5-Methoxycarbonyl-7-phenyl-2,3-dihydro

Dihydro-4,5-dimethyl-3-(hydroperoxy)-2-[4-(methoxycarbonyl)phenyl]isothiazole 1,1-dioxide (AFUPOG) 1.461 1.417 106.6 97... 

Hydroxy-2-oxo-3-phenyl-2,5-dihydro- VI/2, 688 4-Hydroxy-5-oxo-4-phenyl-4,5-dihydro- X/4, 839 Keten Methoxycarbonyl-phenyl-VII/4, 81, 90... 

I -Hydroxy-ethyl) -3-( 2-methoxycarbonyl-phenyl) -5,6-dihydro-1,4,2-dioxazin 100%... 

H-Azepine, 2,6,7-tri(methoxycarbonyl)-ring inversion, 7, 499 Azepine-1-carboxylic acid tricarbonylruthenium complexes, 7, 523 1 H-Azepine-2,3-dicarboxylic acid, 4,7-dihydro-6-phenyl-diethyl ester synthesis, 7, 539-540 1 H-Azepine-3,6-dicarboxylic acid... 

Only one procedure has been reported recently within this category. Thus 7-chloro-l-methyl-5-phenyl-2,3-dihydro-lH-benzodiazepin-2-one 4-oxide (437) with dimethyl acetylenedicarboxylate in methylene chloride at 20° C for 3 days gave a separable mixmre of the primary tricyclic adduct, dimethyl lO-chloro-6-oxo-llb-phenyl-5,6,7, 1 lb-tetrahydroisoxazolo[2,3-t/] [ l,4]benzodiazepine-1,2-dicarboxylate (438), and its rearrangement product, 6-chloro-4-(2-methoxalyl-2-methoxycarbonyl-l-phenylvinyl)-l-methyl-3,4-dihydro-2(lT0-quinoxalinone (439) each product afforded 6-chloro-l-methyl-2(l//)-quinoxalinone (440) on refluxing in ethanol (see also Section 1.7.13). However, the final quinoxaline (440) was best obtained in 75% yield) by simply heating the initial substrate (437) and dimethyl... 

Amino-7-methoxy-2-methoxycarbonyl-3-phenyl-5,8-quinoxalinequinone 6-Amino-7-methoxy-l-methyl-2-oxo-3-phenyl-1,2-dihydro-5,8-quinoxalinequinone 3-Amino-6-methoxy-8-nitro-2-quinoxalinecarbo-nitrile 1,4-dioxide... 

Heterocycles Both non-aromatic unsaturated heterocycles and heteroaromatic compounds are able to play the role of ethene dipolarophiles in reactions with nitrile oxides. 1,3-Dipolar cycloadditions of various unsaturated oxygen heterocycles are well documented. Thus, 2-furonitrile oxide and its 5-substituted derivatives give isoxazoline adducts, for example, 90, with 2,3- and 2,5-dihydro-furan, 2,3-dihydropyran, l,3-dioxep-5-ene, its 2-methyl- and 2-phenyl-substituted derivatives, 5,6-bis(methoxycarbonyl)-7-oxabicyclo[2.2.1]hept-2-ene, and 1,4-epoxy-l,4-dihydronaphthalene. Regio- and endo-exo stereoselectivities have also been determined (259). 

Diese Reaktionsart ist bei den Addukten aus Butadien-carbonsaure-Derivaten mit der Carboxylgmppe in 3-Stellung allein verwirklicht dabei entstehen 3-Amino-a-pyrone [58, 70, 72). So geht das N-p-Chlorphenyl-3-methoxycarbonyl-6-phenyl-3.6-dihydro-1.2-oxazin bei der Chromato-graphie an Aluminiumoxid in 3-p-Chloranilino-6-phenyl-a-pyron uber (55), der Mechanismus ist analog dem der Pyrrolbildung. 

N-CH3 2 c6h5 3-Methoxycarbonyl-7-methyl-3-phenyl-5H-6,7-dihydro-imidazolo [7,2-c] imidazol) 60 117... 

Umsetzung mit 1-(4-Methoxy-pheny])-propen zu 3-Methoxycarbonyl-5-(4-methoxy-phenyl)-4-me-thyl-4,5-dihydro-l, 2-oxazol. 

In Gegenwart von sek. Aminen (z. B. + -tp-Ephedrinen) reagiert 3-Methoxycarbonyl-1-oxo-1,3-dihydro-2-benzofuran mit 2-Nitro-1-phenyl-ethen zu l-Methoxycarbonyl-l-(2-ni-tro-l-phenyl-ethyl)-3-oxo-l, 3-dihydro-2-benzofuran ( 100%) ... 

B) Preparation of 7-Chloro-3-Methoxycarbonyl-5-Phenyl-2-Oxo-2,3-Dihydro-lH-Benzo[f]-l,4-Diazepine (4347 CB) A solution of 9.2 g (0.04 mol) of compound 4356 CB in 20 ml of methanol is added dropwise, in the course of one hour and 30 minutes, to a boiling solution of 9.2 g (0.05 mol) of the hydrochloride of methyl aminomalonate in 30 ml of methanol. When this is completed, heating under reflux is continued for 30 minutes and the product then concentrated to dryness under reduced pressure. The residue is taken up in water and ether, the ethereal layer separated, the product washed with water and dried over sodium sulfate. The solvent is evaporated under reduced pressure. The residue, which consists of the methyl ester, could not be obtained in the crystalline state. It is dissolved in 25 ml of acetic acid, heated under reflux for 15 minutes, the product evaporated to dryness and the residual oil taken up in ether. A colorless solid separates which is filtered by suction and recrystallized from methanol. Colorless crystals are obtained (4.7 9) MPk (Kofler block) 226°C. A second crop (1.5 g) is obtained on concentration of the mother liquor MPk (Kofler block) 222°C total quantity 6.2 g, corresponding to a yield of 47%. 

Methoxycarbonyl-methyl)-5-phenyl-5,6-dihydro- dibenzo b,d]phosphoririy-5-oxid (R = C6H5) 33% 5-Benzyl-6-(methoxycarbonyl-methyl)-5,6-dihydro-(dibenzo[b,d]phosphorin -5-oxid (R — CH2-C6H5) 16% ... 

S)-Methyl 7-chloro-2,5-dihydro-2- [methoxycarbonyl)(4-(trifluoromethoxy)Phenyl]amino)Carbonyl Indenol[l,2-e][l,3 4]Oxadiazine-4a(3/y)-carboxylate... 

Ethan 2-Acetamino-2-hydroxy-l-oxo-1-phenyl- E14a/2, 68 (R-CHO/R-CO-NH2), 215 (R-CHO/Amin) Furo 2,3-b[pyridin 3-Acetoxy-3-methyl-2,3-dihydro- E6b/1, 117 (OH -+ O-CO-CH3) Hydroxylamln N-[4-(rra s-2-Methoxycarbonyl-ethenyl)-phenyl]- E16a, 58 (Nitro-Red.) Malonsanre Methyl- -anilid E5. 

Methoxycarbonyl-ethy l)-3-phenyl- E16c, 691 (aus Pyrazolidin-N-ylid) lH-l,4-Benzodiazepin 2,3-Dimeth-oxy-2,3-dihydro- E9d, 399 (3-Nj —quinolin/NaOR)... 

H-Pyrrol 3 -Methoxycarbonyl-5-phenyl-3,4-dihydro- E14b, 22 (Azirin 4- En)... 

Carboxy-l -et hoxymethyl-2-phenyl-thio- E8c, 152 (H -> Li -> COOH) l-Methoxycarbonyl-2-(2-oxo-2-phenyl-ethylthio)-4,5-dihydro-E4, 1095 (NH N-COOR)... 

When the adduct 1 (R = CH3), obtained from nitrosobenzene and 1,2-dihydro-V-methoxycar-bonylpyridine, is added to a chloroform solution of 2,3-dimethylbutadiene at 20 °C, over a period of 5 days the adduct 1 (R = CH3) undergoes a slow retro-Diels-Alder reaction in solution to give 3,6-dihydro-4,5-dimethyl-2-phenyl-2//-l,2-oxazine even at 20°C. This accounts for the instability of the methoxycarbonyl adduct. In contrast, the benzyloxycarbonyl adduct 1 (R = Bn) is much more stable. 

Bis-[4-methoxy-phenyl]-2-cyclopropenyliden)-9-(dicyano-methylen)-9,10-dihydro- 2975 2(or 3)-Chloromethyl- 2879 lO-Deuterio-9-methoxycarbonyl- 2880 1 -Hy droxy-7-methoxy-1 -(1 -phenylthio-cy clo-propyl)-l,2,3,4-tetrahydro- 1480 9-Melhoxycarbonyl- 2888 7-Methoxy-l-(l-phenylthio-cyclopropyl)-3,4-dihydro- 1480 9-Methyl- 2048... 

Benzyliden-5-oxo-4,5-dihydro- 708 l-Benzyl-3(bzw. 5)-iodmethyl- 577 l-Benzyl-3-methoxycarbonyl- 533 l-(Benzyloxy-methyl)-3-phthalimido- 603 l-Benzyl-3-phenyl- 533, 541 3(5)-Benzyl-5(3)-phenyl- 477... 

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