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United States Patent (19) (11) 3,862,166 Baklien Et Al

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United States Patent (19) (11) 3,862,166 Baklien Et Al United States Patent (19) (11) 3,862,166 Baklien et al. (45) Jan. 21, 1975 (54) CERTAIN (5) Int. Cl............................................. C07d 91/18 3-HALOETHYL-2-IMINOTHIAZOLIDINE 58) Field of Search................... 260/306.7, 306.7 T (75) Inventors: Asbjorn Baklien, Kingsbury, 56) References Cited Victoria; Jan Kolm, Kew, Victoria, both of Australia UNITED STATES PATENTS 3,478,047 1 1/1969 Doyle et al...................... 260/306.7 73) Assignee: ICI Australia Limited, Melbourne, 3,642,809 2/1972 Bullock............................ 260/306.7 Australia 3,679,696 7|1972 Bullock............................ 260/306.7 22) Filed: Apr. 3, 1972 OTHER PUBLICATIONS Wagner et al., Synthetic Organic Chemistry, John 21 ) Appl. No. 240,827 Wiley & Sons, N.Y., 1953, pp. 89-92. Related U.S. Application Data Prelog et al., Chem. Abstracts, 26:2168 (1931). 62 Division of Ser. No. 565,092, July 14, 1966, Pat. No. 3,759,937. Primary Examiner-Richard J. Gallagher Attorney, Agent, or Firm-Cushman, Darby & 30) Foreign Application Priority Data Cushman July 19, 1965 Australia........................... 61653,165 July 26, 1965 Australia........................... 693 1165 57 ABSTRACT Aug. 31, 1965 Australia........................... 63415165 Synthesis of tetramisole and analogues thereof com Sept. 8, 1965 Australia........................... 63786/65 mencing with N-substituted-aziridine. (52) U.S. Cl........................................... 260/306.7 T 4 Claims, No Drawings 3,862,166 1. 2 CERTAIN which is halogen, nitro, acylamino, alkoxy, aryloxy, al 3-HALOETHYL-2-IMINOTHAZOLDINE kylthio, arylthio and wherein R furthermore may be a This application is a division of Ser. No. 565,092, five- or six-membered heterocyclic radical having N, S filed July 14, 1966, now U.S. Pat. No. 3,759,937. or O in the ring and wherein R' is hydrogen whenever This invention relates to a new process for making R" is hydrogen (Reaction 1). Typical acyloxy groups chemical compounds which are useful as intermediates are acetoxy, propionoxy, butyroxy. to biologically active compounds and/or which are The process is of particular interest in respect of cer themselves biologically active. It also relates to new tain valuable compounds for which, as far as we know, and useful chemical compounds. One particular biolog no synthesis of comparable simplicity is known; ac ical activity is the anthelmintic effect of the products of 10 cordingly a preferred process is characterised in that R these processes. stands for phenyl, halophenyl, nitrophenyl, trifluoro It has been demonstrated in South African Patent methylphenyl, naphthyl, alkoxyphenyl, alkylthiophe Application No. 24.67/65 that certain imidazo(2, 1 nyl, arylthiophenyl, methyl, ethyl, benzyl, hydroxy b) thiazoles including those having the formula methyl, methoxymethyl, phenoxymethyl, phenylthi 15 omethyl, 2-thienyl, 4-pyridyl and 2-furyl; R is hydro 7 1. gen, alkyl, aryl, alkaryl or aralkyl, R' is hydrogen or, Air whenever R' is a substituent other than hydrogen R' may also be alkyl, aryl, alkaryl or aralkyl; and 4. 20 A. or the therapeutically acceptable acid addition salts Hs&nd thereof, wherein Ar is a thienyl, furyl, phenyl, halo phenyl, nitrophenyl, aminophenyl, trifluoro is thiocyanic acid or isothiourea. While we consider methylphenyl, naphthyl or benzyl group, and in partic 25 that the latter is in this isomeric form symbolised by the ular certain preferred compounds namely di-2,3,5,6- formula tetrahydro-6-(4-nitrophenyl)imidazo2, 1-bithiazole hydrochloride, dl-2,3,5,6-tetrahydro-6-(4- NH aminophenyl)imidazo[2,1-bithiazole hydrochloride, His c^ N dl-2,3,5,6-tetrahydro-6-phenyl-imidazo[2,1-bthiazole 30 NH hydrochloride and dl-2,3,5,6-tetrahydro-6-(2- thienyl)imidazo. 2, 1-bithiazole hydrochloride have useful, biological, particularly anthelmintic properties. when entering in the nucleophilic attack on the aziri Formulations comprising these compounds, their meth dine ring, it will be understood that the reagent actually 35 added is thioren and changes to its tautomeric form in ods of use in combating undesired animal pests and dis the reaction medium. Throughout this specification the eases and certain process of manufacturing the com terms thiourea and isothiourea are therefore used inter pounds have also been claimed and disclosed in said changeably. It is also obvious that the thiocyanic acid patent application. may be generated in situ from its salts, particularly so We have now discovered a process by which these 40 dium or potassium thiocyanate and a suitable acid. Our and other compounds and certain intermediates useful process is particularly useful for the manufacture of for their synthesis may be manufactured. compounds of formula III wherein R stands for phenyl, Accordingly we provide a process comprising react 2- or 3- or 4-chlorophenyl, 3-bromophenyl, 4 ing a compound of the formula fluorophenyl, 2-nitrophenyl, 3-nitrophenyl, 4 45 nitrophenyl, 4-tolyl, 3-trifluoromethylphenyl, 2,3,4- HR trichlorophenyl, benzyl, phenoxymethyl, phenylthi omethyl, 2-thienyl and 2-furyl and R' and R'' are hy reg HR' (Formula I) drogen. Reaction 1 is conveniently carried out in water or in 50 a mixture of water and a water-miscible organic sol with a compound of the formula vent, in the presence of an acid. Alternatively it may A. also be carried out in an organic solvent in the presence of an acid which in the medium is capable of acting as HS bND (Formula II) a proton donor. Suitable organic solvents are e.g. lower 55 alcohols or acetone, dioxan, tetrahydrofuran, dimethyl to produce a compound of the formula formamide and sulpholane. Suitable acids are e.g. sul phuric, hydrochloric, nitric, perchloric, p-toluenesul R-CHCHN-CHR' phonic, phosphoric, formic, acetic, maleic, thiocyanic and oxalic acids. Excess acid, i.e. acid in excess of that hN^ Ys / (Formula III) 60 required to neutralise the bases formed is preferred; two to three mole equivalents per mole of wherein X is hydroxy, acyloxy or hydrogen; A stands for NH and D stands for hydrogen or both substituents -A and -D are absent; R, R' and R', which may be CFR the same or different, may be hydrogen, alkyl, aryl, al 65 karyl or aralkyl and R may be substituted by a substitu R.CH.CHN ent which is non-reactive with the aziridine ring and k Yir 3,862,166 3 4 are satisfactory; 0.1 to 0.5 mole excess acid is pre tion of the isothiouronium salt e.g. in an organic solvent ferred. Reactant ratios are not highly critical, but a having a boiling point between 120 and 180°C, such as slight excess of thiourea or thiocyanic acid respectively ethylene glycol monoacetate. is preferred. The preferred method of carrying out reaction l is in Reaction temperature for the overall reaction l is not a single step. If in reaction 1 an acid other than the rela narrowly critical; it varies somewhat from thiocyanic tively strong acids listed above is used, the acidity acid to thiourea and also depends on the nature of sub should be adjusted to give a pH meter reading between stituents R' and R''. Thus the ring-closure with thiocy 1 and 3.6. anic acid occurs already at room temperature, but ele The compounds of formula III may be isolated from vated temperatures are required with thiourea. In gen 10 the solvent e.g. water or alcohol, as the salt by evapora eral best results are obtained by maintaining the tem tion, crystallisation or precipitation. We have found perature between -10° and 50°C over an initial period that the thiocyanic acid salt of compound III is spar of 5 to 60 minutes, followed by heating to between 60' ingly soluble in water and in most organic solvents; the and 180°C for a period from 4 to 5 hours, preferably thiocyanic acid salt may be formed by adding, in reac from 4 to 2 hours when thiocyanic acid is used and 5 tion 1, slightly more than two equivalents of thiocyanic from 2 to 4 hours when thiourea is used. Higher and acid, when the latter is the reactant according to for lower temperatures are feasible. We have isolated on mula II, or by addition of one equivalent of thiocyanic intermediate in this process; hence, while we do not acid to the salt of formula III after the reaction had wish to be limited by theory, we consider that the reac been completed. The thiocyanate precipitates and can tion occurs in two steps; in the first step an intermedi 20 then be separated conveniently; when conversion to ate salt is formed, namely an isothiouronium salt as ex the hydrochloride salt is desired, the thiocyanate may emplified in Example 32 method A whenever thiourea be dried and suspended in a non-aqueous inert liquid, is used, and a thiocyanate salt of the formula e.g. isopropanol and reacted with dry hydrogen chlo ride. The hydrochloride is obtained in high purity. Ac 25 cordingly a preferred process comprises precipitating it. CII.C H.N.I.CHR'. CEIIR''.SCN. Acid, compound III as the thiocyanate. A further method of isolating compound III from aqueous media comprises whenever thiocyanic acid is used; in the second step forming its base by neutralising the medium to a pH of said intermediate salt is cyclised to the thiazolidine 10 to 13, extracting the base with a first water ring. In the case of the isothiouronium salt the interme 30 immiscible organic solvent, e.g. chloroform, removing diate salt may be isolated if desired and the two steps water from the extract, adding to the extract a second may be carried out separately, whereas the thiocyanate solvent which is hydrophilic and miscible with the first salt ring-closes more rapidly. Temperature conditions solvent e.g. ethanol, mixing, forming the hydrochloride are virtually the same as when the reaction is carried by adding dry hydrogen chloride and separating the hy out in one step; temperatures from -10° to 50°C, pref 35 drochloride of compound III.
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