Folgeprodukte halogenierter Aldehyde. XVII. Reaktionen des N-(1,2,2,2-Tetrachlorethyl)-trichloracetaldimins mit Alkoholen und Mercaptanen

Derivatives of Halogenated Aldehydes. XVII. Reactions of N-(1,2,2,2-Tetrachloroethyl)trichloroacetaldimine with Alcohols and Thioalcohols Reactions of N-(1,2,2,2-tetrachloroethyl)trichloroacetaldimine 1 with methanol lead to 1,2,2,2-tetrachloroethyl-(2,2,2-trichloro-1-methoxyethyl)amine 2a , N-(2,2,2-trichloro-1-methoxyethyl)trichloroacetaldimine 3a and bis-(2,2,2-trichloro-1-methoxyethyl)amine 5 . After the reaction of the aldimine 1 with ethanol or propanol only the N-(1-alkoxy-2,2,2,-trichloroethyl)trichloroacetaldimines 3b, c are isolated; with thioalcohols only the N-(1-alkylthio-2,2,2-trichloroethyl)-trichloroacetaldimines 4a–c are obtained. The aldimines 3a–c and 4b, c are decomposed on treatment with hydrochloric acid and an excess of an alcohol or thioalcohol to yield the amine hydrochlorides 6a–c, 7b, c , which are transformed into the amines 8a–c and 9b, c . From these amines the derivatives 10–15 are prepared.     

Elektrochemische Darstellung von O,O-Diorgano-O-(2, 2-dichlorvinyl)-phosphorsäureestern

Electrochemical Synthesis of 2, 2-Dichloroethenyl-dialkyl-phosphoric Acid Esters The reaction of O-1,2,2,2-tetrachloroethyl phosphorodichloridate 3 with alcohols or phenols gives symmetrical or unsymmetrical O, O-diorgano-O-1,2,2,2-tetrachloroethyl phosphates 2 , which can be reduced electrochemically. In this reaction two vicinal chlorine atoms are eliminated. This reaction results in compounds with high biological activity, especially as insecticides. The synthesis and the polarographic behaviour of various O, O-di-organo-O-1,2,2,2-tetrachloroethyl phosphates 2 as well as the preparative techniques of the electrochemical elimination of chlorine are described.     

Folgeprodukte halogenierter Aldehyde IX. Die Synthese von Dialkyl-1,2,2,2-tetrachloräthyl- und Alkyl-phenyl-1,2,2,2-tetrachloräthyl-phosphaten

Derivatives of Halogenated Aldehydes. IX. The Synthesis of Dialkyl-1,2,2,2-tetrachloroethyl- and Alkyl-phenyl-1,2,2,2-tetrachloroethyl Phosphates Dialkyl-1,2,2,2-tetrachloroethyl- ( 3a – t ) and alkyl-phenyl-1,2,2,2-tetrachloroethyl phosphates 3u , v are prepared by reactions of 1,2,2,2-tetrachloroethyl phosphorodichloridate 1 with one mole of an alcohol or phenol to give alkyl(phenyl)-1,2,2,2-tetrachlorethyl phosphorochloridates 2a – k , followed by treatment of the latter with a second alcohol. The n.m.r. spectra of 2 and 3 are discussed.     

Folgeprodukte halogenierter Aldehyde. VII [1] Die Synthese von Di-(1,2,2,2-tetrachloräthyl)-chlorphosphat und Tri-(1,2,2,2-tetrachloräthyl)-phosphat

Derivatives of Halogenated Aldehydes. VII. The Synthesis of Di-(1,2,2,2-tetrachloroethyl) phosphorochloridate and Tri-(1,2,2,2-tetrachloroethyl) phosphate Reaction of phosphorus pentachloride with an excess of chloral in carbon tetrachloride yields a mixture of the tetrachloroethoxy-phosphorus-chlorides 1 — 4 . Following elimination of pentachloroethane by heating gives a mixture of phosphorus oxychloride, tetrachloroethyl phosphorodichloridate 6 , di-(tetrachloroethyl)phosphorochloridate 7 and tri-(tetrachloroethyl) phosphate 8 , which are separated by distillation in vacuo. The data of i.r., n.m.r. and mass spectra are concordant with the assigned structures.     

Folgeprodukte halogenierter Aldehyde. XIV [1]. Synthesen mit 1,2,2,2-Tetrachlorethylisocyanat

Derivatives of Halogenated Aldehydes. XIV. Reactions of 1,2,2,2-Tetrachloroethyl Isocyanate 1,2,2,2-Tetrachloroethyl isocyanate 2 reacts with alcohols or phenols to form the N-tetrachloroethyl-O-alkyl(aryl) urethanes 3–6 . With thioalcohols and thiophenols the corresponding thiourethanes 11–12 are obtained. In these compounds the chlorine in position 1 can be substituted by treatment with a nucleophilic compound in the presence of a base by way of an elimination addition mechanism. In these reactions the compounds 7–10 and 13–14 are formed. Amines attack 2 at both active centres to give the substituted ureas 15–18 . Diphenyl amine, some carboxylic acid amides and benzazoles, however, react only with the isocyanate group to form the compounds 19–25 . Reactions of 2-amino-benzazoles, 2-amino-pyridine and amidines with 2 yield the heterocyclic compounds 26–31 .     

Über neue Pyrazolverbindungen. IV Darstellung und Cyclisierungsverhalten einiger akzeptorsubstituierter N-(Pyrazol-3-yl)-thioharnstoffe

New Pyrazol Derivatives. IV. Preparation and Cyclization of Some Acceptor-Substituted N-(Pyrazol-3-yl)-thioureas . 3-Aminopyrazol-4-carboxylic acid derivatives ( 1 , 2 ) were transformed by reaction with different isothiocyanates R²NCS to N-(pyrazol-3-yl)-N^. -substituted thioureas ( 5 , 6 ). Ethyl 3-amino-1-benzylpyrazol-4-carboxylate reacts with CSCl₂ to form ethyl 1-benzyl-3-isothiocyanatopyrazol-4-carboxylate ( 3 ) which yields with amines the corresponding N-(pyrazol-3-yl)-N^. -substituted thioureas ( 5 ). As a byproduct in the reaction with CSCl₂ N,N^. -di-(pyrazol-3-yl)-thiourea ( 4 ) is formed. With hydrazine or phenylhydrazine N-(pyrazol-3-yl)-thiosemicarbazides ( 7a , b ) are obtained. The thioureas ( 5 , 6 ) can be cyclized in basic solution to 4,5,6,7-tetrahydropyrazolo[3,4-d]pyrimidin-4-on-6-thiones ( 8 ) which on alkylation form 6-alkylthio-4,5-dihydropyrazolo[3,4-d]pyrimidin-4-ones ( 9 ). Methyl-N-(pyrazol-3-yl)-N^.-benzoylisothiourea ( 10 ) reacts with ethylamine to form N-benzoyl-N^. -ethyl-N^‥-(pyrazol-3-yl)-guanidine derivative ( 11 ) which on treatment with NaH in dimethylformamide yields 6-benzoylamino-5-ethyl-4,5-dihydropyrazolo[3,4-d]pyrimidin-4-one ( 12 ). By treatment with sulfuric acid the N-(pyrazol-3-yl)-thiourea derivatives ( 5 , 6 ) form new 6-amino substituted pyrazolo[3,4-d][1,3]thiazin-4-ones ( 13 ).     

Pyryliumverbindungen. XXIII. 2-Dialkylamino-2H-pyrane aus tetra- und pentasubstituierten Pyryliumsalzen

Pyrylium Compounds. XXIII. 2-Dialkylamino-2H-pyrans from Tetra- and Pentasubstituted Pyrylium Salts. Tetra- and pentasubstituted pyrylium salts of type 6 react with secondary alkyl amines to give stable crystalline 2-dialkylamino-2h-pyrans 7 . In the case of tetrasubstituted pyrylium salts 6 , R′ = Me, R″ = H the reaction occurs regioselectively leading to 2H-pyrans with Me at C-3 of the heterocyclic ring. The structure of the reaction products was established by n.m.r., i.r., u.v. and mass spectroscopic methods. Electrophilic agents like protons, carboxylic acid chlorides or methyl iodide regenerate the original pyrylium cations from 7 . In refluxing methanol 7a is converted into the 2-methoxy-2H-pyran derivative 8 , whereas in aqueous acetone the pseudobase 9 and with ammonia the pyridine 10 are formed. Reaction of 7a with nitromethane or ethyl cyanoacetate provides the benzene derivatives 11 and 12 , respectively.     

Zur Reaktion von N-(N′,N′-Dialkyl(aryl)amino-thiocarbonyl)benzimidoylchloriden mit Kaliumthiocyanat

Reactions of N-(N′,N′-Dialkyl(aryl)amino-thiocarbonyl)benzimidoylchlorides with Potassium Thiocyanate The treatment of the title compound N-(amino-thiocarbonyl)-benzimidoylchloride 1 with potassium thiocyanate leads in dependence on the solvents (methanol, acetic acid, acetone) either to the 1,3,5-thiadiazine-2-thione 2a–d or to the ring opened isothiocyanate 4a , b . In the case of methanol the N-(amino-thiocarbonyl)benzimidates were formed as by-products. The structure of the products is confirmed by analytical data and by chemical transformations. 2a reacts with methyl iodide to form the 2-methylthio-6-morpholino-4-phenyl-1,3,5-thiadiaziniumiodide 3a . From 4a and water the N-(morpholino-thiocarbonyl)benzamide 5a arises. The reaction of morpholine with 4a yields the benzamidine 6a .     

Formylation products of thioamides. XIV. Synthesis of Substituted Thiazoles and Thiophenes by the reaction of N,N′-bis(aminomethylidene)thioureas or N-(3-aminothioacryloyl)-formamidines with alkylating reagents

N, N′-Bis(aminomethylidene)thioureas 1 react with electron acceptor substituted methyl halides 2 under the formation of 2-formamidinothiazoles 4 . The reaction of N-(3-aminothioacryloyl)-formamidines 5 with substituted methyl halides 2 gives either 2-formamidinothiophenes 7 or 2-aminovinylthiazoles 8 . The 8 can be hydrolysed to corresponding 2-hydroxyvinylthiazoles 9 . 2-Aminovinylthiazoles 11 bearing primary amino groups are obtained by transamination of the N-(3-aminothioacryloyl)-formamidines 5 and subsequent reaction of the resulting 10 with substituted methyl halides 2 .     

Die Nitril-Carboxamid-Umlagerung

The Nitrile Carboxamide Rearrangement By reaction of cyclohexanone-2-carboxamide ( 4 ) with cyan amide 1-cyano-cyclohex-1-en-2-yl-urea ( 6 ) is formed via nitrile carboxamide rearrangement. Whilst compound 6 with 1,2-diaminobenzene hydrochloride forms 11-amino-1 H-2,3,4,5-tetrahydrodibenzo[b,e][1,4]diazepin hydrochloride ( 8 and 8a ), compound 6 and 1,2-diaminobenzene form hexahydro-benzimidazo[1,2-c]-quinazolin-6-one ( 12 ). Compound 8 with sodium hydroxide yields 11-amino-1 H-2,3,4,11a-tetrahydrodibenzo[b,e]-[1,4]diazepin ( 9 ). Compound 6 reacts with cyclohexylamine to form N-(1-cyanocyclohex-1-en-2-yl)-N′-cyclohexyl urea ( 10 ). Compound 10 with 1,4- or 1,2-diaminobenzene hydrochloride yields compound 7 and 8 . In alkaline solution 10 cyclises to 4-amino-3-cyclohexyl-2,3,5,6,7,8-hexahydroquinazolin-2-one ( 11 ). Compound 4 and malonitrile form either 3-amino-4-cyano-1,2,5,6,7,8-hexahydro-isoquinol-1-one ( 13 ) or 1-amino-4-cyano-2,3,5,6,7,8-hexahydro-isoquinol-3-one ( 14 ). Compound 13 and alkaline formaldehyde react to cyanooctahydroisoquinoline-[2,3-c] [1,3,5]oxdiazin-6-one ( 17 ). 2-Cyanoethyl-cyclohexan-one-2-carboxamide ( 22 ), prepared by Michael-reaction from 4 and acrylonitrile, forms via nitrile carboxamide rearrangement 10-cyano-1,2,3,4,5,6,7,10-octahydroquinolin-2-one ( 24 ) and 2-(1′-cyano-cyclohexyl-2′-one)-propionic acid ( 25 ). Nucleophilic attack of the NH₂-group at the cyanogroup of compound 22 forms 5-(spirocyclohexan-2′-one)-hexahydropyridin-2,6-dione ( 27 ).     

α-substituierte Phosphonate. 56. Synthese und Reaktionen von 1-Formylamino-2,2,2-trichlorethanphosphonaten

α-substituted Phosphonates. 56. Synthesis and Reactions of 1-Formylamino-2,2,2-trichloroethanephosphonates The chemical behaviour of formylamino phosphonates 2 , prepared from 1,2,2,2-tetrachloroethylformamid and trialkylphosphites, was investigated. The phosphonate 2b was cleaved under acidic conditions to aminosubstituted phosphonate 3 . The phosphonates 2 and 3 react with bases to 2,2-dichlorovinylphosphonates 8 and 6 , respectively. Oxazoles 9 are formed by treatment of the phosphonate 2 and 8 , respectively, with prim. or sec. amines.     

The alkaline hydrolysis of methacrylates

The hydrolysis of a number of methacrylates in a 2,5% water-alcoholic solution of sodium hydroxide at 25°C was investigated. The hydrolysis of the ester group in 2-(N-methylanilino)ethyl(III), 3- and 4-dimethylaminobenzyl-(IV, V)-2-carboxyphenyl (VI) and 2,2,2-trichloroethyl (VII) methacrylate proceeded at approximately the same rate as in methyl methacrylate (I) and dimethylaminoethyl methacrylate (II); within 25 min, some 80% of the original esters were hydrolyzed. In alkaline solutions of 1,2,2,2-tetrachloroethyl (VIII), 2-(1,2,2,2-tetrachloroethoxy)ethyl (IX) and 1-(4-chlorophenyl)-2,2,2-trichloroethyl(X) methacrylates, the rate of hydrolysis of the ester group is decreasing in the order VIII>IX>X. The hydrolysis of the ester group was characterized by the rate constants of second order.     

Neue Synthese von substituierten 4-Amino-chinazolinen und deren Heteroanalogen

New Synthesis of Substituted 4-Amino-quinazolines and Their Heteroanaloga N-Chloracetyl-anthranilonitriles react with potassium thiocyanate in the presence of alcohol to the (4-aminoquinazolin-2-yl-thio)-acetic acid ester ( 5 ). In the presence of water or primary amine the acetic acid derivative ( 6 ) or the acetic acid amide derivatives ( 7 ) are obtained. 2,4-Diaminoquinazolines ( 8 ) arise if vigorous reaction conditions are employed. With 2-chloracetylamino-cyclopent-1-en-carbonitrile as starting material the pyrimidines ( 11 ) are formed from the reaction with potassium thiocyanate. Analogously, (4-pyrimidyl-2-yl-seleno)-acetic acid ester ( 12 ) and (thiazolo[4,5-d]pyrimid-2-yl-seleno)-acetic acid derivatives ( 16 ) can be prepared with potassium selenocyanate. N-Chloracetyl derivatives of 5-membered heterocycles with enamino-nitrile structure ( 13 , 15 , 18 , 20 ) react with potassium thiocyanate to yield thieno[2,3-d]-, thiazolo[4,5-d]-, pyrrolo[2,3-d]-, furo[2,3-d]- and pyrazolo[4,3-d]pyrimidines ( 14 , 16 , 19a , 19b , 21 ).     

肝胆显像螯合剂IODIDA的合成

以2，6-二乙基苯胺为原料，经氨基保护、选择性碘化、水解、缩合，合成了N-（2，6-二乙基-3-碘苯胺甲酰甲基）亚氨二乙酸（IODIDA），总收率为15.9%。     

Formylation products of thioamides. XIII. Reaction of N-(3-aminothioacryloyl)-formamidines with amines – Synthesis of Pyrimidine Derivatives

N-(3-Aminothioacryloyl)-formamidines 3 react with primary amines to give either 4(1H)-pyrimidinthiones 6 or transaminated N-(3-aminothioacryloyl)-formamidines 5 . Alkylation of the latter compounds gives rise to cyclised 6(1H)-pyrimidinimines 7 . The 4(1H)-pyrimidinthiones 6 can be S-alkylated to 4-alkylmercaptopyrimidinium salts 8 . Subsequent substitution of the alkylmercapto group of the 8 results in the formation of 4-aminopyrimidinium salts 9 , which can also be obtained starting from the 3 by a reversed reaction sequence that is first by S-alkylation to 3-alkylmercapto-2-azapentamethinium salts 10 and subsequent reaction with primary amines.     

3,4-Dihydro-benz[1,3]oxazine Derivatives from 2-Acyl(or aroyl)-cyanatobenzenes

3,4-Dihydro-2H-benz[1,3]oxazin-2-ones 3 are obtained from 2-acyl(or aroyl)-cyanatobenzenes 2 and anisole. The reaction proceeds under Friedel-Crafts conditions via DIMROTH rearrangement. Compounds 2 , dissolved in diethyl ether, react with 1 in the presence of finely powdered KOH at ambient temperature leading to 8 . The structure of 8b is confirmed by X-ray structure analysis. (Z)-4-Ethylidene - 3,4 - dihydro -2H-benz[1,3] oxazin-2-one 9 is formed upon treatment of 2-cyanatopropiophenone 2b with diluted hydrochloric acid. The ethylene derivative 5 is obtained from 4 upon reaction with cyanogen bromide/triethyl amine.     

Hydroaminomethylation of fatty acids with primary and secondary amines — A new route to interesting surfactant substrates

The rhodium catalysed hydroaminomethylation of the unsaturated fatty acid derivatives oleic acid ethyl ester (1) and oleyl alcohol (2) with the primary amines hexylamine (3) , benzylamine (4) , aspartic acid diethyl ester (5) and valinol (6) , and with the secondary amine morpholine (7) , respectively, proceeds with good to excellent yields. Using primary amines the structure of the reaction products depends on the stoichiometry of the reactants. Performing the reaction of (1) with (3) with an excess of the amine compound the corresponding secondary amine (9) (1:1‐adduct) was observed. Working with a 2‐fold excess of (1) the tertiary amine (16) (2:1‐adduct) was the main product.     

Synthesis of oxygenated fatty acid esters from santalbic acid ester

The reaction of methyl octadec-trans-11-en-9-ynoate (1) with mercuric sulfate in the presence or absence of sulfuric acid is described. Treatment of 1 with mercuric sulfate in absolute methanol yielded methyl 9(10)-oxoocta-dec-trans-11-enoates (Product A). This product, upon treatment withm-chloroperbenzoic acid, afforded methyltrans-11,12-epoxy-9-oxooctadecanoate (4) and methyl 10-oxooctadec-trans-11-enoate (2). Sodium borohydride reduction of A furnished the corresponding hydroxy esters. The treatment of 1 with mercuric sulfate in the presence of sulfuric acid gave as major product methyl 9(10)-oxo-11(12)-methoxyoctadecanoates and methyl 9(10)-oxoocta-dec-trans-11-enoates as a minor product. When methyl 11,12-epoxyoctadec-9-ynoate was reacted with acid in methanol, methyl 12-hydroxy-11-methoxyoctadec-9-ynoate was formed, which on treatment with zinc chloride in CCl₄ yielded methyl 9,12-epoxyoctadec-9,11-dienoate exclusively. The preparation of oxo fatty esters from the total methyl esters ofSantalum album was also demonstrated. The structures of the products were established by chemical derivatization and spectral characterization.     

Zur Synthese von 3-Amino-naphth[c]isothiazolen

Synthesis of 3-Amino-naphth[c]isothiazoles 3-Amino-naphthonitrile-2 7 can be readily prepared by ring cleavage of 4-carboxy-methylthio-benzo[g]quinazoline 6 in aqueous medium at pH 9. 1-Amino-naphthonitrile- 2 11 is formed in good yield by thermolysis of 1H-benzo[g]-indoline-2,3-dione-3-oxime 13 (BEDFORD -PARTRIDGE reaction). The scope of both reaction types is studied. Appropriate syntheses of each precursor are reported. By base-catalyzed addition of hydrogen sulfide under pressure 7 and 11 were transformed into amino-thionaphthoic-2-acid amides 17 and 23 . Oxidation of 1-amino-thionaphthoic-2-acid amide 23 with hydrogen peroxide in methanol produced 3-aminonaphth[1,2-c]isothiazole 1b in almost quantitative yield. A similar oxidative cyclization of 3-amino-thionaphthoic-2-acid amide 17 to 3-amino-naphth[2,3-c]isothiazole 3b failed even if the reaction conditions were widely varied. The unsuccessful efforts to synthesize „linear”︁ naphthisothiazoles ( 3a and its 3-amino derivative 3b ) are discussed in terms of the superdelocalizability of these heterocycles. Azo dyes can be obtained from 1b and 7 .     

Deactivation behavior of ruthenium promoted Co/γ-Al2O3 catalysts in Fischer–Tropsch synthesis

Heterogeneous catalytic hydrogenation of cyclohexene, catalyzed by Pt/Al₂O₃, was carried out in solutions of 2-hydroxyethylammonium formate (a room temperature ionic liquid, RTIL) mixed with methanol, ethanol and propan-2-ol at 25 °C. The rate constants of the reaction in ionic liquid alcohol mixtures were higher than alcohol alone. First-order rate constant of the reaction in the RTIL relative to propan-2-ol is approximately 28. Furthermore, the rate constant of the reaction increases with the mole fraction of the ionic liquid. Single-parameter correlations of log k vs. normalized polarity parameter (), hydrogen-bond acceptor basicity (β) and hydrogen-bond donor acidity () do not give acceptable results in the solutions. In addition, log k does not show an acceptable dual-parameter correlation with π* (dipolarity/polarizibility, one of the Kamlet–Taft parameters for solvent that shows the dipolarity of the solvent) and , π* and β and and β. However single-parameter correlation of log k vs. π^* gives reasonable results. The increase of the reaction rate with π^* is attributed to the non-polar nature of the reactants.