2－甲基－3－芳基－7－（5，5－二甲基－3－酮－1－环己烯－1－基）甲酸酯－4（3H）－喹唑啉酮的合成

以2－氨基对苯二甲酸（1）为起始原料，与乙酸酐缩合生成7－羧基乙酰苯邻 甲内酰胺（2）；2和芳胺缩合产生7－羧基－2－甲基－3－芳基－4（3H）－喹唑啉 酮（3）；3和N，N－双环己基碳双亚胺（DCC）加成得到中间体4，4在4－二甲氨基 吡啶（DMAP）催化下和5，5－二甲基－1，3－环己二酮（5）缩合得到目标产物2－ 甲基－3－芳基－7－（5，5－二甲基－3－酮－1－环己烯－1－基）甲酸酯－4（ 3H）－喹唑啉酮（6）。所得15个新型化合物的结构均经^1H NMR、元素分析确证， 部分化合物经IC／MSD确证。     

2-氧代-2-[1-(3-吡啶甲基氨基)-1''''-芳基]甲基-4-芳基-5,5-二甲基-1,3,2-二氧磷杂环己烷的合成与生物活性

采用环状亚磷酸酯与亚胺的加成反应, 合成了9个未见文献报道的含吡啶基的α-氨基环状膦酸酯化合物. 其结构经1H NMR, 31P NMR, MS 和元素分析确证, 同时采用X射线单晶衍射对化合物3i的立体构型进行了进一步确证. 测定了该系列化合物的杀虫、杀菌和除草活性, 结果表明, 化合物的杀虫活性虽然较差, 但所有化合物在药液质量浓度为1.0×10-4 g/mL时都具有较好的除草活性, 部分化合物在5.0×10-5 g/mL时显示出良好的杀菌活性.     

2-氧代-2-[1-（3-吡啶甲基氨基）-1＇-芳基]甲基-4-芳基-5，5-二甲基-1，3，2-二氧磷杂环己烷的合成与生物活性

采用环状亚磷酸酯与亚胺的加成反应, 合成了9个未见文献报道的含吡啶基的α-氨基环状膦酸酯化合物. 其结构经1H NMR, 31P NMR, MS 和元素分析确证, 同时采用X射线单晶衍射对化合物3i的立体构型进行了进一步确证. 测定了该系列化合物的杀虫、杀菌和除草活性, 结果表明, 化合物的杀虫活性虽然较差, 但所有化合物在药液质量浓度为1.0×10-4 g/mL时都具有较好的除草活性, 部分化合物在5.0×10-5 g/mL时显示出良好的杀菌活性.     

Synthesis and Properties of Alkyl 2-[2-(Diarylmethylidene)hydrazinyl]-5,5-dimethyl-4-oxohex-2-enoates

Russian Journal of Organic Chemistry - Ring opening of 3-[(diarylmethylidene)hydrazinylidene]-5-tert-butylfuran-2(3H)-ones by the action of alcohols afforded previously unknown alkyl...     

Synthesis and Some Transformations of Ethyl 5-Alkoxymethyl-3-(2-methyl-3-oxobutyl)-2-oxotetrahydrofuran-3-carboxylates

Michael reaction of ethyl 5-alkoxymethyl-2-oxotetrahydrofuran-3-carboxylates with 3-methyl-3-buten-2-one gave ethyl 5-alkoxymethyl-3-(2-methyl-3-oxobutyl)-2-oxotetrahydrofuran-3-carboxylates. Alkaline hydrolysis of the latter, followed by decarboxylation afforded 5-alkoxymethyl-3-(2-methyl-3-oxobutyl)tetrahydrofuran-2-ones. The bromination of ethyl 5-alkoxymethyl-3-(2-methyl-3-oxobutyl)-2-oxotetrahydrofuran-3-carboxylates provides a convenient method for the preparation of 3-acetyl-8-alkoxymethyl-3-methyl- and 8-alkoxymethyl-3-bromoacetyl-3-methyl-2,7-dioxaspiro[4.4]nonane-1,6-diones in high yields.     

Synthesis and Crystal Structure of 5,5-Dimethyl-2-(4-chlorophenyl)(3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one-2-yl)methyl-3-(4-methoxyphenylamino)-2-cyclohexene-1-one

The title compound 5,5-dimethyl-2-(4-chlorophenyl)(3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one-2-yl)methyl-3-(4-methoxyphenylamino)-2-cyclohexen-1-one has been synthesized,and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic,space group P21/c with a=9.4193(13),b=26.915(4),c=21.188(3),β =101.906(3)°,V =5256.2(13)3,Z =4,C60H68Cl2N2O8,Mr=1016.06,Dc=1.284 g/cm3,F(000)=2160,λ(MoKα)=0.71073,μ=0.182 mm–1,R=0.0530 and wR=0.1131 for 4128 observed reflections (I>2σ(I)). X-ray analysis reveals that there are two independent molecules in the unit and the cyclohexenone rings adopt different conformations. In addition,there are four intramolecular hydrogen bonds in the title molecule.     

3－烷基-4-羟基-2-噻唑烷硫酮-4-羧酸乙酯的一锅煮合成

Ethyl 3-alkyl-4-hydroxy-2-thioxothiazolidine-4-carboxylates were prepared in excellent yields from the reaction of corresponding primary amines with carbon disulfide and ethyl 3-bromo-2-oxopropanoate in the presence of anhydrous potassium phosphate in DMF at room temperature within 1 h. The structures of the highly functionalized products were corroborated spectroscopically （IR, ^1H NMR, ^13C NMR, EI-MS） and by elemental analyses. A plausible mechanism for such type of cyclization was proposed.     

Synthesis of 2-aryl-6-(4-bromophenyl)-4-(2,2-dichlorovinyl)pyridines with the use of 1-aryl-5,5-dichloropenta-2,4-dien-1-ones

Heating 1-aryl-5,5-dichloropenta-2,4-dien-1-ones with 4-bromophenacylpyridinium bromide in AcOH in the presence of AcONH₄ gave 2-aryl-6-(4-bromophenyl)-4-(2,2-dichlorovinyl)pyridines. The reaction products were structurally characterized by¹H and¹³C NMR spectroscopy. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 955–957, May, 2000.     

Lithiation of 2-Alkyl-3-amino- and 2-Alkyl-3-(methylamino)-4(3H)-quinazolinones(1)

3-Amino-2-methyl-4(3H)-quinazolinone has been doubly lithiated, on nitrogen and in the 2-methyl group, with n-butyllithium. The lithium reagent thus obtained reacts with a variety of electrophiles (D(2)O, benzophenone, cyclohexanone, cyclopentanone, acetophenone, benzaldehyde, tetraisopropylthiuram disulfide (TITD)) to give the corresponding 2-substituted derivatives in very good yields. Reactions of the dilithio reagent with 2 molar equiv of methyl iodide or phenyl isocyanate give disubstituted derivatives. Double lithiation of the 2-ethyl and 2-propyl analogues have been achieved using LDA, and subsequent reactions with most electophiles are then similar. In the reaction of the dianion of the 2-ethyl compound with TITD, deamination from position 3 takes place with the formation of the 2-substituted derivative. In reactions with prochiral ketones, the dianion of the 2-ethyl compound gives very high diastereoselectivity. Lithiation and subsequent reactions of 3-(methylamino) analogues take place in a similar manner, thus providing access to a range of substituted 3-(methylamino)-2-alkyl-4(3H)-quinazolinones by a general procedure. Lithiation of 3-(dimethylamino)-2-ethyl-4(3H)-quinazolinone did not take place under similar conditions. Lithiation of 3-amino-2-unsubstituted-4(3H)-quinazolinone was also unsuccessful.     

Synthesis of Alkyl 5,6-Dialkyl-2-amino-3-cyanopyridine-4-carboxylates

An unusual route has been found for the hydrolysis of 3-amino-1,1-dialkoxy-6,7-dialkyl-4-aryl-3a,4,5,7a-tetrahydro-1H-pyrrolo[3,4-c]pyridine-3a,7a-dicarbonitriles in acidic medium which leads to the formation of alkyl 5,6-dialkyl-2-amino-3-cyanopyridine-4-carboxylates.     

Rearrangement in the series of 3-(2-aryl-2-oxoethyl)-3,4-dihydroquinoxalin-2(1H)-ones

4-Acetyl- and 4-succinyl-3-(2-aryl-2-oxoethyl)-3,4-dihydroquinoxalin-2(1H)-ones undergo the rearrangement into (Z)-2-(3-arylquinoxalin-2-ylidene)acetic acids accompanied by the elimination of the acyl groups. The nitration of 3-(2-oxo-2-phenylethyl)-3,4-dihydro-quinoxalin-2(1H)-one affords 5-nitro- and 7-nitro-2-carboxymethylidenequinoxalines. The bromination of quinoxalin-2-ones in AcOH gives 3-aryl-2-carboxymethylidenequinoxalines and the corresponding 7-bromo derivatives, with the former products predominating.     

Novel heterocyclization of 3-(2-aminophenylamino)- 5,5-dimethyl-2-cyclohexen-1-one

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Synthesis of Alkyl 2-Bromomethyl-4-(diethoxyphosphorylmethyl)-5-tert-butylfuran-3-carboxylates and Their Reactions with Nucleophilic Agents

Alkyl 2-methyl-4-(diethoxyphosphorylmethyl)-5-tert-butylfuran-3-carboxylates are selectivelybrominated with N-bromosuccinimide at the methyl group in position 2 of the ring. The resulting bromo-methyl derivatives react with secondary amines to form tertiary amines, with sodium butylthiolate inmethanol to form the corresponding sulfide. The reaction with potassium thiocyanate in DMF at 80°C givesa mixture of thiocyanate and isothiocyanate. When treated with phenolate or alcoholate ions, the bromomethylfurans decompose.     

芳亚甲基双(3-羟基-5,5-二甲基-2-环己烯-1-酮)类化合物的合成

在水溶剂中,酸性离子液体[bmim][HSO4]可以有效地催化芳香醛与5,5-二甲基-1,3-环己二酮反应3～5h,得到产率为76%～86%的芳亚甲基双(3-羟基-5,5-二甲基-2-环己烯-1-酮)类化合物.该反应产物后处理简单,催化剂可以回收利用.催化剂在循环使用五次时对产物的收率影响不大,是一种环境友好的绿色合成方法.     

Synthesis and Transformations of 2-Chloro-4-alkoxy(alkylthio)- 5,5-dimethyl-1,3,2-Δ3-oxazaphospholine 2-Oxide

Russian Journal of General Chemistry -     

2-苯羟甲基-5,5-二甲基-4-苯基-2-氧代1,3,2-二氧磷杂环己烷的合成及表征

以苯甲醛、异丁醛、三氯化磷为原料合成了新型的1,3,2-二氧磷杂环类化合物2-苯羟甲基-5,5-二甲基-4-苯基-2-氧代-1,3,2-二氧磷杂环己烷,总收率为40．8％,并对其进行了NMR研究和结构表征。     

Synthesis of 4-(4-Alkyl-2-morpholinyl)indoles

N-substituted 4-(2-morpholinyl)indoles were prepared from 1-(t-butoxycarbonyl)-4-acetylindole (7) which was itself prepared from 4-cyanoindole. Bromination of ketone 7, followed by reaction with amines and subsequent sodium borohydride reduction, gave amino alcohols. These were converted to α-chloro amides that were cyclized to lactams. Lithium aluminum hydride reduction served both to remove the t-BOC protecting group and to reduce the lactams to the 4-(2-morpholinyl) indoles.