United S ta tes Pa tent [ 1 9 ]

Wiener et : 1 1 .
4 , 6 1 7 , 4 1 9
O c t. 1 4 , 1 9 8 6
[ 1 1 ] Pa tent Number:
[ 4 5 ] Da te o f Pa tent:
[ 5 4 ] PRO CES S FO R PREPARING NATURAL
BENZALDEHYDE AND ACETALDEHYDE,
NATURAL BENZALDEHYDE AND
ACETALDEHYDE CO MPO S ITIO NS ,
PRO DUCTS PRO DUCED THEREBY AND
O RGANO LEPTIC UTILITIES THEREFO R
[ 7 5 ] Inv ento rs : Ch a rl es Wiener, Middl eto w n; Al a n
0 . Pittet, Atl a ntic Hig h l a nds , bo th o f
NJ.
Interna tio na l Fl a v o rs & Fra g ra nc es
Inc . , New Yo rk , NY.
[ 2 1 ] Ap p l . No . : 7 8 0 , 2 9 8
[ 2 2 ] Fil ed: S ep . 2 6 , 1 9 8 5
[ 5 1 ] Int. Cl . 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . c 0 7 0 4 5 /7 2
[ 5 2 ] U. S . c 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 6 8 /4 6 4 ; 5 6 8 /4 5 8 ;
5 6 8 /4 6 1 ; 5 6 8 /4 6 3
[ 5 8 ] Fiel d O f S ea rc h . . . . . . . . . . . . . . . 5 6 8 /4 6 1 , 4 6 3 , 4 6 4 , 4 5 8 ,
5 6 8 /4 5 0
[ 7 3 ] As s ig nee:
[ 5 6 ] Ref erenc es Cited
U. S . PATENT DO CUMENTS
1 , 4 1 6 , 1 2 8 5 /1 9 2 2 S c o tt et a l . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2 6 /4 4
O THER PUBLICATIO NS
Bedo uk ia n, Perf umery a nd Fl a v o ring S y nth es is , 2 nd
Ed. , ( 1 9 6 7 ) , p p . 9 1 , 9 2 a nd 9 7 , El s ev ic Pub. Co .
Ho c k enh a l l , Bio c h em. 1 . , v o l . 5 0 , p p . 6 0 5 - 6 0 9 ( 1 9 5 2 ) .
Ha l p in, Bio c h emis try , v o l . 2 0 , p p . 1 5 2 5 - 1 5 3 3 .
Reev e et a 1 , TAPPI , v o l . 4 8 ( 2 ) , 1 9 6 5 , p p . 1 2 1 et s eq .
Prima ry Exa miner- Werren B. Lo ne
Atto rney , Ag ent, o r Firm- Arth ur L. Liberma n
[ 5 7 ] ABS TRACT
Des c ribed is a p ro c es s f o r p rep a ring na tura l benz a l de
h y de a nd a c eta l deh y de a nd c o mp o s itio ns o f ma tter
c o nta ining na tura l benz a l deh y de a nd a c eta l deh y de a s
w el l a s p ro duc ts p ro duc ed th ereby a nd o rg a no l ep tic
util ities th eref o r, w h ic h p ro c es s c o mp ris es th e s tep o f
c o nta c ting w ith ba s e na tura l l y o c c urring c inna ma l de
h y de o r a na tura l p ro duc t ric h in c inna ma l deh y de s uc h
a s Cey l o n o il o f c inna mo n, Cey l o n c inna mo n ba rk ,
S a ig o n c inna mo n ba rk , c a s s ia o il , Cey l o n c inna mo n
q uil l s , c inna mo n l ea f o il , o il o f c inna mo n Ma da g a s c a r o r
th e l ik e a c c o rding to th e rea c tio n:
th e rea c tio n ta k ing p l a c e in th e a bs enc e o f a ny o th er
rea g ents exc ep t inert s o l v ent.
0 0
l l
[ BAS E] 5 @/\H +
8 Cl a ims , 1 4 Dra w ing Fig ures
GC- l R S PECTRUM FO R EX AMPLE I.
US . Pa tent O c t. 1 4 , 1 9 8 6 S h eet 1 o f 1 0 4 , 6 1 7 , 4 1 9
. H @2 2 5 2 E1 2 3 5 3 ; 5 - 0 0
Q Q JJJ; ,
2 / 2
m H : 2 5 1 2 2 : 2 5 2 - 3
m @j : _ 1 a
4 ,
w d u m
m a / 2 \.
0 1 ,
M,
a O
m m
a . . .
m N O _ n_
s U
v U. S . Pa tent 0 m. 1 4 , 1 9 8 6 S h eet3 o f l 0 4 , 6 1 7 , 4 1 9
. Hm @2 2 5 3 5 : 2 3 : 3 ; 2 . 3
3
ii]
_ _ , . i1
MG;
US . Pa tent O c t. 1 4 , 1 9 8 6 S h eet4 0 f l 0 4 , 6 1 7 , 4 1 9
0 5
F 6 . 4
4 . .
9 1 ,
F| G. 5
U. S . Pa tent O c t. 1 4 , 1 9 8 6 S h eet 5 o f 1 0
4 , 6 1 7 , 4 1 9
2 0 1 5
2 0 1 4
F| G. 6
2 0 I3
2 0 H
2 0 0 2
2 0 I2
2 0 0 3
[ 1 7 7 7 /
I U. S . Pa tent O c t. 1 4 , 1 9 8 6 S h eetS o f l O 4 , 6 1 7 , 4 1 9
. Hmm @5 2 5 3 E: M3 1 2 : 0 . ;
. Q MEEZ E: 5 : 2 3 0 . 5
2 5 /
m. 0 _ n_
o ; 0 3
I US . Pa tent O c t. 1 4 , 1 9 8 6 S h eet9 o f l 0 4 , 6 1 7 , 4 1 9
. Q @1 2 5 3 E 5 : 2 3 0 3
Q M @3 2 5 3 E: S E3 : : 0
7 . ,
J
US . Pa tent O c t. 1 4 , 1 9 8 6 S h eet 1 0 o f l O 4 , 6 1 7 , 4 1 9
M3 1 2 5 ; E: E2
0 3 c o m c o m 0 2 S N O 2 O 2
_ r_ _ _ _ _ F_ _ _ _ _ _ _ _ _ _ b_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
4 l < 1 4
3 % ; w : - 3 o n o
. m2 -
\ |
NE _ . -
3 @
- - _ _ _ _ _ _ _ _ _ _ - _ - _ - _ _ _ _ _ _ _ _ _ _ - _ - _ _ _ _ _ _ _ - _ _ _ _ _ _ _ - _ - - 4 _ _ - _ _ _ , _ _ _ _ _ - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ d
ENE # 0 6 : O V HQ mm : w o um o v um mmnv EN 5 6
o 2
4 , 6 1 7 , 4 1 9
1
PRO CES S FO R PREPARING NATURAL
BENZALDEHYDE AND ACETALDEHYDE,
NATURAL BENZALDEHYDE AND
ACETALDEHYDE CO MPO S ITIO NS , PRO DUCTS 5
PRO DUCED THEREBY AND O RGANO LEPTIC
UTILITIES THEREFO R
BACKGRO UND O F THE INV ENTIO N
A ma jo r us e o f na tura l benz a l deh y de is a s a n ing redi
ent in na tura l c h erry ?a v o r a nd o th er ?a v o rs f o r
a ug menting o r enh a nc ing th e a ro ma o r ta s te o f c o ns um
a bl e ma teria l s inc l uding f o o ds tuf f s , c h ew ing g ums , me
dic ina l p ro duc ts , to o th p a s tes , c h ew ing to ba c c o , s mo k - 1 5
ing to ba c c o a nd s mo k ing to ba c c o a rtic l es .
A ma jo r us e o f na tura l a c eta l deh y de is a s a n ing redi
ent in na tura l o ra ng e ?a v o r a nd o th er ?a v o rs f o r
a ug menting o r enh a nc ing th e a ro ma o r ta s te o f c o ns um
a bl e ma teria l s inc l uding f o o ds tuf f s , c h ew ing g ums , me
dic ina l p ro duc ts , to o th p a s tes a nd c h ew ing to ba c c o .
Na tura l benz a l deh y de h a s been us ed in na tura l c h erry
?a v o rs in th e f o rm o f a n a p ric o t k ernel deriv a tiv e a s is
ta ug h t in US . Let. Pa t. No . 1 , 4 1 6 , 1 2 8 is s ued o n Ma y 1 6 ,
1 9 2 2 . An undes ira bl e f ea ture o f th e k no w n p ro c es s es f o r
p rep a ring na tura l benz a l deh y de f ro m a p ric o t k ernel s o r
reg ro und p res s c a k e is th a t a l o ng w ith th e benz a l de
h y de, to xic h y dro c y a nic a c id is p ro duc ed w h ic h mus t
be s ep a ra ted c o mp l etel y f ro m th e benz a l deh y de a nd
f ro m th e res t o f th e o il p rio r to us e. O th er tec h niq ues f o r
p ro duc ing na tura l benz a l deh y de a re k no w n but th es e
tec h niq ues p ro duc e it in s uc h y iel ds a s to c a us e th e
res ul ting p ro c es s to be unec o no mic a l . Fo r exa mp l e,
Ho c k enh ul l , et a l , Bio c h em. J. , 5 0 , 6 0 5 - 9 , ( 1 9 5 2 ) ( Titl e:
O xida tio n o f Ph eny l a c etic Ac id by Penic il l ium c h rjv s o
g enum ) dis c l o s es p ro duc tio n o f benz a l deh y de s ta rting
w ith Ph eny l a c etic a c id th ro ug h eith er benz y l a l c o h o l o r
ma ndel ic a c id v ia th e s eq uenc es :
D- [ a - 1 3 C] ma ndel a te
[ a - 1 3 C] benz o y l f o rma te
2 0
2
Ph . Cl - l 2 . CO O H
+ 0 p h eny l a c etic a c id
l - l 2 O + 0
CO 2
Ph . CH2 O H & Ph . CI- IO H. CO O H
benz y l a l c o h o l ma ndel ic a c id
_ } 1 2
_ c ( ) H
_ H2 2 2
- CO
>Ph . CHO ( 2 Ph . CO . CO O l - [
benz a l deh y de benz o y l f o rmic a c id.
To w ers , et a 1 , Ca n. J. Zo o l . 1 9 7 2 , 5 0 ( 7 ) , 1 0 4 7 - 5 0
( Def ens iv e s ec retio nz bio s y nth es is o f h y dro g en c y a nide
a nd benz a l deh y de f ro m p h eny l a l a nine by a mil l ip ede )
dis c l o s es a bio s y nth etic p a th w a y f o r th e p ro duc tio n o f
benz a l deh y de f ro m dieta ry p h eny l a l a nine in O xidus
g ra eil is th us l y :
O O H
I!
O H CE N
NH; 5
Ha l p in, et a l , Bio c h emis try , 1 9 8 1 , V o l ume 2 0 , p a g es
1 5 2 5 - 1 5 3 3 ( Titl e: Ca rbo n- 1 3 Nuc l ea r Ma g netic Res o
na nc e S tudies o f Ma ndel a te Meta bo l is m in Wh o l e Ba c =
teria l Cel l s a nd in Is o l a ted, in V iv o Cro s s - Link ed En~
z y me Co mp l exes ) dis c l o s es th e bio c h emic a l p a th w a y
f ro m ma ndel a te io n to benz a l deh y de, th us l y :
ma ndel a te III ( L) - ma ndel a te
ra c ema s e > 1 3 C_ CO 2 deh dro ena s e
c l a n
L- [ a - l 3 C] ma ndel a te
? benz o y l f o r- ma te f ! )
1 3 c _ c O 2 _ dec a rbo xy l a s e ; 1 3 C_ H
{ a - uq benz a l deh y de
benz a l deh y de
deh y dro g ena s e
@ic nz o n.
[ a - 1 3 C] benz y 1 a l c o h o l
Reev es , et a l , TAPPI 4 8 ( 2 ) , p a g es 1 2 1 - 5 , ( 1 9 6 5 ) ( T i
, , tl e: Rea c tio n Pro duc ts Fo rmed Up o n th e Al k a l ine
6 5 Pero xide O xida tio n o f Lig nin- Rel a ted Mo del Co m
p o unds ) dis c l o s es th e ef f ec t o f a l k a l ine h y dro g en p er
o xide o xida tio n o n c inna ma l deh y de w h ereby th e c in
na ma l deh y de is s p l it a t th e do ubl e bo nd w ith th e f o rma
4 , 6 1 7 , 4 1 9
3
tio n o f th e c o rres p o nding benz a l deh y de a nd benz o ic
a c id a c c o rding to th e rea c tio n:
0 5
l l
II E ) 1 0
@MH
At p a g e 1 2 4 , c o l umn' l , p a ra g ra p h 1 , Reev es , et a l
th eo riz es th a t a rev ers e a l do l rea c tio n is no t res p o ns i
bl e f o r th e f o rma tio n o f v era tra l deh y de due to th e f a c t
th a t a c eta l deh y de th e o th er p ro duc t o f th e p o tentia l
rev ers e a l do l rea c tio n w a s no t o bta ined. Th eref o re,
o ur dis c o v ery o f th e retro - a l do l rea c tio n ta k ing p l a c e,
to Wit:
: H: o ii
+ [ BAS E]
2 0
2 5
3 0
w a s unexp ec ted a nd uno bv io us . Th e retro - a l do l rea c
tio n, to w it:
W
indeed, to o k p l a c e due to th e dif f erent rea c tio n c o ndi
tio ns f ro m th o s e p ro p o s ed a nd s et f o rth in Reev es , et a 1 ;
dif f erent ins o f a r a s temp era ture o f rea c tio n a nd time o f 4 5
rea c tio n a re c o nc erned; l o ng er times o f rea c tio n a nd
h ig h er temp era tures o f rea c tio n being th e c o nditio ns in
o ur retro - a l do l rea c tio n a s o p p o s ed to s h o rter times
o f rea c tio n a nd l o w er temp era tures ins o f a r a s th e
Reev es , et a l rea c tio n is c o nc erned.
In o ur o w n inv entio n, no rea g ents o th er th a n ba s e a nd
na tura l l y o c c urring c inna ma l deh y de a nd s o l v ent a re
util iz ed to c a rry o ut th e retro - a l do l rea c tio n o f o ur
inv entio n, to w it:
( 3 /) o
H To BAS E u
+ O [ A /\H +
Th e p ro c es s o f o ur inv entio nth us g iv es ris e to uno b
v io us , unexp ec ted a nd a dv a nta g eo us res ul ts a nd rep re
s ents a n a dv a nc e in th e a rt in th e p ro duc tio n o f na tu
ra l benz a l deh y de ta k en a l o ne o r in c o mbina tio n w ith
5 0
5 5
6 5
4
na tura l c inna ma l deh y de; a nd, f urth er, in th e p ro duc tio n
o f na tura a c eta l deh y de.
S UMMARY O F THE INV ENTIO N
O ur inv entio n is direc ted to th e p ro duc tio n o f na tu
ra l benz a l deh y de a nd/o r na tura l a c eta l deh y de ta k en
a l o ne o r in a dmixture w ith na tura l c inna ma l deh y de
a c c o rding to a rea c tio n w h ere na tura l c inna ma l de
h y de is s ubjec t to a retro - a l do l rea c tio n, th us l y :
( 3 /?
O O
H o [ BAS E] H /H\
+ h ) _ _ _ _ _ _ > @/\H + n.
Wii
Th e c inna ma l deh y de rea c ta nt ma y o c c ur in eith er th e
c is f o rm h a v ing th e s truc ture:
\
H O
a nd/ o r th e tra ns f o rm h a v ing th e s truc ture:
Th e c inna ma l deh y de ma y be in rec o v ered f o rm f ro m
na tura l s o urc es a s by dis til l a tio n o r extra c tio n o r th e
c inna ma l deh y de ma y exis t in its na tura l s ta te immedi
a tel y p rio r to th e rea c tio n, th us l y :
( i) O il o f Cinna mo n Cey l o n;
( ii) Cey l o n Cinna mo n Ba rk ( Cinna mo mum z ey l a ni
c um Nees ex Bl ume ( f a m. La ura c ea e) ) ;
( iii) Th e Ba rk o f S a ig o n Cinna mo n ( Cinna mo mum
Io ureirii Nees ( f a m. La ura c ea e) ;
( iv ) Th e Ba rk o f Ca s s ia c inna mo n ( ex Cinna mo mum
c a s s ia ( Nees ) ) Nees ex Bl ume ( f a m. La ura c ea e) ;
( v ) Th e Ba rk o f S a ig o n c inna mo n;
( v i) O il o f Cinna mo n Ba rk Cey l o n;
( v ii) Q uil l s f ro m Cey l o n c inna mo n ( inc l uding
?nes , Ba rc el o na a nd Ha mburg ) ;
( v iii) Cey l o n c inna mo n q uil l ing s a nd f ea th ering s ;
( ix) Cey l o n c inna mo n c h ip s ;
( x) Cey l o n c inna mo n ba rk o il ;
( xi) O il o f c inna mo n S ey c h el l es ;
( xii) O il o f c inna mo n Ma da g a s c a r;
( xiii) Lea v es o f Ca s s ia ;
( xiv ) Ca s s ia Ba rk ( Ca s s ia l ig nea ) in g ro und o r p o w
dered f o rm;
( xv ) O il o f Ca s s ia .
Th us , th e c inna ma l deh y de s o urc e ma y be trea ted w ith a
ba s e s uc h a s s o dium bic a rbo na te, p o ta s s ium bic a rbo n
a te, s o dium c a rbo na te, p o ta s s ium c a rbo na te, l ith ium
c a rbo na te, l ith ium bic a rbo na te, ma g nes ium h y ro xide,
c a l c ium h y dro xide, c a l c ium c a rbo na te, p ro l ine h a v ing
th e s truc ture:
4 , 6 1 7 , 4 1 9
N
MO ,
c h o l ine h a v ing th e s truc ture:
I
H0
o r a na tura l c h o l ine s o urc e s uc h a s na tura l l ec ith in h a v
ing th e s truc ture:
l l
CHr- O C- R
0
l l
CH- O - C- R'
0 CH3
in th e p res enc e o f ba s e ( w h erein th e res idues :
rep res ent p a l mito y l , s tea ro y l , o l ey l , l ino l ey l , l ino l eny l
a nd C2 0 - C2 2 a c id res idues ) [ exa mp l es o f na tura l l y o c
c urring l ec ith in a re s o y bea n l ec ith in ( ref erenc e: S o y
bea ns , V o l ume II, ( Inters c ienc e Publ is h ing Co mp a ny ,
New Yo rk , 1 9 5 1 ) , p a g es 5 9 3 6 4 7 a nd na tura l p h o s p h a
tide l ec ith in] w h ereby a retro - a l s l o rea c tio n
ta k es p l a c e, th us l y :
A req uirement o f o ur inv entio n is th a t no o th er rea
g ents be p res ent w h ic h w o ul d c a us e th e rea c tio n to g iv e
ris e to a c o mp o s itio n c o nta ining benz a l deh y de o r a c et
a l deh y de w h ic h c a nno t be des c ribed a s na tura . Th us ,
th e us e o f s ubs ta nc es s uc h a s h y dro g en p ero xide a nd/ o r
s o dium h y dro xide in th e rea c tio n ma s s w o ul d g iv e ris e
to a ma teria l no t c o ntemp l a ted w ith in th e s c o p e o f o ur
inv entio n.
Th us , o ur inv entio n s p ec i?c a l l y is intended to ex
c l ude p ro c es s es s uc h a s th o s e o f th e p rio r a rt, f o r exa m
p l e, Reev es , et a 1 , TAPPI, 4 8 ( 2 ) , 1 2 1 - 5 , ( 1 9 6 5 ) w h ic h
dis c l o s es th e rea c tio n:
0 0
l l
[ BAS E] ; @/\H +
2 0
2 5
3 0
4 5
5 5
6 5
Th e rea c tio n o f o ur inv entio n, to w it:
( CD/3
\ o
+ H
ma y be c a rried o ut in a s ta nda rd rea c tio n v es s el p ref era
bl y a t re?ux c o nditio ns ( p ref era bl y w h en th e c in
na ma l deh y de- bea ring rea c ta nt is in th e l iq uid p h a s e,
e. g . , c inna mo n o il o r c a s s ia o il ) ; o r it ma y be c a rried o ut
in s o l id- l iq uid p h a s e rea c tio n eq uip ment, e. g . , S o xh
l et - ty p e eq uip ment ( p ref era bl y w h en th e c inna ma l de
h y de- bea ring rea c ta nt is in th e s o l id p h a s e) . Th us , th e
rea c tio n o f o ur inv entio n ma y be c a rried o ut in a S o xh ~
l et extra c tio n v es s el w ith th e a c tua l rea c tio n ta k ing
p l a c e in th e S o xh l et th imbl e a s mo re s p ec i?c a l l y de
s c ribed, inf ra , o r th e rea c tio n o f o ur inv entio n ma y be
c a rried o ut in a S o xh l et extra c tio n v es s el w ith th e
a c tua l rea c tio n ta k ing p l a c e in th e rebo il er ?a s k o r v es
s el . Th e c a s e w h ere th e rea c tio n ta k es p l a c e in th e
S o xh l et th imbl e o c c urs w h en, f o r exa mp l e, p ul v er
iz ed c inna mo n ba rk o f o ne o f th e a bo v e ty p es is inti
ma tel y a dmixed w ith l ime o r ma g nes ium h y dro xide o r
th e l ik e a nd th e res ul ting s o l id mixture is p l a c ed in th e
S o xh l et th imbl e.
In a ny c a s e, th e rea c tio n ma y ta k e p a l c e in th e p res
enc e o f ( i) C1 - C5 a l c o h o l s , ( ii) w a ter, o r ( iii) a q ueo us
mixtures o f C1 - C5 a l c o h o l s a nd w a ter. Exa mp l es o f
C1 - C5 a l c o h o l s a re meth a no l , eth y l a l c o h o l , is o p ro p y l
a l c o h o l , n- p ro p y l a l c o h o l , n- buta no l , s ec o nda ry buta
no l , tertia ry buta no l , n- a my l a l c o h o l , t- a my l a l c o h o l a nd
is o buta no l . Th e w eig h t ra tio o f a l c o h o l z w a ter w h en a n
a l c o h o l ic s o l utio n is us ed, ma y v a ry , a nd is p ref era bl y
f ro m a bo ut 6 p a rts a l c o h o l : 4 p a rts w a ter ( by w eig h t) up
to a bo ut 1 p a rt a l c o h o l : a bo ut 1 0 p a rts w a ter ( by
w eig h t) .
Th e rea c tio n is c a rried o ut a t temp era tures s uc h th a t
a c eta l deh y de a nd benz a l deh y de a re remo v ed f ro m th e
rea c tio n ma s s a s th ey a re f o rmed th ereby ?a v o ring th e'
retro - a l do l rea c tio n. Henc e, temp era tures s ubs ta n
tia l l y g rea ter th a n th e bo il ing p o int o f a c eta l deh y de a re
to be us ed. Th e bo il ing p o int o f a c eta l deh y de is 2 1 C. a t
a tmo s p h eric p res s ure. Pres s ures o f f ro m a bo ut 0 . 2 a tmo
s p h eres up to a bo ut 1 0 a tmo s p h eres ma y be us ed in
c a rry ing o ut th is rea c tio n. Th us , f o r exa mp l e, re?uxing
w a ter a t 1 a tmo s p h ere g iv es ris e to a rea c tio n temp era
ture o f a bo ut 9 0 C. w h erea s re?uxing 5 0 : 5 0 eth a no l z w a
ter a t a tmo s p h eric p res s ure g iv es ris e to a rea c tio n tem
p era ture o f a bo ut 8 0 C. Th e rea c tio n temp era ture ma y
th us v a ry f ro m a bo ut 4 0 Cup to a bo ut 1 5 0 C. Th e
rea c tio n p res s ure ma y th us v a ry f ro m a bo ut 0 . 2 a tmo ~
4 , 6 1 7 , 4 1 9
7
s p h eres up to a bo ut 1 0 a tmo s p h eres . Th e rea c tio n time
ma y v a ry f ro m a bo ut 5 h o urs up to a bo ut 8 0 h o urs . Th e
l o ng er th e rea c tio n time, th e g rea ter th e deg ree o f
c o mp l etio n o f th e rea c tio n ( g iv ing ris e to a g rea ter
ra tio o f benz a l deh y de: c inna ma l deh y de in th e ?na l p ro d
uc t) . Th e s h o rter th e p erio d o f rea c tio n time th e h ig h er
th e temp era ture req uired in o rder to s ubs ta ntia l l y c o m
p l ete th e rea c tio n ( w h ereby th e w eig h t p erc ent o f
benz a l deh y de in th e rea c tio n ma s s is g rea ter th a n a bo ut
4 0 % ) .
Th us , w ith in th e mea ning o f o ur s p ec i?c a tio n, th e
term c o mp l etio n o f rea c tio n mea ns th e f o rma tio n in
th e rea c tio n ma s s o f a t l ea s t a 1 0 % y iel d o f na tura l
benz a l deh y de a nd a 1 0 % y iel d o f a c eta l deh y de up to
a bo ut a 9 5 % y iel d o f na tura l benz a l deh y de a nd a 9 5 %
y iel d o f na tura l a c eta l deh y de. Ca rry ing o ut o ur p ro
c es s in o rder to y iel d l es s th a n 1 0 % o f benz a l deh y de o r
a c eta l deh y de o r g rea ter th a n 9 5 % y iel d o f benz a l de
h y de o r a c eta l deh y de bec o mes unec o no mic a l a nd is no t
c o ntemp l a ted w ith in th e s c o p e o f o ur inv entio n.
Wh en us ing a s a s o urc e o f c inna ma l deh y de o ne o r
bo th o f th e c o mp o unds h a v ing th e s truc tures :
2 5
a nd
H 3 0
c inna mo n o il o r o il o f c a s s ia o il , th e c inna mo n o il o r o il
o f c a s s ia is a dmixed w ith w a ter o r a C1 - C5 a l c o h o l o r a
mixture o f w a ter a nd a C1 - C5 l o w er a l k a no l a s w el l a s
th e ba s e, e. g . , s o dium c a rbo na te, s o dium bic a rbo na te,
p o ta s s ium c a rbo na te, p o ta s s ium bic a rbo na te, l ith ium
c a rbo na te, l ith ium bic a rbo na te, c a l c ium h y dro xide, c a l
c ium c a rbo na te, ma g nes ium h y dro xide, ma g nes ium
c a rbo na te, p ro l ine h a v ing th e s truc ture:
N
@0 1 1
c h o l ine h a v ing th e s truc ture:
4 0
4 5
5 0
1
H0
o r a l ec ith in- ba s e mixture w ith th e l ec ith in h a v ing th e 5 5
s truc ture:
w h erein th e mo ieties :
a re de?ned, s up ra , th e rea c tio n mixture is th en re?uxed
o r h ea ted f o r a p erio d o f betw een a bo ut 5 h o urs a nd
a bo ut 8 0 h o urs . During th e rea c tio n, it is des ira bl e to
remo v e th e benz a l deh y de- ric h rea c tio n p ro duc t a s it is
f o rmed. Henc e, th e benz a l deh y de- ric h rea c tio n p ro duc t
ma y be remo v ed o v erh ea d th ro ug h a p a c k ed v ertic a l
re?ux c o l umn c o nnec ted to a c o o l ing h ea t exc h a ng er a s
il l us tra ted in FIGS . 7 A, 7 B o r 7 C, inf ra . Th e p ro duc t
th us o bta ined exis ts in tw o p h a s es ; a n up p er a q ueo us
p h a s e a nd a l o w er mo re dens e benz a l deh y de- ric h p h a s e
w h ic h c a n be s ep a ra ted f ro m ea c h o th er us ing a p h a s e
s p l itter; o r th e benz a l deh y de- ric h p h a s e is s ep a ra ted
f ro m th e a q ueo us p h a s e, f o r exa mp l e, by s o l v ent extra c
tio n us ing s uc h s o l v ents a s dieth y l eth er, dimeth y l eth er,
h y dro c a rbo ns o r meth y l ene dic h l o ride, a nd th e h en
z a l deh y de- ric h p h a s e ma y th en be f ra c tio na l l y dis til l ed.
Th e a c eta l deh y de ma y be s ep a ra ted f ro m th e benz a l de
h y de by mea ns o f th e us e o f h ig h ef ?c ienc y f ra c tio n
a tio n c o l umn a nd c o o l ing h ea t exc h a ng er. As w il l be
s een in FIG. 7 A, th e a c eta l deh y de ma y be s ep a ra ted by
tra p p ing s a id a c eta l deh y de in a c o l d tra p .
Th us , a t th e end o f th e rea c tio n o r a t th e end o f th e
des ired time p erio d f o r p ro c eeding w ith th e rea c tio n,
th e na tura l benz a l deh y de a nd na tura l a c eta l deh y de
a re f ra c tio na l l y dis til l ed y iel ding mixtures ric h in na tu
ra l benz a l deh y de a nd/o r a c eta l deh y de. Th e benz a l de
h y de- ric h f ra c tio n a l s o ma y c o nta in a c o ns idera bl e p ro
p o rtio n o f unrea c ted c inna ma l deh y de. Th is res ul ting
p ro duc t ma y , if des ired, be a g a in f ra c tio na l l y dis til l ed in
o rder to enric h th e benz a l deh y de s trea m. Fro m a p ra c ti
c a l s ta ndp o int s uc h a mixture o f c inna ma l deh y de a nd
benz a l deh y de p ro duc ed a c c o rding to th e ?rs t f ra c tio na l
dis til l a tio n is us ua l l y a deq ua te f o r us e in f o o d ?a v o rs ,
f o r exa mp l e, o r in to ba c c o ?a v o rs , f o r exa mp l e.
No rma l l y , but no t nec es s a ril y , th e a c eta l deh y de is
p rep a red f ree o f a ro ma tic a l deh y des f o r us e in f o o d
?a v o rs .
Fro m a p ra c tic a l s ta ndp o int, th e mixtures o f a c eta l de
h y de, benz a l deh y de a nd c inna ma l deh y de th us p ro
duc ed h a v e uno bv io us , unexp ec ted a nd a dv a nta g eo us
p ro p erties f o r a ug menting o r enh a nc ing th e a ro ma o r
ta s te o f c o ns uma bl e ma teria l s inc l uding but no t l imited
to f o o ds tuf f s , c h ew ing g ums , medic ina l p ro duc ts , to o th
p a s tes , c h ew ing to ba c c o s , s mo k ing to ba c c o a nd s mo k
ing to ba c c o a rtic l es , p a rtic ul a rl y a l mo nd, o ra ng e a nd
c h erry ?a v o red f o o ds tuf f s a nd medic ina l p ro duc ts .
Th e ra ng e o f mo l e ra tio o f ba s e to c inna ma l deh y de
( c o nta ined in th e c inna ma l deh y de- bea ring na tura l s ub
s ta nc e, e. g . , c a s s ia o il , c inna mo n ba rk , c inna mo n l ea f
a nd th e l ik e) ma y v a ry f ro m a bo ut 0 . 1 : 1 up to a bo ut 4 : 1 .
Th is mo l e ra tio is ba s ed up o n th e f o l l o w ing :
( a ) Wh eth er th e rea c tio n is c a rried o ut o n a s o l id
c o nta ining th e c inna ma l deh y de s uc h a s p ul v eriz ed
c inna mo n ba rk o r in a dmixture w ith a ba s e s uc h a s
ma g nes ium h y dro xide ( in w h ic h c a s e th e h ig h er
end o f th e ra ng e o f mo l e ra tio s is a p p l ic a bl e) ; o r
w h eth er th e rea c tio n is a l iq uid p h a s e rea c tio n
c a rried o ut in th e p res enc e o f a ba s e s uc h a s c h o
l ine, p ro l ine o r a q ueo us s o dium bic a rbo na te w ith
c inna mo n o il a nd w a ter, a l c o h o l o r a n a q ueo us
4 , 6 1 7 , 4 1 9
9
a l c o h o l mixture ( in w h ic h c a s e th e mo l e ra tio o f
ba s e: c inna ma l deh y de is a t th e l o w er end o f th e
a bo v e- mentio ned ra ng e;
( b) Th e na ture o f th e to ta l energ y inp ut to th e rea c
tio n; ba s ed up o n h ea t inp ut a nd time o f rea c tio n a s
w el l a s temp era ture a nd p res s ure o f rea c tio n ( th us ,
a rel a tiv el y l o ng time o f rea c tio n, e. g . , 8 0 h o urs ,
w il l g iv e ris e to a h ig h er y iel d o f benz a l deh y de
a nd a c eta l deh y de a nd a l o w er c o nc entra tio n o f
c inna ma l deh y de in th e rea c tio n p ro duc t) . Dep end
ing up o n th e ?a v o ris t s req uirements , it ma y be
des ira bl e to c rea te a n ul tima te c o mp o s itio n c o n
ta ining , f o r exa mp l e, g rea ter th a n 8 0 % benz a l de
h y de o r a 5 0 : 5 0 mixture o f benz a l deh y de a nd c in
na ma l deh y de o r s ubs ta ntia l l y p ure a c eta l deh y de
( h a v ing p res ent th erew ith mino r q ua ntities o f o th er
l o w bo il ing c o mp o nents s uc h a s c ro to na l deh y de
a nd a c etic a c id) ; a nd
( c ) Th e p a rtic l e s iz e ( w h ere a p p l ic a bl e) o f th e s o l id
s o urc e o f c inna ma l deh y de, e. g . , p ul v eriz ed c inna
mo n ba rk o r p ul v eriz ed h ig h c inna ma l deh y de- c o n
ta ining c inna mo n l ea f . A s ma l l p a rtic l e s iz e w il l
g iv e ris e to a f a s ter c o nv ers io n o f c inna ma l deh y de
( c o nta ined in th e s o l id c inna ma l deh y de- bea ring
s o urc e) to benz a l deh y de a nd a c eta l deh y de.
In a l l c a s es , o ur inv entio n is c a p a bl e o f y iel ding in a
c o ntro l l a bl e f a s h io n des ired ra tio s o f benz a l deh y de a nd
a c eta l deh y de to c inna ma l deh y de dep ending up o n th e
rea c tio n c o nditio ns emp l o y ed.
Th e rea c tio n p ro duc t c o nta ining th e c inna ma l de
h y de, benz a l deh y de a nd a c eta l deh y de p ro duc ed a c
c o rding to th e rea c tio n:
0
l l
/\\/\H
ma y be c o ns idered a s a na tura l p ro duc t. Th is na tu
ra l p ro duc t ma y be us ed a s is o r it ma y p ref era bl y be
p h y s ic a l l y p uri?ed by s uc h meth o ds a s f ra c tio na l dis til
l a tio n a nd/o r p rep a ra tiv e c h ro ma to g ra p h y . Th e res ul t
ing na tura l p ro duc ts w il l h a v e no v el util ities in a ug
menting o r enh a nc ing th e a ro ma o r ta s te o f c o ns uma bl e
ma teria l s inc l uding but no t l imited to f o o ds tuf f s , c h ew
ing g ums , medic ina l p ro duc ts , to o th p a s tes , c h ew ing
to ba c c o s a nd s mo k ing to ba c c o s p a rtic ul a rl y c h erry
?a v o red, o ra ng e ?a v o red, a l mo nd ?a v o red f o o ds tuf f s
a nd medic ina l p ro duc ts . Ac c o rding l y , f o r exa mp l e,
c o mp o s itio ns o f ma tter c o nta ining mo l e ra tio s o f f ro m
a bo ut 1 0 : 9 0 up to a bo ut 9 9 . 9 : O . l o f benz a l deh y de: c in
na ma l deh y de in th eir na tura l s ta te p rep a red a c c o rding
to th e rea c tio n:
( GAD
H % o
+
0
l l
@N\H
ma y be util iz ed in s uc h c o ns uma bl e ma teria l s , e. g . , f o o d
s tuf f s a s , f o r exa mp l e, ma c a ro o n c o o k ies , ma ra s c h ino
O
2 0
4 5
6 0
6 5
1 0
c h erries , c h erry ?a v o red bev era g es s uc h a s c a rbo na ted
c h erry drink s , a nd th e l ik e.
Furth ermo re, s ubs ta ntia l l y p ure a c eta l deh y de c o n
ta ining mino r a mo unts o f imp urities ma y be util iz ed in
s uc h c o ns uma bl e ma teria l s , e. g . , f o o ds tuf f s s uc h a s
o ra ng e drink s .
Co l l ec tiv el y , th es e a f o rementio ned benz a l deh y de,
c inna ma l deh y de a nd a c eta l deh y de- c o nta ining p ro duc ts
o f o ur inv entio n a re h ereina f ter c a l l ed a l deh y de- c o n
ta ining c o mp o s itio ns .
Th e no v el p ro duc ts o f o ur inv entio n ma y be util iz ed
in f o o ds tuf f s a nd bev era g es in a n a mo unt o f f ro m a bo ut
0 . 5 p p m up to a bo ut 3 % by w eig h t o f th e res ul ting
f o o ds tuf f o r bev era g e. Th e ma teria l s c a n be us ed in s uc h
h ig h p erc enta g es bec a us e o f th e ma nner in w h ic h th ey
a re p ro duc ed; th a t is , f ree o f a ny nitril e- c o nta ining s ub
s ta nc es a s w o ul d be p res ent if th e a l deh y de- c o nta ining
p ro duc ts w ere p ro duc ed f ro m s uc h ma teria l s a s a p ric o t
k ernel s .
As us ed h erein, th e term f o o ds tuf f inc l udes bo th
s o l id a nd l iq uid ing es tibl e ma teria l s w h ic h us ua l l y do ,
but need no t, h a v e nutritio na l v a l ue. Th us , f o o ds tuf f s
inc l udes s o up s , c o nv enienc e f o o ds , bev era g es , da iry
p ro duc ts , c a ndies , v eg eta bl e c erea l s , s o f t drink s , s na c k s
a nd th e l ik e.
As us ed h erein, th e term medic ina l p ro duc ts in
c l udes bo th s o l ids a nd l iq uids w h ic h a re ing es tibl e no n
to xic ma teria l s w h ic h h a v e medic ina l v a l ue s uc h a s
c o ug h s y rup s , c o ug h dro p s a nd c h ew ing medic ina l
ta bl ets .
Th e term c h ew ing g um is intended h erein to be a
f o o ds tuf f c o mp o s itio n c o mp ris ing a s ubs ta ntia l l y w a ter
ins o l ubl e, c h ew a bl e p l a s tic g um ba s e s uc h a s c h ic l e, o r
s ubs titutes th eref o r, inc l uding jel uto ng , g utta k a y rubber
o r c erta in c o mes tibl e na tura l o r s y nth etic res ins o r
w a xes . Inc o rp o ra ted w ith th e g um ba s e in a dmixture
th erew ith ma y be p l a s tic iz ers o r s o f tening a g ents , e. g . ,
g l y c erine a nd a ?a v o ring c o mp o s itio n w h ic h inc o rp o
ra tes o ne o r mo re o f th e a l deh y de- c o nta ining c o mp o s i
tio ns o f o ur inv entio n a nd, in a dditio n, s w eetening
a g ents w h ic h ma y be s ug a rs , inc l uding s uc ro s e o r dex
tro s e a nd/o r a rti?c ia l s w eeteners s uc h a s c y c l a ma tes o r
s a c c h a rin. O th er o p tio na l ing redients ma y be p res ent.
Th e term a ug ment in its v a rio us f o rms is us ed
h erein to mea n th e s up p l y ing , mo dif y ing o r imp a rting o f
a ?a v o r o r a ro ma c h a ra c teris tic no te o r nua nc e to a n
o th erw is e bl a nd, rel a tiv el y ta s tel es s o r no n~o do ro us
s ubs ta nc e o r mo dif y ing a n exis ting ?a v o r o r a ro ma
c h a ra c teris tic w h ere th e na tura l ?a v o r is def ic ient in
s o me reg a rd, o r s up p l ementing th e exis ting ?a v o r o r
a ro ma imp res s io n to mo dif y its q ua l ity , c h a ra c ter, ta s te
o r a ro ma .
Th e term enh a nc e is us ed h erein to mea n th e inten
s i?c a tio n o f a ?a v o r o r a ro ma c h a ra c teris tic o r no te
w ith o ut th e mo di?c a tio n o f th e q ua l ity th ereo f . Th us ,
enh a nc ement o f a ?a v o r o r a ro ma mea ns th a t th e
enh a nc ement a g ent do es no t a dd a ny a dditio na l ?a v o r
no te o r nua nc e.
S ubs ta nc es s uita bl e f o r us e h erein a s c o - ing redients o r
?a v o ring a djuv a nts a re w el l k no w n in th e a rt f o r s uc h
us e, being extens iv el y des c ribed in th e rel ev a nt l itera
ture. It is req uired th a t a ny s uc h ma teria l be ing es tibl y
a c c ep ta bl e a nd th us no n- to xic o r o th erw is e no n
del eterio us , p a rtic ul a rl y f ro m a n o rg a no l ep tic s ta nd
p o int w h ereby th e ul tima te ?a v o r a nd/o r a ro ma o f th e
c o ns uma bl e ma teria l us ed do es no t c a us e th e c o ns um
a bl e ma teria l to h a v e una c c ep ta bl e a ro ma a nd ta s te
nua nc es .
4 , 6 1 7 , 4 1 9
1 1
It is a f urth er req uirement th a t s uc h ma teria l be o r
g a no l ep tic a l l y c o mp a tibl e w ith th e f o o ds tuf f w ith
w h ic h it is us ed s o th a t th e ?a v o r a nd a ro ma nua nc es o f
s uc h ma teria l , ta k en to g eth er w ith th e ?a v o r a nd a ro ma
nua nc es o f th e f o o ds tuf f ( a s a w h o l e) g iv e ris e to a h a r
mo nio us l y a es th etic a l l y p l ea s ing a ro ma a nd ta s te p ro
?l e. S uc h ma teria l , in g enera l , ma y be c h a ra c teriz ed a s
?a v o ring a djuv a nts o r v eh ic l es c o mp ris ing bro a dl y ,
s ta bil iz ers , th ic k eners , s urf a c e a c tiv e a g ents , c o nditio n
ers , o th er f l a v o ra nts a nd ?a v o r intens i?ers .
S ta bil iz er c o mp o unds inc l ude p res erv a tiv es , e. g . ,
s o dium c h l o ride; a ntio xida nts , e. g . , c a l c ium a nd s o dium
a s c o rba te, a s c o rbic a c id, buty l a ted h y dro xy a nis o l e
( mixture o f 2 - a nd 3 - tertia ry - buty l - 4 - h y dro xy a nis o l e) ,
buty l a ted h y dro xy to l uene ( 2 , 6 - di- tertia ry - buty l - 4
meth y l p h eno l ) , p ro p y l g a l l a te a nd th e l ik e a nd s eq ues
tra nts , e. g . , c itric a c id.
Th ic k ener c o mp o unds inc l ude c a rriers , binders , p ro
tec tiv e c o l l o ids , s us p ending a g ents , emul s i?ers a nd th e
l ik e, e. g . , a g a r a g a r, c a rra g eena n, c el l ul o s e a nd c el l ul o s e
deriv a tiv es s uc h a s c a rbo xy meth y l c el l ul o s e a nd meth y l
c el l ul o s e; na tura l a nd s y nth etic g ums s uc h a s g um a ra
bic , g um tra g a c a nth , g el a tin, p ro teina c eo us ma teria l s ;
l ip ids ; c a rbo h y dra tes ; s ta rc h es , p ec tins a nd emul s i?ers ,
e. g . , mo no - a nd dig l y c erides o f f a tty a c ids , s k im mil k
p o w der, h exo s es , p ento s es , dis a c c h a rides , e. g . , s uc ro s e,
c o rn s y rup a nd th e l ik e.
S urf a c e a c tiv e a g ents inc l ude emul s if y ing a g ents , e. g . ,
f a tty a c ids s uc h a s c a p ric a c id, c a p ry l ic a c id, p a l mitic
a c id, my ris tic a c id a nd th e l ik e, mo no - a nd dig l y c erides
o f f a tty a c ids , l ec ith in, def o a ming a nd ?a v o r dis p ers ing
a g ents s uc h a s s o rbita n mo no s tea ra te, p o ta s s ium s tea
ra te, h y dro g ena ted ta l l o w a l c o h o l a nd th e l ik e.
Co nditio ners inc l ude c o mp o unds s uc h a s bl ea c h ing
a nd ma turing a g ents , e. g . , benz o y l p ero xide, c a l c ium
p ero xide, h y dro g en p ero xide a nd th e l ik e, s ta rc h mo di
?ers s uc h a s p era c etic a c id, s o dium c h l o rite, s o dium
h y p o c h l o rite, p ro p y l ene o xide, s uc c inic a nh y dride a nd
th e l ik e, buf f ers a nd neutra l iz ing a g ents , e. g . , s o dium
a c eta te a mmo nium bic a rbo na te, a mmo nium p h o s p h a te,
c itric a c id, l a c tic a c id, v ineg a r a nd th e l ik e, c o l o ra nts ,
e. g . , c a rminic a c id, c o c h inea l , tumeric a nd c urc umin
a nd th e l ik e, ?rming a g ents s uc h a s a l uminum s o dium
s ul f a te, c a l c ium c h l o ride a nd c a l c ium g y l c o na te, textur
iz ers , a nti- c a k ing a g ents , e. g . , a l uminum c a l c ium s ul f a te
a nd triba s ic c a l c ium p h o s p h a te, enz y mes , y ea s t f o o ds ,
e. g . , c a l c ium l a c ta te a nd c a l c ium s ul f a te, nutrient s up
p l ements , e. g . , iro n s a l ts s uc h a s f erric p h o s p h a te, f er
ro us g l uc o na te a nd th e l ik e, ribo ?a v in, v ita mins , z inc
s o urc es s uc h a s z inc c h l o ride, z inc s ul f a te a nd th e l ik e.
O th er ?a v o ra nts a nd ?a v o r intens i?ers inc l ude o r
g a nic a c ids , e. g . , a c etic a c id, f o rmic a c id, 2 - h exeno ic
a c id, benz o ic a c id, n- buty ric a c id, c a p ro ic a c id, c a p ry l ic
a c id, c inna mic a c id, is o buty ric a c id, is o v a l eric a c id,
a l p h a - meth y l - buty ric a c id, p ro p io nic a c id, v a l eric a c id,
2 - meth y l - 2 - p enteno ic a c id, a nd 2 - meth y l - c is - 3 - p en
teno ic a c id; k eto nes a nd a l deh y des o th er th a n th e a l de
h y des o f th e a l deh y de- c o nta ining c o mp o s itio ns o f o ur
inv entio n, e. g . , a c eto p h eno ne, a c eto ne, a c ety l meth y l
c a rbino l , a c ro l ein, n- buta na l , c ro to na l , dia c ety l , beta ,
beta - dimeth y l - a c ro l ein, n- h exa na l , 2 - h exa na l , c is - 3
h exena l , Z- h ep tena l , 4 - ( p - h y dro xy p h eny l ) - 2 - buta no ne,
a l p h a - io no ne, beta - io no ne, 2 - meth y l - 3 - buta no ne, 2 - p en
ta no ne, 2 - p entena l a nd p ro p a na l ; a l c o h o l s s uc h a s l
buta no l , benz y l a l c o h o l , l - bo rneo l , tra ns - Z- buten- l - o l ,
eth a no l , g era nio l , l - h exa no l , Z- h ep ta no l , tra ns - Z- h ex
eno l - l , c is - 3 - h exen- 1 - o l , 3 - meth y l - 3 - buten- l - o l , l - p en
teno l , l - p enten- 3 - o l , p - h y dro xy p h eny l - Z- eth a no l , is o
1 0
5
2 0
2 5
3 0
3 5
4 0
4 5
6 0
6 5
1 2
a my l a l c o h o l , is o f enc h y l a l c o h o l , p h eny I- Z- eth a no l ,
a l p h a - terp ineo l , c is - terp ineo l h y dra te, es ters , s uc h a s
buty l a c eta te eth y l a c eta te, eth y l a c eto a c eta te; eth y l
benz o a te, eth y l buty ra te, eth y l c inna ma te, eth y l c ro to n
a te, eth y l f o rma te, eth y l is o buty ra te, eth y l is o v a l era te,
eth y l a l p h a - meth y l - buty ra te, eth y l p ro p io na te, eth y l
s a l ic y l a te, tra ns - Z- h exeny l a c eta te, h exy l a c eta te, 2
h exeny l buty ra te, h exy l buty ra te, is o a my l a c eta te, is o
p ro p y l buty ra te, meth y l a c eta te, meth y l buty ra te,
meth y l c a p ro a te, meth y l is o buty ra te, meth y l - Z- meth y l
buty ra te, p ro p y l a c eta te, a my l a c eta te, a my l buty ra te,
benz y l s a l ic y l a te, dimeth y l a nth ra nil a te, eth y l meth y l
p h eny l g l y c ida te eth y l s uc c ina te is o buty l c inna ma te a nd
terp eny l a c eta te; es s entia l o il s s uc h a s ja s min a bs o l ute,
ro s e a bs o l ute, o rris a bs o l ute, l emo n es s entia l o il , Bul g a r
ia n ro s e, y a ra y a ra , na tura l ra s p berry o il a nd v a nil l a ;
l a c to nes , s ul ?des , e. g . , meth y l s ul ?de a nd o th er ma teri
a l s s uc h a s ma l to l , a c eto in a nd a c eta l s ( e. g . , 1 , 1 - dieth o x
y eth a ne, 1 , 1 - dimeth o xy eth a ne a nd dimeth o xy meth a ne) .
Th e s p ec i?c ?a v o ring a djuv a nt s el ec ted f o r us e ma y
be eith er s o l id o r l iq uid dep ending up o n th e des ired
p h y s ic a l f o rm o f th e ul tima te p ro duc t, i. e. , f o o ds tuf f ,
w h eth er s imul a ted o r na tura l , a nd s h o ul d, in a ny ev ent,
be c a p a bl e o f p ro v iding a n env iro nment in w h ic h th e
c y c l ic c h emic a l c o mp o unds c a n be dis p ers ed o r a d
mixed to p ro v ide a h o mo g eneo us medium. In a dditio n,
s el ec tio n o f o ne o r mo re ?a v o ring a djuv a nts , a s w el l a s
th e q ua ntities th ereo f w il l dep end up o n th e p rec is e o r
g a no l ep tic c h a ra c ter des ired in th e ?nis h ed p ro duc t.
Th us , in th e c a s e o f ?a v o ring c o mo s itio ns , ing redient
s el ec tio n w il l v a ry in a c c o rda nc e w ith th e f o o ds tuf f to
w h ic h th e ?a v o r a nd a ro ma a re to be imp a rted. In c o n
tra dis tinc tio n, in th e p rep a ra tio n o f s o l id p ro duc ts , e. g . ,
s imul a ted f o o ds tuf f s , ing redients c a p a bl e o f p ro v iding
no rma l l y s o l id c o mp o s itio ns s h o ul d be s el ec ted s uc h a s
v a rio us c el l ul o s e deriv a tiv es .
As w il l be a p p rec ia ted by th o s e s k il l ed in th e a rt, th e
a mo unt o f a l deh y de- c o nta ining c o mp o s itio n o f o ur in
v entio n emp l o y ed in a p a rtic ul a r ins ta nc e c a n v a ry o v er
a rel a tiv el y w ide ra ng e w h ereby its des ired o rg a no l ep
tic ef f ec ts ( h a v ing ref erenc e to th e na ture o f th e p ro d
uc t) a re a c h iev ed. Th us , c o rres p o nding l y g rea ter
a mo unts w o ul d be nec es s a ry in th o s e ins ta nc es w h erein
th e ul tima te f o o d c o mp o s itio n to be ?a v o red is rel a
tiv el y bl a nd to th e ta s te, w h erea s rel a tiv el y mino r q ua n
titl es ma y s uf ?c e f o r p urp o s es o f enh a nc ing th e c o mp o
s itio n merel y de?c ient in na tura l ?a v o r o r a ro ma . Th e
p rima ry req uirement is th a t th e a mo unt s el ec ted ( to be
ef f ec tiv e) be s uf ?c ient to a ug ment o r enh a nc e th e o rg a
no l ep tic c h a ra c teris tic s o f th e p a rent c o mp o s itio n
( w h eth er f o o ds tuf f p er s e o r ?a v o ring c o mp o s itio n) .
Th e us e o f ins uf ?c ient q ua ntities o f a l deh y de- c o nta in
ing c o mp o s itio n o f o ur inv entio n, w il l , o f c o urs e, s ub
s ta ntia l l y v itia te a ny p o s s ibil ity o f o bta ining th e des ired
res ul ts w h il e exc es s q ua ntities p ro v e needl es s l y c o s tl y
a nd in extreme c a s es , ma y dis rup t th e ?a v o r- a ro ma
ba l a nc e, th us p ro v ing s el f - def ea ting . Ac c o rding l y , th e
termino l o g y ef f ec tiv e a mo unt a nd s uf ?c ient
a mo unt is to be a c c o rded a s ig ni?c a nc e in th e c o ntext
o f th e p res ent inv entio n c o ns is tent w ith th e o btentio n o f
des ired ?a v o ring ef f ec ts .
Th us , a nd w ith res p ec t to ul tima te f o o d c o mp o s itio n,
it is f o und th a t q ua ntities o f a l deh y de- c o nta ining c o m
p o s itio n o f o ur inv entio n ra ng ing f ro m a s ma l l but ef f ec
tiv e a mo unt, e. g . , 0 . 5 p p m up to 3 % by w eig h t ba s ed o n
to ta l c o mp o s itio n a re s uita bl e a s s ta ted, s up ra . Co nc en
tra tio ns in exc es s o f th e ma ximum q ua ntity s ta ted a re
no t no rma l l y rec o mmended, s inc e th ey f a il to p ro v ide
4 , 6 1 7 , 4 1 9
1 3
c o mmens ura te enh a nc ement o f o rg a no l ep tic p ro p erties .
In th o s e ins ta nc es w h ere th e a l deh y de- c o nta ining c o m
p o s itio n o f o ur inv entio n is a dded to th e f o o ds tuf f a s a n
integ ra l c o mp o nent o f a ?a v o ring c o mp o s itio n, it is , o f
c o urs e, es s entia l th a t th e to ta l q ua ntity o f ?a v o ring
c o mp o s itio n emp l o y ed be s uf ?c ient to y iel d a n ef f ec tiv e
a mo unt o f a l deh y de- c o nta ining c o mp o s itio n.
Fo o d ?a v o ring c o mp o s itio ns p rep a red in a c c o rda nc e
w ith th e p res ent inv entio n p ref era bl y c o nta in th e a l de
h y de- c o nta ining c o mp o s itio n o f o ur inv entio n ra ng ing
f ro m a bo ut 0 . 1 % up to a bo ut 1 0 0 % by w eig h t ba s ed o n
th e to ta l w eig h t o f s a id ?a v o ring c o mp o s itio n.
Th e c o mp o s itio ns des c ribed h erein c a n be p rep a red
a c c o rding to c o nv entio na l tec h niq ues w el l k no w n a s
ty p i?ed by c a k e ba tters a nd f ruit drink s a nd c a n be
f o rmul a ted by merel y a dmixing th e inv o l v ed ing redi
ents w ith in th e p ro p o rtio ns s ta ted in a s uita bl e bl ender
to o bta in th e des ired c o ns is tenc y , h o mo g eneity o f dis
p ers io n, etc . Al terna tiv el y , ?a v o ring c o mp o s itio ns in
th e f o rm o f p a rtic ul a te s o l ids c a n be c o nv enientl y p re
p a red by mixing th e a l deh y de- c o nta ining c o mp o s itio n
o f o ur inv entio n w ith , f o r exa mp l e, g um a ra bic , g um
tra g a c a nth , c a rra g eena n a nd th e l ik e, a nd th erea f ter
s p ra y - dry ing th e res ul ta nt mixture w h ereby to o bta in
th e p a rtic ul a te s o l id p ro duc t. Pre- p rep a red ?a v o r mixes
in p o w der f o rm, e. g . , a f ruit ?a v o red p o w dered mix, a re
o bta ined by mixing th e dried s o l id c o mp o nents , e. g . ,
s ta rc h , s ug a r a nd th e l ik e a nd a l deh y de- c o nta ining c o m
p o s itio n in a dry bl ender until th e req uis ite deg ree o f
unif o rmity is a c h iev ed.
Th e no v el a l deh y de c o mp o s itio n- c o nta ining s ub
s ta nc es p ro duc ed a c c o rding to th e no v el p ro c es s o f o ur
inv entio n ma y be us ed a s is a s s ta ted, s up ra , o r ma y be
us ed in c o njunc tio n w ith o th er ?a v o r a djuv a nts inc l ud
ing but no t l imited to :
Hel io tro p in;
Terp ineno l - 4 ;
Anis a l deh y de;
Ph eny l a c eta l deh y de;
Benz y l f o rma te;
Benz y l a c eta te;
Cis - 3 - h exeny l benz o a te;
Meth y l Hexa no a te;
Hexa na l ;
Euc a l y p to l ;
Eug eno l ;
Eth y l a c eta te;
Eth y l buty ra te;
Turp entine g um o il ;
Limo nene;
Gum c a mp h o r;
Is o bo rny l a c eta te;
Bo rneo l ;
Cuminic a l deh y de;
Furf ura l ;
Meth y l c inna ma te;
Ca s s ia o il ;
V a nil l in;
Ma l to l ;
Pa ra h y dro xy benz y l a c eto ne;
Dimeth y l s ul ?de;
Al p h a - io no ne;
Ac etic a c id;
Is o buty l a c eta te;
Ac eto ne;
Buty ric a c id;
Fo rmic a c id;
V a l erie a c id;
2 0
2 5
3 0
3 5
4 5
5 0
5 5
6 0
6 5
1 4
Amy l a c eta te;
Amy l buty ra te;
Aneth o l ;
Benz y l s a l ic y l a te;
Dia c ety l ;
Dimeth y l a nth ra nil a te;
Eth y l meth y l p h eny l g l y c ida te;
Eth y l s uc c ina te;
Eth y l v a l era te;
Gera nio l ;
Cis - S - h exen- l - o l ;
2 - Hexeny l a c eta te;
2 - Hexeny l buty ra te;
Hexy l buty ra te;
4 - ( p - Hy dro xy p h eny l ) - 2 - buta no ne;
Beta - io no ne;
Is o buty l c inna ma te;
Ja s mine;
Lemo n es s entia l o il ;
Meth y l buty ra te;
Meth y l c a p ro na te;
Meth y l dis ul ?de;
Meth y l p - na p h th y l k eto ne;
O rris butter;
Ro s e a bs o l ute;
Terp eny l a c eta te;
Ga mma - undec a l a c to ne;
V a nil l a ;
Al c o h o l ;
O il o f Cubeb;
Ph el l a ndrene;
Beta - p h el l a ndrene;
O il o f Co ria nder;
O il o f Pimento Lea f ;
O il o f Pa tc h o ul i;
Al p h a - Pinene;
Beta - Pinene;
Beta - c a ry o p h y l l ene;
Dih y dro c a rv eo l ;
Pip ero na l ;
Pip erine;
Ch a v ic ine;
Pip eridine;
O il o f Bl a c k Pep p er;
Bl a c k Pep p er O l eo res in;
Ca p s ic um;
O il o f Nutmeg ;
Ca rda mo n O il ;
Cl o v e O il ;
S p ea rmint O il ; a nd
O il o f Pep p ermint.
An a dditio na l a s p ec t o f o ur inv entio n p ro v ides a n
o rg a no l ep tic a l l y imp ro v ed s mo k ing to ba c c o p ro duc t
a nd a dditiv es th eref o r, a s w el l a s meth o ds o f ma k ing th e
s a me w h ic h o v erc o me s p ec i?c p ro bl ems h ereto f o re
enc o untered in w h ic h s p ec i?c des ired s w eet a nd f ruity
?a v o r c h a ra c teris tic s o f na tura l to ba c c o a re c rea ted o r
enh a nc ed a nd ma y be rea dil y c o ntro l l ed a nd ma inta ined
a t th e des ired unif o rm l ev el reg a rdl es s o f v a ria tio ns in
th e to ba c c o c o mp o nents o f th e bl end.
Th is inv entio n f urth er p ro v ides imp ro v ed to ba c c o
a dditiv es a nd meth o ds w h ereby v a rio us des ira bl e s w eet
a nd f ruity ?a v o ring c h a ra c teris tic s ma y be imp a rted to
s mo k ing to ba c c o p ro duc ts a nd ma y be rea dil y v a ried
a nd c o ntro l l ed to p ro duc e th e des ired unif o rm ?a v o ring
c h a ra c teris tic s .
In c a rry ing o ut th is a s p ec t o f o ur inv entio n, w e a dd to
s mo k ing to ba c c o ma teria l s o r a s uita bl e s ubs titute th ere
4 , 6 1 7 , 4 1 9
1 5
f o r ( e. g . , dried l ettuc e l ea v es ) o r w e a dd to ?l ters f o r
s mo k ing to ba c c o a rtic l es ( e. g . , c el l ul o s e a c eta te ?l ters )
a n a ro ma a nd ?a v o r a dditiv e c o nta ining a s a n a c tiv e
ing redient th e a l deh y de- c o nta ining c o mp o s itio n o f o ur
inv entio n w h ic h is th e benz a l deh y de/c inna ma l deh y de 5
c o mp o s itio n.
In a dditio n to th e benz a l deh y de/c inna ma l deh y de
c o mp o s itio n o f o ur inv entio n o th er ?a v o ring a nd a ro ma
a dditiv es ma y be a dded to th e s mo k ing to ba c c o ma teria l
o r s ubs tituted th eref o r eith er s ep a ra tel y o r in a dmixture
w ith th e benz a l deh y de/c inna ma l deh y de c o mp o s itio n o f
o ur inv entio n a s f o l l o w s :
I. S YNTHETIC MATERIALS
Beta - eth y l - c inna ma l deh y de;
Eug eno l ;
Dip entene;
Beta - Da ma s c eno ne;
Ma l to l ;
Eth y l ma l to l ;
Del ta undec a l a c to ne;
Del ta dec a l a c to ne;
Amy l a c eta te;
Eth y l buty ra te;
Eth y l v a l era te;
Eth y l a c eta te;
2 - Hexeno l ;
1 , 2 - Meth y l - 5 - is o p ro p y l - 1 , 3 - no na diene- 8 - o ne;
2 , 6 - Dimeth y l - 2 , 6 - undec a diene- 1 0 - o ne;
2 - Meth y l - 5 - is o p ro p y l a c eto p h eno ne;
2 - Hy dr0 xy - 2 , 5 , 5 , 8 a - tetra rneth y l - l - ( 2 - h y dro xy eth y l )
dec a h y dro na p h th a l ene;
Do dec a h y dro - 3 - a , 6 , 6 , 9 a - tetra meth y l
f ura n;
4 - Hy dro xy h exa no ic a c id, g a mma l a c to ne;
Po l y is o p reno id h y dro c a rbo ns de?ned in Exa mp l e V o f
US Pa t. No . 3 , 5 8 9 , 3 7 2 is s ued o n June 2 9 , 1 9 7 1 .
II. NATURAL O ILS
1 5
2 0
2 5
Cel ery s eed o il ;
Co f f ee extra c t;
Berg a mo t O il ;
Co c o a extra c t;
Nutmeg o il ;
O rig a num o il ;
An a ro ma a nd ?a v o ring c o nc entra te c o nta ining th e
benz a l deh y de/c inna ma l deh y de c o mp o s itio n o f o ur in
v entio n a nd, if des ired, o ne o r mo re o f th e a bo v e indi
c a ted a dditio na l ?a v o ring ma teria l s ma y be a dded to th e
s mo k ing to ba c c o ma teria l , to th e ?l ter o r to th e l ea f o r
p a p er w ra p p er. Th e s mo k ing to ba c c o ma teria l ma y be
s h redded, c ured, c a s ed a nd bl ended to ba c c o ma teria l o r
rec o ns tituted to ba c c o ma teria l o r to ba c c o s ubs titutents
( e. g . , l ettuc e l ea v es ) o r mixtures th ereo f . Th e p ro p o r
tio ns o f ?a v o ring a dditiv es ma y be v a ried in a c c o rda nc e
w ith ta s te but ins o f a r a s enh a nc ement o r th e imp a rting
o f na tura l a nd/ o r s w eet no tes , w e h a v e f o und th a t s a tis
f a c to ry res ul ts a re o bta ined if th e p ro p o rtio n by w eig h t
o f th e s um to ta l o f th e benz a l deh y de/c inna ma l deh y de
c o mp o s itio n o f o ur inv entio n to s mo k ing to ba c c o ma te
ria l is betw een 5 a nd 1 0 0 p p m ( 0 . 0 0 0 5 - 0 . 0 l % ) o f th e
a c tiv e ing redients to th e s mo k ing to ba c c o ma teria l . We
h a v e f urth er f o und th a t s a tis f a c to ry res ul ts a re o bta ined
if th e p ro p o rtio n by w eig h t o f th e s um to ta l o f benz a l
deh y de/c inna ma l deh y de c o mp o s itio n o f o ur inv entio n
us ed to ?a v o ring ma teria l is betw een 5 0 a nd 1 0 0 0 p p m
( 0 . 0 0 5 - 0 . 1 % ) .
4 5
5 5
6 0
6 5
1 6
Any c o nv enient meth o d f o r inc o rp o ra ting th e benz a l
deh y de/c inna ma l deh y de c o mp o s itio n o f o ur inv entio n
in th e to ba c c o p ro duc t ma y be emp l o y ed. Th us , th e
benz a l deh y de/c inna ma l deh y de c o mp o s itio n o f o ur in
v entio n ta k en a l o ne o r a l o ng w ith o th er ?a v o ring a ddi
tiv es ma y be dis s o l v ed in a s uita bl e s o l v ent s uc h a s
eth a no l , p enta ne, dieth y l eth er a nd/o r o th er v o l a til e
o rg a nic s o l v ents a nd th e res ul ting s o l utio n ma y eith er
be s p rea d o n th e c ured, c a s ed a nd bl ended to ba c c o
ma teria l o r th e to ba c c o ma teria l ma y be dip p ed into
s uc h s o l utio n. Under c erta in c irc ums ta nc es , a s o l utio n
o f th e benz a l deh y de/c inna ma l deh y de c o mp o s itio n o f
o ur inv entio n ta k en a l o ne o r ta k en f urth er to g eth er w ith
o th er f l a v o ring a dditiv es a s s et f o rth a bo v e, ma y be
a p p l ied by mea ns o f a s uita bl e a p p l ic a to r s uc h a s a brus h
o r ro l l er o n th e p a p er o r l ea f w ra p p er f o r th e s mo k ing
p ro duc t, o r it ma y be a p p l ied to th e f il ter by eith er
s p ra y ing , o r dip p ing o r c o a ting .
Furth ermo re, it w il l be a p p a rent th a t o nl y a p o rtio n
o f th e to ba c c o o r s ubs tituted th eref o r need be trea ted
a nd th e th us trea ted to ba c c o ma y be bl ended w ith o th er
to ba c c o s bef o re th e ul tima te to ba c c o p ro duc t is f o rmed.
In s uc h c a s es , th e to ba c c o trea ted ma y h a v e th e ben
z a l deh y de/c inna ma l deh y de c o mp o s itio n o f o ur inv en
tio n in exc es s o f th e a mo unts o r c o nc entra tio ns a bo v e
indic a ted s o th a t w h en bl ended w ith o th er to ba c c o s , th e
?na l p ro duc t w il l h a v e th e p erc enta g e w ith in th e indi
c a ted ra ng e.
In a c c o rda nc e w ith o ne s p ec i?c exa mp l e o f o ur in
v entio n, a n a g ed, c ured a nd s h redded do mes tic burl ey
to ba c c o is s p rea d w ith a 2 0 % eth y l a l c o h o l s o l utio n o f
a mixture c o nta ining 7 5 % benz a l deh y de a nd 2 5 % c in
na ma l deh y de p rep a red by c a rry ing o ut a rea c tio n in a
S o xh l et a p p a ra tus o f th e ty p e s et f o rth in FIG. 4 us ing
a n Mg ( O H) 2 c a ta l y s t. Th e a mo unt o f benz a l deh y de/c in
na ma l deh y de c o mp o s itio n is 2 0 p p m o n a dry ba s is .
Th erea f ter, th e a l c o h o l is remo v ed by ev a p o ra tio n a nd
th e to ba c c o is ma nuf a c tured into c ig a rettes by th e us ua l
tec h niq ues . Th e c ig a rette w h en trea ted a s indic a ted h a s
a des ired a nd p l ea s ing s w eet a nd f ruity a ro ma w ith f a int
a es th etic a l l y p l ea s ing c h erry nua nc es w h ic h is detec t
a bl e in th e ma in a nd s ide s trea ms w h en th e c ig a rette is
s mo k ed. Th e a ro ma is des c ribed a s being s w eeter, ric h ,
l es s h a rs h , mo re to ba c c o - l ik e a nd h a v ing f ruity no tes .
Wh il e o ur inv entio n is p a rtic ul a rl y us ef ul in th e ma n
uf a c ture o f s mo k ing to ba c c o , s uc h a s c ig a rette to ba c c o ,
c ig a r to ba c c o a nd p ip e to ba c c o , o th er to ba c c o p ro duc ts
f o rmed f ro m s h eeted to ba c c o dus t o r ?nes ma y a l s o be
us ed. Lik ew is e, th e benz a l deh y de/c inna ma l deh y de
c o mp o s itio ns o f o ur inv entio n c a n be inc o rp o ra ted w ith
ma teria l s s uc h a s ?l ter tip ma teria l s , s ea m p a s te, p a c k a g
ing ma teria l s a nd th e l ik e w h ic h a re us ed a l o ng w ith
to ba c c o to f o rm a p ro duc t a da p ted f o r s mo k ing . Fur
th ermo re, th e benz a l deh y de/c inna ma l deh y de c o mp o s i
tio ns o f o ur inv entio n c a n be a dded to c erta in to ba c c o
s ubs titutes o f na tura l o r s y nth etic o rig in ( e. g . , dried
l ettuc e l ea v es ) a nd, a c c o rding l y , by th e term to ba c c o
a s us ed th ro ug h o ut th is s p ec i?c a tio n is mea nt a ny c o m
p o s itio n intended f o r h uma n c o ns ump tio n by s mo k ing
o r o th erw is e, w h eth er c o mp o s ed o f to ba c c o p l a nt p a rts
o r s ubs titute ma teria l s o r bo th .
BRIEF DES CRIPTIO N O F THE DRAWINGS
FIG. 1 is th e GC- IR s p ec trum f o r th e rea c tio n p ro d
uc t o f Exa mp l e I c o nta ining benz a l deh y de a nd c in
na ma l deh y de.
4 , 6 1 7 , 4 1 9
1 7
FIG. 2 is a GC- IR s p ec trum f o r th e dis til l a tio n res i
due o f Exa mp l e I c o nta ining c inna ma l deh y de a nd benz
a l deh y de.
FIG. 3 is a GC- IR s p ec trum f o r th e rea c tio n p ro duc t 5
o f Exa mp l e II c o nta ining benz a l deh y de a nd c in
na ma l deh y de ( Co nditio ns : Ca rbo w a x c o l umn p ro
g ra mmed a t 7 5 - 2 2 5 C. a t 3 C. p er minute) .
FIG. 4 is a c ut- a w a y c ro s s s ec tio na l el ev a tio n v iew o f 1 0
a S o xh l et a p p a ra tus us ed f o r c a rry ing o ut th e rea c tio n:
1 5
0
l l
AH
II
@MH 2 0
w h en th e c inna ma l deh y de is p res ent in a s o l id ma teria l
s uc h a s p ul v eriz ed c inna mo n ba rk a nd w h en th e ba s ic 2 5
c a ta l y s t is a s o l id s uc h a s ma g nes ium h y dro xide o r c a l
c ium h y dro xide.
FIG. S is a s iml i?ed S o xh l et rea c tio n a p p a ra tus ?tting
f o r c a rry ing o ut th e rea c tio n: 3 0
( 2 /3
' O O
H o BA E H /"\ 3 5
+ O 1 % /\H + H.
\ l l H
4 0
FIG. 6 is a dia g ra m o f a s o l id- l iq uid p h a s e rea c tio n
a p p a ra tus us ef ul in c a rry ing o ut th e retro - a l do l rea c tio n,
to w it:
w h en th e c inna ma l deh y de h a v ing th e s truc ture:
o r a mixture th ereo f is in exis tenc e in a na tura l s o l id 6 5
ma teria l s uc h a s c inna mo n ba rk .
FIG. 7 A is a dia g ra m o f a l iq uid- l iq uid p h a s e rea c tio n
a nd rec o v ery a p p a ra tus f o r c a rry ing o ut th e rea c tio n:
1 8
0 0
II II
[ BAS E] E @A H + /\ H
O
- | l
@AAH
a nd rec o v ering th e na tura l benz a l deh y de- c o nta ining
c o mp o s itio n a nd th e na tura l a c eta l deh y de- c o nta ining
c o mp o s itio n o f o ur inv entio n ( a s emp l o y ed in Exa mp l e
V I, inf ra ) .
FIG. 7 B is a dia g ra m o f a s ec tio n o f th e a p p a ra tus o f
FIG. 7 A s h o w ing th e ma g netic c o il - a c tua ted rec o v ery
return mec h a nis m o f th e a p p a ra tus us ef ul in th e p ra c tic e
o f o ur inv entio n.
FIG. 7 C is a dia g ra m o f a c o ntinuo us l iq uid~l iq uid
p h a s e rea c tio n- rec o v ery a p p a ra tus f o r c a rry ing th e re
a c tio n:
a nd rec o v ering th e na tura l benz a l deh y de- c o nta ining
c o mp o s itio n a nd na tura l a c eta l deh y de- c o nta ining c o m
p o s itio n o f o ur inv entio n.
FIG. 8 is th e GLC p ro ?l e o f th e rea c tio n p ro duc t
p ro duc ed a c c o rding to Exa mp l e V I c o nta ining benz a l
deh y de a nd c inna ma l deh y de.
FIG. 9 is th e GLC p ro ?l e o f a ?rs t dis til l a tio n p ro d
uc t o f th e rea c tio n p ro duc t o f Exa mp l e V I ric h in benz
a l deh y de.
FIG. 1 0 is th e GLC p ro ?l e o f a s ec o nd dis til l a tio n
p ro duc t o f th e rea c tio n p ro duc t o f Exa mp l e V I ric h in
benz a l deh y de.
FIG. 1 1 is th e _ GLC p ro ?l e o f a th ird dis til l a tio n
p ro duc t o f th e rea c tio n p ro duc t o f Exa mp l e V I ric h in
benz a l deh y de.
FIG. 1 2 is a to ta l io n c urrent s p ec trum o f a GC- MS
a na l y s is o f a c eta l deh y de- ric h p ro duc t rec o v ered in c o l d
tra p 2 3 1 o f th e a p p a ra tus o f FIG. 7 A.
DETAILED DES CRIPTIO N O F THE
DRAWINGS
FIG. 1 is th e GC- IR s p ec trum f o r th e c rude rea c tio n
p ro duc t o f Exa mp l e I. Th e p ea k indic a ted by ref erenc e
numera l 1 0 is th e p ea k f o r benz a l deh y de in th e rea c tio n
p ro duc t. Th e p ea k indic a ted by ref erenc e numera l 1 1 is
th e p ea k f o r c inna ma l deh y de h a v ing th e s truc tures :
0
l l
a nd
H 0
FIG. 2 is th e GC- IR s p ec trum f o r th e dis til l a tio n
res idue o f Exa mp l e I c o nta ining benz a l deh y de a nd c in
na ma l deh y de. Th e p ea k indic a ted by ref erenc e numera l