A Precautionary Note Regarding Derivatization of Secondary Amines with Dialkylacetals of Formamide Other Than the Diethyl Derivative

Abstract

In an earlier communication we reported GC-MS studies on the reaction products of secondary amino tricyclics and dimethylformamide.¹ The diethyl acetal reaction products were identified as N-ethyl derivatives on the basis of mass spectroscopic analysis. In a follow-up study, we reported the same reaction products were formed from other DMF -dialkyl acetals, such as dimethyl and dipropyl acetals.² In view of this unusual reaction we reinvestigated the structure of the reaction products utilizing alternative spectroscopic methods, viz. NMR and IR.     

ACTION DES CYANOARYLIDENES ACTIVES SUR LES β -CETO- δ -CARBETHOXYPHOSPHONATES ET PHOSPHINEOXYDES: SYNTHESE DE 2-AMINO-6-(PHOSPHONOMETHYL)-4H-PYRANES

The reaction of β-keto-δ-carbethoxyphosphonates and phosphineoxides 1 with active cyanoarylidenes 2 in basic conditions provides a convenient access to the new 2-amino-6-(phosphonomethyl)-4H-pyranes 3. The reaction is found to be highly regioselective. The structure of all obtained products is confirmed by NMR ( ¹ H, ³¹ P, ¹³ C), IR spectroscopy, and in some cases by mass spectrometry.     

Construction of Extended and Polymeric 1,3-Dithiolane and Tetrathiafulvalene Derivatives using Cycloaddition of Bun 3P.CS2

Abstract

Cycloaddition of the adduct between Buⁿ ₃P and CS₂ to strained double bonds such as in norbornene gives novel zwitterionic products such as 5. This dissociates to the ylide 4 so that carrying out the reaction in the presence of an aldehyde leads to a Wittig reaction to give 2-alkylidene-1,3-dithiolanes. The compound 5 reacts with acetylenic dipolarophiles by cycloaddition accompanied by loss of Buⁿ ₃P to give dihydro-TTF derivatives. Both these reaction types also occur for norbornadiene and by using this together with dialdehydes or diacetylenes a range of new sulfur-rich extended and polymeric structures have been obtained.     

Action du Tris(Diméthylamino)phosphine et de l'Oxyde de P,P-dichlorophenylphosphine sur les N 1Tosylamidrazones: Obtention des 3-(Dimethylamino) 1,2,4,3-triazaphospholines et des 3-Oxo1,2,4,3-triazaphospholines

The reaction of N¹-tosylamidrazones with tris(dimethylamino)phosphine and P,P-dichlorophenylphosphine oxide provides respectively a convenient access to the new 3-(dimethylamino)-1,2,4,3-triazaphospholines and 1,2,4,3-triazaphosphlines-3-oxide. The structure of all obtained products is confirmed by NMR (¹ H, ³¹ P, ¹³C) and IR spectroscopy.     

Reactivite Des α -Phosphonylketones Dans la Reaction de Gewald: Synthese de Nouveaux Derives de L′aminophosphonothiophene

The reaction of α -phosphonylketones 1 with active methylenenitriles 2 leads to phosphonoalkylidenes 3 . The reaction of compounds 3 with sulfur under basic conditions leads to the new 2-amino-4-phosphonothiophenes 4 . The structure of all obtained products was confirmed by NMR (¹H, ³¹P, ¹³C) and IR spectroscopy, and in some cases by mass spectrometry.     

水介质中4-芳基-3-甲基-1-苯基-4,5,6,7,8,9-六氢化吡唑并[5,4-b]喹啉-5-酮衍生物的三组分一锅合成

在水介质中有十二烷基磺酸钠(SDS)存在下, 以芳醛、5-氨基-3-甲基-1-苯基吡唑、1,3-环己二酮三组分一锅反应合成了4-芳基-3-甲基-1-苯基-4,5,6,7,8,9-六氢化吡唑并[5,4-b]喹啉-5-酮衍生物, 产物的结构通过IR, ¹H NMR确证, 化合物4e的结构经单晶X射线衍射确证.     

MK-10 clay catalyzed,one pot,three component and efficient synthesis of novel 4-(2′,5′-disubstituted-1′H-indol-3′-yl)-2,6-bis(2″,5″-disubstituted-1″H-indol-3″-yl)pyridine-3,5-dicarbonitrile under conventional and microwave irradiation

Abstract

A series of title compounds were synthesized via a one pot, multicomponent reaction of 2,5-disubstituted indole 3-carboxaldehydes, 3-cyanoacetyl indoles, and ammonium acetate under microwave irradiation and conventional method in a short time to afford the corresponding products in high yields. It is an ideal, efficient, and environmental benign reaction. The structures of products thus obtained are confirmed by their melting point, IR, ¹HNMR, and mass spectral data.     

A Precautionary Note Regarding Derivatization Of Secondary Amines With Dialkyeacetals Of Formamide Other Than The Diethyl Derivative A Correction

Abstract

In an earlier communication we reported GC-MS studios on the reaction products of secondary amino tricyclics and dimethylformamide. ¹ The diethyl acctal reaction products were identified as N-ethyl derivatives on the basis of mass spectroscopic analysis. In a follow-up study, we reported the same reaction products were formed from other DMF-dialkyl acetals, such as dimethyl and dipropyl acetals. ² In view of this unusual reaction we reinvestigated the structure of the reaction products utilizing alternative spectroscopic methods, viz. NMR and IR, and present a correction to our earlier work ()Desipramine (1 mg) was heated with DMF-diethyl acetal (100 μ 1) at 80°C. for 15 min. The product: was dissolved in ethyl acetate (5 ml), extracted into 1 ml of 0.5 N HCl and back extracted into ethyl acetate at pH 11.0. The organic extract was dried over anhydrous sodium sulfate and evaporated to dryness under nitrogen. The resulting residue was used directly in the NMR and IR studies.     

Solid state reactions of nitrogenous heterocyclic compounds (I) —Solid state reactions of 3-methyl-1-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolon(eM PP) with aromatic aldehydes and ketones, benzil derivatives and imides, and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-lphenyl-5-pyrazolone2 were investigated. Some new solid state reactions between the reactants were found, from which a series of new compounds were obtained. The structures of the products were identified by IR,¹H NMR, MS, elemental analyses and also by X-ray crystal analysis, and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed. Project supported by the National Natural Science Foundation of China.     

Efficient and Convenient Method for Synthesis of Benzofuran-3-acetic Acids and Naphthafuran-acetic Acids

Herein, we report an efficient and convenient method for synthesis of benzofuran-3-acetic acids and naphthafuran-acetic acids 5a–p by the reaction of substituted-4-bromomethylcoumarins with aqueous sodium hydroxide at refluxing temperature. The obtained products are characterized by infrared, ¹H NMR, ¹³C NMR, and mass spectral data. Structures 5a and 5e are confirmed by their single x-ray diffraction studies. The advantages of this method are good yields, easy workup, and no chromatographic purifications.     

Spirophosphoranes from the Reaction of Disalicylaldimines with Trivalent Phosphorus Acid Amides

Abstract

A new approach to the synthesis of spirophosphoranes 9, 11, 15a-c containing P-C, P-O, and P-N intramolecular bonds was developed. It is based on the reaction of trivalent phosphorus acid amides with bis(o-hydroxyaryl)diimines. The composition and structure of the products obtained were confirmed by NMR methods, IR spectroscopy, elemental analysis and X-ray analysis.     

One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones,thiones and 2-selenoxo DHPMs using 1-butyl-3-methylimidazolium hydrogen sulfate as non-halogenated ionic liquid

Abstract

1-Butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO₄]) as a non-halogenated ionic liquid (IL) was used for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones and thiones or 2-selenoxo DHPMs in a Biginelli type multi-component reaction. By using this ionic liquid, the reaction time was significantly reduced and the products were obtained in good to high yields. Also, in this method, the synthesis of novel 2-selenoxo DHPMs is introduced in the presence of this ionic liquid and their structures were determined by ¹H and ¹³C NMR, FT-IR, and Elemental analysis.     

Studies of reactions with polymers. V. The reaction mechanism and resultant structure of PVA with PAN in DMSO without any catalyst

The reaction of polyacrylonitrile with poly(vinyl alcohol) in dimethyl sulfoxide without any catalyst was studied, and it showed that the adjacent nitrile groups on polyacrylonitrile could be linked up to form conjugated carbon-nitrogen sequence by the presence of poly(vinyl alcohol). However, no such reaction occurred when poly(vinyl alcohol) was replaced by i-propanol or poly(vinyl alcohol) graft copolymers. The structure of the resulting polymers were proposed by means of IR, UV, ¹H, and ¹³C-NMR spectroscopies. On the basis of the results, the effect of polymer feed and polymerization condition on this reaction were discussed. The compositions were determined by elemental analysis. The viscosity and thermal analysis of the products were also determined. At feed weight ratios of poly(vinyl alcohol) to polyacrylonitrile above one-half, gels were obtained.     

Synthesis and Characterization of Some Novel Dichromophoric Cyanine Dyes

Here, the synthesis of two novel series of dichromophoric cyanine dyes were reported. The first series of novel bis-azacyanine dyes 3a–d was afforded by reaction of 2-(1,3,3-trimethyle indoline-2-ylidene)acetaldehyde with diaminoaromatics, and the second series of novel bis-diazacyanine dyes 4a–d was obtained using quaternization of an amine group in disazo compounds, which were produced by the reaction of disazoaromatics with 2-methylene-1,3,3-trimethyle indoline. The products were identified by ¹H NMR, ¹³C NMR, infrared, UV-vis, and mass spectroscopy.     

Nano catalytic synthesis of flavanone phosphonates using domino Knoevenagel-phospha-Michael route

Abstract

Novel derivatives of diethyl (4-oxo-2-phenylchroman-3-yl) methyl phosphonate have been synthesized under optimal conditions using domino-Knoevenagel-phospha-Michael reaction catalyzed by nano-zinc oxide. The combination of recovery and reusability of catalyst, simple and applicable approach, good reaction time and good yields of products make this method as a suitable route for this purpose. The structures of the products were determined by FT-IR, ¹H-, ¹³C- and ³¹P- Nuclear Magnetic Resonance spectroscopies, and elemental analysis.     

微波辐射下5-取代-2-硫代海因衍生物的合成

微波辐射下, 由硫氰酸铵与α-氨基酸通过两步反应合成了11种5-取代-2-硫代海因衍生物, 并用¹H NMR, IR和元素分析确证了中间产物和终产物的结构. 对比常规加热方法, 微波辐射具有反应时间短(4 min), 每步反应产率高(85%～93%)的优点. 同时对合成化合物2h的反应历程进行了讨论.     

水相中2-氨基-4-芳基-5,6-二氢化-4H-吡喃并[3,2-c]喹啉-5-酮衍生物的合成

以芳亚甲基丙二腈或2-氰基-3-芳基丙烯酸酯和4-羟基喹啉-2-酮为原料, 水为溶剂, 在TEBA(三乙基苄基氯化铵)催化下90 ℃, 合成了2-氨基-4-芳基-5,6-二氢化-4H-吡喃[3,2-c]喹啉-5-酮衍生物. 和其它方法相比, 该反应具有反应条件温和, 产率高(87%～96%)和环境友好等优点. 产物的结构通过熔点, IR, ¹H NMR和元素分析表征. 化合物3m的结构通过X单晶衍射分析确证.     

α-Aminophosphonate derivatives of triethoxysilane for the synthesis of surface-modified silica

Abstract

A convenient synthetic route for the preparation of α-aminophosphonate derivatives of triethoxysilane, attractive precursors for silica surface functionalization, was developed. The condensation of commercially available APTES with carbonyl compounds followed by Pudovik reaction of imines with diethyl phosphite yielded desired N-phosphonomethyl functionalized (3-aminopropyl)triethoxysilanes in high yields without further purification. The chemical structures of obtained products were undoubtedly proved by ¹H, ¹³C and ³¹P NMR spectroscopy, elemental analysis and mass spectrometry.     

Reactivite des β-Cetophosphonates dans la Reaction de Gewald: Synthese de 2-Amino-5-phosphono et de 2-Amino-4-(phosphonomethyl)thiophenes

The reaction of β-ketophosphonates 1 with active methylenenitriles 2 and sulfur in basic conditions led to new 2-amino-5-phos-phonothiophenes 3 and 2-amino-4-(phosphonomethyl)thiophenes 3′. The structure of all obtained products was confirmed by NMR (¹H, ³¹P, ¹³C), IR spectroscopy and in some cases by mass spectrometry.     

TiO2 photocatalytic degradation of haloquinolines in water: Aromatic products GM-MS identification. Role of electron transfer and superoxide

To explain the differences between the product distributions obtained when quinoline (Q) in water is degraded by TiO₂ photocatalysis and by the photo-Fenton process, we have proposed a mechanism based on the reaction between superoxide and quinoline radical-cation (Q^·+), both species resulting from electron transfers at the TiO₂ surface (J. Phys. Chem. B, 101, 2650(1997)). Here is reported a GC-MS identification of the products obtained by TiO₂ photocatalytic degradation of 3-bromoquinoline and of 2-, 4-, and 6-chloroquinolines to determine the substituent effects and verify this mechanism. In all cases, besides halomonohydroxyquinolines, the main products resulted, as in the case of Q, from the oxidative cleavage of the heterocycle and were accounted for by the substituted-Q^·+ + O₂ ^·− reaction. With the halogen substituent on the pyridine ring, the latter reaction also took place on the benzene ring; the steric hindrance to the O₂ ^·− attack onto the pyridine ring of substituted-Q^·+ supports the cycloaddition mechanism for this reaction. To account for the formation of 2-aminobenzaldehyde from 2-chloro and 3-bromoquinoline, initial reductive dehalogenation is assumed to occur to a small extent. The removal rates for 6-chloroquinoline and Q were similar and those for the other haloquinolines were about twice greater, i.e. ring deactivation for electrophilic substitution had no negative effect on these rates.