DE1793609A1 - Polyether complexes and process for their preparation - Google Patents

Description

B. I. DU PONT DE HEMQURS AND COMPAFT Wilmington 98, Delaware / V.St.A ...

Our mark; P 2056

Polyether complexes
and process for their production

The invention relates to complexes containing certain polyaether compounds and to a process for their preparation these complexes.

The complexes of the present invention are those of one macrocyclic polyether with 4 to 8 ether oxygen atoms, with each oxygen atom from the next through at least 2, preferably 2 or 3, carbon atoms are separated and wherein at least 2 of the oxygen atoms sit on vicinal carbon atoms of an aromatic nucleus, preferably with a matching cation j the ether contains at least 12 ring atoms. These polyaethers and methods of making them are detailed in British Patent Hr. 1 108 921 described and form the subject of the German patent

ITr. ., (official file number of the application

P 15 18 103.0).

The complexes can be referred to as "crown complexes". You will usually, but not always, be on one 1: 1 base formed, i.e. one molecule of crown compound

10 9886/1938

8ADORlO (NAt.

on a cation. In most cases, 2 molecules of the crown compound to complex with one would be 2 cations containing salt required.

(It is believed that the molar ratio of crown compound to cation in the complex depends, at least to some extent, on the relative sizes of the cation and the "hole" in the center of the cyclic ether molecule, or in other words the diameter of the ring. ) The size of the charge on the cation does not change the stoichiometry; so both Li ⁺ and Ca ^{++ are} considered to be a single cation. The cation can be either organic or inorganic. Examples of suitable cations are those derived from primary amines and metals in Groups I-III of the Periodic Table; however, many others can also be considered.

This property of crown compounds varies and appears to depend on the arrangement of the oxygen atoms in the Macroring as well as depend on the relative diameter of the ring and the cation. Achieved the best results one evidently if the oxygen atoms are arranged as symmetrically as possible and if the ring diameter is the ion diameter exceeds. For example, the crown connection (3) with an equivalent of lithium (ion diameter 1.2 angstroms) or sodium (1.9 angstroms) form a complex. The expression used above "Matching cations" thus refers to cations which form a complex with a particular crown compound. Typical crown complexes according to the invention are as follows:

109886/1938

(1) 2,3,9 »10-dibenzo-1,4,8,11-tetraoxacyclotetradeea-S, 9-diene with Li ⁺ or Na ⁺ .

(2) -2,3,8,9 "-DIlJeIiZO-I ^ ', 7,10-, l ^ -pentaoxa-cyclopentadeca-2,8-diene with Na ⁺ , K ⁺ , Go ⁺ or Ba ⁺⁺ .

• ('3) 2,3,9,10-dibenzo-1,4,8,11,14-pentaoxacycloh.exadeea-2,9-diene with K ⁺ , Co ⁺ , Ca ⁺⁺ or Na ⁺ .

(4) 2,3,8,9-dibenzo-1,4,7,10,13,16-nexaoxacycloootadeca-2,8-diene with Id ⁺ , Na ⁺ , K ⁺ , Co ⁺ , Ca ⁺⁺ , Sr ⁺⁺ or Ba ⁺⁺ .

(5) 2,3,11,12-dibenzo-l, 4,7,10,13, le-hexaoxacyclooctade ca-2,11-diene with NH ₄ ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Eb ⁺ , Ag ⁺ , Ca ⁺⁺ _f Ba ⁺⁺ , Ce ⁺⁺⁺ , Co ⁺ , Hg ⁺ , La ⁺⁺⁺ , [Dl ⁺ HONH ⁺ , H ₉ N-NH ⁺ ,

4.4.4. Jd. J

i-C.Hq-NH, or Sr.

(6) 2,3,11,12-dibenzo-1,4,7,10,13,18-hexacyclodocosa-2,11-diene with Co ⁺ or K ⁺ .

(7) 2,3,14,15-dibenzo-1,4,7,10,13,16,19,22-octaoxacyclotetracosa-2,14-diene with Na ⁺ , K ⁺ , Sr ⁺⁺ or Ba ⁺⁺ .

(8) 2,3-Benzo ~ l, 4,7A0,13,16-h.exaoxacyclooctadeca-2-eii with Na ⁺ , K ⁺ , Rb ⁺ , Co ^+,. Ag ⁺ , Sr ⁺⁺ or Ba ⁺⁺ .

(9) 2,3,8,9,14.15-Tribeiizo-l, 4,7,10,13, Ιβ-hexaoxacyclooctadeca »2,8,14-triene with Li ⁺ , Na ⁺ , K ⁺ , Co ⁺ Ag ⁺ or Ca ⁺⁺ _#

(10) 2,3 1S1 10 ~ dibenzo-l, 4,8,11,14,17-h.exaoxacyclonoiiadeca »2,9-dieii with Na ⁺ , K ⁺ , Co ⁺ , Ag ⁺ , Ca ⁺⁺ , Sr ⁺⁺ or Ba ⁺⁺ .

(11) 2,3,8,9,14,15-TribeiiE0 ~ l, 4,7 _f 10,13,16-liexaoxacyclononadeca-2,8,14-triene with Na ⁺ or K ⁺ .

109886/1938

(12) 2.3

neicosa-2, ll ~ diene with Na ⁺ , ITH ⁺ , K ⁺ , Go ⁺ , Ca ⁺⁺ , Sr ⁺⁺

J-J- T "

or Ba ⁺⁺

2,3,8,9,14,15-Tribenzo-1,47,110,13,16,19-heptaoxacycloheneicosa-2,8,14-triene with Na ⁺ , NH ⁺ , K ⁺ , Co ⁺ , Ca ⁺⁺ or Ba ⁺⁺ .

(14)

y § - Sr ⁺⁺ or Ba ⁺⁺ .

cyclotetracosa-2,8,14-triene with Na ⁺ , K ⁺ , Co ⁺ , Ca ⁺⁺ ,

(15) 2,3,8,9,14,15,20,21-! Detrabenzo-1, 4,7,10,13,16,19,22-octaoxaeyclotetracosa-2,8,14-triene with Na, NH. ⁺ , K »Co ⁺ , Ca ⁺⁺ , Sr ⁺⁺ or Ba ⁺⁺ .

(16) 2,3- (tert-Butylbenzo) -1, 4,7,10,13,16-hexaoxacyclooctadeca-2-ene with Na ⁺ , K ⁺ , Ca ⁺⁺ or Ba ⁺⁺ .

(17) 2,3-Benzo-1,4 »7» 10,13-pentaoxacyclopentadeca-2-en with Li ⁺ , Na ⁺ , K ⁺ , Sr ⁺⁺ or Ba ⁺⁺ .

(18) 2,3- (tert-Butylbenzo) -1,4,7,10,13-pentaoxacyclopentadeca-2-ene with Na ⁺ , Sr ⁺⁺ or Ba ⁺⁺ .

These complexes were made in methanol according to the general below methods described, although other solvents, including other hydroxylated solvents and polar and non-polar solvents, can be used provided that their solvency for a particular combination of crown compound and cation-donating compound is sufficient. The addition of the cation-supplying compound to the Crown compound can increase or decrease the solubility of the latter, depending on the particular one used

109886/1938

solvent and cation. Also, a relatively insoluble crystalline complex can form from a crown compound contained in a liquid, which has only a low dissolving power for both. The presence of the complex in solution, regardless of whether he as.! Solid can be isolated or not, can be determined by spectrophotometric analysis, since the addition of the appropriate cation the ultraviolet spectral accompanied by a change of m shape of the crown compound in solution is.

As a general rule, the greater the stability of the crown complex in the respective environment, ie the solvent, the greater the prospect of being able to isolate the complex in pure form. The stability constant of the crown complexes depends on the solvent in which they are located. The crown complexes of compound (1) disintegrate in water; the solubility of the compound (1) in water is therefore essentially not changed by the presence of lithium bromide or sodium bromide. On the other hand, the solubility M in methyl alcohol increases almost tenfold when lithium bromide is added. The complex formed from the compound (1) and the lithium ion in methyl alcohol can serve as a means for separating the lithium ion from the alcohol and then releasing it into water.

The increase in solubility due to complex formation is even more pronounced in normal butyl alcohol, in which the addition of lithium bromide causes a ^33facne increase in the solubility of the crown compound '(1). Similarly, the solubility of the compound (5) which has a structure of 18 atoms, the

Oxygen atoms are arranged very symmetrically, "at 26 ° C increased by 5.5 times in the presence of sodium chloride and by 8.9 times in the presence of strontium chloride, but at $ 56 of its normal value in the presence of magnesium chloride, with which it does not form a complex, degraded.

The crown complexes can be prepared by mixing the crown compound with the cation-providing compound in one Solvents are prepared in which at least one of these compounds is soluble. In the cations supplying compound, any anion can be present if only it is not related to the cation one used in the one Solvent forms insoluble salt. The temperature at which the mixing takes place is usually close the boiling point of the solvent, the amount of the solvent is preferably at least sufficient to a to give clear solution at this temperature. If the stability of the crown complex thus formed allows it, becomes a pure, crystalline complex through subsequent cooling, filtration, washing and drying or through evaporation of the solvent obtained. If the crown complex cannot be isolated, it can be in the solvent, in which it was made.

If neither the crown compound nor its complex with a certain cation in the solvent used is sufficient is soluble, the crown compound and a cation-yielding compound are required in the required Portions mixed in the presence of the solvent and this is then stirred and heated. In this case the crystalline crown compound gradually changes to the crystalline complex and the system never forms

C / 1 9 3 3

a clear solution. The formation of the complex can through its melting point can be determined, which of that of the crown compound and the compound providing cations is different; in addition, the complex is identified by its chemical composition.

The formation of crown complexes allows its use certain chemical reagents in non-aqueous or non-alcoholic media in which they normally are insoluble. For example, a benzene-soluble (§ Complex of potassium hydroxide through the reaction of equimolar amounts of potassium hydroxide and the tert-butyl crown compound (10) Prepared in methanol and complete removal of the solvent by evaporation. With a typical Experiment showed that by stirring this solid complex obtained in benzene at 25 ° C and filtration

Benzene solution has a 0.02 normal basicity. ' If, on the other hand, finely divided potassium hydroxide vigorously stirred in boiling benzene and the mixture obtained for separation is filtered of dispersed solid potassium hydroxide, the benzene filtrate contains essentially no potassium hydroxide.

^{'■■■■■ :::} ι

Neither potassium nitrite nor potassium permanganate are in benzene ^ soluble. The former can be done in exactly the same way how potassium hydroxide can be solubilized in benzene. Potassium permanganate is made soluble in benzene by adding one equimolar amounts of potassium permanganate and the tert-butyl crown compound 2,3, ll, 12-bis (tert-butylbenzo) -l, 4,7,10, 13,16-hexaoxacyclooctadeca-2, ll-diene in acetone and then all of the solvent from the crown complex evaporates ... '■■

In general, these benzene-soluble crown complexes form new analytical reagents for use in non-hydroxylated Media in which they are not in the complex

109886/1938

transferred reagents are normally insoluble. They can also be used for technical purposes. The benzene-soluble potassium hydroxide complex can be used to initiate the anionic polymerization of acrylonitrile or pivalolactone to form a polymer with terminal hydroxyl groups as a soluble acid acceptor in systems that are neither acidic nor basic. The benzene-soluble sodium nitrite complex can be used as a corrosion inhibitor for iron and steel are used in non-aqueous systems and for the diazotization and nitrosation of amino compounds in non-hydroxyl-containing media. The benzene-soluble potassium permanganate complex can be used for the cleavage of olefinic compounds. In general, almost any reaction in which the reagents not converted into the crown complex can be used aqueous or alcoholic medium can participate, can now be carried out in non-hydroxyl media using the corresponding tert-butyl crown complex.

^. Potassium 2-ethylhexanoate is almost insoluble in cyclohexane and the electrical resistance of cyclohexane in contact with this salt is not less than that of the ' Solvent alone. The potassium 2-ethylhexaonate converted into a complex with the tert-butyl crown compound is soluble in cyclohexane and lowers its electrical resistance; thus these can be solubilized Crown salts used to increase the electrical conductivity of neither basic nor acidic systems will.

The crown connections are suitable for separating dissolved salts. The salt, the cation of which forms a crown complex:

10 9 8 8 6/1938

1733609

can, can then by means of a non-miscible solvent, which is not complex-bound Salt cannot dissolve, can be extracted. For example can, such as water-soluble salts, which tert-butyl crown complexes form, of salts that do not, by extraction with a water-insoluble solvent be separated for the complex. For example, the compound (5) forms a complex with potassium ions, but not with magnesium ions; thus can use potassium salts can be separated from magnesium salts with the help of this compound ™.

The crown compounds according to the invention can also be used as dye intermediates by introducing an active hydrogen-containing substituent, for example OH "" or the amino groups, into the aromatic nucleus by conventional methods and then coupling the compound with a diazo compound by methods that are likewise known. For example, azo dyes from the crown compounds 2,3,8,9-dibenzo-l, 4,7,10-tetraoxacyclodeca-2,8-diene; Z ^ ill ^ ia-Dibenzo-lj ^ jTAOjl ^ -pentaoxacyclooctadeca-2, ll-diene or (5) prepared as follows: M

The aromatic nitro derivative was obtained by Mix a mixture for 2 hours while stirring very vigorously (a) a chloroform solution of one of these crown compounds (relative concentration 1.5 g / 30 cm) and (b) with a equal volume of water of diluted concentrated nitric

'' S ■ ■ ■

acid (relative concentration 7 cm of this solution to 1-2 g of crown compound) was kept at reflux.

The aromatic amino compound was obtained by reduction the nitro compound obtained in the previous stage with excess metallic. Tin prepared in methanol containing concentrated hydrochloric acid (relative

ORIGINAL

- ίο -

• τ rx

Concentration 50 cm methanol + 5 cm hydrochloric acid / 1-2 g original crown connection).

The amino compound was obtained by treating the solution with an excess ·. a strong aqueous sodium nitrite solution in the presence of ice and decomposition of the excess nitrous acid formed with sodium sulf ainat diazotized.

The azo dye was obtained by adding the solution of the diazo compound thus formed to a strongly alkaline one (Sodium hydroxide) aqueous solution of 1-amino-8-naphthol-3,6-disulfonic acid added, the latter being present in excess over the diazo compound. Fabrics on Cellulose bases such as cloth and paper were prepared by heating with the azo dye solution obtained above, rinsing Stained with clean water and drying. Azo dyes can be obtained from the other crown compounds according to the invention can be obtained in the same or a similar manner.

■ k The following table gives some specific examples which explain the formation of complexes deviating from the crown compounds indicated and identified by the numbers. In all cases the crown compound and the indicated salt were added to the indicated solvent, which was heated to about its boiling point, whereupon the complex formed was isolated.

«AD ORiGfNAL

Tabel

Crown-
link salt solvent Melting point of
Complex (No.) 1 LiCNS Methanol 300 ° C 5 NaCNS Methanol 230 ° - 232 ° C 5 NaNO ₂ Butanol 154 ° - ■ 157 ° C 5 AI ". ■ Methanol 232 ° - 234 ° C 5 NH.CNS Methanol 187 ° - 189 ° C 5 σ Methanol 128 ° - 155 ° C 5 CsCNS Methanol softens at
105 C _t 5 CaCl ₂ Butanol 300 ° C '5 Ba (OH) ₂ Methanol softens at
180 ° C 5 Cd Cl ₂ Butanol 300 ° C 5 Hg Cl ₂ Butanol 238 ° - 249 ° C 5 PbOOcCH ₃ Butanol 167 ° - 198 ⁰ C 16 K CNS Methanol 134 °: ■ - 136 ° C 18th LiCNS Methanol 169-174 ° C

The invention is further illustrated by the following examples explained.

example 1

Potassium rhodanide complex of 2,3,1,12-bis (tert-butylbenzo) -1,4,7,10,13,16-hexaoxacyclooctadeca-2,11-diene. -

A 3 liter flask equipped with a thermometer, a reflux condenser, and a stirrer was attached to 2 6 °. C-with 402 g (1 gram-mol) bis./2-(o-hydroxy-x-tert.-butylphenoxy )-aether/aether, 600 ecm n-butanol, 400 ecm

109886/1938

Water, 80 g (2 gram-mole) sodium hydroxide and 143 g (1 gram-mole) bis (ß-chloroethyl) ether are charged. the Charge was made for 41 hours under nitrogen at atmospheric pressure kept at reflux with vigorous stirring; the end temperature of the flask was 97.5 ° C.

On cooling to 25-30 ° C, the feed separated into two layers. The uppermost organic phase was separated off, evaporated to dryness at 0.5 mm Hg and dissolved in 1250 ecm n-3utanol by heating to 60 ° C. 100 g (.03 mol) of potassium rhodanide were added, and this was crushed and stirred in the system with continued heating on the water bath. When all of the rhodanide had dissolved, the charge was evaporated to dryness at 0.5 mm. The 514 g residue was heated with 1 liter of benzene and the white crystals obtained were filtered off, washed with 100 ecm benzene and 100 ecm petroleum ether (boiling point 30-60 ° C.) and dried. The resulting white crystals weighed 98.4 g and were the potassium rhodanide complex of the desired product: ^ ρβ ^ ΑΟ ^ β ^: KORS and corresponded to 81.6 g of C _{gH.0 0} g.

Example 2

Potassium rhodanide complex of 2,3- (4 ^f and / or 5'-tert-butylbenzo) -1,4,7,10, ^ -pentaoxacyclopentadeca ^ -en.

A 2 liter round bottom flask equipped as above was used with 33.2 g (0.2 gram-mole) of 4-tert-butylcatechol, 700 ecm n-butanol, 17 g (0.425 gram-mole) sodium hydroxide in 40 ecm of water and 46.2 g (0.2 gram-mole) of l, ll-i) chloro-3,6,9-trioxaundecane loaded. The charge was refluxed under nitrogen with vigorous stirring for 17 hours held, the temperature in the flask fell from 103.5 to 100 ° C.

109886/1938

ORIGINAL

1-

- 13 -

The .'Beschickung was then filtered off and in a Rotary vacuum evaporator evaporated to dryness at 60 ° C, The residue (71.2 g) irard extracted with 300 ecm benzene and the extract was 4 χ aqueous with 100 ecm Seigern Washed sodium hydroxide, filtered and evaporated to dryness. The residue (60.8 g) was at 0.45 mm from a Rotary evaporator distilled. The oily distillate contained 91% by weight of the desired product. A 41 g portion (about 0.126 mol) of the distillate was added to a stirred solution of 13 g (0.134 mol) of potassium thiocyanate in 150 ecm Added room temperature methanol. The crown complex formed as white crystals. After adding 50 further ecm of methanol, the mixture was cooled and the crown complex filtered off. .

Example 3

Potassium rhodium complex of 2,3-benzo-1,4,7,10,13,16-hexaoxacyclooctadeca-2-ene.

A 500cc round bottom flask equipped as above was used with 6 g (0.0546 gram mol) of catechol, 200 ecm of n-butanol, 4.4 g (0.11 gram-mole) sodium hydroxide in 10 ecm of water and 15 g (0.0546 gram-mole) 1,4-dichloro-3,6,9,12-tetraoxatetradecane loaded. The feed was refluxed under nitrogen with vigorous stirring for 6.25 hours held during which time the piston temperature of 104.5 to 102.5 ° C. '

The feed was filtered hot and placed on a rotary vacuum evaporator evaporated to dryness at 60 ° C. The viscous, oily residue (18.5 g) was 100 ecm

1098 86/1938

0AD ORIGINAL

Chloroform extracted and the extract was washed 2 χ with 50 ecm 5 $ aqueous sodium hydroxide, dried over anhydrous sodium sulfate and dried to dryness evaporated. The viscous, oily residue (12.5 g) was distilled from a rotary evaporator at 0.4-5 mm. The nearly colorless, viscous distillate (9.9 g) contained 58% by weight of the desired product. A 9 g portion of the The distillate was mixed with a clear solution of 2.8 g of potassium rhodanide in 100 ecm of methanol. The received The complex was made by evaporation of the solvent isolated at room temperature and filtration. After washing out the complex with 25 ecm of tert-butanol and drying 4.3 g of white crystals were obtained.

Analysis: Calculated for C ₁₇ H ₂₄ NOgSK: 49.9 $ 0 *, 5.9 $ H;

3.4 $ N-, 7.8 $ S.

found $ 40.8, $ 40.7 C;

4.5, 4.6 $ Hj. 6.1 $ N; $ 11.5 p.

Example'4

Potassium rhodanide complex of 2,3- (4'-tert-butylbenzo) -l, 4,7, 10,13,16-hexaoxacyclooctadeca-2-'en.

A 1 liter round bottom flask equipped as above was used with 9 g (0.0542 gram-mole) of 4-tert-butylcatechol, 200 ecm n-butanol, 4.4 g (0.11 gram-mole) sodium hydroxide in 10 ecm Water and 15 g (0.0546 gram-mole) 1,4-dichloro-3,6,9,12-tetraoxatetradecane loaded. The charge was refluxed with vigorous stirring under nitrogen for 23 hours held during which time the flask temperature

108886/1938

"BAD ORIGINAL

105 ° C "remained.

The pale orange solution was decanted from the plague and evaporated to dryness in a rotary valaium evaporator. The residue (22.3 g) was extracted with 200 ecm chloroform and the extract was 2 χ with 250 ecm L ^ ige aqueous sodium hydroxide washed out over dried anhydrous sodium sulfate, filtered and evaporated to dryness. The residue (20.6 g) became out distilled on a rotary evaporator at 0.45 mm. That viscous, cellular distillate (17.3 g) contained 71% by weight desired product. A 12 g portion (0.032 mol) of the distillate was added to a solution of 3.5 g (0.036 mol) Iialruinrhodanid added in 50 ecm of methanol. After evaporation of the solvent at room temperature, the The residue (the eronene complex) was triturated with ether and filtered and dried. 7.6 g of a white powder were obtained. . .

Analysis: calculated for

found

54.2 fo C; 6.9 7 ° Hi 3.0 <fi N; 6.9 % S. 51.8 "56 52.1 * C; 6.7> , 7.0 H? $ 3.29 N; 6.7 S.

1098 86/1938

βΑΟ ORIGINAL

Claims (5)

- 16 claims Complex of a macrocyclic polyether with 4 "to 8 ether oxygen atoms j where, each oxygen atom from next is separated by at least 2 carbon atoms and at least 2 of the oxygen atoms © on vicinal carbon atoms an aromatic nucleus, with a matching cation. 2. Complex according to claim 1 _f, characterized in that the »Polyaether has at least 12 carbon atoms and that each oxygen atom is separated from the next by 2 or 3 carbon atoms. 3 # Process for the preparation of a complex according to claim 1 or 2, ds.du.rch characterized in that the polyaether and a compound containing the appropriate cation in the presence of a liquid having a solvent power for both the polyaether and the salt are mixed. 4. The method according to claim 3> characterized in that the polyether and the compound at one temperature ™ should be mixed close to the boiling point of the solvent. 5. Method to make a water soluble cation in non-hydroxyl containing organic solvents for use, for example in analytical processes or for the separation of salt mixtures or for the oxidative cleavage of olefins to make soluble with potassium permanganate, characterized in that a complex of the cation with a macrocyclic polyether according to claim 1 or 2 is formed and dissolved in the solvent. 109886/1938 BATH ORIGINAL