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)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Foreliggende oppfinnelse gjelder en fremgangsmåte for fremstilling av eventuelt substituert 3-fenoksybenzaldehyd eller en acetal derav. The present invention relates to a method for the production of optionally substituted 3-phenoxybenzaldehyde or an acetal thereof.
Kjente fremgangsmåter for fremstilling av 3-fenoksybenzaldehyd, se eksempelvisMonatshefte fiirChemie, Wien, 67 (1935), 598-609, er kompliserte og gir vanligvis lave utbytter av aldehydet. Known methods for the preparation of 3-phenoxybenzaldehyde, see for example Monatshefte fiirChemie, Wien, 67 (1935), 598-609, are complicated and usually give low yields of the aldehyde.
Det er nå funnet at 3-fenoksybenzaldehyd ogIt has now been found that 3-phenoxybenzaldehyde and
visse derivater derav lett kan oppnås i høye utbytter fra lett tilgjengelige utgangsmaterialer. certain derivatives thereof can easily be obtained in high yields from readily available starting materials.
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. The present invention thus provides a method for producing an optionally substituted 3-phenoxybenzaldehyde or an acetal thereof, which method comprises reacting an optionally substituted 3-bromobenzaldehyde or an acetal thereof, with an optionally substituted phenol or an alkali metal salt thereof, in the presence of a aprotic organic solvent and metallic copper and/or a copper compound.
Alkalimetallsaltet av fenolen er fortrinnsvis natrium- eller kaliumsaltet, idet natriumsaltet er spesielt foretrukket fordi det gir høyere selektivitet til The alkali metal salt of the phenol is preferably the sodium or potassium salt, the sodium salt being particularly preferred because it gives higher selectivity to
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. The 3-phenoxybenzaldehyde. The salt is preferably anhydrous since the presence of water reduces the yield of 3-phenoxybenzaldehyde. The anhydrous salt can be prepared by reaction between the phenol and an alkali metal hydroxide followed by removal of water formed as an azeotrope with toluene or xylene. Alternatively, the phenol can be reacted with an alkali metal alkoxide and the alkanol formed can be removed by distillation.
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. The aprotic organic solvent can be an aromatic hydrocarbon such as e.g. toluene or the three xylenes, an aromatic heterocyclic nitrogen compound such as pyridine, 2,4,6-trimethyl-pyridine, quinoline or pyridine-N-oxide, a dialkylamide such as e.g. dimethylformamide or dimethylacetamide or a sulfoxide such as e.g. dimethyl sulfoxide or tetrahydro-tiqfen-1,1-oxide. Mixtures of these solvents can also be used. The copper compound can be a copper (II) compound such as e.g. cupric fluoride, cupric chloride, cupric oxide or cupric-p-chlorobenzoate, or a copper (I) compound such as e.g. cuprous chloride, cuprous bromide, cuprous iodide or cuprous oxide.
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 The 3-bromobenzaldehyde and the phenol or salt can be used in any molar ratio and preferably the molar ratio between benzaldehyde and phenol or salt is from 0.5:1 to 2:1, especially from 0.9:1 to 1.1:1. The molar ratio between the copper compound and the 3-bromobenzaldehyde is preferably from 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. to 10:100. The reaction temperature can, for example, be from 50 to 200°C, preferably from 100 to 150°C, and the reaction time one to five hours.
Eksempler på substituenter som kan være tilExamples of substituents that may exist
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. present in the 3-bromobenzaldehyde or the phenol or the alkali metal salt thereof are methyl and methoxy groups and chlorine atoms. The acetal is preferably obtained from a dihydric alcohol such as e.g. ethylene glycol.
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. The 3-phenoxybenzaldehyde can be reacted with hydrogen cyanide to give alpha-cyano-3-phenoxybenzyl alcohol, or hydrogenated to give 3-phenoxybenzyl alcohol two precursors of esters which are of the pyrethrin insecticide type.
Oppfinnelsen skal ytterligere illustreres ved de følgende eksemplene. The invention shall be further illustrated by the following examples.
Eksempel 1.Example 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. Dry potassium phenolate (0.02 mol) was prepared from phenol (0.02 mol) and potassium hydroxide (0.02 mol) followed by removal of the formed water as an azeotrope with toluene. The phenolate, 3-bromobenzaldehyde (0.02 mol), cuprous chloride (0.0005 mol) and pyridine (5 mL) were heated under reflux for two hours. The mixture was taken up in 50 mL of diethyl ether and the ether solution was washed with water (3x50 mL). and dried over anhydrous sodium sulfate. GLC analysis revealed that 97% of the 3-bromobenzaldehyde was converted, with a selectivity to 3-phenoxybenzaldehyde of 85%. Evaporation of the ether solution and distillation of the residue gave pure 3-phenoxybenzaldehyde boiling at 125° C at 0.8 mm Hg, in a yield of 74%. The 3-phenoxybenzaldehyde could also be purified via the bisulphide complex.
Sammenligningsforsøk A.Comparison test 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. The procedure in example 1 was repeated using 3-chlorobenzaldehyde. A complex mixture of compounds containing only approx. 10% 3-phenoxybenzaldehyde.
Eksempel 2.Example 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. The procedure in example 1 was repeated using 3-bromobenzaldehyde-ethylene glycol acetal and a reaction time of 5 hours. GLC analysis indicated a 90% conversion of the starting materials, with a 90% selectivity to 3-phenoxybenzaldehyde-ethylene glycol acetal.
Sammenligningsforsøk B.Comparison experiment B.
Eksempel 2 ble gjentatt under anvendelse av 3-klorbenzaldehyd-etylenglykolacetal. Det ble oppnådd mindre enn 5% omdannelse etter 6 timer. Example 2 was repeated using 3-chlorobenzaldehyde-ethylene glycol acetal. Less than 5% conversion was achieved after 6 hours.
Eksempler 3 til 5.Examples 3 to 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. The procedure in Example 1 was repeated using three solvents instead of pyridine. Table I indicates the solvents used, the conversions and the selectivity of 3-phenoxybenzaldehyde.
Eksempel 6. Example 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. 0.05 mol of sodium hydroxide and 0.05 mol of phenol were mixed in 75 ml of a commercial mixture of o-, m- and p-xylene. The water formed was removed by azeotropic distillation using a Dean and Stark apparatus. The suspension of sodium phenolate thus prepared was mixed with 25 ml of pyridine, 0.05 mol of freshly distilled 3-bromobenzaldehyde and 0.002 5 mol of cuprous chloride. The mixture was then heated under reflux for 30 minutes.
GLC-analyse viste da at 97% av 3-brombenzaldehydet var omdannet, med en selektivitet til 3-fenoksybenzaldehyd på 97%. GLC analysis then showed that 97% of the 3-bromobenzaldehyde had been converted, with a selectivity to 3-phenoxybenzaldehyde of 97%.
Eksempel 7.Example 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%. The procedure from Example 1 was repeated using 3-bromobenzaldehyde and potassium 4-methoxyphenolate. The product was 3-(4-methoxyphenoxy)benzaldehyde, b.p. 150°C at 0.1 mm Hg with a yield of 40%.
Claims (8)
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 (en) | 1976-12-03 |
Family
ID=10201046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO761850A NO761850L (en) | 1975-06-02 | 1976-05-31 |
Country Status (24)
| Country | Link |
|---|---|
| JP (1) | JPS5944294B2 (en) |
| AR (1) | AR210130A1 (en) |
| AU (1) | AU500419B2 (en) |
| BE (1) | BE842177A (en) |
| BR (1) | BR7603435A (en) |
| CA (1) | CA1075246A (en) |
| CH (1) | CH601155A5 (en) |
| DD (1) | DD124378A5 (en) |
| DE (1) | DE2624360A1 (en) |
| DK (1) | DK238676A (en) |
| ES (1) | ES448384A1 (en) |
| FR (1) | FR2313340A1 (en) |
| GB (1) | GB1539733A (en) |
| HU (1) | HU173926B (en) |
| IE (1) | IE42827B1 (en) |
| IL (1) | IL49686A (en) |
| IT (1) | IT1060881B (en) |
| LU (1) | LU75055A1 (en) |
| NL (1) | NL7605830A (en) |
| NO (1) | NO761850L (en) |
| SE (1) | SE7606116L (en) |
| SU (1) | SU910113A3 (en) |
| TR (1) | TR19245A (en) |
| ZA (1) | ZA763220B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0006155A1 (en) * | 1978-06-08 | 1980-01-09 | Ciba-Geigy Ag | 3-Phenoxybenzyl amines and 3-benzylbenzyl amines and process for their production |
| 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 (en) * | 2015-01-22 | 2018-04-20 | Centre National De La Recherche Scientifique | PROCESS FOR PRODUCING AN ABLATIVE RESIN |
| FR3031978B1 (en) | 2015-01-22 | 2018-04-20 | Centre National De La Recherche Scientifique | PROCESS FOR PRODUCING AN ABLATIVE RESIN |
| CN110256285B (en) * | 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 | Synthetic method of stable isotope labeled pyrethroid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR818032A (en) * | 1936-02-29 | 1937-09-16 | Geigy Ag J R | Process for the preparation of aldehydes of the series of diaryl or polyaryl ethers |
-
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/en not_active IP Right Cessation
- 1976-05-31 IT IT23800/76A patent/IT1060881B/en active
- 1976-05-31 CH CH680776A patent/CH601155A5/xx not_active IP Right Cessation
- 1976-05-31 AR AR263460A patent/AR210130A1/en active
- 1976-05-31 SU SU762439451A patent/SU910113A3/en active
- 1976-05-31 DE DE19762624360 patent/DE2624360A1/en not_active Withdrawn
- 1976-05-31 BR BR7603435A patent/BR7603435A/en unknown
- 1976-05-31 TR TR19245A patent/TR19245A/en unknown
- 1976-05-31 DK DK238676A patent/DK238676A/en not_active Application Discontinuation
- 1976-05-31 IL IL49686A patent/IL49686A/en unknown
- 1976-05-31 FR FR7616352A patent/FR2313340A1/en active Granted
- 1976-05-31 ES ES448384A patent/ES448384A1/en not_active Expired
- 1976-05-31 DD DD193099A patent/DD124378A5/xx unknown
- 1976-05-31 SE SE7606116A patent/SE7606116L/en unknown
- 1976-05-31 AU AU14444/76A patent/AU500419B2/en not_active Expired
- 1976-05-31 NL NL7605830A patent/NL7605830A/en not_active Application Discontinuation
- 1976-05-31 IE IE1151/76A patent/IE42827B1/en unknown
- 1976-05-31 JP JP51062449A patent/JPS5944294B2/en not_active Expired
- 1976-05-31 NO NO761850A patent/NO761850L/no unknown
- 1976-05-31 LU LU75055A patent/LU75055A1/xx unknown
- 1976-06-01 ZA ZA763220A patent/ZA763220B/xx unknown
- 1976-06-02 HU HU76SE1837A patent/HU173926B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TR19245A (en) | 1978-08-02 |
| FR2313340A1 (en) | 1976-12-31 |
| LU75055A1 (en) | 1977-02-15 |
| AU500419B2 (en) | 1979-05-24 |
| CH601155A5 (en) | 1978-06-30 |
| BR7603435A (en) | 1977-02-15 |
| DK238676A (en) | 1976-12-03 |
| CA1075246A (en) | 1980-04-08 |
| SU910113A3 (en) | 1982-02-28 |
| SE7606116L (en) | 1976-12-03 |
| IL49686A0 (en) | 1976-07-30 |
| JPS51143638A (en) | 1976-12-10 |
| AU1444476A (en) | 1977-12-08 |
| DD124378A5 (en) | 1977-02-16 |
| HU173926B (en) | 1979-09-28 |
| IE42827L (en) | 1976-12-02 |
| IL49686A (en) | 1979-05-31 |
| NL7605830A (en) | 1976-12-06 |
| FR2313340B1 (en) | 1978-11-17 |
| ES448384A1 (en) | 1977-08-01 |
| DE2624360A1 (en) | 1976-12-16 |
| AR210130A1 (en) | 1977-06-30 |
| GB1539733A (en) | 1979-01-31 |
| ZA763220B (en) | 1977-05-25 |
| IT1060881B (en) | 1982-09-30 |
| IE42827B1 (en) | 1980-10-22 |
| BE842177A (en) | 1976-11-25 |
| JPS5944294B2 (en) | 1984-10-29 |
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