122-31-6

Basic information

• Product Name: Malonaldehyde bis(diethyl acetal)
• Synonyms: 1,1,3,3-tetraethoxy-propan;Malonaldehyde diethyl acetal;Malonaldehydediethylacetal;Tetraethoxypropane;Tetraethyl malondialdehyde acetal;USAF kf-26;usafkf-26;1,1,3,3-TETRAETHOXYPROPANE
• CAS NO: 122-31-6
• Molecular Formula: C₁₁H₂₄O₄
• Molecular Weight: 220.31
• EINECS: 204-533-1
• Mol File: 122-31-6.mol
• Article Data: 11

Chemical Properties

• Melting Point: -90 °C
• Boiling Point: 220 °C(lit.)
• Flash Point: 190 °F
• Appearance: Clear colorless to yellow/Liquid
• Density: 0.919 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.302mmHg at 25°C
• Refractive Index: n20/D 1.411(lit.)
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Slightly), Ethyl Acetate (Slightly), Methanol (Slightly)
• Water Solubility: insoluble
• BRN: 1209619
• CAS DataBase Reference: Malonaldehyde bis(diethyl acetal)(CAS DataBase Reference)
• NIST Chemistry Reference: Malonaldehyde bis(diethyl acetal)(122-31-6)
• EPA Substance Registry System: Malonaldehyde bis(diethyl acetal)(122-31-6)

Safety Data

• Hazard Codes: Xn
• Statements: 22
• Safety Statements: 36/37/39-26-24/25
• RIDADR: 1993
• WGK Germany: 3
• RTECS: ON8750000
• HazardClass: 3.2
• PackingGroup: III
• Hazardous Substances Data: 122-31-6(Hazardous Substances Data)

Usage

Chemical Properties

CLEAR COLOURLESS TO YELLOW LIQUID

Uses

Different sources of media describe the Uses of 122-31-6 differently. You can refer to the following data:
1. Organic synthesis.
2. 1,1,3,3-Tetraethoxypropane has been used in the preparation of diazabicyclodecenes.

InChI:InChI=1/C7H14O3/c1-3-9-7(5-6-8)10-4-2/h6-7H,3-5H2,1-2H3

Synthetic route

ethyl vinyl ether (109-92-2) + orthoformic acid triethyl ester (122-51-0) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
Stage #1: ethyl vinyl ether; orthoformic acid triethyl ester With boron trifluoride diethyl etherate at 20 - 38℃; Stage #2: With potassium carbonate at 20℃; for 2h;	69.2%
With iron(III) chloride
With boron fluoride ether

vinyl isopropyl ether (926-65-8) + orthoformic acid triethyl ester (122-51-0) → malondialdehyde bis(diethyl acetal) (122-31-6) + 1,3,3-triethoxy-1-(isopropoxy)propane (603151-68-4)

Conditions	Yield
iron(III) chloride at -30℃; for 6h; Product distribution / selectivity;	A 6.5% B 42%
iron(III) chloride at 0℃; for 6h; Product distribution / selectivity;	A 13.6% B 27%

trimethylsiloxyethene (6213-94-1) + orthoformic acid triethyl ester (122-51-0) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
With zinc(II) chloride In ethyl acetate for 3h; Ambient temperature;	76.5%

ethyl vinyl ether (109-92-2) + orthoformic acid triethyl ester (122-51-0) → malondialdehyde bis(diethyl acetal) (122-31-6) + 1,1,3,5,5-pentaethoxy-pentane (5870-87-1)

Conditions	Yield
With boron trifluoride diethyl etherate In diethyl ether at 10℃;	A 64% B 17%

ethanol (64-17-5) + 3.3-diethoxy-propionaldehyde imidechloro stannate → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
at 45℃;

vinyl acetate (108-05-4) + orthoformic acid triethyl ester (122-51-0) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
With iron(III) chloride; sodium hydrogencarbonate 1) 2 h, reflux; 2) 20 deg C, 2 h;	56%
at 80℃; beim Erwaermen in Gegenwart von Katalysatoren (z.B. FeCl3, AlCl3, SnCl2, SnCl4, ZnCl2, HgCl2);

2-ethoxy-1,3-dioxane (76508-46-8) + ethyl vinyl ether (109-92-2) → malondialdehyde bis(diethyl acetal) (122-31-6) + di(1,3-dioxan-2-yl)methane (30963-84-9) + 2-(2,2-diethoxyethyl)-1,3-dioxane (86444-87-3)

Conditions	Yield
zinc(II) chloride In diethyl ether temperature below 30 deg C;	A n/a B n/a C 35%

vinyl acetate (108-05-4) + orthoformic acid triethyl ester (122-51-0) → malondialdehyde bis(diethyl acetal) (122-31-6) + acetic acid-(1,3,3-triethoxy-propyl ester) (91243-91-3) + 1,3-diacetoxy-1,3-diethoxypropane (21633-62-5)

Conditions	Yield
With p-benzoquinone at 30℃; for 24h;

2-Ethoxy-5,5-dimethyl-1,3-dioxane (5783-79-9) + ethyl vinyl ether (109-92-2) → malondialdehyde bis(diethyl acetal) (122-31-6) + bis(5,5-dimethyl-1,3-dioxan-2-yl)-methane (30859-70-2) + 2-(2,2-diethoxyethyl)-5,5-dimethyl-1,3-dioxane (86444-88-4)

Conditions	Yield
zinc(II) chloride In diethyl ether temperature below 30 deg C;

(E)-3-Ureido-but-2-enoic acid ethyl ester (5435-44-9, 22243-66-9) + orthoformic acid triethyl ester (122-51-0) + acetylene (74-86-2) → malondialdehyde bis(diethyl acetal) (122-31-6) + 1,1-diethoxypropane (4744-08-5) + 1,1,4,4-tetraethoxy-2-butyne (3975-08-4)

Conditions	Yield
under 8826.09 - 12503.6 Torr;
at 170℃; under 8826.09 - 12503.6 Torr;

ethanol (64-17-5) + cyclohexa-1,4-diene (1165952-92-0) → malondialdehyde bis(diethyl acetal) (122-31-6) + ethyl 3,3-diethoxypropanoate (10601-80-6) + diethyl malonate (105-53-3)

Conditions	Yield
With hydrogenchloride; ozone -40 deg C, then ca. 30 min reflux;	A n/a B 70% C n/a
With hydrogenchloride; ozone -40 deg C, then ca. 30 min reflux;	A 70% B 70% C n/a
With hydrogenchloride; ozone at -40℃; Product distribution;	A n/a B 70% C n/a

2-bromo-1,1,3-triethoxy-propane (6630-39-3) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: ethanolic KOH-solution 2: hydrogen chloride View Scheme

orthoformic acid triethyl ester (122-51-0) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: boron trifluoride; mercury(II) diacetate 2: iron(III) chloride View Scheme

1,1-dichloro-3,3-diethoxy-propane (42084-63-9) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: NaOEt View Scheme

1-chloro-3,3-diethoxy-propene (14112-65-3) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: ion-exchange resin + form> 2: Na View Scheme

1,3,3-triethoxypropene (5444-80-4) + ethanol (64-17-5) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
With hydrogenchloride

ethanol (64-17-5) + acetic acid-(1,3,3-triethoxy-propyl ester) (91243-91-3) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
With iron(III) chloride

ethanol (64-17-5) + malonaldehyde diethylacetal-imine; chloro stannate → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
at 45℃;

ethanol (64-17-5) + 3,3-diethoxypropanal (6367-37-9) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
With hydrogenchloride

ethanol (64-17-5) + 3-chloro-1,3-diethoxy-propene (20760-42-3) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
With sodium

Propargylic aldehyde (624-67-9) + ethanol (64-17-5) → malondialdehyde bis(diethyl acetal) (122-31-6)

Conditions	Yield
(i) N-methylpiperidine, (ii) HCl; Multistep reaction;

ethanol (64-17-5) + 1-chloro-3,3-diethoxy-propene (14112-65-3) → malondialdehyde bis(diethyl acetal) (122-31-6)

ethanol (64-17-5) + 3-phenoxy-propenal (2862-47-7) → malondialdehyde bis(diethyl acetal) (122-31-6)

vinyl acetate (108-05-4) + iron(III) chloride (7705-08-0) + orthoformic acid triethyl ester (122-51-0) → malondialdehyde bis(diethyl acetal) (122-31-6)

iron(III) chloride (7705-08-0) + ethyl vinyl ether (109-92-2) + orthoformic acid triethyl ester (122-51-0) → malondialdehyde bis(diethyl acetal) (122-31-6)

malondialdehyde bis(diethyl acetal) (122-31-6) + trans-ethyl 4-hydrazinylcyclohexane-1-carboxylate hydrochloride → trans-4-pyrazol-1-yl-cyclohexanecarboxylic acid ethyl ester

Conditions	Yield
In ethanol for 2h; Reflux;	100%
Stage #1: malondialdehyde bis(diethyl acetal); trans-ethyl 4-hydrazinylcyclohexane-1-carboxylate hydrochloride In ethanol Reflux; Stage #2: With sodium hydrogencarbonate In ethanol; water	100%

malondialdehyde bis(diethyl acetal) (122-31-6) + (S)-4-Benzyl-2-oxazolidinone (90719-32-7) → (S,E)-3-(4-benzyl-2-oxooxazolidin-3-yl)acrylaldehyde

Conditions	Yield
With sulfuric acid In chloroform diastereoselective reaction;	99%

malondialdehyde bis(diethyl acetal) (122-31-6) → 1,3-dichloro-1,3-diethoxypropane (50840-17-0)

Conditions	Yield
With phosphorus trichloride at 50℃; for 6h;	98.5%
With tetrachloromethane; phosphorus pentachloride
With pyridine; tetrachloromethane; thionyl chloride
With phosphorus pentachloride; trichlorophosphate

(S)-4-(3,4-dimethoxybenzyl)oxazolidin-2-one (142763-11-9) + malondialdehyde bis(diethyl acetal) (122-31-6) → (5R,10aS)-5-{[(5R,10aS)-7,8-dimethoxy-3-oxo-1,5,10,10a-tetrahydro[1,3]oxazolo[3,4-b]isoquinolin-5-yl]methyl}-7,8-dimethoxy-1,5,10,10a-tetrahydro[1,3]oxazolo[3,4-b]isoquinolin-3-one

Conditions	Yield
With sulfuric acid In chloroform at 20℃; for 12h; Pictet-Spengler Synthesis; diastereoselective reaction;	98%

malondialdehyde bis(diethyl acetal) (122-31-6) + 2,6-diamino-3H-pyrimidin-4-one (100643-27-4, 143504-99-8) → C11H12N8O2 (142168-84-1)

Conditions	Yield
With acetic acid for 3.5h; Heating;	97%

malondialdehyde bis(diethyl acetal) (122-31-6) + 3-hexyl-2-methylbenzo[d]thiazol-3-ium iodide → 2-<5-(3-hexyl-2-benzothiazolylidene)-1,3-pentadienyl>-3-nonylbenzothiazolium iodide

Conditions	Yield
With pyridine for 2h; Heating;	96%

malondialdehyde bis(diethyl acetal) (122-31-6) + 1.3-butanediol (18826-95-4, 107-88-0) → bis(4-methyl-1,3-dioxan-2-yl)methane (71172-96-8)

Conditions	Yield
With KU-2-8 cation exchange resin In benzene at 120 - 130℃; heating until alcohol liberation was complete;	95%

malondialdehyde bis(diethyl acetal) (122-31-6) + 3-nonyl-2-methylbenzothiazolium iodide → 2-<5-(3-nonyl-2-benzothiazolylidene)-1,3-pentadienyl>-3-nonylbenzothiazolium iodide

Conditions	Yield
With pyridine for 2h; Heating;	95%

malondialdehyde bis(diethyl acetal) (122-31-6) + 1-bromo-2-ethoxyethene (18519-95-4) → 2-bromo-1,1,3,5,5-pentaethoxy-pentane (25798-89-4)

Conditions	Yield
With zinc(II) chloride In ethyl acetate for 5.5h; Ambient temperature;	94%
With boron trifluoride diethyl etherate

2-methyl-2,4-pentanediol (107-41-5) + malondialdehyde bis(diethyl acetal) (122-31-6) → bis(4,4,6-trimethyl-1,3-dioxan-2-yl)methane (86444-86-2)

Conditions	Yield
With KU-2-8 cation-exchange resin at 110 - 120℃; heating until alcohol liberation was complete;	94%

malondialdehyde bis(diethyl acetal) (122-31-6) + 2,2-Dimethyl-1,3-propanediol (126-30-7) → bis(5,5-dimethyl-1,3-dioxan-2-yl)-methane (30859-70-2)

Conditions	Yield
With KU-2-8 cation-exchange resin at 110 - 120℃; heating until alcohol liberation was complete;	94%

3-methyl-butane-1,3-diol (2568-33-4) + malondialdehyde bis(diethyl acetal) (122-31-6) → bis(4,4-dimethyl-1,3-dioxan-2-yl)methane (86444-85-1)

Conditions	Yield
With KU-2-8 cation-exchange resin In benzene at 120 - 130℃; heating until alcohol liberation was complete;	93%

malondialdehyde bis(diethyl acetal) (122-31-6) + propylene glycol (57-55-6) → bis(4-methyl-1,3-dioxolan-2-yl)methane (1599-50-4)

Conditions	Yield
With KU-2-8 cation-exchange resin at 110 - 120℃; heating until alcohol liberation was complete;	93%

malondialdehyde bis(diethyl acetal) (122-31-6) + 2-Thiobarbituric acid (91759-32-9) → 5-<3-(6-hydroxy-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidin-5-yl)prop-2-enylidene>-2-thioxo-2,3-dihydropyrimidine-4,6(1H,5H)-dione

Conditions	Yield
With hydrogenchloride for 1.5h; Heating;	93%

malondialdehyde bis(diethyl acetal) (122-31-6) + 4-nitro-2H-pyrazol-3-ylamine hydrochloride → 3-nitro-pyrazolo[1,5-a]pyrimidine (55405-64-6)

Conditions	Yield
With acetic acid	92.5%

malondialdehyde bis(diethyl acetal) (122-31-6) + ethylene glycol (107-21-1) → di(1,3-dioxolan-2-yl)methane (4405-17-8)

Conditions	Yield
With KU-2-8 cation-exchange resin at 110 - 120℃; heating until alcohol liberation was complete;	92%

malondialdehyde bis(diethyl acetal) (122-31-6) + 2.3-butanediol (513-85-9) → bis(4,5-dimethyl-1,3-dioxolan-2-yl)methane (32465-54-6)

Conditions	Yield
With KU-2-8 cation-exchange resin at 110 - 120℃; heating until alcohol liberation was complete;	91%

potassium tetrachloroplatinate + malondialdehyde bis(diethyl acetal) (122-31-6) + 1,2-diamino-benzene (95-54-5) → [(dibenzo[b,i]-1,4,8,11-tetraaza[14]annulene)platinum(II)] (77624-36-3)

Conditions	Yield
With CH3COOH; NaCH3COO In ethanol; water complex reacted with o-phenylenediamine at 60°C in aq. EtOH for 30 min, AcOH and tetraethoxypropane added, mixt. refluxed for 2 h, NaOAcadded, refluxed for 16 h; ppt. filtered while hot, washed with H2O, EtOH, ether, sublimated in vac. at 300°C, 0.01 Torr.;	91%

malondialdehyde bis(diethyl acetal) (122-31-6) + 4-(trifluoromethyl)phenylhydrazine hydrochloride (2923-56-0) → 1-(4-trifluoromethyl-phenyl)-1H-pyrazole (207797-05-5)

Conditions	Yield
With hydrogenchloride In ethanol at 75℃; for 2h;	91%

malondialdehyde bis(diethyl acetal) (122-31-6) + 2,3-dimethyl-2,3-butane diol (76-09-5) → 1,3-bis(4',4',5',5'-tetramethyl-1,3-dioxolan-2-yl)methane (86444-84-0)

Conditions	Yield
With KU-2-8 cation-exchange resin In benzene at 120 - 130℃; heating until alcohol liberation was complete;	90%

malondialdehyde bis(diethyl acetal) (122-31-6) + 3,5-dimethylaminoaniline (108-69-0) → N-<3-(3,5-Dimethylphenylimino)-1-propenyl>-3,5-dimethylanilin-Hydrogenperchlorat

Conditions	Yield
With perchloric acid In ethanol for 2h; Heating;	90%

malondialdehyde bis(diethyl acetal) (122-31-6) + trimethyleneglycol (504-63-2) → di(1,3-dioxan-2-yl)methane (30963-84-9)

Conditions	Yield
With KU-2-8 cation-exchange resin In benzene at 120 - 130℃; heating until alcohol liberation was complete;	89%

malondialdehyde bis(diethyl acetal) (122-31-6) + aniline hydrochloride (142-04-1) → phenyl[3-phenylaminoprop-2-en-1-ylidene]ammonium chloride (23769-16-6, 28140-60-5, 50328-50-2, 58467-94-0, 125367-88-6)

Conditions	Yield
In methanol Heating; Reflux;	89%

malondialdehyde bis(diethyl acetal) (122-31-6) + 2-(trifluoromethyl)phenylhydrazine hydrochloride (3107-34-4) → 1-(2-(trifluoromethyl)phenyl)-1H-pyrazole (84401-17-2)

Conditions	Yield
With hydrogenchloride In ethanol at 75℃; for 2h;	88%

malondialdehyde bis(diethyl acetal) (122-31-6) + 3-Chloro-6-hydrazinopyridazine (17284-97-8) → 3-chloro-6-(1H-pyrazol-1-yl)pyridazine (29334-66-5)

Conditions	Yield
With acetic acid In ethanol for 3h; Reflux;	86%

2-aminopyridine (504-29-0) + malondialdehyde bis(diethyl acetal) (122-31-6) → pyrido[1,2-a]pyrimidinium perchlorate

Conditions	Yield
With perchloric acid In ethanol at 80℃; Inert atmosphere;	86%

2-amino-3-hydroxypyridine (16867-03-1) + malondialdehyde bis(diethyl acetal) (122-31-6) → 9-hydroxy-pyrido<1,2-a>pyrimidin-5-ium perchlorate

Conditions	Yield
With perchloric acid In ethanol at 80℃; for 12h; Inert atmosphere;	85%

malondialdehyde bis(diethyl acetal) (122-31-6) + phenylhydrazine hydrochloride (59-88-1) → 1-phenylpyrazole (1126-00-7)

Conditions	Yield
With hydrogenchloride In ethanol at 75℃; for 2h;	84%
With ethanol

malondialdehyde bis(diethyl acetal) (122-31-6) + 5-amino-3-methyl-N-phenylpyrazole-4-carboxamide (96319-19-6) → 2-methyl-N-phenylpyrazolo<1,5-a>pyrimidine-3-carboxamide (96319-20-9)

Conditions	Yield
With hydrogenchloride In ethanol at 60 - 80℃; for 2h;	84%

malondialdehyde bis(diethyl acetal) (122-31-6) + 3‐cyclopropyl‐4‐thiocyanato‐1H‐pyrazol‐5‐amine → 2‐cyclopropyl‐3‐thiocyanatopyrazolo[1,5‐a]pyrimidine

Conditions	Yield
With hydrogenchloride In water for 24h;	84%
With hydrogenchloride In ethanol; water for 24h;

Upstream product

• 5444-80-4 1,3,3-triethoxypropene 
• 64-17-5 ethanol 
• 91243-91-3 acetic acid-(1,3,3-triethoxy-propyl ester) 
• 109-92-2 ethyl vinyl ether 
• 122-51-0 orthoformic acid triethyl ester 
• 108-05-4 vinyl acetate 
• 5435-44-9 (E)-3-Ureido-but-2-enoic acid ethyl ester 
• 74-86-2 acetylene 
• 6367-37-9 3,3-diethoxypropanal 
• 14112-65-3 1-chloro-3,3-diethoxy-propene 
• 2862-47-7 3-phenoxy-propenal 
• 20760-42-3 3-chloro-1,3-diethoxy-propene 
• 76508-46-8 2-ethoxy-1,3-dioxane 
• 1165952-92-0 cyclohexa-1,4-diene 

Downstream Products

• 3463-30-7 1-(4-nitrophenyl)pyrazole 
• 931-08-8 pyrazole carboxamide 
• 13417-36-2 1-(2,4-dinitrophenyl)-1H-pyrazole 
• 1126-00-7 1-phenylpyrazole 
• 55317-53-8 2-(1H-pyrazol-1-yl)benzoic acid 
• 25688-17-9 1-(2-nitrophenyl)pyrazol 
• 288-14-2 ISOXAZOLE 
• 288-13-1 NH-pyrazole 
• 930-36-9 1-methyl-1H-pyrazole 
• 1450-85-7 2-thioxopyrimidine 
• 542-78-9 Malondialdehyde 
• 36437-19-1 2-chloromalonaldehyde 
• 289-95-2 PYRIMIDINE 
• 42602-63-1 2-Methyl-selenolo-<2,3-b>pyridin 

Relevant articles and documents

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