Methanoic acid synthesis

HCOOCHjCHj. Colourless liquid with the odour of peach-kernels b.p. 54 C, Prepared by boiling ethanol and methanoic acid in the presence of a little sulphuric acid the product is diluted with water and the insoluble ester separated and distilled. Used as a fumigant and larvicide for dried fruits, tobacco and foodstuffs. It is also used in the synthesis of aldehydes. 

Methanesulfonyl chloride, 23 653, 681-683 Methano[60]fullerenes, 12 242 Methanogenic conditions, defined, 3 757t Methanoic acid, physical properties, 5 29t Methanol, 16 299-316. See also Methanol synthesis... 

Oxoglutarate can also serve as a starter piece for elongation by the oxoacid pathway. Extension by three carbon atoms yields 2-oxosuberate (Eq. 21-1). This dicarboxylate is converted by reactions shown in Eq. 24-39 into biotin and in archaebacteria into the coenzyme 7-mercaptoheptanoylthreonine phosphate (HTP), Eq. 21-1. Lipoic acid is also synthesized from a fatty acid, the eight-carbon octanoate. A fatty acid synthase system that utilizes a mitochondrial ACP may have as its primary fimction the synthesis of ocfanoate for lipoic acid formation. The mechanism of insertion of the two sulfur atoms to form lipoate (Chapter 15) is imcerfain. If requires an iron-sulfur protein jg probably similar to the corresponding process in the synthesis of biotin (Eq. 24-39)9 93a formation of HTP (Eq. 21-1). One component of the archaebacterial cofactor methano-furan (Chapter 15) is a tetracarboxylic acid that is formed from 2-oxoglufarafe by successive condensations with two malonic acid imits as in fatty acid synthesis. ... 

Formic acid (also called methanoic acid) is the simplest carboxylic acid. Its chemical formula is HCOOH or HCO2H. It is an important intermediate in chemical synthesis and occurs naturally, most notably in the venom of bee and ant stings. In fact, its name comes from the Latin word for aat, formica, referring to its early isolation by the distillation of ant bodies. Esters, salts, and the anion derived from formic acid are referred to as formates. 

At first sight, a carboxylic acid looks like two functional groups—an alcohol and an aldehyde—that happen to be bonded to the same carbon atom. However, the chemistry of carboxyhc acids differs considerably from the functional groups we have described in previous chapters. The simplest carboxylic acid is methanoic acid, more commonly called formic acid. In this chapter, we consider the structure, properties, reactions, and synthesis of carboxylic acids. 

Another method was developed for the synthesis of 5,8-methano-3,l-benzoxazine-2,4-diones 157. The A-BOC amino acid 156 was prepared from the half ester 155 without purification of the intermediates. Thus, 155 was treated with ethyl chloroformate, and subsequently with sodium azide. 

A total synthesis of ( )-dihydrospiniferin-l (149), an unstable furanosesquiterpene from the Mediterranean sponge Pleraplysilla spinifera, has been reported. It is of interest because (149) is the first reported natural product incorporating the novel l,6-methano[10]annulene carbon framework (80JA4274). The key step in the synthesis is the condensation of the aldehyde (150) with methoxymethylenetriphenylphosphorane in toluene to give the bis-enol ether (151). Treatment of (151) with aqueous hydrochloric acid in diethyl ether affords the furan (149). 

Methano amino acids 6 and 7 (Scheme 6), which have rigidly defined x1 orientations, have been utilized by several groups and shown to induce y-turn structures. Incorporation of (25,35)-c-Met 7 into the anti-opiate peptide H-Phe-Met-Arg-Phe-NH2 (with replacement of the Met residue) using solid-phase synthesis provided an analogue whose lowest energy conformation involved a y-turn centered around the c-Met residue (Scheme 6)J32 ... 

Further discussion and additional references to the synthesis of peptides containing dide-hydro-a-amino acids, reduced peptide isosteres, TV-hydroxy amides and hydrazides, and Ca-tetrasubstituted amino acids including 2,3-methano amino acids can be found in Sections 11.1,10.7,10.8, and 10.3, respectively. 

Yokomatsu, T., Abe. H.. Sato, M., Suemune, K., Kihara, T., Soeda, S., Shimeno, H., and Shibuya, S., Synthesis of l,l-difluoro-5-(l//-9-purinyl)-2-pentenylphosphonic acids and the related methano analogues. Remarkable effect of the nucleobases and the cyclopropane rings on inhibitory activity toward purine nucleoside phosphorylase, Bioorg. Med. Chem., 6, 2495, 1998. 

The synthesis of kifunensine (1) was also achieved from the 5-deoxy-5-azidomannolactone derivative 8, obtained from cw-cyclohexadienediols by microbial oxidation using Pseudomonas putida 39D, ° by isopropylidenation followed by reduction to furnish 9 in 30% yield. Treatment of 9 with dimethyl oxalate followed by methano-lic ammonia furnished intermediate 10 (55%), which underwent oxidation of the primary alcohol to the aldehyde followed by cycUzation in methanolic ammonia to afford 11. Removal of the diacetoiude groups from 11 with 75% trifluoroacetic acid gave (+)-l. 

AI3-15357 Amid kyseliny mravenci Carbamaldehyde CCRIS 6240 EINECS 200-842-0 Formamide Formic acid, amide Formimidic acid HSDB 88 Methanamide Methanoic xid, amide NSC 748. Solvent, softener, intermediate in organic synthesis. Liquid mp = 2.55 bp = 220 d = 1.1334 soluble in H2O, organic solvents LDso (rat orl) = 6570 mg/kg. BASF Corp. Fluka Penta Mfg. Sigma-Aldrich Fine Chem. 

An ingenious synthesis of steroidal annulenes has appeared. The close relationship of annulenes to the classical aromatic substance naphthalene stimulated the synthesis of l,6-methano-[10]annuleno-steroids, which are analogues of equilenin (97). The y,5-cyclopropyl-a -unsaturated ketone (98) was the initial target. Treatment of the cyclopropyl ketone (98) with acetic anhydride and methyl orthoformate in the presence of an acid catalyst then gave (99). Conversion of the cycloheptatriene (99) into the requisite 10 c-electron system (100) was then accomplished by dehydrogenation. ... 

Application of a malonic acid extension procedure with substituted malonates to the cyclopentenone pentanoate 10 afforded the cyclopentenone precursors for various 2-substituted 11-deoxyprostaglandins (Scheme 6) ( ). The preparation from W of cyclopentenone intermediates for the synthesis of 2-nor-(62). 2,3-methano-, and 3-thia-4-homo-ll-deoxyprostaglandins (49) is described in Scheme 7. 

Scheme 4.16, Table 4.6). In the case of synthesis of (2/ ,35)-3-cndo-p-methylbenzy-loxycarbonyl-1,2,3,4-tetrahydro-1,4-methano-naphthalene-2-carboxylic acid (entry 1), the use of ball milling was advantageous, since in solution the starting anhydride was unreactive, whereas nnder ball-milling conditions the asymmetric anhydride opening with p-methylbenzyl alcohol proceeded well, affording hemiester with 32% enantiomeric excess in 78% yield. 

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