸테트라졸(1,5-dimethyltetrazole)을 제조하는 방법에 관한 것이다.The present invention relates to a method for regioselectively producing 1,5-dimethyltetrazole by using aliphatic amides, a chlorosilane compound and an azide compound. .
보다 구체적으로, 본 발명은 N-메틸아세트아마이드(N-methylacetamide)와 트리아지도클로로실란(triazidochlorosilane)을 이용하여 불필요한 폐수와 폐용매 발생 없이 효율적으로 1,5-디메틸테트라졸을 대량생산할 수 있다.More specifically, the present invention can efficiently mass-produce 1,5-dimethyltetrazole without generating unnecessary wastewater and waste solvent using N-methylacetamide and triazidochlorosilane.
본 발명의 반응을 하기 반응식 3에 도시하였다.The reaction of the present invention is shown in
[반응식 3][Scheme 3]
먼저, N-메틸아세트아마이드와 트리아지도클로로실란이 반응하여 이미도일실릴에테르(imidoyl silyl ether)를 생성되고 이어서 N-메틸 아세트이미도일 아자이드가 형성된 후 테트라졸이 형성되면서 목적화합물인 1,5-디메틸테트라졸이 만들어지게 된다.First, N-methylacetamide and triazidochlorosilane react to produce imidoylsilyl ether, then N-methylacetimidoylazide is formed, and then tetrazole is formed to form the target compound 1,5 - Dimethyltetrazole is produced.
즉, 본 발명은 촉매의 도움 없이 지방족 아마이드 또는 방향족 아마이드에서 나이트릴을 거치지 않고 1,5-디메틸테트라졸을 위치선택적으로 합성할 수 있는 효율적인 방법으로서, N-메틸아세트아마이드를 출발물질로 사용하여 트리아지도클로로실란을 이용하여 5-메틸테트라졸 유도체를 거치지 않고 단일공정으로 정제 또는 추출공정 없이 고순도의 1,5-디메틸테트라졸을 제조할 수 있다. 중간체의 분리공정이 없는바 폐수와 폐용매 처리비용을 획기적으로 절감할 수 있고, 여러단계 반응을 한 단계로 줄이는 효과가 있으며, 기존 연구에 비해 온화한 조건에서 더 높은 수율을 나타낸다는 장점이 있다.That is, the present invention is an efficient method for regioselectively synthesizing 1,5-dimethyltetrazole from aliphatic amide or aromatic amide without the aid of a catalyst without going through nitrile, using N-methylacetamide as a starting material. High-purity 1,5-dimethyltetrazole can be produced by using triazidochlorosilane in a single process without going through a 5-methyltetrazole derivative and without a purification or extraction process. Since there is no separation process of intermediates, wastewater and waste solvent treatment costs can be drastically reduced, there is an effect of reducing a multi-step reaction into one step, and it has the advantage of showing a higher yield under mild conditions compared to existing studies.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 이하 특정 실시예들을 도면에 예시하고 상세한 설명에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.The present invention can apply various transformations and can have various embodiments. Hereinafter, specific embodiments will be illustrated in the drawings and described in detail in the detailed description. However, it should be understood that this is not intended to limit the present invention to specific embodiments, and includes all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.
실시예 1 : 1,5-디메틸테트라졸의 제조Example 1: Preparation of 1,5-dimethyltetrazole
500 mL 3구 라운드 플라스크에 N-메틸아세트아마이드 14.62 g을 투입한 후 아세토니트릴 240 mL를 넣었다. 이어서 소듐아자이드 35.1 g, 테트라클로로실란 34 g을 넣은 후 5 시간동안 환류 교반하였다. 반응 종결을 확인한 후 내부 온도를 10℃로 냉각한다음 메탄올 26 g을 천천히 반응용액에 적가하였다. 이어서 정제수 7.2 g을 천천히 반응용액에 적가하고 메틸렌클로라이드 55 mL를 투입하고 30 분동안 교반하였다. 1 시간동안 교반 후 셀라이트를 통해 여과하고 메틸렌클로라이드로 세척하였다. 용매를 감압농축하고 헵탄으로 결정화한 후 45℃에서 8 시간동안 진공건조하여 백색결정 17.07 g(수율 87%), 순도 99.96%를 얻었다.After adding 14.62 g of N-methylacetamide to a 500 mL three-necked round flask, 240 mL of acetonitrile was added thereto. After adding 35.1 g of sodium azide and 34 g of tetrachlorosilane, the mixture was stirred under reflux for 5 hours. After confirming the completion of the reaction, the internal temperature was cooled to 10° C., and then 26 g of methanol was slowly added dropwise to the reaction solution. Subsequently, 7.2 g of purified water was slowly added dropwise to the reaction solution, and 55 mL of methylene chloride was added thereto, followed by stirring for 30 minutes. After stirring for 1 hour, the mixture was filtered through celite and washed with methylene chloride. The solvent was concentrated under reduced pressure, crystallized with heptane, and vacuum dried at 45° C. for 8 hours to obtain 17.07 g of white crystals (yield: 87%) with a purity of 99.96%.
이 때, 용매로서 아세토니트릴 대신에 테트라하이드로퓨란, 디메틸포름아마이드, 디메틸설폭사이드, 디메틸아세트아마이드, 아세톤, N-메틸리폴리돈, 및 이들의 혼합물로 이루어진 군으로부터 선택되는 어느 하나 이상의 화합물이 사용될 수 있다.At this time, instead of acetonitrile as a solvent, one or more compounds selected from the group consisting of tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, acetone, N-methyllipidone, and mixtures thereof may be used. can
아자이드 화합물로서 소듐아자이드 대신에 칼륨아자이드, 트리부틸틴아자이드, 및 테트라아지도실란으로 이루어진 군으로부터 선택되는 어느 하나 이상의 화합물이 사용될 수 있다.As the azide compound, any one or more compounds selected from the group consisting of potassium azide, tributyltin azide, and tetraazidosilane may be used instead of sodium azide.
클로로실란 화합물로서 테트라클로로실란 대신에 트리메틸실란, 테트라클로로실란, 디클로로디아지도실란, 트리아지도클로로실란, 및 트리클로로아지도실란으로 이루어진 군으로부터 선택되는 어느 하나 이상의 화합물이 사용될 수 있다.As the chlorosilane compound, any one or more compounds selected from the group consisting of trimethylsilane, tetrachlorosilane, dichlorodiazidosilane, triazidochlorosilane, and trichloroazidosilane may be used instead of tetrachlorosilane.
실시예 2 : 1,5-디메틸테트라졸의 제조Example 2: Preparation of 1,5-dimethyltetrazole
실시예 1과 동일하게 수행하나, 결정화 용매를 이소프로필에테르로 바꾼 경우, 백색결정 16.3 g(수율 83%), 순도 99.98%를 얻었다.It was carried out in the same manner as in Example 1, but when the crystallization solvent was changed to isopropyl ether, 16.3 g of white crystals (yield: 83%) with a purity of 99.98% were obtained.
비교예 1 : 1,5-디메틸테트라졸의 제조Comparative Example 1: Preparation of 1,5-dimethyltetrazole
2 L 3구 라운드 플라스크에 콘덴서를 연결하고 냉매를 순환시킨 후 정제수 240 g과 가성소다 55.2 g을 넣고 15 분동안 교반한다. 완전용해를 확인하고 5-메틸테트라졸 100.9 g을 넣고 이어서 디메틸설페이트 166.5 g과 아세톤 320 mL을 투입하고 3 시간동안 환류교반하였다. 용매를 감압 하에 제거하고 메틸렌클로라이드를 추출하고 탈수 후 감압농축하여 용매를 제거하고 NMR 분석을 수행하였다(1,5-디메틸테트라졸:2,5-디메틸테트라졸 = 3:1)(도 1 내지 3). 이소프로필에테르 800 mL을 넣고 1 시간동안 실온에서 교반하고 10℃로 냉각하고 30 분 교반한다음 여과를 실시하여 고체를 얻었다. 습체를 45℃에서 8 시간 건조하여 1,5-디메틸테트라졸 63.58 g(수율 54%)을 얻었다. 여과액을 감압농축하여 제거하고 진공증류하여 이성질체인 2,5-디메틸테트라졸 20 g(수율 17%)을 얻었다.Connect a condenser to a 2 L three-necked round flask, circulate the refrigerant, add 240 g of purified water and 55.2 g of caustic soda, and stir for 15 minutes. After confirming complete dissolution, 100.9 g of 5-methyltetrazole was added, followed by 166.5 g of dimethyl sulfate and 320 mL of acetone, followed by stirring under reflux for 3 hours. The solvent was removed under reduced pressure, methylene chloride was extracted, dehydrated, concentrated under reduced pressure to remove the solvent, and NMR analysis was performed (1,5-dimethyltetrazole: 2,5-dimethyltetrazole = 3: 1) (FIG. 1 to 3). 800 mL of isopropyl ether was added thereto, stirred at room temperature for 1 hour, cooled to 10°C, stirred for 30 minutes, and then filtered to obtain a solid. The wet body was dried at 45° C. for 8 hours to obtain 63.58 g (yield: 54%) of 1,5-dimethyltetrazole. The filtrate was concentrated under reduced pressure and distilled in vacuo to obtain 20 g of isomer 2,5-dimethyltetrazole (yield: 17%).
1,5-디메틸 테트라졸 = 1H NMR(CDCl3) δ4.01(s, 3H), δ2.56(s, 3H)1,5-dimethyl tetrazole = 1 H NMR (CDCl 3 ) δ4.01 (s, 3H), δ2.56 (s, 3H)
2,5-디메틸 테트라졸 = 1H NMR(CDCl3) δ4.30(s, 3H), δ2.53(s, 3H)2,5-dimethyl tetrazole = 1 H NMR (CDCl 3 ) δ4.30 (s, 3H), δ2.53 (s, 3H)
비교예 2 : 1,5-디메틸테트라졸의 제조Comparative Example 2: Preparation of 1,5-dimethyltetrazole
(1) 2-(t-부틸)-5-메틸-2H-테트라졸의 제조(1) Preparation of 2-(t-butyl)-5-methyl-2H-tetrazole
250 mL 3구 반응 플라스크에 98% 황산 50 mL을 투입한 후 5-메틸테트라졸 8 g을 넣고 20~25℃에서 교반하였다. 3차 부틸알콜 8.4 g을 반응액에 천천히 적가한 후, 동온도에서 150 분동안 교반하였다. 반응액을 얼음물 400 g에 천천히 투입하고 30 분간 교반하였다. 메틸렌클로라이드 50 mL으로 4회 추출 후 정제수 100 mL을 이용해서 세척하였다. 3% 탄산나트륨 수용액 50 mL로 세척한 후, 황산마그네슘으로 탈수하였다. 여과하고 감압농축한 후 진공증류를 실시하여 2-(t-부틸)-5-메틸-2H-테트라졸 5.47 g(수율 41%)을 얻었다(17mmHg에서 끓는점 74℃) (도 4).After adding 50 mL of 98% sulfuric acid to a 250 mL three-necked reaction flask, 8 g of 5-methyltetrazole was added and stirred at 20 to 25 °C. After slowly adding 8.4 g of tertiary butyl alcohol dropwise to the reaction solution, the mixture was stirred at the same temperature for 150 minutes. The reaction solution was slowly added to 400 g of ice water and stirred for 30 minutes. After
2-(t-부틸)-5-메틸-2H-테트라졸 = 1H NMR(CDCl3) δ2.53(s, 3H), δ1.73(s, 9H)2-(t-butyl)-5-methyl-2H-tetrazole = 1 H NMR (CDCl 3 ) δ2.53(s, 3H), δ1.73(s, 9H)
(2) 1,5-디메틸테트라졸의 제조(2) Preparation of 1,5-dimethyltetrazole
250 mL 플라스크에 상술한 2-(t-부틸)-5-메틸-2H-테트라졸 5.47 g과 디메틸설페이트 5.9 g, 클로로포름 40 mL를 넣고 5 시간동안 환류교반하였다. 용매를 감압하에 제거하고 잔류물에 진한 염산 78 mL를 넣고 5 시간동안 다시 환류교반하였다. 실온으로 냉각한 후 가성소다를 이용해서 중화하고 메틸렌클로라이드 50 mL로 3 회 추출하였다. 유기층을 모아서 정제수 70 mL로 세척하고 황산마그네슘으로 탈수 후 여과하여 농축하였다. 잔류물에 헵탄 30 mL를 넣고 실온에서 30 분동안 교반한 후 여과하였다. 45℃에서 5 시간동안 진공건조하여 백색결정 2.98 g(수율 78%)을 얻었다.5.47 g of 2-(t-butyl)-5-methyl-2H-tetrazole, 5.9 g of dimethyl sulfate, and 40 mL of chloroform were added to a 250 mL flask and stirred under reflux for 5 hours. The solvent was removed under reduced pressure, and 78 mL of concentrated hydrochloric acid was added to the residue, followed by stirring under reflux for 5 hours. After cooling to room temperature, it was neutralized using caustic soda and extracted three times with 50 mL of methylene chloride. The organic layer was collected, washed with 70 mL of purified water, dehydrated with magnesium sulfate, filtered, and concentrated. 30 mL of heptane was added to the residue, stirred at room temperature for 30 minutes, and then filtered. After vacuum drying at 45° C. for 5 hours, 2.98 g of white crystals were obtained (yield: 78%).
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시 양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.As described above, specific parts of the present invention have been described in detail, to those skilled in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
Claims (9)
(2) 상기 반응의 생성물을 결정화하는 단계를 포함하는, 1,5-디메틸테트라졸의 제조방법으로서,
상기 (2) 단계에서 결정화 용매는 수소결합을 형성하지 않는 것을 특징으로 하는, 1,5-디메틸테트라졸의 제조방법.
(1) reacting N-methylacetamide with a chlorosilane compound and an azide compound; and
(2) A method for producing 1,5-dimethyltetrazole, comprising the step of crystallizing the product of the reaction,
The method for producing 1,5-dimethyltetrazole, characterized in that the crystallization solvent in step (2) does not form a hydrogen bond.
상기 클로로실란 화합물은 트리메틸실란, 테트라클로로실란, 디클로로디아지도실란, 트리아지도클로로실란, 및 트리클로로아지도실란으로 이루어진 군으로부터 선택되는 어느 하나 이상인, 1,5-디메틸테트라졸의 제조방법.
According to claim 1,
The chlorosilane compound is any one or more selected from the group consisting of trimethylsilane, tetrachlorosilane, dichlorodiazidosilane, triazidochlorosilane, and trichloroazidosilane. Method for producing 1,5-dimethyltetrazole.
상기 아자이드 화합물은 소듐아자이드, 칼륨아자이드, 트리부틸아자이드, 및 테트라아지도실란으로 이루어진 군으로부터 선택되는 어느 하나 이상인, 1,5-디메틸테트라졸의 제조방법.
According to claim 1,
The azide compound is any one or more selected from the group consisting of sodium azide, potassium azide, tributyl azide, and tetraazidosilane, a method for producing 1,5-dimethyltetrazole.
상기 결정화 용매는 노말헥산, 사이클로헥산, 노말헵탄, 노말펜탄, 디에틸에테르, 이소프로필에테르, 메틸 t-부틸에테르, 에틸아세테이트, 메틸아세테이트, 이소프로필아세테이트 및 이들의 혼합물로 이루어진 군으로부터 선택되는 어느 하나 이상인, 1,5-디메틸테트라졸의 제조방법.
According to claim 1,
The crystallization solvent is any one selected from the group consisting of normal hexane, cyclohexane, normal heptane, normal pentane, diethyl ether, isopropyl ether, methyl t-butyl ether, ethyl acetate, methyl acetate, isopropyl acetate, and mixtures thereof. Method for producing one or more, 1,5-dimethyltetrazole.
상기 결정화 용매는 노말헵탄, 노말헥산, 노말펜탄, 메틸 t-부틸에테르 또는 이소프로필에테르인 것을 특징으로 하는, 1,5-디메틸테트라졸의 제조방법.
According to claim 1,
The crystallization solvent is normal heptane, normal hexane, normal pentane, methyl t-butyl ether or isopropyl ether, characterized in that, a method for producing 1,5-dimethyltetrazole.
상기 (1) 단계에서, N-메틸아세트아마이드, 클로로실란 화합물, 및 아자이드 화합물의 몰비는 1 : 1 : 1 내지 1 : 1 : 10인 것을 특징으로 하는, 1,5-디메틸테트라졸의 제조방법.
According to claim 1,
In step (1), the molar ratio of N-methylacetamide, chlorosilane compound, and azide compound is 1: 1: 1 to 1: 1: 10, characterized in that, Preparation of 1,5-dimethyltetrazole method.
상기 (1) 단계의 용매는 아세토니트릴, 테트라하이드로퓨란, 디메틸포름아마이드, 디메틸설폭사이드, 디메틸아세트아마이드, 아세톤, N-메틸피롤리돈, 및 이들의 혼합물로 이루어진 군으로부터 선택되는 어느 하나 이상인, 1,5-디메틸테트라졸의 제조방법.
According to claim 1,
The solvent in step (1) is at least one selected from the group consisting of acetonitrile, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, dimethylacetamide, acetone, N-methylpyrrolidone, and mixtures thereof, Method for producing 1,5-dimethyltetrazole.
상기 (1) 단계는, 상기 N-메틸아세트아마이드, 클로로실란 화합물, 및 아자이드 화합물을 첨가한 후 4 내지 6시간동안 환류 교반하는 것을 특징으로 하는, 1,5-디메틸테트라졸의 제조방법.
According to claim 1,
In the step (1), after adding the N-methylacetamide, the chlorosilane compound, and the azide compound, reflux stirring is performed for 4 to 6 hours.
상기 (1) 단계 이후 (2) 단계 이전에, 하기의 단계를 추가적으로 포함하는 1,5-디메틸테트라졸의 제조방법:
(a) 냉각 후 메탄올을 적가하는 단계;
(b) 메틸렌클로라이드를 첨가한 후 셀라이트를 통해 여과하는 단계; 및
(c) 용매를 감압농축하는 단계.
According to claim 1,
A method for producing 1,5-dimethyltetrazole further comprising the following steps after step (1) and before step (2):
(a) adding methanol dropwise after cooling;
(b) filtering through celite after adding methylene chloride; and
(c) concentrating the solvent under reduced pressure.
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