- The Rhodium Catalysed Direct Conversion of Phenols to Primary Cyclohexylamines
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Cyclohexylamines are important intermediates in chemical industry, which are currently produced from petrochemical sources. Phenols, however, are an attractive sustainable feedstock. We here demonstrate the transformation of phenols with ammonia to primary cyclohexylamines. In contrast to previously reported chemistry which used palladium catalysts, we here show that rhodium is an excellent catalyst for the formation of primary cyclohexylamines. Different parameters were studied and it was shown that the reaction is applicable to a scope of phenolic compounds providing high selectivity.
- Tomkins, Patrick,Valgaeren, Carlot,Adriaensen, Koen,Cuypers, Thomas,Vos, Dirk E. De
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p. 3689 - 3693
(2018/07/31)
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- PRODUCTION METHOD OF TRANS-DIAMINOCYCLOHEXANE
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PROBLEM TO BE SOLVED: To provide a method to gain a trans isomer by isomerization from a cis isomer of diaminocyclohexane efficiently. SOLUTION: When a cis isomer of diaminocyclohexane (including 1,4-diaminocyclohexane) is isomerized under presence of metal catalyst (including ruthenium-catalyst) and a trans isomer of the diaminocyclohexane is provided, the cis isomer is performed heating and pressure treatment in inert gas (including nitrogen gas). In such the isomerization processing, a reaction temperature can be more than 100°C (e.g., around 150-250°C), and a pressure of the inert gas can be more than 5 MPa (e.g., 7-20 MPa). COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0062; 0073
(2016/12/16)
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- Catalytic hydrogenation of 1,4-phenylenediamine to 1,4-cyclohexanediamine
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Catalytic hydrogenation of 1,4-phenylenediamine to 1,4-cyclohexanediamine using Ru/Al2O3 as a catalyst was carried out in water, and the results were compared with those in isopropanol and SC-CO2. 80% 1,4-phenylenediamine conversion with 87% selectivity to 1,4-cyclohexanediamine was achieved on 5% Ru/Al2O3 catalyst at 90°C and H2 pressure of 4 MPa. The hydrogenation of 1,4-phenylenediamine is influenced by the solvent. A systematic study of the hydrogenation of 1,4-phenylenediamine revealed that the reaction was consecutive. The longer the time, the lower was the CHDA selectivity. Also, the reaction temperature was an important parameter and played a vital role in preventing the formation of side products. Pleiades Publishing, Ltd., 2014.
- Ma, Hongxian,Cai, Jianguo
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p. 397 - 403
(2014/08/18)
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- Direct amination of bio-alcohols using ammonia
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A slightly adapted catalyst system has been successfully applied in the direct amination of primary and secondary alcohols. Moreover, the applicability to diols has been shown, giving high selectivity towards the primary diamines. It was found that the Ru/P ratio as well as the amount of ammonia used are highly important in this system, especially for higher substrate loadings. The catalyst was employed on a larger batch scale for the conversion of isomannide to the corresponding diamine. Additionally, it was shown that the catalyst is stable for at least six consecutive runs. No significant loss of activity and selectivity was observed.
- Pingen, Dennis,Diebolt, Olivier,Vogt, Dieter
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p. 2905 - 2912
(2013/10/21)
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- Preparation of trans cyclohexane 1,4 diisocyanate
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A process is disclosed for selectively making trans-cyclohexane-1,4-diisocyanate, trans-cyclohexane-1,4-diamine, a trans-cyclohexane-1,4-diurethane, a trans-cyclohexane-1,4-diurea and trans-cyclohexane-1,4-disulphonyl urea by reacting ammonia with a mixture of cis and trans-cyclohexane-1,4-dicarboxylic acid, a lower alkyl ester, a glycol ester, an oligomeric ester or a polyester to make a solid trans-dicarboxylic acid diamide in a first step. The diamide is chlorinated to form cyclohexane-1,4-dicarboxylic acid-bis-N-chloramide. The latter compound is then converted into a (a) trans-cyclohexane-1,4-diamine with an alkali metal hydroxide or alkaline earth metal hydroxide; or into a (b) a trans-cyclohexane-1,4-diurethane by reaction with an alcohol or glycol in a reaction mixture containing an alkali metal hydroxide or alkaline earth metal hydroxide; or into (c) a trans-cyclohexane-1,4-diurea by reaction with a primary or secondary amine in a reaction mixture containing an alkali metal hydroxide or alkaline earth metal hydroxide; or into a (d) trans-cyclohexane-1,4-sulphonyl urea by reaction with a primary sulphonamide in a reaction mixture containing an alkali metal hydroxide and dimethyl formamide and water. The diurea prepared in (c) may be converted into trans-cyclohexane-1,4-diisocyanate with gaseous hydrogen chloride in an inert solvent. The diurethane prepared in (b) and the disulphonyl urea prepared in (d) may be thermally decomposed into trans-cyclohexane-1,4-diisocyanate.
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- Synthesis of analogues of N (2 chloroethyl) N' trans 4 methylcyclohexyl) N nitrosourea for evaluation as anticancer agents
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The superior activity of N (2 chloroethyl) N' (trans 4 methylcyclohexyl) N nitrosourea (MeCCNU) against advanced murine Lewis lung carcinoma in comparisons with the cis form and other nitrosoureas prompted the synthesis of a number of MeCCNU analogues, including several cis trans pairs. The methyl group was replaced by a variety of substituents (CO2H, CH2CO2H, CO2Me, CH2OAc, CH2Cl, OMe); the trans 3 methylcyclohexyl, cis 2 methyl 1,3 dithian 5 yl, cis and trans 2 methyl 1,3 dithian 5 yl tetraoxide, and 1 methylhexyl (open chain) analogues were also prepared. Preliminary tests against murine leukemia L1210 revealed therapeutic indices (ED50/LD10) ranging from 0.26 to 0.79; all but 3 analogues effected 50% cure rates at nontoxic doses, the open chain analogue being one of the least active. In terms of therapeutic index, diequatorial (trans 4) isomers were, with one exception, as active as or, in 4 of the 8 examples, somewhat more active than the corresponding axial equatorial (cis 4) isomers. In this series, 4 of the 5 2-fluoroethyl analogues prepared were clearly inferior to the corresponding 2 chloroethyl analogues.
- Johnston,McCaleb,Clayton,Frye,Krauth,Montgomery
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p. 279 - 290
(2007/10/04)
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