Oct. 5, 1952
NOTES
4949
chlorobenzaldehyde and 100 cc. of benzene was distilled azeo- a nitroester. By partial reduction of DL-p-nitrotropically as above. The product (2.5 9 . ) crystallized from phenylalaninate with LiAlH4 they obtained the glacial acetic acid; m.p. 144'. Anal. Calcd. for Cz~Hlscorresponding alcohol in about 68% yield. ON2C12: N, 6.1; C1, 15.5. Found: N, 6.3; C1, 15.0. It has been shown by Felkina that the ester group Bis- ( 0 -chlorobenzylidene)- 1 , l - di-( p-aminophenyl)-2,2 ,Ztrichloroethane (I, X = CHCCla).-The product of the of ethyl p-nitrobenzoate and related compounds can reaction of 3.15 g. of 1,l-di-(p-aminophenyl)-2,2,2-trichloro- be preferentially reduced to the primary alcohol by ethanes and 2.8 g. of o-chlorobenzaldehyde in 100 cc. of benzene was a reddish oil which solidified upon trituration with lithium aluminum hydride without affecting the a small quantity of acetone. The solid (3.2 g . ) was recrys- nitro group. tallized successively from butanol, yethylcyclohexane and It is surprising that by selective reduction of the Anal. Calcd. for ethyl erythro-p-p-nitrophenylserinates with LiAIH4, glacial acetic acid; m.p. 163-164 C28Hl9NZClb:N, 5.0. Found: N, 5.1.
.
(9) L. Haskelberg and D. Lavie, THIS JOURNAL, 69, 2267 (1947).
DANIELSIEFFRESEARCH INSTITUTE WEIZMANN INSTITUTE OF SCIENCE REHOVOTH, ISRAEL
The p-pNitrophenylserines and the Corresponding p-p-Nitrophenylserinols BY G. CARRARA, E. PACEAND G. CRISTIANI RECEIVEDMARCH19, 1952
the corresponding erythro-p-nitrophenyl-2-amino1,3-propanediols can be obtained in a practically quantitative yield when the quantity of LiAlH4 employed is smaller than the quantity calculated for the blockage of the groups containing active hydroand for the reduction of the gen (-OH and -"*) ester group; thus with 0.5 mole of LiAlH4 for one mole of ethyl p-nitrophenylserinate we obtained a yield of about 60%; with one mole of LiAlH4, the yield was 97% of the theoretical. We suppose that LiAlH4 in the case of erythro-pp-nitrophenylserinates reacts first with the oxygenated functions (-OH and -COOR) and subsequently with the nitrogenated functional groups (-NH2 and -NOz). We also made an attempt to apply the same selective reduction to ethyl threo-DL-P-p-nitrophenylserinate and its optical antipodes in order to obtain the corresponding diols. But although the reduction was tried under a variety of conditions, we were unable to obtain the desired diols. Only red oils which gave reactions characteristic of azo compounds are obtained. Table I summarizes the results of the selective reduction carried out with various amounts of Li41H4 for one mole of ethyl m-erythro-p-pnitrophenylserinate.
Recently Moersch, Rebstock, Moore and Hylander' have published a note on the constitution of the j3-p-nitrophenylserines. We have also investigated this subject and have in press a note on ethyl m-erythro-p-p-nitrophenylserinate and its resolution.2 Entirely in accordance with the above-mentioned authors we have demonstrated that the ethyl DL@-p-nitrophenylserinate,m.p. 114-115', obtained by condensation of p-nitrobenzaldehyde with ethyl glycinate is of the erythro configuration. Starting from Erlenmeyer's 0-phenylserine we have also obtained the ethyl DL-@-p-nitrophenylserinates,m.p. 130-132", which we have shown to have the threo confiauration.a In-the above-cited note in press, we have also TABLE I described the Of the DL-erythro-@- SELECTIVEREDUCTIONS OF ETHYLD L - ~ ~ Y ~ } ~ ~ ~ - B - P - N I T R O p-nitrophenylserinate into its optically active forms PHENYLSERINATE by means of dibenzoyltartaric acid, with a recovery Yield, Recovered of the active forms in about 93% yield.4 hloles LiAlH,/mole ester % ester, % This paper summarizes the results achieved in 0.25 .. 85.0 the selective reduction of threo- and erythro-p-p.50 58.9 40.9 nitrophenylserinates with lithium aluminum hy.60 68.4 33.6 dride. Huebner and Scholz5 starting from the .80 80.0 18.8 threo-N-dichloroacetyl- 0 -acetyl - p - nitrophenylser1.05 97.4 .. ine ethyl ester obtained by reduction with LiA1H4 a Experimental gummy substance which could not be induced to DL-erytltro-I-p-Nitrophenyl-2-amino-1 ,%propanediol.crystallize, but which showed an activity approxi- Ethyl D&-erythro-j3-p-nitrophenylserinate (0.01 mole) dismately one-half that of chloramphenicol when solved in ethyl ether (500 ml.) was treated in an atmosphere tested against S. paradysenterke. Bergmann, Ben- of nitrogen, with finely powdered LiAlH4 suspended in das and Taub6 have attempted the reduction with ethyl ether (50 m1.). The addition Of the LiAlH4 suspension was carried out a t room temperature while stirring for 30 LiAIH4 of ethyl p-nitrophenylserinate, but with es- minutes. The mixture was heat$d for 4 hours in a watersentially negative results. Dornow and Winter' bath at a temperature of 35-40 . The excess of LiAlH4 were the first to attempt the selective reduction of was then m u t i a s l ~decomposed by adding 2.5 ml. of water (1) G. W.'Moersch, M. C. Rebstock. A. C. Moore and D. P. Hylander, THIS JOURNAL, 74, 565 (1952). (2) G. Carrsm, G.Cristiani, V. D'Amato, E. Pace and R Pagani. Goes. chim. i f d ,in press. (3) G. Carrara and G. Weitnauer, i b i d . , 79, 856 (1949). (4) G.Carrara and E. Pace, Italian Patent application 16.707 filed on February 5, 1952. ( 5 ) c. F. Huebner and C . R. Scholz, THIS JOURNAL, 73, 2089 (1951). (6) E. D . Bergmann, H. Bendas and W.Taub, J . C h m . sot., 2673 (1951). (7) A. Dornow and G.Winter, Be?., 84, 307 (1951).
and stirring was continued for another half hour. The mixture was filtered. The solution was heated on a steam-bath and evaporated to dryness: unchanged DL-erythro-BP-nitrophenylserinate if any was recovered. The residue was transferred to an erlenmeyer flask and 35 ml. of hy&ocaoric acid was added. The reaction mixture was then heated on a steam-bath until solution was complete. The latter was neutralized with sodium hydroxide t o a pH of 8-9; then it was extracted seven times with 100 ml. of ethyl acetate. The combined extracts were ( 8 ) H . Felkin, Compl. rend., 230, 304 (1950); 231, 1316 (1950).
4950
NOTES
dried over anhydrous sodium sulfate, filtered and the filtrate evaporated to dryness zn vacuo, the residual crystals were collected a n d recrystallized from boiling ethylene dichloride A The colorless crystals so obtained melted a t 109-1 10' niixed melting point with a n authentic sample of the nitrobase of the erythro series gave no depression Calcd. for C9H1&?04: X, 13.20 Found: 1, 13.28. LEPETITS . P . A . RESEARCH D~\-rs~ox 311La4N, ITALP
Preparation of Macrocrystalline Fluorapatite Containing Radioactive Phosphorus BY GLENNV. ELMORE ASD E. 0. NUFFMAX RECEIVED APRIL5, 1952
The properties of fluorapatite, Ca1o(POd)sFz, are important in the technology of phosphate fertilizers, a field with which the Tennessee Valley Authority is concerned. The thermodynamic properties of fluorapatite were evaluated recently,' and other properties of the compound are being studied. Fluorapatite containing radioactive phosphorus was needed in a study of the kinetics of solution of the apatite. X product of high specific activity was wanted, and existing methods of preparationzt3 were considered unsuitable because of the difficulty of conducting such operations as mixing, grinding and screening without undue hazard to the operator. A method devised for the preparation of inacrocrystals of radioactive apatite in a high degree of purity is the subject of the present report. Method of Crystallization .--Fluorapatite can be prepared from a melt of its components in a flus. Thus, when a melt of a n orthophosphate of calcium or potassium in an excess of calcium fluoride was heated at 1400' in a vacuum, part of the solvent calcium fluoride was vaporized, arid crystals of fluorapatite were formed. Removal of the excess calcium fluoride was incomplete, however, even after 24 hours of heating. Substitution of alkali metal fluorides for the calcium fluoride resulted in melts from which the non-apatite fluoride could be evaporated completely a t 1200" in a vacuum. Although good fluorapatite W I S obtained with either sodium fluoride or potassium fluoride, the sodium wlt was preferred because it was less hygroscopic. When the fluoride vas evaporated from the melt in a n externally heated porcelain tube: the vapor attacked the porcelain and caused contamination of the fluorapatite with silica. T o avoid this contamination, the platinum crucible containing the charge was suspended in a vertical glass tube anti heated by iiiduction. The glass wall remained cool and did not contaniinate the apatite. The fluoride vapor condensed on the glass. The melt had a pronounced tendency t o creep over the edge of the crucible during evaporation of the solvent. Crystals formed on the outside of the container, and the inside was essentially empty at the end of a n experiment. This creeping of the melt removed part of the solvent from the hot interior of the crucible to the cooler exterior where its evaporation was incomplete. Complete evaporation of the solvent in 5 hours was effected by suspending the crucible and its contents inside a second platinum crucible of slightly larger diameter and heating the outer crucible a t 1200" by induction. This arrangement provided an external sourer of heat for the crucible containing the charge. Good crystals of fluorapatite were deposited on the outside of the inner crucible. The method fina11y de~veloped for the crystollization of
VOl. 74
fluorapatite was shown to be equally suitable for the preparation of macrocrystalline chlorapatite from a solution of itc.onipoiients in sodium chloride or potassium chloride. 111 subsequent application of the method to the growth ut sentially free of impurities. The method of its preparatioti ltas been described. * 11 spectrographic analysis of a typical macrocrystalline Iluorapstite prepared from the smaller crystals showed the it Jllonkg percentages of impurities: Sa,O, 0.14; MgO. 11.1; SrO, U.111; 5 0 2 , 0.03; Fe:OJ, < 0.01; ALOl, < 0.?1; CuO, < O.UO2. The preparation gave a strong apatite Iiittcrn' by X-ray diffraction. S o other crystalline phase \ V A < detected in the X-ray analysis. A microscopic examination showed that the colorless rod crystals of fluorapatite were optically clear and free of growth imperfections other than elongated air cavities. The crystals ranged from 1 to 5 mm. in length. The (OtOO1 cleavage was prominent. The crystals were hexagonal arid = 1.62: and nW = 1.631. Traces C i i uniaxial ( - 1 with platinum, calcium oxide and a-tricalcium phosphate were detected 3s crystallitic impurities. A 3-hour digestion oi the apatite with a neutral solution of ammonium citrate a t 6b' removed all the calcium oxide and a-tricalcium phosphate except isolated fine-grained dccp-seated inclusions. Incorporation of P32.-To prepare radioactive fluorapatite, 0.1 g. of the microcrystalline apatite was dissolved in several milliliters of concentrated nitric acid and mixed with 2 rnl. of s solution containing SO mc. of carrier-free Pa2 as phoThe amount of P3* was minute i l i phatc in nitric proportioil to the phosphorus from the apatite but ivaenough to impart a high specific activity to the final product. The solution was evaporated in a platinum crucible without boiling. The nitrate in tlie rcsidue was decomposed :tt red heat Sodium fluoride then was added, and fluorapatite was crystallized from the mixture in the manner described. T h e rhdio:tctive crystals, upon microjcopic examination, .ippcared t o be of the same high quality as that reported ior the iioii-radioactive preparations. The refractive i l l t l c ~ e of i the two types of preparations were identical.
Acknowledgment.-K. L. Elmore suggested thc c.r! stallization oi fluorapatite from an alkali fluoride as a solvent. J. R. Lehr made the microscopic esaniinations, J. P. Smith the X-ray ex:~iiiinationsand Frances 11. Youngblood the spectrc-igrnpliicanalyses. K Y ~ A7~6 ,. 387 , (1930,. Sup?lied b y lsotopes Division. Vnited S t a t e s Atomic Energy Cconiinicaion, Oak Ridge, Tenn. St. SLray-Szatio. Z .
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TEXXESSEE \.ALLEY AUTHORITY DIVISIOS O F CIIEMICAL L)EVELOPMEST 1i.11w s I>.ur, ALA.
Bromination, Iodination and Phenylation of Thianaphthenes BY RUSSELL GAERTNER RECEIVED APRIL 28, 1982
In continuation of studies of the effect of a *'blocking" group in the ortho position on abnormal reactions of arylmethyl Grignard reagents,' 2bromo-3- (broinomethyl) -thianaphthene (I) was obtained by the action of N-bromosuccinimide on 2bromo-3-methylthianaphthene. I appeared to react normally in the cyclic Grignard reactor, but only polymers and traces of impure products could be isolated from the reactions with ethyl chloroc a l m l a t e and fornialdehydc. The presence of a t r x c of J coupling product, presumably 1,2-bis-(2l > R Gaertncr
I HIS J O T J R ?I ~ 74, 2091
1952)
