Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
h 1 1 ~ ~ 1 7
!HOD FOR MANUFAC$'URING AIlKYI~G~YcOsID}æS
aA~Q~2
The lnventlon rela~es ~o a method for
msnu~acturing alkylglyco~ide~ by ~i~ect 3ynthe~
~ tarting with fatty alcohols and saccharides ~n~ u~ing
acid catalysts.
The term "alkylylycoside~' withln the fr~mewo~k of
the invention re~er~ to com~ou~d~ ln which alkyl ~e~i~ue~
are bo~ded acetallcally to monomerlc andlor oli~ome~lc
sugar re~idues.
The ~erm "alkyl re~idues" ~e~ers ~o residues
derived from mo~ofunctlonal alcohol . which can b~ linear
or branched and pre~erably contain 8 to ~0 oarbon atoms.
E~peclally 6ultable ~lkyl residue~ are those derlved from
aloohol~ ob~ined ~rom nat~ral ~ub~t~nce~ suqh as ~at~ and
oil~ that u~u~lly con~tltute a mlxtu~e, e.g. h~ C12/~14
chain~, and that can al~o have unsaturated resld~es.
The term "fatty alcohol~" wlth~n th~ fram~work of
the inventlon re~ers both to alcohol~ o~talned from
natur~l p~oduats and to synthetically produced zlcoholc.
~O It i~ known th~t alkylglyco~ides c~n be produced
~rom fatty alcohol~ and saccharid0~ u~in~ an acid
aatalyst. Numerous methodg are de~crlbed in the
lite~ture in whi~h ~ glyco~ide ~ initially obtained ~rom
~aa¢haridc~ by rea~tlng a low-moleculax-we~ght ~lcohol
0uah as methanol, ethAnol, and the like, whlch i~ then
aonverted!to ~he desired alkylglycoside by reacetalization
with a hlgher-molecular-weight alcohol. Numerous
cntalyst~ are recommended ~or thi~ type o~ reactlon.
It is ~l~o known th~ ~ynthe~i~ can be p~r~ormed
from sacoharldes directly by reaction wlth a hlgher~
molec~lar-weight alcohol, i,e, an alaohol with ~ to 22
carbon atoms for example. Numerou~ acld cataly~t~ have
been mentloned ln the llterature for thl3 type of re w tion
as well.
~hus, 40r ex~mple, B8 descrlbed ln European Patent
AppliCatlon 0 132 043, inorganic acid~ ~uch as
hydrochlorlc acld, suIf.urlc acld, and phosphoric aci~ are
) 1 7
recc~anen~ed. AS well p~luenesulfonic acid and boron t:rirluoride are mentioned
for thl~ purpo~ Acoordîng to the t~aching ~ Europ~an
Patont Ap~liaz~tior~ 0 13~ 043, anionic~ ~;ur~aatant~ ~uch a~
~lky} E~ul~te~ lk~lb~nzene oulfona~eo, and alkyl
~ulXon~a ar~ us~d ~g aa~aly~ts to ~k~ lcylglycosldo~
Real~ Trav. ~hlm. Pays-B~ 110, 0~3-024 (19~1)
desarlbe~ the re~ction o~ mono~accharld~ w~th 4-p~nt~nol
in dim~thyl~ul~ox-ida ag the ~3olYent, U3 i ng
tri~luoro~hane~ul~onic Aol~. ~hl~ i~ a glyao6id~ with a
low-molecular-w~$ght alcohol which is un~ultAbl~ a6 raw
~atarl~l for w~hing . In ~dd~ tlon, thQ yl~ld i~ only 55%
a~te~ a re~otlon tix~ of 2 ~ay~ at 90"C wh~n gluço~e 1~
U~Od .
~. Carbohy~rate Che~istry, 8 ~ 63-2~9 (1988J
dewrlbe~ the rQ~ctlon of ~ugar~ wi~h allyl alcohol, us~ng
~r1fluoro~eth~nesulronic: aoid A& ~he catAly t~ Thl~
glyooside ~ro~ ~ low-~ol~oula~ alcohol 1~ ~hqn
~c~tylA~e~ wlth ~nzyl ~laohol. ~harQ i~ nothlng ln
thi~ pu~lio~tion mentionl~ a u~able dlrec~ synthesi~ o~
wa~hlng ~ctlv~ alkylglycosi~e~
Although a wldQ varl~y of m~thod~ ar~ known for
manu~aa~url~g alkyl~ oGide~ by elther the direct o~
lndlroat approach uoing many di~erent cataly~t~, ~n~r~
~tlll ~ noo~ ~or ~mproved method~ o~ d~e~t ~yntheal~
2S The goal a~ the inve~lon there~or~ 1~ to provlde
a method go~ dlrec~ 6yn~h~1a of alkyl~lyco~ otartlng
with ~atty alcohols with a to 2~ a~rbon atom~ and
sacaharides, e~p~clall~ ~ono~acobarid~o, uolng acid
~a~alysto/ on~ wh~oh i~ econo~ical to pe~orm, p~rmit~
faster reac~lon t1~D ~or ~ivon r~action oon~lt~on~,
produc~o a pro~uat With ~ood propertles, and ~B ~mple to
S~or~orn~ and l~ad~ to reproducible results.
The goal o$ th- invent~ on 1~ al80 to provide a
m~thod whlch u~es ~ller a~oun~ o~ CatQly3t than thos~
~5 . known hereto~or~. ~he goal o~ the inventlon i~ 51D to
provide a method that produao~ ~atl~factory yl~l~e ovon at
low temperatur~6 at ~aono~i cally accept~ble reaction
tlme6 .
'.
~lly~l7
~ hi~ go~l i8 aahi6~ved by a m~thod ~or
manu~aaturi nS~ alk~ coside~ by ~eaating mono~achari~s
with ~atty z~looh41s ~.n the l?re~ence o~ an aald aataly~t,
~haract~rlz-~ by th~ ~aat ~hat mono~acoharide~ and fatty
alcohol~ w~th a ca~on number ro~ 8 to 22 ar~ r~at~ in
th~ pra~na~ o~ p~luorinnted ~ul~onla aaid~ as the
cataly~t. Pe~luorln~te~ al~a~e~ul~onic ~cid~ with at
lea~t ~ carbo~ A-~O~ ar~ v~ry ~ui~able, ~or example
porfluorooctan~ul~onic acid, ~arfluorobu~a~e~ulfonlc
aa i~, p er~ luoropro~ an~ul~o nic aci d,
parfluoro~than~sul~onic aa~d, an~ ~ixtur~s thereo~. In
additlon, per~luorinat~d cycloal~ane~ul~onlo aald~ ~u~h
as/ ~or exa~ple, 1,4-per~luoroeth~lcyclohexan~UlfOnia
aai~ have al~a produaed very good re~ulto. In ~noth~r
advantageous embodlment o~ the ~ethod ~aaording to th~
inven~lon, ~r~luorinat~ sulfoc6r~0nlc acid~ and/or thslr
~t~r~, ~or sxample p~rrluoroaul~oaaeti~ aaid, aro U~4~.
Pr4f~rably, glucooo 1~ u~ a~ th~ monoo~och~ride. It 1
advan~ageou~ to use 0.5 to 15 mmol aat~ly~t por mol o~
2C r~or~oaa~chariA~. Th~ qu~ntlty of cataly~t na~u~lly aan
vary w~thin W~d~ l~mit~, both ~pward ~n~ downwara, an~ can
be ~or example 0.~ ~m~l o~ ~0 ~mol per mol o~
monosa~ahar~de.
In ono ~p~clally ~vantag~ou~ 4~bodi~nt,
reactiorl o~ moslo~e~ccharlde with ~atty al~ohol is pe~ormed
contlnuou~ly. : ::
It was especlally surprislng that the method
acaordlng to the inv~n~lon o~ten lea~ in ~u~h shorter
ti~e~ t~ a ~ls~actory r~action o~ th! fatty Alcohol w~th
tho ~onosaooharide. Beaau~e of the high speed~, it 18
po~ib~e to aonduct a r4~ction at low~r to~eratureo ~h~n
the ca~ when ordlnar~ know~ catalyst~ ar~ uaed ~or .;
~u~h re~ction~ al~o po~lbl~ to u~ much omall~r
quantiti~ o~ aataly~t~ Th~ aataly6t csn be regener~ted
a~ ~ll in high ylelds, i~ thi~ is i~deed desired or
neoe86ary~ an~ can b~ used ~gain ~n ~ynth~si~. For thi~
re~on, th~ method ~e very environmen~ally ~r~endly.
~ho m~thod ~an ~e pe~oxmllad con~nuously ln a~1
~p~aially adv~ntas~ou~ mann~r with high y~ 41ds. It 1~
not ne~os~ry to produoE~ glyco3~deh ~ir6t Wit:h lowQr
alcohola and th~n re~aetyllze the~.
S since the amoun~ o~ ca~alys~ re~ain$n~ in ~he end
p~adu~:t 1~ negliglbly ~mall, it u~ually aan r~main in 'cho
~nd ~ro~uct.
~n particul~r, the actlvity wi~h v~ry ~in~ly
pnrt~oulate gluc:o~e i~ ~p~lally high ~ ao~npar~d wi~h
ordinary cat~ly~t~.
I~ w~ al~o 0urpri~ ng tha~ th2 Dlethod ac~ording
to the irlvention provid~ alkylglyao~id~ 'ch~t ~f~r ~ro~
produ~ts m~de b~ oonventlonal metho~o as r~gar~ their
l?xopert~e6. Thu~, ~or ex~mplo, it 1~ poa~le, e~p~aially
wit~ th~ oon~inuou~ pro4edure, to obtAin ~l~cylglyco~
that e~i~it ~ muah low~r vl~c08ity ln an aqu~ou y~tem
wlth an otherwi~e ~dentical wa~hlng pow¢r. Thi6 meAn~
that once aqueou~ ~y6te~0 wl~n muc~ high~r concontr~tion~
o~ ylglyoo~ide can b~ aa~u~4d, so th~t 3ys~em~ w~th up
2~ to 75~ alXylglyco~lde c~n be prepRre~ Another a~vAnt~ge
o~ the ~ethod accordin~ to the inv~ntion $~ ~h~t it
permit~ the ~anu~actu~e ~ ~ro~ucts whlch ~r~ pump~bl~
AqUeOU~ mixturQ~, ~ven ~n hi~her concentr~tlon~. Ordln~ry
p~ducts at higher concsntration~ ~or oxampl~ 50~ or
a5 ~ore, oan be proparod a~ pa~te~ whiah, i~ th~y are to be
pu~ped~ mu~t ~e ~ea~d, whioh lnvolv~ con~i~arabl~
di~advantage~, The produat~ o~ained accordi~g to the
invention on the othe~ hand can be pufflp~d ov~n at hlgh
a~n¢en~ratlons at room temperature~ The inter~A~lal
tens10n ~alue~ and ~he ~olubllizatlon of thQ ~roeuct~
prepared according to the inv~ntlon are out~t~n~ing. The
~oa~ valu-o ouah a~ ~oam height, ~o~ R~illty, an~ tn~
lilce ar~ g~OOa.
It i~ al60 a gr~at advantage that syr~py gluco~e
can be r~actad a~ well, Syrupy glucoo~ 1B an inoxpen~iv~
prod~c~ obtaln~d for example by acid ~r enzymat~c
hy~rolysi~ of ~aro~. Syru~y ~luco~a~ aan al80 be
obtalnQd ~ro~ ~acaharose, li~e tha~ ob~lned ~or ~xample
~ro~ ~ugax beet~. Syrupy ~lucoo~ con~a~n~, in addition to
glucose Rnd w~t~r, oligom~r~ ~n~ a ~mall an~ount Or
poly~ccharld-o .
~rhQ ~nventlon will rlow b~ d.e~c:rib~d in grea~er
5 detall wi~h r~eren~ to th~ ~ollow~n~ ~xampl~
oo~uro ç~ Do~o~ tlon o~ r~u~ ~BO~
A commorclal 1 1~ ter sUa~i glas~ raao~s~r with
dou~.e-~Ack~ h~atinçl, Int~rmiq ~$rr~r, ~o~tom ~rain, ~nd
di~illatlon attaahment wa~ usRd a~ ~he r~ tor.
~h~ ~ollow~n~ xampl~ls war~ pr~par~d wlth ba~ah
op~a~$on, i.e. ~11 o~ th~ ~lucose ~Glc) ~nd all o~ the
fatty alcohDl (FA) were placed. in tha rea~tor and th~
~ix~ur4 wa~ ral~ o th- roquir~ t~mp~ra~ur~ w1 th
Btir~ng and evacuation to 20 ~ar.
1~ ~h~n th~ cataly~t waa aad~d ana thi~ point ~n t~m~
was aon~ld~re~ tha be-ainr,ing o$ the reaction.
The reactlon wat~,r wa~ ~rawn of f oontinuou~ly a~
ot~ an~ pr~alpit~t~d in a graduated ~sel, The wate~
ç~enera~ion rat~ wa~ ~valuata~ a~ th~ conversion r~t~
ZO o~ th~l Gla (1 mol o~ wa~r wa6~ rQ~Qa~d rO~ ¢ach ~ol o~
~ea~ted Glcj.
~he tl~e required ~o~ 99% Glc conversion was termed
the reaatlon ti~e and used ~or ~h~ comparioon~.
o ~
90. ~ g of gluco~e anhy~rou~ ~ere~ta~) with an
a~rerage p~rticle size of 5 ~m w~ro pl~d ir~ tha r~aat~r
tog~th~r w~th 412.0 g of fat~y alcohol ~Na~ol '~14 ~ro~
Cond~ aonta~ning a~proxlmat~ly g4% ~auryl alc:ohol an4
approxi~n~t-ly 44% myrietyl alcohol) and rai~ed to the
re~atlon te~perA~ur~ ~f 110 w1th s~irrin~ a~'ce~
evacuatlon to 2~ mbar. A~te~ 110~ wa~ reAched, 5 ~ol
per~luorooctAne~ulfoni~ aald wa~ added p~r mol o~ gluaose.
A~4r ~0 m~nut~ reaotlon tlmo ~t 110C ~ 1C, 497 mmol
reactlon wA~r ~- 8.3S g) WaB dr~wn o~ ~rom the ~eactor,
corr~pon~lng to 99.09; gluoo~ r~actlon.
~he re~lon pro~uo~ wa~ cl~r and wh~te.
:
Aft~x neutx~lization o~ th- cataiya~ w$th NaOH an~
FA ~ep~ation to l.~ wt.~ the ~ollowing analy~eæ w~r~
po~form~d:
~ree glucos~: c 1 wt.%
~ono~luco~ldG (C~2 + C~ 53.0 wt.%
~x~ple 2
~ h~ example was p~r~orm~ ~nalo~ou~ly to Exampl~
1 wlth the excep~lon that a mixtur~ o~ per~luoroetha~
~ er~luoropropane-, and porrluorob~t~ne~ulfonlc aci~ with
an a~erage ~olecular wo~ght o~ 253.a g/m~l was us~d a3 the
cataly~t. ~lXewi~e a~t~r 60 minutos r~actlon ~im~, 99~ o~
thQ add-~ gluao~6 wa~ re~cted. ~;
~ he whit~, al~ar roactlon produ~t, ~ter ~A
~eparation to 1.8 wt.~, ~how~d the ~ollowing analyti~al value~
Freo gluco~s c 1 ~t.~ :
Monoqluoo~lde ~C12 I C14) 53~2 wt-~
Compa~l~on ~ pl~ 3
~hi~ exa~ple was p~rform~ analo~ou~ly to ~xampl~
1 with th~ ~xc~pt1on that a catalyst aoco~lrg to tha
prior Art
(p-toluonesul~onic Acld) wa~ u~c~.
For 9~ gluco~ reaation, however, 180 ~lnut~ wa~
r~qulr~ ln thi~ ca~e, ~n oth~r wo~ thr~e times that
required ~or tho aatalyst~ a~cord~ng to th~ lnvention.
~ho raw product wa~ ghtly cloudy und beige in
oolor~ a~ter ~ ~parat~en of the gurplu~ FA to 1.4% it
8howea the follow~ng ~alue~:
Fr~ gluaoso: c 1 wt,%
Monogluco~id~ ~Clz ~ Cl4):4~.8 wt-&
.
