Methyl 2-chloro-acrylate

The cycloadducts formed from the Diels-Alder reaction of 3-amino-5-chloro-2(17/)-pyrazinones with methyl acrylate in toluene are subject to two alternative modes of ring transformation yielding either methyl 6-cyano-l,2-dihydro-2-oxo-4-pyridinecarboxylates or the corresponding 3-amino-6-cyano-l,2,5,6-tetrahydro-2-oxo-4-pyridinecarboxylates. From the latter compounds, 3-amino-2-pyridones can be generated through subsequent loss of HCN <96 JOC(61)304>. Synthesis of 3-spirocyclopropane-4-pyridone and furo[2,3-c]pyridine derivatives can be achieved by the thermal rearrangement of nitrone and nitrile oxide cycloadducts of bicyclopropylidene <96JCX (61)1665>. 

In a systematic study of the addition of cyclohexyl radicals to a-substi-tuted methyl acrylates, Giese (1983) has shown that the captodative-substituted example fits the linear correlation line of log with o-values as perfectly as the other cases studied. Thus, no special character of the captodative-substituted olefin is displayed. More recently, arylthiyl radicals have been added to disubstituted olefins in order to uncover a captodative effect in the rate data (Ito et aL, 1988). Even though a-A, A -dimethyl-aminoacrylonitrile reacts fastest in these additions, this observation cannot per se be interpreted as the manifestation of a captodative effect. Owing to the lack of rate data for the corresponding dicaptor- and didonor-substituted olefins, it is not possible to postulate a special captodative effect. The result confirms only that the A, A -dimethylamino-group, as expected from its a, -value, enhances the addition rate. In the sequence a-alkoxy-, a-chloro-, a-acetoxy- and a-methyl-substituted acrylonitriles, it reacts fastest. 

Other 2-substituted cyclopropylideneacetates of type 3-X also entered this cycloaddition (Scheme 15) [19]. The endolexo selectivity is low but usually still higher than that of simple acrylic acid esters. The relative Diels-Alder reactivities of dienophiles 1-Me and 3-X as determined by competition experiments (Scheme 15) suggest a mechanism involving either diradicals or zwitterions as intermediates [19]. Surprisingly, the 2-fluoro derivative 3-F is less reactive than the parent compound 3-H. The 2-chloro and 2-bromo derivatives 1-Me and 3-Br have similar reactivities and cycloadd to furan (57) about 16 times faster than methyl acrylate. 

In 1972 Wright prepared 3-chlorothieno[3,2-6]thiophene-2-carbonyl chloride (94) in 11-13% yield by heating 3-(2-thienyl)acrylic acid, thionyl chloride, and pyridine, a method of synthesis of benzo[6]-thiophene-2-carbonyl chloride derivatives. " Methyl 3,5-dichloro-thieno[3,2-6]thiophene-2-carboxylate (95) and methyl 2-chloro-3-(5-chloro-2-thienyl)acrylate were also isolated. When fte reaction was carried out in refluxing toluene or chlorobenzene, the acid chloride (94)... 

Optically active acrylic, chloro-acrylic and methacrylic esters of sec. butyl alcohol, 2-methyl-butyl alcohol, 1.3-dimethyl-butyl alcohol, 1-methyl-benzyl alcohol, bomeol and menthol have been polymerized mostly by radical mechanism (Tables 16, 17, 18). 

Acrylate Methyl 3-Chloro-2-fluoro-E10b, 332,339 (Eduet)... 

Mori and Tsuji651 have observed that, upon addition of LiCl as cocatalyst to the above system, the reaction takes a different route and the major product is a 1 2 adduct. For example, methyl acrylate with CC14 (4,4 molar ratio) in acetonitrile at 170 °C after 16 hours yielded mainly dimethyl 2-chloro-4-(2,2,2-trichloroethyl) glutarate (equation 87) ... 

PB PBI PBMA PBO PBT(H) PBTP PC PCHMA PCTFE PDAP PDMS PE PEHD PELD PEMD PEC PEEK PEG PEI PEK PEN PEO PES PET PF PI PIB PMA PMMA PMI PMP POB POM PP PPE PPP PPPE PPQ PPS PPSU PS PSU PTFE PTMT PU PUR Poly(n.butylene) Poly(benzimidazole) Poly(n.butyl methacrylate) Poly(benzoxazole) Poly(benzthiazole) Poly(butylene glycol terephthalate) Polycarbonate Poly(cyclohexyl methacrylate) Poly(chloro-trifluoro ethylene) Poly(diallyl phthalate) Poly(dimethyl siloxane) Polyethylene High density polyethylene Low density polyethylene Medium density polyethylene Chlorinated polyethylene Poly-ether-ether ketone poly(ethylene glycol) Poly-ether-imide Poly-ether ketone Poly(ethylene-2,6-naphthalene dicarboxylate) Poly(ethylene oxide) Poly-ether sulfone Poly(ethylene terephthalate) Phenol formaldehyde resin Polyimide Polyisobutylene Poly(methyl acrylate) Poly(methyl methacrylate) Poly(methacryl imide) Poly(methylpentene) Poly(hydroxy-benzoate) Polyoxymethylene = polyacetal = polyformaldehyde Polypropylene Poly (2,6-dimethyl-l,4-phenylene ether) = Poly(phenylene oxide) Polyp araphenylene Poly(2,6-diphenyl-l,4-phenylene ether) Poly(phenyl quinoxaline) Polyphenylene sulfide, polysulfide Polyphenylene sulfone Polystyrene Polysulfone Poly(tetrafluoroethylene) Poly(tetramethylene terephthalate) Polyurethane Polyurethane rubber... 

The oxathiocin 771 was synthesized from a-(bromomethyl)acrylic acid and 3-mercapto-l-propanol in the presence of NEt3 to give - [ (3-hydroxy propy I )thio methyl [acrylic acid 792, which by an intramolecular cyclization in presence of NEt3 and 2-chloro-l-methylpyridinium iodide yielded the eight-membered ring in good yield (Scheme 155) <2005ASC1811>. 

The main product in hydrosilation of a,P-unsaturated ketones and aldehydes catalyzed by chloro-platinic acid, platinum on alumina, or metallic nickel is the corresponding silyl enol ether. With nickel catalyst, product distribution is highly dependent on the enone structure. Hydridosilanes add to a, -unsaturated esters, producing the corresponding silyl enolate as well as carbon silylated products. The course of addition depends on substrate structure and the hydridosilane utilized. Thus, triethylsilane undergoes 1,4-addition to methyl acrylate in the presence of chloroplatinic acid, while trichlorosilane with either chloroplatinic acid or Pt/C gives the -silyl ester (Scheme 65). ... 

Halogenated styrenes can form a number of copolymers, some used in blends with polystyrenes or other polymers. Examples of such copolymers are poly(o-chloro-styrene-co-p-chlorostyrene), polystyrene-co-poly(2-chlorostyrene) [14], poly(methyl acrylate-co-4-chlorostyrene), etc. A few studies on thermal behavior of these polymers are available [15, 16]. 

Benzyloxy(cyano)carbene would be expected to be electrophilic by virtue of the calculated selectivity index, Wp -HjOccN 111- This has not yet been experimentally proved as 3-bcnzyloxy-3-cyano-3//-diazirine is rather labile and cannot be isolated if it is synthesized by the substitution of chlorine by a cyano group in 3-benzyloxy-3-chloro-3if-diazirine consequently, this substitution reaction is carried out in the presence of an alkene, hence, preparing 1-benzyloxy-cyclopropane-l-carbonitrile derivatives. However, the cyanide ion present in the system induces the polymerization of electrophilic alkenes, such as acrylonitrile or methyl acrylate. 

Cyclopropylideneacetates also undergo [4-1-2] cycloadditions to yield spiro[2.5]octene derivatives. The relative Diels-Alder reactivities of 2-heteroatom-substituted 2-cyclo-propylideneacetates, as determined by competition experiments with furan to give 7-oxa-bicyclo[2.2.1]heptanes 18, have been studied. The 2-chloro and 2-bromo derivatives were equally reactive and underwent cycloaddition ca. 16 times faster than methyl acrylate, which in turn is far more reactive than methyl 2-chloro-3,3-dimethylacrylate. Selected examples of [4-1-2] cycloadditions are given in Table 4, for further examples see refs 10, 22, 44 and 45. 

Another method to prepare chloroquine (3) involves reaction of 83 with methyl acrylate to get via 98 and 99 the adduct 100, which is converted into 7-chloro-l,2,3,4-tetrahydroquinoline-4-one (103). Reaction of 103 with novaldiamine (92) under dehydrogenating conditions gives chloroquine in about 25% overall yield [133] (Scheme 3). 

A carbene carrying both a donor and an electron-withdrawing substituent presents a new pattern of reactivity, often called ambiphilic, since such species can show both nucleophilic and electrophilic properties. Thus chloro(methoxy)carbene 4.222 has a low enough energy LUMO, making it electrophilic towards simple alkenes, and yet a high enough HOMO to make it able to react with electrophilic alkenes like methyl acrylate.443 None of the carbenes discussed above is capable of both of these reactions. 

The in situ prepared trialkoxy(chloro)titanium complex is dissolved in CH2C1, (ca. 5 mL per mmol). At -30CC ca. 0.8 equiv of methyl acrylate (5), and after 30 min at the same temperature ca. 2 3 equiv of cyclopcntadiene, are added dropwise. The mixture is kept overnight (ca. 15 h) at - 30 =C, then hydrolyzed with ca. 20 niL of 2 N HC1 and extracted with Ft20. When (R)-binaphthol (7) is used it is extracted with 2 N NaOH. In the case of the 1.3-dioxolanc derivatives it is precipitated by the addition of pentane to the crude reaction mixture, then filtered off. The crude product is purified by flash chromatography. For determination of the oplical rotation a sample is purified by Kugclrohr distillation (130 fC/l 5 Torr). When (3 )-binaphthol (7) is used the adduct is obtained in 77% yield with 50% cc of the (-)-(f )-enantiomer. With the (R.R)-diol 8 derived from tartrate, the (-)-(S)-adduct is predominant (55% yield) with 46% ee. 

Fig. 15-4. Q-e map for a number of important monomers the full horizontal line indi-catea the present choice for the scale of the polarities e the band between the two broken lines represents the location of a more rational e scale (a) chlorotrifiuoroethylene, (b) acrylonitrile, (c) allyl chloride, (d) ct-chloroacrylate, (e) methacrylonitrile, (/) methyl acrylate, (f) vinylidene chloride, (A) methyl methacrylate, (t) vinyl chloride, (j) chloro-prene, -(fc) vinyl acetate, (i) butadiene, (m) styrene, ( ). isobutylene, (o) p-methoxysty-rene. XAlfrey, Bohrer and Mark, Copolyrmruaiion," p. 82, Intencienee Publishers, Ine., New York, 1952.)...

The tosylation of carbon can be accomplished using electron transfer conditions. Treatment of styrene and analogs with Copper(II) Chloride and tosyl chloride or Benzenesulfonyl Chloride results in a formal replacement of the vinyl proton by the sulfonyl moiety (eq 35). The intermediacy of a trans-(S-chloro sulfone has been demonstrated by H NMR. Treatment with base induced the elimination of HCl. A variety of other sulfonyl transfer reagents can be ertployed in the synthesis of isolated /3-chloro sulfones, with good results (60-97% yield) for a variety of alkenes (ethylene, 1-butene, 2-butene, 1-octene, acrylonitrile, methyl acrylate, and 1,3-butadiene). ... 

MEI Meilchen, M.A., Hasch, B.M., and McHugh, M.A., Effect of copolymer composition on the phase behavior of mixtures of poly(ethylene-co-methyl acrylate) with propane and chloro-difluoromethane, A/ocTO/Mo/ecM/es, 24, 4874, 1991. 

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