Process for preparing carbonyl compounds containing at least one functional group other than carbonyl
RIVENDICAZIONI 1. Procedure for the carbonilici compound preparation, containing in lore the structure or pifl groups of the series-OH, - OOCCH3, - C1, - OCH3, - CN, - COOH, - COOR, consisting in making to react carbonilico, chetone or aldehyde-aliphatic, aliciclico or aromatic a compound, containing a metilico or metilenico group in position g regarding the earbonile, with an unsaturated compound, eontenente ones or pifl groups of the listed series, in presence of derivative of metals of transition in quality of catalizzatori.
2. Procedure second rivendicazione 1, characterized from the fact the earbouilico compound bun - metil-chetone, and in particular acetone or metilchetone.
3. Proeedimento seeondo rivendicazione 1, characterized from the fact that the funzionalizzato unsaturated compound constituted from 2-metil-3-buten-2-olo, acetate of 2-metil-3-buten- -2-ile, linalolo.
4. Procedure second rivendicaziene the 1, characterized from the fact the like catalysts, in qualitY, of radicalici initiators, employs in particular Mu (CH3 COO) 3. 2 H Or, (AgO.<br and Mn CHaCOO)/>
Proeedimento second rivendicazione 1, characterized from the fact that the varied molar ratio unsaturated coal bunker/eomposto from 500/1 to 3/1, in particular from 300/1 to 5/1.
6. Procedure second rivendicazione 1, characterized from the fact that the varied molar ratio composed unsaturated initiator/from 1/1 to 0,01/1.
7. Procedure second rivendicazione 1, characterized from the fact the reaction in object lead in presence of aqua in quantity such constituting or an only liquid phase or two fast liquid with the unsaturated mixture of eomposto and earbonilico compound puttinges to reagire.
The present invention concerns a proeedimento for the carbonilici compound preparation containing in the lore structure also or pifl other groups of the series - OH, - OOCCH3, - C1, - OCH3, - CN, - COOH, - COOR.
For a long time famous in literature reaction of radicalica addition of bisulphite to several olefine -- in particular a-define -- promoted from salt and oxides of transition metals and it plows [M.S. Kharasch ET to: J. Org. Chem. 3 175 (1938) and JACS 61 3092 (1939)].
Regarding in particelare the radicalica addition (anti-Markownikov) of chetoni to olefine finishes them, the literature filler how much follows. The begun reaction between cicloesanone and l-ottene from cancellations UV, would give the correspondent composed of addition with yield of only 18% [M.S. Kharasch ET to -- J. Org. Chem. 18 1225 (1953)].
In organic or peressiesteri peroxide presence which sources of radicals, the acetone would carry yields of the 32-62% net correspondents metilalchilehetoni, together to telomeri and products of sclsslone of the initiators [z. Chem. 4 177 (1964); J.
Chem. Associates 1918 (1965); Izv. Akad. Nauk 2065 (1961)].
Analogous operating in acetic acid like dissolvent and acetate presence of transition metals [in particular acetate of Mn (IlI), in quantity double quantity-stoichiometric regarding the olefina], the correspondents metilalchilchetoni in mixture with chetoni unsaturated and y-chetoacetati which prineipali products, with unsatisfactory conversions and selettivit [JACS 93 524 (1971 would obtain themselves); Ger. Often. 1 936 261 (1970); Izv. Akad.
Nauk SSSR, Ser. Khim. 200 (1971)].
An analogous reaction begun from acetate of Mn (III) in acetic acid absence, would carry to indistillabili products beyond to the metilalchilchetoni, these last ones with inferior yields to those obtained with organic peroxides which initiators [Zhur.
Org. Khim. 8 2467 (1972) and 11 947 (1975)].
Aggiuuta of acetone to c - the olefine or cicloesene or of ciclopentanone and cicloesanone to 1-ottene and 1-decene, in presence of Needle, Ag2 Or or oxides of metals of transizioue [es.
Pb 02, Mn 02, Cu Or, Hg Or, and basic oxides of Ni (III) and (IV) and Co (III) and (IV)] it would carry to the correspondents metilalchilchetoni with comprised yields trail 17 and 1 ' 82% and selettivit t of - '-- 82%, regarding the elefina [Tetr. Letters 36 3193 (1974); Czech. Chem. Comm. 41 746 (1976); Synth. 315 (1976); Czech. Appl. 3917-74 (1974); ditto 3807-75 (1975); ditto 7762-75 (1975)].
Present keeps itself the, in these last houses:
-- single work in watery atmosphere rton and absence of tumidity; -- work always and exclusively on sempliei olefine, is containing other groups does not work them in the lore structure; -- rapp0rto the molar catalyst/olefina relatively elevated: from 0,2 to 3 (preferibilmente from 0,4a 0,8) for Ag Or, from 1 to 6 for other oxides of transition metals; -- they are always formed perceutuaii variable and mat negligible of the 0meri pesantit of heavy telomeri (es. 15-28% regarding or! efina).
From brought back how much over it turns out therefore famous and wide described the reaction of radicalica addition of chetoni to - olefine and cicloesene.
It was not instead up to now notes n described, same ripe of reaction between eomposto a carbonilice and conteuente unsaturated compound in own molecule axtche or devout fuuzienali groups, and in particular famous groups like reagents in radicaliche reactions (as an example - OH).
The presence of other flmzionali groups reagents in the mo.
unsaturated lecola -- in particular in position regarding the insaturazione cut the carbonilieo compound is added -- it made to presume new types of reattivit of such moleeola, with consequent such of selettivith net eonfronti of the product of radicalica addition 1:1; with the foretold composed types of not we have instead amazingly found an increment of said selectivity, respect to analogous lead tests beginning from olefine without groups works them, like brought back in literature and previously accennato.
II procedirnento for the preparation of eomposti carb0nilici, containing or pill groups listed in rivendicazione 1 precedeute, second the invention, characterized in For preparing carbonyl compounds containing in their structure one or more groups from the series -OH, -OOCCH3, -Cl, -OCH3, -CN, -COOH and -COOR, a carbonyl compound, ketone compound or aliphatic, alicyclic or aromatic aldehyde compound containing a methyl group or methylene group in the alpha -position relative to the carbonyl is reacted with an unsaturated compound containing one or more groups from the series listed. The reaction proceeds in the presence of transition metal derivatives as catalysts. dure&if Adisst connections in presence of ciaes rvuetalbildenden initiator, thus gefcennzetoh Tjet, hired ijass maa such insatiated Verbaeatagaa uinsetzidie one or aK&rere well Stdiehftfiibktfo&ele groups of e Biflchuee Bfoh of such, which aai raduecftuestben Jteakueo-t$ 2, procedures according to requirement t, thereby characterized, dafi one as Awgfljjg Ecarbonylvcrbaetdung era auephaiiaehes, aBQKcte or aromati&cbea Keton or one eliphaiisdwn,alicydischeti or 19 orometisdien AMeltyd uses their molecule methyl-or Methytengrappe m-Sielluus, related to which carbon yfgnippe, aofwehL 3, procedure aacb Ansfmx 1, tk&irch gekean-LN Ae-Metfiylketoii, msbesondert! Acetone or Methy Uthy Qtcton, uses 4, Verfalue-cn after Anspnrch i. thereby gefcenzeiehnet daQ one a unssesltuegte Verboaedimg uses 4 as fenktk >Tidle groups a oiier js several the catching group contains:-UHP COOR. &VErfahrcn MC*I addressed 4, one as ungesaettigie VE Hjiiidtmg &2-MeUeiyl*3 -,daoe thereby characterized, buten<òi, the acetate of 2-Methjli-3- bi Kcn-2-ylodtf uenalool 6, Vwfahren uses after one of the requirements i bl 5, by it characterized that one as radikalbifdenden Iniueelor MiCHjCOO) j 2 Mn (CH3CXÓ) j or AgO verweridet 7. Procedure after one vorangf the Aji DprUeche, dathjrch characterized that one uses per mol insatiated V&tri dung 3 to SOEO, in particular bit 300 mol of Carbonylverbindimg 9. Procedures after one the preceding Anaprueehe, dathirch admit/- e Jchnet daB UKHIfor each Mo i insatiated connection 0.01 to t Mo i r, and/or initiator, used alkylketoaen, the duktes Aue mil Teiomeren and C (2-C&em, 4, 777 [ t964J the invention refers see to a procedure for the synthesis of Carbony! Connections gemaeB generic term D it H ay pta nsprudi from the literature is it already for a long time admits da$ rsdtfcass&the Addmonsreakdon of Bisul Fit at v Biscmedene CMe Ctna, in particular at Ae-Oiefine, by salts and oxides of Uebergangsmet all and air utwi besch Jeunigt becomes gefoerdflrt (see M-S, Kharasch et ak), Qr&ehem. 3, F?5 ft9 and which in particular the rKUekaUEGChe addition (anti-MarkownikovS of Ketonen endsto&office Cfieftne concerns SAE on is the literature the following to be taken: the reaction between Ctycloehaxanun and 1- (did unier Einfluoe of UV-Betrahtang leads me in a outer one Kbeuie of INTO too drr the appropriate organic Pertoeriden or Peroxyestern in presence vtwi ali ftadifcalqudlen leads Aceion to yields of 32-62% of the appropriate welse into acetic acid ones, cnttrccbeoder with the Affeeftea IC, ttelu hp in Anwesenfaelt of acetates of in double Stoec MoraetriK&it quantity, one trhJUet the e in the Gemt Bch with Kelonen and Keloaceiaten as hauptprodukte erhakeo, whereby the Umact Timg is mdtt unvo Ustfindig and the selectivity masreieheml {JACS-9% 524, [ t9?i| UT-OS 1936261, izv. Akfid Nauk. SSSR, Ser.Knln2t Xt[t97t >one duk dreivtagea Manganacet Ht in Anwcscnheft of acetic acid emgelcaetete ReakUeuen foehn outer Ber to the Meihykikyiketonen to others, does not dejlHueei't-Fen pro parliamentary allowance, andtherefore to more eber germgerca bump out than tn present van organic peroxides than initiators (Zhur. Org. Khim, 8 2467 [ 1972 ] ond t L&47 [ 1975. The addition of Accton oeue A-Olcfine oron or the addition of Cyclopentanon and at i-Odea and t-Deccn in presence vrni AgO, AgfO odtf of oxides of Uebergarigametallen, like PbO?, To MiK >p, CuO, HgO un4 basic Oxideu from droe-and vicrwertigem NT and three-and CO, drive the outer entspraehemien Meen into Anbeuten zwi&chen 17 and 82%, whereby the selectivity, related to which OTefin. is about 40 to 82% (Tfeft of leader, 36, 3,133 [ t374l;Ciech, chem. COMM, 4t, 7'6 ft976 ];Synth, 3t5 [ 197;CSSR-PAnme Jdimgaei. 39t7-74 [ 19741-foeO?-75 [ 1975 ] mid 7762-75 [ the 1973$, in the latter case muB still following to be considered: one works only in onenk&always and exclusive twaeMgen environment under Vefme&ung by humidity as well as with simple Otefinen, which is not further fynkiiooelten groups aufweis&nj the MolverhlltnlE of Kaulysator &i Olcfb: it asks for AgO OJf IMI 3, 0.4 to IfcB. umi more fer aisdtre oxides of 1. bisfii always however not vernadiE5sstgbarer quantity heavy Telomere become admit are also, daue with the synthesis of the Addiikri of Ksstonen at a tonischen mechanism caught can in more different. As catalyst a Lewissaeure BortrifluorM-aetn brAet uses (Synihesis 1972, 75S-become 378) in this case. The task was to the invention at the basis with hoof of the radikalisdien addition of Ketonen because of insatiated connections such Carbonylveifeindungen m erhaae -, in their molecule still one or more funktianeuee groups ten contained, in particular such Grup|>ent ais reactively with raiuekulisehen Reektionen admits are like-OH. Invention KgtHBaeue this task thereby solved dafl oneaolche unges Btugten Veiiiindimgen converts or several zu&frz Ekhefunkttone Jle Gnipp&n einscfttle Qllch more sofcher, RA radtkaiisttei Seaktuemen able shidpoeithaltenT presence of function-hurried and reakt Lonsfahigen groups in Mofek Ql that unges Sitigten connection, which there in particular in A-Ste Hung to the insatiated connection, to which the Carbonylgruppe is added, bingt on sidi for a such Selekuevitat, related to dfls (mol froduta times 100, divided durcfc converted mol Mote Jcfl ] new Reaktionsinoeg Hehkeaetcnalong so d*S divided by mol of Ausga Bgs-MBEj 52% and to expect was,daB f SE Sdeklmtaet for education would decrease voa speaaeeH 1-t-AdaetiEHicpbi Ddu&gftn. Surprisingly nan, daB with obea erwAehssten Verbintfejng Btypen the selectivity was found the GmppeH unfetlonetle in the opposite bease * is ib with Oleftaen drae f, how they are described TA of the literature quoted above. Educate therefore more berowler * after 27 S&mdeD the inacbie Umsetsrnngsgrd 80% and the Sdekoevitfct &59fe out was bzv. scut one one fertilize the uagesltligie Bmdun dne with eker Ver&mduflg over, the gs mindestein the Mdtkul and a desert several funktione Uc groups airfweiat? as radikaM-dende Imtiaetoren uses one thereby derivatives of gemAS the Deftmtioa voa Barnes E lit sirwjrgank Chemistrys, New York, 1972, as if hurry designate are more auecycSIscher the Carb Qtiylkann tan ooepnatischef, or or enlsprecfeentleB a Keion uad has in o-SHelking relatively too Cbonylgruppe sine Msthyl det-or Metfaytsigruppe;voraswe is a ae A -) ethy]keton, tnesssoed Bre Aceion or methyl inh the Cart) OByiverlm AI Bng insatiated Verbinduoegcan do one or more utigeiattigte connections a up-sore and contains auueerdem before or several fur.fetbnelie groups, like z, 8, intuessiorat a derivative z-B-an acetate, an oxide u German Federal Armed Forces of a Uebergaettgsmetaiis?u8-of trivalent Mn, dfdwerllgem CO, trivalent Ni iweiwertigeifi AG or such a thing. With an initiator Mn (CH3COEOe) is preferred 3-2 HLO, the Reektbns Bcmisch can water-free or haltig be, whereby it in the latters! * FHUe m two separate FToesrijen Pbasen or as emzige liquid Ptiasc are present kanti, when working in Anwesenheh of Wassar are smaller the Setefcuevil Bt nfeibl as if protect resembled, TM wa Heifrwn Meduim rfurehgefuehrien R&akiion, 2. He Reaklionsiratiaoren become m of dner quantity assgeftrodediE "rk Uch kuetalyaescn is2. Afigeme Jn billion of the K&talysator m of a quantity of 0,01-1 mol per mol tt Molvarhaeftnis awachpn the two Reakifonstciine Kmeni is dtaegcstclit, daoe nuf 1 mol insatiated connection 3 to 500, in particular 5 to the Bebpielc serves * ur closer explanation of the invention in such a way. Example l with Thermofneter, magnetic agitator Rueckllu Bkuehiermit Aikob Dlbadvon i t it tOQmi glass bulb, that into a bath from Vitseitnoei eintftuecbte became with Z4Sg pure, water-free 2-MEUiji'3-butfin-2-(ri (MBEJ, 5<X2 g Acetofo under RueekfluQ rnh the KMaQ * cleaned, driiliert and over Meri (* ular9d Ten rj Pbe*ahft want acre, and 3 2H?O DBS Mofverhfiitnis acetone feeds 335 E Mn (CHaCQQ);MBE/Katatysator amounted to for instance 30/i/O the mixture became 1 1 Stimden isei WC of unier RueckfluB go-serves, wonuerf the Ura Beiax HiiTHd of MBE (Mtri Ausganp-MBE mbus mol formed MBB times 100, CHt O C Ht \ CH, C OH CHt CHt its structure dufch M eating IR-ond NMR-Spektnim nadewksen became. By NMR-Anslysen with CCU as Loesungsmhtel (iotemer standard KDMS, Magdettempentmr for instance 2SBC} the following Gnpen became naehsse*icscn chemical TA CHj CHf C O O off i, 06 (S) i, 36und i, 5ss(m) 2.Ue3 (S) 235 (t) 2.80 (S) the IR-Spt*tn*m confirms the Anwesenhdt oecr to the following funkikfne Uen Gryppcn >3460 cm-' CQ-Valenzschwinguag 1725 cm"1 by Masstnspfiktrometrffi confirmed that the product a molecular weight of 144 has Beiapiel it became after example 1 worked, whereby [ edoch daa Mdverhaeftnte Aceton/MBE/Ka Uilysator ungefoehr 30/1/0.1 was. After the mixture 31 hours of University of it RGefc Rufl gefialteE was amountedto doer Unttetzungsgrad 46% and the Sekkaevitaei more efe 93%. After 47 hours betrog the Umsetzuagsgrad 36%;the Sekktirttst was invariably example it again after example t worked woebet the MolyerbaeJtnis AcctOT/MBE/Kai Blyassor again 3fJ/tyO belru&however water in a quantity present was, <Bc sAeem As Emrop mh MBE cuisijrach (22 Oew,-bezogen on M). Adding results mirden received;Reaction mixture &Vi hours 9G°C held was, amounted tothe Umsettungsgrad for MT 50% and does Setektivttaet we education of the VcifeimiueQg 1 upper Beispief with Prob&rotir and to magetbchem agitator more equipped \ i-Auickmv out rostfr Elein steel m dessem inside an electrical Widemandishemmg was, became bea Aickt nati 29.3 gpure MBE Wasier TA 49 more than MnfCHjCOOJj with more tfcermometer, magnctisdiem agitator Proberobr of ausruesteter Autoefeue AOS Pcxeas, the m (hCFriTMlstisc Ii gesieueertes bath from Va!moel dived in, became also;6X1 g pure water-free MBE 1 20,0 g gerelniglem Atton (see example i) and 93g MnfCHjCQQV that the Mnlvwhl Umae Aceion/MBE/Katalysaior ll betrog. After iia&mixture 2 hours held 9Q*C more wflr.lwmigder uewaetjngrad the JMBEeiwH 34%;after 4 hours it rose to approximately 52%, the Sefektivhaet forthe education of the connection 1 lay constantly * more ueher like m 3. For instance 3t Vi/G, 5 amounted to Nacbdctn DOS M Betsptefe6bisl7 in 5 autoclaves TOSltreiem steel beofttzien in example became a Yc Rdisreihe leads, with which-to more ner unchanged Anfangsc Harge out ú ÓTg gereim Btem Acetoo verschedwie Mwigcn at pure water-free MBE and Mn (CHaCOOeh-2 H?O sige Hlhrt became;Details come out from the table. N r, Awmn/MBE/Kalal. Tcntp-in C time in fr inft in VEni-% t5/i/Gi2 100 l 45-2 49 30/1/0.1 90 2 32 33 43 ao S 100 l 33 2 40 so 30/1/0.2 90 2 42 so 3.5 53 tOe 109 l 48 2 5g HO l 53 K/l/l 100 3 83 45/1/0-1 tOUe l 29 $4 away is aeung No. Tcmp, in t ' At'etiiti/MNL'KiittL 45/1/(U Õe/1/CM 60/1/9.2 6G/W iQQ m ftt'it in h in SS 87 g&from oath play 12 is one of the advantages invention * g&mBBe&of the procedure legally: one sees, dss twi relatively lifted loitiatoermengen the selectivity/backgone whereby erfinthmgsgem&the sse procedure from the bekatmten differs, with which good results become erreidii only if one did larger quantities of Imt to o r bet (. Examples L8bi*2G it as worked in example 6 to 17 whereby [ edodi the Mn (CHjCOO) was used t abroad water-free, o.h. not starting from MnfCHiCoeO ' 2 HsO. The following results would receive -, in CL conversion N r Arctan/MRg/Kalal èit, in Mul inh-to % 30/1/0.2 100 2 45 fioe/1/0.1 100 i 40 2 53 SS 3 56 IT &uet i/0,2 100 i 50 2 72 SD example DOS in the examples 18 to 20 use! e water-free Mn (CHjTCOOJi became Itergeste Ht by oxidation of MiCHsCOUj! mn km NO *, essigsaeureanhydrued and oenem grteren OberechuS at Elsess with SXFC in dncm from the attempt after example yj solid the mother liquors from the preceding production again too and supplements carrion mixture with KMnOe * and tas%si&reaahyaerid, then mas again MnjOHjCOO received) ith width unit one for conversion with the same load as in Bdspiei 20 to use could one received then nadi to a Reftklroitszeh from 2 hours with iQOe"C a Umseuung of Oe5*Aebeae of i/0ae/2/22). One left the A untouched HtfcueMagemls **! 2 foehn one on glek&B Wmsc aweate granting with Raumtem} >efatur andf a Stfime tion durdi, thus betmg the UmHEtznngsgred 72% knstatMQerte Mn (CIJaCOO) IAB-I/O selectivity 80% and Dftcb of the drillen with the Fioeiercti Gcm Jsdies from Carbonyiver-erhueeH one enien UmsetzuflgsgrBAe of 60% HndmuendOIrfinnadibeeodl Eteri JmseiziiEEaufdem Selettivii St of 76%. Fi Jter zurueckefbende solid was praktisdi velvets the Mn (t BjCOO) s ond could twcckmaeSigerwci ' SE to MfCHOOjj rtcnerieri and ssir wciteie &conversion! , with dct&n if one is used the reatuedien Mtrttcriaagea of the original Heuetefhmg Mao alm for example umldic the n with VergktcbsbaspieJ for the Verg Jetdi became after the DH-QA t9362ssl into a P mh 10g potassium acetate and IQUenue acetic acid one fed Claskoiben 17 g (Qftoe mol) MrCHj CpO) * 2 HjO were introducedand the pistons of unier tubes to the Suecksioffstrorn on the oil bathon as soon as the Mangansali were completely solved, one added a mixture from 220 mi (3 mol) acetone and 4,é (9, oeae mol) MBE too uadheated up as for a long time eitenbis the braufle colouring of Mo * A completely v erschwungen was, as ersichueich. enisprachen the Reakikmuebedingungen exactly in DE-OS 19 36 AI applied, whereby the only difference consisted of the fact that ansteife of l -was used Gcten ltd.;tfssS main KeaktioefJBprodukt was in this skin that 4. l-Adduki. D, h-the Vcfbindiing l. of the Um&etzungsgrad amounted to only 15% and the selectivity 20%, the 1: l-adduct in this case receive ansielle this Ketocsters vngesaetrigissn of the ICetoncs, after the examples 22bis2H Vwsudte unfen in your in Betqjid 5 beachrkbeneo SI Bhlaatoclaven durchgcFuehrit whereby with a mol relationship of of sports association l/Q tn dtw the Tabefle specified different Qldtnverbindungen were used, Wr, OMM *. Tom EL in C eit in h Gtefingtao in % (Mnl-% n Allytalkohol IOG 3 26 3-buten-òl IUEO 3 20 5. Penten-3-ol 100 5 lo f-Penten-4-ol 100 4 49 Vinylsce&t IQUe 2 n 2-M ethyl-2-jieaet&K3 '-3-buien tOtl 4 CSU 2-ME hy l-2-melf Kixi '-3-b uten l Ofl 3 58 H4 thet received in each case with the examples: t-adducts became byGafinUEBBig-Chramauigraphie and example with thermometer, agitator and RGckflu a Bkondensator auigffrusietcr and up-t5BC of geldihlter Ciaskofoeen with a volume of 250 mi became with an electrical Heizmame! umnoeBt and fed mfc the molar ratio Aceton/MBE/Katalysator amounted to about 300/1/2. The mixture was held 6 hours under Ri&kfluB, on which the adduct according to formula t in an educated manner wait MBE-Uemselzxjngsgrad 70%. Selectivity more highly than 95%. Examples 30.3l.