CS207500B1 - method of making the derivates of the malonic acid - Google Patents
method of making the derivates of the malonic acid Download PDFInfo
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- CS207500B1 CS207500B1 CS96678A CS96678A CS207500B1 CS 207500 B1 CS207500 B1 CS 207500B1 CS 96678 A CS96678 A CS 96678A CS 96678 A CS96678 A CS 96678A CS 207500 B1 CS207500 B1 CS 207500B1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 15
- 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 3
- 150000002690 malonic acid derivatives Chemical class 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000002941 palladium compounds Chemical class 0.000 claims description 8
- -1 alkali metal hydrogencarbonate Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 101000867232 Escherichia coli Heat-stable enterotoxin II Proteins 0.000 claims 1
- 101150003085 Pdcl gene Proteins 0.000 claims 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims 1
- 150000001983 dialkylethers Chemical class 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 229940125717 barbiturate Drugs 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 abstract 1
- 235000019156 vitamin B Nutrition 0.000 abstract 1
- 239000011720 vitamin B Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- FGDCQTFHGBAVJX-UHFFFAOYSA-N dimethyl 2-phenylpropanedioate Chemical compound COC(=O)C(C(=O)OC)C1=CC=CC=C1 FGDCQTFHGBAVJX-UHFFFAOYSA-N 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- 239000003326 hypnotic agent Substances 0.000 description 1
- 230000000147 hypnotic effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YSWYYGKGAYSAOJ-UHFFFAOYSA-N phosphane Chemical compound P.P YSWYYGKGAYSAOJ-UHFFFAOYSA-N 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Vynález se týká kyseliny malonové způsobu výroby derivátů obecného vzorceThe present invention relates to malonic acid for the preparation of derivatives of the general formula
0'0 '
IIII
R1 C—OR3 \ / C , / \R1 C — OR3 \ / C, / \
R2 z ve kterémR2 in which
Z značí skupinu —COOR, kde R značí alkyl s 1 až 2 atomy uhlíku, amidovou nebo nítrilovoiu skup inu,Z is -COOR, wherein R is C 1 -C 2 alkyl, amide or nitrile,
R1 sa R2 jsou stejné nebo rozdílné a značí vodík nebo feinyl,R1 and R2 are the same or different and denote hydrogen or phenynyl,
R3 značí alkyl s 1 až 2 atomy uhlíku.R 3 denotes alkyl having 1 to 2 carbon atoms.
Je · známo, že se estery kyseliny malonové vyrábějí z odpovídajících álfathalogenesterů naflhrazeníim’ halogenu nitrilovou skupinou a následnou alkoholýzon nitrilové skupiny. Tento postup vyžaduje psnužití vysoce toxických reakčních složek, jako· je kyanid draselný, a obtížné čištění odpadních surovin.It is known that malonic acid esters are produced from the corresponding alpha-phthalogenic esters by substituting the halogen with a nitrile group and the subsequent alcoholysis of the nitrile group. This process requires the use of highly toxic reagents such as potassium cyanide and difficult to purify waste materials.
Současně je známo, že uvedené produkty jsou využívány při organických syntézách, jako je syntéza baribiturátů, hypnotik a vitaminů Bi a B6.At the same time, it is known that these products are used in organic syntheses such as the synthesis of baribiturates, hypnotics and vitamins Bi and B6.
Nyní bylo· zjištěno· 'ta tvoří podstatu před kládaného vynálezu, že uvedené sloučeniny mohou· být vyrobeny z alfa-halogenesteru, amidu, niitrílu nebes dihalogemmethanu, respektive ze sloučenin obecného vzorceIt has now been found that it is the essence of the present invention that said compounds can be made from alpha-haloester, amide, niitrile or dihalomethanes, respectively from compounds of formula
RiRi
IAND
X—G—Z ,X — G — Z,
IAND
R2 ve kterémR2 in which
Z, Ri a Rs mají výše uvedený význam aZ, R 1 and R 5 are as defined above and
X značí halogen, způsobem dále uvedeným.X is halogen as described below.
Vynález se tedy Sýká způsobu· výroby sloučenin odpovídajících derivátům kyseliny malomové obecného vzorceThe invention thus provides a process for the preparation of compounds corresponding to malomic acid derivatives of the general formula
OO
R C—OR3 \ /R C — OR 3 \ /
C , / \C, / \
Rž· Z ve kterémRz · Z in which
Z značí skupinu —COOR, kde · R značí al-Z stands for —COOR, where · R stands for al-
0 7. 5 0 0 kyl s 1 až 2 atomy uhlíku, amidovou nebo nitrilovou skupinu,0 7 5 0 0 C 1-2 alkyl, amide or nitrile group
Ri a Rž jsou stejné nebo rozdílné a značí vodík nebo fenyl,R 1 and R 2 are the same or different and denote hydrogen or phenyl,
R3 značí alkyl s 1 až 2 atomy uhlíku, reakcí sloučeniny obecného vzorceR 3 denotes alkyl of 1 to 2 carbon atoms, by reaction of a compound of formula
RiRi
IAND
X—c—z ,X — c — z,
IAND
R2 ve kterémR2 in which
Z, Ri a R'2 mají výše uvedený význam a X značí halogen, s alifatickým alkoholem obecného vzorceZ, R 1 and R '2 are as defined above, and X is halogen, with an aliphatic alcohol of formula
R3 OH , ve kterémR 3 OH, wherein
R3 má výše uvedený význam, a s kysličníkem uhelnatým v přítomnosti báze ze skupiny anorganické inebo organické báze a katalyzátoru, tvořeného komplexní sloučeninou ipaládia nebo elementárním paládiem, přičemž se reakce provádí při teplotách v rozmezí od 80 do 150 °C a za tlaku v rozmezí od 0,1 do 20 MPa a s výhodou od 0,1 do 7 MPa.R 3 is as defined above, and with carbon monoxide in the presence of a base selected from an inorganic or organic base and a catalyst consisting of a complex of palladium or elemental palladium, the reaction being carried out at temperatures ranging from 80 to 150 ° C and pressures ranging from 0 1 to 20 MPa and preferably from 0.1 to 7 MPa.
Ve formě báze je možno použít hydrogenuhličitany a uhličitany alkalických kovů a kovů alkalických zemin nebo kysličníků kovů alkalických zemin, popřípadě terciární alifatické aminy a pyridiny.Alkali and alkaline earth metal or alkaline earth metal hydrogencarbonates and carbonates or tertiary aliphatic amines and pyridines may be used as the base.
Jako sloučeniny paládia přicházejí zejména v úvahu sloučeniny obecného vzorceParticularly suitable palladium compounds are compounds of the general formula
PdIz(P РЬз)2, kde P značí fosfin a Ph fenyl.PdIz (P РЬз) 2, where P is phosphine and Ph is phenyl.
Dále je možno použít sloučenin paládia obecných vzorcůFurther, palladium compounds of the general formulas may be used
PdC12(P Ph3)2,PdCl2 (P Ph3) 2,
Pd(OCO СНз)(СООСНз)(Р Ph3)2,Pd (OCO СНз) (СООСНз) (Р Ph3) 2,
Pd(CO)(P РЬз)з aPd (CO) (P РЬз) з a
Pd(COOCH3)2(P РНз)2, ve kterých P a Ph mají výše uvedený význam.Pd (COOCH 3) 2 (P R N 2) 2, wherein P and Ph are as defined above.
Reakce podle vynálezu se provádí výhodně v přítomnosti aktivátoru ze skupiny tvořené halogeinidy a karboxyláty 'alkalických kovů nebo kovů alkalických zemin.The reaction according to the invention is preferably carried out in the presence of an activator selected from the group consisting of alkali metal or alkaline earth metal halides and carboxylates.
Výhodně se použije při reakci organické rozpuštědlo, například polární aprotické rozpouštědlo ze skupiny tvořené tetrahydrofuranem, dioxanean, tetrahydropyraneim, monoa diailkylethery ethylenglykolu a holmologů glykolu a oxyethylenoxyproÍpylenglykolu, hexamethylfosfamidem a tetramethylensulfonem.Preferably, an organic solvent is used in the reaction, for example, a polar aprotic solvent selected from the group consisting of tetrahydrofuran, dioxanean, tetrahydropyraneim, mono-dialethyl ethers of ethylene glycol and glycol and oxyethyleneoxypropyl ethylene glycol, hexamethylphosphamide and tetramethylene sulfone.
Vynález bude dále dokreslen formou příkladů provedení, které jeho podstatu nijak neomezují.The invention will now be illustrated by way of non-limiting examples.
Příklad 1Example 1
Do autoklávu z nerezavějící oceli bylo vsazeno 24,6 g methylchloracetátu, 15,8 g metanolu, 19,1 g hydrogenuhličitanu sodného, 2,2 g PdÍ2 (fosfih-fenyl3)2 a 80 ml hexarnethylfcfcfamidu. Do autoklávu, který byl uzavřen a promyt dusíkem, bylo přiváděno množství odpovídající 5,0 MPa kysličníku uhelnatého a reakční prostor byl po· dobu 4 hodin zahříván na teplotu 100 °C.The stainless steel autoclave was charged with 24.6 g of methyl chloroacetate, 15.8 g of methanol, 19.1 g of sodium bicarbonate, 2.2 g of Pd2 (phosphihphenyl3) 2, and 80 ml of hexamethylphosphamide. The autoclave, which was sealed and purged with nitrogen, was charged with 5 MPa of carbon monoxide and the reaction space was heated at 100 ° C for 4 hours.
Reakční směs byla analyzována chromatografickými postupy (GLC) a zjištěna 100% konverze methylchloracetátu a 79% výtěžek dimethy lmaton átu.The reaction mixture was analyzed by chromatography (GLC) and found 100% conversion of methyl chloroacetate and 79% yield of dimethylmatonate.
Příklad 2Example 2
Do autoklávu bylo vsazeno 39,6 g methylenchloridu, 7,9 g methanolu, 25,2 g triethyl•amiinu, 1,7 g PdC12.(foisfin-fenyl3)2 a 1,6 g jodidu draselného. Do autoklávu byl přiváděn kysličník uhelnatý v množství odpovídajícím 5,0 MPa a reakční prostor byl zahříván po dobu 8 hodin na teplotu 100 °C. Analýza reakční směsi prokázala konverzi methanolu 25 % a selektivitu к dimethylmalonátu 87 %.The autoclave was charged with 39.6 g of methylene chloride, 7.9 g of methanol, 25.2 g of triethylamine, 1.7 g of PdCl2 (foisfin-phenyl3) 2, and 1.6 g of potassium iodide. Carbon monoxide equivalent to 50 bar was fed into the autoclave and the reaction space was heated at 100 ° C for 8 hours. Analysis of the reaction mixture showed a methanol conversion of 25% and a selectivity to dimethyl malonate of 87%.
P ř í к 1 a d 3Example 1 a d 3
Do autoklávu bylo vpraveno 8,0 g beinaalchloridu, 3,9 g methanolu, 10,5 g 2,6-lutiidinu, 1,1 g Pd(OCOCH3) (COOCH3)fosfin-feпу1з)г a 40 ml hexamethylfosfamidu. Do autoklávu byl přiváděn kysličník uhelnatý pod tlakem 5,0 MPa a reakční prostor byl zahříván po dobu 4 hodin na teplotu 100 °C. Analýza reakční směsi prokázala vytvoření dimethylesteru kyseliny fenylmalonové při výtěžku 55 %.8.0 g of beinaal chloride, 3.9 g of methanol, 10.5 g of 2,6-lutiidine, 1.1 g of Pd (OCOCH3) (COOCH3) phosphine phosphine) and 40 ml of hexamethylphosphamide were introduced into the autoclave. Carbon monoxide was introduced into the autoclave under a pressure of 50 bar and the reaction space was heated at 100 ° C for 4 hours. Analysis of the reaction mixture showed formation of phenylmalonic acid dimethyl ester in a yield of 55%.
Příklad 4Example 4
Do autoklávu bylo vsazeno 37,5 g chloracetonitrilu, 23 g ethanolu, 10 g hořčíku, 1,8 gramů Pd(CO)(fosfin-feny 1з)2 a 80 ml „glymu“. Autoikláv byl naplněn kysličníkem uhelnatým pod tlakem 5,0 MPa a reakční prostor byl zahříván po dobu 4 hodin na teplotu 80 aC.The autoclave was charged with 37.5 g of chloroacetonitrile, 23 g of ethanol, 10 g of magnesium, 1.8 g of Pd (CO) (phosphine-phenylene) 2 and 80 ml of " glyme ". The autoclave was charged with carbon monoxide at a pressure of 50 bar and the reaction space was heated at 80 and C for 4 hours.
Analýza; reakční směsi dokázala konverzi 100% selektivitu vzhledem к ethylkyanoacetátu 6'8 %.Analysis; of the reaction mixture showed a conversion of 100% selectivity to ethyl cyanoacetate of 6-8%.
Příklad 5Example 5
Do autoklávu bylo vsazeno· 65 g N,N‘-dletliylchloracutamidu, 25 g ethanoiu, 25 g trieíthylamiinu, 1,5 g Pd(COOCH3)2[fosfm-feпу1з]2 a 1'50 ml N,N‘-dlmethylíormůmiidu. Autokláv byl plněn kysličníkem uhelnatým při přetlaku 5,0 MPa a reakční prostor byl zahříván po dobu 4 hodin na teplotu 100 °C.The autoclave was charged with 65 g of N, Nut-dletliylchloracutamide, 25 g of ethanol, 25 g of triethylamine, 1.5 g of Pd (COOCH3) 2 [phosphine-phosphol] 2 and 1'50 ml of N, N-dimethylaminamide. The autoclave was charged with carbon monoxide at a pressure of 50 bar and the reaction space was heated at 100 ° C for 4 hours.
Analýza reakční směsi prokázala 92% konverzi a 81% selektivitu vzhledem к Ν,Ν’-diethylmalonamidmonoethylesteru.Analysis of the reaction mixture showed 92% conversion and 81% selectivity with respect to Ν, Ν-diethylmalonamide monoethyl ester.
Claims (11)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2064177A IT1075123B (en) | 1977-02-24 | 1977-02-24 | PROCESS FOR THE PREPARATION OF MALONIC ACID DERIVATIVES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS207500B1 true CS207500B1 (en) | 1981-07-31 |
Family
ID=11169929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS96678A CS207500B1 (en) | 1977-02-24 | 1978-02-15 | method of making the derivates of the malonic acid |
Country Status (7)
| Country | Link |
|---|---|
| CH (1) | CH636336A5 (en) |
| CS (1) | CS207500B1 (en) |
| DD (1) | DD134083A5 (en) |
| DE (1) | DE2807625C2 (en) |
| FR (1) | FR2381738A1 (en) |
| GB (1) | GB1574113A (en) |
| IT (1) | IT1075123B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2907873A1 (en) * | 1979-03-01 | 1980-09-11 | Dynamit Nobel Ag | METHOD FOR PRODUCING N-PROPYLCYANIC ACETIC ESTERS |
| CN110950757B (en) * | 2019-12-26 | 2021-11-23 | 中国科学院兰州化学物理研究所 | Production method and system of malonic diester |
| CN117658812A (en) * | 2022-08-26 | 2024-03-08 | 鞍山七彩化学股份有限公司 | A kind of preparation method of malonate ester |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2359963C2 (en) * | 1973-12-01 | 1982-01-28 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of dialkyl malonates |
| DE2403483A1 (en) * | 1974-01-25 | 1975-08-07 | Dynamit Nobel Ag | Alkyl cyanoacetates prodn from chloroacetonitrile - by heating with carbon monoxide alcohol and metal carbonyl catalyst under pressure |
| DE2509017C2 (en) * | 1975-03-01 | 1983-03-03 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of phenylmalonic acid dialkyl esters |
-
1977
- 1977-02-24 IT IT2064177A patent/IT1075123B/en active
-
1978
- 1978-02-06 GB GB473978A patent/GB1574113A/en not_active Expired
- 1978-02-08 CH CH141378A patent/CH636336A5/en not_active IP Right Cessation
- 1978-02-15 CS CS96678A patent/CS207500B1/en unknown
- 1978-02-22 DD DD20379778A patent/DD134083A5/en unknown
- 1978-02-22 DE DE19782807625 patent/DE2807625C2/en not_active Expired
- 1978-02-23 FR FR7805250A patent/FR2381738A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2381738B1 (en) | 1981-07-31 |
| DD134083A5 (en) | 1979-02-07 |
| DE2807625A1 (en) | 1978-08-31 |
| IT1075123B (en) | 1985-04-22 |
| GB1574113A (en) | 1980-09-03 |
| CH636336A5 (en) | 1983-05-31 |
| FR2381738A1 (en) | 1978-09-22 |
| DE2807625C2 (en) | 1982-07-01 |
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