CS266827B1 - 2-isothiocyanato-3-cyan-4,5,6,7-tetrahydrobenzo/b/thiophene and method of its preparation - Google Patents
2-isothiocyanato-3-cyan-4,5,6,7-tetrahydrobenzo/b/thiophene and method of its preparation Download PDFInfo
- Publication number
- CS266827B1 CS266827B1 CS877826A CS782687A CS266827B1 CS 266827 B1 CS266827 B1 CS 266827B1 CS 877826 A CS877826 A CS 877826A CS 782687 A CS782687 A CS 782687A CS 266827 B1 CS266827 B1 CS 266827B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- thiophene
- tetrahydrobenzo
- formula
- cyano
- isothiocyanato
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title description 6
- 229930192474 thiophene Natural products 0.000 title description 3
- QHTDRPQZFMGDLQ-UHFFFAOYSA-N 2-isothiocyanato-4,5,6,7-tetrahydro-1-benzothiophene-3-carbonitrile Chemical compound C1CCCC2=C1SC(N=C=S)=C2C#N QHTDRPQZFMGDLQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 6
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 claims abstract description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000000954 anitussive effect Effects 0.000 description 1
- 239000003430 antimalarial agent Substances 0.000 description 1
- 229940033495 antimalarials Drugs 0.000 description 1
- 239000003434 antitussive agent Substances 0.000 description 1
- 229940124584 antitussives Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- WIRUZQNBHNAMAB-UHFFFAOYSA-N benzene;cyclohexane Chemical compound C1CCCCC1.C1=CC=CC=C1 WIRUZQNBHNAMAB-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229940125723 sedative agent Drugs 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Abstract
Řešení se týká 2-isothiokyanato-3- -kyan-4,5,6,7-tetrahydrobenzo [b] thiofenu vzorce I a způsobu jeho výroby reakcí 2- -amino-3-kyan-4,5,6,7-tetrahydrobenzo[b] - thiofenu vzorce II s thiofosgenem v inertním organickém rozpouštědle v přítomnosti uhličitanu vápenatého nebo hydrogenuhličitanu sodného či draselného při teplotě 20 až 25 °C. Látka vzorce I slouží jako meziprodukt pro syntézu produktů s herbicidními účinky a látek využitelných ve farmakologii a v zemědělství.The solution relates to 2-isothiocyanato-3- -cyano-4,5,6,7-tetrahydrobenzo [b] thiophene of formula (I) and a process for its preparation by -amino-3-cyano-4,5,6,7-tetrahydrobenzo [b] - thiophene of formula II with thiophosgene in inert an organic solvent in the presence calcium carbonate or bicarbonate sodium or potassium at 20 to Deň: 25 ° C. The compound of formula I serves as an intermediate for the synthesis of herbicidal products effects and substances useful in pharmacology and in agriculture.
Description
Vynález se týká 2-isothiokyanato-3-kyan-4,5,6,7-tetrahydrobenzo [b]thiofenu vzorce I (I) a způsobu jeho výroby. Látka vzorce I a způsob její výroby nebyly doposud ρ ' cy, avšak je známo, že příbuzné arylisothiokyanáty lze připravit reakcí arylaminu s thiofosgenem v přítomnosti vody. Výtěžky reakce se pohybují od 60 do 97 % (Dyson G. M., George H. J. , J. Chem. Soc. 125, 1 702 (1924), Dyson G. M., Chem. Ind. 30, 934 (1954), Tietze E., Petersen S., Domagk G. , Ber. 86, 314 (1953).
Předmětem vynálezu je nová látka, 2-isothiokyanato-3-kyan-4,5,6,7-tetrahydrobenzoJbJ-thiofen vzorce I. Bylo nalezeno, že látku vzorce I lze připravit reakcí 2-amino-3-kyan-4,5,6,7--tetrahydro [bj thiofenu vzorce II (II) s thiofosgenem v inertním rozpouštědle v přítomnosti uhličitanu vápenatého nebo hydrogen-uhličitanu sodného či draselného při teplotě 20 až 25 °C. 2-isothiokyanato-3-kyan-4,5,6,7-tetrahydrobenzo [b]thiofen se používá pro syntézy Ν'-substituovaných N-/2-(3-kyan-4,5,6,7-tetrahydrobenzo [bj thíenyl)/thíomočovin, které mají herbicidní účinky nebo se využívají jako prekursory pro syntézu kondenzovaných pyrimidi-nových heterocyklú využívaných ve farmakologii (sedativa, antitusika, antimalarika, antifolika) a zemědělství (herbicidy, stimulátory růstu) . Přiklad K suspenzi obsahující 50 cm"* dichlormethanu, 28,7 g (0,25 mol) thiofosgenu a 34 g (0,40 mol) jemně rozetřeného hydrogenuhličitanu sodného byla za intenzivního míchání za teploty místnosti po dobu 20 minut přikapávána suspenze obsahující 36,7 g (0,20 mol) 2-amino--3-kyan-4,5,6 ,'7-tetrahydro [b] thiofenu v 800 cm* dichlormethanu. Po 60 minutách reakce od počátku přidávání aminové složky byla reakce ukončena, rozpouštědlo a nereagovaný thio-fosgen byly odpařeny na rotační vakuové odparce. Produkt byl překrystalován ze směsi benzen--cyklohexan.
Bylo získáno 38,2 g (86,7 %) 2-isothiokyanato-3-kyan-4,5,6,7-tetrahydrobenzo[b]thiofenu. Žlutá krystalická látka, teplota tání 68 až 70 °C. IČ spektrum (suspenze v bromoformu) : λ) (CN) 2 225, \) (N=C=S) 2 000, Ό (C=C) 1 565 , "S5 (CH) 2 850, 2 870, 2 950 cm-1.
The present invention relates to 2-isothiocyanato-3-cyano-4,5,6,7-tetrahydrobenzo [b] thiophene of formula I (I) and to a process for its preparation. The compound of formula (I) and the process for its preparation have not been previously known, but related arylisothiocyanates are known to be prepared by reacting arylamine with thiophosgene in the presence of water. Reaction yields range from 60 to 97% (Dyson GM, George HJ, J. Chem. Soc. 125, 1702 (1924), Dyson GM, Chem. Ind. 30, 934 (1954), Tietze E., Petersen S , Domagk G., Ber., 86, 314 (1953).
The present invention provides a novel compound, 2-isothiocyanato-3-cyano-4,5,6,7-tetrahydrobenzo [b] thiophene of formula I. It has been found that the compound of formula I can be prepared by the reaction of 2-amino-3-cyano-4,5, 6,7-tetrahydro [b] thiophene of formula II (II) with thiophosgene in an inert solvent in the presence of calcium carbonate or sodium or potassium bicarbonate at 20-25 ° C. 2-isothiocyanato-3-cyano-4,5,6,7-tetrahydrobenzo [b] thiophene is used for the synthesis of Ν'-substituted N- [2- (3-cyano-4,5,6,7-tetrahydrobenzo [b] thienyl) thioureas which have herbicidal activity or are used as precursors for the synthesis of condensed pyrimidine heterocycles used in pharmacology (sedatives, antitussives, antimalarials, antifolics) and agriculture (herbicides, growth promoters). Example K A suspension containing 36% of sodium bicarbonate, 28.7 g (0.25 mol) of thiophosgene and 34 g (0.40 mol) of finely divided sodium bicarbonate was added dropwise to the suspension at 50 DEG C. for 20 minutes. 7 g (0.20 mol) of 2-amino-3-cyano-4,5,6,7-tetrahydro- [b] thiophene in 800 cm < -1 > of dichloromethane. the solvent and the unreacted thio-phosgene were evaporated on a rotary evaporator, and the product was recrystallized from benzene-cyclohexane.
38.2 g (86.7%) of 2-isothiocyanato-3-cyano-4,5,6,7-tetrahydrobenzo [b] thiophene were obtained. Yellow crystalline, mp 68-70 ° C. IR spectrum (suspension in bromoform): λ) (CN) 2 225, (N = C = S) 2 000, Ό (C = C) 1 565, "S5 (CH) 2 850, 2 870, 2 950 cm-1.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS877826A CS266827B1 (en) | 1987-11-02 | 1987-11-02 | 2-isothiocyanato-3-cyan-4,5,6,7-tetrahydrobenzo/b/thiophene and method of its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS877826A CS266827B1 (en) | 1987-11-02 | 1987-11-02 | 2-isothiocyanato-3-cyan-4,5,6,7-tetrahydrobenzo/b/thiophene and method of its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS782687A1 CS782687A1 (en) | 1989-05-12 |
| CS266827B1 true CS266827B1 (en) | 1990-01-12 |
Family
ID=5428105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS877826A CS266827B1 (en) | 1987-11-02 | 1987-11-02 | 2-isothiocyanato-3-cyan-4,5,6,7-tetrahydrobenzo/b/thiophene and method of its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS266827B1 (en) |
-
1987
- 1987-11-02 CS CS877826A patent/CS266827B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS782687A1 (en) | 1989-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1088552A (en) | 4,5-dichloro-imidazole-1-carboxylic acid aryl esters and their use as plant protection agents | |
| CN100390179C (en) | Arylamine-substituted bicyclic heteroaromatic compounds as p38 kinase inhibitors | |
| KR850000678B1 (en) | Process for preparing ureas and isoureas | |
| HU190675B (en) | Herbicidal and plant growth regulating compositions comprising thiophene-sulfonamide-derivatives | |
| EP0298196A1 (en) | Imidazole compounds and biocidal compositions comprising the same | |
| HUP0300139A2 (en) | Method for preparing hydroxypicolinic acid derivatives and use of the obtained compounds | |
| KR20010079546A (en) | Fused-heterocycle dicarboxylic diamide derivatives or salts thereof, herbicides and usage thereof | |
| CS208677B2 (en) | Means for killing the non-desirous vegetation | |
| EP0982992A1 (en) | Fungicides | |
| CA1208221A (en) | N-heterocyclemethyl-phenylamide compounds | |
| EP0073562A2 (en) | Herbicidal triazole ureas | |
| US3726891A (en) | Fused 1,2,4-thiadiazolines | |
| GB2192877A (en) | Herbicidal imidazolinyl compounds | |
| NZ235768A (en) | 2-(imidazolyl, benzimidazolyl or triazolyl)-pyridine-3-carboxylic acid derivatives; preparation processes and herbicidal compositions | |
| JP2641518B2 (en) | Halogenated thiadiazolyl-oxyacetamides, their preparation and novel intermediates and their use as herbicides | |
| JPH0656827A (en) | New sulfonylurea | |
| JPH0655727B2 (en) | Imidazolidinone and imidazolidinethione compounds, herbicidal compositions containing them, and methods for producing them | |
| Mohareb et al. | Synthesis of Thiophenes, Azoles and Azines with Potential Biological Activity by Employing the Versatile Heterocyclic Precursor N‐Benzoycyanoacetylhydrazine | |
| CS266827B1 (en) | 2-isothiocyanato-3-cyan-4,5,6,7-tetrahydrobenzo/b/thiophene and method of its preparation | |
| El-Saghier et al. | New synthetic approaches to condensed and spiro coumarins: coumarin-3-thiocarboxamide as building block for the synthesis of condensed and spiro coumarins | |
| Raslan et al. | Reactivity of 3‐(benzothiazol‐2‐yl)‐3‐oxopropanenitrile: A facile synthesis of novel polysubstituted thiophenes | |
| RU2130021C1 (en) | Picolineamide derivatives, method of preparing thereof, pyridine-6-carbonitrile, herbicidal composition, methods of controlling undesired vegetation | |
| RU2638928C1 (en) | Derivatives of 1h-pyrazolo [3,4-d] pyrimidine and method of their production | |
| SU1274624A3 (en) | Method of producing 5-(2-chlorbenzyl)-5,6,7,7a-tetrahydro-4n-thieno(3,2-c)pyridinon-2 | |
| DE2526990A1 (en) | NEW CEPHALOSPORIN AND PENICILLIN DERIVATIVES |