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Revision as of 13:29, 15 February 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 472478602 of page Di-tert-butyl_dicarbonate for the Chem/Drugbox validation project (updated: '').		Latest revision as of 13:27, 21 November 2024 edit DMacks (talk | contribs)Edit filter managers, Autopatrolled, Administrators186,427 edits Removing from Category:Carbonate esters using Cat-a-lot
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		⚫	{{DISPLAYTITLE:Di-''tert''-butyl dicarbonate}}
	{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}}
	{{chembox		{{chembox
			| Watchedfields = changed
	| verifiedrevid = 443634376		| verifiedrevid = 477001173
⚫	| Name = Di-''tert''-butyl dicarbonate
	| ImageFile = Di-tert-butyl-dicarbonate-2D-skeletal.png		| Name = Di-''tert''-butyl dicarbonate
		⚫	| ImageFile = Di-tert-butyl-dicarbonate-2D-skeletal.png
	<!-- | ImageSize = 200px -->
	| ImageName =		| ImageSize =
			| ImageName =
⚫	| ImageFile1 = Di-tert-butyl-dicarbonate-3D-balls.png
	| IUPACName = Di-''t''-butyl dicarbonate		| ImageFile1 = Di-tert-butyl-dicarbonate-based-on-similar-xtals-3D-balls.png
	| OtherNames = di-''tert''-butyl pyrocarbonate<br />Boc anhydride<br />Boc<sub>2</sub>O		| PIN = Di-''tert''-butyl dicarbonate
			| OtherNames = Di-''t''-butyl pyrocarbonate<br />Boc anhydride<br />Boc<sub>2</sub>O
	| Section1 = {{Chembox Identifiers		| Section1 = {{Chembox Identifiers
	| ChEBI_Ref = {{ebicite|correct|EBI}}		| ChEBI_Ref = {{ebicite|correct|EBI}}
	| ChEBI = 48500		| ChEBI = 48500
	| SMILES = O=C(OC(=O)OC(C)(C)C)OC(C)(C)C		| SMILES = O=C(OC(=O)OC(C)(C)C)OC(C)(C)C
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}		| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChemSpiderID = 81704		| ChemSpiderID = 81704
			| EC_number = 246-240-1
	| PubChem = 90495		| PubChem = 90495
	| InChI = 1/C10H18O5/c1-9(2,3)14-7(11)13-8(12)15-10(4,5)6/h1-6H3		| InChI = 1/C10H18O5/c1-9(2,3)14-7(11)13-8(12)15-10(4,5)6/h1-6H3
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	| CASNo_Ref = {{cascite|correct|CAS}}		| CASNo_Ref = {{cascite|correct|CAS}}
	| CASNo = 24424-99-5		| CASNo = 24424-99-5
			| UNII_Ref = {{fdacite|correct|FDA}}
			| UNII = Z10Q236C3G
	}}		}}
	| Section2 = {{Chembox Properties		| Section2 = {{Chembox Properties
			| C=10|H=18|O=5
	| Formula = C<sub>10</sub>H<sub>18</sub>O<sub>5</sub>
		⚫	| Appearance = Colorless solid or oil
	| MolarMass = 218.25&nbsp;g&middot;mol<sup>&minus;1</sup>		| Density = 0.95&nbsp;g·cm<sup>&minus;3</sup>
⚫	| Appearance = colourless solid
		⚫	| Solubility = Insoluble
	| Density = 0.95&nbsp;g&middot;cm<sup>&minus;3</sup>
			| Solvent = other solvents
⚫	| Solubility = insol
	| Solvent = other solvents		| SolubleOther = Soluble in most organic solvents
			| MeltingPtC = 22 to 24
	| SolubleOther = most organic solvents
			| MeltingPt_notes =
	| MeltingPt = 22–24&nbsp;°C
			| BoilingPtC = 56 to 57
	| BoilingPt = 56–57&nbsp;°C (0.5&nbsp;mmHg)
			| BoilingPt_notes = (0.5&nbsp;mmHg)
	}}		}}
	| Section3 = {{Chembox Structure		| Section7 = {{Chembox Hazards
			| ExternalSDS =
	| Dipole = 0&nbsp;]
			| MainHazards = Very toxic on inhalation T+, LC<sub>50</sub> = 100 mg/m<sup>3</sup> (4 hr, rat)}}
	}}
	| Section7 = {{Chembox Hazards		| Section8 = {{Chembox Related
			| OtherCompounds = ]<br />]<br />]<br />]
	| ExternalMSDS =
	| MainHazards = toxic on inhalation T+
	}}
	| Section8 = {{Chembox Related
	| OtherCpds = ]<br />]
	}}		}}
	}}		}}
			'''Di-''tert''-butyl dicarbonate''' is a ] widely used in ].<ref>M. Wakselman, "Di-''t''-butyl Dicarbonate" in ''Encyclopedia of Reagents for Organic Synthesis'' (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. {{doi|10.1002/047084289X}}.</ref> Since this compound can be regarded formally as the acid anhydride derived from a ''tert''-butoxycarbonyl (Boc) group, it is commonly referred to as '''Boc anhydride'''. This ] reacts with ]s to give ] or so-called Boc derivatives. These carbamate derivatives do not behave as amines, which allows certain subsequent transformations to occur that would be incompatible with the amine ]. The Boc group can later be removed from the amine using moderately strong acids (e.g., ]). Thus, Boc serves as a ], for instance in ]. Boc-protected amines are unreactive to most bases and ]s, allowing for the use of the ] group (Fmoc) as an orthogonal protecting group.
			==Preparation==
			Di-''tert''-butyl dicarbonate is inexpensive, so it is usually purchased. Classically, this compound is prepared from ], ], and ], using ] as a base:<ref name=pope>{{cite journal| vauthors = Pope BM, Yamamoto Y, Tarbell DS |title=DI-tert-BUTYL DICARBONATE|journal=Organic Syntheses|volume=57|year=1977|pages=45|issn=0078-6209|doi=10.15227/orgsyn.057.0045}}</ref>
			]
			This route is currently employed commercially by manufacturers in China and India. European and Japanese companies use the reaction of ] with carbon dioxide, catalysed by ] or ]. This process involves a distillation of the crude material yielding a very pure grade.
			Boc anhydride is also available as a 70% solution in ] or ]. As boc anhydride may melt at ambient temperatures, its storage and handling is sometimes simplified by using a solution.
			==Protection and deprotection of amines==
			{{main article|tert-butyloxycarbonyl protecting group}}
			The Boc group can be added to the amine under aqueous conditions using di-''tert''-butyl dicarbonate in the presence of a base such as ]. Protection of the amine can also be accomplished in ] solution using ] (DMAP) as the base.<ref>{{ cite journal |author1=Yochai Basel |author2=Alfred Hassner | title = Di-''tert''-butyl Dicarbonate and 4-(Dimethylamino)pyridine Revisited. Their Reactions with Amines and Alcohols | journal = ] | year = 2000 | volume = 65 |issue=20 | pages = 6368–6380 | doi = 10.1021/jo000257f |pmid=11052078 }}</ref>
			Removal of the Boc in ]s can be accomplished with strong acids such as ] neat or in ] or with ] in ].<ref>{{cite journal|vauthors = Williams RM, Sinclair PJ, DeMong DE, Chen D, Zhai D|title=ASYMMETRIC SYNTHESIS OF N-tert-BUTOXYCARBONYL a-AMINO ACIDS. SYNTHESIS OF (5S,6R)-4-tert-BUTOXYCARBONYL-5,6-DIPHENYLMORPHOLIN-2-ONE|journal=Organic Syntheses|volume=80|year=2003|pages=18|issn=0078-6209|doi=10.15227/orgsyn.080.0018}}</ref><ref>{{cite journal |author1=E. A. Englund |author2=H. N. Gopi |author3=D. H. Appella | title = An Efficient Synthesis of a Probe for Protein Function: 2,3-Diaminopropionic Acid with Orthogonal Protecting Groups | journal = ] | year = 2004 | volume = 6 | pages = 213–215 | doi = 10.1021/ol0361599 | pmid = 14723531 | issue = 2}}</ref><ref>{{cite journal |author1=D. M. Shendage |author2=R. Fröhlich |author3=G. Haufe | title = Highly Efficient Stereoconservative Amidation and Deamidation of α-Amino Acids | journal = ] | year = 2004 | volume = 6 | pages = 3675–3678 | doi = 10.1021/ol048771l | pmid = 15469321 | issue = 21}}</ref> A complication may be the tendency of the ] intermediate to alkylate other nucleophiles; scavengers such as ] or ] may be used.<ref>{{cite journal | doi = 10.1111/j.1399-3011.1978.tb02896.x | title = Removal of t-Butyl and t-Butoxycarbonyl Protecting Groups with Trifluoroacetic acid | year = 1978 | last1 = Lundt | first1 = Behrend F. | last2 = Johansen | first2 = Nils L. | last3 = Vølund | first3 = Aage | last4 = Markussen | first4 = Jan | journal = International Journal of Peptide and Protein Research | volume = 12 | issue = 5 | pages = 258–268 | pmid = 744685}}</ref><ref>{{cite book | doi = 10.1002/9783527631827.ch1 | chapter = 1. Protection Reactions | author = Andrew B. Hughes |editor1=Vommina V. Sureshbabu |editor2=Narasimhamurthy Narendra | volume = 4 | title = Amino Acids, Peptides and Proteins in Organic Chemistry: Protection Reactions, Medicinal Chemistry, Combinatorial Synthesis| year = 2011 | pages = 1–97 | isbn = 9783527321032 }}</ref>
			Selective cleavage of the N-Boc group in the presence of other protecting groups is possible when using AlCl<sub>3</sub>.
			Reaction with ] in acetonitrile followed by methanol is a mild and versatile method of deprotecting Boc-protected amines.<ref>{{ cite journal |author1=Michael E. Jung |author2=Mark A. Lyster | title = Conversion of alkyl carbamates into amines via treatment with trimethylsilyl iodide | journal = ] | year = 1978 | pages = 315–316 | doi = 10.1039/C39780000315 | issue = 7 }}</ref><ref>{{ cite journal |author1=Richard S. Lott |author2=Virander S. Chauhan |author3=Charles H. Stammer | title = Trimethylsilyl iodide as a peptide deblocking agent | journal = ] | year = 1979 | pages = 495–496 | doi = 10.1039/C39790000495 | issue = 11 }}</ref><ref>{{ cite journal | doi = 10.1016/0040-4020(82)87002-6 | title= Iodotrimethylsilane—a versatile synthetic reagent| year = 1982 | last1 = Olah | first1 = G | last2 = Narang | first2 = S. C. | journal = ] | volume = 38 | issue = 15 | pages = 2225 }}</ref><ref>{{ cite journal |author1=Zhijian Liu |author2=Nobuyoshi Yasuda |author3=Michael Simeone |author4=Robert A. Reamer | title = ''N''-Boc Deprotection and Isolation Method for Water-Soluble Zwitterionic Compounds | journal = ] | year = 2014 | volume = 79 |issue=23 | pages = 11792–11796 | doi = 10.1021/jo502319z | pmid = 25376704 }}</ref>
			The use of ] as a ] scavenger in the presence of trifluoroacetic acid in ] has been shown to lead to increased yields, decreased reaction times, simple work-up and improved selectivity for the deprotection of ''t''-butyl ester and ''t''-butoxycarbonyl sites in protected amino-acids and peptides in the presence of other acid-sensitive protecting groups such as the ], ], ''O''- and ''S''-benzyl and ''t''-butylthio groups.<ref name="MehtaJaouhari1992">{{cite journal|last1=Mehta|first1=Anita|last2=Jaouhari|first2=Rabih|last3=Benson|first3=Timothy J.|last4=Douglas|first4=Kenneth T.|title=Improved efficiency and selectivity in peptide synthesis: Use of triethylsilane as a carbocation scavenger in deprotection of t-butyl esters and t-butoxycarbonyl-protected sites|journal=Tetrahedron Letters|volume=33|issue=37|year=1992|pages=5441–5444|issn=0040-4039|doi=10.1016/S0040-4039(00)79116-7}}</ref>
			==Other uses==
			The synthesis of ], an important bread aroma compound, starting from ] was accomplished using ''t''-boc anhydride.<ref>{{cite journal |author1=T. J. Harrison |author2=G. R. Dake | title = An Expeditious, High-Yielding Construction of the Food Aroma Compounds 6-Acetyl-1,2,3,4-tetrahydropyridine and 2-Acetyl-1-pyrroline | journal = ] | year = 2005 | volume = 70 | issue = 26 | pages = 10872–10874 | doi = 10.1021/jo051940a | pmid = 16356012}}</ref>
			(See ]). The first step in this reaction sequence is the formation of the ] from the reaction of the amide nitrogen with boc anhydride in ] using DMAP as a catalyst.
			:]
			Di-''tert''-butyl dicarbonate also finds applications as a polymer ] due to its decomposition into gaseous products upon heating.<ref>{{cite journal|last1=Wirth|first1=D.|title=Highly Expandable Foam for Lithographic 3D Printing|journal=ACS Appl. Mater. Interfaces|volume=12|issue=16|pages=19033–19043|date=8 April 2020|doi=10.1021/acsami.0c02683|pmid=32267677|s2cid=215603770 }}</ref><ref>{{cite book |last1=Wypych |first1=George |title=Handbook of Foaming and Blowing Agents - 1st Edition |date=20 February 2017 |publisher=ChemTec Publishing |isbn=978-1-895198-99-7 |pages=258 |edition=1st |url=https://www.elsevier.com/books/handbook-of-foaming-and-blowing-agents/wypych/978-1-895198-99-7 |accessdate=4 May 2020}}</ref>
			== Hazards ==
			Bottles of di-''tert''-butyl dicarbonate buildup of internal pressure in sealed containers caused by its slow decomposition to di-''tert''-butyl carbonate and ultimately ''tert-''butanol and CO<sub>2</sub> in the presence of moisture. For this reason, it is usually sold and stored in plastic bottles rather than glass ones.
			The main hazard of the reagent is its inhalational toxicity. Its median lethal concentration of 100&nbsp;mg/m<sup>3</sup> over 4 hours in rats<ref>{{Cite web|url=https://us.vwr.com/store/asset?assetURI=https://us.vwr.com/stibo/hi_res/eng_us/92/73/12019273.pdf|title=Material Safety Data Sheet|last=|first=|date=|website=|publisher=CHEM-IMPEX INTERNATIONAL INC|access-date=2016-09-10}}</ref> is comparable to that of ]<ref>{{Cite web|url=http://webwiser.nlm.nih.gov/getSubstanceData.do?substanceId=59&displaySubstanceName=Phosgene&STCCID=&UNNAID=&selectedDataMenuItemID=78|title=Phosgene|last=|first=|date=|website=Wireless Information System for Emergency Responders|publisher=US National Library of Medicine|access-date=2016-09-10}}</ref> (49&nbsp;mg/m<sup>3</sup> over 50 min in rats).
			==References==
			<references/>
			==External links==
			* {{cite journal | doi = 10.1055/s-2001-12350 | title = Imidazole and Trifluoroethanol as Efficient and Mild Reagents for Destruction of Excess Di-tert-butyl Dicarbonate | year = 2001 | last1 = Basel | first1 = Yochai | last2 = Hassner | first2 = Alfred | journal = Synthesis | volume = 2001 | issue = 4 | pages = 0550| s2cid = 97029361 }}
			{{DEFAULTSORT:Di-Tert-Butyl Dicarbonate}}
			]
			]
			]