DE3050795C2 - Halogen-substituted tetrahydro-α-pyrones and processes for their preparation - Google Patents
Halogen-substituted tetrahydro-α-pyrones and processes for their preparationInfo
- Publication number
- DE3050795C2 DE3050795C2 DE19803050795 DE3050795A DE3050795C2 DE 3050795 C2 DE3050795 C2 DE 3050795C2 DE 19803050795 DE19803050795 DE 19803050795 DE 3050795 A DE3050795 A DE 3050795A DE 3050795 C2 DE3050795 C2 DE 3050795C2
- Authority
- DE
- Germany
- Prior art keywords
- formula
- pyrones
- halogen
- preparation
- processes
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/19—Acids containing three or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
-
- 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
- C07D307/26—Heterocyclic compounds containing five-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
- C07D307/30—Heterocyclic compounds containing five-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
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- 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
-
- 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
- C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
Description
I (TV)I (TV)
worin R1, R2 und R3 die oben angegebenen Bedeutungen haben, in einem inerten Lösungsmittel mit Chlor oder Brom umsetztwherein R 1 , R 2 and R 3 have the meanings given above, reacts with chlorine or bromine in an inert solvent
.10 Die Erfindung betrifft halogensubstituierte Tetrahydro-a-pyrone sowie ein Verfahren zur Herstellung dieser Produkte. Die neuen Pyrone sind nützliche Zwischenprodukte für Cyclopropancarbonsäureester, die bekanntermaßen Vorprodukte zur Herstellung von Insektiziden sind..10 The invention relates to halogen-substituted tetrahydro-a-pyrones and a process for the preparation of these Products. The new pyrones are useful intermediates for cyclopropanecarboxylic acid esters known to be Pre-products for the manufacture of insecticides are.
Es ist bekannt, Acetale der 2,2-Dialkyl-3-formyl-cyclopropancarbonsäureester nach der DE-OS 26 IS 160 durch Umsetzung von Triphenylisopropylphosphoniumiodid mit 4-Oxobutensäurealkylester in Gegenwart stöchiometrischer Menge an Butyllithium herzustellen. Dieses Verfahren hat den Nachteil, daß der Butensäureester schwer zugänglich und Butyllithium nicht einfach handhabbar ist.It is known that acetals of the 2,2-dialkyl-3-formyl-cyclopropanecarboxylic acid esters according to DE-OS 26 IS 160 by reacting triphenylisopropylphosphonium iodide with alkyl 4-oxobutene in the presence of stoichiometric Amount of butyllithium to produce. This process has the disadvantage that the butenoic acid ester difficult to access and butyllithium is not easy to handle.
Der Erfindung lag die Aufgabe zugrunde, Zwischenprodukte für substituierte Cyclopropancarbonsäureester aufzufinden, die auf einfachem Wege, d. h. wirtschaftlicher als mit den bisher bekannten Verfahren möglich, herstellbar sind.The invention was based on the object of providing intermediates for substituted cyclopropanecarboxylic acid esters to find the easy way, d. H. more economical than possible with the previously known processes are.
In Erfüllung dieser Aufgabe wurden halogensubstituierte Tetrahydro-a-pyrone und ein Verfahren zur Herstellung dieser Produkte, wie nachstehend beschrieben, gefunden.In accomplishing this task, halogen-substituted tetrahydro-a-pyrones and a process for their preparation were found of these products as described below.
Die erfindungsgemäßen halogensubstituierten Tetrahydro-a-pyrone werden durch die allgemeine Formel II charakterisiertThe halogen-substituted tetrahydro-a-pyrones according to the invention are represented by the general formula II characterized
R1 R2 R 1 R 2
X OX O
in welcher R1, R2 und R3 Wasserstoff und/oder gleiche oder verschiedene Alkylgruppen mit 1 bis 10 C-Atomen und X Chlor- oder Bromatome bedeuten.in which R 1 , R 2 and R 3 are hydrogen and / or identical or different alkyl groups with 1 to 10 carbon atoms and X are chlorine or bromine atoms.
Das Verfahren zur Herstellung der erfindungsgemäßen Verbindungen der Formel II ist dadurch gekennzeichnet, daß man in an sich bekannter Durchfuhrungsweise 3,4-Dihydrc-a-pyrone der Formel IVThe process for the preparation of the compounds of the formula II according to the invention is characterized in that that 3,4-Dihydrc-a-pyrones of the formula IV
worin R1, R2 und R1 die oben angegebenen Bedeutungen haben, in einem inerten Lösungsmittel mit Chlor oder Brom umsetzt. Die 3,4-Dihydro-a-pyrone der Formel IV sind ihrerseits gemäß dem in der DE-OS 29 52 068 beschriebenen Verfahren leicht zugänglich.wherein R 1 , R 2 and R 1 have the meanings given above, reacts with chlorine or bromine in an inert solvent. The 3,4-dihydro-a-pyrones of the formula IV are, for their part, easily accessible according to the process described in DE-OS 29 52 068.
Die Umsetzungen zur Herstellung der erfindungsgemäßen htlogeruubttituierten Tetrahydro-o-pyrone der Formel II und deren Weiterverarbeitung zu Acetalen der2,2-Dialkyl-3-formyl-cyclopropancarbonsäureesterder The reactions for the preparation of the inventive tetrahydro-o-pyrones of the formula II and their further processing to acetals of the 2,2-dialkyl-3-formyl-cyclopropanecarboxylic acid esters
χ/χ /
NN
X Ν X Ν
\\
οο
R—OR-O
OO
\\
//
Die Halogenaddition an das 3,4-Dihydro-a-pyron der Formel IV erfolgt in an sich für solche Additionen bekannter Weise in einem inerten organischen Lösungsmittel, vorzugsweise in einem flüssigen Chlorkohlenwasserstoff, wie z. B. CCl4, durch Zudosieren des Halogens zwischen -SO und +400C. Vorzugsweise wird bei Temperaturen zwischen -10 und +400C gearbeitet. Das Lösungsmittel wird nach Beendigung der Reaktion durch Destillation bei vermindertem Druck, z. B. im Wasserstrahlvakuum, entfernt Die auf diese Weise erhaltenen Produkte der Fonnel II können ohne weitere Reinigung fur die nächste Reaktionsstufe eingesetzt werden.The halogen addition to the 3,4-dihydro-a-pyrone of the formula IV is carried out in a manner known per se for such additions in an inert organic solvent, preferably in a liquid chlorinated hydrocarbon, such as. B. CCl 4 , by metering in the halogen between -SO and +40 0 C. Temperatures between -10 and +40 0 C are preferably used. After the reaction has ended, the solvent is removed by distillation under reduced pressure, e.g. B. in a water jet vacuum, removed. The products of formula II obtained in this way can be used for the next reaction stage without further purification.
Die Umsetzung der Verbindungen der Formel II zu den offenkettigen Acetaten der Formel III wird mit der 0,8- bis 1 ^fachen stöchiometrischen Menge eines Alkoholats der Formel V in Gegenwart überstöchiometrischer Mengen von Alkylalkoholen der Formel Va als Lösungsmittel,The implementation of the compounds of the formula II to the open-chain acetates of the formula III is carried out with the 0.8 to 1 ^ times the stoichiometric amount of an alcoholate of the formula V in the presence of superstoichiometric amounts of alkyl alcohols of the formula Va as a solvent,
M-OR (V)M-OR (V)
R-OH (Va)R-OH (Va)
in welchen R gleiche oder verschiedene Alkylreste mit 1 bis 4 Kohlenstoffatomen und M Alkali bedeuten, bei Temperaturen zwischen -10 und +600C durchgeführt. Vorzugsweise wird bei Temperaturen zwischen -10 und +400C gearbeitet Der Alkoholüberschuß wird zweckmäßig zwischen zwei- und 200molarem Überschuß variiert Zwecks Isolierung der Verbindungen der Formel III wird, falls mit überstöcbiomei. fachen Mengen Alkoholat gearbeitet wurde, dieses mit Wasser extrahiert und das Rohprodukt destilliert Wenn kein Qberschüssiges Alkoholat vorhanden ist, kann direkt nach der Reaktion destilliert werden.in which R denotes identical or different alkyl radicals having 1 to 4 carbon atoms, and M is alkali mean carried out at temperatures between -10 and +60 0 C. Preferably carried out at temperatures between -10 and +40 0 C, the alcohol excess is suitably between two and 200molarem excess purpose of isolation varies the compounds of formula III is substituted with überstöcbiomei. times the amount of alcoholate has been worked, this is extracted with water and the crude product is distilled. If there is no excess alcoholate, it can be distilled directly after the reaction.
Die Cyclisierung zum Cyclopropancarbonsäureest*r der Fonnel VI wird mit HiUe stöchiometrischer Mengen Alkoholat der Fonnel V durchgeführt. Als Lösungsmittel kommen Alkoholate der Formel Va zum Einsatz, wobei vorzugsweise diejenigen Alkohole verwendet werden, von denen sich das Alkoholat ableitetThe cyclization to the cyclopropanecarboxylic acid ester of formula VI is carried out in stoichiometric amounts Alcoholate of formula V carried out. Alcoholates of the formula Va are used as solvents, preferably those alcohols are used from which the alcoholate is derived
Auch andere inerte Lösungsmittel, wie z. B. Diäthyläther, können verwendet werden. Die Cyclisierung wird bei Temperaturen zwischen +30 und + ISO0C, gegebenenfalls unter Druck, durchgeführt. Die Verbindungen der Formel VI fallen als eis, trans-Gemisch an.Other inert solvents, such as. B. diethyl ether can be used. The cyclization is carried out at temperatures between +30 and + ISO 0 C, optionally under pressure. The compounds of the formula VI are obtained as a cis, trans mixture.
Die Verbindungen der Formel VI können auch ohne Isolierung der Zwischenstufe ΙΠ aus den Verbindungen der Fonnel II hergestellt werden. In diesem Fall wird mit der 1,8- bis 2,2fachen stöchiometrischen Menge eines Alkoholats der Formel V in Gegenwart uberstöchiometrischer Mengen von Alkylalkoholen der Fonnel Va (zweckmäßigerweise zwei- bis 200molarer Überschuß) gearbeitet. Die Temperatur wird anfangs zwischen -10 und +600C gehalten und im Verlauf der Reaktion auf +30 bis +1SO0C gesteigert. Es ist jedoch auch möglich, diese Reaktion ohne Isolierung der Zwischenstufe in einem Temperaturbereich zwischen +30 und +600C durchzuführen.The compounds of the formula VI can also be prepared from the compounds of the formula II without isolating the intermediate stage ΙΠ. In this case, 1.8 to 2.2 times the stoichiometric amount of an alcoholate of the formula V is used in the presence of excess stoichiometric amounts of alkyl alcohols of the formula Va (expediently a two to 200 molar excess). The temperature is initially kept between -10 and +60 0 C and increased to +30 to + 1SO 0 C in the course of the reaction. However, it is also possible to carry out this reaction without isolation of the intermediate in a temperature range between +30 and +60 0 C.
Die Verbindungen der Formel VI können nach bekannten Methoden in die freien Aldehyde überfuhrt werden. Diese Aldehyde sind wichtige Zwischenprodukte zur Herstellung von Insektiziden der Pyrethroidklasse.The compounds of the formula VI can be converted into the free aldehydes by known methods. These aldehydes are important intermediates in the manufacture of insecticides of the pyrethroid class.
17,6 g 4,4-Dimethyl-3,4-dihydro-<r-pyron werden in 45 g CCl4 gelöst, und zu dieser Mischung werden unter Rühren 22,3 g Brom in 59 g CCl4, gelöst bei 5 - 100C, zugetropft. Nach dem Zutropfen wird das Lösungsmittel im Wasserstrahlvakuum entfernt. Man erhält 39,5 g kristallines 2,2-Dimethyl-3,4-dibrom-tetrab.ydro-a-pyron (Fp. 85-87°C aus CCl4).17.6 g of 4,4-dimethyl-3,4-dihydro- <r-pyrone are dissolved in 45 g of CCl 4 , and 22.3 g of bromine in 59 g of CCl 4 , dissolved at 5 - are added to this mixture while stirring 10 0 C, added dropwise. After the dropwise addition, the solvent is removed in a water jet vacuum. 39.5 g of crystalline 2,2-dimethyl-3,4-dibromo-tetrabydro-a-pyrone (melting point 85 ° -87 ° C. from CCl 4 ) are obtained.
Ή-NMR-Spektrum (100 MHZ, CCl4): öfm: 1,16 (s, 3 H), 1,24 (s, 3 H), 2,70 (m, 2 H); Zentren bei 4,32 und4,41 (m, 1 H); Zentren bei 6,46-6,61 (m, 1 H).Ή-NMR Spectrum (100 MHz, CCl 4 ): ö fm : 1.16 (s, 3 H), 1.24 (s, 3 H), 2.70 (m, 2 H); Centers at 4.32 and 4.41 (m, 1H); Centers at 6.46-6.61 (m, 1H).
9,5 g 2,2-Dimethyl-3,4-dibrom-tetrahydro-a-pyron werden in 5 g Methanol gelöst und zu dieser Mischung 1,67 g Na-Methylat, in 11 g Methanol gelöst, innerhalb 2 Stunden unter Rühren bei 2O-3O°C zugetropft. Anschließend gießt man die Reaktionsmischung in 50 ml H2O und extrahiert dies mit Methylenchlorid. Nach9.5 g of 2,2-dimethyl-3,4-dibromo-tetrahydro-a-pyrone are dissolved in 5 g of methanol, and 1.67 g of sodium methylate, dissolved in 11 g of methanol, are added to this mixture over the course of 2 hours while stirring added dropwise at 20-3O ° C. The reaction mixture is then poured into 50 ml of H 2 O and extracted with methylene chloride. To
Trocknen der organischen Phase über ein Molekularsieb und Entfernen des Lösungsmittels im Wasserstrahlvakuum
erhält man 7,8 g SjS-Dünethoxy^brom-S.S-dimethylpentancarbonsäuremethylester.
'H-NMR-Spektrum (30 MHZ, CCl4): <?ppm: UO (s, 6H); 2,53 (s, 2H); 3,45 (s, 6H); 4,48 (s, 2H).
6,2 g S.S-Dimethoxy^-brom-S.S-dimethylpentacarbonsäuremethylester werden in 3,3 g Methanol gelöst und
5 zu dieser Mischung eine Lösung aus 1,3 g Na-methylat und 8,2 g Methanol zugetropft. Danach wird 15 Stunden
bei 500C gerührt. Anschließend wird die Reaktionsmischung auf Wasser gegeben, mit Diäthyläther extrahiert
und die organische Phase getrocknet. Nach Entfernen des Äthers im Wasserstrahlvakuum wird der Rückstand
destilliert. Man erhält 3,55 g cis.trans^^-Dimethyl-S-formyKdimethylacetali-cyclopropancarbonsäuremethylester.
Drying the organic phase over a molecular sieve and removing the solvent in a water jet vacuum gives 7.8 g of SjS-Dünethoxy ^ bromo-SS-dimethylpentanecarboxylic acid methyl ester.
'H-NMR spectrum (30 MHz, CCl 4 ): <? ppm : UO (s, 6H); 2.53 (s, 2H); 3.45 (s, 6H); 4.48 (s, 2H).
6.2 g of SS-dimethoxy ^ -bromo-SS-dimethylpentacarboxylic acid methyl ester are dissolved in 3.3 g of methanol and a solution of 1.3 g of sodium methoxide and 8.2 g of methanol is added dropwise to this mixture. The mixture is then stirred at 50 ° C. for 15 hours. The reaction mixture is then poured into water, extracted with diethyl ether and the organic phase is dried. After removing the ether in a water jet vacuum, the residue is distilled. 3.55 g of cis.trans ^^ - dimethyl-S-formyKdimethylacetali-cyclopropanecarboxylic acid methyl ester are obtained.
|| Beispiel 2|| Example 2
IS 0,5 g 4,4-Dimethyl-3,4-düiydro-ar-pyron werden in 4,5 g Tetrachlormethan gelöst, und in diese Mischung wer-IS 0.5 g of 4,4-dimethyl-3,4-düiydro-ar-pyrone are dissolved in 4.5 g of carbon tetrachloride, and in this mixture are
p den 0,3 g gasförmiges Chlor bei 100C eingeleitet Nach Entfernen des Lösungsmittels im Wasserstrahlvakuump the 0.3 g of gaseous chlorine passed in at 10 ° C. After removing the solvent in a water jet vacuum
fc] !5 erhält man 0,7 g cis,trans-2,2-Diniethyi-3,4-dichlor-tetrahydro-flr-pyron.fc]! 5, 0.7 g of cis, trans-2,2-Diniethyi-3,4-dichloro-tetrahydro-flr-pyrone is obtained.
IS 'H-NMR-Spektrum (30 MHZ, CCl4): <5ppm: 1,25 (bs, 6H); 2,70 (bs, 2H); 4,15; 4,20 (2d, IH); 6,15-6,45IS 'H-NMR spectrum (30 MHz, CCl 4 ): <5 ppm : 1.25 (bs, 6H); 2.70 (br.s, 2H); 4.15; 4.20 (2d, 1H); 6.15-6.45
ψ-ψ- (2d, IH).(2d, IH).
p| 166 g 2,2-Dimethyl-3,4-dichlor-tetrahydro-flr-pyron werden in 124 g Methanol bei Raumtemperatur gelöst,p | 166 g of 2,2-dimethyl-3,4-dichloro-tetrahydro-fluoropyrone are dissolved in 124 g of methanol at room temperature,
£| und zu dieser Lösung wird eine methanolische Natriummethylat-Lösung (48 g NaOCH3 in 247 g Methanol)£ | and a methanolic sodium methylate solution (48 g NaOCH 3 in 247 g methanol) is added to this solution
0: 20 getropft. Es wird 1 Stunde bei Raumtemperatur nachgerührt. Das Methanol wird im Wasser·'vahlvakuum ent- 0: dripped 20th It is stirred for 1 hour at room temperature. The methanol is de-
Ic femt und cer Rückstand in kleinen Portionen im Hochvakuum destilliert. Man erhält 187,5f g 5,5-Dimethoxy-Ic femt and cer residue distilled in small portions in a high vacuum. 187.5 g of 5,5-dimethoxy are obtained
|ΐ 4-chlor-3,i-dimethylpentancarbonsäureru3thylester (Siedepunkt 0,13 mbar: 117-119°C).| ΐ ethyl 4-chloro-3, i-dimethylpentanecarboxylate (boiling point 0.13 mbar: 117-119 ° C).
B 'H-NMR-Spektrum (80 MHZ, CDCl3V <5ppm: 1,19 (s, 6H); 2,51 (m, 2H); 3,43 (s, 3H); 3,44 (s, 3H); B 'H-NMR Spectrum (80 MHz, CDCl 3 V <5 ppm : 1.19 (s, 6H); 2.51 (m, 2H); 3.43 (s, 3H); 3.44 (s , 3H);
' 3,66 (s, 3 H); 4,24 (d, 1 H); 4,50 (d, 1 H).'3.66 (s, 3H); 4.24 (d, 1H); 4.50 (d, 1H).
H 25 8 g S.S-Dimethoxy^-chlor-S^-dimethylpentancarbonsäuremethylester werden in 30 ml Diäthylenglykoldi- H 25 8 g of SS-Dimethoxy ^ -chlor-S ^ -dimethylpentanecarboxylic acid methyl ester in 30 ml of diethylene glycol
: methyläther mit 2,2 g NaOCH3 5 Stunden bei 1100C gerührt. Das entstandene Kochsalz wird abfiltriert, mit Diäthyläther gewaschen, und die organischen Phasen werden vereinigt. Nach Entfernung des Diäthyläthers im: Methyl ether stirred for 3 5 hours at 110 0 C with 2.2 g of NaOCH. The resulting common salt is filtered off, washed with diethyl ether, and the organic phases are combined. After removing the diethyl ether im
;,'·- Vakuum wird der Diäthylenglykoläther im Wasserstrahlvakuum abdestilliert und der Rückstand im Hoch-;, '· - vacuum, the diethylene glycol ether is distilled off in a water jet vacuum and the residue in a high
V vakuum destilliert. Man erhält 5,2 g 2,2-Dimethyl-3-fonnyl-(dimethylacetal)-cyclopropancarbonsäuremethyl-30 ester.V vacuum distilled. 5.2 g of 2,2-dimethyl-3-formyl- (dimethylacetal) -cyclopropanecarboxylic acid methyl-30 are obtained ester.
Claims (2)
R1 1. Halogen-substituted tetrahydro-e-pyrones of the general formula Π
R 1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803050795 DE3050795C2 (en) | 1980-12-06 | 1980-12-06 | Halogen-substituted tetrahydro-α-pyrones and processes for their preparation |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803050795 DE3050795C2 (en) | 1980-12-06 | 1980-12-06 | Halogen-substituted tetrahydro-α-pyrones and processes for their preparation |
| DE19803046059 DE3046059C2 (en) | 1980-12-06 | 1980-12-06 | 4-Halo-5,5-dialkoxypentanoic acid esters, process for their preparation and their use for the preparation of 2,2-dialkyl-3-formylcyclopropanecarboxylic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3050795C2 true DE3050795C2 (en) | 1985-07-18 |
Family
ID=25789563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19803050795 Expired DE3050795C2 (en) | 1980-12-06 | 1980-12-06 | Halogen-substituted tetrahydro-α-pyrones and processes for their preparation |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3050795C2 (en) |
-
1980
- 1980-12-06 DE DE19803050795 patent/DE3050795C2/en not_active Expired
Non-Patent Citations (1)
| Title |
|---|
| NICHTS-ERMITTELT * |
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