GB1585499A - Polyene compounds - Google Patents
Polyene compounds Download PDFInfo
- Publication number
- GB1585499A GB1585499A GB32189/77A GB3218977A GB1585499A GB 1585499 A GB1585499 A GB 1585499A GB 32189/77 A GB32189/77 A GB 32189/77A GB 3218977 A GB3218977 A GB 3218977A GB 1585499 A GB1585499 A GB 1585499A
- Authority
- GB
- United Kingdom
- Prior art keywords
- cyclopent
- trimethyl
- formula
- pent
- dioxo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 Polyene compounds Chemical class 0.000 title claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- DXGGDMSNCNNMOK-KNZSRCDBSA-N 3,5,5-trimethyl-4-[(1e,3e,5e,7e,9e,11e,13e,15e,17e)-3,7,12,16-tetramethyl-18-(2,5,5-trimethyl-3,4-dioxocyclopenten-1-yl)octadeca-1,3,5,7,9,11,13,15,17-nonaenyl]cyclopent-3-ene-1,2-dione Chemical compound CC=1C(=O)C(=O)C(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)C(=O)C(=O)C1(C)C DXGGDMSNCNNMOK-KNZSRCDBSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000004423 acyloxy group Chemical group 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 16
- 230000008020 evaporation Effects 0.000 claims description 16
- 239000000284 extract Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000007858 starting material Substances 0.000 claims description 14
- 238000004040 coloring Methods 0.000 claims description 13
- 150000004714 phosphonium salts Chemical class 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- MKGRMAIAGDEUTL-XYCHTSNDSA-N Actinioerythrol Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)C(=O)C(O)C1(C)C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)C2(C)C MKGRMAIAGDEUTL-XYCHTSNDSA-N 0.000 claims description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004043 oxo group Chemical group O=* 0.000 claims description 9
- GQVGTWFEGUJKDT-UHFFFAOYSA-N 2,7-dimethylocta-2,6-dien-4-ynedial Chemical compound O=CC(C)=CC#CC=C(C)C=O GQVGTWFEGUJKDT-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 238000007127 saponification reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 6
- QZIMKMNQRKMFHR-UHFFFAOYSA-N 3,5,5-trimethyl-4-(3-methylpenta-1,3-dienyl)cyclopent-3-ene-1,2-dione Chemical compound CC=C(C)C=CC1=C(C)C(=O)C(=O)C1(C)C QZIMKMNQRKMFHR-UHFFFAOYSA-N 0.000 claims description 5
- INBQIAMSFFQLES-UHFFFAOYSA-N 3-methyl-5-(2,5,5-trimethyl-3,4-dioxocyclopenten-1-yl)pent-2-en-4-ynal Chemical compound O=CC=C(C)C#CC1=C(C)C(=O)C(=O)C1(C)C INBQIAMSFFQLES-UHFFFAOYSA-N 0.000 claims description 5
- FQBFIMIXUCMTLH-UHFFFAOYSA-N 4-(5-hydroxy-3-methylpent-3-en-1-ynyl)-3,5,5-trimethylcyclopent-3-ene-1,2-dione Chemical compound OCC=C(C)C#CC1=C(C)C(=O)C(=O)C1(C)C FQBFIMIXUCMTLH-UHFFFAOYSA-N 0.000 claims description 5
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- OZJSDYFNCIXSBY-UHFFFAOYSA-N 3,5,5-trimethyl-4-(3-methylpent-3-en-1-ynyl)cyclopent-3-ene-1,2-dione Chemical compound CC=C(C)C#CC1=C(C)C(=O)C(=O)C1(C)C OZJSDYFNCIXSBY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 235000009508 confectionery Nutrition 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- FMKGDHLSXFDSOU-BDPUVYQTSA-N Dienon-Astacin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)C(=O)C(=CC1(C)C)O)C=CC=C(/C)C=CC2=C(C)C(=O)C(=CC2(C)C)O FMKGDHLSXFDSOU-BDPUVYQTSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- XAJOPMVSQIBJCW-UHFFFAOYSA-N pent-3-en-1-yne Natural products CC=CC#C XAJOPMVSQIBJCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 235000003911 Arachis Nutrition 0.000 claims description 2
- 244000105624 Arachis hypogaea Species 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- QAQJMLQRFWZOBN-LAUBAEHRSA-N L-ascorbyl-6-palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](O)[C@H]1OC(=O)C(O)=C1O QAQJMLQRFWZOBN-LAUBAEHRSA-N 0.000 claims description 2
- 239000011786 L-ascorbyl-6-palmitate Substances 0.000 claims description 2
- 235000016911 Ribes sativum Nutrition 0.000 claims description 2
- 235000002355 Ribes spicatum Nutrition 0.000 claims description 2
- 235000016897 Ribes triste Nutrition 0.000 claims description 2
- 244000281209 Ribes triste Species 0.000 claims description 2
- 240000007651 Rubus glaucus Species 0.000 claims description 2
- 235000011034 Rubus glaucus Nutrition 0.000 claims description 2
- 235000009122 Rubus idaeus Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 235000019568 aromas Nutrition 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 235000010385 ascorbyl palmitate Nutrition 0.000 claims description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 238000002329 infrared spectrum Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 235000010384 tocopherol Nutrition 0.000 claims description 2
- 229960001295 tocopherol Drugs 0.000 claims description 2
- 229930003799 tocopherol Natural products 0.000 claims description 2
- 239000011732 tocopherol Substances 0.000 claims description 2
- WOTUXYFVYNNUQB-UHFFFAOYSA-N 2,7-dimethylocta-2,6-dien-4-yne Chemical compound CC(C)=CC#CC=C(C)C WOTUXYFVYNNUQB-UHFFFAOYSA-N 0.000 claims 1
- 230000003287 optical effect Effects 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000011981 lindlar catalyst Substances 0.000 description 6
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 6
- QJCWTRBDOWSVNJ-UHFFFAOYSA-N 4-hydroxy-2,5,5-trimethylcyclopent-2-en-1-one Chemical compound CC1=CC(O)C(C)(C)C1=O QJCWTRBDOWSVNJ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000002940 palladium Chemical class 0.000 description 5
- BFFZXMSXYSWTHN-UHFFFAOYSA-N 4-(5-hydroxy-3-methylpent-3-en-1-ynyl)-3,5,5-trimethylcyclopent-3-ene-1,2-diol Chemical compound OCC=C(C)C#CC1=C(C)C(O)C(O)C1(C)C BFFZXMSXYSWTHN-UHFFFAOYSA-N 0.000 description 4
- AWCZKIPCGURQLM-UHFFFAOYSA-N 5-(4-hydroxy-2,5,5-trimethyl-3-oxocyclopenten-1-yl)-3-methylpent-2-en-4-ynal Chemical compound O=CC=C(C)C#CC1=C(C)C(=O)C(O)C1(C)C AWCZKIPCGURQLM-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 3
- 125000001477 organic nitrogen group Chemical group 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QPPPQRZBXQZBIJ-UHFFFAOYSA-N 2,2,4-trimethylcyclopent-4-ene-1,3-dione Chemical compound CC1=CC(=O)C(C)(C)C1=O QPPPQRZBXQZBIJ-UHFFFAOYSA-N 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 2
- IBAOIICFWCLZNW-UHFFFAOYSA-N 2,5,5-trimethyl-4-trimethylsilyloxycyclopent-2-en-1-one Chemical compound CC1=CC(O[Si](C)(C)C)C(C)(C)C1=O IBAOIICFWCLZNW-UHFFFAOYSA-N 0.000 description 2
- JSCHIKVWARWUJR-UHFFFAOYSA-N 3-methyl-5-(2,5,5-trimethyl-3,4-dioxocyclopenten-1-yl)penta-2,4-dienal Chemical compound O=CC=C(C)C=CC1=C(C)C(=O)C(=O)C1(C)C JSCHIKVWARWUJR-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- OIYWFEMVHCWLNK-UHFFFAOYSA-N 4-(5-hydroxy-3-methylpenta-1,3-dienyl)-3,5,5-trimethylcyclopent-3-ene-1,2-dione Chemical compound OCC=C(C)C=CC1=C(C)C(=O)C(=O)C1(C)C OIYWFEMVHCWLNK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000021466 carotenoid Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 239000012374 esterification agent Substances 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- AYODHZHFDRRQEZ-XDRNSHQHSA-N (2e,4e,6z)-2,7-dimethylocta-2,4,6-trienedial Chemical compound O=CC(/C)=C\C=C\C=C(/C)C=O AYODHZHFDRRQEZ-XDRNSHQHSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- XOUUHJRILISKSA-UHFFFAOYSA-N 1-(5-hydroxy-3-methylpent-3-en-1-ynyl)-2,2,5-trimethylcyclopent-4-ene-1,3-diol Chemical compound OCC=C(C)C#CC1(O)C(C)=CC(O)C1(C)C XOUUHJRILISKSA-UHFFFAOYSA-N 0.000 description 1
- QLTOMLUJRPSRHE-UHFFFAOYSA-N 2,5,5-trimethyl-1-(3-methyl-5-trimethylsilyloxypent-3-en-1-ynyl)-4-trimethylsilyloxycyclopent-2-en-1-ol Chemical compound C[Si](C)(C)OCC=C(C)C#CC1(O)C(C)=CC(O[Si](C)(C)C)C1(C)C QLTOMLUJRPSRHE-UHFFFAOYSA-N 0.000 description 1
- PKUPAJQAJXVUEK-UHFFFAOYSA-N 2-phenoxyacetyl chloride Chemical compound ClC(=O)COC1=CC=CC=C1 PKUPAJQAJXVUEK-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- BOGRNZQRTNVZCZ-UHFFFAOYSA-N 3-methylpenta-1,3-diene Chemical compound CC=C(C)C=C BOGRNZQRTNVZCZ-UHFFFAOYSA-N 0.000 description 1
- LNGSTWKDJTUPDF-UHFFFAOYSA-N 5-(4-hydroxy-2,5,5-trimethyl-3-oxocyclopenten-1-yl)-3-methylpenta-2,4-dienal Chemical compound O=CC=C(C)C=CC1=C(C)C(=O)C(O)C1(C)C LNGSTWKDJTUPDF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 241000786363 Rhampholeon spectrum Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- LVAZZJDLBYTXIG-UHFFFAOYSA-N [2,2,4-trimethyl-3-(3-methyl-5-oxopenta-1,3-dienyl)-5-oxocyclopent-3-en-1-yl] acetate Chemical compound CC(=O)OC1C(=O)C(C)=C(C=CC(C)=CC=O)C1(C)C LVAZZJDLBYTXIG-UHFFFAOYSA-N 0.000 description 1
- ZZVJMNALCMZOJM-UHFFFAOYSA-N [3-(5-hydroxy-3-methylpenta-1,3-dienyl)-2,2,4-trimethyl-5-oxocyclopent-3-en-1-yl] acetate Chemical compound CC(=O)OC1C(=O)C(C)=C(C=CC(C)=CCO)C1(C)C ZZVJMNALCMZOJM-UHFFFAOYSA-N 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000001168 astaxanthin Substances 0.000 description 1
- 229940022405 astaxanthin Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000001659 canthaxanthin Substances 0.000 description 1
- 229940008033 canthaxanthin Drugs 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N cyclopenten-2-one Natural products O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
- A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
- A23G3/36—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
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- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/06—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a five-membered rings
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- 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
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Description
(54) POLYENE COMPOUNDS
(71) We, F. HOFFMANN-LA ROCHE & CO., AKTIENGESELL
SCHAFT, a Swiss Company of 124-184 Grenzacherstrasse, Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to polyene compounds. More particularly, the invention is concerned with novel carotenoid polyene compounds and a process for the manufacture of these compounds and of derivatives thereof.
The novel polyene compounds provided by the present invention have the following general formula
wherein R represents an oxo, acyloxy or hydroxy group and the broken lines denote optional carbon-carbon bonds.
The polyene compounds of the formula
which are embraced by formula I hereinbefore, are deep-red pigments which are suitable for the colouring of foodstuffs, pharmaceuticals and cosmetic preparations. They are also key substances for the manufacture of violerythrin and actinoerythrol.
Violerythrin [2,2'-dinor-astacene] has a deep blue colour which is surprising for a carotenoid. Violerythrin can be converted by reduction into the red actinoerythrol [2,2'-dinor-astaxanthin]. Moreover, actinioerythrol can be oxidised in solution to violerythrin by simply blowing air through the solution.
Violerythrin has hitherto been obtainable in large amounts only by oxidation of 2,2'-dinor-canthaxanthin. Violerythrin is now especially readily accessible from the novel polyene compounds of formula IA hereinbefore as shown in the following
Formula Scheme:
o owv \ violerythrin i .Ji"i"i" r blu/ (Ib) \veow A' Acowe-a ^ ACO AcO 0 (Ic) 0 (Id) \ ,ÓAe \ o o < HO < gt OH HO (Ie) (If) I HO' & H ) OH & a :tinioerythrol o o ro o (Ig) \ o (Ih) (Ih) Wa L I , fviolerythrin The process provided by the present invention for the manufacture of the polyene compounds of formula IA comprises reacting a compound of the general formula
with a compound of the general formula
wherein R represents an oxo or acyloxy group, one of the symbols A and B repre
sents the formyl group and the other symbol represents a triarylphosphonium
methyl group of the formula H2-P [X] ,Y, in which X represents an aryl
group and Y represents the anion of an organic or inorganic acid, and the broken
line denotes an optional carbon-carbon bond, to give a polyene compound of the general formula
wherein R and the broken lines have the significance given earlier, and, if desired, converting the compound of formula I in which R represents an oxo group by partial hydrogenation into violerythrin, or converting a compound of formula
I in which R represents an acyloxy group in optional sequence by partial hydrogenation and saponification into actinioerythrol or by partial hydrogenation, saponification and oxidation or saponification, oxidation and partial hydrogenation into violerythrin.
Of the aforementioned embodiments for the manufacture of the polyene compounds of formula IA there have been found to be especially convenient the procedures denoted as (a), (b), (c) and (d) hereinafter, namely the reaction of
(a) a phosphonium salt of the general formula
wherein X and Y have the significance given earlier, or
(b) a phosphonium salt of the general formula
wherein X and Y have the significance given earlier, or
(c) a phosphonium salt of the general formula
wherein R' represents an acyloxy group and X and Y have the significance given
earlier, or
(d) a phosphonium salt of the general formula
wherein R', X and Y have the significance given earlier, with the dialdehyde of the formula
The starting materials are reacted with one another by means of a Wittig reaction in the presence of an acid-binding agent, for example an alkali metal hydroxide such as potassium hydroxide, an alkalii metal alcoholate such as sodium methyl ate or an alkylene oxide which may be alkyl-substituted, especially in the presence of ethylene oxide or 1,2-butylene oxide, if desired in a solvent, for example an alkanol such as isopropanol, a chlorinated hvdrocarbon such as methvlene chloride or dimethylformamide, at a temperature between room temperature and the boiling point of the reaction mixture.
An acyloxy group denoted by R or R' is derived from a lower or higher alkanecarboxylic acid or alkenecarboxylic acid. The lower members contain up to 6 carbon atoms and the higher members contain from 7 to 20 carbon atoms. Both members can be substituted by halogen, alkoxy or aryloxy. Examples of the lower members are the acetoxy, propionyloxy, butyryloxy, valeryloxy, caprylyloxy, monochloroacetoxy, dichloroacetoxy, ethoxyacetoxy and phenoxyacetoxy groups. Examples of the higher members are the palmitoyloxy, stearoyloxy and oleoyloxy groups.
The acyloxy groups substituted by halogen, alkoxy or aryloxy can be saponified to the hydroxy group without this being converted partially into the oxo group during the saponification.
When it is desired to convert a polyene compound of formula Ic or Id by the aforementioned procedures into actinioerythrol, then such polyene compounds must be substituted by one of the previously mentioned acyloxy groups which are readily cleavable by hydrolysis. When a normal ester of formula Ic or Id is used (e.g. the acetic acid or the palmitic acid ester), then the hydroxy group initially liberated during the saponification is converted immediately into the oxo group under the conditions required for the cleavage of the acyl groups, and violerythrin is obtained as the end nroduct.
Of the acyloxy groups which are cleavable under mild conditions there occupy a preferred position the acyloxy groups substituted by chloro or phenoxy, which can be saponified to the hydroxy group by means of weak alkalis at a temperature between about - 300C and + 500C. The monochloroacetoxy and dichloroacetoxv groups can even be hydrolysed by mere heating in water or in an aqueous alkanol. The (trichloro or trifluoro)acetoxy group is less suitable as the protecting group because of its liability.
The starting materials of the general formulae
wherein R', X, Y and the broken line have the significance given earlier, used in embodiments (a), (b), (c) and (d) of the process are novel. They can be prepared from a common key compound of the formula
which is likewise novel.
The preparation of the starting materials of formula IIAB starting from the triol of formula IX is illustrated in the following Formula Scheme in which X and Y have the significance given earlier:
The preparation of the starting materials of formula IICD starting from the triol of formula IX is illustrated in the following Formula Scheme in which R', X and Y have the significance given earlier:
The preparation of the starting materials of formula IIAB is carried out, in general, as follows:
The triol of formula IX, 5 - [1,4 - dihydroxy - 2,5,5 - trimethyl - cyclopent - 2en - 1 - yl] - 3 - methyl - pent - 2 - en - 4 - yn - 1 - ol is first subjected to an allyl rearrangement to give the triol of formula X, 5 - [3,4 - dihydroxy - 2,5,5 - trimethylcyclopent - 1 - en - 1 - yl] - 3 - methyl - pent - 2 - en - 4 - yn - 1 - ol. The allyl rearrangement is conveniently carried out in an aqueous mineral acid such as sulphuric acid, if desired in the presence of a solvent such as acetone or tetrahydrofuran, or in an organic acid such as formic or acetic acid. If an organic acid is used, then the ester which intermediately results must be saponified (e.g. with an aqueous sodium carbonate solution).
The resulting triol of formula X is subsequently oxidised to the aldehyde of
formula XI, 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3
methyl - pent - 2 - en - 4 - yn - 1 - al. The oxidation can be carried out for example, using nickel peroxide or manganese dioxide. The oxidation is conveniently carried out in a solvent such as diethyl ether, ethyl acetate, dioxan or benzene, and at a temperature between - 30"C and the boiling point of the oxidation mixture.
The resulting acetylenic ketoaldehyde of formula XI is then either partially hydrogentaed to the olefinic ketoaldehyde of formula XII, 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - penta - 2,4 - dien - 1 - al, which is subsequently reduced to the olefinic ketoalcohol of formula XIV, 5 - [3,4 - dioxo2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - penta - 2,4 - dien - 1 - ol, or reduced to the acetylenic ketoalcohol of formula XIII, 5 - [3,4 - dioxo - 2,5,5trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - pent - 2 - en - 4 - yn - 1 - ol, which is subsequently partially hydrogenated to the olefinic ketoalcohol of formula
XIV.
The partial hydrogenation of the ethynylcne to the vinylene group is carried out in a manner known per se using a partially deactivated palladium catalyst (Lindlar catalyst) in a solvent such as benzene, toluene, ethyl acetate or an alkanol such as methanol, conveniently at normal pressure and room temperature.
The conversion of the ketoaldehydes of formulae XI and XII into the ketoalcohols of formulae XIII and XIV is carried out using a reducing agent, for example sodium borohydride in ethanol, dimethylformamide, tetrahydrofuran or diethyleneglycol dimethyl ether, or sodium dihydro - bis(2 - methoxyethoxy)aluminate or diisobutylaluminium hydride in tetrahydrofuran or dimethyl ether, at a temperature below OOC, particularly at - 30"C.
The resulting ketoalcohols of formulae XIII and XIV are subsequently converted by treatment with a halogenating agent, for example phosphorus tribromide, phosphorus oxychloride, thionyl chloride or phosgene in an ether or in dimethylformamide or N-bromosuccinimide in the presence of dimethvlsulphide, into the correspnpding halides, which are converted by reaction with a triarylphosphine (e.g. triphenylphosphine) into the phosphonium salts of formulae IIa and llB which can be generically formulated under formula IIAB.
The preparation of the starting materials of formula IICD is carried out, in general, as follows:
The triol of formula X obtained as previously described from the triol of formula
IX by allyl rearrangement is oxidised to rhe aldehyde of formula XV, 5 - [3 - oxo - 4hydroxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - pent - 2 - en4 - yn - 1 - al. The oxidation is carried out in the same manner as previously described for the oxidation of the triol of formula X to the aldehyde of formula XI. As the oxidation agent there is, however, conveniently used 2,3 - dichloro - 5,6 - dicyano - benzoquinone since this guarantees the desired selectivity.
The resulting acetylenic hydroxyaldehyde of formula XV is either partially hydrogenated to the olefinic hydroxyaldehyde of formula XVI, 5 - (3 - oxo - 4hydroxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - penta - 2,4dien - 1 - al, which is subsequently esterified to an olefinic ester of formula XVIII, a 5 - [3 - oxo - 4 - acyloxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - ylJ - 3 - methyl- penta - 2,4 - dien - 1 - al, or esterified to an acetylenic ester of formula XVII, a 5 - [3 oxo - 4 - acyloxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - ylj - 3 - methyl - pent2 - en - 4 - yn - 1 - al which is subsequently partially hydrogenated if desired to the olefinic ester of formula XVIII.
The sequence in which the partial hydrogenation of the acetylenic compound and the masking of the hydroxy group is carried out is determined by the choice of the esterification agent. When there is used a halogenated carboxylic acid, the halogen atom of which could poison the catalyst, such as, for example, monochloroacetic acid or dichloroacetic acid, then it is recommended to initially partially hydrogenate the acetylenic hydroxyaldehyde of formula XV and subsequently to esterify the resulting olefinic hydroxyaldehyde of formula XVI. On the other hand, when there is used a halogen-free esterification agent, then the acetylenic hydroxyaldehyde of formula XV can initially be esterified and the resulting acetylenic ester of formula XVII can be subsequently partially hydrogenated.
The partial hydrogenation is carried out in an analogous manner to that previously described in detail.
The masking of the hydroxy group by esterification with a lower or higher alkanecarboxylic acid or alkenecarboxylic acid anhydride or halide, which may be substituted by halogen, alkoxy or aryloxy, is carried out, if desired in a solvent such as tetrahydrofuran or methylene chloride, in the presence of an organic nitrogen base such as pyridine or triethylamine at a temperature between about -300C and + 50 C.
The resulting masked ketoaldehydes of formulae XVII and XVIII are subsequently converted into the ester alcohols of formulae XIX and XX in the same manner as described earlier for the conversion of the ketoaldehydes of formulae XI and
XII into the ketoalcohols of formulae XIII and XIV.
The resulting ester alcohols of formulae XIX and XX are subsequently converted, in the same manner as previously described in connection with the alcohols of formulae
XIII and XIV, via the halides into the phosphonium salts of formulae IIC and IID which can be generically formulated under formula IICD.
The dialdehyde starting material of formula IIIA, 2,7 - dimethyl - octa - 2,6dien - 4 - yne - 1,8 - dial, is a known compound.
Likewise known is the analogous 2,7 - dimethyl - octa - 2,4,6 - trien - 1,8 - dial which, by reaction with a phosphonium sak of formula IIB directly yields violerythrin and by reaction with a phosphonium salt of formula IID directly yields actinioerythrol.
The aforementioned key compound of formula IX can be obtained, for example, from 2,5,5 - trimethyl - cyclopent - 2 - ene - 1,4 - dione of formula IV as shown in the following Formula Scheme:
The individual steps of this Formula Scheme are carried out, for example, as follows:
The known 2,5,5 - trimethyl - cyclopent - 2 - en - 1,4 - dione of formula IV is dissolved in an organic solvent (e.g. an alkanol) and reduced at a temperature below 0 C with sodium borohydride. The desired 4 - hydroxy - 2,5,5 - trimethyl - cyclo pent - 2 - en - 1 - one of formula V is isolated by rectification from the isomers mixture which occurs during the working-up.
The 4 - hydroxy - 2,5,5 - trimethyl - cyclopent - 2 - en - 1 - one of formula V is an important compound in the preparation of the aforementioned key compound of formula IX. The 4 - hydroxy - 2,5,5 - trimethyl - cyclopent - 2 - en - 1 - one of formula V is novel and is the subject of our Divisional Application No. 8817/79 serial No. 1 585 500).
The hydroxy group of the hydroxyketone of formula V is subsequently masked by treatment with trimethylchlorosilane in the presence of an organic nitrogen (e.g. triethylamine) in diethyl ether in the cold at about OOC.
The resulting 2,5,5 - trimethyl - 4 - [(trimethylsilyl)oxy] - cyclopent - 2 - en1 - one of formula VI is then condensed in a solvent (e.g. tetrahydrofuran by means of a Grignard reaction with trimethyl - [(trans - 3 - methyl - pent - 2 - en - 4 - yn1 - yl)oxy] - silane of formula VII to give 5 - [2,5,5 - trimethyl - l - hydroxy - 4
[(trimethylsilyl)oxy] - cyclopent - 2 - en - 1 - yl] - 3 - methyl - 1 - [(trimethylsilyl)oxy] - pent - 2 - en - 4 - yne of formula VIII which, without isolation, is saponified by shaking with a dilute aqueous alkali hydroxide solution to give 5 - [1,4 - dihydroxy2,5,5 - trimethyl - cyclopent - 2 - en - 1 - yl] - trans - 3 - methyl - pent - 2 - en - 4yn - 1 - ol of formula IX.
The aforementioned trimethyl - [(trans - 3 - methyl - pent - 2 - en - 4 - yn - 4yl) - oxyj - silane of formula VII can be readily obtained by the action of trimethylchlorosilane at room temperature on trans - 3 - methyl - pent - 2 - en - 4 - yne in an ether such as dimethyl ether in the presence of an organic nitrogen base such as triethylamine.
The following Examples illustrate the present invention:
Example 1.
After the addition of 150 ml of butylene oxide, 8.1 g of 5 - [3,4 - dioxo - 2,5,5trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - penta - 2,4 - diene - 1 - triphenylphosphonium bromide and 820 g of 2,7 - dimethyl - octa - 2,6 - dien - 4 - yn - 1,8dial are stirred at room temperature for 5 hours. The mixture is then introduced into water and extracted with methylene chloride. The extract is evaporated under reduced pressure. The residual 15,15' - didehydroviolerythrin is purified by adsorption on silica gel. U.V. maximum: 520 nm (in chloroform).
The resuking 15,15' - didehydroviolerythrin can be converted into violerythrin as follows:
5.6 g of 15,15' - didehydroviolerythrin are dissolved in 1000 ml of toluene. After the addition of 2 g of partially deactivated palladium catalyst (Lindlar catalyst), the solution is shaken in a hydrogen atmosphere at rooom temperature and normal pressure until the calculated amount of hydrogen has been taken up. The catalyst is then separated. The filtrate is evaporated under reduced pressure. The residual violerythrin melts at 2360-2380C after recrystallisation from methylene chloride/hexane. U.V.
maximum: 580 nm (in chloroform).
The 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methylpenta - 2,4 - diene - 1 - triphenylphosphonium bromide used as the starting material can be prepared as follows:
138 g of 2,5,5 - dimethyl - cyclopent - 2 - ene - 1,4 - dione are dissolved in 1000 ml of methanol. The solution is treated with 10 g of solid sodium borohydride while stirring at --20"C. After the reaction fades away, the mixture is introduced into a saturated aqueous sodium chloride solution and extracted with ethyl acetate. The extract is evaporated under reduced pressure. The residual crude 4 - hydroxy - 2,5,5trimethyl - cyclopent - 2 - en - 1 - one boils at 850-870C/0.S Torr after rectification.
97 g of 4 - hydroxy - 2,5,5 - trimethyl - cyclopent - 2 - en - 1 - one are dissolved in 600 ml of ether. After the addition of 90 ml of triethylamine, the solution is treated dropwise at OOC with 81 ml of trimethylchlorosilane and stirred at 0 C for 4 hours.
The mixture is then introduced into water and extracted with ether. The ether extract is washed with water, dried over sodium sulphate and evaporated under reduced pressure. The residual 2,5,5 - trimethyl - 4 - [(trimethylsilyl)oxyj - cyclopent - 2 - en1 - one boils at 400--43"C/0.02 Torr.
12.1 g of trimethyl - [(trans - 3 - methyl - pent - 2 - en - 4 - yn - 1 - yl)oxy]silane are dissolved in 150 ml of tetrahydrofuran. The solution is added dropwise to a
Grignard solution prepared from 1.73 g of magnesium shavings and 7.78 g of ethyl bromide. The mixture is stirred for 1 hour and then, after the addition of a solution of 10.1 g of 2,5,5 - trimethyl - 4 - [(trimethylsilyl)oxy] - cyclopent - 2 - en - 1 - one in 50 ml of tetrahydrofuran, for a further 20 hours. The mixture is then introduced into a saturated aqueous ammonium chloride solution and extracted with ether. The extract is evaporated under reduced pressure. The residual 5 - [2,5,5 - trimethyl - 1 - hydroxy4 - [(trimethylsilyl)oxyj - cyclopent - 2 - en - 1 - ylj - 3 - methyl - 1 - [(trimethyl silyl)oxyj - pent - 2 - en - 4 - yne, a mixture of two isomers, is dissolved in 140 ml of methanol without purification and separation. After the addition of 28 ml of 5% aqueous potassium hydroxide, the solution is stirred for 5 minutes, subsequently introduced into a saturated aqueous sodium chloride solution and extracted with ether. The ether extract is evaporated under reduced pressure. The residual 5 - [1,4 - dihydroxy2,5,5 - trimethyl - cyclopent - 2 - en - 1 - ylj - trans - 3 - methyl - pent - 2 - en4 - 4 - yn - 1 - ol, a mixture of two isomers, is isomerised as follows without further purification:
90.4 g of 5 - [1,4 - dihydroxy - 2,5,5 - trimethyl - cyclopent - 2 - en - 1 - yl]trans - 3 - methyl - pent - 2 - en - 4 - yn - 1 - ol are dissolved in 1400 ml of methylene chloride. The solution is treated with 380 ml of 98% formic acid, stirred for 45 minutes and subsequently introduced into water. The organic phase is separated and evaporated under reduced pressure. The residue is taken up in 780 ml of methanol, treated with 200 g of potassium carbonate in 500 ml of water, stirred for 1 hour, introduced into water and extracted with ethyl acetate. The 5 - [3,4 - dihydroxy - 2,5,5trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - pent - 2 - en - 4 - yn - 1 - ol isolated from the extract melts at 121,-1220C.
2.35 g of 5 - [3,4 - dihydroxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - pent - 2 - en - 4 - yn - 1 - ol are dissolved in 200 ml of methylene chloride. After the addition of 90 g of activated manganese dioxide, the solution is stirred for 1 hour at room temperature. The mixture is then filtered. The filtrate is evaporated under reduced pressure. The residual 5 - [3,4 - dioxo - 2,5,5 - trimethylcyclopent - 1 - en - 1 - yl] - 3 - methyl - pent - 2 - en - 4 - yn - 1 - al melts at 1410--1420C after purification by adsorption on silica gel.
5 - [3 - Oxo - 4 - hydroxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - ylj - 3- methyl - pent - 2 - en - 4 - yn - 1 - al can be isolated as the byproduct.
4 g of 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - pent - 2 - en - 4 - yn - 1 - al are dissolved in 100 ml of ethyl acetate. The solution is shaken in a hydrogen atmosphere in the presence of 1 g of partially deactivated palladium catalyst (Lindlar catalyst) at room temperature and normal pressure until the calculated amount of hydrogen has been taken up. The catalyst is separated.
The filtrate is evaporated under reduced pressure. The residual 5 - [3,4 - dioxo2,5,5 - trimethyl - cyclopent - 1 - en - 1 - ylj - 3 - methyl - penta - 2,4 - dien - 1 - al is further processed as follows without purification.
4.64 g of 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - penta - 2,4 - dien - 1 - al are dissolved in 150 ml of tetrahydrofuran. The solution is treated dropwise at --70"C with 250 mg of sodium borohydride in 5 ml of water. After 20 minutes, the mixture is introduced into a saturated aqueous sodium chloride solution and extracted with ethyl acetate. The extract is evaporated under reduced pressure. The residual 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1en - 1 - yl] - 3 - methyl - penta - 2,4 - dien - 1 - ol is converted as follows into the desired phosphonium salt without further purification.
4.6 g of S - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - penta - 2,4 - dien - 1 - ol are dissolved in 20 ml of methylene chloride. The solution is added dropwise at 0 C to a suspension of 3.6 g of N-bromosuccinimide in 20 ml of methylene chloride and 2 ml of dimethylsulphide. The mixture is stirred at 0 C for 2 hours, then introduced into water and extracted with ether/hexane (2:1).
The crude 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methylpenta - 2,4 - diene - 1 - bromide remaining after evaporation of the extract is dissolved in 70 ml of ethyl acetate. The solution is treated with 5.3 g of triphenylphosphine. The 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - penta2,4 - diene - 1 - triphenylphosphonium bromide which separates in the course of 24 hours is dried in a high vacuum and then further processed as described in the first paragraph of this Example.
Example 2.
5.6 g of 5 - [3 - oxo - 4 -phenoxyacetyl - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 yl] - 3 - methyl - pent - 2 - en - 4 - yne - 1 - triphenylphosphonium bromide and 0.43 g of 2,7 - dimethyl - octa - 2,6 - dien - 4 - yne - 1,8 - dial are dissolved in 100 ml of isopropanol. After the addition of 4.1 ml of 2-N sodium methylate, the solution is stirred at room temperature for 1 hour. The mixture is then introduced into water and extracted with methylene chloride. The 2,2' - dinor - 7,7',8,8',15,15' - hexadehydroastaxanthin remaining after evaporation of the extract is purified by adsorption on silica gel. In the mass spectrum the compound shows the expected molecular weight of 562.
860 mg of 2,2' - dinor - 7,7',8,8',15,15' - hexadehydroastaxanthin are dissolved in 200 ml of toluene. After the addition of 300 mg of partially deactivated palladium catalyst (Lindlar catalyst), the mixture is hydrogenated in a hydrogen atmosphere at room temperature and normal pressure until the calculated amount of hydrogen has been taken up. The catalyst is then separated. The actinioerythrol [2,2' - dinorastaxanthin] remaining after evaporation of the filtrate melts at 207 208 C after recrystallisation from methylene chloride/hexane.
270 mg of 2,2' - dinor - 7,7',8,8',15,15' - hexadehydroastaxanthin are dissolved in 80 ml of toluene. After the addition of 0.7 g of solid sodium carbonate, air is blown through the solution until the greater portion of the starting material has been converted into 2,2' - dinor - 7,7',8,8',15,15' - hexadehydroastacene. The mixture is filtered.
The crude product remaining after evaporation of the filtrate is purified by adsorption on silica gel. The mass spectrum shows a molecular weight of 558. The pure 2,2'dinor - 7,7',8,8',15,15' - hexadehydroastacene can be converted into violerythrin [2,2'dinor - astacene] in the same manner as described for the hydrogenation of 2,2' - dinor 7,7',8,8',15,15' - hexahydroastaxanthin to actinioerythrol.
The 5 - [3 - oxo - 4 - phenoxyacetyl - 2,5,5 - trimethyl - cyclopent - 1 - en - 1yl] - 3 - methyl - pent - 2 - en - 4 - yne - 1 - triphenylphosphonium bromide used as the starting material can be prepared as follows:
50 g of the 5 - [3,4 - dihydroxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl]3 - methyl - pent - 2 - en - 4 - yn - 1 - ol obtained according to Example 1 are dissolved in 300 ml of dioxan. After the addition of 120 g of 2,3 - dichloro - 5,6 - dicyano - benzoquinone, the solution is stirred at 800C for 5 hours. The mixture is then cooled. The 2,3 - dichloro - 5,6 - dicyano - benzohydroquinone which separates as the byproduct is filtered off. The 5 - [3 - oxo - 4 - hydroxy - 2,5,5 - trimethyl - cyclopent1 - en - 1 - yl] - 3 - methyl - pent - 2 - en - 4 - yn - 1 - al, an oil, which remains after evaporation of the filtrate is purified by adsorption on silica gel and is further processed as follows:
34 g of 5 - [3 - oxo - 4 - hydroxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl]3 - methyl - pent - 2 - en - 4 - yn - 1 - al are dissolved in 400 ml of ether. After the addition of 15 ml of pyridine, the solution is treated dropwise at -200C with 30 g of phenoxyacetic acid chloride. After 30 minutes, the mixture is introduced into water and extracted with ether. The 5 - [3 - oxo - 4 - phenoxyacetyl - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - pent - 2 - en - 4 - which remains after evaporation of the extract shows a U.V. maximum at 487 nm (in chloroform).
1 g of 15,15' - didehydroactinioerythrol dicaetate is dissolved in 200 ml of toluene.
The solution is treated, with the complete exclusion of air, with an equivalent amount of 2-N sodium methylate until the control by thin-layer chromatography indicates the end of the reaction. The mixture is introduced into water. The organic phase is separated and evaporated. The residual 15,15' - didehydroactinioerythrol contaminated by 15,15' - didehydroviolerythrin can be purified by adsorption on silica gel.
420 mg of the resulting crude 15,15' - didehydroactinioerythrol are dissolved in 100 ml of toluene. After the addition of 1 g of solid sodium carbonate, air is blown through the solution until the greater portion of the starting material has been converted into 15,15' - didehydroviolerythrin. The mixture is filtered. The 15,15' - didehydroviolerythrin which remains after evaporation of the filtrate is purified by adsorption on silica gel. The mass spectrum shows a molecular weight of 562. U.V. maximum: 520 nm (in chloroform).
The resulting 15,15' - didehydroviolerythrin can be partially hydrogenated to violerythrin as described in Example 1.
The 15,15' - didehydroactinioerythrol previously obtained can be partially hydrogenated to actinioerythrol as follows:
1.2 g of 15,15' - didehydroactinioerythrol are dissolved in 280 ml of toluene. After the addition of 0.8 g of partially deactivated paladium catalyst (Lindlar catalyst), the solution is hydrogenated in a hydrogen atmosphere at room temperature and normal pressure until the calculated amount of hydrogen has been taken up. The catalyst is then separated. The actinioerythrol which remains after evaporation of the filtrate melts at 207 208 C after recrystallisation from methylene chloride/hexane.
In the same manner as previously described, 15,15' - didehydroactinioerythrol diacetate can be hydrogenated to actinioerythrol diacetate; U.V. maximum: 518 nm (in chloroform).
The 5 - [3 - oxo - 4 - acetyl - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 3 - methyl - penta - 2,4 - diene - 1 - triphenylphosphonium bromide used as the starting material can be prepared as follows:
1 g of the 5 - [3 - oxo - 4 - hydroxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1yl] - 3 - methyl - pent - 2 - en - 4 - yn - 1 - al obtained according to Example 2 is dissolved in 250 ml of ethyl acetate. After the addition of 5 g of partially deactivated palladium catalyst (Lindlar catalyst), the solution is hydrogenated at room temperature and normal pressure with the addition of 0.24 ml of quinoline until the calculated amount of hydrogen has been taken up. The catalyst is separated. The 5 - [3 - oxo4 - hydroxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - penta - 2,4dien - 1 - al which remains after evaporation of the filtrate is processed as follows without further purification:
55 g of 5 - [3 - oxo - 4 - hydroxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl]3 - methyl - penta - 2,4 - dien - 1 - all are dissolved in 700 ml of ether. After the addition of 100 ml of pyridine, the solution is treated dropwise at - 200C with 25 ml of acetyl chloride. After 30 minutes, the mixture is introduced into water and extracted with ether. The practically pure, oily 5 - [3 - oxo - 4 - acetoxy - 2,5,5 - trimethylcyclopent - 1 - en - 1 - yl] - 3 - methyl - penta - 2,4 - dien - 1 - al which remains after evaporation of the extract is further processed as follows:
10 g of 5 - [3 - oxo - 4 - acetoxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl]3 - methyl - penta - 2,4 - dien - 1 - ali are dissolved in 200 ml of tetrahydrofuran and
10 ml of water. 1.5 g of sodium borohydride are introduced portionwise into the solution at --45"C. After 30 minutes, the mixture is introduced into a saturated aqueous sodium chloride solution and extracted with ether. The practically pure, oily 5 - [3oxo - 4 - acetoxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - pent2,4 - dien - 1 - ol [I.R. spectrum: 3550 cm-l and 1730 cm-1] which remains after evaporation of the extract is converted into the desired phosphonium salt as follows:
7.35 g of 5 - [3 - oxo - 4 - acetoxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 yl] - 3 - methyl - penta - 2,4 - dien - 1 - ol are dissolved in 20 ml of methylene chloride. The solution is introduced into a suspension of 9 g of N-bromosuccinimide in 15 ml of methylene chloride and 5 ml of dimethylsulphide. The mixture is stirred at room temperature for 1 hour, then introduced into water and extracted with ether. The crude 5 - [3 - oxo - 4 - acetoxy - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - penta - 2,4 - diene - 1 - bromide which remains after evaporation of the extract is dissolved in 100 ml of ethyl acetate. The solution is treated with 7 g of triphenylphosphine. The 5 - [3 - oxo - 4 - acetoxy - 2,5,5 - trimethyl - cyclopent - 1 en - 1 - yl] - 3 - methyl - penta - 2,4 - diene - 1 - triphenylphosphonium bromine which separates in crystalline form in the course of 24 hours melts at 212--215"C.
Example 4.
7.4 g of 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - pent - 2 - en - 4 - yne - 1 - triphenylphosphonium bromide are stirred at room temperature for 3 hours together with 0.9 g of 2,7 - dimethyl - octa - 2,6 - dien - 4yne - 1,8 - dial in 100 ml of butylene oxide. The mixture is subsequently evaporated.
The residual 2,2' - dinor - 7,7',8,8',15,15' - hexadehydroastacene [7,7',8,8',15,15'- hexadehydroviolerythrin] can be converted by partial hydrogenation into violerythrin as described in Example 2.
The 5 - 13,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methylpent - 2 - en - 4 - yne - 1 - triphenylphosphonium bromide used as the starting material can be prepared as follows:
5.7 g of the 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - pent - 2 - en - 4 - yn - 1 - al obtained according to Example 1 are dissolved in 100 ml of tetrahydrofuran. The solution is treated at - 700C while stirring with 260 mg of sodium borohydride in 5 ml of water. After 30 minutes, the mixture is introduced into a saturated aqueous sodium chlonde solution and extracted with ethyl acetate. The 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - pent - 2 - en - 4 - yn - 1 - ol which remains after evaporation of the extract is processed as follows without further purification:
2.3 g of 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - pent - 2 - en - 4 - yn - 1 - ol are dissolved in 20 ml of methylene chloride.
The solution is added dropwise at O"C to a suspension of 2 g of N-bromosuccinimide in 20 ml of methylene chloride and 3 ml of dimethylsulphide. After 2 hours, the mixture is introduced into water and extracted with ether/hexane (2:1). The crude 5- [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - mtehyl - pent - 2en - 4 - yne - 1 - bromide which remains after evaporation of the extract is dissolved in 100 ml of ethyl acetate. The solution is treated with 2.6 g of triphenylphosphine.
The sticky, oil 5 - [3,4 - dioxo - 2,5,5 - trimethyl - cyclopent - 1 - en - 1 - yl] - 3methyl - pent - 2 - en - 4 - yne - 1 - triphenylphosphonium bromide is dried in a high vacuum after separation of the supernatant solvent. Infrared spectrum: 1755 cml; 1696 cm1.
The following Example illustrates the production of a colouring preparation containing a polyene compound obtained according to the present invention:
Example A.
Production of a colouring preparation suitable for the colouring of foodstuffs:
1.0 g of 15,15' - didehydroviolerythrin, 0.1 g of d,l - xr - tocopherol. 0.4 g of arachis oil and 1.0 g of ascorbyl palmitate are dissolved in 50 ml of hot chloroform.
The solution is homogenised with 4.1 g of gelatin, 1.7 g of sugar, 1.7 g of yellow dextrin and 0.2 g of sodium carbonate - dissolved in 50 ml of water. The homogenate is poured on to a metal sheet, dried chloroform-free in a vacuum and pulverised.
1-50 g of the previously obtained colouring preparation are required for the colouring of 100 kg of candy mass. The colouring preparation, dissolved in 10-500 ml of warm water, is added to the candy mass together with the aromas (e.g. red-currant or raspberry aroma) and the resulting mixture is homogeneously mixed.
WHAT WE CLAIM IS:
1. A process for the manufacture of polyene compounds, which process comprises reacting a compound of the general formula
with a compound of the general formula
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (18)
1. A process for the manufacture of polyene compounds, which process comprises reacting a compound of the general formula
with a compound of the general formula
wherein R represents an oxo or acyloxy group, one of the symbols A and B repre
sents the formyl group and the other symbol represents a triarylphosphonium
methyl group of the formula --CH,,-P[X]3r=, in which X represents an aryl
group and Y represents the anion of an organic or inorganic acid, and the broken
line denotes an optional carbon-carbon bond, to give a polyene compound of the general formula
wherein R and the broken lines have the significance given earlier in this claim, and, if desired, converting the compound of formula I in which R represents an oxo group by partial hydrogenation into violerythrin, or converting a compound of formula
I in which R represents an acyloxy group in optional sequence by partial hydrogenation and saponification into actinioerythrol, or by partial hydrogenation, saponification and
oxidation or saponification, oxidation and partial hydrogenation into violerythrin.
2. A process according to claim 1, wherein a phosphonium salt of the general
formula
wherein X and Y have the significance given in claim 1, is reacted with the dialdehyde of the formula
3. A process according to claim 1, wherein a phosphonium salt of the general formula
wherein X and Y have the significance given in claim 1, is reacted with the dialdehyde of the formula
4. A process according to claim 1, wherein a phosphonium salt of the general formula
wherein R' represents an acyloxy group and X and Y have the significance given
in claim 1, is reacted with the dialdehyde of the formula
5. A process according to claim 1, wherein a phosphonium salt of the general formula
wherein R' represents an acyloxy group and X and Y have the significance given
in claim 1, is reacted with the dialdehyde of the formula
6. A process according to claim 2, wherein a 5 - [3,4 - dioxo - 2,5,5 - trimethyl cyclopent - 1 - en - 1 - yl] - methyl - pent - 2 - en - 4 - yne - 1 - triphenylphosphonium halide is reacted with 2,7 - dimethyl - octa - 2,6 - dien - 4 - yne - 18 - dial.
7. A process according to claim 3, wherein a 5 - [3,4 - dioxo - 2,5,5 - trimethyl cyclopent - 1 - en - 1 - yl] - 3 - methyl - penta - 2,4 - diene - 1 - triphenylphosphonium halide is reacted with 2,7 - dimethyl - octa - 2,6 - dien - 4 - yne - 1,8 - dial.
8. A process according to claim 4, wherein a 5 - [3 - oxo - 4 - (acyloxy) - 2,5,5trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - pent - 2 - en - 4 - yne - 1 - triphenylphosphonium halide is reacted with 2,7 - dimethyl - octa - 2,6 - dien - 4 - yne1,8 - dial.
9. A process acording to claim 5, wherein a 5 - [3 - oxo - 4 - (acyloxy) - 2,5,5trimethyl - cyclopent - 1 - en - 1 - yl] - 3 - methyl - penta - 2,4 - diene - 1 - tri phenylphosphonium halide is reacted with 2,7 - dimethyl - octa - 2,6 - dien - 4 - yne1,8 - dial.
10. A process for the manufacture of polyene compounds, substantially as hereinbefore described with reference to any one of Examples 1 to 4.
11. A polyene compound, when manufactured by the process claimed in any one of claims 1 to 10 inclusive or by an obvious chemical equivalent thereof.
12. Polyene compounds of the general formula
wherein Rl represents an oxo, acyloxy or hydroxy group and the broken lines denote optical carbon-carbon bonds.
13. 2,2' - Dinor - 7,7',8,8',15,15' - hexadehydro - astacene. (Ia).
14, 2,2 - Dinor - 15,15' - didehydro - astacene. (Ib).
15. 2,2' - Dinor - 7,7',8,8',15,15' - hexadehydroastaxanthin diacetate. (Ic).
16. 2,2' - Dinor - 15,15' - didehydroastaxanthin diacetate. (Id).
17. 2,2' - Dinor - 7,7',8,8',15,15' - hexadehydroastaxanthin. (Ie).
18. 2,2' - Dinor - 15,15' - didehydroastaxanthin. (If).
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT570576 | 1976-08-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1585499A true GB1585499A (en) | 1981-03-04 |
Family
ID=3578748
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB32189/77A Expired GB1585499A (en) | 1976-08-02 | 1977-08-01 | Polyene compounds |
GB8817/79A Expired GB1585500A (en) | 1976-08-02 | 1977-08-01 | Hydroxyketone |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8817/79A Expired GB1585500A (en) | 1976-08-02 | 1977-08-01 | Hydroxyketone |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPS5318541A (en) |
DE (1) | DE2733885A1 (en) |
FR (1) | FR2360546A1 (en) |
GB (2) | GB1585499A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2455018A1 (en) * | 1979-04-26 | 1980-11-21 | Roussel Uclaf | ALLETHROLONE DERIVATIVES AND THEIR PREPARATION PROCESS |
EP0826477B1 (en) * | 1996-09-03 | 2002-04-24 | Asahi Kasei Kabushiki Kaisha | Method for molding thermoplastic resin |
-
1977
- 1977-07-26 FR FR7722898A patent/FR2360546A1/en active Granted
- 1977-07-27 DE DE19772733885 patent/DE2733885A1/en not_active Withdrawn
- 1977-07-29 JP JP9048577A patent/JPS5318541A/en active Pending
- 1977-08-01 GB GB32189/77A patent/GB1585499A/en not_active Expired
- 1977-08-01 GB GB8817/79A patent/GB1585500A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5318541A (en) | 1978-02-20 |
FR2360546A1 (en) | 1978-03-03 |
DE2733885A1 (en) | 1978-02-09 |
GB1585500A (en) | 1981-03-04 |
FR2360546B1 (en) | 1979-07-20 |
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