702-82-9

Basic information

• Product Name: 3-Amino-1-hydroxyadamantane
• Synonyms: TRICYCLO[3.3.1.13,7]DECAN-1-OL, 3-AMINO-;CHEMBRDG-BB 4003530;3-AMINO-1-ADAMANTANOL;3-Amino-1-hydroxyadamantane;3-AMINOADAMANTAN-1-OL;AKOS BB-9784;1-AMINO-3-ADAMANTANOL;1-AMINO-3-HYDROXYADAMANTANE
• CAS NO: 702-82-9
• Molecular Formula: C₁₀H₁₇NO
• Molecular Weight: 167.25
• EINECS: 1308068-626-2
• Product Categories: Heterocycles series;Alcohols and Derivatives;Amines and Anilines;Adamantane derivatives;Amines;Adamantanes;Fused Ring Systems;Amino Alcohols;Organic Building Blocks;Oxygen Compounds;Intermediates & Fine Chemicals;Pharmaceuticals;Amino Alcohols;Building Blocks;Chemical Synthesis;Organic Building Blocks;Oxygen Compounds;intermediate;NULL
• Mol File: 702-82-9.mol
• Article Data: 28

Chemical Properties

• Melting Point: 265 °C (dec.)(lit.)
• Boiling Point: 266.8 °C at 760 mmHg
• Flash Point: 230 °F
• Appearance: White to yellow/Crystalline Powder
• Density: 1.252 g/cm³
• Vapor Pressure: 0.00115mmHg at 25°C
• Refractive Index: 1.624
• Storage Temp.: Keep in dark place,Inert atmosphere,Room temperature
• Solubility: DMSO (Slightly), Methanol (Slightly)
• PKA: 15.07±0.40(Predicted)
• Water Solubility: Soluble in organic solvents,insoluble in water.
• CAS DataBase Reference: 3-Amino-1-hydroxyadamantane(CAS DataBase Reference)
• NIST Chemistry Reference: 3-Amino-1-hydroxyadamantane(702-82-9)
• EPA Substance Registry System: 3-Amino-1-hydroxyadamantane(702-82-9)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• HazardClass: IRRITANT
• Hazardous Substances Data: 702-82-9(Hazardous Substances Data)

Usage

Chemical Properties

White solid

Uses

Different sources of media describe the Uses of 702-82-9 differently. You can refer to the following data:
1. It is employed in the synthesis of inhibitors with antihyperglycemic properties. vil- dagliptin is synthesised from 3-Amino-1-adamantanol.
2. As reagent, 3-Amino-1-hydroxyadamantane can be used in the preparation of Vildagliptin.
3. 3-Amino-1-hydroxyadamantane can be employed in the synthesis of inhibitors with antihyperglycemic properties.

InChI:InChI=1/C10H17NO/c11-9-2-7-1-8(3-9)5-10(12,4-7)6-9/h7-8,12H,1-6,11H2

Synthetic route

3-nitroadamantan-1-ol (67496-92-8) → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
	95%

amantadine hydrochloride (665-66-7) → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
With sulfuric acid; nitric acid at 10 - 15℃;	90%
With sulfuric acid; nitric acid at 0 - 10℃; for 2h;	81%
Stage #1: amantadine hydrochloride With sulfuric acid; nitric acid at 0 - 20℃; Inert atmosphere; Stage #2: With sodium hydroxide In water	72%

1-Adamantanamine (768-94-5) → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
Stage #1: 1-Adamantanamine With sulfuric acid; nitric acid In water at 5 - 25℃; Stage #2: With water; sodium hydroxide at 0 - 40℃; for 1h;	90%
With sulfuric acid; nitric acid at 0 - 10℃; for 2h;	81%
With Bromotrichloromethane; water; molybdenum hexacarbonyl at 150℃; for 6h; Inert atmosphere; regioselective reaction;	80%
With sulfuric acid; nitric acid at 90℃; Temperature;

N-(3-hydroxyadamantan-1-yl)acetamide (778-10-9) → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
With isopropyl alcohol; sodium hydroxide at 160℃; for 6h; Temperature; Reagent/catalyst; Autoclave; Inert atmosphere;	90%

N-(1-adamantyl)acetamide (880-52-4) → 1,3-adamantandiol (5001-18-3) + 3-aminoadamantan-1-ol (702-82-9) + N-(3-hydroxyadamantan-1-yl)acetamide (778-10-9)

Conditions	Yield
Stage #1: N-(1-adamantyl)acetamide With nitric acid Stage #2: With acetic acid; urea In water	A 11% B n/a C 13%

C10H17N*BF4(1-)*H(1+) → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
With methyltrifluoromethyldioxirane; sodium carbonate 1.) CH3CN, CH2Cl2, 0 deg C, 3 h, 2.) CH2Cl2, RT, 5 h; Yield given. Multistep reaction;

3-methylenebicyclo<3.3.1>nonan-7-one → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
With ammonium hydroxide at 130℃;

amantadine hydrochloride (665-66-7) → 3-hydroxytricyclo[3.3.1.13.7 ]decan-1-amine + 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
With sodium hydroxide

3-nitro-1-amantadine (243145-00-8) → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
With sodium methylate In methanol at 30℃; for 0.5h; pH=> 14; Solvent; Reagent/catalyst;	19.5g
With water; sodium hydroxide at 80℃; for 1.5h; pH=11 - 14; Temperature; pH-value;	150.6 g

1-adamanthanol (768-95-6) → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
Multi-step reaction with 3 steps 1: 9,10-diphenylanthracene; tetrabutyl-ammonium chloride; methanol; cerium(III) chloride / acetonitrile / 1.1 h / 30 °C / Irradiation; Flow reactor; Inert atmosphere 2: dichloromethane / 2 h / 20 °C 3: hydrogen / methanol / 12 h / 20 °C View Scheme

C10H18N2O*C2HF3O2 → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
With hydrogen In methanol at 20℃; for 12h;

di-tert-butyl (3-hydroxyadamantan-1-yl)hydrazine-1,2-dicarboxylate → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: dichloromethane / 2 h / 20 °C 2: hydrogen / methanol / 12 h / 20 °C View Scheme

3-bromoadamantane-1-carboxylic acid (21816-08-0) → 3-aminoadamantan-1-ol (702-82-9)

Conditions	Yield
Stage #1: 3-bromoadamantane-1-carboxylic acid With diphenyl phosphoryl azide; triethylamine; tert-butyl alcohol at 80 - 110℃; Stage #2: With hydrogen bromide Reflux; Stage #3: With sodium hydroxide at 30℃;

4,6-dichloro-1H-indole-2-carboxylic acid (101861-63-6) + 3-aminoadamantan-1-ol (702-82-9) → 4,6-dichloro-N-(3-hydroxyadamantan-1-yl)-1H-indole-2-carboxamide

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃;	99%

2,4,6-trimethoxybenzaldehyde (830-79-5) + 3-aminoadamantan-1-ol (702-82-9) → 3-((2,4,6-trimethoxybenzylidene)amino)adamantan-1-ol

Conditions	Yield
In benzene Reflux; Dean-Stark;	99%

di-tert-butyl dicarbonate (24424-99-5) + 3-aminoadamantan-1-ol (702-82-9) → tert-butyl (3-hydroxyadamantan-1-yl)carbamate (847795-89-5)

Conditions	Yield
With triethylamine In dichloromethane at 20℃;	97%
With sodium hydroxide In 1,4-dioxane; water at 20℃; for 16h;	65%
With triethylamine In tetrahydrofuran at 20℃; Cooling with ice;

3-aminoadamantan-1-ol (702-82-9) + chloroacetonitrile (107-14-2) → (3-hydroxyadamantan-1-ylamino)acetonitrile

Conditions	Yield
With potassium carbonate; potassium iodide In ethyl acetate at 75℃;	97%

Indole-2-carboxylic acid (1477-50-5) + 3-aminoadamantan-1-ol (702-82-9) → N-(3-hydroxyadamantan-1-yl)-1H-indole-2-carboxamide

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃;	97%

3-aminoadamantan-1-ol (702-82-9) + Glyoxilic acid (298-12-4) → [(3-hydroxyadamantan-1-yl)imino]acetic acid (1334337-69-7)

Conditions	Yield
With acetic anhydride; N-ethyl-N,N-diisopropylamine In tetrahydrofuran for 2h; Reagent/catalyst; Solvent; Temperature; Reflux;	96.1%
In tetrahydrofuran for 3h; Reflux;

3-aminoadamantan-1-ol (702-82-9) + glyoxalic acid monohydrate (6000-59-5) → [(3-hydroxyadamantan-1-yl)imino]acetic acid (1334337-69-7)

Conditions	Yield
With acetic anhydride; N-ethyl-N,N-diisopropylamine In tetrahydrofuran for 2h; Reagent/catalyst; Solvent; Temperature; Reflux;	96.1%

5-methoxy-1H-indole-2-carboxylic acid (4382-54-1) + 3-aminoadamantan-1-ol (702-82-9) → C20H24N2O3

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃;	96%

3-aminoadamantan-1-ol (702-82-9) + acetyl chloride (75-36-5) → N-(3-hydroxyadamantan-1-yl)acetamide (778-10-9)

Conditions	Yield
With triethylamine In tetrahydrofuran; N,N-dimethyl-formamide	95%

3-aminoadamantan-1-ol (702-82-9) + C9H11ClN2O3 → C19H27N3O4

Conditions	Yield
With potassium carbonate; potassium iodide In tetrahydrofuran at 20℃; for 12h; Temperature;	93.4%

6-bromo-indole-2-carboxylic acid(Ref.7.) (16732-65-3) + 3-aminoadamantan-1-ol (702-82-9) → 6-bromo-N-(3-hydroxyadamantan-1-yl)-1H-indole-2-carboxamide

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃;	93%

3-aminoadamantan-1-ol (702-82-9) + benzaldehyde (100-52-7) → 3-benzylaminoadamantan-1-ol

Conditions	Yield
Stage #1: 3-aminoadamantan-1-ol; benzaldehyde In methanol for 3h; Reflux; Stage #2: With sodium tetrahydroborate In methanol at 0 - 5℃;	92.8%
Stage #1: 3-aminoadamantan-1-ol; benzaldehyde In methanol for 10h; Inert atmosphere; Reflux; Stage #2: With methanol; sodium tetrahydroborate at 0 - 25℃;	80%

3-aminoadamantan-1-ol (702-82-9) + benzyl chloroformate (501-53-1) → benzyl ((3-hydroxy)adamantan-1-yl)carbamate (565453-43-2)

Conditions	Yield
With potassium carbonate In tetrahydrofuran at 20℃; for 2.16667h;	92%
With potassium carbonate In tetrahydrofuran at 20℃; for 2h;	85%
With potassium carbonate In tetrahydrofuran at 20℃; for 2h; Cooling with ice;

3-aminoadamantan-1-ol (702-82-9) + (S)-1-(2-chloroacetyl)pyrrolidine-2-carbonitrile (207557-35-5) → (2S)-1-{[{2[(2S)-2-cyanopyrrolidin-1-yl]-2-oxoethyl}[(3-hydroxytricyclo[3.3.1.1(3,7)]dec-1-yl)amino]]acetyl}pyrrolidine-2-carbonitrile (1036959-23-5)

Conditions	Yield
With potassium carbonate; tri tert-butylphosphoniumtetrafluoroborate In dichloromethane at 30℃; for 3h; Solvent; Reagent/catalyst;	91%
With potassium carbonate; potassium iodide In butanone for 4h; Reflux;	77%
With potassium carbonate; potassium iodide In tetrahydrofuran for 5h; Product distribution / selectivity; Heating / reflux;	72%

Upstream product

• 768-94-5 1-Adamantanamine 
• 1885-14-9 phenyl chloroformate 
• 778-10-9 N-(3-hydroxyadamantan-1-yl)acetamide 
• 21816-08-0 3-bromoadamantane-1-carboxylic acid 
• 768-95-6 1-adamanthanol 
• 880-52-4 N-(1-adamantyl)acetamide 
• 243145-00-8 3-nitro-1-amantadine 
• 67496-92-8 3-nitroadamantan-1-ol 
• 665-66-7 amantadine hydrochloride 

Downstream Products

• 565453-39-6 (S)-1-[2-(3-hydroxyadamantan-1-ylamino)acetyl]pyrrolidine-2-carboxylic acid amide 
• 274901-16-5 vildagliptin 
• 1057284-28-2 1-(2-chloro-benzenesulfonyl)-piperidine-3-carboxylic acid (3-hydroxy-adamantan-1-yl)-amide 
• 620171-62-2 (3-cyclohexylcarbamoyloxy-adamantan-1-yl)-carbamic acid benzyl ester 
• 620170-84-5 [3-(4-methoxy-phenylcarbamoyloxy)-adamantan-1-yl]-carbamic acid benzyl ester 
• 620171-36-0 (3-phenylcarbamoyloxy-adamantan-1-yl)-carbamic acid benzyl ester 
• 565453-44-3 (3-tert-butylcarbamoyloxy-adamantan-1-yl)-carbamic acid benzyl ester 
• 620171-50-8 (3-diisopropylcarbamoyloxy-adamantan-1-yl)-carbamic acid benzyl ester 
• 620171-66-6 acetic acid 3-benzyloxycarbonylamino-adamantan-1-yl ester 
• 1026223-11-9 3-[[(cyclohexylamino)carbonyl]oxy]-1-aminoadamantane 
• 1027414-42-1 3-[[(4-methoxyphenylamino)carbonyl]oxy]-1-aminoadamantane 
• 1027175-44-5 3-[[(phenylamino)carbonyl]oxy]-1-aminoadamantane 
• 565453-43-2 benzyl ((3-hydroxy)adamantan-1-yl)carbamate 

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The invention relates to the technical field of organic synthesis, in particular to 3-amino-1-adamantanol and a synthesis method thereof. The synthesis method of 3-amino-1-adamantanol comprises the following steps of: mixing 3-acetyl amino-1-adamantanol, strong base and an alcohol solvent, heating to 100-200 DEG C in a closed environment, reacting for 5-10h, cooling, crystallizing, filtering, washing the filter cake with the alcohol solvent, merging the filtrate, and distilling to remove the solvent, thereby obtaining the 3-amino-1-adamantanol. The synthesis method of 3-amino-1-adamantanol provided by the invention has the characteristics of simple steps, easiness in operation, high yield, high efficiency and suitability for industrial production; and the used raw material is adamantane, and special adamantane derivatives such as amantadine and adamantanecarboxylic acid are not needed as raw materials, so that the production cost is further reduced.

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The invention relates to the technical field of chemical synthesis preparation, in particular to 3 - amino -1 - adamantanol and a preparation method and application thereof. The method comprises the following steps. After a period of time, crushed ice is added, and then crushed ice is added until the reaction solution becomes clear ink green, pH values are adjusted to obtain the product, and the product is refluxed and filtered through the organic solution A and the organic solution B, respectively. After drying, 3 - amino -1 - adamantane is obtained. The 3 - amino -1 - adamantanol with high yield can be obtained through cheap and easily available raw materials and simple operation, and the method is low in cost, fast in reaction and more suitable for industrial production.