(19)
(11)EP 1 099 689 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
03.08.2005 Bulletin 2005/31

(21)Application number: 00124246.0

(22)Date of filing:  10.11.2000
(51)Int. Cl.7C07C 233/36, D06M 13/00, C11D 3/50

(54)

Functional alcohol releasing substance

Eine funktionelle Alkohol abgebende Substanz

Composé à libération d'un alcool fonctionnel


(84)Designated Contracting States:
DE FR GB

(30)Priority: 10.11.1999 JP 31939599

(43)Date of publication of application:
16.05.2001 Bulletin 2001/20

(73)Proprietor: Kao Corporation
Chuo-Ku Tokyo (JP)

(72)Inventors:
  • Murayama, Koichi
    Wakayama-shi, Wakayama (JP)
  • Tanaka, Shigeyoshi
    Wakayama-shi, Wakayama (JP)
  • Katayama, Atsushi
    Sumida-ku, Tokyo (JP)
  • Hirayama, Ryoichi
    Sumida-ku, Tokyo (JP)
  • Gema, Takami
    Sumida-ku, Tokyo (JP)

(74)Representative: HOFFMANN - EITLE 
Patent- und Rechtsanwälte Arabellastrasse 4
81925 München
81925 München (DE)


(56)References cited: : 
EP-A- 0 192 145
WO-A-02/02064
DE-A- 1 950 643
US-A- 4 038 294
EP-A- 0 370 338
WO-A-96/38528
DE-A- 4 135 115
US-A- 5 958 870
  
  • DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; AOYANAGI, MUNEO ET AL: "Bleaches and bleach-detergent compositions" retrieved from STN Database accession no. 119:162920 XP002225723 -& JP 05 065498 A (KAO CORP, JAPAN) 19 March 1993 (1993-03-19)
  • DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; YAMADA, HIROYUKI ET AL: "Bleaching agent and bleaching detergent compositions" retrieved from STN Database accession no. 119:98511 XP002225724 -& JP 05 039500 A (KAO CORP, JAPAN) 19 February 1993 (1993-02-19)
  • DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; SAKATA, YASUSHI ET AL: "Liquid softening agents with good storage stability for textiles" retrieved from STN Database accession no. 123:231242 XP002225725 -& JP 07 102479 A (KAO CORP, JAPAN) 18 April 1995 (1995-04-18)
  • DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; WATANABE, ATSUO ET AL: "Dyeing of acrylic fibers" retrieved from STN Database accession no. 85:125705 XP002225726 & JP 49 029911 B (MORIN CHEMICAL INDUSTRIES LTD., JAPAN) 8 August 1974 (1974-08-08)
  • STAEHLER, K. ET AL: "Novel Hydrocarbon and Fluorocarbon Polymerizable Surfactants: Synthesis, Characterization and Mixing Behavior" LANGMUIR (1998), 14(17), 4765-4775 , XP002225722
 
Remarks:
The file contains technical information submitted after the application was filed and not included in this specification
 
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Background of the Invention


1. Field of the Invention



[0001] This invention relates to a functional alcohol releasing substance which gradually releases a functional alcohol and to a composition such as of a detergent or softening agent, which contains the functional alcohol releasing substance.

2. Description of the Related Art



[0002] In a fragrance, a desired aroma is created by blending a large number of aromatic components so-called top note, middle note and base note having different volatility. During the use of the fragrance, components having higher volatility vaporize in priority and, as a result, the aroma of the fragrance changes with the lapse of time, thus posing a problem in that the aroma cannot be maintained constantly for a prolonged period of time. A gel-like aromatic composition in which a fragrance is included in microcapsules and dispersed in a gel base material is known as a means for solving such a problem (JP-A-63-260567; the term "JP-A" as used herein means an "unexamined published Japanese patent application"). Though this method is effective in gel-like preparations, the desired effect cannot be obtained in the case of liquid preparations having low viscosity due to generation of floating and precipitation of microcapsules.

[0003] In addition to the above, a precursor of fragrance raw material in which a sugar and an amino acid are added to a fragrance raw material and a technique for gradually releasing the fragrance raw material by allowing an enzyme to act upon the precursor have been disclosed (JP-A-4-170961). This method, however, has problems in that its effect in the actual use system varies depending on the presence or absence of the hydrolyzing enzyme and, when the precursor and hydrolyzing enzyme are simultaneously blended in a product system, hydrolysis progresses in the product. It also poses the same problems in volatile antibacterial and antifungal agents, so that it is difficult to maintain their effects. In addition, even a nonvolatile substance, e.g. in the case of a water-soluble substance, cannot maintain its effect due to its washing with water.

[0004] On the other hand, WO 96/38528 discloses a betaine ester quaternary ammonium salt derivative which can gradually release a fragrance raw material alcohol. However, this betaine ester quaternary ammonium salt is apt to cause side reactions at the time of synthesis and has a considerably high hydrolyzing rate even in a neutral to weakly acidic aqueous solution, so that it has a disadvantage of poor blending stability.

Summary of the Invention



[0005] An object of the invention is to provide a functional substance releasing compound which can be stably blended independent of the form and use of preparations and can gradually release a functional substance constantly for a prolonged period of time in an actual use system.

[0006] The invention is a substance which is a betaine ester of a functional alcohol, in which it has an amido bond in its molecule and releases the functional alcohol, and a composition containing the same.

[0007] The term betaine ester as used herein means a structure in which a free acid as the hydration product of betaine and an alcohol are esterificated.

Detailed Description of the Invention



[0008] The functional alcohol releasing substance of the invention is a compound represented by the general formula (I) (to be referred to as betaine ester (I) hereinafter):

wherein each of R1, R2 and R3 independently represents hydrogen atom or a straight- or branched-chain alkyl or alkenyl group having from 1 to 30 carbon atoms, Y represents a straight- or branched-chain alkylene group having from 1 to 4 carbon atoms, 3 Z is a group represented by -R5(OA)n- (wherein R5 is a straight- or branched-chain alkylene group having from 1 to 30 carbon atoms, and A is a straight- or branched-chain alkylene group having from 2 to 4 carbon atoms, and n is a number of from 0 to 10), R4 represents a residue in which one OH is removed from a functional alcohol having at least one hydroxyl group in its molecule, namely, R4 represents a saturated or unsaturated aliphatic hydrocarbon group having from 1 to 11 carbon atoms as defined in claim 1, or aromatic hydrocarbon group having from 1 to 11 carbon atoms as defined in claim 1, or an alkadienyl group, alkatrienyl group, aryl group, arylalkyl group or monocyclic, bicyclic or tricyclic terpene hydrocarbon group, each having from 12 to 30 carbon atoms, wherein a part of the hydrogen atoms on the hydrocarbon group of R4 may be substituted by a halogen atom or hydroxyl group, the methylene group in the hydrocarbon group of R4 may be substituted by carbonyl group, amido bond, oxygen atom or sulfur atom, the methyl group may be substituted by formyl group or -CONH2, the carbon-carbon double bond may be substituted by epoxy group and, when isomers are present in R4, it may be a mixture of isomers, and X- represents an anion.

[0009] In this case, the alkyl group, alkenyl group and alkylene group may have a substituent group, and examples of the substituent group include an aryl group such as phenyl group, an alkoxy group such as methoxy group or ethoxy group and an aryloxy group such as phenoxy group.

[0010] The betaine ester (I) can be obtained for example by allowing a compound represented by a general formula (III) (to be referred to as compound (III) hereinafter) to react with a compound represented by a general formula (IV) (to be referred to as compound (IV) hereinafter) in the presence of a solvent:



wherein R1, R2, R3, R4, X, Y and Z are as defined in the foregoing.

[0011] Examples of the solvent to be used include diethyl ether, acetone and chloroform which are selected in response to the solubility of each material. The reaction temperature can be selected within the range of from 15 to 100°C depending on the boiling point of the solvent used and is preferably from 25 to 50°C, more preferably from 40 to 45°C. Regarding the blending ratio of the compound (III) and compound (IV), it is desirable to use excess amount of the compound (IV) in order to increase the reaction ratio and facilitate purification of the product, and it is preferably within the range of from 1:1 to 1:1.2 by molar ratio for practical purpose.

[0012] The compound (III), when the number of carbons of the acyl group represented by R3CO- is 8 or more, can be quantitatively obtained by heat-melting the corresponding fatty acid at 160 to 180°C in an atmosphere of nitrogen and slowly adding a compound represented by a general formula (V) dropwise thereto, thereby effecting dehydration condensation. Also, when the number of carbons of the acyl group represented by R3CO- is less than 8, it can be obtained by allowing an acid anhydride or acid chloride of the corresponding fatty acid to react with the compound of general formula (V).



[0013] In this formula, R1, R2 and Z are as defined in the foregoing.

[0014] The compound (IV) can be obtained by condensing a compound represented by a general formula (VI) with an alcohol represented by a general formula (VII) in the presence of amine as a base.





[0015] In the above formulae, R4, X and Y are as defined in the foregoing, and B represents a halogen atom.

[0016] Among compounds of the betaine ester (I), particularly preferred is a compound represented by a general formula (II) (to be referred to as betaine ester (II) hereinafter).



[0017] In this formula, R1, R2, R3, R4, n and X- are as defined in the foregoing, R6 represents hydrogen atom or methyl group, a is 1 or 2.

[0018] In the betaine ester (II), each of R1 and R2 is preferably a group having from 1 to 4 carbon atoms, more preferably methyl group. R3 is preferably a group having from 1 to 22 carbon atoms. Preferably, n is from 0 to 3. Examples of the anion represented by X- include halogen ions, sulfate ion, hydrogensulfate ion and perchlorate ion, of which chlorine ion is preferred.

[0019] A saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon group having from 1 to 11 carbon atoms representing R4 is:

[0020] A residue in which one hydroxyl group is removed from an aliphatic alcohol such as leaf alcohol (cis-3-hexenol), 3-octenol, 2,4-dimethyl-3-cyclohexene-1-methanol, 4-isopropylcyclohexanol, 4-isopropylcyclohexylmethanol, 1-(4-isopropylcyclohexyl)ethanol, p-t-butylcyclohexanol, o-t-butylcyclohexanol, 9-decenol, linalool, geraniol, nerol, citronellol, rhodinol, dimethyloctanol, hydroxycitronellol, tetrahydrolinalool, lavandulol, mugol, myrcenol, terpineol, L-menthol, borneol, isopulegol, tetrahydromugol, nopol or glycerol.

[0021] A substituted or unsubstituted aromatic hydrocarbon group having from 1 to 11 carbon atoms representing R4 is:

[0022] A residue in which one hydroxyl group is removed from benzyl alcohol, β-phenylethyl alcohol, γ-phenylpropyl alcohol, cinnamic alcohol, anisic alcohol, dimethylbenzylcarbinol, methylphenylcarbinol, dimethylphenylcarbinol, phenoxyethyl alcohol, styrallyl alcohol, dimethylphenylethylcarbinol, thymol, carvacrol, eugenol, isoeugenol, ethyl vanillin, metha-chloroxylenol, 2,4-dichlorophenol, 2,4-dichlorobenzyl alcohol, hinokithiol or 3-methyl-4-isopropylphenol.

[0023] The alkadienyl group or alkatrienyl group having from 12 to 30 carbon atoms representing R4 can be exemplified by:

[0024] A residue in which one hydroxyl group is removed from a compound such as farnesol or nerolidol.

[0025] The aryl group or arylalkyl group having from 12 to 30 carbon atoms representing R4 can be exemplified by:

[0026] A residue in which one hydroxyl group is removed from a compound such as 2,2-dimethyl-3-(3-methylphenyl)propanol, 3-methyl-5-phenylpentanol, phenylethylmethylethylcarbinol, trichlosan, capsaicin or tocopherol.

[0027] The monocyclic, bicyclic or tricyclic terpene hydrocarbon group having from 12 to 30 carbon atoms representing R4 can be exemplified by:

[0028] A residue in which one hydroxyl group is removed from a compound such as ambrinol, 1-(2-t-butylcyclohexyloxy)-2-butanol, pentamethylcyclohexylpropanol, 1-(2,2,6-trimethylcyclohexyl)-3-hexanol, santalol, cedrol, vetiverol or patchouli alcohol.

[0029] Since the functional alcohol releasing substance of the invention can release functional alcohols such as perfumes and antibacterial and antifungal agents gradually for a prolonged period of time, it can be used alone or in combination with other components as ingredients of, e.g., soaps, shampoos, detergents, cosmetics, spray products, deodorants, aromatics, bathing goods, coloring agents, hair colors, antibacterial agents, antifungal agents, vapor proofing agents, bedclothes, towels, clothes, tissues, sands for pet toilet use, chewing gums, cosmetics for pack use, clay compositions for handicraft use, absorbable articles, cosmetics for massage use, paints, agricultural chemicals, medicaments and inks.

[0030] The composition of the invention contains the functional alcohol releasing substance, and the amount of the functional alcohol releasing substance to be contained in the composition of the invention is preferably from 0.01 to 90% by weight, more preferably from 0.5 to 50% by weight, based on the composition, though it varies depending, e.g., on the kind of composition and the kind of functional alcohol of interest.

[0031] The composition of the invention is particularly useful as, e.g., a softening agent composition containing a textile conditioner or softening agent component, a detergent composition for clothing use containing a detergent component or a detergent composition for hard surface use.

[0032] Examples of the textile conditioner or softening agent component include quaternary ammonium salts, amines and neutral salts of amines, particularly an acid salt of a quaternary ammonium compound or tertiary amine compound having in its molecule one or more ester groups and/or amido groups and two or more alkyl groups or alkenyl groups having from 11 to 20 carbon atoms, an acid salt of a quaternary ammonium compound or tertiary amine compound having in its molecule one alkyl group or alkenyl group having from 11 to 20 carbon atoms and an amphoteric surface active agent having in its molecule one alkyl group or alkenyl group having from 6 to 20 carbon atoms. Also, for the purpose of further improving the softening performance, an alkylene oxide addition product of a higher alcohol or amine, a higher fatty acid or a salt thereof may be added as occasion demands. The amount of the textile conditioner or softening agent component to be used in the composition of the invention is preferably from 1 to 50% by weight, more preferably from 5 to 20% by weight.

[0033] Examples of the detergent component to be used in the composition of the invention include anionic surface active agents such as a polyoxyalkylene alkyl ether sulfate, an alkyl sulfate, an alkylbenzene sulfonate, an α-olefin sulfonate, an alkane sulfonate, a fatty acid salt, an α-sulfofatty acid ester salt, a polyoxyalkylene alkyl ether carboxylate and a polyoxyalkylene alkyl ether phosphate, nonionic surface active agents such as a polyoxyalkylene alkyl ether, an alkyl glucoside, mono- and dialkanolamides of a fatty acid and an active agent of Pluronic system, cationic surface active agents such as a quaternary ammonium salt and amphoteric surface active agents such as carbobetaine and sulfobetaine. Amount of the detergent component in the composition of the invention is preferably from 1 to 80% by weight, more preferably from 20 to 40% by weight, as a detergent composition for clothing use. As a detergent composition for hard surface use, it is preferably from 0.5 to 60% by weight, more preferably from 1 to 50% by weight, based on the composition.

[0034] As occasion demands, other additive agents used in general softening agents and detergents can be optionally added to the composition of the invention within such a range that they do not spoil effects of the invention.

[0035] Examples of the other additive agents which can be added include storage stabilizing agents such as lower alcohols including ethanol and isopropanol, a glycol, a polyol and alkylene oxide addition products thereof; chelating agents such as ethylenediamine tetraacetate, diethylenetriamine pentaacetate, sodium acid pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, zeolite, ethylhydroxy diphosphonate, citric acid, dipicolinic acid, picolinic acid and 8-hydroxyquinoline; solubilizing agents such as sodium salts and potassium salts of toluenesulfonic acid and xylenesulfonic acid and urea; alkali agents such as sodium carbonate and an amorphous alkali metal silicate; viscosity adjusting agents such as a clay mineral and a water-soluble polymer; moisture keeping agents such as glycerol and sorbitol; feel improving agents such as cationic cellulose; extenders such as sodium sulfate; and a pH adjusting agent, a hydrotropic agent, an antifoaming agent, an antioxidant, an enzyme, a perfume, an antibacterial agent, a pigment and an antiseptic/antifungal agent.

Examples



[0036] Unless otherwise noted, the term "part" and "%" in the examples are weight basis.

Synthesis Example 1: Synthesis of N-octadecanoyl-N',N'-dimethyl-1,3-diaminopropane



[0037] A 300 g (1.05 mol) portion of octadecanoic acid was put into a flask and melted by stirring at 180°C in an atmosphere of nitrogen. To this was added dropwise 113.1 g (1.11 mol) of N,N-dimethyl-1,3-diaminopropane spending 3 hours, thereby effecting the reaction while evaporating the generated water. After completion of the dropwise addition, this was further stirred at 180°C for 4 hours in an atmosphere of nitrogen. Thereafter, the unreacted material amine remained in the reaction mixture was evaporated under a reduced pressure to obtain the title compound as a light brown waxy solid (melting point 64 - 67°C).

Synthesis examples 2 to 4



[0038] Hexadecanoic acid, dodecanoic acid or octanoic acid was used instead of octadecanoic acid, and these fatty acids were allowed to react with N,N-dimethyl-1,3-diaminopropane in the same manner as described in Synthesis Example 1 to obtain N-hexadecanoyl-N',N'-dimethyl-1,3-diaminopropane, N-decanoyl-N',N'-dimethyl-1,3-diaminopropane and N-octanoyl-N',N'-dimethyl-1,3-diaminopropane, respectively.

Synthesis Example 5: Synthesis of N-acetyl-N',N'-dimethyl-1,3-diaminopropane



[0039] A 51.1 g (0.50 mol) portion of N,N-dimethyl-1,3-diaminopropane was put into a flask and cooled to 5°C while stirring in an atmosphere of nitrogen. Under ice-cooling, to this was added dropwise 51.1 g (0.50 mol) of acetic anhydride spending 1 hour. After completion of the dropwise addition, this was further stirred at 25°C for 3 hours. Thereafter, the reaction mixture was again ice-cooled and 41.6 g (0.5 mol) of 48% sodium hydroxide aqueous solution was added dropwise thereto spending 15 minutes and then, after completion of the dropwise addition, 350 ml of acetone was added to the reaction mixture and allowed to stand at room temperature for 8 hours. Sodium acetate precipitated in the acetone solution was removed by filtration, acetone was evaporated under a reduced pressure and then 71 g of the remaining yellow oil was distilled under a reduced pressure to obtain the title compound as a transparent oil. Yield 62.4 g (0.433 mol; yield 86.8%, boiling point 116 - 118°C/0.64 kPa).

Synthesis Example 6: Synthesis of 3-methyl-5-phenylpentyl chloroacetate



[0040] A 127.05 g (1.125 mol) of chloroacetyl chloride and 200 ml of dichloromethane were put into a flask and, while stirring under ice-cooling, a mixture consisting of 199.6 g (1.12 mol) of 3-methyl-5-phenylpentanol and 88.59 g (1.12 mol) of pyridine was added dropwise thereto spending 2 hours (reaction temperature 5 to 15°C). After completion of the dropwise addition, this was further stirred at room temperature for 3 hours, and white crystals of the thus precipitated pyridine hydrochloride were removed by filtration. The reaction mixture was washed with water (3 x 300 ml),the organic phase was dehydrated with anhydrous magnesium sulfate and then the solvent was evaporated under a reduced pressure. By distilling the remained yellow oil under a reduced pressure, the title compound was obtained as a light yellow transparent oil. Yield 242.25 g (0.849 mol; yield 84.9%, boiling point 148 - 151°C/0.2 kPa).

Synthesis Example 7: Synthesis of L-menthyl chloroacetate



[0041] By the same method of Synthesis Example 6, the title compound was obtained as a light yellow transparent oil from chloroacetyl chloride and L-menthol. Boiling point 102 - 106°C/0.027 kPa.

Synthesis Example 8: Synthesis ot geranyl chloroacetate



[0042] By the same method of Synthesis Example 6, the title compound was obtained as a light yellow transparent oil from chloroacetyl chloride and geraniol. Boiling point 113 - 115°C/0.13 kPa.

Synthesis Example 9: Synthesis of cis-3-hexenyl chloroacetate



[0043] By the same method of Synthesis Example 6, the title compound was obtained as a transparent oil from chloroacetyl chloride and cis-3-hexenol. Boiling point 89 - 92°C/0.13 kPa.

Synthesis Example 10: Synthesis of 2-phenylethyl chloroacetate



[0044] By the same method of Synthesis Example 6, the title compound was obtained as a transparent oil from chloroacetyl chloride and 2-phenylethyl alcohol. Boiling point 121 - 123°C/0.69 kPa.

Synthesis Example 11: Synthesis of 3-methyl-4-isopropylphenyl chloroacetate



[0045] By the same method of Synthesis Example 6, chloroacetyl chloride was allowed to react with 3-methyl-4-isopropylphenol, the reaction mixture was washed with water and then the solvent was evaporated under a reduced pressure to obtain the title compound as a transparent oil. The title compound was used in the subsequent reaction without distillation.

Inventive Example 1: Synthesis of N,N-dimethyl-N-geranyloxycarbonylmethyl-N-(3-(octadecanoylamino)propyl)ammonium chloride



[0046] A 36.86 g (0.100 mol) portion of N-octadecanoyl-N',N'-dimethyl-1,3-diaminopropane and 100 ml of chloroform were put into a flask, and 23.30 g (0.101 mol) of geranyl chloroacetate was added thereto at 25°C spending 5 minutes. The reaction mixture was stirred at 25°C for 36 hours and then, after confirming by 1H-NMR that chloroacetate was mostly disappeared, the solvent was evaporated under a reduced pressure. The thus obtained viscous oil was dissolved in 200 ml of acetone and cooled to 5 to 10°C to effect precipitation of a white precipitate. The supernatant solvent was discarded, and the precipitated was collected and dried under a reduced pressure to obtain the title compound (to be referred to as betaine ester (1) hereinafter) as a slightly brownish white solid. Yield 49.1 g (0.0819 mol; yield 81.9%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.88 (3 H, t, J = 6.4 Hz, -(CH2)16-CH3), 1.26 (28 H, br s, -(CH2)14-CH3), 1.5 - 1.7 (2 H, m, -CH2-CH2-CONH-), 1.61 (3 H, s, CH3-C=CH-CH2-O), 1. 69 (3 H, s, (CH3)CH3C=C), 1.73 (3 H, s, (CH3)CH3C=C), 1.8 - 2.3 (6 H, br s, N-C-CH2-C-N, CH3-C-CH2-CH2-C=C(CH3)2), 2.29 (2 H, t, J = 7.6 Hz, -CH2-CH2-CONH-), 3.37 (2 H, dt, J = 5, J = 7.6 Hz, -CONH-CH2-C-), 3.49 (6 H, s, CH3-N+-CH3), 4.1 (2 H, t, J = 7.8 Hz, -CH2-CH2-N+-), 4.66 (2 H, s, N+-CH2-C=O), 4.72 (2 H, d, J = 7. 3 Hz, O-CH2-CH=C-), 5.05 (1 H, m, -CH-C=C(CH3)2), 5 . 31 (1 H, t, J = 7.3 Hz, O-CH2-CH=C-), 8.01 (1 H, t, J = 5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3292 (v NH, amide), 3020 (ν CH, =CH-), 2954 (ν asCH3), 2924 (ν asCH2), 2852 (ν sCH2), 1747 (ν C=O, ester), 1645 (ν C=O, amide), 1552 (δ NH, ν C-N), 1464 (δ asCH3; δ CH2), 1377 (δ sCH3), 1198 (ν C-O, ester), 1124, 1020, 984, 719 (CH2)n).

Inventive Example 2: Synthesis of N,N-dimethyl-N-geranyloxycarbonylmethyl-N-(3-(hexadecanoylamino)propyl)ammonium chloride



[0047] The reaction of Inventive Example 1 was repeated, except that 34.59 g (0.10 mol) of N-hexadecanoyl-N',N'-dimethyl-1,3-diaminopropane was used instead of N-octadecanoyl-N',N'-dimethyl-1,3-diaminopropane, and the solvent was evaporated under a reduced pressure. The thus obtained viscous oil was dissolved in 200 ml of acetonitrile instead of acetone and then the title compound (to be referred to as betaine ester (2) hereinafter) was obtained as a yellow viscous solid in the same manner as described in Inventive Example 1. Yield 50.11 g (0.0877 mol; yield 87.7%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.88 (3 H, t, J = 6.4 Hz, -(CH2)14-CH3), 1.26 (24 H, br s, -(CH2)12-CH3), 1.5 - 1.7 (2 H, m, -CH2-CH2-CONH-), 1.61 (3 H, s, CH3-C=CH-CH2-O), 1.69 (3 H, s, (CH3)CH3C=C), 1.73 (3 H, s, (CH3)CH3C=C), 1.8 - 2.3 (6 H, br s, N-C-CH2-C-N, CH3-C-CH2-CH2-C=C(CH3)2), 2.29 (2 H, t, J = 7. 6 Hz, -CH2-CH2-CONH-), 3.37 (2 H, dt, J = 5, J = 7.6 Hz, -CONH-CH2-C-), 3.49 (6 H, s, CH3-N+-CH3), 4.1 (2 H, t, J = 7.8 Hz, -CH2-CH2-N+-), 4.66 (2 H, s, N+-CH2-C=O), 4.72 (2 H, d, J = 7.3 Hz, O-CH2-CH=C-), 5.05 (1 H, m, -CH-C=C(CH3)2), 5.31 (1 H, t, J = 7.3 Hz, O-CH2-CH=C-),
8.01 (1 H, t, J = 5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3320 (ν NH, amide), 3020 (ν CH, =CH-), 2954 (ν asCH3), 2924 (ν asCH2), 2852 (ν sCH2), 1747 (ν C=O, ester), 1649 (ν C=O, amide), 1547 (δ NH, ν C-N), 1466 (δ asCH3; δ CH2), 1379 (δ sCH3), 1198 (ν C-O, ester), 721 ((CH2)n).

Inventive Example 3: Synthesis of N,N-dimethyl-N-geranyloxycarbonylmethyl-N-(3-(dodecanoylamino)propyl)ammonium chloride



[0048] A 22.76 g (0.080 mol) portion of N-dodecanoyl-N',N'-dimethyl-1,3-diaminopropane and 120 ml of diethyl ether were put into a flask, and 18.46 g (0.080 mol) of geranyl chloroacetate was added thereto at 25°C spending 5 minutes. The reaction mixture was stirred at 25°C for 24 hours, and disappearance of the most part of chloroacetate was confirmed by 1H-NMR. Next, the reaction mixture was slowly added dropwise to 600 ml of hexane which was ice-cooled and vigorously stirred, spending 10 minutes, to effect precipitation of the product as a white solid. Thereafter, in the same manner as described in Inventive Example 1, the title compound (to be referred to as betaine ester (3) hereinafter) was obtained as a light yellow viscous oil. Yield 38.50 g (0.0747 mol; yield 93.4%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.88 (3 H, t, J = 6.4 Hz, -(CH2)10-CH3), 1.26 (16 H, br s, -(CH2)3-CH3), 1.5 - 1.7 (2 H, m, -CH2-CH2-CONH-), 1.61 (3 H, s, CH3-C=CH-CH2-O), 1.69 (3 H, s, (CH3)CH3C=C), 1.73 (3 H, s, (CH3)CH3C=C), 1.8 - 2.3 (6 H, br s, N-C-CH2-C-N, CH3-C-CH2-CH2-C=C(CH3)2), 2.29 (2 H, t, J = 7.6 Hz, -CH2-CH2-CONH-), 3.37 (2 H, dt, J = 5, J = 7.6 Hz, -CONH-CH2-C-), 3.49 (6 H, s, CH3-N+-CH3), 4.1 (2 H, t, J = 7.8 Hz, -CH2-CH2-N+-), 4.66 (2 H, s, N+-CH2-C=O), 4.72 (2 H, d, J = 7.3 Hz, O-CH2-CH=C-), 5.05 (1 H, m, -CH-C=C(CH3)2), 5.31 (1 H, t, J = 7.3 Hz, O-CH2-CH=C-), 8.01 (1 H, t, J = 5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3244 (ν NH, amide), 3051, 3022 (ν CH, =CH-), 2954 (ν asCH3), 2924 (ν asCH2), 2854 (ν sCH2), 1747 (ν C=O, ester), 1651 (ν C=O, amide), 1549 (δ NH, ν C-N), 1485, 1466 (δ asCH3; δ CH2), 1377 (δ SCH3),1225, 1198 (ν C-O, ester), 1155, 1124, 1020, 987, 935, 899, 721 ((CH2)n).

Inventive Example 4: Synthesis of N,N-dimethyl-N-geranyloxycarbonylmethyl-N-(3-(octanoylamino)propyl)ammonium chloride



[0049] A 22.84 g (0.100 mol) portion of N-octanoyl-N',N'-dimethyl-1,3-diaminopropane and 250 ml of diethyl ether were put into a flask, and 24.23 g (0.105 mol) of geranyl chloroacetate was added thereto at 0 to 5°C spending 10 minutes. The reaction mixture was stirred at 5 to 25°C for 24 hours, and disappearance of the most part of chloroacetate was confirmed by 1H-NMR. Next, the reaction mixture was slowly added dropwise to 650 ml of pentane which was ice-cooled and vigorously stirred, spending 10 minutes, to effect precipitation of the product as a white solid. Thereafter, in the same manner as described in Inventive Example 1, the title compound (to be referred to as betaine ester (4) hereinafter) was obtained as a light yellow viscous oil. Yield 38.2 g (0.0832 mol; yield 83.2%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.88 (3 H, t, J = 6.4 Hz, -(CH2)6-CH3), 1.26 (8 H, br s, -(CH2)4-CH3), 1.5 - 1.7 (2 H, m, -CH2-CH2-CONH-), 1. 61 (3 H, s, CH3-C=CH-CH2-O), 1.69 (3 H, s, (CH3)CH3C=C), 1.73 (3 H, s, (CH3)CH3C=C), 1.8 - 2.3 (6 H, br s, N-C-CH2-C-N, CH3-C-CH2-CH2-C=C(CH3)2), 2.29 (2 H, t, J = 7.6 Hz, -CH2-CH2-CONH-), 3.37 (2 H, dt, J = 5, J = 7.6 Hz, -CONH-CH2-C-), 3.49 (6 H, s, CH3-N+-CH3), 4.1 (2 H, t, J = 7.8 Hz, -CH2-CH2-N+-), 4.66 (2 H, s, N+-CH2-C=O), 4.72 (2 H, d, J = 7.3 Hz, O-CH2-CH=C-), 5.05 (1 H, m, -CH-C=C(CH3)2), 5.31 (1 H, t, J = 7.3 Hz, O-CH2-CH=C-), 8.01 (1 H, t, J = 5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3244 (ν NH, amide), 3051, 3022 (ν CH, =CH-), 2954 (ν asCH3), 2924 (ν asCH2), 2854 (ν sCH2), 1745 (ν C=O, ester), 1655 (v C=O, amide), 1549 (δ NH, ν C-N), 1485, 1466 (δ asCH3; δ CH2), 1377 (δ sCH3), 1225, 1198 (ν C-O, ester), 1155, 1124, 1020, 987, 935, 899, 721 ((CH2)n).

Inventive Example 5: Synthesis of N,N-dimethyl-N-geranyloxycarbonylmethyl-N-(3-(acetylamino)propyl)ammonium chloride



[0050] A 7.21 g (0.05 mol) portion of N-acetyl-N',N'-dimethyl-1,3-diaminopropane and 150 ml of diethyl ether were put into a flask, and 11.65 g (0.0505 mol) of geranyl chloroacetate was added thereto at 0 to 5°C spending 10 minutes. The reaction mixture was stirred for 2 hours while cooling on ice to observe precipitation of the product. This was further stirred at 25°C for 12 hours, and disappearance of the most part of chloroacetate was confirmed by 1H-NMR. Next, the solvent was evaporated under a reduced pressure, and the reaction mixture as the residual viscous oil was dissolved in 20 ml of dichloromethane and slowly added dropwise to 400 ml of diethyl ether which was ice-cooled and vigorously stirred, spending 5 minutes, to effect precipitation of the product as a white solid. Thereafter, in the same manner as described in Inventive Example 1, the title compound (to be referred to as betaine ester (5) hereinafter) was obtained as a light yellow viscous oil. Yield 15.6 g (41.6 mmol; yield 83.2%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   1.61 (3 H, s, CH3-C=CH-CH2-O), 1.69 (3 H, s, (CH3)CH3C=C), 1.73 (3 H, s, (CH3)CH3C=C), 2.05 (3 H, s, CH3-CONH-), 1 9 - 2.2 (6 H, N-C-CH2-C-N, (CH3)C-CH2-CH2-C=C), 3.36 (2 H, dt, J = 5.5, J = 7.6 Hz, -CONH-CH2-C-), 3.51 (6 H, s, CH3-N+-CH3), 4.08 (2 H, t, J = 7.6 Hz, -CH2-CH2-N+-), 4.64 (2 H, s, N+-CH2-C=O), 4.73 (2 H, d, J = 7.3 Hz, O-CH2-CH=C-), 5.05 (1 H, m, -CH-C=C(CH3)2), 5.31 (1 H, t, J = 7.3 Hz, O-CH2-CH=C-), 8.25 (1 H, t, J = 5.5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3242, 3057, 3020 (ν CH, =CH-), 2968 (ν asCH3), 2929 (ν asCH2), 2858 (ν sCH2), 1743 (ν C=O, ester), 1660 (ν C=O, amide), 1552 (δ NH, ν C-N), 1485, 1444, 1408, 1375 (δ sCH3; CH3-CONH-), 1279, 1198 (ν C-O, ester), 1161, 1111, 1018, 933, 894, 727 (-CH2-).

Inventive Example 6: Synthesis of N,N-dimethyl-N-(3-methyl-5-phenylpentyl)oxycarbonylmethyl-N-(3-(octadecanoylamino)propyl)ammonium chloride



[0051] The title compound (to be referred to as betaine ester (6) hereinafter) was obtained as a white solid in the same manner as described in Inventive Example 1, except that 25.73 g (0.101 mol) of 3-methyl-5-phenylpentyl chloroacetate was used instead of geranyl chloroacetate. Yield 50.8 g (0.0815 mol; yield 81.5%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.88 (3 H, t, J = 6.4 Hz, -(CH2)6-CH3), 0.98 (3 H, d, J = 6 Hz, -CH-CH3), 1.25 (28 H, br s, -(CH2)14-CH3), 1.4 - 1.85 (7 H, -CH2-CH(CH3)CH2-, -CH2-CH2-CONH-), 2.06 (2 H, m, N-C-CH2-C-N), 2.28 (2 H, t, J = 7.6 Hz, -CH2-CH2-CONH-), 2.65 (2 H, dddd, J = 7. 6, 7.6, 5.5, 5.5 Hz, Ph-CH2-CH2-), 3.36 (2 H, dt, J = 5.5, J = 7.6 Hz, -CONH-CH2-C-), 3.47 (6 H, s, CH3-N+-CH3), 4.05 (2 H, t, J = 7.6 Hz, -CH2-CH2-N+-), 4.24 (2 H, t, J = 6.5 Hz, -CH2-O-C=O), 4.59 (2 H, s, N+-CH2-C=O), 7.0 - 7.35 (5 H, m, phenyl), 7.95 (1 H, t, J = 5.5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3292 (ν NH), 3026 (ν CH, phenyl), 2954 (ν asCH3), 2922 (ν asCH2), 2850 (ν sCH2), 1745 (ν C=O, ester), 1639 (ν C=O, amide), 1552 (δ NH, ν C-N), 1467 (δ asCH3; δ CH2, phenyl), 1379 (δ sCH3), 1203 (ν C-O, ester), 1026 (δ CH, phenyl), 744 (phenyl), 721 ((CH2)n), 698 (phenyl).

Inventive Example 7: Synthesis of N,N-dimethyl-N-(3-methyl-5-phenylpentyl)oxycarbonylmethyl-N-(3-(dodecanoylamino)propyl)ammonium chloride



[0052] The title compound (to be referred to as betaine ester (7) hereinafter) was obtained as a yellow viscous oil in the same manner as described in Inventive Example 3, except that 28.45 g (0.1 mol) of N-dodecanoyl-N',N'-dimethyl-1,3-diaminopropane was used, and 25.73 g (0.101 mol) of 3-methyl-5-phenylpentyl chloroacetate was used instead of geranyl chloroacetate. Yield 45.83 g (0.085 mol; yield 85%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.88 (3 H, t, J = 6.4 Hz, -(CH2)16-CH3), 0.98 (3 H, d, J = 6 Hz, -CH-CH3), 1.25 (16 H, br s, -(CH2)8-CH3), 1.4 - 1.85 (7 H, -CH2-CH(CH3)-CH2-, -CH2-CH2-CONH-), 2.06 (2 H, m, N-C-CH2-C-N), 2.28 (2 H, t, J = 7.6 Hz, -CH2-CH2-CONH-), 2.65 (2 H, dddd, J = 7.6, 7.6, 5.5, 5.5 Hz, Ph-CH2-CH2-), 3.36 (2 H, dt, J = 5.5, J = 7.6 Hz, -CONH-CH2-C-), 3.47 (6 H, s, CH3-N+-CH3), 4.05 (2 H, t, J = 7.6 Hz, -CH2-CH2-N+-), 4.24 (2 H, t, J = 6.5 Hz, -CH2-O-C=O), 4.59 (2 H, s, N+-CH2-C=O), 7.0 - 7.35 (5 H, m, phenyl), 7.95 (1 H, t, J = 5.5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3026 (ν CH, phenyl), 2954 (ν asCH3), 2924 (ν asCH2), 2854 (ν sCH2), 1743 (ν C=O, ester), 1651 (ν C=O, amide), 1547 (δ NH, ν C-N), 1493 (phenyl), 1466 (δ asCH3; δ CH2), 1379 (δ sCH3), 1203 (ν C-O, ester), 1026 (δ CH, phenyl), 744 (phenyl), 721 ((CH2)n), 698 (phenyl).

Inventive Example 8: Synthesis of N,N-dimethyl-N-cis-3-hexenyloxycarbonylmethyl-N-(3-(acetylamino)propyl)ammonium chloride



[0053] The title compound (to be referred to as betaine ester (8) hereinafter) was obtained as a transparent glassy substance in the same manner as described in Inventive Example 5, except that 8.65 g (0.060 mol) of N-acetyl-N',N'-dimethyl-1,3-diaminopropane was used, and 11.13 g (0.063 mol) of cis-3-hexenyl chloroacetate was used instead of geranyl chloroacetate. Yield 15.4 g (0.048 mol; yield 80%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.98 (3 H, t, J = 7.5 Hz, -CH2-CH3), 1.8 - 2.2 (4 H, CH3-CH2-C=C-, N-CH2-C-N), 2.04 (3 H, s, CH3-CONH-), 2.42 (2 H, q, J = 7 Hz, -O-CH2-CH2-CH=C), 3.36 (2 H, dd, J = 5.5, 7.2 Hz, -CONH-CH2-C-), 3.52 (6 H, s, CH3-N+-CH3), 4.05 (2 H, t, J = 7.2 Hz, -CH2-CH2-N+-), 4.20 (2 H, t, J = 7 Hz, -O-CH2-CH2), 4.66 (2 H, s, N+-CH2-C=O), 5.36 (1 H, dt, J = 10.8, 7.2 Hz, -C=CH-), 5.55 (1 H, dt, J = 10.8, 7.2 Hz, -CH=C-), 8.25 (1 H, t, J = 5.5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3080 (ν CH, =CH-), 3012 (ν CH, =CH-), 2966 (ν asCH3), 2875 (ν sCH2), 1747 (ν C=O, ester), 1655 (ν C=O, amide), 1556 (δ NH, ν C-N), 1483, 1462 (δ asCH3; δ CH2), 1408 (δ CH2), 1371 (δ sCH3), 1300, 1201 (ν C-O, ester), 1020, 899.

Inventive Example 9: Synthesis of N,N-dimethyl-N-L-menthyloxycarbonylmethyl-N-(3-(acetylamino)propyl)ammonium chloride



[0054] A 7.21 g (0.05 mol) portion of N-acetyl-N',N'-dimethyl-1,3-diaminopropane and 25 ml of diethyl ether were put into a flask, and 11.64 g (0.05 mol) of L-menthyl chloroacetate was added thereto at 0 to 5°C spending 5 minutes. The reaction mixture was stirred at 25°C for 48 hours, and disappearance of the most part of chloroacetate was confirmed by 1H-NMR. After evaporation of the solvent under a reduced pressure, the crude product was dissolved in 30 ml of dichloromethane and then the reaction mixture was slowly added dropwise to 480 ml of hexane which was ice-cooled and vigorously stirred, spending 10 minutes, to effect precipitation of the product as an oily substance. When the supernatant solvent was discarded and 150 ml of diethyl ether was added to the oily substance, the oily substance was solidified. The supernatant organic solvent was discarded and then the white solid was collected and dried under a reduced pressure to obtain the title compound (to be referred to as betaine ester (9) hereinafter) as a white powder. Yield 14.75 g (0.039 mol; yield 78.2%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.88 (3 H, d, J = 6.9 Hz, >CH2-CH3), 0.90 (3 H, d, J = 5.5 Hz, (CH3)2-CH-), 0.93 (3 H, d, J = 5.5 Hz, (CH3)2-CH-), 1.05 (2 H, quint, J = 11 Hz, >CH2), 1.43 (2 H, t, J = 11 Hz, >CH2), 1.69 (2 H, d, J = 11 Hz, >CH2),1 87 (1 H, ddddd, J = 7, 7, 7, 7, 3 Hz, >CH), 1.9 - 2.2 (3 H, >CH, N-C-CH2-C-N), 2.06 (3 H, s, CH3-CONH-), 3.36 (2 H, dt, J = 5.5, 7.2 Hz, -CONH-CH2-C-), 3.51 (3 H, s, CH3-N+-CH3), 3.53 (3 H, s, CH3-N+-CH3), 4.13 (2 H, t, J = 7 Hz, -CH2-CH2-N+-), 4.43 (1 H, d, N+-CH2-C=O, J = 16 Hz), 4.62 (1 H, d, N+-CH2-C=O, J = 16 Hz), 4.79 (1 H, td, J = 4.4, 10.9 Hz, >CH-O-C=O), 8.35 (1 H, t, J = 5.5 Hz, -CONH-).

Inventive Example 10: Synthesis of N,N-dimethyl-N-L-menthyloxycarbonylmethyl-N-(3-(dodecanoylamino)propyl)ammonium chloride



[0055] A 28.45 g (0.100 mol) portion of N-dodecanoyl-N',N'-dimethyl-1,3-diaminopropane and 120 ml of diethyl ether were put into a flask, and 23.27 g (0.100 mol) of L-menthyl chloroacetate was added thereto at 0 to 5°C spending 5 minutes. The reaction mixture was stirred at 25°C for 48 hours, and disappearance of the most part of chloroacetate was confirmed by 1H-NMR. After evaporation of the solvent under a reduced pressure, the crude product was dissolved in 30 ml of dichloromethane, and the reaction mixture was slowly added dropwise to 480 ml of pentane which was ice-cooled and vigorously stirred, spending 10 minutes, to effect precipitation of the product as an oily substance. The oily substance was collected by discarding the supernatant solvent and again added dropwise to 480 ml of pentane and the same step was repeated, and then the supernatant pentane was discarded and the precipitate was collected and dried under a reduced pressure to obtain the title compound (to be referred to as betaine ester (10) hereinafter) as a light yellow transparent oil. Yield 38.65 g (0.075 mol; yield 74.7%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.76 (3 H, d, J = 6.9 Hz, >CH-CH3), 0.90 (3 H, d, J = 5.5 Hz, (CH3)2-CH-), 0.93 (3 H, d, J = 5.5 Hz, (CH3)2-CH-), 1.05 (2 H, quint, J = 11 Hz, >CH2), 1.25 (16 H, br s, -(CH2)3-CH3), 1.4 - 1.9 (7 H, cyclic, >CH2, -CH2-CH2-CONH-), 1.9 - 2.2 (3 H, >CH, N-C-CH2-C-N), 3.36 (2 H, dt, J = 5.5, 7.2 Hz, -CONH-CH2-C-), 3.50 (3 H, s, CH3-N+-CH3), 3.52 (3 H, s, CH3-N+-CH3), 4.13 (2 H, t, J = 7 Hz, -CH2-CH2-N+-), 4.43 (1 H, d, N+-CH2-C=O, J = 16 Hz), 4.62 (1 H, d, N+-CH2-C=O, J = 16 Hz), 4.82 (1 H, td, J = 4.5, 10.9 Hz, >CH-O-C=O), 8.35 (1 H, t, J = 5.5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 2956 (ν asCH3), 2924 (ν asCH2), 2854 (ν sCH2), 1741 (ν C=O, ester), 1651 (ν C=O, amide), 1549 (δ NH, ν C-N), 1466 (δ asCH3; δ CH2), 1390 (gem-dimethyl), 1371 (gem-dimethyl), 1242, 1209 (ν C-O, ester), 1153, 1020, 951, 912, 721 ((CH2)n).

Inventive Example 11: Synthesis of N,N-dimethyl-N-(2-phenylethyl)oxycarbonylmethyl-N-(3-(dodecanoylamino)propyl)ammonium chloride



[0056] A 14.22 g (0.050 mol) portion of N-dodecanoyl-N',N'-dimethyl-1,3-diaminopropane and 120 ml of diethyl ether were put into a flask, and 9.93 g (0.050 mol) of 2-phenylethyl chloroacetate was added thereto at 0 to 5°C spending 5 minutes. The reaction mixture was further stirred at 25°C for 24 hours, and disappearance of the most part of chloroacetate was confirmed by 1H-NMR. Next, the reaction mixture was slowly added dropwise to 600 ml of hexane which was ice-cooled and vigorously stirred, spending 10 minutes, to effect precipitation of the product as a white solid. Thereafter, in the same manner as described in Inventive Example 1, the title compound (to be referred to as betaine ester (11) hereinafter) was obtained as a white powder. Yield 20.10 g (0.0416 mol; yield 83.2%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.88 (3 H, t, J = 6.4 Hz, -(CH2)10-CH3), 1.24 (16 H, br s, -(CH2)8-CH3), 1.5 - 1.8 (2 H, m, -CH2-CH2-CONH-), 1.9 - 2.2 (2 H, m, N-C-CH2-C-N), 2.29 (2 H, t, J = 7.6 Hz, -CH2-CH2-CONH-), 2.98 (2 H, t, J = 7 Hz, -CH2-CH2- phenyl), 3.35 (2 H, dt, J = 5.5, 7.8 Hz, -CONH-CH2-C-), 3.41 (6 H, s, CH3-N+-CH3), 3.99 (2 H, t, J = 7.8 Hz, -CH2-CH2-N+-), 4.44 (2 H, t, J = 7 Hz, -CH2-CH2-phenyl), 4.67 (2 H, s, N+-CH2-C=O), 7.05 - 7.4 (5 H, m, phenyl), 7.9 (1 H, t, J = 5.5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3084 (ν CH, phenyl), 3030 (ν CH, phenyl), 2952 (ν asCH3), 2924 (ν asCH2), 2848 (ν sCH2), 1743 (ν C=O, ester), 1645 (ν C=O, amide), 1607 (phenyl), 1552 (δ NH, ν C-N), 1485, 1381 (δ sCH3), 1230, 1194 (ν C-O, ester), 1151, 1074, 1024, 960, 901, 746.

Inventive Example 12: Synthesis of N,N-dimethyl-N-(3-methyl-4-isopropylphenyl)oxycarbonylmethyl-N-(3-(octadecanoylamino)propyl)ammonium chloride



[0057] A 33.18 g (0.090 mol) portion of N-octadecanoyl-N',N'-dimethyl-1,3-diaminopropane and 120 ml of chloroform were put into a flask, and 22.44 g (0.099 mol) of 3-methyl-4-isopropylphenyl chloroacetate was added thereto at 25°C spending 5 minutes. The reaction mixture was stirred at 25°C for 36 hours and then, after confirming disappearance of the most part of chloroacetate by 1H-NMR, the solvent was evaporated under a reduced pressure. The thus obtained viscous oil was dissolved in 300 ml of acetone and cooled to 5 to 10°C to effect precipitation of a white precipitate. Thereafter, in the same manner as described in Inventive Example 1, the title compound (to be referred to as betaine ester (12) hereinafter) was obtained as a white solid. Yield 41.80 g (0.070 mol; yield 78.0%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.88 (3 H, t, J = 6.4 Hz, -(CH2)16-CH3), 1.21 (6 H, d, J = 6.8 Hz, -CH(CH3)2), 1.26 (28 H, br s, -(CH2)14-CH3), 1.5 - 1.7 (2 H, m, -CH2-CH2-CONH-), 2.0 - 2.3 (2 H, m, N-C-CH2-C-N), 2.28 (2 H, t, J = 7.8 Hz, -CH2-CH2-CONH-), 2.31 (3 H, s, phenyl group 3-methyl), 3.1 (1 H, quint, J = 6.8 Hz, -CH(CH3)2), 3.39 (2 H, dt, J = 5.6, 7.6 Hz, -CONH-CH2-C-), 3.56 (6 H, s, CH3-N+-CH3), 4. 14 (2 H, t, J = 7.6 Hz, -CH2-CH2-N+-), 5.23 (2 H, s, N+-CH2-C=O), 6.89 (1 H, s, phenyl), 6.92 (1 H, J = 2.5, 9.8 Hz, phenyl), 7.22 (1 H, d, J = 8.3 Hz, phenyl), 7.88 (1 H, t, J = 5.6 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3100, 3050 (ν CH, phenyl), 2956 (ν asCH3), 2920 (ν asCH2), 2850 (ν sCH2), 1765 (ν C=O, ester), 1650 (ν C=O, amide), 1552 (δ NH, ν C-N), 1495 (ν C=C, phenyl), 1469, 1383 (δ sCH3), 1363, 1240, 1126 (δCH, phenyl), 1086, 1020 (δCH, phenyl), 987, 901, 822, 762 (phenyl), 719 (-(CH2)n-).

Inventive Example 13: Synthesis of N,N-dimethyl-N-L-menthyloxycarbonylmethyl-N-(3-(octadecanoylamino)propyl)ammonium chloride



[0058] A 110.00 g (0.298 mol) portion of N-octadecanoyl-N',N'-dimethyl-1,3-diaminopropane, 76.38 g (0.328 mol) of L-menthyl chloroacetate and 450 ml of acetone were put into a 1 liter capacity four neck round bottom flask, the reactants were heated under reflux for 6 hours and then disappearance of the most part of chloroacetate was confirmed by 1H-NMR. The reaction mixture was allowed to stand at room temperature for 12 hours and then ice-cooled to effect precipitation of white crystals. The crystals were purified by several times of repetition of a cycle in which the supernatant solvent is discarded by decantation, the remaining crystals are mixed with 30 ml of acetone and again dissolved by heating to 55°C, the solution is ice-cooled while stirring and then the thus precipitated crystals are collected by decantation. By drying under a reduced pressure using a vacuum pump, the title compound (to be referred to as betaine ester (13) hereinafter) was obtained as white crystals. Yield 114.82 g (0.191 mol; yield 64.0%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.75 (3 H, d, J = 6.9 Hz, >CH-CH3), 0.90 - 1.00 (9 H, (CH3)2-CH-, CH3-(CH2)19-), 1.00 - 1.20 (2 H, >-CH2), 1.25 (30 H, br s, -(CH2)15-Me), 1.4 - 1.9 (7 H, cyclic >CH2, >CH, -CH2-CH2-CONH-), 1.9 - 2.2 (3 H, >CH, N-C-CH2-C-N), 2.20 (2 H, t, J = 10.0 Hz, -CH2-CH2-C=O), 3.36 (2 H, dt, J = 5.5, 7.2 Hz, -CONH-CH2-C-), 3.50 (3 H, s, CH3-N+-CH3), 3.52 (3 H, s, CH3-N+-CH3), 4.13 (2 H, dd, J = 5.5 Hz, -CH2-CH2-N+-), 4.43 (1 H, d, N+-CH2-C=O, J = 16 Hz), 4.62 (1 H, d, N+-CH2-C=O, J = 16 Hz), 4.82 (1 H, td, J = 4.5, 10.9 Hz, >CH-O-C=O), 8.10 (1 H, t, J = 5.5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3150, 2954 (ν asCH3), 2920 (ν asCH2), 2850 (ν sCH2), 1736 (ν C=O, ester), 1655 (ν C=O, amide), 1552 (δ NH, ν C-N), 1467 (δasCH3; δCH, -CH2-), 1408 (gem-dimethyl), 1375 (gem-dimethyl), 1227, 1205 (ν C-O, ester), 1155, 1020, 955, 918, 721 ((CH2)n).

Inventive Example 14: Synthesis of N,N-dimethyl-N-L-menthyloxycarbonylmethyl-N-(3-(docosanoylamino)propyl)ammonium chloride



[0059] A 73.51 g (0.168 mol) portion of N-docosadecanoyl-N',N'-dimethyl-1,3-diaminopropane, 46.78 g (0.201 mol) of L-menthyl chloroacetate and 200 ml of toluene were put into a 1 liter capacity four neck round bottom flask, the reactants were stirred at 80°C for 2.5 hours and then disappearance of the most part of chloroacetate was confirmed by 1H-NMR. The solvent was evaporated under a reduced pressure using an evaporator, the crude product was mixed with 500 ml of acetone and dissolved by heating to 55°C, the solution was air-cooled while stirring and then the thus precipitated crystals were collected by filtration under pressure. The thus collected white crystals were again transferred into a flask and mixed with 500 ml of acetone, and the same step was repeated 6 times to remove L-menthyl chloroacetate. By drying under a reduced pressure using a vacuum pump, the title compound (to be referred to as betaine ester (14) hereinafter) was obtained as white crystals. Yield 68.3 g (0.102 mol; yield 60.7%).
1H-NMR (200 MHz, CDCl3): δ [ppm]
   0.75 (3 H, d, J = 6. 9 Hz, >CH-CH3), 0.90 - 1.00 (9 H, (CH3)2-CH-, CH3-(CH2)19-), 1.00 - 1.20 (2 H, >-CH2), 1.25 (38 H, br s, -(CH2)19-Me), 1.4 - 1.9 (7 H, cyclic >CH2, >CH, -CH2-CH2-CONH-), 1.9 - 2.2 (3 H, >CH, N-C-CH2-C-N), 2.20 (2 H, t, J = 10.0 Hz, -CH2-CH2-C=O), 3.36 (2 H, dt, J = 5.5, 7.2 Hz, -CONH-CH2-C-), 3.50 (3 H, s, CH3-N+-CH3), 3.52 (3 H, s, CH3-N+-CH3), 4.13 (2 H, dd, J = 5.5 Hz, -CH2-CH2-N+-), 4.43 (1 H, d, N+-CH2-C=O, J = 16 Hz), 4.62 (1 H, d, N+-CH2-C=O, J = 16 Hz), 4.82 (1 H, td, J = 4.5, 10.9 Hz, >CH-O-C=O), 8.10 (1 H, t, J = 5.5 Hz, -CONH-)
IR (NaCl) [cm-1]
3700 - 3150, 2954 (ν asCH3), 2920 (ν asCH2), 2850 (ν sCH2), 1736 (ν C=O, ester), 1655 (ν C=O, amide), 1552 (δ NH, ν C-N), 1467 (δ asCH3; δCH, -CH2-), 1408 (gem-dimethyl), 1375 (gem-dimethyl), 1227, 1205 (ν C-O, ester), 1155, 1020, 955, 918, 721 ((CH2)n).

Inventive Example 15



[0060] Softening agent compositions shown in Table 1 were prepared using the following components by the following method. Sustained aroma-releasing performance of the thus obtained softening compositions was evaluated by the following method. The results are shown in Table 2.

<Formulation components>


Component (a):



[0061] 



[R; Mixed straight chain alkyl groups having 17 and 15 carbon atoms (17 carbons/15 carbons (weight ratio) = 60/40)]

Component (b):



[0062] 



[R; As defined in the foregoing]

[R'; Mixed straight chain alkyl groups having 12, 14 and 16 carbon atoms (12 carbons:14 carbons:16 carbons (weight ratio) = 60:25:15)]

Component (c):



[0063] 

(c-1): Lunax S-50 (stearic acid, mfd. by Kao)


Component (d)



[0064] 

(d-1): a product prepared by adding 21 mol in average of ethylene oxide to lauryl alcohol


Component (e);



[0065] 

(e-1): calcium chloride

(e-2) : Excel 150 (mixture of mono-, di- and tri-glyceride stearate (mo:di:tri (weight ratio) = 60:35:5), mfd. by Kao)

(e-3-1): geraniol (perfume)

(e-3-2): 3-methyl-5-phenylpentanol (perfume)

(e-4): 99.5% ethanol


Component (f) (betaine esters of the invention):



[0066] 

(f-1): betaine ester (1)

(f-2): betaine ester (6)


<Preparation method>



[0067] Ion exchange water was put into a beaker and heated to 60°C. The components (a) to (e) (excluding (e-4)) were added in succession while stirring, and pH was adjusted to 3.0 with N/10 hydrochloric acid. After further mixing for 30 minutes while keeping at 60°C, the mixture was cooled to 28 to 30°C with stirring (cooling rate 1.5°C/min). After the cooling, the component (f) was dissolved in the component (e-4) and added as an ethanol solution of 40% in concentration of betaine ester. Also, when the component (b-2) was used, it was added after cooling of the addition of the component (f) . Next, the mixture was heated again and, when reached to 55°C, stirred for 5 minutes and then rapidly cooled in a water bath of 5°C. After cooling to a liquid temperature of 30°C or lower spending about 4 minutes, the water bath temperature was changed to 15°C and, when the liquid temperature finally reached 20°C, the stirring was stopped and the mixture was allowed to stand for 1 hour.

[0068] Also, when the component (f) was not added, the same procedure was carried out except that the components (a) to (e) including (e-4) were added in succession.

<Evaluation method of sustained aroma-releasing performance>



[0069] A 0.7 g portion of each softening agent composition was added to 3 liters of tap water, a towel (100% cotton) was thoroughly soaked therein, rinsed twice in 3 liters of tap water and dried by spreading a piece of dehydrating cloth in a room of 25°C in room temperature and 40% in relative humidity, and then changes in the aroma with the lapse of drying time was evaluated by five testers based on the following odor strength criteria. The evaluation value indicates average value of the evaluation results by five testers.

5: very strong

4: slightly strong

3: moderate

2: slightly weak

1: weak

0: no scent

Table 1
 Inventive productComparative product
 15-115-215-315-415-115-215-3
Softening agent composition (%) a-1 8   8   8   8
a-2   15   15   15  
b-1-1 8   8   8   8
b-1-2   1   1   1  
b-2   1   1   1  
c-1 0.6 0.6 0.2 0.2 0.6 0.6 0.6
d-1 2.5 2.5 2.5 2.5 2.5 2.5 2.5
e-1 0.01 0.01 0.01 0.01 0.01 0.01 0.01
e-2 0.1 0.1 0.1 0.1 0.1 0.1 0.1
e-3-1         0.3 0.3  
e-3-2             0.3
e-4 1.8 1.8 1.7 1.7 1.8 1.8 1.7
f-1 1.2 1.2          
f-2     1.1 1.1      
water bal. bal. bal. bal. bal. bal. bal.
Composition pH 2.5 2.5 2.5 2.5 2.5 2.5 2.5
bal: balance
Table 2
Drying time (hr)Inventive productComparative product
 15-115-215-315-415-115-215-3
0 (just after dehydration) 0.5 0.5 0.5 0.5 1.5 1.5 0.5
1 1.0 1.0 1.0 1.0 1.5 1.5 1.5
2 1.0 1.0 1.5 1.5 1.5 1.5 1.5
3 1.0 1.0 1.0 1.0 0.5 0.5 1.0
17 1.0 1.0 0.5 0.5 0 0 0.5
24 1.0 1.0 0.5 0.5 0 0 0.1
72 1.0 1.0 0.5 0.5 0 0 0


[0070] Based on the results of Table 2, it was found that the betaine ester-formulated softening agent compositions of the invention have the effect to sustain scent of perfumes in comparison with the respective compositions in which only their corresponding perfumes were formulated.

Inventive Example 16



[0071] Detergent compositions for hard surface use shown in Table 3 were prepared, and detergency of soap scum stains in a bathroom bathtub and stains in a flush toilet stool, storage stability of the detergent (coloring property) and sustained release of perfumes from the bathroom bathtub were evaluated by the following methods. The results are shown in Table 3.

<Detergency of soap scum stains>



[0072] Using an unwashed polypropylene bathtub which had been used under the same condition for half a year, a piece of cloth impregnated with each detergent composition was adhered to stains of the bathtub for 5 minutes and then the stains were rubbed with a sponge to evaluate removing condition of the stains visually by the following five steps. In this connection, each value shown in Table 3 is the average score of five evaluations.

5: very good washing

4: good washing

3: uneven washing

2: slight washing

1: almost no washing


<Sustained release of aroma>



[0073] The polypropylene bathtub washed by the above method was dried at room temperature for 3 hours, and sustained release of the aroma from the bathtub surface was evaluated by five testers based on the following five step strength of aroma. The evaluation value was expressed by rounding off the fractions of the average value of the evaluation results by five testers to one decimal place.

5: very strong

4: slightly strong

3: moderate

2: slightly weak

1: weak

0: no scent


<Detergency of stains in flush toilet stool>



[0074] Detergency of inorganic-organic complex stains in a flush toilet stool, which cannot be washed off by merely rubbing with a brush, was evaluated by spraying a predetermined amount of each detergent composition, rubbing the stains with a brush and then observing washed condition of the stains with the naked eye based on the following five step criteria.
ⓞ :
good
○ :
slightly good
Δ :
slightly bad
X :
bad

<Storage stability>



[0075] Each detergent composition was sealed in a polypropylene container and stored at 40°C for 3 months. Appearances before and after the storage were compared and evaluated.
O :
no changes in appearance
X :
evident coloring compared to the appearance before storage






[0076] Based on the results of Table 3, it was found that the betaine ester of the invention can be formulated stably in the hard surface detergent and gradually releases the aromatic component by remaining and adhering on the hard surface after washing.

Inventive Example 17



[0077] Detergent compositions for clothing use shown in Table 4 were prepared, and their effect to inhibit the peculiar bad smell generated by indoor drying of clothes washed using these detergent compositions was comparatively evaluated by the following method. The results are shown in Table 5.

<Inhibition effect evaluation method>



[0078] Cotton towels were used by ten persons for 2 weeks for wiping up their bodies soaked with sweet and water and then lightly moistened with ion exchange water, wrapped in vinyl bags and allowed to stand at 30°C for 2 days. Thereafter, each of these cotton towels was cut in half, and 10 pieces of the one side were washed with a comparative detergent system, and 10 pieces of the other side with a test detergent system. After washing and dehydration, they were dried in the same room of 30°C in temperature and 55% in humidity, and the strength of bad smell from the towels after 4 or 10 hours of the commencement of drying was evaluated by five testers based on the following six step criteria to calculate average value of the results. Also, a case in which the smell was felt as the aroma of perfume was evaluated as O, and the other case of unpleasant smell as X.

5: very strong

4: slightly strong

3: moderate

2: slightly weak

1: weak

0: no smell

Table 4
 Test detergentComparative detergent
Detergent Composition (%) LAS *1 20.0 20.0
Sodium palmitate 2.0 2.0
Zeolite *2 20.0 20.0
Amorphous silicate *3 7.0 7.0
Sodium sulfite 2.0 2.0
Sodium sulfate 23.0 23.0
Citric acid 10.0 10.0
PEG *4 2.0 2.0
Betaine ester (1) 1.2 -
Geraniol - 0.3
Moisture 1.0 1.0
Total 100.0 100.0
Shape granular granular
Concentration used 49 g/30 L 40 g/30 L
Washing solution pH 8.0 8.0
*1 LAS: an alkylbenzenesulfonic acid ("Alkene L" (alkyl chain having 10 to 14 carbon atoms), mfd. by Nisseki Senzai) neutralized with 48% sodium hydroxide aqueous solution
*2 Zeolite: 4A type zeolite, average particle size 3 µm
*3 Amorphous silicate: JIS No. 2 sodium silicate
*4 PEG: polyethylene glycol, average molecular weight 8,000
Table 5
 Test towelABCDEFGHIJ
Test detergent system (4 hr drying) Odor strength 0.6 0.6 0.4 0.6 0.6 0.8 0.6 0.6 0.4 0.6
Odor quality
Test detergent system (10 hr drying) Odor strength 0.4 0.4 0.4 0.4 0.4 0.6 0.6 0.4 0.2 0.4
Odor quality
Comparative detergent system (4 hr drying) Odor strength 1.2 1.0 1.0 1.6 1.0 1.6 1.0 1.0 1.0 1.0
Odor quality X X X X X X X X X X
Comparative detergent system (10 hr drying) Odor strength 1.0 1.0 0.8 1.2 1.0 1.2 1.0 1.0 1.0 1.0
Odor quality X X X X X X X X X X

Inventive Example 18



[0079] Using the following test solutions, a fungal resistance test was carried out by the following method. The results are shown in Table 6.

<Test solutions>



[0080] Each of betaine ester (1), betaine ester (3) and geraniol was dissolved in 99.5% ethanol to prepare solutions having the following concentrations and used as test solutions (A), (B) and (C), respectively.

Test solution (A): betaine ester (1), 1.17% in concentration

Test solution (B): betaine ester (3), 1.00% in concentration

Test solution (C): geraniol, 0.300% in concentration


<Fungal resistance test>


(1) Preparation of test cloth



[0081] A 0.3 ml portion of each test solution or 0.3 ml of 99.5% ethanol used as a control was separately coated on a cotton-polyester mixture test cloth cut into a disc of 25 mm in diameter and then the cloth was dried at 25°C under 30% relative humidity for 48 hours to be used as a test cloth. Three sheets of the test cloth were prepared for one test solution and used in the test.

(2) Fungal resistance test



[0082] A plate agar medium having the following composition was prepared to a thickness of 15 mm in a Petri dish of 150 mm in diameter. The medium was used by sterilizing it in advance at 120°C for 20 minutes in an autoclave.

Medium composition;



[0083] Pure water: 1,500ml, glucose: 15 g, agar: 23 g, inorganic salts stock solution (NH4NO3 90 g, KH2PO4 60 g, MgSO4·7H2O, 15 g, KCl 15 g, pure water 1,000 g): 50 ml

[0084] Each test cloth was put on the above medium, and about 1 ml of a spore suspension prepared by dispersing spores of a fungus (Aspergillus niger) in sterile water (containing 0.005% sodium dioctylsulfosuccinate) was sprayed. This was cultured at 29 ± 1°C for 7 days to carry out comparative test of fungal resistance by inspecting growing condition of the fungus on the periphery or surface of the sample, and the results were evaluated based on the following five step criteria by observing growth condition of the fungus on the test cloth surface with the naked eye and under a microscope. That is, when the fungus is not grown on the surface of a test cloth and also, when the test cloth is peeled from the medium, the fungus is not grown on the backside but forming an inhibition zone, the result is judged as excellent in fungal resistance (NG). In this connection, when the inhibition zone was not clearly observed on the medium surface, the test cloth surface was observed with a microscope under 50 x objective using an ocular micrometer to measure the area of fungal growth by millimeter unit, and the fungal resistance was evaluated based on the size of fungal growth area occupying the test cloth surface (TG, SG, MG or HG).

Completely no fungal growth: NG (no growth)



[0085] 

Growth on less than 10% of the surface area: TG (trace of growth)

Growth on 10% or more and less than 30% of the surface area: SG (slight growth)

Growth on 30% or more and less than 60% of the surface area: MG (moderate growth)

Growth on 60% or more of the surface area: HG (heavy growth)

Table 6
Test solution(A)(B)(C)Control (ethanol)
Growth rate (%) 0 0 35 85
0 0 32 75
0 0 40 85
Average 0 0 36 82
Judgment NG NG MG HG


[0086] As a result of the test, it was confirmed that the test cloth on which the betaine ester of the invention was coated has higher effect to inhibit generation of a fungus in comparison with the test cloth on which geraniol was coated and then dried.


Claims

1. A substance which is a betaine ester of a functional alcohol that has an amido bond in its molecule and releases the functional alcohol, represented by a general formula (I)

wherein each of R1, R2 and R3 independently represents hydrogen atom or a straight- or branched-chain alkyl or alkenyl group having from 1 to 30 carbon atoms,
   Y represents a straight- or branched-chain alkylene having from 1 to 4 carbon atoms,
   Z is a group represented by -R5(OA)n- wherein R5 is a straight- or branched-chain alkylene group having from 1 to 30 carbon atoms, and A is a straight- or branched-chain alkylene group having from 2 to 4 carbon atoms, and n is a number from 0 to 10,
   R4 represents a saturated or unsaturated aliphatic hydrocarbon group having from 1 to 11 carbon atoms, being a residue, in which one hydroxyl group is removed from leaf alcohol (cis-3-hexenol), 3-octenol, 2,4-dimethyl-3-cyclohexene-1-methanol, 4-isopropylcyclohexanol, 4-isopropylcyclohexylmethanol, 1-(4-isopropylcyclohexyl)ethanol, p-(t-butyl)cyclohexanol, o-(t-butyl)cyclohexanol, 9-decenol, linalool, geraniol, nerol, citronellol, rhodinol, dimethyloctanol, hydroxycitronellol, tetrahydrolinalool, lavandulol, mugol, myrcenol, terpineol, L-menthol, borneol, isopulegol, tetrahydromugol, nopol or glycerol,
   or aromatic hydrocarbon group having from 1 to 11 carbon atoms, being a residue in which one hydroxyl group is removed from benzyl alcohol, β-phenylethyl alcohol, γ-phenylpropyl alcohol, cinnamic alcohol, anisic alcohol, dimethylbenzylcarbinol, methylphenylcarbinol, dimethylphenylcarbinol, phenoxyehtyl alcohol, styrallyl alcohol, dimethylphenylethylcarbinol, thymol, carvacrol, eugenol, isoeugenol, ethyl vanillin, meta-chloroxylenol, 2,4-dichlorophenol, 2,4-dichlorobenzyl alcohol, hinokithiol or 3-methyl-4-isopropylphenol,
   or an alkadienyl group, alkatrienyl group, aryl group, arylalkyl group or monocyclic, bicyclic or tricyclic terpene hydrocarbon group, each having from 12 to 30 carbon atoms, wherein a part of the hydrogen atoms on the hydrocarbon group of R4 may be substituted by a halogen atom or a hydroxyl group, the methylene group of the hydrocarbon group of R4 may be substituted by a carbonyl group, an amido group, an oxygen atom or a sulfur atom, the methyl group may be substituted by a formyl group or -CONH2, the carbon-carbon double bond may be substituted by an epoxy group and, when isomers are present in R4, it may be a mixture of isomers,
   and X- represents an anion.
 
2. The substance according to claim 1, wherein the betaine ester of a functional alcohol is a compound represented by a general formula (II)

wherein each of R1, R2, R3 and R4 have the same meaning as in claim 1, n is a number of from 0 to 10, X- represents an anion, R6 represents hydrogen atom or methyl group, and a is 1 or 2.
 
3. A composition which contains a functional alcohol releasing substance described in any one of claims 1 or 2.
 
4. The composition according to claim 3, wherein it contains a textile conditioner or softening agent component.
 
5. The composition according to claim 3, wherein it contains a detergent component.
 


Ansprüche

1. Substanz, die ein Betainester eines funktionellen Alkohols mit einer Amidbindung im Molekül ist und den funktionellen Alkohol freisetzt, dargestellt durch die allgemeine Formel (I):

wobei R1, R2 und R3 jeweils unabhängig voneinander ein Wasserstoffatom oder eine geradkettige oder verzweigte Alkyl- oder Alkenylgruppe mit 1 bis 30 Kohlenstoffatomen darstellen,
Y eine geradkettige oder verzweigte Alkylengruppe mit 1 bis 4 Kohlenstoffatomen darstellt,
Z eine durch -R5(OA)n- dargestellte Gruppe ist, wobei R5 eine geradkettige oder verzweigte Alkylengruppe mit 1 bis 30 Kohlenstoffatomen ist, A eine geradkettige oder verzweigte Alkylengruppe mit 2 bis 4 Kohlenstoffatomen ist, und n eine Zahl von 0 bis 10 ist,
R4 eine gesättigte oder ungesättigte, aliphatische Kohlenwasserstoffgruppe mit 1 bis 11 Kohlenstoffatomen darstellt, die ein Rest ist, in dem eine Hydroxylgruppe von Blatteralkohol (cis-3-Hexenol), 3-Octenol, 2,4-Dimethyl-3-cyclohexen-1-methanol, 4-Isopropylcyclohexanol, 4-Isopropylcyclohexylmethanol, 1-(4-Isopropylcyclohexyl)ethanol, p-(t-Butyl)cyclohexanol, o-(t-Butyl)cyclohexanol, 9-Decenol, Linalool, Geraniol, Nerol, Citronellol, Rhodinol, Dimethyloctanol, Hydroxycitronellol, Tetrahydrolinalool, Lavandulol, Mugol, Myrcenol, Terpineol, L-Menthol, Borneol, Isopulegol, Tetrahydromugol, Nopol oder Glycerin entfernt wird,
oder eine aromatische Kohlenwasserstoffgruppe mit 1 bis 11 Kohlenstoffatomen, die ein Rest ist, in dem eine Hydroxylgruppe aus Benzylalkohol, β-Phenylethylalkohol, γ-Phenylpropylalkohol, Zimtalkohol, Anisalkohol, Dimethylbenzylcarbinol, Methylphenylcarbinol, Dimethylphenylcarbinol, Phenoxyethylalkohol, Styrallylalkohol, Dimethylphenylethylcarbinol, Thymol, Carvacrol, Eugenol, Isoeugenol, Ethylvanillin, meta-Chloroxylenol, 2,4-Dichlorphenol, 2,4-Dichlorbenzylalkohol, Hinokithiol oder 3-Methyl-4-isopropylphenol entfernt wird,
oder eine Alkadienylgruppe, Alkatrienylgruppe, Arylgruppe, Arylalkylgruppe oder monocyclische, bicyclische oder tricyclische Terpenkohlenwasserstoffgruppe, die jeweils 12 bis 30 Kohlenstoffatome aufweisen, wobei ein Teil der Wasserstoffatome der Kohlenwasserstoffgruppe von R4 durch ein Halogenatom oder eine Hydroxylgruppe substituiert sein kann, die Methylengruppe der Kohlenwasserstoffgruppe von R4 durch eine Carbonylgruppe, eine Amidgruppe, ein Sauerstoffatom oder ein Schwefelatom substituiert sein kann, die Methylgruppe durch eine Formylgruppe oder -CONH2 substituiert sein kann, die Kohlenstoff-Kohlenstoff-Doppelbindung durch eine Epoxygruppe substituiert sein kann, und, wenn Isomere in R4 vorliegen, eine Mischung der Isomere vorliegen kann,
und X- ein Anion darstellt.
 
2. Substanz gemäss Anspruch 1, wobei der Betainester eines funktionellen Alkohols eine durch die allgemeine Formel (II) dargestellte Verbindung ist:

wobei R1, R2, R3 und R4 jeweils die gleichen Bedeutungen wie in Anspruch 1 haben, n eine Zahl von 0 bis 10 ist, X- ein Anion darstellt, R6 ein Wasserstoffatom oder eine Methylgruppe darstellt und a 1 oder 2 ist.
 
3. Zusammensetzung, die eine in einem der Ansprüche 1 oder 2 beschriebene, einen funktionellen Alkohol freisetzende Substanz enthält.
 
4. Zusammensetzung gemäss Anspruch 3, wobei sie einen Textilkonditionierer oder eine Weichmacherkomponente enthält.
 
5. Zusammensetzung gemäss Anspruch 3, wobei sie eine Detergenzkomponente enthält.
 


Revendications

1. Substance qui est un ester de bétaïne et d'un alcool fonctionnel qui a une liaison amido dans sa molécule et libère l'alcool fonctionnel, représentée par la formule générale (I) :

dans laquelle
chacun de R1, R2 et R3 représente indépendamment un atome d'hydrogène ou un groupe alkyle ou alcényle à chaîne droite ou ramifiée ayant de 1 à 30 atomes de carbone,
   Y représente un alkylène à chaîne droite ou ramifiée ayant de 1 à 4 atomes de carbone,
   Z est un groupe représenté par -R5(OA)n- où R5 est un groupe alkylène à chaîne droite ou ramifiée ayant de 1 à 30 atomes de carbone, et A est un groupe alkylène à chaîne droite ou ramifiée ayant de 2 à 4 atomes de carbone, et n est un nombre de 0 à 10,
   R4 représente un groupe hydrocarboné aliphatique saturé ou insaturé ayant de 1 à 11 atomes de carbone, qui est un résidu, dans lequel un groupe hydroxyle est éliminé de l'alcool de feuilles (cis-3-hexénol), du 3-octénol, du 2,4-diméthyl-3-cyclohexène-1-méthanol, du 4-isopropylcyclohexanol, du 4-isopropylcyclohexylméthanol, du 1-(4-isopropylcyclohexyl)éthanol, du p-(t-butyl)cyclohexanol, du o-(t-butyl)cyclohexanol, du 9-décénol, du linalool, du géraniol, du nérol, du citronellol, du rhodinol, du diméthyloctanol, de l'hydroxycitronellol, du tétrahydrolinalool, du lavandulol, du mugol, du myrcénol, du terpinéol, du L-menthol, du bornéol, de l'isopulégol, du tétrahydromugol, du nopol ou du glycérol,
   ou un groupe hydrocarboné aromatique ayant de 1 à 11 atomes de carbone, qui est un résidu dans lequel un groupe hydroxyle est éliminé de l'alcool benzylique, de l'alcool β-phényléthylique, de l'alcool γ-phénylpropylique, de l'alcool cinnamique, de l'alcool anisique, du diméthylbenzylcarbinol, du méthylphénylcarbinol, du diméthylphénylcarbinol, de l'alcool phénoxyéthylique, de l'alcool styrallylique, du diméthylphényléthylcarbinol, du thymol, du carvacrol, de l'eugénol, de l'isoeugénol, de l'éthylvanilline, du méta-chloroxylénol, du 2,4-dichlorophénol, de l'alcool 2,4-dichlorobenzylique, de l'hinokithiol ou du 3-méthyl-4-isopropylphénol,
   ou un groupe alcadiényle, un groupe alcatriényle, un groupe aryle, un groupe arylalkyle ou un groupe hydrocarboné terpène monocyclique, bicyclique ou tricyclique, ayant chacun de 12 à 30 atomes de carbone, où une partie des atomes d'hydrogène sur le groupe hydrocarboonés de R4 peut être substituée par un atome d'halogène ou un groupe hydroxyle, le groupe méthylène du groupe hydrocarboné de R4 peut être substitué par un groupe carbonyle, un groupe amido, un atome d'oxygène ou un atome de soufre, le groupe méthyle peut être substitué par un groupe formyle ou -CONH2, la double liaison carbone-carbone peut être substituée par un groupe époxy et, quand des isomères sont présents dans R4, il peut s'agir d'un mélange d'isomères,
   et X- représente un anion.
 
2. Substance selon la revendication 1, dans laquelle l'ester de bétaïne et d'un alcool fonctionnel est un composé représenté par la formule générale (II) :

dans laquelle chacun de R1, R2, R3 et R4 a la même signification que dans la revendication 1, n est un nombre de 0 à 10, X- représente un anion, R6 représente un atome d'hydrogène ou un groupe méthyle, et a vaut 1 ou 2.
 
3. Composition qui contient une substance libérant un alcool fonctionnel, décrite dans l'une quelconque des revendications 1 et 2.
 
4. Composition selon la revendication 3, qui contient un composant agent de conditionnement des textiles ou agent assouplissant.
 
5. Composition selon la revendication 3, qui contient un composant détergent.