DE2343826C3 - Process for the manufacture of urethanes - Google Patents

Description

Dimethylensulfon- or Dimethylnnwongruppen, mean.

The group R can be an alky! -. Cycloalkyl-.

The invention relates to a process for the preparation of alkylene. C vcloalkylen- or araikylgruppe scm of urethanes. possibly at the same time with: Ami- * ä whose main carbon chain is desired through nen, by reacting at least one hydroxyl, for example oxygen. Sticku, MT or Nci, sulfur group containing aliphatic or aromatic atoms, Suifoxyd-. Sulion-. Amir.-. Amide. Carbony.-alcohol or phenol with carbon monoxide and eu.er or carboxylic acid ester groups at least one aliphatic containing nitro groups. The main chain can be used as a substituent, for example or aromatic nitro compound at tempera- 3 ° as alkyl. Alkoxy, aryl or aryloxy groups Doors of around 60 to 250 C and pressures of around contain that normally less than 10 carbon-10 to 100 atmospheres in the presence of a metal siofiatome. Particularly suitable verbs: catalyst. fertilize the general formula

So far, urethanes have been used, at least in part.

technically by reacting an isocyanate with a 35 R (OH) _n

a hydroxyl group-containing compound oei

produced at elevated temperature. Monohydric alcohols, such as methyl, ethyl, n- and isocyanate starting compounds and the secondary propyl, n-, iso- and tert-butyl, amyl, hexyl, resulting in toxicity problems made the costly alcohols Lauryl, cetyl. Benzyl, chlorobenzyl and methoxy development of new technical processes required. 4 ° benzy! Alcohols as well as diols such as ethylene glycol, di-From US-PS 33 38 956 and 34 48 140 is known, ethylene glycol, propylene glycol and dipropylene glycol urethanes by looking at a minimum of three triols. such as glycerine, trimethylolpropane, hexanetriol. Hydroxyl group-containing organic compound tetrols, such as pentareythritol and ethers of such polyols with carbon monoxide and a nitrogen compound, with the proviso that at least one OH group which is not ethereal at superatmospheric pressure and elevated temperatures is present. The ethereal temperature in the presence of compounds of Cr, Mo, group of such ether alcohols contains normal -W, Fe, Co, Ni, Ru. Rh, Os and Ir as catalysts wise up to 10 carbon atoms ^ and is preferred to produce. Although cheap silicon connections are an alkyl. Cycloalkyl or araikyl group, fertilize are used, this method obtained which can be substituted, such as. B. a haloalkyl for the industrial production of high-purity urethanes in the 5 ° group.

result in lower product yields, longer reaction times. The phenolic compounds of the general

times and the work required at high formula

Express no economic importance. Many of the R '(CIi) _n

The above catalysts are expensive and can be

It is difficult to get rid of the desired urethanes with substituents in the benzene rings, separate. That makes the process technically un- z. B. Alkylgruppcn and alkoxy groups with up to interesting and also contained an impurity of the 10 carbon atoms and halogen atoms. Urethanes caused by metals. Suitable monohydric and polyhydric phenols include

The object of the invention is therefore to provide a phenol, chlorophenol, methylphenol, ethylphenol, improved process for the production of uretha- ⁶ ° butylphenol and alkylphenols, pyrocatechol, rene, which does not adhere to the above disadvantages. sorcin. Hydroquinone, 4,4'-Dihydroxydiphcnylmcthan, This object is in the invention Ver Naphthole, ChtornaphtMc. Mcthylnaphthol, Ethylfahren of the type mentioned above solved by naphthol, butylnaphtho! and Ociylnaphtho !, Andaß you the reaction in the presence of selenium, thranolc. Chloranthranolc, Methylanthranol, ethyl Schwefcl, a selenium compound, a sulfur ⁶ 5 anthranol, Butylanthranol and Oclylanlhranol, Phcnvcrbindung or a mixture of these Produklc anthro'.e ah. ChI * phenanthrole, methylphenanthrole, catalyst together with at least one base ethylphenanthrole, butylphenanthrole and octylphenanthrole and / or water. anthrol. Pyrogallol, phloroglucinol I hydroxyhydro-

quinone and the ethers of the Pohhv <jro \ yphenols. the contain at least one non-etherified OH group, a The troubling group of such ethers normally contains up to 10 carbon atoms and is preferably an alkyl, cycloalkyl or Αγο! Κ>! Group. The substituted ηίγ, like ζ. Β one-shark alkyl group. From the mentioned aromatic compounds are phenol and chlorophenol. Oayiphenol. 4,4'-D; -hydroxydiphenylmeth;: -. Naphthols. Anthranols and phenanthrols are preferred. while phenol is the most preferred compound:

In accordance with the invention, suitable nitro compounds include mononitro compounds, such as nitrobenzenes, alcohols and alkoxynitrobenzenes, the alkyl groups of which contain two or more carbon atoms, Ar \ '- and aryioxy% r: trobenzok-, the aryl groups phenyl-. ToIvI-. Xylyi, naphthyl, chlorophenyl, chlorotolyl. Chlorxyly'- .'d, " Chiornaj.iithyijruppen contain C'hlornitri" / oils. Dinitro compounds such as dinitrobenzene, e.g. ο-, η - and p-dinitrobenzene, alkyl and alkoxythni'.robenzenes, their alkyl groups up to contain 10 carbon atoms. Aryl and aryloxydinitrobenzenes, du.>i-> aryl group contain one of the groups mentioned above Contain the above-mentioned groups and chlormitrobenzenes as well as similarly substituted mono- and polyn.troderivate of naphthalene, diphenyl, diphenylmethaii-, anthracene and phenanthrene compounds. Substituted or unsubstituted aliphatic nitro compounds, such as nitrobproane, nitro, nitroethane, nitro-methane, nitro-ethane , 2,2-dimethylnitrobutane, nitrocyclopentane, nitrocyclohexane, nitrocyclobutane, 3-methylnitrobutane, nitrooctadecane, 3-nitropropen-1, phenylnitromeihan, ρ - bromophynylnitrometh an, p-nitrophenylnitromethane, p-methoxyphenylnitromethane. Dmitroethane, dimtropropane, dinitrobutane. Dimtrohexane, Dinitrotkcan. Diritrocyclohexane, Diniiromethyleyclohexan and Di-fr.itrocyclohexylJ-methane can be used, of which, however, the primary, secondary and cycloahphaiischen compounds are less preferred, since they lead to a product mixture in which the Lrethane can be a secondary component. From this group before nitro compounds are the aromatic nitro compounds, such as nitrobenzene and nitrotoluene. Dinitrobenzene, Dinitrotoluol, Trinitrobenzol, 4,4'-Dinitrodiphenylmethan, p-Nitroanisole, p-NitrophenetoI, o-NitrophenetoI ^^ - Dinitrianisol ^^ Dinilrophenetol, 3,5-Dinitroben / yiacetat, i -rhior-2,4-diiiici ' nuAy-5-nitrobenzene. 1,4-Dimethoxy -2-nitrobenzene, p-nitrophenylnitromethane and the tertiary aliphatic nitro compounds, such as 2-meth>! -2-nitropropane and 1-methyl-1-nitrocydohexane, are preferred. The aromatic nitro compounds, ie the 2,4-, 2,5- and 2,6-dinitro-toluene, m- and p-dinitrobenzenes and 4,4'-dinilrodiphenylmethane are particularly preferred.

Those suitable for the method according to the invention Catalysts include sulfur, selenium, sulfur compounds, selenium compounds, and mixtures of these products.

Selenium metal, in particular in powder form, is preferably used as the catalyst for the process according to the invention, since this has at least as little effect or better than most selenium compounds. "." Jute bulging but can be n <uh nut selenium compounds achieve as selenium dioxide, Selentrioxyd aN mixtures of these oxides, Seienoxychlond. Tiundiselenid and SeLndisulfid. Also Natnumselenir Zmioelen.t, zinc selenide. Tungsten selenide, Selensuhie. Sciensäurj, dimethylselenide, Diäthylselenid, diet ! ■■ ·! - di'-flenid. R ^ iphenvlselenui and carbonyl .-, eienü k ·; ine: a "., Ct / t will;., And one can, also au ..:; Pu! Vseu..iu_. such as diethyl polyselenide and dibutyl polyselenide. The achievable I mwandluagci

ίο i.:ia Yields, however, are not necessary for all selenium compounds same.

In addition to sulfur, the carbon dioxide catalysts leveled for the process according to the invention are inorganic sulfides such as hydrogen sulfide and carbon sulfide. Carbon disulfide. Natnumsultid. Kaiiur.-sultid or Sehwefeldichlorid. organic sulphides and polysulphides as well as mercaptans and thtoethers up to r-> 2U carbon atoms, such as diethylpolyN.ilfid, Dioct>! -polysulnd, methyl mercaptan, ethyimeicaptan or cetyl mercaptan.

The catalyst material given above can be used as such or on an inert support material on which the catalyst is dispersed to increase the effective surface area. AK carrier materials are used for this purpose: aluminum oxide, silicon dioxide, carbon, barium sulfate, potassium carbonate. Asbestos, bentonite clay, Diaioneenerde, Fulier earth, organic ion exchange resins and similar materials are suitable. A particular example of a catalyst comprising a carrier material in an ion exchange resin which contains selenium as a cation and a sulfoic acid or carboxylic acid function as an anion of the resin, such as a selenium-containing sulfonated macroporous styrofoam divinylbenzene resin. It can also selenium or sulfur-containing molecular sieves as well as complexes of selenium or sulfur mi ^f a 1 ligands are employed.

A base or water must also be present in the reaction mixture. It has been found that both organic bases and metal salts of carboxylic acids are suitable. Organic bases suitable for the reaction include amines, such as triethylamine, pyridine, quinone, Ν, Ν-dimethylaniline, diethylamine, tert-butylamine, 1,4-dia7o-bicyclo- [?. 2. 2] octane, polyethylene polyamines such as NNN, N'-tetramethylethylenediamine, tetramethylenediamine and ethylenediamine. Thus, in the reaction mixture, aliphatic. aliphatic-aromatic and aromatic heterocyclic amines can be used. In addition, the amines can make up part of a polymer ", vie S" ^ ¹ "'D / sU-vinvlnvriHin the case is VeT bonds, which are normally considered to be weak bases, such as the metal salts of carboxylic acids, sulfonic acids and phosphoric acid preferred bases. Examples of such compounds and salts of other weak acids are lithium acetate, sodium acetate, potassium acetate, palladium acetate, ruthenium acetate, the lithium salt of p-toluenesulfonic acid, the lithium salt of methyculfonic acid, acid lithium phosphate, the lithium salt / boric acid, calcium acetate, sodium formate, Lithium formate and antimony triacetate. The acid salts can be added in the pre-formed form or prepared in the reaction mixture by adding the appropriate amounts of the corresponding base and the corresponding acid.

There are no stretches of metal oxides or hydroxides. / B. from 5: 1 to 2000: 1. where jed.-ch ei ·,

Restrictions. Thus, aliphatic. cv.lo- more preferred area of the disproportion of the Vt ,, -

aJiphatic and aromatic acids, such as propionic compound to the catalyst differ from H-. 1 -

acid. Octanoic acid, cyclohexanecarboxylic acid, benzoin- 1000: 1 ranges. It goes without saying that uie. Moles dc-

acid. Oxalic acid and malonic acid are used. 5 catalyst is based on the element selenium or sulfur

However, the oxides and hydroxides of L beraanes- and not on the compounds used, if

metal compounds are more expensive than the alkali metal compounds, the catalyst is a compound

and alkaline earth metal rivdroxides. The situation is similar with the nitro compound. ν.

In view of the determination of the status referenced to the nitro group. so that beTechnik, that water is completely excluded io dinitro compounds. such as B. Dinitr. toluene, half of it the must. when maximum yields are obtained Molmenje, d. H. the equivalent ratio, inserted should, the beneficial effect of water must be.

the reaction of the method according to the invention extends in a similar manner to be surprising. It was gefundeü as-containing ^'(. "The encryption Deten amount of the base, the molar ratio of the nitrated" ending of kristallwasserhaiiig-in connection triumacetat 15 (relative to the nitro group) to the higher conversion Rtn r' .. Base from 50: 1 to 1:10. Although in the absence of compound it works as the veru ^ iunng of water-water and the reaction is only free sodium acetate, in (, "-. The essence of an Orgarian base can be determined by the Sta- (W Technique strictly water- can, it is when water is used before; 115t einzusc of water without use of a base amount of the catalyst, Jn. Thus, relatively high yields have been achieved, e ^s is normally the molar ratio of water / u alysator Ka, 'h. ι Se as desired, both a base and water or S, from about 0.5: 1 to 1000 : To use 3 or more creinz. stretch, with a range from 1: 1 to 200: 1 preferred

Although the method of the invention is more typically added. It was also found that with react

wise and effective in the absence of a solution temperature above 175 C when using

can be carried out by means of, however, a base can be dispensed with from water, whether-

use a solvent. As a solvent, temperatures below 175 C can be used to achieve this

aromatic solvents such as benzene. Toluene. a good yield of the desired products

Xylene, nitrile solvents. such as acetonitrile and benzo-30 base is used and where it is generally

nitrile, amide solvents such as Ν, Ν-dimethylform- is preferred. the base together with lower water

amide and N.N-Dimethvlaeetamid, aliphatic, alimass to be used. This water can be found in Mtu

cychsche or aromatic sulfoxide and sulfone are formed, z. B, if you have a base like Kahum-

solvent. like dimethyl sulfoxide, aliphatic ha-hydroxide. and an acid, such as acetic acid, in equi-

logenated hydrocarbons, such as 1.1.2-Trichior- 35 molar Vfengen, are used as schwaen

1,2,2-trifluoroethane, halogenated aromatic carbon base compound potassium acetate and water in

Hydrogen such as monochlorobenzene and dichlorobenzene form equimolar amounts. In general it is

And trichlorobenzene, ketones, esters and ether solution preferred, as an additional amount of the erfo; Always

medium, such as tetrahydrofuran, 1,4-dioxane and 1,2-di-base, an organic base such as pyridine or triethyl

Metlioxyäthan can be used. The ether connec- 40 amine. to use.

can fertilize z. B. aliphatic, aromatic or It has also been found that, although the Ure-

be heterocyclic and, as monoethers or thanes, can generally be the predominant reaction

Polyethers or as a combination of such products of the invention ".. Process d: sr-

applications are available. If the at least one Hystell, certain by-products are obtained. the

Organic compound containing droxyl groups in 45. The main by-products are amines, which in certain

the applied reaction agreements a liquid reaction conditions as the predominant product

This connection can be held in a certain way. Reaction conditions that

Cases serving as a solvent, which generally promote amine formation, include the use

is preferred. a sulfur cooler and or larger water

At higher temperatures and pressures, this can amount to 50. It appears that the sulfur catalysts favor the process according to the invention with advantage in an amine formation somewhat more strongly than the selenium-inert diluents are carried out. The kata'vsatorc. and that in certain cases the inert diluents which are somewhat preferred are also the larger water oils which promote amine compounds
However, the main aim of the process of the invention is to dissolve reactants, some of which are the production of urethanes, since the amine main substances are similar to solvents (compared to suitable inertness in general) with the technical an-diluents are aliphatic ^ - or aromatic applied alternative processes, economically not hydrocarbons, such as n-Pc-ni.m or toluene - .. how cheap is. Nevertheless, in the following some Bci-Äthcr, Katonc and Γ stcr games indicated, according to which nitrobenzene to aniline

The process of the invention is preferably carried out in 60 and dinitrotoluene to the corresponding mononitro

"Carried out in such a way that the hydroxyl group monoamine compounds are converted,

Reverberant connection of carbon monoxide and the nitro- The series. in which the rcaklionstcilnehmer

Reacts compound in at least molar amounts. be mixed is not critical and can, depending on

Preferably, however, the hydroxyl devices used are varied. One

fTiippcnhalti ^ i connection or the Nitrovcrbindung H simple procedure consists in the Nitrover-

a molar bond containing at least cmc hydroxyl group

The molecular weight of the nitro compound leads to the organic compound, the catalyst, which

The catalyst can dissolve in a mfm-wide freezing process in order to introduce ml of water into the reaction vessel.

bring in the appropriate amount of carbon monoxide in the usual way by filtering, distilling or adding and then heating the mixture to achieve the desired reaction to use other suitable separation processes. For the reaction, a suitable pressure vessel, such as an autoclave, the Au.'gingsmatcrial, the solvent, the Nebenvoizugswcisc with a heating device and with a 5 products, the catalyst is worked for the reaction.
Stirring device, such as a stirrer or a stirrer which is equipped according to the cr-SchüUclmcchanismtis method used. Contained urethanes contain one or more

In general, it is in the free space of the uranium group and can be monomeric or polymeric

KiMktificcrfalicN contain »: Koli1cumoiio \ yd quantity to be. Thus seduction can lead to the production of

sufficient u'ii the desired pressure / u result in 10 Monourcthancn from Mononitroverbin'Jungcn and

and the Ki-.iktioiisieiliichmcr für d.is Verf.i your / u Monohvdroy.yvcrhmdungen and / u ^{r the} production of

put in the MaK. in which the reaction proceeds. Polyurethanes made from polynitro compounds and mono-

/ii^.ii/liches carbon monoxide, either interfunctional hydroxy compounds can be adapted.

mittiL-ieiul oilei konimuierlieh. in da ·. Reaction gel The uretlian products obtained. especially the-

cin ^ ebi.u I11 graze (although usually larger 15 urethanes that do not contain more than three urethanes

or small amounts of carbon dioxide are used which contain groups per molecule

the koiiiH.ti. is generally from the way during the thermally odci 'catalytically in the cntsprc ^v .rnden

Reaction added (the amount of carbon mono- isocyanates is converted

iixvd .Iw,.! 1 Ins about 5d mol. Preferably about K to As has already been stated, after the

I ^s Md kohlcnmi> no \\ d per non-cyclic group, ζτ inventive method also amines produced

in which the Nitiogruppc an · in individual carbon-, where for example from the Mononitrovcr-

ati.'ii bound lsi. The highest carbon monoxide-forming monoamines are formed. As already

kidneys sin »! , in general not specified in a process, are generally the monourethas

fouleriiih continuously represents the predominant product in the kohlenriionmvd, but how out

ziiL'oet / t «, ml. Although it can be seen through a suitable example, it is possible to use the amines

Recirculation of the carbon monoxide containing (jas- to form in equal or predominant amounts. Im

currents, the carbon monowdgesainivcruse considerable- all of the! ^ nitro compounds are obtained for example

liv.h can be reduced as amine products, the monoamine-mononitro-

IVc Rcaktionstcriiperatiii is used in a range of compounds, i. h .. only one of the nitro

ι ·! · λ.ι fin up to about 2M) (preferably in a Uercich 30 groups reduced to the Animogruppc.

\> r ciw ι KHi kept until about 200 C. In addition, the reaction of polynitro-

the temperature range can be avoided by avoiding compounds with polyols and carbon monoxide poly-

U.N? A.niseiiter side reactions a suitable Rcak urethane can be obtained. So you can go straight out

("• -i't-ehwindiL'keii can be achieved. The reaction of diols,! ^ Nitro compounds and carbon monoxide

WTd as already mentioned above, with superatmospheric or from hydroxynitro compounds and carbon

r-! -υ Print / wipe about 10 unil 500 Atmo- monoxvd linear polyurethanes, for example as

■ rl ·, no; duuhguided Preferably, however, fibers or liastomers can be used,

! '. • "! Lülich niailigc kt" hlennn> nox> ddruckc in the range can be obtained, while one can obtain from mixtures of

from about! 0 to about IdH atmospheres applied. Di- or polynitro compounds, diols or poly-

w> in the reaction within this pressure range 40 oil and carbon monoxide crosslinked polyurethanes

suitably obtained at an temperature below about, which as flexible or rigid plastic material

2iiu (is carried out. Accordingly, the ert'in- ahen may be suitable.

The following examples are intended to illustrate the process of lower temperatures and pressures carried out in an advantageous manner. Those shown in these examples. The reactions were compared with the temperature and pressure in stainless steel shaking devices. the Ki of the use so far for the enclave (stainless steel No. 316) carried out. There is a transformation of industrial designs and sticks - however, see that cheaper stainless rods ¹ ·; einhaiiit '-. ii \ erf.in «iuriL'c - im' ^! rc (fi; mpr <>'!'.'l·' c tickannt can be set and if desired also entiricrcn ka! a ', ■ ti-rather. Metals invented.:, ν, ηΔ. speaking reaction vessels, like with Glass lined

Mh-A..h ¹ t! Is ei't'm.iuniiNV.'cniäUc Vcrf. '. Hron hti all- 5 »-J.-tc- <iefaße. can be used. The ones in the

ge "-. !!. Cu .ι '· -n / Ac-i-e expires, the RcAtion gc examples given conversions and

w ■ <-.'...! '.! en! all · ·' ■, .dbki> nti: Hiierln.li or ^ "g.ir k <> r, i, - bags were gas chromatographically and liquid-

'I ·. jiIk! · durdig '' .inrt weriicn. For the Kontmuicrliii-keitschrom.itographi ^c .ch intended.

'vef'.iiirensfuhru'iii ^ ind 1 B. the ion exchanger- „.

r.! * il ·. -.atoren rc-'iHliTs suitable. The reaction / ei '55

..rf! from the Ar ■: ·. r response participant. the tem- 10 ml of nitrohenzene and 15 ml of methanol were in

; vr lUir. the pressure and the type of used an 'in-ml

Κ.Γ, .ι! ·. > .itnr «. Even the device used kept the initial carbon monoxide pressure of 183 atmospheres.

ah \ -rinali-: ^ else the reaction time is less. In the - \ utoklav there were also 1.6 g of selenium metal and

iN 'mi minutes w >> with the effectiveness of the crtin- 60 1.6 ml of pvridine present. After 45 minutes with one

'' v-iciu? eirge-et catalvsat'-ren a full reactor temperature of 200 to 225 C was the conversion

- ■ ■ ■ .- 'i the course of the reaction within a time conversion of nitrobenzene 98 "" and the yield

'■■ ι ·· /WiSvI.en about'. '»Minutes and about 75 minutes your urethane product obtained (Methyi-N-phenyl-

, · ·,. · ,, ν nt carbamate) 88 ",,.

'■ 1 > xkr.i d'c reaction -. «You have to run constantly. 65 If the procedure was repeated but using a reaction time of 3 hours, cmc decomposition occurred. thereby making the maximum urethane product. Loot only? 3 bjtrue

'609 625/26?

; ■> <: '. Hur the re akin >! 1 sH '' sk hung on , r ι ·, 'η ι ¹ '! Ul ld i.e. I) Γ UC kgefaii un- I ι, I ' , ". _t , ·. 'ι ■■' _h ■ rd then in

Example 2 example

10 ml of nitrobenzene and 15 ml of methanol were mixed with 10 ml of nitrobenzene and 65 ml of methanol

introduced a 110 ml autoclave and with a carbon monoxide in a 110 ml Schüttclauloklav

Initial carbon monoxide pressure of 190 atmospheres at a S at a temperature of 2 (X) C and at a carbon

Tcmperatur kept between 200 and about 225 * C. lenmonoxide initial pressure of 21.1 atmospheres.

In the autoclave there were also 1.6 g of metal and 1 g of metal were also in the autoclave

1 g Triäthy2. '.. mn present. After 45 minutes, the bc catalyst and 1.5 ml of pyridine are present. To

The niirobium conversion contributed 72% and their reaction time of 180 minutes was the

Urethane product yield 74 "/. Ic Nitrobenrol conversion NZ '" and the urethane ·

_Example 3 product yield 76%.

10ml nitrobenzene and 15ml methanol were used in Example 9

placed in a 110 ml autoclave and at a 5 ml nitmhcn / ol and ft * ml methanol were in

Initial carbon monoxide pressure of 183 atmospheres was placed in a 110 ml autoclave and, with an initial pressure of 0.5 g sodium carbon monoxide and an initial pressure of 21.1 atmospheres, an acetate hydra! at a temperature / wisch-n 20!) temperature of 2 "" C "umgLsct / t During the reaction and 225 C" held for 45 minutes, the were also 0.5 p silicon metal and 1.5 ml pyridine nitrobene conversion 94 ",, and the urethane used. After 150 minutes the nitro product yield was 68 "" .20 bcn / oil conversion M) "" and the urethane product

If the procedure of Example 3 was repeated with a yield of 67 °,
a reaction temperature of 180 C and treated

one the reaction participants under the same Bc example IO

"Lingungcn for 90 minutes, then the nitro 5ml Nitrobcn / ol and 6S fell _m | Methanol were in

ben / oil conversion from only 23%, while the 25 a 10-ml-Sdiuttcautoklav attached and no Urethane product yield was 68 "with an initial carbon monoxide pressure of 21.1 atmospheres

at 200 C umgcsct / t. Were in the reaction vessel

Example 4 also contains 0.5 g of selenium metal and 1.6 ml of pyridine

,, ....,, with 1 g of sodium metal trihydrate present. To

10 ml of nitrobenzene and 15 ml of methanol were introduced into a 110 ml autoclave in 30 75 minutes, and the urethane product yield was 50 ".
of 1.5 g of selenium metal and 1.6 ml of pyridine with one repeating the procedure of Example IO at

Carbon monoxide initial pressure of 183 atü maintained at an initial carbon monoxide pressure of 15 2 atü temperature of 170 C. After 60 minutes of so, after 60 minutes the nitrobenzene conversion was 22% during 35 minutes 80 "and the urethane product yield was 67".
“I found a urethane product yield of 50%.

Similar conversions are achieved by using Example 11

Nilrocyclohexane and ethylene glycol with carbon 2.5 ml N.troben / ol and 6S _m f methanol were in

monoxide under the m given in this example, a 110 ml Schüttelauloklav attached and be.

Implements conditions. 40 an initial carbon monoxide pressure of 35.2 alQ

Example 5 reacted at 200 ° C. In the reaction vessel were

. _n , ....,. , ,,, _x,. . . ^Ferncr 0.25 selenium metal and Ig sodium acetate

10 ml of normal benzene and 15 ml of ethanol were hydrate present. After a reaction time of 10 minutes, a 110 ml autoclave was introduced into the presence of the product, a nitrobenzene wall of 1.5 g of selenium metal and 1.6 ml of P> ndm resulted in a 45-95% yield of urethane products of 78%.
Carbon monoxide initial pressure of 183 atu at a

Reaction temperature of 200 to 225 C implemented. Example 12

After 60 minutes the nitrobenzene wall was in - 5 ml of nitrobenzene and 30 ml of methanol were in

treatment 10% and urethane product yield 52%. introduced a 1 iO ml shaking autoclave and be.

5 "an initial carbon monoxide pressure of 56.2 atu

Examples implemented at a temperature of 200 C. Addition / lioh

were in the autoclave 0 5s Selenm'tall 35 ml

K) ml of nitrobenzene and 10 ml of methanol were introduced into tetrahydrofuran and 1 g of sodium acetate trihydrate in front of a 10 ml Aiitoklav and kept in the presence. After a reaction time of 10 minutes of 2.2 g of selenium dioxide and 16 ml of pyridine in a 55, the N.trohenrole conversion was 64%, while an initial carbon monoxide pressure of 193 atu at 200 resulted in an urethral product yield of 74%
up to 225 ^J C reacted After 180 minutes, the repetitions were the Reakt.on of Example 12 at

Nitrobenzene conversion 53 "and the urethane product 170 C. This resulted in a nitrobenzene conversion duktausbnite 63 ... of 72%. while after 60 minutes an original

B e i s ρ 1 e 17 thane product yield of 70% was obtained.

10 ml of nitrobenzene and 15 ml of methanol were used in Example 13

placed in a 1110 ml autoclave and in the presence of 5 ml nitrobenzene, 30 ml methanol and 35 ml tetra-

of 3.3 g of selenium oxychloride and 1.6 ml of pyrene. a hydrofuran were placed in a 110 ml schütte autoclave Carbon monoxide initial thickness of 190 atu introduced at 65 and with a carbon monoxide initial

Temperature of 200 to 225 C implemented. After pressure of 56.2 atmospheres at a temperature of 200 C.

The nitrobenzene conversion was 0 minutes. In addition, there was 0.5 g in the autoclave

100% and the L rethanproduxt yield 42 _o . Selenium metal and 2 g N urium acetate hydrate present.

11 12

After 10 minutes, a nitrobenzene temperature of 170 ° C. was achieved. After this had elapsed

conversion of 70% and urethane product reaction time was nitrobenzene conversion

yield of 53%. 100% while using a urethane product

If the reaction of Example 13 was repeated with (methyl N-phenylccrbamate) of 75%,
the difference that a reaction temperature of 5

170 instead of 200 ^° C. was observed, an example 18 resulted
Nitrobenzene conversion of 100%, and achieved

an original product yield of 74%. 10 ml nilrobenzene, 65 ml methanol, 1 g sulfur,

1.6 ml of pyridine and 1 g of sodium acetate trihydrate were added

B c i ν ρ i e 1 14 iu into one. 300 m! Autoclave introduced, which in a

Carbon monoxide initial pressure of 183 atti during

5 ml of nitrobenzene and 30 ml of methanol were kept at a temperature of 200 ° C. for 45 minutes

introduced a 110 ml SchütteiautokIav, which was at. The resulting nitroben / oil conversion

An initial pressure of carbon monoxide of 56.2 atmospheres was 83 ";

and a temperature of 170 C "was operated. 15 hives of 18" "yielded.

In addition, there was 35 ml of tetrahydro- Repeat the procedure of Example ίΚ in the autoclave

furoii. 0.008 mol of lithium acetate monohydrate and 0.5 g with the difference that instead of 1 g of sulfur

Solid metal present. After a reaction time of 2 g sulfur cinsct / tc, a nitro-

10 minutes resulted in a nitroben / oil conversion of 94 ", ', with an original

of 94% and a urethane product yield of 33% was achieved.
yield of 68%.

When repeating example 14 while following example 19
a reaction temperature of 160 ° C. resulted

60 minutes a nitroben / ol conversion of 100 " _u , Fin 300-nil autoclave was with 10 ml Niirobcn / ol.

while a urethane product yield of 83 ", 25 65 ml of methanol. 0.5 g of sulfur and 1g sodium

he / ielen let. acctattrilndrat charged and with a cabbage monster

Example 14 was repeated again, but at an initial oxide pressure of 183 atmospheres at one temperature

an operating temperature of 150 instead of 170 C, so operated from 200 C. After 45 minutes the was

After 60 minutes there was a nitrobenzene / ol-nitrobenzene conversion of 46% and the original

conversion of 87% and a urethane yield of 32%.

of 85%. π 1 -> n

Example 14 was finally carried out at an »egg game 20

Reaction temperature of 130 instead of 170 C through, 10 ml nitroben / ol, 15 ml methanol, 5 5 ml dioxane.

10, after 140 minutes, a Nttrobenzol- 0.29 g lithium hydroxide, 0.72 g acetic acid, 0.10 g

conversion of 89% and a urethane product made from selenium metal and 0.30 g of sulfur were combined into one

loot of 71%. 110 ml autoclave introduced, which was

. monoxide initial pressure of 183 atm for 45 minutes

Ii e ι s ρ 1 e I 15 _{slots heated to a temperature of} 200 C.

5 ml of nitmben / ol and 30 ml of methanol were added. After the reaction time had elapsed, a nitrobenzene conversion of 75.2% and a disulphide and 0.008 mol of lithium acetate monohydrate in an original product yield of 82.5% resulted, together with 35 ml of ammonium profuran, 0.1 g of titanium-4 °.
placed in a 110 ml shaking autoclave. The autoclave was operated at an initial pressure of carbon monoxide Example 2!
operated from 56.2 atü at a temperature of 150 C. After 60 minutes, a nitrobenzene 45 0.29 g lithium hydroxide was obtained. 0.72 g acetic acid. 0.25 g conversion of 96% and a urethane product from sulfur. 0.25 g selenium metal, 10 ml nitrobenzene, 15 ml yield of 88%. Methanol and 15 ml of dioxane were in a 110 ml

Example 15 was repeated without introducing the autoclave, which was

Lithium acetate monohydrate was added, the result was an initial pressure of 183 atmospheres over 45 minutes

Nitrobenzene conversion of 0%. 50 a temperature of 200 ° C was maintained. Gas-

chromatographically, a nitrobenzene wall

Example 16 98% development and a urethane product yield of

88.4% found.

0.29 g lithium hydroxide, 0.72 g acetic acid. 10 ml.

Nitrobenzene. 15 ml of methanol. 15 ml of dioxane and 0.5 g of 55 B e 1 s ρ 1 e I 22

Selenium disulfide was placed in a 110 ml autoclave with 0.29 g lithium hydroxide. 0.72 g acetic acid, 0.5 g

brought. The autoclave was with a carbon selenium metal, 5 ml of nitrobenzene and 65 ml of methanol

monoxide initial pressure of 183 atm for 45 Mi- were placed in a 300 ml autoclave, the

wells kept at a temperature of 200 C. According to a carbon monoxide beginning of 56.2 atm

The nitrobenzene conversion was 100% for 45 minutes at a temperature of 150 ° C. for 60 minutes

and the urethane yield 96%. was operated. The resulting nitrobenzene

_n . , ₁₇ conversion was 100%, while an original

^{a e 1 sp 'e' u} than product yield of 81.2% resulted.

A 300 ml autoclave was charged with u 29 g

Lithium dioxide, 0.72 g acetic acid, 0.5 g sulfur, 65 B ejs ρ ie 1 23
5 ml of nitrobenzene, 30 ml of methanol and 35 ml of tetrahydro r- and operated it for 75 minutes at The following approaches were carried out in a 300-mlinc = -. <·: 'Enmonoxide initial pressure of 56.2 atmospheres autoclave, the itoklav additional

! i / u bisc and / or water with the following Materials was loaded:

10 ml nilrobenzene,
30 ml methanol «
35 ml 1,4-dioxane and
0.5 g of scallop.

The clions were made with carbon monoxide printing carried out from 183 atm for 30 minutes at a temperature of 200 C. In the The following table shows the amounts used in the reaction, in Uasc and / or water, as well as the Nitrobcrizolumwa.idlung indicated

Triethylamine and 0.5 g (0.006 mole) selenium metal powder was placed in the reaction vessel and brought to a pressure of 56.2 atmospheres with carbon monoxide. After a reaction for 60 minutes

at a temperature of 150 ° C. there was a conversion of dinitrololuene of ιύθ%, a diuretic extractc of 73% and a Moiiourcthanausbcutc of 3%, indicating that a nitro group was not completely converted. Overall project frombcutc

"i 76%.

R cis ρ ic 1 20

! r NalnuinacctaHrihydral

1 ρ sodium acetate (melted)

1 g \ <* 'r :: imacct.': T (gcsi Imh l / cnt

And O.2 ρ Ά'.ι-, μ, τ

0.4X g Natriiiiiiiivdroivd

lind 0.72 g I ssigsäurc

I g w.is-crfrcies potassium aictat

1 ι · anhydrous potassium acetate

lind (ι 2 ρ water

Kfinc Hi c and
I *. L-1 τ ι water

() .: tr water

line mixture of 10.9 g (0.06 MlI) 2,4-Dinitm-

' ^{l |} "" ¹ · -'5 »Ί <'>/> Moii ethyl alcohol. M) ml (0 \ 7 mol)

Niii..hcn *. |. 15 l'vndin. 0.56g (0.01 mole) potassium hydroxide, 0.60p ('.01 Mo!) Lssigsaur. · And 0.05 g (0.0006 mol) Selenmctahpulvcr was placed in the reaction vessel, which was brought to cinci with carbon dioxide, pressure from M), - atü. Ik-1 at a temperature of

160 (crpab a 100 "ige for 60 minutes Conversion of Dinitrotoiuols, whereby one as products 1 "" of the two nitroaminotoluene isomers, 19 " Received nitromonourcihan and 71% diurelhan. the (Total amount of urethanes or the selectivity

in terms of urethanes was 90%. In a similar one Approach 0.072 μ (0.006 mol) selenium dioxide was used instead of the metal powder as a catalyst, the reaction was carried out for W minutes at 50 (, resulting in a 100 "ige

Conversion of dmitrotoluene. a product yield of 3 "" nitroaminotoluene, 34 "mono-octane and 56% diurethanes crpab.

Example 27

line mixture of 10.9g (0 06MoI) 2.4-Dinitroti) luol. 65ml (l, Il VIoI) Ätlr.lu'kohoi. 1.12 g (0.02 mol) Potassium hydroxide, 1.2 g (O.02 mol) of acetic acid and 0.05 ρ ((MXHIi, * f .. |) Earth metal powder was added to the

100

100

91

50
100

A series of batches were carried out with 2,4-dinilrololuene in order to show that the corresponding duirethane can be obtained by the 35 • rhndungsgcmäfien method. The following examples, which show the use of 2,4-dinitrotoluene, were chosen from a large number of approaches, with the conditions or participants in 40 _lnullu ,, _{...... "mi} . _n .,. _c , -

ferc.tem measure were varied, so that occasionally w, r μ ρ V ^{ck V <} "' ⁵⁶ ' ^2alu

.wanted low yields or better S C itKnrt "7f" ΐ ^ *!? -> T • ndesired by-products resulted in the in the umw ™, h, ^g , «, ', ^C ' ^{Mch l} " ^ine '^ "' trotoluolfo. , cnd _s examples described ^ approach "! · ERGAS η ΖΑΠΑΓι ^ ^11" '^? "Z *"'

l »hc conversions and yields with regard to the 45 uretha" s and 9 ("Γ '1 ^ ⁰ "?' η · ^Μ "" ° "

targeted products. All approaches were in a what an ÖesT ^ eS νί iff ^ n ,? ^ " im _i cu :: ... T ..... ri .. r ·" ... ^ ¹ '"- ^v ' csaiTitseiektivitat for urethanes from

With a similar Ar,, at /, with which

300 Til shaking autoclave made of stainless steel (No. 316) with an initial pressure of carbon monoxide of 56.2 atmospheres accomplished.

Example 24

[a reaction mixture of 10.9g (O.06 Vlolj 2.4-dinitrotoluene. 65 ml M.11 moli ethyl alcohol. 0.56g (0.01 moles) potassium hydroxy. 1. 0.6Og (Of) I Mol) i ^ sip-

acid and 0.5 g selenium metal powder (0.006 VIoI) were 55 selectivities of 94 into the reaction vessel. '!!, which then contains column monoxide under pressure <-k gfvct / t became. At a A reaction temperature of 170 ° C. after 15 minutes resulted in a 100% conversion of the dinitrotoluene and a diurethane yield of 72%. A similar approach carried out / continued for 60 minutes at 150 Γ resulted in a conversion of dinitrotoluene: ton 100% and a diurethane yield of 72

.., "w". ",., 68p

. Potassium hydroxide, 80 g (0, u, mol) of tacetic acid were used and the other Rcak-5 "tion participants remained the same, was achieved with a reaction time of ν, .η S () minutes at 150 ° C. . · 100% dinitrotoluene conversion and a product _{yield> of V n} \ itroammotoluolen. 50 "Viono-44" diurethanes, which means a Urelh.mbc.

Example 28

r.a mixture of 10.9 g (0.06 mol) 2 4-HiInM. toluene. 35 ml (0.6 mol) of ethyl alcohol. 1 5 ml (0 19 VM.

S'Jl ^ra i, ^{(0! LlMj} "triethylamine and 0. 2 atu was brought lie,

Example 2 ^C

[line mixture of 10.9 g (O.üt> M ,, ly 2,4-dimtrololuene. 35 ml (0.6 Mo!) ethyl alcohol, Mi _m i (Oz! Moli pressure of 56.2 atu was brought to a reaction temperature of 160 C and A reaction time of 60 minutes resulted in a conversion of 100 "" cmc dioluene and a product yield of 8 ", nitroaminotoluenes, 68% mono-urethanes and 15" diurethanes w.is a fics.in ) '

SS »

m ...- ^ Stuic of 78 ",, corresponds. If one to

gic, Ju-n reaction mixture add 0.01g of water the reaction be for 40 ° minutes;

C, a 98% dinitro

oil conversion and a product yield of

Nitroammotoluenes «75" ,, monourethanes and

Diurethanes. wa> a total urethane yield

93 ■ ',. means.

Example 29

To explain a continuous synthesis of uranium, a semi-industrial plant was set up in which the fully fledged reactants were pumped together with a stoichiometric excess of carbon monoxide into a reactor equipped with a stirrer and operated at 70.3 atmospheres. Weight percent technical dinitrotoluene (80% 2,4-dinitrotoluene and 20 ° _o 2,6-dinitrotoluene). 87 percent by weight of technical-grade ethanol (denatured ethanol, containing 2% benzene), 1 percent by weight acetic acid, 1 percent by weight potassium hydroxide and 1 percent by weight selenium dioxide as a soluble catalyst

From the result η obtained under different conditions it was determined that the optimal operating conditions of this system include a reaction temperature of 177 ° C., a reaction time of half an hour and a pressure of 70.3 atmospheres. Under these conditions, a dinitrotoluene conversion of 100% was achieved with selectivities with respect to the diurethanes of 90 to 95%. At temperatures below 177 C, e.g. B. at 163 C. the conversion changes as a function of the residence time, so that a reduction in the residence time from 1 hour to ₂ hours or 1 hour at 63 (reduces the conversion from 100 to 90 or 76 ° _O Furthermore, lower diurethane yields and higher monourethane yields result if one works below 177 _{° C. for 2} hours. If one works at temperatures above 177 ° C. and with residence times of more than ^{1 and} ₂ hours, lower yields of diurethanes are generally poorer quality achieved. the optimum conditions, the Dinitrotoluolumwanoiunc eibst runs at low Katalysatorkon / cn'rationen quickly reached wherein mau z. B having only 0.07 percent by weight of selenium catalyst in the feed conversions of 90 ° ,,.

These continuously carried out approaches show the excellent technical applicability of the edm-

J 11 ti t / P_l_ _

1153g .. 11 ιο

The following examples represent the preparation of amines. These examples are only illustrative Representative of a large number of approaches in which amines were formed as one of the products. at

and 1.6 g (0.02 mol) of pyridine are charged. The autoclave was initially brought to a pressure of 56.2 atmospheres with carbon monoxide, and the reaction mixture was reacted at 220 ° C. for 2 hours.

After cooling to room temperature and venting, it was found to be 77.4 mole percent. of nitroben / ol was converted and aniline with a yield of 56.6 Mjlprozent and urethane with a Yield of 6.5 mole percent were formed.

Example 31

In the same 300 ml autoclave were added 10 ml (0.098 mol) of nitrobenzene, 100 ml of methyl alcohol, 1 g of sodium acetate and 1 g of powdered sulfur. The reaction vessel was brought to a pressure of 35.2 atmospheres with carbon monoxide, and the reaction was carried out at 220 ° C. for 10 minutes. In this way, with a nitrobenzene conversion of 35.5 mole percent, aniline was obtained with a yield (selectivity) of 30.4 mole percent and urethane was obtained with a yield of 39.3 ° ₀ .

Example 32

A mixture of 10.9 g of 2,4-dinitrotoluene, 100 ml of ethyl alcohol, 1.28 g of potassium acetate monohydrate and 0.5 g of welding powder was poured into the 300 ml reactor, which was brought to a pressure of 35.2 atmospheres with carbon monoxide. The reaction was carried out for 1 hour at ^200.degree. C., a conversion of the 2,4-dinitrotoluene of 44.8 mol percent being achieved. The percentage selectivity, based on converted dinitrotoluene, was 40.2 ° for the two monourethane isomers in which one nitro group was not converted, 41% for the nitroaminotoluene isomers and less than 1.5% for the diurethanes.

Example 33

Finp

* ir \ ncmic ^ hiiniT anc 1Ω Q σ 7 4.nimtrn_

.! tr

Toluene, 35 ml of ethyl alcohol, 30 ml of pyridine, 1 g of water and 0.012 g of selenium metal powder were poured into the reactor, which was then brought to a pressure of 56.2 atmospheres with carbon monoxide. The reaction was carried out at 150 ° C. for 90 minutes, a dinitrotoium conversion of 83% being achieved. The yield of mono-nitro-urethanes, which contained a trace of di-urethanes, was 14; _o and a yield of nitroaminotoluene of 73 "". A second batch was carried out under the same conditions as stated above, with the difference that 0.4 g of water and 0.015 g of selenium powder were used. A dinitrotoluene conversion of 90% e a lot, whereby the monourethane with a trace of diurethane in a period of 55% SjM.I ι: io \ tnuminotoluolim> \ n-, lxutt: of I ^ ',. \ MiUi.

Vi-, ti'- ">> igen execution'-η <■■ · - ■ milk that

Ii iTtnKiun ^ stiomaLle Verfallii:,: i ·. · Rv ■ Raged Vor .; 'O -ι' - '/ K ¹ U-It venn.it ;. You egg; :. ' ,,. _t * "jcmaiJc encryption '.ιίιΓι k: ¹ teihriis h / ur Ιϊγγμι lni- ■ <·, w t.Tcthanr'iMj'.KiiN ι, ιιιΙ Aiinr.iiebenprn. ι. ... i high

Ή-iit ■■■> hi ΐι-Ι, ιΐιν musty Hc si;> or.iluren and

- ■! 'I.i.tiTi ii -.- l iiii'or Anwcniiu ^' ■ in. Kur / cr reac-

I ₁ 'is /' - ilr :! . ! ft ¹ »; ' be lull

609 625/267

Claims (1)

The errmduneseemäü suitable hydroxyl groups Claim: containing compounds have the following f-.vmelr ,,. , τ, ", · h, - R (OH) ,, and R (OH) ,, Method of making lretnanei ;. possibly simultaneously with "amines, by fm- 5 _{or r} , ^ setting at least one hydroxyl group en, - ^" * «nc ^ ^ _{) cnfaIK} ^, ^ holding aliphatic or aromatic Λ = -.-- ^ ¹ " - '- , vi.v.linhiitKchen ode -ιίπΊ, hols or phenols mu carbon monoxide and enr «« "^^^ ΐΐΤΐ"; o KohÄ containing at least one nitro group al.ph.i- i ^ he ^ Kc, ^ ^ ^ tischen or aromatic Nitro compound be: ίο ato nen sieni u ... κ.η /, -, ϋ -.- ηρ R, _n ". ·. ,, ■ Temperatures from about 60 to 250 C and pressures. * E, * c n. cht m, -, r al, ure. bcn / ol ^ ne Rin _C , _t u ,, · from about 10 to 100 atmospheres in the presence of tender aromatic. remainder; sL wubu d,,, ο., ιng. of a metal catalyst, d adurc h ge ke η n- ankondenvert. durcn rmfachbK.dung.n drrekt occr • u jo Jt, -.,., - iihe'-Bruci-n ^ ruppen eebunücn his ability, the /. B draws that one the Implementation m tjegeri- " ^rt - 'Bna-yuii. ci <- ι. - ι ι- ι uj «-" si! ir>'or ^T - nitrogen! - oucr sulfur atoms or suI! - wait for selenium, Schwele. a Seienverbmdunj. ! .-> > .iu "r * .i'i. .> n "" ". r, -, j »«, “,,, ι -siilf.> i- \ nnr.- Amu: or carbon \ leruppen a sulfur compound or a \ n> .r.uni oxyu- ^ Li ,, ... .im ... , ,, \ r '. _ff . ■ r> j ι! T ^ ₁ „ ■ mirr \ ^ vL ¹ Ha ^1- UPPCn be ko; ine: i. over cones ^ iri- these products as a catalyst together m ·. ontr ^ ''"i" ⁴ !! ¹ .-. ", • j η j j, ι i u L-piii-; B by Suuerslott- ouer ^ cnweielatome at least one base and or water through chain / -d. uuu.i. - »y« »- _{leads to} sulfoxide, sulfone or iroonyl groups 2o bnvhe'n can be, like 7 B methylene. Oxymethylene