CS209177B1 - Method of manufacture of tetramethylester and tetrakis /1-methylethyl/ ester of dichlormethylenphosphone acid - Google Patents
Method of manufacture of tetramethylester and tetrakis /1-methylethyl/ ester of dichlormethylenphosphone acid Download PDFInfo
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- CS209177B1 CS209177B1 CS691779A CS691779A CS209177B1 CS 209177 B1 CS209177 B1 CS 209177B1 CS 691779 A CS691779 A CS 691779A CS 691779 A CS691779 A CS 691779A CS 209177 B1 CS209177 B1 CS 209177B1
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- methylethyl
- ester
- carbon tetrachloride
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- 150000002148 esters Chemical class 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 11
- 239000002253 acid Substances 0.000 title description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 title description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- -1 tetramethyl ester Chemical class 0.000 claims description 10
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 7
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- OMTPMIYCEZYHFY-UHFFFAOYSA-N 2-[[dichloro-di(propan-2-yloxy)phosphorylmethyl]-propan-2-yloxyphosphoryl]oxypropane Chemical compound CC(C)OP(=O)(OC(C)C)C(Cl)(Cl)P(=O)(OC(C)C)OC(C)C OMTPMIYCEZYHFY-UHFFFAOYSA-N 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- RVDYNQGIJXIAAA-UHFFFAOYSA-N dichloro-bis(dimethoxyphosphoryl)methane Chemical compound COP(=O)(OC)C(Cl)(Cl)P(=O)(OC)OC RVDYNQGIJXIAAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 238000007348 radical reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 4
- 229910052698 phosphorus Inorganic materials 0.000 claims 4
- 239000012298 atmosphere Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003039 volatile agent Substances 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ACSIXWWBWUQEHA-UHFFFAOYSA-N clodronic acid Chemical compound OP(O)(=O)C(Cl)(Cl)P(O)(O)=O ACSIXWWBWUQEHA-UHFFFAOYSA-N 0.000 description 3
- 229960002286 clodronic acid Drugs 0.000 description 3
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- NDHJAUWDMKYTND-UHFFFAOYSA-N 2-[propan-2-yloxy(trichloromethyl)phosphoryl]oxypropane Chemical compound CC(C)OP(=O)(C(Cl)(Cl)Cl)OC(C)C NDHJAUWDMKYTND-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GKYYRSVAKDSFGK-UHFFFAOYSA-N trichloro(dimethoxyphosphoryl)methane Chemical compound COP(=O)(OC)C(Cl)(Cl)Cl GKYYRSVAKDSFGK-UHFFFAOYSA-N 0.000 description 2
- 238000007014 Michaelis-Becker reaction Methods 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- PZQSQRCNMZGWFT-QXMHVHEDSA-N propan-2-yl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(C)C PZQSQRCNMZGWFT-QXMHVHEDSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Description
(54) Způsob výroby tetramethylesteru a tetrakis(l-methylethyl)esteru kyseliny dichlormethylendifosfonové(54) A method for producing tetramethyl ester and tetrakis (1-methylethyl) dichloromethylenediphosphonic acid ester
Vynález se týká způsobu výroby tetramethylesteru kyseliny dichlormethylendifosfonové (I) a tetrakis(l-methylethyl)esteru kyseliny dichlormethylendifosfonové (II), které jsou cennými meziprodukty při synthese složek detergentů, resp. jako přísady do olejů určených pro extrémní tlaky. Mezi vyhovujícími složkami detergentů, které lze získat z produktů tohoto vynálezu, jsou sole alkalických kovů, různě substituovaných aminů, nebo amoniové sole kyseliny dichlormethylendifosfonové (kyseliny klodronové) odvozené od esterů I. a II. Tetramethylester, popřípadě tetrakis (l-methylethyl)ester kyseliny dichlormethylendifosfonové (I) popř. (II), lze na tyto sole převést různými metodami. Příkladem takové přípravy je hydrolysa vroucí koncentrovanou kyselinou chlorovodíkovou, nebo pyrolysa v případě 1-methylethylesteru, za vzniku volné kyseliny, následovaná přidáním base jako je např. hydroxid sodný, ke kyselině za vzniku příslušné sole (U. S. 3,624,188; U. S. 3,422,021; Belg. 627,205; Brit. 1,026,366).The present invention relates to a process for the preparation of dichloromethylenediphosphonic acid tetramethyl ester (I) and dichloromethylenediphosphonic acid tetrakis (1-methylethyl) ester (II), which are valuable intermediates in the synthesis of detergent components, respectively. as an additive to oils intended for extreme pressures. Suitable detergent ingredients obtainable from the products of this invention include alkali metal salts, variously substituted amines, or ammonium salts of dichloromethylenediphosphonic acid (clodronic acid) derived from esters I and II. Tetramethyl ester or tetrakis (1-methylethyl) dichloromethylenediphosphonic acid (I) or tetrakis (1-methylethyl) ester; (II) can be converted to these salts by various methods. An example of such a preparation is hydrolysis of boiling concentrated hydrochloric acid, or pyrolysis in the case of 1-methylethyl ester, to give the free acid followed by addition of a base such as sodium hydroxide to the acid to form the corresponding salt (US 3,624,188; US 3,422,021; Belg. 627,205; Brit., 1,026,366).
SchémaDiagram
CH2X2 + 2 P/0R/3 CH 2 X 2 + 2 P / OR / 3
CH2X2 + 2 NaP0/0R/2 CH 2 X 2 + 2 NaPO / 0R / 2
PO/OR/,PO / OR /,
P0/0R/,P0 / 0R /,
CC1, .po/or/,CC1, .po / or /,
PO/OR/,PO / OR /,
Dosavadní postup výroby tetramethylesteru a tetrakis(l-methylethyl)esteru kyseliny dichlormethylendifosfonové (I) popř. (II) lze shrnout pod obecné Schéma I, kde druhý reakční stupeň (c), chlorace tetraalkylesterů kyseliny methylendifosfonové (III, popř. IV) byla postupem času dovedena takřka k dokonalosti. Výtěžek reakce (c) při použití chlornanu ve vodném prostředí, eventuálně za přítomnosti chloridu uhličitého, dosahuje až 85 % (J. Organometal. Chem. 13, 199 (1968); U. S. 3,624,188; U. S. 3,772,412).The prior art process for the preparation of tetramethyl ester and tetrakis (1-methylethyl) dichloromethylenediphosphonic acid ester (I), respectively. (II) can be summarized under General Scheme I, wherein the second reaction step (c), the chlorination of the methylene diphosphonic acid tetraalkyl esters (III and IV, respectively) has been nearly perfected over time. The yield of reaction (c) using hypochlorite in an aqueous medium, optionally in the presence of carbon tetrachloride, is up to 85% (J. Organometal. Chem. 13, 199 (1968); U. S. 3,624,188; U. S. 3,772,412).
X = halogenX = halogen
R = CH3, CH(CH3)2 CH2X2R = CH 3 , CH (CH 3 ) 2 CH 2 X 2
P/OR/,PORE/,
-RX + CH2XP0/0R/2-RX + CH 2 XP0 / 0R / 2
P/OR/ / PO/OR/2 P / OR / / PO / OR / 2
PO/OR/2 PO / OR / 2
Výchozí surovina pro halogenaci, tetraalkylestery kyseliny methylendifosfonové (III, popř. IV), se připravuje podstatně obtížněji. Michaelis-Arbusovova reakce (a), která u primárních halogenidů probíhá velice snadno, je u dihalogenmethanů spojena se značnými komplikacemi. Výtěžek reakce dijodmethanu s trialkylfosřitem (J. Chem. Soc. 1955, 3092) nepřesáhl 25 %, v případě dibrommethanu byl ještě nižší (J. Amer. Chem. Soc. 75, 5738 (1953); J. Chem. Soc. 1947, 1465). Obtíže dané protichůdnými nároky obou stadií reakce, byly částečně zmenšeny prováděním reakce za přísně kontrolovaných reakčních podmínek, přičemž se vznikající alkylhalogenid neustále oddestilovává. Směs methylenbromidu a tris(l-methylethyl)fosfitu např. vyžaduje přesně stoupající teplotu od 143 °C do 185 °C s reakční dobou okolo 16 hodin; výtěžek je pak cca 90 % (U. S. 3,251,907). Rozdíly v bodech varu v případě methylesteru jsou již tak nevýhodné, že látka III se připravuje z esteru IV přes odpovídající volnou kyselinou esterifikací (J. Organometal. Chem. 13, 199 (1968)).The starting material for the halogenation, the methylene diphosphonic acid tetraalkyl esters (III or IV), is much more difficult to prepare. The Michaelis-Arbus reaction (a), which proceeds very easily in primary halides, is associated with considerable complications in dihalomethanes. The yield of the reaction of diiodomethane with trialkyl phosphite (J. Chem. Soc. 1955, 3092) did not exceed 25% and was even lower for dibromomethane (J. Amer. Chem. Soc. 75, 5738 (1953); J. Chem. Soc. 1947, 1465). The difficulties due to the conflicting claims of both stages of the reaction have been partially alleviated by carrying out the reaction under strictly controlled reaction conditions, with the resulting alkyl halide being constantly distilled off. For example, a mixture of methylene bromide and tris (1-methylethyl) phosphite requires a precisely rising temperature from 143 ° C to 185 ° C with a reaction time of about 16 hours; the yield is then about 90% (U. S. 3,251,907). The differences in the boiling points of the methyl ester are already disadvantageous that the compound III is prepared from the ester IV via the corresponding free acid by esterification (J. Organometal. Chem. 13, 199 (1968)).
X = halogenX = halogen
R = CH3, CH(CH3)2 CH2X2R = CH 3 , CH (CH 3 ) 2 CH 2 X 2
NaP0/0R/NaP0 / 0R /
-^-*-NaX + CH2XPO/OR/2 - ^ - * - NaX + CH 2 XPO / OR / 2
NaP0/0R/NaP0 / 0R /
CH,CH,
PO/OR/2 PO / OR / 2
PO/OR/2 PO / OR / 2
Michaelis-Beckerova reakce (b) probíhá u dihalogenmethanů ještě obtížněji (J. Chem. Soc. 1959, 2266); i při provádění ve dvou oddělených stadiích nepřesáhne celkový výtěžek reakce cca 40 % (Monatsh. Chem. 81, 202 (1950)), a pro přípravu esterů III a IV není prakticky používána.The Michaelis-Becker reaction (b) is even more difficult for dihalomethanes (J. Chem. Soc. 1959, 2266); even in two separate stages, the total reaction yield does not exceed about 40% (Monatsh. Chem. 81, 202 (1950)) and is practically not used for the preparation of esters III and IV.
Podstata způsobu výroby tetramethylesteru, popřípadě tetrakis(l-methylethyl)esteru kyseliny dichlormethylendifosfonové (I, popř. II) spočívá podle vynálezu v tom, že se na chlorid uhličitý působí trimethylfosfitem, popřípadě tris(l-methylethyl)fosfitem, za podmínek umožňujících radikálovou reakci, nejlépe za ozařování středotlakou rtuťovou výbojkou. Primárně vzniklý dimethylester kyseliny trichlormethylfosfonové (V), popř. bis(l-methylethyl)ester kyseliny trichlormethylfosfonové (VI) reaguje s další molekulou trialkylfosfitu za vzniku požadovaného tetramethylesteru I, popř. tetrakis(l-methylethyl)esteru II, které se ze směsi s nadbytečným trimethylfosfitem popř. tris(l-methylethyl)fosfitem, nezreagovaným dialkylesterem V, popř. VI a dalšími produkty izoluje běžnými postupy, jako je např. destilace. Methylchlorid, popř. 1-methylethylchlorid, se oddestilovává v průběhu reakce. Záměna druhého atomu chloru je podstatně pomalejší, než reakce do prvého stupně; třetí atom chloru se za použitých podmínek prakticky nesubstituuje.The process according to the invention consists in treating carbon tetrachloride with trimethylphosphite or tris (1-methylethyl) phosphite under conditions allowing a radical reaction , preferably for irradiation with a medium pressure mercury lamp. The primary trichloromethylphosphonic acid dimethyl ester (V) formed; trichloromethylphosphonic acid bis (1-methylethyl) ester (VI) is reacted with another trialkylphosphite molecule to form the desired tetramethyl ester I, respectively. tetrakis (1-methylethyl) ester II, which is mixed with excess trimethylphosphite or. tris (1-methylethyl) phosphite, unreacted dialkyl ester V; It is isolated by VI and other products by conventional techniques such as distillation. Methyl chloride; 1-methylethyl chloride is distilled off during the reaction. The exchange of the second chlorine atom is considerably slower than the reaction to the first stage; the third chlorine atom is practically unsubstituted under the conditions used.
V R = CH3 VR = CH 3
VI R = CH(CH3)2 VI R = CH (CH 3 ) 2
IR = CH3 IIR = CH(CH3)2 IR IIR = CH3 = CH (CH3) 2
P/OR/PORE/
P/OR/PORE/
P0/0R/,P0 / 0R /,
CC1 cci3po/or/2 CC1 cci 3 po / or / 2
-CC1-CCl
PO/OR/.PO / OR /.
Struktura sirupovitého tetramethylesteru kyseliny dichlormethylendifosfonové (I), destilujícího bez rozkladu při cca 100 °C v lázni a 7 Pa, vyplynula z elementární analysy, ze srovnání s autentickým vzorkem (U. S. 3,624,188) a z výsledku hydrolysy vedoucí ke krystalické kyselině klodronové.The structure of the syrup-like tetramethyl ester of dichloromethylenediphosphonic acid (I), distilling without decomposition at about 100 ° C in a bath and 7 Pa, resulted from elemental analysis, a comparison with an authentic sample (U.S. Pat.
Struktura krystalického tetrakis(l-methylethyl)esteru kyseliny dichlormethylendifosfonové (II), b.t. 50 °C, vyplynula z elementární analysy a ze srovnání s autentickým vzorkem (U. S. 3,772,412).Structure of the crystalline dichloromethylenediphosphonic acid tetrakis (1-methylethyl) ester (II), m.p. 50 ° C, was obtained from elemental analysis and compared to an authentic sample (U. S. 3,772,412).
Při ozařování směsi chloridu uhličitého a trimethylfosfitu v poměru cca 1 : 10 středotlakou rtuťovou výbojkou v atmosféře dusíku po dobu 10 hodin při 80 °C se získá cca 40 % tetramethylesteru kyseliny dichlormethylendifosfonové (I). Výtěžek roste postupně s dobou ozařování. Vyšší poměr složek než 10 : 1 (P(OCH3)3 : CC14) rychlost výrazně nezvyšuje. S rostoucí teplotou rychlost reakce roste, nicméně průběh reakce je uspokojivý i při teplotě laboratoře. Obdobné závislosti platí i pro průběh reakce chloridu uhličitého s tris(l-methylethyl)fosfítem.By irradiating a 1: 10 mixture of carbon tetrachloride and trimethylphosphite with a medium pressure mercury vapor lamp for 10 hours at 80 ° C, about 40% of tetramethyl dichloromethylenediphosphonic acid (I) is obtained. The yield increases gradually with the irradiation time. Component ratios higher than 10: 1 (P (OCH 3 ) 3 : CCl 4 ) do not significantly increase the rate. As the temperature rises, the reaction rate increases, but the reaction progress is satisfactory even at room temperature. Similar relationships are also valid for the reaction of carbon tetrachloride with tris (1-methylethyl) phosphite.
Ve srovnání s dříve popsanými metodami přípravy látky I má postup podle vynálezu tyto výhody:Compared to the previously described methods for the preparation of the compound I, the process according to the invention has the following advantages:
1. Použití chloridu uhličitého místo dibrommethanu nebo dijodmethanu.Use of carbon tetrachloride in place of dibromomethane or diiodomethane.
2. Odpadá jeden reakční stupeň (chlorace).2. One reaction step (chlorination) is eliminated.
3. Experimentální provedení reakce je jednoduché, používá nižší reakční teploty, kratší časy, při srovnatelném výtěžku.3. Experimental execution of the reaction is simple, using lower reaction temperatures, shorter times, with comparable yield.
Příklad 1Example 1
V křemenné aparatuře opatřené ponornou středotlakou rtuťovou výbojkou a zpětným chladičem bylo v atmosféře dusíku smícháno 9,5 ml chloridu uhličitého a 88 g trimethylfosfitu, teplota reakční směsi byla udržována na 75 °C. Sledování množství unikajícího methylchloridu sloužilo k přibližnému odhadu průběhu reakce. Po devítihodinovém ozařování byla reakční směs dělena frakční destilací; po 69 g trimethylfosfitu (50 °C/13 kPa) destiloval dimethylester kyseliny trichlormethylfosfonovéIn a quartz apparatus equipped with a submersible medium pressure mercury lamp and a reflux condenser, 9.5 ml of carbon tetrachloride and 88 g of trimethylphosphite were mixed under a nitrogen atmosphere, maintaining the temperature of the reaction mixture at 75 ° C. Monitoring the amount of escaping methyl chloride served to approximate the progress of the reaction. After irradiation for 9 hours, the reaction mixture was separated by fractional distillation; 69 g of trimethylphosphite (50 ° C / 13 kPa) distilled trichloromethylphosphonic acid dimethyl ester
Claims (3)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS691779A CS209177B1 (en) | 1979-10-11 | 1979-10-11 | Method of manufacture of tetramethylester and tetrakis /1-methylethyl/ ester of dichlormethylenphosphone acid |
| CS80365A CS209178B1 (en) | 1979-10-11 | 1980-01-18 | Manufacturing process of tetramethylester and tetrakis /1-methylethyl/ester of dichlormethylendiphosphone acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS691779A CS209177B1 (en) | 1979-10-11 | 1979-10-11 | Method of manufacture of tetramethylester and tetrakis /1-methylethyl/ ester of dichlormethylenphosphone acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS209177B1 true CS209177B1 (en) | 1981-11-30 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS691779A CS209177B1 (en) | 1979-10-11 | 1979-10-11 | Method of manufacture of tetramethylester and tetrakis /1-methylethyl/ ester of dichlormethylenphosphone acid |
| CS80365A CS209178B1 (en) | 1979-10-11 | 1980-01-18 | Manufacturing process of tetramethylester and tetrakis /1-methylethyl/ester of dichlormethylendiphosphone acid |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS80365A CS209178B1 (en) | 1979-10-11 | 1980-01-18 | Manufacturing process of tetramethylester and tetrakis /1-methylethyl/ester of dichlormethylendiphosphone acid |
Country Status (1)
| Country | Link |
|---|---|
| CS (2) | CS209177B1 (en) |
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1979
- 1979-10-11 CS CS691779A patent/CS209177B1/en unknown
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1980
- 1980-01-18 CS CS80365A patent/CS209178B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS209178B1 (en) | 1981-11-30 |
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