DE2739067A1 - 1,3-DIOXANES, PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS HERBICIDES - Google Patents

Description

"1,3-Dioxanes, process for their preparation and their use as herbicides ^B

The invention relates to new 1,3-dioxanes, processes for their Production, herbicidal compositions containing these compounds and their use as pre-emergence and post-emergence herbicides,

Herbicides substituted in the 2- and 5-positions of the dioxane ring 1,3-Dioxanes are already known. Furthermore, there are 5-substituted 1,3-dioxanes which are unsubstituted in the 2-position are known. In the 1,3-dioxanes described so far, the 4- and 6-positions are therefore unsubstituted.

It has now been found that by substituting the 4-position or the 4- and 6-positions of known herbicidal 1,3-dioxanes, e.g. with a lower alkyl radical, their herbicidal Effectiveness can be maintained and promoted. The new 4-substituted 1,3-dioxanes have compared to the known 4-unsubstituted dioxanes an unexpectedly high herbicidal activity.

The invention relates to herbicidally active 1,3-dioxanes of the general formula I (in which the numbering of the substituents R indicates the position in the 1,3-dioxane ring)

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in which R is a hydrogen atom or an alkyl, haloal

2 'denotes kyl, cyanoalkyl, alkoxyalkyl or phenyl radical, R

2 * 2 is an atom of water or combine R and R to form a spiroalkane structure represent a zv / polyvalent polymethylene group with 2 to 6 carbon atoms, R an alkyl, Means haloalkyl, cyanoalkyl or alkoxyalkyl radical,

4 · 5

R is a hydrogen atom, R is a hydrogen atom or a Is an alkyl radical, R is a hydrogen atom or an alkyl, Represents haloalkyl, cyanoalkyl or alkoxyalkyl radical, R is a hydrogen atom, R is a phenyl, puryl, pyridyl or is a thienyl group, X is a chlorine or fluorine atom or is a methyl group and η is 0, 1 or 2.

In preferred compounds of the invention, the alkyl component contains the substituents R, R or R 1 to 4 carbon

2 atoms. Particularly preferred are compounds in which R is a hydrogen atom or a methyl, ethyl, propyl, isopropyl, chloromethyl, bromomethyl, cyanomethyl, 2-cyano

2 '

Means ethyl or methoxymethyl group, R is a hydrogen atom, R is a methyl, ethyl or propyl group, R ^ is a hydrogen atom, R is a hydrogen atom or a methyl, ethyl or propyl group, R ^{r is} a phenyl group and η den Value 0, 1 (where X is in the 2-position of the phenyl ring) or 2 (where X is in the 2- and 6-position of the phenyl ring).
35

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R ⁴ H R ⁶ (a) alkyl alkyl H (b) alkyl H B. (C) alkyl alkyl alkyl (d) alkyl alkyl

4 »6 · 4

While H and R are always hydrogen atoms and R is always

e 6

is an alkyl radical, R and R, independently of one another, can be hydrogen atoms or alkyl radicals. The following four possible combinations are therefore possible:

theor. number of stereo! someren

If R is taken as a reference group, the benzyloxy, Furylmethoxy, pyridylmethoxy or thienylmethoxy group in the 5-position either axial (cis) or equatorial (trans) be oriented. Palls R and R are alkyl radicals, these can also be either axial or equatorial to the reference be group oriented. The number of possible stereoisomers is far greater than the number of possible substitutions. There are four possible stereoisomers for (a), for (b) all possible stereoisomers, for (c) six possible stereoisomers and for (d) six possible stereoisomers. If thus probably for the four substitution isomers (a), (b), (c). and (d) 20 stereoisomers are conceivable, are due to spatial reasons or due to equilibria that a certain Promote orientation, not all can be produced. In addition, optical isomers are possible because the dioxane molecules have asymmetrical centers.

Particularly preferred herbicides are compounds in which the 5-benzyloxyl, furylmethoxy, pyridylmethoxy or Thienylmethoxy group is to the 2-substituent. Particularly preferred herbicides are compounds in which both the 4-substituent as well as the 5-substituent (e.g. the benzyl

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1 oxy group) are related to the 2-substituent.

The stereochemistry of derivatives of 5-hydroxy-1,3-dioxane has already been discussed in the literature; See, e.g., Baggett et al, J. Chem. Soc. Pp. 2574 (1960) and Dobinson and Foster, J. Chem. Soc. P. 2338 (1961). According to this, one speaks of a cis position between the 5-substituent and the 2-substituents when the 5-substituent is in the axial position and the 2-substituent is in the equatorial position - information The NMR spectra in particular provide information on the structure. For example, an NMR analysis of 2,5-dialkyl-5-hydroxy-1 is known from the patent literature , 3-dioxanes known. Gelas, Bull. Soc. Chim. For example, France (1975) Vol. 5-6, pp. 1237-1242 is one NMR analysis of an isomer mixture of 2,4-dimethyl-5-hydro-

15 xy-1,3-dioxane described.

The preparation of the compounds according to the invention and the intermediates for their preparation are explained in more detail in the following examples. “Reduced pressure ¹¹ is understood to mean the pressure normally achievable with water jet pumps.

The isomerization of hydroxylated dioxolanes and dioxanes by selective distillation in acidic media is at

J. Gelas, Bull. Soc., Chim. France (1970) vol. 11 ,. 4041- ^ 4046. This process is used to prepare an alcohol precursor of the compounds according to the invention; r-2-ethyl-cS-hydroxy ^^ - methyl-i, 3-dioxane ·. The preparation of a mixture of erythro- and threo-1,2,3-butanetriols from a mixture of cis- and trans-crotyl alcohols and its subsequent reaction with acetaldehyde to form an isomer mixture of dioxolanes and 2,4-dimethyl-5-hydroxy-1 , 3-dioxanes is available from Gelas, Bull. Soc. Chim. France (1975) Vol. 5-6, Si 1228-1236. These reactions run after

³⁵ following scheme:

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_R * H KMnOi. R * OH OH H

^ r "^Ha0>> - ^c \

Cataly- H ^X ^ CH ₂ OH

trans- 2-Alken-l-ol ^s | $ ° ^r thre ^ -1,2,3- alkanetriol

^{5 C} (D

OH

1) condensation &

2) De3tillation ~ ^ / _Λ / _π *

——————— ^ —— ^ I Π R

acid '/ ^Η

Manufacture of the intermediate products
A ¹ . threo-1 .2. 5-3utantriol

A stirred mixture of 12.5 g of trans-2-3uten-1-ol and 0.5 g of 2,3,11,12-dicyclohexyl-1,4,7,10,13,16-hexaoxacyclooctadecane ("Dicyclohexyl-IS-crovm-ö") in 125 ml of water is on Maintained 5 ° C and kept at this temperature for 1/2 hour while adding 32.88 g of potassium permanganate. After finished In addition, the temperature of the mixture is allowed to rise to room temperature and the mixture is stirred for a further 2 1/2 hours. The reaction mixture is then filtered and the filtrate evaporated under reduced pressure until a viscous liquid remains. The residue is distilled using a short path still, leaving 6.13 g of clear viscous threo-1,2,3-butanetriol, b.p. 97 to 99 ° C / 0.02 up to 0.25 torr. The assumed structure is confirmed by the IR and NMR spectra.

analysis for C ₄ H 10 ° 3 ^: 45 C. 9 H ber .: 45 , 27; 9 , 50 found: .54, , 58

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no

¹ A. rZ-Ethyl-c - ^ - hydroxy-cA-methyl-i.3-dioxane

A solution of 23.26 g of propionaldehyde, 42.56 g of threo-1,2,3-butanetriol and 0.93 g of ρ-toluenesulfonic acid in 750 ml of hexane is stirred for 1 to 2 hours at room temperature and then kept at reflux temperature for 16 hours, 6.40 ml of water distilling off azeotropically from the mixture, the theoretical amount in the acetalization with the triol is 7.23 7.23 ml). The reaction mixture is cooled to room temperature, a further 3.0 g of propionaldehyde are added and the mixture is refluxed for 2 hours, the remainder of the calculated amount of water being distilled off azeotropically. The reaction mixture is then cooled and washed three times with 75 ml of saturated sodium bicarbonate solution each time and four times with 75 ml of saturated sodium chloride solution each time. The organic layer is then dried with sodium sulfate and filtered, and the filtrate is evaporated under reduced pressure to give 34.76 g of a yellow liquid. The sodium bicarbonate and sodium chloride washing solutions are extracted three times with 200 ml of diethyl ether each time , whereupon the ether phases are combined, twice with

²⁰ per 75 ml of saturated sodium chloride solution washes over

Sodium sulfate dries and filtered. Evaporation of the filtrate under reduced pressure gives 22.88 g of a yellow liquid. The gas chromatographic analysis of the two parts of the yellow liquid shows that they are identical. The fractions are combined, mixed with 0.93 g of p-toluenesulfonic acid and distilled under reduced pressure. Six fractions (A) to (F) are collected and analyzed by gas chromatography. Fraction (F) is combined with the bubble residue and distilled again, giving four fractions (G), (H), (I), (J) which are also analyzed by gas chromatography. A sample of fraction (D) gives the following elemental analysis:
Analysis for C ₇ H ₁₄ O ₃ : CH

³⁵ calc .: 57.51; 9.65;

Found: 57.80; 9.94.

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The fractions C ₁ D, E, G and H are combined, with 31 »36 g of r-2-ethyl-c-5-hydroxy-c-4-ae"Üiyl-1,3-dioixane; bp 78 to 81 ° C / 15 to 17 Torr.

Similarly, starting from suitable alkanetriols and aldehydes produced the following compounds:

B. c-S-Hydroxy-r ^ -isopropyl-c ^ -methyl-i, 3-dioxane, B.p. 72 to 75 ° C / 12 torr;

C. r-2-ethyl-c-5-hydroxy-c-4-propyl-1,3-dioxane, b.p. 34 ° c / 0.025 torr;

D. r ^ -Ethyl-c-S-hydroxy-c- ^ isopropyl-t, 3-dioxane, Bp 42.5 to 45 ° C / 0.55-0.4 torr;

E. c-5-Hydroxy-r-2-c-4-dimethyl-'t, 3-dioxane, Bp 54-55 ° C / 3.75 torr;

15 F. c-5-Hydroxy-c-4 ~ iBethyl-r-2-propyl-1,3-dio3tane, Bp 45 ° C / 0.5 Torr and

G. r ^ -tert.-Butyl-c-S-hydroxy-c- ^ methyl-i, 3-dioxane, M.p. 53.5-54.5 ° C.

20 H ¹ . ervthro-1.2.3-butanetriol

188.7 g of 30 percent hydrogen peroxide (56.6 g of H2O2) are gradually added to a stirred mixture of 100 g of cro ty! Alcohol in 900 ml of p-dioxane and 450 ml of water, whereupon 2.82 g of tungsten oxide (WO) are added as Adding catalyst. After completion of the addition, stirring the reaction mixture for 1 hour at room temperature, 16 hours at 35 ° C, 8 hours at 45 ° C and finally 16 hours at 40 ⁰ C. It is then cooled to room temperature and checked with potassium ^ iodide paper on excess Peroxide. The test is negative. The reaction mixture is filtered through diatomaceous earth to separate the catalyst. The filtrate is then neutralized with aqueous 2 η sodium hydroxide solution and evaporated under reduced pressure. The residue is taken up in 800 ml of methanol and dried over sodium sulfate and magnesium sulfate. The mixture is then filtered through diatomaceous earth and the filtrate is evaporated under reduced pressure. By distilling the

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Residue in a distillation device with short paths gives 110.75 g of erythro-1,2,3-butanetriol; 97 ^° C / 0.03 Torr.
Analysis for C ^ H ₁₀ O ,: CH

5 calc .: 45.27; 9.50;

Found: 44.98; 9.29-

H. r-2-Ethyl-t-5-hvdroxv-c-4-methyl-1,3-dioxane The dioxolane precursor. This compound is based on similar

Prepared in the same way as the above 5-hydroxy compounds using 50 g of erythro-1,2,3-butanetriol, 27.4 g of propionaldehyde and 0.75 g of p-toluenesulfonic acid in 255 ml of hexane. The crude reaction mixture is distilled in 19 fractions to give a mixture of dioxolanes; B.p. 58 to 76.8 ° C / 2.15 to 3.40 torr. Fractions 3 to 3 are combined and redistilled into four fractions, a dioxolane mixture being obtained which mainly consists of cis-2-ethyl-4- (erythro-1-hydroxyethyl) -1,3-dioxolane; B.p. 53-67 ° C / 2.5 Torr. A sample of 8.80 g of fraction 4 of this distillation (boiling point 67 ° C / 2.5 Torr), which, according to gas chromatographic analysis, contains 65.8% cis-2-ethyl-4- (erythro-1-hydroxyethyl) - Contains 1,3-dioxolane, 0.1 g of p-toluenesulfonic acid is added and the mixture is placed in a refrigerator for 6 days in order to equilibrate to r-2-ethyl-t-5-hydroxy-c-4-methyl-1 To effect 3-dioxane. The sample (8.80 g) is then taken up in 150 ml of diethyl ether, the ethereal layer is washed three times with 50 ml of a saturated aqueous sodium bicarbonate solution each time and then three times with 50 ml of a saturated aqueous sodium chloride solution each time, dried over sodium sulfate and filtered. Evaporation of the filtrate under reduced pressure gives a residue which, according to gas chromatographic analysis, consists of 86.8 % r-2-ethyl-t-5-hydroxy-c-4-methyl-1,3-dioxane. The crude product is distilled into five fractions, one being

³⁵ Mixture of dioxolanes and dioxanes is formed; Kp. 87 to

104 C / 18 to 20 torr. Presumably, traces of acid cause im Re-equilibration in the distillation vessel. The factions

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are combined and mixed with 0.1 g of p-toluenesulfonic acid. Equilibration takes place in a refrigerator within 8 days. The equilibration mixture is then taken up in 150 ml of diethyl ether, washed three times with 50 ml of saturated aqueous potassium carbonate solution each time and then three times with 25 ml of saturated aqueous sodium chloride solution each time, dried over sodium sulfate and filtered. Evaporation of the filtrate under reduced pressure gives 8.65 g of a residue which, according to gas chromatographic analysis, contains 82.7 % r-2-ethyl-t-5-hydroxy-c-4-methyl-1,3-dioxane. The crude product is distilled into 15 fractions from a vessel containing 0.05 g of sodium hydroxide using a thin film evaporator; Kp. 87-101 ⁰ C / 12 to 13 Torr. Fractions 9 to 15 become 2.48 g of r-2-ethyl-t-5-hydroxy-c-4-methyl-1,3-dioxane; Bp. 100 to 1O1 ° C / 12-13 Torr, which, according to gas chromatographic analysis, has a purity of 93 to 95 % . The structure is confirmed by the NMR spectrum. Analysis for C ₇ H ₁₄ O ₅ : CH

20 calc.i 57.51; 9.65;

found i 57.42; 9.90.

J ¹ . Mixture of erythro- and threo-3-methyl-2,3,4-pentrantriol A mixture of 75.4 g of 3-methyl-penten-2-ol and 91.44 g of 35 percent hydrogen peroxide (32.0 g of H ₂ O ₂ ) in 500 ml 1.8 g of tungsten oxide (WO) are added as a catalyst to water over the course of 1 hour, while stirring, and the mixture is kept at reflux temperature for about 48 hours. This checks for unreacted hydrogen peroxide and removes the excess with it

30 6.3 g sodium sulfite in 50 ml water. The solution will be

filtered and concentrated under reduced pressure, giving 92.9 g of a reddish yellow dispersion of a solid in a viscous Remaining liquid, which is dissolved in methanol. The solution is then filtered and the filtrate is concentrated under reduced pressure, leaving 60.45 g of a dark brown viscous liquid. Due to the viscous

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Because of the liquid, stable pressures cannot be established. However, there are 35.0 g of erythro- and threo-3-methyl-2,3,4-pentanetriol caught; Bp, 85 to 90 ° C / 0.09 to

0.12 torr.
5

J. r-2-ethyl-c-5-hydroxv-t-4, t-5t c-6-trimethyl-1,3-dioxane and r-2-ethyl-t-5-hydroxv-c-4, c-5 . c-6-trimethyl-1,3-dioxane mixed with diolanes
The mixture is prepared in a manner similar to the above hydroxydioxanes using 35.0 g of a mixture of erythro- and threo-3-methyl-2,3,4-pentanetriol, 15.14 g of propionaldehyde and 0.49 g of p-toluenesulfonic acid in 200 ml of hexane produced. The crude reaction mixture is distilled in a distillation A using a thin-film evaporator under reduced pressure, 37.3 g of a distillate being obtained in eight fractions; B.p. 30 to 65 ° C / 2.75 to 3.30 torr. The gas chromatography analysis of the fractions shows that they are mixtures of ice and

are trans-hydroxy-1,3-dioxanes and dioxolanes. 20th

Fractions 1 to 4 (boiling point 49.5 to 65 ° C. / 2.90 to 3.30 torr) are combined and redistilled in a distillation B, 14.1 g of a distillate being obtained in 6 fractions; Bp 35 to 56.5 ° C / 2.80 to 3.05 torr. The gas chromatographic analysis of the fractions shows that fractions 1 to 4 mainly consist of cis-hydroxy-1,3-dioxane and dioxolane and fractions 5 and 6 as well as the residue in the distillation vessel mainly consist of trans-hydroxy-1,3- dioxane and dioxolane exist. Fraction 4 (boiling point 35 to 55 ° C. / 2.95 to 3.00 torr) is redistilled in a distillation C, an analytical sample of cis-hydroxy-1,3-dioxane and -dioxolane being obtained. Analysis for C ₉ H ₁₈ O ₃ : CH

calc .: 62.04; 10.41; 35 found: 62.29; 10.70.

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Fractions 1, 5 and 6 and the distillation residue from distillation B and fractions 5 to 8 from distillation A are combined and redistilled in a distillation D, 27.3 g of a distillate being obtained in 10 fractions, bp 35 bis 65 ° C / 2.9 to 3.1 torr. According to the gas chromatographic analysis, fraction 2 contains 88.1 % r-2-ethyl-c-5-hydroxy, t-4, t-5, c-6-trimethyl-1,3-dioxane, which is presumably 2-ethyl 4,5-dimethyl-4- (1-hydroxyethyl) -1,3-dioxolane ;. Bp 45 to 49 ° C / 3.0 is torr. The fraction weighs 5.56 g.

K ". For example, 1-hydroxy-1-methyl) -äthv17-2-methvloxirane

A solution of 46.7 g of 2,3-di-methyl-3-buten-2-ol in 602 ml of chloroform is cooled to 0 to 5 ° C. in a dry ice / acetone bath and then a solution of 96 is added dropwise over the course of 4 hours , 5 g of m-chloroperoxybenzoic acid (113.5 g, 85 %) in 966 ml of chloroform were added. The reaction mixture is then kept at 0 to 5 ° C. with stirring. After the addition has ended, the reaction mixture is allowed to warm to room temperature and is stirred for a further 18 hours. A solution of 11.8 g of sodium sulfite in the smallest possible amount of water is then slowly added. The reaction mixture is checked for peroxides with moist acid sodium iodide / starch paper. However, no peroxides can be detected. When the reaction mixture is concentrated to less than half of the original volume, benzoic acid separates out of the reaction mixture, which is filtered off. The concentration, precipitation and filtering is repeated several times until only a small amount of benzene acid precipitates during the last concentration. 16.6 g of a yellow liquid are obtained from which a white solid crystallizes out on standing. The liquid portion is decanted off and the solid is washed with diethyl ether. The ether wash solution is combined with the liquid portion. The white solid having a melting point of 116 ° to 118 ° C and decomposes explosively at 170 to 180 ⁰ C. The liquid portion is in

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a Vigreux column distilled, with 9.32 g of 2 - / "(1-hydroxy-1-methyl ) -ä thy l7-2-methyloxirane; Bp 35 to 65 ° C / 15 to

can be obtained by 20 Torr. The structure is based on the NMR spectrum

confirmed.

K ¹ . 2,3-dimethyl-1,2,3-butanetriol

A mixture of 8.73 g of 2 - / "(1 -hydroxy-1-methyl) -ethyl7 ~ 2-methyloxirane, 7 drops of concentrated sulfuric acid, 15 ml of p-dioxane and 100 ml of water are heated to 55 ° C. for 16 hours.

The reaction mixture is then neutralized using a phenolphthalein indicator with sodium hydroxide solution. At the Evaporation of the mixture under reduced pressure gives a viscous cloudy liquid which is dissolved in ethanol and is filtered. Evaporation of the filtrate under reduced pressure gives 9.82 g of a viscous oil as a residue. which is distilled with the aid of a distillation device with short paths and here 8.16 g of 2,3-dimethyl-1,2,3-butanetriol; Bp 85 to 94 ° C / 0.02 Torr gives. The structure is confirmed by the NMR spectrum.

K. r-2-Ethyl-c-5-hydroxy-c-4, t-4.t-5-trimethyl-1,3-dioxane The compound is prepared in a manner similar to the above hydroxydioxanes using 7.76 g 2,3-Dimethyl-1,2,3 butanetriol, 3.35 g of propionaldehyde and 0.13 g of toluenesulfonic acid in 100 ml of hexane. When the crude product is distilled under reduced pressure, 2.12 g of r-2-ethyl-c-5-hydroxy-c-4, t-4, t-5-trimethyl-1,3-dioxane are obtained; Bp 60.5 to 62.5 ° C / 1.0 to 3.5 torr. The structure is confirmed by the NMR spectrum.

30 Analysis for C ₉ H ₁₈ O ₃ : CH

calc .: 62.04; 10.41; Found: 61.75; 10.49.

In a similar way, the following connections are made:

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L. r-2, c-4-diethyl-c-5-hydroxy-1,3-dioxane, b.p. 44 ° C / O, 5 torr M. c-4-ethyl-c-5-hydroxy-r-2-methyl-1,3-dioxane,

Bp 36 ° C / 0.65 torr;
N. c-4-ethyl-c-5-hydroxy-r-2-isopropyl-1,3-dioxane,

5 bp 39 ° C / 0.5 Torr.

P. threo-2- (2-Methylbenzvloxv) -1.5-buta.ndiol

A solution of 53.9 g of r-2-ethyl-c-4-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane .from Example II and 113.2 ml of 0.75 percent aqueous hydrochloric acid in 226 ml of absolute ethanol is kept at 60 ° C. for 24 hours, after which 244 ml of an azeotrope (boiling point 70 to 83 ° C.) are distilled off. The residue is neutralized with about 12 ml of a 10 percent aqueous sodium hydroxide solution, whereupon the mixture is dissolved in 1500 ml of ethyl acetate picks up and puts the whole thing in a separating funnel. Shake after adding about 100 g of sodium chloride the mixture is thoroughly separated, the organic layer is separated, dried over sodium sulfate and filtered. The filtrate is concentrated under reduced pressure and the residue is distilled under reduced pressure, dividing into 7 fractions 41.10 g of threo-2- (2- (2-methylbenzyloxy) -1,3-butanediol; b.p. 121-122 ° C / 0.008 torr are obtained. The structure is confirmed by the IR and NMR spectra.

²⁵ Q. 2-Methyl-2- (2-methylbenzyloxy) -1,3-propanediol

The compound is prepared in a manner similar to Intermediate P using 250.0 g of r-2-isopropyl-5-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane and 500 ml of 0.75 percent aqueous hydrochloric acid in 1000 ml of ethanol. When recrystallizing of the reaction product from hexane / chloroform (1: 1), 142.6 g of white crystalline 2-methyl-2- (2-methylbenzyloxy) -1,3-propanediol are obtained; F. 90 to 91 ° C. The structure is confirmed by the NMR spectrum.

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¹ R "'· Mixture of dl- and meso-2,3,4-pentanetriols

A stirred mixture of 10 g of cis-3-penten-2-ol and 0.12 g of tungsten oxide in 128 ml of water is mixed with 20.4 g of 30 percent hydrogen peroxide at room temperature. After the addition is complete, the reaction ^{mixture is stirred for 18 hours at 6O 0} C, the pH of the filtered reaction mixture is adjusted to 7 to 7-5 with 10 percent aqueous sodium hydroxide solution, excess peroxide is decomposed with a saturated aqueous solution of sodium sulphite and the water is separated by heating Reaction mixture under reduced pressure. The oily residue is taken up in 250 ml of methanol, stirred and filtered in order to separate off salts. When the filtrate is evaporated under reduced pressure, an oil remains, which is distilled under reduced pressure with the aid of a distillation device with short paths to give 6.5 g of a mixture of dl- and meso-2,3,4-pentanetriols; Bp 92 to 96 ° C / 0.33 torr.

R ". Trans-4- (threo-1-Hydroxväthvl) -2,2.5-trimethvl-1.3-

20 dioxolane

The compound is prepared in a manner similar to Intermediate A using 142.6 g of a mixture of dl- and meso-2,3,4-pentanetriols, 99.1 g acetone and 3.4 g p-toluenesulfonic acid manufactured. 10 g of the crude product from two previously carried out reactions are with the crude product this reaction combined, so that a total of 171.8 g are available. When distilling this material 94.4 g of trans-4- (threo-1-hydroxyethyl) -2,2,5-trimethyl-1,3-dioxolane;

³⁰ bp 62 to 62.5 ° C / 4.7 Torr.

R ¹ . meso-2.3.4-pentanetriol

The compound is prepared in a manner similar to Intermediate P using 84.4 g of trans-4- (threo-1-hydroxyethyl) -2,2,5-trimethyl-1,3-dioxolane and 278.9 ml of 0.75 percent aqueous hydrochloric acid in 560 ml of absolute ethanol manufactured. During the distillation of the crude product in

a still with short distances under Ver L-809809/1079

59.2 g of meso-2,3,4-pentanetriol are obtained in one fraction under reduced pressure. The structure is confirmed by the NMR spectrum.
Analysis for C ₅ H ₁₂ O ₃ ; CH

calc .: 49.99; 10.07; Found: 49.70; 9.91.

R. r ^ -Äthvl-cS-hvdroxv-c ^. c-6-dimethvl-1. , 5-dioxane The compound is prepared in a manner similar to Intermediate A using 55.9 g of meso-2,3,4-pentanetriol, 41.1 g of propionaldehyde and 1.3 g of p-toluenesulfonic acid in 400 ml of anhydrous hexane . When the crude product is distilled under reduced pressure, 30.6 g of r-2-ethyl-c-5-hydroxy-c-4, c-6-di-

¹ S methyl-1,3-dioxane; B.p. 76.5 to 77 ° C / 15 torr. The structure is confirmed by the IR and NMR spectra. Analysis for C ₈ H ₁₆ O ₃ : CH

calc .: 59.97; 10.07 Measured values: 60.28; 9.93

S ¹ " ^1. trans-2- (1-Hydroxväthyl) -3-methvloxiran A solution is added to a stirred solution of 83.2 g of trans-3-penten-2-ol in 1250 ml of methylene chloride at 0 ^° C. within 2 hours of 200.1 g of 3-chloroperoxybenzoic acid in 750 ml of methylene chloride are added dropwise, the temperature of the reaction mixture being kept at 0 to 10 ° C. After the addition has ended, the reaction mixture is allowed to warm to room temperature and is stirred for a further 18 hours The reaction mixture is then evaporated under reduced pressure, the precipitated 3-chlorobenzoic acid being filtered off from time to time. The precipitate is washed with hexane and the washing solutions are combined with the filtrate. The combined liquids are increased to 300 under reduced pressure ml concentrated and poured into 600 ml diethyl ether, the aqueous layer

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is saturated with sodium chloride and separated. The organic layer is saturated 7 times with 50 ml each aqueous sodium bicarbonate solution and washed twice with 50 ml of a saturated aqueous sodium chloride solution each time and finally dried over sodium sulfate. The mixture is filtered and the filtrate under reduced pressure concentrated, leaving an oil which, on distillation under reduced pressure, in 2 fractions 21.1 g trans-2- (1-hydroxyethyl) -3-methyloxirane; B.p. 78 to 81 ° C / 40 Torr results. The washing solutions of the crude product are combined, saturated with sodium chloride and then extracted four times with 200 ml of diethyl ether each time. The United Extracts are dried over sodium sulfate and filtered. Obtained by evaporating the filtrate under reduced pressure an oil is distilled under reduced pressure to give 25.0 g of a distillate, b.p. 77 up to 78 ° C / 40 Torr. Combining the two distillates gives 46.1 g of trans-2- (1-hydroxyethyl) -3-methyloxirane.

20 S ^WED . Mixture of dl- and meso-2.3.4-pentanetriols

A stirred solution of 172.3 g of trans-2- (1-hydroxyethyl) -3-methyloxirane and 3.6 g of concentrated sulfuric acid in 2239 ml of water / water and 100 ml of 1,4-dioxane is added for 18 hours Heated to 55 ° C. The reaction mixture is then cooled and neutralized with 1 η sodium hydroxide solution until the phenolphthalein neutral point is reached. It is then evaporated under reduced pressure until the salts present crystallize out are. The viscous residue is taken up in methanol and filtered. By evaporating the filtrate an oil is obtained under reduced pressure, which under reduced pressure Pressure is distilled and here in a fraction 184.6 g of a mixture of dl- and meso-2,3,4-pentanetriols results; Bp 110 to 112 ° c / 0.1 to 0.2 torr.

The structure is confirmed by the NMR spectrum. 35

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A *

S ⁿ . trans-4- (threo-1-hydroxyl ethyl) -2.2.5-trimethyl-1,3-dioxolane and / or cis-4- (threo-1-hydroxyl ethyl) -2,2.5-trimethyl-1,3-dioxolane

The compound is prepared in a manner similar to Intermediate A using 184.6 g of a mixture of dl- and meso-2,3,4-pentanetriols, 104.2 g of acetone and 4.4 g of p-toluenesulfonic acid in 1475 ml of anhydrous Hexane produced. By distilling the crude product under reduced pressure, 102.8 g of trans-4- (erythro-1-hydroxyethyl) -2,2,5-trimethyl-1,3-dioxolane and / or cis-4- (threo -1-hydroxyethyl) -2,2,5-trimethyl-1,3-dioxolane; Bp 60 to 67 ° C / 4.5 to 5.0 torr.
Analysis for CgH ₁₆ O ₅ : CH

calc .: 59.97; 10.07.15 Measured values: 60.26; 9.83.

S «. dl-2.3.4-pentanetriol

The compound is prepared in a similar manner to intermediate P using 102.8 g of trans-4- (erythro-1-hydroxyethyl) -2,2,5-trimethyl-1,3-dioxolane and / or cis-4- (threo-1-hydroxyethyl) -2,2,5-trimethyl-1,3-dioxolane and 339 ml of 0.75 percent aqueous hydrochloric acid in 542 ml of absolute ethanol. When distilling the crude The reaction product under reduced pressure is obtained in one fraction of 74.1 g of dl-2,3,4-pentanetriol; Kp. 106 to 110 ° C / 0.02 torr.

8. r-2-Ethyl-c-5-hydroxy-c-4, t-6-dimethyl-1,3-dioxane The compound is prepared in a manner similar to Intermediate A using 74.1 g of dl-2, 3,4-pentanetriol, 35.8 g of propionaldehyde and 1.8 g of p-toluenesulfonic acid in 589 ml of anhydrous hexane. The crude reaction product is purified by multiple distillation under reduced pressure and then subjected to medium pressure liquid chromatography on a silica gel column which is eluted with hexane / ethyl acetate (85:15).

809809/1079

A suitable combination of the fractions gives 20.2 g in the distillation under reduced pressure r-2-ethyl-c-5-hydroxy-c-4, t-6-dimethy1-1,3-dioxane; B.p. 78 to 83 ° C / 13 to 15 Torr. The structure is confirmed by the IR and NMR spectra.

Analysis for CqH ₁₆ O,: CH

calc .: 59.98; 10.07 Measured values: 60.27; 10.35

¹⁰ T ^f . threo-2-methyl-1.2.3-butanetriol

The compound is prepared in a similar manner to Intermediate R ^IM using 91.21 g of trans-2-methyl-butene-2-1-ol, which has been-methyl-trans-2 2-butanal obtained by reducing with lithium aluminum hydride , and 2.55 g of tungsten oxide in 800 ml of water and 800 ml of 1,4-dioxane as a solvent and of 43.23 g of hydrogen peroxide (144.10 g of a 30 percent aqueous hydrogen peroxide solution). The crude product is distilled under reduced pressure with the aid of a short-path still, whereby 82.02 g of fhreo-2-methyl-1,2,3-butanetriol; Bp. 110 ° C / <0.001 Torr.

T. r-2-Ethyl-c-5-hydroxy-t-4 «t-5-dimethyl-1,3-dioxane

The compound is made in a manner similar to that of the intermediate A using 50.00 g of threo-2-methyl-1,2,3-butanetriol, 24.15 g propionaldenyde and 1.18 g p-toluenesulfonic acid made in 250 ml of anhydrous hexane. By distilling the crude reaction product under reduced Pressure is obtained in 10 fractions 30.02 g of r-2-ethyl-c-5-hydroxy-t-4, t-5-dimethyl-1,3-dioxane; Bp 41 ° C / O.96 torr. The structure is confirmed by IR and NMR spectra.

Analysis for ^c -j5 ^H 22 ° 3 ^{: CH}

calc .: 71.97; 8.86;

Found: 72.22; 8.91. 35

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The compounds according to the invention are prepared by adding a substituted 5-hydroxy-1,3-dioxane in a solvent, e.g. toluene, at temperatures from room temperature to the reflux temperature of the solvent with a Reacts alkali metal base and the resulting alkali metal alcoholate at the reflux temperature of the solvent with a Aryl methyl halide, e.g. aryl methyl chloride or bromide, or with a heteroaryl methyl halide, such as 2-chlorine thy I-furan, etherified. Sodium compounds are preferred as the alkali metal bases. If necessary, another procedure is used applied, especially to compounds in which the 2-substituent during treatment with the alkali metal base can be attacked (e.g. in the case of the chloromethyl group) or for a selective distillation of the 5-hydroxy-1,3-dioxane is too voluminous (e.g. in the case of the Pheny! group). In this process, a compound of the invention bearing suitable 4- and 5-substituents is subjected to the acid hydrolysis and puts the 1,3-diol obtained in the presence an acidic catalyst, e.g. p-toluenesulphonic acid, under reflux in a solvent such as hexane with a suitable carbonyl compound such as benzaldehyde or their Acetal, e.g. chloroacetaldehyde diethy! Acetal, where a 1,3-Dioxane is formed, which while retaining the 4- and 5-substituents in the desired configuration

²⁵ desired 2-substituents carries.

Example I.

r-2-Äthvl-c-5- (2-fluorobenzvloxv) -c-4-methvl-1.3-dioxane 2.53 g of a sodium hydride suspension in mineral oil (weight ratio 1: 1) are introduced into a reaction vessel and twice with each 50 ml of anhydrous hexane and washed twice with 50 ml of toluene each time. 100 ml of anhydrous toluene are then added to the sodium hydride and 7.0 g of r-2-ethyl-c-5-hydroxy-c-4-methyl-1,3-dioxane are added dropwise over 15 minutes with stirring. The exothermic reaction increases the temperature of the reaction mixture from 23 to 33 ° C. The reaction mixture is then refluxed for 5 1/2 hours, then cooled to room temperature and

^L 809809/1079 ^J.

sets within 5 minutes with 7.62 g of 2-fluorobenzyl chloride. The reaction mixture is refluxed for 18 hours and then washed three times with 50 ml of cold water / water each time. until the wash water has a pH of about 5.

The organic layer is separated, dried over sodium sulfate and filtered. By concentrating the filtrate below reduced pressure, 11.87 g of a yellow liquid are obtained, which in the distillation under reduced pressure 7.85 g of r-2-ethyl-c-5- (2-fluorobenzyloxy) -c-4-methyl-1,3-dioxane; B.p. 95.5 to 98 ° C / 0.05 to 0.075 torr. The structure is confirmed by IR and MIR spectra.

analysis for C ₁₄ H ₂₉ FO ₃ : 66 C. H 53; ber .: 66 , 12; 7, 55. found: , 40; 7,

Example II

c ^ - (2-methylbenzyloxv) -1,5-dioxane

The procedure of Example 1 is repeated but used one 2.53 g of the mineral oil suspension of sodium hydride and 7.0 g of r-2-ethyl-c-5-hydroxy-c-4-methyl-1,3-dioxane and 7.41 g of 2-methylbenzyl chloride instead of 2-fluorobenzyl chloride. The washed, dried and filtered reaction mixture is concentrated under reduced pressure, with 11.73 g of a dark yellow liquid remaining. This will by column chromatography on a silica gel column with high-boiling petroleum ether and high-boiling petroleum ether / Purified ethyl acetate (98: 2) as eluant until 245 fractions are collected. The fractions 95 bis 122 are combined and concentrated to 6.32 g of a yellow liquid. The two proportions are reduced under Distilled under pressure and the combined distillates give 6.90 g of r-2-ethyl-c-4-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 104 to 106 ° C / 0.505 to 0.075 torr. The structure is confirmed by IR and NMR spectra.

³⁵ Analysis for C ₁₅ H ₂₂ O ₃ : CH

calc .: 71.97; 8.86; Found: 72.02; 8.89.

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¹ Example III

c-5- (2-Chlorben2vloxv) -r-2-ethyl-c-4-methYl-1,3-dioxane The procedure of Example I is carried out using 2.53 g of the mineral oil suspension of sodium hydride and 7.0 g of r -2-Ethyl-c-5-hydroxy-c-4-methyl-1,3-dioxane and 8.48 g of 2-chlorobenzyl chloride instead of 2-fluorobenzyl chloride were repeated. The washed, dried and filtered reaction mixture is concentrated under reduced pressure and the residue (12.96 g) is distilled under reduced pressure, whereby 7.46 g of c-5- (2-chlorobenzyloxy) -r-2-ethyl-c- 4-methyl-1,3-dioxane; Bp 110 to 114 ° C / 0.32 to 0.40 torr. The structure is confirmed by IR and NMR spectra.
Analysis for C ₁ ^ H ₁₆ ClO ₃ : CH

¹⁵ calc .: 62.10; 7.07;

Found: 62.40; 7.09.

Example IV

c-5-Benzyloxv-r-2-ethyl-c-4-methvl-1,3-dioxane The procedure of Example I is carried out using 2.52 g of the mineral oil suspension of sodium hydride and 7.0 g of r-2-ethyl -c-5-hydroxy-c-4-methyl-1,3-dioxane and 6.62 g of benzyl chloride instead of 2-fluorobenzyl chloride were repeated. After refluxing for 16 hours

the reaction mixture was washed five times with 100 ml Y / ater each time, until the wash water has a pH of about 5. The organic layer is separated, dried over sodium sulfate and filtered. By concentrating the filtrate under reduced pressure, 11.56 g of a residue is obtained

is distilled under reduced pressure. 6.57 g of c-5-3enzyloxy-r-2-ethyl-c-4-methyl-1,3-dioxane; Bp 110-114 ° C / O, O1 torr obtained. The structure is confirmed by IR and NMR spectra. Analysis for C ₁ → H ₂₀ O ₃ ; CH calc .: 71.15 * 8.53

Found: 71.43; 8.33;

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Following the procedure of Examples I to IV, the following compounds are prepared:

Examples
V-cS-benzyloxy-rZ-isopropyl-cA-methyl-1,3-dioxane;

Bp 110-113 ° C / 0.020 torr; C 72.20 %, H 8.57 %. VI - c-5- (2-fluorobenzyloxy) -r-2-isopropyl-cA-methyl-1,3-dioxane; Bp 103-105 ° C / 0.020 torr, C 67.14 %, H 7.83 %.

VII - r-2-isopropyl-c-4-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 115-117 ° C / 0.020 torr, C 72.74 %, H 9.14 %.

VIII - c-5- (2-chlorobenzyloxy) -r-2-isopropyi-c-4-methyl-

1,3-dioxane; bp. 126-130 ° C / 0.020 torr; ¹⁵ C 62.96 % _y H 7.25 %.

IX - c-5-benzyloxy-r-2-ethyl-c-4-propyl-1,3-dioxane;

B.p. 125 ° C / 0.01 torr; C 72.38 %, H 9.29 %.

X - r-2-ethyl-c-5- (2-fluorobenzyloxy) -c-4-propyl-1,3-

dioxane; Bp 140 ° C / 0.01 torr; C 68.20 yo, H 8.54%. XI- r-2-ethyl-c-5- (2-methylbenzyloxy) -c-4-propyl-

1,3-dioxane; Bp 130 ° C / 0.010 torr; C 73.10 %

H 9.41 %.
XII - c-5- (2-chlorobenzyloxy) -r-2-ethyl-c-4-propyl-1,3-

dioxane; Bp 120-125 ° C / 0.01 torr; C 64.00%, H 7.57 %.

Comparative Example XIII

-t ^ - (2-methylbenzvloxv) -1.3-dioxane

The compound is according to 3 example I using 2.48 g r-2-ethyl-t-5-hydroxy-c-4-methyl-1,3-dioxane (intermediate H), 260 g of 2-methylbenzyl chloride and 0.45 g (0.90 g of the 50 percent dispersion in mineral oil) sodium hydride in 70 ml of toluene. By distilling the crude reaction mixture gives 2.41 g of r-2-ethyl-c-4-methyl-t-5- (2-methylbenzyloxy) -1,3-dioxane; Bp. 93 - 95 ° C /

25th
0.011 torr, n ^ = 1.5284. The structure is defined by IR and

NMR spectra confirmed. ^L 809809/1079

1 analysis for C ₁₅ H ₂₂ O ₃ : CH

calc .: 71.97; 8.86; Found: 72.60; 8.90.

5 Example XIV

r-2-ethyl-t-4. t-5. c-6-trimethyl-c-5- (2-methylbenzvloxv) -1.3-dioxane in a mixture with 2-Äthvl-4.5-dimethvl-4- / i- (2-methylbenzvloxv) -äthyl7-1.3-dioxolane A solution of 6 , 22 g of a mixture of r-2-ethyl-c-5-hydroxy-t-4, t-5, c-6-trimethyl-1,3-dioxane and 2-ethyl-4,5-dimethyl-4- (1-hydroxyethyl) -1,3-dioxolane (intermediate J) and 2.42 g of sodium ethylate (15 percent sodium ethylate solution in ethanol) in anhydrous toluene are heated to a temperature at which the ethanol distills off azeotropically from the reaction mixture. Additional toluene is added to the reaction mixture as needed. As soon as the temperature of the distillate reaches 110 ^° C., 50 ml of the distillate are collected and the reaction mixture is cooled to room temperature. The reaction mixture is then treated all at once with a solution of 5.02 g of 2-methylbenzyl chloride, heated under reflux for 20 hours and then poured into 50 ml of cold water. The toluene layer is separated off and the water layer is washed three times with 50 ml of toluene each time. The combined toluene layers are washed three times with 25 ml of water each time and then dried over sodium sulfate. The mixture is filtered and the filtrate is concentrated under reduced pressure. By distilling the residue under reduced pressure with the aid of a distillation device with short paths, 3.0 g of a distillate, boiling point 25 to 42 ° C./0.01 torr, is obtained in one fraction. According to the gas chromatographic analysis, the fraction consists of a mixture which contains a large proportion of the o-methylbenzyl chloride used. The distillation residue from this distillation (5.59 g) is distilled under reduced pressure, 4.58 of a clear liquid being obtained in one fraction, boiling point 118-122 ° C./0.07 Torr. After

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According to gas chromatographic analysis, the distillate consists of a mixture of 62 % t * -2-ethyl-tA, t-5, c-ö-trimethyl-c -? - (2-methylbenzyloxy) -1,3-dioxane and 23 % 2- Ethyl 4,5-dimethyl-4- / i- (2-methylbenzyloxy) -ethyl / -1,3-dioxolane. the

5 structures are confirmed by the NMR spectra.

Comparative Example XV

r-2-Ethyl-c-4.t-4.t-5-trimethyl-c-5- (2-methylbenzvloxv) -1.3-dioxane

The compound is prepared according to Example I using 5.78 r-2-ethyl-c-5-hydroxy-c-4, t-4, t-5-trimethyl-1,3-dioxane (intermediate product K), 5, 13 g of 2-methylbenzyl chloride and 0.88 g of sodium hydride (1.75 g of a 50 percent mineral oil dispersion) in 100 ml of anhydrous toluene. The crude reaction product is subjected to column chromatography on 150 g of silica gel in a glass column 3.6 cm in diameter. The eluent used is 100% high-boiling petroleum ether, high-boiling petroleum ether / ethyl acetate (99: Ό, high-boiling petroleum ether / ethyl acetate (95: 5) and 100 % ethyl acetate. Fractions 70 to 156 are combined and evaporated, leaving 4.19 g of an oil which is distilled with the aid of a short-path still, in which 1.06 g of r-2-ethyl-c-4-t-4, t-5-trimethyl-c-5- (2-methylbenzyloxy) -1,3-dioxane, boiling point 89.5 to 93 ° C. O. O. O. 5 Torr. The structure is confirmed by IR and NMR spectra.

analysis for C ₁₇ H ₂₆ O ₃ : C. 9 H ber .: 73.34; 9 , 41; found: 73.38; , 56.

Example XVI

c-5-Benzyloxv-o-4-methyl-r-2-propyl-1,3-dioxane A mixture of 6.0 g of c-5-hydroxy-c-4-methyl-r-2-propyl-1, 3 dioxane (intermediate F) and 3.40 g of sodium methylate ( ¹ 3.6 g of a 25 percent strength sodium methylate solution in methanol) in 150 ml of anhydrous toluene is heated with stirring to a temperature at which the methanol distills off as an azeotrope with toluene. After separating the methanol

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15th

anhydrous toluene is added to replace the lost azeotrope volume, the mixture is cooled to about 80 ° C. and 7.90 g of benzyl chloride are added dropwise. When the addition is complete, the reaction mixture is refluxed for 19 hours. After cooling to room temperature, the mixture is washed six times with 60 ml of water each time and once with 60 ml of a salt solution and dried over sodium sulfate. The mixture is filtered and the filtrate concentrated under reduced pressure to leave 14.6 g of a residue which is distilled under reduced pressure. 8.0 g of c-5-benzyloxy-c-4-methyl-r-2-propyl-1,3-dioxane; Bp 107-109 ° C / 0.13 torr. The structure is confirmed by IR and NMR spectra.
Analysis for C ₁₅ H ₂₂ O ₃ : CH

calc .: 71.97; 8.86.

found: 72.20 9.12.

Following the procedure of Example XVI or the other procedures described, the following compounds are prepared: Examples

XVII - c-5- (2-fluorobenzyloxy) -c-4-methyl-r-2-propyl-1,3-

dioxane; Bp 143-145 ° C / 0.015 torr; C 67.09 %; H 8.02 %.

XVIII - c-4-methyl-c-5-methylbenzyloxy) -r-2-propyl-1,3-dioxane; Bp 114-118 ° C / 0.005 torr; C 72.35 %,

H 9.09 %.

XIX - c-5- (2-chlorobenzyloxy) -c-4-methyl-r-2-propyl-1,3-

dioxane; Bp 114-118 ° C / 0.005 fforr; C 63.36 %, H 7.31%
XX-c-5-benzyloxy-r-2, c-4-diethyl-1,3-dioxane;

Bp 113-115 ° C / 0.15 torr; C 72.25% H 8.74 %.

XXI - r-2, c-4-diethyl-c-5- (2-fluorobenzyloxy) -1,3-dioxane;

Bp 115-117 ° C / 0.15 torr; C 67.39% H 7.71 si.

XXII - r-2, c-4-diethyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; B.p. 118-12O ° C / 0.110 torr; C 73.01 %, H 8.98%

XXIII - c-5- (2-chlorobenzyloxy) -r-2, c-4-diethyl-1,3-dioxane;

B.p. 127-130 ° C / 0.15 torr; C 63.57 %, H 7.30 %.

809809/1079

XXIV - c-5-benzyloxy-c-4-ethyl-r-2-methyl-1,3-dioxane;

Bp 118-123 ° C / 0.15 torr; C 71.10 %, H 8.60 %.

XXV - c-4-ethyl-c-5- (2-fluorobenzyloxy) -r-2-methyl-1,3-

dioxane; Bp 115-118 ° C / 0.11 torr; C 66.41 %, H 7.61 %.

XXVi - c-4-ethyl-r-2-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 114-120 ° C / 0.06 torr; C 72.25 %, H 8.84 %.

XXVII - c-5- (2-chlorobenzyloxy) -c-4-ethyl-r-2-methyl-1,3-

dioxane; B.p. 123-128 ° C / 0.13 torr; C 62.39%,

XXVIII - c-5-Benzyloxy-c-4-ethyl-r-2-isopropyl-1,3-

dioxane; Bp 106-108 ° C / 0.01 torr; C 73.02%, H 9.46%.

H 6.96 %.

XXIX - c-4-ethyl-c-5- (2-fluorobenzyloxy) -r-2-isopropyl-

1,3-dioxane; Bp 115-118 ° C / 0.01 torr; C 68.36 %, H 8.26 %.

XXX - c-4-ethyl-r-2-isopropyl-c-5- (2-methylbenzyloxy) -

1,3-dioxane; Bp 105-1O6 ° C / O, O3 torr; C 73.65 %, H 9.56 %.

XXXI - c-5- (2-chlorobenzyloxy) -c-4-ethyI-r-2-isopropyl-

1,3-dioxane; B.p. 123-125 ° C / C.01 torr; C 64.51 %, H 7.93 %.

According to the method for preparing Intermediate A, threo-2- (2-methylbenzyloxy) -1,3-butanediol (Intermediate P) and threo-2-benzyioxy-1,3-butanediol) with an appropriate carbonyl compound or its acetal are as follows Connections implemented:
Examples

XXXII - c-4-methyl-c-5- (2-methylbenzyloxy) -r-2-phenyl-

1,3-dioxane; Bp 165 ° C / 0.005 torr; Mp 52-57 ° C; C 76.12 %, H 7.60 %.

XXXIII - cis-2-methyl-3- (2-methylbenzyloxy) -1,5-dioxaspiro-

/5.5/undecane; Bp 135-137 ° C / 0.012 torr; C 74.15 %, H 9.20 %.

XXXIV-A - r-2-Chloromethyl-c-4-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; 120-121 ° C / 0.005 Torr; C 62.41%, K 7.20 %.

809809/1079

XXXIV-B - r -2-Chloromethyl-t-4-methyl-t-5- (2-methylbenzyloxy) -1,3-dioxane; Kp. Not determinable; NMR spectrum is consistent with the assumed structure. XXXV - cS-Benzyloxy-r ^ -chloromethyl-c ^ -methyl-i, 3-dioxane; Bp 102-110 ° C / 0.012 torr; C 60.72 %,

H 6.40 %.

Example XXXVI cis -4-Methvl-5- (2-methylbenzvloxv) -1,3-dioxane

The compound is prepared in a manner similar to Intermediate A using 12.0 g of threo-2- (2-methylbenzyl oxy) -1,3-butanediol (Intermediate P), 3.33 g of paraformaldehyde and 9.30 g of p-toluenesulfonic acid made in 300 ml of anhydrous hexane. By recrystallizing the crude reaction product from ethanol / water, 7.40 g of cis-4-methyl-5- (2-methylbenzyloxy) -1,3-dioxane are obtained; Mp 54 ° C. The structure is confirmed by the NMR spectrum. Analysis for C ₁₃ H ₁₈ O ₃ : CH

calc .: 70.24; 9.16;

20 found: 70.46; 8.07-

Comparative example XXXVII 5-methyl-5- (2-methylbenzyloxy) -1 , 3-QJoxane

The compound is prepared in a manner similar to Intermediate A using 6.0 g of 2-methyl-2- (2-methylbenzyloxy) -1,3-propanediol (Zv / ischenproduct Q), 1.66 g of paraformaldehyde and 0.13 g of p-toluenesulfonic acid prepared in 150 ml of anhydrous hexane. By distilling the crude reaction product under reduced pressure with the aid of a still with a short V / egen, 3.64 g of 5-methyl-5- (2-methylbenzyloxy) -1,3-dioxane are obtained in one fraction; B.p. 106 10 8 ° C / O, O1 torr. The structure is confirmed by IR and NMR spectra.
Analysis for C ₁₃ H ₁₈ O ₃ : CH

calc .: 70.24; 8.16;

35 found : 70.02; 8.31.

809809 / 1.079

The following 4-substituted 1,3-dioxanes are prepared using the procedures described above: Examples
XXXVIII - c-5-Benzyloxy-r-2-ethyl-c-4, c-6-diraethyl-1,3-

5 dioxane; Bp. 108 - 110 ° C / O.011 Torr, which is ver

solidifies, mp 31-33 ° C; C 72.30 %, H 8.92 %.

dioxane; Bp 92-94 ° C / 0.05 torr; C. 72.10 %, H 9.15 %.
XL- c-5-Benzyloxy-r-2-ethyl-t-4, t-5-dimethyl-1,3-

dioxane; Bp 109-110 ° C / 0.011 torr; C 72.22%

H 8.91%
XLI - r-2- (2-cyanoethyl) -c-4-methyl-c-5- (2-methylbenzyl-

oxy) -1,3-dioxane: F. 50 - 51.5 ° C, C 70.04 %, H 7.59%

XLII - r-2-ethyl-c-5 - / (2-furyl) -methoxy7-c-4-methyl-1,3-

dioxane; Bp 70-72 ° C / 0.003 torr; C 64.02 %>

H 7.99 %.

XLIII - cis-5-benzyloxy-4-ethyl-1,3-dioxane; Bp 96-100 ° C / 20 0.01 torr; C 70.52 %, H 8.20 %.

XLIV - c-5-benzyloxy-r-2-ethyl-c-4-isopropyl-1,3-dioxane;

Bp 108-125 ° C / 0.12 torr; C 72.11 _% H 9.02 %. XLV - r-2-Xthyl-c-5- (2-fluorobenzyloxy) -c-4-isopropyl-1,3-

dioxane; Bp 100-110 ° C / 0.005-0.027 torr; C 68.10 %, H 8.41 %.

XLVI - r-2-ethyl-c-4-isopropyl-c-5- (2-fluorobenzyloxy) -

1,3-dioxane; Bp 123-124 ° C / 0.11-0.12 torr;

C 73.49 %, H 9.47 %.
XLVII - c-5- (2-chlorobenzyloxy) -r-2-ethyl-c-4-isopropyl-

1,3-dioxane; Bp 116-117 ° C / 0.022 torr; C 65.13 ^c / o,

H 7.91 %.
XLVIII - c-5-benzyloxy-r-2, c-4-dimethyl-1,3-dioxane; Kp.

90-94 ° C / 0.008 torr; C 70.03 %, H 8.18 %. XLIX - c-5- (2-fluorobenzyloxy) -r-2, c-4-dimethyl-1,3-dioxane;

Bp 83-83.5 ° C / 0.009 torr; C 64.81 %, H 7.42 %. L - r-2, c-4-dimethyl-c-5- (2-methylbenzyloxy) -1,3-

dioxane; B.p. 100-1O5 ° C / O, 005 torr; C 71.16 %,

H 8.64 %.

809809/1079

- 39 -

LI - c-5- (2-chlorobenzyloxy) -r-2, c-4-dimethyl-1,3-dioxane;

Bp 113 ° C / O, 023 torr; C 60.51 %, H 6.76 tf. LII - c-5-benzyloxy-r-2-tert-butyl-c-4-methy1-1,3-dioxane;

Bp 84-87 ° C / 0.006 torr; C 72.96 %, H 9.41 %. LIII - r-2-tert-butyl-c-5- (2-fluorobenzyloxy) -c-4-methyl-

1,3-dioxane; Bp 79-81 ° C / 0.008 torr; C 67.84 %,

H 8.37 %.
LIV - r-2-tert-butyl-c-5- (2-methylbenzyloxy) -c-4-methyl-1,3-dioxane; Bp 95-99 ° C / 0.13 torr; C 72.96 #, H 9.52 %.

LV - r-2-tert-butyl-c-5- (2-chlorobenzyloxy) -c-4-methyI-

1,3-dioxane; Bp 107-112 ° C / 0.14 torr; C 63.99 %,

H 7.77%

LVI - r-2-ethyl-c-5- (3-fluorobenzyloxy) -c ~ 4-methyl-1,3-dioxane; Bp 101.5-102 ° C / 0.015-0.02 torr;

C 66.38 54, H 7.66 #.
LVII - r-2-ethyl-c-5- (4-fluorobenzyloxy) -c-4-methyl-1,3-

dioxane; B.p. 92.5-93 ° C / O, 0.1 torr; C 65.81 %, H 7.71 %.
LVIII- c-5- (2,6-difluorobenzy? UOxy) -r-2-ethyl-c-4-methyl-1,3-

dioxane; Bp 82-84 ° C / 0.004 torr; C 61.90 %,

H 6.67 %.
LIX - r-2-ethyl-c-4-methyl-c-5- (3-diethylbenzyloxy) -1,3-dioxane; B.p. 88-90.5 ° C / O, 0.35 torr; C 71.79 %, H 9.03 %.

LX r-2-ethyl-c-4-methyl-c-5- (4-methylbenzyloxy) -1,3-

dioxane; Bp 106-110 ° C / 0.006 torr; C 71.71 %,

H 8.85%.

LXI- r-2-Ä ■ thyl-c-4-methyl-c-5- (2,6-dimethylbenzyloxy) -

1,3-dioxane; F. 74-74.5 ⁰ C; C 72.76 %, H 8.90 %.

LXII - c-5- (3-chlorobenzyloxy) -r-2-ethyl-c-4-methyl-1,3-

dioxane; Bp 146.5-147.5 ° C / 0.29 torr; C 62.12%,

H 6.96 %.

LXIII - c-5- (4-chlorobenzyloxy) -r-2-ethyl-c-4-methyl-1,3-dioxane; Bp 109.5-111.5 ° C / O, O3 torr; C 61.89 %,

H 7.04 %.

809809/1079

¹ LXIV -

LXV 5

LXVI -

¹ O LXVII LXVIII

¹⁵ LXIX LXX -

LXXI LXXII -

LXXIII LXXIV -

LXXV LXXVI -

c-5- (2,6-dichlorobenzyloxy) -r-2-ethyl-c-4-methyl-1,3

dioxane; B.p. 131-132 ° C / O, O2 torr; C 55.21 ϊ>,

H 5.94 %.

c-4-butyl-r-2-ethyl-c-5- (2-fluorobenzyloxy) -1,3-

dioxane; Bp 136-137 ° C / 0.15 torr; C 69.14 %,

H 8.34 %.

c ^ -Butyl-r - ^ - ethyl-c-S- (2-methylbenzyloxy) -1,3-

dioxane; 119-122 ° C / 0.013-0.019 torr;

C 74.39 %, H 9.68%.

c-4-butyl-c-5- (2-chlorobenzyloxy) -r-2-ethyl-1,3-

dioxane; Bp 154-159 ° C / 0.25 torr; C 65.48, H 8.01 %

- r-2-ethyl-c-5- (2-fluorobenzyloxy) -c-4-pentyl-1,3-dioxane; 119-121 ° C / 0.019 torr; C 69.61 %,

H 8.57 %.

r-2-ethyl ~ c-5- (2-methylbenzyloxy) -c-4-pentyl-1,3-

dioxane; B.p. 125-126.5 ° C / 0.024 torr; C 74.33%

H 9.88 %.

c-5- (2-chlorobenzyloxy) -r-2-ethyl-c-4-pentyl-1, 3-

dioxane; Bp 136-137.5 ° C / 0.02 torr; C 66.48 %,

H 8.48 %.

c-5-benzyloxy-c-4-ethyl-r-2-propyl-1,3-dioxane; Bp 105-110 ° C / 0.02 torr; C 72.70% H 9.29 %.

c-4-ethyl-c-5- (2-methylbenzyloxy) -r-2-propyl-1,3-

dioxane; Bp 110-116 ° C / 0.02 torr; C 73.13 %,

H 9.39 %.

- c-5-Benzyloxy-r-2-butyl-c-4-methyl-1,3-dioxane;

Bp 95-102 ° C / 0.0C3 torr; C 72.61 %, H 8.91 %. r-2-butyl-c-5- (2-fluorobenzyloxy) -c-4-methyl-1,3-dioxane; Bp 101-1O7 ° C / O, 005 torr; C 68.06% H 8.00 %.

r-2-butyl-c-4-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 115 ° C / O, 005 Torr; C 73.37 %, H 9.52 %. r-2-butyl-c-5- (2-chlorobenzyloxy) -c-4-methyl-1,3-dioxane; Bp 93-1O6 ° C / O, 003 torr; C 64.63% H 7.62 %.

809809/1079

LXXVII - r -2-hexyl-c-4-raethyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 140-150 ° C / 0.15 torr; C 74.38 Ji,
H 9.93 %.

LXXVIII - r -2-methoxymethyl-c-4-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 124-128 ° C / 0.04 torr;

C 67.48 %, H 8.56 %.

LXXIX - r-2-bromomethyl-c-4-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 132.5-135 ° C / 0.16 torr;
C 53.46 %, H 6.06 %.

LXXX - r-2-ethyl-c-5- (2-fluorobenzyloxy) -c-4, c-6-dimethyl-1,3-dioxane; Bp 101-1O3 ° C / O, O3 torr; Mp 43-45.5 ° C; C 67.10 ^, H 7.76 %.
LXXXI - r-2-ethyl-c-4, c-6-dimethyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 112 ° C / 0.04 torr; F. 56-58 ⁰ C;
C 72.62 ϊί, Κ 9.00 %.

LXXXII - c-5- (2-chlorobenzyloxy) -r-2-ethyl-c-4, c-6-dimethyl-1,3-dioxane; Bp 112-118 ° C / 0.013 torr;
M.p. 58.5-60 ° C; C 63.28 %, H 7.42 %.

LXXXIII - r-2-ethyl-c-5- (2-fluorobenzyloxy) -c-4, t-6-dimethyl-1,3-dioxane; Bp 102-106 ° C / 0.025 torr;

C 67.40 %. H 8.04 ^r / b.

LXXXIV - r-2-ethyl-c-4, t-6-dimethyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 98-100 ° C / 0.015-0.020 torr;
C 72.73 %, H 8.86 %.

LXXXV - c-5- (2-chlorobenzyloxy) -r-2-ethyl-c-4, t-6-dimethyl-1,3-dioxane; Bp 106-1O8 ° C / 0.12 torr;
C 63.37 %, H 7.54%.
LXXXVI - r-2-ethyl-c-5- (2-fluorobenzyloxy) -t-4, t-5-dimethyl-

1,3-dioxane; Bp 118-122 ° C / 0.015 torr; 30 C 67.42> Ό, H 8.16 V ».

LXXXVII - c-5- (2-chlorobenzyloxy) -r-2-ethyl-t-4, t-5-dimethyl-1,3-dioxane; Bp 110 ° C / 0.01 torr; C 63.25 %,
H $ 7.38 S.

LXXXVIII-r-2-cyanomethyl-c-4-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane; Bp 167-177 ° C / 0.008 torr; C 69.23 %,

H 7.39 %.

809809/1079

LXXXIX -

XC -

XCI -

10 XCII - XCIII - 15th XCIV - XCV - XCVI - 20th XCVII - XCVIII 25th XCIX - C - CI -

CII -

r - ^ - ethyl-c - ^ - methyl-c- 5- / Ϊ 2-pyridyl) -methoxy / -

1,3-dioxane; Bp 85-87 ° C / 0.004 torr;

C 65.98 Si, H 7.96 %.

r-2-ethyl-c-4-methyl-c-5 - / (3-pyridyl) methoxy / -

1,3-dioxane; Bp 96-98 ° C / 0.003 torr; C 66.00? I,

H 8.11 %.

r-2-ethyl-c-4-methyl-c-5 - / (4-pyridyl) -methoxx / -

1,3-dioxane; Bp 110-112 ° C / 0.005 torr; C 66.07 %,

H 8.32 %.

r-2-ethyl-c-4-methyl-c-5 - / (2-thienyl) -methoxx / -

1,3-dioxane; Bp 98-100 ° C / 0.005 torr; C 59.53 %,

H 7.33 Si.

cis -4-ethyl-5- (2-fluorobenzyloxy) -1,3-dioxane;

M.p. 72.5-73 ° C; C 65.02 Ji, H 6.90 %.

cis -4-ethyl-5- (2-methylbenzyloxy) -1,3-dioxane;

M.p. 71.5-73 ° C; C 70.88 Si, H 8.27 Si.

eis-A-ethyl-5- (2-chlorobenzyloxy) -1,3-dioxane;

M.p. 73-75 ° C; C 60.62 %, H 6.59 %.

cis -4-Athy1-5- (2,6-difluorobenzyloxy) -1,3-dioxane;

M.p. 91-92 ° C; C, 60.58 Ji; H 6.46 Ji.

cis -5-benzyloxy-4-methyl-1,3-dioxane; Mp 35-36 ° C;

C 69.34 Si, H 7.78 Si.

cis -5 (2-fluorobenzyloxy) -4-methyl-1,3-dioxane;

M.p. 38-40 ° C; C 64.03 %, H 6.86

cis -5 (2-chlorobenzyloxy) -4-methyl-1,3-dioxane;

M.p. 73-75 ° C; C 59.31 #, H 6.29 Si.

cis -5 (2,6-difluorobenzyloxy) -4-methyl-1,3-dioxane;

M.p. 64-66 ° C; C 58.81 Si, H 5.93 %.

c-5-benzyloxy-c-4-tert-butyl-r-2-ethyl-1,3-dioxane;

Bp 100-1O5 ° C / O, 007 torr; C 73.19 Si, H 9.23 %.

c-4-tert-butyl-r-2-ethyl-c-5- (2-fluorobenzyloxy) -

1,3-dioxane; Bp 101-103 ° C / 0.02 torr; C 68.96 Si,

H 8.71 Si.

809809/1079

The herbicidal activity of the compounds according to the invention results from the following experiments:

Seedling rows of Lima beans (Phaseolus lunatus), maize (Zeamays), oat grass (Avena fatua), lettuce (Lactuca. Sativa), Mustard (Brassica juncea) and fingergrass (Digitaria sanguinalis) are planted in shallow troughs of 20 15 χ 8 cm in size, which contain about 5 cm of sandy loam soil. A thin layer of earth (about 1 cm) is spread over the surface around the To cover seedlings. In addition, pots are used which contain tubers capable of propagation at a depth of 2.5 cm Cypergrass (Cyperus rotundus) included.

In the pre-emergence application, an aqueous acetone solution of the test compounds containing an amount of acetone sufficient to dissolve is used contains, in an application rate of 8.96 kg / ha or parts thereof (4.48, 2.24, 1.12, 0.56 or 0.28 kg / ha) on the Sprayed soil, which the seedlings in the troughs or /. the tubers covered in the pots, the total volume being 760 liters / ha is equivalent to. The troughs and pots are kept in a greenhouse for 10 to 14 days with interrupted strong light intensity held, whereupon the herbicidal effectiveness of the compounds is determined. For this purpose, individual plant varieties are compared examined with untreated plants. Tables I and II show those according to the invention in the pre-emergence application Compounds obtained results along with results from parallel tests on known compounds found in the 4- and 6-positions of 1,3-dioxane are unsubstituted, reproduced.

From Table I it can be seen that the compounds from Examples I, II, III and IV are herbicidally effective against grassy species such as maize and fingergrass at application rates of 0.56 kg / ha or below, while the known known, used as the standard, 1,3-dioxane unsubstituted in the 4- and 6-positions is significantly less active. The compounds of Examples I, II and III are in the control of

L 809809/1079 -J

cypergras at 2.24 kg / ha about twice as effective as the known comparison compound. The compound from Comparative Example XV is completely inactive at A, 48 kg / ha or below, at an application rate of 8.96 kg / ha, it shows only very little activity against maize and finger grass. This connection differs from the known comparison compound in that it has two methyl groups in the 4-position of the dioxane ring. It has practically no herbicidal activity. The compound from Comparative Example XIII is completely inactive at 8.96 kg / ha. This compound only differs from the compound from Example II by the stereochemical relationship between the 2-ethyl substituent and the 5- (2-methylbenzyloxy) substituent. These substituents are present in the active compound from Example II ice to one another, while they are trans to one another in the case of the inactive compound from Comparative Example XIII.

A number of other plant varieties are also used for pre-emergence, e.g. Sesbania spp., Sugar beet (Beta vulgaris), soybeans (Glycine max.), Cotton (Gossypium hirsutum), black millet (Sorghum vulgare), rock cress (Cassia obtusifolia), barley (Hordeum vulgare), chicken millet (Echinochloa crusgalli), peanut plants (Arachis hypogaea), safflower (Carthamus tinctorius), tomatoes (Lycopersicon esculentum), rice (Oryza sativa), wheat (Triticum aestivum), purple bindweed (Ipomoea purpurea), rapeseed (Brassica campestris), Sida spinosa L., foxtail grass (Setaria faberii), oats (Avena sativa), downy bristle (Bromus tectorura) and Sesbania exaltata.

In this extended test of the compounds according to the invention the compound from Example I with the comparative standard A, the compound from Example II with the comparative standard B and the compound from Example III with the same standard C compared. The comparison standards are known compounds that differ from the

809809/1079

JS

inventive compounds differ only in that they do not have a 4-substituent. Those summarized in Table II Results show that the 4-substituted Dioxanes of the invention are far more active than the corresponding 4-unsubstituted known compounds. Also owns the well-known dioxane (comparative standard D), which has a 5-methyl substituent instead of the 4-methyl substituent of the has compounds according to the invention, lower herbicidal Effect on maize, oat grass, fingergrass, barn millet, foxtail grass, oats, barley and rice than those according to the invention Links. The compounds of the invention are less toxic to wheat than the known dioxane, while they are non-toxic to lettuce, tomatoes and peanut plants and to soybeans, cotton and sugar

t5 rübeii, in each case with application rates of 4.48 kg / ha or less, are practically non-toxic.

The results of pre-emergence tests with further compounds according to the invention are compiled in Table III.

A comparison of the results with the compounds from Example XXXVI and Comparative Example is particularly important here XXXVII of interest. None of these compounds contains a 2-substituent, but the compound from Example XXXVI with a cis-4-methyl substituent opposite the three Grasses extremely active, while the compound from Comparative Example XXXVII with a 5-methyl substituent at 8.96 kg / ha is significantly less active.

For the post-emergence tests, those are planted with seedlings Troughs are kept in a greenhouse until the first three-part leaves of the bean plants have unfolded. the Plants are then sprayed with an aqueous acetone solution of the test compounds as in the pre-emergence tests. On that the plants are returned to the greenhouse and kept for 10 to 14 days with interrupted high-intensity light irradiation. The herbicidal activity of the compounds is then determined. Table IV shows the post-emergence

^L - 809809/1079 -J

application of the compounds according to the invention achieved results reproduced.

The active 1,3-dioxanes of the invention can be used in various Formulations used as herbicides, e.g. together with agricultural auxiliaries and agricultural carriers in the form of herbicidal agents. These agents contain about 0.01 to 95 percent by weight of the active 1,3-dioxane combined with about 4 to 98 »5 percent by weight of a conventional carrier and about 1 to 15 percent by weight of a wetting agent. It is well known that the formulation and type of application can influence the activity of a particular material. The compounds according to the invention can, depending on the desired type of application, e.g. as emulsion concentrates, Granules with a relatively large particle size, wettable powders, solutions or other common forms can be formulated.

Emulsion concentrates are in water or other dispersants dispersible homogeneous liquids or pastes, which can consist either entirely of a compound according to the invention and a liquid or solid emulsifier or can additionally contain a common liquid carrier, e.g. xylene, heavy aromatic naphtha cuttings, Isophorone or other non-volatile organic solution

25 medium. A special emulsion concentrate ("4EC") with

0.479 kg active ingredient / liter concentrate contains e.g. 53.01 parts r-2-ethyl-c-4-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane, 6.0 parts of a mixture of alkylnaphthalene sulfonates and polyoxyethylene ethers as emulsifiers, 1.0 part of an epoxy

30 dated soybean oil as a stabilizer and 39.99 parts of one

High flash point petroleum distillate as a solvent.

Granular formulations are particularly suitable for treating surfaces and to penetrate dense leaf umbrellas. Various granular formulations can be used. at Soaked granules are usually called the active ingredient

809809/1079

Solution in a solvent applied to coarse particles of an absorbent carrier, for example attapulgite or kaolin clay, corn bran or expanded mica. Surface-coated granules can be prepared by spraying the molten active ingredient onto the surface of a generally non-absorbent particle or by spraying a solution of the active ingredient in a solvent. Water-soluble substances, for example fertilizers, or insoluble substances, such as sand, marble fragments or coarse-grained talc, are suitable as the core material. Particularly preferred are granules in which a spray powder is applied as a surface coating to sand or another insoluble particle so that the spray powder can become dispersed on contact with moisture. Granules can be produced by compacting dusts and powders with press rollers, by extrusion or with the aid of a granulating disk. Granular formulations can have a wide range of concentrations; for example 0.5 up to 95 % of the active ingredient.

Wettable powders, which are suitable for both pre-emergence and post-emergence use, are finely divided powders that are easily dispersed in water or other dispersants. The soil or unwanted plant growth are treated with the wettable powder either in the form of finely divided dry material or as an emulsion in water or another liquid. Typical carriers for wettable powders are, for example, Fuller's earth, kaolin clays, silicon dioxide and other highly absorbent materials that can be easily wetted with inorganic diluents. The wettable powders usually contain about 5 to 80 % of the active ingredient, depending on the absorbability of the active ingredient and the absorption capacity of the carrier. They also usually contain a small amount of a wetting agent, dispersant or emulsifier to facilitate dispersion, common surface-active agents of this type are, for example, alkyl

809809/1079

and alkylarylsulfonates and sulfates and their sodium salts, Polyethylene oxides, sulfonated oils, fatty acid esters of polyhydric alcohols and other commercially available surfactants Middle. The surfactant, if used, constitutes about 1 to 15 percent by weight of the herbicidal • By means of.

The formulations can be used either without further dilution or as dilute solutions, emulsions or suspensions in Water or other suitable diluents can be used. The funds can be applied to the surfaces to be treated by spraying the unwanted vegetation or the soil surface if they are liquid, or by spreading it with mechanical devices, if solid, can be used. The material applied to the floor surface can either remain unchanged or be mixed with the upper layer of soil by cultivating the soil in order to achieve the best possible results Achieve results.

The herbicides of the invention can optionally together with insecticides, fungicides, nematicides, plant growth regulators, Fertilizers and other agricultural chemicals and / or applied. When using the herbicides according to the invention either alone or together with others An amount and concentration of 1,3-dioxane which is sufficient for the herbicidal effect is used for agricultural chemicals used. While this effective amount is variable, it will generally give 0.1 to 9 kg / ha, e.g., 0.28 to 4.48 4.48 kg / ha, sufficient if applied evenly

³⁰ effect.

809809/1079

Table I.
Pre-emergence herbicidal activity of 4-substituted 1,3-dioxanes

link

the end

Example plant species

Lima beans

Corn

Oat grass

Lettuce

mustard

Fingergrass

Cypergrass

Lima beans

Corn

Oat grass

Lettuce

mustard

Fingergrass

Cypergrass

Death rate (%) at the following application quantities

(kg / hectare)

0.2F "

III

Lima beans

Corn

Oat grass

Lettuce

mustard

Fingergrass

Cypergrass

0756

100 100

0
100

100

40

100
75

100 10

0
100

1.12

100 95 *

0 100

100 95 * 0 0

100 25

100 90 *

0 100

2.24

100 95 * 0 0

100 95 * 0 0

4.48 8.96 60 * 80 * 100 100 100 100 0 O 0 * 0 * 100 100 75 * 75 * 40 * 90 * 100 100 100 100 0 0 10 * 0 100 100 75 * 100 10 90 * 100 100 100 100 0 0 0 10 * 100 100 80 * 100

OO CD O

Oil

Table I - continued

0.28

0.56

1.12

2.24

4.48

8.96

IV co XV Lima beans O 0 0 0 0 * 0 * I. O Corn 70 * 100 100 100 100 100 ^ P co Oat grass 20th 40 80 * 100 100 100 ^ "I. 00 Lettuce 0 - 0 0 0 0 O mustard 0 0 0 0 60 * 100 to Fingergrass 100 100 100 100 100 100 O AXxX Cypergrass - - - - - -4 Lima beans 0 «0 Corn mm - - 0 Oat grass mm _ - - 0 Lettuce _ - - - 0 mustard _ - - 0 Fingergrass - - - - - 0 Lima beans _ 0 0 0 0 0 Corn 0 0 0 0 30th OO Oat grass _ 0 0 0 0 0 CO Lettuce - _ 0 0 0 0 0 O mustard 0 0 0 0 0 CO Fingergrass 0 0 0 0 0 Cypergrass - 0 0 0 0 0

8 S <Ä ο α.

Table I - continued

0.28 0.56 1.12 2.24 4.48 8.96

Standard Lima Beans - 0 0 0

α » for ver maize - ο 70 * 70 *

ο equal to ** oat grass ο 0 40

co lettuce - ο * ■ 0 ^ O

⁰⁰ mustard - 0 0 0

° fingergrass - ο 100 -

Cypergrass ο 0 25

* Plants that have not been exterminated are severely damaged and will grow probably not recover

** r-2-Ethyl-5-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane.

- ■ "Irish

Table II

Extended testing of the pre-emergence herbicidal activity of 4-substituted 1,3-dioxanes

Connection off
example

Plant species

Absteri> erate 00 with the following application quantities (kp; / hectare)

0.28

Lima beans 0

Corn 0

Oat grass 0

Lettuce 0

Mustard 0

Fingergrass' 90 *

Soybeans ο

Cotton 0

Purple bindweed 0 Sesbania exaltata ο

Chicken millet 20

Foxtail grass 30

Fluffy bristle 0

Rockcress 0

Sida spinosa L. 0

Wheat 0

Carrots 0

Oats 10

Barley go *

Sugar beet 0

Tomatoes 0

Rice 80 *

Safflower 0

Peanut 0

Rapeseed 0

Comparison Lima beans
Standard corn
A oat grass
Lettuce
mustard

Fingergrass
Soybeans
cotton
Purple bindweed

0 0 0 0 0 0 0 0 0

Sesbania exaltata 0

Chicken millet 0

Foxtail grass 0

Fluffy bristle 0

Rockcress 0

Sida spinasa L. q

Wheat q

Carrots 0

Oats 0

Barley 0

0.56Γ7Τ22.24

0
100

0
100

70 *
70 *

20th

50

100

0
100

0
20th

10
30th

0
20th

100
20th

0
100

70 *
100
20th

70
80 *
100

0
100

30th
20th

0
50

30th
50

20th
80 *

100

50

100 0 0 0 0

100

100

40

100 80 *

100 0 0

100 0 * 0 0

100

40

100 0 0 0 0

100

70

40

100

70 * 100

4.48

0 * 100 100

0 * 100

0 * 100 100 80 *

20 100 100 100

100 50 *

100 60

0 100

100 100 100

100 100 100

809809/1079

Table II - continued

Plant species Mortality rate (%) at following 0.56 1.12 2.24 4.48 sugar beet Applications (kg / hectare) Connect tomatoes 0 0 0 0 application rice 6/28 0 0 0 0 Example Safflower 0 50 100 100 Peanut 0 0 0 0 0 Rapeseed 0 0 0 0 0 Lima beans 0 0 0 0 0 Corn 0 0 0 0 0 * Oat grass 0 100 100 100 100 Lettuce 0 40 70 * 100 100 II mustard 0 0 0 0 0 Fingergrass 30th 0 0 0 50 * Soybeans 0 100 100 100 100 cotton 0 0 0 0 0 * Purple bindweed 0 0 0 0 0 * Sesbania exaltata 70 * 0 0 0 0 Chicken millet 0 0 0 0 0 * Foxtail grass 0 50 100 100 100 Downy bristle 0 30th 50 * 100 100 Rock cress 0 0 0 50 70 * Sida spinosa L. 30th 0 0 0 0 * V / eizen 20th 0 0 0 0 * Carrot millet 0 0 0 0 30th oats 0 40 70 * 90 * 100 barley 0 70 80 * 100 100 sugar beet 0 100 100 100 100 tomatoes 0 0 0 0 0 rice 50 0 0 0 0 Safflower 50 * 100 100 100 100 Peanut 0 0 0 0 40 Rapeseed 0 0 0 0 0 Lima beans 80 * 0 0 0 0 * Corn 0 0 0 0 0 Oat grass 0 0 70 30th 100 Lettuce 0 0 0 0 40 Ver mustard 0 0 0 0 0 equal Fingergrass 0 0 0 0 0 default Soybeans 0 50 70 70 * 100 B. cotton 0 0 0 0 0 Purple bindweed 0 0 0 0 0 Sesbania exaltata 50 0 0 0 0 Chicken millet 0 0 0 0 0 Foxtail grass 0 0 30th 70 70 * Downy bristle 0 50 30th 50 60 * 0 0 0 30th 70 0 0 0

809809/1079

-ItK-

Table II - continued

link

^ouch ? ^egg ~ plant species rockcress

Sida spinasa L.

wheat

Carrot millet

oats

Gers te

sugar beet

tomatoes

rice

Safflower

Peanut

Rapeseed

III Lima Bean Corn

Oat grass Lettuce mustard

Fingergrass Soybeans Cotton Purpurv: inde Sesbania exaltata Chicken Millet Foxtailgrass Fluffy Trespe Rockcress Si da spinosa L. Wheat
Millet oats
barley
Sugar beet tomato rice
Safflower
Peanut
Rapeseed

Lima beans are like corn
Standard oat grass C lettuce

mustard

Fingergrass Soybean Mortality Rate (%) at the Following Ad (kg / hectare)

7Τ2ΊΓ "οΤΊΠΓ 1.12 '2ΓΖΤ

0 0 0 0 0 0 0 0 0 0 0 0

0 0 0 0 0

30th 0 0 0 0 0 0

0 0 0 0 0

50 0 0

30 0 0 0

40 80 *

0 50

0 0 0 100 10 30th 0 0 0 0 100 100 0 0 0 0 0 0 0 0 20th 90 * 50 90 * 0 0 0 0 0 0 0 0 0 0 30th 50 30th 50 0 0 0 0 50 100 0 0 0 0 0 0

0 0 0 0 0

50 0

100

30th

100 0 0 0 0

100

100

20th

70 * 100 0 0

100 0 0 0

0 0 0 0 0

80 * 0

100

70

100 0 0 0 0

100

100

30th

80 * 100 0 0

100 0 0 0

30 0 0 0

100 0

4.46

100

0 100

100

100

0 * 100 0 * 0 0 0

100 100 80 * 0

20th

20th

100

100

100 50 0 0 *

100 20

0 100

809809/1079

Table II - continued

Connect Plant species Mortality rate (SO 0.56 1.12 with the following 4.48 application Applications 0 0 (k.?/cectar) 0 example cotton 0 0 0 Purple bindweed 0.28 0 0 2.24 0 . Sesbania exaltata 0 0 20th 0 90 * Chicken millet 0 70 100 0 100 Foxtail grass 0 0 0 0 20th Downy bristle 0 0 0 70 0 Rock cress 0 0 0 70 0 Sida spinosa L. 0 0 0 0 0 wheat 0 0 0 0 60 Carrot millet 0 0 0 0 60 oats 0 0 0 0 100 barley 0 0 0 20th 0 sugar beet 0 0 0 30th 0 tomatoes 0 0 50 50 80 rice 0 0 0 0 0 Safflower 0 0 0 0 0 Peanut 0 0 0 50 0 Rapeseed 0 . 0 0 0 0 Lima beans 0 0 0 0 100 Corn 0 0 0 0 60 Ver Oat grass 0 0 0 0 0 equal Lettuce 0 0 0 30th 0 * default mustard 0 0 60 20th 100 D. Fingergrass 0 0 0 0 0 Soybeans 0 0 0 0 0 Baumvrolle 0 0 0 100 0 Purple bindweed 0 0 0 0 0 Sesbania exaltata 0 30th 40 0 100 Chicken millet 0 0 0 0 70 Foxtail grass 0 0 0 0 80 Downy bristle 0 0 0 70 * 0 Rock cress 0 0 0 60 0 Sida spinosa L. 0 0 0 20th 60 wheat 0 0 0 0 70 * Carrot millet 0 0 20th 0 100 oats 0 50 * 70 * 20th 100 barley 0 0 0 20th _ sugar beet 0 0 0 70 0 tomatoes 0 30th 50 100 100 rice 0 0 0 0 0 * Safflower 0 0 0 0 0 Peanut 0 0 0 100 0 * Rapeseed 0 0 0 0 0 0

809809/1079

Table II - continued

Comparison standards:

A. cis -2-ethyl-5- (2-fluorobenzyloxy) -1,3-dioxane. 5 B. cis-2-ethyl-5- (2-methylbenzyloxy) -1,3-dioxane,

C. cis -2-ethyl-5- (2-chlorobenzyloxy) -1,3-dioxane.

D. r-2-Ethyl-5-methyl-c-5- (2-methylbenzyloxy) -1,3-dioxane.

* Plants that have not died are badly damaged and are unlikely to recover.

809809/1079

Table III

co O CO OO CD CO

Pre-emergence herbicidal activity of 4-sul Mortality rate (# oats ) at 8.96 0 established grass Head sa 0 kg / hectare link
οι ι e Τ2λ ί Lima Corn 100 lat 0 from ΰβι-
game beans 100 100 0 mustard V O 100 80 * 0 0 VI O 100 0 0 0 VII O 100 70 0 0 VIII O 100 100 0 0 IX ** O 100 90 * 0 0 X ** O 100 80 0 0 XI ** O 100 70 0 0 XII ** O 100 95 * 100 0 XVI 20th 100 80 * 0 0 XVII 60 * 100 50 0 0 XVIII 60 100 100 0 0 * XIX 0 100 100 0 0 XX 100 100 100 0 0 XXI 100 100 100 0 0 XXII 60 * 100 100 0 0 XXIII 100 100 100 0 0 XXIV 100 100 100 0 0 XXV 0 * 100 100 0 0 XXVI 100 100 100 0 - 0 XXVII 100 100 100 0 0 XXVIII 100 100 100 0 XXIX 60 * 100 100 - XXX 0 100 0 XXXI 0 0

Pinger Cyper 0 grass grass 100 100 100 100 75 * 0 0 100 75 100 100 100 0 100 50 100 100 100 100 100 50 100 0 100 75 100 75 100 75 100 50 100 100 100 100 100 100 100 50 100 0 100 0 100 0 100 100

cn

Table III - continued

Connection off

example

XXXII XXXIII XXXIV-A XXXIV-B

XXXVI XXXVII XXXVIII XXXIX

XLVII XLVIII

Lima
beans Corn oats
grass head
salad mustard 0 Finger-
grass ^ Cyp he
grass 0 100 90 0 0 100 η 0 100 95 0 0 * 100 η 0 100 100 0 0 100 W.
ο 0 0 0 0 0 0 * 40 * 100 100 0 0 100 ο 40 * 100 100 0 0 100 100 0 60 0 0 0 . 100 η 0 100 95 0 0 100 V
75 0 100 95 * 0 0 100 η 0 100 100 0 0 100 W.
η 20th 100 95 0 0 100 75 0 100 30th 0 0 80 * O 0 0 0 0 0 ο 0 0 0 0 0 ο 0 0 0 _ 0 ο 0 0 0 0 0 ο Q 80 * 100 40 0 0 100 100 60 * 100 80 0 0 100 100 0 100 95 0 0 100 100 40 * 100 50 0 0 100 AVW
100 0 0 0 0 0 0 25th 0 0 0 0 0 40 0 0 0 0 0 0 95 * O 0 0 0 0 0 O η 20th 100 100 0 100 \ j
0

Sä

Table III - continued

Connection from example

LVIII

• LXII ° LXIII

S ^LXIV

ο LXV co LXVI - ^ LXVII - * LXVIII

LXX LXXI LXXII LXXIII LXXIV LXXV LXXVI LXXVII LXXVIII LXXIX

Lima Corn Oats- head mustard finger Cyper 0 beans 100 ^ ras salad 0 grass grass 100 O 100 100 0 0 * 100 0 100 100 100 0 0 100 0 0 100 10 0 0 100 100 0 100 20th 0 0 100 0 0 100 90 * 0 0 100 0 0 100 70 0 0 100 0 0 100 95 * 0 100 100 0 100 100 100 0 0 100 0 0 0 95 * 0 0 100 0 0 0 0 0 0 90 0 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 80 * 0 0 100 0 0 70 80 * 0 60 * 100 100 0 0 100 0 0 100 100 0 0 100 75 * 100 100 100 0 0 * 100 100 60 * 100 100 20th 0 100 50 0 100 100 0 0 100 0 0 0 80 * 0 0 100 50 0 100 0 0 0 100 100 0 100 100 0 0 100 0 100 0 100

LD O CT)

OD
O
CO

Connection off

example

LXXX

LXXXI LXXXII LXXXIII LXXXIV LXXXV LXXXVI LXXXVII LXXXIX

XCVII XCVIII XCIX

Lima, - Corn oats head mustard 0 Pinger C yp er beans 100 grass salad 0 grass grass O 100 100 0 0 100 50 O 100 95 0 0 100 50 O 100 95 * 0 0 100 50 O 100 95 * 0 0 100 100 O 100 100 0 0 * 100 75 O 100 100 0 0 100 100 O 100 100 0 0 - 100 100 O 100 90 0 0 80 0 O* 0 100 0 0 100 0 0 100 20th 0 0 30th 0 0 * 100 95 * 0 0 100 50 40 100 100 0 0 100 50 40 * 100 95 * 0 0 100 100 0 * 0 100 0 0 100 75 0 0 0 0 90 0 0 0 0 80 50

* Plants that are not dead are badly damaged and will grow probably not recover.

** Application rate: 4.48 kg / ha.

/ 5 Lima
polisher 4 * substituted oats
grass head
salad WW \ * XT W finger
grass - 5 ^s !
Table IV Post-emergence herbicide effect of
1,3-dioxanes 0 fc death rate (%) at 8, 0 20th 100 0 ι corn 0 20th , 96 kg / hectare 90 * Connect
application
example 0 30 * O 100 mustard 100 I. 0 70 * 40 0 0 90 * II 0 0 * 50 - 10 100 III 0 70 * 30th - «0 * 60 IV 0 0 20th 0 0 0 V 0 0 20th 0 0 0 VI 0 0 0 0 0 0 VII 0 0 0 0 0 0 VIII 0 0 XIII 0 0 XV 0

* Plants that are not dead are badly damaged and are unlikely to recover.

809809/1079

Claims (2)

"1,3-Dioxanes, processes for their production and their ver application as herbicides " Priority: August 31, 1976, V.St.A., no.719 June 30, 1977, V.St.A., no.811 Claims γΊ.ι 1,3-dioxanes of the general formula »" O CH O - CB, - K ^r .CH. I. R * in which R is a hydrogen atom or an alkyl, haloal denotes kyl, alkoxyalkyl, cyanoalkyl or phenyl radical, R ^a 2a 2 is a hydrogen atom or R and R together form a divalent polymethylene group to form a spiro structure with 2 to 6 carbon atoms, R is an alkyl, haloalkyl or cyanoalkyl radical, R ^ is a hydrogen atom or an alkyl radical, R is a hydrogen atom or represents an alkyl, haloalkyl or cyanoalkyl radical, r
R is a phenyl, furyl, pyridyl, thienyl or by a or two chlorine atoms, fluorine atoms and / or methyl groups substituted ^L 809809/1079 ^J ι Γ 2 tuated phenyl group and -OCH ₂ - R is to R, if this is not a hydrogen atom. 2. Compounds according to claim 1, characterized in that that R is a hydrogen atom or an alkyl, haloalkyl 2a
or cyanoalkyl radical, R is a hydrogen atom, R represents an alkyl, haloalkyl or cyanoalkyl radical, R- * is a hydrogen atom or an alkyl radical and R represents a hydrogen atom or an alkyl, haloalkyl or cyanoalkyl radical. 3. Compounds according to claim 2, characterized in that Δ «5 f. that R is an alkyl radical, R ^ is a hydrogen atom and R is a water is a hydrogen atom or an alkyl radical. 15th 4. Compounds according to claim 3, characterized in that 2 f>
that R and R are hydrogen atoms. 5. Compounds according to claim 3, characterized in that R is an alkyl radical and R is a hydrogen atom. 6. Compounds according to claim 3, characterized in that R is a haloalkyl radical and R is a hydrogen atom. 7. Compounds according to claim 3, characterized in that 2 6 that R is a cyanoalkyl radical and R is a hydrogen atom. 8. Compounds according to claim 3, characterized in that 2 6
that R and R are alkyl radicals. 9. Compounds according to claim 2, characterized in that R ^{r is} a phenyl group or a phenyl group substituted by one or two chlorine atoms, fluorine atoms and / or methyl groups.
35 609809/1079 10. Compounds according to claim 9 »characterized in that R is an alkyl radical, R. is hydrogen and R is hydrogen or alkyl. 11. Compounds according to claim 10, characterized in that R and R are hydrogen atoms. 12. Compounds according to claim 10, characterized in that R is an alkyl radical and R is a hydrogen atom. 10 13 * Compounds according to claim 10, characterized in that R is a haloalkyl radical and R is a hydrogen atom. 14. Compounds according to claim 10, characterized in that that R is a cyanoalkyl radical and R is a hydrogen atom. 15 · Compounds according to claim 10, characterized in that R and R are alkyl radicals. 16. Herbicidal agents, characterized in that they contain at least one compound according to claim 1 and an extender contain. 17. Use of the compounds according to claims 1 to 15 as herbicides and plant growth regulators. 18. A process for the preparation of compounds according to claim 1, characterized in that a substituted 5-hydro xy-1, 3-dioxane of the formula 30 _R ^0H N, 109809/1079 in which the hydroxyl group is cis to R if this is not hydrogen atom is reacted with an alkali metal base in a solvent, the alkali metal alcoholate obtained with a Arylmethyl or heteroarylmethyl chloride or bromide of ⁵ Formula: R ^r -CH ₂ -Cl or R ^r -CH ₂ -Br converts or a threo-2-arylmethyl-1,3-diol of the general formula R * HO - CH '° " in the presence of an acidic catalyst with a carbonyl compound 2 2a bond of the formula R R C = O or the acetal thereof. 19 · Method according to claim 18, characterized in that a sodium compound is used as the alkali metal base. 20th 809809/1079