- Preparation of linear aromatic disulfonic acids: New linker molecules for metal-organic frameworks
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Four linear aromatic disulfonic acids were prepared, which are structurally similar to dicarboxylic acids commonly used as linker molecules for metal-organic frameworks. 4,4-Biphenyldisulfonic acid was prepared in three steps from 4,4-dibromobiphenyl (54% overall yield). Direct sulfonation of terphenyl gave the respective all-para-constituted disulfonic acid in 73% yield. Tolane-4,4-disulfonic acid was obtained by a three-step sequence consisting of Sonogashira coupling, oxidative degradation of a thioester, and hydrolysis in 20% overall yield. By using a Glaser coupling, the bis(4-sulfophenyl)butadiyne was analogously prepared in 30% overall yield. Georg Thieme Verlag Stuttgart - New York.
- Muesmann, Thomas W.T.,Wickleder, Mathias S.,Christoffers, Jens
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experimental part
p. 2775 - 2780
(2011/10/31)
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- Reductive desulfurization of organosulfur compounds with sodium in liquid ammonia
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Greater than 95% sulfur removal was observed when dialkyl mono or polysulfides were treated with Na in liquid ammonia. Polycyclic aromatic sulfur heterocycles were only moderately desulfurized under these conditions while phenylthio derivatives gave thiophenol as the major product and dithiophenols as the minor products.
- Yu, Zhengkun,Verkade, John G.
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- Synthesis, acidic and basic properties of thiols and sulfinic acids from the series of diphenyl bridging compounds
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A series of dithiols and disulfinic acids belonging to diphenyl bridging compounds was prepared and identified. The conditions of reduction for the corresponding sulfonyl chlorides were optimized resulting in production of the target compounds in 85-95% yields. The acidity constants of the compounds obtained were measured. A correlation between pKa and δSH, was established for thiols. Therewith the dissociation constants of thiols are readily evaluated by the chemical shift of the thiol group proton.
- Alov,Nikiforov,Novikov,Kobylinskii,Moskvichev,Kryukova,Yasinskii,Budanov
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p. 1160 - 1164
(2007/10/03)
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- Selective hydrolysis of phosphate esters, nitrophenyl phosphates and UpU, by dimeric zinc complexes depends on the spacer length
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Zn(II) complexes of monomers and dimers derived from 1,4,7-triazacyclododecane and 1,5,9-triazacyclotetradecane were examined as catalysts for the hydrolyses of p-nitrophenyl phosphate and bis(p-nitrophenyl) phosphate and for the cyclizations of p-nitrophenyl 2-hydroxypropyl phosphate and 3′,5′-uridyluridine (UpU). The dimers with 1,4-phenyl and 1,3-phenyl linkers were more effective than were monomers or a longer dimer - with a 4,4′-biphenyl linker - in the hydrolysis of p-nitrophenyl phosphate, suggesting that two Zn(II) ions coordinate to the phosphate group, as in the enzyme alkaline phosphatase. However, for the hydrolysis or cyclization of the phosphate diesters, the longer biphenyl linker was preferred. In this case one Zn(II) coordinates to the phosphate group while the other delivers a nucleophilic oxide anion. Bell-shaped pH vs rate profiles were seen in both cases, but with different pK's related to the specific mechanisms in the two cases.
- Chapman Jr., William H.,Breslow, Ronald
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p. 5462 - 5469
(2007/10/02)
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- Process for preparation of aromatic thiols
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Disclosed is a process for preparation of an aromatic thiol corresponding to the structure wherein A is a substituted or unsubstituted aromatic radical and n is 1, 2, 3, 4, 5 or 6 comprising contacting at a temperature of at least 80° C. an aromatic halide corresponding to the structure wherein A is the same as above, X is bromine or iodine and n is 1, 2, 3, 4, 5, or 6 with thiourea in the presence of nickel metal.
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