NEW QUATERNARY AMMONIUM COMPOUNDS

Abstract

The invention concerns new quaternary ammonium compounds with surfactant properties and improved biodegradability.

##STR00001##

Claims

1. An ionic compound of general formula I ##STR00100## wherein A is a tetravalent linker selected from the group consisting of A-1 to A-6 ##STR00101## Q.sub.1 to Q.sub.4, which may be identical or different from each other, are selected from the group consisting of hydrogen, R and X, wherein R, which may be the same or different at each occurrence, is a C.sub.5-C.sub.27 aliphatic group, m, m′, m″ and m′″, which may be the same or different at each occurrence, are 0, 1, 2 or 3, k, k′ k″, k′″ and k″″, which may be the same or different, are 0, 1, 2 or 3, and X, which may be the same or different at each occurrence, is represented by formula II ##STR00102## wherein Z.sub.1, Z.sub.2 and Z.sub.3, which may be the same or different, are O, S or NH, Y is a divalent C.sub.1-C.sub.6 aliphatic radical, R′, R″ and R′″, which may be the same or different, are hydrogen or a C.sub.1 to C.sub.4 alkyl group, n and n′ are 0 or 1 with the sum of n+n′ being 1 or 2, wherein at least one of Q.sub.1 to Q.sub.4 is represented by X and at least two of groups Q.sub.1 to Q.sub.4 are represented by R, which groups R may be the same or different at each occurrence, and wherein, if the ionic compound is such that (i) A is represented by A-6 with m, m′, m″ and m′″ equal to 0, (ii) one and only one of Q.sub.1 to Q.sub.4 is represented by a substituent X and n in the substituent X is equal to 0 and (iii) two and only two of Q.sub.1 to Q.sub.4 are represented by substituents R, then the difference of the number of carbon atoms of the two substituents R is 0, 1, 3 or more than 3.

2. The compound in accordance with claim 1, wherein the compound comprises one or two groups X and two and only two groups R.

3. The compound in accordance with claim 1 wherein n+n′ is 1.

4. The compound in accordance with claim 1 wherein n+n′ is 2.

5. The compound in accordance with am claim 1, wherein n′ is 1 and Y is a C.sub.2-C.sub.6 aliphatic group.

6. The compound in accordance with claim 1, wherein A is represented by A-6, m, m′, m″ and m′″ are 0, Z.sub.1 to Z.sub.3 are O and wherein the compound comprises two groups R and one group X.

7. The compound in accordance with claim 6 wherein n is 0 and n′ is 1.

8. The compound in accordance with claim 6 wherein n is 1.

9. The compound in accordance with claim 1, wherein A is represented by A-3 or A-4, m, m′, m″, m′″ and k′″ are 0 and two of substituents Q.sub.1 to Q.sub.4 are represented by groups X with both X attached to the same carbon atom of linker A and two groups R attached to the same or to different carbon atoms of linker A.

10. The compound in accordance with claim 1, wherein A is represented by A-1, m and m′ are 1, m″ and m′″ are 0, k is 0 and two substituents Q.sub.1 to Q.sub.4 are represented by groups X with both groups X being attached to the —(CH.sub.2).sub.m and —(CH.sub.2).sub.m′— groups directly attached to the nitrogen atom of linker A.

11. The compound in accordance with claim 1, wherein A is represented by A-2, k′ is 0, k″ is 1, m is 1, m′, m″ and m′″ are 0 and two of substituents Q.sub.1 to Q.sub.4 are represented by groups X attached to two adjacent carbon atoms of linker A.

12. The compound in accordance with claim 1, wherein A is represented by A-5, m, m′, m″, m′″ and k″″ are 0, two of substituents Q.sub.1 to Q.sub.4 are X with each carbon atom of linker A carrying one group X and one group R wherein X and R might be the same or different at each occurrence.

13. The compound in accordance with claim 12 wherein in groups X, n is 1, n′ is 0, and Y is CH.sub.2.

14. An electroneutral compound of general formula (III) ##STR00103## wherein A, Q.sub.1 to Q.sub.4 are as defined in claim 1, W is an anion or an anionic group bearing w negative charges and r is the number of substituents Q.sub.1 to Q.sub.4 which are represented by a group X.

15. (canceled)

16. (canceled)

Description

WORKING EXAMPLES

Example 1—Synthesis of a Quaternary Ammonium Compound of Formula IV Wherein J is J3, i.e. Wherein n and n′ in Group X are Each 1, Starting from 12-Tricosanol

[0553] C.sub.23 12-tricosanol was obtained from C.sub.23 12-tricosanone through catalytic hydrogenation according to US-A 2018/093936 (see example 3 in this document).

[0554] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0555] Fresh commercial anhydrous CHCl.sub.3 (amylene stabilized), anhydrous toluene and anhydrous acetonitrile were used as such. Choline chloride (which is hygroscopic) was washed several times with anhydrous THF and dried under vacuum prior to use.

[0556] Into a 500 mL round bottom flask equipped with a condenser, a temperature probe, a heater and a magnetic stirrer were added 38.37 g of 12-tricosanol (112.7 mmol) followed by 150 mL of toluene. The mixture was then allowed to stir at room temperature and 0.1 g of solid KOH (1.7 mmol, 1.6 mol %) was then added followed by 18.26 g of carbonyldiimidazole (112.7 mmol, 1 eq.) and an additional 20 mL of toluene.

[0557] The mixture was then allowed to stir at 70° C.; at this temperature the mixture became transparent. Reaction progress was followed by .sup.1H-NMR and after three hours at 70° C., an alcohol conversion of 99% was reached.

[0558] All the volatiles were then removed through distillation at 50° C., 9 mbar to afford 59.4 g of a residue which was used in the next stage without purification.

[0559] The residue was then solubilized in a mixture of 40 mL CHCl.sub.3 and 40 mL of acetonitrile and 15.74 g of choline chloride (112.7 mmol, 1 eq.) was added at room temperature. The mixture was then allowed to stir at 50° C. overnight.

[0560] Over the course of the reaction, the reaction medium turned homogeneous and green. The reaction progress was followed by .sup.1H-NMR and a conversion of 89% was obtained at this stage. The solvent was then removed under vacuum to afford around 79.1 g of crude.

[0561] The crude residue was purified by chromatography on silica gel (330 g of silica) in order to remove impurities and imidazole by-product (the specification is <0.5 wt % of imidazole) using an ethylacetate/methanol (AcOEt/MeOH) eluent (going from 100% AcOEt to 50:50 AcOEt:MeOH).

[0562] Five fractions were collected: the first fraction corresponding to the intermediate imidazole carbonate as well as the second fraction corresponding to the imidazole were discarded and the three remaining fractions were collected and re-purified.

[0563] For the second chromatography on silica gel, 200 g of silica was used with the same eluent system. Two fractions were collected: the first one was a mixture of product and imidazole and the second one was the pure product.

[0564] Finally the first fraction was purified again using 30 g of silica gel and the same eluent system to afford additional amount of product.

[0565] All clean fractions were collected affording 39.8 g of product as a white wax corresponding to 70% isolated yield.

[0566] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 4.65 (quint, 1H), 4.61-4.51 (m, 2H), 4.22-4.02 (m, 2H), 3.52 (s, 9H), 1.61-1.44 (m, 4H), 1.32-1.12 (m, 36H), 0.84 (t, J=8.0 Hz, 6H).

[0567] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 154.21, 80.88, 64.92, 61.24, 54.59, 33.96, 32.10, 29.83, 29.82, 29.80, 29.70, 29.68, 29.54, 25.36, 22.88, 14.31 (terminal CH.sub.3).

Example 2—Synthesis of a Quaternary Ammonium Compound of Formula IV Wherein J is J3, i.e. Wherein n and n′ in Group X are Each 1, Starting from 16-Hentriacontanol

[0568] C.sub.31 16-hentriacontanol was obtained from C.sub.31 16-hentriacontanol through catalytic hydrogenation according to US-A US2018/093936 (see example 3 in this document).

[0569] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0570] Fresh commercial anhydrous CHCl.sub.3 (amylene stabilized), anhydrous toluene and anhydrous acetonitrile were used as such. Choline chloride (which is hygroscopic) was washed several times with anhydrous THF and dried under vacuum prior to use.

[0571] In a 500 mL round bottom flask equipped with a condenser, a temperature probe, a heater and a magnetic stirrer were added 45.2 g of 16-hentriacontanol (99.9 mmol) followed by 150 mL of toluene. The mixture was then allowed to stir at room temperature and 0.1 g of solid KOH (1.7 mmol, 1.7 mol %) was then added followed by 17.0 g of carbonyldiimidazole (105 mmol, 1.05 eq.) and an additional 50 mL of toluene.

[0572] The mixture was then allowed to stir at 60° C.; at this temperature the mixture became transparent. Reaction progress was followed by .sup.1H-NMR and after one hour at 60° C., an alcohol conversion >99% was reached.

[0573] All the volatiles were then removed through vacuum to afford a white residue which was used in the next stage without purification.

[0574] The residue was then solubilized in a mixture of 80 mL CHCl.sub.3 and 80 mL of acetonitrile and 13.95 g of choline chloride (99.9 mmol, 1 eq.) was added at room temperature. The mixture was then allowed to stir at 55° C. overnight.

[0575] The reaction progress was followed by .sup.1H-NMR and only a weak conversion of 30% was obtained at this stage. This weak conversion could be explained by KOH decomposition (for example by reaction with CHCl.sub.3).

[0576] 0.3 g of KOH (5.1 mmol) was then added and the mixture was stirred at reflux during an additional 3 hours. The conversion level reached 78% according to NMR.

[0577] An additional 0.2 g of KOH was again added followed by stirring at reflux during twelve hours.

[0578] At this stage, conversion level was 83% and the color of the mixture was brown.

[0579] The solvent was then removed under vacuum to afford around 84 g of crude.

[0580] The crude residue was purified by chromatography on silica gel (2 columns with 330 g of silica) in order to remove impurities and imidazole by-product (the specification is <0.5 wt % of imidazole) using an AcOEt/MeOH eluent (going from 100% AcOEt to 50:50 AcOEt:MeOH).

[0581] Four fractions were collected: the first fraction corresponded to the intermediate imidazole carbonate and the second fraction corresponded to the imidazole. The third fraction contained a mixture of imidazole and desired product and the last fraction corresponded to the desired product.

[0582] The fourth fractions of each column were collected and subjected to a second chromatography on silica gel. 330 g of silica was used with the same eluent system to afford the desired product with good purity.

[0583] 36.6 g of product as a white wax was obtained corresponding to 60% isolated yield.

[0584] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 4.66 (quint, 1H), 4.62-4.52 (m, 2H), 4.24-4.04 (m, 2H), 3.53 (s, 9H), 1.62-1.46 (m, 4H), 1.34-1.14 (m, 52H), 0.85 (t, J=6.8 Hz, 6H).

[0585] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 154.20, 80.87, 64.91, 61.23, 54.58, 33.96, 32.11, 29.90, 29.85, 29.82, 29.72, 29.69, 29.55, 25.36, 22.88, 14.31 (terminal CH3).

Example 3—Synthesis of a Mixture of Quaternary Ammonium Compounds Wherein A is Represented by A-2 or A-3 (a Mixture of Compounds of Formula (V) and (VI)) Starting from C.SUB.31.-16-Hentriacontanone

[0586] Knoevenagel Condensation to Afford Diester Intermediate:

##STR00091##

[0587] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0588] Fresh commercial anhydrous CHCl.sub.3, anhydrous THF and anhydrous pyridine were used as such.

[0589] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser, an addition funnel and a temperature probe were added 36.5 mL of TiCl.sub.4 (63.00 g, 0.332 mole), followed by 146.3 mL of CHCl.sub.3.

[0590] The mixture was stirred at −10° C. and anhydrous THF (358 mL) was slowly added through the addition funnel at a rate avoiding a temperature increase of the reaction medium above +5° C. During THF addition, a yellow precipitate appeared. Then 15.3 mL of dimethyl malonate (17.69 g, 0.134 mole) were added into the reaction mixture which was then allowed to stir at room temperature for 1 hour in order to allow malonate complexation to occur.

[0591] Then the mixture was allowed to cool down to 0° C. and a solution of 71.80 mL of anhydrous pyridine (70.50 g, 0.891 mole) in 23 mL of THF was slowly added into the reactor. During addition, the colour of the mixture turned red. The mixture was then allowed to stir at room temperature during 20 minutes to allow deprotonation to occur.

[0592] Finally, 50.00 g of C.sub.31 ketone (0.111 mole) was added into the reaction mixture which was allowed to stir at room temperature during one night and during one more day at 35° C. 250 mL of water were then carefully added into the reactor followed by 250 mL of diethyl ether. The organic phase was separated and washed 4 times with 250 mL of water and one time with 200 mL of a saturated aqueous NaCl solution in order to remove pyridinium salts. The aqueous phases were combined and re-extracted with 3 times 250 mL of diethyl ether. The final organic phase was dried over MgSO.sub.4, filtered and evaporated under vacuum to afford 70.08 g of crude orange oil. At this stage the crude contains residual amount of starting ketone as well as a main impurity corresponding to the condensation (aldolisation+crotonisation) of 2 equivalents of ketone.

[0593] The product could be easily purified by dissolving the oil in ethanol (the by-product and the starting ketone being not soluble in ethanol) followed by a filtration over celite.

[0594] The filtrate was evaporated, re-dissolved in CHCl.sub.3, filtered again and evaporated to afford 52.57 g of oil with 95% of purity (RMN).

[0595] The overall purified yield was 79%.

[0596] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 3.68 (s, 6H), 2.32-2.19 (m, 4H), 1.45-1.39 (m, 4H), 1.30-1.10 (m, 48H), 0.81 (t, J=6.4 Hz, 6H).

[0597] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 166.30, 164.47, 123.65, 52.15, 34.61, 32.15, 30.16, 29.92, 29.91, 29.87, 29.76, 29.60, 28.65, 22.92, 14.34 (terminal CH3).

[0598] Transesterification with Dimethylaminoethanol to Afford Diamine Mixtures Intermediates:

##STR00092##

[0599] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0600] Fresh commercial anhydrous toluene and dimethylaminoethanol were used as such.

[0601] In a 2 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser with a distillation apparatus and a temperature probe were added 42.7 g of the internal ketone/dimethyl malonate adduct (75.6 mmol) followed by 50 mL of toluene. The mixture was stirred at room temperature and 30.4 mL of dimethylaminoethanol (26.9 g, 302.2 mmol, 4 eq.) was added to the reaction system followed by 50 mL of toluene. Then 0.9 g of the catalyst dibutyltin oxide (3.8 mmol, 5 mol %) was added to the reaction mixture followed by 200 mL of toluene.

[0602] Then the mixture was allowed to stir at 120° C. and the reaction progress was followed by NMR analysis. To run a proper analysis an aliquot of the reaction medium was sampled and diluted in diethyl ether, quenched with water, decanted and the organic phase was evaporated under vacuum to be analysed in CDCl.sub.3 NMR solvent. After 4 days of stirring at 120° C. NMR analysis showed that the conversion level was around 83% with 91% selectivity. In addition, by-product methanol was also present in the distillation flask. The reaction mixture was then allowed to cool down at room temperature and quenched with 500 mL of water. The medium was decanted and the aqueous phase was extracted with three times of 500 mL of diethyl ether. The organic phases were collected and washed three times with 500 mL of water and one time with 500 mL of a saturated aqueous NaCl solution in order to remove excess of dimethylaminoethanol. The organic phase was then dried over MgSO4, filtered and evaporated to give 47.9 g of a crude dark oil. At this stage the crude contained a residual amount of the starting malonate.

[0603] The product was then purified by flash chromatography on silica gel with a first eluent consisting on CHCl.sub.3/AcOEt mixture going through a gradient from 100% CHCl.sub.3 to 100% AcOEt.

[0604] In order to remove all the product from the column, the column was also flushed with isopropanol+NEt.sub.3 mixture (10% vol NEt.sub.3) allowing getting additional pure product.

[0605] The clean fractions were collected affording, after solvent evaporation, 27.8 g of a pure product corresponding to 54% isolated yield.

[0606] NMR analysis showed that the product was in the form of a mixture of two position isomers with the following ratio: 54 mol % of the isomerized product (cis and trans diastereoisomers) and 46 mol % of methylenated product.

[0607] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 5.45-5.13 (m, 1H: isomer 2 cis+trans), 4.42 (s, 1H, isomer 2 cis or trans), 4.24-4.06 (m, 4H, isomer 1+2), 3.99 (s, 1H, isomer 2 cis or trans), 2.58-2.40 (m, 4H, isomer 1+2), 2.32-2.24 (m, 4H, isomer 1), 2.20 (s, 12H, isomer 1), 2.19 (s, 12H, isomer 2), 2.09-1.89 (m, 4H, isomer 2 cis+trans), 1.45-0.99 (m, 51H, isomer 1+2), 0.81 (t, J=6.8 Hz, 6H).

[0608] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 168.60, 168.41, 165.49, 164.05, 132.07, 131.57, 131.12, 130.77, 123.73, 63.35, 62.76, 58.08, 57.49, 57.45, 53.45, 45.73, 34.45, 30.07, 30.03, 29.72, 29.68, 29.58, 29.53, 29.45, 29.38, 28.46, 28.43, 28.27, 28.09, 22.70, 14.13 (terminal CH.sub.3).

[0609] Methylation to Afford a Mixture of Compounds (V) and (VI):

[0610] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0611] Fresh commercial anhydrous THF and dimethylsulfate were used as such.

[0612] In a 1 L double-jacketed reactor equipped with a mechanical stirrer, a condenser, an addition funnel and a temperature probe were added 100 mL of dry THF and 6.9 mL of dimethylsulfate (9.14 g, 72 mmol, 2 eq.). A solution of 24.6 g of the esteramine (36 mmol, 1 eq.) in 154 mL of THF was preliminary prepared in the addition funnel and was progressively added into the reactor under stirring at room temperature in order to limit the temperature increase. The mixture was then stirred at room temperature under argon and the reaction progress was monitored by NMR analysis. After 2 hours the mixture was brought to 40° C. and 0.2 mL of dimethyl sulfate (2 mmol, 0.06 eq.) were added to allow stirring and to achieve complete conversion.

[0613] Reaction was completed after one hour of stirring at 40° C. and all the volatiles (THF and remaining DMS) were removed under vacuum in order to afford 33.15 g of a 95 mol % purity product as a beige wax with 94% yield.

[0614] NMR analysis showed the presence of 2 position isomers with 55:45 ratio between isomerized derivative (cis and trans diastereoisomers) and conjugated non-isomerized methylenated derivative.

[0615] .sup.1H NMR (MeOD, 400 MHz) δ (ppm): 5.60-5.25 (m, 1H: isomer 2 cis+trans), 4.80 (s, 1H, isomer 2 cis or trans), 4.75-4.50 (m, 4H, isomer 1+2), 4.38 (s, 1H, isomer 2 cis or trans), 3.84-3.72 (m, 4H, isomer 1+2), 3.69 (s, 6H, isomer 1+2), 3.22 (s, 18H, isomer 2), 3.21 (s, 18H, isomer 1), 2.50-2.35 (m, 4H, isomer 1), 2.22-2.02 (m, 4H, isomer 2 cis+trans), 1.60-1.09 (m, 35H, isomer 1+2), 0.90 (t, J=6.8 Hz, 6H).

[0616] .sup.13C NMR (MeOD, 101 MHz) δ (ppm): 169.22, 169.01, 168.96, 165.52, 134.16, 133.22, 132.94, 131.74, 65.90, 65.81, 60.23, 60.18, 59.73, 55.27, 54.66, 54.62, 35.66, 35.54, 33.24, 33.23, 31.76, 31.01, 30.94, 30.91, 30.87, 30.85, 30.77, 30.74, 30.71, 30.66, 30.65, 30.63, 30.60, 29.73, 29.62, 29.45, 29.27, 23.89, 14.61 (terminal CH.sub.3).

Example 4—Synthesis of a Mixture of Quaternary Ammonium Compounds Wherein A is Represented by A-2 or A-3 (a Mixture of Compounds of Formula (V) and (VI)) Starting from C.SUB.23.-12-Triocosanone

[0617] Knoevenagel Condensation to Afford Diester Intermediate:

[0618] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0619] Fresh commercial anhydrous CHCl.sub.3, anhydrous THF and anhydrous pyridine were used as such.

[0620] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser, an addition funnel and a temperature probe were added 48.6 mL of TiCl.sub.4 (84.02 g, 0.443 mole), followed by 146 mL of CHCl.sub.3. The mixture was stirred at −10° C. and anhydrous THF (358 mL) was slowly added through the addition funnel at a rate avoiding a temperature increase of the reaction medium above +5° C. During THF addition, a yellow precipitate appeared. Then 20.4 mL of dimethyl malonate (23.41 g, 0.177 mole) were added into the reaction mixture which was then allowed to stir at room temperature during 1 hour in order to allow malonate complexation to occur.

[0621] Then the mixture was allowed to cool down to 0° C. and a solution of 95.5 mL of anhydrous pyridine (93.44 g, 1.181 mole) in 23 mL of THF was slowly added to the reactor. During addition, the colour of the mixture turned red. The mixture was then allowed to stir at room temperature during 20 minutes to allow deprotonation to occur.

[0622] Finally, 50.00 g of C.sub.23 ketone (0.148 mole) was added to the reaction mixture which was allowed to stir at room temperature during one night and during one more day at 35° C. 250 mL of water were then carefully added into the reactor followed by 250 mL of diethyl ether. The organic phase was separated and washed four times with 250 mL of water and one time with 200 mL of a saturated aqueous NaCl solution in order to remove pyridinium salts. The aqueous phases were collected and re-extracted with three times 250 mL of diethyl ether. The final organic phase was dried over MgSO.sub.4, filtered and evaporated under vacuum to afford 69.5 g of crude orange oil. At this stage the crude contained residual amount of starting ketone as well as a main impurity corresponding to the condensation (aldolisation, crotonisation) of 2 equivalents of ketone.

[0623] The product could be easily purified by dissolving the oil in methanol (the by-product and the starting ketone being not soluble in methanol) followed by a filtration over celite.

[0624] The filtrate was evaporated to afford 54 g of oil with 95% of purity (RMN).

[0625] The overall purified yield was 77%.

[0626] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 3.72 (s, 6H), 2.33-2.29 (m, 4H), 1.48-1.40 (m, 4H), 1.34-1.17 (m, 32H), 0.85 (t, J=6.4 Hz, 6H).

[0627] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 166.28, 164.44, 123.63, 52.14, 34.6, 32.12, 30.13, 29.84, 29.73, 29.58, 29.55, 28.64, 22.90, 14.32 (terminal CH.sub.3).

[0628] Transesterification with Dimethylaminoethanol to Afford Diamine Mixtures Intermediates:

[0629] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0630] Fresh commercial anhydrous toluene and dimethylaminoethanol were used as such.

[0631] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser with a distillation apparatus and a temperature probe was added a solution of 51.1 g of the internal ketone/dimethyl malonate adduct (110 mmol, 1 eq.) in 300 mL of toluene. The mixture was stirred at room temperature and 45.5 mL of dimethylaminoethanol (40.5 g, 450 mmol, 4 eq.) was added to the reaction medium followed by 1.37 g of the catalyst dibutyltin oxide (5.5 mmol, 5 mol %).

[0632] Then the mixture was allowed to stir at 120° C. and the reaction progress was followed by NMR analysis. To run a proper analysis an aliquot of the reaction medium was sampled and diluted in diethyl ether, quenched with water, decanted and the organic phase was evaporated under vacuum to be analysed in CDCl.sub.3 NMR solvent. After 2 days of stirring at 120° C. the mixture was allowed to cool down at room temperature and was concentrated under vacuum. 200 mL of water was then added to the residue followed by 200 mL of diethyl ether. The organic phase was decanted and washed three times with 300 mL of water and one time with 300 mL of a saturated aqueous solution of NaCl in order to remove excess of dimethylaminoethanol. The aqueous phases were collected and re-extracted with 700 mL of diethyl ether. The organic phases were collected and then dried over MgSO4, filtered and evaporated. The residue obtained was re-dissolved in methanol and the precipitated solid was filtered. The filtrate was evaporated to afford 59.04 g of crude yellow oil. At this stage the crude contained residual amount of the starting malonate and some by-products.

[0633] The product was then purified by flash chromatography on silica gel with an eluent consisting on CHCl.sub.3/isopropanol mixture going through a gradient from 100% CHCl.sub.3 to 100% isopropanol.

[0634] The clean fractions were collected, affording after solvent evaporation 22.9 g of a pure product corresponding to 35% isolated yield.

[0635] NMR analysis showed that the product is in the form of 2 position isomers mixture with the following ratio: 60 mol % of the isomerized product (cis and trans diastereoisomers) and 40 mol % of methylenated product.

[0636] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 5.45-5.15 (m, 1H: isomer 2 cis+trans), 4.42 (s, 1H, isomer 2 cis or trans), 4.24-4.08 (m, 4H, isomer 1+2), 3.99 (s, 1H, isomer 2 cis or trans), 2.65-2.40 (m, 4H, isomer 1+2), 2.32-2.24 (m, 4H, isomer 1), 2.20 (s, 12H, isomer 1), 2.19 (s, 12H, isomer 2), 2.10-1.90 (m, 4H, isomer 2 cis+trans), 1.50-0.95 (m, 35H, isomer 1+2), 0.81 (t, J=6.4 Hz, 6H).

[0637] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 168.81, 168.62, 165.71, 164.24, 132.27, 131.78, 131.33, 130.97, 123.95, 63.57, 62.98, 58.29, 57.69, 57.65, 53.71, 45.94, 34.66, 34.28, 32.13, 31.02, 30.23, 29.90, 29.87, 29.78, 29.65, 29.57, 29.55, 28.67, 28.64, 28.47, 28.29, 22.90, 14.33 (terminal CH.sub.3).

[0638] Methylation to Afford Mixture of Compounds V and VI:

[0639] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0640] Fresh commercial anhydrous THF and dimethylsulfate were used as such.

[0641] In a 200 mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser, an addition funnel and a temperature probe were added 100 mL of dry THF and 7.59 mL of dimethylsulfate (10.1 g, 80 mmol, 2 eq.). A solution of 22.94 g of the esteramine (40 mmol, 1 eq.) in 154 mL of THF was preliminary prepared in the addition funnel and was progressively added into the reactor under stirring at room temperature in order to limit the temperature increase. The mixture was then stirred at room temperature under argon and the reaction progress was monitored by NMR analysis. Reaction was completed after one hour of stirring at room temperature and all the volatiles (THF and remaining DMS) were removed under vacuum in order to afford 32.6 g of product as a beige wax with 99% yield.

[0642] NMR analysis showed the presence of two position isomers with 60:40 ratio between isomerized derivative (cis and trans diastereoisomers) and conjugated non-isomerized methylenated derivative.

[0643] .sup.1H NMR (MeOD, 400 MHz) δ (ppm): 5.60-5.25 (m, 1H: isomer 2 cis+trans), 4.80 (s, 1H, isomer 2 cis or trans), 4.75-4.50 (m, 4H, isomer 1+2), 4.38 (s, 1H, isomer 2 cis or trans), 3.84-3.72 (m, 4H, isomer 1+2), 3.69 (s, 6H, isomer 1+2), 3.22 (s, 18H, isomer 2), 3.21 (s, 18H, isomer 1), 2.50-2.35 (m, 4H, isomer 1), 2.22-2.02 (m, 4H, isomer 2 cis+trans), 1.60-1.09 (m, 35H, isomer 1+2), 0.90 (t, J=6.8 Hz, 6H).

[0644] .sup.13C NMR (MeOD, 101 MHz) δ (ppm): 169.22, 169.01, 168.96, 165.52, 134.16, 133.22, 132.94, 131.74, 65.90, 65.81, 60.23, 60.18, 59.73, 55.27, 54.66, 54.62, 35.66, 35.54, 33.24, 33.23, 31.76, 31.01, 30.94, 30.91, 30.87, 30.85, 30.77, 30.74, 30.71, 30.66, 30.65, 30.63, 30.60, 29.73, 29.62, 29.45, 29.27, 23.89, 14.61 (terminal CH.sub.3).

Example 5—Synthesis of a Compound Wherein a is Represented by A-1, Specifically a Compound of Formula VII Starting from C.SUB.23 .12 Tricosanone

[0645] Reductive Amination to Afford Primary Amine

##STR00093##

[0646] All the reactions were conducted under an inert argon atmosphere.

[0647] In a 5 L three necked round bottom flask equipped with a magnetic stirrer, a condenser, a temperature probe and a heater a solution of tricosan-12-one (100 g, 0.295 mol, 1 eq.) in 700 mL of methanol was prepared.

[0648] Then NH.sub.4OAc (227.386 g, 2.95 mol, 10 eq.) followed by NaCNBH.sub.3 (74.15 g, 1.18 mol, 4 eq.) are added to the mixture in small portions. The reaction medium was stirred at room temperature for 1 hour. Finally, the mixture was heated under reflux during 16 hours. Then the reaction medium was cooled down to room temperature and concentrated under vacuum.

[0649] Finally, 500 mL of a saturated NaHCO.sub.3 aqueous solution and 500 mL of methyl tert. butyl ether (MTBE) were added to the residue and the mixture was stirred at room temperature for one hour. Concentrated aqueous NaOH solution was added in order to adjust the pH to about 9. The product was extracted with MTBE and the organic phase was washed several times with water and brine. The organic phase was dried with K.sub.2CO.sub.3, filtered and concentrated in vacuum to afford 100.4 g of crude yellow oil.

[0650] The crude was then purified through flash chromatography column over silica gel using dichloromethane (DCM):methanol mixture as the eluent with a gradient going from DCM:MeOH=100:1 to DCM:MeOH=10:1+1% Et.sub.3N. After solvent evaporation 93.5 g (0.275 mol) of pure light yellow oil was obtained.

[0651] Yield: 93%

[0652] Alkylation of Primary Amine to Afford Amino-Diester Intermediate

##STR00094##

[0653] The reaction was carried out under an inert argon atmosphere.

[0654] In a 1 L round bottom flask equipped with a condenser, a temperature probe, a magnetic stirrer and a heater were added: 62.0 g (0.18 mol, 1 eq.) of the C.sub.23 fatty primary amine. 700 mL of methyl-THF. 63.7 g of methyl 2-chloroacetate (0.59 mol, 3.3 eq.).

[0655] 81.5 g of K.sub.2CO.sub.3 (0.59 mol, 3.3 eq.). 97.94 g of KI (0.59 mol, 3.3 eq.).

[0656] The mixture was then allowed to stir at reflux (78-80° C.) during one night.

[0657] At the end of the reaction the mixture was filtered and concentrated under vacuum to give 98.0 g of crude material that still contained methyl 2-chloroacetate.

[0658] The product was then purified by flash chromatography over silica gel using petroleum ether:ethyl acetate mixture (50:1) as the eluent to afford after solvent evaporation 52 g of pure material (0.108 mol).

[0659] Yield: 60%

[0660] Ester Hydrolysis to Afford Iminodiacetic Acid Intermediate.

##STR00095##

[0661] In a 2 L round bottom flask equipped with a magnetic stirrer were added:

[0662] 27.3 g of NaOH (0.683 mol, 6.0 eq.)

[0663] 300 mL of water

[0664] 300 mL of methanol

[0665] 300 mL of THF

[0666] The solution obtained was then allowed to stir at 0° C. and 55 g of the amino-diester (0.113 mol, 1 eq.) were slowly added.

[0667] The reaction medium was then stirred at room temperature overnight.

[0668] At the end of the reaction, the pH was adjusted from 11 to 1 by the addition of concentrated HCl solution and the product was extracted using two times 3 L of dichloromethane.

[0669] The organic phases were collected and washed several times with brine, dried over MgSO.sub.4, filtered and the solvent was evaporated under vacuum to afford 55 g of product which was used as such for the next step.

[0670] Quantitative Yield

[0671] Esterification with dimethylaminoethanol to afford diester intermediate

##STR00096##

[0672] The reaction was carried out under an inert argon atmosphere.

[0673] In a 2 L round bottom flask equipped with a magnetic stirrer were added:

[0674] 53.3 g (0.117 mol, 1 eq.) of the iminodiacetic acid intermediate

[0675] 2 L of dichloromethane

[0676] 104.2 g of dimethylaminoethanol (1.17 mole, 10 eq.)

[0677] 142 g of trimethylamine (1.40 moles, 12 eq.)

[0678] 189.7 g of HOBt (1.40 moles, 12 eq.)

[0679] The mixture was allowed to cool down to 0° C. and 220 g of EDCl (1.15 moles, 10 eq.) were added into the reaction vessel.

[0680] The mixture was allowed to stir at room temperature during twenty hours allowing the reaction to reach completion.

[0681] The reaction mixture was then washed with water and the organic phase was dried over MgSO.sub.4, filtered and evaporated under vacuum to afford 118 g of crude product as dark yellow oil.

[0682] The crude material was then purified through flash chromatography over silica gel using first petroleum ether:CH2Cl2 mixture (9:1) as the eluent and then CH.sub.2Cl.sub.2:isopropanol (50:1)+1.5% NEt.sub.3 mixture.

[0683] Two fractions were obtained: a first fraction containing 31.0 g of product and a second fraction containing 35 g of material.

[0684] The second fraction was then purified a second time to afford 29.2 g of deep yellow oil.

[0685] Overall 60.2 g (101 mmoles) of pure product were obtained as a yellow oil.

[0686] Yield: 86%

[0687] Quaternization to Obtain Compound of Formula (VII)

[0688] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0689] Fresh commercial anhydrous THF and dimethylsulfate were used as such.

[0690] In a 200 mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser, an addition funnel and a temperature probe were added 100 mL of dry THF and 8.0 mL of dimethylsulfate (10.6 g, 84 mmol, 2 eq.). A solution of 25.2 g of the esteramine (42 mmol, 1 eq.) in 154 mL of THF was prepared in the addition funnel and was progressively added to the reactor under stirring at room temperature in order to limit the temperature increase. The mixture was then stirred at room temperature under argon and the reaction progress was monitored by NMR analysis. Reaction was completed after one hour of stirring at room temperature and all the volatiles (THF and remaining DMS) were removed under vacuum in order to afford 35.7 g of product as a beige wax in quantitative yield.

[0691] .sup.1H NMR (MeOD, 400 MHz) δ (ppm): 4.59-4.50 (m, 4H), 3.78-3.71 (m, 4H), 3.68 (s, 6H), 3.59-3.51 (brs, 4H), 3.25 (s, 18H), 2.68-2.54 (m, 1H), 1.60-1.00 (m, 40H), 0.90 (t, J=6.4 Hz, 6H).

[0692] .sup.13C NMR (MeOD, 101 MHz) δ (ppm): 173.02, 66.13, 65.49, 59.35, 55.26, 54.69, 54.34, 33.23, 32.82, 31.04, 30.95, 30.93, 30.91, 30.63, 28.27, 23.89, 14.61 (terminal CH.sub.3).

Example 6—Synthesis of a Compound Wherein a is Represented by A-1, Specifically a Compound of Formula VII Starting from C.SUB.31 .16-Hentriacontanone

[0693] Reductive Amination to Afford Primary Amine.

[0694] Same protocol as described in Example 5 above for the C.sub.23 derivative was followed.

[0695] Alkylation of Primary Amine to Afford Amino-Diester Intermediate.

[0696] The reaction was carried out under an inert argon atmosphere.

[0697] In a 500 mL round bottom flask equipped with a condenser, a temperature probe, a magnetic stirrer and a heater were added:

[0698] 18.0 g (40 mmoles, 1 eq.) of the C.sub.31 fatty primary amine.

[0699] 500 mL of methyl-THF.

[0700] 12.48 g of methyl 2-chloroacetate (132 mmoles, 3.3 eq.).

[0701] 18.24 g of K.sub.2CO.sub.3 (132 mmoles, 3.3 eq.).

[0702] 21.92 g of KI (132 mol, 3.3 eq.).

[0703] The mixture was then allowed to stir at reflux (78-80° C.) during one night.

[0704] At the end of the reaction the mixture was filtered over a plug of celite. The solid was washed with THF and the filtrate was concentrated under vacuum to afford a crude material that still contained methyl 2-chloroacetate.

[0705] The product was then purified by flash chromatography over silica gel using petroleum ether:ethyl acetate mixture (100:1) as the eluent to afford after solvent evaporation 22.4 g of pure material (37.6 mmoles).

[0706] Yield: 94%

[0707] Ester Hydrolysis to Afford Imino-Diacetic Acid Intermediate.

[0708] In a 1 L round bottom flask equipped with a magnetic stirrer were added:

[0709] 11.3 g of NaOH (0.282 mol, 6.0 eq.)

[0710] 100 mL of water

[0711] 100 mL of methanol

[0712] 100 mL of THF

[0713] The solution obtained was then allowed to stir at 0° C. and 28 g of the amino-diester (0.047 mol, 1 eq.) was slowly added.

[0714] The reaction medium was then stirred at room temperature overnight.

[0715] At the end of the reaction, the pH was adjusted from 11 to 2 by the addition of 1M HCl aqueous solution and the product was extracted using dichloromethane.

[0716] The organic phases were collected and washed several times with brine and finally concentrated. The residue was redissolved in THF and the organic solution was dried over MgSO.sub.4, filtered and the solvent was evaporated under vacuum to afford 26 g of product (45.8 mmoles) which was used as such for the next step.

[0717] Yield: 97%.

[0718] Esterification with Dimethylaminoethanol to Afford Diester Intermediate.

[0719] Same protocol as described in Example 5 for the C.sub.23 derivative was followed.

[0720] Quaternization to Obtain Compound of Formula VII

[0721] Same protocol as described in Example 5 for the C.sub.23 derivative was followed.

[0722] .sup.1H NMR (MeOD, 400 MHz) δ (ppm): 4.52-4.36 (m, 4H), 3.71-3.61 (m, 4H), 3.58 (s, 6H), 3.46-3.39 (brs, 4H), 3.15 (s, 18H), 2.58-2.39 (m, 1H), 1.60-1.00 (m, 56H), 0.80 (t, J=6.8 Hz, 6H).

[0723] .sup.13C NMR (MeOD, 101 MHz) δ (ppm): 173.09, 66.09, 65.23, 59.31, 55.25, 54.69, 54.29, 33.25, 32.82, 31.03, 30.99, 30.96, 30.91, 30.87, 30.66, 28.24, 28.13, 23.91, 14.68 (terminal CH.sub.3).

Example 7—Synthesis of a Compound of Formula (VIII) Starting from 16-Hentriacontanone

[0724] Reductive Amination to Afford Aminodiol Intermediate

##STR00097##

[0725] The reaction was conducted under an inert argon atmosphere.

[0726] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser and a temperature probe were added:

[0727] 50 g of 16-hentriacontanone (111 mmoles, 1 eq.)

[0728] 281 mL of CHCl.sub.3

[0729] 17.73 mL of 3-amino-1,2-propanediol (20.8 g, 222 mmoles, 2 eq.)

[0730] The mixture was then stirred at room temperature and 54.71 mL of Ti(OEt).sub.4 (59.52 g, 222 mmoles, 2 eq.) was added into the reactor. The mixture was then stirred at 65° C. overnight and it was observed that during the course of the reaction the mixture became homogeneous.

[0731] At the end of the reaction, the temperature was cooled down to 40° C. and 56 mL of anhydrous methanol was added into the reactor followed by the careful and slow addition of 8.74 g of NaBH.sub.4 (222 mmoles, 2 eq.). Care was taken to avoid foaming during NaBH.sub.4 addition.

[0732] The reaction medium was then stirred at 40° C. during three hours.

[0733] Then the mixture was cooled down to room temperature and 100 mL of water were added followed by 100 mL of diethyl ether. During water addition precipitation of TiO.sub.2 occurred.

[0734] The suspension was filtered, the solid was washed several times with diethyl ether and the biphasic filtrate was separated. The organic phase was again filtered over celite and was washed with water and brine. The organic phase was then dried over MgSO.sub.4, filtered and evaporated to afford the crude material as a yellow paste (48.9 g).

[0735] The crude was then purified through flash chromatography over silica gel using CHCl.sub.3:isopropanol mixture as the eluent with a gradient going from 100:0 to 50:50.

[0736] After solvent evaporation 28.75 g of pure product was obtained (54.70 mmoles).

[0737] Yield: 49%

[0738] .sup.1H NMR (MeOD, 400 MHz) δ (ppm): 3.78-3.64 (m, 1H), 3.62-3.42 (m, 2H), 2.78 (dd, J=11.6 Hz, J=3.6 Hz, 1H), 2.62-2.40 (m, 2H), 1.70-1.11 (m, 56H), 0.90 (t, J=6.4 Hz, 6H).

[0739] .sup.13C NMR (MeOD, 101 MHz) δ (ppm): 71.78, 66.46, 59.03, 51.08, 34.67, 33.26, 31.08, 31.04, 30.97, 30.95, 30.92, 30.83, 30.80, 30.66, 26.87, 26.85, 23.91, 14.62 (terminal CH.sub.3).

[0740] Esterification with Glycine Betaine to Afford Quaternary Ammonium Compound of Formula VIII

[0741] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0742] Commercial anhydrous THF, anhydrous toluene and anhydrous CHCl3 stabilized with amylene were used as such.

[0743] Glycine betaine hydrochloride was dried through several washings with anhydrous THF followed by drying under vacuum prior to use.

[0744] In a 250 mL four necked round bottom flask equipped with a condenser, a distillation apparatus connected to a NaOH trap, a temperature probe, a magnetic stirrer and a heater were added:

[0745] 7.13 g of betaine hydrochloride (46.4 mmol)

[0746] 10 mL of SOCl.sub.2 (16.38 g, 136.9 mmol) was then carefully introduced into the reactor vessel and the resulting suspension was progressively heated to 70° C. under stirring. It was observed that when the temperature reached 68° C., gas was released (SO.sub.2 and HCl) and the mixture turned homogeneously yellow.

[0747] The mixture was then allowed to stir at 70° C. during two hours and hot anhydrous toluene (25 mL, 80° C.) was added into the vessel. The mixture was stirred and decanted at 0° C. to make the betainyl chloride precipitate. The upper phase of toluene was then removed through cannula and the operation of toluene washing was repeated four times in order to remove all SOCl.sub.2 excess.

[0748] NMR analysis showed complete conversion of glycine betaine hydrochloride but also formation of NMe.sub.3.HCl adduct (NMe.sub.3.HCl content in the solid: 19.3 mol %).

[0749] 20 mL of CHCl.sub.3 was then added to the solid betainyl chloride.

[0750] A solution of the fatty diol (9.85 g, 18.7 mmol) in 30 mL of CHCl.sub.3 was then prepared and was added dropwise to the betainyl chloride/CHCl.sub.3 suspension at −3° C. at a rate avoiding the temperature of the reaction medium to go above 5° C. At the end of the addition the mixture was allowed to warm-up at room temperature and was then stirred at 50° C. for the night.

[0751] All the volatiles were then removed under vacuum at 30° C. to afford 16 g of a beige wax.

[0752] NMR analysis showed that the purity of the resulting product is around 73 wt % (the remaining by-products are: protonated starting alcohol, NMe.sub.3.HCl, betaine hydrochloride and mono-ester).

[0753] Yield: 75% (14 mmoles)

[0754] .sup.1H NMR (CDCl.sub.3-MeOD, 400 MHz) δ (ppm): 5.55-5.63 (m, 1H), 4.93 (d, J=16.8 Hz, 1H), 4.92 (d, J=16.8 Hz, 1H), 4.81 (d, J=16.8 Hz, 1H), 4.70 (d, J=16.8 Hz, 1H), 4.49 (dd, J=12 Hz, J=3.6 Hz, 1H), 4.39 (dd, J=12 Hz, J=6.4 Hz, 1H), 3.36 (s, 9H), 3.33 (s, 9H), 3.32-3.28 (m, 2H), 1.80-1.45 (m, 4H), 1.45-1.10 (m, 52H), 0.84 (t, J=6.8 Hz, 6H).

[0755] .sup.13C NMR (MeOD, 101 MHz) δ (ppm): 166.06, 71.18, 65.29, 64.59, 64.28, 61.35, 54.99, 54.87, 45.99, 45.55, 33.24, 30.96, 30.93, 30.91, 30.80, 30.64, 30.61, 30.60, 26.34, 26.21, 23.89, 14.61 (terminal CH.sub.3).

Example 8—Synthesis of a Quaternary Ammonium Compound Wherein a is Represented by A-5 and Corresponding to Formula (IX) Starting from C.SUB.31 .16-Hentriacontanone

[0756] C.sub.31 internal olefin was obtained from palmitic acid according to the protocol described in U.S. Pat. No. 10,035,746, example 4.

[0757] Epoxidation of Internal Olefin to Fatty Epoxide

##STR00098##

[0758] The reaction was conducted under an inert argon atmosphere.

[0759] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser, an addition funnel and a temperature probe were added 61.9 g of C.sub.31 alkene (0.142 mol), followed by 16.3 mL (17.1 g, 0.285 mol) of acetic acid and 13.6 g (22 wt %) of Amberlite® IR 120H resin. The mixture was heated to 65° C. to melt the fatty alkene. The agitation was started and then 21.8 mL (24.2 g, 0.214 mol) of an aqueous solution of H.sub.2O.sub.2 (conc. 30%) was slowly added to the mixture using the addition funnel at a rate avoiding a significant temperature increase. This required about one hour. The temperature was then increased to 75° C. and the reaction mixture was allowed to stir overnight (after 15 min, NMR analysis showed that the conversion level was already around 60% with 99% selectivity). Then additional 10.2 mL (11.3 g, 0.1 mol) of an aqueous solution of H.sub.2O.sub.2 (30%) was added slowly and after 4 hours following the second addition of H.sub.2O.sub.2 NMR analysis showed that the conversion level was around 88% (98% selectivity). Another addition of 8.14 mL of acetic acid (8.55 g, 0.142 mol) followed by 11.6 mL of 30% H.sub.2O.sub.2 (12.91 g, 0.114 mol) was finally performed in order to increase the conversion level.

[0760] The mixture was allowed to stir a second night at 75° C.

[0761] Finally NMR analysis showed a conversion level of 93% (95% selectivity).

[0762] The mixture was allowed to cool down to room temperature and then 300 mL of chloroform were added. The mixture was transferred to a separating funnel and the organic phase was washed three times with 300 mL of water and then the aqueous phase was extracted twice with 100 mL of chloroform. The Amberlite® solid catalyst stayed in the aqueous phase and was removed during the first separation with the aqueous phase. The organic phases were collected, dried over MgSO.sub.4, filtered and evaporated to give 65.3 g of a white solid with a purity of 91% w/w (epoxide+di-alcohol).

[0763] The yield taking into account the purity was 92%.

[0764] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 2.91-2.85 (m, 2H, diastereoisomer 1), 2.65-2.6 (m, 2H, diastereoisomer 2), 1.53-1.00 (m, 54H), 0.86 (t, J=6.8 Hz, 6H).

[0765] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 58.97, 57.28, 32.18, 31.96, 29.72, 29.6, 29.4, 27.86, 26.95, 26.63, 26.09, 22.72, 14.15 (terminal CH.sub.3).

[0766] Hydrolysis of Fatty Epoxide to Afford Fatty Diol

##STR00099##

[0767] The reaction was conducted under an inert argon atmosphere.

[0768] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser and a temperature probe were added 82.9 g of C.sub.31 epoxide (purity: 94.5 wt %, 0.174 mol) followed by 480 mL of methyl-THF.

[0769] The mixture was allowed to stir at room temperature and 73 mL of a 3 M aqueous solution of H.sub.2SO.sub.4 was then added. The reaction medium was then stirred at 80° C. during 90 minutes. NMR analysis showed that the reaction was completed. The biphasic mixture was allowed to cool down to room temperature and the organic phase was separated. The solvent was then removed under vacuum and the residue was suspended in 200 mL of diethyl ether. The suspension was filtered and the resulting solid was washed 3 times with 50 mL of diethyl ether. The white solid was finally washed 2 times with 50 mL of methanol and was dried under vacuum to remove traces of solvent.

[0770] At the end 75.53 g of product was obtained as a white powder with a purity of 95.7% w/w corresponding to a yield of 89%.

[0771] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 3.61-3.55 (m, 2H, diastereoisomer 1), 3.43-3.25 (m, 2H, diastereoisomer 2), 1.88 (brd, J=2.4 Hz, OH, diastereoisomer 2), 1.72 (brd, J=3.2 Hz, OH, diastereoisomer 1), 1.53-1.10 (m, 54H), 0.86 (t, J=6.8 Hz, 6H).

[0772] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 74.71, 74.57, 33.66, 31.96, 31.23, 29.71, 29.39, 26.04, 25.68, 22.72, 14.15 (terminal CH.sub.3)

[0773] Esterification of Fatty Diol with Trimethylglycine to Afford Compound of Formula IX

[0774] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0775] Fresh commercial anhydrous CHCl.sub.3 (amylene stabilized) and anhydrous toluene were used as such.

[0776] Betaine hydrochloride (19.66 g, 128.4 mmoles) was washed ten times with 20 mL of anhydrous THF followed by drying under vacuum to remove traces of solvent prior to use.

[0777] In a 100 mL four-neck round-bottom flask equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and a curved distillation column connected to two traps of NaOH were quickly added: 19.66 g of dried betaine hydrochloride (128.4 mmoles) and 28 mL of SOCl.sub.2 (45.86 g, 0.386 mol).

[0778] The heterogeneous mixture was stirred and the temperature was then slowly increased to 70° C. It was observed that when the temperature reached 68° C., gas was released (SO.sub.2 and HCl) and the mixture turned homogeneous yellow.

[0779] The mixture was then allowed to stir at 70° C. during two hours and hot anhydrous toluene (25 mL, 80° C.) was added into the vessel. The mixture was stirred and then decanted at 0° C. (white-yellow precipitate formation) and the upper phase of toluene was removed through a cannula. The operation of toluene washing was repeated seven times in order to remove all SOCl.sub.2 excess. NMR analysis showed complete conversion of glycine betaine hydrochloride but also formation of NMe.sub.3.HCl adduct (NMe.sub.3.HCl content in the solid: 12.3 mol %).

[0780] 20 mL of dry CHCl.sub.3 was then added to the solid betainyl chloride.

[0781] A solution of 26.19 g (56 mmol) of fatty diol in 90 mL of anhydrous CHCl.sub.3 was prepared at 55° C. and was added dropwise under stirring to the reaction vessel at room temperature (exothermicity and emission of HCl was observed). The mixture was then allowed to stir at 55° C. overnight. Over the course of the reaction, the mixture turned homogeneously orange. NMR analysis showed that the conversion level was around 100%.

[0782] The mixture was then allowed to cool down to room temperature and the solvent was evaporated under vacuum.

[0783] The residue was solubilized in methanol at 0° C. and the formed precipitate was filtered out. The obtained filtrate was then evaporated to give 39.7 g of crude product.

[0784] This product was then deposited on a sinter filter and washed with cyclohexane to remove some remaining organic impurities. The resulting washed solid was dried under vacuum to afford 22 g of crude material. A final purification with a mixture of CH.sub.2Cl.sub.2/cyclohexane 50:50 was carried out; the solid was solubilized again in this solvent mixture at 50° C. and was allowed to cool down to room temperature. The formed precipitate was filtered out and after evaporation of the filtrate 19 g of a beige wax was obtained with the following composition:

[0785] 95 wt % of glycine betaine diester

[0786] 1.5 wt % of methyl betainate

[0787] 2 wt % of trimethylamine hydrochloride

[0788] 1.5 wt % of glycine betaine hydrochloride.

[0789] The purified yield was 44%.

[0790] .sup.1H NMR (MeOD-d4, 400 MHz) δ (ppm): 5.3-5.2 (m, 2H), 4.68 (d, J=16.8 Hz, 2H), 4.50 (d, J=16.8 Hz, 2H), 4.53 (s, 1H), 4.48 (s, 1H), 3.37 (s, 18H), 1.75-1.55 (m, 4H), 1.39-1.10 (m, 50H), 0.9 (t, J=6.8 Hz, 6H).

[0791] .sup.13C NMR (MeOD-d4, 101 MHz) δ (ppm): 164.58, 75.76, 62.43, 53.10, 31.68, 30.05, 29.41, 29.38, 29.33, 29.28, 29.15, 29.09, 28.96, 24.71, 22.34, 13.05 (terminal CH.sub.3).

Example 9—Evaluation of Adsorption Properties on Nanocellulose Crystals

[0792] Adsorption of cationic surfactant on negatively charged surface is an important property for various applications. This property is linked to the minimal concentration of cationic surfactant needed to produce aggregation of negatively charged cellulose nano crystal (CNC) in suspension in aqueous media. Comparison of the aggregate size can be monitored by dynamic light scattering (DLS).

[0793] Following the protocol described in literature (Ref.: E. K. Oikonomou, et al., J. Phys. Chem. B, 2017, 121 (10), pp 2299-2307), adsorption properties of quaternary ammonium were investigated by monitoring the ratio X=[surfactant]/[CNC] or the mass fraction M=[surfactant]/([surfactant]+[CNC]), at fixed [surfactant]+[CNC]=0.01 wt % in aqueous solution, required to induce the agglomeration of the cellulose nano crystal.

[0794] The range of CNC aggregation correspond to the range of ratio X (or M) triggering an aggregation of CNC, i.e. the range where the aggregate size measured by DLS is higher than a pure aqueous solution of CNC or an aqueous solution of surfactant at 0.01 wt %.

[0795] Ranges of X and M of aggregation of CNC are summarized in Table 1. The lower range of aggregation X or M, the better the adsorption properties on negatively charged surface

TABLE-US-00001 TABLE 1 Range of CNC Range of CNC aggregation (Ratio) aggregation (Mass X = [surfactant]/[CNC] fraction) Compound of X.sub.min − X.sub.max M.sub.min − M.sub.max Fentacare® TEP .sup.1 1-33 0.50-0.97 Example 1 0.1-1.82 0.09-0.65 Example 3 0.1-1.82 0.09-0.65 Example 4 0.9-1.1  0.47-0.52 .sup.1 Fentacare ® TEP was used as a comparison. Fentacare ® TEP is a commercial surfactant representing the benchmark.

[0796] The data show that the surfactant properties of the compounds in accordance with the present invention are superior compared to the commercial surfactant Fentacare® TEP.

[0797] The properties of the compounds of Examples 2 and 5 to 8, as far as adsorption of cellulose nanocrystals is concerned are similar to the properties of the compounds of Examples 1, 3 and 4 for which values are given in Table 1.

Example 10—Determination of Biodegradability

[0798] Biodegradability of the test substances has been measured according to the 301 F OECD protocol.

[0799] A measured volume of inoculated mineral medium, containing a known concentration of the test substance in order to reach about 50 to 100 mg ThOD/l (Theoretical Oxygen Demand) as the nominal sole source of organic carbon, was stirred in a closed flask (OxitopTmrespirometric flask) at a constant temperature (20±2° C.) for up to 28 days. Oxitop™ respirometric bottles were used in this test in order to access the biodegradability of the test samples: sealed culture BOD flasks were used at a temperature of 20±2 C during 28 days.

[0800] Evolved carbon dioxide was absorbed by pellets of Natrium or Potassium hydroxide present in the head space of the bottle. The amount of oxygen taken up by the microbial population (=oxygen consumption expressed in mg/l) during biodegradation process (biological oxidation of the test substance) decreased the pressure of the head space (A P measured by the pressure switch) and was mathematically converted in mg O.sub.2 consumed/litre. Inoculum corresponded to a municipal activated sludge washed in mineral medium (ZW media) in order to decrease the DOC (Dissolved Oxygen Carbon) content. Control solutions containing the reference substance sodium acetate and also toxicity control (test substance+reference substance) were used for validation purposes. Reference substance, sodium acetate, has been tested in one bottle (at a nominal concentration of 129 mg/l corresponding to 100 mg ThOD/l) in order to check the viability of the inoculum. Toxicity control corresponds to the mixture of the substance reference and the test substance; it will check if the test substance is toxic towards the inoculum (if so, the test has to be redone at a lower test substance concentration, if feasible regarding the sensitivity of the method).

[0801] As the substances of the present invention are for a majority of them not very soluble in water (if some are soluble in water, their metabolite after hydrolysis containing the alkyl chain has often very low solubility in water), we used a specific protocol named the “emulsion protocol”. This protocol enabled us to increase the bioavailability of the poorly water soluble substance in the aqueous phase where we had the inoculum.

[0802] Emulsion protocol consisted of adding the test substance in the bottle through a stock solution made in an emulsion.

[0803] Emulsion was a 50/50 v/v mixture of a stock solution of the test substance dissolved in a non-biodegradable surfactant (Synperonic® PE 105 at 1 g/l) and then mixed with a mineral silicone oil AR 20 (Sigma).

[0804] The first dissolution of the test substance in the non-biodegradable surfactant solution often required magnetic stirrer agitation followed by ultrasonication.

[0805] Once the dissolution was made, we mixed the aqueous solution with a mineral silicone oil at a 50/50 volume/volume ratio. This emulsion was maintained by magnetic stirrer agitation and was sampled for an addition in the corresponding bottle in order to reach the required test substance concentration.

[0806] Two emulsion controls were run in parallel during the test in order to remove their value from the emulsion bottle containing the test substance added through the emulsion stock solution.

[0807] The results of the biodegradability test are summarized in Table 2

TABLE-US-00002 Compound of Biodegradability after 28 days Example 2  0% (OECD 301F) Example 3 17% (OECD 301D) Example 7 15% (OECD 301F) Example 8 92% (OECD 301F)

[0808] The results show that the compound of example 8 has the best biodegradability amongst the compounds used in the working examples, i.e. the biodegradablity of compounds in accordance with the present invention wherein A is represented by A-5 and specifically the compounds of formula IX is higher than for other compounds. This beneficial effect is achieved without detrimentally affecting the surfactant properties of the compounds.

Example 11—Synthesis of a Quaternary Di-Ammonium Compound Starting from 16-Hentriacontanone

[0809] 16-hentriacontanone was purchased from TCI, but could have been obtained from palmitic acid following Piria ketonization protocol described in US 2018/0093936.

[0810] Hydrogenation of 16-Hentriacontanone to 16-Hentriacontanol

[0811] In a 100 mL autoclave equipped with a mechanical stirrer (Rushton turbine) were added: [0812] 4.36 g of Ru/C (4.87% Ru) catalyst (5 wt % of dry catalyst with respect to the ketone, catalyst containing 54.9% H.sub.2O) [0813] 39.3 g (87.2 mmol) of melted C.sub.31 ketone.

[0814] The reaction was performed under 20 bar hydrogen pressure. 4 nitrogen purges are performed followed by 3 purges of hydrogen at 20 bars. The temperature of the reaction mixture was then set at 100° C. to melt the ketone substrate. The temperature was left at 100° C. during 10 min and stirring was slowly started at 200 rpm. When proper stirring was confirmed, the stirring rate was increased at 1200 rpm and the temperature was set at 150° C.

[0815] After 6 h reaction time at 150° C., heating was stopped and the mixture was allowed to cool down at 90° C. while stirring. Stirring was then stopped. The mixture was cooled down to room temperature and the autoclave was carefully depressurized.

[0816] NMR analysis in CDCl.sub.3 of the crude showed a ketone conversion level >99% and molar purity of 99% for the fatty alcohol. The compact solid containing the product and the catalyst was grounded to powder and then introduced into a 1 L flask. 500 mL of chloroform were added and the flask was then heated at 60° C. to dissolve completely the alcohol. The suspension was filtered at 60° C. over celite. The solid cake was rinsed with hot chloroform at 60° C. several times. The filtrate was evaporated to give 35.6 g (78.7 mmol) of white powder with a weight purity around 99% for the desired C.sub.31 fatty alcohol corresponding to 90% isolated yield.

[0817] Dehydration of 16-Hentriacontanol to Internal Olefin

[0818] The reaction was conducted under an inert argon atmosphere. In a 200 mL quartz reactor equipped with a heating mattress, a mechanical stirrer (A320-type stirring mobile manufactured by 3D-printing with Inox SS316L), a condenser connected to a 50 mL two-neck distillate collection flask and a temperature probe were added: [0819] 56.1 g of C.sub.31 fatty alcohol (124 mmol, 1 eq.) [0820] 5.61 g (10 wt %) of Al.sub.2O.sub.3-η.

[0821] The temperature of the reaction media was then increased to 150° C. to melt the alcohol and stirring was started (about 500 rpm). Finally the temperature was set-up at 300° C. and the mixture was allowed to stir at 1000 rpm under argon. Reaction progress was monitored thanks to NMR analysis with a borosilicate glass tube.

[0822] After 2 hours reaction at 300° C., NMR analysis in CDCl.sub.3 showed complete conversion of the fatty alcohol and the presence of 1.5 mol % ketone which had been formed as a by-product.

[0823] Stirring and heating were then stopped. The temperature was lowered to 80° C. and the molten crude was transferred to a beaker. The reactor vessel and the stirring mobile were rinsed with chloroform (Al.sub.2O.sub.3 is insoluble). The suspension was filtered and the solvent was evaporated under vacuum to afford 52.24 g (120.2 mmol) of transparent oil which became a white solid (99 wt % purity) at room temperature corresponding to 97% isolated yield (NMR).

[0824] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 5.38-5.29 (m, 2H), 2.03-1.93 (m, 4H), 1.35-1.19 (m, 48H), 0.86 (t, J=6.8 Hz, 6H).

[0825] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 130.6, 130.13, 32.84, 32.16, 30.01, 29.93, 29.8, 29.6, 29.55, 29.4, 22.93, 14.35 (terminal CH.sub.3).

[0826] Epoxidation of Internal Olefin to Oxirane

[0827] The reaction was conducted under an inert argon atmosphere. In a double-jacketed 1 L reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser and a temperature probe were added 92.4 g of C.sub.31 alkene (0.212 mol), followed by 18.2 mL (19.1 g, 0.319 mol) of acetic acid and 27.7 g (30 wt %) of Amberlite® IR 120H resin.

[0828] The mixture was heated to 75° C. in order to melt the fatty alkene. The agitation was then started and 32.6 mL (36.1 g, 0.319 mol) of aqueous H.sub.2O.sub.2 30% were slowly added into the mixture using an addition funnel while reaction mass temperature was monitored to avoid temperature increase. The addition required about one hour.

[0829] After the end of H.sub.2O.sub.2 addition, the temperature was increased to 85° C. and reaction progress was followed thanks to NMR analysis. After 4 hours reaction time, the olefin conversion level was >99% with around 99% selectivity toward the desired epoxide (trace amounts of valuable diol were also formed during the reaction).

[0830] Heating was then stopped and 300 mL of chloroform were added to the reaction vessel when the temperature was around 50° C. The mixture was transferred to a separating funnel. The organic phase was washed 3 times with 300 mL of water. Then, the aqueous phase was extracted twice with 100 mL of chloroform. Amberlite® resin was removed during phase separation with the aqueous phase. The organic phase was dried over MgSO.sub.4, filtered and evaporated to give 95.3 g of a white solid with a purity of 98% w/w (epoxide+diol). The yield taking into account the purity was 97%.

[0831] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 2.91-2.85 (m, 1.5H), 2.65-2.6 (m, 0.5H), 1.53-1.36 (m, 4H), 1.35-1.19 (m, 48H), 0.86 (t, J=6.8 Hz, 6H).

[0832] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 58.97, 57.28, 32.18, 31.96, 29.72, 29.6, 29.4, 27.86, 26.95, 26.63, 26.09, 22.72, 14.15 (terminal CH.sub.3).

[0833] Condensation with Chloroacetic Acid (with H.sub.2SO.sub.4 as an Optional Catalyst)

[0834] The reaction was conducted under an inert argon atmosphere in a 500 mL three necked round bottom flask equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and an insulated addition funnel. In the round bottom flask itself were added 128.7 g of chloroacetic acid (1.35 moles, 8 eq). In the insulated addition funnel maintained at 65° C. were added 77.8 g of melted fatty epoxide (98 wt % purity, 0.169 moles, 1 eq).

[0835] The first step of intermediate hydroxyl-ester formation was conducted at 65° C. by the slow addition of the fatty epoxide into chloroacetic acid in order to limit the formation of ketone and epoxide self-condensation by-products. The fatty epoxide was therefore added drop-wise over 30 minutes into the reactor containing chloroacetic acid at 65° C. under stirring.

[0836] At the end of the addition, the mixture was allowed to stir at 65° C. during additional 20 min. NMR analysis showed a conversion level >99% for the starting epoxide.

[0837] Then, for the formation of the final bis-ester, 0.19 mL of 95% H.sub.2SO.sub.4 (3.37 mmol, 2 mol %) was added into the reactor and the condenser was replaced by a curved distillation column.

[0838] The mixture was allowed to stir at 140° C. during 3 h 30 under a light vacuum (800 mbar) in order to remove water formed as a by-product during the esterification reaction.

[0839] After 3 h 30 at 140° C., NMR analysis showed a selectivity (monoester+bis-ester) of 83 mol % and the following approximate crude mixture composition: 80 mol % of bis-ester, 3 mol % of mono-ester, 2 mol % of esterified dimer and 4 mol % of ketone.

[0840] The mixture was then cooled down at room temperature (about 23° C.) and 300 mL of toluene were added. The solution was transferred into a separating funnel and the organic phase was washed 3 times with 500 mL of an aqueous solution of NaOH (0.3M) to remove excess of chloroacetic acid. The organic phase was dried over MgSO.sub.4, filtered and then evaporated to give 102.7 g of crude product.

[0841] The product could be easily purified by dissolving the oil in ethanol (the starting ketone being not soluble in ethanol) followed by a filtration over celite. The filtrate was evaporated to afford 94 g of black oil with a purity of 89 wt % for the bis-ester corresponding to a isolated yield of 80% (RMN).

[0842] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 5.11-5.02 (m, 2H), 4.04 (s, isomer 1, 2H), 4.03 (s, isomer 2, 2H), 1.66-1.49 (m, 4H), 1.43-1.19 (m, 50H), 0.86 (t, J=6.8 Hz, 6H).

[0843] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 167.14, 167, 76.22, 75.83, 40.92, 40.82, 31.96, 30.6, 29.72, 29.69, 29.63, 29.54, 29.39, 29.33, 29.28, 28.85, 25.47, 24.96, 22.72, 14.15 (terminal CH.sub.3).

[0844] Condensation with Chloroacetic Acid (with Triflic Acid as an Optional Catalyst)

[0845] The reaction was conducted under an inert argon atmosphere in a 500 mL three necked round bottom flask equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and an insulated addition funnel. In the round bottom flask itself were added 85.63 g of chloroacetic acid (0.897 mol, 5 eq). In the insulated addition funnel were added 83.3 g of melted fatty epoxide (97 wt % purity, 0.179 mol, 1 eq).

[0846] The first step of monoester formation was conducted at 65° C. without triflic acid to limit the formation of ketone and dehydration by-products. The fatty epoxide was therefore added drop-wise over 2 h into the reactor containing chloroacetic acid at 65° C. under stirring in order to limit the self-condensation of fatty epoxide. At the end of the addition, the mixture was left at 65° C. under stirring during an additional hour. NMR analysis showed a conversion level >99% for the starting epoxide.

[0847] For the formation of the bis-ester, 3.2 μL of 99% triflic acid (0.036 mmol, 0.02 mol %) were then added into the reaction mixture. The condenser was replaced by a curved distillation column and the mixture was allowed to stir at 140° C. during 5 h 00 under a light vacuum (975 mbar) in order to remove water formed as a by-product of the esterification reaction.

[0848] After 5 h 00, NMR analysis showed a selectivity (monoester+bis-ester) of 88 mol % and a composition of 82 mol % of bis-ester, 6 mol % of mono-ester, 5 mol % of esterified dimer and 3 mol % of ketone.

[0849] The vacuum was then increased to 800 mbar and progressively until 10 mbar in order to distil chloroacetic acid, triflic acid catalyst and to complete conversion of mono-ester toward bis-ester.

[0850] Once all chloroacetic acid had been distilled out (verified by NMR analysis), the mixture was allowed to cool down at room temperature and atmospheric pressure was restored. The crude oil was transferred into a flask for purification. The product could be easily purified by dissolving the oil in ethanol (the starting ketone being not soluble in ethanol) followed by a filtration over celite. The filtrate was evaporated to afford 107.3 g of a black oil with a purity of 93 wt % for the bis-ester corresponding to an isolated yield of 89%.

[0851] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 5.11-5.02 (m, 2H), 4.04 (s, isomer 1, 2H), 4.03 (s, isomer 2, 2H), 1.66-1.49 (m, 4H), 1.43-1.19 (m, 50H), 0.86 (t, J=6.8 Hz, 6H).

[0852] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 167.14, 167, 76.22, 75.83, 40.92, 40.82, 31.96, 30.6, 29.72, 29.69, 29.63, 29.54, 29.39, 29.33, 29.28, 28.85, 25.47, 24.96, 22.72, 14.15 (terminal CH.sub.3)

[0853] Quaternization reaction with NMe.sub.3

[0854] The reaction was conducted under an inert argon atmosphere. In a 1 L double-jacketed reactor equipped with a mechanical stirrer, a condenser and a temperature probe, were added: [0855] 107.3 g (93 wt % purity, 0.16 mol, 1 eq.) of chloroacetate bis-ester C.sub.31 [0856] 687 mL (1.28 mol, 8 eq.) of a solution of trimethylamine (NMe.sub.3) in THF (˜2 mol/L) dried beforehand on molecular sieve activated the day before.

[0857] The reaction mixture was heated at 40° C. and stirring was started at 1000 rpm. After 6 h, NMR analysis in d.sub.4-MeOH showed a conversion level >99% for the starting bis-ester with a molar composition of ˜86 mol % for glycine betaine bis-ester. The reactor was drained, rinsed with CH.sub.2Cl.sub.2 and the volatiles were evaporated under vacuum.

[0858] The brown solid was reduced into a powder, deposited on a sinter filter and washed 5 times with 200 mL of ethyl acetate. The solid was dried under vacuum.

[0859] Then, the product was transferred into a 1 L reactor equipped with a mechanical stirrer, a condenser, a heater and a temperature probe. The product was solubilized into 800 mL of chloroform and 150 g of activated charcoal pellets were added. The mixture was stirred at 40° C. for 2 hours in order to whiten the product.

[0860] After 2 h, the suspension was filtrated over celite and the solvent was evaporated to afford 109 g of a brown wax with a weight composition of ˜95 wt % of quaternary di-ammonium compound of formula (IX), 2 wt % of quaternary mono-ammonium, 0.1 wt % of C.sub.31 ketone and 4 wt % of the ether by-product. The purified yield of the glycine betaine bis-ester was ˜87%.

Example 12—Synthesis of a Quaternary Di-Ammonium Compound Starting from C.SUB.16.-C.SUB.18 .(30:70) Fatty Acid Cut

[0861] Piria Ketonization Toward Internal C.sub.31-C.sub.35 Ketones Cut

[0862] The reaction was conducted under an inert argon atmosphere in a 200 mL quartz reactor equipped with a mechanical stirring (A320-type stirring mobile manufactured by 3D-printing with Inox SS316L), an insulated addition funnel, a distillation apparatus, a heating mattress and a temperature probe.

[0863] In the reactor were introduced: [0864] 12.5 g of MASCID™ acid 1865 (from Musim Mas Group) composed of 33.7 wt % of palmitic acid and 65.3 wt % of stearic acid (0.045 mole of fatty acids), and [0865] 0.935 g of MgO (0.023 mole).

[0866] In the insulated addition funnel were added 37.5 g of the same melted fatty acids mixture (0.135 mole).

[0867] The temperature of the reaction media was then raised to 250° C. Once the temperature reached 150° C., stirring was started (1200 rpm). After 2 h 00 reaction time at 250° C., FTIR analysis showed complete conversion of the starting fatty acids into the intermediate magnesium carboxylate complex.

[0868] The temperature of the reaction mass was then raised further to 330° C. and the mixture was allowed to stir at this temperature during 1 h 30 in order to allow decomposition of the intermediate magnesium carboxylate complex to the desired ketone.

[0869] Then, 12.5 g of the melted fatty acid mixture was progressively added into the reactor thanks to the addition funnel during 30 minutes and the mixture was stirred at 330° C. during an additional 1 h 00. FTIR analysis showed complete conversion of fatty acids and magnesium complex to the desired ketone.

[0870] Two additional cycles of 12.5 g fatty acid addition during 30 minutes followed by additional 1 h 00 stirring at 330° C. were then realized.

[0871] After the last cycle the mixture was allowed to stir at 330° C. during an additional 1 h 00 to ensure complete conversion of the intermediate magnesium complex to the desired ketone which was confirmed by FTIR analysis.

[0872] The temperature of the reaction mixture was then allowed to cool down at room temperature and the crude was solubilized in hot CHCl.sub.3. The suspension was filtered on a plug of silica (70 g) and the product was further eluted with additional amounts of CHCl.sub.3.

[0873] After solvent evaporation 41.83 g (0.086 mole) of product was obtained as a white wax corresponding to an isolated yield of 96%.

[0874] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 2.45-2.25 (t, J=7.6 Hz, 4H), 1.62-1.46 (m, 4H), 1.45-1.05 (m, 54H), 0.86 (t, J=6.8 Hz, 6H).

[0875] .sup.13C NMR (CDCl3, 101 MHz) δ (ppm): 212.00, 43.05, 32.16, 29.93, 29.91, 29.88, 29.84, 29.72, 29.65, 29.59, 29.51, 24.13, 22.92, 14.34 (terminal CH.sub.3).

[0876] Hydrogenation of Ketones Mixture Toward Internal C.sub.31-C.sub.35 Fatty Alcohols Mixture

[0877] Same protocol as the one described in example 11 under “Hydrogenation of 16-hentriacontanone to 16-hentriacontanol” part was followed to obtain the desired fatty alcohols mixture in excellent yield.

[0878] Dehydration of C.sub.31-C.sub.35 Fatty Alcohols into Internal Olefins

[0879] All the reactions were conducted under an inert argon atmosphere.

[0880] In a 200 mL quartz reactor equipped with a heating mattress, a mechanical stirrer (A320-type stirring mobile manufactured by 3D-printing with Inox SS316L), surmounted by a condenser connected to a 50 mL two-neck distillate collection flask and a temperature probe were added: [0881] 41.3 g of the C.sub.31-35 fatty alcohol (85 mmol, 1 eq.), and [0882] 4.13 g (40 mmol, 10 wt %) of Al.sub.2O.sub.3-η.

[0883] The temperature of the reaction media was increased to 150° C. to melt the alcohol and stirring was started (about 500 rpm). Then, the temperature was set-up at 300° C. and the mixture was allowed to stir at 1000 rpm under argon. The reaction progress was monitored thanks to NMR analysis with a borosilicate glass tube.

[0884] After 2 hours reaction at 300° C., NMR analysis in CDCl.sub.3 showed complete conversion of the fatty alcohol and the presence of 1.5 mol % of ketone which had been formed as a by-product.

[0885] Stirring and heating were then stopped and the temperature was lowered to 80° C. The molten crude was transferred to a beaker. The reactor vessel and the stirring mobile were rinsed with chloroform (Al.sub.2O.sub.3 is insoluble).

[0886] The mixture was filtered and the solvent was evaporated under vacuum to afford 39 g of a clear yellow oil which solidified at room temperature to give a white solid in the form of wax (98 wt % purity) corresponding to 97% yield (NMR).

[0887] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 5.38-5.29 (m, 2H), 2.03-1.93 (m, 4H), 1.35-1.19 (m, 55H (average H number)), 0.86 (t, J=6.8 Hz, 6H).

[0888] .sup.13C NMR (CDCl3, 101 MHz) δ (ppm): 130.6, 130.13, 32.84, 32.16, 30.01, 29.93, 29.8, 29.6, 29.55, 29.4, 22.93, 14.35 (terminal CH.sub.3).

[0889] Epoxidation of Internal Olefins to Afford C.sub.31-35 Oxiranes

[0890] The reaction was conducted under an inert argon atmosphere.

[0891] In a 300 mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows) and baffles, a condenser and a temperature probe were added: [0892] 38.2 g of C.sub.31-35 alkene (98 wt % purity, 80 mmol) [0893] 6.9 mL (7.2 g, 120 mmol) of acetic acid, and [0894] 11.3 g (30 wt %) of Amberlite® IR 120H resin.

[0895] The mixture was heated to 75° C. to melt the fatty alkene. The agitation was then started and 12.3 mL (13.7 g, 120 mmol) of H.sub.2O.sub.2 30% were slowly added into the mixture using an addition funnel while monitoring temperature of the reaction medium to prevent temperature increase of the reaction mass (exothermicity). This required about 20 min. During the addition, the agitation was increased to improve transfers due to the heterogeneous nature of the reaction media.

[0896] At the end of the addition, the temperature of the reaction medium was increased at 85° C. and after 6 h 10 of stirring at this temperature, NMR analysis showed that the conversion level was around 99% with 98% selectivity.

[0897] Heating was then stopped and 150 mL of chloroform were added when the temperature of the reaction mass was around 50° C. The mixture was transferred to a separating funnel and the organic phase was washed 3 times with 150 mL of water. The resin catalyst that stayed in the aqueous phase was removed during phase separation. The aqueous phase was extracted twice with 50 mL of chloroform. The organic phase was dried over MgSO.sub.4, filtered and evaporated to afford 39.2 g of a white solid with a purity of 98 wt % (epoxide+di-alcohol by-product). The yield taking into account the purity was 99%.

[0898] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 2.91-2.85 (m, 1.5H), 2.65-2.6 (m, 0.5H), 1.53-1.36 (m, 4H), 1.35-1.19 (m, 55H (aver. H number)), 0.86 (t, J=6.8 Hz, 6H).

[0899] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 58.97, 57.28, 32.18, 31.96, 29.72, 29.6, 29.4, 27.86, 26.95, 26.63, 26.09, 22.72, 14.15 (terminal CH.sub.3).

[0900] Condensation with Chloroacetic Acid to Afford Chloroacetate Bis-Ester C.sub.31-35 (with H.sub.2SO.sub.4 as an Optional Solvent)

[0901] The reaction was conducted under an inert argon atmosphere in a 250 mL three necked round bottom flask equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and an insulated addition funnel. In the round bottom flask itself were added 59.2 g of chloroacetic acid (0.62 mol, 8 eq). In the insulated dropping funnel maintained at 60° C., were added 38.3 g of melted C.sub.31-35 epoxide (purity: 98 wt %, 77.6 mmol, 1 eq).

[0902] The first step of hydroxyl-ester formation was conducted at 70° C. without sulfuric acid to limit the formation of ketone and dehydrated by-products and through progressive addition of fatty epoxide into chloroacetic acid in order to limit epoxide self-condensation. The reaction mixture was allowed to stir at 70° C. in order to melt the chloroacetic acid.

[0903] The melted epoxide was then added drop-wise into the reaction mixture under stirring over 1 h 00 in order to limit self-condensation of the epoxide.

[0904] At the end of the addition, the mixture was allowed to stir at 70° C. for an additional 20 min. At this stage NMR analysis showed nearly a complete conversion of the epoxide to the intermediate monoester.

[0905] For the conversion of the mono-ester to the bis-ester, 87 μL of 95% H.sub.2SO.sub.4 (1.6 mmol, 2 mol %) were added into the reaction mixture. The condenser was replaced by a curved distillation column and the mixture was allowed to stir at 140° C. during 6 h 30 while applying a 800 mbar vacuum to facilitate water removal. After 6 h 30 reaction time, NMR analysis showed the estimated composition of the crude media: [0906] 79 mol % of bis-ester [0907] 6 mol % of mono-ester [0908] 1 mol % of esterified dimer by-product, and [0909] 5 mol % of ketone by-product.

[0910] The mixture was cooled down at room temperature and 150 mL of toluene were added to the crude. The organic solution was transferred into a separating funnel and was washed 7 times with 250 mL of an aqueous NaOH solution (0.15M) to remove excess of chloroacetic acid. The aqueous phase was extracted 2 times using 100 mL of toluene.

[0911] The organic phases were gathered and washed with 150 mL of an aqueous HCl (0.1N) solution and then with 150 mL of saturated NaCl solution. The organic phase was dried over MgSO.sub.4, filtered and then evaporated to give 48 g of the crude product.

[0912] The product could be easily purified by dissolving the oil in isopropanol (the starting ketone being not soluble in isopropanol) followed by a filtration over celite. The filtrate was evaporated to give 45.7 g of black oil with an estimated purity of 91 wt % for the bis-ester corresponding to a yield of 81% (RMN).

[0913] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 5.11-5.02 (m, 2H), 4.04 (s, isomer 1, 2H), 4.03 (s, isomer 2, 2H), 1.66-1.49 (m, 4H), 1.43-1.19 (m, 55H (average H number)), 0.86 (t, J=6.8 Hz, 6H).

[0914] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 167.14, 167, 76.22, 75.83, 40.92, 40.82, 31.96, 30.6, 29.72, 29.69, 29.63, 29.54, 29.39, 29.33, 29.28, 28.85, 25.47, 24.96, 22.72, 14.15 (terminal CH.sub.3).

[0915] Quaternization with NMe.sub.3

[0916] The reaction was conducted under 5 bar nitrogen pressure. In a 750 mL autoclave equipped with a mechanical stirrer (Rushton turbine), were added: [0917] 45.7 g (91 wt % purity, 63 mmol, 1 eq.) of chloroacetate bis-ester C.sub.31-35, and [0918] 169 mL (316 mmol, 5 eq.) of trimethylamine solution in THF (˜2 mol/L) that had been dried beforehand on molecular sieve activated the day before.

[0919] Three nitrogen purges are performed. The reaction mixture was heated at 40° C. and stirring was started at 1000 rpm.

[0920] After 4 h 15 reaction time, NMR analysis in MeOD/CDCl.sub.3 showed a conversion level of approximately 99% for the starting chloroacetate bis-ester with approximately 81 mol % of the desired glycine betaine bis-ester.

[0921] The mixture was allowed to cool down at room temperature, the reactor was depressurized and the solution was then drained. The reactor is rinsed with CH.sub.2Cl.sub.2 and the solvent evaporated to afford 43 g of crude product.

[0922] The solid was then deposited on a sinter filter and washed several times with ethyl acetate to remove some organic impurities. The solid was dried under vacuum and transferred into a 500 mL three necked round bottom flask equipped with a magnetic stirrer, a heater, a condenser and a temperature probe.

[0923] The product was solubilized in 250 mL of chloroform and 25 g of activated charcoal were added. The reaction mixture was then heated under reflux for 2 hours in order to whiten the product.

[0924] After cooling down at room temperature, the suspension was filtered over celite then evaporated to give 33 g of a beige wax with the following approximate composition: 92 wt % of quaternary di-ammonium compound of formula (IX), 5 wt % of quaternary mono-ammonium compound and 3 wt % of an ether by-products.

[0925] .sup.1H NMR (MeOD-d.sub.4, 400 MHz) δ (ppm): 4.78 (s, 1H), 4.74 (s, 1H), 4.53 (s, 1H), 4.49 (s, 1H), 3.38 (s, 18H), 1.77-1.6 (m, 4H), 1.51-1.25 (m, 55H (average H numbers)), 0.9 (t, J=6.8 Hz, 6H).

[0926] .sup.13C NMR (MeOD-d.sub.4, 101 MHz) δ (ppm): 166.39, 166.12, 79.62, 78.17, 77.28, 64.25, 63.98, 54.8, 54.65, 33.21, 31.61, 30.95, 30.83, 30.69, 30.64, 30.5, 30.44, 29.81, 26.7, 26.21, 23.9, 14.58 (terminal CH.sub.3).

Example 13—Synthesis of a Quaternary Di-Ammonium Compound Starting from C.SUB.16.-C.SUB.18 .(60:40) Fatty Acid Cut

[0927] Piria ketonization toward internal C.sub.31-C.sub.35 ketones cut

[0928] The reaction was conducted under an inert argon atmosphere in a 200 mL quartz reactor equipped with a heating mattress, a mechanical stirring (A320-type stirring mobile manufactured by 3D-printing with Inox SS316L), an insulated addition funnel, a distillation apparatus and a temperature probe.

[0929] In the reactor itself were introduced: [0930] 15 g of MASCID™ acid 1801 (from Musim Mas Group) with the following composition: 60.9 wt % of palmitic acid and 38.2 wt % of stearic acid (0.056 mole of fatty acids), and [0931] 1.15 g of MgO (0.028 mole).

[0932] In the insulated addition funnel were added 45 g of the same melted fatty acids mixture (0.167 mole).

[0933] The temperature of the reaction mixture was then raised to 250° C. and once the temperature had reached 150° C., the stirring was started (1200 rpm). After 1 h 15 reaction time at 250° C., FTIR analysis showed complete conversion of the starting fatty acids into the intermediate magnesium carboxylate complex.

[0934] The temperature of the reaction mass was then raised further to 330° C. and the mixture was allowed to stir at this temperature during 1 h 30 in order to allow decomposition of the magnesium complex to the desired ketone.

[0935] Then 15 g of the melted fatty acid mixture were progressively added to the reactor thanks to the addition funnel during 15 minutes and the mixture was stirred at 330° C. during one additional hour. FTIR analysis confirmed complete conversion of fatty acids and magnesium complex to the desired ketone.

[0936] Two additional cycles of 15 g fatty acid addition during 15 minutes followed by one hour stirring at 330° C. were then realized. Following the last addition cycle the mixture was allowed to stir at 330° C. during one additional hour in order to ensure complete conversion of the intermediate magnesium carboxylate complex to the desired ketone, which was confirmed thanks to FTIR and NMR analysis according to the following protocol: the sample was dissolved in chloroform and washed three times with 2N HCl aqueous solution and the solvent was evaporated. NMR and IR analysis on the residue did not show any presence of starting fatty acid that might have been formed by complex hydrolysis.

[0937] The temperature of the reaction mixture was allowed to cool down at 60° C. and the crude was solubilized in 350 mL of hot CHCl.sub.3 (60° C.). The suspension was filtered on a plug of silica (100 g) and the product was further eluted with additional amounts of CHCl.sub.3. After solvent evaporation 50.5 g of crude product were obtained.

[0938] The product was washed 3 times with 200 mL of isopropanol on a sintered filter in order to remove trace of by-products. The solid was dried to afford the desired ketone as a white powder with a purity of 100 mol % corresponding to a yield of 90%.

[0939] .sup.1H NMR (CDCl3, 400 MHz) δ (ppm): 2.35 (t, J=7.6 Hz, 4H), 1.62-1.46 (m, 4H), 1.34-1.16 (m, 54.8H (average number)), 0.86 (t, J=6.8 Hz, 6H).

[0940] .sup.13C NMR (CDCl3, 101 MHz) δ (ppm): 212.00, 43.06, 32.16, 29.92, 29.89, 29.85, 29.72, 29.66, 29.6, 29.52, 24.16, 22.93, 14.35 (terminal CH.sub.3).

[0941] Hydrogenation of Ketones Mixture Toward Internal C.sub.31-C.sub.35 Fatty Alcohols Mixture

[0942] Same protocol as the one described in example 11 under “Hydrogenation of 16-hentriacontanone to 16-hentriacontanol” part was followed to obtain the desired fatty alcohols mixture in excellent yield.

[0943] Dehydration of C.sub.31-C.sub.35 Fatty Alcohols to Internal Olefins

[0944] The reaction was conducted under an inert argon atmosphere. In a 200 mL quartz reactor equipped with a heating mattress, a mechanical stirrer (A320-type stirring mobile manufactured by 3D-printing with Inox SS316L), surmounted by a condenser connected to a 50 mL two-necked distillate collection flask and a temperature probe were added: [0945] 43.6 g of the C.sub.31-35 fatty alcohol (92 mmol, 1 eq) [0946] 4.4 g (43 mmol, 10 wt %) of Al.sub.2O.sub.3-η.

[0947] The reaction medium was first heated at 150° C. in order to melt the fatty alcohol mixture and stirring was started (about 500 rpm). Then, the temperature was increased up to 300° C. and the mixture was allowed to stir at 1000 rpm under argon atmosphere. The reaction progress was monitored thanks to NMR analysis. After 2 hours reaction time at 300° C., NMR analysis in CDCl.sub.3 showed complete conversion of the fatty alcohol and also presence of 0.3 mol % of ketone which had been formed as a by-product.

[0948] Stirring and heating were then stopped to allow the crude media to cool down. Once the temperature had decreased to about 80° C. the molten crude was transferred to a beaker. The reactor vessel and the stirring mobile were rinsed with chloroform (Al.sub.2O.sub.3 is insoluble).

[0949] The suspension was filtered to remove catalyst and the solvent was evaporated under vacuum to afford 40.1 g of a clear yellow oil which solidified at room temperature to give a white compact solid in the form of a wax (>99 wt % purity) and 95% yield (NMR).

[0950] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 5.42-5.29 (m, 2H), 2.04-1.9 (m, 4H), 1.35-1.19 (m, 52.8H (average number)), 0.86 (t, J=6.8 Hz, 6H).

[0951] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 130.59, 130.13, 32.84, 32.16, 30.02, 29.93, 29.77, 29.6, 29.55, 29.4, 27.44, 22.93, 14.35 (terminal CH.sub.3).

[0952] Epoxidation of Internal Olefins to Afford C.sub.31-35 Oxiranes

[0953] The reaction was conducted under an inert argon atmosphere. In a 300 mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows) and baffles, a condenser, an addition funnel and a temperature probe were added: [0954] 39 g of C.sub.31-35 alkene (>99 wt % purity, 86 mmol) [0955] 7.3 mL (7.7 g, 128 mmol) of acetic acid, and [0956] 11.7 g (30 wt %) of Amberlite® IR 120H resin.

[0957] The mixture was heated to 75° C. in order to melt the fatty alkene. Stirring was then started and 13.1 mL (14.6 g, 128 mmoles) of H.sub.2O.sub.2 30% were slowly added into the mixture using the addition funnel while monitoring temperature of the reaction medium in order to avoid temperature increase of the reaction mass (slight exothermicity). This required about 20 min. During the addition, stirring rate was increased to improve mass transfers due to the heterogeneous nature of the reaction media. At the end of the addition, the temperature of the reaction medium was increased to 85° C. After 4 h 30 of stirring, NMR analysis showed an alkene conversion level around 97%.

[0958] In order to complete the reaction, additional 4.4 mL (4.8 g, 43 mmol) of H.sub.2O.sub.2 30% were added to the reaction media. After 7 hours of total reaction time at 85° C., NMR analysis showed a complete conversion level for the alkene.

[0959] Stirring was then stopped in order to allow the liquid phases to separate in the reactor at 85° C. Solid Amberlite® resin had sedimented at the bottom of the reactor. Aqueous phase was removed by draining through the bottom valve. 100 mL of water were then added into the reactor and the mixture was allowed to stir during 15 minutes. The phases were again separated and the aqueous phase was removed.

[0960] Finally, the melted organic phase was drained into a PYREX® beaker (with the catalyst) and the reactor was rinsed 2 times with 100 mL of chloroform in order to recover remaining product. The organic phase was dried over MgSO.sub.4, filtered and evaporated to afford 40.1 g of a white compact solid with a purity of 99 wt % (epoxide+di-alcohol by-product). The yield taking into account the purity was 98%.

[0961] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 2.91-2.85 (m, 1.5H), 2.65-2.6 (m, 0.5H), 1.53-1.36 (m, 4H), 1.35-1.19 (m, 52.8H (average number)), 0.86 (t, J=6.8 Hz, 6H).

[0962] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 58.97, 57.29, 32.18, 31.96, 29.73, 29.6, 29.49, 29.4, 27.86, 26.63, 26.09, 22.72, 14.15 (terminal CH.sub.3).

[0963] Catalyst-Free Condensation with Chloroacetic Acid to Afford Chloroacetate Bis-Ester C.sub.31-35

[0964] The reaction was conducted under an inert argon atmosphere in a 500 mL three necked round bottom flask reactor equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and an insulated addition funnel. In the bottom flask reactor itself were added 39.19 g of chloroacetic acid (410.5 mmol, 5 eq). In the insulated addition funnel maintained at 65° C. were added 38.6 g of melted fatty epoxide (purity: 99 wt %, 82.1 mmol, 1 eq).

[0965] The first step of hydroxyl-ester formation was conducted at 65° C. to limit the formation of ketone and dehydration by-products. The fatty epoxide was therefore added drop-wise over 1 h 30 into the reactor containing chloroacetic acid at 65° C. under stirring in order to limit the self-condensation of two fatty epoxide molecules. Upon completion of the addition of the fatty epoxide, the mixture was allowed to stir at 65° C. during 30 min. NMR analysis showed a conversion level >98% for the starting epoxide.

[0966] For the formation of the final bis-ester, the condenser was replaced by a curved distillation column and the mixture was allowed to stir at 140° C. during 5 h 30 under a light vacuum (975 mbar) in order to assist the removal of water which was formed as a by-product of the esterification reaction. After 5 h at 140° C., NMR analysis showed a selectivity (monoester+bis-ester) of 92 mol % and the following approximate crude mixture composition: 90 mol % of bis-ester, 2 mol % of mono-ester, 1 mol % of esterified dimer and 2 mol % of ketone.

[0967] The pressure was then decreased down to 800 mbar and progressively until 10 mbar in order to distil the excess of chloroacetic acid and to complete conversion of mono-ester toward bis-ester. Once the whole amount of chloroacetic acid had been distilled out (verified by NMR analysis), the mixture was cooled down to room temperature and the atmospheric pressure was re-established. The crude oil was then transferred into a flask for purification.

[0968] The product could be easily purified by dissolving the oil in 300 mL of isopropanol (the starting ketone being not soluble in isopropanol) followed by a filtration over celite. The filtrate was evaporated to afford 49.1 g of a black oil with a purity of 93 wt % for the bis-ester corresponding to an isolated yield of 86% (RMN).

[0969] .sup.1H NMR (CDCl.sub.3, 400 MHz) δ (ppm): 5.11-5.02 (m, 2H), 4.04 (s, isomer 1, 2H), 4.03 (s, isomer 2, 2H), 1.66-1.49 (m, 4H), 1.43-1.19 (m, 52.8H (average number)), 0.86 (t, J=6.8 Hz, 6H).

[0970] .sup.13C NMR (CDCl.sub.3, 101 MHz) δ (ppm): 167.14, 167, 76.22, 75.83, 40.92, 40.82, 31.96, 30.6, 29.73, 29.64, 29.54, 29.39, 29.28, 28.85, 25.47, 24.96, 22.72, 14.15 (terminal CH.sub.3).

[0971] Quaternization with NMe.sub.3

[0972] The reaction was conducted under an inert argon atmosphere. In a 1 L double-jacketed reactor equipped with a mechanical stirrer, a condenser and a temperature probe, were added: [0973] 48.1 g (69 mmol, 1 eq) of chloroacetate bis-ester C.sub.31-35 (purity: 93 wt %) [0974] 334 mL (625 mmol, 9 eq) of a solution of trimethylamine in THF (˜2 mol/L).

[0975] The reaction mixture was then stirred (1000 rpm) at 40° C. After 3 h, the mixture was allowed to cool down at room temperature and stirred overnight. The next day, NMR analysis (d.sub.4-MeOD) showed a full conversion of the starting bis-ester with an approximate selectivity of 92 mol % (NMR) toward the desired product glycine betaine bis-ester. The reactor was drained, rinsed with THF and the volatiles were removed under vacuum.

[0976] The product was reduced to a powder, deposited on a sinter filter and washed 5 times with 100 mL of ethyl acetate in order to remove the organic impurities. The solid was dried under vacuum to afford 53 g of a brown wax with the following approximate weight composition: 94 wt % of NQ19 quaternary bis-ammonium, 2 wt % of quaternary mono-ammonium, 0.1 wt % of N(Me).sub.3.HCl and 3.5 wt % of an ether by-products. The purified yield of the glycine betaine bis-ester was 94%.

[0977] .sup.1H NMR (MeOD-d.sub.4, 400 MHz) δ (ppm): 5.3-5.13 (m, 2H), 4.79 (s, 1H), 4.75 (s, 1H), 4.53 (s, 1H), 4.49 (s, 1H), 3.38 (s, 18H), 1.78-1.63 (m, 4H), 1.49-1.2 (m, 52.8H (average number)), 0.9 (t, J=6.8 Hz, 6H).

[0978] .sup.13C NMR (MeOD-d.sub.4, 101 MHz) δ (ppm): 166.39, 166.12, 79.62, 78.17, 77.28, 64.25, 63.98, 54.8, 54.65, 33.21, 31.61, 30.95, 30.83, 30.69, 30.64, 30.5, 30.44, 29.81, 26.7, 26.21, 23.9, 14.58 (terminal CH.sub.3).

[0979] Overall, the compounds of the present invention show a good combination of surfactant properties combined with a reasonable to good biodegradabilty—a combination which is in many cases not achieved by commercial surfactants.

[0980] Since the compounds of the present invention are also easily available starting from internal ketones which are easily accessible from fatty acids or fatty acid derivatives, the compounds of the present invention also provide economical benefits over the prior art compounds.