DE3046059C2 - 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 - Google Patents
4-Halo-5,5-dialkoxypentanoic acid esters, process for their preparation and their use for the preparation of 2,2-dialkyl-3-formylcyclopropanecarboxylic acid estersInfo
- Publication number
- DE3046059C2 DE3046059C2 DE19803046059 DE3046059A DE3046059C2 DE 3046059 C2 DE3046059 C2 DE 3046059C2 DE 19803046059 DE19803046059 DE 19803046059 DE 3046059 A DE3046059 A DE 3046059A DE 3046059 C2 DE3046059 C2 DE 3046059C2
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- Prior art keywords
- preparation
- acid esters
- halo
- dialkyl
- formula
- 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.)
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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
in der R gleiche oder verschiedene Alkylgruppen mit 1 bis 4 C-Atomen, R1, R2 und R3 Wasserstoffalome und/oder Alkylgruppen mit 1 bis 10 C-Atomen und X ein Chlor- oder Bromatom bedeuten.in which R is identical or different alkyl groups with 1 to 4 carbon atoms, R 1 , R 2 and R 3 are hydrogen atoms and / or alkyl groups with 1 to 10 carbon atoms and X is a chlorine or bromine atom.
2. Verfahren zur Herstellung von 4-Halogen-5.5-dialkoxypentansäureestern nach Anspruch I, dadurch gekennzeichnet, daß man ein halogensubstituiertes Lacton der allgemeinen Formel II,2. A process for the preparation of 4-halo-5,5-dialkoxypentanoic acid esters according to Claim I, characterized in that characterized in that a halogen-substituted lactone of the general formula II,
ODOD
in der R1, R2, R3 und X die im Anspruch 1 angegebene Bedeutung haben, mit der 0,8- bis 1.2fachen stöchiometrischen Menge eines Alkoholate der allgemeinen Formel R — OM in Gegenwart überstöchiometrischer Mengen von Alkylalkoholen der allgemeinen Formel R — OH, worin R die im Anspruch 1 angegebene Bedeutung hat und M ein Alkalimetallatom bedeutet, bei Temperaturen zwischen — IO und +600C umsetzt.in which R 1 , R 2 , R 3 and X have the meaning given in claim 1, with 0.8 to 1.2 times the stoichiometric amount of an alcoholate of the general formula R - OM in the presence of superstoichiometric amounts of alkyl alcohols of the general formula R - OH, wherein R has the meaning given in claim 1 and M represents an alkali metal atom, at temperatures between - IO and +60 0 C is reacted.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man die Umsetzung bei Temperaturen zwischen —10 und +400C durchführt.3. The method according to claim 2, characterized in that the reaction at temperatures between -10 and +40 0 C is carried out.
4. Verwendung der 4-Halogen-5,5-dialkoxypcnlansäurecster nach Anspruch 1 zur Herstellung von Acei.ilcnder2,2-Dialkyl-3-formyl-cyclopropancarbonsäurealkylestcrderallgcmeinen Formel Hl,4. Use of the 4-halo-5,5-dialkoxypinlansäurecster according to claim 1 for the production of aci.ilcnder2,2-dialkyl-3-formyl-cyclopropanecarboxylic acid alkyl esterallgcmeinen Formula Hl,
R-OR-O
R-OR-O
CHCH
COORCOOR
(ΠΙ)(ΠΙ)
worin R, R1. R2 und R3 die im Anspruch 1 angegebene Bedeutung haben, durch Umsetzung mit der stöchiometrischen Menge eines Alkoholate der allgemeinen Formel R — OM. in der M ein Alkalimetallatom bedeutet, bei Temperaturen zwischen +30 und +1500C.wherein R, R 1 . R 2 and R 3 have the meaning given in claim 1, by reaction with the stoichiometric amount of an alcoholate of the general formula R - OM. in which M means an alkali metal atom, at temperatures between +30 and +150 0 C.
Die Erfindung betrifft 4-Halogen-5,5-dialkoxypentancarbonsäureester, deren Herstellung und deren Weiterverarbeitung zu substituierten Cyclopropancarbonsäurecstcrn. Letztere sind bekannte Vorprodukte zur Herstellung von Insektiziden.The invention relates to 4-halo-5,5-dialkoxypentanecarboxylic acid esters, their preparation and their further processing to substituted cyclopropanecarboxylic acids. The latter are known preliminary products for production of insecticides.
Es ist bekannt, Acetale der 2,2-Dialkyl-3-formyl-cyclopropancarbonsäurecstcr nach der DE-OS 2b 15 IbO durch Umsetzung von Triphcnylisopropylphosphoniumjodid mit 4-Oxo-bulensäurealkylesler in Gegenwart bo 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 chain according to DE-OS 2b 15 IbO by reacting Triphcnylisopropylphosphoniumjodid with 4-Oxobulensäurealkylesler in the presence bo 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.
I)ci Erfindung lag die Aufgabe zugrunde, substiluierlc Cyelopropancarbonsaureester auf einfachem Wege, d. h. wirtschaftlicher als mit den bisher bekannten Verfahren möglich, herzustellen.I) ci invention was based on the object to substiluierlc Cyelopropancarbonsaureester in a simple way, d. H. more economical than possible with the previously known processes.
Diese Aufgabe wurde gelöst durch das Auffinden neuer 4 llalogen-S.i-dialknxvpenlaneaiboiisaiiieoslcr, ein b·) Verfahren /u deren Herstellung gemäß Anspruch 2 und deren Verwendung zur Herstellung von substituierten Cyclopropanciirbonsäurealkylcstern entsprechend Anspruch 4, gelöst.This object was achieved by finding new 4 llalogen-Si-dialknxvpenlaneaiboiisaiiieoslcr, a b) process / and their production according to claim 2 and their use for the production of substituted cyclopropaneci-alkyls according to claim 4.
Die erfindungsgemäßen 4-Halogcn-5.5-dialkoxypentancarborlsäuι■eesler werden durch die l'ormel 1 charakte-The 4-Halogcn-5.5-dialkoxypentancarborlsäuι ■ eesler are characterized by the formula 1
:h hc: h hc
>—CH C = O> - CH C = O
X-CH HC-R3 RO-X-CH HC-R 3 RO-
RORO
OROR
in der R gleiche oder verschiedene Alkylgruppen mit 1 bis 4 C-Atomen, R1, R2 und R1 Wasserstoffatome und/oder Alkylgruppen mit 1 bis 10 C-Atomen und X Chlor- oder Bromatome bedeuten.in which R is identical or different alkyl groups with 1 to 4 carbon atoms, R 1 , R 2 and R 1 are hydrogen atoms and / or alkyl groups with 1 to 10 carbon atoms and X is chlorine or bromine atoms.
Als Ausgangsprodukte zur Herstellung der neuen Pentancarbonsäurederivate dienen ebenfalls neue Lactone der allgemeinen Formel IlNew lactones are also used as starting materials for the production of the new pentanecarboxylic acid derivatives of the general formula II
R1 R2 X V R3 R 1 R 2 XVR 3
XOQXOQ
in welcher R1, R2 und RJ Wasserstoff und/oder gleiche oder verschiedene Alkylgruppen mit 1 bis 10 C-Atomen und X Chlor- oder Bromatome bedeuten, die ihrerseits einfach aus den Verbindungen der Formel IVin which R 1 , R 2 and R J are hydrogen and / or identical or different alkyl groups with 1 to 10 carbon atoms and X are chlorine or bromine atoms, which in turn are simply derived from the compounds of the formula IV
(IV)(IV)
worin R1, R2 und R3 Wasserstoff und/oder gleiche oder verschiedene Alkylresic mit 1 bis IOC-Atomen bedeuten, erhältlich sind. Verbindungen enisprechend der Formel IV sind nach dem in der deutschen Patentanmeldung P 29 52 068.1 beschriebenen Verfahren leicht zugänglich.wherein R 1 , R 2 and R 3 are hydrogen and / or identical or different alkylresic with 1 to IOC atoms, can be obtained. Compounds corresponding to the formula IV are easily accessible by the process described in German patent application P 29 52 068.1.
Die Umsetzungen zur Herstellung der Verbindungen der Formeln I und Il sowie die Verwendung der letztgenannten Verbindungen zur Herstellung von Acctalen der 2,2-Dialkyl-3-formyl-cycloprop;insüurecstcr der Formel III verlaufen nach folgendem Schema:The reactions for the preparation of the compounds of the formulas I and II and the use of the last-mentioned compounds for the preparation of acetals of the 2,2-dialkyl-3-formyl-cycloprop; insüurecstcr of the formula III proceed according to the following scheme:
R3 R 3
X0OX 0 O
MOR ROH MOR RAW
R1 R2 R 1 R 2
roro
OROR
ROHRAW
(D(D
MORMOR
R-OR-O
R-OR-O
COORCOOR
Die Halogenaddition an das Dihydropyron der Formel IV erfolgt in an sich für solche Additionen bekannter Weise in einem inerten organischen Lösungsmittel, vorzugsweise in einem flüssigen Chlorkohlenwasserstoff, wie CCLt, durch Zudosieren des Halogens zwischen —50 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 Formel II können ohne weitere Reinigung für die nächste Reaktionsstufe eingesetzt werden.The addition of halogen to the dihydropyrone of formula IV is carried out in per se known for such additions manner in an inert organic solvent, preferably in a liquid chlorinated hydrocarbon, such as CCLT, by the metered addition of the halogen of between -50 and +40 0 C. Preferably, at temperatures between -10 and +40 0 C worked. 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 the 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 offenkeltigen Acetalen der Formel I wird mit der 0,8-bis l,2fachen stöchiometrischen Menge eines Alkoholats MOR (M = Alkali. R = C,_4-Alkyl) in Gegenwart überstöchiometrischer Mengen von Ci —i-Alkylalkoholen als Lösungsmittel,The reaction of compounds of formula II is to the offenkeltigen acetals of the formula I with 0.8 to l, 2-fold stoichiometric amount of an alkoxide MOR (M = alkali. R = C, _ 4 alkyl) in the presence of more than stoichiometric amounts of C - i-alkyl alcohols as solvents,
M-OR VM-OR V
R-OH VaR-OH Va
bei Temperaturen zwischen —10 und +600C durchgeführt. Vorzugsweise wird bei Temperaturen zwischen —10 und +40°C gearbeitet. Der Alkoholüberschuß wird zweckmäßig zwischen zwei- und 200molarem Überschuß variiert. Zwecks Isolierung der neuen Pentancarbonsäurederivate der Formel I wird, falls mit überstöehiometrischen Mengen Aikoholat gearbeitet wurde, dieses mit Wasser extrahiert und das Rohprodukt destilliert. Wenn kein überschüssiges Aikoholat vorhanden ist, kann direkt nach der Reaktion destilliert werden.carried out at temperatures between -10 and +60 0 C. It is preferred to work at temperatures between -10 and + 40 ° C. The excess of alcohol is expediently varied between a two molar and a 200 molar excess. For the purpose of isolating the new pentanecarboxylic acid derivatives of the formula I, if more than stehiometric amounts of alcoholate have been used, this is extracted with water and the crude product is distilled. If there is no excess alcoholate, distillation can take place immediately after the reaction.
Die Cyclisierung zum Cyclopropancarhonsäureester der Formel III wird mit Hilfe stöchiometrischer Mengen Alkalialkoholai durchgeführt Als Lösungsmittel kommen Alkohole mit 1 —4 C-Atomen zum Einsatz, wobei vorzugsweise diejenigen Alkohole verwendet werden, von denen sich das Aikoholat ableitet.The cyclization to the cyclopropanecarboxylic acid ester of the formula III is carried out with the aid of stoichiometric amounts Alkalialkoholai carried out Alcohols with 1 to 4 carbon atoms are used as solvents, whereby preferably those alcohols are used from which the alcoholate is derived.
Auch andere inerte Lösungsmittel wie Diäthyläther können verwendet werden. Die Cyclisierung wird bei Temperaturen zwischen +30 und + 150°C, gegebenenfalls unter Druck, durchgeführt. Die Verbindungen der Formel 111 fallen als eis, trans-Gemisch an.Other inert solvents such as diethyl ether can also be used. The cyclization is at Temperatures between +30 and + 150 ° C, if necessary under pressure, carried out. The connections of the Formula III is obtained as an ice, trans mixture.
Die Verbindungen der Formel IH können auch ohne Isolierung der Zwischenstufe I aus den Verbindungen der Formel Il hergestellt werden. In diesem Fall wird mit der 1,8- bis 2,2fachen stöchiometrischen Menge eines Alkalialkoholats in Gegenwart überstöchiometrischer Mengen von Alkylalkoholen (zweckmäßigerweise zweibis 200molarer Überschuß) gearbeitet. Die Temperatur wird anfangs zwischen —10 und +600C gehalten und im Verlauf der Reaktion auf +30 bis +150°C gesteigert. Es ist jedoch auch möglich, diese Reaktion ohne Isolierung der Zwischenstufe in einem Temperaturbereich zwischen +30 und +60" C durchzuführen.The compounds of the formula IH can also be prepared from the compounds of the formula II without isolating the intermediate I. In this case, 1.8 to 2.2 times the stoichiometric amount of an alkali metal alcoholate is used in the presence of more than stoichiometric amounts of alkyl alcohols (expediently a two to 200 molar excess). The temperature is initially held between -10 and +60 0 C and increased in the course of the reaction to +30 to + 150 ° C. However, it is also possible to carry out this reaction in a temperature range between +30 and +60 ° C. without isolating the intermediate stage.
Die Verbindungen der Formel III können nach bekannten Methoden in die freien Aldehyde überfühn werden. Diese Aldehyde sind wichtige Zwischenprodukte zur Herstellung von Insektiziden der Pyrethroidklassc.The compounds of the formula III can be converted into the free aldehydes by known methods. These aldehydes are important intermediates in the manufacture of insecticides of the pyrethroid class.
a) 17,6 g 4,4-Dimethyl-3,4-dihydro-i*-pyron werden in 45 g CCU gelöst, und zu dieser Mischung werden unter Rühren 22,3 g Brom in 59 g CCU, gelöst bei 5— 100C, zugetropft. Nach dem Zutropfcn wird das Lösungsmittel im Wasserstrahl vakuum entfernt. Man erhält 39,5 g kristallines 4,4-Dimclhyl-5.6-dibrom-r)'-vulerolacton. (Fp.85-87"CausCCU).a) 17.6 g of 4,4-dimethyl-3,4-dihydro-i * -pyron are dissolved in 45 g of CCU, and 22.3 g of bromine in 59 g of CCU, dissolved at 5- 10 0 C, added dropwise. After the dropping, the solvent is removed in vacuo in a water jet. 39.5 g of crystalline 4,4-dimethyl-5,6-dibromo-r) '- vulerolactone are obtained. (M.p. 85-87 "CausCCU).
'H-NMR-Spcktrum (100 MH/., CCU): (fPI„„ = 1,16 (s, 3 H), 1.24 (s. 3 H), 2,70 (m. 2 11); Zentren bei 4,32 und 4,41 (m, 1 H); Zentren bei 6,46-6,6! (m, 1 H).'H-NMR spectrum (100 MH /., CCU): (f PI "" = 1.16 (s, 3 H), 1.24 (s. 3 H), 2.70 (m. 2 11); centers at 4.32 and 4.41 (m, 1H); centers at 6.46-6.6! (m, 1H).
b) 9,5 g 4,4-Dimethyl-5,6-dibrom-J-valero!aclon 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 20—300C zugetropft. Anschließend
gießt man die Reaktionsmischung in 50 ml H2O und extrahiert dies mit Methylenchlorid. Nach
Trocknen der organischen Phase über einem Molekularsieb und Entfernen des Lösungsmittels im Wasserstrahlvakuum
erhält man 7,8 g 5,5-Dimethoxy-4-brom-3,3-dimethylpentancarbonsäuremethylester.
'H-NMR-Spektrum(30 MHz.CCU):^,,,,, = 1,20(s,6 H);2,53(s, 2 H);3,45(s,6 H);4,48(s, 2 H).b) 9.5 g of 4,4-dimethyl-5,6-dibromo-J-valero / aclon are dissolved in 5 g of methanol and 1.67 g of sodium methylate are added to this mixture. dissolved in 11 g of methanol was added dropwise over 2 hours with stirring at 20-30 0 C. The reaction mixture is then poured into 50 ml of H2O and extracted with methylene chloride. After drying the organic phase over a molecular sieve and removing the solvent in a water jet vacuum, 7.8 g of methyl 5,5-dimethoxy-4-bromo-3,3-dimethylpentanecarboxylate are obtained.
'H-NMR Spectrum (30 MHz.CCU): ^ ,,,,, = 1.20 (s, 6H); 2.53 (s, 2H); 3.45 (s, 6H); 4.48 (s, 2H).
c) 6.2 g 5,5-Dimethoxy-4-brorn-3,3-dimethylpentanearbonsäuremethylester werden in 3,3 g Methanol gelöst und zu dieser Mischung eine Lösung aus 1,3 g Na-Methylat und 8,2 g Methanol zugetropfl. Danach wirdc) 6.2 g of 5,5-dimethoxy-4-bromo-3,3-dimethylpentanearboxylic acid methyl ester are dissolved in 3.3 g of methanol and a solution of 1.3 g of sodium methylate and 8.2 g of methanol was added dropwise to this mixture. After that, will
so 15 Stunden bei 500C gerührt. Anschließend wird die Reaktionsrnischung 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 eis, trans-2,2-Dimelhyl-3-formyl-(dimethylacetal)-cyclopropancarbonsäuremet hy !ester.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 ice, trans-2,2-dimethyl-3-formyl- (dimethylacetal) -cyclopropanecarboxylic acid methyl ester are obtained.
a) 0,5 g 4,4-Dimethyl-3,4-dihydro-Ä-pyron werden in 4,5g TetracSilormethan gelöst, und in diese Mischung werden 0,3 g gasförmiges Chlor bei 10cC eingeleitet. Nach Entfernen des Lösungsmittels im Wasscrstrahlvakiium erhält man 0,7 g eis, lrans-4,4-Dimethyl-5,6-dichlor-<)-valerolacton.a) 0.5 g of 4,4-dimethyl-3,4-dihydro-Ä-pyrone are dissolved in 4.5 g TetracSilormethan, and 0.3 g of gaseous chlorine at 10 c C are introduced into this mixture. After removing the solvent in a water-jet vacuum, 0.7 g of ice, trans-4,4-dimethyl-5,6-dichloro - <) - valerolactone is obtained.
w) 'H-NMR-Spektrum(30MH/„ CCI4): J,,,,,,, 1.25 (bs, 6 H); 2,70 (bs. 2 H); 4.15; 4,20 (2 d, 1 H); 6.15-b,45 (2 d.w) 'H-NMR spectrum (30MH / "CCI 4 ): J ,,,,,,, 1.25 (bs, 6 H); 2.70 (br. 2H); 4.15; 4.20 (2d, 1H); 6.15-b, 45 (2 d.
I H).I H).
b) 1 bb £ 4,4-Dimcthvl-5,6-dichlorvalerolacton werden in 124 g Methanol bei Raumtemperatur gelöst, und zu dieser Lösung wird eine methanolische Natriummethyla.-LöMing (48 g NaOCHi in 247 g Methanol) getropft. Hs wird 1 Stunde bei Raumtemperatur nachgerührt. Das Methanol wird im Wasserstrahlvakuumb) 1 bb £ 4,4-Dimcthvl-5,6-dichloro valerolactone are dissolved in 124 g of methanol at room temperature, and to a methanolic sodium methylene solution (48 g NaOCHi in 247 g methanol) is added dropwise to this solution. Hs is stirred for 1 hour at room temperature. The methanol is in a water jet vacuum
v> eiuierm und der Rückstand in kleinen Portionen im Hochvakuum destilliert. Man crhiilt 187,8 g 5.5-Dime-v> egg and the residue is distilled in small portions in a high vacuum. 187.8 g of 5.5-dimen-
tho\y-4-chlor3.3-dimethylpentancarbonsäiircmethylestcr (Siedepunkt 0,133 mbar: 117 — 119°C).
'H-NMR-Spektnim (SO MtIz, CDCIj): <*,„„„ = 1,19(s, 6 H); 2,51 (m. 2 H); 3.43 (s. 3 H); 3,44 (s, 3 H); 3,66 (s,
3H):4.24(d. I H):4.50(d. I II).tho \ y-4-chloro3,3-dimethylpentanecarboxylic acid methyl ester (boiling point 0.133 mbar: 117-119 ° C).
'H-NMR spectrum (SO MtIz, CDCIj): <*, """= 1.19 (s, 6 H); 2.51 (m. 2H); 3.43 (s. 3 H); 3.44 (s, 3H); 3.66 (s, 3H): 4.24 (d. IH): 4.50 (d. I II).
c) 8 g 5,5-Dimcthoxy-4-chlor-J,J-dimclhylpcntanearbonsäurcmcthyle!iier werden in JO ml DiäthylengUkuldimeihyläther mit 2,2g NaOCII ι 5 Stunden bei 110"CgCiUhIt. Das entstandene Kochsalz wird abfiltriert, mit Diiithyläther gewaschen, und die organischen Phasen werden vereinigt. Nach Entfernung des Diülhyla'thcrs im Vakuum wird der Diäihylenglykoläther im Wasserstrahlvakuum abdesiilliert und der Rückstand im Hochvakuum destilliert. Man erhält 5,2 g 2,2-Dimethyl-J-formyl-(dimethylacetal)-cyclopmpunairbonsauremethylester. c) 8 g of 5,5-dimethyl-4-chloro-J, J-dimethylpcntanarboxylic acid methylene are dissolved in 1 o ml of diethylene glycol dimethyl ether with 2.2 g NaOCII ι 5 hours at 110 "CgCiUhIt. The resulting common salt is filtered off, with Washed diethyl ether, and the organic phases are combined. After removal of the diulhydrate in vacuo, the diethyl glycol ether is distilled off in a water jet vacuum and the residue in Distilled under high vacuum. 5.2 g of 2,2-dimethyl-J-formyl- (dimethylacetal) -cyclopmpunairboxemethylester are obtained.
Claims (1)
1. 4-Halogen-5,5-dialkoxypentansäureester der allgemeinen Formel IPatent claims:
1. 4-Halo-5,5-dialkoxypentanoic acid ester of the general formula I
Priority Applications (10)
| 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 |
| EP80107955A EP0031932B1 (en) | 1979-12-22 | 1980-12-17 | Substituted lactones, pentanoic acid derivatives and process for their preparation |
| DE8080107955T DE3071987D1 (en) | 1979-12-22 | 1980-12-17 | Substituted lactones, pentanoic acid derivatives and process for their preparation |
| US06/218,593 US4348535A (en) | 1979-12-22 | 1980-12-19 | Substituted lactones and processes for their preparation |
| CA000367357A CA1205814A (en) | 1979-12-22 | 1980-12-22 | Substituted lactones and processes for their preparation |
| JP18061680A JPS56150078A (en) | 1979-12-22 | 1980-12-22 | Substituted lactone, its manufacture and pentanecarboxylic acid derivative |
| US06/282,689 US4424369A (en) | 1979-12-22 | 1981-07-13 | Substituted pyran-2-ones |
| US06/375,060 US4508914A (en) | 1979-12-22 | 1982-05-05 | 3H-Furanones |
| US06/540,731 US4562270A (en) | 1979-12-22 | 1983-10-11 | Process for preparing unsaturated six-membered lactones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 (2)
| Publication Number | Publication Date |
|---|---|
| DE3046059A1 DE3046059A1 (en) | 1982-07-15 |
| DE3046059C2 true DE3046059C2 (en) | 1984-06-28 |
Family
ID=6118502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19803046059 Expired DE3046059C2 (en) | 1979-12-22 | 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 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3046059C2 (en) |
-
1980
- 1980-12-06 DE DE19803046059 patent/DE3046059C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3046059A1 (en) | 1982-07-15 |
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