United States Patent 1191 1111 3,931,208 Offermanns Et Al
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United States Patent 1191 1111 3,931,208 Offermanns et al. [451 Jan. 6, 1976 [54] PROCESS FOR THE PRODUCTION OF formula: THlAZOLINES-( 3) [75] Inventors: lleribert Offermanns, Grossauheim; Friedrich Asinger, Rott; Wolf-Dieter Pfeifer, Grossauheim; Paul (l) Scherberich, Neu lsenburg; Gerd Schreyer, Grossauheim, all of Germany in which R‘, R2, and R3 and R4 are the same or differ [73] Assignee: Deutsche Gold- und _ ent, R‘ and R2 are straight or branched chain lower Silber-Scheideanstalt vormals alkyl, alkenyl ‘or aralkyl groups or together are a Roessler, Frankfurt am Main, straight or branched chain alkylene or ethylenically Germany unsaturated divalent aliphatic hydrocarbon group which joins with the adjacent carbon atom to form a 1221 Filed: Nov. 5, 1973 ring and R3 and R4 are similarly de?ned except R3 can 1211 Appl. No.: 413,048 also be hydrogen by reaching a 2,2’ dioxodisul?deof the formula ‘ [30] Foreign Application Priority Data Nov. 9, 1972 Germany .............. .... 2254701 ' [52] U.S. Cl ......................................... .. 260/306.7 R [5]] Int. Cl.2 ...................................... .. C07D 277/10 [58] Field of Search ............................ .. 260/306.7 R V[ 56] References Cited UNITED STATES PATENTS 2,879,273 3/1959 Asinger ct al .............. .. 260/3()6.7 R 3,004,981 l0/l96l Asingcr ct al .............. .. 26()/306.7 R 3.700.683 10/1972 Asinger ct al ............. .._. 260/306.7 R Primary Examiner—Richard J. Gallagher Assistant E.raminer—Anne Marie T. Tighe Attorney, Agent, or Firm——Cushman, Darby & Cushman and with ammonia and hydrogen sulfide in the pres ence of an amine and an ammonium salt. ' [57] _ ABSTRACT ‘ 2 and S substituted thiazoline-(3) compounds of the 22 Claims, No Drawings 3,931,208 1 2 thiazoline-(3); 2»methyl-2-is0pr0pyl~5,S-dipropyl PROCESS FOR THE PRODUCTION OF thiazoline-(3 ); 2-methyl-2-ethyl-5,5-diisopropyl thiazo THlAZOLINES-(3) line-(3); 2-isopropyl-5,5-dimethyl-thiazoline-(3); 2,2 dimethyl-S,5-dibutyl-thiaZoline‘(3); 2,2,5-trimethyl-5 The present invention is directed to a process for the 5 amyl thiazoline-(3); 2,5,5-trimethyl-2-hexvl thiazoline production of 2 and S substituted thiazoline-(3) com (3); 2,2-dimethyl-5-ethyl,5-sec. butyl thiazoline-(3); pounds by reacting a 2,2'-dioxodisul?de with an oxo 2,2-dimethyl-5-ethyl-5-vinyl thiazoline-(3); 2,2-divi compound, ammonia and hydrogen sulfide. nyl-5,5-dimethyl thiaZoline-(3); 2-allyl-2,5,5-trimethyl It is known to produce 2,5,5-substituted thiazoline- l thiazoline-(3); 2-butenyl,2-methyl-5,5-diethyl thiazo (3) compounds by reaction of sulfur with an oxo com 0 line-(3); 2,5-dimethyl,2-ethyl,5-butenyl thiazoline-(3); pound and ammonia in the presence of an amine, see 2-phenethyl-5,5-dimethyl thiazoline-(3); 2,2-dimethyl German Offenlegungsschrift No. 1,795,299 and to cor 5-benzyl-5-ethyl thiazoline-(3); 2,2,5-trimethyl-5 responding Asinger US. Pat. No. 3,700,683, the entire phenethyl thiazoline-( 3 ); 2,~phenpropyl-2,2,5 disclosure of which is hereby incorporated by refer trimethyl thiazoline-(3); 2,2,5,5-di(pentamethylene) ence. According to this process, there can only be thiazoline-(3); 2,2-pentamethylene-5,5 ~hexa-methy— obtained 2,5,5-substituted thiazoline-(3) compounds lene thiazoline-(3); 2,2-heptamethylene S-methyl which have a branched chain alkyl group in the 2-posi 5-ethyl thiazoline-( 3 ); 2,2-dimethyl-5,5~octamethylene tion. thiazoline-( 3 ); 2,2-dodecamethylene-5 ,S-dimethyl It has also been proposed to produce 2,2,5,5-sub thiazoline-(3); , 2,2-dimethyl-5,S-undecamethylene stituted thiazoline-(3) compounds by reaction of 2,2’ 20 thiazoline-( 3 ); 2-methallyl-2-methyl-5-ethyl-5-propyl dioxodisul?des with oxo compounds, ammonia and thiazoline~(3). ’ hydrogen sul?de, see the .lahrbuch 1967, Landesamt The 2,2'-dioxodisul?de of formula ll can be prepared fur Forschung des Landes Nordrhein-Westfalen, pages for example according to Niederhauser US. Pat. No. 2| to 22. This process gives yields of 57% at most. 12,580,695, the entire disclosure of which is hereby There has now been found a process for the produc 25 incorporated by reference. There are preferably em tion in improved yields of 2' and S substituted thiazo ployed 2,2'-dioxodisul?des in which R1 and R2 are line-(3) compounds of the formula branched or straight chain alkyl groups of 1 to 6 carbon atoms, branched or straight chain alkenyl groups with 2 to 5 carbon atoms or branched or straight chain aralkyl 30 R Hi = N R, groups having 1 to 3 carbon atoms in the alkyl radical. The alkyl or alkenyl groups can be closed to form rings with the adjacent carbon atom, especially to rings with 5 to 12 carbon atoms. Suitable compounds are for example 2,2’-dithio-bis(2-ethyl butyraldehyde), 2,2’ in which R,, R2, R3 and R4 are the same or different, R, 35 dithio-bis(2-methyl butyaldehyde), 2,2’-dithio bis (2 and R2 represent straight or branched chain lower al phenylpropionaldehyde), 2,2’ kyl, alkenyl or aralkyl groups or straight or branched dithio-dicyclooctanealdehyde, 2,2’~dithio-di chain lower alkyl or alkenyl groups which form a ring, cyclododecanealdehyde, 2,2'-dithio-di-isobutyralde~ R3 represents hydrogen and R4 represents straight hyde, 2,2'-dithio-di-cyclohexanealdehyde, 2,2'-dithio chain lower alkyl groups or straight or branched chain 40 di-cyclopentanealdehyde, 2,2’-dithio-di-cyclohex lower alkenyl or aralkyl groups or R3 and R, a closed enealdehyde, 2,2'-dithio-di-cyclopentenealdehyde, carboxylic ring and R3 and R1 are as de?ned for R1 and 2,2'-dithio-bis(2-phenyl butyraldehyde), 2,2'-dithio R2 with the further proviso that R;, can be hydrogen. bis(2 -phenylvaleraldehyde), 2,2'-dithio-bis(2-benzyl The thiazoline-(3) compounds (I) are prepared by butyraldehyde), 2,2'-dithio bis(2-phenethyl propional reacting a 2,2'-dioxodisulfide of the formula 45 dehyde, 2,2’-dithio bis(2-methylvaleraldehyde), 2,2’ dithio bis(2-methylhexaldehyde, 2,2'-dithio bis(2 methyl octane-aldehyde), 2,2'-dithio bis(2-ethyl isobu tyraldehyde), 2,2'-dithio bis(2-methyl sec.valeralde hyde),,2,2’-dithio bis(2-butyl hexaldehyde),2,2'-dithio bis(2-hexyl octaaldehyde), 2,2'-dithio bis(2-methyl 2 2 crotonaldehyde), 2,2'-dithio bis(2-vinyl propionalde hyde), 2,2'-dithio bis(2-ethyl A -4 pentenaldehyde), in which R, and R2 are as de?ned above with an oxo 2,2’-dithio bis(2-methyl propionaldehyde), 2,2'-dithio compound of the formula bis(2-ethyl hexaldehyde). Preferably compound ll is 55 2,2'~dithio-diisobutyraldehyde or 2,2’-dithio-di cyclohexanaldehyde. = (III) As oxo compound corresponding to formula [II there R,/ v can be especially employed either those in which R3 is hydrogen and R4 is a straight chain or branched alkyl where R_-, and R4 are as defined above with ammonia 60 group with l to 6 carbon atoms, a straight or branched and hydrogen sul?de in the presence of an amine and chain alkenyl group with 2 to 6 carbon atoms or a an ammonium salt. There is usually employed an am straight or branched chain aralkyl group with‘ l to 3 monium salt other than ammonium sul?de. carbon atoms in the alkyl group or those compounds in Examples of compounds within the present invention which R3 and R4 are straight or branched chain alkyl in addition to those set forth in the working examples 65 groups with l to 6 carbon atoms, branched or straight are 2-methyl-2-propyl-5-ethyl-5-butyl thiazoline-(3); chain alkenyl groups with 2 to 6 carbon atoms. 2,2.5.S-tetraethyl-thiazoline-(3); 2.2-dimethyl-5.5 branched or straight chain aralkyl groups with l to 3 dihexyl-thiazoline-(3); 2,2-dihexy1-5.5-dimethyl carbon atoms in the alkyl radical. The alkyl or alkenyl 3,931,208 4 groups can be closed to form a ring with the adjacent trate, ammonium oleate, ammonium stearate. The pre~ carbon atom, especially rings with 5 to 12 carbon ferred salts are ammonium chloride, ammonium sulfate atoms. Suitable compounds are, for example. acetalde and ammonium acetate. The ammonium salt can be hyde, propionaldehyde, n-butyraldehyde, cyclopen added as such or can be formed in the reaction mixture tanealdehyde. cyclohexanealdehyde. cyclooctanealde from ammonia and the particular acid or acids. hyde, cyclododecanealdehyde, valeraldehyde, hex For each mole of 2,2’-dioxodisul?de there are re anealdehyde, heptanealdehyde, Z-phenylacetaldehyde, quired 2 moles of carbonyl compound lll. It is advanta 3-phenyl-propionaldehyde, 4 -phenylbutyraldehyde, geous to employ an excess of carbonyl compound up to isobutyraldehyde, sec. valeraldehyde, aerolein, croton about 6 moles (i.e., a total of 8 moles). Preferably there aldehyde, A -6 hexenaldehyde, acetone, methyl ethyl are employed about 4 to 6 moles of carbonyl com ketone, diethyl ketone, methyl isob'utyl ketone, hepta pound per mole of the 2,2'-dioxodisul?de. There are none-4-phenylacetone, pentanone-2, cyclopentanone, also required per mole of the 2,2’-dioxodisul?de 2 cyclohexanone, dibenzyl ketone, cyclooctanone, cy moles of ammonia and 1 mole of hydrogen sul?de. It is clododecanone, methyl heptyl ketone, dibutyl ketone, also advantageous to have an excess of these sub~ di sec. butyl ketone, diisobutyl ketone, divinyl ketone, stances, e.g., up to about 4 moles in excess (i.‘e., a total diallyl ketone, methyl hexen-l-yl ketone, dimethallyl of 6 moles of ammonium or 5 moles of hydrogen sul ketone, methyl vinyl ketone, ethyl vinyl ketone, methyl ?de).