DE1443363A1 - Process for nitrating alkylbenzenes - Google Patents

Description

Process sun nitration of alkylbenzenes

The invention relates to the nitration of 1,3 * 5-Trialky3. " banzolen and especially from Hosltylen.

Mononitro derivatives of 1,3 »5-TriaUcylbenolen, beiepiela- -.ίβίοβ Heuitjlen, are hay ^ eatollt, indeia a GecilDCh of carbon / UBeuretoffes with liq uous acid and / or Acetic anhydride sulpeteric acid was auguöetsst · Dieaea Terfahren has some liaiitoile, namely 1.) are Ssaigeäuro and ksoigoaureanhydride relatively expensive, 2.) A lot of nitric acid is lost because it is in large Overhead must be used, 3 ·) int the insulation of the reaction producta, in which the reaction seeds are nit a large Ken e water and then diluted with

809805/0991

Ether extracted is not harmless and costly, 4) the disposal of the acetic acid waste products entails the risk of pre-pollution, or the alternative recovery of acetic acid from the waste liquid is costly, 5.) lot the use of a genius of nitric acid and acetic acid not safe and 6) the method requires the use of a m ± t auegekleideten smooth or made of a special alloy system "are increased by the cost dos traversed.

Serve night Elle can be largely avoided when an _f Geniach of saltpeter "and sulfuric acid (" mixed acid ") is used as Hitierungenittel. However, it is stated in the literature that the reaction of mesitylene with such a nitrating acid only gives polynitro compounds. (Se La Hure and Ridd, "Arozaatlo Substitution, Ritration and Halogenation", Acadeoic Press, Inc, Hew York, HY ·, 1959, p. 51).

The present invention now consists in a method * ur nitration οΙηβΒ 1,3,5-trialkylbeneolB see below of the corresponding Honoaitro derivative using an Oeiaioohee of nitric acid and sulfuric acid

809805/0991

1 * 43363

GeniiQ the method of discovery are Hononitro-1, alkylbenzenes in which each alkyl group has 1 to 3 Ko contains atoms, indene the corresponding 1,3,5-Triolkylbeneole by adding nitric acid in The presence of such an amount of sulfuric acid that the sulfur concentration 64 bin 8OfS, calculated as

Si 4 Sa
100 χ

Si + Sa + Wi + Wa + 0.285H

where Si and Wi are the original reaction genes in deia present weights of sciiefel3äure and Uneoer Sa and Wa are then added to the reaction mixture genes of sulfuric acid and Viaseer aind and H the ' gei.iech «ußeo would be the amount of weight of nitric acid, W * wearing. Nitric acid is preferably used in an amount from 0.8 to 1.2 Hols 1,3,5 ~ Trialkylbenaol used per Hol.

In the case of the tinning of the sulfuric acid concentration At one point in time, of course, only the materials that have been moved up to that point in time will be billed.

today will be Terfehren

. jß hdhiErr yield in the aröiienprdnunjs of sth | 60 ilia iufi d ^ r theory obtained with only a small amount of the corresponding dinitro compounds.

BATH ORIGINAL

8 U 9 8 0 5. "0831....

Dl · 1 * 3t5 ~ trialkylb «nsols, dl« can be «nitrated» according to 41 ··· * processes, and those in which each alkyl group contains 5 carbons, »eleplelewelee 1 _f 3,5-! Priaothylb "Iiol _t (Meeltyl"), 1,3,5-trilitliylbenBol, 1,3,5-tri-n-propylbeniol, 1,5,5-Trl-liwpropyXbgnaol, 1-methyl-3,5-diethylben "ol and 1-

T "rfahr" n the invention can dorohff "ftJ2urt w * r4" B "lndMi dl" KitrlereÄtnr · d «a 1.3 _t 5-Trlal3cylb <MeOL n« «« «tst is * nd will fool 'ugeveiee in the way carried out that dl · htrlerettur «an 8uep« nei <md ·· 1 _f 3 _t 5-frimUgrlWmmol · i »• la ·», geei «net« i TerdUrjjtmnwalttel, how a toraneeh becomes a toraneeh ·

Di · seh% * «f * l * & U3« kotia * mtrfttlatt dee Realcloiieeaie ^ i— is emlelt during the seecueten THRseteunf fcei 64 m ? ohvefeleäureJccnj;?! "eo • rfelft '·'.. er.trat or vmter <i ^ Abelakt · isaerwilneobt strong O ^ rd" tien "ad BUAang" rtl "he ÄAterlmllen V mm dl" Seltwefele * Mgefawi "eutmtli" Since eetiftehtllehe over 8OjC content «wild, beUplel · * iM the relheafolfe of the Su« Aee from SH «r · lad ejro ·

BATH ORIGINAL

becomes, · ο takes place la H- or SrIaItViMTOBf * Torsugsvel

bread der Tt «ad 70« eheltea.

Μ turns 41

SarehftttuniafeXora de · Terfahrea · der Mftataaf becomes · 1μ VltrUMlnr · old I ₁ O THTMBd · «· Bt» v | dlcMV 17/15 Vl-

29/57 · 29/15 or

■ "* ■ * ·. J"

«Ι« IM · fHrittel, · #! -

fwtteefciJB Who ■ lleä la Uftlta

B · 1 · «but« Ma b0 * LM » dl «ntvienlnr · la

·! ■ 1.2 μ 1

BATH

809806/0991

MolTürhaltennieee τοη wenlcar al · 0.8 iu 1 drove su lower Conversion of the aromatic compound, and MolYerhÄltnieee More than 1.2 mi 1 result in a deep nitration Tonnig A MolYerhftltnie τοη 0.9 to 1.1 iu 1 is applied

The hitriereöure becomes privileges / eise allaUhlioh au de «R« a *> tlonaaenleoh »ugeaetst, beiopieleweie * continuously or In one part of a speed τοη about 0.1 • la about 1 eq-5 <of the 111 trieräur · 1 · minute. Toraugewala according to the statement after the end of the SJforeaugat · nooh • o long fortaohreiten, stay the optimal · amount · of the g · - vUneooten MononitroTerblndune formed iat, example level 1/2 stand

The temperature of the refraction is best at -10 and 40 ⁰ O. The maintenance of a lower reaction temperature requires a lot of coolant and results in a low conversion rate, while higher temperatures initiate the integration and oxidation. Special gmt · Brg · * »nieee« is kept in mind when the reaction temperature svleeham ♦ 5 «mt 40 ⁹ O is kept« Oewöhnlioh let ee erwunseht »• Ims t« U (eeiepieleweiee 1/2 bl · 5/4) of the literature «At a temperature, for example 5-10 ⁰ O, atumMtaam« ml dl · Mttreaugab · and dl · Uta »et solution with a hollow

809805/0991

door, beiepielewelae 24-4O ⁰ O ₉ * u exit. Against or against termination of the set, for example during the separation of the products, even higher temperatures can be used

Vm the formation of tar-like products lifting suppress au, ee erwUnecht that Vitrlerung in the presence of a small amount "is beiepleleveiee 1 ₉ 0 to 1.5 Oew.-Jt, lied on dme TrlaDqrlbencol, durofcsufUhren on Sulfaeineüure or urea. Yorsugewelee is about 1 _t 25? T sulfamine acid used. Particularly good results are obtained if about a third of the middle, ie sulphanous acid, is added before the addition of the literary acid, about a third after the addition of about 50% of the literary acid and about 1/5 after adding the acidic acid. Experienced 4er invention, a conventional system, such as ate leioht eralltlloh iet, can be used. They can be made from stainless steel, OuS-eiaea "nuletahl or eiae. tweokBäAigerweiee value efficeae means eur cooling dee Reaktlonegefttiee ₉ belepielewelse a HIhImentel or KUhleohlangen, Torgeeenem «tone gate part and also a virkeaeie itttunror- ^! rlohtttmg ₉ a TeBperetmranfeelohnung Trriehtwng and other ·· for the ·· type of facilities usual help center.

BATH ORIGINAL

809805/0991

D% · raw * Mononitvo «1 ♦ SiJ-trifakyJ.bsmsrl can after known Method * lelefet το »der Η« α3ε * 1 $ 2! 9 »& β ·· must be separated. Beiapieleveiae viril dl · Reaktloaaaaa ·· at "lner T" ~ perattsr from «tv» 5 0 tH »« r δββ Ois, h »<9l» jTm> rt dor Maaanitro-

gth ^ lttn, bin «in« 'tmmamg in iw «l 8oheh« n tr- ^ vfoaaoh di «ob« r «orgwiiecha layer, which contains Ame jproduct, doroh De) casitl« r «ii from the lower dtr «N 8 chi oh t ebg · is separated. Alternatively, know the "R" tJ £ tion "e"! Ble <sh "- cools wfydi & t bl" the WoEvonitrover ^ inrtur ^ au "kriet"! Lteiert, tmd dlüen! "Stm daim ab.ftltrl * ^ od""ra ^ entrlfuel «rt verden»

• Ine
Gate of the 2HarohfahnmgT & leaer Terfahrcn kami dl · roh ·

• Diluted in water

* Q irt ^ ltenÄ raw Sfo ^ imltro-1,3,5 «^ rlÄlkgrlVas» «l« tenet olöh 1 »all ^ tselmera without w« lt # rc behind! Was ftir old vtor-; «e ^ ltoe ^ h th case * case of the product

a £ Bd «rcn f ^ tlgn ^ t ·» Jfetlwrfi * gertinS ^ t v «r *? e».

1 »f934« & A «a äö? \ *» 4 you Β · 1βρ1 · 1 «κ nMher werdea. Part «and JProM ^ taaeataa eeülAm al« h

da »f« gwlolit ·

BATH ORIGINAL

• t-

BUl JmUm IM 200 StIlM 7O] UiMV BalwafalaBiira Md tOlM (2 BaX) hmaltyUm vmrda krlfUg "stirs Md Mf 9 ⁰ O MkMlt · BMm MiUm UmI mm 740 falla tttriaratoa Μ · ITJayMaXf« talp «tami * rMmr ·) »

la 1 · 1/2 StandM Mg ^ * mutt * dl · t «ip« vmtttv d ·· Mi 3 - 10 * 0 MMltM · BmH Uv B — ktt 0MgMl Mm BMh «Im · QarMi« mi dl · fp ** t mat «turn 30 ⁰ O lia * Xm ÜMM MU tmrllmrt · dl · 8eln» J

Wv * Mmat vi OB ^ m MMgsiMmt TOJl TmIi BImMtMm dar iBMatammg'vmd atiim 73 hai

«Rfolft» · »1 · wimv

Okrt OTMnlMM 8MiMt Blaam * Amv (ok

, \ «D in Τ

Μ «Ittfctai

919 MO · H> MflTW Mg · —ft. BMh

iian 8tMdb «around

BATH

809805/0991

After the addition of the bison powder, the reaction was boiled for eight hours, and 50 pieces of calcium hydroxide were added. The reaction reagent was drawn off and the distillate, since an upper oily base and a lower aqueous base consisted of a template, so that the aqueous phase was continuously stirred into oil, the oily base (237 parts! de · · distillates was separated and deetilliert under Termiaderteei Druek. at 101-107 ⁰ C and 10 m were 213.4 part · Meeidin (Auebeut · «4.5 ^, beaogen on Meeitylen) above.

Belepiel 3

Dilution of Heeitylen is carried out as described in Example 1. However, the reduction τοη IltroBesltylen "u Meeidin weggelaeeen" and dl · 17 / ί5-ϊ1 "trier acid is set in individual lattiles", ee the close-together colar preservation of eelpeteric acid su Nesltylasl of 0.50, 0.75 , 95 _t 1 »0O and 1 ₉ 05 set wbxw den. laoh Sugebe Every part of saltpeteisaur · is · ice · pro ·· of the reaction— ■ ·· entnoMMn, “aoheipander sit Waeaer, wMJrigesi latrlumoarbeüftt and Vaaaer gewaaohsei, getrooknet xm & duroh Deepfphaeen-ChroÄatographie” nal7 ". 2He) Irdl · ··· Tereuoh ·· and Ia TabeU · I

BATH

809805/099 1

Table X

i * jC Kononltro- + Dlnitro-

Meeytrlen neeitvlen

0.3 42.4 33.3 1.1

0.75 3β, 7 53.9 2.1

0.85 15.5 77.9 2.6

0.93 11.2 β 1.7 3.4

1.00 2.6 90.0 3.4

1.03 0.1 91.6 3.5

The bitterness of the four sums of the three analyzed Components and 100Jt did 41 · Quantity · not needed idtlfUl t Tii l d Pdkt Si S

p J g

t «n T« rttnr «iBicasut« ii la dt «product. Si · Sr <«bxii ··· b ·«! · - h «B sieve me with the flUohtl ^ e fraction de

Beleplel 3

Yerlmf · «laer hour · wtarAea« iam Oeaieoh von Ua (1.25 *> 1) lleeltjlen did 0.5 parts BuIfamine · »·, on 3 ⁰ O was carbonized, under krUfti« «« Wtoxm 449 «Hl · 17 / 45-11trlereaure eu «« eettt _v 41 · KftaveaA der Gansen TSeeetauai a Sahvefeleaureconsentratlon taken from the o «• geJbaata Ber« ohmag of 74) 1 set and 77.7 (1.2 Hol) saltpete trough contained. Veiter · AateU · vmj · 0.3 · 11 «η OnTfejrtneiure been sugeaetet« naohdea 9OfS «as 100Jt of the Vltrie ^ fture were supposed to have been. Wthread dartagabe the eretea 75jt the litrleretture was the Temperatav a

BATH ORIGINAL

809805/0991

Hold R «acti <m« g «Bieeh» tb «i 5-10 ⁰ O« «. Μφι-ΜΜΙ 4 «r d» rl # t »t« n 29f (dtr litrltrmftur «11 · 0 Mn dl ·« uf 25-30 ⁰ O * t) lg «&. I * eh »#« ndi «ua« der I ** «ReektioaiMMui ·· in« ines · hold an hour · «uf 40 ° 0« miming and then b «i dl * e« rt «mp« ratur etth «ng« Xa «M & _f MLe SohlAV felldvmf« rfolft ·· Dl «oter · orfanleoh« 8ohloht _f dl «mm 201 part« raw ·· litroaweitylÄ (Autbmit · 9ejC) to stand,

and, la w «*« nUlöh «n wl · in Β« 1 · ρ1 · 1 t

4-12

from Bolepi «! 5
at dl «SttßÄrsKttii? · **» »« der ffitri ^ raiwm rajpiieFt imrd ^ n · ©

«ΒίΜΐ Wolvez4iÄl ^» i0 TOm Bftlpe ^ rsAere se

ta Tub <5llo ΣΧ

BATH ORIGINAL

809805/099 1

ZX

4th
9

§
10

11

O OO

• 5

04 94

100

w SmIAUi (BesofM

49 49 52 «4 91

• la

(4 Ma) HMltjlai «Ml 4 9 # il« l

· ■■ * ■ I

Wj 19-> S0 ° 0 MteltM «

B ^ D ORIGINAL

$ 09805/0991

~ 14 -

Hour at 25-30 ⁰ C gorührt. Dae Gen! Ah became eof! 50 ⁰ O would be and stand galaaeen until the blooming came up. Upper organic r.ciiioht from raw "" 3itrcsa * eitjle "(yield 97.5 ^, Sratarrungapun & t 29.9 ⁰ C) was separated from the lower sole ax from used acid. V © on a rope aw 1 «tater en phase in water Eisgetysgea ward®» so the solution obtained was only slightly cloudy «, vu« αί parasitic absence of tarry products

Example 14

9itration of hesitylene was carried out with a length of 3 years Beiopiel 13 beohrdUben. However, the SulfaaiasfSure became omitted · Both the raw litroaeaitylen and the Layers consisting of used acid were voa darker Color · as the corresponding products of Example 15 · tfesa a layer of spent acid bordering the layer ia water was entered, s * was the received * £ 8stst £ trUbet wtia on the presence of tarry ffesenprodokta, which are formed during nitriding iet · ". ... '

example

2) The VltrieroBf of Kesitylen takes place «ia« esentlloltt &

BAD CRIGiNiAL 809805/088 1 ^{C0? Y}

described in example 1, however the nitrating acid was sugeaetst 1 »terlaufe clay for about 4 hours. From 120 parts Heeltylen "order 163 parts (98 _f 6 # of theory) raw Hitro-" •• itylaa (Bretarrungepusirt 35 ⁰ O) -receive ·

crude product was old 300 parts of water veraiee & i and τοη by adding sodium carbonate saf a pH of about 8 "4a" gsatsllt · The SäGieah vard "n 0.2 parts" B & oeonol * BE _t a A3jQlne, tritia8ulXosuit _t ond 0.3 part D ^e Tween * 6O ₉ mia & m ozTml ^ lssdeTi-vat by SortltEaaonqot ^ arat »aagese ^ stt» dos 3 * ffilcsh VUT & ® osäf 50 ⁰ O erwSrat * mä aunt? Äsfiftts ^ ron & a £ 3 ⁰ C. Daa »I chilled from & ieidende crystalline ^ mrde filtered off, with Scalt ^ si Ifasee? g * vfiia? 3Jitn and yielded 130 ropes (73 * 7 ^)

example

60 | elle (O ₉ 5 mol) Kesitylen vurdcn m an 8-15 ⁰ O rare "Saalaeh rm 370 parts of 17/65 ~ 91 ^ ^ Πβ79 ΰ" ΐ "Al" 1 liel SeU.petersämr "contained xmtl ,,! 100 parts 7 ^ i ^ «r So ^ efQleftOS« «oeosebea. Sas lcrlstsaiine solid S & teslml * <5aa see b «i the Sugabe d» s ^ »eityleas formed» wirSd Vaaoar gevaaähen tmd e $ t? Oa & ä®f »Bfes ^ j ^ si ^ lt 103

9 3 Π 5/0 <

BATH
'COFY

(9 * 3: 0 Xttaitroaeeltyleit το »? Β5» «5 ^ο 0 · This« Seiepi ·! Illustrates “that the acclaimed addition of the reaction“ t · lint ijaer ”leads to the desired effect.

Belepiel 1?

240 TtIl * (2 HeI) Meaitjltn wasn iat essential as In Example 1 beaohri «b« a, nitrided «However, all Ii-

435 UUa 29 ^ 65 ~ Iitriereäur «old · 1α« «2 MoX Saltttereiiar« Yer ^ ®nd «t · 1 * 1 <3iee # r ttewiiii« rt «die BcS» / ef «leHiir9k & 2 ^ tntr (ttkioa von BlAeets« a The implementation until ^ u? 7 _t T? t at your end. Kam received raw timmnitvömmltylm in good

te

Su $ 560 files (50 Hol) Hseitylm of "2 ^ 0 were 15 ftil" 8ulfamin "Mur" sugeeetiit. Then within a few hours "" en 1ΟΘ59 files 17 ₉ 5 ^ Iitrier "4er® with" in """stop ron 1β9 files (50 Hol) Salpeterstttr® suge""were done. Baohdeei 5420 felle nitrating acid au ^ eetate warea «wird« »next · 15 feil · sulphate -ilUw« eugesetst · laoh Jie ^ isdigimg der Flugab · der

ΒΛΓ π:

309805/099 1

. 17 -

Acid were noon 16 parts · Sulphaic acid sugcsetst · During the addition · the first 75 * of the acid, the temperature of the reaction was kept at O ₉ S ⁰ O · During the addition of the last 25 * bitleric acid, the temperature was allowed to rise to 18 ⁰ O. Within one hour, the reaction was warmed to 40 ⁰ O, and for one hour at this temperature, sowing took place over and over again. The separated organic layer consisted of crude isolated product (4793 parts »yield 97 *) and had an iron freezing point τοη 34 ⁰ O.

These examples indicate that there are new procedures for dl · t «onnisohe production of τοη hononitro-1,3,5-trialkylbemiols suitable. The above examples veraneehaullohem • in the diakontinulorliohe · procedure. The procedure can Jedooh anon can be carried out continuously.

ftegenufor the known process, the process of the the present Irfindun «a look! of advantages · of All the more essential aittdi

¹ ) las ^ mttiai'- ¹ ^ organieche · löeungaalttel is not • rfUrderlioh »so that di · mUhaamen and often costly dl · Wl dear use · oil rather solvent

BATH ORIGINAL

809805/0991

are required »not applicable. The ones in the processors The agents used in the invention are easy to handle and do not pose any unusual risk Persons or systems with calibration

2) Economics - Bio reagents used are readily available and inexpensive. The process came to be carried out both batchwise and continuously

?) ^y lrksa "keit - The process of the invention, because Kit carried out a" minimal excess of heat "leads to excellent yields in the range of 60 to 97% of the theory and to a" product of high quality, dao eich all one without further concern door the use is suitable

809805/0991

Claims (1)

1. The division into a honon-1,3,5-trialylbene-ols, la since each alkyl group contains 1 or 3 carbon atoms, which means that there are 1, 3, 5 -Trlalb3rlbenM> l is nitrated, while lh «Balpeterailar · la OaeasMurt from · οτ! · 1 Sohwefeleäure that dl · SohwefelUkurekMUMntratloa 6A * to BOfL ₉ Toreueeweiee 72 bl · 76? T, calculated al · 81 100 s 81 ♦ 8a ♦ ¥ i ♦ Va ♦ 0.2851 worla Ui. and Vl dlureprUnglloh In dia Reaktlon «g« nla4i anwee «nd« n O «vlohtemeneen an Sobwefeleture and waaa« r vat 8a and Va dl »daaaoh dea Reactioaegealeah sueeaetate« Oa »wlohte ad — nfen am Sohwefel I die deei Reaktloae «« Bleoh sueoeetite 0 «wiehtemenff · an Salpetete let, 2 Terfmhrcn naoh Anepruoh 1 ₉ dadurah eekennMloluwt _# da je Hol au altlerend Trlallqrlbeisol 0.8 bl 1.2 MbI SaI- will. 5. Tavfaloraa naoh Anepruoh 1 or 2, daduroh gelrenMMioh-Mi ₉ daf the feaperatur d ·· B * aktlonegeal * ohe · b «l -10 * 0 bit BAD ORlGIMAL 809805/0991 4O ⁰ Ot TOrsugavalaa is initially kept below 10 ⁰ O and danaoh bal 25-40 ⁰ C. 4 «Tarfahran according to a dar Anaprüohe 1 bla 3, daduroh characterized that the TJtaaetaung is carried out in the presence of SuXfamineaure or urea · 5 · Tarfahran naoh a dar AnaprUoha 1-4 »daduroh marked that the nitric acid of the Qaaieoh allaBhlioa in the Torrn elnee Oamlaohea is constituted by nitric acid and sulphurous garnish. 6 «Tarfahran naoh einaa dar AnaprQche 1 - 5t daduroh can be rewarded, that Heeitylen is not used 7 · Tarfahran according to Anepruoh 6, daduroh ketmlielohnet, AaJ dl · litrierelure, dia 17 * nitric acid, 65 * Sohwefelaiara and ie * V & BWBC contains, alls & hllcdi su an Oaelaoh of sulphurous aluminum and meeltylan old one (} eeohvlndlgkeit of 0.1 * dar IltrleraÄura Yes »nute xugeeetat we« and dej dia Xugftbe dar litrieraäure ao is continued for a long time, bia dam ReeJctionegenieoh ja NoI »eaitylen 0.9 to 1» 1 mol Salpetereätire sugoeetat alnd, wabel dia Qaaetmmg la Oeganwart of not »or ale 1, 5 Oew .- * Sulphaalnattare, beginning because "Heeltylan, is carried out" SAD 809805/0991