US2006173172A1PendingUtilityA1

Method for producing novel spinosyn derivatives

54
Assignee: JESCHKE PETERPriority: Jul 20, 2001Filed: Feb 9, 2006Published: Aug 3, 2006
Est. expiryJul 20, 2021(expired)· nominal 20-yr term from priority
C07D 313/00C07H 17/08C12P 19/62C12P 17/181
54
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Claims

Abstract

The present invention relates to methods for producing novel spinosyn derivatives which are substituted with a 1-hydroxy-ethyl radical in the C-21 position and to novel spinosyn derivatives of this type per se and to their use for producing novel spinosyns.

Claims

exact text as granted — not AI-modified
1 . A method for producing compounds of the general formula (I),  
       
         
           
           
               
               
           
         
       
       in which 
 A-B is any of the following groups: —HC═CH—, —HC═C(CH 3 )—, —H 2 C—CH 2 — or —H 2 C—CH(CH 3 )—,  
 D is the group  
                     
 R 1  is hydrogen or an amino sugar and  
 R 2  is hydrogen or a su gar,  
 characterized in that compounds of the general formula (II),  
                     
 in which  
 A-B, D and R 1  are as defined above,  
 are contacted with a microorganism in an aqueous nutrient medium under aerobic conditions or with an enzyme extract prepared therefrom or with one or more enzymes isolated therefrom.  
 
     
     
         2 . The method as claimed in  claim 1 , characterized in that compounds of the general formula (II) are used,  
       in which formula, in the case (1) that 
 A-B is any of the following groups: —HC═CH—, —HC═C(CH 3 )—, —H 2 C—CH 2 — or —H 2 C—CH(CH 3 )— and  
 D is the group  
                     
 R 1  is an amino sugar of the formula 1a  
                     
  and  
 R 2  is a sugar of the formula 2a  
                     
 or in which, in the case (2) that  
 A-B is the group —HC═CH— or —H 2 C—CH 2 — and  
 D is as defined above,  
 R 1  is an amino sugar of the abovementioned formula 1a and  
 R 2  is hydrogen or a sugar of the formula 2b, 2c, 2d, 2e or 2f  
                     
                     
 or in which, in the case (3) that  
 A-B is any of the following groups: —HC═CH—, —HC═C(CH 3 )— or —H 2 C—CH 2 — and  
 D is as defined above,  
 R 1  is hydrogen or an amino sugar of the formula 1b  
                     
 and  
 R 2  is hydrogen or a sugar of the abovementioned formula 2a  
 or in which, in the case (4) that  
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is as defined above,  
 R 1  is an amino sugar of the abovementioned formula 1a and  
 R 2  is a sugar of the formula 2g, 2h, 2i, 2j or 2k  
                     
 or in which, in the case (5) that  
 A-B is the group —HC═CH— or —H 2 C—CH 2 — and  
 D is as defined above;  
 R 1  is an amino sugar of the abovementioned formula 1a and  
 R 2  is a sugar of the formula 2l or 2m.  
                     
 or in which, in the case (6) that  
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is as defined above,  
 R 1  is hydrogen or an amino sugar of the abovementioned formula 1b or an amino sugar of the formula 1c  
                     
 and  
 R 2  is a sugar of the abovementioned formula 2b, 2c, 2g or 2h or a sugar of the formula 2n  
                     
 or in which, in the case (7) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is an amino sugar of the abovementioned formula 1a and  
 R 2  is a sugar of the formula 2o  
                     
 or in which, in the case (8) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is an amino sugar of the abovementioned 1b and  
 R 2  is a sugar of the abovementioned formula 2d, 2i or 2j or a sugar of the formula 2p  
                     
 in which, in the case (9) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is hydrogen or an amino sugar of the abovementioned formula 1c and  
 R 2  is a sugar of the abovementioned formula 2i or 2p  
 or in which, in the case (10) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is an amino sugar of the formula 1d, 1e or 1f  
                     
 and  
 R 2  is a sugar of the abovementioned formula 2a  
 or in which, in the case (11) that  
 A-B is the group —HC═CH— and  
 D is the group  
                     
 R 1  is hydrogen or an amino sugar of the abovementioned formula 1a.  
 
     
     
         3 . The method as claimed in  claim 1  or  2 , characterized in that compounds of the general formula (II) are used, 
 in which formula, in the case (12) that    A-B is the group —HC═CH— or —HC═C(CH 3 )— and    D is the group                          R 1  is an amino sugar of the formula 1a and    R 2  is a sugar of the formula 2a, 2g or 2h    or in which, in the case (13) that    A-B is the group —HC═CH— and    D is as defined above,    R 1  is an amino sugar of the formula 1a and    R 2  is hydrogen or a sugar of the formula 2d, 2e, 2l, 2m or 2o    or in which, in the case (14) that    A-B is the group —HC═CH— or —HC═C(CH 3 )— and    D is as defined above,    R 1  is hydrogen or an amino sugar of the formula 1b and    R 2  is hydrogen or a sugar of the formula 2a    or in which A-B, D and R 1  are as defined as in the case (11).    
     
     
         4 . The method as claimed in any of  claims 1  to  3 , characterized in that compounds of the general formula (II) are used,  
       in which formula, in the case (15) that 
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is the group  
                     
 R 1  is an amino sugar of the formula 1a and  
 R 2  is a sugar of the formula 2a  
 or in which, in the case (16) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is an amino sugar of the formula 1a and  
 R 2  is hydrogen or a sugar of the formula 2d, 2l or 2m  
 or in which A-B, D and R 1  are as defined in the case (11).  
 
     
     
         5 . The method as claimed in any of  claims 1  to  4 , characterized in that compounds of the general formula (II) are used,  
       in which formula in the case (17) that 
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is the group  
                     
 R 1  is an amino sugar of the formula 1a and  
 R 2  is a sugar of the formula 2a  
 or in which, in the case (18) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is hydrogen and  
 R 2  is hydrogen.  
 
     
     
         6 . The method as claimed in any of  claims 1  to  5  characterized in that the microorganism used is a microorganisms from the group of actinomycetes.  
     
     
         7 . The method as claimed in  claim 6 , characterized in that the microorganism used from the group of actinomycetes is a microorganism of the genus  Streptomyces.    
     
     
         8 . The method as claimed in  claim 7 , characterized in that the microorganism used of the genus  Streptomyces  is a strain of the species  Streptomyces djakartensis, Streptomyces griseofuscus, Streptomyces caelestis, Streptomyces antibioticus, Streptomyces griseus  or  Streptomyces aureofaciens.    
     
     
         9 . The method as claimed in  claim 8 , characterized in that the strain has the characteristic features of the strains  Streptomyces djakartensis  DSM 14327,  Streptomyces griseofuscus  DSM 14330,  Streptomyces caelestis  DSM 14328,  Streptomyces antibioticus  DSM 14329,  Streptomyces griseus  DSM 14331 or  Streptomyces aureofaciens DSM 14332.  
     
     
         10 . The method as claimed in any of  claims 1  to  9 , characterized in that the compounds of the general formula (I) are isolated.  
     
     
         11 . A compound of the general formula (I),  
       
         
           
           
               
               
           
         
       
       in which 
 A-B is any of the following groups: —HC═CH—, —HC═C(CH 3 )—, —H 2 C—CH 2 — or —H 2 C—CH(CH 3 )—,  
 D is the group  
                     
 R 1  is an amino sugar and  
 R 2  is a sugar.  
 
     
     
         12 . The compound as claimed in  claim 11 , characterized in that,  
       in the case (1) that 
 A-B is any of the following groups: —HC═CH—, —HC═C(CH 3 )—, —H 2 C—CH 2 — or —H 2 C—CH(CH 3 )— and  
 D is the group  
                     
 R 1  is an amino sugar of the formula 1a  
                     
  and  
 R 2  is a sugar of the formula 2a  
                     
 or, in the case (2) that  
 A-B is the group —HC═CH— or —H 2 C—CH 2 — and  
 D is as defined above,  
 R 1  is an amino sugar of the abovementioned formula 1a and  
 R 2  is hydrogen or a sugar of the formula 2b, 2c, 2d, 2e or 2f  
                     
 or, in the case (3) that  
 A-B is one of the following groups: —HC═CH—, —HC═C(CH 3 )— or —H 2 C—CH 2 — and  
 D is as defined above,  
 R 1  is hydrogen or an amino sugar of the formula 1b  
                     
  and  
 R 2  is hydrogen or a sugar of the abovementioned formula 2a  
 or, in the case (4) that  
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is as defined above,  
 R 1  is an amino sugar of the abovementioned formula 1a and  
 R 2  is a sugar of the formula 2g, 2h, 2i, 2j or 2k  
                     
 or, in the case (5) that  
 A-B is the group —HC═C—H— or —H 2 C—CH 2 — and  
 D is as defined above,  
 R 1  is an amino sugar of the abovementioned formula 1a and  
 R 2  is a sugar of the formula 2l or 2m  
                     
 or, in the case (6) that  
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is as defined above,  
 R 1  is hydrogen or an amino sugar of the abovementioned formula 1b or an amino sugar of the formula 1c  
                     
  and  
 R 2  is a sugar of the abovementioned formula 2b, 2c, 2g or 2h or a sugar of the formula 2n  
                     
 or, in the case (7) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is an amino sugar of the abovementioned formula 1a and  
 R 2  is a sugar of the formula 2o  
                     
 or, in the case (8) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is an amino sugar of the abovementioned formula 1b and  
 R 2  is a sugar of the abovementioned formula 2d, 2i or 2j  
  or a sugar of the formula 2p  
                     
 or, in the case (9) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is hydrogen or an amino sugar of the abovementioned formula 1c and  
 R 2  is a sugar of the abovementioned formula 2i or 2p  
 or, in the case (10) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is amino sugar of the abovementioned formula 1d, 1e or an amino sugar of the formula 1f  
                     
 and  
 R 2  is a sugar of the abovementioned formula 2a  
 or, in the case (11) that  
 A-B is the group —HC═CH— and  
 D is the group  
                     
 R 1  is hydrogen or an amino sugar of the abovementioned formula 1a.  
 
     
     
         13 . The compound as claimed in  claim 12 , characterized in that,  
       in the case (12) that 
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is the group  
                     
 R 1  is an amino sugar of the formula 1a and  
 R 2  is a sugar of the formula 2a, 2g or 2h  
 or, in the case (13) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is an amino sugar of the formula 1a and  
 R 2  is hydrogen or a sugar of the formula 2d, 2e, 2 1 , 2m or 2o  
 or, in the case (14) that  
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is as defined above,  
 R 1  is hydrogen or an amino sugar of the formula 1b and  
 R 2  is hydrogen or a sugar of the formula 2a  
 or A-B, D and R 1  are as defined as in the case (11).  
 
     
     
         14 . The compound as claimed in  claim 12 , characterized in that,  
       in the case (15) that 
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is the group  
                     
 R 1  is an amino sugar of the formula 1a and  
 R 2  is a sugar of the formula 2a  
 or, in the case (16) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is an amino sugar of the formula 1a and  
 R 2  is hydrogen or a sugar of the formula 2d, 2l or 2m  
 or A-B, D and R 1  are as defined as in the case (11).  
 
     
     
         15 . The compound as claimed in  claim 12 , characterized in that,  
       in the case (17) that 
 A-B is the group —HC═CH— or —HC═C(CH 3 )— and  
 D is the group  
                     
 R 1  is an amino sugar of the formula 1a and  
 R 2  is a sugar of the formula 2a  
 or, in the case (18) that  
 A-B is the group —HC═CH— and  
 D is as defined above,  
 R 1  is hydrogen and  
 R 2  is hydrogen.  
 
     
     
         16 . The compound as claimed in  claim 12 , characterized in that 
 A-B is the group —HC═CH—,    D is the group                          R 1  is an amino sugar of the formula 1a and    R 2  is a sugar of the formula 2a,    or in which    A-B is the group —HC═CH— or —HC═C(CH 3 )—,    D is as defined above,    R 1  is hydrogen and    R 2  is a sugar of the formula 2a,    or in which    A-B is a group —HC═CH—,    D is as defined above,    R 1  is hydrogen and    R 2  is hydrogen.    
     
     
         17 . The use of compounds as claimed in any of  claims 11  to  16  for producing novel spinosyn derivatives.

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