DE1230416B - Process for the preparation of triple chlorinated aromatic compounds - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 40S7 ¥ W PATENTAMT Int. Cl .:

C07c

EDITORIAL

German class: 12 ο -5/09

Number: 1230416

File number: H 43221IV b / 12 ο

Filing date: July 22, 1961

Opening day: December 15, 1966

The invention relates to a method of manufacture triple chlorinated aromatic compounds of the general formula

CH ₂ -O-X-OH

in which X an optionally substituted alkylene containing at least two carbon atoms, Alkyleneoxyalkylene or oxyalkylene group, which is characterized in that an im Ring chlorinated compound of the formula

Cl ₃

CH ₂ Cl

with a compound of the general formula HO - X - OH, in which X has the above meaning has, in a manner known per se, preferably in the presence of an acid acceptor, to react is brought.

Examples of compounds which can be prepared according to the invention are 2,4,5-, 2,3,4-, 2,3,6-, 2,4,6- and 3,4,5-trichlorobenzyloxyethanols, propanols, butanols, pentanols, -hexanols, -heptanols, -octanols and their mono-, di- and tri-lower alkylated substitution products and their oxy- and oxa-substituted ones Analogous, insofar as such substitutions are possible.

The compounds prepared according to the invention can be used to regulate plant growth, as Herbicides, flame retardants and plasticizers. According to the invention Compounds or isomer mixtures produced can be used as "pre-emergence" and as »Post-emergence herbicide« can be used. Particularly effective herbicides are mixtures of trichlorinated ones Benzyloxy ethanols, propanols, butanols, pentanols and hexanols and their monooxa- and monooxy substituted analogs.

If these substances are used as herbicidal agents, where the cheapness and easy availability of these compounds are particularly important, those isomer mixtures are preferred which contain at least 30% 2,3,6-trichlorobenzyloxyethanol or 2,3,6-trichlorobenzyloxypropanol contain. The new compounds are low-melting, waxy solids or liquids. which can be obtained by chlorination of toluene or o-chlorotoluene or, less conveniently, by processes for the preparation of triply chlorinated
aromatic compounds

Applicant:

Hooker Chemical Corporation,

Niagara Falls, N.Y. (V. St. A.)

Representative:

Dr. V. Vossius, patent attorney,

Munich 23, Siegesstr. 26th

Named as inventor:

Jack Samuel Newcomer, Wilson, N. Y .;

Edward David Weil, Lewiston, N. Y .;

Edwin Dorfman, Grand Island, N. Y .;

Jerome Linder,

Niagara Falls, N.Y. (V. St. A.)

Claimed priority:

V. St. v. America April 11, 1961 (102 099)

Chlorination of 2,6-dichlorotoluene, 2,5-dichlorotoluene, 2,3-dichlorotoluene or by chlorination of a mixture obtained therefrom, the chlorination being carried out until three in the aromatic ring Chlorine atoms are included and another chlorine atom is introduced into the side chain. The reaction product, which consists of a mixture that Contains at least 30% of the 2,3,6-trichloro isomer, is then according to the invention in a molar excess with a compound of the general formula HO - X - OH in the presence of an acid acceptor brought to reaction, where X has the meaning given above.

A product in particular has proven to be suitable for use as a herbicidal agent which consists of an isomer mixture containing at least 30% 2,3,6-trichlorobenzyl chloride Reaction with a molar excess of ethylene glycol or 1,2-propanediol is obtained. The pure ones 2,3,6-trichlorobenzyl chlorides are highly effective, however, there is no need to split these mixtures into their individual components, as one

609 747 '341

such separation would be very cumbersome and costly. Another reason to use of the isomeric reaction mixture or a mixture enriched with the 2,3,6-isomers is that astonishingly the 2,4,5-, 2,3,4-, 3,4,5- and 2,4,6-isomers in an isomer mixture which contains at least 30% of the 2,3,6-isomer, have considerable herbicidal activity, while these isomers alone have almost no herbicidal effect. An explanation for this behavior can be not be given.

It is thus according to a preferred embodiment of the invention, an isomer mixture, which contains 40 to 70% of the 2,3,6-trichloro isomer. When a higher proportion of 2,3,6 isomers is desired, the content of this isomer in the mixture is up to 100% Enriched by the by B r i m e 1 ο w and coworkers in J. Chem. Soc, pp. 1208 to 1212 (1951) used the procedure given.

There is a further advantage of the compounds produced by the process according to the invention in that, despite its high phytotoxic activity against weeds, it is a selective herbicide Have effect and against certain plants, such as corn, sugar cane, and grapes also have only a low phytotoxic effect on turf, which makes it possible that the very labor-intensive and costly removal of weeds using machines or by means of give up the hand and still get weed-free plantings.

The selective and only slight phytotoxic effect of the method according to the invention produced compounds over broad-leaved plants is not the only advantage of this Compounds, and some other advantages are given below.

For example, the compounds prepared by the process according to the invention can be used their use as herbicides are applied in various degrees of purity, namely from the highly purified oily or crystalline product to the technical crude product. Continue to bid These herbicidal agents have the advantage of being compatible with a variety of other herbicidal agents including trichlorophenylacetic acids, tetrachlorophenylacetic acids, sodium borates, calcium borates, of 2,4-dichlorophenoxyacetic acid and other herbicidal phenoxycarboxylic acids and esters as well as 4-chloro-2,6-ethylamine-5-triazine and other herbicidal triazines and 3- (p-chlorophenyl) -lJ-dimethylureaS-phenyl-Ll-dimethylurea, 3- (3,4-dichlorophenyl) -14-dimethylurea and other herbicidal ureas, of herbicidal chlorates, Petroleum products, hexachlorocyclopentadiene, pentachlorophenol, dinitro-o-alkylphenols, sodium trichloroacetate and sodium 2,3-dichloropropionate and with fungicidal agents such as Metal dimethyldithiocarbamates and ethylene bis (dithiocarbamates) as well as with insecticidal agents such as benzene hexachloride and 1,2,4,

^ y
hydroindan and also with fertilizers such as urea and ammonium nitrate and various known additives and diluents are compatible. The compounds prepared according to the invention can thus be used either as such or in the form of a wide variety of liquid or solid preparations. For example, these compounds can be used in the form of liquid preparations by diluting them with surface-active substances, dispersing, dissolving or emulsifying them in these substances, or by adding them to water or organic solvents such as petroleum, hydrocarbons, alcohols, ketones, Dissolves, disperses or emulsifies esters, glycols or mixtures thereof. Furthermore, the compounds prepared according to the invention can also be used in the form of solid preparations, for example in the form of scattering powder, wettable scattering powder or in the form of granules by adding diluents such as lime, clay, floury substances, starch, diatomaceous earth, mica, alkaline earth oxides, Carbonates and phosphates used in finely divided or granular form.

The liquid preparations, both the solutions and the dispersions of the active ingredient in a liquid solvent as well as the wettable powder preparations, can also be one or contain several surfactants in an amount sufficient to dissolve the preparation in water easy to make dispersible. The term "surface-active substances" includes wetting agents, dispersants, To be understood as emulsifying agents and the like. A sufficient but not complete one Compilation of such substances is in an article in "Soap and Chemical Specialies", Vol. 31, No. 7, pp. 50 to 61, as well as No. 8, pp. 48 to 61, No. 9, pp. 52 to 67 and No. 10, pp. 38 to 67, 1955, contain.

The manner in which the compounds prepared by the process according to the invention are used than herbicide is. varies and depends on the climatic conditions to be treated Plants, the weeds to be destroyed and the equipment to be used for this.

The amount to be used may vary due to the different resistance levels of the different Weed and useful plant species, due to the different degrees of growth of weeds and Useful plants as well as due to the different types of soil and different climatic conditions cannot be specified. Generally there will be at least about 0.3 kg of active ingredient per hectare and in consideration of cost, used no more than about 110 kg per hectare, the preferred being Amount range is between about 0.5 and 50 kg per hectare. When the weeds are in a If it is at an early stage of growth, it is naturally more sensitive, and in this case it is sufficient Quantities of around 0.5 to 4.5 kg per hectare, while weeds are more advanced in growth or for weeds that are to be completely destroyed, such as in borders or on Lawn, amounts greater than about 4 kg per hectare are used. In those cases where the weed growth is well advanced and where already ripe weed plants are to be combated, under Quantities of 50 kg per hectare and more may be required. For the destruction of what is deeply rooted Perennial weeds, such as from field winds, have amounts of about 10 to 100 kg per hectare proved to be useful. The examples illustrate the invention.

example 1

Toluene was chlorinated at a temperature of 60 to 7O ⁰ C in the presence of 0.1% iron (III) chloride as a catalyst until the increase in weight indicated that about 2.5 moles of chlorine were reacted. The product obtained was distilled and the ^{fraction boiling between 120 and 140 °} C. (20 mm Hg) was collected. Infrared analysis showed an isomer content of 25 to 40% of 2,4,5 isomer, 40 to 50% of 2,3,6 isomer and 10 to 15% of 2,3,4-trichlorotoluene. This trichlorotoluene was chlorinated at 100 to 200 ^° C. under irradiation with a mercury vapor lamp until 0.7 to 0.8 mol of hydrogen chloride per mol of trichlorotoluene had evolved. The product obtained was then fractionated to give the trichlorobenzyl chloride fraction having a boiling point of 131 to 152 ° C (6 mm Hg).
The Trichlorbenzylchlorid obtained was added with stirring to 1.5 molar equivalents of sodium hydroxide in a molar excess of said glycol in the table, and at a temperature of 140 to 150 ⁰ C, whereupon the reaction mixture heated and stirred for about 3 hours. The mixture was then poured into water, extracted thoroughly with toulol and distilled under reduced pressure to obtain the desired product. Infrared analysis showed that these products have essentially the same isomeric distribution as the intermediate trichlorotoluene.

middle
No. Group —X - Glycol used Description of the product Ana
calculated
Cl lysis
found
Cl la -CH ₂ CH ₂ - Ethylene glycol Semi-solid, boiling point 181 to
192 ° C (6 mm) 41.6 41.2 Ib -CH ₂ CH ₂ CH ₂ CH ₂ - 1,4-butanediol Viscous syrup, boiling point
140 to 168 ⁰ C (0.25 mm) 37.6 37.3 Ic -CH ₂ CH (CH ₂ ) - 1,2 propane
diol Viscous syrup, boiling point
140 to 168 ⁰ C (0.5 mm) 39.5 37.9 Id -CH ₂ CHOHCH ₂ - Glycerin Very viscous syrup,
Decomposition on distillation 37.5 39.3 Ie -CH ₂ CH ₂ OCH ₂ CH ₂ - Diethylene
glycol Viscous syrup, boiling point
175 to 185 ⁰ C (0.05 mm) 35.5 34.0 If - CHCH (CH ₃ ) OCh ₂ CH (CH ₃ ) - Dipropylene
glycol Viscous syrup, boiling point
180 to 185 ° C (0.05 mm) 32.5 32.7 ig -CH (CH ₃ ) CHCH (CH ₃ ) - 2,3-butanediol Viscous syrup, boiling point
170 to 176 ° C (5 mm) 37.7 42.0 lh -CH ₂ CH ₂ CH (CH ₃ ) - 1,3-butanediol Viscous syrup, boiling point
177 to 182 ° C (5 mm) 37.7 37.3 Ii - (CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ - Triethylene
glycol Viscous syrup, boiling point
210 to 250 ° C (0.38 mm) 31.0 28.8 Ij -CH ₂ CH ₂ - Ethylene glycol Semi-solid, boiling point 175 to
190 ° C (5 mm) 41.6 41.0 Ik -CH ₂ CH (CH ₃ ) - *) 1,2 propane
diol Viscose, semi-solid, boiling
point 145 to 16O ⁰ C
(0.5mm) 39.5 39.0

*) A preparation was used which was made from orthochlorotoluene (infrared analysis shows 60 to 70% of the 2,3,6 isomer and 30 up to 40% of the 2,4,5-isomer) had been produced.

Example 2

Production of 2- (2,3,6-trichlorobenzyloxyethanol)

It was 2,3,6-trichlorotoluene, which had been prepared by the method of Brimelow, Jones and Metcalf (U. Chem. Soc, 1951, p. 1208) at a temperature of 100 to 120 ⁰ C under irradiation with a Mercury vapor lamps are chlorinated until 0.7 to 0.8 moles of hydrogen chloride per mole of toluene have evolved. The 2,3,6-trichlorobenzyl chloride obtained, having a boiling point of 150 to 155 ^° C. (18 mm Hg), is separated from the unreacted 2,3,6-trichlorotoluene by fractionation. A solution is prepared of 44 parts of caustic soda in 250 parts of ethylene glycol by heating to 185 ⁰ C and subsequent cooling to 145 ⁰ C and treated her with this 115 parts of 2,3,6-Trichlorbenzylchlorid. After 3 hours of reaction at 145 to 150 ⁰ C, the reaction mixture with 2000 parts water and 1000 parts of toluene there is added. The toluene layer is then separated and fractionated. 65 parts of 2- (2,3,6-trichlorobenzyloxy) -ethanol with a boiling point of 181 to 192 ° C. (6 mm Hg) are obtained.

C ₉ H ₉ Cl ₃ O ₂ :
Calculated
found

Cl 41.6%;
Cl 41.2%.

Example 3

According to the process according to Example 2, 2,3,6-trichlorobenzyl chloride is reacted with propylene glycol, a colorless liquid with a boiling point of 180 ^° C. (0.05 mm Hg) being obtained.

C10H11CI3O2:
Calculated ... Cl 39.5%;
found ... Cl 39.2%.

Example 4

The procedure of Example 2 was used, with the difference that the starting material was used 2,4,5-trichlorotoluene was used. The product obtained was a waxy solid with a boiling point of 155 to 162 ° C (0.75mm Hg).

The use of the compounds prepared by the process according to the invention as herbicidal Means is illustrated by the following experiments.

Attempt a

One of the seeds of annual broad-leaved weeds (mainly Jacob's weed, gray-haired Foxtail and Melde) as well as annual broad-leaved grasses (mainly finger grass and millet grass) infested area was plowed, worked with a disc harrow and in subdivided individual test fields which were planted with maize. Then the individual Test fields with the various active substances to be tested in quantities of around 4.5 kg per hectare sprayed. A month later the test fields with regard to the achieved weed control and examined with regard to the damage to the useful plants.

40

45

% Annihilation both
Grasses damage
of corn Active ingredient at the
wide
leafy
weed 100 no 2,3,6 - trichlorobenzyl
oxyethanol 100 5 track 2,4,5 - trichlorobenzyl
oxyethanol 5 95 small amount Mixture according to Bei
game la (40 to 50%
2,3,6-, 25 to 40%
2,4,5-, the rest mainly
neuter 2,3,4- and
2,4,6 - trichlorobene
zyloxyethanol .... 95 100 track Mixture according to Bei
game Ij (60 to 70%
2,3,6-, and 30 to
40% 2,4,5-trichloro
benzyloxyethanol. 100 100 no 2,3,6 - trichlorobenzyl
oxypropanol 100 5 track 2,4,5 - trichlorobenzyl
oxypropanol . 5

6c

% Annihilation both
Grasses damage
of corn Active ingredient at the
wide
leafy
weed 95 track Mixture according to Bei
game Ic (40 to 50%
2,3,6-, 25 to 40%
2,4,5-, the rest mainly
neuter 2,3,4- and
2,4,6 - trichlorobene
zyloxypropanol) .. 95 100 track Mixture according to Bei
game Ik (60 to 70%
2,3,6- and 30 to
40% 2,4,5-trichloro
benzyloxypropanol) 100 0 to 10 track 2,4 - dichlorophenoxy
acetic acid 100 100 no Ν, Ν-diallyl-a-chloro-
acetamide '(Randox) 0 to 10 0 Untreated field
share 0

Attempt B

A field infested with well-developed field winds (Convolvulus arvensis) was divided into individual sections divided and in early spring with emulsions of the compounds given in the table below sprayed with the amounts specified there. In the following autumn the individual field sections were inspected and it was the success of fighting field winds by comparison with untreated control sections estimated.

55

Connection after Fight success per hectare 8th from Field winch *) until 10 example 1 27 kg until 3 54 kg per hectare 5 1 a 6th until 10 10 Ib 2 until 9 lc 9 9 3 5 ld until 3 5 le 2 until 10 If 2 5 3 5 Ig until 3 5 lh 2 until 9 until 10 Ii 2 until 10 until 10 Ij 7th until Ik 9 9 9 9

*) Scale: 0 = no effect; 1 to 3 = low suppression; 4 to 5 = moderate oppression, regrowth probably; 6 to 8 = essentially suppressed, re-growth doubtful; 9 = complete annihilation, no regrowth expected and 10 = complete annihilation, no viable shoots.

One year after the treatment, sugar cane, Wheat and barley can be grown without seriously damaging the seedlings occurred by remaining active ingredient.

Claims (2)

1 230 416 10 9 Claim Attempt C The trial area used was from the following well-developed, perennial and biennial Weed species infested: bindweed, pisang, wild carrot, Canada thistle, yarrow, daisy, Spurge and Mercury. It was trichlorobenzyloxyethanol (by chlorination of Toluene prepared according to Example 1) in the early summer in an amount of about 90 kg per hectare brought to use. A year later the treated area was completely free of vegetation, indicating that 100% soil sterilization had been achieved. Attempt D An area infested with field mercury (Agropyron repens) was infected with a logarithonic spray device, with the amount of in parallel field parts chemicals used ranged from about 9 to about 1.2 kg per hectare. 2 weeks later The sprayed areas as well as the unsprayed control strips are plowed and with the disc harrow treated, and field corn was grown on them. After 6 weeks, those parts of the field which were treated with about 9 kg of 2,3,6-trichlorobenzyloxyethanol and 2,3,6-trichlorobenzyloxypropanol were found a 50% decrease in the infestation with field mercury. On corn was with these Quantities per hectare no damage found. Process for the preparation of triply chlorinated aromatic compounds of the general formula CH ₂ -O-X-OH in which X contains at least two carbon atoms, optionally substituted Alkylene, alkylene-oxy-alkylene or oxyalkylene group means characterized by that a compound of the formula trichlorinated in the ring Cl ₃ CH ₂ Cl with a compound of the general formula HO - X - OH, in which X has the above Has meaning, in a manner known per se, preferably in the presence of an acid acceptor, is made to react. Considered publications:
U.S. Patent Nos. 2,606,213, 2,564,214;
Swiss Patent No. 294 966;
Journal of the Organic Chemistry 19 (1954), pp. 1646-1651. 609 747.341 12.66 Bundesdruckerei Berlin