Sodium Alkoxide In Alcohol Research Articles

Synthesis of Novel Benzosuberone Derivatives using Organophosphorus Reagents and their Antitumor Activities

2-Arylidenebenzosuberones react with a Wittig-Horner reagent in the presence of sodium hydride as a base to give the novel dimethyl (4-(4-methoxyphenyl)-2-oxa-2,3,4,5,6,7-hexahydrobenzo- [6,7]cyclohepta[1,2-b]pyran-3-yl)phosphonate. On the other hand, 6,7-dihydrobenzo[6,7]cyclohepta- [1,2-b]pyran-2(5H)-ones were isolated from the reaction of 2-arylidenebenzosuberones withWittig- Horner reagents using alcoholic sodium alkoxide. The reaction of 2-arylidenebenzosuberones with trialkyl phosphites affords the alkyl phosphonate derivatives. Tris(dialkylamino)phosphines react with 2-arylidenebenzosuberones to give the oxaphospholanoxide products. 2-Arylidenebenzosuberones react with Lawesson’s reagent to yield the corresponding dimers. Some of the prepared products were screened for antitumor activity

Reactions of 5(4H)-Oxazolones with Wittig-Horner Reagents: Novel Synthesis of Dioxopyrrolidinephosphonates and Phosphonoalkanoates with Anticipated Schistosomicidal Activity

Abstract 4-Benzylidene-2-phenyl-5(4H)-oxazolones react with Wittig-Horner reagents in the presence of alcoholic sodium alkoxide to give novel dioxopyrrolidinephosphonates, diethyl [3-(benzoylamino)- 1-cyano-2-oxo-4-phenylbut-3-en-1-yl]phosphonate and phosphonoalkenoate derivatives. Both the phosphonate adducts and the ester products were also isolated from the reaction of oxazolones with triethyl phosphonoacetate using alcoholic sodium ethoxide and/or sodium hydride as a base. Possible reaction mechanisms are considered, and the structural assignments are based on analytical and spectroscopic results. The biological evaluation of the new compounds is reported.

Studies on the Synthesis of Some New Cyanopyridine-Thione and Thieno[2,3-b]pyridine Derivatives

The work included in this article involves the synthesis of new cyanopyridinethiones as good synthons for new thieno[2,3-b]pyridines with anticipated biological activities. Thus, the reaction of β–aryl-α-thiocarbamoylacrylonitrile ( 1a–c ) with (2-thenoyl)-ω,ω,ω-trifluoroacetone led to an unexpected formation of 4-aryl-3-cyano-6-(2-thienyl)pyridine-2(1H)-thiones ( 4a–c ). In contrast, the reaction of 1a,b with ethyl acetoacetate produced 4-aryl-3-cyano-5-ethoxycarbonyl-6-methylpyridine-2(1H)-thiones ( 12a,b ). The reaction of compound 4a with methyl iodide gave 2-methylthio derivative 6 , which upon treatment with hydrazine hydrate furnished pyrazolopyridine 7 . Treatment of 4a–c with chloroacetaimde, in the presence of sodium ethoxide, led to the formation of 3-amino-4-aryl-6-(2-thienyl)thieno[2,3-b]pyridine-2-carboxamides ( 8a–c ). The reactions of 8a with some aromatic aldehydes and/or cycloalkanones were carried out and their products were identified. Compounds 12a,b were reacted with chloro-N-arylacetamides to give ethyl 4-aryl-2-(N-aryl)carbamoylmethylthio-3-cyano-6-methylpyridine-5-carboxylates ( 13a–j ). Upon treatment of compounds 13a–j with sodium alkoxide in alcohol, they underwent an intramolecular Thorpe-Ziegler cyclization to furnish ethyl 3-amino-4-aryl-2-(N-aryl)carbamoyl-6-methylthieno[2,3-b]pyridine-5-carboxylates ( 14a–j ). Compounds 14a–j , in turn, were reacted with triethyl orthoformate and/or carbon disulfide to give corresponding pyridothienopyrimidinone derivatives 15a–j and 18 . Pyridothienotriazinone analogs 17a–j were synthesized via diazotisation of compounds 14a–j .

The Reaction of Wittig and Wittig-Horner Reagents and Alkyl Phosphites with 1,2-Naphthoquinone-1-benzimide

Carbomethoxymethylene and carbethoxymethylene triphenylphosphoranes (1a, b) react with 1,2-naphthoquinone-1-benzimide (8) to give the corresponding 1-benzoylimino-1H-naphthalen-2-ylidene-acetic esters 9a,b and 2-(1-benzoylamino-naphthalen-2-yl)-but-2-enedioic esters 10a,b together with 1-benzamido-2-naphthol (11). Application of Wittig-Horner reagents 4a,b on 8 at room temperature and in the presence of alcoholic sodium alkoxide renders 2-(1-benzoylamino-naphthalen-2-yl)-3-phosphonylsuccinic esters 12a,b. Conducting the reaction in refluxing toluene and in the presence of sodium hydride led to the formation of 2-benzamido-naphthol-1-ethyl ether (13). 1-Benzamido-2-naphthol (11) was also isolated from both reaction media. Trimethyl and dimethyl phosphites (7a,b) react with 8 to 14 as the sole product. Mechanisms accounting for the formation of the new products are discussed, and the probable structures of the products are presented based on analytical and spectroscopic data.

Reactions with aziridines, 51: Ring opening of cis‐2‐Benzyl‐3‐phenyl‐1‐(phenylsulfonyl)aziridine by alkoxide. The first eliminative fission of an aziridine with uncharged nitrogen

AbstractThe title compound 2 can be ring‐opened in three ways by alcoholic sodium alkoxide: nucleophilic substitutive opening in (the benzylic) position 3 [attack (a)] and in position 2 [attack (b)] as well as the novel nucleophilic eliminative opening which is initiated by deprotonation of the benzylic substituent [attack (c)]. The primary cleavage product 5 of attack (c) is an allylic sulfonamide that slowly isomerizes to give the elusive enamide 6, the precursor of the isolated ketone 7. Attack (a) predominates with methoxide and less so with ethoxide. Attack (c) increases with size (and basicity?) of the alkoxide and is the only detected reaction with tert‐butoxide.

Heteryladamantanes. Communication 6. Synthesis and some properties of 6-(1-adamantyl)-3-cyanopyridin-2(1H)-one

1. 6-(1-Adamantyl)-3-cyanopyridin-2(1H)-one has been obtained for the first time by reaction of the sodium salt of 3-(1-adamantyl)-1-hydroxyprop-1-en-3-one with cyanoacetamide. 2. The regioselectivity of the alkylation reaction on the oxygen atom of the substituted pyridone by halomethylene-active compounds has been established. 3. A nucleophilic substitution reaction where an OCH2COOR group is replaced by an OR group has been discovered in 6-(1-adamantyl)-2-alkoxycarbonylmethoxy-3-cyanopyridines when they are treated with excess sodium alkoxide in alcohol.

Indole β-nucleophilic substitution. Part 6. Photochemical transformations of oxepino[3,2-b]indolones

[2]Benzoxepino[4,3-b]indol-11-ones and pyrido[x′,y′:5,6]oxepino[3,2-b]indol-5-ones are transformed in the presence of light into indole-spiro(2-alkyl-2-aroyl)-3-ones. These, in the presence of air, in alcohol as solvent (or in some cases with alcoholic sodium alkoxide) are further converted into indolo[1,2-b]isoquinoline-6,12-diones and aza-analogues respectively.

Synthesis of N-acyl-1,3-oxathiol-2-imines

A facile synthesis of N-acyl-1,3-oxathiol-2-imines, 7, is reported. It comprises the reaction of O-alkyl acylcarbamothioates, 4, with 2-chloroketones in the presence of alcoholic sodium alkoxide. The resulting O-alkyl-S-substituted-N-acylcarbonimidothiates, 6, undergo cyclization with elimination of alcohol, spontaneously, or upon heating in boiling toluene to form 7.

Selenium Catalyzed Synthesis of of Carbonates. The Reaction of Alkoxide with Carbon Monoxide and Oxygen in the Presence of Selenium

Abstract A novel selenium catalyzed synthetic reaction of carbonates was investigated. The reaction of alkoxides with carbon monoxide in the presence of stoichiometric amount of selenium gave carbonates in high yields under atmospheric pressure at 20°C in THF. When the resultant reaction solution was made to react continuously with the mixture gas of carbon monoxide and oxygen, catalytic formation of carbonates was achieved. Isolation of Se-alkyl monoselenocarbonate from the reaction mixture by addition of alkyl halide indicated that carboalkoxy sodium selenide might be formed as an intermediate in the course of present reaction. In connection with these reactions, the reaction of carbonyl selenide with sodium alkoxide in alcohol was also studied.

A NOVEL ETHER FORMATION REACTION VIA CHLOROACETYLHYDRAZONES

Abstract Chloroacetylhydrazones were allowed to react with sodium alkoxide in alcohol to give acetic ester of the alcohol and unsymmetrical ethers derived from the alkoxide and the alkylidene moiety of the hydrazones. Secondary and tertiary alkoxides failed to afford any amount of ethers. High yields of ethers were realized especially in the reaction of cyclohexanone chloroacetylhydrazone.

Preparation of α-Bromo-4-nitrostilbenes and Diphenylacetylenes

α-Bromo-4-nitrcstilbenes and diphenylacetylenes were prepared by utilizing the modified Wittig reaction.Diethyl a-bromo-p-nitrobenzylphosphonate [2] was obtained quantitatively by bromination of diethyl p-nitrobenzylphosphonate [1].Treatment of [2] with aromatic aldehydes in the presence of an equivalent amount of sodium alkoxide in alcohol at room temperature gave the corresponding a-bromo-4-nitrostilbenes in good yield.The use of two equivalent amounts of base gave diphenylacetylenes. Similarly the reaction of α-iodo-p-nitrobenzylphosphonate with aromatic aldehydes was investigated.