DE2820410C2 - - Google Patents

Description

The invention relates to a process for the preparation of gem-dichloro- or gem-dibromocyclopropane derivatives that are suitable as Intermediates for the preparation of pesticidally active compounds.

A method of adding a dihalomethylene to a unsaturated compound to form a dihalocyclopropane derivative is described in GB-PS 9 83 203. Doing so an initially essentially water-free mixture of one Alkali hydroxide, a haloform containing at least one Chlorine or bromine atom, and an unsaturated compound applied. The reactants can be in equimolar amounts are available. However, it is generally convenient to have one Use excess unsaturated compound. A disadvantage this known method is that not enough Haloform for reaction with the unsaturated compound Available. The resulting cyclopropane derivatives are therefore obtained in a correspondingly low yield. Most the experiments described in the examples of this document were carried out at temperatures of at least 90 ° C. At such high temperatures go most of the in situ Dihalomethylene undesirable side reactions. This naturally leads to an insufficient use of the haloform.  

Attempts have now been made to make the known one mentioned above Process for the conversion of esters of 2-alkenoic acids to esters of 2,2-dihalocyclopropanecarboxylic acids to apply. However, it has been shown that this conversion not taking place.

In the aforementioned patent specification it is stated that the Use of an ether or a cycloparaffin sulfone as Solvent increases the yield of cyclopropane derivatives. However, it has now been shown that in the presence of such Solvent esters of 2-alkenoic acids only in very low Extent and after a longer reaction time to be converted.

According to GB-PS 14 32 540 are gem-dihalocyclopropane derivatives prepared by containing an aqueous phase containing an alkali hydroxide with an organic phase a haloform and an ethylenically unsaturated compound, in the presence of certain onium compounds as catalysts brings together. The reaction mixture obtained in this process contains a liquid organic phase, an aqueous one Phase and a solid inorganic phase. The dihalocyclopropane derivative can be isolated from this reaction mixture by water is added until the solid organic phase is dissolved and then the organic phase from the aqueous phase separated and the organic phase distilled. With this procedure however large amounts of water are required and consequently large vessels. In addition, emulsion problems can occur. Optionally, the solid inorganic phase is filtered off, the organic phase separated from the aqueous phase and distilled. This filtration is often quite difficult, as is that Separation of the organic from the aqueous phase. Besides, is often a relatively high molar ratio in these processes from alkali hydroxide to olefin, e.g. B. 4 to 10, required to increase the yield of dihalocyclopropane derivative.  

It has now surprisingly been found that it is possible to use gem-dichloro or gem-dibromocyclopropane derivatives in a much higher yield with relatively high speed in a reaction mixture from which they can be easily isolated.

The invention relates to the method specified in the main claim. A preferred way of working is in the subclaim specified.

The reaction mixture obtained in the process according to the invention comprises an organic phase containing the formed Dichloro or dibromocyclopropane derivative, a solid organic phase and the onium catalyst. By simply decanting the organic phase and distillation of this organic phase the dichloro- or dibromocyclopropane derivative is usually obtained in one very high yield. Obtained from this distillation Excess chloroform or bromoform can be used again.

As starting compounds serve ethylenically unsaturated compounds with up to 30 carbon atoms per molecule and 1 to 3 carbon-carbon double bonds, for. B. alkenes, cycloalkenes and cycloalkatrienes. The alkene can be linear or branched and have a terminal or middle double bond and have a cis or trans structure. Examples of suitable alkenes are ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 3-methyl-1-butene, 3-methyl-1-hexene , 1-decene, 2-pentene, 2-hexene, 3-heptene, 2-methyl-2-butene, 2-octene and 3-nonen. Examples of suitable cycloalkenes are Δ³ -carene, cycloheptene, cyclooctene, cyclonones, cyclodecene, cycloundecene, cyclotridecene, cyclotetradecene and the 1-methyl and 1-ethyl derivatives thereof. Examples of cycloalkatrienes are 1,3,5-cyclononatriene and 1,5,9-cyclododecatriene. The latter connection is particularly suitable. Other examples of ethylenically unsaturated compounds are butadiene, isoprene and 1,4-pentadiene.

There is a particular advantage of the method according to the invention in that it becomes possible to use esters of 2,2-dichloro- or 2,2-dibromocyclopropanecarboxylic acids obtainable in high yield from Esters of 2-alkenoic acids. These esters can be derived primary, secondary or tertiary alcohols. Esters of tertiary alcohols are very suitable. Examples of tertiary Alcohols are tert-butyl alcohol, 2-methyl-2-butanol and 3-methyl-3-pentanol. Very good results are achieved with tert-butyl-3-methyl-2-butenoate. It has been observed that by Addition of an ether or a cycloparaffin sulfone as a solvent the yield of 2,2-dichloro- or 2,2-dibromocyclopropane carboxylates  generally decreases. The method according to the invention can but also in the presence of aliphatic hydrocarbons, such as pentane, hexane or heptane as a solvent will.

The process according to the invention is essentially absent carried out an aqueous phase, a corresponding smaller reaction vessel can be used.

The formation of an aqueous phase in the reaction mixture will preferably by using a water-binding agent prevents e.g. B. by applying an excess of solid Alkali hydroxide. The molar ratio of alkali hydroxide to unsaturated Connection can be relatively low, preferably in the range of the stoichiometric amount up to 10 times the stoichiometric amount and preferably from 1.5  times up to 4 times the stoichiometric amount, the excess being chosen so that the formation of a aqueous phase is avoided. The stoichiometric ratio refers to the number of dichloro or dibromomethyl residues that be taken up by one mole of the unsaturated compound have to. For example, this stoichiometric ratio is 1, if alkenes are used and can be 3, when cycloalkatrienes are used as unsaturated compounds will.

Examples of other water-binding agents that are additional can be used are anhydrous sodium sulfate, anhydrous sodium carbonate, anhydrous potassium carbonate and Silica gel.

The use of an initially essentially anhydrous Mixture serves to form an aqueous phase to avoid and thereby the yield of dichloro or dibromocyclopropane derivative to increase. An essentially water-free one at first Mixture can be obtained by removing water, insofar as this is available, from the unsaturated compound, chloroform or bromoform and, if used, the solvent, e.g. B. by drying with anhydrous magnesium sulfate and by using a dry alkali hydroxide.

The molar ratio of chloro- or bromoform to unsaturated compound can preferably be greater than 1, due to the excess Chloro or bromoform is the yield of dichloro or dibromo cyclopropane derivative is increased and the chloroform or bromoform is used as a solvent. The process can be carried out at a temperature in the range of 0 to 100 ° C will, but will preferably be proportionate low temperatures, especially in the range of 15 to 45 ° C carried out. At these relatively low temperatures the inclination of the dichloromethylene or dibromomethylene generated in situ, To have side reactions, significantly reduced. The leads to an effective use of chloroform or bromoform. Room temperatures are generally favorable.  

Of the alkali hydroxides, i.e. H. Lithium, sodium, potassium, Rubidium and cesium hydroxide, sodium hydroxide is preferred, because it usually leads to the highest yield of dichloro or dibromo cyclopropane derivatives.

Examples of catalysts are methyl nitrile (1-methyl-heptyl) ammonium chloride, tetrabutylammonium chloride, ethyldi (1-methylundecyl) sulfonium ethyl sulfate, ethyl hexadecyl undecyl sulfonium ethyl sulfate, triethyl sulfonium iodide, methyldi (1-methylnonyl) sulfonium chloride, Hexadecyldimethylsulfonium methyl sulfate, ethyl 1-methylpenta decyl-1-methyl-undecylsulfonium-ethyl sulfate, dimethyl-1-methyl pentadecylsulfonium iodide, ethylmethyl-1-methylpentadecyl  sulfonium tosylate, dimethyl-1-methylpentadecyl sulfonium tosylate, trimethylsulfonium bromide and dibutylmethylsulfonium iodide.

The molar ratio of catalyst to chloroform or bromoform is not critical and can vary within wide limits. Usually the catalyst is present in such an amount indicated by the term "catalytic amount" can. The molar ratio of catalyst to chloroform or bromoform is preferably in the range of 0.1: 1 to 0.0001: 1. Excellent Results were obtained using a ratio from 0.01: 1 to 0.0005: 1.

The invention is illustrated by the following examples.

Each of the experiments described below was carried out in one Three-necked round bottom flask carried out in the water bath and with stirrer, thermometer, reflux condenser and calcium chloride tube was provided. In the comparison tests and in the examples 1, 2, 3, 7 and 8 became a magnetic stirrer and in the other examples used a paddle stirrer. The starting substances were put in the flask, it was stirring started and samples of the contents from the flask as in the Tables specified, taken. These samples were Liquid chromatography analyzed. A dash in the Tables means that no analysis has been carried out. The Experiments were carried out at a temperature between 20 and 25 ° C unless otherwise stated.  

Examples 1 to 3 and comparative experiments A and B Preparation of 13,13-dichlorobicyclo (10,1,0) tridecane

Table I shows the amount of starting substances, that was applied. The cyclododecene contained 7 mol% Cyclododecane. The starting substances were initially anhydrous.

Table I

Table II shows the results. The two comparison tests and obtained in the three examples Mixtures did not contain an aqueous phase.

Table II

A comparison of example 1 with comparative experiment A shows that methyltri (1-methylheptyl) ammonium chloride the Yield on the title compound increased significantly.

A comparison of example 1 with comparative experiment B shows that methyltri (1-methylheptyl) ammonium chloride the yield on title compound increased more than the bis (2-methoxyethyl) ether. After stirring for 45 h, the reaction mixture was after comparative experiment B became so thick that stirring was stopped had to become.

A comparison of Example 2 with Example 1 shows that the Presence of anhydrous sodium sulfate the yield somewhat increased in title connection.  

A comparison of example 3 with comparative experiment A. shows that tetrabutylammonium chloride the yield of the title compound also significantly increased.

A comparison of Example 3 with Example 2 shows that a Molar ratio of sodium hydroxide to cyclododecene of 2: 1 instead of 1: 1 to a higher yield of the title compound leads, assuming that the two are different quaternary ammonium chlorides have the same influence exercise.

Examples 4 to 6 and Comparative Experiment C Preparation of 13,13-dichlorobicyclo (10,1,0) tridecane

The amounts of starting substances are given in Table III, that were applied. The cyclododecene contained 7 mole% cyclododecane. The starting substances of the examples 5 and 6 were initially anhydrous.

Table III

Table IV shows the results.

The reaction mixtures obtained according to the three examples did not contain an aqueous phase.

Table IV

A comparison of example 4 with comparative experiment C shows that the yield of the title compound is increased significantly, if the amount of water is reduced so much that no water Phase is present.

A comparison of Example 5 with Example 4 shows that if initially no water is present, the yield of the title compound is further increased.

After stirring for 8 hours, the liquid phase in the reaction mixture of Example 6 decanted from the solid phase and evaporated at a pressure of 15.96 mbar, one Obtained residue consisting of the title compound and in which the yield was 99.0%.  

Examples 7 and 8 and comparative tests D and E Manufacture of tert. Butyl 2,2-dichloro-3,3-dimethylcyclopropane carboxylate

Table V shows the amounts of starting substances used specified.

Table V

The starting substances were initially anhydrous.

Table VI shows the results. The one after the two comparative tests mixtures obtained in both examples did not contain an aqueous phase.  

Table VI

A comparison of example 7 with comparative test D shows that the presence of ethyl di (1-methylundecyl) sulfonium ethyl sulfate to a substantial conversion of tert. Butyl-3-methyl-2-butenoate with a high selectivity towards of the title link.

A comparison of comparative experiment D with E shows that the Presence of bis (2-methoxyethyl) ether is only a minor Conversion of tert. Butyl-3-methyl-2-butenoate, the absence of anhydrous sodium sulfate in the comparative example E is neglected.

A comparison of Examples 7 and 8 shows that in the absence of bis (2-methoxyethyl) ether a high conversion of tert. Butyl 3-methyl-2-butenoate and a much higher selectivity compared to the title compound can be achieved.

Example 9 Preparation of 15,15-dichlorobicyclo (12,1,0) pentadecane

The starting substances were:

Cyclotetradecen 21.6 mmol powdered sodium hydroxide 54 mmol Chloroform 195 mmol Methyl tri (1-methylheptyl) ammonium chloride 0.16 mmol Pentane 40 ml

The starting substances were initially anhydrous. The temperature the contents of the flask were kept at 35 ° C.

After 4 hours of stirring, the cyclotetradecene was complete converted and the reaction mixture contained no aqueous Phase. The liquid phase in the reaction mixture was from decanted the solid phase and at a pressure of 15.96 mbar evaporated to leave a residue from the title compound existed and the yield was 97%.  

Example 10 Preparation of 9,9-dichloro-1-methylbicyclo (6,1,0) nonane

The starting substances were:

1-methylcyclooctene 15 mmol powdered sodium hydroxide 22.5 mmol Chloroform 60 mmol Methyltri (1-methylheptyl) ammonium chloride 0.05 mmol anhydrous sodium sulfate 10.5 mmol Pentane 20 ml

The starting substances were initially anhydrous. After 2.5 hours A quantitative yield was obtained on stirring The title compound and the reaction mixture contained none aqueous phase.

Example 11 Preparation of 5,5,10,10,15,15-Hexachlortetracyclo (12,1,0,0 ^4.6, 0 ^9.11) pentadecane

The starting substances were:

1,5,9-cyclododecatriene 255 mmol powdered sodium hydroxide535 mmol Chloroform 5000 mmol Methyltri (1-methylheptyl) ammonium chloride 2.55 mmol

The starting substances were initially anhydrous. The temperature the contents of the flask were kept at 40 ° C. Another powdery Sodium hydroxide and onium compound became the in the times indicated in Table VII and in the times indicated there Amounts added. Table VII also shows the results specified. The reaction mixture contained no aqueous phase.  

Table VII

Selectivity to a particular compound, expressed in% is defined as

where "a" is as defined above and "c" is the molar amount of dihalocarbene acceptor reacted.

The liquid phase contained in the reaction mixture was from decanted the solid phase and at a pressure of 15.96 mbar evaporated to give a residue containing the adducts III and II in yields of 93 and 6%, respectively.

Example 12 Preparation of 2,2-dichloro-3,3-dimethylcyclopropane

A suspension of 2.4 moles of sodium hydroxide and 1 mole of anhydrous Sodium sulfate in 1 liter of pentane was under atmospheric pressure saturated with isobutene. After adding 0.00135 mol of methyl tri (1-methylheptyl) ammonium chloride was 6 moles of chloroform added dropwise within 1.5 h. The reaction partners and that Pentane was initially anhydrous. After stirring for 2.5 hours again 0.00135 mol of methyl (1-methylheptyl) ammonium chloride added and at the same time the addition of isobutene ended. It was an additional 10 h after the isobutene addition was complete touched. The reaction mixture contained no aqueous phase. The liquid phase was decanted from the solid phase and evaporated, containing 0.35 mol of the title compound.

Example 13 Manufacture of tert. Butyl 2,2-dichloro-3,3-dimethylcyclopropane carboxylate

The starting substances were:

tert. Butyl 3-methyl-2-butenoate 12.8 mmol Powdered potassium hydroxide 60.7 mmol Chloroform 150 mmol Tetrabutylammonium chloride 0.25 mmol

The starting substances were initially anhydrous. The temperature the flask contents were kept at 45 ° C. The potassium hydroxide was added to the other substances within 1 h. At the At the end of this hour the conversion from tert. Butyl 3-methyl-2-butenoate 80% with a selectivity towards the title link of 31%. There was no aqueous phase.

Example 14 Manufacture of tert. Butyl 2,2-dichloro-3,3-dimethylcyclopropane carboxylate

The starting substances were:

tert. Butyl 3-methyl-2-butenoate 12.8 mmol Powdered potassium hydroxide 60.7 mmol Chloroform 150 mmol Ethylhexadecylundecylsulfoniumethylsulfat0.25 mmol

The starting substances were initially anhydrous. The potassium hydroxide became the other starting substances within 1 h added, keeping the temperature at 45 ° C has been. After this time, the yield of the title compound was 50%.

The mixture was then stirred at a temperature of 22 ° C. for a further 4 h. At the end of these 4 h, the conversion of tert. Butyl 3-methyl-2-butenoate 90% with a selectivity to that 100% title link. There was no aqueous phase.

A comparison with Example 13 shows that the sulfonium compound provides the title compound in a higher yield than the quaternary ammonium compound.  

Example 15 Preparation of 13,13-dibromobicyclo (10,1,0) tridecane

The starting substances were:

Cyclododecene 26 mmol powdered sodium hydroxide 62.4 mmol Bromoform 171 mmol Methyltri (1-methylheptyl) ammonium chloride 0.11 mmol Water 0.5 mmol

The reaction mixture contained no aqueous phase. After 2 hours Stirring was the yield of the title compound 66%. Then another 0.055 mmol of methyltri (1-methylheptyl) ammonium chloride admitted. After another 5 hours With stirring, the yield of the title compound was more than 95%.

Example 16 Preparation of 15,15-dibromobicyclo (12,1,0) pentadecane

The starting substances were:

Cyclotetradecene 5.2 mmol powdered sodium hydroxide 10.4 mmol Bromoform 114 mmol Methyltri (1-methylheptyl) ammonium chloride 0.054 mmol Water 0.1 mmol

The reaction mixture contained no aqueous phase.

The yield of the title compound was 50% after 1 h and after 73% stirring for 2.5 hours. After stirring for 3.5 h another 15.6 mmoles of powdered sodium hydroxide and 0.054 mmoles Methyltri (1-methylheptyl) ammonium chloride added. The yield of the title compound after a total time of 20 h was more than 95%.  

Example 17 Preparation of 3,8,8-trimethyl-4,4-dichlorotricyclo [5,1,0,0 ^3,5 ] octane

The starting substances were:

(+) - 3-carene 294 mmol Chloroform678 mmol Methyltri (1-methylheptyl) ammonium chloride 0.9 mmol

525 mmoles of powdered sodium hydroxide were removed within Added for 1 hour so that the temperature was kept at 40 ° C. As after stirring for a further 0.5 h, the temperature rose Fell 35 ° C, the cooling bath was removed. That led to one Temperature rose to 49 ° C within 30 min and then fell the temperature within 5 h to 20 ° C. Then 10 g anhydrous sodium sulfate was added and the solid was filtered off. The filtrate was washed with 50 ml dichloromethane and the solvent is evaporated off, giving 62.2 g of a Residue received, completely from the title compound duration. The yield was 97%.

Example 18 Preparation of 2,2-dichloro-1-phenylcyclopropane

The starting substances were:

Styrene 400 mmol powdered sodium hydroxide 680 mmol Chloroform 1200 mmol Methyl tri (1-methylheptyl) ammonium chloride 4 mmol Sodium sulfate 400 mmol

The yield of the title compound was 0.5 h Stir at 65 ° C 100%.

Claims (2)

1. A process for the preparation of gem-dichloro- or gem-dibromocyclopropane derivatives by reacting an ethylenically unsaturated compound with chloroform or bromoform in the presence of a solid alkali metal hydroxide and a catalytic amount of a tetraalkylammonium or a trialkylsulfonium compound, the alkyl groups each having 1 to 20 carbon atoms and the onium compound is in the form of a hydroxide, chloride, bromide, iodide, sulfate or alkyl sulfate, characterized in that the ethylenically unsaturated compound used is one having 1 to 3 carbon-carbon double bonds and up to 30 carbon atoms in the molecule and the reaction is carried out under essentially performs anhydrous conditions. 2. The method according to claim 1, characterized, that the reaction in the presence of a water-binding agent carries out.