HU193487B - Process for production of 1-substituated-2,2-dichloreaevinile compound with reductive elimination - Google Patents

Abstract

Process for the preparation of compounds I <IMAGE> (wherein R' stands for a straight or branched chain alkyl or alkenyl group containing 1 to 4 carbon and 0 to 2 halogen atoms) by reductive elimination of a compound of the formula II <IMAGE> (wherein R stands for hydrogen or an aliphatic or aromatic acyl or sulphonyl group containing 1 to 8 carbon atoms, and R' is as defined above which comprises treating the compound (II) in solution with zinc, iron or aluminium in the presence of a metal or metal ion promoter which is less metallic in character than the metal used for reduction but has an oxidation-reduction potential of +0.4 V metal/metal ion as a maximum. 1,1-dichloro-4-methyl-pentadiene-1,3 (or 1,4) may be prepared. <IMAGE>

Description

The present invention relates to a process for the preparation of 2-substituted 1,1-dichloroethylene derivatives of formula (I) wherein R 'is a linear or branched alkenyl group having 3 to 4 carbon atoms. by the reductive elimination of 2-substituted 1,1,1-trichloroethyl alcohols or esters of the formula wherein R is hydrogen, C 1-7 alkanoyl, benzoyl, or p-toluenesulfonyl.

Known representatives of the 2-substituted -, 1-chloro-ethylene compounds of formula (I) are 1,1dichloro-4-methylpentadienes (1,3 and 1,4 isomers), which are important intermediates in the synthesis of photostable pyrethroids. Several methods have been developed for their preparation (e.g., Arit D., Jantelat M. and Lantzsch R., Angewandte Cheime 93,719 (1981)).

One of the simple and low-cost variants of these syntheses is the so-called. Wolf method (Farkas., Kourim P., Sorm F., Coll.Czech.Chem. Commun 24, 2230 (1959); Ger Of fen 2,616,681) which is obtained by the Prins reaction of isobutylene and chloral, isomerization, acylation and reductive elimination. to the desired product.

The final step in the synthesis, the conversion of 1,1,1-trichloro-2-acetoxy-4-methyl-3-pentene to 1,1-dichloro-4-methyl-1,3-pentadiene, is carried out with 1-4 molar equivalents of zinc powder in the presence of acetic acid. .

There is also a reference to the use of higher zinc 3-15 molar equivalents (e.g. Chemické Listy, 52,688 (1958)). No. 181,795. Hungarian Patent No. 6,198,123, relates to the reduction of compounds of the type corresponding to the 2-substituted 1,1,1-trichloro ester of formula II wherein R 'is 2-chloro-2-methylpropyl,

The reduction is carried out in a protic organic solvent with 0.5-1.5 molar equivalents of zinc or aluminum powder, if necessary in the presence of an ammonium chloride or mercury (II) chloride activator.

No. 183,503. According to a Hungarian patent, in the presence of one equivalent of a strong inorganic acid, the reaction is easier to control and 1 to 2 equivalents of zinc powder are sufficient. The described zinc or. A common disadvantage of aluminum reductions is that production varies greatly by 20-30% depending on the origin, morphology and impurities of the reducing metal. Such a high degree of reproducibility hampers plant implementation

The present invention is based on the discovery that if The reductive elimination of a compound of the general formula (1) not with pure zinc or aluminum, but in the presence of a metal or metal ion promoter with a metal / metal ion redox potential of less than metal used for the reduction but not more than +0.4 V, significantly increases zinc or aluminum. selectivity and near quantitative yield of the compound of formula I can be obtained. Moreover, under these conditions, iron production, which is otherwise very low in activity, can produce excellent production.

The effect of the process according to the invention can be explained by the fact that in the presence of the reducing metal (zinc, iron or aluminum), the metallic promoter metal, which is less positive than the reducing metal, is deposited rapidly on the surface of the reducing metal. amount is ionized. Further chemical reductions involve the already formed alloy and not the pure zinc, iron or iron. aluminum.

Alloy formation may result in changes in zinc / zinc (II) ion, iron / iron (II) ion, or aluminum / aluminum (III) ion redox potential and this is probably due to the increase in production and selectivity in the reductive elimination reaction.

The process of the present invention comprises reacting the compound of formula (II) in water or in a water miscible solvent (e.g., methanol, ethanol, i-propanol, acetone, dimethylformamide, tetrahydrofuran, acetic acid) or a mixture of 1 to 3 molar equivalents of zinc, iron or aluminum powder or filament, metal with a redox potential more positive than the reducing metal, but not more than &gt; 0.4 metal / metal ion. in the presence of a metal ion promoter and an acid. The promoter metal is present in an amount of 0.1-5 mol% based on the reducing metal.

The reaction is a fast, exothermic process under atmospheric conditions which may be conveniently controlled by adding the compound of formula (II) or the solvent or the reducing metal (or the promoted reducing metal) to the other two mixtures. The reaction may be carried out at a temperature in the range of from 20 ° C to the boiling point of the solvent mixture, preferably from 40 to 90 ° C.

The acid used is inorganic acids, preferably hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, sodium or potassium hydrogen sulfonate, or organic acids, preferably formic acid, acetic acid or propionic acid.

It has been found that the same good results are obtained either by adding the promoter metal salt directly to the reaction mixture or by pre-cementing the promoter metal onto the reducing metal.

Metal ions which may be used in the promoter can be: galI (II) -, gallium (II) -, iron (II) -, iron (II) cadmium (II) -, thallium (II) -, indium (II) -, cobalt (II) ), nickel (II), molybdenum (II), tin (II), lead (II), bismuth (II), azene (II) antimony (II) and rose (II) ions. Zinc (II) (on aluminum, aluminum) and zinc formed during cementation. iron (II) or iron (III) ions do not interfere with the chemical reaction and do not need to be removed.

For best results, use the following metal pairs:

zinc-cadmium, zinc-copper, zinc-iron, zinc-lead, aluminum-cadmium, aluminum-lead, aluminum-tin, iron-lead, iron-tin.

The promoter metal is an optional inorganic or organic acid salt of the metal (e.g.

-2193487 nitrate, sulfate, chloride, acetate, perchlorate), provided that the salt is at least partially soluble under the conditions of cementation. The appropriate metal oxide or metal hydroxide may also be used, but it must be ensured that at least an equivalent amount of acid is present during the cementation.

During pre-cementation, the reducing metal and the promoter metal compound (e.g., lead acetate, ferric chloride, tin chloride, copper sulfate, cadmium acetate) in a polar solvent (e.g., water, methanol, ethanol, acetic acid, 2- propanol) (e.g. stirring, shaking), and after the appropriate promoter metal has precipitated on the surface of the reducing metal, the latter is filtered off and used as described in Scheme II. for the reductive elimination of the compound. Cementation temperatures, as with reductive elimination, may be between 20 ° C and the boiling point of the solvent mixture.

The reducing metal can also be powder, chips, chips, wire, foil, granules, granules or filings.

The main advantages of the process according to the invention are:

- the use of a promoted reducing metal produces an equally good production regardless of the quality of the metal;

- promoted aluminum, iron or steel. Zinc produces higher production and without selectivity, as in the case of promotion, the environmental impact of technology is also reduced;

- Promoted aluminum, iron or steel. zinc can be formed very easily in the reaction mixture itself, without the need for a separate operation, - the reaction can be carried out at atmospheric pressure in a standard apparatus;

The product is obtained by fractional distillation at a purity of at least 99%.

The following examples illustrate the process of the invention without limiting it.

Example 1

Weigh 36.8 g of 0.15 mol into a 250 cm flask. 1,1,1-trichloro-2-acetoxy-4-methyl-3-pentene (hereinafter TMPAC-3), 10 cm acetic acid, 27 cm ³ methanol, 0.8 cm ³ 5% sulfuric acid and 40-45 At C, 12.5 g of 0.19 mol of zinc powder was added over 45 minutes with stirring and cooling. After stirring for an additional 45 minutes, the mixture was cooled to 20 ° C, filtered, extracted with water (60 cm ³ ) and analyzed by gas chromatography after drying the organic phase over sodium sulfate. The yield of 1,1-dichloro-4-methyl-1,3-pentadiene (hereinafter DCD-1,3) was 79.5%.

Gas chromatographic analysis: Chrom-III. Chromatograph, 2.4mx6mm column, 9% Arzone L + 1% PEG 20M / 80-100 mesh Chromosorb W Charger, 240 "C evaporator and 110" C column temperature, argon carrier gas, ionisation detector, 0 , 3 ul sample.

Calibration was performed on pure substances for quantification.

Example 2

Example 1, except that the reduction is carried out using not lead zinc powder but lead-promoted zinc powder 12.5 g 0.19 mol of zinc powder are used to prepare the promoted zinc powder were mixed with 0.95 g of 2.5 mmol of lead acetate trihydrate in 10 cm ³ of methanol .oldatával and the alloy was filtered. The yield of DCD-1.3 was 93.1%.

Example 3

Into a 250 cm flask was added 40.7 g of 0.20 mole of 1,1,1-trichloro-2-hydroxy-4-methyl-3-pentene (hereinafter TMP-3), 21 cm ^{3 of} acetic anhydride and 2 drops. sulfuric acid. After 10 minutes at 90 "Cos, the mixture was cooled to 15-20" C, 0.5 cm ^{3 of} water, 30 cm ^{3 of} methanol, 0.6 g of 2.2 mmol of ferric sulfate heptahydrate and At -46 ° C, 16.3 g of 0.25 mol of zinc powder was added over 45 minutes. After stirring for a further 45 minutes, the mixture was cooled to 20 ° C, filtered, extracted, with 100 cm ^{3 of} water and the organic phase dried over sodium sulfate. GC analysis showed 3% ΤΜΡ-3 and 86% DCD-1,3.

Example 4

The experiment was carried out as in Example 3, but instead of ferric (II) sulfate heptahydrate, 0.12 g (0.7 mmol) of copper (II) chloride dihydrate was added. The product mixture contains 1% TMP-3, 2% TMPAc-3 and 85% DCD-1,3.

example

The experiment was carried out as in Example 1 by adding 1.35 g of the reaction mixture

4.7 mmol cadmium acetate trihydrate and pure zinc were also used for the reduction. The DCD -1.3 yield was 87.9%.

example

The experiment was carried out as in Example 1, except that the 1,1,1-trichloro-2-hydroxy-4-methyl-4-pentene (hereinafter TMP 4) isomer was not TMP-3 and the reduction was 14.1 g. 22 moles of zinc powder, previously promoted with a mixture of 1.4 g of 3.7 mmol of lead acetate trihydrate and 10 cm @ 3 of water. The product: 1,1-dichloro-4-methyl-1,4-pentadiene (hereinafter DCD-1,4), yield 92.2%.

Example 7

Into a 250 cm flask was placed 1.15 g of 3.0 mmcl of lead (II) acetate trihydrate in 12.5 g of 0.19 moles of zinc powder and 30 cm ^{3 of} water. While stirring, it is heated to 5055 ° C and added dropwise over a period of 40 minutes to produce the following acylation reaction:

Into a 100 cm flask was added 30.5 g of 0.15 moles of ΤΜΡ-4, 16.3 cm ^{3 of} acetic anhydride and 2 drops of conic acid. After 10 minutes at 90 ° C, the mixture was cooled to room temperature.

followed by filtration, 2x100 cm aqueous extraction and drying with sodium sulfate. Gas chromatography analysis showed DCD-1.4 yield 89.7%, m.p.

-3193487 lectivity (based on TMP 4 reacted) 93.2%.

Example 8

Into a 250 cm ³ flask was added 36.8 g 0.15 mole of 1.1.1 trichloro-2-acetoxy-4-methyl 4-pentene (hereinafter TMPAc ~ 4), 0.3 cm ³ concentrated hydrochloric acid 60 cm ³ 90% ethanol and 12 cm @ ^{3 of} 95% acetic acid. 6.2 g (0.23 mol) of aluminum shavings were added at 75-80 ° C with stirring over 90 minutes, and the mixture was cooled to room temperature after 30 minutes. filtered, extracted with water (2x150 cm ³ ) and the organic phase dried over sodium sulfate. Gas chromatography analysis showed 28.2% yield of DCD-1.4 and 86.5% selectivity (based on TMPAc 4 reacted).

By repeating the reaction by adding 5 mmol of a metal promoter salt to the reaction mixture prior to the addition of aluminum, the yield changes as follows.

salt DCD-1.4 Production% DCD-1.4 selectivity% cadmium (II) acetate trihydrate 28.2 91.0 86.5 92.2 cobalt (II) acetate tetrahydrate 26.9 81.7 cobalt (II) chloride hexahydrate 32.1 85.2 nickel (II) nitrate hexahydrate 20.9 81.1 iron (II) nitrate non-hydrate 32.1 86.9 iron (III) chloride hexahydrate 33.6 84.5 copper (II) chloride dihydrate 29.6 85.8 lead (II) acetate trihydrate 94.2 97.5 lead (II) - nitrate 95.0 97.1 tin (II) chloride dihydrate 41.6 92.6

Example 9

A 250 cm ³ flask was charged with 36 g of 0.15 moles of TMP Ac-3, 15 cm ^{3 of} water, 60 cm ^{3 of} ethanol, 1.05 g of 3.2 mmol. lead (II) nitrate and 0.3 cm ³ concentrated hydrochloric acid. The mixture was heated to 80-85 ° C and 5.2 g of 0.19 mol aluminum filings were added with stirring over 60 minutes. After stirring for 30 minutes, the mixture was cooled to room temperature, filtered, shaken with 150 cm ^{3 of} water and the organic phase washed with 2 x 100 cm ^{3 of} water.

Gas chromatography analysis showed 100% conversion and 96.2% DCD-1.3 yield.

Example 10

Into a 250 cm flask was added 36.8 g of 0.15 moles of TMP Ac-4, 11 cm ^{3 of} acetic acid, 1.1 g of 2.9 mmol of lead (II) acetate trihydrate, 60 cm ^{3 of} ethanol 4 and 5. , 2 g of 0.19 mol aluminum filings. The mixture is heated to 50 ° C and after the reaction has commenced, the temperature is maintained at 55-60 ° C until the exothermic reaction is largely complete (about 30 minutes). After stirring for a further 90 minutes, the mixture is cooled to 15-20 [deg.] C., filtered, extracted with 1 cm <^{3> of} water, the organic phase is washed with 2x80 cm <^{3> of} water and dried over sodium sulfate. The yield of DCD-1.4 is 94.5% and the selectivity (based on the material reacted) is 97.2%.

Example 11

TMP-4 (30.5 g), acetic anhydride (163 cm ³⁾ and pyridine (40 cm ³ ) were stirred at 60 ° C for 3 hours and then poured into aqueous hydrochloric acid under ice-cooling.

After extraction with benzene, the benzene phase is washed to neutral, the benzene is evaporated and 10 cm ^{3 of} water, 0.6 g of 1.6 mmol of lead (II) acetate trihydrate and 5.2 g of 0.19 mol of aluminum chips are added. The mixture was heated to JO-75 C and 60 cm ^{3 of} ethanol was added dropwise over 60 minutes. After stirring for an additional 1 hour, the mixture was cooled, filtered, extracted with 2x120 cm ^{3 of} water, the organic phase dried over sodium sulfate and analyzed by gas chromatography. The yield of DCD-1.4 was 96.5%.

Example 12

The experiment was carried out as in Example 11, but the total reaction time of the acylating agent benzoyl chloride and the reduction was 80 minutes. The DCD is 1.4 production

95.7%.

Example 13

The experiment was carried out as in Example 11, but the acylating agent was p-toluenesulfonic acid chloride. The DCD-1.4 yield was 96.9%.

Example 14

The experiment was carried out as in Example 11, but the starting material was a 5: 1 mixture of TMP-4 and TMP-3.

DCD -1.4 and DCD-1.3 production combined

95.8%.

Example 15

,5-3 (30.5 g), acetic anhydride (16.3 cm ³⁾ and sulfuric acid (2 drops) were stirred at 90 ° C for 10 minutes and then cooled to 20 ° C. After addition of 60 cm ³ of water, 0.76 2.0 mmol of lead (II) acetate trihydrate and 60 to 65 "C was added 5.2 g of 0.19 mol aluminum powder is cooled to 120 ° C elegyet20 minutes after 30 minutes utókeverós , filter, shake with 150 cm ^{3 of} water and dry the organic layer over sodium sulfate. The DCD -1.3 yield was 97.6%.

Example 16

The experiment was carried out as in Example 15, but using 1.13 g of 5.4 mmol cadmium (II) sulfate instead of lead (II) acetate trihydrate and 60 cm ^{3 of} 90% ethanol instead of water. The yield of DCD-1.3 was 89.2% and the selectivity was 92.0%.

-4193487

Example 17

The experiment was performed as in Example 15, 2.6 g, 9.1 mmol cadmium (II) instead of the reduction of lead (II) acetate trihydrate - acetate trihydrate, using 60 cm ^J ethanol instead of water. The DCD 1.3 yield was 91.2%.

Example 18 fi. The experiment was carried out as in Example 15 but the reduction was carried out at 90-95 ° C instead of 60-65'C. The DCD-1.3 yield was 93.2 ° / o.

Example 19

Into a 250 cm ³ flask was added 36.8 g of 0.15 moles of TMP-Ac-3 *, 0.3 cm ^{3 of} concentrated hydrochloric acid and 10 cm ^{3 of} 15% 5.2 mmol cadmium (II) acetate / acetic acid. . Heat to 76-80 ° C and add 6.8 g of 0.25 mol of aluminum filament and 100 cm ^{3 of} water: acetic acid - 2:10 over 60 minutes with stirring.

After stirring for 1.5 hours, the mixture was cooled to 10-15 ° C, adjusted to pH 3 with 1: 1 HCl and filtered.

The filtrate is shaken with 100 cm @ ^{3 of a} watermark and the organic phase is washed with 2x60 cm @ 3 water and dried over sodium sulfate. DCD-1.3 production is 90.8%,

Example 20

250crn a flask 30,5g0,15 mole of TMP-4, 16.3 cm ³ of acetic anhydride and 0.05 cm ³ of sulfuric acid. After 10 minutes at 90 ° C, the mixture is cooled to 0 ° C, 30 cm ^{3 of} ethanol, 22.3 g of 0.4 mol of iron shavings are added and the mixture is refluxed for 4 hours. After sleeve ₃ heating and filtration the filtrate was extracted with 15 <J cm ³ of water, the organic layer was washed with 2x50 cm ³ of water and dried over sodium sulfate. DCD-1.4 production is only 6.1%.

Repeating the reaction by adding 5 mmol of cadmium (II) acetate trihydrate or lead (II) acetate trihydrate prior to the addition of iron, the yield was 69.1%, respectively.

74.5%.

Example 21

The reaction was carried out as in Example 20, but using 30 cm ^{3 of} water instead of ethanol as the promoter, 5 mmol of lead (II) acetate trihydrate. The DCD -1.4 yield was 87.2%, and the selectivity for the reacted TMP-4 was 95.0%.

Example 22 ^ a

Weigh into a 250 cm ³ flask 30.5 g of 0.15 moles of ΤΜΡ-4, 75 cm ^{3 of} water, 7.5 cm ^{3 of} acetic acid, 3 cm ^{3 of} concentrated hydrochloric acid and 1.4 g of 3.7 mmol of lead (II). Acetate trihydrate, 5.26 g of 0.2 mol of aluminum powder are added over 1 hour and the product is refluxed for 4 hours. After cooling, it is filtered, and after separation, the organic phase is washed twice with 100 cm <^{3> of} water and dried over calcium chloride. The DCD 1.4 yield was 89.5%.

Example 23

Into a 250 cm ³ flask was added 40.7 g of 2 molar ΤΜΡ-4, 28.9 g of propionic anhydride and a drop of conic acid, after which the mixture was cooled to below 30 ° C for 15 minutes, was added 2 ^cm3 of water, 355 cm ³ of acetone, 1.1 g of 3.4 mmol of lead (II) acetate and 30 to 40 ~ C on bead golu 16.7 g, 0.26 mol of zinc powder 50-55 minutes . Additional 60 minutes stirring; After cooling to 20 DEG C., filter, shake with 80 cm @ ^{3 of} water and dry the organic layer over sodium sulfate. Gas chromatography analysis shows 1.5% TMP-4 and 96.2% DCD-1.4. .

Example 24 Experiment fi was conducted as in Example 23, but 1.0 g of 4.2 mmol of nickel (II) chloride hexahydrate was added to the reaction mixture instead of lead acetate. After a total reaction time of 2.5 hours, the yield of DCD-1.4 was 94.7%.

Example 25

The experiment was carried out as in Example 23, but 30 cm ^{3 of} dimethylformamide was added to the reaction mixture instead of acetone. DCD-1.4 production

93.9%.

Example 26

The experiment was performed as in Example 23, but 1.4 g, 5.9 mmol of cobalt (II) in 35 cm ³ of tetrahydrofuran and lead acetate in place of acetone - chloride hexahydrate were charged. After a total reaction time of 160 minutes, the processed product contained 95.6% DCD-1.4.

Example 27

The experiment was carried out as in Example 23, but using 10.1 g 98% formic acid instead of propionic anhydride and 22.4 g acetic anhydride as water scavenger. Gas chromatography analysis indicated that the reaction mixture contained 0.5% TMP-4 and 98.7% DCD-1.4.

Example 28

The experiment was carried out as in Example 3, but using 37.9 g of 0.2 mol of 1.1.1 trichloro-2-hydroxy-4-pentene instead of TMP-3. Gas chromatography analysis showed 2.0% starting material, 6.4% acylate derivative and 80.3% 1,1-dichloro-pentadiene 1.3.

EXAMPLE 1b Experimental Example 28 was carried out as in Example 28, but using 0.8 g of 2.1 mmol Ohl (II) acetate as the activator, yield 81.9%, 1,1-dichloropentadiene 1.3.

examples

Four-necked flask and 250 cc of input Runkel 0.2 mole (40.7 g) TMP-4 dispenser, 0.38g, 1 mmol of lead (II) - acetate in 30 cm ³ of methanol. To the mixture was added 7.5 g of 0.28 µmol aluminum powder and 27 cm @ 3 of 26% hydrochloric acid under vigorous stirring and cooling at 50 ° C over a period of 120 minutes. After stirring for an additional 30 minutes, water (30 cm ³ ) was added, cooled to 20 ° C, filtered. After separation, the organic phase is washed with 5C cm ^{3 of} 1% aqueous hydrochloric acid. Gas chromatographic analysis of the product

-5193487

Contains 0.5% starting material and 94.2% DCD 1.4.

Example 31

The experiment was carried out as in Example 30, but 38 cm ^{3 of} 30% formic acid was added to the reaction mixture, not hydrochloric acid. Yield: DCD-1.4 by gas chromatography

93.6%.

Claims (1)

1. / Process 1,1-dichloroethylene derivatives of formula (I) - where R 'is a linear or branched alkenyl group having from 3 to 4 carbon atoms - from compounds of formula II - where R is hydrogen, C 1 -C 7 alkanoyl, benzoyl, or p-toluenesulfonyl R 'has the above reductive elimination, characterized in that the compound of formula II is intensively contacted with 1 to 3 molar equivalents of zinc, aluminum or iron in water or in a water-miscible organic solvent or in a mixture thereof, but is less metallic than the reducing metal. up to +0.4 V phosphorus / metal ion in the presence of 0.1-5 mol% metal or metal ion promoter and acid at 20 ° C and 5 in the temperature range determined by the boiling point of the solvent mixture. The process of claim 1, wherein the promoter metal salt is added directly to the reaction mixture, or the promoter metal is deposited on the surface of the reducing metal by ¹⁰ m cementation. Method according 37 claim 1, wherein the water-miscible organic solvent is an alcohol - preferably methanol, ¹⁵ ethanol, i - propanolt- ethers - preferably tetrahydrofuran; carbonyl compounds - preferably acetone, methyl ethyl ketont-, acids - preferably ecetsavat- or amides preferably, dimethylformamide ₀ - is used. The process according to claim 1, wherein the acid is inorganic acids, preferably hydrochloric acid, sulfuric acid, or organic acids, preferably formic acid, acetic acid or Propionic acid was used. The process of claim 1, wherein the reaction is preferably carried out at a temperature in the range of 40 to 90 ° C.