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A Process for the Production of 2-Alkyl Or 2-Cycloalkyl-4-Methyl-6-Hydroxypyrimidines Joseph T

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A Process for the Production of 2-Alkyl Or 2-Cycloalkyl-4-Methyl-6-Hydroxypyrimidines Joseph T University of Richmond UR Scholarship Repository Chemistry Faculty Publications Chemistry 1979 A Process for the Production of 2-Alkyl or 2-Cycloalkyl-4-methyl-6-hydroxypyrimidines Joseph T. Blackwell III John T. Gupton University of Richmond, [email protected] Teruko U. Miyazaki James B. Nabors Joseph R. Pociask Follow this and additional works at: http://scholarship.richmond.edu/chemistry-faculty- publications Part of the Organic Chemistry Commons Recommended Citation Blackwell, Joseph T., III, John T. Gupton, Teruko U. Miyazaki, James B. Nabors, and Joseph R. Pociask. A Process for the Production of 2-Alkyl or 2-Cycloalkyl-4-methyl-6-hydroxypyrimidines. US Patent 4163848, filed August 8, 1978, and issued August 7, 1979. This Patent is brought to you for free and open access by the Chemistry at UR Scholarship Repository. It has been accepted for inclusion in Chemistry Faculty Publications by an authorized administrator of UR Scholarship Repository. For more information, please contact [email protected]. United States Patent c191 [11) 4,163,848 Blackwell, III et al. [45] Aug. 7, 1979 [54] PROCESS FOR THE PRODUCTION OF [56] References Cited 2-ALKYL- OR U.S. PATENT DOCUMENTS CYCLOALKYL-4-METHYL-6-HYDROX· YPYRIMIDINES 3,997,536 12/1976 Boller et al. ........ .. .. ..... ... ..... 544/319 4,012,506 3/1977 Balke et al ........................... 544/319 4,014,879 3/1977 Balke et al ........................... 544/319 [75] Inventors: J01eph T. Blackwell, ID, 4,018,771 4/i977 Gupton et al. ....................... 544/319 Greensboro; John T. Gupton, 4,052,396 10/1977 Pociask ................................ 544/319 Jamestown; Teruko U. Miyazaki, 4,052,397 10/1977 Blackwell et al .................... 544/319 Greensboro, all of N.C.; James B. Primary Examiner-Donald G. Daus Nabors, Baton Rouge, La.; Joseph R. Assistant Examiner-James H. Turnipseed Pociask, Greensboro, N.C. Attorney, Agent, or Firm-Karl F. Jorda [57] ABSTRACT [73] Assignee: Ciba-Geigy Corporation, Ardsley, N.Y. Production of 2-alkyl- or cycloalkyl-4-methyl-6- hydroxypyrimidines by first neutralizing an alkyl imi­ date ester hydrochloride with a base in the presence of [21) Appl. No.: 93.2,087 a water-immiscible solvent for the alkyl imidate ester to be freed thereby; condensing the alkyl imidate ester with diketene to form an oxazinone intermediate, which Aug. 8, 1978 [22] Filed: is then reacted in organic solution with gaseous ammo­ nia and recovering the desired substituted 6-hydrox­ [51] Int. Cl,2 ...•........................................ C07D .239/36 ypyrimidine. [52) U.S. Cl ........................................ 544/319; 544/97 [58] Field of Search ......................................... 544/319 18 qaims, No Drawings 4,163,848 1 2 -continued PROCESS FOR THE PRODUCTION OF 2·ALKYL­ OR CYCLOALKYL-4-METHYL-6-HYDROXYPYRIMI· DINES s N~ FIELD OF THE INVENTION R-l. N ~o- Na+ + HCI ~ The present invention relates to a new and improved manufacturing process for 2-alkyl- or 2-cycloalkyl-4- 10 methyl-6-hydroxypyrimidines of the formula: N~ R-l. N ~OH + NaCl IS N~ Recently the above conventional manufacturing pro- R-l. N ~OH cess has been improved and optimized by a continuous ring-closure/neutralization process as claimed in U.S. wherein R represents an alkyl or cycloalkyl group. Pat. No. 4,014,879, issued Mar. 29, 1977. Alkyl groups denoted by R are straight or branched 20 Alternate processes for the preparation of these hy- chain lower alkyl groups having preferably l to 4 car- droxypyrimidines have been published in the Japanese bon atoms such as, methyl, ethyl, n-propyl, isopropyl, Patent literature. Japanese Pat. No. 557,103 teaches that n-butyl, secondary butyl, isobutyl, or tertiary butyl. these hydroxypyrimidines can be prepared by various Cycloalkyl groups denoted by R have 3 to 6 ring heat treatments from .13-acylaminocrotonamides pre- carbon atoms. Preferred cycloalkyl groups are cyclo- 2s. pared from .13-aminocrotonamides (derived from dike­ propyl, cyclopentyl or cyclohexyl. tene and ammonia) and acid halides or anhydrides. Ac­ cording to published Japanese Patent Application SHo- BACKGROUND OF THE INVENTION 48-39-942 these hydroxypyrimidines can be prepared by The compounds of formula I are important interme- reacting .13-aminocrotonamide and an organic acid ester diates for the preparation of, e.g., phosphoric acid esters 30 in the presence of certain alkaline reactants such as of substituted hydroxypyrimidines as disclosed and alkali metals or their alcoholates. claimed in U.S. Pat. No 2,754,243 and in particular Rec~ntly there have been patented alternate ways of O,O-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl)-thio- prepanng the compounds of Formula I including U.S. phosphate (DIAZINON) which has great commercial Pat. No. 3,618,771, which issued Apr. 19, 1977 and U.S. value. It is a well-established insecticide and acaricide 35 Pat. No. 4,052,396 and U.S. Pat. No. 4,052,397, which and is useful in pest control. issued on Oct. 4, 1977. These substituted hydroxypyrimidines have been U.S. Pat. No. 4,018,771 teaches the synthesis of these produced in commercial practice in a laborious multi- compounds by reacting diketene with lower alkanoic step manner as follows: acid amides in the presence of catalysts and then treat- 40 ing the resulting N-acetoacetyl alkanoic acid amides with ammonia in the presence of acidic catalysts. a) Iminoether Step: U.S. Pat. No. 4,052,396 discloses the reaction of dike­ R-C =:N + C2HsOH + 2 HCI ~ tene with alkanoic acid nitriles in the presence of acidic ; NH.HCI catalysts followed by the treatment of the reaction R-C + HCI 45 product with ammonia. U.S. Pat. No. 4,052,397 discusses the preparation of OC2H5 the hydroxypyrimidines of Formula I by sequentially b) Amidine Step: " treating, in organic solvent, diketene with ammonia and NH.HCI ; then treating the resulting ,8-aminocrotonamide, after R-C +NH3~ 50 water removal, with an alkanoic acid ester and an alkali OC2Hs metal alkoxide. " NH.HCI However, all of these prior art procedures leave ; something to be desired from the standpoint of efficient R-C + C2HsOH economical large-scale commercial manufacturing. It is NH2 SS an object of this invention to provide a better synthetic c) Ring-closure Step: " route to these materials. NH.HCI ; THE INVENTION R-C + CH3COCH2COOCH3 NaOH > The present invention provides a better and cheaper "NH2 60 technology which unexpectedly is based upon the easily prepared imidate (imidine) hydrochloride intermediate of the earliest synthetic route and proceeds to prepare therefrom these products by simple steps, in batch or continuous processing, to yield the desired product in Na+ 65 excellent yield and high purity. The process which proceeds easily under mild conditions comprises the steps of neutralizing an imidate hydrochloride of the d) Neutralization Step: formula: 4,163,848 3 4 ganic, such as, an alkali metal hydroxide and carbonate NH.2HCI II or an organic acid~acceptor base. Among the latter, ; trialkylamines of C14alkyl, such as, trimethylamine or R-C triethylamine perform very well, with trimethylamine OR' S being preferred. Pyridine is also an excellent acid­ ' acceptor base. with an aqueous solution of a strong acid-accepting base Among the water-immiscible solvents used to dis- in the presence of a water-immiscible solvent to obtain solve the neutralized (free) imidate are the liquid aro­ the free imidate. R is, as noted above, alkyl of 1 to 4 matic and aliphatic hydrocarbons and the liquid chlori­ carbon atoms or cycloalkyl of 3 to 6 ring carbon atoms 10 nated hydrocarbons, including benzene, toluene, xy­ and R' is alkyl of 1 to 4 carbon atoms. lene, hexane, heptane, 1,1,1-trichloroethane, 1,1,2-tri- The organic phase containing the free imidate is sepa­ chloroethane, tetrachloroethylene, dichloromethane, rated from the aqueous phase and dried and the imidate ethylene dichloride with toluene being preferred as it is reacted with diketene in organic solution and in the subsequently provides greater ease in water removal. presence of a catalyst to form an oxazinone having the lS A possible temperature range for this reaction step is formula: · -30 to so• C.; a preferable range is -10 to 2S° C. and a most preferable range is 0 to 10. However, if this HJC~ reaction step is carried out continuously, the tempera­ 1- 1=0 ture should preferably range between 10 to 20° C. 0 NH 20 The reaction time for this step may range between S to 120 minutes and preferably between 10 to 60 minutes. RXOR' The water removal ensures a purer product in better yield and thus is important in commercial practice. The wherein R and R' are as above. water is initially removed by phase-separation of the Upon completion of the diketene addition, the result- 2s immiscible organic solvent with the free imidate dis­ ing oxazinone in organic solution is reacted with gase­ solved therein. Any residual water in the solvent is ous ammonia. Any water formed is removed and the removed by azeotropic distillation or contact with dry­ 2-alkyl-4-methyl-6-hydroxypyrimidine recovered upon ing agents, such as, molecular sieves or anhydrous dry­ removal of the organic solvent in substantially pure ing salts, such as, anhydrous sodium sulfate. Of these form and excellent. yield. 30 drying steps, the contact drier,c; are preferred in the DETAILED DESCRIPTION OF THE laboratory but azeotropic distillation is preferred on an INVENTION industrial scale. The dry imidate base is then reacted with diketene to The basic reaction scheme may be illustrated as fol- form the oxazinone. The imidate and the diketene pref­ lows: 3S erably should be dissolved in solvents. It is preferred if a mutual solvent, such as, toluene, NH.HCI NH tetrachloroethylene or trichloroethylene is used, but ; Base/H20 ; R-C __,,.....--->;1ooR-C individual solvents for each component may be used if Solvent '- 40 they are mutually miscible.
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