DE1642501C - New biocidal compounds - Google Patents

Description

The present invention relates to nowe biocide ugn. In particular , it relates to new biocidal compositions for the treatment of hot water and circulating water in papermaking, which contain at least one of the compounds of general formula I as the active substance;

R -, - C-

-C-CO ₂ R ₄
R "

in which R 'and R "are a halogen (chlorine, bromine or iodine), a hydrogen atom or an alkyl radical with 1 or 2 carbon atoms, R _{1 is} a halogen atom (chlorine, bromine or iodine), R ₂ and R _{3 are} a halogen ( Chlorine, bromine or iodine), a hydrogen atom or a low molecular weight alkyl radical and R ₄ denotes a low molecular weight alkyl radical, or a copper salt of these compounds and, in addition, a carrier inactive as bioeid.

The new compositions of the invention are useful in the industrial field, in particular to combat and destroy harmful organisms such as bacteria, germs, fungi and algae that can develop in the waters used to make various industrial products serve.

In particular, the compounds mentioned are excellently suited to the formation of microbial moles to prevent or eliminate them in the circulating water of paper production.

They can also be used to treat the pulp for preservation purposes. As is known, the paper industry uses previously defibered hob and as a starting material reduces this to a pulp that generally contains 50% moisture, hence the pulp suffers decomposition reactions during storage and transport, to a large extent Fungal degradation and, to a lesser extent, bacterial degradation.

Another example of the possible uses of the new compounds according to the invention in the industrial field is the treatment of hides. vegetable tanning solutions and leather, which can be damaged by the growth of microorganisms.

The / i-keto acid esters. in the new according to the invention Compositions act as an active material, compulsorily carry a halogen (chlorine. Bromine or iodine) in, position and thus clearly differ from those from the British Patent 874 (lf> 4 known α-halo-acetyl acetic acid esters. who have the property necessary for education responsible for microbeing sludge in industrial waters Fight microorganisms.

This structural difference gives the invention according to compositions very advantageous properties, so is their biocidal effect of those Of compositions on the basis of «-halogen- ' Acetyl acetic acid esters superior. Because of the difference to the a-halo-acetyl acetic acid cysts are the compounds of general formula 1 in addition, practically no tear-irritating substances; it therefore accounts without any inconvenience And without special precautions in the new compositions for all industrial Applications are used where these compounds find their application.

The novel compositions according to the invention can be prepared by dissolving a Compound of general formula I in one with γ / water miscible solvents such as atbylacetylacetate and diacetone alcohol, It can also be beneficial be done by dissolving the active material in a water-immiscible solvent to produce, such as a hydrocarbon, and possibly a tension-active agent for this solution to be added to facilitate dispersion in water.

The final concentration of active material in the medium to be treated can be very low.

So z. B. in papermaking the applied dose between IO and 90 g active Material per ton of paper pulp (based on dry matter) and preferably between 30 and 45 g.

Of the compounds of the general formula I, those should be listed in particular for which the biological tests have shown particularly convincing results. They are the following:

- ethyl 4-bromo-3-oxo-butanoate or

Connection A,

- ethyl 2,4-dibromo-3-oxo-butanoate or

Connection B,

- EthyM-chloro-S-oxo-butanoate or

Compound C,

- methyl 4-bromo-3-oxo-butanoate or

Connection D,

- EthyM-bromo-S-oxo-butanoate,
Copper (II) salt, or compound E.

The compositions based on compound A can be used in particular in the paper industry be used. For this purpose, compound A is dissolved in ethyl acetylacetate in an amount of 60 per 100 g of solvent, and in this form the circulating slurry with which a machine for packaging cardboard production is added to the destruction of the sensitive To ensure microorganisms that develop in this environment and their reproduction unites can result in poor performance of the whole. The usable dose is of the order of magnitude from 30 to 60 g of active material per ton of dry pulp.

The compositions based on the compounds B. C. D and E can also be used for treatment of pulp can be used, or they can be added to the storage containers for these pulps to prevent fungus or microbes from developing.

The compound A can be prepared by the action of magnesium on the ethyl bromoacetate according to R, Stolle (reports [1908], 41, 954) or by the action of bromine on ethyl acetyl acetal in carbon disulfide according to Conrad (Be "richte [1896], 29, 1043), ^

Compound D is prepared by an analogous process, replacing ethyl acetylacetate with methyl acetylacetate.

Compound B can be caused by the action of bromine on ethyl - 4 - bromo - 3 - oxo * butanoate (cf. B e i 1 s t e i n, 3, 665) or through the action of 2 molecules of bromine on Älhylacelylacctai in carbon disulfide be won,

i 64g501

Pie connection C can be established throw through Exposure to magnesium nnf ethyl chloroacetate according to P, K, Alexen drew (reports [1913], 46.1022).

The compound E can be produced by the action of copperdlJ acetate on ethyl 4-bromo-3-oxo-butanoate.

The other compounds of the general formula I can by appropriate application of the abovementioned Methods are obtained,

Manufacturing methods
Ethyl 4-bromo-3-oxo-butanoate or compound A

130 g of ethyl acetylacelate and 250 ml of carbon disulfide are placed in a 1-1 flask equipped with a stirrer and a reflux cooling device. The mixture is cooled to 10 ^° C. and 160 g of bromine are added using a dropping funnel while stirring. The addition takes 2 hours.

After the addition has ended, stirring is continued for 1 hour at 10 ^° C. and then for 24 hours at 20 ^° C. The carbon disulfide is then distilled off in vacuo. The distillation residue is washed several times with a solution of sodium bicarbonate and dried over sodium sulfate.

The product is then distilled under vacuum at 1 to 3 mm of mercury. Those between 70 and 80 ° C übergeixnde fraction is recovered and consists of ethyl 4-bromo-3-'nxo-butanoate or compound A.

Ethyl 2,4-dibromo-3-oxo-butanoate or compound B

130 g of ethyl acetylacetate and 250 ml of carbon disulfide are placed in a 1-1 flask equipped with a stirrer and a reflux cooling device. The mixture is cooled to 5 ^° C. and 320 g of bromine are added using a dropping funnel while stirring. The addition takes about 5 hours. After the addition has ended, the temperature is allowed to rise to about 20 ^° C. The carbon disulfide is then distilled off under vacuum. The distillation residue is washed several times with a sodium bicarbonate solution.

The product thus obtained consists of ethyl 2,4-dibromo-3-oxo-butanoate or connection B.

50

Ethyl 4-chloro-3-oxo-butanoate or compound C "

In a 1-1 flask. which is equipped with a stirring and a reflux cooling device. bring one 12 g magnesium spinner. a few milliliters of diethyl ether and ethyl chloroacetate.

Man bnngi an iodine crystal with the magnesium in contact and heated for a few minutes. The reaction sets in quickly and you stop it by adding a mixture of diethyl ether and ethyl chloroacetate up to the amount of 1 molecule of the latter in progress. After cooling, the mixture is poured onto crushed ice and neutralized with it dilute sulfuric acid.

The ether phase is decanted, washed with dilute sulfuric acid and dried over sodium sulfate. The ether is then erdampft \ and the residue fractionated under vacuum. The ethyl 4-chloro * 3-oxobulanoate distills between 94 and 96 "C at 10 mm Hg.

od ^e r Compound P

This compound is made by the same method used for the corresponding ethyl ester is used by making ethyl acetylacetate through Methyl acetylacelate replaced,

Copper (II) salt of ethyl 4-bromo-3-ox> butanoate or connection E

70 g of copper (II) acetate are dissolved in 1400 ml of water, 70 g of ethyl bromo-S-oxobutanoate are also dissolved in 300 ml of ethyl ether, this latter solution is quickly brought to the one dissolved in water copper (II) acetate at room temperature and stir

rs, 3 hours at 20 ^° C., the green precipitate formed is filtered off, washed with water and dried. The bromine content of the product obtained is 33%.

Biological studies

a) Experiments with reconstituted paper pulp

This attempt approaches the conditions of

Practice. A suspension of fibers in water is made under precisely defined conditions (artificial paper pulp). One vaccinates with an aerospace

genes microorganism Aerobacter and leaves

Incubate for 24 hours at 37 ° C, then take a sample to determine the amount of germs per milliliter. Then ethyl 4-bromo-3-oxobutanoate or compound A is added.

The test batch is returned to the drying cabinet at 37 ° C.

Starting with the treatment, determinations were then carried out after increasing times.

The results shown in Tables I and Ia below were obtained.

40

Table I.

dose
ppm
Connection Λ

120
90
60
30th

Number of germ ». \: Millions
per milliliter of fiber suspension

I hour

before loading

jilung

54.3
54.3
63
48.6

I hour
after treatment

20.6
33.3
31.6
36.3

1 hour
after treatment ^

1.4

3.9
16.6
28

6 hours
after treatment

0.12
3.26
9.76

24 hours Bchandl ung

Table 1 a

I hour Percentage desoldering. 3 hours fi hours dose
ppm before Be calculated on output population km after loading according to Be Connect plot 1 hour 1 act plot dung Λ _ according to Be 97.4 100 - plot 92.8 99.7 120 62 73.6 94.7 90 - 38.6 42.3 90.2 60 49.8 30th 25.3

24 hours after treatment

100
100
100
100

I 642 501

b) Bjpoide investigations

and bactericidal effect

There were also the bnkteriostittischen, ATiang ν, -erte determines, (the set which the expansion in prevents the nutrient solution) and the initial bactericidal values (no resurgence of growth in gelose stirring medium), the following tables give an overview of the effect on some bacteria,

Table II

Bacteripstatic effect on Aerobacter aerogenes (Gram-negative) Table ΪΠ ft

Bactericidal effect ίμιΓ pseud, pmpnas (Gi)

Λ ■ - Conc ntrnlipncn. j η ppm fin nktivem 50 05 ! Q. Products Mftferffll V ₄ T T T 75 ' O ³ AT T ¹⁰ connection A ,,,, O ^] / ₄ τ τ τ Connection B ,,., τ T τ Connection D ,,,., O Connection C ,, _t , O

T = control: see! developed.

Products

Connection A

Connection B

Compound C

Connection D 0

T = control: fully developed.

Consentrations in ppm of active material

250

100

T 0

T T 0 T

50

T T T T

Table Ha

Bactericidal effect on Aerobacter aerogenes (Gram-negative)

Concentrations i η ppm of active 100 75 50 Products material T T T 250 0 V ₄ τ T Connection A .... 0 V ₄ T V ₂ T T Connection B .... V ₂ T T T Compound C .... 0 Connection D .... 0

T = control: fully developed,

ppm = parts per million parts.

0 - no development.

' _Λ Τ - development' / _{4 of} the control probc.

T = development as control sample.

Table IU

Bacteriostatic effect on Pseudomonas aeruginosa (Grarrwiegativ)

1 Concentrations in ppm of active ■ material

Verbini!
Verbini '
Connect
Connection

75 50 25th 10 0 T T 0 T 0 T T 0 V ₂ T T T

Fungistatic and fu-. ^ Jcide effect

The initial values for the fungistatic and fungicidal effects were also determined using analogous methods In the following Tables IV and IVa, for example, those with Aspergillus flavus reproduced the results obtained.

Table IV Fungistatic Effect

Products

Connection A

Connection B

Connection D

Compound C

Control: 5/5.

Concentrations

in ppm of active

material

50

25th

10

Table IVa Fungicidal Effect

Products

Connection A
Connection B
Connection D
Compound C

Control: 5/5.

Active material concentrations in ppm

250

100

75

sense

sense

50

25 10

Lanes 2 5

Production of ethyl 4-bromo-3-oxn-2-chlorobutanoate

developing

In 41.8 ethyl-4-bromo-3-oxo-butanoate, 29 g (Cl896 Reports], 1043] to 27 g of sulfuryl chloride dropwise resulting in a (FC, brings the temperature to 20 ⁰ C, stirred for 16 hours at this Temperature, removes hydrogen chloride gas and sulfurous anhydride that have formed under reduced pressure, rectifies the residue and receives 26 g of EthyM-bromo-B-oxo ^ -chlorobutanoate, b.p. = ITC at 0.5 mm Hg.

Analysis (p. ₆
Calculate
found

Ö29 _f 59 _f H 3, Ii, - St I4 ₍ S6% {
d'29.6, H 3 <i> Cf 14.4%,

Ünfsüchuhgcief biöcideri ^ Properties Of
Ethyi-4-bromo-3-öxo-2-chiöf-bütänÖät

9.7 liters of paper pulp with a concentration of 12.5 g / l are produced. adds 200 ecm 2% resin glue. causes infestation by inoculation with 100 ecm Aerobacter aerogenes and then incubated with stirring at 35'C (1st day).

On the 2nd day (i.e. 24 hours after the start of the experiment) a first count of the germs treated is carried out then the approach by adding the product to be examined, in concentrations of 200, 100, 50 and 25 ppm, readjusts the level with sterile water and then performs 1,4, 7 and The germs were counted 23 hours after the treatment (1st table).

On the 3rd day (i.e. 48 hours after the start of the experiment), the germs are counted and this is established Level of the approach with sterile water again, causes an infestation of the pulp by inoculation with 100 ecm Aerobacter and then leads 1, 4, 7 and 23 hours after inoculation {i.e. H. 25, 28, 31 and 47 hours after treatment or 49, 52, 55 and 71 hours after the start of the experiment) counts (2nd table).

On the 4th day (72 hours after the start of the experiment) the same measures as on the 3rd day are repeated (3rd table).

The results are expressed in terms of percent antibacterial effectiveness. The following tables summarize the test results received

together. 1. table Time after
treatment 200 ppm 100 ppm 50 ppm 25 ppm 1 hour .... 100 99.6 99.3 41.7 4 hours ... 100 100 99.9 96.7 Percentage effectiveness 7 hours,, . 100 100 100 92.3 23 hours ... 100 100 100 99.4

1 table
Percentage of potency after the first inoculation

^ Time after
treatment 200 ppm loaded ppm- 50 ppm 25. ppm 25 sulphides ". ..
28 hours ...
⁰ 31 hours ...
47 hours ... 99.7
99.9
100
100 99.1
99.5
99.8
100 98.7
97.9
95.5
67.8 97.0
87.8
80.9
0

3. Table
Percentage effectiveness after the second inoculation

/ cit according to
treatment

49 hours ..
52 hours ..
55 hours ..

200 ppm in ppm 50 ppm 99.4 99.1 68.8 99.8 98.9 53.5 100 99.2 18.8

25 ppm

7.5

16.2

The compound according to the invention was ethyl 4-bromo-3-oxo-butyrate (Compound A) and, as comparison compound, 2-chloro-3-oxo-butyric acid ethyl ester (Compound B), known from German Auslegeschrift 1 201 778, is used.

Thereby, the bacteriostatic threshold value and the bactericide threshold value for the following gram-negative bacteria determined: Aerobacter aerogenes, Pseudomonas aeruginosa and Serratia marcescens.

Test conditions

A meat bouillon that has been enriched with a liquid peptone and has different concentrations containing two products was inoculated with one of the named bacterial cultures. After a Incubation time of 48 hours at 37 ° C is the bacteriostatic threshold by an absence reached by bacterial disturbances that result from insufficient concentration.

Based on this investigation, the bactericidal threshold was determined by taking some Solution drops (medium + toxic compound) from the previous examination for a gelatinous Peptone broth. which are free of toxic compounds

was fertilize, dripped on. Any resulting bank development was determined after an incubation time of 48 hours at 37 ° C. The results obtained are summarized in Tables I and II below.

Table I Bacteriostatic Threshold

Aerobacter aerosehes 60 ΐ 4ff PseudbmönäS aeruginosa 8Ö 60 40 . 20th 40- Serrati rnarcescens 10 G product Concentration m ppm 0 . - Concentration in ppm : - - 100 0 - Concentration in ppm 100 0 80] 100 0 100 0 - - 100 20th - - A. iöö ■ - 209618 / $ 1 B. - 0

product

A.
B.

Aeröbaclcr acrögenes concentration in ppm

200

100

100

60

100! 0

O!

Table H Bactcricider Thresholds

Pseudomonas aeruginosa concentration in ppm

200

100

100

100 100

80

100 50

60

50 0

inosa
PPI " 20th 100 Serrati marccsccns
Concentration in ppm 80 60 40 20th '10 8th 40 0 100 100 50 0 100 50 0 50

Tables I and II clearly show that the compound A according to the invention in comparison to the known compound B a superior bacteriostalic effect compared to Pseudomonas aeruginosa and Serrati marcescens. The bactericidal effect of the compound according to the invention A against Aerobacter aerogenes, Pseudomonas aeruginosa and Serrati marcescens is the one also considerably superior to the comparison compound. This superior biocidal effect the compound according to the invention compared to the compound of the prior art represents a considerable surprising technical progress. step dar.

Furthermore, a comparison of the physical properties of the compounds examined shows that the compound according to the invention is considerably more stable than the comparison compound B, which may be explosively spontaneously dehalogenated. Furthermore, the compounds according to the invention do not have the disadvantage of the comparison compound of causing tear irritation.

Claims (1)

Claim: Bioeide compositions for the treatment of industrial water and of circulating water in paper manufacture, characterized in that they contain at least one of the compounds of the general formula _R _ _R as the active material. R ₂ -CC C-CO ₂ R ₄ R ₃ O R " in which R 'and R "are a halogen (chlorine, bromine or iodine), a hydrogen atom or an alkyl radical with 1 to 2 carbon atoms, R _{1 is} a halogen atom (chlorine, bromine or iodine), R ₂ and R _{3 are} a halogen ( Chlorine, bromine or iodine), a hydrogen atom or a low molecular weight alkyl radical and R ₄ denotes a low molecular weight alkyl radical, or contain a copper (II) salt of these compounds and a carrier which is inactive as bioeid.