HEXAMETHYLENETETRAMINE
HEXAMETHYLENETETRAMINE
Hexamethylenetetramine = Hexamine = Methenamine = HMTA
Hexamethylenetetramine, also known as methenamine, hexamine, or urotropin, is a heterocyclic organic compound with the formula (CH2)6N4.
This white crystalline compound is highly soluble in water and polar organic solvents. It has a cage-like structure similar to adamantane.
It is useful in the synthesis of other organic compounds, including plastics, pharmaceuticals, and rubber additives.
It sublimes in vacuum at 280 °C.
Hexamethylenetetramine appears as odorless white crystalline powder or colorless lustrous crystals. Sublimes in a vacuum at about 505° F with some decomposition. Solutions are strong bases (pH of 0.2 molar aqueous solution is 8.4). (NTP, 1992)
Hexamethylenetetramine a crystalline compound C6H12N4 used especially as an accelerator in vulcanizing rubber and as a urinary antiseptic
EC / List no.: 202-905-8
CAS no.: 100-97-0
Mol. formula: C6H12N4
Hexamethylenetetramine is a versatile reagent in organic synthesis. It plays a major role in modern organic synthesis
Main Applications of Hexamethylenetetramine are Resin hardeners, foaming agents, rubber vulcanization accelerators and pharmaceuticals
Hexamine is also known as hexamethylenetetramine, aminoform, crystamine, methenamine or formin.
Hexamethylenetetramine was first prepared in 1859 by Butlerov of Russia.
Hexamethylenetetramine is a white, crystalline powder with a slight amine odor.
Hexamethylenetetramine is soluble in water, alcohol, and chloroform, but it is insoluble in ether.
However the aqueous solutions exhibit inverse solubility, i.e., less hexamine dissolves as the temperature increases.
The hydrate, can be crystallized from the aqueous solution at temperatures below
Applications
Hexamethylenetetramine is used as a formylation agent in the synthesis and as a precipitating agent.
Hexamethylenetetramine is also used in the production of phenolic resins and its moulding compounds, which finds application as binders in fire proof materials, brake and clutch linings.
Hexamethylenetetramine is involved in the preparation of 5-tert-butyl-2-hydroxy-isophthalaldehyde.
Hexamethylenetetramine is useful for the treatment of urinary tract infection. Further, Hexamine is used in the Duff reaction, Sommelet reaction and in the Delepine reaction.
Notes
Hexamine is Hygroscopic.
Hexamine is incompatible with strong oxidizing agents and strong acids.
Avoid conditions like flames, sparks and moisture.
Hexamethylenetetramine is found in antibiotics, solid fuel tablets used for cooking while camping or hiking, rubber/textile adhesives, paints, lacquers, photography products, and in the production of deodorants and hair products. It is used as a preservative in cheeses, in test carpets for fire-protection, and as a hardening component to binders such as brake and clutch linings, abrasive products, nonwoven textiles, and fireproof materials.
Hexamethylenetetramine, also known as methenamine, is a white crystalline heterocyclic organic compound that is highly solubi.in water and polar organic solvents.
Its chemical formula is (CH2)6N4. The flammable solid has a cage-like structure similar to adamantine.
Hexamethylenetetramine is used in the synthesis of other chemical compounds such as plastics, pharmaceuticals, and rubber additives.
Hexamethylenetetramine is dominantly used in the production of powdery or liquid preparations of phenolic resins and phenolic resin molding compounds where it is added as a hardening component. These products are used as binders in the manufacture of brake and clutch linings, abrasive products, non-woven textiles, formed parts produced by molding processes, and fireproof materials. It is also used in the medical profession for the treatment of urinary tract infections.
Because it is smokeless when burned, has a high energy density of 30.0 megajoules per kilogram (MJ/kg), does not liquify while burning, and leaves no ashes, hexamethylenetetramine is a component of hexamine fuel tablets used by campers, hobbyists, the military and relief organizations for heating camping food as well as military rations.
The crystalline compound is also used as a reagent in organic chemistry, a food additive as a preservative, and as the base component in the manufacture of certain explosives.
Consumer Uses
Adhesives and Sealants
Agricultural Products (non-pesticidal)
Automotive Care Products
Building/Construction Materials not covered elsewhere
CBI
Plastic and Rubber Products not covered elsewhere
Hexamethylenetetramine (HMTA) (CAS 100-97-0) Market Segmentation, On the Basis of Applications:
Textiles
Plastic
Pharmaceutical
Paints and Coatings
Adhesives
Energy and Fuel
Food and Beverages
Hexamethylenetetramine
Application Notes
Hexamethylenetetramine is used for amino acid preparation.
Hexamethylenetetramine is also used in synthesis as a formylation agent and is employed in preparing specialized materials.
Hexamethylenetetramine is also used as a precipitating agent.Hexamethylenetetramine (HMTA) may be used as:
• Raw material in the synthesis of blue emitting boron carbon oxynitride (BCNO) phosphors and Zinc oxide (ZnO) nanorods.
• Catalyst in the synthesis of 2-amino-4H-pyran derivatives.
• Surfactant in the synthesis of HMTA capped transition metals doped ZnS nanoparticles.
• Precipitant and template in the synthesis of Ni(OH)2.
IUPAC name: 1,3,5,7-Tetraazatricyclo[3.3.1.13,7]decane
Other names: Hexamine; Methenamine;
Urotropine; 1,3,5,7- tetraazaadamantane, Formin, Aminoform
CAS Number: 100-97-0
EC Number: 202-905-8
E number: E239 (preservatives)
Properties
Chemical formula: C6H12N4
Molar mass: 140.186 g/mol
Appearance: White crystalline solid
Odor: Fishy, ammonia like
Density 1.33 g/cm3 (at 20 °C)
Melting point: 280 °C (536 °F; 553 K) (sublimes)
Solubility in water: 85.3 g/100 mL
Solubility: Soluble in chloroform, methanol, ethanol, acetone, benzene, xylene, ether
Solubility in chloroform: 13.4 g/100 g (20 °C)
Solubility in methanol: 7.25 g/100 g (20 °C)
Solubility in ethanol: 2.89 g/100 g (20 °C)
Solubility in acetone: 0.65 g/100 g (20 °C)
Solubility in benzene: 0.23 g/100 g (20 °C)
Acidity (pKa): 4.89
Pharmacology
ATC code J01XX05 (WHO)
Hazards
Main hazards: Highly combustible, harmful
Flash point: 250 °C (482 °F; 523 K)
Autoignition temperature: 410 °C (770 °F; 683 K)
Methenamine is a heterocyclic organic compound with antibiotic activity. In the body methenamine is converted to formaldehyde, a nonspecific bactericidal agent. Methenamine is typically used long-term to treat chronic urinary tract infections and to prevent the recurrence of infections.
NCI Thesaurus (NCIt)
Methenamine is a urinary tract antiseptic that is used as suppressive therapy for chronic or recurrent urinary tract infections. Methenamine has not been linked to serum enzyme elevations or to instances of clinically apparent acute liver injury.
LiverTox
Methenamine is a heterocyclic organic compound with a cage-like structure similar to adamantane. In salt form it is used for the treatment of urinary tract infection (Example: methenamine hippurate which is the hippuric acid salt of methenamine).
Synthesis, structure, reactivity
Hexamethylenetetramine was discovered by Aleksandr Butlerov in 1859.
It is prepared industrially by combining formaldehyde and ammonia.
The reaction can be conducted in gas phase and in solution.
Synthesis Hexamine.svg
The molecule has a symmetric tetrahedral cage-like structure, similar to adamantane, whose four “corners” are nitrogen atoms and “edges” are methylene bridges. Although the molecular shape defines a cage, no void space is available at the interior for binding other atoms or molecules, unlike crown ethers or larger cryptand structures.
The molecule behaves like an amine base, undergoing protonation and N-alkylation (e.g. Quaternium-15).
Applications
The dominant use of hexamethylenetetramine is in the production of powdery or liquid preparations of phenolic resins and phenolic resin moulding compounds, where it is added as a hardening component. These products are used as binders, e.g. in brake and clutch linings, abrasive products, non-woven textiles, formed parts produced by moulding processes, and fireproof materials.[4]
It has been proposed that hexamethylenetetramine could work as a molecular building block for self-assembled molecular crystals.[5][6]
Medical uses
As the mandelic acid salt (generic methenamine mandelate, USP[7]) it is used for the treatment of urinary tract infection. It decomposes at an acidic pH to form formaldehyde and ammonia, and the formaldehyde is bactericidal; the mandelic acid adds to this effect. Urinary acidity is typically ensured by co-administering vitamin C (ascorbic acid) or ammonium chloride. Its use had temporarily been reduced in the late 1990s, due to adverse effects, particularly chemically-induced hemorrhagic cystitis in overdose,[8] but its use has now been re-approved because of the prevalence of antibiotic resistance to more commonly used drugs. This drug is particularly suitable for long-term prophylactic treatment of urinary tract infection, because bacteria do not develop resistance to formaldehyde. It should not be used in the presence of chronic kidney disease.
Methenamine in the form of cream and spray is successfully used for treatment of excessive sweating and concomitant odor.[medical citation needed]
Histological stains
Methenamine silver stains are used for staining in histology, including the following types:
Grocott’s methenamine silver stain, used widely as a screen for fungal organisms.
Jones’ stain, a methenamine silver-Periodic acid-Schiff that stains for basement membrane, availing to view the “spiked” Glomerular basement membrane associated with membranous glomerulonephritis.
Solid fuel
Together with 1,3,5-trioxane, hexamethylenetetramine is a component of hexamine fuel tablets used by campers, hobbyists, the military and relief organizations for heating camping food or military rations. It burns smokelessly, has a high energy density of 30.0 megajoules per kilogram (MJ/kg), does not liquify while burning, and leaves no ashes, although its fumes are toxic.
Standardized 0.149 g tablets of methenamine (hexamine) are used by fire-protection laboratories as a clean and reproducible fire source to test the flammability of carpets and rugs.[9]
Food additive
Hexamethylene tetramine or hexamine is also used as a food additive as a preservative (INS number 239). It is approved for usage for this purpose in the EU,[10] where it is listed under E number E239, however it is not approved in the USA, Russia, Australia, or New Zealand.[11]
Reagent in organic chemistry
Hexamethylenetetramine is a versatile reagent in organic synthesis.[12] It is used in the Duff reaction (formylation of arenes),[13] the Sommelet reaction (converting benzyl halides to aldehydes),[14] and in the Delepine reaction (synthesis of amines from alkyl halides).[15]
Explosives
Hexamethylenetetramine is the base component to produce RDX and, consequently, C-4[4] as well as Octogen, hexamine dinitrate, hexamine diperchlorate and HMTD.
Historical uses
Hexamethylenetetramine was first introduced into the medical setting in 1899 as a urinary antiseptic.[16] However, it was only used in cases of acidic urine, whereas boric acid was used to treat urinary tract infections with alkaline urine.[17] Scientist De Eds found that there was a direct correlation between the acidity of hexamethylenetetramine’s environment and the rate of its decomposition.[16] Therefore, its effectiveness as a drug depended greatly on the acidity of the urine rather than the amount of the drug administered.[17] In an alkaline environment, hexamethylenetetramine was found to be almost completely inactive.[17]
Hexamethylenetetramine was also used as a method of treatment for soldiers exposed to phosgene in World War I. Subsequent studies have shown that large doses of hexamethylenetetramine provide some protection if taken before phosgene exposure but none if taken afterwards.[18]
Producers
Since 1990 the number of European producers has been declining. The French SNPE factory closed in 1990; in 1993, the production of hexamethylenetetramine in Leuna, Germany ceased; in 1996, the Italian facility of Agrolinz closed down; in 2001, the UK producer Borden closed; in 2006, production at Chemko, Slovak Republic, was closed. Remaining producers include INEOS in Germany, Caldic in the Netherlands, and Hexion in Italy. In the US, Eli Lilly and Company stopped producing methenamine tablets in 2002.[9] In Australia, Hexamine Tablets for fuel are made by Thales Australia Ltd. In México, Hexamine is produced by Abiya.
methenamine
Hexamethylenetetramine
100-97-0
Hexamine
Urotropine
Aminoform
Urotropin
Hexamethylenamine
1,3,5,7-Tetraazaadamantane
Methenamin
HMTA
Hexamethylenetetraamine
Hexamethylene tetramine
Formamine
Uritone
Aminoformaldehyde
Ammonioformaldehyde
Ammoform
Antihydral
Cystamin
Cystogen
Duirexol
Hexaform
Hexaloids
Metramine
Resotropin
Uratrine
Urodeine
Xametrin
Formin
Heterin
Hexasan
Uramin
Preparation AF
Hexamethyleneamine
Hexilmethylenamine
Hexa-Flo-Pulver
Ekagom H
methenaminum
Aceto HMT
Herax UTS
Hexamethylentetramin
Metenamina
Hexaminum
Formin (heterocycle)
Nocceler H
Sanceler H
1,3,5,7-Tetraazatricyclo[3.3.1.13,7]decane
Hexamine (heterocycle)
Vulkacit H 30
Hexamethylentetraminum
Hexamethylentetramine
Hexasan (VAN)
Mandelamine
S 4 (heterocycle)
Hexamethylenetetraminum
Uro-phosphate
1,3,5,7-tetraazatricyclo[3.3.1.1~3,7~]decane
Esametilentetramina
Metenamine
Methamin
Vesaloin
Hexa (vulcanization accelerator)
UNII-J50OIX95QV
1,3,5,7-Tetraazatricyclo (3.3.1.1(3,7))decane
HMT
Hexamine (JAN)
Hexamine (TN)
Hexamethylenetetramine (aliphatic)
Methenamine (USP/INN)
MFCD00006895
1,3,5,7-Tetraazatricyclo(3.3.1.13,7)decane
J50OIX95QV
1,3,5,7-Tetraazatricyclo(3.3.1.1(sup 37))decane
CHEBI:6824
H.M.T.
Formin (the heterocyclic compound)
NSC26346
1,3,5,7-tetraazatricyclo[3.3.1.1^{3,7}]decane
NSC-26346
1,3,5,7-Tetraazatricyclo(3.3.1.1(sup 3,7))decane
NCGC00094719-04
E239
Hexamine Silver
DSSTox_CID_692
Hexamethylenetetramine-palladium chloride adduct
Methenamine Silver
Silver Methenamine
DSSTox_RID_75739
Hexamethylenetetramine, 99%
1,3,5,7-tetraazatricyclo[3.3.1.1?,?]decane
DSSTox_GSID_20692
1,3,5,7-Tetraazatricyclo[3.3.1.1(3,7)]decane
Caswell No. 482
Methenamine [USAN:INN]
Sanceler HT
Metenamina [INN-Spanish]
Methenaminum [INN-Latin]
Heksa K
Hexamine Superfine
Nocceler H-PO
Sanceler HT-PO
Hexa B
1,3,5,7-Tetraazatricyclo(3.3.1.13,7)decane hydroiodide
CAS-100-97-0
Esametilentetramina [Italian]
Hexamethylentetramin [German]
SMR000857139
Cohedur H 30
CCRIS 2297
HSDB 563
hexamethylene-tetramine
NSC403347
Rhenogran HEXA 80
Thixon 715B
Methenamine, >26% in a non hazardous diluent
NSC-403347
1,3,5,7-Tetraazotricyclo[3.3.1.13,7]decane
SR-05000002024
Methenamine [USP:INN]
1,3,5,7-tetraazatricyclo[3.3.1.1<3,7>]decane
1,3,5,7-Tetraazatricyclo[3.3.1.1{3,7}]decane
EINECS 202-905-8
NSC 26346
UN1328
1,3,5,7-Tetraazatricyclo[3.3.1.1(sup 3,7)]decane
EPA Pesticide Chemical Code 045501
NSC 403347
Hexamethylenetetramine, 98.5%, contains an anticaking agent
Hexamethylamine
Naphthamine
Vesalvine
Urisol
Carin
EL 10 (corrosion inhibitor)
Hexamethylenetetramine solutions
AI3-09611
Methenamine-d12
HEXAMETHYLENETETRAMINE, ACS
EL 10
Prestwick_79
Vulkacit H30
1,3,5,7-Tetraazatricyclo[3.3.1.13,7 ]decane
Grasselerator 102
Cystex (Salt/Mix)
hexam-ethylenetetraamine
hexamethylene tetraamine
PubChem20918
Spectrum_000991
ACMC-20ahs9
Methenamine (Mandelamine)
Formaldehyde-ammonia 6:4
[16]-Adamazane, INN
component of Uro-Phosphate
Uro-phosphate (Salt/Mix)
1,5,7-Tetraazaadamantane
EC 202-905-8
Hexamethylentetramin(german)
Hexamethylenetetramine, 8CI
SCHEMBL33785
BSPBio_003380
Hexamethylenetetramine, tech.
KBioGR_001563
KBioSS_001471
Hexamethylenetetramine [UN1328] [Flammable solid]
Pharmakon1600-01500394
1,5,7-Tetraazatricyclo[3.3.1.13,7]decane
D00393
Hexamethylenetetramine, ACS reagent, >=99.0%
AB00052038_08
AB00052038_09
1,3,5,7-tetraaza-tricyclo[3.3.1.13,7]decane
1,3,5,7-tetraazatricyclo-[3.3.1.13,7]decane
1,3,5,7-tetraazatricyclo[3,3,1,13,7]decane
1,5:3,7-Dimethano-1,3,5,7-tetraazacyclooctane
AE-641/00560026
WLN: T66 B6 A B-C 1B I BN DN FN HNTJ
Hexamethylenetetramine [UN1328] [Flammable solid]
Hexamethylenetetramine, analytical reference material
Hexamethylenetetramine, p.a., ACS reagent, 99.0%
Hexamethylenetetramine, SAJ first grade, >=98.5%
J-000293
J-521456
SR-05000002024-1
SR-05000002024-3
1,3,5,7-tetraaza-tricyclo[3.3.1.1*3,7*]decane
1,3,5,7-Tetraazatricyclo-[3.3.1.1(3,7)]decane
BRD-K30114692-001-10-0
Hexamethylenetetramine, JIS special grade, >=99.0%
F2173-0429
Z362014242
Methenamine, European Pharmacopoeia (EP) Reference Standard
Methenamine, United States Pharmacopeia (USP) Reference Standard
Hexamethylenetetramine, anhydrous, free-flowing, Redi-Dri(TM), ACS reagent, >=99.0%
67931-01-5
Hexamethylenetetramine, meets analytical specification of Ph.??Eur., BP, 99-100.5% (calc. to the dried substance)
Hexamethylenetetramine, puriss. p.a., Reag. Ph. Eur., >=99.5% (calc. to the dried substance)
Hexamethylenetetramine preserves food products such as fish and marinated mussels. It hydrolysed in acidic medium to produce formaldehyde, which is a broad-spectrum antimicrobial agent. However, its relatively high toxicity limits its application to provolone cheese. It can be easily determined by acidification of an aqueous extract, followed by a characteristic reaction, for instance, with chromotropic acid and subsequent spectrophotometry at 570 nm.
Nisin is a polypeptide bacteriocin that exhibits antibacterial activity against a wide range of Gram-positive bacteria. It is permitted to use in cream products, beer, salad dressings, cheese and cheese products, and so on. The determination of nisin in foods is typically carried out using immunoassay or bioassay. Recently, chromatographic method involving LC-MS/MS has been developed for this additive.
Natamycin has a polyene structure and is a naturally occurring antifungal agent produced during fermentation by the bacterium Streptomyces natalensis. It is used to protect food from mold and yeast growth. The EFSA approved the usage of this substance only as a surface preservative for dried cured sausages and semihard/semisoft cheese. It should not present at a depth of 5 mm or more, and the surface layer of the aforementioned products should not contain more than 1 mg dm− 2.
hexamethylenetetramine (CHEBI:6824) has role antibacterial drug (CHEBI:36047)
hexamethylenetetramine (CHEBI:6824) is a polyazaalkane (CHEBI:39474)
hexamethylenetetramine (CHEBI:6824) is a polycyclic cage (CHEBI:33640)
hexamethylenetetramine (CHEBI:6824) is a tetramine (CHEBI:39166)
Incoming quaternium-15 (CHEBI:59607) has functional parent hexamethylenetetramine (CHEBI:6824)
IUPAC Name
1,3,5,7-tetraazaadamantane
INNs Sources
metenamina Español
méthénamine Français ChEBI
methenamine
methenaminum LINGUA LATINA
Synonyms
1,3,5,7-tetraazatricyclo[3.3.1.13,7]decane
hexamethylenamine
hexamethylene tetramine
hexamethylenetetramine
Hexamethylentetramin Deutsch
hexamethylentetraminum LINGUA LATINA
hexamine
hexaminum
HMT
HMTA
ACETO HMT
AMINOFORM
AMMOFORM
AMMONIOFORMALDEHYDE
ANTIHYDRAL
CYSTOGEN
DUIREXOL
EKAGOM H
FORMAMINE
FORMIN
FORMIN (HETEROCYCLE)
HA
HERAX UTS
HETERIN
HEXA
HEXA (VULCANIZATION ACCELERATOR)
HEXA-FLO-PULVER
HEXAFORM
HEXAMETHYLENAMINE
HEXAMETHYLENETETRAMINE
HEXAMINE
HEXAMINE (HETEROCYCLE)
HEXASAN
HMT
METHENAMIDE
METHENAMIN
METHENAMINE
METHENEAMINE
NOCCELER H
PREPARATION AF
S 4
S 4 (HETEROCYCLE)
SANCELER H
1,3,5,7-TETRAAZAADAMANTANE
URAMIN
URATRINE
URITONE
URODEINE
UROTROPIN
VULKACIT H 30
XAMETRIN
Hexamethylenetetramine as a reagent has been used as a source of –CH=N– and –CH= functions.
Hexamethylenetetramine has a cage-like structure and is considered to be a crucial basic material for the chemical industry.
Hexamethylenetetramine has been used in many fields including as a curing agent for phenolic resins (1), as an accelerant in vulcanisation (2), in food preservatives (3) and explosives (4) because of its useful properties including high solubility in water and polar organic solvents (5).
In addition, Hexamethylenetetramine can act as a multifunctional ligand, using its N atom to form coordination complexes with many transition metals (6–10).
Hexamethylenetetramine has been employed to prepare complexes with metals, and has been increasingly applied in chemical synthesis where it has received increasing attention due to its simple operation, mild conditions and environmental
• 1,3,5,7-Tetraazaadamantane
• 1,3,5,7-Tetraazatricyclo(3.3.1.1(3,7))decane
• 1,3,5,7-Tetraazatricyclo(3.3.1.1(sup 3,7))decane
• 1,3,5,7-Tetraazatricyclo(3.3.1.1(sup 37))decane
• AI3-09611
• Aceto HMT
• Aminoform
• Aminoformaldehyde
• Ammoform
• Ammonioformaldehyde
• Antihydral
• CCRIS 2297
• Caswell No. 482
• Cystamin
• Cystogen
• Duirexol
• EINECS 202-905-8
• EPA Pesticide Chemical Code 45501
• Ekagom H
• Esametilentetramina
• Esametilentetramina [Italian]
• Formamine
• Formin
• Formin (heterocycle)
• HMT
• HSDB 563
• Herax UTS
• Heterin
• Hexa (vulcanization accelerator)
• Hexa-Flo-Pulver
• Hexaform
• Hexaloids
• Hexamethylenamine
• Hexamethyleneamine
• Hexamethylenetetraamine
• Hexamethylenetetramine
• Hexamethylenetetraminum
• Hexamethylentetramin
• Hexamethylentetramin [German]
• Hexamethylentetramine
• Hexamethylentetraminum
• Hexamine
• Hexamine (heterocycle)
• Hexaminum
• Hexasan
• Hexasan (VAN)
• Hexilmethylenamine
• Metenamina
• Metenamina [INN-Spanish]
• Methenamin
• Methenamine
• Methenaminum
• Methenaminum [INN-Latin]
• Metramine
• NSC 26346
• NSC 403347
• Nocceler H
• Preparation AF
• Resotropin
• S 4 (heterocycle)
• Sanceler H
• Uramin
• Uratrine
• Uritone
• Urodeine
• Urotropin
• Urotropine
• Vulkacit H 30
• Xametrin
Chemical Properties
Hexamethylenetetramine has an adamantane structure with high degree of symmetry and the characteristics of tertiary amines.
Each of the four nitrogen atoms has a pair of unshared electron with being able to form coordination compound with many kinds of inorganic compounds.
It can have heating reaction with strong inorganic acid to generate formaldehyde and ammonium salts.
In the presence of zinc powder, it can have reaction with hydrochloric acid to generate the hydrochloride salt of trimethylamine and ammonium chloride.
It can also be subject to nitrification and generate RDX.
It can also have reaction with nitrous acid to form N’N’-Dinitroso pentamethylene tetramine.
It can have reaction with hydrogen peroxide and hydrogen cyanide.
It can also have reaction with sulfur and sulfur compounds or react with the alkali metal salts, alkaline earth metal, and rare earth metal salts to form a complex.
In acidic medium, it can react with alcohol. It can also react with organic acid to form salt.
It can also react with halides, phenols and amides as well as some natural products such as protein and fiber.
It is irritating to the skin and can cause dermatitis. Intravenous-Rats LD50: 1200 mg/kg; Intraperitoneal injection-mice LD50: 512mg/kg.
the formula of hexamethylenetetramine
Figure 1 is the formula of hexamethylenetetramine
Pharmacological effects
It is a therapeutic drug for treating the bacterial urinary tract infections.
Hexamethylenetetramine itself has no antibacterial effect. After oral absorption, it can be secreted out by renal with being broken down into ammonia and formaldehyde in acidic urine with the later one being able to effectively inhibit the G-bacteria, especially having a strong antibacterial effect on Escherichia coli, Enterobacter aerogenes and Pseudomonas aeruginosa. It can be used for treating urinary tract infections caused by susceptible strains. When it is subject to oral administration, the patients should also take vitamin C or ammonium chloride at the same time in order to acidify the urine (pH≤5.5).
Chemical Properties
It is white hygroscopic crystalline powder or shiny colorless rhombic crystals.
It is almost odorless with sweet and bitter taste. It is soluble in water and chloroform but less soluble in carbon tetrachloride, acetone, benzene and ether and insoluble in petroleum ether.
The above information is edited by the Chemicalbook of Dai Xiongfeng.
Uses
It can be used as the curing agent for resins and plastics, the vulcanization accelerator of rubber (accelerator H) and textiles shrink-proof agent.
It can also be used for making antibacterial drug, explosives and so on.
As medicine, after oral administration, it can be decomposed when coming across acidic urine to generate formaldehyde and exerts its antibacterial effect used for treating mild urinary tract infection; it can be externally used for treating ringworm, antiperspirants, and treatment of underarm odor.
Its being mixed with caustic soda and sodium phenol can be used as the phosgene absorber of gas masks.
It can be used as a kind of anti-microbial agents.
It can be used as anti-shrinking textile finishing agent, bleaching agents of sodium chlorite and the buffer of waterproofing agents CR.
Hexamethylenetetramine is mainly used as the curing agent of plastic and resin, the catalyst and foaming agent of aminoplast, rubber vulcanization accelerator (accelerator H), and the shrink-proof agents of textiles. Hexamethylenetetramine is the raw material for organic synthesis and can be used for the production of chloramphenicol in the pharmaceutical industry.
Hexamethylenetetramine can be used as the disinfectant of urinary system with itself having no antibacterial effect and being effective in treating gram-negative bacteria.
Its 20% solution can be used for the treatment of underarm odor, sweaty feet, tinea and so on.
Its being mixed with caustic soda and sodium phenol can be used as the phosgene absorber of gas masks.
It can also be used for the manufacture of pesticides. Hexamethylenetetramine can react with fuming nitric acid to obtain highly explosive cyclonite, briefly referred as RDX. Hexamethylenetetramine can be used as the reagent and chromatography reagents for determination of bismuth, indium, manganese, cobalt, thorium, platinum, producing magnesium, lithium, copper, uranium, beryllium, tellurium, bromide, and iodide.
In the liver function tests, it can be used for formulating thymol turbidity, test and measurement of object such as bismuth, iron, manganese, cobalt, thorium, platinum and magnesium as well as the determination and identification of lithium, iron cyanide, iron bromide and iodide.
It can also be used for the determination of copper, uranium, beryllium, tellurium etc.
Moreover, it can be used as gas chromatography fixed solution (maximum usage temperature of 180 ℃ with the solvent being chloroform).
Production method
It can be made from the condensation reaction of formaldehyde and ammonia. Place the formaldehyde solution in a reactor, put through the ammonia with condensation reaction being carried out in alkaline solution and the reaction temperature being maintained at 50-70 ℃; the material liquid was cooled and fed into the film vacuum evaporator and subject to evaporation at 60-80 ℃ to make its concentration be increased from 24% to 38%-42%. Then the reaction mixture was filtered and subjected to vacuum evaporation and crystallization, filtration drying to derive the hexamethylenetetramine product.
Put the formaldehyde (37% aqueous solution) and excess amount of ammonia for 3 h at 38 ℃.
After completion of reaction, the reaction mixture was further subject to clarification, filtration, membrane evaporation (pressure 9.806~9.866 kPa) for twice with concentrated liquid subjecting cooling and crystallization, filtration, and drying at 150 ℃ to obtain the products. It is obtained through the reaction between formaldehyde and the calculated amount of ammonia.
Description
Hexamethylenetetramine is a hardener in epoxy resins of the bisphenol A type and can also be used as an anticorrosive agent. It is a sensitizing agent in ceramics workers.
Chemical Properties
White or almost white, crystalline powder or colourless crystals.
Uses
Used in the treatment of urinary track infection.
Uses
antibacterial, tuberculostatic
Uses
Hexamethylenetetramine is a versatile reagent in organic synthesis.
It is used in the Duff reaction, the Sommelet reaction, and in the Delepine reaction.
Definition
ChEBI: A polycyclic cage that is adamantane in which the carbon atoms at positions 1, 3, 5 and 7 are replaced by nitrogen atoms.
Definition
A white crystalline organic compound made by condensing methanal with ammonia.
It is used as a fuel for camping stoves, in vulcanizing rubber, and as a urinary disinfectant.
Hexamine can be nitrated to make the high explosive cyclonite.
brand name
Uritone (Parke- Davis); Urotropin (Parke-Davis).
General Description
Odorless white crystalline powder or colorless lustrous crystals. Sublimes in a vacuum at about 505° F with some decomposition.
Solutions are strong bases (pH of 0.2 molar aqueous solution is 8.4).
Air & Water Reactions
Highly flammable. Burns readily on contact with a flame with a smokeless flame. Finely powdered dust is significant dust explosion hazard. Water soluble.
Reactivity Profile
Hexamethylenetetramine is hygroscopic. Hexamethylenetetramine is sensitive to exposure to heat.
Hexamethylenetetramine is incompatible with oxidizing agents. Hexamethylenetetramine is also incompatible with acids.
Hexamethylenetetramine reacts violently with sodium peroxide. Hexamethylenetetramine reacts explosively with 1-bromopentaborane(9) at temperatures above 194° F.
The complex with iodine deflagrates at 280° F. The 1:1 addition complex with iodoform has exploded at 352° F.
Hexamethylenetetramine is corrosive to some metals, such as aluminum and zinc .
Special Hazards of Combustion Products: Formaldehyde gas and ammonia may be given off when hot [USCG, 1999].
Hazard
Skin irritant. Flammable, dangerous fire risk.
Fire Hazard
Special Hazards of Combustion Products: Formaldehyde gas and ammonia may be given off when hot.
Pharmaceutical Applications
Methenamine (hexamine, hexamethylenetetraamine), under the name Urotropin, was successfully used in cystitis by the German physician Nicolaier in 1895.
It has no intrinsic antibacterial activity and owes its effect to decomposition in acid conditions to formaldehyde, which is non-specifically microbicidal, and ammonia.
It is often used in the form of organic acid salts, methenamine hippurate and methenamine mandelate, which have been claimed (unconvincingly) to keep the urinary pH low. Mandelic acid has some antibacterial activity in its own right and is sometimes given alone as a urinary antiseptic, usually as the calcium or ammonium salt.
Infection with urea-splitting organisms such as Proteus spp. causes the urine to become alkaline and methenamine is unsuitable for these infections.
Methenamine is absorbed from the gut and mainly excreted unchanged in the urine, achieving concentrations of around 2–60 mg/L, sufficient to inhibit most bacteria and yeasts.
Higher concentrations are achieved by the hippurate salt.
It is given in enteric-coated tablets to prevent the liberation of formaldehyde by gastric acid.
There is little breakdown in the blood and no systemic effect or toxicity.
Some patients complain of gastrointestinal upset or frequent and burning micturition.
Attempts to control these side effects with alkali will abolish the antibacterial effect of the drug.
Contact dermatitis and anterior uveitis have occasionally been encountered. Prolonged administration or high dosage may produce proteinuria, hematuria and bladder changes.
Methenamine should not be given to patients with acidosis, gout or hepatic insufficiency.
There have been fears about the potential carcinogenicity of formaldehyde.
Methenamine and its salts are unsuitable for the treatment of acute urinary tract infection.
Their main use, now largely supplanted by other agents, has been in the long-term prophylaxis of recurrent cystitis.
Contact allergens
Hexamethylenetetramine is used in the foundry, tire and rubber, and phenol formaldehyde resins industries and in other applications such as a hardener in epoxy resins Bisphenol A type and as an anticorrosive agent.
It is an ammonia and formaldehyde releaser sometimes used in topical medicaments and cosmetics
Clinical Use
A venerable drug used for the disinfection of acidic urine, methenamine is a low-molecular-weight polymer of ammonia and formaldehyde that reverts to its components under mildly acidic conditions. Formaldehyde is the active antimicrobial component.
Methenamine is used for recurrent urinary tract infections.
The drug is available in various dosage forms as well as various salts, including the hippurate and mandelate.
Carcinogenicity
No significantly increased incidence of tumors was observed in rats or mice given HMTA for their lifetimes.
Exposures in rats included 400 mg/day for 1 year, 10,000 ppm in drinking water for 2 years in each of three generations, 10,000 ppm in water for a lifetime (261), and up to 1000 ppm in the diet for 2 years.
In mice, testing conditions included up to 10,000 ppm in drinking water for 60 weeks or 50,000 ppm for 30 weeks and a lifetime holding period, and up to 10,000 ppm in the diet for 2 years.
Injection of 25–30 g subcutaneously per mouse led to an increase in subcutaneous sarcomas in two experiments (418, 419) but not in two other studies.
The relevance of this methodology to the workplace condition is questionable.
Purification Methods
It is soluble in H2O (67%), CHCl3 (10%), EtOH (8%) and Et2O (0.3%), and a 0.2M solution has a pH of 8.4.
Dissolve it in hot absolute EtOH (reflux, Norit), filter using a heated funnel, cool at room temperature first, then in ice.
Wash the crystals with cold Et2O, dry them in air or under a vacuum.
A further crop can be obtained by adding Et2O to the filtrate. It sublimes above 260o without melting.
The picrate has m 179o(dec). [pK2 0 4.85: Reilley & Schmid Anal Chem 30 947 1958, pK2 0 6.30: Pummerer & Hofmann Chem Ber 56 1255 1923.] [Beilstein 26 I 306, 26 II 200, 26 III/IV 1680.]
The inhibitive effect of hexamethylenetetramine on the acid corrosion of steel
The efficiency of hexamethylenetetramine (HMTA), as corrosion inhibitors for steel in de-aerated 0.3 M HCl, 0.1 M H2SO4 and 0.1 M H2SO4 + 1.0 × 10−3 M HCl solutions have been determined by electrochemical studies.
It was found that the HMTA acts a good corrosion inhibitor for steel corrosion in acids solutions.
Increase in inhibition efficiency with the increase of concentrations of HMTA shows that inhibition actions are due to adsorption on the steel surface and adsorption follows the Langmuir isotherm. From the adsorption isotherms values of equilibrium constant (Kads), values of free energies of adsorption (), were calculated.
The effect of temperature on the corrosion behaviour in the presence of 1.0 × 10−1 M inhibitors was studied in the temperature range of 293–323 K.
The inhibition efficiency of HMTA increased with increasing temperature up to 323 K.
Activation energies () were calculated from the obtained corrosion rates at different temperatures.
Results obtained from both potentiodynamic polarisation and AC impedance measurements reveal that the compound is an effective inhibitor for the corrosion of steel and behave better in HCl than in H2SO4.
Surface analyses were also carried out to establish the mechanism of corrosion inhibition of steel in acidic media.
HEXAMETHYLENETETRAMINE
hexamethylenetetramine
Methenamine
methenamine; hexamethylenetetramine
Translated names
1,3,5,7-tetraazaadamantan (cs)
1,3,5,7-tetraazaadamantan (pl)
1,3,5,7-tetraazatricyklo[3.3.1.13,7]dekan (pl)
esametilentetrammina (it)
eżametilentetrammina (mt)
heksametilentetramin (hr)
heksametilentetramin (sl)
heksametilentetraminas (lt)
heksametilēntetramīns (lv)
heksametyleenitetramiini (fi)
heksametylenotetraamina (pl)
heksametylentetramin (no)
heksametüleentetramiin (et)
heksamina (pl)
hexamethyleentetramine (nl)
hexamethylentetramin (cs)
hexamethylentetramin (da)
Hexamethylentetramin (de)
hexametilenotetramina (pt)
hexametilentetramina (es)
hexametilentetramină (ro)
hexametiléntetramin (hu)
hexametylentetramin (sv)
hexametyléntetramín (sk)
hexaméthylènetétramine (fr)
meteenamiin (et)
meteeniamiini (fi)
metenamin (hr)
metenamin (no)
metenamin (sl)
metenamin (sv)
metenamina (es)
metenamina (pt)
metenaminas (lt)
metenamină (ro)
metenammina (it)
metenammina (mt)
methenamin (cs)
methenamin (da)
Methenamin (de)
methenamine (nl)
meténamin (hu)
metēnamīns (lv)
méthénaminehexaméthylènetétramine (fr)
urotropin (cs)
urotropina (pl)
urotropín (sk)
εξαμεθυλενοτετραμίνη (el)
μεθεναμίνη· (el)
метенамин (bg)
хексаметилентетрамин (bg)
CAS names
1,3,5,7-Tetraazatricyclo[3.3.1.13,7]decane
IUPAC names
1,3,5,7-Tetraazaadamantan
1,3,5,7-Tetraazaadamantane
1,3,5,7-tetraazatricyclo(3.3.1.1(sup37))decane
1,3,5,7-tetraazatricyclo[3,3,1,1. ]decane
1,3,5,7-Tetraazatricyclo[3.3.1.1 3,7]decane
1,3,5,7-Tetraazatricyclo[3.3.1.1(3,7)]decane
1,3,5,7-tetraazatricyclo[3.3.1.1(3,7)]decane
1,3,5,7-Tetraazatricyclo[3.3.1.1.(3,7)]decane
1,3,5,7-Tetraazatricyclo[3.3.1.13,7]decane
1,3,5,7-tetraazatricyclo[3.3.1.13,7]decane
1,3,5,7-Tetraazatricyclo[3.3.1.1^(3,7)]decane
1,3,5,7-tetraazatricyclo[3.3.1.1^{3,7}]decane
1,3,5,7-tetraazatricyclo[3.3.1.1~3,7~]decane
1,3,5,7-tetraazatricyclo[3.3.1.1³,7]decane
1,3,5,7-Tetraazatricyclodecane
1,3,5,7-tetraazotriciklo-(3.3.1.1)dekanas; metenaminas
HEXA
HEXAMETHYLENE TETRAMINE
Hexamethylene tetramine
Hexamethylenetetramine
hexamethylenetetramine methenamine
Hexamethylenetetramine, Hexamine
hexamethylenetretramine
Hexametilén-tetramin
HEXAMINE
Methamine
Methenamin
METHENAMINE
Methenamine
methenamine
Methenamine
methenamine
methenamine; hexamethylenetetramine
MethenamineHexamethylenetetramine
Trade names
Aminoform
Formine
Hexamethylene Tetramine
Hexamethylenetetramine
Hexamethylentetramin grobkristallin
Hexamethylentetramin kristallin
Hexamethylentetramine
Hexamine
Methenamin p.a. (R)
Methenamine
methenamine
Stabilised Hexamine, HMT
Uritone
Urizole
Urotropine
Urotropine technical
Urotropine technical stabilized
Hexamethylenetetramine is used for various applications such as curing accelerators for thermosetting resins and raw materials for pharmaceuticals.
However, when river water containing hexamethylenetetramine is chlorinated at a water treatment plant, it is known to change into toxic formaldehyde.
Therefore a highly sensitive analytical method for hexamethylenetetramine is required.
As hexamethylenetetramine has high polarity, retention is weak in reverse phase mode, and traditional methods require derivatization or the use of ion pair agents.
Also called methenamine, it is a white crystalline solid. It is moderately soluble in water and is very soluble in most organic solvents.
It is a heterocyclic organic compound that can be prepared by a reaction of formaldehyde and ammonia. Uses: As an antibiotic, solid food tablet for cooking, in the production of other compounds, in rubber and textile adhesives, paints, lacquers, in the production of explosives, and as a corrosion inhibitor. CAS# (100-97-0)
Hexamethylenetetramine is used as a catalyst in the synthesis of phenol, melamine and urea-formaldehyde based resins and as a curing agent in the preparation of novolac phenolic resin systems.
These resins are versatile synthetic materials with outstanding mechanical properties, bonding performance,chemical and water resistance and flame retardancy
Other uses of Hexamethylenetetramine in Personal care: A formaldehyde donor at use levels of 0.01-1.0 phr
• Cosmetics, foot cream and deodorants as an antibacterial and fungicidal agent
• Hair dye fixative as a preservative in Curing agent for rubber and epoxy: Use levels of 0.5-2.5 phr
• High-temperature accelerators with medium to long curing ranges and slow curing rates, preventing early stage rubber sagging
• Secondary accelerators to control curing rates such as mercapto, sulphenamide, thiuram and dithiocarbamate
In Combustion: As a fuel additive in combustible solid fuel cubes and in RDX for the explosive industry
In Adhesives: In elastic glues as an adhesion promoter for direct bonding of
• Rubber-to-fabric
• Rubber-to-metal (steel cords)
In Intermediate: For the synthesis of chelating agents and other agro compounds
In Food additives: As a cheese preservative and fungicide for citrus fruits
In Medical: As a methenamine mandelate and hippurate treatment of urinary tract infections
In Rubber: The manufacturing of dinitrosopentamethylene-tetramine, a blowing agent for rubber
Hexamine [JAN]
1,3,5,7-Tetraazatricyclo[3.3.1.13,7]decan [German] [ACD/IUPAC Name]
1,3,5,7-Tetraazatricyclo[3.3.1.13,7]decane [ACD/Index Name] [ACD/IUPAC Name]
1,3,5,7-Tétraazatricyclo[3.3.1.13,7]décane [French] [ACD/IUPAC Name]
1,3,5,7-Tetraazatricyclo[3.3.1.13,7]decane
100-97-0 [RN]
202-905-8 [EINECS]
hexamethylene tetramine
Hexamethylenetetramine [Wiki]
Hexamethylentetramin [German]
HMT
HMTA
metenamina [Spanish] [INN]
methenamine [INN] [USAN] [USP]
Méthénamine [French] [INN]
methenaminum [Latin] [INN]
MFCD00006895 [MDL number]
Urotropin
Urotropine
Гексаметилентетрамин [Russian]
метенамин [Russian] [INN]
ميثينامين [Arabic] [INN]
乌洛托品 [Chinese] [INN]
1,3,5,7-tetraazaadamantane
1,3,5,7-Tetraazatricyclo(3.3.1.1(3,7))decane
1,3,5,7-Tetraazatricyclo(3.3.1.1(sup 3,7))decane
1,3,5,7-Tetraazatricyclo(3.3.1.13,7)decane
1,3,5,7-tetraazatricyclo[3.3.1.1(3,7)]decane
1,3,5,7-Tetraazatricyclo-[3.3.1.1(3,7)]decane
1,3,5,7-Tetraazatricyclo[3.3.1.1(sup 3,7)]decane
1,3,5,7-Tetraaza-tricyclo[3.3.1.1*3,7*]decane
1,3,5,7-tetraazatricyclo[3.3.1.1,3,7]decane
1,3,5,7-tetraazatricyclo[3.3.1.13,7]decane
1,3,5,7-Tetraazatricyclo[3.3.113,7]decane
1,3,5,7-Tetraazatricyclodecane
1,3,5,7-Tetraazotricyclo[3.3.1.13,7]decane
11103-67-6 secondary RN [RN]
15978-33-3 secondary RN [RN]
23304-08-7 [RN]
24911-88-4 [RN]
56549-34-9 secondary RN [RN]
74734-16-0 secondary RN [RN]
91773-48-7 secondary RN [RN]
Aceto HMT
Aminoform
Aminoformaldehyde
Ammoform
Ammonioformaldehyde
Antihydral
Cystamin
Cystogen
DB06799
decane, 1,3,5,7-Tetraazatricyclo(3.3.1.13,7)
Duirexol
E239
Ekagom H
Esametilentetramina [Italian]
Formamine
Formin [Trade name]
Grasselerator 102
Herax UTS
Heterin
Hexa-Flo-Pulver
Hexaform
Hexaloids
Hexamethylamine
hexamethylenamine
Hexamethyleneamine
Hexamethylenetetraamine
Hexamethylenetetramine, Hexamine, Formin, Urotropin
Hexamethylenetetraminum
Hexamethylentetramin
Hexamethylentetramine
hexamethylentetraminum
Hexamine Silver
hexaminum
Hexasan
Hexilmethylenamine
Hiprex [Trade name]
https://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:6824
Mandelamine [Trade name]
Metenamina
Metenamine
Methamin
Methenamin
méthénamine
Metramine
Naphthamine
Nocceler H
Preparation AF
Resotropin
Sanceler H
STR00289
T66 B6 A B-C 1B I BN DN FN HNTJ [WLN]
Tetraazaadamantane
Uramin
Uratrine
Urex [Trade name]
Urisol
Uritone
Urodeine
Urotropine 100 µg/mL in Methanol
Urotropine 100 µg/mL in Methanol
Vesaloin
Vesalvine
Vulkacit H 30
Vulkacit H30
Xametrin
метенамин
ميثينامين
乌洛托品
Hexamethylenetetramine, also known as methenamine, hexamine, or urotropin, is a heterocyclic organic compound with the formula (CH2)6N4. This white crystalline compound is highly soluble in water and polar organic solvents. It has a cage-like structure similar to adamantane. It is useful in the synthesis of other organic compounds, including plastics, pharmaceuticals, and rubber additives. It sublimes in vacuum at 280 °C.
Synthesis, structure, reactivity
Hexamethylenetetramine was discovered by Aleksandr Butlerov in 1859.
It is prepared industrially by combining formaldehyde and ammonia.
The reaction can be conducted in gas phase and in solution.
Also called methenamine, it is a white crystalline solid. It is moderately soluble in water and is very soluble in most organic solvents. It is a heterocyclic organic compound that can be prepared by a reaction of formaldehyde and ammonia. Uses: As an antibiotic, solid food tablet for cooking, in the production of other compounds, in rubber and textile adhesives, paints, lacquers, in the production of explosives, and as a corrosion inhibitor. CAS# (100-97-0).
Substance name:Hexamethylenetetramine
Trade name:Hexamine
EC no:202-905-8
CAS no:100-97-0
HS code:29336940
KH product code:100124
Formula:C6H12N4
Synonyms:1,3,5,7-tetraazaadamantane / 1,3,5,7-tetraazatricyclo[3.3.1.1(3,7)-]decane / 1,3,5,7- tetrazatricyclo(3.3.1.1*3.7)decane / aceto HMT (= aceto hexamethylenetetramine) / aminoform / aminoformaldehyde / ammoform / ammonioformaldehyde / amoform / antihydral / carin / cystamin / cystogen / duirexol / ekagom H / formaldehyde:ammonia 6:4 / formamine / formin / formine / herax UTS / heterin / hexa (= hexamethylenetetramine) / hexa-flo-pulver / hexaform / hexamethylenamine / hexamethyleneamine / Hexamethylenetetramine / hexasan /
hexilmethylenamine / HMT (= hexamethylenetetramine) / HMTA (= hexamethylenetetramine) / mandelamine / methamin / methenamine / metheneamine / metramine / naphthamine / preparation AF / resotropin / URAMIN / uratrine / urisol / uritone / urodeine / urotropin / urotropine / vesaloin / vesalvine / vulkacit H30 / xametrin / xametrine