GB2189244A - Process for the preparation of (+)-13-norfaranal - Google Patents
Process for the preparation of (+)-13-norfaranal Download PDFInfo
- Publication number
- GB2189244A GB2189244A GB08708603A GB8708603A GB2189244A GB 2189244 A GB2189244 A GB 2189244A GB 08708603 A GB08708603 A GB 08708603A GB 8708603 A GB8708603 A GB 8708603A GB 2189244 A GB2189244 A GB 2189244A
- Authority
- GB
- United Kingdom
- Prior art keywords
- compound
- general formula
- formula
- process according
- stands
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 56
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- -1 p- toluenesulfonyloxy Chemical group 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 5
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052987 metal hydride Inorganic materials 0.000 claims description 4
- 150000004681 metal hydrides Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- RCBVKBFIWMOMHF-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium;pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1.O[Cr](=O)(=O)O[Cr](O)(=O)=O RCBVKBFIWMOMHF-UHFFFAOYSA-L 0.000 claims description 3
- 125000005948 methanesulfonyloxy group Chemical group 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 230000002140 halogenating effect Effects 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- KDCIHNCMPUBDKT-UHFFFAOYSA-N hexane;propan-2-one Chemical compound CC(C)=O.CCCCCC KDCIHNCMPUBDKT-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NEXRYLFKZCYFFB-MMJTVPDGSA-N (3s,4r,6e)-3,4,7,11-tetramethyldodeca-6,10-dienal Chemical compound O=CC[C@H](C)[C@H](C)C\C=C(/C)CCC=C(C)C NEXRYLFKZCYFFB-MMJTVPDGSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229940086542 triethylamine Drugs 0.000 description 3
- JSCUZAYKVZXKQE-JXMROGBWSA-N (2e)-1-bromo-3,7-dimethylocta-2,6-diene Chemical compound CC(C)=CCC\C(C)=C\CBr JSCUZAYKVZXKQE-JXMROGBWSA-N 0.000 description 2
- 101150041968 CDC13 gene Proteins 0.000 description 2
- XIFWHIKDTORZQI-MSOLQXFVSA-N C[C@@H](CCOCOC)[C@@H](CC=C(CCC=C(C)C)/C)C Chemical compound C[C@@H](CCOCOC)[C@@H](CC=C(CCC=C(C)C)/C)C XIFWHIKDTORZQI-MSOLQXFVSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- 241000257303 Hymenoptera Species 0.000 description 2
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 2
- NFGXHKASABOEEW-LDRANXPESA-N methoprene Chemical compound COC(C)(C)CCCC(C)C\C=C\C(\C)=C\C(=O)OC(C)C NFGXHKASABOEEW-LDRANXPESA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- AMFDSAVMBKVRFK-CVEARBPZSA-N C[C@@H](CCO)[C@@H](CC=C(CCC=C(C)C)/C)C Chemical compound C[C@@H](CCO)[C@@H](CC=C(CCC=C(C)C)/C)C AMFDSAVMBKVRFK-CVEARBPZSA-N 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 102000003960 Ligases Human genes 0.000 description 1
- 108090000364 Ligases Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- VCLWSWMAOCDYJR-UHFFFAOYSA-N dodeca-2,6,10-trien-1-ol Chemical compound CC=CCCC=CCCC=CCO VCLWSWMAOCDYJR-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- FFOWJDCTFSWUMJ-JXMROGBWSA-N geranyl phosphate Chemical compound CC(C)=CCC\C(C)=C\COP(O)(O)=O FFOWJDCTFSWUMJ-JXMROGBWSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229930014550 juvenile hormone Natural products 0.000 description 1
- 239000002949 juvenile hormone Substances 0.000 description 1
- 150000003633 juvenile hormone derivatives Chemical class 0.000 description 1
- AHNJTQYTRPXLLG-UHFFFAOYSA-N lithium;diethylazanide Chemical compound [Li+].CC[N-]CC AHNJTQYTRPXLLG-UHFFFAOYSA-N 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 125000005905 mesyloxy group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000017448 oviposition Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Natural products C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/292—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with chromium derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
Description
GB2189244A 1
SPECIFICATION
Process for the preparation of (+)-13-norfaranal This invention relates to a new process for the preparation of (+)-13- norfaranal, which is the 5 tracing feromone of Pharaoh's ant.
From the insect pests settled in the environment of men Pharaoh's ant is the most difficult to control. Pharaoh's ant hides its nests in the walls of flats and here the queens which provide for race preservation, propagation and quick reproduction are practically unavailable for conventional insecticides. 10 Recently compounds having juvenile hormone effect were succesfully used in the control of Pharaoh's ant (e.g. methopren). The Pharaoh's ants carry foodstuff treated with methopren into the anthill and this inhibits oviposition of the queens.
Pharaoh's ant uses 20-25 m long routes when seeking for food and the ants mark these routes by a specific luring material-the so-called -tracing feromon"- being characteristic of this 15 species. (+)-faranal is the most active component of the said tracing feromon of Pharaoh's ant and this compound induces the Pharaoh's ant workers to leave the anthill and hollow the trace even in a concentration of 1 pg/cm. This compound can be effectively used for the control of Pharaoh's ant when combined with juvenoides.
According to Hoyama et al [Naturwissenschaften 70, 469 (1983)l (+)-13norfaranal, having a 20 more simple structure than (+)-faranal, exerts a very strong tracing effect on Pharaoh's ant workers, the said effect being almost as high as that of (+)-faranal. Thus (+)-13-norfaranal is also suitable for use in the control of Pharaoh's ant when combined with juvenoides.
(+)-13-norfaranal has not yet been prepared in pure form so far. In prior art a single synthesis is disclosed [T. Koyama, M. Matsubara, K. Ogura, I.E.M. BrOggemann, A. Vrielink: Naturwissen- 25 schaften 70, 469 (1983)l which results in the formation of a 40:60 mixture of (+)-13-norfaranal and the diastereomer thereof having a (3R,4R)-configuration. Geraniol is used as starting material, which is phosphorilated, and the geranyl phosphate thus obtained is coupled with (Z)-3-methyl-3pentenyl-pyrophosphate with the aid of a purified synthetase enzyme system extracted from pig liver. This reaction gives with low yield the pyrophosphate of (4R)-(2E, 6E)-3,4,7,1 1-tetramethyl- 30 2,6,10-dodecatriene-l-ol, the product thus obtained is hydrolyzed by means of a phosphatase enzyme system and the (4R)-(2E,6E)-3,4,7,1 1-tetramethyl-2,6,10- dodecatrien-l-oI is oxidized with activated manganese oxide. The (4R)-(2E,6E)-3,4,7,1 1 -tetramethyi-2,6- 1 0-dodecatrienal thus ob tained is reduced with a tetrakis-(triphenylphosphite)-pailadium tributyl- tin-hydride system to a 40:60 mixture of (3S,4R)-(E)-3,4,7,1 1-tetramethyl-6,10-dodecadienal and (3R,4R)-(E)-3,4,7,1 1-tet- 35 ramethy]-6,10-dodecadienal; the said two components are not separated.
It is the object of the present invention to overcome the drawbacks of the known method and to provide a readily feasible process for the preparation of (+)-13- norfaranal.
According to the present invention there is provided a process for the preparation of (+) (3S,4R)-3,4,6, 11 -tetramethyl-6, 1 0-dodecadienal [(+)- 1 3-norfaranai)l of the Formula (1) 40 CHO which comprises forming an anion from the compound of the Formula (11) 45 50 0ú0 with a - strong base; reacting the anion thus obtained with a compound of the general Formula (111) 55 60 (wherein X stands for chlorine, bromine, iodine., methanesulfonyloxy or p- toluenesulfonyloxy); esterifying the compound of the Formula (IV) 2 GB2189244A 2 0) 0 ([V) 5 thus obtained; treating the compound of the general Formula (V) OH (V) 1 10 COOR1 thus obtained (wherein R' stands for a straight or branched chain alkyl group having 1-6 carbon atoms) with an agent capable of protecting the hydroxy group; reducing the compound of the general Formula (V1) 15 OR2 (V1) COORI 20 thus obtained with a metal hydride (wherein W) is as stated above and R2 stands for methoxy methyl, 1-ethoxy-ethyl or 2-tetrahydropyranyl); reacting the compound of the general Formula (VII) 25 OR2 (V11) 1 IOH 30 thus obtained (wherein R2 is as stated above) with a halogenating or acylating agent; reducing the compound of the general Formula (V111) 35 (VIII) -,X 40 thus obtained (wherein R2 and X are as stated above); hydrolysing the compound of the general Formula (IX) 45 OR2 (IX) 50 thus obtained (wherein R2 is as stated above); and oxidizing the compound of the Formula (X) (X) 55 thus obtained into (+)-13-norfaranal of the Formula (1).
The present invention is based on the recognition that (+)-13-norfaranal of the Formula (1) can 60 be easily prepared in pure form from the readily available optically active compond of the Formula (11) [C.S. Chen, Y. Fujimoto, G. Girdaukas, C.J. Sih: J. Am. Chem. Soc. 104, 7297 (1982)1. In the first step of the synthesis from (S)-4-methyi-tetrahydro2H-pyrane-2-one of the Formula (11) an anion is formed with the aid of a strong base (preferably with lithium diethylamide prepared from diethyl amine and butyl lithium), the anion thus formed is reacted without isolation 65 3 GB2189244A 3 with a compound of the general Formula (111) (wherein X is chlorine, bromine, iodide, mesyloxy, tosyloxy) preferably with the readily available geranyl bromide of the general Formula (111) (wherein X stands for bromine); P. Gosselin, G. Madman F. Roussac: [Synthesis 877, (1984)].
The reaction is carried out at low temperature, preferably between -78C and -30'C. From the reaction mixture the compound of the Formula (IV) thus formed being contaminated by 5-6% of 5 the (3S,4S)-diastereomer thereof is isolated by extraction and purified by column chromato graphy.
The compond of the Formula (N) is converted into an ester of the general Formula (V) (wherein R' stands for a straight or branched chain alkyl group having 1- 6 carbon atoms). It is preferred to form a methyl ester in methanol with trimethyl amine. The ester of the general 10 Formula (V) thus obtained is isolated, if desired, and thereafter converted into a compound of the general Formula (V1) (wherein R' is as stated above and 112 stands for methoxymethyl, 1 ethoxy-ethyl or 2-tetrahydropyranyl). This reaction is carried out in a manner known per se, e.g.
by reacting the compound of the general Formula (V) with chloromethyl methyl ether to yield a compound of the general Formula (V1), wherein R' is methyl and R 2 stands for methoxymethyl. 15 The compound of the general Formula (V1) is reduced with a metal hydride (preferably with lithium tetrahydrido aluminate) in an anhydrous aprotic solvent (preferably in dry tetrahydrofurane) to yield the compound of the general Formula (VII) (wherein R 2 is as stated above).
The compound of the general Formula (VII) is isolated and converted into a compound of the general Formula (VIII) by methods known per se (wherein X and R2 are as stated above). One 20 may proceed preferably by using mesyl chloride and preparing a mesylate of the general Formula (VIII) (wherein R2 is as stated above, preferably methoxymethyl and X stands for mesyloxy). The compound thus obtained is reduced with a metal hydride (preferably lithium tetrahydrido alumi nate) in an anhydrous aprotic solvent (preferably anhydrous tetrahydrofurane) to yield a com pound of the general Formula (IX) (wherein R2 is as stated above). 25 The compound of the general Formula (IX) is isolated, whereupon the protecting group is removed by acid-catalysed hydrolysis-preferably by using 0.1-0.01 M methanolic hydrogen chloride. The compound of the general Formula (X) thus obtained is isolated and oxidized with a known oxidizing agent (preferably pyridinium dichromate). From the reaction mixture the desired compound of the Formula (1) ((+)- 1 3-norfa ra nail is isolated with an isomer purity of 94-95%. 30 Further details of the present invention are to be found in the following Examples without limiting the scope of protection to the said Examples.
Example 1 (-)-(3R,4S)-(E)-4-methyi-3(3,7-dimethyi-2,6-octadienyi)-tetrahydro-2Hpyrane -2-one (compound of 35 the Formula IV) To a solution of 1.2 g (1.7 m[, 16.7 millimoles) of diethylamine and 15 mi of anhydrous tetrahydrofurane 12.4 mi (16.7 millimoles) of a hexane solution of nbutyl lithium are added at a temperature below - 1 O'C and the mixture is stirred at - 1 O'C for half an hour under argon atmosphere. The mixture is cooled to a temperature between -70'C and - 78'C and at this 40 temperature a solution of 1.9 9 (16.7 millimoles) of (S)-4-methyitetrahyaro-2H-pyrane-2-one (compound of the Formula 11) and 3 mi of anhydrous tetrahydrofurane is added dropwise. The reaction mixture is stirred at -78'C for an hour, whereupon a solution of 3.62 g (3.04 mi, 16.7 millimoles) of geranyl bromide (compound of the general Formula Ill, X=Br) and 2 mi of anhydrous hexamethyl phosphoric acid triamide is added, the mixture is stirred at -713C for an 45 hour and allowed to stand at -30'C overnight.
To the reaction mixture 10 mi of water and 50 mi of ether are added, the etheral phase is separated, the aqueous layer is extracted with 50 mi of ether and the united etheral solutions are washed subsequently with 10 mi of 5% hydrochloric acid and 10 mi of a saturated hydrochloric sodium chloride solution and dried over magnesium suffate. The solvent is removed 50 in vacuo on a water-bath and the residue is purified by low-pressure column chromatography (Kieselgel 60 HR, a 10:1 mixture of hexane and acetone) Thus 2.6 g of the desired compound are obtained, yield 63%, colourless oil.
[a125= -5Z; 55 D [a] 25 1 g= - 6.9' (C=2.7, chloroform).
4 GB2189244A 4 TLC: Rf0.57 (hexane-acetone 5:2) Ge:Rt= 11.83 [SP 2100, 30m x 0.25 mm, 160-260'C, WC/min, N21, main component ([V); 94.1% 3SAS-isomer: Rt= 11.64 min, 5.9%.
[R (film): 1730 (C0), 1660 (C=Q 1450, 1380, 1270, 1200, 1140, 1100, 1070 cm-1. 5 H-NMR (CDC13): 1.09 (3H, d, J=6Hz, CH.), 1.4-1.95 (12H, m, 3CHJ, CH2, CH), 2.05 (6H, me, 3CH2), 2.4 (1H, me, CH), 4.25 (2H, me, CH-0), 5.09 (2H, m, 2 CH=C).
13C-NMR (CDC'3): 16.23, 17.67, 20.65, 25.71 (4CH3), 20.50, 27.67 (2CH2), 2984 (CH), 30.95, 39.89 (CH2), 48.26 (CH), 67.54 (O-CH2), 120.63, 124.17, 131.31, 137.66 (4-C=), 173.75 (-COO). 10 MS: m/z 250 (37) [M++], 207 (18), 194 (3), 181 (30), 137 (23), 136 (23), 127 (19), 114 (100, 109) (26), 99 (39), 69 (74).
Example 2 (2R,1'S)-(E)-methyi[2-(3-hydroxy-1-methyi-propyi)-5,9-dimethyi-4,8decadieno atej (V:W=CHj 15 To a mixture of 5 mi of triethyl amine and 15 mi of anhydrous methanol 1. 9 9 (7.6 millimoles) of (3R,4S)-(E)-4-methyf-3-(3,7-dimethyl-2,6-octadienyi)-tetrahydro-2Hpyrane-on e (R) are added.
The reaction mixture is stirred for 18 hours. The solvent is distilled off in vacuo and the residue is purified by column chromatography (Kieselgel 60 HR, a 10:1 mixture of hexane and acetone).
Thus 1.69 9 of the desired compound are obtained in the form of a colourless oil, yield 79%. 20 TLC: Rf=0.48 (hexane-acetone 5:2) ]R (film): 3380 (OH), 1730 (C0), 1660 (C-=C), 1440, 1380, 1185, 1150, 1100, 1050 cm-1.
H-NIVIR (CDCI.,): 0.95 (3H, d, J=6 Hz, CH3), 1.4-1.95 (3H, m, CH2, CH), 1. 6 (6H, br s, 2 CH3), 1.66 (3H, s, CHJ, 3.63 (2H, t, J=6 Hz, OCHJ, 5.06 (2H, m, 2CH=C).
MS: m/z 282 (10) [M+] 250 (6), 239 (10), 207 (16), 195 (11), 181 (24), 145 (13), 134 (20), 25 113 (22), 108 (31), 96 (19), 93 (20), 81 (29), 79 (16), 69 (100), 55 (22), 43 (12), 41 (63).
Example 3 (2R,1'S)-(E)-methyi-[5,9-dimethyi-2-[1-methyi-3-(methoxy-methoxy)-propyll4, 8-decadienoatej (V1: 30 W=CH3: R2= -CH2-OCH3).
Method A 1.62 9 (5.74 millimole) of (2R,1S')-(E)-methyi-2-(3-hydroxy-1-methyi- propyi)-5,9-dimethyi-4,8decadienoate (V: Rl=CH3) are dissolved in 10 mi of dimethoxy methane, whereupon 0.1 9 (1.15 35 millimole) of lithium bromide and 0. 1 9 (0.06 millimole) of p-toluene suifonic acid are added and the mixture is stirred at room temperature for 45 minutes. The reaction mixture is evaporated in vacuo on a water-bath, the residue is dissolved in 50 mi of ether, the etheral solution is washed with 5 mi of a saturated sodium carbonate solution, 5 mi of water and 5 mi of a saturated sodium chloride solution, dried and the ether is distilled off in vacuo. The residue is purified by 40 column chromatography (Kieselgel 60 HR, a mixture of hexane and ether). Thus 0.9 9 of the desired compound are obtained in the form of a colourless oil, yield 48%.
Method 8 0.81 g (2.87 millimoles) of compound V (RI=CH,) and 0.3 9 (0.41mi, 1.3 millimoles) of 45 triethyl amine are dissolved in 8 mi of anhydrous ether whereupon to the solution 0.69 9 (8.6 millimoles) of ch;oromethyi-methylether are added and the mixture is stirred at room temperature for 8 hours. To the reaction mixture 50 mi of ether are added, the mixture is washed with 5 mi of 5% hydrochloric acid, 5 mi of a saturated sodium bicarbonate solution, 5 mi of 'I saturated sodium chloride solution and dried. The solvent is distilled off. The residue is purified as 50 described in Example 1. Yield 0.68 9 (73%).
TLC: Rf=0.52 (hexane-acetone 10:1) GC: Rt=14.70 min main product (VI:RI=CH,, R2=CH2-0-CH3): 95% 2S,1'S-isomer: Rt=14.57 min, 5%. 55 IR (film): 1730 (C0), 1660 (C=Q 1440, 1200, 1160, 1120, 1040 cm-1.
H-NMR (CDCI,): 0.95 (3H, d, J6 Hz, CH,), 1.2-1.8 (3H, m, CH, CH)1.59 (6H, br s, 2CHJ, 1.67 (3H, a, CH3), 1.9-2.4 (7H, m, 3CH2, CH), 3.34 (3H, s, OCHJ, 3.55 (2H, t, J=7Hz, CH2-0), 3.63 (3H, s, OCH, 4.68 (2H, s, O-CH2-0), 5.06 (2H, m, CH=C). 60 MS: m/z 326 (20) [M+], 294 (12), 281 (10), 265 (4), 263 (5), 249 (10), 225 (7), 195 (24), 181 (7), 157 (8), 149 (17), 135 (24), 69 (88), 55 (17), 45 (100), 41 (55).
Example 4 (-)-(2R,1'S)-(E)-5,9-dimethy]-2-[1-methyi-(3-methoxymethoxy)-propyll-4,8dec adien-l-ol (VIl: R2= 65 GB2189244A 5 -CH2-OCH3) To a suspension of 0. 17 9 (4.5 millimoles) of lithium-tetrahydrio- aluminate (111) and 7 mi of anhydrous tetrahydrofurane 0.7 g (2.14 millimoles) of (2R,1'S)-(E)methyi[5,9-dimethyl-2-[1-methyi-3-(methoxymethoxy)propyi]-4,8-decadienoatej (V1: RI=CH., R2= -CH,OCHj in 3 mi of anhydrous tetrahydrofurane are added. The reaction mixture is stirred at room temperature for an 5 hour, decomposed by adding 2 mi of water, 10 mi 1:1 hydrochloric acid are added and the mixture is extracted with 60 mi of ether in three portions. The united etheral solutions are washed with 10 mi of a saturated sodium hydrogen carbonate solution and 10 mi of a saturated sodium chloride solution, dried and the solvent is distilled off in vacuo. Thus 0.54 g of the desired compound are obtained in the form of a colourless oil, yield 85%. 10 a22 E= - 13; [a]22g=2.0 (c=3.2, CH0J 54 TILC: Rf=0.48 (hexane-ethyl-acetate 10:5) Rf=0.50 (hexane-acetone 5:2) 15 [R (film): 3420 (OH), 1660 (C=C), 1460, 1380, 1160, 1120, 1040 cm-1.
H-NMR (CDC]3): 0.94 (3H, cl, J=6 Hz, CH3), 1.4-1.9 (4H, m, CH2, 2CH), 1. 61 (6H, br s 2CH3), 1.68 (31-1, s, CH3), 1.9-2.4 (61-1, m,3 CH2), 3.29 (3H, s, OCH3), 3.46 (2H, cl, J=6 Hz, CH270), 3.52 (2H, t, J=6 Hz, CH2-0), 4.50 (2H, s, O-CH270), 5.09 (21-1, m, 2 CH=C). 20 MS: m/z 298 (1) [M+], 280 (3) [M-H201, 266 (3), 235 (20), 205 (3), 123 (19), 111 (21), 85 (51), 81 (47), 69 (94), 55 (24), 45 (100), 41 (51).
Example 5 (+)-(3S,4R)-(E)-3,7,1 1 -trimethyl- 1 -(methoxymethoxy)-4(mesyloxymethyi)-6, 1 0-dodecadiene (V111; 25 R2= -CH2-OCH3, X=OMesyl) To a solution of 0.24 9 (2.1 millimoles) of mesyl chloride and 2 mi of anhydrous ether a solution of 0.50 9 (1.68 millimoles) of (2R,1'S)-(E)-5,9-dimethyi-2-[1- methyi-3-(methoxymethoxy)propyll-4,8-decadiene-l-ol (Vil: R2=, -CH2-OCH3) and 0.25 9 (0.35 mi, 2.S millimole) of triethyl amine in 5 mI of ether is added at O'C under cooling and stirring. The reaction mixture is stirred 30 at room temperature for 2 hours, 20 mi of ether and 5 mi of 5% hydrochloric acid are added, the etheral phase is separated, washed with 5 mi of a saturated sodium chloride solution dried and evaporated in vacuo. Thus 0.53 g of the desired compound are obtained in the form of an oil, yield 84%. 35 [a]21 = + 1. 7'; D [a] 21 ,g= +1.9 (c=5.22, C1-103) TLC: Rf: 0.52 (hexane-ethyl acetate 11) M (film): 1660 (C=C), 1460, 1380, 1350, 1200, 1170, 1150, 1100, 1050, 1030, 960, 940, 40 820 cm-1.
H-NMR (CC],): 0.92 (31-1, d, J=6 Hz, CH3), 1.57 (6H, m, 2CH.), 1.64 (3H, s, CH3), 1.4-1.9 (4H, m, CH2, 2CH), 1.9-2.4 (6H, m, 3CH2), 2.86 (31-1, m, CH3-SO2), 3.25 (3H, s, OCH3), 3.47 (21-1, t, J6 Hz, CH2-0), 4.04 (2H, cl, J=6 Hz, CH,-D), 4.46 (21-1, s, O-CH2-0), 5.05 (2H, m, 2 CH=C). 45 MS: mlz 344 (12) [M-CH3-OHI, 331 (13), 280 (7), 248 (5), 235 (20), 205 (5), 179 (10), 161 (8), 149 (16), 135 (20), 123 (25), 111 (23), 109 (22), 107 (28), 85 (49), 81 (46), 69 (100), 67 (23), 55 (33), 45 (85), 41 (49).
Example 6 50 (-)-(3S,4R)-(E)-3,4,7,11-tetramethyl-l-(methoxymethoxy)-6,10-dodecadiene (M R2= -CH2-OCH3) To a suspension of 2.209 9 (5.52 millimole) of lithium tetrahydrido aluminate in 5 mi of anhydrous tetrahydrofurane a solution of 0.52 g (1.38 millimole) of (3S, 4R)-(E)-3,7,1 1-trimethyl 1-(methoxymethoxy)-4-mesyloxymethyl)-6,10-dodecadiene (Vill: R2= -CH2OCH3, X= -OMesyl) is added dropwise under stirring. The reaction mixture is heated to boiling for an hour, cooled to 55 room temperature, 2 m] of acetone and 2 mi of water are added. The mixture is diluted with 30 mi of ether and extracted with 10 m[ of 5% hydrochloric acid. The aqueous layer is extracted with a total amount of 20 mi of ether, the united etheral solutions are washed with 10 m] of a saturated sodium chloride solution, dried and the solvent is distilled off in vacuo. Thus 0.354 9 of the desired compound are obtained in the form of a colourless oil, yield 81%. 60 [a122= -4.5, 22 lal,,g= -5.4 (c=4.63, CHClj 6 GB2189244A 6 TILC: Rf=0.56 (hexane-acetone 5:0.2) [R (film): 1660 (C=C), 1460, 1380, 1265, 1120, 1060, 1040 cm-1.
H-NIVIR (CC[4): 0.80 (3H, d, J=6 Hz, CH3), O87 (3H, d, J=6 Hz, CH.), 1.41.9 (4H, m, CH2, 2CH), 1.58 (6H, br s, 2CH3), 1.64 (3H, s, CH3), 2.01 (6H, m, 3CH,), 3.24 (3H, s, OCH3), 3.45 (2H, t, J=6 Hz, CH2-0), 4.46 (2H, s, O-CH2-0), 5.06 (2H, m, 5 2CH=C).
MS: m/z 282 (7) [M--], 250 (9), 237 (13), 208 (10), 177 (7), 163.(5), 137 (20), 113 (12), 109 (21), 99 (26), 95 (45), 83 (20), 81 (45), 69 (96), 55 (27), 45 (100), 41 (53).
Example 7 10 (-)-(3S,4R)-(E)-3,47,1 1 -tetramethyl-6, 1 0-dodecadiene- 1 -ol 0.35 9 (1.24 millimoles) of (3S,4R)-(E)-3,4,7,1 1 -tetramethyl- 1 (methoxymethoxy)-6, 1 0-dodecadiene (IX: R2= -CH2-OCH,) are dissolved in 5 mi of methanolic hydrogen chloride (0.05 mole/1) and the solution is stirred at room temperature for 48 hours. The solvent is removed in vacuo and the residue is purified by column chromatography (Kieselgel 60 HR, a 10:0.2 mixture of 15 hexane and acetone). Thus 0. 183 9 of the desired compound are obtained in the form of colourless oil, yield 62%.
23 3.8, D [a]23 4g= -4.8 (c=4.2, CF1C13) 20 IR (film): 3350 (OH), 1660 (C=Q 1460, 1380, 1210, 1100, 1060 cm-1 H-NMR (C13CIj: 0.84 (3H, d, J=6 Hz, CH3), 0.89 (3H, d, J=6 Hz; CH3), 1.4- 1.9 (4H, m, CH2, 2CH), 1.59 (6H, br s, 2CH3), 1.68 (3H, s, CH3), 2.03 (6H, m, 3CH2), 3.62 (2H, t, J=6 Hz, CH,-0) 5.10 (2H, m, 2CH=Q 25 13C-NIVIR (C13C13): 16.09, 16.76, 17.67, 25.71, (6CH3), 26.71, 31.53 (2CH2), 33.73 (CH), 35.95 (CH2), 38.78 (CH), 39.9 (CH2), 61.63 63 (OCH2), 123.91, 124.44, 131.22, 135.32 (4 -CH=).
MS: m/z 238 (11) [M+], 195 (12), 177 (4), 165 (4), 137 (7), 123 (39), 109 (25), 99 (24), 95 (49), 83 (42), 81 (37), 69 (100), 55 (41), 41 (48). 30 Example 8 (+)-(3S,4R)-(E)-3,4,7,1 1 -tetramethyl-6, 1 0-dodecadienal (1) [(+)- 1 3- norfaranall To a solution of 0. 106 g (0.45 millimoles) of (3S,4R)-(E)-3,4,7,1 1 - tetramethyl-6, 1 0-dodecadien 1-ol (X) and 5 mi of anhydrous dichloro methane 0.216 g (0.58 millimoles) of pyridinium-dichloro 35 methane 0.216 g (0.58 millimoles) of pyridinium-dichromate are added. The reaction mixture is stirred at room temperature for 3 hours, filtered through a column packed with 8 9 of silicagel, the column is washed with 30 mi of ether, the united solutions are evaporated in vacuo and the residue is purified by low pressure column chromatography. (Kieselgel 60 HR, a 10:05 mixture of hexane and acetone). Thus 0.071 g of the desired compound are obtained in the form of a 40 colourless oil, yield 67%.
(a122= + 14.2, [a]22 45,,g= +15.8 (c=2.56, CH0J 45 TILC: Rf=0.53 (hexane-acetone 5.02) [R (film): 2720, 1660 (C=C), 1450, 1380, 1115, 1080, 1020 cm-1.
H-NMR (CDC13): 0.83 (3H, d, J=6 Hz, CH,), 0.88 (314, d, J=6 Hz, CH3), 1.41.9 (2H, m, 2CH), 1.59 (6H, br s, 2CH3), 1.68 (3H, s, CH3), 2.01 48 H, m, 4 CH2) 5.09 (2H, m, 2CH=Q 9.45 (1H, dd, CHO). 50 13C-NIVIR (CDC'3): 15.97, 16.09, 17.55, 17.67, 25.71 (5CH3), 26.62, 31.91 (2CH2), 32.0, 38.49 (2CH), 39.84, 47.42 (2CH2), 133.09, 124.29, 131.31, 135.9 (4 -C=), 203.21 (-CHO).
MS: m/z 236 (4) [M+], 193 (22) [M-CH2-CHO], 175 (5), 149 (5), 137 (5), 124 (33), 109 (17), 81 (23), 69 (100), 41 (40). 55
Claims (10)
1. Process for the preparation of (+)-(3S,4R)-3,4,7,1 1 -tetra methyl-6, 1 0-dodecadiena 1 [(+)-13 norfaranai)l of the Formula (1) 60 CHO (1) which comprises forming an anion from the compound of the Formula (11) 65 7 GB2189244A 7 OAO 5 with a strong base; reacting the anion thus obtained with a compound of the general Formula 10 X (wherein X stands for chlorine, bromine, iodine, methanesulfonyloxy or p- toluenesulfonyloxy); 15 esterifying the compound of the Formula (IV) (IV) 20 0 0 thus obtained; treating the compound of the general Formula (V) 25 OH (V) OORI 30 thus obtained (wherein R' stands for a straight or branched chain alkyl group having 1-6 carbon atoms) with an agent capable of protecting the hydroxy group; reducing the compound of the general Formula (V1) 35 lOR2 (V1) COORI thus obtained with a metal hydride (wherein R' is as stated above and R2 stands for methoxy- 40 methyl, 1-ethoxy-ethyl or 2-tetrahydropyranyl); reacting the compound of the general Formula (V11) OR2 (V11) 45 I-101-1 thus obtained (wherein R2 is as stated above) with a halogenating or acylating agenT; reducing 50 the compound of the general Formula (V111) .I 5 -1k ()R2 (V111) 55 thus obtained (wherein R2 and X are as stated above); hydrolysing the compound of the general Formula (IX) 60 (1x) OR2 8 GB2189244A 8 thus obtained (wherein R2 is as stated above); and oxidizing the compound of the Formula (X) OH (X) 5 thus obtained into (+)-13-norfaranal of the Formula (1).
2. Process according to Claim 1 which comprises oxidizing the compound of the Formula (X) with pyridinium dichromate. 10
3. Process according to Claim 1 or 2 which comprises carrying out hydrolysis of the compound of the general Formula (IX) with methanolic hydrogen chloride.
4. Process according to any of Claims 1-3 which comprises reducing the compound of the general Formula (V111) (wherein X stands for methanesulfonyloxy) with lithium tetrahydrido alumi- nate. 15
5. Process according to any of Claims 1-4 which comprises using for the preparation of the compound of the general Formula (IX) a compound of the general Formula (V111) wherein X is methanesulfonyloxy.
6. Process according to any of Claims 1-5 which comprises using for the preparation of the compounds of the general Formula (V111) a compound of the general Formula (V11) wherein R2 is 20 methoxymethyl.
7. Process according to any of Claims 1-6 which comprises using for the preparation of the compound of the general Formula (V11) a compound of the general Formula (V]) wherein R' is methyl.
8. Process according to any of Claims 1-7 which comprises reducing the compound of the 25 general Formula (V1) with lithium tetrahydrido aluminate.
9. A process as claimed in claim 1, wherein any one of the process steps is substantially as hereinbefore described in any one of Examples 1 to 8.
10. (+)-13-norfaranal of the general formula (1) prepared by a process as claimed in any one of claims 1 to 9. 30 Printed for Her Majesty's Stationery Office by Burgess & Son (Abingdon) Lid, Dd 8991685, 1987. Published at The Patent Office, 25 Southampton Buildings, London, WC2A 'I AY, from which copies may be obtained.
i;i
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU861526A HU195178B (en) | 1986-04-11 | 1986-04-11 | Process for producing (+)-13-norfaranal of tracer activity for monomorium pharaonis |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8708603D0 GB8708603D0 (en) | 1987-05-13 |
| GB2189244A true GB2189244A (en) | 1987-10-21 |
| GB2189244B GB2189244B (en) | 1989-11-22 |
Family
ID=10954878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8708603A Expired GB2189244B (en) | 1986-04-11 | 1987-04-10 | Process for the preparation of (+)-13-norfaranal |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS62249943A (en) |
| BE (1) | BE1001613A4 (en) |
| CH (1) | CH671013A5 (en) |
| DE (1) | DE3712528A1 (en) |
| ES (1) | ES2004598A6 (en) |
| FR (1) | FR2597094A1 (en) |
| GB (1) | GB2189244B (en) |
| HU (1) | HU195178B (en) |
| IT (1) | IT1203879B (en) |
| NL (1) | NL8700847A (en) |
| SU (1) | SU1533625A3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8097746B2 (en) | 2005-04-05 | 2012-01-17 | Kuraray Co., Ltd. | Method for producing 2-isopropenyl-5-methyl-4-hexen-1-yl 3-methyl-2-butenoate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2328856B1 (en) * | 2008-09-22 | 2017-03-08 | The Procter and Gamble Company | Specific polybranched aldehydes, alcohols surfactants and consumer products based thereon |
-
1986
- 1986-04-11 HU HU861526A patent/HU195178B/en not_active IP Right Cessation
-
1987
- 1987-04-09 CH CH1367/87A patent/CH671013A5/de not_active IP Right Cessation
- 1987-04-10 SU SU874202347A patent/SU1533625A3/en active
- 1987-04-10 IT IT20078/87A patent/IT1203879B/en active
- 1987-04-10 FR FR8705145A patent/FR2597094A1/en active Pending
- 1987-04-10 ES ES8701045A patent/ES2004598A6/en not_active Expired
- 1987-04-10 BE BE8700383A patent/BE1001613A4/en not_active IP Right Cessation
- 1987-04-10 GB GB8708603A patent/GB2189244B/en not_active Expired
- 1987-04-10 NL NL8700847A patent/NL8700847A/en not_active Application Discontinuation
- 1987-04-11 JP JP62087938A patent/JPS62249943A/en active Granted
- 1987-04-13 DE DE19873712528 patent/DE3712528A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8097746B2 (en) | 2005-04-05 | 2012-01-17 | Kuraray Co., Ltd. | Method for producing 2-isopropenyl-5-methyl-4-hexen-1-yl 3-methyl-2-butenoate |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8720078A0 (en) | 1987-04-10 |
| BE1001613A4 (en) | 1989-12-19 |
| CH671013A5 (en) | 1989-07-31 |
| JPH0533930B2 (en) | 1993-05-20 |
| HUT43313A (en) | 1987-10-28 |
| SU1533625A3 (en) | 1989-12-30 |
| DE3712528A1 (en) | 1987-10-15 |
| HU195178B (en) | 1988-04-28 |
| JPS62249943A (en) | 1987-10-30 |
| GB8708603D0 (en) | 1987-05-13 |
| IT1203879B (en) | 1989-02-23 |
| GB2189244B (en) | 1989-11-22 |
| NL8700847A (en) | 1987-11-02 |
| FR2597094A1 (en) | 1987-10-16 |
| ES2004598A6 (en) | 1989-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5455362A (en) | Preparation of astaxanthin novel intermediates therefor and the preparation thereof | |
| US4245109A (en) | Process for producing astaxanthin | |
| US4153615A (en) | Method of producing coloring agents | |
| US5414156A (en) | Process for producing ortho-isopropylated phenol derivatives | |
| US7345181B2 (en) | Process for preparing prostaglandin derivatives and starting materials for the same | |
| GB2189244A (en) | Process for the preparation of (+)-13-norfaranal | |
| US4233231A (en) | Novel vinyl-stannyl derivatives | |
| US4051153A (en) | Intermediates in the synthesis of vitamin E | |
| HU181328B (en) | Process for producing 7-bracket-e-bracket closed, 9-bracket-z-bracket closed-alkadienol derivatives | |
| US4088662A (en) | Optically active amides and process for producing the same | |
| US4395561A (en) | Synthesis of 3-hydroxyoxetane | |
| Montgomery et al. | De novo synthesis of carbohydrates by stereoselective aldol reaction: l-cladinose | |
| US3950381A (en) | Preparation of aroyl acidic esters | |
| US4201874A (en) | 3-Isopropenyl-6-heptenoic acid | |
| US4237308A (en) | Process for preparing 2-cyclopentenone derivative and perfume composition containing the derivative | |
| EP0116375B1 (en) | (1rs, 4sr, 5rs)-4-(5-hydroxy-4,8-dimethyl-8-nonen-1-yl)-4-methyl-3,8-dioxybicyclo(3.2.1.)octane-1-acetic acid and process for its preparation | |
| US3682970A (en) | Production of unsaturated carbocyclic ketones | |
| US3686215A (en) | Production of 5,6,7,7a-tetrahydroindan-5-ones | |
| JP3541417B2 (en) | Phenyl-substituted hydroxycyclopentenones, pentanones and phenyl-substituted prostaglandin I2 intermediates, and their production and optical resolution | |
| US5225554A (en) | Polyoxa tetracyclic compounds | |
| HU180386B (en) | Process for producing 11-dodecen-1-ol and 11-dodecen-1-yl-acetate of insect-feromone activity | |
| US4603213A (en) | Total synthesis of 1RS,4SR,5RS-4-(4,8-dimethyl-5-hydroxy-7-nonen-1-yl)-4-methyl-3,8-dioxabicyclo[3.2.1]octane-1-acetic acid | |
| US4322557A (en) | 1-Aryloxy-2-(S)-hydroxy-3-(triarylphosphonio)-propane derivatives as prostaglandin intermediates | |
| US3855250A (en) | CERTAIN 2-OXO-2H-CYCLOPENTA (b)-FURANS | |
| US3716558A (en) | 5-propargyl thenyl alcohols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |