Bimolecular displacement reactions. III. Reaction of phenols with triphenylphosphine and bromine

Schaefer, John P.; Higgins, Jerry

doi:10.1021/jo01280a069

Cited by 28 publications

(4 citation statements)

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“…The target compound was obtained from 2-bromonaphthalene in hexane. 1 H NMR (500 MHz, THF- d 8 , 298 K) δ 8.34 (s, 1H), 8.12 (d, J = 7.3 Hz, 1H), 7.57–7.50 (m, 2H), 7.32 (d, J = 7.4 Hz, 1H), 7.15 (t, J = 7.3 Hz, 1H), 7.07 (t, J = 7.3 Hz, 1H).…”

Section: Methodsmentioning

confidence: 99%

Aggregation Behavior of Lithionaphthalenes in Solution: Experimental and Theoretical Study

et al. 2020

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The aggregation of a series of mono- and dilithionaphthalenes in THF solutions in the presence of tetramethylethylenediamine (TMEDA) and pentamethyldiethylenetriamine (PMDTA) was studied by NMR spectroscopy and quantum chemical calculations. The stability of dimeric species in diluted solutions as well as reasons of their disaggregation in some cases has been discussed. For the lithioderivatives of 1,8-bis(dimethylamino)naphthalene (DMAN) the possibility of NMe2 group coordination to the lithium atom in ortho-position of naphthalene core under steric pressure of substituents was demonstrated by quantum chemical calculations. For the first time, dilithionaphthalenes were studied by 1H, 13C, and 7Li NMR spectroscopy. It was shown that while β-dilithionaphthalenes form oligomeric aggregates in solutions, α-dilithionaphthalenes exist as solely monomeric species with each lithium atom coordinated to both peri-positions.

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Section: Methodsmentioning

confidence: 99%

Aggregation Behavior of Lithionaphthalenes in Solution: Experimental and Theoretical Study

et al. 2020

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“…Treatment of farnesol with PPh 3 -CBr 4 at 0 °C afforded farnesyl bromide. 4 The bromide contained less than 5% of the (2Z,6E)-isomer and was used for the following reaction without further purification. Treatment of the bromide with dimethyl malonate (5 equiv.)…”

Section: ′mentioning

confidence: 99%

Synthesis of norsesterterpene rac- and ent-rhopaloic acid A

Takagi¹,

Sasaoka²,

Kojima³

et al. 1997

Chem. Commun.

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Scheme 3 Reagents and conditions: i, Et 3 N (1.2 equiv.), pivaloyl chloride (1.2 equiv.), THF, then N-lithiooxazolidin-2-one, THF, 278 °C, 15 h, 66%; ii, LDA (1.1 equiv.), THF, 278 °C, 30 min, then allyl bromide (4 equiv.), 220 to 210 °C, 6 h, 44%; iii, LiAlH 4 (3 equiv.), THF, 0 °C, 15 h, 92% iv, NaH (1 equiv.), Me 2 CHSH (1 equiv.), (EtO) 2 P(O)(NCH 2 )CO 2 Et, THF, 0 °C, 10 min, then 10*, 25 °C, 28 h, 46% (Z isomer only); v, MeI (3 equiv.), AgBF 4 (1 equiv.), CH 2 Cl 2 , 5 h then Bu 4 NF (3 equiv.), THF, 25 °C, 13 h, 35%; vi, aq. KOH (excess), reflux, 18 h, 56%

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“…These compounds in the solid state are found crucially dependent on the nature of the solvent used in the synthesis process 10 . Compounds of the formula R 3 PX 2 ; [R= Ph, Me, n-octyl, n-hexyl, n-butyl X=Cl, Br, I] and compounds of the formula [11][12][13] Ph 3 PXY; (XY=Br 2 , I 2 , IBr) that have been prepared in acetonitrile, dichloromethane or in nitrobenzene [14][15][16] are ionic with tetrahedral geometry and the correct form will be [R 3 polar solution leads to the formation of another geometrical structure of these compounds which is a four co-ordinate molecular spoke structure of the formula R 3 E-X-X in the solid state as it has been proved by x-ray crystallographic studies. In CDCl 3 solution, which is a highly polar solvent, all the compounds ionise completely to form [R 3 3 ] have been synthesized in diethyl ether.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystallographic Characterization and Density Functional Study of Novel Spoke-Molecular Tetravent ethyltriphenylphosphorous Dibromide

2016

Chem Sci Trans

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Abstract:A novel molecular tetravalent ethyltriphenylphosphorous dibromide ((C 6 H 5 ) 3 PCH 2 Br 2 ) has been synthesized in toluene and has been characterized by single crystal x-ray crystallography. Theoretical studies have been conducted utilizing DFT(B3LYP/6-311+G(d,p) level of theory both in gas phase and solution using diverse solvents. Potential surface energy calculations revealed the existence of the tetravalent diionic form as a global minimum except in dimethylsulfoxide where our adduct is more stable. Calculations showed that the Br-Br bond distance is in quadratic variation with the medium dielectric constant. The unusual Br-Br lengthen is reasonably rationalized in terms of charge transfer of electron density from the π clouds in phenyl moieties to the σ* of the dibromine entity. The average harmonic oscillator index of aromaticity of the complex are found suffering a deviation from unity.

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Bimolecular displacement reactions. III. Reaction of phenols with triphenylphosphine and bromine

Cited by 28 publications

References 0 publications

Aggregation Behavior of Lithionaphthalenes in Solution: Experimental and Theoretical Study

Aggregation Behavior of Lithionaphthalenes in Solution: Experimental and Theoretical Study

Synthesis of norsesterterpene rac- and ent-rhopaloic acid A

Synthesis, Crystallographic Characterization and Density Functional Study of Novel Spoke-Molecular Tetravent ethyltriphenylphosphorous Dibromide

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