Supporting InformationSupporting Information For An eco-compatible pathway to new hydrotropes from...

Supporting Information

For

An eco-compatible pathway to new hydrotropes from tetraolsAurélien Herbinski,a Estelle Métay,a Eric Da Silva,a, Estelle Illous b, Jean-Marie Aubry b* and Marc Lemairea*

a. Univ Lyon, Université Claude Bernard Lyon1, CNRS, INSA-Lyon, CPE-Lyon, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, ICBMS, UMR 5246, Equipe CAtalyse, SYnthèse et ENvironnement (CASYEN), 43, bd du 11 novembre 1918, F-69622 Villeurbanne cedex, France.

b. Unité de Catalyse et Chimie du Solide, Université Lille, CNRS, Centrale Lille, ENSCL, Université d’Artois, F-59000 Lille, France.

† Fax: +33(0)-472-431-408; phones: +33(0)-472-448-507; e-mails:, [email protected] [email protected]

1. General information

All reagents were obtained from commercial sources and used as received. Erythritol (>99%

purity) was purchased from Sigma-Aldrich. Pentaerythritol (>98% purity) was purchased from

ACROS. Valeraldehyde, octanal, decanal and dodecanal were supplied by Sigma-Aldrich or

Alfa-Aesar. Camphorsulfonic acid was purchased from Chimex, Amberlyst 35 were bought

from Rohm and Haas. Pd/C (5 or 10%, Pd on activated carbon, reduced and dry, Escat 1431)

was purchased from Strem Chemicals. All other reagents and solvents were used as received

without further purification. Reactions were monitored by TLC or GC and chromatographic

separations were performed over silica gel 60H (40-63μ). Acetalisation were carried in a 20mL

sealed tube and methylation in 50mL sealed tube. Direct reductive alkylations were undertaken

in a 300mL steel Parr autoclave equipped with a mechanic stirrer.

All compounds were characterized by spectroscopic data. The nuclear magnetic resonance

(NMR) spectra were recorded either on a Bruker ALS 300 (1H: 300 MHz, 13C: 75 MHz), a

DRX 300 (1H: 300 MHz, 13C: 75 MHz) or a Bruker DRX 400 (1H: 400 MHz, 13C: 100 MHz)

spectrometer, in CDCl3 or DMSO-d6 at 293K. Chemical shifts are reported in parts per million

(ppm) and are calibrated on residual solvent peaks: CDCl3 7.16 ppm in 1H and 77.16 ppm in 13C, or DMSO-d6 2.50 ppm in 1H and 39.52 ppm in 13C. Spin-spin coupling constants (J) are

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2018

mailto:[email protected]

given in Hz. The peak patterns are indicated as follows: (s, singlet; d, doublet; t, triplet; q,

quartet; m, multiplet, and br. for broad).

IR spectra were recorded by using a Spectro Nicolet IS10 Smart ITR instrument with an

Attenuated Total Reflectance (ATR) diamond.

ESI HRMS mass spectra were recorded in positive-ion mode by using a hybrid quadrupole

time-of-flight mass spectrometer (Micro-TOFQ-II, Bruker Daltonics, Bremen) with an ESI ion

source. The flow of spray gas was 0.4 bar, and the capillary voltage was 3.5 kV. The solutions

were infused at 10 mL.min-1 in a mixture of solvents (methanol/

dichloromethane/water=45:40:15). The mass range of the analysis was m/z=50–1000, and the

calibration was performed with sodium formate.

GC analyses were performed on a Shimadzu Gas Chromatograph GC-2025 equipped with a

ZB-5-MS column (30.0 m × 0.25mm × 0.25µm). The carrier gas was N2 at a flow rate of 1.27

mL/min. Column temperature was initially 70 °C for 2 min, then gradually increased to 310 °C

at 15 °C/min and finally kept at 310 °C for 10 min. The injector temperature was 280 °C and

for detection a FID was used at 315 °C.

General procedure for the preparation of acetals.

In a round bottom flask equipped with a condenser fitted with a CaCl2 guard, under an argon

atmosphere, the corresponding polyol (10.00 g, 85.0mmol, 3 equiv.) was dissolved in dry EtOH.

The aldehyde (27.3 mmol, 1 equiv.) was added dropwise, followed by camphorsulfonic acid

(10 wt%/aldehyde). Then, the mixture was magnetically stirred at 80 °C for 15 hours. The

mixture was cooled down to room temperature and the solvent was evaporated under reduced

pressure. The residue was triturated in EtOAc and the excess of polyol was filtered off and

washed with cold EtOAc. This operation was repeated two times in order to remove any traces

of polyol. The residue was concentrated, in the case of erythritol, a mixture of regioisomers

acetals were obtained. The ratio of compounds has been determined by H1 NMR. Acetal is

crystalized with the minimum of diethylether in a 250mL round bottom flask. The solution is

cold-filtered by a sintered glass. Purified acetal contained in the solid part is dried under reduced

pressure.

General procedure for the recycling of acid catalyst and excess of polyol.

Same protocol as described above was made for the acetalisation, but after cooling, the acid

resin and the excess of polyol recrystallized and filtrated were dried under vacuum. The mixture

of polyol and acid resin obtained was completed by fresh polyol to restart acetalisation.

General procedure for the preparation of corresponding ethers.

The corresponding acetal (10 mmol) was diluted in dry CPME (100 mL) and 5%-Pd/C (1.06 g,

5 mol% in Pd) was added in a 300 mL stainless steel autoclave. The reactor was tightly closed,

purged three times with hydrogen and hydrogen pressure was introduced (30 bar). The system

was heated at 130 °C and mechanically stirred for 15 hours. After cooling to room temperature,

hydrogen pressure was released and the reaction mixture was then dissolved in EtOAc (100

mL), filtered (Millipore Durapore filter 0.01 μm), and washed two times with 20 mL of EtOAc.

The filtrate was evaporated under reduced pressure and the residue was purified by flash

chromatography to give corresponding ethers, in erythritol case, a mixture of 2 regioisomers

were obtained. The ratio of compounds has been determined by GC.

Thermogravimetric analysisThermoGravimetric Analysis (TGA) experiments were performed with a TA Instruments TGA

Q500 apparatus. Approximately 20 mg of each compound was introduced into a platinum

crucible and a temperature ramp of 5 °C/min was applied from 20 °C to 300 °C under nitrogen

atmosphere. The decrease of the mass was followed as a function of time and temperature.

Table 1: Boiling point/decomposition temperature, half-evaporation-temperature T50ù of O-alkylerythritols (mixture of 1-O and 2-O isomers), O-alkylpentaerythritols, 1-O-alkylglycerols

R Ratio 2 : 9Tboil

Tdecc

(°C)

T50%

(°C)

2.a: 9.a C4H9 60 :40 245 1912.a: 9.a C4H9 100 :0 316 n.d.2.b : 9.b C5H11 58 :42 329 2012.c : 9.c C7H17 59 :41 307c 2212.d : 9.d C9H19 70:30 350 2302.e : 9.e C11H23 65:35 342 237

13.a C4H9 - 302 19613.b C5H11 - 333c 21013.c C7H17 - 315c 22313.d C9H19 - 338c 23913.e C11H23 - 329c 24615.a C4H9 - 258 n.d.15.b C5H11 - n.d. n.d.15.c C7H17 - 301c 14915.d C9H19 - 328c 18415.e C11H23 - n.d.c 204

The table 1 described the values of the second endothermic peak observed by DSC, which are

assigned to the boiling point or the decomposition temperature of the compounds.

ThermoGravimetric Analysis (TGA) is carried out to distinguish whether the endothermic

peaks observed with O-alkylerythritol and O-alkylpentaerythritol correspond to the boiling or

degradation of the compound tested. Since the ATG analysis is carried out in an open capsule

and under a stream of nitrogen, compounds evaporate at a temperature substantially below its

boiling point (T ≈ 60-100°C), thus avoiding its decomposition. Figure 1 shows the TGA

profile of the O-alkylpentaerythritol derivatives

Figure 1 : Mass loss (%) vs temperature of O-alkylpentaerythritol derivatives determined by TGA (5°C/min)

while Figure 2 show the evolution of the boiling points of the most volatile amphiphiles and the half-evaporation-temperature T50% of heavier compounds.

0

50

100

150

200

250

300

350

4 5 6 7 8 9 10 11 12 13

T 50%

(°C

)

Number of carbon x

Figure 2: Half-evaporation-temperature, T50% (°C) vs number of carbon x of the alkyl chain of ()O-alkylerythritol (mixture of 1-O and 2-O isomers), () O-alkylpentaerythritol and () 1-O-alkylglycerol and () n-alcohols Cx-OH

2. Characterization data

All erythritol compounds are a mixture of diastereoisomers

2-butyl-4-(hydroxymethyl)-1,3-dioxan-5-ol 4a:

O

O

Chemical Formula: C9H18O4Molecular Weight: 190,24

HO

HO

1

23

4

5

98

7

6

White solid (Mp =102-104°C). Eluent for isolation: 6:4~4:6 cyclohexane/EtOAc, or crystallization in Et2O. 1H NMR: δ = 0.89 (t, J = 7.1 Hz, 3H, CH3 1), 1.25-1.42 (m, 4H, 2xCH2 2,3), 1.58-1.64 (m, 2H, CH2 4), 2.6 (br, 2H, 2xOH), 3.38 (t, J = 10.4 Hz, 1H, CH2 6), 3.40-3.46 (dt, J = 8.3, 3.8 Hz, 1H, CH 8), 3.72-3.81 (m, 1H, CH 7), 3.83-3.85 (dd, J = 4.1, 1.9 Hz, 2H, CH2 9), 4.15 (dd, J = 10.7, 5.4 Hz, 1H, CH2 6), 4.52 (t, J = 5.2 Hz, 1H, CH 5) 13C NMR: δ = 14.2 (CH3 1), 24.6 (CH2 2), 26.4 (CH2 3), 34.2 (CH2 4), 62.5 (CH2 9), 62.7 (CH 7), 70.7 (CH2 6), 80.8 (CH 8), 102.2 (CH 5). GC: retention time: 9.9 min.; MS (ESI+) calcd for C9H18O4: [M+Na]+ = 213.1103; found: 213.1097.

2,6-dibutyltetrahydro-[1,3]dioxino[5,4-d][1,3]dioxine 6:

O

OO

OChemical Formula: C14H26O4

Exact Mass: 258,1831

White solid (Mp = 74-76°C). Eluent for isolation: 8:2 cyclohexane/EtOAc. 1H NMR: δ = 0.88 (t, J = 7.1 Hz, 6H, 2xCH3), 1.27-1.38 (m, 8H, 4xCH2), 1.56-1.63 (m, 4H, 2xCH2), 3.48-3.61 (m, 4H, 2xCH and CH2), 4.11 (dd, J = 9.4, 3.1 Hz, 2H, CH2), 4.60 (t, J = 5.2 Hz, 2H, 2xCH); 13C NMR: δ = 14.1 (2xCH3), 22.6 (2xCH2), 26.3 (2xCH2), 34.2 (2xCH2), 68.6 (2xCH2), 73.7 (2xCH), 103.1 (2xCH). GC: retention time: 11.75 min.; MS (ESI+) calcd for C14H26O4: [M+Na]+ = 281.1729; found: 281.1721.

2-pentyl-4-(hydroxymethyl)-1,3-dioxan-5-ol 4b:

O

OHO

HOChemical Formula: C10H20O4


White solid (Mp = 104-106°C). Crystallization in Et2O. 1H NMR: δ = 0.89 (t, J = 6.8 Hz, 3H, CH3), 1.25-1.42 (m, 6H, 3xCH2), 1.58-1.64 (m, 2H, CH2), 2.04-2.22 (br, 2H, 2xOH), 3.39 (t, J = 10.4 Hz, 1H, CH2), 3.43-3.49 (dt, J = 9.1, 4.5 Hz, 1H, CH), 3.73-3.82 (m, 1H, CH), 3.86 (t, J = 3.9 Hz, 2H, CH2), 4.15 (dd, J = 10.7, 5.4 Hz, 1H, CH2), 4.52 (t, J = 5.2 Hz, 1H, CH); 13C NMR: δ = 14.1 (CH3) 22.7 (CH2), 24.0 (CH2), 31.8 (CH2), 34.5 (CH2), 63.0 (CH and CH2), 70.7 (CH2), 80.7 (CH), 102.2 (CH). GC: retention time: 10.2 min.; MS (ESI+) calcd for C10H20O4: [M+Na]+ = 227.1259; found: 227.1254.

2-heptyl-4-(hydroxymethyl)-1,3-dioxan-5-ol 4c:

O

OHO


Exact Mass: 232,17

White solid (Mp =108°C). Crystallization in Et2O. 1H NMR: δ = 0.87 (t, J = 6.6 Hz, 3H, CH3), 1.27-1.38 (m, 10H, 5xCH2), 1.57-1.64 (m, 2H, CH2), 2.27 (br, 2H, 2xOH), 3.39 (t, J = 10.5 Hz, 1H, CH2), 3.42-3.47 (dt, J = 12.6, 3.3 Hz, 1H, CH), 3.73-3.81 (m, 1H, CH), 3.85 (dd, J = 4.2, 2.6 Hz, 2H, CH2), 4.15 (dd, J = 10.7, 5.3 Hz, 1H, CH2), 4.53 (t, J = 5.2 Hz, 1H, CH); 13C NMR: δ = 14.2 (CH3), 22.8 (CH2), 24.3 (CH2), 29.3 (CH2), 29.5 (CH2), 31.9 (CH2), 34.5 (CH2), 62.5 (CH2), 62.9 (CH), 70.7 (CH2), 80.8 (CH), 102.2 (CH). GC: retention time: 12.4 min.; MS (ESI+) calcd for C12H24O4: [M+Na]+ = 255.1572; found: 255.1562.

2-nonyl-4-(hydroxymethyl)-1,3-dioxan-5-ol 4d:

O

OHO

HO

Chemical Formula: C14H28O4Exact Mass: 260,1988

White solid (Mp =114°C). Crystallization in Et2O. 1H NMR: δ = 0.88 (t, J = 6.7 Hz, 3H, CH3), 1.26-1.40 (m, 14H, 7xCH2), 1.58-1.62 (m, 2H, CH2), 1.96-2.00 (br, 1H, OH), 2.10 (d, J = 5 Hz, 1H, OH), 3.39 (t, J = 10.4 Hz, 1H, CH2), 3.43-3.49 (dt, J = 9.2, 4.6 Hz, 1H, CH), 3.73-3.81 (m, 1H, CH), 3.83-3.88 (m, 2H, CH2), 4.16 (dd, J = 10.7, 5.4 Hz, 1H, CH2), 4.54 (t, J = 5.2 Hz, 1H, CH); 13C NMR: δ = 14.3 (CH3), 22.8 (CH2), 24.3 (CH2), 29.4 (CH2), 29.6 (CH2), 29.7 (3xCH2), 32.0 (CH2), 34.5 (CH2), 62.9 (CH and CH2), 70.7 (CH2), 80.7 (CH), 102.2 (CH). GC: retention time: 13.9 min.; MS (ESI+) calcd for C14H28O4: [M+Na]+ = 283.1885; found: 283.1881.

2-undecyl-4-(hydroxymethyl)-1,3-dioxan-5-ol 4e:

O

OHO



White solid (Mp =114-116°C). Crystallization in EtOH. 1H NMR: δ = 0.88 (t, J = 6.7 Hz, 3H, CH3), 1,25-1.36 (m, 18H, 9xCH2), 1.57-1.64 (m, 2H, CH2), 2.00 (br, 2H, 2xOH), 3.39 (t, J = 10.4 Hz, 1H, CH2), 3.43-3.49 (dt, J = 9.2, 4.6 Hz, 1H, CH), 3.74-3.82 (m, 1H, CH), 3.86 (t, J = 3.8 Hz, 2H, CH2), 4.15 (dd, J = 10.7, 5.3 Hz, 1H, CH2), 4.53 (t, J = 5.2 Hz, 1H, CH); 13C NMR: δ = 13.9 (CH3), 22.1 (CH2), 23.8 (CH2), 28.7 (CH2), 28.9 (CH2), 29.0

(5xCH2), 31.3 (CH2), 34.1 (CH2), 60,8 (CH2), 60.9 (CH), 70.4 (CH2), 82.6 (CH), 101.9 (CH). GC: retention time: 15.2 min.; MS (ESI+) calcd for C16H32O4: [M+Na]+ = 311.2198; found: 311.2193.

(2-butyl-1,3-dioxane-5,5-diyl)dimethanol 11a [775-74-6] 1 :

O

OHO

OHChemical Formula: C10H20O4


White solid (Mp = 80-81°C). Crystallization in Et2O. 1H NMR: δ = 0.79 (t, J = 6.9 Hz, 3H, CH3), 1.15-1.32 (m, 4H, 2xCH2), 1.48-1.57 (m, 2H, CH2), 2.13 (br, 2H, 2xOH), 3.36 (s, 2H, CH2), 3.44 (d, J = 11.8 Hz 2H, CH2), 3.90 (d, J = 14.4 Hz, 2H, CH2), 3.93 (s, 2H, CH2), 4.35 (t, J = 5.0 Hz, 1H, CH); 13C NMR: δ = 14.1 (CH3), 22.7 (CH2), 26.1 (CH2), 34.6 (CH2), 38.9 (C), 64.3 (CH2), 65.8 (CH2), 69.7 (2xCH2), 103.0 (CH). GC: retention time: 10.8 min.; MS (ESI+) calcd for C10H20O4: [M+Na]+ = 227.1259; found: 227.1248.

3,9-dibutyl-2,4,8,10-tetraoxaspiro[5.5]undecane 12 [5703-81-1]1:

O

O


O

O

White solid (Mp = 57-59°C). Extraction with cyclohexane. 1H NMR: δ = 0.86 (t, J = 7.0 Hz, 6H, 2xCH3), 1.22-1.35 (m, 8H, 4xCH2), 1.53-1.60 (m, 4H, 2xCH2), 3.23-3.33 (m, 2H, CH2), 3.46-3.55 (m, 4H, 2xCH2), 4.39 (t, J = 5.0 Hz, 2H, 2xCH), 4.51 (m, 2H, CH2); 13C NMR: δ = 14.0 (2xCH3), 22.6 (2xCH2), 25.9 (2xCH2), 32.4 (C), 34.5 (2xCH2), 70.2 (2xCH2), 70.6 (2xCH2), 103.0 (2xCH). GC: retention time: 12.3 min.; MS (ESI+) calcd for C15H28O4: [M+Na]+ = 295.1885; found: 295.1877.

2-pentyl-1,3-dioxane-5,5-diyl)dimethanol 11b [5684-87-7] 2 :

O

OHO



White solid (Mp = 82-84°C). Crystallization in Et2O. 1H NMR: δ = 0.88 (t, J = 6.8 Hz, 3H, CH3), 1.27-1.30 (m, 6H, 3xCH2), 1.57-1.64 (m, 2H, CH2), 3.47 (s, 2H, CH2), 3.53 (d, J = 11.9 Hz, 2H, CH2), 4.01 (d, J = 11.9 Hz, 2H, CH2), 4.04 (s, 2H, CH2), 4.45 (t, J = 5.0 Hz, 1H, CH); 13C NMR: δ = 14.2 (CH3), 22.7 (CH2), 23.7 (CH2), 31.8 (CH2), 34.9 (CH2), 38.9 (C), 64.5 (CH2), 65.9 (CH2), 69.7 (2xCH2), 103.0 (CH). GC: retention time: 11.5 min.; MS (ESI+) calcd for C11H22O4: [M+Na]+ = 241.1416; found: 241.1413.

1 W. Conrad, B. Gesner, L. Levasseur, R. Murphy and H. Conrad, J. Org. Chem., 1961, 26, 3571–3574.2 G.-W. Wang, X.-Y. Yuan, Y.-C. Liu and X.-G. Lei, J. Am. Oil Chem. Soc., 1994, 71, 727–730.

2-heptyl-1,3-dioxane-5,5-diyl)dimethanol 11c 2 :

O

OHO



White solid (Mp = 85-86°C). Crystallization in Et2O. 1H NMR: δ = 0.86 (t, J = 6.6 Hz, 3H, CH3), 1.25-1.38 (m, 10H, 5xCH2), 1.55-1.62 (m, 2H, CH2), 3.07 (br, 2H, 2xOH), 3.42 (s, 2H, CH2), 3.50 (d, J = 11.9 Hz, 2H, CH2), 3.96 (d, J = 11.6 Hz, 2H, CH2), 4.98 (s, 2H, CH2), 4.43 (t, J = 5.0 Hz, 1H, CH); 13C NMR: δ = 14.2 (CH3), 22.8 (CH2), 24.0 (CH2), 29.3 (CH2), 29.6 (CH2), 31.9 (CH2), 34.9 (CH2), 39.0 (C), 63.6 (CH2), 65.2 (CH2), 69.7 (2xCH2), 103.0 (CH). GC: retention time: 13.1 min.; MS (ESI+) calcd for C13H26O4: [M+Na]+ = 269.1729; found: 269.1717.

2-nonyl-1,3-dioxane-5,5-diyl)dimethanol 11d 2 :

O

OHO



White solid (Mp = 88-90°C). Crystallization in Et2O. 1H NMR: δ = 0.87 (t, J = 6.7 Hz, 3H, CH3), 1.25-1.36 (m, 14H, 7xCH2), 1.57-1.64 (m, 2H, CH2), 2.18 (br, 2H, 2xOH ), 3.47 (s, 2H, CH2), 3.53 (d, J = 11.9 Hz, 2H, CH2), 4.00 (d, J = 11.9 Hz, 2H, CH2), 4.04 (s, 1H, CH2), 4.45 (t, J = 5.1 Hz, 1H, CH); 13C NMR: δ = 14.3 (CH3), 22,8 (CH2), 24.0 (CH2), 29.4 (CH2), 29.7 (3xCH2), 32.0 (CH2), 35.0 (CH2), 38.9 (C), 64.5 (CH2), 65.9 (CH2), 69.7 (2xCH2), 103.0 (CH). GC: retention time: 14.4 min.; MS (ESI+) calcd for C15H30O4: [M+Na]+ = 297.2042; found: 297.2036.

2-undecyl-1,3-dioxane-5,5-diyl)dimethanol 11e 2 :

O

OHO



White solid (Mp = 93-94°C). Crystallization in Et2O. 1H NMR: δ = 0.87 (t, J = 6.7 Hz, 3H, CH3), 1.25-1.36 (m, 18H, 9xCH2), 1.57-1.63 (m, 2H, CH2), 2.48 (br, 2H, 2xOH ), 3.46 (s, 2H, CH2), 3.52 (d, J = 11.8 Hz, 2H, CH2), 4.00 (d, J = 14.4 Hz, 2H, CH2), 4.02 (s, 2H, CH2), 4.44 (t, J = 5.1 Hz, 1H, CH); 13C NMR: δ = 14.3 (CH3), 22.9 (CH2), 24.0 (CH2), 29.5 (CH2), 29.6 (CH2), 29.7 (2xCH2), 29.8 (2xCH2), 32.1 (CH2), 35.0 (CH2), 38.9 (C), 64.3 (CH2), 65.7 (CH2), 69.7 (2xCH2), 103.0 (CH). GC: retention time: 15.2 min.; MS (ESI+) calcd for C17H34O4: [M+Na]+ = 325.2355; found: 325.2348.

1-O-pentylerythritol 2a:

O

OHHO

OH


Colorless liquid. Eluent for isolation: 4:6~2:8 cyclohexane/EtOAc. 1H NMR: δ = 0.87 (t, J = 6.9 Hz, 3H, CH3), 1.26-1.31 (m, 4H, 2xCH2), 1.52-1.59 (m, 2H, CH2), 3.45 (t, J = 6.8 Hz, 2H, CH2), 3.48-3.58 (m, 2H, CH2), 3.64-3.68 (m, 1H, CH), 3.70-3.71 (m, 2H, CH2), 3.77-3.81 (m, 1H, CH), 3.95 (br, 3H, 3xOH); 13C NMR: δ = 14.1 (CH3), 22.6 (CH2), 28.3 (CH2), 29.2 (CH2), 63.5 (CH2), 71.1 (CH), 72.0 (CH2), 72.1 (CH2), 72.9 (CH). GC: retention time: 10.2 min.; MS (ESI+) calcd for C9H20O4: [M+Na]+ = 215.1259;

found: 215.1247.

2-O-pentylerythritol 9a:

OH

OHHO

O


Colorless liquid. Eluent for isolation: 4:6~2:8 cyclohexane/EtOAc. 1H NMR: δ =0.87 (t, J = 6.9 Hz, 3H, CH3), 1.26-1.31 (m, 4H, 2xCH2), 1.51-1.60 (m, 2H, CH2), 3.33-3.38 (m, 1H, CH), 3.41-3.48 (m, 1H, CH2), 3.57-3.65 (m, 5H, 2xH of CH2 and 3xOH), 3.66-3.69 (m, 2H, CH2), 3.72-3.83 (m, 2H, 1xCH and 1xH of CH2); 13C NMR: δ = 14.1 (CH3), 22.6 (CH2), 28.3 (CH2), 29.8 (CH2), 60.6 (CH2), 63.4 (CH2), 71.0 (CH2), 71.8 (CH), 80.0 (CH). GC: retention time: 10.5 min.; MS (ESI+) calcd for C9H20O4: [M+Na]+ = 215.1259; found: 215.1254.

1-O-hexylerythritol + 2-O-hexylerythritol 2b:

OH

OHHO

O

O

OHHO

OH


Colorless liquid. Eluent for isolation: 4:6~2:8 cyclohexane/EtOAc. 1H NMR: δ = 0.87 (t, J = 6.8 Hz, 3H, CH3), 1.28-1.33 (m, 6H, 3xCH2), 1.52-1.59 (m, 2H, CH2), 2.52 (br, 3H, 3xOH), 3.25-3.30 (m, 0.4x1H, CH secondary ether), 3.44-3.81 (m, 10.6H, 0.58x(3xCH2 and 2xCH for primary ether), 0.42x(CH and 3xCH2 for secondary ether), 3H for -OH); 13C NMR: δ = 14.1 (CH3), 22.7 (CH2), 25.8 (CH2), 29.6 (CH2), 30.0 (CH2 secondary ether), 31.8 (CH2), 60,8 (CH2 secondary ether), 64.0 and 63.6 (CH2), 70.7 (CH2 secondary ether), 71.1 (CH primary ether), 71.6 (CH2 primary ether), 72.0 (CH2 primary ether), 72.1 (CH secondary ether), 72.9 (CH for primary ether), 80.1 (CH secondary ether). GC: retention time: 10.4 and 10.7 min.; MS (ESI+) calcd for C10H22O4: [M+Na]+ = 229.1416; found: 229.1416.

1-O-octylerythritol + 2-O-octylerythritol 2c:

OH

OHHO

O

O

OHHO

OH


Sticky white solid. Eluent for isolation: 4:6~1:9 cyclohexane/EtOAc. 1H NMR: δ = 0.88 (t, J = 6.7 Hz, 3H, CH3), 1.27-1.36 (m, 10H, 5xCH2), 1.55-1.60 (m, 2H, CH2), 2.52 (s, 3H, 3xOH), 3.37-3.41 (m, 0.4x1H, CH secondary ether), 3.46-3.85 (m, 7.6H, 0.59x(3xCH2 and 2xCH for primary ether), 0.41x(CH and 3xCH2 for secondary ether); 13C NMR: δ = 14.1 (CH3), 22.7 (CH2), 26.1 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 primary ether), 30.0 (CH2 secondary ether), 31.9 (CH2), 60.5 (CH2 secondary ether), 64.0 and 63.4 (CH2), 70.5 (CH2 secondary ether), 71.0 (CH

primary ether), 71.4 (CH2 primary ether), 72.0 (CH2 primary ether), 72.1 (CH secondary ether), 72.8 (CH for primary ether), 80.1 (CH secondary ether). GC: retention time: 12.7 and 12.9 min.; MS (ESI+) calcd for C12H26O4: [M+Na]+ = 257.1729; found: 257.1734.

1-O-decylerythritol + 2-O-decylerythritol 2d:

OH

OHHO

O

O

OHHO

OH


White solid (Mp = 39-41°C). Eluent for isolation: 4:6~1:9 cyclohexane/EtOAc. 1H NMR: δ = 0.86 (t, J = 6.7 Hz, 3H, CH3), 1.22-1.29 (m, 14H, 7xCH2), 1.51-1.58 (m, 2H, CH2), 3.25-3.27 (m, 0.30x1H, CH secondary ether), 3.45 (m, 10.7H, 0.70x(3xCH2 and 2xCH for primary ether), 0.30x(CH and 3xCH2 for secondary ether), 3H for -OH); 13C NMR: δ = 14.2 (CH3), 22.8 (CH2), 26.2 (CH2), 29.4 (CH2), 29.6 (CH2), 29.7 (CH2 primary ether), 29.7 (2xCH2), 30.1 (CH2 secondary ether), 32.0 (CH2), 60,7 (CH2 secondary ether), 64.0 and 63.5 (CH2), 70.7 (CH2 secondary ether), 71.1 (CH primary ether), 71.5 (CH2 primary ether), 72.0 (CH2 primary ether), 72.1 (CH secondary ether), 72.9 (CH for primary ether), 80.1 (CH secondary ether). GC: retention time: 14.1 and 14.3 min.; MS (ESI+) calcd for C14H30O4: [M+Na]+ = 285.2042; found: 285.2029

1-O-dodecylerythritol + 2-O-dodecylerythritol 2e:

OH

OHHO

O

O

OHHO

OH


White solid (Mp = 49-51°C). Eluent for isolation: 4:6~1:9 cyclohexane/EtOAc. 1H NMR: δ = 0.88 (t, J = 6.7 Hz, 3H, CH3), 1.24-1.36 (m, 18H, 9xCH2), 1.53-1.60 (m, 2H, CH2), 2.34 (s, 3H, 3xOH), 3.36-3.41 (m, 0.35x1H, CH secondary ether), 3.46-3.84 (m, 7.7H, 0.65x(3xCH2 and 2xCH for primary ether), 0.35x(CH and 3xCH2 for secondary ether); 13C NMR: δ = 14.2 (CH3), 22.8 (CH2), 26.2 (CH2), 29.5 (CH2), 29.6 (CH2), 29.7 (CH2 primary ether), 29.8 (4xCH2), 30.1 (CH2 secondary ether), 32.0 (CH2), 60,7 (CH2 secondary ether), 64.0 and 63.6 (CH2), 70.7 (CH2 secondary ether), 71.1 (CH primary ether), 71.5 (CH2 primary ether), 72.0 (CH secondary ether and CH2 primary ether), 72.9 (CH for primary ether), 80.1 (CH secondary ether). GC: retention time: 15.4 and 15.6 min.; MS (ESI+) calcd for C16H34O4: [M+Na]+ = 313.2355; found: 313.2335

O-pentylpentaerythritol 13a:

HOOHOOH


Colorless liquid. Eluent for isolation: 4:6~1:9 cyclohexane/EtOAc. 1H NMR: δ = 0.89 (t, J = 6.9 Hz, 3H, CH3), 1.27-1.32 (m, 4H, 2xCH2), 1.51-1.58 (m, 2H, CH2), 3.40 (t, J = 6.6 Hz, 2H, CH2), 3.43 (s, 2H, CH2), 3.53 (br, 3H, 3xOH), 3.68 (s, 6H, 3xCH2); 13C NMR: δ = 14.1 (CH3), 22.6 (CH2), 28.4 (CH2), 29.3 (CH2), 45.0 (C), 64.3 (3xCH2), 72.3 (CH2), 73.6 (CH2). GC: retention time: 11.0 min.; MS (ESI+) calcd for C10H22O4: [M+Na]+ = 229.1416; found: 229.1407.

O-hexylpentaerythritol 13b:

HOOHOOH


Colorless liquid. Eluent for isolation: 4:6~1:9 cyclohexane/EtOAc. 1H NMR: δ = 0.87 (t, J = 6.9 Hz, 3H, CH3), 1.27-1.30 (m, 6H, 3xCH2), 1.49-1.58 (m, 2H, CH2), 3.24 (br, 3H, 3xOH), 3.40 (t, J = 6.6 Hz, 2H, CH2), 3.43 (s, 2H, CH2), 3.67 (s, 6H, 3xCH2); 13C NMR: δ = 14.1 (CH3), 22.7 (CH2), 25.9 (CH2), 29.5 (CH2), 31.7 (CH2), 45.0 (C), 64.4 (3xCH2), 72.3 (CH2), 73.7 (CH2). GC: retention time: 11.8 min.; MS (ESI+) calcd for C9H20O4: [M+Na]+ = 243.1572; found: 243.1560.

O-octylpentaerythritol 13c:

HOOHOOH


Colorless liquid. Eluent for isolation: 2:8 cyclohexane/EtOAc. 1H NMR: δ = 0.85 (t, J = 6.7 Hz, 3H, CH3), 1.21-1.30 (m, 10H, 5xCH2), 1.47-1.54 (m, 2H, CH2), 3.37 (t, J = 6.6 Hz, 2H, CH2), 3.39 (s, 2H, CH2), 3.63 (s, 6H, 3xCH2), 3.69 (br, 3H, 3xOH); 13C NMR: δ = 14.2 (CH3), 22.7 (CH2), 26.2 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 31.9 (CH2), 45.0 (C), 63.9 (3xCH2), 72.2 (CH2), 73.4 (CH2). GC: retention time: 13.2 min.; MS (ESI+) calcd for C13H28O4: [M+Na]+ = 271.1885; found: 271.1870.

O-decylpentaerythritol 13d3:

HOOHOOH


White solid (Mp = 93-94°C). Crystallization in Et2O. 1H NMR: δ = 0.87 (t, J = 6.7 Hz, 3H, CH3), 1.25-1.32 (m, 18H, 9xCH2), 1.50-1.56 (m, 2H, CH2), 3.01 (br, 3H, 3xOH ), 3.40 (t, J = 6.6 Hz, 2H, CH2), 3.44 (s, 2H, CH2), 3.69 (s, 6H, 3xCH2); 13C NMR: δ = 14.3 (CH3), 22.8 (CH2), 26.2 (CH2), 29.4 (CH2), 29.6 (2xCH2), 29.7 (2xCH2), 32.0 (CH2), 45.0 (C), 64.7 (3xCH2), 72.3 (CH2), 73.7 (CH2). GC: retention time: 14.3 min.; MS (ESI+) calcd for C15H32O4: [M+Na]+ = 299.2198; found: 299.2196.

O-dodecylpentaerythritol 13e:

HOOHOOH


White solid (Mp = 61°C). Eluent for isolation: 3:7~1:9 cyclohexane/EtOAc. 1H NMR: δ = 0.86 (t, J = 6.7 Hz, 3H, CH3), 1.22-1.29 (m, 18H, 9xCH2), 1.49-1.58 (m, 2H, CH2), 3.39 (t, J = 6.7 Hz, 2H, CH2), 3.42 (s, 2H, CH2), 3.53 (br, 3H, 3xOH), 3.67 (s, 6H, 3xCH2); 13C NMR: δ = 14.2 (CH3), 22.8 (CH2), 26.2 (CH2), 29.5 (CH2), 29.6 (2xCH2), 29.7 (2xCH2), 29.8 (2xCH2), 32.0 (CH2), 45.0 (C), 64.3 (3xCH2), 72.3 (CH2), 73.6 (CH2). GC: retention time: 15.4 min.; MS (ESI+) calcd for C17H36O4: [M+Na]+ = 327.2511; found: 327.2508.

3 J. Berry, J. Org. Chem., 1960, 25, 1272–1274.

2,2-bis((pentyloxy)methyl)propane-1,3-diol 14a:

HOOOOH


Colorless liquid. Eluent for isolation: 6:4 cyclohexane/EtOAc. 1H NMR: δ = 0.88 (t, J = 6.8 Hz, 6H, 2xCH3), 1.22-1.32 (m, 8H, 4xCH2), 1.45-1.55 (m, 4H, 2xCH2), 2.99 (s, 2H, 2xOH), 3.39 (t, J = 6.5 Hz, 4H, 2xCH2), 3.47 (s, 4H, 2xCH2), 3.62 (s, 4H, 2xCH2); 13C NMR: δ = 14.1 (2xCH3), 22.6 (2xCH2), 28.4 (2xCH2), 29.3 (2xCH2), 44.6 (C), 65.4 (2xCH2), 72.1 (2xCH2), 73.1 (2xCH2). GC: retention time: 12.7 min.; MS (ESI+) calcd for C21H44O4: [M+Na]+ = 299.2198; found: 299.2182.

2,2-bis((hexyloxy)methyl)propane-1,3-diol 14b:

HOOOOH


Colorless liquid. Eluent for isolation: 6:4 cyclohexane/EtOAc. 1H NMR: δ = 0.84 (t, J = 7.0 Hz, 6H, 2xCH3), 1.26-1.33 (m, 12H, 6xCH2), 1.48-1.57 (m, 4H, 2xCH2), 3.01 (br, 2H, 2xOH), 3.37 (t, J = 6.6 Hz, 4H, 2xCH2), 3.46 (s, 4H, 2xCH2), 3.62 (s, 4H, 2xCH2); 13C NMR: δ = 14.1 (2xCH3), 22.7 (2xCH2), 25.8 (2xCH2), 29.5 (2xCH2), 31.7 (2xCH2), 44.6 (C), 65.2 (2xCH2), 72.1 (2xCH2), 73.0 (2xCH2). GC: retention time: 13.9 min.; MS (ESI+) calcd for C17H36O4: [M+Na]+ = 327.2511; found: 327.2508.

2,2-bis((octyloxy)methyl)propane-1,3-diol 14c:

HOOOOH


Colorless liquid. Eluent for isolation: 8:2 cyclohexane/EtOAc. 1H NMR: δ = 0.85 (t, J = 6.7 Hz, 6H, 2xCH3), 1.22-1.32 (m, 20H, 10xCH2), 1.45-1.55 (m, 4H, 2xCH2), 2.99 (s, 2H, 2xOH), 3.39 (t, J = 6.5 Hz, 4H, 2xCH2), 3.47 (s, 4H, 2xCH2), 3.62 (s, 4H, 2xCH2); 13C NMR: δ = 14.2 (2xCH3), 22.7 (2xCH2), 26.2 (2xCH2), 29.3 (2xCH2), 29.5 (2xCH2), 29.6 (2xCH2), 29.8 (2xCH2), 31.9 (2xCH2), 44.6 (C), 65.3 (2xCH2), 72.1 (2xCH2), 73.0 (2xCH2). GC: retention time: 15.5 min.; MS (ESI+) calcd for C21H44O4: [M+Na]+ = 383.3137; found: 383.3119.

2,2-bis((dodecyloxy)methyl)propane-1,3-diol 14e:

HOOOOH


White solid (Mp = 54-56°C). Eluent for isolation: 8:2 cyclohexane/EtOAc. 1H NMR: δ = 0.87 (t, J = 6.7 Hz, 6H, 2xCH3), 1.23-1.31 (m, 36H, 18xCH2), 1.50-1.57 (m, 4H, 2xCH2), 2.79 (s, 2H, 2xOH), 3.41 (t, J = 6.5 Hz, 4H, 2xCH2), 3.49 (s, 4H, 2xCH2), 3.64 (s, 4H, 2xCH2); 13C NMR: δ = 14.6 (2xCH3), 22.8 (2xCH2), 26.2 (2xCH2), 29.5 (2xCH2), 29.6 (2xCH2), 29.7 (4xCH2), 29.8 (6xCH2), 32.1 (2xCH2), 44.6 (C), 65.5 (2xCH2), 72.2 (2xCH2), 73.3 (2xCH2). GC: retention time: 20.4 min.; MS (ESI+) calcd for C29H60O4: [M+Na]+ = 495.4389; found: 495.4378.

4. Spectra

2-butyl-4-(hydroxymethyl)-1,3-dioxan-5-ol

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.16

4.21

2.09

2.06

2.02

1.09

1.96

1.01

1.00

0.86

850.

8924

0.91

561.

2469

1.32

941.

4194

1.57

801.

5954

1.60

281.

6105

1.62

091.

6271

1.64

49

2.60

76

3.34

793.

3828

3.40

643.

4183

3.43

423.

4366

3.45

073.

4643

3.83

503.

8416

3.84

893.

8547

4.11

494.

1327

4.15

054.

1683

4.50

344.

5207

4.53

80

7.26

04

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.0

892

22.6

438

26.4

432

34.1

740

62.5

664

62.7

231

70.6

751

77.1

605

80.8

228

102.

1715

HOHO

OO

HOHO

OO

2,6-dibutyltetrahydro-[1,3]dioxino[5,4-d][1,3]dioxine

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

6.36

8.14

4.07

4.01

1.96

2.00

0.85

980.

8836

0.90

681.

2941

1.30

991.

3198

1.33

191.

3445

1.35

681.

3672

1.37

781.

5651

1.58

241.

5901

1.59

721.

6080

1.61

413.

4787

3.48

663.

4951

3.50

403.

5166

3.52

443.

5311

3.54

503.

5524

3.55

843.

5777

3.61

14

4.08

954.

1010

4.12

174.

1311

4.58

554.

6027

4.61

98

7.26

01

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.0

667

22.6

349

26.3

459

34.2

058

68.5

686

73.7

100

77.1

596

103.

0877

O

OO

O

O

OO

O

2-pentyl-4-(hydroxymethyl)-1,3-dioxan-5-ol

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.03

6.00

2.05

1.95

2.01

1.19

1.70

1.01

1.00

0.86

280.

8857

0.90

811.

2727

1.28

591.

2961

1.30

411.

3223

1.35

291.

5763

1.59

361.

6064

1.62

32

2.03

95

2.21

88

3.35

713.

3919

3.42

673.

4405

3.45

593.

4712

3.48

573.

7846

3.84

303.

8559

3.86

894.

1266

4.14

444.

1622

4.51

104.

5283

4.54

55

7.26

01

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

449

22.6

817

24.0

023

31.7

890

34.4

724

62.9

699

70.6

823

77.1

596

80.7

206

102.

1601

HOHO

OO

HOHO

OO

2-heptyl-4-(hydroxymethyl)-1,3-dioxan-5-ol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.01

10.2

7

2.03

2.03

2.03

1.14

1.93

1.02

1.00

0.85

020.

8733

0.89

491.

2653

1.26

921.

3215

1.34

141.

3632

1.37

681.

5726

1.58

991.

6023

1.61

96

2.26

79

3.35

073.

3855

3.42

053.

4288

3.45

953.

4736

3.83

823.

8474

3.85

24

4.11

954.

1373

4.15

51

4.50

444.

5217

4.53

89

7.26

01

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

172

22.7

764

24.3

163

29.3

031

29.5

398

31.8

951

34.4

975

62.7

687

62.8

506

70.6

837

77.1

602

80.7

747

102.

1778

HOHO

OO

HOHO

OO

2-nonyl-4-(hydroxymethyl)-1,3-dioxan-5-ol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.04

14.1

6

2.32

0.98

0.95

1.14

0.94

1.14

2.03

1.04

1.00

0.85

290.

8760

0.89

76

1.25

991.

3966

1.57

651.

5897

1.60

621.

6235

1.95

631.

9756

1.99

752.

0913

2.10

81

3.35

873.

3935

3.42

863.

4446

3.46

003.

4753

3.48

993.

8479

3.85

503.

8673

4.12

884.

1467

4.16

45

4.50

994.

5271

4.54

43

7.26

04

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

536

22.8

171

24.3

133

29.4

393

29.5

808

29.6

451

32.0

227

34.4

985

62.8

976

70.6

763

77.1

599

80.7

421

102.

1662

O

OHO

HO

O

OHO

HO

2-undecyl-4-(hydroxymethyl)-1,3-dioxan-5-ol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.06

18.3

5

2.00

2.01

1.78

1.08

1.99

0.99

0.88

0.85

340.

8765

0.89

78

1.25

341.

3447

1.36

341.

5751

1.59

271.

6220

1.64

22

2.00

19

3.35

723.

3920

3.42

713.

4421

3.45

753.

4728

3.48

723.

8436

3.85

653.

8695

4.12

704.

1447

4.16

26

4.50

854.

5257

4.54

29

7.26

05

0102030405060708090100110120130140150160170180190200210f1 (ppm)

13.9

406

22.1

081

23.8

161

28.7

341

28.9

302

29.0

061

31.3

150

34.1

200

39.5

202

60.8

271

60.9

310

70.3

803

82.6

274

100.

9054

O

OHO

HO

O

OHO

HO

1-O-pentylerythritol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

2.98

4.04

1.97

1.90

2.03

1.14

1.82

1.00

3.14

0.85

650.

8740

0.89

121.

2578

1.26

761.

2729

1.28

271.

2911

1.29

521.

3047

1.30

891.

5221

1.53

931.

5572

1.57

491.

5927

3.42

903.

4460

3.46

313.

4818

3.49

753.

5064

3.52

213.

5463

3.55

703.

5709

3.58

163.

6447

3.66

743.

6730

3.68

373.

6967

3.70

753.

7665

3.78

143.

7923

3.80

713.

9539

7.25

98

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

201

22.5

985

28.2

750

29.2

904

63.4

538

71.0

560

71.9

489

72.0

563

72.8

786

O

OHHO

OH

O

OHHO

OH

2-O-pentylerythritol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

3.10

4.00

2.08

1.00

1.05

5.02

2.11

2.14

0.85

190.

8751

0.89

771.

2619

1.27

441.

2860

1.29

791.

3101

1.51

171.

5342

1.55

711.

5802

1.60

323.

3295

3.34

633.

3599

3.37

543.

4075

3.43

013.

4383

3.45

293.

4610

3.48

373.

5738

3.59

633.

6130

3.62

703.

6313

3.63

763.

6446

3.64

913.

6615

3.67

153.

6756

3.68

403.

6888

3.72

773.

7452

3.76

323.

7849

3.80

243.

8184

3.83

39

7.25

99

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.0

858

22.5

644

28.2

582

29.7

593

60.6

298

63.4

429

71.0

061

71.8

393

77.1

600

79.9

624

OH

OHHO

O

OH

OHHO

O

1-O-hexylerythritol + 2-O-hexylerythritol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.00

6.12

2.02

0.42

10.3

8

0.84

960.

8727

0.89

481.

2785

1.28

801.

3023

1.32

991.

5198

1.53

981.

5626

1.58

041.

5862

3.25

473.

2687

3.28

003.

2906

3.30

283.

4386

3.46

113.

4836

3.54

983.

5593

3.57

333.

7186

3.76

573.

7811

3.80

74

7.26

01

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

367

22.7

019

25.8

232

29.6

011

30.0

393

31.7

557

60.7

686

63.5

903

64.0

143

70.6

788

71.0

762

71.5

747

72.0

024

72.0

478

72.9

115

77.1

600

80.0

707

OH

OHHO

O

O

OHHO

OH

OH

OHHO

O

O

OHHO

OH

1-O-octylerythritol + 2-O-octylerythritol

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.00

10.0

3

1.90

3.04

0.40

7.55

0.85

610.

8793

0.90

091.

2688

1.28

671.

3283

1.35

721.

5546

1.57

701.

5959

2.25

683.

3655

3.38

203.

3980

3.41

443.

4616

3.48

363.

5058

3.51

453.

5379

3.55

723.

5707

3.58

933.

6045

3.61

733.

6215

3.63

683.

7137

3.72

743.

7592

3.77

043.

7755

3.79

773.

8111

3.81

463.

8288

3.84

403.

8544

7.25

95

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

385

22.7

123

26.0

996

26.1

230

29.3

470

29.5

327

29.5

966

30.0

184

31.9

031

60.4

727

63.3

837

64.0

147

70.5

866

71.0

174

71.3

858

71.9

448

72.0

674

72.8

314

77.1

598

80.0

458

OH

OHHO

O

O

OHHO

OH

OH

OHHO

O

O

OHHO

OH

1-O-decylerythritol + 2-O-decylerythritol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.00

14.3

4

2.09

0.30

10.7

0

0.83

930.

8623

0.88

39

1.24

60

1.51

491.

5353

1.55

691.

5781

3.24

853.

2587

3.26

983.

4039

3.41

183.

4288

3.45

143.

4740

3.48

523.

5064

3.51

843.

5285

3.53

893.

5507

3.56

513.

5825

3.59

793.

6291

3.64

713.

6633

3.68

303.

7104

3.72

403.

7530

3.80

32

7.26

05

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

075

22.7

844

26.1

586

29.4

403

29.6

092

29.6

504

29.7

054

29.7

259

30.0

812

32.0

081

60.6

559

63.5

262

64.0

361

70.6

621

71.0

600

71.5

059

72.0

057

72.0

593

72.8

876

77.1

604

80.0

542

OH

OHHO

O

O

OHHO

OH

OH

OHHO

O

O

OHHO

OH

1-O-dodecylerythritol + 2-O-dodecylerythritol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.02

18.0

6

2.00

3.10

0.35

7.65

0.85

470.

8777

0.89

94

1.25

71

1.53

201.

5537

1.57

581.

5950

2.33

97

3.46

063.

4828

3.50

463.

5372

3.55

623.

5696

3.58

833.

6034

3.63

583.

7244

3.73

673.

7428

3.75

833.

7695

3.77

543.

7967

3.81

063.

8277

3.84

37

7.26

03

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

328

22.8

083

26.1

802

29.4

842

29.6

219

29.6

673

29.7

714

29.8

054

30.1

040

32.0

436

60.7

322

63.5

862

70.6

971

71.0

720

72.0

316

72.9

032

77.1

602

80.0

751

OH

OHHO

O

O

OHHO

OH

OH

OHHO

O

O

OHHO

OH

(2-butyl-1,3-dioxane-5,5-diyl)dimethanol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.04

4.14

2.07

2.14

1.98

2.00

2.00

2.12

1.00

0.76

850.

7918

0.81

471.

2045

1.23

271.

2434

1.25

711.

2821

1.31

261.

4790

1.49

671.

5052

1.52

45

2.13

18

3.36

473.

4055

3.44

49

3.87

903.

9270

4.33

104.

3478

4.36

46

7.15

97

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

128

22.6

915

26.1

315

34.6

316

38.9

276

64.3

284

65.8

099

69.7

037

77.1

604

102.

9634

O

OHO

OH

O

OHO

OH

3,9-dibutyl-2,4,8,10-tetraoxaspiro[5.5]undecane

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

6.26

8.17

4.24

3.09

3.48

2.00

1.74

0.82

650.

8501

0.87

341.

2170

1.23

811.

2611

1.28

401.

2926

1.30

451.

3170

1.32

651.

3325

1.34

451.

3552

1.53

471.

5514

1.56

001.

5615

1.56

611.

5823

1.59

961.

6047

3.22

773.

2746

3.31

313.

3222

3.33

113.

4587

3.49

833.

5079

3.53

773.

5465

3.55

08

4.37

594.

3925

4.40

904.

4841

4.49

164.

5220

4.52

95

7.26

04

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.0

391

22.6

288

25.9

495

32.4

246

34.4

998

70.2

307

70.6

491

77.1

603

102.

9557

O

O

O

O

O

O

O

O

2-pentyl-1,3-dioxane-5,5-diyl)dimethanol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.04

6.05

2.05

1.98

2.03

2.08

2.00

1.00

0.86

010.

8830

0.90

541.

2708

1.28

421.

2944

1.30

221.

4024

1.41

111.

5737

1.59

041.

6035

1.62

001.

6429

3.47

453.

5109

3.55

05

3.98

524.

0249

4.03

93

4.43

294.

4497

4.46

65

7.26

01

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

576

22.7

126

23.7

091

31.8

448

34.9

379

38.9

366

64.5

047

65.9

343

69.7

201

77.1

599

102.

9835

O

OHO

OH

O

OHO

OH

2-heptyl-1,3-dioxane-5,5-diyl)dimethanol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.04

10.0

8

2.09

2.03

1.88

2.08

3.93

1.00

0.83

860.

8616

0.88

291.

2571

1.30

951.

3315

1.35

301.

3829

1.55

661.

5734

1.58

641.

6030

1.62

37

3.07

14

3.42

213.

4830

3.52

26

3.95

053.

9765

3.98

93

4.41

164.

4284

4.44

52

7.25

95

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

926

22.7

476

24.0

113

29.3

150

29.5

531

31.8

785

34.9

046

38.9

815

63.6

413

65.2

201

69.6

812

77.1

596

102.

9679

O

OHO

OH

O

OHO

OH

2-nonyl-1,3-dioxane-5,5-diyl)dimethanol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

3.02

14.2

5

2.03

2.07

1.98

2.05

2.03

1.96

1.00

0.84

850.

8717

0.89

32

1.25

441.

3432

1.36

381.

5709

1.61

761.

6385

2.17

61

3.47

373.

5086

3.54

82

3.98

344.

0230

4.03

82

4.42

954.

4465

4.46

32

7.25

99

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

671

22.8

246

24.0

255

29.4

416

29.6

549

32.0

258

34.9

592

38.9

109

64.4

855

65.9

347

69.7

010

77.1

600

102.

9721

O

OHO

OH

O

OHO

OH

2-undecyl-1,3-dioxane-5,5-diyl)dimethanol

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

f1 (ppm)

3.11

18.1

1

2.10

2.17

1.94

2.04

4.01

1.00

0.85

040.

8736

0.89

511.

2492

1.31

861.

3421

1.36

031.

5685

1.58

521.

5982

1.61

481.

6355

2.48

07

3.46

143.

5029

3.54

23

3.97

614.

0240

4.42

584.

4428

4.45

96

7.26

03

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

586

22.8

263

24.0

278

29.4

872

29.6

286

29.6

802

29.6

974

29.7

624

29.7

815

32.0

569

34.9

505

38.9

351

64.2

764

65.7

417

69.7

044

77.1

602

102.

9878

O

OHO

OH

O

OHO

OH

O-pentylpentaerythritol

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

2.99

4.04

2.00

1.98

1.86

3.12

6.13

0.86

610.

8837

0.90

081.

2718

1.27

831.

2879

1.29

631.

3108

1.31

531.

5125

1.52

911.

5360

1.54

691.

5566

1.56

441.

5815

3.38

203.

3984

3.41

493.

4297

3.53

433.

6778

7.26

03

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

360

22.5

658

28.3

724

29.2

623

44.9

791

64.3

420

72.2

532

73.6

272

77.1

597

HOOHOOH

HOOHOOH

O-hexylpentaerythritol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.00

6.03

1.99

3.09

2.22

2.00

6.00

0.84

950.

8726

0.89

481.

2696

1.27

461.

2852

1.29

981.

4935

1.51

541.

5397

1.55

681.

5623

1.58

43

3.23

643.

3754

3.39

733.

4193

3.42

853.

6731

7.26

01

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

381

22.6

824

25.8

630

29.5

423

31.7

011

44.9

978

64.4

308

72.2

692

73.6

598

77.1

648

HOOHOOH

HOOHOOH

O-octylpentaerythritol

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.09

10.1

0

2.00

4.00

6.03

3.02

0.82

600.

8491

0.87

08

1.24

261.

4732

1.49

451.

5168

1.53

85

3.34

773.

3698

3.39

373.

6302

3.68

98

7.25

98

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

472

22.7

069

26.1

483

29.2

970

29.4

518

29.5

438

31.8

780

45.0

419

63.9

304

72.2

191

73.3

952

77.1

597

HOOHOOH

HOOHOOH

O-decylpentaerythritol

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.01

14.1

5

2.04

3.09

2.06

2.00

6.00

0.84

920.

8723

0.89

39

1.25

481.

3166

1.50

151.

5231

1.54

541.

5672

3.00

95

3.38

233.

4042

3.42

613.

4423

3.69

37

7.25

99

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

464

22.8

126

26.2

270

29.4

440

29.5

488

29.6

085

29.6

970

32.0

212

44.9

575

64.7

061

72.3

052

73.7

255

77.1

604

HOOHOOH

HOOHOOH

O-dodecylpentaerythritol

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.07

18.2

0

2.05

2.29

1.94

2.99

6.00

0.84

070.

8638

0.88

54

1.24

36

1.51

201.

5340

1.55

54

3.36

753.

3895

3.41

183.

4202

3.52

733.

6668

7.26

02

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

254

22.7

976

26.2

042

29.4

690

29.5

533

29.5

932

29.6

990

29.7

400

29.7

506

29.7

806

32.0

283

45.0

144

64.2

753

72.2

843

73.5

961

77.1

595

HOOHOOH

HOOHOOH

HOOHOOH

2,2-bis((pentyloxy)methyl)propane-1,3-diol

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

5.98

7.85

4.00

2.06

4.04

3.82

3.80

0.85

540.

8782

0.90

071.

2361

1.24

311.

2625

1.27

521.

2867

1.29

891.

3108

1.49

951.

5216

1.54

441.

5672

1.59

03

2.93

47

3.37

893.

4007

3.42

243.

4807

3.62

88

7.26

00

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

195

22.5

629

28.4

080

29.3

062

44.6

283

65.4

086

72.1

223

73.1

441

77.1

595

HOOOOH

HOOOOH

2,2-bis((hexyloxy)methyl)propane-1,3-diol

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

6.32

12.4

4

4.14

2.00

4.00

4.05

4.16

0.83

260.

8559

0.87

791.

2563

1.26

051.

2691

1.28

501.

3110

1.33

451.

4770

1.49

861.

5230

1.54

561.

5673

3.00

90

3.36

233.

3841

3.40

583.

4562

3.61

54

7.25

98

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.0

869

22.6

524

25.8

485

29.5

339

31.6

735

44.6

451

65.1

564

72.0

926

72.9

620

77.1

599

HOOOOH

HOOOOH

2,2-bis((octyloxy)methyl)propane-1,3-diol

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

6.00

20.1

1

4.04

2.00

4.01

4.01

4.01

0.83

120.

8544

0.87

61

1.25

291.

3016

1.48

241.

5042

1.52

681.

5488

2.99

18

3.36

573.

3875

3.40

923.

4664

3.61

83

7.26

01

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.1

661

22.7

353

26.2

146

29.3

360

29.4

735

29.6

034

31.9

089

44.6

458

65.2

905

72.1

009

73.0

321

77.1

605

2,2-bis((dodecyloxy)methyl)propane-1,3-diol

HOOOOH

HOOOOH

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

6.27

36.2

6

4.32

2.19

4.00

4.01

4.21

0.84

840.

8716

0.89

31

1.25

06

1.52

331.

5457

1.56

74

2.79

41

3.38

703.

4088

3.43

053.

4935

3.61

413.

6357

7.26

05

0102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

549

22.8

275

26.2

708

29.4

957

29.5

740

29.6

541

29.7

343

29.7

628

29.7

770

29.8

084

32.0

570

44.6

229

65.5

289

72.1

809

73.2

653

77.1

602

HOOOOH

HOOOOH

Supporting InformationSupporting Information For An eco-compatible pathway to new hydrotropes from...

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Transcript of Supporting InformationSupporting Information For An eco-compatible pathway to new hydrotropes from...