(IO)  Patent No.:  US 8,884,053 B2  Nov. 11, 2014  (45)  Date of Patent:  c12)  United States Patent  Notte et al.  (54)  METHOD FOR THE MANUFACTURE OF  AMINOALKYLENE PHOSPHONIC ACID  (75)  Inventors:  Patrick Notte,  Wavre (BE);  Albert  Devaux,  Mont-Saint-Guibert (BE)  (73)  Assignee:  Straitmark Holding AG,  Zug (CH)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 723 days.  (21)  Appl. No.:  12/989,306  (22)  PCT Filed:  Apr. 25, 2009  (86)  PCT No.:  PCT /EP2009/055000  § 371 (c)(l),  (2), ( 4) Date:  Dec. 8, 2010  (87)  PCT Pub. No.:  WO2009/130322  (51)  Int. Cl.  C07F 9/44  C07F 9/38  (2006.01)  (2006.01)  (52)  U.S. Cl.  CPC ....................................  C07F 9/3817  (2013.01)  USPC . ... ... ... .. ... ... ... ... ... .. ... ... ... ... ... .. ... ... ... ... ..  562/11  ( 58)  Field of Classification Search  USPC ............................................................ 562/11  See application file for complete search history.  16 Claims, No Drawings  (57)  ABSTRACT  OTHER PUBLICATIONS  FOREIGN PATENT DOCUMENTS  (65)  Prior Publication Data  (30)  Foreign Application Priority Data  (56)  References Cited  U.S. PATENT DOCUMENTS  3,288,846 A  11/1966 Irani et al.  6,238,637 Bl  5/2001 Heise et al.  Apr. 25, 2008  Nov. 21, 2008  (EP) ..................................... 08155198  (EP) ..................................... 08169648  CA  DE  DE  DE  EP  EP  EP  EP  GB  GB  HU  HU  JP  WO  WO  WO  2070949  206363  222597  292214  1008552  1681294  1886976  2112156  1142294  1230121  36825  199488  57075990  9640698  9943612  2009130322  12/1993  1/1984  5/1985  7 /1991  6/2000  7/2006  2/2008  10/2009  2/1969  4/1971  10/1981  2/1990  5/1982  12/1996  9/1999  10/2009  6,440,380 Bl  6,476,256 Bl  2011/0008231 Al  8/2002 Heise et al.  11/2002 Heise et al.  1/2011 Schipper  PCT Pub. Date:  Oct. 29, 2009  US 2011/0118502 Al  May 19, 2011  US008884053B2  "The Direct Synthesis of a-Aminomethylphosphonic Acids, Man› nich-Type Reactions with Orthophosphorus Acid," Moedritzer and  Irani, J. Org. Chem., vol. 31 pp. 1603-1607 (1966).  Primary Examiner  - Sikarl Witherspoon  (74)  Attorney, Agent, or Firm  - Husch Blackwell LLP  A method for the manufacture of amino alkylene phosphonic  acids is disclosed. Pure P  $_{4}$0 $_{6 }$is hydrolyzed in the presence of  a homogeneous Broensted acid catalyst whereby the pH of  the reaction medium is maintained below 5 and the free water  content of said reaction medium is, after the P  $_{4}$0 $_{6 }$hydrolysis  has been completed, from  O  to 40%. The required amine  component can be added before, during, or in one preferred  execution, after the P  $_{4}$0 6  hydrolysis has been completed.  Formaldehyde is then added and the reaction mixture con› taining the P  $_{4}$0 6  hydrolysate, the amine and the formalde› hyde is reacted in presence of a Broensted acid catalyst  selected from homogeneous and heterogeneous species. The  amino alkylene phosphonic acid reaction product can then be  recovered in a manner known per se. 