JPS5912093B2 - Process for producing cyclobutanone or cyclobutenone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (1) or () [wherein Hal is F, . Represents Cl or Br, R1
, R2, R3 and R4 may each be the same or different and represent a hydrogen atom or an alkyl or alkenyl group optionally substituted by an alkoxy, penzyloxy or alkoxycarbonyl group, or alkoxycarbonyl or R1 and R3 together or R2 and R4 together form an alkylidene group, or one of R1 and R3 and one of R2 and R4 represent the two groups to which they are attached. cyclobutanone or cyclobutenone which forms a carbocyclic ring together with the carbon atoms of

The alpha-halocyclobutanone described in British Patent No. 1,194,604 is a (2+2) cycloaddition of a haloketene to an olefin (CyclOadditiOn).
) is obtained by

The cycloaddition is described in J. A. C. S Volume 87 (1965)
5257-9 and Tetrahedron Letters S)
,1,PP. 135-9 (1966), by dehydrochlorination of dichloroacetyl chloride with triethylamine. The dichloroketene formed in situ reacts with olefin to yield alpha-archlorocyclobutanone, but alpha-archlorocycloptanone reacts with triethylamine to form quaternary ammonium chloride, resulting in a low yield. can get. Cycloaddition is also described in J. Org. Ch
em.

31 (1966), pages 626-8, dehalogenation of alpha haloacetyl bromide using zinc powder in an inert solvent can also be achieved. The latter document describes a dichloroketene-only preparation starting from trichloroacetyl bromide and zinc. The dichloroketene is isolated in a hydrocarbon solvent such as hexane or octane, and the solution thus obtained is used as a source of dichloroketene (see GB Pat. It is stated that after the organisms have been removed, the haloketenes are reacted with olefins). The literature does not mention anything about the isolation of monohaloketenes obtained from dihaloacetyl halides and zinc, since this is not possible and monohaloketenes are unstable compounds and must be prepared at very low temperatures. It shows that even the polymers can be easily polymerized. This is Synthesisll August 97l, PP4l
5-22, which document states that when monochloroketene is prepared by dehydrohalogenation of monochloroacetyl chloride with triethylamine in the presence of chloral, cis- and trans-4-
Trichloromethyl-2-oxetanone (Oxetan0
It has been described that a mixture of nes) is formed, whereas when monochloroketene is prepared by dehalogenation of dichloroacetyl chloride with zinc in the presence of chloral, only alpha, beta dichlorovinyl dichloroacetate is formed. ing. Therefore, dehydrohalogenation and dehalogenation methods are not equivalent. In fact, the applicant has found that isolation of monochloroketene is not possible.

It is because dichloroacetyl chloride and zinc in diethyl ether form a reaction mixture that does not contain any monochloroketene and after removal of the zinc does not produce any cyclobutanone by the addition of 2,3-dimethyl-2-butene. It is. Surprisingly, it was found that the monochloroketene formed in situ by dehalogenation is capable of engaging in (2+2) cycloaddition. The present invention is based on the general formula (1) or () [wherein HaI is F. Represents Cl or Br, R1,
Each of R2, R3 and R4 may be the same or different and represents a hydrogen atom, an alkyl or alkenyl group optionally substituted by an alkoxy, benzyloxy or alkoxycarbonyl group, or an alkoxy represents a carbonyl group, or R1 and R3 together or R2 and R4 together form an alkylidene group, or one of R1 and R3 and one of R2 and R4 represent the 2 to which they are attached. cyclobutanone or cyclobutenone with the formula () [where each Hal is F, . 2,2-dihaloacetyl halide of the formula () or () representing Cl or Br] in a dialkyl ether or ketone as a solvent.
[Here, R1, R2, R3 and R4 have the above meanings] Defined as the above production method characterized by contacting the unsaturated compound of [herein, R1, R2, R3 and R4] in the presence of zinc and/or tin at a temperature higher than 5 ° C. can be done.

The process according to the invention and the 2,21-dihaloacetyl halides of general formula () are hereinafter referred to as the new process and acetyl halides, respectively.

Cyclobutanone of general formula (1) and cyclobutenone of general formula () are both referred to as cyclic compounds. Ethylenically unsaturated compounds of general formula () and algines of general formula (V) are both referred to hereinafter as unsaturated compounds. The ketene formed in situ is represented by the general formula: where Hal has the meaning given above.

The new process is preferably carried out using zinc, since this metal usually gives cyclic compounds in higher yields than tin.

The symbol Hal in the general formula () represents a fluorine, chlorine or bromine atom in any combination.

Examples of compounds of general formula () are dichloroacetyl chloride and acetyl halides obtained by replacing one or more chlorine atoms in this compound by bromine atoms. Very good results are obtained with dichloroacetyl chloride. Depending on the site specificity of the cycloaddition involved, an ethylenically unsaturated compound asymmetric with respect to the double bond may form two different cyclobutanones, and an arginine asymmetric with respect to the triple bond may form two different cyclobutanones. Different cyclobutenones may be formed.

For an explanation of the concept of site specificity, see “MethOden
derOrganischenChemie] (HO
uben-Weyl), 4th edition (1971), vol. 14, p. 143. Unsaturated compounds are for example isopropyl 3-methyl-2-butenyl ether, benzyl 3-methyl 2-butenyl ether and ethyl 2-butenyl ether.
an alkoxy group, a benzyloxy group, as in 3,5-trimethyl-2,4-hexadienoate,
It may have non-hydrocarbyl substituents such as ethoxycarbonyl groups or it may be hydrocarbon.

However, substituted unsaturated compounds usually yield cyclic compounds in relatively low yields, for example less than 20% based on acetyl halide. Unsubstituted unsaturated compounds usually give higher yields of cyclic compounds and are therefore preferred. Alkenes are particularly preferred and usually give cyclobutanone in yields of 50-75%. Alkenes may have straight or branched chains and may have a cis or trans configuration. Examples of alkenes include ethene, propene, 1-butene, cis-2-butene, trans-2-butene, isobutene, 2-benzene, 2-hexene, 3-hexene,
-heptene, 3-heptene, 2-methyl-2-butene,
3-methyl-2-benzene, 3-methyl-3-hexene, 2,4-dimethyl-3-hexene, 2,3,4-trimethyl-2-benzene, 1-octene, 2-octene,
3-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-eicosene, 1-docosene, methylenecyclobutane, methylenecyclopentane, methylenecyclohexane and the corresponding isopropylidene There are cycloalkanes. Very good results are obtained with 2,3-dimethyl-2-butene and 2-methyl-2-benzene.
2,5-dimethyl-2,4-hexadiene reacts stereospecifically with monochloroketene to form trans-
2-chloro-4,4-dimethyl-3-(2-methyl-1
-propenyl)cyclobutanone and trans-2-chloro-3,3-dimethyl-4-(2-methyl-1-propenyl)cyclobutanone.

For an explanation of the concept of stereospecificity, see “MethOde
"Organischen Chemie" (HO
uben-Weyl). 4th Edition (1971), Volume 14, Page 143. The importance of such stereospecificity is further explained below. Unsaturated compounds with an allenic structure yield alkylidenecyclobutanones. Examples of aret-unsaturated compounds are:
Allen, 1,2-butadiene, 2,3-pentadiene,
2,4-dimethyl-2,3-pentadiene, 3,5-dinityl-3,4-heptadiene, 5-methyl-1,2
-hexadiene, 2,8-dimethyl-4,5-nonadiene, 3-nonyl-1,2-dodecadiene and 1,2-
There is pentadecadiene.

When the ethylenically unsaturated compound is a cyclic compound, a bicyclic compound having a cyclobutanone ring is formed.

The starting cyclic compound may be, for example, 5, 6, 7 or 8 membered and may be substituted or unsubstituted and may have a second carbon-carbon double bond. Examples of substituents include halogen atoms that are not bonded to double bonded carbon atoms in molecules that have only one carbon-carbon double bond, and alkyl groups. Examples of cyclic unsaturated compounds are cyclohexene, cycloheptene, cyclooctene, 1,2-dimethylcyclobenzene, 2-methylcyclohexene and 3-methylcyclohexene. Examples of algines include propyne, 1-butyne, 2-butyne, 1-pentyl, 2-pentyl, 1-hexyl, 1-pentyl,
These include heptine, 1-dodecine and 2-methyl-1-pentyl.

Double-bonded and triple-bonded carbon atoms in ethylenically unsaturated compounds and algines, each having only one double or triple bond, carry inert substituents such as halogen atoms, carboxyl groups or esterified carboxyl groups. The reason is that such substituted unsaturated compounds rarely form cyclic compounds.

It has been found that in order to prevent or reduce the occurrence of side reactions as much as possible, the reaction must be carried out in an inert approach polar solvent.

Dialkyl ethers and ketones have been found to be very suitable solvents, especially ketones in which no more than one of the carbon atoms attached to the carbonyl group is a quaternary carbon atom. It is also possible to carry out the reaction according to the invention in a mixture of inert approach polar solvents, such as a mixture of diethyl ether and methyl-tert-butyl ketone.

Small amounts of inert solvents such as toluene or xylene may also be tolerated. Examples of dialkyl ethers are diethyl ether, di-n-propyl ether, n-propyl i-propyl ether, diisopropyl ether and di-n-butyl ether.

Among the ethers, diethyl ether is preferred, since in this solvent the cyclic compound is usually obtained in the highest yield. The acetyl halide can be applied at any concentration in the dialkyl ether, and is preferably applied at a concentration lower than 1 mol/dialkyl ether 1e, as at higher concentrations the yield of the cyclic compound decreases with increasing concentration. do.

The concentration preferably ranges from 0.1 to 0.6 mol/e. The unsaturated compound and acetyl halide may be dissolved in any molar ratio in the dialkyl ether.

Cyclic compounds are obtained with increased yields at increased molar ratios of unsaturated compounds to acetyl halide, for example at molar ratios of 4 the yields are higher than 90%. From this, the molar ratio is preferably in the range from 2 to 20 and in particular from 2 to 10. Ketones, especially alkanones, are the most attractive solvents found to date, in which 1 mol/f
! Cyclic compounds can be obtained in high yields at increasingly higher concentrations of acetyl halide.

This applies in particular to alkanones which have at least two branches in the carbon skeleton of the molecule and where no more than one of the two carbon atoms attached to the carbonyl group is quaternary. . Diisobutyl ketone and methyl tert-butyl ketone are preferred. In the ketone, the acetyl halide is partially converted into a cyclic compound and converted into a polymer.
Parts are transformed and the rest remain unchanged. The presence of unchanged acetyl halide is an advantage of using ketones, which is not produced by dialkyl ethers, in which the acetyl halide is partly converted to a cyclic compound and the rest is converted into a cyclic compound. Converted to high molecular weight substances. Relatively large amounts of polymeric material may be formed in some ketones, originating from acetyl lard and/or unsaturated compounds. In diisobutyl ketone and methyl tert-butyl ketone, little or very little polymer is formed. When higher concentrations of acetyl halide in ketones are applied, the yield of cyclic compounds decreases.

However, these yields are 1 ton of ketone! Concentrations of up to 15 and especially up to 10 mol per mol are still very high. In this regard, the acetyl halide is preferably applied in a concentration ranging from 1 to 15 mol per ketone 1e, especially from 3 to 10 mol. Regardless of the concentration of acetyl halide, the yield decreases rapidly as the concentration of unsaturated compounds increases above 15 mol/e, and the zinc and tin halides formed become increasingly insoluble in the liquid range. . At increasing concentrations above 40 mol/e, these halides become little, if any, soluble;
Therefore, the formation of cyclic compounds is accompanied by great difficulty.

The selectivity towards cyclic compounds when using ketones as solvent is hardly influenced by the molar ratio of unsaturated compound to acetyl halide increasing above 0.5.

In this respect, the molar ratio is preferably selected in the range from 0.5 to 10, especially in the range from 1 to 2. Selectivity to cyclic compounds increases as the molar ratio of zinc or tin to acetyl halide increases.

Therefore, the molar ratio is desirably selected in the range of 1 to 10, particularly 1 to 5. Very good selectivity is usually 3
．． Obtained in molar ratios ranging from 5 to 4.5. The selectivity towards cyclic compounds is also advantageously influenced by a homogeneous distribution of zinc or tin in the liquid. If zinc powder with a relatively high specific surface area is used, the selectivity will be relatively low, but if zinc particles with a relatively low specific surface area are used, the selectivity will be at least, e.g.
The selectivity is even higher when zinc particles with a maximum dimension of 111 are used. High selectivity is 0.5-5
obtained using particles with a maximum dimension of mu. When modifying the new process by applying temperatures no higher than 5° C., no measurable jig addition occurs.

The yield of cyclic compounds increases with increasing temperature above 5°C, typically reaching a maximum at temperatures in the range of 25°C to 60°C, and increasing temperature above the temperature that gives maximum yield. It was found that it decreases with time. In this regard, the novel process is preferably carried out at a temperature in the range 15<0>C to 100<0>C, even more preferably at a temperature in the range 25<0>C to 60<0>C. The best results are usually obtained when the new process is carried out at temperatures between 35°C and 50°C. The contacting method can be carried out by any desired method.

For example, acetyl halide is added to a stirred suspension of zinc or tin in a solution of the unsaturated compound, either once or slowly, preferably over a period of up to 5 hours, for example. It is best to add the acetyl halide fairly rapidly, for example over a period of 0.25 to 0.75 hours. ] As the addition time increases, the yield of the cyclic compound usually decreases.
It is preferred to add the acetyl halide gradually;
The reason is that acetyl halide forms monohaloketones in situ, which are easily converted to undesired high molecular weight substances, so the gradual addition of acetyl halide favorably influences the selectivity towards cyclic compounds. It is from. However, in some cases, after most or all of the acetyl halide has been added, cycloaddition begins abruptly, with concomitant heat generation and significant polymer formation. 25% of the total amount of acetyl halide to be used
A suspension of zinc or tin in a solvent containing an amount of less preferably 2 to 10% is continuously stirred, the unsaturated compound is introduced into the suspension, and the remaining amount of acetyl halide is added. Sometimes, cycloaddition begins immediately and proceeds smoothly without substantial accumulation of acetyl halide concentrations. Also when zinc or tin is added gradually to a solution of acetyl halide and an unsaturated compound, or especially when acetyl halide and an unsaturated compound are added together to a stirred suspension of zinc or tin in a solvent, The selectivity is advantageously influenced. The selectivity to cyclobutanone or cyclobutenone is usually improved when the new process is carried out in the presence of an inorganic halide.

Such a catalytic amount of halide is very suitable, and 2.
0.1 calculated based on 2-dihaloacetyl halide
A range of 10% mole is preferred. Very suitable inorganic halides are mercuric iodide, sodium chloride, and especially potassium iodide and ammonium chloride. The cyclic compounds produced by the new method are brought into pure form by distilling the reaction mixture after removal of zinc or tin and washing with water for removal of the resulting zinc or tin halide. It can be isolated by When the cyclic compound is a 2-halocyclobutanone, after removal of zinc or tin and their halides, the reaction mixture is heated with water in the presence of a base, resulting in ring contraction (RingcOntractiOn), as shown in the general formula Can form salts of cyclopropanecarboxylic acid.

The salts are often obtained in yields of 90-100% calculated on the 2-halocyclobutanone. Substituted cyclopropane carboxylic acid esters are particularly suitable for use as insecticides; they have low mammalian toxicity and high insecticidal activity. Thus, the 2,2-dihaloacetyl halide represented by the general formula () is ethylenically unsaturated in the presence of zinc and/or tin in a dialkyl ether or ketone solvent at a temperature higher than 5°C. A compound represented by general formula (1) or () is prepared by reacting with a compound or alginic acid, and the obtained compound is heated with water in the presence of a base, and the obtained cyclopropanecarboxylic acid Provided is a method for producing cyclopropanecarboxylic acid represented by the general formula () by a method characterized by converting a salt of into a free acid.

For example, as described above, 2,5-dimethyl-2.
4-Hexadiene was reacted with monochloroketene formed in situ to give 2-chloro-4,4-dimethyl-3-(
2'-methyl-1'-probenyl)cyclobutanone and 2-chloro-3,3-dimethyl-4-(2'-methyl-1'-propenyl)cyclobutanone can be formed.

The latter two compounds were converted to cis- and trans-chrysanthemum monocarboxylic acids (2.
2-dimethyl-3-isobutenylcyclopropanecarboxylic acid), which can be easily converted to the free acid. Approximately 96% of the chrysanthemum monocarboxylic acid formed has a trans configuration, indicating that trans-chrysanthemum monocarboxylic acid has a significantly higher degree of insecticidal activity than cis-chrysanthemum monocarboxylic acid. It is an attractive feature because it has When 2,4-dimethyl-2,3-pentadiene is reacted with the in situ formed monochloroketene, 2-chloro-3
- 3-dimethyl-4-isopropylidenecyclobutanone and 2chloro-4,4-dimethyl-3-isopropylidenecyclobutanone are formed.

The latter two compounds were converted to 2.2- by the ring contraction method described above.
It is converted to the salt of dimethyl-3-isopropylidenecyclopropanecarboxylic acid. Cyclopropanecarboxylic acid is
The salt can be precipitated from an aqueous solution by adding an aqueous solution of a strong inorganic acid.

The precipitated carboxylic acids obtained by treating 2-halocyclobutanone with the ring contraction/conversion method have higher purity and lighter color when less polymer is simultaneously formed in the novel method of the present invention. .

Therefore, methyl tert-butyl ketone and diisobutyl ketone are 2-
It is the preferred solvent when halocyclobutanone is produced. Cyclobutenone can be hydrogenated to give the corresponding cyclobutanone, which can be used as described above.

The invention is further illustrated by the following example.

The described examples were carried out in a three-necked flask equipped with a paddle stirrer, a dosing funnel with a pot, a thermometer, an inlet for nitrogen, and a water-cooled reflux condenser with a drying tube. Experiments were conducted under nitrogen. Formula (1),
Some of the compounds shown in () or () are new compounds.

The experiments described in Examples 1 through were performed as described below, unless otherwise noted.

A flask was charged with 2,3-dimethyl-2-butene, zinc particles and dry diethyl ether 1e.

Zinc particles are 1w! It had a maximum dimension of t. The suspension in the flask was brought to a boil under reflux, and dichloroacetyl chloride was added dropwise through the dosing funnel over a period of 4 hours.
The reaction mixture thus formed was stirred under reflux for a further 8 hours. A stirrer kept the zinc homogeneously distributed in the liquid during the experiment. The dichloroacetyl chloride is totally converted and henceforth
2-chloro-3,3,4,referred to as "compound A"
One portion was converted to 4-tetramethylcyclobutanone and the remainder to high molecular weight product. The reacted 2,3-dimethyl-2-butene was completely converted to compound A. The yield of Compound A was calculated based on the starting dichloroacetyl chloride. The compounds 2,3-dimethyl-2-butene and dichloroacetyl chloride were referred to as DMB and DCAC, respectively, and their concentrations were expressed in moles per e of solvent. Example 1 Concentrations of DMB and DCAC and DCAC as shown in Table 1
Five experiments were performed using the molar ratio of zinc to

Table 1 also shows the calculated molar ratio of DMB to DCAC and the yield of Compound A. EXAMPLE Five experiments were carried out using DMB and DCAC each at a concentration of 0.24 mol/e and the molar ratio of zinc to DCAC as shown in the table.

The table also shows the yield of Compound A. Example Using the same molar amounts of DMB and DCAC, a molar ratio of zinc to DCAC of 2 and DCA (
Five experiments were performed using 3 degrees.

In experiments 4 and 5, DCAC was added for 16 and 24 hours, respectively, instead of 4 hours. The table also shows the yield of Compound A. Example (instead of DCAC only) a mixture of DCAC and DMB (DMBl
(instead of the mixture of zinc particles and diethyl ether) was added to the stirred mixture of diethyl ether and zinc particles.

Three experiments were thus conducted, with a molar ratio of zinc to DCAC of 2, and the molar ratio of DMB to DCAC and concentrations of DCAC as shown in the table. The table also shows the yield of Compound A. The yields obtained in experiments 1 and 3, applying the same DCAO crop rate, were higher than those of example experiments 2 and 3, respectively.

Example v Experiment A One experiment was conducted with a molar ratio of DMB to DCAC of 0.75 and a molar ratio of zinc to DCAC of 7.4.

400 ml of diethyl ether was charged into the flask instead of 1e. DCAC was used by dissolving 0.16 mol in 100 ml of diethyl ether. The reaction mixture was stirred for an additional 2 hours (instead of 8 hours) after the DCAC was added. The yield of Compound A was 57%. Experiment B (outside the scope of the invention) 50 ml of diethyl ether, . 0.012 mol DCAC and 0.036 zinc particles with maximum dimension 171 tm
The molar mixture was stirred vigorously under reflux at 34°C.

After 16 hours of stirring, DCAC completely disappeared. The zinc is then removed by decantation and the resulting liquid contains DMBO. 2 moles of O1 were added. The mixture thus formed was stirred vigorously at 34° C. for 3 hours. At the end of the elapsed time period, there were no detectable amounts of cyclobutanone in the mixture. The experiments described in Examples through X were performed as described below, unless otherwise noted. DCAClO mmol,
KIO. 6 mmol, maximum dimension 0.8417 Itm [2
0 Metsuyu, US Sieve Series (SieveSeri)
es), A. S. T. M. -E-11-61] and 20 ml of solvent were charged into a three-necked flask.

The initial temperature of the mixture thus formed was 38°C. The mixture was heated to 43° C., stirred for 1 hour and then 48 mmol (5.7 ml) of DMB were added in one portion.
52 mmol of DCAC was then added over 35 minutes and the reaction mixture thus formed was heated for a further 1.25 hours.
Stirring was carried out at a stirring speed of 2000 revolutions per minute. Six experiments were conducted using the solvents shown in the table.

The table also shows the yield of Compound A calculated based on the starting DCAC. The polymers formed in Experiments 1 and 2 originated from DCAC and DO.

The DMB reacted in Experiments 3, 4 and 5 was completely converted to Compound A. Zncl2 formed on the surface of zinc particles in Experiment 6 was not dissolved. The color of the reaction mixture darkened as more polymer was formed.
EXAMPLES Four experiments were performed using diisobutyl ketone as the solvent and DMB and DCAC concentrations as listed in the table.

The table also shows D calculated from the concentrations of DMB and DCAC.
The molar ratio of DMB to CAC and the yield of Compound A are also shown. DMB was completely converted to Compound A. The Zncl2 formed did not dissolve well in run 3 and did not dissolve at all in run 4. EXAMPLE Three experiments were conducted using diisobutyl ketone as the solvent, 62 mmol of DCAC, and the molar ratio of zinc to DCAC listed in the table.

The table also shows the yield of Compound A. DMB reacted
was completely converted to Compound A. EXAMPLES Three experiments were conducted using diisobutyl ketone as the solvent and a molar ratio of DMB to DCAC of 0.78.

The used concentrations of DMB and DCAC and the yield of Compound A are shown in the table. Example x Two experiments were carried out using diisobutyl ketone as the solvent and at the temperatures shown in Table x.

The table also shows the yield of Compound A. Example M DCAClO. 3 mmol of diisobutyl ketone 20-
was added to a stirred suspension of 240 mmol of zinc shavings (same size as in the example), 6 mmol of ammonium chloride and 0.6 mmol of potassium iodide at 38°C.

The solution turned yellow and rose in temperature within 3 minutes.
The temperature was maintained at 40°C to 45°C. After 10 minutes, 2-methyl-
96 mmol of 2-benzene was added in one portion.

Then DCAC 5l. for 30 minutes. 7 mmol was added. The mixture was then stirred at 40°C to 45°C for 1.25 hours. The orange-yellow solution thus obtained was decanted into a separator funnel, the excess zinc was washed three times with acetone, and the acetone washings were added to the orange-yellow solution and the mixture thus formed. water 200W
It was washed with 1 t.

A precipitate formed which dissolved after acidification with a few drops of concentrated aqueous hydrochloric acid. The acidified solution contains the novel compounds 2-chloro-3-ethyl-4.l-dimethylcyclobutanone and 2-chloro-4-ethyl-3.3-dimethylcycloptanone, and the acidified solution is 1M to
0 at 22°C with 110d of aqueous sodium hydroxide solution.
．． Stirred for 75 hours. The mixture was then separated into aqueous and organic layers. The aqueous layer was acidified using 7.5 d of concentrated aqueous hydrochloric acid. The oil thus obtained was extracted with diethyl ether and the extracted phase was dried over anhydrous magnesium sulfate. Evaporation of diethyl ether yielded 84% by weight of 2,2-dimethyl-3-ethylcyclopropanecarboxylic acid.
3.8 tons of viscous oil was obtained. The yield of the new acid is
It was calculated based on DCAC to be 42%. Selectivity to the acid was greater than 50%. Approximately 60% of the acid had a trans configuration. Example DCAClO. 3 mmol, diisobutyl ketone 20
Added at 40° C. to a stirred suspension of 240 mmol of zinc shavings (same size as in the example), 6 mmol of ammonium chloride and 0.6 mmol of potassium iodide in r111.

The solution turned yellow within 3 minutes and an increase in temperature was observed. The temperature was kept at 40°C to 45°C. 8 minutes later 2.
96 mmol of 5-dimethyl-2,4-hexadiene
It was added at the same time.

Next, DCAC5l. 7 mmol was added over 30 minutes. The mixture was then stirred at 40°C to 45°C for 1 hour. The orange-yellow solution thus formed was decanted into a separator funnel, the excess zinc was washed three times with Ajotone, and the acetone wash was added to the orange-yellow solution thus obtained. The resulting mixture was washed with 175 ml of water.

The washed mixture contains two new compounds 2-chloro-
4,4-dimethyl-3-(2-methyl-1-propenyl)cyclobutanone and 2-chloro-3,3-dimethyl-4-(2-methyl-1-propenyl)cyclobutanone; Stirred with 110 ml of 1M aqueous sodium hydroxide solution at 22° C. for 0.75 h. The mixture was then separated into aqueous and organic layers. The aqueous layer was acidified using 7.57!12 liters of concentrated aqueous hydrochloric acid.
The oil thus obtained was extracted using chloroform and the extracted phase was dried over anhydrous magnesium sulfate.
Chloroform was evaporated from the extracted phase to obtain 5.5 f of a viscous oil containing 70% by weight of chrysanthemum monocarboxylic acid. The yield of the acid was 37% based on DCAC.
Approximately 96% of the acid had a trans configuration. Example DCAClO. 3 mmol, diisobutyl ketone 20
240 mmol of zinc shavings (same dimensions as in the example), 6 mmol of ammonium chloride, and 0 potassium iodide in Tn1
．． 6 mmol was added to a stirred suspension at 40°C.

The temperature was kept at 40°C to 45°C. After 3 minutes, 48 mmol of isopropyl 3-methyl-2-butenyl ether were added in one portion.

Next, DCAC5l. 7 mmol was added over 20 minutes. The mixture was then heated to 0.25°C at 4°C to 45°C.
Stir for hours. Decant the yellow solution thus formed into a separator funnel and remove excess zinc with acetone.
The acetone wash was added to the yellow solution and the mixture thus obtained was washed with 175 ml of water.

The washed mixture contains two new compounds 2-chloro-
The washed mixture containing 4-isopropoxymethyl-3,3-dimethylcyclobutanone and 2-chloro-3-isopropoxymethyl-4,4-dimethylcyclobutanone was mixed with 110 m2 of 1M aqueous sodium hydroxide solution at 22°C. Stirred for 0.75 hours. The mixture was then separated into aqueous and organic layers. The aqueous layer is 75ml of concentrated aqueous hydrochloric acid.
It became sexualized. The oil thus obtained was extracted with chloroform and the extracted phase was dried over anhydrous magnesium sulfate. The chloroform was evaporated from the extract phase to obtain 2.65 f of a viscous oil containing 64% by weight of 2,2-dimethyl-3-isopropoxymethylcyclopropanecarboxylic acid.
The yield of the new acid was 15% based on DCAC. Approximately one of the acids had a trans configuration. Example tile DCAC5l. 7 mmol, diisobutyl ketone 10
A stirred suspension of 1200 mmol of zinc shavings (same dimensions as in the example), 29.9 mmol of ammonium chloride and 3.0 mmol of potassium iodide in 0 ml was added at 35°C.

The solution turned yellow within 5 minutes and an increase in temperature was observed. The temperature was kept at 40°C to 45°C. After 5 minutes, 240 mmol of benzyl 3-methyl-2-butenyl ether were added in one portion and the temperature rose to 50°C.

Five minutes after addition of benzyl 3-methyl-2-butenyl ether, 310 mmol of DCAC was added over 35 minutes. The mixture was then stirred at 40°C to 45°C for 0.75 hours. The solution thus formed was decanted into a separator funnel, excess zinc was washed three times with acetone, the acetone wash was added to the solution and the mixture thus obtained was washed with 500 ml of water. .

The washed mixture contains two new compounds 2-benzyloxymethyl-4-chloro-3,3-dimethylcyclobutanone and 3-benzyloxymethyl-2-chloro-
4,4-dimethylcyclobutanone, and the washed mixture was mixed with 550 ml of 1M aqueous sodium oxide solution.
Stirred at 2°C for 0.75 hours. The mixture was then separated into aqueous and organic layers. The aqueous layer was acidified with 40 m2 of concentrated aqueous hydrochloric acid. The oil thus obtained was extracted with chloroform and the extracted phase was dried over anhydrous magnesium sulfate. Evaporation of the chloroform from the extraction phase yields a viscous oil containing 53% by weight of the new compound 2-benzyloxymethyl-3,3-dimethylcyclopropanecarboxylic acid14.
I got 0y. The yield of the acid was 8% based on DCAC. Approximately 57% of the acid had the trans configuration. Example XV 10 ml of diethyl ether, 3 mmol of unsaturated compound and 6 mmol of zinc particles were charged into a three-necked flask and the temperature was maintained at 35° C. with stirring.

Then 6 mmol of DCAC was added in one portion. Seven experiments were performed, each using a different unsaturated compound.

Table M shows the unsaturated compounds used and the yield of formed cyclic compounds based on DCAC at various times after the start of the experiment. 2-chloro-3,3,4,4-
The cyclic compounds formed other than tetramethylcyclobutanone are novel compounds.

EXAMPLE

The suspension in the flask is kept boiling under reflux and 50 ml of dry diethyl ether] DCACO.
The 24 molar solution was dripped through the dosing funnel over a period of 4 hours. The reaction mixture thus obtained was stirred under reflux for a further 8 hours. After cooling to 20'C, the reaction mixture was washed with an equal volume of water.

The two phases were separated, the organic phase obtained (containing compound A) was stirred with a solution of 0.5 ml of sodium hydroxide in 500 mj of water, and the diethyl ether was distilled off while stirring.

20% by weight aqueous hydrochloric acid is then subsequently added to the resulting residue to bring the pH to 2.5, the solution is steam distilled and the distillate is separated by filtering to separate the aqueous phase and the solid 2. 2,3,3-tetramethylcyclopropanecarboxylic acid. The yield of the acid was 57% calculated based on DCAC.
Example X The process of Example X was repeated using four other ethylenically unsaturated compounds.

Claims (1)

[Claims] 1 General formula (I) or (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, Hal is F, C
1 or Br, each of R^1, R^2, R^3 and R^4 may be the same or different and represents a hydrogen atom or is optionally substituted by an alkoxy, benzyloxy or alkoxycarbonyl group; represents an optionally substituted alkyl or alkenyl group, or represents an alkoxycarbonyl group, or R^1 and R
^3 together or R^2 and R^4 together form an alkylidene group, or one of R^1 and R^3 and one of R^2 and R^4 are In the production of cyclobutanone or cyclobutenone which together with the two bonded carbon atoms form a carbocyclic ring,
Formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [
Here, each Hal represents F, Cl or Br]
・Formula (IV) or (IV) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (IV) R^1-C=C- in dialkyl ether or ketone using 2-dihaloacetyl halide as a solvent
R^2(V) [wherein R^1, R^2, R^3 and R^4 have the meanings given above] in the presence of unsaturated compounds and zinc and/or tin above 5 °C The above manufacturing method is characterized by contacting at a temperature.