Reaction with chloroformates

Chitin hydrogels, partially deacetylated, degradation, 182-184 Chloroformates, reaction with polysaccharides, 191,193-195... 

Phenol Chloroform (]) Reaction with formaldehyde. Discussed in Sec. 32.7. 

When lithium aluminum hydride was applied, besides reduction of the C-4—N-5 double bond, the ester group was converted to a hydroxymethyl group. S By reaction with dry formic acid under reflux conditions, the pyrroloquinazoline-2-carboxylates 63 yielded the 6-formyl-5,6-dihydro derivatives 65. S The formyl group was transformed into a methyl group by diborane. S The NH group of the dihydro derivatives 64 was acylated by ethyl chloroformate. Reaction with ethyl acrylate and acrylonitrile involved a Michael addition.The ethoxycarbonyl moiety in position 2 and on the side chain in position 6 was hydrolyzed to a carboxylic group by the action of potassium hydroxide in aqueous methanol and was reduced to a hydroxymethyl group by lithium aluminum hydride in ether. 

Cyclopropyl-2,3-dihydro-17f-benzo[/ ][l,5]diazepin-2-ones 2, obtained in one step from 1,2-phenylenediamines 1, give allylic bromides 3 when treated with A-bromosuccinimide in refluxing chloroform. Reaction with Af-chlorosuccinimide under the same conditions resulted in chlorination at C3 without attack of the cyclopropane. ... 

Chloroform, reaction with 1-octene to give l,l,3-trichloro- -nonane, 45, 104... 

Reaction with chlorosulphonic acid ( chlorosulphonyl-ation ). Sulphonamides. Many aryl hahdes, either alone or in chloroform solution, when treated with excess of chlorosulphonic acid afford the corresponding sulphonyl chlorides in good yield (compare Section IV.106) the latter may be readily converted into the aryl sulphonamides by reaction with concentrated ammonia solution or with sohd ammonium carbonate. 

Dissolve 1 0 g. of the compound in 5 ml. of dry chloroform in a dry test-tuhe, cool to 0°, and add dropwise 5g. (2-8 ml.) of redistilled chloro-sulphonic acid. When the evolution of hydrogen chloride subsides, allow the reaction mixture to stand at room temperature for 20 minutes. Pour the contents of the test-tube cautiously on to 25 g. of crushed ice contained in a small beaker. Separate the chloroform layer and wash it with a httle cold water. Add the chloroform layer, with stirring, to 10 ml. of concentrated ammonia solution. After 10 minutes, evaporate the chloroform on a water bath, cool the residue and treat it with 5 ml. of 10 per cent, sodium hydroxide solution the sulphonamide dissolves as the sodium derivative, RO.CgH4.SO,NHNa. Filter the solution to remove any insoluble matter (sulphone, etc.), acidify the filtrate with dilute hydrochloric acid, and cool in ice water. Collect the sulphonamide and recrystallise it from dilute alcohol. 

The ester 870 is prepared by the cross-coupling of the chloroformate 869 with an organotin reagent. Some chloroformates are easily decomposed by a Pd catalyst, and hence the reaction should be carried out by slow addition of the chloroformates. Similarly, the amide 872 is prepared by the reaction of the carbamoyl chloride 871 [742]. The coupling of alkylcopper with ethyl chloroformate catalyzed by Pd affords esters[743]. 

Acetaldehyde reacts with phosphoms pentachloride to produce 1,1-dichloroethane [75-34-3] and with hypochlorite and hypoiodite to yield chloroform [67-66-3] and iodoform [75-47-8], respectively. Phosgene [75-44-5] is produced by the reaction of carbon tetrachloride with acetaldehyde in the presence of anhydrous aluminum chloride (75). Chloroform reacts with acetaldehyde in the presence of potassium hydroxide and sodium amide to form l,l,l-trichloro-2-propanol [7789-89-1] (76). 

A iridine traces in aqueous solution can be determined by reaction with 4-(p-nitroben25l)pyridine [1083-48-3] and potassium carbonate [584-08-7]. Quantitative determination is carried out by photometric measurement of the absorption of the blue dye formed (367,368). Alkylating reagents interfere in the determination. A iridine traces in the air can be detected discontinuously by absorption in Folin s reagent (l,2-naphthoquinone-4-sulfonate) [2066-93-5] (369,370) with subsequent chloroform extraction and hplc analysis of the red dye formed (371,372). The detection limit is ca 0.1 ppm. Nitrogen-specific thermal ionisation detectors can be used for continuous monitoring of the ambient air. 

The reaction of phosgene with alcohols yields chloroformates, and with a basic catalyst present, carbonates ate formed ... 

Ahyl alcohol undergoes reactions typical of saturated, aUphatic alcohols. Ahyl compounds derived from ahyl alcohol and used industriahy, are widely manufactured by these reactions. For example, reactions of ahyl alcohol with acid anhydrides, esters, and acid chlorides yield ahyl esters, such as diahyl phthalates and ahyl methacrylate reaction with chloroformate yields carbonates, such as diethylene glycol bis(ahyl carbonate) addition of ahyl alcohol to epoxy groups yields products used to produce ahyl glycidyl ether (33,34). 

The potentiometric micro detection of all aminophenol isomers can be done by titration in two-phase chloroform-water medium (100), or by reaction with iodates or periodates, and the back-titration of excess unreacted compound using a silver amalgam and SCE electrode combination (101). Microamounts of 2-aminophenol can be detected by potentiometric titration with cupric ions using a copper-ion-selective electrode the 3- and... 

Hydroxyhc Compounds. Chloioformates on reaction with water give the patent hydroxy compound, HCl, and CO2 as weU as the symmetrical carbonate formed by the reaction of the hydroxy compound with chloroformate. 

Aliphatic Alcohols and Thiols. Ahphatic alcohols on reaction with chloroformates give carbonates and hydrogen chloride. Frequendy, the reaction proceeds at room temperature without a catalyst or hydrogen chloride acceptor. However, faster reactions and better yields are obtained in the presence of alkaU metals or their hydroxides, or tertiary amines. Reactions of chloroformates with thiols yield monothiolocarbonates (14). 

Heterocyclic Alcohols. Thek reactions with chloroformates lead to carbonates. Thus furan- and tetrahydrofuran-derived alcohols give the corresponding carbonates in 75% yield (15). Inorganic bases and tertiary amines as acid acceptors increase the rate and yield in this reaction. 

Ethyl chloroformate is used in the manufacture of ore flotation agents by reaction with various xanthates (48). 

Diethylene glycol bis (chloroformate) [106-75-2] is the starting material for diethylene glycol bis(allyl carbonate) [142-22-3] CR-39, or Nouryset 200, monomer, used in the manufacture of break-resistant optical lenses, which is obtained by the reaction with aHyl alcohol [107-18-6] (59). Alternatively, it can be obtained from aHyl chloroformate [2937-50-0] and diethylene glycol (60) (see Allylmonomers and polymers). 

Reaction with Water. The alkyl carbonate esters, especially the lower ones, hydroly2e very slowly in water when compared to the carbonochloridic esters (chloroformates). Under alkaline conditions, the rates of hydrolysis are similar to those of the corresponding acetic acid esters. 

The most common reaction of methylene chloride is its reaction with chlorine to give chloroform and carbon tetrachloride. This occurs by a free-radical process initiated by heat or light in the gas or Hquid phase. Catalytic chlorination to these same products is also known (see Chlorocarbons and Cm OROHYDROCARBONS, Cm OROFORM). 

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