Isopropyl acetate bromide

The industrial production of Crixivan (9 H2S04) took advantage of the chirality of (IS,2R)-aminoindanol to set the two central chiral centers of 9 by an efficient diastereoselective alkylation-epoxidation sequence.17 The lithium enolate of 12 reacted with allyl bromide to give 13 in 94% yield and 96 4 diastereoselective ratio. Treatment of a mixture of olefin 13 and V-chlorosuccinimide in isopropyl acetate-aqueous sodium carbonate with an aqueous solution of sodium iodide led to the desired iodohydrin in 92% yield and 97 3 diastereoselectivity. The resulting compound was converted to the epoxide 14 in quantitative yield. Epoxide opening with piperazine 15 in refluxing methanol followed by Boc-removal gave 16 in 94% yield. Finally, treatment of piperazine derivative 16 with 3-picolyl chloride in sulfuric acid afforded Indinavir sulfate in 75% yield from epoxide 14 and 56% yield for the overall process (Scheme 24.1).17-22... 

Chloro-(/7-cyanophenyl)phenylphosphine 349 Dichloro(phenyl)phosphine (60 g) is added to a slurry of i -cyanobenzenediazonium tetrafluoroborate (72 g) and copper(i) bromide (2.4 g) in dry isopropyl acetate (300 ml). After about 20 min a violent reaction sets in which is moderated by external cooling so that the temperature remains between 20° and 40°. When gas evolution ceases, aluminum turnings (8 g) are added and the mixture is stirred for 2 h at 40-50°. Then the liquid is decanted from unused aluminum, and phosphorus oxychloride (51 g) is added to decompose the aluminum chloride complex. Distillation then affords a forerun (5 g), followed by the main fraction (39 g, 47%) between 15870.7 mm and 195°/ 3.1 mm (owing to unavoidable decomposition the pressure does not remain constant during the distillation). Further distillation gives a product boiling at 16270.2 mm. 

Cyclopropyl thien-2-yl ketone (34), available commercially, was subjected to a Grignard reaction with 21 to yield a carbinol (31) in excellent yield. Bromotrimeth-ylsilane-mediated opening of the cyclopropyl ring led to the 4-bromo derivative 32. Condensation with ethyl i -(-)-pipeildme-3-carboxylate (16) was conducted in isopropyl acetate as a solvent with anhydrous lithium carbonate as the base. The transformation was cleaner and did not provide any of the diene (26) arising from elimination of hydrogen bromide. The alkylation of the nipecotate residue could also be directly effected with a mixture of the tartrate salt of 16, lithium carbonate, and isopropyl acetate. Compound 33 was readily isolated as the hydrochloride isopropyl acetate was superior to all other solvents used in this reaction. Since it is not itself prone to hydrolysis, it is preferable to ethyl acetate. Moreover, it appears to crystallize hydrochlorides much better. 

Isopropyl Acetate 108-21-4 Magnesium Nitrate 10377-60-3 Methyl Bromide 74-83-9... 

Amyl acetate, chlorobenz e, chloroform, cyclohexyl acetate, dichlorobenzene,, 2-dimethoxy-ethane, ethyl bromide, ethyl acetate, r>-fluorotoluene, hydrocarbons, hydrogenated lene. isopropyl acetate, MEK (above 20°C), octylamine, phenetol (above 13 C), trichloroethylene... 

To a well stirred suspension of 9 g of sodium phenyl acetate and 2.4 g of magnesium turnings in 25 cc of anhydrous ether, a solution of 9.4 cc of isopropyl bromide in 50 cc of anhydrous ether are added. The mixture is refluxed for one hour (during which time propane is evolved) and then 5 cc of cyclopentanone in 25 cc of anhydrous ether are added dropwise. The mixture is then refluxed for one hour and poured over ice water containing some hydrochloric acid. The ether solution is separated and extracted with 200 cc of 5% sodium hydroxide. The alkaline solution on acidification gives the free acid which is filtered off, dried in a desiccator and recrystallized from a mixture of ethylene dichloride and petroleum ether. 

Indenopyrene, see Indeno[l,2,3-crf pyrene l//-Indole, see Indole Indolene, see Indoline Inexit, see Lindane Inhibisol, see 1,1,1-Trichloroethane Insecticide 497, see Dieldrin Insecticide 4049, see Malathion Insectophene, see a-Endosulfan, p-Endosulfan Intox 8, see Chlordane Inverton 245, see 2,4,5-T lodomethane, see Methyl iodide IP, see Indeno[l,2,3-crf pyrene IP3, see Isoamyl alcohol Ipaner, see 2,4-D IPE, see Isopropyl ether IPH, see Phenol Ipersan, see Trifluralin Iphanon, see Camphor Isceon 11, see Trichlorofluoromethane Isceon 122, see Dichlorodifluoromethane Iscobrome, see Methyl bromide Iscobrome D, see Ethylene dibromide Isoacetophorone, see Isophorone a-Isoamylene, see 3-Methyl-l-butene Isoamyl ethanoate, see Isoamyl acetate Isoamylhydride, see 2-Methylbutane Isoamylol, see Isoamyl alcohol Isobac, see 2,4-Dichlorophenol Isobenzofuran-l,3-dione, see Phthalic anhydride 1,3-Isobenzofurandione, see Phthalic anhydride IsoBuAc, see Isobutyl acetate IsoBuBz, see Isobutylbenzene Isobutane, see 2-Methylpropane Isobutanol, see Isobutyl alcohol Isobutene, see 2-Methylpropene Isobutenyl methyl ketone, see Mesityl oxide Isobutyl carbinol, see Isoamyl alcohol Isobutylene, see 2-Methylpropene Isobutylethylene, see 4-Methyl-l-pentene Isobutyl ketone, see Diisobutyl ketone Isobutyl methyl ketone, see 4-Methyl-2-pentanone Isobutyltrimethylmethane, see 2,2,4-Trimethylpentane Isocumene, see Propylbenzene Isocyanatomethane, see Methyl isocyanate Isocyanic acid, methyl ester, see Methyl isocyanate Isocyanic acid, methylphenylene ester, see 2,4-Toluene-diisocyanate... 

Nitric acid, N-Methyl gluconamide. Acetic anhydride. Sodium bicarbonate. Methanol Dimethylurea, Nitric acid, Sulfuric acid. Methylene chloride, Sodium carbonate Anhydrous hydrazine, Cyanogen bromide, Isopropyl alcohol, Sodium nitrite, Sodium bicarbonate, Copper nitrate trihydrate, Nitric acid, Diethyl ether, Dimethyl sulfate... 

For the preparation of MIPM, the above phenol, 2,5-dimethoxyphenol was isopropylated with isopropyl bromide in methanolic KOH giving 2,5-dimethoxy-l-(i)-propoxybenzene as an oil. This formed the benzaldehyde with the standard Vilsmeier conditions, which melted at 77-78 °C from hexane and which gave a yellow malononitrile derivative melting at 171.5-173 °C. The nitrostyrene, from nitroethane in acetic acid was orange colored and melted at 100-101 °C from either methanol or hexane. This was reduced with lithium aluminum hydride in ether to give 2,5-dimethoxy-4-(i)-propoxyamphetamine hydrochloride (MIPM). The properties of the isolated salt were strange (soluble in acetone but not in water) and the microanalysis was low in the carbon value. The molecular structure had a pleasant appeal to it, with a complete reflection symmetry shown by the atoms of the amphetamine side chain and the isopropoxy side chain. But the nature of the actual product in hand had no appeal at all, and no assay was ever started. 

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