DE2511888A1 - PROCESS FOR THE PRODUCTION OF AETHERPOLYCARBOXYLATES - Google Patents

Description

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENT LAWYERS

8 MÜNCHEN 86, POSTFACH 86 02

REQUIRED

Attorney's file 25 8l6

MONSANTO COMPANY St. Louis, Missouri 63166 / USA

"Process for the production of ether polycarboxy

laten "

This invention relates to methods of making ether polycarboxylates.

Xtherpolycarboxylates have the following general formula

509841/0956

8 Munich 80, MauerkircheistraBe 45 Banks: Bayerische Vereinsbank Manchen 453100

Teletrams: BERGSTAPFPATENT Munich Hypo-Bank Munich 3892623 TELEX: 0524560 BERG d Postscheck Munich 65343-808

COOM COOM

CH 0 CH

I I

COOM X

where M is an alkali metal and X is a hydrogen atom or a COOM group. They are called complex building Agent for metal and alkaline earth metal ions and suitable as detergent builder. Although method of manufacture of such compounds (for example by means of the Williamson reaction of the ether type) are described further processes for their production are desirable.

The invention relates to a process for the preparation of the above-described ether polycarboxylates and their acids and esters of certain imidacarboxylafeen, their O-carboxylates and amide carboxylates.

According to the method of this invention, ether * polycarboxylates of the general formula below

COOM COOM I I

CH 0 - CH

t!

COOM X

and their acids and esters by using imide carboxylates, their O-carboxylates or amido carboxylates hydrolyzed.

The carboxylates used in the reaction can there-

509841/0956

2511883 - 3 -

be prepared by one or both heterocyclic CH ^ components of the imides of the following general formula

CH ₂ CH ₂ -

carboxylated, where in the formula R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or is a phenyl group. (Such imides and processes for their preparation are known). In some In carboxylation processes, when E is hydrogen, the imide nitrogen can also be carboxylated. In general, the carboxylation of the imide group only leads to the monocarboxylation of one or both CHo moieties, however, under particularly severe carboxylation conditions, one or both of the CBU moieties dicarboxylate can be. It can therefore be the imide carboxylates formed by the following general formula

509841/0956

R '

R "

where E ^{1 is} a. Hydrogen atom or a COOM 'group (where M ^{1 is} an alkali metal, ammonium or 1/2 magnesium) and E "is an alkyl group having 1 to 12 carbon atoms, a phenyl or COOM group. At least one of the E' substituents must COOM ¹ , whereby it should be noted that the E 'substituents need not be the same. Depending on the carboxylation conditions, the acid or ester forms of such imidearboxylates can be more easily obtained than the salt forms. Of course, the salt forms can also be converted into the acid or ester forms It should be noted that certain imide carboxylates may have enolate forms, for example

Il

.0

R "

509841/0956

when H is ¹ "1/2 Hg or

ι.

when M ^{1 is} a monovalent metal. Although the imide carboxylates used in this invention are shown only in the keto structure (I) for reasons of convenience, this representation is also intended to include the enolate forms of these compounds, which may exist under various conditions.

Ureter carboxylation conditions can imide and / or their carboxylates O-carboxylates (i.e. carbonates) the formula below

N
R "

0 COOM '

form. These O-carboxylates are used in the description and referred to in the claims as O-carboxylates of the imide carboxylates in order to clarify their relationship to the To indicate imide carboxylates and to prevent the Avoid nomenclature that would otherwise be required to indicate the possible configurations when one

50984

956

or both imide oxygen are carboxylated. It is however, it should be noted that there is no restriction on the O-carboxylates of the imidacarboxylates must be derived from imide carboxylates "

If the carboxylation reaction is carried out in the presence of alcohols, water or a base, will Amide dearboxylates of the following general formula

^R '\ A

C C

R ¹

O = C

HNR

R ¹

C = O I

formed (with such amide dearboxylates formed as well can, if the imide dearboxylates subsequently with Alcohol, water or a base are reacted), which, after further carboxylation, compounds of the following general formula

i I

• N 0R ^IV M'OOC R "

5 0 9.8 4 1/0956

deliver. It can therefore use the amide carboxylates given above summarized by the following general formula

R «0

O.

O = C

R 'R "

C = O
ORlV

characterized v / ground, where in the last three formulas B is a hydrogen atom, H ^{1 is} an alkyl group with 1 to 12 carbon atoms, a phenyl group or a phenyl group which is optionally substituted with up to three alkyl groups ^ each with 1 to 12 carbon atoms and v / at least one of the R ^f ~ substituents attached to a carbon atom is a COOM 'group.

The desired product of the formula

COOM

CH -

: oom

COOM
-CH

I.
χ

or its acids or esters are obtained by the fact that the imide or amide bonds of the above-described Iraidcarboxylate, their O-Carboxylates and Amidcarbo: xylate 5 09.84 1/0956 · -Ö-

hydrolyzed. The term "hydrolyze" is used here defined as including hydrolysis reactions carried out either in acidic or basic medium or in The presence of alcohols can be carried out to obtain the salt, acid or ester forms, as desired,

The hydrolysis, for example by reaction of an alkali metal base (for example alkali metal hydroxide, carbonate or bicarbonate) with carboxylates in which a O-linked carbon atom is carboxylated, provides a compound of the formula

COOM COOM

I I

CH 0 CH ₀

I -

COOM ",

while reacting with carboxylates in which both O-linked carbon atoms are carboxylated, compounds the formula

COOM -0 - COOM I. I. CH - CH 1 I. COOM COOM

can provide- Dicarboxylated O-linked carbon atoms can, if formed, one of the carboxylate substituents by decarboxylation in the hydrolysis reaction lose. The NR "part can be used as an amine (or Ammonia, if R "is COOM) is split off in the reaction

509841/09 56

511888 "

will. The use of carboxylates in which at least one R 'substituent on each O-linked carbon atom is a hydrogen atom is preferred »because such compounds are easier to form than Compounds containing dicarboxylated carbon atoms.

The use of carboxyl ats where only one 0-linked Carbon atom is carboxylated, is im. generally preferred because that obtained by hydrolysis Ether tricarboxylate is more easily biodegradable than the ether tricarboxylates that are made from Compounds obtained in which both O-linked carbon atoms are carboxylated. However "form for some Purposes Mixtures of ether tri- and tetracarboxylates superior builders which make the use of mixtures of compounds desirable in which one and wherein both O-linked carbon atoms are desirably carboxylates siad.

The above-described imide carboxylates are preferably obtained, their O-carboxylates and amide dearboxylates of this invention by carboxylation of the imide as shown. All of the carboxylates described, including their acid and ester forms, are carboxylation products consider, which are obtained by carboxylation of at least one CEU- ^ il of the imide. It's on it

509841/0956

point out that the respective carboxylates or their mixtures according to the carboxylation conditions and whether the water, alcohol or base required for amide carboxylate formation is present is or not.

The carbonylation of the imide is preferably in one Any solvent that does not unduly participate in competing side reactions, can be used. In general, aprotic solvents are used with relatively high (1 or greater) Dipole moments and dielectric constants that are greater than 10 or solvent mixtures that are at least 3C $ contain solvents with such high dipole moments, preferred because the use of solvents with higher dipole moments usually higher yields deliver, especially when alkali metal phenate-carbon dioxide complexes can be used as carboxylating agents as described below. For example, solvents, such as dimethylfornania, hexamethylphosphoric triamide, Pyridine, dimethyl sulfoxide, tetramethylurea, N-methylpyrolidone, bis-2-methoxyethyl ether, tetrahydrofuran and ethyl acetate, can be used for most carboxylation reactions. In some cases it will be when using mixed solvent systems (including Systems that contain solvents with low dipole moments, such as benzene, toluene, hexane, etc.,

509.84 1 / 09S8

which, when used alone, in general do not give good yields) improves the yield and / or reduced gel formation - Optimal solvents or solvent mixtures can be used for the respective Reaction systems can be determined by routine examinations.

If desired, the carboxylated imide can be derived from the Reaction mixture using conventional methods such as separated by filtration, centrifugation, etc. In some cases, for example, when alkali metal phenate-COp complexes When used as a carboxylating agent it can get a little tricky not reacted imide, phenol and solvent from the carboxylated one Separate imide by means of mechanical processes. In such cases, the separation can expediently can be achieved by using V / water to form an aqueous phase containing the carboxylate contains, adds and the aqueous phase with a water-immiscible Solvent for the imide and phenol (but not for the carboxylate), for example with Toluene or chloroform, extracted.

Particularly preferred solvents, especially when using alkali metal phenate / carbon dioxide complexes, are 4-substituted Pyridines such as # -picoline. When using as a solvent, the addition of water leads to the

509841/0956

^- -LX et * ™

-'Me -

Reaction mixture to form 2 phases. The watery Phase contains the imide carboxylate, some y-picoline and some sodium bicarbonate (derived from the carboxylating agent) and is essentially free of non-reaction starting materials and other organic contaminants. The ^ picoline present forms an azeotropic one Mixture with water and can be removed by simple distillation, eliminating the need for separation by means of extraction is not necessary. The organic phase is ö'-PIcoline, which is some water, non-carboxylated imide and Contains phenol (from the carboxylating agent).

The ^ -Picolin can in turn easily be separated from the other organic materials by azeotropic distillation, which enables an economical recycling of starting materials which have not been converted. The azeotropic mixture of water and picolin removed from one or both phases can also be recycled. If ^ picoline is used as the solvent, reaction temperatures of 60 to 150 ⁰ C are preferred in order to create an optimal balance of the viscosity and reaction kinetics.

In a preferred process for the preparation of the compounds of this invention, one carboxylates an ImId,

- 11b -

509841/0956

- veh -

N-alkyl ^ .S-morpholinedione, by reaction with methyl methoxymagnesium carbonate. The carboxylation was preferably carried out in a solvent such as dimethylformamide

- 12 -

609841/0956

or a mixture of dimethyl formamide and bis-2-methoxyethyl ether, at temperatures of 100 to 160 ⁰ C, preferably 135 carried out to 145 ° C to reasonable reaction times with a correspondingly low thermal decomposition to erzielen- (This temperature range is, for \? eckmäßig at atmospheric pressure If reduced pressures are used to facilitate ethanol removal, the temperature range can be decreased). This reaction gives, depending on the concentration of the reactants, the length of the reaction time, etc., imide carboxylates in which one CHp part is carboxylated or in which both CH ^ parts are carboxylated, or mixtures thereof. The ratio of compounds in which both CHp parts are carboxylated can be increased by increasing the ratio of carboxylating agent to imide and / or by prolonging the reaction. The ratio can of course also be decreased by lowering the amount of the carboxylating agent and / or shortening the reaction time.

The magnesium carboxylates thus obtained can with alkali metal hydroxide to form a mixture of Ithertri- and tetracarboxylates are implemented. Preferably however, the magnesium carboxylates are first dissolved in cold phosphoric acid and treated with ammonia, to precipitate magnesium and form ammonium carboxylates, which are then unset with alkali metal hydroxide.

509841/0956

In a further preferred embodiment of the Invention is the imide by reaction with a Carboxylating agent that is carboxylated by Combining carbon dioxide with a phenate of the general formula

OH

where E ^{llf is} an alkyl group having 1 to 12 carbon atoms and η is an integer from 0 to 3. (Carboxylating agents of this type are described in U.S. Patent 3,658,874, incorporated herein by reference). The carboxylation is preferably carried out in a solvent with a high dipole moment, as described above, at temperatures from 0 to 150 ° C., preferably 25 to 100 ° C., under sufficient pressure to avoid carbon dioxide losses. Solvent, temperature and pressure are of course brought into relation with one another in such a way that optimum solubility, reaction rate, etc. are achieved. This reaction can be used to obtain imide carboxylates in which one or both CEo parts are carboxylated, or mixtures thereof. The relative amounts of these compounds can be varied by adjusting the amount of carboxylating agent and the reaction time accordingly, as described in the above.

609841/0956 5

embodiment of this invention has been shown. This embodiment leads to the formation of imide carboxylate enplatcarbonate, ζμΐη example

H CH—

CH

I i

COOM '
OCOOM '

R "

Amides, for example

CH ₂ -— 'C

R "

CHCOOM '

'M00C-rr

__CH C

or

O = C

NH

and amide carboxylates, for example

M'OOC—

M'OOC-C

C '

O = CC ^:

! 1

M ¹ OOC -NR! J

509841/0958

-Kf-

as well as. Imide carboxylates.

The carboxylation of the imide can continue by means of Multi-stage reactions can be achieved. For example, the imide

CH ₂ CH ₇ I 2, 2

I.
H

reacted with lithium diisopropylamide (preferably in tetrahydrofuran at about -4-0 to -70 ⁰ C) and the reaction product treated with carbon dioxide for carbonylation of a CHp part (COOLi substituents) and the imide nitrogen.

Carboxylation of imides can also be used of an alkali metal arbate salt under COp pressure, preferably at a temperature between 140 and 270 ° C can be achieved. The conversion speed increases generally with increased COp pressures. The for Achieving a respective conversion rate required COp-Eruck can when using catalysts reduces grounding, such as of Group VIII transition metals and their derivatives, such as for example iron and nickel, and Group IB and VB metals and their derivatives. The use of lo-

509841/0 956 ^1e

Al

solvents, such as molten salts with low melting points, for example sodium formate as a solution medium can speed up the reaction, improve heat transfer and remove the reaction products facilitate.

Other suitable carbosylating agents and optimal ones Conditions for their use can be determined through routine experimentation.

Preferably, the carboxylates (I, II, III) with an alkali metal base (usually, with at least one 2 # stoichiometric excess of the base and at temperatures from 90 to 150 C) implemented "with the formation of

and or

COOH

COOM

COOM

CH O

COOH

COCi-I

COOM CH

1.

COOM

It can also these products by acid hydrolysis of carboxylates (preferably, with aqueous mineral acid at temperatures of 25 to 10O ⁰ C) was obtained and the Heutralisierung Hydrolysenprodukts with alkali metal base

will. In general, the immediate response will be 509841/0956

of the carboxylate with the AXkalimetalbase preferred to possible decarboxylation during hydrolysis and / or to avoid salt formation - The use of sodium or potassium hydroxide, especially sodium hydroxide, in the saponification or neutralization reaction, with a view to the preference of the corresponding Sodium or potassium ether arboxylates are preferred as detergent builders.

The invention is further carried out by the following Examples illustrate where all parts and percentages are by weight unless that is so is stated otherwise.

example 1

About 14 · g of sodium phenoxide in 100 ml Dimethylfornamid is stirred under a carbon dioxide atmosphere, and to rise the temperature of 25 ⁰ C to 33 ° C vrährend 5 to 10 · minutes läßt- Man the Eildung observed a precipitate which dissolves on further stirring, if the mixture is allowed to cool to 25 ° C. After about 3 hours, the carbon dioxide atmosphere is replaced by a nitrogen atmosphere and a solution of about 7 * 7 e N-Hethyl-3-5-niorpholindione in 20 ml of diethylformamide is added to the mixture, which is then left to stand for about 20 hours. The reaction mixture is poured into 200 ml

9841/0956

id carboxylate al

Diet ether and filtered to use the imide carboxylate as Isolate white solid, which was dissolved in 100 ml of water will. Sodium hydroxide (20 g) is added and the solution is kept at 85 ° C. for 2 hours with stirring. One concentrates the Losiaag to about 50 n »l by means of vacuum distillation.

A solid is precipitated by adding 200 ml of methanol. Product identified by nuclear magnetic resonance analysis as

ÖOONa

CH- 0 COONa

GOONa

If the above procedure is repeated using a 4: 1 ratio of carboxylating agent to Iraid, this gives a mixture of

COONa

OH 0

I.
COONa

COONa

OH

and

COONa

GH

OOONa

. C.

H
J

COONa

Example 2

About 115 ωΐ (2.3 molar) hexane solution of n-butyllithium is added under a nitrogen atmosphere to a mixture of * J-00 ml of tetrahydrofuran and 24 g of diisopropylamine, which was pre-cooled to -40 ° C. This mixture it is cooled to -70 C and a solution of 12.5 g of 3 · 5-

509841/0956

Morpholinedione in 100 ml of tetrahydrofuran and pearls a stream of carbon dioxide into the mixture for about 1 hour. The mixture is evaporated, leaving a dry powdery residue is obtained which contains the following compound

CH CH COOLi

I ² I
cc

COOLi

which one dissolves in 150 ml of water and an acidic ion exchange column (the one with a sulfonated Fisher Scientific "Company's polystyrene resin under the V7 symbol REXTN 101 is packed). The sour Solution is neutralized with sodium hydroxide. Nuclear magnetic resonance analysis shows that the solution is sodium 3 «5-nio ^ pholindioii-2-carboxylate contains. Reacting this product with hot sodium hydroxide and adding methanol as in Example 1 gives

COONa COONa COONa

Example 5

Carbon dioxide is bubbled through a mixture of about 16 g of potassium phenoxide in 100 ml of dimethylformamide. The Tenpera-

- 20 "- 509841/0956

door increases from 25 ⁰ C to 41 ° C in about 10 minutes and slowly decreases to 25 ° C, giving, where the formation and the solution is observed a Peststoffs. After 3 hours, the pumping in of carbon dioxide is stopped and the mixture is brought under a nitrogen atmosphere, a solution of 7 »7 S N-methyl-3« 5-morpholinedione is added. in 15 ml of dimethylformamide and the mixture is allowed to stand for 4 days at about 2 ° C. The mixture is then poured into 200 ml of diethyl ether and filtered to obtain a solid, which is dissolved in 100 ml of water and mixed with 20 g of sodium hydroxide Reacts at 85 ° C for two hours, whereby

COONa COONa

I I

CH 0 CH ₂ "

COONa

obtained in a mixture with some potassium salts.

Example 4-

About 0.05 mol of N-methyl-3 »5-morpholinedione in 12 ml of dimethylformamide is added over about 4-0 minutes to 1.4 ha of methyl methoxymagnesium carbonate in 50 ml of a 75/25 mixture of bis-2-methoxyethyl ether / diicetylformamide . The resulting mixture is kept for one hour at 120 to 14-0 ⁰ C, it is then poured into 200 ml of ethyl ether and filtered to ge \ d.nnen the solid Kagnesiumimidcarboxylatprodukt, which is added to aqueous phosphoric acid (the 1 mol Η, ΡΟχ per Mol of magnesium in the initial methyl methoxy

509841/0956

23 25T1888

magnesium carbonate solution) adds. The received Solution is neutralized to a pg value of 9 with . Ammonia, forms the ammonium salt of carboxylate and the magnesium precipitates as hydrogenated MgNH ^ PO ^. the Carboxylate solution is separated from the precipitate Filter and put them in a layer of sodium hydroxide

l "

shot during 2 hours b «i & 5? G , whereby one

COONa COONa

fr—

COONa
receives

Example 5

About 12.9 g of H-methyl-3,5-morpholinedione and 41.5 g of potassium carbonate is heated for ^ CO under -pressure at 200 atmospheres for about 2 1/2 hours at 200 ⁰ C. The mixture is cooled and the product dissolves in it V / ater , add potassium hydroxide and boil the mixture to remove methylamine and evaporate to dryness. The analysis of the product shows that it .- '

COOK COOK

CH O CE ₂

COOK

contains

S09841 / 0956

Two mixtures containing 1 mole of N-methyl-3-5 ~ iaorpholinedione and 3 moles of sodium carbonate are prepared. The mixture is heated to about 215 ^° C. under 150 atmospheres of carbon dioxide and this temperature is maintained for 2 hours. The other mixture is treated in the same way, after which it is mixed with 2 moles of sodium formate.

Both mixtures are then dissolved. in water ", is heated to nand with sodium hydroxide to expel methylamine.

Analysis shows that "both mixtures have one of the formula

COONa

GOORa

gh

(J

COONa

contain., an etv / a five times greater yield from the sodium formate-containing mixture is obtained. It is believed _s Dab the Sfatriumf orraiat the reaction thereby promotes _s that it contains as solvent for the H-methyl-3 - ^ - ^
serves.

Example 7

Etv / a 0.05 mol of N-methyl-3,5-morpholinedione in 12 ml of di-

-23-

509841/0956

Methylformamide is added to 1.4 mol of methyl methoxymagnesium carbonate in 50% of a 75/25 mixture of bis-2-metho: xyethyl ether / dimethylfcriaamide over a ^{period of about 2 minutes.} The mixture obtained is kept at 120 ° to 140 ° C. for one hour. The mixture is poured into 200 ml of ethyl ether and filtered, whereby solid magnesium imide carbosylate is obtained, which is added to aqueous phosphoric acid (which contains 1 mole of HaPO ₂ per mole of magnesium in the initial methyl methozymagnesium carbonate solution) With ammonia, forms the ammonium salt of the carboxylate and the magnesium precipitates out as hydrated Kg] SELPO ₂ .

The carboxylate solution is separated from the precipitate by filtering and concentrating to a syrup-like consistency - ethyl alcohol is added and crystals are precipitated from

CH ₀ CH COQiIH ,.

I ² I ⁴

O = C NH C

the end. This product is boiled in sodium hydroxide solution to drive off ammonia and amine and obtain it

COONa COONa

I ι

CH ₂ 0 CH

COONa

509841/0 956

-24-

Examples 8-10

The procedure of Example 1 is repeated with the imides shown in the table below, which .be used instead of N-methyl-3.5-morpholindione!

Example 8

Imide

CH ₂ CH ₂

CH ₃ CH CH

, · F

/ ^ O

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In each example you get as a product

COONa

COONa

I CH ₂ 0 CH

COONa

Example 11

The procedure of Example 1 is repeated using different ones set out in the table below Solvent and a 2: 1 molar ratio of carboxylating agent to imide. The product yields are based on the imide fed to the reactions.

^ Yield ^ Yield COONa COONa COONa COONa

Solution
middle dipole
moment 1.03 Donicity Dimethyl
formamide 3.86 3.47 26.6 Hexamethyl
phosphofcri-
amide ι
4.31 0.085 38.8 Ethyl acetate 1.88 3.44 17.1 bis-2-methoxy-
ethyl ether 1.97 3.9 not
certainly Nitrobenzene 4.4 Tetramethyl
urea 29.6 Hexane not
certainly Acetonitrile 14.1 Dimethyl
sulfoxide 29.8

CH "- 0 - CH

CH- 0- CH \ Il COONa COONa COONa

48

68 16

22 1

44

24 49

-26-

50984 1/0956

table (continuation)

certainly

33.1

not

certainly

5118

<1

high Donigitat (a standard for basicity
generally perform higher examinations "

Anhydrous Katriusplienat (2J2 g) was dispersed in a Joint solvent, the 350 nu Soluol -and- 550 nsl Dinethylforsanid contains "One bubbling carbon dioxide for about 30 minutes in the mixture, while maintaining the temperature of the mixture at 25 ° G," You are crystalline I-Hethjl-3 "^ - ^ o ^ pnolindion (128 g) and holds the Gesiissfe at 4-5 0 under a Kobleadioxiddrusk" SRON about 1 ₅ 7 Ätaosphärea "Man, are about 800 ml of water to the
Reaction to _? the Garbo3 ^ 1at product _s i

509841/0956

COONa OCOONa

contains and converts a major part of this product by hydrolysis in

CH ₂ HCCOONa; ^, ^ CHo C * 5 ^ _

An aqueous phase containing the carboxylates and sodium bicarbonate The aqueous phase is extracted with chloroform to remove residual solvent to remove. Sodium hydroxide is added to the aqueous phase, which is then boiled to make the imide car- boxylates and their hydrolysis products in trisodium-2-oxa ~ 1 · 1 -3 ~ P * to convert opane tricarboxylate.

The organic phase and the chloroform extract are combined and the mixture is distilled to remove unreacted N-methyl-3,5-morpholinedione to win that is returned in the cycle

1/0956

Example 13

1 liter of a 2 molar solution of sodium phenate in pyridine is prepared by distilling a mixture of phenol, 50% aqueous sodium hydroxide and pyridine with removal of water. The solution is cooled to 50 ° C. and carbon dioxide is bubbled through it for about 30 minutes. Priority 1 gmol N-methyl-3 '5-n * 03? PkoliBdion to and maintaining the reaction mixture 4 hours at 50 ⁰ C · About 800 ml of water is added and the mixture is extracted in countercurrent with 800 ml of toluene in three Steps to remove phenol, unreacted N-methyl-3 »5-morpholinedione and pyridine. The aqueous phase obtained is boiled in order to drive off any remaining solvent and the carbonate is consumed by the subsequent reactions

CH ₂ CHCOONa

ι ^z i

CH,

U.

CH ₂ CHCOONa

II ^{+ C0} 2 -C COONa

Century

CH ₃

and

CH ₂ CHCOONa = C COONa

CH,

COONa COONa

COONa

-'29-

.509841 / 0956

Sodium hydroxide is added to make up the remaining imide carboxylate and amide carboxylate too

COONa COOlia

I I

CH ₂ 0 CE

COONa

to convert.

The organic phase was distilled to Bohmaterialien solvent and recover the one m ± circuit used *

Example 14 .

The carboxylation of Example 1 we el · repeated with the exception that instead of ^ picoline DimethyIformamid as solvent \ ilrd and the reaction temperature used is in the range of 80 to 90 ⁰ C under four atmospheres CQ_-pressure is maintained for about 2 hours.

The reaction mixture is cooled to 50 ° C. and water (50% by weight of the reaction mixture) is added. The mixture is separated into two liquid phases: a first phase, consisting mainly of ^ -picoline, phenol, unreacted Imide and some water and a 2nd phase, consisting essentially of water, carboxylated products, something Carbonates and ^ -picoline.

- 29a 509841/0956

The second phase is heated to remove% picoline and water which are recycled. Further sodium hydroxide is then added in order to convert the partially hydrolyzed product into a mixture, which is the main constituent

COONa COONa CH - 0 - CH ₂ GOOMa

and a lesser amount

COONa COONa HC - 0 - CH COONa -COONa

contains.

- 30 -

509841/0958

Claims (1)

25118 Patent claims: Λ ψ Process for the preparation of compounds of the general formula COOM - 0 - COOM I. I. CH
I. -CH COOM X wherein M is an alkali metal and X is hydrogen or a COOM group, as well as their acids and esters, d a by characterized in that the imide and amide bonds are hydrolyzed in a carboxylate are present, namely in imide carboxylates the general formula wherein the R 'substituents are hydrogen atoms and / or COOM' groups, where M ^{1 is} alkali metal, ammonium or 1/2 magnesium and at least one R 'substituent is a COOM ¹ group and the R ¹ ' substituent is an alkyl group with 1 to 12 carbon atoms, a phenyl group and / or a COOM group, -31-509841 / 0956 JM in acids and esters of imide carboxylates, in O-carboxylates of imide carboxylates, in amide dearboxylates of the following general formula o = .c I , I i wherein R is an alkyl group having 1 to 12 carbon atoms, a hydrogen atom, M 'or a phenyl group having 0 to 3 alkyl substituents having 1 to 12 carbon atoms and at least one of the R' substituents attached to the carbon atom is a COOM '- Group is and / or
in acids and esters of amide dearboxylates. 2. The method according to claim 1, characterized in that the imide and amide bonds of the carboxylate is hydrolyzed by reacting the carboxylate with an alkali metal base. 3 · Method according to claim 2, characterized that one is a carboxylate of the general formula -32- 509841/0956 CH CH- -R ' ι- used. 4. Method according to claim 2, characterized that one is a carboxylate of the general formula CH, CH-I COOM ¹ T I t f used. 5. The method according to claim 2, d a d u r ch characterized in that one is a carboxylate of the general formula COOM OCOOH used· 509841/0956 -33- -25- 6. The method according to claim 2, characterized in g e that one is a carboxylate of the general formula Vv 0 C COOM 11 used. 7. The method according to claims, characterized that one is a carboxylate of the general formula C I CHCOOM I COOM used. 8. The method according to claim 6, characterized that one is a carboxylate of the general formula 509-8 41/0956 MOOCCH CH ₀ O = C COOM H-N-R * ¹ used. 9 · Process for the preparation of compounds of the general formula COOM COOM I l CH 0 CH I I COOM X, wherein M is an alkali metal and X is a hydrogen atom or a COOM group, as well as their acids and esters, characterized in that one at least one heterocyclic CH ^ portion of an imide the general formula CH ₂ carboxylated, where in the formula R is a hydrogen atom, an alkyl group with Λ to 20 carbon atoms or a phenyl group and that the imide and -35- 509841/0956 Amide bonds of the carboxylates formed and their hydrolysis products are hydrolyzed. 10. The method according to claim 9 »characterized in that the carboxylation in the presence of an alcohol with the formation of an amidliar / boxylate. 11 · Process according to claim 9 »characterized in that the carboxylates formed are hydrolyzed by reaction with an alkali metal base · 12. The method according to claim 9 »characterized that the imide is carboxylated by reaction with a carboxylating agent, which in turn can be obtained by combining carbon dioxide and a phenate of the general formula OM forms, where in the formula E ¹¹ * is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms and η is an integer from 0 to 5. 13 · The method according to claim 12, characterized in that - 509841/0956 indicates that one is a phenate of the formula ONa used and that the imide is carboxylated in pyridine. . Process according to Claim 9 »characterized in that the imide 3» 5-morpholinedione used and that the imide by reaction with Lxthiumdxisopropylamxd with the following reaction carboxylated with carbon dioxide. 15. The method according to claim 13, characterized that after the carboxylation reaction, the reaction mixture is extracted with water and extracting the aqueous extract with a water-immiscible solvent for the unreacted imide. 16. Process for the preparation of a compound of the formula COONa COONa I I CH 0 CH ₂ COONa characterized in that one -37-5098Λ1 / 0956 in pyridine N-methyl-3 »5-morpholinedione is reacted with a carboxylating agent formed by combining carbon dioxide and sodium phenate, water
mixed with the reaction mixture and an aqueous phase is separated off, the aqueous phase is extracted with a water-immiscible solvent for the N-methyl-3,5-morpholinedione and the aqueous phase is reacted with an alkali metal base. 17. The method according to claim 12, characterized in that the imide In ^ picoline
is carboxylated. 18. The method according to claim 17 »characterized that following the carboxylation reaction, water was added to the reaction mixture is, the mixture in a first phase, containing predominantly water, carboxylated imide and # -picolin and separated into a second phase, containing predominantly ^ -picoline, phenol, non-carboxylated imide and water will and ^ -Picolin and water from each phase by azeotropic Distillation can be removed. 19 »Process for the preparation of a compound of the formula - 38 509841/0956 COONa COONa
CH - 0 - CH ₂
COONa characterized in that N-methyl-3 »5-morpholinedione in y-picoline with a carboxylating agent for reaction brings, which was obtained by combining carbon dioxide and sodium phenate, that the reaction mixture with Mixing water and separating an aqueous phase containing carboxylated N-methyl-3,5-morpholinedione and ^ -picoline, the ^ picoline from the aqueous phase as an azeotropic mixture of ^ -Picolin and water distilled off and the aqueous phase is reacted with a sodium base. SG9841 / 0956 ORIGINAL INSPECTED