36768-62-4

Basic information

• Product Name: Triacetonediamine
• Synonyms: TEMP;TAD;TIMTEC-BB SBB001789;2,2,6,6-tetramethyl-4-piperidinamin;2,2,6,6-Tetramethyl-4-piperidinamine;4-amino-2,2,6,6-tetramethyl-piperidin;Piperidine, 4-amino-2,2,6,6-tetramethyl-;TRIACETONEDIAMINE
• CAS NO: 36768-62-4
• Molecular Formula: C₉H₂₀N₂
• Molecular Weight: 156.27
• EINECS: 253-197-2
• Product Categories: Piperidines, Piperidones, Piperazines;Building Blocks;Heterocyclic Building Blocks;Piperidines
• Mol File: 36768-62-4.mol
• Article Data: 23

Chemical Properties

• Melting Point: 16-18 °C(lit.)
• Boiling Point: 188-189 °C(lit.)
• Flash Point: 162 °F
• Appearance: Clear, slightly yellow liquid
• Density: 0.912 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.597mmHg at 25°C
• Refractive Index: n20/D 1.470(lit.)
• Storage Temp.: Store below +30°C.
• PKA: 10.83±0.10(Predicted)
• Water Solubility: soluble
• BRN: 105038
• CAS DataBase Reference: Triacetonediamine(CAS DataBase Reference)
• NIST Chemistry Reference: Triacetonediamine(36768-62-4)
• EPA Substance Registry System: Triacetonediamine(36768-62-4)

Safety Data

• Hazard Codes: Xn,Xi,C
• Statements: 22-36/37/38-34-52/53-41
• Safety Statements: 26-36/37-45-36/37/39-61
• RIDADR: UN 2735 8/PG 3
• WGK Germany: 2
• RTECS: TM4290100
• TSCA: Yes
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 36768-62-4(Hazardous Substances Data)

Usage

Chemical Properties

CLEAR SLIGHTLY YELLOW LIQUID

Uses

Different sources of media describe the Uses of 36768-62-4 differently. You can refer to the following data:
1. Triacetonediamine have been investigated as new anticancer drugs with high activity and low toxicity.
2. Additive for light and heat stability of polyamide 6 containing hindered piperidine amines and tertiary aminesTemplate for preparation of ammoniopiperidinium hydrogen phosphatesFiber-reactive yellowing inhibitor for partial brightness stabilization of peroxide-bleached pulpsReactant for thermostability of soybean / sunflower oils

Safety Profile

Moderately toxic by ingestion.When heated to decomposition it emits toxic vapors ofNOx.

InChI:InChI=1/C9H20N2/c1-8(2)5-7(10)6-9(3,4)11-8/h7,11H,5-6,10H2,1-4H3/p+2

Synthetic route

4-hydroxyimino-2,2,6,6-tetramethylpiperidine (4168-79-0) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
With sulfuric acid electrochemical, Pb cathode; i=400 mA/cm2;	98%
With sodium In pentan-1-ol at 90℃; for 3h;	94%
With sodium In propan-1-ol for 1h; Reflux;	80%

C9H18N2 → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
With ammonium formate at 190℃; under 22502.3 Torr; for 2h; Temperature; Pressure; Reagent/catalyst;	95.5%

2,2,6,6-Tetramethyl-4-piperidone (826-36-8) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
With ammonium formate at 200℃; for 6h; Temperature;	94.7%
With sulfuric acid; hydroxylamine electrochemical, Pb cathode; i=400 mA/cm2;	85%
Multi-step reaction with 2 steps 1: 95 percent / NH2OH / aq. H2SO4 / 1 h 2: aq. HCl / electrochemical synthesis, var. electrodes, var. solvents View Scheme

4-amino-2,2,6,6-tetramethyl-1-piperidine-1-oxyl (14691-88-4) + diazodiphenylmethane (908093-98-1) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + benzophenone (119-61-9)

Conditions	Yield
In acetonitrile Product distribution; Rate constant; Mechanism; Ambient temperature; Irradiation; in isooctane;	A n/a B 90%
In acetonitrile Product distribution; Rate constant; Mechanism; Ambient temperature; Irradiation; in chlorobenzene;	A n/a B 90%

tris-2-oxypropylamine (63206-89-3) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
With ammonia; hydrogen; nickel In methanol at 65℃; under 67505.4 Torr; for 3h;	78%

phorone (504-20-1) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
With ammonia; acetic acid In methanol	71%
With acetic acid In methanol	64%
With ammonia; acetic acid In methanol	54%
With ammonia; acetic acid In methanol	41.5%
With acetic acid In methanol	38%

phorone (504-20-1) + cobalt (7440-48-4) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
With ammonia; acetic acid In methanol	65.5%

2,2,6,6-tetramethyl-4-oxopiperidine hydrazone (85884-12-4) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
In sulfuric acid at 20℃; electrochemical synthesis, lead electrode, 400 A*m-2;	65%
Multi-step reaction with 2 steps 2: 22 °C / electrochemical synthesis, 400 A*m-2, var. electrodes View Scheme

2,2,6,6-Tetramethyl-4-piperidone (826-36-8) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 4-hydroxy-2,2,6,6-tetramethylpiperidine (2403-88-5)

Conditions	Yield
With ammonium sulfate electrosynthesis, var. pH;
With ammonia; hydrogen; B113W In water at 55 - 100℃; under 30003 Torr; for 3h; Product distribution / selectivity;	A 92.10 %Chromat. B 5.49 %Chromat.

2,2,6,6,-tetramethyl-4-oxo-piperidine azine (18528-42-2) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
at 22℃; electrochemical synthesis, 400 A*m-2, var. electrodes; Yield given;

2C88H112O8*C9H20N2 (138847-23-1) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 5,11,17,23,29,35,41,47-octakis(tert-butyl)-49,50,51,52,53,54,55,56-octakis(hydroxy)calix[8]arene (68971-82-4)

Conditions	Yield
In acetonitrile at 25℃; Equilibrium constant;

2C44H56O4*C9H20N2 (138847-17-3) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene (157432-87-6, 288302-11-4, 288302-12-5)

Conditions	Yield
In acetonitrile at 25℃; Equilibrium constant;

hydrogenchloride (7647-01-0) + N,N'-bis-(2,2,6,6-tetramethyl-[4]piperidyl)-thiourea (85938-92-7) → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
at 130 - 140℃; im Rohr;

4-hydroxyimino-2,2,6,6-tetramethylpiperidine (4168-79-0) + i-Amyl alcohol (123-51-3) + sodium → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

triacetonamine oxime → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

Conditions	Yield
With hydrogenchloride; zinc
With i-Amyl alcohol; sodium

hydrogenchloride (7647-01-0) + 4-hydroxyimino-2,2,6,6-tetramethylpiperidine (4168-79-0) + ethanol (64-17-5) + water (7732-18-5) + zinc → 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4)

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + acetic anhydride (108-24-7) → N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide (40908-37-0)

Conditions	Yield
In diethyl ether at 5 - 10℃; for 3.5h;	100%
In diethyl ether at 15℃; for 0.5h;	91.7%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 1-methylbenzene-2,4-diisothiocyanate (4891-66-1) → C27H46N6S2

Conditions	Yield
In dichloromethane at 20℃; for 5h; Inert atmosphere;	99.6%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + acetic anhydride (108-24-7) → 4-acetylamino-2,2,6,6-tetramethyl-1-piperidinium acetate (136708-43-5)

Conditions	Yield
In diethyl ether for 3h;	99%
In diethyl ether at 0℃;	94%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + methoxymethyl isocyanate (6427-21-0) → 1-methoxymethyl-3-(2,2,6,6-tetramethyl-piperidin-4-yl)-urea (66650-99-5)

Conditions	Yield
In toluene	99%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + trifluoroacetic anhydride (407-25-0) → 2,2,6,6-tetramethyl-4-(2,2,2-trifluoroacetamido)piperidinium trifluoroacetate (61948-17-2)

Conditions	Yield
In diethyl ether at 0℃; for 1h;	99%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 1,4-dibromo-butane (110-52-1) → C17H34BrN2(1+)*Br(1-)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 16h; Reflux;	99%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 1,10-dibromodecane (4101-68-2) → C29H58Br2N2

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 15h; Reflux;	99%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 1,1’-diethyl-3-hydroxyazetidinium chloride (15314-03-1) → C16H35N3O

Conditions	Yield
In water at 80℃; for 24h;	99%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 2,3-Epoxypropyl methacrylate (106-91-2) → C16H30N2O3

Conditions	Yield
In acetonitrile at 20℃; for 24h;	99%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + Decyl-oxiran (2855-19-8) → C21H44N2O

Conditions	Yield
In tetrahydrofuran at 20℃; for 24h;	99%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + dimethyl Isophthalate (1459-93-4) → N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide (42774-15-2)

Conditions	Yield
With sodium methylate In methanol at 60 - 110℃; for 1.5h; Temperature; Inert atmosphere; Large scale;	98.5%
In octane at 150 - 160℃; under 6750.68 - 8250.83 Torr; for 15h; Pressure; Solvent; Temperature; Autoclave; Inert atmosphere;	97%
With solid supported catalyst C1 In acetonitrile at 20 - 70℃; for 15h; Reagent/catalyst;	96.7%
at 190 - 230℃; for 7h; Large scale;	93.5%
at 190 - 230℃; for 7h; Large scale;	93.5%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + acetic anhydride (108-24-7) → 4-(acetylamino)-2,2,6,6-tetramethylpiperidinium acetate

Conditions	Yield
In diethyl ether for 0.5h; Ambient temperature;	98%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + benzyl chloroformate (501-53-1) → 4-benzyloxycarbonylamino-2,2,6,6-tetramethylpiperidine hydrochloride salt

Conditions	Yield
In dichloromethane for 3h;	98%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + hexa[p-(formyloxy)chlorophenoxy]cyclotriphosphazene → C96H138N15O12P3

Conditions	Yield
With triethylamine In tetrahydrofuran for 12h; Concentration;	97.5%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 1,2,2,6,6-pentamethyl-4-(oxiran-2-ylmethoxy)piperidine (71882-90-1) → C22H45N3O2

Conditions	Yield
With ethanol In toluene at 85℃; for 9h; Temperature;	97.41%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + teroxirone (2451-62-9) → tris[2-hydroxy-3-(2,2,6,6-tetramethyl-4-piperidylamino)propyl] isocyanurate (144923-25-1)

Conditions	Yield
	97.4%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + benzene-1,3-dicarbonyl dichloride (99-63-8) → N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide (42774-15-2)

Conditions	Yield
With aluminum (III) chloride; sodium hydroxide In toluene at 110℃; Concentration;	97.38%
With sodium hydroxide In water; isopropyl alcohol at 30 - 130℃; under 1125.11 - 2475.25 Torr; Alkaline aqueous solution;	95.3%
With sodium hydroxide In chloroform Solvent; Reflux;	94.9%
With sodium hydroxide In water at 7 - 25℃; for 3.5h; Alkaline aqueous solution;	83.6%
With sodium hydroxide In water; isopropyl alcohol at 100℃;	200 g

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + dibutyl isophthalate (3126-90-7) → N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide (42774-15-2)

Conditions	Yield
With sodium methylate In methanol at 60 - 130℃; under 37.5038 Torr; for 3h; Inert atmosphere; Large scale;	97.3%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 2-(1',1'-dimethyl-3'-carbonyl-1'-butylamino)-4-methyl-3-pentene → 2-(1',1'-dimethyl-3'-(2',2',6',6'-tetramethyl-4-piperidinyl)-1'-butylamino)-4-methyl-3-pentene

Conditions	Yield
With sodium acetate; hydroquinone In tetrahydrofuran at 115℃; for 6h; Solvent; Temperature; Reagent/catalyst;	97.1%
With sodium acetate; hydroquinone In toluene at 100℃; for 4h;	95.9%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + chloroacetyl chloride (79-04-9) → 2-chloro-N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide hydrochloride

Conditions	Yield
In dichloromethane at 0℃; for 0.666667h;	97%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + diethyl isophthalate (636-53-3) → N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide (42774-15-2)

Conditions	Yield
With solid supported catalyst C2 In acetonitrile at 20 - 60℃; for 17h; Reagent/catalyst;	96.3%
In 1,3,5-trimethyl-benzene at 190 - 200℃; under 4500.45 - 5250.53 Torr; for 12h; Autoclave; Inert atmosphere;	93%
at 190 - 230℃; for 8h; Large scale;	91.6%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + diisopropyl isophthalate (1528-44-5) → N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide (42774-15-2)

Conditions	Yield
With solid supported catalyst C3 In acetonitrile at 20 - 80℃; for 12h; Reagent/catalyst;	96.2%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + acrylonitrile (107-13-1) → 4-<(2'-cyanoethyl)amino>-2,2,6,6-tetramethylpiperidine (66536-36-5)

Conditions	Yield
In ethanol for 3h; Heating;	96%
	90.8%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + difluoro(diethoxyphosphinyl)acetyl chloride (97480-49-4) → diethyl 1,1-difluoro-2-oxo-2-(2,2,6,6,-tetramethylpiperidin-4-ylamino)ethylphosphonate (1217898-89-9)

Conditions	Yield
With pyridine; dmap In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	96%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + 1-pyrenebutyric acid (3443-45-6) → N-(2,2,6,6-tetramethylpiperidine-4-yl)-4-(pyren-1-yl)butanamide

Conditions	Yield
Stage #1: 1-pyrenebutyric acid With oxalyl dichloride; N,N-dimethyl-formamide In tetrahydrofuran at 20℃; for 0.5h; Stage #2: 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE In tetrahydrofuran at 20℃; for 12h;	96%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + dianhydride [18]-crown-6-R,R-tartaric acid (76777-45-2) → (2R,3R,11R,12R)-(+)-N,N'-di-4'-(2',2',6',6'-tetramethylpiperidine)-2,11-dicarboxamido-1,4,7,10,13,16-hexaoxacyclooctadecane-3,12-dicarboxylic acid (111216-14-9)

Conditions	Yield
With triethylamine In dichloromethane	95%

4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE (36768-62-4) + acetyl compound → N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide (40908-37-0)

Conditions	Yield
	95%

Upstream product

• 504-20-1 phorone 
• 7440-48-4 cobalt 
• 7647-01-0 hydrogenchloride 
• 4168-79-0 4-hydroxyimino-2,2,6,6-tetramethylpiperidine 
• 64-17-5 ethanol 
• 7732-18-5 water 
• 123-51-3 i-Amyl alcohol 
• 85938-92-7 N,N'-bis-(2,2,6,6-tetramethyl-[4]piperidyl)-thiourea 
• 826-36-8 2,2,6,6-Tetramethyl-4-piperidone 
• 14691-88-4 4-amino-2,2,6,6-tetramethyl-1-piperidine-1-oxyl 
• 908093-98-1 diazodiphenylmethane 
• 63206-89-3 tris-2-oxypropylamine 
• 138847-17-3 2C₄₄H₅₆O₄*C₉H₂₀N₂ 
• 138847-23-1 2C₈₈H₁₁₂O₈*C₉H₂₀N₂ 

Downstream Products

• 201165-74-4 4-(4-nitrophenylamino)-2,2,6,6-tetramethylpiperidine 
• 271790-43-3 trans-(4-amino-2,2,6,6-tetramethyl-piperidine-N⁽⁴⁾)bis(pentane-2,4-dionato-O,O')(triphenylphosphine-P)cobalt(III) hexafluorophosphate dichloromethane solvate 
• 1610473-44-3 C₂₄H₄₂N₂O 
• 1610473-47-6 C₃₆H₄₉BN₂O 
• 1610473-48-7 C₃₆H₅₁BN₂O 
• 29211-91-4 N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,4-benzenedicarboxamide 
• 778645-56-0 [4-(4-bromophenyl)pyrimidin-2-yl]-(2,2,6,6-tetramethylpiperidin-4-yl)amine 
• 42774-15-2 N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide 
• 99779-87-0 (chloro-4 phenoxy)-isobutyrate d'hydroxy-4 N-((tetramethyl-2,2,6,6 piperidinyloxy)-4)butyramide 
• 99779-90-5 (chloro-4 phenoxy)-isobutyrate d'hydroxy-4 N-((tetramethyl-2,2,6,6 piperidinyl)-4)butyramide 
• 99779-86-9 N-((tetramethyl-2,2,6,6 piperidinyloxy)-4) (chloro-4 phenoxy)-isobutyramide 
• 82576-63-4 N,N-bis(2-chloroethyl)-3-(2,2,6,6-tetramethyl-4-piperidinyl)tetrahydro-2H-1,3,2-oxazaphosphorin-2-amine 2-oxide 
• 83144-40-5 1-cyclohexyl-3-(2'.2'.6'.6'-tetramethyl-piperidin-4'-yl-1'-oxyl)-urea 
• 83144-39-2 2,2,6,6-tetramethyl-4-(3-methyl-3-nitrosoureido)piperidine-1-oxyl 

Relevant articles and documents

CONDENSATION PRODUCTS OF 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE AND AMINOPIPERIDINOXYL RADICALS WITH ALDEHYDES

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2,2,6,6-tetramethyl-4-piperidinamine preparation method

The invention relates to a 2,2,6,6-tetramethyl-4-piperidinamine preparation method, which comprises: adding a raw material 2,2,6,6-tetramethylpiperidone, an amine reactant and a solvent into a reaction kettle, stirring and premixing at 10-50 DEG C to form an imine intermediate, reducing the imine intermediate by using a reducing agent at a certain temperature under a certain pressure, and reactingfor a certain time to finally synthesize the target product 2,2,6,6-tetramethyl-4-piperidinamine compound. According to the invention, 2,2,6,6-tetramethyl-4-carbonyl piperidone reacts with an amine compound to generate an imine intermediate, and a reducing agent is used for replacing catalytic hydrogenation to perform reduction, so the product yield can reach more than 92%, the generation of the2,2,6,6-tetramethylpiperidone hydrogenation byproduct tetramethylpiperidinol is avoided, the hydrogenation process with a high risk coefficient is avoided, and the method is an ideal process for achieving industrialization.

Method for preparing intermediate 2,2,6,6-tetramethyl-4-piperidylamine

The invention relates to a method for preparing intermediate 2,2,6,6-tetramethyl-4-piperidylamine. The method is characterized by comprising the following steps: step 1), in the presence of a catalyst1, reacting acetone with ammonia gas to produce 2,2,6,6-tetramethyl-4-piperidinone and water; and step 2), in the presence of a catalyst 2, reacting the 2,2,6,6-tetramethyl-4-piperidinone with ammonia gas to produce 2,2,6,6-tetramethyl-4-piperidylimine and water, and reacting the 2,2,6,6-tetramethyl-4-piperidylimine with hydrogen gas to produce the 2,2,6,6-tetramethyl-4-piperidylamine, wherein the catalyst 1 is ammonium nitrate, and the catalyst 2 is a sodium hydroxyphenyl phosphate modified framework nickel catalyst. The method provided by the invention has the advantages of short synthetictime, a high conversion rate of the acetone and a high repeating utilization rate of the raw materials.