SE458033B - Metod foer dealkylering av alkyl-aryl-etrar - Google Patents

Metod foer dealkylering av alkyl-aryl-etrar

Info

Publication number
SE458033B
SE458033B SE8405262A SE8405262A SE458033B SE 458033 B SE458033 B SE 458033B SE 8405262 A SE8405262 A SE 8405262A SE 8405262 A SE8405262 A SE 8405262A SE 458033 B SE458033 B SE 458033B
Authority
SE
Sweden
Prior art keywords
solvent
benzene
alkyl
cyclohexane
ether
Prior art date
Application number
SE8405262A
Other languages
English (en)
Other versions
SE8405262L (sv
SE8405262D0 (sv
Inventor
S G B Andersson
Original Assignee
Chemical Dynamics Dev Ab
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemical Dynamics Dev Ab filed Critical Chemical Dynamics Dev Ab
Priority to SE8405262A priority Critical patent/SE458033B/sv
Publication of SE8405262D0 publication Critical patent/SE8405262D0/sv
Priority to DE8585905244T priority patent/DE3570648D1/de
Priority to EP85905244A priority patent/EP0198880B1/en
Priority to US06/881,027 priority patent/US4695659A/en
Priority to PCT/SE1985/000399 priority patent/WO1986002634A1/en
Publication of SE8405262L publication Critical patent/SE8405262L/sv
Publication of SE458033B publication Critical patent/SE458033B/sv

Links

Classifications

    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group

Landscapes

  • 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)

Description

458 033 Reaktionsformeln kan skrivas: R-0~Ar+P-lïa n-'R-æm Ar-'oH+R-I 2) H20 R = alkyl Ar = aryl I det följande kommer metoden att närmare beskrivas med exempel.
Exemgel 1 Aluminiumpulver (2,5 g, 93 mmol) och jod (l9.0 g, 150 mmol) blandades i 130 mm bensen (eller cyklohexan) och refluxades tills jodfärgen försvunnit (ca. l 1/2 h). Bland- ningen kyldes. En lösning av anisol (fenyl-metyl-eter,' 5,4 g, 50 mmol) och n-Bu4N+I“ (Tetra-n-butylammoniumjodid, 0,05 g, 0,14 mmol) löst i 25 ml bensen (cyklohexan) till- sattes droppvis och reaktionsblandningen värmdes och fick refluxa 20 min. Efter kylning hydrolyserades med 150 ml vatten. Organiska fasen avskildes och vattenfasen extra- herades med 2 x 25 ml eter. De organiska faserna förenades och extraherades med 30 ml 2N NaoH. Vattenfasen avskildes, surgjordes med konc. Hcl och extraherades med 3 x 25 ml eter. De organiska faserna torkades (Na2S04) och indrevs, varvid ren fenol kristalliserades. Utbyte = 99%. Smp. 41-42°C. ' Exemgel 2 Aluminiumpulver (75, 279 mmol) och jod (S7 g, 450 mmol) blandades och refluxades enl. ex. l. Efter kylning till- sattes en lösning av pyrogallotrimetyleter, l,2,3-trime- toxibensen (8.4 g, 50 mmol) och n-Bu4N+I' (0.l g, 0,28 mmol) löst i 25 ml bensen. Efter l/2 H reflux, hydrolyse- rades blandningen med 150 ml vatten. Bensenfasen avskildes, tvättades med 2 x 20 ml vatten, som förenades med vattenfasen. 458 033 De förenade vattenfaserna extraherades med 6 x 50 ml etyl- acetat (Et0Ac). Et0Ac-faserna förenades, torkades (Na2SO4) och indunstades, vaèvid ren pyrogallol erhölls i 95% utbyte.
Smp. 132-l33°C. 4 458 Cfšïsjande tabell ger en översikt över andra genomförda de- alkyleringar enligt metQden_ .« _ M°l_ .Mol- Eter Lösn t förh' förh- . ' Reak. Utb te ' medel _ A13/ Étššz tid(h) % Y Prgdukt 'eter 4 ' OCH3 _ OH bensen 1 360 l/3 kvant 100 anisol fenol Cyklohexan 1 360 1/3 kvant 100 än F) m HJ / \ g ocn3 'csz 1 aso 1/3 91 <::} _ Gå \ ocn3 , OH / ¿ bensen 1 360 1/3 94 \ \ 2-metoxy- 2-hydroxy- naftalen - naftalen C O CHO à bensen 1 :_60 1/2 va OH OCH3 p-Hydroxybensal- p-Metoxybensaldehyd dehyd CHO HO ü cyklonexan 1 360 1/2 so c \ ocn ' _* OH 3 p-Hyd:oxybensal- * dehyd CF” ao /'1 bensen 1 360- 1/2 84 EÉÉ9 \ C53 -\ *on _. _? I-n m-metoxybensaldehyd _ geäšä*°xybensa° OCH cH 0 '3 ocH ' OH 3 / I/ 3 bensen 3 180 1/2 95 HO OH e, í 1. pyrogallotrlmecvl- \*“/ eter ' Pyrogallol CHO / | bensen 4.8 350 1-5 " 53 \ ocs.
HO vanLll¿n _ f 2.3-Dlqydroxvbêfls aldehyc I) _ Mob M'°1_ .458 033 förh f" h Reak- íßter Lösn. Al /' eâšrz tid JUtbyte Pro- % d k - medel etår R4NI (h) u t pêflsên l l Spår fenol Difenyleter OCäH5 OH [3] cyklohexan 1 360 1-0 90 Ei] E toxybensen fenol CH3 CH ,/ ÉÉUCHB cyklonexan 2 'mo 0.7 se \ 1% OH OH 4-Hydroxy-3-me- 3.4-Dihy- ' toxytoluen droxytoluen ef” cno cyklohexah 5.5 120 2.5 ' 14 I OH SH OC 3 OH Isovanillin 3-4_Dihydr0xy- bensaldehyd=pro tokotechualdehyd CHO CHO Cíj cyklohexan 4.5 120 l-5 84 | \ f o-/O \ I H 3.4.Metylendioxy ¥ __ Oh bensaldehyd = piperonal= =heliotropin CEO CFO ocsa , OH / cyklohexan 1.5 100 14 88 1 \ H ' 3_3 100 1.5 90 H _ _ Haco oc: " 5.5 wo 1.5 91 - caus- 3 -- IM) 50 .o.o ss' 2,4,5-TtLmeccxybens- aldehyd (J 4.5-DLmecoxj- saïïcvlaldënyc 6 (J 458. G33 ¶ Eter« Lösn.' Molförh- Reakt.:Utbyte 3 medel A13/eger tid'(h)' ' Prod. 1/ CHO ' cno ' cyklohexan 1.5 12,0 7(1;¿1(2) _3390 OCH: 1- 3,3 6,0 lsmfsuz) Ham OC H u 5,5 15,0 l0(l),81(2) 3 OCH . _ 3 _ 4.5-D1metoxy-2- ~3,4,5-Trimetoxyl hydroxybensaldehyd bensaldehyd ' _ - + CQO Molförhàllande eter/R NI- var 100 _ _ _ 4 H-co H v1d samtllga tre försök med 3 0 3 3,4,5-trimetoxybensaldehyd 3_5-0imet0xy_4_ ' hydroxybensaldehyfi 2/ CHO H3ÉGH OH. _ 3.4~Dihydroxy-5- metoxybensaldehyd + C30 Û Ho f on OCH3 3,5-Dihyåroxy-4- metoxybensaldehyd

Claims (1)

10 15 20 458 033 PATENTKRAV l. Metod för dealkylering av alkyl-aryl-etrar med alumi- niumnitrijod, som framställts insitu ur jod och alumi- niumpulver, k ä n n e t e c k n a d av, att reaktionen sker i ett inert lösningsmedel av alifatisk, cykloalifatisk eller aromatisk karaktär, i närvaro av.katalytiska mängder av ett kvaternärt ammoniumsalt med den allmänna formeln R4N+I', där R är alkylgrupp. Metod enligt patentkrav 1, k ä n n e t e c k n a d av, att det kvaternära ammo- niumsaltet är tetra-n-butylammoniumjodid. Metod enligt patentkrav l - 2, k ä n n e t e c k n a d av, att som lösningsmedel användes cyklohexan. Metod enligt patentkrav l - 2, k ä n n e t e c k n a d av, att som lösningsmedel användes bensen. Metod enligt patentkrav l - 2, k ä n n e t e c k n a d av, att som lösningsmedel användes toluen; Metod enligt patentkrav l --2, k ä n n e t e c k n a d av, att som lösningsmedel användes xylen.
SE8405262A 1984-10-22 1984-10-22 Metod foer dealkylering av alkyl-aryl-etrar SE458033B (sv)

Priority Applications (5)

Application Number Priority Date Filing Date Title
SE8405262A SE458033B (sv) 1984-10-22 1984-10-22 Metod foer dealkylering av alkyl-aryl-etrar
DE8585905244T DE3570648D1 (en) 1984-10-22 1985-10-17 A method for dealkylation of alkyl-aryl ethers
EP85905244A EP0198880B1 (en) 1984-10-22 1985-10-17 A method for dealkylation of alkyl-aryl ethers
US06/881,027 US4695659A (en) 1984-10-22 1985-10-17 Method for dealkylation of alkyl-aryl ethers
PCT/SE1985/000399 WO1986002634A1 (en) 1984-10-22 1985-10-17 A method for dealkylation of alkyl-aryl ethers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
SE8405262A SE458033B (sv) 1984-10-22 1984-10-22 Metod foer dealkylering av alkyl-aryl-etrar

Publications (3)

Publication Number Publication Date
SE8405262D0 SE8405262D0 (sv) 1984-10-22
SE8405262L SE8405262L (sv) 1986-04-23
SE458033B true SE458033B (sv) 1989-02-20

Family

ID=20357436

Family Applications (1)

Application Number Title Priority Date Filing Date
SE8405262A SE458033B (sv) 1984-10-22 1984-10-22 Metod foer dealkylering av alkyl-aryl-etrar

Country Status (5)

Country Link
US (1) US4695659A (sv)
EP (1) EP0198880B1 (sv)
DE (1) DE3570648D1 (sv)
SE (1) SE458033B (sv)
WO (1) WO1986002634A1 (sv)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3815292A1 (de) * 1988-05-05 1989-11-16 Basf Ag Verfahren zur herstellung von hydroxybenzaldehyden
DE102007058741A1 (de) 2007-12-03 2009-06-04 Jenabios Gmbh Verfahren zur O-Dealkylierung von Alkylarylethern
CN103864578A (zh) * 2014-03-19 2014-06-18 中国科学技术大学 一种4-甲基邻苯二酚的合成方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL129847C (sv) * 1961-06-21
GB1227144A (sv) * 1967-04-05 1971-04-07
DE1768050B2 (de) * 1967-04-05 1976-11-25 Continental Oil Co., Ponca City, OkIa. (V.StA.) Verfahren zur durchfuehrung von heterogenen organischen ionenreaktionen
US4172960A (en) * 1975-06-28 1979-10-30 Fisons Limited Process for preparing pyrogallol
US4112003A (en) * 1976-02-12 1978-09-05 Givaudan Corporation Process for preparing polyphenols
US4087410A (en) * 1976-06-14 1978-05-02 Eli Lilly And Company 5-(Tertiary alkyl) resorcinol preparation and intermediates therefor
IT1087474B (it) * 1977-11-08 1985-06-04 Zambeletti Spa L Metodo per l'idrolisi di eteri mediante impiego di cloroioditi di tensioattivi ammonici quaternari

Also Published As

Publication number Publication date
WO1986002634A1 (en) 1986-05-09
US4695659A (en) 1987-09-22
SE8405262L (sv) 1986-04-23
EP0198880A1 (en) 1986-10-29
DE3570648D1 (en) 1989-07-06
SE8405262D0 (sv) 1984-10-22
EP0198880B1 (en) 1989-05-31

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