DE1642543C3 - Mixed anhydrides of sorbic acid with carboxylic acids and their use for preserving bread and baked goods - Google Patents

Description

Antimicrobially active substances are often directly suitable for the food to be preserved Mix in the form in order to achieve an even distribution in it. When it comes to baked goods The simplest method of incorporation is adding it to the dough. Such an addition of preservatives can cause difficulties if the dough is loosened microbiologically, that is made with the help of yeast or sourdough. All previously known preservatives for door baked goods, like ζ. B. acetic acid, propionic acid, dehydroacetic acid and sorbic acid - such as from DT-PS 11 89 932 and DT-PS 11 83 453 known - and their Salts influence both the yeast activity required for loosening the dough and that "Growth of undesirable molds, so that so far with the use of a preservative in the case of baked goods, which have a good mold-preventing effect, also a considerable undesirable inhibition yeast activity occurs when the substance is worked into the dough before the baking process (see A. Schulz, Bread and Pastry, 11 [1957]), P. 131, and Y. Po me ranz, Food Res., 22 [1957], p. 553).

The undesired inhibitory effect on the baker's yeast cannot be avoided in practice either avoid reducing the amount of preservative added, as this will improve the protective effect «The finished baked goods are saved or greatly reduced from mold growth. The ones known so far Preservatives are therefore also used in practice to provide adequate protection against mold infestation only suitable to a limited extent because they have no selective effect against molds.

A preservative for baked goods is physiologically harmless and antibacterial effectiveness is still required that no taste or odor influence when Manufacture of the dough and occurs during baking and that the preserved baked goods are organoleptic does not differ from an unpreserved specimen. Finally, the used preservative is allowed Do not volatilize or decompose at the necessary baking temperature, otherwise there is no permanent protection could unfold in the finished baked goods.

It is also known that mixed anhydrides of the general formula

R, -CO-O-CO-R ₂ ,

in which one of the radicals R _{1 and R 2 can} also mean the radical OR ₃ and the radicals R 1. R ₂ and R _{3 are} organic residues that can preserve food and other perishable substances. For example, acetic acid-sorbic acid anhydride or propionic acid-sorbic acid anhydride can be used for fermentation. Avoid chimney infestation and signs of putrefaction in the same way (cf. DT-PS 11 98 659).

The invention now relates to mixed sorbic acid hydrides with saturated or inviting or polyunsaturated aliphatic carboxylic acids having 6 to 30 carbon atoms.

Below are some of the invention Sorbic anhydrides are characterized by their physico-chemical data as follows:

Sorbic acid-caproic acid anhydride, colorless liquid, freezing point: -19.5 C: Sorbic acid-caproic acid anhydride, colorless liquid. Freezing point: - 16.5 ^C C; sorbic acid-capric acid-anhydride usual liquid. Freezing point: 1.0 Ci-sorbic acid-lauric acid-anhydride, yellowish liquid. The freezing point: 16.0 C: sorbic acid-myristic anhydride, white powder. Melting point: 30.2 C sorbic acid-palmitic acid anhydride, white PuKe: Melting point: 42.0 C: sorbic acid-stearic acid-Λη hydride, white powder. Melting point: 49.5 C: sorbic acid-undecylenic acid-anhydride, yellowish liquid, freezing point: 1.5 C: sorbic acid-oleic acid anhydride pale yellow liquid, freezing point: -19.5 C: sorbic acid-linoleic acid anhydride yellowish liquid, freezing point: - 35 bi: "-37 C; sorbic acid-linolenic acid anhydride. Yellow liquid, freezing point: -55 to -57 C

Another object of the invention is the use of such mixed anhydrides as dough additive for the preservation of bread and baked goods

It was surprising that they mixed! Anhydrides from sorbic acid and higher fatty acids! basically from other mixed anhydrides differ in that they have the activity of the micro biological dough loosening agents, such as. B. yeast uiu Sourdough, do not inhibit and at the same time have a good mold preventing effect. Since they also physio logical, smell, taste and organoleptic not influence and also by higher tempera Doors are not inactivated or decomposed mixed anhydrides of sorbic acid and higher fatty acids as preservatives for baked goods! particularly suitable.

Suitable aliphatic carboxylic acids are ge called palmitic acid, stearic acid, oleic acid. Caproic acid. Caprylic acid, capric acid, lauric acid. My ristic acid. Linoleic acid, linolenic acid, lignoceric acid, elaidic acid, arachidic acid, behenic acid. Ccrotinic acid c Ricinoleic acid and licanic acid. The carboxylic acids preferably have 10 to 30 carbon atoms.

For physiological reasons, those acids that are in natural fats are particularly preferred oils occur. It is therefore preferred that mai for the preparation of the second anhydride component the mixed sorbic acid aninine according to the invention dride from a uiu by splitting natural fats oils obtained mixture of fatty acids with 12 bi 18 carbon atoms emanates, which without the usual separation into the individual fatty acids in itself be In a known manner, into a mixture of fatty acid halides, preferably fatty acid chlorides, or even voi Salts, preferably potassium salts, of the fatty acids passed over and subsequently in a likewise known manner is converted to mixed sorbic anhydride mixtures.

The preservatives are added directly to the dough as a solution or emulsion or dispersion or nacl Mixing with the shortening and / or loosening the dough

7 16

medium added. The preservatives according to the invention can be used regardless of the type of partial loosener. You own both door baked goods in which the dough is loosened by sourdough or yeast fermentation, as well as those made using the known chemical dough-loosening agents, e.g. B. baking powder, getting produced. The necessary additional menus of the preservatives according to the invention are 0.01 to 3 percent by weight, preferably of up to 1.5 percent by weight, based on the weight of the dough.

The advantages of using the mixed anhydrides according to the invention are that they no influence on sourdough and yeast fermentation, particle quality. Dough yield and proofing time. Even after baking, the browning, pores and crumb texture of the baked goods are correct completely identical to the control piece without the addition of preservatives. On the smell and The preservatives according to the invention have no effect on taste. The durability of the Baked goods preserved by the claimed method are very good.

example 1

A dough of the following composition

Wheat flour T \ pe 405 50 (X) g

Water '. 3 (XX) g

Baked margarine 250 g

Table salt '80 g

Sugar 30 g

Yeast 140 g

was each with 0.5 "ο of a mixed anhydride of sorbic acid mixed with various organic acids. Jc KK) g of the dough produced in this way placed in a wide beaker with a capacity of 600 ml. The time was measured within which the Tete at 30 C reached a volume of 230 ml, above Table 1 provides information about the results:

Table I.

I riebdaucr ties I ciucs in minutes

Control sample 40 45

Sorbic acid acetic anhydride. 121 131

Sorbic acid propionic acid

Anhydride HK 129

Bultic anhydride IOS 120

Sorbic acid palmitic acid

Anhydride 38 43

Sorbic acid undecylenic acid

Anhydride 40 46

Sorbic acid c-stearic acid anhydride 3 *) 47

Sorbic acid myristic acid

Anhydride .... "- ™ ⁴⁴

The dough's shoot duration is. as can be seen from Table I, shorter when using a mixed anhydride according to the invention than, for example, when the use of corresponding anhydrides of sorbic acid with shorter-chain carboxylic acids or of butyric anhydride.

B is ρ ie 1 2 _6j

A dough according to the recipe of Example 1 was made with different amounts of sorbic acid-palmitic anhydride (I) offset. Each HX) g of the 543 produced in this way

Doughs were placed in a wide beaker with a capacity of 600 ml. The time was measured within which the dough reached a volume of 230 ml at 30.degree. C. gives the results obtained in the table 11 Digestion:

Table II

Drive duration of the part

in minutes

Control sample 40 45

Addition 0.3% 1 38-43

Addition 0.5% 1 40-43

Addition 1.0% 1 39-46

The growth time of the dough is determined by adding different amounts of sorbic acid-palmitic acid-anhydride not significantly affected.

Example 3

A dough according to the recipe of Example 1 was made with different amounts of sorbic acid-palmitic acid-anhydride (I) and baked in the usual way as a loaf of bread (resting time 55 to 65 minutes. Baking time 60 minutes, baking temperature 180 to 200 C). A dough that was baked and prepared under the same conditions without serving as a control sample Additive.

All samples showed the same bread volume: the bread samples with a content of 1 were the same Resting time worked out just as well as the control samples. Neither in terms of the bread volume, the Crust and crumb texture, pores and crumb elasticity, even in the organoleptic Properties, I-containing samples and control samples showed any differences.

The finished bread, after being cut into slices for the purpose of infecting it, became very moldy exposed to contaminated atmosphere. A part of the Brolscheiden was then in the incubator (30 C, 95 to 100% relative humidity), another part at room temperature in polyethylene bags stored, about the mold growth occurring in the individual samples is given in Table III Exposure:

Explanation of symbols for table III (at the same time
Door Tables IV to IX):

- = No visible mold growth.

4 = weak pebbles. isolated

small colonies.

4- 4- - ■ Heavy mold growth, several colonies.

4- 4 4 - Heavy mold growth.

Table III

Storage in the incubator

Mold growth after 2 to S 1 "ημοη Lauer / eil

Control sample 4 4-4-4-4-

0.15% 1 - 4-

0.3% I - -

0.5% 1 - -

(ι Η

l · 4-4-4- 4-4-4-4-

4-4-4- 4- 4 -t- 4-

+ 4-4-4-

Store at room temperature

Mold formation after 2 to> 20 days of storage / fast ropes

Control sample -4-4-

0.15% I - - -

0.3% I - - -

0.5% I ■ - - -

16

4- -

4-

20th

4-4-4-4-4-4-

Example 4

A dough according to the recipe of Example I was made with different amounts of sorbic acid-caproic acid-anhydride (II) and baked in the usual way as loaf bread (resting time 55 to 65 minutes, Baking time 60 minutes, baking temperature 180 to 200 C). A dough without baked and baked under the same conditions served as a control sample Additive.

All samples showed the same bread volume: the bread samples with a II content were the same Resting time worked out just as well as the control samples. Neither in terms of the bread volume, the Crust and crumb texture, pores and crumb elasticity still in the organoleptic Properties, samples containing II and control samples showed any differences.

The finished bread, after being cut into slices for the purpose of infecting it, became very moldy exposed to contaminated atmosphere. Some of the bread slices were then placed in the incubator (30 C, 95 to! 00% relative humidity), another part at room temperature in polyethylene bags stored, or that which occurs in the individual samples Mold growth is shown in Table IV:

Table IV

Storage in the incubator

Shiininel formation after 2 to 5 days of storage / eil Days

45

Control sample 4- 4-4-4-4- 4-4-4-4- 4- + 4- + 55 0.05% II - 4-4- 4-4-4-4- 4- 4- 4- 4- 0.10% II - 4-4- 4- 4- + 4th 4- + + ⁵ ° 0.15% II - 4-4- 4- -f 4- 0.3% II - - - - storage at Room temperature

Control sample
0.01% II
0.05% Il
0.1% II
0.15% Il
0.3% Il

Schinimclhikliing after 2 to 20 redemptions l.ager / cH

Days

2 -4 X! (1 20

f 4 4- 4- 4-4-4- 4- 4 4- -f

f 4- 4- 4- 4- 4- 4- f 4-

4- + 4- 4- 4 4-

4- 4- 4-4-

6o

Example 5

A dough according to the recipe of Example I was made with different amounts of sorbic acid-lauric acid anhydride (III) and baked in the usual way as cheese bread (resting time 55 to 65 minutes. Baking time 60 minutes, baking temperature 180 to 2 (K) C). A test under the same conditions was used as a control sample produced and baked dough without additives.

All samples showed the same volume of broi: the Bread samples with a III content had risen just as well as that with the same resting time Control samples. Neither with regard to the bread volume, the crust and crumb texture, the Pore size and crumb elasticity, nor in the organoleptic properties, showed samples with a Content of 111 and control samples any differences.

The finished Brol, after being cut into slices for the purpose of infection, was exposed to an atmosphere heavily contaminated with mold. Some of the bread slices were then stored in an incubator (30 C, 95 to 100% relative humidity), some at room temperature in plastic bags. Table V provides information on the mold growth occurring in the individual samples:

Table V

Storage in the incubator

40

III Schimmd education 4th 4- 4 - -f ! ■ ach 2 to p 1 agen i. agc r / eil III lukewarm 4- III 4- 4- (1 ^s II 4- 4- - 4- 4- 4th _i- 4- 4- -I. - - "+ 4. 4- 4- 4- 4- + - - - 4- 4- 4- 4- 4 ⁴ - Control sample - 4- 4 4- 4- 4- 0.05% _ - 0.10% 0.15% 0.3% 1

Store at room temperature

Mold formation after 2 to 20 days •position

- Control sample 4th X Id 2 (1 4th -I- i 0.01% III 4- _; 4- 4 4-4-4- 4th -I 4- 4 0.05% III - ■ 4- 4- 4-4-4- 4- 4- + 4 0.1% III - - 4- 4- 4- 4th 4- 0.15% III - - 4- 0.3% IiI - 4-

Example 6

Hin dough according to the recipe of Example I was mil different amounts of sorbic acid-oleic acid-anhyd (IV) added in the form of a 20% alcoholic solution and in the usual way as a loaf of bread Baked (resting time 55 to 65 minutes. Baking 60 minutes, baking temperature ISO up to 200 C). When A dough made under the same conditions and baked without additives served as the control sample.

All samples showed the same bread volume: the bread samples with an IV content were the same Resting time worked out just as well as with control samples. Neither in terms of the bread volume, the Crust and crumb texture, pores and 5 crumb elasticity in the organoleptic. Properties, samples containing IV and control samples showed any differences.

After being cut into slices for the purpose of infection, the finished bread was exposed to an atmosphere heavily contaminated with molds. A part of the bread slices was stored then in the incubator (3O ⁰ C, 95 to 100% relative humidity), another part at room temperature in Polyäthylenbeuteln over which occur in the individual samples 15 mold growth is given in Table Vl digestion:

Occurring mold growth is shown in Table VII:

Table VIl

Storage in the incubator

Mold formation after 2 to 8 days in a warehouse

Days

2 4 6 8 ■

Table VI

Storage in the incubator

20th

Control sample + + + + + + + + + + + + + +

0.5% V - -

Store at room temperature

Mold formation after 2 to 20 days of storage

16

20th

Mold formation after 2 to K days of storage

Days

2 4 6. «.

Control sample "T" + + + + + + + + ^{+ +} + + 0.15% IV - + + + + ^{+ +}

0.5% IV - -

Storage at room temperature Control sample 0.15% V
0.3% V
0.5% v '

Shingling after 2 to 20 days of storage Days

16

20th

Control sample - +

0.15% IV
0.3% IV
0.5% IV

Example 7

A dough according to the recipe of Example 1 was ra different amounts of sorbic acid-capry acid anhydride (V) offset. The preservative was previously worked into the shortening. the Dough was then made in the usual way as a box bread baked (resting time 55 to 65 minutes, baking time 60 minutes. baking temperature 180 to 2OTC). As a control sample served a dough prepared and baked under the same conditions without additives.

All samples showed the same bread volume .the bread samples containing V were with gle more rest time as well risen as rehearse ^ ^ ^onlro. Either in terms of the volume of the bread crust and Krumebeschaffenheit, the Po ™ ngund the Krumeelastizität still in its organoleptic properties, samples containing ν <*, and controls any ^Un J ^{ersc "iea} ^ _n ■

The finished bread was; After cutting the slices for the purpose of infection, they were exposed to an atmosphere heavily contaminated with mold, the bread slices were then placed in an _{incubator 6j} (30C, 95 to 100% relative humidity), another part at room temperature in Po'y ⁸ * " * ¹ ™ "pouches stored on top of that in each I roocn

Example 8

A rye flour sourdough of the usual composition was mixed with different amounts of sorbic acid-capric acid anhydride (VI) and baked in the usual way as bread (resting time 4 hours, baking time 60 minutes, baking temperature 230 to ¹ SOX). A control sample was used under the same conditions produced and baked dough without

Additive. .

All samples showed the same volume of Brol: the Bread samples with a VI content had risen just as well as the controls with the same resting time. Neither with regard to the bread volume, the crust and crumb texture, the pores and the kruir elasticity nor in the organoleptic properties showed samples with a content of VI and Control samples any differences.

The finished bread became strong with mold after being cut into slices for the purpose of infection exposed to contaminated atmosphere. Some of the bread slices were then placed in the incubator (3 * 0 C 95 to 100% relative humidity), another Part stored in polyethylene bags at room temperature, over which in the individual prober Occurring mold growth is shown in Table VII:

Table VIII

Storage in the incubator

Mold formation

after 2 to 5 days of storage / express

Days

Control sample
0.15% Vi
0.3% VI
0.5% Vl

-f +

509 686 / 7J

(ρ

ίο

Store at room temperature

VI Mold formation 2 to 20 days storage time 20th VI after ; + VI Days 4th X 16 + VI 2 - + + + -f - - - + + - - - + - - - - - - _ - - Control sample - 0.1% 0.2% 0.3% 0.5%

bags stored over that in the individual samples Occurring mold growth is shown in Table IX:

Table IX

Storage in the incubator

Mold growth after 2 to 8 days of storage

Days
2 4

Control sample

An equally good effect settled on with mixed i ₅ '° th anhydrides of sorbic acid and stearic acid' linoleic acid or linolenic achieve. 0.5% VII

Example 9

A dough according to the recipe of Example 1 was made with different amounts of a mixed anhydride of sorbic acid with a mixture of technical fatty acids with 12 to 18 carbon atoms (VII) offset. The substance was previously worked into the shortening. The dough then became more usual Baked as a box of bread. (Rest time 55 to 65 minutes, baking time 60 minutes, baking temperature 180 to 200 ° C). One under equals served as a control Conditions prepared and baked dough without additives.

All samples showed the same bread volume; the breads with a VH content were the same Resting time worked out just as well as the controls. Neither with regard to the bread volume, the crust and the texture of the crumb, the pores and the elasticity of the curvature nor in the organoleptic properties showed samples containing VII and control samples any differences.

The finished bread, after being cut into slices for the purpose of infection, was exposed to an atmosphere heavily contaminated with mold. A part of the bread slices was then in the incubator (30 ⁰ C, 95 to 100% relative .Luftfeuchte), another part at room temperature in polyethylene storage at room temperature

20 Mold formation after 2 to 20 days of storage

Days

2 4 8 16 20

Control sample
0.15% VI
0.3% VII
0.5% VII

30 Example 10

In a solution of 137.5 g of palmitoyl chloride in 1000 ml of petroleum ether (bp. 40 to 80 ⁰ C) 56 g of sorbic acid are suspended. The suspension is cooled to 0 to 5 ° C. With vigorous stirring, 50.5 g of triethylamine are slowly added dropwise to 500 ml of petroleum ether. The mixture is stirred at 5 ° C. for a further 1 hour. Then the crystallized hy-

hydrochloride of triethylamine filtered off. The filtrate is concentrated in a rotary evaporator at room temperature in vacuo. Crystalline sorbic acid-palmitic acid anhydride is precipitated by cooling to about -20 ⁰ C.

Yield: 120 g. Melting point: 42 ° C.

Claims (2)

Patent claims: 1. Mixed anhydrides of sorbic acid with saturated or mono- or polyunsaturated aliphatic carboxylic acids having 6 to 30 carbon atoms. 2. Use of the mixed anhydrides according to claim 1 as a dough additive for preserving Bread and baked goods.