CS256084B1

CS256084B1 - Process for producing formic esters

Info

Publication number: CS256084B1
Application number: CS865554A
Authority: CS
Inventors: Julius Kalamar; Dusan Mravec; Milina Cihova; Jan Vojtko; Jan Ilavsky
Original assignee: Julius Kalamar; Dusan Mravec; Milina Cihova; Jan Vojtko; Jan Ilavsky
Priority date: 1986-07-22
Filing date: 1986-07-22
Publication date: 1988-04-15
Also published as: CS555486A1

Abstract

Riešenie sa týká sposobu výroby esterov kyseliny mravčej s alifatickými alkoholmi s počtom uhlíkov 1 až 10, alkylaromatickými alkoholmi, kde alkyl má počet uhlíkov 1 až 3, cyklopentanolom alebo cyklohexanolom. Podstatou riešenia je, že esterifikácia sa uskutočňuje za přítomnosti chloridu vápenatého alebo chloridu vápenatého s přísadou kyseliny chlorovodíkovej pri teplote 35 až 110 °C. Estery kyseliny mravčej sa používajú ako chuťové a vonné látky v potravinárskom a kozmetickom priemysle a ako rozpúšťadlá v lakárskom priemysle.The solution relates to a method for producing esters of formic acid with aliphatic alcohols with a carbon number of 1 to 10, alkylaromatic alcohols, where alkyl has a carbon number of 1 to 3, cyclopentanol or cyclohexanol. The essence of the solution is that the esterification is carried out in the presence of calcium chloride or calcium chloride with the addition of hydrochloric acid at a temperature of 35 to 110 ° C. Formic acid esters are used as flavorings and fragrances in the food and cosmetic industries and as solvents in the paint industry.

Description

Vynález sa týká sposobu přípravy esterov kyseliny mravčej.The present invention relates to a process for preparing formic acid esters.

Estery nižších karboxylových kyselin sa používajú ako rozpúšťadlá a niektoré v potravinárskom priemysle ako chuťové a vonné látky ako aj v kozmetlke ako vonné látky. Tieto estery sa obecne pripravujú kysle katalyzovanou esterifikáciou karboxylových kyselin příslušnými alkoholmi, pričom sa pracuje bez přídavku katalyzátora a reakciu katalyzuje kyselina mravčia [Werner W.: Chem. Res. Synop. (1980) (6). 196 (CA: 93, 220 363 f)].Lower carboxylic acid esters are used as solvents and some in the food industry as flavorings as well as in cosmetics as fragrances. These esters are generally prepared by acid-catalyzed esterification of the carboxylic acids with the appropriate alcohols, working without the addition of a catalyst and catalizing the reaction [Werner W .: Chem. Res. SYNOP. (1980) 6. 196 (CA: 93,220,363 f)].

Ako katalyzátory sa používají! minerálně kyseliny, z ktorých obecne kyselina sírová, ďalej chlorovodíková ako je uvedené v Vogel A. i.: J. Chem. Soc. 1948, 1 809, 1 811 a chlórsulfónová [Erdos J., Salazar Μ. E.: Sciencia (Mex.) 12, 228—230 (1953) (CA: 48, 6 988 a).The catalysts used are! mineral acids, generally sulfuric acid, and hydrochloric acid as described in Vogel A. i .: J. Chem. Soc. 1948, 1 809, 1 811 and chlorosulfonic [Erdos J., Salazar zar. E .: Sciencia (MEX) 12, 228-230 (1953) (CA: 48, 6 988 a).

Benzylformiát sa tiež připravuje vařením kyseliny mravčej s nadbytkom benzylalkoholu za katalýzy oxidu titaničitého T1O2 pri 150 stupňoch Celzia, alebo oxidu toričitého ThO₂pri 200 až 220 °C [Sabatier P., Mailhe A.: Compte Rendu 152, 1045 (1911)]. Benzylformiát je možné pripravií reakciou benzylátu sodného v benzylalkohole s oxidom uholnatým za tlaku 50 at pri 60 až 65 °C [NSR pat. 588 763 (1932)], alebo vařením benzylalkoholu s kyselinou mravčou za odstraňovania vznikajúcej vody azeotropickou destiláciou s izopropylesterom kyseliny mravčej (NSR pat. 721 300 (1939)].Benzyl formate are also prepared by boiling an excess of formic acid with benzyl alcohol under the catalysis of the titanium dioxide T1O2 at 150 degrees C, and thorium oxide ThO ₂ at 200-220 DEG C. [Sabatier, P., A .: Mailhe Compte Rendu 152, 1045 (1911)]. Benzyl formate can be prepared by reacting sodium benzylate in benzyl alcohol with carbon monoxide at 50 at 60 to 65 ° C [NSR Pat. 588 763 (1932)], or by boiling benzyl alcohol with formic acid to remove the water formed by azeotropic distillation with isopropyl ester of isopropyl ester (German Pat. No. 721,300 (1939)).

Cyklohexylforinitá a cyklopentylforniiát sa připravuje reakciou příslušného alkoholu s kyselinou mravčou za katalýzy kyseliny chlorovodíkové) (Vogel A. I.: J. Chem. Soc. 1948, 1 809, 1 811.Cyclohexylforinite and cyclopentylforniiate are prepared by reacting the corresponding alcohol with formic acid to catalyze hydrochloric acid (Vogel, A.I .: J. Chem. Soc. 1948, 1 809, 1 811).

Ako sa zistilo, kyselina sírová sa u niektorých esterov ako napr. u benzylformiátu, tiež bouzylacetátu a 3-fenylpropylformiátu ukázala ako nevhodná z toho důvodu, že pri izo'ácii esteru z reakčnej zmesi, kedy sa kyselina sírová zakoncentruje, působí dehydratacím a v konečnom důsledku to vedie k zoživičnateniu reakčnej zmesi a tým k úplnému znehodnoteniu produktu. V tomto případe sa neukázali vhodné ani katexy obsahujúce — SO3H skupinu. Pre přípravu esterov kyseliny mravčej, ktorá je velmi reaktivita a jej estery sa najobtiažnejšie pripravujú, sa preto navrhuje postup, v ktorom sa používá ako katalyzátor a súčasne dehydratačné činidlo chlorid vápenatý, resp. v kombinácii s kyselinou chlorovodíkovou, ktorá urýchluje esterifikačnú reakciu. V tomto případe sa esterifikácia uskutočňuje bez přídavku vynášadla reakciou vznikajúcej vody.As has been found, sulfuric acid is found in some esters such as e.g. for benzyl formate, also bouzylacetate and 3-phenylpropyl formate, proved to be unsuitable because isolating the ester from the reaction mixture, when the sulfuric acid is concentrated, causes dehydration and ultimately results in the reaction mixture becoming leaner and thus completely destroying the product. In this case, cation exchangers containing a - SO3H group have not been shown to be suitable either. For the preparation of formic acid esters, which are very reactive and their esters are the most difficult to prepare, it is therefore proposed a process in which both calcium chloride and the dehydrating agent are used. in combination with hydrochloric acid, which accelerates the esterification reaction. In this case, the esterification is carried out without the addition of a propellant by the reaction of the resulting water.

Podlá vynálezu sa estery kyseliny mravčej s alifatickými alkoholmi s počtom uhlíkov 1 až 10, alkylaromatickými alkoholmi, kde alkyl má počet uhlíkov 1 až 3, cyklopentanolom alebo* cyklohexanolom, vyrábajú esterifikáciou, ktorej podstatou je, že sa uskutočňuje za přítomnosti chloridu vápenatého alebo chloridu vápenatého s přísadou kyseliny chlorovodíkovej tak, že sa na 1 mol alkoholu použije 1 až 1,5 molu kyseliny mravčej, a na 1 mól alkoholu sa použije 0,1 až 0,2 molu samotného chloridu vápenatého, alebo 0,1 až 0,2 molu chloridu vápenatého s prídavkom 0,005 až 0,05 molu kyseliny chlórovodíkovej a esterifikácia sa uskutočňuje pri teplote 35 až 110 °C. Připravený ester sa izoluje z reakčnej zmesi destiláciou po oddělení vrstvy vodného roztoku chloridu vápenatého a přefiltrovaní, ktoré však nie je nutné. Výtažky esterov po ich izolácii a predestilovaní sa pohybujú v rozmedzí 76 až 92 % pri čistotě esterov 98 až 99 %.According to the invention, esters of formic acid with aliphatic alcohols having a carbon number of 1 to 10, alkylaromatic alcohols in which the alkyl number has a carbon number of 1 to 3, cyclopentanol or cyclohexanol are produced by esterification which is carried out in the presence of calcium chloride or calcium chloride. with the addition of hydrochloric acid, using 1 to 1,5 mol of formic acid per mol of alcohol and 0,1 to 0,2 mol of calcium chloride alone, or 0,1 to 0,2 mol per mol of alcohol of calcium chloride with an addition of 0.005 to 0.05 moles of hydrochloric acid and the esterification is carried out at a temperature of 35 to 110 ° C. The prepared ester is isolated from the reaction mixture by distillation after separation of the aqueous calcium chloride solution and filtration, but this is not necessary. The yields of the esters after isolation and distillation are in the range of 76-92% with an ester purity of 98-99%.

Výhodou postupu podfa vynálezu je možnost přípravy esterov kyseliny mravčej vo vysokých výfažkocli a čistotě, vylúčením kyseliny sírovej z procesu a tým k odstráneniu problému zoživičnatenia reakčnej zmesi v případe alkylaromatických esterov, najma u benzylformiátu.An advantage of the process according to the invention is that it is possible to prepare formic acid esters in high yields and purity, by eliminating sulfuric acid from the process and thereby eliminating the problem of making the reaction mixture liable in the case of alkylaromatic esters, especially benzyl formate.

Ďalšou výhodou podfa postupu tohoto vynálezu je vylúčenie potřeby přítomnosti vynášadia vody počas esterifikácie, pretože vznikajúca voda sa viaže na chlorid vápenatý vo formě roztoku, ktorý sa může v priebehu, alebo· po reakcií odstrániť. Nie je preto potřebné vydestilovat organické vynášad lo vody, čo prináša značné energetické úspory a znižuje nebezpečie vzniku požiaru.A further advantage of the process of the present invention is to avoid the need for the presence of a water dispenser during esterification, since the water formed binds to calcium chloride in the form of a solution which can be removed during or after the reactions. There is therefore no need to distill out organic water carriers, which brings considerable energy savings and reduces the risk of fire.

Vysoká konvtrzía východiskového alkoholu sa dosiahne už pri mól. pomere alkohol/ /kyselina mravčia = 1:1, čo pri iných postupoch prakticky nie je možné.A high conversion of the starting alcohol is already at the pier. alcohol / formic acid ratio = 1: 1, which is virtually impossible in other processes.

V ďalšom je vynález opísaný v příkladech prevedenia, na ktoré sa však neobmedzuje.In the following, the invention is described by way of non-limiting examples.

Příklad 1Example 1

Do esterifikačného reaktora (trojhrdlá banka o obsahu 500 cín³) opatřeného miešadlom, teplomerom a spatným chladičom sa nadávkovalo 32,4 g (0,704 molu) kyseliny mrače), 54,1 g (0,5 mólu) benzylalkoholu a 10 g (0,09 mólu) chloridu vápenatého. Reakčná zmes sa zahriala na 100 °C a táto teplota sa udržiavala za miešania počas 15 minút. Spočiatku pevný chlorid vápenatý rýchlo priberal reakciou vznikajúcu vodu a vytváral súvislú spodnú vrstvu. Z reakčnej zmesi sa po ochladení oddělila spodná vrstva chloridu vápenatého a po přefiltrovaní sa organická fáza predestilovala tak, že sa najskůr oddestilovala nezreagovaná kyselina mravčia a potom benzylformiát. Získalo sa 60 g esteru o čistotě 93 %, t. j. výťažok bol 82 % teorie.To the esterification reactor (three-necked 500 tin ³ flask) equipped with a stirrer, thermometer, and a reflux condenser was charged 32.4 g (0.704 mol) of glacial acid), 54.1 g (0.5 mol) of benzyl alcohol and 10 g (0.1 g). 09 mol) of calcium chloride. The reaction mixture was heated to 100 ° C and this temperature was maintained with stirring for 15 minutes. Initially, solid calcium chloride rapidly gained water by the reaction and formed a continuous bottom layer. The lower calcium chloride layer was separated from the reaction mixture after cooling, and after filtration, the organic phase was distilled by first distilling off unreacted formic acid and then benzyl formate. 60 g of an ester of 93% purity were obtained, i.e. the yield was 82% of theory.

Příklad 2Example 2

Do zariadenia uvedeného v příklade 1 sa nadávkovalo 23 g (0,5 mólu) kyseliny mravčej, 54,1 g (0,5 móluj benzylalkoholu a 4g chloridu vápenatého. Reakčná zmes sa udržiavala za miešania na teplote 95 °C počas 15 minút. Potom po zastavení miešadla sa spodná fáza odpustila, přidalo sa 2 g chloridu vápenatého, v reakcii sa pokračovalo za rovnakých podmienok 15 minút a rovnako sa oddělila spodná fáza. Ďalej sa přidalo23 g (0.5 mol) of formic acid, 54.1 g (0.5 mol of benzyl alcohol and 4 g of calcium chloride) were metered into the apparatus of Example 1. The reaction mixture was kept under stirring at 95 ° C for 15 minutes. after the stirrer was stopped, the bottom phase was drained, 2 g of calcium chloride was added, the reaction was continued under the same conditions for 15 minutes, and the bottom phase was separated as well.

3,7 g kyseliny mravčej a dalšie 2 g chloridu vápenatéhoi a v reakcii sa pokračovalo dalších 15 minút. Po zliatí a přefiltrovaní organickej fázy sa táto destilovala za zníženého tlaku (2,7 kPa), pričom sa ako 1. frakcia oddělila nezreagovaná kyselina mravčia a ako 2, frakcia destiloval ester, ktorý sa získal v množstve 60,2 g o čistotě 98 %, čo představuje výťažok 86,6 % teorie.3.7 g formic acid and a further 2 g calcium chloride were added and the reaction continued for a further 15 minutes. After decanting and filtering the organic phase, it was distilled under reduced pressure (2.7 kPa), unreacted formic acid was separated as the first fraction and, as the 2 fraction, the ester obtained in 60.2 g and 98% purity was distilled, which represents a yield of 86.6% of theory.

P r í k 1 a d 3 'Example 1 '

Do zariadenie ako v příklade 1 sa nadávkovalo 32,4 g (0,704 molu) kyseliny mravčej, 68 g (0,5 mola) 3-fenylpropanolu a postupné třikrát 3 g chloridu vápenatého*, vždy s medzioddelením spodnej fázy. Pracovalo sa pri teplote 95 °C trikrát 15 minút. Po ukončení esterifikácie sa oddělila organická fáza, ktorá sa potom destilovala. Po odstránení nezreagovanej kyseliny mravčej jej oddestilovaním sa surový ester destiloval při tlaku 2,7 kPa a získalo sa 76 g formiátu o čistotě 99 pere. čo zodpovedá výtažku 91,6 % teoret. množstva.32.4 g (0.704 mole) of formic acid, 68 g (0.5 mole) of 3-phenylpropanol and 3 g of 3 g of calcium chloride *, each with an intermediate phase separation, were metered into the apparatus as in Example 1. The reaction was run at 95 ° C three times for 15 minutes. After the esterification was complete, the organic phase was separated and then distilled. After the unreacted formic acid was removed by distillation, the crude ester was distilled at 2.7 kPa to give 76 g of 99 peat formate. corresponding to a yield of 91.6% of theory. amount.

Příklad 4Example 4

Do esterifikačnébo reaktora (příklad lj sa předložilo 32,4 g (0,704 mólu) kyseliny mravčej, 50 g (0,5 mólu) cyklohexanolu, 2X5 g chloridu vápenatého s medzioddelením vodnej vrstvy, pričom k prvému podielu sa pridal 1 cm³ 36,5 % kyseliny chíorovodíkovej. Pracovalo sa pri teplote 90 °C po. dobu celkové 30 minút (2X15 minút).To the esterification reactor (Example 1j) was charged 32.4 g (0.704 mol) of formic acid, 50 g (0.5 mol) of cyclohexanol, 2X5 g of calcium chloride with the separation of an aqueous layer, with 1 cm ^{3 of} 36.5 being added to the first. The reaction was run at 90 ° C for a total of 30 minutes (2 x 15 minutes).

Po ukončení esterifikácie sa esterová vrstva přefiltrovala a spracovala vakuovou destiláciou (pri 2,7 kPa). Získalo sa 54,6 g esteru o čistotě 98 %, t. j. výťažok esteru bol 83,6 % teorie.After the esterification was complete, the ester layer was filtered and treated by vacuum distillation (2.7 kPa). 54.6 g of an ester with a purity of 98% were obtained, m.p. j. the ester yield was 83.6% of theory.

Příklad 5Example 5

Do esterifikačnébo reaktora (příklad 1.j sa nadávkovalo 32,4 g (0,704 málu) kyseliny mravčej, 37 g (0,5 mólu) n-butanolu a dvakrát 4 g chloridu vápenatého s medzioddelením spodnej vrstvy. Teplota esterifikácie bota 98 C a celková doba esterifikácie bola dvakrát 10 minút.The esterification reactor (Example 1.j) was charged with 32.4 g (0.704 mol) of formic acid, 37 g (0.5 mol) of n-butanol, and twice with 4 g of calcium chloride with intermediate layer separation. the esterification time was twice 10 minutes.

Po neutralizácii kyseliny mravčej sa organická fáza vysušila síranom sodným a destilovala za atmosferického tlaku. Získalo sa 45 g produktu o čistotě 99 °/o, t. j. výťažok esteru bol 87,3 % teoret. množstva.After the formic acid was neutralized, the organic phase was dried over sodium sulfate and distilled at atmospheric pressure. 45 g of a product with a purity of 99% were obtained, m.p. j. the ester yield was 87.3% of theory. amount.

Příklad 6Example 6

Do esterifikačného reaktora ako v příklade 1 sa nasadilo 32,4 g (0,704 mólu) kyseliny mravčej, 30,5 g (0,5 mólu) izopropanoiu a v dvoch dávkách sa přidal v množstve 5 g chlorid vápenatý. Pracovalo sa pri teplote 69 stupňov Celzia.In the esterification reactor as in Example 1, 32.4 g (0.704 mol) of formic acid, 30.5 g (0.5 mol) of isopropanol were charged, and 5 g of calcium chloride were added in two portions. The temperature was 69 degrees Celsius.

Izolácia esteru sa uskutečnila vydestilováním za použitia malej rektifikačnej kolony o účinnosti 2 TP, Ako 1. frakcia destiloval izopropylformiát v množstve 35 g o čistotěIsolation of the ester was accomplished by distillation using a small rectification column with an efficacy of 2 TP. As the 1st fraction, isopropyl formate was distilled in an amount of 35 g of purity.

99.9 %, t. j. výťažok bol 79,5 % teorie.99.9%; j. the yield was 79.5% of theory.

Claims

with 6256084 the bottom phase was forgiven, 2 g of calcium chloride was added, the reaction was continued for 15 minutes under the same conditions and the bottom phase was also separated. Next, 3.7 g of formic acid and another 2 g of calcium chloride were added and the reaction was continued for 15 minutes. After decanting and filtering the organic phase, it was distilled under reduced pressure (2.7 kPa), leaving unreacted formic acid as the 1 st fraction and as 2, the ester fraction distilled to give 60.2 g purity. 98%, representing a yield of 86.6% of theory. EXAMPLE 3 32.4 g (0.704 mole) of formic acid, 68 g (0.5 mole) of 3-phenylpropanol and 3 g of calcium chloride are added to the device as in Example 1, each time with 3 g of calcium chloride. separation of the lower phase. The temperature was 95 ° C three times 15 minutes. After the esterification was complete, the organic phase was separated and then distilled. After removing the unreacted formic acid by distilling it off, the crude ester was distilled at 2.7 kPa and 76 g of 99pere pure formate was obtained. corresponding to 91.6% of theory. EXAMPLE 4 32.4 g (0.704 mole) of formic acid, 50 g (0.5 mole) of cyclohexanol, 2 * 5 g of calcium chloride were added to the esterification reactor (Example 1) with the separation of the aqueous layer, with 1 cm 3 of 36.5% hydrochloric acid. Worked at 99 ° C for a total of 30 minutes (2X15 minutes). Upon completion of the esterification, the ester layer was filtered and vacuum dried (2.7 kPa). 54.6 g of ester having a purity of 98% were obtained, i.e. the ester yield was 83.6% of theory. EXAMPLE 5 32.4 g (0.704 moles) of formic acid, 37 g (0.5 moles) of n-butanol and two times 4 g of calcium chloride with an intermediate layer of the lower layer were siphoned into the esterification reactor (Example 1). The esterification temperature of fco-La 98 C and the total esterification time were two times 10 minutes. After neutralizing the formic acid, the organic phase was dried over sodium sulfate and distilled at atmospheric pressure. 45 g of 99% pure product were obtained, i.e. the ester was 87.3% of theory. quantity. EXAMPLE 6 32.4 g (0.704 mol) of formic acid, 30.5 g (0.5 mol) of isopropanol were added to the esterification reactor in Example 1 in two portions of 5 g of calcium chloride. Worked at a temperature of 69 degrees Celsius. Isolation of the ester was accomplished by distillation using a small rectification column of activity

2 TP, as the first fraction, distilovalisopropyl formate in an amount of 35 g with a purity of 99.9%, i.e. the yield was 79.5% of theory. SUBJECT A process for the production of formic esters with siphatic alcohols having carbon numbers of 1 to 10 by alkylaromatic alcohols, wherein the alkyl has carbon numbers of 1 to 3, cyclopentanoyl or cyclohexanol, characterized in that the esterification is carried out in the presence of calcium chloride or chlorine of calcium with the addition of hydrogen chloride, by using 1 to 1.5 moles of formic acid per mole of alcohol, and 0.1 to 0.2 moles of calcium chloride per mole of alcohol; up to 0.2 mol of calcium chloride with the addition of 0.005 to 0.05 mol of hydrochloric acid and esterification at 35 to 110 ° C.