DE2603870C3 - Process for the preparation of α-halobutenols - Google Patents

Description

C "C

I I

OH X

CH,

where X stands for Cl or Br, thereby characterized in that one 0.5 to 5 mol 2 Methyl-I-butyne-2-oI in vapor form at 70 to 200 ° C and a pressure of 200 to 760 now I Ig in Presence of a salt, particularly a halide, a Group 1, II or VIII metal of the periodic table as a catalyst with 1 mole of anhydrous chlorine b / w. Converts hydrogen bromide, wherein the / u using catalyst in a Concentration of 0.1 to 20% of the carrier weight is applied to a conventional porous carrier.

It is known from the specialist literature that! Melhylbuti Get with a halogenated hydrogen. especially C hlorvvjssersioff. reacts in the liquid phase in the presence of clones. Here there is predominantly one Reaction between the flydroxyl group of Meihylbu ünoli and the anion of the halogenated hydrogen sun, whereby a molecule of water is released and it is formed a halogenieries. z. B. chlorinated product of Aceiy type ^ -Methyli-chloro-j-butyne). This becomes in follow a proton shift promoted by the presence of salts already during the Implementation itself other chlorinated isomers are formed, all of them by the empirical .Summenformula (M I Cl can be represented. Such isomers, from of which there are usually four to six have unsaturated bonds of the acetylene or aile type or koii | ugierie multiple bonds. The separation of these compounds, which by complex isomers are equal and very close together Boiling points are marked is extraordinary difficult

It has now been found that the reaction of methylbiitinol in the vapor phase with anhydrous hydrogen chloride or hydrogen bromide in the presence of certain chemical salts. »Lic are applied to a porous carrier. is obtained as the main product substances which never arise in the known reaction in the liquid phase in fact also, / B mn HCI .ils hydrogen halide, the analytical data have shown that the composition of the obtained substance that of \ C hlorbulenol (2 methyl i buten 5 chloro 2 oil) corresponds to The structure of the compound was also confirmed by mass spectrometry, among other things.

The reaction product is therefore the result of the addition of a molecule of hydrogen chloride or hydrogen bromide to the acetylic triple bond of methylbutiol. The halogen atom is in the alpha position to the hydroxyl group and to the alkylene carbon atom, who wears less water loafalome, bound.

The inventive method for producing CFI ₁

CII ₁

C) II X

where X stands for CI or Br, is characterized in that that 0.5 to 5 mol of 2 methyl-5 butyn-2-ol in

κι Dampffomi at 70 to 200 C and a pressure of 200 up to 7b0 mm Hg in the presence of a salt, in particular of a halide, a metal of group I, II or VIII of the periodic table as a catalyst with 1 mol of anhydrous hydrogen chloride or hydrogen bromide

ι> implements, the catalyst to be used in a Concentration of 0.1 to 20% of the carrier weight a conventional porous carrier is applied

The chlorine or bromobutylol derived from the process according to the invention is characterized by

- <> two free functions. d. H. through the hydroxyl group and «read halogen atom, and equally / hurriedly by the presence of a double bond. Such in the organic chemistry also as ethylenically unsaturated Halohydrins »defined substances are very

- '· responsive. In practice they can. similar to that saturated halohydrins, for example with advantage for the production of special types with [poxides. Glycols. or amino alcohols can be used. Their main characteristic is the presence of an unsaturated

ι »th bond of the ethylene type in their molecule and they can be purchased as vinyl monomers, which are characterized by two special functions and as such can be converted into polymerization! ('«! Use the polymerisation process. Man ei hall

ι · thereby polymers, which are considerable by cmc Number of free functions distinguish what they are used for further implementation makes it particularly suitable.

With continuous implementation of the invention Method ai is preferably cured by m

ι »cylindrical reactors, called the Vcihallnis between length and diameter between 20 and 150: 1. Good results can also be achieved when working in I bed reactors.

The basic parameters of chemical and

The type of catalyst which play a role in the production of the lalogenbulenole according to the invention is of a physical nature. the implementation temperature. the ratio of the participants in the action and
while working continuously - -lie hourly «. '

> ii Diirchsatzquote per I. Her catalyst.

Effective catalysts for the addition of the hydrogen halide into the triple bond of the Melhylbutynols are salts, especially those Ilalogen salts, of metals from the I. Il iinil VIII

> i group of the periodic table.

The catalvic character of this silt is special pronounced when one. like «.lies erfmdiingsgcmall the case is. as I rager Siibst.in/eri with great specific surface surfaces are used as Irager

wi therefore activated carbon. Pumice stone and aluminum oxide obtained preferred as they are commonly known as catalyst supports;

The catalyst is uniformly applied to the carrier in a concentration of 0.1 to 20% of the carrier weight.

f) ¹ ) tes distributed, the amount of which depends on the type of salt used and the Rcüklionsbcdingiingcti.
The reaction temperature is within 70 to 200 "C

unil muli be so high, dali the Mclhylhuliiicil and the Reaction products at the pressure at which this is Procedures carried out are available in D.inipffnrm. In the interests of good implementation and, above all, tier Selectivity of the reaction with regard to vllalogenbuienol all other things being equal is the ratio between the con / enlr.ition of methylbutynol and those of chlorine or hydrogen bromide are important. Generally speaking, the molar con / enirion lies ratio of the two respondents / wipe> undo. ") and preferably / wisehen 5.0 undo,"): I.

The continuous flow rate through the reactor filled with the catalyst applied to the support (expressed in liters of methylbutynol under standard conditions per liter of catalyst) 0.01 to 2.01 one with the implementation selectivity values for \ C hlorb / w. χ Brombutenol et lullen that even ^{exceed 40 1} VIi.

Normally the yield, ie the degree of ionization, is for methylbuiinol. / between 60 and 90 ¹ VIi.

Isopropylene acetylene is produced as a secondary product and some chlorinated or brominated isomers of the empirical formula CMbI IaI.

The vHalogen butenol came from the resulting products in the usual way, e.g. B. by fractional Distillation with reduced drink, without further ado in will keep practically pure I -'οπή egg.

Example I.

I in cylindrical Reaklcrinu a · ratio length to diameter of elwa 100: I, activated carbon, aiii in a con / enir.ition of 5% mercuric chloride (JIgCL) is distributed. loaded. The temperature read Öliiuintels around the reactor is thermostatically increased 150 C and the internal pressure of the reactor to 760 mm I Ig held. In continuous operation and in Appropriate mixture are the reactor beforehand evaporated methylbiiiinnl and anhydrous chlorine supplied with hydrogen, the molar ratio of the concentration being marked by a value of 2.1 net is.

The passage / speed (liters of methylene mol under standard conditions / I.itcr catalyst / per hour) has a value of 0.5. where “standard conditions” mean a pressure of 7hl) mm Hg and a temperature of 20 C / u .

Implementation is ongoing. As a gas chromatographic analysis showed, with a degree of conversion for Mcihvlbuiinol of about 15%. In the reaction profiles there is a concentration of 40% hloibutenol, which corresponds to a concentration of 89%. In addition, the following were produced: isopropene acelvles. The reaction products are removed by distillation under reduced pressure. The chlorohulene oil thus obtained is a colorless liquid with a boiling point of I SI to I 52 C. At a vacuum of 20 mm Hg, the product boils at 40 to 42 ° C.

The substance is finer characterized by a specific gravity of 1.0563 g / cm ¹ and a Refniktionsindcx of 1.4489, respectively at 20 ⁰ C.

Analysis:

Gcf. C 49.64, H 7.48, Cl 29.11;
bcr. C49.80, H 7.52, Cl 29.40.

The NMR spectrum of the Pmdukie has three signals fi: I: I of relative intensity; the first two are centered at 1.4 and 5.2 ppm, respectively, the third signal falls to about 5 ppm and is characteristic of the hydroxyl group; it shifts according to temperature and concentration. The first signal is a typlet and was assigned to the C 11 i groups in terms of position and intensity; the signal is at 5.2 ppm a doublet with separation at 5OcP, which due to the unshielded different effect of the Halogens is attributable to the two non-equivalent vinyl protons.

The internal coupling constant between the two protons is 1.4 cP.

L-as IR spectrum shows the following bands:

- strong peaks at 5400 (} · O-H), 2949.2980. 1625 () 'C' = C), 1090 () 'C-O). 975 and 890 (vinyl) em '.

- medium peaks at 1465 (isopropyl), 1190, 1170. 1140 and 780 cm '.

The mass spectrum / has a few main peaks, which are characterized by the following ratios of mass / u charge at the percentages mentioned:

4 5 (50%); 59 (82.5 '/.)); 85 (17%);
105 (100%) and 120 (10%).

The masses 120 (starting mass ·) and 105. correspondingly the chlorohydrin; xybuienylion. are accompanied by the respective masses +2. characteristic of the chlorine derivatives and in quantitative agreement mild isotropic ratio (!>, C l ,, ·.

All the values obtained by the above-mentioned investigations are in agreement with the fur the main product of the implementation adopted structure, as in this way unambiguously for the first time is defined.

Example 2

1: In a cylindrical reactor, in which the ratio of length / diameter is about 100: 1, is charged with activated charcoal in which 5% mercury chloride (1 IgCl ..) are dispersed. The temperature of the oil tank is kept at 150 "C. The reactor is then continuously fed an intimate mixture of previously evaporated methylbulinol and anhydrous hydrogen chloride gas in a molar ratio of I: I. there is an I imset / img of methylbutinol of about 82%

I li,: he is the proportion of the reaction products \ (hlorbutenol 4 5%. which gives a selectivity of 5 5% is equivalent to.

Example 5

When working according to Example 2, where the molar concentration between methylbiol and HCI was changed somewhat, a conversion of methylbiolum of about 95% could be achieved. Major .AnUiI an. -Chlorbiltcnol in the Reaklioiisprodtikt is 40 ¹ Vl), which corresponds to a selectivity of 38%.

Example 4

A reactor is used in which the ratio of length to diameter is 200 and in which Oil jacket a temperature of 110 ° C prevails. In the Reactor uses activated carbon with a surface of elwa

IH (K) ni-7g introduced, mil which is evenly distributed with ^{a concentration of H 1 Mi I'K'Ij.} A thin mixture of moth} Irumiuil and anhydrous chlorine (iissiTMi) f [in a disproportion of 0.52: 1 is continuously fed in. The duration of the protection is set at 0.075 l / l. The samples show a constant composition. the coating of meibylbiiienol is in the order of 87%.

\ ('hlorbutenol is present in a concentration of about 76%. Under these conditions the Selectivity of the reaction 87%. The through factional Crystallization separated α-chlorobulcnol melts in pure form at around -2 C and boils at 131 to 132 C.

Example 5

A reactor similar to that used in the previous example. is charged with activated charcoal on which 10% Mcrcuriehlorid (HgCI ..) are distributed and heated to 70 C. With a R ^ sldiuck of 20i! mm Ug, the reactor is then continuously charged with a mixture of Meiliylbutinoldämpfep and hydrogen chloride in the disproportion of 1.2: I. The flow rate is 0.15 l / h. With a 75% conversion, 57% iv chlorobutenol is obtained. Other reaction products are: Isopropenylacetylene and some isomers with the I ormcl C ", H ₁ -Cl.

Example 6

I. in a cylindrical reactor in which the ratio of Length to diameter was faO: 1, is with Charcoal charged, on which 5% cuprichloride (CuCΊ. ·) are then evenly distributed a mixture of Mcthvlbutinoldämplcri and anhydrous hydrogen chloride introduced continuously at a disproportionate 1.07: 1 at a flow rate of 0.3 l / h and the temperature was kept constant at 130 ° C. With an implementation of 72%, the proportion is <v (hlorbutenol in the reaction products approximately 34%.

Example 7

In a cylindrical reactor with a length to diameter ratio of 200, half of it is filled with very finely granulated activated carbon which has absorbed 3% of mcrcurium chloride (HgCl.). filled. With the help of a Siicksioffstrnnics the catalyst is echoed in rapid motion. The temperature is kept constant at 150.degree. The diversion of methylbiitinoldampl and anhydrous hydrogen chloride in a molar ratio of 1.5: 1 is then started, the flow rate being 0.1 l / h. After steady conditions are reached, the flow of slick material is so throttled that inside the reactor just sufficient turbulence heslehi The leaving the reactor I'rodiiklc VK ground condensed and continuously by gas chromatography lintelsiu lit Μίΐη erhall I Imsetzungswertc 57-61% . Among the reaction products, the iv-chlorobutefiol is present in an amount of 38 to 40%.

Example 8

Rin reactor me example I is made with activated carbon that 5% mercury chloride (UgCb) contains, loaded and with llille of a heating fluid in the jacket with IiOC held.

With c'iicr Diirehsalzgeseliwindigkcii of 0.15 l / h v.-ircl then a mixture of methyl butinol vapor and anhydrous Bromwnssersttßl (molar ratio 0.9: 1) introduced. With an H1% conversion, one holds vBiombiuenol in a yield of h (>%.

I »Example 4

!. in the reactor according to Example 1 is charged mn [single-grain pumice stone, based on J.5% mercury chloride (HgCI ') are deposited. The reactor is then aul

r> 140 C and with a mixture of methylbuli noldänipfen and hydrogen chloride (molar ratio 1.92: 1). At a throughput speed wedge a conversion of 35% is obtained from 0.4 l / h. The yield of Λ-Chlorbutcnol is 21% with one

- '(ι selectivity of 60%

Example 10

Lin reactor with a ratio of length / u

y < diameter of 150: 1 is charged with activated carbon.

which contains around 5% silver chloride (AgCI). Then you lead at 200 C a mixture of melhylbutinol vapors and anhydrous hydrogen chloride in the molar ratio 1.25: I 7ii. With a permanent salt flow rate of 0.5 l / h

in the implementation reaches a maximum value of 59%.

The vChlorbulenol is obtained in a bulge of 21%, which corresponds to a selectivity of 35.5%.

Vei sliding example l I

A cylindrical reactor, in which the length / diameter ratio is 100: 1, is charged with granulated activated carbon on which 4.9% mercuric chloride (HgCl.-) are applied. Dan; becomes a

JH Introduced mixture of methylbulinol vapors and anhydrous hydrogen chloride in a molar ratio of 0.33: 1. The throughput speed is 0.31 l / h and the reaction temperature is 190 C. A reaction of methylbutino is obtained! of W ¹ A, where the

■ n share of vChlorbuteno! but is only 7%. That The reaction product is mainly composed of isopropyl alkyls (15%) and isomers of the empiric see I'ormcl C-, H, -Cl (39%) as well as a twofold chlorinated product (3 (hloi 3 methyl 2 chlorobutene).

-> ii the lsi present in a concentration of 37%

Comparative example 2

'' wu .in cylindrical reactor in accordance with the comparison ίί bcispicl I. as introduced there into the catalyst of the same ^r Jc. wildly continuously heschicki with Melhylbutinoldämpleii and wasscifiüeiii Chlorvvass'.T substance in a molar ratio of 0.25: 1. The salting speed is 0.3 l / h and the Reaklionsierii ho peralur 190 C., vian achieved a 98.1% conversion of Melhylbutinol. the proportion of \ (chlorobutenol, however, is only 5%. The other reaction products are isopropenyl acetylene (16%). Isoii'iCrc of the empirical formula C? H; CI (39%) and a doubly ι »chlorinated product (S-chlorine- Sniclhyl - ^ - clilor-S-bulcn), which is present in a concentration of 37.5%.

The table gives an overview of Examples I. to 10 and comparative example 1 and 2.

7th Activated carbon llinsclzg. in % 98 26th Kalalysiiforlyp 03 870 Relation length / u
Diirchm 8th MIi: HX Tabel Activated carbon 45 98.1 I IgCI 100 2.1 example
No Carrier material Table 82 I IgCI. Catalyst-
amount in "'■ · 100 Failure / -
speed in l / h 1.0 I. Activated carbon example
No 95 HgCI. 3 100 0.5 0.5 2 Activated carbon I. 87 PtCI j 3 200 0.5 0.52 3 Activated carbon 2 75 HsCI ₃ 3 200 0.5 1.2 4th Activated carbon 3 72 CuCl ₂ 8th 60 0.075 1.07 5 Activated carbon 4th 57-61 HgCl, U) 200 0.15 1.5 6th Activated carbon 5 81 HgCI, 5 100 0.30 0.9 7th Activated carbon 6th 35 HgCl ₂ 3 100 0.10 1.92 8th Activated carbon 7th 59 AsCI 5 150 0.15 1.25 9 pumice 8th Comparative example 3.5 0.40 ic Activated carbon 9 1 HgCI ₁ 2.5 100 0.50 0.33 Comparative example 10 2 HgCIv 100 0.25 I. 4.9 0.31 2 Yield an I IaIo-
genbulcrio! in % 4.9 iumek in
mm I Ig 0.30 Temp, in
C. 40 760 150 43 Selectivity in% 760 Siiure 150 40 89 760 iici 150 76 53 760 HCI i ίο 57 38 200 HCI 70 39 87 760 HCl 130 38-40 76 760 HCI 150 66 54 760 HCI 130 21 67-65 760 HCl 140 21 81 760 HBr 200 60 HCI 7th 35.5 760 HCI 190 5 760 190 7.2 HCI 5.1 HCl

Claims (1)

Claim: Process for the production of alpha halogen biitenols the general formula of I lalogenbutenolen animal general [oriiiel: CFI, CH ₁