KR0149006B1 - 찌글러-나타 촉매 제조에 유용한 디에테르 - Google Patents
찌글러-나타 촉매 제조에 유용한 디에테르Info
- Publication number
- KR0149006B1 KR0149006B1 KR1019890014158A KR890014158A KR0149006B1 KR 0149006 B1 KR0149006 B1 KR 0149006B1 KR 1019890014158 A KR1019890014158 A KR 1019890014158A KR 890014158 A KR890014158 A KR 890014158A KR 0149006 B1 KR0149006 B1 KR 0149006B1
- Authority
- KR
- South Korea
- Prior art keywords
- ppm
- dimethoxypropane
- preparation
- vii
- multiplet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title description 17
- 239000003054 catalyst Substances 0.000 title description 3
- 150000005690 diesters Chemical class 0.000 title description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 238000009835 boiling Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- HBMODDNTUPGVFW-UHFFFAOYSA-N (1,3-dimethoxy-2-phenylpropan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(COC)(COC)C1=CC=CC=C1 HBMODDNTUPGVFW-UHFFFAOYSA-N 0.000 description 4
- IOLQAHFPDADCHJ-UHFFFAOYSA-N 5-methyl-2-propan-2-ylhex-2-enal Chemical compound CC(C)CC=C(C=O)C(C)C IOLQAHFPDADCHJ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- -1 aldehyde esters Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- PTRCHMOHGGDNIJ-UHFFFAOYSA-N 2,2-bis(2-methylpropyl)propane-1,3-diol Chemical compound CC(C)CC(CO)(CO)CC(C)C PTRCHMOHGGDNIJ-UHFFFAOYSA-N 0.000 description 3
- NDYJEAUUNHDJMC-UHFFFAOYSA-N 2,2-diphenylpropane-1,3-diol Chemical compound C=1C=CC=CC=1C(CO)(CO)C1=CC=CC=C1 NDYJEAUUNHDJMC-UHFFFAOYSA-N 0.000 description 3
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- DHVBZZMFCXFEMF-UHFFFAOYSA-N bis(2-methylpropyl) 2-ethylpropanedioate Chemical compound CC(C)COC(=O)C(CC)C(=O)OCC(C)C DHVBZZMFCXFEMF-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000012259 ether extract Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- GHRHEZKWNJRYHY-UHFFFAOYSA-N 1,3-dimethoxy-2,2,4-trimethylpentane Chemical compound COCC(C)(C)C(OC)C(C)C GHRHEZKWNJRYHY-UHFFFAOYSA-N 0.000 description 2
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 description 2
- NGMVWDKVVMVTTM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylbutane Chemical compound COCC(C(C)C)COC NGMVWDKVVMVTTM-UHFFFAOYSA-N 0.000 description 2
- ZGHOZASFRNLRAS-UHFFFAOYSA-N 2-(3-methylbutyl)-2-propan-2-ylpropane-1,3-diol Chemical compound CC(C)CCC(CO)(CO)C(C)C ZGHOZASFRNLRAS-UHFFFAOYSA-N 0.000 description 2
- FGRKWXPJHRBZHK-UHFFFAOYSA-N 3,3-bis(methoxymethyl)bicyclo[2.2.1]heptane Chemical compound C1CC2C(COC)(COC)CC1C2 FGRKWXPJHRBZHK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ZVGIBQMBZHWERX-UHFFFAOYSA-N [2-(cyclohexylmethyl)-3-methoxy-2-(methoxymethyl)propyl]cyclohexane Chemical compound C1CCCCC1CC(COC)(COC)CC1CCCCC1 ZVGIBQMBZHWERX-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MEPSBRTXOHFWCF-UHFFFAOYSA-N (2-cyclohexyl-1,3-dimethoxypropan-2-yl)cyclohexane Chemical compound C1CCCCC1C(COC)(COC)C1CCCCC1 MEPSBRTXOHFWCF-UHFFFAOYSA-N 0.000 description 1
- BEDHCUAJOBASSZ-UHFFFAOYSA-N (2-cyclopentyl-1,3-dimethoxypropan-2-yl)cyclopentane Chemical compound C1CCCC1C(COC)(COC)C1CCCC1 BEDHCUAJOBASSZ-UHFFFAOYSA-N 0.000 description 1
- WJLFNLNAXRVNGL-UHFFFAOYSA-N 1,1-bis(methoxymethyl)cyclohexane Chemical compound COCC1(COC)CCCCC1 WJLFNLNAXRVNGL-UHFFFAOYSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- OUPPKRIDJAMCCA-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,3-dimethylbutane Chemical compound COCC(C)(C(C)C)COC OUPPKRIDJAMCCA-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- FJZBADSJNSFVDO-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylpentane Chemical compound COCC(C(C)C)(C(C)C)COC FJZBADSJNSFVDO-UHFFFAOYSA-N 0.000 description 1
- RGHIYOCUMCUWAQ-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,5-dimethylhexane Chemical compound COCC(COC)(CC(C)C)C(C)C RGHIYOCUMCUWAQ-UHFFFAOYSA-N 0.000 description 1
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 1
- PYHOSWIHPZRHDU-UHFFFAOYSA-N 4,4-bis(butoxymethyl)-2,6-dimethylheptane Chemical compound CCCCOCC(CC(C)C)(CC(C)C)COCCCC PYHOSWIHPZRHDU-UHFFFAOYSA-N 0.000 description 1
- VVEYETJZOMJKNK-UHFFFAOYSA-N 4,4-bis(ethoxymethyl)-2,6-dimethylheptane Chemical compound CCOCC(CC(C)C)(CC(C)C)COCC VVEYETJZOMJKNK-UHFFFAOYSA-N 0.000 description 1
- WOLQDDKBJWHVQK-UHFFFAOYSA-N 4,4-bis(methoxymethyl)heptane Chemical compound CCCC(CCC)(COC)COC WOLQDDKBJWHVQK-UHFFFAOYSA-N 0.000 description 1
- DNZXTVCIOVBBGV-UHFFFAOYSA-N 5,5-bis(methoxymethyl)-2,8-dimethylnonane Chemical compound CC(C)CCC(COC)(CCC(C)C)COC DNZXTVCIOVBBGV-UHFFFAOYSA-N 0.000 description 1
- ZGHNQOOXLQKDSD-UHFFFAOYSA-N 6,6-bis(methoxymethyl)tridecane Chemical compound CCCCCCCC(COC)(COC)CCCCC ZGHNQOOXLQKDSD-UHFFFAOYSA-N 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- FXMXWAXLRQUWLO-UHFFFAOYSA-N CC(C)CC(C)(CC(C)C)OC(=O)CC(=O)O Chemical compound CC(C)CC(C)(CC(C)C)OC(=O)CC(=O)O FXMXWAXLRQUWLO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PQIDFVXMOZQINS-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]cyclohexane Chemical compound COCC(COC)(C(C)C)C1CCCCC1 PQIDFVXMOZQINS-UHFFFAOYSA-N 0.000 description 1
- XMYDKOZNENQEHO-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]cyclopentane Chemical compound COCC(COC)(C(C)C)C1CCCC1 XMYDKOZNENQEHO-UHFFFAOYSA-N 0.000 description 1
- HLXKHZZBHUAIQI-UHFFFAOYSA-N [2,2-bis(methoxymethyl)-3-methylbutyl]cyclohexane Chemical compound COCC(COC)(C(C)C)CC1CCCCC1 HLXKHZZBHUAIQI-UHFFFAOYSA-N 0.000 description 1
- URYLLQVLNOEEBA-UHFFFAOYSA-N [2-benzyl-3-methoxy-2-(methoxymethyl)propyl]benzene Chemical compound C=1C=CC=CC=1CC(COC)(COC)CC1=CC=CC=C1 URYLLQVLNOEEBA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UAQYREPFSVCDHT-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3-carbaldehyde Chemical compound C1CC2C(C=O)CC1C2 UAQYREPFSVCDHT-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/10—Saturated ethers of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/115—Saturated ethers containing carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/164—Unsaturated ethers containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Materials For Photolithography (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
내용 없음
Description
본 발명은 신규 종류의 디에테르에 관한 것이다.
본 발명은 디에테르는 연료에 대한 첨가제(옥탄가를 증가 시키는 기능)로서, 용매로서, 금속이온에 대한 착물형성제로서 및 찌글러-나타 촉매의 제조에 유용하다.
상기 디에테르는 하기 일반식을 갖는다.
상기식에서 R,RI, RII, RIII, RIV및 RV는 같거나 다르며, H 또는 탄소원자수 1내지 18의 직쇄 또는 분지쇄알킬, 시클로알킬, 아릴, 알킬아릴 또는 아릴알킬라디칼이며(단, R 및 RI은 둘다 H 또는 CH3가 아니거나 CH3및 n-프로필이 아님) ; RVI및 RVII는 같거나 다르며, 탄소 원자수 1내지 18의 직쇄 또는 분지쇄알킬, 시클로알킬, 아릴, 알킬아릴라디칼이며 ; R∼RVII중 하나 또는 그 이상은 결합하여 고리형 구조를 형성할 수 있다.
바람직하게는 RVI및 RVII이 탄소원자수 1내지 6의 알킬라디칼이며, RII, RIII, RIV및 RV가 수소이다. R 및 RI이 알킬라디칼인 경우, 이들은 바람직하게는 탄소원자수가 3이상이다.
본 신규 디에테르는 다양한 방법에 따라 제조할 수 있다. 예로서, 이들은 하기 일반식에 해당되는 디올로부터 출발하여 하기의 공지 에테르화 반응에 따라서 제조할 수 있다.
1) 식 II의 디올 또는 사용하는 알칼리성 알코올레이트와 식RVI- X, RVII- X, 또는 이들의 혼합물(식중에서 X = C1, Br, I, C6H5- SO3, P CH3C6H5SO3, CH3SO3)과의 반응, 여기에서 R,RI, RII, RIII, RIV및 RV는 상기에 주어진 것과 동일한 의미를 갖는다.
2) 알칼리성 조건하에서 식 II의 디올과 식 R2 VISO4또는 R2 VIISO4의 디알킬술페이트와의 반응
3) 식 II의 디올로부터 출발하여 공지 기술을 사용하는 것에 의한, 하기 일반식 III의 유도체와 RVI- OM 및 RVII- OM 알코올레이트(식중에서 M = Na, K, Mg, Ca 또는 이들의 혼합물임)와의 반응
(상기식에서 R ∼ RV및 X는 상기 지적된 의미를 가짐)
4) 일반식(III)의 디올과, RVIOM 또는 RVIIOM 알코올 또는 이들의 혼합물과의 혼합물의 열 또는 촉매적 탈수 반응.
이들 또는 기타 적당한 방법들이 하기 문헌들에 기재되어 있다 :
- Houben Weil - Metoden der Organischen Chemie Vol VI/3 Verlag ed. Stuttgard 1965.
- G.W.Gokel and Coll. Syntesis 1976, 168.
- G. Johns and Coll. ibid. 1976, 515
- D. Achet and Coll. ibid. 1986, 642.
일반식 (II)의 디올은 예컨대, 일반식(IV) 및 (V)의 상용하는 디에스테르, 디알데히드, 디케톤, 케토알데히드 또는 디카르복실산 및 일반식(VI)의 케로에스테르 및 알데히드에스테르의 환원과 같은 공지의 방법에 따라서 차례로 합성할 수 있다.
(식중에서 R,RI, RII, RIII라디칼은 앞에서 지적된 의미를 갖는다)
이들 방법의 예들이 하기 문헌들에 기재되어 있다
- H. Adkin, Organic Reactions s, 1 (1954)
- N. G. Gaylord, Reduction with Complex Metal Hydrides, Interscience Publishers, N. Y., London 1956.
- R. F. Nystrom, W. G. Brown, J. Am. Chem. Soc. 69, 1197(1947)
식 II의 또 다른 디울 (식중에서 RII, RIII, RIV및 RV는 H임)은 일반식(VII)의 알데히드로부터 카니자로 반응에 의거하여 알칼리성 포름알데히드의 작용에 의해 역시 제조할 수 있다(예컨대 Organic Reactions Vol II, pag. 94 - J. While ed. - N. Y., 1944를 참조).
(상기식에서 R 및 RI는 앞에서 지적된 의미를 가짐)
일반식 II의 디올은 공지 방법에 의해 상용하는 III 유도체로 용이하게 전환될 수 있다.(Houben Weil - Metoden der Organischen Chemie, Band V/3, V/4, IX ; Verlag ed. Stuttgard를 참고).
하기 실시예는 본 발명의 하기 에테르 및 그 제조 방법을 예시한다.
- 2-메틸, 2-이소프로필-1, 3-디메톡시프로판
- 2, 2-디이소부틸-1, 3-디메톡시프로판
- 2, 2-디페닐-1, 3-디메톡시프로판
- 2, 2-디벤질-1, 3-디메톡시프로판
- 2, 2-비스(시클로헥실메틸) 1, 3-디메톡시프로판
- 2, 2-디이소부틸-1, 3-디메톡시프로판
- 2, 2-디이소부틸-1, 3-에톡시프로판
- 2-이소펜틸, 2-이소프로필-1, 3-디메톡시프로판
- 2, 2, 4-트리메틸-1, 3-디메톡시펜탄
- 1, 1'-비스메톡시메틸시클로헥산
- (+/-)2, 2-비스(메톡시메틸)노르보르난(라세미 혼합물).
에테르의 기타 예는 다음과 같다 :
2-이소프로필-2-3, 7-디메틸옥틸-1, 3-디메톡시프로판,
2, 2-디이소프로필-1, 3-디메톡시프로판
2-이소프로필-2-시클로헥실메틸-1, 3-디메톡시프로판
2, 2-디이소펜틸-1, 3-디메톡시프로판
2-이소프로필-2-시클로헥실-1, 3-디메톡시프로판
2-이소프로필-2-시클로펜틸-1, 3-디메톡시프로판
2, 2-디시클로펜틸-1, 3-디메톡시프로판
2-헵틸-2-펜틸-1, 3-디메톡시프로판
2, 2-디시클로헥실-1, 3-디메톡시프로판
2-이소프로필-2-이소부틸-1, 3-디메톡시프로판
2, 2-디프로필-1, 3-디메톡시프로판
[실시예 1]
2, 2-디이소부틸-1, 3-디메톡시프로판의 제조
a) 디이소부틸에틸말로네이트의 제조
교반기, 냉각기, 장입 깔때기, 온도계 및 기체 유입용관을 장치한 250ml 플라스크 속에 질소 기체 흐름하에 100g의 무수 에탄올과 5g(0.22몰)의 Na를 장입한다. Na가 완전히 용해되면, 16g(0.1몰)의 디에틸말로네이트를 유입하고 실온에서 수분간 교반한다. 다음에 28g의 이소부틸브로마이드(0.21몰)를 가하고 혼합물을 진탕 시키면서 6시간동안 환류 시킨다. 계속해서 7.5g의 건조 나트륨에틸레이트(0.12몰)와 14g의 이소부틸브로마이드(0.1몰)를 가한다. 진탕 및 환류 가열은 8시간동안 더 계속한다. 대부분의 용매를 감압(50mmHg)으로 증류제거하고 잔류물을 200ml 헥산으로 추출한다. 증류된 헥산 용액은 끓는점이 145∼146℃/20mmHg인 디이소부틸에틸말로네이트 15.5g을 제공한다. 생성물은 기체 크로마토그래피법 순도(주요 피크 면적)가 97.5%이며, 문헌(Bently and Perkin, J. Chem. Soc. 73, 61)에 의거하여 제조된 디이소부틸에틸말로네이트 시료와 일치한다.
b) 2, 2-디이소부틸-1, 3-프로판디올의 제조
상기 a)에서 기술된 것과 동일한 장치 내에 질소 기체 흐름하에 100ml의 디에틸에테르와 3g의 LiAlH4(0.079몰)를 유입한다. 다음에 1시간에 걸쳐 격렬한 진탕을 유지하면서 상기 a)로 부터의 디이소부틸에틸말로네이트 15.5g을 적가하고 혼합물을 30분간 환류시킨다. 반응 혼합물을 다음에 묽은 염산으로 산성화된 얼음 100g을 담은 용기 속에 붓고 3분량의 에틸에테르 100ml로 추출한다. 에테르를 증발시키면 10g의 원료 물질이 제조되며, 이를 헥산으로 결정화하여 융점 75∼77℃이고 원소분석에서 C = 70.3% 및 H = 12.6%인 2, 2-디이소부틸-1, 3-프로판디올 8.5g을 수득한다. C11H24O2에 대한 이론치는 C = 70.21%, H = 12.7%이다.
c) 2, 2-디이소부틸-1, 3-디메톡시프로판의 제조
상기 a)에서 기술된 것과 동일한 장치속에 질소 흐름하에 8.5g(0.06몰)의 2, 2-디이소부틸-1, 3-프로판디올, 200ml의 디옥산 및 15.4g(0.136몰)의 칼륨 t-부틸레이트를 유입한다. 혼합물을 실온에서 30분간 교반한 다음에 20g의 CH3I(0.14몰)를 적가한다. 이 과정 동안에 온도는 50℃까지 자발적으로 상승한다. 2시간후, 추가량의 칼륨 t-부틸레이트(154g, 0.136몰)와 CH3I(20g, 0.14몰)를 가하고 혼합물을 1시간동안 환류시킨다. 반응 물질을 여과하고 여액을 감압 증류 시킨다. 여타 생성물 중에서, 끓는점이 100∼101℃/22mmHg이고 기체층 크로마토그래피(GLC)로써 순도 99%(크로마토그래피 피크면적)인 2, 2-디이소부틸-1, 3-디메톡시프로판 7.4g을 수득한다.
nD20 = 1.4337.
1HNMR(300MHz, CDCl3, TMS 내부 표준) :
시그널 0.89 ppm (doublet 12H)
1.21 ppm (doublet 4H)
1.68 ppm (multiplet 2H)
3.16 ppm (singlet 4H)
3.26 ppm (singlet 6H)
상기 a), b) 및 c)의 방법을 사용하여 하기 화합물을 수득한다 :
1) 2-메틸-2-이소프로필-1, 3-디메톡시프로판
nD20 = 1.4209, 끓는점 160∼161℃ / 760mmHg
2) 2, 2-디벤젠1, 3-디메톡시프로판
p.f. 105℃(석유에테르로부터)
3) 2, 2-디이소부틸-1, 3-디부톡시프로판
nD20 = 1.4378, 끓는점 115∼117℃ / 1mmHg
4) 2, 2-디이소부틸-1, 3-디에톡시프로판
nD20 = 1.4302, 끓는점 118∼120℃ / 20mmHg
[실시예 2]
2, 2-비스(시클로헥시메틸)-1, 3-디메톡시프로판의 제조
앙코트(anchor) 교반 시스템을 갖춘 스테인레스강 오토클레이브 속에, 실시예 1에 의거하여 제조된 5.8g(0.02몰)의 (C6H5CH2)2C(CH2OCH3)2, 100ml의 n-헥산 및 3부분의 50cc무수에탄올에 뒤이어 3부분의 50cc 헥산으로 경사분리하여 세척한 10g의 라니니켈을 유입한다.
오토클레이브를 17atm의 수소로 가압하고 8시간동안 진탕하면서 135℃(내부온도)까지 가열한다.
냉각후, 반응 혼합물을 촉매로부터 여과하고 진공 증발시켜 순도 99%, nD20 = 1.4790인 무색오일 5.9g을 수득한다. 박층 크로마토그래피(TLC)에 의해 검출 가능한 단독 화합물은 2, 2-비스(시클로헥실, 메틸)-1, 3-디메톡시프로판이다.
1HNMR(300MHz, CDCl3, TMS 내부 표준) :
시그널 0.96 ppm (multiplet 4H)
1.18 ppm (multiplet 12H)
1.63 ppm (multiplet 10H)
3.15 ppm (singlet 4H)
3.27 ppm (singlet 6H)
[실시예 3]
2, 2-디페닐-1, 3-디메톡시프로판의 제조
a) 2,2-디페닐-1,3-프로판디올의 제조
실시예1 a)에서 기술된 것과 동일한 장치 속에 10.6g(0.054몰)의 (C6H5)2CHCHO (Fluka), 4.03g(0.028몰)의 K2CO3, 10cc의 물, 40%(0.176몰) 포름알데히드 수용액 13.2ml 및 순도 99%의 에탄올 35ml를 유입한다.
혼합물을 6시간동안 교반 및 환류시키고, 냉각하고 200ml의 물로 희석한다. 그렇게 해서 생성된 침전을 여과하고 물로 씻고 벤젠으로 결정화하여 9.6g의 2, 2-디페닐-1, 3-프로판디올을 수득한다. 융점 102∼104℃
b) 2, 2-디페닐-1, 3-디메톡시프로판의 제조
a)에 기재된 것과 동일한 장치속에, 무수 테트라푸란 400ml에 용해된 2, 2-디페닐-1, 3-프로판디올 9.6g을 장입하고 질소하에 3.8g의 NaH(55% NaOH 악셀린오일 분산액)와 함께 수소 생성이 멈출때까지 교반한다.
20분에 걸쳐, 9.6ml의 CH3I를 가하고 2시간동안 교반을 계속한다. THF 대부분을 증류 제거한 다음, 생성물을 물(200ml)로 희석하고 2 × 50ml 분량의 디에틸에테르를 추출한다. 에테르 추출액을 진공 증류하므로써, TLC - 크로마토그래피에서 단일 물질인 끓는점 188∼190℃ / 20mmHg 및 nD20 = 1.5558 인 2, 2-디페닐-1, 3-디메톡시프로판 3.5g을 수득한다.
상기 a) 및 b)에 기술된 것과 동일한 방법에 따라서 헥사히드로벤젠알데히드 및 노르보르난-2-카르복스알데히드로부터 각각 출발하여 하기 화합물들을 제조한다.
A) 1, 1-비스메톡시메틸시클로헥산
끓는점 97∼98℃ / 20mmHg ; nD20 = 1.4487
1HNMR(300MHz, CDCl3, TMS 내부 표준) :
시그널 1.36 ppm (multiplet 10H)
3.20 ppm (singlet 4H)
3.29 ppm (singlet 6H)
B) (+/-) 2, 2-비스메톡시메틸노르보르난
끓는점 106∼108℃ / 20mmHg ; nD20 = 1.4659
1HNMR(300MHz, CDCl3, TMS 내부 표준) :
시그널 0.72 ppm (doublet 1H)
1.14 ppm (doublet 1H)
1.06 ppm (multiplet 1H)
1.34 ppm (multiplet 2H)
1.51 ppm (multiplet 3H)
1.97 ppm (singlet (broad) 1H)
2.15 ppm (singlet (broad) 1H)
3.06 ppm (system AB 1H)
3.14 ppm (system AB 1H)
3.33 ppm (system AB 1H)
3.36 ppm (system AB 1H)
3.29 ppm (multiplet 6H)
[실시예 4]
2, 2, 4-트리메틸-1, 3-디메톡시펜탄의 제조
교반기, 냉각기, 장입 깔때기, 온도계 및 기체 도입용관을 갖춘 2ℓ 플라스크 속에 질소 흐름하에 29.2g(0.2몰)의 2, 2, 4-트리메틸-1, 3-프로판디올, 600ml의 디옥산 및 10g(0.2몰)의 NaH(와셀린오일증의 50% 농도)를 장입한다. 내용물을 기체 생성이 멈출때까지 교반한 다음 80℃까지 가열하고 18ml의 CH3I (0.28몰)를 적가하여 유입한다. 2시간후 악셀린오일 중 50% 농도인 10g NaH(0.2몰)과 40cc CH3I(0.62몰)를 가한다.
8시간동안의 환류 가열후에 반응 혼합물을 1.5ℓ의 물로 희석하고 3분량의 헥산(각 100ml)으로 추출한다.
추출액을 물로 씻고 건조 및 진공 증류하여 GLC에 의한 순도가 98.6%이고 nD20 = 1.4227인 끓는점 105℃ / 170mmHg의 2, 2, 4-트리메틸-1, 3-디메톡시프로판 22.5g을 수득한다.
1HNMR(60MHz, CDCl3, TMS 내부 표준) :
시그널 1.5 ppm (multiplet 12H)
3.7 ppm (multiplet 3H)
4.1 ppm (multiplet 6H)
[실시예 5]
2-이소펜틸-2-이소프로필-1, 3-디메톡시프로판의 제조
a) 이소펜틸리덴이소펜타날의 제조
50g의 이소펜타날을 DRP 643341(1933 I. G. Farb.) 및 DRP 544192(1933 I. G. Farb.)에 기재된 방법에 따라서 반응 시킨다. 끓는점 98∼102℃ / 20mmHg의 2-이소펜틸리덴이소펜타날 27g을 수득한다.
b) 2-이소펜틸리덴이소펜타날의 제조
문헌 [J. V. Braun and G. Manz, Ber 1969, 67(1934)]에 기재된 수소화 방법에 따라서 27g의 2-이소펜틸리덴이소펜타날로 부터 출발하여, 특성화되지 않은 원료 물질 27g을 수득한다. 측정된 수소흡수는 보고된 반응과 일치한다.
c) 2-이소프로필-2-이소펜틸-1, 3-프로판디올의 제조
실시에 1 a)에서와 동일한 장치 속에 상기 b)로 부터의 원료 알데히드 27g, 16g의 K2CO3,200ml의 99% 순도 에탄올 및 40% 농도 CH2O 수용액 52ml를 유입하고 4시간동안 진탕 시키면서 환류 시킨다. 다음에 반응 혼합물을 1ℓ의 물로 희석하고 2 × 250ml분량의 에테르로 추출한다.
에테르를 증발시키고 에테르 추출액을 건조 시키고 감압 증류시켜(여타 화합물 중에서) 끓는점이 165℃ / 20mmHg 이고 TLC에서 단일한 2-이소프로필-2-이소펜틸-1, 3-프로판디올 9g을 얻는다. 이 물질을 더 이상 분석하지 않고 다음 반응에 사용한다.
d) 2-이소프로필-2-이소펜틸-1, 3-디메톡시프로판의 제조
실시예 1 a)의 장치 속에 질소 흐름하에 상기 c)로부터의 원료물질 9g, 200cc의 디옥산 및 15g의 (CH3)3COK (칼륨t-부틸레이드)를 장입하고 약 30분간 진탕한다. 다음에 1시간에 걸쳐 10ml의 CH3I를 유입하고 내용물을 5시간동안 환류시킨다. 반응 혼합물을 1ℓ의 물로 희석하고 디에틸에테르로 추출한다. 에테르를 증발시키고 에테르 추출액을 건조시키고 감압 증류한다. 여타 화합물 중에서, 끓는점 130∼133℃ / 35mmHg이고 기체 크로마토 그래피법 순도가 98.6%(피크면적)인 2-이소프로필-2-이소펜틸-1, 3-디메톡시프로판을 수득한다.
nD20 = 1.4365
1HNMR(300MHz, CDCl3, TMS 내부 표준) :
시그널 0.87 ppm (doublet 6H)
0.89 ppm (doublet 6H)
1.11 ppm (multiplet 2H)
1.28 ppm (multiplet 2H)
1.42 ppm (multiplet 1H)
1.76 ppm (multiplet 1H)
3.23 ppm (singlet 2H)
3.24 ppm (singlet 2H)
[실시예 6]
500ml 플라스크 속에 진탕하면서 60ml의 n-헵탄과 67ml의 테트라-부특시-티타늄을 45℃까지 가열한다. 3시간에 걸쳐, n-헵탄(108ml)중의 AlEt2Cl(44.8ml)의 용액을 서서히 유입한다.
온도를 1시간동안 60℃까지 올린 다음 실온까지 냉각시킨다.
고체를 분리하고 100ml 분량의 헵탄으로 4번 세척한 다음, 진공 건조 시킨다.
플라스크 속에, 이 고체 8.1g을 20.3 밀리몰의 사염화 티탄, 20.3ml의 톨루엔 및 20.3밀리몰의 2, 2-디아소부틸-1, 3-디메톡시프로판과 함께 유입하고 1시간동안 60℃까지, 다음에 100℃에서 4시간 동안 가열한다. 반응 혼합물을 다음에 실온에서 식히고 고체 생성물을 분리하고, 여액내에 염소 이온이 없어질 때까지 n-헵탄으로 세척하고 질소 흐름하에 오븐 내에서 건조 시킨다.
자기(magnetic) 교반기를 장치한 120ml 오토클레이브내에, 질소 흐름하에 건조 시킨후, 250mg의 AlEt2Cl, 12.4mg의 상기 제조한 고체 및 80ml의 액체 프로필렌을 유입하고 60℃까지 가열하고 1시간동안 진탕하면서 이 온도에 유지시킨다. 과량의 미반응 프로필렌을 방출시키고 이소택틱지수가 96.8%인 폴리프로필렌 16.9g을 수득한다(4시간동안 비등 n-헵탄으로 추출).
Claims (3)
- 하기식의 디에테르 :상기 식에서 R 및RI, RII, RIII, RIV및 RV는 같거나 다르며 H 또는 탄소원자수 1내지 18의 직쇄 또는 분지쇄알킬, 시클로알킬, 아릴, 알킬아릴 또는 아릴알킬라디칼이고(단, R 및RI은 둘다 H 또는 CH3가 아니거나 CH3및 n-프로필이 아님) ; RVI및 RVII는 같거나 다르고 탄소 원자수 1내지 18의 직쇄 또는 분지쇄알킬, 시클로알킬, 아릴, 아릴아킬라디칼이며, R∼RVII중 두 개 또는 그 이상은 결합하여 고리형 구조를 형성할 수 있다.
- 제1항에 있어서, RVI및 RVII이 탄소원자수 1내지 6의 알킬라디칼이며, RII, RIII, RIV및 RV가 수소이고, R 및RI가 알킬라디칼인 경우에 이들의 탄소원자수가 3 이상인 디에테르.
- 제2항에 있어서, 하기로 구성되는 군에서 선택되는 디에테르 :
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT8822152A IT1227260B (it) | 1988-09-30 | 1988-09-30 | Dieteri utilizzabili nella preparazione di catalizzatori ziegler-natta |
| IT22152A/88 | 1988-09-30 |
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| Publication Number | Publication Date |
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| KR900004664A KR900004664A (ko) | 1990-04-12 |
| KR0149006B1 true KR0149006B1 (ko) | 1998-10-15 |
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| KR1019890014158A Expired - Fee Related KR0149006B1 (ko) | 1988-09-30 | 1989-09-30 | 찌글러-나타 촉매 제조에 유용한 디에테르 |
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| EP (1) | EP0361493B1 (ko) |
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| KR (1) | KR0149006B1 (ko) |
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| FI (1) | FI93721C (ko) |
| HU (1) | HU206644B (ko) |
| IL (1) | IL91684A0 (ko) |
| IT (1) | IT1227260B (ko) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE888999C (de) * | 1943-01-13 | 1953-09-07 | Chemische Werke Huels Ges Mit | Verfahren zur Herstellung von Diaethern von 1, 3-Glykolen |
| US3290387A (en) * | 1961-05-08 | 1966-12-06 | Exxon Research Engineering Co | Oxyalkylated dimethylol and trimethylol alkanes |
| FR2467186A1 (fr) * | 1979-10-15 | 1981-04-17 | Elf France | Alkylethers de polyols, leur preparation et leurs emplois |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100105857A (ko) * | 2007-12-21 | 2010-09-30 | 다우 글로벌 테크놀로지스 인크. | 두자리 내부 공여체를 가진 자기-제한성 촉매 조성물 |
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