DE2359283C3 - Process for the acetylation of activated CH groups - Google Patents

Description

. From the llaiipipatenl 176X773 isl a procedure · ο / ur Acelylation of activated CH-Cinippen in compounds of the general formula HCXi, in which the activating radicals X are identical to one another, but can also be different from one another and

COV or -CN, where at most one X js can also be a water atom, Y is C) R, N (Rt. Or R and R a branched or unbranched, saturated or unsaturated, optionally substituted, mono- or divalent alkyl or aralkyl with I to SC-Atonien or unsubslituierter \ o or substituted aryl radical is known by reaction mil ketene at elevated temperature in the presence of alkali catalysts, which is characterized in. that the reaction in the presence son alkali salts of carboxylic acids and / or Sulphon- i> viureii as catalysts, if necessary in an inert solvent, carried out In industrial applications, it has been shown that in this process, strong formation of by-products occurs as soon as the batches are carried out on a larger scale, ^ n

Is now a process for the acetylation of activated Cll-Cmippen in compounds of the general formula Ch ₁ -CO-CH ₁ -X. in which X is a CII.-CO- or ROOC-Ciruppe, where R is a branched one or a branched one. saturated or unsaturated, possibly substituted, mono- or divalent alkyl radical with 1 to 8 carbon atoms isl, by reaction with Kelen in the presence of alkali metal salts of carboxylic acids as catalysts, optionally in an inert solvent, found that thereby Isl characterized in that the reaction is carried out at temperatures of 10-35 ° C.

Surprisingly zeigie in fact, that the Nchcnprodukihiliiiing usually by 2 to 3läehe, in some cases (Table 3 Heispiele 2 (1) goes back 15 and 18 or ss Verglcuhsheispiele Id and to d.is h- to 7lä.l'e , if you do not use higher! "emv» 1. lines but at 10-35 C, preferably 15-30
.iiheilei

I) .is cilindungsgeinäße method is advanta- i ">

hall .'lim Manufacture of, for example: l'riacelvl-HK ¹ Ih.uv I li.u ei \ lessigs.iurenieiln lesler. Diacelv lessi ;!

s.uiK .illu i.'slci. l) iaccl \ Icssigs.i.irehulN lcslci. I) iai.el> I- -.N; ■■> .uiι »■ -1." * .IlIn Ihe w I- tester and I Ιι, ιαΊΐ lcssigsäuie-

lil ·. I.

.-MiinlimiisiicnuHe \ eil.ihieii Ι.Ίϋ skh um. 1 ι Κίιι or ei Hohlleiii DriU'k. hcuirzwv'l ahei hot ι! '.., k 1I111 ehl iihl eη

Working at the claimed, low temperatures is particularly necessary for approaches on an industrial scale. Already at the beginning from K)! (discontinuous) or in a reaction vessel with an overflow at approx. 101 contents (continuous) the formation of neural products increases very sharply at higher temperatures, while that of the claimed low temperatures is not the case. This effect persists with larger approaches.

In technology, one generally works with a reaction vessel inhalation of up to 20 m ', preferably from 50 I up to 50 m '.

The alkali metal salts of carboxylic acids, z.H. of formic acid, liquid acid, Propionic acid, llulleric acid. isohulleric acid, the higher acids. /. H. of caprylic acid. Capric acid, lauric acid, versalic acids, isotridecanoic acid and Stearic acid; chlorinated acids, e.g. I). of chloroacetic acids. It is sufficient to have concentralizations from 0.01-3%, preferably 0.04-0.6%, based on the starting maierial to work. The salts can can be used individually or in a mixture. It is generally advantageous to use them in pressed form.

The process can also be carried out in solvents which are indifferent to the reactants carry out. For example, hydrocarbons are suitable, e.g. Ii. Petroleum ether, cyelohexane, benzene, Toluene; Chlorinated hydrocarbons, e.g. B. Methylene chloride. Chloroform, chlorobenzenes, trichlorethylene, carbon tetrachloride; Tclraulk oxy silicon compounds. /. B. Siliciunitelraäthylal; Nitriles, e.g. IJ. Acetonitrile; Carboxylic acid ester, /. IJ. Acid methyl ester, acetic acid hydrolyser, Buller's acid ethyl ester; Ether, z. IJ. Diethyl ether, 1 elrahydrofuran, I, 4-I) ioxane.

In general, it proves to be advantageous if the reaction product itself is used as a solvent will.

The process according to the invention can be carried out both batchwise and continuously. Intended to to be worked discontinuously, simple flasks, kettles or autoclaves can be used as the apparatus to serve. In the case of continuous operation, the flasks or kettles are equipped with overflows through the reaction product formed, optionally mixed with the solvent, to the extent of its Failure is discharged. Reaction tubes, Towers and gyroscopes with pumped around them Reaction mixture can be used, e.g. 15. liquid ring pump 11.

The products are suitable for manufacturing, for example of plastics, as an aid to the artisanal discovery, z. IJ. Plasticizers, catalysts, as well for the production of physiologically active substances.

Discontinuous laboratory tests im I ritlenlurni

In a workshop, 1 McI of was to be acetylated Compound and the catalyst (see table Il mil Kelen (the applied set isl; itis Dragonfly I to see I at 'Ut in the I ahelle I emperjhir IhIuiuIcIi.

The i'.asL'hi'iimatiigi.i,) hisi. he An.il> se lies Kohpiuiluktes isl .ms der l'.ibelle I ersichllKh. The Auslveiiu ik's Rohproilukli's \\ M in all VcimicIkii l.isl ιμι.ιηΐι l.iliv \) \ c \ mil .UK Ii Im the other WiMkhi-

Tabc I II- I

Discontinuous production of the diacet \ lessigs; iurealh \ leMers im! ahormassiab

Vcrs- Rcaklion catalyst ("'.. " I MuI ketone Experimental 7 "DiaceUl- "/ .. Λ cct- "■» near η- No lempcralur ie MoI üaiier vinegar ester vinegar ester Products Art Acclcssig- i. Raw i. Raw 2.3 ester product product (() 0.4 IhI I. 20-22 CM ₁ CO ₁ Na 2.3 1.0 1.5 77.8 9.6 12.6 2 20-22 CH ₁ CO ₁ Na 5.9 0.97 1.5 76.4 12.6 11.0 90 CH, COjNa 1.0 1.03 1.5 83.0 3.9 4th 20-22 CICH ₁ CC) ₁ Na 1.05 1.5 78.9 lO.i 11.0 S. 130 CICH ₁ CO ₁ Na 1.0 1.0 84.8 3 2 12.0

It can be clearly seen from the test results that the howling occurs at low and high temperatures is roughly the same. - The acetic acid ester can be extracted from the crude product by fractional vacuum distillation to be recovered. -

The yield is around 88 "/., The formation of by-products (Light boilers, more highly acctylated compounds and ./f-Aceloxycrotonic acid ethyl ester) in all babble by 12%.

Example I Discontinuous experiments in a 20 l reactor

The experiment was carried out and analyzed in exactly the same way as in the previous experiments. The results obtained and the reaction conditions used are shown in Table 2 / u see.

Table 2

Discontinuous precipitation of the dialysis acid esters of the formula (CH ₁ CO), CHCOOR on a 10 -! - scale

Wr, .- Re: ikt.- catalyst (% o) Mole Wrsuehs- 7, ge % The end "/ .. secondary R No.') Temp. Kctcn ihiiier wish gangly product Art per mole IhI Connect connect i. Raw The end- dung i. dung i. product g.ings- Raw Raw prndtikl product product

there 18th 6 b 90 7 a 20th 7 a 90 8 a 24 9 a 24 9 b 130 10a 25th !If 130 Ha 24 11b 87 12 a 24 13 a 23 14 a 26th

Ib

Na acetate

Na acetate

Na-stcarat

Na-slsarat

K-acctate

Na butyrate

Na butyrate

Na chloroacetate

Na chloracelate

Na acetate

Na acetate

Na acetate

Na-acclat

Na acetate

Na acetate

1.1

5.3 5.5 5.5 1.8 U 1.1 2.0 1.0 1.1 1.1 1.1

1.1

1.01

I.Ol

1.01

0.99

0.98

0, "9

0.98

0.99

1.0

1.02

1.04

1.14

1.19

1.17

■ is 85.7 69.4 77.1 68.9 74.3 79.2 66.4 79.7 72.4 87.1 73.1 85.0 80.4 74.3

61.3

7.6 8.9 7.0 7.8 8.7 6.9 7.3 6.1 4.3 6.6 4.2 7.6 < >, l 12.4

5

6.7 21.7 15.9 23.3. 17.0 13.9 26.3 14.2 23.3

6.3 22.7

7.3 10.5 13.3

υ. x

C, H, C ₁ II, t \ H <CII ₅

CjII ₄ CjIIs CjIIs

(, Ils

CjII,

CIl ₁ CH,

CHjCH (CIUIUIUH CIU IU ME CII CIIC II

ill

Müi Mch! sole 1.K ¹ MiIiI .- !!. there!' Μ aü '/ n Vi / rck-ichsivispK'l.'ii the Nflii-nprocluklhililune (I eichticder. H η Ik ¹ I .uvh MltIc \ er h indium ι. Η and Ii- Vclnwcmtcn-Ιιγ-'ίτ lii'L 'l as rvi the iMitsprci h 11 <Iν. η

Examples.

Example 2 Diskon.inuicritche experiments with 2Mi I-kettle

The acctylating was carried out in a coolable 25 μl kettle Connection (213KMoI. He AeCt) IaCeIiIn: 413KMoI) lulled, the catalyst in a filter

basket hung and the mixture unigepumpl. I in

running speed: 14 m '/ h. The cup was duii h ^ _n V _ilULhmhr t, _{ini; c | cJtc,.}

The conditions of sale and the howling h / w The anaiv sen of the crude product can be seen from the map

I ahelle '

Discontinuous production of D-acetyl acetic acid allyl ester and I nacetyl methane in a 250 l stirred tank

\ ers.-No

15th
16
(Comparison)

(Comparison)

Reaction temperature

23-24

25th

J-32

Na-aeelal Mol Vjis, - ge Aus' .side- Aiis.it/-

Kelen d.iuer »neglected imiigs- product griilV

per mole of verhin- i. Rnh-

Alisgaiijs- dung ιΐιιημ product

product i raw ι roIi-

(ol ilii product product (ic Mull

1.0

1.02 I.OI

1.15 1.04 1.16

IO

^l > 5.4 X 1.2

SS.2

2.1 2.4

X. 3

3.5

10.3

24.0

\ USl!,! HL '-

1.3 Acetylacetone 1.3 Accl> lacclon 0.65 Acel vinegar siiure.ithv 1- esler 0.65 Acetoacetic acid s; ilire; ilh> l- estcr 0.65 Acel vinegar acid ethyl c you ι

Here is the I lies from Examples 15 and 17 and formation (low boilers, higher ethylated compounds from the associated comparative examples 16 and 1 ⁽ )! higher temperature rises 6 to 71 times.

Example 3
Continuous experiments in the Irittcnturni (Llbcrlaulbci MO ml) and in the reaction vessel (IJberlaul he IK) I)

The discontinuously produced crude product was not working in the Irittenturm this measure

submitted and the catalyst (sodium acetate) in gc- required.

Pressed I orm hung in a sieve pot. In the case of the reaction conditions as well as the analyzes of the

of the kettle, the reaction mixture was because of the 45 reaction products are given in Table 4, better mixing umgcpunipt (14 mVh). At the

Table 4

Continuous experiments for the preparation of the diacetyl acetate in the laboratory and technical staff

Vers.-No.

Rcaktions- Mol Kclen kg Ai'Messig- Verwcil / cit "» Diacetyl- "A Acclessi ^" i per Mi) I acetester per SUI. vinegar ester product

((Ί

vinegar lcr

17th
24
'«)

25th
'Kl

0.94

1.1

1. (13

1.0

1. (1

05/11

16.13

16.13

(1.16

(1.16

i. Crude product i. Crude product i. Raw product

7S.5 7 ¹ JX 6S.I XO .; "K. ')

13.6

10.6

6. "

KVI II. ¹

2 \ 0 ¹ 1.7 'I''

Di. ¹ I .iiv.'lk ¹ 4 / c ι μ t. dalt the formation wm Nchemirndiiklcn (I calibrated boilers. higher acel \ herte connections and /f-Aietiiwcriilnns.iiiie.illn lesterl mn home ailn'ihn at high temperatures rises if one discharges sub \ oi> i I ibdtm.iHstab <N cisui.li 22)

Claims (1)

Claim: Long-term acetylation of activated Cll groups in compounds of the general l-'ormcl CII. (O CM. -X, in which X is a CH, -CO-orcr a R () () C-C <group, where K is a branched or un \ er / wigler, saturated or unsaturated, optionally substituted, emiider divalent alkylrc ..: ant is I to 8 carbon atoms. by reacting with Kelen in the presence of Alkali salts of carboxylic acids as catalysts, optionally in an inert solvent, characterized in that the implementation at temperatures of IO 35 C durchluhri.