CS195277B2 - Method of producing n-formyl-5,6,7,8-tetrahydro-7-oxocyclobenzo or 8-oxocyclohepta/b/thiophene-4-amines - Google Patents
Method of producing n-formyl-5,6,7,8-tetrahydro-7-oxocyclobenzo or 8-oxocyclohepta/b/thiophene-4-amines Download PDFInfo
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- CS195277B2 CS195277B2 CS781231A CS123178A CS195277B2 CS 195277 B2 CS195277 B2 CS 195277B2 CS 781231 A CS781231 A CS 781231A CS 123178 A CS123178 A CS 123178A CS 195277 B2 CS195277 B2 CS 195277B2
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- Czechoslovakia
- Prior art keywords
- formula
- acid
- formyl
- tetrahydro
- alkyl
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 8
- -1 8-oxocyclohepta (b) thiophen-4-amines Chemical class 0.000 claims description 7
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229940117975 chromium trioxide Drugs 0.000 claims description 5
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical group [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- SJFXHSBXVOAPJM-UHFFFAOYSA-N n-(4,5,6,7-tetrahydro-1-benzothiophen-4-yl)formamide Chemical compound O=CNC1CCCC2=C1C=CS2 SJFXHSBXVOAPJM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- DKGYESBFCGKOJC-UHFFFAOYSA-N thiophen-3-amine Chemical compound NC=1C=CSC=1 DKGYESBFCGKOJC-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
Vynález se týká způsobu výroby N-formyl-5,6,7,8-tetrahydro-7-oxocyklobenzo nebo 8-oxocyklohepta (b)thiofen-4-aminů vzorce I a IIThe present invention relates to a process for the preparation of N-formyl-5,6,7,8-tetrahydro-7-oxocyclobenzo or 8-oxocyclohepta (b) thiophen-4-amines of formula I and II
kde Z znáči vodík nebo Ci — Cá — alkyl, Y znamená vodík, Ci — C4 — alkyl, halogen, kyanovou, acetylovou nebo acetylaminovou skupinu nebo zbytek vzorce Ri — NHCONH —- a Ri značí vodík nebo Ci — C4 — alkyl, vyznačený tím, že se jeden molekvivalent sloučeniny vzorců I nebo II awherein Z represents hydrogen or C 1 -C 6 -alkyl, Y represents hydrogen, C 1 -C 4 -alkyl, halogen, cyano, acetyl or acetylamino or a radical of the formula R 1 -NHCONH- and R 1 represents hydrogen or C 1 -C 4 -alkyl, characterized by in that one mole equivalent of a compound of formulas I or II; and
kde Ri, Y a Z mají shora uvedený význam a U je — CHz — nebo >CHOH, oxiduje 2 až 8 molekvivalenty oxidačního činidla vybraného ze skupiny zahrnující dusičnan ceričitoamonný, dusičnan stříbrný, kysličník chromový a dvojchroman sodný v přítomnosti vodného roztoku rozpouštědla vybraného ze skupiny zahrnující kyselinu octovou, acetonitril, tetrahydrofuran, dioxan, dimethoxyethan a diethylenglykoldimethylether, přičemž uvedené roztoky mohou obsa193277 hovat kyselinu dusičnou, kyselinu fosforeč- , nou, kyselinu chloristou nebo kysličník chromový v acetanhydridu při teplotě 0 až 100 stupňů Celsia.wherein R 1, Y and Z are as defined above and U is -CH 2 - or> CHOH, oxidizes 2 to 8 mol equivalents of an oxidizing agent selected from the group consisting of cerium ammonium nitrate, silver nitrate, chromium trioxide and sodium dichromate in the presence of an aqueous solvent selected from including acetic acid, acetonitrile, tetrahydrofuran, dioxane, dimethoxyethane, and diethylene glycol dimethyl ether, wherein said solutions may contain nitric acid, phosphoric acid, perchloric acid, or chromic oxide in acetic anhydride at 0 to 100 degrees Celsius.
Způsob podle vynálezu se s výhodou provádí za použití 4 až 5 molekvivalentů oxidačního činidla uvedeného druhu při teplotě 20 až 60 °C.The process according to the invention is preferably carried out using from 4 to 5 mol equivalents of the oxidizing agent of this kind at a temperature of 20 to 60 ° C.
Po skončení oxidace ,sé získané oxosloučeniny hydrolyzují ve zředěné minerální kyselině. Tímto způsobem získané soli aminů s kyselinami se mohou nechat reagovat s kyanátem nebo thiokyanátem alkalického kovu při pH 5 až 7, přičemž se získají odpovídající močoviny nebo thiomočoviny, které mají účinek na růst zvláště zvířat. Sloučeniny podle vynálezu jsou cennými meziprodukty k výrobě takových cykloalkanofb j-thienylmočovin.Upon completion of the oxidation, the oxo compounds obtained are hydrolyzed in dilute mineral acid. The amine acid salts thus obtained can be reacted with an alkali metal cyanate or thiocyanate at a pH of 5-7 to obtain the corresponding ureas or thioureas which have an effect on the growth of the animals in particular. The compounds of the invention are valuable intermediates for the preparation of such cycloalkanophobi-thienyl ureas.
V dalším je vynález blíže objasněn na příkladech provedení.In the following, the invention is illustrated in more detail by means of exemplary embodiments.
Příklad 1Example 1
Výroba N-formyl-4,5,6-tetrahydro-7-oxobenzo (b) thlof en-4-aminu g N-formyl-4,5,6,7-tetrahydrobenžo(b)-thiofen-4-aminu se rozpustí ve 375 ml 50% vodné kýsellny octové a v průběhu 10 minut se při teplotě 25 až 35 °C po částech přidá 75 g dusičnanu ceričito-amonného. Roztok se míchá dalších 5 minut a potom přidá 10 mililitrů vody. Roztok se dvakrát extrahuje methylenchloridem (450 a 350 ml), načež se spojené extrakty promyjí 100 ml vody. Organický extrakt se ve vakuu odpaří k sušině. Překrystalizací takto získaného zbytku se získá N-formyl-tetrahydro-7-oxobenzo(b)thiofen-4-amin s bodem tání 118 až 120 °C (rozklad).Preparation of N-formyl-4,5,6-tetrahydro-7-oxobenzo (b) thlophen-4-amine g dissolve N-formyl-4,5,6,7-tetrahydro-benzo (b) -thiophen-4-amine in 375 ml of 50% aqueous acetic acid and 75 g of ceric ammonium nitrate are added portionwise at 25 to 35 ° C. The solution was stirred for an additional 5 minutes and then 10 ml of water was added. The solution was extracted twice with methylene chloride (450 and 350 mL) and then the combined extracts were washed with 100 mL of water. The organic extract was evaporated to dryness in vacuo. Recrystallization of the residue thus obtained gave N-formyl-tetrahydro-7-oxobenzo (b) thiophen-4-amine, m.p. 118 DEG-120 DEG C. (decomposition).
Když se dusičnan ceričito-amonný nahradí kysličníkem stříbrným, kysličníkem chromovým nebo dvojchromanem sodným, tak se získají rovněž shora uvedené 7-oxosloučeniny.Také reakce s kysličníkem chromovým v acetanhydridu s následující hydrolýzou vede k 7-oxosloučeninám.When the cerium ammonium nitrate is replaced with silver oxide, chromium trioxide or sodium dichromate, the above 7-oxo compounds are also obtained. Also, reaction with chromium trioxide in acetic anhydride followed by hydrolysis results in 7-oxo compounds.
P ř í k 1 a d 2Example 1 a d 2
Výroba N-formyl-5,6,7,8-tetrahydro-4 H-8-oxocyklohepta (b ] thiof en-4-aminuPreparation of N-formyl-5,6,7,8-tetrahydro-4H-8-oxocyclohepta (b) thiophen-4-amine
Způsobem popsaným v příkladu 1 še nechá reagovat N-formyl-5,6,7,8-tetrahydro-4 H-cyklóheptafbjthiofen-4-amin, který taje při 164 až 166 °C, se 4 ekvivalenty dusičnanu ceričito-amonného, čímž se získá sloučenina uvedená v názvů.In the manner described in Example 1, N-formyl-5,6,7,8-tetrahydro-4H-cycloheptaphthiophen-4-amine, which melts at 164-166 ° C, is reacted with 4 equivalents of cerium ammonium nitrate, thereby to give the title compound.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS781231A CS195277B2 (en) | 1975-01-22 | 1978-03-27 | Method of producing n-formyl-5,6,7,8-tetrahydro-7-oxocyclobenzo or 8-oxocyclohepta/b/thiophene-4-amines |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS75448A CS195276B2 (en) | 1974-01-25 | 1975-01-22 | Method of preparing cycloalkano/b/thieny lureas |
| CS781231A CS195277B2 (en) | 1975-01-22 | 1978-03-27 | Method of producing n-formyl-5,6,7,8-tetrahydro-7-oxocyclobenzo or 8-oxocyclohepta/b/thiophene-4-amines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS195277B2 true CS195277B2 (en) | 1980-01-31 |
Family
ID=5336550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS781231A CS195277B2 (en) | 1975-01-22 | 1978-03-27 | Method of producing n-formyl-5,6,7,8-tetrahydro-7-oxocyclobenzo or 8-oxocyclohepta/b/thiophene-4-amines |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS195277B2 (en) |
-
1978
- 1978-03-27 CS CS781231A patent/CS195277B2/en unknown
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