GB2486686A - Process for producing 2 alkyl-cyclopent-2-enone compounds - Google Patents
Process for producing 2 alkyl-cyclopent-2-enone compounds Download PDFInfo
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- GB2486686A GB2486686A GB1021753.7A GB201021753A GB2486686A GB 2486686 A GB2486686 A GB 2486686A GB 201021753 A GB201021753 A GB 201021753A GB 2486686 A GB2486686 A GB 2486686A
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- Prior art keywords
- cyclopentanone
- process according
- acid
- alcohol
- linear
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 36
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclo-pentanone Natural products O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 45
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003377 acid catalyst Substances 0.000 claims abstract description 19
- -1 alkylidene cyclopentanone Chemical compound 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000011541 reaction mixture Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000010924 continuous production Methods 0.000 claims abstract description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010923 batch production Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims abstract description 3
- 150000007513 acids Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920005990 polystyrene resin Polymers 0.000 claims description 3
- 239000001120 potassium sulphate Substances 0.000 claims description 2
- 150000003138 primary alcohols Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 239000003054 catalyst Substances 0.000 abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- NTSJRFHRTPPSND-UHFFFAOYSA-N methanesulfonate 1-methylpyrrolidin-1-ium-2-one Chemical compound CS([O-])(=O)=O.C[NH+]1CCCC1=O NTSJRFHRTPPSND-UHFFFAOYSA-N 0.000 abstract 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 abstract 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 abstract 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 abstract 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 abstract 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 150000003460 sulfonic acids Chemical class 0.000 abstract 1
- YZKUNNFZLUCEET-UHFFFAOYSA-N 2-pentylidenecyclopentan-1-one Chemical compound CCCCC=C1CCCC1=O YZKUNNFZLUCEET-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 12
- ILHZVKAXFCDFMT-UHFFFAOYSA-N 2-pentylcyclopent-2-en-1-one Chemical compound CCCCCC1=CCCC1=O ILHZVKAXFCDFMT-UHFFFAOYSA-N 0.000 description 10
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012433 hydrogen halide Substances 0.000 description 6
- 229910000039 hydrogen halide Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- DYVAUIYAEICDNS-UHFFFAOYSA-N 2-(1-hydroxypentyl)cyclopentan-1-one Chemical compound CCCCC(O)C1CCCC1=O DYVAUIYAEICDNS-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- UPGJEXJIJFSFDQ-UHFFFAOYSA-N 2-(1-hydroxycyclopentyl)cyclopentan-1-one Chemical compound C1CCC(=O)C1C1(O)CCCC1 UPGJEXJIJFSFDQ-UHFFFAOYSA-N 0.000 description 1
- PTJIHSFXKYSPOA-UHFFFAOYSA-N 2-pent-1-enylcyclopentan-1-one Chemical compound CCCC=CC1CCCC1=O PTJIHSFXKYSPOA-UHFFFAOYSA-N 0.000 description 1
- UUKWKUSGGZNXGA-UHFFFAOYSA-N 3,5-dinitrobenzamide Chemical compound NC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UUKWKUSGGZNXGA-UHFFFAOYSA-N 0.000 description 1
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BGTOWKSIORTVQH-HOSYLAQJSA-N cyclopentanone Chemical class O=[13C]1CCCC1 BGTOWKSIORTVQH-HOSYLAQJSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- WOPKYMRPOKFYNI-UHFFFAOYSA-N hydroxycyclopentenone Natural products OC1=CCCC1=O WOPKYMRPOKFYNI-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/395—Saturated compounds containing a keto group being part of a ring of a five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/597—Unsaturated compounds containing a keto groups being part of a ring of a five-membered ring
-
- 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
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Process for producing 2-alkyl-cyclopent-2-enone according to Formula 1 comprising isomerising 2-Âalkylidene cyclopentanone according to Formula 2, where R is linear or branched alkyl chain, at temperature greater than 150 °C in non-aqueous, halogen ion-free reaction mixture comprising alkylidene cyclopentanone, alcohol solvent and acid catalyst, wherein the weight ratio of alcohol to alkylidene cyclopentanone is greater or equal to 3:1. R is preferably linear or branched C1-8 alkyl chain and is most preferably pentyl. Preferably, reaction temperature is 160 oC to 230 oC. The alcohol solvent may be C3-22 linear or branched alcohol and is preferably 1-butanol or octanol. The catalyst may be sulfonic acids, sulfuric acid, potassium hydrogen sulfate, sulfamic acid, and acidic ionic liquids such as N-methyl-2-pyrrolidinone methane sulfonate. The catalyst may be solid supported, a sulfated zirconia, phosphotungstic acid, silicotungstic acid, acid zeolite, or sulfonated polystyrene resin. The isomerization may be a batch or continuous process.
Description
Process for producing 2-alkyl-cyclopent-2-enone compounds The invention relates to a process for producing 2-alkyl-cyclopent-2-enone compounds. Tn particular, the invention relates to processes comprising isomerising 2-ailcylidene cyclopentanone compounds. In a prefeffed embodiment, the invention relates to a process for producing 2-pentyl cyclopent-2-enone by isomerisation of pentylidene cyclopentanone, also known as 2-(1 -pentenyl) cyclopentanone.
A synthetic process for producing methyl dihydrojasmonate (MDHJ) is disclosed in GB 907,431, said process utilising a Grignard addition to cyclopentane-1,2-dione isobutyl enol ether. An alternative MDHJ synthesis is disclosed in US4260830, said process comprising an initial stage comprising a base catalysed condensation of cyclopentanone and valeraldehyde, followed by an oxalic acid catalysed dehydration and isomerisation using 5% HBr in butanol. The purified 2-pentyl cyclopent-2-enone is then reacted with dimethyl malonate and this adduct is then hydrolysed at approximately 200 °C using water to produce MDHJ. This process can be conveniently summarised as follows: 0 Aldol 0 OH Dehydration 0 Condensation a + Isomerisation IIIII Hydrolysss CO2Me Numerous modifications and/ or improvements have been made to the MDHJ synthesis process disclosed in US4260830 and, in particular, a number of processes associated with the isomerisation of pentylidene cyclopentanone to 2-pentyl cyclopent-2-enone are known. For example, in addition to US 4260830, further isomerisation reactions are known which utilize hydrogen halide catalysts, e.g. HC1 or HBr. Such reactions are disclosed in JP 59080625, ES 540432, JP 06080606, JP 05092934 and JP 2000-327618. However, it is known that most hydrogen halide catalysed isomerisation reactions may be run under reflux conditions, but such conditions encourage catalyst loss by evaporation. Furthermore, hydrogen halides react with alcohol solvents to form alkyl halides and water and/or catalyse the formation of ethers and additional water. Consequently, it is difficult to maintain steady catalyst levels and consistent reaction profiles when using such catalysts. Furthermore, recycling of solvent is difficult due to the production of numerous impurities during such hydrogen halide catalysed reactions.
It is also known to use nitrogen containing compounds such as picoline as a co-catalyst with hydrogen halides. For instance, JP 06080606 discloses the use ofpyridine.HC1, and EP 1134210 discloses the use of HC1 or HBr with picoline, pyridine or quino line. Although the use of a hydrogen halide / nitrogen compound co-catalyst may reduce the need to continually top up catalyst levels because formation of amine hydrochloride salts can act as a hydrogen halide reservoir, impurities such as ethers and alkyl halides continue to be produced. Further, such reactions tend to be slow, with better yields being obtained at higher temperatures. Often the use of high boiling, expensive alcohol solvents produce high boiling point ethers which are difficult to remove from the product. Furthermore, a post isomerisation acid wash followed by base neutralization step is required in order to remove the nitrogen compound co-catalyst. In addition, further recycling steps may be required prior to re-use of the co-catalyst.
As an alternative to the above hydrogen halide catalysts, platinum group metals may be utilized.
For instance, WO 2009128347 discloses the use of hydrogen activated platinum or palladium catalysts under slightly reduced N2/H2 pressure. However, such metals are expensive, and so may affect commercial viability. Further, such catalysts may require pre-activation under hydrogen which can give rise to a pyrophoric material. Furthermore, such processes may provide decreased yields due to olefin reduction and can be relatively slow, e.g. 5 to 6 hours.
It is also known to use other acids, both protic and Lewis as a catalyst for the isomerisation reaction. For instance, JP 2001-26 1608 discloses a dehydration and isomerisation reaction utilising sulphuric or alkyl sulphonic acid and a high boiling point solvent such as 1,9-nonanediol heated to 160°C, from which the product needs to be continually distilled to achieve an acceptable yield.
Iodine or bromine are also known catalysts for such isomerisation reactions. For instance, such a reaction is disclosed in EP 1316541 wherein low levels ofT2 or Br2 are refluxed in a hydrocarbon solvent. However, such reactions may require the use of distilled feedstock and careful quality control to achieve the best results. Further, the use of iodine, particularly HI, can cause blockage problems as it tends to sublime and is corrosive.
The use of solid acids as catalysts for the isomerisation reaction has also been reported, albeit at high temperature (250-450°C) and in the vapour phase in JP 55120533. More usually the use of a solid acid has been applied to the dehydration step before reverting to other methods for the isomerisation. For instance, WO 2009125713 discloses a combined dehydration/isomerisation reaction by reacting the aldol with a solid acid dehydration catalyst in the presence of a platinum group metal catalyst.
Further, simultaneous condensation, dehydration and isomerisation reactions are disclosed in WO 2006072775 and WO 2006072785. In the disclosed reactions, cyclopentanone and valeraldehyde are added to a complex ionic liquid containing proline.
It is also known that the isomerisation reaction can be carried out in a continuous process. For example, JP 2009084176 provides a continuous reaction wherein pentylidene cyclopentanone, butanol and HC1 are passed through a Raschig ring packed column.
It is an object of the present invention to provide alternative processes for the production of 2-alkyl-cyclopent-2-enone compounds, in particular 2-pentyl cyclopent-2-enone.
It is a further object of the present invention to provide for the production of 2-alkyl-cyclopent-2-enone compounds which overcomes one or more deficiencies associated with conventional production processes.
It is a further objective of the present invention to provide processes for the production of 2-alkyl-cyclopent-2-enone compounds with improved product yields in comparison with conventional alkylidene cyclopentanone isomerisation processes.
The present invention, in its various aspects, is as set out in the accompanying claims.
In one aspect, the present invention provides a process for producing a 2-alkyl-cyclopent-2-enone of Formula 1: Formula 1 said process comprising isomerising a 2-ailcylidene cyclopentanone of Formula 2:
R
Formula 2 wherein R represents a linear or branched alkyl chain, at a temperature in excess of 150 °C in a non-aqueous, halogen ion-free reaction mixture comprising said ailcylidene cyclopentanone, an alcohol solvent and an acid catalyst, wherein the weight ratio of said alcohol to said ailcylidene cyclopentanone is greater than or equal to 3:1.
Preferably, R represents a linear or branched C1 to C8 alkyl chain, more preferably R represents a linear C1 to C8 ailcyl chain, and most preferably R is a linear C4 alkyl chain.
Preferably, the isomerisation reaction is carried out at a temperature of from 160 °C to 230 °C, more preferably at a temperature of from 180 °C to 200 °C, and most preferably at 190°C.
Preferably, the alcohol solvent is a C3-C22 linear or branched alcohol, more preferably the alcohol solvent is a linear C4-C3 alcohol.
Preferably, the alcohol solvent is a primary alcohol, more preferably butanol, hexanol or octanol, even more preferably butanol, and most preferably 1 -butanol.
Preferably, the weight ratio of alcohol solvent to ailcylidene cyclopentanone is from 3:1 to 10:1, more preferably 3.5:1 to 10:1, more preferably 3.5:1 to 6:1, and most preferably 4:1.
Preferably, in the reaction mixture the catalyst is present in a liquid or solid form. By "liquid" or "solid", we mean that the catalyst is in that physical form during the reaction of the reaction mixture.
When the catalyst is present in the reaction mixture in a liquid form, the acid catalyst preferably comprises at least one compound selected from the group consisting of sulphonic acids, sulphuric acid, potassium hydrogen sulphate, sulphamic acid and non-aqueous acidic ionic liquids, preferably a Bronsted acidic ionic liquid such as N-methyl-2-pyrolidinone methane sulphonate and l-(4-sulphobutyl)-3-methylimidazolium hydrogen sulphate, ofwhich N-methyl- 2-pyrolidinone methane sulphonate is a preferred example. More preferably, the acid catalyst comprises one or more sulphonic acids, and most preferably, the acid catalyst is p-toluene sulphonic acid.
When the catalyst is present in the reaction mixture in a solid form, the acid catalyst preferably comprises at least one compound selected from the group consisting of supported sulphonic acids, sulphated zirconias, phosphotungstic acids, silicotungstic acids, acid zeolites and sulphonated polystyrene resins. More preferably, the acid catalyst is a supported p-toluenesulphonic acid or an acidic zeolite. Most preferably, the acid catalyst is a supported acidic zeolite.
The term "supported sulphonic acids" is readily understood by persons skilled in the art, however for the for the avoidance of any doubt it is intended that such a term means a sulphonic acid compound absorbed and/or adsorbed onto a solid support structure that is inert to the reaction mixture. Preferably, the sulphonic acid compound is adsorbed onto a polar support structure.
Preferably, the molar ratio of acid catalyst to allcylidene cyclopentanone is from 1:1,000 to 1:10, preferably from 1:250 to 1:30.
Preferably, the isomerisation reaction of the present invention is carried out in a batch or continuous process.
When the isomerisation reaction is performed in a batch process, it is preferred that the batch process is carried out at a temperature of from 160 to 230°C, more preferably from 180 to 200°C.
In a preferred batch process, the weight ratio of alcohol to ailcylidene cyclopentanone is from 3:1 to 6:1, more preferably from 3.5:1 to 5:1. In apreferredbatchprocess, the molarratio of acid catalyst to ailcylidene cyclopentanone is from 1:1,000 to 1:10, more preferably from 1:250 to 8:250.
In a preferred batch process, the reaction mixture is maintained at a pressure from 1 to 50 atmospheres, more preferably from 1 to 10 atmospheres. In a preferred batch process, the isomerisation reaction time is from 15 to 360 minutes, more preferably from 30 to 120 minutes.
When the isomerisation reaction is performed in a continuous process, it is preferred that the continuous process is carried out at a temperature of from 160 to 230°C, more preferably from to 200°C. In a preferred continuous process, the weight ratio of alcohol to ailcylidene cyclopentanone is from 3:1 to 6:1, more preferably from 3.5:1 to 5:1. In a preferred continuous process, the molar ratio of acid catalyst to ailcylidene cyclopentanone is from 1:1,000 to 1:10, more preferably from 1:250 to 8:250.In a preferred continuous process, the reaction mixture is maintained at a pressure from 1 to 50 atmospheres, more preferably from 1 to 10 atmospheres. In a preferred continuous process, the reactor residence time is from 6 to 360 minutes, more preferably from 15 to 60 minutes.
V/hen the isomerisation process is performed in a continuous process, it is preferred that the isomerisation reaction step is performed in a tubular reactor, wherein the length of the tubular reactor is at least 5 times greater than its internal diameter, more preferably the length of the tubular reactor is at least 10 times greater than its internal diameter.
It has been surprisingly found that the novel process of the present invention results in improved 2-alkyl-cyclopent-2-enone yields in comparison with known alkylidene cyclopentanone isomerisation processes.
The present invention shall now be more specifically described and explained by way of the following non-limiting examples: Example 1: Preparation of 2-(1-hydroxypentyl) cyclopentanone: 567.81g, 6.75mo1 Cyclopentanone and 750.Og, 4l.63mo1 water are charged to a 3.SL stirred jacketed reactor and cooled to 0°C under nitrogen. Approximately 7.2%, 37.35g. 67.Smmol aqueous sodium hydroxide is added, then a mixture of cyclopentanone (l324.89g, l5.75mo1) and freshly distilled valeraldehyde (775.00 g, 9.OOmol) is continuously added by pump at a rate of 7.OOg/h over 5h. Ten additional aliquots of sodium hydroxide (20%, 3.l85g, l5.7Smmol each) are dosed into the reactor at 30 minute intervals. At the end of the additions, the reaction mixture is stirred for a further 2h at 0°C before neutralising with 85% phosphoric acid (25.94g, 0.225mo1) and water (20.OOg, 1.1 lmol). Upon warming to 30°C a lower aqueous layer is rnn off and the resulting organic phase analysed by UC using hexadecane as an internal standard. The resulting intermediate contained l2.5g, 82.2mmolpentylidene cyclopentanone, 1391.4g, 8.l7mol 2-(l-hydroxypentyl) cyclopentanone and 26.3g, l56mmol 2-(1-hydroxycyclopentyl) cyclopentanone. The calculated yield of was 91.7%.
Example 2: Batch Isomerisation: Octanol (160g, 1.23mo1) was pre-heated to 190°C and stirred under nitrogen. A solution of distilled pentylidene cyclopentanone (40.Og, 97% assay, 0.2SSmol), hexadecane UC standard (1.6g) and methanesulphonic acid (9 10mg, 9.48mmol) was added and the mixture stirred for 30 minutes. The resulting product contained 2-pentylcyclopent-2-enone, 32.07g, 0.2lmol, 82.6% yield, conversion 98.8%.
Example 3: Batch Isomerisation: Similar to Example 2, octanol (bOg, 0.77mol) was reacted with pentylidene cyclopentanone (40g, 0.2SSmol), hexadecane UC standard (1.6g) and methanesulphonic acid (518mg, 5.39mmol) at 170°C for 75 minutes. The resulting product contained 2-pentylcyclopent-2-enone, 30.38g, 0.2Omol, 78.3% yield, conversion 99.3%.
Example 4: Batch Isomerisation: A 3Oml Carius pressure tube is charged with 1-butanol (16.Og, 0.22mo1), distilled pentylidene cyclopentanone (4.OOg, 97% assay, 25.Smmol), p-toluenesulphonic acid (0.l625g, 0.7O87mmol) and hexadecane (0.08g) UC standard, sealed and immersed in an oil bath at 190°C and stirred for 30 minutes. The resulting mixture contained 2-pentylcyclopent-2-enone, 3.490g, 22.9mmol, 89.6% yield Example 5: Batch Isomerisation: A mixture of 1-butanol (21.0kg, 283mo1) and crude pentylidene cyclopentanone (3.56kg, 23.38mo1) was charged to a lOOL autoclave and pre-heated to 180°C producing a rise in pressure to 5.3bar. A solution of p-toluenesulphonic acid monohydrate (25.Og, 0.13 imol) in 1-butanol (225g, 3.O3mol) was added giving a rise in pressure to -â.7bar and the reaction mixture stirred for 2h before cooling, releasing the pressure and neutralising with 10% aqueous sodium hydroxide. Quantitative UC analysis using hexadecane as internal standard gave 2-pentylcyclopent-2-enone (3.31kg, 21.73mol, 92.9% yield) and pentylidene cyclopentanone (83.7g, 0.SSmol).
Example 6: Continuous Isomerisation: A continuous "pumped tube" reactor was developed using either a Hewlett Packard, HP 1050 or Gilson 305 pump to supply reactants to a 316 stainless steel tube (OD 6mm, ID 4mm, length 16m, nominal volume ?-200ml) immersed in a Huber Unistat CC oil bath. Following reaction the reagents are cooled to room temperature by flowing through a coil in a water/ice bath and emitted via a pressure sustaining valve to a sample collection point.
The continuous "pumped tube" reactor is prepared for reaction by slowly pumping 1 -butanol (flow = lml/min), the pressure is increased to 20 bar using the pressure sustaining valve and the temperature of the oil bath set at 200°C. On reaching stable operating conditions, the flow rate is increased to 1 Oml/min and the pump supply swapped to provide a mixture of crude pentylidene cyclopentanone (50.OSg, 77.3%, 0.254mo1, pentylidene cyclopentanone), 75% aqueous p-TSA (1.24g, 5.4 mmol) and 1-butanol (199.95g, 2.7Omol). As the supply reservoir empties additional charges are added until 250.0g of crude pentylidene cyclopentanone (-A000.Og,1 -butanol and -6.2g 75% pTSA) are processed. The reactor output is collected as 200g fractions and each neutralised with 10% aqueous sodium hydroxide. Quantitative analysis of the second and fourth fractions reveals pentylidene cyclopentanone (0.61 g, 4.Ommol) and 2-pentyl cyclopent-2-enone (28.45g, 0.l87mol) and pentylidene cyclopentanone (0.56g, 3.7mmol) and 2-pentyl cyclopent-2-enone (28.57g, 0.188mo1), respectively. This conesponds to a conversion of98.0% and yield of 91.9% for fraction 2 and 98.2% conversion and 92.3% yield for fraction 4.
Example 7: Heterogeneous Batch Isomerisation A 30m1 Carius pressure tube is charged with 1 -butanol (l6.Og, 0.22mol), distilled pentylidene cyclopentanone (3.85g, 97% assay, 24.Smmol), solid catalyst (0.1 -0.4g,) and hexadecane (0. 15g) GC standard, sealed and immersed in an oil bath at 190°C and stirred using a magnetic stir bar for 90 minutes. The results for a number of solid catalysts are shown in Table 1
Table 1
Catalyst Catalyst Amount/g Conversion/% Yield/% Supported p-toluenesulphonic acid 0.105 99.0 83.9 Suiphated Zirconia 0.4298 94.2 79.7 Silicotungstic Acid on silica/alumina 0.2054 97.6 79.3 Silicotungstic Acid/silica 0.1055 98.8 80.7 Zeolite ZD06014 (Zcolyst) 0.3994 98.9 89.1 Sulphonated Polystyrene Resin (Quadrapure) (Reaxa) 0.4161 99.1 84.1 Sulphonic Acid on Silica 0.4117 97.9 84.5 (Quadrasil) (Reaxa)
Claims (4)
- Claims 1) A process for producing a 2-allcyl-cyclopent-2-enone of Formula 1: 1 Formula said process comprising isomerising a 2-alkylidene cyclopentanone of Fonnula 2:RFormula wherein R represents a linear or branched alkyl chain, at a temperature in excess of 150 °C in a non-aqueous, halogen ion-free reaction mixture comprising said alkylidene cyclopentanone, an alcohol solvent and an acid catalyst, wherein the weight ratio of said alcohol to said ailcylidene cyclopentanone is greater than orequalto 3:1.
- 2) A process according to claim 1, wherein R represents a linear or branched C1 to C3 alkyl chain, preferably a linear Ci to Cs ailcyl chain, more preferably a linear C4 alikyl chain.
- 3) A process according to any of the preceding claims, wherein the isomerisation is carried out at a temperature of from 160 °C to 230 °C, preferably at a temperature of from 180°C to 200 °C, such as 190°C.
- 4) A process according to any of the preceding claims, wherein the alcohol solvent is a C3-C22 linear or branched alcohol, more preferably a linear C4-C3 alcohol 5) A process according to any of the preceding claims, wherein the alcohol solvent is a primary alcohol, preferably butanol, hexanol or octanol, more preferably butanol, most preferably 1 -butanol.6) A process according to any of the preceding claims, wherein the weight ratio of alcohol solvent to ailcylidene cyclopentanone is from 3:1 to 10:1, preferably 3.5:1 to 10:1, more preferably 3.5:1 to 6:1, such as 4:1.7) A process according to any of the preceding claims, wherein in the reaction mixture the acid catalyst is in a liquid or solid form.8) A process according to any of the preceding claims, wherein said acid catalyst comprises at least one compound selected from the group consisting of sulphonic acids, sulphuric acid, potassium hydrogen sulphate, suiphamic acid and acidic ionic liquids, preferably a Bronsted acidic ionic liquid of which N-methyl-2-pyrolidinone methane sulphonate is a prefeffed example, preferably the acid catalyst is one or more sulphonic acids.9) A process according to claim 7, wherein the acid catalyst comprises at least one compound selected from the group consisting of suiphonic acids absorbed or adsorbed on a solid inert support, sulphated zirconias, phosphotungstic acids, silicotungstic acids, acid zeolites and suiphonated polystyrene resins.10) A process according to any of the preceding claims, wherein the molar ratio of acid catalyst to ailcylidene cyclopentanone is from 1:1,000 to 1:10, preferably from 1:250 to 1:30.11) A process according to any of the preceding claims, wherein the isomerisation is performed in a batch process.12) A process according to claim 11, wherein: i) the batch process is carried out at a temperature of from 160 to 230°C, preferably from 180 to 200°C; ii) the weight ratio of alcohol to alkylidene cyclopentanone is from 3:1 to 6:1, preferably from 3.5:1 to 5:1; iii) the molar ratio of acid catalyst to alkylidene cyclopentanone is from 1:1,000 to 1:10, preferably from 1:250 to 8:250; iv) the reaction mixture is maintained at a pressure from 1 to 50 atmospheres, preferably from 1 to 1 Oatmospheres; and v) the isomerisation reaction time is from 15 to 360 minutes, preferably from 3Oto 120 minutes.13) A process according to any of claims ito 10, wherein the isomerisation is performed in a continuous process, preferably in a tubular reactor.14) A process according to claim 13, wherein: i) the continuous process is carried out at a temperature of from 160 to 23 0°C, preferably from 180 to 200°C; ii) the weight ratio of alcohol to alkylidene cyclopentanone is from 3:i to 6:1, preferably from 3.5:1 to 5:1; iii) the molar ratio of acid catalyst to alkylidene cyclopentanone is from 1:1,000 to 1:10, preferably from i:2SOto 8:250; iv) the reaction mixture is maintained at a pressure from 1 to 50 atmospheres, preferably from 1 to 10 atmospheres; and v) the reactor residence time is from 6 to 360 minutes, preferably from iS to 60 minutes.
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| CN114478217A (en) * | 2022-02-18 | 2022-05-13 | 山东新和成药业有限公司 | Preparation method of 2-n-pentylcyclopent-2-enone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5123240A (en) * | 1974-08-14 | 1976-02-24 | Toray Industries | 22 arukiru 22 shikuropentenonno seizoho |
| JPH0592934A (en) * | 1991-09-30 | 1993-04-16 | Nippon Zeon Co Ltd | Production of 2-alkyl-2-cycloalkene-1-one compounds |
| JP2001261608A (en) * | 2000-03-15 | 2001-09-26 | Kao Corp | Method for producing 2-alkyl-2-cyclopentenone |
-
2010
- 2010-12-22 GB GB1021753.7A patent/GB2486686A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5123240A (en) * | 1974-08-14 | 1976-02-24 | Toray Industries | 22 arukiru 22 shikuropentenonno seizoho |
| JPH0592934A (en) * | 1991-09-30 | 1993-04-16 | Nippon Zeon Co Ltd | Production of 2-alkyl-2-cycloalkene-1-one compounds |
| JP2001261608A (en) * | 2000-03-15 | 2001-09-26 | Kao Corp | Method for producing 2-alkyl-2-cyclopentenone |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478217A (en) * | 2022-02-18 | 2022-05-13 | 山东新和成药业有限公司 | Preparation method of 2-n-pentylcyclopent-2-enone |
| CN114478217B (en) * | 2022-02-18 | 2023-08-08 | 山东新和成药业有限公司 | Preparation method of 2-n-amyl cyclopent-2-enone |
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