NO761850L - - Google Patents
Info
- Publication number
- NO761850L NO761850L NO761850A NO761850A NO761850L NO 761850 L NO761850 L NO 761850L NO 761850 A NO761850 A NO 761850A NO 761850 A NO761850 A NO 761850A NO 761850 L NO761850 L NO 761850L
- Authority
- NO
- Norway
- Prior art keywords
- phenoxybenzaldehyde
- bromobenzaldehyde
- phenol
- acetal
- copper
- Prior art date
Links
- MRLGCTNJRREZHZ-UHFFFAOYSA-N 3-phenoxybenzaldehyde Chemical class O=CC1=CC=CC(OC=2C=CC=CC=2)=C1 MRLGCTNJRREZHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- -1 alkali metal salt Chemical class 0.000 claims description 14
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical class BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Chemical class CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 10
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000005749 Copper compound Substances 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 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 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 description 1
- ZXGXGZGKWSUMJK-UHFFFAOYSA-N 2,4,6-Trimethyl-chinolin Natural products N1=C(C)C=C(C)C2=CC(C)=CC=C21 ZXGXGZGKWSUMJK-UHFFFAOYSA-N 0.000 description 1
- GXUQMKBQDGPMKZ-UHFFFAOYSA-N 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-UHFFFAOYSA-N 0.000 description 1
- WLFDEVVCXPTAQA-UHFFFAOYSA-N 3-(4-methoxyphenoxy)benzaldehyde Chemical compound C1=CC(OC)=CC=C1OC1=CC=CC(C=O)=C1 WLFDEVVCXPTAQA-UHFFFAOYSA-N 0.000 description 1
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NOCQQZLSUGMTIS-UHFFFAOYSA-M potassium;4-methoxyphenolate Chemical compound [K+].COC1=CC=C([O-])C=C1 NOCQQZLSUGMTIS-UHFFFAOYSA-M 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
Foreliggende oppfinnelse gjelder en fremgangsmåte for fremstilling av eventuelt substituert 3-fenoksybenzaldehyd eller en acetal derav.
Kjente fremgangsmåter for fremstilling av 3-fenoksybenzaldehyd, se eksempelvisMonatshefte fiirChemie, Wien, 67 (1935), 598-609, er kompliserte og gir vanligvis lave utbytter av aldehydet.
Det er nå funnet at 3-fenoksybenzaldehyd og
visse derivater derav lett kan oppnås i høye utbytter fra lett tilgjengelige utgangsmaterialer.
Foreliggende oppfinnelse skaffer således en fremgangsmåte for fremstilling av et eventuelt substituert 3-fenoksybenzaldehyd eller en acetal derav, hvilken fremgangsmåte omfatter å omsette et eventuelt substituert 3-brombenzaldehyd eller en acetal derav, med en aventuelt substituert fenol eller et alkalimetallsalt derav, i nærvær av et aprotisk organisk løsningsmiddel og metallisk kobber og/eller en kobberforbindelse.
Alkalimetallsaltet av fenolen er fortrinnsvis natrium- eller kaliumsaltet, idet natriumsaltet er spesielt foretrukket fordi det gir høyere selektivitet til
3-fenoksybenzaldehydet. Saltet er fortrinnsvis vannfritt siden nærvær av vann reduserer utbyttet av 3-fenoksybenzaldehyd. Det vannfrie saltet kan fremstilles ved reaksjon mellom fenolen og et alkalimetallhydroksyd fulgt av fjerning av vann som dannes som en azeotrop med toluen eller xylen. Alternativt kan fenolen omsettes med et alkalimetallalkoksyd og den dannede alkanol kan fjernes ved destillasjon.
Det aprotiske, organiske løsningsmidlet kan være et aromatisk hydrokarbon som f.eks. toluen eller de tre xylenene, en aromatisk, heterocyklisk nitrogenforbindelse som f.eks. pyridin, 2,4,6-trimetyl-pyridin, kinolin eller pyridin-N-oksyd, et dialkylamid som f.eks. dimetylformamid eller dimetylacetamid eller et sulfoksyd som f.eks. dimetylsulfoksyd eller tetrahydro-tiqfen-1,1-oksyd.Blandinger av disse løsningsmidler kan også brukes. Kobberforbindelsen kan være en kobber(II)-forbindelse som f.eks. kuprifluorid, kupriklorid, kuprioksyd eller kupri-p-klorbenzoat, eller en kobber (I)—forbindelse som f.eks. kuproklorid, kuprobromid, kuprojodid eller kuprooksyd.
3-brombenzaldehydet og fenolen eller saltet kan anvendes i ethvert molforhold og fortrinnsvis er molforholdet mellom benzaldehyd og fenol eller salt fra 0,5:1 til 2:1, spesielt fra 0,9:1 til 1,1:1. Molforholdet mellom kobberforbindelsen og 3-brombenzaldehydet er fortrinnsvis fra 1:100
til 10:100. Reakspnstemperaturen kan eksempelvis være fra 50 til 200°C, fortrinnsvis fra 100 til 150°c, og reaksjonstiden en til fem timer.
Eksempler på substituenter som kan være til
stede i 3-brombenzaldehydet eller fenolen eller alkalimetallsaltet derav er metyl- og metoksygrupper og kloratomer. Acetalen oppnås fortrinnsvis fra en dihydrisk alkohol som f.eks. etylen-glykol.
3-Fenoksybenzaldehydet kan omsettes med hydrogen-cyanid for å gi alfa-cyano-3-fenoksybenzylalkohol, eller hydrogeneres for å gi 3-fenoksybenzylalkohol to forløpere for estere som er av pyretrin-insekticid-typen.
Oppfinnelsen skal ytterligere illustreres ved de følgende eksemplene.
Eksempel 1.
Tørt kaliumfenolat (0,02 mol) ble fremstilt fra fenol (0,02 mol) og kaliumhydroksyd (0,02 mol) fulgt av fjerning av det dannede vann som en azeotrop med toluen. Fenolatet, 3-brombenzaldehyd (0,02 mol), kuproklorid (0,0005 mol) og pyridin (5 ml) ble oppvarmet under tilbakeløp i to timer.Blandingen ble opptatt i 50 ml dietyleter og eterløsningen ble vasket med vann (3x50 ml) og tørket over vannfritt natriumsulfat.GLC-analyse avslørte at 97% av 3-brombenzaldehydet var omdannet, med en selektivitet til 3-fenoksybenzaldehyd på 8 5%.Fordampning av eterløsningen og destillasjon av resten ga rent 3-fenoksybenzaldehyd som kokte ved 12 5°C ved 0,8 mm Hg, i et utbytte av 74%. 3-fenoksybenzaldehydet kunne også renses via bisulfidkomplekset.
Sammenligningsforsøk A.
Fremgangsmåten i eksempel 1 ble gjentatt med anvendelse av 3-klorbenzaldehyd. Det ble oppnådd en kompleks blanding av forbindelser som inneholdt bare ca. 10% 3-fenoksybenzaldehyd.
Eksempel 2.
Fremgangsmåten i eksempel 1 ble gjentatt med anvendelse av 3-brombenzaldehyd-etylenglykolacetal og en reaksjons-tid på 5 timer.GLC-analyse indikerte en 90%-ig omdannelse av utgangsmaterialene, med en 90%-ig selektivitet til 3-fenoksybenzaldehyd-etylenglekolacetal.
Sammenligningsforsøk B.
Eksempel 2 ble gjentatt under anvendelse av 3-klorbenzaldehyd-etylenglykolacetal. Det ble oppnådd mindre enn 5% omdannelse etter 6 timer.
Eksempler 3 til 5.
Fremgangsmåten i eksempel 1 ble gjentatt under anvendelse av tre løsningsmidler istedenfor pyridin. Tabell I angir de anvendte løsningsmidler, omdannelsene og selektiviteten til 3-fenoksybenzaldehyd.
Eksempel 6.
0,0 5 mol natriumhydroksyd og 0,0 5 mol fenol ble blandet i 75 ml av en kommersiell blanding av o-, m- og p-xylen. Det vann som ble dannet ble fjernet ved azeotrop destillasjon ved hjelp av et Dean og Stark-apparat. Suspensjonen av natriumfenolat fremstilt på denne måten ble blandet med 2 5 ml pyridin, 0,05 mol nydestillert 3-brombenzaldehyd og 0,002 5 mol kuproklorid. Blandingen ble så oppvarmet under tilbakeløp i 30 minutter.
GLC-analyse viste da at 97% av 3-brombenzaldehydet var omdannet, med en selektivitet til 3-fenoksybenzaldehyd på 97%.
Eksempel 7.
Fremgangsmåten fra eksempel 1 ble gjentatt under anvendelse av 3-brombenzaldehyd og kalium-4-metoksyfenolat. Produktet var 3-(4-metoksyfenoksy) benzaldehyd, kp. 150°C ved 0,1 mm Hg med et utbytte på 40%.
Claims (8)
1.F remgangsmåte for fremstilling av et eventuelt substituert 3-fenoksybenzaldehyd eller en acetal derav, karakterisert ved at et eventuelt substituert 3-brombenzaldehyd eller en acetal derav omsettes med en fenol eller et alkalimetallsalt derav, i nærvær av et aprotisk organisk løsningsmiddel og kobber og/eller en kobberforbindelse.
2. Fremgangsmåte ifølge krav 1,
karakterisert ved at det som alkalimetallsalt anvendes natrium- eller kaliumsalt.
3.F remgangsmåte ifølge krav 1 eller 2, karakterisert ved at det som løsningsmiddel anvendes pyridin.
4. Fremgangsmåte ifølge et av kravene 1 til 3, karakterisert ved at det som kobberforbindelse anvendes en kobber (I )-forbindelse.
5.F remgangsmåte ifølge et av kravene 1 til 4, karakterisert ved at det anvendes et molforhold mellom 3-brombenzaldehyd og fenol eller et alkalimetallsalt derav i området av fra 0,5 til 2.
6. Fremgangsmåte ifølge et av de foregående krav, karakterisert ved at det anvendes en temperatur på fra 50 til 200°C.
7.F remgangsmåte ifølge krav 1, karakterisert ved at den er i det vesentlig som beskrevet, under henvisning til et av eksemplene.
8. Et eventuelt substituert 3-fenoksybenzaldehyd eller en acetal derav, når det er fremstilt ved en fremgangsmåte som er krevet i et av kravene 1 til 7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB23770/75A GB1539733A (en) | 1975-06-02 | 1975-06-02 | Preparation of 3-phenoxybenzaldehydes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO761850L true NO761850L (no) | 1976-12-03 |
Family
ID=10201046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO761850A NO761850L (no) | 1975-06-02 | 1976-05-31 |
Country Status (24)
| Country | Link |
|---|---|
| JP (1) | JPS5944294B2 (no) |
| AR (1) | AR210130A1 (no) |
| AU (1) | AU500419B2 (no) |
| BE (1) | BE842177A (no) |
| BR (1) | BR7603435A (no) |
| CA (1) | CA1075246A (no) |
| CH (1) | CH601155A5 (no) |
| DD (1) | DD124378A5 (no) |
| DE (1) | DE2624360A1 (no) |
| DK (1) | DK238676A (no) |
| ES (1) | ES448384A1 (no) |
| FR (1) | FR2313340A1 (no) |
| GB (1) | GB1539733A (no) |
| HU (1) | HU173926B (no) |
| IE (1) | IE42827B1 (no) |
| IL (1) | IL49686A (no) |
| IT (1) | IT1060881B (no) |
| LU (1) | LU75055A1 (no) |
| NL (1) | NL7605830A (no) |
| NO (1) | NO761850L (no) |
| SE (1) | SE7606116L (no) |
| SU (1) | SU910113A3 (no) |
| TR (1) | TR19245A (no) |
| ZA (1) | ZA763220B (no) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0006155A1 (de) * | 1978-06-08 | 1980-01-09 | Ciba-Geigy Ag | 3-Phenoxybenzylamine sowie 3-Benzylbenzylamine und Verfahren zu ihrer Herstellung |
| GB2185016B (en) * | 1985-12-20 | 1989-11-29 | Hardwicke Chemical Co | Process for preparing 3-phenoxybenzaldehydes |
| US4691033A (en) * | 1985-12-20 | 1987-09-01 | Hardwicke Chemical Company | Process for preparing 3-phenoxybenzaldehydes |
| EP3816155A1 (en) * | 2013-08-23 | 2021-05-05 | Virginia Commonwealth University | Ester nitrates derivatives of aromatic aldehydes with multiple pharmalogic properties to treat sickle cell disease |
| FR3031977B1 (fr) * | 2015-01-22 | 2018-04-20 | Centre National De La Recherche Scientifique | Procede de fabrication d'une resine ablative |
| FR3031978B1 (fr) | 2015-01-22 | 2018-04-20 | Centre National De La Recherche Scientifique | Procede de fabrication d'une resine ablative |
| CN110256285B (zh) * | 2019-07-09 | 2022-03-18 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | 一种稳定同位素标记拟除虫菊酯的合成方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR818032A (fr) * | 1936-02-29 | 1937-09-16 | Geigy Ag J R | Procédé pour la préparation d'aldéhydes de la série des éthers diaryliques ou polyaryliques |
-
1975
- 1975-06-02 GB GB23770/75A patent/GB1539733A/en not_active Expired
-
1976
- 1976-04-28 CA CA251,331A patent/CA1075246A/en not_active Expired
- 1976-05-25 BE BE1007409A patent/BE842177A/xx not_active IP Right Cessation
- 1976-05-31 JP JP51062449A patent/JPS5944294B2/ja not_active Expired
- 1976-05-31 SE SE7606116A patent/SE7606116L/xx unknown
- 1976-05-31 BR BR7603435A patent/BR7603435A/pt unknown
- 1976-05-31 DK DK238676A patent/DK238676A/da not_active Application Discontinuation
- 1976-05-31 NL NL7605830A patent/NL7605830A/xx not_active Application Discontinuation
- 1976-05-31 IT IT23800/76A patent/IT1060881B/it active
- 1976-05-31 DE DE19762624360 patent/DE2624360A1/de not_active Withdrawn
- 1976-05-31 ES ES448384A patent/ES448384A1/es not_active Expired
- 1976-05-31 TR TR19245A patent/TR19245A/xx unknown
- 1976-05-31 SU SU762439451A patent/SU910113A3/ru active
- 1976-05-31 AR AR263460A patent/AR210130A1/es active
- 1976-05-31 IL IL49686A patent/IL49686A/xx unknown
- 1976-05-31 LU LU75055A patent/LU75055A1/xx unknown
- 1976-05-31 CH CH680776A patent/CH601155A5/xx not_active IP Right Cessation
- 1976-05-31 FR FR7616352A patent/FR2313340A1/fr active Granted
- 1976-05-31 AU AU14444/76A patent/AU500419B2/en not_active Expired
- 1976-05-31 DD DD193099A patent/DD124378A5/xx unknown
- 1976-05-31 IE IE1151/76A patent/IE42827B1/en unknown
- 1976-05-31 NO NO761850A patent/NO761850L/no unknown
- 1976-06-01 ZA ZA763220A patent/ZA763220B/xx unknown
- 1976-06-02 HU HU76SE1837A patent/HU173926B/hu not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| GB1539733A (en) | 1979-01-31 |
| JPS5944294B2 (ja) | 1984-10-29 |
| DD124378A5 (no) | 1977-02-16 |
| DK238676A (da) | 1976-12-03 |
| HU173926B (hu) | 1979-09-28 |
| SE7606116L (sv) | 1976-12-03 |
| ES448384A1 (es) | 1977-08-01 |
| IL49686A0 (en) | 1976-07-30 |
| IE42827L (en) | 1976-12-02 |
| SU910113A3 (ru) | 1982-02-28 |
| JPS51143638A (en) | 1976-12-10 |
| IE42827B1 (en) | 1980-10-22 |
| AR210130A1 (es) | 1977-06-30 |
| AU1444476A (en) | 1977-12-08 |
| IL49686A (en) | 1979-05-31 |
| CA1075246A (en) | 1980-04-08 |
| FR2313340A1 (fr) | 1976-12-31 |
| FR2313340B1 (no) | 1978-11-17 |
| CH601155A5 (no) | 1978-06-30 |
| TR19245A (tr) | 1978-08-02 |
| DE2624360A1 (de) | 1976-12-16 |
| AU500419B2 (en) | 1979-05-24 |
| BR7603435A (pt) | 1977-02-15 |
| NL7605830A (nl) | 1976-12-06 |
| LU75055A1 (no) | 1977-02-15 |
| BE842177A (nl) | 1976-11-25 |
| ZA763220B (no) | 1977-05-25 |
| IT1060881B (it) | 1982-09-30 |
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