PL196645B1 - Novel n-oxides di-amidoamines-derivatives of 2-alkylmallonic acid and method of obtaining them - Google Patents

Abstract

1. New di-amidoamine N-oxides of 2-alkylmalonic acid derivatives named 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}-alkane di-N-oxides of the general formula 1, wherein R is a straight or branched hydrocarbon chain CnH2n+1 and n is in the range from 8 to 18. 2. A method for producing new di-amidoamine N-oxides of 2-alkylmalonic acid derivatives named 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}-alkane di-N-oxides of the general formula 1, wherein R is a straight or branched hydrocarbon chain CnH2n+1 and n is in the range from 8 to 18, characterized in that 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkanes of the general formula 2, wherein R and n have the meanings given above, are reacted with hydrogen peroxide in the form of an aqueous solution in a solution of a polar solvent at an elevated temperature, preferably in the range of 50-60°C.

Description

REPUBLIC

POLAND

Patent Office of the Republic of Poland (12) PATENT DESCRIPTION (19) PL (11) 196645 (13) B1 (21) Application number: 351628 (51) Int.Cl.

C07C 291/04 (2006.01) C07C 233/35 (2006.01) (22) Date of filing: 10/01/2002

New N-oxides of diamidoamines derived from 2-alkylmalonic acid and a method for their preparation

(73) Patent holder: Wrocław University of Technology, Wrocław, Poland (43) The application was published on: 14/07/2003 BUP 14/03 (72) Inventor(s): Andrzej Piasecki, Wrocław, Poland Sławomir Karczewski, Opole, Poland (45) The patent was granted on: January 31, 2008, WUP 01/08 (74) Representative: Winohradnik J. Halina, Wrocław University of Technology, Office for Inventions and Patent Protection

⁽⁵⁷⁾ 1. New N-oxides of di-amidoamines derived from 2-alkylmalonic acid called di-N-oxides

1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkanes of the general formula 1, wherein R is a straight or branched hydrocarbon chain CnH2n+1 and n is in the range from 8 to 18.

2. A method for producing new di-amidoamine N-oxides derived from 2-alkylmalonic acid named 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkane di-N-oxides of the general formula 1, wherein R is a straight or branched hydrocarbon chain CnH2n+1 and n is in the range from 8 to 18, characterized in that 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkanes of the general formula 2, wherein R and n have the meanings given above, in a solution of a polar solvent, at an elevated temperature, preferably in the range of 50-60°C, are reacted with hydrogen peroxide in the form of an aqueous solution.

_/ CNH(CH ₂ )3ń(CH3) ₂

R-CH ^X CNH(CH ₂ )3N(CH 3 )2

II f o o pattern 1

PL 196 645 B1

Description of the invention

The subject of the invention are new di-amidoamine N-oxides of 2-alkylmalonic acid derivatives, belonging to the group of tertiary amine N-oxides, which show high activity at interphase boundaries and are suitable for use as active ingredients of household chemicals and cosmetics industry products.

The subject of the invention is also a method for producing new diamidoamine N-oxides derived from 2-alkylmalonic acid.

Known tertiary amine N-oxides are a group of surface-active compounds classified as cationic, amphoteric, or nonionic depending on the pH of their aqueous solutions, due to the strongly polar N > O bond present in their molecules. Amine N-oxides can be prepared by oxidation of the corresponding tertiary amines with strong oxidizing agents. The preferred oxidizing agent is hydrogen peroxide in the form of dilute or concentrated aqueous solutions, which is used in stoichiometric amounts or in excess relative to the tertiary amine. Other known oxidizing agents include peracids: perbenzoic acid from AC Cope, PM Towle, J. Am. Chem. Soc., 71: 3423 (1949); AM Wragg, TS Stevens, DM Ostle, J. Chem. Soc., 1958, 4057, monoperphthalic or m-chloroperbenzoic acid from US patent 3567254, organic hydroperoxides such as cumene, t-butyl, p-methylisopropylbenzene, t-amyl, menthane, etc., oxygen from European patent No. 0092862 B1 (1986) and from US patent No. 5639880, or ozone. The oxidation reaction is carried out in the absence or presence of a catalyst. The reaction is catalyzed by, for example, the addition of a low-molecular-weight organic acid, as described in European Patent EP No. 0866058 A2 (1998), carbon dioxide according to U.S. Patent No. 4,247,480, carbon dioxide and aluminum metal according to U.S. Patent No. 4,942,260, and mixtures of carbonates and polyphosphates described in U.S. Patent No. 3,333,000. The oxidation reaction is also promoted by the addition of chelating agents, e.g., diethylenetriaminepentaacetic acid, as described in U.S. Patent No. 3,283,007. The oxidation reaction is usually carried out in a polar solvent, water, and especially a low-molecular-weight aliphatic alcohol. Surface-active N-oxides are prepared from tertiary amines typically containing one or two long-chain hydrocarbon or perfluorocarbon substituents, an alkylamidoalkyl or alkylaminoalkyl substituent, and one or two short alkyl or hydroxyalkyl substituents as discussed in J.D. Sauer, Amine Oxides, in Cationic Surfactants: Organic Chemistry, J.M. Richmond (Ed.), Marcel Dekker, Inc., Surfactant Science Series, vol. 34, New York, 1990, pp. 275-295. DE Patent No. 664425 discloses a method for preparing dodecyldimethylamine N-oxide having surface activity. US Patent No. 3410903 discloses a method for preparing dimethyltetradecylamine N-oxide in 44% yield by the action of t-butyl hydroperoxide. According to U.S. Patent No. 3,457,312, N,N-bis(2-hydroxyethyl)alkylamines are oxidized to surface-active N-oxides in isopropyl alcohol solution by treatment with a 37.5% by weight aqueous hydrogen peroxide solution. The preparation and application fields of surface-active and biologically active amidoamine N-oxides of the general formulae R-CONH( _CH2 ) _n N(R'R') or R-CONH( _CH2 ) _n N(->O)R'(CH2)nHNC(O)R, where n = 1 - 6, from the corresponding amidoamines in which R is a long-chain hydrocarbon or perfluorocarbon substituent and R' is usually a short _C1 - _C6 alkyl substituent have been widely described in the literature: L.W. Burnette, Miscellaneous Nonionic Surfactants, in Nonionic Surfactants, M.J. Schick (Ed.), Marcel Dekker, Inc., Surfactant Science Series, vol. 1, New York, 1967, pp. 395-418; U.S. Patent Nos.; US 3995996, US 3819539, US 4093711, US 4539161 and US 5866718 and in Japanese patents No. JP 10176187 A2 (1998), JP 10130223 A2 (1998) and JP 11005775 (1999).

There are no known di-amidoamine N-oxides of 2-alkylmalonic acid derivatives called 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkane di-N-oxides.

The invention relates to new di-amidoamine N-oxides derived from 2-alkylmalonic acid, named 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkane di-N-oxides of the general formula 1, wherein R is a straight or branched hydrocarbon chain CnH2n+1 and n is in the range from 8 to 18.

The invention also relates to a method for preparing new di-amidoamine N-oxides derived from 2-alkylmalonic acid of the general formula 1, wherein R is a straight or branched hydrocarbon chain CnH2n+1 and n is in the range from 8 to 18.

The essence of the invention is that 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkanes of the general formula 2, wherein R and n have the meanings given above, in a solution of a polar solvent,

PL 196 645 B1, preferably in the form of isopropyl alcohol, is reacted with hydrogen peroxide, preferably in the form of a 30% by weight aqueous solution, at an elevated temperature, preferably in the range of 50-60°C. After the reaction is completed, the solvent is removed and the residue is purified by known methods. It is preferred that the molar ratio of 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkane to hydrogen peroxide is in the range of 1:2 to 1:6.

The new di-amidoamine N-oxides derived from 2-alkylmalonic acid may find use as active ingredients in household chemicals and cosmetics. The new compounds are suitable as components of detergents, cleansing agents, wetting agents, foaming agents, emulsifying agents, dispersing agents, solubilizing agents, and cosmetic formulations, as well as foam stabilizers or agents increasing the viscosity of aqueous solutions, individually or in mixtures of homologues or in mixtures with other surface-active substances.

The main advantages of the invention consist in the production of compounds with high surface activity and solubility in water regulated by the length of the R substituent from available raw materials, i.e. 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkanes, produced by the reaction of 2-alkylmalonic acid diesters with N,N-dimethyl-1,3-propanediamine, and an aqueous solution of hydrogen peroxide, as well as the simplicity of implementation and high efficiency of the process.

The method according to the invention is illustrated in examples of surface-active 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkane di-N-oxides and in a scheme showing the oxidation reaction of 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}alkane with hydrogen peroxide.

E x a m p l e

To a solution of 6.61 g (0.015 mol) of 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}tridecane in 0.025 dm ³ of isopropyl alcohol, with vigorous stirring, at a temperature of 50-60°C, is added dropwise 0.010 dm ³ of 30% by weight aqueous hydrogen peroxide solution - the molar ratio of di-amidoamine to hydrogen peroxide is about 1:6. Stirring and heating are continued for about 4.5 hours. After cooling to room temperature, the solvents are evaporated under reduced pressure to a constant weight of the residue. The crude product is purified by crystallization from acetone to obtain 5.7 g, i.e. 80.3 mol%, of very water-soluble 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}tridecane di-N-oxide with melting point 66-67°C. Chemical formula C25H52N4O4. C, H, N content calculated 63.52, 11.09, 11.85% by weight, respectively; determined 63.25, 10.85, 11.89% by weight, respectively. Surface tension of 0.1 and 0.01% by weight aqueous solutions at 25°C is 35.3 and 33.8 mN/m, respectively.

Example II

To a solution of 7.03 g (0.015 mol) of 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}pentadecane in 0.025 dm ³ of isopropyl alcohol, with vigorous stirring, at a temperature of 50-60°C, is added dropwise 0.010 dm ³ of 30% by weight aqueous hydrogen peroxide solution - the molar ratio of di-amidoamine to hydrogen peroxide is approximately 1:6. Stirring and heating are continued for approximately 4.5 hours. After cooling to room temperature, the solvents are evaporated under reduced pressure to a constant weight of the residue. The crude product is purified by crystallization from a mixture of acetone/methyl alcohol taken in a volume ratio of 95:5 to give 8.0 g, i.e. 80.0 mol%, of pure, readily water-soluble 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}pentadecane di-N-oxide, having a melting point of 90-92°C and moderate hygroscopicity. Chemical formula C27H56N4O4. C, H, N content calculated 64.76, 11.27, 11.19% by weight, respectively; determined 64.71, 10.87, 10.97% by weight, respectively. The surface tension of 0.1 and 0.01 wt% aqueous solutions at 25°C is 35.6 and 38.7 mN/m, respectively.

Example III

To a solution of 7.45 g (0.015 mol) of 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}heptadecane in 0.025 dm ³ of isopropyl alcohol, with vigorous stirring, at a temperature of 50-60°C, is added dropwise 0.010 dm ³ of 30% by weight aqueous hydrogen peroxide solution - the molar ratio of di-amidoamine to hydrogen peroxide is approximately 1:6. Stirring and heating are continued for approximately 4.5 hours. Proceeding as in Example I, crude, readily water-soluble 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}heptadecane di-N-oxide is obtained. The crude product is purified by crystallization from a mixture of acetone/chloroform/methyl alcohol taken in a volume ratio of 15:2:1, obtaining 6.58 g, i.e. 83.0 mol% of pure di-N-oxide

1,1-bis{[3-(N,N-dimethylamino)propyl]amido}heptadecane, melting point 105-108°C and marked hygroscopicity. Summary formula C29H60N4O4. C, H, N content calculated, correct 4

PL 196 645 B1 n.o., 65.87, 11.44, 10.60%-by weight; determined to be 65.52, 11.39, 10.60%-by weight, respectively. The surface tension of 0.1 and 0.01%-by weight aqueous solutions at 25°C is 42.3 and 42.2 mN/m, respectively.

Example IV

To a solution of 7.87 g (0.015 mol) of 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}nonadecane in 0.025 dm ³ of isopropyl alcohol, with vigorous stirring, at a temperature of 50-60°C, is added dropwise 0.010 dm ³ of 30% by weight aqueous hydrogen peroxide solution - the molar ratio of di-amidoamine to hydrogen peroxide is about 1:6. Stirring and heating are continued for about 4.5 hours. Proceeding as in Example 1, crude, moderately water-soluble 1,1-bis{[3-(N,N-dimethylamino)propyl]amido}nonadecane di-N-oxide is obtained. The crude product is purified by crystallization from acetone/chloroform solvent mixture taken in a volume ratio of 5:1 to give 6.18 g, i.e. 74.0 mol%, of pure 1,1-bis{[3-(N,N-dimethylamino)propyl]amidono}nodecane di-N-oxide. Melting point 115-116°C and distinct hygroscopicity. Chemical formula C31H64N4O4. C, H, N content calculated 66.86, 11.58, 10.06 wt%, respectively; determined 66.72, 11.67, 10.08 wt%, respectively. Surface tension of 0.1 and 0.01 wt% aqueous solutions at 25°C are 41.2 and 41.9 mN/m, respectively.

Claims (4)

Patent claims 1. New N-oxides of di-amidoamines derived from 2-alkylmalonic acid called di-N-oxides 1,1-bis {[3- (N, N-dimethylamino) propyl] amido} alkanes of general formula I, wherein R is a straight or branched chain CnH2n + 1 hydrocarbon and n ranges from 8 to 18. 2. Method for the preparation of new di-amidoamine N-oxides of 2-alkylmalonic acid derivatives called di-N-oxides of 1,1-bis {[3- (N, N-dimethylamino) propyl] amido} alkanes of the general formula 1, wherein R is a straight or branched chain hydrocarbon CnH2n + 1 and ranging from 8 to 18, characterized in that 1,1-bis {[3- (N, N-dimethylamino) propyl] amido} alkanes of general formula 2 in which R and n are as defined above, is reacted with hydrogen peroxide in the form of an aqueous solution in a polar solvent solution at elevated temperatures, preferably in the range of 50-60 ° C. 3. Process according to claim 2, characterized in that the molar ratio of 1,1-bis {[3- (N, N-dimethylamino) propyl] amido} alkane to hydrogen peroxide ranges from 1: 2 to 1: 6. 4. The method according to p. A process according to claim 2 or 3, characterized in that the oxidation reaction is carried out in an isopropyl alcohol solution, using hydrogen peroxide in the form of a 30% by weight aqueous solution, and the obtained product is purified after removal of the solvent.