Proceedings of the chemical section, of the Frankin Institute

Jan., 189x.]

~heJm'ca/

Sectio/z.

55

PROCEEDINGS OF 2'tt1'3

@HEMICAL SECTION, 01' THE FRANKLIN

I NNTIT

UTE.

[Sla#d lJtee/ing, held a/ ~lie hlsfilu[e, Tuesday, 1)ccember z6, 189o. ] H A L L O F THE F R A N K L I N INSTITUTE,

PHILADELPHIA, December I6, 189o, Mr. T. C. Palmer, president, in the chair. Members present: Prof. E. F. Smith, Prof. L. B. Hall, Dr. Win. H. Wahl, Mr. Lee K. Frankel, Mr. It. Pemberton, Jr., Mr. Reuben Haines, Dr. S. C. Hooker, Prof. Henry Trimble, and several visitors. Dr. Wahl, as chairman of the committee to prepare a circular to be addressed to the chemists of the country, reported progress, and the committee was continued. T h e secretary read his annual report to the section, which was accepted. The election of officers followed, and, on motion, it was decided that the secretary cast the vote of the section for the ticket nominated at the November meeting. Dr. Wahl was escorted to the chair by the retiring president, and, on taking his seat, made a brief address appropriate to the occasion. On motion of Dr. Hall, it was voted that the officers, president, secretary and treasurer, constitute three of the seven members of the committee on admissions. The following gentlemen were then nominated an(t elected to fill the remaining vacancies in the committee, viz : Mr. H . Pemberton, Jr., Dr. S. E. Hooker, Prof. E. F. Smith, Dr. L. B. H a l l The president appointed Messrs. Haines and Frankel to act with the secretary as members of the finance committee. Dr. Wahl referred to the approaching convention of chemists, to be held shortly in this city, stating what had been done by the local committee to arrange for the event, and expressed the wish that the members of the section would second the efforts of the local committee to m a k e the visitors welcome. Dr. Greene exhibited specimens of the alloys of sodium and lead, dis= cussed in the paper by himself and Dr. Wahl at the last meeting. They were examined with much interest. Adjourned. W ~ . C. DAY, Secretary.

56

C'/zemical 5cctioll.

ON SOM>: I ) E R I V A T I V E S

[J. F. I.,

()1." L A P A C I I I C ACID (I).

By SAMUI';LC. HOOKER and WM. H. GREENE.

[/dead b@re t/le (.7eemica/ 5)'ction, ~Ifarch zS, zggo. ~

In a preliminary paper:" published by t h e authors, it w a s shown that the conversion of lapachic acid into lapachone,+ by the action of strong mineral acids, p r o b a b l y occurs in t w o stages, as indicated in the following e q u a t i o n s : C,0It,

I ()._, CIt = CH - - C:~ttr ;, H.,O == OH l,apachlc Acid.

C~ot-t~ CH,_,-- C H ( O I t ) - - C~.H7 = OH OxyhydrolapachicAcid.

O,. CIoH~ CH.,

l

-

-

CH - - Catt; + t-t,,O

0 Lapachone.

In support of this view it was s t a t e d t h a t lapaehone c a n be readily converted into o x y h y d r o l a p a c h i c acid, and t h a t this acid, u n d e r the influence of m i n e r a l acids, again r e a d i l y passes into its a n h y d r i d e lapachone. T h e details of these experiments, w h i c h h a v e not y e t been printed, will be published in this paper. CONVERSION OF LAPACltONE INTO

OXYHYDROLAPACHIC

ACII).

T h e action of aqueous potash on l a p a e h o n e has b e e n studied by Paterno,, who writes as follows: " I n aqueot*s potash of m e d i u m concentration l a p a e h o n e does not dissolve in the eold; on h e a t i n g it passes into a fine p u r p l e - r e d * This Journal, 1 2 8 , 142.

Gazz. cMm. Ital., 12, 372. ~. Gazz. cMm. I[aL; 12, 372.

Jan., ~89r.j

CTze~Jzzcal ~eclion.

57

solution which, filtered while hot, deposits on cooling beautiful orange needles of silky lustre, recognized by their fusing point (i54°-I55 °) to be lapaehone. On the addition of hydrochloric acid the alkaline filtrate yields a precipitate, which, purified by recrystallization, was similarly found to be lapaehone." This statement is misleading. The facts are t h e s e : Lapachone dissolves with some difficulty in hot aqueous potash, but in so doing undergoes a change. A new compound, an acid, is formed, and this, and not lapaehone, exists in the solution obtained. If hydrochloric acid, in very slight excess, be added to the cold alkaline solution, the new compound separates as a yellow oil, which gradually assumes a crystalline form. If, however, a larger quantity of hydrochloric acid be employed, the color of the turbid solution is seen gradually to change. The bright yellow gives place to orange, and finally red crystals of lapachone may be observed floating in the liquid. The new compound has, in fact, been reconverted, by the excess of hydrochloric acid employed, into lapachone. The experiment has been repeated a n u m b e r o£ times, but the authors have not once observed the separation of crystals of lapachone from the alkaline solution as described by Paterno. The action of potash on lapachone is shown in the following equation : Cl0H~ C H ~ CH. C3H~ ~" O _-~

H20 =

Lapachone.

C1uH~ CH2. CH(OH). C3H7 OH Oxyhydrolapachic Acid.

In order to prepare oxyhydrolapachie acid, eigh t grams of lapachone, four grams of caustic potash and I5o ec. of water are heated together. If the crystals of lapachone be large, they should be first powdered. As the lapachone is

58

[J. F. I.,

C/tem#a/ .%cfiolt.

dissolved, the color of the solution b e c o m e s very i n t e n s e , b e i n g similar to that of the salts of lapachie acid. A f t e r boiling several minutes, t h e solution is filtered t o r e m o v e any crystals which m a y have e s c a p e d t h e action o f the potash, and an excess of acetic acid is tlnen added. A yellow oil is i m m e d i a t e l y precipitated, w h i c h collects in t h e b o t t o m of beaker, and then appears c o n s i d e r a b l y d a r k e r than when first seen in a fine state of division. In t h e course of an h o u r or so, it solidifies to a yellow crystallirle mass which, after some hours, m a y b e s e p a r a t e d and w a s h e d well with water, T h e acid, as thus o b t a i n e d , t h o u g h slightly colored at the surface, is in a v e r y p u r e c o n d i t i o n and can be rendered a b s o l u t e l y so b y crystallization once o r twice from alcohol, in which it dissolves v e r y readily a n d from which it separates slowly in m o n o s y m m e t r i c c r y s t a l s . T h e yield is theoretical ; eight g r a m s of l a p a c h o n e gave 8 " 4 grams of the crude acid; t h a t r e q u i r e d b y theory b e i n g 8"59 grams. The following figures were o b t a i n e d on analysis : (I) 'i965 grain gave "497oCO..,and -- H~O (II) "4932 . . . . I'25to CO.~ " "2743 H,,O (III) "2o93 . . . . . 53o6 COs " "116o H,~O C. . . . . . . . . . . . H. . . . . . . . . . .

1.

Found. f [.

III.

C~thrulated fo~,ClaH1~O~.

68'96

69'18

69"13

69"23

lost

6'I8

6'I5

6"I5

Oxyhydrolapachie acid melts at ~25°. It is r e a d i l y soluble in most of t h e ordinary solvents, from which i t crystallizes after standing some time; if, however, t h e solvent be allowed to evaporate rapidly, t h e acid is left a s a yellow oil. U n d e r ordinary conditions it is a p e r f e c t l y stable body, which can be crystallized from acetic acid u n c h a n g e d ; but in contact w i t h mineral acids, even w l i ~ n dilute, it is readily converted into its a n h y d r i d e l a p a c h o n e , which w as identified b y its fusing p o i n t a n d o t h e r p r o p e r t i e s , and b y analysis. T h e barium salt is ext.remely characteristic, s e p a r a t i n g from a claret-colored solution in b r i g h t orange, silk-like needles, g r o u p e d together in w a v y tufts. In order to p r e pare it, the acid was dissolved in a solution of baric h y d r a t e ,

Jan., I891.]

C/Lemica/

59

S:cliom

from which the excess of b a r i u m was precipitated at the boiling t e m p e r a t u r e by m e a n s of carbon dioxide. T h e solution was t h e n c o n c e n t r a t e d to the crystallizing point. ,Ks t h e ewtporation proceeds, a film of the salt, in an a m o r p h o u s condition, and of the s a m e color as the solution, forms at t h e edge of the liquid, on the e v a p o r a t i n g basin. T h e salt is m u c h more soluble in hot t h a n in cold water. A f t e r reerystallization, t h e orange needles g a v e the following figures on analysis : (I) .2152 gram substance gave '0744 B~SO4. (II) "2883 " "0987 " (111) "2478 . . . . . . . 0854 " L'

Fou rid. II. 2o"I2

Calculated f o r

IIl. ( Clg,HI~,O4),2Ba, H~tO.

( ClsH150¢)~Ba.

Ba(percent.).. 20'32 °-0'26 20"35 2o'91 The above figures were o b t a i n e d from different preparations, dried over sulphurie acid, and also at 1 10% The salt e v i d e n t l y contains one molecule of water of crystallization, a l t h o u g h the a t t e m p t s to determine this b y loss were unsuccessful. H e a t e d to I10 ° for several hours, no c h a n g e in w e i g h t occurred, and decomposition commenced at s o m e w h a t h i g h e r t e m p e r a t u r e s . It was, however~ observed t h a t the o r a n g e crystals, w h e n rubbed, became dark magenta-red, a n d analysis proved t h e altered salt, dried at i o 5 ° - t m °, to be anhydrous. U n d e r the microscope, it showed no definite Structure, a n d w h e n m o i s t e n e d with water it b e c a m e i m m e d i a t e l y orange, at t h e same t i m e swelling up and t h e n p a s s i n g into solution. On evaporation, the characteristic orange needles of the salt, as above described, were a g a i n obtained. The a n h y d r o u s salt was prepared for analysis b y thoroughly g r i n d i n g the o r a n g e crystals, in small quantities at a time, in an a g a t e mortar. T h e conversion was not easily • accomplished, and it seemed as if a resinous substance were being d e a l t w i t h , T h e g r o u n d substance was h e a t e d to I to ° until c o n s t a n t in weight. (I) ,3368 gram substance gave 'II82 BaSO4. (II) "2834 . . . . . . IOO2 '

L

Found. II.

Calculaled for (C15H1604)~Ba.

Ba, . . . . . . . 20"63 p.c. 20"78 p.c. 2o'9! p.c. The two d e t e r m i n a t i o n s were m a d e w i t h different preparations.

60

[J. F. I..

C/lemical 5;ectiatz.

T h e calcium salt is entirely different f r o m t h e b a r i u m salt just described. It separates from its s o l u t i o n on e n v a p o ration in small dark-red crystals, and is o n l y v e r y s p a r i n g l y soluble in both hot and cold Water. A f t e r d r y i n g over sulphurie acid, it did not lose in weight w h e n e x p o s e d for o v e r an hour to a temperature of I05°-IIO °. A n a l y s i s shows it to be anhydrous. (I) .3 t 13 gram gave 'o8o8 CaSO4 (II) "2594 . . . . . 0635 " f.

Ca. . . . . . . . .

T63 p.c.

Found.

f ]',

7"19 p.c.

Calculated f o r ( C15flI1504)~C~L

7'I6 p.c.

The preparations analyzed were different. (I) w a s obtairted by adding the theoretical quantity of c a l c i u m chloride t o the slightly ammoniacaI solution of the acid ; on e x p e l l i n g the excess of ammonia by heat, the salt s e p a r a t e d . (II) w a s prepared as above described for orange v a r i e t y of the b a r i u m salt. The silver salt was obtained by p r e c i p i t a t i n g a eortcentrated neutral solution of the a m m o n i u m salt with t h e calculated q u a n t i t y of silver nitrate. I t separates in a semi-resinous condition, becoming g r a n u l a r a f t e r some t i m e . It is decidedly soluble in water, also in d i l u t e alcohol, f r o m which it separates, on spontaneous evaporation, in s m a l l dark-red needles. T h e figures it gave on analysis lie between those required for CLsH~50,Ag a n d C,,~H150,Ag -H20. It is probable, therefore, that the c o m p o u n d was n o t obtained in a pure condition.