Reaction of esters,ortho esters,acetals, thioacetals and epoxides with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (Lawesson reagent)

2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide,LR, reacted with ethyl formate, triethoxymethane, 1,1,1-triethoxyethane and tetraethoxymethane to give2a and3. 1,1-diethoxymethylbenzene when treated withLR produced2a,3,7,8, and9b. Triethoxymethylbenzene when heated withLR gave2a,8 and11. The reaction of benzyl formate, tris(benzyloxy)methane and 1,1-dibenzyloxy-N,N-dimethylmethanamine withLR afforded2b. Bis(methylthio)methane, tris(ethylthio)methane and 1,1-bis(butylthio)ethane withLR gave9. 1,1-Bis(2,2-dimethylpropoxy)-N,N-dimethylmethanamine withLR yielded2c and17. The reaction of 1,2-epoxyethylbenzene withLR gave20, while 1,2-epoxypropane or 1,2-epoxybutane withLR afforded23 a,b.

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Reaktionen von Estern, Orthoestern, Acetalen, Thioacetalen und Epoxiden mit 2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetan-2,4-disulfid (Lawesson Reagens)

Zusammenfassung Lawesson-Reagens (LR) reagiert mit einer Vielzahl von Verbindungen zu entsprechenden Derivaten. Es wurden folgende Reaktionspartner fürLR eingesetzt: Ethylformiat, Triethoxymethan, 1,1,1-Triethoxyethan, Tetraethoxymethan, 1,1-Diethoxymethylbenzol, Triethoxymethylbenzol, Benzylformiat, Tris(benzyloxy)methan, 1,1-Dibenzyloxy-N,N-dimethylmethanamin, Bis(methylthio)methan, Tris(ethylthio)methan, 1,1-Bis(butylthio)ethan, 1,1-Bis(2,2-dimethylpropoxy)-N,N-dimethylmethanamin, 1,2-epoxyethylbenzol, 1,2-epoxypropan und 1,2-Epoxybutan. Die entstandenen Produkte wurden mittels MS und¹³C- bzw.¹H-Spektroskopie charakterisiert.

     

The Synthesis of Triazolothiadiazines and Thiadiazoles From 1,2-Bis-(4-amino-5-mercapto-1,2,4-triazol-3-yl)- Ethanol and Ethane

The reaction of DL-malic and succinic acids with thiocarbohydrazide afforded 1,2-bis[4-amino-5-mercapto-1,2,4-triazol-3-yl]-ethane derivatives 3a and 3b. The reaction of 3a,b with phenacyl bromide and benzoin afforded 1,2-bis-1,2,4-triazolo [3,4-b][1,3,4]thiadiazine derivatives 4 and 5. The carboethoxymethylation of 3a and 3b gave 6a and 6b, respectively, and their reactions with carbon disulfide and benzoylisothiocyanate gave the 1,2-bis-1,2,4-triazolo[3,4-b][1,3,4]thiadiazole 7 and 9, and with p-nitrobenzaldehyde gave a Schiff's base and dihydrothiadiazole 8. The structures were confirmed by using ¹ H and ¹³ C NMR spectra. Selected members of these compounds were screened for antimicrobial activity.     

Spectroscopic studies of new Co(II), Cu(II), and Ni(II) complexes with 1,2-Bis(<Emphasis Type="Italic">m</Emphasis>-aminophenoxy)ethane

1,2-Bis(m-aminophenoxy)ethane was prepared in a one-stage process. In this reaction, Pd/C was used as a catalyst. 1,2-Bis(m-aminophenoxy)ethane was synthesized from 1,2-bis(m-nitrophenoxy)ethane. Diamine complexes [CoLCl₂], [CuLCl₂] and [NiL₂]Cl₂ have been synthesized and characterized by elemental analyses, Λ_M, IR, UV-Vis, ¹H NMR and magnetic measurements.     

Syntheses of Acyclo‐C‐nucleoside Analogs from 2,3:4,5‐Di‐O‐isopropylidene‐D‐xylose

Treatment of 1,2‐dideoxy‐4,5:6,7‐di‐O‐isopropylidene‐D‐xylo‐hept‐1‐yn‐3‐uloses 4a,b with hydrazine hydrate and amidines yielded the 3‐(1,2:3,4‐di‐O‐isopropylidene‐D‐xylo‐1,2,3,4‐tetrahydroxy‐butyl)‐5‐phenyl‐1H(2H)‐pyrazole 5 and the substituted 4‐(1,2:3,4‐di‐O‐isopropylidene‐D‐xylo‐1,2,3,4‐tetrahydroxy‐butyl)pyrimidines 7a–f, respectively. Reaction of 4a,b with 2‐amino‐benzimidazol afforded the 2‐(1,2:3,4‐di‐O‐isopropylidene‐D‐xylo‐1,2,3,4‐tetrahydroxy‐butyl)benzo[4,5]imidazo[1,2‐a]pyrimidines 9a,b. Compound 4a and 5‐amino‐pyrazole‐4‐carbonic acid derivatives yielded the 5‐(1,2:3,4‐di‐O‐isopropylidene‐D‐xylo‐1,2,3,4‐tetrahydroxy‐butyl)pyrazolo[1,5‐a]pyrimidines 11a–d. Deprotection of pyrazole 5, pyrimidine 7a, and pyrazolo[1,5‐a]pyrimidine 11b yielded the acyclo‐C‐nucleosides 6, 8, and 12, respectively.     

A new diaryl 1, 2-diketone from the heartwood of Dalbergia latifolia

A new diaryl 1,2-diketone, named 1-(2,5-dihydroxy-4-methoxyphenyl)-2-phenylethane-1,2-dione (1), along with eight known compounds (2–9), were isolated from the heartwood of Dalbergia latifolia. They were identified on the basis of spectral data. Compounds 1–7 were obtained from the Dalbergia genus for the first time. Compounds 8 and 9 were firstly isolated from the plant. Compound 1 exhibited inactive against Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 21530 with the minimum inhibitory concentrations of 10.0 and 10.0 mg/mL, respectively.     

Acylation of aliphatic diamines with methyl nitroacetate

N,N-Bis(nitroacetyl)diamines were synthesized for the first time by the reaction of methyl nitroacetate with aliphatic diamines in H₂O or EtOH in the presence of pyridine or imidazole. In the case of 1,2-ethylenediamine, theN-mononitroacetyl derivative was isolated as an intermediate product.Translated fromIzvestiva Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2363–2366, September, 1996     

Synthesis of “Reversed” Pyrazole‐C‐nucleoside Precursors from Push‐pull Activated Monosaccharide Derivatives

3‐O‐Benzyl‐6‐deoxy‐1,2‐O‐isopropylidene‐α‐d‐xylo‐hept‐5‐ulofuranurononitrile (1) was reacted with N,N‐dimethylformamide dimethylacetal in tetrahydrofuran to furnish the (E)‐3‐O‐benzyl‐6‐deoxy‐6‐dimethylaminomethylene‐1,2‐O‐isopropylidene‐α‐d‐xylo‐hept‐5‐ulofuranurononitrile (2) as a major product. Furthermore, treatment of compound 1 with carbon disulphide and methyl iodide under basic conditions afforded 3‐O‐benzyl‐6‐deoxy‐1,2‐O‐isopropylidene‐6‐[bis(methylsulfanyl)methylene]‐α‐d‐xylo‐hept‐5‐ulofuranurononitrile (6). Reaction of 2 and 6 with hydrazines yielded the “reversed” pyrazole‐C‐nucleoside analogs 4, 5a, 5b, 7, 8, and 9, respectively.     

Further Insight into the Reactivity of Oxazinones Toward Phosphorus Reagents

Abstract

A series of quinoline derivates has been obtained from the reaction of 3‐phenyl‐2,4‐benzoxazin‐1‐one (1) with alkylidenephosphoranes. With ester ylides 3a,b, the reaction affords hydroxyquinolines 8a,b and new stable phosphorus ylide 9, whereas with keto ylides 3c,d, quinolinones 12a,b, hydroxyindoles 10a,b and benzoazepines 14a,b are obtained. 1 reacts with allyl‐4, methyl‐5a and ethyltriphenylphosphonium bromides 5b in the presence of LiH to afford 2‐hydrophenyloxazolo[1,2‐a]‐ 4‐hydroxyquinoline (16) from the first reaction whereas alkoxyquinolines 21a,b and hydroxyazepines 22a,b are obtained from 5a,b.     

Synthesis and crystal structure of a macrocyclic complex precursor: Bis-(2-amino-1-methyliminobenzene)1,2-ethane nickel(II) dichloride

NiLCIl₂ (L?=?bis-(2-amino-1-methyliminobenzene)1,2-ethane) crystallizes in space group P-1 with a?=?9.042(2), b?=?10.263(10), c?=?11.045(2) Å, α?=?94.76(10), β?=?108.30(10), γ?= 109.86(10)°, Z?=?2, and represents a precursor of a tetradentate azamacrocyclic complex. The structure is stabilized by a system of intramolecular and intermolecular H-bonding involving chloride ions and nitrogen atoms. The coordination geometry about nickel(II) is slightly distorted octahedral.     

New acenaphthene-1,2-diimine and its reduction to the tetraanion. Molecular structures of 1,2-bis[(trimethylsilyl)imino]acenaphthene and its lithium derivatives

1,2-Bis[(trimethylsilyl)imino]acenaphthene (1) was synthesized by the reaction of acenaphthenequinone with (Me₃Si)₂NLi in toluene followed by treatment of the reaction product with trimethylchlorosilane. The dianionic derivative [(tms-BIAN)Li₂]₂ (3) was obtained as the final product by reduction of compound 1 with lithium in toluene, whereas reduction in diethyl ether afforded the tetraanion [(tms-BIAN)Li₄(Et₂O)₃]₂ (5). The formation of the paramagnetic mono-and trianions in solution was confirmed by ESR spectroscopy. Compounds 3 and 5 were isolated in the crystalline state and characterized by elemental analysis, IR spectroscopy, and NMR spectroscopy. The crystal structures of 1, 3, and 5 were established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 697–705, April, 2006.     

Synthesis and photophysical behavior of thia-aza macrocycles with 9-anthracenylmethyl moiety as fluorescent appendage

1,3-Bis(bromomethyl)-2-methoxy-5-methylbenzene, 1,3-bis(bromomethyl)-2,4,6-trimethylbenzene, 1,3- and 1,4-bis(bromomethyl)benzene undergo nucleophilic substitution with methyl mercaptoacetate to provide respective diesters 6–9. These diesters (6–9) on stirring with bis(3-aminopropyl)amine and diethylenetriamine in methanol–toluene (1:1) mixture undergo intermolecular cyclization to give respective thia-aza macrocycles 10–15. The alkylation of macrocycles 10–13 with 9-anthracenylmethyl chloride gave amine N-(anthracenylmethyl) substituted macrocycles 16–19. The extraction profile of macrocycles 10–15 towards alkali (Li⁺, Na⁺, K⁺), alkaline earth (Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺), Ag⁺, Tl⁺ and Pb²⁺ picrates shows preferential extraction of Ag⁺ with these macrocycles. The macrocycles 16–19 show fluorescence spectrum typical of anthracene moiety and depending on their structures exhibit 0–80 times increase in fluorescence on addition of transition metal ions. Fluorescent receptors 16, 17, and 19 are capable of functioning as a very efficient multi input OR logic gate.

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Graphical abstract 1,3- and 1,4-Bis(bromomethyl)benzene and its substituted derivatives undergo nucleophilic substitution with methyl mercaptoacetate to provide respective diesters 6–8. These diesters (6–8) on stirring with bis(3-aminopropyl)amine in methanol–toluene (1:1) mixture undergo intermolecular cyclization to give respective thia-aza macrocycles 10–12. The alkylation of macrocycles 10–12 with 9-anthracenylmethyl chloride gave amine N-(anthracenylmethyl) substituted macrocycles 16–18. The macrocycles 16–18 exhibit 0–80 times increase in fluorescence on addition of transition metal ions.

     

Rate constants of O2(1Δg)

The rate constants of O₂(¹Δ_g) with aliphatic alcohols, terpenes, unsaturated hydrocarbons, chlorinated hydrocarbons, oxygen, and diamines have been studied in thepresence of NO₂. The rate constants for oxygen, 1,2-ethane diamine, and 1,2-propane diamine are (9.9 ± 0.4) × 10², (8.7 ± 0.7) × 10⁴, and (1.4 ± 0.3) × 10⁴ 1/mol/s, respectively. The rate constants for all other compounds are less than the oxygen rate constant.     

1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolan und 1,2-Bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborin: Synthese und Struktur sowie Berechnungen zur Molekülstruktur

1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolane and 1,2-Bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborine: Synthesis and Structure as well as Calculations on the Molecular Structure The diphosphides K₂[(C₆H₅)P? (C₆H₅)P? P(C₆H₅)], 4 or K₂[(tBuP)? (tBuP)₂? P(tBu)], 5 , react with (ClBNMe₂)₂ to form the binary 5-membered ring system 1,2-bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolane (C₆H₅P)₃(BNMe₂)₂, 2a , and the 6-membered ring system 1,2-bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborine, (tBuP)₄(BNMe₂)₂, 3a , respectively. 2a and 3a could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analyses. The two ring systems are folded; 2a exists in the ?envelope”?- 3a in the ?boat”?-conformation. Ab initio computations for 3,4,5-triphospha-1,2-diborolane M5 show that the global minimum is characterized by one B? P double bond. The parent compound geometry M6 is characterized by transannular bonding in the PH? BH? BH? PH moiety which differs in character from those in the four- and five-membered rings (BH)₂(PH)₂ and (BH)₂(PH)₃ M5 d , respectively. Explicit calculation of the influence of amino substituents on boron improved agreement of the bond length between computed and X-ray data.     

Zur Chemie des Bis(methylsulfonyl)-amins (Dimesylamins). IV. Synthese von N-Alkyldimesylaminen mit Tetra-n-butylammonium-dimesylaminid

Investigations on Bis(methylsulfonyl)-amine (Dimesylamine). IV. Synthesis of N-Alkyl-dimesylamines with Tetra-n-butylammonium Dimesylaminide Primary and secondary alkyl iodides, diiodomethane, and α,ω-diiodoalkanes I[CH₂]_nI with n > 2 react with [(C₄H₉)₄N]N(SO₂Me)₂ in boiling CHCl₃ to form the corresponding dimesylamino alkanes. By this procedure, the new compounds 3 — 9 , 11 , 13 and 14 were prepared. Addition of bromine to the allyl compound 9 affords 10 . Alkyl chlorides and bromides do not react under these conditions. Cyclohexyl and tert.-butyl iodide eliminate olefins. ICH₂CH₂I is decomposed, forming I₂. 1,2-Bis(dimesylamino)-ethane ( 12 ), however, is prepared from ICH₂CH₂I and (MeSO₂)₂NCl. The kinetics of the alkaline hydrolysis of MeN(SO₂Me)₂ ( 1 ) is investigated.     

On the chemistry of pyrrole pigments,XCVI: An efficient synthesis of corrphycenes

Summary By means of copper catalyzed intramolecular coupling of the easily accessible 1,2-bis-(1-iodo-dipyrrin-9-yl)-ethanes and subsequent demetallation of the intermediate copper complexes corrphycenes could be prepared in nearly 40% overall yields.

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Zur Chemie von Pyrrolpigmenten, 96. Mitt.: Eine effiziente Synthese von Corrphycenen

Zusammenfassung Durch Kupfer katalysierte intramolekulare Kupplung der leicht zugänglichen 1,2-bis-(1-Iod-dipyrrin-9-yl)-ethane und anschließende Demetallierung der gebildeten Kupferkomplexe ergibt Corrphycene in Gesamtausbeuten von fast 40%.

     

Synthesis and electrochemical characterization of complexes of 1,2-bis[2-(pyridylmethylideneamino)phenylthio]ethanes with transition metals (CoII, NiII, CuII)

Transition metal (Ni^II, Co^II, and Cu^II) complexes with 1,2-bis[2-(3-pyridylmethylideneamino)phenylthio]ethane (1) and 1,2-bis[2-(4-pyridylmethylideneamino)phenylthio]ethane (2) were synthesized for the first time by slow diffusion of solutions of compounds 1 or 2 in CH₂Cl₂ into solutions of MX₂ · nH₂O (M = Ni, Co, or Cu; X = Cl or NO₃; n = 2 or 6) in ethanol. The reactions with Co^II and Cu^II chlorides afford complexes of composition M(L)Cl₂ (L = 1 or 2). The reactions of compound 1 with Ni^II salts produce complexes with 1,2-bis(2-aminophenylthio)ethane. The molecular structure of dinitrato[1,2-bis(2-aminophenylthio)ethane]nickel(ii) was confirmed by X-ray diffraction. The ligands and the complexes were investigated by cyclic voltammetry and rotating disk electrode voltammetry. The initial reduction of the complexes proceeds at the metal atom. The oxidation of the chlorine-containing complexes proceeds at the coordinated chloride anion. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–355, February, 2008.     

Reactions of germanium(II), tin(II), and antimony(III) chlorides with acenaphthene-1,2-diimines

Reactions of diimines dtb-BIAN and dph-BIAN with GeCl₂ afford germanium(II) complexes with radical-anionic ligands, (dtb-BIAN)GeCl (5) and (dph-BIAN)GeCl (6a), respectively, where dtb-BIAN is 1,2-bis[(2,5-di-tert-butylphenyl)imino]acenaphthene and dph-BIAN is 1,2-bis[(2-biphenyl)imino]acenaphthene. The latter reaction gives 6a along with [(dph-BIAN)GeCl]⁺[GeCl₃]⁻ (6b). The reactions of tin(II) and antimony(III) chlorides with dtb-BIAN and dpp-BIAN produce complexes of these halides with neutral coordinated diimines, viz., (dtb-BIAN)SnCl₂ (7) and (dpp-BIAN)SbCl₃ (8) (dpp-BIAN is 1,2-bis[(2,6-di-isopropylphenyl)imino]acenaphthene). Paramagnetic complexes 5 and 6a were studied by ESR spectroscopy. Diamagnetic compounds 7 and 8 were characterized by ¹H NMR spectroscopy. The structures of complexes 5, 6a,b, 7, 8, and (dpp-BIAN)Ge (9) were established by X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 71–80, January, 2006.     

NEW HETEROAROMATIC π -LIGANDS CONTAINING BORON

The heteroaromatic anions 2-(diisopropylamino)-1,2-thiaborolide(2a), 1-ethyl-2-phenyl-1,2-azaborolide(2b), and 2-(diisopropylamino)-1,2-oxaborolide(2c) have been prepared by a multi-step synthesis using the Grubbs ring-closing metathesis. Reactions of 2a, 2b, and 2c with Cp*ZrCl ₃ afforded the corresponding Zr(IV) complexes 3.     

A Common Sugar as Model for Many‐Sided Natural Product Modification. From D‐Fructose via D‐Tagatose to 2‐C‐Chlorodifluoro‐methylated D‐Arabinopyranos‐5‐ulose Derivatives

Abstract

Starting with 3,4‐O‐[(R)‐2,2,2‐trichloroethylidene]‐1,2‐O‐isopropylidene‐β‐D‐tagatopyranose 2 obtained from 1,2‐O‐isopropylidene‐β‐D‐fructopyranose 1 by a non‐classical one‐step acetalization with chloral/DCC, the fluoroalkylated glycosyl donors 15 and 17 were synthesised in 3–4 steps. By this sequence, one stereogenic center was inverted, one new chiral center was introduced, and one stereogenic center, for the time being eliminated, was later re‐introduced. The glycals 11 and 12, key intermediates of the synthesis sequence, were accessible from triflate precursors (e.g., 10) by treatment with DBU. Corresponding halogeno‐(6, 7), tosyl‐(5, 8), or mesyl‐(9) precursors were unsuitable. The stereoselective introduction of a chlorodifluoromethyl group was realised by dithionite‐mediated CF₂ClBr‐addition to the glycal double bond. Subsequently, either the chlorodifluoromethylated glycosyl bromide (13) or the corresponding pyranoses (14 and 16) were isolated. The latter were still acetylated to the 1‐O‐acetyl derivatives 15 and 17, respectively. An x‐ray analysis is given for the 5‐O‐tosylate 8.     

Synthesis of perhydro-1,2,5,6-tetrazocine and derivatives

Synthetic routes to the title compounds were explored. 1,2,5,6-Tetraacetylperhydro-1,2,5,6-tetrazocine ( 6 , 36%) was produced from ethylene glycol bis-p-toluenesulfonate and the potassium salt of 1,2-bis(N,N′ -diacetylhydrazino)ethane in refluxing mesitylene. Its acid-catalyzed hydrolysis led to perhydro-1,2,5,6-tetrazocine ( 9 ), an air-sensitive, crystalline solid, the first reported unsubstituted tetraazacyclooctane and the first example of an unsubstituted macrocycle incorporating two or more endocyclic hydrazino groups. 1,2-Bis(hydrazino)ethane ( 4 ) and diisobutyl oxalate in refluxing dimethylformamide gave 1,4-diamino-2,3-diketopiperazine ( 11 ) rather than 3,4-diketoperhydro-1,2,5,6-tetrazoeine ( 12 ). The acid-catalyzed reaction of benzil with 4 gave 3,4,7,8-tetraaza-1,2,9,10-tetraphenyl-2,8-dccadien-1,10-dione ( 20 ).