DE2040194A1 - Nitrilotriacetic acid derivatives and process for their preparation - Google Patents

Description

ADELONSTRASSfc 58 "

Our no.16504

Stauffer Chemical Company New York, N.Y., V.St, A.

Nitrilotriacetic acid derivatives and process for their manufacture .

The invention relates to new nitrilotriacetic acid derivatives, namely, monomeric nitrilotriacetic anhydride (hereinafter referred to as monomeric NTE anhydride ") and dimeric Nitrilotriacetic anhydride (hereinafter referred to as ITE dimeric anhydride referred to), which Neten after a simple, very quickly feasible and suitable for large-scale production Process by implementing clay nitrilotriacetic acid (hereinafter NTE) with a suitable dehydration » medium in the presence of an amine or amide as a solvent medium obtained, as well as other nitrilotriacetic acid derivatives, by direct reaction with either the aforementioned anhydrides or a mixture thereof a number of different connections arise; These products find a wide variety of uses in the industry.

109810/2263

The monomeric and dimeric NTE anhydrides according to the invention obtained by reacting NTE with a suitable dehydrating agent in the presence of an amine or amides as solvents. The products thus obtained are suitable for the production of industrially useful chelating agents by direct reaction of the monomeric or dimeric NTE anhydrides with suitable compounds, such as amines, hydroxylamines, hydrazines, amides, alcohols, Alkanolamines, phenols, mercaptans and so on. Usable amines are ammonia, N-substituted alkylamines such as N-methylamine, N-ethylamine and the like; N-substituted Arylamines such as aniline, p-toluidine, a-naphthylamine, 1,2,3,4-tetrahydroquinoline and the like. Typical hydroxylamines are hydroxylamine as such, then N-substituted hydroxylamines such as N-phenylhydroxylamine, N-butylhydroxylamine and the like. As hydrazine, for example, Ν, Ν'-diethylhydrazine and the like. Suitable amides are acetamide, formamide, propionamide and the like. Usable alcohols are e.g. alkanols such as methanol, ethanol, butanol and the like .. The alkanolamines are N, N-dimethylethanolamine, diethanolamine, Triethanolamine and the like. In question.

Per mole of monomeric NTE anhydride, about one mole of the reactant, e.g. amine, hydroxyl amine, Hydrazine, amide, alcohol, phenol, mercaptan or the like. Used, while on about one mole of dimeric NTE anhydride about three moles of the reactant come in. If monosubstituted derivatives are desired, then set only about one mole of amine, hydrazine or the other reaction agent with 1 mole of monomeric anhydride is obtained therefrom NTE monoamides, NTE monoesters, etc. A mixture from mono- and di-substituted nitriloacetic acid derivatives occurs when using dimeric NTE anhydride.

10 9 8 10/2263

The derivatives of monomeric and dimeric NTE anhydride are generally obtained by direct reaction of one of the two aforementioned anhydrides with suitable substances, that is to say with compounds which have a functional function
Acyl group-replaceable hydrogen atom, including those compounds that contain a nitrogen,
Have oxygen, phosphorus or sulfur atom. The derivatives obtained in this way can be used in many ways, for example as chelating agents, as protective agents, stabilizers, coagulants, fire retardants, as builders for detergents, as chemicals for agriculture and the like.

The monomeric and dimeric NTE anhydrides according to the invention correspond to the formulas:

C-CH ₂

(D

C-CH ₉ O O CH ₉ -C

N-CH ₂ -COC-CH ₂ -N

(II)

109810 /? 263

They are obtained by reacting NTE with a suitable dehydrating agent in the presence of a solvent serving amines or amides.

Suitable dehydrating agents are, for example, anhydrides aliphatic carboxylic acids with up to about 22 carbon atoms such as acetic acid, propionic acid, butyric acid, valeric acid, Capric acid, lauric acid, myristic acid, palmitic acid, Stearic acid, eicosanoic acid and the like, including mixtures of such anhydrides as formic acid-ZE acetic acid-

anhydride, formic / capric anhydride and the like; Anhydrides of aliphatic halocarboxylic acids such as anhydrides of chlorobutyric acid, bromobutyric acid, chloroacetic acid, Dichloroacetic acid, trichioracetic acid, trifluoroacetic acid and the like; Anhydrides of aromatic carboxylic acids such as anhydrides of benzoic acid, naphthoic acid, Toluic acid, including alkyl and alkoxy substituted derivatives of aromatic carboxylic acids (the alkyl and carry alkoxy groups of up to 6 carbon atoms) and halogen- and nitro-substituted derivatives of such aromatic Carboxylic acids; also anhydrides of dibasic acids with more than 5 carbon atoms such as anhydrides of adipic acid, Pimelic acid, suberic acid and the like, as well as carbodiimides,

e.g. N.N'-disubstituted carbodiimides such as N, N'-dicyclo hexyl-carbodiimide, N.N'-Diisopropylcarbodiimide etc ..

Particularly suitable dehydrating agents are Acetic anhydride and !!,! I'-dicyclohexyl-carbodiimide.

Amides suitable as solvents for the reaction are, for example, compounds of the formula:

1098 1 Π /? 26 3

Y-C-N

^ 2
Y ^

in which Y, T " and γ ² hydrogen atoms, alkyl groups, substituted alkyl groups

(namely haloalkyl, alkoxyalkyl, aminoalkyl and especially tertiary aminoalkyl groups), aryl groups or substituted aryl groups such as tolyl, phenethyl, Naphthyl groups, etc.

mean, or the formula:

in which Y, Y and Y ^ have the same meanings and η is an integer from 2 to 5.

In the above formulas, the alkyl groups include groups with up to 22 carbon atoms, such as methyl, ethyl, propyl, Butyl, isobutyl, pentyl, hexyl, octyl, decyl, dodecyl, Tridecyl, pentadecyl, octadeoyl, bicosyl, Doeosyl groups and the like including substituted Alkyl groups such as 2-chloropropyl, 3-methoxybutyl, dimethylaminoethyl, N-morpholinopropyl groups etc.

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Aryl groups in the above formulas can be phenyl or naphthyl groups as well as by alkyl radicals (with up to 6 carbon atoms), Halogen atoms, nitro and alkoxy radicals (with up to 6 carbon atoms) substituted derivatives of these groups and the like. Mean.

Amides that can be used as solvents are e.g. formamides, benzamides, butyrolactams such as N-ethyl-butyrolactam, N, N-dimethylbenzamide and the like. Particularly suitable amides are N-methylpyrrolidone, dimethylformamide, N, N-dimethylacetamide and the like ..

For the preparation of the desired monomeric or dimeric Amines which can be used as solvents for NTE anhydrides are, for example, tertiary amines, i.e. tertiary alkylamines, arylamines or heterocyclic amines, such as trimethylamine, tri-ethylamine, Tributylamine, triphenylamine, phenyl dimethylamine, Phenyldipropylamine, pyridine, quinoline, picoline, Alkyl piperidines such as methyl, ethyl piperidine and the like; Alkyl pyrrolidones such as N-methylpyrrolidone, N-ethylpyrrolidone etc. Pyridine is particularly suitable.

The inventive method for the preparation of monomeric and dimeric NTE anhydride is useful in Temperatures up to about 130.degree. C., usually within a temperature range of about 30 to about 100.degree. C., are carried out. Of course it is also possible to work at a low temperature, i.e. at room temperature, but this works Implementation is correspondingly slower. In the upper part of the temperature range mentioned, the conversion time is right In short, i.e. the desired NDE anhydrides are obtained very quickly, namely within a few minutes. Is preferred dimeric NTE anhydride in large quantities and non-monomeric NTE anhydride is desired, then the reaction is carried out under

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use of a larger excess of dehydrating agent carried out or maintained for a long time.

Opposite the NDE, the dehydrating agent becomes used in excess. Up to about a 50 molar excess of this can be appropriate. In a special case in which acetic anhydride is used as a dehydrating agent is used, about 9 to 10 moles of acetic anhydride are used per mole of the monomeric NTE, which is about a 5 »5 molar excess of dehydrating agent is equivalent to.

The weight ratio of amide to starting NTE is at least about 0.2: 1.0, expediently 3 to 10 μl.

In a typical implementation, monomeric and dimeric NTE anhydride is obtained by dehydrating NTE using acetic anhydride in the presence of a solvent such as pyridine or N-methylpyrrolidone, this implementation is given by the following equations:

⁰ O N-methylpyrrolidone CH ₃ C \

"θ 0

OH ₃ -O ^ ₀

0 N-GH ₂ CO ₂ H

10981Π / 2263

O C-CH ₂
■ ν O O
Il Il CH ₂ - G O O O O N-CH ₂ -COC-CH ₂ -N G-CH ₂ ' CH ₂ - C.

A mole ratio of escetic anhydride to NT3 of about 1: 1 to about 100: 1 and a weight ratio of amine or amide solvent to NTE of about 0.5: 1 to about 15: 1 is employed. The implementation
runs very quickly and the acetic acid obtained as a by-product can easily be removed by simple distillation
separate from the solvent. The NTE anhydrides can be produced in high yield, ie in a yield of over $ 80 of the product mixture of monomeric
and NTE dimeric anhydride.

As already stated, monomeric or dimeric NTE anhydride can be implemented with a variety of different compounds. To produce a monosubstituted nitrilotriacetic acid derivative, at least about 1 mol of monomeric or dimeric NTE anhydride is generally required
used per mole of reactants; however used
one for the corresponding di-substituted nitrilotriacetic acid derivative per mole of dimeric NTE anhydride at least about 3 moles of the reactant.

Monomeric or dimeric NTE anhydride can generally be reacted with compounds that have a

1 (.,; ^R j R 1 η / ■ '7 ι; ι

functional acyl group have replaceable hydrogen atom, compounds with an oxygen, Nitrogen, phosphorus or sulfur atom can be used. The derivatives thus obtained are versatile Uses, e.g. as chelating, as coagulating and antistatic agents, protective agents, stabilizers, flame retardants, as builders for detergents, as chemicals for agriculture, etc. Compounds with one through one functional acyl group exchangeable hydrogen atom are e.g. ammonia, amines (primary and secondary amines such as alkylamines and arylamines), alkanolamines such as e.g. Triethanolamine, tripropanolamine, Ιϊ, ΪΤ-dimethylethanol amine, Ν, Ν-diethylethanolamine, hydroxyethylpiperidine, Hydroxymethylpiperidine and the like; Monoalkyl and monoaryl hydroxylamines, dialkyl and diarylhydroxylamines incl. Hydroxylamine as such; Hydrazines including hydrazine itself, N, H-dialkylhydrazines such as dimethylhydrazine, Diethylhydrazine and the like, as well as diarylhydrazines; then primary or secondary amides such as formamides, acetamides, butyramides, N-methylacetamide and the like; Diamines, finally Ethylenediamine, p-phenylendiamine, etc .; Dihydrazines such as 1,4-dihydrazinobutane and the like; Ureas and guanidines including N-alkyl and aryl substitutes ™ ter ureas or guanidines, their alkyl group up to Has 10 carbon atoms and their aryl group, the phenyl, naphthyl, tolyl, mtrophenyl, chlorophenyl group or Aralkyl groups such as phenethyl group and the like. Be can; furthermore cyclic N-compounds such as morpho line, Piperidines and aziridines including substituted morpholine and piperidine compounds such as 4 ™ ethyl morpholine, 3-chloromorpholine, 1,4-diazaeyelohexane, etc .; Imidazolines including substituted imidazolines;

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2040134

Tetrahydrooxazoles, tetrahydrothiazoles, benzodiazepines and the like; then polyalkyleneamines such as polyethylene amines, Ethylenediamine, diethylenetriamine, 1,5,9,13-tetraazatridecane etc.; Amino acids such as glycine, ß-alanine-iminodiacetic acid, Glutamic acid, etc .; Alkylenediamine polycarboxylic acids such as ethylenediamine mono-, di- or triacetic acid and the like; Amino and iminonitriles such as aminoacetonitrile, iminodiacetonitrile and the like; Hydroxyl groups containing carboxylic acids such as glycolic acid, citric acid, tartaric acid, etc .; oxygen-containing compounds such as phenols, cresols including bisphenol-A, and Polyols, glycols such as ethylene glycol, propylene glycol, butylene glycol etc.; Sugars and polysaccharides such as glucose, sucrose, starches, cotton and the like; Polyvinyl compounds such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and the like; Dialkylajminoalkylphosphonate like Diethanolaminoethyl phosphonate, dipropanolaminoethyl phosphonate etc.; Aminoalkylphosphonic acids such as amino methylphosphonic acid, ß-Aminoäthylphosphonsäuren one finally the esters, amides and derivatives thereof; N-methylolamides such as N-methylolphenamide, N-methylolacetamide etc.; N-methylolamines such as N-methylolmelamine, N- ^ ethylolureas like dimethylolurea etc. Also others Groups of compounds that have a sulfur or phosphorus atom together with one through an acyl group exchangeable hydrogen atom can with NTE anhydrides react. Examples are mercaptans, alkyl mercaptans, substituted alkyl mercaptans, aryl mercaptans and the like ..

The products from the direct reaction of monomeric or dimeric NTE-Anhydrld with compounds that a carry a hydrogen atom that can be replaced by an acyl group,

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-I-

correspond to the following formulas:

GO ₂ H

GH ₀ III

, ^ OE
κ ι

HO ₂ G CH ₂ -N-GH ₂ CNZ

(These compounds are obtained by reacting about 1 mol of monomeric NTE anhydride with about 1 mol a compound of the formula

• \
NO

; J

where R is a hydrogen atom, alkyl groups with up to 22 carbon atoms, substituted alkyl groups (with halogen, Nitro, vinyl, cyano, alkoxy substituents, etc.), aryl groups, e.g. (phenyl, naphthyl, anthracyl groups etc.) * Substituted aryl groups (e.g. with nitro, halogen, vinyl, cyano, alkoxy substituents, etc.), peptide groups (e.g. tetraglycyl, polylysine, polyglutamic acid groups, etc.), substituted carboxyalkyl groups (e.g. Glycyl, iminodiacetyl, 2-amino-3-hydroxysuccinyl groups etc.), carboxyalkyl groups, carbohydrate, mono- and polysaccharide groups, heteroaryl and alkyl-substituted groups Heteroaryl groups (such as pyridyl, thenyl, quinolyl groups etc.), cycloalkyl groups with up to 22 G atoms, Gycloalkenyl groups with 4 to 12 carbon atoms, e.g. cyclo-

butene, cyclodecene groups, etc .; Heterocycloalkenyl or heterocycloalkyl groups, (piperazine, piperidine, morpholine groups, etc.), where when R is a Cycloalkyl or heterocycloalkyl group means, Z and R are connected via an alkylene bridge (the heteroatoms are 0, S, N, P, Si, As, Sn, Sb and Hg), or the formula

RRO

_C- -C- -P

0-R

0-R

R m

corresponds, in which m is a number from 0 to 20, and Z is a hydrogen atom, alkyl groups with up to 22 carbon atoms, substituted alkyl groups (with halogen, nitro, vinyl, cyano, alkoxy substituents, etc.), aryl groups (e.g. Phenyl, naphthyl, anthracyl groups etc.), substituted aryl groups (with e.g. nitro, halogen, vinyl, cyano, Alkoxy substituents, etc.), peptide groups (such as tetra glycyl, polylysine, polyglutamic acid groups, etc.), substituted carboxyalkyl groups (e.g. glycyl, imino diacetyl, 2-amino-3-hydroxysuccinyl groups, etc.), carbohydrate, mono- and polysaccharide, carboxyalkyl, heteroaryl and alkyl-substituted heteroaryl groups (e.g. pyridyl, Thenyl, quinolyl groups, etc.), cycloalkyl groups with up to 22 carbon atoms (e.g. cyclohexyl, cyclopentyl, Cyclodecyl groups etc.), cycloalkenyl, heterocydo alkenyl or heterocycloalkyl groups (e.g. piperazinyl, piperidinyl, morpholinyl groups, etc.) or one of the formulas:

109810/776 3

/ R / R -C-
ti / R / R / -R CN
Il R , -C-N ^, S. -N , -CNN,
Il IR -CNN
ι,, ^X R O N O R SR

-N, -OH, -OR or

Q € NCS M

corresponds, where R has the aforementioned meaning, Μ® an alkali or alkaline earth metal and m a number is from 0 to 20; or the Foimel

HO ₂ C-CH ₂

0 R

It I

C-N-Z ι

CH ₂ -CNZ η ι 0 R

IV

corresponds, in which R and Z have the aforementioned meaning; (these compounds are mixed with compounds of the Formula III obtained when about 1 mole of dimeric NIE anhydride

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with about 3 moles of a compound of the formula H.

NO

implemented), or the formula

CO ₂ H

CH,

N "

CH ₂ -COR

corresponds, in which R corresponds to the above meaning; (These compounds are formed by reacting about 1 mole of monomeric NTE anhydride with about 1 mole of a compound of the formula R-OH), or of the formula

C-OR VI

CH ₂

• O

κ "

HO ₂ C CH CH ₂ -C-OR

corresponds, in which R has the above meaning; (These compounds are obtained in a mixture with compounds of the formula V when about 1 mol of dimeric NTE anhydride is used

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about 3 moles of a compound of the formula R OH reacted will), or the formula

CO ₂ H 2 0
It I. 2 ^H -C-S-R CH
t 2 N-CH ₂ t CH
t CO

VII

corresponds, in which R has the preceding meaning; (These compounds are obtained by reacting monomeric or NTE dimeric anhydride with R-SH in a molar ratio of 1: 1), or the formulas

CH ₂ -CSR

HO ₂ C-CH ₂ CH ₂ -CSR

It

or :

1 0 9 8 1 Π Il ■■ 2 B 3

HO ₂ C-CH ₂ .

HO ₂ C-CH ₂

² "n / a

(R ₁ -CR,

C -

N t

(H ₁ -CR ₂ ).

-C

Rc

C. ι

corresponds, where R and Z have the above meaning, m = 0 to 20, η = 1 to 10,000 and q = 0 to 10,000;
(These compounds are obtained by reacting the corresponding polymeric amines with nitrilotriacetic anhydride), or the formula

C—

R,

H
N

HO ₂ C-CH ₂

CH ₂ CO ₂ H

N
t

CH ₀ ι ^

C = O

N -

is equivalent to,

(these connections are obtained by implementing the

10981Π / 2263

speaking polymeric amino compound with Hi tril οtriacetic acid anhydride), or the formula

Il

CH ₉ CO ₉ H

/ C-CH ₀ -N Ö ^ά ^

(R

CO 1 "κ * —Χν · 2 / ■ * ·

i- \

Y ⁿ

XI

corresponds, where R ₁ ι, η and q have the above meaning.

(These compounds are obtained by converting the appropriate polymeric alcohol with nitrilotriacetic anhydride).

NTE derivatives according to the invention are, for example:

Polyamine-nitrilοtriacetamide,

Polyol nitrilotriacetate,

(with more than one polyamine group)

(with more than one polyol group)

Ethylenediamine-bis-nitrilotriaoetamide, ÄTE-mono-N, N-dibutylami d,

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NDE-bis-anilide,

Triethanolamine-tris-nitrilotriacetate, diphenylnitrilotriacetate, p-nitrobenzyl-nitrilotriacetate, NTE-monoglycine amide,
NTE-bis-glycinamide,
Ethylene glycol-bis-nitrilotriacetate, NTE-monohydroxamic acid, NTE-bis-hydroxamic acid,
NTE-bi sN-phenylhydroxamic acid, NTE-monoureid,

NDE-to-guanidid, "

NTE-bis-p-methoxythiophenyl ester,

Grlucose-nitrilotriacetate, e.g. glucose-tetrakis-nitrilotriacetate,

Diethanolaminomethylphosphonate bis-nitrilotriacetate, Polyvinyl alcohol nitrilotriacetate, Polyethyleneimine nitrilotriacetate, syni.-Ethylenediaminediacetic acid bis-nitrilotriacetamide, Glycolyl nitrilotriacetate, Bis (ß-naphthyl) nitrilotriacetate, N- (V; -imidazolylpropylJ-nitrilotriacetamide, NTE-mono-piperidinamide, tris-diethylenetriamine-nitrilotriacetamide,

NTE-hydrazide (mono-, bis-, N-, Ν, Ν'-di-, e.g. NTE-N, N ¹ -dimethylhydrazide),

Carbohydrate nitrilotriacetate, e.g. sucrose nitrilotriacetate, starch nitrilotriacetate etc. (mono-, oligo- and polysaccharide esters)),

NTE amino acid amides such as glycine amides.

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The following examples serve to illustrate the invention.

Example 1:

20 ml of N-methylpyrrolidone were mixed with 30 ml of acetic anhydride and 5 »Üü g NTE offset. The mixture was stirred for 24 hours at 50-70 ° C. Solvent, acetic acid and unreacted acetic anhydride was removed under vacuum. A further 20 ml of acetic anhydride were added to the kick and the volatile substances were removed Vacuum. This was repeated again. The residue was placed in a Soxhlet insert and then with benzene extracted. There was a residue of NTE anhydrides in the benzene solvent, mainly monomeric Anhydride. The melting point was 132-133 ° C. (decomposition). The mass spectrum of the anhydride showed a Main peak at m / e = 173; this corresponds to the monomer Anhydride.

The osmometric molecular weight (in dimethylformamide) of this substance was determined. The value found of 185 indicated the presence of a certain amount of thin anhydride.

Example 2:

2 ml of methanol-containing N, N-dimethylformamide were with about 100 mg NTE anhydride (prepared according to Example 1, consisting mainly of monomeric anhydride).

1 09810/9263

The material was refluxed for five minutes and then turned off overnight. The obtained solution was subjected to mass spectroscopy. It became a Mixture of NTE monomethyl ester and NTE dimethyl ester was obtained. Accordingly, both monomeric and dimeric anhydride were present in the NTE anhydride reacted with methanol.

Example 3:

10.0 g of NTE were used together with 40 ml of N-methylpyrrolidone and 40 ml of acetic anhydride heated to 60-70 ° C. Solvent, acetic acid and unreacted acetic anhydride were stripped off under vacuum. The oily kick was rubbed with benzene.

3.69 g of the oily residue were placed in a Soxhlet insert and extracted with benzene for 24 hours; 2.35 g of brittle amorphous NTE anhydride remained in use, another 0.36 g of crystalline NTE anhydride were in the benzene flask. The crystalline fraction melted at 130 ° C. (decomposition). The crystalline and the amorphous anhydride in the extraction use showed virtually the same infrared spectrum (split carbonyl absorption at 5.49 and 5.60 to 5.75 and at 5.82 and / -in). The NMR spectrum of the crystalline anhydride showed absorbance at 3.46 and 3.1 ppm in an area ratio of about 2: 1.

Example 4:

The procedure was as in Example 1, but replaced acetic anhydride by butyric anhydride and obtained the desired NTE anhydride in good yield.

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Example 5:

The procedure was as in Example 1, but acetic anhydride was replaced by benzoic anhydride and received the desired NTE anhydride.

Example 6 :

The procedure was as in Example 1, but replaced IT-methyl pyrrolidone with Ν, Ν-dimethylacetamide and obtained the desired NTE anhydride.

Example 7;

50 ml of pyridine was added with 10.0 g NTE offset "mixture was stirred for 10 minutes at 50 ⁰ C, put 50 ml of acetic anhydride are added and heated the mixture for 10 minutes at 100 ° G. The solvent was removed by heating under vacuum and an additional 50 ml of acetic anhydride was added. The volatiles were again removed by heating under vacuum. The residue remaining was 10.0 pounds of impure oily NTE anhydride. The infrared spectrum of this substance showed a split carbonyl absorption at 5.50 and 5.65 / ^ m. No further strong or medium absorptions were found in the carbonyl or carboxylate range of the infrared spectrum. Accordingly, the NIE anhydride synthesized under these conditions consisted mainly of dimeric anhydride.

Example 8;

0.0525 moles of NTE anhydride was added dropwise with 3.85 g

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(0.052 mol) Ν, Ν-diethylamine added. The reaction mixture reached a maximum temperature of 48 G. After 10 minutes a gel formed which settled. One moved the mass with about 75 ecm of diethyl ether. The amide was washed with ether and benzene. Obtained after air drying an amide with a melting point of 194 ° C. After recrystallization of this product from ethanol / water fell 11.1 g (yield = 86 $) NTE-mono-N, N-dimethylamide (melting point 2O5-2O6 ° C). The amide contained 10.9% nitrogen (theoretical 11.4%).

Example 9:

0.2 mol of NTE-anhydri dgemi sch in dimethyl acetamide containing triethylamine were mixed with 0.35 mol of hydroxylamine hydrochloride offset. The triethylamine hydrochloride was removed from the reaction mixture and a mixture was obtained from NTE mono- and di-hydroxamic acids. The hydroxamic acid represents a useful chelating agent with iron specificity; it is particularly suitable for to control the formation of scale.

Iron (III) chloride was slowly added to a solution of the hydroxamic acid. After adjusting the reaction mixture to pH 9.4, a strongly colored solution was obtained. but no precipitate formed. This indicates strong chelation.

Example 10:

0.15 mol NTE anhydride in pyridine N-dimethylhydrazine were reacted with 0.15 moles of N,. After removal of the solvent and completion of purification , ΝΤΕ-Ν, Ν-di-methylhydrazide was obtained. The hydrazide is suitable as a growth

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regulators for plants and as a chelating agent. Example 11;

0.03 moles of NTE anhydride in dimethylformamide were used with 0.03 mol of 1,2-dimercaptoethane were added. The mercury complex of the product, namely NTE-ß-mercapto-ethylthioester, is suitable as a fungicide.

Example 12;

0.040 mol of NTE anhydride in dimethylformamide were reacted with 0.011 mol of sucrose. After a reaction time after 18 hours, the sucrose nitrilotriacetate formed was isolated and removed from the remaining solvent, Freed small amounts of tar and unreacted material. The product is suitable as a G-builder for the detergent industry.

Example 13;

8.6 g of polyethyleneimine in dimethylformamide were with 35 g of NTE anhydride are added. The implementation took place a Week at room temperature. The resulting polymer NTE-amide was precipitated with ether which became the solvent washed out and the product dried. This is as a coagulation aid in waste processing usable.

Example 14;

A solution of 2.56 g of NTE anhydride in 10 ml of N-methyl

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1.70 g of β-mercaptoethylamine were added to pyrrolidone. After removal of the solvent and excess amine, symmetrical NTE-bis (N-ß-mercaptoethyl) amide was obtained.

An aqueous solution of the amide was slowly diluted with Hydrogen peroxide was added until all mercapto groups were converted into disulfide bonds. The received Compound was an effective brightener for the electrodeposition of copper.

The following is an example of the excellent properties of this substance.

The following substances were used in the specified concentrations to produce a plating master bath: 209.73 g CuSO ₄ - ¹ PH ₂ O per liter, 59.92 g concentrated H ₂ SO ₄ per liter and 39.63 ecm 37 ^ HCl per liter.

There were panels in a Hull cell at 3 amps plated, resulting in a plating area with current densities 53.82 and 1614.60 amps / m (5 - 150 amps./sq.ft.). With the stock solution was on a normal board a dull, matt copper layer electrolytically generated (plating time 5 minutes at room temperature). When adding the previously described, disulphide-bound Polyamide in a concentration of 0.05992 g / l to the stock solution, however, resulted in bright, glossy deposits with a current density in the range of 53.82 - 1076.42 A / m.

Example 15t

9.47 g (0.05 mol) of NTE anhydride mixture in 50 ml of N, N-dimethylacetamide 3.04 (0.095 mol) of hydrazine were added. After a reaction time of 5 hours, the solvent became removed under vacuum. Through ion exchange

1098in /? 2S3

Chromatography of an aqueous solution of the residue was performed unreacted hydrazine removed. After withdrawal of the watery Solvent, a mixture of NIE mono- and di-hydrazide.

Example 16:

17.3 S (0.10 mol) of monomeric NTE anhydride in 80 ml of N-methylpyrrolidone were combined with 10.0 g (0.13 mol) of glycine. The reaction time was 24 hours at 50-60 ° C. The N-methylpyrrolidone used as solvent was removed under vacuum. After the unreacted GIy one had been separated off, the crude glycinamide was repeatedly triturated with hot benzene. The NTE-glycinamide was recrystallized from ethanol / water mixtures.

Starting materials and molar ratios with which different ver novel NTE anhydride derivatives of the specified Formulas are compiled in the tables below. (In it, R and Z have the mentioned Meaning).

Table I:

0 OR

tt ti I

Nf CH ₂ CNZ) _p ρ m 1.2

3-p

NTE-anhydride reaction partner _R \ product

monomeric diphenylamine 1 /> \\ / f

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Table I (continued)

monomeric Hydrazine 1 H NH ₂ dimeric Hydroxylamine 2
1 H
H -OH
-OH monomeric Iminodiessig
acid 1 -CHgCOgH -CHgCOgH dimeric Glycine 2 -CHgCOgH H 1 -CHgCOgH H monomeric Iminodiaceto
nitrile 1 -CHgCN -CHgCN monomeric N, N-dimethyl
urea 1 -H / C
-CN
C. Il ^v
0

monomeric

histamine

-H

-CH ₉ -CH ₉ T 'MH

IJ

monomeric

Guanidine

NH

Il

-C-NH,

monomeric

Morpholine

Z and R aind -CH ₂ -CH ₂

and are connected like an alkylene bridge

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Table I (continued)

monomeric tetraglycine 10

-C- J ₂ MH-CH ₂ CO ₂ HH

monomeric V -Mercapto- -CHp-CHpCHp-SH propylamine 1

dimeric K- (o-hydroxy-

phenyl) -hydro- ² xylamine

-OH

HO

-OH

monomeric

-CH ₂ CH ₂ -SS-CH ₂ CH _{2 -H}

monomeric 3- (ß-aminoethyl) thiophene

-CH ₂ -CH ₂

In the case of monomeric NTE anhydride, the above. called the reaction partner in a ratio of around IiI used; in the case of dimeric HTE anhydride, the ratio is about 3: 1 «(usually you get a mixture with practically equal amounts of the corresponding mono- and di-substituted Product).

109 8 1 n - /? 26

Table II:

Il

I »

(HO-CCHg) - N -f CHgC-ORj 3-P

P = I,

NTE anhydride reactant (ROH p R in the product

monomeric

phenol

monomeric glycolic acid -CH ₀ CO ₀ H

gCOg

monomeric

Citric acid CHgCO ₂ H

-CH-COgH

CHgCO ₂ H

dimeric

p-nitrobenzyl alcohol -CH ₀ // ^

WNO,

-CH,

NO,

monomeric

Triethanolamine (- CH ₂ -CH ₂ -;

dimeric

Salicylic acid

HOgC

HOgC

1 0 9 8 1 Π /? 2 6

table II (continued:

monomeric glucose

H 0 G

- OH

HO

. ^0H

- OH CH ₂ -

monomeric sucrose

CH ₂ OH

CH ₂ OH

'< _0H v

V ⁰ y

\ HO A

/ CH ₂ -

OH

HO

dimeric hexafluoroisopropyl 2
panol

CF ₅ -CH-CF ₅

monomeric cellophane loop

Penta-β-1,4-glu cosyl

monomeric polyoxypropylene with end- (-0-CHp-CH-)

permanent hydroxyl, ⁿ

group _CH ^

monomeric hexafluoromaphenol A.

/ 7 ~ \ »" r ν

109810/2263

Table II (continued)

monomeric tartaric acid 1 0 0
H tt 1.2 -CH CH- (HO-C-CH ₂ ) - Nf CH ₂ C-SR) ρ =
3-Ρ P. I I HTE anhydride reaction tempera
tur (RSH) 2 CO ₂ H CO ₂ H Table 3: dimeric butyl mercaptan 1 1 monomeric Ν, Ν-dimethylcysteine R in the product CH ₃ CH ₂ OH ₂ CH ₂ - CH ₅ CH ₂ CH ₂ CH ₂ - -CH ₂ -CH-CO ₂ H

monomeric thiophenol

monomeric dipentene dimercaptan 1

CH

CH

monomeric 1,4-butanedithiol

-CH ₂ CH ₂ CH ₂ CH ₂ -

109810/226

Table IV:

.0

N-Z

(R ₁ -CI

H,

H Z

χ R

5 m

η = 1-10,000, q = 0-10,000

NTE anhydride reaction temperature ZR ₁

₅ R ₄ R ₅ rm

monomeric hydrogenated polyacrylonitrile HH H HH Hl 1

monomeric / hydrogenated dimeric polymetha-

Mixture of acrylonitrile

HH H OH ₅ H; H 1

monomeric

of poly-1-acetamido-4-poly (1-hydroxydra- «ino-4- butene) HHH II HZ

10 981 Π /? 263

2040134

Table V:

CO ₂ H GH ₂

CH ₂ -CU ₂ H

R »

R »

CH ₉ C = ON -

NTE-anhydri d Polymeric reac -
partner R. product
m η monomeric Ethylenediamine H 2 1 end permanent
Amine groups
in reaction
partner monomeric Pentaethyiene hexamine H 2 5 monomeric / di-
Beer mixture of hydrolyzed
Polyoxazoline ab
directed polydi-
methylenamine H 2 100-1200

monomeric

derived from hydrolyzed polyoxazine Polytrimethylene amine

10-40

Ί0981Π / 9263

Table VI:

"1

CH ₂ CO ₂ H
ι

C-CH ₂ -N-CH ₂ CO ₂ H

OH »

(RCR) r ι

'R ι

■ C

VR / ία

y
ΚΡΓΕ-anhydri d partner

Polymerization st

monomeric
monomeric

monomeric

H ₁ Ε,

Polyvinyl alcohol P ol y all yl alk ohol

Polyphenyl vinyl alcohol

HHH

I ^ R ₅ rm

HHOl HHIl

H-HOl

109810/2263

Claims (1)

Claims; / Λ
^ζ Λ · Nitrilotriacetic acid and nitrilotriacetic acid anhydride derivatives of the formulas: 0 C-CH,
C-CH, 0 ^ά N-CH ₂ CO ₂ H (I) 0 ^ or y- ^ Z ^ "» CH ₉ -C D N-CH ₂ -COC-CH ₂ -N * ^v 0 (II) C-CH ₉ CH ₀ -O. ο ^u or CO ₂ H CH ₉ O R ¹ ^ " ¹ (III) HO ₂ C CH ₂ -N-CH ₂ CNZ or Il I C-N-Z ? ^H 2 (IV) HO-CH ₉ C ₀ - ^{N v} - ₀ CH -CNZ ί d C. ", 0 R where only one of the radicals R and Z can be hydrogen and Z and R are connected via an alkylene bridge » 109810/2263 "- 35 - when R is a cycloalkyl or heterocycloalkyl group, or CO ₀ H ι * ? ^H 2 N »HOgC -CHg ^H CHg-GOR (V) or C-OR (VI) ^CH 2 N «HOgC CHg CH ₂ -C-OR or GO ₂ H CR ₂ C N-CH ₂ -Ii-SR (VII) CHg COgH or CHg-C-S-R ι HOgC-CHg CH ₂ -CSR (VIII) Il or 109810/7 2040134 HO ₂ C-CH ₂ HO ₂ C-CH ₂ N-CH ₂ -C N-Z C ι 4- C - H Z m n or (IX) H N HO ₂ C-CH ₂ m (
W i ⁿ R -
I.
C ¹ -JN
I.
CH ₀ '~
I ^
C = O
t
Kf " I. I. j HpC R / ' or (X) 1098ΐη / ?? 0? -'37 - CH ₀ CO ₉ H
ι t- έ CH ₂ CO ₂ H (R-C-R) (χι) where R is hydrogen, alkyl groups, substituted alkyl groups, Aryl groups, substituted aryl groups, peptide groups, Carboxyalkyl groups, substituted carboxy alkyl groups, Heteroaryl groups, alkyl substituted heteroaryl groups, cycl oalkyl groups, cycloalkenyl groups, Heterocycloalkenyl groups, heterocycloalkyl groups, carbohydrate groups or means mono- or polysaccharide groups and Z is hydrogen, alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, peptide groups, Carboxyalkyl groups, substituted carboxy alkyl groups, Heteroaryl groups, alkyl-substituted heteroaryl groups, cycloalkyl groups, cycloalkenyl groups, Heterocycloalkenyl groups, heterocycloalkyl groups, carbohydrate groups or mono- or polysaccharide groups means or one of the formulas R. » R. -C-N ' , R C-N Il ~ "· Il N O R. C-N ¹¹ \ S R -C-N-N it ι O R -C-N-N II, \ S R R 109810/2263 -H, -OH, -OR or —- C - * N-C-S M R m ^{above sea level} corresponds to ", where: ■; +
M is an alkali or alkaline earth metal, m is a number from 0 to 20, η is a number from 1 to 10,000 and q is a number from 0 to 10,000 means. 2. Monomeric nitrilotriacetic anhydride according to claim 1 according to the formula ζ. C-CH ₂ O '^ N-CH ₂ CO ₂ H 3 · Dimer nitrilotriacetic anhydride according to claim according to the formula: 109810/7263 ⁰ .C-GH _2x J ?, _X ^CH 2- ° C O. ^ N-CH ₂ -COC-CH ₂ -N .; ^ O ■ C-CH ₀ 'CH ₉ -C. 0 ^d - Ό 4. nitrilotriacetic acid derivative according to claim 1 in the form of a nitrilotriacetic acid mono- or bis-hydrazide. 5. nitrilotriacetic acid derivative according to claim 1 in the form of a mono- or bis-hydroxamic acid. 6. nitrilotriacetic acid derivative according to claim 1 in the form of a mono- or dialkyl nitrilotriacetamide. 7. nitrilotriacetic acid derivative according to claim 1 in the form of a polyamine nitrilotriacetamide. 8. nitrilotriacetic acid derivative according to claim 1 in the form of an N-substituted mono- or polynitrilotriacetamide. 9. nitrilotriacetic acid derivative according to claim 1 in the form of a polyol nitrilotriacetate. 10. nitrilotriacetic acid derivative according to claim 1 in the form of a carbohydrate nitrilotriacetate. 11. nitrilotriacetic acid derivative according to claim 10 in the form of a glucose, sucrose or starch nitrilotriacetate 109610/2263 _ 40 - or of a nitrilotriacetic acid mono-, oligo- or polysaccharide ters. 12. nitrilotriacetic acid derivative according to claim 1 in the form of a nitrilotriacetate ester of a carbohydrate. 15. Process for the preparation of monomeric and dimeric Nitrilotriacetic anhydride according to one of the claims 1 to 3, characterized in that nitrilo triacetic acid with an alkyl or aryl carboxylic acid anhydride, a polymeric linear dicarboxylic acid anhydride, an N, N'-disubstituted one Carbodiimide or an aliphatic halocarboxylic acid anhydride as a dehydrating agent in the presence of an amine serving as a solvent or one Amids of the Fownles: ⁰ ·· Y-C-N ^x 2 1 2 in which Y, Y and Y are each hydrogen, alkyl groups, aryl groups or are substituted aryl groups, or ■ c (On N-Y 1 2 converts, in which Y, Y and Y have the aforementioned meaning and η is a number from 2 to 5. 1098 1/7263 - 41 - ■■■ -. '■■■ 14. The method according to claim 13 »characterized in that that the solvent used is an amide of the Foimel 0 π "/ ^
YCN ρ
Y used, in which Y, Y * ^ and Y have the aforementioned meaning and the alkyl groups contain 1 to 22 carbon atoms. 15. The method according to claim 13, characterized in that that the solvent used is an amide of the formula used, in the Y, ι, Y and η the aforementioned meaning and the alkyl groups contain 1 to 22 carbon atoms. 16. The method according to any one of claims 13 to 15, characterized in that the dehydrating agent an anhydride of benzoic acid, naphthoic acid or toluic acid or a corresponding alkyl, alkoxy, nitro or halogen-substituted anhydride is used. 17 »Method according to one of claims 13 to 16, 109810/7263 characterized in that a weight ratio of Amide to nitrilotriacetic acid of at least about 0.2: 1.0 applies. 18. The method according to claim 17, characterized in that there is a weight ratio of amide to nitrilotriacetic acid from about 3 to about 10: 1 applies. 19. The method according to claim 13, characterized f shows that an aliphatic carboxylic acid anhyaride is used as the dehydrating agent. 20. The method according to claim 13, characterized in that there is a molar ratio of dehydrating agent to nitrilotriacetic acid of up to about 50: 1. 21. The method according to claim 20, characterized in that there is a molar ratio of dehydrating agent to nitrilotriacetic acid of about 10i1. 22. The method according to claim 13, characterized in that the amide used is N-methylpyrrolidone. 23 · The method according to claim 13 »characterized in that the amide used is N, N-dimethylacetamide. 24. The method according to claim 13 »characterized in that one nitrilotriacetic acid in the presence of a Reacts tertiary amide with acetic anhydride. 109810/2263 25. The method according to claim 24, characterized in that that as a tertiary amide N-methylpyrrolidone or N, H-dimethylacetamide used. 26. The method according to claim 13 »characterized in that that the dehydrating agent used is N, N'-dicyclo hexylcarbodiimide used and the implementation under use ^ generation of a tertiary amide. 27. The method according to claim 2b, characterized in that the tertiary amide used is dimethylformamide, 28. The method according to claim 13, characterized in that one for the preparation of dimeric nitrilotriacetic anhydride Reacts monomeric nitrilotriacetic anhydride with acetic anhydride. 29. Process for the preparation of nitrilotriacetic acid derivatives of the formulas III to XI according to claim 1, wherein R and Z have the meaning given in claim 1, characterized in that monomeric or dimeric nitrilotriacetic anhydride is reacted with a compound, which contains a hydrogen atom which can be replaced by a functional acyl group. 30. The method according to claim 29, characterized in that for the preparation of compounds of the üOnnel III about 1 mole of monomeric Ifitrilotri acetic acid anhydride with about 1 mole of a compound of the formula: 109810/2263 ORIGJNAL NO in which R and Z have the meaning given in claim 1. 31. The method according to claim 29, characterized in that that one for the production of compounds of the formula For IV about 1 mole of di.meres tiitrilotriacetic anhydride with about 3 moles of a compound of the form el NO in which R and Z have the meaning given in claim 1. 32. The method according to claim 291, characterized in that that for the preparation of compounds of the formula V monomeric nitrilotriacetic anhydride with about 1 mol of a compound of the formula R-OH, in which R has the meaning given in claim 1, is reacted. 33. The method according to claim 291, characterized in that that about 1 mol of dimeric nitrilotriacetic anhydride is used for the preparation of compounds of the formula VI with about 3 moles of a compound of the formula R-OH, in which R has the meaning given in claim 1, is reacted. 34. The method according to claim 29 »characterized in that for the preparation of compounds of the formula VII 1 mole of monomeric nitrilotriacetic anhydride with about 1 mole a compound of the formula R-SH in which R has the meaning given in claim. 35 · The method according to claim 29, characterized in that that about 1 mol of dimeric nitrilotriacetic anhydride is used for the preparation of compounds of the formula VIII with about 3 mol of a compound of the formula R-SH, in which R has the meaning given in claim 1, is reacted. For: Stauffer Chemical Company Lawyer COPY 109810/2213