Sulfonyl chloride groups

Phthalocyanine sulfonic acids, which can be used as direct cotton dyes (1), are obtained by heating the metal phthalocyanines in oleum. One to four sulfo groups can be introduced in the 4-position by varying concentration, temperature, and reaction time (103). Sulfonyl chlorides, which are important intermediates, can be prepared from chlorosulfonic acid and phthalocyanines (104). The positions of the sulfonyl chloride groups are the same as those of the sulfonic acids (103). Other derivatives, eg, chlormethylphthalocyanines (105—107), / /f-butyl (108—111), amino (112), ethers (109,110,113—116), thioethers (117,118), carboxyl acids (119—122), esters (123), cyanides (112,124—127), and nitrocompounds (126), can be synthesized. 

In the presence of excess acid, a sulfonyl chloride group (—SO2CI) can be attached to an aromatic group, ie, chlorosulfonation can occur,... 

The distribution of chlorine atoms along the polymer chain has been studied in great detail. The distribution in various functional types is shown in Table 4 (18). High density polyethylene chlorosulfonated to 35% G1 and 1% S has been found to contain only 1.7% highly active chlorines, ie, reactive to weak bases. AH of these are attributed to the chlorine in the sulfonyl chloride group and those in beta position to SO2GI. No vicinal chlorides groups were found (19). 

The sulfonyl chloride group is the cure site for CSM and determines the rate and state of cure along with the compound recipe. It is less stable than the Cl groups and therefore often determines the ceiling temperature for processing. The optimum level of sulfonyl chloride to provide a balance of cured properties and processibiUty is about 2 mol % or 1—1.5 wt % sulfur at 35% Cl. It also undergoes normal acid chloride reactions with amines, alcohols, etc, to make useful derivatives (17). 

Early recommendations for cross-linking CSM involved the use of divalent metal oxides to form metal sulfonate cross-links (24). The mechanism involves the hydrolysis of the sulfonyl chloride group with a carboxyHc acid, ie, stearic acid, which produces water at curing temperatures. 

The best heat resistance is obtained when nickel dibutyldithiocarbamate [13927-77-0] (NBC) is incorporated into the compound. NBC contributes to the heat resistance by causing the elimination of unused sulfonyl chloride groups which are then unavailable for additional cross-linking during heat aging. The presence of large amounts of Htharge probably also result in some ionic cross-link formation. 

V,/V dipheny1ethy1enediamine. The cure mechanism probably involves an amine-catalyzed decomposition of the sulfonyl chloride group or a path of radical anions. The cross-link probably involves the HVA-2. Calcium hydroxide or other SO2 absorbers must be included for development of good mechanical properties. 

Chlorination of natural rubber, involving both addition and substitution (with some cyclization), yields a product with improved chemical and corrosion resistance. Chlorination of polyethylene in the presence of sulfur dioxide results in substituting both chloride and sulfonyl chloride groups into the polymer. A commercially useful material is one which contains about 12 chlorides and one sulfonyl chloride per 40-45 repeating units. This extensive substitution converts the polyethylene, a plastic, into an elastomer by destroying crystallinity. 

A sulfonyl chloride group rapidly reacts with amines in the pH range of 9-10 to form stable sulfonamide bonds. Under these conditions, it also may react with tyrosine —OH groups, aliphatic alcohols, thiols, and histidine side chains. Conjugates of sulfonyl chlorides with sulf-hydryls and imidazole rings are unstable, while esters formed with alcohols are subject to nucleophilic displacement (Nillson and Mosbach, 1984 Scouten and Van der Tweel, 1984). The only stable derivative with proteins therefore is the sulfonamide, formed by reaction with e-lysine... 

Miller and Walling1 6 have shown that both bromine and sulfonyl chloride groups can be displaced during the photochemical reaction of chlorine with p-bromobenzenesulfonyl chloride and that a similar displacement of the sulfonyl group of benzenesulfonyl chloride occurs to give chlorobenzene. 

Compounds containing active hydrogens react with chlorosulfonyl isocyanate first at the isocyanate group to give N-sub-stituted sulfamyl chlorides which may react further with more active hydrogen compound at the sulfonyl chloride group.3,7 10... 

Sulfonation at C-4 can be accomplished with sulfur trioxide complexed with dioxane. Chlorosulfonic acid introduces the sulfonyl chloride group into the ring from which esters and sulfonamides can be made (79AP977,81AP470, 503). 

Polyolefins can be chemically modified with the purpose of changing some of their properties. For example, polyethylene can be chlorinated or chlorosulfonated. Chlorosulfonation can be done with a mixture of chlorine and sulfur dioxide, leading to a material partially chlorinated and partially containing sulfonyl chloride groups. This treatment imparts elastomer character and the capability to be crosslinked, for example, with metallic oxides. 

Reducing agents such as hydroiodic acid, hydrobromic acid, hypophosphorus acid, and hydrazine can be utilized in this reaction. Sulfonyl chloride group (S02C1), the most common starting chemical moiety, can be prepared from the sulfonic acid group by reaction with phosphorus pentachloride or phosphorus trichloride and chlorine (18, 20, 21, 36, 37,... 

In accordance with the above reactions, pendant carboxylic acid has one less carbon atom than the original pendant. Some patent applications report a method to prepare the pendant containing carboxylic acid in which the number of carbon atoms equal to or greater than that in the original, by application of an addition reaction with the sulfonyl chloride group or -CF X(X=I or Br). 

Although perfluorocarbon sulfonic acid groups are very stable chemically as well as thermally, perfluorocarbon sulfonyl halide, especially sulfonyl chloride groups, are quite reactive. For example, sulfonyl chloride groups react with oxidants, reductants, various amines, phenol compounds, iodine compounds, etc. and give carboxylic acid, sulfinic acid, sulfonic acid amide, -CF2I and so forth. Some examples of how this feature can be used to generate various kinds of membranes will next be described... 

To examine the resulting membrane, the reflective infrared spectrum of this membrane was measured. It was found that the absorption band at 1060 cm observed in the sulfonic acid-type membrane disappeared, and a strong absorption band corresponding to the sulfonyl chloride group was observed at 580 and 1420 cm . ... 

The same membranous material as mentioned in 1) having a thickness of 100 jjl was set in a reactor of the design which would allow only one surface of the membrane to contact with reaction reagents. Thereafter, the reactor compartment was filled with vapour of phosphorous pentachloride ( at 170°C for an hour ) to have one surface of the membrane reacted. The reflective infrared spectrum and dyeing test respectively showed that the membrane had sulfonyl chloride groups and that approximately 5 JJL of non-dyed layer was stratified at the membrane surface where phosphorous pentachloride had contacted. The electric resistance of this membrane was about 1500 ft- cm2 in a 1.0 N hydrochloric acid solution at 25°C when measured by 1000 cycle A.C. The electric resistance of the same membrane before the reaction with phosphorous pentachloride was only 0.38ft - cm2 under the same conditions. 

The membrane which had a thin layer of sulfonyl chloride groups was treated by triethylamine at room temperature for 16 hours, washed with water and then heated at 170°C. Thereafter, the membrane was also immersed in the same mixed solution composed of water, dimethyl sulfoxide and potassium hydroxide as mentioned before. Electric resistance of the membrane was 1.5ft- cm2 when measured in the environment of 3.5 N sodium chloride solution to... 

The membrane having the sulfonyl chloride groups was treated by an aqueous n-butyl amine solution for 2 hours, washed with water, heated in air for 24 hours at 90°C and then dipped in 10% methanol solution of sodium hydroxide. The reflective infrared spectrum showed that absorption band ascribable to the sulfonyl chloride disappeared and new absorption bands appeared at 1620, 1680 and 3400 cm l, The electric resistance and the electrolysis results of both of the treated and untreated membranes are shown in Table II respectively. 

The membranous copolymer as mentioned before reinforced by a plain woven cloth of polytetrafluoroethylene was reacted with vapour of phosphorous pentachloride to form a membrane having sulfonyl chloride groups on its only one side. The membrane having sulfonyl chloride groups on its only one surface was treated by 29 % aqueous ammonia solution for 30 min. at 25 C. After the ammonia treatment, the absorption bands ascribable to... 

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