1,5,7-Triazabicyclo[4.4.0]dec-5-ene Chemical Properties

Melting point:

125-130 °C(lit.)

Boiling point:

222.3±23.0 °C(Predicted)

Density 

1.28±0.1 g/cm3(Predicted)

storage temp. 

under inert gas (nitrogen or Argon) at 2–8 °C

solubility 

toluene: soluble1 g/15 mL

form 

powder to crystal

pka

14.47±0.20(Predicted)

color 

White to Almost white

Water Solubility 

acetonitrile: soluble
ethanol: soluble
organic solvents: soluble
water: soluble

BRN 

3242

InChI

InChI=1S/C7H13N3/c1-3-8-7-9-4-2-6-10(7)5-1/h1-6H2,(H,8,9)

InChIKey

FVKFHMNJTHKMRX-UHFFFAOYSA-N

SMILES

C12=NCCCN1CCCN2

CAS DataBase Reference

5807-14-7(CAS DataBase Reference)

Safety Information

Hazard Codes 

C

Risk Statements 

34

Safety Statements 

26-36/37/39-45-27

RIDADR 

UN 1759 8/PG 2

WGK Germany 

3

F 

9-21-34

HazardClass 

8

PackingGroup 

III

HS Code 

29335990

MSDS

• Language:English Provider:SigmaAldrich

1,5,7-Triazabicyclo[4.4.0]dec-5-ene Usage And Synthesis

Description

1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) is a bicyclic guanidine that has found extensive application in organic chemistry, notably as a powerful catalyst for polymer synthesis and recycling, CO2 utilization, and carboxylic acid derivative synthesis. Bearing both a nucleophilic nitrogen and an electrophilic N?H group, TBD is a multifunctional reagent. It can serve as an organic superbase, an acyl transfer reagent, and a hydrogen bonding activator. It is an excellent catalyst for Michael and Michael-type reactions. The readily available organocatalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was used for the rapid synthesis of 3-hydroxyisoindolin-1-ones from 3-alkylidenephthalides[1-2].

Chemical Properties

Light yellow crystalline

Uses

1,5,7-Triazabicyclo[4.4.0]dec-5-ene may be used as organocatalyst for aminolysis of esters. It may be used as catalyst for direct addition of P(O)-H bonds (dialkyl phosphites and diphenyl phosphonite) across various activated alkenes. Polymer supported 1,5,7-triazabicyclo[4.4.0]dec-5-ene (PTBD) was used as a base and a reagent scavenger for the synthesis of aryl ethers from phenols and alkyl or aryl halides.

Definition

ChEBI: 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine is a member of pyrimidines.

General Description

1,5,7-Triazabicyclo[4.4.0]dec-5-ene, a bicyclic guanidine base, has been found to be an excellent catalyst for Michael and Michael-type reactions. It forms 1:1 complex with lasalocid acid and crystal structure of the complex has been studied by X-ray diffraction, FT-IR spectroscopy and ¹H NMR.

Reactivity Profile

1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) is a strong bicyclic guanidine base with a pKa = 24.97. It has been shown to promote various reactions, including the Horner–Wadsworth–Emmons reactions, nitroaldol (Henry) reaction, secondary amine alkylation, carboxylation of propylene glycol with CO2, Michael reactions, synthesis of symmetrically N, N′-substituted ureas, 5- and 6-enolexo aldolisation of acyclic ketoaldehydes, intramolecular aldolization of acyclic ketoaldehydes etc. In these reactions, TBD shows good activity and selectivity[3].

reaction suitability

reaction type: solution phase peptide synthesis
reactivity: proton reactive

Synthesis

To a 100 mL autoclave equipped with a reflux condenser and an electric stirrer, 20 mL of aqueous GHC (6.0 mmol/mL) and 20 mL (5.0 mmol/mL) of APA solution in homotrimethylbenzene were added, as well as 0.578 g of pretreated atmospheric anion-exchange resin (D201).The reaction was carried out under argon gas protection for 9 h at 120°C. The reaction was completed by filtration. Upon completion of the reaction, the D201 resin in the reaction mixture was first recovered by filtration (the washed and dried recovered resin was used to repeat the synthesis experiments). Subsequently, the oil-water system was filtered, and the homotrimethylbenzene in the oil phase was separated and recovered using a partition funnel. The aqueous phase was distilled to yield a pale yellow viscous liquid, which was extracted with 30 mL of dichloromethane. Dichloromethane was recovered by distillation through rotary evaporator. The resulting colorless oily liquid was placed in a freezer at 12°C for 12 hours and then allowed to stand at room temperature (15 to 25°C), gradually converting to a pale yellow solid. Finally, it was dried under vacuum at 40°C for 40 h to afford 1,5,7-triazabicyclo[4.4.0]decen-5-ene (TBD) 7.66 g in 55% yield.

Purification Methods

1,5,7-Triazabicyclo[4.4.0]dec-5-ene crystallises from Et2O but readily forms white crystals of the carbonate. It is a strong base (see pK, i.e. about 100 times more basic than tetramethylguanidine). The picrate has m 220.5-222o (from EtOH). It forms the 5-nitro derivative m 14.5-160o that gives a 5-nitro nitrate salt m 100-101o (from EtOH/Et2O) and a 5-nitro picrate m 144-145o (from H2O) [McKay & Kreling Can J Chem 35 1438 1957, Schwesinger Chimia 39 369 1985, Hilpert et al. J Chem Soc, Chem Commun 1401 1983, Kamfen & Eschenmoser Helv Chim Acta 72 185 1989]. [Beilstein 26 III/IV 60.]

References

[1] Chunling Blue Lan, Prof. Karine Auclair. “1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD): An Organocatalyst for Rapid Access to 3-Hydroxyisoindolin-1-ones.” European Journal of Organic Chemistry 27 12 (2024).
[2] Weiping Ye. “1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) catalyzed Michael reactions.” Tetrahedron Letters 46 40 (2005): Pages 6875-6878.
[3] Iuliana Cota . “1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) an efficient homogeneous catalyst for aldol condensation reactions. Study of the catalyst recovery and reusability using CO2.” Tetrahedron Letters 52 3 (2011): Pages 385-387.

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