CS202239B1 - Process for preparing new 11h-dibenzo/b,e/-1,4-dithiepine - Google Patents
Process for preparing new 11h-dibenzo/b,e/-1,4-dithiepine Download PDFInfo
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- CS202239B1 CS202239B1 CS309378A CS309378A CS202239B1 CS 202239 B1 CS202239 B1 CS 202239B1 CS 309378 A CS309378 A CS 309378A CS 309378 A CS309378 A CS 309378A CS 202239 B1 CS202239 B1 CS 202239B1
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- dibenzo
- dithiepine
- formula
- preparing new
- bromophenyl
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- 238000004519 manufacturing process Methods 0.000 title description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229940116318 copper carbonate Drugs 0.000 claims 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- QEPDGDBSYSTKQC-UHFFFAOYSA-N 1-(bromomethyl)-2-[[2-(bromomethyl)phenyl]disulfanyl]benzene Chemical compound BrCC1=CC=CC=C1SSC1=CC=CC=C1CBr QEPDGDBSYSTKQC-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 2
- ZPZGXSDRHRPPLU-UHFFFAOYSA-N 6h-benzo[c][1,5]benzodithiepine Chemical compound C1SC2=CC=CC=C2SC2=CC=CC=C12 ZPZGXSDRHRPPLU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000013078 crystal Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LZSYGJNFCREHMD-UHFFFAOYSA-N 1-bromo-2-(bromomethyl)benzene Chemical compound BrCC1=CC=CC=C1Br LZSYGJNFCREHMD-UHFFFAOYSA-N 0.000 description 1
- YUQUNWNSQDULTI-UHFFFAOYSA-N 2-bromobenzenethiol Chemical compound SC1=CC=CC=C1Br YUQUNWNSQDULTI-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 101100311330 Schizosaccharomyces pombe (strain 972 / ATCC 24843) uap56 gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 bis [2- (2-bromophenylthiomethyl) phenyl] disulfide Chemical compound 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000000508 neurotrophic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000506 psychotropic effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 101150018444 sub2 gene Proteins 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Description
Vynález se týká způsobu přípravy nového HH-dibenzo(b, e)-1,4-dithiepinu vzorce IThe invention relates to a process for the preparation of the novel HH-dibenzo (b, e) -1,4-dithiepine of the formula I
•X .4 meziproduktu výroby farmakodynamicky účinných tricyklických sloučenin, zvláště látek neurotropních a psychotropních. Z tohoto důvodu je látka technicky důležitá.X.4 of the intermediate for the production of pharmacodynamically active tricyclic compounds, in particular neurotrophic and psychotropic substances. For this reason, the substance is technically important.
Podle vynálezu se látka vzorce I připravuje tak, že se 2-bromfenyl-2'-merkaptobenzylsulfid vzorce IIAccording to the invention, the compound of the formula I is prepared by reacting 2-bromophenyl-2'-mercaptobenzylsulfide of the formula II
cyklizuje působením bezvodého uhličitanu alkalického kovu a mědí v prostředí dimethylformamidu, při teplotě varu reakční směsi.cyclized by treatment with anhydrous alkali metal carbonate and copper in dimethylformamide, at the boiling point of the reaction mixture.
Při provedení způsobu podle vynálezu je možno použit k cyklizáci látky vzorce II v čistém stavu nebo též in šitu, tj. bez izolace v čistém stavu. Oběma cestami lze získat látku vzorce I jako krystalickou sub2 stanci, krystalující z methanolu ve dvou krystalových modifikacích. Níže tající má t. t. 44 až 45 °C, výše tající 55,5 až 56 °C.In carrying out the process according to the invention, it is possible to use the compounds of formula (II) in pure state or in situ, i.e. without isolation in pure state, for cyclization. In both ways, the compound of formula I can be obtained as a crystalline sub2 station, crystallizing from methanol in two crystal modifications. Melting point: mp 44-45 ° C; melting point: 55.5-56 ° C.
Výchozí látka vzorce II je látka nová, jejíž způsoby přípravy jsou popsány v příkladech provedení. Získá se z těchto známých látek: bis(2-brommethylfenyl)disulfidu (R. M. Pierson se sp., USA pat. č. 3 072 707), 1,2benzendithiolu (I. Degani, R. Fochi, Synthesis 1976, 471) a 2-brombenzyibromidu (R. L. Letsinger, J. H. Skoog, J. Am. Chem. Soc. 77, 5176, 1955).The starting material of formula (II) is a novel material, the preparation methods of which are described in the examples. It is obtained from the following known substances: bis (2-bromomethylphenyl) disulfide (RM Pierson et al., U.S. Pat. No. 3,072,707), 1,2-benzenedithiol (I. Degani, R. Fochi, Synthesis 1976, 471) and 2. bromobenzyibromide (RL Letsinger, JH Skoog, J. Am. Chem. Soc. 77, 5176, 1955).
Další podrobnosti způsobu přípravy látky vzorce I podle tohoto vynálezu uvádějí příklady provedení, které jsou ovšem jen ilustrací možností vynálezu a není jejich účelem všechny tyto možnosti popisovat.Further details of the process for the preparation of the compound of the formula I according to the invention are given by way of example, which are only illustrative of the possibilities of the invention and are not intended to describe all these possibilities.
Příklady provedení:Examples:
1. Z Izolovaného meziproduktu II1. From the isolated intermediate II
Směs 17,1 g 2-bromfenyl-2'-merkaptobenzylsulfidu, 300 ml dimethylformamidu, 8,3 g bezvodého uhličitanu draselného a 1,5 g čerstvě vyredukované mědi se vaří v dusíkové atmosféře 6 hodin pod zpětným chladičem. Potom se dimethylformamid ve vakuu oddestiluje, zbytek se zředí 200 ml vody a extrahuje benzenem. Extrakt se vysuší síranem hořečnatým a odpaří. Zbytek se rozpustí za tepla v 25 ml ethanolu a ponechá krystalizaci. Stáním se vyloučí 2,1 g nežádoucí krystalické látky s t. t. 171 až 172 °C,A mixture of 17.1 g of 2-bromophenyl-2'-mercaptobenzylsulfide, 300 ml of dimethylformamide, 8.3 g of anhydrous potassium carbonate and 1.5 g of freshly reduced copper was heated under reflux for 6 hours. The dimethylformamide was then distilled off in vacuo, the residue was diluted with 200 ml of water and extracted with benzene. The extract was dried (MgSO4) and evaporated. The residue was dissolved in 25 ml of ethanol while warming and left to crystallize. On standing, 2.1 g of an undesired crystalline substance of m.p.
202 239202 239
202 239 . . 4 která se odsaje a odstraní. Filtrát se odpaří do sucha a podrobí destilaci. Získá se 5,25 g surového llH-dibenzo(b, e)-_l,4-dithiepinu s t. v. 175 až 190 °C/160 Pa. Čistá látka se získá chromatografii na sloupci silikagelu při eluci petroletherem, přičemž se předem odstraní malý podíl méně polární látky. Čistý produkt krystaluje z methanolu ve formě dvou krystalových modifikací s t. t. 44 až 45 °C a 55,5 až 56 °C. Obě formy poskytují uspokojivou analýzu a jejich spektra jsou ve shodě s uvedenou strukturou látky I.202 239. . 4 which is aspirated and removed. The filtrate was evaporated to dryness and distilled. 5.25 g of crude 11H-dibenzo (b, e) -1,4-dithiepine, m.p. 175 DEG-190 DEG C./0.1 mbar, are obtained. Pure material was obtained by silica gel column chromatography eluting with petroleum ether, removing a small portion of the less polar material beforehand. The pure product crystallizes from methanol in the form of two crystal modifications with mp 44-45 ° C and 55.5-56 ° C. Both forms provide satisfactory analysis and their spectra are consistent with the stated structure of substance I.
Použitý výchozí 2-bromfenyl-2'-merkaptobenzylsulfid (II) je látkou novou, kterou lze připravit dále uvedeným postupem ze známého bis (2-brommethylfenyl) disulfidu (literatura citována).The starting 2-bromophenyl-2'-mercaptobenzyl sulfide (II) used is a novel compound which can be prepared by the following procedure from the known bis (2-bromomethylphenyl) disulfide (literature cited).
K roztoku 6,1 g hydroxidu draselného ve 200 ml ethanolu se přidá 18,4 g 2-bromthiofenolu (Van Hově, Bl. Acad. Belgique (5) 12, 937; Chem. Zentralbl. 1927 I, 1821; 1928 I, 491) a 19,6 g bis (2-brommethylfenyl) disulfidu a směs se vaří v dusíkové atmosféře 6 hodin pod zpětným chladičem. Potom se ethanol oddestiluje, zbytek se zředí 100 ml vody a produkt se izoluje extrakcí benzenem. Zpracováním extraktu se získá 31 g surového olejovitého bis/2-( 2-bromf enylthiomethyl )fenyl/disulfidu.To a solution of 6.1 g of potassium hydroxide in 200 ml of ethanol is added 18.4 g of 2-bromothiophenol (Van Hove, Bl. Acad. Belgique (5) 12, 937; Chem. Zentralbl. 1927 I, 1821; 1928 I, 491). ) and 19.6 g of bis (2-bromomethylphenyl) disulfide and the mixture was refluxed for 6 hours. Then the ethanol is distilled off, the residue is diluted with 100 ml of water and the product is isolated by extraction with benzene. Workup of the extract yielded 31 g of crude oily bis [2- (2-bromophenylthiomethyl) phenyl] disulfide.
K roztoku 13,2 g trifenylfosfinu v 70 ml dioxanu se přidá 31 g předešlého surového disulfidu v 80 ml dioxanu. Za míchání se potom během 5 minut přikape 30 ml vody okyselené 4 kapkami kyseliny chlorovodíkové. Směs se míchá 1 hodinu při 40 °C v dusíkové atmosféře, dioxán se odpaří za sníženého tlaku, zbytek se rozpustí ve 150 ml etheru a kyselý produkt se převede protřepáním do 3krát 200 ml 5% roztoku hydroxidu sodného. Spojené alkalické roztoky se okyselí 100 ml 3N kyseliny chlorovodíkové a produkt se izoluje extrakcí, benzenem. Destilací vysušeného extraktu se získá 18,5 g (60 %) žádaného 2-bromfenyl-2'-merkaptobenzylsulfidu s t. v. 168 °C/27Pa. Destilát stáním tuhne na krystalickou látku, kterou lze překrystalovat z ethanolu; čistý produkt taje při 66 až 68 °C.To a solution of 13.2 g of triphenylphosphine in 70 mL of dioxane was added 31 g of the previous crude disulfide in 80 mL of dioxane. While stirring, 30 ml of water acidified with 4 drops of hydrochloric acid are then added dropwise over 5 minutes. The mixture was stirred at 40 ° C for 1 hour under nitrogen, the dioxane was evaporated under reduced pressure, the residue was dissolved in 150 ml of ether and the acidic product was transferred by shaking into 3 x 200 ml of 5% sodium hydroxide solution. The combined alkaline solutions were acidified with 100 ml of 3N hydrochloric acid and the product isolated by extraction with benzene. Distillation of the dried extract yielded 18.5 g (60%) of the desired 2-bromophenyl-2'-mercaptobenzylsulfide, m.p. 168 ° C / 27Pa. The distillate solidifies on standing to a crystalline substance which can be recrystallized from ethanol; the pure product melts at 66-68 ° C.
2. Z meziproduktu II „in sítu“,, tj. bez jeho izolace .2. From intermediate II 'in situ', ie without isolation.
K roztoku 9,4 g benzen-l,2-dithiolu (lit. cit.) ve 200 ml dimethylformamidu se přidáTo a solution of 9.4 g of benzene-1,2-dithiol (cit. Cit.) In 200 ml of dimethylformamide is added
7,25 g bezvodého uhličitanu draselného a7.25 g of anhydrous potassium carbonate a
13,3 g 2-brombenzylbromidu (lit. cit.); směs se bez zahřívání míchá 1 hodinu, čímž dojde k vytvoření 2-bromfenyl-2'-merkaptobenzylsulfidu. Aniž by se tento izoloval, přidá se k směsi dalších 10 g uhličitanu draselného a 0,8 g Čerstvě vyredukované mědi a směs se nyní vaří 6 hodin pod zpětným chladičem. Po stání přes noc se dimethylformamid oddestiluje ve vakuu, zbytek se zředí vodou a extrahuje benzenem. Extrakt se promyje vodou, vysuší uhličitanem draselným a odpaří. Zbytek poskytne destilací ve vakuu 7,1 g (58%) surového llH-dibenzo(b, e)1,4-dithiepinu (I) s t. v. 170 až 180 °C/150 Pa. Produkt stáním krystaluje a vylučuje se ve formě níže tající modifikace s t. t. 44 až 45,5 °C.13.3 g of 2-bromobenzyl bromide (ref. Cit.); the mixture was stirred without heating for 1 hour to form 2-bromophenyl-2'-mercaptobenzylsulfide. Without isolation, an additional 10 g of potassium carbonate and 0.8 g of freshly reduced copper were added to the mixture and the mixture was now refluxed for 6 hours. After standing overnight, dimethylformamide was distilled off in vacuo, the residue was diluted with water and extracted with benzene. The extract was washed with water, dried over potassium carbonate and evaporated. The residue was distilled under vacuum to give 7.1 g (58%) of crude 11H-dibenzo (b, e) 1,4-dithiepine (I), m.p. 170-180 ° C / 150 Pa. The product crystallizes on standing and precipitates in the form of the following melting point, m.p. 44-45.5 ° C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS309378A CS202239B1 (en) | 1978-05-13 | 1978-05-13 | Process for preparing new 11h-dibenzo/b,e/-1,4-dithiepine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS309378A CS202239B1 (en) | 1978-05-13 | 1978-05-13 | Process for preparing new 11h-dibenzo/b,e/-1,4-dithiepine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS202239B1 true CS202239B1 (en) | 1980-12-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS309378A CS202239B1 (en) | 1978-05-13 | 1978-05-13 | Process for preparing new 11h-dibenzo/b,e/-1,4-dithiepine |
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| Country | Link |
|---|---|
| CS (1) | CS202239B1 (en) |
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1978
- 1978-05-13 CS CS309378A patent/CS202239B1/en unknown
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