DE1010530B - Process for the preparation of tetrahydro-ª † -pyrones alkylated in the 2-position - Google Patents
Process for the preparation of tetrahydro-ª † -pyrones alkylated in the 2-positionInfo
- Publication number
- DE1010530B DE1010530B DEF20616A DEF0020616A DE1010530B DE 1010530 B DE1010530 B DE 1010530B DE F20616 A DEF20616 A DE F20616A DE F0020616 A DEF0020616 A DE F0020616A DE 1010530 B DE1010530 B DE 1010530B
- Authority
- DE
- Germany
- Prior art keywords
- tetrahydro
- pyrones
- alkylated
- preparation
- mercury
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 3
- -1 propargyl alcohols Chemical class 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000007659 semicarbazones Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BCIXOLAZTUNRJF-UHFFFAOYSA-N 5-methylhex-5-en-2-yn-1-ol Chemical compound CC(=C)CC#CCO BCIXOLAZTUNRJF-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PHYAXJNGPOYIIR-UHFFFAOYSA-N hept-5-en-2-yn-1-ol Chemical compound CC=CCC#CCO PHYAXJNGPOYIIR-UHFFFAOYSA-N 0.000 description 2
- KSOMTIQGBYHOJM-UHFFFAOYSA-N hex-5-en-2-yn-1-ol Chemical compound OCC#CCC=C KSOMTIQGBYHOJM-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940082150 encore Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung in 2-Stellung alkylierter Tetrahydro-y-pyrone Es ist bekannt, daß man in 2-Stellung alkylierte Tetrahydro-y-pyrone nach verschiedenen Verfahren erhalten kann, z. B. durch Hydratisierung der Kondensationsprodukte aus Carbonylverbindungen, wie Acetaldehydoder Aceton mit Vinylacetylen (vgl. I. N. N az ar o v, I.B. TorgovundL.N. Terekhova, ChemicalAbstracts, Bd. 38, S. 1729 A944]). Diese Verfahren haben aber unter anderem den Nachteil, daß sie von technisch schwer zugänglichen Verbindungen ausgehen.Process for the preparation of tetrahydro-γ-pyrones alkylated in the 2-position It is known that tetrahydro-y-pyrones alkylated in the 2-position can be used in various ways Process can be obtained, e.g. B. by hydration of the condensation products Carbonyl compounds such as acetaldehyde or acetone with vinyl acetylene (cf. I. N. N az ar o v, I.B. Torgov and L.N. Terekhova, Chemical Abstracts, vol. 38, p. 1729 A944]). However, these processes have, inter alia, the disadvantage that they are technically difficult run out of accessible connections.
Es wurde nun gefunden, daß man durch Hydratisierung von Propargylalkoholen, die in 3-Stellung durch gegebenenfalls alkylsubstituierte Allylreste substituiert sind, in 2-Stellung alkylierte Tetrahydro-y-pyrone erhalten kann.It has now been found that by hydration of propargyl alcohols, substituted in the 3-position by optionally alkyl-substituted allyl radicals are, in the 2-position alkylated tetrahydro-y-pyrones can be obtained.
Für das erfindungsgemäße Verfahren geeignete Propargylalkohole sind z. B. 5-Hexen-2-in-l-ol, 5-Hepten-2-in-1-ol oder 5-Methyl-5-hexen-2-in-l-ol.Propargyl alcohols suitable for the process according to the invention are z. B. 5-hexen-2-yn-1-ol, 5-hepten-2-yn-1-ol or 5-methyl-5-hexen-2-yn-1-ol.
Die Wasseranlagerung kann nach an sich bekannten Verfahren erfolgen, z. B. in saurer Lösung in Gegenwart von Quecksilberverbindungen. Desgleichen kann die Aufarbeitung nach bekannten Verfahren erfolgen, indem man z. B. mit Äther extrahiert und den Extrakt anschließend destilliert.The accumulation of water can take place according to methods known per se, z. B. in acidic solution in the presence of mercury compounds. Can do the same the work-up carried out by known methods by z. B. extracted with ether and the extract is then distilled.
Beispiel 1 In eine auf 50' erwärmte Lösung von 1 g Quecksilber(II)-sulfat in 333 ccm 10°/oiger Schwefelsäure wurden unter Rühren innerhalb von 10 Minuten 56 g 5-Hexen-2-in-l-ol eingetropft. Unter weiterem Rühren wurden sechsmal nach je 30 Minuten 0,5 g Quecksilber (II)-sulfat hinzugefügt. Die Gesamtdauer der Umsetzung betrug 5 Stunden.Example 1 In a 50 'heated solution of 1 g of mercury (II) sulfate in 333 ccm 10% sulfuric acid were stirred with stirring within 10 minutes 56 g of 5-hexen-2-yn-1-ol were added dropwise. With further stirring were added six times each 0.5 g of mercury (II) sulfate added for 30 minutes. The total duration of the implementation was 5 hours.
Das nach Erkalten mit Äther extrahierte Reaktionsprodukt lieferte bei der Destillation 40 g einer farblosen, wasserlöslichen Flüssigkeit (Kp." = 60 bis 64°) der Formel C, HI, 02 Die Verbindung enthält keinen aktiven Wasserstoff, gibt ein Semicarbazon vom Schmelzpunkt 175 bis 176° und ein p-N itrophenylhydrazon der Formel C12 H15 Na 03 vom Schmelzpunkt 141'.The reaction product extracted after cooling with ether yielded 40 g of a colorless, water-soluble liquid (bp "= 60 to 64 °) of the formula C, HI, 02 during the distillation The compound contains no active hydrogen, gives a semicarbazone with a melting point of 175 to 176 ° and a pN itrophenylhydrazone of the formula C12 H15 Na 03 with a melting point of 141 '.
Beispiel 2 Zu einem Gemisch von 44,1 g 5-Hepten-2-in-l-ol, 80 ccm 10°/aiger Schwefelsäure und 100 ccm Aceton wurden unter Rühren bei 65 bis 70° in Abständen von einer Stunde insgesamt 9 g Quecksilber(II)-sulfat in 1-g-Portionen hinzugefügt. Nach insgesamt 9 Stunden wurde abgekühlt, mit 200 ccm Wasser verdünnt und das gebildete 2-Äthyltetrahydro-y-pyron der Formel mit Äther extrahiert und destilliert. Erhalten wurden 16,5 g (32°/0); Kp.l 43°; WO = 1,4491. Die Substanz lieferte ein p-Nitrophenylhydrazon der Formel C13 H17 03N3 vom Schmelzpunkt 122°.EXAMPLE 2 A total of 9 g of mercury were added to a mixture of 44.1 g of 5-hepten-2-yn-1-ol, 80 cc of 10% sulfuric acid and 100 cc of acetone with stirring at 65 to 70 ° at intervals of one hour (II) sulfate added in 1 g portions. After a total of 9 hours, the mixture was cooled, diluted with 200 cc of water and the 2-ethyltetrahydro-y-pyrone of the formula formed extracted with ether and distilled. This gave 16.5 g (32%); Bp l 43 °; WO = 1.4491. The substance provided a p-nitrophenylhydrazone of the formula C13 H17 03N3 with a melting point of 122 °.
Beispiel 3 Zu einem Gemisch von 46 g 5-Methyl-5-hexen-2-in-l-ol und 125 g 5°/oiger Schwefelsäure wurden bei 80° unter Rühren 7 g Quecksilber(II)-sulfat in 1-g-Portionen in Abständen von je 30 Minuten hinzugefügt. Nach der letzten Zugabe wurde noch 1 Stunde bei 80° weitergerührt.Example 3 To a mixture of 46 g of 5-methyl-5-hexen-2-yn-1-ol and 125 g of 5% sulfuric acid became 7 g of mercury (II) sulfate at 80 ° with stirring added in 1 g portions at 30 minute intervals. After the last encore the mixture was stirred for a further 1 hour at 80 °.
Bei der üblichen Aufarbeitung wurden 18 g 2, 2-Dimethyl-tetrahydro-y-pyron der Formel als farblose Flüssigkeit erhalten. Kp.h 68°; WD = 1,4490. Die Analyse entsprach der Summenformel C,H"02. Die Abwesenheit von Hydroxylgruppen wurde durch Analyse bestätigt, das Vorhandensein der Carbonylgruppe durch Darstellung des Semicarbazons (F. 170°).In the usual work-up, 18 g of 2,2-dimethyl-tetrahydro-y-pyrone of the formula were obtained obtained as a colorless liquid. Bp 68 °; WD = 1.4490. The analysis corresponded to the empirical formula C, H "02. The absence of hydroxyl groups was confirmed by analysis, the presence of the carbonyl group by representation of the semicarbazone (mp 170 °).
Beispiel 4 In ein auf 50° erwärmtes Gemisch von 25 ccm konzentrierter Schwefelsäure, 1 g Quecksilber(II)-sulfat und 400 ccm Wasser werden unter Rühren 75 g 4 -'Vlethyl-5-hexen-2-in-l-ol innerhalb 30 Minuten eingetropft. Im Laufe weiterer 30 Minuten wird die Temperatur auf 70° erhöht, worauf noch 6 g Quecksilber(II)-sulfat in 1-g-Portionen in Abständen von 30 Minuten zugegeben werden. Nach insgesamt 4 Stunden wird abgekühlt und aufgearbeitet. Es werden 48 g (55 °/a der Theorie) 2; 3-Dimethyltetrahydro-y-pyron erhalten. Kp." 65 bis 70°; n' = 1,4530. Das Semicarbazon hat einen Schmelzpunkt von 187° und das p-Nitrophenylhydrazon einen Schmelzpunkt von 155°.EXAMPLE 4 75 g of 4-ethyl-5-hexen-2-yn-1-ol are poured into a mixture, heated to 50 °, of 25 cc of concentrated sulfuric acid, 1 g of mercury (II) sulfate and 400 cc of water, while stirring Dripped in minutes. In the course of a further 30 minutes, the temperature is increased to 70 °, whereupon 6 g of mercury (II) sulfate are added in 1 g portions at intervals of 30 minutes. After a total of 4 hours, the mixture is cooled and worked up. There are 48 g (55 ° / a of theory) 2; 3-dimethyltetrahydro-γ-pyrone obtain. Bp. 65 to 70 °; n '= 1.4530. The semicarbazone has a melting point of 187 ° and the p-nitrophenylhydrazone a melting point of 155 °.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF20616A DE1010530B (en) | 1956-06-25 | 1956-06-25 | Process for the preparation of tetrahydro-ª † -pyrones alkylated in the 2-position |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF20616A DE1010530B (en) | 1956-06-25 | 1956-06-25 | Process for the preparation of tetrahydro-ª † -pyrones alkylated in the 2-position |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1010530B true DE1010530B (en) | 1957-06-19 |
Family
ID=7089746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF20616A Pending DE1010530B (en) | 1956-06-25 | 1956-06-25 | Process for the preparation of tetrahydro-ª † -pyrones alkylated in the 2-position |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1010530B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014028946A3 (en) * | 2012-08-17 | 2014-10-16 | The Broad Institute, Inc. | Modulators of hepatic lipoprotein metabolism |
-
1956
- 1956-06-25 DE DEF20616A patent/DE1010530B/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014028946A3 (en) * | 2012-08-17 | 2014-10-16 | The Broad Institute, Inc. | Modulators of hepatic lipoprotein metabolism |
| US9526720B2 (en) | 2012-08-17 | 2016-12-27 | The Broad Institute, Inc. | Modulators of hepatic lipoprotein metabolism |
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