DE2243685A1 - SUBSTITUTED DIOXANS, PROCESS FOR THEIR PRODUCTION AND HERBICIDAL COMPOSITIONS CONTAINING THESE COMPOUNDS - Google Patents

Description

Dr. F. Zumsteln is ι. - Or. E. Assmanri 2 2 4 3 6 8 5 Dr. R. Koenlgsberger - Dlpl.-Phys. t <. Holzbauer - Dr. F. Zumsteln jun.

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 225341

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BANK ACCOUNT: BANKHAUS H. AUFHÄUSER

8 MUNICH 2,

BRÄUHAUSSTRASSE 4/111

FMC case 4224

"Substituted dioxanes, processes for their preparation and herbicidal compositions containing these compounds "

The invention relates to substituted dioxane processes for their preparation, herbicidal compositions containing these compounds and a method of control of unwanted plant growth due to pre-emergence and post-emergence treatment with the herbicidally active compounds.

The invention particularly relates to substituted dioxanes the general formula:

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- if - CH ₂ C5
N ι CH ₂ O - 3
O - ^ O - CH ₂ - "r5

wherein the -OCH _p -R ^r -r group is cis to the τοη

2 material different group R is,

2 ■

R is a hydrogen atom, an alkyl group, a haloalkyl, group, a cyanoalkyl group, an aryl group, an aryloxyalkyl group, an arylalkoxyalkyl group or an alkoxyalkyl group denotes, where the alkyl groups or the substituted alkyl groups have 1 to 6 carbon atoms and the aryl group is a phenyl group, a furyl group © or represents a thienyl group which optionally has a substituent X which represents a fluorine atom, a chlorine atom, a bromine atom, a low molecular alkyl group, a low molecular alkoxy group or a benzyloxy group

can be,
pa

R represents a hydrogen atom or a methyl group

a 2

oa 2
or the groups R ^ and R together can form two or more methylene groups and thus a spiro grouping (so that the stereoisomers are in vibrational equilibrium and cannot be separated), R ^ a hydrogen atom, an alkyl group or a haloalkyl group, such as a chloroalkyl group or denotes a bromoalkyl group, the alkyl groups containing 1 to 4 carbon atoms,

R ^{r is} a monovalent aromatic phenyl, furyl, thienyl or pyridyl group, which optionally has 1, 2 or 3 »TorzugBweise less than 3 substituents Y, the fluorine atoms, chlorine atoms, bromine atoms, cyano groups CF, groups, low molecular weight alkyl groups or represent low molecular weight alkoxy groups, with the caveat that when the group R ^r

is an unsubstituted phenyl group, and the group R

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- 1 ■■

represents a hydrogen atom, the group R from an unsubstituted one Phenyl group is different. The above cis configuration occurs when the group

r '2

-OCH ₂ -R are in the axial position and the group R is in the equatorial position.

Preferred herbicidal compounds are those wherein

2 '

the group R is an alkyl group, a haloalkyl group or a cyanoalkyl group having 1 to 4 carbon atoms, a phenyl group or a phenyl group containing a substituent X in the 3-position (meta-position) and R ^{r is} a phenyl group or a phenyl group in the 2-position (ortho Position) denote a phenyl group having a substituent Y. Particularly preferred herbicidal compounds are

ρ
those in which the group R is an alkyl group or a haloalkyl group having 1 to 4 carbon atoms and the group R ^{r is} a phenyl group, a 2-chlorophenyl group, a 2-r-fluorophenyl group or a 2-methylphenyl group.

Classical routes can be used to prepare the cis-5-arylmethoxy-1,3-dioxane compounds which are substituted in the 2-position according to the invention. The compounds, which may have a Y substituent, can be prepared by etherifying the corresponding cis-5-hydroxy-1,3-dioxane in xylene or another suitable solvent with benzyl chloride. For example, 5-hydroxydioxane can be reacted in solution with sodium hydride, whereby the corresponding sodium alcoholate is obtained, which is then reacted with the chloride. The 5-hydroxydioxane, which is a cyclic acetal, can be prepared by reacting glycerin with an aldehyde. In these reactions, 4-hydroxymethyl-1,3-dioxolanes are normally formed as by-products, " _F. . ""

■ -. ^"-;; ■ -;"".." ■ ■■ - "- ■■■ ρ The compounds of the general formula wherein the group R.

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means a hydrogen atom could be produced by it be that the sodium alcoholate of J? -Hydroxy-1,3-dioxane, obtained by acetal formation from glycerol and formaldehyde, with an aryl methyl chloride or -bromide etherified. It can also be achieved by an acetal formation reaction with formaldehyde and a 2-arylmethoxy-1,3-propanediol produce. The latter compounds are obtained by methods known per se, for example by acidic Hydrolysis of the corresponding iiJ-arylmethoxy-2-aryl-i, 3-dioxanes.

Alternatively, the dioxanes according to the invention by a acetal-forming reaction of an aldehyde or a ketone with a suitable 2-arylmethoxy-1,3-propanediol will. This procedure is particularly beneficial when

2
the group R is a group such as, for example, the chloromethyl group, which is attacked by the alkaline reagents normally used in the above-mentioned etherification reaction.

For the preparation of the compounds of the general formula in which the group R ^x differs from hydrogen, the process which starts from 5-alkylidene-1,3-dioxanes is particularly advantageous. The correspondingly substituted 5-alkylidene-1,3-dioxane is converted into an epoxy compound, whereupon the epoxy compound is hydrogenated to obtain the corresponding 5-hydroxy-5-alkyl-1,3-dioxane, which is then etherified as described above .

When the compounds according to the invention are used as herbicides, the active ice compounds can be used together use with the trans isomers and the mixtures can even contain a predominant proportion of the latter compounds contain. In general, it is particularly economical by syntheses in which the formation of the trans isomer suppressed or avoided, manufactured materials

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to be used with a high ice content. The higher the content of cis isomer, the higher the herbicidal effect of a given mixture of cis and trans isomers. Most prefer- test the cis compound is present in an amount that is at least the same as that of the corresponding trans compound and e.g. the cis: trans ratio is higher than 3: 2, more preferably higher than 2: 1 and even more preferably higher than at least 3: 1. The aforementioned dioxolanes can in the Mixture may also be included as impurities.

When the 5-hydroxydioxanes used as starting materials are in the cis form, the products obtained have a high content of herbicidally active cis-5-arylmethoxy-2-aryl-1,3 ^ -dioxanes on. It is also often found that one is involved in the crystallization of the products (from reaction mixtures containing a solvent such as xylene) followed by recrystallization (e.g. from a benzene / ligroin or a benzene / petroleum ether mixture) solid products are obtained which contain more active cis compounds than trans compounds and that preferably Dioxolane can be dissolved.

The invention represents a new class of herbicidal ma- * materials with both pre-emergence and post-emergence effects ready. The materials are intended for the control and elimination of grasses, especially annual grasses, in Presence of broad-leaved crops such as cotton, sugar beet, peanut plants, soybeans, green beans, lima ' Beans, tomatoes or cuttings (nursery stock) are suitable.

The preparation, the properties and the herbicidal effects of representative representatives of the compounds according to the invention are explained in more detail ^{in the following examples, in which all temperatures are given in ° C.} If, in the examples, reference is made to a reduced pressure without this pressure being specified in greater detail, then

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it is the pressure that you get with a water jet pump can reach. Compounds that have a substituent in the 5-position are with the usual cis and trans designations named to help configure this in the 5-position substituents $ u dein in the 2-position standing substituents to indicate. If two Substituents are present in the 5-position, one is denoted by c (cis) or t (trans) to indicate its configuration, to indicate based on the substituent in the 2-position, which is denoted by r (reference), while the other substituent in the 5-position is not provided with a nomenclature. To the cis and trans configurations were determined by gas chromatographic investigations and nuclear magnetic resonance spectra are used,

example

Ih this example, a white crystalline sample of 5-benzyloxy-2-phenyl-1,3-dioxane (F 75-76 ⁰ C) having a high cis content used.

The pre-emergence and post-emergence herbicidal effects of this Materials were examined as follows:

Green beans, corn, lettuce, mustard, and fingergrass were planted side by side in flat-bottomed trays filled with a mixture of equal amounts of clay, mud, and sandy mud soil. The material to be examined was dissolved in an acetone / water mixture and sprayed onto the soil in an amount of 8.96 kg / ha to determine the pre-emergence test. In the investigation of the post-emergence effect, the plants were sprayed about Z weeks after planting, a point in time at which the painting plants had developed 3 to 4 real leaves, with the acetone / water solution mentioned in an amount of 8.96 kg / ha. Two weeks after treatment, the phytotoxicity of the

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• - 7 ■ ·

Materials both in the pre-emergence examination and both Post-emergence examination assessed. In both examinations untreated plants were used for comparison purposes. It was essentially a complete kill detect maize and fingergrass both in the pre-emergence and post-emergence tests, while none of the other plants were killed.

example

In this example a cis-5-benzyloxy-2-phenyl-1,3-dioxane sample, manufactured as follows:

4.0 g of a 60% suspension of sodium hydride in mineral oil were added in portions to a solution of 16.8 g of cis-5-hydroxy-2-phenyl-1,3-dioxane in 150 ml of xylene. The mixture was then ^{kept at 40 °} C. for 1 hour. To this solution was added 13.9 g of benzyl chloride dropwise. Then, the temperature of the reaction mixture was kept for 6 hours at 11O ⁰ C. After the reaction mixture was cooled, it was filtered off and evaporated under reduced pressure. The solid obtained was recrystallized from a benzene / ligroin mixture. The melting point of the recrystallized product was 73 to 75 ^° C. The thin-layer chromatographic investigation and the NMR investigations showed that 80 to 90 % of the product was cis-5-benzyloxy-2-pheny1-1,3-dioxane Product showed an excellent selective herbicidal pre-emergence and post-emergence action, as indicated in the following table ί, in which the numbers represent the percentage destruction at the indicated dosages.

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TABLE I.

Herbicidal pre-emergence and post-emergence effects of cis-5-benzyloxy-2-phenyl-1,3-dioxane '.' ■ ',

Examined plants

Corn

Serif

Fingergrass

Chicken millet

cotton

Percentage kill at a dose of 6.72 kg / ha

Yor casserole
100

100

40

Post-emergence 100

100

100

Example 3

5- (4-methylbenzyloxy) -2-phenyl-1,3-dioxane

Using the procedure described in Example 2, 16.8 g (0.1 mol) of cis-5-hydroxy-2-phenyl-1,3-dioxane were reacted with 14.0 g (0.1 mol) of 4-methylbenzyl chloride. Since a solid began to separate out after the reaction mixture "" was cooled, the entire reaction mixture was concentrated under reduced pressure. The solid product was slurried with water and filtered off. The solid cake was dried in a vacuum oven, leaving 23 »2 g
a solid (106-109 ⁰ C). Recrystallization from benzene / ligroin mixture gave 9.1 g of the product (109 F τ 11O ⁰ C). A second recrystallization raised the melting point to 112.5-113 ° C. Thin layer chromatographic analysis showed that the obtained

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Product practically pure cis-5- (4-methylbenzyloxy) -2-phenyl 1,3-dioxane was.

example

j? -Benzyloxy-1,3-dioxane

(a) 12 g (0.066 mol) of 2-benzyloxy-1,3-propanediol, 2.0 g of trioxymethylene, 0.1 g of p-toluenesulfonic acid and 100 ml of benzene

"were placed in a flask fitted with a stirrer, reflux condenser, and Dean-Stark humidity" trap. ¹ The flask was heated to 80 ⁰ C and the reflux was continued until 1.4ml of water had been collected, the mixture was then cooled to room temperature, washed twice with 100 ml of an aqueous 2% sodium bicarbonate solution and then twice with 100 ml of water. The washed benzene layer was dried over magnesium sulfate, filtered off, and the solvent was evaporated under reduced pressure. The remaining oil was distilled, giving a fraction (5-benzyloxy-1,3-dioxane) which distilled over at a flask temperature of 72 to 80 ° C./10 −4 mm Hg.

(b) In another process for the production of 5-benzyloxy-1,3-dioxane, 5-hydroxy-1,3-dioxane was used as the starting material (Tetrahedron 2 »10-18 (1959)).» The latter material was prepared by reacting glycerol with trioxymethylene in the presence of HCl as a catalyst, a mixture of the cyclic acetals being obtained (J. Am. Chem _o Soc. £ 0, 3124 (1928)), This Ace-

. talmischung was esterified in the presence of pyridine with benzoyl chloride to give, after recrystallization of the benzoate 5-hydroxy-1,3-dioxane (F 71 --72 ⁰ C) received (J. Am. Chem. Soc. £ 0, 3120 (1928)). This ester

3 0 9 8 13/1197.

was then split up in chloro form by reaction with sodium methylate, with purified S-hydroxy-1,3 ~. dioxane received in the form of a fraction which ^{distilled over at 95 to 96 0} C / 22 mm Hg. 3 g (0.029 Kai) ′ of the last-mentioned product and 100 ml of benzene were placed in a flask, and 1.1 g of sodium hydride were added in portions with stirring, during which hydrogen was evolved. The resulting slurry was stirred at room temperature for 1/2 hour without further addition of reagents and then 3 »65 g of benzyl chloride was added dropwise over 15 minutes. After all of the benzyl chloride had been added, the mixture was brought to 80 ^° C. and stirred at this temperature for 24 hours. The slurry thus obtained was washed twice with 100 ml of water, and the resulting organic layer was dried over MgSO 4. The drying agent was filtered off and the solvent was removed under reduced pressure to give an oil, which was distilled under reduced pressure to obtain a fraction of (5 ~ B # nzyloxy ~ 1,3-dioxane) with an estimated purity of about 85 % .

example

cis -5 (2-methylbenzyloxy) -2-phenyl-1,3-dioxane

2.0 g (0.05 mol) of 61% sodium hydride was added to 8.5 g (0.05 mol) of cis-5-hydroxy-2-phenyl-1,3-dioxane in 150 ml of xylene. The slurry was stirred at room temperature for 1/2 hour after which time 9.3 g (0.05 mol) of 2-methylbenzyl bromide was added. The reaction mixture was then heated for 6 hours at 10t) ⁰ C, cooled and washed with 2 χ 75 ml of water. The organic layer was separated, dried over magnesium sulfate and concentrated to give 12.4 g of the product

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tes (F 77-82 ⁰ C) received. Recrystallization from a benzene / ligroin mixture gave 5 _t 3 g of the product (B * 78 79 ⁰ C). Analysis by thin-layer chromatography showed that the product consisted of 100% cis-5- (2-methylbenzyloxy) -2-phenyl-1,3-dioxane.

Example '

cis -5 (2-fluorobenzyloxy) -2-phenyl-1,3-dioxane

Using the procedure described in Example 5, 8.4 grams (0.047 moles) of cis-5-hydroxy-2-phenyl-1,3-dioxane was reacted with 2.0 grams (0.047 moles) of sodium hydride (61%). The sodium salt obtained was 7.2 g (0.05 mol) of 2-fluoro. benzyl chloride to give man / ligroin mixture 2.8 g after Umkristaliisation from benzene a white solid (F "65-67 ^C C) and, after further recrystallization gave a solid having a melting point of 70 to 71 ⁰ C. The thin-layer chromatography. Analysis showed that the product consisted of 90% cis-5- (2-fluorobenzyloxy) -2-phenyi-1,3-dioxane.

example

5-benzyloxy-2- (3-fluorophenyl) -1,3-dioxane .

A. Preparation of 5-hydroxy-2- (3-fluorophenyl) -1,3-dioxane

A mixture of 24.8 g (0.2 mol) 3-fluorobenzaldehyde, 18.4 g (0.2 mol) of glycerin and 2.0 ml of 40% sulfuric acid in 200 ml of benzene was stirred in a. Dean-Stark apparatus heated until (after about 2.5 hours) no more water passed over. The mixture was then cooled with Potassium carbonate neutralized and washed after the addition of 200 ml of ether with 3 x 100 ml of water. The washed solution was dried over magnesium sulfate and under reduced pressure

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Pressure concentrated to give 29.0 g of a colorless oil which is at a pressure of 0.025 mm Hg in a distillation device Kureweg distilled to give τοη at a bath temperature 86-105 ⁰ C 18.9 g of 5-hydroxy-2 - (3-fluorophenyl) -1,3-dioxane (n ^ 1.5160).

B. Preparation of 5-Benzyloxy-2- (3-fluoiThenyl) -1,3-dioxane

A slurry of 3.7 g (0.096 mol) of sodium hydride (62 %) in 100 ml of benzene and 100 ml of xylene was stirred at room temperature, 18.9 g (0.096 mol) of 5-HydroXy-2 being added dropwise over the course of 1 hour - (3-fluorophyl) -1,3-dioxane was added. The mixture was stirred for an additional hour and then 12.2 g (0.096 mol) of benzyl chloride were added over 1/2 hour. The mixture was heated to reflux for 18 hours, cooled and filtered, and the piltrate was washed with 2 × 200 ml of water. The washed solution was dried over magnesium sulfate and concentrated, giving 19.7 g of an oil which was distilled at a pressure of 2 × 10 mm Hg, bath temperatures of 98 to 119 ^° C. (fraction 1), 119 to 139 ° C (fraction 2) and 139-143 ⁰ C (Group 3) received three fractions. Fraction 2 (9.1 g) was shown according to the NMR analyzes as a mixture of cis and trans dioxanes and the corresponding dioxolane. Fraction 3 (1.5 g, F 70 - 71 ⁰ C) consisted of NMR analysis corresponding to 100% of cis-5-benzyloxy-2- (3-fluorophenyl) -1,3-dioxane. This fraction 3 was used in the further investigations.

Example 8 . · ". ■ ,, j« ..

5- (2 ~ fluorobenzyloxy) -2- (3-fluorophenyl) -1 _Λ 3 ~ dloxan

Using the procedure described in Example 5, there was obtained 16.8 g (0.085 moles) of 5-hydroxy-2- (3-fluorophenyl) -1,3-dioxane reacted in 150 ml of benzene with 3.4 g of 60% sodium hydride, whereupon the sodium salt thus formed with 12.3 g

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(0.085 mol) 2-fluorobenzyl chloride was reacted so that one Received 22.4 g of an oil, with the formation of 11.4 gdes

-Zi

Product was distilled at a pressure of 1 10 mm Hg »The renewed distillation at a pressure of 1 χ 10 mm Hg gave three fractions which, at bath temperatures of 138 to 145 ⁰ C (fraction 1), 145 to 150 ⁰ C ( Fraction 2) and 150 to 152 ^O C (fraction 3) overdistilled. The factions 2 and? were combined (4.0 g) and NMR analysis showed this product to contain 30% Cls-5- (2-fluorobenzyloxy) -2- (3-fluorophenyl) -1,3-dioxane. .

At s ρ i el

5-Benzyloxy-2-methyl-1,3-dioxane ..-.-:

A. Preparation of 5-hydroxy-2-methyl-1 _f 3-dioxane .

44 were slowly added to a 500 ml three-necked flask equipped with a stirrer, a reflux condenser and a Dean-Starte trap (for azeotropic removal of water) and in which a mixture of 92 g of glycerol and 6 drops of concentrated sulfuric acid was stirred g acetaldehyde. The reaction mixture was then ^{heated to 100 °} C. for 3 hours, cooled to room temperature and neutralized with solid potassium carbonate. The mixture was washed with 100 ml of petroleum ether and then distilled at 58 to 60 ° C./Q, 75 mm Hg, 68.4 g of a mixture of the dioxanes and the dioxolanes being obtained. ·

One! Peil of the dioxane / dioxolane mixture was about 0.6 g Hydrogen chloride gas & reacted and then 1/2 hour on one Steam bath heated. After the mixture has reached room temperature Was cooled, 150 ml of dry pyridine was added. 71 g of benzoyl chloride were then slowly added to this mixture and the suspension obtained was stirred for 1 hour at room temperature. The reaction mixture was then in 1 »j? Ltr «, cold Poured water, with an oil parted. The water

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ge layer was extracted with 2 × 200 ml of ether, whereupon the ether extracts were added to the UI. This organic mixture was washed successively with 2 × 100 ml of a 5% sodium hydroxide solution, 2 × 100 ml of a 3% sulfuric acid solution and with water. After the ether solution had been dried over potassium carbonate, the solvent was removed by evaporation. 100 ml of petroleum ether were then added to the remaining oil, from which, after cooling, 14.4 g of $ -BenBoyloxy-2-methyl-1,3-dioxane (F 76 - 78 ⁰ C) failed.

For the hydrolysis of the benzoyloxy-1,3-dioxane, a solution of 1j8 g sodium in 25 ml methanol was added in portions to a stirred mixture of 14.0 g 5-benzoyloxy-2-methyl-1,3-dioxane and 80 ml chloroform reaction mixture was then stirred at 60 ⁰ C 4β hours »cooled to room temperature and neutralized with solid" carbon dioxide. After Han had removed the solvents under reduced pressure, the residue was dissolved in water. The solution was washed with petroleum ether and then extracted with ether. After the ether extracts had been dried over magnesium sulphate, the ether was sucked off under reduced pressure, giving 9.1 g of 9-hydroxy-2-methyl-1,3-dioxane. The infrared spectrum of the product was consistent with the stated structure.

B. Production of 5- * benzyloxy-2-methyl - 1 ₁ 3-dioxane

1.6 g of sodium hydride were added in portions to a mixture of 4.8 g of 5-hydroxy-2-methyl-1,3-dioxane U & d 100 ml of benzene. This mixture was stirred for 1/2 hour at room temperature and then 5.1 g of benzyl chloride were added in portions over the course of 1 hour. The reaction mixture was ^{heated to 80 °} C. for 24 hours while stirring. The reaction mixture was then washed with 2 × 100 ml of water and the organic layer was dried over magnesium sulfate. The solvent was then suctioned off under reduced pressure, giving 7.5 g of an oil which was distilled, with

309113/1137

man 4.1 g of 5-benzyloxy-2-methyl-1,3-dioxane were obtained (boiling point 111-112 ° C. / 0.4 mm Hg, n * p 1.5013). The IR and NMR spectra were consistent with the structure indicated and showed that the product was 70 % of the cis isomer and
Contained 30 % of the trans isomer.

Analysis: Calculated for C ₁₂ H ₁₆ O ₃ : C, 69.21; H 7.74 »Found: C 68.97; H 7.76.

Example 10

2-ethyl-5- (2-fluorobenzyloxy) -5-methyl-1,3-dioxane

A. Preparation of 2- (2-fluorobenzyloxy) -2-methyl-1,3-propane diol _; ' _ ■ _

In a 2 liter flask fitted with a stirrer, thermometer, dropping funnel and reflux condenser
Drying tube was provided, 88.4 g of 2-fluorobenzyl alcohol was added dropwise over 45 minutes to a stirred suspension of 20.2 g of sodium hydride in 1200 ml of anhydrous toluene. After the addition had taken place at 25 to 30 ^° C., the reaction mixture was ^{heated to 90 °} C. for 1 1/2 hours, then cooled and, in the course of 11/4 hours at 30 to 50 ^° C., with 177.1 g of 2-bromine -2-methylmalonic acid diethyl ester added. The reaction mixture was ^{heated to 90 to 95 °} C. for 2 hours and then cooled, whereupon it was left to stand at room temperature overnight. The reaction mixture and 500 ml of ether were then poured into a flask containing 1 liter of saturated sodium bicarbonate solution and 1 kg of crushed ice. After the ice had melted, the aqueous phase was separated off and extracted with 3 × 500 ml of ether. The ether solutions were combined, washed with 3 × 500 ml of water and dried by filtering over sodium sulfate. After separating off the ether and the remaining toluene oil under reduced pressure, 176.2 g of 2- (2-fluorobenzyloxy) -2-methylmalonic acid diethyl ester were obtained, the structure of which was confirmed by the IR spectrum

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A suspension of 25.8 g of lithium aluminum hydride in 1000 ml of anhydrous ether was prepared in a 2 liter flask equipped with a stirrer, a dropping funnel and a reflux condenser with a drying tube. 101.6 g of diethyl 2- (2-fluorobenzyloxy) -2-methylmalonate were then added to the stirred suspension at a rate sufficient to maintain reflux Rinsed with ether and refluxed the reaction mixture for a further 4 hours. The mixture was then cooled and kept in an ice bath while the excess reducing agent was destroyed by the dropwise addition of a saturated sodium sulfate solution. 250 ml of ice water and 1150 ml of 10 % strength sulfuric acid were then added to the stirred reaction mixture. The aqueous phase was separated from the ether solution, saturated with sodium chloride and extracted with 2 × 500 ml of ether. The ether solutions were combined, dried over sodium sulfate and concentrated to an oil. The volatile impurities were removed by distillation at a pressure of 0.01 mm Hg to give a residue which was recrystallized from a petroleum ether / chloroform mixture, 27.5 g of 2- (2-fluorobenzyloxy) -2-methyl- 1,3 ~ propanediol was (F 74.5 to 75 ⁰ C). The IR and NMR spectra were consistent with the structure indicated.

Analysis: Calculated for C ₁₁ H ₁ ^ FO: C, 61.66; H 7.06; Found: C, 61.44; H 6; 95.

B. Preparation of 2-ethyl-5- (2-fluorobenzyloxy) -5-methyl- 1,3-dioxane

In a 500 ml flask fitted with a stirrer, a Dean-Stark trap and a reflux condenser with a drying tube was provided, a mixture of 9.4 g of 2- (2-fluorobenzyl-I oxy) -2-methyl-1,3-propanediol, 2.8 g propionaldehyde, 300 ml Hexane and a catalytic amount of p-toluenesulfonic acid Held at reflux for 2 hours. After the reaction

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The mixture was allowed to stand overnight, it was filtered off and the filtrate was concentrated under reduced pressure to give an oil, which was dissolved in 300 ml of benzene. The benzene solution was washed with 100 ml of a 10% sodium carbonate solution and twice with 100 ml of water, dried over sodium sulfate, and then under ver. concentrated to an oil under reduced pressure. The oil was applied to a column filled with silica gel (30 × 310 cm) and first with petroleum ether (fractions 1 to 3) and then with a petroleum ether / ethyl acetate mixture (99/1 for fractions 4 to 19 and 9/1 for fractions 20 to 23) eluted. Fraction 1 had a volume of 200 ml, fractions 2, 3, 24 and 25 had a volume of 100 ml while fractions 4 to 23 had a volume of 50 ml each. The elution was followed by thin layer chromatography. The product obtained from fractions 9 to 12 was distilled, giving 2.0 g of r-2-ethyl-t-5- (2-fluorobenzyloxy) -5-tmethyl-1,3-dioxane (boiling point 78-79 ° C / 4 χ 10 mm Hg, njp 1.4878) The product of fractions 15 to 25 was also distilled and gave 3.7 g of r-2-ethyl-c-5- (2-fluorobenzyloxy) -5-methyl- 1,3-dioxane. (Boiling point 82-86 ° C / 4 χ 10 "" ⁴ mm Hg, n | p 1.4909). The IR and NMR-T spectra of the two isomers were consistent with the stated configurations and indicated that each isomer was free of the other isomer. The purity was also determined by thin layer chromatography.

. Analysis: Calcd for C ^ H _{1 1} QFO _3: C, 66.12; H 7.53; found (t-isomer): C, 66.30; H 7.62; found (c-isomer): C, 66.08; 'H 7.65.

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Example 11 2 ~ ethyl ~ 5- (2-methylbenzyloxy) -5-methyl-1 _t 3 ~ dioxane

A. Preparation of 2-ethyl ~ 5-methylene ~ 1,3 - dlo: ican

A mixture of 16.3 g of propionaldehyde, 20.2 g of 1-hydroxy-2-hydroxymethyl- 2: ~ propene, O ₁ 16 g of p-toluenesulfonic acid and 1200 ml of hexane were stirred under reflux for 2 hours, 5 »3 ml of water being collected in the Dean-Stark trap. The reaction mixture was then concentrated under reduced pressure to a volume of about 50 ml and then taken up in 200 ml of ether. The ether solution was washed with 75 ml of a 10% sodium carbonate solution and then twice with 75 ml of water. After drying over magnesium sulfate, the ethereal solution was concentrated under reduced pressure to give 26.5 g of a yellow oil. The crude product was fractionated under reduced pressure, 21.5 g of 2-ethyl-5-methylene-1,3-dioxane (boiling point 68 ° C / 41 mm Hg) being obtained. The NMR spectrum was consistent with the structure indicated. The synthesis was later repeated, according to which the refractive index of the

25 product was determined as follows: n _Q 1.4432.

^B · Production of 6-ethyl-1,5> 7-trioxaspiro / 2.5 / octane

5.0 g of 2-ethyl-5-methylene-1,3-dioxane, 4.1 g of benzonitrile, 4.3 g of potassium bicarbonate and 25 ml of absolute methanol. The mixture was then stirred at room temperature (25 to 30 ^° C.), 4 ml of 30% strength hydrogen peroxide being added dropwise over the course of 5 hours. After the addition was complete, the reaction mixture was stirred at room temperature overnight. To the rea-

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tion mixture was then added to 75 ml of water and the aqueous solution extracted three times with 40 ml of chloroform. The chloroform extracts were combined, initially with 40 ml of a 10% strength. Sodium carbonate solution and then washed with 40 ml of water and dried over sodium sulfate. The chloroform solution was concentrated almost to dryness under reduced pressure. The resulting slurry was filtered off and the solid material was washed with ether. The filtrate was then concentrated, whereupon 6.1 g of a clear. Fluid received. The NMR spectrum indicated that 50 % of the methylene compound had been converted to the epoxide, 95 % of which was the epoxide of the desired form. This crude product was combined with other material from a similar batch for distillation. Fractional distillation gave 4.8 g of a colorless liquid (b.p. 84-95 ⁰ C / 11 mm Hg), which was in accordance with the NMR spectrum of a mixture containing the desired epoxidized methyl compound. This crude product was combined with 10.0 g of a crude product prepared in a similar manner and fractionally distilled (spinning band column), 4.2 g of a colorless liquid (boiling point 90-91 ° C./11 mm Hg, ⁿ D ¹ >> 5O5) obtained which, by NMR spectroscopy, was essentially pure 6-ethyl-1 ^, y-trioxaspiro /^^./ octane. The product was distilled for analysis purposes again (boiling point 94 ⁰ C / 10 mm Hg, n ^ ⁵ 1.4505). The IR and NJIR spectra were consistent with the structure indicated.

Analysis: Calculated. C ₇ H ₁₂ O ₃ : C 58.31 »H 8.39; Found: C, 58.60; H 8.09.

C. Preparation of 2-ethyl-5-hydroxy-5-methyl-1,3-dioxane

7.6 g of 6-ethyl-1 ^^ - trioxaspiro / ^^ yoctane, 1.5 g of a catalyst (10 % palladium on activated carbon) and 75 ml of absolute ethanol were placed in a pressure flask and the mixture was hydrogenated at 25 ° C Lapse of one hour at a pressure of 3.16 kg / cm (45 psi). where 2.27 kg (5 pounds) of water

3.0bö 1 3 / Ί 1 97 · ■

substance have been included. The solution was filtered off and concentrated under reduced pressure, giving 6.8 g of a clear liquid which was taken up with 100 ml of ether, washed three times with 20 ml of water and dried over magnesium sulfate. The ether solution was then concentrated under reduced pressure to give 3.6 g of a clear liquid. The wash waters were saturated with sodium chloride and extracted three times with 50 ml of Xther. These ether extracts were dried over magnesium sulfate and then concentrated under reduced pressure to give 2.6 g of a clear liquid. The organic fractions were combined and fractionally distilled, 6.0 g of 2 ~ ethyl-5-hydroxy-5-methyl ~ 1,3-dioxane being obtained (boiling point 62 ° C / 10 mm Hg, n | p 1.4378) . The IR and NMR spectra were consistent with the structure shown and showed that the product consisted of 95% of the cis-isomer.

Analysis calc. C ₇ H ₁ ^ O ₃ I ^c 57.51 JH 9 * 6 $; found j C 57.80; H 9.39.

D. Production of 2-ethyl ~ 5- {2-methylbenzyloxy) -5-methyl- 1,3-dioxane ,

1.1 g of sodium hydride in 75 ml of dimethylformamide were stirred in a flask equipped with a stirrer, a dropping funnel, a thermometer and a reflux condenser with a drying tube, during which 5.9 g were added dropwise over 3/4 hour 2-Ethyl-5-hydroxy-5-methy1-1,3-dioxane in 25 ml of dimethylformamide was added. The mixture was then stirred for a further 11/2 hours and then 6.2 g of 2-methylbenzyl chloride were added and the mixture was heated to 90 to 95 ^° C. for 21 hours. The reaction mixture was then distilled to a volume of narrowed about 60 mm. The concentrated reaction mixture was then poured onto 200 g of ice and stirred until it had melted. A trace of a white solid was filtered off from the aqueous solution, which was then washed four times with 100 ml of Xther ex- *

309813/1197 *

was watered. The ether extracts were combined, dried over magnesium sulfate and concentrated under reduced pressure, giving 9.8 g of a yellow liquid. This product was taken up with 175 ml of ether and washed three times with 50 ml of water. The ether solution was dried over magnesium sulfate and concentrated under reduced pressure to give 8.4 g of an amber liquid. Fractional distillation gave 4.8 g of R-2-ethyl-c-5- (2-methyl-benzyloxy) -5-methyl-1,3-dioxane in the form of a colorless liquid (boiling point 82.5 C ⁰ / 0.14 mm Hg, njp 115075). The NMR and IR spectra were consistent with the structure shown and indicated that the product contained approximately 96 % pure c-isomer.

Example 12 5-benzyloxy-2- (2-füryl) -1,3-dioxane

A. Preparation of 2-benzyloxy-1,3-propanediol

A solution of 370 g of 5-benzyloxy-2-phenyl-1,3-dioxane and 35 ml of concentrated sulfuric acid in 750 ml of water and 1.2 liters of ethanol was refluxed for two hours. The ethanol was then evaporated under reduced pressure and benzaldehyde was removed as a by-product by steam distillation. The aqueous mixture was then saturated with potassium carbonate and the product extracted from the aqueous medium with ether. The ether solution was evaporated 'dried over MgSO ^ and concentrated under reduced pressure to give a solid product which after recrystallization from a benzene / Ligrain mixture 218 g of 2-benzyloxy-1,3-propanediol (F 38-39 ⁰ C ) resulted.

^B · Preparation of 5-benzyloxy-2- (2-furyl) -1,3-dloxane

A mixture of 18.2 g of 2-benzyloxy-1,3-propanediol, 9.6 g Furaldehyde and 4 g of an ion exchange resin in the H + form

3,098 13/1197 -

(Dowex 5OW X 8 resin) in 100 ml of benzene was refluxed until the theoretical amount of water (1.8 g) had formed. The water obtained as a by-product was distilled off azeotropically while boiling under reflux (2.2 ml of water being collected). After the ion exchange resin had been removed, the benzene solution was washed twice with 50 ml of a 1% ammonium hydroxide solution, dried over magnesium sulfate, filtered and evaporated under reduced pressure, 13 g of an oil being obtained. The oil was then distilled under vacuum, and were distilled over, the fractions at 128 to 13O ° C / 1O ~ ⁴ mm Hg (NJP 1.5412 and 1.5415 jXQ), collected in the form of an oil which to form 6 , 0 g of 5-benzyloxy-2- (2-furyl) ~ 1,3-dioxane (F 50-52 ⁰ C) crystallized out.

Analyzed calcd. C ₁₅ H ₁₆ O ^: C 69.21 j H 6.2 Oi found: C 69.44; H 6.00.

The NMR spectrum of the product indicated that it was a mixture of the cis and trans isomers in a ratio of was about 30j70, the cis shape having a cis configuration between the -OCHp - ^^ group and the furyl group. The separation of the isomers by fractionated Crystallization from hexane and benzene led to the pure cie compound (F 63-64 ° C).

Example 13 5-Benzylo3cy-2-chloromethyl-1,3-dioxane

A. 2-Benzyloxy-1,3-propanediol

A solution of 370 g of 5-benzyloxy-2-phenyl-1,3-dioxane and 35 ml of concentrated sulfuric acid in 750 ml of water and 1.2 liters of ethanol was refluxed for 2 hours. then the ethanol was evaporated under reduced pressure and the benzaldehyde obtained as a by-product by water

309813/1197 *

removed by steam distillation. The aqueous mixture was saturated with potassium carbonate and the product was extracted from the aqueous medium with ether. The ether solution was dried over MgSO ^ and concentrated under reduced pressure, giving a solid product which, after recrystallization from a benzene / ligroin mixture, 218 g of 2-benzyloxy-1,3-propanediol (F 38-39 ⁰ C).

^B. 5-Benzyloxy-2-chlororenethyl-1,3-dioxane

A mixture of 5.0 g of 2-benzyloxy-1,3-propanediol, 3.5 g of chloroacetaldehyde dimethyl acetal and 0.3 g of p-toluenesulfonic acid was placed in a three-necked round bottom flask equipped with a stirrer, thermometer and reflux condenser , heated from 25 to 130 ^{0 C in an oil bath.} In the course of the reaction, 63 % of the theoretical amount of the methanol obtained as a by-product was distilled off by distillation. The reaction mixture was then cooled to room temperature and dissolved in ether. The ethereal solution was washed with a 10% sodium carbonate solution and then with water. After drying over anhydrous sodium sulfate, the ether was stripped off under reduced pressure. Distillation of the crude oil gave 3.3 g of 5-benzyloxy-2-chloromethyl-1,3-dioxane (boiling point ^{100-105 ° C. / 0.025 mm Hg, n ^ 5} 1.5228). The NMR spectrum was consistent with the structure shown and showed that the product contained 30 % 5% of the cis isomer and the remainder the trans isomer.

Analysis: Calculated C ₁₂ H ₁₅ ClO ₃ : C 59.38; H 6.23i found. C 59.56; H 6.49.

. The preparation was repeated and the mixture of isomers was separated by column chromatography. The pure cis-isomer was in the form of a solid (F 38-39 ⁰ C) while the trans isomer was incurred as a liquid (NJP ■ 1.5200).

309 813/1197

f - 24 - ■ j

B e 1 a ρ ie 1 14 )

—— «t It IHI Il II Il II I

2-chloromethyl-5- (2-fluorobenzylosy ) -5-methyl-1,3-dloxane . '\

A. 2- (2-Fluorbengylo3ty) -2-methylmalonic acid ethyl ether /

To one in a 2 liter flask fitted with a stirrer, j

a thermometer, a dropping funnel and a reflux cooler j was fitted with a drying tube, a suspension of 20.2 g of sodium hydride f contained in 12 ml of anhydrous toluene was added over 45 minutes at a temperature of 25-30 ⁰ C 88.4 g 2-fluorobenzyl alcohol. The Reaktionsmi- / research was then heated to 1 1/2 hours at 90 ⁰ C. After the mixture had cooled, it was added in the course of 11/4 hours ^! at a temperature of 30 to 50 ⁰ C, 177.1 g of 2-Broa-2-methylmaloneäurediäthyleeter to. The reaction mixture then nurde 2 hours 90 bit 95 ⁰ C heated. After standing overnight at room temperature, the reaction mixture was introduced together with 500 ml of ether into a vessel containing 1 liter of a saturated sodium bicarbonate solution and 1 kg of crushed ice. After the ice had melted, the aqueous phase was separated off and extracted three times with 500 ml of ether. The ether solutions were combined, washed three times with 500 ml of water and dried by filtration over sodium sulfate. The separation of the ether and the remaining toluene (under reduced pressure) gave 176.2 g of 2- (2-fluorobenzyloxy) -2-methylmaloneIur © diethyl ester, the identity of which was determined by the IR spectrum.

B. 2- (2-fluorobenzyloxy) -2-methyl-1,3-propanedol

A dispersion of 19 g of lithium aluminum hydride in 600 ml of anhydrous Ether was in a 1 liter flask equipped with a stirrer, a dropping funnel and a reflux cooler Was equipped drying tube, introduced. This dispersion was added at a rate sufficient to

309813/1197 '

2243B85

to maintain reflux, 74.6 g of 2- (2-fluorobenzyloxy) -2-methylmalonic acid diethyl ester. After the addition, the reaction mixture was refluxed for 2 hours. The mixture was then cooled and the excess reducing agent was decomposed with a saturated sodium sulfate solution. 200 ml of ice water and 1 liter of 10% strength sulfuric acid were then added, the aqueous phase obtained was saturated with sodium chloride and extracted twice with 400 ml of ether. The ether solutions were combined, dried over Na ^ SO ^ and concentrated to give an oil. The remaining volatile materials were removed by distillation at a pressure of 0.01 mm Hg to give a solid which was recrystallized from a petroleum ether / chloroform mixture to give 17.8 g of 2- (2-fluorobenzyloxy) -2 -methyl-1;., 3-propanediol (F 72 "5-74.5 ⁰ C). A small sample of this material was recrystallized twice from carbon tetrachloride, white needles with a melting point of 75 to 76 ^° C. being obtained. The IR and NMR spectra were consistent with the structure indicated.

Analysis: calcd. C 1 H ^ i-FÖ * r C 62.66; H 7.06; Found: C, 62.63; H 7.21.

C. 2-Chloromethyl-5- (2-fluorobenzyloxy) -5-methyl-1,3-dioxane

A mixture of 8.6 g of 2- (2-fluorobenzyloxy) -2-methyl-1,3-propanediol, 6.5 g of chloroacetaldehyde diethylacetäl and 0.5 g of p-toluenesulfonic acid were in a 25 ml still heated. In the course of the reaction, 3.1 g of ethanol were removed by distillation. The warm residue was in 200 ml Benzene dissolved and the benzene solution was with 2 χ 50 ml a 10% sodium carbonate solution and twice with Washed 50 ml of water. The washed benzene solution was dried over Na2 $ 0 ^ and concentrated under reduced pressure, whereby a brown liquid was obtained. The isome-

3098 13/1197

ran were separated with the help of a column filled with silica gel (3 × 0 × 33 cm), the course of elution being followed by thin-film chromatography. The IeomerenmißChung was then applied with a small amount Petrollther to the column, followed by 250 ml of high-boiling Fetroläther (boiling point 65 to 11O ⁰ C) was run through the column. The isomers were then eluted with a petroleum ether / ethyl acetate mixture (99/1), 50 ml fractions (fractions 3 to 36) being collected. Fractions 16 to 20 gave, after the solvent had been separated off, a liquid which, with the formation of 3 »45 g of r-2-chloroethyl-t-5- (2-fluorobenzyloxy) -5-methyl-1,3-dioxane (boiling point 96-101 ° C / 0.13 to 9 × 10 * "* mm Hg) was distilled. After removal of the solvent, the fractions 22 to 36 gave a solid, which was recrystallized from low-boiling petroleum ether to give 5.3 gr ~ 2-chloromethyl-c-5- (2-fluoro-benzyloxy) -5-methyl-1,3-dioxane (F 42-44 ⁰ C) received a sample of the solid product was recrystallized for elemental analysis..

Analysis: Calculated. C ₁₃ H ₁₆ FClO ₃ : C, 56.83; H 5.87; found (t-isomer): C, 56.69; H 5.97; found (c-isomer): C, 56.58; H 6.05.

Example 15 2-chloromethyl-5- (2-methylbenzyloxy) -1,3-dioxane

A mixture of 124 g of chloroacetaldehyde dimethyl acetal, 92 g of glycerin and 1 g of p-toluenesulfonic acid was placed in a flask equipped with a stirrer, reflux condenser, Dean-Stark trap and thermometer. The mixture was then ^{heated to 80 to 85 °} C. until 76 ml of methanol had been collected and no additional methanol passed over. The solution was then cooled, neutralized with sodium carbonate and extracted with ether. the

309813/1197

Distance deβ ether under reduced pressure gave 151 g of a light yellow oil that was distilled and 108.5 g of 2-chloromethyl-5-hydroxy-1,3-dioxane (boiling point 78-80 ⁰ C / 0.15 mm Hg, 17, 1 % cis isomer).

30; 2 g of 2-chloroethyl-5-hydroxy-1,3-dioxane and 125 ml of toluene were placed in a flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. Then 8.6 g of 57% sodium hydride were carefully added in small portions with stirring. After the addition was complete, the slurry was stirred for 30 minutes at room temperature and then 37.0g of a-bromo-o-xylene was added dropwise. After this addition was complete, the reaction mixture was heated and refluxed for 3 hours. The cooled reaction mixture was washed twice with 100 ml of water and the organic layer was dried over sodium sulfate. The solvent was removed in vacuo to give 52 g of an oil which was distilled to give 33.1 g of a material boiling at 128 to 134 ° C / 0.15 mm Hg. This distillate was redistilled using a spinning band column to give 27.5 g of a distillate (boiling point 102 to 104 ⁰ C / 0.1 mm Hg) received. The residue contained in the distillation still crystallized upon cooling from (F 58-61 ⁰ C). After recrystallizing twice from benzene and ligroin, this residue gave 2.2 g of 2-chloromethyl-5- (2-methylbenzyloxy) -1,3-dioxane (F 62 to 63 ^° C.) which, according to NMR analysis, was 98 % out consisted of the cis isomer. The sample recrystallized for analysis purposes had a melting point of 63 to 63.5 ° C.

Analysis: Calculated. C ₁₃ H ₁₇ ClO ₃ : C, 60.82; H 6.82; Found: C, 60.84; H 6.66.

309813/1197

■■■ Ψ Κ ■■. ·? '■':

Example 16

5- (2-fluorobenzyloxy) -2- (methoxymethyl) -5-methyl * -1,3-dioxane j Into a 25 ml round bottom flask equipped with a stirrer and a / lurzweg distilling device was placed | 10.0 g of 2- (2-fluorobenzyloxy) -2-methyl-1,3-propaediol (prepared according to Example 10), 7.69 g of methoxyaetaldehyde f diethylacetal and 0.5 g of p-toluenesulfonic acid. The mixture was heated until no more ethanol was released y. (collected 4.1 g, theoretical amount 4.3 g). The contents of the flask were then dissolved in 200 ml of benzene, the solution was washed with an aqueous sodium carbonate solution, dried over sodium sulfate and concentrated under reduced pressure to give 12.7 g of a mixture of isomers V. The isomers were then determined by chromatography.

separated over a column filled with silica gel, wherein mixtures of petroleum ether and ethyl acetate (initially pure petroleum ether, then petroleum ether, which is mixed with ethyl acetate was added and finally a mixture of petroleum ether and ethyl acetate in a ratio of 90:10) as the eluent used, the occurrence of the isomers being followed by thin-layer chromatography.

The first fractions were combined and concentrated, giving 5.2 g of t-5- (2-fluorobenzyloxy) -r-2-methoxymethyl-5-methyl-1,3-dioxane (Boiling point 151 - 152 ° C / 1.5 mm Hg, njp 1.4920) received.

The later fractions were combined and concentrated to give 3.0 g of c-5- (2-fluorobenzyloxy) -r-2-methoxyfflethy; L-5-methyl-1,3-dioxane (F 31-32 ⁰ C). The IR and NMR spectra of the two products were consistent with the structure indicated.

Analysis: _calcd . C 1Zf H _ig FO _Zf : C 62.21; H 7.09?

found (t-isomer): C, 62.44; H 6.85J |

found (c-isomer): C, 62.25; H 6.85. · I

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Example 17 5-benzyloxy-2-methyl-2-phenyl-1,3-dioxane

A mixture of 18.2 g of 2-benzyloxy-1,3-propanediol, 12.1 g of acetophenone and 0.1 g of p-toluenesulfonic acid in 75 ml of benzene and 75 ml of toluene was heated in a Dean-Stark apparatus until Had collected 2.0 ml of water. The mixture was then washed twice with 75 ml of a 5 # aqueous sodium bicarbonate solution and finally with water. After drying over magnesium sulfate the solution was concentrated under reduced pressure to give 1.6 g obtained an oil which on standing crystallized to a solid (F 76-79 ⁰ C). Recrystallization gave 5-benzyloxy-2-methyl-2-phenyl-1,3-dioxane (F 87-88 ⁰ C). The IR and NMR spectra were consistent with the structure indicated. The NMR spectrum indicated that the material contained 50 % of the cis isomer and 50 % of the trans isomer.

Example 18

2,5-diethyl-5- (2-fluorobenzyloxy) -1,3-dioxane

Using the procedure described in Example 17, propionaldehyde and 2-ethyl-2- (2-fluorobenzyloxy) -1,3-propanediol were reacted using hexane as the solvent. After separation by column chromatography, r-2-ethyl-5-ethyl-t-5- (2-fluorobenzyloxy) .- 1,3-dioxane (boiling point 89-90 ° C./0.01 mm Hg, nj * ⁶ l) was obtained , 4895) and r-2 ^ ethyl-5-ethyl-c-5- (2-fluorobenzyloxy) -1,3-dioxane (boiling point 93 - 95 ° C / O, O1 mm Hg, n ^ ⁶ 1.4902) . The IR and NMR spectra were consistent with the structure indicated.

Analysis: Calculated. C ₁₅ H ₂₁ FO ₃ : C 67.14, · H 7f89j

found (t-isomer): C 67.05ϊ H 7.77 »

. found (c-isomer): C 66.91 »H 7.62.

3098 13/1197

. " ³⁰ ". 224368S

-. ■ 1.

Example 19

c - 5- (2-fluorobenzyloxy) -r-2- (2-cyanoethyl) -5-methyl-1,3-dioxane

To a mixture of 2.9 g of r-2- (2-chloroethyl) -c-5- (2 ~ fluorobenzyloxy ) -5-methyl-1,3-dioxane and 0.76 g of sodium cyanide in 2.9 ml of deionized water were given 0.076 g of tributylhexadecylphosphonium bromide and quickly heated the mixture to the reflux temperature where it was held for 4 hours. The mixture was then cooled and washed with 75 ml of diethyl ether extracted. The ether extract was washed with 3 x 25 ml of water, dried over magnesium sulfate and formed concentrated by 2.8 g of a yellow oil. The yellow oil was distilled and gave 2.4 g of c-5- (2-fluorobenzyloxy) -r-2- (2-cyanoethyl) -5-methyl-1,3-dioxane (Boiling point 132 ° C / 0.01 mm Hg, njp 1.5015). The IR and NMR spectra were available consistent with the specified structure.

Analysis: Calculated. C ₁₅ H ₁₈ FNO ₃ : C, 64.50; H 6.50; N 5.01; Found: C, 64.48; H 6.37; N 4.77.

Using the same procedure, r-2- (2-chloroethyl) -t-5- (2-fluorobenzyloxy) -5-methyl-1,3-dioxane was reacted with sodium cyanide in water in the presence of tributylhexadecylphosphonium bromide, whereby r -2- (2-cyanoethyl) -t-5- (2-fluorobenzyloxy) -5-methyl-1,3-dioxane (boiling point 133 ^° C. / 0.01 mm Hg).

Analysis: Calculated. C ₁₅ H ₁₈ FNO ₃ : C, 64.50; H 6.50; N 5.01; Found: C, 64.63; H 6.57; N 4.74.

Further herbicidally active compounds were prepared with the aid of the procedures described in the preceding examples and include the compounds given below:

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Example connection

20 cis-5- (3, ^ - dichlorobenzyloxy) -2-phenyl-1,3-dioxane, P 77 to 78 ° C; almost pure cis connection.

21 cis-5- (2-chlorobenzyloxy) -2-phenyl-1,3-dioxane, P 95 to 96.5 ° C; 85 % cis connection.

22 cis-SC ^ -Chlorbenzy loxy) ~ 2-pheny 1-1,3-dioxane, F 110 to 111 ° G; 87 % cis connection.

23 cis-5- (2, ¹ <-dichlorobenzyloxy) -2-phenyl-1 _s 3-dioxane,, F 116 to 117 ° C; almost pure cis connection *

2k 5- (3-methylbenzyloxy) -2-phenyl-1,3-dioxane, melting point 65 to 66.5 ° C; 51 % cis connection.

25 cis-5- (2,6-dichlorobenzyloxy) = 2-phenyl-l _i 3-dioxane,

F 90 to 92 ° C; 75 % cis connection. '.

26 cis -5 (3-chlorobenzyloxy) -2-phenyl-1,3-diQxane _J F 57 to 58 ° C; 87 % cis connection.

27 ■ cis-5- (3, ^ - dimethylbenzyloxy) -2-phenyl-1,3-dioxane _>

P 88 to 90 ^° C; 82 % cis connection.

28 cis -5 (3-fluorobenzyloxy) -2-phenyl-1,3-dioxane, F Sk up to 65 ° C; 79 % cis connection.

29 cis-5- ( ¹ * -fluorobenzyloxy) -2-phenyl-l _i 3-dioxane,

F 57 to 59 ° C; 69 % cis and 2 % trans compound.

30 cis ~ 5- (2,5-dichlorobenzyloxy) -: 2-phenyl-1,3-dioxane, F 76 to 77 ° C; almost pure cis connection. '

309813/1197

Example connection '

5- (2,3,6-trichlorobenzyloxy) -2-phenyl-1,3-dioxane ,. F 113 to 114 ⁰ C; 3 ^ -39 % ice and 61-66 % trans connection.

cls-5- (2,4-dimethylbenzyloxy) -2-phenyl-1,3-dioxane, P 93.5 to 9 ° C; almost pure cis connection.

eis-5- (2,5-dimethylbenzyloxy) -2-phenyl-1,3-dioxane, P 102 to 103 ° C; almost pure cis connection.

cis-5-Benzyloxy-2- (2-chlorophenyI) -I, 3-dioxane, P 100 to 100.5 ° Cj almost pure cis compound.

cis-5-benzyloxy-2 - (^ - chlorophenyl) -l, 3-dioxane, P 125 bis.126 ⁰ C; 95 % cis connection.

cis -5-benzyloxy-2- (3-chlorophenyl) -1, 3'-dioxane, melting point 85 to 85.5 ° C; 97 % cis connection.

cis -5 (3-fluoromethylbenzyloxy) -2-phenyl-1,3-dioxane, melting point 43 to 45 ° C; 84 % ice and 9 % trans connection.

cis-5- (2-cyanobenzyloxy) -2-phenyl-1,3-dioxane, 115 to 16 ° C; almost pure cis connection.

cis -5 (2-bromobenzyloxy) -2-phenyl-1,3-dioxane, melting point 93 to 94 ° C; 85 % cis and 31 % trans connection.

5- (4-cyanobenzyloxy) -2-phenyl-3,3-dioxane, m.p. 112 to 113 ° C; 66 % cis and 33 % trans connection.

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Example connection

^41:

Bp 180 to 190 ⁰ CZiQ * ' ⁵ mm Hg; 72 1 cis compound * cis-5-benzyloxy-2- (2 ~ broinphenyl) -i, 3-dioxane _>

Sdp, 210 to 215 ^O CZ10 ~ 5 mm Hg; almost pure ice connection.

5-Benzyloxy-2- (2-ethoxypheny1) -1,3-dioxanj bp. 180 to 185 ° CZ10 '" ⁵ mm Hg; 11 % cis- * 27 % trans compound and 62 % of the isomeric dioxolane.

5-benzyloxy-2- (2-methoxyphenyl) -1,3-dioxane _J 'bp 190 to 195 ⁰ CZ10 "" ⁵ mm Hg; 14 % cis compound, 31 % trans compound and 55 % of the isomeric dioxolane.

45 5-Benzyioxy-2- (2-fluorophenyl) ~ lj3-dioxane,

Bp 165-170 ° C / 10 " ⁵ mm Hg; 32 % ice compound

~ cis-5-benzyloxy-2- (3-bromophenyl) -l _i 3-dioxane, P 92-93 ⁰ G; almost pure cis connection "

dioxane »-F 68 to 69 ° C; almost pure cis connection.

cis-5-Ben _Z yioxy-2- (3-methylphenyl) -l, 3-dioxane _> F 68 to 70 ° C; almost pure cis connection.

cis-5- (2-fluorobenzyloxy) -2- (3-chlorophenyl) -l _> 3-dioxane _> F 85 to 86 ° C; almost pure cis connection. -,.

5- (2-methylbenziyloxy) -2- (3-chlQrphenyl) -l j3-

Sdp. 160 to 170 ⁰ CZlO " ¹¹ mm Hg; 18.Ϊ cis- ^ erbinden.

309813/1197

BtIspiel connection

5-benzyloxy-2- (3-benzyioxyphenyl) -1, 3-dioxane, P 77 to 78 ° C; 31 % cls connection.

5-benzyloxy-2- (3-methoxyphenyl) -1,3-dioxane,

Bp. 200 to 206 ⁰ CZ10 "* ¹ mm Hg; 37.2 cis-connection.

cis-5-benzyloxy-2-ethyl-1 _> 3-dioxane,

. B.p. 85-91 ° C / O _t O25 - 0.03 mm Hg "n ^ ⁵ 1.5050; 90 % cis connection,

cis-5- (2-Pluorbenzyloxy) -2-methyl-l-dioxane _{i t} 3 bp 70 to 7H ⁰ CZlO ^'1 * mm Hg. 90 Ji cis connection.

2-Methy1-5- (2-raethyIbenzyloxy) - !, 3-dioxane, bp. 110 to 114 ⁰ CZ10 "mm Hg; 60 % els and ήθ % trans compound.

56 c-5- (2-chlorobenzyloxy) -r-2-ethyl-5-wefchyl-l »3-dioxane, bp. 102 to 10% CZ0.0 <
96.5 % cis veneer.

. B.p. 102 to 104 ⁰ C / 0.0002 mm Hg; n ^ ⁵ 1.5186;

5- {2-FluorbenÄyloxy) -2- (2-furyl) -l, _3-l dioxaft F 50.5 to 52 ° C.

S | ■ ■ 2- (2-Puryl) -5- (2-Baethylbenzyioxy) -l _t 3 * 'tii "> iae _t f * 6" to 65 ⁰ C.

5-Benzyloxy-2-broiOTiethyl-1,3-diöxaii »

Bp. 130 to 133 ° G / iO nan Hg, κζ ⁵ |, 53? 5ϊ 30 Ϊ clB-connection '· ..' .. '.; ■, _: . ... .. '

309813 / 11Sf

Example . ^N connection

cS-Benzyloxy-r ^ -bromomethyl-S-methyl-1,3-dioxane, ν F 55 to 56 ^Q C; ·

L-1,3-dioxane ,. Bp. 116 to 119 ° C / Ji, 5 x 10 "ran Hg, n _D 1.5308.

c-5-Benzyloxy-r-2-chloromethyl-5-niethyl ~ 1,3-dioxane, F 50 to 51 ° C; ■ t-S-Benzyloxy-r ^ -chlorinethyl-S-methyl-1,3-dioxane, Bp. 88 to 112 ° C / 2 χ 10 mm Hg.

cis-2-chloromethyl 1- (2-fluorobenzyloxy) -1, 3-dioxane,. F 60 to 62 ° C; 9 * \% cis and 6 % trans connection.

r-2-chloromethyl-c-5- (2-methylbenzyloxy) -5-methyl-1,3-dioxane, F 57 to 5.8 ° C;

r-2-Chloromethyl-t-5- (2-methylbenzyloxy) -5-ynethyl-1,3-dioxane, b.p. 117 ° C / O, OO5 mm Hg, n ^ ⁵ 1.5175.

6H r-2-chloromethyl-c-5- (2-chlorobenzyloxy) -5-methyl-l, 3-

dioxane, F 53 to 5 ° C;

r-2-Chloromethyl-t-5- (2-chlorobenzyloxy) -5-ynethyl-1,3-dibx'an, b.p. 10 ^ to 10 7 ° C / 0, 02 mm Hg, n ^ ⁵ 1.5280.

r-2- (2-chloroethyl) -c-5- (2-fluorobenzyloxy) -5-methyl-1,3-dioxane, bp 120 ° C / 0.01 mm Hg, njp 1.5050; r-2- (2-chloro ^> ethyl) -t-5- (2-fluorobenzyloxy) -5-ynethyl-1,3-dioxane, b.p. 130 ° C / O, OO5 mm Hg, n ^ ⁵ 1.5026 .

5-benzyloxy-2-benzylΌxyInethyl-1,3-dioxane, n _ß 1,5 ^ 38; 28 % cis and 72 ί trans connection.

5-benzyloxy-2- (3-chlorophenoxymethyl) -1, 3 ^ ΰ n ^ 5 1.5587; ¹ JO % cis and 6 0 % trans connection.

309813/1197

BATH ORIGINAL

Example connection

c-5- (2-fluorobenzyloxy) -r-2-methyl-5-ynethyl-1,3-diQxane,

n ^ ⁵ 1.1939;

t-5- (2-fluorobenzyloxy) -r - ^ - methyl-S-wethyl-1,3-dioxane,

np ⁵ 1.11902.

c-5- (2-Pluorbenzyloxy) -r-2- (3-fluorophenyl) -5-niethyl-1,3-dioxane, F 86-87 ⁰ C; t-5- C 2-fluorobenzyloxy) -r-2- (3-fluorophenyl) -5 ~ methyl-1,3-dioxane, F 83, up to 84 ° C.

c-5- (2-fluorobenzyloxy) -5-methyl-r-2-thlenyl-1,3-dioxane, M 111 to 112 ° C; t-5- (2-Fluoro-benzyloxy) -5-methyl-r-2-thienyl-l, 3-dioxane, F 8k to 85 ⁰ C.

71 3- "Benzyloxy-1,5-dioxaspiΓo <f5.5 / undecan _t

O,

Bp. 120 to 121 ^U C / O, P5 mm Hg.

cis-2-Phenyl-5- (2-pyridyl) -methoxy-1,3-dloxane, P 95 to 98 ⁰ C.

cir, -2-phenyl-5- (2-thienyl) methoxy-l, 3-dioxane, F 68.5 to 69 ⁰ C.

c-5- (2-fluorobenzyloxy) -r-2- (2-furyl) -5-methyl-1,3 dioxane, m.p. 92.5 to 9.5 ° C; t-5- (2-fluorobenzyloxy) -r-2- (2-furyl) -5-methyl-l, 3 dloxan, F 67.5 to 69 ⁰ C.

75 5

dioxane, F 77 to 79 ° C

BATH ORIGINAL

309813/1197

Example_ _ ,._ " _. link

T6 5-Benzyibxy ^ _J 2-äiinethyl-i »3 äiöxan, ^ characterized by NMR spectrum.

r-2-Butyl-e-5- (2-fluorobenzylGxy) -5-methyl-i _> 3-dloxane, bp 105 ° C / ^{0.15 mm Hg, n ^ 5} 1.4865;

■ i »-.- 2-Butyl- ^ t-5- (2-fluorobenzyloxy) -5-methyl-1,3-aioxah, Sdp, 105 ^Q C / O _a ö5 mm Hg ^ n ^ ⁵ 1, 4840 »

^ r-2-tert-butyl-c-5- (2-fluorobehzyloxy) -5-methyl ~

1,3-dioxane, F 85-87 ° C;

r-2-tert-butyl-t-5- (2-pluorbenzyloxy) -5 "methyl-1,3-dioxane, P 50 to 52 ° C. \.

3- (2-Pluorbenzyloxy) -3-methyl-1,5-dioxaspii-o / 5.57 ^un deean, bp 170 to 174 ^o C / 0.03 mm Hg, ii ^ ⁵ 1.5081.

5-butyl-r-2-ethyl-c-5- (2-fluorobenzyloxy) -l, 3 'dioxane, b.p. 122 ° C / _I O O25 mm, n 1.4860 ^ ^_5.!; 5-Butyl-r-2-ethyl-t-5- (2-fluorobenzyloxy) -1,3-dioxane, b.p. 107 to 110 ^G C / 0.02 mm Hg, n ^ ⁵ 1.4855.

c-5- (2-Pluorbenzyloxy) -5-methyl-r- ⁱ 2-phenyl-1,3-dioxane, M 51.5 to 52.5 ° C; almost pure cis connection.

c-5 " (2-pluorbenzyloxy) -r-2-hexyi-5-methyl-1,3-dioxane, bp. 124 ° C / O, O3 ram Hg, n ^ ⁵ l, 4835i almost pure cis compound.

c-5- (2-Pluorbenzyloxy) -5-methyl-r-2 ^ propyl-1,3-dioxane, Sd ^. 98 to 100 ^o C / 0.015 mm Hg, n ^ 1.4870; almost pure cls connection. "'".'-

309813/1197

Example . link

r-2-ethyl-5-ethyl-c-5- (2-niethylbenzyXoxy) rl, 3-. dioxane, bp 103 ° C / 5.5 x 10 ~ ⁵ mm Hg, n ^ ⁵ 1.5090; 88 % cis connection.

85 c-5- (2-chlorobenzyloxy) -r - 2-ethyl-5-ethyl-1,3-dioxane, bp, 112 to 118 ° C / 2.2 χ 10 "^ mm Hg ,, ^ 1, 5198; 90 Seis connection.

86 c-5- (2-chlorobenzyloxy) -r-2- (2-cyanoethyl) -5-ethyl-1,3-dioxane, P 77 to 78 ° C; almost pure ice connection.

c-5-benzyloxy-r-2-ethyl-5-methyl-l, 3-dioxan _l b.p. 113-114 ° C / O, 19 mm Hg, 1.5097 NJP. almost pure cis connection.

c-5-Benzyloxy-r-2-ethyl-5-ethyl-1 _t 3-dioxane, bp 101 to 106 ⁰ CZlO " ¹¹ ram Hg, n ^ ⁵ 1.5025; almost pure cis compound.

309813/1197

B e i ε ρ ie 1 89

Investigation of the herbicidal pre-emergence and post-emergence effects of substituted 5-benzyloxy-1,3-dioxanes:

To determine the herbicidal effect of the substituted 5-Benzyloxy-1,3-dioxane was that described in Example 1 Procedure Used * Doses of 4.48 and 6.72 kg / ha were used. The results of the pre-emergence underestimation are summarized in Table II and the results of the post-emergence investigation in Table III:

3 0 9 8 13/1197

TABLE II

Herbicidal pre-emergence effects of substituted 5-benzyloxy-1,3-dioxanes

(percentage destruction with the dosage used) Combination of additional dosage * test plants

game 3 kg / ha A. B. C. D. E. P. G 5 6.72 0 0 0 0 100 100 0 6th 6.72 100 20 ^b 100 100 7th 6.72 100 o ^a 100 100 8th 4.48 100 0 100 100 0 9 4.48 ** 100 0 100 100 0 10
c-isomer 6.72 ** 100 30 ^b 100 ₉₅ a 10
t-isomer 4.48 75 " 100 o ^b o ^b 100 11 Μβ *
0 o ^b 0 0 10 ^b 12th
pure cis isomer 4.48 75 ^a 100 o ^b o ^b 100 13th 4.48 100 o ^b 100 100 0 c-isomer * 1, IU 100 o ^b 100 90 ^a 0 . 15th
cis isomer 4.48 75 ^b 100 o ^b o ^b 100 16
c-isomer 4.48 70 ^a o ^b 100 100 o ^b 17th 4.48 o ^b 100 0 o ^b , 100 18th
c-isomer 4.48 ** 0 o ^b 70 ^b 50 " 0 4.48 100 100 o ^b o ^b 100

309813/1197

TABLE II (Porting):

link
of example Dosage*
kg / ha _A B. Test plants _t D. E. F. G 19th
c-isomer 4.48 0 ^bc 100 C. o ^bc . 100 ft 19th
t-isomer 4.48 _o bc 100 _o bc _o bc 80 ^a 25th 6.72 20 ^b O 0 0 100 100 33 6.72 0 0 T5 ^b 75 ^b 36 6.72 0 100 0 100 100 0 39 6.72 ** 100 o ^b 100 100 41 6.72 .. 100
t o ^b 100 80 ^a .45 6.72 O 100 0 100 47 4.48 60 ^a 0 8o ^a 100 0 '48 4.48 80 ^a 20th 100 100 0 49 4.48 .100 0 100 95 ^a 0 50 4.48 ** 20 ^a Ö ' 100 100 0 51 4.48 ** o ^b o ^b 0 50 ^a 50 ^a 0 52 4.48 ** 100 O 1Ό0 100 0 53 4.48 ** 100 o ^a 100 100 0 54 - 4.48 ** 100 o ^b 100 100 0 55 4.48 ** 100 o ^a 100 100 0 56 4.48 100 o ^b . 100 57 4 _# 48 100 o ^b 100 100 Q ^b 58 4.48 70 ^a o ^b 100 90 ^a o ^b 59 ■ 4.48 ** 100 o ^b ■ 100 100 0 60 4.48 '■ 100 o ^b 100 100 0 c-isomer

309813/1197

TABLE II (continued):

link
of example Dosage*
kg / ha A. B. Test plants D. E. P. G 61
c-isomer 4.48 100 C. o ^b 100 100 0 61
t-isomer 4.48 0 0 0 0 0 62
cis isomer 4,4.8 100 o ^b 100 100 0 63
c-isotneres 4.48. o ^b 100 o ^b 100 64
e-isomer 4.48 0 ^b 100 0 ^b o ^b 100 65
c-isoraeres 4.48 o ^b 100 0 ^b o ^b 100 66 4.48 ** 20 ^a 0 ^b 0 100 70 ** 0 67 4.48 ** 40 ^a 0 90 ^a 30 ^a 0 c-isoraeres 4.48 50 ^b 100 o ^b 100 69
c-isomer 4.48 0 100 0 ^b o ^b 100 70
q isomer 4.48 o ^b 100 o ^b ■ o ^b 100 • ■ ■ ₇ i 6.72 0 100 o ^b * o ^b 100 100 72 4.48 100 0 100 50 ^a 0 73 4.48 100 o ^b 100 100 0 74
ο-isomer 4.48 30 ^b 10.0 o ^b 100 75 4.48 0 100 o ^b o ^b 100 "" Vy 6.72 0 80 ^b 0 0 60 ^b 77
c-isomer 4.48 o ^b 100 0 0 100 78
c isomer 4.48
Ah. λ 0 .100 o ^b 0 100 0

309813/1197

TABLE II (continued):

2243885

Link. Dosage * of example kg / ha

Test plants

JD

79

. 80 '
c-isomer

8.1
82

83.

85
86

87 88

"8th 48

100

O ¹

O ¹ O ¹ O ¹ 0

30 ^a ■ 0 ^b

100 '

o ^b

100 100 100 100 100 100

O ¹
0 ^!

O
O

ο ¹ ο ¹ ο ¹

100

30 ^pounds

100

100 100 100 100 100 100

100

The plants examined are:.

A - green beans,

B - corn,. -

C - green salad,

D - mustard,

E - fingergrass.,

F - Chicken iret. and

G - cotton.

* The dosage is calculated without taking into account the cis content, as indicated in each example.

** The dosage is that of the applied cin isomer.

a The surviving plants have been severely damaged likely not to recover.

b The surviving plants are damaged, but will probably recover.

c The plants bind strongly inhibited in their growth.

3098 13/1197

BATH ORIGINAL

TABLE III

Herbicidal post-emergence effects of substituted 5-benzyloxy-1,3-dioxanes

(percentage destruction with the dosage used),

Connection of dosage * example

Test plants

CO CJO

10 12 13 18

; / xia Corn mustard Finger-
grass Chicken
millet tree
wool 6, 72 0 0 0 ^a 0 ^a 6 * 72 0 ^a 0 100 100 H, 48 100 o ^b 100 100 •. "0 ^b 6> 72 **. o ^b
o ^b 0
0 60 ^a
20 ^b 20 ^b
80 ^b ή, 48 - .100 0 100 100 o ^b 6, 72 ■ Q o ^a io ^b

des cis-Oebml ^ es, as he is in

* The dosage is given without any example being given.

** The dosage is that of the applied cis-Ieomer.

a The surviving plants are badly damaged and likely will not recover-

b The surviving plants are damaged but are likely to recover.

For herbicidal use, the active 1,3-dioxanes are mixed in herbicidally effective amounts with adjuvants and carrier materials normally used to facilitate the dispersion of the active ingredients for agricultural use, taking into account the fact that the formulation and the The type of application of a toxin can influence the activity of the material at a given application farm Application form. Preferred formulations for both herbicidal pre-emergence and post-emergence application are wettable powders, emulsifiable concentrates and granules. These formulations can Q _t J? contain up to 95 wt., -9 & or more of the active ingredient «

The wettable powders are in the form of finely divided particles that are easily dispersed in water or another dispersant. The wettable powder is applied to the ground either in the form of a dry stagnation or dispersed in water or other liquid. Typical substrates for wettable powders include filler soil, kaolin clays, silicas, and other readily wettable organic or inorganic diluents. The wettable powders are usually formulated in such a way that pie about to £ 9 wt% -2 ^ of the active ingredient and for relief; cter wetting the dispersion contain a small amount of a wetting, dispersing or emulsifying agent * Si ««. Example contains a wettable powder nützliciiee 8Q ₁ Q öew "-feile the active DiQxans" IIT ₁ S-Qew. parts of Palmetto fon and ßew as a wetting agent 1.0, -feile Natriumlig ^ insulfonat and CU3 wt * -feile a sulfonated, aliph ^ these polyesters.

The emulsifiable concentrates are homogeneous liquid compositions which can be dispersed in water or another liquid carrier material and which consist exclusively of the active dioxane, either together with a liquid or solid emulsifying agent, or which in turn contain a liquid carrier material such as xylene, aromatic heavy raw gasoline, May contain isophorone or other non-oil-free organic solutions. For herbicidal use, these concentrates are dispersed in water QiItI * another liquid carrier material and normally sprayed onto the area to be treated. The percentage by weight of the active ingredient may vary depending on the form of use, but generally makes up from 0.9 to 95% by weight of the herbicidal composition. fun example containing a suitable emulsifiable concentrate IN) ₁ O parts by weight of active dee dioxanes, 75 parts by weight and 5 56 HmiiSeWrdrbfnzol _f 0 parts by weight of sulfated ethoxylated nonylphenol.

The granules, which contain the poison on relatively coarse particles, are usually applied without dilution to the area in which the vegetation is to be suppressed. Typical carrier materials for the granules include sand, Fuller-Brd®, bentonite clays, vermiculite, perlite IHIi other organic "or inorganic materials that can absorb or be coated with the toxin." The granules are normally produced in such a way that they contain about 5 bla 25% of the active ingredient and these materials can also contain small amounts of other ingredients, such as surface-active agents, wetting agents, dispersants or emulsifiers, oils such as heavy aromatic petroleum, kerosene or other petroleum fractions or vegetable Contain oils and / or adhesives, such as bextrins, glue or synthetic resins. The average particle size of the granules is normally between 190 and 2400 / U. For example contains

308113/1197

a suitable granule formulation 5.05 parts by weight of the active dioxane, 5.00 parts by weight of corn oil and 89.95 parts by weight crushed corn on the cob.

Typical wetting, dispersing or emulsifying agents for the formulations used in agricultural operations include, for example: alkyl and alkyl aryl sulfonates and sulfates, and the sodium salts of these compounds, ethoxylated alcohols, ethoxylated Alkyl phenols, sulfonated oils, ethoxylated fatty amine salts, fatty acid esters of polyhydric alcohols and other types surfactants, many of which are commercially available are including the anionic, nonionic, cationic and amphoteric representatives of these materials. The surfactant, when used, normally constitutes 1 to 15% by weight of the herbicidal Composition from.

Dusts in the form of free-flowing mixtures of the active ingredient with finely divided solids, such as talc, clays, flours and other organic or inorganic solids, which serve as dispersants and carrier materials for the toxin make useful formulations that can be worked into the soil. The finely divided Solids have an average particle size less than about 5Q / U.

For special purposes, pastes can be used that homogeneous suspensions of a finely divided solid toxin in a liquid carrier material such as water or oil. These formulations usually contain about 5 to 95 wt .-% of the active ingredient and can also be used for To facilitate dispersion, contain small amounts of a wetting, dispersing or emulsifying agent. When applying ^ In addition, the pastes are usually diluted and sprayed onto the area to be treated. . .- ·, ..: ...

309813: / 11 97, Λ

Other useful formulations for the herbicidal compositions include simple solutions of the active ingredient in a dispersant, in which this is mixed with the desired Concentration is completely soluble, such as acetone, alkylated naphthalenes, xylene or other organic Solvent. It can also be pressurized Sprays, i.e. typically aerosols, are used in which the active ingredient in finely divided form Evaporation of a low-boiling dispersant, as Solvent-acting carrier material, such as a freon » is dispersed.

Typically, the herbicidal compositions in the solid state (e.g. the wettable powders, the dusts or the granules) are packed in paper (or plastic) bags, which are e.g. 0.91, 2.27, 4.54 or 6.80 kg (2nd , 5, 10 or 15 pounds) of the herbicidal composition, and which are provided with the instructions for use. Liquid herbicidal compositions (eg, _o emulsifiable concentrates or pastes) are (1 quart or 1 gallon) normally in solid container, for example, O, '951 Ltr. Or 3.79 liters. Accommodation, similar for example in jars or cans, in which Way are provided with instructions for use. The herbicidal compositions of the invention can be packaged in a similar manner.

309813/1 19 7

Claims (1)

PATENT CLAIM E 1. Substituted dioxanes of the general formula O - CKo. O - CH ₉ - R ^{r 2} \ / " Q - CH ₂ in which 2 - R- denotes a hydrogen atom, an alkyl group, a haloalkyl group, a cyanoalkyl group, an aryl group, an aryloxyalkyl group, an arylalkoxyalkyl group or an alkoxyalkyl group, the alkyl groups or the substituted alkyl groups containing 1 to 6 carbon atoms and the aryl group being unsubstituted or having a substituent X. , which may be a fluorine atom, a chlorine atom, a bromine atom, a low molecular alkyl group, a low molecular alkoxy group or a benzyloxy group, substituted phenyl group, furyl group or Is thienyl group, 2 ^a R represents a hydrogen atom or a methyl group 2
or together with the group R can form two or more methylene groups and thus a spiro grouping, Rr is a hydrogen atom, an alkyl group, a chloroalkyl group or a bromoalkyl group with 1 to β carbon atoms, 309813 / 1t9? 2243665 R ^{r is} an unsubstituted or substituted by 1, 2 or 3 substituents T, which can be fluorine atoms, chlorine atoms, bromine atoms, cyano groups, CF groups, low molecular weight alkyl groups or low molecular weight alkoxy groups, monovalent aromatic phenyl ™, furyl, thienyl or pyridyl group mean, with the proviso that if the group R ^{r is} an unsubstituted phenyl group, the group R is a hydrogen atom and the group R is a hydrogen atom or a methyl 2
group, the group R is different from an unsubstituted phenyl group and the -OCH ₂ -R ^r group in cis-X configuration to any one of hydrogen - ■ '■■■' ■■ 2 ■ ' -whose group R is. - ..... 2. Compounds according to claim 1, characterized in that the group R ^{r is} a phenyl group or a phenyl group which in an ortho position has at least • inen substituents other than hydrogen. 3 / Compounds according to claim 2, characterized in that the phenyl group in the ortho position has a 'Q: fluorine substituent. '■■ ^ 4 »Connections according to claim 2, characterized in that that the phenyl group in the ortho position carries a 'chlorine substituent. 5. Compounds according to claim 2, characterized in that the phenyl group in the ortho position is one Carries methyl substituents. 6. Compounds according to claim 1 _r characterized 'indicates that' the group R is an alkyl group, a haloalkyl group or a cyanoalkyl group with 1 to 4 carbon atoms off atoms, a phenyl group or a phenyl group which 309813/1187 2243885 one of YTasser substance different substituents in the has meta position, Compounds according to claim 6, characterized in that the group R is an ethyl group. 8. Compounds according to claim 6, characterized p
indicates that the group R is a chloromethyl group or a 2-chloroethyl group. , .. "■"'-, 9. "- Compounds according to claim 6, characterized in that the substituent other than hydrogen is a fluorine atom. ■ 10. Compounds according to claim 1, characterized in that that the group R is a hydrogen atom. 11. r-2-Ethyl-5-ethyl-c-5- (2-fluorobenzyloxy) -1,3-dioxane. 12. r - ^ - Ethyl-S-ethyl-c-S- (2-methylbenzyloxy) -1,3-dioxane. . 13. c-5- (2-chlorobenzyloxy) -r-2-ethyl-5-ethyl-1,3-dioxane. . cis -5r benzyloxy-2- (3-fluorophenyl) -1,3-dioxane. 15. cis -5 (2-fluorobenzyloxy) -2- (3-fluorophenyl) -1,3-dioxane. cis -5-benzyloxy-2-ethyl-1,3-dioxane. 30 9813/1197 17. cl8-5-Benzyloxy-2-chloromethyl-1,3-clioxane. 18. cis -2-chloroethyl-5- (2-fluorobenzyloxy) -1,3-dioxane. 19. cis -5-Benzyloxy-2-bromomethyl-1,3-dioxane. 20. c ~ 5-Benzyloxy-r-2-bromomethyl-5-methyl-1 _f 3- (iioxane. \. '■ · ■■■ 21. r-2-Chloromethyl-c-5- (2-fluorobenzyloxy) -5-methyl-1 _f 3-dioxane. 22. r-2-Ethyl-c-5 ~ (2-fluorobenzyloxy) -5-methyl-1,3-dioxane. i 23. c-5- (2-Fluorobenzyloxy) ~ 5-methyl-r-2-phenyl-1,3-dioxane. 24. r-2-Ethyl-c-5- (2-methylbenzyloxy) -5- methyl-1,3-dioxane. 25. c-5- (2-chlorobenz3 »-ioxy) -r-2-ethyl-5-methyl-1» 3-dioxane. 26. c-5- (2-Pluorbenzyloxy) -5-methyl-r-2-propyl-1,3-dioxane. ^v 27. r-2-Butyl-c-5- (2-fluorobenzyloxy) -5-methy1-1,3-dioxane. 28. r-2-tert-butyl-c-5- (2-fluorobenzyloxy) -5-diethyl-I 1 _t 3-dioxane. 309813/1197 29. c-5- (2-fluorobenzyloxy) -r ~ 2-methoxymethyl-5-methyl-1,3-dioxane ". · 30. c-5- (2-Fluorobenzyloxy) -r-2- (3-fluorophenyl) -5-methyl-1,3-dioxane. 31. r-2- (2-chloroethyl) -c-5- (2-fluorobenzyloxy) -5-methyl-1,3-dioxane. 32. r-2- (2- cyanoethyl) -c-5- (2-fluorobenzyloxy) -5-methyl-1,3-dioxane. 33. 5-Butyl-r-2-ethyl-c-5- (2-fluorobenzyloxy) -1,3-dioxane. 34.. c-5- (2-chlorobenzyloxy) -r-2- (2-cyanoethyl) ~ 5-ethyl-1,3-dioxane. 35. cis -5 (2-fluorobenzyloxy) -2-phenyl-1,3-dioxane. 36. cis -5-Benzyloxy-2- (2-furyl) -1,3-dioxane. 37. cis -2-chloromethyl-5- (2-methylbenzyloxy) -1,3-dioxane. 38. c-5-Benzyloxy-r-2-ethyl-5-ynethyl-1,3-dioxane. 39. c-5-Benzyloxy-r-2-ethyl-5-ethyl-1,3-dioxane. 40. Herbicidal compositions, characterized in that · they (a) a compound as an active ingredient in a herbicidally effective amount according to claims 1 to 39 and (b) contain an inert carrier material suitable for agricultural purposes. 309813/1197 41. Herbicidal compositions according to claim ¹ IO, characterized in that in the cases where the group 2 · R is different from hydrogen, the cis compound in an amount is present which is at least as large as the amount of the corresponding, if present, present trans isomers of the compound. 42. Herbicidal compositions according to claim 39 » 2 characterized in that in the cases where the group R is different from hydrogen, the cis compound in an amount is present which is at least twice as large as the amount of the corresponding, if present, present trans isomers of the compound. 43 herbicidal compositions according to claim 39, characterized in that in cases where the group ο
R is different from hydrogen, the cis-compound is present in an amount which is at least three times as great as the amount of any trans-isomer of this compound. 44. methods of controlling undesired plant growth, characterized in that a herbicidal amount of a compound according to the claims is applied to the soil to be treated 1 to 39 applies. 45 · Process for the preparation of the compounds according to Claim 1, characterized in that one (a) either (1) a substituted 5-hydroxy-l, 3-dioxane of the general ! my formula 309813/1197 R ² O-CH ₂ OH IT 0 - CH ₂ RV 2 2 ^a 5 wherein the substituents R, R and R are in claim 1 have given meanings, in a solvent with sodium hydride with training of the corresponding sodium alcoholate which is then reacted with an aryl methyl chloride or bromide the general formulas R ^r -CH ₂ -Cl or R ^r -CH ₂ -Br, wherein the group R ^{r has} the meanings given in claim 1, converts or ^! (2) a 2-arylmethpxy-1,3-propanediol of the general Formula. R ^r -CH ₂ -0-CH- (CH ₂ OH) ₂ wherein the group R is those given in claim 1 Has meanings with a carbonyl compound of the formula 2 2 ^a
ΒΓΈΓ C = O 2 2 ^a wherein the groups R and R are those given in claim 1 Have meanings, and reacts in the presence of an acidic catalyst (b) separating the product from the reaction mixture. 46. The method according to claim 44, characterized in 309813/1197 net that a product is separated off from the reaction mixture which contains a major proportion of the cis-isomer. 309813/1197