DD299643A5 - PROCESS FOR THE PREPARATION OF NEW N-CARBOXYMETHYL-N-ALKYL-2.6-MORPHOLINI BEQUINES - Google Patents

Abstract

The invention relates to a process for the preparation of novel * It is characterized in that one prepares carboxymethyl betaines gemaesz the formula by reacting * and / or * with Halogenessigsaeureester in alcoholic solution under reflux, using the reaction conditions below, the reaction controls so that z quaternized as the 2,6-position isomers predominantly reclaims the reaction-inert 2,5-position isomers from the reaction mixture, as reaction conditions: solvent: alcohol from C1 to C4, type of alkylating agent: BrCH2COOCH2CH3 or ClCH2COOCH2CH3 (or JCH2COOCH2CH3 in the exclusive use of * molar ratio (amine : Alkylating agent): 1: 1.1 to * Reaction time: 5-10 h, and converting the resulting quaternary ammonium salts to corresponding betaines by alkaline saponification at 15-65 ° C. in a strongly alkaline medium The advantage of the solution according to the invention lies in the reindars The use of positional isomers and the consequent possibility of exploiting their specific properties, ie when using * N-alkyl-dimethylmorpholines, gives selective carboxymethylation of the 2,6-isomer compounds and extractive recovery of unreacted 2,5-isomer compounds. Formula {procedures; manufacture; * Carboxymethyl betaines; * Haloacetic acid ester; Ammonium salts; saponification; Betaine; positional}

Description

Field of application of the invention

The invention relates to a process for the preparation of N-carboxymethyl-N-alkyl ^. -Morpholiniumbetainen. The compounds of the invention are industrially and in the land use applicable.

Characteristic of the known state of the art In addition to the direct carboxymethylation of tertiary amines with haloacetates (A.M. Schwartz and J.W. Perry, Surface Active Agents VoM (1949) p.226, K. Linner, Textilhilfsmittel u. Washing Raw Materials (1954) S. G65-568,0. Liebreich, Chem. Reports

2/12 [1869], F. B. Downing US Pat. No. 2,129,264 (1938)), there is another variant in the reaction of tertiary amines with

Halogenesssigsäureester. Only by a downstream of the actual alkylation alkaline saponification reaction is the desired Betaine accessible.

IT

R - N + X-CH ₂ COOR

R '

-CH ₂ COOR ^ '

R '

R - N®-CH ₂ C00R R '

+ NaOH

 > R -

N ^ -CH ₂ COO

- NaX

R = long-chain alkyl radical R '= methyl, ethyl, hydroxyethyl R "= methyl, ethyl, hydroxyethyl The preparation of the quaternion ammonium compounds according to equation 1) is known (OE-PS 1167588, Angewandte Chemistry 77 [1965], pp. 327-333). As has been assumed in DD 263685, it is generally accepted that both the Position isomers (2.6 / 2.5) and the configuration isomers are quaternized to the same extent. On the production

corresponding Betainverbindung according to equation 2 has not been received.

Carboxylmethylbetaine based on additionally substituted in the morpholine ring tertiary amines, eg. N-carboxymethyl-N-alkyl-2,6-

Dimethylmorpholiniumverbindungen are not previously described in the literature.

Reasons »is this in the following assumptions:

- The unsatisfactory yields achieved with the use of open-chain N-alkyl-bis (2-hydroxyethyl) -amines as raw material base for the carboxymethylation led to a further drop in yield due to additional steric influence on the nitrogen atom for the N-alkyl bis (2-hydroxypropyl) amines ,

- Appiikationsseitig has been waived further detailed processing quaternized tetrahydrooxazines in the context of the investigations carried out by König and co-workers, as z. B. the additional blocking of the lone pair of electrons on the nitrogen atom did not increase the fungicidal properties of Tetrahydrooxazinderivaten impacted.

The listed quaternary ammonium structures included in the test were:

N-tridecyl-2, e-dimethylmorpholine salts

N-tridecyf-2,6-dimethylmorpholinium oxides

N-tridecyl-N-methyl-1-dimethylmorpholinium methosulfate, bromide and

N-tridecyl-N-benzyl-e-dimethylmorpholinium chloride.

Recent studies according to DD-PS 263685 to 263690 are concerned with the implementation of N-alkyl-2,6 / 2,5-cis / ledrdimethylmorpholinen with Haiogenessigsäureester. These patents assume, under the given conditions, that both the positional and conformational isomers are reacted equally with the quaternary ammonium salt.

Object of the invention

The aim of the invention is a process for preparing neat N-carboxymethyl-N-alkyl-2,6-morpholiniumbelainen by Q'iaternisierung of N-alkyl-2,6-dimethylmorpholinen and / or N-alkyl-2,6 / 2, 5-dimethylmorpholinen by means of Halognentigsäureester and subsequent saponification for Betainen.

Explanation of the essence of the invention

The object of the invention is a process for the preparation of novel N-carboxymethyl-N-alkyl ^ .e-morpholiniumbetainen by quaternization of N-alkyl-2,6-cis- and / or N-alkyl-2,6-trans-dimethylmorpholine and / or N-alkyl-2,6 / 2,5-cis / transdimethylmorpholine by Haiogenessigsäureester and subsequent saponification to betaines.

-3- "99 643

According to the invention, this object is achieved by reacting the novel N-carboxymethyl-N-alkyl ^ .e-morpholinlumbetalne according to the formula

CH ₃

+ CH ₂ - CH ₂ R - N / °

- ClT

CH ₂ CH ₃

COO "where

R = -1-C ₁₃ H ₂₇ , -C _n H _{2n + 1} (with η = 8-18), -ciT7cH ₂ ) ₁₁ or -CH ₂ ^ CH (CH ₃ ) -CH ₂ -C ₆ H ₄ - C (CH ₃ ) ₃

M is prepared by reacting N-alkyl-2,6-cis · and / or N-alkyl-2,6-trans-dimethylmorpholine and / or N-alkyl-2,6 / 2,5-cis / transdimethylmorpholine with haloacetic acid ester reacting in alcoholic solution under reflux, using the reaction conditions mentioned below, the reaction is controlled so that quaternized primarily the 2,6-position isomers, which recovers the substantially reaction-inert 2,5-position isomers from the reaction mixture, as

Reaction conditions: Solvent: alcohol from C to C ₄ ArtdesAlkylierungsmittels: BrCH ₂ COOCH ₂ CH _{3 of} the CICH ₂ COO

-CH ₂ CH ₃ (or else JCH ₂ COOCH ₂ -

-CH3 with exclusive use of

N-alkyl-2,6-cis / trans-dimethylmorpholinone) molar ratio

(Amine: alkylating agent): 1: 1.1 to 1: 1.5

Reaction time: 5-1oh

applies and converts the quaternary ammonium salts thus obtained by alkaline saponification at 15-65 ⁰ C in a strongly alkaline medium to corresponding betaines.

By using the process according to the invention, it is possible to recover the positional isomers 2,6-betaines when 2,6 / 2,5-N-alkyldimethylmorpholines are used, with N-alkyl-2,6-dimethylmorpholines being recovered at the same time. When N-alkyl-2,6-cis / trans-dimethylmorpholines are used, the cis formation predominates. The advantage of the solution according to the invention consists in the purification of positional isomers and in the consequent possibility of exploiting their specific properties, that is to say when 2.6 / 2, S -constitution isomers of N-alkyldimethylmorpholines are used, selective carboxymethylation of the 2,6- Isomeric compounds and the extractive recovery of unreacted 2,5-Isomerverbindungen given.

embodiments Example 1 . Zvyeistufen-betainization

(Carboxymethylation by means of ethyl bromoacetate)

In a 100 ml three-necked flask fitted with thermometer, stirrer and reflux condenser, 14.1 g (= 0.05 mol) of N-I fecyl-

2,6-cis-dimethylmorpholine, 9,19g (= 0,055mol) ethyl bromoacetate and 155ml abs. Submitted methanol and reacted at 64 ⁰ C under reflux for 10 hours. After completion of the quaternization reaction is cooled to room temperature, 4.4 g (0.11 mol) sodium hydroxide solution cookies carefully added and stirred at about 40 ⁰ C in

Solution brought. Then the reaction mixture is heated to 64 ⁰ C and saponified for 3 hours. Of unreacted N-dodecyl-2,6-cis-dimethylmorpholine, 1.08 g was recovered (degree of conversion 92.4%). To

When the target compound was purified several times, 15.2 g of N-carboxyethyl-N-n-dodecyl-2,6-cis-dimethylmorpholinium betaine having the following analytical characteristics were obtained:

% H ₂ O = 5.2 % cr = 2.7 % Sulphated ash = 5.48 % N-titriart = 4.80 % N-corrected = 3.72.

The determined key figures result in purities of 90.4% (calculated on the content of secondary components) or 90.73% determined by potentiometric titration according to J.Gyenes, "Titration in non-aqueomedia" Akademia Kiado Budapest (1967) Taking into account this degree of purity, this results in a yield of 80.2% based on 100% active substance content of betaine.

The obtained reaction product could be unambiguously identified as "N-carboxymethyl-N-n-dodecyl", cis-dimethyldimethylmorpholiniumbetaine by "C-NMR spectroscopy.

Example 2 N carboxymethyl-N-n-dodecyl ^ .e.-trans-dimethylmorpholiniumbetaln In a 100 ml three-necked flask fitted with thermometer, stirrer and reflux condenser, 14.1 g (= 0.05 mol) of N-dodecyl

2,6-trans-dimethylmorpholine, 9.19g (= 0.055mol) of ethyl bromoacetate and 155.5ml abs. Submitted methanol and reacted at 64 ⁰ C under reflux for 10 hours. After completion of Quaternislerungsreaktlon is on

Room temperature cooled reaction mixture 4.4 g (0.11 mol) sodium hydroxide solution carefully added and stirring

at about 4O ⁰ C brought into solution. Then the reaction mixture is heated to 64 ⁰ C and saponified for 3 hours.

Unreacted N-dodecyl-2,6-trans-dimethylmorpholine was recovered to 4.01 g (degree of conversion 71.6%). awake

repeated purification of the target compound, 10.8 g of N-carboxymethyl-N-n-dodecyl-2,6-trans-dimothylmorpholinlumbetain were obtained, with the following analytical characteristics:

% H, 0 = 9,19 % cr = 4.70 % Sulphated ash = 9.55 % N-titration = 5.29 % N-corrected = 3.49.

The determined key figures result in purities of 83% (calculated over contents of minor components) or 85.1%,

determined by potentiometric titration.

Both values are in good approximation. Taking into account these degrees of purity results in a yield of

53.0% based on 100% active ingredient content of betaine.

The reaction product obtained could be identified structurally as "N-carboxymethyl-N-n-dodecyl-2,6" by means of "C-NMR spectroscopy.

trans-dimethylmorpholiniumbetaine be identified beyond doubt.

Example 3 N-carboxymethyl-N-n-cocoalkyl ^ .ecis / trans dimethylmorpholiniumbetain Distillative purification of the product "Falimorph" The used for the synthesis of Falimorph 2,2'-dichloro-di-isopropyl ether contains, such as' H-NMR spectroscopic Studies show about 15% of 2,2'-dichloroisopropyl-n-propyl ether. This results in the Falimorph

characteristic constitutional isomer ratio of about 85% 2,6-isomer and about 15% of 2,5-isomeric compounds. Since <3

Practical product "Falimorph" was only available as undistilled product and was purified by distillation Distillate has the following constitution and configurational isomer composition (capillary GC):

2,6-cis isomer compounds = 44.0%

2,6-trans isomer compounds _v = 41.2% 2,5-cis / trans-l8omer compounds = 14.3%.

The following key data were determined elementally for this distillate:

% N (theor. = 4.82) found: 4.83 / 4.82

% C (theor. = 76.55) found: 76.35 / 76.47

% H (theor. = 13.10) found: 12.87 / 12.96. MG (theor. = 290)

This distillatively purified Falimorph wild carboxymethylated using molar amounts in multiple cycles untei the reaction conditions given in Example 1. The extracted, unreacted tertiary amines have the following composition:

Cycles extracted GC composition (%) Quantity (g). 2,6-cis 2,6-trans 2,5-cis / trans

1 43.7 12.7 39.3 46.2

3 "28.3 0.2 27.5 70.8

10 9.1 - 0.1 98.9

Claims (1)

Process for the preparation of novel N-carboxymethyl-N-alkyl-e-morpholinium betaines, characterized in that carboxymethylbetaine according to the formula + / CH ₂ - CH
RN ⁷ O | ^X CH ₂ - Ch /
CH ₂ CH ₃ COO "
in which R =. -IHS ^ ₃ H ₂₇ . -C _n H _{2n + 1} (with η r 8-18); -CH-JjCH ₂ ) H or
-CH ₂ -CH (CH ₃ ) -CH ₂ -C ₆ H ₄ -C (CH ₃ ) ₃ M is prepared by reacting N-alkyl-2,6-cis- and / or N-alkyl-2,6-trans-dimethylrnorpholine and / or N-alkyl-2,6 / 2,5-cis / transdimethylmorpholine with haloacetic acid ester reacting in alcoholic solution under reflux, using the reaction conditions mentioned below, the reaction is controlled by quaternizing the 2,6-position isomers predominantly, which recovers the substantially reaction-inert 2,5-position isomers from the reaction mixture, as reaction conditions: Solvent: alcohol from Ci to C ₄ ArtdesAlkylierungsmittels: BrCH ₂ COOCH ₇ CH, or CICH ₂ COO -CH ₂ CH ₃ (or else JCH ₂ COOCH ₂ -> - CH ₃ with exclusive use of N-alkyl-2,6-cis / trans-dimethylmorpholines) molar ratio (Amine: alkylating agent): 1: 1.1 to 1: 1.5 Reaction time: 5-1oh applies and converts the quaternary ammonium salts thus obtained by alkaline saponification at 15-65 ⁰ C in a strongly alkaline medium to corresponding betaines.