Whiting reaction

Heating the white reaction product to 140 C for one hour in vacuum caused a visible iodine evolution and approximately 40% weight loss. No further weight loss was observed up to 250°C. The gaseous products from the pyrolysis were not collected. The green product from pyrolysis analyzed Pu, 43 3% I, 50 2% C, 4.9 1%. The empirical formula PuI2C2H3 has the calculated composition Pu, 45.88% I, 48.75% C, 4.79%. 

In a lOmL round-bottomed flask equipped with a magnetic stirrer bar were placed tetrahydrofuran (0.8 mL) and immobilized poly-D-leucine (100 mg). (7 )-Benzylidene acetophenone (50 mg), l,8-diazabicyclo[5.4.0] undec-7-ene (90 mg), and urea-hydrogen peroxide (27 mg) were added to the mixture. The thick white reaction mixture was stirred vigorously for 30 minutes. 

A. exo-3,4 -Dichlorobicyclo[3.2.l]oct-2-ene. A 1-1. four-necked round bottomed flask is fitted with an efficient stirrer, a thermometer, a reflux condenser protected by a calcium chloride tube, and a 500-ml. stoppered addition funnel equipped with a pressure-equalizing side tube. After the addition of a solution of 52.5 g. (0.56 mole) of norbornene (Note 1) in 400 ml. of petroleum ether (Note 2, b.p. 45-60°) to the flask, 112 g. (2.06 moles) of sodium methoxide (Note 3) is added, and stirring is begun. The flask is immersed in an ice-salt mixture (Note 4). Three hundred forty-nine grams (1.8 moles) of ethyl trichloroacetate (Note 5) is placed in the addition funnel and allowed to drip slowly into the stirred mixture at a rate such that the temperature does not rise above 0° (Note 6). The addition requires about 4 hours, and the originally white reaction mixture becomes increasingly yellow in color. The mixture is stirred at a temperature below... 

Whiting reaction. Alkynediols are reduced by lithium aluminum hydride in ether or tertiary amines to dienes. 

Dehydro r rr(9-carotene (48) was also synthesized via the diol 34, an intermediate from the synthesis of isozeaxanthin (129). The diol 34 was transformed into 48 in low yield by the Whiting reaction with UAIH4 [9] (Scheme 8). 

Wharton Reaction Whiting Reaction Wichterle Reaction Widman-Stoermer Synthesis... 

The egg-white anaphylactoid reaction is accompanied by haemoconcentration and hypothermia [243, 247, 248], both of which are probably a consequence of the increased vascular permeability and oedema of the Reaction. The adrenal cholesterol, circulating eosinophil count and blood concentration of corticosteroids remain unchanged after egg-white is administered to rats. The adrenal ascorbic acid, however, is significantly decreased, but this does not correlate with the severity of the anaphylactoid oedema [641, 642]. Other studies show that there is a reduction of the adrenal medullary catecholamines during the egg-white reaction and these amines may condition the resistance of the rats to the effects of egg-white [392]. 

Specific inhibitors of 5-HT, but not mepyraniine (a specific histamine antagonist [427]), inhibits the egg-white reaction in reactor [35,55,487,489,668] and in non-reactor [36] rats. Other studies have shown that egg-white reduces the 5-HT content of rat skin [447, 465, 487] and releases this amine from the perfused hindquarters of reactor [257, 485] and non-reactor [423] rats. These results, therefore, suggest that the amine largely responsible for the egg-white anaphylactoid reaction in both types of animal is 5-HT. 

Leger and Masson [401] reported that pretreatment with the parathyroid hormone did not influence the egg-white reaction. Moreover, after confirming an earlier report [402] that female rats seemed less sensitive to egg-white than male rats, it was shown that ovariectomy or castration did not influence the incidence or severity of the response. 

Hypophysectomy, which produces an atrophy of the adrenal cortex, has been reported to inhibit [122, 298] and to enhance [425] the egg-white reaction or to have no effect on the egg-white [401] and dextran [396] reactions. More recently, Gabbiani and Bocskor [199] reported that hypophysectomy reduces the sensitivity of rats to iron-dextran and that normal sensitivity is restored by the transfusion of plasma from an animal with an intact pituitary. This suggests that a plasma substance is produced in the pituitary gland which has a permissive action on the anaphylactoid reaction. This report has yet to be confirmed. 

M.Medakovi6, Egg White Reaction in Rats and 5-Hydroxytryptamine, Archs int. Physiol. Biochim. 67, 294-305 (1959). 

Modified Whiting reaction s. 11, 111 Arenes from quinones... 

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