DE2233245B2 - I, 3-Dioxolanes and processes for their production and flavor compositions containing these compounds - Google Patents
I, 3-Dioxolanes and processes for their production and flavor compositions containing these compoundsInfo
- Publication number
- DE2233245B2 DE2233245B2 DE2233245A DE2233245A DE2233245B2 DE 2233245 B2 DE2233245 B2 DE 2233245B2 DE 2233245 A DE2233245 A DE 2233245A DE 2233245 A DE2233245 A DE 2233245A DE 2233245 B2 DE2233245 B2 DE 2233245B2
- Authority
- DE
- Germany
- Prior art keywords
- compounds
- compositions
- dioxolanes
- butyric acid
- coo
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 28
- 150000001875 compounds Chemical class 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 9
- 239000000796 flavoring agent Substances 0.000 title claims description 8
- 235000019634 flavors Nutrition 0.000 title claims description 8
- 235000014121 butter Nutrition 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 4
- 235000014594 pastries Nutrition 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 125000006091 1,3-dioxolane group Chemical class 0.000 claims description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims 2
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 claims 1
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 235000012976 tarts Nutrition 0.000 claims 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims 1
- 235000012141 vanillin Nutrition 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- BOHGAOWOIJMTPZ-UHFFFAOYSA-N 1,3-dioxolan-4-ylmethanol Chemical compound OCC1COCO1 BOHGAOWOIJMTPZ-UHFFFAOYSA-N 0.000 description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- -1 2,2,4-trisubstituted dioxolanes Chemical class 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000020374 simple syrup Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/24—Radicals substituted by singly bound oxygen or sulfur atoms esterified
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/205—Heterocyclic compounds
- A23L27/2052—Heterocyclic compounds having oxygen or sulfur as the only hetero atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Seasonings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Fats And Perfumes (AREA)
Description
cyclisiert oder daß man 100°cyclized or that 100 °
b) ein 4-Hydroxymethyl-dioxolan der allgemei- 30 wird 1 Gewichtsteil des nach Beispiel 1 hergestellten nen Formel 2 - (1' - Propcnyl) - 4 - η - butyroxymethyl - dioxolans zu-b) a 4-hydroxymethyl-dioxolane of the general 30 is 1 part by weight of that prepared according to Example 1 formula 2 - (1 '- Propcnyl) - 4 - η - butyroxymethyl - dioxolane to-
2 3 gefügt. Die so erhaltene Zusammensetzung B ist der 2 3 joined. Composition B thus obtained is that
R s J*· Zusammensetzung A (mit dem bekannten Buller- R s J * Composition A (with the well-known Buller
^ / aroma Diacetyl) geschmacklich eindeutig überlegen.^ / aroma diacetyl) clearly superior in taste.
χ, ''"' 35 Wird nämlich mit den Zusammensetzungen A und B χ, ''"'35 Is namely with the compositions A and B
/ \ Gebäck hergestellt, wobei die Dosierung der Aromen-/ \ Pastries, whereby the dosage of the aromas
Y Y kompositionen bei 50 g pro 100 kg Teig (0,5° 00) liegt,YY compositions is 50 g per 100 kg of dough (0.5 ° 00 ),
... _ r„ _ ' _' so weist das mit der Zusammensetzung B aromatisierte... _ r "_ '_' is what the flavored with the composition B indicates
HU LH2 LH CH2 Gebäck einen eindeutig feineren Buttergeschmack auf.HU LH 2 LH CH 2 pastries have a clearly finer butter taste.
mit n-Buttersäure oder einem funktionellen Derivat Versuch 2
derselben verestert, wobei in den Formeln diewith n-butyric acid or a functional derivative Experiment 2
the same esterified, whereby in the formulas the
Reste R2 und R3 die im Anspruch 1 angegebene Zu der in Versuch 1 genannten Butteraromen-Bedeutung besitzen, zusammensetzung A werden 10 Teile des nach Bei-3. Geschmackstoffzusammensetzung, gekenn- 45 spiel 2 hergestellten 2-Methyl-2-(r-hydroxyäthyl)-zeichnet durch einen Gehalt an einer Verbindung 4-n-bulyroxymelhyl-dioxolans zugefügt. Die so erhalgemäß Anspruch 1. tene Zusammensetzung C wird zur AromatisierungR 2 and R 3 radicals have the meaning given in claim 1 to the butter flavor meaning mentioned in experiment 1, composition A is 10 parts of the composition according to case-3. Flavor composition, gekenn- 45 game 2 produced 2-methyl-2- (r-hydroxyethyl) -characterized by a content of a compound 4-n-bulyroxymelhyl-dioxolane added. The composition C thus obtained according to claim 1. is used for flavoring
von Gebäck in einer Dosierung von 0,50Zq0 verwendet.of pastries used in a dosage of 0.5 0 Zq 0 .
Das mit der Zusammensetzung C aromatisierte Ge-The product flavored with the composition C
50 back ist dem mit 0,5°oo der ZusammensetzungA50 back is the one with 0.5 oo of composition A.
aromatisierten geschmacklich eindeutig überlegen.
Die Erfindung betrifft 1,3-Dioxolane der allgemeinenflavored clearly superior in taste.
The invention relates to 1,3-dioxolanes in general
Formel Versuch 3Formula experiment 3
R2 R-1 R 2 R- 1
\ / 55 Aus einem Gemisch D, bestehend aus 1000 Gc-\ / 55 From a mixture D, consisting of 1000 Gc-
C (I) wichtsteilen der Aromazusammensetzung A des Vcr-C (I) parts by weight of the flavor composition A of the
/ \ suchs 1 und lOOGewichlsteilen des nach Beispiels/ \ suchs 1 and lOOGewichlstteile of the example
0 O hergestellten 2-(2'- Mcthyl-propylj-4-n-bulyroxy-0 O produced 2- (2'-methyl-propylj-4-n-bulyroxy-
1 I mcthyl-dioxolaris wie einem Gemisch E, bestehend CH1-CH2-CH2-COO-CH2-CII-Ch2 60 aus 1000 Gcwichtstcilen der Aromazusammenscl-1 I methyl-dioxolaris like a mixture E, consisting of CH 1 -CH 2 -CH 2 -COO-CH 2 -CII-Ch 2 60 from 1000 parts by weight of the aroma compositions
zungAund 100 Gcwichtstcilen des aus dem Beispiel 32zungA and 100 parts by weight of the example 32
lh der R2 ein Wasserstoffatom oder einen Methylrest der DT-OS 14 93 572 bekannten 2-(l'-lsopropyl)-lh the R 2 is a hydrogen atom or a methyl radical of DT-OS 14 93 572 known 2- (l'-isopropyl) -
Hnd R-1 den l'-Propenylrcst, l'-Hydroxyäthylrest oder 4-n-bulyroxymcthyl-dioxolans, wurde jeweils eineWhen R- 1 denotes the l'-propenyl residue, l'-hydroxyethyl residue or 4-n-bulyroxymethyl-dioxolane, each became one
J'-Melhylpropylresl darstellt, und Verfahren zu deren l%igc Lösung in Propylcnglykol hergestellt und dieseIs J'-Melhylpropylresl, and process for their 1% igc solution in Propylcnglykol and these
Merstellung sowie solche Verbindungen enthaltende 65 wiederum als 0,05%ige Lösung in Zuckersirup durchMerstellung as well as 65 containing such compounds in turn as a 0.05% solution in sugar syrup
Geschmackstoffzusammensetzungen. eine Expcrtcngruppe aus 5 Personen auf ihren Ge-Flavor compositions. an expert group of 5 people on their own
Dic crfindungsgcmäßen Verbindungen I zeichnen schmack geprüft. Dabei wurde festgestellt, daß dasThe compounds of the invention I draw taste-tested. It was found that the
■ich überraschenderweise durch besondere geschmack- Gemisch D ein intensiv sahniges Aroina nach frischer■ Surprisingly, I get an intensely creamy aroina with a fresher taste thanks to the special flavor mixture D
Butter besitzt, während dem Gemisch E die frische Butternote völlig fehlt.Has butter, while mixture E completely lacks the fresh butter note.
Die 1,3-Dioxolane der obigen Formel I werden dadurch hergestellt, daß man in an sich bekannter Weise entwederThe 1,3-dioxolanes of the above formula I are prepared by being known per se Way either
a) den Glycerin-u-mono-n-buttersäure-ester der Formela) the glycerol-u-mono-n-butyric acid ester of formula
CH3-CH2-CH2-COO-CH2-CHOH-CH2-OhCH 3 -CH 2 -CH 2 -COO-CH 2 -CHOH-CH 2 -Oh
IOIO
mit einer Carbonyl verbindung der allgemeinen Formel R2 —CO —R3 (II)with a carbonyl compound of the general formula R 2 —CO —R 3 (II)
cyclisiert oder daß mancyclized or that one
b) ein 4-Hydroxymethyl-dioxolan der allgemeinen Formelb) a 4-hydroxymethyl-dioxolane of the general formula
R2 R3 R 2 R 3
C (III)C (III)
0 O0 O
1 I1 I.
HO — CH2 CH CH2 HO - CH 2 CH CH 2
mit n-Buttersäurc oder einem funktioneilen Derivat derselben verestert, wobei in den Formeln die Reste R2 und R3 die oben angegebene Bedeutung besitzen.esterified with n-butyric acid or a functional derivative thereof, the radicals R 2 and R 3 in the formulas being as defined above.
Bei der Methode a) wird ein Aldehyd bzw. Keton der allgemeinen Formel 11 mit dem betreffenden Ester wie üblich acetalisiert bzw. ketalisiert. Die Acetalisierung bzw. Realisierung erfolgt vorleilhafterweise durch Erhitzen des Gemisches der Reaktionspartner in Gegenwart eines Lösungsmittels und zweckmäßigerweise unter Verwendung eines sauren Katalysators sowie fortlaufender Entfernung des sich bildenden Wassers, z. B. mittels eines Schleppmittels.In method a), an aldehyde or ketone of the general formula 11 is used with the ester in question acetalized or ketalized as usual. The acetalization or realization takes place as a precaution by heating the mixture of reactants in the presence of a solvent and expediently using an acidic catalyst as well as progressive removal of the one that forms Water, e.g. B. by means of an entrainer.
Als Schleppmittel können die hierfür üblichen Lösungsmittel, wie aromatische und gesättigte aliphatische Kohlenwasserstoffe, z. B. Benzol, Toluol oder n-Penian, verwendet werden.The solvents customary for this purpose, such as aromatic and saturated aliphatic ones, can be used as entrainers Hydrocarbons, e.g. B. benzene, toluene or n-peniane can be used.
Als saure Katalysatoren eignen sich die für Acetalisierungen bzw. Realisierungen üblichen Verbindungen^. B. Mineralsäuren, wie Schwefelsäure, Phosphorsäure, Perchlorsäure; starke organische Säuren, wie Trichloressitisäurc oder p-Toluolsulfonsäure oder Bortrilluorid. Suitable acidic catalysts are those for acetalizations or realizations of usual connections ^. B. mineral acids such as sulfuric acid, phosphoric acid, Perchloric acid; strong organic acids such as trichloroessitic acid or p-toluenesulphonic acid or boron trilluoride.
Die Veresterungsmethode b) wird nach an sich bekannten Methoden durchgeführt, z. B. durch Acylierung nach Schotten Baumann in Gegenwart einer Base, oder durch Umsetzung des Alkohols III mit der n-Buttersäure oder deren Anhydrid in Gegenwart eines sauren Katalysators, zweckmäßigerweise unter Verwendung eines Lösungsmittels und unter fortlaufender Entfernung von sich bildendem Wasser. Als saure Katalysatoren kommen die oben für die Methode a) erwähnten Verbindungen in Frage.The esterification method b) is carried out according to methods known per se, e.g. B. by acylation according to Schotten Baumann in the present a base, or by reacting the alcohol III with n-butyric acid or its anhydride in the presence of an acidic catalyst, expediently using a solvent and with continuous removal of water that forms. They come as acidic catalysts above for the method a) mentioned compounds in question.
Für 2,4-di- bzw. 2,2,4-trisubstiluierte Dioxolane, wie sie die Verbindungen I darstellen, sieht die Theorie eine eis- und eine trans-Form vor (vergleiche z. B. J. Chem. Soc. 1970, 263). Die Formel I soll die eis- und Irans-Formen sowie Gemische dieser beiden Formen umfassen. Die erfindungsgemäß nach den Verfahrensvarianten a) und b) hergestellten Verbindungen I fallen zumeist als cis-trans-Isomerengemische mit etwa gleichen Mengen an eis- und trans-Form an.For 2,4-di- or 2,2,4-trisubstituted dioxolanes, as represented by the compounds I, the theory looks ahead an cis and a trans form are available (compare, for example, J. Chem. Soc. 1970, 263). The formula I is said to be the ice and Iran forms as well as mixtures of these two forms. According to the invention according to the process variants Compounds I prepared a) and b) mostly fall as cis-trans isomer mixtures with approximately the same Amounts of cis and trans forms.
300 gGiycerin-u-mono-n-buttersäureesterund 150 g Crotonaldehyd werden in 1200 ml Benzol gelöst und in Gegenwart von 4 g p-Toluolsulfonsäure an einem Wasserabscheider gekocht. Nach Abkühlen des Reaktionsgemisches wird dieses in einen Scheidetrichter übergeführt und nacheinander mit Wasser, 5%iger Natriumbicarbonatlösung und Wasser neutral gewaschen. Anschließend wird das Lösungsmittel abdestilliert und der Rückstand an einer Füllkörperkolonne fraktioniert destilliert. Das hierbei mit einer Ausbeute von 75% anfallende 2-fl'-Propenyl]-4-n-butyroxymeihyl-dioxolan siedet unter einem Druck von 0,4 mm bei 101 bis 1020C; η if = 1,4520.300 g of glycerol-u-mono-n-butyric acid ester and 150 g of crotonaldehyde are dissolved in 1200 ml of benzene and boiled on a water separator in the presence of 4 g of p-toluenesulfonic acid. After the reaction mixture has cooled, it is transferred to a separating funnel and washed successively with water, 5% sodium bicarbonate solution and water until neutral. The solvent is then distilled off and the residue is fractionally distilled on a packed column. The case with a yield of 75% obtained 2-FL 'propenyl] -4-n-butyroxymeihyl-dioxolane boils under a pressure of 0.4 mm at 101-102 0 C; η if = 1.4520.
In einem 4-Halsrührkolben mit aufgesetztem Wasserabscheider werden 200 g Acetylmethylcarbinol, 366 g Glycenn-u-mono-n-buttersäureester, 1300 ml Benzol und 8 g p-Toluolsulfonsäure gemischt und unter Rühren am Rückfluß gekocht. Nach 5 Stunden beträgt die ausgeschiedene Wassermenge etwa 40 ml entsprechend einem annähernd vollständigen Umsatz. Das Reaktionsgemisch wird abgekühlt und in 500 ml gesättigte wäßrige Natriumbicarbonatlösung eingegossen. Die Benzollösung wird im Scheidetrichter abgetrennt und mit Wasser gründlich gewaschen. Nach kurzer Trocknung wird das Benzol abdestilliert und der Rückstand an einer Füllkörperkolonne fraktioniert. In a 4-neck stirred flask with attached water separator 200 g of acetylmethylcarbinol, 366 g of Glycenn-u-mono-n-butyric acid ester, 1300 ml Benzene and 8 g of p-toluenesulfonic acid mixed and refluxed with stirring. After 5 hours the amount of water excreted is about 40 ml, corresponding to an almost complete conversion. The reaction mixture is cooled and poured into 500 ml of saturated aqueous sodium bicarbonate solution. The benzene solution is separated off in a separating funnel and washed thoroughly with water. After a short drying period, the benzene is distilled off and the residue is fractionated on a packed column.
Man erhält 182g 2-Methyl-2-[l'-hydroxyäthyQ-4-n-butyroxymethyl-dioxolan vom Kp. 0,2.'104 bis 106 C; η"' = 1,4487 in Form eines Gemisches von 2 Stereoisomeren im Verhältnis von etwa 1:1.182 g of 2-methyl-2- [l'-hydroxyäthyQ-4-n-butyroxymethyl-dioxolane with a boiling point of 0.2.104 to 106.degree. C. are obtained; η "' = 1.4487 in the form of a mixture of 2 stereoisomers in a ratio of about 1: 1.
Nach der in den Beispielen 1 und 2 beschriebenen Methode wurde unter Verwendung der entsprechenden Ausgangsstoffe das 2 - (2' - Methyl - propyl)-4-n-butyroxymethyl-dioxolan vom Kp. 0,3/85 C. »■■'■ = 1,4378, hergestellt.According to the method described in Examples 1 and 2, using the appropriate starting materials, 2 - (2 '- methylpropyl) -4-n-butyroxymethyl-dioxolane with a boiling point of 0.3 / 85 ° C. was obtained = 1.4378, established.
23 g 2-[Γ- PropenyO-4-hydroxymethyl- dioxolan werden zusammen mit 12,5 g absolutem Pyridin und 250 ml Chloroform in ein Reaktionsgefäß gegeben, und das Gemisch wird auf -10" C gekühlt. Innerhalb 20 Minuten läßt man hierauf 18 g n-Buttersäurechlorid zutropfen und rührt weitere 5 Stunden, wobei man die Temperatur allmählich auf Raumtemperatur ansteigen läßt. Das Reaktionsgemisch wird dann mit Natriumbicarbonat und Wasser gewaschen, getrocknet und vom Lösungsmittel befreit. Durch Destillation des Rückstandes erhall man 28 g 2-f l'-Propenyl]-4-n-butyroxymethyl-dioxolan vom Kp. 0,05/90 bis 92"C;n> = 1,4535.23 g 2- [Γ-propenyO-4-hydroxymethyldioxolane are placed in a reaction vessel together with 12.5 g of absolute pyridine and 250 ml of chloroform, and the mixture is cooled to -10 ° C. 18 g of n-butyric acid chloride are left on this over the course of 20 minutes add dropwise and stir for a further 5 hours, the temperature gradually rising to room temperature leaves. The reaction mixture is then washed with sodium bicarbonate and water, dried and freed from the solvent. By distilling the residue, 28 g of 2-f l'-propenyl] -4-n-butyroxymethyl-dioxolane are obtained from bp 0.05 / 90 to 92 "C; n> = 1.4535.
Claims (2)
rest oder 2'-Methylpropylrest darstellt. .. , .in which R 2 is a hydrogen atom or a methyl taste properties of some residues according to the invention and R 3 is the l'-propenyl residue, 1'-hydroxyethyl compounds,
represents radical or 2'-methylpropyl radical. ..,.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1089371 | 1971-07-23 | ||
| CH1089371A CH557814A (en) | 1971-07-23 | 1971-07-23 | Process for the production of new flavors. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2233245A1 DE2233245A1 (en) | 1973-02-01 |
| DE2233245B2 true DE2233245B2 (en) | 1975-06-26 |
| DE2233245C3 DE2233245C3 (en) | 1976-02-05 |
Family
ID=
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0150398A3 (en) * | 1984-01-11 | 1985-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Methylphenyldioxolanes, their preparation and use as odoriferous substances and smelling compositions containing them |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0150398A3 (en) * | 1984-01-11 | 1985-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Methylphenyldioxolanes, their preparation and use as odoriferous substances and smelling compositions containing them |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2147091B1 (en) | 1977-12-30 |
| NL7207891A (en) | 1973-01-25 |
| FR2147091A1 (en) | 1973-03-09 |
| CH557814A (en) | 1975-01-15 |
| US3883558A (en) | 1975-05-13 |
| IT1048945B (en) | 1980-12-20 |
| JPS532946B2 (en) | 1978-02-01 |
| ES405074A1 (en) | 1975-07-16 |
| JPS5512908B1 (en) | 1980-04-04 |
| JPS5163969A (en) | 1976-06-02 |
| BR7204528D0 (en) | 1973-06-26 |
| DE2233245A1 (en) | 1973-02-01 |
| NL149805B (en) | 1976-06-15 |
| GB1352092A (en) | 1974-05-15 |
| BE786556A (en) | 1973-01-22 |
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| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| 8339 | Ceased/non-payment of the annual fee |