44:
35:
303:
228:
799:) deprotonates the protonated DMAP, reforming the catalyst. The reaction runs through the described nucleophilic reaction pathway irrespective of the anhydride used, but the mechanism changes with the pKa value of the alcohol used. For example, the reaction runs through a base-catalyzed reaction pathway in the case of a phenol. In this case, DMAP acts as a base and deprotonates the phenol, and the resulting phenolate ion adds to the anhydride.
486:
738:
614:
835:
Kaljurand, I.; Kütt, A.; Sooväli, L.; Rodima, T.; Mäemets, V.; Leito, I.; Koppel, I. A. (2005). "Extension of the Self-Consistent
Spectrophotometric Basicity Scale in Acetonitrile to a Full Span of 28 pKa Units: Unification of Different Basicity Scales".
899:
Nachtergael, Amandine; Coulembier, Olivier; Dubois, Philippe; Helvenstein, Maxime; Duez, Pierre; Blankert, Bertrand; Mespouille, Laetitia (9 February 2015). "Organocatalysis
Paradigm Revisited: Are Metal-Free Catalysts Really Harmless?".
494:
466:
783:
gets cleaved to generate the catalyst and the ester. The described bond formation and breaking process runs synchronous concerted without the appearance of a tetrahedral intermediate. The
548:
627:
779:. Here the acetate acts as a base to remove the proton from the alcohol as it nucleophilically adds to the activated acylpyridinium. The bond from the acetyl group to the
1033:
1031:
Shimizu, Shinkichi; Watanabe, Nanao; Kataoka, Toshiaki; Shoji, Takayuki; Abe, Nobuyuki; Morishita, Sinji; Ichimura, Hisao (2007). "Pyridine and
Pyridine Derivatives".
352:
1170:
728:
DMAP can be prepared in a two-step procedure from pyridine, which is first oxidized to 4-pyridylpyridinium cation. This cation then reacts with
807:
DMAP has a relatively high toxicity and is particularly dangerous because of its ability to be absorbed through the skin. It is also corrosive.
936:
1142:
I. Held; P. von den Hoff; D. S. Stephenson; H. Zipse (2008). "Domino
Catalysis in the Direct Conversion of Carboxylic Acids to Esters".
1050:
317:
1185:
1070:; H. Zipse (2005). "The DMAP-Catalyzed Acetylation of Alcohols - A Mechanistic Study (DMAP = 4-(dimethylamino)-pyridine)".
544:
634:
538:
260:
969:
281:
1122:"Esterification of Carboxylic Acids with Dicyclohexylcarbodiimide/4-Dimethylaminopyridine: tert-Butyl Ethyl Fumarate"
436:
43:
34:
1175:
967:
Höfle, G.; Steglich, W.; Vorbrüggen, H. (1978). "4-Dialkylaminopyridines as Highly Active
Acylation Catalysts".
552:
750:
705:
223:
816:
185:
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508:
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478:
62:
17:
713:
83:
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717:
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1005:
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302:
227:
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729:
426:
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216:
737:
935:
Donald J Berry; Charles V Digiovanna; Stephanie S Metrick; Ramiah
Murugan (2001).
249:
1121:
784:
573:
530:
1105:
997:
995:
Ryan P. Wurz (2007). "Chiral
Dialkylamine Catalysts in Asymmetric Synthesis".
398:
196:
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526:
701:
1153:
1092:
1084:
1017:
981:
921:
857:
720:
experiments of mainly secondary alcohols and Evans auxiliary type amides.
518:
796:
780:
693:
678:
654:
941:
768:
763:
the currently accepted mechanism involves three steps. First, DMAP and
236:
1009:
913:
849:
522:
604:
Except where otherwise noted, data are given for materials in their
775:
adds to the acetylpyridinium, and elimination of pyridine forms an
776:
677:
N. This white solid is of interest because it is more basic than
514:
184:
174:
716:
of β-lactams and many more. Chiral DMAP analogues are used in
787:
formed will then protonate the DMAP. In the last step of the
286:
42:
33:
767:
react in a pre-equilibrium reaction to form an ion pair of
421:
110 to 113 °C (230 to 235 °F; 383 to 386 K)
692:
Because of its basicity, DMAP is a useful nucleophilic
622:
771:
and the acetylpyridinium ion. In the second step the
431:162 °C (324 °F; 435 K) at 50 mmHg
326:InChI=1S/C7H10N2/c1-9(2)7-3-5-8-6-4-7/h3-6H,1-2H3
336:InChI=1/C7H10N2/c1-9(2)7-3-5-8-6-4-7/h3-6H,1-2H3
248:
160:
1034:Ullmann's Encyclopedia of Industrial Chemistry
8:
712:, tritylation, the Steglich rearrangement,
301:
226:
204:
22:
268:
894:
892:
890:
888:
871:
869:
867:
827:
357:
322:
297:
937:"Catalysis by 4-dialkylaminopyridines"
217:
329:Key: VHYFNPMBLIVWCW-UHFFFAOYSA-N
7:
1066:S. Xu; I. Held; B. Kempf; H. Mayr;
696:for a variety of reactions such as
456:of conjugate acid in acetonitrile)
339:Key: VHYFNPMBLIVWCW-UHFFFAOYAL
239:
14:
736:
612:
484:
1120:B. Neises; W. Steglich (1990).
608:(at 25 °C , 100 kPa).
1171:Reagents for organic chemistry
16:For the cyanide antidote, see
1:
791:the auxiliary base (usually
1106:DMAP MSDS - Fischer Science
970:Angew. Chem. Int. Ed. Engl.
562:or concentration (LD, LC):
139:-Dimethyl-4-aminoazabenzene
130:4-(Dimethylamino)azabenzene
77:Dimethyl(pyridin-4-yl)amine
75:Dimethyl(pyridin-4-yl)azane
29:
1202:
1148:11/12 (11–12): 1891–1900.
882:. Retrieved on 2015-09-03.
748:
580:deer mice: oral, 450 mg/kg
403:122.17 g/mol
15:
1136:, vol. 7, p. 93
945:: 201–226. Archived from
880:4-(Dimethylamino)pyridine
602:
583:mice: oral, 350 mg/kg/day
558:
465:
460:
368:
348:
313:
144:
113:-Dimethyl-4-aminopyridine
104:4-(Dimethylamino)pyridine
101:
82:
61:
56:
28:
1043:10.1002/14356007.a22_399
539:Precautionary statements
95:-Dimethylpyridin-4-amine
73:-Dimethylpyridin-4-amine
24:4-Dimethylaminopyridine
1186:Dimethylamino compounds
1037:. Weinheim: Wiley-VCH.
751:Steglich esterification
745:Esterification catalyst
706:Baylis-Hillman reaction
683:resonance stabilisation
647:4-Dimethylaminopyridine
117:4-Dimethylaminopyridine
1154:10.1002/adsc.200800268
1085:10.1002/chem.200500398
982:10.1002/anie.197805691
817:4-Pyrrolidinylpyridine
587:fly: oral, 0.15 mg/mL
449:9.6 in water, 17.95 (p
128:-dimethyl-4-aminoazine
119:4-(Dimethylamino)azine
47:
38:
653:) is a derivative of
46:
37:
18:4-Dimethylaminophenol
714:Staudinger synthesis
585:rat: oral, 250 mg/mL
84:Preferred IUPAC name
25:
1145:Adv. Synth. Catal.
718:kinetic resolution
635:Infobox references
48:
39:
23:
1134:Collected Volumes
1127:Organic Syntheses
1079:(16): 4751–4757.
1068:Wolfgang Steglich
1010:10.1021/cr068370e
1004:(12): 5570–5595.
914:10.1021/bm5015443
902:Biomacromolecules
876:Sigma-Aldrich Co.
850:10.1021/jo048252w
761:acetic anhydrides
643:Chemical compound
641:
640:
594:Safety data sheet
509:Hazard statements
282:CompTox Dashboard
186:Interactive image
52:
51:
1193:
1176:4-Aminopyridines
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883:
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862:
861:
844:(3): 1019–1028.
832:
811:Related compound
765:acetic anhydride
740:
710:hydrosilylations
659:chemical formula
625:
619:
616:
615:
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376:Chemical formula
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1114:Further reading
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789:catalytic cycle
755:In the case of
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698:esterifications
688:
681:, owing to the
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360:n1ccc(N(C)C)cc1
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1052:978-3527306732
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1023:
987:
976:(8): 569–583.
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927:
908:(2): 507–514.
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863:
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757:esterification
749:Main article:
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606:standard state
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549:P305+P351+P338
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1073:Chem. Eur. J.
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949:on 2007-09-27
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839:
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815:
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810:
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800:
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794:
793:triethylamine
790:
786:
782:
778:
774:
770:
766:
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739:
735:
734:
733:
731:
730:dimethylamine
723:
721:
719:
715:
711:
707:
703:
699:
695:
690:
689:substituent.
684:
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427:Boiling point
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424:
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417:Melting point
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299:DTXSID0044369
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218:ECHA InfoCard
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968:
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951:. Retrieved
947:the original
940:
930:
905:
901:
841:
838:J. Org. Chem
837:
830:
806:
754:
727:
691:
685:from the NMe
650:
646:
645:
582:
559:
500:
467:
450:
440:
411:white solid
145:Identifiers
136:
132:
125:
121:
110:
106:
102:Other names
92:
88:
70:
66:
785:acetic acid
724:Preparation
574:median dose
560:Lethal dose
495:Signal word
408:Appearance
369:Properties
224:100.013.049
63:IUPAC names
1165:Categories
998:Chem. Rev.
953:2006-11-27
823:References
702:anhydrides
479:Pictograms
399:Molar mass
270:PFP1R6P0S8
197:ChemSpider
173:3D model (
152:CAS Number
1181:Catalysts
657:with the
553:P337+P313
470:labelling
162:1122-58-3
1093:15924289
1018:18072804
922:25490408
858:15675863
797:pyridine
781:catalyst
694:catalyst
679:pyridine
655:pyridine
461:Hazards
942:Arkivoc
773:alcohol
769:acetate
628:what is
626: (
437:Acidity
393:
237:PubChem
1091:
1049:
1016:
920:
856:
803:Safety
704:, the
623:verify
620:
596:(SDS)
501:Danger
353:SMILES
57:Names
777:ester
759:with
700:with
318:InChI
250:14284
206:13646
175:JSmol
1089:PMID
1047:ISBN
1014:PMID
918:PMID
854:PMID
651:DMAP
545:P280
531:H335
527:H319
523:H315
519:H310
515:H301
261:UNII
115:DMAP
1150:doi
1081:doi
1039:doi
1006:doi
1002:107
978:doi
910:doi
846:doi
795:or
661:(CH
468:GHS
287:EPA
240:CID
1167::
1131:;
1124:.
1087:.
1077:11
1045:.
1012:.
974:17
939:.
916:.
906:16
904:.
887:^
878:,
866:^
852:.
842:70
840:.
732::
708:,
669:NC
570:50
568:LD
551:,
547:,
529:,
525:,
521:,
517:,
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439:(p
387:10
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1152::
1138:.
1095:.
1083::
1055:.
1041::
1020:.
1008::
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980::
956:.
924:.
912::
860:.
848::
687:2
675:4
673:H
671:5
667:2
665:)
663:3
649:(
618:Y
576:)
572:(
454:a
451:K
444:a
441:K
391:2
389:N
385:H
383:7
381:C
289:)
285:(
177:)
137:N
135:,
133:N
126:N
124:,
122:N
111:N
109:,
107:N
93:N
91:,
89:N
71:N
69:,
67:N
20:.
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