FR2655984A1 - Process for the preparation of 3-alkoxy-4-hydroxybenzaldehydes - Google Patents
Process for the preparation of 3-alkoxy-4-hydroxybenzaldehydes Download PDFInfo
- Publication number
- FR2655984A1 FR2655984A1 FR8917213A FR8917213A FR2655984A1 FR 2655984 A1 FR2655984 A1 FR 2655984A1 FR 8917213 A FR8917213 A FR 8917213A FR 8917213 A FR8917213 A FR 8917213A FR 2655984 A1 FR2655984 A1 FR 2655984A1
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- France
- Prior art keywords
- radical
- copper
- hydroxy
- benzaldehyde
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 alkali metal alkoxide Chemical class 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005749 Copper compound Substances 0.000 claims abstract description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 18
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 150000001340 alkali metals Chemical class 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- UOTMHAOCAJROQF-UHFFFAOYSA-N 4-hydroxy-3-bromo-benzaldehyde Natural products OC1=CC=C(C=O)C=C1Br UOTMHAOCAJROQF-UHFFFAOYSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000003948 formamides Chemical class 0.000 claims description 6
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 5
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 5
- 229940116318 copper carbonate Drugs 0.000 claims description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 5
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SXRHGLQCOLNZPT-UHFFFAOYSA-N 2,6-dibromo-4-formylphenol Natural products OC1=C(Br)C=C(C=O)C=C1Br SXRHGLQCOLNZPT-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- ARLWNJVPRBPURR-UHFFFAOYSA-N 2-(hydroxymethylidene)propanedioic acid Chemical class OC=C(C(O)=O)C(O)=O ARLWNJVPRBPURR-UHFFFAOYSA-N 0.000 claims description 2
- KRTGJZMJJVEKRX-UHFFFAOYSA-N 2-phenylethan-1-yl Chemical compound [CH2]CC1=CC=CC=C1 KRTGJZMJJVEKRX-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- GVSGSHGXUXLQNS-UHFFFAOYSA-N BDB Natural products OC1=CC(C=O)=CC(Br)=C1O GVSGSHGXUXLQNS-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- SWGXDLRCJNEEGZ-UHFFFAOYSA-N N-cyclohexylformamide Chemical compound O=CNC1CCCCC1 SWGXDLRCJNEEGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- GNWVUSJJFONIKF-UHFFFAOYSA-L copper;pyridine-2-carboxylate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=N1.[O-]C(=O)C1=CC=CC=N1 GNWVUSJJFONIKF-UHFFFAOYSA-L 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical group C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000002757 morpholinyl group Chemical group 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001241 acetals Chemical class 0.000 abstract 1
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 20
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 14
- 230000009466 transformation Effects 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- LMWRGAKQZPUJBW-UHFFFAOYSA-N diethyl 2-(hydroxymethylidene)propanedioate Chemical compound CCOC(=O)C(=CO)C(=O)OCC LMWRGAKQZPUJBW-UHFFFAOYSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MJRJDGKISPWEMD-OEAKJJBVSA-N (2E)-3-(3,5-dibromo-4-hydroxyphenyl)-N-[2-(3,5-dibromo-4-hydroxyphenyl)ethyl]-2-hydroxyiminopropanamide Chemical compound BrC=1C=C(C=C(C=1O)Br)CCNC(/C(/CC1=CC(=C(C(=C1)Br)O)Br)=N/O)=O MJRJDGKISPWEMD-OEAKJJBVSA-N 0.000 description 3
- 150000001299 aldehydes Chemical group 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MSSDTZLYNMFTKN-UHFFFAOYSA-N 1-Piperazinecarboxaldehyde Chemical compound O=CN1CCNCC1 MSSDTZLYNMFTKN-UHFFFAOYSA-N 0.000 description 1
- KLSHZDPXXKAHIJ-UHFFFAOYSA-N 3-bromo-4-hydroxy-5-methoxybenzaldehyde Chemical compound COC1=CC(C=O)=CC(Br)=C1O KLSHZDPXXKAHIJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- DIRVEOCOAHGVJV-UHFFFAOYSA-N n-methyl-n-pyridin-2-ylformamide Chemical compound O=CN(C)C1=CC=CC=N1 DIRVEOCOAHGVJV-UHFFFAOYSA-N 0.000 description 1
- CBLGQEBXWDKYDI-UHFFFAOYSA-N piperazine-1,4-dicarbaldehyde Chemical compound O=CN1CCN(C=O)CC1 CBLGQEBXWDKYDI-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Classifications
-
- 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)
Abstract
Description
PROCEDE DE PREPARATION D'ALCOXY-3 HYDROXY-4 BENZALDEHYDES
La présente invention concerne un procédé de préparation d'alcoxy-3 hydroxy-4 benzaldéhydes à partir de halogéno-3 hydroxy-4 benzaldéhydes.PROCESS FOR THE PREPARATION OF ALCOXY-3 HYDROXY-4 BENZALDEHYDES
The present invention relates to a process for the preparation of 3-alkoxy-4-hydroxy-benzaldehydes from 3-halo-4-hydroxy benzaldehydes.
Un article de Canadian Journal of Chemistry 31, page 476 (1953) décrit la méthoxylation des halogéno-5 hydroxy-4 méthoxy-3 benzaldéhydes (ou halogéno-5 vanillines) par le méthylate de sodium, dans le méthanol et en présence d'un composé du cuivre II. An article from Canadian Journal of Chemistry 31, page 476 (1953) describes the methoxylation of 5-halo-4-hydroxy-3-methoxy-benzaldehydes (or 5-halo-vanillins) by sodium methylate, in methanol and in the presence of a composed of copper II.
Le rendement obtenu avec le dérivé bromé est d'environ 60 %. The yield obtained with the brominated derivative is approximately 60%.
Le brevet américain n"4218567 décrit notamment la préparation du diméthoxy-3,5 hydroxy-4 benzaldéhyde. US Patent No. 4,218,567 describes in particular the preparation of 3,5-dimethoxy-4-hydroxy-benzaldehyde.
Le brevet GB-A-2089672 décrit la préparation de diméthoxy-3,5 hydroxy-4 benzaldéhyde à partir du bromo-5 hydroxy-4 méthoxy-3 benzaldéhyde et du méthylate de sodium, en présence d'un catalyseur constitué d'un ester de l'acide formique et d'un sel de cuivre I. Dans ce procédé la fonction aldéhyde est préalablement protégée en la transformant en acétal. La réaction est très lente. Patent GB-A-2089672 describes the preparation of 3,5-dimethoxy-4-hydroxy-benzaldehyde from 5-bromo-4-hydroxy-3-methoxy-benzaldehyde and sodium methylate, in the presence of a catalyst consisting of an ester formic acid and a copper salt I. In this process, the aldehyde function is protected beforehand by transforming it into acetal. The reaction is very slow.
La présente invention se propose de réaliser l'alcoxylation des dérivés halogénés de l'hydroxy-4 benzaldéhyde dans un alcool et sans qu'il soit nécessaire de protéger la fonction aldéhyde sous forme d'acétal. The present invention proposes to carry out the alkoxylation of the halogenated derivatives of hydroxy-4-benzaldehyde in an alcohol and without it being necessary to protect the aldehyde function in the form of acetal.
Plus précisément l'invention consiste en un procédé de préparation d'alcoxy-3 hydroxy-4 benzaldéhydes par réaction d'halogéno hydroxy-4 benzaldéhydes de formule générale (I)
dans laquelle
- X représente un atome d'iode, de brome ou de chlore
- R1 représente un atome d'hydrogène, un atome d'iode, un
atome de brome, un atome de chlore, un radical alkyle
ayant 1 à 4 atomes de carbone, un radical alcoxy
ayant 1 à 4 atomes de carbone, un radical hydroxyle, avec un alcoolate de métal alcalin, ayant 1 à 4 atomes de carbone et en présence d'un composé du cuivre, caractérisé en ce que l'on opère en présence d'une quantité efficace d'un cocatalyseur tel que le monoxyde de carbone, un formamide ou ses acétals, ou un composé générateur de monoxyde de carbone.More precisely, the invention consists in a process for the preparation of 3-alkoxy-4-hydroxybenzaldehydes by reaction of 4-hydroxy halo-benzaldehydes of general formula (I)
in which
- X represents an iodine, bromine or chlorine atom
- R1 represents a hydrogen atom, an iodine atom, a
bromine atom, chlorine atom, alkyl radical
having 1 to 4 carbon atoms, an alkoxy radical
having 1 to 4 carbon atoms, a hydroxyl radical, with an alkali metal alcoholate, having 1 to 4 carbon atoms and in the presence of a copper compound, characterized in that one operates in the presence of a quantity effective of a cocatalyst such as carbon monoxide, a formamide or its acetals, or a compound generating carbon monoxide.
Les formamides qui sont utilisés dans le procédé sont plus particulièrement des composés de formule générale (II) :
dans laquelle
- n est égal à 1 ou à 2
- R2 et R3, identiques ou différents, représentent
. un atome d'hydrogène,
. un radical alkyle, linéaire ou ramifié ayant 1 à 6
atomes de carbone,
. un radical cycloalkyle ayant 5 à 12 atomes de carbone,
un radical aryle ayant 6 à 12 atomes de carbone,
. un radical aralkyle ayant 7 à 14 atomes de carbone,
. un radical aryle ayant 6 à 12 atomes de carbone portant
1 ou 2 substituants alkyle ayant 1 à 4 atomes de
carbone,
. un radical hétérocyclique saturé ou insaturé,
- R2 et R3 forment ensemble et avec l'atome d'azote du formamide un hétérocycle saturé comportant éventuellement en outre un atome d'azote, d'oxygène ou de soufre,
- lorsque n est égal à 2, R2 et R3 représentent un radical éthylène.The formamides which are used in the process are more particularly compounds of general formula (II):
in which
- n is equal to 1 or 2
- R2 and R3, identical or different, represent
. a hydrogen atom,
. an alkyl radical, linear or branched having 1 to 6
carbon atoms,
. a cycloalkyl radical having 5 to 12 carbon atoms,
an aryl radical having 6 to 12 carbon atoms,
. an aralkyl radical having 7 to 14 carbon atoms,
. an aryl radical having 6 to 12 carbon atoms carrying
1 or 2 alkyl substituents having 1 to 4 atoms of
carbon,
. a saturated or unsaturated heterocyclic radical,
R2 and R3 form together and with the nitrogen atom of the formamide a saturated heterocycle optionally further comprising a nitrogen, oxygen or sulfur atom,
- when n is equal to 2, R2 and R3 represent an ethylene radical.
Parmi les formamides de formule (II), on utilisera le plus souvent ceux dans la formule desquels
- n est égal à 1 ou à 2
- R2 et R3, identiques ou différents, représentent
. un atome d'hydrogène
. un radical alkyle, linéaire ou ramifié ayant 1 à 4
atomes de carbone tel que méthyle, éthyle, isopropyle,
n-propyle, n-butyle, isobutyle, sec-butyle, terti obutyl e,
. un radical cyclopentyle ou cyclohexyle,
. un radical phényle ou naphtyle,
. un radical benzyle ou phénéthyle,
. un radical alkylphényle dont la partie alkyle comporte 1
à 4 atomes de carbone,
. un radical pyridinyle-2, pyridinyle-3 ou pyridinyle-4
- R2 et R3 forment ensemble et avec l'atome d'azote du formamide un cycle pipéridinyle, un cycle morpholinyle, un cycle pipérazinyle, un cycle pyrrolidinyle
- R2 et R3 représentent un radical éthylène lorsque n est égal à 2.Among the formamides of formula (II), we will most often use those in the formula of which
- n is equal to 1 or 2
- R2 and R3, identical or different, represent
. a hydrogen atom
. an alkyl radical, linear or branched having 1 to 4
carbon atoms such as methyl, ethyl, isopropyl,
n-propyl, n-butyl, isobutyl, sec-butyl, terti obutyl e,
. a cyclopentyl or cyclohexyl radical,
. a phenyl or naphthyl radical,
. a benzyl or phenethyl radical,
. an alkylphenyl radical of which the alkyl part contains 1
with 4 carbon atoms,
. a pyridinyl-2, pyridinyl-3 or pyridinyl-4 radical
- R2 and R3 together form and with the nitrogen atom of the formamide a piperidinyl cycle, a morpholinyl cycle, a piperazinyl cycle, a pyrrolidinyl cycle
- R2 and R3 represent an ethylene radical when n is equal to 2.
Les acétals des formamides de formule (II) sont plus particulièrement ceux qui répondent à la formule générale (III)
dans laquelle R2 et R3 ont les significations indiquées précédemment pour les formamides de formule (II) et R4 représente un radical méthyle ou éthyle.The acetals of the formamides of formula (II) are more particularly those which correspond to the general formula (III)
in which R2 and R3 have the meanings indicated above for the formamides of formula (II) and R4 represents a methyl or ethyl radical.
A titre d'exemples non limitatifs de formamides de formule (II), on peut citer le formamide, le diméthylformamide, le diéthylformamide, le N-phénylformamide (ou formanilide), le N-phényl
N-méthylformamide (ou N-méthyl formanilide), le N-cyclohexylformamide, le N-pyridinyl-2 N-méthyl formamide, la N-hydrocarbonyl-morpholine, la
N-hydrocarbonyl-pipérazine, le N-hydrocarbonyl-pipéridine, la
N,N'-bis (hydrocarbonyl) pipérazine. As non-limiting examples of formamides of formula (II), mention may be made of formamide, dimethylformamide, diethylformamide, N-phenylformamide (or formanilide), N-phenyl
N-methylformamide (or N-methyl formanilide), N-cyclohexylformamide, N-pyridinyl-2 N-methyl formamide, N-hydrocarbonyl-morpholine,
N-hydrocarbonyl-piperazine, N-hydrocarbonyl-piperidine,
N, N'-bis (hydrocarbonyl) piperazine.
Lorsque le monoxyde de carbone est utilisé comme cocatalyseur, il peut être dilué à l'aide d'un gaz inerte tel que l'azote ou l'argon par exemple. When carbon monoxide is used as cocatalyst, it can be diluted using an inert gas such as nitrogen or argon for example.
On opére sous une pression de CO de 0,1 à 10 MPa. The operation is carried out under a CO pressure of 0.1 to 10 MPa.
Comme exemples non limitatifs de composés générateurs de monoxyde de carbone, on peut citer les hydroxyméthylènemalonates de dialkyle, notamment de diméthyle, de diéthyle, de di-n-propyle, de di-isopropyle, de di-n-butyle, de di-isobutyle, de di-sec-butyle et de di-tertiobutyle et leurs sels de métaux alcalins, notamment de sodium. As nonlimiting examples of compounds that generate carbon monoxide, mention may be made of dialkyl hydroxymethylenemalonates, in particular of dimethyl, diethyl, di-n-propyl, di-isopropyl, di-n-butyl, di-isobutyl , di-sec-butyl and di-tert-butyl and their alkali metal, especially sodium, salts.
Le sel de sodium de l'hydroxyméthylènemalonate de diéthyle est le plus féquemment utilisé. The sodium salt of diethyl hydroxymethylenemalonate is most commonly used.
Parmi les alcoolates de métaux alcalins mis en oeuvre dans le procédé de l'invention, les alcoolates de sodium ou de potassium des alcanols primaires ou secondaires ayant 1 à 4 atomes de carbone conviennent particulièrement bien. Among the alkali metal alcoholates used in the process of the invention, the sodium or potassium alcoholates of the primary or secondary alkanols having 1 to 4 carbon atoms are particularly suitable.
Les plus fréquemment utilisés sont le méthylate de sodium et ltéthylate de sodium. The most frequently used are sodium methylate and sodium ethylate.
Les composés du cuivre servant de catalyseurs sont connus. Ce sont d'une manière générale tous les composés organiques ou inorganiques du cuivre I ou du cuivre II. The copper compounds serving as catalysts are known. These are generally all the organic or inorganic compounds of copper I or copper II.
Le cuivre métal peut être utilisé, mais son action est beaucoup plus lente, car il faut préalablement qu'il se transforme en partie en cuivre I ou cuivre II. Copper metal can be used, but its action is much slower, because it must first transform into copper I or copper II.
A titre non limitatif, on peut citer comme composé du cuivre le chlorure cuivreux, le chlorure cuivrique, le carbonate cuivreux, le carbonate de cuivre II basique, le nitrate cuivreux, le nitrate cuivrique, le sulfate cuivrique, l'acétate cuivrique, le trifluorométhylsulfonate cuivrique, l'hydroxyde cuivrique, le picolinate de cuivre II, le méthylate de cuivre I, le méthylate de cuivre II, le chélate de cuivre II de la 8-quinoléine. As a non-limiting example, copper compound, cuprous chloride, cupric chloride, cuprous carbonate, basic copper carbonate II, cuprous nitrate, cupric nitrate, cupric sulfate, cupric acetate, trifluoromethylsulfonate, may be mentioned as a copper compound. cupric, cupric hydroxide, copper picolinate II, copper methylate I, copper methylate II, copper chelate II of 8-quinoline.
La quantité de composé du cuivre utilisée dans le procédé de l'invention peut varier très largement. The amount of copper compound used in the process of the invention can vary widely.
Habituellement le rapport molaire composé du cuivre/composé de formule (I) est de 1 % à 50 % et de préférence de 2 % à 20 %. Usually the molar ratio of copper / compound of formula (I) is from 1% to 50% and preferably from 2% to 20%.
La quantité d'alcoolate de métal alcalin utilisé est égale ou supérieure à la quantité stoechiométrique nécessaire, d'une part pour transformer le composé de formule (I) en phénate de métal alcalin (c'est-à-dire à salifier le ou les groupements OH) et d'autre part pour transformer le ou les atomes d'halogène en groupements alcoxy. The amount of alkali metal alcoholate used is equal to or greater than the stoichiometric amount necessary, on the one hand to transform the compound of formula (I) into alkali metal phenate (that is to say to salify the one or more OH groups) and on the other hand to transform the halogen atom (s) into alkoxy groups.
Généralement l'alcoolate de métal alcalin mis en oeuvre représentera de 1 fois à 4 fois la quantité stoechiométrique ainsi définie et de préférence de 1,5 à 3 fois. Generally the alkali metal alcoholate used will represent from 1 to 4 times the stoichiometric amount thus defined and preferably from 1.5 to 3 times.
Le solvant utilisé dans le procédé est le plus souvent l'alcanol correspondant à l'alcoolate de métal alcalin utilisé. The solvent used in the process is most often the alkanol corresponding to the alkali metal alcoholate used.
De manière pratique l'alcoolate de métal alcalin est formé in situ, en faisant réagir un excès d'alcanol avec le métal alcalin choisi. Conveniently the alkali metal alcoholate is formed in situ, by reacting an excess of alkanol with the selected alkali metal.
La concentration en composé de formule (I), exprimée en poids de composé (I) par rapport au poids total composé (I) + solvant est généralement de 3 % à 40 % et de préférence de 10 % à 30 %. The concentration of compound of formula (I), expressed by weight of compound (I) relative to the total weight of compound (I) + solvent is generally from 3% to 40% and preferably from 10% to 30%.
La quantité de formamide, d'acétal de formamide ou de générateur de monoxyde de carbone utilisé comme cocatalyseur dans le procédé de l'invention est telle que l'on ait généralement un rapport molaire cocatalyseur/composé du cuivre de 1,0 à 20,0 et de préférence de 1,0 à 10. The amount of formamide, formamide acetal or carbon monoxide generator used as cocatalyst in the process of the invention is such that there is generally a cocatalyst / copper compound molar ratio of 1.0 to 20, 0 and preferably from 1.0 to 10.
Cette quantité de cocatalyseur peut également être exprimée par rapport au composé de formule (I), en ce qui concerne sa limite supérieure. This amount of cocatalyst can also be expressed relative to the compound of formula (I), with regard to its upper limit.
Ainsi généralement on utilisera au plus 2 moles de cocatalyseur pour 1 mole de composé de formule (I) et de préférence 1 mole de cocatalyseur pour 1 mole de composé de formule (I). Thus generally, at most 2 moles of cocatalyst will be used for 1 mole of compound of formula (I) and preferably 1 mole of cocatalyst for 1 mole of compound of formula (I).
Parmi les halogéno hydroxy-4 benzaldéhydes de formule (I) qui servent de substrats de départ dans le présent procédé, les bromo-3-, dibromo-3,5-, iodo-3- et diodo-3,5-hydroxy-4 benzaldéhydes conviennent tout particulièrement bien. Among the 4-hydroxy halo benzaldehydes of formula (I) which serve as starting substrates in the present process, the bromo-3-, dibromo-3,5-, iodo-3- and diodo-3,5-hydroxy-4 benzaldehydes are particularly suitable.
A titre d'exemples de tels substrats on peut citer
- le bromo-3 hydroxy-4 benzaldéhyde,
- le dibromo-3,5 hydroxy-4 benzaldéhyde,
- le bromo-3 hydroxy-4 méthoxy-5 benzaldéhyde,
- le bromo-3 dihydroxy-4,5 benzaldéhyde,
- le iodo-3 hydroxy-4 benzaldéhyde,
- le diiodo-3,5 hydroxy-4 benzaldéhyde,
- le iodo-3 hydroxy-4 méthoxy-5 benzaldéhyde,
- le iodo-3 dihydroxy-4,5 benzaldéhyde,
- le bromo-3 éthoxy-5 hydroxy-4 benzaldéhyde,
- le iodo-3 éthoxy-5 hydroxy-4 benzaldéhyde.Examples of such substrates that may be mentioned
- 3-bromo-4-hydroxy benzaldehyde,
- 3,5-dibromo-4-hydroxybenzaldehyde,
- 3-bromo-4-hydroxy-5-methoxy-benzaldehyde,
- 3-bromo-4,5 dihydroxy benzaldehyde,
- iodo-3 hydroxy-4 benzaldehyde,
- 3,5-diiodo-4-hydroxy benzaldehyde,
- 3-iodo-4-hydroxy-5-methoxy-benzaldehyde,
- iodo-3 dihydroxy-4,5 benzaldehyde,
- 3-bromo-5-ethoxy-4-hydroxy benzaldehyde,
- 3-iodo-5-ethoxy-4-hydroxy benzaldehyde.
La température à laquelle est réalisé le procédé est généralement de 90"C à 200 C et de préférence de 100"C à 1800C. The temperature at which the process is carried out is generally from 90 "C to 200 C and preferably from 100" C to 1800C.
La pression n'est pas un paramètre critique en soi, mais pour atteindre les températures indiquées précédemment et ne pas perdre de solvant, le procédé est habituellement réalisé sous pression autogène. The pressure is not a critical parameter in itself, but to reach the temperatures indicated above and not to lose solvent, the process is usually carried out under autogenous pressure.
Généralement cette pression autogène du mélange réactionnel est inférieure ou égale à 5MPa (50 bars). Generally this autogenous pressure of the reaction mixture is less than or equal to 5 MPa (50 bars).
Les exemples qui suivent illustrent l'invention. The following examples illustrate the invention.
EXEMPLE 1
Dans un réacteur téfloné de 40 cm3, muni d'un système de chauffage et d'une agitation, on charge
- 2,22 g (0,0096 mol) de bromo-3-hydroxy-4-méthoxy-5
benzaldéhyde (BHMB)
- 2,16 g (0,040 mol) de méthylate de sodium
- 20 cm3 de méthanol
- 0,110 g (0,0005 mol) de carbonate de cuivre II basique
- 0,37 g (0,005 mol) de diméthylformamide.EXAMPLE 1
In a 40 cm3 teflon-coated reactor, equipped with a heating system and a stirrer, the charge is
- 2.22 g (0.0096 mol) of bromo-3-hydroxy-4-methoxy-5
benzaldehyde (BHMB)
- 2.16 g (0.040 mol) sodium methylate
- 20 cm3 of methanol
- 0.110 g (0.0005 mol) of basic copper carbonate II
- 0.37 g (0.005 mol) of dimethylformamide.
On chauffe sous agitation pendant 2 h à 125"C. On refroidit à température ambiante, puis on dilue le mélange réactionnel par 80 cm3 d'eau distillée. On ajuste ensuite à 4 le pH du mélange obtenu à l'aide d'acide sulfurique. The mixture is heated with stirring for 2 h at 125 "C. It is cooled to room temperature, then the reaction mixture is diluted with 80 cm 3 of distilled water. The pH of the mixture obtained is then adjusted to 4 using sulfuric acid .
On filtre la partie insoluble et on dose par chromatographie liquide haute performance (CLHP) le BHMB restant et le syringaldéhyde (hydroxy-4 diméthoxy-3,5 benzaldéhyde) formé. The insoluble part is filtered and the remaining BHMB and the syringaldehyde (4-hydroxy-3,5-dimethoxy-benzaldehyde) formed are assayed by high performance liquid chromatography (HPLC).
On obtient les résultats suivants :
- taux de transformation (TT) du BHMB : 100 %
- rendement (RT) en syringaldéhyde par
rapport au BHMB transformé : 99 %
EXEMPLE 2
On répète l'exemple 1, avec les mêmes charges, les mêmes conditions opératoires (sauf en ce qui concerne la durée de chauffage 1 h au lieu de 2 h) en remplaçant le diméthylformamide par 0,005 mol de
N-méthylformanilide.The following results are obtained:
- BHMB transformation rate (TT): 100%
- yield (RT) of syringaldehyde by
ratio to transformed BHMB: 99%
EXAMPLE 2
Example 1 is repeated, with the same charges, the same operating conditions (except with regard to the heating time 1 h instead of 2 h) by replacing dimethylformamide with 0.005 mol of
N-methylformanilide.
On obtient les résultats suivants
- taux de transformation (TT) du BHMB : 94,5 %
- rendement (RT) en syringaldéhyde : 98 %
EXEMPLE 3
On répète l'exemple 2, avec les mêmes charges, les mêmes conditions opératoires mais en chauffant le mélange réactionnel pendant 2 h au lieu d'une heure.The following results are obtained
- BHMB conversion rate (TT): 94.5%
- yield (RT) of syringaldehyde: 98%
EXAMPLE 3
Example 2 is repeated, with the same charges, the same operating conditions but by heating the reaction mixture for 2 hours instead of one hour.
On obtient les résultats suivants
- taux de transformation (TT) du BHMB : 96 %
- rendement (RT) en syringaldéhyde : 99 %
EXEMPLE 4
Dans un réacteur téfloné de 40 cm3, muni d'un système de chauffage et d'une agitation magnétique, on charge
- 2,26 g (0,0098 mol) de bromo-3 hydroxy-4-méthoxy-5
benzaldéhyde (BHMB)
- 1,84 g (0,034 mol) de méthylate de sodium
- 0,099 g (0,001 mol) de chlorure de cuivre I
- 20 cm3 de méthanol
- 0,396 g (0,00188 mol) du sel de sodium de
lthydroxyméthylènemalonate de diéthyle
On chauffe 4 h 30 à 125"C sous agitation. On refroidit à température ambiante, on dilue à l'eau distillée, on ajuste le pH du mélange réactionnel à 4 à l'aide d'acide sulfurique et on dose par
CLHP.The following results are obtained
- transformation rate (TT) of BHMB: 96%
- yield (RT) of syringaldehyde: 99%
EXAMPLE 4
In a 40 cm3 teflon-coated reactor, fitted with a heating system and a magnetic stirrer,
- 2.26 g (0.0098 mol) of bromo-3 hydroxy-4-methoxy-5
benzaldehyde (BHMB)
- 1.84 g (0.034 mol) sodium methylate
- 0.099 g (0.001 mol) of copper chloride I
- 20 cm3 of methanol
- 0.396 g (0.00188 mol) of the sodium salt of
diethyl hydroxymethylenemalonate
The mixture is heated for 4 h 30 min at 125 ° C. with stirring. It is cooled to room temperature, diluted with distilled water, the pH of the reaction mixture is adjusted to 4 using sulfuric acid and the mixture is dosed with
HPLC.
On obtient les résultats suivants
- taux de transformation (TT) du BHMB : 98,5 %
- rendement (RT) en syringaldéhyde : 94,5 %
EXEMPLE 5
On répète l'exemple 4, avec les mêmes charges, les mêmes conditions opératoires (sauf en ce qui concerne la durée de chauffage 1 h au lieu de 4 h 30), en remplaçant le sel de sodium de l'hydroxyméthylènemalonate de diéthyle par 0,003 mol de l'acétal méthylique du diméthylformamide.The following results are obtained
- transformation rate (TT) of BHMB: 98.5%
- yield (RT) of syringaldehyde: 94.5%
EXAMPLE 5
Example 4 is repeated, with the same charges, the same operating conditions (except with regard to the heating time 1 h instead of 4 h 30), replacing the sodium salt of diethyl hydroxymethylenemalonate with 0.003 mol of methyl acetal of dimethylformamide.
On obtient les résultats suivants
- taux de transformation (TT) du BHMB : 83 %
- rendement (RT) en syringaldéhyde : 99 %
EXEMPLE 6
On répète l'exemple 4, avec les mêmes charges, les mêmes conditions opératoires (sauf en ce qui concerne la durée de chauffage 1 h au lieu de 4 h 30), en remplaçant le sel de sodium de l'hydroxyméthylènemalonate de diéthyle par 0,003 mol de N-méthyl
N-(pyridyl-2) formamide.The following results are obtained
- BHMB conversion rate (TT): 83%
- yield (RT) of syringaldehyde: 99%
EXAMPLE 6
Example 4 is repeated, with the same charges, the same operating conditions (except with regard to the heating time 1 h instead of 4 h 30), replacing the sodium salt of diethyl hydroxymethylenemalonate with 0.003 mol of N-methyl
N- (2-pyridyl) formamide.
On obtient les résultats suivants
- taux de transformation (TT) du BHMB : 54 S
- rendement (RT) en syringaldéhyde : 80 %
EXEMPLE 7
On répète l'exemple 4, avec les mêmes charges, les mêmes conditions opératoires (sauf en ce qui concerne la durée de chauffage 1 h au lieu de 4 h 30), en remplaçant le sel de sodium de l'hydroxyméthylènemalonate de diéthyle par 0,003 mol de N-formyl pipérazine.The following results are obtained
- transformation rate (TT) of BHMB: 54 S
- yield (RT) of syringaldehyde: 80%
EXAMPLE 7
Example 4 is repeated, with the same charges, the same operating conditions (except with regard to the heating time 1 h instead of 4 h 30), replacing the sodium salt of diethyl hydroxymethylenemalonate with 0.003 mol of N-formyl piperazine.
On obtient les résultats suivants
- taux de transformation (TT) du BHMB : 70 %
- rendement (RT) en syringaldéhyde : 99 %
EXEMPLE 8
On répète l'exemple 4, avec les mêmes charges, les mêmes conditions opératoires (sauf en ce qui concerne la durée de chauffage 1 h au lieu de 4 h 30), en remplaçant le sel de sodium de l'hydroxyméthylènemalonate de diéthyle par 0,003 mol de diéthylformamide.The following results are obtained
- transformation rate (TT) of BHMB: 70%
- yield (RT) of syringaldehyde: 99%
EXAMPLE 8
Example 4 is repeated, with the same charges, the same operating conditions (except with regard to the heating time 1 h instead of 4 h 30), replacing the sodium salt of diethyl hydroxymethylenemalonate with 0.003 mol of diethylformamide.
On obtient les résultats suivants
- taux de transformation (TT) du BHMB : 42 %
- rendement (RT) en syringaldéhyde : 98 %
EXEMPLE 9
On répète l'exemple 4, avec les mêmes charges, les mêmes conditions opératoires (sauf en ce qui concerne la durée de chauffage 3 h au lieu de 4 h 30), en remplaçant le sel de sodium de l'hydroxyméthylènemalonate de diéthyle par 0,003 mol de diformyl-1,4 pipérazine.The following results are obtained
- transformation rate (TT) of BHMB: 42%
- yield (RT) of syringaldehyde: 98%
EXAMPLE 9
Example 4 is repeated, with the same charges, the same operating conditions (except with regard to the heating time 3 h instead of 4 h 30), replacing the sodium salt of diethyl hydroxymethylenemalonate with 0.003 mol of 1,4-diformyl-piperazine.
On obtient les résultats suivants
- taux de transformation (TT) du BHMB : 96 %
- rendement (RT) en syringaldéhyde : 90 %
EXEMPLE 10
Dans un réacteur téfloné de 40 cm3, muni d'un système de chauffage et d'une agitation, on charge
- 2,80 g (0,010 mol) de dibromo-3,5 hydroxy-4 benzaldéhyde
(DBHB)
- 2,27 g (0,042 mol) de méthylate de sodium
- 21 cm3 de méthanol
- 0,110 g (0,0005 mol) de carbonate de cuivre II basique
- 0,40 g (0,0055 mol) de diméthylformamide.The following results are obtained
- transformation rate (TT) of BHMB: 96%
- yield (RT) of syringaldehyde: 90%
EXAMPLE 10
In a 40 cm3 teflon-coated reactor, equipped with a heating system and a stirrer, the charge is
- 2.80 g (0.010 mol) of 3,5-dibromo-4 hydroxy-benzaldehyde
(DBHB)
- 2.27 g (0.042 mol) of sodium methylate
- 21 cm3 of methanol
- 0.110 g (0.0005 mol) of basic copper carbonate II
- 0.40 g (0.0055 mol) of dimethylformamide.
On chauffe sous agitation pendant 2 h à 125"C. On refroidit à température ambiante, puis on dilue le mélange réactionnel par 80 cm3 d'eau distillée. On ajuste ensuite à 4 le pH du mélange obtenu à l'aide d'acide sulfurique. The mixture is heated with stirring for 2 h at 125 "C. It is cooled to room temperature, then the reaction mixture is diluted with 80 cm 3 of distilled water. The pH of the mixture obtained is then adjusted to 4 using sulfuric acid .
On filtre la partie insoluble et on dose par chromatographie liquide haute performance (CLHP) le DBHB restant et le syringaldéhyde (hydroxy-4 diméthoxy-3,5 benzaldéhyde) formé. The insoluble part is filtered and the remaining DBHB and the syringaldehyde (4-hydroxy-3,5-dimethoxy-benzaldehyde) formed are assayed by high performance liquid chromatography (HPLC).
On obtient les résultats suivants
- taux de transformation (TT) du DBHB : 100 %
- rendement (RT) en syringaldéhyde par
rapport au DBHB transformé : 99 %
EXEMPLE 11
On répète l'exemple 10 avec les charges suivantes
- 1,01 g (0,005 mol) de bromo-3 hydroxy-4 benzaldéhyde (BHB)
- 2,16 g (0,040 mol) de méthylate de sodium
- 20 cm3 de méthanol
- 0,055 g (0,00025 mol) de carbonate de cuivre II basique
- 0,50 g (0,0068 mol) de diméthylformamide.The following results are obtained
- DBHB transformation rate (TT): 100%
- yield (RT) of syringaldehyde by
ratio to processed DBHB: 99%
EXAMPLE 11
Example 10 is repeated with the following charges
- 1.01 g (0.005 mol) of 3-bromo-4-hydroxy benzaldehyde (BHB)
- 2.16 g (0.040 mol) sodium methylate
- 20 cm3 of methanol
- 0.055 g (0.00025 mol) of basic copper carbonate II
- 0.50 g (0.0068 mol) of dimethylformamide.
On obtient les résultats suivants
- taux de transformation (TT) du BHB : 100 %
- rendement (RT) en vanilline : 98 %
ESSAI COMPARATIF
Dans un réacteur téfloné de 40 cm3, muni d'un système de chauffage et d'une agitation, on charge
- 2,22 g (0,0096 mol) de bromo-3-hydroxy-4-méthoxy-5
benzaldéhyde (BHMB)
- 2,16 g (0,040 mol) de méthylate de sodium
- 10 cm3 de méthanol
- 0,099 g (0,001 mol) de chlorure de cuivre I
- 10 cm3 (0,13 mol) de diméthylformamide.The following results are obtained
- BHB transformation rate (TT): 100%
- vanillin yield (RT): 98%
COMPARATIVE TEST
In a 40 cm3 teflon-coated reactor, equipped with a heating system and a stirrer, the charge is
- 2.22 g (0.0096 mol) of bromo-3-hydroxy-4-methoxy-5
benzaldehyde (BHMB)
- 2.16 g (0.040 mol) sodium methylate
- 10 cm3 of methanol
- 0.099 g (0.001 mol) of copper chloride I
- 10 cm3 (0.13 mol) of dimethylformamide.
On chauffe sous agitation pendant 10 h à reflux (on effectue un prélèvement pour dosage après 1 h de chauffage). On refroidit à température ambiante, puis on dilue le mélange réactionnel par 80 cm3 d'eau distillée. On ajuste ensuite à 4 le pH du mélange obtenu à l'aide d'acide sulfurique. The mixture is heated with stirring for 10 h at reflux (a sample is taken for dosing after 1 h of heating). Cool to room temperature, then dilute the reaction mixture with 80 cm3 of distilled water. The pH of the mixture obtained is then adjusted to 4 using sulfuric acid.
On filtre la partie insoluble et on dose par chromatographie liquide haute performance (CLHP) le BHMB restant et le syringaldéhyde (hydroxy-4 diméthoxy-3,5 benzaldéhyde) formé. The insoluble part is filtered and the remaining BHMB and the syringaldehyde (4-hydroxy-3,5-dimethoxy-benzaldehyde) formed are assayed by high performance liquid chromatography (HPLC).
On obtient les résultats suivants pour 1 heure de chauffage
- taux de transformation (TT) du BHMB : 19 %
- rendement (RT) en syringaldéhyde par
rapport au BHMB transformé : 99 %
On obtient les résultats suivants pour 10 heures de chauffage
- taux de transformation (TT) du BHMB : 100 %
- rendement (RT) en syringaldéhyde par
rapport au BHMB transformé : 99 % The following results are obtained for 1 hour of heating
- transformation rate (TT) of BHMB: 19%
- yield (RT) of syringaldehyde by
ratio to transformed BHMB: 99%
The following results are obtained for 10 hours of heating
- BHMB transformation rate (TT): 100%
- yield (RT) of syringaldehyde by
ratio to transformed BHMB: 99%
Claims (19)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8917213A FR2655984B1 (en) | 1989-12-20 | 1989-12-20 | PROCESS FOR THE PREPARATION OF ALCOXY-3 HYDROXY-4 BENZALDEHYDES. |
| EP19900403588 EP0434517A3 (en) | 1989-12-20 | 1990-12-14 | Process for the preparation of mono- or poly-alkoxylated aromatic compounds |
| CA002032580A CA2032580A1 (en) | 1989-12-20 | 1990-12-18 | Process for preparing aromatic mono or polyalkoxylated derivatives |
| JP2419320A JPH04305550A (en) | 1989-12-20 | 1990-12-20 | Method of manufacturing mono- or poly-alkoxylated aromatic compound |
| AU68366/90A AU6836690A (en) | 1989-12-20 | 1990-12-20 | Process for the preparation of mono- or polyalkoxylated aromatic compounds |
| IE464390A IE904643A1 (en) | 1989-12-20 | 1990-12-20 | Process for the preparation of mono- or poly-alkoxylated¹aromatic compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8917213A FR2655984B1 (en) | 1989-12-20 | 1989-12-20 | PROCESS FOR THE PREPARATION OF ALCOXY-3 HYDROXY-4 BENZALDEHYDES. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2655984A1 true FR2655984A1 (en) | 1991-06-21 |
| FR2655984B1 FR2655984B1 (en) | 1993-07-02 |
Family
ID=9388979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8917213A Expired - Fee Related FR2655984B1 (en) | 1989-12-20 | 1989-12-20 | PROCESS FOR THE PREPARATION OF ALCOXY-3 HYDROXY-4 BENZALDEHYDES. |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2655984B1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4218567A (en) * | 1978-05-30 | 1980-08-19 | Hoffmann-La Roche Inc. | Process for aromatic ethers |
| US4588835A (en) * | 1982-03-29 | 1986-05-13 | Otsuka Kagaku Yakuhin Kabushiki Kaisha | Process for preparing alkoxyphenols |
-
1989
- 1989-12-20 FR FR8917213A patent/FR2655984B1/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4218567A (en) * | 1978-05-30 | 1980-08-19 | Hoffmann-La Roche Inc. | Process for aromatic ethers |
| US4588835A (en) * | 1982-03-29 | 1986-05-13 | Otsuka Kagaku Yakuhin Kabushiki Kaisha | Process for preparing alkoxyphenols |
Non-Patent Citations (1)
| Title |
|---|
| SYNTHESIS, 1983, page 308; D.V. RAO et al.: "An efficient synthesis of 3,4,5-trimethoxybenzaldehyde from vanillin" * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2655984B1 (en) | 1993-07-02 |
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