Acid halogenides

Acid Halogenides. For acid halogenides the name is formed from the corresponding acid radical if this has a special name (Sec. 3.1.2.10) for example, NOCl, nitrosyl chloride. In other cases these compounds are named as halogenide oxides with the ligands listed alphabetically for example, BiClO, bismuth chloride oxide VCI2O, vanadium(lV) dichloride oxide. 

The usual methods for the preparation of acid amides cannot be used with lysergic acid. On trying to transform it into the acid halogenide it becomes transformed into a useless resin. By using lysergic acid methylester, which can be obtained from lysergic acid by treating it with diazomethane, no better result is obtained, as under the conditions necessary for the preparation of acid amides, this compound becomes decomposed. 

Kolitowska (25) has investigated the hydrolysis of diphosphorus tetraicdide, P2I4, which is formally regarded as an acid halogenide of 2 2... 

Electrophilic Route Ether Functional Monomer Acid Halogenide... 

Many proteins have been labeled with organometallic complexes, mostly for analytical purposes. Some of those are mentioned in Section 1.31.5 of this chapter, and the topic has been comprehensively reviewed by Salmain. Ryabov published an earlier review on the topic.The labeling techniques are mostly the same as for organic derivatives, that is, cysteine-selective reactions (maleiimides, acetic acid halogenides), activated acids, aldehydes, or thiocyanates that react with lysines, biotin-(strept)avidine labeling, and others. 

Carboxylic acid halogenides are formed with hydrogen halides (4) [459, 460]. 

Activated acid derivatives, e. g., acid halogenides or anhydrides, are used as acylating agents ... 

To a solution of 5 mmol of 1,3-diphcnyl 3-[(S )-2-mcthoxymethyl-l-pyrrolidinyl]-2-propenyl[lithium in 10 mL of tort-butyl methyl ether (prepared according to Section D. 1.1.1.2.2.3.) at 0°C. 6.25 mmol of the aldehyde (and eventually 6.25 mmol of lithium halogenide in 27 mL of leri-butyl methyl ether) are added dropwise. Stirring is continued for 2 h and 0.39 g (5.0 mmol) of acetyl chloride are added. After 2 h stirring at r.t., 10 mL of the solvent, 50 mL of diethyl ether and 10 mL of 2 N aq hydrochloric acid are added and stirring is continued for 2 h at 20 C. The organic layer is extracted with three 20 mL-portions of water and the aqueous solutions are reextracted with diethyl ether. The combined aqueous solutions are dried over Na,S04, concentrated in vacuum and the residue distilled to yield a mixture of xyn- and on/i-ketones >90% ee, determined by H-NMR with Pr(hfc)3. 

This reaction also takes place with halogenides of dibasic acids. Thus adipoyl chloride and diethyl phosphite are reacted at 90°C for 8 h yielding adipyl-diphosphonic acid diethyl ester, according to Eq. (41). 

Palladium and platinum. These are resistant to chemical attack (Pt more than Pd). Both metals dissolve in fused alkali metal oxides and peroxides. Pt is attacked, at high temperature, by molten alkali and alkaline earth halogenides and by several compounds of B, Si, Pb, P, As, Sb, Bi. Pd dissolves slowly in oxidizing acids Pt is dissolved by aqua regia. 

Exhaustive studies on well-defined systems are rather scarce (4) nevertheless 3 systems thoroughly analyzed by independant research groups are of outstanding interest a) the quaternization of polyvinylpyridines by alkyl halogenides (20-25) b) the chlorination of polyethylene (13,26-28) c) the basic or acid hydrolysis of PMMA (29-31). On the other hand, neighbouring groups effects have been quantitatively taken into account for the kinetic analysis of periodate oxidation of amylose (32,33). 

It is prepared by reaction of phenoxyacetic acid alkali salts with allyl halogenide and used in technical perfumery. 

The terminal carhanionic sites of "living" polymers can be reacted with various electrophilic compounds of yield (o)-functional polymers. Esters, nitriles, acid chlorides, anhydrides, lactones, epoxides, benzyl or allyl halogenides have been used for their high reactivity with metal organic sites, to yield appropriate functions.2 Carbon dioxide is also an efficient reagent to yield terminal carboxylic functions. 

From the values given in the table the equilibrium constants of the hydrogen halogenides can be calculated by use of the equation AF° = —RTlnK. The calculated values are somewhat uncertain because of uncertainty in the estimate of the standard free energy of solution of the dissociated molecules. The values obtained in this way are 2 X 10 for HC1, 5 X 10s for HBr, and 2 X 109 for HI. These acids are accordingly very strong acids. 

It can be concluded from these experimental results that in alkaline media the 2-octyl nitrate behaves like a typical ester (Day and Ingold (50]). In neutral media, on the other hand, it behaves like an alkyl halogenide or like an ester of sulphuric acid. 

Reactions of 02 with esters and halogenides of carbonic acids also pass nucleophilic substitution as an initial step (Sawyer Gibian 1979). Final products are acyl peroxides or carbonic acids, Scheme 1-79 ... 

The processes involving the aziridine cycle are very diverse. For instance, reactions of alkylation by alkyl halogenides [63], bromoacetic acid derivatives [29, 30] and acetoxypropene [64], are known. The use of arylboronic acids for synthesis of TV-alkyl derivatives, e.g., compound 45, is described in [63] (Scheme 1.13). The one-step reaction at room temperature of aziridinyl ketones 46 with chloroacetamides 47 and sulfur in the presence of Et3N yields mono-thio-oxamidines 48 [65]. 

Reaction of 4,5-disubstituted imidazole 1-oxides 263 with POCl3 or POBr3 produces 2-chloro or 2-bromoimidazole 301 (Hal = Cl or Br) (1975JCS(P1)275, 2002AG(E)2290). A possible mechanism in line with that in play by acylation comprises O-phosphorylation to be followed by addition of halogenide ion and subsequent elimination of halophosphoric acid as outlined in Scheme 89. 

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