[ CAS No. 5536-61-8 ] {[proInfo.proName]}

Name: 5536-61-8|Sodium methacrylate|98%
Brand: Ambeed
SKU: A996470
Price: 5.0 USD
Availability: InStock
Rating: 91 (29 reviews)

,{[proInfo.pro_purity]}

Cat. No.: {[proInfo.prAm]}

2D 3D

Structure of 5536-61-8 * Storage: {[proInfo.prStorage]}

Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

For Research Only 110K+ Compounds Competitive Price 1-2 Day Shipping

Quality Control of [ 5536-61-8 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 5536-61-8 ]

SDS Specification

Alternatived Products of [ 5536-61-8 ]

Product Details of [ 5536-61-8 ]

CAS No. :	5536-61-8	MDL No. :	MFCD00045886
Formula :	C₄H₅NaO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	SONHXMAHPHADTF-UHFFFAOYSA-M
M.W :	108.07	Pubchem ID :	3255932
Synonyms :

Calculated chemistry of [ 5536-61-8 ]

Physicochemical Properties

Num. heavy atoms :	7
Num. arom. heavy atoms :	0
Fraction Csp3 :	0.25
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	20.7
TPSA :	40.13 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	No
P-gp substrate :	Yes
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.3 cm/s

Lipophilicity

Log Po/w (iLOGP) :	-5.12
Log Po/w (XLOGP3) :	0.93
Log Po/w (WLOGP) :	-0.69
Log Po/w (MLOGP) :	0.38
Log Po/w (SILICOS-IT) :	-0.03
Consensus Log Po/w :	-0.91

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	2.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-1.03
Solubility :	10.1 mg/ml ; 0.0933 mol/l
Class :	Very soluble
Log S (Ali) :	-1.36
Solubility :	4.73 mg/ml ; 0.0438 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	0.02
Solubility :	113.0 mg/ml ; 1.04 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.17

Safety of [ 5536-61-8 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 5536-61-8 ]

* 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.

Upstream synthesis route of [ 5536-61-8 ]
Downstream synthetic route of [ 5536-61-8 ]

[ 5536-61-8 ] Synthesis Path-Upstream 1~8

1
[ 5536-61-8 ]
[ 541-41-3 ]
[ 760-93-0 ]
[ 1609-47-8 ]
[ 21982-91-2 ]
[ 105-58-8 ]

Reference： [1] Patent: US6346650, 2002, B1, . Location in patent: Page column 6-7

2
[ 5536-61-8 ]
[ 541-41-3 ]
[ 760-93-0 ]
[ 21982-91-2 ]

Yield	Reaction Conditions	Operation in experiment
87.5%	With 4-methoxy-phenol In H₂O (water) < 309.3g; toluene 192g at 15℃; for 4 h;	309.3 g of an aqueous 33.5percent sodium methacrylate solution stabilized with 0.8 g of hydroquinone methyl ether are loaded in. 192 g of toluene are then introduced, followed by 0.02 mol of tetra-n-butylammonium bromide per mole of sodium methacrylate. 125.1 g of ethyl chloroformate are then introduced with stirring, while controlling the temperature of the medium at 15°C. (ethyl chloroformate/sodium methacrylate molar ratio: 1.2). The reaction progress is monitored as in Example 3. After reaction for 4 hours, the degree of conversion of the sodium methacrylate is greater than 99percent. The phases of the crude product are then separated out by settling but not washed, and stripped of volatiles under vacuum at a temperature of less than 35°C. The NMR analysis of the product stripped of volatiles is as follows: carboethoxymethacrylic anhydride 95.5percent methacrylic anhydride 4.5percent The yield of carboethoxymethacrylic anhydride is 87.5percent.

Reference： [1] Patent: US6346650, 2002, B1, . Location in patent: Page column 7
[2] Patent: US6346650, 2002, B1, . Location in patent: Page column 4-5
[3] Patent: US6346650, 2002, B1, . Location in patent: Page column 8

3
[ 5536-61-8 ]
[ 541-41-3 ]
[ 760-93-0 ]
[ 21982-91-2 ]
[ 105-58-8 ]

Yield	Reaction Conditions	Operation in experiment
80%	With 4-methoxy-phenol In water at 20℃; for 3 h;	445.1 g of aqueous 33.2percent sodium methacrylate solution stabilized with 1.2 g of hydroquinone methyl ether are loaded in. 8.8 g of tetra-n-butylammonium bromide (0.02 mol/mole of sodium methacrylate) are then introduced. Next, 193.2 g of ethyl chloroformate are introduced with stirring and while maintaining the temperature of the medium at 20 C. (ethyl chloroformate/sodium methacrylate molar ratio =1.3). The reaction mixture is left stirring while controlling the temperature at 20°C. The reaction progress is monitored by assaying the residual sodium methacrylate in the aqueous phase separated out by settling (the phases of the mixture separate out by settling as soon as the stirring is stopped). After reaction for 3 hours, the degree of conversion of the sodium methacrylate is greater than 99percent. The reactor is then emptied, the phases of the reaction mixture are separated by settling at room temperature, the organic phase is washed with 57 g of water and the washed organic phase is separated out by settling. 234.5 g of crude washed product are thus recovered, which product is stabilized with 0.02 g of di-tert-butyl-para-cresol. The excess chloroformate is removed under vacuum using a rotary evaporator at a temperature of less than 35°C. 198 g of carboethoxymethacrylic anhydride are obtained, the NMR purity of which is indicated, with the yield, in Table 2 below. Example 6 is repeated, varying the ethyl chloroformate/sodium methacrylate molar ratio. The results are reported in Table 2.

Reference： [1] Patent: US6346650, 2002, B1, . Location in patent: Page column 5-7
[2] Patent: US6346650, 2002, B1, . Location in patent: Page column 8
[3] Patent: US6346650, 2002, B1, . Location in patent: Page column 8

4
[ 5536-61-8 ]
[ 541-41-3 ]
[ 760-93-0 ]
[ 1609-47-8 ]
[ 21982-91-2 ]
[ 105-58-8 ]

Reference： [1] Patent: US6346650, 2002, B1, . Location in patent: Page column 6-7

5
[ 5536-61-8 ]
[ 2530-87-2 ]
[ 2530-85-0 ]

Yield	Reaction Conditions	Operation in experiment
88 %Chromat.	at 100℃; for 3 h;	COMPARATIVE EXAMPLES 1, 2, AND 4; EXAMPLES 3 AND 5-9; Comparative Example 1; This example was conducted without the use of polymerization inhibitors. To a 100 ml 4-neck round bottom flask fitted with a reflux condenser, thermocouple and magnetic stirrer was charged 4.98 grams (46 mmoles) of sodium methacrylate, 32.3 grams (163 mmoles) of chloropropyltrimethoxysilane and 0.10 grams (0.38 mmole) of hexaethylguanidinium chloride. The mixture was heated to 100° C. and held at that temperature for 3 hours. After this time the reaction mixture was cooled to room temperature and analyzed by gas chromatography. The crude reaction mixture was found to contain 29.2percent methacryloxytrimethoxysilane. This represents an 88percent yield based on the theoretical amount of contained product.
94 %Chromat.	With 4,4'-Methylenebis(2,6-di-tert-butylphenol) In chlorobenzene; xylene at 100℃; for 5 h;	Comparative Example 4; This example illustrates the alternate preparation of methacryloxypropyltrimethoxysilane using a diluent solvent and water wash (extraction) to remove by-product sodium chloride salt from the crude product. To a 1000 ml 4-neck round bottom flask fitted with a reflux condenser, thermocouple, and mechanical stirrer was charged 153.21 grams (1.42 moles) of sodium methacrylate, 0.59 grams (1.4 mmoles) Ethanox 702.(R)., 253.24 grams (1.27 moles) chloropropyltrimethoxysilane, and 112.33 grams of xylene. The mixture was heated to 100° C. At this temperature 38.66 grams of a 14.5percent solution of hexaethylgaunidinium chloride in chlorobenzene was added. The reaction mixture was held at 100° C. for 5 hours. The resultant dark purple solution was then cooled to 50° C. and 257.5 grams of de-ionized water was added to the reaction vessel and stirred until the salt dissolved. The flask contents were poured into a 1-liter separatory funnel and the water layer removed. The organic portion was analyzed by gas chromatography and found to contain 63.7 weight percent methacryloxypropyltrimethoxysilane (94percent of theory).
98 %Chromat.	at 100℃; for 5.5 h;	C. Use of Co-Dried Sodium Methacrylate and Hexaethylguanidinium Chloride; To a 500 ml 4-neck round bottom flask fitted with a reflux condenser, thermocouple, and mechanical stirrer was charged 45.29 grams of the sodium methacrylate/hexaethylgaunidinium chloride prepared in the above preparation. This mixture contains 0.797 grams (3.02 mmoles) of hexaethylgaunidinium chloride and 44.49 grams (412 mmole) of sodium methacrylate. Also charged to the reaction vessel was 122.89 grams (618 mmole) of chloropropyltrimethoxysilane and 0.16 (0.37 mmole) of Ethanox 702.(R).. This mixture was heated to 100° C. and held at that temperature for 5.5 hours. A sample of the crude reaction mixture contained 69.9 weight percent (98percent of theory) methacryloxypropyltrimethoxysilane as determined by gas chromatography.

98 %Chromat.	With 2,6-di-tert-butyl-4-methyl-phenol; 4,4'-Methylenebis(2,6-di-tert-butylphenol) In 1,2-dichloro-benzene at 100℃; for 4 h;	Comparative Example 2; This example was conducted with the use of polymerization inhibitors. To a 250 ml 4-neck round bottom flask fitted with a reflux condenser, thermocouple, and mechanical stirrer was charged 31.34 grams (290 mmole) of sodium methacrylate, 83.22 g (419 mmoles) chloropropyltrimethoxysilane, 0.04 grams of 2,6-di-t-butyl-4-methylphenol (BHT, 0.18 mmole), 0.12 grams of Ethanox 702.(R)., and 6.0 grams of a 20percent solution of hexaethylguanidinium chloride in o-dichlorobenzene (1.2 grams hexaethylguanidinium chloride, (4.5 mmole). This mixture was heated to 100° C. for 4 hours. After this time the resultant dark purple solution was analyzed by gas chromatography and found to contain 68.0percent of methacryloxypropyltrimethoxysilane (98percent of theory).
72.3 %Chromat.	at 110℃; for 3 h;	Example 5; This example illustrates the use of sodium methoxide as the neutralizing base. To a 500 ml 4-neck round bottom flask equipped with a reflux condenser, addition funnel, thermocouple and magnetic stirrer was charged 38.67 grams (0.45 moles) of methacrylic acid and 52.12 grams of methanol. To the addition funnel was charged 95.89 grams of a 25percent solution of sodium methoxide in methanol (23.97 grams of contained sodium methoxide, 0.44 moles, 98.6percent of theoretical). The sodium methoxide solution was slowly added to the methacrylic acid over a 1.3 hour period with vigorous stirring. Near the end of the addition the amount of formed solids made stirring difficult. After all of the sodium methoxide solution was charged, the addition funnel was rinsed with 17.53 grams of methanol. To the resulting thick slurry was added 3.21 grams of a 34percent aqueous solution of hexaethylguanidinium chloride solution (1.09 grams of contained hexaethylguanidinium chloride, 4.1 mmoles). This material was rinsed into the reaction flask with 7.58 grams of methanol. The methanol was removed by mildly heating the reaction slurry under vacuum. The remaining paste was further dried by heating in a vacuum oven at 90° C. and 125 mmHg overnight. The resulting dry solids were broken up with a spatula and the reaction flask fitted with a reflux condenser, thermocouple and mechanical stirrer. To the solids were added 0.192 grams (0.45 mmoles) of 4,4'-methylenebis(2,6-di-t-butylphenol), 0.081 grams (0.36mmoles) of butylated hydroxytoluene (BHT) and 131.58 grams (0.66 moles) of chloropropyltrimethoxysilane. The mixture was then heated to 110° C. for 3 hours. During this time the color of the reaction mixture changes from purple to yellow. Analysis of the final product by gas chromatograpy indicated that the crude reaction mixture contained 72.3percent of the desired gamma-methacryloxypropyltrimethoxysilane.

Reference： [1] Patent: US2007/32673, 2007, A1, . Location in patent: Page/Page column 4
[2] Patent: US2007/32673, 2007, A1, . Location in patent: Page/Page column 4-5
[3] Patent: US2007/32673, 2007, A1, . Location in patent: Page/Page column 4
[4] Patent: US2007/32673, 2007, A1, . Location in patent: Page/Page column 4
[5] Patent: US2007/32673, 2007, A1, . Location in patent: Page/Page column 5

6
[ 5536-61-8 ]
[ 100-39-0 ]
[ 2495-37-6 ]

Reference： [1] Patent: US2018/57429, 2018, A1, . Location in patent: Page/Page column 0087-0088

7
[ 79-41-4 ]
[ 5536-61-8 ]

Yield	Reaction Conditions	Operation in experiment
92.2%	With sodium hydroxide In water; acetone	Example 2 Preparation of Sodium Methacrylate A 12.23 g (0.3058 mol) sample of sodium hydroxide was placed in a 50-ml Erlenmayer flask equipped with 10 ml water and a magnetic stirring bar, and the mixture was stirred to dissolution. The sodium hydroxide solution was then poured into a 250-ml beaker containing 30.70 g (0.3570 mol) methacrylic acid (exothermic reaction) with constant stirring. The mixture was allowed to cool, 50 ml of acetone were added, and the precipitate vacuum filtered. The recovered carboxylate salt was first allowed to air dry under a hood, and then dried in an oven at 55°-60° C. for 12-15 hours to afford 30.43 g (92.2percent yield) of sodium methacrylate.

Reference： [1] Patent: US5491244, 1996, A,
[2] Patent: US5380884, 1995, A,
[3] Patent: US4755262, 1988, A,
[4] Patent: US2007/32673, 2007, A1, . Location in patent: Page/Page column 4
[5] Patent: US2007/32673, 2007, A1, . Location in patent: Page/Page column 5

8
[ 760-93-0 ]
[ 71-00-1 ]
[ 5536-61-8 ]
[ 13282-13-8 ]

Reference： [1] Langmuir, 2016, vol. 32, # 25, p. 6544 - 6550

[ 5536-61-8 ] Synthesis Path-Downstream 1~88

1
[ 1719-57-9 ]
[ 5536-61-8 ]
[ 15946-98-2 ]

Reference： [1]Journal of general chemistry of the USSR,1977,vol. 47,p. 1304 - 1305
Zhurnal Obshchei Khimii,1977,vol. 47,p. 1423 - 1424

2
[ 994-30-9 ]
[ 5536-61-8 ]
[ 17985-46-5 ]

Reference： [1]Macromolecules,2011,vol. 44,p. 9108 - 9117
[2]Journal of general chemistry of the USSR,1960,vol. 30,p. 2763 - 2765
Zhurnal Obshchei Khimii,1960,vol. 30,p. 2782 - 2784
[3]Russian Journal of General Chemistry,1996,vol. 66,p. 1257 - 1259

3
[ 2401-73-2 ]
[ 5536-61-8 ]
[ 2003-87-4 ]

Reference： [1]Journal of general chemistry of the USSR,1965,vol. 35,p. 758
Zhurnal Obshchei Khimii,1965,vol. 35,p. 756

4
[ 3582-71-6 ]
[ 5536-61-8 ]
[ 1873-78-5 ]

Reference： [1]Journal of general chemistry of the USSR,1965,vol. 35,p. 758
Zhurnal Obshchei Khimii,1965,vol. 35,p. 756

5
[ 2474-02-4 ]
[ 5536-61-8 ]
[ 1873-79-6 ]

Reference： [1]Journal of general chemistry of the USSR,1965,vol. 35,p. 758
Zhurnal Obshchei Khimii,1965,vol. 35,p. 756

6
[ 14741-59-4 ]
[ 5536-61-8 ]
[ 1873-80-9 ]

Reference： [1]Journal of general chemistry of the USSR,1965,vol. 35,p. 758
Zhurnal Obshchei Khimii,1965,vol. 35,p. 756

7
[ 20614-18-0 ]
[ 5536-61-8 ]
[ 32813-69-7 ]

Reference： [1]Journal of Organic Chemistry USSR (English Translation),1971,vol. 7,p. 984 - 988
Zhurnal Organicheskoi Khimii,1971,vol. 7,p. 967 - 971

8
[ 32813-77-7 ]
[ 5536-61-8 ]
[ 32813-72-2 ]

Reference： [1]Journal of Organic Chemistry USSR (English Translation),1971,vol. 7,p. 984 - 988
Zhurnal Organicheskoi Khimii,1971,vol. 7,p. 967 - 971

9
[ 39074-38-9 ]
[ 5536-61-8 ]
[ 50888-17-0 ]

Reference： [1]Patent: DE2214057,1973,
Chem.Abstr.,1974,vol. 80

10
[ 20614-19-1 ]
[ 5536-61-8 ]
[ 32813-75-5 ]

Reference： [1]Journal of Organic Chemistry USSR (English Translation),1971,vol. 7,p. 984 - 988
Zhurnal Organicheskoi Khimii,1971,vol. 7,p. 967 - 971

11
[ 5536-61-8 ]
[ 75-78-5 ]
[ 6999-46-8 ]

Reference： [1]Journal of general chemistry of the USSR,1960,vol. 30,p. 2763 - 2765
Zhurnal Obshchei Khimii,1960,vol. 30,p. 2782 - 2784

12
[ 5536-61-8 ]
[ 1719-53-5 ]
[ 6999-47-9 ]

Reference： [1]Journal of general chemistry of the USSR,1960,vol. 30,p. 2763 - 2765
Zhurnal Obshchei Khimii,1960,vol. 30,p. 2782 - 2784

13
[ 5536-61-8 ]
[ 1558-33-4 ]
[ 63696-08-2 ]

Reference： [1]Journal of general chemistry of the USSR,1977,vol. 47,p. 1304 - 1305
Zhurnal Obshchei Khimii,1977,vol. 47,p. 1423 - 1424

14
[ 186581-53-3 ]
[ 17342-77-7 ]
[ 5536-61-8 ]
[ 71674-93-6 ]
[ 4513-62-6 ]
[ 87817-19-4 ]
[ 139623-17-9 ]

Reference： [1]Journal of the Chemical Society. Chemical communications,1992,p. 105 - 106

15
[ 17342-77-7 ]
[ 5536-61-8 ]
[ 10297-25-3 ]
[ 5363-70-2 ]
[ 87817-18-3 ]
hex-1-ene-2,4-dicarboxylic acid [ No CAS ]

Reference： [1]Journal of the Chemical Society. Chemical communications,1992,p. 105 - 106

16
[ 5536-61-8 ]
[ 76899-07-5 ]
[ 129441-36-7 ]

Reference： [1]Heterocycles,1990,vol. 30,p. 567 - 581

17
[ 5536-61-8 ]
[ 21988-86-3 ]
[ 77361-96-7 ]

Reference： [1]Heterocycles,1981,vol. 16,p. 243 - 246

18
[ 5536-61-8 ]
[ 344883-86-9 ]
[ 85673-26-3 ]

Reference： [1]Journal of the American Chemical Society,1983,vol. 105,p. 6712 - 6714

19
[ 5536-61-8 ]
[ 344901-59-3 ]
[ 87282-44-8 ]

Reference： [1]Journal of the American Chemical Society,1983,vol. 105,p. 6712 - 6714

20
[ 110-52-1 ]
[ 5536-61-8 ]
[ 21217-78-7 ]

Reference： [1]Macromolecules,2003,vol. 36,p. 7552 - 7559

21
Locust Bean Gum-graft-6-O-(2-bromopropyl)-2-yl-carboxy, M_n = 36050 (SEC), M_w = 64580 (SEC), PDI = 1.79 (SEC) [ No CAS ]
[ 5536-61-8 ]
Locust Bean Gum-graft-methacrylate, atom transfer radical polymerisation [ No CAS ]

Reference： [1]Chemical Communications,2007,p. 362 - 364

22
[ 1032820-90-8 ]
[ 79-41-4 ]
[ 5536-61-8 ]
C₁₉H₄₂O₆Si₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With 4-methoxy-phenol; at 100℃; for 8h;	EXAMPLE 4-4; [00200] Into a 100 mL recovery flask, methanol (10.3 g), n-hexane (10.1 g) and distilled water (20.0 g) were added and cooled to 0 0C in ice-bath. A mixture of 3- glycidoxypropyldimethoxymethylsilane (15.06 g, 0.068 mol) and dimethylethylsilylchloride (33.7 g, 0.27 mol) was added dropwise for 1 hour. After addition, the reaction mixture was stirred at 0 C for 2 hours. The organic layer was washed with sat. NaHCO3 aq. (50 mL) and with sat. NaCl aq. (50 mL) and repeat to wash with the same solutions again. The mixture was dried with anhydrous Na2SO4. After filtration of sodium sulfate, the solvent was evaporated. The crude material was purified by vacuum distillation (115 - 118 0C / 0.2 mmHg) and was obtained as the silicone compound represented by the Formula below.[00201] Potassium hydroxide (6.19 g, 0.11 mol) in 50 wt% methanol aqueous solution (12.6 mL) was cooled to O 0C. 3-(3-chloro-2- hydroxypropyloxy)propylbis(dimethylethylsiloxy)methylsilane (25.0 g, 0.062 mol) obtained above was added in one portion. The mixture was allowed to room temperature and stirred at room temperature for 18 hours. Distilled water (60 mL) was added to the reaction mixture and the organic layer was put aside. The aqueous layer was extracted with diethyl ether (60 mL) twice. The extracts and the organic layer were put together and washed with distilled water (100 mL) three times and dried with anhydrous Na2SO4, filtered, evaporated. The crude material was purified with distillation (108 - 113 C / 0.2 mmHg) and was obtained as the silicone compound represented by the Formula below. <n="56"/>[00202] A mixture of p-methoxyphenol (13.5 mg, 0.12 mmol), <strong>[5536-61-8]sodium methacrylate</strong>(0.4 g, 3.70 mmol), 3-glycidoxypropylbis(dimethylethylsiloxy)methylsilane (4.5 g, 12.3 mmol) obtained above and methacrylic acid (4.2 mL, 49.4 mmol) was stirred at 100 0C for 8 hours. Diethyl ether (40 mL) was added. The mixture was washed with IN sodium hydroxide aqueous solution (5 x 20 mL) and with sat. NaCl aq. (2 x 20 mL) and dried with anhydrous Na2SO4. After filtration of sodium sulfate, the mixture was evaporated and the crude material was obtained. The material was purified by silica gel column chromatography (silica gel 22 g, hexane / ethyl acetate = 1 / 0, 19 / 1, 15 / 1, 9 / 1, 4 / 1, 3 / 1, 3 / 1 (40 mL of each)) and was obtained as the silicone compound represented by the Formula (4p4).

Reference： [1]Patent: WO2008/42163,2008,A1 .Location in patent: Page/Page column 54-55

23
[ 5536-61-8 ]
[ 541-41-3 ]
[ 760-93-0 ]
[ 1609-47-8 ]
[ 21982-91-2 ]
[ 105-58-8 ]

Yield	Reaction Conditions	Operation in experiment
		Example 6 is repeated, varying the ethyl chloroformate/<strong>[5536-61-8]sodium methacrylate</strong> molar ratio. The results are reported in Table 2.

Reference： [1]Patent: US6346650,2002,B1 .Location in patent: Page column 6-7

24
[ 5536-61-8 ]
[ 541-41-3 ]
[ 760-93-0 ]
[ 21982-91-2 ]

Yield	Reaction Conditions	Operation in experiment
87.5%	With 4-methoxy-phenol;tetrabutylammomium bromide; In H2O (water) < 309.3g; toluene 192g; at 15℃; for 4h;	309.3 g of an aqueous 33.5% sodium methacrylate solution stabilized with 0.8 g of hydroquinone methyl ether are loaded in. 192 g of toluene are then introduced, followed by 0.02 mol of tetra-n-butylammonium bromide per mole of sodium methacrylate. 125.1 g of ethyl chloroformate are then introduced with stirring, while controlling the temperature of the medium at 15C. (ethyl chloroformate/sodium methacrylate molar ratio: 1.2). The reaction progress is monitored as in Example 3. After reaction for 4 hours, the degree of conversion of the sodium methacrylate is greater than 99%. The phases of the crude product are then separated out by settling but not washed, and stripped of volatiles under vacuum at a temperature of less than 35C. The NMR analysis of the product stripped of volatiles is as follows: carboethoxymethacrylic anhydride 95.5% methacrylic anhydride 4.5% The yield of carboethoxymethacrylic anhydride is 87.5%.
	With 4-methoxy-phenol; In water; at 5 - 35℃; for 7 - 30h;	408 g of an aqueous 26.5% sodium methacrylate solution, into which are introduced 900 mg of hydroquinone methyl ether, are introduced into a jacketed reactor whose temperature is maintained with the aid of a circulation of water thermostatically adjusted to 20C.; next, 162.8 g of ethyl chloroformate (ethyl chloroformate/sodium methacrylate molar ratio: 1.5:1) are introduced over 5 minutes. The heterogeneous mixture is stirred for 15 hours. The phases are then separated by settling at room temperature. The organic phase is dried over calcium sulphate and the volatiles are then stripped off under vacuum at a temperature of less than 35C., in order to remove the excess chloroformate. 153 g of product are thus obtained (yield: 96.7%) in a carboethoxymethacrylic anhydride NMR purity of 95%, the remaining 5% consisting of methacrylic. Example 1 is repeated, modifying the temperature and the ethyl chloroformate/sodium methacrylate molar ratio. The results are reported in Table 1.
	tributylphenylphosphonium chloride; at 10℃; for 3h;	Example 6 is repeated, working at 10 C. and varying the nature of the phase-transfer catalyst, which is introduced in an amount of 0.01 mol/mole of sodium methacrylate.

Reference： [1]Patent: US6346650,2002,B1 .Location in patent: Page column 7
[2]Patent: US6346650,2002,B1 .Location in patent: Page column 4-5
[3]Patent: US6346650,2002,B1 .Location in patent: Page column 8

25
[ 5536-61-8 ]
[ 541-41-3 ]
[ 760-93-0 ]
[ 21982-91-2 ]
[ 105-58-8 ]

Yield	Reaction Conditions	Operation in experiment
80 - 85.5%	With 4-methoxy-phenol;tetrabutylammomium bromide; In water; at 20℃; for 3h;	445.1 g of aqueous 33.2% sodium methacrylate solution stabilized with 1.2 g of hydroquinone methyl ether are loaded in. 8.8 g of tetra-n-butylammonium bromide (0.02 mol/mole of sodium methacrylate) are then introduced. Next, 193.2 g of ethyl chloroformate are introduced with stirring and while maintaining the temperature of the medium at 20 C. (ethyl chloroformate/sodium methacrylate molar ratio =1.3). The reaction mixture is left stirring while controlling the temperature at 20C. The reaction progress is monitored by assaying the residual sodium methacrylate in the aqueous phase separated out by settling (the phases of the mixture separate out by settling as soon as the stirring is stopped). After reaction for 3 hours, the degree of conversion of the sodium methacrylate is greater than 99%. The reactor is then emptied, the phases of the reaction mixture are separated by settling at room temperature, the organic phase is washed with 57 g of water and the washed organic phase is separated out by settling. 234.5 g of crude washed product are thus recovered, which product is stabilized with 0.02 g of di-tert-butyl-para-cresol. The excess chloroformate is removed under vacuum using a rotary evaporator at a temperature of less than 35C. 198 g of carboethoxymethacrylic anhydride are obtained, the NMR purity of which is indicated, with the yield, in Table 2 below. Example 6 is repeated, varying the ethyl chloroformate/sodium methacrylate molar ratio. The results are reported in Table 2.
	tetrabutyl phosphonium bromide; at 10℃; for 4.5h;	Example 6 is repeated, working at 10 C. and varying the nature of the phase-transfer catalyst, which is introduced in an amount of 0.01 mol/mole of sodium methacrylate.
	methyl(tri-n-octyl)ammonium bromide; at 10℃; for 1.5h;	Example 6 is repeated, working at 10 C. and varying the nature of the phase-transfer catalyst, which is introduced in an amount of 0.01 mol/mole of sodium methacrylate.

Reference： [1]Patent: US6346650,2002,B1 .Location in patent: Page column 5-7
[2]Patent: US6346650,2002,B1 .Location in patent: Page column 8
[3]Patent: US6346650,2002,B1 .Location in patent: Page column 8

26
chloropropylsilane-octylsilane co-oligomer [ No CAS ]
[ 5536-61-8 ]
the chloropropylsilane-octylsilane co-oligomer with sodium methacrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N,N'-diphenyl-1,4-phenylenediamine; In DMF (N,N-dimethyl-formamide); at 115℃; for 12h;	[0065] 102 g of the co-oligomer from Example 2, 30 g of <strong>[5536-61-8]sodium methacrylate</strong> and 50 mg of N,N'-diphenyl-p-phenylenediamine in 100 ml of DMF are placed in a 1 liter capacity autoclave equipped with stirrer. After rendering the contents inert by forcing in nitrogen twice, the contents are stirred for 12 hours at 115 C. under the intrinsic pressure. After cooling to room temperature, filtering off the precipitated sodium chloride, removing the ethanol from the filtrate and renewed filtration, 112 g of a clear colorless liquid are obtained. [0066] 1H-NMR (CDCl3): delta 0.60 (m, 2 H, Si-CH2-(CH2)6-CH3), 0.70 (m, 2 H, Si-CH2-CH2-CH2-O-C(O)-C(CH3)CH2)), 0.95 (t, 3 H, 3JH-H=7 Hz, Si-CH2-(CH2)6-CH3), 1.20 (m, 12 H, CH3-CH2-O-Si), 1.3-1.5 (m, 12 H, Si-CH2-(CH2)6-CH3), 1.80 (m, 2 H, Si-CH2-CH2-CH2-O-C(O)-C(CH3)CH2), 2.00 (m, 3 H, Si-CH2-CH2-CH2-O-C(O)-C(CH3)CH2), 3.80 (m, 8 H, CH3-CH2--O-Si), 4.15 (m, 2 H, Si-CH2-CH2-CH2-O-C(O)-C(CH3)CH2), 5.50 and 6.10 (2 s, H Si-CH2-CH2-CH2-O-C(O)-C(CH3)CH2).

Reference： [1]Patent: US2004/158090,2004,A1 .Location in patent: Page 4

27
[ 79-41-4 ]
[ 7422-52-8 ]
[ 5536-61-8 ]
[ 69861-02-5 ]
C₂₈H₅₈O₁₁Si₄ [ No CAS ]
C₃₁H₆₆O₁₁Si₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With 4-methoxy-phenol; at 90℃; for 15h;Conversion of starting material;	To a three-neck, 125 mL round bottom reaction flask equipped with a magnetic stir bar, condenser with an attached drying tube, and a thermocouple, was added 6.88 gm methacrylic acid and methacrylic acid salt listed in Table 2, in the amounts listed in Table 2. The reaction was stirred. With stirring, was added 13.44 g Epoxide (obtained from Silar, 40 MMOL). The reaction mixture was heated to 90 C. After fourteen hours, the reaction mixture was removed from heat, allowed to cool to about 50 C and transferred to a separatory funnel using No.21. 5 mL hexanes for transfer and to dilute the mixture. The hexanes layer was washed successively with 3 X No.33. 3 ML 0.5 N aqueous NAOH, and 3x 33.3 mL 2.5 weight % aqueous NACL. The organic layer was then dried over NA2S04 and filtered. The resulting SIMAA2 was analyzed by LC-MS for purity. Purity results are listed in Table 2, below.
	With 4-methoxy-phenol; In toluene; at 90℃; for 15h;Conversion of starting material;	To a three-neck, 125 mL round bottom reaction flask equipped with a magnetic stir bar, condenser with an attached drying tube, and a thermocouple, was added 6.88 gm methacrylic acid and methacrylic acid salt listed in Table 2, in the amounts listed in Table 2. The reaction was stirred. With stirring, was added 13.44 g Epoxide (obtained from Silar, 40 MMOL). The reaction mixture was heated to 90 C. After fourteen hours, the reaction mixture was removed from heat, allowed to cool to about 50 C and transferred to a separatory funnel using No.21. 5 mL hexanes for transfer and to dilute the mixture. The hexanes layer was washed successively with 3 X No.33. 3 ML 0.5 N aqueous NAOH, and 3x 33.3 mL 2.5 weight % aqueous NACL. The organic layer was then dried over NA2S04 and filtered. The resulting SIMAA2 was analyzed by LC-MS for purity. Purity results are listed in Table 2, below.

Reference： [1]Patent: WO2005/5445,2005,A1 .Location in patent: Page/Page column 9
[2]Patent: WO2005/5445,2005,A1 .Location in patent: Page/Page column 9

28
[ 5536-61-8 ]
AF-343 [ No CAS ]
4-(3-[(7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)phenylamino]phenoxy)ethyl-2-methylprop-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20%	With potassium iodide; In N,N-dimethyl-formamide; at 20℃;	EXAMPLE 13 4-(3-[(7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)phenylamino]phenoxy) ethyl-2-methylprop-2-enoate A mixture of N-3-(2-bromoethoxy)-phenyl-7-(benzothiazol-2-yl)-9,9-diethylfluoren-2-amine (Example 11, 1.26 g, 2.0 mmol.), <strong>[5536-61-8]methacrylic acid sodium salt</strong> (1.08 g, 10 mmol.), potassium iodide (0.075 g, 0.45 mmol.) and dimethylformamide (10 ml), was stirred under nitrogen at room temperature for a week, and poured onto water. The separated yellow solids were filtered, washed with water and air-dried. These were then transferred to a column of silica gel and the column was eluted with 3:1 toluene-heptane to recover the unreacted starting material, 0.25 g, (20%), m.p. 135.5-137.5 C. Elution with toluene gave the product, which was recrystallized from hexanes, 0.75 g, (58% yield), m.p. 169.5-171 C. DSC showed only melting, and no exotherm until 250 C. Mass spectrum (m/z):650 (M+). IR (KBr): 1719 cm-1. 1H NMR (delta ppm in CDCl3): 0.35, 0.38, 0.41 (t, 6H, methyls on the fluorene), 1.93 (s, 3H, Methyl), 1.90-2.11 (m, 4H, methylenes), 4.09-4.13 (m, 2H, OCH2), 4.41-4.45 (m, 2H, OCH2), 5.56,5.57 (d, 1H, olefinic), 6.11,6.12 (d, 1H, olefinic), 6.57-6.74 (m, 2 ArH), 7.02-8.09 (m, 17 ArH). 13C NMR (delta in ppm; CDCl3): 8.61, 12.29, 32.63, 56.41, 63.04, 65.86 (sp3C) 108.85, 110.12, 116.69, 119.05, 119.39, 121.03, 121.44, 121.52, 122.93, 123.11, 123.57, 124.52, 124.95, 126.04, 126.27, 127.28, 129.27, 129.90, 131.52, 134.91, 135.55, 135.92, 144.42, 147.61, 147.90, 149.17, 150.67, 152.05, 154.24, 159.45, 167.25, 168.81 (sp2 C). Anal. Calcd for C42H38N2SO3: C, 77.51%; H, 5.89%; N, 4.30%, S, 4.93%. Found: C, 77.63%, H, 5.81%, N, 4.66%, S, 4.80%.

Reference： [1]Patent: US7067674,2006,B1 .Location in patent: Page/Page column 8

29
[ 894085-34-8 ]
[ 5536-61-8 ]
4-(3-[(7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)phenylamino]phenoxy)butyl-2-methylprop-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With Aliquat 336; In water; toluene; at 70℃; for 48h;	EXAMPLE 14; 4-(3-[(7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)phenylamino]phenoxy) butyl-2-methylprop-2-enoate; A mixture of <strong>[5536-61-8]sodium methacrylate</strong> (2.715 g, 25.1 mmol.), N-3-(4-bromobutyloxy)phenyl-N-phenyl-7-(benzothiazol-2-yl)-9,9-diethylfluoren-2-amine (3.556 g, 5.29 mmol), Aliquat-336 (tricaprylmethyl ammonium chloride; 0.25 g, 0.62 mmol.), toluene (10 ml) and water (10 ml) was kept at 70 C. for a total of 48 hours. To the mixture, additional amounts of <strong>[5536-61-8]sodium methacrylate</strong> (1.35 g, 12.5 mmol. and 1.30 g, 12.0 mmol.), were added after 24 and 30 hours respectively. The mixture was cooled, diluted with toluene, toluene phase was washed with water, dried and concentrated to get a pale yellow viscous liquid, 4,34 g. This was transferred to a column of silica gel, and elution of the column with toluene gave the methacrylate as a yellow brittle glass, 1.78 g, (51% yield), melting range, 60.4-65 C. The DSC did not show any melting, but showed an exotherm at 137 C. Mass spectrum (m/z):678 (M+). IR (KBr): 1715 cm-1. 1H NMR (delta ppm in CDCl3): 0.35, 0.38, 0.41 (t, 6H, methyls), 1.82-2.14 (m, 11H, methyl and methylenes), 3.88 (br t, 2H, OCH2), 4.18 (br t, 2H, OCH2), 5.52-5.31 (m, 1H, olefinic), 6.08 (s, 1H, olefinic), 6.55-6.71 (m, 3 ArH), 7.01-7.52 (m, 10 ArH), 7.60-7.70 (m, 2 ArH), 7.88-8.09 (m, 4 ArH). 13C NMR (delta ppm in CDCl3): 8.61, 18.32, 25.37, 25.92, 32.63, 56.41, 64.28, 67.13 (sp3C), 108.85, 110.00, 116.40, 118.96, 119.39, 121.00, 121.41, 121.52, 122.94, 122.99, 123.48, 124.43, 124.95, 125.35, 126.28, 127.28, 129.24, 129.85, 131.49, 134.91, 135.43, 136.35, 144.48, 147.70, 147.99, 149.05, 150.67, 152.02, 154.24, 159.80, 167.40, 168.81.(sp2C). Anal. Calcd. for C44H42N2O3S: C, 77.84%; H, 6.23%; N, 4.12%; S, 4.72%. Found: C, 77.81%, H, 6.31%; N, 4.12%; S, 4.66%.

Reference： [1]Patent: US7067674,2006,B1 .Location in patent: Page/Page column 8-9

30
[ 894085-35-9 ]
[ 5536-61-8 ]
4-(3-[(7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)phenylamino]phenoxy)-hexyl-2-methylprop-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
48%	With benzyltri(n-butyl)ammonium chloride; In water; toluene; at 70℃; for 120h;	EXAMPLE 15 4-(3-[(7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)phenylamino]phenoxy) hexyl-2-methylprop-2-enoate A mixture of N-3-(6-bromohexyloxy)-phenyl-N-phenyl-7-(benzothiazol-2-yl)-9,9-diethylfluoren-2-amine (3.51 g, 5 mmol.), <strong>[5536-61-8]sodium methacrylate</strong> (2.71 g, 25 mmol.), benzyl tributylammonium chloride (0.161 g, 0.52 mmol.), toluene (10 ml) and water (10 ml) was kept at 70 C. for 5 days. During this period, additional amounts of <strong>[5536-61-8]sodium methacrylate</strong> (1.35 g, 12.5 mmol., and 0.62 g, (6 mmol.) were added on the third and fourth day of the reaction. The reaction was then cooled, diluted with toluene; toluene phase was washed with water, dried and concentrated to get 3.70 g of a yellow viscous liquid. This was chromatographed over silica gel and elution with toluene gave the product, 1.70 g, (48%), as a viscous liquid. Mass spectrum (m/z):706 (M+). IR (KBr): 1726 cm-1. 1H NMR (delta in ppm; CDCl3): 0.38 (t, 6H), 1.40-1.44 (m, 4H), 1.65-1.75 (m, 4H), 1.90-2.11 (m, 4H), 3.84 (t, 2H), 4.13 (t, 2H), 5.52 (t, 1H), 6.08 (s, 1H), 6.56-6.71 (m, 3 ArH), 7.03-7.51 (m, 10 ArH), 7.59-7.70 (m, 2ArH), 7.87-8.09 (m, 4 ArH). 13C NMR (delta in ppm): 8.61, 18.32, 25.77, 28.51, 29.14, 32.60, 56.39, 64.59, 67.62 (sp3C), 108.91, 110.03, 116.28, 118.90, 119.34, 120.98, 121.38, 121.50, 122.94, 123.45, 124.40, 124.92, 125.21, 126.25, 127.25, 129.21, 129.79, 131.46, 134.89, 135.38, 136.41, 144.45, 147.67, 147.99, 149.00, 150.64, 151.99, 154.21, 159.94, 167.46, 168.78 (sp2C). Anal. Calcd. for C46H46N2O3S: C, 78.15%; H, 6.55%, N, 3.93%, S, 4.53%. Found: C, 78.14%; H, 6.52%; N, 3.78%; S, 4.56%.

Reference： [1]Patent: US7067674,2006,B1 .Location in patent: Page/Page column 10

31
[ 79-41-4 ]
[ 5536-61-8 ]

Yield	Reaction Conditions	Operation in experiment
92.2%	With sodium hydroxide; In water; acetone;	Example 2 Preparation of Sodium Methacrylate A 12.23 g (0.3058 mol) sample of sodium hydroxide was placed in a 50-ml Erlenmayer flask equipped with 10 ml water and a magnetic stirring bar, and the mixture was stirred to dissolution. The sodium hydroxide solution was then poured into a 250-ml beaker containing 30.70 g (0.3570 mol) methacrylic acid (exothermic reaction) with constant stirring. The mixture was allowed to cool, 50 ml of acetone were added, and the precipitate vacuum filtered. The recovered carboxylate salt was first allowed to air dry under a hood, and then dried in an oven at 55-60 C. for 12-15 hours to afford 30.43 g (92.2% yield) of sodium methacrylate.
	With sodium hydroxide;	Example 1 Preparation of sodium methacrylate: After 5 kg (37.5 mol) of a 30% aqueous solution of sodium hydroxide was cooled below 60 C., 3.23 kg (37.5 mol) of methacrylic acid was added drop by drop while stirring. The aqueous solution of sodium methacrylate obtained by the neutralization reaction was spray-dried with 300 C. hot air to yield 4.04 kg of a dry powder of sodium methacrylate. The water content of this powder was 0.08%.
	With sodium hydroxide;	EXAMPLE 1 Sodium methacrylate was synthesised by the neutralization of 119.5 g (1.389 mols) of methacrylic acid with 55.5 g (1.389 mols) of sodium hydroxide. A mixture consisting of 150.0 g of substantially anhydrous sodium methacrylate obtained by dehydrating the product of the neutralization and 642.4 g (6.945 mols) of epichlorohydrin was placed in a flask provided with a stirrer, a thermometer, and a reflux condenser.

	With sodium hydroxide; In water; at 20 - 50℃; for 2.5h;Product distribution / selectivity;	Example 3; A. Preparation of Sodium Methacrylate Solution; To a five liter 4-neck round bottom flask fitted with a reflux condenser, thermocouple, and mechanical stirrer was charged 1500.11 grams of de-ionized water. To this was incrementally added a total of 511.63 grams (12.79 moles) of sodium hydroxide pellets. The addition rate was such that the pot temperature did not exceed 50 C. After the solution cooled to room temperature, 1115.40 grams (12.82 moles) of methacrylic acid was added over the course of 2.5 hours. The temperature of the reaction mixture was kept below 50 C. throughout the methacrylic acid addition. This preparation resulted in a clear, colorless solution containing 44.1% by weight sodium methacrylate.
	With sodium methylate; In methanol; for 1.3h;Product distribution / selectivity;	Example 5; This example illustrates the use of sodium methoxide as the neutralizing base. To a 500 ml 4-neck round bottom flask equipped with a reflux condenser, addition funnel, thermocouple and magnetic stirrer was charged 38.67 grams (0.45 moles) of methacrylic acid and 52.12 grams of methanol. To the addition funnel was charged 95.89 grams of a 25% solution of sodium methoxide in methanol (23.97 grams of contained sodium methoxide, 0.44 moles, 98.6% of theoretical). The sodium methoxide solution was slowly added to the methacrylic acid over a 1.3 hour period with vigorous stirring. Near the end of the addition the amount of formed solids made stirring difficult. After all of the sodium methoxide solution was charged, the addition funnel was rinsed with 17.53 grams of methanol. To the resulting thick slurry was added 3.21 grams of a 34% aqueous solution of hexaethylguanidinium chloride solution (1.09 grams of contained hexaethylguanidinium chloride, 4.1 mmoles). This material was rinsed into the reaction flask with 7.58 grams of methanol. The methanol was removed by mildly heating the reaction slurry under vacuum. The remaining paste was further dried by heating in a vacuum oven at 90 C. and 125 mmHg overnight. The resulting dry solids were broken up with a spatula and the reaction flask fitted with a reflux condenser, thermocouple and mechanical stirrer. To the solids were added 0.192 grams (0.45 mmoles) of 4,4'-methylenebis(2,6-di-t-butylphenol), 0.081 grams (0.36mmoles) of butylated hydroxytoluene (BHT) and 131.58 grams (0.66 moles) of chloropropyltrimethoxysilane. The mixture was then heated to 110 C. for 3 hours. During this time the color of the reaction mixture changes from purple to yellow. Analysis of the final product by gas chromatograpy indicated that the crude reaction mixture contained 72.3% of the desired gamma-methacryloxypropyltrimethoxysilane.

Reference： [1]Patent: US5491244,1996,A
[2]Patent: US5380884,1995,A
[3]Patent: US4755262,1988,A
[4]Patent: US2007/32673,2007,A1 .Location in patent: Page/Page column 4
[5]Patent: US2007/32673,2007,A1 .Location in patent: Page/Page column 5

32
[ 109911-78-6 ]
[ 74-31-7 ]
[ 5536-61-8 ]
[ 2530-87-2 ]
[ 7727-32-4 ]

Yield	Reaction Conditions	Operation in experiment
90.3%		EXAMPLE 3 54 g (0.5 mol) of <strong>[5536-61-8]sodium methacrylate</strong> were admixed with 99.3 g (0.5 mol) of 3-chloropropyltrimethoxysilane, 1.6 g (0.006 mol) of 1-(2'-ethylhexyl)-4-dimethylaminopyridinium chloride and 0.4 g of N,N'-diphenyl-p-phenylenediamine, and the mixture was heated at 120 C. for 1.5 hours, while stirring. The sodium chloride which precipitated as a by-product was filtered off and washed with 80 g of methanol. The methanol was evaporated from the combined filtrates, and the residue was distilled under reduced pressure, whereby 112 g of 3-methacryloxypropyltrimethoxysilane having a boiling point of 82 C. (0.4 mbar) were obtained. The yield was 90.3% of theory, based on the amount of <strong>[5536-61-8]sodium methacrylate</strong> used. The purity of the product was 98.5%. In the gas chromatogram only traces of 2-ethylhexyl methacrylate and 4-dimethylaminopyridine were detectable.

Reference： [1]Patent: US5117027,1992,A

33
[ 5536-61-8 ]
[ 79-41-4 ]

Yield	Reaction Conditions	Operation in experiment
		EXAMPLE 9 Carbon dioxide at 2400+-200 psig (164+-13.6 Atm, 16547103 +-1379103 Pag) and 48+-2 C. was used to extract methacrylic acid from 15 ml of aqueous 0.25 M <strong>[5536-61-8]sodium methacrylate</strong>. The <strong>[5536-61-8]sodium methacrylate</strong> concentration in the aqueous phase dropped by about 17%. About 10% of the total <strong>[5536-61-8]sodium methacrylate</strong> was recovered as methacrylic acid in bomb 32, trap 33 and trap 34. The pH of the aqueous phase rose from 5.8 to 8.6.

Reference： [1]Patent: US4250331,1981,A

34
[ 79-41-4 ]
[ 5536-61-8 ]
[ 507-09-5 ]
(S)-3-thioacetyl-2-methyl propionic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In toluene;	Example IV preparation of enantiomerically enriched (S)-3-thioacetyl-2-methyl propionic acid To 95 ml of toluene, 40.1 mg (0.37 mmol) of <strong>[5536-61-8]sodium methacrylate</strong> and 1.72 g (20 mmol) of methacrylic acid were added at 70ØC. The resulting mixture was stirred for 15 minutes. 3 ml of the catalyst solution prepared in example 1(1 mmol of Ti-catalyst) was added at 70ØC. After addition of the catalyst the mixture was stirred for an additional 15 minutes at 70ØC. 1.56 ml (22.7 mmol) of thioacetic acid was dosed to the reaction mixture at 70ØC within 15 minutes. The reaction mixture was stirred for 1 hour at 70ØC to complete the conversion. The e.e. of (S)-3-thioacetyl-2-methylpropionic acid in the reaction mixture, as determined by HPLC, was 44%.
	In toluene;	Example IX preparation of enantiomerically enriched (S)-3-thioacetyl-2-methylproprionic acid To 100 ml of toluene, 180 mg (1.67 mmol) of <strong>[5536-61-8]sodium methacrylate</strong> and 8.60 g (100 mmol) of methacrylic acid were added at 23ØC. The resulting mixture was stirred for 15 minutes at 23ØC. 15 ml of the catalyst solution prepared in example 1 was added at 23ØC, followed by stirring the mixture for an additional 15 minutes at 23ØC. 7.6 g (100 mmol) of thioacetic acid was added in 15 minutes and the mixture was stirred for 72 hours at 23ØC. The conversion was > 90% according to HPLC. The e.e., as determined by HPLC, was 23%.
	In toluene;	Example V preparation of enantiomerically enriched (S)-3-thioacetyl-2-methyl propionic acid To 95 ml of toluene, 82 mg (0.76 mmol) of <strong>[5536-61-8]sodium methacrylate</strong> and 1.72 g (20 mmol) of methacrylic acid were added at 70ØC. The resulting mixture was stirred for 15 minutes. 6 ml of the catalyst solution prepared in example 1 (2 mmol of Ti-catalyst) was added at 70ØC. After addition of the catalyst the mixture was stirred for an additional 15 minutes at 70ØC. 1.56 ml (22.7 mmol) of thioacetic acid was dosed to the reaction mixture at 70ØC within 15 minutes. The reaction mixture was stirred for 1 hour at 70ØC for completion of the conversion. The e.e. of (S)-3-thioacetyl-2-methylpropionic acid in the reaction mixture, as determined by HPLC, was 53 %.

	In toluene;	Example VI preparation of enantiomerically enriched (S)-3-thioacetyl-2-methyl propionic acid To 95 ml of toluene, 156 mg (1.44 mmol) of <strong>[5536-61-8]sodium methacrylate</strong> and 1.72 g (20 mmol) of methacrylic acid were added at 70ØC. The resulting mixture was stirred for 15 minutes. 12 ml of the catalyst solution prepared in example 1 (4 mmol Ti-catalyst) was added at 70ØC. After addition of the catalyst the mixture was stirred for an additional 15 minutes at 70ØC. 1.56 ml (22.7 mmol) of thioacetic acid was dosed to the reaction mixture at 70ØC within 15 minutes. The reaction mixture was stirred for 1 hour at 70ØC to complete the conversion. The e.e. of (S)-3-thioacetyl-2-methylpropionic acid in the reaction mixture, as determined by HPLC, was 48%.
	In toluene;	Example XI preparation of enantiomerically enriched (S)-3-thioacetyl-2-methylproprionic acid To 100 ml of toluene, 180 mg (1.67 mmol) of <strong>[5536-61-8]sodium methacrylate</strong> and 8.60 g (100 mmol) of methacrylic acid were added at 70ØC. The resulting mixture was stirred for 15 minutes at 70ØC. 15 ml of the catalyst solution prepared in example 1 was added at 70ØC, followed by stirring the mixture for an additional 15 minutes at 70ØC. 7.6 g (100 mmol) of thioacetic acid was added in 15 minutes and the mixture was stirred for 3 hours at 70ØC. The conversion was > 90% according to HPLC. The e.e., as determined by HPLC, was 45%.

Reference： [1]Patent: EP1325908,2003,A1
[2]Patent: EP1325908,2003,A1
[3]Patent: EP1325908,2003,A1
[4]Patent: EP1325908,2003,A1
[5]Patent: EP1325908,2003,A1

35
[ 98-91-9 ]
[ 79-41-4 ]
[ 5536-61-8 ]
(S)-3-thiobenzoyl-2-methylpropionic acid [ No CAS ]