Morpholine, chlorination

Iron-arene complexes are known to exhibit extremely high photoactivity as initiators. Quantum efficiencies have been found to be greater than I in the photopolymerisation of dicyanate esters. Phenylglycine derivatives have been found to be excellent co-synergists for the iron-arene complexes when used in conjunction with dyes and amines. Complexes of various types have also been proposed. Maleic anhydride-THF complexes have been used for the photopolymerisation of oligourethane acrylates while metal-ion complexes of spiropyran copolymers undergo reversible polymer precipitation. Azo and polyazo initiators have been used to make butadiene-isoprene block copolymers while charge-transfer complexes of morpholine-chlorine induce the radical polymerisation of methyl methacrylate. The presence of zinc chloride enhances the... 

Carr and England211 investigated the kinetics of the hydrochloric acid-catalysed chlorination of phenol by N-chloro-succinimide, -acetamide, and -morpholine, and found that the latter compound gave third-order kinetics, viz. 

An abnormal (tele) substitution of chlorine in both 2,3- and 2,6-dichloropyrazines 91, 92 occurred on reaction with dithiane anion, while morpholine gave the normal //wo-substitution <06TL31>. Another paper described the highly selective ipso monosubstitution of the 2,3-dichloro compound by enolates in toluene <06T9919>. 

Methylthiopyrido[2,3-e][ 1,2,4]triazine 41 was prepared (76KGSI140) by cyclization of 2-amino-3-hydrazinopyridine 40 with carbon disulfide followed by methylation. Oxidation of 41 with chlorine afforded the 3-methylsulfonopyridotriazine 42. Heating 41 with morpholine or pyrrolidine gave 43, whereas the reaction at 20°C gave 44. 

A limited number of such reactions have been recently published, and the results are compiled in Table 5. The first example is the reduction of azido compound 76 by sodium dithionite to the corresponding amine 77. Furthermore, some nucleophilic substitutions of the chlorine substituents of heterocycles 78 and 80 have also been reported these compounds, when reacted with morpholine and w-bromoaniline, respectively, furnished the substitution products 79 and 81. 

Hydrogen peroxide converts morpholine into its 4-hydroxy derivative (50JA2280), but TV-alkyl morpholines yield 3-oxo compounds if ruthenium(VIII) oxide or sodium metaperiodate are used as oxidants (76S598). Chlorine at -70 °C oxidizes the thiomorpholine (116) to the dihydro-1,4-thiazine (117) (73JCS(Pl)l32l), but more vigorous conditions result in the formation of S-oxides. 

This oxidative chlorination-cyclization strategy has also been applied to the synthesis of the bicyclic /3-sultam 166 from chiral morpholine derivatives (Scheme 51) <2004HCA90>. 

Dichloroquinoxaline (101) is aminated by morpholine in the presence of excess cesium fluoride/18-crown-6 with simultaneous exchange of chlorine by fluorine to give 102 in 78% yield, whereas glycine ethylester-hydrochloride affords 103 in 61% yield (87HI215). 

Direct bromination readily yields the 6-bromo derivative (111), just as with uracil. Analogous chlorination and iodination requires the presence of alkalies and even then proceeds in low yield. The 6-chloro derivative (113) was also obtained by partial hydrolysis of the postulated 3,5,6-trichloro-l,2,4-triazine (e.g., Section II,B,6). The 6-bromo derivative (5-bromo-6-azauracil) served as the starting substance for several other derivatives. It was converted to the amino derivative (114) by ammonium acetate which, by means of sodium nitrite in hydrochloric acid, yielded a mixture of 6-chloro and 6-hydroxy derivatives. A modified Schiemann reaction was not suitable for preparing the 6-fluoro derivative. The 6-hydroxy derivative (115) (an isomer of cyanuric acid and the most acidic substance of this group, pKa = 2.95) was more conveniently prepared by alkaline hydrolysis of the 6-amino derivative. Further the bromo derivative was reacted with ethanolamine to prepare the 6-(2-hydroxyethyl) derivative however, this could not be converted to the corresponding 2-chloroethyl derivative. Similarly, the dimethylamino, morpholine, and hydrazino derivatives were prepared from the 6-bromo com-pound. ... 

Treating l-(morpholin-4-yl)cyclohexene with CBT in the presence of triethylamine yields bicyclo[3.1.0]hexane derivative 100 in 70% yield [94H(38)319], Reaction proceeds through the formation of an intermediate chlorinated enamine and subsequent elimination of chlorine followed by the addition of benzotriazole (Scheme 78). 

O-Demethylation has been observed as well as, or instead of, nucleophilic displacement on reaction of 3,4,5-chloro/methoxy pyridazines and 4,5-chloro/methoxy-2-methyl-3(2//)-py-ridazinones with morpholine (e.g.. Scheme 63). Demethylation was observed at all ring positions, but usually adjacent to chlorine or a carbonyl group, and A -methylmorpholine was isolated, consistent with demethylation rather than hydrolysis. The demethylation can also occur with other primary and secondary amines such as diethylamine, butylamine, and piperidine, but not with pyrrolidine and aniline <87H(26)1 >. 3-Phenolic ethers of pyridazines are resistant to reductive cleavage of the aryl ether bond under the conditions of phase transfer catalytic hydrogenolysis <82T3775>. 

The chlorine atoms in the 1,3,5,2/l -triazaphosphinines have acid chloride character and are readily replaced by nucleophiles. In the 2,2,4-trichloro compounds (229) the reaction with amines occurs selectively. At a molar ratio of (229) to amine of 1 2 only the C-4 chlorine is replaced. With excess of amine (dimethylamine, morpholine, ethylamine) the triamino derivatives (231) are formed, even at 20 °C. The reaction with diethylamine stops at the stage of the monoamino derivative (230) for steric reasons (Scheme 47) <79ZOBi777>. 

Various 2-oxo compounds have been subjected to a variety of reactions. Alkylation and acylation result in the formation of 1,3-disubstituted products.Similarly the Mannich reaction with morpholine gives products such as the bis compound 107. Halogenation of the 0x0 compound 108 with bromine in acetic acid," or chlorine in acetic acid, ° or with sulfuryl chloride results in formation of the monohalo derivatives 109. The chlorine atom in 109 (R = Cl) can be removed by hydrogenation over palladium on charcoal. Nitration of the chloro compound 110 with a mixture of nitric and sulfuric acids provides the nitro derivative 111, which may be catalytically reduced to the amino compound 112. If the reduction is carried out in the presence of an aldehyde, the product is a substituted amino derivative (113). Alternatively the amine 112 can be condensed with an aldehyde and the resultant Schiff base reduced to give the product 113. 

AI3-24289 CCRIS 6691 EINECS 203-640-0 Methylmorpholine Morpholine, 4-methyl- Morpholine, N-methyl- 4-Methylmorfolin 1-Methylmorpholine 4-Methylmorpholine N-Methylmorpholine NSC 9382 Texacat NMM UN2535. Catalyst for polyester urethane flexible foam, high rise rigid foam panels, extraction solvent stabilizer for chlorinated hydrocarbons self-polishing waxes corrosion inhibitor pharmaceuticals. Oil mp = -65° bp = 116° d = 0.9051 soluble in H2O, EtOH, Et20 LDsO (rat orl) = 1960 mg/kg. Texaco. 

When the two chlorine atoms of sj/m-dichlorodiethyl ether are replaced by the imino group through the action of anhydrous ammonia, morpholine is obtained (example 6, p. 399). The S30ithesis is carried out by treating sym-dichlorodiethyl ether dissolved in benzene with anhydrous ammonia at 50°C. ... 

Only a few solvents are known to dissolve cellulose completely, and solid cellulose decomposes before melting. Therefore, it is difficult to study the mesophase behavior of cellulose. Chanzy et al. [32] reported lyotropic mesophases of cellulose in a mixture of jV-methyl-morpholine-Af-oxide and water (20-50%), but were unable to determine the nature of the mesophase. Lyotropic cholesteric mesophase formation in highly concentrated mixtures of cellulose in trifluoroa-cetic acid + chlorinated-alkane solvent [33] and in ammonia/ammonium thiocyanate solutions [34] has been studied, and although poor textures were obtained in the polarizing microscope, high optical rotatory power has been measured in an optical rotation (ORD) experiment, which could be fitted to the de Vries equation [Eq. (3)] for selective reflection beyond the visible wavelength region and was taken as proof of a lyotropic chiral nematic phase. 

Cellulose/NMMNO (iV-methyl-morpholine-iV-oxide) [32, 40, 41] Cellulose/TFA +chlorinated alkanes (1,2-dichloroethane, CH2CI2) [33] right-handed... 

For example, high-temperature chlorination of the morpholine derivative (LXXVI) affords the heterocyclic imidoyl chloride (LXXVII)... 

Perhalogenated imidoyl chlorides are also obtained by the direct high-temperature chlorination of carbamoyl chlorides. For example, chlorination of morpholine N-carbonyl chloride (LIII) at 200°C yields the perchloro derivative LIV ( ). 

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