3568-90-9

Basic information

• Product Name: deoxylapachol
• Synonyms: deoxylapachol;DESOXYLAPACHOL;2-(3-Methyl 2-butenyl)-1,4-naphthoquinone;2-(3-Methyl-2-butenyl)-1,4-naphthoquinone;1,4-Naphthalenedione,2-(3-Methyl-2-buten-1-yl)-
• CAS NO: 3568-90-9
• Molecular Formula: C₁₅H₁₄O₂
• Molecular Weight: 226.27
• Mol File: 3568-90-9.mol
• Article Data: 12

Chemical Properties

• Boiling Point: 359.2 °C at 760 mmHg
• Flash Point: 134.8 °C
• Appearance: /
• Density: 1.125 g/cm³
• Vapor Pressure: 2.42E-05mmHg at 25°C
• Refractive Index: 1.57
• CAS DataBase Reference: deoxylapachol(CAS DataBase Reference)
• NIST Chemistry Reference: deoxylapachol(3568-90-9)
• EPA Substance Registry System: deoxylapachol(3568-90-9)

Safety Data

• Hazardous Substances Data: 3568-90-9(Hazardous Substances Data)

Usage

Description

Deoxylapachol is the main allergen identified in teak (Tectona grandis). Sensitization often concerns people in woodwork.

Contact allergens

Deoxylapachol is the main allergen identified in teak (Tectona grandis). Sensitization often concerns people involved in woodwork.

InChI:InChI=1/C15H14O2/c1-10(2)7-8-11-9-14(16)12-5-3-4-6-13(12)15(11)17/h3-7,9H,8H2,1-2H3

Synthetic route

(1R*,4S*,4aR*,9aS*)-1,4,4a,9-tetrahydro-4a-prenyl-1,4-methanoanthracene-9,10-dione + (1R*,4S*,4aS*,9aR*)-1,4,4a,9-tetrahydro-4a-prenyl-1,4-methanoanthracene-9,10-dione → deoxylapachol (3568-90-9)

Conditions	Yield
In 5,5-dimethyl-1,3-cyclohexadiene for 2h; Inert atmosphere; Reflux;	98%

(3-methyl-2-butenyl)trifluorosilane (114067-34-4) + [1,4]naphthoquinone (130-15-4) → deoxylapachol (3568-90-9)

Conditions	Yield
With iron(III) chloride In formamide for 24h; Ambient temperature;	96%
With iron(III) chloride In N,N-dimethyl-formamide; acetonitrile at 20℃;	96%

1,4-dimethoxy-2-(3-methyl-2-butenyl)-naphthalene (137414-53-0) → deoxylapachol (3568-90-9)

Conditions	Yield
With ammonium cerium(IV) nitrate In water; acetonitrile at 0℃; for 0.25h;	92%

2-chloro-1,4-naphthoquinone (1010-60-2) + prenylindium sesquibromide → deoxylapachol (3568-90-9) + 2,2-di-(3-methyl-but-2-enyl)-2,3-dihydro-1,4-naphthoquinone (82214-84-4)

Conditions	Yield
In N,N-dimethyl-formamide at -23℃; for 3h;	A 53% B 37%

4,4,5,5-tetramethyl-2-(3-methylbut-2-enyl)-1,3,2-dioxaborolane (141550-13-2) + [1,4]naphthoquinone (130-15-4) → deoxylapachol (3568-90-9)

Conditions	Yield
In chloroform-d1 at 20℃; for 24h; Inert atmosphere;	53%

prenyl bromide (870-63-3) + [1,4]naphthoquinone (130-15-4) → deoxylapachol (3568-90-9)

Conditions	Yield
With lead(II) bromide; aluminium In acetonitrile for 10h;	50%
With zinc In tetrahydrofuran at 55 - 60℃; for 1.5h; Further byproducts given;	500 mg

(3-methyl-2-butenyl)trifluorosilane (114067-34-4) + [1,4]naphthoquinone (130-15-4) → 1,4-Dihydroxynaphthalene (571-60-8) + deoxylapachol (3568-90-9) + 2,2-di-(3-methyl-but-2-enyl)-2,3-dihydro-1,4-naphthoquinone (82214-84-4)

Conditions	Yield
With tetrabutyl ammonium fluoride In tetrahydrofuran at -20℃; for 1h;	A 38% B 28% C 32%

[1,4]naphthoquinone (130-15-4) → 1,4-Dihydroxynaphthalene (571-60-8) + deoxylapachol (3568-90-9) + 2,2-di-(3-methyl-but-2-enyl)-2,3-dihydro-1,4-naphthoquinone (82214-84-4)

Conditions	Yield
With (3-methyl-2-butenyl)trifluorosilane; tetrabutyl ammonium fluoride In tetrahydrofuran at -20℃; for 1h;	A 38% B 28% C 32%

tricarbonyl<4-methoxy-2(3)-(3-methyl-2-butenyl)-1-naphthol>chromium(0) → deoxylapachol (3568-90-9)

Conditions	Yield
With silver(l) oxide	38%

4-methyl-pent-3-enoic acid (504-85-8) + [1,4]naphthoquinone (130-15-4) → deoxylapachol (3568-90-9) + 2,3-di-(3-methyl-but-2-enyl)-1,4-naphthoquinone (58880-17-4)

Conditions	Yield
With ammonium persulfate; silver nitrate In water; acetonitrile at 65 - 70℃; for 6h;	A 35% B 8%

2-chloro-1,4-naphthoquinone (1010-60-2) + prenyl bromide (870-63-3) → deoxylapachol (3568-90-9) + 2,2-di-(3-methyl-but-2-enyl)-2,3-dihydro-1,4-naphthoquinone (82214-84-4)

Conditions	Yield
With indium(III) chloride; water; zinc In tetrahydrofuran for 4h; Ambient temperature;	A 32% B 14%

1,4-Dihydroxynaphthalene (571-60-8) + 2-methyl-3-buten-2-ol (115-18-4) → deoxylapachol (3568-90-9)

Conditions	Yield
(i) BF3*Et2O, dioxane, (ii) Ag2O, Et2O; Multistep reaction;

4-methyl-pent-3-enoic acid (504-85-8) + [1,4]naphthoquinone (130-15-4) → deoxylapachol (3568-90-9)

Conditions	Yield
With ammonium peroxydisulfate; silver nitrate

2-chloro-1,4-naphthoquinone (1010-60-2) + prenyl bromide (870-63-3) → deoxylapachol (3568-90-9) + 2-chloro-3-(3-methylbut-2-enyl)naphthalene-1,4-dione (82214-83-3) + 2-chloro-2,3-dihydro-3,3-di-(3-methyl-but-2-enyl)-1,4-naphthoquinone (82214-85-5)

Conditions	Yield
With zinc In tetrahydrofuran for 4h; Further byproducts given;	A 20 mg B 300 mg C 0.3 (unit not given)
With zinc In tetrahydrofuran for 4h; Further byproducts given;	A 20 mg B 300 mg C 0.3

prenyl bromide (870-63-3) + [1,4]naphthoquinone (130-15-4) → deoxylapachol (3568-90-9) + 2,3-di-(3-methyl-but-2-enyl)-1,4-naphthoquinone (58880-17-4) + 2,2-di-(3-methyl-but-2-enyl)-2,3-dihydro-1,4-naphthoquinone (82214-84-4)

Conditions	Yield
With zinc In tetrahydrofuran at 55 - 60℃; for 4h;	A 20 mg B 400 mg C 1.2 (unit not given)
With zinc In tetrahydrofuran at 55 - 60℃; for 4h;	A 20 mg B 400 mg C 1.2

1,4-Dihydroxynaphthalene (571-60-8) + 3-methyl-2-buten-1-ol (556-82-1) → deoxylapachol (3568-90-9)

Conditions	Yield
(i) BF3-Et2O, dioxane, (ii) Ag2O, MgSO4, Et2O; Multistep reaction;

catalponol (34168-56-4, 57231-36-4, 70368-23-9) → deoxylapachol (3568-90-9)

Conditions	Yield
With manganese(IV) oxide In benzene

[1,4]naphthoquinone (130-15-4) + 1.) prenylindium sequibromide → deoxylapachol (3568-90-9) + 2,2-di-(3-methyl-but-2-enyl)-2,3-dihydro-1,4-naphthoquinone (82214-84-4)

Conditions	Yield
With sodium sulfate; silver(l) oxide 1.) DMF, -23 deg C, 3 h, 2.) Et2O, reflux, 1 h; Yield given. Multistep reaction. Yields of byproduct given;

deoxylapachol (3568-90-9) + prenylindium sesquiiodide → (Z)-2,3-benzo-5-methyl-5-(3,7-dimethylocta-2,6-dienyl)cyclohexane-1,4-dione (137554-07-5) + 2,2-di-(3-methyl-but-2-enyl)-2,3-dihydro-1,4-naphthoquinone (82214-84-4)

Conditions	Yield
In N,N-dimethyl-formamide at -23℃; for 3h; Yields of byproduct given. Title compound not separated from byproducts;	A n/a B 100%

deoxylapachol (3568-90-9) → 2-(3-methyl-but-2-enyl)-2,3-epoxy-1,4-naphthoquinone (137492-06-9)

Conditions	Yield
With dihydrogen peroxide; sodium carbonate In water; acetone at 0℃;	82%

deoxylapachol (3568-90-9) → 2,2-dimethyl-3,4-dihydro-2H-benzo[h]chromene-5,6-dione (4707-32-8)

Conditions	Yield
With iron(III) chloride; toluene-4-sulfonic acid In water; toluene at 90℃; for 0.5h; Reagent/catalyst; Solvent;	76%

deoxylapachol (3568-90-9) → hemitectol (1187181-61-8)

Conditions	Yield
With pyridine for 24h; Reflux; Inert atmosphere;	75%

deoxylapachol (3568-90-9) → (+)-2-(3-Methyl-2-butenyl)-1,4-naphthoquinone 2,3-epoxide (73377-79-4)

Conditions	Yield
With sodium hydroxide; dihydrogen peroxide; N-benzylcinchonidinum chloride In water; toluene at 35 - 40℃;	53%

deoxylapachol (3568-90-9) → 1.4-Dihydroxy-2-(3-methyl-buten-(2)-yl)-naphthalin (90685-35-1)

Conditions	Yield
(i) SnCl2, aq. HCl, dioxane, (ii) ZnCl2; Multistep reaction;

deoxylapachol (3568-90-9) + acetic anhydride (108-24-7) → 2-(γ,γ-Dimethylallyl)-naphthohydrochinon-1,4-diacetat (17532-55-7)

Conditions	Yield
With sodium acetate; zinc Heating;

deoxylapachol (3568-90-9) → 2-(2,3-epoxy-3-methylbutyl)-1,4-naphthoquinone (909576-31-4)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 16h;

deoxylapachol (3568-90-9) → 6-methoxy-2,2-dimethyl-3,4-dihydro-2H-naphtho[1,2-b]pyran-3-ol (645413-83-8)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: m-chloroperbenzoic acid / CH2Cl2 / 16 h / 20 °C 2.1: sodium dithionite / diethyl ether; H2O / 0.5 h / 20 °C 2.2: 1.26 g / acetic acid; sulfuric acid / H2O / 6 h / 20 °C 3.1: 90 percent / K2CO3 / acetone / 3 h / Heating View Scheme

deoxylapachol (3568-90-9) → 5-bromo-6-methoxy-2,2-dimethyl-2H-naphtho[1,2-b]pyran (909576-35-8)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: m-chloroperbenzoic acid / CH2Cl2 / 16 h / 20 °C 2.1: sodium dithionite / diethyl ether; H2O / 0.5 h / 20 °C 2.2: 1.26 g / acetic acid; sulfuric acid / H2O / 6 h / 20 °C 3.1: 90 percent / K2CO3 / acetone / 3 h / Heating 4.1: 95 percent / N-bromosuccinimide / CH2Cl2 / 0.17 h / 20 °C 5.1: pyridine / 16 h / 20 °C 6.1: 73 percent / KOtBu / tetrahydrofuran / 6 h / 20 °C View Scheme

Upstream product

• 870-63-3 prenyl bromide 
• 130-15-4 [1,4]naphthoquinone 
• 141550-13-2 4,4,5,5-tetramethyl-2-(3-methylbut-2-enyl)-1,3,2-dioxaborolane 
• 137414-53-0 1,4-dimethoxy-2-(3-methyl-2-butenyl)-naphthalene 
• 504-85-8 4-methyl-pent-3-enoic acid 
• 1010-60-2 2-chloro-1,4-naphthoquinone 
• 34168-56-4 catalponol 
• 571-60-8 1,4-Dihydroxynaphthalene 
• 556-82-1 3-methyl-2-buten-1-ol 
• 114067-34-4 (3-methyl-2-butenyl)trifluorosilane 
• 115-18-4 2-methyl-3-buten-2-ol 

Downstream Products

• 4707-32-8 2,2-dimethyl-3,4-dihydro-2H-benzo[h]chromene-5,6-dione 
• 137492-06-9 2-(3-methyl-but-2-enyl)-2,3-epoxy-1,4-naphthoquinone 
• 573-13-7 lapachenole 
• 55481-88-4 mollugin 
• 909576-34-7 5-bromo-6-methoxy-2,2-dimethyl-3-tosyloxy-3,4-dihydro-2H-naphtho[1,2-b]pyran 

Relevant articles and documents

-

-

Direct allylation of quinones with allylboronates

Allylboronates undergo C-H allylation of unsubstituted or monosubstituted benzoquinone and naphthoquinone substrates. In the case of 2,5-or 2,6-disubstituted quinones addition involving the substituted carbon takes place. Allylation with stereodefined allylboronates occurs with retention of the configuration.

Synthesis of mollugin

The total synthesis of mollugin, a major constituent of rubiaceous herbs, using a straightforward synthetic approach starting from 1,4-naphthoquinone via a sequence of reactions, including selective prenylation, epoxidation, reduction of the quinone moiety, acid-catalysed ring expansion, bromination, dehydration and methoxycarbonylation is presented.