Divinyl

The reaction of alkenyl iodides or triflates, alkenylstannanes, and CO affords divinyl ketones[397,398]. Thus the capnellene skeleton 538 has been synthesized by the carbonylation of the cyclopentenyl triflate 536 with the alkenyltin 537[392], The macrocyclic divinyl ketone 540 has been prepared in a moderate yield by the carbonylative cyclization of 539[399]. 

Aryl and alkenyl phenyl sulfides are prepared by the reaction of aryl and alkenyl halides and inflates with tributylstannyl phenyl sulfide. 2-Chloropyrimidine (737) is used for the coupling[606,607]. The diaryl or divinyl sulfide 739 is prepared by the reaction of distannyl sulfide (738)[548], N,N-Diethylaminotributyltin (740) reacts with aryl halides to give arylamines[608]. 

The last step in the synthesis of divinyl ether (used as an anesthetic under the name Vinethene) involves heating CICH2CH2OCH2CH2CI with potassium hydroxide Show how you could prepare the necessary starting material CICH2CH2OCH2CH2CI from ethylene... 

Vinyl polymers cross-linked with divinyl monomers, for example, polystyrene polymerized in the presence of divinyl benzene. 

Treatment with acidic catalysts dehydrates i j -butenediol to 2,5-dihydrofuran [1708-29-8], C H O (100). Cupric (101) or mercuric (102) salts give 2,5-divinyl-l,4-dioxane [21485-51-8], presumably via 3-butene-l,2-diol. 

Vinyl Ethers. The principal commercial vinyl ethers are methyl vinyl ether (methoxyethene, C H O) [107-25-5], ethyl vinyl ether (ethoxyethene, C HgO) [104-92-2], and butyl vinyl ether (1-ethenyloxybutane, C H 20) [111-34-2]. (See Table 8 for physical properties.) Others such as the isopropyl, isobutyl, hydroxybutyl, decyl, hexadecyl, and octadecyl ethers, as well as the divinyl ethers of butanediol and of triethylene glycol, have been offered as development chemicals (see Ethers). 

The methodology for preparation of hydrocarbon-soluble, dilithium initiators is generally based on the reaction of an aromatic divinyl precursor with two moles of butyUithium. Unfortunately, because of the tendency of organ olithium chain ends in hydrocarbon solution to associate and form electron-deficient dimeric, tetrameric, or hexameric aggregates (see Table 2) (33,38,44,67), attempts to prepare dilithium initiators in hydrocarbon media have generally resulted in the formation of insoluble, three-dimensionally associated species (34,66,68—72). These precipitates are not effective initiators because of their heterogeneous initiation reactions with monomers which tend to result in broader molecular weight distributions > 1.1)... 

Reaction conditions depend on the reactants and usually involve acid or base catalysis. Examples of X include sulfate, acid sulfate, alkane- or arenesulfonate, chloride, bromide, hydroxyl, alkoxide, perchlorate, etc. RX can also be an alkyl orthoformate or alkyl carboxylate. The reaction of cycHc alkylating agents, eg, epoxides and a2iridines, with sodium or potassium salts of alkyl hydroperoxides also promotes formation of dialkyl peroxides (44,66). Olefinic alkylating agents include acycHc and cycHc olefinic hydrocarbons, vinyl and isopropenyl ethers, enamines, A[-vinylamides, vinyl sulfonates, divinyl sulfone, and a, P-unsaturated compounds, eg, methyl acrylate, mesityl oxide, acrylamide, and acrylonitrile (44,66). 

Similar polyacetals were prepared by BASF scientists from CO-aldehydic aUphatic carboxyUc acids (189,190) and by the addition of poly(hydroxycarboxyhc acid)s such as tartaric acid to divinyl ethers (191) as biodegradable detergent polymers. 

D,L-Arahinitol can be prepared by the action of hydrogen peroxide in the presence of formic acid on divinyl carbinol (36) and, together with ribitol (Fig. ld),fromD,L-erythron-4-pentyne-l,2,3-triol,HOCH2CHOHCHOHC=CH (37). 

Vinyl chloride reacts with sulfides, thiols, alcohols, and oximes in basic media. Reaction with hydrated sodium sulfide [1313-82-2] in a mixture of dimethyl sulfoxide [67-68-5] (DMSO) and potassium hydroxide [1310-58-3], KOH, yields divinyl sulfide [627-51-0] and sulfur-containing heterocycles (27). Various vinyl sulfides can be obtained by reacting vinyl chloride with thiols in the presence of base (28). Vinyl ethers are produced in similar fashion, from the reaction of vinyl chloride with alcohols in the presence of a strong base (29,30). A variety of pyrroles and indoles have also been prepared by reacting vinyl chloride with different ketoximes or oximes in a mixture of DMSO and KOH (31). 

Although they lack commercial importance, many other poly(vinyl acetal)s have been synthesized. These include acetals made from vinyl acetate copolymerized with ethylene (43—46), propjiene (47), isobutjiene (47), acrylonitrile (48), acrolein (49), acrylates (50,47), aHyl ether (51), divinyl ether (52), maleates (53,54), vinyl chloride (55), diaHyl phthalate (56), and starch (graft copolymer) (47). 

Finally, using divinyl compounds instead of diynes, surprisingly stable polypyrazolines (747) can be obtained. 

Aziridine, 2,3-diphenyl-l-(2,4,6-trinitrophenyl)-irradiation, 7, 61 Aziridine, 1,2-divinyl-rearrangement, 7, 539 Aziridine, 2,3-divinyl-rearrangement, 7, 42, 65, 539 Aziridine, N-ethyl-inversion, 7, 6 Aziridine, 2-halo-reactions, 7, 74 Aziridine, A/-halo-invertomers, 7, 6 Aziridine, 2-methyl- N NMR, 7, 11 Aziridine, methylene-ring-ring valence isomerizations, 7, 22 synthesis, 7, 92 Aziridine, iV-nitroso-reactions, 7, 74 Aziridine, iV-phosphino-inversion, 7, 7 Aziridine, 1-phthalimido-UV irradiation, 7, 62-63 Aziridine, l-(3-thienyl)-2-vinyl-rearrangement, 4, 746 Aziridine, 7V-trimethylsilyl-inversion, 7, 7 Aziridine, 1,2,3-triphenyl-irradiation, 7, 61 Aziridine, vinyl-isomerization, S, 287 Aziridinecarboxylic acid ring expansion, 7, 262 Aziridine-2,2-dicarboxylic acid, 1-methoxy-diethyl ester... 

Benzimidazolinone, 1,3-dimethyl-Friedel-Crafts reaction, 5, 429 Benzimidazolinone, 1,3-divinyl-synthesis, 5, 393 Benzimidazolinone, 6-methyl-Friedel-Crafts reaction, 5, 429 Benzimidazolin-2-one polymers, 1, 281 Benzimidazolinones alkylation, 5, 390 Friedel-Crafts reaction, 5, 429 Mannich reaction, 5, 390 nitration, 5, 429 reactions, 5, 442... 

Hydantoin, 5,5-diaryl-2,4-dithio-methylation, 5, 444 Hydantoin, 1,3-divinyl-polymers, 1, 280 Hydantoin, 5-methylene-polymers, 1, 280 Hydantoin, 5-phenyl-2-thio-tautomerism, 5, 370 Hydantoin, thio-... 

---