Levulinic Acid. Iii. The Hydrogenation of Certain of Its Alkyl Esters in the Presence of Platinum Catalyst

Thomas, Ralph W.; Schuette, H. A.; Cowley, Milford A.

doi:10.1021/ja01361a028

Cited by 4 publications

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“…The x-ray powder pattern was determined: [lo] 5.54; [7] 6.41; [5] The acidified filtrate later precipitated 0.10 g. of 1 ,4-t~-methylene-A6-cyclohexene-2, 3-11dicarboxylic acid (I), m.p. 172-174", identified by mixture melting point.…”

Section: Vol 20mentioning

confidence: 99%

“…per g.) raised this melting point to 212.5-214°. The x-ray diffraction pattern of XXII was: [10] 9.44, 6.96; [9] 4.62, 4.11; [5] Found: C, 29.5; H, 2.93; OCH3, 6.92. Dimethyl B-i-hydroxy-6-i-chloromercuri-l ,4-^-ethylenecyclohexane-B ,S-H-dicarboxylate (XXIII).…”

Section: T H I S C O N T E N T Imentioning

confidence: 99%

“…It is estimated that 15-20% was present. The x-ray diffraction pattern was: [10] 6.75; [8] 9.82; [6] 4.11; [5] 13.67, 7.43; [4] 4.25; [3] 3.70; [2] 5.25, 5.05, 4.51, 3.86.…”

Section: T H I S C O N T E N T Imentioning

confidence: 99%

“…Then if the 5-J,-hydroxy groups adds to the 3-j-earbomethoxy group as is shown in XI elimination of methanol ought to occur with ease. The constraint in the bicyclic structure may be expected to accentuate the known tendency for 7-hydroxy esters to be transformed into 7-lactones (5,6). The resulting monoester, XII, might be expected to be water soluble until it is converted to the chloromercurial.…”

mentioning

confidence: 99%

“…5.62,3.92; [3] 3.26;[2] 3.51, 3.02, 2.86. The identical product was obtained by treatment of a methanolic solution of XXI with aqueous sodium chloride.Anal.…”

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confidence: 99%

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Oxymercuration of Bridged Cycloölefins

McNeely¹,

Rodgman²,

Wright³

1955

J. Org. Chem.

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X-ray diffraction studies indicate that addition of the elements of alkoxymercuric salts occurs with inversion at one of the vicinal carbon atoms in alkenes (1). By contrast our studies with 1 , 4-~~-methylene-As-cyclohexene-2, 3-14dicarboxylic acid (I) and with 1 , 4-~~-ethylene-A3-cyclohexene-2, 3-JJ-dicarboxylic ester (XV1II)l seem to show that addition in these compounds occurs directly, Le. without inversion at either carbon atom comprising the alkene linkage.The configuration of 1, 4-TT-methylene-A5-cyclohexene-2, 3-JL-dicarboxylic acid (I) has been demonstrated by Alder and Stein (2) who prepared it by hydrolysis of the adduct from cyclopentadiene and maleic anhydride. When I is boiled with aqueous mercuric acetate the mercuric salt which is formed immediately is slowly transformed into an oxymercurial which is either 5-L-hydroxyanhydro -[6-J-hydroxymercuri-2-J-carboxy] -1 ,4 -TTmethylenecyclohexsne-3-J-carboxylic acid (11) or 5-J-hydroxy-6-~-hydroxymercuri-2-J-carboxy-1,4-~~methylene-cyclohexane-3-J-carboxylic acid lactone (IIa). When this compound is treated with acetic anhydride an equivalent of water is lost and 5-4-hydroxyanhydro -[6-J-hydroxymercuri-Z-J-carboxy] -1,4 -TTmethylenecyclohexane -3-L-carboxylic acid, y-lactone (111) is formed. Alternatively I11 may be formed directly from I by treatment with mercuric acetate in either 2,5-dioxahexane or methanol. It may be noted that this lactonized carboxymercurial is similar in the type with the esterified acetoxymercurial obtained by the addition of mercuric acetate to cyclohexene. Presumably both I1 and I11 are preceded in the system by the mercuric salt IV since the initial precipitate in the reaction system forms mercuric oxide when treated with alkali whereas the final precipitate only dissolves in this reagent.The existence of the lactonized anhydro-hydroxymercurial I11 would seem to require that oxymercuration occurs directly (without inversion) but this conclusion depends on the existence of the mercurial as the monomer 111. No evidence has previously been presented to show that anhydro-hydroxymercuri-The use of the prefixes "exo" and "endo" for specification of configuration in these bridged cycloalkanes and cycloalkenes becomes confusing when more than two substituents must be located, and this situation cannot be ameliorated by introduction of the alreadyabused terms "cis" and "trans". Therefore we have elected in this discussion to use arrows which, if the largest cycloalkane ring is considered as flattened, will designate "up" or "down" in respect of this ring. According to our present nomenclature endo-norbornene-2,3-dicarboxylic acid (I) becomes 1,4-~~-methylene-~6-cyclohexene-2,3-J~-dicarboxylic acid, while disodium 5-endo-hydroxy-6-exo-hydroxymercurinorbornane-2,3-endodicarboxylate (XVI) becomes 5-~-hydroxy-6-~-hydroxymercuri-l,4-f~-methylenecyclohexane-2,3-iJ-dicarboxylate. Likewise endo-5-chloromercuri-6-hydroxy[2.2.2]bicyclooctane-~rans-2,3-dicarboxylic acid y-lactone (XXV) becomes 5-J-hydroxy-6-~-chloromercuri-2-~-carboxy-1,4-ff-eth...

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Section: Vol 20mentioning

confidence: 99%

Section: T H I S C O N T E N T Imentioning

confidence: 99%

“…It is estimated that 15-20% was present. The x-ray diffraction pattern was: [10] 6.75; [8] 9.82; [6] 4.11; [5] 13.67, 7.43; [4] 4.25; [3] 3.70; [2] 5.25, 5.05, 4.51, 3.86.…”

Section: T H I S C O N T E N T Imentioning

confidence: 99%

mentioning

confidence: 99%

“…5.62,3.92; [3] 3.26;[2] 3.51, 3.02, 2.86. The identical product was obtained by treatment of a methanolic solution of XXI with aqueous sodium chloride.Anal.…”

mentioning

confidence: 99%

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Oxymercuration of Bridged Cycloölefins

McNeely¹,

Rodgman²,

Wright³

1955

J. Org. Chem.

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Catalytic hydrogenation of levulinic acid in aqueous phase

Delhomme

Schaper

Zhang‐Preße

et al. 2013

Journal of Organometallic Chemistry

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Hydrogenation of Carboxylic Acids, Esters, and Related Compounds over Heterogeneous Catalysts: A Step toward Sustainable and Carbon-Neutral Processes

Junge

Beller

2023

Chem. Rev.

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The catalytic hydrogenation of esters and carboxylic acids represents a fundamental and important class of organic transformations, which is widely applied in energy, environmental, agricultural, and pharmaceutical industries. Due to the low reactivity of the carbonyl group in carboxylic acids and esters, this type of reaction is, however, rather challenging. Hence, specifically active catalysts are required to achieve a satisfactory yield. Nevertheless, in recent years, remarkable progress has been made on the development of catalysts for this type of reaction, especially heterogeneous catalysts, which are generally dominating in industry. Here in this review, we discuss the recent breakthroughs as well as milestone achievements for the hydrogenation of industrially important carboxylic acids and esters utilizing heterogeneous catalysts. In addition, related catalytic hydrogenations that are considered of importance for the development of cleaner energy technologies and a circular chemical industry will be discussed in detail. Special attention is paid to the insights into the structure–activity relationship, which will help the readers to develop rational design strategies for the synthesis of more efficient heterogeneous catalysts.

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Levulinic Acid. Iii. The Hydrogenation of Certain of Its Alkyl Esters in the Presence of Platinum Catalyst

Cited by 4 publications

References 0 publications

Oxymercuration of Bridged Cycloölefins

Oxymercuration of Bridged Cycloölefins

Catalytic hydrogenation of levulinic acid in aqueous phase

Hydrogenation of Carboxylic Acids, Esters, and Related Compounds over Heterogeneous Catalysts: A Step toward Sustainable and Carbon-Neutral Processes

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