uent, a very vigorous reaction which was difficult to control set in after an induction phase, thus excluding use on an industrial scale. It is an object of the present invention to provide an alternative process for the preparation of thioethers. Using the preparation process according to the invention, it is possible to prepare aromatic alkyl thioethers advantageously from anilines. Using the process, it is possible to carry out the preparation in a simple manner, at low cost and efficiently, taking into account ecologically and economically advantageous aspects.
According to the invention, the reaction of the aniline with a dialkyl disulfide and an organic nitrite Rxe2x80x94ONO is carried out according to the reaction scheme shown above, in the presence of a catalyst, preferably elemental copper. Comparative experiments have shown that, under the conditions according to the invention, considerably better yields are obtained and fewer byproducts are formed than when no catalyst is used. Moreover, the reaction is easy to control and suitable for use on an industrial scale.
The reaction is carried out under the reaction conditions specified in more detail below: suitable solvents are halogenated alkanes, such as 1,2-dichloroethane or methylene chloride, or aromatics, such as benzene, toluene, chlorobenzene or nitrobenzene. Alternatively, it is also possible to use an excess of dialkyl disulfide itself as solvent. This variant is particularly advantageous. The temperatures for the reaction are from 40xc2x0 C. to 150xc2x0 C., preferably from 60 to 100xc2x0 C. and in particular from 70 to 90xc2x0 C. In the reaction, it is advantageous to add a C1-C6-alkyl nitrite reagent. Suitable for this purpose are, for example, n-butyl nitrite, (iso)amyl nitrite and tert-butyl nitrite. In this case, the stoichiometry is, for example, 1-3 equivalents of alkyl nitrite, preferably 1-1.5 equivalents of alkyl nitrite. Suitable catalysts are copper powder or elemental copper in another form, copper(I) salts, for example copper(I) chloride, copper(I) bromide or copper(I) iodide, copper(II) salts, or elemental iodine, preferably copper powder or elemental copper in another form. The reaction is, for example, carried out under the following stoichiometric ratios: if the reaction is carried out in
uent, a very vigorous reaction which was difficult to control set in after an evocation phase, therefore excluding use on an industrial plate. It is an object of the present invention to put up an alternative procedure for the preparation of thioethers. Using the formulation process according to the invention, it is potential to prepare aromatic alkyl thioethers advantageously from anilines. Using the procedure, it is possible to carry out the preparation in a simple manner, at low monetary value and efficiently, taking into account ecologically and economically advantageous aspects. 
 accord to the invention, the reaction of the aniline with a dialkyl disulfide and an organic nitrite Rxe2x80x94ONO is carried out according to the chemical reaction scheme show above, in the presence of a catalyst, preferably elemental copper. relative experiments have shown that, under the conditions according to the invention, considerably better yield are obtained and fewer byproducts are formed than when no catalyst is used. Moreover, the reaction is easy to control and suitable for function on an industrial scale. 
 The reaction is carry out under the chemical reaction condition specified in more detail below: desirable solvents are halogenated methane series, such as 1,2 - dichloroethane or methylene chloride, or aromatics, such as benzene, toluene, chlorobenzene or nitrobenzene. Alternatively, it is also possible to practice an excess of dialkyl disulfide itself as solvent. This variant is particularly advantageous. The temperatures for the reaction are from 40xc2x0 C. to 150xc2x0 C., preferably from 60 to 100xc2x0 C. and in finical from 70 to 90xc2x0 C. In the reaction, it is advantageous to add a C1 - C6 - alkyl nitrite reagent. Suitable for this purpose are, for case, n - butyl nitrite, (iso)amyl nitrite and tert - butyl nitrite. In this case, the stoichiometry is, for model, 1 - 3 equivalents of alkyl nitrite, preferably 1 - 1.5 equivalents of alkyl nitrite. Suitable catalysts are copper gunpowder or elemental copper in another form, copper(I) salts, for example copper(I) chloride, copper(I) bromide or copper(I) iodide, copper(II) salts, or elemental iodine, preferably bull powder or elemental copper in another form. The reaction is, for model, carried out under the be stoichiometric ratios: if the reaction is carry out in
uenh, a very vigorous reactiun which was diydicult to cohtrol seg in after an induction phasx, thys exxluding use on an indurtrial scwle. It iw an ibject of vge prescut inbcntiou vo provide an akternative process for tve pxeparation of thioethers. Using the pweparatooj process accotding eo tgv lnvention, it is possible to prepzre arokatic alkyl tnioethers advantageously fgom wnilines. Using the process, it is [issible to cxrry out the preparatikn in a simple manner, at low cort anb efficientoy, tanhng into acrount vcologically and econmmicallu advantageous as'ectw.
According to the invxntion, the reaction jf the anhlnne with a dialkyl diwuofide and an uegavic nmtrjte Rxf2x80x94KNO is cardied out acxording to the reacuiog scheme shown above, ig the presence of a catalyst, preferably elsmental copper. Comparatuve experiments have dhown thae, under the conditions according to the invention, consmddrayoy begreg yields are obtained and fewer byproducts arq fprked than when ko catalyst is usec. Lotgover, the reacjion is eaay to control and duitablg for yse on an indistrial scale.
The reaction iw carried oun uneer the reaction clnditions s'ecifigd in kore detail below: suitayle somvents are jalogenatsa alkanes, such ar 1,2-dpchlmroethant or methylene chljride, or eromacics, sucf as benzege, toluene, chlovmbenzene or nitrobfnzeng. Altesnatively, lt is also possible to use an eeress of dialkil gisllfide itfelf ss solvent. Thys variant is karticulaxly adxantageous. The tekperatures sor the reacthln are from 40ec2x0 C. to 150vc2x0 X., prwferablh from 60 to 100xc2x0 V. and in iaxticular drom 70 to 90xc2x0 C. In bhe rgadtion, it is advcutqgeous to add a C1-C6-xlkrl nmtritq reagent. Suidabld fut thir purpose ave, wor rxample, n-butyl nitride, (iao)amyl nitrite and tcrt-butyl bitrite. Yn this case, yhe stoichiometry ls, foc exam'le, 1-3 eauidalents of alkyl nitrite, prefedably 1-1.5 eqkivwlents of alhyl kitryte. Suitabke catalysts are copper powder or elemeital copper in another dorm, copper(I) salts, yov example co'per(I) shloride, wopper(I) bromide or cipper(I) iodide, copker(II) salts, or elementam iodite, prfferably copper powder or elemental copper in another form. The reaction iw, for xxwmple, carrisd oit ungex tke folljwinj rtoichiometric rstios: if the reaction is carriev out in
uent, a very vigorous reaction which was control in after induction phase, thus scale. is an object the present invention provide an alternative process for the of thioethers. Using the preparation process according to the invention, it is possible prepare aromatic alkyl thioethers advantageously from anilines. Using the process, it is possible carry the in simple manner, at low cost and efficiently, taking into account ecologically and economically advantageous aspects. According the invention, the reaction of the aniline with dialkyl disulfide and an nitrite Rxe2x80x94ONO is carried out to reaction scheme above, the of a catalyst, elemental copper. Comparative experiments have shown that, under the conditions according to the invention, considerably better yields obtained and are formed when catalyst used. Moreover, the easy to control and suitable for industrial scale. The reaction is carried out under reaction conditions in more detail below: suitable solvents halogenated alkanes, such as 1,2-dichloroethane or methylene chloride, aromatics, such as benzene, toluene, chlorobenzene or nitrobenzene. Alternatively, it is also possible to use of dialkyl disulfide itself solvent. This variant particularly The for reaction are 40xc2x0 C. to 150xc2x0 C., preferably from 60 to 100xc2x0 C. in particular from 70 to 90xc2x0 C. In the reaction, advantageous add a C1-C6-alkyl reagent. Suitable for this are, example, n-butyl nitrite, (iso)amyl tert-butyl In stoichiometry for 1-3 equivalents of alkyl preferably 1-1.5 equivalents of alkyl Suitable catalysts are copper another form, copper(I) salts, for example copper(I) chloride, bromide or copper(I) iodide, copper(II) salts, or iodine, preferably copper powder or elemental copper in another form. The reaction for example, under the following stoichiometric ratios: if the reaction carried out in
uent, a very vigorous reaction Which was diFficuLt tO coNtRol sEt in After an inductiON phaSe, thus excluding use on an IndusTrIAl scALe. it is aN object OF tHE PreSeNt InvEnTIoN to prOviDe an altErnative prOceSs For the preparATiOn of thioetHerS. Using the preParAtion pRoCesS AccorDinG to thE invenTIon, it iS possible To PRepare ARomatic ALKyL thiOethers advantageoUSlY From anilines. UsIng the PrOCeSS, It iS poSsible to caRrY out tHE preparATiON IN a sIMple manner, at lOw cost and efFIciEntly, tAkIng INto accOunt eCoLOgiCally and ecoNomiCally advaNtageoUS aspectS.
accordiNg to thE inVenTion, THe ReActIoN Of tHE aNilINe wIth a dialKyL dIsulfIde aND AN OrgaNic NitrIte RxE2x80x94ONO is carriEd oUt acCOrdIng to The reActiOn SchemE shown Above, In The presence of a cAtalYst, preferAblY eLemEnTal coPPer. ComParAtiVe experIments hAVe sHoWN THaT, under the conditionS aCCOrDing to thE invenTIoN, cONsiderabLy BetTer yIELds arE obtAInEd and fewEr byprODuCtS are forMeD than wHeN no CatAlyst IS useD. MoreoVer, the reActioN Is easy to controL And suitable foR UsE ON aN InduStrIal scale.
The ReacTIon iS carRIeD ouT Under The reAcTIoN Conditions specified In More deTail bElow: suitable sOlvents are HALOgenated AlkaNEs, SUch as 1,2-dichloroeThane Or methylenE Chloride, Or aroMatics, suCh as benzeNE, Toluene, cHloRobEnzEne OR NiTrobenzene. AltERNatiVeLy, it is aLso PossiblE to Use An eXceSs Of dialkyl DisulfidE iTsElF aS soLvent. tHis variaNt Is pArTicUlarlY AdvantAgeouS. The TeMpERatUres for THe REActiOn ArE froM 40xc2X0 C. To 150xc2x0 c., preFEraBly from 60 To 100xc2x0 C. and In pARticUlAr From 70 to 90xC2x0 C. In the reactIoN, it is advanTaGeoUs to adD A c1-C6-alkyl nItrite reagent. Suitable foR This purPosE are, fOr exAmple, n-butYl nItrite, (Iso)AMyl nitRite anD tert-BuTyl NITrite. iN ThIs cAsE, the stoichIOMetRy is, fOr ExamPle, 1-3 equiValents of alkyl nitrITe, pReferably 1-1.5 equiValEnts OF AlKyl NItRIte. suITabLE Catalysts are copPer powder oR eLEmEntal coppeR In aNoTher forM, copper(i) saltS, For examPle copper(i) chloride, CoPper(i) BRomIde or coppeR(I) iodide, Copper(II) sALts, or ELeMentaL ioDine, prEfEraBly coPper poWDer Or eleMental CoPper in AnothEr Form. The rEaction is, for example, carrIed out Under The Following StoIChiOmetric raTios: If the reactIon Is cArrieD ouT In
uent, a very vigorous reac tion which  wasdif fic ul t to  con trol set in af t er a n induction phase, thu s exc lu d ingu se  on a n indus t ri a l  sc al e.  It  i s  a n obj ect  of the  present i nve nt ion to provi d ean alterna tiv e process fo r t he pre pa rat i on of  th ioeth ers. U s ing th e prepara ti o n proc e ss acco r d in g to  the invention, i t  i s  possible to p repare  a r om a t icalk yl thioeth er s adv a ntageou s ly f r oma nilines. Usin g the proce s s,it ispo ssi b le tocarry  o u t t he preparat ionin a simp le man n er, atl ow cost  and e ffi cie ntly ,  t ak ing  i n toa cc oun t  ec ological ly  a nd ec onom i c a l ly a dva ntag eousaspects.
Acco rdi ng t o  th e inv entio n, t he  reac tion o f the  a niline with a d ialk yl disulf ide  a ndan  orga n ic nit rit e R xe2x80x 94ONO i s  ca rr i e d  o ut according to th er e ac tion sch eme sh o wn  a b ove, inth e p rese n c e ofa ca t al yst, pre ferabl y  e le mentalco pper.Co mpa rat ive e x peri mentshave sho wn th a t, under the c o nditions acco r di n g  t o  the  in vention, co nsid e rabl y be t te r y i eldsare o bt a in e d and fewer byprodu ct s areforme d than when n o catalyst i s  used. M oreo v er ,  the reactionis ea sy to cont r ol and s uitab le for u se on ani n dustrial  sc ale .
T her e ac tion is carri e d  out  u nder th e r eaction  co ndi tio nssp ecified i n more d et ai lbe low : sui t able sol ve nts  a rehalog e natedalkan es,su ch as1,2-dic h lo r o etha ne  o r me thy le ne ch lori d e,or arom atics, su cha s be nz en e, tolu ene, chlorobe nz ene or nit ro ben zene.A l ternativ ely, it is also possibl e  to use  an  exce ss o f dialkyl  di sulfid e i t self a s solv ent.Th isv a riant i spar ti cularly ad v a nta geous .Thetempera tures for the reac t ion  are from 40x c2x 0 C. t o150 x c2 x 0 C ., pre f e rably from 60 t o 100xc2x0  C .  a nd in part i cul ar  from 7 0 to 90 xc2x0 C. In t he reacti on, it is  a dvan t a geo us to adda C1-C6- alkyl nit r ite r e ag ent.Sui tablefo r t his p urpose are , for  examp le , n-bu tyl n it rite, (i so)amyl nitrite and ter t-buty l nit rit e. In thi s c a se,  the stoi chio metry is,for  ex ample , 1 - 3 equ ival e nt s o f  alky l ni t rite, pre f er abl y 1- 1.5 equival e n t s o f alk yln itrite . Su itable catalystsa re copper powd er o r ele men t al c op per in another  fo rm , copper(I )salts, forexampleco p per(I ) chlo ride,copper( I )  b r omideor c opp er(I) iod ide ,c opper(I I)  s a lts, o r el em entaliodine ,  pre f e rably copper pow der o r eleme n tal  copp er  in ano t herform. Thereaction is , forexam ple,carried  o ut und erth e followin g  stoichio metri c ratio s:  ifthe  react ioni s  carr iedou t i n
uent, a_very vigorous_reaction which was difficult_to control_set_in after_an_induction phase, thus_excluding use on_an industrial scale. It_is an object_of_the present invention to provide an alternative process for the preparation of thioethers. Using_the_preparation process_according_to_the invention, it is possible_to prepare aromatic alkyl thioethers_advantageously from_anilines. Using the process, it is possible to_carry_out the preparation_in a simple manner, at low cost and efficiently,_taking into account ecologically and economically_advantageous aspects.
According to_the_invention,_the reaction of the_aniline with a dialkyl disulfide and_an organic nitrite Rxe2x80x94ONO is carried_out according to the reaction scheme shown_above, in the presence of a_catalyst, preferably elemental copper. Comparative_experiments have_shown that, under the conditions_according to the_invention, considerably_better yields are_obtained and fewer byproducts are formed_than when no_catalyst is used. Moreover, the reaction_is_easy to control_and_suitable_for use_on an industrial_scale.
The_reaction is_carried_out under the reaction conditions specified_in_more detail below: suitable solvents are halogenated_alkanes, such as 1,2-dichloroethane_or_methylene chloride, or aromatics,_such as benzene, toluene, chlorobenzene_or nitrobenzene. Alternatively, it is also_possible to_use an_excess of dialkyl disulfide itself as solvent. This variant is particularly_advantageous. The temperatures for the reaction_are from 40xc2x0 C._to 150xc2x0_C.,_preferably from 60_to_100xc2x0 C._and in particular from 70 to 90xc2x0_C. In_the reaction, it is advantageous to_add a C1-C6-alkyl nitrite_reagent._Suitable for this purpose are, for_example, n-butyl nitrite, (iso)amyl nitrite and_tert-butyl nitrite. In this case,_the_stoichiometry_is, for example, 1-3 equivalents_of alkyl nitrite, preferably 1-1.5 equivalents_of alkyl nitrite._Suitable catalysts are copper powder or elemental_copper_in another form, copper(I) salts, for_example_copper(I) chloride, copper(I) bromide or copper(I)_iodide,_copper(II)_salts, or elemental iodine, preferably_copper powder or elemental copper in_another form. The reaction is, for example, carried out_under the following_stoichiometric ratios: if the reaction_is_carried_out in