The reaction of allene with β-diketonatoiridium(I) complexes: synthesis,properties and crystal structures of bis(η3-allyllic) complexes of iridium(III) and of iridocyclopentane derivatives

Allene reacts with compounds of the type (β-diketonato)Ir(η-C₈H₁₄)₂| (I) to give iridium(III) derivatives of formula (β-diketonato)IrC₁₂H₁₆ (II) in which an allene tetramer i.e. the 2,3,6,7-tetramethyleneoctane-1,8-diyl group, is bonded to the iridium atom by two η₃-allylic groups. The molecular structures of these complexes were deduced by ¹H NMR studies and by single-crystal X-ray analysis of (hfacac)IrC₁₂H₁₆ (IIb). The reactions of the complexes II with hydrogen and with CO are described.The reaction of (acac)Ir(η-C₈H₁₄)₂ with allene, at -78°C, gives a thermally unstable compound of probable stoichiometry (acac)Ir(C₃H₄)₄ (VI). Its low-temperature IR spectrum and its reaction with bromine indicate that VI contains two η²-bonded allene molecules and teh 3,4-dimethyleneiridocyclopentane moiety. VI reacts with pyridine with loss of an allene molecule to give an iridium(III) derivative of formula (acac)Ir(C₆H₈)(C₃H₄)py (IX). Complex IX was shown by single-crystal X-ray analysis to contain the 3,4-dimethyleneiridocyclopentane moiety and one η²-bonded allene molecule.The role of irido cycles as precursors of the bis(allylic) complexes II is discussed.     

Synthesis and characterization of novel Schiff bases containing pyrimidine unit

The work involves synthesis of novel Schiff base derivatives containing a pyrimidine unit starting with chalcones. 4-Aminoacetophenone was reacted with 4-nitrobenzaldehyde or 4-chlorobenzaldehyde in basic medium giving chalcones, [I]_a and [I]_b, respectively, by Claisen-Schemidt reaction. The chalcones [I]_a and [I]_b were reacted with urea in HCl medium giving oxopyrimidines, [II]_a and [II]_b. They were also reacted with thiourea in basic medium to give thioxopyrimidines, [III]_a and [III]_b. The novel mono and bis Schiff bases, [VIII]_na, [VIII]_nb, [IX]_na, [IX]_nb, [X]_na, [X]_nb, [XI]_na, and [XI]_nb were synthesized by the reaction of pyrimidine derivatives; oxopyrimdines, [II]_a and [II]_b and thioxopyrimidines, [III]_a and [III]_b with 4-(4′-n-alkoxybenzoloxy)benzaldehyde [VI] and polymethylene-α,ω-bis-4-oxybenzaldehydes [VII]_m, respectively, in dry benzene using drops of glacial acetic acid as a catalyst. The synthesized compounds were characterized by melting points, elemental analysis, FTIR, and ¹H NMR spectroscopy.     

Hypocholesterolemic alkaloids of lentinus edodes (berk.) sing. II. A novel synthesis of eritadenine

A novel and convenient method for the synthesis of eritadenine (I) was established. Direct condensation of adenine and 2,3-O-isopropylidene-D -erythronolactone (II) under basic condition, followed by removal of the protecting group, afforded eritadenine (I) in fairly good yield, with accompany of a small amount of the N₃-isomer (VI). A similar reaction of adenine 1-oxide gave exclusively eritadenine oxide (VII), which was catalytically reduced to give eritadenine (I). This procedure also provided pyrimidinyl derivatives (VIII, IX and X) corresponding to cytosine, uracil, and thymine.     

Reaction of 2-carboxy-1-methylindole-3-acetic acid anhydride with amines and with S-methylisothiosemicarbazide

2-Carboxy-1-alkylindole-3-acetic acid anhydrides (I) condensed with S-methylisothiosemicarbazide in DMF to form 5,11-dihydro-6-methyl-2-methylthioindolo[3′,2′:4,5]pyrido[1,2-b]-s-triazol-5-one (II). Compound II underwent ring opening on refluxing with sodium hydroxide solution to give IV. The anhydride I reacted with primary amines in benzene to give 2-carboxy-1-alkylindole-3-acetanilide derivatives (VI) which yielded l-methylindole-3-acetic acid by decarboxylation followed by hydrolysis. Compound II oxidised to the diketo compound X which could be prepared by the hydrolysis of the azomethine derivative IX with acetic acid-hydrochloric acid mixture. Compound II reacted with benzyl chloride to yield the dibenzyl derivative XII, condensed with p-chlorobenzaldehyde to form the 11-p-chlorobenzylidene derivative XI and coupled with arenediazonium salt to give the 11-arylhydrazone derivatives XIII.     

Action of 1,2-diamines and o-aminophenols on 1-alkyl-3-carboxyindole-2-acetic acid anhydrides. Preparation of new ring systems

1-Alkyl-3-carboxyindole-2-acetic acid anhydrides (I) react with ethylenediamine and with o-phenylenediamine to give directly 10-alkylimidazo[3,2:1′,2′]pyrido[4,5-b]indol-5(1H)-ones (II) and 5,6-dihydro-5-alkyl-13H-indolo[2′,3′:4,5]pyrido[1,2-a]benzimidazol-13-one (V), respectively. However, anhydrides I react with o-aminophenol and with o-aminothiophenol to give carboxyindole-acetanilide derivatives IX, which can be cyclised to indolo[2′,3′:4,5]pyrido[2,1-b]benzoxazolone and indolo[2′,3′:4,5]pyrido[2,1-b]benzthiazolone (XI). Some derivatives of II and V were prepared to help in elucidating the structures.     

Synthesis of novel thiazoles bearing hydrazine,thiosemicarbazide, thiazole,and thiazolidinone moieties

Thiazolecarboxylate esters (I) and (II) react with hydrazine hydrate to give the acid hydrazides (III) and (IV), which then react with KSCN and PhNCS to give high yields of the thiosemicarbazides (V)-(VIII). Cyclocondensation of the thiosemicarbazide (V) with 3-phenyl-3-chloro-2-oxopropionic acid derivatives gives compounds with two thiazole moieties (IX)-(XIV). The reaction of the phenylthiosemicarbazides (VII) and (VIII) with chloroacetyl chloride and (or) chloroacetic acid affords the thiazolidinonethiazoles (XV) and (XVI).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2832–2836, December, 1991.     

Synthesis of heterocycles. Part II. New routes to acetylthiadiazolines and alkylazothiazoles

Methylglyoxalyl chloride arylhydrazones (III) react with an ethanolic solution of thiourea to give 2-amino-4-methyl-5-arylazothiazoles (XII) instead of the expected 2-acetyl-4-aryl-5-imino-Δ²-1,3,4-thiadiazolines (V) which were obtained from III and potassium thiocyanate. 3-Thiocyanato-2,4-pentanedione (IV) coupled with diazotized anilines to give V. The postulated routes to formation of V and XII from III are given. Nitrosation of V gave the corresponding N-nitroso derivatives (VI) which decomposed upon refluxing in dry xylene to give 2,4-disubstituted-Δ²-1,3,4-thiadiazolin-5-ones (VII). Boiling of either V or VI with hydrochloric acid gave the hydrochloride salt (VIII). The thiadiazolines V gave the respective N-acyl derivatives (IX) and (X) with acetic anhydride and benzoyl chloride in pyridine.     

New routes to aroylthiadiazolines and arylazothiazoles from phenylglyoxalyl bromide arylhydrazones and phenacyl thiocyanate

Reaction of phenylglyoxalyl bromide arylhydrazones (III) with thiourea in ethanol produces 2-amino-4-phenyl-5-arylazothiazoles (XI) instead of the expected 2-benzoyl-4-aryl-5-imino-Δ^2?1,3,4-thiadiazolines (V) obtained from III and potassium thiocyanate. Phenacyl thiocyanate (IV) couples with diazotized anilines to give V. The mechanisms of formation of V and XI from VI and III, respectively, are postulated. Nitrosation of V gives the corresponding N-nitroso derivatives (VII), which decompose upon refluxing in xylene to give 2,4-disubstituted Δ² ?1,3,4-thiadiazolin-5-ones (VIII). The thiadiazolines V give the respective N-aeyl derivatives IX and X with acetic anhydride and benzoyl chloride in pyridine.     

Synthèse d'homologues de la (–)--(1R,2S)-norephedrine

Synthesis of (–)-(1R,2S)-Norephedrine Homologues The amino function of esters of some simple natural amino acids I is blocked in the form of a cyanoenamine by means of 2-oxocyclopentanecarbonitrile, so that the corresponding cyanoenamino esters II are obtained. The reaction of a disubstituted lithium amide with II leeds to the cyanoenamino-amides VI . The amide function present in VI is then transformed into an aromatic ketone by means of phenyllithium, to give the (benzoylalkyl)aminocyclopentenecarbonitriles VII . Reduction of Compounds VII with NaBH₄ in EtOH ?80° affects only the keto function and leads to the [(α-hydroxybenzyl)alkyl]amino-cyclopentenecarbonitriles VIII . The amino function is then deprotected by acid hydrolysis to give the amino-alcohols IX with yields close to 50%; in every amino-alcohol IX , the erythro isomer, homologous to natural (–)-(1R,2S)-norephedrine is the more abundant or the single product. All the polyfunctional compounds prepared conserve optical activity; it has been demonstrated that the amino-alcohols IX are pure enantiomers and that no racemisation lakes place at any step of their synthesis.     

SPIONs as a nanomagnetic catalyst for the synthesis and anti-microbial activity of 2-aminothiazoles derivatives

A series of aminothiazole derivatives have been synthesized by using ultrasmall superparamagnetic iron oxide nanoparticles (SPIONs) nanomagnetic catalysis, which were prepared by reducing the Fe(II) and Fe(III) precursors using aqueous ammonia then characterized by the XRD, FTIR, SEM, and TEM. The 2-aminothiazole derivatives were obtained by coupling 2-aminothiazole diazonium salt with active methylene compounds then cyclization with hydrazine hydrate to afford pyrazolyl derivatives. The one-pot reaction of 2-aminothiazole with an aromatic aldehydes in the presence of Fe₃O₄ NPs to give Schiff bases derivatives. An efficient protocol is developed proudest yields and reduction reaction time and easy separation. Therefore, all synthesized compounds were evaluated for anti-microbial activity.     

Chemistry of sulfonyl isocyanates and sulfonyl isothiocyanates. IX. Routes to substituted oxazolidin-2-ones and oxazolidine-2-thiones

4-Chlorobenzenesulfonyl isocyanate (I) reacted with 2-chloroethanol and 1-chloro-2-propanol to give, respectively, 2-chloroethyl 4-chlorobenzenesulfonyl carbamate (III) and 1-chloro-2-propyl 4-chlorobenzenesulfonyl carbamate (VI). The carbamates III and VI cyclized under the influence of pyridine to afford, respectively, 3-(4-chlorobenzenesulfonyl)oxazolidin-2-one (IV) and 3-(4-chlorobenzenesulfonyl)-5-methyloxazolidin-2-one (VII). The oxazolidin-2-ones were stable toward hydrochloric acid but hydrolyzed in 2M sodium hydroxide solution to N-(2-hydroxyethyl)-4-chlorobenzenesulfonamide (V) and N-(2-hydroxy-1-propyl)-4-chlorobenzene-sulfonamide (VIII), respectively. 4-Toluenesulfonyl isothiocyanate (II) reacted with 2-chloroethanol to give 2-chloroethyl 4-chlorobenzenesulfonyl thiocarbamate (IX), which was converted by pyridine to 3-(4-toluenesulfonyl)oxazolidine-2-thione (X).     

Beiträge zur Chemie der Silicium-Stickstoff-Verbindungen. C. Die partielle Ammonolyse des Siliciumtetrachlorids Hexachlordisilazan. Hexachlorcyclotrisilazan

Partial ammonolysis of silicon tetrachloride in diethylether below ?60°C gives hexachlorodisilazane (I; yield 40%), hexachlorocyclotrisilazane (II; 3–5%) and polychlorosilazanes, mainly [Cl₂SiNH]_x (III). For a survey of the single steps of this reaction, see scheme 2. Cleavage of III with HCl, HBr (in benzene or ether) or SiCl₄ (elevated temperature and pressure) gives more I in moderate and octachlorotrisildiazane (IV) in very low yield. I reacts with butyllithium to lithium-bis(trichlorosilyl)amide (IX). This compound forms deutcrohexachlorodisilazane on reaction with heavy water and decomposes on heating into LiCl and decachloro-bis(silyl)-cyclodisilazane (XIX). Physical properties and analytical data of the conpounds are summarized in tables 2 and 3. Many other reactions of I, II and IX may be seen in chapter 4a, b as well as in schemes 3, 4 and 6.     

Heteropolycyclic molecules. Part IX. Synthesis of some new benzo[b]thiophene,oxofluoreno[4,3-b]thiophene,cyclic hydrazides and acridine compounds

p-Tolyl 2-thienyl ketone (I) condensed with dimethyl succinate in the presence of potassium t-butoxide to give the trans (SC₄H₃/CO₂Me) half-ester (IIIa) whose configuration was deduced by cyclization to the corresponding benzo[b]thiophene derivatives. Carbamates, esters, cyclic hydrazides and substituted phenolic and acetic acids useful as antibacterial and antiinflamatory agents were obtained. The reaction of ketone I with malononitrile to give ylidenemalononitrile II was also considered.     

Über in 6-Stellung basisch substituierte Morphanthridine. 8. Mitteilung über siebengliedrige Heterocyclen

Morphanthridines III with a basic substituent in position 6, which show neuroleptic activity, have been synthesised as follows: Chlorination of the lactams I with POCl₃ gave the iminochlorides II, which were converted by bases to the amidines III. The 11-oxo-morphanthridines VI and VII were synthesised using the same procedure, 2-(1-methylpiperazine-4-carbonyl)-2′-amino-benzophenone (XI) was obtained directly from the 6-chloro-11-oxo-morphanthridine (V) or by extended heating of VI with N-methylpiperazine. Reduction of the 11-oxo-compounds VI and VII with NaBH₄ gave the 11-hydroxy-compounds IX and X. 3-(2-aminophenyl)-phtalide (VIII) resulted from the acid hydrolysis of IX.     

(2-Chlorovinyl)chlorocarbenes: Generation and reactions with alkenes

The treatment of Z-1,1,3-trichloro-4,4-dimethyl-2-pentene (Ia) with t-C₄H₉OK in boiling hexane or benzene gave rise to (Z-2-chloro-3,3-dimethyl-1-butenyl)chlorocarbene (IVa), which reacted with alkenes to give the cyclopropane derivatives (V) in 44–57% yields. Dichloro-(2-chloro-1-alkenyl)methanes (Ib-d), which have a hydrogen atom at the C₃ position of the alkenyl substituent, were also used as carbene precursors under these conditions. These compounds gave rise to mixtures of the cyclopropanes (VI)–(VIII) (obtained in up to 57% yields) and the dienes (IX)–(XI) (yields up to 54%). The reaction of cis-2-butene with (2-chloro-1-cyclopentenyl)chlorocarbene (IVd) was found to be completely stereospecific, indicating that this carbene exists in a singlet ground state.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2552–2558, November, 1991.     

Synthesis and reactions of some 6-aryl and 2,6-diaryl-4-(4′-antipyrinyl)-2,3,4,5-tetrahydropyridazin-3-ones and screening for their antibacterial activities

Some new pyridazinone derivatives(3) were synthesized through addition of antipyrin to β-aroylacrylic acids (1) followed by cyclization of the adducts. Reactions of 3 with ethyl bromoacetate, benzenesulfonyl chloride, benzoyl chloride and POCl₃ give N-substituted products and monochlorosubstituted pyridazines (4), respectively. The reactions of the latter with thiourea give unexpected dithio-derivatives (5), which react with phenylhydrazine to give pyrazolopyridazino pyridazine derivatives (6). Reactions of 2 with NH₂OH in ethanol and pyridine afford oxime and oxazinone derivatives 7 and 8, respectively. The antibacterial activities of several compounds were screened.     

SYNTHESIS AND REACTIONS OF SOME NEW THIENO[2,3-b]-PYRIDINES AND THE ANTIMICROBIAL EFFECTS

Abstract

3,5-Dicyano-6-mercapto-4-phenylpyridin-2(1H)-one (1) was reacted with ethyl chloroacetate to give compound (II) which on reaction with hydrazine hydrate gave the corresponding hydrazide derivative (III). Acylation of (III) with acetic acid, phenylisocyanate, or phenylisothiocyanate gave different monoacyl derivatives (IV-VI). Condensation of III with aromatic aldehydes and acetylacetone gave compounds VII_a-c, VIII respectively. Compound I was reacted with chloroanilides, bromoacetone and phenacyl bromide to yield the IX-XI; these and compound II gave thieno[2,3-b]-pyridines (XU-XV) on treatment with sodium ethoxide solution. Reaction of XII with acetic anhydride gave the diacetyl derivative XVI. Hydrolysis of compound XII with sodium hydroxide gave the corresponding acid (XVII) which on treatment with acetic anhydride gave the oxazine derivative (XVIII). Reaction of oxazine compound XVIII with ammonium acetate and hydrazine hydrate gave pyrido[3′,2′:4,5] thieno[3,2-d]pyrimidin-4.7-dione derivative (XIX) and (XX) respectively. The N-amino derivative (XX) was reacted with 4-nitrobenzaldehyde to give the corresponding azomethine (XXI).

Significant in vitro gram-positive and gram negative antibacterial activities as well as anti-fungal effect were observed for some members of the series.     

Synthesis of protoheme IX derivatives with a covalently linked proximal base and their human serum albumin hybrids as artificial hemoprotein

The simple one-pot reaction of protoporphyrin IX and omega-(N-imidazolyl)alkylamine or O-methyl-L-histidyl-glycine with benzotriazol-1-yl-oxytris(dimethylamino)phosphonium hexafluorophosphate at room temperature produced a series of protoporphyrin IX species with a covalently linked proximal base at the propionate side-chain. The central iron was inserted by the general FeCl2 method, converting the free-base porphyrins to the corresponding protoheme IX derivatives. Mesoporphyrin IX and diacetyldeuteroporphyrin IX analogues were also prepared by the same procedure. The Fe(II) complexes formed dioxygen (O2) adducts in dimethylformamide at 25 degrees C. Some of them were incorporated into the hydrophobic domain of recombinant human serum albumin (rHSA), providing albumin-heme hybrids (rHSA-heme), which can bind and release O2 in aqueous media (pH 7.3, 25 degrees C). The oxidation process of converting the dioxygenated heme in rHSA to the inactive Fe(III) state obeyed first-order kinetics, indicating that the mu-oxo dimer formation was prevented by the immobilization of heme in the albumin scaffold. The rHSA-heme, in which the histidylglycil tail coordinates to the Fe(II) center, showed the most stable O2 adduct complexes.     

Synthese von borylgekoppelten Cyclotri- und -tetrasilazanen und viergliedrigen Cycloborasilazanen – Thermischer Abbau zu SiC und BN

Synthesis of Boryl-coupled Cyclotri- and -tetrasilazanes and four-membered Cycloborasilazanes – Thermal Decomposition to SiC and BN Dilithiated octamethylcyclotetrasilazane reacts with a difluoroboryl substituted cyclotrisilazane to give the BF coupled 6-8-6-membered cyclosilazane 1 , with Me₂SiHCl structural isomeric cyclotetra- and cyclotrisilazanes of the type I and II, and with Me₃SiCl structural isomeric cyclodisilazanes of the type III and IV are formed. The dilithium derivatives of the cyclosilazanes I and II as well as III and IV react with BF₃ and a BF₂-substituted cyclotrisilazane to give four-membered cyclo-borasilazanes which are coupled with a cyclodisilazane via a SiMe₂-group ( 2 – 4 ). The six-membered cycloborasilazane 5 is a byproduct in the reaction with BF₃. The reaction mechanisms are discussed. The pyrolysis with formation of SiC and BN and a crystal structure analysis were carried out with 1 .     

Die chemie der schweren carben-analogen R2M,M = Si,Ge, Sn: X. 7-sila-norbornadiene: reaktionen mit halogenen und thermolyse in genewart von metallorganischen oder organischen halogeniden

The 7-sila norbornadienes (I–IV) react rapidly with halogens at −20 to +20°C to yield Me₂SiHal₂ (Hal = Cl, Br, I) and the naphthalene or benzene derivatives (V–VIII). Bromine in CCl₄ at 0°C, however, caused surprising rearrangement in I giving the 2-bromosilylated naphthalene (IX), since an attack at the alkene group seemed to be preferred. Methylation and methoxylation of IX gave respectively X and XI. Careful hydrolysis of IX yielded the disiloxane VII. Insertions of Me₂Si into the SiHal, SiH, SiC, or SnC bonds were not observed at 160–200°C, whereas insertions into SnCl or SnH bonds occurred smoothly via a one-step mechanism. Halogen is abstracted from different CHal bonds leading to Me₂SiHal₂ and sometimes to Me₄Si₂Hal₂. The degradation of the silylene precursors in these cases is always first order and resembles that of spontaneous thermolysis.