Старый 12.05.2006, 19:06   #17
Andrej
 
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Цитата:
Сообщение от VL
На IE у меня ссылка тоже не хочет открываться, а Mozilla сразу предложила сохранить файл на диск. Попробуйте выйти на страничку
В этом нет надобности – Вы же прислали мне по эмэил этот файл Чтобы не было проблем у других людей, кто будет читать эту ветку, выложил этот первую страницу "The Synthesis of Dicyanine A" by S. Palkin по следующему адресу: http://emrism.agni-age.net/forum/Dicyanin_A.pdf Кроме того, оцифровал её – смотрите в приложение.

Интересное на этой странице следующее:
The only available supply of the photosensitizing dye, dicyanine, before its preparation in this laboratory, was the German product, "Hoechst dicyanine.”

Что на русском будет звучать так:
До приготовления в этой лаборатории единственной доступной поставкой красителя повышения фото-чувствительности, dicyanine, было немецкое изделие, "Hoechst dicyanine".

И это написано в 1923 году, что делает наши предположения, что Кильнер мог использовать только краситель от фирмы Hoechst. Но я бы не стал особо обращать внимания на рецепт приготовления, который приводится в этом журнале за 1923 г., т.к. там речь идёт уже о немного других характеристиках дицианина, а именно о 620 и 670 нанометрах, что прямо говорит о том, что спектр американского дицианина съехал в область видимого спектра. (см. предыдущий пост – цитату из L.A. MIKESKA, H. L. HAULER AND R. Q. ADAMS). Поэтому нужно акцентировать внимание на розыске оригинального описания Hoechst dicyanine А. Заказал несколько книг по архивам этой фирмы, в частности Chronik der Hoechst-Aktiengesellschaft: 1863 – 1988. Посмотрим, может найду что-нибудь хорошее.

Цитата:
Сообщение от VL
Цитируя слова Кирлиана, я не ошибся в источнике. Это фраза из его замечательной книги "В мире чудесных разрядов". Она есть по адресу http://meteo-hacker.narod.ru/other.html Весит до 5 Мб из-за фотографий, хотя брошюра небольшая. Если кто не читал, очень советую. Много души в неё вложено. Но и технических подробностей немало.
Давно хотел достать эту книгу. Спасибо за ссылку. Скачивал часа три. Чтобы люди не мучались, выкладываю эту книгу на быстром сервере по следующему адресу:
http://emrism.agni-age.net/forum/Kirlian_V_mire.zip (4,7 Мб)


_____приложение_________

http://emrism.agni-age.net/forum/Dicyanin_A.pdf

Журнал: INDUSTRIAL AND ENGINEERING CHEMISTRY
апрель 1923 г.

"The Synthesis of Dicyanine A" by S. Palkin1

In a previous paper,2 in which attention was called to the fact that there is no American commercial source of dicyanine dyes, an improved method was described for the preparation of 2,4-dimethyl-6-ethoxyquinoline, one of the principal bases for dicyanine A. In this paper is described a study of the conditions affecting the synthesis of dicyanine A and an improved process of preparation which yields at least twelve times as much dicyanine A per unit weight of intermediate as that obtainable by the Mihesiga-Haller-Adams method.3
The process depends on the action of sodium sulfide on a-y-quinoline intermediates in alcoholic solution, in the presence of small amounts of chloroform. Dicyanine A, prepared by the method given here, was tested by the Bureau of Standards and found to be an efficient sensitizer.

The only available supply of the photosensitizing dye, dicyanine, before its preparation in this laboratory, was the German product, "Hoechst dicyanine.” A method of preparation described by O.Fischer4 is based on the action of potassium hydroxide on an a-y-quinoline quaternary salt in alcohol. An improved method, developed by Mikeska, Haller, and Adams,3 is based on the action of sodium ethylate on the a-y-quinoline quaternary salt in a medium of absolute alcohol. The yields of dye in both methods are so exceedingly low that unless a large quantity of intermediate is used and great care is taken in the preparation, no solid dye, or a product greatly contaminated with cyanine and tar, can be obtained.
In the preparation of dicyanine by the action of sodium ethylate on a-y-quinoline intermediate (quaternary salt), at least two types of dyes are formed. One shows a maximum light absorption in the region of 6200 A. (cyanine), and the other one in the region of 6700 A. (dicyanine). The relative proportions of these dyes varied in different experiments in which the same intermediate was used. It was obvious that the presence in the original base of other quinolines, such as quinaldines, was not the only or even the principal cause for the formation of contaminating dyes. In order to determine their effect on the speed of reaction, relative tendency toward predominance of cyanine or dicyanine, tar formation, etc., it was therefore decided to test the influence of the following factors-kind of solvent used, concentration of OH-ion, type of alkali, catalysts, water, oxygen, time, and temperature.
No space will be taken for detailed description or for recording results of the numerous qualitative experiments made other than to call attention to the important features.

VARIATION OF SOLVENT

The first set of experiments involved the variation in the type of solvent. Of the solvents tried-methanol, ethyl alcohol, amyl alcohol, chloroform, pyridine, quinoline, acetoneonly chloroform showed any marked effect on the reaction, either when used by itself or in alcoholic solution. Two distinct effects were obtained-the speed of reaction was greatly increased, and cyanine was formed almost to the exclusion of dicyanine. All the other solvents either were no better than, or were inferior to, alcohol, so that the next set of experiments was made with ethyl alcohol as the medium, to test the effect of different alkalies and salts giving an alkaline reaction on hydrolysis. Alcoholic solutions of the following were triedsodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide, potassium sulfide, and sodium sulfide. Striking results were observed with sodium sulfide. The speed of reaction was markedly increased and the presence of three types of dyes was observed spectro-scopically - the two previ ously described and a third showing a maximum in the region Of 7200 A. Of these, dicyanine (6700 A.) predominated. As 95 per cent alcohol seemed to be somewhat superior to absolute alcohol for this Work, and as heat hastened the reaction without apparently introducing injurious factors, as a basis for further study 95 per cent alcohol was used as the medium and sodium sulfide as the alkaline salt, and heat was applied to the reaction.
The first few quantitative experiments (recorded as b, H1 and H2 in Table I) showed that the yield of dicyanine was from two to three times as large as that obtained with sodium ethylate,a and their quality as observed spectroscopically was about the same. At this point the general plan of study that had been outlined was suddenly interrupted. Accidentally, recovered alcohol was used in some of the experiments instead of the pure 95 per cent alcohol. As recorded in Experiments K1 and K2, the yield of dicyanine was decidedly increased. Since the number of impurities known to be present in the recovered alcohol used was rather large, it was some time before it was experimentally proved that this increase was due to a small amount of chloroform. This was somewhat startling, in view of the early experiments which showed clearly that chloroform inhibited the formation of dicyanine to the extent that cyanine was the predominating product. That this was true only when sodium ethylate was used is clearly shown in Experiments G, E, F, C, D, and A, Table I. The yield of dye obtained by the use of sodium sulfide and chloroform was over twelve times that obtained by the Mikeska-Haller-Adams method…

1 Presented before the Division of Dye Chemistry at the 64th Meeting of the American Chemical Society, Pittsburgh, Pa., September 4 to 8, 1922.
2 This Journal, 14 (1922), 704.
3 J. Am. Chem. Soc., 42 (1920), 2392.
4 Fischer, Bauer, Scherbe, and Muller, J. prakt. Chem., 98 (191, 204.
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