Phenols alkyl sulphates

Another method of replacing hydrogen by methyl, in addition to the use of alkyl halide and alkyl sulphate, is by the action of dIazomethane on the phenol... 

Conversion of phenols into their methyl or ethyl ethers by reaction with the corresponding alkyl sulphates in the presence of aqueous sodium hydroxide affords a method which avoids the use of the more expensive alkyl halides (e.g. the synthesis of methyl 2-naphthyl ether and veratraldehyde, Expt 6.111). Also included in Expt 6.111 is a general procedure for the alkylation of phenols under PTC conditions.38,39 The method is suitable for 2,6-dialkylphenols, naphthols and various functionally substituted phenols. The alkylating agents include dimethyl sulphate, diethyl sulphate, methyl iodide, allyl bromide, epichlorohy-drin, butyl bromide and benzyl chloride. 

Steol Series Alcohol and alkyl phenol ethoxy sulphates... 

Alkyl phenol ethoxylates have been over many years the workhorses as nonionic emulsifiers for emulsion polymerization. Depending on availability and price of buten and propen, nonyl (tripropylene)phenol ethoxylates or octyl (dibutylene) phenol ethoxylates have been very broadly used, whereas dodecyl (tetrapropylene or tributylene)phenol and tri tert-butylphenol ethoxylates were merely regarded as specialties. These aUcyl phenol ethoxylates can also be used as intermediates for the synthesis of anionic alkyl phenol ether sulphates. Sulphation by chlorosul-phonic acid or sulphur trioxide besides formation of the ether sulphate end group inevitably leads to certain amounts of ring sulphonation in the phenyl group, whereas amidosulphonic acid gives sulphonate-free aUcyl phenol ether sulphate ammonium salts. 

Dyes Aldehydes, ketones, phenols, terpenes, thiophene, alkyl sulphates, polychlorinated biphenyls... 

Fatty acid and salts of fatty acids Alkyl aryl sulphonates Alkyl sulphates Phenol ethoxylates... 

Sulphate conjugates, once called ethereal sulphates because of their extraction characteristics, are of two major types aryl or alkyl sulphates (which are esters of phenols or alcohols) and steroid sulphates. The sulphate moiety is transferred from the cofactor adenosine-3 -phosphate-S -phosphosulphate (PAPS) to an acceptor by enzymes known as sulphotransferases or sulphokinases. The enzymes which catalyse the formation of PAPS as well as the sulphokinases are in the soluble fraction of liver ... 

Methyl and ethyl ethers of phenols are most conveniently prepared by alkylation with dimethyl sulphate and diethyl sulphate respectively in weakly alkaline solution, for example ... 

O-Alkylation of phenols Phenol/cresols/catechols, alkyl halides/dimethyl sulphate/diethyl sulphate... 

In other reactions also the OH-group of the phenols shows itself to be more reactive than that of the aliphatic alcohols. Phenols, but not alcohols, react easily with diazomethane. With other alkylating agents also, such as alkyl halides, and dialkyl sulphates, the phenols react even in aqueous alkaline solution whilst the alcohols do not react under such conditions. Benzoyl derivatives, most of which crystallise readily, are excellently adapted for the characterisation of phenols (Schotten-Baumann reaction). 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

This reagent has proved especially important in the study of the constitution of the sugars, and of cellulose. A series of methyl-celluloses has been obtained, and by the study of their hydrolysis, or decomposition in a vacuum, some light has been thrown on the structure of the cellulose molecule. (J. S. C. I., 41, 362 R.) In the laboratory dimethyl sulphate is much employed in the methylation of phenols and naphthols. Diethyl sulphate is not so suitable for such alkylations as its lower homo-logue. 

As mentioned above, the hydrophilic head group may be unionised [e.g., alcohols or poly(ethylene oxide) (PEO) alkane or alkyl phenol compounds], weakly ionised (e.g., carboxylic acids), or strongly ionised (e.g., sulphates, sulphonates, and quaternary ammonium salts). The adsorption of these different surfactants at the A/W and O/W interfaces depends on the nature of the head group. With nonionic surfactants, repulsion between the head groups is small and these surfactants are usually strongly adsorbed at the surface of water from very dilute solutions. Nonionic surfactants have much lower cmc values when compared to ionic surfactants with the same alkyl chain length typically, the cmc is in the region of... 

Surfactants Ionic, anionic (e.g., sodium dodecyl sulphate, Cj2H250S03 Na ), cationic (e.g., cetyl trimethyl ammonium chloride, Ci,H33-N+(CH3)3C1-), zwitterionic [e.g., 3-dimethyldodecylamine propane sulphonate (betaine CJ2H25-N" (CH3)2-CH2-CH2-CH2-S03)], nonionic, alcohol ethoxylates C H2 +i-0-(CH2-CH2-0) -H, alkyl phenol ethoxylates C H2 +i-CgH4-0-(CH2-CH2-0) -H, amine oxides (e.g., decyl dimethyl amine oxide, C10H21-N ( 113)2 0), and amine ethoxylates. 

Alkyl phenol ethoxylates can also react with P4O10 yielding alkyl phenol etherphosphates as a mixture of mono-/diesters or with maleic anhydride to yield maleic acid monoesters, which then react with NaHS03 to yield sulphosuccinate monoesters. Alkylphenolpolyglycolether sulphates, phosphates or sulphosuccinates are mainly used as primary anionic emulsifiers for the manufacturing of acrylic, styrene/acrylic or vinyl acetate co-polymer dispersions. Another type of non-ionic emulsifier is block copolymers of ethylene oxide with propylene oxide. 

Chromanones.—A new two-stage synthesis of these rather elusive compounds (145) employs the oxiran (144) and phenol the first stage is catalysed by BFa EtaO, and cyclization is brought about by PPA. When 3-chromanone was treated with various alkyl halides or sulphates in the presence of Et4N Br , at 20 °C, a mixture of products was obtained." ... 

Dimethyl sulphate is sometimes preferable to methyl-iodide for the alkylation of phenols and all other classes of compounds capable of alkylation. With phenols it is employed in alkaline aqueous solution as in the Schottcn-Baiimann method (cf p. 

Alkylation of a phenol is most frequently accomplished by reaction of an alkyl halide or sulphate, in the presence of a base, with a phenol or an acylated phenol. Reagents and the typical conditions for the more commonly used alkyl groups are listed in Table 4.3. 

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