DD149902A5 - MIXING FOOD OR PRE-MIXED FOR THE MANUFACTURE THEREOF - Google Patents

Abstract

The invention relates to feed mixtures containing (2,2-dimethyl-1,2-dihydro-quinolin-4-yl) -methylsulfonsÄure u. their salts contain. The new compounds act as antioxidant in the mixture. The mixture contains from 0.001 to 10% by weight of (2,2-dimethyl-1,2-dihydro-quinolin-4-yl) -methylsulfonic acid and / or its salts and, if desired, another antioxidant.

Description

The invention relates to a compound feed or a premix for the preparation thereof, a process for the preparation thereof and the use of a new substance as an antioxidant

Characteristic of the known technical solutions:

To stabilize the biologically active, oxidation-sensitive components of feed used on a large scale in livestock rearing plants xverden have been used for a long time generally effective as antioxidants substances. These substances must not cause any harmful side effects in the organism in the concentration used and must be eliminated from the organism quickly and without residue. It is known that some 1,2-dihydroquinoline derivatives are preferred as antioxidants.

can be. The most commonly used derivatives are described in HU-PS 149 469, 157 370, 1616 515, 162 358, in ZA-PS 712 702, and in JP-PS 70 48-11103.

The commercially available 1,2-dihydroquinoline derivatives effective as antioxidants are dark-colored, difficult to define, generally non-homogeneous, viscous or amorphous substances. As a result of the good lipid solubility and poor water solubility of the compounds, the compounds in the organism of the animals may become fatty Deposit tissues and discolor them.

Object of the invention:

The invention is intended to provide feed mixtures or premixes therefor with an improved antioxidant.

Explanation of the essence of the invention:

According to the invention is used as the antioxidant (2,2-dimethyl-l, 2-dihydro-quinolin-4-yl) -methyl-sulfonic acid or a salt thereof ·

(2,2-dimethyl-l, 2-dihydro-quinolin-4-yl) -methyl-sulfonic acid, hereinafter referred to as sulfonic acid and the salts of this sulfonic acid can be prepared by reacting 2,2,4-trimethyl-l, 2-dihydroquinoline sulfonated under mild conditions in a suitable reaction medium and, if desired, converted into a sulfonic acid salt.

Under mild conditions, the avoidance of unwanted side reactions is to be understood. When using strong sulfonating agents, e.g. Oleum, becomes the 7 position

"3 -

of the Dihydrochinä.lin Ring'es sulfonated (WH Cliffe, J. Chem. Soc 1933, page 1327). The sulfonation is carried out at 20 ⁰ C bia 80 ⁰ C, preferably at 35 ° C to 45 ° C. As sulfonating preferably sulfuric acid, chlorosulfonic acid and / or sulfur trioxide in embossing.

As a suitable reaction medium, organic solvents are used which do not show any undesired side reactions with the sulfonating agents. Chlorinated hydrocarbons such as methylene chloride or carbon tetrachloride, saturated hydrocarbons such as gasoline and saturated heterocyclic compounds such as dioxane are preferably used.

The salt formation can preferably be carried out without isolating the sulfonic acid. Known basic agents, e.g. Hydroxyde, carbonates and acetates of mono- and bivalent cations can be used. Among others, ammonium salts, as well as alkali and alkaline earth metal salts, such as ZoB. Sodium, potassium, magnesium, calsium salts and salts of other metals, e.g. Iron and zinc salts are produced. The salts are preferably isolated by pouring the mixture on ice or, after extraction, with acetone. The salts can be recrystallized for further purification. The products thus obtained may contain water of crystallization, optionally by heating or e.g. can be removed by boiling with toluene. The free sulfonic acid may be released from its salt, preferably by use of a cation exchange resin.

The starting 2,2,4-trimethyl-l, 2-dihydro-quinoline can be prepared according to the HU-PS 149 4 & 9: be reacted by 1 mol of aniline and 2 moles of acetone in the presence of an iodine catalyst.

The antioxidative effect of the sulfonic acid according to the invention can be seen in Table 1. "The table shows the average results of comparative model experiments. The experiments used sunflower oil without natural antioxidant substances. The samples were held in an open flask in a thermostat at 28 ⁰ C. The Peroxydv number was determined according to the Wehler method at the times indicated in the table. The table shows that in the model experiments, the best antioxidant effect was achieved by the compounds of the invention.

The excellent antioxidant activity of the compounds according to the invention was also demonstrated by a test series in which the carotene-sparing effect of lucerne meal was investigated. The results are summarized in Table 2. As a reference substance alfalfa flour without antioxidant and once with the known antioxidant with the trade name BHT was used.

The change of alfalfa meal was examined under natural conditions at 26 ⁰ C and 70 % relative humidity in scattered light. From Table 2 shows that the carotene-preserving effect of the compounds of the invention is very good.

Due to the low toxicity, the good antioxidant activity and the advantageous physical properties (microcrystalline structure, powder form, good water solubility, white color), the new compounds can be used in the fields of the food industry, the plastics and rubber industry, the pharmaceutical industry, the cosmetic industry and in particular in feed mixtures and feed and in premixes.

The antioxidant agents may be conveniently introduced by additives and / or premixes in the compound feed. Thus, the biological equality

weight of the feed essential oxidizable substances (beta-carotene, vitamins A, E and D) are already stabilized at the beginning of use. This fact is especially important when the premixes included substances that act catalyzing in the oxidation _β

According to the broad scope of the new compounds, the invention provides mixtures containing the new compounds in a thickness of 0.001 to 10% by weight. Furthermore, a process for the preparation of these mixtures and their use are the subject of the invention «

The products according to the invention can without harming the existing products in the oxidation sensitive biologically active substances iverden stored for long periods _o When mixing the antioxidant substances with the premixes and additives they are used in an amount from 100 to 100,000 ppm. The amount used depends on the intended use,

The admixing is preferably carried out in such a way that the antioxidant is first homogenized with the oxidation-sensitive substances, after which the other components of the premix are admixed. The premixes may contain as carriers dry feed seeds and products of the milling industry. The premixes can be converted with other feed components by known methods into finished feedstuffs.

Maize semolina, bran, soybean meal, fish meal, beet sugar, wheat semolina, alfalfa meal or sunflower extract can be used as feed components. As feed additives

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dicalcium phosphate, feed lime, feed salt or feed briquette are suitable. Diluents, lubricants, carriers and formulating agents may also be used as additives. The feed additive can be mixed into the feed in the form of powders, granules, powder mixtures, solutions or emulsions.

The compounds according to the invention can be used in the dietary and feed mixtures in an amount of 0.001 to 1% by weight.

The sulphonic acid salts may also be added to the feedingstuffs or compound feedstuffs by admixing the compounds not with the oxygen-sensitive premixes containing additives, but by mixing with inert substances an "antioxidant mixture" or by mixing with lipids an "antioxidant fat mixture" produces this mixture in the feed and feed mixtures. If desired, an emulsifier may be used to prepare the "antioxidant fat blend".

The sulfonic acid according to the invention and its salts are not toxic in a concentration of 0.001 to 1.0% by weight, in contrast to the known substances which act as antioxidants. The compounds form well-defined, microcrystalline, water-soluble, white, powdery products that can be incorporated without difficulty in premixes, additives, feed mixtures and feed.

Poultry fed with the new products failed to detect any harmful residues. The compounds do not accumulate in the animal's organism and are rapidly excreted or degraded. As a result

the feed stabilizing effect increases the weight gain of the animals.

The compounds according to the invention can be combined with lipophilic antioxidant active substances, especially when the oxidation-sensitive substances themselves are lipophilic. A mixture of the sodium salt of the sulfonic acid according to the invention with the known ethoxyquin In a ratio of 2: 1 can be used with advantage (see data in the table) 1)·

The sodium salt of the sulfonic acid according to the invention - if (four times the usual concentration) used in a concentration of 1000 ppm - exerts a radical protective effect against rancidity of the sunflower oil (Table l) _e This is particularly useful when long storage times of great importance. It should be noted that the known antioxidant agents provide better protection even at a higher concentration.

EXAMPLES

Further details of the invention can be seen from the examples.

_m example 1

32 ml of concentrated sulfuric acid are added with stirring to 40 ml of carbon tetrachloride. The solution is added at ^{0 0} C 17.3 g (0.1 mol) of 2,2,4-trimethyl-l, 2-dihydrochipolin, • after which the solution is kept at 40 ⁰ C for 4 hours. The obtained two phases are separated. The lower phase is extracted with 40 ml of carbon tetrachloride and poured onto ice, after which 2 × 100 ml of 5 N and 150 ml of 10 % sodium hydroxide solution are added in stages and the

932 0

Volume supplemented to 65O ml. The alkaline solution is extracted with acetone. The acetone phase is concentrated in vacuo and the resulting dark oil is poured to the ethyl acetate. The suspension obtained is stirred for 1 hour, filtered, washed with an ethyl acetate-methanol mixture and dried protected from light. This gives 21.5 g (76 %) of the sodium salt of (2,2-dimethyl-l, 2-dihydro-quinoline-4- ^ l) -methyl-sulfonic acid · mp: 66 to 68 ⁰ C.

 NMR: chemical shift: 6.66 to 7.5 5.9 4.1 1.33

Intensity: 6

Multiplicity: Analysis: C Calculated: 43.76 Found: 42.97 Y / assergehalt: (DSC)

N / A 0 1 2 72 4 6.99 29 singlet 53 t: multiplet 7.00 S HN 16.4 % , 17 9, 6.07 4.25 16 % 9 5.91 4.23 Example 2 calculated: , found:

To 40 ml of carbon tetrachloride is added 23.3 g (0.2 mol) of chlorosulfonic acid. 17.3 g (0.1 mol) of 2,2,4-trimethyl-1,2-dihydroquinoline are added to the resulting solution at ⁰ ° C., whereupon the mixture is kept at 40 ^° C. for 4 hours. The mixture is obtained as further processed in Example 1. The quality of the product obtained (28.8 g) corresponds to the product according to Example 1 within the error limits of the measuring technique

 Yield: 87.5%.

Example 3

The procedure is as in Example 2. The mixture is poured onto ice and the acidic solution is neutralized with a 5 N sodium hydroxide solution. The volume of the solution is

tm Q -

supplemented by adding a 35 % aqueous calcium acetate solution to 650 ml. The resulting suspension is mixed with 500 ml of acetone. The phases are separated. The acetone phase is processed further as described in Example 1. To obtain the calcium salt of (2,2-dimethyl-l, 2-dihydro-quinolin-4-yl) -methyl ~ sulfonic acid in a yield of 29.9 g (86.6%) _o 72 to Schmp.i 75 ° C.

Calcium content: calculated: 11.3 % found: 11.1 % _o

Water content: calculated: 15.6 % found: 15.3 % (DSG)

Example 4

A solution of 6.5 g of sodium salt of (2,2-dimethyl-1,2-dihydro-quinolin-4-yl) is introduced into a 120 g Dowex 50 VVX 10 cation exchange resin column previously activated in hydrogen form. Methyl sulfonic acid x3 moles of water of crystallization in 20 ml of water »The column is washed with distilled water and the eluted solution is concentrated. The precipitated product is filtered, washed with ethyl acetate and dried at room temperature.

This gives 4.5 g of (2,2-dimethyl-l, 2-dihydro-quinolin-4-yl) -methylsulfonsäure

Yield: 88 % » mp .: 256 to 26o ° C.

Example 5 ,

To a solution of 13.2 g of the sodium salt of (2,2-dimethyl-1,2-dihydro-quinolin-4-yl) -methylsulfonic acid in 10 ml of methylene chloride.

- 10 -

-.10 -

ethanol gives 2.7 g of zinc chloride. The mixture is stirred for 2 hours at room temperature and diluted with 40 ml of water. The solution is concentrated in vacuo in a water bath.

This gives 9 g of the zinc salt of (2,2-dimethyloyl, 2-dihydro-quinolin-4-yl) -sulfonic acid

Yield: 87 %. Scbmp ·: 98 to 100 ⁰ C.

Example 6

In a three-stage countercurrent rapid stirrer, a broiler premix of the following composition is prepared:

Vitamin A Vitamin D-3 Vitamin E Vitamin K Vitamin B-I Vitamin B-2 Vitamin B-6 Vitamin B-12 Vitamin C-Ca-d-pantothenate Polyacid Nicotinic acid Biotin

Antioxidant according to Example 1 choline chloride

Clopidol (3,5-dichloro-2,6-dimethyl-4-pyridinol)

corresponding to ^ O corresponding to CoSO, x7H ₂ O correspondingly

-. '. , :. , - 11 -

100 000 HE 220 000 ME 1 500 KE 250 mg 200 mg 600 mg 200 mg 2 mg 1 500 mg 1 300 mg 30 mg 3 500 mg 2 mg 14 000 mg 60 000 mg 12 500 mg 5 200 mg Zn ^2x 100 mg (I) 15 2+ mg (co)

6 600 mg 2 ⁺ Mn, 500 mg Cu ² 3 000 mg 2 ⁺ Fe * 8th mg (Se) 1 000 6

93

MnO amorphous according to CUSO4X5H2O corresponding to FeS0 "x7Hp0 corresponding to Hsu, Se Oo corresponding to carrier (wheat flour) ad

The prepared premix is mixed with 100 kg of feed

τη r ^ η mixed, optionally adding phosphorus and calcium-containing feed additives, after which the mixture is homogenized ·

Example 7

In a three-stage, countercurrent, high speed agitator, a laying poultry premix of the following composition is prepared.

Vitamin A Vitamin D-3 Vitamin E Vitamin K Vitamin B-I Vitamin B-2 Vitamin B-6 Vitamin B-12 Vitamin C Ca-d-pantothenate Folic acid Nicotinic acid

Antioxidants-Etoxyquine according to Example 1

(2: 1 mixture) Choline Chloride DL-Methiοηin ZnSO.xJ ^ O accordingly

- 12 -

1 000 - r-ί 000 000 NE 200 1 000 300 NE 1 600 30 NE 3 200 000 mg 12 200 000 mg 50 500 000 mg 40 200 000 mg 5 2 200 mg mg mg mg mg mg mg mg mg Zn

219320

Ca (10o) p corresponding to 100 mg (I)

2 ⁺ CoS0 ₄ x7Hp0 corresponding to 15 mg Co

MnO amorphous corresponding to 6 600 mg Mn

CuS0, x5H ₂ 0 corresponding to 500 mg of Cu

₂ O accordingly. , 3,000 mg Fe

corresponding to 8 mg Se

Carrier (wheat flour) ad 1 000 g

PEOO

The premix is added to 100 kg of compound feed and optionally stirred homogeneously with phosphorus and calcium-containing feed additives.

Example 8

Is a fattening pig premix of the following composition prepared:

Vitamin A 1 000 000 ES

Vitamin D-3 140 000 MB

Vitamin E. '1 600 IiE

Vitamin K-3 I60 mg

Vitamin B-2 500 mg

Vitamin B-6 '· 200 mg

Vitamin B-12 2 mg

Vitamin C . 250 mg

Ca-d-pantothenate 1 200 mg

Nicotinic acid · 1 500 mg

Antioxidant according to Example 1 1 500 mg

Choline chloride 40,000 mg

Zinc baeitracin 1 500 mg

L-lysine HCl 40,000 mg

2 o corresponding to 9 000 mg Zn

corresponding to 100 mg I

- 13 -

3 500 mg Co 2 ⁺ 5 000 mg Cu 2 ⁺ 12 000 mg Fe 2 ⁺ 1 000 G

CoS0, x7Hp0 corresponding to CuS0, x5H ₂ 0 corresponding to FeS0, x7H ₂ 0 corresponding to carrier (wheat flour) ad

The premix is mixed with 100 kg of feed mixture and stirred until homogeneous.

Example 9

In a two-stage Nautor Planetrührmaschine a dairy cattle premix of the following composition is produced.

Vitamin A

Vitamin D-3

Antioxidant according to Example 1 MgO accordingly

O accordingly

g accordingly

MnO amorphous corresponding to CoS0, x7H ₂ 0 corresponding to CuSo, x5H ₂ 0 accordingly

FeSO ^ xTH ₂ O corresponding to '

Carrier (Y / eizenmehl) ad

The premix is added to 100 kg concentrated feed and, if appropriate, homogeneously mixed with phosphorus- and calcium-containing feed additives »

350 000 IT ₂ + 300 000 EE 1 000 mg (Zn ²⁺ ) 150 000 mg (D 14 000 mg (Mn ₊ ²⁾ 500 mg (CO ² ) 9 000 mg P ⁺ (Cu ^2. ) 600 mg (Fe ² ) 2 500 mg 30 000 mg 1 000 S

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Example 10

On the basis of the broiler premix according to Example 6, a broiler feed of the following composition is prepared:

corn grits Example 11 56.3 % V / eizengrieß 10.0 % Soybean meal (extracted, 47 %) 22.0 % Fishmeal (70 %) ..'.... 8.0 % dicalcium 1.3 % feed lime 1.0 % food salt 0.4 % Broiler premix 1.0 % 100.0 %

On the basis of the laying poultry premix prepared according to example 7, a laying poultry feed of the following composition is produced:

Corn semolina 54, §

Wheat semolina '10,0

Fishmeal (70 %) 1.0

Soybean meal (47 %) 16.5

Extracted sunflower 3,5

Lucerne flour 5.0

Dicalcium phosphate 1.6

Food briquette 6.5

Feed salt 0.4

Laying poultry premix 1.0 %

100.0 %

- 15 -

Example "12

0.5 part by weight of antioxidant according to Example 1 are homogeneously mixed with 2.5 parts by weight of 50% soybean lecithin and the putter of Example 13 intended for the rearing of rats (experimental animals) is optionally prepared from the antioxidant-fat mixture.

Example 13

From the antioxidant fat mixture according to Example 12, a feed for rats (experimental animals) of the following composition is prepared:

Fishmeal (with 70% crude protein) 13.0 %

Soy meal (extracted, with 70 % protein) 34.0 % antioxidant fat mixture

Example 12. 4.0 %

Maxi semolina 26,0%

Bran 8.0 %

Beet sugar 10.0 %

Minerals 3.0 %

Premix 2.0 %

Example 14

The antioxidant according to Example 1 (25 g) is mixed homogeneously with 975 g of lime powder and the resulting premix is incorporated in an amount of 1 % in the compound feed.

Example 15

An antioxidant according to Example 1 (16 g) is mixed with 8 g of etoxyquin adsorbed on 4 g of silica. The Vorgemisc'h obtained is incorporated in an amount of 0.5 % in the compound feed.

- 16 -

table

Rancid of sunflower oil

Peroxide number

without antioxidant

at 250 ppm. XAX content

at 250

Athoxyquin- »content

at 250 at 250 ppm ppm of antioxidant BHT content according to Example 1 at 250 ppm of antioxidant-Äthoxyquingemisch (2: 1) according to Example 1

at 1000 ppm Antioxidant content according to Example 1

XAX m Methylenebis (2,2,4-trimethyl-1,2-dihydro-quinoline) ethoxyquin-6-ethoxy-2,2,4-trimethyl-1,2-dihydro-quinoline BHT. ~ 2,6-di-tert. Butyl-4-methyl «i> phenol

2 1 1 1 1 1 0 ί ι 12 9 8th 8th 7 6 2 CTN 24 20 18 15 13 5 I 55 45 39 37 35 33 11 90 68 58 55 54 55 16: 139 96 81 76 72 76 19

.1932 0 -i7-

Table 2

Change of carotene content of alfalfa flour

(Average Result)

days without anti oxydans carotene mg / kg 135 at 250 ppm BHT content I ₀ 114 137 at 250 ppm anti oxydansgehalt according to Example 1 7o .80 124 28 " 57 98 49th 34 71 70th 46 138 131 112 92 84

- 18 -

Claims (7)

invention claim 1. compound feed or premix for the preparation thereof, characterized in that it contains as an additive 0.0001 to 10 wt. % (2,2-Dimethyl-l, 2-dih7dro-quinolin-4-yl) -methyl-sulfonic acid and / or Salts thereof and, if desired, from 0.001% to 10% by weight of further antioxidant, 2. premix or compound feed according to item 1, characterized in that it contains 0.001 to 1 wt% _e % (2,2-di-ethyl-l, 2-dihydro-quinolin-4-yl) -methyl-sulfonic acid and / or salts thereof. 3. Premix according to item 1, characterized in that it contains 0.01-10 wt.% (2,2-Dimethyl-l, 2-dihydro-quinolin-4-yl) -methylsulfonsäure and / or salts thereof and inert carriers , 4. Premix according to item 3 »characterized in that it contains 0.01 to 2% by weight of (2,2-dimethyl-1,2-dihydro-quinolin-4-yl) -methylsulfonic acid and / or salts thereof, lipids and / or or emulsifier contains, " 5. Premix or compound feed according to item 1, characterized in that it is 6-ethoxy-2,2,4-trimethyl-l, 2-dihydro-quinoline, preferably in half the amount of the (2,2-dimethyl-l , 2-dihydro-quinolin-4-yl) -methylsulfonic acid and / or its salts. 6. A process for the preparation of oxydationsempfindliche substances containing premixes or compound feeds, characterized in that comprising a multi-component system with 0.001 to 10 wt,% (2,2-dimethyl-l, 2-dihydrochinolin-4-yl) -methyl- sulfonic acid and / or salts thereof and - 19 - if desired, mixed with 0.001 to 10 parts per million antioxidant. 7. The method according to item 6, characterized in that homogeneously mixed 0.01 to 10 wt.% ^^ - Dimethyl-l ^ -dihydro-quinolin-yl) -methyl-sulfonic acid and / or salts thereof with inert carriers , 8 »Method according to item 7 for the preparation of antioxidative fat mixtures, characterized in that 0.01 to 2 wt.% (2,2-Dimeth7l-l, 2-dihydro-quinolin-4-yl) -methylsulfonsäure and / or salts the same homogeneously mixed with lipids and emulsifiers. Process according to item 7, characterized in that 6-ethoxy-2,2,4-trimethyl-1,2-dihydro-quinoline, preferably in half the amount of 2,2-dimethyll, 2- dihydro-quinolin-4-yl) -methy1-sulfonic acid and / or its salts. Use of (2,2-dimethyl-l, 2-dihydro-quinolin-4-yl) -methylsulphonic acid and / or salts thereof in a fragrance mixture containing oxidation-sensitive substances _e . - 20 -