NO823010L - 1,1-DITIENYL- (3) -1-HYDROXY-ALKYLHALOGENIDES. - Google Patents
1,1-DITIENYL- (3) -1-HYDROXY-ALKYLHALOGENIDES.Info
- Publication number
- NO823010L NO823010L NO823010A NO823010A NO823010L NO 823010 L NO823010 L NO 823010L NO 823010 A NO823010 A NO 823010A NO 823010 A NO823010 A NO 823010A NO 823010 L NO823010 L NO 823010L
- Authority
- NO
- Norway
- Prior art keywords
- thienyl
- general formula
- ether
- bromine
- compound
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000011877 solvent mixture Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 230000007306 turnover Effects 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 150000004996 alkyl benzenes Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 5
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- -1 dithienyl compound Chemical class 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001983 dialkylethers Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- SNHOZPMHMQQMNI-UHFFFAOYSA-N lithium;2h-thiophen-2-ide Chemical compound [Li+].C=1C=[C-]SC=1 SNHOZPMHMQQMNI-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- DBSMLQTUDJVICQ-CJODITQLSA-N onametostat Chemical compound NC1=C2C=CN([C@@H]3C[C@H](CCC4=CC=C5C=C(Br)C(N)=NC5=C4)[C@@H](O)[C@H]3O)C2=NC=N1 DBSMLQTUDJVICQ-CJODITQLSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Oppfinnelsen vedrører nye 1,1-ditienyl-(3)-1-hydroksy-alkyl-halogenider med den generelle formel The invention relates to new 1,1-dithienyl-(3)-1-hydroxy-alkyl halides with the general formula
hvori Alk betyr en rettlinjet eller forgrenet C^-C^-alkylengruppe og X betyr klor, brom eller jod samt en fremgangsmåte til deres fremstilling. De nye forbindelser med den generelle formel I fåes ifølge oppfinnelsen ved omsetning av tienyl-(3)- eller tienyl-(2)-litium med en forbindelse med den generelle formel hvori Alk betyr en rettlinjet eller forgrenet C^-C^-alkylengruppe, fortrinnsvis en rettlinjet C^-C^-alkylengruppe, Z betyr en lavere alkoksygruppe, klor, brom, jod eller en tienyl-(3)-rest eller en tienyl-(2)-rest og Hal er klor, brom eller jod ved lave temperaturer, fortrinnsvis under -50°Ci i et inert middel. Herved oppstår forbindelsen med formel I i et utbytte på eksempelvis 96% av det teore-tiske . in which Alk means a straight or branched C 1 -C 2 -alkylene group and X means chlorine, bromine or iodine and a method for their preparation. The new compounds with the general formula I are obtained according to the invention by reacting thienyl-(3)- or thienyl-(2)-lithium with a compound of the general formula in which Alk means a straight or branched C₁-C₂ alkylene group, preferably a linear C₁-C₁ alkylene group, Z means a lower alkoxy group, chlorine, bromine, iodine or a thienyl-(3) residue or a thienyl-(2) residue and Hal is chlorine, bromine or iodine at low temperatures, preferably below -50°Ci in an inert agent. Hereby, the compound with formula I is produced in a yield of, for example, 96% of the theoretical.
De hittil kjente analoge omsetninger, eksempelvis av tienyl-(3)-litium med o>-fenyletylamino-propionsyreestere (se tysk patent 1 921 453) forløper derimot ikke enhetlig og den ønskede ditienyl-(3)-forbindelse kan bare isoleres i utbytter på maksimalt 30%. Spesielt oppstår herved alltid andre tienyl-isomere i større mengder. Dessuten er adskillelsen og resning av den ønskede ditienyl-forbindelse fra de øvrige reaksjonsprodukter meget vanskelig, og eksempelvis bare mulig ved omstendelig og flere gangers omkrystallisering i kombina-sjon med en aktivkullbehandling. The previously known analogous reactions, for example of thienyl-(3)-lithium with o>-phenylethylamino-propionic acid esters (see German patent 1 921 453), on the other hand, do not proceed uniformly and the desired dithienyl-(3)-compound can only be isolated in yields of maximum 30%. In particular, other thienyl isomers always occur in larger amounts. Moreover, the separation and recovery of the desired dithienyl compound from the other reaction products is very difficult, and for example only possible by extensive and repeated recrystallization in combination with an activated carbon treatment.
I den generelle formel II betyr resten Z spesielt en mettet alifatisk alkoksygruppe med 1-6 C-atomer, fortrinnsvis 1-4 C-atomer, som også kan være forgrenet, klor eller brom. Z kan imidlertid også være en tienyl-(2)-rest eller en tienyl-(3)-rest. In the general formula II, the radical Z means in particular a saturated aliphatic alkoxy group with 1-6 C atoms, preferably 1-4 C atoms, which may also be branched, chlorine or bromine. However, Z can also be a thienyl-(2) residue or a thienyl-(3) residue.
Omsetningen av tienyllitium-forbindelsen, spesielt av tienyl-(3)-litium med forbindelsen II, foregår i en inert flytende oppløsningsmiddelblanding som fortrinnsvis består av en mettet eter og et mettet hydrokarbon og/eller med C-^-C-j-mono- eller dialkylrester substituert benzen. Som halogen-C2~Cg-alkankarboksylsyreestere kommer det eksempelvis på tale: 3-halogen-propionsyreester, -smørsyreester eller -valeriansyreester. The reaction of the thienyllithium compound, especially of thienyl-(3)-lithium with the compound II, takes place in an inert liquid solvent mixture which preferably consists of a saturated ether and a saturated hydrocarbon and/or with C-^-C-j-mono- or dialkyl radicals substituted benzene. Halogen-C2~Cg-alkanecarboxylic acid esters include, for example: 3-halo-propionic acid ester, -butyric acid ester or -valeric acid ester.
Består oppløsningsmiddelblandingen av en eter og mettet hydrokarbon, så anvendes eksempelvis på en volumdel hydrokarbon 0,3-3, fortrinnsvis 0,8-3 volumdeler eter. For en oppløsningsmiddelblanding av eter og mono- eller dialkylben-zen gjelder eksempelvis pr. 1 volumdel alkylbenzen 0,1-3, fortrinnsvis 0,2-1 volumdeler eter. Består oppløsnings-middelblandingen av de tre komponenter: eter, mettet hydrokarbon og alkylbenzen, da er eksempelvis blandingsforholdet av de tre komponenter eter:hydrokarbon:benzen = 0,1-0,9: 0,1-0,9:0,1-0,9. Som mettet eter kommer det spesielt på tale alifatiske symmetriske eller usymmetriske dialkyleter, idet alkylgruppene fortrinnsvis består av 1-6 C-atomer, If the solvent mixture consists of an ether and saturated hydrocarbon, then 0.3-3, preferably 0.8-3, parts by volume of ether are used, for example, per volume of hydrocarbon. For a solvent mixture of ether and mono- or dialkylbenzene applies, for example, per 1 volume part alkylbenzene 0.1-3, preferably 0.2-1 volume parts ether. If the solvent mixture consists of the three components: ether, saturated hydrocarbon and alkylbenzene, then for example the mixing ratio of the three components is ether:hydrocarbon:benzene = 0.1-0.9: 0.1-0.9:0.1- 0.9. Saturated ethers are particularly aliphatic symmetrical or unsymmetrical dialkyl ethers, the alkyl groups preferably consisting of 1-6 C atoms,
og eksempelvis er metyl, etyl, isopropyl, propyl, isobutyl eller butyl. Videre kommer det som eter eksempelvis også and examples are methyl, ethyl, isopropyl, propyl, isobutyl or butyl. Furthermore, things like ether also come, for example
i betraktning C^-Cg-alkyleter av mettede cykloalkanoler og considering C^-Cg alkyl ethers of saturated cycloalkanols and
alkylsubstituerte cykloalkanoler, idet cykloalkanolringen hver gang består av 3, 4, 5 eller 6 C-atomer. Fortrinnsvis er eterene flytende i området mellom -80 og +20°C. alkyl-substituted cycloalkanols, the cycloalkanol ring each time consisting of 3, 4, 5 or 6 C atoms. Preferably, the ethers are liquid in the range between -80 and +20°C.
Ved de mettede hydrokarboner dreier det seg om alifatiske eller cykloalifatiske hydrokarboner som er flytende i tempera-turområdet mellom -80 og +20°C, og eksempelvis har 5-9, fortrinnsvis 6-7 C-atomer og også kan være forgrenet. De cykloalifatiske hydrokarboner er fortrinnsvis substituert en eller også flere ganger (2 ganger, 3 ganger) med C-^-C^-alkylrester, spesielt metyl-, etyl- eller propylrester, idet antallet ringatomer kan være 3, 4, 5, 6 eller 7. De mettede alkyl-rester som kommer på tale som substituenter for benzen er metyl, etyl, propyl, isopropyl, butyl, isobutyl, tert.-butyl, 1-metylpropyl. The saturated hydrocarbons are aliphatic or cycloaliphatic hydrocarbons which are liquid in the temperature range between -80 and +20°C, and for example have 5-9, preferably 6-7 C atoms and can also be branched. The cycloaliphatic hydrocarbons are preferably substituted one or more times (2 times, 3 times) with C-^-C^-alkyl residues, especially methyl, ethyl or propyl residues, the number of ring atoms being 3, 4, 5, 6 or 7. The saturated alkyl residues that come into question as substituents for benzene are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 1-methylpropyl.
Eksempler for de angjeldende oppløsningsmidler er: dietyleter, diisopropyleter, metylcyklopentyleter, heksan, cykloheksan, toluen, xylen, metylcykloheksan, metylcyklopentan, etyl-cykloheksan, dimetylcykloheksan. Examples of the relevant solvents are: diethyl ether, diisopropyl ether, methylcyclopentyl ether, hexane, cyclohexane, toluene, xylene, methylcyclohexane, methylcyclopentane, ethylcyclohexane, dimethylcyclohexane.
Det er fordelaktig når forbindelsen II, spesielt når det dreier seg om 8-halogen-alkankarboksylsyreestere, tildoseres som sådanne eller i form av en oppløsning i hydrokarbonet og/eller eter (eksempelvis diisopropyleter og/eller toluen) til den til reaksjonstemperatur foravkjølte tienyllitium It is advantageous when the compound II, especially when it concerns 8-halo-alkanecarboxylic acid esters, is added as such or in the form of a solution in the hydrocarbon and/or ether (for example diisopropyl ether and/or toluene) to the thienyllithium precooled to reaction temperature
(som tienyl-(3)-litium) og deretter holdes reaksjonsblandingen enda i 1-4 timer ved reaksjonstemperatur. Deretter blandes eksempelvis reaksjonsoppløsningen med vann, eventuelt etter oppvarming til -20 til +20°C. Den organiske fase tørkes (MgSO^, Na2SO^) og inndampes under nedsatt trykk. Det således dannede rå 1,1-bis-[tienyl- (3 eller 2)]-3-halogen-alkanol kan anvendes uten ytterligere rensing for omsetningen med eksempelvis aminer. Tienyllitium-forbindelsene, eksempelvis tienyl-(3 eller 2)-litium, fremstilles vanligvis hver gang på forhånd av 3-brom- eller 2-brom-tiofen eller 3-jod-resp. 2-jod-tiofen i eteren og en C-^-C^-alkyllitium- eller (as thienyl-(3)-lithium) and then the reaction mixture is kept for a further 1-4 hours at the reaction temperature. Then, for example, the reaction solution is mixed with water, optionally after heating to -20 to +20°C. The organic phase is dried (MgSO^, Na2SO^) and evaporated under reduced pressure. The crude 1,1-bis-[thienyl-(3 or 2)]-3-haloalkanol thus formed can be used without further purification for the reaction with, for example, amines. The thienyllithium compounds, for example thienyl-(3 or 2)-lithium, are usually prepared each time in advance from 3-bromo- or 2-bromo-thiophene or 3-iodo-resp. 2-iodo-thiophene in the ether and a C-^-C^-alkyllithium or
aryllitium-forbindelse i eter-hydrokarbon-blåndingen, idet det som eter og hydrokarboner (innbefattende alkylbenzener) kommer på tale det allerede nevnte (som eter, spesielt dialkyleter).Alkylresten av alkyllitium-forbindelsen kan være rettlinjet eller forgrenet. Eksempeler er: butyllitium, sec.-butyllitium, tert.-butyllitium, metyllitium, etyllitium, fenyllitium, naftyllitium. aryllithium compound in the ether-hydrocarbon mixture, as ether and hydrocarbons (including alkylbenzenes) are those already mentioned (as ether, especially dialkylether). The alkyl residue of the alkyllithium compound can be linear or branched. Examples are: butyllithium, sec.-butyllithium, tert.-butyllithium, methyllithium, ethyllithium, phenyllithium, naphthyllithium.
Konsentrasjonen av alkyl- resp. aryllitium-forbindelseneThe concentration of alkyl or the aryllithium compounds
i det eventuelle oppløsningsmiddel ligger eksempelvis mellom 5 og 30 vekt-%. Konsentrasjonen av brom-tiofenet eller jod-tiofenet i det eventuelle oppløsningsmiddel ligger eksempelvis mellom 10 og 100 vekt-%. in the possible solvent is, for example, between 5 and 30% by weight. The concentration of bromo-thiophene or iodo-thiophene in the possible solvent is, for example, between 10 and 100% by weight.
Vanligvis går man fram således at brom- eller jod-tiofenet inndoseres som sådant eller i form av en oppløsning i eteren eller flytende alifatisk hydrokarbon eller alkylbenzen til litiumalkyl eller litiumaryl, som er oppløst resp. suspen-dert i en av d e nevnte etere eller en blanding av eter og alifatisk hydrokarbon (forhold 1-1,5:1) eller eter og alkylbenzen (forhold 0,2-0,5:1) (konsentrasjon av litium-forbindelsen mellom 5 og 30 vekt-%) og er avkjølt til temperaturer under -70°C, således at temperaturen ikke øker over -70°C. Reaksjonskomponentene med formel II tilsettes da eksempelvis Usually, the procedure is such that the bromo- or iodo-thiophene is dosed as such or in the form of a solution in the ether or liquid aliphatic hydrocarbon or alkylbenzene to lithium alkyl or lithium aryl, which is dissolved resp. suspended in one of the aforementioned ethers or a mixture of ether and aliphatic hydrocarbon (ratio 1-1.5:1) or ether and alkylbenzene (ratio 0.2-0.5:1) (concentration of the lithium compound between 5 and 30% by weight and is cooled to temperatures below -70°C, so that the temperature does not rise above -70°C. The reaction components with formula II are then added, for example
i form av en 10-100%-ig oppløsning (vekt-%) i en som allerede angitt dialkyleter eller alkylbenzen, likeledes således at temperaturen ikke øker over -70°C. in the form of a 10-100% solution (% by weight) in one of the already mentioned dialkyl ethers or alkylbenzene, likewise so that the temperature does not rise above -70°C.
I. en foretrukket utførelsesform av fremgangsmåten ifølge oppfinnelsen gjennomføres reaksjonen i en oppløsningsmiddelbland-ing av toluen og diisopropyleter og etter hydrolyse av reaksjonsblandingen underkastes den organiske fase en fraksjonert vakuumdestillasjon, idet oventil fjernes de lettkokende deler av blandingen som eksempelvis diisopropyleter, tiofen, butyl-bromid og andre samt en del av det anvendte toluen og som sumpresidu fåes oppløsning av 1,1-bis-[tienyl-(3)- og/eller In a preferred embodiment of the method according to the invention, the reaction is carried out in a solvent mixture of toluene and diisopropyl ether and, after hydrolysis of the reaction mixture, the organic phase is subjected to a fractional vacuum distillation, the high-boiling parts of the mixture being removed above, such as diisopropyl ether, thiophene, butyl bromide and others as well as part of the toluene used and as sum residue a solution of 1,1-bis-[thienyl-(3)- and/or
-tienyl-(2) -w-halogen-alkanol i toluen som direkte anvendes-thienyl-(2)-w-halo-alkanol in toluene which is directly used
i fremgangsmåtens neste trinn.in the next step of the procedure.
Reaksjonsdeltagerne kan eksempelvis anvendes i følgende molforhold: tieny 1--litium: forbindelse (II) = 2,0-4,0:1. The reaction participants can, for example, be used in the following molar ratio: tieny 1--lithium: compound (II) = 2.0-4.0:1.
Refererer man til litiumalkyl og brom- eller jodtiofen, så kommer eksempelvis følgende molforhold på tale: alkyllitium-forbindelse: brom- eller jodtiofen:forbindelse (II) = 2,5-5,0: 2,0-4,0:1, spesielt 2,0-5,0:2,0-4,0:1. If one refers to lithium alkyl and bromo- or iodothiophene, the following molar ratio is used, for example: alkyllithium compound: bromo- or iodothiophene: compound (II) = 2.5-5.0: 2.0-4.0:1, especially 2.0-5.0:2.0-4.0:1.
Reaksjonstemperaturen bør eksempelvis ikke overstige -50°C, fortrinnsvis er gjennomføring av reaksjonen eksempelvis ved temperaturer mellom -65 og-75°C. Fortrinnsvis overholdes en temperatur under -70°C, eksempelvis -80 og -70°C. The reaction temperature should not, for example, exceed -50°C, preferably carrying out the reaction at temperatures between -65 and -75°C, for example. A temperature below -70°C is preferably observed, for example -80 and -70°C.
Den dannede 1,1-bis-[ tienyl-( 3 og/eller 2) ]-co-halogen-alkanol med formel I kan omsettes direkte uten ytterligere rensing med aminer. Denne omsetning kan foregå med eller uten oppløsnings- resp. suspensjonsmiddel. Som inert opp-løsnings- eller suspensjonsmidler egner det seg eksempelvis de samme midler som kommer på tale for reaksjonsen av tienyllitium med forbindelse II, eksempelvis diisopropyleter, toluen og lignende. Dessuten kan eksempelvis også anvendes andre alkyl- og dialkylbenzener, dialkyleter, alifatiske ketoner og alifatiske og cykloalifatiske alkoholer. Det er også mulig direkte å omsette reaksjonsblandingen, hvori forbindelsen med formel I fremkommer med aminer. Da i en slik reaksjonsblanding dessuten det ved reaksjonen dannede alkylhalogenid er tilstede, er det eventuelt nødvendig å anvende tilsvarende overskudd av amin. The formed 1,1-bis-[thienyl-(3 and/or 2)]-co-halo-alkanol of formula I can be reacted directly without further purification with amines. This turnover can take place with or without dissolution or suspending agent. Suitable as inert solvents or suspension agents are, for example, the same agents used for the reaction of thienyl lithium with compound II, for example diisopropyl ether, toluene and the like. In addition, for example, other alkyl and dialkylbenzenes, dialkyl ethers, aliphatic ketones and aliphatic and cycloaliphatic alcohols can also be used. It is also possible to directly react the reaction mixture, in which the compound of formula I appears with amines. Since in such a reaction mixture the alkyl halide formed by the reaction is also present, it is possibly necessary to use a corresponding excess of amine.
Spesielt egner det seg for den videre omsetning av forbindelsene med formel I aminer av formel ^NY, hvori Y betyr en C^-C^-cykloalkylrest, en benzylrest, en metylendioksy-benzylrest, en en- eller toganger eller tre ganger med ci~C4~alkyl- eller C^-C^-alkoksygruppe substituert benzylrest eller en rettlinjet eller forgrenet C^-C^-alkylrest, som også kan være substituert med en aminogruppe, en di-C^-C^- alkylaminogruppe, en mono-C-^-C^-alkylaminogruppe, en morfolino-gruppe, en piperazinogruppe eller en 4-(C^-C^-alkyl)-piperazinogruppe eller betyr resten idet R er hydrogen eller en C-^-C^-alkylgruppe og fenylringen også kan inneholde en hydroksygruppe eller en C2_Cg-alkanoyl-gruppe eller hvori gruppen -NHY betyr resten In particular, it is suitable for the further reaction of the compounds of formula I with amines of formula ^NY, in which Y means a C^-C^-cycloalkyl radical, a benzyl radical, a methylenedioxy-benzyl radical, a one-, two-fold or three-fold with ci~ C4-alkyl- or C^-C^- alkoxy group substituted benzyl residue or a straight or branched C^-C^-alkyl residue, which may also be substituted with an amino group, a di-C^-C^- alkylamino group, a mono- C-^-C^-alkylamino group, a morpholino group, a piperazino group or a 4-(C^-C^-alkyl)-piperazino group or means the residue wherein R is hydrogen or a C-^-C^-alkyl group and the phenyl ring may also contain a hydroxy group or a C2_Cg-alkanoyl group or in which the group -NHY means the residue
og R' betyr hydrogen, en fenylrest, en fenylrest som er substituert 1- til 2-ganger med C^-C^-alkylgrupper, C^-C^-alkoksygrupper eller halogenatomer, videre betyr en C^-Cg-alkylrest, en C^-C^-oksalkylrest eller en fenyl-C^-C^-alkylrest som i fenylringen også kan være substituert med 1-3 C1-C4-alkoksygrupper. and R' means hydrogen, a phenyl radical, a phenyl radical which is substituted 1- to 2-times by C₁-C₁-alkyl groups, C₁-C₁-alkyl groups or halogen atoms, further means a C₁-Cg-alkyl radical, a C₁-C₂-oxalkyl radical or a phenyl-C₁-C₂-alkyl radical which in the phenyl ring can also be substituted with 1-3 C₁-C₄- alkoxy groups.
De under anvendelsene av ifølge oppfinnelsen fremstilte mellomforbindelser II fremstilte sluttprodukter er praktisk isomerfrie og fåes etter en gangs omkrystallisering i til-fredsstillende renhet. The final products produced during the use of intermediate compounds II prepared according to the invention are practically isomer-free and are obtained after a single recrystallization in satisfactory purity.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1120/77A GB1579541A (en) | 1977-01-12 | 1977-01-12 | Process for the production of (1,1 - dithien - (3)-yl - 1 - hydroxy - (3) - propyl) - (1-phenyl - 1 - hydroxy - (2) - propyl)-amine and (1,1 - dithien - (3) - yl-(1) - propen - (3) - yl) - (1 - phenyl-1 - hydroxy - (2) - propyl)- amine |
| GB1121/77A GB1597591A (en) | 1977-01-12 | 1977-01-12 | Dithienyl alkylamines and alkenylamines and a process for their production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO823010L true NO823010L (en) | 1978-07-13 |
Family
ID=26236487
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO780101A NO780101L (en) | 1977-01-12 | 1978-01-11 | NEW DITIENYLALKYLAMINES AND PROCEDURES FOR THEIR PREPARATION |
| NO823010A NO823010L (en) | 1977-01-12 | 1982-09-06 | 1,1-DITIENYL- (3) -1-HYDROXY-ALKYLHALOGENIDES. |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO780101A NO780101L (en) | 1977-01-12 | 1978-01-11 | NEW DITIENYLALKYLAMINES AND PROCEDURES FOR THEIR PREPARATION |
Country Status (1)
| Country | Link |
|---|---|
| NO (2) | NO780101L (en) |
-
1978
- 1978-01-11 NO NO780101A patent/NO780101L/en unknown
-
1982
- 1982-09-06 NO NO823010A patent/NO823010L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO780101L (en) | 1978-07-13 |
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