2- alcohols reactions with

A reaction of N02 similar to reaction (14) occurs with alcohols. The reaction with methanol, for example, produces methyl nitrite  

The homogeneous gas-phase reaction is slow, depending on the square of the N02 concentration and with a third-order rate constant at room temperature of ku, = (5.7 0.6) X 10 17 cm6 molecule-2 s-1 (Niki et al., 1982 Koda et al., 1985). 

This particular reaction may be important when sampling exhaust from methanol-fueled combustion sources. For example, significant concentrations (46-69 ppm) of methyl nitrite have been reported in the exhaust of a methanol-fueled bus (Hanst and Stephens, 1989). Such large concentrations would be of concern if 

However, if one applies the heterogeneous kinetics reported by Takagi et al. (1986), one can calculate that methyl nitrite concentrations of the order measured in the exhaust sample could arise by reactions of unburned methanol and N02 on the walls of the sampling bag prior to analysis (Finlayson-Pitts et al., 1992). 

In short, while such heterogeneous reactions are not at all well understood, they may play very important roles in laboratory apparatus, in sampling systems, and perhaps in ambient air, where a variety of surfaces are available. 

2-Fluoro-2-trifluoromethylthiazolo[3,2-a]benzimidazol-3(2//)-one (508 A = benzimidazole nucleus, R = F, R = CF3), on heating in alcohol even for a short period, undergoes alcoholysis to give ester 512. The electron-withdrawing nature of the fluorine and trifluoromethyl groups at 

Similar to water, alcohols can also attack phosphorous acid triesters. The reaction can be used for the synthesis of phosphite hgands by transesterification (see above), but they may also play a role in degradation processes, where alcohols produced from the reduction of product aldehydes interfere with the phosphite ligand. 

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Most aromatic acid chlorides impart a strongly acid reaction when shaken with water (compare Section 111,88). All are completely hydrolysed by boiling with solutions of caustic alkalis and yield no product volatile from the alkaline solution (compare Eaters, Sections 111,106 and IV, 183). They may be distinguished from acids by their facile reactions with alcohols (compare Section 111,27), phenols (compare Section IV,114), and amines (compare Sections 111,123 and IV.lOO). 

Reaction with alcoholic silver nitrate. To carry out the test, treat 2 ml. of a 2 per cent, solution of silver nitrate in alcohol with 1 or 2 drops (or 0 05 g.) of the compound. If no appreciable precipitate appears at the laboratory temperature, heat on a boiling water bath for several minutes. Some organic acids give insoluble silver salts, hence it is advisable to add 1 drop of dilute (5 per cent.) nitric acid at the conclusion of the test most silver salts of organic acids are soluble in nitric acid. 

Reactions with Alcohols, Phenols, and Other Hydroxy Compounds... 

Reactions with Alcohols, Mercaptans, and Phenols. Alcohols add readily to acetaldehyde in the presence of trace quantities of mineral acid to form acetals eg, ethanol and acetaldehyde form diethyl acetal [105-57-7] (65). Similarly, cycHc acetals are formed by reactions with glycols and other polyhydroxy compounds eg, ethylene glycol [107-21-1] and acetaldehyde give 2-methyl-1,3-dioxolane [497-26-7] (66) ... 

Reactions with Alcohols. The addition of alcohols to acrolein may be catalyzed by acids or bases. By the judicious choice of reaction conditions the regioselectivity of the addition maybe controlled and alkoxy propionaldehydes, acrolein acetals, or alkoxypropionaldehyde acetals produced in high yields (66). 

Isocyanates are Hquids or soHds which are highly reactive and undergo addition reactions across the C=N double bond of the NCO group. Reactions with alcohols, carboxyUc acids, and amines have been widely exploited ia developiag a variety of commercial products. Cycloaddition reactions involving both the C=N and the C=0 double bond of the NCO group have been extensively studied and used for product development (1 9). 

Halosdanes are very reactive toward protic chemicals. They generally react violendy with water, forming siUcon dioxide and the respective hydrohalogens. Other examples include reaction with alcohols and amines as follows ... 

Silver Permanganate. Silver permanganate [7783-98-4] AgMnO, is a violet soHd formed when a potassium permanganate solution is added to a silver nitrate solution. It decomposes upon heating, exposure to light, or by reaction with alcohol. 

MSC undergoes reactions with alcohols, amines, active methylene compounds (in the presence of bases), and aromatic hydrocarbons (in the presence of Friedel-Crafts catalysts) to replace, generally, a hydrogen atom by a methanesulfonyl group (382—401). 

Reactions with Alcohols. The tendency of titanium(IV) to reach coordination number six accounts for the rapid exchange of alkoxy groups with alcohols. Departure of an alkoxy group with the proton is the first step in the ultimate exchange of all four alkoxyls. The four-coordinated monomer is expected to react... 

Separation and Purification of Isomers. 1-Butene and isobutylene caimot be economically separated into pure components by conventional distHlation because they are close boiling isomers (see Table 1 and Eig. 1). 2-Butene can be separated from the other two isomers by simple distHlation. There are four types of separation methods avaHable (/) selective removal of isobutylene by polymeriza tion and separation of 1-butene (2) use of addition reactions with alcohol, acids, or water to selectively produce pure isobutylene and 1-butene (3) selective extraction of isobutylene with a Hquid solvent, usuaHy an acid and (4) physical separation of isobutylene from 1-butene by absorbents. The first two methods take advantage of the reactivity of isobutylene. Eor example, isobutylene reacts about 1000 times faster than 1-butene. Some 1-butene also reacts and gets separated with isobutylene, but recovery of high purity is possible. The choice of a particular method depends on the product slate requirements of the manufacturer. In any case, 2-butene is first separated from the other two isomers by simple distHlation. 

Cyanuiic chloiide is a convenient piecuisoi to alkyl oi aiyl cyanurates by reaction with alcohols or phenols, or to substituted melamines by reaction with amines alkaline conditions ate employed in both cases and yields are generally high. 

M or Tl catalyzed tetfamedzallon d trtanerization of acetylene and reactions with alcohols, amines, caiboxyNe adds, thiols. 

Phenyl isocyanates are generally more reactive than alkyl isocyanates in their reactions with alcohols, but with CuCl catalysis even alkyl isocyanates will react readily with primary, secondary, or tertiary alcohols (45-95% yield). ... 

Cellobiose was prepared first by Skraup and Konig by the saponification of the octaacetate with alcoholic potassium hydroxide, and the method was improved by Pringsheim and Merkatz.3 Aqueous barium hydroxide also has been employed for the purpose, and methyl alcoholic ammonia has been used extensively for the hydrolysis of carbohydrate acetates. The method of catalytic hydrolysis with a small quantity of sodium methylate was introduced by Zemplen,i who considered the action to be due to the addition of the reagent to the ester-carbonyl groups of the sugar acetate and the decomposition of the addition compound by reaction with alcohol. The present procedure, reported by Zemplen, Gerecs, and Hadacsy, is a considerable improvement over the original method (see Note 2). 

Aldehydes and ketones undergo reversible addition reactions with alcohols. The product of addition of one mole of alcohol to an aldehyde or ketone is referred to as a hemiacetal or hemiketal, respectively. Dehydration followed by addition of a second molecule of alcohol gives an acetal or ketal. This second phase of the process can be catalyzed only by acids, since a necessary step is elimination of hydroxide (as water) from the tetrahedral intermediate. There is no low-energy mechanism for base assistance of this... 

The addition of nucleophiles to cyclic fluoroolefins has been reviewed by Park et al. [2 ]. The reaction with alcohols proceeds by addition-elimination to yield the cyclic vinylic ether, as illustrated by tlie reaction of l,2-dichloro-3,3-di-fluorocyclopropene Further reaction results in cyclopropane ring opening at the bond opposite the difluoromethylene carbon to give preferentially the methyl and ortho esters of (Z)-3-chloro-2-fluoroacrylic acid and a small amount of dimethyl malonate [29] (equation 8). 

Bis(2,2,2-trifluoroethyl)]phosphite can be used to prepaie esters of phos phorous acid by a transestenfication reaction with alcohols and phenols [750] (equation 78)... 

Reaction with alcohols (Section 15.8) Acid anhydrides react with alcohols to form esters. 

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