SK1612000A3 - Process for the preparation of esters of cyanoacetic acid - Google Patents
Process for the preparation of esters of cyanoacetic acid Download PDFInfo
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- SK1612000A3 SK1612000A3 SK161-2000A SK1612000A SK1612000A3 SK 1612000 A3 SK1612000 A3 SK 1612000A3 SK 1612000 A SK1612000 A SK 1612000A SK 1612000 A3 SK1612000 A3 SK 1612000A3
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- Prior art keywords
- alkyl
- process according
- cyanoacetic acid
- sodium
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- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 14
- 150000002148 esters Chemical class 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 239000011630 iodine Substances 0.000 claims abstract description 3
- 239000012074 organic phase Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 3
- JAUCIKCNYHCSIR-UHFFFAOYSA-M sodium;2-cyanoacetate Chemical compound [Na+].[O-]C(=O)CC#N JAUCIKCNYHCSIR-UHFFFAOYSA-M 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 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 claims description 2
- 159000000011 group IA salts Chemical class 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 claims 1
- -1 arylalkyl halide Chemical class 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 abstract 3
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- ANGDWNBGPBMQHW-UHFFFAOYSA-N methyl cyanoacetate Chemical compound COC(=O)CC#N ANGDWNBGPBMQHW-UHFFFAOYSA-N 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 2
- RCUIWQWWDLZNMS-UHFFFAOYSA-N benzyl 2-cyanoacetate Chemical compound N#CCC(=O)OCC1=CC=CC=C1 RCUIWQWWDLZNMS-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000007333 cyanation reaction Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Spôsob výroby esterov kyseliny kyanoctovejA process for preparing cyanoacetic acid esters
Oblasť technikyTechnical field
Vynález sa týka spôsobu výroby esterov kyseliny kyanoctovej.The invention relates to a process for preparing cyanoacetic acid esters.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Zvyčajná syntéza esterov kyseliny kyanoctovej sa uskutoční kyanáciou sodnej soli kyseliny chlóroctovej vo vodnom roztoku, potom nasleduje esterifikácia so zodpovedajúcim alkoholom za kyslej katalýzy, pričom sa vytvorená voda azeotropicky oddestiluje. Podstatným nedostatkom tohto dvojstupňového spôsobu je to, že sa po kyanácii voda musí odstrániť, pretože nasledujúca esterifikácia je možná iba za značne bezvodých podmienok. Pri priemyselnej výrobe sa to zvyčajne uskutočňuje odparovaním vody. Pretože sodná soľ kyseliny kyanoctovej je ako medziprodukt navyše veľmi dobre rozpustná vo vode, požaduje sa taká metóda, ktorá by umožnila jej esterifikáciu vo vode ako rozpúšťadla.The usual synthesis of cyanoacetic acid esters is accomplished by cyanating the sodium chloroacetic acid salt in aqueous solution, followed by esterification with the corresponding alcohol under acid catalysis, whereby the water formed is azeotropically distilled off. An essential drawback of this two-step process is that water must be removed after cyanation, since subsequent esterification is only possible under considerably anhydrous conditions. In industrial production, this is usually done by evaporating water. Since, in addition, the cyanacetic acid sodium salt is very well soluble in water as an intermediate, a method is required which would allow its esterification in water as solvent.
Úlohou predloženého vynálezu bolo teda vyvinúť spôsob, pri ktorom je možné kyanáciou vzniknutý vodný roztok sodnej soli kyseliny kyanoctovej priamo esterifikovať.It is an object of the present invention to provide a process in which the aqueous cyanacetic acid sodium salt solution can be directly esterified directly by cyanation.
Podstata vynálezuSUMMARY OF THE INVENTION
Podstata spôsobu výroby esterov kyseliny kyanoctovej všeobecného vzorca I kde R znamená Cvio-alkyl, Cs-w-alkenyl alebo aryl-Ci^-alkyl, spočíva podľa vynálezu v tom, že sa na alkalickú soľ kyseliny kyanoctovej v dvojfázovom systéme voda/organická fáza za prítomnosti fázovotransférového katalyzátora pôsobí halogenidom všeobecného vzorca IIAccording to the invention, a process for the preparation of cyanoacetic esters of the general formula I wherein R represents C 1-10 -alkyl, C 3-8 -alkenyl or aryl-C 1-4 -alkyl is to convert the alkali metal salt of cyanacetic acid into a biphasic water / organic phase system. in the presence of a phase-transfer catalyst, it acts with a halide of formula II
R—X (II), kde R má hore uvedený význam a X znamená chlór, bróm alebo jód. Ako organická fáza tu môže slúžiť sám halogenid II alebo v zmesi s organickým rozpúšťadlom.R = X (II) wherein R is as defined above and X is chlorine, bromine or iodine. Here, the halide II itself or in admixture with an organic solvent may serve as the organic phase.
Pod pojmom Ci.w-alkyl sa tu rozumejú všetky lineárne alebo rozvetvené primárne, sekundárne alebo terciáme alkylové skupiny s 1 až 10 atómami uhlíka. Sú to najmä skupiny ako je metyl, etyl, propyí, izopropyl, butyl, izobutyl, sek-butyl, tercbutyl, pentyl, hexyl, heptyl, oktyl, nonyl alebo decyl.The term C1-4-alkyl as used herein refers to all linear or branched primary, secondary or tertiary alkyl groups having 1 to 10 carbon atoms. They are especially groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
Pod pojmom C3.io-alkenyl sa rozumejú zodpovedajúce skupiny s 3 až 10 atómami uhlíka a najmenej s jednou C=C-dvojitou väzbou, pričom dvojitá väzba je výhodne oddelená od voľnej valencie aspoň jedným nasýteným atómom uhlíka. Sem patria najmä skupiny ako je alyl, metalyl, but-2-enyl (krotyl), but-3-enyl atď.The term C 3 -alkenyl .io means corresponding groups of 3 to 10 carbon atoms and at least one C = C double bond, the double bond is preferably separated from the free valence of at least one saturated carbon atom. These include, in particular, groups such as allyl, metalyl, but-2-enyl (crotyl), but-3-enyl, etc.
Pod pojmom aryl-Ci.4-alkyl sa rozumejú najmä fenylsubstituované Ci.4-alkylovéskupiny, ako napríklad benzyl, fenetyl alebo 3-fenylpropyl, pričom fenylová skupina môže niesť jeden alebo viacej rovnakých alebo rozdielnych substituentov, ako napríklad C^-alkyl, C^-alkoxy alebo halogén.The term aryl-C 1-4 -alkyl means, in particular, phenyl-substituted C 1-4 -alkyl. 4- alkyl groups such as benzyl, phenethyl or 3-phenylpropyl, wherein the phenyl group may carry one or more of the same or different substituents such as C 1-4 -alkyl, C 1-4 -alkoxy or halogen.
Ako alkalická soľ kyseliny kyanoctovej sa výhodne používa kyanoctan sodný.As the alkaline salt of cyanoacetic acid, sodium cyanate is preferably used.
Kyanoctan sodný sa obzvlášť výhodne použije vo forme vodného roztoku, ktorý vzniká pri reakcii chlóroctanu sodného s kyanidom sodným.Sodium cyanoacetate is particularly preferably used in the form of an aqueous solution resulting from the reaction of sodium chloroacetate with sodium cyanide.
tT
X je výhodne chlór alebo bróm.X is preferably chlorine or bromine.
Ako fázovotransférový katalyzátor sa výhodne použije kvartérna amóniová soľ. Obzvlášť výhodné kvartérne amóniové soli sú tetra-n-C4-w-alkylamónium-, benzyltri-n-Ci-e-alkylamónium- alebo metyltri-n-C4-io-alkylamóniumhaiogenidy, najmä chloridy alebo bromidy.The quaternary ammonium salt is preferably used as the phase transfer catalyst. Particularly preferred quaternary ammonium salts are tetra-n-C 4-6 -alkylammonium, benzyltri-n-C 1-6 -alkylammonium or methyltri-n-C 4-10 -alkylammonium halides, especially chlorides or bromides.
Rovnako obzvlášť výhodné je použitie terc-butylmetyléteru alebo chlórbenzénu ako rozpúšťadla v organickej fáze.Also particularly preferred is the use of tert-butyl methyl ether or chlorobenzene as a solvent in the organic phase.
Nasledujúce príklady objasňujú uskutočnenie spôsobu podľa vynálezu bez toho, aby to znamenalo obmedzenie. Všetky reakcie sa uskutočňovali v autokláve s vnútorným objemom cca 250 ml. Stanovenie výťažku sa uskutočnilo plynovou chromatografiou pomocou interného štandardu.The following examples illustrate the process of the invention without limiting it. All reactions were performed in an autoclave with an internal volume of about 250 ml. Determination of yield was performed by gas chromatography using an internal standard.
* l* l
Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
Príklad 1Example 1
Metylester kyseliny kyanoctovejCyanoacetic acid methyl ester
K zmesi 1,70 g (0,02 mol) kyseliny kyanoctovej, 0,8 g (0,02 mol) hydroxidu sodného a 0,64 g (2,0mmol) tetrabutylamóniumbromidu v 15 ml terc-butylmetyléteru/vody 2:1 sa zaviedlo 10,0 g (9,9 ekviv., 0,20 mol) metylchloridu. Reakčná zmes sa v priebehu 30 min. zahriala na vnútornú teplotu 100 °C (110 °C teplota olejového kúpeľa), pričom sa tlak v autokláve zvýšil z 0,4 na 1 MPa. PoTo a mixture of 1.70 g (0.02 mol) of cyanoacetic acid, 0.8 g (0.02 mol) of sodium hydroxide and 0.64 g (2.0 mmol) of tetrabutylammonium bromide in 15 ml of tert-butyl methyl ether / water 2: 1 is added. introduced 10.0 g (9.9 equiv., 0.20 mol) of methyl chloride. The reaction mixture was stirred for 30 min. was heated to an internal temperature of 100 ° C (110 ° C oil bath temperature) while the autoclave pressure was increased from 0.4 to 10 bar. After
3,5 hod. pri 100 °C sa reakčná zmes ochladila a odtlakovala. pH vodnej fázy sa upravilo pomocou 3,10 g 1 M hydroxidu sodného s pH 2,9 na hodnotu pH 5,9, organická fáza sa oddelila a vodná fáza sa extrahovala s terc-butylmetyléterom (2x6 ml). Spojené organické fázy sa sušili so síranom sodným, pridal sa dimetylester kyseliny jantárovej (ako interný štandard) a analyzovalo sa plynovou chromatografiou. Získalo sa 1,36 g (68 %) metylesteru kyseliny kyanoctovej.3,5 hours at 100 ° C, the reaction mixture was cooled and depressurized. The aqueous phase was adjusted to pH 5.9 with 3.10 g of 1 M sodium hydroxide, pH 2.9, the organic phase was separated and the aqueous phase was extracted with tert-butyl methyl ether (2 x 6 ml). The combined organic phases were dried with sodium sulfate, dimethyl succinate (as an internal standard) was added and analyzed by gas chromatography. 1.36 g (68%) of methyl cyanoacetate were obtained.
I • Porovnávací príklad 1I • Comparative Example 1
Metylester kyseliny kyanoctovejCyanoacetic acid methyl ester
Postupovalo sa ako v príklade 1, avšak bez pridania tetrabutylamóniumbromidu. Výťažok metylesteru kyseliny kyanoctovej bol iba 13 %.The procedure was as in Example 1, but without the addition of tetrabutylammonium bromide. The yield of methyl cyanoacetate was only 13%.
Príklad 2Example 2
Etylester kyseliny kyanoctovejCyanacetic acid ethyl ester
Zmes 1,70 g (0,02 mol) kyseliny kyanoctovej, 0,8 g (0,02 mol) hydroxidu sodného, 10,90 g (0,10 mol, 5 ekviv.) etylbromidu a 0,64 g (2,0 mmol) tetrabutylamóniumbromidu v 15 ml chlórbenzénu/vody (2:1) sa v priebehu 30 min. zahriala na vnútornú teplotu 100 °C a 3,5 hod. sa miešala pri 100 °C (110 °C teplota olejového kúpeľa). Potom sa reakčná zmes ochladila, fázy sa oddelili a vodná fáza (pH = 6,85) sa extrahovala s terc-butylmetyléterom (2x5 ml). Spojené organické fázy sa sušili so síranom sodným, pridal sa dimetylester kyseliny jantárovej (ako interný štandard) a analyzovalo sa plynovou chromatografiou. Získalo sa 1,46 g (65 %) etylesteru kyseliny kyanoctovej.A mixture of 1.70 g (0.02 mol) of cyanoacetic acid, 0.8 g (0.02 mol) of sodium hydroxide, 10.90 g (0.10 mol, 5 equiv) of ethyl bromide and 0.64 g (2, 0 mmol) of tetrabutylammonium bromide in 15 ml of chlorobenzene / water (2: 1) over 30 min. was heated to an internal temperature of 100 ° C for 3.5 hours. was stirred at 100 ° C (110 ° C oil bath temperature). After the reaction mixture was cooled, the phases were separated and the aqueous phase (pH = 6.85) was extracted with tert-butyl methyl ether (2 x 5 ml). The combined organic phases were dried with sodium sulfate, dimethyl succinate (as an internal standard) was added and analyzed by gas chromatography. 1.46 g (65%) of ethyl cyanoacetate were obtained.
Príklad 3Example 3
Benzylester kyseliny kyanoctovejCyanoacetic acid benzyl ester
Zmes 1,70 g (0,02 mol) kyseliny kyanoctovej, 0,8 g (0,02 mol) hydroxidu sodného, 7,60 g (0,06 mol, 3 ekviv.) benzylchloridu a 0,64 g (2,0 mmol) tetrabutylamóniumbromidu v 15 ml terc-butylmetyléteru/vody (obj.:obj. = 2:1) sa 3 hod. miešala pri 100 °C (110 ’C teplota olejového kúpeľa). Potom sa pH vodnej fázy upravilo pomocou 3,15 g 1 M hydroxidu sodného s pH 0,2 na hodnotu pH 6,3, organická fáza sa oddelila a vodná fáza sa extrahovala s terc-butylmetyléterom (2x5ml). Spojené organické fázy sa sušili so síranom sodným a analyzovalo sa plynovou chromatografiou. Získalo sa 2,45 g (70 %) benzylesteru kyseliny kyanoctovej.A mixture of 1.70 g (0.02 mol) of cyanacetic acid, 0.8 g (0.02 mol) of sodium hydroxide, 7.60 g (0.06 mol, 3 equiv) of benzyl chloride and 0.64 g (2, Tetrabutylammonium bromide in 15 ml of tert-butyl methyl ether / water (v / v = 2: 1) for 3 hours. stirred at 100 ° C (110 ° C oil bath temperature). Then the pH of the aqueous phase was adjusted to pH 6.3 with 3.15 g of 1 M sodium hydroxide, pH 0.2, the organic phase was separated and the aqueous phase was extracted with tert-butyl methyl ether (2 x 5 ml). The combined organic phases were dried with sodium sulfate and analyzed by gas chromatography. 2.45 g (70%) of benzyl cyanoacetate were obtained.
Claims (7)
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| Application Number | Priority Date | Filing Date | Title |
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| EP99102286 | 1999-02-09 |
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| SK1612000A3 true SK1612000A3 (en) | 2000-08-14 |
| SK284992B6 SK284992B6 (en) | 2006-04-06 |
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| SK161-2000A SK284992B6 (en) | 1999-02-09 | 2000-02-03 | Process for the preparation of cyanoacetic esters |
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| EP (1) | EP1028105B1 (en) |
| JP (1) | JP2000229930A (en) |
| KR (1) | KR100606626B1 (en) |
| CN (1) | CN1137092C (en) |
| AT (1) | ATE264836T1 (en) |
| CA (1) | CA2297636C (en) |
| CZ (1) | CZ300354B6 (en) |
| DE (1) | DE50006109D1 (en) |
| ES (1) | ES2220265T3 (en) |
| HK (1) | HK1030205A1 (en) |
| HU (1) | HUP0000559A3 (en) |
| IL (1) | IL134110A (en) |
| NO (1) | NO325421B1 (en) |
| PL (1) | PL201839B1 (en) |
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| WO2011075401A1 (en) * | 2009-12-14 | 2011-06-23 | The Lubrizol Corporation | Lubricating composition containing a nitrile compound |
| US9976103B2 (en) * | 2009-12-14 | 2018-05-22 | The Lubrizol Corporation | Lubricating composition containing an antiwear agent |
| TW201238940A (en) * | 2011-03-23 | 2012-10-01 | Toagosei Co Ltd | Process for producing cyanoacetic acid esters |
| CN105732374B (en) * | 2016-01-30 | 2018-03-30 | 张家界久瑞生物科技有限公司 | A kind of method of 3,4,5-tri-methoxybenzoate of one-step synthesis method |
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| US4174347A (en) * | 1978-06-19 | 1979-11-13 | Shell Internationale Research Maatschappij B.V. | Preparation of esters |
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| Publication number | Publication date |
|---|---|
| DE50006109D1 (en) | 2004-05-27 |
| EP1028105A1 (en) | 2000-08-16 |
| CN1137092C (en) | 2004-02-04 |
| HUP0000559A2 (en) | 2001-01-29 |
| PL338284A1 (en) | 2000-08-14 |
| EP1028105B1 (en) | 2004-04-21 |
| ES2220265T3 (en) | 2004-12-16 |
| IL134110A0 (en) | 2001-04-30 |
| JP2000229930A (en) | 2000-08-22 |
| SK284992B6 (en) | 2006-04-06 |
| PT1028105E (en) | 2004-09-30 |
| NO325421B1 (en) | 2008-04-21 |
| CN1266845A (en) | 2000-09-20 |
| CZ2000452A3 (en) | 2000-09-13 |
| NO20000625L (en) | 2000-08-10 |
| HU0000559D0 (en) | 2000-04-28 |
| HK1030205A1 (en) | 2001-04-27 |
| HUP0000559A3 (en) | 2003-02-28 |
| KR100606626B1 (en) | 2006-07-28 |
| PL201839B1 (en) | 2009-05-29 |
| CZ300354B6 (en) | 2009-04-29 |
| CA2297636A1 (en) | 2000-08-09 |
| NO20000625D0 (en) | 2000-02-08 |
| ATE264836T1 (en) | 2004-05-15 |
| CA2297636C (en) | 2009-04-28 |
| IL134110A (en) | 2004-12-15 |
| KR20000057793A (en) | 2000-09-25 |
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