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Research Article pubs.acs.org/journal/ascecg

Toward the Sustainable Synthesis of Biosourced Divinylglycol from Glycerol Nicolas Sotto,† Clément Cazorla,† Carole Villette,‡ Muriel Billamboz,‡ and Christophe Len*,† †

Sorbonne Universités, Université de Technologie de Compiègne, Centre de Recherches de Royallieu, CS 60319, F-60203 Compiègne cedex, France ‡ Ecole Supérieure de Chimie Organique et Minérale, 1 allée du Réseau Jean-Marie Buckmaster, F-60200 Compiègne, France S Supporting Information *

ABSTRACT: Two high yielding protocols for the dehydration of glycerol to acrolein have been designed using strong Brönsted acid immobilized on silica gels. Acrolein is obtained with yield ranging from 91 to 95% in organic solvent or under solvent free conditions. The optimized solventless protocol has been then adapted for the direct formation of divinylglycol from glycerol. Neo-formed acrolein is directly coupled to divinylglycol by a double addition process giving 72% of the target divinylglycol in 1 h at a 10 g scale. This process could be referred as a two-chamber reactor with no accumulation of acrolein. Moreover, the reaction rate can be monitored by the rate of glycerol addition, which allows securing the whole system. KEYWORDS: Glycerol, Acrolein, Pinacol coupling, Divinylglycol, Solvent free

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INTRODUCTION One the one hand, given the potential increasing amount of glycerol (1) that could be produced in the future from biomass, the industry needs to discover new processes for the transformation of glycerol into higher value products. Different strategies including microbiology, fermentation, and chemistry have already been developed to transform glycerol into propan1,3-diol, succinic acid, dihydroxyaceton, hydroxypropionaldehyde, and epichlorohydrine, and some ideas are to use glycerol as a synthon for a novel drug delivery system or for the reticulation of polymer.1−6 On the other hand, divinylglycol 3 is a interesting plateform molecule widely used for synthesize analogues of natural products, stereocontrolled compounds,7−12 or polyenes.13,14 Diol 3 is also actually used as a cross-linker agent for commercially available polymers, and some patents relate its use to make new copolymers.15−18 In conclusion, the potential of divinylglycol and its derivatives could be expanded and lead to lots of innovative products in different applications: medicinal chemistry, polymer industry, ... Diol 3 can be obtained from (i) D-mannitol;19−23 (ii) Ltartaric acid,24−26 or (iii) glycerol via acrolein27−31 (Scheme 1). Starting from the chiral pool allowed the synthesis of enantiopure divinylglycol 3 but the use of acrolein (2) led to the racemic form of diol 3 as a mixture of dl and meso forms. The synthetic routes coming from D-mannitol and L-tartaric acid present a lot of protection/deprotection steps and poor global yields (from 20 to 52% global yield). In contrast the synthetic route using acrylic aldehyde 2 does not imply any protection/deprotection step and led to divinylglycol 3 in good © XXXX American Chemical Society

Scheme 1. Synthetic Routes to Divinylglycol 3

yield (average 75−80% yield). Moreover, glycerol (1) has been identified as a key feedstock and our reported strategies to valorize the dimer of allylic alcohol 3 are compatible with the racemic form.32 As a consequence, our present work focused on the synthesis of divinylglycol 3 from glycerol (1) via acrolein (2). In a first time, some protocols to form acrylic aldehyde 2 from glycerol (1) will be discussed. In a second time, the storage of toxic acrolein (2) will be avoided and a methodology Received: August 10, 2016 Revised: September 26, 2016

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DOI: 10.1021/acssuschemeng.6b01900 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering

successfully used for this type of dehydration (Table 1, entries 9 and 10).43−45 The most recent works deal with the neat reaction of glycerol in the presence of the acid catalyst with moderate to good results (Table 1, entries 11 and 12).46−48 From all these data, it is notable that: (i) high temperature is required for dehydration of glycerol; (ii) an acidic medium is beneficial to this transformation; (iii) organic or inorganic solvents can be used; (iv) neat reaction is possible; and (v) a large range of acid catalysts can be designed for this transformation. With the optic of an industrial production of divinylglycol 3, our works were focused on developing a robust, clean and cheap methodology for the production of acrolein (2) from glycerol (1) in liquid phase. Our first attempts were realized using paraffin oils as solvent. In order to obtain an efficient and selective transformation of glycerol (1) into aldehyde 2, the solvent was preheated at 320 °C in the presence of a variable quantity of sulfuric acid as homogeneous catalyst. When the defined temperature (320 °C) was reached, glycerol (1) was added dropwise on the hot medium and formed acrylic aldehyde 2 was distilled and condensed (Table 2, entries 1 and 2). In such conditions, a

for a direct transformation of neo-formed aldehyde 2 to diol 3 without any accumulation of aldehyde 2 will be investigated (Scheme 2). Scheme 2. Proposed Pathway to Divinylglycol 3 from Glycerol (1) via Acrolein (2)

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RESULTS AND DISCUSSION Glycerol Dehydration to Acrolein (Step 1). Dehydration reaction of glycerol (1) to acrolein (2) has been widely studied over the past two decades mainly in the gas phase. Numerous patents, articles and reviews deal with the particular transformation, principally realized over heterogeneous acidic catalysts such as heteropolyacids (HPA), zeolites, and mixed metallic oxide.33 Few examples of glycerol dehydration have been reported in liquid phase (Table 1). The first one was

Table 2. Screening of Acid for the Dehydration of Glycerol (1) in Liquid Phase

Table 1. Literature Data for Glycerol Dehydration in Liquid Phase

entry

acid catalyst/solvent

T (°C)

1 2 3 4 5 6 7 8 9 10 11 12

H2SO4/water supported H3PO4/hydrocarbon H2SO4/water water ZnCl2/water H2SO4/water PO4/Nb2O5/water molecular sieves/water KHSO4/parrafin H3[P(W2O10)4]/Al2O3/diesel oil HSiW/neat AlPO4/neat

190 290 350 450 360 400 240 250 280 320 300 270

P (MPa)

34.5 40 25 34.5 nd 7 nd

2 (%)

entry

acid

acid (mol %) in paraffin oils

4934 7235 4736 1237 3839 7440 5041 9042 8043 9244,45 7946 2347,48

1 2 3 4 5 6 7 8 9 10

H2SO4 H2SO4 H2SO4 H2SO4 33 wt % H2SO4·SiO2 (5−40 μm) 33 wt % H2SO4·SiO2 (5−40 μm) 33 wt % H2SO4·SiO2 (5−40 μm) Amberlyst H15 H2PW12O40 SiO2

5 10 0 5 5 10 20 5 30 20

acid (mol %) in glycerol 2 (%)a 0 0 10 5

55b 49b 30c 33d 57b 87b 91b 50b 20b 1b

a

The yield was calculated from HPLC analysis using catechol as internal standard. bReaction conditions: a mixture of acid and paraffin oils (50 mL) was heated at 320 °C for 1 h, then 1 (9.0 g, 97.8 mmol) was added dropwise over 1 h on this mixture at 320 °C. Acrolein (2) was immediately formed, distilled, and condensed in a flask containing 50 mL of water and 100 mmol of catechol as stabilizer. cReaction conditions: paraffin oils (50 mL) were heated at 320 °C for 1 h, then a mixture of 1 (9.0 g, 97.8 mmol) and acid was added dropwise over 1 h on the solvent at 320 °C. dReaction conditions: a mixture of acid and paraffin oils (50 mL) was heated at 320 °C for 1 h, then a mixture of 1 (9.0 g, 97.8 mmol) and acid was added dropwise over 1 h on the solvent at 320 °C.

reported by the Shell society in 1936, in the presence of aqueous sulfuric acid at 190 °C and gave the corresponding aldehyde 2 in 49% yield (Table 1, entry 1).34 After that pionneering work, Hoyt and Manninen developed a methodology using supported phosphoric acid in an high boiling organic solvent to led to 72% in acrolein (2) at around 290 °C (Table 1, entry 2).35 Sub- and supercritical water have been used to transform glycerol (1) to acrylic aldehyde 2 at temperature over 350 °C and high pressure (Table 1, entries 3−6).36−40 Some efforts have also been devoted to the development of continuous flow process for conversion of glycerol (1) to acrolein (2).38 Some protocols in water were realized at lower temperature 240−250 °C in the presence of super acidic medium41 or structurally defined molecular sieves42 (Table 1, entries 7 and 8). Other organic solvent with high boiling points such as paraffin or diesel oils have been

moderate average 50% yield is obtained at the end of the process. Using 5 or 10 mol % of sulfuric acid did not significantly impact on the yield. Some carbonated residues were observed in the solvent at the end of the process, for a complete conversion of glycerol (1). Moreover, hazardous reaction between the paraffin oils and the liquid acid was observed during the preheating. As a consequence, adding the B


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The results obtained for 10 and 20 mol % are quite similar, with excellent yields obtained with 26 and 33 wt % H2SO4·SiO2 (5− 40 μm). Increasing the quantity of acid immobilized on silica did not lead to any improvement. From these data, the optimum ratio acid/silica was determined at 33 wt %. This immobilized catalyst used at 20 mol % led to 91% yield in aldehyde 2. In order to improved the acid catalytic system, an investigation on the nature of the support was then realized with a ratio acid/silica of 33 and 41 wt % using 20 mol % of acid (Table 3). Montmorillonite K10 is one of the most

acid with glycerol (1) was attempted but the yield in acrolein (2) was lower than expected (Table 2, entry 3). Sharing the acid amount between the solvent and the glycerol did not allow to increase the yield in aldehyde 2 (Table 2, entry 4). As a consequence, to improve the safety aspects, liquid sulfuric acid was avoided and efforts were devoted to the use of some supported or solid acids as heterogeneous catalysts. Sulfuric acid supported on silica [33 wt % H2SO4·SiO2 (5−40 μm)] was prepared according to reported protocols.47,48 Fine silica gel 5− 40 μM was used for a first batch preparation. Using 5 mol % of this immobilized acid catalyst gave 57% in acrylic aldehyde 2, which is comparable with the results obtain for liquid sulfuric acid in the same amount (Table 2, entry 1 compared with entry 5). However, using the supported acid, no reaction with the solvent nor degradation were observed, which is a real improvement compared with liquid sulfuric acid. As it is immobilized on silica, sulfuric acid seems more stable. Increasing its amount to 10 then 20 mol % allowed to reach excellent yields in the target aldehyde 2 up to 91% (Table 2, entries 6 and 7). It is notable than the reaction is complete at the end of the addition of glycerol (1) and than no accumulation of the toxic aldehyde 2 has been observed. From security aspects and monitoring facilities, it is noteworthy than the dehydration of glycerol (1) began as soon as glycerol met the acidic medium and than the rate of production of acrolein (2) can be managed by the rate of addition of glycerol. The use of commercially available acidic resins such as Amberlyst H15 led to a medium yield (50%) but with physical damages of the particles of supported acid due to the wellknown instability of the resin at high temperature (Table 2, entry 8). Suspending a phosphotungstic heteropolyacid in paraffin oils led to a moderate 20% yield, even at 30 mol % (Table 2, entry 9). As expected, sole silica gel (5−40 μM) was not able to promote the dehydration of glycerol (Table 2, entry 10). As a consequence, further optimization of the ratio silica/ sulfuric acid and the amount of acid in the medium was realized (Figure 1).

Table 3. Study on the Supported Sulfuric Acid and Its Quantity in Paraffin Oilsa

entry 1 2 3 4 5 6 7 8 9 10

support SiO2 (5−40 μm) montmorillonite K10 celite charcoal zeolite ZSM-5

quantity of supported acid (wt %) 2 (%)b 33 41 33 41 33 41 33 41 33 41

91 85 60 73 10 68 30 32 36 44

a

Reaction conditions: immobilized sulfuric acid (20 mol %) and paraffin oils were heated at 320 °C for 1 h, then 1 (9 g, 97.8 mmol) was added dropwise over 1 h on this mixture at 320 °C. Acrolein (2) was immediately formed, distilled, and condensed in a flask containing 50 mL of water and 100 mmol of catechol as stabilizer. bThe yield was calculated from HPLC analysis using catechol as internal standard.

intensively explored catalytic materials in heterogeneous catalysis due to its low cost and ecofriendliness. In our hands, montmorillonite K10 displayed good results but lower activity than silica gel at the same amount (Table 3, entries 3 and 4). Celite presented good activity at 41 wt % with a similar result as with montmorillonite K10 (Table 3, entry 6) and gave poor yield of aldehyde 2 at 33 mol % (Table 3, entry 5). Charcoal, consisting of carbon and any remaining ash, presented a good activity with high conversion but a low selectivity for acrolein (2) with only 30% yield obtained (Table 3, entries 7 and 8). Zeolite ZSM-5, well-known for its acidic properties, promoted the dehydration of glycerol and led to 36% yield in aldehyde 2 (Table 3, entry 9). Immobilizing sulfuric acid on zeolite ZSM-5 at 41 wt % did not allowed any significant increase in yield (Table 3, entry 10). As a consequence, silica gel SiO2 (5−40 μm) was conserved as support. Using sulfuric acid supported on silica [33 wt % H2SO4·SiO2 (5−40 μm)] (20 mol %) in paraffin oils at 320 °C (Table 3, entry 1), dehydration of glycerol (1) occurred smoothly to give 91% of acrylic aldehyde 2. Analysis of the paraffin oils have been done and no glycerol have been detected proving its complete conversion at the end of the process. In our hands, no acrolein polymerization and only traces of undetermined carbonated compounds have been observed. However, in the frame of green chemistry, solvent free reactions are more and more developed for their high selectivity and rate. In our case,

Figure 1. Variation of the ratio acid/silica at different amounts for H2SO4·SiO2 (5−40 μm) and the quantity of acid in paraffin oils.

Various amounts of sulfuric acid between 26 and 60 wt % were immobilized on silica gel (5−40 μM). Then the dehydration process was realized by suspending a fixed amount of supported acid (5−20 mol %) in paraffin oils at 320 °C, followed by the dropwise addition of pure glycerol (1). Using 5 mol % of acid in the medium did not allow yields over 70% probably due to a lack of available acid catalyst in the medium. C


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conditions (Figure 2). Regardless of the acid concentration (26−50 wt %), the use of H2SO4·SiO2 (5−40 μm) led to

such conditions could lead to an improvement in selectivity, as glycerol (1) could be directly poured on the acid medium without any dilution. From a practical viewpoint, supported acids were heated under stirring at 320 °C and glycerol (1) was then added dropwise on the solid. Aldehyde 2 were distilled and condensed. Various parameters have been screened in such neat conditions (Table 4). Table 4. Study on the Immobilized Acid and Its Quantity in Solvent Free Conditionsa

entry

acid

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

H2SO4

support SiO2 (5−40 μm) montmorillonite K10 celite charcoal SiO2 (70−200 μm)

H3PO4

SiO2 (5−40 μm) SiO2 (70−200 μm)

quantity of supported acid (wt %)

2 (%)b

33 41 33 41 33 41 33 41 33 41 50 33 41 33 41

85 85 60 80 45 45 29 22 58 75 85 81 85 81 95

Figure 2. Screening of immobilized acid and the quantity of acid on solvent free conditions.

acrolein (2) with identical yield (85%). Against by the use of other support with different granulometry H2SO4·SiO2 (70− 200 μm), glycerol (1) produced the aldehyde 2 with yields which increase with the amount of acid used. Similar remarks were done using H3PO4·SiO2 (70−200 μm) and H3PO4·SiO2 (70−200 μm) with the best result obtained in the presence of 41 wt % H3PO4·SiO2 (70−200 μm) (20 mol %). To conclude, two different protocols have been optimized for the formation of acrylic aldehyde 2 by dehydration of glycerol (1). The first one is realized in liquid phase by suspending 33 wt % H2SO4·SiO2 (5−40 μm) (20 mol %) in paraffin oils at 320 °C and gave 91% yield in acrolein (2). The second one is realized in solvent-free conditions on 41 wt % H3PO4·SiO2 (7− 200 μm) (20 mol %) and led to the aldehyde 2 in 95% yield. The two optimized protocols are robust, reproducible and fast. It is notable than the reaction is complete at the end of the addition of glycerol and than no accumulation of the toxic aldehyde 2 has been observed. From security aspects and monitoring facilities, it is noteworthy than the dehydration of glycerol (1) began as soon as glycerol met the acidic medium and than the rate of production of acrolein (2) can be managed by the rate of addition of glycerol. Following our objective, these two protocols were combined to synthezise target divinylglycol 3. Divinylglycol from Glycerol (Steps 1 + 2). The main goal of our work was the design of a secured process for the formation of diol 3 from glycerol (1) (Scheme 3). This means to avoid the storage and handling of toxic aldehyde 2. As a consequence, efforts were devoted to transform acrolein as soon as it was produced without any intermediate storage. Diol 3 is obtained by the pinacol coupling of the corresponding aldehyde 2. From dehydration of itol 1, acrolein

a

Reaction conditions: immobilized acid (20 mol %) was heated at 320 °C for 1 h, then 1 (9g, 97.8 mmol) was added dropwise over 1 h on this mixture at 320 °C. Acrolein (2) was immediately formed, distilled, and condensed in a flask containing 50 mL of water and 100 mmol of catechol as stabilizer. bThe yield was calculated from HPLC analysis using catechol as internal standard.

To our delight, using sulfuric acid supported on silica [33 or 41 wt % H2SO4·SiO2 (5−40 μm)] (20 mol %) in neat conditions led to acrolein (2) in good yield (85%). Neither unexpected degradation nor hazardous reaction occurred in such solvent free conditions (Table 4, entries 1 and 2). Changing the support in solvent free reaction for sulfuric acid led to similar results than those obtained in the presence of paraffin oils (Table 4, entries 3−8). It is well-known that fine silica gel (5−40 μM) presents security and handling issues due to its volatility and explosivity. As a consequence, the catalytic ability of silica gel 70−200 μM has been investigated (Table 4, entries 9−11). For the same acid amount on silica, the yields in aldehyde 2 are lower. It is necessary to increase the amount of acid to 50 wt % to obtain similar yield (85%). This could be due to a less intimate contact between glycerol (1) and acid due to steric hindrance of the bigger particles. However, orthophosphoric acid was also tested in such conditions and no dramatic impact of the silica particle size was observed for this strong triacid (Table 4, entries 12−15). Similar results have been obtained for fine or bigger silica at 33 and 41 wt % with a maximal 95% yield in acrylic aldehyde 2 obtained (Table 4, entry 15). Further investigations were performed for both acids (sulfuric acid and orthophosphoric acid) in solvent-free

Scheme 3. Direct Formation of Divinylglycol 3 from Glycerol (1) without Isolation of Acrolein (2)

D


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Using the conditions defined by Trost et al.,28 after 24 h of stirring, 50% yield in dimer of allylic alcohol 3 are obtained from the corresponding itol 1 (Table 5, entry 1). No trace of unreacted toxic acrolein (2) has been detected in the crude product, but allylic alcohol 4 (around 5%) and traces of acrylic acid 5 and polymers have been observed. The resulting medium is white with a lot of solids which could be zinc salts but also polymers coming from acrolein derivatives. From our point of view, the medium proposed by Trost et al. is not sufficiently active to promote the pinacol coupling of acrolein (2) before its degradation or side-reaction. In fact, during the process, acrylic aldehyde 2 is produced drop by drop, and at a fixed time, its concentration is really low. As a consequence, intermolecular pinacol coupling is not favored. Aluminum trichloride is known to promote pinacol coupling and increase the reaction rate.51 In our hands, in the presence of 0.33 equiv AlCl3 and 3 equiv zinc, the pinacol coupling reaction occurred but the global yield in divinylglycol 3 is moderate (44%) (Table 5, entry 2). Moreover, 16% of allylic alcohol 4 has been quantified, accompanied by various side products. No residual toxic acrolein (2) and no acrylic acid 5 have been detected. This result can be explained by the production of HCl when aluminum chloride is dissolved in sole water. In fact, HCl has been proved to favor direct reduction in allylic alcohol and side reactions.50 Using Amberlyst H15 as supported acid at 70 °C did not allow any improvement for the production of diol 3. In fact, each drop of formed aldehyde 2 is preferently converted to allylic alcohol 4 (45%), probably due to the higher temperature and low concentration (Table 5, entry 3). The following works were realized with acetic acid as promoter. Our group proved than acetic acid is a powerful booster for the pinacol coupling as this particular reaction was completed in only 20 min at room temperature. Moreover, it was reported a direct correlation between the concentration of AcOH in water and the yield in pinacol product, with an optimum for 2 equiv.49 This data has to be adapted to our continuous production of acrolein. When placing 1.5 equiv of acetic acid in water at the beginning of the process, a global 27% yield in diol 3 is obtained, with few allylic alcohol 4 formed (3%) (Table 5, entry 4). As expected, decreasing the initial amount of acetic acid to 0.5 equiv led to an improvement of yield to 46% of divinylglycol 3 (Table 5, entry 5). Considering this correlation between yield and acid concentration, it was proposed to add acetic acid at the same rate as glycerol (1) (Table 6). When 1.5 equiv of acetic acid was added over 1 h and in the same rate than glycerol, yield of divinylglycol 3 dramatically increased from 27 to 58% (Table 5, entry 4 and Table 6, entry 1), proving the significant impact of the acid concentration on the pinacol coupling step. Varying the concentration of acetic acid from 0.44 to 1.5 equiv, the optimal concentration was then adjusted to 0.55 equiv of acetic acid slowly added to the pinacol coupling medium as far as acrolein (2) was distilled. This double addition process allowed the one-pot, two-step formation of diol 3 from glycerol (1) in 60% yield. Only 5% of allylic alcohol 4 was quantified at the end of the process, accompanied by a trace of acrylic acid 5 (less than 1%) (Table 6, entry 5). Substitution of water by ethanol, two green solvents, produced the diol 3 in 72% yield starting from glycerol (1) in a one-pot, two-step process (Table 6, entry 7). This last result permitted to vary the nature of the solvent for the pinacol coupling in function of the solubility of aldehyde and diol.

(2) is formed accompanied by water. As a consequence, the pinacol coupling methodologies have to be compatible with water. Following our previous works on pinacol coupling49,50 and literature data,28,51 five different protocols in aqueous media with zinc as metal redactor were selected. Each protocol was tested under our optimized conditions for solvent free production of acrolein (2). The neo-formed aldehyde 2 was condensed in the pinacol coupling medium under stirring. In a first attempt, all reactants were put in the reaction flask at the beginning of the process, considering that all the polyol 1 will be dehydrated to the aldehyde 2. The process could be referred as a two-chambers reactor. In the first batch, glycerol (1) was dehydrated to aldehyde 2 that was immediately distilled and condensed in the coupling medium. No accumulation of toxic acrolein (2) was detected and each drop of the intermediate was directly put in contact with zinc and promoter in the second chamber of the reactor (Figure 3).

Figure 3. Two chambers reactor for the production of divinylglycol 3 starting from glycerol (1) via a one-pot, two-step process.

The reaction was realized on a 10.0 g scale of glycerol (1) in a maximal concentration of 1 M for divinylglycol 3. Some side products were expected such as allylic alcohol 4 coming from the direct reduction of compound 2 or acrylic acid 5 coming from the oxidation of aldehyde 2 (Table 5). Table 5. Study on the Direct Production of Divinylglycol 3 Starting from Glycerol (1)a

entry

acid and solvent

1 2 3

THF/NH4Clsat AlCl3/H2O 2 equiv Amberlyst H15/H2O 1.5 equiv AcOH/H2O 0.5 equiv AcOH/H2O

4 5

equiv Zn

T (°C)

t (h)

3 3 3

rt rt 70

24 24 2

50 44 25

5 16 45

2 2

rt rt

1 1

27 46

3 4

3 (%)b 4 (%)b

a

Reaction conditions: glycerol (9.8 g, 100 mmol) was added on 41 wt % H3PO4·SiO2 (70−200 μm) (20 mol %) at 320 °C during 1 h. Then, neo-formed acrolein (2) was distilled and condensed in 50 mL of water containing additives as defined from selected protocols. When addition of glycerol is finished, the stirring of the pinacol coupling medium remained during a defined time. bThe yield was calculated from HPLC analysis using catechol as an internal standard. E


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General Procedure for the Formation of Acrolein (2) by Dehydration of glycerol (1) in Solvent Free Conditions. The system is composed of a round-bottom flask equipped with a distillation column, a condenser and a heating mantle. The immobilized acid 41 wt % H3PO4·SiO2 (70−200 μm) (20 mol %) was stirred ad heated at 320 °C during 1 h. Glycerol (1, 9.0 g, 97.8 mmol) was then added dropwise over 1 h on the hot catalyst. Acrolein (2) was immediately formed, distilled and condensed in a flask containing 50 mL of water and 100 mmol of catechol as stabilizer. The resulting mixture of acrolein in water was quantified by HLPC as catechol as an internal standard. General Procedure for the Formation of Divinylglycol 3. In a first part, the system is composed of a round-bottom flask equipped with a distillation column, a condenser, and a heating mantle. The pinacol coupling part is composed of a round-bottom flask with a magnetic stirrer. The immobilized acid 41 wt % H3PO4·SiO2 (70−200 μm) (20 mol %) was stirred and heated at 320 °C during 1 h. The pinacol coupling medium was prepared by suspending zinc dust (2 equiv, 6.5 g) in 50 mL of ethanol. Glycerol (1, 9.0 g, 97.8 mmol) was then added dropwise over 1 h on the hot catalyst. In the same time, acetic acid (0.55 equiv, 1.6 mL) was added dropwise to the suspension of zinc in EtOH. Acrolein (2) was immediately formed, distilled and condensed in the flask containing zinc, EtOH and a evoluting amount of acetic acid. At the end of the additions, the resulting mixture is stirred during 20 additional minutes. A sample is used for HPLC analysis (UV detection) to observe the presence of any side products. The mixture is then filtered off to eliminate zinc salts. Ethanol is evaporated under vacuum. The resulting crude product is purified by flash chromatography using cyclohexane/AcOEt as eluting solvent giving divinylglycol as a colorless oil. (2E,6E)-Hexa-2,6-diene-4,5-diol (dl and meso) (3). Colorless oil. 1 H NMR (400 MHz, CDCl3) δ ppm: 2.89 (bs, 2H, CH−OH), 3.92 (d, 1H, CH−OH, J = 3.2 Hz, dl or meso form), 4.14 (d, 1H, CH−OH, J = 4.9 Hz, dl or meso form), 5.31−5.16 (m, 4H, CH2CH), 5.84− 5.76 (m, 2H, CH2CH). 13C NMR (100 MHz, CDCl3, ppm): δ = 75.4 (CH−OH), 75.8 (CH−OH), 117.4 (CH2CH), 117.4 (CH2 CH), 135.9 (CH2CH), 136.6 (CH2CH). m/z (ESI) = 115.07 [MH]+.

Table 6. Study on the Direct Production of Divinylglycol 3 Using a Double Addition of Acetic Acid and Glycerola

entry

equiv AcOH

solvent

3 (%)b

4 (%)b

1 2 3 4 5 6 7

1.5 0.8 0.7 0.6 0.55 0.44 0.55

H2O

58 51 56 55 60 52 72

5 5 5 5 5 5 4

EtOH

a

Reaction conditions: glycerol (9.8 g, 100 mmol) was added on 41 w% H3PO4·SiO2 (70−200 μm) (20 mol %) at 320 °C during 1 h. Then, neo-formed acrolein (2) was distilled and condensed in 50 mL of solvent containing zinc dust (2 equiv) and an evoluting amount of acetic acid. When addition of glycerol is finished, the stirring of the pinacol coupling medium remained during 20 min. bThe yield was calculated from HPLC analysis using catechol as an internal standard.

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CONCLUSION Two high yielding protocols for the selective dehydration of glycerol (1) to acrolein (2) have been designed using immobilized strong acids on silica gel. Each protocol has been optimized on a 10 gram scale of glycerol (1) at 320 °C. The first one is realized in paraffin oils and gave 91% yield acrolein using 33 wt % H2SO4·SiO2 (5−40 μm) (20 mol %) as catalyst. The second one is a solvent free reaction on 41 wt % H3PO4·SiO2 (70−200 μm) (20 mol %) conducting to a 95% yield in acrolein. This latter protocol has been adapted to the target production of divinylglycol 3 by the direct condensation of the neo-formed acrolein (2). Using a double addition protocol for acetic acid and glycerol (1), the target diol 3 is produced over 1 h in 72% yield with a high selectivity. Allylic alcohol 4, acrylic acid 5, and some carboneous residues have been observed as side products but in low amounts. Moreover, no trace of residual toxic acrolein (2) is detected, which is notable from a security point of view.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.6b01900. Copies of NMR spectra (PDF)

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EXPERIMENTAL SECTION

General Information. Glycerol and solvents were used without further purification. Reactions were monitored by HPLC (Shimadzu) in the presence of catechol as internal reference and with detection by UV at 200 nm. Flash column chromatography was performed on an automatic apparatus, using silica gel cartridges. 1H and 13C NMR spectra were recorded on a 400 MHz/54 mm ultralong hold. Chemical shifts (δ) are quoted in parts per million (ppm) and are referenced to TMS as an internal standard. Coupling constants (J) are quoted in hertz. Comparisons with known or reported compounds have been used to confirm the NMR peak assignments. General Procedure for the Formation of Acrolein (2) by Dehydration of Glycerol (1) in Paraffin Oils. The system is composed of a round-bottom flask equipped with a distillation column, a condenser and a heating-mantle. The immobilized acid 33 wt % H2SO4·SiO2 (5−40 μm) (20 mol %) was suspended in 50 mL of paraffin oils and heated at 320 °C during 1 h. Glycerol (1, 9.0 g, 97.8 mmol) was then added dropwise over 1 h on the heated medium. Acrolein (2) was distilled and condensed in a flask containing 50 mL of water and 100 mmol of catechol as stabilizer. The resulting mixture of acrolein in water was quantified by HLPC as catechol as an internal standard.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was performed, in partnership with the SAS PIVERT, within the frame of the French Institute for the Energy Transition (Institut pour la Transition Energétique (ITE) P.I.V.E.R.T. (www.institut-pivert.com) selected as an Investment for the Future (“Investissements d’Avenir”). This work was supported, as part of the Investments for the Future, by the French Government under the reference ANR-001-01.

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REFERENCES

(1) Katryniok, B.; Paul, S.; Bellière-Baca, V.; Rey, P.; Dumeignil, F. Glycerol dehydration to acrolein in the context of new uses of glycerol. Green Chem. 2010, 12, 2079−2098.

F


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ACS Sustainable Chemistry & Engineering (2) Len, C.; Merlot, A. S.; Postel, D.; Ronco, G.; Villa, P.; Goubert, C.; Jeufrault, E.; Mathon, B.; Simon, H. Synthesis and antifungal activity of novel bi(dithiocarbamate) derivatives of glycerol. J. Agric. Food Chem. 1996, 44, 2856−2858. (3) Len, C.; Postel, D.; Ronco, G.; Villa, P.; Goubert, C.; Jeufrault, E.; Mathon, B.; Simon, H. Synthesis of carbamic esters derivatives of itols: antifungal activity against various crop diseases. J. Agric. Food Chem. 1997, 45, 3−6. (4) Rafin, C.; Veignie, E.; Sancholle, M.; Postel, D.; Len, C.; Villa, P.; Ronco, G. Synthesis and antifungal activity of novel bisdithiocarbamate derivatives of carbohydrates against Fusarium oxysporum f. sp. Lini. J. Agric. Food Chem. 2000, 48, 5283−5287. (5) DeSousa, R.; Thurier, C.; Len, C.; Pouilloux, Y.; Barrault, J.; Jerome, F. Regioselective functionalization of glycerol with a dithiocarbamate moiety: an environmentally friendly route to safer fungicides. Green Chem. 2011, 13, 1129−1132. (6) Kumari, M.; Billamboz, M.; Leonard, E.; Len, C.; Böttcher, C.; Prasad, A. K.; Haag, R.; Sharma, S. K. Self-assembly, photoresponsive behavior and transport potential of azobenzene grafted dendronized polymeric amphiphiles. RSC Adv. 2015, 5, 48301−48310. (7) Küfner, U.; Schmidt, R. A short synthesis of d,l-exo-brevicomin from divinylglycol. Synthesis 1985, 11, 1060−1062. (8) Burke, S. D.; Voight, E. A. Formal synthesis of (+)-3-deoxy-Dglycero-D-galacto-2-nonulosonic acid (KDN) via desymmetrization by ring-closing metathesis. Org. Lett. 2001, 3, 237−240. (9) Voight, E. A.; Rein, C.; Burke, S. D. Formal synthesis of (−)-Nacetylneuraminic acid (Neu5Ac) via desymmetrization by ring-closing metathesis. Tetrahedron Lett. 2001, 42, 8747−8749. (10) Voight, E. A.; Rein, C.; Burke, S. D. Synthesis of sialic acids via desymmetrization by ring-closing metathesis. J. Org. Chem. 2002, 67, 8489−8499. (11) Quinn, K. J.; Isaacs, A. K.; Arvary, R. A. Concise total synthesis of (−)-muricatacin by tandem ring-closing/cross metathesis. Org. Lett. 2004, 6, 4143−4145. (12) Quinn, K. J.; Isaacs, A. K.; Arvary, R. A.; DeChristopher, B. A.; Szklarz, S. C. Asymmetric total synthesis of Rollicosin. Org. Lett. 2005, 7, 1243−1245. (13) Spangler, C. W.; McCoy, R. K.; Dembek, A. A.; Sapochak, L. S.; Gates, B. D. Preparation of p,p′-disubstituted-a,w-diphenyl polyenes. J. Chem. Soc., Perkin Trans. 1 1989, 1, 151−154. (14) Tona, R.; Häner, R. Synthesis and bioconjugation of dienemodified oligonucleotides. Bioconjugate Chem. 2005, 16, 837−842. (15) Bader, A.; Weiss, F. Hydroxy alkylene ethers of divinyl glycol. Patent Appl. US 3714265 (A), January 9, 1970. (16) Skochdopole, R. E.; Rubens, L. C.; Jones, G. D. Dow Chemical CO. Process for the production of foamed cross-linked polymers. Patent Appl. GB965030 (A), August 9, 1962. (17) Michelin & Cie. Improvements in or relating to the production of polyurethane elastomers. Patent Appl. GB 955972 (A), April 22, 1964. (18) Stogryn, E. L.; Passannante, A. J. Exxon research Engineering CO. Divinyl ethylene oxide. Patent Appl. GB 1061019 (A), November 26, 1963. (19) Rama Rao, A. V.; Mysorekar, S. V.; Gurjar, M. K.; Yadav, J. S. Synthesis of (3R,4R)-1,5-hexadien-3,4-diol and its unsymmetrical derivatives: application to (R)-(+)-a-lipoic acid. Tetrahedron Lett. 1987, 28, 2183−2186. (20) Burke, S. D.; Sametz, G. M. Total synthesis of 3-deoxy-Dmanno-2-octulosonic acid (KDO) and 2deoxy-b-KDO. Org. Lett. 1999, 1, 71−74. (21) Crombez-Robert, C.; Benazza, M.; Frechou, C. F.; Demailly, G. Efficient synthesis of a,w-dibromodideoxyalditols as precursors for a,wdithioalkylalditols. Carbohydr. Res. 1997, 303, 359−365. (22) Aravind, A.; Mohanty, S. K.; Pratap, T. V.; Baskaran, S. Regioselective cleavage of the bis-benzylidene acetal of D-mannitol under oxidative and reductive conditions: a new approach to C2symmetric chiral ligands. Tetrahedron Lett. 2005, 46, 2965−2968. (23) Winn, C. L.; Goodman, J. M. Studies on the formation of a tricyclic C2-symmetric sulfide. Tetrahedron Lett. 2001, 42, 7091−7093.

(24) Michaelis, S.; Blechert, S. Total synthesis of (+)-phomopsolide C by ring-size selective ring-closing metathesis/cross-metathesis. Org. Lett. 2005, 7, 5513−5516. (25) Mash, E. A.; Nelson, K. A.; Van Deusen, S.; Hemperly, S. B. 1,4Di-O-alkyl threitols from tartaric acid: 1,4-di-O-benzyl-L-threitol. Org. Synth. 1990, 68, 92. (26) Robbins, M. A.; Devine, P. M.; Oh, T. Synthesis of chiral nonracemic diols from (S,S)-1,2,3,4-diepoxybutane: (2S,3S)-dihydroxy1,4-diphenylbutane. Org. Synth. 1999, 76, 101. (27) Braun, R. A. Preparation of 4,5-dihydrooxepine and 1,2divinylethylene oxide. J. Org. Chem. 1963, 28, 1383−1384. (28) Trost, B. M.; Aponick, A. Palladium-catalyzed asymmetric allylic alkylation of meso- and dl-1,2-divinylethylene carbonate. J. Am. Chem. Soc. 2006, 128, 3931−3933. (29) Clavier, H.; Giordano, L.; Tenaglia, A. Palladium-mediated phosphine-dependent chemoselective bisallylic alkylation leading to spirocarbocycles. Angew. Chem., Int. Ed. 2012, 51, 8648−8651. (30) Billamboz, M.; Legeay, J.-C.; Hapiot, F.; Monflier, E.; Len, C. Novel strategy for the bis-butenolide synthesis via ring-closing metathesis. Synthesis 2012, 44, 137−143. (31) Schwarzwalder, G. M.; Steinhardt, S. E.; Pham, H. V.; Houk, K. N.; Vanderwal, C. D. Synthesis of the tetracyclic core of exiguaquinol. Org. Lett. 2013, 15, 6014−6017. (32) Cazorla, C.; Billamboz, M.; Chevrin-Villette, C.; Hapiot, F.; Monflier, E.; Len, C. Conjugated dienyl derivatives by green bisallylic substitution: synthetic and mechanistic insight. ChemCatChem 2016, 8, 2321−2328. (33) Talebian-Kiakalaieh, A.; Amin, N. A. S.; Hezaveh, H. Glycerol for renewable acrolein production by catalytic dehydration. Renewable Sustainable Energy Rev. 2014, 40, 28−59. (34) Groll, H. P. A.; George, H. Shell Dev. Process of converting a polyhydric alcohol to a carbonyl compound. Patent Appl. US 2042224, 1936. (35) Hoyt, H. E.; Manninen, T. H. US Ind. Chemicals. Inc. Production of acrolein from glycerol. Patent Appl. US 2558520, 1951. (36) Ramayya, S.; Brittain, A.; DeAlmeida, C.; Mok, W.; Antal, M. J. Acid-catalysed dehydration of alcohols in supercritical water. Fuel 1987, 66, 1364−1371. (37) Bühler, W.; Dinjus, E.; Ederer, H. J.; Kruse, A.; Mas, C. Ionic reactions and pyrolysis of glycerol as competing reaction pathways in near- and supercritical water. J. Supercrit. Fluids 2002, 22, 37−53. (38) Len, C.; Luque, R. Continuous flow transformations of glycerol to valuable products: an overview. Sustainable Chem. Processes 2014, 2, 1−10. (39) Ott, L.; Bicker, M.; Vogel, H. Catalytic dehydration of glycerol in sub- and supercritical water: a new chemical process for acrolein production. Green Chem. 2006, 8, 214−220. (40) Watanabe, M.; Iida, T.; Aizawa, Y.; Aida, T. M.; Inomata, H. Acrolein synthesis from glycerol in hot-compressed water. Bioresour. Technol. 2007, 98, 1285−1290. (41) Lee, Y. Y.; Lee, K. A.; Park, N. C.; Kim, Y. C. The effect of PO4 to Nb2O5 catalyst on the dehydration of glycerol. Catal. Today 2014, 232, 114−118. (42) De Oliveira, A. S.; Vasconcelos, S. J. S.; de Sousa, J. R.; de Sousa, F. F.; Filho, J. M.; Oliveira, A. C. Catalytic conversion of glycerol to acrolein over modified molecular sieves: activity and deactivation studies. Chem. Eng. J. 2011, 168, 765−774. (43) Suzuki, N.; Takahashi, M. KAO Corp. Method for producing acrolein. Patent Appl. JP 2006290815, 2006. (44) Yoshimi, Y.; Masayuki, Y.; Torakichi, A.; Takanori, A. Method for producing acrolein. Showa Denko. Patent Appl. JP 2009179569, 2009. (45) Zsigmond, A.; Bata, P.; Fekete, M.; Notheisz, F. Catalytic dehydration of glycerol under mild condition: an environmentally benign acrolein production. J. Environ. Prot. 2010, 1, 201−205. (46) Shen, L.; Yin, H.; Wang, A.; Feng, Y.; Shen, Y.; Wu, Z.; Jiang, T. Liquid phase dehydration of glycerol to acrolein catalyzed by silicotungstic, phosphotungstic, and phosphomolybdic acids. Chem. Eng. J. 2012, 180, 277−283. G


Research Article

ACS Sustainable Chemistry & Engineering (47) Richel, A.; Laurent, P.; Wathelet, B.; Wathelet, J.-P.; Paquot, M. Microwave-assisted synthesis of D-glucuronic acid derivatives using cost-effective solid acid catalysts. Tetrahedron Lett. 2010, 51, 1356− 1360. (48) Kogelbauer, A.; Vassena, D.; Prins, R.; Armor, J. N. Solid acids as substitutes for sulfuric acid in the liquid phase nitration of toluene to nitrotoluene and dinitrotoluene. Catal. Today 2000, 55, 151−160. (49) Billamboz, M.; Sotto, N.; Chevrin-Villette, C.; Len, C. Simple and expeditious pinacol coupling of non usual a,b-unsaturated carbonyl compounds in water. RSC Adv. 2015, 5, 46026−46030. (50) Sotto, N.; Billamboz, M.; Chevrin-Villette, C.; Len, C. Selective pinacol coupling on regeneratable supported acids in sole water. J. Org. Chem. 2015, 80, 6375−6380. (51) Hazarika, B. K.; Dutta, D. K. Zn-AlCl3.6H2O-mediated reaction in aqueous media: pinacol coupling reaction. Synth. Commun. 2011, 41, 1088−1093.

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