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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2013/11/03 02:16:55」(JST)

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For other uses, see DCC (disambiguation).

N,N'-Dicyclohexylcarbodiimide is an organic compound with the chemical formula C₁₃H₂₂N₂ whose primary use is to couple amino acids during artificial peptide synthesis. Under standard conditions, it exists in the form of white crystals with a heavy, sweet odor. The low melting point of this material allows it to be melted for easy handling. It is highly soluble in dichloromethane, tetrahydrofuran, acetonitrile and dimethylformamide, but insoluble in water. The compound is often abbreviated DCC.

Structure and spectroscopy[edit]

The C-N=C=N-C core of carbodiimides (N=C=N) is linear, being related to the structure of allene. Three principal resonance structures describe carbodiimides:

RN=C=NR ↔ RN⁺≡C-N^-R ↔ RN^--C≡N⁺R

The N=C=N moiety gives characteristic IR spectroscopic signature at 2117 cm⁻¹.^[1] The ¹⁵N NMR spectrum shows a characteristic shift of 275.0 ppm upfield of nitric acid and the ¹³C NMR spectrum features a peak at about 139 ppm downfield from TMS.^[2]

Preparation[edit]

Of the several syntheses of DCC, Pri-Bara et al. use palladium acetate, iodine, and oxygen to couple cyclohexyl amine and cyclohexyl isocyanide.^[3] Yields of up to 67% have been achieved using this route:

C₆H₁₁NC + C₆H₁₁NH₂ + O₂ → (C₆H₁₁N)₂C + H₂O

Tang et al. condense two isocyanates using the catalyst OP(MeNCH₂CH₂)₃N in yields of 92%:^[1]

DCC has also been prepared from dicyclohexylurea using a phase transfer catalyst by Jaszay et al. The disubstituted urea, arenesulfonyl chloride, and potassium carbonate react in toluene in the presence of benzyl triethylammonium chloride to give DCC in 50% yield.^[4]

Reactions[edit]

DCC is a dehydrating agent for the preparation of amides, ketones, nitriles. In these reactions, DCC hydrates to form dicyclohexylurea (DCU), a compound that is insoluble in most organic solvents and in water and hence is readily removed by filtration. DCC can also be used to invert secondary alcohols.

Moffatt oxidation[edit]

A solution of DCC and dimethyl sulfoxide (DMSO) effects the so-called Pfitzner-Moffatt oxidation. This procedure is used for the oxidation of alcohols to aldehydes and ketones. Unlike metal-mediated oxidations, the reaction conditions are sufficiently mild to avoid over-oxidation of aldehydes to carboxylic acids. Generally, three equivalents of DCC and 0.5 equivalent of proton source in DMSO are allowed to react overnight at room temperature. The reaction is quenched with acid.

Dehydration[edit]

Alcohols can also be dehydrated using DCC. This reaction proceeds by first giving the O-acylurea intermediate which is then hydrogenolyzed to produce the corresponding alkene:

RCHOHCH2R' + (C₆H₁₁N)₂C → RCH=CHR' + (C₆H₁₁NH)₂CO

Inversion of secondary alcohols[edit]

Secondary alcohols can be stereochemically inverted by formation of a formyl ester followed by saponification. The secondary alcohol is mixed directly with DCC, formic acid, and a strong base such as sodium methoxide.

Esterification[edit]

Main article: Steglich esterification

A range of alcohols, including even some tertiary alcohols, can be esterified using a carboxylic acid in the presence of DCC and a catalytic amount of DMAP.^[5]

DCC-promoted peptide coupling[edit]

During protein synthesis (such as Fmoc solid-state synthesizers), the N-terminus is often used as the attachment site on which the amino acid monomers are added. To enhance the electrophilicity of carboxylate group, the negatively charged oxygen must first be "activated" into a better leaving group. DCC is used for this purpose. The negatively charged oxygen will act as a nucleophile, attacking the central carbon in DCC. DCC is temporarily attached to the former carboxylate group forming a highly electrophilic intermediate, making nucleophilic attack by the terminal amino group on the growing peptide more efficient.

Safety[edit]

DCC is a potent allergen and a sensitizer, often causing skin rashes.

References[edit]

^ ^a ^b Tang, J.; Mohan, T.; Verkade, J. G. (1994). "Selective and Efficient Syntheses of Perhydro-1,3,5-triazine-2,4,6-triones and Carbodiimides from Isocyanates Using ZP(MeNCH₂CH₂)₃N Catalysts". Journal of Organic Chemistry 59 (17): 4931–4938. doi:10.1021/jo00096a041.
^ Yavari, I.; Roberts, J. D. (1978). "Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy. Carbodiimides". Journal of Organic Chemistry 43 (25): 4689–4690. doi:10.1021/jo00419a001.
^ Pri-Bar, I.; Schwartz, J. (1997). "N,N-Dialkylcarbodiimide Synthesis by Palladium-Catalysed Coupling of Amines with Isonitriles". Chemical Communications 1997 (4): 347–348. doi:10.1039/a606012i.
^ Jászay, Z. M.; Petneházy, I.; Töke, L.; Szajáni, B. (1987). "Preparation of Carbodiimides Using Phase-Transfer Catalysis". Synthesis 1987 (5): 520–523. doi:10.1055/s-1987-27992.
^ Neises, B.; Steglich, W. (1985), "Esterification of Carboxylic Acids with Dicyclohexylcarbodiimide/4-Dimethylaminopyridine: Tert-Butyl Ethyl Fumarate", Org. Synth. 63: 183 ; Coll. Vol. 7: 93

External links[edit]

An excellent illustration of this mechanism can be found here: [1].

English Journal

Indole-based novel small molecules for the modulation of bacterial signalling pathways.

Biswas NN1, Kutty SK, Barraud N, Iskander GM, Griffith R, Rice SA, Willcox M, Black DS, Kumar N.
Organic & biomolecular chemistry.Org Biomol Chem.2015 Jan 21;13(3):925-37. doi: 10.1039/c4ob02096k.
Gram-negative bacteria such as Pseudomonas aeruginosa use N-acylated l-homoserine lactones (AHLs) as autoinducers (AIs) for quorum sensing (QS), a major regulatory and cell-to-cell communication system for social adaptation, virulence factor production, biofilm formation and antibiotic resistance. S
PMID 25406997

Preparation of photocrosslinked fish elastin polypeptide/microfibrillated cellulose composite gels with elastic properties for biomaterial applications.

Yano S1, Mori M2, Teramoto N3, Iisaka M4, Suzuki N5, Noto M6, Kaimoto Y7, Kakimoto M8, Yamada M9, Shiratsuchi E10, Shimasaki T11, Shibata M12.
Marine drugs.Mar Drugs.2015 Jan 9;13(1):338-53. doi: 10.3390/md13010338.
Photocrosslinked hydrogels reinforced by microfibrillated cellulose (MFC) were prepared from a methacrylate-functionalized fish elastin polypeptide and MFC dispersed in dimethylsulfoxide (DMSO). First, a water-soluble elastin peptide with a molecular weight of ca. 500 g/mol from the fish bulbus arte
PMID 25584682

Aliphatic organoimido derivatives of polyoxometalates containing a bioactive ligand.

She S1, Bian S, Hao J, Zhang J, Zhang J, Wei Y.
Chemistry (Weinheim an der Bergstrasse, Germany).Chemistry.2014 Dec 15;20(51):16987-94. doi: 10.1002/chem.201404317. Epub 2014 Oct 24.
A series of aliphatic organoimido derivatives of hexamolybdate based on amantadine, namely (nBu4 N)2 [Mo6 O18 (NC10 H15 )] (1), (nBu4 N)2 {cis-[Mo6 O17 (NC10 H15 )2 ]} (2), (nBu4 N)2 {trans-[Mo6 O17 (NC10 H15 )2 ]} (3), and (nBu4 N)2 [Mo6 O16 (NC10 H15 )3 ] (4), was synthesized in reason
PMID 25346326

Japanese Journal

Membrane eicosapentaenoic acid is involved in the hydrophobicity of bacterial cells and affects the entry of hydrophilic and hydrophobic compounds

Nishida Takanori,Hori Ryuji,Morita Naoki,Okuyama Hidetoshi
FEMS Microbiology Letters 306(2), 91-96, 2010-05-00
… In contrast, IK-1 was less resistant than IK-1Δ8 to two hydrophobic uncouplers: carbonyl cyanide m-chloro phenylhydrazone (CCCP) and N,N′-dicyclohexylcarbodiimide (DCCD). …
NAID 120003005547

Synthesis and Characterization of Methotrexate Polyethylene Glycol Esters as a Drug Delivery System

Yousefi Gholamhossein,Foroutan Seyed Mohsen,Zarghi Afshin [他],Shafaati Alireza
Chemical and Pharmaceutical Bulletin 58(2), 147-153, 2010
… Polymeric esters (MTX-PEGs) of MTX with low, medium and high molecular weight PEGs (750 D, 5000 D and 35000 D, respectively) were synthesized using dicyclohexylcarbodiimide (DCC) as coupling agent and triethylamine (TEA) as catalyst. …
NAID 130000161584

Root tip-dependent, active riboflavin secretion by Hyoscyamus albus hairy roots under iron deficiency

Higa Ataru,Miyamoto Erika,Rahman Laiq ur,Kitamura Yoshie
Plant Physiology and Biochemistry 46(4), 452-460, 2008-04-04
… Additions of proton-pump inhibitors, N,N'-dicyclohexylcarbodiimide (DCCD) at 100 and 10 μM and erythrosine B at 100 μM, suppressed the pH decline at 100 and 10 μM accompanied by inhibition of riboflavin secretion and root growth; …
NAID 120000916834

Related Pictures

★リンクテーブル★

リンク元	「DCC」「ジシクロヘキシルカルボジイミド」「DCCD」

「DCC」

N,N'-Dicyclohexylcarbodiimide
	IUPAC name N,N'-dicyclohexylcarbodiimide
	Other names DCC
Identifiers
CAS number	538-75-0
PubChem	10868
ChemSpider	10408
ChEBI	CHEBI:53090
ChEMBL	CHEMBL162598
RTECS number	FF2160000
Jmol-3D images	Image 1
	SMILES N(=C=N\C1CCCCC1)\C2CCCCC2 ;
	InChI InChI=1S/C13H22N2/c1-3-7-12(8-4-1)14-11-15-13-9-5-2-6-10-13/h12-13H,1-10H2 ; Key: QOSSAOTZNIDXMA-UHFFFAOYSA-N InChI=1/C13H22N2/c1-3-7-12(8-4-1)14-11-15-13-9-5-2-6-10-13/h12-13H,1-10H2; Key: QOSSAOTZNIDXMA-UHFFFAOYAO ;
Properties
Molecular formula	C13H22N2
Molar mass	206.33 g mol−1
Appearance	white crystalline powder
Density	1.325 g/cm3, solid
Melting point	34 °C, 307 K, 93 °F
Boiling point	122°C (395 K at 6 mmHg)
Solubility in water	not soluble
Hazards
R-phrases	R22 R24 R41 R43
S-phrases	S24 S26 S37/39 S45
NFPA 704	1 3 0
Flash point	113 °C
Related compounds
Related carbodiimides	DIC,EDC
	(verify) (what is: /?); Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
	Infobox references

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「ジシクロヘキシルカルボジイミド」

　　[★]

英: dicyclohexylcarbodiimide DCC DCCD
同: カルボジシクロヘキシルイミド carbodicyclohexylimide

「DCCD」

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同: dicyclohexylcarbodiimide

同: dicyclohexylcarbodiimide

[tang-1] Tang, J.; Mohan, T.; Verkade, J. G. (1994). "Selective and Efficient Syntheses of Perhydro-1,3,5-triazine-2,4,6-triones and Carbodiimides from Isocyanates Using ZP(MeNCH₂CH₂)₃N Catalysts". Journal of Organic Chemistry 59 (17): 4931–4938. doi:10.1021/jo00096a041.

[2] Yavari, I.; Roberts, J. D. (1978). "Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy. Carbodiimides". Journal of Organic Chemistry 43 (25): 4689–4690. doi:10.1021/jo00419a001.

[3] Pri-Bar, I.; Schwartz, J. (1997). "N,N-Dialkylcarbodiimide Synthesis by Palladium-Catalysed Coupling of Amines with Isonitriles". Chemical Communications 1997 (4): 347–348. doi:10.1039/a606012i.

[4] Jászay, Z. M.; Petneházy, I.; Töke, L.; Szajáni, B. (1987). "Preparation of Carbodiimides Using Phase-Transfer Catalysis". Synthesis 1987 (5): 520–523. doi:10.1055/s-1987-27992.

[5] Neises, B.; Steglich, W. (1985), "Esterification of Carboxylic Acids with Dicyclohexylcarbodiimide/4-Dimethylaminopyridine: Tert-Butyl Ethyl Fumarate", Org. Synth. 63: 183 ; Coll. Vol. 7: 93

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案内

dicyclohexylcarbodiimide