Asymmetric synthesis of organoelemental analogs of natural compounds. 7. (2R,3S)-2-amino-3-hydroxy-5-phosphonovaleric acid

The reaction of the Ni(II) complex of the Schiff base of glycine with (S)-2-N-(N¹-benzylprolyl)-o-aminobenzophenone with diethyl-3-bromo-2-hydroxypropyl phosphonate yields the corresponding complex from which (2R, 3S)-2-amino-3-hydroxy-5-phosphonovaleric acid is separated with HCl.See [1] for Communication 6.Institute of Bioorganic Chemistry and Petrochemistry, Ukrainian Academy of Sciences, 252660 Kiev; N. A. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1172–1175, May, 1992.     

Reaction of 1-amino-2-phenylethynyl-and 2-acylethynyl-1-amino-9,10-anthraquinones with HNO2. Synthesis of 1H-3-acylnaphtho[2,3-g]indazole-6,11-diones

The reactions of 1-amino-2-phenylethynyl-and 2-acylethynyl-1-amino-9,10-anthraquinones with HNO₂ in a mixture of dioxane and a mineral acid at 20 °C were studied. Under these conditions, 2-alkynyl-1-amino-9,10-anthraquinones, irrespective of the structure of the C=CR substituent, are cyclized into 3-substituted 1H-naphtho[2,3-glindazole-6,11-diones. The nature of the acetylenic group in the initial compound and the choice of the mineral acid determine the structure of the substitutent in position 3 of the product (1,1-dichloroalkyl or acyl) but have no effect on the regiospecificity of cyclization. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 110–114, January, 1997.     

Reactions of methyl 1-acetylenyl-9,10-anthraquinone-2-carboxylates with hydrazine

Methyl 1-acetylenyl-9,10-anthraquinone-2-carboxylates react with NH₂NH₂ in ethanol at 80°C to give commensurable amounts of substituted 7H-dibenzo[de,h]quinolin-7-ones and 3,4-dihydro-3-aminonaphtho[2,3-f]isoquinoline-4,7,12-triones. The main, route of the reaction apparently includes nucleophilic addition of the reagent to the triple bond of the ester followed by intramolecular cyclization of the adduct with either the carbonyl or the methoxycarbonyl groups involved. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10 pp. 2031–2035, October, 1998.     

1-Methyl-2(3,4)-(1-vinylpyrrol-2-yl)pyridinium iodides: some structural features revealed by 1H and 13C NMR spectroscopy

The reactions of 2-, 3-, and 4-(1-vinylpyrrol-2-yl)pyridines with methyl iodide afford the corresponding quaternary salts. Analysis of their ¹H and ¹³C NMR spectra showed that the quaternization of the nitrogen atom considerably enhances the -acceptor effect of the pyridine ring on the pyrrole ring and on the vinyl group. 1-Methyl-2-(1-vinylpyrrol-2-yl)pyridinium iodide contains no weak intramolecular C--H...N hydrogen bond present in the starting compound.     

Photochemical and thermal rearrangements of 2-arylamino-1-(4-tert-butylphenoxy)-9,10-anthraquinones

Photochemical transformations of 2-arylamino-1-(4-tert-butylphenoxy)-9,10-anthraquinones involve migration of thetert-butylphenyl group either to theperi-located carbonyl oxygen to give 2-arylamino-9-(4-tert-butylphenoxy)-1,10-anthraquinones or to the nitrogen atom to give 2-aryl(4-tert-butylphenyl)amino-1-hydroxy-9,10-anthraquinones (typical products of the Smiles rearrangement). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2519–2522, December, 1998.     

2-氨基-6-氟-9-(4-羟基-3-羟甲基丁基)嘌呤的合成

报道了2-氨基-6-氟-9-(4-羟基-3-羟甲基丁基)嘌呤(1)的合成, 通过对起始原料2-氨基-6-氯-9-(4-乙酰氧基-3-乙酰氧甲基丁基)嘌呤(2)水解脱去乙酰基, 得到2-氨基-6-氯-9-(4-羟基-3-羟甲基丁基)嘌呤(3). 化合物3与三甲胺乙醇溶液在混合溶剂[V(THF)∶V(DMF)＝3∶1]中反应得到相应的氯化铵盐4, 然后与KF在DMF溶剂中反应, 得到化合物1. 产品经UV-vis, IR, ¹H NMR, ¹⁹F NMR和MS表征. 考察了反应温度、氟化试剂等因素对氟化反应的影响, 为6位含氟的嘌呤核苷类化合物的合成提供了一种直接、简易的新方法.     

A multinuclear NMR study in the solid state and in solution of thallium(I) tris-(pyrazol-1-yl)borates (thallium scorpionates)

The ¹H, ¹³C and ¹⁵N NMR spectroscopic properties of six thallium tris-(pyrazol-1-yl)borates, including a tetrakis derivative, were determined. The results in solution were necessary to understand those, more complicated, in the solid state. A collection of ²⁰⁵Tl-¹⁵N and ²⁰⁵Tl-¹³C couplings was measured in the latter state. Among those, a very large coupling constant (between 194 and 282 Hz) has been measured on the carbon at the position 4 of the pyrazole ring in several compounds and particularly for the cyclobutyl derivative [Tl(Tp^Cbu)]. It has been assigned to a direct interaction of the 4-C-H ? Tl type and related to the X-ray structures, when available.     

1-(1-Adamantyl)diaziridine

The reaction of 1-aminoadamantane with CH₂O and H₂NOSO₃H in the presence of K₂CO₃ under phase-transfer conditions leads to hitherto unknown 1-(1-adamantyl)diaziridine and (1-adamantyl)aminoacetonitrile, characterized by spectral data. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 861–862, April, 1997.     

Transformations of 1-amino-2-(3-hydroxyalk-1-ynyl)-9,10-anthraquinones in the presence of amines

When heated in piperidine, 1-amino-2-(3-hydroxyalk-1-ynyl)-9,10-anthraquinones undergo cyclization into 2-(1-hydroxyalkyl)naphtho[2,3-g]indole-6,11-diones. In contrast, 1-amino-2-(3-hydroxy-3-phenylpropynyl)-9,10-anthraquinone reacts with primary and secondary amines to give the corresponding 1-amino-2-(1-amino-2-benzoylvinyl)-9,10-anthraquinones, which undergo cyclization into 4-dialkylamino- or 4-alkylamino-2-phenylnaphtho[2,3-h]quinoline-7,12-diones. Heating of the starting phenylpropynol with Et₃N causes its dehydrogenation and isomerization.     

Determination of the structure of 7-diethylamino-4-(1,2,3-triazol-1-yl)-2H-1-benzopyran-2-one derivatives using two-dimensional heteronuclear chemical-shift correlated NMR techniques

¹H and¹³C NMR spectra of 7-diethylamino-4-(1,2,3-triazol-1-yl)-2H-1-benzopyran-2-one derivatives have been studied. The location of the substituent in the 1,2,3-triazole ring was determined by the 2D COLOC method. It was established that the H(3) and H(5) protons in the coumarin moiety experience anisotropic influence of the phenyl subsituent at the C(5) atom in the triazole ring.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1330–1332, July, 1994.     

1H and 13C spectral assignment of 2(1H)-pyridone derivatives

1H and 13C NMR spectroscopic data for 4-aryl-3,4-dihydro-6-methyl-2(1H)pyridone derivatives were fully assigned by a combination of one- and two- dimensional experiments (DEPT, HMBC, HMQC, COSY, NOE).     

(S)-2-氨基-1,1-二苯基-1-丙醇的合成

以L-丙氨酸为原料,经苄基保护、格氏反应和脱苄基反应合成了(S)-2-氨基-1,1-二苯基-1-丙醇,总收率48.1%,其结构经1H NMR,IR,EI-MS和元素分析表征。     

Synthesis and characterization of some novel cadmium(II) complexes with 3-hydroxypicolinic acid (3-OHpicH): Crystal and molecular structures of [CdI(3-OHpic)(3-OHpicH)(H2O)]2, [Cd(3-OHpic)2(H2O)2] and [Cd(3-OHpic)2]n

Cadmium(II) complexes of 3-hydroxypicolinic acid, namely [CdI(3-OHpic)(3-OHpicH)(H₂O)]₂ (1), [Cd(3-OHpic)₂(H₂O)₂] (2) and [Cd(3-OHpic)₂]_n (3) were prepared and characterized by spectroscopic methods (IR, NMR) and their molecular and crystal structures were determined by X-ray crystal structure analysis. Complexes 1 and 2 were prepared in similar reaction conditions using different cadmium(II) salts: cadmium(II) iodide and cadmium(II) acetate dihydrate, respectively, while 3 was prepared by recrystallization of 2 from N,N-dimethylformamide solution. Various coordination modes of 3-OHpicH in 1–3 were established in the solid state: bidentate N,O-chelated mode in 1 and 2, monodentate mode through the carboxylate O atom from zwitterionic ligand in 1 and bidentate N,O-chelated and bridging mode in 3. In the DMF solution of all prepared complexes, only monodentate mode of 3-OHpicH binding to cadmium(II) through the carboxylate O atom was established by ¹H, ¹³C, ¹⁵N and ¹¹³Cd NMR spectroscopy.     

2,4-二酮-5-咪唑烷基尿的~(15)N和~(13)C核磁共振研究

本实验测定了2.4-二酮-5-咪唑烷基尿的~(15)N和~(13)C NMR谱并确认了谱线归属。根据化学位移及其在脱质子化过程中的变化,讨论了化合物的互变异构平衡及立体构型的转化问题。结果表明,在溶液中此化合物以酮式结构(A)为主要构型。     

(3S,4S)-4-氨基-3-羟基-6-甲基庚酸的合成

价廉易得的L-亮氨酸先以苄基同时保护氨基及羧基得(S)-2-(二苄胺基)-4-甲基戊酸苄酯,进而在碱性条件下与乙腈发生亲核取代反应得(S)-4-(二苄胺基)-6-甲基-3-氧代庚腈,再经硼氢化钠选择性还原羰基得(3S,4S)-4-(二苄胺基)-3-羟基-6-甲基庚腈,用双氧水氧化得(3S,4S)-4-(二苄胺基)-3-羟基-6-甲基庚酸,最后在Pd(OH)2/C-H2作用下脱掉苄基得到(3S,4S)-4-氨基-3-羟基-6-甲基庚酸,即(3S,4S)-statine。整个合成路线总产率为33.6%。     

Structure and spectroscopy of diorganotin(IV) complexes derived from N′-(2-hydroxy-3-methoxybenzylidene)benzohydrazide

Three new diorganotin(IV) complexes of the general formula R₂Sn[3-(OMe)-2-OC₆H₃CHN-NC(O)Ph] (R = Ph, Ia; R = Me, Ib; R = n-Bu, Ic) have been synthesised from the corresponding diorganotin(IV) dichlorides and the ligand, N′-(2-hydroxy-3-methoxybenzylidene)benzohydrazide in methanol at room temperature in the presence of trimethylamine. All the complexes have been characterized by elemental analysis, IR and ¹H, ¹³C, ¹⁵N, ¹¹⁹Sn NMR spectra, and their structures have been confirmed by single crystal X-ray diffraction analysis of one representative compound Ia. Complex Ia crystallises in the orthorhombic system, space group Pna2₁ with a = 12.424(5), b = 9.911(5), c = 18.872(5) Å; Z = 4. The ligand N′-(2-hydroxy-3-methoxybenzylidene)benzohydrazide (H₂L) coordinates to the metal centre in the enolate form via the phenolic O, imino N and enolic O atoms. In Ia, the central tin atom adopts a distorted trigonal bipyramidal coordination geometry with the oxygen atoms in axial positions, while the imino nitrogen atom of the Schiff base and the two phenyl groups occupy the equatorial sites. The δ(¹¹⁹Sn) values for the complexes Ia, Ib and Ic are −327.3, −151.7 and −187.2 ppm, respectively, thus indicating penta-coordinated Sn centres in solution.     

(1)H and (13)C chemical shifts for 2-aryl and 2-N-arylamino benzothiazole derivatives

The (1)H and (13)C NMR resonances for forty-three 2-aryl and 2-N-arylamino benzothiazole derivatives were completely assigned using a concerted application of one- and two-dimensional experiments (DEPT, gs-COSY, gs-HMQC and gs-HMBC).     

Synthesis of 2-oxazolidinones from (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol

A series of isomeric 2-oxazolidinones has been synthesized from (1S, 2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 579–584, April, 2006.     

Various approaches to the use of 3-acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile in heterocyclic synthesis

Two approaches to the use of 3-acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile (1) in heterocyclic synthesis are considered. A method for preparing 3-acetyl-4-amino-5-cyano-2-methylpyridine directly from1 andN,N-dimethylformamide dimethylacetal (DMF DMA) was proposed, together with a synthetic route to 2-(2-amino-3-cyano-6-hydroxy-phenyl)-8-cyano-5-hydroxy-4-methylquinoline based on the transformation of hydroxyvinyl ketone1 into its diphenylboron chelate and condensation of the latter with DMF DMA. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 127–130, January, 1997.     

Stereochemicai study of 7-aryl-1,7,8,8a-tetrahydro-3(2H)indolizinones by1H and13C NMR

Stereochemistry of 7-aryl-1,7,8,8a-tetrahydro-3(2H)-indolizinones was studied by¹H and¹³C NMR. Complete assignment of¹H NMR signals and analysis of¹H-¹H coupling constants were performed using the iterative PANIC program. Values of³ J _6,7,³ J _7,8endo, and⁴ J _5,7 allow one to unambiguously identify the correspondingexo- andendo-stereoisomers. For stereoisomers with exo-orientation of H(7), complete assignment of¹³C NMR signals was performed on the basis of analysis of the¹³C-¹H coupling constants using two dimensional heteronuclear shift-correlating spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 591–593, March, 1996.