Morpholine, At-

Amines normally have no effect on the isothiazole ring, but 3-chloro-4-nitroisothiazole (49) reacts with cyclic amines such as morpholine at 0 °C to give the enamine (50) (75JOC955). The mechanism may involve attack either at sulfur or at the 5-position (Scheme 6). 

The thermolysis of 4-azidophenyl methyl ketone in morpholine at 170°C yields a mixture of the expected 5-acetyl-2-morpholino-3f/-azepine (33) and 6-acetyl-2-morpholino-3//-azepine (34), the product of a unique and totally unexpected thermal rearrangement of the 5-acetyl derivative.119 Similar results can be obtained in hot piperidine, whereas thermolysis of 4-azido-diphenyl ketone under similar conditions yields only the 6-benzoyl-2-(cycloalkylamino)-3//-azepines (7-18%) accompanied by much tar. 

Dithiocarbamate complexes of copper have been sythesized at a high rate. Reports of new complexes include the morpholine-4- (44), thio-morpholine, AT-methylpiperazine-4-, and piperidine- (291) dithiocarba-mates. Novel, polymeric complexes of the type Cu(pipdtc)2 (CuBr) in = 4, or 6) and Cu(pipdtc)2 (CuCl)4 have been prepared by reactions of[Cu(pipdtc)2] with the respective copper halide in CHCla-EtOH (418). The crystal structures of the polymers are known to consist of sheets of individual [Cu(pipdtc)2] molecules linked to polymeric CuBr chains via Cu-S bonds. A series of copper(I) dtc complexes have been the subject of a Cu and Cu NQR-spectral study (440). 

Formex A process for extracting aromatic hydrocarbons from petroleum reformate, using N-formyl morpholine at 40°C. Developed by SNAM-Progetti. 

A regiospecific solid-phase synthesis of 3-methylthiazolo[3,2-c][l,2,3]triazole 105 has been achieved using poly-styrene-sulfonyl hyrazide resin (PS-Ts-NHNH2) 287. The reaction of resin 287 with l-thiazol-2-yl-ethanone in 5% TiCU/MeOH provides hydrazone 288 and subsequent treatment of this latter compound with morpholine at 95 °C gave fused triazole 105 in 60% yield (Scheme 29) <2004TL6129>. 

IV-Methylmethanesulfonamide, 23 685 IV-Methyl morpholine-AT-oxide (NMMO) as cellulose solvent, 11 266, 267, 268 environmental issues related to,... 

The reaction of 3-benzisothiazolylaminomethylenemalonate (1561) with morpholine at 100°C for 1 hr gave 3-(4-morpholinyl)-l,2-benzisothiazole-1,1-dioxide (1562) (701JC499). 

In particular, when pentachloronitrobenzene (16) is heated at 50 °C for 20 h with 6.0 molar equivalent of morpholine at 0.60 GPa in tetrahydrofuran (THF) solution in the presence of 5.0 molar equivalent of triethylamine, several products were isolated and are shown in Scheme 9. 

The borane adducts of phosphines having hydrogen, methyl or methylene groups adjacent to the phosphoms can be easily deprotonated by strong bases and the resulting anions react with various nucleophiles affording borane-protected tertiaiy phosphines as air stable, crystalline materials [23], Quantitative deprotection of the phosphoms can be achieved by treatment with morpholine at 110 °C followed by evaporation to dryness. Dissolution of the solid residue and addition of THF results in precipitation of the products such as -among others-19. 

In a subsequent paper (87), the same authors investigated the palladium-catalyzed allylic aminations with pyrphos-functionlized PPI and PAMAM dendrimers as multidentate ligands. Zero to four generation PPI-(pyrphosPdCl2)x and PAMAM-(pyrphosPdCl2)x neutral dendrimers (97) showed a strong positive dendritic effect on the selectivity of the allylic amination of 1,3-diphenyl-1-acetoxypropene with morpholine (at 45°C in DMSO). 

Nitrile 241 was reduced to the amine 242 with Red-Al in morpholine at —40 °C. However aluminium hydrides are mostly unsuitable if there is an A-acetyl group that is required to be conserved and this is discussed further in Section 8.06.8. Also, 240 could be prepared from the ester 243 by reaction with ammonia <1982AP538>. 

Treatment of 1 with morpholine at room temperature results in an exothermic reaction and the reaction mixture turns dark red in colour. Addition of water results in the separation of 2 as yellowish-green needles in 54% yield. 

Treatment of CH2C12 solutions of 2,5-dihydro-l,2,3-selenadiazoles 218 with 1 equiv of morpholine at room temperature led to ethyl l,2,3-selenadiazole-4-carboxylates 219 in 90-98% yield (Equation 22) <2000HCA539>. 

Subtle reactivity differences are also found in the reaction of 6-bromo[l,2,5]thia- (or selena) diazolo[3,4-/)]pyridines (92) with morpholine and cuprous cyanide which afford the C(7)-amine (94) and C(6)-nitrile (95), respectively (Scheme 15). Under identical reaction conditions, 6-bromo-benzo[l,2,5]thiadiazole affords exclusive C(6)-amination and C(6)-cyanation. The anomalous regio-chemistry in the formation of (94) is attributed to initial formation of a hetaryne intermediate (93), which adds morpholine at the more electron-deficient C-7 position <79IJC(B)13,86IJC(B)500>. 

Asymmetric hydroamination using a chiral PIGIPHOS-Ni(II) complex has also been achieved in ionic liquids, as shown in Scheme 9.38.11431 A number of different imidazolium and picolinium ionic liquids were tested and relative to THF, much higher turnover numbers (300 vs. 20) were observed in the reaction between methacrylonitrile and morpholine at comparable selectivity (64% ee vs. 69%). Moreover, the catalyst in the ionic liquid solution is less sensitive to air and moisture so that non-distilled reagents can be used. 

Concurrently with this contribution from Buchwald and co-workers, the Hartwig group reported that the P(t-Bu)3P/Pd-catalyst system first reported by Koie and co-workers [36] is sufficiently active to couple aryl bromides with secondary amines at room temperature [50]. For example, 2-bromotoluene is efficiently aminated with morpholine at in 96% yield, Eq. (19). This catalyst is capable of the room temperature coupling of acyclic secondary amines and aryl bromides as well as the coupling of aryl chlorides at elevated temperatures. 

The fluorene linker 1.14 (71), which is easily attached to an aminomethyl PS resin, has been used to support C-terminal Boc-proteeted amino acids during oligopeptide synthesis. The cleavage of this linker requires the use of 20% piperidine, or better 20% morpholine at rt over 2 h. 

Normal nucleophilic substitution occurred on treatment of 2-carbamoyl-3-chloropyrazine with alcoholic methylamine at 130° (423, 836) 2-chloro-3-(4 -morpholinocarbonyOpyrazine with morpholine at reflux in benzene (867) 2dimethyl sulfoxide at 65° (857) and cyclohexylamine in benzene at reflux (946) 3-chloro-2-methoxycarbonyl-5-phenylpyrazine with alcoholic methylamine at 140° (375) 2-carboxy-3-chloropyrazine with anhydrous ammonia at 100° for 5 hours (947) 2-carbamoyl-6-chloropyrazine with aqueous methylamine at reflux (940) 2-chloro-6-(4 -morpholinocarbonyl)pyrazine (and other amides) and 2-chloro-6-methoxycarbonylpyrazine with morpholine (and other amines) (870, 948, 949) and 2-chloro-6-methoxycarbonylpyrazine with liquid ammonia at 80° (870). 2-Chloro-3-methoxycarbonylpyrazine fused with guanidine carbonate gave 2-amino4-hydroxypteridine and its 7-methyl-, 7-phenyl, and 6,7-diphenyl analogues were prepared similarly (371,375). 

OrBenzeneselenenylation. The introduction of a conjugated double bond to a carbonyl compound can take advantage of the facile selenenylation by the Se-substituted morpholine at room temperature. Subsequent oxidation and in situ elimination completes the process which is readily adaptable to a-ketoesters. 

The l,3-dithiolylium-4-olate (58) reacted with morpholine at the 4-position with formation of the thiobenzomorpholide (59) and the thiophenylacetomorpholide (60) (Scheme 12) the disulfide (61) is obtained from (60) by oxidation <78CB3178>. 

Reaction of Polyimides with Morpholine. For exploratory work, test tube solutions of the polymers in N-methylpyrrolidinone (10% by weight) were prepared. Morpholine at twice the polymer weight was added. After thorough mixing, the solutions were allowed to stand at room temperature for a day. The modified polymers were collected by precipitation in water, filtration, washing with more water, and drying in vacuo over phosphorous pentoxide for ten days. IR spectra were then recorded of KBr pellets containing the modified polymers. In... 

With 2-nitropropene as the acceptor, the enamine derived from cyclohexanone and morpholine at 0°C in ether gives heterocycle 4.1. If 4.1 is warmed to 25-30°C or if the reaction is carried out in acetonitrile (< 0°C) a mixture of the regioisomeric enamines 4.2 and 4.3 is formed. Addition of the same enamine to 1-nitropropene in petroleum ether at 0°C gives the product with the less substituted enamine (4.4, Eq. [2]). 

Acrylonitrile and the anion of 58 (formed by KOH-MeOH) give the bis-cyanoethyl adduct 117.74- The cyclic amide bond in compound 58 was slowly cleaved by amines morpholine at elevated temperatures affords the sulfonamide-carboxamide 118.46 Pyrrolidine reacts similarly.40... 

The reality of the excitation exchange between 5 and fi is demonstrated by the fact that a polymerization can be initiated under laser irradiation at 440 nm (a wavelen h which is only absorbed by S in the presence of S fi but not in presence of S atone. The relative quantum yield of polymerization obtained is similar to that of the system S+morpholine (at =363 nm under CW At laser) but considerably less than that of at the same irradiation wavelength [26]. This observation is in good agreement with the assumption of an electron transfer process predominating in non-polar media. 

Substance g. Solute in 100 g. Morpholine at 25 C Substance g. Solute in Morpholine... 

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