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organosulfur chemistry Organosulfur chemistry is the study of the properties and synthesis of organosulfur compounds, which are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur der ...
, organosulfates are a class of
organic compound Some chemical authorities define an organic compound as a chemical compound that contains a carbon–hydrogen or carbon–carbon bond; others consider an organic compound to be any chemical compound that contains carbon. For example, carbon-co ...
s sharing a common
functional group In organic chemistry, a functional group is any substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions r ...
with the structure . The core is a
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ...
group and the R group is any
organic residue Organic matter, organic material or natural organic matter is the large source of carbon-based compounds found within natural and engineered, terrestrial, and aquatic environments. It is matter composed of organic compounds that have come fro ...
. All organosulfates are formally
ester In chemistry, an ester is a compound derived from an acid (either organic or inorganic) in which the hydrogen atom (H) of at least one acidic hydroxyl group () of that acid is replaced by an organyl group (R). These compounds contain a distin ...
s derived from
alcohol Alcohol may refer to: Common uses * Alcohol (chemistry), a class of compounds * Ethanol, one of several alcohols, commonly known as alcohol in everyday life ** Alcohol (drug), intoxicant found in alcoholic beverages ** Alcoholic beverage, an alco ...
s and
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...
() although many are not prepared in this way. Many sulfate esters are used in
detergent A detergent is a surfactant or a mixture of surfactants with Cleanliness, cleansing properties when in Concentration, dilute Solution (chemistry), solutions. There are a large variety of detergents. A common family is the alkylbenzene sulfonate ...
s, and some are useful
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
s. Alkyl sulfates consist of a
hydrophobic In chemistry, hydrophobicity is the chemical property of a molecule (called a hydrophobe) that is seemingly repelled from a mass of water. In contrast, hydrophiles are attracted to water. Hydrophobic molecules tend to be nonpolar and, thu ...
hydrocarbon chain, a polar
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ...
group (containing an anion) and either a cation or
amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...
to neutralize the sulfate group. Examples include:
sodium lauryl sulfate Sodium dodecyl sulfate (SDS) or sodium lauryl sulfate (SLS), sometimes written sodium laurilsulfate, is an organic compound with the formula and structure . It is an anionic surfactant used in many cleaning and hygiene products. This compound ...
(also known as sulfuric acid mono dodecyl ester sodium salt) and related potassium and ammonium salts.


Applications

Alkyl sulfates are commonly used as anionic
surfactant Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. The word ''surfactant'' is a Blend word, blend of "surface-active agent", coined in ...
s in liquid soaps and detergents used to clean wool, as surface cleaners, and as active ingredients in laundry detergents, shampoos and conditioners. They can also be found in household products such as toothpaste, antacids, cosmetics and foods. Generally they are found in consumer products at concentrations ranging from 3-20%. In 2003 approximately 118,000 t/a of alkyl sulfates were used in the US.


Synthetic organosulfates

A common example is
sodium lauryl sulfate Sodium dodecyl sulfate (SDS) or sodium lauryl sulfate (SLS), sometimes written sodium laurilsulfate, is an organic compound with the formula and structure . It is an anionic surfactant used in many cleaning and hygiene products. This compound ...
, with the formula CH3(CH2)11OSO3Na. Also common in consumer products are the sulfate esters of
ethoxylated In organic chemistry, ethoxylation is a chemical reaction in which ethylene oxide () addition reaction, adds to a Substrate (chemistry), substrate. It is the most widely practiced alkoxylation, which involves the addition of epoxides to substrat ...
fatty alcohol Fatty alcohols (or long-chain alcohols) are usually high-molecular mass, straight-chain primary alcohols, but can also range from as few as 4–6 carbon atoms to as many as 22–26, derived from natural fats and oils. The precise chain length vari ...
s such as those derived from lauryl alcohol. An example is sodium laureth sulfate, an ingredient in some
cosmetics Cosmetics are substances that are intended for application to the body for cleansing, beautifying, promoting attractiveness, or altering appearance. They are mixtures of chemical compounds derived from either Natural product, natural source ...
. Alkylsulfate can be produced from alcohols, which in turn are obtained by
hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to redox, reduce or Saturated ...
of animal or vegetable oils and fats or using the Ziegler process or through oxo synthesis. If produced from
oleochemical Oleochemistry is the study of vegetable oils and animal oils and fats, and oleochemicals derived from these fats and oils. The resulting product can be called oleochemicals (from Latin: oleum "olive oil"). The major product of this industry is so ...
feedstock or the Ziegler process, the
hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and Hydrophobe, hydrophobic; their odor is usually fain ...
chain of the alcohol will be linear. If derived using the oxo process, a low level of branching will appear usually with a methyl or ethyl group at the C-2 position, containing even and odd amounts of alkyl chains. These alcohols react with
chlorosulfuric acid Chlorosulfuric acid (IUPAC name: sulfurochloridic acid) is the inorganic compound with the formula HSO3Cl. It is also known as chlorosulfonic acid, being the sulfonic acid of chlorine. It is a distillable, colorless liquid which is hygroscopic and ...
: : Alternatively, alcohols can be converted to the half sulfate esters using
sulfur trioxide Sulfur trioxide (alternative spelling sulphur trioxide) is the chemical compound with the formula SO3. It has been described as "unquestionably the most conomicallyimportant sulfur oxide". It is prepared on an industrial scale as a precursor to ...
: :


Laboratory routes

Specialized organosulfates can be prepared by the Elbs persulfate oxidation of phenols and the Boyland–Sims oxidation of anilines.


Dialkylsulfates

A less common family of organosulfates have the formula RO-SO2-OR'. They are prepared from sulfuric acid and the alcohol. The main examples are diethyl sulfate and
dimethyl sulfate Dimethyl sulfate (DMS) is a chemical compound with formula (CH3O)2SO2. As the diester of methanol and sulfuric acid, its formula is often written as ( CH3)2 SO4 or Me2SO4, where CH3 or Me is methyl. Me2SO4 is mainly used as a methylating agen ...
, colourless liquids that are used as
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
s in
organic synthesis Organic synthesis is a branch of chemical synthesis concerned with the construction of organic compounds. Organic compounds are molecules consisting of combinations of covalently-linked hydrogen, carbon, oxygen, and nitrogen atoms. Within the gen ...
. These compounds are potentially dangerous
alkylating agent Alkylation is a chemical reaction that entails transfer of an alkyl group. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting ...
s. Dialkylsulfates do not occur in nature.


Natural sulfate esters

Heparin is a medication and naturally occurring organosulfate. Several classes of sulfate esters exist in nature. Especially common are sugar derivatives such as
keratan sulfate Keratan sulfate (KS), also called keratosulfate, is any of several sulfated glycosaminoglycans (structural carbohydrates) that have been found especially in the cornea, cartilage, and bone. It is also synthesized in the central nervous system whe ...
,
chondroitin sulfate Chondroitin sulfate is a sulfated glycosaminoglycan (GAG) composed of a chain of alternating sugars (N-Acetylgalactosamine, N-acetylgalactosamine and glucuronic acid). It is usually found attached to proteins as part of a proteoglycan. A chondroit ...
, and the anticoagulant
heparin Heparin, also known as unfractionated heparin (UFH), is a medication and naturally occurring glycosaminoglycan. Heparin is a blood anticoagulant that increases the activity of antithrombin. It is used in the treatment of myocardial infarction, ...
.
Post-translational modification In molecular biology, post-translational modification (PTM) is the covalent process of changing proteins following protein biosynthesis. PTMs may involve enzymes or occur spontaneously. Proteins are created by ribosomes, which translation (biolog ...
s of some proteins entail sulfation, often at the phenol group of
tyrosine -Tyrosine or tyrosine (symbol Tyr or Y) or 4-hydroxyphenylalanine is one of the 20 standard amino acids that are used by cells to synthesize proteins. It is a conditionally essential amino acid with a polar side group. The word "tyrosine" is ...
residues. A steroidal sulfate is estradiol sulfate, a latent precursor to the hormone estrogen. A major portion of soil sulfur is in the form of sulfate esters.


Metabolism

Sulfate is an inert anion, so nature activates it by the formation of ester derivative of adenosine 5'-phosphosulfate (APS) and 3'-phosphoadenosine-5'-phosphosulfate (PAPS). Many organisms utilize these reactions for metabolic purposes or for the
biosynthesis Biosynthesis, i.e., chemical synthesis occurring in biological contexts, is a term most often referring to multi-step, enzyme-Catalysis, catalyzed processes where chemical substances absorbed as nutrients (or previously converted through biosynthe ...
of sulfur compounds required for life. The formation and hydrolysis of natural sulfate esters are catalyzed by
sulfatase In biochemistry, sulfatases are a class of enzymes of the esterase class that catalyze the hydrolysis of sulfate esters into an Alcohol (chemistry), alcohol and a bisulfate: :\ce \quad \xrightarrow
text Text may refer to: Written word * Text (literary theory) In literary theory, a text is any object that can be "read", whether this object is a work of literature, a street sign, an arrangement of buildings on a city block, or styles of clothi ...
\quad \ce These may be found on a rang ...
s (aka sulfohydrolases).


Safety

Because they are widely used in commercial products, the safety aspects of organosulfates are heavily investigated.


Human Health

Alkyl sulfates if ingested are well-absorbed and are metabolized into a C3, C4 or C5 sulfate and an additional metabolite. The highest irritant of the alkyl sulfates is sodium laurylsulfate, with the threshold before irritation at a concentration of 20%.
Surfactant Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. The word ''surfactant'' is a Blend word, blend of "surface-active agent", coined in ...
s in consumer products are typically mixed, reducing likelihood of irritation. According to OECD TG 406, alkyl sulfates in animal studies were not found to be skin sensitizers. Laboratory studies have not found alkyl sulfates to be
genotoxic Genotoxicity is the property of chemical agents that damage the genetic information within a cell causing mutations, which may lead to cancer. While genotoxicity is often confused with mutagenicity, all mutagens are genotoxic, but some genotoxic s ...
,
mutagenic In genetics, a mutagen is a physical or chemical agent that permanently changes genetic material, usually DNA, in an organism and thus increases the frequency of mutations above the natural background level. As many mutations can cause cancer in ...
or
carcinogenic A carcinogen () is any agent that promotes the development of cancer. Carcinogens can include synthetic chemicals, naturally occurring substances, physical agents such as ionizing and non-ionizing radiation, and Biological agent, biologic agent ...
. No long-term reproductive effects have been found.


Environment

The primary disposal of alkyl sulfate from used commercial products is wastewater. The concentration of alkylsulfates in effluent from waste water treatment plants (WWTP) has been measured at and lower. Alkyl sulfates biodegrade easily, even starting likely before reaching the WWTP. Once at the treatment plant, they are rapidly removed by
biodegradation Biodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. It is generally assumed to be a natural process, which differentiates it from composting. Composting is a human-driven process in which biodegrada ...
. Invertebrates were found to be the most-sensitive trophic group to alkyl sulfates. Sodium laurylsulfate tested on ''Uronema parduczi'', a protozoan, was found to have the lowest effect value with the 20 h-EC5 being . Chronic exposure tests with C12 to C18 with the invertebrate '' Ceriodaphnia dubia'' found the highest toxicity is with C14 ( NOEC was 0.045 mg/L). In terms of thermal stability, alkyl sulfates degrade well before reaching their boiling point due to low vapor pressure (for C8-18 from 10-11 to 10-15 hPa). Soil sorption is proportional to carbon chain length, with a length of 14 and more having the highest sorption rate. Soil concentrations have been found to vary from {{convert , 0.0035, to, 0.21, mg/kg, oz/lb, sigfig=2 dw.


References