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4-Dimethylaminopyridine

CAS No.
1122-58-3
Chemical Name:
4-Dimethylaminopyridine
Synonyms
DMAP;QCFA;26DCLPY;(4-DMAP);DMAP 25 G;AURORA KA-6495;4-DiMethylaMin;4-DMA PYRIDINA;JACS-1122-58-3;DMAP solution
CBNumber:
CB9852862
Molecular Formula:
C7H10N2
Formula Weight:
122.17
MOL File:
1122-58-3.mol
MSDS File:
SDS

4-Dimethylaminopyridine Properties

Melting point 112 °C
Boiling point 162 °C
Density 0.906 g/mL at 25 °C
vapor pressure 0.169 hPa at 20 °C
refractive index n20/D 1.431
Flash point 110 °C
storage temp. Store below +30°C.
solubility methanol: 50 mg/mL, clear
form prilled
pka pKa (20°): 9.7
color off-white to yellow
Odor characteristic odor
PH Range 9.7 (10% aq soln)
PH 11 (60g/l, H2O, 20℃)
Water Solubility 76 g/L (25 ºC)
Merck 14,3389
BRN 110354
Stability Stable. Incompatible with acids, oxidizing agents.
CAS DataBase Reference 1122-58-3(CAS DataBase Reference)
EWG's Food Scores 1
FDA UNII PFP1R6P0S8
NIST Chemistry Reference 4-Pyridinamine, N,N-dimethyl-(1122-58-3)
EPA Substance Registry System 4-(Dimethylamino)pyridine (1122-58-3)

SAFETY

Risk and Safety Statements

Symbol(GHS) 
GHS08,GHS02,GHS06,GHS07,GHS05
Signal word  Danger
Hazard statements  H314-H318-H402-H301-H310-H315-H319-H335-H302-H311-H351-H225-H302+H312-H336
Precautionary statements  P260h-P301+P310a-P303+P361+P353-P501a-P264-P270-P273-P302+P352+P310+P361+P364-P305+P351+P338+P337+P313-P405-P501-P262-P280-P302+P352+P310-P305+P351+P338-P361+P364-P301+P312+P330-P302+P352+P312-P304+P340+P312-P337+P313-P301+P310+P330-P210-P370+P378-P403+P235
Hazard Codes  T,C,T+,Xn,F
Risk Statements  25-34-24/25-36/37/38-27-36-24-20-61-40-23/24/25-67-66-21/22-11-36/37-22-19
Safety Statements  36/37/39-45-28A-26-28-36/37-53-27-22-16
RIDADR  UN 2811 6.1/PG 2
WGK Germany  3
RTECS  US8400000
Autoignition Temperature 420 °C
Hazard Note  Toxic/Corrosive
TSCA  T
HazardClass  8
PackingGroup  II
HS Code  29333999
Toxicity LD50 orally in Rabbit: 140 mg/kg LD50 dermal Rabbit 90 mg/kg

4-Dimethylaminopyridine price More Price(86)

Manufacturer Product number Product description CAS number Packaging Price Updated Buy
Sigma-Aldrich 8.20499 4-(Dimethylamino)pyridine for synthesis 1122-58-3 5 g $24.5 2022-05-15 Buy
Sigma-Aldrich 8.20499 4-(Dimethylamino)pyridine for synthesis 1122-58-3 25 g $52.7 2022-05-15 Buy
Sigma-Aldrich 8.51055 DMAP 4-(Dimethylamino)pyridine Novabiochem? 1122-58-3 25 g $42.2 2022-05-15 Buy
Sigma-Aldrich 8.20499 4-(Dimethylamino)pyridine for synthesis 1122-58-3 100 g $154 2022-05-15 Buy
Sigma-Aldrich PHR2925 Valacyclovir Related Compound G certified reference material, pharmaceutical secondary standard 1122-58-3 500MG $402 2022-05-15 Buy
Product number Packaging Price Buy
8.20499 5 g $24.5 Buy
8.20499 25 g $52.7 Buy
8.51055 25 g $42.2 Buy
8.20499 100 g $154 Buy
PHR2925 500MG $402 Buy

4-Dimethylaminopyridine Chemical Properties,Uses,Production

Overview

4-Dimethylaminopyridine is highly powerful catalyst of organic synthesis. The treatment of substrates such as alcohols, phenols and amines with acetic anhydride (or acetyl chloride) in the presence of pyridine has provided a general acetylation method since the turn of the 20th century. However, this approach often proves to be unsatisfactory for the acetylation of deactivated substrates. It was not until the late 1960’s that certain 4-dialkylaminopyridines were found (independently by two research groups)[1, 2] to be much superior to pyridine as catalysts for difficult acetylations or acylations, in general.

Figure 1 the chemical structure of DMAP

4-Dialkylaminopyridines were soon found to have general applicability for catalysis of a wide variety of reactions. 4-dimethylaminopyridine’s (DMAP) wide applicability has been frequently reviewed since the first review appeared in 1978. [3] The accelerating pace of reported applications for DMAP and the availability of DMAP in commercial quantities, at modest prices, have continued to stimulate great interest in its use as a catalyst in the fields of organic, polymer, analytical and biochemistry. Today there are thousands of examples of the use of DMAP in far ranging fields of chemistry in both patents and the research literature. Many full-scale production processes utilizing DMAP have been and are being operated. Several pharmaceutical and agricultural products that rely on DMAP’s superior catalytic properties in their synthetic sequences have been produced for years. Since 1976 more than 11,000 US patents have been granted which mention DMAP or dimethylaminopyridine.
The functional groups and class of compounds that are involved in the reactions with DMAP include alcohols, amines, arenes, azides, carbenes, enols, epoxides, hydrazines, hydroxylamines, phenols, thiols, lipids, sugars, aminoacids, peptides, alkaloids, steroids, terpenes, and others. Reactions that have been published in the literature using DMAP fall into, but are not limited to, the following types of reactions: Acylation; Acetylation; Alkylation; Benzoylation; Bischler-Naperalski cyclization, Carbonylation; Carbo-diimidation; Cyclization; Dehydration; Esterificaton; Indole Synthesis; Nucleophilic Substitution; Rearrangement; Silylation; Sulfonamidation; Sulfonation; Tritylation; Formylation; Carbamoylation; Phosphorylation; Lactonization; Pivaloylation; Dakin-West Reaction; Baylis-Hillman Reaction.

Chemical Properties

DMAP (m.p. 112-113°C) and PPY (m.p. 57-58°C)[4] are colorless, crystalline substances which are very soluble in methanol, ethyl acetate, chloroform, methylene chloride, 1,2-dichloroethane, acetone, and acetic acid and less soluble in cold hexane, cyclohexane, and water. DMAP can be recrystallized from ethyl acetate and PPY from pentane or hexane. The basicities of DMAP[5] and PPY in water as well as the dipole moment of DMAP[7-9] in benzene and dioxane have been determined by several groups. Of especial interest are the thermodynamic investigations concerned with the protonation of DMAP in water[11] and calculations whereby the influence of substituents on the basicity has been determined[6, 9, 10].

Reactions

DMAP reacts readily with electrophilic reagents. It is possible to quaternize DMAP in high yield with either methyl iodide or ethyl bromide, decomposes quantitatively in the presence of aqueous alkali to N-methy1-4-pyridone[17].
Addition of DMAP to S, S'-diethyl-S, S'-dimethyl-S, S-1, 2vinylenedisulfonium salts results in the smooth formation of the salt with concomitant generation of ethyl methyl sulfide[19]. Reaction of DMAP with acetylenedicarboxylic acid leads spontaneously to the bis-adduct in high yields[20].
On reaction with perbenzoic acid the strongly polar N-oxide is formed. Nitration of DMAP with HNO3/H2SO4 gives the 3-nitro derivatives in 81 % yield and, under forcing condition; the 3,5-dinitro compounds are obtained[16]. Reaction with O-(p-toluenesulfony1)hydroxylamine affords the N-amino compound in 67% yield which is isolated as the perchlorate. By treatment with D2O it is possible to selectively exchange the a-protons in DMAP, with DClO4 to exchange the P-protons to furnish and with D2O/NaOD to replace all aromatic protons by deuterium[18].

Application as acylation catalysts

Acylation of alcohol
The high catalytic activity of DMAP and PPY can be used for acylating sterically hindered secondary or tertiary alcohols with carboxylic anhydrides or acyl halides when the pyridine method fails. In most cases, it is necessary to use only 0.05-0.2 mol of catalyst per mol of substance and the acid that is formed can be bound with an equivalent amount of trimethylamine[21, 22] or pyridine[20]. Such solvents as hexane, toluene, benzene, methylene chloride, chloroform, ethyl acetate, tetrahydrofuran, triethylamine, pyridine, or acetic anhydride are suitable for use with these catalysts.
Among the tertiary alcohols which can be easily acylated with DMAP and PPY, mention should be made of l-methyl cyclohexanol, 1-ethynylcyclohexanol, 1,l-diphenylethanol, linalool, l, l-dimethoxy-2-methyl-3-buten-2-ol, 5,5-dimethoxy-2-methyI-3-pentyn-2-ol, and cis-4- (1-hydroxyisopropyl)-2-methylcyclohexanone.
Acylation of phenols
In the acylation of phenols, DMAP and PPY effect a similar increase in reaction rate as is found in the case of alcohols. Hence, the method is of interest for the acylation of sterically hindered phenols. For example, mesitol can be smoothly acetylated with acetic anhydride/DMAP to 2,5-ditert-butylphenol and analogous compounds can be transformed into acyl derivatives of the type in high yields[24]. 11,12-Dihydroglaziovine smoothly affords the acyl derivative[23, 25].
Acylation of amines
DMAP and PPY have been seldom used for the acylation of amines. The kinetic investigations of Lituinenko and Kirichenko [26] have shown that an enormous increase in reaction rate is observed when acylations are carried out in aprotic solvents. These authors have determined the following relative rate constants (in parentheses) for the amine-catalyzed acylation of m-chloroaniline with benzoyl chloride in benzene: N, N-dimethylaniline (0.1); triethylamine (0.072); 2,6-dimethylpyridine (0.03); pyridine (1.80); 4-methylpyridine (10.0); and DMAP (10600).
Acylation of enolates
Acylations involving CH-acid compounds which can be performed with pyridine or triethylamine as catalyst are found to proceed at a much higher rate when DMAP or PPY is used. The Dakin-West reaction of N-acyl amino acids, in which a 2-oxazolin-5-one is acetylated at C-4 with a carboxylic anhydride in pyridine with formation of a new C-C bond, has been extensively investigated[27]. The combination products, consisting of the ambident oxazolin-5-one anions and N-acylpyridinium cations initially formed under kinetic control, are transformed via the ion pair into the thermodynamically most stable product[28]. Decarboxylative ring opening by the subsequently formed carboxylic acid yields the a-acyl amino ketone[29, 30].
Reactions of isocyanates
Pyridine-catalyzed reactions of isocyanates with carboxylic acids to form amides are found to be strongly accelerated on replacement of pyridine by DMAP. Phenylacetic acid is found to react with phenyl isocyanate in 1,2-dichloroethane at 24°C to give the amide in 66 % yield in less than 5 min; whereas on using the same amount of pyridine only 53% could be isolated after 2h. With triethylamine, only very little is formed besides diphenylurea[31].
Miscellaneous Applications
DMAP has been used in the hardening of epoxy resins with dicyanodiamine, in the transformation of nitriles into thionamides, and in the transfer of silyl groups to tertiary hydroxyl groups[32, 33].
Transfer of Functional Groups
Dimethylarninopyridinium salts are interesting reagents for the transfer of acyl and also cyano and phosphono groups in aqueous medium[34, 35].

References

  1. Litvinenko, L. M.; Kirichenko, A. I. Dok. Akad. Nauk SSSR, Ser. Khim. 1967, 176, 97;
  2. Steglich, W.; Höfle, G. Angew. Chem. 1969, 81, 1001; Angew. Chem. Int. Ed. 1969, 8, 981.
  3. Scriven, E. F. V.; 4-Dialkylaminopyridines: Super Acylation and Alkylation Catalysts; Chem. Soc. Rev.
  4. H. Vorbriiggen, Angew. Chem. 84, 348 (1972); Angew. Chem. Int.
  5. Ed. Engl. 11, 305 (1972). L. Pentimalli, Gazz. Chim. Ital. 94, 902 (1964).
  6. R. W Taft, C. A. Grob, J . Am. Chem. SOC. 96, 1236 (1974).
  7. C. W N. Cumper, A. Singleton, J . Chem. SOC. B 1967, 1096.
  8. A. R. Katritzky, E. Fi! Randall, L. E. Sutton, J. Chem. SOC. 1957 1769.
  9. H. Lumbroso, J. Barassin, Bull. SOC. Chim. Fr. 1965, 3143.
  10. C. D. Johnson, I. Roberts, P. G. Taylor, J. Chem. SOC.C hem. Commun 1977, 897.
  11. M. R. Chakrabarty, C. S. Handloser, M. W Mosher, J. Chem. SOC. Perkin Trans. I1 1973, 938
  12. Pyridine syntheses, 1st Communication.-2nd Communication: H. Vorbriiggen, J. Kottwitz, K. Krolikiewicz, Chem. Ber., in preparation. This publication gives a complete survey of the various syntheses of DMAP and PPY; H. Vorbriiggen, DOS 2517774 (1975), Schering AG; Chem. Abstr. 86, 55293d (1977).
  13. W Steglich, G. Hofle, Tetrahedron Lett. 1970, 4727.
  14. E. Koenigs, H. Friedrich, H. Jurany, Ber. Dtsch. Chem. Ges. 58, 2571 (1925).
  15. A. C. Satterthwait, W P. Jencks, J. Am. Chem. SOC. 96, 7031 (1974).
  16. A. G. Burton, R. D. Frampton, C. D. Johnson, A. R. Katritzky, J. Chem. SOC. Perkin Trans. 11 1972, 1940.
  17. G. B. Barlin, J. A. Benbow, J . Chem. SOC. Perkin Trans. I1 1975,1385.
  18. J. A. Zoltewicz, J. D. Meyer, Tetrahedron Lett. 1968, 421.
  19. H. Braun, A. Amann, M. Richter, Angew. Chem. 89,488 (1977); Angew. Chem. lnt. Ed. Engl. 16, 471 (1977).
  20. B. P. Schaffner, H. Wehrli, Helv. Chim. Acta 55, 2563 (1972).
  21. 4-Dialkylaminopyridines as acylation catalysts, 4th Communication.-3rd Communication: G. Hofle, W Steglich, Synthesis 1972, 619.
  22. W Steglich, G. Hofle, Angew. Chem. 81, 1001 (1969); Angew. Chem. Int. Ed. Engl. 8, 981 (1969).
  23. J. E. McMurry, J . H. Musser, M. S. Ahmad, L. C. Blaszczak, J. Org. Chem. 40, 1829 (1975).
  24. D. J. Zwanenburg, W A. P. Reynen, Synthesis 1976, 624.
  25. 1. S. Bindra, A. Grodski, J. Org. Chem. 42, 910 (1977).
  26. H. Paulsen, H. Hohne, Carhohydr. Res. 58, 484 (1977).
  27. W Steglich, G. Hiiye, Tetrahedron Lett. 1968, 1619.
  28. W Steglich, G. HoJe, Chem. Ber. 104, 3644 (1971).
  29. W Steglich, G. HoJe, Chem. Ber. 102, 1129 (1969).
  30. G. HiiJe, A. Prox, W Steglich, Chem. Ber. 105, 1718 (1972).
  31. P. W Henniger, J. K. Van der Drift, DOS 2235390 (1973), Koninklijke Nederlandsche Gist-en Spiritusfabriek N. V.; Chem. Abstr. 78, 124608j
  32. J. Maurer, DOS 180867O(US Pat. 3530093) (1967), Ciba-Geigy; Chem. Abstr. 71, 1032541 (1969).
  33. P . C . Sriuastaua, M, Pickering, L. B. Allen, D. G. Streeter, M . 7: Campbell, J. R. Witkowski, R. W Sidwell, R. K. Robins, J. Med. Chem. 20, 256 (1977).
  34. S. D. Larsen, S. A. Monti, J. Am. Chem. SOC. 99, 8015 (1977).
  35. M. Wakselman, E. Guibl-Jampel, Tetrahedron Lett. 1970, 1521.

Chemical Properties

White solid

Uses

4-Dimethylaminopyridine (Valaciclovir EP Impurity G; Valacyclovir USP Related Compound G) is a highly efficient catalyst for acylation reactions.

Uses

In a wide variety of organic syntheses as a catalyst.

Uses

DMAP is a useful highly basic nucleophilic catalyst for a variety of reactions such as esterifications with anhydrides, the Baylis-Hillman reaction, hydrosilylations, tritylation, the Steglich rearrangement.

Uses

A highly fluorescent adenosine analogue, which in a dimethoxytrityl, phosphoramidite protected form, can be site-specifically inserted into oligonucleotides through a 3?5?phosphodiester linkage using an automated DNA synthesizer

Uses

4-Dimethylaminopyridine is a versatile hypernucleophilic acylation catalyst, it is used to improve the yield, reduce the reaction time, improving relaxation process conditions. Widely used in perfumes, dyes, pigments, pesticides, pharmaceuticals and polymer compounds and other fields. Also used as a catalyst for the synthesis of polyurethane, a curing agent and a blowing catalyst.

General Description

Valacyclovir Related Compound G, also called as 4-(Dimethylamino)pyridine (DMAP) is an excellent catalyst for acylation of hindered alcohols and in chemical transformations. It is highly nucleophilic in nature.

Purification Methods

Recrystallise DMAP from toluene [Sadownik et al. J Am Chem Soc 108 7789 1986]. [Beilstein 22 V 112.] § A polystyrene supported version (PS-DMAP) is commercially available.

4-Dimethylaminopyridine Preparation Products And Raw materials

Raw materials

Preparation Products

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View Lastest Price from 4-Dimethylaminopyridine manufacturers

Image Release date Product Price Min. Order Purity Supply Ability Manufacturer
2022-05-20 4-Dimethylaminopyridine
1122-58-3
US $3212.50 / G 5G API Standards 10G CLEARSYNTH LABS LTD.
2022-04-02 4-Dimethylaminopyridine
1122-58-3
US $30.00 / KG 1KG 99% 20 Tons Wuhan wingroup Pharmaceutical Co., Ltd
2022-03-19 4-Dimethylaminopyridine
1122-58-3
US $5.00 / kg 1kg 99% 100mt Jinan Finer Chemical Co., Ltd
AKOS BBS-00004314 AURORA KA-6495 26DCLPY 4-(Dimethylamino)pyridine, 99%, prilled 4-(DIMETHYLAMINO)PYRIDINE SOLUTION 4-(Dimethylamino)pyridine, ReagentPlus, 99% N,N'-DIMEHTYL-4-PYRIDINAMINE 4-(Dimethylamino)PyridineForSynthesis 4-Dimethylaminopyridine,>99% Dmap(4-Dimethylaminopyridine) 4-Pyridinamine, N,N-dimethyl- 4,4-dimethylaminopyridine 4,4-DIMETHYLAMINOPYRIDINE (DMAP) 4-(DIMETHYLAMINO)PYRIDINE 99.7% 4-Dimethylaminopyridine DMAP N,N-Dimethylpyridin-4-amine 4-DMAP DIMETHYLPYRIDIN-4-YLAMINE 4-Amino-2,6-dimethyl-8-(2’-deoxy--D-ribofuranosyl)-7(8H)-pteridone 4-(DiMethylaMino)pyridine puruM, >=98.0% (NT) 4-(DiMethylaMino)pyridine ReagentPlus(R), >=99% 4-DiMethylaMin 4-Dimethylaminopyridine N,N-Dimethylpyridin-4-amine Valaciclovir impurity G (PhEur) Valaciclovir Related Compound G (USP) 4-(Dimethylamino)pyridine, ChemDose? tablets The diMethyl aMinopyridine Famciclovir Dimethylaminopyridine Impurity (USP) 4-(Dimethylamino)pyridine solution 0.5 M in ethyl acetate 4-(Dimethylamino)pyridine, prilled, 99% 4-(N,N-dimethlyamino)pyridine 4-DMA PYRIDINA 4-Dimethylaminopyridine≥ 99% (HPLC) DMAP 4-(Dimethylamino)pyridine Novabiochem Valaciclovir EP Impurity G imethylaminopyridine Valacyclovir Impurity 7(Valacyclovir EP Impurity G) JACS-1122-58-3 N,N-Dimethylpyridin-4-amine DMAP 4-Dimethylaminopyridine 1122-58-3 In stock 4-Dimethylaminopyridine 1122-58-3 In stock N,N-Dimethylpyridin-4-amine DMAP 4-DIMETHYLAMINOPYRIDINE, 99%4-DIMETHYLAMINOPYRIDINE, 99%4-DIMETHYLAMINOPYRIDINE, 99% Valacyclovir EP Impurity G 4-DIMETHYLAMINOPYRIDINE extrapure 4-(Dimethylamino)-pyridine, synthesis grade 4-Dimethylaminopyrid DMAP solution 4-(Dimethylamino)pyridine, ChemDose(R) tablets DMAP, ChemDose(R) impregnated tablets, ChemDose(R), 4-(Dimethylamino)pyridine impregnated tablets N,N-Dimethyl(4-pyridyl)amine N,N-Dimethylpyridin-4-amine, DMAP Valacyclovir Related Compound G (50 mg) (N,N-dimethylpyridin-4-amine) DiMethyl-pyridin-4-yl-aMine (DMAP) 4-DiMethylaMinopyridine, 99% 100GR 4-DiMethylaMinopyridine, 99% 25GR 4-DiMethylaMinopyridine, 99% 5GR DMAP N-(4-Pyridyl)dimethylamine Valacyclovir IMpurity-G DMAP)4-DiMethylaMinopyr