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Chemical Structure| 83883-25-4

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Product Details of [ 83883-25-4 ]

CAS No. :83883-25-4
Formula : C13H18O4
M.W : 238.28
SMILES Code : O=C(O)C1=CC=C(OCCCCCCO)C=C1
MDL No. :MFCD00971624

Safety of [ 83883-25-4 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319
Precautionary Statements:P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313

Application In Synthesis of [ 83883-25-4 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 83883-25-4 ]

[ 83883-25-4 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 83883-25-4 ]
  • [ 79-10-7 ]
  • [ 83883-26-5 ]
YieldReaction ConditionsOperation in experiment
70% With toluene-4-sulfonic acid; hydroquinone; In benzene; for 5h;Dean-Stark; Inert atmosphere; Synthesized above 4- (6-hydroxyhexyloxy) benzoic acid (13.47g, 56.53mmol) and the acid catalyst is p- toluenesulfonic acid (2.23g, 13mmol), a polymerization inhibitor, hydroquinone (2.3g, 20.9mmol) and excess acid (15ml, 07.2mmol) in benzene under nitrogen was introduced into the dissolution Dean-Stark trap (Dean stark trap) was refluxed for 5 hours until the removal of water generated in the reaction flask is connected sikimyeo. Dissolving the reaction material from the solvent under reduced pressure and then ends in diethyl ether and was thoroughly washed with distilled water until the pH is about 4-5. The obtained organic solvent into the magnesium sulfate (magnesium sulfate) the layer after removal of the water filtration by distillation under reduced pressure and was recrystallized from material with isopropanol (Isopropanol) solid product in powder form striking a pale pink title compound (Yield: 70.0percent ) was obtained.
35.3% With toluene-4-sulfonic acid; hydroquinone; In benzene; for 12h;Reflux; Dean-Stark; 14.0 g (58.8 mmol) of the obtained 4-(6-hydroxyhexyloxy)benzoic acid, 36.0 g (500 mmol) of acrylic acid, 2.00 g (11.7 mmol) of p-toluenesulfonic acid as an acid catalyst, and 1.20 g (11.8 mmol) of the polymerization inhibitor hydroquinone was dissolved in benzene. The mixed solution was refluxed in a flask connected to a Dean stark trap for about 12 hours until the amount of stoichiometry of water produced through the reaction was removed. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was dissolved in 300 mL of ethyl acetate. The mixed solution was washed with distilled water until no acrylic acid was found. At this time, the pH of the distilled water was checked to determine the presence of acrylic acid. Magnesium sulfate was added to the organic solution layer to dry the water. After filtration, the solvent was distilled off under reduced pressure, recrystallized from isopropyl alcohol to obtain 4-(6-(acryloyloxy)hexyloxy) benzoic acid as a white powdery solid.
21.3% With toluene-4-sulfonic acid; hydroquinone; In benzene;Dean-Stark; The compound of Formula 1-1 (8.3 g, 34.83 mmol),Acrylic acid (21.58 g, 299.47 mmol),P-toluenesulfonic acid (1.37 g, 8.01 mmol) as an acid catalyst,The polymerization inhibitor hydroquinone (1.40 g, 12.90 mmol) was dissolved in benzene and reacted in a flask connected with a dean-stark trap until the resulting stoichiometric amount of water was removed to about 4-5 Lt; / RTI & gt;After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained product was dissolved in diethyl ether (200 ml). The mixed solution was washed with distilled water until no acrylic acid was found. At this time, the pH of distilled water was checked to confirm the presence of acrylic acid. The resulting filtrate was distilled under reduced pressure, and the obtained product was recrystallized from isopropyl alcohol to obtain the compound of Formula 1-2 (yield: 21.3percent) as a pinkish white powder.
22g With toluene-4-sulfonic acid; In toluene; for 4h;Dean-Stark; Reflux; Then, a stirrer, a condenser and a Dean-Stark equipped with a reaction vessel, the compound shown in the formula (23) prepared in 17g (71 mmol), acrylic acid 10g (140 mmol), p- toluenesulfonic acid 1g, toluene He was charged with 100ml.Heating the reaction vessel to toluene reflux for 4 hours as it was.After the reaction, the reaction solution was then washed with saturated sodium bicarbonate and neutralized with 10percent hydrochloric acid solution, and washed with saturated aqueous sodium chloride, the organic layer was dried over anhydrous sodium sulfate.Oil distilled off the solvent to give the compound 22g as shown in equation (24).

  • 2
  • [ 83883-25-4 ]
  • [ 814-68-6 ]
  • [ 83883-26-5 ]
YieldReaction ConditionsOperation in experiment
~ 100% In ISOPROPYLAMIDE; at 25 - 30℃; for 1.25h;Product distribution / selectivity; Example 3 (E 3) ; synthesis of compound 1:; In a 250 ml chemical reactor are dissolved 23.89 G (0.10 mol) of 4- (6-hydroxyhexyloxy) benzoic acid (PURITY-100percent, preparation e. g. literature mentioned in example 1) in 100 G of dimethyl- acetamide at ca. 20°C. To the dear, stirred solution are gradually added 10.26 g (0.11 mol) of acryloyl chloride (Aldrich 96percent), keeping the reaction temperature below 35°C by external cooling. After the addition, which takes about 15 minutes, the reaction mixture is stirred for 1 hours at 30°C, when TLC analysis (Silicagel, Cyclohexane : ETHYLACETATE : Acetic acid = 50: 50: 2, parts b. volume, UV fluorescence indicator) indicates completion of the reaction. A nearly colourless suspension is formed. It is gradually precipitated into 400 ml of cold water using a high speed stirrer (1300 rpm). After finishing the addition, the suspension is stirred for 1/2hour and filtered. The filter residue is washed twice with warm (-40°C) water (400 ml), filtered and the residue dried in vacuo at 25°C. The thus obtained colourless, crystalline solid is dissolved in 93.40 G toluene at 70°C, 0.14 9 of di-tert. butyl-p-cresole (BHT, polymerisation inhibitor) added and the solution cooled slowly to 0°C. The crystalline precipitate is filtered off and dried in vacuum at 35°C to constant weight. 24.40 G (83.5percent o. th. ) of colourless, crystalline 4- (6-ACRYLOYLOXYHEXYLOXY) benzoic acid = compound (1) are obtained.
95% In 1-methyl-pyrrolidin-2-one; toluene; at 25 - 40℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
92% With 10H-phenothiazine; In 1-methyl-pyrrolidin-2-one; at 25 - 30℃; for 3h;Product distribution / selectivity; Example 1 (E 1); Synthesis of compound 1:; In a 30 litre chemical reactor are dissolved 4766.00 G (PURITY-100percent, 20.00 mol) of 4- (6- hydroxyhexyloxy) benzoic acid (preparation e. g. M. Portugal, H. Ringsdorf, R. Zentel, Makromol. Chem. 183,2311-2321 (1982) ) and 2.91 G phenothiazin (polymerisation inhibitor) in 10 000 mi of N-methyl pyrrolidone at ca. 20°C. To the clear, stirred solution 2074 g of acryloyl chloride (Aldrich, 96percent, 22 mol) are gradually added, keeping the reaction temperature BELOW 30°C by external cooling. After the addition, which takes about 1 hour, the reaction mixture is stirred for 2 hours at 25°C, when TLC analysis (Silicagel, Cydohexane: Ethylacetate : Acetic acid = 50: 50: 2, parts b. volume, UV fluorescence indicator) indicates completion of the reaction. A yellowish suspension is formed. It is gradually precipitated into 33'000 ML of water using a high speed stirrer (1300 rpm) and keeping the temperature below 25°C. After finishing the addition, the suspension is stirred for 1/2 HOUR and filtered. The filter residue is washed twice with 5000 ml of warm (-40°C) water and redispersed in 33'000 ML of warm water FOR 1/2 HOUR, FILTERED and the residue washed twice with 5000 ml of warm water. The moist residue is added to 20'000 ml of toluene, 2.93 g of di-tert. butyl-p-cresole (BHT, polymerisation inhibitor) are added and the mixture heated to 65°C to dissolve. A slightly coloured emulsion of some water in toluene results. The water phase is separated off and to the toluene solution is added 150.00 g of Bleicherde Tonsil Standard 312 ff (Fullers earth, Achenbach BUSCHHUTTEN GmbH, D-57223 KREUZTAL, Germany) and 150.00 g of Hyflo (diatomaceous earth, Mansville Corp. ) and the suspension stirred for 1/2HOUR at 65°C. The suspension is filtered and the clear filtrate cooled to 0°C and kept for several hours to crystallize the product, which is filtered off and dried in vacuum at T = 35°C. 5383.60 G (92percent o. th. ) of COLOURLESS, CRYSTALLINE 4-(6-ACRYLOYLOXYHEXYLOXY) benzoic ACID = compound (1) is obtained.
89% In 1-methyl-pyrrolidin-2-one; acetonitrile; at 25℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
89.6% In 1-methyl-pyrrolidin-2-one; acetone; at 0 - 5℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
86% In tetramethylurea; at 25 - 40℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
85% With N,N-dimethyl-aniline; In tetrahydrofuran; for 12h; Next, tetrahydrofuran (150 mL) of p- (6-hydroxyethoxy) benzoic acid (7.1 g, 30 mmol), acryloyl chloride (2.5 g, 27 mmol), dimethylaniline (DMA) (3.3 g, 27 mmol), The suspension was stirred for 12 hours. After completion of the reaction, water and ethyl acetate were added to carry out liquid separation. The solvent is distilled off, the residue is purified by silica gel chromatography, and the solvent is distilled off to give 4- [6- (acryloyloxy) hexyloxy] benzoic acid in 85percent yield (7.4 g, 26 mmol). I got it.
83.5% With 10H-phenothiazine; In 1-methyl-pyrrolidin-2-one; at 10 - 15℃; for 6h;Product distribution / selectivity; Example 2 (E 2); synthesis of compound 1:; Example 1 is repeated, but instead of allowing a temperature of <30°C during the addition of the acryloyl chloride, the temperature this time is kept below 15°C during said addition by additional external cooling. After the addition the mixture is stirred for 6 hours at 10°C. The product isolation procedure is the same as described in example 1. 5506.70 G (94percent o. th.) of colourless, crystalline 4- (6-ACRYLOYLOXYHEXYLOXY) benzoic ACID = compound (1) is obtained.
81.6% In 1-methyl-pyrrolidin-2-one; at -5 - 80℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
64% With triethylamine; In tetrahydrofuran; at 20℃; The compound of formula 10 (10 g, 42 mmol) is added into triethylamine (5 ml) and tetrahydrofuran (30 ml), and acryloyl chloride (6.6 g, 63 mmol) is dropwise added in 0.5 h. The mixture reacts overnight at room temperature, and then is transferred into water (150 ml). The generated precipitate is filtrated, and the crude product is recrystallized with ethyl alcohol. The obtained compound of formula 11 is colourless powder (8.2 g), and the yield is 64percent. (0069) 1H NMR, delta: 8.06 (d, 2H, J=8.7 Hz), 6.93 (d, 2H, J=8.7 Hz), 6.48 (dd, 1H, J=1.5, 17.4 Hz), 6.21 (dd, 1H, J=10.2, 17.4 Hz), 5.86 (dd, 1H, J=1.5, 10.2 Hz), 4.17 (t, 2H, J=6.6 Hz), 4.05 (t, 2H, J=6.6 Hz), 1.85-1.81 (m, 2H), 1.75-1.70 (m, 2H), 1.53-1.46 (m, 4H).
In 1-methyl-pyrrolidin-2-one; acetonitrile; at 25 - 40℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
In tetrahydrofuran; 1-methyl-pyrrolidin-2-one; at 25 - 40℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
In DMF (N,N-dimethyl-formamide); at 25 - 30℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
In acetonitrile; at 25 - 40℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
In dimethyl sulfoxide; at 25 - 40℃;Reactivity (does not react); Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
In tetrahydrofuran; at 25 - 40℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
In N-methylcaprolactam; at 25 - 40℃;Product distribution / selectivity; Inventive (E 3-E 10) and comparative (CE 1-CE 8) Examples : synthesis of compound 1:; The reactions are conducted according to the procedure given in detail for Example 3.
In 1,4-dioxane; water; N,N-dimethyl-aniline; isopropyl alcohol; c 4-(6-Acryloyloxyhexyloxy)benzoic acid 16.0 g (0.067 mole) 4-(6-hydroxyhexyloxy)benzoic acid is added to a solution of 9.34 mL (0.074 mole) N,N-dimethylaniline in 90 mL 1,4-dioxane. At 60° C., 6.01 mL (0.074 mole) of freshly distilled acryloyl chloride was added slowly dropwise. It was then stirred for 2 hours at 60° C. When water was added, the product precipitated as a white precipitate and was then filtered off. For purification, the product was recrystallized in 200 mL 2-propanol. After drying 14.6 g (75percent) of white crystals were obtained. Characterization: 1 H NMR (CDCl3): 1.45 (m, 4H); 1.70 (M, 2H); 1.80 (m, 2H); 4.00 (t, 2H); 4.15 (t, 2H); 5.80 (dd, 1H); 6.10 (dd, 1H); 6.38 (dd, 1H); 6.90 (d, 2H); 8.05 (d, 2H) ppm IR(KBr): 2940; 1730; 1688; 1607; 1431; 1410; 1315; 1296; 1198; 1169; 986; 770 cm-1
With 2,6-di-tert-butyl-4-methyl-phenol; N,N-dimethyl-aniline; In tetrahydrofuran; for 4h;Heating / reflux; In accordance with Scheme 3 below, an acrylic compound 3 having an oxetanyl group (acrylic compound 3) was synthesized. The 1H-NMR spectrum of the acrylic compound 3 is shown in Fig. 3.
1.66 g 3 g of the obtained compound E was dissolved in anhydrous tetrahydrofuran (THF,And 3.51 ml of triethylamine (Acros) was added thereto. The mixture was cooled to 0 ° C and stirred for 30 minutes.2.05 ml of acryloyl chloride (TCI) was dissolved in 12 ml of anhydrous tetrahydrofuran (THF, THF), stirred at 0 ° C for 1 hour, and then stirred for 24 hours while being warmed to room temperature.After completion of the reaction, the reaction mixture was removed under reduced pressure, and the resultant was subjected to column purification to obtain 1.66 g of compound F (4- (6- (acryloyloxy) hexyloxy) benzoic acid.

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