[Organophosphorus Chemistry] Organophosphorus Chemistry Volume 11 || Halogenophosphines and related compounds

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  • 3 Halogenophosphines and Related Compounds

    BY J. A. MILLER

    1 Introduction Halogenophosphine chemistry, over the year being reviewed, has nearly all been directed towards new examples of established reactions. In the halo- genophosphorane field, iodophosphoranes are fast emerging from the shadows of obscurity. Considerable effort is still being expended in structural studies of halogenophosphoranes. Overall, the field remains an active one, but aimed generally at consolidation of existing views.

    2 Halogenophosphines Preparation.-Scarcely any significant synthetic work on halogenophosphines has appeared during the year, and none of it departs from established methods. Thus t-butyl(di-iodo)phosphine (1) has been prepared by halogen exchange.l A number of silylphosphines have been prepared via alkali-metal phosphides, e.g. (2),a (3),3 and (4) and (5).4

    A micro-scale synthesis of highly active a3PCl, has been published.s

    W P C ~ + 2 ~ i 1 bray+ B ~ ~ P I , (1) 93%

    Ph,PNa + ClMR, --+ Ph,PMR, (2) R = Ph, M = Si56%

    R = Ph, M = S n 4 2 %

    RPLi, + 2C1SiMe3 -+ RP(SiMe,), (3)

    Me ,Si,

    MeP L l l L W DU, Si. MePHLi

    MePHLi + - I I

    Me,SiC1, Me,Si , I PMe \ f -+ MeP

    But zS iCl, si Butz

    \ P / SiMe2 Me

    (4) (5 ) 1 N. G. Feshchenko and E. A. Melnichuk, J . Gen. Chem. USSR (Engl. Transl.), 1978,48,329. 2 A. Antoniadis and U. Kunze, 2. Naturforsch., Teil B, 1979, 34, 116. 3 G. Becker, 0. Mundt, M. Rossler, and E. Schneider, Z. Anorg. Allg. Chem., 1978,443,42. 4 G . Fritz and R. Uhlmann, 2. Anorg. Allg. Chem., 1978, 442, 95. ti D. V. Woo, A. F. Rupp, and J. K. Poggenburg, J . Labelled Compd. Radiopharm., 1978,15,

    117.

    51

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  • 52 Organophosphorus Chemistry

    Reactions with Alkenes and Alkynes.-Details have appeared of the preparation of phospha-steroids via cycloaddition to dienes.6a Cycloaddition was particularly facile in the 17-phospha-steroid series, and gave (6) after a hydrolytic work-up. The isomeric oxide (7) was formed in poorer yield, after hydrolysis of the complex formed over 21 days. Control of temperature and pH during hydrolysis resulted in the formation of A3-phospholen l-oxides (8) in the tricyclic series. A range of other cycloadditions of dichloro(methyl)phosphine, leading also to polycyclic phospholen oxides, is reported in the same paper?

    ( 6 ) 66%

    (7) 21%

    0 Me Me ,p

    @ (i)MePCL,+ (ii) H,O + Me0 \ Me0 \ Me0 \

    (8) 5370 (both isomers)

    Complex product mixtures can result when halogenophosphine-aluminium chloride complexes are treated with vinylcyclopropanes (9).8 In the absence of water, the products are either phosphorinens (lo), resulting from cycloaddition, or acyclic phosphine oxides (11). When water is added to these reactions, cyclo- addition is not observed, and the products are the oxides (12) and (13).8

    Alkyne additions of phosphorus tribromide in the presence of oxygen continue to generate confusion. The latest contribution to this field describes the require- ment for oxygen to initiate addi t i~n,~ but, unlike other reports,1 describes the

    6 C. Symmes and L. D. Quin, J. Org. Chem., 1979,44, 1048. 7 C. Symmes, J. Morris, and L. D. Quin, Tetrahedron Lett., 1977, 335. 8 Y. Kashman and A. Rudi, Tetrahedron Lett., 1979, 1077. 9 A. S. KrugIov, A. V. Dogadina, B. 1. Ionin, and A. A. Petrov, J. Gen. Chem. USSR (Engl.

    Transl.) 1978, 48, 649. 10 V. Okamato and H. Sakurai. Chem. Lett., 1973, 599.

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  • Halogenophosphines and Related Compounds 53 0 -

    Me dp(H)ph II (10) R = Me or Ph (11) R = Ph

    c 1

    products as vinylphosphines (14), i.e. oxygen is not incorporated. Furthermore, (14) generally seems to be one isomer, characterized on the basis of 3 J ~ ~ v a l u e s as the (E)-isomer. Previous considerations had suggested that the products had the (2) configuration.ll

    "'">-i" 0 RC-CH + PBr, A R Br (14) R = Ph, But, or BrCH, 50-70%

    BufPC1, + 2BufCH,MgC1 __f BdP(CH,Buf), (15)

    Reactions with Carbaniom.-Grignard routes to the phosphines (15) la and to (16) and (17),13 as shown in Scheme 1, have been described. The preparation of (1 6) involved a cadmium reagent.

    (minor) (major)

    (16) Reagents: i, Mg; ii, CdCla; iii, PC13; iv, MeMgI.

    Scheme 1 11 S. V, Fridland, J. M. Shchukareva, and R. A. Salakhutdinov, Zh. Obshch. Khim., 1976,46,

    12 H. Quast and M. Heuschmann, Angew. Chem., Int. Ed. Engl., 1978, 17, 867. 13 L. D. Quin and L. B. Littlefield, J. Org. Chem., 1978, 43, 3508.

    1232.

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  • 54 Organophosphorus Chemistry

    The substituted phenylmagnesium bromides (1 8) give monohalogeno- phosphines with phosphorus trichloride, and the failure to observe trisubstitution has been ascribed to steric fa~t0rs . l~ A related reaction of the internally complexed Grignard reagent (19) leads to the first (also see ref. 45) substantiated phosphor- anide anion (20).16 Chemical evidence for (20) includes its protonation to give a phosphorane. l6

    X = Me 46% x = c1 35% X = OMe failed

    (20)

    Simple sodium enolates of ketones, on treatment with monohalogeno- phosphines, give phosphorus(n1) esters (21) or ketones (22). Ionizing solvents favour O-phosphinylation to form (21), as does a change in halogenophosphine from R=Pri to R=NEtZ.I6

    R = NEt,, OEt, or Pri

    Reactions with Functional Groups containing Oxygen and/or Nitrogen.-Di- phosphorus tetraiodide (23) is gaining more attention as a reagent that has general synthetic utility. Thus alkyl iodides can be prepared from alcohols using (23). The sequence works well for tertiary iodides, gives inversion in a secondary system, and generally is free from side-reactions that involve rearrangement of carbonium ions.17 The tetraiodide (23) also converts oxirans into alkenes and aldoximes into nitriles:l* see Scheme 2 for details. 14

    16 1 6

    ir

    18

    A. A. Shvets, 0. A. Moiseeva, and 0. A. Osipov, J . Gen. Chem. USSR (Engl. Transl.), 1978,48, 208. I. Granoth and J. C. Martin, J. Am. Chem. SOC., 1978, 100, 7434. 2. S. Novikova, A. N. Kurkin, and I. F. Lutsenko, J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 271. M. Lauwers, B. Regnier, M. Van Eenoo, J. N. Denis, and A. Krief, Tetrahedron Lett., 1979, 1801. u C11miti T Fnchita. A. Iwasa. and T. Mishina. Svnthesis, 1978, 905.

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  • Halogenophosphines and Related Compounds

    RI (R is primary, secondary, or tertiary alkyl)

    RCH=NOH P,I, RC-N (37-85%)

    L

    55

    Scheme 2

    Formamidine derivatives (24) are formed efficiently from cyanamides and phosphorus trich10ride.l~ Simple hydrazones are known to react with phosphorus trichloride to give 2H- 1,2,3 a2-diazaphospholes (25).20 Re-investigation of this reaction has revealed that the isomeric 1H-phosphole (26) is also formed.21 The isomers are not interconvertible, and an X-ray study of (26) suggests that it is similar to pyrazole in its n-electron distribution. 21

    R , N C F N + PCl, 20"ct R,NC(CI)=NPCI, (24) 90-97%

    MeNHN=CMe, + PCI, -+

    (25) (26)

    The silylamino-phosphines (27) have been prepared by standard methods.' Quaternization at phosphorus and treatment with base yields the phosphine imines (28), which result from a 1,341~1 migration in the ylide intermediate."

    R2 Li Me I (i) Me,SiNRZ I /./

    R'PCl, RIP-N

    R' = C1 or Ph 'SiMe, (27) Rz = Me or Ph

    (i) Me1 (i) BuLi I

    le SiMe, /

    CJ 'R2

    19 V. I. Shevchenko, N. P. Pisanenko, and I. M. Kosinskaya, J. Gen. Chern. USSR (Engl.

    80 J. Luber and A. Schmidpeter, Angew. Chem., Znt. Ed. Engl., 1976, 15, 111. 21 J. H. Weinmaier, J. Luber, A. Schmidpeter, and S. Pohl, Angew. Chem., Znt. Ed. Engl.,

    22 J. C . Wilburn and R. H. Neilson, Inorg. Chem., 1979, 18, 347.

    Transl.), 1978, 48, 1078.

    1979,18, 412.

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  • 56 Organophosphorus Chemistry

    Dichloro(pentafluoropheny1)phosphine reacts with the silylated urea (29) to form the phosphorane (30) in high yield.23 Structural studies of (30) show that it is 21 % distorted from a trigonal bypyramid, towards a square pyramid.23

    ArN NMe

    0 K

    (30) Ar = in-CF3-C6H4 87%

    Arsenate esters (31) react with phosphorus(II1) chloridea4 or with arsenic(r1r) halides 2 4 9 26 to give a range of ligand-exchange and condensation products. A selection of these reactions is outlined in Scheme 3.

    RCI +

    ROPCI, (mainly) A (RO) ,A~Q ROA~CI,

    (ROASQJ, 62-97%

    (BuO),AsBr t BuOAsBr, F,AsOR

    Reagents: i, PC13; ii, AsC13; iii, AsF3; ivy AsBrs. Scheme 3

    Reactions with Carbonyl Compounds, Carboxylic Acids, and their Derivatives.- The phosphine oxides (32), (33), and (34) have been isolated from the reaction of di-t-butyl(ch1oro)phosphine with acetic acid. a6 Their formation presumably depends upon a pre-equilibrium (see Scheme 4), since an earlier study2 of the reaction of acetyl chloride with di-t-butylphosphine oxide described the same products. These results resemble those previously reported for chloro(dipheny1)- phosphine with trifluoroacetic acid 28 and with acetic acid,2g and the product differences seem to be ascribable to the electronic effect of the CF, group, or to differences in reaction conditions. 23 H. W. Roesky, K. Ambrosius, and W. S. Sheldrick, Chem. Ber., 1979, 112, 1365. 24 V. S. Gamayurova, M. M. Aladzhev, R. M. Nigmatullina, and B. D. Chernokalskii,

    25 V. S. Gamayurova, M. M. Aladzhev, R. M. Nigmatullina, and B. D. Chernokalskii, J.

    26 T. Kh. Gazizov, V. A. Kharlamov, and A. N. Pudovik, Bull. Acad. Sci. USSR, Diu.

    27 A. N. Pudovik and T. M. Sudakova, Dokl. Akad. Nauk. SSSR, 1970, 190, 1121. 28 J. A. Miller, in Organophosphorus Chemistry, ed. S . Trippett (Specialist Periodical

    29 J. A. Miller, in Organophosphorus Chemistry, ed. S. Trippett (Specialist Periodical

    J. Gen. Chem. USSR (Engl. Transl.), 1978, 48, 643.

    Gen. Chem. USSR (Engl. Transl.), 1978, 48, 734.

    Chem. Sci., 1978, 1418.

    Reports), The Chemical Society, London, Vol. 8, p. 55.

    Reports). The Chemical Society, London, Vol. 9, p. 55.

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  • Halogenophosphines and Related Compounds

    0

    Buf2PCl + AcOH @ But,POAc + HCl a But2PH + AcCl I1

    kist illation

    57

    0 0 0 0 II I I II II

    (B u',P),C(OH) Me + B u:PA c + B uf,PCH (Me)OPB u*,

    (32) 12% (33) 23% (34) 27% Scheme 4

    The same type of equilibria appear to be involved in the series of simplecarbonyl- addition reaction~~O-~~ outlined in Scheme 5. In each system, the product is an a-hydroxyalkyl-phosphinoyl chloride, probably formed by addition of a halide R(CI)P(O)H to the carbonyl compound in question.

    0 I I I

    EtPC1, + AcOH * EtPCl + AcCl H

    0 0

    PhPCl, + PhPH + 2PhPH PhP I I 1 I

    Cl OH 70%

    0 0 0 I 1 1 1 R,C=O 11

    PhPH + AcCl + PhPH ___f PhPC(OH)R, I I ref. 32 I OH c1 c1

    R = Me 70% + AcOH R, = C,H,, 85%

    Scheme 5

    30 S. Kh. Nurtdinov, N. M. Ismagilova, T. V. Zykova, R. A. Salakhutdinov, and V. S.

    31 N. A, Kardanov, N. N. Godovikov, and M. I. Kabachnik, Bull. Acad. Sci. USSR, Diu.

    32 N . A. Kardanov, N. N. Godovikov, and M. 1. Kabachnik, Bull. Acad. Sci. USSR, Diu.

    Tsivunin. J. Gen. Chem. USSR (Engl. Transl.), 1977, 41, 2447.

    Chem. Sci., 1978, 1282.

    Chem. Sci., 1978, 1720.

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  • 58 Organophosphorus Chemistry

    A related reaction of halogenophosphines in the presence of alkyl carbamates (35) leads to reasonable yields of a-amino-phosphorus(1v) products. 33 The carba- mate (35) clearly functions as an amino-group donor, but it is not known at which stage this becomes attached to the original carbonyl

    Molecules possessing both a carbonyl group and an adjacent hydroxyl group are capable of forming cyclic and spirocyclic compounds with halogenophos- phines. Further examples of this behaviour come from the hydroxamic acids (36),*4 also studied earlier in 1977.36 A much more spectacular example comes from treatment of o-hydroxyacetophenone (37) with dichloro(pheny1)phosphine. *6 The phosphorane product (38) has an equatorial phenyl group in a slightly distorted trigonal b i ~ y r a m i d . ~ ~

    0

    (37)

    PhPC1, Et,N benzene * Ph

    The existence of the phosphorane (39) was discussed several years A re- examination of the acylation reactions of diphenyl(fluoro)phosphine has led to the isolation of (39).38 Another example has appeared of acylation of a silyl- phosphine, in this case the bisphosphine (40). 39 The phospha-alkene structure (41) has been confirmed by X-ray crystal analysis, the P--C bond lengths (1.69 and 1.85 A) being quite different.39

    39 J. Oleksyszyn, R. Tyka, and P. Mastalerz, Synthesis, 1978, 479. 34 E. V. Hinrichs and I. Ugi, J. Chem. Res. (S) , 1978, 338. ~4 E. Fluck and M. Vargas, 2. Anorg. Allg. Chem., 1977, 437, 53 . 86 G. M. L. Cragg, B. Davidowitz, G . V. Fazakerley, L. R. Nassimbeni, and R. J. Haines,

    a7 C. Brown, M. Murray, and R. Schmutzler, J. Chem. SOC. (C) , 1970, 878. 38 S. Neumann, D. Schomburg, G. Richtarsky, and R. Schmutzler, J. Chem. SOC., Chem.

    sB G. Becker and 0. Mundt, Z. Anorg. Allg. Chem., 1978,443, 53.

    J. Chem. SOC., Chem. Commun., 1978, 510.

    Commun., 1978, 946.

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  • Halogenophosphines and Related Compounds

    0 I1 PhCOF

    Ph,POEt + PhCF d PhPF ____t

    59

    Similar phospha-alkene structures have been implicated in the reaction of the bis(trimethylsily1)phosphine (42) with phosgene.40 This reaction is known'l to lead to poly(phenyl)phosphines, and two intermediates, (43) and (44), the latter of uncertain structure, have now been suggested to be involved.

    OSiMe, cocl, / COCJ

    \

    Ph (43)

    PhP(SiMe,), pentaner PhP-C * [(PhP),(COSiMe,)l, P-%Me,

    / cw/ (44) (42)

    COCl PhPCL, I (PhP),

    n = 4 o r 5

    Reactions with Phosphorus(m) Compounds.-l,2-Bis(phosphino)ethane (45) reacts with a range of halogenophosphines (X = C1 or Br ; R = C1, Ph, or Me) to give 1,2,5,6-tetraphosphabicyclo[3.3.O]octane (46).4a The best yield of the reductive dimer comes from dichloro(methyl)phosphine, and detailed spectral evidence in support of structure (46) has been pre~ented.'~

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