1,4-Butanediol

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1,4-Butanediol
1,4-butanediol.svg
14bd3d.png
Identifiers
CAS number 110-63-4 YesY
ChemSpider 13835209 YesY
UNII 7XOO2LE6G3 YesY
EC-number 203-786-5
DrugBank DB01955
ChEMBL CHEMBL171623 YesY
RTECS number EK0525000
Jmol-3D images Image 1
Image 2
Properties[1][2]
Molecular formula C4H10O2
Molar mass 90.12 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)
Solubility in water Miscible
Solubility in ethanol Soluble
Refractive index (nD) 1.4460 (20 °C)
Hazards[2][3]
GHS pictograms Acute Tox. (oral) 4
GHS signal word WARNING
GHS hazard statements H302
GHS precautionary statements P264, P270, P301+312, P330, P501
EU Index not listed
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oil Health code 1: Exposure would cause irritation but only minor residual injury. E.g., turpentine Reactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogen Special hazards (white): no codeNFPA 704 four-colored diamond
Flash point 121 °C (250 °F; 394 K)(open cup)
Autoignition temperature 350 °C (662 °F; 623 K)
Related compounds
Related butanediols 1,2-Butanediol
1,3-Butanediol
2,3-Butanediol
Related compounds Succinaldehyde
Succinic acid
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 YesY (verify) (what is: YesY/N?)
Infobox references

1,4-Butanediol, colloquially known as BD, is the organic compound with the formula HOCH2CH2CH2CH2OH. This colorless viscous liquid is derived from butane by placement of alcohol groups at each end of the chain. It is one of four stable isomers of butanediol.

Synthesis[edit]

In its industrial synthesis, acetylene reacts with two equivalents of formaldehyde to form 1,4-butynediol. This type of acetylene-based process is illustrative of what is known as "Reppe chemistry", after German chemist Walter Reppe. Hydrogenation of 1,4-butynediol gives 1,4-butanediol.

LyondellBasell manufactures 1,4-butanediol in a multi-step process without the use of acetylene. First, propylene oxide is converted to allyl alcohol. The allyl alcohol is then hydroformylated to 4-hydroxybutyraldehyde. Hydrogenation of this aldehyde yields 1,4-butanediol.[4]

It is also manufactured 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.[5]

A biological route to BDO has been commerciallized that uses a genetically modified organism.[6] The biosynthesis proceeds via 4-hydroxybutyrate.

Industrial use[edit]

1,4-Butanediol is used industrially as a solvent 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.[7] At about 200 °C in the presence of soluble ruthenium catalysts, the diol undergoes dehydrogenation to form butyrolactone.[8]

World production of 1,4-butanediol was claimed to be about one million metric tons per year and market price is about 2,000 USD (1,600 EUR) per ton (2005). In 2013, worldwide production was claimed to be billions of lbs (consistent with approximately one million metric tons).[9]

Almost half of it is dehydrated to tetrahydrofuran to make fibers such as Spandex.[10] The largest producer is BASF.[11]

Health effects and use as a drug[edit]

FDA warning against products containing GHB and its prodrugs, such as 1,4-butanediol.

It is also used as a recreational drug known by some users as "One Comma Four", "One Four Bee" or "One Four B-D-O". It exerts effects similar to γ-hydroxybutyrate (GHB), which is a metabolic product of 1,4-butanediol.[12][13] Misuse has also resulted in addiction and death.[14]

Pharmacokinetics[edit]

1,4-Butanediol is converted into GHB 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.[15] While co-administration of ethanol and GHB already poses serious risks including death, co-administration of ethanol with 1,4-butanediol is likely to have even more potentially fatal risks. This is because the same enzymes are responsible for metabolizing alcohol so there is a strong chance of a dangerous drug interaction.[15][16] 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.[15]

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

Pharmacodynamics[edit]

1,4-Butanediol 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 that are not due to this conversion.[16] One should note that the study arrived at this conclusion based on the finding that 1,4-butanediol co-administered 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 acetaldehyde 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 in rats of 1,4-butanediol.[17] This contradicts the hypothesis that 1,4-butanediol having inherent alcohol-like pharmacological effects.

Like GHB, 1,4-butanediol is only safe 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 1,4-butanediol is not currently scheduled federally in the United States, a number of states have classified 1,4-butanediol as a controlled substance. Additionally, individuals have been prosecuted for 1,4-butanediol under the Federal Analog Act as substantially similar to GHB.[18] A federal case in New York in 2002 ruled that 1,4-butanediol could not be considered an analog of GHB under federal law,[19] but that decision was later overturned by the Second Circuit.[20] 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 1,4-butanediol. The toy consists of small beads that stick to each other by sprinkling water. 1,4-Butanediol was detected by GC-MS.[21] The production plant seems to have intended to cut costs by replacing less toxic 1,5-pentanediol with 1,4-butanediol. ChemNet China listed the price of 1,4 butanediol 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.[22]

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. .
  2. ^ a b 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 Risk Management Authority, retrieved 2009-08-29 
  4. ^ ACS Patent Watch - December 7, 2009, The American Chemical Society
  5. ^ Ashford's Dictionary of Industrial Chemicals (3rd ed.), 2011, p. 1517, ISBN 978-0-9522674-3-0 
  6. ^ http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO1&Sect2=HITOFF&d=PALL&p=1&u=%2Fnetahtml%2FPTO%2Fsrchnum.htm&r=1&f=G&l=50&s1=8067214.PN.&OS=PN/8067214&RS=PN/8067214
  7. ^ Karas., L.; Piel, W. J., "Ethers", Kirk-Othmer Encyclopedia of Chemical Technology, New York: John Wiley, ISBN 9780471238966 
  8. ^ 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 
  9. ^ "Commercial-scale production of bio-based BDO announced", Chemical Engineering, Feb 2013, retrieved 2013-02-21 
  10. ^ "Butanediol (price and demand in market)", Chemical Week, 12 April 2006, retrieved 2008-11-21 
  11. ^ "Malaysia: New 1,4-butanediol plant used below capacity", Asian Textile Business, April 2004, retrieved 2008-11-21 
  12. ^ Satta, Rosalba; Dimitrijevic, Nikola; Manev, Hari (2003), "Drosophila metabolize 1,4-butanediol into γ-hydroxybutyric acid in vivo", Eur. J. Pharmacol. 473 (2–3): 149–52, doi:10.1016/S0014-2999(03)01993-9, PMID 12892832 
  13. ^ Carai, Maurio A. M.; Colombo, Giancarlo; Reali, Roberta; Serra, Salvatore; Mocci, Ignazia; Castelli, M. Paola; Cignarella, Giorgio; Gessa, Gian Luigi (2002), "Central effects of 1,4-butanediol are mediated by GABAB receptors via its conversion into γ-hydroxybutyric acid", Eur. J. Pharmacol. 441 (3): 157–63, doi:10.1016/S0014-2999(02)01502-9, PMID 12063087 
  14. ^ Zvosec, Deborah L.; Smith, Stephan W.; McCutcheon, J. Rod; Spillane, Joe; Hall, Bradley J.; Peacock, Elizabeth A. (2001), "Adverse events, including death, associated with the use of 1,4-butanediol", New Engl. J. Med. 344 (2): 87–94, doi:10.1056/NEJM200101113440202, PMID 11150358 
  15. ^ a b c Benzer, Theodore I.; Cameron, Scott; Russi, Christopher Scott (8 January 2007), Toxicity, Gamma-Hydroxybutyrate, eMedicine, retrieved 2009-08-29 
  16. ^ a b Poldrugo, Flavio; Snead, O. Carter, III (1984), "1,4 Butanediol, γ-hydroxybutyric acid and ethanol: Relationships and interactions", Neuropharmacology 59 (23): 109–13, doi:10.1016/0028-3908(84)90226-0, PMID 6717752 
  17. ^ 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 
  18. ^ USA v Washam (2002) 312 F.3d 926, 930; http://cases.justia.com/us-court-of-appeals/F3/312/926/608696/
  19. ^ http://www.erowid.org/chemicals/14b/14b_law1.shtml
  20. ^ United States v. Roberts, 363 F.3d 118 (2d Cir. 2004); http://scholar.google.com/scholar_case?case=13457043198797192346&q=363+F.3d+118&hl=en&as_sdt=6,39
  21. ^ Wang, Linda (9 November 2007), "Industrial Chemical Sullies Popular Children's Toy", Chemical & Engineering News, retrieved 2009-08-11 
  22. ^ "US mother says her son began to stumble and vomit after eating Chinese-made toy, now recalled", Boston Herald (Associated Press), 8 November 2007 

External links[edit]