Abstract:Chemical substances and processes that play a fundamental role in the 12 principles of Green Chemistry representing conservative evolution and/or industrial metabolism were reviewed.
“…We demonstrated that LA can be converted to GVL in H-Cube ® reactor under 100 bar of H 2 at 100°C exhibiting productivity (hereafter P (mol GVL g metal –1 h –1 )) of 0.83 for Ru/C and 0.2 for Pd/C in water at 100 bar, respectively [53]. From the viewpoint of green chemistry, the use of water or alcohols as reaction media are much more favourable, since they have been considered as environmentally benign or even renewable-based solvents having low negative impacts on the environment [54].…”
Heterogeneous continuous transformation of methyl levulinate (ML) and ethyl levulinate (EL) to
γ
-valerolactone (GVL), as a promising C
5
-platform molecule was studied at 100°C. It was proved that the H-Cube
®
continuous hydrogenation system equipped with 5% Ru/C CatCart
®
is suitable for the reduction of both levulinate esters. While excellent conversion rates (greater than 99.9%) of ML and EL could be achieved in water and corresponding alcohols, the selectivities of GVL were primarily affected by the solvent used. In water, 100% conversion and
ca
50% selectivity that represent
ca
0.45 mol
GVL
g
metal
−1
h
−1
productivity towards GVL, were obtained under 100 bar of total system pressure. The application of alcohols as a solvent, which maintained high conversion rates up to 1 ml min
–1
flow rate, resulted in lower productivities (less than 0.2 mol
GVL
g
metal
−1
h
−1
) of GVL. Therefore, from a synthesis point of view, the corresponding 4-hydroxyvalerate esters could be obtained even at a higher reaction rate. The addition of sulfonated triphenylphosphine ligand (TPPTS) allowed reduction of the system pressure and resulted in the higher selectivity towards GVL.
“…We demonstrated that LA can be converted to GVL in H-Cube ® reactor under 100 bar of H 2 at 100°C exhibiting productivity (hereafter P (mol GVL g metal –1 h –1 )) of 0.83 for Ru/C and 0.2 for Pd/C in water at 100 bar, respectively [53]. From the viewpoint of green chemistry, the use of water or alcohols as reaction media are much more favourable, since they have been considered as environmentally benign or even renewable-based solvents having low negative impacts on the environment [54].…”
Heterogeneous continuous transformation of methyl levulinate (ML) and ethyl levulinate (EL) to
γ
-valerolactone (GVL), as a promising C
5
-platform molecule was studied at 100°C. It was proved that the H-Cube
®
continuous hydrogenation system equipped with 5% Ru/C CatCart
®
is suitable for the reduction of both levulinate esters. While excellent conversion rates (greater than 99.9%) of ML and EL could be achieved in water and corresponding alcohols, the selectivities of GVL were primarily affected by the solvent used. In water, 100% conversion and
ca
50% selectivity that represent
ca
0.45 mol
GVL
g
metal
−1
h
−1
productivity towards GVL, were obtained under 100 bar of total system pressure. The application of alcohols as a solvent, which maintained high conversion rates up to 1 ml min
–1
flow rate, resulted in lower productivities (less than 0.2 mol
GVL
g
metal
−1
h
−1
) of GVL. Therefore, from a synthesis point of view, the corresponding 4-hydroxyvalerate esters could be obtained even at a higher reaction rate. The addition of sulfonated triphenylphosphine ligand (TPPTS) allowed reduction of the system pressure and resulted in the higher selectivity towards GVL.
“…Interestingly, application of these two powerful methods in combination for a C–C bond formation process shorten the synthesis sequence for the assembly of the target molecules and thus enhances the ease of preparation of various functional molecules. These processes are considered as “green” because of atom economy and synthetic brevity [ 52 ] involved in these reactions [ 12 , 53 – 54 ]. Additionally, several methods are available to remove palladium and ruthenium impurities in minor amounts from the reaction mixture.…”
This account provides an overview of recent work, including our own contribution dealing with Suzuki–Miyaura cross coupling in combination with metathesis (or vice-versa). Several cyclophanes, polycycles, macrocycles, spirocycles, stilbenes, biaryls, and heterocycles have been synthesized by employing a combination of Suzuki cross-coupling and metathesis. Various popular reactions such as Diels–Alder reaction, Claisen rearrangement, cross-metathesis, and cross-enyne metathesis are used. The synergistic combination of these powerful reactions is found to be useful for the construction of complex targets and fulfill synthetic brevity.
“…As postulated by the second law of thermodynamics, any process only occurs with the degradation (anergy) of a part of useful energy (exergy) and transformation of matter from a low entropy state (high organization) to a high entropy state (low organization, high stability) [5,50]. Thus, the idea of a circular (or closed) economy is inconceivable (although it has permeated GC discussions) [3,[60][61][62][63][64][65][66][67], since the total energy is maintained throughout the process, but the possibility of its use is always diminished [50, 68,69]. Besides the physical limits imposed on technologies, which inexorably lead to environmental degradation, there are also problems of technological efficiency, i.e., it is not always that theoretical yields are attained in practice [53].…”
Section: Green Chemistry: Environment Economy and Society?mentioning
The current research on systems thinking criticizes the additive nature of green chemistry (GC) not being supportive of systems thinking to achieve holism in its practices. This paper argues that systems thinking should comprise of the social issues, and, therefore, it studies renowned papers by GC pioneers and reviews on the field regarding how they address the social dimension of sustainability. It points out how GC has ignored social sustainability in its discourses, practices, and evaluations, leading to a reductionist interpretation of sustainability. Then, this paper presents some challenges to be overcome in order to achieve balanced sustainability. A systemic chemical thinking is advocated, considering chemistry in culture and chemistry as culture, expanding the chemistry rationality from ontological and technological dimensions into the epistemological and ethical ones. It is then discussed how chemistry education can help to promote sustainability in a broad and systemic way.
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