Synthesis and spectroscopic studies of some heterocyclic compounds. Reaction of 3-aryl-1-phenyl-2-propen-1-ones with ethyl phenylacetate

3-Aryl-1-phenyl-2-propen-1-one I reacted with ethyl phenylacetate (II) in the presence sodium ethoxide at room temperature to give the corresponding ethyl β-aryl-γ-benzoyl-α-phenyl-butyrate III. However,' when the same ketones were refluxed with ethyl phenylacetate, they gave the corresponding 4-aryI-3,6-diphenyl-3,4-dihydro-2H-pyran-2-ones IV. The reactions of III and IV with hydrazine hydrate afforded the corresponding hydrazones VI and 2-pyridones VIII, respectively. The structure and configuration of the products are based on chemical and spectroscopic evidence.     

Reactions of substituted pyridines and their N-oxides with ethanolic sodium hydroxide and various alkoxides

2-Benzoylpyridine 1-oxide with ethanoiic sodium hydroxide yielded acyl nucleophilic displacement products and a redox product, 2-(α-hydroxybenzyl)pyridine. 3-Benzoylpyridine 1-oxide under the same conditions yielded only a reduction product, 3-(α-hydroxybenzyl)-pyridine 1-oxide, whereas 4-benzoylpyridine 1-oxide yielded only a redox product, 4-(α-hydroxy-benzyl)pyridine. The redox reaction which is promoted by base occurs with an α-hydroxybenzylpyridine 1-oxide which results from a carbonyl reduction of the starting material. The benzoyl-pyridine 1-oxides reacted qualitatively the same with sodium ethoxide or isopropoxide as they did with ethanoiic sodium hydroxide, but they reacted differently with potassium t-butoxide or aluminum isopropoxide. The cyano- and benzenesulfonyl-pyridine 1-oxides reacted with ethanolic sodium hydroxide to yield pyridinecarboxylic acids and 1-hydroxypyridones, respectively.     

Synthesis of 2(3H)-benzofuranone derivatives by copper (i)-promoted substitution reactions of active methylene carbanions

Activation of soft carbanions by copper(I) in the sub-stitution reaction toward aryl halides and allyl halides was demonstrated. Derivatives of 2(3H)-benzofuranones (2, 14 -18) were prepared in a one-pot procedure by the reaction of copper(I) diethyl malonate with sodium o-bromophenoxide. 2-Hydroxybenzofuran (4) and its 2-amino derivative (5) were obtained by using copper(I) salts of ethyl acetoacetate and ethyl cyanoacetate. The reaction of sodium p-bromophenoxides with copper(I) diethyl malonate yielded p-1,1,2,2-tetracaeboethoxyethylphenols (7, 8). 3-Carboethoxy-3-β-methallyl-2-benzofuranone (14) was converted into spiro[2-benzofuranone-3,3'-(5',5'-dimethyl)-γ-butyrolactone] (22) under acidic conditions. The latter compound was further decarboxylated to give spiro [2-benzofuranone-3,1'-(2',2'-dimethyl)cyclopropane] (23) by the treatment with sodium ethoxide.     

Aryl hydrazidates—I. Synthesis and their conversion into hydrazides A new chapman-like rearrangement in the hydrazone series

N-arylbenzhydrazidic halides (I) with phenols and thiophenol in ethanol in presence of sodium ethoxide give aryl N-arylbenzhydrazidates (II) and phenyl thiohydrazidates (V), respectively. The esters II resisted hydrolysis but strong acid cleaved them to 2-aroyl-1-arylhydrazines (VII). At high temperatures esters of type II (but not V) undergo quantitative intramolecular rearrangement to give 2-aroyl-1,1- diarylhydrazines (XIV). Structural assignments have been made on the basis of IR and UV spectra and independent synthesis.     

Heterocycles. Part V. Reaction of α,β-unsaturated carbonyl compounds with arylacetamides. A synthesis of 2-pyridone derivatives

The reaction of 1,3-diaryl-2-propene-1-ones I with arylacetamides II, in the presence of sodium ethoxide under reflux, for two hours, gave the corresponding 3,4,6-triaryl-3,4-dihydro-2(1H)-pyridones IV. However, when the reaction of these ketones was carried out in the presence of sodium hydride, they gave the corresponding 3,4,6-triaryl-2(1H)-pyridones VI or a mixture of IV and VI. When 1,3-diaryl-2-propyne-1-ones V were reacted with arylacetamides, in the presence of sodium hydride, they yielded the corresponding 2-pyridones VI. Treatment of compounds IV with selenium produced the corresponding 2-pyridones VI. Acetylation of the latter compounds gave the corresponding 2-acetyl derivatives VIII. The structure of all products was confirmed by chemical and spectroscopic evidence, and the mechanism of the reactions was discussed.     

Synthesis and reactions of N-Aryl-C-arylsulfonylformohydrazidoyl bromides

Bromination of 1-arylsulfonyl-1,2-propanedione-1-aryl-hydrazones 7 in a mixture of acetic acid and acetic anhydride in the presence of sodium acetate gave N-aryl-C-arylsulfonylformohydrazidoyl bromides 5. Treatment of 5 with dibenzoylmethane, acetylacetone, ethyl acetoacetate and ethyl benzoylacetate in ethanol in the presence of sodium ethoxide yielded the pyrazole derivatives 8-11 , respectively. Reaction of 5 with potassium thiocyanate afforded the thiadiazoline derivative 14. The bromides 5 also react with nucleophiles such as morpholine, piperidine, phenoxide, thiophenoxide and benzenesulfinate anions to give the corresponding substitution products 19-23 , respectively. The structures of the products 8-23 were assigned and confirmed on the basis of their spectral and elemental analyses, their chemical behaviour and alternate synthesis wherever possible.     

Reactions of azidoheterocyclic compounds with C - H acids

1-Phenyl-4-azido-5-chloro-6-pyridazone (I) reacts with acetylacetone, benzoylacetone, dibenzoylmethane, and acetoacetic ester in the presence of triethylamine to give 1,2,3-triazolyl-6-pyridazones. Diazodicarbonyl derivatives were obtained with diethyl malonate and acetoacetic ester in the presence of sodium ethoxide. Dimedone and indane-1,3-dione react with I to give 1-phenyl-4-amino-5-chloro-6-pyridazone and 2-diazodimedone and 2-diazoindane-1,3-dione, respectively.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 256–258, February, 1973.     

Synthesis and Reactions of Some New Thienopyrimidines

4-Methyl-6-mercapto-2-phenylpyrimidine-5-carbonitrile ( 1 ) was reacted with different halo compounds, namely ethylchloroacetate, chloroacetone, bromoacetanilide, p-chlorobromoacetanilide, and p -methoxy chloroacetanilide in ethanol in the presence of sodium acetate yielded the corresponding S-alkylated derivatives ( 2a-e ). The latter compounds underwent cyclization into thienopyrimidines ( 4a-e ) upon treatment with sodium ethoxide in ethanol. The reaction of ( 4a ) with hydrazine hydrate led to the formation of 5-amino-4-methyl-2-phenylthieno[2,3-d]pyrimidine-2-carbohydrazide ( 5 ). Compound ( 5 ) was reacted with a variety of reagents to produce other new thienopyrimidines as well as oxadiazolylthienopyrimidines ( 6, 11 ).     

Acetylinic ketones. Part II.. Reaction of acetylenic ketones with nucleophilic nitrogen compounds

Aroylphenylacetylenes (I) reacted with ethyl and phenyl hydrazinecarboxylates (II) to give ω-aroylacetophenone-N-ethoxycarbonyl-(Vla-f) and N-phenoxycarbonyl-(VIg-l) hydrazones, respectively. When these were healed with acetic anhydride they were converted to 5-aryl-1-ethoxycarbonyl-and 1-phenoxycarbonyl-3-phenylpyrazoles (VII), respectively, which on hydrolysis with rnethanolic potassium hydroxide gave the corresponding 5(3)aryl-3(5)phenylpyrazoles (VIII). Reaction of the above acetylenic ketones with guanidine hydrochloride in the presence of sodium carbonate gave the corresponding 2-amino-6-aryl-4-phenylpyrimidines (XII). Similarly, reaction of benzoylphenylacetylene with thiourea and with urea in the presence of sodium ethoxide gave rise to 2,4-diphenylpyrimidine-2-thione (XVIII) and 2,4-diphenyl-2(1H)pyrimidin-one (XV), respectively.     

乳液聚合型品红成色剂的合成

2，4，6-三氯苯肼与β-乙氧基-β-亚氨基-丙酸乙酯在乙醇钠的存在下，经缩 合成环生成1-(2＇，4＇，6＇-三氯苯基)-3-氨基-5-吡唑啉酮(3)．3和它的4-位衍 生物与甲基丙烯酰氯反应生成了三种可聚合的成色剂单体．将这些单体与丙烯酸丁 酯共聚得到了三种乳液聚合型品红成色剂．给出了合成反应中间体及单体的红外光 谱与核磁共振光谱数据，讨论了影响合成反应及乳液聚合反应的一些因素．     

Reactions of α,β-unsaturated ketones with cyanoacetamide

3-Aryl-1-phenyl-2-propen-1-ones Ia-f and aroylphenylacetylenes Va-d reacted under reflux for 3 hours with cyanoacetamide in the presence of sodium ethoxide to give the corresponding 4-aryl-3-cyano-6-phenyl-2-(1H)pyridones VI. However, when ketones Ia-e were refluxed with cyanoacetamide for one hour in the presence of sodium ethoxide or piperidine, they gave the corresponding 4-aryl-3-cyano-3,4-dihydro-6-phenyl-2-(1H)pyridones IIIa-e, which upon heating with selenium gave the corresponding 2-pyridones VI. The structures of the products are based on chemical and spectroscopic evidence.     

Synthesis of 6-(2-hydroxyaryl)-2-pyridones by the reaction of chromones with cyanoacetic,acetoacetic, and malonic acid amides

A reaction of chromones with cyanoacetic, acetoacetic, and malonic acid amides in the presence of sodium ethoxide furnished a number of new 3-substituted 6-(2-hydroxyaryl)-2-pyridones in good yields, including those containing a polyfluoroalkyl group at position 4.     

Synthesis and biological assessment of some fused Pyran derivatives

Pyran was formed by reacting methyl 3-methoxyacrylate (1) with 2-benzylidenemalanonitrile to form compound 2 . The pyrano derivatives 3–6 were obtained by reacting the second molecule with 2-benzylidenemalanonitrile, carbon disulfide, formamide, and benzylidene cyclohexanone. Compound (2) interacted with ethyl chloroacetate to form compound 8 , which then cyclized in the presence of sodium ethoxide to form compound 9 . Compound 7 was formed when compound (2) was treated with acetic acid in the presence of sulfuric acid and reacted with ethylchloroacetate to form compound 10 and then was converted to compound 11 by the addition of sodium ethoxide. Analytical and spectral data have been used to determine the structures of the newly synthesized substances and they were then tested for their antibacterial and antioxidant activities. In terms of antioxidant activity, compounds 2 and 8 were found to have the greatest and lowest levels, respectively, against Enterobacter aerogenes.     

氟氯代β-二酮的合成

从二氟氯乙酸乙酯与甲基酮的Claisen酯缩合反应合成了一些氟氯代β-二酮.用格氏试剂与氟代羧酸酯加成,多氟芳基镉与乙酰氯反应以及氟代β-酮酸酯水解等方法合成了一些新的多氟烃基甲基酮R_FCOCH_3.     

Study on synthesis of fluotochloroalkyl β-diketones

Several fluorochloroalkyl β-diketones were synthesized from Claisen condensation of ethyl difluorochloroacetate with methyl ketone in the presence of sodium ethoxide. The fluorinated methyl ketones, which were used as one of the reactants in the Claisen condensation were synthesized by the following methods, namely: the addition of methyl Grignard reagent to ethyl difluorochloroacetate; the addition of bis(m-chlorotetrafluorophenyl) cadmium to acetyl chloride and the hydrolytic decomposition of β-keto ester.     

Synthesis of optically active poly(2-phenylvinyl alkyl thioethers) and corresponding monomers

Cis-(S)(+)-2-phenylvinyl alkyl thioethers having 1-methylpropyl (I), 2-methylbutyl (II), and 3-methylpentyl as alkyl groups, were prepared by condensation of phenylacetylene with sodium thioalcoholates in the presence of sodium ethoxide. Thioethers I, II, and III did not polymerize with radical initiators but could be polymerized cationicaly with BF₃·Et₂O or SnCl₄ in bulk at room temperature to oligomers with molecular weights about 2000. Specific rotations of polymers were compared with those of phenylethyl alkyl thioethers, and it was found that there was no difference in the rotation of polymers having molecular weights up to 2000 and model compounds.     

A Convenient Synthesis of NovelDerivatives of Pyrido[2,3- d ][1,2,4]triazolo[4,3- a ]pyrimidine-5,6-dione

 Reaction of 6-Amino-2-thiouracil with hydrazonoyl halides yielded regioselectively 7-amino-1,3-disubstituted-1,2,4-triazolo[4,3-a]pyrimidine derivatives. Upon treatment with methyl (Z)-2-benzoylamino-3-dimethylaminopropenoate, the corresponding methyl (Z)-2-benzoylamino-3-([1,2, 4]triazolo[4,3-a]pyrimidin-7-yl)-amino propenoates were obtained which cyclized in the presence of sodium ethoxide to afford novel derivatives of pyrido[2,3-d][1,2,4]triazolo[4,3-a]pyrimidine-5,6-(1H,8H)-diones.     

Alkoxide-induced reactions of N-substituted saccharins. Synthesis of 1,2-benzothiazocine 1,1-dioxide and 2,3-dihydropyrrolo[1,2-b]-[1,2]benzisothiazole 5,5-dioxide derivatives

The reactions of saccharin derivatives 1 with sodium alkoxides were studied. Under mild conditions, compounds 1a-f gave the corresponding open sulfonamides 5a-f . Under drastic conditions, β-(saccharin-2)propionic acid derivatives 1a,b reacted with sodium ethoxide affording saccharin and β-ethoxypropionic acid derivatives 4a,b . γ-(Saccharin-2)butyric acid derivatives 1c,d and γ-(saccharin-2)-butyrophenone 1f reacted with sodium t-butoxide in dimethyl sulfoxide affording 5-substituted 6-hydroxy-3,4-dihydro-2H-1,2-benzothiazocine 1,1-dioxides 9 . From mother liquors, 1-substituted 2,3-dihydro-pyrrolo[1,2-b][1,2]benzisothiazole 5,5-dioxides 10 were isolated several hours later, though not detected immediately after completing the reaction. When the reactions were carried out in t-butyl alcohol, the yields of 9 diminished and those of 10 increased with product ratio inversion. Different experimental observations on the possible pathway generating 9 and 10 are discussed.     

O-Alkylations of pyridoxine and pyridoxamine

O-Alkylations of pyridoxine 1 and pyridoxamine 5 were carried out in acetone in the presence of sodium ethoxide and potassium iodide to give 5-alkoxy-6-methyl-3,4-(bishydroxymethyl)pyridines 2a-j and 5-alkoxy-4-aminomethyl-6-methyl-3-hydroxyrnethylpyridines 6a-e .     

Reactions of 2-(trifluoromethyl)chromones with cyanoacetamides, ethyl cyanoacetate and diethyl malonate. Unexpected synthesis of benzo[c]coumarin derivatives

While 2-(trifluoromethyl)chromones react with cyanoacetamides in the presence of sodium ethoxide to produce 6-(2-hydroxyaryl)-4-(trifluoromethyl)-2-oxo-1,2-dihydropyridine-3-carbonitriles, their reactions with ethyl cyanoacetate and diethyl malonate under the same conditions took an entirely different course and gave novel functionalized derivatives of 6H-benzo[c]chromen-6-one.