DE10064751A1 - Production of alk-3-en-1-ol compounds, useful as intermediates in chemical synthesis, involves reacting formaldehyde with optionally 2-substituted propene in the presence of a mixture of hydrogen phosphates and dihydrogen phosphates - Google Patents
Production of alk-3-en-1-ol compounds, useful as intermediates in chemical synthesis, involves reacting formaldehyde with optionally 2-substituted propene in the presence of a mixture of hydrogen phosphates and dihydrogen phosphatesInfo
- Publication number
- DE10064751A1 DE10064751A1 DE10064751A DE10064751A DE10064751A1 DE 10064751 A1 DE10064751 A1 DE 10064751A1 DE 10064751 A DE10064751 A DE 10064751A DE 10064751 A DE10064751 A DE 10064751A DE 10064751 A1 DE10064751 A1 DE 10064751A1
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- phosphates
- hydrogen
- mixture
- series
- 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.)
- Withdrawn
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- -1 2-substituted propene Chemical class 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 239000000543 intermediate Substances 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 title 1
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 35
- 125000004805 propylene group Chemical class [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 6
- 125000004986 diarylamino group Chemical group 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000003738 xylenes Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 6
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 description 4
- 235000019800 disodium phosphate Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 4
- 235000019799 monosodium phosphate Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 150000002012 dioxanes Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XGJWQNKXTXSVML-UHFFFAOYSA-N 1,3,5,7-tetraoxocane Chemical compound C1OCOCOCO1 XGJWQNKXTXSVML-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- MQZGYYYBCTXEME-UHFFFAOYSA-N [Rb][Rb] Chemical compound [Rb][Rb] MQZGYYYBCTXEME-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- IOPOLWHQYJSKCT-UHFFFAOYSA-L barium(2+);dihydrogen phosphate Chemical compound [Ba+2].OP(O)([O-])=O.OP(O)([O-])=O IOPOLWHQYJSKCT-UHFFFAOYSA-L 0.000 description 1
- LYSTYSFIGYAXTG-UHFFFAOYSA-L barium(2+);hydrogen phosphate Chemical compound [Ba+2].OP([O-])([O-])=O LYSTYSFIGYAXTG-UHFFFAOYSA-L 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- QPTUMKXXAAHOOE-UHFFFAOYSA-M cesium;hydron;phosphate Chemical compound [Cs+].OP(O)([O-])=O QPTUMKXXAAHOOE-UHFFFAOYSA-M 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- MOJITMJAFATXAX-UHFFFAOYSA-M dihydrogen phosphate;rubidium(1+) Chemical compound [Rb+].OP(O)([O-])=O MOJITMJAFATXAX-UHFFFAOYSA-M 0.000 description 1
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 1
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- HKSVWJWYDJQNEV-UHFFFAOYSA-L strontium;hydron;phosphate Chemical compound [Sr+2].OP([O-])([O-])=O HKSVWJWYDJQNEV-UHFFFAOYSA-L 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Alk-3-en-1-olen durch Um setzung von Formaldehyd mit Propenen, welche an 2-Position einen Substituenten aus der Reihe Wasserstoff, Alkyl oder Aryl tragen, in Gegenwart einer Mischung aus Dihydrogenphosphaten und Hydrogenphosphaten.The invention relates to a process for the preparation of alk-3-en-1-ols by Um settlement of formaldehyde with propenes which have a substituent at the 2-position from the series carry hydrogen, alkyl or aryl in the presence of a mixture of Dihydrogen phosphates and hydrogen phosphates.
Alk-3-en-1-ole sind wertvolle Zwischenprodukte bei der Synthese organischer Verbindungen. 3-Methyl-3-buten-1-ol wird beispielsweise als Ausgangskomponente zur Herstellung von Isopren eingesetzt. 3-Buten-1-ol ist eine Feinchemikalie, für die bislang nur sehr kostenintensive technische Syntheseverfahren existieren.Alk-3-en-1-oles are valuable intermediates in the synthesis of organic Links. 3-methyl-3-buten-1-ol is used, for example, as a starting component used for the production of isoprene. 3-buten-1-ol is a fine chemical for which So far, only very cost-intensive technical synthesis processes exist.
Die Herstellung von Alk-3-en-1-olen durch Umsetzung von Propylen oder substituierten Propenen ist bekannt. Als mögliche Nebenprodukte treten beispielsweise Alk-2-en-1-ole und/oder Dioxanderivate auf.The production of alk-3-en-1-ols by reacting propylene or substituted propenes is known. Occur as possible by-products for example, alk-2-en-1-ols and / or dioxane derivatives.
In GB 1 205 397 B wird die Umsetzung von Isobuten mit Formaldehyd in Gegenwart von Zinnchlorid beschrieben. Nachteilig an diesem Verfahren ist, dass 3-Methyl-3- buten-1-ol nur mit einer Selektivität von maximal 22% erhalten wurde.GB 1 205 397 B describes the reaction of isobutene with formaldehyde in the presence described by tin chloride. The disadvantage of this process is that 3-methyl-3- buten-1-ol was only obtained with a selectivity of at most 22%.
In US 3,574,773 wird die Umsetzung von Propylen mit Formaldehyd bei Temperaturen von 235-400°C beschrieben. Nachteilig an diesem Verfahren ist, dass unter diesen Reaktionsbedingungen mit 65% eine relativ niedrige Selektivität für 3- Buten-1-ol erzielt wurde. Weiterhin nachteilig sind die geringen Umsätze (s. Beispiel 3 der vorliegenden Anmeldung).In US 3,574,773 the reaction of propylene with formaldehyde Temperatures of 235-400 ° C described. The disadvantage of this method is that under these reaction conditions with 65% a relatively low selectivity for 3- Buten-1-ol was achieved. Another disadvantage is the low sales (see example 3 of the present application).
In US 4,028,424 ist die Umsetzung von Propylen mit Paraformaldehyd in Gegenwart von Natriumhydrogenphosphat beschrieben. Nachteilig an dieser Reaktionsführung ist, dass 3-Buten-1-ol mit einer vergleichsweise geringen Selektivität von 63% erhalten wurde. Auch hier sind geringe Umsätze von Nachteil (s. Beispiel 2 der vorliegenden Anmeldung).In US 4,028,424 the reaction of propylene with paraformaldehyde is in the presence described by sodium hydrogen phosphate. A disadvantage of this reaction procedure is that 3-buten-1-ol with a comparatively low selectivity of 63% was obtained. Here, too, low sales are disadvantageous (see example 2 of the present application).
Es bestand daher Bedarf an einem Verfahren zur Herstellung von Alk-3-en-1-olen durch Umsetzung von Propenen mit Formaldehyd, welches sich durch hohe Selektivitäten auszeichnet und somit eine aufwendige, komplizierte und kostenintensive Abtrennung unerwünschter Nebenprodukte vermieden werden kann.There was therefore a need for a process for the preparation of alk-3-en-1-ols by reacting propenes with formaldehyde, which is characterized by high Selectivities distinguishes and thus a complex, complicated and costly separation of unwanted by-products can be avoided.
Überraschenderweise wurde nun ein Verfahren zur Herstellung von Alk-3-en-1-olen durch Umsetzung von Formaldehyd mit Propenen, welche an 2-Position einen Substituenten aus der Reihe Wasserstoff, Alkyl oder Aryl tragen, gefunden, welches dadurch gekennzeichnet ist, dass die Umsetzung in Gegenwart einer Mischung aus Dihydrogenphosphaten und Hydrogenphosphaten durchgeführt wird.Surprisingly, there has now been a process for the preparation of alk-3-en-1-ols by reacting formaldehyde with propenes which have a 2-position Carrying substituents from the series hydrogen, alkyl or aryl, found which is characterized in that the reaction in the presence of a mixture of Dihydrogen phosphates and hydrogen phosphates is carried out.
Im erfindungsgemäßen Verfahren werden Alk-3-en-1-ole mit hohen Selektivitäten und guten Ausbeuten erhalten. Zudem werden kaum Nebenprodukte ähnlicher Siedepunkte und/oder Dioxanderivate gebildet, was besonders für eine groß technische Durchführung des Verfahrens von Vorteil ist, da die Abtrennung dieser Produkte problematisch und kostenintensiv ist.In the process according to the invention, alk-3-en-1-ols are used with high selectivities and get good yields. In addition, hardly any by-products are more similar Boiling points and / or dioxane derivatives formed, which is especially great for a Technical implementation of the method is advantageous because the separation of this Products is problematic and costly.
Im erfindungsgemäßen Verfahren werden Propene, welche an 2-Position einen Substituenten aus der Reihe Wasserstoff, Alkyl oder Aryl tragen, eingesetzt, wobei der genannte Substituent Aryl seinerseits einen oder mehrere Substituenten aus der Reihe lineares und verzweigtes C1-Cg-Alkyl und C1-C8-Alkoxy, halogeniertes lineares und verzweigtes C1-C8-Alkyl und C1-C8-Alkoxy, lineares und verzweigtes C1-C8-Alkyloxycarbonyl und Aryloxycarbonyl, C1-C8-Dialkylamino, Diarylamino, Cyano und Halogene wie F, Cl, Br und I tragen kann und der genannte Substituent Alkyl seinerseits einen oder mehrere Substituenten aus der Reihe lineares und verzweigtes C1-C8-Alkyl, lineares und verzweigtes C1-C8-Alkyloxycarbonyl und Aryloxycarbonyl, C1-C8-Dialkylamino und Diarylamino tragen kann. Vorzugsweise werden im erfindungsgemäßen Verfahren Propene eingesetzt, welche an 2-Position einen Substituenten aus der Reihe Wasserstoff, C1-C4-Alkyl oder Phenyl tragen, wobei der genannte Substituent Phenyl seinerseits einen oder mehrere Substituenten aus der Reihe lineares und verzweigtes C1-C8-Alkyl und C1-C8-Alkoxy, halogeniertes lineares und verzweigtes C1-C8-Alkyl und C1-C8-Alkoxy, lineares und verzweigtes C1-C8-Alkyloxycarbonyl und Aryloxycarbonyl, C1-C8-Dialkylamino, Diarylamino, Cyano und Halogene wie F, Cl, Br und I tragen kann und der genannte Substituent C1-C4-Alkyl seinerseits einen oder mehrere Substituenten aus der Reihe lineares und verzweigtes C1-C4-Alkyl, lineares und verzweigtes C1-C4- Alkyloxycarbonyl und Aryloxycarbonyl, C1-C4-Dialkylamino und Diarylamino tragen kann. Besonders bevorzugt werden Propene eingesetzt, welche einen Substituenten aus der Reihe Wasserstoff, Methyl, Ethyl, n-Propyl, Isopropyl und n- Butyl tragen. Ganz besonders bevorzugt wird Propylen und Isobutylen eingesetzt.In the process according to the invention, propenes which carry a substituent from the hydrogen, alkyl or aryl series at the 2-position are used, the aryl substituent in turn being one or more substituents from the series consisting of linear and branched C 1 -C g -alkyl and C 1 -C 8 alkoxy, halogenated linear and branched C 1 -C 8 alkyl and C 1 -C 8 alkoxy, linear and branched C 1 -C 8 alkyloxycarbonyl and aryloxycarbonyl, C 1 -C 8 dialkylamino, diarylamino, Can carry cyano and halogens such as F, Cl, Br and I and said substituent alkyl in turn one or more substituents from the series linear and branched C 1 -C 8 alkyl, linear and branched C 1 -C 8 alkyloxycarbonyl and aryloxycarbonyl, C 1 -C 8 dialkylamino and diarylamino can wear. In the process according to the invention, preference is given to using propenes which carry a substituent from the series hydrogen, C 1 -C 4 -alkyl or phenyl at the 2-position, the phenyl substituent mentioned in turn being one or more substituents from the series linear and branched C 1 - C 8 alkyl and C 1 -C 8 alkoxy, halogenated linear and branched C 1 -C 8 alkyl and C 1 -C 8 alkoxy, linear and branched C 1 -C 8 alkyloxycarbonyl and aryloxycarbonyl, C 1 -C 8 -Dialkylamino, diarylamino, cyano and halogens such as F, Cl, Br and I can carry and said substituent C 1 -C 4 alkyl in turn one or more substituents from the series linear and branched C 1 -C 4 alkyl, linear and can carry branched C 1 -C 4 alkyloxycarbonyl and aryloxycarbonyl, C 1 -C 4 dialkylamino and diarylamino. Propenes which carry a substituent from the series hydrogen, methyl, ethyl, n-propyl, isopropyl and n-butyl are particularly preferably used. Propylene and isobutylene are very particularly preferably used.
Der im erfindungsgemäßen Verfahren eingesetzte Formaldehyd kann gasförmig, in polymerer Form oder in Form einer wässrigen Lösung eingesetzt werden. Wird Formaldehyd im erfindungsgemäßen Verfahren in Form einer wässrigen Lösung ein gesetzt, so wird vorzugsweise eine 35 bis 55%ige Lösung, besonders bevorzugt eine 35%ige Lösung eingesetzt. Wird Formaldehyd im erfindungsgemäßen Verfahren in polymerer Form eingesetzt, so werden vorzugsweise 1,3,5-Trioxan, 1,3,5,7-Tetroxan oder Paraformaldehyd, welcher einen Polymerisationsgrad von 8 bis 100 aufweist, eingesetzt. Ganz besonders bevorzugt wird im erfindungsgemäßen Verfahren Paraformaldehyd oder gasförmiger Formaldehyd eingesetzt.The formaldehyde used in the process according to the invention can be gaseous polymeric form or in the form of an aqueous solution. Becomes Formaldehyde in the process according to the invention in the form of an aqueous solution is set, then preferably a 35 to 55% solution, particularly preferably one 35% solution used. Is formaldehyde in the inventive method in polymeric form, 1,3,5-trioxane, 1,3,5,7-tetroxane are preferably used or paraformaldehyde, which has a degree of polymerization of 8 to 100, used. It is very particularly preferred in the process according to the invention Paraformaldehyde or gaseous formaldehyde is used.
Im erfindungsgemäßen Verfahren können Formaldehyd und die erfindungsgemäß einzusetzenden Propene in stöchiometrischen Mengen umgesetzt werden, vorzugs weise werden die erfindungsgemäß einzusetzenden Propene jedoch im Überschuss eingesetzt. Dabei werden vorzugsweise 1,5 bis 100 Mol der erfindungsgemäß einzu setzenden Propene pro Mol Formaldehyd eingesetzt, insbesondere 2 bis 60 Mol, be sonders bevorzugt 3 bis 30 Mol. In the process according to the invention, formaldehyde and those according to the invention Propenes to be used are implemented in stoichiometric amounts, preferably however, the propenes to be used according to the invention are used in excess used. It is preferably 1.5 to 100 moles of the invention setting propenes used per mole of formaldehyde, in particular 2 to 60 moles, be particularly preferably 3 to 30 mol.
Das erfindungsgemäße Verfahren wird in Gegenwart einer Mischung aus Dihydro genphosphaten und Hydrogenphosphaten durchgeführt. Bevorzugte Dihydrogen phosphate und Hydrogenphosphate sind diejenigen der Alkali- und/oder Erdalkali metalle wie beispielsweise Dilithiumhydrogenphosphat, Lithium dihydrogenphosphat, Dinatriumhydrogenphosphat, Natriumdihydrogenphosphat, Dikaliumhydrogenphosphat, Kaliumdihydrogenphosphat, Dicäsiumhydrogen phosphat, Cäsiumdihydrogenphosphat, Dirubidiumhydrogenphosphat, Rubidiumdihydrogenphosphat, Magnesiumhydrogenphosphat, Magnesium dihydrogenphosphat, Calciumhydrogenphosphat, Calciumdihydrogenphosphat, Bariumhydrogenphosphat, Bariumdihydrogenphosphat, Strontiumhydrogenphosphat, Strontiumdihydrogenphosphat. Bevorzugte Dihydrogen- und Hydrogenphosphate sind weiterhin Diammoniumhydrogenphosphat und Ammoniumdihydrogenphosphat. Besonders bevorzugt wird im erfindungsgemäßen Verfahren eine Mischung aus Dialkalimetallhydrogenphosphaten und Alkalimetalldihydrogenphosphaten einge setzt, vorzugsweise eine Mischung aus Dikalium- und/oder Dinatrium hydrogenphosphat und Kalium- und/oder Natriumdihydrogenphosphat. Die Mischung kann auch aus verschiedenen Dihydrogenphosphaten und Hydrogenphosphaten bestehen.The process according to the invention is carried out in the presence of a mixture of dihydro gene phosphates and hydrogen phosphates carried out. Preferred dihydrogen phosphates and hydrogen phosphates are those of alkali and / or alkaline earths metals such as dilithium hydrogen phosphate, lithium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, Dipotassium hydrogen phosphate, potassium dihydrogen phosphate, diceium hydrogen phosphate, cesium dihydrogen phosphate, dirubidium hydrogen phosphate, Rubidium dihydrogen phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, Barium hydrogen phosphate, barium dihydrogen phosphate, strontium hydrogen phosphate, Strontiumdihydrogenphosphat. Preferred dihydrogen and hydrogen phosphates are also diammonium hydrogen phosphate and ammonium dihydrogen phosphate. A mixture of is particularly preferred in the process according to the invention Dialkalimetalhydrogenphosphaten and alkali metal dihydrogenphosphaten inserted sets, preferably a mixture of dipotassium and / or disodium hydrogen phosphate and potassium and / or sodium dihydrogen phosphate. The Mixture can also be made from various dihydrogen phosphates and Hydrogen phosphates exist.
Die Mischungen aus Hydrogenphosphaten und Dihydrogenphosphaten werden im er findungsgemäßen Verfahren vorzugsweise im Stoffmengenverhältnis 5 : 1 bis 1 : 2, be sonders bevorzugt im Stoffmengenverhältnis 3 : 1 bis 1 : 1,5, eingesetzt.The mixtures of hydrogen phosphates and dihydrogen phosphates are in the Process according to the invention preferably in a molar ratio of 5: 1 to 1: 2, be particularly preferably in a molar ratio of 3: 1 to 1: 1.5.
Die Mischungen aus Hydrogenphosphaten und Dihydrogenphosphaten werden im er findungsgemäßen Verfahren vorzugsweise in einer Menge von 0,1 bis 30 Mol%, bevorzugt von 0,5 bis 25 Mol% und besonders bevorzugt von 0,5 bis 15 Mol%, bezogen auf Formaldehyd, eingesetzt.The mixtures of hydrogen phosphates and dihydrogen phosphates are in the process according to the invention preferably in an amount of 0.1 to 30 mol%, preferably from 0.5 to 25 mol% and particularly preferably from 0.5 to 15 mol%, based on formaldehyde.
Das erfindungsgemäße Verfahren wird vorzugsweise bei Temperaturen von -20°C bis 320°C, besonders bevorzugt bei 50°C bis 300°C und ganz besonders bevorzugt bei 180°C bis 280°C durchgeführt. The inventive method is preferably at temperatures of -20 ° C. up to 320 ° C, particularly preferably at 50 ° C to 300 ° C and very particularly preferred performed at 180 ° C to 280 ° C.
Das erfindungsgemäße Verfahren wird vorzugsweise bei Drücken von 100 bis 250 bar, besonders bevorzugt 100 bis 230 bar und ganz besonders bevorzugt 110 bis 200 bar durchgeführt.The inventive method is preferably at pressures from 100 to 250 bar, particularly preferably 100 to 230 bar and very particularly preferably 110 to 200 bar carried out.
Das erfindungsgemäße Verfahren kann in Gegenwart eines Lösungsmittels oder in Substanz durchgeführt werden. Vorzugsweise wird in Gegenwart eines Lösungsmittels gearbeitet. Bevorzugte Lösungsmittel sind gesättigte aliphatische Kohlenwasserstoffe, alicyclische Kohlenwasserstoffe, aromatische Kohlenwasser stoffe, Alkohole, Ester oder Ether. Beispielsweise können als Lösungsmittel Pentan, Hexan, Heptan, Octan, Cyclohexan, Benzol, Toluol, Xylole, Ethylbenzol, Mesitylen, Dioxan, Tetrahydrofuran, Diethylether, Dibutylether, Diisopropylether, Diethylen glykol-dimethylether, Methanol, Ethanol, Propanol, Isopropanol, n-Butanol, Isobutanol, sek.-Butanol, tert.-Butanol, Amylalkohol, Hexanol, Heptanol, Octanol, Methylacetat, Ethylacetat, Propylacetat, tert.-Butylacetat oder Phthalsäureester wie beispielsweise Dioctylphthalat eingesetzt werden. Besonders bevorzugt werden Ether, wie beipielsweise Diisopropylether oder Diethylenglykol-dimethylether oder substituierte aromatische Kohlenwasserstoffe, wie beispielsweise Toluol, Xylole, Ethylbenzol oder Mesitylen eingesetzt. Ganz besonders bevorzugt werden Toluol und Xylole eingesetzt.The inventive method can in the presence of a solvent or in Substance are carried out. Preferably in the presence of a Solvent worked. Preferred solvents are saturated aliphatic Hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons substances, alcohols, esters or ethers. For example, pentane, Hexane, heptane, octane, cyclohexane, benzene, toluene, xylenes, ethylbenzene, mesitylene, Dioxane, tetrahydrofuran, diethyl ether, dibutyl ether, diisopropyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, isopropanol, n-butanol, Isobutanol, sec-butanol, tert-butanol, amyl alcohol, hexanol, heptanol, octanol, Methyl acetate, ethyl acetate, propyl acetate, tert-butyl acetate or phthalic acid esters such as for example, dioctyl phthalate can be used. Be particularly preferred Ethers, such as diisopropyl ether or diethylene glycol dimethyl ether or substituted aromatic hydrocarbons, such as toluene, xylenes, Ethylbenzene or mesitylene used. Toluene is very particularly preferred and xylenes used.
Das erfindungsgemäße Verfahren wird vorzugsweise so durchgeführt, dass Form aldehyd, vorzugsweise Paraformaldehyd oder gasförmiger Formaldeyhd, zusammen mit einer Mischung aus Hydrogenphosphaten und Dihydrogenphosphaten vorzugsweise in einem Lösungsmittel vorgelegt wird. Anschließend erfolgt die Zugabe der erfindungsgemäß einzusetzenden Propene.The method according to the invention is preferably carried out in such a way that shape aldehyde, preferably paraformaldehyde or gaseous formaldehyde with a mixture of hydrogen phosphates and dihydrogen phosphates is preferably presented in a solvent. Then the Addition of the propenes to be used according to the invention.
Zur Isolierung der erfindungsgemäß hergestellten Alk-3-en-1-ole wird das Reak tionsgemisch nach Beendigung der Reaktion vorzugsweise filtriert. Das Filtrat kann nun beispielsweise destillativ oder durch Extraktion aufgearbeitet werden. Vorzugsweise wird die Aufarbeitung so durchgeführt, dass die Alk-3-en-1-ole destillativ abgetrennt werden.To isolate the alk-3-en-1-ols prepared according to the invention, the reak tion mixture preferably filtered after completion of the reaction. The filtrate can can now be worked up, for example, by distillation or by extraction. Preferably the workup is carried out so that the alk-3-en-1-ole is distilled be separated.
2 g Paraformaldehyd (0,066 Mol) wurden zusammen mit 10 Mol% einer Mischung aus 400 mg Natriumdihydrogenphosphat und 472 mg Natriumhydrogenphosphat (Stoffmengenverhältnis 1 : 1) in 80 ml Toluol in einem 300 ml-Autoklaven vorgelegt. Es wurden 80 g Propylen (1,9 Mol) zudosiert. Nach Erwärmung der Reaktionsmischung auf 220°C wurde Stickstoff bis zu einem Druck von 150 bar aufgedrückt und die Reaktionsmischung für eine Dauer von 12 Stunden gerührt. Nach Beendigung der Reaktion wurde 3-Buten-1-ol mit einer Selektivität von 97% bei einen Umsatz von 36% erhalten (gaschromatographische Analyse mit Diethylenglykol-Dimethylether als interner Standard.2 g of paraformaldehyde (0.066 mol) was added together with 10 mol% of a mixture from 400 mg sodium dihydrogen phosphate and 472 mg sodium hydrogen phosphate (Mole ratio 1: 1) in 80 ml of toluene in a 300 ml autoclave. 80 g of propylene (1.9 mol) were metered in. After heating the Reaction mixture at 220 ° C was nitrogen up to a pressure of 150 bar pressed on and the reaction mixture was stirred for a period of 12 hours. After the reaction, 3-buten-1-ol was selected with a selectivity of 97% obtained with a conversion of 36% (gas chromatographic analysis with Diethylene glycol dimethyl ether as an internal standard.
9 g Paraformaldehyd (0,3 Mol) wurden zusammen mit 0,22 g Natriumhydrogen phosphat und 60 ml tert.-Butanol in einem 300 ml-Autoklaven vorgelegt. Es wurden 80 g (120 ml) Propylen (1,9 Mol) zudosiert. Nach Erwärmung der Reaktionsmischung auf 230°C wurde für eine Dauer von 4 Stunden gerührt. Nach Beendigung der Reaktion wurde 3-Buten-1-ol mit einer Selektivität von 51% bei einem Umsatz von 6% erhalten (gaschromatographische Analyse mit Diethylenglykol-Dimethylether als interner Standard).9 g of paraformaldehyde (0.3 mol) were added along with 0.22 g of sodium hydrogen phosphate and 60 ml of tert-butanol in a 300 ml autoclave. There were 80 g (120 ml) of propylene (1.9 mol) were metered in. After heating the Reaction mixture at 230 ° C was stirred for 4 hours. To The reaction was terminated with 3-buten-1-ol with a selectivity of 51% received a conversion of 6% (gas chromatographic analysis with Diethylene glycol dimethyl ether as an internal standard).
800 ml 37%ige Formalinlösung wurden in einem 700 ml-Autoklaven vorgelegt. Es wurden 213 g (320 ml) Propylen zudosiert. Die Reaktionsmischung wurde auf 310°C erwärmt und für eine Dauer von 1 Stunde gerührt. Nach Beendigung der Reaktion wurde 3-Buten-1-ol mit einer Selektivität von 68% bei einem Umsatz von 6% erhalten (gaschromatographische Analyse mit Diethylenglykol-Dimethylether als interner Standard).800 ml of 37% formalin solution were placed in a 700 ml autoclave. It 213 g (320 ml) of propylene were metered in. The reaction mixture was brought to 310 ° C warmed and stirred for 1 hour. After the reaction has ended was 3-buten-1-ol with a selectivity of 68% with a conversion of 6% obtained (gas chromatographic analysis with diethylene glycol dimethyl ether as internal standard).
2 g Paraformaldehyd (0,066 Mol) wurden zusammen mit 10 Mol% einer Mischung aus 400 mg Natriumdihydrogenphosphat und 472 mg Natriumhydrogenphosphat (Stoffmengenverhältnis 1 : 1) in 80 ml Toluol in einem 300 ml-Autoklaven vorgelegt. Es wurden 120 ml Isobutylen (1,26 Mol) zudosiert. Nach Erwärmung der Reaktionsmischung auf 220°C wurde Stickstoff bis zu einem Druck von 150 bar aufgedrückt und die Reaktionsmischung für eine Dauer von 12 Stunden gerührt. Nach Beendigung der Reaktion wurde 3-Methyl-3-buten-1-ol mit einer Selektivität von 98% bei einen Umsatz von < 99% erhalten (gaschromatographische Analyse mit Diethylenglykol-Dimethylether als interner Standard.2 g of paraformaldehyde (0.066 mol) was added together with 10 mol% of a mixture from 400 mg sodium dihydrogen phosphate and 472 mg sodium hydrogen phosphate (Mole ratio 1: 1) in 80 ml of toluene in a 300 ml autoclave. 120 ml of isobutylene (1.26 mol) were metered in. After heating the Reaction mixture at 220 ° C was nitrogen up to a pressure of 150 bar pressed on and the reaction mixture was stirred for a period of 12 hours. After the reaction was over, 3-methyl-3-buten-1-ol was selected obtained from 98% with a conversion of <99% (gas chromatographic analysis with Diethylene glycol dimethyl ether as an internal standard.
Claims (11)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10064751A DE10064751A1 (en) | 2000-12-22 | 2000-12-22 | Production of alk-3-en-1-ol compounds, useful as intermediates in chemical synthesis, involves reacting formaldehyde with optionally 2-substituted propene in the presence of a mixture of hydrogen phosphates and dihydrogen phosphates |
| PCT/EP2001/014445 WO2002051776A2 (en) | 2000-12-22 | 2001-12-10 | Method of producing alk-3-ene-1-ols |
| AU2002231683A AU2002231683A1 (en) | 2000-12-22 | 2001-12-10 | Method of producing alk-3-ene-1-ols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10064751A DE10064751A1 (en) | 2000-12-22 | 2000-12-22 | Production of alk-3-en-1-ol compounds, useful as intermediates in chemical synthesis, involves reacting formaldehyde with optionally 2-substituted propene in the presence of a mixture of hydrogen phosphates and dihydrogen phosphates |
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| Country | Link |
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| AU (1) | AU2002231683A1 (en) |
| DE (1) | DE10064751A1 (en) |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008037693A1 (en) * | 2006-09-26 | 2008-04-03 | Basf Se | Continuous method for producing citral |
| CN102557876A (en) * | 2011-12-29 | 2012-07-11 | 南通天泽化工有限公司 | Process for producing 3-methyl-3-buten-1-ol |
| CN104387234A (en) * | 2014-11-21 | 2015-03-04 | 山东新和成药业有限公司 | Method for synthesizing 3-methyl-3-butene-1-ol |
| WO2020049111A1 (en) | 2018-09-05 | 2020-03-12 | Basf Se | Process for producing isoprenol |
| WO2022189652A1 (en) | 2021-03-12 | 2022-09-15 | Basf Se | Process for recovering isoprenol |
| WO2025078316A1 (en) | 2023-10-13 | 2025-04-17 | Basf Se | Process for the preparation of prenal and isovaleraldehyde |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3763696B1 (en) | 2014-06-02 | 2023-07-05 | Kuraray Co., Ltd. | Production method for gamma, delta-unsaturated alcohols |
| EP3578537B1 (en) | 2017-01-31 | 2021-10-06 | Kuraray Co., Ltd. | Method for producing gamma, delta-unsaturated alcohol |
| CN110997606B (en) * | 2017-08-11 | 2023-03-10 | 巴斯夫欧洲公司 | Process for recovering 3-methylbut-3-en-1-ol |
| EP3853195B1 (en) | 2018-09-18 | 2024-05-01 | Basf Se | Process to recover high quality 3-methyl-but-3-en-1-ol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH509241A (en) * | 1967-02-25 | 1971-06-30 | Basf Ag | Process for the preparation of compounds with an alk-3-en-1-ol structure |
| US4028424A (en) * | 1974-11-15 | 1977-06-07 | Japan Synthetic Rubber Co., Ltd. | Process for preparing unsaturated alcohols |
-
2000
- 2000-12-22 DE DE10064751A patent/DE10064751A1/en not_active Withdrawn
-
2001
- 2001-12-10 AU AU2002231683A patent/AU2002231683A1/en not_active Abandoned
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008037693A1 (en) * | 2006-09-26 | 2008-04-03 | Basf Se | Continuous method for producing citral |
| CN102557876A (en) * | 2011-12-29 | 2012-07-11 | 南通天泽化工有限公司 | Process for producing 3-methyl-3-buten-1-ol |
| CN104387234A (en) * | 2014-11-21 | 2015-03-04 | 山东新和成药业有限公司 | Method for synthesizing 3-methyl-3-butene-1-ol |
| CN104387234B (en) * | 2014-11-21 | 2016-08-17 | 山东新和成药业有限公司 | A kind of synthetic method of 3-methyl-3-butene-1-alcohol |
| WO2020049111A1 (en) | 2018-09-05 | 2020-03-12 | Basf Se | Process for producing isoprenol |
| WO2022189652A1 (en) | 2021-03-12 | 2022-09-15 | Basf Se | Process for recovering isoprenol |
| WO2025078316A1 (en) | 2023-10-13 | 2025-04-17 | Basf Se | Process for the preparation of prenal and isovaleraldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002051776A3 (en) | 2002-12-05 |
| AU2002231683A1 (en) | 2002-07-08 |
| WO2002051776A2 (en) | 2002-07-04 |
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