KR20220105537A - Method for preparing ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) and its analogue - Google Patents
Method for preparing ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) and its analogue Download PDFInfo
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- KR20220105537A KR20220105537A KR1020210008358A KR20210008358A KR20220105537A KR 20220105537 A KR20220105537 A KR 20220105537A KR 1020210008358 A KR1020210008358 A KR 1020210008358A KR 20210008358 A KR20210008358 A KR 20210008358A KR 20220105537 A KR20220105537 A KR 20220105537A
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- HFEAMIKDDWKNAG-UHFFFAOYSA-N bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1PC1=CC=CC=C1OC HFEAMIKDDWKNAG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- -1 (2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene) Chemical class 0.000 title abstract description 30
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 15
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- MWYXORYWUKRJEX-UHFFFAOYSA-N bis(2-methoxyphenyl)-oxophosphanium Chemical compound COC1=CC=CC=C1[P+](=O)C1=CC=CC=C1OC MWYXORYWUKRJEX-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000008213 purified water Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 20
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 16
- 229920001470 polyketone Polymers 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000003446 ligand Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- 239000002685 polymerization catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- CEWDAROJZGKUGQ-UHFFFAOYSA-N 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane Chemical compound CC1(C)OCC(CBr)(CBr)CO1 CEWDAROJZGKUGQ-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 3
- SXXPTCXIFIOPQF-UHFFFAOYSA-N 3-bis(2-methoxyphenyl)phosphanylpropyl-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CCCP(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC SXXPTCXIFIOPQF-UHFFFAOYSA-N 0.000 description 2
- PTIJGLJFVHCNHJ-UHFFFAOYSA-N C[SiH](O[SiH](C)C)C.C[SiH](O[SiH](C)C)C Chemical compound C[SiH](O[SiH](C)C)C.C[SiH](O[SiH](C)C)C PTIJGLJFVHCNHJ-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 2
- IIKVDSGDRQSJPE-UHFFFAOYSA-N [3-[bis(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxaspiro[5.5]undecan-3-yl]methyl-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)CC1(CP(C=2C(=CC=CC=2)OC)C=2C(=CC=CC=2)OC)COC2(CCCCC2)OC1 IIKVDSGDRQSJPE-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FCPRDUXJWIUVPZ-UHFFFAOYSA-M magnesium;methoxybenzene;bromide Chemical compound [Mg+2].[Br-].COC1=CC=CC=[C-]1 FCPRDUXJWIUVPZ-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/304—Aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 폴리케톤 중합체의 제조에 사용되는 촉매를 구성시키기 위한 리간드로 사용될 수 있는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀) 또는 그의 유사체의 제조 방법에 관한 것이다.The present invention relates to ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis (2-methoxyphenyl) phosphine) or an analog thereof.
일산화탄소와 에틸렌성 불포화 화합물의 공중합체인 폴리케톤, 특히 일산화탄소 유래의 반복단위와 에틸렌성 불포화 화합물 유래의 반복단위가 교대로 연결된 구조의 폴리케톤은 기계적 성질 및 열적 성질이 우수하고, 내마모성, 내약품성, 가스 배리어성 등이 우수하여 고강도 섬유 및 플라스틱의 원료와 같은 다양한 용도로 사용되고 있다.Polyketone, which is a copolymer of carbon monoxide and an ethylenically unsaturated compound, especially a polyketone having a structure in which repeating units derived from carbon monoxide and repeating units derived from an ethylenically unsaturated compound are alternately connected, has excellent mechanical and thermal properties, abrasion resistance, chemical resistance, Because of its excellent gas barrier properties, it is used for various purposes such as raw materials for high-strength fibers and plastics.
이러한 일산화탄소 유래의 반복단위와 에틸렌성 불포화 화합물 유래의 반복단위가 교대로 연결된 구조의 폴리케톤 중에, 완전 교대 공중합 폴리케톤은 더욱 높은 기계적 성질 및 열적 성질과 더불어 경제성이 또한 우수하여 엔지니어링 플라스틱재로서 특히 유용한 것으로 여겨진다. Among polyketones having a structure in which repeating units derived from carbon monoxide and repeating units derived from ethylenically unsaturated compounds are alternately connected, the fully alternating copolymerized polyketone has higher mechanical and thermal properties as well as excellent economic feasibility, making it particularly suitable as an engineering plastic material. It is considered useful.
따라서, 이러한 폴리케톤의 합성은 일산화탄소를 유용한 물질로 변환시킨다는 측면과 물리적 특성이 우수한 고분자 화합물을 제공할 수 있다는 측면에서 산업적인 이용성이 우수하다. 예를 들어, 완전 교대 공중합 폴리케톤은 내마모성이 매우 우수하여 자동차의 기어 등의 부품에 유용하고, 내약품성이 또한 우수하여 화학물질 수송 파이프의 라이닝재 등에 유용하며, 가스 배리어성이 또한 우수하여 경량 가솔린을 위한 탱크 등에 유용하다. 또한, 고유점도 2 이상의 초고분자량 폴리케톤을 섬유에 이용하는 경우, 고배율의 연신이 가능해지고 연신방향으로 배향된 고강도 및 고탄성율을 가져서, 벨트, 고무호스 등의 보강재, 타이어 코드, 콘크리트 보강재, 건축재료 및 산업자재로의 용도에 매우 적합한 재료가 된다.Therefore, the synthesis of such polyketone has excellent industrial applicability in terms of converting carbon monoxide into useful substances and providing a high molecular compound having excellent physical properties. For example, fully alternating copolymerized polyketone has very good wear resistance and is useful for parts such as gears of automobiles. Useful for tanks for gasoline, etc. In addition, when ultra-high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fiber, it is possible to draw at a high magnification and has a high strength and a high modulus of elasticity oriented in the stretching direction. And it becomes a material very suitable for use as an industrial material.
이러한 폴리케톤의 제조에 사용되는 중합촉매는 일반적으로 Pd(II)/바이덴테이트 포스핀 리간드(Bidentate Phosphine Ligand)/산(Acid)의 시스템으로 구성된다.The polymerization catalyst used for the preparation of these polyketones is generally composed of a system of Pd(II)/Bidentate Phosphine Ligand/Acid.
예를 들어, 한국 특허 공개 공보 10-2015-0010031호 및 한국 특허 공개 공보 10-2017-0030279호는 A) 금속 이온; (B) 리간드로서 하기 화학식 1의 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀); 및 (C) 산;으로 이루어진 폴리케톤 중합촉매를 개시하고 있다.For example, Korean Patent Application Laid-Open No. 10-2015-0010031 and Korean Patent Application Laid-Open No. 10-2017-0030279 A) metal ions; (B) ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) of the following formula (1) as a ligand; and (C) an acid; discloses a polyketone polymerization catalyst consisting of.
상기 한국 특허 공개 공보 10-2015-0010031호 및 한국 특허 공개 공보 10-2017-0030279호에서는 (a) 질소 대기하에서 비스(2-메톡시페닐)포스핀 및 디메틸설폭시드를 반응용기에 투입하고 상온에서 수소화나트륨을 가한 뒤 교반하는 단계; (b) 얻어진 혼합액에 5,5-비스(브로모메틸)-2,2-디메틸-1,3-디옥산 및 디메틸설폭시드를 가한 뒤 교반하여 반응시키는 단계; (c) 반응 완료 후 메탄올을 투입하고 교반하는 단계; (d) 톨루엔 및 물을 투입하고 층분리 후 유층을 물로 세척한 다음 무수황산나트륨으로 건조 후 감압 여과를 하고 감압 농축하는 단계; 및 (e) 잔류물을 메탄올 하에서 재결정하여 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)를 얻는 단계;를 포함하는 것을 특징으로 하는 폴리케톤 중합촉매용 리간드의 제조방법을 개시하고 있다.In the Korean Patent Application Laid-Open No. 10-2015-0010031 and Korean Patent Publication No. 10-2017-0030279, (a) bis (2-methoxyphenyl) phosphine and dimethyl sulfoxide were added to a reaction vessel under a nitrogen atmosphere, and then at room temperature After adding sodium hydride in the stirring step; (b) adding 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the obtained mixture, followed by stirring to react; (c) adding methanol after completion of the reaction and stirring; (d) adding toluene and water, washing the oil layer with water after layer separation, drying over anhydrous sodium sulfate, filtration under reduced pressure, and concentration under reduced pressure; and (e) recrystallizing the residue in methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) Disclosed is a method for preparing a ligand for a polyketone polymerization catalyst, comprising the step of obtaining a.
그러나, 한국 특허 공개 공보 10-2015-0010031호 및 한국 특허 공개 공보 10-2017-0030279호의 방법에서의 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)을 제조하는 방법은 비스(2-메톡시페닐)포스핀 제조에 사용되는 원료로 트리클로로포스핀과 트리클로로실란을 사용하는데 유독한 산가스를 발생시키고 산폐수를 유발하는 문제가 있고 유독물질을 사용하는데 제약사항이 많아서 문제가 있다.However, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene) in the methods of Korean Patent Application Laid-Open No. 10-2015-0010031 and Korean Patent Publication No. 10-2017-0030279 )) The method for producing bis(bis(2-methoxyphenyl)phosphine) uses trichlorophosphine and trichlorosilane as raw materials used for the production of bis(2-methoxyphenyl)phosphine, which is a toxic acid. There is a problem of generating gas and causing acid wastewater, and there are many restrictions on the use of toxic substances.
이와 같이, 트리클로로포스핀이란 물질은 생산단계에서 -60℃ 이하의 저온반응을 진행해야 하고 생성되는 불순물의 제거에 유기용제를 다량 사용하는 문제점과 트리클로로포스핀은 생화학 무기를 만들 때 사용하는 물질로서 사용에 제한이 있고 다량의 산가스와 산폐액을 만들어내어 환경에 악영향을 끼칠 수 있다. As such, trichlorophosphine has to undergo a low-temperature reaction below -60°C in the production stage, and the problem of using a large amount of organic solvent to remove the generated impurities. As a substance, its use is limited and it can adversely affect the environment by generating a large amount of acid gas and acid waste.
또한 상기 종래 기술에서 사용되는 트리클로로실란은 다량의 산가스와 산폐액을 만들어내고 압력용기를 사용해야 하는 문제로 이송과 보관중 누출사고시 인명피해를 초래할 수 있다.In addition, trichlorosilane used in the prior art is a problem that produces a large amount of acid gas and acid waste and requires the use of a pressure vessel, which may cause personal injury in case of leakage during transport and storage.
또한, 수소화나트륨은 화재위험에 노출되어 있어 사용시 많은 주의가 필요하다.In addition, sodium hydride is exposed to fire risk, so a lot of caution is required when using it.
이에, 상기 문제를 해소시켜 경제적이고 안전하게 대량 생산할 수 있는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀) 및 그의 유사체를 제조하는 방법이 요구되고 있다.Accordingly, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl) which can be mass-produced economically and safely by solving the above problems There is a need for methods for preparing phosphines) and analogs thereof.
[종래 기술 문헌][Prior art literature]
[특허 문헌][Patent Literature]
(특허 문헌) 한국 특허 공개 공보 10-2015-0010031호(Patent Document) Korean Patent Publication No. 10-2015-0010031
한국 특허 공개 공보 10-2017-0030279호 Korean Patent Publication No. 10-2017-0030279
상기 문제를 해결하고자, 본 발명에서는 1,1,3,3-테트라메틸실록산 또는 폴리메틸하이드로실록산 및 디에틸포스파이트를 사용하여 공정 위험성과 환경적인 문제를 해결할 수 있으면서 안전하고 경제적인 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀) 및 그의 유사체의 제조 방법을 제공하고 있다.In order to solve the above problems, in the present invention, safe and economical ((2) provided is a process for the preparation of ,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) and analogs thereof.
따라서, 본 발명의 목적은 공정상 및 환경적으로 안전하게 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀) 및 그의 유사체를 수득함을 포함하여, 폴리케톤 중합촉매용 인 리간드의 제조방법을 제공하는 것이다.Accordingly, it is an object of the present invention to safely process ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl) To provide a method for preparing a phosphorus ligand for a polyketone polymerization catalyst, including obtaining phosphine) and analogs thereof.
따라서, 상기 목적을 달성시키기 위해서, 본 발명은 비스(2-메톡시페닐)포스핀을 1,1,3,3-테트라메틸실록산" 또는 "폴리메틸하이드로실록산을 사용하여 리간드 화합물을 수득하는 단계를 포함하는 폴리케톤 중합촉매용 인 리간드, 즉, ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀) 및 그의 유사체의 제조방법을 제공하고 있다.Therefore, in order to achieve the above object, the present invention provides a step of obtaining a ligand compound using 1,1,3,3-tetramethylsiloxane or polymethylhydrosiloxane for bis(2-methoxyphenyl)phosphine Phosphorus ligand for polyketone polymerization catalyst containing fin) and a method for preparing its analogues.
또한, 본 발명은 비스(2-메톡시페닐)포스핀 옥사이드를 금속알콜사이드로 반응 후 수득한 화합물을 1,1,3,3-테트라메틸실록산 또는 폴리메틸하이드로실록산을 사용하여 리간드 화합물을 수득하는 단계를 포함하는 폴리케톤 중합촉매용 인 리간드, 즉, ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀) 및 그의 유사체의 제조방법을 제공하고 있다.In addition, the present invention provides a ligand compound by using 1,1,3,3-tetramethylsiloxane or polymethylhydrosiloxane for the compound obtained after reacting bis(2-methoxyphenyl)phosphine oxide with a metal alkoxide. Phosphorus ligand for polyketone polymerization catalyst comprising the step of, that is, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl) ) phosphine) and a method for preparing analogs thereof.
본 발명에 따르면, 1,1,3,3-테트라메틸실록산 또는 폴리메틸하이드로실록산을 사용하여 트리클로로실란 및 디에틸포스파이트를 사용함으로써 종래 기술에서의 공정 및 환경상의 안전성의 문제를 해소시키면서, 경제적이고 안전하게 폴리케톤 중합촉매용 인 리간드, 즉, ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀) 및 그의 유사체를 대량 생산할 수 있다.According to the present invention, by using trichlorosilane and diethylphosphite using 1,1,3,3-tetramethylsiloxane or polymethylhydrosiloxane, while solving the problem of process and environmental safety in the prior art, Economical and safe phosphorus ligand for polyketone polymerization catalyst, that is, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phos fins) and their analogs can be mass-produced.
본 발명은 폴리케톤 중합촉매의 리간드로서 사용되는 하기 화학식의 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀) 또는 그의 유사체의 제조방법에 관한 것이다:The present invention relates to ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl) ) phosphine) or an analog thereof.
바람직하게는, 본 발명은 하기 화학식(I) 또는 (I')의 화합물을 제조하는 방법으로서, i) 반응기에 하기 화학식(II)의 비스(2-메톡시페닐)포스핀 옥사이드와, 테트라하이드로퓨란 또는 톨루엔, 및 티타늄 이소프로폭사이드 또는 트리플레이트 구리(II), 및 1,1,3,3-테트라메틸디실록산 또는 폴리메틸하이드로실록산을 투입하고 환류시켜 하기 화학식(III)의 비스(2-메톡시페닐)포스핀을 생성시키는 단계; ii) 질소 대기하에서 반응기에 상기 단계 i)에서 얻은 화학식(III)의 비스(2-메톡시페닐)포스핀과 디메틸설폭사이드 또는 테트라하이드로퓨란을 투입 후 교반하여 용해시키고, 포타슘 터트-부톡사이드를 투입한 후 교반하는 단계; 및 iii) 상기 단계 ii)로부터 얻은 용액에, 디메틸설폭사이드 또는 테트라하이드로퓨란에 용해시킨 화학식(IV) 또는 (IV')의 화합물을 20~25℃에서 적가하고 교반하여 화학식(I) 또는 (I')의 화합물을 수득하는 단계를 포함하는, 화학식(I) 또는 (I')의 화합물을 제조하는 방법을 제공한다:Preferably, the present invention provides a method for preparing a compound of formula (I) or (I'), i) comprising bis(2-methoxyphenyl)phosphine oxide of formula (II) Furan or toluene, titanium isopropoxide or copper triflate (II), and 1,1,3,3-tetramethyldisiloxane or polymethylhydrosiloxane are added and refluxed to reflux bis(2) of the following formula (III) -Methoxyphenyl) generating phosphine; ii) bis(2-methoxyphenyl)phosphine of formula (III) obtained in step i) and dimethylsulfoxide or tetrahydrofuran were added to the reactor under a nitrogen atmosphere, and stirred to dissolve, and potassium tert-butoxide Stirring after the input; and iii) a compound of formula (IV) or (IV') dissolved in dimethyl sulfoxide or tetrahydrofuran was added dropwise to the solution obtained in step ii) at 20 to 25° C. and stirred to add formula (I) or (I) There is provided a process for preparing a compound of formula (I) or (I') comprising the step of obtaining a compound of '):
상기 식에서,In the above formula,
R은 서로 독립적으로 H, C1-6 알킬, C1-6 알콕시, 또는 C1-6 알콕시페닐이고,R is independently of each other H, C 1-6 alkyl, C 1-6 alkoxy, or C 1-6 alkoxyphenyl;
X는 Cl, Br, OTf, OMs, OTs 또는 ONs이다.X is Cl, Br, OTf, OMs, OTs or ONs.
상기 본 발명의 화학식(I) 및 (I')의 화합물의 제조방법의 개략적인 반응도식은 다음과 같다:A schematic reaction scheme of the process for preparing the compounds of formulas (I) and (I') of the present invention is as follows:
반응도식(I)Scheme (I)
상기 반응도식(I)에서,In the above scheme (I),
R은 서로 독립적으로 H, C1-6 알킬, C1-6 알콕시, 또는 C1-6 알콕시페닐이며,R is independently of each other H, C 1-6 alkyl, C 1-6 alkoxy, or C 1-6 alkoxyphenyl;
X는 Cl, Br, OTf, OMs, OTs 또는 ONs이고, X is Cl, Br, OTf, OMs, OTs or ONs,
TMDS는 1,1,3,3-테트라메틸디실록산(1,1,3,3-Tetramethyldisiloxane)이며, PHMS는 폴리메틸하이드로실록산(Polymethylhydrosiloxane)이고, 이들 모두는 시중 구입 가능하다.TMDS is 1,1,3,3-tetramethyldisiloxane (1,1,3,3-Tetramethyldisiloxane) and PHMS is polymethylhydrosiloxane, all of which are commercially available.
바람직하게는, 본 발명은, 상기 본 발명의 방법에서, R이 서로 독립적으로 -CH3이어서, ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)을 제조하는 방법을 제공한다.Preferably, the present invention provides that, in the method of the present invention, R independently of each other is —CH 3 followed by ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene) ) bis(bis(2-methoxyphenyl)phosphine).
또한, 바람직하게는, 상기 본 발명의 방법은, 단계 i) 후에, 얻은 혼합물에 메틸렌클로라이드와 20% 수산화칼륨 수용액을 투입 후 유기층을 분층 후, 10% 염화나트륨 수용액으로 세척하고 무수 황산나트륨으로 수분을 제거하고, 얻은 잔사에 무수 에탄올을 넣고 공비한 후 노르말 헥산으로 슬러리화하여 여과한 다음 건조함을 추가로 포함한다.Also, preferably, in the method of the present invention, after step i), methylene chloride and 20% aqueous potassium hydroxide solution are added to the obtained mixture, the organic layer is separated, washed with 10% aqueous sodium chloride solution, and moisture is removed with anhydrous sodium sulfate Then, anhydrous ethanol was added to the obtained residue, followed by azeotroping, slurried with normal hexane, filtered, and dried.
또한, 바람직하게는, 상기 본 발명의 방법은, 상기 단계 iii) 후에, 얻은 혼합물에 메틸렌클로라이드와 정제수를 투입 후 분층하고, 유기층을 10% 염화나트륨 수용액으로 세척한 다음, 무수 황산나트륨으로 수분을 제거하고 메탄올로 재결정함을 추가로 포함한다.In addition, preferably, in the method of the present invention, after step iii), methylene chloride and purified water are added to the obtained mixture, then separated, the organic layer is washed with 10% aqueous sodium chloride solution, and then moisture is removed with anhydrous sodium sulfate, It further comprises recrystallization from methanol.
또한, 본 발명은 하기 화학식(I) 또는 (I')의 화합물을 제조하는 방법으로서, i) 질소 대기하에서 반응기에 화학식(II)의 비스(2-메톡시페닐)포스핀 옥사이드와 테트라하이드로퓨란을 투입 후 용해시키고, 포타슘 터트-부톡사이드를 투입한 후 교반시키고, 얻은 용액에, 테트라하이드로퓨란에 용해시킨 화학식(IV) 또는 (IV')의 화합물을 30℃ 이하의 온도에서 적가하고 교반하여 화학식(V) 또는 (V')의 화합물을 얻는 단계; 및 ii) 질소 대기하에서 반응기에 상기 단계 i)에서 얻은 화학식(V) 또는 (V')의 화합물과 톨루엔, 티타늄 이소프로폭사이드, 및 1,1,3,3-테트라메틸디실록산 또는 폴리메틸하이드로실록산을 투입 후 환류하여 반응시켜 화학식(I)의 화합물을 수득하는 단계를 포함하는, 하기 화학식(I) 또는 (I')의 화합물을 제조하는 방법을 제공한다:In addition, the present invention is a method for preparing a compound of formula (I) or (I'), i) bis(2-methoxyphenyl)phosphine oxide of formula (II) and tetrahydrofuran in a reactor under nitrogen atmosphere was added and dissolved, potassium tert-butoxide was added and stirred, and to the obtained solution, a compound of formula (IV) or (IV') dissolved in tetrahydrofuran was added dropwise at a temperature of 30° C. or less and stirred. obtaining a compound of formula (V) or (V'); and ii) toluene, titanium isopropoxide, and 1,1,3,3-tetramethyldisiloxane or polymethyl with the compound of formula (V) or (V') obtained in step i) above in a reactor under a nitrogen atmosphere. It provides a method for preparing a compound of the following formula (I) or (I'), comprising the step of reacting by adding hydrosiloxane to reflux to obtain a compound of formula (I):
상기 식에서,In the above formula,
R은 서로 독립적으로 H, C1-6 알킬, C1-6 알콕시, 또는 C1-6 알콕시페닐이고,R is independently of each other H, C 1-6 alkyl, C 1-6 alkoxy, or C 1-6 alkoxyphenyl;
X는 Cl, Br, OTf, OMs, OTs 또는 ONs이다.X is Cl, Br, OTf, OMs, OTs or ONs.
상기 본 발명의 화학식(I) 또는 (I')의 화합물의 또 다른 제조방법의 개략적인 반응도식은 다음과 같다:A schematic reaction scheme of another method for preparing the compound of formula (I) or (I') of the present invention is as follows:
반응도식(II)Scheme (II)
상기 반응도식(I)에서,In the above scheme (I),
R은 서로 독립적으로 H, C1-6 알킬, C1-6 알콕시, 또는 C1-6 알콕시페닐이며,R is independently of each other H, C 1-6 alkyl, C 1-6 alkoxy, or C 1-6 alkoxyphenyl;
X는 Cl, Br, OTf, OMs, OTs 또는 ONs이고, X is Cl, Br, OTf, OMs, OTs or ONs,
TMDS는 1,1,3,3-테트라메틸디실록산(1,1,3,3-Tetramethyldisiloxane)이며, PHMS는 폴리메틸하이드로실록산(Polymethylhydrosiloxane)이고, 이들 모두는 시중 구입 가능하다.TMDS is 1,1,3,3-tetramethyldisiloxane (1,1,3,3-Tetramethyldisiloxane) and PHMS is polymethylhydrosiloxane, all of which are commercially available.
바람직하게는, 본 발명은, 상기 또 다른 방법에서, R이 서로 독립적으로 -CH3이어서, ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)을 제조하는 방법을 제공한다.Preferably, the present invention provides that, in another method, R is independently of each other -CH 3 followed by ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene)) A method for preparing bis(bis(2-methoxyphenyl)phosphine) is provided.
또한, 바람직하게는, 본 발명의 상기 또 다른 방법은, 단계 i) 후에, 얻은 혼합물에, 정제수과 메틸렌클로라이드를 투입 후 분층하고 유기층을 5% 염화나트륨 수용액으로 세척 후 무수 황산나트륨으로 수분을 제거하고, 감압하여 농축한 다음, 메탄올로 슬러리화한 후 여과하고 건조한 후에, 재결정함을 추가로 포함한다.Also, preferably, in the another method of the present invention, after step i), purified water and methylene chloride are added to the obtained mixture, then separated, the organic layer is washed with 5% sodium chloride aqueous solution, water is removed with anhydrous sodium sulfate, and the pressure is reduced. and concentrated, then slurried with methanol, filtered and dried, and then recrystallized.
또한, 바람직하게는, 본 발명의 상기 또 다른 방법은, 단계 ii) 후에, 얻은 혼합물에, 메틸렌클로라이드와 정제수를 투입 후 20% 수산화칼륨 수용액을 적가하고, 셀라이트 여과 후에 유기층을 분층하고, 5% 염화나트륨 수용액으로 세척하고, 무수 황산나트륨으로 수분을 제거하고 메틸렌클로라이드-메탄올로 재결정함을 추가로 포함한다.In addition, preferably, in the another method of the present invention, after step ii), methylene chloride and purified water are added to the obtained mixture, then 20% aqueous potassium hydroxide solution is added dropwise, and the organic layer is separated after celite filtration, 5 % aqueous sodium chloride solution, removing moisture with anhydrous sodium sulfate, and recrystallizing from methylene chloride-methanol.
이하, 본 발명이 실시예를 참조로 하여 상세히 기재될 것이지만, 이로 본 발명이 제한되는 것으로 의도되지 않음이 이해될 것이다.Hereinafter, the present invention will be described in detail with reference to examples, but it will be understood that the present invention is not intended to be limited thereto.
실시예Example
참고예: 비스(2-메톡시페닐)포스핀 옥사이드의 제조(J.Am.Chem.Soc., 2012, 134, 6136-6139 참조)Reference Example: Preparation of bis (2-methoxyphenyl) phosphine oxide (see J. Am. Chem. Soc., 2012, 134, 6136-6139)
질소 대기하에서 반응기에서 마그네슘(29.9g, 1.231mol)과 테트라하이드로퓨란 (300ml), (2-메톡시페닐)마그네슘 브로마이드 1.0M 2-메틸테트라하이드로퓨란 용액 (2ml)를 투입하였다. 30~35℃에서 1-브로모-2-메톡시벤젠(223.85g, 1.1948mol)과 테트라하이드로퓨란(450ml)의 혼합용액을 적가한 후, 43~47℃에서 2시간 교반하였다. 디에틸포스파이트(50g, 0.3620mol)를 0~10℃에서 적가한 다음 실온에서 12시간 교반하였다. H2O (220g)을 10℃ 이하에서 적가하고, 감압하여 테트라하이드로퓨란을 감압농축하였다. 농축잔사에 메틸렌클로라이드(660ml)을 투입 후 6N HCl 수용액(240g)을 적가한 후 유기층을 분층하였다. 분리한 유기층을 포화 탄산소소나트륨수용액(500g)으로 1회 세척하고, 10% 염화나트륨 수용액(500g)으로 2회 세척하였다. 유기층을 무수 황산나트륨으로 수분을 제거한 다음 감압하여 농축하였다. 농축잔사에 초산에틸(50ml)를 투입 후 교반한 다음 여과 및 건조하여 비스(2-메톡시페닐)포스핀 옥사이드(72.02g, 75.30%)를 얻었다.In a reactor under nitrogen atmosphere, magnesium (29.9 g, 1.231 mol), tetrahydrofuran (300 ml), and (2-methoxyphenyl) magnesium bromide 1.0 M 2-methyltetrahydrofuran solution (2 ml) were added. A mixed solution of 1-bromo-2-methoxybenzene (223.85 g, 1.1948 mol) and tetrahydrofuran (450 ml) was added dropwise at 30-35°C, followed by stirring at 43-47°C for 2 hours. Diethyl phosphite (50 g, 0.3620 mol) was added dropwise at 0 to 10° C., followed by stirring at room temperature for 12 hours. H 2 O (220 g) was added dropwise at 10° C. or less, and tetrahydrofuran was concentrated under reduced pressure under reduced pressure. After methylene chloride (660ml) was added to the concentrated residue, 6N HCl aqueous solution (240g) was added dropwise, and the organic layer was partitioned. The separated organic layer was washed once with a saturated aqueous sodium bicarbonate solution (500 g), and washed twice with a 10% aqueous sodium chloride solution (500 g). The organic layer was dried with anhydrous sodium sulfate, and then concentrated under reduced pressure. Ethyl acetate (50ml) was added to the concentrated residue, followed by stirring, followed by filtration and drying to obtain bis(2-methoxyphenyl)phosphine oxide (72.02 g, 75.30%).
1H NMR (CDCl3): 7.63~7.57(dd, 2H), 7.44 ~ 7.40 (dt, 2H), 6.99~6.95 (dt, 2H), 6.83~6.80(dd, 2H), 3.65(s, 6H). 1 H NMR (CDCl 3 ): 7.63-7.57 (dd, 2H), 7.44-7.40 (dt, 2H), 6.99-6.95 (dt, 2H), 6.83-6.80 (dd, 2H), 3.65 (s, 6H) .
31P NMR (CDCl3): 10.02. 31 P NMR (CDCl 3 ): 10.02.
실시예 1. 비스(2-메톡시페닐)포스핀 중간체의 제조Example 1. Preparation of bis(2-methoxyphenyl)phosphine intermediate
질소 대기하에서 반응기에 비스(2-메톡시페닐)포스핀 옥사이드(10g, 37.8444mmol)과 테트라하이드로퓨란(100ml), 티타늄 이소프로폭사이드(8.94g, 31.41084mmol), 1,1,3,3-테트라메틸디실록산(12.71g, 94.6110mmol)를 투입하고, 24시간 환류하였다. 실온으로 냉각 후 감압하여 농축하고, 농축잔사에 메틸렌 클로라이드(100ml)와 20% 수산화칼륨 수용액 (20g)을 투입 후 1시간 교반하였다. 유기층을 분층 후 10% 염화나트륨 수용액으로 2회 세척하고 무수 황산나트륨으로 수분을 제거 및 감압하여 농축하였다. 농축잔사에 무수 에탄올로 넣고 2회 공비한 후 노르말 헥산으로 슬러리하여 여과한 다음 건조하여 비스(2-메톡시페닐)포스핀(7.72g, 82.83%)를 얻었다.Bis (2-methoxyphenyl) phosphine oxide (10 g, 37.8444 mmol) and tetrahydrofuran (100 ml), titanium isopropoxide (8.94 g, 31.41084 mmol), 1,1,3,3 in a reactor under nitrogen atmosphere -Tetramethyldisiloxane (12.71 g, 94.6110 mmol) was added and refluxed for 24 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure, and methylene chloride (100 ml) and 20% aqueous potassium hydroxide solution (20 g) were added to the concentration residue, followed by stirring for 1 hour. After separation, the organic layer was washed twice with 10% aqueous sodium chloride solution, water was removed with anhydrous sodium sulfate, and concentrated under reduced pressure. Anhydrous ethanol was added to the concentrated residue, azeotroped twice, filtered through a slurry with normal hexane, and dried to obtain bis(2-methoxyphenyl)phosphine (7.72 g, 82.83%).
1H NMR (CDCl3): 7.31(t, 2H), 7.224(t, 2H), 6.91~6.86(m, 4H), 5.11~5.33(d, 1H), 3.82(s, 6H) 1 H NMR (CDCl 3 ): 7.31 (t, 2H), 7.224 (t, 2H), 6.91-6.86 (m, 4H), 5.11-5.33 (d, 1H), 3.82 (s, 6H)
31P NMR (CDCl3): -74.21 31 P NMR (CDCl 3 ): -74.21
실시예 2. 비스(2-메톡시페닐)포스핀 중간체의 제조Example 2. Preparation of bis(2-methoxyphenyl)phosphine intermediate
실시예 1에서 테트라하이드로퓨란 대신 톨루엔을 사용하여 동일한 방법으로 비스(2-메톡시페닐)포스핀(6.89g, 73.93%)을 얻었다.In Example 1, bis(2-methoxyphenyl)phosphine (6.89 g, 73.93%) was obtained in the same manner using toluene instead of tetrahydrofuran.
실시예 3. 비스(2-메톡시페닐)포스핀 중간체의 제조Example 3. Preparation of bis(2-methoxyphenyl)phosphine intermediate
실시예 1에서 티타늄 이소프로폭사이드 대신 트리플레이트 구리(II)를 사용하여 동일한 방법으로 비스(2-메톡시페닐)포스핀(7.53g, 80.51%)을 얻었다.In Example 1, bis(2-methoxyphenyl)phosphine (7.53 g, 80.51%) was obtained in the same manner using triflate copper (II) instead of titanium isopropoxide.
실시예 4. 비스(2-메톡시페닐)포스핀 중간체의 제조Example 4. Preparation of bis(2-methoxyphenyl)phosphine intermediate
질소 대기하에서 반응기에 비스(2-메톡시페닐)포스핀 옥사이드 (1g, 3.844mmol)과 테트라하이드로퓨란 (10ml), 티타늄 이소프로폭사이드(0.89g, 3.1411mmol), 폴리메틸하이드로실록산(3ml)를 투입 후 12시간 환류하였다. 실온으로 냉각 후 감압하여 농축하고, 농축잔사에 메틸렌클로라이드(10ml)와 20% 수산화칼륨 수용액 (2g)을 투입 후 1시간 교반하였다. 유기층을 분층 후 10% 염화나트륨 수용액(10ml)으로 2회 세척하고 무수 황산나트륨으로 수분을 제거 및 감압하여 농축하였다. 농축 잔사에 무수 에탄올 (50ml)를 넣고 2회 공비한 후 노르말 헥산 (20ml)로 슬러리하여 여과한 다음 건조하여 백색 고체인 비스(2-메톡시페닐)포스핀 (0.72g, 77.14%)를 얻었다.Bis (2-methoxyphenyl) phosphine oxide (1 g, 3.844 mmol) and tetrahydrofuran (10 ml), titanium isopropoxide (0.89 g, 3.1411 mmol), polymethylhydrosiloxane (3 ml) in a reactor under nitrogen atmosphere was refluxed for 12 hours after input. After cooling to room temperature, the mixture was concentrated under reduced pressure, and methylene chloride (10 ml) and 20% aqueous potassium hydroxide solution (2 g) were added to the concentration residue, followed by stirring for 1 hour. After separation, the organic layer was washed twice with 10% aqueous sodium chloride solution (10 ml), water was removed with anhydrous sodium sulfate, and concentrated under reduced pressure. Anhydrous ethanol (50ml) was added to the concentrated residue, azeotroped twice, filtered and filtered with normal hexane (20ml), and then dried to obtain bis(2-methoxyphenyl)phosphine (0.72g, 77.14%) as a white solid. .
실시예 5. 비스(2-메톡시페닐)포스핀 중간체의 제조Example 5. Preparation of bis(2-methoxyphenyl)phosphine intermediate
실시예 4에서 테트라하이드로퓨란 대신 톨루엔을 사용하여 동일한 방법으로 비스(2-메톡시페닐)포스핀(0.46g, 49.21%)를 얻었다.In Example 4, bis(2-methoxyphenyl)phosphine (0.46 g, 49.21%) was obtained in the same manner using toluene instead of tetrahydrofuran.
실시예 6. 비스(2-메톡시페닐)포스핀 중간체의 제조Example 6. Preparation of bis(2-methoxyphenyl)phosphine intermediate
실시예 4에서 티타늄 이소프로폭사이드 대신 트리플레이트 구리(II) 사용하여 동일한 방법으로 비스(2-메톡시페닐)포스핀(0.57g, 61.33%)를 얻었다.In Example 4, bis(2-methoxyphenyl)phosphine (0.57 g, 61.33%) was obtained in the same manner using triflate copper (II) instead of titanium isopropoxide.
실시예 7. 비스(2-메톡시페닐)포스핀 중간체의 제조Example 7. Preparation of bis(2-methoxyphenyl)phosphine intermediate
실시예 4에서 테트라하이드로퓨란 대신 톨루엔을 사용하였고, 티타늄 이소프로폭사이드 대신 트리플레이트 구리(II)를 사용하여 동일한 방법으로 비스(2-메톡시페일)포스핀(0.58g, 62.18%)을 얻었다.In Example 4, toluene was used instead of tetrahydrofuran, and bis(2-methoxypal)phosphine (0.58 g, 62.18%) was obtained in the same manner using triflate copper (II) instead of titanium isopropoxide. .
실시예 8. ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)의 제조Example 8. Preparation of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine)
질소 대기하에서 반응기에 비스(2-메톡시페닐)포스핀(5.0g, 18.922mmol)과 디메틸설폭사이드(50ml)을 투입 후 교반하여 용해시키고, 포타슘 터트-부톡사이드(0.26g 22.706)을 투입한 후 30분 교반하였다. 5,5-비스(브로모메틸)-2,2-디메틸-1,3-디옥산(2.9g, 9.461mmol)을 디메틸설폭사이드(20ml)에 용해시킨 후 20~25도에서 적가하고 30분 교반하였다. 메틸렌클로라이드(50ml)와 정제수(50ml)를 투입 후 분층하고 유기층을 10% 염화나트륨 수용액으로 3회 세척하였다. 무수 황산나트륨으로 수분을 제거하고 감압농축 메탄올로 재결정하여 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀) (8.51g, 71.15%)를 얻었다.Bis (2-methoxyphenyl) phosphine (5.0 g, 18.922 mmol) and dimethyl sulfoxide (50 ml) were added to the reactor under a nitrogen atmosphere and dissolved by stirring, and potassium tert-butoxide (0.26 g 22.706) was added. After 30 minutes, the mixture was stirred. 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane (2.9 g, 9.461 mmol) was dissolved in dimethyl sulfoxide (20 ml) and added dropwise at 20 to 25 degrees for 30 minutes stirred. After adding methylene chloride (50ml) and purified water (50ml), the layers were separated, and the organic layer was washed 3 times with 10% aqueous sodium chloride solution. Moisture was removed with anhydrous sodium sulfate and recrystallized from concentrated methanol under reduced pressure ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phos pin) (8.51 g, 71.15%) was obtained.
1H NMR (CDCl3): 7.20~7.18(m, 4H), 7.17~7.12(m, 4H), 6.80~6.77(m, 4H), 6.72~6.70(m, 4H), 3.81(s, 4H), 3.61(s, 12H), 2.4(d, 4H), 1.32(s, 6H) 1 H NMR (CDCl 3 ): 7.20-7.18 (m, 4H), 7.17-7.12 (m, 4H), 6.80-6.77 (m, 4H), 6.72-6.70 (m, 4H), 3.81 (s, 4H) , 3.61(s, 12H), 2.4(d, 4H), 1.32(s, 6H)
31P NMR (CDCl3): -47.80 31 P NMR (CDCl 3 ): -47.80
실시예 9. ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)의 제조Example 9. Preparation of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine)
실시예 8에서 디메틸설폭사이드 대신 테트라하이드로퓨란을 사용하여 동일한 방법으로 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)(7.15g, 59.77%)을 얻었다.((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methyl) in Example 8 using tetrahydrofuran instead of dimethylsulfoxide toxyphenyl)phosphine) (7.15 g, 59.77%) was obtained.
실시예 10. (1,5-디옥사스피로[5.5]운데칸-3,3-디일비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)의 제조Example 10. Preparation of (1,5-dioxaspiro[5.5]undecane-3,3-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine)
실시예 8에서와 유사한 방법으로 (1,5-디옥사스피로[5.5]운데칸-3,3-디일비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)을 얻었다.(1,5-dioxaspiro[5.5]undecane-3,3-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine) was obtained in a manner similar to Example 8.
1H NMR(CDCl3): 7.22-7.11 (m,8H), 6.89-6.80 (m,8H), 3.86(s,4H), 3.72(s,12H), 2.40(d,4H), 1.78 (s,4H), 1.47(s,4H), 1.32(bs,2H). 1 H NMR (CDCl 3 ): 7.22-7.11 (m,8H), 6.89-6.80 (m,8H), 3.86(s,4H), 3.72(s,12H), 2.40(d,4H), 1.78 (s) , 4H), 1.47 (s, 4H), 1.32 (bs, 2H).
31P NMR(CDCl3): -45.35. 31 P NMR (CDCl 3 ): -45.35.
실시예 11. 1,3-비스(비스(2-메톡시페닐)포스피노)프로판의 제조Example 11. Preparation of 1,3-bis(bis(2-methoxyphenyl)phosphino)propane
실시예 8에서와 유사한 방법으로 1,3-비스(비스(2-메톡시페닐)포스피노)프로판을 얻었다.1,3-bis(bis(2-methoxyphenyl)phosphino)propane was obtained in a similar manner to Example 8.
1H NMR(CDCl3): 7.26-7.11(m,8H), 6.92-6.83(m,8H), 2.37(d,4H), 3.70(s,12H), 1.62(m, 2H). 1 H NMR (CDCl 3 ): 7.26-7.11(m,8H), 6.92-6.83(m,8H), 2.37(d,4H), 3.70(s,12H), 1.62(m, 2H).
31P NMR(CDCl3): -47.22. 31 P NMR (CDCl 3 ): -47.22.
실시예 12. (2,2-디메틸프로판-1,3-디일)비스(비스(2-메톡시페닐)포스핀의 제조Example 12. Preparation of (2,2-dimethylpropane-1,3-diyl)bis(bis(2-methoxyphenyl)phosphine
실시예 8에서와 유사한 방법으로 (2,2-디메틸프로판-1,3-디일)비스(비스(2-메톡시페닐)포스핀을 얻었다.(2,2-dimethylpropane-1,3-diyl)bis(bis(2-methoxyphenyl)phosphine was obtained in a similar manner as in Example 8.
1H NMR(CDCl3): 7.15 - 7.09(m, 8H), 7.01 - 6.78(m, 12H), 2.41(d, 4H), 1.04(s,6H). 1 H NMR (CDCl 3 ): 7.15 - 7.09 (m, 8H), 7.01 - 6.78 (m, 12H), 2.41 (d, 4H), 1.04 (s, 6H).
31P NMR(CDCl3): -48.41. 31 P NMR (CDCl 3 ): -48.41.
실시예 13. (2,2-디에틸프로판-1,3-디일)비스(비스(2-메톡시페닐)포스핀의 제조Example 13. Preparation of (2,2-diethylpropane-1,3-diyl)bis(bis(2-methoxyphenyl)phosphine
실시예 8에서와 유사한 방법으로 (2,2-디에틸프로판-1,3-디일)비스(비스(2-메톡시페닐)포스핀을 얻었다.(2,2-diethylpropane-1,3-diyl)bis(bis(2-methoxyphenyl)phosphine was obtained in a similar manner as in Example 8.
1H NMR(CDCl3): 7.23 - 7.12 (m, 8H), 6.97 - 6.77 (m, 12H), 2.34 (d, 4H), 1.32 (q,4H), 0.54(t. 6H). 1 H NMR (CDCl 3 ): 7.23 - 7.12 (m, 8H), 6.97 - 6.77 (m, 12H), 2.34 (d, 4H), 1.32 (q, 4H), 0.54 (t. 6H).
31P NMR(CDCl3): -48.55. 31 P NMR (CDCl 3 ): -48.55.
실시예 14. ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀 옥사이드)의 제조Example 14. Preparation of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine oxide)
질소 대기하에서 반응기에 비스(2-메톡시페닐)포스핀 옥사이드(1.0g, 3.7844mmol)과 테트라하이드로퓨란(10ml)을 투입 후 용해시키고, 포타슘 터트-부톡사이드(0.51g, 4.5413mmol) 투입 및 30분 교반하였다. 5,5-비스(브로모메틸)-2,2-디메틸-1,3-디옥산(0.68g, 2.2706mmol)을 테트라하이드로퓨란(2ml)에 용해시킨 후 30℃ 이하에서 적가하고, 1시간 교반하였다. 정제수(10ml)과 메틸렌 클로라이드(10ml)을 투입 후 분층하고 유기층을 5% 염화나트륨 수용액으로 3회 세척 후 무수 황산나트륨으로 수분을 제거하였다. 감압하여 농축한 다음, 메탄올로 슬러리 한 후 여과하고 건조한 후 재결정하여 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀 옥사이드)(1.94g, 77.12%)를 얻었다.Bis (2-methoxyphenyl) phosphine oxide (1.0 g, 3.7844 mmol) and tetrahydrofuran (10 ml) were added and dissolved in a reactor under a nitrogen atmosphere, and potassium tert-butoxide (0.51 g, 4.5413 mmol) was added and Stirred for 30 minutes. 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane (0.68 g, 2.2706 mmol) was dissolved in tetrahydrofuran (2 ml) and then added dropwise at 30° C. or less, 1 hour stirred. After adding purified water (10ml) and methylene chloride (10ml), the layers were separated, and the organic layer was washed three times with a 5% aqueous sodium chloride solution, and then moisture was removed with anhydrous sodium sulfate. After concentration under reduced pressure, slurry with methanol, filtration, drying, and recrystallization ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methyl) toxyphenyl)phosphine oxide) (1.94 g, 77.12%) was obtained.
1H NMR (CDCl3): 7.64~7.65 (m, 4H), 7.45~7.42(m, 4H), 7.00~6.96(m, 4H), 6.87~6.65(m, 4H), 3.93(s, 4H), 3.71(s, 12H), 3.15(dd, 4H), 1.23(s, 6H) 1 H NMR (CDCl 3 ): 7.64-7.65 (m, 4H), 7.45-7.42 (m, 4H), 7.00-6.96 (m, 4H), 6.87-6.65 (m, 4H), 3.93 (s, 4H) , 3.71 (s, 12H), 3.15 (dd, 4H), 1.23 (s, 6H)
31P NMR (CDCl3): 29.95 31 P NMR (CDCl 3 ): 29.95
실시예 15. ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)의 제조Example 15. Preparation of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine)
질소 대기하에서 반응기에 (2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(2-메톡시페닐)포스핀 옥사이드(5.0g, 7.5226mmol)와 톨루엔(50ml), 1,1,3,3-테트라메틸디실록산(10.1g, 75.2264mmol), 티타늄 이소프로폭사이드(5.0g, 17.3021mmol)을 투입 후 12시간 환류하여 반응하였다. 반응 후 감압하여 농축하고, 메틸렌클로라이드(50ml)와 정제수(50ml)를 투입 후 20% 수산화칼륨 수용액(10ml)을 적가 하였다. 셀라이트 여과 후 유기층을 분층하고, 5% 염화나트륨 수용액으로 3회 세척하였다. 무수 황산나트륨으로 수분을 제거하고 감압 농축 후 메틸렌클로라이드-메탄올로 재결정하여 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)(3.73g, 78.36%)를 얻었다.(2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(2-methoxyphenyl)phosphine oxide (5.0 g, 7.5226 mmol) and toluene in a reactor under nitrogen atmosphere (50ml), 1,1,3,3-tetramethyldisiloxane (10.1 g, 75.2264 mmol), and titanium isopropoxide (5.0 g, 17.3021 mmol) were added, followed by refluxing for 12 hours to react. After the reaction, the mixture was concentrated under reduced pressure, methylene chloride (50 ml) and purified water (50 ml) were added, and then 20% aqueous potassium hydroxide solution (10 ml) was added dropwise. After filtration through Celite, the organic layer was separated and washed three times with 5% aqueous sodium chloride solution. Moisture was removed with anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride-methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methyl) toxyphenyl)phosphine) (3.73 g, 78.36%) was obtained.
1H NMR (CDCl3): 7.27~7.23(m, 4H), 7.21~7.19(m, 4H), 6.87~6.84(m, 4H), 6.79~6.77(m, 4H), 3.89(s, 4H), 3.69(s, 12H), 2.47(d, 4H), 1.40(s, 6H) 1 H NMR (CDCl 3 ): 7.27 to 7.23 (m, 4H), 7.21 to 7.19 (m, 4H), 6.87 to 6.84 (m, 4H), 6.79 to 6.77 (m, 4H), 3.89 (s, 4H) , 3.69(s, 12H), 2.47(d, 4H), 1.40(s, 6H)
31P NMR (CDCl3): -47.78 31 P NMR (CDCl 3 ): -47.78
실시예 16. ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)의 제조Example 16. Preparation of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine)
실시예 15에서 1,1,3,3-테트라메틸디실록산 대신 폴리메틸하이드로실록산을 이용하여 동일한 방법으로 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)(2.49g, 52.39%)를 얻었다.((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis((2,2-dimethyl-1,3-dioxane-5,5-diyl) methylene))bis(bis(2-methoxyphenyl)phosphine) (2.49 g, 52.39%) was obtained.
본 발명이 바람직한 구체예 및 실시예를 참조로 하여 예시되었지만, 본 발명은 이로 제한되는 것이 아니고, 청구범위에 기재된 범위에 의해서 한정되어야 함을 이해할 수 있을 것이다.While the present invention has been illustrated with reference to preferred embodiments and examples, it will be understood that the present invention is not limited thereto, but should be limited by the scope set forth in the claims.
Claims (8)
i) 반응기에 하기 화학식(II)의 비스(2-메톡시페닐)포스핀 옥사이드와, 테트라하이드로퓨란 또는 톨루엔, 및 티타늄 이소프로폭사이드 또는 트리플레이트 구리(II), 및 1,1,3,3-테트라메틸디실록산 또는 폴리메틸하이드로실록산을 투입하고 환류시켜 하기 화학식(III)의 비스(2-메톡시페닐)포스핀을 생성시키는 단계;
ii) 질소 대기하에서 반응기에 상기 단계 i)에서 얻은 화학식(III)의 비스(2-메톡시페닐)포스핀과 디메틸설폭사이드 또는 테트라하이드로퓨란을 투입 후 교반하여 용해시키고, 포타슘 터트-부톡사이드를 투입한 후 교반하는 단계; 및
iii) 상기 단계 ii)로부터 얻은 용액에, 디메틸설폭사이드 또는 테트라하이드로퓨란에 용해시킨 화학식(IV) 또는 (IV')의 화합물을 20~25℃에서 적가하고 교반하여 화학식(I) 또는 (I')의 화합물을 수득하는 단계를 포함하는, 화학식(I) 또는 (I')의 화합물을 제조하는 방법:
상기 식에서,
R은 서로 독립적으로 H, C1-6 알킬, C1-6 알콕시, 또는 C1-6 알콕시페닐이고,
X는 Cl, Br, OTf, OMs, OTs 또는 ONs이다.A process for preparing a compound of formula (I) or (I'),
i) bis(2-methoxyphenyl)phosphine oxide of formula (II), tetrahydrofuran or toluene, and titanium isopropoxide or copper triflate (II), and 1,1,3 in a reactor, adding 3-tetramethyldisiloxane or polymethylhydrosiloxane and refluxing to produce bis(2-methoxyphenyl)phosphine of the following formula (III);
ii) bis(2-methoxyphenyl)phosphine of formula (III) obtained in step i) and dimethyl sulfoxide or tetrahydrofuran were added to the reactor under nitrogen atmosphere, and stirred to dissolve, and potassium tert-butoxide Stirring after the input; and
iii) To the solution obtained in step ii), a compound of formula (IV) or (IV') dissolved in dimethyl sulfoxide or tetrahydrofuran is added dropwise at 20-25° C. and stirred to add formula (I) or (I') ) A process for preparing a compound of formula (I) or (I') comprising the step of obtaining a compound of
In the above formula,
R is independently of each other H, C 1-6 alkyl, C 1-6 alkoxy, or C 1-6 alkoxyphenyl;
X is Cl, Br, OTf, OMs, OTs or ONs.
R이 서로 독립적으로 -CH3인 또는 -OCH3인, 방법.The method according to claim 1,
R is independently of each other -CH 3 or -OCH 3 The method.
상기 단계 i) 후에, 얻은 혼합물에 메틸렌클로라이드와 20% 수산화칼륨 수용액을 투입 후 유기층을 분층 후, 10% 염화나트륨 수용액으로 세척하고 무수 황산나트륨으로 수분을 제거하고, 얻은 잔사에 무수 에탄올을 넣고 공비한 후 노르말 헥산으로 슬러리화하여 여과한 다음 건조함을 추가로 포함하는, 방법.The method according to claim 1 or 2,
After step i), methylene chloride and 20% aqueous potassium hydroxide solution were added to the obtained mixture, the organic layer was separated, washed with 10% aqueous sodium chloride solution, water was removed with anhydrous sodium sulfate, and anhydrous ethanol was added to the obtained residue and azeotropic. The method further comprising slurrying with normal hexanes, filtering, and then drying.
상기 단계 iii) 후에, 얻은 혼합물에 메틸렌클로라이드와 정제수를 투입 후 분층하고, 유기층을 10% 염화나트륨 수용액으로 세척한 다음, 무수 황산나트륨으로 수분을 제거하고 메탄올로 재결정함을 추가로 포함하는, 방법.The method according to claim 1 or 2,
After step iii), methylene chloride and purified water were added to the obtained mixture, followed by partitioning, washing the organic layer with 10% aqueous sodium chloride solution, removing moisture with anhydrous sodium sulfate, and recrystallizing with methanol.
i) 질소 대기하에서 반응기에 화학식(II)의 비스(2-메톡시페닐)포스핀 옥사이드와 테트라하이드로퓨란을 투입 후 용해시키고, 포타슘 터트-부톡사이드를 투입한 후 교반시키고, 얻은 용액에, 테트라하이드로퓨란에 용해시킨 화학식(IV) 또는 (IV')의 화합물을 30℃ 이하의 온도에서 적가하고 교반하여 화학식(V) 또는 (V')의 화합물을 얻는 단계;
ii) 질소 대기하에서 반응기에 상기 단계 i)에서 얻은 화학식(V) 또는 (V')의 화합물과 톨루엔, 티타늄 이소프로폭사이드, 및 1,1,3,3-테트라메틸디실록산 또는 폴리메틸하이드로실록산을 투입 후 환류하여 반응시켜 화학식(I)의 화합물을 수득하는 단계를 포함하는, 하기 화학식(I) 또는 (I')의 화합물을 제조하는 방법:
상기 식에서,
R은 서로 독립적으로 H, C1-6 알킬, C1-6 알콕시, 또는 C1-6 알콕시페닐이고,
X는 Cl, Br, OTf, OMs, OTs 또는 ONs이다.A process for preparing a compound of formula (I) or (I'),
i) bis(2-methoxyphenyl)phosphine oxide of formula (II) and tetrahydrofuran were added and dissolved in a reactor under a nitrogen atmosphere, potassium tert-butoxide was added and stirred, and in the resulting solution, tetrahydrofuran was added A compound of formula (IV) or (IV') dissolved in hydrofuran is added dropwise at a temperature of 30° C. or lower and stirred to obtain a compound of formula (V) or (V');
ii) toluene, titanium isopropoxide, and 1,1,3,3-tetramethyldisiloxane or polymethylhydrogen with a compound of formula (V) or (V') obtained in step i) in a reactor under nitrogen atmosphere A method for preparing a compound of formula (I) or (I′), comprising the step of reacting siloxane with reflux to obtain a compound of formula (I):
In the above formula,
R is independently of each other H, C 1-6 alkyl, C 1-6 alkoxy, or C 1-6 alkoxyphenyl;
X is Cl, Br, OTf, OMs, OTs or ONs.
R이 서로 독립적으로 -CH3인 또는 -OCH3인, 방법.The method according to claim 1,
R is independently of each other -CH 3 or -OCH 3 The method.
단계 i) 후에, 얻은 혼합물에, 정제수과 메틸렌클로라이드를 투입 후 분층하고 유기층을 5% 염화나트륨 수용액으로 세척 후 무수 황산나트륨으로 수분을 제거하고, 감압하여 농축한 다음, 메탄올로 슬러리화한 후 여과하고 건조한 후에, 재결정함을 추가로 포함하는, 방법.6. The method of claim 5,
After step i), purified water and methylene chloride were added to the resulting mixture, separated, and the organic layer was washed with a 5% aqueous sodium chloride solution, dried over anhydrous sodium sulfate, concentrated under reduced pressure, slurried with methanol, filtered and dried. , the method further comprising recrystallizing.
단계 ii) 후에, 얻은 혼합물에, 메틸렌클로라이드와 정제수를 투입 후 20% 수산화칼륨 수용액을 적가하고, 셀라이트 여과 후에 유기층을 분층하고, 5% 염화나트륨 수용액으로 세척하고, 무수 황산나트륨으로 수분을 제거하고 메틸렌클로라이드-메탄올로 재결정함을 추가로 포함하는, 방법.6. The method of claim 5,
After step ii), to the obtained mixture, methylene chloride and purified water were added, and then 20% aqueous potassium hydroxide solution was added dropwise, the organic layer was separated after celite filtration, washed with 5% aqueous sodium chloride solution, water was removed with anhydrous sodium sulfate, and methylene and recrystallizing from chloride-methanol.
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| KR20170066866A (en) * | 2015-12-07 | 2017-06-15 | 에스티팜 주식회사 | A Method for Preparing Polymerization Catalyst Ligand for Polyketone |
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| KR20170066866A (en) * | 2015-12-07 | 2017-06-15 | 에스티팜 주식회사 | A Method for Preparing Polymerization Catalyst Ligand for Polyketone |
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