NO753168L - - Google Patents
Info
- Publication number
- NO753168L NO753168L NO753168A NO753168A NO753168L NO 753168 L NO753168 L NO 753168L NO 753168 A NO753168 A NO 753168A NO 753168 A NO753168 A NO 753168A NO 753168 L NO753168 L NO 753168L
- Authority
- NO
- Norway
- Prior art keywords
- carboxylate
- methyl
- carboxylic acid
- methylthio
- methylsulfonylxanthone
- Prior art date
Links
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 56
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000007964 xanthones Chemical class 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims 7
- -1 ester compounds Chemical class 0.000 description 23
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007858 starting material Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 125000004414 alkyl thio group Chemical group 0.000 description 6
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001350 alkyl halides Chemical class 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001347 alkyl bromides Chemical class 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 2
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- GIUUCQVKMWBSRT-UHFFFAOYSA-N 2-bromododecane Chemical compound CCCCCCCCCCC(C)Br GIUUCQVKMWBSRT-UHFFFAOYSA-N 0.000 description 1
- HLAUCEOFCOXKNF-UHFFFAOYSA-N 2-bromoheptane Chemical compound CCCCCC(C)Br HLAUCEOFCOXKNF-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Fremgangsmåte for fremstilling av mellomprodukter forProcess for the production of intermediates for
syntese av xanton-derivater.synthesis of xanthone derivs.
Foreliggende oppfinnelse angår fremstilling av mellomprodukter for syntese av xanton-derivater i henhold til patent nr.. (søknad 753167 og 753168), hvilke mellomprodukter har formelen: hvor en av gruppene R"*" betegner hydroksy og den andre gruppen R"*" betegner -S-R, The present invention relates to the production of intermediates for the synthesis of xanthone derivatives according to patent no.. (application 753167 and 753168), which intermediates have the formula: where one of the groups R"*" denotes hydroxy and the other group R"*" denotes -S-R,
hvor R er lik lavere alkyl og hvor R betegner hydrogen eller lavalkyl. where R is equal to lower alkyl and where R denotes hydrogen or lower alkyl.
De aktuelle mellomprodukter kan fremstilles og brukes som det fremgår av følgende reaksjonsskjerna: The relevant intermediates can be prepared and used as shown in the following reaction core:
hvor hver av gruppene R<7>, R Q , R<10>og R<11>har den ovenfor angitte where each of the groups R<7>, R Q , R<10>and R<11> has the above indicated
7' 14 7' 14
betydning, R er hydrogen eller lavere alkyl og R er en alkylgruppe med 1-12 .karbonatomer» og ved meaning, R is hydrogen or lower alkyl and R is an alkyl group with 1-12 carbon atoms" and by
Reaksjonsskjerna B'Reaction nucleus B'
Forbindelsene med formel (4') kan alternativt fremstilles i overensstemmelse med følgende reaksjonsskjema: The compounds of formula (4') can alternatively be prepared in accordance with the following reaction scheme:
7 7' 10 11 13 ^ 7 7' 10 11 13 ^
hvor hver,av gruppene R , R , R , R og R har den ovenfor angitte betydning, og R 15 er en. alkylgruppe med 1-12 karbonatomer. where each of the groups R , R , R , R and R has the above meaning, and R 15 is one. alkyl group with 1-12 carbon atoms.
Under henvisning til de ovenstående reaksjonsskjemaer A' og B', så blir 5~alkoksy-7_lavere alkyltiosyrene eller estrene (16) og 5-lavere alkyltio-7-metoksysyrene eller estrene (22), fortrinnsvis metoksyforbindelsene, omdannet til deres tilsvarende 5-hydroksy-7_lavere alkyltiosyrer (17) og 5-lavere alkyltio-7-hydroksysyrer (23) ved behandling med hydrojod- eller hydrobromsyre i nærvær av et egnet oppløsningsmiddel, f.eks. eddiksyreanhydrid, eddiksyre eller propionsyre. With reference to the above reaction schemes A' and B', the 5-lower alkylthio-7-lower alkylthio acids or esters (16) and the 5-lower alkylthio-7-methoxy acids or esters (22), preferably the methoxy compounds, are converted into their corresponding 5-hydroxy -7-lower alkylthio acids (17) and 5-lower alkylthio-7-hydroxy acids (23) by treatment with hydroiodic or hydrobromic acid in the presence of a suitable solvent, e.g. acetic anhydride, acetic acid or propionic acid.
Forbindelsene med formler (17) og (23) blir deretter eventuelt forestret med et alkylhalogenid, f.eks. metyljodid, etylbromid og lignende, i nærvær av et organisk oppløsningsmiddel, 'f.eks. dimetylformamid, dimetylacetamid, N-metylpyrrolidén og lignende, og litiumkarbonat, for oppnåelse av esterforbindelsene med formlene (18) og (24). The compounds with formulas (17) and (23) are then optionally esterified with an alkyl halide, e.g. methyl iodide, ethyl bromide and the like, in the presence of an organic solvent, e.g. dimethylformamide, dimethylacetamide, N-methylpyrrolidene and the like, and lithium carbonate, to obtain the ester compounds of formulas (18) and (24).
5-hydroksy-7-lavere alkyltiosyrene (17) eller estrene (18) og 5-lavere alkyltio-7_hydroksysyrene (23) eller estrene (24), foretres med et alkylhalogenid, fortrinnsvis alkylbromid, f.eks. etylbromid, 2-brompropan (isopropylbromid), 1-brombutan (n-butyl-bromid), 1-brom-3-metylbutan (isopentylbromid), 1-bromheksan (heksy bromid), 1-bromheptan (heptylbromid), 2-bromheptan, 1-bromoktan (oktylbromid), 1-bromdodekan (dodecylbromid), 2-bromdodekan, og lignende, i nærvær av et organisk oppløsningsmiddel, f.eks. dimetyl formamid, dimetylacetamid, aceton, og lignende, og kaliumkarbonat, for oppnåelse av 5-alkoksy-7_lavere alkyltioforbindelsene (19) og 5-lavere alkyltio-7-alkoksyforbindelsene (25), respektivt. The 5-hydroxy-7-lower alkylthioacids (17) or esters (18) and the 5-lower alkylthio-7-hydroxyacids (23) or esters (24) are etherified with an alkyl halide, preferably alkyl bromide, e.g. ethyl bromide, 2-bromopropane (isopropyl bromide), 1-bromobutane (n-butyl bromide), 1-bromo-3-methylbutane (isopentyl bromide), 1-bromohexane (hexy bromide), 1-bromoheptane (heptyl bromide), 2-bromoheptane, 1-bromooctane (octyl bromide), 1-bromododecane (dodecyl bromide), 2-bromododecane, and the like, in the presence of an organic solvent, e.g. dimethyl formamide, dimethylacetamide, acetone, and the like, and potassium carbonate, to obtain the 5-alkoxy-7_lower alkylthio compounds (19) and the 5-lower alkylthio-7-alkoxy compounds (25), respectively.
Forbindelsene med formlene (19) og (25) oksyderes til sulfinylforbindelsene med formler (20) og (26) og sulfonylforbindel med formler (21) og (27), som beskrevet i norsk søknad 2495/72. Estrene med formlene (20),:(;26), (21) og £27) underkastes eventuelt basehydrolyse, ifølge den metode som er beskrevet i nevnte søknad, og dette gir 5_alkoksy-7~lavere alkylsulfonylsyrene, 5-lavere alkylsulfinyl-7-alkoksysyrene, 5-alkoksy-7-lavere alkylsulfonylsyre og 5-lavere alkylsulfonyl-7-alkoksysyrene. Frie syrer med formler (20) , (21), (26) og (27) omdannes eventuelt til deres salter, estere og amider som beskrevet i det nedenstående. The compounds with formulas (19) and (25) are oxidized to the sulfinyl compounds with formulas (20) and (26) and sulfonyl compounds with formulas (21) and (27), as described in Norwegian application 2495/72. The esters with the formulas (20), ::(;26), (21) and £27) are optionally subjected to base hydrolysis, according to the method described in the aforementioned application, and this gives the 5-alkyl-7-lower alkylsulfonyl acids, the 5-lower alkylsulfinyl-7 -Alkoxy acids, 5-Alkoxy-7-lower alkylsulphonyl acid and 5-Lower alkylsulphonyl-7-Alkoxy acids. Free acids with formulas (20), (21), (26) and (27) are optionally converted into their salts, esters and amides as described below.
5-hydroksy-7-lavere alkyltioforbindelsene (17) og (18) 5-lavere alkyltio-7-hydroksyforbindelsene (23) og (24), blir alternativt først oksydert til sulfinylforbindelser, formler (20a) og (26a), og sulfonylforbindelser, formler (21a) og (27a), som beskrevet i ovennevnte norske søknad. Forbindelsene med formler (20a), (26a), :('21a) og (27a) blir deretter foretret med et alkylhalogenid, på samme måte som beskrevet ovenfor for omdannelsene (18) til (19) og (24) til (25) hvilket gir forbindelsene (20), (26) (21) og (27), respektivt. For mellomproduktene (19), (20a), (21a), (25), (26a) og (27a), kan en fri syre forestres og en ester kan hydrolyseres til den frie syre. The 5-hydroxy-7-lower alkylthio compounds (17) and (18) the 5-lower alkylthio-7-hydroxy compounds (23) and (24), are alternatively first oxidized to sulfinyl compounds, formulas (20a) and (26a), and sulfonyl compounds, formulas (21a) and (27a), as described in the above-mentioned Norwegian application. The compounds of formulas (20a), (26a), :('21a) and (27a) are then etherified with an alkyl halide, in the same manner as described above for the transformations (18) to (19) and (24) to (25) giving compounds (20), (26), (21) and (27), respectively. For intermediates (19), (20a), (21a), (25), (26a) and (27a), a free acid can be esterified and an ester can be hydrolyzed to the free acid.
Følgende eksempler illustrerer oppfinnelsen. Når det har vært nødvendig er eksemplene blitt gjentatt for å få tilveie-bragt utgangsmaterialene for de etterfølgende eksempler. The following examples illustrate the invention. When it has been necessary, the examples have been repeated in order to obtain the starting materials for the subsequent examples.
Eksempel 1Example 1
Til en suspensjon av 500 mg metyl-5-hydroksy-7-metyltio-xanton-2-karboksylat (fremstilt som i eksempel 5, del B) i 20 ml dimetylformamid, ble det ved romtemperatur dråpevis tilsatt en oppløsning av 320 mg m-klorperbenzosyre i 3 ml dimetylformamid. Etter omrøring i 15 min. ble 50 ml 1% vandig natriumbisulfitt tilsatt, det resulterende bunnfall ble filtrert, vasket med vann, deretter med aceton, og dette ga 480 mg metyl-5-hydroksy-7-nietyl-sulfinylxanton-2-karboksylat, sm.p. 289"291°C (dekomp.). To a suspension of 500 mg of methyl-5-hydroxy-7-methylthio-xanthone-2-carboxylate (prepared as in example 5, part B) in 20 ml of dimethylformamide, a solution of 320 mg of m-chloroperbenzoic acid was added dropwise at room temperature in 3 ml of dimethylformamide. After stirring for 15 min. 50 ml of 1% aqueous sodium bisulfite was added, the resulting precipitate was filtered, washed with water, then with acetone, and this gave 480 mg of methyl 5-hydroxy-7-niethyl-sulfinylxanthone-2-carboxylate, m.p. 289"291°C (decomp.).
Ved å erstatte metyl-5-metyltio-7_hydroksyxanton-2-karboksylat (fremstilt i eksempel 5, del B) medmmetyl-5-hydroksy-7-metyltioxanton-2-karboksylat får man på samme måte metyl-5-metyl-sulfinyl-7-hydroksyxanton-2-karboksylat, sm.p. 322-323°C (dekomp.). By replacing methyl-5-methylthio-7-hydroxyxanthone-2-carboxylate (prepared in example 5, part B) with methyl-5-hydroxy-7-methylthioxanthone-2-carboxylate, methyl-5-methyl-sulfinyl-7 -hydroxyxanthone-2-carboxylate, m.p. 322-323°C (decomp.).
Ved i stedet for de ovenfor angitte utgangsmaterialer å benytte den tilsvarende frie 2-karboksylsyre eller en annen lavere alkylester derav, kan man på samme måte fremstille f.eks. 5_hydroksy-7-metylsulfinylxanton-2-karboksylsyre, etyl-5-hydroksy-7-metylsulfinylxanton-2-karboksylat, pentyl-5-hydroksy-7-metylsulfinylxanton-2-karboksylat, 5-metylsulfiny1-7-hydroksyxanton-2-karboksylsyre, etyl-5-metylsulfiny1-7-hydroksyxanton-2-karboksylat og pentyl-5-metylsulfiny1-7-hydroksyxanton-2-karboksylat. By using the corresponding free 2-carboxylic acid or another lower alkyl ester thereof instead of the above-mentioned starting materials, one can prepare e.g. 5_hydroxy-7-methylsulfinylxanthone-2-carboxylic acid, ethyl 5-hydroxy-7-methylsulfinylxanthone-2-carboxylate, pentyl 5-hydroxy-7-methylsulfinylxanthone-2-carboxylate, 5-methylsulfiny1-7-hydroxyxanthone-2-carboxylic acid, ethyl 5-methylsulfinyl 1-7-hydroxyxanthone-2-carboxylate and pentyl 5-methylsulfinyl 1-7-hydroxyxanthone-2-carboxylate.
På lignende måte, ved å bytte ut de ovenfor angitte metyltio-utgangsmaterialer, kan man fremstille tilsvarende etylsulfinyl-, propylsulfinyl-, butylsulfinyl- og pentylsulfinyl-forbindelser. In a similar way, by replacing the above-mentioned methylthio starting materials, corresponding ethylsulfinyl, propylsulfinyl, butylsulfinyl and pentylsulfinyl compounds can be prepared.
Eksempel 2Example 2
Ved å utgå fra 5-hydroksy-7-metyltioxanton-2-karboksylsyre, 5_metyltio-7-hydroksyxanton-2-karboksylsyre eller en lavere alkylester derav, og foreta oksydasjonsmetoden som angitt i eksempel 4, kan man fremstille f.eks.: 5-hydroksy-7-metylsulfonylxanton-2-karboksylsyre, metyl-5_hydroksy-7-metylsulfonylxanton-2-karboksylat, pentyl-5-hydroksy-7-metylsulfonylxanton-2-karboksylat, 5-metylsulfony1-7-hydroksyxanton-2-karboksylsyre, metyl-5-metylsulfonyl-7-hydroksyxanton-2-karboksylat, og pentyl-5-metylsulfony1-7-hydroksyxanton-2-karboksylat. By starting from 5-hydroxy-7-methylthioxanthone-2-carboxylic acid, 5-methylthio-7-hydroxyxanthone-2-carboxylic acid or a lower alkyl ester thereof, and carrying out the oxidation method as stated in example 4, one can prepare, for example: 5- hydroxy-7-methylsulfonylxanthone-2-carboxylic acid, methyl 5_hydroxy-7-methylsulfonylxanthone-2-carboxylate, pentyl-5-hydroxy-7-methylsulfonylxanthone-2-carboxylate, 5-methylsulfony1-7-hydroxyxanthone-2-carboxylic acid, methyl- 5-methylsulfonyl-7-hydroxyxanthone-2-carboxylate, and pentyl-5-methylsulfonyl-7-hydroxyxanthone-2-carboxylate.
På samme måte, ved å benytte lavere alkyltio-utgangsmaterialer i stedet for de nevnte metyltio-utgangsmaterialene, kan man fremstille de tilsvarende etylsulfonyl-, propylsulfonyl-, butylsulfonyl- og pentylsulfonyl-forbindelser. Similarly, by using lower alkylthio starting materials instead of the aforementioned methylthio starting materials, one can prepare the corresponding ethylsulfonyl, propylsulfonyl, butylsulfonyl and pentylsulfonyl compounds.
Eksempel 3Example 3
Ved å starte med de passende 5(7)-hydroksy-7(5)-laverealkylsulfinylforbindelsene fra eksempel 7, og benytte alkyleringsmetoden i eksempel 11, del C, under anvendelse av det passende alkylhalogenid med 1-12 karbonatomer, og eventuelt hydrolysere en karboksylsyreester ifølge metoden i eksempel 11, del F, kan man f.eks. fremstille: 5-metoksy-7-metylsulfinylxanton-2-karboksylsyre, By starting with the appropriate 5(7)-hydroxy-7(5)-lower alkylsulfinyl compounds from Example 7, and using the alkylation method of Example 11, part C, using the appropriate alkyl halide of 1-12 carbon atoms, and optionally hydrolyzing a carboxylic acid ester according to the method in example 11, part F, one can e.g. prepare: 5-methoxy-7-methylsulfinylxanthone-2-carboxylic acid,
metyl-5-metoksy-7_metylsulfinylxanton-2-karboksylat, pentyl-5-metoksy-7-metylsulfinylxanton-2-karboksylat, 5-etoksy-7-metylsulfinylxanton-2-karboksylsyre, smp. 273-27^°C, me'tyl-5-et oksy-7-metylsulf inylxant on-2-karboksy lat, pentyl-5-etoksy-7_metylsulfinylxanton-2-karboksylat, 5~propoksy-7-metylsulfinylxanton-2-karboksylsyre, smp. 265-267°C, metyl-5-propoksy-7-metylsulfinylxanton-2-karboksylat, penty1-5_propoksy-7-metylsulfinylxanton-2-karboksylat, 5-isopropoksy-7_metylsulfinylxanton-2-karboksylsyre, smp. 280-282°( metyl-5-isopropoksy-7-metylsulfinylxanton-2-karboksylat, penty1-5_ isopropoksy-7-metylsulfinylxanton-2-karboksylat, 5-butoksy-7-metylsulfinylxanton-2-karboksylsyre, smp. 269-270°C, mety1-5-butoksy-7-metylsulfinylxanton-2-karboksylat, pentyl-5-butoksy-7-metylsulfinylxanton-2-karboksylat, 5-pentoksy-7-metylsulfinylxanton-2-karboksylsyre, smp. 263-265°C, metyl-5-pentoksy-7-metylsulfinylxanton-2-karboksylat, pentyl-5-pentoksy-7-metylsulfinylxanton-2-karboksylat, 5-isopentoksy-7-metylsulfinylxanton-2-karboksylsyre, smp. 271-273°( mety1-5-isopentoksy-7-metylsulfinylxanton-2-karboksylat, penty1-5-isopentoksy-7_metylsulfinylxanton-2-karboksylat, 5-oktyloksy-7-metylsulf inylxant on-2-karboksy lsyre , smp . 258-2'60°C, mety1-5-oktyloksy-7-metylsulfinylxanton-2-karboksylat, pentyl-5-oktyloksy-7-metylsulfinylxanton-2-karboksylat, 5-dodecyloksy-7-metylsulfinylxanton-2-karboksylsyre, smp. 254-255°< metyl-5-dodecyloksy-7-metylsulfinylxanton-2-karboksylat, penty1-5-dodecyloksy-7-metylsulfinylxanton-2-karboksylat, methyl 5-methoxy-7_methylsulfinylxanthone-2-carboxylate, pentyl 5-methoxy-7-methylsulfinylxanthone-2-carboxylate, 5-ethoxy-7-methylsulfinylxanthone-2-carboxylic acid, m.p. 273-27^°C, methyl 5-ethoxy-7-methylsulfinylxanthone-2-carboxylate, pentyl-5-ethoxy-7-methylsulfinylxanthone-2-carboxylate, 5-propoxy-7-methylsulfinylxanthone-2-carboxylic acid , m.p. 265-267°C, methyl 5-propoxy-7-methylsulfinylxanthone-2-carboxylate, penty1-5_propoxy-7-methylsulfinylxanthone-2-carboxylate, 5-isopropoxy-7_methylsulfinylxanthone-2-carboxylic acid, m.p. 280-282° ( methyl 5-isopropoxy-7-methylsulfinylxanthone-2-carboxylate, penty1-5_ isopropoxy-7-methylsulfinylxanthone-2-carboxylate, 5-butoxy-7-methylsulfinylxanthone-2-carboxylic acid, m.p. 269-270° C, methyl 1-5-butoxy-7-methylsulfinylxanthone-2-carboxylate, pentyl 5-butoxy-7-methylsulfinylxanthone-2-carboxylate, 5-pentoxy-7-methylsulfinylxanthone-2-carboxylic acid, mp 263-265°C, methyl 5-pentoxy-7-methylsulfinylxanthone-2-carboxylate, pentyl 5-pentoxy-7-methylsulfinylxanthone-2-carboxylate, 5-isopentoxy-7-methylsulfinylxanthone-2-carboxylic acid, mp 271-273° ( methyl -isopentoxy-7-methylsulfinylxanthone-2-carboxylate, penty1-5-isopentoxy-7-methylsulfinylxanthone-2-carboxylate, 5-octyloxy-7-methylsulfinylxanthone-2-carboxylic acid, m.p. 258-2'60°C, methyl 1- 5-octyloxy-7-methylsulfinylxanthone-2-carboxylate, pentyl 5-octyloxy-7-methylsulfinylxanthone-2-carboxylate, 5-dodecyloxy-7-methylsulfinylxanthone-2-carboxylic acid, mp 254-255°< methyl-5-dodecyloxy -7-methylsulfinylxanthone-2-carboxylate, penty1-5-dodecyloxy-7-methylsulfiny xanthone-2-carboxylate,
samt som de tilsvarende 7-etylsulfinyl-, propylsulfinyl-, butylsulfinyl- og pentylsulfinylforbindelsenei og as well as the corresponding 7-ethylsulfinyl, propylsulfinyl, butylsulfinyl and pentylsulfinyl compounds and
5-metylsulfinyl-7-metoksyxanton-2-karboksylsyre, 5-methylsulfinyl-7-methoxyxanthone-2-carboxylic acid,
metyl-5-mety1sulfinyl-7-metoksyxanton-2-karboksylat, pentyl-5-mety 1sulfiny1-7-metoksyxanton-2-karboksylat, 5-metylsulfiny1-7-etoksyxanton-2-karboksylsyre, methyl 5-methylsulfinyl-7-methoxyxanthone-2-carboxylate, pentyl 5-methylsulfinyl-7-methoxyxanthone-2-carboxylate, 5-methylsulfinyl-7-ethoxyxanthone-2-carboxylic acid,
metyl-5-metylsulfinyl- 7~etoksyxanton-2-karboksylåt, methyl 5-methylsulfinyl-7~ethoxyxanthone-2-carboxylate,
pentyl-5-metylsulfinyl-7-etoksyxanton-2-karboksylat, 5-metylsulfinyl-7_propoksyxanton-2-karboksylsyre, pentyl-5-methylsulfinyl-7-ethoxyxanthone-2-carboxylate, 5-methylsulfinyl-7_propoxyxanthone-2-carboxylic acid,
mety1-5-metylsulfinyl-7-propoksyxanton-2-karboksylat, penty1-5-metylsulfinyl-7-propoksyxanton-2-karboksylat, 5-metylsulfinyl-7-isopropoksyxanton-2-karboksylsyre, smp. 276-278°C, metyl-5-metylsulfinyl-7-isopropoksyxanton-2-karboksylat, pentyl-5-metylsulfinyl-7-isopropoksyxanton-2-karboksylatj5-metylsulfinyl-7_butoksyxanton-2-karboksylsyre, methyl1-5-methylsulfinyl-7-propoxyxanthone-2-carboxylate, penty1-5-methylsulfinyl-7-propoxyxanthone-2-carboxylate, 5-methylsulfinyl-7-isopropoxyxanthone-2-carboxylic acid, m.p. 276-278°C, methyl 5-methylsulfinyl-7-isopropoxyxanthone-2-carboxylate, pentyl-5-methylsulfinyl-7-isopropoxyxanthone-2-carboxylatej5-methylsulfinyl-7-butoxyxanthone-2-carboxylic acid,
mety1-5-metylsulfinyl-7"butoksyxanton-2-karboksylat s pentyl-5-metylsulfinyl-7-butoksyxanton-2-karboksylat, 5-metylsulfiny1-7-pentoksyxanton-2-karboksylsyre, smp. 242-244°C, metyl-5-metylsulfinyl-7-pentoksyxanton-2-karboksylat, penty1-5-metylsulfiny1-7-pentoksyxanton-2-karboksylat, 5-metylsulfiny1-7-isopentoksyxanton-2-karboksylsyre, metyl-5-metylsulfinyl-7-isopentoksyxanton-2-karboksylat, penty1-5-metylsulfinyl-7-isopentoksyxanton-2-karboksylat, 5-metylsulfiny1-7-oktyloksyxanton-2-karboksylsyre, smp. 2l8-219°C, metyl-5-metylsulfinyl-7-oktyloksyxanton-2-karboksylat, pentyl-5-metylsulfiny1~7_oktyloksyxanton-2-karboksylat, 5-metylsulfiny1-7-dodecyloksyxanton-2-karboksylsyre, smp. 196-197°Cjmetyl-5-metylsulfinyl-7-dodecyloksyxanton-2-karboksylat, penty1-5-metylsulfiny1-7-dodecyloksyxanton-2-karboksylat}methyl 1-5-methylsulfinyl-7"butoxyxanthone-2-carboxylate s pentyl-5-methylsulfinyl-7-butoxyxanthone-2-carboxylate, 5-methylsulfiny1-7-pentoxyxanthone-2-carboxylic acid, m.p. 242-244°C, methyl- 5-methylsulfinyl-7-pentoxyxanthone-2-carboxylate, penty1-5-methylsulfinyl-7-pentoxyxanthone-2-carboxylate, 5-methylsulfinyl-7-isopentoxyxanthone-2-carboxylic acid, methyl 5-methylsulfinyl-7-isopentoxyxanthone-2-carboxylate carboxylate, penty1-5-methylsulfinyl-7-isopentoxyxanthone-2-carboxylate, 5-methylsulfiny1-7-octyloxyxanthone-2-carboxylic acid, mp 2l8-219°C, methyl 5-methylsulfinyl-7-octyloxyxanthone-2-carboxylate, pentyl-5-methylsulfiny1~7_octyloxyxanthone-2-carboxylate, 5-methylsulfiny1-7-dodecyloxyxanthone-2-carboxylic acid, mp 196-197°Cjmethyl-5-methylsulfinyl-7-dodecyloxyxanthone-2-carboxylate, penty1-5-methylsulfiny1-7 7-dodecyloxyxanthone-2-carboxylate}
samt som de tilsvarende. 5_etylsulfinyl-, propylsulfinyl-, butylsulf inyl- og pentyls.ulf inylf orbindelser. as well as the corresponding ones. 5_ethylsulfinyl, propylsulfinyl, butylsulfinyl and pentylsulfinyl compounds.
Eksempel j| .Example j| .
Ved å starte med de passende 5(7)-hydroksy-7(5)~laverealkylsulfonylforbindelsene fra eksempel 2, og følge alkyleringsmetoden i eksempel 5, del C, under anvendelse av det passende alkylhalogenid med 1-12 karbonatomer, og eventuelt hydrolysere en karboksylsyreester ifølge metoden i eksempel 5 ., By starting with the appropriate 5(7)-hydroxy-7(5)~lower alkylsulfonyl compounds from Example 2, and following the alkylation method of Example 5, Part C, using the appropriate alkyl halide of 1-12 carbon atoms, and optionally hydrolyzing a carboxylic acid ester according to the method in example 5.,
del F, kan man f.eks. fremstille: 5-metoksy-7_metylsulfonylxanton-2-karboksylsyre 5 part F, one can e.g. prepare: 5-methoxy-7-methylsulfonylxanthone-2-carboxylic acid 5
metyl-5-metoksy-7-metylsulf onylxanton-2-karboksylat, penty1-5-metoksy-7-metylsulfonylxanton-2-karboksylat, 5-etoksy-7-metylsulfonylxanton-2-karboksylsyre, metyl-5_etoksy-7-metylsulfonylxanton-2-karboksylat, penty1-5-etoksy-7-metylsulfonylxanton-2-karboksylat, 5-propoksy-7-metylsulfonylxanton-2-karboksylsyre, mety1-5-propoksy-7-metylsulfonylxanton-2-karboksylat5pentyl-5-propoksy-7-metylsulfonylxanton-2-karboksylat, 5-isoproppksy-7-metylsulfonylxanton-2-karboksylsyre, smp. 3l8°C, metyl-5-isopropoksy-7_mety1sulfonylxanton-2-karboksylat, pentyl-5-isopropoksy-7-metylsulfonylxanton-2-karboksylat, 5-butoksy-7-metylsulfonylxanton-2-karboksylsyre, metyl-5-butoksy-7-metylsulfonylxanton-2-karboksylat, pentyl-5-butoksy-7-metylsulfonylxanton-2-karboksylat, 5-pentoksy-7-metylsulfonylxanton-2-karboksylsyre, metyl-5-pentoksy-7-metylsulfonylxanton-2-karboksylat, pentyl-5_pentoksy-7-metylsulfonylxanton-2-karboksylat, 5-isopentoksy-7-metylsulfonylxanton-2-karboksylsyre, metyl-5-isopentoksy-7-metylsulfonylxanton-2-karboksylat, pentyl-5-isopentoksy-7-metylsulfonylxanton-2-karboksylat, 5-oktyloksy-7-metylsulfonylxanton-2-karboksylsyre, metyl-5-oktyloksy-7-metylsulfonylxanton-2-karboksylat, penty1-5-oktyloksy-7-metylsulfonylxanton-2-karboksylat} 5-dodecyloksy-7-metylsulfonylxanton-2-karboksylsyre, metyl-5-dodecyloksy-7-metylsulfonylxanton-2-karboksylat}pentyl-5-dodecyloksy-7-metylsulfonylxanton-2-karboksylat, samt de tilsvarende 7-etylsulfonyl-, propylsulfonyl-, butylsulfonyl og pentylsulf onylf orbindelsene ms og methyl 5-methoxy-7-methylsulfonylxanthone-2-carboxylate, penty1-5-methoxy-7-methylsulfonylxanthone-2-carboxylate, 5-ethoxy-7-methylsulfonylxanthone-2-carboxylic acid, methyl 5_ethoxy-7-methylsulfonylxanthone-2-carboxylate -carboxylate, penty1-5-ethoxy-7-methylsulfonylxanthone-2-carboxylate, 5-propoxy-7-methylsulfonylxanthone-2-carboxylic acid, methyl 1-5-propoxy-7-methylsulfonylxanthone-2-carboxylate 5pentyl-5-propoxy-7-methylsulfonylxanthone -2-carboxylate, 5-isopropoxy-7-methylsulfonylxanthone-2-carboxylic acid, m.p. 3l8°C, methyl 5-isopropoxy-7-methylsulfonylxanthone-2-carboxylate, pentyl-5-isopropoxy-7-methylsulfonylxanthone-2-carboxylate, 5-butoxy-7-methylsulfonylxanthone-2-carboxylic acid, methyl 5-butoxy-7- methylsulfonylxanthone-2-carboxylate, pentyl-5-butoxy-7-methylsulfonylxanthone-2-carboxylate, 5-pentoxy-7-methylsulfonylxanthone-2-carboxylic acid, methyl 5-pentoxy-7-methylsulfonylxanthone-2-carboxylate, pentyl-5_pentoxy- 7-methylsulfonylxanthone-2-carboxylate, 5-isopentoxy-7-methylsulfonylxanthone-2-carboxylic acid, methyl 5-isopentoxy-7-methylsulfonylxanthone-2-carboxylate, pentyl 5-isopentoxy-7-methylsulfonylxanthone-2-carboxylate, 5- Octyloxy-7-methylsulfonylxanthone-2-carboxylic acid, methyl 5-octyloxy-7-methylsulfonylxanthone-2-carboxylate, penty1-5-octyloxy-7-methylsulfonylxanthone-2-carboxylate} 5-dodecyloxy-7-methylsulfonylxanthone-2-carboxylic acid, methyl-5-dodecyloxy-7-methylsulfonylxanthone-2-carboxylate}pentyl-5-dodecyloxy-7-methylsulfonylxanthone-2-carboxylate, as well as the corresponding 7-ethylsulfonyl-, propylsulfonyl-, butylsulfonyl l and the pentylsulfonyl compounds ms and
5-metylsulfonyl-7-metoksyxanton-2-karboksylsyre, metyl-5-metylsulfony1-7-metoksyxanton-2-karboksylat, pentyl-5-metylsulfonyl-7-metoksyxanton-2-karboksylat, 5-metylsulfony1-7-etoksyxanton-2-karboksylsyre, metyl-5-metylsulfonyl-7-etoksyxanton-2-karboksylat, pentyl-5-metylsulfonyl-7-etoksyxanton-2-karboksylat, 5-metylsulfony1-7-propoksyxanton-2-karboksylsyre, metyl-5-metylsulfonyl-7~propoksyxanton-2-karboksylat, pentyl-5-metylsulfony1-7-propoksyxanton-2-karboksylat, 5-metylsulfony1-7-isopropoksyxanton-2-karboksylsyre, smp. 308-309°C, 5-methylsulfonyl-7-methoxyxanthone-2-carboxylic acid, methyl 5-methylsulfonyl 1-7-methoxyxanthone-2-carboxylate, pentyl 5-methylsulfonyl-7-methoxyxanthone-2-carboxylate, 5-methylsulfonyl 1-7-ethoxyxanthone-2-carboxylate carboxylic acid, methyl-5-methylsulfonyl-7-ethoxyxanthone-2-carboxylate, pentyl-5-methylsulfonyl-7-ethoxyxanthone-2-carboxylate, 5-methylsulfonyl1-7-propoxyxanthone-2-carboxylic acid, methyl-5-methylsulfonyl-7~ propoxyxanthone-2-carboxylate, pentyl-5-methylsulfony1-7-propoxyxanthone-2-carboxylate, 5-methylsulfony1-7-isopropoxyxanthone-2-carboxylic acid, m.p. 308-309°C,
metyl-5-nietylsulf ony 1~7-i sopropoksyxant on-2-karboksy lat, pentyl-5-metylsulfonyl-7-isopropoksyxanton-2-karboksylat, methyl-5-niethylsulfony 1~7-isopropoxyxanthone-2-carboxylate, pentyl-5-methylsulfonyl-7-isopropoxyxanthone-2-carboxylate,
5-metylsulfonyl-7-butoksyxanton-2-karboksylsyre, 5-methylsulfonyl-7-butoxyxanthone-2-carboxylic acid,
metyl-5-metylsulfony1-7-butoksyxanton-2-karboksylat, methyl 5-methylsulfony1-7-butoxyxanthone-2-carboxylate,
penty1-5-metylsulfonyl-7-butoksyxanton-2-karboksylat, 5-metylsulfony1-7-pentoksyxanton-2-karboksylsyre, penty1-5-methylsulfonyl-7-butoxyxanthone-2-carboxylate, 5-methylsulfonyl1-7-pentoxyxanthone-2-carboxylic acid,
metyl-5-metylsulfonyl-7-pentoksyxanton-2-karboksylat, penty1-5-metylsulfonyl-7-pentoksyxanton-2-karboksylat, 5-metylsulfonyl-7-isopentoksyxanton-2-karboksylat, metyl-5-mety1sulfony1-7-isopentoksyxanton-2-karboksylat, pentyl-5-metylsulfonyl-7_isopentoksyxanton-2-karboksylat, 5-metylsulfony1-7-oktyloksyxanton-2-karboksylsyre, metyl-5-metylsulfonyl-7_oktyloksyxanton-2-karboksylat, pentyl-5-metylsulfonyl-7-oktyloksyxanton-2-karboksylat, 5-metylsulfony1-7-dodecyloksyxanton-2-karboksylsyre, mety1-5-mety1sulfony1-7-dodecyloksyxanton-2-karboksylat, pentyl-5-metylsulfony1-7-dodecyloksyxanton-2-karboksylat, methyl 5-methylsulfonyl-7-pentoxyxanthone-2-carboxylate, penty1-5-methylsulfonyl-7-pentoxyxanthone-2-carboxylate, 5-methylsulfonyl-7-isopentoxyxanthone-2-carboxylate, methyl 5-methyl1sulfony1-7-isopentoxyxanthone-2-carboxylate 2-carboxylate, pentyl-5-methylsulfonyl-7_isopentoxyxanthone-2-carboxylate, 5-methylsulfony1-7-octyloxyxanthone-2-carboxylic acid, methyl 5-methylsulfonyl-7_octyloxyxanthone-2-carboxylate, pentyl-5-methylsulfonyl-7-octyloxyxanthone-2-carboxylate 2-carboxylate, 5-methylsulfony1-7-dodecyloxyxanthone-2-carboxylic acid, methyl 1-5-methylsulfony1-7-dodecyloxyxanthone-2-carboxylate, pentyl 5-methylsulfony1-7-dodecyloxyxanthone-2-carboxylate,
samt de tilsvarende 5_etylsulfonyl-, propylsulfonyl-, butylsulf onyl-,■ og pentylsulfonylforbindelsene. as well as the corresponding 5-ethylsulfonyl, propylsulfonyl, butylsulfonyl, and pentylsulfonyl compounds.
Eksempel 5Example 5
A. Til en suspensjon av 14,5 g 5-metøksy-7-(metyltio)-xanton-2-karboksylsyre i 350 ml eddiksyreanhydrid, tilsettes 100 ml 47% hydrojodsyre dråpevis under avkjøling med is. Etter tilbakeløpskoking.av den resulterende blanding i 20 timer, blir den fortynnet med 750 ml varmt vann og avkjøles. Det gule produkt frafiltreres, vaskes med vann og tørkes og dette gir 12,8 g A. To a suspension of 14.5 g of 5-methoxy-7-(methylthio)-xanthone-2-carboxylic acid in 350 ml of acetic anhydride, 100 ml of 47% hydroiodic acid is added dropwise while cooling with ice. After refluxing the resulting mixture for 20 hours, it is diluted with 750 ml of hot water and cooled. The yellow product is filtered off, washed with water and dried, and this gives 12.8 g
. 5-hydroksy-7-(metyltio^anton-2-karboksylsyre.. 5-Hydroxy-7-(methylthio-anthone-2-carboxylic acid).
Ved å benytte 5-metyltio-7_metoksyxanton-2-karboksylsyre i steden for 5_metoksy-7-(metyltio)-xanton-2-karboksylsyre oppnås på samme måte 5_metyltio-7-hydroksyxanton-2-karboksylsyre. By using 5-methylthio-7-methoxyxanthone-2-carboxylic acid instead of 5-methoxy-7-(methylthio)-xanthone-2-carboxylic acid, 5-methylthio-7-hydroxyxanthone-2-carboxylic acid is obtained in the same way.
På lignende måte oppnås andre 5-hydroksy-7_(lavere alkyltio)-xanton-2-karboksylsyrer og 5-lavere alkyltio-7~hydroksy-xanton-2-karboksylsyrer. In a similar manner, other 5-hydroxy-7-(lower alkylthio)-xanthone-2-carboxylic acids and 5-lower alkylthio-7-hydroxy-xanthone-2-carboxylic acids are obtained.
B. En blanding av 6,65 g 5-hydroksy-7~(metyltio)-xanton-2-karboksylsyre, 4,5 g tørt litiumkarbonat, 4 ml metyljodid og 70 ml dimetylformamid, omrøres ved romtemperatur i 20 timer. Etter til-setning, av et overskudd eddiksyre/vann (1:1), fjernes overskudd metyljodid i en roterende fordamper. D.et krystallinske produkt frafiltreres, vaskes og tørkes og dette gir 6,8 g metyl-5-hydroksy-7-(metyltio)-xanton-2-karbbksylat, smp. 286°C (dekomp.). B. A mixture of 6.65 g of 5-hydroxy-7-(methylthio)-xanthone-2-carboxylic acid, 4.5 g of dry lithium carbonate, 4 ml of methyl iodide and 70 ml of dimethylformamide, is stirred at room temperature for 20 hours. After addition of excess acetic acid/water (1:1), excess methyl iodide is removed in a rotary evaporator. D. a crystalline product is filtered off, washed and dried and this gives 6.8 g of methyl 5-hydroxy-7-(methylthio)-xanthone-2-carboxylate, m.p. 286°C (decomp.).
Ved at man i ovenstående metode benytter 5-metyltio-7-hydroksyxanton-2-karboksylsyre oppnås likeledes metyl-5-.metyltio-7-hydroksyxanton-2-karboksylat, smp. 290°C (dekomp.). By using 5-methylthio-7-hydroxyxanthone-2-carboxylic acid in the above method, methyl 5-methylthio-7-hydroxyxanthone-2-carboxylate is also obtained, m.p. 290°C (decomp.).
Metoden gjentas under anvendelse av forskjellige lavere alkyljodider for dermed å fremstille lavere alkylsyreestere herav, f.eks. etyl-5~hydroksy-7-(metyltio)-xanton-2-karboksylat, penty1-5-hydroksy-7-(metyltio)-xanton-2-karboksylat og etyl-5-metyltio-7-hydroksyxanton-2-karboksylat og. The method is repeated using different lower alkyl iodides to thereby prepare lower alkyl acid esters thereof, e.g. ethyl 5-hydroxy-7-(methylthio)-xanthone-2-carboxylate, pentyl-5-hydroxy-7-(methylthio)-xanthone-2-carboxylate and ethyl 5-methylthio-7-hydroxyxanthone-2-carboxylate and .
pentyl-5-metyltio-7-hydroksyxanton-2-karboksylat.pentyl 5-methylthio-7-hydroxyxanthone-2-carboxylate.
C. 1,55 g metyl-5-hydroksy-7_(metyltio)-xanton-2-karboksylat omrøres ved romtemperatur med 2,5 g oktylbromid og 1,0.g kaliumkarbonat i 30 ml dimetylformamid i 18 timer. Etter surgjøring med fortynnet saltsyre, ekstraheres blandingen med kloroform, ekstraktene vaskes med vann, tørkes over magnesiumsulfat og inndampes. Filtrering av en kloroformoppløsning av det urene produkt gjennom aluminiumoksyd (aktivitet II) ga 2,0 g metyl-5-n-oktyloksy-7-(metyltio)-xanton-2-karboksylat. C. 1.55 g of methyl 5-hydroxy-7-(methylthio)-xanthone-2-carboxylate is stirred at room temperature with 2.5 g of octyl bromide and 1.0 g of potassium carbonate in 30 ml of dimethylformamide for 18 hours. After acidification with dilute hydrochloric acid, the mixture is extracted with chloroform, the extracts are washed with water, dried over magnesium sulfate and evaporated. Filtration of a chloroform solution of the crude product through alumina (activity II) gave 2.0 g of methyl 5-n-octyloxy-7-(methylthio)-xanthone-2-carboxylate.
Ved i foregående metode å benytte metyl-5-metyltio-7_ hydroksyxanton-2-karboksylat oppnås på samme måte metyl-5-metyltio-7-n-oktyloksyxanton-2-karboksylat. By using methyl-5-methylthio-7-hydroxyxanthone-2-carboxylate in the preceding method, methyl-5-methylthio-7-n-octyloxyxanthone-2-carboxylate is obtained in the same way.
Ovenstående metode gjentas under anvendelse av andre høyere alkylbromider for dermed å oppnå 5- og 7-høyere alkoksy-forbindelser som f.eks. metyl-5-n-heksyloksy-7-(metyltio)-xanton-2-karboksylat, mety1-5-n-heptyloksy- 7-(metyltio)-xanton-2-karboksylat, metyl-5-n-dédecyloksy-7-(metyltio)-xanton-2-karboksylat, og mety1-5-metyltio-7-n-heksyloksyxanton-2-karboksylat, metyl-5-metyltio-7-n-heptyloksyxanton-2-karboksylat, og mety1-5-metyltio-7-n-dodecyloksyxanton-2-karboksylat. The above method is repeated using other higher alkyl bromides in order to obtain 5- and 7-higher alkoxy compounds such as e.g. methyl 5-n-hexyloxy-7-(methylthio)-xanthone-2-carboxylate, methyl 1-5-n-heptyloxy-7-(methylthio)-xanthone-2-carboxylate, methyl 5-n-dedecyloxy-7- (methylthio)-xanthone-2-carboxylate, and methyl 1-5-methylthio-7-n-hexyloxyxanthone-2-carboxylate, methyl 5-methylthio-7-n-heptyloxyxanthone-2-carboxylate, and methyl 1-5-methylthio- 7-n-dodecyloxyxanthone-2-carboxylate.
På lignende måter kan andre lavere alkylestere benyttes i steden, for metylesteren og ved bruk av et passende høyere alkylbromid, oppnås f.eks. ety1-5-n-oktyloksy-7-(metyltio)-xanton-2-karboksylat, pentyl-5-n-oktyloksy-7-(metyltio)-xanton-2-karboksylat, ety1-5-n-heksyloksy-7-(metyltio)-xanton-2-karboksylat, In similar ways, other lower alkyl esters can be used instead, for the methyl ester and by using a suitable higher alkyl bromide, e.g. ethyl 1-5-n-octyloxy-7-(methylthio)-xanthone-2-carboxylate, pentyl 5-n-octyloxy-7-(methylthio)-xanthone-2-carboxylate, ethyl 1-5-n-hexyloxy-7- (methylthio)-xanthone-2-carboxylate,
pentyl-5-n-heptyloksy-7-(metyltio)-xanton-2-karboksylat, pentyl 5-n-heptyloxy-7-(methylthio)-xanthone-2-carboxylate,
etyl-5-n-dodecyloksy-7_(metyltio)-xanton-2-karboksylat, etyl-5-metyltio-7-n-oktyloksyxanton-2-karboksylat, ethyl 5-n-dodecyloxy-7_(methylthio)-xanthone-2-carboxylate, ethyl 5-methylthio-7-n-octyloxyxanthone-2-carboxylate,
penty1-5-metyltio-7-n-oktyloksyxanton-2-karboksylat, etyl-5-metyltio-7~n-heksyloksyxanton-2-karboksylat, pentyl-5-metyltio-7-n-heksyloksyxanton-2-karboksylat, og etyl-5-metyltio-7-n-dodecyloksyxanton-2-karboksylat. penty1-5-methylthio-7-n-octyloxyxanthone-2-carboxylate, ethyl 5-methylthio-7~n-hexyloxyxanthone-2-carboxylate, pentyl 5-methylthio-7-n-hexyloxyxanthone-2-carboxylate, and ethyl -5-methylthio-7-n-dodecyloxyxanthone-2-carboxylate.
D. Til 2,0 g metyl-5-n-oktyloksy-7-(metyltio)-xanton-2-karboksylat i 60 ml kloroform tilsettes langsomt en oppløsning av 910 mg m-klorperoksybenzosyre i 40 ml kloroform mens temperaturen holdes ved ca. 0°C. Etter at tilsetningen.>er ferdig filtreres oppløsningen gjennom aluminiumoksyd (aktivitet III) og .inndampes, og dette gir 2,0 g metyl-5-n-oktyloksy-7-metylsulfinyl-xanton- 2-karboksylat . D. To 2.0 g of methyl-5-n-octyloxy-7-(methylthio)-xanthone-2-carboxylate in 60 ml of chloroform, a solution of 910 mg of m-chloroperoxybenzoic acid in 40 ml of chloroform is slowly added while the temperature is maintained at approx. 0°C. After the addition is complete, the solution is filtered through aluminum oxide (activity III) and evaporated, and this gives 2.0 g of methyl-5-n-octyloxy-7-methylsulfinyl-xanthone-2-carboxylate.
Ved i foregående metode.:'år-bénytte -metyl-5-métylt io-7_n_ dktyloksyxåhton^2-karboksylat oppnås på samme måte metyl-5-metyl-sulfinyl-7-n-oktyloksyxanton-2-karboksylat. In the preceding method, methyl-5-methyl io-7-n-octyloxyxanthone-2-carboxylate is obtained in the same way methyl-5-methyl-sulfinyl-7-n-octyloxyxanthone-2-carboxylate.
Ved å benytte de andre forbindelsene fremstilt i del C i dette eksempel i steden for.5-n-oktyloksy-7-(metyltio)-xanton-2-karboksylat, oppnås f.eks.: mety1-5-n-heksyloksy-7-metylsulfinylxanton-2-karboksylat, metyl-5-n-heptyloksy-7-metylsulfinylxanton-2-karboksylat, metyl-5-n-dodecyloksy-7-metylsulfinylxanton-2-karboksylat, etyl-5-n-oktyloksy-7-metylsulfinylxanton-2-karboksylat, pentyl-5-n-oktyloksy-7-metylsulfinylxanton-2-karboksylat, etyl-5-n-heksyloksy-7_metylsulfinylxanton-2-karboksylat, pentyl-5-n-heptyloksy-7-metylsulfinylxanton-2-karboksylat, og etyl-5-n-dodecyloksy-7-metylsulfinylxanton-2-karboksylat, og metyl-5-metylsulfiny1-7-n-heksyloksyxanton-2-karboksylat, metyl-5-metylsulfinyl-7-n-heptyloksyxanton-2-karboksylat,■ metyl-5-metylsulfinyl-7-n-dodecyloksyxanton-2-karboksylat, etyl-5-metylsulfinyl-7-n-oktyloksyxanton-2-karboksylat, penty1-5-metylsulfinyl-7~n-oktyloksyxanton-2-karboksylat, etyl-5-metylsulfinyl-7-n-heksyloksyxanton-2-karboksylat, penty1-5-metylsulfinyl-7-n-heksyloksyxanton-2-karboksylat, og etyl-5-metylsulfinyl-7-n-dodecyloksyxanton-2-karboksylat. By using the other compounds prepared in part C in this example in place of 5-n-octyloxy-7-(methylthio)-xanthone-2-carboxylate, for example: methyl 1-5-n-hexyloxy-7 -methylsulfinylxanthone-2-carboxylate, methyl 5-n-heptyloxy-7-methylsulfinylxanthone-2-carboxylate, methyl 5-n-dodecyloxy-7-methylsulfinylxanthone-2-carboxylate, ethyl 5-n-octyloxy-7-methylsulfinylxanthone -2-carboxylate, pentyl-5-n-octyloxy-7-methylsulfinylxanthone-2-carboxylate, ethyl 5-n-hexyloxy-7_methylsulfinylxanthone-2-carboxylate, pentyl-5-n-heptyloxy-7-methylsulfinylxanthone-2-carboxylate , and ethyl 5-n-dodecyloxy-7-methylsulfinylxanthone-2-carboxylate, and methyl 5-methylsulfinyl-7-n-hexyloxyxanthone-2-carboxylate, methyl 5-methylsulfinyl-7-n-heptyloxyxanthone-2-carboxylate ,■ methyl 5-methylsulfinyl-7-n-dodecyloxyxanthone-2-carboxylate, ethyl 5-methylsulfinyl-7-n-octyloxyxanthone-2-carboxylate, penty1-5-methylsulfinyl-7~n-octyloxyxanthone-2-carboxylate, ethyl 5-methylsulfinyl-7-n-hexyloxyxanthone-2-carboxylate, penty1-5-methylsulfinyl-7-n-hexyloc syxanthone-2-carboxylate, and ethyl 5-methylsulfinyl-7-n-dodecyloxyxanthone-2-carboxylate.
E. Metyl-5-n-oktyloksy-7-(metyltio)-xanton-2-karboksylat (750 mg;);, 2 ml hydrogenperoksyd (30$) og 40 ml eådiksyre oppvarmes på et dampbad (80°C) i 90 minutter. Tynnsjiktskromatografi indikerer fravær av utgangsmateriale. Blandingen fortynnes med 60 ml varmt vann og blandingen avkjøles, det faste stoff frafiltreres og tørkes hvilket gir metyl-5-n-oktyloksy-7-metylsulfonylxanton-2-karboksylat som kan omkrystalliseres fra eddiksyre/vann. E. Methyl 5-n-octyloxy-7-(methylthio)-xanthone-2-carboxylate (750 mg);, 2 ml of hydrogen peroxide (30$) and 40 ml of acetic acid are heated on a steam bath (80°C) for 90 minutes. Thin layer chromatography indicates the absence of starting material. The mixture is diluted with 60 ml of hot water and the mixture is cooled, the solid is filtered off and dried to give methyl 5-n-octyloxy-7-methylsulfonylxanthone-2-carboxylate which can be recrystallized from acetic acid/water.
Likeledes, ved å benytte metyl-5-metyltio-7-n-oktyloksy-2-karboksylat i foregående metode oppnås metyl-5_metylsulfonyl-7-n-oktyloksyxanton-2-karboksylat. Likewise, by using methyl 5-methylthio-7-n-octyloxy-2-carboxylate in the preceding method, methyl 5-methylsulfonyl-7-n-octyloxyxanthone-2-carboxylate is obtained.
På samme måte, ved å benytte de andre forbindelsene fremstilt i del C i dette eksempel i steden for 5-n-oktyloksy-7~Similarly, using the other compounds prepared in part C of this example in place of 5-n-octyloxy-7~
(metyltio)-xanton-2-karboksylat, oppnås f.eks.: mety1-5-n-heksyloksy-7-metylsulfonylxanton-2-karboksylat, mety1-5-n-heptyloksy-7-metylsulfonylxanton-2-karboksylat, metyl-5_n-dodecyloksy-7-metylsulfonylxanton-2-karboksylat, ety1-5-n-oktyloksy-7-metylsulfonylxanton-2-karboksylat, penty1-5-n-oktyloksy-7-metylsulfonylxanton-2-karboksylat, etyl-5_n-heksyloksy-7-metylsulfonylxanton-2-karboksylat, pentyl-5-n-heptyloksy-7-metylsulfonylxanton-2-karboksylat, og etyl-5-n-dodecyloksy-7_metylsulfonylxanton-2-karboksylat, og metyl-5-metylsulfonyl-7-n-heksyloksyxanton-2-karboksylat, metyl-5-metylsulfony1-7-n-heptyloksyxanton-2-karboksylat, metyl-5-metylsulfonyl-7-n-dodecyloksyxanton-2-karboksylat, etyl-5-metylsulfonyl-7-n-oktyloksyxanton-2-karboksylat, pentyl-5-metylsulfonyl-7-n-oktyloksyxanton-2-karboksylat, etyl-5-metylsulfonyl-7-n-heksyloksyxanton-2-karboksylat, pentyl-5-metylsulfonyl-7-n-heksyloksyxanton-2-karboksylat, og etyl-5-metylsulfonyl-7-n-dodecyloksyxanton-2-karboksylat. (methylthio)-xanthone-2-carboxylate, obtained e.g.: methyl 1-5-n-hexyloxy-7-methylsulfonylxanthone-2-carboxylate, methyl 1-5-n-heptyloxy-7-methylsulfonylxanthone-2-carboxylate, methyl- 5_n-dodecyloxy-7-methylsulfonylxanthone-2-carboxylate, ethyl 1-5-n-octyloxy-7-methylsulfonylxanthone-2-carboxylate, penty1-5-n-octyloxy-7-methylsulfonylxanthone-2-carboxylate, ethyl 5_n-hexyloxy- 7-methylsulfonylxanthone-2-carboxylate, pentyl-5-n-heptyloxy-7-methylsulfonylxanthone-2-carboxylate, and ethyl 5-n-dodecyloxy-7-methylsulfonylxanthone-2-carboxylate, and methyl-5-methylsulfonyl-7-n- hexyloxyxanthone-2-carboxylate, methyl 5-methylsulfonyl1-7-n-heptyloxyxanthone-2-carboxylate, methyl 5-methylsulfonyl-7-n-dodecyloxyxanthone-2-carboxylate, ethyl 5-methylsulfonyl-7-n-octyloxyxanthone-2-carboxylate 2-carboxylate, pentyl-5-methylsulfonyl-7-n-octyloxyxanthone-2-carboxylate, ethyl 5-methylsulfonyl-7-n-hexyloxyxanthone-2-carboxylate, pentyl-5-methylsulfonyl-7-n-hexyloxyxanthone-2-carboxylate carboxylate, and ethyl 5-methylsulfonyl-7-n-dodecyloxyxanthone-2-carboxylate.
P. 2,0 g metyl-5-n-oktyloksy-7-metylsulfinylxanton-2-karboksylat kokes under tilbakeløp i 30 minutter med 0,5 g kaliumhydroksyd i 80 ml etanol inneholdende 20 ml vann. Etter surgjøring med fortynnet saltsyre, isoleres bunnfallet ved filtrering med sug og omkrystalliseres fra tetrahydrofuran/ etanol, hvilket gir 1,8 g 5-n-oktyloksy-7-metylsulfinylxanton-2-karboksylsyre. P. 2.0 g of methyl-5-n-octyloxy-7-methylsulfinylxanthone-2-carboxylate is refluxed for 30 minutes with 0.5 g of potassium hydroxide in 80 ml of ethanol containing 20 ml of water. After acidification with dilute hydrochloric acid, the precipitate is isolated by suction filtration and recrystallized from tetrahydrofuran/ethanol, which gives 1.8 g of 5-n-octyloxy-7-methylsulfinylxanthone-2-carboxylic acid.
Likeledes, ved som utgangsmateriale å benytte deLikewise, by using them as starting material
andre forbindelsene oppnådd i del D og del E i dette eksempel i steden for metyl-5-n-oktyloksy-7-metylsulfinylxanton-2-karboksylat, oppnås f.eks.: 5-metylsulfinyl-7-n-oktyloksyxanton-2-karboksylsyre, 5-n-oktyloksy-7-metylsulfonylxanton-2-karboksyl syre, 5-metylsulfony1-7-n-oktyloksyxanton-2-karboksylsyre, 5-n-heksyloksy-7-metylsulfinylxanton-2-karboksylsyre, 5-n-heptyloksy-7-metylsulfinylxanton-2-karboksylsyre, 5-n-dodecyloksy-7-metylsulfinylxanton-2-karboksylsyre, 5-metylsulfiny1-7-n-heksyloksyxanton-2-karboksylsyre, 5-metylsulfinyl-7~n-heptyloksyxanton-2-karboksylsyre, og 5-metylsulfinyl-7-n-dodecyloksyxanton-2-karboksylsyre, 5-n-heksyloksy-7-metylsulfonylxanton-2-karboksylsyre, 5-n-heptyl-oksy-7-metylsulf onylxanton-2-karboksy lsyre , 5-n-dodecyloksy-7-metylsulfonylxanton-2-karboksylsyre, 5-metylsulfony1-7-n-heksyloksyxanton-2-karboksylsyre, the other compounds obtained in part D and part E in this example instead of methyl 5-n-octyloxy-7-methylsulfinylxanthone-2-carboxylate are obtained, for example: 5-methylsulfinyl-7-n-octyloxyxanthone-2-carboxylic acid , 5-n-octyloxy-7-methylsulfonylxanthone-2-carboxylic acid, 5-methylsulfonyl 1-7-n-octyloxyxanthone-2-carboxylic acid, 5-n-hexyloxy-7-methylsulfinylxanthone-2-carboxylic acid, 5-n-heptyloxy- 7-methylsulfinylxanthone-2-carboxylic acid, 5-n-dodecyloxy-7-methylsulfinylxanthone-2-carboxylic acid, 5-methylsulfinyl-7-n-hexyloxyxanthone-2-carboxylic acid, 5-methylsulfinyl-7~n-heptyloxyxanthone-2-carboxylic acid, and 5-methylsulfinyl-7-n-dodecyloxyxanthone-2-carboxylic acid, 5-n-hexyloxy-7-methylsulfonylxanthone-2-carboxylic acid, 5-n-heptyl-oxy-7-methylsulfonylxanthone-2-carboxylic acid, 5-n -dodecyloxy-7-methylsulfonylxanthone-2-carboxylic acid, 5-methylsulfonyl-1-7-n-hexyloxyxanthone-2-carboxylic acid,
5-metylsulfonyl-7-n-heptyloksyxanton-2-karboksylsyre, og 5-metylsulfony1-7-n-dodecyloksyxanton-2-karboksylsyre. 5-methylsulfonyl-7-n-heptyloxyxanthone-2-carboxylic acid, and 5-methylsulfonyl-7-n-dodecyloxyxanthone-2-carboxylic acid.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO753168A NO753168L (en) | 1974-01-08 | 1975-09-17 |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05431794 US3894049A (en) | 1972-06-05 | 1974-01-08 | Disubstituted xanthone carboxylic acid compounds |
| NO744506A NO744506L (en) | 1974-01-08 | 1974-12-13 | |
| NO753168A NO753168L (en) | 1974-01-08 | 1975-09-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO753168L true NO753168L (en) | 1975-07-09 |
Family
ID=27352716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO753168A NO753168L (en) | 1974-01-08 | 1975-09-17 |
Country Status (1)
| Country | Link |
|---|---|
| NO (1) | NO753168L (en) |
-
1975
- 1975-09-17 NO NO753168A patent/NO753168L/no unknown
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