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US005093538A

Umted States Patent [191 [11] Patent Number: 5,093,538

Woell [45] Date of Patent: Mar. 3, 1992

[54] PROCESSES FOR THE CONVERSION OF [56] References Cited

MYRCENE To CITRAL FOREIGN PATENT DOCUMENTS
[75] Inventor: James B. Woell, Lawrenceville, N]. 7605749 12/1976 Netherlands ...................... .. 568/485

[73] Assignee: Union Camp Corporation, Wayne, OTHER PUBLICATIONS

NJ. Fahey et al., “Joumal of Organic Chemistry", vol. 39,
pp. 3276-3277 (1.974).
[211 App]‘ No‘: "L180 Primary Examiner-Werren B. Lone
[22] Filed: Jam 26 1990 Attorney. Agent, or Firm-William K. Wissing
_ [57] ABSTRACT
Related US. Application Data A novel process for convening myrcene to citral using
[63] Continuation-impart of Ser. No. 363,808, Jun. 9. 1989, Pan‘idl‘lm (H) chloride in ‘he Presence "f “"5” a“
pa No_ 49783041,“; Sen No_ 269.278, Nov_ 9’ 1988, lmmlsclble solvent, a phase transfer agent, and a metal
paL No_ 5,017,726 ' oxoanionic salt. A novel process for converting a pal
v ladium-myrcene complex to citral using a phase transfer
[51] Int. Cl.5 ..................... .. C07C 45/00; CO7C 45/43 agent and a metal oxoanionic salt in the presence of
[52] US. Cl. .................................. .. 568/491; 568/448; water and an immiscible solvent is also disclosed.
568/449; 568/485
[58] Field of Search .............. .. 568/448, 485, 491, 449 25 Claims, No Drawings
 5,093,538
1 2
PROCESSES FOR THE CONVERSION OF SUMMARY OF THE INVENTION
MYRCENE TO CITRAL The present invention provides a novel and highly
efficient process for the production of citral comprising
RELATED APPLICATION contacting myrcene with palladium (II) chloride in the
This application is a continuation-in-part of copend presence of water, an immiscible solvent, a phase trans
ing applications U.S. Ser. No. 363,808 ?led June 9, 1989, fer agent, and a metal oxoanionic salt. The phase trans
now US. Pat. No. 4,978,804, issued Dec. 18, 1990, and fer agent is preferably an onium salt such as an ammo
U5. Ser. No. 269,278 ?led Nov. 9, 1988, now US. Pat. ‘0 nium, phosphonium or sulfonium salt. Preferably, the
No. 5,017,726. process is carried out in the presence of an oxidizing
agent. Also, preferably, the process is conducted at
BACKGROUND OF THE INVENTION temperatures ranging from about 80° C. to about 90° C.
The availability of adequate supplies of monoterpene The present invention also provides a process for
aldehydes, particularly citral, is an issue of great impor producing citral comprising contacting a palladium
tance to a number of industries. Although some pro
myrcene complex of the formula
cesses for the commercial production of citral are avail
able, new and/or improved synthetic routes are needed. /PdCl/2
Organometallic chemistry has been used by a number
of researchers in an attempt to effect various monoter 20
pene transformations. Early experiments are reported in OH
K
McQuillin et.al., J. Chem. Soc. Perkin Trans. pp. 809-815
(1974), and Dunne et.al., J. Chem. Soc. (C), pp.
2196-2200, 2200-2203, and 2203-2206 (1970). In these
studies, the authors prepared several allyl palladium 25
complexes of terpene compounds, including those re with a phase transfer agent, and a metal oxoanionic salt,
sulting from the reaction of palladium with myrcene. in the presence of water and an immiscible solvent.
Cyclization of myrcene, however, was found to occur, Preferably, the phase transfer agent is an onium salt
and citral was never obtained from the described pro such as an ammonium, phosphonium or sulfonium salt.
cesses. 30 Also preferably, the process is carried out at tempera
tures ranging from about 80° C. to about 90° C.
' Adding to this earlier work, Takahashi et.al., Journal
Using the foregoing processes, citral production can
of Organomemllic Chemistry. Vol. 266, pp. 327-336 be ef?ciently and effectively carried out with a high
(1984) successfully prepared a mixture of citral and yield of and high selectivity to this very important end
nerol utilizing a two-step method. First, myrcene was product.
35
reacted with dichlorobis(acetonitrile)palladium in the
solvent hexamethylphosphoric triamide (HMPA) or in DETAILED DESCRIPTION OF THE
the presence of a base such as Ll203 using dimethyl INVENTION
formamide (DMF) as solvent, to yield a non-cyclized The subject invention involves the production of the
palladium-myrcene complex. Although the reported 40 monoterpene aldehyde citral (that is, 3,7-dimethyl
yield for the HMPA process was relatively good, the (E,Z)-2,6—octadienal), a compound of signi?cant impor
Li2CO3/DMF process yield was somewhat low, ap tance to the ?avor, fragrance and synthetic vitamin
proximately 33%. In the second step of the reported industries. Specifically, in one aspect, the present inven
process, the complex was isolated, and then treated tion provides a two-phase system for the direct produc
with base to yield terpene aldehydes and alcohols such 45 tion of citral comprising contacting myrcene with a
as citral and nerol. One major drawback of these pro palladium (II) chloride in the presence of water, an
cesses, however, is that they necessitate two steps, re immiscible solvent, a phase transfer agent, and a metal
quiring isolation of the intermediate before further pro oxoanionic salt.
cessing. Moreover, the product obtained using these The myrcene employed in the subject processes may
methods is a mixture of both citral and nerol. Further 50 be pure myrcene or other suitable mixtures of com
more, the reactions are saddled with the added disad pounds containing myrcene, as will be apparent to those
vantage of a temperature limitation, since at tempera skilled in the art. One readily available and relatively
tures above about 60° C. the solvents I-IMPA and DMF inexpensive source of myrcene is a myrcene and limo
are decomposed by the palladium species. See Bombieri nene mixture in a ratio ‘of about 80 to about 20, respec
55 tively, a product which is commercially available from
et. al., Inorganic Chimica Acta, Vol. 86, pp. 121-125
Aldrich Chemical Company, Milwaukee, Wisconsin.
(1984); Fahey et.al., Journal of Organic Chemistry, Vol. Since myrcene is relatively unstable to oxygen, it is
9, pp. 3276-77 (1974). In addition, the use of HMPA in preferable to utilize a myrcene mixture containing an
this, or any process, is clearly undesirable, since HMPA antioxidant such as 2,6-di-tertiary-butyl-4-methyl
is an extremely potent toxin, as well as a suspected phenol, commonly referred to as butylated hydroxy
carcinogen. toluene (BHT) and sold under the trademark Ionol by
Citral is a compound of high signi?cance to the fla Shell Chemical Company, New York, NY.
vor, fragrance and synthetic vitamin industries. Addi The palladium (II) chloride may be added directly as
tional and/or better processes for their commercial PdClz. Alternatively, it may be formed in situ by the
production, particularly processes employing the 65 addition of a source of chloride ion, such as LiCl or
readily available starting material myrcene, are needed. NaCl, to a palladium (II) salt, such as PdSO4, Pd(NO3)2,
The present invention is directed to this very important Pd3(PO4)z and Pd(BF4)2. Other sources of chloride ion
end. and palladium (II) salts suitable for in situ generation of
 5,093,538
3
the palladium (Il) chloride will be apparent to those
skilled in the art. If desired, the PdCl; compound may
be complexed with loosely coordinated ligand donors,
such as acetonitrile, benzonitrile, l,5-cyclooctadiene More preferably, the metal oxoanionic salt is selected
and dimethyl sulfoxide. Thus, the palladium (II) chlo from the group consisting of Li1B4O7, Li2B10O16, Liz
ride may be in the form of, for example, di SiO3, LigM0O4, NazB4O7, 1432310016, Na2SiO3,
chlorobisaceto-nitrile palladium, that is, NazMo O4, K2B4O7, K2B10016, K2Si03, KzMOOa,
PdCl2(CH3CN)2. Other suitable ligand donors for coor MgB4O7, MgBmOm, MgSiO3, MgMOO 4, Cu1B4O7,
dination with the PdCl; compound will be apparent to CuzBmOm, Cu2SiO3, Cu2M004, CUB407, CuBwO 16,
those skilled in the art. These and other obvious varia CuSiO3, CuMOOIt, 511E407, 5111310016, SnSiO3,
tions are intended to be within the ambit of the phrase SnMoO4, Sn(B4O7)2, Sn(B|0O16)z, Sn(SiO3)2 and
palladium (II) chloride, as used herein. Preferably, the Sn(MoO4)z. Most, preferably, the metal oxoanionic salt
palladium (ll) chloride is PdCl; or PdClz(CH3CN)2. is selected from the group consisting of Li2MoO4, N32.
As used herein, the term immiscible, employed in M004 and K1M004.
connection with the term solvent, denotes those liquids As one skilled in the art will recognize, such salts
which will not substantially mix with water, thus en may, if desired, be formed in situ.
abling the formation of a two—phase system under the Suitable phase transfer agents include onium salts
conditions of the subject process. Suitable immiscible such as ammonium, phosphonium and sulfonium salts.
solvents will be readily apparent to those skilled in the Other phase transfer agents suitable for use in the pres
art and include substituted and unsubstituted aromatic 20 ent process will be readily apparent to those skilled in
compounds, as well as substituted C3 to C12 alkyls the art, armed with the present disclosure.
wherein the alkyl is substituted with one or more of Various quaternary ammonium salt phase transfer
such functionalities as hydroxy, ketone, ether or cyano agents are suitable for use in the present invention, as
groups. Examples of suitable aromatics include ben will be readily apparent to those skilled in the art. Pref
zene, toluene, and xylene. Examples of suitable substi 25 erably, the quaternary ammonium salt phase transfer
tuted alkyls include butanol, pentanol and hexanol. agents consist of a nitrogen compound having three
Other suitable immiscible solvents will be apparent to C1-C3 alkyl substitutes and one Clo-C20 alkyl substitu
those skilled in the art. Preferably, the solvent is a sub ent on the nitrogen species or, alternatively, the nitro
stituted aromatic compound or a substituted C3 to C12 gen is incorporated in an aromatic ring structure, like a
alkyl wherein the alkyl is substituted with one or more pyridine or quinoline structure, with a fourth nitrogen
hydroxy groups. More preferably, the solvent is se valence being supplied by a Clo-C10 alkyl substituent.
lected from the group consisting of toluene and butanol. Preferably, the salt is a halide salt. Most preferably, the
Not only do the preferred immiscible solvents of the agents are selected from the group consisting of cetyl
invention provide, in combination with the water em trimethylammonium chloride (“CTAC”), cetyltrimeth
ployed in the present process, a two-phase system yl-ammonium bromide (“CTAB’”), dodecyltrime
which efficiently and effectively promotes the conver thylammonium chloride (“DTAC”), dodecyltrime
sion ofmyrcene to citral, in addition, these solvents lack thylammonium bromide (“DTAB‘”), cetylpyridinium
the toxic and carcinogenic properties found in HMPA. chloride (“CPC”), and cetyl-pyridinium bromide
Any of the variety of metal oxoanionic salts available (“CPB"). '
may be employed in the present process. Preferable 40 Various quaternary phosphonium salt phase transfer
metal oxoanionic salts include Li2B4O7, LizBwBm, Liz. agents are also suitable for use in the present invention,
SiO3, Li3PO4, Li2WO4, LizCrO4, LizM0O4, LiTiO3, as will be readily apparent to those skilled in the art.
LiCoOg, Li2CO3, LizSO4, LizSnOa, Li3VO4, Li2TeO4, Preferably, the salt is a halide salt. Most preferably, the
NazBa O7, NazBmOm, Nazslogn Na3PO4, Na2WO4, agents are quaternary phosphonium halides selected
Na2CrO4, Na2MoO4, NaTiOg, NaCoO2, Na2CO3, N82. 45 from the group consisting of tributyldecyl-phos
S04, N82SI104, N33VO4, Na1TeO4, KzBa O7, phonium iodide, triphenyldecylphosphonium iodide,
KzBmOm, K2SlO3, K3PO4, Kzwoa, KzCrOa, tn'butylhexadecylphosphonium iodide, hexadecyltribu
XzMOOa, KTiO 3, KCOOZ, K2CO3, K2502, KL2SnO4, tyl-phosphonium bromide, and homologues thereof
K3VO4, K2TeO4, MgB407, MgBloo 16, MgSiO3, having chlorine, ?uorine, bromine or iodine atoms sub
Mg3(PO4)2, Mgwo4, MgCt’O4, MgMOO4, Mg(TiO3)2, stituted for the specified halogen atom. As one skilled in
Mg(C002)2, Mgcos, M3504, C8340?’ (381310016. the art would recognize, trisubstituted phosphine com
CaSiO3, Ca3(PO4)2, CaWO4, CaCrO4, Ca(TiO3)z, Ca( pounds substituted with hydrocarbons, such as tri-n
C0O2)2, C8CO3, C8504, CUZB4O7, CuzBwOw, Cu butyl phosphine, may be convened to quaternary phos
2Si03, CU3PO4, Cu2WO4, CU2CI’O4, CUZMOO4, phonium salts under the present reaction conditions,
CuTiOg, CuCoOg, Cu2CO3, CuzSO4, CuB4O7, CuB1. and as such, are also suitable for use in the subject pro
0016, CUSlO3, CU3(PO4)Z, CuWOa, CuCrO4, CUMOO4, cess as phase transfer agents.
Cu(TiO3)2, Cu(CoO2)2, CIJCO3, CuSO4, Ag2B4O7, Representative sulfonium salt phase transfer agents
agzawolt, Agzsios, ASBPOM agzwot, agzcrot, include ternary sulfonium halides such as lauryl-dime
ASTiOs, Agcooz, Agzcos, 442304. Al2(B407)3, thylsulfonium iodide, and homologues thereof having
Alphd 2(Bl0Ol6)3» Al2($i03)s, MP0 4, Al2(W04)3, chlorine, ?uorine or bromine atoms substituted for the
A12(Cf04)3, Al2(M0O4)s, Alfl'iosh, Al(C002)s, A12 iodine atom. As one skilled in the art would recognize,
(C03)3 , M26003, SnB4B7, 5111310016, snsios, disubstituted sulfur compounds substituted with hydro
Sn3(PO4)2, SnWO4, SnCr O4, SnMoO4, Sn(TiO3)2, carbons may be converted to ternary sulfonium salts
SH(COO2)2, snsos, SNSO4, $N(B407)2, 51103100162, under the present reaction conditions, and as such, are
$n(5i03)2, SHsG’OO-i, 511N002, $n(Cr04)2, also suitable for use in the subject process as phase
511040002, 51107094, $?(C0O2)4, Sn(CO3)2, transfer agents.
Sn(SO4)1, PdB4O7, PCKBwOm, PdSiO3, Pd3Pd3(PO4)2, The amount of myrcene, palladium (II) chloride,
PdWO4, PdCrO4, PdMoO4, Pd(TiO3) 2, Pd(CoO1)2, metal oxoanionic salt, phase transfer agent, water and
 5,093,538
5 6
immiscible solvent employed in the foregoing process 269,278, ?led on Nov. 9, 1988, and entitled "Processes
can vary widely, as will be recognized by those skilled for the Conversion of Myrcene to Nerol and Citral“,
in the art. By way of guidance, however, palladium (II) and copending application U.S. Ser. No. 363,808, filed
chloride and phase transfer agent are preferably present on June 9, 1989, and entitled “Processes for the Conver
in about equal amounts, and preferably each are present sion of Myrcene to Citral”, the disclosures of each of
in a molar amount equal to about 0.1 to about 0.6 times which are hereby incorporated by reference herein.
the molar amount of myrcene employed. Metal oxoan The immiscible solvents, metal oxoanionic salts, and
ionic salt is preferably present in a molar amount equal phase transfer agents which may be employed in the
to about 4 to about 10 times the molar amount of the latter embodiment of the invention, including the pref
palladium (II) chloride utilized. The water and immisci erences therefor, are as previously described.
ble solvent preferably together comprise about 70% to The amount of palladium-myrcene complex, metal
about 90% of the total reaction mixture volume, the oxoanionic salt, phase transfer agent, water and immis
water and immiscible solvent combination being com
cible solvent employed in the latter process can vary
prised of about 25% to about 75% of immiscible solvent
and a corresponding amount of about 25% to about widely, as will be recognized by those skilled in the art.
5
75% of water, on a total water and immiscible solvent By way of guidance, however, the metal oxoanionic salt
volume basis. is preferably employed in a molar amount equal to
The foregoing reaction proceeds best at temperatures about 5 to about 20 times the molar amount of palladi
ranging from about 80° C. to at least about 90° C., al um-myrcene complex employed. The water and immis
though higher or lower temperatures may be employed, 20 cible solvent preferably together comprise about 70%
if desired. The reaction may be conducted at atmo to about 90% of the total reaction mixture volume, the '
spheric pressure, and generally runs to completion water and immiscible solvent combination being com
within a few hours. To maximize yields, slow but con prised of about 25% to about 75% of immiscible sol
tinual stirring, such as by use of a magnetic stirrer, may vent, and a corresponding amount of about 25% to
be employed. If desired, the reaction may be carried out 25 about 75% of water, on a total water and immiscible
in an inert atmosphere, such as in the presence of, for solvent volume basis.
example, nitrogen, carbon dioxide, or argon gas. Preferably, the latter reaction is carried out at tem
In a preferable embodiment, the foregoing process is peratures ranging from about 80° C. to about 90° C.,
carried out in the presence of an oxidizing agent. Such although as will be understood by those skilled in the
oxidizing agents include, for example, hydrogen perox art, higher or lower temperatures may be employed.
ide, benzoguinone, copper (II) salts such as copper The foregoing processes clearly provide efficient and
chloride, cerium (IV) salts, iron (Ill) salts and silver (I) commercially viable pathways to the important com
salts. Other suitable oxidizing agents will be apparent to pound citral.
those skilled in the art. As a skilled artisan would recog The citral compound produced by the subject pro
nize, where copper (II) or iron (III) salts are employed, 35 cesses is useful in a variety of ways, for example, it may
for example, oxygen or air may, if desired, be intro be employed as a fragrance or a flavor additive or as a
duced into the reaction vessel to assist in reoxidation of
the metal salts. Preferably, the oxidizing agent is se
precursor for the synthesis of vitamins A and E. See
lected from the group consisting of hydrogen peroxide, Derfer et.al., “Terpenoids", pp. 709-762 in Kirk-Othmer
benzoguinone and copper (II) salts, particularly copper Encyclopedia of Chemical Technology, 3rd ed., Vol. 22,
chloride. Most preferably, the oxidizing agent is hydro Wiley lnterscience Publications (New York, 1983), the
gen peroxide or copper (ll) salts, particularly copper disclosures of which are incorporated by reference
chloride. herein.
The amount of oxidizing agent employed can vary The present invention is further described in the fol
widely as will be readily apparent to those skilled in the 45 lowing Examples. These Examples are not to be con
art. Preferably, the oxidizing agent is added in a molar strued as limiting the scope of the appended Claims.
amount equal to about 1 to about 5 times the molar
EXAMPLES
amount of the palladium (II) chloride utilized.
The present invention further contemplates a process In the Examples which follow, the myrcene em
for producing citral comprising contacting a palladium ployed was a myrcene and limonene mixture in a ratio
myrcene complex of the formula of about 80 to about 20, respectively, obtained from
Aldrich Chemical Company, Milwaukee, Wisconsin.
The cetyltrimethylammonium chloride was used as an
/PdCl/2 aqueous solution, 25% by weight, also obtained from
55 Aldrich.
k OH The resulting products were analyzed using internal
standard gas chromatography (GC), unless otherwise
noted, and yield results recorded. Yield calculations in
all of the Examples are based on the initial level of the
with a phase transfer agent, and a metal oxoanionic salt, 60 palladium (II) salt.
in the presence of water and an immiscible solvent. EXAMPLE 1
The palladium-myrcene complex employed can be
obtained by using a number of different methods known A solution of CuCl; (0.1528 g), PdCl2(Cl-I3CN)2
to those skilled in the art, such as the methods disclosed (0.3008 g), Li2MoO4 (1.1047 g) and H20 (3.5 ml) was
in Takahashi et.al., Journal of Organomerallic Chemistry, 65 prepared. The solution was stirred at room temperature
Vol. 266, pp. 327-336 (1984). The palladium-myrcene for about 10 min. To the solution was then added myr
complex can also be produced using the processes de cene (0.66 ml), toluene (7.5 ml) and cetyltrimethylam
scribed in copending application U.S. Serial No. monium chloride (1.5 ml). Carbon dioxide was bubbled
 5,093,538
7 8
through for about 20 min, the solution was heated to prepared. The solution was stirred at room temperature
about 90° C. for about 2.5 hrs, and product recovered. for about 10 min, To the solution was then added myr
The resulting yield of citral was 27%. cene (2.83 ml), toluene (7.5 ml) and cetyltrimethylam
EXAMPLE 2
monium chloride (1.32 ml). Oxygen was bubbled
through for about 20 min, the solution was heated to
A solution of CUC12 (0.15-12 g), PdCl;(CH3CN); about 90° C. for about 4 hrs, and product recovered.
(0.3008 g), Li2MoO4 (1.1031 g) and H20 (5 ml) was The resulting yield of citral, analyzed using external
prepared. The solution was stirred at room temperature standard gas chromatography, was 20%.
for about 10 min. To the solution was then added myr
cene (0.66 ml), toluene (7.5 ml) and cetyltrimethylam 10 EXAMPLE 8
monium bromide (0.4157 g). Carbon dioxide was bub A solution of CuCl; (0.1522 g), PdCl2(CH3CN)z
bled through for about 20 min, the solution was heated (0.3010 g}, Li1MoO4 (1.1047 g) and H20 (5 ml) was
to about 90° C. for about 2.5 hrs, and product recov prepared. The solution was stirred at room temperature
ered. for about 10 min. To the solution then added myrcene
The resulting yield of citral was 14%. 15 (0.66 ml), l-butanol (7.5 ml) and hexadecyltributyl
EXAMPLE 3
phosphonium bromide (0.5077 g), and CO2 was bubbled
through the solution for about 15 min. The solution was
A solution of CuCl; (0.1520 g), PdClz(CH3CN)2 heated to about 90° C. for about 2.5 hours, while con
(0.3000 g), Li2MoO4 (1.1046 g) and H20 (3.67 ml) was tinuing to introduce CO2 into the reaction vessel. Prod
prepared. The solution was stirred at room temperature 20 uct was then recovered.
for about 10 min. To the solution was then added myr The resulting yield of citral was 12%.
cene (0.66 ml), n-butanol (7.5 ml) and cetyltrimethylam Various modi?cations of the invention in addition to
monium chloride (1.32 ml). Carbon dioxide was bub those shown and described herein will be apparent to
bled through for about 20 min, the solution was heated those skilled in the art from the foregoing description.
to about 90° C. for about 2.5 hrs, and product recov 25 Such modi?cations are also intended to fall within the
ered. scope of the appended claims.
The resulting yield of citral was 46%. What is claimed is:
l. A process for producing citral comprising contact
EXAMPLE 4
ing myrcene with palladium (I1) chloride in the pres
A solution of CuCl; (0.0675 g), PdCl2(CH3CN)2 30 ence of water, a solvent immiscible with water, a phase
(0.1300 g), L12MOO4 (0.4849 g) and E20 (3.67 ml) was transfer agent, and a metal oxoanionic salt wherein said
prepared. The solution was stirred at room temperature metal of said metal oxoanionic salt is selected from the
for about 10 min. To the solution was then added myr~ group consisting of Li, Na, K, Mg, Ca, Cu, Ag, Al, Sn,
cene (3 ml), n-butanol (7.5 ml) and cetyltrimethylam and Pd.
monium chloride (1.32 ml), and 02 was bubbled through 35 2. A process according to claim 1 wherein the pro
the solution for about 15 min. The solution was heated cess is carried out at a temperature ranging from about
to about 90° C. for about 6 hrs, while continuing to 80° C. to about 90° C.
introduce 02 into the reaction vessel. Product was then 3. A process according to claim 1 wherein the palla
recovered. dium (ll) chloride is selected from the group consisting
The resulting yield of citral was 43%. of PdClz and PdClg loosely coordinated with ligand
donors.
EXAMPLE 5
4. A porcess according to claim 3 wherein the palla
A solution of CuCl; (0.0678 g), PdClz(CH3CN)2 dium (II) chloride is dichlorobisacetonitrile palladium.
(0.1308 g), Li2MoO4 (0.4764 g) and H20 (3.67 ml) was 5. A process according to claim 1 wherein the immis
prepared. The solution was stirred at room temperature 45 cible solvent is selected from the group consisting of
for about 10 min. To the solution was then added myr substituted and unsubstituted aromatic compounds and
cene (3 ml), n-butanol (7.5 ml) and cetyltrimethylam substituted C3 to C12 alkyls wherein the alkyl is substi
monium chloride (1.32 ml), and 02 was bubbled through tuted with one or more hydroxy, ketone, ether or cyano
the solution for about 15 min. The solution was heated groups.
to about 90‘ C. for overnight, while continuing to intro 50 6. A process according to claim 5 wherein the sol
duce 01 into the reaction vessel. Product was then re vent is selected from the group consisting of substituted
covered. aromatic compounds and substituted C3 to C12 alkyls .
The resulting yield of citral was 66%. wherein the alkyl is substituted with one or more hy
EXAMPLE 6
droxy groups.
55 7. A process according to claim 6 wherein the sol
A solution of CuCl; (0.0678 g), PdCl2(CH3CN)2 vent is selected from the group consisting of toluene
(0.1312 g), Li2MoO4 (0.4782 g) and H20 (5 ml) was and l-butanol.
prepared. The solution was stirred at room temperature 8. A process according to claim 1 wherein the metal
for about 10 min. To the solution was then added myr oxoanionic salt is selected from the group consisting of
cene (3 ml), n-butanol (7.5 m1) and cetylpyn'dinium 1.128407, Li2B1QO16, L13PO4, Lizwolt, Li2CrO4, L12.
chloride (0.3586 g). Carbon dioxide was bubbled M004, LiTiO3, LiCOOZ, Li1CO3, Li2SO4, P18213407,
through for about 20 min, the solution was heated to NazBmOw, NazSiOg, N83PO4, Na1WO4, Na2CrO4,
about 90' C. for about 2.5 hrs, and product recovered. Na2MoO4, N8Ti03, NaCoO2, N32C03, Na,SO4,
The resulting yield of citral was 66%. X21340‘), KZB1QO16, X25103, K3PO4, KL2WO4,
EXAMPLE 7
65 K2CrO4, K2M0O4, KTiO}, KLCOOZ, K2CO3, K2504,
MgB407, P48310016, Mgsios, Mg3(PO4)2, Mgwot,
A solution of CuCl; (0.6731 g), PdCl2(CH3CN)2 MgCrO4, MgMoO4, Mg(TiO3)2, Mg(CoO2);, MgCO3,
(0.0886 g), Li2MoO4 (1.0042 g) and H20 (5 ml) was MgS04, (3813401, caBlools, Casios, C83(P04)2,
 5,093,538
9 10
CaWO4, CaCrO4, Ca(TiO3)2, Ca(C0O2)1, CaCO3, 17. A process according to claim 16 wherein the
C8504, Cu2B4O7, CU2B10016, Cu2SiO3, CU3PO4, C112. process is carried out at a temperature ranging from
W04, CuzCrO4, Cu2MoO'4, CuTiOg, CuCoOg, CU2CO3, about 80° C. to about 90° C.
18. A process according to claim 16 wherein the
CUZSO4, CuB4B4O7, CuBmOm, CuSiO3, Cu3(PO 4);, solvent is selected from the group consisting of substi
CuWO4, CuCrO4, CuMoO4, Cu(TiO3)1, Cu(CoO2)2, tuted and unsubstituted aromatic compounds and substi
CUCO3, CD894, Ag2B4O7, AgzBmOw, Agzsiog, Ag3. tuted C3to C12 alkyls wherein the alkyl is substituted
P04, Ag2wO4, AgzCrO 4, AgTiO3, AgCOOz, AgzCO3, with one or more hydroxy, ketone, ether or cyano
1482504, Al2(B4O7)s. A12(l0016)s, Al 2($i03)3, A1P04, groups.
Al2(W04)3, A12(Cr04)s. Al2(M004)3. Al(Ti0s)s, A1( 19. A process according to claim 18 wherein the
COO 2)3, Al2(CO3)3, M26003, SHE-107, 511310016. solvent is selected from the group consisting of substi
SnSiO3, Sn3(PO4 (1, SnWO4, SnCrO4, SnMoO4, Sn(Ti tuted aromatic compounds and substituted C3 to C12
alkyls wherein the alkyl is substituted with one ore
more hydroxy groups.
20.' A process according to claim 19 wherein the
solvent is selected from the group consisting of toluene
Sn(CO3);, Sn(SO4)2, PdB407, PdBmOm, PdSiO3, and l-butanol.
Pd3(PO4)2, PdWO4, PdCr04, PdMoO4, Pd(TiO3)2, 21. A process according to claim 16 wherein the
Pd(CoO2);, PdCO3, OdCO3, PdSO4, Pd(B4O7)2, metal oxoanionic salt is selected from the group consist
K103100102, Pd($i03)2. Pd3(P04, Pd(w04)2, ing Of Li2B4O7, LigBwOm, Li2SiO3, Li3PO4, Li2WO4,
Pd(C1'04)2. P6040002, Pd(Ti03)4, Pd(C002)4, Li2C1’O4, Li2MOO4, LiTiO3, LiCOOZ, Li2CO3, Li2SO4,
Pd(CO3)2, and Pd(SO4)2. Na2B4O7, NagBmlG, Na2SiO3, Na3PO4, Na2wO4, N82.
9. A process according to claim 8 wherein the metal CrO4, Na2MoO4, NaT iO3, NaCoOz, N82CO3, Na2SO4,
oxide is selected from the group consisting of Li2MoO4 X23407, KZBIOOK» Kzsios, K 3P04, K2WO4, K2Cr04,
and K2MoO4. K2MoO4, KTiO3, KCoOg, K2CO3, K1804, MgB4O7,
10. A process according to claim 1 wherein the myr
MgBmOm, MgSiO3, Mg3(PO4)z, MgWO4, MgCrO4,
MgMoO4, Mg(TiO3)2, Mg(CoO2)2, MgCO3, MgSO4,
cene is in the form of a myrcene and limonene mixture. CaB4O7, CaB10O16, C3Si03, Ca3(PO4)2, CaWO4, Ca
11. A process according to claim 10 wherein the Cl’04, Ca(TiO3)2, Ca(CoO2)2, CaCO3, CaSOri, CUZB
myrcene to limonene ratio is about 80 to about 20. 407, CU2B10016, CuzSiOz, CU3PO4, Cu2WO4, Cu2CrO4,
12. A process according to claim 1 which is carried CUZMOO4, CUTiO3, CUCOOZ, Cuzco}, Cu2SO4, CUB
out in the presence of an oxidizing agent. 407, CUBmOw, CUSiO3, CU3(PO4) 2, CUWO4, CuCrO4,
13. A process according to claim 1 wherein the phase CuMoO4, Cu(TiO3)2, Cu(CoO2)2, CuCO3, CuSO4, Agz.
transfer agent is selected from the group consisting of
ammonium, phosphonium and sulfonium salts.
14. A process according to claim 13 wherein the
phase transfer agent is a quaternary ammonium salt.
15. A process according to claim 14 wherein the
quaternary ammonium salt is selected from the group
consisting of cetyltrimethylammonium chloride, cetyl
trimethylammonium bromide, dodecyltrimethylam‘
monium chloride, dodecyltrimethylammonium bro
mide, cetylpyridinium chloride, and cetylpyridinium
bromide.
16. A process for producing citral comprising con~
tacting a palladium-myrcene complex of the formula 22. A process according to Claim 21 wherein the
metal oxoanionic, salt is selected from the group con
sisting Li2MOO4, Na2MoO4 and KZMOO4.
/PdCl/2 23. A process according to claim 16 wherein the
phase transfer agent is selected from the group consist
ing of ammonium, phosphonium and sulfonium salts.
24. A process according to claim 23 wherein the
phase transfer agent is a quaternary ammonium salt.
25. A process according to claim 24 wherein the
quaternary ammonium salt is selected from the group
with a phase transfer agent, and a metal oxoanionic salt
consisting of cetyltrimethylammonium chloride, cetyl
tri-methylammonium bromide, dodecyltrimethylam
wherein said metal of said metal oxoanionic salt is se monium chloride, dodecyltrimethylammonium bro
lected from the group consisting of Li, Na, K, Mg, Ca, mide, cetyl-pyridinium chloride, and cetylpyridinium
Cu, Ag, Al, Sn, and Pd, in the presence of water and a bromide.
solvent immiscible with water. ‘ Q i ‘ t