6674-22-2

Basic information

• Product Name: 1,8-Diazabicyclo[5.4.0]undec-7-ene
• Synonyms: 1,5-DIAZABICYCLO(5,4,0)UNDEC-5-ENE;1,8-DIAZABICYCLO[5,4,0]-7-UNDECENE;1,8-DIAZABICYCLO[5.4.0]UNDEC-7-ENE;1,8-DIAZABICYCLO[5.4.0]UNDEC-7-ENE (1,5-5);1,8-DIAZABICYCLO(5,4,0)UNDECENE-7;1,8-DIAZEBICYCLO[5.4.0]UNDEC-7-ENE;2,3,4,6,7,8,9,10-OCTAHYDROPYRIMIDO[1,2-A]AZEPINE;2,3,4,6,7,8,9,10-OCTAHYDROPYRIMIDOL[1,2-A]AZEPINE
• CAS NO: 6674-22-2
• Molecular Formula: C₉H₁₆N₂
• Molecular Weight: 152.24
• EINECS: 229-713-7
• Product Categories: pharmacetical;Pyridines;Other Reagents;Biochemistry;Reagents for Oligosaccharide Synthesis;Biochemics;OLED materials,pharm chemical,electronic;A clear, light yellow liquid of relatively low volatility. It has only a slight ammonia-like odor, is miscible with water and is soluble in most organic solvents.;pharmaceutical raw material;Organic intermediates
• Mol File: 6674-22-2.mol
• Article Data: 28

Chemical Properties

• Melting Point: -70 °C
• Boiling Point: 80-83 °C0.6 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: Clear colorless to light yellow/Liquid
• Density: 1.019 g/mL at 20 °C(lit.)
• Vapor Pressure: 5.3 mm Hg ( 37.7 °C)
• Refractive Index: n20/D 1.523
• Storage Temp.: Store at R.T.
• Solubility: soluble
• PKA: 13.28±0.20(Predicted)
• Explosive Limit: 1.1-6.5%(V)
• Water Solubility: soluble
• Sensitive: Air Sensitive
• Stability: Stable. Incompatible with strong oxidizing agents, acids, acid chlorides, acid anhydrides.
• BRN: 508906
• CAS DataBase Reference: 1,8-Diazabicyclo[5.4.0]undec-7-ene(CAS DataBase Reference)
• NIST Chemistry Reference: 1,8-Diazabicyclo[5.4.0]undec-7-ene(6674-22-2)
• EPA Substance Registry System: 1,8-Diazabicyclo[5.4.0]undec-7-ene(6674-22-2)

Safety Data

• Hazard Codes: C,F
• Statements: 22-34-52/53-35-40-37-19-11-67
• Safety Statements: 26-36/37/39-45-61-27-16
• RIDADR: UN 3267 8/PG 2
• WGK Germany: 2
• F: 34
• TSCA: Yes
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 6674-22-2(Hazardous Substances Data)

Usage

Description

DBU is a bicyclic amidine base. It is non-nucleophilic, sterically hindered, tertiary amine base in organic chemistry. It is reported to be superior to amine catalyst in Baylis-Hillman reaction.It promotes the methylation reaction of phenols, indoles and benzimidazoles with dimethyl carbonate under mild conditions.

Chemical Properties

Colorless to yellow liquid

Uses

Different sources of media describe the Uses of 6674-22-2 differently. You can refer to the following data:
1. DBU may be used:as catalyst for carboxylic acid esterification with dimethyl carbonatein the synthesis of duocarmycin and CC-1065 analogsas catalyst in aza-Michael addition and Knovenegal condensation reactionas base for dehalogenation of halogenated Diels-Alder adducts and the resulting activated 2,4-dienones were subjected to regio- and stereo-directed Michael additions, using Yamamoto′s reagent (CH3Cu · BF3)in a new synthesis of the ABCD ring system of CamptothecinDBU may be used as an catalyst for the dissolution and activation of cellulose by a reversible reaction of its hydroxyl groups with carbon dioxide. This dissolved cellulose system can be derivatized to form cellulose mixed esters.Used in a new synthesis of the ABCD ring system of Camptothecin.
2. DBU is used in organic synthesis as a catalyst, a complexing ligand, and a non-nucleophilic base. It is used as a protecting agent for the synthesis of cephalosporin and as a catalyst for polyurethane.

General Description

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Flammability and Explosibility

Nonflammable

Synthesis

The synthesis of DBU is as follows:As a base, sodium hydroxide was used at a concentration of 25% by weight and 2.3 times molar equivalent. A stirrer was placed in a 100 mL screw tube, and 11.5 g (50 mmol) of DBU hydrochloride, 8.5 g of toluene and 18.5 g (116 mmol) of 25% sodium hydroxide aqueous solution were charged at room temperature. It was placed on a magnetic stirrer and mixed for 1 hour with stirring. The mixture was separated with a 100 mL separatory funnel to obtain 18.8 g of the upper layer containing DBU and 18.4 g of the lower layer of the aqueous layer. The upper layer portion was analyzed by gas chromatography and contained 31.9% by weight of DBU, and the yield was 6.0 g (39.4 mmol) in a yield of 78.8%.

Purification Methods

Fractionally distil DBU under vacuum. Also purify it by chromatography on Kieselgel and eluting with CHCl3/EtOH/25% aqueous NH3 (15:5:2) and checking by IR and MS. [Oediger et al. Chem Ber 99 2012 1962, Angew Chem, Int Ed Engl 6 76 1967, Guggisberg et al. Helv Chim Acta 61 1057 1978, Beilstein 23/5 V 271.]

InChI:InChI=1/C9H16N2/c1-2-5-9-10-6-4-8-11(9)7-3-1/h1-8H2/p+1

Synthetic route

1-(2,3,4,6,7,8,9,10-Octahydro-pyrimido[1,2-a]azepin-10-yl)-1-phenyl-ethanol (107645-81-8) → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + acetophenone (98-86-2)

Conditions	Yield
at 150℃; for 2h; Product distribution;	A n/a B 90%

(2,3,4,6,7,8,9,10-Octahydro-pyrimido[1,2-a]azepin-10-yl)-diphenyl-methanol (107645-80-7) → benzophenone (119-61-9) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
at 180℃; for 2h; Product distribution;	A 85% B n/a

1,8-diazabicyclo<5.4.0>undec-7-ene hidrochloride (78204-84-9) → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
With tri-n-propylamine; sodium methylate In methanol	85%

1,8-diazabicyclo[5.4.0]undec-7-ene hydrochloride → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
With sodium hydroxide In water; toluene at 20℃; for 1h; Reagent/catalyst;	78.8%

pyrrole (109-97-7) + methyl 1,8-diazabicyclo[5.4.0]undec-6-ene-8-carboxylate (1309041-52-8) → methyl 1H-pyrrole-1-carboxylate (4277-63-8) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In chloroform-d1 at 19.84℃; for 56h;	A 78% B n/a

(2,3,4,6,7,8,9,10-Octahydro-pyrimido[1,2-a]azepin-10-yl)-phenyl-methanol (107645-82-9) → benzaldehyde (100-52-7) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
at 180℃; for 2h; Product distribution;	A 32% B n/a

(Z)-1-(2,3,4,6,7,8,9,10-Octahydro-pyrimido[1,2-a]azepin-10-yl)-2-phenyl-ethenol + cyclohexanol (108-93-0) → phenylacetic acid cyclohexyl ester (42288-75-5) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In diethylene glycol dimethyl ether for 24h; Product distribution; Mechanism; Heating;	A 14% B n/a

methanol (67-56-1) + (Z)-1-(2,3,4,6,7,8,9,10-Octahydro-pyrimido[1,2-a]azepin-10-yl)-2-phenyl-ethenol → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + benzeneacetic acid methyl ester (101-41-7)

Conditions	Yield
for 65h; Product distribution; Mechanism; Heating;	A n/a B 6%

C9H16N2*C8H7N2O4(1-)*H(1+) → 1-nitro-1-(4-nitrophenyl)ethane (29342-38-9) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In toluene at 20℃; Kinetics; Equilibrium constant; Thermodynamic data; other temperatures, other solvent, ΔH (excit.), ΔS(excit.);

C9H16N2*C7H4N3O6(1-)*H(1+) → 2,4,6-Trinitrotoluene (118-96-7) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In acetonitrile at 25℃; Rate constant; different solvents;

C9H16(2)HN2(1+)*C7H2(2)H2N3O6(1-) → 2,4,6-trinitro(α,αα-D3)toluene (52886-05-2) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In 1,2-dichloro-ethane at 25℃; Rate constant;

2,3,4,6,7,8,9,10-octahydro-1H-pyrimido[1,2-a]azepin-5-ylium; bromide → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
With amberlite IRA 400 (OH(-)) In methanol

N-(3-azidopropyl)-ε-caprolactam (674303-37-8) → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
Multi-step reaction with 3 steps 1: oxalyl bromide / 1,2-dichloro-ethane / 7 h / 0 - 25 °C 2: anisole; MeOH / 1,2-dichloro-ethane / 0.5 h / 25 °C 3: amberlite IRA 400 (OH(-)) / methanol View Scheme

1-bromo-2,3,4,6,7,8,9,10-octahydro-1H-pyrimido[1,2-a]azepin-5-ylium; bromide → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: anisole; MeOH / 1,2-dichloro-ethane / 0.5 h / 25 °C 2: amberlite IRA 400 (OH(-)) / methanol View Scheme

caprolactam (105-60-2) → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: NaH / tetrahydrofuran / 0.5 h / 20 °C 1.2: tetrabutylammonium iodide / tetrahydrofuran / 20 °C 2.1: oxalyl bromide / 1,2-dichloro-ethane / 7 h / 0 - 25 °C 3.1: anisole; MeOH / 1,2-dichloro-ethane / 0.5 h / 25 °C 4.1: amberlite IRA 400 (OH(-)) / methanol View Scheme

C25H26N2O2 → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + 2-benzylidene-indan-1,3-dione (5381-33-9)

Conditions	Yield
In acetonitrile at 20℃; Equilibrium constant; Further Variations:; concentrations;

→ 5-(4-methoxybenzylidene)-2,2-dimethyl-[1,3]dioxane-4,6-dione (15795-54-7) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In acetonitrile at 20℃; Equilibrium constant; Further Variations:; concentrations;

C23H30N4O4 → 5-(4-methoxy-benzylidene)-1,3-dimethyl-pyrimidine-2,4,6-trione (57270-82-3) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In acetonitrile at 20℃; Equilibrium constant; Further Variations:; concentrations;

C2F6NO4S2(1-)*C8H18NO3(1+)*C9H16N2 → 2-hydroxyethyl(dimethyl)isopropylammonium bis(trifluoromethylsulfonyl)imide (1003581-59-6) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
Inert atmosphere; Heating;

C2F6NO4S2(1-)*C7H11N2O3(1+)*C9H16N2 → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + 1-(2-hydroxyethyl)-3-methylimidazolium bis((trifluoromethane)sulfonyl)amide

Conditions	Yield
at 120℃; for 0.25h; Inert atmosphere;

methanol (67-56-1) + methyl 1,8-diazabicyclo[5.4.0]undec-6-ene-8-carboxylate (1309041-52-8) → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + carbonic acid dimethyl ester (616-38-6)

Conditions	Yield
In chloroform-d1 at 19.84℃; for 16h; Inert atmosphere;	A 100 %Spectr. B 100 %Spectr.

4-methylbenzophenone-(1,8-diazabicyclo[5.4.0]undec-7-ene)ammonium tetraphenylborate → 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In dimethyl sulfoxide Quantum yield; Irradiation;

pyrrole (109-97-7) + phenyl 1,8-diazabicyclo[5.4.0]undec-6-ene-8-carboxylate (1309041-53-9) → 1-phenoxycarbonyl pyrrole (56880-01-4) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

[RuII(2,2':6',2''-terpyridine)(1-(2,2':6',2''-terpyridin-4'-yl)-3-phenylurea(-H))]+ + 1,8-diazabicyclo[5.4.0]undec-7-ene cation (227008-07-3, 857293-63-1) → (4'-phenylurea-2,2':6',2''-terpyridine)(2,2':6',2''-terpyridine)ruthenium(II) (1429345-86-7) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In acetonitrile Equilibrium constant; Solvent;

1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + methyl iodide (74-88-4) → 8-Methyl-8-aza-1-azonia-bicyclo<5.4.0>undec-1(7)-en-jodid (41315-96-2)

Conditions	Yield
In dichloromethane at 20℃; for 12h;	100%
In benzene	9 g

1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + dimethyl acetylenedicarboxylate (762-42-5) → methyl 2-oxo-4,8-diazatricyclo[6.4.1.04,13]tridec-Δ1,13-en-3-ylideneacetate (173069-03-9)

Conditions	Yield
In dichloromethane at -45 - 20℃;	100%
In chloroform for 0.0333333h; Ambient temperature;	96%

1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + methyl trifluoromethanesulfonate (333-27-7) → 1-methyl-2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium trifluoromethanesulfonate

Conditions	Yield
In dichloromethane at 20℃; for 0.666667h;	100%
at 20℃; for 2h;	95%

benzyl chloride (100-44-7) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 1-benzyl-2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium chloride

Conditions	Yield
for 4h; Heating;	100%
In ethyl acetate at 20℃; for 48h;
In chloroform at 20℃; for 2h;
In chloroform at 20℃; for 2h;
In ethyl acetate at 20℃; for 48h;

ethyl bromide (74-96-4) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 1-ethyl-2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium bromide

Conditions	Yield
for 0.333333h; Heating;	100%
In ethyl acetate for 48h;
In acetonitrile for 48h;

n-Butyl chloride (109-69-3) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 1-butyl-2,3,4,6,7,8,9,10-octahydro-pyrimido[1,2-a]azepin-1-ium chloride

Conditions	Yield
for 5h; Heating;	100%
In acetonitrile at 75℃; for 24h; Inert atmosphere;	99%
at 50℃; for 24h; Inert atmosphere;	87%
In acetonitrile for 96h; Reflux;	56%

cis-dichlorobis(triphenylphosphine)platinum(II) (10199-34-5, 14056-88-3, 15604-36-1) + {Me2Sn(disulphurdinitrido)}2 + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → cis-Pt(disulphurdinitrido)(PPh3)2

Conditions	Yield
In not given byproducts: (CH3)2SnCl2; not isolated, identified by NMR spectroscopy;	100%

cis-dichlorobis(trimethylphosphine)platinum(II) (19471-47-7, 15630-86-1, 21545-76-6) + {Me2Sn(disulphurdinitrido)}2 + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → Pt(disulphurdinitrido)(PMe3)2 (104185-14-0)

Conditions	Yield
In not given byproducts: (CH3)2SnCl2; not isolated, identified by NMR spectroscopy;	100%

cis-[bis(dimethylphenylphosphane)dichlroplatinum(II)] (15393-14-3) + {Me2Sn(disulphurdinitrido)}2 + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → cis-Pt(disulphurdinitido)(PMe2Ph)2 (104185-15-1)

Conditions	Yield
In not given byproducts: (CH3)2SnCl2; not isolated, identified by NMR spectroscopy;	100%

[platinum(II)dichloride(1,2-bis(diphenylphosphino)ethane)] (83095-83-4, 14647-25-7) + {Me2Sn(disulphurdinitrido)}2 + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → (Pt(S2N2)(Ph2PCH2CH2PPh2)) (104185-17-3)

Conditions	Yield
In not given byproducts: (CH3)2SnCl2; not isolated, identified by NMR spectroscopy;	100%

cis-dichlorobis(methyldiphenylphosphine)platinum(II) (16633-72-0, 53585-56-1, 60103-85-7) + {Me2Sn(disulphurdinitrido)}2 + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → cis-Pt(disulphurdinitrido)(PMePh2)2

Conditions	Yield
In not given byproducts: (CH3)2SnCl2; not isolated, identified by NMR spectroscopy;	100%

Methyl 3-aminothiophene-2-carboxylate (22288-78-4) + triethylchlorogermane (994-28-5) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → (C2H5)3GeNHC6H5O2S (135302-90-8) + 1,8-diazabicyclo<5.4.0>undec-7-ene hidrochloride (78204-84-9)

Conditions	Yield
In benzene inert atmosphere; addn. of DBU soln. to soln. of Et3GeCl and thiophene derivative, then 36 h, 20°C; filtration off of DBU.HCl, evapn. (reduced pressure), distn. (vac.); elem. anal.;	A 59% B 100%

Methyl 3-aminothiophene-2-carboxylate (22288-78-4) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + dichlorodiphenylgermane (1613-66-7) → (C6H5)2ClGeNHC6H5O2S (135389-29-6) + 1,8-diazabicyclo<5.4.0>undec-7-ene hidrochloride (78204-84-9)

Conditions	Yield
In benzene inert atmosphere; addn. of DBU soln. to soln. of Ph2GeCl2 and thiophene derivative, then 36 h, 20°C; filtration off of DBU.HCl, evapn. (reduced pressure), distn. (vac.); elem. anal.;	A 99% B 100%

Methyl 3-aminothiophene-2-carboxylate (22288-78-4) + dichlorodimesitylgermane (96481-42-4) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → ((CH3)3C6H2)2ClGeNHC6H5O2S (144975-54-2, 135389-30-9) + 1,8-diazabicyclo<5.4.0>undec-7-ene hidrochloride (78204-84-9)

Conditions	Yield
In benzene inert atmosphere; addn. of DBU soln. to soln. of Mes2GeCl2 and thiophene derivative, then 24 h, 20°C; filtration off of DBU.HCl, evapn. (reduced pressure);	A 98% B 100%

C23H30N2O5 → 5-(4-methoxybenzylidene)-2,2-dimethyl-[1,3]dioxane-4,6-dione (15795-54-7) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2)

Conditions	Yield
In acetonitrile at 20℃; Equilibrium constant; Further Variations:; concentrations;

tricarbonylbis(triphenylphosphite)iron (15526-65-5, 20516-74-9) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → C9H17N2(1+)*Fe(CO)2(P(OC6H5)3)((C6H5O)2POC6H4)(1-)=[C9H17N2][Fe(CO)2(P(OC6H5)3)((C6H5O)2POC6H4)] (415704-04-0)

Conditions	Yield
In tetrahydrofuran Irradiation (UV/VIS); under N2; stirred soln. Fe(CO)3(P(OPh)3)3 in THF cooled; irradiated for 1-2 h (monitored by IR); C9H16N2 added; stirred for 2 min; not isolated;	100%

acetic acid (64-19-7) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 2,3,4,5,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium acetate (36443-65-9)

Conditions	Yield
In dichloromethane at 20℃; for 6h;	100%
at 60℃; for 18h; Schlenk technique;	95%
at 5 - 20℃;

1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 1,8-diazabicyclo<5.4.0>undec-7-ene hidrochloride (78204-84-9)

Conditions	Yield
With ammonium chloride In methanol at 20℃; for 6h;	100%
With hydrogenchloride In diethyl ether for 1h; Inert atmosphere;	90%
With ammonium chloride In methanol

triisopropylsilyl trifluoromethanesulfonate (80522-42-5) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → CF3O3S(1-)*C18H37N2Si(1+) (1211543-89-3)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; Inert atmosphere;	100%

trifluorormethanesulfonic acid (1493-13-6) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 1H-2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium trifluoromethanesulfonate

Conditions	Yield
In chloroform at 20℃;	100%
In dichloromethane at 20℃; for 6h;	92%
In methanol at 0℃; for 24h; Inert atmosphere;
In methanol at 60℃;

tetra-15-crown-5-phthalocyanine (110682-72-9) + erbium(III) acetate dihydrate + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → [Er(tetra-15-crown-5-phthalocyaninate)(1,8-diazabicyclo[5.4.0]undec-7-ene)(acetato)]

Conditions

Yield

In 1,2-dichloro-benzene placing of tetra-15-crown-5-phthalocyanine (1 equiv.) and Er(OAc)3*2H2O (8 equiv.) in flask with reflux condenser, addn. of 1,2-dichlorobenzene and 1,8-diazabicyclo(5.4.0)undec-7-ene (40 equiv.), heating to 180.degr ee.C, reflux for 4.5 h; cooling, pptn. with hexane, filtration, washing with hexane, dissolving in CHCl3, pptn. with hexane, sonication in acetone for 30 min, addn. of hexane to the volume ratio acetone:hexane=1:1, cooling to -18°C, pptn., filtration, drying;

100%

1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + p-nitrobenzyl imidazole-N-carboxylate → (4-nitrophenyl)methyl 3-(2-oxoazepan-1-yl)propylcarbamate (1450985-90-6)

Conditions	Yield
at 70℃; for 2h;	100%

1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + Trp (54-12-6) → 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium (D,L)-2-amino-3-(1H-indol-3-yl)propanoate

Conditions	Yield
In dichloromethane at 20℃; for 20h;	100%

1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 1,8-diazabicyclo[5.4.0]undec-7-ene hydrobromide (613257-41-3)

Conditions	Yield
With ammonium bromide In methanol at 20℃; for 6h;	100%
With hydrogen bromide In water at 5 - 20℃; for 24h;	99%
With hydrogen bromide In acetonitrile at 0 - 20℃; for 2h;
With hydrogen bromide for 6h;

S-methyl-S-(2-cyanoethyl) ethylphosphonodithioate + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → C3H9OPS2*C9H16N2

Conditions	Yield
In tetrahydrofuran at 20℃; for 1.5h;	100%

ciprofloxacin (85721-33-1) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → C17H18FN3O3*C9H16N2

Conditions	Yield
In methanol; water at 20℃; for 2h;	100%

methyl 4-hydroxy-4-methyl-2-pentynoate (25294-59-1) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 4-hydroxy-4-methyl-N-[3-(2-oxo-1-azepanyl)propyl]-2-pentynamide

Conditions	Yield
With water In acetonitrile at 20 - 25℃; for 48h; chemoselective reaction;	100%

1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 1,8-diazabicyclo[5.4.0]-7-undecene hydroiodide (93000-98-7)

Conditions	Yield
With ammonium iodide In methanol at 20℃; for 6h; Reagent/catalyst; Solvent;	100%
With hydrogen iodide In 1,4-dioxane; water at 20℃; for 12h;	98%

1,4-butane sultone (1633-83-6) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → 1,8-bis(butanesulphonic acid)-diazobicyclo[5.4.0]undec-7-enium hydrogen sulfate

Conditions	Yield
Stage #1: 1,4-butane sultone; 1,8-diazabicyclo[5.4.0]undec-7-ene at 20℃; for 0.0833333h; Stage #2: With sulfuric acid at 20℃;	100%

1,4-butane sultone (1633-83-6) + acetic acid (64-19-7) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) → C17H34N2O6S2(2+)*2C2H3O2(1-)

Conditions	Yield
Stage #1: 1,4-butane sultone; 1,8-diazabicyclo[5.4.0]undec-7-ene at 20℃; for 0.0833333h; Stage #2: acetic acid at 20℃;	100%

1,4-butane sultone (1633-83-6) + 1,8-diazabicyclo[5.4.0]undec-7-ene (6674-22-2) + trifluoroacetic acid (76-05-1) → C17H34N2O6S2(2+)*2C2F3O2(1-)

Conditions	Yield
Stage #1: 1,4-butane sultone; 1,8-diazabicyclo[5.4.0]undec-7-ene at 20℃; for 0.0833333h; Stage #2: trifluoroacetic acid at 20℃;	100%

Upstream product

• 1485432-29-8 C₁₅H₁₀O₄*C₉H₁₆N₂ 
• 1198425-21-6 C₉H₁₆N₂*C₁₆H₁₄O₃ 
• 105-60-2 caprolactam 
• 107-13-1 acrylonitrile 
• 51301-55-4 DBU formate 
• 227008-07-3 1,8-diazabicyclo[5.4.0]undec-7-ene cation 
• 109-97-7 pyrrole 
• 1309041-52-8 methyl 1,8-diazabicyclo[5.4.0]undec-6-ene-8-carboxylate 
• 1309041-53-9 phenyl 1,8-diazabicyclo[5.4.0]undec-6-ene-8-carboxylate 
• 67-56-1 methanol 
• 78204-84-9 1,8-diazabicyclo<5.4.0>undec-7-ene hidrochloride 

Downstream Products

• 93675-57-1 10-Benzyl-2,3,4,6,7,8,9,10-octahydro-pyrimido[1,2-a]azepine 
• 175791-97-6 Benzene-1,3,5-tricarboxylic acid tris(2-benzoyl>hydrazide) 
• 643-58-3 2-methylbiphenyl 
• 437764-46-0 benzyl 4-bromo-2-fluorobenzoate 
• 374641-86-8 5-(adamantan-1-yloxymethyl)-2-o-tolyl-2H-pyrazol-3-ol 

Relevant articles and documents

Photoinduced redox initiation for fast polymerization of acrylaytes based on latent superbase and peroxides

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The present invention provides a 1, 8 - diazabicyclo synthetic method, the technical scheme of the DBU synthetic route to an innovative design. Specific perspective, the invention first of all the use of ε-caprolactam, acrylonitrile and hydroquinone reaction generating N - (β - cyanoethyl) - ε-caprolactam, on this basis, will it and to toluene sulfonic acid in catalytic reaction under the condition, and then carry on ice bath, and then under the protection of nitrogen with benzyl chloride reaction, the resulting product to EDTA as the catalyst with high sodium borate reaction, the product of the reaction 3 - phenylpropanoic acid mixed with 4 - nitro benzyl chloride reaction to obtain the product. For the reaction product, filtered and the filtrate is extracted with ethyl acetate, the combined solid-liquid separation after solid phase, then the solid phase for reducing the drying to obtain the final product. The invention adopts the brand new synthetic route, its mild reaction conditions, material cost is relatively low, promotion prospect. (by machine translation)

MANUFACTURING METHOD OF DIAZABICYCLO COMPOUND

PROBLEM TO BE SOLVED: To provide a manufacturing method for providing a diazabicyclo compound from hydrochloric acid having a diazabicyclo group, which is suitable for industrial production. SOLUTION: There is provided a method for manufacturing a diazabicyclo compound by neutralization with using 20 wt.% to 50 wt.% of an alkali metal hydroxide solution or 10 wt.% to 50 wt.% of an alcohol solution of alkali metal alkoxide of 2.0 times molar equivalent to 3.5 times molar equivalent to hydrochloric acid having a diazabicyclo group. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPO&INPIT