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December 21, 2016
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January 5, 2009
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February 12, 1959
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Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7 25X1 Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7 Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7 (a,:PaY3.a,1 OcKON.3D3. Yilf. spiv-1;31JD PpoeEaTIS3 et DLNWLDOIO SO138 Mtihallor, 3. 14. aal (avet, Y. A. la ono of the authors' yrtylokls communication/I,. setbod of 4iphanylboria acid and its :erivatives has beg& asecribed (1), of these 4frivatives had the di.ssire to ftrther ssimblisli (Confirm) ,La the literaturdo latapertaising to other diaryloris Said, bar* authorS to usdertate the synthesie of adaitiosal nolbors of tido sommlottl. Thi, following preparations weaS Loadertntea wt % smemss, 4$.1-trompbenyl au& -chlorphonyl boric acids. Isobstyl.seterS ms1101 Acids vere obtattel ta 40-6:11 of theoretical yield, as sell esters of the correspondirg omomryl borie arid*, fraa the profte action of two equivalents of aryl mo..otemiambrceddes with, one *gni itobwitiborstmo Ttess reactions wsre earrie4 out arid's, cOOditl eynthesit of isobutyl ester ot ifS'LL'esql bort3 &eii (i)t, 2ArM03,4/1(1-Oes10)* Arr.B(i-ocalle).+ i-"Isgs014(r rc141.01;er, ;.C1C.64 The eherseteristis IrePertf of these sYmthatoiSed 'store acids is their stability with xesleect to water had dilute slapril Their seco64 characteristic is tLeir hinh solubility is olkaliao ths conS$14mmt formatloa of*alto of dinrylisobotoar brts ao (M211(GNI - ;s3 ? nattsg the wet oolutions of s4eh *alto, cbtained fro& , esters of 4isry1bOr1e soils with %Ilevai Alkali metal end alkali' ' reoults Lasepoaificatioa of tc 1xf rouS id the 4A/04 with. formation of malts of dieryibcris (AraB(02/-1.-40Cel!si ?'Eso ? (Ara(Q13)ti -CelOag Thus the barium aalts of Aisryltori3 Solis are easily 010 direct treatment of diarylorie soli with saturated water eolutioll droxids. Ta this ut1f, oaame aaioa sapoaification forms the mat of (gAry1is....1,ut.,cy aoria a'i-i, blt the /reaction yr0 to yr Coluhility of tAri..3 .-Alts of 4it.ey1tcril aci4s. e eaters of r1;1411e1 an4 ii-p-br*pheml.borie se easily with aveoull t,i,..1c,a..10'formi,-"..4?aoht...m,sAlts of Correa sei4e0 rt* estel of 41-;-,"'l2.'-rO;',,t'nY1 h,:rto soli i* im this essil Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7 Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7 it is not aff*cted,bt4c/tootts &count& *Ye* oPoa hotting., The diarrlhorie acid salts of the den0r01 forals [Arsa(c)I)s) Me af151, ite Ile, At ',4-C1017 p-BreAMO, -clealw oa a0141ficatioa Aro transformod into vadat (Arad(011)*) 14. e ?? AragosY ? ita ? me MO fat/ Of this di naphthyl and di -d -brOMPhis I hod* atidi 0014, the oorrtapolding diarylborio acids, chile the salt of dl-p-c Voris said yields is said which correq*nds, fro* aaaltilli to the . to 41, 1114. chloropheayl bort. said, ii vat alretdy roportei (1) is the 0 it Owl toe, acid, , whets ???? 111 contrast to diphenylborlo said, the other diaryl by the authors, do not fore anhydrides os beating iss vac sou, ilias IL. fornadupoes loss of ons aryl radical. the, aahrdri treatment with thloatl chlorlds as 'bora ii at exempla with aside , (4-C100v)a3(011) * 00c1* ---) (0v-Clogi)s* ? a ? a ? oonclusion it is vial to pause, and oonsider the the litsraturt, portaiaing to the Ilarylbori0 adds. 2b0 di via rocently obtained by tatsinger (2) and his co-vorkero it itfeniaoethyl estor. As to the 41.p-broaapheay1 and the 'torte acids, described by Oafs and scharinhoca (,) aed casainatica of thslastbods of their preparation as used t 040 to doubt it the above avatimed acid, wort actually oh ache:latch and later Molnikoff used the, rosotio4 of 09110010e magnesinabroaldt and trfbutrl borate tor preparatim of the e Atter working up the, reaction product with &lido mineral tell the sionoaryl, bort* toil by-products thel residue, under UN. Dish onataia the unsaponitiol ester ot this diarylborie acid en it..].'. tants and Ocharinbeck deterainad the melting point o said to b? 113,'Cl, vh110 In reality it mat* at 910. The data *We the 41.p.ch1oropheni1 hest* acid to Ws the following 3(01), 'hilt in realitr its coevoeitiot is (Cleoao)0(010.40. Pbr.eoyer, Melnikoft, at al erionfoonelp show* that solervaatittes of p-chIoropbenyl angueslusibronia0 with tr the 41-0-chlorophon4 boric sold :with t 17% yield together vi (1S$ of theoretical) of thie no p-chlorophanyl bodes sold. work, los falai& thtt under the shove stated conditioas oar the borti sold is obtained A41 0.40 AO ester of 41-1-ch1oroPbspyl obtainot. ' ii aside, *Wool tiedaccaarrl bolo act DO obtatoOd by aoophthylberia (A-aloarhe is, ernedleir is saphtkyl bort, said thd teat htitallis" 4-4 eAdAimMAUKI tkott (4)-timi 00 aathofor load, . latig oat opattlties of aryl gmeaboros conpounds. and lsolatioa of tic**, oottld at not the troll acid ,41-11:bracothaarli ahlalkoff, LUCA 6:1414)1 Matto' of et. borate Ilal4s a saillect Ada tiagMelalkott's -ebloroPh0NY1 ?'10 40101.10 Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7 Approved For Release 2009/01/05 : CIA-RDP80T00246 A005600100002-7 To * 1 soli, ether -benzene eolution of 0.5 40110 broads maintained is the -20 to .10'0 temperature range? of triisobutyl beret*, dissolved in 50 ml of or ether, ,.machaalcal otttetlea is a period of 11 minutes. (Vas comp borate ester, the reaatioa tcoperlituri is lowered to tbs - raw NA the agitatio* of the remotion mass is costinue4 . -Venswadtdar.tba-r40.11.9111;TARcts are treated with 350 ml The ather.baseens late* is separsted inlif,'tffe 'IVO- solidi ether. The combined ether -benzene extracts are dried over The ether-benzene is this removed by distillatiol. Ms yellowish reside* upon dilution with 50 ad of isopeataae ail/. The reaction residue was then filtered hod sucked lova:two soli then dried under norms. field 41.5 gran* isobutyl este* of di.A.naphthyl hoes acid, malting point lisation frosts hszems). 1W04. 44 081.20) 6,0 *CV) 6i17 I )47 Cale. for csoa,kao $t 081.22 116.8,5 3 .1?19 Its isopeateae filtrate) attetreneval of the 1 distIlletioa IS osteritied with isobutyl (dead. tea of 4110obsty1 ester offt-mapthyl bort* said are obtained, KO aft CM, ' found $1 Ciofr) 115.mi 1,54) 15.60, MT fog (eloSr),(00age), $1 exc.* 4 .42; DI.76` The ieobwtyl ester of di....4 -naphtha beris *el. 11A0 subateaces *mill' soluble in 'beaten* sad ehlorofori, petroleum ether atei methyl alcohol, and insoluble is i of et -as41011. Berle acid is a colorless liquid. upon set moisture, it is *sally hydrolysei, liberating the 114 -mug* 1 tropius Salt ?till-A- ohthyl borie aeld. Tea areas of isohutyl ester of di-.4-aaphihyl he 2G.]. of seth,ft alcohol. 35.1 of .50$ aqueous anemia er* tice. A *lett **Utica is produced momentarily, et.* ttd, putstaacs is formed. Atter halt hour agitation, the ern sucked dry, rube' with methyl alcohol and dried under tt: weight. die14, 8.8 gams of the tempauml eat of di -4. - roProseetisd $7.5 theoretical, 4.0. 101-107'0. After roc sotkil eloohol, salt moats at 107-108C. ' , found igs Ciao 71.4*, 011r. for ((c3ol7)0(01)$) PS $1 C1030 0111 all)-17, The 141001114 salt of di-0.-rmihtbirlboria 401410 000Vouad, lilt, soluble. in beanies and it hot mist191 111 te oeld *ethyl alcohol, and insoluble is rate ft the 4rdrelfeed.with liberetion of moods and naphtbaleni and ? t Armaplothylmagnes Jun' .221 sole* (3* grow) added with istsasiv* Was of Waiting . to .71'4 temperstere or ePoriod bre. of 5,thydroehleria *aid. ratrestet with- athydrcee sodiun seltet11. tug decent slightly up SP a installs* carefttly imbed with 6111 of theoretical) of 044?0 (Ott* mrpotal,.. 3.44 0 a **darter* or/stet* slighttr eelmble t* .0. alsehstfl ester . Of etsorPboriS bort* sel& is mat are nixed with with hi** *eta. colones* erystallinet are filtered lad until ocostant tlql harts mil, sta3.lisatic01 fro* 3.??4, 1.20) it 4.12) 4.09 3. 4.ki. 010c1.008 tall!** selablit Itcalits roe the A .40gohthr4 Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7 Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7 bort* Sett. tri.6k-nakhtliatorie acid. k.94 area of the emsloollus out of 41.4.43apht,41 is 50 ml of listhylsthmr. To the mixture 3 ml of 62 erfroohl with iatessiwe snitstioa with the reoultirs raattioa mixture rod. The ether /Arse is eePoreto4 out, while the wstst layer With diatlirl *that. The combtromi mthcr astiacts are thescre remove ether, sifter which the residue is heated to 034 for 1 reactios Product (the resits) Is thee dimsoIwel is minimum them promipitsted gutty addition of 1021 of isopmetsee. tii."-mkplatbyl bort. aci4 are obtsinsd, rapresentlat 71.7% of seltit4 Poise 113-11110'0. After recrystallimation fros petrel 41-A-maptly1 bort* soil was founI to mmlt at 114.5-11$'1. INgusd Ot e4.85, 84.90) 4 5.26, 5.,41 3.21# Oils tot de01ls20 $1 d8513 353j 2343 ? the 41.0444aphhhrl, boric aoitt is a oolorlefer_ errs re411.1.17 eoloble iihessants very slishtli soluhle is ether, to4,,, Ivo* hwoh trolgtepo is vaomme, ehewe solitisipoisto *4 titetaefo *se of the seYetlY1 groups Is split off as maohthal borts soil; is chtsined. rls sci4 are mixol xis soli, ars added mini sell to Aveloe Is extrsete4 distille4 -18 istmetee the laintat of by 1.15 gram OS theoretical yield, ether* the pars 0 to gruel of 41 -0`stephtbyl Dori* 6114 are dispel ohlori40 mitts soletios ralurs4 for 2 hours. Vbe thiemrI retors4 iS neap*, WI residue is recrystelllx04 fro* that 'mixture, 1.9 gram (98 percent of theoretical yield) of the "aalthrtrido ere ohteiee4) ealtirn point 190.192'0. Found Olaf 21.80, 91.96; 2 10.2k csis." tor (Clogr)aIKCCI,03021 Cioiir 92.28 111 4.3k This anhydride is acacrledia, crystalline ribstase soluble is basses* and itsoluble is either petrolous ether or tedlostr1 *Oatof 414-troeopharri bone soli S2 a I molar ether solutloa of 0,63 moles of p-h prepers4 by the method described by Pia (1), 0.25 terstes 41ssolyet is 1004 of sbeoluto ether, are Adotritt Nritstiosiis the 40 to ,50?43 temperature veto' withie spirt tto renitis41 resstios **AC it thee &Wore agitate,. tor 0 teoperature tsa? the Mottos products ere thee tree 4tialochtorie Soil. the residue, atter ethot rewrap lies 120)1041. tlotel NA fraotionstest is remain fro. OlerSea by Utmost, The distillate is obtained as two entOtiCe., tolPtresWo LW4i tte setoat is the 138-1010.3 raw, both at 0$001 fertber frsotiogatioe, 38 gram' (39$ Of theoritioel 7140 of 4t-f-troNorbeell borts amid, a.p, 161.163?0 at I MS Agi theoretical 71,14) of Allsobutyl ester of $-trosopbomyl, hoes at / el, SO (441 /./.140) 414 obt4144. 140$1 eeleeeitnt lee of tellsohutyl tessivesechisioal of aN0 bat 20mh is th, with kto_11 00 et 'Mika, 10, at is stmeepters of at IA the 1.01-136io no se 921110111114 of isdbutit sitar 30 itrols OS 02 lis 16,14 10941000 dl Approved For Release 2009/01/05 : CIA-RDP80T00246A005600100002-7 Approved For Release 2009/01/05 : CIA-RDP80T00246A005600100002-7 . Found $s BrelsR4 i8,73, /0.0; I 2:63, 2. for 4Th 3(c414) 8ree4R4-0.8* - - ? I 205 ? /mad $t IWO* 42.72, 49.811 s 3.270 11 Cale. for (hrea14)1004,4 $: BsAlto 119.83 3)./16 The isolmatyl ester of di-p-brumophenyl bogie acid is colorless" very vlecous 1lcah4 rubstwo that slc,rly "sets" vv.* st,?4?440g at tmapersture. It iS soluble La most of oremmic **Ismaili and is slimaY deocapo is the ate* The diisobutyl ester of p-bromopbanyl. bort* *cid is a colorless liquid whist is vapidly saponified is thi. sir tor:erg p-brasophetail bode sett. Ammont4 salt of 41-p-bronapheny1borie sett. ' 2.2$ v, us of isobutyl ester of ii-p-brommphsall 'bort told ars lased _ with j al of 30, rater splutioa of ammonia. lb* resulting' cry, alit* presipitated La filtered, sucked dry, washed with rater ant tried ia vacua* stastestt VOSS. 1.85 greas of the tamoniva salt of di-p-brcoophesyl 'bort* said ? dtained (1.1. 13,1-13,5'0). 1M,11 represents 81.5$ of theoretical, field. Atter riesTstalli,* sstica from bantam*, the a.p. vas found to be 134.1)r0.. found $t 3resP4 8).421 I 2. 2.92) Ilt* 3.61 We for (OresR40211(02)8) Bre.64 65.23/ ? 2. The eingsmilor salt of di-p-bromophavatorie said is a colarlesip *Of+ loss, crystalline substance, soluble is eth71 oo4oethr/ alootto * rit-0411 soluble titan:eat ia isopentame CstdaseLvi salt of 414-broaolhanyl boric sulk 1.21 grams of isobutyl ester of di-p-bassaphisql bort *arid in the eguivaleat Tomtit, of s rater solution of Potooll (3,614 of 0.81) meter which the 'star is flails roared under ? . TWO teeperature raviti La the small sweep of nitroge. The re *moist* of colorless crystals. Attar recrystallisation fras b mizture, 0.8 soma of product ars cbtainel. Pound $1 Breolfg,, 78.58, 710.67) 3 2.71' 2. Cale for I(Bre0.4)aDOS)2114" $t Brco$4 7e.70. '3 243 Its potsseitus salt of 1.1.-p-bromaptow1 Dori sett ill rater and alcohol*, insoluble La btneer.e, petrol.mba ttbse ot treatment with dilute mineral act% the di-p-bAmoplassyl bar'. guntitatircly. All-brcasothemyl Dori* &silt. 1.65 gramie of the annonium salt of di-b-brasetkbeevyt treated with diluted hydrochloric acid. The rematios product is with ether, after vbiet ether is rewired by viscutus erreporstion. Admired, it i saall glantity of isopentant. 1.30 gams (86 of of 4.14-brcompbasyl boric acid, are obtained. Atter recrpe owe ether, the melting point vas fount to be 9041.'0. Sett as* lit* 1011rcaddet it ties 60.. till rvisidad ans?enstlerad. I 9.31p 9.ett 181 soluble ia I teal. tVall ii is regenerated ?aeld ars' this esstristed The resifts is tbeorrtiml yield) tits from petrol* Fount $1 0 42.610 142.69, s2.85, 2.66k 3).18, PAT..% 47.10 ale. for CadaDOBra $ s0 42. hl H2.6/ 33. 18 , 05 ? . ? Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7 Approved For Release 2009/01/05 CIA-RDP80T00246A005600100002-7 The di-p-brotsoPhen4 borio ail da 'e color/eee crYstalline eu solublt ix alcobols and is 'benzene, slightly soluble Lap/Aro is isopesteme. It nal also bo obteited upon eoidificstios o as maationed previously. 0.889 Srlme of potessitla salt yield upon acidification with dilute hyirochlorie. Isobutyl ester of di-p-chloroheiy1 bcrio &eft. 20, 1 molar other solution vt 0.6 moles of P-chlo irati-airniteitainitt-lartt, -.)50t to Atte.tprkerttor? m404 O. isobutyl borate, di000lweiJis 100 ml of dry ithet," aro mtiv, one halt bor with intensive mechanical agitation: the react further cool*" to .70 to -75'0 ani agitated for a 941104 of a next day the reaction products ere trested with 450 ml of) P acid. the residue, lifter removal of ether is estorifiedsdth alcohol and attor removal of coals alcohol by distillation (ras the Claysio flask is *stream of dry nitrates. is obtained its tro separate fro:times Tho 70-140 haat, 1141-16Y0 fraction (at 2 me 4). %Yvon further fractionation /*col ooluma is I stress of'dry nitrogem )1 gm*. of ikkoetY/ ehloroPheayi, Doris sold aro obtained at 134-136?0 (1 represosts 140 percent of theoretical yield Also 11 grass, of ' p-eh1orepheey1 bone soil ar44 ohtsismt at 93"95.4 (14111M4). 000tiod 25$ of theoretical yield. iround $:0/0014 72.56, 72.25 15.'3, 5.5 Cal'. for (0,c44)0(oc09) $xc1eer4 72.68 I 1.52 140,44 $0100,4 141.,A, )41.09 3 1.9(4 4. We. toe (adolso)4(08409)*$:c1c,34 hi. 3. /sobityl ester of 41 -p-chlorophanyl borie soil ii 0 viscous liquid. It is immiseibl0 Idtb vast, stiOeible with* solvents. /t 10 rapidly decomposed in the all. The ditiobm *ADA hoee said is a co/crless, mobile liquid, mIseiblewl orgasio solvents. It is instantly hydrolyzed is the dr, t 04.1011. 1)ette telt. Barium salt of 414.ch.lcrophasy1 boric acid. ? , 1.73 crams of isobutyl eater of di -P-ohlq.?01W/' bc for $.10 minutes with 19 al of I seturstall solution 01, rOaat barius hydroxi40. ThO voluaniousk flocculent pritelPitat44, vhf stouts,' is filtered off, sucked dri, washed with water *offs waight webs Plcuumt. 1.7 Aram, of dry product are obtained, putout of theotaticol yield. for dsterminstion orbs:lust kn prOduct, were heated withskaown anuust of 1 I hydrochlorio sai is the* titratodivith stattsrt 1 X alkali. :gm" "St ps 20.21), 20.26, 01064 61. Cale* for 21044 t(08)alaan St Da 20.t0) dlesge 66. The bariust salt of 41 -$ -chlorogemfl bort. sail Is 4 lino substancO. The salt is not soluble lentos, brume., i quite solublo in meth,/ and ethyl alcohols. Act164"of dilute Yield free di -chlorophonyl bort, acid. henfl teldnadius I mole, of krt.* ' tibia-sported' of, as mixture IS thus 9 hour*. 00 the ? last hydrochlorie 25 ml of isObetyl 14 remittal prodeots (sk a ale $4) awl the tit the aid, of *star of di -P- 1.1414. thig ischmtyl Mtge' Of 1.00618 ropfc. is ailid are shaken atlas) of Is lovas atter a foe of to oototoo4 eh roproosato 89.5 weight* of Um ? /b0 *geese said I 61.91, 20.14,3.09 25.21 ogosloolo. cilstal- taae, it is Marie laid Approved For Release 2009/01/05 CIA-RDP80T00246A005600100002-7 Approved For Release 2009/01/05 : CIA-RDP80T00246A005600100002-7 Di-p-chiorophanyl boric acid. 2.0 grams of the tari,...a salt of 11-9..:chloroPhaA7t With 10 al of 101 diluted hydrochloric Acid. it. a6nestar1 changes to t colorless crystallite substance, .which 1$ tilt.z reshot with rotor awl driei over anbydryus calcium chloride. produsty which melts it 76-78'0, is obtained. Ay U44,1,1111 i notohydrate of 4.1.p-ch1orophely1 bcric acid. Wavle Ar7iAt ,chlorobeatene ant p-chloropheuyl boric acid.' : found $1 c54.55, sk.29; 0440, 4.281 k.o8, Cals. for Cloh~o $i C53.55 12 02 its monohydrate of 11-p-chloroptenyi tor!, aeig, ts nethil and ethyl alcohol, insoluble ia water. 1*iiiu salt of boric aeit. 2.8k vans of ischutyl ester of di-p-chloropheafX solve., in aa squints** amouat of sodium hydroxide' OA Ai of resulting solution is heated to about 60-70'S ant then vats* distillation under a reduied pressure. The residue in washed Inlet in vacuun. field 2.2 exams of dri product. fnulut $1 Cale. tor ClaSiopOsCloltls Its sotiux salt is benzin,' patroleunk ether and Al-p-chlorophsayl:boris sea r10 said are shaken fOrnet.senlsios off, racket 4ry, 1.ias of 447 corrssposste del oVeses It into .83 Cl 26.36 26.66 c240 141. tebeassuri Is r.420 1.56 3 3.'3, 3.6* s 3.7a quite soluble is alcohols emirs isopentans. aeidificaiion # is obtained. COACTZOIOSI rsobutyl *stark, of ii*c(-naPhthfl, 4.1-p'br(4?Vhe*4 8" 41 acid, vets obtainel. rag shank that the isobutyl esters of tii..04-aaphtkf1, gi_p_emoropheayl boric acid, upon heating with potassiws al wsli as upon action of n.mmontuis or barium hydroxides*, f iag metal salts of ths ab enantivned said,. 3.1 Acidification of the above menti ,..ted astal salts pr....Antes itli4r0a0Pbanfl ant tt-p-nhlcrophanyl torte acids. k. Some of tee late, previously reported; ;ortaisias to p-chlorophaayl boric acids were iphywn Obis erroneous. LrTERAM (1) Mikhailow, 11.14. and fairer, f.A., 0.4.1 10.111.),531, 119551. Skoog, J., Ames, Y. $.AN.Chem.Soe. 7?,4041' (19541. 0) Kdtie j.preicaeg.1411,133,4950]. (4) Malnikcw, I I Robitskaildf. (190). (5) Pi1 I., 1.a.cl.Soe.122), i2 hi (6) wittie,4 Adckerb, A., Ailf, A., Ann. gl.? 110-(1949). p-chloropbesql bOrie lbraeopbeskyl end sodlua 19,1roxidas, ra the correspond. re* dd. 4-taphth71, Approved For Release 2009/01/05: CIA-RDP80T00246A005600100002-7