CN1237572A - Preparation method of diethyl malonate - Google Patents
Preparation method of diethyl malonate Download PDFInfo
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- CN1237572A CN1237572A CN 99114644 CN99114644A CN1237572A CN 1237572 A CN1237572 A CN 1237572A CN 99114644 CN99114644 CN 99114644 CN 99114644 A CN99114644 A CN 99114644A CN 1237572 A CN1237572 A CN 1237572A
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- diethyl malonate
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- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims abstract description 4
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical class CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 208000012839 conversion disease Diseases 0.000 abstract description 32
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 abstract 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- -1 halogenated acetic acids ester Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229960002895 phenylbutazone Drugs 0.000 description 1
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical compound O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation method of diethyl malonate is characterized by that by the action of a compound as catalyst, using KI or NaI as catalyst promotor, using triethylamine or tripropyl amine as neutralizing agent and using aromatic hydrocarbon or dimethylformamide as solvent it uses ethyl chloro-acetate, carbon monoxide and ethyl alcohol, and makes them produce reaction for 10-72 hr, at 70-145 deg.C and carbon monoxide pressure of 0.5-4 Mpa so as to obtain the diethyl malonate. The reaction conversion rate is up to 98%, its side reaction is a little, reaction condition is moderate, so that it is suitable for industrial production, and possesses high research and application value.
Description
The present invention relates to the preparation of organic compound, particularly belong to the technical field for preparing malonic ester.
Propanedioic acid and derivative thereof are widely used in industry such as pharmacy, spices, foodstuff additive, polyester, are important fine chemical material and intermediates.Especially aspect medicine intermediate, propanedioic acid and derivative thereof are widely used in synthetic crust than peace acid, amino acid, VITMAIN B1, B2 and B6, the multiple medicines such as medicine and phenylbutazone of sleeping peacefully.
At present, the method for industrial production propanedioic acid and ester thereof mainly is by Mono Chloro Acetic Acid and sodium cyanide reaction, obtains after hydrolysis then, the esterification.This method has also been used the highly toxic substance sodium cyanide except that technical process is long, brought great difficulty for operation and liquid waste disposal.For this reason, developed the synthetic method of some new propanedioic acid and derivative thereof in the last few years in succession, as propylene or vinyl cyanide oxidation style (Phys, Chem.225,517,1974), with the ketene is the synthesis method (EP6611 of raw material, 1978), carbonyl process (DE2359963,1975 of carbonyl process of Potassium ethanoate or acetic ester (JP 46-26926,1971) and halogenated acetic acids ester, DE2524389,1976, DE2553931,1977).In addition, also have to be carried on the RhCl on the gac
33H
2O is a catalyzer, by the synthetic malonic ester (Bull.Chem.Soc.Jpn., 58,3082,1985) of the gas phase oxonation of chloracetate; Under a solid liquid phase jump condition, use (PPh respectively
3)
2PdCl
2(two-the triphenylphosphine palladium chloride) (Appl.Catal., 32,357,1987) and Co
2(CO)
8Or CoCl
2(Synth.Commun., 20,2631,1990) make catalyzer, have obtained the malonic ester of high yield under the condition of gentleness.Usually the complex compound of VIII family transition element such as Fe, Co, Ni, Rh and Pd should be as the catalyzer (Organometallics of synthetic propanedioic acid of halogenated acetic acids ester oxonation and derivative thereof, 5,947,1986.OrganicSynthesis via Metal Carbonyls, Vol.2,297-516,1977, DE 2606655,1977), wherein, the most commonly used with the cobalt-carbonyl complex compound, and mostly with Co
2(CO)
8Be catalyst precursor.And be catalyzer with the metallic palladium title complex of biphosphine ligand, to the research of carbon-halogen bond in-depth oxonation (Chem.Rev., 94,1047,1994) at the early-stage.
The object of the present invention is to provide a kind of new catalyst system, be used for preparing diethyl malonate through carbonylation, esterification, reach high conversion, high yield, reaction conditions gentleness, be easy to the purpose of suitability for industrialized production from the chloracetic acid ethyl ester.
The objective of the invention is to realize by following technical solution:
With chloracetic acid ethyl ester, carbon monoxide and ethanol be with general formula
Compound be under the catalyst, with KI or NaI is promotor, triethylamine or tripropyl amine or Tributylamine are neutralizing agent, and aromatic hydrocarbon or dimethyl formamide are solvent, under 70-145 ° of temperature, 0.5-4MPa carbon monoxide pressure under, reacted 10-72 hour, and made diethyl malonate, wherein, in the catalyzer general formula, Z=-(CH
2) n-(n=1,2,3,4,5,6),
[R=C
6H
5(phenyl), C
2H
5(ethyl), n-C
3H
7(n-propyl),
I-C
3H
7(sec.-propyl), n-C
4H
9(normal-butyl)],
M=Pd, Ni; X=CI, Br, I, CN, SCN, NO
2Its consumption mol ratio is: chloracetic acid ethyl ester: ethanol: catalyzer: promotor: neutralizing agent: solvent (liter)=1: 1.0～1.2: 2.3 * 10
-3～2.5 * 10
-2: 1.0 * 10
-2～1.6 * 10
-1: 1.0～1.5: 1～5.
In the such scheme, catalyzer better is following compound:
(dppmPdCI
2)
(dppePdCI
2)
(dppp
rPdCI
2)
(dppbPdCI
2)
(dppp
ePdCI
2)
(dpphPdCI
2)
(dppmNiCI
2)
(dppeNiCI
2)
(dppp
rNiCI
2)
(depePdCI
2)
(dp
r nPePdCI
2)
(dp
r ip
ePdCI
2)
(dBu
nPePdCI
2)
(depePdBr
2)
(depePdI
2)
(depePd (CN)
2)
(depePd (SCN)
2)
(depePd (NO
2)
2)
(dppbePdCI
2)
(dppfPdCI
2)
(dptePdCI
2)
(dmp
zMPdCI
2)
(dmp
zEPdCI
2)
In the aromatic hydrocarbon solvent, solvent is a toluene preferably, dimethylbenzene and methyl-phenoxide.Better tangible 85～125 ℃ of temperature of reaction, reaction pressure is tangible 1.5～3.0MPa better, and the reaction times better is at 20～60 hours.
The catalytic carbonylation esterification that the metal complexes that the present invention will contain bidentate class part first is used for the chloracetic acid ethyl ester as catalyzer is sent out should, helping under the catalysis of KI or NaI, successfully prepared diethyl malonate, and selectivity reaches as high as 98%, side reaction is few, the reaction conditions gentleness is easy to suitability for industrialized production, has higher research and using value.
Be embodiments of the invention below.
Embodiment one
The carbonylation esterification is carried out in 25ml glass inner-lining telescopic stainless steel autoclave.With 2.1 * 10
-2The dppmPdCl of mmol
2, 0.2ml (1.87mmol) ClCH
2COOC
2H
5, 0.27ml (1.94mmol) Et
3N, 0.12ml (2.0mmol) EtOH, 20mg (0.12mmol) KI, 5ml toluene adds in the reactor, mixes.Tighten kettle cover, fill the 1.0MPa carbon monoxide and wash still 5 times, charge into the 2.0MPa carbon monoxide then.Place constant temperature oil bath in 115 ℃ of reactions down, induction stirring reactor.Reacted 48 hours, and took out reactor, naturally cool to room temperature, product draws reaction result through gas chromatographic analysis and is: transformation efficiency 77.8%, select 72%, productive rate 56%.
Embodiment two
With dppePdCl
2Be catalyzer, other is with embodiment one, and reaction conversion ratio is 57.9%, and selectivity is 41.5%, productive rate 24%.
Embodiment three
With dppp
rPdCl
2Be catalyzer, other is with embodiment one, and reaction conversion ratio is 56.1%, and selectivity is 38.7%, productive rate 21.7%.
Embodiment four
With dppbPdCl
2Be catalyzer, other is with embodiment one, and reaction conversion ratio is 55.6%, and selectivity is 36%.Productive rate 20%.
Embodiment five
With dppp
ePdCl
2Be catalyzer, other is with embodiment one, and reaction conversion ratio is 67.6%, and selectivity is 21.9%, productive rate 14.8%.
Embodiment six
With dpphPdCI
2Be catalyzer, other is with embodiment one, and reaction conversion ratio is 64.6%, and selectivity is 15.7%, productive rate 97%.
Embodiment seven
With dppmNiCl
2Be catalyzer, the add-on of KI is 23mg (0.14mmol), and other is with embodiment one, and reaction conversion ratio is 49.8%, and selectivity is 23.1%, and productive rate is 11.3%.
Embodiment eight
With dppeNiCl
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 30.5%, and selectivity is 8%, and productive rate is 3%.
Embodiment nine
With depePdCl
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 69.6%, and selectivity is 32.6%, and productive rate is 22.7%.
Embodiment ten
With dp
r iPePdCl
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 65.4%, and selectivity is 27.7%, and productive rate is 18%.
Embodiment 11
With dp
r nPePdCl
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 84%, and selectivity is 15%, and productive rate is 13%.
Embodiment 12
With dmp
zMPdCl
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 64.4%, and selectivity is 98%, and productive rate is 45.5%.
Embodiment 13
With dmp
zEPdCl
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 61.7%, and selectivity is 81.4%, and productive rate is 51.1%.
Embodiment 14
With dptePdCl
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 54.9%, and selectivity is 93.7%, and productive rate is 51.4%.
Embodiment 15
With dppfPdCl
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 47.8%, and selectivity is 56.3%, and productive rate is 26.9%.
Embodiment 16
With depePdBr
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 69.6%, and selectivity is 32.6%, and productive rate is 22.7%.
Embodiment 17
With depePdI
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 86.5%, and selectivity is 16%, and productive rate is 13.78%.
Embodiment 18
With depePd (NO
2)
2Be catalyzer, other is with embodiment seven, and reaction conversion ratio is 68.5%, and selectivity is 15%, and productive rate is 10.3%.
Embodiment 19
NaI with 0.14mmol is a promotor, and other is with embodiment one, and reaction conversion ratio is 76.1%, and selectivity is 70.1%, and productive rate is 53.7%.
Embodiment 20
With the tripropyl amine is neutralizing agent, and other is with embodiment one, and reaction conversion ratio is 70.1%, and selectivity is 52.5%, and productive rate is 36.8%.
Embodiment 21
With the Tributylamine is neutralizing agent, and other is with embodiment one, and reaction conversion ratio is 51%, and selectivity is 37%, and productive rate is 19%.
Embodiment 22
With the para-xylene is solvent, and 0.14mmol KI is a promotor, and other is with embodiment one, and reaction conversion ratio is 50%, and selectivity is 86%, and productive rate is 43%.
Embodiment 23
With the methyl-phenoxide is solvent, and other is with embodiment 22, and reaction conversion ratio is 71.1%, and selectivity is 49.2%, and productive rate is 39.9%.
Embodiment 24
With the dimethyl formamide is solvent, and other is with embodiment 22, and reaction conversion ratio is 70.1%, and selectivity is 47.1%, and productive rate is 33%.
Embodiment 25
Temperature of reaction is 70 ℃, and the consumption of KI is 0.14mmol, and all the other are with embodiment one, and reaction conversion ratio is 54%, and selectivity is 31.5%, productive rate 17%.
Embodiment 26
Temperature of reaction is 140 ℃, and all the other are with embodiment 25, and reaction conversion ratio is 80%, and selectivity is 30%, productive rate 24%.
Embodiment 27
Reaction pressure is 1.0MPa, and the KI consumption is 0.14mmol, and all the other are with embodiment one, and reaction conversion ratio is 70%, and selectivity is 53.1%, productive rate 37.2%.
Embodiment 28
Reaction pressure is 4.0MPa, and all the other are with embodiment 27, and reaction conversion ratio is 81%, and selectivity is 69.1%, productive rate 56%.
Embodiment 29
Reaction times is 12 hours, and the KI consumption is 0.14mmol, and all the other are with embodiment one, and reaction yield is 8%.
Embodiment 30
Reaction times is 72 hours, and all the other are with embodiment 36, and reaction yield is 56%.
The embodiment hentriaconta-
DppmPdCl
2Add-on be 0.443 * 10
-2Mmol,
KIAdd-on be 0.14mmol, other is with embodiment one, reaction conversion ratio is 30%, selectivity is 69%, productive rate 20.7%.
Embodiment 32
DppmPdCl
2Add-on be 4.69 * 10
-2Mmol, other is with the embodiment hentriaconta-, and one, reaction conversion ratio is 86%, selectivity is 61.6%, productive rate 53%.
Embodiment 33
The add-on 0.002mmol of KI, other is with embodiment one, and reaction conversion ratio is 57%, and selectivity is 22.2%, and productive rate is 12.7%.
Embodiment 34
The add-on 0.3mmol of KI, other is with embodiment one, and reaction conversion ratio is 80%, and selectivity is 71.3%, and productive rate is 57%.
Claims (4)
1. the preparation method of a diethyl malonate prepares diethyl malonate with chloracetic acid ethyl ester, carbon monoxide and ethanol synthesis, it is characterized in that with general formula being
Compound be under the catalyst, with KI or NaI is promotor, triethylamine or tripropyl amine or Tributylamine are neutralizing agent, and aromatic hydrocarbon or dimethyl formamide are solvent, under 70-145 °, 0.5-4MPa carbon monoxide pressure under, reacted 10-72 hour, and made diethyl malonate, wherein, in the catalyzer general formula, Z=-(CH
2) n-(n=1,2,3,4,5,6),
[R=C
6H
5(phenyl), C
2H
5(ethyl), n-C
3H
7(n-propyl), i-C
3H
7(sec.-propyl), n-C
4H
9(normal-butyl)],
M=Pd, Ni; X=CI, Br, I, CN, SCN, NO
2Its consumption mol ratio is: chloracetic acid ethyl ester: ethanol: catalyzer: promotor: neutralizing agent: solvent (liter)=1: 1.0～1.2: 2.3 * 10
-3～2.5 * 10
-2: 1.0 * 10
-2～1.6 * 10
-1: 1.0～1.5: 1～5.
2. the preparation method of diethyl malonate according to claim 1, it is characterized in that described catalyzer with following compound for well:
(dppmPdCI
2)
(dppePdCI
2)
(dppp
rPdCI
2)
(dppbPdCI
2)
(dppp
ePdCI
2)
(dpphPdCI
2)
(dppmNiCI
2)
(dppeNiCI
2)
(dppp
rNiCI
2)
(depePdCI
2)
(dp
r nPePdCI
2)
(dp
r iP
ePdCI
2)
(dBu
nPePdCI
2)
(depePdBr
2)
(depePdI
2)
(depePd (CN)
2)
(depePd (SCN)
2)
(depePd (NO
2)
2)
(dppbePdCI
2)
(dppfPdCI
2)
(dptePdCI
2)
(dmp
zMPdCI
2)
(dmp
zEPdCI
2)
3. the preparation method of diethyl malonate according to claim 1, it is characterized in that described aromatic hydrocarbon solvent with toluene, dimethylbenzene, methyl-phenoxide for well.
4. according to the preparation method of claim 1,2,3 described diethyl malonates, it is characterized in that described temperature of reaction 85～125 ℃ for well, reaction pressure at 1.5～3.0MPa for well, the reaction times at 20～60 hours for well.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114644A CN1115324C (en) | 1999-01-26 | 1999-01-26 | Preparation method of diethyl malonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114644A CN1115324C (en) | 1999-01-26 | 1999-01-26 | Preparation method of diethyl malonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1237572A true CN1237572A (en) | 1999-12-08 |
| CN1115324C CN1115324C (en) | 2003-07-23 |
Family
ID=5277700
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99114644A Expired - Fee Related CN1115324C (en) | 1999-01-26 | 1999-01-26 | Preparation method of diethyl malonate |
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| Country | Link |
|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453521C (en) * | 2006-12-13 | 2009-01-21 | 井冈山学院 | Prepn and application of ethyl diisopropyl carboxylate |
| CN106045854A (en) * | 2016-06-02 | 2016-10-26 | 三峡大学 | Preparation method of diethyl malonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1104628A (en) * | 1993-12-30 | 1995-07-05 | 中国科学院兰州化学物理研究所 | Oxo-synthesis of diethyl malonate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453521C (en) * | 2006-12-13 | 2009-01-21 | 井冈山学院 | Prepn and application of ethyl diisopropyl carboxylate |
| CN106045854A (en) * | 2016-06-02 | 2016-10-26 | 三峡大学 | Preparation method of diethyl malonate |
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| CN1115324C (en) | 2003-07-23 |
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