Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1999-05-13
2000-05-16
Powers, Fiona T.
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
564158, 564161, 564337, 568 31, 568 32, C07D26310, C07C23364, C07C23368, C07C31714
Patent
active
060639326
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
The present invention relates to arthropodicidal oxazolines and processes and intermediates for the preparation thereof.
BACKGROUND OF THE INVENTION
The present invention relates to the preparation of novel intermediates and particular oxazolines which are known to have arthropodicidal activity. Although WO 96/11190, EP 594179-A1 and U.S. Pat. No. 5,354,905 disclose methodologies for oxazoline preparation, the present invention provides a potential commercial preparation of these particular oxazolines which has been limited because previous preparations were too expensive or complicated. There is a continuing need to discover new processes for the preparation of oxazolines where the preparation offers distinct advantages that add to their desirability. The processes of the present invention provide novel and direct routes typically using well-known and commercially available starting materials.
SUMMARY OF THE INVENTION
The present invention pertains to novel compounds having Formula I and processes for the preparation thereof: ##STR2## wherein R is selected from H, --C(O)CH.sub.2 R.sup.4, --CH(OH)CH.sub.2 R.sup.4, --CH(NH.sub.2)CH.sub.2 R.sup.4 and ##STR3## and salts thereof; R.sup.4 is OC(O)Ar, Cl, or Br;
The present invention further pertains to compounds of Formula I wherein R is: ##STR4## and a composition comprising a mixture of compounds of Formula I, having the stereogenic center designated by *, which compounds are enantiomerically enriched in the S configuration.
This invention further pertains to a process for preparing a racemic or enantiomerically enriched arthropodicidal oxazoline of Formula II: ##STR5## wherein Ar is 2,6-difluorophenyl, 2-chlorophenyl or 2-chloro-6-fluorophenyl; ##STR6## wherein X is Cl, Br or OSO.sub.2 A;
The present invention further pertains to a process comprising the additional step of preparing a compound of Formula III by reacting a compound of Formula IV: ##STR7## where m is 0, 1 or 2 with ArCN provided that when m is 0 an oxidation is performed to provide the compounds where n is 1 or 2, and a process comprising the additional step of preparing the compound of Formula V: ##STR8## by reducing a compound of Formula VI: ##STR9## and a process comprising the additional step of preparing the compound of Formula VI wherein m is 1 or 2, by reacting a compound of Formula VII: ##STR10## with ClCH.sub.2 C(O)Cl in the presence of aluminum trichyloride.
The present invention further pertains to a process comprising the additional step of preparing a compound of Formula III wherein X is Cl, comprising reacting a compound of Formula VII with a compound selected from compounds of the formula ArC(O)NHCH.dbd.CHCl, ArC(O)NHCHOHCH.sub.2 Cl and ArC(O)NHCH(CH.sub.2 Cl)OCH(CH.sub.2 Cl)NHC(O)Ar and mixtures thereof.
The present invention further pertains to a compound having the formula selected from ArC(O)NHCH.dbd.CHCl, ArC(O)NHCHOHCH.sub.2 Cl and ArC(O)NHCH(CH.sub.2 Cl)OCH(CH.sub.2 Cl)NHC(O)Ar wherein Ar is 2,6-difluorophenyl, 2-chlorophenyl or 2-chloro-6-fluorophenyl, and particularly a compound having Formula VIII: compound of Formula VIII by reaction of an amide of Formula IX:
DETAILS OF THE INVENTION
The present invention includes novel processes illustrated by Schemes A1, A2, A3, B1, B2, B3, C1, C2 and C3 for preparing compounds of Formula 1 (including compounds of Formula II) and key intermediates leading thereto which are racemic or enantiomerically-enriched at the stereogenic center indicated by the asterisk. ##STR11## wherein n is 0, 1 or 2; and identify stereogenic centers, [H] indicates reductions, and [O] indicates oxidations. ##STR12## wherein n is 1 or 2; ##STR13## wherein n is 1 or 2; ##STR14## wherein n is 1 or 2; ##STR15## wherein R.sup.1 is N(CH.sub.3).sub.2 or OR.sup.2 ; ##STR16## wherein n is 0, 1 or 2; ##STR17## wherein Ar is 2,6-difluorophenyl, 2-chlorophenyl or 2-chloro-6-fluorophenyl. ##STR18## wherein R.sup.1 is N(CH.sub.3).sub.2 or OR.sup.2 ; ##STR19## wherein R.sup.1 is N(CH.sub.3).sub.2 or OR.sup.2 ; ##STR20## wherein R.sup.1 i
REFERENCES:
patent: 5354905 (1994-10-01), Sato et al.
Lusskin, Robert M. et al., A New Reaction of Nitriles. V. Preparation of N-(2-Halo-1-ethyl)-amides, Journal of The American Chemical Society, 72, 5577-5578, Dec. 1950.
Christol, Henri et al., Transpositions acidocatalysees (X.sup.e memoire). Reaction de Ritter sur les alcools benzyliques secondaires et les benzylcarbinols, Bulletin de la Societe Chimique de France, 8, 2313-2318, 1961.
Annis Gary David
Shapiro Rafael
E. I. Du Pont de Nemours and Company
Powers Fiona T.
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