DE2812673A1 - 2,5,5-TRIMETHYL-3-CARBALCOXY-4- (BETA, BETA-DIHALOGENVINYL) -4,5-DIHYDROFURANE - Google Patents

Description

28 Ι 2673

Trcisdorf, March 22nd "~ ·"'ί OZ .: 78 022 (28 * 7 )

DYNAMIT NOBEL -AKTIEiJGESELLSGHAFT Troisdorf, district Cologne

2,5,5-Ti * iraethyl-3-carTDalkoxy - ^ - (ß, ß-di-dialo-vinyl) -4,5-iihjiro-

furans

The invention _{relates to 2,5 5} 5-triciethyl - ^ - carbalkoxy dihal ο genvinyl) -4,5- <iihycLro furans of the general formula I.

Ί
in which B is a straight-chain or branched alkyl radical and X is Cl or Br.

Another object of the invention is a method for Herstεΐΐι of dihydrofurans of the formula I.

B can be an alkyl radical with Λ "to 18 carbon atoms, preferably with 1 to 8 carbon atoms, in particular with 1 or 2 carbon atoms.

2,5 / 5-trimethyl ~ 3-carbalkoxy-4- (ß, ß-dihalogenvinyl) -4-, 5-dihycro ~ furans are not yet known.

The 2,5,5-trimethyl - ^ - carbalkoxj '- ^ - (ß, ß-dihalovinyl) -4,5-dihydrofurans is obtained when 2,4,4-TriTaethyl-T-3-carbal "iox7-5i-

i (ß, ß-dihalovinyl) - ⁱ <-, 5-dihydricfurans of the general formula ZI

909839 / 0A54

CCUR ¹

II

in which R \ md I have the above meaning, thermally rearranged.

The thermolysis of the compounds of the formula II is expediently carried out in the gas phase. If necessary, a mixture of a compound of the formula II and an inert solvent can be subjected to thermolysis will. It is advisable to use solvents that are in the gaseous state at the thermolysis temperature are present.

In principle, the thermolysis can also be carried out in the liquid phase if necessary in the presence of an inert solvent.

Suitable solvents are aromatic hydrocarbons, such as e.g. benzene, or halogenated hydrocarbons such as carbon tetrachloride.

The thermal lysis temperature is in; generally in the range between 200 and 50O ⁰ C, but it can also be chosen higher if the thermo] yse time is shortened.

The molar mixing ratio of solvent to compounds of the formula II can be varied within wide ranges. Good results are obtained e.g. by looking at one mole of the compound

! of the formula II approx. 1 to 1000% of the solvents or solvent mixtures are used. But also higher amounts of solvent are [possible,
ι

jZur .Erleichterung the \ fena-xiung 'ie-x- liquid or the thermolysis! is subjected to the liquid as a thin layer or as fine droplets [the Hitrebehandlung.

909839/0454

For this one can use, for example, an operable reaction tube, the surface of which is enlarged through the use of random packings is. The pipe, which is arranged vertically, for example, is rit at the head an import opening for the starting product to be treated so; ie provided with a gas inlet device for an inert gas.

In the case of thermolysis, for example, one can proceed in such a way that the connection of the formula II, optionally dissolved in a solvent, at the top of the ξ Rohres, preferably continuously, dripped in as a liquid ods ~ possibly using an inert gas as pressure and transport medium jet in. The connection to thennolysieren.de, possibly in Ger.iscr. with an inert solvent can also be gaseous in the actual Thermolysis apparatus can be introduced continuously or in batches.

The flow rate of the gas to be thermolyzed and thus the thermolysis time can, depending on the dimensions of the reactor, the filling level, the dimension on and the type of? body, the temperature of the reaction area, by adjuster; the required pressure drop between the inlet and outlet openings of the pipe and regulated by the dosage rate will. The optimal conditions are expedient in goal tests determined.

After passing the hot reaction zone \ fird the gaseous Tr.erc.:- Iysat e.g. cooled to room temperature. The condensate will then a fractional distillation, preferably with application a vacuum.

The method according to the invention is used, for example, in a quartz reactor. However, other reactor materials are also suitable., V; . e.g. ceramics and the like Quartz, but possibly also other materials such as ceramics.

The thermolysis can take place under regional pressure, overpressure as well as can be anticipated under reduced pressure.

It can be carried out continuously or discontinuously.

909839 / 04S4

BATH ORIGINAL

It is advisable to exclude the presence of acid in the thermolysis to make sure that the thermolysis equipment is appropriate before thermolysis with an inert gas, e.g. nitrogen, noble gases, how argon and / or helium is purged. Even during the years. ~ Oljs: an inert gas should expediently be present.

The starting compounds of the formula II are, un new Substances whose production is described in the previously unpublished German patent application P 27 4-0 4-79-1.

In this process, the starting compounds of Porr.e ~ are obtained II, in which R is a straight-chain or branched alkyl radical and X is Gl or Br, by reaction of a β-alkoxycrotonic acid ester the general formula

OR ¹

CII ₇ -C = C-COpR

H - HI

j -j

■ in which R and R can be the same or different and straightness or represent branched alkyl radicals with ja) a 1,1,1-trihalo-4-riethyl-3-penben-2-ol of the general rule 'Formula

HH CH ₅ . IV 3

₅
3

jin the X means Cl or Br, in the presence of an acidic catal; - isator and / or with

ib) a 1,1,1-Tx'ihrilogen ~ 4-methyl ~ 4-penten-2-ol of the general genes i formula

"GH ..
y

909839/0454

"- 28TZE73" ""

- ι -

in which X is Cl or Br, in the presence of an acidic catalyst.

R and R are Allcylreste having from 1 to 18, preferably ι atoms ICohler.-bis above, in particular having 1 or 2 carbon atoms.

Examples of suitable catalysts are Lewis acids such as AICI ₇ , JZnCIp, BF ₇ ^ FeCl ₇ and the like, protonic acids (Brönsted acids), such as HpSO ^ ,, H ₇ POy. ,, p-toluenesulfonic acids, trichloroacetic acid, ic.ur =! Ion exchanger and Like. Also mixtures of the individual acids. .: cii ■ be used.

The catalysts are used in amounts up to 20 iIol-%, less than 10 KoI- #, especially in smaller, from 0.1 to 4 mol - ..!, related on the used starting material of the general Forr.-.si III used.

The alcohols and hydrogen halides released during the reaction Preferably removed during conversion.

The implementation; is increased in the absence of V / assex ¹ and at :? Temperature. In general, temperatures from 50 ° to 200 ° C. are suitable.

The process is generally carried out as follows: The β-alkoxycrotonic acid ester (III) is heated with IV and / or V with stirring in the presence of the catalyst, the desuüher.i alcohol being removed by distillation during the reaction. ^r ir'I. As a precaution, III is added in portions or continuously while maintaining;: r. dor reaction temperature to IV or V or v /. metered in to a mixture of IV xmd V. Ede metering extends to 2v. ^r ec ': rJi'.: i ^ over the entire reaction time, e.g. 2 to 12 hours. The conversion product can mm, preferably after removal; of

ι ■

Catalyst, preferably, the orfindungsgemäßen thermolysis werden► subjected, but is u-rriaetzangsprodukt fractionated d &^c;!. Riiliert purpose of separating the übarschüssigen starting compounds, the I ^r orr.sl III or IV and / or V.vor the -Light‖

909839/0454

281267a

The method of the present invention can be used with particular advantage Apply the invention in the preparation of the chlorine compounds.

The compounds of general formula I are intermediates for S7 / ntheses of insecticides. "

The present invention is illustrated by the following examples.

909839/0 ^ 54

example 1

10 g 2 _i 4-, 4-trimethyl-3-carbomethoxy-5- (ß, ß-dichlorviri3a) -4,5-dihydrofuran are dissolved in 2OQ g -benzene and this solution through a vertical quartz tube, which is equipped with quartz balls Diameter 0.4 cm is filled, dripped through in the presence of nitrogen. The 1 m long quartz tube had a diameter of 3.5 cm. The filling level (= heating zone) was JO cm. The quartz tube is heated from the outside so that an internal temperature of 350 C is measured .. (measurement in the middle of the heating zone). The dripping speed is. 40 g solution / hour. The gaseous thermolysate emerging from the bore is collected in a receiver and cooled to room temperature. After fractional distillation of the condensate in vacuo, a uniform fraction is obtained (boiling point 10 _Torr : 91-92 ° C.) (yield 7.9 g = 79%) which, based on NMR spectroscopic and mass spectroscopic investigations, is classified as 2, 5,5-trimethyl-3-carbomethoxy ~ 4- (β, β-dichlorovinyl) -4,5-dihydrofuran is identified.

KMR spectrum (100 MEIz, CCl ₄ ); / = 5.72 (d, IC); 3.72 (dq, 1H); 3.65 (s, 3H); 2.16 (d. 3H); 1.41 (s, 3H); 1.31 (s,

10 g of 2,4,4-trimethyl-3-carboethoxy-5- (β, β-dichlorovinyl) -4,5-dihydrofuran are thermolyzed analogously to Example 1. 7 »3 g (= 73 % ) 2.5 _? 5-trimethyl-3-carboethoxy-4- (ß, ß-dichlorovinyl) -4,5-dihydrofuran (bp _{Λ c φ.} 102-105 ⁰ C).

Nuclear Magnetic Resonance Spectrum (100 MHz, CDCl ₃₅ ): ^ = 5.74 (d, 1H); 4.14 (m. 2H); 3.78 (bd, 1H); 2.10 (br.s, 3H); 1.48 - 1.10 (m,

909839/0454

Claims (1)

Pat ent claims 1. 2,5,5-trimethyl-3-c & jH} a] Jco; -: y- ~ '' J ~ (·.: ·, 3-dihalogetivir.yl) - ^, 5-dihydroiurane of the general l- ' oi "· ¹ :;! I Vf-CH-CX ₀ in the R a straight-chain or branched Ai-tylre.st isx; and X is Cl or Br. 2 »" Compounds of the general formula I in which R is a straight chain or branched alkylx-.-.sb with 1 to 8 carbon atoms. ?. Process for the production of 2, ^: ;, p-'Trinet} i: / l- J .-- f.arba3 koxy-4- (β, β-dihalovinyl) -'- '·, 5-dihyc3Xii? Urane der allt .-. v ^r :: ole a formula 1
I, in which E is a straight chain branched alkyl radical 3.5t ; and X is Cl or Br, by thermal rearrangement of a • 2, ^/ ) -, 4-trimethyl-3-carbalko: cy-5- ( ^!; , ß ~ dihalogenvin.yi) - '+, ^ - dij hydro furans der general form ci II CO ₀ K 'CH-, \ / CH = CX, - i ^ ! in which R is a straight-chain or branched alkyl radical un; 1 X is Cl or 3r. YES. Method according to claim?, D ä du r chgeke η η ί draws that the thermal rearrangement in the gas; phase carried out v / ird. \ ^, Veriah.TH; j ": according to claim if odor · -, d. Adurchgeke η η j ζ eic Ii net that the animal ~ it-; che Uialap; eruag ii · a temperature range zv / icchen 200 b; ^ 3 5CO ⁰ C carried out v / ird. Ö09839 / 0454 ORiGHSJAL'- -z- Ve χ ¹ propelled s according to one of Annprüche 3 to 5i characterized in that the "hermisciie rearrangement in the presence of an inert Lösmigsiaittels which at the Un: - came pass into the gasforinigen state storage temperatures, performed v; ird. 909839/0454