5687-07-0

Basic information

• Product Name: 1,5-DIAZACYCLOOCTANE
• Synonyms: 1,5-DIAZACYCLOOCTANE;Octahydro-1,5-diazocine;1,5-Diazocine, octahydro-
• CAS NO: 5687-07-0
• Molecular Formula: C₆H₁₄N₂
• Molecular Weight: 114.19
• Mol File: 5687-07-0.mol
• Article Data: 6

Chemical Properties

• Boiling Point: 194℃
• Flash Point: 84℃
• Appearance: /
• Density: 0.852
• PKA: 11.03±0.20(Predicted)
• CAS DataBase Reference: 1,5-DIAZACYCLOOCTANE(CAS DataBase Reference)
• NIST Chemistry Reference: 1,5-DIAZACYCLOOCTANE(5687-07-0)
• EPA Substance Registry System: 1,5-DIAZACYCLOOCTANE(5687-07-0)

Safety Data

• Hazardous Substances Data: 5687-07-0(Hazardous Substances Data)

Usage

General Description

1,5-Diazacyclooctane, also known as tetramethylethylenediamine, is a chemical compound with the molecular formula C6H14N2. It is a saturated heterocyclic compound containing two nitrogen atoms in a ring structure. This chemical is commonly used as a ligand in coordination chemistry, where it can form complexes with various metal ions. It is also used as a reagent in organic synthesis, particularly in the formation of N-heterocyclic carbenes. 1,5-Diazacyclooctane has a wide range of industrial applications, including as a catalyst in polymerization reactions and as a stabilizer for PVC. Additionally, it is used in pharmaceutical and agricultural industries for the synthesis of various compounds.

Synthetic route

1,5-diazabicyclooctane dihydrobromide (40422-46-6) → 1,5-diazacyclooctane (5687-07-0)

Conditions	Yield
With sodium methylate In methanol at 70℃; for 0.166667h;	98%

1,5-bis(p-toluenesulphonyl)-1,5-diazacyclooctane (67761-04-0) → 1,5-diazacyclooctane (5687-07-0)

Conditions	Yield
With hydrogen bromide; phenol at 80℃; for 60h;	86%

azetidine (503-29-7) + formaldehyd (50-00-0) → 1,5-diazacyclooctane (5687-07-0)

Conditions	Yield
at 120℃; im Rohr;

1,5-diazabicyclo[3.3.0]octane (5397-67-1) → 1,5-diazacyclooctane (5687-07-0)

Conditions	Yield
With water; nickel Hydrogenation;
With diisobutylaluminum hydride

N1-(cyanoethyl)-1,3-propanediamine (35513-93-0) → 1,5-diazacyclooctane (5687-07-0)

Conditions	Yield
With sodium; butan-1-ol

1,5-diazoniatricyclo<3.3.3.0>undecane bistetrafluoroborate → 1,5-diazacyclooctane (5687-07-0) + 1,5-diazabicyclo<3.3.1>nonane (281-17-4)

Conditions	Yield
With tetrafluoroboric acid for 0.5h; Product distribution; Heating; t1/2; further reagent:NaOH/D2O;

N.N'-di-p-toluenesulfonyl- → 1,5-diazacyclooctane (5687-07-0)

Conditions	Yield
With hydrogenchloride at 180℃;

ethanol (64-17-5) + 1,3-Dichloropropane (142-28-9) + hydrazine (302-01-2) → pyrazolidine (504-70-1) + 1,5-diazacyclooctane (5687-07-0) + 1.2-trimethylene-pyrazolidine

3-propyl tosylate (75321-10-7) → 1,5-diazacyclooctane (5687-07-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) sodium hydride / 1.) DMF, 80 deg C, 2.5 h, 2.) DMF, 80 deg C, 24 h 2: 86 percent / phenol, 33percent HBr in acetic acid / 60 h / 80 °C View Scheme

N-tosyl-bis(3-hydroxypropyl)amine (56187-12-3) → 1,5-diazacyclooctane (5687-07-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 65 percent / triethylamine, 4-dimethylaminopyridine (DMAP) / CH2Cl2 / 2 h / Ambient temperature 2: 1.) sodium hydride / 1.) DMF, 80 deg C, 2.5 h, 2.) DMF, 80 deg C, 24 h 3: 86 percent / phenol, 33percent HBr in acetic acid / 60 h / 80 °C View Scheme

{Cu(1,5-diazocane)2}(2+) (46755-00-4, 46755-01-5) → 1,5-diazacyclooctane (5687-07-0) + copper(II) ion

Conditions	Yield
In hydrogenchloride Kinetics; hydrolysis reaction in HCl/NaCl solns.; depending on H(1+) concn.; spectrophotometry (abs. max. at 595 nm);

{Cu(1,5-diazocane)2}(2+) (46755-00-4, 46755-01-5) → 1,5-diazacyclooctane (5687-07-0) + copper(II)(1,5-diazacyclooctane)(2+)

Conditions	Yield
With acetate buffer In water Kinetics; dissociation of Cu(daco)2(2+)in the presence of acetate buffer, at 20°C, pH = 4.24 - 5.05; monitored by stopped flow spectrophotometry;
With 4-morpholineethanesulfonic acid In water Kinetics; acid dissociation of Cu(daco)2(2+) with 2-(N-morpholino)ethane and the corresponding sodium salt (1:1), at 20°C, pH = 5.81 - 6.41; monitored by stopped flow spectrophotometry;
With potassium dihydrogenphosphate In water Kinetics; dissociation of Cu(daco)2(2+)in the presence of potassium dihydrogen phosphate, at 20°C; monitored by stopped flow spectrophotometry;

(Ni(DACO)2)(2+) (41685-78-3) + {Ph3PhCH2P}{H2F3} → 1,5-diazacyclooctane (5687-07-0) + {Ni(1,5-diazocane)}(2+)

Conditions	Yield
In hydrogenchloride hydrolysis reaction in HCl/NaCl solns., depending on H(1+) concn.; spectrophotometry( abs. max. at 595 nm);

copper(II)(1,5-diazacyclooctane)(2+) → 1,5-diazacyclooctane (5687-07-0) + copper(II) ion

Conditions	Yield
With perchloric acid In water Kinetics; acid dissociation of Cu(daco)(2+)with perchloric acid (pH=8.5), at 20°C; monitored by stopped flow spectrophotometry;

1,5-diazacyclooctane (5687-07-0) + (4S)-2-chloromethyl-4-ethyl-2-oxazoline → (S,S)-1,5-bis(4-ethyloxazolin-2-ylmethyl)-1,5-diazacyclooctane

Conditions	Yield
With potassium carbonate In acetonitrile Heating;	87%

1,5-diazacyclooctane (5687-07-0) + (S)-2-(chloromethyl)-4-isopropyl-4,5-dihydrooxazole (221196-91-4) → (S,S)-1,5-bis(4-isopropyloxazolin-2-ylmethyl)-1,5-diazacyclooctane

Conditions	Yield
With potassium carbonate In acetonitrile Heating;	83%

1,5-diazacyclooctane (5687-07-0) + 5-chloro-pentanal (20074-80-0) → 7-aza-1-azoniatricyclo<5.3.3.01,6>tridecane chloride (84904-88-1)

Conditions	Yield
With magnesium sulfate In dichloromethane	82%

1,5-diazacyclooctane (5687-07-0) + (4S)-2-chloromethyl-4-methyl-2-oxazoline → (S,S)-1,5-bis(4-methyloxazolin-2-ylmethyl)-1,5-diazacyclooctane

Conditions	Yield
With potassium carbonate In acetonitrile for 10h; Heating;	81%

1,5-diazacyclooctane (5687-07-0) + (4S)-2-chloromethyl-4-isobutyl-2-oxazoline → (S,S)-1,5-bis(4-isobutyloxazolin-2-ylmethyl)-1,5-diazacyclooctane

Conditions	Yield
With potassium carbonate In acetonitrile Heating;	79%

1,5-diazacyclooctane (5687-07-0) + (4S)-2-chloromethyl-4-benzyl-2-oxazoline (221196-90-3) → (S,S)-1,5-bis(4-benzyloxazolin-2-ylmethyl)-1,5-diazacyclooctane

Conditions	Yield
With potassium carbonate In acetonitrile Heating;	75%

1,5-diazacyclooctane (5687-07-0) + 4-chlorobutyraldehyde (6139-84-0) → 6-aza-1-azoniatricyclo<4.3.3.01,5>dodecane chloride (82407-78-1)

Conditions	Yield
With magnesium sulfate In dichloromethane	74%

1,5-diazacyclooctane (5687-07-0) + vinyldiphenylphosphine oxide (2096-78-8) → 1,5-bis(2-diphenylphosphoryethyl)-1-azonia-5-azacyclooctane (165273-23-4)

Conditions	Yield
In benzene at 150 - 160℃; for 6h;	67%

3-n-butoxy-5-chloropyridine (303161-67-3) + 1,5-diazacyclooctane (5687-07-0) → 1-(5-butoxy-pyridin-3-yl)-[1,5]diazocane

Conditions	Yield
With potassium tert-butylate In 1,2-dimethoxyethane at 20℃; for 1.5h;	63%

3,5-dibromopyridine (625-92-3) + 1,5-diazacyclooctane (5687-07-0) → 1-(5-bromo-pyridin-3-yl)-[1,5]diazocane

Conditions	Yield
at 150℃; for 48h;	63%

1,5-diazacyclooctane (5687-07-0) + 8-bromomethyl-quinoline (7496-46-0) → N,N'-bis(quinolin-8-ylmethyl)-1,5-diazacyclooctane

Conditions	Yield
With potassium hydroxide In ethanol	60%

1,5-diazacyclooctane (5687-07-0) + 2-chloromethyl-1-methyl-imidazol hydrochloride (78667-04-6) → 1,5-bis(N-1-methylimidazol-2-methyl)-1,5-diazacyclooctane

Conditions	Yield
With potassium hydroxide In ethanol	60%

4-(Chloromethyl)pyridine (10445-91-7) + 1,5-diazacyclooctane (5687-07-0) → 1,5-bis(pyridin-4-ylmethyl)-1,5-diazacyclooctane

Conditions	Yield
With potassium hydroxide In ethanol at 20℃; for 72h; pH=9;	60%

3,6-dichlorpyridazine (141-30-0) + 1,5-diazacyclooctane (5687-07-0) → 1-(6-Chloro-3-pyridazinyl)-1,5-diazacyclooctane (223795-03-7)

Conditions	Yield
In toluene Heating / reflux;	42%

1,5-diazacyclooctane (5687-07-0) + 2-methyl-2-propenethiol (5954-68-7) → N,N'-bis(2-methyl-2-mercaptopropyl)-1,5-diazacyclooctane (152241-93-5)

Conditions	Yield
In benzene for 48h; Ambient temperature;	40.8%

1,5-diazacyclooctane (5687-07-0) + formaldehyd (50-00-0) + Diphenylphosphine oxide (4559-70-0) → 1,5-bis(diphenylphosphorylmethyl)-1,5-diazacyclooctane

Conditions	Yield
In benzene at 150 - 160℃; for 6h;	32%

1,5-diazacyclooctane (5687-07-0) + 3,5-dichloropyridine (2457-47-8) → 1-(5-chloro-pyridin-3-yl)-[1,5]diazocane

Conditions	Yield
at 150℃;	2.5%

3-Fluoropyridine (372-47-4) + 1,5-diazacyclooctane (5687-07-0) → 1-(3-pyridyl)-1,5-diazacyclooctane

Conditions	Yield
In 1,4-dioxane at 160℃; for 18h;	1.5%

1,5-diazacyclooctane (5687-07-0) + p-toluenesulfonyl chloride (98-59-9) → 1,5-bis(p-toluenesulphonyl)-1,5-diazacyclooctane (67761-04-0)

1,5-diazacyclooctane (5687-07-0) + Dichlorophenylphosphine (644-97-3) → 9-phenyl-1,5-diaza-9-phospha-bicyclo[3.3.1]nonane (35661-66-6)

Conditions	Yield
With triethylamine In diethyl ether

Upstream product

• 5397-67-1 1,5-diazabicyclo[3.3.0]octane 
• 67761-04-0 1,5-bis(p-toluenesulphonyl)-1,5-diazacyclooctane 
• 64-17-5 ethanol 
• 142-28-9 1,3-Dichloropropane 
• 302-01-2 hydrazine 
• 46755-00-4 {Cu(1,5-diazocane)2}⁽²⁺⁾ 
• 40422-46-6 1,5-diazabicyclooctane dihydrobromide 
• 41685-78-3 (Ni(DACO)2)⁽²⁺⁾ 
• 75321-10-7 3-propyl tosylate 
• 35513-93-0 N¹-(cyanoethyl)-1,3-propanediamine 
• 503-29-7 azetidine 
• 50-00-0 formaldehyd 
• 56187-12-3 N-tosyl-bis(3-hydroxypropyl)amine 

Downstream Products

• 96097-97-1 1-(phenylmethyl)octahydro-1,5-diazocine 
• 161885-62-7 1-[1-(4-fluorophenylmethyl)-1H-benzimidazol-2-yl]-1,5-diazacyclooctane 
• 165273-23-4 1,5-bis(2-diphenylphosphoryethyl)-1-azonia-5-azacyclooctane 
• 82407-78-1 6-aza-1-azoniatricyclo<4.3.3.0^1,5>dodecane chloride 
• 35661-66-6 9-phenyl-1,5-diaza-9-phospha-bicyclo[3.3.1]nonane 
• 67761-04-0 1,5-bis(p-toluenesulphonyl)-1,5-diazacyclooctane 

Relevant articles and documents

An Alternative Synthesis of Cyclic Aza Compounds

A series of cyclic mono-, di- and poly-aza compounds has been synthesised in moderate to good yields by reaction of p-toluenesulfonamide and either α,ω-ditosylates or α,ω-dichlorides.

DEPROTONATION OF HYDRAZINIUM DICATIONS IN THE DIAZONIAPROPELLANE SERIES TO FORM BRIDGEHEAD IMINIUM IONS; EXTERNAL AND INTRAMOLECULAR TRAPPING

The reactions of hexa-alkylhydrazinium dications with bases and nucleophiles are described. 1,5-Diazonia-tricyclodecane (1) is hydrolysed rapidly by SN2 attack on the four-membered ring with ring opening (C-N+ cleavage).In all other cases deprotonation at α-C with concomitant N+-N+ cleavage (E2 reaction) is the only primary process.The cis-1,6-dimethyl-1,6-diazoniabicyclodecane ion (6), is exclusively deprotonated at a methyl group (Hofmann orientation). 1,5-Diazoniatricycloundecane (2), 1,6-diazoniatricyclododecane (3), 1,6-diazoniatricyclotridecane (4), and 1,6-diazoniatricyclotetradecane (5) ions generate bridgehead iminium ions, which may be trapped intramolecularly by the transannular amino group or externally by added nucleophiles.Reaction with cyanide ion gives detailed information on the regio- and stereo-chemistry of the trapping sequence.Although intramolecular/external trapping is truly competitive, the products of these reactions (α-amino-ammonium ions and α-aminonitriles) may be interconverted under different reaction conditions.The solvolysis of 1-(3-phenoxypropyl)-1,5-diazabicyclooctanium bromide in aqueous 48percent HBr is 103 faster than that of 3-phenoxypropyltrimethylammonium bromide, and the products are consistent with the intermediacy of the dication (2).These observations provide an explanation for the formation of 1,5-diazacyclo-octane in the reaction of 1,3-dibromopropane with hydrazine.