DD236092A1 - PROCESS FOR PREPARING 4,5-DISUBSTITUTED 1,3-DITHIOL-2-THIONES - Google Patents
PROCESS FOR PREPARING 4,5-DISUBSTITUTED 1,3-DITHIOL-2-THIONES Download PDFInfo
- Publication number
- DD236092A1 DD236092A1 DD27498385A DD27498385A DD236092A1 DD 236092 A1 DD236092 A1 DD 236092A1 DD 27498385 A DD27498385 A DD 27498385A DD 27498385 A DD27498385 A DD 27498385A DD 236092 A1 DD236092 A1 DD 236092A1
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- dithiol
- thiones
- alkyl
- benzoyl
- general formula
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 cyanomethyl Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 4
- 125000004849 alkoxymethyl group Chemical group 0.000 claims abstract description 3
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 3
- 150000002825 nitriles Chemical group 0.000 claims abstract description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000005079 alkoxycarbonylmethyl group Chemical group 0.000 claims description 2
- 125000004190 benzothiazol-2-yl group Chemical group [H]C1=C([H])C([H])=C2N=C(*)SC2=C1[H] 0.000 claims description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- WYKJWNVWJOKVQP-UHFFFAOYSA-N 1,3-dithiole-2-thione Chemical class S=C1SC=CS1 WYKJWNVWJOKVQP-UHFFFAOYSA-N 0.000 abstract description 7
- YYFVNSLIEHKDBT-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-ylsulfanyl)-1-phenylethanone Chemical class N=1C2=CC=CC=C2SC=1SCC(=O)C1=CC=CC=C1 YYFVNSLIEHKDBT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 239000000314 lubricant Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000000361 pesticidal effect Effects 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- MWRLAEXCURUTGN-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-2-sulfanylacetic acid Chemical class C1=CC=C2SC(C(S)C(=O)O)=NC2=C1 MWRLAEXCURUTGN-UHFFFAOYSA-N 0.000 abstract 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XAKBSHICSHRJCL-UHFFFAOYSA-N [CH2]C(=O)C1=CC=CC=C1 Chemical group [CH2]C(=O)C1=CC=CC=C1 XAKBSHICSHRJCL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZZUQWNYNSKJLPI-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-ylsulfanyl)acetic acid Chemical class C1=CC=C2SC(SCC(=O)O)=NC2=C1 ZZUQWNYNSKJLPI-UHFFFAOYSA-N 0.000 description 1
- 206010022998 Irritability Diseases 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- FJIFGGQHUVANGE-UHFFFAOYSA-N methyl 2-(1,3-benzothiazol-2-ylsulfanyl)acetate Chemical compound C1=CC=C2SC(SCC(=O)OC)=NC2=C1 FJIFGGQHUVANGE-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 239000012989 trithiocarbonate Substances 0.000 description 1
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
Abstract
Die Erfindung betrifft ein neues Verfahren zur Herstellung von substituierten 1,3-Dithiol-2-thionen der allgemeinen Formel II, in der R eine Alkoxycarbonyl-, Nitril-, Acetyl-, subst. Benzoyl- oder Benzoylgruppe und R eine Alkyl-, Cyanmethyl-, Alkoxycarbonyl-, Alkoxymethyl-, Benzoylmethyl-, Acetylmethyl- oder Alkyl- bzw. Arylthiomethylgruppe bedeuten. Ziel der Erfindung ist eine einfach durchfuehrbare Herstellung der substituierten 1,3-Dithiol-2-thione. Erfindungsgemaess werden die Derivate der 2-(Benzothiazol-2-yl)-thioglykolsaeure bzw. die 2-(Phenacylthio)-benzothiazole mit Schwefelkohlenstoff in dipolar aprotischem Loesungsmittel mit einer Base versetzt und mit Halogenderivaten RX umgesetzt. 1,3-Dithiol-2-thione sind Ausgangsstoffe fuer "organische Metalle", fuer pestizide Verbindungen sowie antioxidative Zusaetze fuer Schmiermittel.The invention relates to a novel process for the preparation of substituted 1,3-dithiol-2-thionen of the general formula II, in which R is an alkoxycarbonyl, nitrile, acetyl, subst. Benzoyl or benzoyl group and R is an alkyl, cyanomethyl, alkoxycarbonyl, alkoxymethyl, benzoylmethyl, acetylmethyl or alkyl or arylthiomethyl group. The aim of the invention is an easily carried out preparation of the substituted 1,3-dithiol-2-thiones. According to the invention, the derivatives of 2- (benzothiazol-2-yl) -thioglycolic acid or the 2- (phenacylthio) -benzothiazoles are mixed with carbon disulfide in dipolar aprotic solvent with a base and reacted with halogen derivatives RX. 1,3-Dithiol-2-thiones are starting materials for "organic metals", for pesticidal compounds and antioxidant additives for lubricants.
Description
Die Erfindung betrifft ein neues Verfahren zur Herstellung von substituierten 1,3-Dithiol-2-thionen der allgemeinen Formel II, in der R' eine Alkoxycarbonyl-, Nitril-, Acyl-, subst. Benzoyl- oder Benzoylgruppe, R" eine Alkyl-, Cyanmethyl-, Alkoxycarbonylmethyl-, Alkoxymethyl-, Benzoylmethyl-, Acetylmethyl-, Alkyl- bzw. Arylthiomethylgruppe bedeuten. 1,3-Dithiol-2-thione sind Ausgangsstoffe für „organische Metalle". Sie können ferner als pestizide Verbindungen sowie als antioxidative Zusatzstoffe für Schmiermittel dienen.The invention relates to a novel process for the preparation of substituted 1,3-dithiol-2-thionen of the general formula II, in which R 'is an alkoxycarbonyl, nitrile, acyl, subst. Benzoyl or benzoyl group, R "is an alkyl, cyanomethyl, alkoxycarbonylmethyl, alkoxymethyl, benzoylmethyl, acetylmethyl, alkyl or arylthiomethyl group. 1,3-Dithiol-2-thiones are starting materials for" organic metals ". They may also serve as pesticidal compounds as well as antioxidant additives for lubricants.
Die Suche nach neuen Synthesen für 1,3-Dithiol-2-thione wurde durch das Auffinden elektrisch leitender Materialien bei Derivaten dieser Substanzklasse stark belebt.The search for new syntheses for 1,3-dithiol-2-thiones has been greatly stimulated by the discovery of electrically conductive materials in derivatives of this class of compounds.
Man erhält 1 ,3-Dithiol-2-thione nach einer Reihe von Verfahren.1, 3-Dithiol-2-thiones are obtained by a number of methods.
Besonders günstig erwies sich für charakteristisch substituierte Derivate die Umsetzung von Alkylxanthogenessigsäurederivaten oder S-(Phenacyl)-xanthogenaten mit Schwefelkohlenstoff (DDR-Pat. 2081.52).The reaction of alkylxanthogeneacetic acid derivatives or S- (phenacyl) -xanthogenates with carbon disulfide proved to be particularly favorable for characteristically substituted derivatives (DDR Pat.
Die Anlagerung von Schwefelkohlenstoff an die Anionen der Alkylxanthogenessigsäurederivate bzw. S-(Phenacyl)-xanthogenate oder der entsprechenden Dithiocarbamate bzw. Trithio-carbonate analoger Struktur liefert die Titelverbindungen.The addition of carbon disulfide to the anions of Alkylxanthogenessigsäurederivate or S- (phenacyl) xanthogenates or the corresponding Dithiocarbamate or trithio-carbonates analogous structure provides the title compounds.
Das Ziel der Erfindung ist die Herstellung der substituierten 1,3-Dithiol-2-thione aus leicht zugänglichen Synthesebausteine auf einfach durchführbare Weise.The object of the invention is the preparation of the substituted 1,3-dithiol-2-thiones from readily available synthetic building blocks in an easily feasible manner.
Der Erfindung liegt die Aufgabe zugrunde, ein neues Verfahren zur Herstellung dieser Thione aufzufinden.The invention has for its object to find a new method for producing these Thione.
Erfindungsgemäß gelingt es, die Verbindungen der Formel Il dadurch herzustellen, daß man die S-(Benzothiazol-2-yl)-thioglykolsäurederivate oder 2-(Phenacylthio)benzothiazole und Schwefelkohlenstoff in einem dipolar aprotischen Lösungsmittel, wie г. B. DMF löst, bei 00C die doppelt molare Menge einer geeigneten Base, z. B. Natriumtertärbutanolat, einrührt und 2 Stunden bei Raumtemperatur nach rührt. Dann alkyliert man mit einer halogenaktiven Verbindung der allgemeinen Formel R" X, wie beispielsweise Alkylhalogenide, a-Halogencarbonsäurederivaten, Halogenmethylthioverbindungen oder subst.According to the invention it is possible to prepare the compounds of formula II by reacting the S- (benzothiazol-2-yl) -thioglykolsäurederivate or 2- (phenacylthio) benzothiazoles and carbon disulfide in a dipolar aprotic solvent, such as. B. DMF dissolves, at 0 0 C, the double molar amount of a suitable base, for. B. Natriumtertärbutanolat, stirred and stirred for 2 hours at room temperature. Then alkylated with a halogen-active compound of the general formula R "X, such as alkyl halides, a-halocarboxylic acid, halomethylthio or subst.
ω-Halogenacetophenonen.ω-haloacetophenones.
Bei dieser Reaktionsführung findet überraschenderweise eine Cyclisierung und Spaltung des Benzothiazolringes statt, die zu den 1,3-Dithiol-2-thionen der allgemeinen Formel Il führt. Die zu erwartenden Keten-S,S-acetale bilden sich nicht.Surprisingly, this reaction procedure involves cyclization and cleavage of the benzothiazole ring, which leads to the 1,3-dithiol-2-thiones of the general formula II. The expected ketene S, S-acetals do not form.
Das Formelschema 1 veranschaulicht das erfindungsgemäße Verfahren zur Herstellung der Verbindungen II.The formula scheme 1 illustrates the process according to the invention for the preparation of the compounds II.
In Tabelle 1 sind Beispiele für erfindungsgemäß hergestellte Substanzen aufgeführt.Table 1 lists examples of substances produced according to the invention.
Die S-(benzothiazol-2-yl)-thioglykolsäurederivate und 2-(Phenacylthio)benzothiazole sind nach bekannten Verfahren aus 2-Mercaptobenzothiazol und a-Halogenessigsäurederivaten bzw. subst. ω-Halogenacetophenonen zugänglich.The S- (benzothiazol-2-yl) -thioglycolic acid derivatives and 2- (phenacylthio) benzothiazoles are prepared by known methods from 2-mercaptobenzothiazole and a-haloacetic acid derivatives or subst. ω-Halogenacetophenonen accessible.
Beispiel 1 S-Methoxycarbonyl^-methylthio-i^-dithiol^-thionExample 1 S-Methoxycarbonyl-methylthio-1-dithiol-thione
2,39g (0,01 Mol) S-(Benzothiazol-2-yl)-thioglykolsäuremethylesterund 1,52 ml Schwefelkohlenstoff werden in 50 ml abs. DMF gelöst. Unter Eiskühlung trägt man 0,02MoI Base ein, wobei unter Stickstoffatmosphäre gearbeitet wird. Die Mischung wird rot.2.39 g (0.01 mol) of S- (benzothiazol-2-yl) -thioglycolic acid methyl ester and 1.52 ml of carbon disulfide are dissolved in 50 ml of abs. DMF solved. While cooling with ice, 0.02 mol of base is introduced while working under a nitrogen atmosphere. The mixture turns red.
Man entfernt das Kühlbad und rührt 2 Std. bei Zimmertemperatur.Remove the cooling bath and stir for 2 hrs. At room temperature.
Danach gibt man 3g Methyliodid zu. Es wird eine Farbveränderung nach gelb beobachtet. Nach 2 Std. Rühren gießt man in Eis, saugt das gebildete Produkt ab und kristallisiert aus n-Butanol um (Verbindung 1 in Tabelle 1).Thereafter, 3 g of methyl iodide are added. A color change to yellow is observed. After stirring for 2 hours, it is poured into ice, the product formed is filtered off with suction and crystallized from n-butanol (compound 1 in Table 1).
Das 1H-NMR-Spektrum dieser Verbindung (in CDCI3) weist keine aromatischen Protonen mehr auf. Es werden 2 Signale beobachtet: δ = 2,54ppm, SingulettfürSCH3undS = 3,80ppm, Singulett für OCH3.The 1 H NMR spectrum of this compound (in CDCI 3 ) no longer shows any aromatic protons. Two signals are observed: δ = 2.54 ppm, singlet for SCH 3 and S = 3.80 ppm, singlet for OCH 3 .
Das13C-NMR-Spektrum in CDCI4 weist das Signal für die Thiocarbonylgruppe bei δ = 207 ppm auf. Die anderen Signale entsprechen der Struktur.The 13 C-NMR spectrum in CDCl 4 has the signal for the thiocarbonyl group at δ = 207 ppm. The other signals correspond to the structure.
-2- 749 83-2- 749 83
Beispiele S-Cyan-^methylthio-I.S-dithiol^-thionExamples S-cyano-methylthio-1S-dithiol-thione
2,06g S-(Benzothiazol-2-yl)-thioglykolsäurenitril und 1,2m! Schwefelkohlenstoff werden in SOmltrockenem DMFgelöst. Man verfährt weiter wie im Beispiel 1 beschrieben und erhält Verbindung Nr. 3 in Tabelle 1.2.06 g of S- (benzothiazol-2-yl) thioglycolic acid nitrile and 1.2m! Carbon disulfide is dissolved in SOmt dry DMF. The procedure is as described in Example 1 and receives compound no. 3 in Table 1.
C5H3NS4 (205,33)C 5 H 3 NS 4 (205.33)
berechnet % gefunden %calculated% found%
C: 29,29 C: 29,33C: 29.29 C: 29.33
H: 1,48 H: 1,46H: 1.48 H: 1.46
N: 6,82 N: 6,79N: 6.82 N: 6.79
Verb. Nr.Verb no.
R'R '
Schmp. [0C]Schmp. [ 0 C]
Ausb.Y.
COOCH3 COOCH 3
COOC2H5 COOC 2 H 5
CNCN
COC6H4-P-BrCOC 6 H 4 -P-Br
COC6H4-P-CICOC 6 H 4 -P-CI
COOC2H5 COOC 2 H 5
COOC2H5 COOC 2 H 5
CH3 CH 3
CH3 CH 3
CH3 CH 3
CH3 CH 3
CH3 CH 3
CH2SCH3 CH 2 SCH 3
CH2COC6H4-P-CICH 2 COC 6 H 4 -P-CI
144-146 127-128 114-115 181-183 164-166 62-63 151-152144-146 127-128 114-115 181-183 164-166 62-63 151-152
39 25 49 33 38 78 7139 25 49 33 38 78 71
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD27498385A DD236092A1 (en) | 1985-04-09 | 1985-04-09 | PROCESS FOR PREPARING 4,5-DISUBSTITUTED 1,3-DITHIOL-2-THIONES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD27498385A DD236092A1 (en) | 1985-04-09 | 1985-04-09 | PROCESS FOR PREPARING 4,5-DISUBSTITUTED 1,3-DITHIOL-2-THIONES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD236092A1 true DD236092A1 (en) | 1986-05-28 |
Family
ID=5566718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD27498385A DD236092A1 (en) | 1985-04-09 | 1985-04-09 | PROCESS FOR PREPARING 4,5-DISUBSTITUTED 1,3-DITHIOL-2-THIONES |
Country Status (1)
| Country | Link |
|---|---|
| DD (1) | DD236092A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5661176A (en) * | 1996-07-10 | 1997-08-26 | The Dow Chemical Company | (2-one (or thione)-1,3-dithiole-4,5-diyl)-bis(thiomethylthiocyanate), compounds for use as antimicrobial and marine antifouling agents |
-
1985
- 1985-04-09 DD DD27498385A patent/DD236092A1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5661176A (en) * | 1996-07-10 | 1997-08-26 | The Dow Chemical Company | (2-one (or thione)-1,3-dithiole-4,5-diyl)-bis(thiomethylthiocyanate), compounds for use as antimicrobial and marine antifouling agents |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0039844A2 (en) | Process for the preparation of O-substituted derivatives of (+)-cyanidan-3-ols | |
| EP0089011B1 (en) | Process for the preparation of 5-oxonitriles | |
| DE2024694B2 (en) | Process for the preparation of 3,4-dihydro-1,2,3-oxathiazin-4-ones | |
| DE69803909T2 (en) | Processes and intermediates that can be used in the manufacture of antifolates | |
| EP0074121B1 (en) | 2,3,4,5-tetrahydro-1-benzoxepine-3,5-dione derivatives and process for their preparation | |
| DD236092A1 (en) | PROCESS FOR PREPARING 4,5-DISUBSTITUTED 1,3-DITHIOL-2-THIONES | |
| EP0184981B1 (en) | Pyrrolinones and their intermediate products | |
| SU415876A3 (en) | METHOD FOR PRODUCING DERIVATIVES OF BENZIMIDAZOLE | |
| DE2710382A1 (en) | METHOD FOR PRODUCING 2,1,3-THIADIAZINE-4-ON-2,2-DIOXIDE DERIVATIVES | |
| DE1153375B (en) | Process for the preparation of benzoxazine- (1, 3) -dione- (2, 4) | |
| EP0161617A2 (en) | Intermediates and process for the preparation of intermediates in the synthesis of cephalosporins | |
| AT258916B (en) | Process for the preparation of new alkyl 3-amino-5-chloro-6-X-pyrazinoates | |
| DE1901291A1 (en) | Process for the preparation of substituted 3-amino-benzothiophenes | |
| EP0365914A2 (en) | Fluorine-containing acetophenones optionally halogenated in the CH3-group, and their preparation from fluorinated benzonitriles | |
| DE3216851A1 (en) | METHOD FOR PRODUCING SUBSTITUTED BIPHENYL COMPOUNDS | |
| AT364836B (en) | METHOD FOR PRODUCING NEW O-SUBSTITUTED DERIVATIVES OF (+) - CYANIDAN-3-OLS AND THE SALTS THEREOF | |
| DE3590057C1 (en) | Process for the preparation of diacyldianhydrohexites | |
| CH562814A5 (en) | ||
| DE2233520A1 (en) | Process for the preparation of penicillin and penicillin sulphide esters | |
| EP0175264B1 (en) | Process for the preparation of 2-amino-3-cyano-5-dialkoxymethyl pyrazines and intermediates for this process | |
| DE965490C (en) | Process for the preparation of aromatic sulfonium compounds | |
| EP0043024A1 (en) | Process for the preparation of 5-amino isoxazoles | |
| CH618702A5 (en) | ||
| DE69119068T2 (en) | NITROANILIDES AND METHOD FOR THE PRODUCTION THEREOF | |
| JPS6051180A (en) | Preparation of 1,2,4-triazolin-5-one |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENJ | Ceased due to non-payment of renewal fee |