ITEM No. 8,22

FILE No. XXIV - 19

ANORGANA G.M.B.H. WERK GENDORF

COMBINED INTELLIGENCE OBJECTIVESSUB-COMMITTEE

ANORGANA GmbH WEEK GENDORF

GENDORF. GERMANY

MISCELLANEOUS CHEMICALS

1S-19 May 19^5

Reported by:

V.C. BIDLACK - TIIC ChemicalsF. J. CURTIS - CW3, Hq ETOUSAJ. M. HARRIS - CWS, Hq ETOUSA

12 June 19^5

CIOS Target Numbers S/S6, 22/1 (f), 22/534Chemical Warfare

COMBINED INTELLIGENCE OBJECTIVES SUB-COMMITTEE0-2 Division, 3HAEF (Rear) APO 4-1 3

2

•S6Ti*.-S

TABLE OP CONTENTS

Page No*Subject

i c General 32. Chemicals Manufactured from Acetylene 93. Chemicals Projected from Acetylene 194* Application Data on Surface Coatings 275. Pharmaceuticals —- 286. Miscellaneous Items 317 • Charts -

Acetylene + Formaldehyde —~ 33-Butyrolactont —————————— 35

Acetylene + Acetaldehyde 37

PERSONNEL OP INSPECTION TEAM

Lt. Col. P.R. TIER- CWS,Hq ETOUSACol.J. H. ROONEY M. of S.Lt. Col. S.B. GORMAGK— M. of S.Lt. Col. J.W. CRAWFORD- M. of S.Major T. LOVE M. of S.Major H.N. RYDON M. of S.Mr. V. G. BIDLAGK CWS,Hq ETOUSAMr. P. J. CURTIS CWS,HQ ETOUSAMr. J. M. HARRIS CWS,Hq ETOUSAMr. I. H. JOKES Petroleum AttacheMr. Gr. M. KLINE OD, Hq ETOUSAMr. E. B. PECK — Petroleum Attache

36Ti4,-5

ANORGAKA GmbH

WERK GENDORF

MISCELLANEOUS CHEMICALS

1 • GENERAL

Anorgana GmbH was started as a subsidiary of I.G. Farben-industrie AG in June, 1940 and financed by Montan Industrie WerkeAG, a subsidiary formed by the German Government to handle suchmatters. The cost of construction was 120,000,000 marks. Duringthe war and while construction was going on 4000 workers were em-ployed, partly foreign. It is estimated that normally 2000 workerswould be needed for full operation and for the present situationabout 1000 could be used.

a. Organization

Names and positions of officials of the Anorgana GmbH:

Managing director Dir. Dr. M. WittwerInorganic department Dr. M. GruberOrganic department Dr. G-. HagenSales Service department Dr. J. E. v. KlenckAccounting W* JansenSocial department Dr. E. LederleOrdnance department Supt. K. Wurzler

Name and position of official of I.G. Farbenindustrie AGt

Research and pharmaceuticals Dir .Dr. W. Reppe

b. Present Daily Manufacture

Leonil (detergent) - 300 kgLuphen (lacquer) - 1,000 kgEther (narcotic) - 250 kgEthylchloride techn. - 3>000 kgEtiylchloride pro narpose- 250 kg

c. Rav; Materials and Finished Products on Hand

Common salt 2.477 tons Formaldehyde 30°/o 30 tonsBarium carbonate 354 " Ethylene oxide 52 "

Aluminum chloride 6l tonsCopper sulphate 2.5 ”

Adipic acid 30 11

Ethylglycol 11 "

Ceresin 2.5 ”

Urea techn. 5 H

Resin 6.7Naphthlene 2 "

Ootadeoylaloohol 2.5 ”

Castor oil 9*3 *

Sesame oil 20 ”

Rape-seed oil 4*5 rt

Olive oil Illrdquality 4.5 "

Paraffin 20 "

Stearic acid 11.6 H

Benzene 48 "

Active carbon 5 ”

Orthodichloro-benzene 15 ”

Carbon tetra-chloride 2.5 **

Phosphorus-trichloride 2.3 n

Triglycol 114.8 wGlysantin withtri (Prestone) 65*7 "

Carbide 3*108Acetaldehyde 380 "

Soda 65*4 tonsSodium bisulphite

as S02 100$ 19 "

Hydrochloric acidas HG1 100$ 36 ”

Graphite 290 "

Mercury 62 *7 H

Sulphuric acid asSO, 127 "

Chlorine 90 wCaustic soda insolution as 100$ 350 w

Ferrous sulphate 32.5 ”

Nitric acid 62$ 8.4 ”

Methylated spirit 270.4 "

Phenylglycine 43*6 M

Coke 80 "

Diethylbsnzene 122 n

Sulphur 950 w

Chloride of lime 27 nCaustic potash 10 w

Calcium chloride 10 w

Methanol 0*3 wEthylene chloride

crude 171 nEthylene chloridepure 208 w

Glycol 565 *

Diglycol 677 ”

d. Supplies Needed

Coal Prom; Pensherg or HaushamCoke Munich or other municipal

cokeriesCarbide HartSalt Heilbronn near StuttgartOils Stores in Passau, TBging and

RegensburgTolueneBenzenePhenol

Ruhr Territory

AmmoniaNitric acid Middle Germany

3&rsuf.-Jt

Sulphuric acid Kelheim near RegensburgNitrocellulose AschauPeroxide of hydrogen Krai bargSolvents BurghausenPlastics BurghausenUrea OppauPorraamide OppauMethanol Regensburg

e, Production Capacities in tons/month(1) Lacquers

Luphene 35Phtalop&l 100

(2) Plasticizers

Palatinol 50Soronline 10

(3) Plastic*

Lupolene 5Luvitherrae 10

(4) Solvents

Glycol 1,000Glycolether

(Ethyl, butyl) 100

(5) Detergents

Leonil 50Igepon 125

(6) Waterproofing Agents

Ramasite 20

(7) Organic Chemicals

Ethylchloridetechn. 90

Etl^ylenechloride ifOOAcetaldehyde 2,000

StTH.*. -JB

(8) Inorganic Chemicals

Chlorine 2,500Caustic soda 3>000

(9) -Pharmaceut icals

Principal products in kg per month:

Ether 5>000Ethylchioride 7,500Hartosol 5>000Postonal 1,000

Specialities in g per month:

Kresival 20,0002ephirol 5,000Phanodorm 1,000Evipan 1,000Eunarcon 500Novocain 1,000Adrenalin 1,000Acetylphenothiazine 500Avertin 1,000Insulin according to delivery

of glandsPeriston according to delivery

(Solution of butandiol-l,A.

f• Research

(l) Organic Section

Formation of Butadiene out of EthanolGlycol-ethersVinyl-chiorideAlcohols of AcetaldehydeDulcinTextile auxiliariesEthylbenzeneStyrenePolystyreneLacquers (Resins)EthylchlorideChlorination of benzeneChlorination of fatty acids

3VT!M<.-3

3 AT**.-*

PolyethyleneOxidation-experiments (ethylbenzene and others)Rubber-ooraposit ionsChloralInsecticides (chloral and chlorobenzene)Purification of crude ethylenechlorideAldolEther for narcoseGrotonalde hydeCrotonioacid

(2) Sales management

Preparation of varnishes and lacquers based upon

NitrocellulosePhenolic-resinsPolyviiylohlor ides

PlasticizersSolventsResinsShoe-polishFloor-polishGluesEsters of diglycolicacid as plasticizersPolymerization of crude butyleneTextile auxiliaries as:

DetergentsWaterproofing-agentsSofteners

(3) Inorganic Section

Water electrolysisCarbonmonox ideProduction of charcoalRegeneration of potassium permanganateSilver catalyst for formaldehyde synthesisBasic Aluminium chloridePhosgene (for organic synthesis)Thionyl chloride (for organic synthesis)Chlorosulfonic acidAmmonium nitrateAluminium acetate

5b72.fc.-3

(4) Main Laboratory

(a) Pliarmaceutical products:

Ether pro narcosiEthylchloride pro narcosiMitigal (DimethyIthianthrene)Hartosol (isopropylalcohol)Kresival (Calcium salts of eresolsulfonic-acid)Zephirol (D imetliyl-benzyl-aliyl -ammonium-

chloride)Phanodorm (5-ethyl-A-1-cyclohexenyIbarbituric-acid)

Evipan (3#5-Diinethyl-5-A-l-cyclohexenyl-barbituric-acid)

Eunarcon ( 3-Methy 1-3-H -bromallyl-5-isopropyl-barbituric-acid)

NovocainAdrenalinAcetyIphenot hiazineAvertin (i.1.1-Tribromoethanol-2)InsulinPostonalAbasin ( 1-Acetyl-3-(bromodiethyl)-acetyl-

carbamide)Perist on (poly-N-vinylpyrrolidone )

Sulfonamide:

Frontosilum albumPyrimalEleudronEubasin

Urotropine (Ilexametbylentet ramine)Camphor oilBarium sulphate

(b) Organic Intermediates:

Formaldehyde from methanolEthanol from EthyleneOctadecylalcohol from vegetable oils by highpressure hydrogenation

Higher alcohols from long chained olefinesEster of OxyraethylviryIketone from butin-2-diol-1,4

•9

(o) Plasticizers, lacquers and plastics section:

Resins of phenol formaldehyde (Luphen L) withor without plasticizers

Resins of phenol acetylene for plasticsResins of melamine formaldehyde by reaction of

dicyandiamide with melamine (nitrogen calcium)Organic thioplastics (Thiokol a*s*o*)Ethyl cellulose

(d) Textile auxiliaries s

Igepon A with intermediate productsIgepon T from Ethylamina including inter-mediates*

Igepon from monoethanolamine

(e) Inorganic auxiliaries s

and SCI2 2 2Interviewed: Dr* Ambros*

2. CHEMICALS MANUFACTURED FROM ACETYLSNS

a* Preparation of Acetylene

Acetylene was made at Gendorf from calcium carbide producedlocally (Trostberg)* In spite of the high cost of the carbide(180 RM per T) it is claimed that ethylene (See b below) made fromacetylene was cheaper than ethylene made from ethanol*

Acetylene was generated by both the "wet” and the "dry"gasification processes* The "wet” process, in which carbide wasfed to water in an agitated vessel and the resulting lime slurrythrown away, is old and needs no farther description* The gener-ator used for the "dry” process consisted of a rotating cylindercontaining an inner wire mesh cylinder about 8 inches smaller indjameter* The two cy7i.inders rotated about an axis inclined about8 from the horizontal after the manner of a rotary kiln drier.Carbide was fed in lumps about the size of a walnut to the upperend of the generator and was tumbled about on the rotating screen*Water was added at five different points causing the evolutionof acetylene and the lumps of carbide to crumble to a dust whichpassed through the wire mesh inner cylinder and rode to thelower discharge end of the generator through the annulus between

Sb7X.tt.~S

3<»ys.tt. - 3

the two cylinders* The Ca(0H)2 discharged contained about 5% waterand could be readily handled by a screw conveyor* The acetylenewas dried by passage over the incoming carbide, passed throughcyclone dust separators and finally emerged with a purity of 98%,The chief impurity was nitrogen with which the carbide was blanketedduring shipment. According to Dr. G-ruber, the operation of the*dryw generator had been unsatisfactory and several difficulties(e.g. the steady feeding of the carbide) had not been eliminated.

Acetylene from carbide was pure enough for the preparationof acetaldehyde, but before it could be hydrogenated to ethyleneit must be purified as follows:

I - Scrubbed with dilate chlorine water to removeHgS and PH,.

II - Scrubbed with a solution of caustic soda toremove chlorine and for partial drying.

An attempt was made to purify the acetylene by passingit through active carbon but the process was unsuccessful and wasabandoned.

Carbide was used in the amount of 150,000 tons per year -

equivalent to about 47,000 tons of acetylene •

b. Preparation of Ethylene from Acetylene

Ethylene was prepared by the hydrogenation of acetylene.The acetylene was prepared and purified as described above. Thehydrogen was a mixture of electrolytic hydrogen and hydrogen pre-pared by the ”steamiron" process. It required no purification asits chief impurity was carbon monoxide, which was hydrogenatedto methane and did no harm.

The reaction was carried out in 22 converters arrangeddown two sides of a large building, 20 of these manifolded sothat they may be operated in parallel. All the production ofthese 20 was passed through the other two in series for theremoval of the last traces of acetylene. The converters werevertical cylinders about 10 ft. in diameter by 15 ft. high.Inside each cylinder were alternate layers of catalyst and bubblecap plates. The plates act as gas distributors and did notsupport any liquid. The gas mixture recycled through the con-verters contained about 5$ acetylene, 8$ hydrogen, water vaporand ethylene. The converters were operated at 7-10 p.s.i.ga.and at a temperature of 180-320°C depending on the age andadtivity of the catalyst.

Fiqu re XEthqleneChlorhqdnn Equipment

G e n d or fWote r

ft ecuole

c2 h4 c i (oh)HC IC, HiCUWater.1/ent

C h 1 or i n &

Chlorine

Water10“ 15°C 1 &Q po h i f i c t*

*

n gi e n e

(T) Feactor i BricUlihed C.I. x 12M(2) Condenser - Scrubbe r; B rick 1 med C.I.0 Still Uq-for deqasificaiion of product® blower ~ to recqde qoses(5) Pipe conv'eqinq liquid - qas mixture to still Leq.0 Pipe returnincj qases to reactor

Mavj 2®,

The catalyst was silica gel containing traces of palladiumsthe exact amount of palladium not being known as the catalyst wasprepared at Ludwigshafen• It was estimated at 4-8 parts permillion. Catalyst .life was about 12 months.

The exit gas after cooling contained 65$ ethylene and wasfree from acetylene. It was dried over silica gel and liquefied bythe Linde Process. A three column system was used. The partiallyliquefied mixture was fed to the middle of the first column fromthe bottom of which high boiling compounds (C, -Gq) are removed.Hydrogen, methane and nitrogen were removed from the top of thesecond column from the bottom of which liquids passed to the sideof the third column. Ethylene passed from the top of the thirdcolumn and ethane from the bottom.

A second fractionation of the ethylene will give materialfree from ethane and having a purity of 98$ but at an appreciableextra cost.

The output of the G-endorf plant was 25*000 to 30,000 T.ethylene per year.

c. Preparation of Ethylene Chlorhydrin

Ethylene chlorhydrin was prepared by the action of chlorineand water on ethylene. The equipment is sketched in Figure I.Ethylene was fed to the side of the reactor and chlorine at pointsabove and below the ethylene. The following reactions occurred:

(ethylene chlorhydrin)

There was also a side reaction:

(dichiore thane)

Four of the units described (Figure I) required per hour:

2000 V? Ethylene (gas)1000 V? Water (liq.)6000 kg Chlorine

The Ghlorhydrin produced was not isolated but was hydrolyzedimmediately to ethylene oxide. The yields of chlorhydrin were notknown but the above feed rate produced 2.7 T. of ethylene oxideper hour.

Diehlorethane in the amount of 0.7 T. per hour was producedsimultaneously.

3&T2.^.-3

F i q u r e ItEthqlene Oxide Equipment

CZH4OH 2 0 60&H z O 56%'

Ca(0A]2 \2%c 2 h4 (oh)ci.

-IOO°C

Plates heatedtndirecflq withSteam ~

0 Soponifier C.I. 2.5M(J)X 6M0 Oephieqmoiior to reduce loss of wafer with product/jn Plates, steam heated, with., vertical baffles to

qive lanq tortuous path for reaction fnixt.

J.WA.H.Moq 5Q FM5-

367Z/J.-3

Gendorf operating personnel believed that future chlor-hydrin reactors should be made smaller and that all the chlorineshould be introduced below the ethylene inlet to suppress theformation of dichlorethane• The latter modification is basedon the theory that if all the chlorine has reacted with thewater before ethylene is introduced, reactions I and II occur* Ifchlorine comes in direct contact with ethylene reaction III takesplace•

d. Preparation of Ethylene Oxide

Ethylene oxide was prepared from the chiorhydrin by thefollowing reactions

The reaction was carried out in the equipment sketched inFigure II* There are four of these "saponifiers*1

, each connecteddirectly to one of the four chlorlydrin units described in Figure T#The chlorhydrin, HG1, water mixture and milk of lime were fed to thesaponifier through concentric feed pipes in the proportion of 2 vol.chlorhydrin mixture to 1 vol* 12$ Ca(0H)2 slurry* The resultingreaction slurry was led through a long tortuous path in thesaponifier on baffled, steam heated plates as shown* Ethylene oxideand steam distilled out the top of the reactor through the dephl-egmator which removed some of the steam. A calcium chloride -

calcium hydroxide solution was dhawn off from the bottom.

The ethylene oxide-water mixture was fractionated in a threecolumn, continuous distillation unit. The first two columnsoperated in parallel and received the ethylene oxide - water mixturefrom the "saponifier." They contain 50 bubble cap plates andreceived the

Qfeed on the 17th plate* The reboilers were steam

heated to 55 0* The top column temperature was 12°C. These twocolumns were operated with a reflux ratio of 3/1 and producedAj0-50 T. per day of 98$ ethylene oxide.

Residues from the first two columns were fed to a thirdcolumn having a reboiler at 80°C. The water was removed from thisreboiler.

Vapors from the third column were fed to the first twocolumns on the 33**8. plate •

The yield of ethylene oxide based on ethylene amounted to70 - 75$ of the theoretical.

All three columns were made of oast iron.

S67ZM.- I

Dichlorethane was removed from the hottan of the thirdcolumn, washed with sulfurio acid, hydrochloric acid, and causticsoda solution and finally distilled batctarise*

e • Preparation of Glycols

Ethylene glycol was prepared by the reaction*

Steam and ethylene oxide were passed up through an ironcolumn packed with steel Raschig rings* The ethylene glycol pro-duced was purified by fractionation* By altering the temperature,pressure, and feed ratios the same equipment can to used for theproduction of diglycols, for examples

f. Detergents

"Leonil" detergents were made from long chain alcohols andethylene oxide* The type reaction is;

The compound made from 8 ethylene oxide molecules and onealoohol molecule is water soluble and is a detergent* The com-pound made from stearyl alcohol was made up as a 30$ watersolution and sold as "Leonil 0 Lag," or Genapol* It was actuallybeing sold in considerable quantities because of the soap shortage*As it contains no sodium it cannot form salts and may, therefore,be used with hard or soft water* It is excellent for wool scour-ing in either acid or neutral media* When used for domesticlaundry soda is added* It does not foam and therefore does notsell readily*

As of May 19, 1945» enough raw material was available atGendorf to prepare 42 T of Genapol (weight of water included)* Forsubsequent production it will be necessary to prepare the fattyalcohols by hydrogenation of fatty acids*

These compounds were prepared in an enamel lined kettleunder 45 p*s*i*ga* and at 165°C* The fatty acid was charged and

J4TM.-S

the ethylene oxide introduced until the batch shows the correcttitre, sp.gr., mol. wt., etc.

The preparation of "Igepon 0" may he outlined as follows:

"Igepon A”

"Igepon A” decomposes at about 100°G; therefore it cannotbe used if laundry must be boiled*

"Igepon G-" was not made from ethylene oxide. Its preparationis outlined in section 6 of this report (miscellaneous chemicals).

g. Emulsifiers

Compounds made from 20 ethylene oxide molecules and one'fatty alcohol molecule sure emulsifiers sold as "Eraulphor C w aniwere used in the preparation of emulsions used for spinning wool.

One oleic acid molecule combined with 6 ethylene oxidemolecules gives Emulphor A, used for emulsifying machine oils likespindle oil.

Castor oil plus 40 ethylene oxide molecules gave "SmulphorE.L."

h. Textile Aids

Compounds of 20 ethylene oxide molecules with one fattyalcohol molecule, were used as levelling agents for dyestuffs andwere sold as "Polatinechtsolze." A water solution of thismaterial was sold as "Diazopon"; a solution as "Peregal 0."

Stearic acid combined with ethylene oxide gave "SorominS.G.", which was sold as a softener for artificial silk.

i. Waxes

Waxes may be made by the polymerization of ethylene oxide -

the so-called "polyethylene oxide waxes.” None have been preparedat Gendorf lately.

E.L."

Jtr.A.H. Moq5l,ISA5

Condenser.C-I-

Water AceiicAcid

waterocrubber

(?)

DiluteAldchtjdeStoroqe

(S)Tract.Col.

-

2SPlote6

finishedProd.51oraqe

Fiqure

HI

AcetaIdshqde

Equipment Water

(T)

ReactionTower

©

Condenser©

MercurySeparatorsteo

m

Acetij

leneS5°C Cot

'

HS

._

aj»7s.*.-3

3* Thiodiglycol (Oxol

The thiodiglycol plant had never been run and Dr. Hagen wasunable to give ary data as to production capacity. An aluminumtower, 6 m high x 0.66 m dia., packed with Raschig rings and equippedwith cooling and heating coils is filled with thiodiglycol fromprevious manufacture. Hydrogen sulfide gas and ethylene oxide arepassed in at the bottom maintaining a temperature of 90°G. Theproduct overflows continuously to a cooler and to storage. Com-plete absorption of the gases is obtained.

If it is desired to purify the thiodiglycol, it is driedunder vacuum and treated with enough ethylene oxide to unitewith the hydrogen sulfide present as determined by titration.

k. Acetaldehyde from Acetylene

Acetaldehyde was made from acetylene in two units and thecrude product was purified in a continuous fractionating column.

Production from the two units amounted to 1800 T. aldehydeper month.

The essential reaction is;

This reaction was carried out in two vertical cylindersabout 2 m. diameter by 8 m. high. These cylinders are made of V2Aand contain no packing. The heads are designed to act as entrain-ment separators.

A layer of mercury stays in the bottom of the reactor at alltimes. The reactor was charged with a batch consisting of;

3000 kg Pe SO,1600 kg8400 kg Y/ater

Acetylene in the amount of 860 per hour and under apressure of about 25 p.s.i.ga. was introduced below the level ofthe mercury which is thereby agitated until there was a mercuryemulsion throughout the batch. Live steam was introduced near thebottom to help the agitation and to keep the batch temperature atabout 95°C. Approximately IT. of steam v/as required per batch.

The vapors from the top of the reactor were cooled to 40°Gby passage through a water cooled condenser* They k then passed to amercury separator from which mercury and condensate passed back to36T»*.-3

S672*.-3

the reactor tower. Mercury lost by this process amounted to 1 kgper T of aldehyde produced.

Vapors from the mercury separator passed to a water scrubberpacked with Raschig rings in which the aldehyde and a trace ofacetic acid were washed from the gas. The scrubbing liquor from thebottom contained about 7*5% aldehyde plus a trace of acetic acid.It was sent to a continuous fractionating column. Gases from the topof the scrubber, chiefly acetylene, were x-ecycled to the reactor.

The aldehyde solution corresponding to an acetylene feedrate of 860 per hour amounted to 21770 kg per hour. It passedthrough a heat exchanger, a steam heater, and was fed to the 21stplate of a 29 plate column. This column is 2 m in diameter by 10 mhigh, from the feed plate down, it is const meted of V2A, Abovethe feed plate it is cast iron. The top column temperature was 21 C,the boiling point of pure acetaldehyde. The roboiler temperaturewas 100 C, The residue from it was water plus a trace of acetic acid.The reflux ratio was constant at 2/1. The aldehyde taken off wasdegassed in a small column with a reboiler at the bottom. Theacetylene recovered was put back in the recycle gas. The final pro-duct from the reboiler was 99*9% acetaldehyde.

During the reaction the ferric iron content of the catalystsolution gradually decreased until a point is reached at which con-version fell off. The catalyst was then drawn off to a settling tankin which the mercury settled out. It then passed down through abrick lined tower packed with ceramic Raschig rings in which it wasblown with live steam. Next it went to a second settling tank inwhich more mercury was recovered, and from there to the oxidizer. Inthe oxidizer the ferrous iron v/as oxidized continuously to ferric withnitric acid." On leaving the oxidizer, the solution was dark browndue to the presence of which was broken down by air blowing.The oxides of nitrogen from the blowing were recovered by waterscrubbing in 5 towers in which the water was recycled counter currentto the gas flow. The 15% nitric acid thus obtained v/as blendedwith fresh acid to a concentration of 25% and used again in theoxidizer. The catalyst solution after air blowing was ready forreuse*

5. CHEMICALS PROJECTED FROM ACETYLENE

Dr. Reppe removed his laboratory to Gendorf when it v/as bombedout at Ludwigshafen last fall. Dr. Reppe is a very creative re-search worker on the reactions of acetylene and has evolved a largenumber of schemes, few of which have been put into operation.

20

a • General Schemes for Development of Acetylene Compounds

Much of the framework of Dr, Reppe*s ideas is contained inthe three attached charts;

(1) Acetylene + Formaldehyde.

(a) Y- butyrolactone.

(2) Acetylene + Acetaldehyde,

b. Processes Reduced to Practice

(1) 1*4.butanediol (1,4 butylene glycol)

Several thousand tons/mo, of 1,4 butanediol were pro-duced at Ludwigshafen, largely as an intermediate for butadiene.1,4 butinediol was first made in a tower 18 m. high x 1.5 m. diametercontaining 20 cu. m. of a contact mass of copper acetylide onsilica gel where the copper compound is 10-12$ of the contact mass.Five times the theoretical acetylene and formaldehyde diluted to 10%with liquor from the bottom of the tower were passed into the topof the tower under a pressure of 5 atmospheres of which 4 were dueto acetylene and 1 to water vapor evaporated in the process. Temper-ature was 100 Go 1 cu. ra, contact mass produced 1 ton of 100%butinediol per day.

The product was a 30$ solution in water, which canbe evaporated off and the diol crystallized from ethyl acetate. Thediol can be distilled under ordinary pressure. Propargyl alcoholgoes off in the first part of the distillation and can be recir-culated with the formaldehyde.

The reaction is;

A side reaction to give propargyl alcohol also takesplace;

Yields are;

Acetylene 92$Formaldehyde 95$

+ 4$ to propargyl alcohol

The 1,4 hutinediol was hydrogenated by running itdown a tower over copper nickel in the presence of hydrogen at 200-300 atmospheres and at 80-130 • A yield of 96$ to 1,4 butanediol

S6TZ4--3

is formed which is converted with ammonia to the £ -caprolactamOT

was obtained with the balance going to butanol# Coat of 1,4butanediol were 60 pfg/kg and it is expected that it may be reducedto 40#

o. Tetrahydrofurane and Adipic Acid

Tetrahydrofurane was produced from 1,4 butanediol in 92$yield by passing over a catalyst of phosphoric acid containing 3/2- 1$ phosphine at 260°C and 70 atmospheres pressure# The productis a good solvent and is known as Losungsmittel T#

When tetrahydrofurane was reacted with two mols#, carbonmonoxide and one mol# water at 200 atm# and 270°C with 10$ nickelcarbonyl a yield of 90$ of adipic acid was obtained#

In practice the water containing 1$ of its weight ofiodine in the form of niokel iodide and the tetralydrofurane inwhich the niokel carbonyl is dissolved were passed into the bottomof a tcwer with the CO gas. Adipic acid flowed out the top pre-sumably with sane tetrahydrofurane. The GO gas and nickel car-bonyl passed to a separator to remove the latter and the CO re-turned to the tower. Throughput of the tower was 300-600 cu. n/hr.of the furane.

d. Propargyl Alcohol

The reaction for 1,4 butinediol can be run to give 80$propargyl alcohol instead of 4$ if desired. By hydrogenation withan iron catalyst under pressure, propargyl alcohol was convertedto allyl alcohol and with a copper catalyst to propionaldehyde•

Oxidation of propargyl alcohol with air at 50°G over acupric chloride catalyst gave hexadiindiol 1,6

HOHgC - G: a C - C a C - GHgOHwhich on further reduction goes to the hexanediol 1,6.

By conversion of the hexanediol to the double aldehydefollowed by an internal Canizzaro reaction g-caprolactone

GB^GHgCHgCHgI !

CH2 -0 - OG

GHg-MT- OC

for the polyamide known as Igamid B.

e. -y-Butyrolactone and N-viryl Fyrollidone

1,4 butane diol may be dehydrogenated in a tower in thepresence of copper strips at 200°C to form y butyrolactone in 96$yield* Reaction with ammonia gives a 90$ yield of pyrollidonewhich on treatment with acetylene furnished N-vinyl pyrollidonein 90$ yield*

— CHo\

2CHo G = 0

V �NfCH = CEp

The N-vinyl pyrollidones are the bases of a new series ofpolymers, largely water soluble and of a character resemblingalbumen* They are used for glues and plastics but few uses have asyet been developed except the blood substitute ’’periston”, de-scribed in report on the I.G. at Elberfeld* The degree of poly-merization is controlled by the amount of hydrogen peroxide whichis varied from 0.05 to 1.0$. The more peroxide used, the shorteris the polymer chain.

(1) Methods of polymerization

(a) Bloc]:, type

35 kg K-vinyl pyrollidone were mixed with 150 cc3C$ peroxide solution and UK, equivalent to 3/2 the ILOg and heat-ed to 110°C. Without further heating the temperature went to 180-190 C. The hot polymer flowed out of the kettle and was cooledin blocks. The product has a yellowish color due to the hightemperature, has a low K value (30-35) and contained about ICf/omonomer which was extracted with ether before solution of thefinal product in water and filtration.

,rPeristonu is a 2.5?o solution of a product madein this way where the temperature is kept to 70-80 G.

These products can be used as glues and bindersfor films, for adhesives, thickeners for emulsions and solutions,and assistants in dyeing causing darkening of the color.3672.*-»

(b) Solution Type

To 30 parts N-vinyl pyrollidone in 70 partswater was added 0.5 parts 30$ peroxide solution and 0.1$ ammonia(100$) at 20°C. In presence of the oxygen of the air no reactiontakes place, but in a stream of nitrogen it begins immediatelyand is complete in 2 hours. The product has a K value of 56.

(2) Acetylene polymers Cyclopolyolefines

By condensation of an excess of acetylene under a totalpressure of 10-20 atmospheres of which 5 atmospheres is nitrogenpartial pressure and in the presence of a solvent such as tetra-lydrofurane, cyclooctotetraene CgHg was obtained at 60-70°C inliquid phase by means of a catalyst of nickel cyanide on a carrierwith a yield of 90$. The reaction took place in a tower, both gasand liquid entering at the top. The liquid product v/as distilledand the tetrahydrofurane returned for reuse.

Small amounts of C 1 qH-Lq and soluble resins,and cuprene were also formed and particularity dy raising the temper-ature the proportion of these can be increased. The best temperaturefor is 80-90°C and for about 130-140°C. Azulen formsas a by product when the temperature is 80-130°C.Gycl 00ctatetraene CgHg 142-143°C Golden Yellow

Cyclodecapentaene G SPg 48-50°bBP?50 190-195°C Deep Yellow

Cyclododeoahexaene G BPn c, 60-65°Q230-235 G Bright Yellow

Azulen C 10H8 W 99.5°C Deep Blue

The constitutions of CgHg and of Azulen are definit-ely determined, the former being:

OH » GHV

GH GH5h >

= GH

The constitutions of CinHnQ and need furtherclarification.

The CqH8 and have been investigated pharma-cologically v;ithout finding ary action. On the contrary. Prof. Kuhn

36Ti*.-5

36T*-*.- 5

determined that the growth of certain pathogenic bacteria wascompletely suppressed in a dilution of 1:100,000 by thefraction which because of small amounts of azulen (about 5%) wascolored deep blue.

(3) Ethyl Alcohol

Dr. Reppe claimed that a practical process bad beendeveloped for direct hydration of ethylene which, in Germany, islikely to be produced from acetylene. The process is applicablealso to propylene and butylene.

The olefine and water were run into the top of atower packed with a catalyst consisting of a mixture of WOg andWO, made from ammonium wolframite and promoted with 5$ zinc oxide.The catalyst is carried on silica gel and the mass contains 20$ W.

in the tower was 200-300 atmospheres and the temperature300 0. In practice the whole system was kept under ethylenepressure as above, new ethylene being pumped in to replace thatused up.

A 20$ solution of ethyl alcohol flowed from thebottom of the tower to the rectifiers. The catalyst converted1 liter ethanol per liter catalyst per hour.

(4) Acetylene and Alcohols

The type reaction for aliphatic alcohols is;

RQH + C2 = ROGH: digThis reaction must be carried out with the alcohol in

the liquid phase. The lower the molecular weight of the alcohol,the lower the optimum temperature of reaction, hence when the boil-ing point of the alcohol is lower than the reaction temperature,sufficient pressure must be maintained to keep the alcohol in theliquid phase.

(a) Acetaldehyde

These principles are used in the Reppe processfoi* acetaldehyde which is not new. Methanol is treated withacetylene at 20 atmospheres pressure and 90 C to form methylviryl ether. By treatment of the latter with water vapor atatmospheric pressure, iydrolysis takes place to methanol and vinylalcohol, the latter immediately rearranging to acetaldehyde. Themethanol is reused. Since the process uses no mercury, whichbecame scarce in Germany, a plant for 200 tons/raonth was erected inLudwigshafen, but was bombed out after being operated for a short

while* Mercury poisoning troubles are eliminated, but Dr* Reppeadmitted that the method was somewhat more expensive than the con-ventional mercury process*

(b) Polyvinyl oleyl Ether

The reaction of acetylene with oleyl alcohol takesplace at 130-180°C with the use of 1% KDH as catalyst. No pressureis necessary* A 4 cu. m* tower capacity produced 10-20 tons/day at

yield* The polymerized vinyl oleyl ether is used as a pour pointdepressant for lubricating oils, but Dr* Reppe could furnish nodetails of its effectiveness.

(5) Vinyl Phenols

In the aromatic series' phenols and naphthola react asfollows;

Phenol was treated with acetylene in the presence ofzinc naphthenate catalyst at 10 - 20 atmospheres and about at itsboiling point (182°C)* The vinyl phenol polymerizes directly* Byreaction of these compounds with hexamethylenetetramine a * series ofresins were produced with properties varying from thermo plasticto thermosetting depending on whether 1, 2 or 3 molecules ofacetylene are reacted with the phenol* Koresin for synthetic rubberwas made similarly, starting with butyl phenol*

(6) Acrylic Acid

Acetylene in its isofom H C = cC. reacts with CO togive methylene ketene H|C=C=CO which in turn gives

HgCssCH GOOH, acrylic acid*

In practice the reaction runs;

H2O + + 1A Hi(OO) + yz HC1 Aq =

HgC = OH COOH + 0/4 Aq + 0/4 Hg.Alcohols can be substituted for water to give the ester*

Stoichiometric proportions of raw materials are used with the nickelcarbonyl furnishing the (X); the presence of acid or halogen isnecessary to bind the metal of the carbonyl as a salt* Technically

hydrochloric acid was used and the reaction ran5i 7,SJf. -3

5672-/f-3

very actively at 40-42°C with practically quantitative yields ofacrylic derivatives.

In the laboratory process for the preparation of ester,alcohol is placed in a three-necked flask with the cone HC1, theair is swept out with acetylene and the necessary amount of nickelcarbonyl allowed to drop out of a burette. Temperature is 40-42°C•It is important that sufficient acetylene be furnished, as otherwisethe rate of absorption is so great as to form a vacuum. Afterdistillation of the acrylic ester - alcohol mixture from the nickelchloride, the acrylic ester is obtained in pure form-by washing anddistillation.

Regeneration of the nickel carbonyl from nickelchloride is carried out ty treating the chloride solution with aslight excess of ammonia above that necessary to form the complexhexamin nickel-2-chloride and then with CO at about 80 °G and 50-100 atm. The nickel carbonyl is formed quantitatively, leaving insolution the excess ammonia, ammonium chloride and ammonium car-bonate •

The acrylic acid process can be run continuously andwithout pressure except in the recovery of nickel.

(7) Products from Butadiene

As butadiene in Germany is produced fundamentally fromacetylene. Dr. Reppe *s ideas on this subject are included herein.

Butadiene in benzene as a solvent is converted tovinyl oyclohexene at 270°C and 200 atmospheres with nickel carbonylas a catalyst if no water is present. 70 - 90% yield is obtained.

In the presence of water four products are obtained:

COOH

CHCHj

COOHv

O'CHaCH0-oh^With longer time a mixture of the following which

cannot be separated is obtained;COOH

H00C 'rOl “^hch 30COOH GOOH

WOC

COOH/■vCHGH}0hdcxT^-^

3471*.-S

The mixture serves as a base for plasticizers andwhen free of monocarboxylic acids, for polyamides*

4. APPLICATION DATA ON SURFACE COATINGS

Lacquers, varnishes, waxes and emulsions were discussed; noneof these products were being made at Gendorf but were made by I.G*Parbenindustrie in Ludwigshafen. Essentially, they produced thebasic materials for further processing by surface coating manu-facturers •

Lacquer information possessed at the Gendorf plant is basedon standard formulation using glycolesters as the active solventsfor nitro cellulose, cellulose acetate, cellulose butyrate andcellulose trix>ropionate, The resin portion at this time is estergum, although various synthetic resins will be employed when avail-able. The diluent is benzene which is apparently permissible inGermany regardless of its toxicity.

Synthetic waxes were purchased from Ludwigshafen and theharder types were preferred in the 12G to 18G series,'such as thepalmitic esters.

Consideration is being given to the manufacture of resinemulsions and these will be based on modifications of methacrylate,polyvirylacetate and phthalic anhydride resins. Production ofthese products will depend upon the availability of the necessaryraw materials at Gendorf.

Three grades of so-called varnishes, sold under the trade nameLuphen, v/ere made in Ludwigshafen. These are condensates of thephenol-formaldehyde type in butyl alcohol. The end product contains75% resin and 25% butyl alcohol and is known as Luphen L. Theprocess involves the reaction of approximately 1 part phenol, 1part aldehyde in the presence of 4 to 6 parts butyl alcohol for 6to 8 hours at 120 to 140°C. The addition of 1 to 5% HG1 justprior to application is employed for final conversion of Luphen Lresin. Ordinarily the resin solution was reduced to 50% solidswith alcohol for spray purposes and was used where chemicalresistance is required.

Lupen 0 H is Luphen L without hardener and is recommendedfor finishing wood or metal, either clear or pigmented.

The reaction for Luphen 145 is not carried as far as Luphen Land is soluble in ethyl alcohol. It was primarily used for cancoatings which are baked at l65°G.

Chlorinated polyvinylchloride resin under the trade name Vinoplexwas made at the Bitterfeld plant of I.G-, Parbenindustrie. It wasproduced by passing chlorine gas into a 20$ solution of polyviryl-chloride resin (32 to 3&% Cl) in carbon tetrachloride at 30 to 40°C*resulting in the addition of 2 to 4$ chlorine above the theoreticalamount. The dried product (Vinoplex) is a white powder which issoluble in mixed solvents of ketones and aromatics and the castfilms have excellent chemical resistance. ’This is the basis ofIGELIT-PC.

Other products which are on the agenda of the laboratoryfor further study are the chlorinated Buna rubbers, chlorinatedpolystyrenes and polyethylene resins.

The interview was with Mr. Eichstadt, Ghem. Engineer.

3. PItAPMAGSUT ICA3J3

The work on pharmaceuticals at G-endorf is entirely in the labatory stage. The following notes were given as indicating thedirections of work:

a. Phanodorm and Evipan

Condensation of cyclohexanone with malonic ester in thepresence of piperidine acetate gives cyclohexylidene malonic ester.Gyclohexenyl ethyl (or methyl) malonic ester is obtained by treat-ment ’with sodium ethylate followed by reaction with ethyl bromideor methyl iodide, phanodorm (MP 171 o) is produced by condensationof the ethyl compound with urea and Evipan (MP 346°) by a similarreaction of the methyl compound with methyl urea.

b. Avertin (Tribromoethyl Alcohol)

Equimolecular amounts of bromal and benzaldehyde are re-acted with good cooling in the presence of about 30% on the weightof bromal of aluminum isopropylate in solution in absolute ether.After completion of the reaction, the batch is heated 1-2 hours onthe water bath, the mixture is decomposed with 3% hydrobroraic acidand then taken up in ether.

The ethereal solution is washed with pure water, then withdilute sodium carbonate solution and dried over sodium sulfate.After distilling off the ether the remainder is distilled underreduced pressure. Boiling point = 92 - S4°C.

For further purification the avertin fraction is re-crystallized from petroleum ether - MP = 80°C.34T2.4.-B

c. Adrenalin

The preparation of adrenalin takes place in three steps;

(1) Pyrooatechol is dissolved together with monochlor-acetio acid and phosphorus oxychloride in dry benzene and boiled24 hours under a reflux condenser. Dioxyphenyl chloromethyl ketoneis formed and is obtained from the above mixture after volatil-ization of the benzene in vacuum and after heating up with carbontetrachloride by crystallization from water. M.P = 173°G.

(2) The powdered dioxyphenyl chlormethyl ketone in alcoholsuspension is shaken with a aqueous solution of methyl aminefor 24 hours, then filtered washed with cold alcohol. The4-methyl amino acetopyrocatechol formed is purified by solution inhydrochloric acid and reprecipitation with ammonia. The decom-position point is 230°C.

(3) In the last step the above compound is reduced, eitherin the presence of aluminum amalgam or eleotrocatalytically bymeans of a nickel or palladium electrode and addition of apalladium chloride solution, to the optically inactive d,1 adrenalin.

The inactive forms can be separated by means of thebitartarates into the optically active components.

d. Eunarcon

N-methyl-5 isopropyl bromoalkyl barbituric acid.-

Molar amounts of isopropyl bromide and sodium malonic esterare reacted. The isopropyl malonic diethyl ester is again con-verted to the sodium compound and decomposed with oC bromalkylbromide to isopropyl bromalkyl malonic diethyl ester. The pre-paration of the bromalkyl bromide takes place according to thepublication of Von Tollens by decomposition of 1, 2, 3 tribrom-propane in ether solution with sodium. By condensation of theisopropyl bromalkyl malonic diethyl ester with methyl urea, ringclosure takes place to N-raethyl-5-isopropyl brcmoalkyl barbituricacid.

e. Insulin

Extraction of the comminuted pancreas glands with dilute60% alcohol containing HC1 is followed by filtration and pre-cipitation of impurities by ammonia. Sulfuric acid is added andthe alcohol distilled off in vacuum at a maximum temperature of 30°C*The insulin is fractionally precipitated from the aqueous solutionwith salt and finally by repeated precipitation at the isoelectricpoint. The insulin is crystallized from phosphate buffer solutionafter addition of zinc chloride.SbTJL/i. - 5

f. Zephirol

Dimethyl benzoyl alkyl ammonium chloride,

A fatty alcohol such as octadecylalcohol is converted at130 G in a corrosion-resisting autoclave with dry HC1 gas underpressure to the corresponding alkyl chloride. The chlorohydro-carbon purified by distillation under high vacuum is brought intoreaction at 100-130°C with 1,5 mols, dimethylamine in benzenesolution. The hydrochloride obtained is crystallized from alcohol,slurried with ether and the free amine prepared by shaking withcaustic potash solution. Finally the nitrogen of the dimethylaminooctadecane is converted to quaternary by addition of 1 mol, ofbenzyl chloride.

g, Mitigal

Dimethylthianthrene •

A solution of 600 gms SGI in 1,2 liters toluene is allowedto flow into 2.8 liters of toluene and 400 gms aluminum chloridewith heavy stirring. Stirring is continued at room temperature.The reaction product is poured on to ice and separated. The excesstoluene is removed thru steam distillation and the reaction mixturegiven a fractional distillation. Chief product = 170 - 180° •

h. Novocaine

P-nitro benzoyl chloride is condensed \vith diethylaminoethanol in boiling benzene. The p-nitrobenzoic diethylamino ethylester is reduced with a chrome nickel catalyst at 2 atmospherespressure. The amino compound is converted into the hydrochloride,Novocaine•

i • N-Ace tylphenothiazine

cwCOGH^

A mixture of diphenylamine and sulfur is heated wherebyphenothiazine is obtained.

OCO3672.**.-3

This is heated with acetic anhydride, whereby the nitrogenis acetylated. Actually a mixture of sulfur andacetic anhydride can be heated together, and also obtain theN-ace tyIphenothiaz ine•

6, MISCELLANEOUS ITEMS

a, Igepon G-.

The preparation of Igepon G- may be outlined as follows:H H

—* -G -GaO -G -CI^GHsNH

Acetaldetyde Aldol Aldimin©

h2 H „

> CHj-C-CU2-CHg mQH*0H (oleio) 3 OH 2 *

Amine

hso3ciGH,. CH-CIU-CHpMiOGR

OSO^Na"Igepon Gf""Igepon G?"

b. Water Softener - "Trilon"

The sodium salt of the compound prepared by the reaction '

is a water softener sold as "Trilon,"

Manufacture was started at Ludwigshafen just before thewar.

c. Detergent

Dr, Reppe spoke of work done on a detergent developed bythe Japanese, Dr, Otta, with whan, however, he claimed to have nodirect contact. The product is made by reaction of a fatty acidamide and formaldehyde -‘sulfite -

This is not as good as the Igepon but is cheaper andeasier to manufacture.

3C,73Ut--i

cU Ramasite

Ramasite is a water proofing agent consisting of an emul-sion of paraffins (from brown coal) of different types hard anisoft with less than 1% Nekal with a solution of basic aluminumacetate (or formate or chloride) and urea*

For use the emulsion is diluted 1 to 10 or 20 with waterand the fabric drenched, then dried at over 100°0 for the formatesbut at 70°C for the acetates. The water proofing effect is statedto be better than Yelan (Zelan) but is removed by washing.

e. Blattan

Dr. Ambros mentioned a contact insecticide developed byDr. Schroeder at Elberfeld -

0CK HfilN -P

j

f• Polystyrene

A styrene polymerisation tower had been shipped from Lud-wigshafen to G-endorf and was lying in the freight yard. It wasbuilt of five steam Jacketed sections and contained two steam coilsin the lower sections. In practice the monomer styrene would passto two prepolymerization kettles in parallel where it would beheld with stirring at 50 - 80°C for two days catalyst.From these kettles it passed to the top of the tower at 70 C andflowed slowly thru with a total time of sojourn in the tower of 24hours. The temperature down the tower gradually rose to 200°Cat the conical exit which was heated electrically. The tower wasestimated to be 15 feet high x 2.5 feet diameter and to produce1 ton polystyrene per day. Prom the conical outlet the moltenpolymer passed thru an electrically heated screw conveyor to acontinuous metal belt carried on cooled rollers where it solid-ified and passed to the guiding system.

The chief grades of polystyrene produced were No. 5 witha molecular weight of 100,000 and No. 4 of 200,000. The No. 3grade being the most important. It was stated- that the styrene iscompletely polymerized.

3672.*"5

*

*Polyamid resins

Allylalcohol

—>

glycerinPropionaldehyde

-»2methyl

butanol3al1-*2

methyl

butanediol1,5-)

isoprene

'Hexadiine2.4diol1,6

—*

Hexanedicl1,6—

4£

Capro-

lactam*

£

caprolactam—

>

polyamides1,4dichlorbut

ine

di-

acetylene n-butanol Racemicormeso

Eiythritol1,4

dichlorobutaneEsterse.g,

maleic&

polymers

Additionproducts

e*g*to

anthraceneketo-

Tartaricacid1

Malicacid

V

4"PlasticsPolyurethanes Succinicacid

pimelicacid

ACBTYIENB+

PQRMAIJXSHYDEPropargyl

AlcoholButine2diol1,4

Butene2diol1,4

.Butanediol

1,4

CHART1

Butanediol1,2fOxymethyl

vinyl

ketonefButanone

2diol

1.4

/

Hexamet

hylol-**•

benzene—y

butyrolactone(PlasticizersEsters(Alkyd

resins (Textilewaxes

Chloroallylalcohol

Propargylaldehyde

<

2,5Dimethoxy

1,4*

dioxan Tetrahydrofurane3,4oxide

Dihydrof

urane4r"

3

Oxytet

rahydrofuranc1,3»4

Butanetriol(—

Melliticacid)

<_

Pyromelliticacid)

SeeChart2

Polymers Acetal^—347*/*.-3

—%

PyrroleDiazoaminocompounds(insecticides)

7

R

naphthylpyroll-

idine(antioxidant)PolyamideResins

4dichlorobutane

—-*adipo-

nitrilebexamethylene

,

diamine1,6Dodecahydrotriphergrlene Pyrollidine

Butadiene1,3

mixedpolymers

adipicacid;

Butanediol1,4-)

Succinic1

Acid

CHART1

(Continued)ACETYLENE+

PORMAIDBHYDE Tetrahydro- furane Buna

DicWjOrdibutylether

Polyamines.

2,3

dichlorotetrahydrofuranePolytetrahydrofurane phenantbrene£—

*'

3chloro2

alkoxy-

tet

rahydrofurane

Piperidene

Pentamethylene

Piperidin

Diamine1#

5

AlkydsGlutario

Clutaricacid

Polyamideester

dinitrileG-lutaricG-lutaric

acidacidimide

/

,»

NaGN Cyanbutvricf

acidI

Pentanediol1,5

PolyamidesThiodibutyricacid

Sstersfor

waxes,plasticizers resins

/

Dibutyricacid

sulfoneHaSH

V-Butvrolaot

oneCHART1A

Dipropylether Carboxylic

acidPolyamide AlkydsPolyesters PlasticizersNaQH

Chloro- butyricacidHG1

Esters72.4--S

36

amino butyric aoid Resins-HJ+IHj pyrollidonew Amino

i

ethylpyrollidoneN-vinylPyrollidone Polymers

Textile assistantsCHART1A

(Continued) -oxy butyric amide Pyrrolm3

V

-ButyrolactonePhe

nosy- butyricacid

Phenol SoligensTetralon

�Phenylbutyric

acid Phenylene dibutyricacid alkyds polyamidsBenzene3A7X.ft.-3

2

methyltetrahydrofurane

Pentine3did2,3

Pentanedid2,3

I

+

2H2-

HgO V

piperylene

ACETYLENE+

ACETALDEHYDECHART2

Vinylmethyl

ketoneButins-

3-ol-2Butanol-2-on-3

p

I

+

HgO -V

1

Acetaldehyde+

1

Acetylene—

HoO *2

VinylAcetylene Butansdiol

2,3

3«

Hexatriene1,3»5

-2HoO

2,5dimethyl

tetrahydrofuranel,ifdimethyl

butadiene1,5

(Hexadiene2,4)

ACETYLSHS+

ACETALDEHYDE.Hexine-

3

-

diol2,5

Hexene-3-

diol2,5

•

\

CHART2

(Continued) -HgO-*y>+

H2

Hexanediol2,5

t

*h2

2

Acetaldehyde+

Acetylene -2^

Hexadione2,3

(Acetonylacetone)