134-32-7

Basic information

• Product Name: 1-Aminonaphthalene
• Synonyms: 1-Aminonaftalen;1-aminonaftalen(czech);1-Naftilamina;1-Naftylamin;1-Naftylamine;1-Naphthalamine;1-Naphthalenamine;1-Naphthylamin
• CAS NO: 134-32-7
• Molecular Formula: C₁₀H₉N
• Molecular Weight: 143.19
• EINECS: 205-138-7
• Product Categories: Intermediates of Dyes and Pigments;Anilines, Aromatic Amines and Nitro Compounds;Chemistry;Amines;Aromatics;Intermediates;Building Blocks;C10;Chemical Synthesis;Nitrogen Compounds;Organic Building Blocks;Fluorescent
• Mol File: 134-32-7.mol
• Article Data: 196

Chemical Properties

• Melting Point: 47-50 °C(lit.)
• Boiling Point: 301 °C(lit.)
• Flash Point: >230 °F
• Appearance: light tan to purple/flakes
• Density: 1.114 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.00108mmHg at 25°C
• Refractive Index: 1.6703
• Storage Temp.: 2-8°C
• Solubility: 1.7g/l
• PKA: 3.92(at 25℃)
• Water Solubility: Insoluble. 0.1698 g/100 mL
• Merck: 14,6398
• BRN: 386133
• CAS DataBase Reference: 1-Aminonaphthalene(CAS DataBase Reference)
• NIST Chemistry Reference: 1-Aminonaphthalene(134-32-7)
• EPA Substance Registry System: 1-Aminonaphthalene(134-32-7)

Safety Data

• Hazard Codes: C,N,Xn,T
• Statements: 34-51/53-22-45
• Safety Statements: 26-36/37/39-45-61-24-53
• RIDADR: UN 2790 8/PG 3
• WGK Germany: 2
• RTECS: QM1400000
• F: 8-23
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 134-32-7(Hazardous Substances Data)

Usage

Chemical Properties

α-Naphthylamine exists as white needle-like crystals which turn red on exposure to air. Has a weak ammonia-like odor. Solubility in water is 0.16% at 20℃. It behaves as a typical primary aromatic amine in forming salts with strong acids (but not with acetic or benzoic acid) and readily forming N-acyl derivatives. 1-Naphthylamine couples with diazo compounds in the 4-position, with up to 10 % byproduct being formed by coupling in the 2-position.

Physical properties

White to yellow crystals or rhombic needles with an unpleasant odor. Becomes purplish-red on exposure to air. Odor threshold concentrations were 140–290 μg/m3 (quoted, Keith and Walters, 1992).

Uses

1-Naphthylamine is used as a chemical intermediate in the synthesis of a wide variety of chemicals, the most important of which include dyes, tonic prints, Toning prints made with cerium salts, antioxidants, and herbicides.

Preparation

1-Naphthylamine is prepared by reduction of 1-nitronaphthalene: Purified 1-nitronaphthalene was traditionally reduced with iron in boiling dilute hydrochloric acid, but modern plants use hydrogenation with a nickel catalyst. The 1-naphthylamine produced is further purified by distillation under vacuum. The content of 2-naphthylamine in the commercial product is specified at <10 ppm.

Application

1-Naphthylamine is mainly used for the production of 1-naphthol. Other major uses are in the production of aminonaphthalenesulfonic acid dye intermediates and as a component of azo dyes.1-Naphthylamine can also be used as a starting material to synthesize:[(S)-HY-Phos], a novel chiral phosphine-phosphoramidite ligand for use in rhodium-catalyzed asymmetric hydrogenation of various functionalized olefins.N-(naphthalen-1-yl)picolinamide.Pitnot-2, an inactive analog of clathrin inhibitor Pitstop 2.

Definition

ChEBI: 1-naphthylamine is a naphthylamine that is naphthalene substituted by an amino group at position 1. It has a role as a human xenobiotic metabolite.

Synthesis Reference(s)

Tetrahedron Letters, 25, p. 429, 1984 DOI: 10.1016/S0040-4039(00)99903-9Chemical and Pharmaceutical Bulletin, 34, p. 1524, 1986 DOI: 10.1248/cpb.34.1524

General Description

1-naphthylamine appears as a crystalline solid or a solid dissolved in a liquid. Insoluble in water and denser than water. Contact may slightly irritate skin, eyes and mucous membranes. May be slightly toxic by ingestion. Used to make other chemicals.

Air & Water Reactions

Sensitive to exposure to air and light. Insoluble in water. Napthyl amines can be slowly hydrolyzed, releasing NH3 as a byproduct [N.L. Drake, Org. React. 1, (1942), 105].

Reactivity Profile

1-Aminonaphthalene is incompatible with oxidizing agents. 1-Aminonaphthalene is also incompatible with nitrous acid. 1-Aminonaphthalene reduces warm ammoniacal silver nitrate. .

Hazard

Toxic, especially if containing the β isomer; a questionable carcinogen.

Health Hazard

1-Naphthylamine is a moderately toxic and cancer-causing substance. The toxic symptoms arising from oral intake or skin absorption of this compound include acute hemorrhagic cystitis, dyspnea, ataxia, dysuria, and hematuria. An intraperitoneal LD50 value in mice is 96 mg/kg. Inhalation of dusts or vapors is hazardous, showing similar symptoms. 1-Naphthylamine caused leukemia in rats. There is substantial evidence of its cancer-causing effects in animals and humans.

Fire Hazard

Special Hazards of Combustion Products: Toxic nitrogen oxides are produced in a fire.

Safety Profile

Confirmed carcinogen with experimental tumorigenic data. Along with p-naphthylamine and benzidine, it has been incriminated as a cause of urinary bladder cancer. Poison by subcutaneous and intraperitoneal routes. Moderately toxic by ingestion. Mutation data reported. Combustible when exposed to heat or flame. Incompatible with nitrous acid. To fight fire, use dry chemical, CO2, mist, spray. When heated to decomposition it emits toxic fumes of NOx.

Potential Exposure

α-Naphthylamine is used as an intermediate in dye production; for manufacturing herbicides and antioxidants; in the manufacture of condensation colors, rubber, and in the synthesis of many chemicals, such as α-naphthol, sodium naphthionate; o-naphthionic acid; Neville and Winther’s acid; sulfonated naphthylamines, α-naphthylthiourea (a rodenticide); and N-phenyl- α-naphthylamine.

Carcinogenicity

1-Naphthylamine has been tested for carcinogenic activity in mice, hamsters, and dogs by oral administration, in newborn mice by SC injection, and in mice by bladder implantation. Most of these studies reported negative findings, while a few found marginal or equivocal results. In contrast, with the exception of bladder implantation study, 2-naphthylamine gave positive results in virtually all these studies. Mixed results were reported in various genotoxicity tests. 1-Naphthylamine was positive in the Ames test and in vitro chromosome aberration, negative in micronucleus, cell transformation, and recessive lethal mutation in Drosophila, and inconclusive in sister chromatid exchange assays.

Environmental fate

Biological. 1-Naphthylamine added to three different soils was incubated in the dark at 23 °C under a carbon dioxide-free atmosphere. After 308 d, 16.6 to 30.7% of the 1-naphthylamine added to soil biodegraded to carbon dioxide (Graveel et al., 1986). Li and Lee (1999) investigated the reaction of 10 mL of 7 mM 1-naphthylamine with 4 g of a Chalmers soil (pH: 6.5, 11.1% sand, 72.8% silt, 16.0% clay). After 120 h, the soil was washed with acetonitrile and the extractant analyzed using GC/MS. The primary transformation product was a dimer tentatively identified as N-(4-aminonaphthyl)-1-naphthylamine. The investigators hypothesized that the formation of this compound and two other unidentified dimers was catalyzed by minerals present in the soil. Heukelekian and Rand (1955) reported a 5-d BOD value of 0.89 g/g which is 34.6% of the ThOD value of 2.57 g/g. In activated sludge inoculum, following a 20-d adaptation period, no degradation was observed (Pitter, 1976). Photolytic. Low et al. (1991) reported that the photooxidation of aqueous primary amine solutions by UV light in the presence of titanium dioxide resulted in the formation of ammonium and nitrate ions. Chemical/Physical. Kanno et al. (1982) studied the aqueous reaction of 1-naphthylamine and other substituted aromatic hydrocarbons (aniline, toluidine, 2-naphthylamine, phenol, cresol, pyrocatechol, resorcinol, hydroquinone, and 1-naphthol) with hypochlorous acid in the presence of ammonium ion. They reported that the aromatic ring was not chlorinated as expected but was cleaved by chloramine forming cyanogen chloride. The amount of cyanogen chloride that formed increased as the pH was lowered (Kanno et al., 1982). At influent concentrations (pH 3.0) of 10, 1.0, 0.1, and 0.01 mg/L, the GAC adsorption capacities were 250, 140, 79, and 44 mg/g, respectively. At pHs 7.0 and 9.0, the GAC adsorption capacities were 360, 160, 75, and 34 mg/g at influent concentrations of 10, 1.0, 0.1, and 0.01 mg/L, respectively (Dobbs and Cohen, 1980).

Shipping

UN2077 alpha-Naphthylamine, Hazard Class: 6.1; Labels: 6.1-Poisonous materials. PGIII.

Purification Methods

Sublime the amine at 120o in a stream of nitrogen, then crystallise it from pet ether (b 60-80o), or absolute EtOH then diethyl ether. Dry it in vacuo in an Abderhalden pistol. It has also been purified by crystallisation of its hydrochloride (see below) from water, followed by liberation of the free base and distillation; it is finally purified by zone melting. The styphnate has m 181-182o (from EtOH). [Beilstein 12 III 2846, 12 IV 3009.] CARCINOGEN.

Incompatibilities

Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides, nitrous acid, organic anhydrides, isocyanates, aldehydes. Oxidizes on contact with air.

Waste Disposal

Controlled incineration whereby oxides of nitrogen are removed from the effluent gas by scrubber, catalyst, or thermal device. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal.

InChI:InChI=1/C10H9N/c11-10-7-3-5-8-4-1-2-6-9(8)10/h1-7H,11H2

Synthetic route

1-Nitronaphthalene (86-57-7) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With triethylsilane; palladium dichloride In ethanol at 20℃; for 0.166667h; Inert atmosphere;	100%
With hydrazine hydrate at 90℃; for 1h; chemoselective reaction;	100%
With Zr12(μ3-O)5[(μ3-O)CoCl]8[(μ2-O)2(μ3-O)CoCl]3Li3(triphenyldicarboxylate)9; hydrogen; sodium triethylborohydride In toluene at 110℃; under 30003 Torr; for 42h; Catalytic behavior; Inert atmosphere; Schlenk technique;	100%

naphthalene (91-20-3) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
Stage #1: naphthalene With pyridine; trifluorormethanesulfonic acid; tetrabutylammonium tetrafluoroborate In acetonitrile at 25℃; Electrochemical reaction; Stage #2: With piperidine In acetonitrile at 80℃; for 12h; Electrochemical reaction;	99%
With oxygen; potassium carbonate; ammonium chloride In acetonitrile at 20℃; for 48h; pH=8 - 10; UV-irradiation;	53%
With boron carbon nitride; ammonia; oxygen In dimethyl sulfoxide under 760.051 Torr; Irradiation;	53%

N-(2-naphthyl) allylcarbamate (25216-21-1) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With chloro-trimethyl-silane; cyclopentadienyl titanium(IV) trichloride; magnesium; triethylamine In tetrahydrofuran at 50℃; for 24h;	99%

1-tetralone oxime (3349-64-2, 68253-36-1, 100485-58-3) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With Pd(OH)x/LDH In N,N-dimethyl acetamide at 150℃; for 6h; Schlenk technique; Inert atmosphere;	99%

C29H23NO2 → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With palladium 10% on activated carbon In tetrahydrofuran; water at 45℃; for 6h;	99%

1-azidonaphthalene (6921-40-0) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With D-glucose; potassium hydroxide In water at 85℃; for 0.166667h; Green chemistry; chemoselective reaction;	98%
With methanol; sodium tetrahydroborate In tetrahydrofuran for 1h; Heating;	94%
With zinc(II) tetrahydroborate In 1,2-dimethoxyethane for 1.5h; Ambient temperature;	94%

1-Bromonaphthalene (90-11-9) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With 2-((dicyclohexylphosphino)methyl)-1,3-bis(2,6-diisopropylphenyl)-4,5-dimethyl-1H-imidazol-3-ium iodide; ammonia; palladium diacetate; sodium t-butanolate In 1,4-dioxane at 120℃; under 7500.75 Torr; for 24h; Autoclave; Inert atmosphere;	98%
With ammonia; triethylamine In water at 20℃; for 10h;	97%
With ammonium hydroxide In water at 20℃; for 9h; Green chemistry;	95%

benzhydrylidene-[1]naphthyl-amine (32566-86-2) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With hydrogenchloride In tetrahydrofuran; water Ambient temperature;	98%
With hydrogenchloride In tetrahydrofuran at 20℃;	80%
With hydrogenchloride In tetrahydrofuran; water at 20℃;	18.1 mg

1'-naphthacetophenone (941-98-0) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With methanol; O-benzenesulfonyl-acetohydroxamic acid ethyl ester; toluene-4-sulfonic acid at 23℃; for 24h; Inert atmosphere;	98%
With O-benzenesulfonyl-acetohydroxamic acid ethyl ester; toluene-4-sulfonic acid In ethanol at 20℃; for 24h;	62%

1-Chloronaphthalene (90-13-1) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With 2-((dicyclohexylphosphino)methyl)-1,3-bis(2,6-diisopropylphenyl)-4,5-dimethyl-1H-imidazol-3-ium iodide; ammonia; palladium diacetate; sodium t-butanolate In 1,4-dioxane at 120℃; under 7500.75 Torr; for 24h; Autoclave; Inert atmosphere;	97%
With ammonium sulfate; (R)-(-)-1-[(SP)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-tert-butylphosphine; bis(tri-ortho-tolylphosphine)palladium(0); sodium t-butanolate In 1,4-dioxane at 100℃; for 12h; Inert atmosphere; Glovebox;	97%
With ammonium hydroxide; potassium phosphate In dimethyl sulfoxide at 80℃; UV-irradiation;	90%

3-(Naphthalen-1-ylcarbamoyloxy)-cyclohex-1-enecarboxylic acid ethyl ester (92599-49-0) → ethyl cyclohex-2-enyl-acetate (55510-68-4, 200637-78-1) + 1-amino-naphthalene (134-32-7)

Conditions	Yield
With lithium di-n-butylcuprate In N,N,N,N,N,N-hexamethylphosphoric triamide; diethyl ether at -50 - -20℃; for 2h; in presence other reagents (Zn, CrCl2), too;	A 97% B n/a

1-Iodonaphthalene (90-14-2) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With ammonium hydroxide In water at 20℃; for 9h; Green chemistry;	97%
With copper(I) oxide; ammonium hydroxide In 1-methyl-pyrrolidin-2-one at 80℃; for 15h;	96%
Stage #1: 1-Iodonaphthalene With copper(l) iodide; D-glucosamine hydrochloride; potassium carbonate In water; acetone at 90℃; for 0.166667h; Stage #2: With ammonia In water; acetone at 90℃; for 24h;	95%

1,2-di(naphthalen-1-yl)diazene (487-10-5) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With zinc In methanol at 25℃; for 0.15h; Inert atmosphere;	96%
With perchloric acid In isopropyl alcohol; acetonitrile at 25℃; for 0.666667h; pH=2; Inert atmosphere; Irradiation;	92%
With formic acid; zinc In methanol at 20℃; for 0.266667h;	85%
With ammonium formate; nickel In methanol at 20℃; for 0.266667h;	85%
With ammonium acetate; zinc In methanol at 20℃; for 0.0833333h;	85%

3,4-dihydronaphthalene-1(2H)-one (529-34-0) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
	95%
With ethene; 5%-palladium/activated carbon; ammonium acetate In acetonitrile at 90℃; under 760.051 Torr; for 48h; Reagent/catalyst; Schlenk technique;	89%
Multi-step reaction with 2 steps 2: hydrogen chloride; acetic acid; acetic acid anhydride View Scheme

2-[(naphthalen-1-ylamino)methylidene]malonic acid diethyl ester (131775-94-5) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With ethylenediamine In ethanol at 20℃; for 5h;	95%

naphthalen-1-ylcarbamic acid benzyl ester (6336-03-4) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With methanol; sodium tetrahydroborate; nickel(II) chloride hexahydrate at 20℃; for 0.25h; chemoselective reaction;	94%
With methylmagnesium bromide; hydrogen; palladium diacetate; nickel diacetate In water at 45℃; for 18h;	91%
With 4-methyl-morpholine; tetrahydroxydiboron; 5%-palladium/activated carbon In 1,2-dichloro-ethane at 50℃; for 1.5h;	76%

1-N-ethylnaphthylamine (118-44-5) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With piperidine; dichloro(dimethylglyoxime)(dimethylglyoximato)cobalt(III); (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate In acetonitrile at -78℃; for 24h; Reagent/catalyst; Sealed tube; Inert atmosphere; Irradiation;	94%

1-Bromonaphthalene (90-11-9) → N,N-di(naphth-1-yl)amine (737-89-3) + 1-amino-naphthalene (134-32-7)

Conditions	Yield
Stage #1: 1-Bromonaphthalene With ammonia; sodium t-butanolate; [(CyPF-tBu)PdCl2] In 1,2-dimethoxyethane at 90℃; under 4137.29 - 10343.2 Torr; for 20h; Stage #2: With hydrogenchloride In 1,2-dimethoxyethane; water at 20℃; for 0.0833333h; Stage #3: With sodium hydrogencarbonate In 1,2-dimethoxyethane; water Product distribution / selectivity;	A n/a B 92%
Stage #1: 1-Bromonaphthalene With lithium amide; [(CyPF-tBu)PdCl2] In 1,2-dimethoxyethane at 80℃; for 20h; Sealed vial; Stage #2: With hydrogenchloride In 1,2-dimethoxyethane; water at 20℃; for 0.0833333h; Stage #3: With sodium hydrogencarbonate In 1,2-dimethoxyethane; water Product distribution / selectivity;	A n/a B 89%
With C28H30Cl5N3Pd; ammonia; lithium isopropoxide; sodium t-butanolate In 1,4-dioxane at 100℃; for 2h; Reagent/catalyst; Inert atmosphere; Schlenk technique;	A n/a B 82%

1-Naphthylboronic acid (13922-41-3) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With copper(I) oxide; ammonium hydroxide; air In methanol at 20℃; for 16h;	92%
With potassium carbonate; ammonium hydroxide In methanol at 60℃; for 17h;	90%
With O-(2,4-dinitrophenyl)hydroxylamine In toluene at 50℃; for 24h; Inert atmosphere;	84%

1-naphthyl N,N-diethylcarbamate (85630-39-3) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With ammonium sulfate; C43H60ClFeNNiP2; sodium t-butanolate In o-xylene at 100℃; for 16h; Reagent/catalyst; Inert atmosphere; Autoclave;	91%
With (CyPFCy)Ni(o-tol)Cl; ammonia; sodium t-butanolate In 1,4-dioxane at 80℃; for 24h; Reagent/catalyst; Inert atmosphere; Sealed tube;	60%

2-(naphthalen-1-ylamino)-1-phenylethan-1-one (33555-03-2) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With magnesium; acetic acid In methanol at 20℃;	90%

naphthalen-1-yl-carbamic acid tert-butyl ester (72594-62-8) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With 3-butyl-l-methyl-1H-imidazol-3-iumtrifloroacetate In 1,4-dioxane; water at 70 - 72℃; for 2h;	89%
With water at 150℃; for 8h; Subcritical conditions;	88%
With methanol; oxalyl dichloride at 20℃; for 2h; Temperature;	87%

1-tetralone pivaloyl oxime (1234464-24-4) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With palladium diacetate; potassium carbonate; tricyclopentylphosphine In toluene at 95℃; for 8h; Reagent/catalyst; Glovebox;	87%

1-naphthylboronic acid pinacol ester (68716-52-9) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With potassium tert-butylate; 1-amino-1,4-diazabicyclo[2.2.2]octane-1,4-diium iodide In tetrahydrofuran at 100℃; for 1h; Sealed tube;	87%

(E)-di-[1]naphthyl-diazene (6141-93-1) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With nickel; hydrazinium monoformate In methanol for 0.25h; Heating;	85%

4-Bromo-1-naphthylamine (2298-07-9) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
Stage #1: 4-Bromo-1-naphthylamine With palladium dichloride In water at 20℃; for 0.0333333h; Stage #2: With 1,1,3,3-Tetramethyldisiloxane for 2.46667h;	85%

N,N-dimethyl-3-(naphthalen-1-ylamino)propionamide → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With Imidazole hydrochloride at 150℃; for 9h;	85%
With Imidazole hydrochloride In neat (no solvent) at 150℃; for 9h; Schlenk technique;	85%

1-naphthylmagnesiumbromide (703-55-9) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
Stage #1: 1-naphthylmagnesiumbromide With zinc(II) chloride In tetrahydrofuran at -3 - 20℃; Inert atmosphere; Stage #2: With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; N,N-diphenylaminobenzene; acetone oxime-o-p-benzenesulfonic ester; copper(l) chloride In tetrahydrofuran at 20℃; for 1.5h; Inert atmosphere; Stage #3: With hydrogenchloride; water In tetrahydrofuran at 20℃; for 4h; Inert atmosphere;	84%
With hydrogenchloride; O-(diphenylphosphinyl)hydroxylamine In tetrahydrofuran for 12h; Ambient temperature;	31%
Multi-step reaction with 2 steps 1.1: tetrahydrofuran / -5 - 20 °C / Inert atmosphere 2.1: triphenylphosphine; acetone oxime-o-p-benzenesulfonic ester / tetrahydrofuran / 0.08 h / 20 °C / Inert atmosphere 2.2: 20 °C / Inert atmosphere View Scheme

N-methylnaphthalen-1-amine (2216-68-4) → 1-amino-naphthalene (134-32-7)

Conditions	Yield
With piperidine; dichloro(dimethylglyoxime)(dimethylglyoximato)cobalt(III); (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate In acetonitrile at -78℃; for 24h; Reagent/catalyst; Sealed tube; Inert atmosphere; Irradiation;	84%

chloroformic acid ethyl ester (541-41-3) + 1-amino-naphthalene (134-32-7) → ethyl (naphthalen-1-yl)carbamate (5255-68-5)

Conditions	Yield
With potassium carbonate In tetrahydrofuran; water at 20℃; for 12h;	100%
With triethylamine In tetrahydrofuran for 1h; Heating;	99%

acetic anhydride (108-24-7) + 1-amino-naphthalene (134-32-7) → 1-acetamidonaphthalene (575-36-0)

Conditions	Yield
In dichloromethane at 20℃; Inert atmosphere;	100%
With silica gel for 0.05h; Microwave irradiation; neat (no solvent);	98%
With rice husk ash at 20℃; Green chemistry;	98%

ammonium thiocyanate (1147550-11-5) + 1-amino-naphthalene (134-32-7) → naphthalen-1-yl-thiourea (86-88-4)

Conditions	Yield
Stage #1: ammonium thiocyanate With benzoyl chloride In acetone for 0.333333h; Reflux; Stage #2: 1-amino-naphthalene In acetone for 1h; Reflux; Stage #3: With sodium hydroxide In water at 80℃; for 0.5h;	100%
With hydrogenchloride; water
With hydrogenchloride at 100℃;

1-amino-naphthalene (134-32-7) + 4-nitrobenzaldehdye (555-16-8) → N-(napht-1-yl)-N-(p-nitrobenzylidene)amine (967-13-5)

Conditions	Yield
for 24h; Ambient temperature;	100%
In ethanol	85%
With ethanol

1-amino-naphthalene (134-32-7) + benzaldehyde (100-52-7) → N-benzylidenenaphthalen-1-amine (890-51-7)

Conditions	Yield
With aluminum oxide for 5h; Milling;	100%
In water at 20℃; for 2h;	80%
In dichloromethane for 10h; Reflux;	70%

1-amino-naphthalene (134-32-7) + 4-hydroxy-benzaldehyde (123-08-0) → (E)-4-((naphthalen-1-ylimino)methyl)phenol (93324-84-6)

Conditions	Yield
for 2h; Ambient temperature;	100%
at 80℃; for 0.0833333h;	78%

1-amino-naphthalene (134-32-7) + vanillin (121-33-5) → 2-methoxy-4-(1-naphthyliminomethyl)phenol (78174-01-3)

Conditions	Yield
for 24h; Ambient temperature;	100%
In ethanol at 20 - 23℃;	92%
With ethanol
In ethanol

1-amino-naphthalene (134-32-7) + p-toluenesulfonyl chloride (98-59-9) → N-tosyl-1-naphthylamine (18271-17-5)

Conditions	Yield
With triethylamine In dichloromethane at 4℃;	100%
With pyridine	98%
at 20℃; for 0.166667h;	94%

1-amino-naphthalene (134-32-7) + diethyl 2-ethoxymethylenemalonate (87-13-8) → 2-[(naphthalen-1-ylamino)methylidene]malonic acid diethyl ester (131775-94-5)

Conditions	Yield
High vacuum;	100%
In ethanol at 28℃; for 6h;	98%
at 130℃; for 2.75h; Substitution;	91%

1-amino-naphthalene (134-32-7) → 1-azidonaphthalene (6921-40-0)

Conditions	Yield
With tert.-butylnitrite; trimethylsilylazide In acetonitrile at 0 - 20℃; for 1h;	100%
With dmap; 2-azido-1,3-dimethylimidazolin-1-ium hexafluorophosphate In dichloromethane at 50℃; for 1.5h; Inert atmosphere;	92%
With dmap; 2-azido-1,3-dimethyl-4,5-dihydro-1H-imidazol-3-ium hexafluorophosphate (V) In dichloromethane at 30℃; for 5h; Reagent/catalyst; Solvent; Inert atmosphere;	92%

4-chlorobenzaldehyde (104-88-1) + 1-amino-naphthalene (134-32-7) → (E)-N-(4-chlorobenzylidene) naphthalen-1-amine (135569-53-8)

Conditions	Yield
for 2h; Ambient temperature;	100%
In benzene for 4h; Heating;
In benzene Heating;

2,2,2-trifluoro-N-{2,2,2-trifluoro-1-(trifluoromethyl) ethylidene}acetamide (52225-57-7) + 1-amino-naphthalene (134-32-7) → N-(α-trifluoroacetylaminohexafluoroisopropyl)-α-naphthylamine (121825-80-7)

Conditions	Yield
In chloroform at -20℃;	100%

1,1,1-trifluoro-4,4-diethoxy-3-buten-2-one (40657-29-2) + 1-amino-naphthalene (134-32-7) → (E)-4-Ethoxy-1,1,1-trifluoro-4-(naphthalen-1-ylamino)-but-3-en-2-one (128648-67-9)

Conditions	Yield
In acetonitrile for 18h; Ambient temperature;	100%

1-amino-naphthalene (134-32-7) + N,N-diethylaminomethylene-1,1,1,5,5,5-hexafluoroacetylacetone (74888-65-6) → 1,1,1,5,5,5-Hexafluoro-3-(naphthalen-1-ylaminomethylene)-pentane-2,4-dione (155495-74-2)

Conditions	Yield
With iron(III) chloride	100%

1-amino-naphthalene (134-32-7) + N-α-Tosyl-4-cyanphenylalaninchlorid (80852-48-8) → 3-(4-Cyano-phenyl)-N-naphthalen-1-yl-2-(toluene-4-sulfonylamino)-propionamide (80852-66-0)

Conditions	Yield
In benzene for 1.5h; Ambient temperature;	100%

3-Methylindene (767-60-2) + 1-amino-naphthalene (134-32-7) + benzaldehyde (100-52-7) → (6S,6aR,11bR)-11b-Methyl-6-phenyl-6,6a,7,11b-tetrahydro-5H-benzo[h]indeno[1,2-c]quinoline

Conditions	Yield
With (polyallyl)scanduium trifylamide ditriflate In dichloromethane; acetonitrile at 40℃; for 15h;	100%

1-amino-naphthalene (134-32-7) + 4-bromo-benzaldehyde (1122-91-4) → [1-(4-Bromo-phenyl)-meth-(E)-ylidene]-naphthalen-1-yl-amine (116401-74-2)

Conditions	Yield
for 2h; Ambient temperature;	100%
In benzene Reflux;

cis,trans-2,5-dimethoxytetrahydrofuran (696-59-3) + 1-amino-naphthalene (134-32-7) → N-naphthylpyrrole (92163-14-9)

Conditions	Yield
With bismuth (III) nitrate pentahydrate at 75℃; for 0.0833333h; Microwave irradiation; neat (no solvent);	100%
With bismuth (III) nitrate pentahydrate at 20℃; for 0.0833333h; Sonication; Neat (no solvent);	95%
With scandium tris(trifluoromethanesulfonate) In 1,4-dioxane at 100℃; for 0.5h; Clauson-Kaas condensation;	94%

di-tert-butyl dicarbonate (24424-99-5) + 1-amino-naphthalene (134-32-7) → naphthalen-1-yl-carbamic acid tert-butyl ester (72594-62-8)

Conditions	Yield
Stage #1: 1-amino-naphthalene With triethylamine In tetrahydrofuran; water at 20℃; for 0.0833333h; Stage #2: di-tert-butyl dicarbonate In tetrahydrofuran; water at 0 - 20℃; for 6h;	100%
In ethanol at 30℃; for 24h;	99%
With iron oxide In ethanol at 20℃; for 3h; Green chemistry; chemoselective reaction;	99%

1-amino-naphthalene (134-32-7) + acetylenedicarboxylic acid diethyl ester (762-21-0) → C18H19NO4 (1148148-44-0)

Conditions	Yield
In methanol Reflux;	100%
In ethanol at 20℃; for 0.5h;

4,4'-bicyclohexanone (23391-99-3) + 1-amino-naphthalene (134-32-7) → C32H36N2

Conditions	Yield
With sodium tris(acetoxy)borohydride; acetic acid In dichloromethane at 20℃; for 16h; Cooling with ice;	100%

tetrakis(hydroxymethyl)phosphonium chloride (124-64-1) + 1-amino-naphthalene (134-32-7) → C44H40N4P(1+)*Cl(1-)

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

4-Butylaminomethyl-1,2-dimethoxy-naphthalene (305836-05-9) + 1-amino-naphthalene (134-32-7) → C19H25NO3

Conditions	Yield
With hydrogenchloride; sodium hydrogencarbonate; triethylamine; acetyl chloride In dichloromethane	100%

1-amino-naphthalene (134-32-7) → 1-Fluoronaphthalene (321-38-0)

Conditions	Yield
Stage #1: 1-amino-naphthalene With hydrogenchloride; sodium nitrite In water at 5 - 75℃; Stage #2: With tetrafluoroboric acid In water for 0.25h; Stage #3: at 85 - 90℃; Temperature;	99.8%
With potassium nitrite; hydrogen fluoride
With tert.-butylnitrite; silicon tetrafluoride 1.) CH2Cl2, room temp., 1 h, 2.) 130-140 deg C, 1 h; Yield given. Multistep reaction;

thiophosgene (463-71-8) + 1-amino-naphthalene (134-32-7) → 1-isothiocyanatonaphthalene (551-06-4)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 1h;	99%
With triethylamine In dichloromethane at 20℃; for 1h;	99%
With chloroform; water

1-amino-naphthalene (134-32-7) + 2,5-hexanedione (110-13-4) → 2,5-dimethyl-1-(naphthyl)-pyrrole (18494-86-5)

Conditions	Yield
With amberlite IR 120 acidic resin at 20℃; for 0.666667h; Paal-Knorr pyrrole synthesis; Neat (no solvent);	99%
With bentonite In neat (no solvent) at 20℃; for 0.05h; Reagent/catalyst; Paal-Knorr Pyrrole Synthesis; Milling; Green chemistry;	97%
In neat (no solvent) at 20℃; for 0.383333h; Paal-Knorr Pyrrole Synthesis; Green chemistry;	97%

carbon disulfide (75-15-0) + 1-amino-naphthalene (134-32-7) → 1-isothiocyanatonaphthalene (551-06-4)

Conditions	Yield
Stage #1: carbon disulfide; 1-amino-naphthalene With triethylamine In tetrahydrofuran at 0 - 20℃; Stage #2: With dmap; di-tert-butyl dicarbonate In tetrahydrofuran at 0 - 20℃; for 2h;	99%
With S,S'-bis(1-phenyl-1H-tetrazol-5-yl) dithiocarbonate; triethylamine In acetonitrile for 0.333333h;	75%
With sodium hydroxide; diethyl chlorophosphate In toluene for 4h; Reflux;	55%

1-amino-naphthalene (134-32-7) + 5-(2-nitrophenyl)-2-furoyl isothiocyanate (140160-24-3) → 1-naphthalen-1-yl-3-[5-(2-nitro-phenyl)-furan-2-carbonyl]-thiourea

Conditions	Yield
at 20℃; for 0.05h;	99%

Upstream product

• 3349-64-2 1-tetralone oxime 
• 84-89-9 1-aminonaphthalene-5-sulfonic acid 
• 90-13-1 1-Chloronaphthalene 
• 6921-40-0 1-azidonaphthalene 
• 4921-84-0 N-(naphthalen-1-ylcarbamothioyl)benzamide 
• 2766-77-0 brilliant crystal scarlet 
• 92599-49-0 3-(Naphthalen-1-ylcarbamoyloxy)-cyclohex-1-enecarboxylic acid ethyl ester 
• 109-89-7 diethylamine 
• 132-66-1 naptalam 
• 86-57-7 1-Nitronaphthalene 
• 88-14-2 2-furanoic acid 
• 5435-44-9 (E)-3-Ureido-but-2-enoic acid ethyl ester 
• 62-53-3 aniline 
• 7647-01-0 hydrogenchloride 

Downstream Products

• 2933-59-7 N-(2-hydroxyethyl)-1-naphthylamine 
• 82238-92-4 N-(1-naphthyl)pyrrolidine 
• 86-83-9 N-1-naphthyl-3-oxobutyramide 
• 40337-07-3 N-(1-naphthyl)furan-2-carboxamide 
• 5333-99-3 2-(naphthalen-1-yl)isoindoline-1,3-dione 
• 132-66-1 naptalam 
• 4444-48-8 2-hydroxy-dibenzofuran-3-carboxylic acid-[1]naphthylamide 
• 33829-10-6 2-Oxo-3-indolyliden-α-naphthylamin 
• 575-36-0 1-acetamidonaphthalene 
• 35190-06-8 1-(diacetylamino)naphthalene 
• 5924-21-0 p-hydroxyphenyl-α-naphthylamine 
• 73953-69-2 N-(2-chloro-ethyl)-N'-[1]naphthyl-urea 
• 86-56-6 N,N-dimethyl-1-naphthalenamine 
• 2216-68-4 N-methylnaphthalen-1-amine 

Relevant articles and documents

Reactivity of 1-nitronaphthalene and 1,3-dinitronaphthalene with conjugated dienes. An easy access to N-naphthylpyrroles

1-Nitronaphthalene reacts at high temperature with poor and moderately reactive dienes affording N-naphthylpyrroles while, with the same dienes, 1,3-dinitronaphthalene exhibits the dienophilic character of naphthalenic C3-C4 bond producing the corresponding phenanthrenes through a classical Diels-Alder process.

-

-

-

-

Excited-State Proton-Transfer Reactions of Naphthylammonium Ion-18-Crown-6 Complexes

Proton-transfer reactions in the excited singlet state of naphthylammonium ion-18-crown-6 complexes in MeOH-H2O (9:1) mixtures have been studied by means of the single photon counting method with fluorimetry.It is found that the complex formation of naphthylammonium ions with 18-crown-6 decreases markedly the proton-transfer rate (k1) in the excited state, resulting in an increase of its lifetime.The back protonation rate in the excited state is negligibly small compared with those of the other decay processes; there is no excited-state prototropic equilibrium in the naphthylammonium ion-crown complexes (RN(1+)H3-crown).The one-way proton transfer reaction is elucidated by the presence of the excited neutral amine-crown complex (RNH2-crown)* produced by deprotonation of (RN(1+)H3-crown)*, where protonation to the amino group is structurally blocked by 18-crown-6 and the naphthyl group (R) of the complex.However, proton-induced quenching (k'q) occurs effectively especially in the 1-naphthylammonium ion-crown complex.The ground-state association constants (Kg) of the complexes can be determined easily by the fluorescence titration method.Temperature effects upon the excited-state proton-transfer reactions of the complexes have been also carried out in order to study their thermodynamic properties.A Corey-Pauling-Kolton model of the anilinium ion-18-crown-6 complex proposed by Izatt et al. is strongly supported by the present work.

Hydrolysis of naptalam and structurally related amides: Inhibition by dissolved metal ions and metal (hydr)oxide surfaces

In metal ion-free solutions, the secondary amide naptalam hydrolyzes more rapidly as the pH is decreased; intramolecular nucleophilic attack by a carboxylate side group is very likely involved. Millimolar levels of dissolved Cu(II) and Zn(II) inhibit hydr

Selective optical detection of HSO4 ? via hydrolysis of a simple Schiff Base

A very simple Schiff Base derived from 1-Naphthylamine and 4-(Trifluoromethy) benzaldehyde (L) was prepared as a selective colorimetric and turn-on fluorescent sensor for hydrogen sulfate. In the CH3CN:H2O (3:2, v/v) solvent system, L shows a highly selective colorimetric response to HSO4 ? ions by changing its color from yellow to colorless immediately. In addition, the weakly fluorescent receptor L shows a highly selective enhancement of fluorescence intensity at 425?nm for HSO4 ? upon excitation at 320?nm. The recognition process is proven to be hardly influenced by the other tested competitive anions. The sensing is suggested to involve a hydrolysis process promoted by HSO4 ? which has been further supported by UV–Vis, 1H NMR and HRMS spectroscopic studies. Applicability of L to detect HSO4 ? in tap water has been demonstrated. An easy-to-prepare test strip of L has also been made for the naked-eye detection of HSO4 ? in real samples.

Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene and Nucleophilic Ring-Opening Reactions

Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate. These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral trans-disubstituted cyclohexadiene

-

-

-

-

A new access to 1-naphthylamines by an equivalent Semmler-Wolff reaction

A new access to 1-naphthylamines from the corresponding 3,4-dihydro-1(2H)-naphthalenones (α-tetralones) is described. It proceeds in a two-step sequence: preparation of the benzyl Schiff's base of an α-tetralone followed by aromatization over palladium ca

Relationship between azo dye structure and rat hepatic azoreductase activity

The rate of reduction was determined for a variety of azo dyes using the rat hepatic azoreductase enzyme system. In decreasing order, the rates of reduction for the azo dyes expressed as nmol of arylamine product formed/min/0.25 g of liver were amaranth (33.2), azosulfamide (32.5), orange G (12.4), 1,2-dimethyl-4-p-(carboxyphenylazo)-5-hydroxybenzene (CPA) (9.27), brilliant crystal scarlet (8.00), sulfachrysoidine (7.27), and Sudan I (1.03). A comparison of the partition coefficient with its rate of reduction indicated that the water-soluble azo dyes were reduced more rapidly than the lipid-soluble ones. Furthermore, higher rates of reduction were observed for those dyes containing electron-withdrawing groups on the aromatic rings.

Rearrangement of 2-Quinolyl- and 1-Isoquinolylcarbenes to Naphthylnitrenes

2-Quinolylcarbene 23 and 1-isoquinolylcarbene 33 are generated by flash vacuum thermolysis (FVT) of the corresponding triazolo[1,5-a]quinoline and triazolo[5,1-a]isoquinoline 19 and 29, as well as 2-(5-tetrazolyl)quinoline and 1-(5-tetrazolyl)isoquinoline 20 and 30, respectively. These carbenes rearrange to 1- and 2-naphthylnitrene 21 and 31, respectively, and the nitrenes are also generated by FVT of 1- and 2-naphthyl azides 18 and 28. The products of FVT of both the nitrene and carbene precursors are the 2- and 3-cyanoindenes 26 and 27 together with the nitrene dimers, viz. azonaphthalenes 25 and 35, and the H-abstraction products, aminonaphthalenes 24 and 34. All the azide, triazole, and tetrazole precursors yield 3-cyanoindene 26 as the principal ring contraction product under conditions of low FVT temperature (340-400 °C) and high pressure (1 Torr N2 as carrier gas for the purpose of collisional deactivation). This ring contraction reaction is strongly subject to chemical activation, which caused extensive isomerization of 3-cyanoindene to 2-cyanoindene under conditions of low pressure (10-3 Torr). 2-Cyanoindene is calculated to be ca. 1.7 kcal/mol below 3-cyanoindene in energy; accordingly, high-temperature FVT of these cyanoindenes always gives mixtures of the two compounds with the 2-cyano isomer dominating. Photolysis of trizolo[1,5-a]quinoline 19 and triazolo[5,1-a]isoquinoline 29 in Ar matrixes causes partial ring opening to the corresponding 2-diazomethylquinoline 19′ and 1-diazomethylisoquinoline 29′. The photolysis of the former gives rise to a small amount of the cyclic ketenimine 22, the intermediate connecting 2-quinolylcarbene and 1-naphthylnitrene.

Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction

The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.

Porous polymeric ligand promoted copper-catalyzed C-N coupling of (hetero)aryl chlorides under visible-light irradiation

A porous polymeric ligand (PPL) has been synthesized and complexed with copper to generate a heterogeneous catalyst (Cu@PPL) that has facilitated the efficient C-N coupling with various (hetero)aryl chlorides under mild conditions of visible-light irradiation at 80 °C (58 examples, up to 99% yields). This method could be applied to both aqueous ammonia and substituted amines, and is compatible to a variety of functional groups and heterocycles, as well as allows tandem C-N couplings with conjunctive dihalides. Furthermore, the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration, affording reaction mixtures containing less than 1 ppm of Cu residue. [Figure not available: see fulltext.]