CERTIFICATE
Scheme 4.7: Pincer-Ru and pincer-Mn catalysts reported for the upgradation of ethanol to n- butanol
4.3 Result and discussion
4.3.2 Catalytic transformation of ethanol to bio-butanol under thermal condition
In the Chapter III it has been described that, the reactivity (Table 3.3) of aliphatic alcohols towards -Alkylation is very poor. Therefore, the optimization conditions were revisited for the upgradation of ethanol using (Cy2NNN)RuCl2(CO) (4.20a) (Table 4.4) at 140 °C in the presence of various base. For variations with NaOtBu as a base, the productivity was higher (195 TON) with 0.05 mol % 4.20a in the presence of 10 mol % NaOtBu (entry 1, Table 4.4).
Use of KOH resulted in slightly lower reactivity and n-butanol selectivity (entry 3, Table 4.4).
The reactivity was very low with the use of KOtBu as base (entry 4, Table 4.4). No reactions were observed when Et3N, K2CO3 and Mg were used (entries 5, 6 and 7, Table 4.4). Upon employing NaH, the productivity (260 TON) improved with comparable selectivity (90%)
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Kanu Das, Ph.D Thesis, IIT Guwahati 146 towards n-butanol (entry 8, Table 4.4). In the presence of NaOH (10 mol %), the 4.20a (0.05 mol %) catalyzed reaction provided higher turnovers (310) at a selectivity of 85% towards n- butanol (entry 9, Table 4.4). These productivity and selectivity values hardly changed with increase in temperature and at prolonged reaction times (entries 12 and 13, Table 4.4). On increasing the base loading to 20 mol %, while the selectivity dropped to 70%, the turnovers slightly increased (entry 11, Table 4.4).
Table 4.4: Optimization of Guerbet reaction catalyzed by 4.20a.a Entry Base (X mol %) n-Butanolb
yield (%)
Selectivity of n- butanolg
Total TONc
1 NaOtBu (10) 8.4 90 195
2 NaOtBu (20) 6.9 95 145
3 KOH (10) 6.1 85 155
4 KOtBu (10) 2.2 85 65
5 Et3N (10) 0 0 0
6 K2CO3 (10) 0 0 0
7 Mg (10) 0 0 0
8 NaH (10) 10.8 90 260
9 NaOH (10) 12.5 85 310
10 NaOH (5) 5.9 85 150
11 NaOH (20) 11.6 80 330
12d NaOH (10) 12.6 90 290
13d,e NaOH (10) 13.9 90 320
14f NaOEt (10) 13.9 90 335
15e, f NaOEt (10) 17.1 90 410
aReaction conditions: 8.56 mmol of ethanol, X mol % of base and 4.28 µmol of 4.20a. bSelectivity and TON were calculated by GC analysis using toluene as an internal standard. cTotal ethanol converted to products. dThe reaction was carried out at 150 °C. eReaction was carried out for 48 h. fNaOEt was generated in-situ using ethanol (110 mol %) and Na(10 mol %) prior to addition of 4.20a. gSelectivity = Yield of n-butanol/Conversion of 4.1.
Following up on our recent approach of generating the base in situ, when 10 mol % Na was used to generate 10 mol % NaOEt very high turnovers (ca. 335) were obtained with 90%
selectivity towards n-butanol after 24 h (entry 14, Table 4.4). Upon continuing the reaction to 48 h, the productivity was further enhanced with no loss of selectivity (entry 15, Table 4.4).
This condition was used for further optimization with various catalysts (Table 4.5 and Table 4.6).
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Kanu Das, Ph.D Thesis, IIT Guwahati 147 Table 4.5: Guerbet reaction catalyzed by phosphine based pincer-ruthenium complexes.a
Entry Catalyst Time (h) n-Butanol
(TON)
n-Butanol selectivity (%)c
Total (TON)b
1
0.5 85 90 90
3.0 185 80 225
9.0 240 80 300
72 340 75 450
2
0.5 160 95 170
3.0 310 80 385
9.0 370 80 475
72 375 75 495
3
0.5 145 90 160
3.0 250 80 320
9.0 260 75 340
72 300 75 395
4
0.5 45 80 60
3.0 200 75 270
9.0 240 70 335
72 250 70 355
5
0.5 50 80 60
3.0 550 85 660
9.0 800 75 1090
72 780 70 1115
6
0.5 270 65 420
3.0 285 65 430
9.0 305 65 450
72 375 60 620
aReaction conditions: 8.56 mmol of ethanol, 0.86 mmol of NaOEt and 0.05 mol % of catalyst. bCalculated by GC analysis using toluene as an internal standard. cSelectivity = Yield of n-butanol/Conversion of 4.1.
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Kanu Das, Ph.D Thesis, IIT Guwahati 148 Table 4.6: Guerbet reaction catalyzed by carbonyl based pincer-ruthenium complexes.a
Entry Catalyst Time (h) n-Butanol
(TON)b n-Butanol
selectivity (%)c Total (TON)b
1
0.5 125 90 135
3.0 200 85 235
9.0 235 75 310
72 260 80 335
2
0.5 100 95 105
3.0 225 90 250
9.0 235 80 300
72 255 75 340
3
0.5 85 90 90
3.0 175 90 190
9.0 310 80 385
72 385 75 520
4
0.5 115 75 150
3.0 125 75 165
9.0 140 60 238
72 135 65 215
5
0.5 295 85 355
3.0 710 80 880
9.0 720 80 920
72 765 80 975
6
0.5 135 75 180
3.0 165 75 230
9.0 205 75 275
72 280 75 385
aReaction conditions: 8.56 mmol of ethanol, 0.86 mmol of NaOEt and 0.05 mol % of catalyst. bCalculated by GC analysis using toluene as an internal standard. cSelectivity = Yield of n-butanol/Conversion of 4.1.
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Kanu Das, Ph.D Thesis, IIT Guwahati 149 Table 4.7: Ethanol upgradation catalyzed by varying amount of 4.22a.a
Entry Catalyst (x mol %) Time (h) n-butanol (4.2)b TONb Yield (%) Selectivity (%)c 4.2 Total
1 0.025
0.5 5.23 95 330 335
3.0 19.80 80 795 1015
9.0 32.02 85 1280 1495
72 37.73 70 1510 2100
2 0.035
0.5 8.44 90 155 267
3.0 26.73 80 740 970
9.0 33.28 80 925 1155
72 36.58 65 1045 1670
3 0.055
0.5 14.82 85 300 355
3.0 35.44 80 710 880
9.0 35.81 80 715 920
72 38.21 80 765 975
4 0.075
0.5 18.84 95 250 255
3.0 35.44 80 475 580
9.0 32.88 75 440 585
72 36.07 65 480 740
5 0.099
0.5 21.26 95 215 225
3.0 36.94 80 370 475
9.0 38.52 75 385 500
72 43.32 75 435 585
aReaction conditions: 8.56 mmol of ethanol, 0.86 mmol of base and x mol % of 4.22a. bCalculated by GC analysis using toluene as an internal standard. cSelectivity = Yield of n-butanol/Conversion of 4.1.
The ethanol upgradation was first tested for a series of NNN pincer-ruthenium complexes containing PPh3 ancillary ligands (Table 4.5). With catalyst 4.19d, the rate of the reaction was low and the productivity levelled off after 9 hours (entry 4, Table 4.5). The rate of 4.19a catalyzed ethanol upgradation was about 1.5 times that of rate obtained with 4.19d (entry 1, Table 4.5). Both the catalysts 4.19b and 4.19c demonstrated rates that were about 1.75 folds higher than the corresponding rate observed with 4.19a (entry 2 and 3, Table 4.5). Kumar and co-workers have recently reported that complex 4.21a that has less steric crowding around the Ru center efficiently catalyzes the dehydrogenation of glycerol.74 When 4.21a was explored for the Guerbet reaction of ethanol, it exhibited a rate similar to that observed with 4.19d but with a much higher (3.1 folds) productivity (1115 TON after 72 h) (entry 5, Table 4.5). On the
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Kanu Das, Ph.D Thesis, IIT Guwahati 150 other hand, complex 4.21b demonstrated a rate (ca. 840 TO/h) about 7 folds higher than its N- H analogue 4.21a before levelling off almost quickly.
Table 4.8: Ethanol upgradation catalyzed by 4.22a with varying amount ethanol concentration.a
Entry Ethanol (M) Time (h) n-butanol (4.2)b TONb
Yield (%) Selectivity (%)c 4.2 Total 1 6.11
0.5 10.7 95 215 225
3.0 23.6 80 470 585
9.0 23.6 75 470 610
72 23.3 70 465 680
2 8.56
0.5 11.8 95 235 240
3.0 21.6 85 430 500
9.0 28.3 80 565 690
72 27.8 75 555 710
3 12.23
0.5 14.82 85 300 355
3.0 35.44 80 710 880
9.0 35.81 80 715 920
72 38.21 80 765 975
4 13.46
0.5 15.4 65 305 480
3.0 32.1 65 640 1015
9.0 35.5 65 710 1100
72 39.6 60 795 1380
aReaction conditions: X mmol of ethanol, 0.86 mmol of base and 0.05 mol % of 4.22a. bCalculated by GC analysis using toluene as an internal standard. cSelectivity = Yield of n-butanol/Conversion of 4.1.
The phosphine-free complexes (4.20a-d and 4.22a-b) were also tested as catalysts for the Guerbet reaction (Table 4.6). In comparison to 4.19a and 4.19d, their phosphine-free counterparts 4.20a and 4.20d exhibited a better rate towards the ethanol upgradation reaction (entries 1 and 4, Table 4.6). The rate of ethanol upgradation catalyzed by 4.20b and 4.20c were comparable (entries 2 and 3, Table 4.6) and about 1.3-1.5 times slower than 4.20a and 4.20d.
The rate of 4.22b catalyzed (entry 6, Table 4.6) Guerbet reaction was two folds faster than that catalyzed by 4.20b and 4.20c. Among all the catalysts screened, the catalyst 4.22a demonstrated not only very good rate (ca. 710 TO/h) but also high productivity (975 TONs at 49% ethanol conversion) (entry 5, Table 4.6). Hence, further exploration involving the variation of catalyst loading for Guerbet reaction was carried out using the phosphine-free catalyst 4.22a (Table 4.6).
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Kanu Das, Ph.D Thesis, IIT Guwahati 151 Figure 4.8: Plot depicting the (a) initial rate vs. [4.22a] and (b) initial rate vs. [Ethanol] in the ethanol upgradation catalyzed by 4.22a.