Chloromethyl with ammonia

Curing the treated fibers with ammonia chemically attaches the compound to the cloth. The corresponding sulfate has replaced much of the hydroxide because under certain conditions of manufacture or use the carcinogen bis(chloromethyl) ether may form. 

Chloromethyl)quinazoline 3-oxides, c.g. 8, react with ammonia and primary amines to yield 3//-1,4-benzodiazepine 4-oxides 10, sometimes accompanied by the simple substitution products 9.219 Dimethylamine220 and pyrrolidine221 react analogously, but other secondary amines afford only products of type 9. 

Electrophilic substitution of the ring hydrogen atom in 1,3,4-oxadiazoles is uncommon. In contrast, several reactions of electrophiles with C-linked substituents of 1,3,4-oxadiazole have been reported. 2,5-Diaryl-l,3,4-oxadiazoles are bromi-nated and nitrated on aryl substituents. Oxidation of 2,5-ditolyl-l,3,4-oxadiazole afforded the corresponding dialdehydes or dicarboxylic acids. 2-Methyl-5-phenyl-l,3,4-oxadiazole treated with butyllithium and then with isoamyl nitrite yielded the oxime of 5-phenyl-l,3,4-oxadiazol-2-carbaldehyde. 2-Chloromethyl-5-phenyl-l,3,4-oxadiazole under the action of sulfur and methyl iodide followed by amines affords the respective thioamides. 2-Chloromethyl-5-methyl-l,3,4-oxadia-zole and triethyl phosphite gave a product, which underwent a Wittig reation with aromatic aldehydes to form alkenes. Alkyl l,3,4-oxadiazole-2-carboxylates undergo typical reactions with ammonia, amines, and hydrazines to afford amides or hydrazides. It has been shown that 5-amino-l,3,4-oxadiazole-2-carboxylic acids and their esters decarboxylate. 

Omeprazole is obtained [15] by the reaction of acetyl ethyl propionate 1 with ammonia to give ethyl -3-amino-2,3-dimethyl acrylate 2. Compound 2 was converted to to 2,4-dihydroxy-3,5,6-trimethyl pyridine 3 by treatment with methyl diethylmalonate. Treatment of compound 3 with phosphorous oxychloride produced 2,4-dichloro-3,5/6-trimethyl pyridine 4. 4-Chloro-3/5,6-trimethyl pyridine 5 was obtained by treatment of compound 4 with hydrogen. On treatment of compound 5 with hydrogen peroxide and acetic acid, 4-chloro-3,5,6-trimethyl-pyridine-N-oxide 6 was produced. Treatment of compound 6 with acetic anhydride gave 4-chloro-2-hydroxymethyl-3,5-dimethyl pyridine 7 which was converted to 2-hydroxymethyl-3,5-dimethyl-4-methoxypyridine 8 by treatment with sodium methoxide. Compound 8 was treated with thionyl chloride to produce 2-chloromethyl-3,5-dimethyl-4-methoxypyridinc 9. Compound 9 interacts with 5-methoxy-2-mercaptobenzimidazole to give 5-methoxy 2-[((4-methoxy-3,5-dimethyl-2-pyridinyl)methyl)thio]-lH-bcnzimidazole 10 which is oxidized to omeprazole 11. 

The weak-base anion-exchange resins, that is, the secondary RCH2NHR and tertiary amine RCH2NR2, are produced by reacting the chloromethylated resin with lower substituted amines or with ammonia [124],... 

On treatment with ammonia or primary amines, 6-substituted 2-chloromethyl-4-phenylquin-azoline 3-oxides 1 undergo rearrangement to 2-amino derivatives of 7-substituted 5-phenyl-3//-1,4-benzodiazepine 4-oxide 2, Reaction with secondary amines proceeds without rearrangement with formation of the expected 2-(aminomethyl)-4-phenylquinazoline 3-oxides (cf. Section 6.3.1.1.10.3.). 2o. s2i... 

CHLOROMETHYL SULFONE (124-63-0) Combustible liquid (flash point >212°F/ >100°C). Reacts with water, acid, or acid fumes, forming hydrochloric acid. Violent reaction with ammonia, caustics, strong oxidizers. Aqueous solution incompatible with sulfuric acid, ammonia, aliphatic amines, alkanolamines, bases, isocyanates, alkylene oxides, epichlorohydrin. Attacks metals in the presence of moisture. 

Zinc powder (1.75 g) was added within 10 min to a stirred suspension of 5-(chloromethyl)-uracil (0.2 g) in 6n-DC1 (75 ml) at 60-75°C, and the mixture was stirred at that temperature for 2.5 h. The liquid was then decanted from the excess of metal powder, and the zinc was washed several times with water. After cooling, the aqueous solution was exactly neutralized with ammonia, freed from precipitated zinc hydroxide, and concentrated in a vacuum. The crystals that separated were collected. Recrystallization from water gave [oc-Di]thymine (0.04 g), m.p. 327-329°C (dec.). 

The number of nitrogens in the chain can vary from two on up. In many cases the nitrogen-carbon bond is an integral part of the polymer network. There are more than two carbons between nitrogens in some cases, and the carbons may carry other substitutions. The actual ionogenic functionality is a mixture of primary, secondary and tertiary amines. Polyamine resins made by condensing phenol, formaldehyde and polyamine were among the first commercial resins. Other methods of manufacture include the reaction of a polyamine with a chloromethylated styrene-divinyl-benzene copolymer, and condensation of epichlorhydrin with ammonia or polyamines. 

V-Alkylation. (Chloromethyl)dimethylphenylsilane (1) has been utilized for the alkylation of nitrogen nucleophiles including amines, a-aminoesters (eq 5), anilides and anilines (eq 6), 4 benzimidazole, potassium cyanate (with in situ treatment with ammonia to afford a nitrosourea), and sodium azide (eq 1)P Although 1 has been utilized for IV-alkylation of a variety of nitrogen nucleophiles, the reaction conditions tend to be similar and usually involve employing an exogenous base, elevated temperatures, and polar aprotic solvents (e.g., DMF, DMSO, DMPU) to effect the M-alkylation. In some cases, for instance, alkylation of Q -aminoester 9, potassium iodide is incorporated to facilitate the reaction. 

Krespan ° has prepared a number of macrocycles, having both aza- and oxa-linkages in them, based on the 3,3-dimethyleneoxetane unit (see also Sect. 8.4 and Eq. 8.12). Typically, 3,3-bis(chloromethyl)oxetane is treated with a diol as shown in Eq. (3.40), in the presence of base. Once the bicyclic system is formed, further treatment with other nucleophiles (e.g., ammonia) can lead to opening of the 4-membered ring. 

Reaction of a-chloromethyl ketones with (3-ketoesters and ammonia to assemble pyrroles. 

However, with liquid ammonia or anhydrous methylamine 1,2,4-oxadiazines (88) are formed. 5-(Chloromethyl)-l,2,4-oxadiazoles (e.g., (86) react with urotropin to form salts, which are hydrolyzed with hydrochloric acid to 5-(aminomethyl) compounds (the Delepine reaction). Alternatively, 5-(aminomethyl)-l,2,4-oxadiazoles have been prepared by condensation of amidoximes with a-amino-acids <72JHC435>. 

A few representatives of this heterocyclic system 35 were synthesized in very high yield (85-90%) by the intramolecular nucleophilic cyclization of the acetylene derivatives 36 (81RTC10), which in turn were obtained by treatment of alkynyl(chloromethyl) sulfides with one equivalent of Na2Te, the latter being prepared from elemental sodium and tellurium in liquid ammonia. 

Methyl-l-penten-3-one-l-ol 1 and glacial acetic acid in benzene was added to pyrrolidine to give 2-methyl-l-pen ten-1-[N-pyrrolidinyl]-3-one 2. Compound 2 when treated with oxalyl chloride and methanol was added, 3,5-dimethyl-2-methoxycarbonyl-4-pyrone 3 was produced. Treatment of compound 3 with sodium borohydride in methanol gives 3,5-dimethyl-2-hydroxymethyl-4-pyrone 4. Compound 4 was converted to 3,5-dimethyl-2-hydroxymethyl-4-pyridone 5 by heating compound 4 with aqueous ammonia in a sealed flask. Compound 5 was converted to 4-chloro-2-chloromethyl-3,5-dimethyl pyridine 6 by treatment with phosphorous oxychloride. Treatment of compound 6 with 5-methoxy-2-mer-captobenzimidazole in tetrahydrofuran gave 2-[2-(4-chloro-3,5-dimethyl pyridinyl)methylthio]-5-methoxy benzimidazole 7. When compound 7 was treated with potassium hydroxide in dimethyl sulfoxide containing methanol, 2-[2-(3,5-dimethyl-4-methoxypyridinyl)methylthio]-5-methoxy... 

Primary amines.9,22,62 Direct amination of chloromethyl-trimethylsilane illustrates the diliiculty of stopping the reaction at the monoalkylation level with the formation of up to 30% of the bis(trimethylsilylmethyl) amine even when a large excess of ammonia is employed. The same process has been used to prepare aminomethylsiloxanes where the formation of a small amount of the secondary amine is also observed.63 See also Ref. 24. 

In conclusion, all results obtained thus far on this reaction show that it is especially the 4-position in the 3-nitro-l,8-naphthyridines which is strongly favored toward the attack of the carbanion of chloromethyl phenyl sulfone. When position 4 is occupied by a substituent no reaction occurs. This behavior is in accordance with the behavior observed in reactions with liquid ammonia and liquid methylamine. 

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