DE2726393C2 - Verfahren zur Herstellung von 5-(quartär-Alkyl)resorcinen - Google Patents
Verfahren zur Herstellung von 5-(quartär-Alkyl)resorcinenInfo
- Publication number
- DE2726393C2 DE2726393C2 DE2726393A DE2726393A DE2726393C2 DE 2726393 C2 DE2726393 C2 DE 2726393C2 DE 2726393 A DE2726393 A DE 2726393A DE 2726393 A DE2726393 A DE 2726393A DE 2726393 C2 DE2726393 C2 DE 2726393C2
- Authority
- DE
- Germany
- Prior art keywords
- dimethoxy
- alkyl
- hydroxy
- dimethylheptyl
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 34
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 title description 7
- 238000002360 preparation method Methods 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 53
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 33
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 29
- -1 alkali metal salts Chemical class 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- 125000003118 aryl group Chemical group 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- DHTQKXHLXVUBCF-UHFFFAOYSA-N diethyl phenyl phosphate Chemical compound CCOP(=O)(OCC)OC1=CC=CC=C1 DHTQKXHLXVUBCF-UHFFFAOYSA-N 0.000 description 6
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KBCNUEXDHWDIFX-UHFFFAOYSA-N 2-methyloctan-2-ol Chemical compound CCCCCCC(C)(C)O KBCNUEXDHWDIFX-UHFFFAOYSA-N 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- GWBGUJWRDDDVBI-UHFFFAOYSA-N 5-(2-methyloctan-2-yl)benzene-1,3-diol Chemical compound CCCCCCC(C)(C)C1=CC(O)=CC(O)=C1 GWBGUJWRDDDVBI-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VFZRZRDOXPRTSC-UHFFFAOYSA-N 3,5-Dimethoxybenzaldehyde Chemical compound COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 2
- IWPZKOJSYQZABD-UHFFFAOYSA-N 3,5-dimethoxybenzoic acid Chemical compound COC1=CC(OC)=CC(C(O)=O)=C1 IWPZKOJSYQZABD-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052740 iodine Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- BDMBWENRFFKJON-JWQCQUIFSA-N n-[(2r,4r)-1,4-dihydroxy-4-phenylbutan-2-yl]hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)N[C@@H](CO)C[C@@H](O)C1=CC=CC=C1 BDMBWENRFFKJON-JWQCQUIFSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- UFFAFBPZFGAMJJ-UHFFFAOYSA-N (2-methoxy-4,6-dimethylphenyl)boronic acid Chemical compound COC1=CC(C)=CC(C)=C1B(O)O UFFAFBPZFGAMJJ-UHFFFAOYSA-N 0.000 description 1
- AUDBREYGQOXIFT-UHFFFAOYSA-N (3,5-dimethoxyphenyl)methanol Chemical compound COC1=CC(CO)=CC(OC)=C1 AUDBREYGQOXIFT-UHFFFAOYSA-N 0.000 description 1
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 1
- MYYOUJBZUGHFNX-UHFFFAOYSA-N 1,3-dimethoxy-5-(2-methyloctan-2-yl)benzene Chemical compound CCCCCCC(C)(C)C1=CC(OC)=CC(OC)=C1 MYYOUJBZUGHFNX-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CCAWDIFJOBKBSE-UHFFFAOYSA-N 1-(chloromethyl)-3,5-dimethoxybenzene Chemical compound COC1=CC(CCl)=CC(OC)=C1 CCAWDIFJOBKBSE-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N 1-butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- RAVCUFDAEOYXPH-UHFFFAOYSA-N 2,6-dimethoxy-4-(2-methyloctan-2-yl)phenol Chemical compound CCCCCCC(C)(C)C1=CC(OC)=C(O)C(OC)=C1 RAVCUFDAEOYXPH-UHFFFAOYSA-N 0.000 description 1
- WFRBDWRZVBPBDO-UHFFFAOYSA-N 2-methyl-2-pentanol Chemical compound CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 description 1
- HANZCFMKZJDWMT-UHFFFAOYSA-N 2-phenylhexan-2-ol Chemical compound CCCCC(C)(O)C1=CC=CC=C1 HANZCFMKZJDWMT-UHFFFAOYSA-N 0.000 description 1
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 1
- OXTNCQMOKLOUAM-UHFFFAOYSA-N 3-Oxoglutaric acid Chemical compound OC(=O)CC(=O)CC(O)=O OXTNCQMOKLOUAM-UHFFFAOYSA-N 0.000 description 1
- JEWXYDDSLPIBBO-UHFFFAOYSA-N 3-methyl-3-octanol Chemical compound CCCCCC(C)(O)CC JEWXYDDSLPIBBO-UHFFFAOYSA-N 0.000 description 1
- HTOJWBXEIXMEHL-UHFFFAOYSA-N 4-(1-adamantyl)-2,6-dimethoxyphenol Chemical compound COC1=C(O)C(OC)=CC(C23CC4CC(CC(C4)C2)C3)=C1 HTOJWBXEIXMEHL-UHFFFAOYSA-N 0.000 description 1
- JGVWWKMGFNTMRC-UHFFFAOYSA-N 5-(1-adamantyl)benzene-1,3-diol Chemical compound OC1=CC(O)=CC(C23CC4CC(CC(C4)C2)C3)=C1 JGVWWKMGFNTMRC-UHFFFAOYSA-N 0.000 description 1
- CMWWASSEHWHAAY-UHFFFAOYSA-N 7-phenyltridecan-7-ol Chemical compound CCCCCCC(O)(CCCCCC)C1=CC=CC=C1 CMWWASSEHWHAAY-UHFFFAOYSA-N 0.000 description 1
- 229930188104 Alkylresorcinol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DQHUZEIHOYMCAW-UHFFFAOYSA-N C(C)[ClH]P(=O)[ClH]CC Chemical compound C(C)[ClH]P(=O)[ClH]CC DQHUZEIHOYMCAW-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 208000020401 Depressive disease Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- AITBWAWXCRRGKU-UHFFFAOYSA-N [4-(1-adamantyl)-2,6-dimethoxyphenyl] diethyl phosphate Chemical compound C1=C(OC)C(OP(=O)(OCC)OCC)=C(OC)C=C1C1(C2)CC(C3)CC2CC3C1 AITBWAWXCRRGKU-UHFFFAOYSA-N 0.000 description 1
- QXBMOUQKWWNESC-UHFFFAOYSA-N [I].[I].[I].[I].[C] Chemical compound [I].[I].[I].[I].[C] QXBMOUQKWWNESC-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940030600 antihypertensive agent Drugs 0.000 description 1
- 239000002220 antihypertensive agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000012649 demethylating agent Substances 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- PUINPNFEXGNBEY-UHFFFAOYSA-N ethyl phenyl hydrogen phosphite Chemical compound CCOP(O)OC1=CC=CC=C1 PUINPNFEXGNBEY-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- XWCQLLDGXBLGMD-UHFFFAOYSA-M magnesium;pentane;bromide Chemical compound [Mg+2].[Br-].CCCC[CH2-] XWCQLLDGXBLGMD-UHFFFAOYSA-M 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
die Substituenten R2 und R3 unabhängig voneinander Ci- GrAJky) bedeuten und
die auf diese Weise erhaltene Verbindung der allgemeinen Formel IV durch Umsetzen mit einem Alkalimetall in das entsprechende 1 -(quartär-Alkyl)-3,5-dimethoxybenzol der allgemeinen Formel V
die Verbindung der allgemeinen Formel V mit Hilfe von Pyridinhydrochlorid, Bortribromid, Bortrichlorid, Aluminiumbromid, Aluminiumchlorid oder Bromwasserstoffsäure in Essigsäure entmethyliert.
X-P
Ci — Cr Alkyl oder
Ä
Die Stufe (A) wird in Gegenwart von Methansulfonsäure. Schwefelsäure und/oder p-Toluolsulfonsäure durchgeführt, wobei Methansulfonsäurc bevorzugt ist. Hierzu vermischt man im allgemeinen etwa äquimolarc Mengen 2.6-Dimethoxyphcnol und des jeweiligen tertiären Carbinols in Gegenwart der jeweiligen Säure. Die Säuremenge ist nicht kritisch, und es kann
erfindungsgemäßen Verfahrens jo
delta 3,9 (s, 6H1OCH3)
delta 6,58 (s, 2H. aromatisch)
NMR-Spektrum (CDCl3):
5,4 (breites s, 1H, Hydroxyl)
4,8 (doppeltes s, 6H, Methoxyl)
5,4(breites s, IH, Hydroxyl)
33 (s,6H, Methoxyl)
13—0,8 (m, 17H, Methylsubstituent;
Cyclohexylsubstituent)
3,9 (ε 6Η, Methoxyl)
6.5 (s. 2H. aromatischer Ring)
3,8 (s, 6H, aromatisches Methoxyl)
4,3 (q, 4H, Phosphonatmethylen)
3,9 (s, 6H, aromatische Methoxylreste)
1,9-1,1 (m, 17H, Cyclohexyl,
Phosphonatmethyl)
6,5 (m, 2H, aromatischer Ring)
4,4 (m,4H, Phosphonatmethylen)
2,2—0,7 (m, 22H, Methylsubstituent,
Phosphonatmethylreste)
5,8—4,1 (m,4H, Phosphonatmethylen)
2,2—0,8 (m, 20H, Methylsubstituent,
Ausbeute= 100%.
erfindungsgemäßen Verfahrens
6,25 (t, 1H, C-4-aromatisch)
3,75 (s, 6H1OCH3)
1,25 (s,6H, C(CH3J2)
erfindungsgemäßen Verfahrens
6,15 (t, 1H, aromatisch)
5,20 (breites s, 2H, OH)
UO (s, 6H, QCHa)2)
l,8-0,5(m,13H, Alkyl)
6,15 (t, IH, aromatisch)
5,2 (breites s, 2H1OH)
1,20 (s,6H, QCHj)2)
Smp. 108 bis 110° C
delta 7,8 (breit, 2H, Hydroxy)
7,3 (s, 5H, Phenylsubstituent)
6,3 (enges m, 3H, aromatischer Ring)
1,6 (s, 6H, Methylsubstituent) eJS^U-DimethylcyclohexylmethylJresorcin, Smp. 145 bis 147°C
Methyl-und Hexylsubstituent)
Methylsubstituenten)
Claims (1)
- 7 26Patentanspruch:Verfahren zur Herstellung von 5-{quartär-AIkyl)-resorcinen der allgemeinen Formel 1HOOHCH3O
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/695,674 US4087410A (en) | 1976-06-14 | 1976-06-14 | 5-(Tertiary alkyl) resorcinol preparation and intermediates therefor |
Publications (2)
Publication Number | Publication Date |
---|---|
DE2726393A1 DE2726393A1 (de) | 1977-12-22 |
DE2726393C2 true DE2726393C2 (de) | 1984-04-12 |
Family
ID=24794013
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2759964A Expired DE2759964C2 (de) | 1976-06-14 | 1977-06-10 | 2,6-Dimethoxy-4-(quaternäre-alkyl)phenyl-disubstituierte-phosphate und Verfahren zu ihrer Herstellung |
DE2726393A Expired DE2726393C2 (de) | 1976-06-14 | 1977-06-10 | Verfahren zur Herstellung von 5-(quartär-Alkyl)resorcinen |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2759964A Expired DE2759964C2 (de) | 1976-06-14 | 1977-06-10 | 2,6-Dimethoxy-4-(quaternäre-alkyl)phenyl-disubstituierte-phosphate und Verfahren zu ihrer Herstellung |
Country Status (11)
Country | Link |
---|---|
US (2) | US4087410A (de) |
JP (3) | JPS52153921A (de) |
BE (1) | BE855601A (de) |
CA (1) | CA1099709A (de) |
CH (3) | CH630052A5 (de) |
DE (2) | DE2759964C2 (de) |
FR (1) | FR2354987A1 (de) |
GB (1) | GB1579557A (de) |
IE (1) | IE44971B1 (de) |
IL (3) | IL52291A (de) |
NL (1) | NL7706505A (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6033732U (ja) * | 1983-08-12 | 1985-03-07 | オムロン株式会社 | 高周波リレ− |
JPS6033731U (ja) * | 1983-08-12 | 1985-03-07 | オムロン株式会社 | 高周波リレ− |
JPS60136037U (ja) * | 1984-02-21 | 1985-09-10 | 松下電器産業株式会社 | マグネツトリレ−の取付装置 |
SE458033B (sv) * | 1984-10-22 | 1989-02-20 | Chemical Dynamics Dev Ab | Metod foer dealkylering av alkyl-aryl-etrar |
FR2636061B1 (fr) * | 1988-09-07 | 1990-11-09 | Cird | Procede de preparation de derives de l'adamantane-1 |
US5414130A (en) * | 1993-12-23 | 1995-05-09 | The Dow Chemical Company | Process for the preparation of diaminoresorcinol |
JP4965270B2 (ja) * | 2007-01-16 | 2012-07-04 | 出光興産株式会社 | アダマンチルカルボニル基含有芳香族ジオール、その誘導体及びそれらの製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2888503A (en) * | 1955-12-29 | 1959-05-26 | Universal Oil Prod Co | 2, 6 dialkoxy, 4 alkyl phenol antiozidants |
US3107164A (en) * | 1962-03-27 | 1963-10-15 | Stauffer Chemical Co | Herbicidal methods employing omicron, omicron-diallyl omicron-aryl phosphate esters |
US3729519A (en) * | 1969-01-22 | 1973-04-24 | Hoffmann La Roche | Process for the preparation of alkyl substituted resorcinols |
US3838181A (en) * | 1969-01-22 | 1974-09-24 | Hoffmann La Roche | Process for the preparation of alkyl substituted resorcinols |
CH540209A (de) * | 1969-01-22 | 1973-08-15 | Hoffmann La Roche | Verfahren zur Herstellung von Resorcinderivaten |
US3790636A (en) * | 1971-09-16 | 1974-02-05 | Hoffmann La Roche | Process for the preparation of alkyl substituted resorcinols |
CH574888A5 (de) * | 1972-12-07 | 1976-04-30 | Ciba Geigy Ag |
-
1976
- 1976-06-14 US US05/695,674 patent/US4087410A/en not_active Expired - Lifetime
-
1977
- 1977-05-27 JP JP6270177A patent/JPS52153921A/ja active Granted
- 1977-06-09 CA CA280,211A patent/CA1099709A/en not_active Expired
- 1977-06-09 GB GB24261/77A patent/GB1579557A/en not_active Expired
- 1977-06-10 DE DE2759964A patent/DE2759964C2/de not_active Expired
- 1977-06-10 IE IE1193/77A patent/IE44971B1/en unknown
- 1977-06-10 DE DE2726393A patent/DE2726393C2/de not_active Expired
- 1977-06-10 BE BE1008184A patent/BE855601A/xx not_active IP Right Cessation
- 1977-06-10 IL IL52291A patent/IL52291A/xx unknown
- 1977-06-13 CH CH725777A patent/CH630052A5/de not_active IP Right Cessation
- 1977-06-13 FR FR7718052A patent/FR2354987A1/fr active Granted
- 1977-06-13 NL NL7706505A patent/NL7706505A/xx not_active Application Discontinuation
-
1978
- 1978-02-01 US US05/874,183 patent/US4131656A/en not_active Expired - Lifetime
-
1980
- 1980-05-01 IL IL59962A patent/IL59962A0/xx unknown
- 1980-05-01 IL IL59963A patent/IL59963A0/xx unknown
- 1980-08-06 JP JP10815680A patent/JPS56131538A/ja active Granted
- 1980-08-06 JP JP55108155A patent/JPS5828877B2/ja not_active Expired
-
1981
- 1981-10-13 CH CH655181A patent/CH631181A5/de not_active IP Right Cessation
- 1981-10-19 CH CH666781A patent/CH631146A5/de not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
IL52291A (en) | 1982-07-30 |
CA1099709A (en) | 1981-04-21 |
JPS56131538A (en) | 1981-10-15 |
NL7706505A (nl) | 1977-12-16 |
DE2759964C2 (de) | 1986-03-20 |
JPS5748537B2 (de) | 1982-10-16 |
DE2726393A1 (de) | 1977-12-22 |
CH630052A5 (de) | 1982-05-28 |
CH631146A5 (de) | 1982-07-30 |
JPS56131595A (en) | 1981-10-15 |
JPS5828877B2 (ja) | 1983-06-18 |
FR2354987A1 (fr) | 1978-01-13 |
BE855601A (fr) | 1977-12-12 |
IE44971L (en) | 1977-12-14 |
IL59963A0 (en) | 1980-07-31 |
JPS52153921A (en) | 1977-12-21 |
IL52291A0 (en) | 1977-08-31 |
US4087410A (en) | 1978-05-02 |
CH631181A5 (de) | 1982-07-30 |
JPS5736264B2 (de) | 1982-08-03 |
IL59962A0 (en) | 1980-07-31 |
US4131656A (en) | 1978-12-26 |
GB1579557A (en) | 1980-11-19 |
IE44971B1 (en) | 1982-05-19 |
FR2354987B1 (de) | 1980-09-19 |
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