DE2456823A1 - AMINOAMIDATES AND METHOD OF PREPARING THESE COMPOUNDS - Google Patents

Description

The invention relates to nitrogen-containing compounds and in particular to ammonioamidates, for example can be used to modify the properties of polymers.

According to the invention, ammonioamidates of the formula

A-O-CO-N-N

proposed, wherein A represents an alkyl group having at least 5 carbon atoms, a cycloalkyl group, a Alkenyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group

5 09823/1007

Bank details ι Bayer. Vereinsbank Munich, account 620 404 · Posticheckkonto ι Munich 270 44-602

12 "5

Group, and R, R and Pr, which are the same or different can be, for an optionally substituted alkyl, alkenyl, cycloalkyl or aralkyl group stand-

1 2
hen or R and R together with the nitrogen atom connecting them form a heterocyclic ring or

12 "5

R, R and R ^ together with the nitrogen atom connecting them form one or two heterocyclic rings.

Examples of groups represented by A are alkyl groups such as hexyl, octyl, capryl, decyl, Lauryl, myristyl, cetyl and stearyl, cycloalkyl groups, such as cyclohexyl, alkenyl groups such as vinyl, 1-methylvinyl, allyl, 1-propenyl, butenyl and oleyl, substituted alkyl groups such as the radicals of polyalkylene oxides, e.g. polyethylene oxide and Polypropylene oxide, halogenated alkyl groups such as perfluoroalkyl groups, substituted oxyalkyl groups, such as ß-Acryloyloxyäthyl, ß-Methacryloyloxyäthyl, Crotonoyloxyethyl, vinylacetyloxyethyl, allylacetyloxyethyl and ß, ß, ß-tris (allyloxymethyl) ethyl, and alkyl groups that carry phenolic or arylamine residues, which are bonded directly or via bridging groups, optionally substituted aryl groups, such as e.g. Alkylphenyl, for example nonylphenyl, and alkenylphenyl, aryl groups attached to an alkyl or alkenyl group are bound by a linking group such as -0-, -CO-O-, -CO-NH-, and such groups, in which the hydrogen is substituted by an alkyl or alkenyl group, -0-CO-NH- and such Groups in which the hydrogen is substituted by an alkyl or alkenyl group, and groups in including any of the above optionally substituted aryl groups on the remainder of the ammonioamidate molecule by a polyethylene oxide or polypropylene

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oxide compound group is bound, dye residues, Groups that are bacteriζide, fungicidal or other biological Effects result, and polymeric groups, including silicones.

1 2 Examples of substituted groups denoted by R, R

or R ^ are represented, are alkyl groups, vile for example, methyl, ethyl, n- and isopropyl, η-butyl, n-pentyl, n-hexyl, decyl, dodecyl and octadecyl, Cycloalky! groups such as cyclohexyl, alkenyl groups such as Allyl, aralkyl groups, such as benzyl and β-phenylethyl, and substituted derivatives thereof, such as β-hydroxyethyl, β-methoxyethyl, β-cyanoethyl, β-hydroxypropyl, β, v-di-

¹ ι hydroxypropyl and ß-HydroxyoctyI. Each of the groups R,

2 "5
R or Br can be attached to the same group in a second ammonioamidate residue to form an optionally substituted hydrocarbon linking group such as an alkylene group.

12 As heterocyclic rings denoted by R and R and that Nitrogen atom can be formed, are morpholino, piperidino, pyrrolidino, piperazino and hexamethyleneimino mentioned, and as heterocyclic rings passing through

12 3
R, R, Br and the nitrogen atom are formed, there may be mentioned pyridinium, picolinium, quinolinium, dipyridylium, quinuclidinium, 1,4-bisazoniabicyelo [2.2.2] octane and substituted derivatives thereof such as carboxypyridinium groups.

1 2
It is preferred that R and R be alkyl groups of up to 4 carbon atoms, and especially methyl groups, and that Br be either an alkyl group as defined by

1 2
R or R- is represented, or a ß-Hydroxyäthy 1-

12 3 or ß-hydroxypropy! Group or that R, R and Br

$ 09823/1007

together with the nitrogen atom form a pyridinium ring.

Specific examples of ammonioamidates of the invention are Ν, Ν, Ν-trimethylammonlo-ß-acryloyloxy- (or methacryloyloxy) -ethoxyformamidates and Ν, Ν, Ν-trimethylammonio- (or l-pyrldinlo) -n-dodecyloxyformamidate.

According to the invention there is also a method of manufacture proposed the ammonioamidate according to the invention, which is carried out by using a hydrazide the formula

R ¹

+ / ₂ A - 0 - CO - NH - N - ^ - RM

12 3
wherein A, R, R and R ^ have the meanings given above and M stands for an anion, is reacted with a basic compound.

Examples of basic compounds are alkalis such as alkali metal hydroxides, e.g. sodium and Potassium hydroxide, alkali metal carbonates such as sodium and potassium carbonate, alkali metal carbonates and anion exchange resins in the hydroxide form.

The process according to the invention is expediently carried out by stirring the hydrazide and the basic compound, which is preferably used in an excess of up to 100 % , in a solvent such as a lower alcohol, for example ethanol. Reaction temperatures between room temperature and 10O ⁰ C

509 8 2 3/1007

can be used. The preferred temperature in each case depends on the circumstances, e.g. of the basic compound used. The ammonioamidate can usually be isolated by inorganic materials are removed, for example by precipitation with ethyl ether, and that an evaporation, preferably under reduced pressure.

The hydrazides used according to the invention can be prepared from the corresponding compounds of the formula A-O-CO-halogen can be produced, the halogen preferably consists of chlorine by a conversion

1 2 with a hydrazine of the formula NH ₀ -NR R,

12 to make a hydrazide of formula A-O-CO-NH-NR R, and by quaternizing with an alkylating agent of the formula R ^ M, where M is an anion-forming Group stands, such as bromine, iodine, p-toluenesulfonate or methosulfate. The procedure

1 2 "5

cannot be used if R, R and ßr together with the nitrogen atom form one or two heterocyclic rings.

Alternatively, the hydrazide can be obtained by reacting the compounds of the formula A-0-CO-halogen with a quaternary hydrazine of the formula (NH ₂ -NR R R - ^) M, in which M is an anion-blending group as above, in Reacts the presence of a basic compound. This reaction and the conversion of the hydrazine to an ammonioamidate can be carried out in one step. This represents a further feature of the invention. This process is suitable for the preparation of any ammonioamidates according to the invention.

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An alternative process suitable for the preparation of ammonioamidates of the invention wherein R · ^

stands for a ß ~ hydroxyalkyl group, consists in that

1 2 the hydrazine derivative of the formula A-O-CO-NH-NR R with an epoxide, such as ethylene or propylene oxide. The process can be carried out in a suitable protic or aprotic solvents such as tert-butanol, isopropanol or ethylene glycol dimethyl ether, for a Temperature between 20 ° C and 80 ° C can be carried out.

Alternatively, a disubstituted hydrazine of the formula

12 1 2
NR R, in which R and R have the meanings given above, are reacted with an epoxide in an aqueous alcoholic solvent such as tert-butanol or isopropanol, whereupon the reaction product with a compound of the formula A-0-CO-halogen in The presence of a suitable base, such as sodium or potassium carbonate or sodium bicarbonate, is treated, with

1 2 an ammonioamidate is obtained, wherein R and R the

Have the meanings given above and R ^ for a /? - Hydroxyalkyl group, such as ß-hydroxyethyl or ß-hydroxypropyl, stands.

The hydrazides used in the process according to the invention can also be prepared by hydrazine derivatives of the formula AO-CO-NH-NH ₂ or

A-O-CO-NH-NHR with an alkylating agent such as e.g.

ρ
RM, alkylated. These procedures are only suitable for

the production of ammonioamidates in which R,

2. ~ *> 2. "*>
R and Br or R and Br are the same.

The invention according to ammonioamidates can also by thermal decomposition of azido formates in the presence of tertiary amines, for example pyridines

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Temperatures below the decomposition temperature of the derived ammonioamidates can be obtained.

The ammonioamidates according to the invention are liquid or preferably solid. They are soluble in water, except in those cases in which the group "A" does not have any water-solubilizing agents Has groups and forms a major part of the ammonioamidate molecule.

To modify the properties of a polymer, the polymer, such as rubber, can be mixed with the ammonioamidate and then optionally shaped and heated or exposed to UV light to bring about the reaction with the polymer. However, it is usually more expedient and more economical if, as is usually the case, only the surface of the shaped polymer is to be modified, the polymer in the shaped form, for example as a thread, yarn, textile. to treat with a solution of the ammonioamidate in, for example, water and then to heat the treated polymer to drive off the water or solvent and then to heat it more strongly, for example to a temperature between 100 and 220 ^° C., or to expose it to UV light.

The group A is chosen so that the ammonioamidate suitable properties are given and that they are used for the modification of the desired properties of the Polymers are useful. For example, long-chain alkyl groups give the polymer water repellency, result in alkenyl and other unsaturated groups on the polymer chain reactive sites, for example

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are effective in crosslinking or in improving adhesion to polymers such as rubber yield polyalkylene oxides anti-static and anti-pollution properties, colored residues create coloring effects that go with the Polymer can be linked to phenolic and arylamine residues give a polymer-bound stability against oxidation and give fluoroalkyl and silicone residues a water and oil repellency.

In some cases the ammonioamidates are used outside the field of polymer modification. Example catfish the ammonioamidates, in which A stands for a long-chain alkyl group or alkaryl group, have surface-active substances Properties, which is why they are wetting agents and detergents. The ammonioamidates in which A

stands for a polymerizable unsaturated group,

polymers

can be polymerized to produce / ammonio aridates, which are described in GB-PA 55659/75. the Ammonioamidates are also generally accelerators for the sulfur vulcanization of rubber and catalysts for the formation of polyurethanes from polyisocyanates and polyhydroxylic compounds for which Trimerization of isocyanate groups into isocyanurate groups and for other base-catalyzed reactions. Ammonloamidate groups are also useful in achieving this temporary solubility of, for example, dyes, surfactants and detergents in water regardless of any subsequent reaction or decomposition.

The use of the above-mentioned ammonioamidates represents a further feature of the invention.

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2A56823

The invention is further illustrated by the following examples explains, in which all parts and percentages are expressed by weight, unless otherwise stated is.

example 1

174 parts (1.5 mol) of 2-hydroxyethyl acrylate were added dropwise to a stirred suspension of 400 parts of methylene dichloride, 225 parts (2.27 mol) of phosgene and 84 parts (0.84 mol) of calcium carbonate at 0 to 5 ^° C. for 1 hour admitted. The temperature was then ^{raised to 10 °} C. over 3 hours. The reaction mixture was stirred for a further 14 hours at 10 ^° C., after which excess phosgene was removed by bubbling dry nitrogen through the reaction mixture. The reaction mixture was filtered and the filter cake was washed with 200 parts of methylene dichloride. The filtrates and V / aschflüssigkeiten were combined and evaporated to a constant weight at 3O ⁰ C under reduced pressure to obtain 220 parts of 2-Chlorocarbonyloxyäthyl acrylate in the form of a pale yellow liquid.

60 parts (1.0 mole) of N, N-Dimethy! Hydrazine were dissolved in 300 parts of toluene, and the solution was cooled to 10 ⁰ C. 89.25 parts (0.5 mol) of 2-chlorocarbonyloxyethyl acrylate were then added dropwise to the solution over 45 minutes at 10 to 20 ° C, whereupon the reaction mixture was stirred for an additional 2 hours. A solid that separated out from the toluene was filtered off.

The filtrates were evaporated to constant weight at 30 ^° C. under reduced pressure, 51 parts of the hydrazide remaining as a pale yellow liquid.

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" ¹⁰ " 2A56823

Analysis found: N 15.6 % calculated for CgH ₁ ^ N ₂ (K: N 15.9 %

A mixture of 20 parts (0.2 mol) of the above hydrazide and 50 parts of methyl iodide was stirred for 24 hours during which time a yellow solid formed. The solid was filtered off, washed with diethyl ether and dried in vacuo over calcium chloride, 27 parts of N'-β-acryloyloxyethoxycarbonyl-N ^ N-trimethylhydrazinium iodide in the form of a pale yellow powder with a melting point of 70 ^° C. being obtained.

99.6 parts (0.3 mol) of the above iodide were mixed with 300 parts of ethyl alcohol and 55.2 parts (0.4 mol) of potassium carbonate, and the mixture was stirred at 25 ° C for 12 hours. The reaction mixture was filtered to potassium carbonate / bicarbonate to remove, and the ethyl alcohol was evaporated from the liquid at 30 ⁰ C under reduced pressure. The residue was dissolved in 400 parts of chloroform and the solution was shaken twice with 250 parts of water. The solution was then dried over anhydrous magnesium sulfate, filtered, and the filtrates were evaporated to constant weight at 30 ° C. under reduced pressure. The residue obtained consisted of 49 parts of N-trimethylammonio-ß-acryloyloxyethoxyformamidate in the form of a pale yellow oil. Analysis found: N 12.8 %; for C ₉ H ₁ 5N ₃ O ^: N 13.0 %.

The infrared spectrum showed characteristic bands for carbonyl at 1640 and 1725 cm " ¹ .

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If ethyl iodide is used instead of methyl iodide, then the corresponding N-dimethylethyl compound is obtained.

Beisgiel_2

The procedure of Example 1 was followed using 2-hydroxyethyl methacrylate instead of 2-hydroxyethyl acrylate repeated. There were similar intermediates and a similar ammonioamidate, namely N-trimethylamraonio-ß-methacryloyloxyethoxyformamidate, obtain. Similar intermediates and a corresponding N-dimethylethyl compound are also obtained if ethyl iodide was additionally used instead of methyl iodide.

Example

A mixture of 17.8 parts (0.1 mol) of 2-chlorocarbonyloxyethyl prepared according to Example 1, 22 parts (0.2 mol) of 1-aminopyridinium iodide (prepared by the method described in Organic Syntheses, I96j , 4j, page 2), 41.4 parts (0.3 mol) of potassium carbonate and 500 parts of chloroform were ^{stirred at 25 °} C. for 48 hours. The reaction mixture was filtered to remove the carbonate and the solution was shaken twice with 250 parts of water. The chloroform solution was dried over anhydrous magnesium sulfate and filtered, and the Piltrat was evaporated below 25 ⁰ C and under reduced pressure to constant weight, 14.5 parts of N-ß-pyridinio acrylqyloxyäthoxyformamidat were obtained as a brownish thick oil.

5098 23/1007

Example_4

Using the from 2-hydroxyethyl methacrylate according to Example 2 obtained chloroformate was a methacrylate pyridinioformamidate obtained which was similar to the pyridinioformamidate described in Example 3.

Example_5

(a) A solution of 289 parts (1.5 moles) of n-dodecanol in 200 parts of methylene dichloride was added dropwise to a stirred suspension containing 150 parts (1.5 moles) of calcium carbonate, 300 parts (3.0 moles) of phosgene and Contained 800 parts of methylene dichloride. The addition took place at 0 to 5 ^° C. for 1 hour. The reaction ^{temperature was raised to 25 °} C. over the course of 2 hours, and the reaction mixture was ^{stirred at 25 °} C. for a further 14 hours. Excess phosgene was removed by blowing dry nitrogen through the suspension. The reaction mixture was then filtered. The solvent was ^{removed at JO 0} C under reduced pressure, and the residue was distilled under nitrogen at 1.0 mm pressure, 338 parts of n-dodecyl chloroformate being obtained as a colorless liquid with a boiling point of 105 to 110 ° C / 1.0 mm became.

βθ parts (1.0 mol) Ν, Ν-dimethylhydrazine were dissolved in 400 parts of toluene, and the solution was ^{cooled to 10 °} C. in ice / water. Then added dropwise (0.5 mol) of n-Dodecylchloroformiat was added in 100 parts of toluene to cool solution for 1 hour at 10 to 15 ⁰ C, a solution of 124.25 parts. The reaction mixture was then ^{warmed to 25 °} C. and stirred for a further 2 hours, after which it was filtered to remove the amine hydrochloride. The filtrates were treated under reduced pressure

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Evaporated 45 ⁰ C to constant weight, wherein parts of the hydrazide I38 n-dodecyloxycarbonyl-NJN-dimethy! Hydrazine in the form of a · were pale-yellow solid with a melting point of 4J5 ° C obtained.

A mixture of 68 parts (0.25 mol) of n-dodecyloxycarbonyl Ν, Ν-dimethylhydrazine, 40 parts of methanol and 200 parts Methyl iodide was refluxed for 24 hours. That Solvent and excess methyl iodide were taking distilled off under reduced pressure, and the residue was dried in vacuo over phosphorus pentoxide, whereby 105 parts of the quaternary hydrazinium iodide as yellow solid with a mp of 71 ° C were obtained.

41.4 parts (0.1 mol) of n-dodecyloxycarbonyl-N, N, N-trimethylhydrazinium iodide, 250 parts of ethyl alcohol and 41.4 parts (0.3 mol) of potassium carbonate were mixed together at 40.degree Stirred for 12 hours after which the reaction mixture was filtered to remove the carbonate. The filtrates were at 35 ° C under reduced pressure to constant weight evaporated and the residue was dissolved in 250 parts of chloroform. The solution was shaken twice with 150 parts of water, over anhydrous Dried magnesium sulfate and filtered. The solution was kept constant at 35 ° C under reduced pressure Weight evaporated, leaving 21 parts of N-triraethylammonio-n-dodecyloxyformamidate in the form of a white solid with a mp of 55 ° C.

(b) Similar products were obtained by 27.2 parts of n-dodecyloxycarbonyl NiN-dimethylhydrazine with 20 parts of dimethyl sulfate in 100 parts of acetone neutral two hours were reacted at 50 ⁰ C and the so obtained 42 parts quaternary Hydrazlnium-tnetho-

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sulfate in 250 parts of ethyl alcohol with 27.6 parts of potassium carbonate were treated ^{at 25 0 C for 56 hours.}

Example 6

The chloroformate obtained from n-dodecanol was reacted according to the procedures described in Example J> with 1-aminopyridinium iodide, and N-n-pyridinio dodecyloxyformamidat with a Pp of 68 ⁰ C was obtained.

ExampleJ7

4-1.4 parts of myristyl chloroformate were added dropwise over 1 hour to a mixture of 41.4 parts of potassium carbonate, 100 parts of water, 33 * 3 parts of 1-aminopyridinium iodide and 150 parts of t-butanol, and the reaction mixture became 24 hours Stirred at 25 ° C. for hours. The reaction mixture was then evaporated to dryness at 15 mm pressure / 45 ° C., whereupon the residue was extracted at 60 ° C. with petroleum ether. The extract was dried over anhydrous magnesium sulfate, filtered and evaporated at 45 ° C under reduced pressure to dryness to give 48 parts of N-pyridinio ntetradecyloxyformamidat were obtained as a gray solid having a melting point of 85 ⁰ C.

Examples_8_to_l8

Using that in Example 5 for N-trimethylammonioamidate and procedures described in Example 7 for N-pyridinioamidate were the following compounds made from the corresponding chloroformate:

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N-trimethylammonio-n-decyloxyformamidate, Mp 42 ° C

N-trimethylammonio-n-tetradecyloxyformamidate, Mp 60 ° C

N-trimethylammonio-n-hexadecyloxyformamidat, mp 62 ⁰ C

N-trimethylammonio-n-octadecyloxyformamidate, Mp 80 ° C

N-trimethylammonio-oleyloxyformamidate (oil)

N-trimethylammonio-4-nonylphenyloxyformamidate (oil) N-pyridinio-n-decyloxyformamidate, m.p. 40 ° C

N-pyridinio-n-hexadecyloxyformamidate, m.p. 71 ° C

N-pyridinio n-octadecyloxyformamidat, mp 82 ⁰ C

N-pyridinio-oleyloxyformamidate, m.p. 35 ° C

N-pyridinio-4-nonylphenyloxyformamidat, mp 90 ⁰ C

Example 8 Example 9 Example 10

Example 11 Example 12

Example I3 Example 14

Example I5

Example 16 Example I7

Example 18

27.65 parts (0.1 mol) of tetradecyl chloroformate were dropwise at 7 to 13 ° C. to a mixture of 14.0 parts of N, N-dimethyl-N-2-hydroxypropylhydrazinium hydroxide (prepared according to the method of Bull.Soc.Chem., 1939, 6, 708), 30 parts of water and 27.6 parts of potassium carbonate admitted. The mixture was then stirred at room temperature for 24 hours at which time it decreased under a Pressure was evaporated to dryness at 50 ° C. Then 250 parts of chloroform were added, were that Filtered off potassium chloride and carbonate and the filtrate was evaporated to dryness, 3 ^ parts of a light brown oil were obtained. Elute this material from an alumina column with chloroform and crystallize from light gasoline resulted in N, N-dimethyl-N-

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(2-hydroxypropyl) ammonio-n-tetradecyloxyformamidat in the form of a white solid with a mp 62-64 ⁰ C,

At S £ ielJ20

75 parts of polyethylene glycol monomethyl ether with a molecular weight of approximately 750 were in 100 parts
Methylene dichloride dissolved, and the solution was added over J) O 4o minutes parts of liquid phosgene at 10 ⁰ C. The mixture was then left at 30 to 35 ° C for 3 hours
stirred, whereupon the excess phosgene with a
dry nitrogen stream was blown off. The solution
of the chloroformate was then reacted with excess N, N-dimethylhydrazine, the hydrazide was quaternized with methyl iodide, and the trimethylammonium iodide was treated with potassium carbonate according to the procedure of Example 5, wherein N-trimethylammonio-co-methoxypolyäthylenoxyformamidat, which differs from methoxypolyethylene glycol with approximately 16 Ethylene oxide residues derived, was obtained in an amount of 85 parts as a waxy solid.

Similar products were made from methoxypolyethylene glycol (12 ethylene oxide residues) and from methoxypolyethylene glycol (7 ethylene oxide residues) obtained.

Example_21

2-Hydroxyäthylperfluorooctanoat was reacted with phosgene by the method described in Example 20,
and the obtained chloroformate was then reacted with excess N, N-dimethylhydrazine, whereupon a
Treatment with methyl iodide and potassium carbonate as in
Example 5 followed, wherein N-trimethylammonioperfluoro-

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octanoyloxyformamidate was obtained as a white, waxy solid.

Similar products were obtained from oxyethylated perfluorooctanoic acid, CF ₃ (CF ₂ ) -CO (OGH ₂ CH ₂ ) _n OH, where η> 2. The oxyformamidates containing perfluorocarbon groups, which were applied either from an aqueous solution or a solvent to nylon, polyester and polyester / cotton fabrics at 180 to 200 ° C., exhibited excellent oil repellency.

Example_22

N-ethyl-N-ß-hydroxyethylaniline was sequentially treated with phosgene, Ν, Ν-dimethylhydrazine, methyl iodide and potassium carbonate by the procedure of Example 5 to give N ', N', N ¹ -trimethylammonio-ß-CN-ethyl janilinoethoxyformamidate .

A solution of the trimethylammonioformamidate prepared according to the above procedure in aqueous acetone was with an aqueous solution of diazotized! p-chloroaniline (1 molar equivalent) titrated at 0 to 5 ° C and pH 8 to 9 with stirring. The precipitated dye was collected, washed with acetone and ether and dried, whereby a scarlet dye, namely Ν ', Ν', Ν'-trimethylammonio-ß- [4- (4'-chloro) phenylazo-N-ethyl] -anilinoethoxyformamidate, was obtained.

The use of p-nitroaniline in place of p-chloroaniline gives a similar red dye.

The dyes dye wool and acrylic fibers from neutral. len aqueous solutions red.

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example

The wetting force of the prepared according to Example 6 Formamidates was measured by letting various powders slowly hit the surface of aqueous solutions of the formamidate were sprinkled and. the lowest concentration of formamidate was determined which was necessary was that the powder was wetted and sank through the solution. Similar attempts were made with a commercially available non-ionic wetting agent (an alkylphenol / ethylene oxide condensate).

powder Commercially available
non-ionic
Medium (conc
tration in %) Product of
Example 6
(Concentr
tion in %) talc 0.0025 0.0075 sulfur 0.001 0.00075 Boric acid 0.0025 0.00025 Titanium oxide
(with silicone
treated) 0.0075 0.0075 seven organi
cal pigments 1 at 0.0005
2 at 0.001
4 at 0.0025 1 at 0.000075
4 at 0.00025
1 at 0.0005
1 at 0.005

Example_24

The wetting force of the formamidates produced according to Examples 5 and 6 was measured by a heavy cotton cloth through a Benz padding machine at a pressure of 25 kg / 2.5 cm and at a speed of J5 m / min using an aqueous solution containing 0.5 g of the agent

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contained per liter. Similar attempts have been made below Use of two commercial anionic surfactants performed viz

(a) with the sodium salt of isopropylated naphthalin-2-sulfonic acid and

(b) with the sodium salt of sulfated methyl oleate. The moisture absorption in each case was as follows: ■■■ '

Commercial mean (a) 7.6 % Commercial mean (b) 7.8 %

Product of Example 5 10.4 % ■

Product of example β 11.6 %

Beisgiel_25

The surface-active properties according to the examples Formamidates prepared 5 and 6 were compared with those a commercial cationic agent (long chain quaternary alkylammonium bromide) and one, commercial non-ionic agent (alkylphenol / Ethylene oxide condensate) compared by at different Concentrations of the surface tension (Du Nouy ring method), the contact angle with waxed microscope slides. And the sinking time of quadratic Pieces with 1 cm edge length of a botany wool serge or 2.5 cm long pieces of unwashed Egyptian cotton that lay on the surface of the watery Solution were placed, were measured. The results are given in the table below.

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«Η ο to οο κ » CJ

middle concentration
% Surface
chenspan
tion Contact-
angle Sink time (seconds) cotton Product of example 5 1.0
0.1
0.01
0.001 29.2
29.3
29.3
29.3 35 °
34
36
51 Wool 2
2
3
16.5 Product of example 6 1.0
0.1
0.01
0.001 28.1
28.7
29.1
32.3 28 °
38
60 2
2
4th
8th 2
5
5
48 Not commercially available
ionic agent 1.0
0.1
0.01
0.001 34.1
34.1
34.6
35.5 34 °
39
.42
53 3
11
6th
28 2
2
10
> 2 minutes Commercially available kat
ionic agent 1.0
0.1
0.01
0.001 36.7
35.0
36.6
53.5 52 °
57
60
59 momentary
2
8th
> 2 minutes 4th
64
> 2 minutes
> 2 minutes 2
3
> 2 minutes
> 2 minutes

ro O

ro

cn cx> οο KJ GO

Example_26. ·.: ".-- ^: ..-

41 parts of polyethylene glycol monomethyl ether with having a molecular weight of approximately 750 according to the procedure of Example 20 were obtained with 14.3 parts of 1-aminopyridinium sulfate and 27 parts Potassium carbonate suspended in a mixture of 100 parts of tert-butanol and 50 parts of water, Treated at 10 ° C for 48 hours. The reaction mixture was filtered to remove potassium sulfate, and the solution was evaporated to constant weight under reduced pressure below 40 ° C. The residue was dissolved in 200 parts of chloroform, and the Solution was treated with charcoal> over magnesium sulfate dried and filtered. The filtrates were brought to constant weight under reduced pressure at 40 ° C evaporated, 4o parts of N-pyridino-co-methoxypolyäthylenoxyformamidat, which contained approximately 16 ethylene oxide residues, obtained in the form of a pale yellow oil became. '

The above product and the product of Example 20, which had been applied to nylon, polyester and polyester / cotton fabrics at l8o to 200 ⁰ C, resulted in a stain removal test (the fabric was stained with a motor oil, and then 12 minutes at 60 ° C) and excellent results in a static Hayek and Chromey test.

Example_27. "

6.6 parts of 1-amino-2- (p-chlorosulfonyl) phenoxy-4-hydroxyanthraquinone were as a solution in 120 parts of dioxane with 4.9 parts of 1-aminopyridinium iodide and 60 parts of a η

50 9823 / TO 07

alcoholic potassium hydroxide solution 5 hours at 20 to 4o ° C implemented. The reaction mixture was evaporated to dryness under reduced pressure and the residue was washed with water and dried. The pesticide was extracted with 50 parts of pyrldine and the solution was filtered and evaporated under reduced pressure, whereby 4.25 g of l-amino-2- (p-N-pyridiniosulfonamidato) ~ phenoxy-4-hydroxy-anthraquinone as a purple solid were obtained.

Analysis found: N 8.7; S 6.7 ^;

for C ₂₅ H ₁₇ N ₅ OgS: N 8.6; S 6.7 %.

The dye dyes wool and acrylic fibers from aqueous neutral solutions bluish-red.

Example_28

49.7 parts Dodecylchloroformiat in 300 parts of chloroform was added at 5 ⁰ C to a mixture of 55 * 4 parts of 4-Aminomorpholin.HCl and 16 parts of sodium hydroxide in water. The reaction mixture was allowed to slowly warm to room temperature. The two layers were allowed to separate and the chloroform layer was drained and dried over magnesium sulfate. Chloroform was distilled off to 6l, 2 parts of 4-morpholin-Dodecyloxycarbonylamino were obtained as a cream colored solid having a melting point 100.5 to 102 ⁰ C.

53 * 4 parts of 4-Dodecyloxycarbonylaminomorpholin were reacted for 65 hours at 50 ⁰ C with 85 parts methyl iodide. The excess methyl iodide was distilled off and the residue was dissolved in 150 parts of ethanol. By adding diethyl ether the

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quaternary iodide precipitated, which in the form of 62.9 parts of an off-white pest with one Pp from 92 to 94 ° C was obtained. . . ... ,

76 parts of the quaternary iodide were stirred with 4.55 parts of anhydrous potassium carbonate in 600 parts of ethanol at room temperature for 90 hours. The reaction mixture was filtered and the filtrates were evaporated to dryness. The resulting solid was washed with 500 parts of chloroform and cooled, and the insoluble potassium iodide was filtered off. Evaporation of the chloroform filtrates gave 9.8 parts of 4-methylmorpholinio-dodecyloxyformamidate as a yellow oil - which crystallized on standing. After recrystallization from petroleum ether (00 to 80 ° C) the Pp Kj was> up to 45 ° C.

Example_29

If tetradecyl chloroformate is used in place of the dodecyl chloroformate in the example, then the resulting product consists of 4-methylmorpholinio-tetradecyloxyformamidate in the form of a white solid with a melting point of 60 to 63 ^° C.

Example_J0

20 parts of phosgene were introduced into 15 parts of methylene chloride at 0 to 5 ° C, and then a solution of 16.1 parts of 2-Hydroxyäthy1-3- (2,5-di-tert-butyl-4-hydroxyphenyl) propionate was in 65 parts of methylene chloride were added dropwise at 0 to 5 ^° C. After stirring for J> hours at 0 to 5 ^° C. and slowly warming to room temperature, the excess phosgene was removed from the reaction mixture by passing dry nitrogen through it

509823/1007

became. The methylene chloride solvent was below 40 ° C and removed under reduced pressure, the 2-chlorocarbonyloxyethyl ester in the form of 17 »6 parts of a brown Oil was left behind.

Analysis found: Cl = 9.35 % ',

calculated for C ₂₀ H ₂₉ O ₅ Cl: Cl = 9, 21%;

17.4 parts of 2-chlorocarbonyloxyethyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate in 20 parts of toluene slowly became a solution at less than 10 ° C of 5> 4 parts of N, N-dimethylhydrazine in 80 parts of toluene admitted. The reaction mixture was allowed to warm slowly to room temperature and then with 10% saline washed. The toluene layer was separated and dried over magnesium sulfate and the toluene was removed removed at 40 ° C under reduced pressure, wherein

18.8 parts of a brown oil remained.

20.9 parts of the above 2- [3- (3,5-di-tert-butyl-ij-hydroxyphenylpropionyloxyäthoxycarbpnyl] -1,1-dimethylhydrazine was refluxed with methyl iodide for 7 days.

The excess methyl iodide was removed by distillation, leaving the quaternized iodide in the form of 24.6 parts of a viscous red-brown oil. Analysis found: J = 22.73 %

for C ₂₅ H ₅₉ O ₅ N ₂ J: J = 23.09 %.

22.6 parts of the hydrazinium iodide in 150 parts of chloroform were applied to a column containing 700 parts of washed alumina and with chloroform eluted. After 44o parts of chloroform through the column passed through, a fraction of 1,100 parts of chloroform was collected. The chloroform was de distilled off, with 14 parts of trimethylammonio 2-

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- (3, 5- <ai-tert-butyl-4-hydroxyphenyl) propionyloxy] ethoxyformamidate were obtained as a light brown oil which crystallized on standing. Pp 156-157 ° C after recrystallization from toluene / petroleum ether (BP 100 to 120 ⁰ C). "

Example Jl

Instead of the 2-hydroxyethyl-3- (5,5-di-tert-butyl-4-hydroxyphenyl) propionate from Example 50, 2, β-di-tert-butylhydroquinone was used. The product obtained was trimethylammonio-3,5-di-tert-butyl-4-hydroxyphenoxyformamidate with a melting point of 224 ° C. after recrystallization from ethanol / water. The oxyformamidates of Examples JO and J> 1 gave effective protection against oxidative deterioration in 06-olefin homopolymers, copolymers, polymers with dienes and natural rubber.

.H. HACiZ, f-trt -. Rt! I

50 9 823/1007

Claims (1)

where A is an alkyl group with at least 5 carbon atoms, a cycloalkyl group, an alkenyl group, represents a substituted alkyl group, a substituted aryl group or a heterocyclic group and R, 2 "5
R and Rr, which can be the same or different, each stand for an optionally substituted alkyl, alkenyl, cycloalkyl or aralkyl group or 1 2
R and R together with the connecting nitrogen 1 2 atoms form a heterocyclic ring or R, R and Vr together with the nitrogen atom connecting them form one or two heterocyclic rings. 2. ammonioamidates according to claim 1, characterized in that A is a long-chain alkyl group or an aralkyl group stands. 3. ammonioamidates according to claim 1, characterized in that that A stands for an unsaturated group. k. Ammonioamidates according to Claim 1, characterized in that A stands for a polyalkylene oxide radical. 5. ammonioamidates according to claim 1, characterized in that A stands for a dye residue. 50982 3/1007 6. ammonioamidates according to claim 1, characterized in that that A stands for an antioxidant phenol or arylamine radical. 7. ammonioamidates according to claim 1, characterized in that A stands for a fluoroalky! Group. 8. ammonioamidates according to any one of the preceding claims, 12 characterized in that R and R represent alkyl groups with up to 4 carbon atoms. 9. ammonioamidate according to any one of the preceding claims, characterized in that R represents an alkyl group with up to 4 carbon atoms. '. "- ■ 10. ammonioamidates according to any one of claims 1 to 8, characterized in that Yr for e
ß-hydroxypropyl group. characterized in that Yr is a ß-hydroxyethyl or 11. ammonioamidates according to any one of claims 1 to J, characterized '■' - · ■ '■ 12 "5" indicates that R, R and Br together with the nitrogen atom connecting them form a pyridinium ring. 12. Process for the preparation of ammonioamidates according to Claim 1, characterized in that a hydrazide der.Formel . _R l AO-CO-NH-N <—— R ² Μ.- 1 2 '"" 5 ■ "■ -... · .. in which A, R, R and R ^ have the meanings given above 50 9 823/1007 and M stands for an anion, reacts with a basic compound. 1J>. Process according to Claim 12, characterized in that the hydrazide is prepared in situ by reacting a compound of the formula AO-CO-halogen with a quaternary hydrazine of the formula (NH ₂ -NR RR ^- OM in the presence of a basic compound. 14. Process for the preparation of the ammonioamidates according to claim 10, characterized in that one is a hydrazine of 1 2 Formula NH ₂ -NR R reacts with ethylene or propylene oxide and the product with a compound of the formula A-O-CO-halogen in the presence of a basic compound implements. 15. Process for the preparation of the ammonioamidates according to claim 1, characterized in that an azidoformate is reacted in the presence of a tertiary amine. 16. A method for modifying the properties of a polymer, characterized in that an ammonioamidate is used according to any one of claims 1 to 11 is mixed with the polymer and the polymer is heated or exposed to UV light. 17. A method for modifying the properties of a polymer, characterized in that the shaped Treated polymer with a solution of an ammonioamidate according to any one of claims 1 to 11 and that treated polymer heated or. Exposing to UV light. 18. Process for the vulcanization of rubber, characterized thereby 50 9 823/1007 draws that the unvulcanized rubber with Mixes sulfur and an ammonia, midate according to any one of claims 1 to 11 and heats the rubber. 19. Process for the trimerization of isocyanate groups too Isocyanurate groups, characterized in that a compound which has one or more isocyanate groups contains, heated with an ammonioamidate according to any one of claims 1 to 11. 20. Process for the production of polyurethanes, thereby characterized in that a polyisocyanate and a polyhydroxylic compound in the presence of a Ammonioamidate according to any one of claims 1 to 11 heated. - MiMTANWXLTf M / 4NO.H.FINCKE, DIPt.-IN & .M * OMi (MOl .IM »s ST SO 9823/1007