Acryloyl chloride

Property AcryHc acid Acrolein AcryHc anhydride Acryloyl chloride Acrylamide... 

Carboxylic Acid Functional Group Reactions. Polymerization is avoided by conducting the desired reaction under mild conditions and in the presence of polymeriza tion inhibitors. AcryUc acid undergoes the reactions of carboxyUc acids and can be easily converted to salts, acryhc anhydride, acryloyl chloride, and esters (16—17). 

Jicyylic anhydride is formed by treatment of the acid with acetic anhydride or by reaction of acrylate salts with acryloyl chloride. Jicryloylchloride is made by reaction of acryhc acid with phosphorous oxychloride, or benzoyl or thionyl chloride. Neither the anhydride nor the acid chloride is of commercial interest. 

Acryloyl chloride can be used to cause ring enlargement with the production of a bicyclodiketone when it is treated with a cyclohexanone enamine. This is shown by the reaction of acryloyl chloride (25) with 1-N-morpholino-1-cyclohexene (26), affording diketone 27 upon hydrolysis (32,33). 

Acryloyl chloride (0.2 mol) in dry benzene (60 ml) was added over 0.5 hour with mechanical stirring to pentane-1,5-diol (0.1 mol), triethylamine (0.2 mol) and pyrogallol (0.1 g) in dry benzene (100 ml). Further dry benzene (ca 100 ml) was added followed by triethylamine (10 ml), and the mixture stirred at 50°C for 0.5 hour. The triethylamine hydrochloride was fii-tered off and the solvent removed In vacuo to leave a yellow oil which was distilled in the presence of a trace of p-methoxyphenol, excluding light, to give 1,5-pen tarn ethylene diacrylate (12.9g 61% BP90°to95°C/0,01 mm Hg),... 

Benzoctamine HCI ChlorthenoxazIne Hydroxytryptophan Letosteine Methionine Acrylonitrile Fenproporex Acryloyl chloride... 

HOOC C ( ) = polymer 40 ( ) = from acryloyl. chloride 4/ ( ) =from styrene-acryloyl chloride (1 1) 42 ( ) =from styrene-acryloyl chloride 5 1)... 

Attempts to prepare 5-vinyl-5F7-dibenz[b,/]azepine by alkylation of 5i/-dibenz[b,/]azepine with 2-chloroethyl-p-toluenesulfonate followed by dehydrochlorination, or by direct vinylation with acetylene under pressure in toluene or in dimethyl sulfoxide, have failed.194 Also, 5H-dibenz[b,/]azepine fails to react with acryloyl chloride, although the 5-acryloyl derivative 8 (R = COCH = CH2 mp 122 — 123 C) has been prepared in 65% yield by condensing dibenz-azepine 5 with 3-chloroacryloyl chloride, followed by dehydrochlorination of the product with l,8-diazabicyclo[5.4.0]undec-7-ene in dimethyl sulfoxide at 80-90°C.194... 

Several wide-porous affinity and size-exclusion chromatographic supports were prepared by Ivanov, Zubov et al. by means of acylation of aminopropyl-glass supports by copolymers of N-vinyl pyrrolidone (N-VP,1) and acryloyl chloride (AC,2), M = 7700 and 35000 respectively [50, 51]. The copolymers prepared by free radical copolymerization contain their units almost in equimolar proportion, with high tendency to alternation expected from the copolymerization parameters (rj = 0.035, r2 = 0.15 [52]). Residual carbonyl chloride groups of the chemisorbed copolymer could be transformed to 2-hydroxyethylamides which were solely... 

Indeed, the polymeric interface seems to be highly diffuse and hydrophilic because copolymers of N-vinylpyrrolidone and N- (2-hydroxyethyl) acrylamide are readily soluble in water [53]. Besides, aminopropyl-glass adsorbs the acryloyl chloride copolymer so that only 10% of its active functions become amidated. The rest is located on the loops and tails of the attached macromolecules [51]. Thus the steric repulsion of the bonded phase is a probable reason for the high inertness of the packing towards viruses. 

A container of acryloyl chloride containing 0.05% of phenothiazine used as an inhibitor, was expos to very unfavourable climatic conditions that brought it to a temperature of 50°C for two days. After this time, it polymerised violently, shattering its container and forming a voluminous foam. Yet the container label mentioned that it could not be stored at temperatures greater than 4°C. 

Chiral dienophiles, prepared from an aldehyde and asparagine in water followed by reacting with acryloyl chloride, reacted with cyclopentadiene at room temperature in water or ethanol-water to provide cycloadducts diastereoselectively and chiral products upon separation and hydrolysis (47-64% ee for the endo isomers endo/exo 82 18) (Eq. 12.18).61... 

The scheme used to prepare the direct 8-aza-analogue 21 of estrone bears at least formal similarity to the Torgov-Smith steroid total synthesis sequence. Acylation of the phenethylamine 9 with acryloyl chloride gives amide 16. Michael addition of dimethylamine followed by Bischler-Napieralski cyclodehydration gives the dihydroisoquinoline, 17. 

Acylation of the tryptamine-based /3-enamino esters 458 with acryloyl chloride and its derivatives results in acylation of the enamine nitrogen and formation of the pyridiniminium ion intermediate 459. Electrophilic attack at C-3 of the indole and rearrangement of the spiro intermediate gives the indoloquinolizines 460 (Scheme 102) <2003TL6527>. 

Additionally, the authors chose 3-chloropropionyl chloride as the immobilized building block in order to carry out a ring-expansion approach, which led to the generation of a 14-member library of thioxotetrahydropyrimidinones [85, 86], The initially prepared polymer-bound chloropropionyl ester was efficiently transformed into the corresponding diamines by transamination utilizing several primary amines. These diamine intermediates could also be obtained by treatment of the pure polymeric support with acryloyl chloride and subsequent addition of the appropriate amines (Scheme 7.74). 

Finally, another related study from the Sun laboratory concerned the synthesis of hydantoins utilizing acryloyl chloride to prepare a suitable polymer support [87]. All steps were carried out under reflux conditions in a dedicated microwave instrument utilizing 50-mL round-bottomed flasks. Identical reactions under classical thermal heating did not proceed in the same time period. 

In a related study, the group of Bazureau applied their polyethylene glycol-grafted ionic liquid phases (ILPs) to the preparation of 2-thioxotetrahydropyrimidinones [105], After the initial formation of acrylate-bound ILPs utilizing acryloyl chloride in refluxing dichloromethane, several primary amines were attached in a Michael addi-... 

Reactions of selenoureas with ketones, haloacyl halides and chloroacetonit-rile provides 1,3-selenazole derivatives,289 295 whereas reactions with acryloyl chloride gives 1,3-selenazine derivatives (Scheme 87).296... 

Dipolar addition is closely related to the Diels-Alder reaction, but allows the formation of five-membered adducts, including cyclopentane derivatives. Like Diels-Alder reactions, 1,3-dipolar cycloaddition involves [4+2] concerted reaction of a 1,3-dipolar species (the An component and a dipolar In component). Very often, condensation of chiral acrylates with nitrile oxides or nitrones gives only modest diastereoselectivity.82 1,3-Dipolar cycloaddition between nitrones and alkenes is most useful and convenient for the preparation of iso-xazolidine derivatives, which can then be readily converted to 1,3-amino alcohol equivalents under mild conditions.83 The low selectivity of the 1,3-dipolar reaction can be overcome to some extent by introducing a chiral auxiliary to the substrate. As shown in Scheme 5-51, the reaction of 169 with acryloyl chloride connects the chiral sultam to the acrylic acid substrate, and subsequent cycloaddition yields product 170 with a diastereoselectivity of 90 10.84... 

As shown by the two examples represented in Scheme 99, chiral enaminoesters are good candidates for the synthesis of saturated or partially saturated oxazolo[3,2- ]pyridine derivatives (Scheme 99) acylation of 374 with acryloyl chloride or conjugate addition of 376 to 377 afford in both cases substrates that readily undergo cyclization, respectively to 375 <2002TL2521> and 378 <1996JOC1890>. 

Hexafluoro-2-hydroxy-2-(4-fluorophenyl)propane (HFAF) was obtained from Central Glass Co., Japan, and was distilled under argon prior to use. Ethyl bromoacetate, methyl acrylate, acryloyl chloride, and methacryloyl chloride were obtained from Aldrich and were used as received. Hydroxyethyl methacrylate and hydroxypropyl methacrylate, also from Aldrich, were purified as described in the literature.6... 

Triethylamine was fractionally distilled from lithium aluminum hydride under nitrogen and acryloyl chloride was distilled under nitrogen. 1,1,2-Trichlorotrifluoroethane (Freon 113) was distilled from phosphorus pentoxide under nitrogen. Azobisisobutyronitrile (AIBN) was used as received. Methyl ethyl ketone peroxide (MEKP) (9% Organic Peroxide VN 2550) was obtained from Witco. Alumina (neutral, Brockman activity 1, 80-200 mesh) was obtained from Fisher Scientific Co. All reagents were obtained from Aldrich unless otherwise specified. 

The etherdiacrylate 6 was prepared by a modification of the procedure of Griffith and O Rear.11 To a solution of etherdiol (3 g, 3.78 mmol) in Freon 113 (10ml) in an ice-water bath under nitrogen, triethylamine (0.791 g, 7.81 mmol) in Freon 113 (5 ml) was added dropwise in 10 min. After 10 min more, acryloyl chloride (0.707g, 7.81 mmol) in Freon 113 (5 ml) was added dropwise in 20min a precipitate formed immediately. After stirring for 2 h at room temperature, filtration through Celite to remove the solid, followed by evaporation at room temperature in vacuo, 3.02 g of a viscous liquid was obtained. 

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