SYNTHESIS OF DIASTEREOMERIC ETHYL 1-BENZOYL-6-(BROMOMETHYL)-2,2,2,4-TETRAPHENYL-3,7-DIOXA-2λ5-PHOSPHABICYCLO- [3.2.0]HEPT-4-ENE-6-CARBOXYLATE

Stable diastereomeric ethyl 1-benzoyl-6-(bromomethyl)-2,2,2,4-tetra- phenyl-3,7-dioxa-2λ ⁵ -phosphabicyclo[3.2.0]hept-4-ene-6-carboxylate was obtained in 98% yield from the reaction between dibenzoylacetylene as electron-deficient acetylenic compound, and ethyl 3-bromopyruvate in the presence of triphenylphosphine in dry ether.     

Synthesis of Novel 5H-1,2,4-Triazolo[5′,1′:2,3] [1,3]Thiazino[5,6-c]Quinoline-5-Ones

4-chloroquinoline-3-carboxylates 2 and 5-mercapto-1,2,4-triazoles 3 have been cyclised to a novel heterocyclic system 4 .     

SYNTHESIS AND POLYMERIZATION KINETICS OF 1-BROMOMETHYL-7,7-DIMETHYLBICYCLO[2.2.1]HEPT-2-YL ACRYLATE

Starting from camphene and NBS the 1-bromomethyl-7, 7-dimethylblcyclo-[2.2.1]hept-2-yl acrylate [BMCHA] has been synthesized by two steps. The polymerization kinetics equation of this monomer was obtained as follows: Rp=K[BPO]~(0.50)[BMCHA]~(1.0) and the apparent activation energy of the polymerization was evaluated to be 82.96KJ/mol.     

Synthesis of New Derivatives Benzo[4′,5′]imidazo[2′,1′:6,1]pyrido[2,3-d]pyrimidine

Russian Journal of Organic Chemistry - The reactions of 4-methyl- and (RS)-4,6-dimethyl-2-phenyl-5,6-dihydrobenzo[4′,5′]imidazo-[2′,1′:6,1]pyrido[2,3-d]pyrimidines and...     

Domino reactions in the synthesis of benzothieno[2,3-c]pyridines. New one-pot method of preparing 2-([1]benzothieno-[2,3-c]pyridin-1-yl)benzoic acids and 8,13b-dihydro[1]benzothieno[2',3':3,4]pyrido-[2,1-a]isoindol-5(7?H)-ones

A series of previously unknown 2-([1]benzothieno[2,3-c]pyridin-1-yl)benzoic acids and 8,13b-dihydro-[1]benzothieno[2',3':3,4]pyrido[2,1-a]isoindol-5(7 H)-ones has been synthesized using domino reactions, taking place at the cyclization of 2-[3-oxo-4-(phenylsulfanyl)butyl]-1,3-isoindolinediones in polyphosphoric acid.     

Synthesis of Novel Pyrrylthieno[2,3-d]Pyrimidines and Related Pyrrolo[1″,2″:1″,6″]Pyrazino[2″,3″:4,5]Thieno[2,3-d]Pyrimidines

4-Methyl-2-phenyl-5-(1-pyrryl)-6-substituted-thieno[2,3-d]pyrimidines ( 3a-c , 4a-c , 5a , b , and 6 ) have been synthesized. Some of the substituents in position 6 were used to build up different sulfur-, nitrogen- and/or oxygen-containing heterocyclic rings at that position. The 4-methyl-2-phenyl-5-(1-pyrryl)-thieno[2,3-d]pyrimidine-6-carboazide ( 20 ) was also used as a key intermediate in the synthesis of the target pyrrolo[1",2":1',6']pyrazino[2',3':4,5]thieno[2,3-d]pyrimidines.     

Pyrido[2,3-d]dipyrimidines 8. Synthesis of pyrrolo(2′,3′∶4,5)pyrido[2,3-d]pyrimidines

The reaction of 1,3-dimethyl-5-chloro-6-nitropyrido[2,3-d]pyrimidine-2,4-dione with CH-acids yielded 5-substituted pyridol[2,3-d]pyrimidines which were used in the synthesis of pyrrolo(2,34,5)pyrido[2,3-d]pyrimidines.For Communication 7, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 800–803, June, 1993.     

Synthesis of Some New Thieno[2,3-b]pyridines,Pyrimidino[4′,5′:4,5]thieno[2,3-b]-pyridines,and 2,3-Dihydro-1,3,4-thiadiazoles

Thieno[2,3-b]pyridines were synthesized from 6-benzofuran-2-yl-4-phenyl-2-sulfanylpyridine-3-carbonitrile and each of chloro acetone, ethyl chloroacetate, ω -bromoacetophenone, and chloroacetonitrile. These compounds were conveniently converted into novel pyrido[4′,5′:4,5]thieno[3,2-d]pyrimidines. Also, 2,3-dihydro-1,3,4-thiadiazole was synthesized from hydrazonoyl halides and 2-benzofuran-2-yl-3-(phenylamino)-3-thioxopropanenitrile. The structures of the products have been elucidated by elemental analyses, spectral data studies, and alternative syntheses whenever possible. The newly synthesized compounds were tested towards microorganisms.     

Competitive [2,3]- and [1,2]-oxonium ylide rearrangements. Concerted or stepwise?

The axial-equatorial conformational isomer distribution of the reactant diazoacetoacetate or its metal carbene intermediate is reflected in Rh(II) catalyzed oxonium ylide forming reactions of 3-(trans-2-arylvinyl)tetrahydropyranone-5-diazoacetoacetates that afford diastereoisomeric products for both the symmetry-allowed [2,3]- and the formally symmetry-forbidden [1,2]-oxonium ylide rearrangements.     

Pyrido[2,3-d]pyrimidines 7. Reactions of 1,3-dimethyl-5,7-dichloro-6-nitropyrido-[2,3-d]pyrimidine-2,4-dione with amines. Synthesis of derivatives of triazolo(4′,5′:4,5)pyrido[2,3-d]pyrimidine

The reaction of 5,7-dichloro-6-nitropyrido[2,3-d]-pyrimidine-2,4-dione with amines gave products of the substitution of one or two chlorine atoms by ammo groups. The catalytic reduction of 6-nitro-5,7-disubstituted pyrido[2,3-d]pyrimidines with hydrogen over palladium oxide on carbon leads to 5,6-diamino- and 5,6,7-triaminopyridopyrimidines, the reaction of which with amyl nitrite in acetic acid gives triazolo(4,5:4,5) pyrido[2,3-d]pyrimidines.For communication 6 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 398–401, March, 1993.     

双环[2.2.1]庚-5-烯-2,3-二羧酸酐封端的“PMR”型聚酰胺-酰亚胺树脂及其复合材料

以乙醇作溶剂,双环[2.2.1]庚-5-烯-2,3-二羧酸单乙酯、1,2,4-偏苯三羧酸-2-(或-1-)乙酯和4,4’-二氮基二苯甲烷为原料,合成了“PMR”型(Polymerization of Monomer Reactants)聚酰胺-酰亚胺树脂。用它制成的复合材料能在260℃长期使用。利用模型化合物对聚酰胺-酰亚胺形成的机理进行了研究。     

双环[2.2.1]庚-5-烯-2,3-二羧酸酐封头的聚酰亚胺树脂及其复合材料

合成了以乙醇为溶剂,双环[2.2.1]庚-5-烯-2,3-二羧酸乙酯、二苯甲酮四酸二乙酯和4,4’-二胺基二苯甲烷为单体的“PMR型”聚酰亚胺树脂。此树脂适用于制备复合材料。300℃恒温热老化实验表明,与玻璃布复合的增强塑料可在 250℃—300℃ 下长期使用。实验证明树脂溶液是单体的酯铵盐溶液,解决了树脂溶液分层的问题。初步研究了酰胺化、酰亚胺化和交联反应的历程。     

关于双环[2.2.1]庚-5-烯-2,3-二甲酰亚胺

对以NA封头的“PMR型”聚酰亚胺溶液中产生的沉淀物进行了分离和鉴定。测定了NA乙酯、二苯甲酮四甲酸二乙酯与二氨基二苯甲烷的反应速度常数,并对树脂溶液的稳定性和低聚物的结构进行了讨论。     

CHARACTERIZATION AND THERMAL STABILITY OF PMR POLYIMIDES USING 7-OXA-BICYCLO[2,2,l]HEPT-5-ENE-2,3-DICARBOXYLIC ANHYDRIDE AS END CAPS

An anhydride monomer containing ether oxide bridge,7-oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride (ONA),was successfully synthesized by Diels-Alder reaction of furan and maleic anhydride.The ONA was also studied as an end-cap for the polymerization of monomer reactant(PMR) type polyimides.Three molecular weight levels of the ONA end-capped PMR resins were evaluated.The effects of process conditions of these novel PMR resins on thermal and mechanical properties were investigated.It was demonstr...     

Zur kenntnis von [O2]+[Mn2F9]−

[O₂]⁺[Mn₂F₉]^? has been prepared for the first time by reaction of MnO₂ or MnF_x (x = 2,3,4) with a mixture of fluorine and oxygen (P_F2/O₂ ≈ 300–3500 atm., t ≈ 350–550°C) either as a dark red powder or as ruby red needles or plates. From single crystal studies the space group is C2/c - C⁶_2h (No. 15) with a = 17.55₂, b = 8.37₃, c = 9.10₁ Å, β = 102.3°, Z = B (at ?150°C). The crystal structure has been refined to R = 0.053 (1619 unique reflections). From the structure determination [O₂]+[Mn₂F₉] has ‘mänder’ like bands of double chains of [MnF₆] octahedra, which are stacked up in layers parallel to (100) with O₂⁺-cations (d_0?0 = 1.10₀ Å) located between the layers. ν_O2 is at 1838 cm^?1 and the magnetic moment μ_eff = 5.63 B.M. is as expected for a ‘spin only’ case without spin-spin interaction.     

Dihydrodiazepine aus valenzisomeren diazatricyclo[3.2.0.0.2,4]Heptanen1)

Cycloaddition of diazoalkanes to diazabicyclo[2.2.0]hexenes and subsequent extrusion of nitrogen afford diazatricyclo[3.2.0.0^2,4]heptanes that are easily valence isomerized to novel dihydrodiazepines.     

Zur kenntnis von [O2]22+[Ti7F30]2−

[O₂]²⁺₂[Ti₇F₃₀]^2? has been obtained by reaction of TiO₂ with a mixture of fluorine and oxygen (p_F2/O2 ≈ 300–3500 atm., t ≈ 300–450°C) either as colourless powder or in form of colourless, clear needles. From single crystal studies the spacegroup is P$\text{3}$ - C_3i¹ (No. 147) with a = 10.19₂, c = 6.50_o Å, Z = 1. The crystal structure has been refined to R = 0.086 [R_w = 0.058] (748 unique reflexions [F_o > 2σ(F_o)]). From the structure determination [O₂]²⁺₂[Ti₇F₃₀]^2? has isolated columns of partially distorted [TiF₆] octahedra (- column structure) which are connected only quite loosely by (disordered) O₂⁺ cations. ν_O2+ is at 1857 cm^?1, the magnetic moment μ_eff = 2.35 B.M. (295 K) is quite as expected for a ‘spin-only’ case.     

双环[2.2.1]庚-5-烯-2-羧酸乙酯的Prins反应

本文讨论了双环[2.2.1]庚-5-烯-2-羧酸乙酯在采用无水甲酸作反应介质时的Prins反应.在反应中发现有Wagner-Meerwein类重排发生,并分到重排产物,也有未经重排但发生内酯化的产物存在.