Perfume compositions – Perfume compositions – Oxygen containing active ingredient
Reexamination Certificate
2000-03-23
2002-12-31
Ludlow, Jan (Department: 1743)
Perfume compositions
Perfume compositions
Oxygen containing active ingredient
C512S002000, C512S003000, C512S025000, C512S026000, C554S115000, C560S126000, C560S051000, C560S174000
Reexamination Certificate
active
06500797
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to methods for preparing &bgr;-ketoester fragrance pro-accords, said pro-accords useful for providing sustained fragrance to items which deliver perfume for aesthetic reasons inter alia laundry detergent compositions, fabric softeners, personal care and personal hygiene items, shampoos, body lotions, and fabric re-fresheners. The process of the present invention relates to the use of 1,3-dioxane-4,6-diones as a synthon for the facile formation of &bgr;-ketoesters, especially &bgr;-ketoesters which comprise a tertiary alcohol subunit.
BACKGROUND OF THE INVENTION
Esters which release perfume alcohols are currently of interest for their different odor profiles in products, as well as their odor profiles during and after use. Particularly desirable are such esters which have a prolonged release characteristic from use in a home laundering process. Deposition onto a substrate, for example, onto fabric during the wash process followed by delayed release of the perfume after drying, is especially desirable. The challenge for using such esters include not only the right combination of storage stability and odor release profile, but also the challenge of making such esters in a cost effective manner.
&bgr;-Ketoesters are a particularly desirable class of materials, but such materials can present a particular challenge for a cost effective production. The di-functionality (ketone and carboxylic ester functionality in the same compound) of these compounds limits the types of reactions and conditions under which these compounds can be made. Add on the industrial scale and cost constraints that the use of specialty reactants add to the possible synthesis methods, and the large scale of production of such &bgr;-ketoester compounds for use in high volume consumer products becomes problematic.
Accordingly there remains a need in the art for a method for a simple, high yield, cost-effective means for preparing &bgr;-ketoester fragrance pro-accords. In addition there is a need for convenient methods which produce &bgr;-ketoesters capable of releasing tertiary alcohols inter alia dihydromyrcenol and linalool.
BACKGROUND ART
The following relate to the preparation of &bgr;-ketoesters from 1,3-dioxane-4,6-diones. Oikawa et al.,
J. Org. Chem
., Vol 43, No 10, 1978, pg. 2087; Capozzi et al.,
J. Org. Chem
., Vol 58, No 27, 1993, pg. 7932; Organic Synthesis Collective Volumes, pg 359, Oikawa et al., submitters; and Houghton et al., “A Modified Preparation of &bgr;-Keto Esters”,
Synthesis
, pg 451, (1982).
SUMMARY OF THE INVENTION
It has now been surprisingly discovered that molecules which releasably comprise fragrance raw material alcohols, namely &bgr;-ketoester fragrance pro-accords, can be suitably prepared from activated acyl adducts, for example, acid chlorides, and 1,3-dioxan-4,6-diones followed by reacting the product with a fragrance raw material alcohol. It is especially desirable that the fragrance raw material alcohols which become a subunit of the &bgr;-ketoester fragrance pro-accord are tertiary alcohols, for example, linalool and dihydromycenol.
The first aspect of the present invention relates to a process for preparing &bgr;-ketoester fragrance pro-accords comprising the steps of:
a) reacting in the presence of a base a 1,3-dioxane-4,6-dione having the formula:
wherein R
1
and R
2
are each independently C
1
-C
10
alkyl, C
2
-C
10
alkenyl, C
7
-C
22
alkylenearyl, C
6
-C
10
aryl, and mixtures thereof; with an activated acyl group having the formula:
wherein R
3
, R
4
, and R
5
are each independently hydrogen, C
1
-C
30
substituted or unsubstituted linear alkyl, C
3
-C
30
substituted or unsubstituted branched alkyl, C
3
-C
30
substituted or unsubstituted cyclic alkyl, C
1
-C
30
substituted or unsubstituted linear alkoxy, C
3
-C
30
substituted or unsubstituted branched alkoxy, C
3
-C
30
substituted or unsubstituted cyclic alkoxy, C
2
-C
30
substituted or unsubstituted linear alkenyl, C
3
-C
30
substituted or unsubstituted branched alkenyl, C
3
-C
30
substituted or unsubstituted cyclic alkenyl, C
2
-C
30
substituted or unsubstituted linear alkynyl, C
3
-C
30
substituted or unsubstituted branched alkynyl, C
6
-C
30
substituted or unsubstituted alkylenearyl; or R
3
, R
4
, and R
5
can be taken together to form C
6
-C
30
substituted or unsubstituted aryl; and mixtures thereof; X is an acyl activating unit; to form an acyl 1,3-dioxane-4,6-dione, the enol tautomer of which having the formula:
b) optionally, isolating said acyl 1,3-dioxane-4,6-dione; and
c) reacting said acyl 1,3-dioxane-4,6-dione from step (a) or (b) with a fragrance raw material alcohol having the formula:
ROH
to form a &bgr;-ketoester fragrance pro-accord having the formula:
wherein R
3
, R
4
, and R
5
are the same as defined herein above.
The present invention more specifically relates to the preparation of &bgr;-ketoester fragrance pro-accords which comprise a secondary or tertiary alcohol subunit, more preferably a tertiary alcohol subunit. These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims.
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a process for preparing &bgr;-ketoester fragrance pro-accords from 1,3-dioxan-4,6-diones, preferably from 2,2-dimethyl-1,3-dioxan-4,6-dione. Variations of the present process include isolation and purification of the intermediate acyl 1,3-dioxane-4,6-dione formed in Step (a) prior to subsequent reaction with a fragrance raw material alcohol. However, the formulator, depending upon several variables inter alia the structure of the final &bgr;-ketoester, the amount of material to be produced, the type of process (i.e. batch reactions vs. continuous process) may produce the final product without isolation of the acyl 1,3-dioxan-4,6-dione intermediate.
For the purposes of the present invention the term “substituted” as it applies to linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl, branched alkenyl, cyclic alkenyl, branched alkoxy, cyclic alkoxy, alkynyl, and branched alkynyl units are defined as “carbon chains which comprise substitutents other than branching of the carbon atom chain”, for example, other than the branching of alkyl units (e.g. isopropyl, isobutyl). Non-limiting examples of “substituents” include hydroxy, C
1
-C
12
alkoxy, preferably methoxy; C
3
-C
12
branched alkoxy, preferably isopropoxy; C
3
-C
12
cyclic alkoxy; nitrilo; halogen, preferably chloro and bromo, more preferably chloro; nitro; morpholino; cyano; carboxyl, non-limiting examples of which are —CHO; —CO
2
−
M
+
, —CO
2
R
9
; —CONH
2
; —CONHR
9
; —CONR
9
2
; wherein R
9
is C
1
-C
12
linear or branched alkyl); —SO
3
−
M
+
; —OSO
3
−
M
+
; —N(R
10
)
2
; and —N
+
(R
10
)
3
X
−
wherein each R
10
is independently hydrogen or C
1
-C
4
alkyl; and mixtures thereof; wherein M is hydrogen or a water soluble cation; and X is chlorine, bromine, iodine, or other water soluble anion.
For the purposes of the present invention substituted or unsubstituted alkyleneoxy units are defined as moieties having the formula:
wherein R
7
is hydrogen; R
8
is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 10.
For the purposes of the present invention substituted or unsubstituted alkyleneoxyalkyl are defined as moieties having the formula:
wherein R
7
is hydrogen, C
1
-C
18
alkyl, C
1
-C
4
alkoxy, and mixtures thereof; R
8
is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 10 and the index y is from 2 to about 18.
For the purposes of the present invention substituted or unsubstituted aryl units are defined as phenyl moieties having the formula
Ortiz Rafael
Schectman Lee Arnold
Sivik Mark Robert
Wos John August
Cole Monique T.
Ludlow Jan
McBride James F.
Miller Steven W.
The Procter & Gamble & Company
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