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United States Patent (19) (11 3,878,194 Moffatt Et Al United States Patent (19) (11 3,878,194 Moffatt et al. (45) Apr. 15, 1975 54 NOVEL PHOSPHORYLATED 58) Field of Search.............................. 260/211.5 R PHOSPHONIUM YLIDS (75) Inventors: John G. Moffatt; Gordon H. Jones, (56) References Cited both of Los Altos, Calif. UNITED STATES PATENTS 73 Assignee: Syntex (U.S.A.) Inc., Palo Alto, 3,583,974 6/197 Jones et al................... 260/21 15 R Calif. Primary Examiner-Johnnie R. Brown 22 Filed: Oct. 15, 1971 Attorney, Agent, or Firm-Lawrence S. Squires; 21 ) Appl. No.: 189,562 William B. Walker Related U.S. Application Data (57) ABSTRACT (60) Division of Ser. No. 709,234, Feb. 29, 1968, Pat. No. 3,662,03, which is a continuation-in-part of Ser. No. Novel phosphorylated phosphonium ylids are pre 654,056, June 18, 1967, abandoned. pared by reacting a monosubstituted phosphonium ylid with an appropriately disubstituted phosphoryl (52) U.S. Cl............... 260/21 1.5 R; 260/954; 7786; halide or thiophosphoryl halide. The novel ylids are 71/87; 260/956; 195/28 N; 252/46.6; useful as intermediates in the preparation of phos 260/968; 260/247.7 D; 260/252; 424/200; phonic acid or thiophosphonic acid derivatives there 260/254; 260/256.4 E; 424/80; 260/293.4 from and as intermediates for the preparation of insec B; 260/293.4 R 424/203; 260/502.4 Ri ticides, herbicides, oil additives and 5,6'-dideoxyhex 260/551 P; 424/219; 260/927 R; 260/932 ofuranosylnucleoside 6'-phosphonic acid. 51 Int. C. C07d 51150; C07d 105/04; C07f 9/54 8 Claims, No Drawings 3,878, 194 2 NOVEL PHOSPHORYLATED PHOSPHONM A primary object of the present invention is to pro Y1)S vide a new class of phosphorylated phosphonium ylids This is a livision of application Ser. No (“. filed which can be reacted with a wide variety of aldehydes Feb. 29, 9 (S. ninw l S. P. t. No. 3 (Yes, which is a and ketones, thereby providing unsaturated phs sph)- continuation-in-part of application Sel. N. (n54.56. S nate or thiophosphonate derivatives thereof. Another filed July N, 1967, and now alanck met object of the invention is to provide a process for react This invention relates to a new class of the Shinry la ing the novel phosphorylated phosphonium ylid with a led phosphynium y lils and to a rice SS fir the Tearl nucleoside 5'-aldehyde to form the corresponding 5.6- tion of 5 ,6'-dides vy hexofuranos y nullet Side ( - '-clideoxyhe N-5'-enofuranosylnucleosicle 6'- ( phosphonate. The latter unsaturated nucleoside is cata phosphonic acids there with. More particularly, the in lytically hydrogenated or chemically reduced and then vention relates to a new class of hushtty lated phos converted to a corresponding 5,6'-dide Nyhex phonium ylids having the following formula: ofuranosylnucleoside 6'-phosphonic acid by hydrolysis, hydrogenolysis, anionic dealkylation, or enzymatic ile 5. tion or combinations thereof. The novel phosphorylated phosphonium ylids of For mula (A ) are prepared according to the following Teac tin: () R Y l R Y 7 RNP-cil R - X-1 a- RSr-c-f- wherein / N each of R. R. and R is lower alkyl, aryl or Suhsti R3 22 R R 22 tuted aryl: (l) (II) (A) R. R. and R together are tri-N-piperidyl, tri-N- morpholiny kr tricyclohexyl. R is hydrogen low crulkyl cyclohexyl, aryl. Or Substi where in X is chlor) or bromo; and all other substitu ents are as defined hereinabove. tute aryl. in the practice of the above sequence, a monosubsti Y is xygen if sulfur. tuted phosphonium yid ( ) is condensed under sub each of 7 and Z is the group OR. SR" stantially anhydrous conditions with an appropriately 1. / N disubstituted phosphoryl halide or thiophosphoryl hal N , N O, or ide (l) in a non-reactive organic solvent such as tetra N. Y-1 hydrofuran, dioxane, dimethylformanide, dimethyl or NR'R' in which each of R and R" is lower alkyl, 35 sulfoxide, benzene, diethyl ether, hexane, and the like, lower alkenyi. aryl r substituted aryl, and each of R and mixtures thereof, at a temperature of about 0°C to and R is low cr alkyl, of aryl, and the reflux temperature of the solvent, for a period of about 2 to about 12 hours. Preferably, the condens:- Z and Z together are the group tion is performed in diethyl ether, hexane, tetrahydro O O S () Y Y N furan, benzene, or mixtures thereof, with an appropri IR. R9. or R / / / ately disubstituted phosphoryl chloride or thiophos O S. phoryl chloricle ( II), i.e. wherein X is chloro. Further in which R" is alkylene or arylene. more, reactions of the monosubstituted phosphonium The term 'lower alkyl means a straight (rhranched ylid (l), wherein R is hydrogen, alkyl or cyclohexyl, chain hydrocarhon group containing from 1 to 6 car are preferably performed at room temperature for a pe bon atoms, inclusive. Such as methyl ethyl. n-propyl. riod of about 5 minutes to about 1 hour; and reactions i-butyl, t-butyl, and the like. The term lower alkenyl of the monosubstituted phosphonium ylid (l), wherein means an alkyl group containing one carbon carbon R" is aryl or substituted aryl are preferably performed double bond such as allyl and the like. The term aryl at the reflux temperature of the solvent for a period of means a hydrocarbon group consisting of one or more about 2 hours or longer. aromatic rings and containing from 6 to 2 carbon Although the molar proportion of the monosuhsti atoms. inclusive, such as phenyl. benzyl. (y-toly, m tuted phosphonium yid ( ) to the disubstitute phos tolyi. p-tolyl. 3.5-xylyl, pentamethylphenyl, naphthyl, phoryl halide or thiophosphoryl halide (II) is not criti and the like. The term 'substituted aryl means an aryl cal, a preferred embodiment of two moles of the mono group having one or more halo. nitro, alkoxy, or dial 5 5 substituted phosphonium ylid per mole of the disubsti kylamino Suhstituents in the aromatic ring such as p tuted phosphoryl halide or thiophosphoryl halide () is chlorohenzyl. p-bromohenzyl, 2,4,6-trichlorophenyl, convenient. p-nitrophenyl, p-nitrobenzyl, p-anisyl, p in the practice of the above sequence, the reaction is methoxybenzyl, p-dinnethylaminophenyl. and the like. advantageously performed in the presence of an inert The term lower alkylene means the group) --(CH atmosphere such as a nitrogen atmosphere, an argon - in which in has a value of from to 4, inclusive. atmosphere, and the like. In addition, the mont Suhsti Such as ethylene. trimethylene and tetru methylene. Said tuted phosphonium ylid ( ) is generated in situ hy con group can be further substituted with one or more alkyl ventional techniques known to those skilled in the art. orary groups such as in 2.2-dimethyltrimethylene, 1,2- Included among the monosubstituted phosphonium diphenylethylene and the like. The terhn 'arylene' ylids ( ) which can be condensed with the disubstituted means an aryl group having two sites of attachment phosphoryl halide or thiophosphoryl halide (l) are such as ()-phenylene and the like. methylenetrialkyl? including cycloalkyl)phosphoranes 3,878, 194 3 4 such as methylenetri-n-butyl) phosphorine, methylen like, disubstituted chloridodithioates such as S.S. etrimethylphosphorane, methylenetricyclohexylphos diethyl phosphorochloridodithioate, S.S.-dibutyl phorane, and the like: methylenealkylarylphospho phosphorochloridodithioate, and the like, disubstituted ranes such as methylene ethyldiphenylphosphorane, n chloridotrithioles such as tiethyl phosphorochlorido ethylenennethyldiphenylphosphorane. methyleneciphe trithioate, and the like. disubstituted phosphoro nyl-t-butylphosphorane, and the like: methylenetriaryl bromidothioates such as O.O-diethyl phosphoro phosphoranes such as methylene triphenylphospho bromidothioate. O,O-diphenyl phosphorobromidothio rane, methylene tri-p-tolylphosphorine. methylenetri ite and the like disubstitute phosphorodiamidic chlo p-a I isyphosphorne, and the like: ilky liclenetrialkyl rides such as tetraethylphosphorcycliamidic chloricle. phosphoranes such iS ethyliclene- (n- () phosphorodimorpholidic chloride, N.N'-dimethylphos butyl phosphorane, and the like, alkyliclenealkylaryl phorodinalidic chloride, tetramethyl phosphorodia phosphoranes such as ethylidene methyldiphenylphos midic chlorile, and the like, disubstituted phos phorane, and the like: alkyl idenetriurylphosphorunes phorodian idic bromides such as phosphorodimorphol such as ethylidenetriphenylphosphorane, propylidenet idic bronhide and the like: mixed disubstituted phos riphenylphosphorane, butyliciene triphenylphospho 5. phoramidochloridates such as O-phenyl N,N-diethyl rune, penty licene triphenylphosphorane, cyclohexylme phosphoramidochloridate, O-ethyl N,N-diethylphos thylene triphenylphosphorane, {3-phenylethylidenetri phoramidochloridate, O-isopropyl N,N-dimethylphos phenylphosphorane, 3-methylbutylide metriphenylphos phoramidochloridate, and the like; mixed disubstituted phorane, and the like, arylmethylenetrialkylphospho phosphoramidochloridothioates such as S-butyl N,N- rank S. Such as benzylic enetrimethylphosphorane, benz diethylphosphoramidochloridothioate, O-ethyl N,N- yielenetricyclohexylphosphorane, and the like: arylme diethylphosphoramidochloridothioate, O-2,4,5- thylenetriary phosphoranes such as henzylidenetri trichlorophenyl N,N-dimethylphosphoramido phenylphosphorane, p-nitrobenzyliclene triphenylphos chloridothioate, and the like. phorane, p-methoxybenzylidenetriphenylphosphorane, Additionally, other disubstituted phosphoryl halides benzylidenediphenyl-p-dimethylaminophenylphospho or thiophosphoryl halides ( ) are obtained by conven rane, and the like; and methylenetri-N-morpholinyl tional techniques as described hy G. N. Kosolapoff. phosphorane.
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