- Method for preparing diazacyclooctane intermediate and diazacyclooctane
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The invention provides a method for preparing a diazacyclooctane intermediate and diazacyclooctane. The preparation method comprises the following steps: synthesizing 1,5-bis(p-toluenesulfonyl)-1,5-diazacyclooctane from 1,3-bis(p-toluenesulfonyl)-1,3-dioxypropane, 1,3-bis(p-toluenesulfonyl)-1,3-propane diamine and sodium methoxide under a temperature condition of 60-100 DEG C; then synthesizing 1,5-diazacyclooctane bromate from 1,5-bis(p-toluenesulfonyl)-1,5-diazacyclooctane, phenol and hydroacetic acid; and finally, synthesizing 1,5-diazacyclooctane from 1,5-diazacyclooctane bromate and sodium methoxide. According to the method, the yield of the 1,5-bis(p-toluenesulfonyl)-1,5-diazacyclooctane can be increased, and the reaction time for synthesizing the 1,5-diazacyclooctane can be shortened.
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Paragraph 0019; 0023-0048
(2020/06/17)
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- An Alternative Synthesis of Cyclic Aza Compounds
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A series of cyclic mono-, di- and poly-aza compounds has been synthesised in moderate to good yields by reaction of p-toluenesulfonamide and either α,ω-ditosylates or α,ω-dichlorides.
- Boerjesson, L.,Welch, C. J.
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p. 621 - 626
(2007/10/02)
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- Kinetics of Acid Hydrolysis of Nickel(II) and Copper(II) Compounds with the Cyclic Diamines 1,5-Diazocane and 4,4-dimethyl-7-(5,5,7-trimethyl-1,4-diazepan-1-yl)-5-azaheptan-2-ol
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The kinetics of acid-promoted hydrolysis reactions of nickel(II) and copper(II) complexes of the cyclic diamines 1,5-diazocane (daco) and 4,4-dimethyl-7-(5,5,7-trimethyl-1,4-diazepan-1-yl)-5-azaheptan-2-ol (pyaz) in NaCl/HCl media (-> = 2 mol dm-3) are reported.For 2+, beyond small +>, an acid-limited rate constants of 2.0x10-5 s-1, involving dissociation of the first daco ligand, and for 2+ a similarly acid-limited rate constant of 1.5x10-2 s-1, involving dissociation of the second daco ligand, were measured at 50 deg C.For 2+ and 2+ the rate of the hydrolysis reactions are again acid-limited, effectively independent of acid with rate constant of 1.0x10-2 s-1 for 2+ while for 2+ the rate follows the expression kobs = 6.0x10-2+>/(1+4.6+>) s-1, both measured at 25 deg C.
- Collier, Wendy,Curtis, Linda S.,Curtis, Neil F.,Pomer, Izabela J.
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p. 1611 - 1616
(2007/10/02)
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- DEPROTONATION OF HYDRAZINIUM DICATIONS IN THE DIAZONIAPROPELLANE SERIES TO FORM BRIDGEHEAD IMINIUM IONS; EXTERNAL AND INTRAMOLECULAR TRAPPING
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The reactions of hexa-alkylhydrazinium dications with bases and nucleophiles are described. 1,5-Diazonia-tricyclodecane (1) is hydrolysed rapidly by SN2 attack on the four-membered ring with ring opening (C-N+ cleavage).In all other cases deprotonation at α-C with concomitant N+-N+ cleavage (E2 reaction) is the only primary process.The cis-1,6-dimethyl-1,6-diazoniabicyclodecane ion (6), is exclusively deprotonated at a methyl group (Hofmann orientation). 1,5-Diazoniatricycloundecane (2), 1,6-diazoniatricyclododecane (3), 1,6-diazoniatricyclotridecane (4), and 1,6-diazoniatricyclotetradecane (5) ions generate bridgehead iminium ions, which may be trapped intramolecularly by the transannular amino group or externally by added nucleophiles.Reaction with cyanide ion gives detailed information on the regio- and stereo-chemistry of the trapping sequence.Although intramolecular/external trapping is truly competitive, the products of these reactions (α-amino-ammonium ions and α-aminonitriles) may be interconverted under different reaction conditions.The solvolysis of 1-(3-phenoxypropyl)-1,5-diazabicyclooctanium bromide in aqueous 48percent HBr is 103 faster than that of 3-phenoxypropyltrimethylammonium bromide, and the products are consistent with the intermediacy of the dication (2).These observations provide an explanation for the formation of 1,5-diazacyclo-octane in the reaction of 1,3-dibromopropane with hydrazine.
- Alder, Roger W.,Sessions, Richard B.,Gmuender, John O.,Grob, Cyril A.
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p. 411 - 418
(2007/10/02)
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- SYNTHESIS OF MEDIUM-RING BICYCLIC BRIDGEHEAD DIAMINES FROM MONOCYCLIC DIAMINES VIA α-AMINOAMMONIUM IONS
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Condensation of 4-chlorobutanal and 5-chloropentanal with six cyclic diamines gave twelve α-aminoammonium salts; cleavage of these with LiAlH4 gave medium-ring bicyclic diamines.
- Alder, Roger W.,Eastment, Paul,Moss, Richard E.,Sessions, Richard B.,Stringfellow, Martin A.
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p. 4181 - 4184
(2007/10/02)
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