U.S. patent application number 09/871873 was filed with the patent office on 2001-11-15 for n-(2-mercaptoethyl)-1,3-thiazolidines and their use as odorants and flavorings.
Invention is credited to Engel, Wolfgang, Guntert, Matthias, Lambrecht, Stefan, Schieberle, Peter.
Application Number | 20010041800 09/871873 |
Document ID | / |
Family ID | 7914472 |
Filed Date | 2001-11-15 |
United States Patent
Application |
20010041800 |
Kind Code |
A1 |
Engel, Wolfgang ; et
al. |
November 15, 2001 |
N-(2-mercaptoethyl)-1,3-thiazolidines and their use as odorants and
flavorings
Abstract
Substituted N-Mercaptoethyl-1,3-thiazolidines are novel
compounds which can be used in odorants and flavorings.
Inventors: |
Engel, Wolfgang; (Neufahrn,
DE) ; Schieberle, Peter; (Freising, DE) ;
Guntert, Matthias; (Teterboro, NJ) ; Lambrecht,
Stefan; (Holzminden, DE) |
Correspondence
Address: |
BAYER CORPORATION
PATENT DEPARTMENT
100 BAYER ROAD
PITTSBURGH
PA
15205
US
|
Family ID: |
7914472 |
Appl. No.: |
09/871873 |
Filed: |
June 1, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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09871873 |
Jun 1, 2001 |
|
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09610757 |
Jul 6, 2000 |
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Current U.S.
Class: |
548/146 ;
512/10 |
Current CPC
Class: |
C07D 277/04 20130101;
C11B 9/0096 20130101 |
Class at
Publication: |
548/146 ;
512/10 |
International
Class: |
A61K 007/46; C07D
277/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 12, 1999 |
DE |
19932495.6 |
Claims
What is claimed is:
1. Compounds of the formula 3wherein R.sub.1, R.sub.2 and R.sub.3
are identical or different and R.sub.1is hydrogen, methyl, ethyl,
propyl, or isopropyl; R.sub.2 is hydrogen, acetyl, propionyl,
isobutyryl, methyl, ethyl, propyl, or isopropyl and R.sub.3 is
hydrogen or 4
2. A compound according to claim 1, wherein said compound is
N-(2-Mercaptoethyl)-1,3-thiazolidine.
3. Odorant and flavoring compositions comprising compounds of the
formula 5wherein R.sub.1, R.sub.2 and R.sub.3 are identical or
different and R.sub.1 is hydrogen, methyl, ethyl, propyl, or
isopropyl; R.sub.2 is hydrogen, acetyl, propionyl, isobutyryl,
methyl, ethyl, propyl, or isopropyl and R.sub.3 is hydrogen or
6
4. Odorant and flavoring compositions according to claim 3, wherein
said compound is N-(2-Mercaptoethyl)-1,3-thiazolidine.
5. Flavoring in liquid and dry flavors for foods and drinks and in
flavors for packages comprising N-(2-Mercaptoethyl)-1,3
-thiazolidine.
6. Flavoring in liquid and dry flavors for packages of foods and
drinks and for spraying of food aromas and for room air fragrancing
comprising N-(2-Mercaptoethyl)-1,3-thiazolidine.
Description
FIELD OF THE INVENTION
[0001] The invention relates to
N-(2-Mercaptoethyl)-1,3-thiazolidines, processes for their
preparation and their use as aromatizing substance in foods and
drinks and for spraying food aromas and for room air
fragrancing.
BACKGROUND OF THE INVENTION
[0002] In the flavor industry, there is still a great demand for
substances which impart an ol-factory impression to foods and
drinks such as results in the thermal treatment during boiling,
baking and roasting of foods. The resultant aromatizing compounds
exhibit especially roasted notes. However, these compounds in
particular have been scarcely available. In addition to the flavor,
which is largely actually perceived retronasally as an odor, the
orthonasally perceived odor currently plays an important role.
Therefore, flavor compounds are also of importance which impart a
corresspondingly strong and typical odor to a food or drink.
[0003] The most important reaction which proceeds in the thermal
treatment of foods is the reaction between reducing sugars and
amino acids which is called the Maillard reaction. During this
Maillard reaction, flavorings of the heterocycle class of chemical
substances are formed. These compounds contain one or more
heteroatoms, various side chains and are aromatic or partially
hydrogenated (P. A. Finot, H. U. Aeschbacher, R. F. Hurrell, R.
Liardon, The Maillard Reaction in Food Processing, Human Nutrition
and Physiology, BirkHuser Verlag, Basle, 1990).
SUMMARY OF THE INVENTION
[0004] As a novel class of odorant and flavoring substances,
N-(2-Mercaptoethyl)-1,3-thiazolidines and their disulphildes of the
formula 1
[0005] have been found, wherein R.sub.1, R.sub.2 and R.sub.3 are
identical or different and R.sub.1 is hydrogen, methyl, ethyl,
propyl or isopropyl, R.sub.2 is hydrogen, acetyl, propionyl,
isobutyryl, methyl, ethyl, propyl or isopropyl and R.sub.3 is
hydrogen or 2
[0006] Substituted N-Mercaptoethyl-1,3-thiazolidines and their
disulphides are odorants and flavorings.
DETAILED DESCRIPTION OF THE INVENTION
[0007] The inventive Substituted N-Mercaptoethyl-1,3-thiazolidines
and their disulphides, in particular
N-(2-Mercaptoethyl)-1,3-thiazolidine, surprisingly have very low
threshold values. For example, the inventive
N-(2-Mercaptoethyl)-1,3-thiazolidine has a surprisingly low
threshold value at 0.005 ng/l in air. This makes it possible to use
it as an aromatizing constituent at very low concentrations. In
addition, N-(2-Mercaptoethyl)-1,3-thiazolidine imparts a
particularly strong and typically roasted flavor to foods.
[0008] Compared with the thiazolines, among which, especially
2-acetyl-2-thilazoline is a known flavoring (J. Kerler, J. G. M.
van der Veen, II. Weenan, Food Rev. Int., 1997, 13, 553-575),
little is known to date on the thilazoline class of substances as
flavorings. Although in the scientific literature, thiazolidines
are also described as reaction products of sugars and amino acids,
these thiazolidines are not, however, distinguished by
corresponding aromatizing properties and therefore do not appear
either as industrially used flavorings.
[0009] Surprisingly, N-(2-Mercaptoethyl)-1,3-thiazolidine develops
virtually no retronasal flavor activity in aqueous solutions, that
is to say, on tasting, it is scarcely perceived to have flavor.
However, it has a very strong orthonasal action and develops an
intensive roasted odor note. Thus, although the flavoring
N-(2-Mercaptoethyl)-1,3-thiazolidine of the present invention has
similar sensory properties to furfuryhthiol, it has a much more
intense aroma and has a considerably lower odor threshold. This was
determined at 0.005 ng/l in air. Thus, the compound belongs to the
most aroma-intensive compounds, which are known in flavor
chemistry.
[0010] N-(2-Mercaptoethyl)-1,3-thiazoline was identified as a
thermal reaction product of cysteamine with fructose (Example 1).
Its structural origin, however, is not as simple to explain.
Presumably, cysteamine and formaldehyde contribute to its thermal
formation. It was identified by fractionating the extract from the
reaction mixture by gas chromatography and subsequent mass
spectromectric analysis. N-(2-Mercaptoethyl)-1,3-thia- zolidine was
unambiguously identified by comparison with the analytical data of
an authentic sample.
[0011] In addition, systematic experiments have also been carried
out by using a chromatograpic method which is termed gas
chromatography-olfactom- etry (GC-O). In this method, the compounds
which were separated during the chromatographic process are sniffed
individually with the nose at the end of the capillary column.
Using these methods, the olfactory and gustatory qualities of
N-(2-Mercaptoethyl)-1,2-thiazolidine were pre-evaluated.
[0012] The structure was demonstrated by comparison with
synthesized N-(2-Mercaptoethyl)-1,3-thiazolidine.
N-(2-Mercaptoethyl)-1,3-thiazolidin- e can be prepared starting
from thiazolidine. Thiazolidine is admixed with ethylene sulphide
and heated under an inert gas atmosphere for 24 hours at 80.degree.
C. After purification N-(2-Mercaptoethyl)-1,3-thiazolidine is
obtained (Example 2).
[0013] The compound of the present invention
N-(2-Mercaptoethyl)-1,3-thiaz- olidine is, because of its
outstanding organoleptic character, particularly suitable as a
flavoring for use in flavor compositions. It is particularly
surprising that N-(2-Mercaptoethyl)-1,3-thilazoline imparts a very
intensive roasted note to the relevant compositions at extremely
low concentrations. In this case the flavor is perceived
particularly by smell (orthonasally).
[0014] In ready-to-use flavors, the amount of the compound of the
present invention used is preferably between 0.00005 and 1% by
weight, in particular between 0.0001 and 0.5% by weight, based on
the total composition. Flavor compositions of this type can be used
in the entire food and drink sector. In particular, they are
suitable for aromatizing snacks, soups, sauces, ready-to-eat meals,
fat compositions, bakery products, yogurt, ice cream and
confectionery products. The dosage of flavor compositions of this
type is preferably 0.005 to 2% by weight, in particular between
0.01 and 1% by weight, based on the finished food or drink.
[0015] The ready-to-use flavors can be used in liquid form or in
spray-dried form or in en- capsulated for. Whereas, in liquid form,
they are used in a solvent which is cus- tomary in practice, such
as ethanol, propyleine glycol, vegetable oil triglycerides or
triacetin, the dry flavors are produced by splay-drying or by
encapsulation according to a process customarily in the flavor
industry. These are the extrusion and spray granulation
processes.
[0016] Owing to the intense odor activity, the compound of the
present invention N-(2-Mercaptoethyl)-1,3-thiazolidine is also
suitable, in particular, for aromatizing packages of foods and
drinks, and also for other applications (e.g. spraying of food
aromas and for room air fragrancing).
[0017] The invention is further illustrated but is not intended to
be limited by the following examples in which all parts and
percentages are by weight unless otherwise specified.
EXAMPLES
Example 1
Reaction Between Cysteamine and Fructose
[0018] 3.3 mmol of cysteamine and 10 mmol of fructose arc heated to
145.degree. C. in 20 minutes in a phosphate buffer at pH 7. The
flavorings are obtained by extraction with ethyl ether and
subsequent concentration. They were identified by GC/MS.
Example 2
Preparation of 2-Substituted
N-(2-Mercaptoethyl)-1,3-Thiazolidines
[0019] a) Preparation of 2-substituted thiazolidines
[0020] 1.1 mmol of carbonyl compound or dicarbonyl compound ire
reacted with 1.1 mmol of cysteamine hydrochloride in oxygen-free
aqueous phosphate buffer solution (pH=7) under a protective gas
atmosphere. The reaction is carried out, in the case of the
reactive components formaldehyde, acetaldehiyde and
miethiylglyoxal, at 0.degree. C. The reaction is followed by gas
chromatography. After work-up and chromatographic purification, the
corresponding thiazolidines are obtained.
[0021] b) Preparation of the 2-substituted N-(2-N-Mercaptoethyl)-
1,3-thiazolidines
[0022] 10 mmol of 2-substituted thiazolidine are admixed in a glass
autoclave with 10 mmol of ethylene sulphide and heated without
solvent at 80.degree. C. for 24 hours under a protective gas. The
reaction mixture is taken up in sodium hydroxide Solution and
washed with dichiloromiethane. The aqueous phase is adjusted to pH
8 with hydrochloric acid and extracted with dichitoromethane. The
N-(2-Mercaptoethyl)-thiazolidines are obtained at a purity of
approximately 90-96% and in a yield of 75-88%.
[0023] Mass spectrum of N-(2-Mercaptoethyl)-thiazolidine
1 Intensity m/z % 27 12 28 12 42 45 45 12 56 12 57 13 59 9 61 15 88
7 102 100
EXAMPLE 3
Preparation of a Roasted Flavor
[0024] The following were mixed (all quantities in g):
2 3-Methylthiopropanal (1% in vegetable oil triglycerides) 1.0
2,3-Diethyl-5-methylpyrazine 1.0 Isoamyl caprylate 1.0 Diacetyl
(10% in triacetin) 2.0 2-Methylbutyric acid 5.0 Isoamyl alcohol
10.0 Delta-dodecalactone 10.0 2- Phenylethanol 15.0 2-Methylbutanal
20.0 Capiylic acid (10% in triacetin) 25.0 Dimethyloxyfurone (1% in
propylene glycol) 100.0 2,5-Dimethyl-4-hydroxy-3(2H)-furanone (15%
in 500.0 propylene glycol) Vegetable oil triglycerides 9310.0 Total
10000.0
[0025] When 0.1-0.5 g of the solvent vegetable oil triglycerides
were replaced by 0.1-0.5 g of N-(2-Mercaptoethyl)-thiazolidine, the
flavor became markedly more typical in the direction towards
roasted bread crust.
[0026] Although the invention has been described in detail in the
foregoing for the purpose of illustration, it is to be understood
that such detail is solely for that purpose and that variations can
be made therein by those skilled in the art without departing from
the spirit and scope of the invention except as it may be limited
by the claims.
* * * * *