SE1630105A1 - Process for the production of mixed 2,2-dialkyl-1,3-propanediols - Google Patents

Process for the production of mixed 2,2-dialkyl-1,3-propanediols Download PDF

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SE1630105A1
SE1630105A1 SE1630105A SE1630105A SE1630105A1 SE 1630105 A1 SE1630105 A1 SE 1630105A1 SE 1630105 A SE1630105 A SE 1630105A SE 1630105 A SE1630105 A SE 1630105A SE 1630105 A1 SE1630105 A1 SE 1630105A1
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SE1630105A
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Mpampos Konstantin
Andersson Thomas
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Perstorp Ab
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Priority to SE1630105A priority Critical patent/SE1630105A1/en
Priority to CN201780028660.2A priority patent/CN109153624B/en
Priority to PCT/SE2017/050386 priority patent/WO2017196225A1/en
Priority to EP17796480.6A priority patent/EP3455200A4/en
Publication of SE1630105A1 publication Critical patent/SE1630105A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

9 fflšSï'R¿f-\(Éfš* Dísclosed is a process 'ñivr productiøn of :xxixed 2,2~diašk§f!-1,3~p~r0paz1ecïi0ls by' akïfßí reactionand sulfssequcxït crøssed czannizizaæro reactíorz: Wheåreby f'unnaïldehyde in gafescncc af a strong baseis subjectcd to aïdøï faxa-tion and slubsßqpxsnt cannizzaro :samma With Ewnetígflpropë-Lnal and atleast one (vther lalkyšaïkanaš. Said Zanefltqflïarøpsaxnal and said at lezlst one otšler Qfalíqf-*lzïïkaïxal.a1re*px'csent. in a xvc.šght1'at_ío of 60-9596 lny wsígšzt of l-xnetï1ylp1ïnpzxz1afil and 5-409/5 by Waight ofsemi ai šfzast one other 2~a11kyf1a1kanaJ :md said process yíelcls a ccmwssponding mixtuïe mi' 2,2;- dixïïetíïffíd,3~pr0pan+:dioí :uid ai íeast (me: otíïer 2,.,Z«cííalky'I~'i_ß-propaïnßcíioí.

Description

PRÜCElÉšS WÉBR. PRÜDUCÛFIÛN GF EVHXED 2,2~DEALKY'L~1,3-PR(),PLIXNEÉŧ)ICII..S The present ímenïšon reíates to a process 'for profíuerirn: ofmixed 2,2-dia1kyl- i Qïproparreriíolswiirereirr íorrnakielxyfde in pxzfeserzee of ae 'base is subjected to aídoš reaction and subsequerxrterossed eanrorízzaro reaction vvíth Z-methyiprrrparlal and at Iezrst one other 241314 ylaïkarr al yíeldíngav mixture :of 2,12-di1r1eth3fi-l gš-prïapalïredioï :nad ai least one other Éfiæííallcyfh 1 ß-glropanedíol.
Diols bin/ing for iostanee a neopenïyfi structure, such. as ZßdíaïkyH ßpropsanerdiols, aretypíealšy srynthesísed in. an alkali eatalysed alldol eondensartioxfz, at for insrtarzrce 3()«6lI)°Cï, ofibrrnaldeíïyde and a second aldehyde yielriírfrg a methyirvíaïvdehyrde. Said Lnetšïylolaldehyde is ina subsequerrt step reducerí, at a temperature of for instauzrce 6Û-90°(I, to Corresponding díoï by:rtrearns of a so called crosseci cannizzaro reaction xxfíïh a ñlrther ecwíxfalent of íbnnaídehyde inthe presence of a strong base, such as an alkaši or aïkaline earth nretzaí hydroxidev, an amine orother cornpoxzzrd producing OFF? The aidoí and cannizzaro reactions are typieally' perfornxed ata pflH of 8-12. The cannízzarcí) reaction earn ašterrratively' be replaced by eatajšflxfïríe hydrogenatíon.The syratrresis vvelï as recoverfyf of rvbtzæined reaction proríuct norrnally yielcl secondaryproducts such as formaïes and acetals.
Tru: reactions taking ïnlaee in above processes can, tàiiirïg, ZQ-dirrnetifryiflíß-propaznedirol(neopentyl gíjycrnl) as an exampâïe, be sulnmarised fïlcïol condernsation:(CHQQCHCPIO + .HCHO mmm* HC)C,H;¿(CH3}2CTCHO Carnnizzåzro rearction: x~roerrzçcfrgygecfHo + Her-ro + c>r~r@ e (crrgzrcrrciflgcarrgg + Hcïooç; Balanced tbrmuïa:.rcrrigygaïrrrïflo + 2 HcfHo mig) ---e (Cïeïsàzflïfï-Hgßflfë; + HCOÛQAlnove sc:}1en1»es are valid for other 'rÉQ-:iíalifry/*Lí ,3~propar1edio1s, suefh as 2-b1rt3.fš~2-et11§;í~i,3~ propanerliol, by proíveor replacement and, ehroiee oifthe Sesam-d aídeáhyde anti aecrvrdi11g1y *yíešoedmethyíoíaidešljrde in the aldoï eoncšensartion.
The ineeliixiiisnis behind aldulisatitili and cannizzairisaatiíiii are since long »well knmx-'ii in the art.The 'hineticts of sixid reactions, wfariotis prneesses fin? iiidtistrial pifidtictifan aiid reeoxfery, reaetiuiiiaarainetera and the like are thornnghlyf diselesed and discussed in a large nuinber nfhfandlicifiks,taatents and otfner publications, such as Kirk-Ütliiner “Erzcifcíupeiniifz Qftffheiiiiccil Iiechriolcigy"lim. Vel. l, 1978 "fïllc'oi'fzul.s'. f*o.ff;.fhåxi'dz~íc'*, pp. 755-789 (inel. Bilalielgrapflhš/fl, ".S'.fifi:z'ies' eniiizlurnzedíivftezs' Jizifciliieu' in the finltlieivíiv cgfil-“enraieiïgfíßifuïtfyi cirza' Relczfecz' A ícfeitfilis" Patte l-Vl, Jan-Erili Vik, .Aieta (Ilieinica Scandinavia 26~28 (1972-74), and "ófii-*fiïesf av 2~E¿}='I¥2~B~zi1z§ifl~1?3~EÜf-'ngacii-zfiíírillfl h/likael Karlssnri, 900202, lšeyal Institute otiil-echiinlegy, Stoeklwlni, Stafetten. Aselection ofpnblisheil Patents and Patent .flipplieatioiie ivili cover iiiest of the 20th century and»still lifuni the l94(}'s to present clay iiielticle puhliciztiuiis stieh as (flermaii Patent 733 S49, U SPatient 2,1 ïlhöåil, US Patent 2,79Û,837, European Patent O 343 415, Burepeaii Patent Ü 708 073and US Patent iíßdhßfil Diols, such as said 2,2»dialky'l~l ES-propaneitiiols, are *Frequently tised raw inaterials inproduction of fur instanee pelyesters, including alkyfd resins, pnlycairhenates and pOhIQaÅllQ/leiieplithaliites), polyetliers and polyurethaiies før various applications, such as deeerative aiidproteetnfe cciatings, adliesives, synthetie lubrifcants, plastieisers, perforniance additives. PETeeiitaiiiiers, teams, elastoiiiers, sjffiitlietic fihres and the like as ilisclused in a large iiiinibei' oftheses and handbooks en diollpolyfnl czninprising applications. lt is fuitherinere emninuii to inixtive of rnore 2,2~idiall§yi«lQl-propaiiediols, xvith for iiistance varyiiig alkyl eliaiii lengths, tonbtztiiied certain and flesired *product progierties, stuzh as liardness, ilexibility", tfanspareney,tenn peratiire stahility and the like. There accordinglsf exists a certain desire and need fot inixed2,2~dialk:y'l-lß-»propanediols as ai single product instead of niixiiig tvvn of more dinls. 'Thepresent inventioii prnvicles tiie iiiajuir advantage ef providing a ready fnr Lise diel inixture. 'Theprocess of the present inxfentiivn gives hi gb yields oftivu or infart: LÉQ-dialkyl-l ß-ptreiiaiietliolsin a single reaetorifgzflrodiietioii plant lind quite unexpectedlyf cin not give any cinsi -aldol coupliiigof the substfrate aldehydes, tliat is 2aiiethylpifnpanaii and said at least eine other .ÉV-alkylalkaniil.A ñuthei' iiiajoi~ advantage is that yiielded 2,2-diall Tho iirssonii iriveritiiiiiv aiocorciiiigiy' riofers to a procoss [for pifodi-.ctiozi oiïniixod 2,2~aiiaii§y'l-i,3-iiiopaiieciiois iiy aidoi reaction and subseqiisiit crossed caniiizzziro reaoiioii wfiieroiiiforniaiiiohjycic in -prosooco :if a siroiig “oase is subjootcd to aidoi feaciiciii and suiïisoqjiifiaiitcanniZZziiwJ reazctiiin ii-iiih 2-11:otifiyfiiariiiisnai and ai ieaisi one oiiiiei* 2~alkyiaikaiiiaii_ at a iiioiar ratio'ibiiiifiifiisiiywie to LfZ-iïioiiiyipriipanal and said ai least one other Zflaiikyiaikaiiai ofiioiifasoii 2-22: i .2-mstiiyi-iiriiyaariai and said ai 'ieast one other Z-aIky-“iaIRaiiaÉI ars, in einbivdiinoots oi*tiie presentinvoiiiion, prcforabiy mosont in a ivoighi ratio ofbeiiwfcen 9921 and i 299, such as betwveon 6Û:4Ûand 9525. Said as ai least one iithor E-aiiqfiaikaiiizil being author tiian Z-nietiigfipriipanai is inospsoiziiiy' proiowoii emborliriioiiis, bouâ iiiot iiiiiiteci to, a Lsšikyibiitanfai, s Lbaiiqfipeiitaiiiai., a 2-aikyiiicxaiisi, a 2~aikyihepiaiiai andfioi' a, IZ-sikyioiztiinai, vviicrcby said proizess yieiiis a.iooricospciiidiiig imixtiirs oiQQ-iiiniethyii- i ß-priipfsneoioi (noopontyi giycoi) and att ieast one ciiherPqlšfdiiæikyfbiß-piïqfiaiieciicii. Said alkyi is in iikevifiso especially prsifcrreii enibciiiiineiits (Ii-Gigiinoai' or branchod aikyi, such as iiiothyi, sihyi. propyi, butyi of poniyi.
Said st icsst one othoi* 2_,2-<_iiaii<}/i~ißvpropsnodioi is, but not iimitoci to, in the niost profenfëdornbfidiiiients o i' the -prosoint iiivoiiitiiin 2 Qfiiieftiiiyfi - i ,3 -propanedi oi, 2,2 -diboiyi- i ß -propaiiiocii oi,Éß-di (iiioiiiyipraipyiy i ,3 »priipfiiieiciiai i, Z-etiiiyiiáfifiiioiiiyi- i ß-propoiieciioi, ßprcipyi-Z-insthyi-i ,3«proipaiiod.ioi aiidfkir Lbutyi-Q-otiiyi - i ,3 -propa11odioi.
Said base iiiiiiseci in the aidoi and cannízziiro roaotioxis of ”the present invaniioii is suitabiy anaikiaii of aikaiiiiio :earth inotai iiydioxicic oi' csifoonaio ancifoi' an ainino, such :is potassi Lim, sodiiiiiiaiicifior caiciuiiii iiydroxido or carbonaio aiicifoi' an aniine, such as triothyiziioiiio. fšaid aidoirioaotioii is proièrabiy perficirnied at a íeiiiperiiiuife iii' BO-ÖÜOC and said caniiizzaro roacïiiin iikovifise proiíirraiaiy, pieiiorinoed ai ÖO-QWC 'and iacitifi roaiiztiiins som suiíabiy' lnerfoiïried ai a pH oi'ifor iiistaiico 8-12. 'Tho Z-nieíhyipifogianai and said at least one other Z-aikyiaiicaiiai can oitiisi' of:preniixed piior to addition of foiiniaidehyfiie and other rcagonits of ohargod soparateiy' and yieiiioii2.,2-ciiiniethyi-iß-priipaineciioi and yfioided ai ieast one cither lfi~ giropancii ioi s.
Vsfitiiiout iiiftiior oisbciratioii, it is "boiiovoii iiiat Liiie skiiieci in the :in maxi, iisiiig tiio pioooiiiiig(íësilriivtiiiii, iiiiiiso the presoni iiiveriiiiiii io iis iíiiiost exieiii. Tin: 'foiiovving iïnfeišziiefl specificoiiiiiiicliiiisiiis are, iiiorefiire, to in? construod iiisreiyf .iiiustratiiøe and not iimitative of timifoniaiiidoi' of the disciiisiiii: in ainy way' vi-'haitsaiox-for. .in the iiiiiiiwviiig exaxnpics 1-6 an: iiiixed QQ-diinethyfi-ifi-proptiiiedioi and 2.-biity'1~2~eti1§f1-1ß-propariediiii procitieteti at varytfng iveigiitratio" L?.~met1i yiprtipzinzii to 2~et11y111exan_a1.
Exampie 1 A reaction soiutioii coinpifising 101.9 iaarts iny weight of an aideiiyfcie inixtiire eonsistiitg of 95%by iveight of Zmiethyipropziiiel and 5% by iiteigiit of B-etiiyfihexaiiaí, 180.7 parts by »i-feigiit of48941 itq. ítiiiinaiicieiiyde, 121.1 parts by vveightt of 511% ao, studium iiydroxitie and 550.0 parts by'weight of »Valter vt-fas Subj ected to aidoi iï-:zictitin and siibseqtueiit cannsizziato rezietitiii. 1(147.9 giartsbyt iifeigiit. oi' a reaction niixture were, etter conipieted reactions, isfišated and the pH ivasadjusted to 5.5 by addition of 8.4 parts hy ti-feigiit of fotniic acid, "Pite Synthesis restiiteti, twitterteeovery and ptiriticatioii, in a ZÅ-dirnethyi-ißfitïiropanedioi yieici tit'9fl1.9“fíi aiid :i Li-iiutyflisš-ethyi- 1 ,3~protïiandiii1 yieiti of91 99-15. The amount of Linrezieteci aideiiydes »vas determined to be<4 0.194» of Zfinetitiyfiisvttipiinai, < tÉliÉi-'íi tifletiiyihexziiiai and 1169/11 of forniaidehyde.
Experimental: E-inetiiyipropaiiai and l-ethyihexiziiiai iii/ere in said sinouiits preinixed, 'Fhereactoi* “fas charged ii-*íth the specified znnfiuiit ot" »water 'and tioniiialdeiiyde aiiid the rnixture iifasiinder stirring adjusted 20°C' :utter a iaeriod of 10 niinutes. After said 11) ininutes, eiiarging ofsodiutn iiydtoxide began fiilioififed by eiiargiiig tifthe 2.-n1et1iy1propana1ff2-etiiyiiiexaiiai inixtuiïeivvith a niinute delay-x 'ifotai eiiaisgiiig time ivas 30 iiiiiiittes. The teinpeirature i 'as set to iiieteasefioni 20°CT to 30°C during the sann: period. 'Tiie temperatiire vvas after etiinepieteti eiiargiiig ofreaetaiits iiiereased tio (iWC over a period of 15 niintttes foiioii-'ed by stiriiitg at said teniperaturefor a ftii-tiier 30 iniiiutes. Yieided i-eactioii niixture aims, efter eonipieteti reeietíoni eooied to ateinperattire of fi 301012 and pH tva: adjusted by addition of tiirmie zieiti. 'The reaction ntixtiire»vas tioaiiy reeowfeteti, puiíitieci :and anaiyseti.
Exampie 2 A reaetioii soiuticixi eomivrisiing 107.2 paits by »iteight oi" :in eiicieiiyfiie .niixture eonsistiiig iirfšiíiíšfiiby ii-'eigiit of Q-nietiiylptopansi and 109% hy iveigiit ofLethyiiiexaiitai, 187.3 inatts by iveigiit of483,4» aq. tiimiaidehytie, 125.0 parts by iveigtit fat" 509%» aq. sodítini hydtoxide and 670.0 paits byiveigiit ofwater vaas suiiieeteti to aidioi reaction and siihsetiiient caitiiizzzzro reaction. 110817 partsby xixeigiit of a reaction tiiixtute iixere, ttfter etmipieteti reactions, istiizitecti :uid the pH wasatijiisted to 5.5 by addition of 9.6 iïttirts by vweigiit tiffonnie ziciti. The Synthesis resiiiteti, remwfery zind ptirificiitiiïiii, in a 2,2-diinet11§,f1-1ß-propatiediiii yieid of 91.394; and a E-butyi-Q- ethy1-1 _.,3-1nropasnd.iai1 yiekï of Qílíïš/ß. "111-2 amouiit of imreziarteii aldehydes *w-'zis cífztiemiiiiefl m bf:< (110/6 of Z-methgfšprfiparial, <1 (1. 1% oiÉ-stšxjqlšxexanal aiid Of/“ffó of 1biíi1.1a1c1ei1yde.
Expcriinental: fås in Exanipif: 1.Exampíe 3 1åi*eactioii solutími cimiprising 1 12.? parts by »af-eight of :i iiiíxitixre cønsistiiig :if 85911;- by »x-'sightof Il-inetíiyflgnriupanal and iïïfiï-'iä by iiveigiit of 2~et11§f111e.xa1ia1, 19212 imrts 133' xx-'sigiit of 48% aq.ihrrnaldzâiycie, 128.1 parts by xvciglit of 50943 aq. sodiiiiii hyiiroxide and 685.0 paiits by wx-'eightcrf *Avatar was subjecteci to aidoiš reaction. and siibsfiqiiexit cfannizzaro reaction- 1112.? paris hy*afeight of a reaction inixiurc wxfers, 21:11:21' coniphaàed feiactions, isfilated and. the pH Vas adjïistedto 5.5 by additíciri (r1Ü11.Û parts hy weight of fomiic zicid. The Synthesis çresiilïed, :after recfn-feryfand 'purificaticiiy in 2.2-diinetfh§z1-1J-pfcipznifsdšoiš yieki of 118.194» and a 2.-bL1tyl-2-eïhy'1~1,3~propandiiil yield of 95.191). 'Tha aniuunt of unræzacted axkíehjycbss »vas deïermined to be < 1119-15 ofl-iïietíiyliißriagßn-ail. <1 0.195 oiQ-ci11y111exai1a1 and (181143fnffcim1a1dehyde.
Expcriifientai: As in Exampic 1.Exzimlaše 4 A reactioii soliitioii coniprísíng 5.4 parts by waighf oi” 2-ei11y11iexai1a1, 96.1 *parts by Weight of2~inetfhy1pr0pana1, 181.0 parts by xvaighi si* ßiêšïfß aq. iïinnaa1cše1iyfde, 121.2 paus by weight of50915 aq. sodiiini *liydroxiiiß :md 650.0 parts by weight of water siüqjecteii io a1do1 reactionand. subsequeiit carinízzairo reaction. 10412 parts hy vec-right of a. reaction inixtiire wvere, cimtipleted reactiøris, ísoiaiteid and the pH »vas :iifgiustcd to 5.5 by ai-Liditiivii 01109 11mm. by vveightof 'íbrmíc acid. The Synthesis resiiited. afier recovery 'and puriiïczitifliii, in a 2,2..-díin.eï1i5f1-1,3--prøpancdiol yiekš nf91.3% :and a 2-bu1y1-2~etl^iy1«_1.Išqøroivanciíøí yíe1d of Élliyå/b. The amountUf unreaßted ziidehyfdfls 1- 'as iieteiwiiiiieii. io be <1 (1191) of 2~1net11§r1priipaiiai, < (119/6 of 2~ et1i§f1hexanai1 and 1183121 of _foi°i11a1de11yc1e.
Eixperinieiitai: 'The rsactor xxfas charged ufith ihe specíiieci arnoum of water, ibrnialcichjydf: and2~ethy1hexana1 and. the inixïiire *ams iii-idea' stirring adjusted ZOUC over a iierinid of 111 ininiiti-zs.Afisi* siaídl 10 ininutes. chargirig of siwdiuiii hydiroxiciei ccimnieiiced iiäiloweii by' chargirig fiftheZ-iiiethyfbpi-ivpanaI wiih a. rninute deíay. 'Totaií cliargiiig time “fas 311 niinuïes. "File temperiatuiw:was sei to iniïreasß froin LZUCCï to EOÜC iiuring the same periiiai. 'The temperature xx-*as after corx1_p1cà§:c1 clïlznfgiïxg of reactanïs irlclroasocí to 60°C over a period of 15 oiníntztes ío11maf6d. bystírršog at said ternperature for a further 30 ïninutes. Yïehíod roactíozf: zfnixturf: vms, afteroonflpletod reaction, coo1od to <1 31100 anë pH x-xfas adj us1ec1 by addition of flnimic acid. *Tfhe reaction mixturc "was 11112111 y recovcreci, puriíïogí and aaæïašyseéí.Exfaïnpfie 5 A reaction solution oonfqarisíng 11.2 parts by' wfeíghå ofâ-ei1ayflhofxa1ïa1, 96.2 parts by xxfoíght of2*fnethyípropanal, 187.6 paus by 'w-'eight of 4851-11 aq. ííänfrxaïdohyde, 125.2 paris by weight of50% aq. sfadixlrn hydroxicle and 67110 pzms by wxfoíght of wfater “fas sobj avstod to a1do1 roacåiorzand subsoqvxlont cannízzalï: reactšon. 10845 parts hy mfeight of a reaction 'mixture were, afioroon1p1ctec1 reactions, iso1a1ted and t11ep1~1xfzas aašjxsstecí to 5.5 byf :addition of 1 1.2 parts hy *weightof íonfoíc acid. The syxïtïxesis resulteá, afisr refzoxfery and 1=)11r113ca.1šo11, in o 2,2~cíí1net11§f1-1,3~prqëaxïocíiçfl yíohi of 97.294; and a 2~1>L1ï}*1-2.~e1hy1-1ßflpfopandíol yioíö of 96159/5. The zunollnïof unnzacted ahflehydes was detennincd to be <4' (LW/ii of šflnethyharfapaxxaü, < 11.194; of 2- otšxyf1š1exa11a1 anal '1.=1% of ofonnzüdehydfl..Experínaent-al: As in Exaznple 4.Example 6 A reaction So1uïíon cornprisixng 16.8 parts by wx-'oíglzt oflä-othyflšfiixaxtxaí, 964 paixfts byfxxfoig11t of2~1not1^1y1propanz1l, 192.5 parts by vvfeiglaf. of 1118134 aq. Éb11nz1k1eš1yx1e, 128.8 parts by xw-'oígíxt of593%; aq. sodítnn hydiroäaíde and (5830 pzxrts by *weight of xmtor vvas subjßcted to aldoí .reaction'and sub-soquoxut oanrxizzzafav reaction. 111815 parts by wveight of a roaotioll soluïion xvero, aftercoinpïetocå roacïiorxs, šsoïafaïed and 'the pH Was adjusïoà to 5.5 by adäitianz of parts by xvoígšxiof foïmic acid. "Fhc Synthesis resuítod., afler rec-oxfory- and. ¿:Lx1'i1ïcz1tio11, in a 2,2-dí:neï113»'1~1.,3-propanec1io1 :field of 97.991: find a 2-bzxtyf1-2-ot1ïyf1-l,3-prcwpar1c1io1 yioolflš of 95.1*š~å. The aynountcví*ur1roactoL1 zdâehjyfdc-:s wfaïs cíoterfninoo to bo < 01% of 2~1ï1oï11§f1pr<>pfi^na1, < 011% of 2- ethjyüïoxanzæl and OBWÉ» of íor:1xaæ1c1e11§fde.
Exporšnxentafl: 1515 in Examplo 4.

Claims (1)

1. (fšgffiiï-:BS t. AV process tbr production of niixett 3,2~dititky']~1,_3~pr@p-ai1f:di01s by atdot reaction anti,subsetgueitt crtvssecl cannizztufti iwsaictitiii, c h air a c t e t' i s e d in, thzit tkirrnatdehyïlß in tvfesenceof 21 strong base is siibjectfid to aidol reactiøn aitd subsequent carnnizzaro reaction xvith 2-mstifiyfiiartipaimt and at least ams titiici' .ffï-atkylaïlkaiial at a flämtar ratio; ftirniaitiehyde m 2«lnettiytizrtiiwaiittzii 'and siaid at least. una (ither Q-'alkyialkzinzii of 2-22; i, that B-inetttytiíirtvtfiziiial andsaid a: teast inte: ottïer B-atkytaitkaiiai am prfisent in a i-veíght ratio infbetii-'eeii t :99 and 599.1, suchas betufceil 60:49 and 95:13, and that saidt process yiclds a, inixttire Lif 2,2-dín1c:tt1yi-1,3-iaropancctícit :and at tea-ist one ottisi' LB-diaiikyt-tß-propztnediot. IE. .ffxprocess afizcording to Ctaim I a: h a r a. c t e r i s d i n, that said at least una Luther 2~aikyíalkaiïial is a 2~a.1ky1;a1'tvpa11a.t, a B-aïkyttititattaí, a Q-ialttytpientanal, a. laikythexanal, .Z-atkgflheptztnzil antifior a lalkylcictzinaš. 3. A pifictess according td Cftaini 1 of 2 c h a r a t: t e r i s e d i n, tia-at said aikyi is methyt,ethyl, pfrotpyí, butyl m' pentyl. 4. A iítrncfiss according tf: any ofthe Claims t~3 c h a i' a c: t :a i* i s e d in, that said at teaistune (vttier 2,2~cšia.ti<;yt-iäÉš-iarøpaiiediol is Išßïfidicïttiyd-íÄßpropzinedität, 2-ett1yi~2~n1eti1§11~l,3~propanediøl, 2-prop3f1~2~1netit1yt-- t ß -propanediol aindfor É-'otitgft-E-ethyii--I ßpropaneditut. 5. A process according to aiiiy of tha: Ctaíms 1-4 t: h a r a c t. a: ri ts i: d i n, that said base is an zilkati or ëttkatinß ezntht mata! hyttrøxíde or carbøriati: atndftit' at: zanïiine. 6. A pmcess according to any ntthe Claims 1-5 c h a, r a. c t f; r i s e d i n, that said is potassšmn, sodiurti and/oi" catcitmi hffdrtixitie oi* carbønatfs. 7. A process according to any otttte (fïiaiitis t-é c. h a r a c t e r i s e d i n, ttiat said aidoi reauftiøii is pevtbzïiifted at' a teniperature of fštš-ötPífií. 8. A process according tø :any ofthe Ciaims tf! c h :i r a c t eri s e d in, that said ttannizzart) raactíon is performcti at 60~90°C. 9. A pinccss according to 11113' cstfthe (It-aims 1-8 c h a r a c t. e r i s t: d i n, tim: isaiti aidol3. reaction and said csnliiizzaro reaction is pertbnneti at a pH of 8-1 ííš. A process aacvcoz-flšíxxg to any of thfi (flams 1-9 c h a r a c t f: r i e d i n, that 2-inetißfíïpropanai and said at least one othør 2~a1k3f1aikanafi ars mixed prior to zxdziition of 'íbnnašaißlflyxia and other reagents. 11.. A process accurciing to any of tim (Ilaims i-š Û f; h a r a c t e r i, s s: d i n., thízü yíeïcïfixl'7 'P-cïilnethyblß-prupancdiol 2111:11 yielcïcd at lßast one üïhez' 2å,2»díaí1<;~'i-1,3~propa11edí0l are -_.¿,;_. separatcd and on filrïhcr prmcessíng used as sepßaraïs products. EZ. A 'process acconííng 6:0 any of the Claims 3-1 0 c h a r a c i' e r i s e d i n, tšixexfr yfíelnieaï2,2-§in1f:thy1~Ißqoropanedíoi and yíešcïed at least one other 2,2~<~lía}kyí-šjš-prfapanecíioi on fürther mocessíng are Lzscïd as a mixed product.
SE1630105A 2016-05-12 2016-05-12 Process for the production of mixed 2,2-dialkyl-1,3-propanediols SE1630105A1 (en)

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US2135063A (en) * 1937-07-06 1938-11-01 Du Pont Method of producing pentaglycol
US2413803A (en) * 1945-06-22 1947-01-07 Us Ind Chemicals Inc 2-ethyl-2-butyl propanediol-1,3
US2468718A (en) * 1947-01-10 1949-04-26 Trojan Powder Co Method of making methylol alkanes
US2761881A (en) * 1953-03-13 1956-09-04 Montrose Chemical Company Process for production of 2, 2-disubstituted propanediols
US5608121A (en) * 1994-10-20 1997-03-04 Mitsubishi Gas Chemical Company, Inc. Process for producing polyhydric alcohol
GB9519975D0 (en) * 1995-09-28 1995-11-29 Davy Process Techn Ltd Process
FI102963B1 (en) * 1996-08-19 1999-03-31 Neste Oyj Process for the preparation of 2-butyl-2-ethyl-1,3-propanediol
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