+adhi

"Diethylmalonat"OR"Diethylmalonate"OR"Malonatededithyle"OR"diethylpropanedioate"OR"Malonicaciddiethyles

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Mandarin
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Processforproducingdiethylmalonate
CN1092638C
ABSTRAKditerjemahkandaribahasaMandarin
Thepresentinventionisamethodforthepreparationofdiethylmalonate,ethyl
acetateischlorinated,carbonmonoxideandethanolinthegeneralformula(R

DESKRIPSIditerjemahkandaribahasaMandarin
Preparationofdiethylmalonate

Nomorpublikasi
Jenispublikasi
Nomoraplikasi
Tanggalpublikasi
Tanggalpengajuan
Tanggalprioritas

CN1092638C
Pemberian
CN99114642
16Okt2002
26Jan1999
26Jan1999

Jugadipublikasikan
sebagai

CN1237570A

Penemu

,,,,

Pemohon

EksporKutipan

BiBTeX,EndNote,RefMan

KutipanPaten(2),Klasifikasi(2),PeristiwaHukum(4)
TautanEksternal:SIPO,Espacenet

Thepresentinventionrelatestothepreparationoforganiccompounds,especially
thosebelongingtothetechnicalfieldofthepreparationofthemalonate.
Propionicacidanditsderivativesarewidelyusedinthepharmaceutical,spices,

KLAIM (3)diterjemahkandaribahasaMandarin

foodadditives,polyesterandotherindustries,isimportantfinechemicalraw

1.Aprocessforpreparingmalonicaciddiethylesterisethylchloroacetate,

materialsandintermediates.Especiallyintermsofpharmaceuticalintermediates,

preparedbythereactionofcarbonmonoxideandethanoldiethylmalonate,

propionicacidanditsderivativesarewidelyusedinthesynthesisofBabiAn

characterizedinthatinthegeneralformula(R1R2R3P)aMClbcompoundis

acid,aminoacids,vitaminsB1,B2andB6,hypnoticsandphenylbutazoneand

catalyzedbyacatalysttoKIorNaIascocatalyst,triethylamineortripropylamine

otherdrugs.

asneutralizingagent,anaromatichydrocarbonordimethylformamideasa

Currently,industrialproductionofpropionicacidanditsestersmainlybyreaction
ofchloroaceticacidwithsodiumcyanidefollowedbyhydrolysis,esterification
obtained.Inadditiontoalongprocessofthelaw,butalsotheuseofhighlytoxic
substancessodiumcyanide,tooperationsandwastetreatmenthasbrought
greatdifficulties.Forthisreason,inrecentyearshavedevelopedanumberof
newmethodsfortheirsynthesismalonatederivatives,suchaspropyleneor
acrylonitrileoxidation(Phys,Chem.225,517,1974),asarawmaterialinthe
synthesisofketeneFrance(EP6611,1978),potassiumacetateoracetate
carbonylationmethod(JP4626926,1971)andhaloacetatesOxonationAct
(DE2359963,1975,DE2524389,1976,DE2553931,1977).Inaddition,inorderto
loadontoactivatedcarbonRhCl33H2Oasthecatalyst,thereactionsynthesis
malonate(Bull.Chem.Soc.Jpn,58,3082,1985.)Bygasoxonationchloroacetates

solvent,atatemperatureof70145,thecarbonmonoxidepressureis0.5
4MPa,andthereaction1072hours,toobtaindiethylmalonatewhereinthe
catalystofformula(R1R2R3P)aMClbin,R1=Ph,2CH3OC6H4,2CH3O5
CH3C6H3,2CH35ClC6H3,2OHC6H4,cyclohexyl,C6H5OR2=Ph,2
CH3OC6H4,2CH3O5CH3C6H3,2CH35ClC6H3,2OHC6H4,cyclohexyl,
C6H5OR3=Ph,2CH3OC6H4,2CH3O5CH3C6H3,2CH35ClC6H3,2
OHC6H4,cyclohexyl,C6H5O,Me,Et,npropyl,nbutyl,isobutyl,secbutyl,tert
butyl,npentylgroup,nhexylgroup,M=Pd,Ni,Pt,Rh,Ru,Ir(CO)inaddition,
aandbcanalsobedifferentdependingonM,respectively3and2,3and1and
2and1,theamountofmolesratio:chloroethylacetate:ethanol:Catalyst:
cocatalyst:Neutralizingagent:Solvent=1:1.0~1.2:2.3103~2.5102:1.0
102~1.6101:1.0~1.5~5.

insolid,respectively,underphasetransferconditionsusing(PPh3)2PdCl2(bis

2.Preparationofdiethylmalonateaccordingtoclaim1,whereinsaid

triphenylphosphinepalladiumdichloride)(Appl.Catal,32,357,1987.),andCo2

aromatichydrocarbonsolventistoluene,xylene,anisole.

(CO)8orCoCl2(Synth.Commun,.20,2631,1990)asacatalystundermild
conditionstoobtainhighyieldsofthemalonate.TypicallyFe,thecatalyst

3.Themethodofdiethylmalonatewaspreparedaccordingtoclaim1,

(Organometallicspropionicacidanditsderivativesshouldbeusedasthe

characterizedinthatthereactiontemperatureis85~125,reaction

halogenatedaceticacidestercomplexesofCo,Ni,RhandPdandotherGroup

pressure1.5~3.0MPa,reactiontimeis20to60hours.

VIIItransitionelementofthehydroformylationreaction,
5,947,1986.OrganicSynthesisviaMetalCarbonyls,Vol.2,297516,1977,DE
2606655,1977),whereinthecobaltcarbonylcomplexesinthemostcommon,andmostwithCo2(CO)8ascatalyst
precursor.
Objectofthepresentinventiontoprovideanovelcatalystsystemfortheethylchloroacetatecatalyzedbytransitionmetal
complexeshydroformylation,esterificationofdiethylmalonate,toachievehighconversion,highyield,thereaction
conditionsmild,thepurposeofindustrialproductioniseasy.
Objectofthepresentinventionisachievedbythefollowingtechnicalsolution:Achlorinatedethylacetate,carbonmonoxide
andethanolinthegeneralformula(R1R2R3P)aMClbcompoundiscatalyzedbythecatalysttococatalystisKIorNaI,
triethylamineortripropylamineasaneutralizingagent,anaromatichydrocarbonordimethylformamideasasolvent,ata
temperatureof70145,underacarbonmonoxidepressureis0.54MPa,andthereaction1072hourstogivediethyl
malonatewhereinthecatalystofformula(R1R2R3P)aMClbin,R1=C6H5,2CH3OC6H4,2CH3O5CH3C6H3,2CH35
ClC6H3,2OHC6H4,Cy(cyclohexyl),C6H5OR2=C6H5,2CH3OC6H4,2CH3O5CH3C6H3,2CH35ClC6H3,2
OHC6H4,Cy,C6H5OR3=C6H5,2CH3OC6H4,2CH3O5CH3C6H3,2CH35ClC6H3,2OHC6H4,Cy,C6H5O,Me
(methyl),Et(ethyl),Prn(npropyl),Bun(nbutyl),Bui(isobutyl),Busec(sec),But(tertbutyl),Pen(npentyl),Hen(nhexyl)
M=Pd,Ni,Pt,Rh,Ru,Ir(CO)inaddition,aandbcanberespectivelydifferentdependingonM3and2,3and1and2
and1.Inanamountofmolarratioof:chloroethylacetate:ethanol:Catalyst:cocatalyst:Neutralizingagent:Solvent(L)=
1:1.0~1.2:2.3103~2.5102:1.0102~1.6101:1.0~1.5:1~5.

Above,thecatalystmayalsobeused(Ph3As)2PdCl2or(Ph3Sb)2PdCl2.Thecatalystofthegeneralformula,preferredare
thefollowingcompounds:(Ph3P)2PdCl2,(Ph3P)2NiCl2,(Ph3P)2PtCl2,(Ph3P)3RhCl,(Ph3P)3RuCl2,(Ph3P)2Ir(CO)
Cl,[(2MeOC6H4)3P]2PdCl2,[(2MeO5MeC6H3)3P]2PdCl2,[(2Me5C1C6H3)3P]2PdCl2,[(2OHC6H4)3P]
2PdCl2,(Ph2CyP)2PdCl2,(PhCy2P)2PdCl2,(Cy3P)2PdCl2,(Ph2MeP)2PdCl2,(Ph2EtP)2PdCl2,(Ph2PrnP)2PdCl2,
(Ph2BunP)2PdCl2,(Ph2BuiP)2PdCl2,(Ph2BusecP)2PdCl2,(Ph2ButP)2PdCl2,(Ph2PenP)2PdCl2,(Ph2HenP)2PdCl2,
[(PhO)3P)2PdCl2,thearomatichydrocarbonsolventispreferablytoluene,xylene,anisole.
Thereactiontemperatureispreferably85125,thereactionpressureispreferablyat1.53.0MPa,thereactiontimeis
preferably2060hours.
ThepresentinventionusesaKIorNaIascocatalyst,thecatalyticreactionofethylchlorideOxonationesterification
malonatehaveagreatroleinpromotingsuchthattheyieldofdiethylmalonatearemoresubstantialincrease,reduceside
effects,theexperimentalresultsshowedthatwiththecocatalystisaddedgraduallyincreasetheamountofreaction
conversion,selectivityandyieldrateshaveagreaterincrease,buttheamountisgreaterthanchloroethylacetate1/10
(mol),theconversionrateandtheyieldofthereactionalmostneverincreases.
So,malonatepresentinventionprovidesapreparationmethodenablestheconversionratereached93.6%,theyieldreached
64.3%,andmildreactionconditions,easeofindustrialproduction,withahighvalue.
Thefollowingareexamplesofthepresentinvention.
AhydroformylationreactionwascarriedoutinExampleesterification25mlglasslinedstainlesssteelautoclavecasing.The
2.1102mmolof(Ph3P)2PdCl2,0.2ml(1.87mmol)ClCH2COOC2H5,0.27ml(1.94mmol)Et3N,0.12ml(2.0mmol)EtOH,
20mg(0.12mmol)KI,5mltoluenewasaddedtothereactor,mixed.Thelidwastightened,theautoclavecharge1.0MPa
monoxidewashed5times,thenchargedwithcarbonmonoxide2.0MPa.Thekettlewasplacedinaconstanttemperatureoil
bathat115reaction,electromagneticstirring.For48hours,removethereactor,cooledtoroomtemperature,theproduct
wasobtainedbygaschromatographyanalysisresultsofthereactionof:theconversionof93.6%,theselectivity68.7%,
yield64.3%.
SecondEmbodimentIn(Ph3P)3RuCl2ascatalyst,theotherone,thereactionconversionratewas60.9%inExample,the
selectivitywas55.6%,yield34%.
Inthethirdexample(Ph3P)3NiCl2ascatalyst,withotherembodimentsofareactionconversionwas70.5%,theselectivity
was33.6%,yield24%.
Inthefourthembodiment(Ph3P)3RhClasacatalyst,theotherone,thereactionconversionratewas65.0%inExample,
theselectivityof30.1%.Yield20%.
Embodiment5In(Ph3P)3PtCl2ascatalyst,withtheotherembodimentsofareactionconversionwas49.5%,the
selectivitywas18.4%.
ExampleVIwas(Ph3P)3Ir(CO)Clasacatalyst,otherembodimentswithareactionconversionwas39.3%,theselectivity
was21.7%.
ExampleVIIwith[(2MeOC6H4)3P]2PdCl2asthecatalyst,KIisaddedinanamountof23mg(0.14mmol),theotherone,
andthereactionconversionwas60%inExample,theselectivity70%,yield40%.
Intheeighthembodiment[(2MeO5MeC6H3)3P]2PdCl2asthecatalyst,theotherwiththeseventhembodiment,the
reactionconversionwas65%andtheselectivity60%,yield38%.
ExampleIXwas[(2MeO5ClC6H3)3P]2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereaction
conversionwas50%andtheselectivitywas90%andtheyieldwas43%.
Inthetenthembodiment[(2OHC6H4)3P]2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereaction
conversionratewas60%andtheselectivitywas80%andtheyieldwas50%.
Exampleelevento(Ph2CyP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversionrate
was82%andtheselectivity70%,yield59.2%.
Exampletwelveto(PhCy2P)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversionrate
was75%andtheselectivitywas73%andtheyieldwas55.6%.
Examplethirteento(Cy3P)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversionrate
was68.1%,theselectivity70%,yield51.1%.
Examplefourteento(Ph2MeP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversionrate
was75%andtheselectivity70%,yield48.6%.
Examplefifteento(Ph2EtP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversionwas
68%andtheselectivity70%,yield47.0%.
Examplesixteento(Ph2PrnP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversionwas
65%andtheselectivitywas70%andtheyieldwas45.9%.
Example67Inthe(Ph2BunP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversionrate

was60%andtheselectivitywas70%andtheyieldwas43.4%.
Exampleeighteento(Ph2BuiP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversion
was55%andtheselectivity80%,yield42.2%.
Examplenineteento(Ph2BusecP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversion
was65%andtheselectivitywas60%andtheyieldwas37%.
Exampletwentyto(Ph2ButP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversionwas
65%andtheselectivity63%,yield33.5%.
Exampletwentyoneto(Ph2PenP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversion
was55%andtheselectivity80%,yield44.0%.
Exampletwentytwoto(Ph2HenP)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversion
ratewas35%andtheselectivitywas90%andtheyieldwas36.0%.
Exampletwentythreewith(PhO)3P)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereaction
conversionratewas40%andtheselectivitywas90%andtheyieldwas35%.
Exampletwentyfourto(Ph3A3)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversion
was65%andtheselectivitywas60%andtheyieldwas40%.
Exampletwentyfiveto(Ph3Sb)2PdCl2asthecatalyst,theotherwiththeseventhembodiment,thereactionconversion
ratewas40%andtheselectivity15%,yield8%.
Exampletwentysixto0.14mmolofNaIascocatalyst,withotherembodimentsofareactionconversionwas89.6%,the
selectivity67%,yield60.1%.
Exampletwentysevenwithtripropylamineastheneutralizingagent,theotherwithExampleI,thereactionconversionrate
was79%andtheselectivity50%,yield39%.
ExampletwentyeighttributylamineastheneutralizingagenttotheotherasinExampleI,thereactionconversionwas50%
andtheselectivity40%,yield20%.
Exampletwentynineinxyleneasasolventtoone,0.14mmolKIascocatalyst,withtheotherembodimentsone,the
reactionconversionratewas53.3%,theselectivitywas88.2%andtheyieldwas47%.
Examplethirtyanisoleassolvent,theotherinExample29.Thereactionconversionratewas75%andtheselectivity57%,
yield43%.
Examplethirtyoneindimethylformamideassolvent,theotherinExample29.Thereactionconversionratewas75%and
theselectivity48%,yield36%.
ThirtyreactiontemperatureofExample70,KIinanamount0.14mmol,andtherestwithoneembodiment,thereaction
conversionratewas60%andtheselectivity39%,yieldof23.4%.
Thirtythirdembodimentofthereactiontemperatureis140,therestinExampleXXXII,thereactionconversionwas90%
andtheselectivitywas32.9%,yield30%.
ExampleThirtypressurereaction1.0MPa,KIdosage0.14mmol,andtherestwithoneembodiment,thereactionconversion
ratewas80%andtheselectivity57%,yieldof45.6%.
Examplethirtyfivereactionpressurewas4.0MPa,andtherestwiththeembodimentthirtyfour,thereactionconversionwas
88%andtheselectivity68%,yield60%.
ExampleThirtysixreactiontimewas12hours,KIdosage0.14mmol,andtherestwithoneembodiment,thereactionyield
was13%.
Thirtysevenembodimentofreactiontimefor72hours,andtheremainingthirtysixwithanembodiment,thereactionyieldof
65%.
Thirtyeight(Ph3P)2PdCl2amountembodimentis0.443102mmol,KIisaddedinanamount0.14mmol,other
embodimentswithareactionconversionratewas45%andtheselectivity69%,yield31%.
Thirtyninepatients(Ph3P)amount2PdCl2implementationof4.69102mmol,thirtyeightothersimilarembodiments,the
reactionconversionwas90%,withaselectivityof67%,ayieldof60.3%.
ExampleFortyKIisaddedinanamount0.002mmol,28%yieldwiththeotherembodimentofareactionconversionwas
70%,theselectivitywas40%.
FortyoneembodimenttheamountofKIaddedto0.3mmol,theotherone,andthereactionconversionwas92%inExample,
theselectivitywas67.9%,ayieldof63%.

KUTIPAN PATEN
PatenyangDirujuk

Tanggalpengajuan

Tanggalpublikasi

Pemohon

Judul

CN1010930A

CN1104628A*

30Des1993

Judultidak
tersedia
5Jul1995

Oxosynthesisofdiethyl
malonate

*Dikutipolehpenguji

KLASIFIKASI
KlasifikasiInternasional

C07C67/36,C07C69/38

PERISTIWA HUKUM
Tanggal

Kode

Peristiwa

29Mar2006

C19

Cessationofpatentright(cessationofpatentrightduetononpaymentoftheannualfee)

Deskripsi

16Okt2002

C14

Granted

27Jun2001

C10

Requestofexaminationastosubstance

8Des1999

C06

Publication

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