CS225375B1 - 2-formylethylmethacrylate and its preparation - Google Patents
2-formylethylmethacrylate and its preparation Download PDFInfo
- Publication number
- CS225375B1 CS225375B1 CS502882A CS502882A CS225375B1 CS 225375 B1 CS225375 B1 CS 225375B1 CS 502882 A CS502882 A CS 502882A CS 502882 A CS502882 A CS 502882A CS 225375 B1 CS225375 B1 CS 225375B1
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- CS
- Czechoslovakia
- Prior art keywords
- methacrylate
- preparation
- formylethyl
- hydrolysis
- acids
- Prior art date
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- KFCSRIXJBSMZBM-UHFFFAOYSA-N 3-oxopropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC=O KFCSRIXJBSMZBM-UHFFFAOYSA-N 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- -1 aldehyde ester Chemical class 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AVUJQRQKPGLUMY-UHFFFAOYSA-N 2,2-diethoxypropyl 2-methylprop-2-enoate Chemical compound CCOC(C)(OCC)COC(=O)C(C)=C AVUJQRQKPGLUMY-UHFFFAOYSA-N 0.000 description 1
- CPARKAXEDHCHNX-UHFFFAOYSA-N 3,3-diethoxypropyl 2-methylprop-2-enoate Chemical compound CCOC(OCC)CCOC(=O)C(C)=C CPARKAXEDHCHNX-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Vynález se týká 2-formylethylmethakrylátu a způsobu jeho přípravy.The invention relates to 2-formylethyl methacrylate and to a process for its preparation.
2-Formylethylmethakrylát nebyl dosud znám a pro podobné sloučeniny není známý žádný obecně použitelný způsob přípravy, protože se jedná o malou složitou molekulu se třemi reaktivními funkčními skupinami.2-Formylethyl methacrylate has not been known so far and no generic preparation method is known for similar compounds as it is a small complex molecule with three reactive functional groups.
Předmětem vynálezu je 2-formylethylmethakrylát vzorce IThe present invention provides 2-formylethyl methacrylate of formula I
CH2 = C — COOCH2CH2CH = OCH 2 = C - COOCH 2 CH 2 CH = O
I I.I I.
ch3 ch 3
Látka vzorce I se vyrábí tak, že se odpovídající dialkylacetal, tj. 3,3-dialkoxypropylmethakrylát, kde alkyl je methyl nebo ethyl, hydrolyzuje v kyselém prostředí při teplotě 60—100 °C. Hydrolýza se přitom provádí s výhodou v přítomnosti O-kyselin nebo solí O-kyselin a N-bází. Výhodně se používají O-kyseliny, jejichž pKa je v rozmezí 2,0 až 4,0. Hydrolýzy se s výhodou provádí v přítomnosti l-fenyl-3-pyrazolidinonu, čímž se zabrání nežádoucí oxidaci případně polymeraci.The compound of formula I is prepared by hydrolyzing the corresponding dialkylacetal, i.e., 3,3-dialkoxypropyl methacrylate, wherein alkyl is methyl or ethyl, at an acidic temperature at 60-100 ° C. The hydrolysis is preferably carried out in the presence of O-acids or salts of O-acids and N-bases. O-acids whose pK a is in the range of 2.0 to 4.0 are preferably used. The hydrolysis is preferably carried out in the presence of 1-phenyl-3-pyrazolidinone, thereby avoiding undesired oxidation or polymerization.
Použitý 3,3-dialkoxypropylmethakrylát lze vyrobit působením 3-halogen-l,l-dialkoxypropanu na kaliummethakrylát v přítomnosti dimethylformamidu při teplotě 120 až 170 °C.The 3,3-dialkoxypropyl methacrylate used can be produced by treating 3-halo-1,1-dialkoxypropane on potassium methacrylate in the presence of dimethylformamide at 120-170 ° C.
Látka vzorce I je vhodným monomerem s esterovou a aldehydovou skupinou, který polymerací poskytne polymer s vysokým obsahem aldehydových skupin, s dobře definovanou strukturou, v němž aldehydové skupiny mají nesníženou reaktivitu alifatických nízkomolekulárních aldehydů.The compound of formula (I) is a suitable monomer with an ester and aldehyde group, which by polymerization gives a high aldehyde group polymer with a well-defined structure in which the aldehyde groups have unreacted reactivity of aliphatic low molecular weight aldehydes.
V dalším je vynález blíže objasněn na příkladech provedení.In the following, the invention is illustrated in more detail by means of exemplary embodiments.
Příklad 1Example 1
Příprava 2-formylethylmethakrylátu (FEMA) hydrolysou s pyridinium-4-toluensulfonátem (sůl kyseliny pKa 0,87 a báze pKb 8,83).Preparation of 2-formylethyl methacrylate (FEMA) by hydrolysis with pyridinium 4-toluenesulfonate (pKa 0.87 salt and pKb base 8.83).
K roztoku pyridinium-4-toluensulfonátu (7,18 g, 30,8 mmol), hydrochinonu (0,10 gj, l-fenyl-3-pyrazolidinonu (0,20 gj ve vodě (400 ml) byl v dusíkové atmosféře za velmi intensivního mechanického míchání přidán 2,2-diethoxypropylmethakrylát (20,00 gramů, 92,5 mml). Směs byla za míchání co nejrychleji zahřáta na 75 °C a míchána po dobu dvojnásobnou než jaká byla potřeba k vymizení posledních kapiček acetalu (celkem asi 40 minut). Hydrolysát byl rychle ochlazen na 10 °C, neutralisován pevným hydrogenuhličitanem sodným (2,59 g, 30,8 mmol), vytřepán etherem (6 X 60 ml), extrakt vysušen bezvodým síranem horečnatým a po přidání l-fenyl-3-pyrazolidinonu (50 mg) byl zbaven rozpouštědla za sníženého tlaku při 35 °C a zbytek byl destilován s použitím chladiče pro nízkotepelnou destilaci. Výtěžek 10,65 g (81%) aldehydesteru FEMA, b. v. 34,5 až 35,5 °C/27 Pa. IR spektrum (film, cm-1) : 3108 (C = CH2), 2840 (CHO), 2740 (CHO), 1721 (C=O), 1637 (C = CH2), 946 (C=CH2), 819 (CHO). fH-NMR spektrum (deuteriochloroforum, Ó) : 9,83 (t, J = 1,5 Hz, 1H, CHO), 6,09 (m, W = 9,8 Hz, 1H, (C=CH), 5,57 (m, W = = 10,5 Hz, 1H, C = CH), 4,47 (t, J = 6,2 Hz, 2H, O—CH2—C), 2,83 (d t, 2H, C—CH2—C), 1,93 (t, 4J = 1,1 Hz, 3H, CH3—C = C). GC-MS spektrum, m/z (tkoi. 130 °C, tvyp. 160 °C, 0,5 μΐ 10 % roztoku v dichlormethanu) : 86,69 (CH2=C(CH3)C = O)+, 41 (CH2=C(CH3)]+, 99 (M — CH2CHO)+, 114 (M — CO)+. ProTo a solution of pyridinium-4-toluenesulfonate (7.18 g, 30.8 mmol), hydroquinone (0.10 gj, 1-phenyl-3-pyrazolidinone (0.20 gj in water (400 mL)) under a very high nitrogen atmosphere was 2,2-diethoxypropyl methacrylate (20.00 grams, 92.5 mml) was added by vigorous mechanical stirring, and the mixture was heated to 75 ° C as rapidly as possible and stirred for twice as much as needed to eliminate the last acetal droplets (total of about 40 grams). The hydrolyzate was rapidly cooled to 10 ° C, neutralized with solid sodium bicarbonate (2.59 g, 30.8 mmol), shaken with ether (6 X 60 mL), dried over anhydrous magnesium sulfate and added 1-phenyl-3. -pyrazolidinone (50 mg) was stripped of solvent under reduced pressure at 35 ° C and the residue distilled using a low-temperature distillation cooler to yield 10.65 g (81%) of FEMA aldehyde ester, bv 34.5 to 35.5 ° C. 27 Pa. IR spectrum (film, cm -1 ): 3108 (C = CH 2), 2840 (CHO), 2740 (CHO), 1721 (C = O), 1637 (C = CH2), 946 (C = CH2), 819 (CHO). F H NMR (deuteriochloroforum, o): 9.83 (t, J = 1.5 Hz, 1H, CHO), 6 09 (m, W = 9.8 Hz, 1H, (C = CH)), 5.57 (m, W = 10.5 Hz, 1H, C = CH), 4.47 (t, J = 6, 2 Hz, 2H, O-CH2-C), 2.83 (dt, 2H, C-CH2 -C), 1.93 (t, 4 J = 1.1 Hz, 3H, CH 3 -C = C ). GC-MS spectrum m / z (t i ko. 130 ° C, t off. 160 ° C, 0.5 μΐ 10% solution in dichloromethane): 86.69 (CH 2 = C (CH 3) C = O ), 41 (CH 2 = C (CH 3 )] +, 99 (M - CH 2 CHO) +, 114 (M - CO) + .
C7Hi0O3 (142,16) vypočteno: 59,14% C, 7,10 % H; nalezeno: 58,86 % C, 7,24 % H. Příklad 2C 7 H 10 O 3 (142.16) calculated: 59.14% C, 7.10% H; Found: C, 58.86; H, 7.24. Example 2
Příprava 2-formylethylmethakrylátu (FEMA) hydrolysou s kyselinou vinnou (pKa 3,02).Preparation of 2-formylethyl methacrylate (FEMA) by hydrolysis with tartaric acid (pKa 3.02).
Hydrolysa 3,3-diethoxypropylmethakrylátu (20,00 g, 92,5 mmol) byla provedena za katalysy kyselinou vinnou (4,62 g, 30,8 mmol) analogicky podle příkladu 1 při teplotě 70 °C, doba hydrolysy asi 10 minut. Výtěžek 9,73 g (74%) aldehydesteru FEMA, b. v. 34,4 až 35,5 °C/27 Pa (0,2 torr). 1H-NMR spektrum (deuteriochloroform): identické se spektrem látky podle příkladu 1.Hydrolysis of 3,3-diethoxypropyl methacrylate (20.00 g, 92.5 mmol) was carried out under tartaric acid catalysis (4.62 g, 30.8 mmol) analogously to Example 1 at 70 ° C, hydrolysis time about 10 minutes. Yield 9.73 g (74%) of FEMA aldehyde ester, bp 34.4-35.5 ° C / 27 Pa (0.2 torr). 1 H-NMR (CDCl 3): identical to that of Example 1.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS502882A CS225375B1 (en) | 1982-07-01 | 1982-07-01 | 2-formylethylmethacrylate and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS502882A CS225375B1 (en) | 1982-07-01 | 1982-07-01 | 2-formylethylmethacrylate and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS225375B1 true CS225375B1 (en) | 1984-02-13 |
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ID=5394333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS502882A CS225375B1 (en) | 1982-07-01 | 1982-07-01 | 2-formylethylmethacrylate and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS225375B1 (en) |
-
1982
- 1982-07-01 CS CS502882A patent/CS225375B1/en unknown
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