NO167587B - CONTINUOUS PROCEDURE WITH HIGH AVERAGE AVERAGE RATE FOR HYDROOLYSE OF CARBOHYDRATES TO ETHANOL USING IMMOBILIZED MICROORGANISMS AND ENZYMES. - Google Patents

Abstract

A process enables production of ethanol, butyl alcohol, acetone, lactic acids and glycerine from substrates normally not fermentable during a single fermentation stage by the simultaneous addition of hydrolysing and immobilizing enzymes and flock-type bacteria in a tower reactor. For this purpose enzyme flocks are produced having similar physical properties to those of bacteria flocks, and they are introduced with the latter in the tower reactor. The reactor comprises a widened end piece and a cylinder inserted in the latter so that the product which overflows out of the cylinder is in a non-turbulent region. The enzymes thus remain in the reaction chamber and the bacteria become richer without the need for filters or membranes.

Description

Insecticide and herbicide preparation.

The present invention relates to insecticides and herbicides which, in addition to usual fillers and carrier materials, as an active component contain at least one compound with the formula I

and R, an alkyl group with 1-10 carbon atoms or phenyl, or isomers thereof where the substituents in the 3- and 5-position have been interchanged. The exact position of the substituents in the isothiazole ring has not yet been unequivocally established.

The above-mentioned compounds have shown an outstanding effect as insecticides and herbicides and are characterized by an exceptionally wide range of action.

In the new compounds according to formula I, Rt means an alkyl group or phenyl group. The most relevant alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-, sec.-, iso- and tert.-butyl, but the higher homologues with up to 10 carbon atoms are also relevant.

The new compounds are easy to manufacture.

Thus, e.g. 5-(or 3-)-(3'-(or 5')chloro-4'-cyanisothiazolyl)-amino-3-(or 5-)chloro-4-cyano-isothiazole by reaction of 3,5 -dichloro-4-cyano-isothiazole with ammonia. Dimethylformamide is preferably used as a solvent. It is preferred to pass the ammonia into the reaction mixture over several hours. In general, the whole thing is allowed to stand for a further few hours. It has proven advantageous to carry out the reaction at a somewhat elevated temperature, e.g. between approx. 40 and 80°C. The reaction gives 3-(or 5-)-chloro-5-(or 3-)amino-4-cyano-isothiazole as a by-product. The further processing takes place in the usual way, e.g. by fractional crystallization and/or by chromatographic purification.

The compounds where R is CORt can e.g. is obtained by acylation of 3-(or 5-)chloro-5-(or 3-)amino-4-cyano-isothiazole. This acylation can be carried out using all the usual methods for the acylation of amino groups. It is preferred to carry out the reaction with the corresponding acid chlorides or anhydrides in organic solvents, especially in dimethylformamide or pyridine. The reaction can be carried out at room temperature. As a rule, the reaction mixture is heated by mixing the individual components. In order to achieve complete reaction, it may be advantageous to heat the reaction mixture further for some time at an elevated temperature or with cooling. Further processing is carried out in the usual way. 3-(or 5-)chloro-5-(or 3-)amino-4-cyano-isothiazole which is obtained by the preparation of 5-(or 3-)-(3'-(or 5'-) chloro-4'-cyano-isothiazole)-amino-3-(or 5-)chloro-4-cyano-isothiazole can also be used as starting material.

The new compounds have the great advantage in terms of insecticidal activity that, in contrast to ordinary insecticides, they only work when ingested. They are neither contact nor inhalation poisons. This selective effect is new in connection with insecticides and makes it possible to combat insects while sparing useful insects to a large extent.

The compounds' insecticidal effect, e.g. on housefly (Musea domestica) and cockroach (Blatta orientalis), was investigated. In the first case, the active substance was incorporated into a milk-sugar solution using small amounts of emulsifiers and carrier materials and placed as a lure for 7-day-old flies in food bowls that only allowed oral ingestion of the active substance. The amount of the ingested active substance was determined on the basis of the weight gain of the flies and the concentration of the solution. With the aid of a stepwise concentration series, the DLS0 and DLn values could be calculated with the starting point in the consumed amount of active substance and the percentage mortality of the flies after 4 hours.

The investigation with Blatta orientalis was carried out by placing the active substance dissolved in acetone on half of a wafer with a diameter of 20 mm. The active substance-free part of the wafer was placed in a cork slot and used as bait for hungry cockroaches. Here, too, the test substance was used in a dilution series. Based on the amount of active substance and the percentage of dead cockroaches after 7 days, the DL50 and DL^ values could be produced graphically.

The results with two of the new compounds are reproduced in the following table:

When used in herbicidal preparations, the selective effect of the new compounds is of particular interest because this enables the use of the new herbicides in cultivated plant fields. Monocotyledonous plants show e.g. even during early stages of development a considerable resistance to the new agents compared to dicotyledonous weeds.

The herbicides containing the new active ingredients can also be used together with other herbicides, as today it is generally preferred to use combination preparations when fighting weeds. Combinations with weight of herbicides and/or growth resp. morpho-regulators are particularly beneficial. Among herbicides, the derivatives of phenoxy-alkanecarboxylic acids are particularly important, e.g. 2-methyl-4-chlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxypropionic acid and 2,4-dichlorophenoxypropionic acid and salts and esters of these compounds. Among morphoregulators, particular interest is linked to the derivatives of fluorene-9-carboxylic acid and 2-chloro-resp. 2,7-dichloro-fluorenol carboxylic acid. Good results are also obtained if ammonium thiocyanate and/or ammonium sulfate are added to the agents according to the present invention.

To investigate the herbicidal effect was

as an example, the following investigations carried out: I: Selective effect when fighting weeds in cultivated plant fields

a) In cotton and soy

Methodology:

The experimental plants were sown in 13 x 18 cm experimental dishes (the cultivated plants were placed in rows

and the weeds in patches) and pre-cultivated until the experimental stage was reached. The application took place by spraying on the leaves, as the cultivated plants were still in the bud stage while the weeds were in leaf stage 1-2. From an aqueous dilution series, each

times 10 ml of a 50% spray powder of 3-(or 5-)-chloro-5-(or 3-)acetylamino-4-cyano-isothiazole distributed over a 400 cm2 spray cone base surface. After 3 weeks, the bowls were placed under open field conditions. In the following table, the effect is shown using the following symbols:

0 = no effect

1 = slight transient damage

2 = moderately severe damage, persistent but curable 3 = severe persistent damage, only very slowly curable 4 = very severe damage, practically decomposing

-f- == completely extinct.

It appears from table 1 that considerably more damage occurs to weeds than to cultivated plants

b) In wheat and rice

In the same way, the influence of the

mentioned weeds in wheat and rice cultures examined. The test plants' respective development stages are indicated in the columns to the right of table 2.

II: Underleaf spraying of weeds in crops.

Methodology:

Small-plot trial (open field), 50 percent spray powder. Weed-infested beds were divided into parcels with a size of 5 x 1 metres. Per 5 m2 parcel, 250 ml of each concentration of the aqueous dilution series with the 50% spray powder formulation of 3-(or 5-)chloro-5-(or 3- )-acetylamino-4-cyano-isothiazole sprayed outwards in such a way that the foliage of the cultivated plants remained largely untreated (underleaf spray things with 500 liters per hectares). The effect was assessed after 3 weeks and assessed as indicated above. The results are compiled in table 3. Here again, the selective effect is clearly demonstrated.

II: Spraying a young, weed-infested lawn.

Methodology :

Small-plot trial (open field), 50 percent spray powder.

An experimental plot was sown with a mixture of the following grass seeds: Arrhenatorum elatior, Ho-lous lanatus, Bromus inermis, Daotylis glome-rata, Phleum pratense, Lolium perenne, Poa pra-tensis, Festuoa rubra, Festuca ovina and Agrostis tenuis. After the sprouted young grass had developed approx. 3-4 leaves and the young weed 3-6 young leaves, the surface was sprayed with 500 ml per 10 m2 (500 liters per hectare) of the aqueous dilution of a 50% spray powder of 3-(or 5-)-chloro-5-(or 3-)acetylamino-4-cyano-iso -thiazole. The effect was assessed 14 days after treatment.

This table also shows the selective effect of the new compounds. Moreover, when compared with the known herbicide 3-chloro-5-amino-4-isothiazolecarbonitrile described in the U.S. patent no.

3 155 678, example XIII, and which shows herbicidal action when used in an amount of approx. 18 kg per hectare, it appears from the table that the herbicidal effect of 3-chloro-5-acetylamino-4-cyano-isothiazole is approx. 10 times better as this compound has full effect when used in a quantity of 1-2.5 kg per hectare (500 liters per hectare of a 0.2-0.5 per cent solution).

IV: Spraying after germination.

Chamomile flowers (Matricaria chamonilla) were sprayed in doses in pots under a spray system shortly before the beginning of stretching of the inflorescence axis. The spraying was carried out with the following preparation: A: Dilution series of a 50% spray powder of 3-(or 5-)-chloro-5-(or 3-)acetyl-amino-4-cyano-isothiazole.

B: Solution A with an addition of 0.05% ammonium thiocyanate.

The assessment took place after 7 and 21 days, whereby the following grading was carried out:

0 = no effect

1 —weak effect (necrosis and chlorosis of the paired leaves) 2 = moderate effect (up to 33 per cent of the leaves extinct) 3 = strong effect (up to 75 per cent of the leaves extinct) 4 = very strong effect (the whole plant almost completely extinct )

+ — - completely extinct

The table shows activation of the effect (faster and stronger effect) for a herbicide according to the invention by adding ammonium thiocyanate in amounts that are ineffective alone. The activation increases with increased ammonium thiocyanate concentration. Similar results were obtained with ammonium sulphate.

The new compounds can be combined with all common additives and carrier materials for pesticides. For insecticides, e.g. especially spray powders, bait formulations, emulsion concentrates and granules for use. The amount of active ingredient in bait formulations and in granules is generally between 5 and 10 per cent, while spray powder contains approx. 5-95 per cent, preferably 50-90 per cent, and the emulsion concentrates approx. 30-95 per cent, preferably approx. 50-95 percent, active substance. The new agents can of course also be used together with other insecticides if necessary.

However, the new compounds can also be processed into all common forms of preparation for plant protection products and plant protection products. The agents can thus be used in solid or liquid form by spraying, watering, sprinkling or pollination according to the usual known methods of plant protection. Common additives and fillers such as red clay, kaolin, bentonite, shale flour, talc, chalk, dolomite or diatomaceous earth can be used if it concerns preparations in solid form. For liquid formulations, xylene, solvent naphtha, petroleum, acetone, cyclohexane, dimethylformamide or aliphatic alcohols are preferably used as solvents. Emulsion concentrates produced in this way can be marketed as such. Before use, the emulsion concentrates are diluted with water in the usual way. If agents are used that contain water-soluble substances as active ingredients, water can of course also be used as a dissolving or diluting agent when preparing the concentrate. The total amount of active substance in these preparations is generally between 5 and 95 per cent.

A particularly good herbicidal effect is obtained by using the compounds of the above-mentioned formula I, respectively of their isomers, together with wetting and/or dispersing agents. The herbicidal effect of the new compounds is greatly increased by the wetting or dispersing agent. In this preferred embodiment of the present invention, all common wetting and dispersing agents for plant protection products can be used. The wetting and dispersing agents are preferably used in a concentration of 0.01-1 per cent, calculated on the finished mixture.

The new connections can e.g. produced as follows:

Example A

16 g of 3-(or 5-)chloro-5-(or 3-)amino-4-cyano-isothiazole are dissolved in 75 ml of pyridine and mixed dropwise with 16 g of acetyl chloride while stirring. The reaction solution is thereby heated to approx. 60°. The whole is then heated for a further 1 hour in a water bath, and the solution is then poured into water. The crystals that precipitated after rubbing and standing were suctioned off and recrystallized from ethanol with the addition of active carbon. 3-(or 5-)chloro-5-(or 3-)acetyl-amino-4-cyano-isothiazole with a melting point range of 225-228°C is obtained.

By using benzoyl chloride instead of acetyl chloride, 3-(or 5-)chloro-5-(or 3-)benzoylamino-4-cyano-isothiazole is obtained in a similar manner.

Example B

80 g of 3-(or 5-)chloro-5-(or 3-)amino-4-cyano-isothiazole were dissolved cold in 200 ml of dimethylformamide and mixed dropwise with 80 g of acetyl chloride while stirring. The temperature of the solution thereby rose to 40°C. After finishing the addition, the whole was heated for 1 hour in a water bath and then allowed to stand overnight. The separated crystals of 3-(or 5-)chloro-5-or 3-)Acetyl-amino-4-cyano-isothiazole was filtered off with suction and recrystallized from ethanol with the addition of active carbon. The product had a melting point range of 227-229°C.

In the same way, by using the corresponding acid chlorides instead of acetyl chloride, 3-(respectively 5-)-chloro-5-(respectively 3-)butyrylamino-4-cyano-isothiazole and 3-(respectively 5-)chloro-5 -(resp. 3-)-caprinoylamino-4-cyano-isothiazole obtained.

Example C

A strong stream of ammonia gas was introduced into a solution of 600 g of 3,5-dichloro-4-cyanoisothiazole in 1400 ml of dimethylformamide at 50-60°C for 5 hours. After standing overnight, the precipitated ammonium chloride was sucked off and the filtrate concentrated under vacuum. The oily residue was brought to crystallisation by the addition of water and suctioned off. The aqueous filtrate was concentrated again and the remaining oil again mixed with water. The combined crystallisates were recrystallized from 96% ethanol with the addition of active carbon. As a first fraction, 142 g of 5-(or 3-)amino-3-(or 5-)chloro-4-cyano-isothiazole were obtained. The mother liquor was gradually concentrated and the precipitated crystals were suctioned off. The final residue consisted of an oil. The obtained, combined crystallisates from the mother liquor were dried and recrystallized from acetic acid ester. 94 g of 5-(or 3-)-(3'-(or 5'-)chloro-4'-cyano-isothiazolyl)-amino-3-(or 5-)chloro-4- cyano-isothiazole with a melting point of 243°C. By careful concentration of the mother liquor, a further 64 g is obtained with a melting point range of 240-242°C. The filtrate was concentrated again, and the remaining residue crystallized from 96% ethanol, leaving 67 g of 5-(or 3-)amino-3-(or 5-)chloro-4-cyano-isothiazole with a melting point range of 212-214°C was obtained. The remaining mother liquor was chromatographically treated using a silica gel column, whereby acetic acid was used for elution. A further 45 g of 5-(or 3-)amino-3-(or 5-)chloro-4-cyano-isothiazole and 58 g of 5-(or 3-)-(3'-(or 5'- )-chloro-4'-cyano-isothiazolyl)-amino-3-(respectively 5-)chloro-4-cyano-isothiazole was isolated.

The yield of 5-(respectively 3-)-(3'-(respectively 5'-)chloro-4'-cyano-isothiazolyl)-amino-3-(respectively 5-)chloro-4-cyano-isothiazole was 216 g, which corresponds to 42 per cent of the theoretical yield.

254 g of 5-(or 3-)amino-3-(or 5-)-chloro-4-cyano-isothiazole were formed as a by-product.

Example 1.

Spray powder

50% 3-(or 5-)chloro-5-(or 3-)acetylamino-4-cyano-isothiazole

0.5% alkyl naphthalene sulfonate

10% sulphite bleach powder

1% silicic acid

38.5% red clay (bolus)

Example 2.

Spray powder

75% 5-(or 3-)-(3'-(or 5'-)chloro-4'-cyano-isothiazolyl)-amino-3-(or 5-)chloro-4-cyano-isothiazole

8% oleic acid-N-methyltauride

17% chalk

Example 3.

Sprinkleable bait

5% 3-(or 5-)chloro-5-(or 3-)acetylamino-4-cyano-isothiazole

10% talc

85% bran

Example 4.

Granules

5% 5-(or 3-)-(3'-(or 5'-)chloro-4'-cyano-isothiazolyl)-amino-3-(or 5-)chloro-4-cyano-isothiazole

3% gelatin

10% red clay

5% wheat flour

77% bran

Example 5.

Spray powder

50% 3-(or 5-)chloro-5-(or 3-)butyrylamino-4-cyano-isothiazole

0.5% alkyl naphthalene sulfonate

10% sulphite bleach powder

1% silicic acid

38.5% red clay

Example 6.

Spray powder

75% 3-(or 5-)chloro-5-(or 3-)benzoylamino-4-cyano-isothiazole

8% oleic acid-N-methyltauride

17% chalk

Example 7.

Sprinkleable bait

5% 3-(or 5-)chloro-5-(or 3-)caprinoylamino-4-cyano-isothiazole

10% talc

85% bran

Example 8.

Spray powder

20.0% 3-(or 5-)chloro-5-(or 3-)acetylamino-4-cyano-isothiazole

30.0% 2-methyl-4-chloro-phenoxyacetic acid iso-octyl ester

40.0% fused silica 10.0% alkylphenol polyglycol ether

Example 9.

Spray powder

60.0% 3-(or 5-)chloro-5-(or 3-)acetylamino-4-cyano-isothiazole

20.0% 2,4-dichlorophenoxyacetic acid sodium salt 1.0% alkylbenzene sulfonate 5.0% sulphite powder

14.0% diatomaceous earth

Example 10.

Spray powder

40.0% 3-(or 5-)chloro-5-(or 3-)acetylamino-4-cyano-isothiazole 40.0% 9-hydroxyfluorene-9-carboxylic acid n-butyl ester

6.0% oleic acid-N-methyltauride 14.0% feldspar aluminum silicate

Example 11.

Spray powder

30.0% 5-(respectively/3-)-(3'-(respectively 5'-)chloro-4'-cyano-isothiazolyl)-amino-3-(respectively 5-)chloro-4-cyano- isothiazole

20.0% 2-methyl-4-chlorophenoxypropionic acid iso-octyl ester

10.0% 2-chloro-9-hydroxyfluorene-9-carboxylic acid methyl ester

1.0% alkyl sulfonate

6.0% sulphite powder

33.0% feldspar calcium silicate

Example 12.

Dispersion

30.0% 3-(or 5-)chloro-5-(or 3-)acetylamino-4-cyano-isothiazole 10.0% 2,4-dichlorophenoxypropionic acid sodium salt 1.0% carboxymethylcellulose 1.0% bentonite

1.5% polyoxyethylene ester of fatty and resin acids

56.5% water

Example 13.

Dispersion

30.0% 5-(or 3-)-(3'-(or 5'-)chloro-4'-cyano-isothiazolyl)amino-3-(or 5-)chloro-4-cyano-isothiazole

10.0% 2-chloro-9-hydroxyfluorene-9-carboxylic acid methyl ester

1.0% carboxymethylcellulose 1.5% bentonite

2.5% alkylphenol polyglycol ether 55.0% water.

Claims (3)

1. Insecticide and herbicidal preparation, characterized in that it contains as an active component at least one compound with the formula where R is COR, or and R, an alkyl group with 1-10 carbon atoms or phenyl, or isomers thereof where the substituents in the 3- and 5-position are interchanged. 2. Preparation according to claim 1, characterized in that it contains 3-(or 5-)chloro-5-(or 3-)-acetylamino-4-cyano-isothiazole. 3. Herbicidal preparation according to claim 1 or 2, characterized in that it also contains ammonium thiocyanate.