Title of Invention

SYNTHESIS OF CYCLOPENTENONES

Abstract The invention relates to a process for the preparation, in a single step, of substituted 2-cyclopenten-1-ones by reacting a substituted enone with an aldehyde in the presence of a catalytic system. Said catalytic system consists of a metal complex, snch as a [Ti(Cl)3(alkoxy)], and a co-ingredient, such as a carboxylic acid anhydride or an anhydrous salt.
Full Text Technical field
The present invention relates to the field of organic synthesis and more precisely to
a single step process for the synthesis of a cyclopentenone derivative of formula

as defined further below.
Prior art
Ishii et ah, in J.Org.Cbem., 1993, 58, 4497, reports the synthesis of
cyclopentenone derivatives from the reaction of a ketone with two equivalents of an
aldehyde or by the reaction of an enone with an aldehyde, which is catalyzed by Zirconium
chloride derivatives such as ZrOCl2 or ZrCl4, the oxide being described as the best catalyst.
However, the procedure reported by Ishii requires severe conditions such as high
temperature (between 130 and 200°C, the upper part of the range giving the best results,
see Table I). Such severe conditions may result in poor yields (for example 17% when all
the ring substituents are methyl groups, reaction carried out at 200°C). These conditions
are not of high industrial interest since are not environmentally friendly, and require much
energy and produce high amounts of wastes.
Description of the invention
In order to overcome all or part of the problems aforementioned, the present
invention relates to a process for the preparation of cyclopentenone derivatives that can be
carried out with soft conditions and accessory can result in high yields.
One of the objects of the invention is a process for the preparation of a compound
of formula


wherein R represents a C1-8 alkyl or alkenyl group optionally substituted or a C5-6
aromatic, optionally substituted; and
R1, R2, R3 and R4 represent, simultaneously or independently, a hydrogen atom, a C1-8
alkyl or alkenyl group optionally substituted or a C5-6 aromatic group, optionally
substituted;
said process comprising the reaction between an enone of formula

wherein R, R1, R3 and R4 have the same meaning as in formula (I);
with an aldehyde of formula

wherein R2 has the same meaning as in formula (I); and
the reaction between said enone (II) and the aldehyde (III) being performed in the presence
of a catalytic system comprising:
i) at least one metal complex of formula

wherein M is Ti(IV) or Zr(IV), R5 represents a C1-6 linear or branched alkyl group, X
• represents a halide and n represents an integer from 1 to 3; and
ii) at least one co-ingredient selected from the group consisting of
a) an alkyl or aromatic carboxylic acid anhydride containing 2 to 10 carbon atoms;

b) an anhydrous sulfate, chloride or bromide of a metal cation selected from the group
c) an insoluble inorganic material capable to form a clathrate with water; and
d) a C4-C15 orthoester, BF3, N-methyl-N-trimethylsilyl-trifluoroacetamide,
1-trimethylsilylimidazole and ClSi(R6)3, R6 representing a C1-5 alkyl group.
Possible optional substituents of said groups R, R1, R2, R3 and R4 are groups which
do not affect the reactivity of the enone (II) or of the aldehyde (III). Examples of said
optional substituents, when said R, R1, R2, R3 and R4 groups represent alkyl or alkenyl
group, include one or two methyl, ethyl, methoxy or ethoxy groups. Examples of said
optional substituents, when said R, R1, R2, R3 and R4 groups represent an aromatic group,
include one or two methyl, ethyl, methoxy, ethoxy or nitro groups.
According to a particular embodiment of the invention, R represents a C1-8 alkyl or
alkenyl group or C5-6 aromatic group optionally substituted. Alternatively, R1, R2, R3 and
R4 represent, simultaneously or independently, a hydrogen atom, a C1-8 alkyl or alkenyl
group or a C5-6 aromatic group optionally substituted.
In particular according to said embodiment, R represents a C1-8 alkyl or alkenyl
group, and R1, R2, R3 and R4 represent, simultaneously or independently, a hydrogen atom,
a C1-8 alkyl or alkenyl group.
In another embodiment of the invention, there is obtained an enone of formula (I),
from the corresponding compounds (II) and (III), wherein R represents a methyl, ethyl or
pentyl group or a phenyl group optionally substituted. Alternatively, or simultaneously, R1,
R2, R3 and R4 represent, simultaneously or independently, a hydrogen atom, a methyl, ethyl
or pentyl group or a phenyl group optionally substituted.
In particular according to said embodiment, R represents a methyl, ethyl or pentyl
group, and R1, R2, R3 and R4 represent, simultaneously or independently, a hydrogen atom,
a methyl, ethyl or pentyl group.
According to any one of the above-mentioned embodiments, R4 represents a
hydrogen atom. In particular, said R, R1, R2 or R3 represents, simultaneously or
independently, a methyl, ethyl or phenyl group optionally substituted, or just a methyl or
ethyl group, while R4 represents a hydrogen atom.

According to a further embodiment of the invention, the ketone (II) can be
obtained in situ by reacting together a ketone (V) and a ketone or aldehyde (VI), in the
presence of the same catalytic system of the invention's process, according to Scheme 1.

wherein R, R1, R3 and R4 have the same meaning as indicated above.
Therefore the present invention concerns also a process further comprising the step
mentioned above.
Particular examples of suitable ketones (II), (V) or (VI) are diethyl ketone,
dibenzyl ketone, methyl phenyl ketone, ethyl phenyl ketone or hexyl methyl ketone.
Particular examples of suitable aldehydes (III) or (VI) are acetaldehyde,
formaldehyde, propanaldehyde or benzaldehyde.
According to a further embodiment of the invention, the process comprises a first
step wherein are reacted together a diethyl ketone and acetaldehyde to obtain a ketone of
formula (II), which is subsequently reacted with acetaldehyde.
According to an embodiment of the present invention the molar ratio between the
enone (II) and the aldehyde (III) is comprised between 1.1/1 and 1/6, more preferably
between 1/1 and 1/5 and even more preferably between 1/1.1 and 1/5. Furthermore, the
molar ratio between the ketone (V) and the compound (VI) is comprised between 1/1 and
1/8, more preferably between 1/2.5 and 1/6 and even more preferably between 1/3 and 1/5.
As mentioned above, the process of the invention is carried out in the presence of a
catalytic system, which consists of a metal complex and of a co-ingredient. The metal
complex is used in substoechiometric, or catalytic amounts, relative to the starting
aldehyde or ketone.
The metal complex has a general formula:



wherein M, n, R and X have the meaning given above. According to a particular
embodiment of the invention, M represents Ti(IV), R5 represents a linear or branched C3-4
alkyl group, X represents a Cl atom and the index n represents 2 or 3.
The use of a mixture of metal complexes of formula (IV) is also convenient,
especially if the catalyst is synthesized in situ, and without purification, prior to its use in
the process.
According to a particular embodiment of the invention, the co-ingredient of the
catalytic system is selected from the group consisting of an alkyl or aromatic carboxylic
acid anhydride containing 4 to 8 carbon atoms, BF3, ClSi(R6)3, R6 representing a C1-5 alkyl
group, and an anhydrous sulfate, chloride or bromide of a metal cation selected from the
group consisting of Na+, K+, Mg2+, Ca2+, Zn2+, Fe3+.
Preferably, the co-ingredient is selected from the group consisting of acetic,
propionic or butyric anhydride, BF3, ClSi(R6)3, R6 representing a methyl or ethyl group,
the anhydrous Na2SO4 or K2SO4 and an anhydrous chloride or bromide of Mg2+, Fe3+ or
Zn2+.
The use of a mixture of two or three co-ingredients is also possible.
The metal complex can be added to the reaction medium in a large range of
concentrations. As non-limiting examples, one can cite catalyst concentrations ranging
from 0.01 to 0.20 molar equivalents, relative to the molar amount of the starting
ketone (II) or (V). Preferably, the metal complex concentration will be comprised between
0.01 and 0.10 molar equivalents. It goes without saying that the optimum concentration of
catalyst will depend on the nature of the latter and on the desired reaction time.
The co-ingredient can be added to the reaction medium in a large range of
concentrations. As non-limiting examples, one can cite salt concentrations ranging from
0.05 to 1.2 molar equivalents, relative to the number of moles of the starting ketone (II) or
(V). Preferably, the salt concentration will be comprised between 0.10 and 0.60 molar
equivalent. Yet, in another preferred embodiment, the salt concentration will be comprised
between 0.20 and 0.50 molar equivalents. It goes without saying that the optimum
concentration of the additional agent will depend on the nature of the latter.


The process of the invention can be carried out in the presence or absence of
solvent, but in any case it is advantageously performed in anhydrous conditions,wherein
by "anhydrous" it is meant here a solvent which has a content in water below 1% by
weight, preferably below 0.1%. When a solvent is required, it is possible to use a pure
solvent or a mixture of solvents. Said solvent must be chemically compatible with the
reaction conditions, i.e. not interfere with the reaction, and not deactivate the catalyst, e.g.
a weak or non-coordinating solvent. Preferred solvents for the process of the invention
have a boiling point higher than 60°C and are selected from the group consisting of ethers,
esters, aromatic solvents, and linear or branched or cyclic hydrocarbons. More preferably,
the solvent is an ester such as butyl acetate.
Furthermore, the solvent can be the starting ketone (II) or (V) or the starting
aldehyde (III) or (VI).
The temperature at which the process of the invention can be carried out is
comprised between 60°C and 140°C, preferably between 70°C and 100 or 110°C. Of
course a person skilled in the art is also able to select the reaction temperature as a
function of the melting and boiling point of the starting and final products and/or the
possible solvent.
The invention will now be described in further detail by way of the following
examples, the temperatures are indicated in degrees centigrade (°C); the NMR spectral
data were recorded with a 360MHz machine in CDCl3, the chemical displacement 8 are
indicated in ppm with respect to the TMS as standard, the coupling constant J are
expressed in Hz and all the abbreviations have the usual meaning in the art.
Example 1
Synthesis of 2.3.4.5-tetramethvl-2-cvclopenten-l-one
a) Preparation of the metal catalyst solution
A catalytic solution containing the TiCl3(OiPr) complex is obtained according to the
procedure described in E.V. Vedejs et al., J. Org. Chem., (1988), 53, 1593 but using
the TiCl4 and the Ti(OiPr)4 complexes as starting materials. The quantities were

modified in order to obtain catalytic solution .with a concentration of 1.3 mmole of
metal per gram of catalytic solution.
All the resulting solutions were used without further manipulation.
b) Preparation of 2,3,4,5-tetramethyl-2-cyclopenten-1-one
In a bottom round flask equipped with a mechanical stirrer, a dropping funnel and a
reflux condenser was loaded 2000g (23.2 mol) of the starting ketone with 75% w/w of
butylacetate as the solvent, 0.35 molar equivalents of anhydrous magnesium chloride
and the aforementioned titanium catalytic solution containing 0.06 molar equivalents of
the trichloropropoxytitaniurn complex. The resulting suspension was stirred vigorously
and allowed to heat to 90°C. Then 2 molar equivalents of the acetaldehyde were added
dropwise over 3h at 90°C. The reaction was continued for an additional hour and
cooled to 40°C. The reaction mixture was hydrolysed with a 10% aqueous acetic acid
solution and neutralised with a 20% aqueous potassium carbonate solution.
The resulting organic phase was directly fractionated into a laboratory Sulzer packed
column, to afford the title compound, as a mixture of isomers transxis = 85:15, in 27 %
yield (B.p. = 70-80°C at P = 8 mbar) and the enone (II), (i.e. 4-methyl-4-hexen-3-one)
in 31 % yield (B.p. = 45-65°C at P = 8 mbar).
1H-NMR (isomer trans): 1.15 (d 3H); 1.19 (d 3H); 1.68 (s 3H); 1.88 (m 1H); 1.98 (s..
3H); 2.25 (m 1H).
13C-NMR (isomer trans): 8.5; 14.6; 15.1; 17.7; 46.2; 48.4; 134.5; 171.6; 211.0.
Example 2
Synthesis of 3,4-diethyl-2.5-dimethyl-2-cyclopenten-l -one
In a bottom round flask equipped with a mechanical stirrer, a dropping funnel and a reflux
condenser were loaded 265g (3.08 mol) of the diethyl ketone with 252 g of butylacetate as
the solvent, 0.36 molar equivalents of anhydrous magnesium chloride and the
aforementioned titanium catalytic solution containing 0.053 molar equivalents of the
trichloropropoxytitaniurn complex. The resulting suspension was stirred vigorously and
allowed to heat to 85°C. Then 2.1 molar equivalents of propionaldehyde were added
dropwise over 2h at 85°C. The reaction was continued for an additional hour and cooled


to 40°C. The reaction mixture was hydrolyzed with a 10% aqueous acetic acid solution
(500g), decanted and washed with a 10% aqueous acetic acid solution (200g) and 50 g of
NaCl. The organic phase was then washed twice with a 20% aqueous potassium carbonate
solution.
After drying over Na2SO4, the solvent was evaporated. The crude product (419.6 g), was
distilled through a Vigreux column and then fractionated through a Fischer column, to
afford the title compound in 17% yield (B.p. = 58°C at P = 3 mbar) and the enone (II) (i.e.
4-methyl-4-hepten-3-one) in 32 % yield (B.p. = 84°C at P = 43 mbar).
MS: 166 (76); 151 (37); 138 (100); 137 (94); 109 (72); 67 (54); 41 (30).
1H-NMR: 2.52 (1H; m); 2.29 (2H; m); 2.01(1H; dq; 2.5 Hz; 8 Hz); 1.90-1.80 (1H; m);
1.69 (3H; br s); 1.34-1.22 (1H; m); 1.17 (3H; d; J=6 Hz); 1.10 (3H; d; J=7 Hz);
0.94 (3H; d; J=8 Hz).
13C-NMR: 211.8 (s); 175.9 (s); 134.4 (s); 50.5 (d); 45.2 (d); 25.2( t); 21.8 (t); 16.9 (q),
11.8(q);11.4(q);8.0(q).
Example 3
Synthesis of various compounds of formula (I)
General procedure for cyclopentenone process
In a bottom round flask equipped with a mechanical stirrer, a dropping funnel and a reflux
condenser was loaded 1 molar equivalents of the starting ketone (see further below) neat
or with 75% w/w of butylacetate as the solvent, 0.35 molar equivalents of anhydrous
magnesium chloride and the aforementioned titanium catalytic solution containing
0.05 molar equivalents of the trichloropropoxytitanium complex. The resulting suspension
was stirred vigorously and allowed to heat to 90-100°C. Then the aldehyde of formula
(III) (see further below) was dropped over 3 hours at 90-l00°C. The reaction was
continued an additional hour at 90-100°C and cooled to 40°C. The reaction mixture was
hydrolyzed with a 10% hydrochloric acid solution and neutralized with a 20% potassium
carbonate solution.
The resulting organic phase was directly fractionated into a laboratory Sulzer packed
column. The results are summarized herein below.

Experiment A)
Starting ketone: 4-methyl-4-hexen-3-one
Starting aldehyde: benzaldehyde (1.2 molar equivalents)
Products:
4-phenyl-2,3,5-trimethyl-2-cyclopenten-l-one + 3-phenyl-2,4,5-trimethyl-2-
cyclopenten-1-one (20/80)
yield: 25% (based on used starting ketone)
yield: 45% (based on converted starting ketone)
Analysis for the major product (3-phenyl-2,4,5-trirnethyl-2-cyclopenten-l-one):
1H-NMR: 1.08 (d, 3H); 1.25 (d, 3H); 1.88 (s, 3H); 2.05 (m, 1H); 2.85 (m, 1H); 7.3-7.5
(m, 5H).
13C-NMR: 9.5; 15.5; 19; 45; 48.5; 127-129 (6C); 135; 170.5; 211.
Experiment B)
Starting ketone: 4-methyl-4-hexen-3-one
Starting aldehyde: 10-undecenal (0.9 molar equivalents)
Products:
4-(9-decenyl)-2,3,5-trimethyl-2-cyclopenten-l-one + 3-(9-decenyl)-2,4,5-trimethyl-27
cyclopenten-1-one (33/66)
yield: 36% (based on used starting ketone)
yield: 72% (based on converted starting ketone)
Analysis of the mixture obtained:
1H-NMR: 1.15 (d); 1.17 (d); 1.25-1.40 (m); 1.70 (s); 1.90 (m); 2.0 (s); 2.05 (m); 2.35 (m);
2.50 (m); 4.95 (m, 2H); 5.80 (m, 1H).
13C-NMR: 8; 15; 17; 18; 27; 28-30; 33; 34; 44; 47; 49; 52; 114; 135; 135.5; 139; 171;
175.5; 211.
Experiment C)
Starting ketone: 5-ethyl-4-methyl-4-hepten-3-one
Starting aldehyde: acetaldehyde (1.2 molar equivalents)
Products:
4,4-diethyl-2,3,5-trimethyl-2-cyclopenten-1 -one

yield: 40% (based on used starting ketone)
yield: 58% (based on converted starting ketone)
Analysis of the product:
1H-NMR: 0.45 (t, 3H); 0.78 (t, 3H); 1.08 (d, 3H); 1.35-1.70 (m, 4H); 1.70 (s, 3H); 1.85
(s, 3H); 2.20 (q, 1H).
13C-NMR: 7.95; 8.75; 9.60; 10.10; 12.30; 27.55; 29.95; 46.40; 51.85; 136.3; 171.1; 210.3.
Experiment D)
Starting ketone: Diethylketone
Starting aldehyde: Benzaldehyde (3.0 molar equivalents)
Products:
3,4-diphenyl-2,5-dimethyl-2-cyclopenten-l-one cis/trans: 15/85
yield: 32% (based on used starting ketone)
yield of ketone (II): 24% (based on used starting ketone)
Analysis of the product:
Trans isomer
1H-NMR: 1.34 (d, J=7.17, 3H); 2.02 (s, 3H); 2.40 (dq, J,=7.17, h= 2.56, 1H);3.97 (sb,
1H); 7.0-7.3 (m 10H)
13C-NMR: 10.1; 15.3; 51.25; 56.33; 126-129 (10 CH); 135.2 ; 136.7; 142 ; 167; 210.9
Cis isomer
1H-NMR: 0.75 (d, J=7.68, 3H); 2.08 (s, 3H); 2.92 (m, 1H); 4.6 (d, J=6.14, 1H); 7.0-7.3
(m, 10H)
13C-NMR: 9.8; 12.3; 45.5; 52.5; 126-129 (10 CH); 135.7 ; 136.9; 139.2 ; 166.3; 211.4
Experiment E)
Starting ketone: 1-3 diphenylacetone
Starting aldehyde: acetaldehyde (3.0 molar equivalents)
Products:
3,4-dimethyl-2,5-diphenyl-2-cyclopenten-l-one cis/trans: 15/85
yield: 48% (based on used starting ketone)
yield of ketone (II): 36% (based on used starting ketone)
Analysis of the product:

Trans isomer
1H-NMR: 1.35 (d, J=6.65, 3H); 2.17 (s, 3H); 2.87 (dq, J1=6.65, J2= 3.07, 1H); 3.23 (d,
J=3.07, 1H); 7.1-7.4 (m, 10H)
13C-NMR: 15.9; 18.1; 47.7; 60.7; 126-129 (10 CH); 131.8 ; 138.9; 139.5 ; 174; 205.
Cis isomer
1H-NMR: 0.8 (d, J=7.17, 3H); 2.15 (s, 3H); 3.15 (m, 1H); 3.95 (d, J=7.17, 1H); 7.1-7.4
(m, 10H).
13C-NMR: 16.1; 16.3; 42.8; 56.7; 126-129 (11 CH); 137.7; 139.7 ; 174.7; 206.5

WE CLAIM:
1. A process for the preparation of a compound of formula

wherein R represents a C1-8 alkyl or alkenyl group optionally substituted or a C5-6
aromatic, optionally substituted; and
R1, R2, R3 and R4 represent, simultaneously or independently, a hydrogen atom, a C1-8
alkyl or alkenyl group optionally substituted or a C5-6 aromatic group, optionally
substituted;
said process comprising the reaction between an enone of formula

wherein R, R1, R3 and R4 have the same meaning as in formula (I);
said optional substituents, when said R, R1, R2, R3 and R4 groups represent alkyl or
alkenyl group, are one or two methyl, ethyl, methoxy or ethoxy groups; and said
optional substituents, when said R, R1, R2, R3 and R4 groups represent an aromatic
group, are one or two methyl, ethyl, methoxy, ethoxy or nitro groups
with an aldehyde of formula

wherein R2 has the same meaning as in formula (I); and

the reaction between said enone (II) and the aldehyde (III) being performed at a
temperature comprised between 60°C and 140°C and in the presence of a catalytic system
comprising:
i) at least one metal complex of formula
M(OR5) 4-nXn (TV)
wherein M is Ti(IV) or Zr(IV), R5 represents a C1-6 linear or branched alkyl group, X
represents a halide and n represents an integer from 1 to 3; and
ii) at least one co-ingredient selected from the group consisting of
a) an alkyl or aromatic carboxylic acid anhydride containing 2 to 10 carbon atoms;
b) an anhydrous sulfate, chloride or bromide of a metal cation selected from the
group consisting of Li+, Na+, K+, Cs+, Mg2+, Ni2+, Ca2+, Zn2+, Fe3+ and Al3+;
c) an insoluble inorganic material capable to form a chlatrate with water; and
d) a C4-C15 orthoester, BF3, N-methyl-N-trimethylsilyl-trifluoroacetamide,
1-trimethylsilylimidazole and ClSi(R6)3, R6 representing a C1-5 alkyl group.
2. A process as claimed in claim 1, wherein R represents a C1-8 alkyl or
alkenyl group; and
R1, R2, R3 and R4 represent, simultaneously or independently, a hydrogen atom, a C1-8
alkyl or alkenyl group.
3. A process as claimed in claim 1, wherein R represents a methyl, ethyl or
pentyl group or a phenyl group optionally substituted.
4. A process as claimed in claim 1, wherein R1, R2, R3 and R4 represent,
simultaneously or independently, a hydrogen atom, a methyl, ethyl or pentyl group or a
phenyl group optionally substituted.
5. A process as claimed in claim 1, wherein R, R1, R2 or R3 represents,
simultaneously or independently, a methyl, ethyl or phenyl group optionally substituted,
and R4 represents a hydrogen atom.

6. A process as claimed in claim 1, wherein the enone (II) is obtained in situ
by reacting together a ketone of formula

with an aldehyde or ketone of formula

wherein R, R1, R3 and R4 have the same meaning as in claim 1;
in the presence of a catalytic system as defined in claim 1.
7. A process as claimed in claim 1, wherein M represents Ti(IV), R5
represents a linear or branched C3-4 alkyl group, X represents a Cl atom and the index n
represents 2 or 3
8. A process as claimed in claim 5, wherein the co-ingredient of the catalytic
system is selected from the group consisting of an alkyl or aromatic carboxylic acid
anhydride containing 4 to 8 carbon atoms, BF3, CISi(R6)3, R6 representing a C1-5 alkyl
group, and an anhydrous sulfate, chloride or bromide of a metal cation selected from the
group consisting of Na+, K+, Mg2+, Ca2+, Zn2+, Fe3+.


The invention relates to a process for the preparation, in a single step, of substituted 2-cyclopenten-1-ones by reacting
a substituted enone with an aldehyde in the presence of a catalytic system. Said catalytic system consists of a metal complex, snch
as a [Ti(Cl)3(alkoxy)], and a co-ingredient, such as a carboxylic acid anhydride or an anhydrous salt.

Documents:

01802-kolnp-2007-abstract.pdf

01802-kolnp-2007-assignment.pdf

01802-kolnp-2007-claims.pdf

01802-kolnp-2007-correspondence others 1.1.pdf

01802-kolnp-2007-correspondence others.pdf

01802-kolnp-2007-description complete.pdf

01802-kolnp-2007-form 1.pdf

01802-kolnp-2007-form 3 1.1.pdf

01802-kolnp-2007-form 3.pdf

01802-kolnp-2007-form 5.pdf

01802-kolnp-2007-gpa.pdf

01802-kolnp-2007-international publication.pdf

01802-kolnp-2007-international search report.pdf

01802-kolnp-2007-pct request form.pdf

01802-kolnp-2007-priority document.pdf

1802-KOLNP-2007-(10-02-2012)-CORRESPONDENCE.pdf

1802-KOLNP-2007-ABSTRACT 1.1.pdf

1802-KOLNP-2007-AMANDED CLAIMS.pdf

1802-KOLNP-2007-ASSIGNMENT.pdf

1802-KOLNP-2007-CORRESPONDENCE1.1.pdf

1802-KOLNP-2007-DESCRIPTION (COMPLETE) 1.1.pdf

1802-KOLNP-2007-EXAMINATION REPORT.pdf

1802-KOLNP-2007-FORM 1-1.1.pdf

1802-KOLNP-2007-FORM 13.1.pdf

1802-KOLNP-2007-FORM 13.pdf

1802-KOLNP-2007-FORM 18.pdf

1802-KOLNP-2007-FORM 2.pdf

1802-KOLNP-2007-FORM 3-1.2.pdf

1802-KOLNP-2007-FORM 3.pdf

1802-KOLNP-2007-FORM 5-1.1.pdf

1802-kolnp-2007-form-18.pdf

1802-KOLNP-2007-GPA.pdf

1802-KOLNP-2007-GRANTED-ABSTRACT.pdf

1802-KOLNP-2007-GRANTED-CLAIMS.pdf

1802-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

1802-KOLNP-2007-GRANTED-FORM 1.pdf

1802-KOLNP-2007-GRANTED-FORM 2.pdf

1802-KOLNP-2007-GRANTED-SPECIFICATION.pdf

1802-KOLNP-2007-INTERNATIONAL SEARCH REPORT 1.1.pdf

1802-KOLNP-2007-MISCLLENIOUS.pdf

1802-KOLNP-2007-OTHERS 1.1.pdf

1802-KOLNP-2007-OTHERS.pdf

1802-KOLNP-2007-PETITION UNDER RULE 137.pdf

1802-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

1802-KOLNP-2007-REPLY TO EXAMINATION REPORT1.1.pdf


Patent Number 252102
Indian Patent Application Number 1802/KOLNP/2007
PG Journal Number 17/2012
Publication Date 27-Apr-2012
Grant Date 25-Apr-2012
Date of Filing 21-May-2007
Name of Patentee FIRMENICH SA
Applicant Address 1, ROUTE DES JEUNES, P.O. BOX 239, CH-1211 GENEVA 8
Inventors:
# Inventor's Name Inventor's Address
1 JACOBY, DENIS 81, ROUTE DU BOIRON, CH-1260 NYON
2 KELLER, FABRICE 74B, CHEMIN PRÉ-GENTIL, CH-1242 SATIGNY
PCT International Classification Number C07C 45/74
PCT International Application Number PCT/IB2005/053717
PCT International Filing date 2005-11-11
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 PCT/IB2004/003719 2004-11-11 IB
2 PCT/IB2004/003854 2004-11-18 IB