2-propanol addition reaction product

Apart from these SET reactions, solvent effects in reactions of organomagnesium reagents with carbonyl compounds have been studied rather extensively. The reaction of ethylmagnesium bromide with benzophenone (Scheme 15) in diethyl ether yields 94% of the expected addition reaction product, 1,1-diphenyl-1-propanol, and 6% benzhydrol, resulting from a reduction reaction of the Grignard reagent [36]. In tetrahydrofuran this reaction yields 21 and 77%. respectively, of both products. 

Condensation of vinyl chloride with formaldehyde and HCl (Prins reaction) yields 3,3-dichloro-l-propanol [83682-72-8] and 2,3-dichloro-l-propanol [616-23-9]. The 1,1-addition of chloroform [67-66-3] as well as the addition of other polyhalogen compounds to vinyl chloride are cataly2ed by transition-metal complexes (58). In the presence of iron pentacarbonyl [13463-40-6] both bromoform [75-25-2] CHBr, and iodoform [75-47-8] CHl, add to vinyl chloride (59,60). Other useful products of vinyl chloride addition reactions include 2,2-di luoro-4-chloro-l,3-dioxolane [162970-83-4] (61), 2-chloro-l-propanol [78-89-7] (62), 2-chloropropionaldehyde [683-50-1] (63), 4-nitrophenyl-p,p-dichloroethyl ketone [31689-13-1] (64), and p,p-dichloroethyl phenyl sulfone [3123-10-2] (65). 

The enzyme activity was assayed by measuring the production of optically active mandelonitrile synthesized from benzaldehyde and cyanide. The standard assay solution contained 300 gmo citrate buffer (pH 3.5-6.0), 50 /rmol of benzaldehyde, 100 /rmol potassium cyanide and 100 jA of the enzyme in a final volume of 1.0 mL. The reaction was started by an addition of 100 fx of the enzyme solution and incubated at 25 °C for 1-120 min. Aliquots (100 jiY) were withdrawn at various reaction times and the reaction was stopped by the addition of 0.9 mL of organic solvent (9 1 hexane iso-propanol by volume). The mandelonitrile formed was extracted and the supernatant, obtained by centrifugation (15,000 x g, 1.0 min at 4 °C), was assayed by HPLC. A blank reaction was also performed without enzyme and the amount of mandelonitrile obtained was deducted from the biocatalyzed reaction product. One unit of the enzyme is defined as the amount of the enzyme that produces 1 /imol of (R)-mandelonitrile under reaction conditions in 1 min. 

The addition of chiral amines to a,/(-unsaturated sulfoximines has been employed for the resolution of racemic sulfoximines 3 utilizing 0.5 equivalents of a chiral amine in chloroform 117. After completion of the reaction, the unreacted starting material is isolated by column chromatography and its optical purity determined by comparison with the reported optical rotation, or by HNMR using a chiral shift reagent. While (—)-(l/f,2.S,)-2-mcthylamino-1-phenyl-l-propanol [(l/ ,2S)-ephedrine] affords material of moderate optical purity, racemic products are isolated from addition reactions with (—)-l-phenyl-2-propanamine [(—)-am-phetamine] or ( + )-( )-l-phenylethylamine. 

Strecker-type addition of cyanide to imines has been reported to be catalyzed by chiral Ti Schiff base-tripeptide complexes (Sch. 65) [161]. The reaction is efficient (> 93 % conversion) and proceeds with excellent enantioselectivity (85-97 % ee) in the presence of 1.5 equiv. 2-propanol. Hoveyda and Snapper pointed out that catalyst turnover is significantly facilitated by the presence of 2-propanol. Optically pure products are usually isolated in > 80 % yields. 

The conversion of 1-propanol over H-ZSM-5 or H-Y was not found to yield any C3 oxygenated products for a range of reaction conditions and the products are mainly propene and butenes. This confirms that the introduction of the carbon-carbon double bond into the reactant molecule significantly affects the reactivity. Conversion of 2-propanol over H-ZSM-5 was found to give significant selectivity to acetone at low flow rates and this indicates that this could be a possible reaction intermediate. In addition, reaction of propene oxide over H-ZSM-5, under comparable conditions to those utilised for allyl alcohol, produced significant selectivities of both acetone and allyl alcohol. 

Firstly, we have the acetone aldol self-condensation reaction over basic sites to give diacetone alcohol (DAA). Dehydration of this alcohol yeilds mesityl oxide (MSO) winch, in turn, can be selectively hydrogenated over reduced metal sites to finally give methyl isobutyl ketone (MIBK). In addition to the aldol condensation route, the acetone carbonyl functional group can also be directly hydrogenated over reduced metal sites yielding 2-propanol. Other reaction by-products such as methane, propane, diisopropyl ether and diisobutyl ketone have been detected in some experiments, but in very low amounts, lower than 2% of the total reaction products. 

If after the addition of IM formaldehyde to IM l-amino-2-methy 1-propanol from the resulting 2-(N-hydro-xymethyl)-2-methyl-propanol 1 M H2O is eliminated, the condensation reaction leads to 100% 4,4-dimethyl-1,3-oxazohdine which, compared with other amine-formaldehyde-reaction-products, where water is not completely ehminated and an equilibrium exists between the N-hydroxymethyl compound and the condensation product, has solubility properties favouring its incorporation in to oil concentrates (e.g. lubricoolants) and its application in fuels to inhibit microbial growth in fuel oil bottom water. 

The importance of the dipolar resonance forms is reflected in the stabihties of isomeric carbonyl compounds. Propanal is approximately 27 kj mole" less stable than propanone. For addition reactions, two isomeric products with different stabihties also form. Therefore, we also have to consider the relative stabihties of the products. Hydrogenation of propanal and propanone gives isomeric alcohols. 1-Propanol is approximately 16 kJ mole" less stable than 2-propanol. Since the difference in the stabihties of the reactants is greater than the difference in the stabilities of the products, the equihbrium constants for the addition reactions of carbonyl compounds depend on more differences in the structure of the carbonyl compound than on the differences in the structure of the addition product. Thus, because ketones are more stable than aldehydes, the addition reactions of ketones are less favorable (have smaller equihbrium constants) than addition reactions of aldehydes. 

First, the countercation of 4.5 and the other anionic species is the hydronium ion, i.e., protonated water. If a ligand such as PPhj is added, it gets converted to HPPhj which acts as the countercation. Second, 4.5 to 4.6 is an oxidative addition reaction, 4.6 to 4.7 is an insertion reaction, and 4.8 to 4.5 is a reductive elimination reaction. Third, although the main product-forming reaction is the reductive elimination step, hydrolysis of 4.8 to 4.9 also gives acetic acid. The complex 4.9 plays an important role in the carbonylation of propanol and other higher alcohols (see Section 4.3). 

Now let s draw the forward scheme. Upon treatment with PCC, 1-propanol is oxidized to give propanal. Treating propanal with sodium hydroxide then gives a P-hydroxyaldehyde (via an aldol addition reaction between two molecules of propanal). Reduction with LAH, followed by water work-up, gives the product. 

Suitable catalysts include the hydroxides of sodium (119), potassium (76,120), calcium (121—125), and barium (126—130). Many of these catalysts are susceptible to alkali dissolution by both acetone and DAA and yield a cmde product that contains acetone, DAA, and traces of catalyst. To stabilize DAA the solution is first neutralized with phosphoric acid (131) or dibasic acid (132). Recycled acetone can then be stripped overhead under vacuum conditions, and DAA further purified by vacuum topping and tailing. Commercial catalysts generally have a life of about one year and can be reactivated by washing with hot water and acetone (133). It is reported (134) that the addition of 0.2—2 wt % methanol, ethanol, or 2-propanol to a calcium hydroxide catalyst helps prevent catalyst aging. Research has reported the use of more mechanically stable anion-exchange resins as catalysts (135—137). The addition of trace methanol to the acetone feed is beneficial for the reaction over anion-exchange resins (138). 

Hydrogen hahdes normally add to form 1,2-dihaLides, though an abnormal addition of hydrogen bromide is known, leading to 3-bromo-l-chloropropane [109-70-6], the reaction is beUeved to proceed by a free-radical mechanism. Water can be added by treatment with sulfuric acid at ambient or lower temperatures, followed by dilution with water. The product is l-chloro-2-propanol [127-00-4]. 

One of the drawbacks of the Skraup/Doebner-von Miller reaction is the isolation of the desired product from the starting aniline and co-formed alkyl anilines and 1,2,3,4-tetrahydroquinaldine. Isolation can be simplified greatly by addition of one equivalent of zinc chloride at the end of the reaction all of the basic products were precipitated. Washing the brown solids with 2-propanol removed all impurities and left the desired quinoline as a 2 1 complex with zinc chloride in yields of 42-55%. 

To a suspension of 3.0 g of 7-[D-(-)-a-amino-p-hydroxyphenylacetamido] -3-[5-(1-methyl-1,2,3,4-tetrazolyl)thiomethyl] -A3arboxylic acid in 29 ml of water was added 0.95 g of anhydrous potassium carbonate. After the solution was formed, 15 ml of ethyl acetate was added to the solution, and 1.35 g of 4-ethyl-2,3-dioxo-1 -piperazinocarbonyl chloride was added to the resulting solution at 0°C to 5°C over a period of 15 minutes, and then the mixture was reacted at 0°C to 5°C for 30 minutes. After the reaction, an aqueous layer was separated off, 40 ml of ethyl acetate and 10 ml of acetone were added to the aqueous layer, and then the resulting solution was adjusted to a pH of 2.0 by addition of dilute hydrochloric acid. Thereafter, an organic layer was separated off, the organic layer was washed two times with 10 ml of water, dried over anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The residue was dissolved in 10 mi of acetone, and 60 ml of 2-propanol was added to the solution to deposit crystals. The deposited crystals were collected by filtration, washed with 2-propanol, and then dried to obtain 3.27 g of 7-[D-(-)-a-(4-ethyl-2,3-dioxo)-1 -piperazinocarbonylamino)-p-hydroxyphenylacetamido] -3-[5-(1 -methyl-1,2,3,4-tetrazolyl)thiomethyl]-A product forms crystals, MP 1BB°C to 190°C (with decomposition). 

To a solution of 4 g of sodium in 200 ml of n-propanol is added 39 g of homovanillic acid-n-propyl ester (boiling point 160°C to 162°C/4 mm Hg) and the mixture is concentrated by evaporation under vacuum. After dissolving the residue in 200 ml of dimethylformamide and the addition of 0.5 gof sodium iodide, 26.2 g of chloracetic acid-N,N-diethylamide are added drop-wise with stirring at an internal temperature of 130°C, and the mixture is further heated at 130°C for three hours. From the cooled reaction mixture the precipitated salts are removed by filtering off with suction. After driving off the dimethylformamide under vacuum, the product is fractionated under vacuum, and 44.3 g of 3-methoxy-4-N,N-diethylcarbamido-methoxy phenyl acetic acid-n-propyl ester are obtained as a yellowish oil of boiling point 210°C to 212°C/0,7 mm Hg,... 

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