Triphenylphosphine-carbon Tetrachloride Research Articles

ChemInform Abstract: A Convenient Synthesis of Diethyl 1-Chloroalkylphosphonates.

The title compounds were obtained in high yield by the reaction of diethyl 1-hydroxyalkylphosphonates with triphenylphosphine carbon tetrachloride

Development of Nonsymmetrical 1,4-Disubstituted Anthraquinones That Are Potently Active against Cisplatin-Resistant Ovarian Cancer Cells

A novel series of 1,4-disubstituted aminoanthraquinones were prepared by ipso-displacement of 1,4-difluoro-5,8-dihydroxyanthraquinones by hydroxylated piperidinyl- or pyrrolidinylalkylamino side chains. One aminoanthraquinone (13) was further derivatized to a chloropropylamino analogue by treatment with triphenylphosphine-carbon tetrachloride. The compounds were evaluated in the A2780 ovarian cancer cell line and its cisplatin-resistant variants (A2780/cp70 and A2780/MCP1). The novel anthraquinones were shown to possess up to 5-fold increased potency against the cisplatin-resistant cells compared to the wild-type cells. Growth curve analysis of the hydroxyethylaminoanthraquinone 8 in the osteosarcoma cell line U-2 OS showed that the cell cycle is not frozen, rather there is a late cell cycle arrest consistent with the action of a DNA-damaging topoisomerase II inhibitor. Accumulative apoptotic events, using time lapse photography, indicate that 8 is capable of fully engaging cell cycle arrest pathways in G2 in the absence of early apoptotic commitment. 8 and its chloropropyl analogue 13 retained significant activity against human A2780/cp70 xenografted tumors in mice.

Conversion of Alcohols to Bromides Using a Fluorous Phosphine.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Conversion of alcohols to bromides using a fluorous phosphine

Abstract Reaction of alcohols with the fluorous phosphinecarbon tetrabromide complex in toluene or in a two-phase toluene-FC-72 system afforded the corresponding bromides in good yields. The fluorous-phosphine oxide is readily separated by liquid–liquid extraction, providing an alternative to the homogeneous triphenylphosphine–carbon tetrachloride conversion, as well as to the polymer-supported phosphine method. The fluorous phosphine oxide could be reduced and the product reused.

The Dimerisation of 5,6-Dimethoxy-Indene

The reaction of 5,6-dimethoxy-indanol with acids or with triphenylphosphine-carbon tetrachloride afforded several dimeric compounds; in the dimerisation of 5,6-dimethoxy-indene with SiO2–AgNO3 only a single dimer was obtained.

Isotope Effect and Kinetic Studies of the Reaction of Tertiary Alcohols with Triphenylphosphine–Carbon Tetrachloride: Ion Pair or Concerted?

Kinetics of the reactions of 1,2,3-triphenyl-2-propanol ( 1), 1,2-diphenyl-2-propanol ( 2) and 3,3,3-trideuterio-1,2-diphenyl-2-propanol ( 3) with triphenylphosphine–carbon tetrachloride in the temperature range of 25–78°C in several solvents are investigated. In a non-polar solvent (CCl 4), the reaction of ( 2) proceeds via intermolecular anti E2 elimination and/or intermolecular S N2 nucleophilic substitution (28% substitution, ratio of 2-alkene/1-alkene=1.06, E/ Z≥49). In a polar solvent (CH 3CN) reaction proceeds via E1 and/or S N1 (24% substitution, 2-alkene/1-alkene=1.9, E/ Z≥6. At equilibrium, the ratio of 2-alkene/1-alkene is equal to 99 with E/ Z≥4.21. The primary kinetic isotope effect ( k H/ k D) for the elimination pathway in the non-polar solvent is equal to 4.90 and 3.90 at temperatures of 25 and 60°C, respectively. A small secondary β-isotope effect of 1.10 was observed for substitution reaction at both temperatures. Direction of substitution (S N2 vs. E2) depends on temperature and polarity of the solvent. The energetics (Δ S ‡, Δ G ‡, Δ H ‡), the rate orders, and optimization of molecular geometry of intermediates by semiempirical methods (AM1 and CNDO) all agree with intermolecular E2 and S N2 mechanisms. New rules for stereoselectivity and Hofmann–Saytzeff eliminations are considered.

Synthesis of Ocimin, A 1,5-Diene, by a Bis- Grignard Reaction

Ocimin, 1,6-bis-(4-methoxyphenyl)-(E)-(E)-hexa- 1,5-diene, was synthetized by the bis-Grignard reaction of p-anisaldehyde with 1,4-bis- (br0momagnesium)butane and the dehydration of the intermediate diol using triphenylphosphine-carbon tetrachloride.

A Convenient Synthesis of Diethyl 1-Chloroalkylphosphonates

The title compounds were obtained in high yield by the reaction of diethyl 1-hydroxyalkylphosphonates with triphenylphosphine carbon tetrachloride.

Synthesis of N-phenylalkanehydrazonoyl chlorides.

N-Phenylalkanehydrazonoyl chlorides (5), hitherto unknown, were synthesized from the corresponding arylhydrazides of aliphatic carboxylic acids (1) with triphenylphosphine-carbon tetrachloride in good yields.

Chlorination of Acyclic β-Diketones. Formation and Stability of β-Chloro-β,γ-unsaturated Ketones

Abstract Chlorination of acyclic β-diketones with triphenylphosphine–carbon tetrachloride and the other chlorinating reagents predominantly afforded β-chloro-β,γ-unsaturated ketones except the cases of the terminal alkyl group of the diketones was methyl or t-butyl. In these reactions, the isomerization of the β-chloro-α,β-unsaturated ketones to the β,γ-unsaturated isomers was involved; the isomerization was achieved by triphenylphosphine–carbon tetrachloride as well as by some acid catalysts.

Ribonucleoside cyclic 3′,5′-phosphoramidates: synthesis, stereochemistry, and conversion into ribonucleoside cyclic 3′,5′-phosphorothioates and -[18O]phosphates

Base- and O2′-protected nucleoside cyclic 3′,5′-phosphates (1) react with aniline in the presence of triphenylphosphine–carbon tetrachloride to give the nucleoside cyclic 3′,5′-phosphoranilidates (2), which after separation into individual diastereoisomers are converted in stereoretentive manner into the corresponding nucleoside cyclic 3′,5′-phosphorothioates (3). Isotopomers of adenosine cyclic 3′,5′-[18O] phosphates (9a) are prepared via two independent routes: (a) reaction of adenosine cyclic 3′,5′-phosphoranilidates (2a) with sodium hydride–[18O]benzaldehyde (retention) or (b) acid-catalysed hydrolysis of adenosine cyclic 3′,5′-N,N-dimethylphosphoramidates (10a)(inversion).Adenosine cyclic 3′,5′-phosphoranilidothioates (Sp)-(23) and (Rp)-(23), prepared via cyclisation of the corresponding 5′-[O-(4-nitrophenyl)phosphoranilidothioates](22), have been converted into P-achiral adenosine cyclic 3′,5′-phosphorodithioate (26).

Preparation and determination of configuration of 3-halogeno-3-methyl-5α-cholestane epimers

3α-Chloro-3β-methyl- and 3β-chloro-3α-methyl-5α-cholestane were prepared by reaction of hydrochloric acid with the two epimeric 3-hydroxy-3-methyl-5α-cholestanes. A better yield and cleaner conversion could be obtained with tetramethyl-1-chlorovinylamine as chlorinating agent. Reaction of the two 3-methyl-5α-cholestanols with triphenylphosphine–carbon tetrachloride or phosphorus trichloride oxide–pyridine gave mixtures of 3-methyl-5α-cholest-2-ene, 3-methyl-5α-cholest-3-ene, and 3-methylene-5α-cholestane. The two epimeric 3-fluoro-3-methyl-5α-cholestanes were obtained by treatment of the two 3-methyl-5α-cholestan-3-ols with (diethylamino)sulphur trifluoride. The configuration of the 3-halogeno-3-methyl-5α-cholestanes was determined from their 13C n.m.r. spectra. The availability of both 3-halogeno-3-methyl-5α-cholestane epimers allowed an unambiguous interpretation of the i.r. spectra in the 800–400 cm–1 region.

Stereochemical aspects of the reaction of dialkyl phosphates with amine in the presence of triphenylphospine and carbon tetrachloride

Activation of P-chiral dialkyl phosphates with triphenylphosphine-carbon tetrachloride involves intermediate phosphonium salt 1 which undergoes nucleophilic attack by aniline or pyridine with inversion of configuration at the chiral phosphorus atom.

CHLORINATION OF ACYCLIC β-DIKETONES. FORMATION OF β-CHLORO-β,γ-UNSATURATED KETONES

Abstract Chlorination of acyclic β-diketones with triphenylphosphine-carbon tetrachloride and the other chlorinating reagents afforded β-chloro-β,γ-unsaturated ketones except when the terminal alkyl group was methyl or t-butyl. Unsymmetrical acyclic β-diketones yielded a mixture of the products chlorinated on each carbonyl carbon.

Dichloromethylenation of esters and lactones by triphenylphosphine-carbon tetrachloride reagent

Reaction of triphenylphosphine-carbon tetrachloride reagent with esters and lactones produced 1-substituted 2,2-dichlorovinyl ethers. Hydrolysis of these ethers in acidic conditions afforded the dichloromethyl ketones.

5-thio- l-rhamnose

Two routes for the synthesis of methyl 5- S-acetyl-6-deoxy-2,3- O-isopropylidene-5-thio- l-mannofuranoside (8) have been examined. Reaction of l-rhamnose with methanol in the presence of the cation-exchange resin gives methyl 6-deoxy-α- l-mannofuranoside (2), which on conventional acetonation yields methyl 6-deoxy-2,3- O- isopropylidene-α- l-mannofuranosides (3). Compounds 3 is also obtained by acetonation of l-rhamnose followed by treatment with a mixture of methanol, acetonation, Amberlite IR-120(H +) resin. Chlorination of 3 with triphenylphosphine-carbon tetrachloride gives methyl 5-chloro-5,6-dideoxy-2,3- O-isopropylidene-β- d-gulofuranoside (7), which reacts with potassium thioacetate to give 8. Alternatively, 3 is iodized with ruthenium tetraoxide to methyl 6-deoxy-2,3- O-isopropylidene-α- l- lyxo-hexofuranosid-5-ulose (9), which reduced by sodium borohydride mainly to methyl 6-deoxy-2,3- O-isopropylidene-β- d-gulofuranoside (10). The O-tosyl derivative of 10 reacts with potassium thioacetate to produced 8. Hydrolysis of 8 with 90% aqueous triflouroacetic acid, followed by acetolysis with a solution of acetic acid, acetic anhydride, and sulfuric acids gives an anomeric mixture of 1,2,3,4,-tetra- O-acetyl-6-deoxy-5-thio- l-mannopyranoses (12), together with a small proportion of 1,2,3,-tri- O-acetyl-5- S-acetyl-6-deoxy-5-thio-β- l-mannofuranose (13). Deacetylation of 12 or 13 gives 5-thio- l-rhamnose (6), from which crystalline 1,2,3,4-tetra- O-( p-nitrobenzoyl)-5-thio-β- l-rhamnopyranose (14) is obtained.

Selective, reductive dechlorination of chlorodeoxy sugars. Structural determination of chlorodeoxy and deoxy sugars by 13C nuclear magnetic resonance spectroscopy

The reductive dechlorination of chlorodeoxy sugars by hydrogenation over Raney nickel in the presence of potassium hydroxide or triethylamine has been investigated; a selective dechlorination was observed in most cases with triethylamine. Several new, chlorodeoxy furanoid derivatives have been synthesized by the use of triphenylphosphine–carbon tetrachloride. 13C magnetic resonance spectroscopy has been employed for the assignment of structure to the chlorodeoxy sugars and the corresponding reduced products.

On the mechamism of the reaction of triphenylphosphine-carbon tetrachloride with alcohols, acids and enolizable ketones

On the mechamism of the reaction of triphenylphosphine-carbon tetrachloride with alcohols, acids and enolizable ketones

Conversion of some bicycloheptanols to chlorides using triphenylphosphine-carbon tetrachloride. Stereochemistry and mechanistic implications

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTConversion of some bicycloheptanols to chlorides using triphenylphosphine-carbon tetrachloride. Stereochemistry and mechanistic implicationsRichard G. Weiss and Eugene Irving SnyderCite this: J. Org. Chem. 1970, 35, 5, 1627–1632Publication Date (Print):May 1, 1970Publication History Published online1 May 2002Published inissue 1 May 1970https://doi.org/10.1021/jo00830a079RIGHTS & PERMISSIONSArticle Views294Altmetric-Citations48LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (775 KB) Get e-Alerts Get e-Alerts