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1,4-Butanediol

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1,4-Butanediol
Names
Preferred IUPAC name
Butane-1,4-diol
Other names
Tetramethylene glycol
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.003.443 Edit this at Wikidata
EC Number
  • 203-786-5
RTECS number
  • EK0525000
UNII
  • InChI=1S/C4H10O2/c5-3-1-2-4-6/h5-6H,1-4H2 checkY
    Key: WERYXYBDKMZEQL-UHFFFAOYSA-N checkY
  • InChI=1/C4H10O2/c5-3-1-2-4-6/h5-6H,1-4H2
  • OCCCCO
  • C(CCO)CO
Properties[1][2]
C4H10O2
Molar mass 90.122 g·mol−1
Density 1.0171 g/cm3 (20 °C)
Melting point 20.1 °C (68.2 °F; 293.2 K)
Boiling point 235 °C (455 °F; 508 K)
Miscible
Solubility in ethanol Soluble
-61.5·10−6 cm3/mol
1.4460 (20 °C)
Hazards[3][4]
GHS labelling:
Acute Tox. (oral) 4
Warning
H302, H336
P261, P264, P270, P271, P301+P312, P304+P340, P312, P330, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1
1
0
Flash point (open cup) 121 °C (250 °F; 394 K)
350 °C (662 °F; 623 K)
Related compounds
Related butanediols
 1,2-Butanediol
1,3-Butanediol
2,3-Butanediol
cis-Butene-1,4-diol
Related compounds
 Succinaldehyde
Succinic acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

1,4-Butanediol, also called Butane-1,4-diol (other names include 1,4-B, BD, BDO and 1,4-BD),[5] is a primary alcohol and an organic compound with the formula HOCH2CH2CH2CH2OH. It is a colorless viscous liquid first synthesized in 1890 via acidic hydrolysis of N,N'-dinitro-1,4-butanediamine by Dutch chemist Pieter Johannes Dekkers, who called it "tetramethylene glycol".[6][7]

Synthesis

[edit]
Conversion of butane to butanediol or butyrolactone via oxidation to maleic anhydride followed by hydrogenation over copper chromite.[8]

In one industrial chemical synthesis, acetylene reacts with two equivalents of formaldehyde to form butyne-1,4-diol. Hydrogenation of butyne-1,4-diol gives butane-1,4-diol.[9] It is also made on an industrial scale from maleic anhydride in the Davy process, which is first converted to the methyl maleate ester, then hydrogenated. Other routes are from butadiene, allyl acetate and succinic acid.

A biological route to BD has been commercialized that uses a genetically modified organism.[10] The biosynthesis proceeds via 4-hydroxybutyrate.

Industrial use

[edit]

Butane-1,4-diol is used industrially as a solvent[additional citation(s) needed] and in the manufacture of some types of plastics, elastic fibers and polyurethanes. In organic chemistry, 1,4-butanediol is used for the synthesis of γ-butyrolactone (GBL). In the presence of phosphoric acid and high temperature, it dehydrates to the important solvent tetrahydrofuran.[11] At about 200 °C in the presence of soluble ruthenium catalysts, the diol undergoes dehydrogenation to form butyrolactone.[12] It is used to synthesize 1,4-Butanediol diglycidyl ether which is then used as a reactive diluent for epoxy resins.[13]

1,4-Butanediol is used in the production of polybutylene terephthalate (PBT) plastic.[14]

World production of butane-1,4-diol was claimed to be about one million metric tons per year and market price is about US$ 2,000 (€1,600) per ton (2005). In 2013, worldwide production was claimed to be billions of pounds (consistent with approximately one million metric tons).[15]

Almost half of it is dehydrated to tetrahydrofuran to make fibers such as Spandex.[16] The largest producer is BASF.[17]

Use as a recreational drug

[edit]
FDA warning against products containing GHB and its prodrugs, such as butane-1,4-diol.

Butane-1,4-diol is also used as a recreational drug known by some users as "Bute",[18] "One Comma Four", "Liquid Fantasy", "One Four Bee" or "One Four B-D-O".

Some federal courts in the USA have stated that 1,4-butanediol exerts effects similar to its metabolite, GABA analogue gamma-hydroxybutyrate (GHB), but several other federal courts have ruled that it does not.

Pharmacokinetics

[edit]

Butane-1,4-diol is rapidly converted into GHB acid by the enzymes alcohol dehydrogenase and aldehyde dehydrogenase, and differing levels of these enzymes may account for differences in effects and side effects between users.[19] While co-administration of ethanol and GHB already poses serious risks, co-administration of ethanol with 1,4-butanediol will interact considerably and has many other potential risks. This is because the same enzymes that are responsible for metabolizing alcohol also metabolize 1,4-butanediol so there is a strong chance of a dangerous drug interaction.[19][20] Emergency room patients who overdose on both ethanol and 1,4-butanediol often present with symptoms of alcohol intoxication initially and as the ethanol is metabolized the 1,4-butanediol is then able to better compete for the enzyme and a second period of intoxication ensues as the 1,4-butanediol is converted into GHB.[19]

Metabolic pathway of butane-1,4-diol, γ-butyrolactone and γ-hydroxybutyric acid (GHB).

Pharmacodynamics

[edit]

Butane-1,4-diol seems to have two types of pharmacological actions. The major psychoactive effects of 1,4-butanediol are because it is metabolized into GHB; however there is a study suggesting that 1,4-butanediol may have potential alcohol-like pharmacological effects on its own.[20] The study arrived at this conclusion based on the finding that butane-1,4-diol coadministered with ethanol led to potentiation of some of the behavioral effects of ethanol. However, potentiation of ethanol's effects may simply be caused by competition for the alcohol dehydrogenase and aldehyde dehydrogenase enzymes with co-administered 1,4-butanediol. The shared metabolic rate-limiting steps thus leads to slowed metabolism and clearance for both compounds including ethanol's known toxic metabolite acetaldehyde.

Another study found no effect following intracerebroventricular injection of butane-1,4-diol in rats.[21] This contradicts the hypothesis of butane-1,4-diol having inherent alcohol-like pharmacological effects.

Like gamma-hydroxybutyric acid, butane-1,4-diol is safe only in small amounts. Adverse effects in higher doses include nausea, vomiting, dizziness, sedation, vertigo, and potentially death if ingested in large amounts. Anxiolytic effects are diminished and side effects increased when used in combination with alcohol.

Legality

[edit]

While butane-1,4-diol is not currently scheduled federally in the United States,[22] a number of states have classified 1,4-butanediol as a controlled substance. Individuals have been prosecuted for possession of 1,4-butanediol under the Federal Analog Act as substantially similar to GHB.[23] A federal case in New York in 2002 ruled that 1,4-butanediol could not be considered an analog of GHB under federal law,[24] but that decision was later overturned by the Second Circuit.[25] A jury in Federal District Court in Chicago found that 1,4-butanediol was not an analog of GHB under federal law, which was not disputed on the case's appeal to the Seventh Circuit Court of Appeals, however this finding did not affect the outcome of the case.[26] In the United Kingdom, 1,4-butanediol was scheduled in December 2009 (along with another GHB precursor, gamma-butyrolactone) as a Class C controlled substance. In Germany, the drug is not explicitly illegal, but might also be treated as illegal if used as a drug. It is controlled as a Schedule VI precursor in Canada.

2007 contamination of Bindeez toy

[edit]
See also: Bindeez

A toy called "Bindeez" ("Aqua Dots" in North America) was recalled by the distributor in November 2007 because of the presence of butane-1,4-diol. The toy consists of small beads that stick to each other by sprinkling water. Butane-1,4-diol was detected by GC-MS.[27] The production plant seems to have intended to cut costs by replacing less toxic pentane-1,5-diol with butane-1,4-diol. ChemNet China listed the price of butane-1,4-diol at between about US$1,350–2,800 per metric ton, while the price for 1,5-pentanediol is about US$9,700 per metric ton.[28]

2021 poisoning at Darmstadt Technical University

[edit]

In August 2021, several people fell severely ill after consuming drinks at building L2.01 at the Lichtwiese Campus of Darmstadt Technical University, Germany. Seven showed severe symptoms, two were transported to a hospital in Frankfurt am Main, and a 30-year-old person was, for a time, in a critical state. Butane-1,4-diol had been detected in milk packages, as well as in water filters. At the location, detectives also found bromophenols and dicyclohexylamine.[29]

See also

[edit]

References

[edit]
  1. ^ Weast, Robert C., ed. (1981), CRC Handbook of Chemistry and Physics (62nd ed.), Boca Raton, FL: CRC Press, p. C-190, ISBN 0-8493-0462-8{{cite book}}: CS1 maint: overridden setting (link)
  2. ^ 1,4-Butanediol, International Chemical Safety Card 1104, Geneva: International Programme on Chemical Safety, March 1999
  3. ^ HSNO Chemical Classification Information Database, New Zealand Environmental Protection Authority
  4. ^ "1,4-Butanediol Laboratory Chemical Safety Summary"{{cite web}}: CS1 maint: overridden setting (link)
  5. ^ "1,4-Butanediol - Uses, Side Effects, and More", WebMD, retrieved 31 March 2024
  6. ^ Dekkers, M. P. J. (January 1890), "Le glycol tétraméthylénique", Recueil des Travaux Chimiques des Pays-Bas, 9 (4): 92–102, doi:10.1002/recl.18900090403, ISSN 0165-0513
  7. ^ Dekkers, Pieter Johannes (1890), Over het Tetramethyleenglycol: Proefschr. ... te verdedigen ... door Pieter Johannes Dekkers (in Dutch), L. van Nifterik Hz.
  8. ^ Rylander, Paul N. (2000), "Hydrogenation and Dehydrogenation", Ullmann's Encyclopedia of Industrial Chemistry, doi:10.1002/14356007.a13_487, ISBN 3-527-30673-0
  9. ^ "1,4-Butanediol Production And Uses", 30 July 2023, retrieved 30 July 2023
  10. ^ "United States Patent: 8067214 - Compositions and methods for the biosynthesis of 1,4-butanediol and its precursors", uspto.gov, retrieved 1 April 2018{{cite web}}: CS1 maint: overridden setting (link)
  11. ^ Karas, L.; Piel, W. J., "Ethers", Kirk-Othmer Encyclopedia of Chemical Technology, New York: John Wiley, doi:10.1002/0471238961, ISBN 9780471238966
  12. ^ Zhao, Jing; Hartwig, John F. (2005), "Acceptorless, neat, ruthenium-catalyzed dehydrogenative cyclization of diols to lactones", Organometallics, 24 (10): 2441–46, doi:10.1021/om048983m
  13. ^ Monte, Salvatore J. (1998), Pritchard, Geoffrey (ed.), "Diluents and viscosity modifiers for epoxy resins", Plastics Additives: An A-Z reference, Polymer Science and Technology Series, vol. 1, Dordrecht: Springer Netherlands, pp. 211–216, doi:10.1007/978-94-011-5862-6_24, ISBN 978-94-011-5862-6, retrieved 29 March 2022
  14. ^ "Polybutylene Terephthalate (PBT) Material Guide & Properties Info", omnexus.specialchem.com, archived from the original on 24 November 2023, retrieved 24 November 2023
  15. ^ "Commercial-scale production of bio-based BDO announced", Chemical Engineering, February 2013, archived from the original on 4 February 2015, retrieved 21 February 2013
  16. ^ "Butanediol (price and demand in market)", Chemical Week, 12 April 2006, retrieved 21 November 2008
  17. ^ "Malaysia: New 1,4-butanediol plant used below capacity", Asian Textile Business, April 2004, retrieved 21 November 2008
  18. ^ Australian Associated Press (30 May 2024), "Date-rape drug 'bute' increasingly linked to sexual assaults in Australia, police say", the Guardian, retrieved 30 May 2024
  19. ^ a b c Benzer, Theodore I.; Cameron, Scott; Russi, Christopher Scott (8 January 2007), Toxicity, Gamma-Hydroxybutyrate, eMedicine, retrieved 29 August 2009
  20. ^ a b Poldrugo, Flavio; Snead III, O. Carter (1984), "1,4-butanediol, γ-hydroxybutyric acid and ethanol: Relationships and interactions", Neuropharmacology, 23 (1): 109–13, doi:10.1016/0028-3908(84)90226-0, PMID 6717752, S2CID 54415695
  21. ^ Carter, LP; Koek, W; France, CP (2006), "Lack of effects of GHB precursors GBL and 1,4-BD following i.c.v. Administration in rats", The European Journal of Neuroscience, 24 (9): 2595–600, doi:10.1111/j.1460-9568.2006.05146.x, PMID 17100847, S2CID 24609982
  22. ^ "21 U.S. Code § 841 - Prohibited acts A", LII / Legal Information Institute, retrieved 2 August 2016{{cite web}}: CS1 maint: overridden setting (link)
  23. ^ USA v Washam (2002) 312 F.3d 926, 930; http://cases.justia.com/us-court-of-appeals/F3/312/926/608696/
  24. ^ "Erowid 1,4-Butanediol Vault : Law : New York Federal Court Rules Analogue Act Unconstitutionally Vague with regard to 1,4-Butanediol", www.erowid.org, retrieved 1 April 2018{{cite web}}: CS1 maint: overridden setting (link)
  25. ^ United States v. Roberts, 363 F.3d 118 (2d Cir. 2004); https://scholar.google.com/scholar_case?case=13457043198797192346&q=363+F.3d+118&hl=en&as_sdt=6,39
  26. ^ United States v. Turcotte, 405 F.3d 515 (7th Cir. 2005) "With specific regard to 1,4 Butanediol, the jury has returned a special verdict which states that 1,4-Butanediol is not a Schedule I Narcotic Drug Controlled Substance analogue, because 1,4-Butanediol's chemical structure is not significantly similar to the chemical structure of GHB.
  27. ^ Wang, Linda (9 November 2007), "Industrial Chemical Sullies Popular Children's Toy", Chemical & Engineering News, retrieved 11 August 2009
  28. ^ "US mother says her son began to stumble and vomit after eating Chinese-made toy, now recalled", Boston Herald, Associated Press, 8 November 2007
  29. ^ "Ermittler finden nach Vergiftungen an TU Darmstadt offenbar K.-o.-Tropfen in Küche", Stern, 27 August 2021, retrieved 1 September 2021{{cite web}}: CS1 maint: overridden setting (link)
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