CA2043251A1 - Methanethiols, process for their preparation and their use - Google Patents
Methanethiols, process for their preparation and their useInfo
- Publication number
- CA2043251A1 CA2043251A1 CA002043251A CA2043251A CA2043251A1 CA 2043251 A1 CA2043251 A1 CA 2043251A1 CA 002043251 A CA002043251 A CA 002043251A CA 2043251 A CA2043251 A CA 2043251A CA 2043251 A1 CA2043251 A1 CA 2043251A1
- Authority
- CA
- Canada
- Prior art keywords
- methanethiols
- formula
- ethyl
- group
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Seasonings (AREA)
Abstract
Methanethiols, process for their preparation and their use A b s t r a c t The invention relates to new methanethiols of the formula
Description
~32~1 The invention relates to new methanethiols, to a process for their preparation and ~o their use as flavourings.
New methanethiol~ of the formula ~ (I) ~ 2 have now been found in which X represents an oxygen or sulphur atom, and one of the radicals Rl or R2 represents a mercaptomethyl group and the other represents an ethyl group, It has additionally been found that these methanethiols of ~he formula (I) have useful organoleptic properties.
The invention therefore relates to the new methanethiols of the formula (I) and their use as flavourings.
~ he methanethiols according to the invention are obtained by reaGtion of hydroxymethyl compounds of the formula ~ R'1 (II) R'2 in which X has the maaning indicated under formula ~I), and one of the radicals R'1 or R'2 represents a hydroxymethyl group and the other t ,: , . ., ' .~ ' 2~3251 represents an ethyl group, with thionyl chloride and subsequen~ reaction of the resulting chloromethyl compound with thiourea.
The invention therefore also relates to a process for the preparation of methanethiols of the for~ula (I~, which is characterised in that compounds of the fo~nula (II) are reacted with thionyl chloride in an inert sol-vent, preferably ~n ether, at ~empexatures from 0C to 40C, preferably at room temperature, and the resulting chloromethyl compound is reacted in an alcohol, prefer-ably methanol or ethanol, at temperature~ of 20C up to the boiling poin~ of the alcohol used, preferably at the boiling point, with thiourea.
The starting compounds of the formula (II) are obtainable by customary preparation processes from compounds which are known from the literature.
The compounds according to the invention are useful flavourings which are distingui hed by very low taste threshold valuesO Thus, for example, the taste thre~hold value of [3-~2-ethyl-furyl)]-methanethiol, tested by 5 specially trained testers, i8 0. 1 ppt. The taste descriptions for some typical representatives of the compounds according to ~he invention, determined in O.5% strength aqueous sodium chloride solution, read for [2-(3-ethyl-thienyl)]-methanethiol:
at 1.25 ppt: fatty, stock, liver, fullness at 12.5 ppt: fatty, chicken, meat, liver, roast character, crusts ~3-(2-ethyl-thienyl)~-methanethiol:
at 1.25 ppt: kohlrabi, burning, roasts, roa~t .
2~32~
character [3-t2-ethyl-furyl)]-methanethiol:
at 0.15 ppt: fullness, fatty7 meat stock, chicken fat S at 1.5 ppt: fullness, fatty, blood character, pork, meat stock With their specific taste towards meat, the compounds of ~he formula (I) according ~o the invPntion act in a taste-reinforcing and -rounding off manner in meat flavour composi~ions. However, in other flavour compositions, for example nut flavourings, ~he compounds according to the invention also cause a rounding-off of the flavour and an increase in the fullness of taste.
The flavour compositions prepared using the compounds according to the invention can be employed in the entire foodstuff and luxury yoods sector, and also in animal feed. They are suitable, in particular, for fatty materials, baking goods, extruded products, ready-to-serve meals, meat and sausage produc~s, ~oup8, sauces, vegetable preserves and all types of industrially prepared anLmal feed.
The new methanethiols according to the invention are used in amounts of 5 ppt to 1%, preferably 100 ppt to 100 ppm, relative to the ready to-consume foodstuff.
The percentage data used in the examples are percentages by weight.
Examples Example 1 A solution of 3 g of 2-bromo-3-eth~lthiophene (Chem. Scr. 1974, 217) in 10 ml of ether was ~lowly added .
2~43~
dropwise at -78C under dry nitrogen to 9 ml of a 20~
strength solution of n-butyllithium in toluene ~uch that the temperature did no~ exceed -60C. 1.2 g of para formaldehyde were then added and the mixture was warmed ~o room temperature for 1.5 hours. The reaction mixture was poured into dilute hydroc~loric acid and ex~racted using ether. ~fter distilling off the solvent, 2.~ g of crude product remained which contained 65.7% of 3-ethyl-2-hydroxymethyl-thiophene according to the gas chromato-gram.
1.26 g of thio~yl chloride were added to 1.4 g of this crude produc~ and 1 g of pyridine in 25 ml of ether.
After stirring at room temperature for 4 hours, the reaction mixture was poured into dilute hydrochloric acid and extracted several ~imes using ether. The organic phase was washed until neutral, dried and concentrated.
The residue was dissolved in 50 ml of ethanol and heated to reflux temperature with 0.8 g of thiourea for 30 minutes. After stripping off the solvent, the residue was stirred under nitrogen a~ 60C with 50 ml of 5N sodium hydroxide solution for 1 hour. The mixture was then acidified using dilute hydrochloric acid and e~tracted using ether. The crude product which remained after stripping off the solvent was distilled at 71C and 0.3 mbar. 0.2 g of [2 (3-ethyl-thienyl)]-methanethiol were obtained.
If, instead of 3-ethyl-2-hydro~ymethyl-thiophene~
the isomeric 2-ethyl-3-hydroxymethyl-thiophene ~US Patent 4,560,701) was employed, 3~(2-ethyl-thienyl)-methanethiol was obtained in identical yield. [3-(2-ethyl-furyl~]-` ` 2~4~25~
methanethiol was obtained analogously from 2-ethyl-3-hydroxymethyl-furan (Farmaco, Ed. Sci. 1982, 398). The IR, NMR and mass spectra of the compounds agreed with the structures given.
Example 2 A meat flavour composition was prepared by mixing the following constituents in the parts by weight indi-cated:
50:50 mixture of Na inosinate and Na guanilate Monosodium glutamate 19 Lactic acid, spray-dried 30 Vegetable protein hydrolysate (Type RFB
from Food Ingredient~ Specialities 350 Sweet whey powder 100 Table salt 500 1, 000 A 1~ aqueous solution of this composition was used as a control sample.
I~ 15 ppt of r2-(3-ethyl-thienyl)]-methanethiol were added to the control sample, the flavour was described by a test group as distinctly stronger and fuller towards beef s~ock, gravy and roast meat with a liver character in the background in comparison to the control sample.
On adding 75 ppt of [3-(2-ethyl-fury~
methanethiol to the control sample, the flavour i8 judged as distinctly fuller towards roast meat.
. ,, :
New methanethiol~ of the formula ~ (I) ~ 2 have now been found in which X represents an oxygen or sulphur atom, and one of the radicals Rl or R2 represents a mercaptomethyl group and the other represents an ethyl group, It has additionally been found that these methanethiols of ~he formula (I) have useful organoleptic properties.
The invention therefore relates to the new methanethiols of the formula (I) and their use as flavourings.
~ he methanethiols according to the invention are obtained by reaGtion of hydroxymethyl compounds of the formula ~ R'1 (II) R'2 in which X has the maaning indicated under formula ~I), and one of the radicals R'1 or R'2 represents a hydroxymethyl group and the other t ,: , . ., ' .~ ' 2~3251 represents an ethyl group, with thionyl chloride and subsequen~ reaction of the resulting chloromethyl compound with thiourea.
The invention therefore also relates to a process for the preparation of methanethiols of the for~ula (I~, which is characterised in that compounds of the fo~nula (II) are reacted with thionyl chloride in an inert sol-vent, preferably ~n ether, at ~empexatures from 0C to 40C, preferably at room temperature, and the resulting chloromethyl compound is reacted in an alcohol, prefer-ably methanol or ethanol, at temperature~ of 20C up to the boiling poin~ of the alcohol used, preferably at the boiling point, with thiourea.
The starting compounds of the formula (II) are obtainable by customary preparation processes from compounds which are known from the literature.
The compounds according to the invention are useful flavourings which are distingui hed by very low taste threshold valuesO Thus, for example, the taste thre~hold value of [3-~2-ethyl-furyl)]-methanethiol, tested by 5 specially trained testers, i8 0. 1 ppt. The taste descriptions for some typical representatives of the compounds according to ~he invention, determined in O.5% strength aqueous sodium chloride solution, read for [2-(3-ethyl-thienyl)]-methanethiol:
at 1.25 ppt: fatty, stock, liver, fullness at 12.5 ppt: fatty, chicken, meat, liver, roast character, crusts ~3-(2-ethyl-thienyl)~-methanethiol:
at 1.25 ppt: kohlrabi, burning, roasts, roa~t .
2~32~
character [3-t2-ethyl-furyl)]-methanethiol:
at 0.15 ppt: fullness, fatty7 meat stock, chicken fat S at 1.5 ppt: fullness, fatty, blood character, pork, meat stock With their specific taste towards meat, the compounds of ~he formula (I) according ~o the invPntion act in a taste-reinforcing and -rounding off manner in meat flavour composi~ions. However, in other flavour compositions, for example nut flavourings, ~he compounds according to the invention also cause a rounding-off of the flavour and an increase in the fullness of taste.
The flavour compositions prepared using the compounds according to the invention can be employed in the entire foodstuff and luxury yoods sector, and also in animal feed. They are suitable, in particular, for fatty materials, baking goods, extruded products, ready-to-serve meals, meat and sausage produc~s, ~oup8, sauces, vegetable preserves and all types of industrially prepared anLmal feed.
The new methanethiols according to the invention are used in amounts of 5 ppt to 1%, preferably 100 ppt to 100 ppm, relative to the ready to-consume foodstuff.
The percentage data used in the examples are percentages by weight.
Examples Example 1 A solution of 3 g of 2-bromo-3-eth~lthiophene (Chem. Scr. 1974, 217) in 10 ml of ether was ~lowly added .
2~43~
dropwise at -78C under dry nitrogen to 9 ml of a 20~
strength solution of n-butyllithium in toluene ~uch that the temperature did no~ exceed -60C. 1.2 g of para formaldehyde were then added and the mixture was warmed ~o room temperature for 1.5 hours. The reaction mixture was poured into dilute hydroc~loric acid and ex~racted using ether. ~fter distilling off the solvent, 2.~ g of crude product remained which contained 65.7% of 3-ethyl-2-hydroxymethyl-thiophene according to the gas chromato-gram.
1.26 g of thio~yl chloride were added to 1.4 g of this crude produc~ and 1 g of pyridine in 25 ml of ether.
After stirring at room temperature for 4 hours, the reaction mixture was poured into dilute hydrochloric acid and extracted several ~imes using ether. The organic phase was washed until neutral, dried and concentrated.
The residue was dissolved in 50 ml of ethanol and heated to reflux temperature with 0.8 g of thiourea for 30 minutes. After stripping off the solvent, the residue was stirred under nitrogen a~ 60C with 50 ml of 5N sodium hydroxide solution for 1 hour. The mixture was then acidified using dilute hydrochloric acid and e~tracted using ether. The crude product which remained after stripping off the solvent was distilled at 71C and 0.3 mbar. 0.2 g of [2 (3-ethyl-thienyl)]-methanethiol were obtained.
If, instead of 3-ethyl-2-hydro~ymethyl-thiophene~
the isomeric 2-ethyl-3-hydroxymethyl-thiophene ~US Patent 4,560,701) was employed, 3~(2-ethyl-thienyl)-methanethiol was obtained in identical yield. [3-(2-ethyl-furyl~]-` ` 2~4~25~
methanethiol was obtained analogously from 2-ethyl-3-hydroxymethyl-furan (Farmaco, Ed. Sci. 1982, 398). The IR, NMR and mass spectra of the compounds agreed with the structures given.
Example 2 A meat flavour composition was prepared by mixing the following constituents in the parts by weight indi-cated:
50:50 mixture of Na inosinate and Na guanilate Monosodium glutamate 19 Lactic acid, spray-dried 30 Vegetable protein hydrolysate (Type RFB
from Food Ingredient~ Specialities 350 Sweet whey powder 100 Table salt 500 1, 000 A 1~ aqueous solution of this composition was used as a control sample.
I~ 15 ppt of r2-(3-ethyl-thienyl)]-methanethiol were added to the control sample, the flavour was described by a test group as distinctly stronger and fuller towards beef s~ock, gravy and roast meat with a liver character in the background in comparison to the control sample.
On adding 75 ppt of [3-(2-ethyl-fury~
methanethiol to the control sample, the flavour i8 judged as distinctly fuller towards roast meat.
. ,, :
Claims (3)
1. Methanethiols of the formula (I) in which X represents an oxygen or sulphur atom, and one of the radicals Rl or R2 represents a mercaptomethyl group and the other represents an ethyl group,
2. Process for the preparation of the methanethiols of the formula (I) in which X represents an oxygen or sulphur atom, and one of the radicals R1 or R2 represents a mercaptomethyl group and the other represents an ethyl group, characterised in that compounds of the formula (II) in which X has the meaning indicated under formula (I) and one of the radicals R1 or R2 represents a hydroxymethyl group and the other represents an ethyl group, are reacted with thionyl chloride and the resulting chloromethyl compound is reacted with thiourea.
3. Use of the methanethiols according to Claim 1 as flavourings.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4017242A DE4017242A1 (en) | 1990-05-29 | 1990-05-29 | METHANTHIOLE, PROCESS FOR THEIR PRODUCTION AND THEIR USE |
| DEP4017242.2 | 1990-05-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2043251A1 true CA2043251A1 (en) | 1991-11-30 |
Family
ID=6407397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002043251A Abandoned CA2043251A1 (en) | 1990-05-29 | 1991-05-24 | Methanethiols, process for their preparation and their use |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0459230B1 (en) |
| CA (1) | CA2043251A1 (en) |
| DE (2) | DE4017242A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7408383A (en) * | 1973-08-07 | 1975-02-11 | Int Flavors & Fragrances Inc | PROCESS FOR PREPARING 3-THIAFURANS AND 3-MERCAPTOFURANS. |
| NL163104C (en) * | 1975-02-19 | 1980-08-15 | Int Flavors & Fragrances Inc | A PROCESS FOR IMPROVING OR STRENGTHENING NICE ACCENTS OF A MEAT-FOOD FOOD, AND A METHOD FOR PREPARING A SUITABLE PREPARATION. |
| DE3025305A1 (en) * | 1980-07-04 | 1982-01-28 | Haarmann & Reimer Gmbh, 3450 Holzminden | Flavorings for animal feed |
| DE3831981A1 (en) * | 1988-09-21 | 1990-03-29 | Haarmann & Reimer Gmbh | HALBMERCAPTALE, METHOD FOR THEIR PRODUCTION AND THEIR USE |
-
1990
- 1990-05-29 DE DE4017242A patent/DE4017242A1/en not_active Withdrawn
-
1991
- 1991-05-16 DE DE59102698T patent/DE59102698D1/en not_active Expired - Fee Related
- 1991-05-16 EP EP91107894A patent/EP0459230B1/en not_active Expired - Lifetime
- 1991-05-24 CA CA002043251A patent/CA2043251A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0459230A1 (en) | 1991-12-04 |
| DE59102698D1 (en) | 1994-10-06 |
| DE4017242A1 (en) | 1991-12-05 |
| EP0459230B1 (en) | 1994-08-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |