Cyanamides
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Cyanamide is an
organic compound In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. The ...
with the
formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwee ...
C N2 H2. This white solid is widely used in agriculture and the production of pharmaceuticals and other organic compounds. It is also used as an alcohol-deterrent drug. The molecule features a
nitrile In organic chemistry, a nitrile is any organic compound that has a functional group. The prefix ''cyano-'' is used interchangeably with the term ''nitrile'' in industrial literature. Nitriles are found in many useful compounds, including met ...
group attached to an
amino In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent s ...
group. Derivatives of this compound are also referred to as cyanamides, the most common being
calcium cyanamide Calcium cyanamide is the inorganic compound with the formula CaCN2. It is the calcium salt of the cyanamide () anion. This chemical is used as fertilizer and is commercially known as nitrolime. It was first synthesized in 1898 by Adolph Frank and ...
(CaCN2).


Tautomers and self-condensations

Containing both a nucleophilic and electrophilic site within the same molecule, cyanamide undergoes various reactions with itself. Cyanamide exists as two
tautomer Tautomers () are structural isomers (constitutional isomers) of chemical compounds that readily interconvert. The chemical reaction interconverting the two is called tautomerization. This conversion commonly results from the relocation of a hydr ...
s, one with the connectivity N≡C–NH2 and the other with the formula HN=C=NH ("
carbodiimide In organic chemistry, a carbodiimide (systematic IUPAC name: methanediimine) is a functional group with the formula RN=C=NR. They are exclusively synthetic. A well known carbodiimide is dicyclohexylcarbodiimide, which is used in peptide synthesis. ...
" tautomer). The N≡C–NH2 form dominates, but in a few reactions (e.g.
silylation Silylation is the introduction of one or more (usually) substituted silyl groups (R3Si) to a molecule. The process is the basis of organosilicon chemistry. Of organic compounds Alcohols, carboxylic acids, amines, thiols, and phosphates can be sil ...
) the diimide form appears to be important. Cyanamide dimerizes to give 2-cyanoguanidine (dicyandiamide). This dimerization is disfavored by acids and is inhibited by low temperatures. The cyclic trimer is called
melamine Melamine is an organic compound with the formula C3H6N6. This white solid is a trimer of cyanamide, with a 1,3,5-triazine skeleton. Like cyanamide, it contains 67% nitrogen by mass, and its derivatives have fire retardant properties due t ...
.


Production

Cyanamide is produced by hydrolysis of
calcium cyanamide Calcium cyanamide is the inorganic compound with the formula CaCN2. It is the calcium salt of the cyanamide () anion. This chemical is used as fertilizer and is commercially known as nitrolime. It was first synthesized in 1898 by Adolph Frank and ...
, which in turn is prepared from
calcium carbide Calcium carbide, also known as calcium acetylide, is a chemical compound with the chemical formula of Ca C2. Its main use industrially is in the production of acetylene and calcium cyanamide. The pure material is colorless, while pieces of tec ...
via the Frank-Caro process. :CaCN2 + H2O + CO2 → CaCO3 + H2NCN The conversion is conducted on slurries.


Reactions and uses

Cyanamide can be regarded as a functional single carbon fragment which can react as an
electrophile In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carries ...
or
nucleophile In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are ...
. The main reaction exhibited by cyanamide involves additions of compounds containing an acidic proton. Water, hydrogen sulfide, and hydrogen selenide react with cyanamide to give
urea Urea, also known as carbamide, is an organic compound with chemical formula . This amide has two amino groups (–) joined by a carbonyl functional group (–C(=O)–). It is thus the simplest amide of carbamic acid. Urea serves an important r ...
,
thiourea Thiourea () is an organosulfur compound with the formula and the structure . It is structurally similar to urea (), except that the oxygen atom is replaced by a sulfur atom (as implied by the ''thio-'' prefix); however, the properties of urea ...
, and
selenourea Selenourea is the organoselenium compound with the formula SeC(NH2)2. It is a white solid. This compound features a rare example of a stable, unhindered carbon-selenium double bond. The compound is used in the synthesis of selenium heterocycles ...
, respectively: :H2NCN + H2E → H2NC(E)NH2 (E = O, S, Se) In this way, cyanamide behaves as a dehydration agent and thus can induce condensation reactions. Alcohols, thiols, and amines react analogously to give alkylisoureas, "pseudothioureas", and
guanidine Guanidine is the compound with the formula HNC(NH2)2. It is a colourless solid that dissolves in polar solvents. It is a strong base that is used in the production of plastics and explosives. It is found in urine predominantly in patients experie ...
s. The anti-ulcer drug
cimetidine Cimetidine, sold under the brand name Tagamet among others, is a histamine H2 receptor antagonist that inhibits stomach acid production. It is mainly used in the treatment of heartburn and peptic ulcers. The development of longer-acting H2 rec ...
is generated using such reactivity. Related reactions exploit the bifunctionality of cyanamide to give
heterocycle A heterocyclic compound or ring structure is a cyclic compound that has atoms of at least two different chemical element, elements as members of its ring(s). Heterocyclic chemistry is the branch of organic chemistry dealing with the synthesis ...
s, and this latter reactivity is the basis of several pharmaceutical syntheses such as the aminopyrimidine
imatinib Imatinib, sold under the brand names Gleevec and Glivec (both marketed worldwide by Novartis) among others, is an oral chemotherapy medication used to treat cancer. Imatinib is a small molecule inhibitor targeting multiple receptor tyrosine kin ...
, and agrichemicals
Amitrol 3-Amino-1,2,4-triazole (3-AT) is a heterocyclic organic compound that consists of a 1,2,4-triazole substituted with an amino group. 3-AT is a competitive inhibitor of the product of the HIS3 gene, imidazoleglycerol-phosphate dehydratase. Imidazol ...
and
hexazinone Hexazinone is an organic compound that is used as a broad spectrum herbicide. It is a colorless solid. It exhibits some solubility in water but is highly soluble in most organic solvents except alkanes. A member of the triazine class herbicides ...
. The hair-loss treatment
minoxidil Minoxidil, sold under the brand name Rogaine among others, is a medication used for the treatment of high blood pressure and pattern hair loss. It is an antihypertensive vasodilator. It is available as a generic medication by prescription in ora ...
and the
anthelmintic Anthelmintics or antihelminthics are a group of antiparasitic drugs that expel parasitic worms (helminths) and other internal parasites from the body by either stunning or killing them and without causing significant damage to the host. They may a ...
s
albendazole Albendazole (also known as albendazolum) is a broad-spectrum anthelmintic and antiprotozoal agent of the benzimidazole type. It is used for the treatment of a variety of intestinal parasite infections, including ascariasis, pinworm infection, h ...
,
flubendazole Flubendazole is an anthelmintic. Its brand name is Flutelmium which is a paste manufactured by Janssen Pharmaceutica N.V. used by veterinarians for protection against internal parasites and worms in dogs and cats. Other brand names are Flubenol, ...
, and
mebendazole Mebendazole (MBZ), sold under the brand name Vermox among others, is a medication used to treat a number of parasitic worm infestations. This includes ascariasis, pinworm infection, hookworm infections, guinea worm infections, hydatid disease, ...
feature 2-aminoimidazole substructures derived from cyanamide. Cyanamide is also used in the synthesis of other pharmaceutical drugs including
tirapazamine Tirapazamine (SR-4233) is an experimental anticancer drug that is activated to a toxic radical only at very low levels of oxygen ( hypoxia). Such levels are common in human solid tumors, a phenomenon known as tumor hypoxia. Thus, tirapazamine is ...
,
etravirine Etravirine (ETR, brand name Intelence, formerly known as TMC125) is a drug used for the treatment of HIV. Etravirine is a non-nucleoside reverse transcriptase inhibitor (NNRTI). Unlike the currently available agents in the class, resistance to o ...
, revaprazan, and dasantafil. The cyanamide
anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
has the character of a pseudo
chalcogen The chalcogens (ore forming) ( ) are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the radioact ...
, cyanamide can therefore be regarded as analogue to
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
or
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...
. A convenient method for the preparation of secondary amines which are not contaminated with primary or tertiary amines is the reaction of cyanamide with alkyl halides to ''N,N''-dialkylcyanamides which can easily be hydrolyzed to dialkylamines and then decarboxylated. Cyanamide adds itself in the presence of N-bromosuccinimide to olefinic double bonds. The addition product is converted by bases to N-Cyanaziridine, cyclized in the presence of acids to imidazolines, which can be further reacted to vicinal diamines by alkaline cleavage. Cyanamide is also a versatile synthetic building block for heterocycles: it forms 2-aminobenzimidazole with
1,2-diaminobenzene ''o''-Phenylenediamine (OPD) is an organic compound with the formula C6H4(NH2)2. This aromatic diamine is an important precursor to many heterocyclic compounds. It is isomeric with ''m''-phenylenediamine and ''p''-phenylenediamine. Preparation ...
and it forms with the readily available cyclic
enamine An enamine is an unsaturated compound derived by the condensation of an aldehyde or ketone with a secondary amine. Enamines are versatile intermediates. : The word "enamine" is derived from the affix ''en''-, used as the suffix of alkene, and th ...
4-(1-cyclohexenyl)morpholine and with elemental
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
a 2-aminothiazole in good yields. Sodium dicyanamide is available in good yield and high purity from cyanamid and
cyanogen chloride Cyanogen chloride is a highly toxic chemical compound with the formula CNCl. This linear, triatomic pseudohalogen is an easily condensed colorless gas. More commonly encountered in the laboratory is the related compound cyanogen bromide, a room-te ...
, which is suitable as an intermediate for the synthesis of active pharmaceutical ingredients. A guanidino group is introduced by reaction of cyanamide with
sarcosine Sarcosine, also known as ''N''-methylglycine, or monomethylglycine, is a monopeptide with the formula CH3N(H)CH2CO2H. It exists at neutral pH as the zwitterion CH3N+(H)2CH2CO2−, which can be obtained as a white, water-soluble powder. Like some ...
In the industrial synthesis of
creatine Creatine ( or ) is an organic compound with the nominal formula (H2N)(HN)CN(CH3)CH2CO2H. It exists in various modifications (tautomers) in solution. Creatine is found in vertebrates where it facilitates recycling of adenosine triphosphate ( ...
: This synthesis route mostly avoids problematic impurities like
chloroacetic acid Chloroacetic acid, industrially known as monochloroacetic acid (MCA), is the organochlorine compound with the formula ClCH2CO2H. This carboxylic acid is a useful building block in organic synthesis. It is a colorless solid. Related compounds ...
,
iminodiacetic acid Iminodiacetic acid is the organic compound with the formula HN(CH2CO2H)2, often abbreviated to IDA. A white solid, the compound is a dicarboxylic acid amine (the nitrogen atom forms a secondary amino group, not an imino group as the name suggests ...
, or dihydrotriazine that occur in other routes. The physiological precursor guanidinoacetic is obtained analogously by reacting cyanamide with
glycine Glycine (symbol Gly or G; ) is an amino acid that has a single hydrogen atom as its side chain. It is the simplest stable amino acid (carbamic acid is unstable), with the chemical formula NH2‐ CH2‐ COOH. Glycine is one of the proteinogeni ...
. Methods to stabilize cyanamidefmel make it available on an industrial scale. Due to the strong affinity towards self-condensation in alkaline media (see above) solutions of cyanamide are stabilized by the addition of 0.5 wt% of
monosodium phosphate Monosodium phosphate (MSP), also known as monobasic sodium phosphate and sodium dihydrogen phosphate, is an inorganic compound of sodium with a dihydrogen phosphate (H2PO4−) anion. One of many sodium phosphates, it is a common industrial chemical ...
as buffer. Solid cyanamide is produced by careful evaporation of the solvent and subsequent addition of a hydrolysis-labile
ester In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ar ...
of
formic acid Formic acid (), systematically named methanoic acid, is the simplest carboxylic acid, and has the chemical formula HCOOH and structure . It is an important intermediate in chemical synthesis and occurs naturally, most notably in some ants. Es ...
. The ester absorbs traces of moisture (suppression of urea formation), neutralizes alkalinity (ammonia) and continually releases small amounts of formic acid.


Agricultural use

Cyanamide, under the trade name Dormex, is a common agricultural rest-breaking agent applied in spring to stimulate uniform opening of
bud In botany, a bud is an undeveloped or embryonic shoot and normally occurs in the axil of a leaf or at the tip of a stem. Once formed, a bud may remain for some time in a dormant condition, or it may form a shoot immediately. Buds may be spec ...
s, early foliation and bloom. Cyanamide can effectively compensate for the moderate lack of
chilling unit The chilling requirement of a fruit is the minimum period of cold weather after which a fruit-bearing tree will blossom. It is often expressed in chill hours, which can be calculated in different ways, all of which essentially involve adding up t ...
s accumulated in the previous autumn and save the harvest that would otherwise be lost. It is particularly effective for woody plants such as blueberries, grapes, apples, peaches and kiwifruit. Most recently the product was approved for use on almonds and pistachios in the USA. Overdosage, high concentration and error in timing of application can damage the buds (especially of
peach The peach (''Prunus persica'') is a deciduous tree first domesticated and cultivated in Zhejiang province of Eastern China. It bears edible juicy fruits with various characteristics, most called peaches and others (the glossy-skinned, non-fu ...
trees). Growers may avoid damage by applying 30 days prior to bud break according to the label. A 50% aqueous solution of cyanamide is also used as a
biocide A biocide is defined in the European legislation as a chemical substance or microorganism intended to destroy, deter, render harmless, or exert a controlling effect on any harmful organism. The US Environmental Protection Agency (EPA) uses a slig ...
(disinfectant) particularly in
pig farming Pig farming or pork farming or hog farming is the raising and breeding of domestic pigs as livestock, and is a branch of animal husbandry. Pigs are farmed principally for food (e.g. pork: bacon, ham, gammon) and skins. Pigs are amenable t ...
, because it effectively kills salmonella and shigella and fights
flies Flies are insects of the order Diptera, the name being derived from the Greek δι- ''di-'' "two", and πτερόν ''pteron'' "wing". Insects of this order use only a single pair of wings to fly, the hindwings having evolved into advanced ...
in all stages of development.


Environmental aspects

Cyanamide degrades via hydrolysis to urea, an excellent fertilizer.
Fungi A fungus ( : fungi or funguses) is any member of the group of eukaryotic organisms that includes microorganisms such as yeasts and molds, as well as the more familiar mushrooms. These organisms are classified as a kingdom, separately from ...
, like ''
Myrothecium verrucaria ''Myrothecium verrucaria'' is a species of fungus in the order Hypocreales. A plant pathogen, it is common throughout the world, often found on materials such as paper, textiles, canvas and cotton. It is a highly potent cellulose decomposer. It ...
'', accelerate this process utilizing the enzyme cyanamide hydratase.


Cyanamide functional group

Cyanamide is the name for a functional group with the formula NCNRR' where R and R' can be a variety of groups. These compounds are called cyanamides. One example is naphthylcyanamide, C10H7N(H)CN Some cyanamides are prepared by
alkylation Alkylation is the transfer of an alkyl group from one molecule to another. 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 ...
of calcium cyanamide. Others, such as the naphthyl derivative, are produced indirectly.


Cyanamide in space

Due to its high permanent dipole moment (i.e., 4.32 ± 0.08 D), cyanamide was detected by spectral emissions coming from the Sgr B2
molecular cloud A molecular cloud, sometimes called a stellar nursery (if star formation is occurring within), is a type of interstellar cloud, the density and size of which permit absorption nebulae, the formation of molecules (most commonly molecular hydrogen ...
(T < 100 K) through its microwave transitions as the first known interstellar molecule containing the NCN frame.


Safety

It is used as an alcohol-deterrent drug in Canada, Europe, and Japan. Cyanamide has a modest toxicity in humans. Workplace exposure to hydrogen cyanamide sprays or exposure in people living in the vicinity of spraying have been reported as causing
respiratory The respiratory system (also respiratory apparatus, ventilatory system) is a biological system consisting of specific organs and structures used for gas exchange in animals and plants. The anatomy and physiology that make this happen varies grea ...
irritation,
contact dermatitis Contact dermatitis is a type of acute or chronic inflammation of the skin caused by exposure to chemical or physical agents. Symptoms of contact dermatitis can include itchy or dry skin, a red rash, bumps, blisters, or swelling. These rashes are ...
,
headache Headache is the symptom of pain in the face, head, or neck. It can occur as a migraine, tension-type headache, or cluster headache. There is an increased risk of depression in those with severe headaches. Headaches can occur as a result ...
, and
gastrointestinal symptom Gastrointestinal diseases (abbrev. GI diseases or GI illnesses) refer to diseases involving the gastrointestinal tract, namely the oesophagus, stomach, small intestine, large intestine and rectum, and the accessory organs of digestion, the liver, g ...
s of nausea,
vomiting Vomiting (also known as emesis and throwing up) is the involuntary, forceful expulsion of the contents of one's stomach through the mouth and sometimes the Human nose, nose. Vomiting can be the result of ailments like Food-poisoning, foo ...
, or
diarrhea Diarrhea, also spelled diarrhoea, is the condition of having at least three loose, liquid, or watery bowel movements each day. It often lasts for a few days and can result in dehydration due to fluid loss. Signs of dehydration often begin wi ...
.


References


External links

* *
OSHA guideline for cyanamide
{{Authority control Acetaldehyde dehydrogenase inhibitors Inorganic carbon compounds Nitrogen cycle