SE458033B - Metod foer dealkylering av alkyl-aryl-etrar - Google Patents
Metod foer dealkylering av alkyl-aryl-etrarInfo
- 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
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.
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 |
EP85905244A EP0198880B1 (en) | 1984-10-22 | 1985-10-17 | A 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 |
DE8585905244T DE3570648D1 (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 |
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)
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NO107714C (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 |
-
1984
- 1984-10-22 SE SE8405262A patent/SE458033B/sv not_active IP Right Cessation
-
1985
- 1985-10-17 DE DE8585905244T patent/DE3570648D1/de not_active Expired
- 1985-10-17 WO PCT/SE1985/000399 patent/WO1986002634A1/en active IP Right Grant
- 1985-10-17 US US06/881,027 patent/US4695659A/en not_active Expired - Fee Related
- 1985-10-17 EP EP85905244A patent/EP0198880B1/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
WO1986002634A1 (en) | 1986-05-09 |
SE8405262D0 (sv) | 1984-10-22 |
EP0198880A1 (en) | 1986-10-29 |
DE3570648D1 (en) | 1989-07-06 |
SE8405262L (sv) | 1986-04-23 |
US4695659A (en) | 1987-09-22 |
EP0198880B1 (en) | 1989-05-31 |
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