AMMONOLYSIS OF 1,2-EPOXYCYCLOHEXANE AND TRANS-2-BROMOCYCLOHEXANOL

1958 ◽  
Vol 36 (1) ◽  
pp. 220-227 ◽  
Author(s):  
L. R. Hawkins ◽  
R. A. B. Bannard
Keyword(s):  
Primary Amine ◽  
Aqueous Ammonia ◽  
Secondary Amines ◽  
Optimum Conditions ◽  
Fold Excess ◽  
Methanolic Ammonia

Optimum conditions for the preparation of trans-2-aminocyclohexanol by ammonolysis of 1,2-epoxycyclohexane or trans-2-bromocyclohexanol are realized by use of a 20-fold excess of aqueous alcoholic ammonia at 100°. Under these conditions formation of secondary amines is minimized. Lower ammonia–reactant ratios, or the use of absolute methanolic ammonia or aqueous ammonia, lead to lower yields of primary amine and higher yields of secondary amines. 1,2-Epoxycyclohexane has been isolated from the interaction of trans-2-bromocyclohexanol with aqueous ammonia. The oxide reacts more rapidly with aqueous alcoholic ammonia than the bromohydrin and the rate of conversion of the latter to amine is thus controlled by the rate of conversion of bromohydrin to oxide.

Aminkomplexe des Goldes, Teil 9: Gold(I)-halogenid-Komplexe mit primären und azyklischen sekundären Aminen und ihre Oxidation zu Gold(III)-Derivaten

2018 ◽  
Vol 73 (1) ◽  
pp. 43-74 ◽  
Author(s):  
Cindy Döring ◽  
Peter G. Jones
Keyword(s):  
Hydrogen Bonds ◽  
Structure Analysis ◽  
Secondary Amine ◽  
Primary Amine ◽  
Solvent Free ◽  
Secondary Amines ◽  
Primary Amines ◽  
Direct Reaction ◽  
X Ray

AbstractThe reaction of (tht)AuX (X=Cl or Br; tht=tetrahydrothiophene) with various primary amines L leads to products of the form [L2Au]+X−. Packing diagrams of the corresponding structures are dominated by N–H···X hydrogen bonds and (in some cases) aurophilic contacts. The cyclohexylamine derivative was already known as its dichloromethane ⅔-solvate; we have isolated the solvent-free compound and its pentane ¼-solvate, which all show different packing patterns. With acyclic secondary amines, the products are more varied; LAuX and [L2Au]+[AuX2]− were also found. These gold(I) products were generally formed in satisfactory quantities. The attempted oxidation to Au(III) derivatives with PhICl2 or Br2 proved impossible for the primary amine derivatives [although isopropylamine-trichloridogold(III) was obtained unexpectedly from the corresponding cyanide] and unsatisfactory for the secondary amine derivatives. Products LAuX3 and [L2AuX2]+[AuX4]− were identified but were formed in disappointing yields. In isolated cases protonated products (LH)+[AuCl4]−, (LH+)3[AuCl4]−(Cl−)2 or [(Et2N)2CH]+[AuBr4]− were formed, presumably by involvement of the dichloromethane solvent and/or adventitious water. Here also the yields were poor, and some products arose as mixtures. Direct reaction of amines with AuCl3 or (tht)AuX3 was also unsuccessful. All products were characterized by X-ray structure analysis.

Coordination of 5-Methyl-3,7-diazanonane-1,5,9-triamine (L) to Rhodium(III). Crystal Structure of fac-[Rh(H2L)Cl3] Cl(ClO4).3H2O

1994 ◽  
Vol 47 (5) ◽  
pp. 829 ◽  
Author(s):  
TW Hambley ◽  
TW Hambley ◽  
GA Lawrance ◽  
GA Lawrance ◽  
M Maeder ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Structure Determination ◽  
Primary Amine ◽  
Hot Water ◽  
Secondary Amines ◽  
Primary Amines ◽  
Triclinic Space Group ◽  
X Ray ◽  
Shortest Distance

The branched, potentially quinquedentate , 5-methyl-3,7-diazanonane-1,5,9-triamine (1) reacts in hot water with rhodium(III) chloride to yield fac -[ Rh (H2(1))Cl3]2+. Only upon extended reflux for several weeks is coordination as a quinquedentate achieved. The fac complex was crystallized readily as a mixed chloride perchlorate trihydrate salt, in the triclinic space group Pī , a 8.666(2), b 10.319(2), c 12.558(3) Ǻ, α 94.34(2), β 98.86(2), γ 97.75(2)°, Z = 2; a single-crystal X-ray structure determination was refined to Rw 0.037 for 3703 'observed' reflections. The central primary amine and two adjacent secondary amines occupy an octahedral face, with the chloro ligands then necessarily fac also. The Rh -N distances vary, with the shortest distance to the primary amine [2.023(2)Ǻ] rather than to the secondary amines [2.066(2), 2.077(2) Ǻ], as do the Rh-Cl distances [range 2.345(1)-2.369(1)Ǻ]. The two primary amines on the chain terminals remain uncoordinated, the central facially capping unit preferring coordination first, possibly indicating a general intermediate for coordination of polydentate l igands containing this type of unit.

Synthetic use of the ribosyl derivatives of 2,4- and 2,5-thiazolidinediones

1979 ◽  
Vol 44 (5) ◽  
pp. 1475-1482 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Zdeněk Točík ◽  
Jiří Beránek
Keyword(s):  
Hydrazine Hydrate ◽  
Hydrogen Chloride ◽  
Sodium Methoxide ◽  
Aqueous Ammonia ◽  
Hydroxylamine Hydrochloride ◽  
Acetyl Derivative ◽  
High Yield ◽  
Derivatives Of ◽  
Methanolic Ammonia

On ribosidation of 2,4-thiazolidinedione (2,5-thiazolidinedione, respectively), the 3-β-D-ribofuranosyl derivative is formed in high yield, either the benzoyl derivative Ia (IIa) or the acetyl derivative Ib (IIb). The unsubstituted ribosyl derivative Ic is formed from the acetyl derivative Ib by methanolic hydrogen chloride. The benzoylated ribosyl-2,4-thiazolidinedione Ia affords the benzoylated ribosylurea III on reaction with aqueous ammonia, the hydroxyethylurea derivative IVa with 2-aminoethanol, the semicarbazide derivative Va with hydrazine hydrate, the ribosylhydroxyurea derivative VIa on reaction with hydroxylamine hydrochloride and triethylamine, the benzoyl derivative of ribosylbiuret VII with O-methylisourea hydrochloride and triethylamine, and (analogously) ribosylisothiobiuret VIII with S-methylisothiourea. Methanolysis of the benzoyl derivative of hydroxyethylurea IVa with sodium methoxide affords the unprotected riboside IVb. Ribosylhydroxyurea VIb is formed on debenzoylation of compound VIa with methanolic ammonia. Acetylation of compound VIb furnishes the pentaacetyl derivative VIc.

Reactions of lumiflavin with amine radicals

1985 ◽  
Vol 63 (7) ◽  
pp. 1357-1364 ◽  
Author(s):  
Parminder S. Surdhar ◽  
Douglas E. Bader ◽  
David A. Armstrong
Keyword(s):  
Quantum Yield ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
Primary Amine ◽  
Pulse Radiolysis ◽  
Ethylene Diamine ◽  
Secondary Amines ◽  
Diamine Tetraacetate ◽  
Effects Of Ph ◽  
Electron Reduction

The amino radicals (•AH) formed by the 60Co radiolysis of N2O-saturated 0,05 M solutions of ethylene diamine tetraacetate (EDTA) at pH 7 and 11.2 and of glycine at pH 11.2 brought about an efficient two-electron reduction of lumiflavin (Fl). The spectra of the products were identical to those formed by photolysis of the same solutions and by reduction of the lumiflavin with •CO2− radicals. The products were reoxidised to flavin by oxygen. The quantum yield for flavin disappearance was 0.52 ± 0.07 and 0.17 ± 0.01 in the presence of EDTA at pH 7 and 11.2 and 0.065 ± 0.008 and 0.17 ± 0.01 for glycine at the same pHs, respectively.The overall two-electron reduction can be explained by the mechanism:[Formula: see text]The rate constants of reaction [4] were found by pulse radiolysis to be 1.8 ± 0.3 × 109 and 1.5 ± 0.3 × 109 M−1s−1 for the radicals of glycine and EDTA at pH 7 and 3.6 ± 0.3 × 108 M s−1 for glycine radicals at pH 11.2. The spectrum of •FlH formed by glycine radicals at pH 7 is similar to that produced by•CO2−, but there was some perturbation, which is apparently due to interaction with the amine.The radicals formed from the secondary amines piperazine and diethylamine at pH 11.8 also effected reversible two-electron reduction. However, the radicals from glycine anhydride and the primary amine ethylamine yielded significant amounts of non-oxidisable products. The reaction mechanisms are discussed and effects of pH are considered.

Improvement of Hydrolysis and Fermentation of Sugarcane Bagasse by Soaking in Aqueous Ammonia and Methanolic Ammonia

2013 ◽  
Vol 77 (7) ◽  
pp. 1379-1383 ◽  
Author(s):  
Abolghasem HEDAYATKHAH ◽  
Hossein MOTAMEDI ◽  
Hossein NAJAFZADEH VARZI ◽  
Gholamreza GHEZELBASH ◽  
Mostafa AMOPOUR BAHNAMIRY ◽  
...  
Keyword(s):  
Sugarcane Bagasse ◽  
Aqueous Ammonia ◽  
Methanolic Ammonia ◽  
Soaking In Aqueous Ammonia

Formation of an imidosuccinimide by cyclisation of a sterically hindered β-cyanoester with the lithium salt of a primary amine

2000 ◽  
Vol 2000 (3) ◽  
pp. 124-125 ◽  
Author(s):  
Francisco Ros
Keyword(s):  
Primary Amine ◽  
Room Temperature ◽  
Lithium Salt ◽  
Sterically Hindered ◽  
Fold Excess

The reaction of β-cyanoester 1 with a two-fold excess of the lithium salt of homoveratrylamine in THF at 0 °C to room temperature affords the imidosuccinimide 3, which undergoes derivation to the succinimide monooxime 4 by treatment with m-chloroperoxybenzoic acid.

Quinquedentate Coordination of 10-Methyl-1,4,8,12-tetraazacyclopentadecan-10-amine (L) to Rhodium(III). Crystal Structure of cis-[Rh(L)Cl][ClO4]2.H2O And Comparative Activation Volumes for Base Hydrolysis of [M(L)Cl]2+ (M = Rh, Co, Cr)

1992 ◽  
Vol 45 (2) ◽  
pp. 351 ◽  
Author(s):  
GA Lawrance ◽  
M Martinez ◽  
BW Skelton ◽  
R Vaneldik ◽  
AH White
Keyword(s):  
Primary Amine ◽  
Metal Ion ◽  
Exchange Chromatography ◽  
Hot Water ◽  
Base Hydrolysis ◽  
Secondary Amines ◽  
Orthorhombic Space Group ◽  
Pendant Arm ◽  
Base Mechanism ◽  
Hydrolysis Of

The pendant-arm macrocycle 10-methyl-1,4,8,12-tetraazacyclopentadecan-10-amine (1) reacts slowly in hot water with rhodium(III) chloride to yield, following cation-exchange chromatography, exclusively cis -[ Rh (l) Cl ]2+. The cis -complex was crystallized readily as a perchlorate monohydrate salt, in the orthorhombic space group Pn21a, a 16.854(3), b 13.341(3), c 9.985(1) � , Z = 4, isomorphous with its cobalt(III) counterpart; a single-crystal X-ray structure determination was refined to R 0.027 for 1626 'observed' reflections. The pendant primary arnine and two adjacent secondary amines necessarily occupy an octahedral face, with the chloro ligand cis to the primary amine, and secondary amines adopt R,R,S,S stereochemistries. The Rh -N distances [2.056(6) � (pendant primary amine), average 2.08 � (secondary amines)], are at the short end of the range for Rh-N bonds. The Rh-Cl distance is 2.347(2) �. Activation volumes for chloride base hydrolysis were determined for cis -[ Rh (l) Cl ]2+as +19.5( � 1.2), for cis -[Co(l) Cl ]2+ as +27.1(�0.4), and for trans-[Cr(l) Cl ]2+ as +31.1( �0.1) cm3 mol-l, and are consistent with a conjugate base mechanism in each case; variations with metal ion are discussed.

Large-cluster and combined fluorescent and gold immunoprobes

1996 ◽  
Vol 54 ◽  
pp. 892-893
Author(s):  
Richard D. Powell ◽  
James F. Hainfeld ◽  
Carol M. R. Halsey ◽  
David L. Spector ◽  
Shelley Kaurin ◽  
...  
Keyword(s):  
Metal Cluster ◽  
Sulfonyl Chloride ◽  
Gel Filtration ◽  
Cross Linking ◽  
Site Specific ◽  
Fab Fragments ◽  
Cluster Label ◽  
Covalently Linked ◽  
Texas Red ◽  
Fold Excess

Two new types of covalently linked, site-specific immunoprobes have been prepared using metal cluster labels, and used to stain components of cells. Combined fluorescein and 1.4 nm “Nanogold” labels were prepared by using the fluorescein-conjugated tris (aryl) phosphine ligand and the amino-substituted ligand in the synthesis of the Nanogold cluster. This cluster label was activated by reaction with a 60-fold excess of (sulfo-Succinimidyl-4-N-maleiniido-cyclohexane-l-carboxylate (sulfo-SMCC) at pH 7.5, separated from excess cross-linking reagent by gel filtration, and mixed in ten-fold excess with Goat Fab’ fragments against mouse IgG (obtained by reduction of F(ab’)2 fragments with 50 mM mercaptoethylamine hydrochloride). Labeled Fab’ fragments were isolated by gel filtration HPLC (Superose-12, Pharmacia). A combined Nanogold and Texas Red label was also prepared, using a Nanogold cluster derivatized with both and its protected analog: the cluster was reacted with an eight-fold excess of Texas Red sulfonyl chloride at pH 9.0, separated from excess Texas Red by gel filtration, then deprotected with HC1 in methanol to yield the amino-substituted label.

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