DE1543317A1 - Process for the amidation of alcohols - Google Patents

Description

Dlpl.-lng. R. H. Bahr Dlpl.-Phy «. E. Betzier Dlpl.-lng. W. Herrmann-Trentepohi

PATENT LAWYERS

Hem ·, the 1543317 Fr * ll! Gr * thitr »6e 19 Poettach 1« Telephone: H a r η · 5 09 30 and 515 S2 TeItX 08229863

is, £ 6 Sep 1966

Alter St. Qeorgsplatz 9/11 Telephone: Munich 38 »2β T <* I e χ 05 24 SK

Poebustelhing «concrete 489 Herne, Poetfadi 140

File no. .u Cu, "H" 3 Please state in the answer

ArL-U ^r i {AD ÜC AWti

t-01 north, / absh avenue,

Chicago, Illinois

Approval for Ajiiieraa.-i / oti

This iirfindun ^ ^ concerns the AuiiiieiMii of alcohols and refer SiCN ± λβ special experience to a / to Aiiidieriing of alcohols ..lit el ne..i i <itril in eineai fliiasigen i'luorvvasserstoffiiiediujj. The iliiorwasaer & toff-ijediäta serves as an acid catalyst as well as a lic Lcsiinr.-s-agent. The iteaktioii can go through the iiaci standing aiigef level

: jclie.!) a

will:

9 0 9 8 ö 1/1 3 9 9

^BAD ORi

dCd

1 Ηϊ

T-T

I -iäurg oaer base +

The Auiidierung of alcohols: Λ: eine.ii i: itril is known per se (... Compare EaIl occ Ohiai ir'ince 1957> ^r ieite 596-610), the allerdinrs ^ rcielten Aasteuten are sov / ie the tfi he ed Obtaining the niciituüii-replaced aur-i «n £ substance & or the catalyst is poor. In addition, it is the more difficult to dehydrate alcohols, such as, for example, the secondary and pri, u ^:. '. This is in £ -; fe ^^ verötänalich, as it is known that the ease of i) ehy- lratisierang of alcohols from the tertiary through the secondary to ^ u the primary alcohols atni.rjuit. The eiuzire aisnaiuie is given when the dehydration leads to a bond which is resonance-stabilized by a conjugated double bond or an adjacent nucleus.

An aim of the present invention is to provide a new / experienced to the Ajiäieruxif of Al ^ or-olerx.

Another aim is to provide a method of the type indicated above, v / eicnei. so.vohl 5'if

] riJi " ^: re is also applicable to secondary and tertiary alcohols.:

.. further hit: ilev, die 2rfiulu ': _ _: the development of / experiencing the ν- ^' standing on. e _? level .xrt set to the sewer, which enables an effective and economical recovery of the liatalysfctoi'ß iji connection aii the Jjsetzun-er ^ ''.

, / pus icle er present l / rfindüii. ·; «E.-ier. : ³ including the following λ »; j / airangen.

£ .efu;: cen, da. ": Alcohols, eiriscliliealich terti-ire, seicundare and, surprisingly, so = .ar primary alcohols, then ji.it eini l-.itrile aaiidiex-v, if a groier [ '' TerscliuS of waser-free flü & Bi | reai EF 'is available, and we are in aϊ rarti en -lenken, iaS .aaii speak of a solvent .iia used., In particular, here us je srelli ;, that alcohols, ciie uurser the levels below j'or

R ₂ -C-OH

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(GE ₀ )

R ₄ OH

II

wherein R ^, R ₂ and R, a hydrogen atom, an alkyl, aryl

alkyl or cycloalkyl group as well Washings of these groups with at least

a group other than 'hydrogen mean, vvoLei the groups 2 - 4- Ilohlenotoffatoae contain,

R., H ^ and jig hydrogen, all ^ l-, arylalkyl- or

r3- ^r kloalki ^; lgruppen and di schunden DIE 'ser Grupi: en unu represent the SuiCiie of

a f b ♦ c one, / ert from 2-9 ausiiacht, · '

fellen.unüer \ / ei ".vendunf _: an organic nitrile of the general formula

III

wherein R «is hydrogen, an alkyl, aminoalkyl or Aryl radical and metal salts of the atniiioalkylreBtes and the residues contain 1 - 21 Zolilenstoffatome,

909881/1399

a ^ idiert v / erden know if a gvjdex ^ tersc .α !; ' an anhydrous liquid HiV, vorau ^ sv / ice in the range of ~ - 25 ..iols per ilol alcohol is used ".

The alkyl portion of the radical dea i * Shalyapin's Museum III canoe eradkettig, branched or ^r 'yklaalkylrest A'in.

The xieaictionsteaiperature used is jjüJi ^, it lies between 0 and 1 '* 0 C and Yorzuf-sweiae between 25 and IOC ⁰ G; the reaction time is Kura, they schvankt iinuben and between-5 2 hours can thereby in a simple rjisetauni'r ixe i / eiöe tforui in a continuous T experie ens durchgefiüii't be. From this it emerges that '; that / experience, which is carried out under unfavorable conditions, is very suitable for a technical implementation.

The healing proceeds under Sinsata of a large range of the starting materials. If the nitrile / alcohol ratio is at least 1; 1, then the hea ^ ctionsstoichiouietrie is satisfied. In fact, however, an amount of nitrile is used in excess of the amount required by the strobiOinetric method. If the ratio of nitrile to alcohol is about 1.1: 1.0 to about 4.0: 1.0, then particularly satisfactory results are obtained. Additional citrile can be used, but this is not practical for economic reasons. -

909881/1399 ^BAD

- O -

The amount of fluoro-hydrogen can vary within wide ranges. If hydrogen fluoride has a catalytic effect, it also serves as a reaction device. A ratio of hydrogen to alcohol greater than about 3 is preferred. A hydrogen fluoride: alcohol ratio of β: 25 has been found to be particularly satisfactory. Larger amounts of hydrogen fluoride can also be used, although this is not favorable for economic reasons.

The reaction will proceed over a wide range of pressures. Deliver pressures from atmospheric pressure up to 20 atmospheres satisfying results. The preferred one used Pressure is between Atjjosphe'r pressure and 5 atmospheres, although any pressure which is sufficient to do so will reduce the reaction mixture keeping in the liquid phase is satisfactory. However, excessively high pressures are required as a result of this Systems uneconomical.

Good yields of Aaid are usually obtained during a Obtained a period of time from 5 minutes to a few hours, depending on the raw materials used and the reaction conditions applied.

The amides formed fall under those given below Formulas:

909881/1399

Γ j>

H ₀ -O-IIH-CR ₇ IV

wherein ^ ₁ , R ₂ and R _{5 are} hydrogen, alkyl, arylalkyl or

Cycloalky groups and mixtures of these groups with at least one group other than hydrogen, where the radicals 2 - 48 carbon atoms contain,

R ₄₁ R ₅ and Rg hydrogen, alkyl, arylalkyl or

Represent cycloalkyl radicals and mixtures of these radicals, the Suuajie of

a + b ^ c is between 2 and 9 and

R _{7 stands} for hydrogen, an alkyl, aminoalkyl or aryl radical and also for metal salts of the aminoalkyl radical, these radicals containing 1 to 21 carbon atoms.

The amides formed can be obtained from the reaction mixture different processes can be separated. A procedure

909881/1399

consists in diluting it with water by simply pouring the entire reaction mixture into a large excess of cold water. The product can then be extracted with ether, whereupon the extracts are washed free of hydrogen fluoride and the jither is removed in vacuo. Another isolation method makes use of the separation by means of a tank, whereby excess hydrogen fluoride is driven off by simply heating the reaction mixture to about 150-2C0 ° C. under guidance. Such a heating separation process is particularly well suited for large scale processes. In addition, the hydrogen fluoride driven off by heating the reaction mixture can be condensed for reuse in a simple manner.

The hydrolysis of the intermediate amide can be carried out using a hydrolysis agent consisting of any suitable acid or base in aqueous or alcoholic solution. Aqueous sulfuric acid, aqueous sodium hydroxide, sodium in alcohol and aqueous alcohol, aqueous potassium hydroxide, and potassium hydroxide can be mentioned as preferably used in alcohol hydrolyzing agent, wherein the concentration is conveniently about 50 $>. Good results have been obtained with concentrations around $ 30-70. Concentrations outside this range have only a partial hydrolysis of the effect is the mole

• 909881/1399

Amide: hydrolysis agent ratio greater than 1.0: 1.0, then the stoichioujetry of the reaction is satisfied ". Preferred Amide: hydrolytic agent molar ratios ran between about 1: 3 to 1: 6.

The amide can be hydrolyzed within a wide temperature range. Good results have been achieved at temperatures of around 50-300 ° G, depending on the hydrolysis agent used. An aqueous sulfuric acid solution used, preferably the temperature employed is about 100-120 ° G. I ^r is atriumhydroxyd used in aqueous or alcoholic solution, is then preferably applied '-Temperature between 150 and 250 ° G.

The hydrolysis can also take place within a wide range of pressures take place. Pressures from atmospheric to 20 atmospheres are satisfactory, although any pressure sufficient to keep the reaction mixture in the liquid phase to keep is satisfactory. Excessively high pressures, however, are uneconomical due to expensive printing systems «

The amines obtained during the hydrolysis of the amides correspond the following sormelm

₂ GH ₂ VI

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711

where R ₁ , H ₂ and H ^, hydrogen / alkyl, arylalkyl or

Cycloalkyl radicals as well as mixtures of these radicals are at least one, ^r n xiest except *, Yasser3toff, where the radicals 2 - 4-8 contain carbon atoms,

R «, Rc and Rg far, / water, alkyl, arylalkyl or ir Cycloalkyl radicals like these Leftovers stand and the Su: njie of

a --f .b + c is between 2 and 9.

The amines can be extracted from the hydrolysis mixture by cooling the mixture to about Zimjierteuiperatur, adding a
large excess Viasser, separation of the aqueous phase and distillation of the amine.

The following examples "illustrate the invention without it to restrict:

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Example 1

Amidation of Z - butanol

In a 100 ml Monel autoclave, 12C g (6.0% oil) of liquid hydrogen fluoride, 49.2 g of acetonitrile (1.2%) and 29 _{% of} 65 g of 2-butanol (C, 4%> 1) are added charged about 0 ° C. The autoclave is closed and the temperature is increased to 60-65 ° C. over 1 hour. The heater is then cooled to 5-10 ° C and opened, whereupon the reaction mixture is filled into a 500-liter flask made of red-free steel, which is equipped with an electric oil and a stirrer . t * - the j'luor'vaeser.'itoff 'vird durcii £ rhitzen the LVCA ^ tioHc- ^ i ^ CLAIX call IJC ⁰ O aborted "by lläekttand kaim q .-; ji_i in un ef'Üir 4CC ail. Aether ^ el'oat and jiit small -. Direct aqueous aluminum carbonate to be washed until the washing fluids are clear. The initiation solution obtained is dried over anhydrous sodium sulfate and treated in vacuo; this yields about ZZ g (69.5% yield) of N-butyl acetaai-d, the analysis of which results in the following

Lieutralization equivalent: 126.5 (calculated 115) Amide: $ 91>

. . · BATHROOM OHIGINAL

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Atfliüiν run ,; before: 2-lIc; ν tp-d seri

A; 'CtJ-iul-iuoneli-Jtokli) V: -ird jiit ¹ JO f Il'irxi; gh j'luorwac :: cretoff (4, ^r : - lüol), 35, S, acetonitrile (c / j -UoI) and 77 »C _c ί - '" θτ1 aaec.-nol (C,' * vioi.) Ivc-i uiu-fefy.hr CU LescnicKt. The ..ier "-" gate becomes cr; ii; i versciJ c. ^! Serj. And the '.'e.iirer'j'tur w'üirend c on GC- -b ° U ta ^ ht. Then the reactor

! Ulf UiV; ef ^; .Uir 5 - IC ⁰ cooled and opened, whereupon the lieaktions ui I. κ c'.iun _f ; .i ^ i ICGO .nl cold .YaB .ser tef _: oß;: en y / irä. 1 1 lit her we to e _c "el: en ui .. uie vvU ^ ri. E uchicht al 'separated. The or ^ aaii.-C ^l ie Ihiiee will then .uit a few portions of salt water from * i ^r ' aEeerBtofffluorid freeif ewaiic'ien. The Xther 1 ^ 'sun ^'., 'is then dried over wasL-erfreiji ratriu ^ Eulfat. and concentrated iji / akuuin; 84.0 e (aut yield 94.5 ° P) N- (nee - 'hej.tadeC ^ l) -acetanide an analysis of which the following, i are obtained:

ITeutralization equivalent: 319.5 (calculated 297.5) Aoiid: 93 fo

Example 3 of -2-ethyl hexanol

A 300 μl i.lon.autoclave is filled with 120 g of liquid hydrogen fluoride (6.0 moles), 49.2 g acetonitrile (1.2 moles) and 13.02 g 2-ethylhexanol (C, 1 mole) at about 0 ° 0.

909881/1399

The Ieactor is then closed and the IE temperature increased to 60-65 G over a period of 30 minutes. The reactor is at about 5 * - ■ IC G cooled and opened _t on which the iieaktionsoiischiing in loco ml of cold, Tasser cast vill. 1 liter of iither is added and the aqueous layer is separated off. The organic phase is then washed free of hydrogen fluoride in a few portions of salt water. The Ütherlösung is then over anhydrous 1; Dried atrium sulfate and concentrated in vacuo, about 9.5 g (yield 55.5 / o) of a KT-Octylacetaaiids are obtained, the analysis of which gives the following 7ths:

Neutralization equivalent j 243 (calculated 171.2) Aiiiidi 70.5, * -

Example 4 Amidierong of n-pecanol

A 300-liter Monel autoclave is filled with 90 g of liquid hydrogen fluoride (4.5 moles), 18 ^ 4 g acetonitrile (0.45 hol) and 47.5 g n-decanol (Q, 3 moles) is charged at about 0G. The autoclave is closed and the temperature increased to 80-85 ° G over a period of 20 minutes. Then will an additional 18.4 g of acetonitrile (0.45 mol) for 5 minutes pumped into the reaction mixture, the additional 15 minutes is held at 80 - 85 ° G for a long time. ! laughs at the translation

9 Q 9 8 8 T / 1 3 9 9.. bad ofbqinal

is cooled 10 ° C and opened "whereupon the Reaivtionsaiscaung in IGCC JJI cold" .fässer ge-.gousen 1 1 I'ther is then added and the aqueous layer separated, the or ^ ani.ciie phase - of the reactor to about 5.. salt water is washed free of hydrogen fluoride with a few portions. The atiating solution is then dried over anhydrous calcium sulfate and concentrated i, a / "acuua. 27.0 g (yield 45.2%) H-Dec ; / licetaj] id, the analysis of which yields the following values: ■; ■ -,

"eutralization equivalent: 100t (calculated 19 ^, 3) A ^ iid: 19, '-} j>

example 5

Aiflidation of cyclohexanol . .. ■ -.-

A 300 mm ionic autoclave equipped with a stirrer is filled with 12C g of liquid hydrogen fluoride (6.0 Iol) and 39.2 g of acetonitrile (1.20 mol) at about 0 G. The heater is closed, whereupon the temperature is brought to 54 G. Then 40.0 g of 3ylohexariol (0.4 G mol) are added over a period of 27 minutes at 54-56 ^{G :.} Las jäüiiren? / Is continued for another 3C minutes at ' ¹ } 6 - 62 G ^: The content is then continued. 5 G cooled and the autoclave opened. The Reai: tionaischun _f ; is poured into ICCO ώΐ cold water, whereupon IGGC Jl ither is added. The organic phase is separated and removed from hydrogen fluoride

90988 1/1399

- Yj -

15A33T7

f wash clean. The Itherl '^ un-, ird then Uler anhydrous ^T *' atriu.iisulfat dried, lei the I on centering i. " Vacu: -? .. u fall .V-, 5 g of a wide solid material .jit aji F. of 105 - ICo ⁰ C (ÄUi-'lcute 61.7>). Declared force: 1C4 G. -

36 Auiio: 97.5

; .ei aer GasckroJiato ^ raOhie is only eii, 1-eal:. preserved.

Ajidi e run.v of 2 -ionanol

A 30 (.-- JiI- uom l'-a ^ oklatf · becomes .üit νC, -. (4, - l.ol) fliFsi-e .:]? Luorvvast3erh; tcff and ^7. " ₁ 9 g (^ >? - ^ o3) Acetonitrile \> ei u: i'e- ■ for OO V. esc'iicrt. The autoclave is vented, before the temperature is reduced to a value of up to 49 G _c elrac: it -wirij then herding 4 -, 3 g (0.7 -lol) ^2-:;? onanoi während- a time £ r: i: ine of; 'Vei 5 uinuten a' _x 2euV he door. from 49-5β augepuaipt. The heating is continued for a further 3C minutes "at 5B - 60 °. The contents are then removed to 5G, whereupon the autoclave is opened. The reaction mixture is poured into 10C ml of cold water, whereupon 10C ml of ether The organic phase is separated off and washed free of hydrogen fluoride. The ionizing solution is then dried over anhydrous sodium sulfate. The concentration in vacuo gives 51.7 g of a pale yellow viscous oil (yield 93.0 $) .

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/ ο juid: 93.5

The infrared analysis time that the samples from one substituted amide without the use of alcohol is available.

The Isomereverteiluiir "is by G-aschroniatographie like is determined as follows:

2-Aiüinononan: 23.9 ! °

3-ainononane: 33.6 / o

4 * -aminononane: 42.5 f>

At sr-iel 7

Adiidation of n-dodecanol

A 3CC Jil-i'Jonc autoclave is 9C g (4.5 alol) of liquid hydrogen fluoride and 55.3 g (0.3 ioI) n-dodecanol at about 0 ° G charged. The autoclave is closed, whereupon the temperature is brought to a value of up to 90 ° G; thereupon are 36.9 g (0.9 4ol) of acetonitrile over a period of 35 minutes at a temperature of 90-98 ° C to ^ epumpt. Stirring is continued for a further 30 minutes at 92-95 ° G continued. The contents are then cooled to 0-5 ° C, whereupon the reactor is opened. The reaction mixture is poured into 1000 ml cold (barrels, whereupon 1000 ml Chloroform can be added. The organic phase is separated off and washed free of hydrofluoric acid.

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The chloroform solution is then dried over anhydrous sodium sulfate. When concentrating in vacuo, 42.2 g of a dark brown, mobile layer are obtained (yield 61.8 </ o).

> Amide; 6.37

Example 8

Aiaid ation b y t-ert. -Amyl alcohol

A 30C-uil-i <ion autoclave is charged with 120 g (0.0 mol) of liquid hydrogen fluoride and 49.2 g (1.2.0 mol) of acetonitrile at 0-5.degree. The autoclave is closed, "before the temperature is brought to a value of up to 60 ° G; 35.4 g (C, 4 mol) of tert-amyl alcohol are then added over a period of 20 minutes at an ambient temperature of 60-65 The stirring is continued for a further 30 minutes at 60-65 ° C. The contents are then cooled to approximately 5 G, whereupon the reactor is opened Hydrogen fluoride is driven off by heating the reaction mixture to 2CC ° G. The residue is then dissolved in ether and washed free of traces of hydrogen fluoride. The ether solution is then dried over anhydrous tiatrium sulphate and concentrated in the vial: u.uüi, 15 g of tert. -A-iiylacetamide (yield 29 #) .

^. . _AQ v 'r. ■ ORIGINAL BATHROOM

f> amide: 83.5

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Example 9
^; from 'j -ilt

A 300-ail-ion autoclave is jrLt 12C g (6.0 liol) fli'ssi, eoi iluorwasser-tcff and 4- ^! , 2 u, (l, c _; .lol) Acetonixril;: ei C - 5 ° C bescuix-t. Lter a ^ u ^ or .vird / ez jcnlo. : .c: i, in front of the! Je: ϊ e ^ .t-Jir a.if eke :,, --- rt Li3 su -: C 0 eru ^ .it .vira; then ./ercpu ί ", ί> fi 'C, 4 ..1 ^ 1; i5 -."! thyl-; ^; -]; e ^ tc-iiül v / ^; ; iirend eiiier ^ eitsj; -. ^T .rie / jn cvj ..linuie .. ¹ ^ i ei.ior: eu; οίε * .tar of OC - 3 ^ ° 3. ■■ '.-.-; ei uj ^ t. Jxe ..fliir-- · ι -: IRF v.-el, ere '' X ... i / r te / i at ^ C - iS Ο: or: - eset ^ i. j ^ .. · liialt iro u .r

u .rm ^ l.ί Lu; e-

■ fi.hr 5 ° G at _e .ek'ult, \; cra ^ l -er ^. ; ^ or e ^; 'f ■ :.'. et will.

jiiscriuiiie v / ird in ICCC ul --aite ^ ia ;; er., ecOÄen, whereupon ICoC dI; 'ther zajesf-t ^ iv / er-ieu. DIT ei "anlache IH ^ e" is from;, etrerjjit and ^jiluorv: = i.br; erBtofi 'freiyewascnen. The Atiierlcs'J ....- is daixii over anhydrous.!] ITi.triaiisulfat, ^ etrocicnet. With the Ilona entrierun§ ia vacuum, 59.5 g of the product are obtained (yield 62.5 ', 0).

Aaid:

The results of the preceding examples are in the following Facts classified as:

909881/1399

-ig -

Hurry

i. * o Iv received-

Alcohol 2-Butanol 2-NonanoI 2-Ileptadecanol Cyclohexanol 2-.uvh; y "1hexanol n-Oecstnol n-Dodecnnol tert -A.iiylalkoliol 3 -λ t hy 1 - 3 - ρ ent ano

Ii
C. alcohol
I _x ClT: , 0 : l, Q - since 1 ^ n,
Teajp. C. .tie action yield f-5 Amide
JS 1 ~ 7. "■ ■
: 3 .C : 15 , C - 6G / 6C-55 69 , c • vi, ο 1 : I. .0 : 15 .0 5-c / -19-58 20, 58-? 3 93 , 5 33.4 1 : 5 Λ : 15 .0 - eCv'60-65 94 , 7 93.0 1 : θ .0 : 6C .0 27 / '54 - ^ -ü / 50-52 61 , 5 ■ ■. 97.5 1 : U .0 : 15 .0 - 3.0 / 50 -S 5 55 , 2 70.5 1 Y 3 .0 : 15 - 40 / 80-85 45 ,8th IS, 9 1 · "* 2r .0 »15 3V9C-9 "- TC / 92-95 ■ 51 , 0 ■ 5.37 1 : S. .0 : -15 2C / 60-05 30, 6D-65 29 , 5 83.5 1 2O / 6G-65 30 / 60-05 62

909881/1399

Claims (6)

-2C- 1 5 A 3 31 7 a t e: it ansyr ■ lclie: 1. / learned about the transformation from alcohols to amines, characterized by the fact that an alcohol falls under the following rules Marg • c R ₂ -C-OH una wherein 'R ^, R ^ and R. _x Yfossstoff, alkyl, arylalkyl or Cycloalkyl radicals and iilischangen this rests with at least one reads mean except hydrogen, where the Contain residues 2-48 carbon atoms, R ^, R ^ and R ^ ', hydrogen, alkyl, arylalkyl or Cycloalkyl radicals and mixtures of these radicals represent uni the Sujiaie of a \ b 4 c is between 2 and 9, • 909881/1399 BAD ORIG / nal aiD Mtril the Foroiel in which IL _{7 stands} for hydrogen, an alkyl, aminoalkyl or aryl radical as well as for metal salts of the AJiinoalkylresxes, the radicals 1 - 21 containing carbon atoms, in .Cre ^ en-wart of hydrogen fluoride at a temperature of ■ about 25 - 100 ° C converted to form an amide that falls under one of the following formulas: R ₂ -C-HH-C 909881/1399 where Xi ₁ , E ₂ , Iy R ₄ , Ii ₅ , R ₆ , B ₇ as well as a, b and c have the meanings given above, then the Aaid with a hydrolyzing agent at a temperature of less than SC - 3CL ⁰ G anfcei · tilaai :: Aj ₁ in ο η ux-e is that ilen under the formulas It: R-, '" ^Hi -2 and (CHO in which the substituents have the meanings given above, and the amines are separated off from the reaction mixture will. 2. The method according to claim 1, characterized in that the molar ratio of nitrile: alcohol is about 1.1: 1.0 to is approximately 4.0: 1.0. 909881/1399 3. method η- * c, λαό rue. 1, uadarch ;; e.it: "ai; if - .: ic-Li-.t that iui; ef ^: 'lir J .it .. 4, / experienced i. ^ C'-i .'jit;ru'ca 1, did ι: · el:; eLenn: .eiclu: fct, ds ^ das ■., io.lver - »." Itiiir Vlyor.va -> - erc t ^ ff: alcohol · - J. ^s .ui, <; f? In · 0:25 t-etr "/" t. 1-. procedure u-icr. Aii &. ^ Rnc 1, da-aarch .- c ': ii: r -.:>- ichrJ: rt, cuu ". The'ie.Ji-'erytar der ersuen ΛλΙe tei ■ · .. !! - ef ' ^: . _t r t. - l '^ TG lie / t. 6. /erx'i·.'i't-n after Ane ^ racii 1, aua iron; ^r e ^ ^{ennseiciifi:;} t because .. "the Je ι ■ (r u tu.r Sivitcae.i ± efshr -2 '. u- IOE It ^{f 0} J li'e.-...? t. BATH 909881/1399