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| | 1,8-Bis(dimethylamino)naphthalene Basic information |
| Product Name: | 1,8-Bis(dimethylamino)naphthalene | | Synonyms: | N,N,N',N'-TETRAMETHYL-1,8-NAPHTHALENEDIAMINE;N,N,N',N'-BIS(DIMETHYLAMINO) NAPHTHALENE;PROTON-SPONGE(R);N,N,N',N'-TetraMethyl-1,8-naphthalenediaMine puruM, >=99.0% (NT);N-N-N-Tetramethyl-1-8-naphthalenediamine;1,8-Naphthalenediamine,N1,N1,N8,N8-tetramethyl-;1,8-Naphthalenediamine,N,N,N’,N’-tetramethyl-;8-Naphthalenediamine,N,N,N’,N’-tetramethyl-1 | | CAS: | 20734-58-1 | | MF: | C14H18N2 | | MW: | 214.31 | | EINECS: | 244-001-6 | | Product Categories: | Amines and Anilines | | Mol File: | 20734-58-1.mol |  |
| | 1,8-Bis(dimethylamino)naphthalene Chemical Properties |
| Melting point | 49-51 °C(lit.) | | Boiling point | 144-145°C (3.7505 mmHg) | | density | 1.12 | | Fp | >230 °F | | storage temp. | Keep in dark place,Inert atmosphere,Room temperature | | solubility | Soluble in organic solvents. | | form | Crystalline Powder | | pka | 12.1(at 25℃) | | color | Pale brownish-pink | | Water Solubility | insoluble | | Sensitive | Light Sensitive | | Merck | 14,3388 | | BRN | 396782 | | InChIKey | GJFNRSDCSTVPCJ-UHFFFAOYSA-N | | CAS DataBase Reference | 20734-58-1(CAS DataBase Reference) | | NIST Chemistry Reference | 1,8-Naphthalenediamine, N,N,N',N'-tetramethyl-(20734-58-1) |
| | 1,8-Bis(dimethylamino)naphthalene Usage And Synthesis |
| Description | Significant attention in organic chemistry has been given to the so-called proton sponges, which are bi-center nitrogen bases that show spectacularly high basicity and very low nucleophilic character. The first member of this class of compounds 1,8-bis(dimethylamino)naphthalene or DMAN dragged attention due to its unexpectedly high basicity (pKa: DMAN 12.1; 1,8-diaminonaphthalene: 4.6) after its discovery in 1941[1]. It is prepared with an 82% yield from 1,8-diaminonaphthalene, dimethyl sulfate, and sodium hydride.
| | Chemical Properties | 1,8-Bis(dimethylamino)naphtalene is pale brownish-pink crystalline powder | | Uses | 1,8-Bis(dimethylamino)naphthalene, also referred to as protone sponge, is a lipophilic proton trapping agent. 1,8-Bis(dimethylamino)naphthalene is used in the matrix for mass spectroscopy analysis of
lipids and fatty acids. | | Uses |
1,8-Bis(dimethylamino)naphthalene can be used as a very strong base in organic synthesis and catalysis.
| | Definition | ChEBI: N1,N1,N8,N8-tetramethylnaphthalene-1,8-diamine is a member of naphthalenes. | | General Description | Proton-sponge is also referred as 1,8-dimethylamino naphthalene. It is very strong base with weak nucleophilic character due to steric effects. It also participates in the reactions between arachno-6,9-C2B8H14 and selected acyl chlorides. It has been tested as an effective H+ scavenger. | | Mechanism of action | A possibility of non-conventional two-step protonation of 1,8-bis(dimethylamino)naphthalene (proton sponge) is discussed. Unlike the generally accepted mechanism, involving relatively slow direct penetration of a proton into the cleft between the peri-NMe2 groups, it consists of the rapid addition of a proton to the out-inverted NMe2 group with the subsequent slower rotational transfer of the proton into the inter-nitrogen space to produce a stable chelated cation. The conclusion is that both pathways of proton sponge protonation, traditional and non-conventional, contribute in parallel with a still undefined ratio. The estimated out-basicity of the proton sponge is at least 5.5 orders of magnitude lower than the directly measured in-basicity[2]. | | Solubility in organics | Soluble in most organic solvents, such as methanol and chloroform. | | Purification Methods |
1,8-Bis(dimethylamino)naphthalene is prepared by methylating 1,8-diaminonaphthalene, and likely impurities are methylated products. The tetramethyl compound is a stronger base than the unmethylated, di and trimethylated derivatives. The pKa values are: 1,8-(NH2)2 = 4.61, 1,8-(NHMe)2 = 5.61, 1-NHMe-8-NHMe2 = 6.43 and 1,8-(NMe2)2 = 12.34. The mixture is then treated with H2O at pH 8 (where all but the required base are protonated) and extracted with Et2O or CHCl3. The dried extract (K2CO3) yields the tetramethyldiamine on evaporation which can be distilled. It is a strong base with weak nucleophilic properties, e.g. it could not be alkylated by refluxing with EtI in MeCN for 4 days; and on treatment with methyl fluorosulfonate only the fluorosulfonate salt of the base is obtained. [NMR: Adler et al. J Chem Soc, Chem Commun 723 1968, Brown & Letang J Am Chem Soc 63 358 1941, Brzezinski et al. J Chem Soc Perkin Trans 2 857 1991.] Alternatively, crystallise proton sponge from EtOH and dry it in a vacuum oven. Store it in the dark in a CO2-free atmosphere. [Benoit et al. Can J Chem 65 996 1987, Beilstein 13 IV 344.]
| | References |
[1] Utsab Bhattacharyya, Ralph Puchta, Renjith Thomas . “The proton sponge 1,8-bis(dimethylamino)naphthalene: The quicker-picker-upper also for s-block metal cations?” Chemical Physics Letters 777 (2021): Article 138735.
[2] Ozeryanskii, Valery A. et al. “Out-Basicity of 1,8-bis(dimethylamino)naphthalene: the experimental and theoretical challenge??.” Organic & Biomolecular Chemistry 15 (2013): 2360–2369.
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| | 1,8-Bis(dimethylamino)naphthalene Preparation Products And Raw materials |
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