Amine oxalates

In our studies of the open-framework zinc oxalates, we have recently isolated monomeric, dimeric, ID linear chain, 2D layer, and 3D structures by the reaction of amine oxalates with Zn2+ ions,21 suggesting thereby that the presence of a hierarchy of structures is not unique to the phosphates alone. We believe that the evidence provided by our studies for the existence of an Aufbau principle of open-framework complex structures is of considerable significance. Many other complex inorganic structures are also likely to be formed by similar building-up processes, involving basic building units and self-assembly. 

Vaidhyanathan, R. Natarajan, S. Rao, C. N. R. Synthesis of a hierarchy of open-framework zinc oxalates from amine oxalates, communicated. 

After providing a brief description of zeolitic structures, we discuss the hierarchy of structures of open-framework metal phosphates ranging from zerodimensional monomeric units and one-dimensional linear chains to complex three-dimensional structures. Aspects related to the likely pathways involved in the assemblage of these fascinating structures are examined, pointing out how the formation of the complex three-dimensional structures of open-framework metal phosphates involves the transformation and assembly of smaller units. Besides the role of the four-membered monomer, the amine phosphate route to the formation of the three-dimensional structures is discussed. The last step in the formation of these structures from preformed units of the desired structure is likely to be spontaneous. Our recent studies of open-framework metal oxalates have shown the presence of a hierarchy of structures. Reactions of amine oxalates with metal ions yield members of the oxalate family with differing complexity. 

What is significant is that zinc oxalates with one-, two- and three-dimensional architectures, in addition to the monomeric and dimeric oxalates, could be synthesized by using amine oxalates. In Fig. 7.34, the various types of structure obtained are presented to demonstrate the similarities and relationships. As can be seen, the structure of the dimer can be derived from that of the monomer, the chain from the dimer, and the layer from the chain. Just as the four-membered ring monomeric phosphate unit plays a crucial role in the building of framework phosphates [18, 38], it is possible that the monomeric and dimeric oxalates are involved in the construction of the extended oxalate framework structures. 

Several open-framework metal oxalates have been synthesized and characterized in last two to three years. They include ID, 2D and 3D structures. Following the success of the amine phosphate route to open-framework metal phosphates, reactions of organic amine oxalates with metal ions have been carried out. These reactions have yielded a hierarchy of zinc oxalates as shown in Figure 7. These different structures are mutually related. 

Aliphatic hydrocarbons Ammonia Chlorine Butanes Glycol ethers Hydrochloric acid Methylene chloride Monoethanol amine Oxalic acid Phosphoric acid Sodium hydroxide Sodium metasilicate Sulfuric acid Surfactants Tetrachloroethylene 1,1,1-Trichloroethane... 

Luminescence has been used in conjunction with flow cells to detect electro-generated intennediates downstream of the electrode. The teclmique lends itself especially to the investigation of photoelectrochemical processes, since it can yield mfonnation about excited states of reactive species and their lifetimes. It has become an attractive detection method for various organic and inorganic compounds, and highly sensitive assays for several clinically important analytes such as oxalate, NADH, amino acids and various aliphatic and cyclic amines have been developed. It has also found use in microelectrode fundamental studies in low-dielectric-constant organic solvents. 

COj liberated. All acids esters which hydrolyse easily, e.g., methyl oxalate (p. 357) salts of amines nitrophenols. 

The b.p. under diminished pressure has been given as 80-81°/18 mm. To obtain a very pure sample of the amine, dissolve 1 part (by weight) of the above product with a sohitiuii of 1-04 parts of crystallised oxalic acid in 8 parts of hot water, add a little deculeiirisiiig carbon, and tilter. The liltered solution deposits crystals uf the acid oxalate about o g. of tliis salt remains in each 100 ml. of... 

Primary synthesis of arylazopyrimidines is used (52JCS3448). It is exemplified in the condensation of phenylazomalondiamidine with diethyl oxalate to give the azopyrimidine (833) (66JCS(C)226). Finally, 5-phenylazopyrimidine may be made by the condensation of pyrimidin-5-amine with nitrosobenzene (5UCS1565) but the reaction seems to have been overlooked for many years. 

Dry air is blown through the solution to remove the excess of ammonia, and the solution is then dissolved in its own volume of absolute alcohol. A sample of this solution is titrated with standard oxalic acid, litmus being used as an outside indicator (Note 3). The amount of oxalic acid (Note 4) necessary to form the acid salt is placed in a large evaporating dish and dissolved in 4 1. of 95 per cent alcohol. The amine solution is then slowly run into the acid with constant stirring. During the addition of the last half of the amine solution, the container must be cooled in order to avoid the formation of the neutral oxalate,... 

The volume of the diluted amine is usually between 800 and 860 cc. A lo-cc. portion of this may be conveniently drawn off with a pipette and usually requires from 35 to 50 cc. of 0.5 N oxalic acid. 

If very pure amine is desired the product described above is dissolved with 1.04 parts of crystalline oxalic acid in eight parts of hot water. After clarification with Norite, the filtered solution on cooling deposits crystals of the acid oxalate. About 5 g. of the salt remains in each 100 cc. of the mother liquor most of this can be obtained by evaporation and further crystallization. The amine is liberated from the pure oxalate with potassium hydroxide, distilled with steam, and purified as described above. When a known amount of amine is desired in water solution (as for optical resolution) a weighed amount of the (anhydrous) oxalate is decomposed and the amine is distilled quantitatively with steam. 

In context with the formation of peraminosubstituted 1,4,5,8-tetraazaful-valenes of type 85 it must be mentioned that the bis-vinylogous compounds 94 can be easily prepared by reaction of acetamidine with bisimidoylchlo-rides derived from oxalic acid (96S1302). In the course of a complex reaction a cyclic ketene aminal was produced it immediately underwent an oxidative dimerization to yield deeply colored TAFs. Tlieir high chemical stability can be compared with that of indigoid dyes and manifests itself, for example, by the fact that they are soluble in hot concentrated sulfuric acid without decomposition. Tire same type of fulvalene is also available by cy-... 

One of the syntheses of f1 udalanine begins with base promoted condensation of ethyl fluoroacetate and ethyl oxalate to give This is then converted by hydrolytic processes to the insoluble hydrated lithium salt of fluoropyruvate (58). This last is reductively aminated by reduction with sodium boro-deuteride and the resulting racemate is resolved to give D-flu-dalanine (59). 

Diethyl Amino Ethyl Amine Ethyl Oxalate 2-Chlorobenzyl Chloride... 

The initiating radicals are assumed to be SCN, ONO or N3 free radicals. Tris oxalate-ferrate-amine anion salt complexes have been studied as photoinitiators (A = 436 nm) of acrylamide polymer [48]. In this initiating system it is proposed that the CO2 radical anion found in the primary photolytic process reacts with iodonium salt (usually diphenyl iodonium chloride salt) by an electron transfer mechanism to give photoactive initiating phenyl radicals by the following reaction machanism ... 

EDTA, leading to a postulate that more than one equivalent of Ca2+ can be captured by X (e.g. one Ca2+ sequestered by the three amines and the three carboxylates and another Ca2 + by the remaining half the donor groups), as the Dreiding model suggests. The fact that there was no interaction at neutral pH of X with phosphate or oxalate anions was separately confirmed. Thus, the dissolution of Ca3(P04)2 and Ca(C204) is entirely due to the cation complexation mechanism. 

Methylkasugaminide (5) by Cold Alkaline Hydrolysis of C9-Amine (3) with Barium Hydroxide. A solution of C9-amine (519 mg., 2.24 mmoles) dissolved in 5 ml. of water free from carbon dioxide was treated with 50 ml. of barium hydroxide saturated solution at room temperature for 48 hours. Generation of ammonia was observed and barium oxalate (241 mg., 0.99 mmole) was obtained. After removal of barium oxalate, barium carbonate produced by neutralization with dry ice was also removed by filtration. The filtrate thus obtained was placed on a column of Amberlite CG-50 (ammonium form, 1.5 x 25 cm.) and developed with water. After the similar treatment as described in the cold hydrolysis of kasugamycin, ninhydrin-positive fractions afforded a colorless crystalline material (154 mg., 0.62 mmole), m.p. 223°-225°C. (dec.), [ ]D20 +110° (c=1.7, H20), pK a 1.8 and 7.9, which was identified to be C9-acid (15). Anal. Calcd. 

As expected, similar treatment of 3-nitroarenes furnishes mixtures of 4- and 6-substituted 3H-azepines, 54 and 55, respectively.176 Comparable yields of mixed azepines were also obtained by deoxygenation of 3-nitroarenes with alkylphophorous triamides, formed in situ from hexa-methylphosphorous triamide and excess of a secondary amine.66 In a few cases the 3//-azepines were separated by fractional crystallization of their oxalate salts66 but, in general, pure isomers were not isolated and the yields cited in the table were determined by HNMR spectroscopy. 

Mixtures of 3//-azepines are also formed from l,2-dimethyl-4-nitrobenzene, which in diethyl-amine yields A,./V-diethyl-5,6-dimethyl-3//-a7cpin-2-amine (9%) and AfN-diethyl-4,5-dimeth-yl-3f/-azcpin-2-aminc (22% oxalate mp 119-120°C).66 Likewise, 2,4-dimethyl-l-nitrobenzene furnishes a mixture of /V.A-diethyl-5,7-dimethyl-3//-azepin-2-amine (7% oxalate mp 140-141UC) and /V,A-diethyl-3,5-dimethyl-3//-azepin-2-amine (2% oxalate mp 85-86 C). The symmetrically substituted l,3-dimethyl-5-nitrobenzene, as expected, yields only (V.tV-diethyl-4,6-dimethyl-3//-azepin-2-amine (46% bp 96 99 (2/1.3 Torr). 

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