Propylene, with acetyl chloride

Propylene, with acetyl chloride, aluminum chloride, and quinoline to give trans-3-penten-... 

Propylene, with acetyl chloride, aluminum chloride, and quinoline to give fnms-3- wnten-2-one, 51,115 with acetyl chloride and aluminum chloride to give 4-chloropentan-2-one, 51,116... 

Preparation. Odom and Pinder1 recommend preparation of the reagent by Friedel-Crafts acylation of propylene with acetyl chloride to give 2-chloropropyl methyl ketone, which is then dehydrochlorinated to give the reagent. The pro-... 

Alenylacetylenes, 50,101 Aluminum chloride, with ethylene and p-methoxyphenylacetyl chloride to give 6-methoxy-/3-tetralone, 51,109 with propylene and acetyl chloride to give 4-chloropentan-2-one, 51,116 Amine oxides, anhydrous, 50, 55, 58 Amines, protecting group for, 50,12 AMINES FROM MIXED CARBOXYLIC-CARBONIC ANHYDRIDES 1-PHENYLCYCLOPENTYLAMINE,... 

With acetyl chloride, methylpropylcarbinol is formed and propylene evolved. In a similar way butyryl chloride gives dipropyl carbinol. ... 

Sulfonated styrene—divinylbensene cross-linked polymers have been appHed in many of the previously mentioned reactions and also in the acylation of thiophene with acetic anhydride and acetyl chloride (209). Resins of this type (Dowex 50, Amherljte IR-112, and Permutit Q) are particularly effective catalysts in the alkylation of phenols with olefins (such as propylene, isobutylene, diisobutylene), alkyl haUdes, and alcohols (210) (see Ion exchange). Superacids. 

A suspension of 37.3 g (0.1 mol) of 7/3-amino-3-methoxy-3-cephem-4-carboxylic acid hydrochloride dioxanate in 500 ml methylene chloride is stirred for 15 minutes at room temperature under an argon atmosphere and treated with 57.2 ml (0.23 mol) of bis-(trimethylsilyl)-acetamide. After 45 minutes the faintly yellow slightly turbid solution is cooled to 0°C and treated within 10 minutes with 31.2 g (0.15 mol) of D-Ct-amino-Ct-d, 4-cyclohexadienyl (acetyl chloride hydrochloride. Thirty minutes thereafter 15 ml (about 0.21 mol) of propylene oxide is added and the mixture is further stirred for 1 hour at 0°C. A cooled mixture of 20 ml of absolute methanol in 200 ml of methylene chloride is added within 30 minutes, after another 30 minutes the precipitate is filtered off under exclusion of moisture, washed with methylene chloride and dried under reduced pressure at room temperature. The obtained hygroscopic crystals of the hydrochloride of 7j3-[D-a-(1,4-cyclohexadienyl)acetylamino] -... 

Chemical modifications were also performed on copolymers of ethylene (E) or propylene (P) with acrylic (A) or methacrylic (M) acid. In a first time the gases used were sulfur tetrafluoride, acetyl chloride vapor and ammonia. The expected reaction are as follows ... 

To a 1-liter, stainless steel pressure rocker bomb cooled vrith dry ice-acetone is added 33 ml (0.41 mole) of liquid propylene followed by 33 ml (0.75 mole) of liquid sulfur dioxide. Then 4 ml of paraldehyde is added and the bomb sealed. The bottle is rocked without cooling for approximately 2-3 hr. The bomb is cooled and opened to afford a solid. The solid is ground finely in a mortar, washed with two 50-ml portions of ethyl ether and dried to give 40 gm (83%) of the white amorphous polymer, PMT approximately 250°-270°C (decomp). The polymer is insoluble in chloroform, carbon tetrachloride, dioxane, ether, ethyl acetate, benzene, acetone, and acetyl chloride. The polymer dissolves in concentrated sulfuric acid without change. 

Epichlorohydrin, 6—CihCH—CH2CI, can be obtained by the oxidation of allyl chloride with peracids, by the high-temperature chlorination of propylene with subsequent addition of chlorine/water and elimination of hydrogen chloride, or by a three-stage process starting with acrolein. Elastomers resistant to oil, ozone, and cold can be obtained from the homopolymerization of epichlorohydrin with, for example, Et3Al/H20/acetyl acetone as initiator ... 

Friedel-Crafts reaction catalysts like anhydrous aluminum chloride are readily soluble in the nitroalkanes. Solutions containing up to 50% aluminum chloride are easily prepared in nitroalkane solvents. These catalytically active complexes, AICI3-RNO2, can be isolated and used in solvents other than the nitroalkane. The reactants in the Friedel-Crafts reaction are often soluble in the nitroalkane reaction medium. Other catalysts like boron trifluoride (BF3), titanium tetrachloride (TiC ), and stannic tetrachloride (SnClj) are also soluble in the nitroalkane solvents. Reaction types which use nitroparaffins as solvents include alkylation of aromatics, acetylation of aromatics, halogenations, nitrations, and the reaction of olefins and hydrogen sulfide to yield mercaptans. Nitroparaffins are used with catalysts such as alkyl-metal (e.g., triethylaluminum, vanadium, or titanium) salts in the polymerization reactions of alkylene oxides, epichlorohydrin, propylene, butylene, vinyl chloride, and vinyl ethers. The nitroparaffin acts as an activator for the catalyst or can serve as the reaction solvent. 

Acetyl chloride cleavage is also applicable to analysis of block EO/PO copolymers, as well as products containing butylene oxide (68). Propylene oxide groups are converted mainly to 2-chloro-l-methylethyl acetate and 2-chloropropyl acetate, with traces of 1,2-propylene diacetate. Simple GC determination of the ratio of chloroethyl acetate to total chloroethyl and chloropropyl acetates provides an accurate figure for EO content of copolymers up to about 30% EO. A calibration curve must be used for higher ratios (69). 

Carbonyl Compounds. Cychc ketals and acetals (dioxolanes) are produced from reaction of propylene oxide with ketones and aldehydes, respectively. Suitable catalysts iaclude stannic chloride, quaternary ammonium salts, glycol sulphites, and molybdenum acetyl acetonate or naphthenate (89—91). Lactones come from Ph4Sbl-cataly2ed reaction with ketenes (92). 

Microwave studies of equilibrium orientations of methyl groups show that the forces act like repulsions, i.e., the hydrogens are staggered with respect to the atoms at the other end, at least in ethyl chloride, methyl silane, methyl fluorosilane, and methyl germane. Where there are only two attached atoms at one end, one connected by a single, the other by a double bond, as in acetaldehyde, propylene, acetyl fluoride and chloride, one of the methyl hydrogens is opposite the double bond, i.e., eclipsed. 

Synthesis of racemic naproxene Friedel-Crafts acylation (aluminum chloride - nitrobenzene) of p-naphthol methyl ether affords 2-acetyl-6-methoxy naphthalene, which, when treated with either dimethyl sulfonium or dimethylsulfoxonium methylide, gives 2-(6-methoxynaphthalen-2-yl)propylene oxide. Treatment of the latter with boron trifluoride etherate in tetrahydrofuran gives 2-(6-methoxynaphthalen-2-yl)propionaldehyde, which is oxidized using Jones reagent (4 M chromic acid) to yield the racemic 2-(6-methoxynaphthalen-2-yl)propionic acid. 

Hydroxypropyl) trimethylammonium chloride may be prepared by the addition of propylene chlorohydrin to trimethylamine, which on acetylation with acetic anhydride yields the official compound. 

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