4746-97-8

Basic information

• Product Name: 1,4-Dioxaspiro[4.5]decan-8-one
• Synonyms: 1,4-CYCLOHEXANEDIONE MONOETHYLENE ACETAL;1,4-CYCLOHEXANEDIONE MONOETHYLENE KETAL;1,4-DIOXASPIRO[4.5]DECAN-8-ONE;1,4-DIOXASPIRO[4.5]-8-DECANONE;CYCLOHEXANEDIONE(1,4-) MONOETHYLENE;4-Cyclohexanedione Monoethylene acetal;1,4-Dioxaspiro[4.5]decan-8-one 99%;Cyclohexane-1,4-dione monoethylene ketal, Cyclohexane-1,4-dione monoethylene acetal
• CAS NO: 4746-97-8
• Molecular Formula: C₈H₁₂O₃
• Molecular Weight: 156.18
• EINECS: -0
• Product Categories: blocks;BuildingBlocks;Liquid Crystal intermediates;Carbonyl Compounds;Heterocycles;ketone;Dioxanes & Dioxolanes;Dioxolanes
• Mol File: 4746-97-8.mol
• Article Data: 32

Chemical Properties

• Melting Point: 70-73 °C(lit.)
• Boiling Point: 112C
• Flash Point: 106.7 °C
• Appearance: White to beige/Crystalline Powder or Crystals
• Density: 1.0887 (rough estimate)
• Vapor Pressure: 0.00776mmHg at 25°C
• Refractive Index: 1.4430 (estimate)
• Storage Temp.: Store below +30°C.
• Solubility: Soluble in chloroform & methanol.
• Sensitive: Moisture Sensitive
• BRN: 117631
• CAS DataBase Reference: 1,4-Dioxaspiro[4.5]decan-8-one(CAS DataBase Reference)
• NIST Chemistry Reference: 1,4-Dioxaspiro[4.5]decan-8-one(4746-97-8)
• EPA Substance Registry System: 1,4-Dioxaspiro[4.5]decan-8-one(4746-97-8)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 22-24/25-36/37/39-26
• WGK Germany: 3
• F: 8-10-21
• Hazardous Substances Data: 4746-97-8(Hazardous Substances Data)

Usage

Chemical Properties

1,4-Dioxaspiro[4.5]decan-8-one is white to beige crystalline powder or crystals

Uses

Different sources of media describe the Uses of 4746-97-8 differently. You can refer to the following data:
1. 1,4-Dioxaspiro[4.5]decan-8-one is used in the preparation of series of potent analgesic compounds. 1,4-Cyclohexanedione Monoethylene Acetal is also used as a building block in the synthesis of tritium labelled probes for the autoradiography study of the dopamine reuptake complex.
2. Intermediates of Liquid Crystals
3. 1,4-Cyclohexanedione is used in the preparation of series of potent analgesic compounds. 1,4-Cyclohexanedione is also used as a building block in the synthesis of tritium labelled probes for the autoradiography study of the dopamine reuptake complex.

Purification Methods

Recrystallise it from pet ether. It sublimes slowly on attempted distillation. Also purify it by dissolving it in Et2O and adding pet ether (b 60-80o) until turbid and cooling. [Gardner et al. J Am Chem Soc 22 1206 1957, Britten & Lockwood J Chem Soc Perkin Trans 1 1824 1974.] [Beilstein 19/4 V 93.]

InChI:InChI=1/C8H12O3/c9-7-1-3-8(4-2-7)10-5-6-11-8/h1-6H2

Synthetic route

dimethyl 2,5-dioxocyclohexane-1,4-dicarboxylate (6289-46-9) + ethylene glycol (107-21-1) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With 1-butyl-3-methylimidazolium hydrogen sulfate; water; 1-ethylimidazolium tetrafluoroborate at 110 - 132℃; for 5.5h; Temperature; Reagent/catalyst;	97.8%

ethylene glycol (107-21-1) + 1,4-Cyclohexanedione (637-88-7) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With triethylmethylammonium chloride at 50℃; for 1h; Temperature; Reagent/catalyst;	96%
With toluene-4-sulfonic acid In benzene at 100℃; for 1.5h;	35%
With toluene-4-sulfonic acid In benzene for 4h; Heating;

Bis<1,4-dioxaspiro<4.5>decan-8-yliden>hydrazin (64554-48-9) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With HOF* CH3CN In dichloromethane at 0℃; for 0.0166667h;	95%

3,5-dimethyl-1H-pyrazole (67-51-6) + 4-hydroxycyclohexane mono-ketal → cyclohexanedione monoethylene ketal (4746-97-8) + 1,4-Cyclohexanedione (637-88-7)

Conditions	Yield
In dichloromethane; ethyl acetate	A 91% B n/a

1,4-dioxaspiro[4.5]deca-6,9-dien-8-one (35357-34-7) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With hydrogen; N-ethyl-N,N-diisopropylamine; 1% Pd/C In 2-methyltetrahydrofuran at 30℃; under 75007.5 Torr; Autoclave;	91%

4,4-ethylenedioxycyclohexan-1-ol (22428-87-1) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With Oxone; sodium ortho-iodobenzenesulfonate; sodium sulfate In ethyl acetate at 70℃; for 8h; Inert atmosphere;	86%
With potassium peroxymonosulfate; sodium ortho-iodobenzenesulfonate; sodium sulfate In ethyl acetate at 70℃; for 8h;	86%
With pyridine; chromium(VI) oxide
With tert.-butylhydroperoxide; Cs5V14As8O42Cl In water; acetone at 20℃; for 48h;	20 %Chromat.
With tert.-butylhydroperoxide; Cs5V14As8O42Cl In water; acetone at 20℃; for 48h; Sealed tube;

1,4,9,12-Tetraoxa-dispiro[4.2.4.2]tetradecane (183-97-1) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With formaldehyd; silica gel; iron(III) chloride In water for 1h; Ring cleavage;	86%
With water In acetic acid; trifluoroacetic acid at 45℃; for 14h;

1,4-Dioxa-9,13-dithia-dispiro[4.2.5.2]pentadecane → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With periodic acid In tetrahydrofuran; diethyl ether at -10℃; for 0.333333h;	86%

8-Methylsulfanyl-8-(toluene-4-sulfonyl)-1,4-dioxa-spiro[4.5]decane (98253-09-9) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With sodium hydrogencarbonate In 1,4-dioxane; water Irradiation;	83%

ethyl 8-oxo-1,4-dioxaspiro[4.5]decane-7-carboxylate (14160-65-7, 77793-24-9, 122090-88-4) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With potassium hydroxide In water for 6h; Ambient temperature;	80%
With magnesium chloride In N,N,N,N,N,N-hexamethylphosphoric triamide at 150℃; for 2h;	92 % Chromat.

C20H24O5 (124293-54-5) → cyclohexanedione monoethylene ketal (4746-97-8) + (1S,2R)-1,4-Dimethyl-1,2-dihydro-naphthalene-1,2-diol (114390-56-6)

Conditions	Yield
With acetic acid; zinc at 16℃; for 0.333333h;	A 77% B n/a

1,4,9,12-Tetraoxa-dispiro[4.2.4.2]tetradecane (183-97-1) + 1,4-Cyclohexanedione (637-88-7) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 100℃; for 1.25h;	74%

4(-Ethylenedioxy)cyclohexanone oxime O-acetate → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
Stage #1: 4(-Ethylenedioxy)cyclohexanone oxime O-acetate With dicobalt octacarbonyl; triethylamine In diethyl ether at 20℃; for 0.25h; deoximation; Stage #2: With water In methanol at 20℃; for 0.5h; Hydrolysis;	74%

8-methylene-1,4-dioxaspiro[4.5]decane (51656-90-7) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With 2,6-dimethylpyridine; sodium periodate; ruthenium(III) chloride trihydrate In dichloromethane; water; acetonitrile at 20℃; for 1h; Inert atmosphere;	72%

8,8-Dimethoxy-1,4-dioxa-spiro[4.5]decane (124414-04-6) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
In water; dimethyl sulfoxide at 150℃; for 8h;	64.7%

1,4,9,12-Tetraoxa-dispiro[4.2.4.2]tetradecane (183-97-1) → cyclohexanedione monoethylene ketal (4746-97-8) + 1,4-Cyclohexanedione (637-88-7)

Conditions	Yield
With formaldehyd; silica gel; iron(III) chloride at 20℃; for 0.416667h;	A 58% B 22 % Chromat.

N,N-dimethylformamide ethylene acetal (19449-26-4) + 1,4-Cyclohexanedione (637-88-7) → cyclohexanedione monoethylene ketal (4746-97-8) + 1,4,9,12-Tetraoxa-dispiro[4.2.4.2]tetradecane (183-97-1)

Conditions	Yield
With acetic acid In dichloromethane at 20℃; for 30h;	A 34% B 7%

ethylene glycol (107-21-1) + 1,4-Cyclohexanedione (637-88-7) → cyclohexanedione monoethylene ketal (4746-97-8) + 1,4,9,12-Tetraoxa-dispiro[4.2.4.2]tetradecane (183-97-1)

Conditions	Yield
With toluene-4-sulfonic acid In benzene Heating;	A 28% B 25%
With toluene-4-sulfonic acid In hexane; benzene Heating;	A 24% B 25%

ethyl 3-<2-<2-(ethoxycarbonyl)ethyl><1,3>dioxolan-2-yl>propionate (19719-88-1) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With sodium; xylene

ethyl 3-<2-<2-(ethoxycarbonyl)ethyl><1,3>dioxolan-2-yl>propionate (19719-88-1) → cyclohexanedione monoethylene ketal (4746-97-8) + ethyl 8-oxo-1,4-dioxaspiro[4.5]decane-7-carboxylate (14160-65-7, 77793-24-9, 122090-88-4)

Conditions	Yield
With sodium; xylene

Trimethyl-(1,4,9,12-tetraoxa-dispiro[4.2.4.2]tetradec-2-ylmethyl)-silane → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With lithium tetrafluoroborate In acetonitrile for 0.5h; Product distribution; Heating; var. reag.: 0.1M HF in water, 15 min, RT;

tetrachloromethane (56-23-5) + ethyl 3-<2-<2-(ethoxycarbonyl)ethyl><1,3>dioxolan-2-yl>propionate (19719-88-1) + sodium Oleate (143-19-1) + sodium → cyclohexanedione monoethylene ketal (4746-97-8) + ethyl 8-oxo-1,4-dioxaspiro[4.5]decane-7-carboxylate (14160-65-7, 77793-24-9, 122090-88-4)

4-oximinocyclohexanone ethylene ketal (180918-12-1) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: Et3N / diethyl ether / 7 h / 20 °C 2.1: Co2(CO)8; Et3N / diethyl ether / 0.25 h / 20 °C 2.2: 74 percent / H2O / methanol / 0.5 h / 20 °C View Scheme

2.2-Bis-β-chlorethyl-1.3-dioxolan (75945-89-0) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 62 percent / NaH / dimethylformamide / 25 - 60 °C 2: 83 percent / NaHCO3 / dioxane; H2O / Irradiation View Scheme

4-hydroxycyclohexanone (13482-22-9) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: benzene; toluene-4-sulfonic acid / Erwaermen des Reaktionsprodukts mit methanol. Natronlauge 2: chromium (VI)-oxide; pyridine View Scheme

4-oxopimelate (6317-49-3) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: benzene; toluene-4-sulfonic acid / Entfernen des entstehenden Wassers 2: sodium; xylene View Scheme

3-hydroxycyclohexanone (823-19-8) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: benzene; toluene-4-sulfonic acid 2: chromium (VI)-oxide; pyridine View Scheme

4-methoxycyclohexanone ethylene ketal (56292-99-0) → cyclohexanedione monoethylene ketal (4746-97-8)

Conditions	Yield
With calcium hypochlorite; acetic acid In water; acetonitrile at 0℃; regioselective reaction;	76 mg

cyclohexanedione monoethylene ketal (4746-97-8) + bromobenzene (108-86-1) → 4-hydroxy-4-phenyl-cyclohexanone ethylene ketal (94112-58-0)

Conditions	Yield
Stage #1: bromobenzene With magnesium In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Reflux; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran for 0.5h; Inert atmosphere; Reflux;	100%
Stage #1: bromobenzene With iodine; magnesium In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran at 0 - 55℃; Inert atmosphere;	41%
With tert.-butyl lithium 1.) THF, -60 deg C, 3 h, 2.) THF, RT, overnight; Yield given. Multistep reaction;
Stage #1: bromobenzene With n-butyllithium In tetrahydrofuran; hexane at -40℃; for 0.5h; Inert atmosphere; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;

cyclohexanedione monoethylene ketal (4746-97-8) + diethoxyphosphoryl-acetic acid ethyl ester (867-13-0) → ethyl 1,4-dioxaspiro[4,5]dec-8-ylideneacetate (51656-91-8)

Conditions	Yield
With sodium hydride In 1,2-dimethoxyethane for 11.5h; Ambient temperature;	100%
With sodium hydride In tetrahydrofuran at 0℃; for 0.666667h; Horner-Wadsworth-Emmons reaction;	100%
Stage #1: cyclohexanedione monoethylene ketal With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 1h; Stage #2: diethoxyphosphoryl-acetic acid ethyl ester In tetrahydrofuran; mineral oil at -20 - 20℃; for 3h;	100%

cyclohexanedione monoethylene ketal (4746-97-8) + 1-chloroethyl p-tolyl sulfoxide (50635-71-7, 50635-72-8, 31350-93-3) → 8-[1-Chloro-1-(toluene-4-sulfinyl)-ethyl]-1,4-dioxa-spiro[4.5]decan-8-ol (134970-38-0)

Conditions	Yield
at -70℃;	100%
With lithium diisopropyl amide In tetrahydrofuran at -70℃;	90%
With lithium diisopropyl amide 1.) THF; Multistep reaction;

cyclohexanedione monoethylene ketal (4746-97-8) + benzylamine (100-46-9) → 4-(N-benzylamino)cyclohexanone ethylene acetal (131511-13-2)

Conditions	Yield
Stage #1: cyclohexanedione monoethylene ketal; benzylamine With sodium tris(acetoxy)borohydride In dichloromethane at 20℃; for 20h; Stage #2: With sodium hydroxide In dichloromethane; water	100%
Stage #1: cyclohexanedione monoethylene ketal; benzylamine With sodium tris(acetoxy)borohydride In dichloromethane at 20℃; for 2h; Stage #2: With water; sodium hydrogencarbonate In dichloromethane	100%
Stage #1: cyclohexanedione monoethylene ketal; benzylamine In dichloromethane at 20℃; for 6h; Molecular sieve; Stage #2: With sodium tetrahydroborate In methanol at 20℃; for 1h;	99%

cyclohexanedione monoethylene ketal (4746-97-8) → 4,4-ethylenedioxycyclohexan-1-ol (22428-87-1)

Conditions	Yield
With sodium tetrahydroborate In methanol for 2.5h;	100%
With sodium tetrahydroborate In methanol at 0 - 20℃; for 3h;	100%
With sodium tetrahydroborate In methanol at 0 - 20℃;	100%

cyclohexanedione monoethylene ketal (4746-97-8) + ethyl (triphenylphosphoranylidene)acetate (1099-45-2) → ethyl 1,4-dioxaspiro[4,5]dec-8-ylideneacetate (51656-91-8)

Conditions	Yield
In toluene for 24h; Heating;	100%
In benzene for 12h; Heating / reflux;	90%
In benzene for 24h; Wittig reaction; Heating;	90%
In benzene for 24h; Wittig Reaction; Heating / reflux;	90%
In benzene for 1h; Heating;	89%

cyclohexanedione monoethylene ketal (4746-97-8) + methyl (triphenylphosphoranylidene)acetate (21204-67-1) → 8-(methoxyformylmethylene)-1,4-dioxaspiro[4.5]decane (172270-85-8)

Conditions	Yield
In toluene for 45h; Inert atmosphere; Reflux;	100%
In toluene Heating;	94%
In toluene for 18h; Heating / reflux;	81%
In toluene for 18h; Inert atmosphere; Reflux;	60%

cyclohexanedione monoethylene ketal (4746-97-8) + Methyltriphenylphosphonium bromide (1779-49-3) → 8-methylene-1,4-dioxaspiro[4.5]decane (51656-90-7)

Conditions	Yield
With potassium tert-butylate In benzene at 25℃; for 1h;	100%
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 0.666667h; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran; hexane at 20℃;	92%
With sodium hydride In dimethyl sulfoxide	90%

propylamine (107-10-8) + cyclohexanedione monoethylene ketal (4746-97-8) → 4-propylaminocyclohexan-1-one ethylene acetal (676124-70-2)

Conditions	Yield
Stage #1: propylamine With hydrogenchloride In methanol at 0 - 5℃; for 0.5h; pH=6 - 7; Stage #2: cyclohexanedione monoethylene ketal In methanol at 5℃; for 0.25h; Stage #3: With hydrogenchloride; sodium cyanoborohydride; sodium carbonate more than 3 stages;	100%
With hydrogen; palladium 10% on activated carbon In methanol under 3000.3 Torr;	100%
With hydrogen; palladium 10% on activated carbon In methanol under 3000.3 Torr;	100%

cyclohexanedione monoethylene ketal (4746-97-8) + ethyl 2-cyanoacetate (105-56-6) → 2-amino-6-(2'-spiro[1',3']dioxolane)-6,7-dihydro-4H-benzo[b]thiophen-3-carboxylic acid ethyl ester (173032-58-1)

Conditions	Yield
With morpholine; sulfur In ethanol at 50℃; for 16h; Gewald's 2-aminothiophene reaction;	100%
With morpholine; sulfur In ethanol at 20℃; for 96h;	99%
With morpholine; sulfur In ethanol at 20℃; for 96h;	99%

cyclohexanedione monoethylene ketal (4746-97-8) + (1-hexadecyl)triphenylphosphonium bromide (14866-43-4) → 8-hexadecylidene-1,4-dioxaspiro[4.5]decane (503869-34-9)

Conditions	Yield
Stage #1: (1-hexadecyl)triphenylphosphonium bromide With potassium hexamethylsilazane In tetrahydrofuran at 20℃; for 15h; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran at 20℃; for 12h; Wittig reaction;	100%

cyclohexanedione monoethylene ketal (4746-97-8) + phenylbis[(trifluoromethyl)sulfonyl]amine → 1,4-dioxaspiro[4.5]dec-7-en-8-yl trifluoromethanesulfonate (170011-47-9)

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran; toluene at -78℃; for 4h;	100%
Stage #1: cyclohexanedione monoethylene ketal With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: phenylbis[(trifluoromethyl)sulfonyl]amine In tetrahydrofuran; hexane at -78℃; Cooling;	33%

cyclohexanedione monoethylene ketal (4746-97-8) + 1-chloropropyl p-tolyl sulfoxide → 8-[1-chloro-1-(p-tolylsulfinyl)propyl]-1,4-dioxaspiro[4.5]decan-8-ol (733016-42-7)

Conditions	Yield
	100%

cyclohexanedione monoethylene ketal (4746-97-8) → 1,4-dioxaspiro[4.5]decan-8-amine (97096-16-7)

Conditions	Yield
With ammonia; hydrogen; palladium 10% on activated carbon In methanol under 3000.3 Torr;	100%
With ammonium formate; C25H31ClIrN2OP at 50℃; for 18h; Leukardt-Wallach Amination; Sealed tube;	99%
Stage #1: cyclohexanedione monoethylene ketal With sodium tris(acetoxy)borohydride; benzylamine In methanol; dichloromethane Stage #2: With hydrogen; palladium(II) hydroxide In methanol	93%

cyclohexanedione monoethylene ketal (4746-97-8) + N,N-phenylbistrifluoromethane-sulfonimide (37595-74-7) → 1,4-dioxaspiro[4.5]dec-7-en-8-yl trifluoromethanesulfonate (170011-47-9)

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran; toluene at -78℃; for 4h;	100%
With lithium hexamethyldisilazane In tetrahydrofuran at -78 - 20℃; for 0.5h; Inert atmosphere;	100%
With lithium hexamethyldisilazane at -78 - 20℃; Inert atmosphere;	100%

cyclohexanedione monoethylene ketal (4746-97-8) + allyl bromide (106-95-6) → 8-allyl-1,4-dioxaspiro[4,5]decan-8-ol (429691-42-9)

Conditions	Yield
With ammonium acetate; zinc In tetrahydrofuran cooling;	100%
Stage #1: allyl bromide With magnesium In diethyl ether at 20℃; for 1.5h; Stage #2: cyclohexanedione monoethylene ketal In diethyl ether at 20℃; for 3.5h; Grignard reaction;
With water; ammonium chloride; zinc In tetrahydrofuran at 20℃;
With ammonium chloride; zinc In tetrahydrofuran; water at 20℃;

cyclohexanedione monoethylene ketal (4746-97-8) + Methoxyallene (13169-00-1) → C12H18O4

Conditions	Yield
Stage #1: Methoxyallene With n-butyllithium In diethyl ether; hexane at -40℃; for 0.5h; Inert atmosphere; Stage #2: cyclohexanedione monoethylene ketal In diethyl ether; hexane at -78℃; Inert atmosphere;	100%
Stage #1: Methoxyallene With n-butyllithium In diethyl ether; hexane at -40℃; for 0.333333h; Stage #2: cyclohexanedione monoethylene ketal In diethyl ether; hexane at -78℃; for 2.5h; Further stages.;

cyclohexanedione monoethylene ketal (4746-97-8) + (2S)-2-amino-3-(4-methoxyphenyl)propan-1-ol (20989-19-9) → (S)-3-[(4-methoxyphenyl)methyl]-1,4-oxazaspiro[4.5]decan-8-one ethylene acetal

Conditions	Yield
With molecular sieve In dichloromethane at 20℃; for 2h;	100%

cyclohexanedione monoethylene ketal (4746-97-8) + o-hydroxyacetophenone (118-93-4) → dispiro[chromane-2,1'-cyclohexane-4',2''-[1,3]dioxolan]-4-one (911228-28-9)

Conditions	Yield
With pyrrolidine In methanol for 10h; Heating / reflux;	100%
With pyrrolidine In ethanol at 80℃; for 12h; Kabe Chromanone Synthesis;

cyclohexanedione monoethylene ketal (4746-97-8) + N-(5-chloropyridin-2-yl)-1,1,1-trifluoro-N-[(trifluoromethyl)sulphonyl]methanesulphonamide (145100-51-2) → 1,4-dioxaspiro[4.5]dec-7-en-8-yl trifluoromethanesulfonate (170011-47-9)

Conditions	Yield
With lithium diisopropyl amide In tetrahydrofuran at -78 - -20℃;	100%
Stage #1: cyclohexanedione monoethylene ketal With lithium hexamethyldisilazane In tetrahydrofuran at -78 - 0℃; for 1h; Stage #2: N-(5-chloropyridin-2-yl)-1,1,1-trifluoro-N-[(trifluoromethyl)sulphonyl]methanesulphonamide In tetrahydrofuran at -78 - -40℃; for 4h;	88%
With lithium hexamethyldisilazane In tetrahydrofuran at -78 - 20℃; for 2h;	72%

cyclohexanedione monoethylene ketal (4746-97-8) + 1-[3-(trifluoromethoxy)phenyl]methanamine (93071-75-1) → N-[3-(trifluoromethoxy)benzyl]-1,4-dioxaspiro[4.5]decan-8-amine (1031289-46-9)

Conditions	Yield
Stage #1: cyclohexanedione monoethylene ketal; 1-[3-(trifluoromethoxy)phenyl]methanamine With sodium tris(acetoxy)borohydride; acetic acid In tetrahydrofuran at 20℃; Stage #2: With sodium hydroxide In tetrahydrofuran; water	100%

cyclohexanedione monoethylene ketal (4746-97-8) + trimethylsilylacetylene (1066-54-2) → 8-((trimethylsilyl)ethynyl)-1,4-dioxaspiro[4.5]decan-8-ol (320342-34-5)

Conditions	Yield
Stage #1: trimethylsilylacetylene With n-butyllithium In tetrahydrofuran; hexane at -76℃; for 1h; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran; hexane at -74℃; for 2h;	100%
With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere;	77%
Stage #1: trimethylsilylacetylene With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran; hexane at -78℃; for 1h; Stage #3: With water; ammonium chloride In tetrahydrofuran; hexane

cyclohexanedione monoethylene ketal (4746-97-8) + 1,1-dimethylhydrazine (57-14-7) → 2-[1,4-dioxaspiro[4.5 ]decan-8-ylidene]-1,1-dimethylhydrazine (1037668-50-0)

Conditions	Yield
In toluene at 20℃; Dean-Stark; Reflux;	100%
In toluene Dean-Stark; Reflux;	100%
With trifluoroacetic acid In benzene Heating;	86%
With toluene-4-sulfonic acid In benzene for 6h; Reflux;
at 20℃; Neat (no solvent);

4-fluoroindole (387-43-9) + cyclohexanedione monoethylene ketal (4746-97-8) → 3-(1,4-dioxa-spiro[4,5]dec-7-en-8-yl)-4-fluoro-1H-indole (282546-98-9)

Conditions	Yield
With potassium hydroxide In methanol Heating;	100%

cyclohexanedione monoethylene ketal (4746-97-8) → 4-Methylencyclohexanol (22428-85-9)

Conditions	Yield
Stage #1: cyclohexanedione monoethylene ketal With n-butyllithium; Methyltriphenylphosphonium bromide In tetrahydrofuran at -10 - 25℃; for 17h; Stage #2: With oxalic acid In water; acetone at 25℃; for 3.5h; Stage #3: With sodium tetrahydroborate In tetrahydrofuran at 25℃; for 3h;	100%
Multi-step reaction with 3 steps 1.1: n-butyllithium / hexane; tetrahydrofuran / 1 h / -10 °C 1.2: 4 h / -10 - 20 °C 2.1: water; oxalic acid / acetone / 3 h / 20 °C 3.1: sodium tetrahydroborate / methanol / 2 h / 0 - 20 °C View Scheme
Multi-step reaction with 3 steps 1.1: n-butyllithium / tetrahydrofuran; hexanes / 1 h / -10 °C 1.2: 4 h / 20 °C 2.1: oxalic acid / water; acetone / 3 h / 20 °C 3.1: sodium tetrahydroborate; methanol / 2 h / 0 - 20 °C View Scheme
Multi-step reaction with 3 steps 1.1: n-butyllithium / tetrahydrofuran / 1 h / -10 °C 1.2: 4 h / 20 °C 2.1: oxalic acid / water; acetone / 3 h / 20 °C 3.1: sodium tetrahydroborate; methanol / 2 h / 0 - 20 °C View Scheme

cyclohexanedione monoethylene ketal (4746-97-8) + trimethylsilylacetylene (1066-54-2) → 8-ethynyl-1,4-dioxaspiro[4.5]decan-8-ol (70097-74-4)

Conditions	Yield
Stage #1: trimethylsilylacetylene With n-butyllithium In tetrahydrofuran; hexane at -76℃; for 1h; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran; hexane at -74℃; for 2h; Stage #3: With potassium carbonate In methanol at 20℃; for 2h;	100%
Stage #1: trimethylsilylacetylene With n-butyllithium In tetrahydrofuran; hexane at -70℃; for 0.833333h; Stage #2: cyclohexanedione monoethylene ketal In tetrahydrofuran; hexane at -70℃; Stage #3: With methanol; potassium carbonate for 0.5h;	98%

cyclohexanedione monoethylene ketal (4746-97-8) + 4,4-difluoropiperidine hydrochloride → 1-(1,4-dioxa-spiro[4.5]dec-8-yl)-4,4-difluoro-piperidine (1373516-35-8)

Conditions	Yield
Stage #1: cyclohexanedione monoethylene ketal; 4,4-difluoropiperidine hydrochloride With sodium tris(acetoxy)borohydride; acetic acid In dichloromethane at 20℃; for 20h; Stage #2: With sodium hydroxide In dichloromethane pH=12;	100%
With sodium tris(acetoxy)borohydride; acetic acid In dichloromethane at 20℃; for 24h; Inert atmosphere;	2 g

cyclohexanedione monoethylene ketal (4746-97-8) + methylamine (74-89-5) → N-(1,4-dioxaspiro-[4,5]-decan-8-yliden)-methanamine (1071066-97-1)

Conditions	Yield
In ethanol at 20℃;	100%
In ethanol at 20℃; for 2 - 24h;	100%

cyclohexanedione monoethylene ketal (4746-97-8) + trimethylsilyl cyanide (7677-24-9) + 2-iodophenylamine (615-43-0) → C15H17IN2O2

Conditions	Yield
With acetic acid at 20℃; for 12h;	100%

cyclohexanedione monoethylene ketal (4746-97-8) + isopropenylmagnesium bromide (13291-18-4) → 8-(Prop-1-en-2-yl)-1,4-dioxaspiro[4.5]decan-8-ol

Conditions	Yield
In tetrahydrofuran at 0 - 5℃; for 2h; Inert atmosphere;	100%
In tetrahydrofuran at 0 - 5℃; for 4h; Inert atmosphere;
In tetrahydrofuran at 5℃; for 2h;

Upstream product

• 22428-87-1 4,4-ethylenedioxycyclohexan-1-ol 
• 19719-88-1 ethyl 3-<2-<2-(ethoxycarbonyl)ethyl><1,3>dioxolan-2-yl>propionate 
• 183-97-1 1,4,9,12-Tetraoxa-dispiro[4.2.4.2]tetradecane 
• 14160-65-7 ethyl 8-oxo-1,4-dioxaspiro[4.5]decane-7-carboxylate 
• 98253-09-9 8-Methylsulfanyl-8-(toluene-4-sulfonyl)-1,4-dioxa-spiro[4.5]decane 
• 107-21-1 ethylene glycol 
• 637-88-7 1,4-Cyclohexanedione 
• 67-51-6 3,5-dimethyl-1H-pyrazole 
• 35357-34-7 1,4-dioxaspiro[4.5]deca-6,9-dien-8-one 
• 6289-46-9 dimethyl 2,5-dioxocyclohexane-1,4-dicarboxylate 
• 51656-90-7 8-methylene-1,4-dioxaspiro[4.5]decane 
• 18068-06-9 4-methoxycyclohexan-1-ol 
• 556-48-9 1,4-Cyclohexanediol 
• 13482-23-0 4-methoxycyclohexanone 

Downstream Products

• 120686-08-0 1',5',7',8'-tetrahydrospiro<1,3-dioxolane-2,6'(2'H)-quinolin>-2'-one 
• 209391-67-3 8-[Chloro-(toluene-4-sulfinyl)-methyl]-1,4-dioxa-spiro[4.5]decan-8-ol 
• 172270-85-8 8-(methoxyformylmethylene)-1,4-dioxaspiro[4.5]decane 
• 199010-68-9 8-[2-Benzenesulfonyl-1-(2-trimethylsilanyl-ethoxymethyl)-1H-imidazol-4-yl]-1,4-dioxa-spiro[4.5]decan-8-ol 
• 221533-40-0 8-(4-chlorobenzylidene)-1,4-dioxaspiro<4.5>decane 
• 221533-17-1 8-(3-trifluoromethylbenzylidene)-1,4-dioxaspiro<4.5>decane 
• 221533-28-4 8-(3,4,5-trimethoxybenzylidene)-1,4-dioxaspiro<4.5>decane 
• 54621-11-3 1,4-dioxa-spiro[4.5]decan-8-one phenylhydrazone 
• 221533-04-6 8-(3-methylbenzylidene)-1,4-dioxaspiro<4.5>decane 
• 221533-02-4 8-(2-methylbenzylidene)-1,4-dioxaspiro<4.5>decane 
• 221533-23-9 8-(2,5-dimethoxybenzylidene)-1,4-dioxaspiro<4.5>decane 
• 171492-75-4 8-(4-methoxybenzylidene)-1,4-dioxaspiro<4.5>decane 
• 221533-11-5 8-(2-methoxybenzylidene)-1,4-dioxaspiro<4.5>decane 
• 221533-13-7 8-(3-methoxybenzylidene)-1,4-dioxaspiro<4.5>decane 

Relevant articles and documents

Studies on the synthesis of Schisandraceae natural products: Exploring a cyclopropylcarbinol ring expansion strategy

Acid mediated cyclopropylcarbinol ring expansion has been shown to be a viable method for the construction of the AB ring framework of lancifodilactone F and related terpenoids of the Schisandraceae family of natural products. We found that this rearrangement proceeds with good stereochemical control based on inversion of the C10 cyclopropyl center. Our studies indicate that the cis-decalin motif of 31 could be used as a key synthetic precursor of certain Schisandraceae metabolites. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Synthesis method of 1,4-cyclohexanedione monoethylene ketal

The invention relates to the technical field of organic synthesis, and particularly discloses a synthesis method of 1,4-cyclohexanedione monoethylene ketal. The synthesis method comprises the following step: with dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate, ethylene glycol and water as raw materials and acidic ionic liquid as a reaction medium and a catalyst, sequentially carrying out heatingto 105-120 DEG C and 130-140 DEG C for reactions respectively to obtain the 1,4-cyclohexanedione monoethylene glycol ketal. According to the synthesis method disclosed by the invention, one-pot synthesis from dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate to 1,4-cyclohexanedione monoethylene glycol ketal is realized, and the problems of low industrial production efficiency and low yield of 1,4-cyclohexanedione monoethylene glycol ketal in the prior art are solved.

An investigation into the role of 2,6-lutidine as an additive for the RuCl3-NaIO4 mediated oxidative cleavage of olefins to ketones

2,6-Lutidine has been identified as a beneficial additive for the oxidative cleavage of olefins to ketones by NaIO4 in the presence of catalytic RuCl3, improving the yield and shortening the reaction times. In the absence of 2,6-lutidine reactions stalled at the diol intermediate with incomplete conversion to the desired ketones. The reaction protocol described herein also avoids the use of harmful solvents such as CCl4 and DCE and is tolerant of a range of functional groups.