BIOBASED SURFACTANTS

Abstract

Compound of the general formula (Ia), (Ib) and (Ic) R.sub.50 and R.sub.60 are different form each other and are selected from the group consisting of R.sub.70, ZR.sub.70, ZOH, ZNH.sub.2, ZSH, ZOC(O)R.sub.70, OC(O)R.sub.70, COOH and its corresponding salts, C(O)NH.sub.2, C(O)NHR.sub.70, C(O)N(R.sub.70).sub.2, COOR.sub.70, ZCOOH and its corresponding salts, ZC(O)NHR.sub.70, ZC(O)NH.sub.2, ZC(O)N(R.sub.70).sub.2, ZCOOR.sub.70, CH(COOH).sub.2 and its corresponding salts, CH(COOR.sub.70).sub.2, and ZSO.sub.3 wherein R.sub.70 is selected from the group consisting of a linear or branched C.sub.1 to C.sub.20 alkyl, (C.sub.1 to C.sub.10)-alkyloxy-(C.sub.1 to C.sub.10)-alkyl, C.sub.2 to C.sub.10 alkenyl, C.sub.6 to C.sub.12 aryl, C.sub.3 to C.sub.10 cycloalkyl, cycloalkylalkyl and cycloalkylalkenyl, wherein Z is a linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.3 to C.sub.10 cycloalkyl, a linear or branched C.sub.6 to C.sub.10 aryl or a (C.sub.1 to C.sub.10)-alkyloxy-(C.sub.1 to C.sub.10)-alkyl, cycloalkylalkyl and cycloalkylalkenyl.

##STR00001##

Claims

1. A compound of the general formula (Ia), (Ib) or (Ic) ##STR00058## R.sub.50 and R.sub.60 are different form each other and are selected from the group consisting of R.sub.70, ZR.sub.70, ZOH, ZNH.sub.2, ZSH, ZOC(O)R.sub.70, OC(O)R.sub.70, COOH and its corresponding salts, C(O)NH.sub.2, C(O)NHR.sub.70, C(O)N(R.sub.70).sub.2, COOR.sub.70, ZCOOH and its corresponding salts, ZC(O)NHR.sub.70, ZC(O)NH.sub.2, ZC(O)N(R.sub.70).sub.2, ZCOOR.sub.70, CH(COOH).sub.2 and its corresponding salts, CH(COOR.sub.70).sub.2, and ZSO.sub.3 wherein R.sub.70 is selected from the group consisting of a linear or branched C.sub.1 to C.sub.20 alkyl, (C.sub.1 to C.sub.10)-alkyloxy-(C.sub.1 to C.sub.10)-alkyl, C.sub.2 to C.sub.15 alkenyl, C.sub.6 to C.sub.12 aryl, C.sub.3 to C.sub.10 cycloalkyl, cycloalkylalkyl and cycloalkylalkenyl, wherein Z is a linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.3 to C.sub.10 cycloalkyl, a linear or branched C.sub.6 to C.sub.10 aryl or a (C.sub.1 to C.sub.10)-alkyloxy-(C.sub.1 to C.sub.10)-alkyl, cycloalkylalkyl and cycloalkylalkenyl.

2. The compound of the general formula (Ib) or (Ic) according to claim 1, wherein R.sub.50 or R.sub.60 is R.sub.70 and wherein R.sub.70 is a linear C.sub.7 to C.sub.19 alkyl.

3. The compound of the general formula (Ib) according to claim 2, wherein R.sub.50 is R.sub.70 and wherein R.sub.70 is a linear C.sub.7 to C.sub.19 alkyl.

4. The compound of the general formula (Ic) according to claim 2, wherein R.sub.60 is R.sub.70 and wherein R.sub.70 is a linear C.sub.7 to C.sub.19 alkyl.

5. The compound of the general formula (Ia) according to claim 1, wherein one of R.sub.50 or R.sub.60 is R.sub.70 and the other is COOH or its corresponding salt and wherein R.sub.70 is a linear C.sub.7 to C.sub.19 alkyl.

6. The compound of the general formula (Ib) according to claim 1, wherein R.sub.50 is R.sub.70 and wherein R.sub.70 is a linear C.sub.2 to C.sub.15 alkenyl.

7. A compound of the general formula (V) ##STR00059## wherein R.sub.90 is selected from the group consisting of a linear or branched C.sub.1 to C.sub.20 alkyl, (C.sub.1 to C.sub.10)-alkyloxy-(C.sub.1 to C.sub.10)-alkyl, C.sub.2 to C.sub.10 alkenyl, C.sub.6 to C.sub.12 aryl, C.sub.3 to C.sub.10 cycloalkyl, cycloalkylalkyl and cycloalkylalkenyl.

8. The compound of the general formula (V) according to claim 8, wherein R.sub.90 is a linear C.sub.7 to C.sub.19 alkyl.

9. A cosmetic, food, frying, pharmaceutical or cleaning product comprising the compound according to claim 1.

10. A cosmetic, food, frying, pharmaceutical or cleaning product comprising the compound according to claim 7.

Description

EXAMPLES

Synthesis of docosanol-substituted diglyoxylic acid xylose (2,3) and characterization

##STR00039##

[0091] The synthesis of diglyoxylic acid-xylose (1) from xylose and biomass is known to the skilled person. Docosanol (0.56 g, 1.7 mmol) dissolved in 25 ml of chloroform and diglyoxylic acid-xylose (1) (0.5 g, 1.9 mmol) dissolved in 15 ml of 1,4-dioxane were mixed in 100 ml round-bottom flask. Sulfuric acid (98% pure, 200 mkl) was added to the reaction mixture and the reaction mixture was heated at 65 C. for 24 h to obtain slightly pink solution. The reaction mixture was analyzed by HPLC (C18 column, isopropanol/methanol 1:9 mobile phase) and TLC (hexane/ethyl acetate 1:8), and one-side protected product was identified (2,3 or their mixture).

Synthesis of octanol-substituted diglyoxylic acid xylose (2,3) and characterization

##STR00040##

[0092] The synthesis of diglyoxylic acid-xylose (1) from xylose and biomass is known to the skilled person. 1-octanol (0.2 g, 1.7 mmol) and diglyoxylic acid-xylose (1) (0.5 g, 1.9 mmol) were mixed in 30 ml of 1,4-dioxane in 100 ml round-bottom flask. Sulfuric acid (98% pure, 200 mkl) was added to the reaction mixture and the reaction mixture was heated at 85 C. for 5 h. The reaction mixture was analyzed by HPLC (C18 column, isopropanol/methanol 1:9 mobile phase) and TLC (hexane/ethyl acetate 1:8), and one-side protected product was identified (2,3, or their mixture).

[0093] The mixture was neutralized until pH 7, and dissolved in a non-miscible system of ethyl acetate and water to do a quick emulsion test. FIG. 1a shows the formation of emulsion of an extract of a mixture of compounds 2 and 3 in a system comprising ethyl acetate and water (vial 1) in comparison with pure 1-octanol in the same system (vial 2) and the system itself (vial 3). It can be seen that vials 2 and 3 have phase separated while in vial 1 there is no phase separation occurred.

Emulsion Stability Measurements

[0094] The emulsions were prepared by mixing 1 ml of water (with 1 mg/ml of Acian blue dye) and 2 ml cyclohexane containing 3,5-O-dodecylidene-xylose or 2-((dodecyloxy)methyl) tetrahydrofuran-3,4-diol) at a concentration of 0.1% and then mixed by vortex for 30 s.

[0095] Emulsions were characterized using a bright-field microscope (Leitz Ergolux) during the storage after preparation. FIG. 1b and FIG. 1c show that the aqueous bubbles in oil phase can maintain stable for at least 30 days without obvious coalescence. Besides, a water/oil emulsion (67% water and 33% cyclohexane) containing 1% 3,5-O-dodecylidene-xylose was kept for about 1 year to observe its possible destablization. FIG. 2 shows a thin oil layer and a clarification layer was developed after 1 year, but most of the volume maintained the form of emulsion.

Synthesis of 1,2-O-dodecylidene-xylose (6) and 3,5-O-dodecylidene-xylose (7) from xylose

##STR00041##

[0096] In a 1-neck round bottom flask, 1 molar equivalent of D-xylose was mixed with 0.9 molar equivalent dodecanal and 0.1 molar equivalents of sulfuric acid catalyst in dioxane. The reaction was conducted at 65 C. for 24 h. Then, the solution was neutralized with 1M NaOH solution until the pH value becomes around 7. The solution was concentrated on a rotavap with a bath temperature of 45 C. under reduced pressure (80 mbar). Then the residue viscous yellow oil was washed with brine solution and extracted with EtOAc. The organic phase was then evaporated on a rotavap and purified using column chromatography to obtain light yellow solid and yellowish oil. They were characterized by Heteronuclear Single Quantum Coherence Spectroscopy (HSQC) NMR.

Synthesis of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (9) from 3,5-O-dodecylidene-xylose (7)

##STR00042##

[0097] In a 1-neck round bottom flask, 1 molar equivalent of 3,5-O-dodecylidene-xylose (7) (MAX12) was mixed with 2 molar equivalent of glyoxylic acid monohydrate in dioxane. Amberlyst A15 was used as catalyst and molecular sieve was added to remove produced water. The reaction was conducted at 80 C. for 4 h. Then, the solution was filtered and concentrated on a rotary evaporator with a bath temperature of 45 C. under reduced pressure (80 mbar). Then the reaction mixture was purified using column chromatography (hexane-ethyl acetate with 1% acetic acid) to obtain 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (9) (GMAX) as a light yellow solid.

Synthesis of sodium 1,2-O-carboxylate-3,5-O-dodecylidene-xylose (10) from 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (9)

##STR00043##

[0098] 1 molar equivalent of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (9) react with 1 molar equivalent of sodium hydroxide solution produce sodium 1,2-O-carboxylate-3,5-O-dodecylidene-xylose (10) with pH around 7.

Synthesis of didodecylidene-xylose (8) from xylose

##STR00044##

[0099] In a 1-neck round bottom flask, 1 molar equivalent of D-xylose was mixed with 2.05 molar equivalent dodecanal and 0.2 molar equivalents of sulfuric acid catalyst in dioxane. The reaction was conducted at 65 C. for 24 h. Then, the solution was neutralized with 1M NaOH solution until the pH value becomes around 7. The solution was concentrated on a rotavap with a bath temperature of 45 C. under reduced pressure (80 mbar). Then the resultant viscous pale-yellow oil was washed with brine solution and extracted with EtOAc. The organic phase was then evaporated on a rotavap and purified using flash chromatography. The product was collected and crystalized in hexane in the fridge to afford white didodecylidene-xylose crystals (8).

Synthesis of 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol

##STR00045##

[0100] Didodecylidene-xylose (8) was dissolved in cyclopentyl methyl ether (CPME) and transferred to a 50-mL Parr reactor together with 10% Pd/C catalyst. The reactor was sealed and purged with hydrogen gas three times and hydrogen pressure was introduced (30 bar), and then heated to 135 C. for 15 hours with stirring. The reactor was depressurized after cooled to room temperature and the reaction mixture was filtered. The filtrate was evaporated on a rotary evaporator and the residue was purified by flash chromatography to give 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol (11) and other dodecyl-xylose ethers and acetals.

3,5-O-(E)-dodec-2-en-1-ylidene-xylose (MAX12:1(2))

##STR00046##

[0101] In a 1-neck round bottom flask, 1 molar equivalent of D-xylose (5) was mixed with 1.2 molar equivalent (E)-2-dodecenal and 0.02M of sulfuric acid catalyst in dioxane. In order to shift the equilibrium to the product, molecular sieve was added to remove produced water. The reaction was conducted at 45 C. for 15 h. Then, the solution was neutralized with 1M NaOH solution until the pH value becomes around 7. The solution was concentrated on a rotavap with a bath temperature of 45 C. under reduced pressure (80 mbar). Then the residue viscous yellow oil was washed with brine solution and extracted with EtOAc. The organic phase was then evaporated on a rotavap and purified using column chromatography to get two yellowish oil as the products (12). They were characterized by NMR and GCMS.

Analytical Methods

Terminology

[0102] In the context of the present invention the expression MAXn and DAXn refer to xylose compounds, wherein the term n defines the length of the variable linear alkyl group. For example the term MAX12 refers to 3,5-O-dodecylidene-xylose, the term MAX10 refers to 3,5-O-decylidene-xylose and the term MAX8 refers to 3,5-O-octylidene-xylose. On the other hand the expression DAXn refers to similar xylose targets, where the term n defines the length of both variable linear alkyl groups. For example the term DAX12 refers to didodecylidene-xylose, the term DAX10 refers to didecylidene-xylose and the term DAX8 refers to dioctylidene-xylose.

NMR

[0103] All NMR spectra (.sup.1H, .sup.13C, HSQC) were acquired using a Bruker Avance III 400 MHz spectrometer using the standard pulse sequences from Bruker.

GC-MS

[0104] Gas chromatography-mass spectrometry spectra of 3,5-O-octylidene-xylose (MAX8), 3,5-O-decylidene-xylose (MAX10), 3,5-O-dodectylidene-xylose (MAX12) (all FIG. 3A), dioctylidene-xylose (DAX8), didectylidene-xylose (DAX10), didodectylidene-xylose (DAX12) (all FIG. 4A), 3,5-O-(E)-dodec-2-en-1-ylidene-xylose (MAX12:1(2) (FIG. 5) and 3,5-O-octadecylidene-xylose (MAX18) (FIG. 6) were obtained using an Agilent 7890B series GC equipped with a HP5-MS capillary column and an Agilent 5977A series Mass Spectroscopy detector (FIGS. 3B and 4B). A silylation derivatization was applied to all compounds mentioned above by adding 100 L N-Methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA) and 100 L pyridine and kept under r.t. for 30 min before detection. The GC-MS method was performed as follows: The injection temperature was 300 C. 1 L of sample was injected with an autosampler in split mode (split ratio: 25:1). The column was initially kept at 40 C. for 3 min, then was heated at a rate of 30 C. min.sup.1 to 100 C., followed by a heating rate of 40 C. min.sup.1 to 300 C. and held for 5 min.

HPLC (pH 2 Aqueous-Phase Chromatography)

[0105] HPLC analyses for the accelerated aqueous decomposition of MAXn were performed using a HPX-87H Column (300 mm7.8 mm; column temperature=60 C.) using pH 2 water as eluent (flow rate=0.6 ml.Math.min.sup.1, V.sub.inj=20 L) with 1260 Refractive Index Detector (RID) (G1362A)

Characterization Data of Xylose Acetals

1,2-O-dodecylidene--D-xylofuranose (Ic)

##STR00047##

[0106] .sup.1H NMR (400 MHz, CDCl.sub.3) 5.96 (d, J=3.7 Hz, 1H), 5.17 (t, J=4.7 Hz, 0.52H), 4.92 (t, J=4.8 Hz, 0.48H), 4.49 (d, J=3.6 Hz, 1H), 4.42-4.31 (m, 2H), 4.16-3.93 (m, 4H), 1.16-1.42 (m, 18H), 0.86 (t, J=6.7 Hz, 6H).

[0107] .sup.13C NMR (101 MHz, CDCl.sub.3) 106.91, 105.62, 104.65, 104.55, 86.43, 86.22, 81.47, 78.79, 77.09, 76.96, 61.33, 61.20, 34.72, 34.09, 32.03, 29.80, 29.76, 29.75, 29.73, 29.71, 29.63, 29.62, 29.56, 29.54, 29.48, 29.46, 23.85, 23.65, 22.80, 14.24.

[0108] HRMS (nanochip-ESI/LTQ-Orbitrap) m/z: [M+H].sup.+ Calcd for C.sub.17H.sub.33O.sub.5.sup.+317.2323; Found 317.2318.

1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (Ia) (GMAX)

##STR00048##

[0109] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.22 (dd, J=33.6, 3.7 Hz, 1H), 5.48 (d, J=54.7 Hz, 1H), 4.69 (dd, J=57.0, 3.7 Hz, 1H), 4.46 (td, J=5.3, 3.1 Hz, 1H), 4.33-4.18 (m, 2H), 4.01 (q, J=1.8 Hz, 1H), 3.91 (ddd, J=13.5, 6.5, 2.0 Hz, 1H), 1.67-1.50 (m, 2H), 1.26 (d, J=4.3 Hz, 18H), 0.88 (t, J=6.8 Hz, 3H).

[0110] .sup.13C NMR (101 MHz, CDCl.sub.3) 176.92, 171.60, 170.81, 106.66, 106.58, 100.56, 100.48, 100.19, 99.83, 85.97, 84.72, 77.96, 77.80, 73.47, 73.45, 67.19, 66.28, 65.99, 34.75, 34.72, 32.06, 29.78, 29.76, 29.67, 29.62, 29.49, 23.89, 22.83, 20.74, 14.26.

2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol (Va)

##STR00049##

[0111] .sup.1H NMR (400 MHz, CDCl.sub.3) 4.27 (dt, J=3.9, 1.6 Hz, 1H), 4.24-4.17 (m, 2H), 4.16-4.09 (m, 1H), 3.91-3.78 (m, 2H), 3.74-3.67 (m, 1H), 3.58-3.42 (m, 2H), 1.63-1.53 (m, 2H), 1.34-1.22 (m, 18H), 10.87 (t, J=6.8 Hz, 3H).

[0112] .sup.13C NMR (101 MHz, CDCl.sub.3) 79.39, 78.24, 78.16, 73.70, 72.62, 70.06, 32.04, 31.56, 29.78, 29.75, 29.72, 29.67, 29.61, 29.53, 26.13, 22.81, 14.24.

[0113] HRMS (ESI/QTOF) m/z: [M+Na].sup.+ Calcd for C.sub.17H.sub.34NaO.sub.4.sup.+325.23452; Found 325.23455.

3-O-dodecyl-1,2-O-dodecylidene-xylose (Ie)

##STR00050##

[0114] .sup.1H NMR (400 MHz, CDCl.sub.3) 5.96 (d, J=3.7 Hz, 1H), 5.17 (t, J=4.7 Hz, 1H), 4.49 (dd, J=3.7 Hz, 1H), 4.34-4.37 (m, 1H), 4.09-4.14 (m, 1H), 3.78-3.89 (m, 2H), 3.40-3.56 (m, 2H), 1.20-1.36 (m, 36H), 0.87 (t, J=7.08 Hz, 6H).

[0115] .sup.13C NMR (101 MHz, CDCl.sub.3) 106.79, 104.68, 86.28, 80.59, 76.99, 72.72, 69.45, 34.77, 32.94, 32.05, 29.83, 29.80, 29.78, 29.76, 29.73, 29.67, 29.65, 29.58, 29.56, 29.53, 26.25, 23.70, 22.83, 14.25.

[0116] HRMS (ESI/QTOF) m/z: [M+Na].sup.+ Calcd for C.sub.29H.sub.56NaO.sub.5.sup.+507.4020; Found 507.4026.

5-O-dodecyl-1,2-O-dodecylidene-xylose (Id)

##STR00051##

[0117] (b) .sup.1H NMR (400 MHz, CDCl.sub.3) 5.94 (d, J=4.0 Hz, 1H), 4.92 (t, J=4.8 Hz, 1H), 4.39 (d, J=4.0 Hz, 1H), 4.31 (d, J=2.6 Hz, 1H), 4.18 (q, J=3.1 Hz, 1H), 4.00-3.87 (m, 2H), 3.68-3.43 (m, 2H), 1.72-1.57 (m, 2H), 1.51-1.61 (m, 2H), 1.33-1.23 (m, 36H), 0.87 (t, J=6.7 Hz, 6H).

[0118] .sup.13C NMR (101 MHz, CDCl.sub.3) 105.40, 104.58, 86.02, 77.97, 76.88, 72.85, 69.29, 34.12, 32.94, 32.06, 29.81, 29.79, 29.77, 29.75, 29.73, 29.67, 29.64, 29.58, 29.55, 29.53, 26.09, 23.90, 22.83, 14.26.

[0119] HRMS (ESI/QTOF) m/z: [M+Ag].sup.+ Calcd for C.sub.29H.sub.56AgO.sub.5.sup.+591.3173; Found 591.3180.

Didodecylidene-xylose (DAX12) (Ia)

##STR00052##

[0120] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.01 (d, J=3.8 Hz, 1H), 4.94 (t, J=4.8 Hz, 1H), 4.51-4.39 (m, 2H), 4.32-4.22 (m, 1H), 4.20 (d, J=2.1 Hz, 1H), 4.02-3.98 (m, 1H), 3.96-3.88 (m, 1H), 1.72-1.55 (m, 4H), 1.43-1.17 (m, 36H), 0.87 (t, J=6.98 Hz, 6H).

[0121] .sup.13C NMR (101 MHz, CDCl.sub.3) 105.48, 105.34, 100.57, 84.42, 78.48, 72.55, 66.22, 34.81, 34.77, 32.06, 32.05, 29.76, 29.68, 29.64, 29.62, 29.58, 29.51, 29.48, 29.39, 29.32, 29.21, 24.85, 23.97, 23.92, 23.80, 22.83, 14.26.

Didecylidene-xylose (DAX10) (Ia)

##STR00053##

[0122] .sup.1H NMR (400 MHz, CDCl.sub.3) 5.99 (d, J=4.0 Hz, 1H), 4.94 (t, J=4.8 Hz, 1H), 4.50-4.39 (m, 1H), 4.33-4.23 (m, 2H), 4.20 (d, J=2.2 Hz, 1H), 3.96-3.82 (m, 2H), 1.72-1.52 (m, 4H), 1.44-1.22 (m, 28H), 0.87 (t, J=6.8 Hz, 6H).

[0123] .sup.13C NMR (101 MHz, CDCl.sub.3) 107.28, 105.45, 100.57, 84.41, 78.49, 75.09, 72.55, 66.22, 34.77, 34.07, 32.02, 32.00, 29.63, 29.62, 29.60, 29.58, 29.55, 29.50, 29.43, 29.42, 23.96, 23.92, 23.80, 23.66, 22.81, 14.25.

Dioctylidene-xylose (DAX8) (Ia)

##STR00054##

[0124] .sup.1H NMR (400 MHz, CDCl.sub.3) 5.99 (d, J=4.0 Hz, 1H), 4.94 (t, J=4.8 Hz, 1H), 4.52-4.39 (m, 2H), 4.33-4.23 (m, 1H), 4.20 (d, J=2.2 Hz, 1H), 4.04-3.98 (m, 1H), 3.96-3.82 (m, 1H), 1.72-1.52 (m, 4H), 1.45-1.14 (m, 20H), 0.90-0.82 (m, 6H).

[0125] .sup.13C NMR (101 MHz, CDCl.sub.3) 107.28, 105.48, 100.57, 84.41, 78.49, 75.09, 72.55, 66.40, 34.77, 34.07, 31.87, 31.85, 29.54, 29.51, 29.46, 29.29, 29.28, 23.96, 23.92, 23.80, 23.66, 22.77, 22.75, 14.22.

3,5-O-(E)-dodec-2-en-1-ylidene-xylose (MAX12:1(2)) (Ib)

##STR00055##

[0126] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.12-6.69 (m, 1H), 6.20-5.78 (m, 1H), 5.66 (dd, J=8.5, 3.8 Hz, 1H), 5.38 (ddt, J=5.7, 2.0, 1.1 Hz, 1H), 4.82 (dd, J=4.2, 3.3 Hz, 10H), 4.64-3.62 (m, 5H), 2.36-1.84 (m, 2H), 1.20 (d, J=12.3 Hz, 14H), 0.81 (t, J=6.6 Hz, 3H).

[0127] .sup.13C NMR (101 MHz, CDCl.sub.3) 159.34, 136.95, 136.85, 132.93, 125.80, 125.43, 124.62, 104.29, 99.30, 99.14, 97.74, 92.71, 80.52, 79.35, 79.12, 77.34, 77.23, 77.03, 76.71, 75.30, 73.60, 71.56, 66.85, 61.76, 32.76, 32.06, 32.04, 31.89, 31.85, 29.51, 29.50, 29.46, 29.44, 29.35, 29.31, 29.28, 29.26, 29.22, 29.18, 29.14, 28.57, 27.84, 22.67, 22.66, 14.11.

3,5-O-dodecylidene-xylose (MAX12) (Ib)

##STR00056##

[0128] .sup.1H (400 MHz, CDCl.sub.3) 5.69 (d, J=3.8 Hz, 0.6H), 5.17 (s, 0.4H), 4.51-4.40 (m, 1H), 4.25-4.16 (m, 2H), 4.16-4.05 (m, 2H), 4.00-3.78 (m, 1H), 1.65-1.53 (m, 2H), 1.41-1.21 (m, 18H), 0.87 (t, J=6.7 Hz, 3H).

[0129] .sup.13C NMR (101 MHz, CDCl.sub.3) 104.32, 100.52, 80.46, 73.94, 71.85, 67.40, 34.94, 34.83, 29.69, 29.64, 29.55, 29.47, 23.69, 22.80, 14.24.

[0130] HRMS (Sicrit plasma/LTQ-Orbitrap) m/z: [M+H10-1].sup.+ Calcd for C.sub.1-7H.sub.31O.sub.4+299.2217; Found 299.2214.

3,5-O-octadecylidene-xylose (MAX18) (Ib)

##STR00057##

[0131] .sup.1H NMR (400 MHz, CDCl.sub.3) 5.65 (d, J=3.7 Hz, 0.6H), 5.11 (s, 0.4H), 4.25-4.16 (m, 2H), 4.16-4.05 (m, 2H), 4.00-3.78 (m, 1H), 1.65-1.53 (m, 2H), 1.42-1.01 (m, 30H), 0.81 (t, J=6.7 Hz, 3H).

[0132] .sup.13C NMR (101 MHz, CDCl.sub.3) 104.32, 100.52, 80.46, 73.94, 71.85, 67.40, 34.94, 34.83, 29.69, 29.64, 29.55, 29.47, 23.69, 22.80, 14.24.

Interfacial Tension Measurements

[0133] To test the amphiphilic properties of each molecule, we measured the water/oil interfacial tension using pendant drop test. In a typical test, we inject the organic solution with surfactants slowly into the water phase with a bent needle with 1 mm diameter. The interfacial tension is calculated by the force balance with the buoyancy force. The critical micelle concentration (CMC) can be obtained by checking the critical point of interfacial tension-concentration graph. FIG. 7 shows that MAX12 has lowest CMC (0.35 mg/mL) among tail length between 8-12. The CMC of MAX10 and MAX8 are around 2.5 mg/mL.

[0134] FIG. 8 shows that the CMC of 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol (e) is around 0.5 g/L, and it can reduce the interfacial tension (cyclohexane/water) to a plateau value about 1.0 mN/m. 1,2-O-dodecylidene-xylose (d) has a CMC around 1 g/L and induce a decrease of the interfacial tension (cyclohexane/water) to a plateau value about 2.7 mN/m.

[0135] The reaction mixture without purification also has amphiphilic properties, which vary depending on the alkyl chain length shown by FIG. 9a. Among the length from C.sub.8 to C.sub.1-2, DAXn reaction mixture demonstrates the best ability of reducing the interfacial tension to a plateau value about 3 mN/m (cyclohexane/water). And the amphiplic properties of reaction mixture show differences under different hydrogenolysis conditions. For example, 135 C. for 15 h lowered the interfacial tension (cyclohexane/water) to 6 mN/m at 0.5 g/L, while 200 C. for 3 h lowered the interfacial tension(cyclohexane/water) to 11.5 mN/m at 0.5 g/L shown in FIG. 9b.

[0136] FIG. 10 shows the interfacial tension measurements of cyclohexane-water (50.2 mN/m) interface at different concentrations of 1,2-O-dodecylidene -D-xylofuranose (Ic) and some of the most common commercial surfactants such as Span 20, Span 80 and ECOSURF SA-4.

[0137] FIG. 11 shows the interfacial tension measurements of cyclohexane-water (50.2 mN/m) interface at different concentrations of 2-((dodecyloxy)methyl)tetrahydrofuran-3,4-diol (Va) and some of the most common commercial surfactants such as Span 20, Span 80 and ECOSURF SA-4.

[0138] FIG. 12 shows the interfacial tension measurements of cyclohexane-water (50.2 mN/m) interface at different concentrations of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (GMAX) (Ia) and some of the most common commercial surfactants such as Span 20, Span 80 and ECOSURF SA-4.

[0139] FIG. 13 shows the interfacial tension measurements of cyclohexane-water (50.2 mN/m) interface at different concentrations of 3,5-O-(E)-dodec-2-en-1-ylidene-xylose (MAX12:1(2)) (Ib) and some of the most common commercial surfactants such as Span 20, Span 80 and ECOSURF SA-4.

[0140] FIG. 14 shows the interfacial tension measurements of cyclohexane-water (50.2 mN/m) interface at different concentrations of 3,5-O-octadecylidene-xylose (MAX18) (Ib) and some of the most common commercial surfactants such as Span 20, Span 80 and ECOSURF SA-4.

Surface Tension Measurement

[0141] Amphiphilic properties of 1,2-O-carboxylidene-3,5-O-dodecylidene-xylose (GMAX) and sodium 1,2-O-carboxylate-3,5-O-dodecylidene-xylose (SGMAX), the ability of reducing the surface tension of the water, was measured using the pendant drop test. Prepare a series of different concentration surfactant aqueous solutions and load in a 1 mL syringe and install onto a Kruss SDA 30 drop shape analyzer. In a typical test, we slowly make a pendant drop of the surfactant aqueous solution and calculate the surface tension of water by analyzing the shape of the pendant drop (Young-Laplace equation) using the Kruss Advance software (v.1.6.2.0). The critical micelle concentration (CMC) is obtained by checking the point where the plateau starts to form in the surface tension-concentration graph (FIG. 15).

Accelerated Aqueous Decomposition Test

[0142] To gain insight into the degradation products of 1,2-O-dodecylidene-xylose (MAX12) in water, an accelerating aging test was performed by boiling it in water. Samples were taken at various time points and analyzed by HPLC (pH2 aqueous-phase chromatography, HPX-87H Column (300 mm7.8 mm; 125-0140), 1260 Refractive Index Detector (RID) (G1362A), flow rate=0.6 ml.Math.min.sup.1, V.sub.inj=20 L, column temperature=60 C.). It shows that MAX12 can be cleaved into xylose and fatty aldehyde in boiling water in 2 days. And to our knowledge, fatty aldehydes can be oxidized into fatty acids catalyzed by the aldehyde dehydrogenase enzyme. Xylose and fatty acids are readily biodegradable. The result shows that the MAX12 can be easily decomposed and degraded after use (FIG. 16).