Download PDF
Synthesis 2010(14): 2437-2445  
DOI: 10.1055/s-0029-1218817
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Preparation of Dialkyl 1-(Alkylamino)alkylphosphonates, Alkyl [1-(Alkylamino)alkyl]phenylphosphinates and [1-(Alkylamino)alkyl]di­phenylphosphine Oxides via ‘In Situ’ Generated Iminium Ions

Waldemar Goldeman, Mirosaw Soroka*
Politechnika Wrocawska, Department of Chemistry, Wybrzeże Wyspiańskiego 27, 50370 Wrocaw, Poland
Fax: +48(71)3284064; e-Mail: miroslaw.soroka@pwr.wroc.pl;
Further Information

Publication History

Received 27 January 2010
Publication Date:
15 June 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

The reaction of trialkyl phosphites, dialkyl phenylphosphonites or alkyl diphenylphosphinites with N-alkylalkanimines in the presence of hydrogen chloride gives dialkyl 1-(alkylamino)alkylphosphonates, alkyl [1-(alkylamino)alkyl]phenylphosphinates or [1-(alkylamino)alkyl]diphenylphosphine oxides respectively, via Arbusov-like reaction of iminium salts generated ‘in situ’ from N-alkylalkanimines. This reaction is an alternative and competitive to known method of preparation based on the addition of H-P compounds to N-alkylalkanimines, because it gives higher yields, no heating is necessary, and the isolation of products is easy.

Key words

aminophosphonates - aminophosphinates - imines - Schiff bases - nucleophilic addition

    References and Notes

  • 1 Goldeman W. Soroka M. Synthesis  2006,  3019 
    Thieme Connect
  • This statement is rather intuitive because there is no way to have the imine and the corresponding iminium salts exactly in the same reaction environment. However, experiments ‘in silico’ indicated that the iminium ions have a lower barrier than the corresponding imines. See for example:
  • 2a Tomoda S. Senju T. Kawamura M. Ikeda T. J. Org. Chem.  1999,  64:  5396 
    Search in Google Scholar
  • 2b Iafe RG. Houk KN. J. Org. Chem.  2008,  73:  2679 
    Search in Google Scholar
  • Also the conclusions reached from crystallographic data are similar. See for example:
  • 2c Childs RF. Shaw GS. Lock CJL. J. Am. Chem. Soc.  1989,  111:  5424 
    Search in Google Scholar
  • 3 Soroka M. Zygmunt J. Synthesis  1988,  370 
    Thieme Connect
  • 4 Kowalik J. Kupczyk-Subotkowska L. Mastalerz P. Synthesis  1981,  57 
    Thieme Connect
  • 5 When our work was finished Metlushka et al. described an addition of trialkyl phosphites into Betti bases in the presence of TFA. We would like to thank a referee for this reference: Metlushka KE. Kashemirov BA. Zheltukhin VF. Sadkova DN. Büchner B. Hess C. Kataeva ON. McKenna CE. Alfonsov VA. Chem. Eur. J.  2009,  15:  6718 
    CrossrefSearch in Google Scholar
  • Searching common databases gives a few hundred publications concerning aminophosphonates, more than three hundred 1-(alkylamino)alkylphosphonates, and about 150 papers describing their synthesis and properties. Since citation of all of them in this short article is inappropriate, we cite here only these papers that are strongly connected to our work. First, general methods of synthesis of these compounds based on the addition of dialkyl phosphonates to alkanimines was described by Pudovik and co-workers and independently by Fields in 1952:
  • 6a Pudovik AN. Dokl. Akad. Nauk SSSR  1952,  83:  865 ; Chem. Abstr. 1953, 47, 25297
    Search in Google Scholar
  • 6b Pudovik AN. Korchemkina MV. Izv. Akad. Nauk SSSR, Ser. Khim.  1952,  831 ; Chem. Abstr. 1954, 48, 24762
  • 6c Pudovik AN. Korchemkina MV. Izv. Akad. Nauk SSSR, Ser. Khim.  1952,  940 ; Chem. Abstr. 1953, 47, 61788
  • 6d Fields J. J. Am. Chem. Soc.  1952,  74:  1528 
    Search in Google Scholar
  • More recently see, for example:
  • 6e Pak VD. Kozlov N. S. Balyakova I. A. Gartmann G. A. Zh. Obshch. Khim.  1976,  46:  1012 ; Chem. Abstr. 1976, 85, 108711
    Search in Google Scholar
  • 6f Pak VD. Gartman GA. Yaganova NN. Neifel’d PG.
    Zh. Obshch. Khim.  1998,  68:  1930 ; Chem. Abstr. 1999, 131, 73260
    Search in Google Scholar
  • 6g Harger MJP. Williams A. J. Chem. Soc., Perkin Trans. 1  1989,  563 
  • 6h Kabachnik MM. Ternovskaya TN. Zobnina EV. Beletskaya IP. Zh. Org. Khim.  2002,  38:  504 ; Chem. Abstr. 2002, 138, 24766
    Search in Google Scholar
  • 6i Kabachnik MM. Ternovskaya TN. Zobnina EV. Beletskaya IP. Zh. Org. Khim.  2002,  38:  508 ; Chem. Abstr. 2002, 138, 24766
    Search in Google Scholar
  • 6j Kabachnik MM. Zobnina EV. Beletskaya IP. Zh. Org. Khim.  2005,  41:  517 ; Chem. Abstr. 2005, 144, 350758
    Search in Google Scholar
  • The reaction was successfully improved by mixing aldehydes or ketones with alkylamines and dialkyl phosphonates in one pot, for examples see:
  • 6k Ivanova ZhM. Kim TV. Suvalova EA. Boldeskul IE. Gololobov YuG. Zh. Obshch. Khim.  1976,  46:  236 ; Chem. Abstr. 1976, 85, 21540
    Search in Google Scholar
  • 6l Burpitt RD. Goodlett VW. J. Org. Chem.  1965,  30:  4307 
    Search in Google Scholar
  • 6m Gancarz R. Tetrahedron  1995,  51:  10627 
    Search in Google Scholar
  • 6n Gancarz R. Gancarz I. Walkowiak U. Phosphorus, Sulfur Silicon Relat. Elem.  1995,  104:  45 
    Search in Google Scholar
  • The ¹H NMR study of dialkyl phosphonates confirmed finally that these compounds exist as non-nucleophilic phosphonate (so-called ‘keto’) tautomers, since the presence of nucleophilic dialkyl phosphite tautomers was not found: see
  • 7a Bailey WJ. Fox RB. J. Org. Chem.  1963,  28:  531 ; and references cited therein
    Search in Google Scholar
  • The properties of the dialkyl phosphonates were reviewed by:
  • 7b Doak GO. Freedman LD. Chem. Rev.  1961,  61:  31 
    Search in Google Scholar
  • 8 Pudovik AN. Pudovik MA. Zh. Obshch. Khim.  1969,  39:  1645 ; Chem. Abstr. 1969, 71, 91592
    Search in Google Scholar
  • 9 Zefirov NS. Matveeva ED. ARKIVOC  2008,  (i):  1 ; and references cited therein. The catalytic Kabachnik-Fields reaction was reviewed in this paper
    Search in Google Scholar
  • 10 Shono T. Matsumura Y. Tsubata K. Tetrahedron Lett.  1981,  22:  3249 
    CrossrefSearch in Google Scholar
  • 11 Seebach D. Charczuk R. Gerber C. Renaud P. Berner H. Schneider H. Helv. Chim. Acta  1989,  72:  401 
    Search in Google Scholar
  • 12a Corcoran RC. Green JM. Tetrahedron Lett.  1990,  31:  6827 
    Search in Google Scholar
  • 12b Maury C. Gharbaoui T. Royer J. Husson H.-P. J. Org. Chem.  1996,  61:  3687 
    Search in Google Scholar
  • 13 Thai A. Tap Chi Hoa Hoc  1977,  15:  18 ; Chem. Abstr. 1979, 90, 152289
    Search in Google Scholar
  • In 1953, Pudovik reported an addition of alkyl phosphonites [H-P(O)(R¹)OR²] to alkanimines, and described the preparation of eight new alkyl [1-(alkylamino)alkyl]phenyl-phosphinates:
  • 14a Pudovik AN. Dokl. Akad. Nauk SSSR  1953,  92:  773 ; Chem. Abstr. 1955, 49, 15792
    Search in Google Scholar
  • The same reaction was later described by others:
  • 14b Rohovec J. Vojtisek P. Lukes I. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  148:  79 
    Search in Google Scholar
  • 14c Kabachnik MM. Ternovskaya TN. Zobnina EV. Beletskaya IP. Russ. J. Org. Chem. (Engl. Transl.)  2002,  38:  480 ; Chem. Abstr. 2002, 137, 370153; see also ref. 6h
    Search in Google Scholar
  • 14d Szabo A. Jaszay ZM. Hegedus L. Toke L. Petnehazy I. Tetrahedron Lett.  2003,  44:  4603 
    Search in Google Scholar
  • 14e Szabo A. Petnehazy I. Jaszay ZM. Heteroat. Chem.  2003,  14:  235 
    Search in Google Scholar
  • 14f Bobrikova AA. Koroteev MP. Stash AI. Bel’skii VK. Nifant’ev EE. Russ. J. Org. Chem. (Engl. Transl.)  2008,  44:  1150 ; Chem. Abstr. 2008, 150, 515386
    Search in Google Scholar
  • Instead of alkanimine Issleib et al. and Solodenko et al. used 1,3,5-trialkyltria-zanes:
  • 14g Issleib K, Moegelin W, Balszuweit A, Thust U, Guenther E, and Pallas M. inventors; DD  205167.  ; Chem. Abstr. 1984, 101, 55339
  • 14h Issleib K. Moegelin W. Synth. React. Inorg. Met.-Org. Chem.  1986,  16:  645 
    Search in Google Scholar
  • 14i Solodenko VA. Kukhar VP. Zh. Obshch. Khim.  1989,  59:  2684 ; Chem. Abstr. 1990, 113, 24475
    Search in Google Scholar
  • Also an addition of silylated phosphonites to the alkanimines was described:
  • 14j Afarinkia K. Cadogan JIG. Rees CW. Synlett  1990,  415 
  • 14k Afarinkia K. Rees CW. Cadogan JIG. Tetrahedron  1990,  46:  7175 
    Search in Google Scholar
  • 14l Afarinkia K. Cadogan JIG. Rees CW. Synlett  1992,  124 
  • Finally, the so-called 3CC reaction (Kabachnik reaction) was also reported:
  • 14m Duan J. Yu J. Liu X. Xiang J. Hecheng Huaxue  2006,  14:  588 ; Chem. Abstr. 2007, 147, 72830
    Search in Google Scholar
  • Representative (1-aminoalkyl)phenylphosphinic acids were also prepared directly from PhPCl2:
  • 14n Oleksyszyn J. Synthesis  1980,  722 
  • [1-(Alkylamino)alkyl]diphenylphosphine oxides were mentioned in the literature, and also in this case, the most frequently employed method was a simple addition of diphenylphosphine oxide to the alkanimines. For examples: see refs. 6h, 14f, and:
  • 15a Pudovik AN. Batyeva ES. Izv. Akad. Nauk SSSR, Ser. Khim.  1968,  2391 ; Chem. Abstr. 1969, 71, 3438
  • 15b Messinger P. Arch. Pharm. (Weinheim, Ger.)  1971,  304:  842 
    Search in Google Scholar
  • 15c Tyka R. Pr. Nauk. Inst. Chem. Org. Fiz. Politech. Wroc.  1972,  4:  54 ; Chem. Abstr. 1975, 82, 98120
    Search in Google Scholar
  • 15d Sukale S, Niclas HJ, Richter HJ, and Zoelch L. inventors; DD  234869.  ; Chem. Abstr. 1986, 105, 227005
  • 15e Niclas HJ. Sukale S. Richter HJ. Z. Chem.  1985,  25:  368 
    Search in Google Scholar
  • 15f Rohovec J. Vojtisek P. Lukes I. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  148:  79 
    Search in Google Scholar
  • 15g Yamakoshi K. Harwood SJ. Kanai M. Shibasaki M. Tetrahedron Lett.  1999,  40:  2565 
    Search in Google Scholar
  • 15h Boduszek B. Synth. Commun.  2003,  33:  4087 
    Search in Google Scholar
  • 15i Olszewski TK. Boduszek B. Pol. J. Chem.  2005,  79:  553 
    Search in Google Scholar
  • 15j Olszewski TK. Boduszek B. Sobek S. Kozlowski H. Tetrahedron  2006,  62:  2183 
    Search in Google Scholar
  • 15k Goldeman W. Olszewski TK. Boduszek B. Sawka-Dobrowolska W. Tetrahedron  2006,  62:  4506 
    Search in Google Scholar
  • 15l Guzik M. Olszewski TK. Boduszek B. Pol. J. Chem.  2007,  81:  1879 
    Search in Google Scholar
  • 15m Koroteev AM. Bobrikova AA. Koroteev MP. Lysenko KA. Nifant’ev EE. Russ. J. Gen. Chem. (Engl. Transl.)  2008,  78:  185 ; Chem. Abstr. 2008, 150, 191752
    Search in Google Scholar
  • 15n Du L.-Z. Gong J.-F. Zhu Y. Wu Y.-J. Song M.-P. Inorg. Chem. Commun.  2006,  9:  529 
    Search in Google Scholar
  • 15o Afarinkia K. Rees CW. Cadogan JIG. Tetrahedron  1990,  46:  7175 
    Search in Google Scholar
  • 15p Frolovskii VA. Studnev YuN. Rozantsev GG. Zh. Obshch. Khim.  1996,  66:  692 ; Chem. Abstr. 1996, 125, 276015
    Search in Google Scholar
  • It is worthy of note that N-unsubstituted (1-aminoalkyl)diphenylphosphine oxides could be obtained also in amidoalkylation reaction
  • 15q Oleksyszyn J. Synthesis  1981,  444 
  • 15r Oleksyszyn J.
    J. Prakt. Chem.  1987,  329:  19 
    Search in Google Scholar
  • 16 Tyka R. Tetrahedron Lett.  1970,  11:  677 
    CrossrefSearch in Google Scholar
  • 17a Gilmore WF. McBride MA. J. Am. Chem. Soc.  1972,  94:  4361 
    Search in Google Scholar
  • 17b Gowiak T. Sawka-Dobrowolska W. Kowalik J. Mastalerz P. Soroka M. Zoń J. Tetrahedron Lett.  1977,  18:  3965 
    Search in Google Scholar
  • 18a Łukszo J. Tyka R. Synthesis  1977,  239 
  • 18b Łukszo J. Tyka R. Pol. J. Chem.  1978,  52:  321 
    Search in Google Scholar
  • 18c Łukszo J. Tyka R. Pol. J. Chem.  1978,  52:  959 
    Search in Google Scholar
  • 18d Łukszo J. Kowalik J. Mastalerz P. Chem. Lett.  1978,  1103 
  • 19a Baylis EK. Campbell CD. Dingwall JG. J. Chem. Soc., Perkin Trans. 1  1984,  2845 
  • 19b Issleib K. Doepfer KP. Balszuweit A. Z. Naturforsch., B  1981,  36:  1392 
    Search in Google Scholar
  • 20a Moedritzer K. Synth. React. Inorg. Met.-Org. Chem.  1972,  2:  317 
    Search in Google Scholar
  • 20b Zoń J. Mastalerz P. Rocz. Chem.  1976,  50:  1403 
    Search in Google Scholar
  • 20c Hoffmann H. Foerster H. Monatsh. Chem.  1968,  99:  380 
    Search in Google Scholar
  • 20d Kreutzkamp N. Storck K. Naturwissenschaften  1960,  47:  497 
    Search in Google Scholar
  • 20e Wieczorek JS. Gancarz R. Rocz. Chem.  1976,  50:  2171 
    Search in Google Scholar
  • 20f Drauz K. Koban HG. Martens J. Schwarze W. Liebigs Ann. Chem.  1985,  448 
  • 20g Lugovkin BP. Zh. Obshch. Khim.  1976,  46:  2498 ; Chem. Abstr. 1977, 86, 106726
    Search in Google Scholar
  • 20h Gartman GA. Pak VD. Kozlov ND. Zh. Obshch. Khim.  1979,  49:  2375 
    Search in Google Scholar
  • 21a Rachoń J. Wasielewski C. Z. Chem.  1973,  13:  254 
    Search in Google Scholar
  • 21b Wasielewski C. Antczak K. Rachoń J. Pol. J. Chem.  1978,  52:  1315 
    Search in Google Scholar
  • 21c Rachoń J. Wasielewski C. Tetrahedron Lett.  1978,  19:  1609 
    Search in Google Scholar
  • 21d Nifantev EE. Zyk NV. Koroteev MP. Dokl. Akad. Nauk. SSSR  1974,  218:  1371 ; Chem. Abstr. 1975, 82, 73099
    Search in Google Scholar
  • 22 However, there is a note in the paper published by Sobanov et al., that ‘the reaction between Schiff bases and dialkyl hydrogen phosphonates thoroughly purified from traces of acidic admixtures does not take place: Sobanov AA. Zolotukhin AV. Galkina IV. Galkin VI. Cherkasov RA. Russ. J. Gen. Chem. (Engl. Transl.)  2006,  76:  421 ; Chem. Abstr. 2006, 146, 62804
    CrossrefSearch in Google Scholar