DE1047763B - Process for the conversion of organic halogen compounds into their homologous aldehydes - Google Patents

Description

GERMAN

It has been found that organic halogen compounds can be converted into their homologous aldehydes, by quataxing the halogen compounds with tertiary phosphines, especially triphenylphosphine Converts phosphonium salts, the latter by treatment with hydrogen halide binding agents in the corresponding Converts phosphonium ylides, allows formic acid esters to act on the latter and hydrolyzes the reaction product.

The reaction sequence can be formulated as follows, for example in the case of using benzyl chloride and triphenylphosphine as starting materials for sodium acetylide as the hydrogen halide binding agent and methyl formate as the last component:

C ₆ H ₆ - CH _a a

* [■

C _B H ₅ -CH ₂ -P <C ₆ H ₅ ) ₃ | a

b) IC ₆ H ₈ - CH ₂ -P (C ₆ H ₅ ) _S J er

+ NaC = CH - +

»» C ₆ H ₅ -CH-P (C ₆ H ₅ ),

+ NaCl + C ₂ H ₂

+ CH ₃ O-CH = O

♦ - C ₄ H ₅ -CH-P (C ₆ H ₅ J ₃
CH ₈ O-CH-O "

d) C ₆ H ₅ -CH-

i
CH ₃ O-CH-O

- CH

+ OP (C ₆ HJ ₃

CILO-CH

e) C ₆ H ₅ -CH = CH-OCH ₃
+ H ₂ OC ₆ H ₅

^V + CH ₈ OH

CH ₂ -CH =

A wide variety of aliphatic, Use cycloaliphatic or araliphatic halogen compounds which are attached to the halogen atom bearing carbon atom still have at least one hydrogen atom; the halogen compounds can be saturated or one or more isolated or conjugated double and / or triple bin processes for transfer

organic halogen compounds

into their homologous aldehydes

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr, Horst Pommer, Ludwigshafen / Rhem,
and Dr. Georg Wittig, Heidelberg,
have been named as inventors

fertilize and also carry those substituents that the Ylidbildimg according to reaction b) of the above scheme do not interfere. So, for example, they come into consideration straight-chain © and branched primary and secondary alkyl halides, such as methyl, propyl, isopropyl, hexyl, Dodecyl chloride, cyclohexyl chloride, benzyl and diphenyl methyl chloride, Methoxy, chlorine or carbethoxybemzyl bromide, ÄHylbromid, jS-Cyclogeranylbromid, Ionylbromid, Ethoxyethyl bromide, chloroacetic acid ester, chloroacetonitrile, 1,4-dichlorobutane or ethylene bromide; latter can be reacted with 1 or 2 moles of triphenylphosphine. The implementation to the quaternary phosphonium salts according to a) .does in the usual way, e.g. B. by dissolving the components in ether, benzene, tetrahydrofuran or dimethylformamide and heating, required LichenfaMs in the pressure vessel (Kosolapoff: »Organophosphorous Compounds ", 1950, pp. 78 and 79).

As a hydrogen halide binding agent for formation the phosphonium ylides according to b) can be organometallic compounds such as methyl, butyl or phenyllithium, Methyl or phenyl magnesium bromide, calcium or sodium acetylide, also sodium or potassium amide and use alkali or alkaline earth metal alcoholates (G. Wittig and U. Schöllkopf, Ber. 87 [1954], P. 1318 ff; German patents 1003 730 and 943 648).

Also from the German patents 1 001256, 954247 and 957 942 the implementation of YMden of phosphorus with carbonyl compounds to those of Vitamin-Α and yS-carotene series known. After this It is also known that carboxylic acid esters, ζ. Β.

809 727/471

■■■ - ■■ 3; 4th

Ethyl acetate or benzoic acid, partially crystalline with ylides of triphenylphosphonium methylide; Phosphorus does not turn into unsaturated compounds - for the most part, however, it remains dissolved. Well be

set (cf. G. Wittig and U. Schöllkopf, Ber. 87, carefully added 105 parts of butyl formate, [1954], pp. 1318 ff.), It was surprising that the esters, whereby the violence of the reaction by intermittent

react the formic acid in the claimed sense. 5 cooling is mitigated. After stirring for 12 hours at

The ylides obtained are, advantageously without them, the usual temperature, the mixture is still

isolate from the solutions or suspensions, heated to boiling for 3 hours, then cooled, dated

Formic acid esters, such as methyl, ethyl, benzyl or precipitated triphenylphosphinoyd filtered off and that ! Phenyl formate, implemented. In the process, filtrate appears to be formed on a column distilled, with 62 parts

first after c) an additive product which, in particular, go over vinyl butyl ether. He lets himself be known in

on heating, according to d) with formation of phosphine-manner with acids; to hydrolyze acetaldehyde,

Oxide and vinyl ether break down. The latter can in itself; .

known manner to hydrolyze the corresponding aldehyde, Example 4

be sated, e.g. by heating with dilute As in Example 3, 385 parts of n-propyl-triphenyl-

Mineral acid. 15 phosphonium bromide, which is produced by reacting triphenyl

The new synthetic process is broadest applied phosphine with n-propyl bromide was produced with

capable. It allows the synthesis of many, previously n-butyllithium in ether to propenylideii-triphenyl-

Part of phosphine that is not or much more difficult to access and then with 80 parts of ethyl formic acid

Aldehydes from easily accessible starting materials; so ester implemented. After stirring for 12 hours, the

can it e.g. B. for the production of / ?, y-unsaturated 20 sucks and the filtrate by distillation to 'a small

Aldehydes from a, j8-unsaturated halogen compounds · '· column freed from solvent. The residue will

to serve. Such ^, ^ - unsaturated aldehydes are important with 10 parts of oxalic acid and steam

Intermediate products for syntheses in the vitamin A series are distilled. The steam distillate is at a

(See, for example, O. Isler, Chimia, Vol. 4 [1950], p. 116 ff., and the column is distilled, passing over at up to 95 ° C

Zeitschrift für Angewandte Chemie, Vol. 68 [1956], p. 547 25 shares. The n-butyr- contained in the distillate

to 553). ^ - -; "_; ■ aldehyde is converted into the bisulfite compound

The parts mentioned in the examples are separated by weight and removed from them by treatment with

share. . '. ■. Sodium carbonate (see Lipp, Liebigs Ann. Chem., Vol. 205

Example 1 [1880], p. 2) set free. It will be 52 parts

217 parts of β-cyclogeranyl bromide are used in conventional n-butyraldehyde with a _{boiling point of 76O} = 75 to 76 ° C.

Way with 268 parts of triphenylphosphine to the quaternary,.

Phosphonium salt. From the obtained / J-Cyclo example

90 parts of geranyl triphenylpliosphonium bomide are dissolved. As in Example 4, 385 parts of isopropyl triphenylin are added to 200 parts of dimethylformamide and, under nitrogen phosphonium bromide, 10 parts of finely powdered sodium acetylide are added. 35 phosphine was prepared with isopropyl bomide, after stirring for 1 hour at 20 ° C, one adds to the ent-n-butyUithium in ether to isopropylidene-triphenyl-state deep red solution of triphenylphosphonium phosphine and further with 80 parts of ethyl formic acid - /? - eyelogeranylid 30 parts Formic acid ethers and esters reacted. In similar working up as in Beier-warming for 5 hours at 60 ° Q. After cooling comparable game 4 48 parts of isobutyraldehyde, bp. _7G0 = 62 are employed with 50 parts of 10 ⁰ /, jiger sulfuric acid, distilled 40-6 * 4 ° C obtain,
with steam all volatile reaction products over Beismel 6
and - extracting the distillate with methylene chloride. After ^

Evaporation of the extractant is the back To a solution of 95 parts of dodecyl triphenyl

stood fractionally distilled, after a phosphonium chloride, which is obtained by reacting dodecyl-

14 mm pressure at about 67, up to 80 ° C boiling forerun 45 bromide with triphenylphosphine was made in

19Parts 2 ', 6', 6'-trimethyleyelohexen- (l ') - yl- (l') - a.cet-. 250 parts of absolute tetrahydrofuran are allowed to

aldehyde of b.p. ₁₄ = 108 to 112 ° C. That in a comfortable temperature gradually a 1.4 parts of lithium

conventionally produced phenylsemicarbazone containing absolutely essential solution of phenyl

Aldehyde melts at; 157 ° C. lithium flow in. The formation of the deep yellow dodec-

'Λ _- ..? - ₁ _ 50 cylidene-triphenylphosphine finds ^Λ almost instantly

^ice P ^ie . ■ -..-. instead of. Now add all-

Man sets in the usual way 127 parts of benzyl chloride gradually 20 parts of ethyl formic acid and stirs

with 268 parts of triphenylphosphine to form the quaternary phosphate for 24 hours at ordinary temperature. According to Abdestil-

phonium salt around. 90 parts of the resulting benzyl trilating of the solvent are extracted and the residue is extracted

phenylphosphonium chloride in 200 parts of di- 55 with petroleum ether, the triphenylphosphine formed

methylformamide dissolved and then largely undissolved under nitrogen with oxide. The petroleum ether extract

10 parts of sodium acetylide in the tripbenylphosphonium are shaken for 18 hours with a 20% strength aqueous solution

converted to benzylide. The red solution obtained is a phosphoric acid solution. After separating the petroleum ether

30 parts of ethyl formate are added. The layer is washed over several times with water

Working up as in Example 1 gives 18 parts of 60 dried sodium sulfate and that after the evaporation of the

Phenylacetaldehyde with a _{boiling point of 15} = 88 ° C. The residue obtained from petroleum ether is distilled in vacuo,

-r, .. "■" ■. ', »At 18 Torr pressure, the tridecen-

Example ό aldehyde at 147 to 150 ° C over. The distillate solidifies

. To a suspension of 350 parts of methyl triphenyl crystalline on cooling and then melts at 13

phosphonium bromide, which by reacting triphenyl 65 to 14 ° C.. .

phosphine was made with methyl bromide in 1200 Example 7

Parts of absolute ether are left slowly with cooling to a suspension of 425 parts of cyclohexyl-tri-

a 7 parts of lithium containing solution of η-butyl phenylphosphonium bromide, which by reacting

lithium flow in absolute ether. While the salt is cyclohexyl bromide made with triphenylphosphine

gradually dissolves, the deep yellow 70 becomes separated, in 1200 parts of absolute ether one leaves slowly

1 U4 / / bo

an ethereal solution of n-ButyUithium containing 7 parts of lithium. After 6 hours of stirring, the formation of cyclohexylidene-triphenylphosphine is complete, and 80 parts of ethyl formate are carefully added. After stirring for 24 hours at normal temperature, the mixture is refluxed for a further 3 hours, then cooled and the triphenylphosphine oxide which has precipitated out is filtered off. The filtrate is freed from the solvent and, after adding 10 parts of oxalic acid, rapidly distilled with steam. The steam distillate is extracted with ether and, after the addition of 0.1 part of hydroquinone, the ether extract is distilled, 61 parts of hexahydrobenzaldehyde with a b.p. ₁₈ = 72 to 74 ° C. being obtained.

Example 8

To a suspension of 150 parts of 1,4-butane-bis-triphenylphosphonium bromide (produced by reacting 1 Moll, 4-dibromobutane with 2 moles of triphenylphosphine) in 500 parts of absolute tetrahydrofutane, an ethereal solution containing 2.8 parts of lithium is added Methyl lithium. After 4 hours of stirring, the salt has gone into solution and the formation of the deep yellow 1,4-butadiene- (1,3) -bis-triphenylphosphine completed. After adding 16 parts of ethyl formate, the mixture is stirred for 48 hours at ordinary temperature. whereupon the solvent is distilled off, 12 parts of oxalic acid are added and then with steam distilled. The adipine dialdehyde is obtained in good yield from the pungent pungent smelling distillate.

Example 9

A concentrated alcoholic sodium ethylate solution prepared from 23 parts of sodium is added to a solution of 340 parts of cyanomethyl triphenylphosphonium chloride (prepared by reacting cyanomethyl chloride with triphenylphosphine) in 1000 parts of absolute alcohol. Almost instantly the formation of cyanomethylene triphenylphosphine takes place, some of which precipitates out as a thick precipitate. After adding 80 parts of ethyl formate, the mixture is stirred for 48 hours at ordinary temperature, after which the alcohol is largely distilled off in vacuo and the residue is shaken with a concentrated aqueous oxalic acid solution for 6 hours. Then it is extracted with ether and the ethereal extract is fractionally distilled on a small column, with 31 parts of formylacetonitrile from Κρ. _7β0 = 71 to 73 ° C can be obtained.

Example 10

90 parts of a 30% solution of sodium methylate in methanol are added to a solution of 260 parts of ß-ionyl triphenylphosphonium bromide, which has been prepared by reacting ß-ionyl bromide with triphenylphosphine, in 500 parts of dimethylformamide. The red-violet / 3-ionylidene-triphenylphosphine is formed with little heat generation. After stirring for 3 hours at ordinary temperature, 40 parts of ethyl formate are added. The mixture is stirred for a further 24 hours, the mixture is then extracted exhaustively with petroleum ether and, after washing with water and adding 10 parts of oxalic acid, the extract is distilled with steam. The distillate is extracted with petroleum ether, the light yellow petroleum ether solution is washed with water, dried over sodium sulfate and distilled. _{A mixture of so-called / SC 14} aldehyde and 4- [2 ', 6', 6 '-trimethylcyclohexen- (1') -yl- (1 ')] - distills at 0.05 Torr and 75 to 90 ° C. 1-ethoxy-2-methylbutadiene- (l, 3) over. For separation, it is dissolved in a little petroleum ether and chromatographed on aluminum oxide (standardized according to Brockmann). 22 parts of β-C ^ aldehyde (4- [2 ', 6', 6'-trimethylcyclohexene (l ') - yl- (I ')] -2-methylbutene- (2) -al- (1) eluted, bp _{0) 05} = 76 to 77 ° C, phenyisemicarbazone, m.p. 184 ° C; . "··:, · '- ■ -

34 parts of 4- [2 ', 6', 6 '-trimethylcyclohexan (1') -yl- (1 ')] -1-ethoxy-2-methylbutadiene-1 are eluted with petroleum ether-benzene (2: 1), 3, l _max 258 to 259 mμ (e = 15,000); _Bp . OiO5 = 71 to 73 ° C.

Example 11

In the same manner as in Example 10 260 parts be jS-Ionyl bromide with 90 parts of a 30 ° / ₀ sodium methylate solution and then reacted with 40 parts of ethyl formate. After the exhaustive extraction with petroleum ether, the reaction product is distilled directly, with 61 parts of 4- [2 ', 6', 6'-trimethylcyclohexen- (I ') -yl- (I')] -I -ethoxy-2-methylbutadiene- (l, 3) = ₀ are obtained, bp, ₀₅ 71 to 73 ° C, X _max = 258 ηιμ (ε = 14 500). the vinyl ether is then saponified in the usual way with acid to give the free / 3-C ₁₄ aldehyde.

Example 12

A suspension of 206 parts of 4-chlorobenzyl triphenylphosphonium chloride, which was prepared by reacting 4-chlorobenzyl chloride with triphenylphosphine, in 1000 parts of absolute benzene is shaken with 200 parts of an approximately 30% suspension of sodium amide in absolute benzene for 48 hours. Ammonia escapes and the orange-red 4-chlorobenzylidene triphenylphosphine is formed. The excess sodium amide and the precipitated sodium chloride are filtered off with exclusion of moisture. The clear orange-red benzene solution obtained is mixed with 40 parts of ethyl formate and stirred for 48 hours at ordinary temperature. Then, the solvent is distilled off and, after addition of 300 parts of a 10 ° / ₀ phosphoric acid solution for 10 hours at ordinary temperature. The reaction mixture is then extracted with petroleum ether, the petroleum ether extract is washed with water, dried over sodium sulfate at -5 ° C. and distilled. At b.p. ₁₃ = 114 to 116 ° C., 34 parts of 4-chlorophenylacetaldehyde pass over.

Example 13

To a suspension of 205 parts of 4-methoxybenzyltriphenylphosphonium chloride, which was prepared by reacting 4-methoxybenzyl chloride with triphenylphosphine, in 1000 parts of absolute tetrahydrofuran is added 12 parts of a magnesium-containing solution of ethylmagnesium bromide in tetrahydrofuran. After stirring for 5 hours, the formation of the orange-red 4-methoxybenzylidene-triphenylphosphine has ended. 40 parts of ethyl formate are carefully added, the mixture is stirred for 24 hours at ordinary temperature and the procedure is continued as in Example 12. 36 parts of 4-methoxyphenylacetaldehyde with a boiling point of ₁₃ = 142 to 143 ° C. are obtained; its semicarbazone melts at 180 to 181 ° C.

Claims (1)

Claim Process for converting organic halogen compounds into their homologous aldehydes, thereby characterized in that the halogen compounds with tertiary phosphines, especially triphenylphosphine, converts to quaternary phosphonium salts, the latter by handling with hydrogen halide binding agents Converts agents into the corresponding phosphonium ylides, on the latter formic acid 7th allows ester to act and the reaction product Angewandte Chemie, 68 (1956), pp. 805 to 808, hydrolyzed. to 553; "* Reports of the German Chemical Society, Publications considered: (1954), p. 1318; Kosolapoff: Organophosphorous Compounds, 1950, 5 German patents No. 1001256, 954247, Pp. 78, 79, 85; 957 942, © 809 727W71 12.58