PL135546B1 - Process for preparing novel derivatives of betaines - Google Patents

Process for preparing novel derivatives of betaines Download PDF

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PL135546B1
PL135546B1 PL23638482A PL23638482A PL135546B1 PL 135546 B1 PL135546 B1 PL 135546B1 PL 23638482 A PL23638482 A PL 23638482A PL 23638482 A PL23638482 A PL 23638482A PL 135546 B1 PL135546 B1 PL 135546B1
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general formula
formula
betaines
group
betaine
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PL23638482A
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Polish (pl)
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PL236384A1 (en
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Ewa Lekawska
Ewa Zielinska
Dionizy Gasztych
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Politechnika Slaska Im Wincent
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Przedmiotem wynalazku jest sposób otrzymywania nowych pochodnych betain jak winianowa, cytrynianowa i fosforanowa o wzorze ogólnym 1, w którym R oznacza lancuch alkilowy prosty o 12-22 atomach wegla, a I oznacza grupe winianowa, cytrynianowa lub fosforanowa o wzorze ogólnym 2f3 lub 4.Stwierdzono, ze mozna otrzymac nieznane pochodne betain jak winianowe, cytrynianowe i fosforanowe, które w odróznieniu od znanych sulfonowych betain, z uwagi na zawartosc w czasteczce skladników wystepujacych w organizmach zywych, latwo rozkladalnych biologicznie / pochodne kwasów cytrynowego, winowego ,fosforowego/ nie stanowia zagrozenia dla srodowiska naturalnego. Maja one bardzo dobre wlasnosci suspendowania brudu, a takze wlasnosci bakteriobójcze, dezynfekcyjne, sekwestrujace, antyelektro¬ statyczne* Zapobiegaja redepozycji brudu, nie wywoluja eutrofizmu, nie draznia oczu.Sposób otrzymywania nowych pochodnych betain o wzorze ogólnym 1, w którym R oznacza lancuch alkilowy prosty o 12-22 atomach wegla, a I oznacza grupe o wzorze ogólnym 2,3 lub 4 wedlug wynalazku polega na tym, ze epichlorohydryne poddaje sie reakcji w tempera¬ turze okolo 100°C z cytrynianem dwusodowym, winianem jednosodowym lub fosforanem dwusodowym tak dlugo, az zawartosc soli sodowej spada ponizej 1#, po czym otrzymana mieszanine zawierajaca zwiazek o wzorze ogólnym 5 w którym X oznacza grupe o wzorze ogólnym 2/3 lub 4, którego sie nie wyodrebnia, traktuje sie trzeciorzedowa amina o wzorze ogólnym 6, w którym R ma znaczenie takie jak we wzorze lf w temperaturze 90-100 C w srodowisku wodnym. Reakcje prowadzi sie tak dlugo, az zawartosc aminy osiagnie wartosc ponizej 0,3#. Otrzymane zwiazki o wzorze ogólnym 1 osusza sie przez oddestylowanie wody na wyparce prózniowej,oczyszcza od chlorku sodowego przez ekstrakcje izopropanolem oraz od aminy przez ekstrakcje eterem naftowym.2 135 546 Przyklad I. Do kolby czteroszyjnej o pojemnosci 250cnr zaopatrzonej w mieszadlo teflonowe, termometr, wkraplacz i chlodnice zwrotna wprowadzono 0,2 mola cytrynianu dwusodowego oraz 4 mole wody destylowanej, podgrzewano do 100 C i wkraplano w czasie 30 minut 0,46 mola epichlorohydryny. Po wkrppleniu mieszanine ogrzewano w 100°C tak dlugo, az zawartosc* cytrynianu dwusodowego wyniosla ponizej l/. Nastepnie dodawano 0,2 mola N,N - dwumetylo-N-dodecyloarainy i prowadzono dalej rekacje w 90-100°C, az zawartosc aminy osiagala wartosc ponizej 0,5$. Z mieszaniny poreakcyjnej usuwano wode w wyparce prózniowej w temperaturze 50°C# Surowy produkt oddzielono od chlorku sodowego przez ekstrakcje izopropanolem, a od aminy przez ekstrakcje eterem naftowym.Wydajnosc 82$. Otrzymana betaina miala pontac bezbarwnego smaru, jej rozpuszczalnosc w wodzie w temperaturze 30°C wynosila 91,4#, zdolnosc myjaca 75# napiecie powierzchniowe w N/m t 38,0 . 10~3 / przy pH = 2/, 39,6 • 10~3/pH = 6/,37,5*10~3/pH=10/.Przyklad II. Do aparatury opisanej w przykladzie I wprowadzono 0,2 mola winianu jednosodowego oraz 3 mole wody destylowanej podgrzewano do 100 C i wkraplano w czasie 30 minut 0,46 mola epichlorohydryny. Po wkropleniu mieszanine ogrzewano w 100°C tak dlugo, az zawartosc winianu wynosila ponizej !$• Nastepnie dodawano 0,2 mola N,N-dwumetylo-N- dodecyloaminy i prowadzono dalej reakcje w 90-100°C, az zawartosc aminy wynosila ponizej 0,5#* Dalej postepowano tak jak w przykladnie I. Wydajnosc 85#.Otrzymana betaina miala postac bezbarwnego smaru, jej rozpuszczalnosc w wodzie w temperaturze 300°C wynosila 90,8$ zdolnosc myjaca 78$, napiecie powierzchniowe w N/ m 5 35,5 . 10~3 /pH = 2/,37,2 • 10"5/pH = 6/, 34,2 • 10"3 / pH = 10/# Przyklad III. Aparatura, substraty i parametry reakcji jak w przykladzie II, z ta róznica, ze zastosowano II,N-dwumetylo-N-oktadecyloamine.Wydajnosc 80^. Otrzymana betaina"byla cialem stalym o temperaturze topnienia 60-63 0, jej rozpuszczalnosc w wodzie w 30°C wynosila 88,6'of zdolnosc myjaca 76°, napijcie powierzchniowe w N"m : 36,2 • 10~3 /pil = 2/, 38,0 • 10"3 /pil = 6/ 34,0 *10"3/pH=10/.Przyklad IV. Do aparatury opisanej w przykladzie I wprowadzono 0,2 mola fosforanu dwusodowego oraz 4 mole wody destylowanej, podgrzewano do 100 C i wkraplano *w czasie 30 minut 0,46 mola epichlorohydryny. Po wkropleniu mieszanine ogrzewano w 100 C tak dlugo, az zawartosc fosforanu wynosila ponizej 1$• Nastepnie dodawano 0^2 mola NfN-dwumetylo-N-oktadecyloaminy i prowadzono dalej reakcje w 90-100°C, az zawartosc aminy wyniosla ponizej 0,5#« Dalej postepowano tak jak w przykladzie I. Wydajnosc 83$. Otrzymana betaina byla cialem stalym o temperaturze topnienia 122-124°Cf jej rozpuszczalnosc w wodzee w 30° C wynosila 85,2# zdolnosc myjaca 78#, napiecie powierzchniowe w N/m : 41,8 • 10"3 /pH = 2/f 44,3 • 10"3/Ph=6/, 37, 0 . 10~3 / pH = 10/.Ocena mikrobiologiczna skutecznosci dzialania na drobnoustroje betain CH o wzorze 3 R-N-CHg -CH-CH2- x CH, OH Nazwa betainy Cytrynianobetaina Winianobetaina Winianobetaina Posforanobetaina R C15H25 C12H25 C18H37 °18H37 Stezenie drobnoustrojobójcze w # 1 Escherlchia coli 0,5 0,25 0,3 0,6 Pseudomonas aeruginosa 0,5 1 0,8 0,5 Staphylococcus aureus 0,012 0,5 0,1 0,6 Candida albicans 0,25 0,1 0,1 0,6135 546 Zastrzezenie patentowe Sposób otrzymywania nowych pochodnych betain o wzorze ogólnym lf w którym R oznacza lancuch alkilowy, prosty o 12-22 atomach wegla X oznacza grupe o wzorze cgolnym 2,3 lub 4f znamienny tymf ze epichlorohydryne poddaje sie reakcji w temperaturze okolo 100°C z cytrynianem dwusodowym, winianem Jednosodowym lub fosforanem dwusodowym, po czym otrzymana mieszanine, zawierajaca zwiazek o wzorze ogólnym 5f w którym X oznacza grupe o wzorze ogólnym 2,3 lub 4, traktuje sie trzeciorzedowa amina o wzorze ogólnym 6, w którym R ma wyzej okreslone znacznie, w temperaturze 90-100°C w srodowisku wodnym. ch, i© R-N-CH,-CH-CH2-X CHa OH wzór 1 OH I -C-i 0 cooNa 1 <= 0-C-CH2-C-CH;rC00u wzór 2 H H o-c-c—c-coou II I I 0 OH OH -OPO3Na0 wzór4 wzór3 Cl-CH2-CH-CH2-X OH wzór 5 CH3 I R—N I CH3 wzór 6 PLThe subject of the invention is a method for the preparation of new betaine derivatives, such as tartrate, citrate and phosphate derivatives of general formula 1, in which R is a straight alkyl chain with 12-22 carbon atoms, and I is a tartrate, citrate or phosphate group of general formula 2f3 or 4. that it is possible to obtain unknown derivatives of betaines, such as tartrate, citrate and phosphate, which, unlike the known sulphonic betaines, due to the content in the molecule of components found in living organisms, easily biodegradable / derivatives of citric, tartaric, phosphoric acids the natural environment. They have very good properties of suspending dirt, as well as bactericidal, disinfecting, sequestering, anti-electrostatic properties * They prevent the redeposition of dirt, do not cause eutrophication, do not irritate the eyes. having 12-22 carbon atoms and I is a group of general formula 2,3 or 4 according to the invention, epichlorohydrin is reacted at a temperature of about 100 ° C with disodium citrate, monosodium tartrate or disodium phosphate as long as until the sodium salt content drops below 1 #, then the resulting mixture containing the compound of general formula 5 in which X is a group of general formula 2/3 or 4, which is not isolated, the tertiary amine of general formula 6 is treated in which R has the same meaning as in formula 1f at a temperature of 90-100 ° C in an aqueous environment. The reactions are carried out until the amine content is below 0.3 #. The obtained compounds of the general formula I are dried by distilling off the water in a vacuum evaporator, purified from sodium chloride by extraction with isopropanol and from amine by extraction with petroleum ether. 2 135 546 Example I. and reflux condensers, 0.2 moles of disodium citrate and 4 moles of distilled water were introduced, heated to 100 ° C, and 0.46 moles of epichlorohydrin was added dropwise over 30 minutes. After dropping, the mixture was heated at 100 ° C until the content * of disodium citrate was below 1 /. Then 0.2 mole of N, N-dimethyl-N-dodecylaraine was added and the reaction was continued at 90-100 ° C until the amine content was below 0.5 $. Water was removed from the reaction mixture in a vacuum evaporator at 50 ° C. The crude product was separated from the sodium chloride by extraction with isopropanol, and from the amine by extraction with petroleum ether. Yield 82 $. The obtained betaine was supposed to float a colorless lubricant, its water solubility at 30 ° C was 91.4%, washing power 75%, surface tension in N / m t 38.0. 10 ~ 3 / at pH = 2 /, 39.6 · 10 ~ 3 / pH = 6 /, 37.5 * 10 ~ 3 / pH = 10 /. Example II. To the apparatus described in example 1, 0.2 moles of monosodium tartrate were introduced and 3 moles of distilled water were heated to 100 ° C and 0.46 moles of epichlorohydrin were added dropwise over 30 minutes. After the dropwise addition, the mixture was heated at 100 ° C until the tartrate content was below! $ • Then 0.2 mole of N, N-dimethyl-N-dodecylamine was added and the reaction continued at 90-100 ° C until the amine content was below 0.5 # * The next step was as in example I. Yield 85 #. The obtained betaine was in the form of a colorless lubricant, its solubility in water at 300 ° C was 90.8 $, washing power 78 $, surface tension in N / m 5 35.5. 10 ~ 3 / pH = 2 /, 37.2 • 10 "5 / pH = 6 /, 34.2 • 10" 3 / pH = 10 / # Example III. Apparatus, substrates and reaction parameters as in example II, except that II, N-dimethyl-N-octadecylamine was used. Yield 80 ° C. The obtained betaine "was a solid with a melting point of 60-63 ° C, its solubility in water at 30 ° C was 88.6'of, washing capacity 76 °, surface tension in N" m: 36.2 • 10 ~ 3 / pil = 2 /, 38.0 • 10 "3 / pil = 6 / 34.0 * 10" 3 / pH = 10 /. Example IV. To the apparatus described in example 1, 0.2 moles of disodium phosphate and 4 moles of distilled water were introduced, heated to 100 ° C, and 0.46 moles of epichlorohydrin was added dropwise over 30 minutes. After the dropwise addition, the mixture was heated at 100 ° C until the phosphate content was below 1 ° C. Then 0 ^ 2 moles of NfN-dimethyl-N-octadecylamine were added and the reactions were continued at 90-100 ° C until the amine content was below 0.5 # «The next step was as in example 1. Yield 83 $. The obtained betaine was a solid with a melting point of 122-124 ° Cf its water solubility at 30 ° C was 85.2 #, washing ability 78 #, surface tension in N / m: 41.8 • 10 "3 / pH = 2 / f 44.3 • 10 "3 / Ph = 6 /, 37, 0. 10 ~ 3 / pH = 10 /. Microbiological evaluation of the microbial efficacy of betaines CH of formula 3 RN-CHg -CH-CH2- x CH, OH Betaine name Citrate Betaine Tartrate Betaine Tartrate Betaine Phosphate Betaine R C15H25 C12H25 C18 Antimicrobials37 ° 1H37 coli 0.5 0.25 0.3 0.6 Pseudomonas aeruginosa 0.5 1 0.8 0.5 Staphylococcus aureus 0.012 0.5 0.1 0.6 Candida albicans 0.25 0.1 0.1 0, 6135 546 Claim A method for the preparation of new betaine derivatives of the general formula lf in which R represents a straight alkyl chain with 12-22 carbon atoms X represents a group of general formula 2,3 or 4f characterized by reacting epichlorohydrin at a temperature of about 100 ° C C with disodium citrate, monosodium tartrate or disodium phosphate, then the resulting mixture containing a compound of general formula 5f in which X is a group of general formula 2,3 or 4 is treated with a tertiary amine of general formula 6 in which R is as above determined significantly, in temp at 90-100 ° C in the aquatic environment. ch, i © RN-CH, -CH-CH2-X CHa OH formula 1 OH I -Ci 0 cooNa 1 <= O-C-CH2-C-CH; rC00u formula 2 HH occ — c-coou II II 0 OH OH -OPO3Na0 formula4 formula3 Cl-CH2-CH-CH2-X OH formula 5 CH3 IR — NI CH3 formula 6 PL

Claims (1)

1. Zastrzezenie patentowe Sposób otrzymywania nowych pochodnych betain o wzorze ogólnym lf w którym R oznacza lancuch alkilowy, prosty o 12-22 atomach wegla X oznacza grupe o wzorze cgolnym 2,3 lub 4f znamienny tymf ze epichlorohydryne poddaje sie reakcji w temperaturze okolo 100°C z cytrynianem dwusodowym, winianem Jednosodowym lub fosforanem dwusodowym, po czym otrzymana mieszanine, zawierajaca zwiazek o wzorze ogólnym 5f w którym X oznacza grupe o wzorze ogólnym 2,3 lub 4, traktuje sie trzeciorzedowa amina o wzorze ogólnym 6, w którym R ma wyzej okreslone znacznie, w temperaturze 90-100°C w srodowisku wodnym. ch, i© R-N-CH,-CH-CH2-X CHa OH wzór 1 OH I -C-i 0 cooNa 1 <= 0-C-CH2-C-CH;rC00u wzór 2 H H o-c-c—c-coou II I I 0 OH OH -OPO3Na0 wzór4 wzór3 Cl-CH2-CH-CH2-X OH wzór 5 CH3 I R—N I CH3 wzór 6 PL1. Claim The method for the preparation of new betaine derivatives of the general formula lf in which R is a straight alkyl chain with 12-22 carbon atoms X represents a group of general formula 2,3 or 4f characterized by reacting epichlorohydrin at a temperature of about 100 ° C C with disodium citrate, monosodium tartrate or disodium phosphate, then the resulting mixture containing a compound of general formula 5f in which X is a group of general formula 2,3 or 4 is treated with a tertiary amine of general formula 6 in which R is as above significantly determined at a temperature of 90-100 ° C in an aquatic environment. ch, i © RN-CH, -CH-CH2-X CHa OH formula 1 OH I -Ci 0 cooNa 1 <= O-C-CH2-C-CH; rC00u formula 2 HH occ — c-coou II II 0 OH OH -OPO3Na0 formula4 formula3 Cl-CH2-CH-CH2-X OH formula 5 CH3 IR — NI CH3 formula 6 PL
PL23638482A 1982-05-12 1982-05-12 Process for preparing novel derivatives of betaines PL135546B1 (en)

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