Synthesis of 2,6- and 2,3-Difluorophenyldimethyl(thio)phosphines

Grobe, I.; Goryunov, L. I.; Shteingarts, V. D.

doi:10.1007/s11178-006-0025-9

Russ J Org Chem

2005

DOI: 10.1007/s11178-006-0025-9

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Synthesis of 2,6- and 2,3-Difluorophenyldimethyl(thio)phosphines

I. Grobe

L. I. Goryunov

V. D. Shteingarts

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Cited by 6 publications

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“…Thus, in the present work we synthesized individual phosphines VI and VII from 1-bromo-2,3-and 1-bromo-2,6-difluorobenzenes, respectively (Scheme 2). Compounds VI and VII were obtained previously as a mixture in the reaction of 1,2,3-trifluorobenzene with Me 2 PSiMe 3 [3].…”

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Reaction of chloropentafluorobenzene and 2,3- and 2,6-difluorobromobenzenes with lithium dimethylphosphide

et al. 2009

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Reaction of chloropentafluorobenzene and 2,3- and 2,6-difluorobromobenzenes with lithium dimethylphosphide

et al. 2009

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“…and pentafl uoropyridine [1,2], and also in 1,2,3-and 1,3,5-trifl uoro-, 1,2-and 1,3-difl uorobenzenes [3,4]. In this study the reagent was applied to the preparation of benzene-1,2-diylbis(dimethylphosphane) (II) and its new analog, 3-fl uorobenzene-1,2-diylbis(dimethylphosphane) (III), chelating ligands for transition metal complexes as had been described for phosphane II [5,6].…”

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“…Mass of molecular ions was determined on a high-resolution mass spectrometer Thermo Scientifi c DFS (70 eV). The preparation of Me 3 SiPMe 2 (I) and its reactions with haloarenes were performed as previously described [1][2][3][4]8].…”

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Synthesis of (2-X,3-Y-phenyl)dimethylphosphanes (X, Y = Me2P, H; Me2P, F; Br, F) and their complexes with PdCl2

et al. 2011

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Earlier the trimethylsilyldimethylphosphane Me 2 PSiMe 3 (I) was utilized for the substitution of fl uorine atom with PMe 2 groups in polyfl uoroarenes C 6 F 5 X (X = H, F, Cl, CF 3 , etc.) and pentafl uoropyridine [1,2], and also in 1,2,3-and 1,3,5-trifl uoro-, 1,2-and 1,3-difl uorobenzenes [3,4]. In this study the reagent was applied to the preparation of benzene-1,2-diylbis(dimethylphosphane) (II) and its new analog, 3-fl uorobenzene-1,2-diylbis(dimethylphosphane) (III), chelating ligands for transition metal complexes as had been described for phosphane II [5,6].The reaction of ortho-difl uorobenzene with exess phosphane I at relatively high temperature led to the formation (in keeping with the data of 19 F and 31 P NMR spectra) a mixture of dimethyl(2-fl uorophenyl)phosphane (32%) [4] and diphosphane II (68%) isolated in 60% yield (Scheme 1). Lately diphosphane II was synthesized from dimethyl-(2-chlorophenyl)phosphane by metallation with lithium followed by the treatment with dimethylchlorophosphane [5] of by alkylation of 1,2-diphosphanobenzene sodium salts with methyl iodide [7] in 11 and 68% yield respectively.Phosphane IV obtained formerly by phosphanedebromination of 2,6-F 2 C 6 H 3 Br with lithium dimethylphosphide (V) [8] reacted with phosphane I under milder conditions affording in 96% yield diphosphane III that was isolated in 57% yield (path a, Scheme 2).Phosphane I in contrast to phosphide V reacts with 2,6-F 2 C 6 H 3 Br to give 92% of (2-bromo-3-fl uorophenyl) dimethylphosphane (VI) and 7% of phosphane IV (Scheme 2, path b). The main product was isolated in 62% yield. The discovered difference in the results of the reaction between 2,6-F 2 C 6 H 3 Br and reagents I and V is probably due to the difference in the mechanism of reactions involving nucleophiles I and V: With Me 2 PLi this is the mechanism S RN 1 initiated by the electron transfer from the nucleophile to the substrate (cf. [8]), and in the process with Me 2 PSiMe 3 it is synchronic mechanism A N D N apparently observed in its reactions with di-and trifl uorobenzenes [4]. In this respect it is illustrative that the ratio (VI)-(IV) equal 13:1 indicates a weaker element-effect compared to reactions S N Ar: In the products of reaction between bromofl uorobenzenes with sodium methylate in a mixture DMSO-MeOH the Br -ions have not been found even in traces [9]. Probably the relatively low selectivity with respect to the nature of the substituted halogen is characteristic of the A N D N mechanism combining in a cerScheme 1.

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Di‐ and Trifluorobenzenes in Reactions with Me₂EM (E = P, N; M = SiMe₃, SnMe₃, Li) Reagents: Evidence for a Concerted Mechanism of Aromatic Nucleophilic Substitution

et al. 2010

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Dimethyl(trimethylsilyl)phosphane (Me3SiPMe2) has been successfully used for the substitution of fluorine variously in 1,3‐ (1) or 1,2‐difluorobenzene (2) or in 1,3,5‐ (3) or 1,2,3‐trifluorobenzene (4) by the Me2P group at 150–190 °C either in benzene solution or without solvent to give 1‐(dimethylphosphanyl)‐3‐fluorobenzene (5) from 1, 1‐(dimethylphosphanyl)‐2‐fluorobenzene (6) from 2, 1‐(dimethylphosphanyl)‐3,5‐difluorobenzene (7) from 3 or a 1:1 mixture of 1‐(dimethylphosphanyl)‐2,3‐difluorobenzene (8) and 1‐(dimethylphosphanyl)‐2,6‐difluorobenzene (9) from 4. The substrate selectivities and regioselectivities exhibited by 4 with Me3SiPMe2 and in competitive reactions between 1 and 2 or 3 and 4 with Me2PSiMe3, Me2PSnMe3 or Me2PLi indicate relative fluorine substituent rate factors fo‐F > fm‐F, whereas for reactions that proceed through a two‐step SNAr mechanism the opposite sequence is typical. High‐level quantum‐chemical DFT and MP2 calculations predict that the gas‐phase reactions should each proceed by a concerted mechanism with a single transition state. These predictions are in good agreement with the experimental observations, especially because the structural features of the Meisenheimer adduct are unfavourable for the SNAr mechanism. This proposal is consistent with the observation of the opposite sequence (fm‐F > fo‐F) for the reactions between the same substrates and MeONa in DMSO/CH3OH solvent mixtures. The novel phosphanes were characterized by spectroscopic (NMR) and spectrometric (MS) investigation, preparation of the thiophosphanes ArFPSMe2 10–12, their spectroscopic data and, in the case of 12, by its X‐ray structure. The phosphanes 5–9 were treated with bis(benzonitrile)dichloropalladium(II) to afford the corresponding bis(phosphane)palladium dichloride complexes 17–21 and 23 in isolated yields of up to 95 %.

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Synthesis of 2,6- and 2,3-Difluorophenyldimethyl(thio)phosphines

Cited by 6 publications

References 8 publications

Reaction of chloropentafluorobenzene and 2,3- and 2,6-difluorobromobenzenes with lithium dimethylphosphide

Reaction of chloropentafluorobenzene and 2,3- and 2,6-difluorobromobenzenes with lithium dimethylphosphide

Synthesis of (2-X,3-Y-phenyl)dimethylphosphanes (X, Y = Me2P, H; Me2P, F; Br, F) and their complexes with PdCl2

Di‐ and Trifluorobenzenes in Reactions with Me₂EM (E = P, N; M = SiMe₃, SnMe₃, Li) Reagents: Evidence for a Concerted Mechanism of Aromatic Nucleophilic Substitution

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Synthesis of 2,6- and 2,3-Difluorophenyldimethyl(thio)phosphines

Cited by 6 publications

References 8 publications

Reaction of chloropentafluorobenzene and 2,3- and 2,6-difluorobromobenzenes with lithium dimethylphosphide

Reaction of chloropentafluorobenzene and 2,3- and 2,6-difluorobromobenzenes with lithium dimethylphosphide

Synthesis of (2-X,3-Y-phenyl)dimethylphosphanes (X, Y = Me2P, H; Me2P, F; Br, F) and their complexes with PdCl2

Di‐ and Trifluorobenzenes in Reactions with Me2EM (E = P, N; M = SiMe3, SnMe3, Li) Reagents: Evidence for a Concerted Mechanism of Aromatic Nucleophilic Substitution

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Product

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Di‐ and Trifluorobenzenes in Reactions with Me₂EM (E = P, N; M = SiMe₃, SnMe₃, Li) Reagents: Evidence for a Concerted Mechanism of Aromatic Nucleophilic Substitution