DE2355534A1 - METHOD FOR MANUFACTURING CISOLEFINS - Google Patents

Description

FARBWERKE HOECHST AKTIENGESELLSCHAFT
formerly -Master Lucius & Brüning

File number: HOE 73 / F 336

Date: November 6, 1973 Dr. Tg / br

Process for the production of. cis-O lefins

It is known to carry out stereospecific syntheses of olefins according to the Wittig reaction with the aid of salt-free ylides (Angew, Chem. 7j8 (1966), 677). Such ylide solutions have hitherto had to be produced by the technically very complex sodium amide method (Liebigs Ann. Chem. 6 19 <(1958), 10; An ₁ SeW. Chem. 77 (1965). 609).

The invention is now a process for the preparation of cis-olefins, which is characterized in that one Alkali or alkaline earth metal in hexaalkylphosphoric acid triaraide dissolves, to this solution a phosphonium salt of the general formula

H ₅ ) ₃ Br I

gives, wherein R is a straight-chain or branched (C. -C. _r ) -alkyl-

1 y. j

or (C ₀ -C., _) - Alkenyl group means the reaction mixture thus obtained with an aldehyde of the formula

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offset, where R is a straight-chain or branched \ ^c i ~ ^G 20> ~ alkyl or (C ₂ -C) -alkenyl group, which is also in (3) - or a more distant. Position to the aldehyde group can be substituted by a hydroxy, low molecular weight carbalkoxy or (C ^ -CoJ-acyloxy group, and the resulting cis-olefin of the general formula

HH
RC = CR III

isolated by methods known per se.

The alkali or alkaline earth metals that can be used are preferably Li, Na ₁ Mg, in particular potassium, and also Ca, Sr or Ba.

The alkyl groups in Kexalkylphosphorsauretriamid can be identical or different, preferably the same; they preferably have 1 to ¹ l , in particular 1 or 2, carbon atoms. Above all, the known and readily available hexatethylpliosphoric acid triamide is preferred.

The process is generally carried out in such a way that, under a nitrogen atmosphere, a zex-smaller alkali or alkaline earth metal is added to hexaalkylphosphoric triamide, preferably hexamethylphosphoric triamide (HMPT), with stirring or shaking, the initially blue color of the solution soon changing to reddish brown. For the sake of simplicity, the dissolution takes place at room temperature, but it can generally be carried out in an interval of 10 to 80 ° C., advantageously in an interval of 15 to 30 ° C. After everything Alkall- or alkaline earth metal is dissolved. (After about 1-3 hours), are added to the solution thus obtained, an equivalent amount or optionally an excess of up to 20% _t, preferably up to 10%, of a phosphonium salt of the formula I , where R preferably contains up to 10 carbon atoms. Compounds of this type can be obtained by processes known from the literature, in particular by reacting corresponding bromine compounds with triphenylphosphine. The phosphonium salt can be used as such or

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can advantageously be added as a slurry in ΙΊΜΡΤ. the total per mmol of phosphonium salt or in vol of alkali or Alkaline earth metal required amount of HMPT is in general. 0.5 to 5 ml or more, advantageously 0.8 to 2 ml. The upper limit is not critical.

^{The ylide solution obtained in this way is treated with an aldehyde of the formula II, in which R 1 is} preferably 2 to 15, in particular 3 to 10 ° C., at temperatures of 0 ° to 30 ° C., preferably 15 ° to 20 ° C., for the sake of simplicity at room temperature -Atoms and in (3) - or a higher position to the aldehyde group, preferably terminally strong, can be substituted by an acyloxy group, preferably a fortnyloxy or acetoxy group.

The reaction mixture is stirred at the chosen reaction temperature until the reaction has ended; between 8 and 15 hours are required at room temperature. The olefin formed is isolated in a conventional manner, for example by Abdostillieren or higher boiling compounds by pouring into ice water and subsequent sulphoxide extraction

It is also possible to generate the _{aldehyde by oxidation of the ylide solution, for example by introducing dry oxygen in situ. Symmetrical cis-olefins of the formula are then obtained

HH
RC = CR IHa

The cis-olefins obtained, which, according to gas chromatographic and spectroscopic investigations, have a purity of more than 95 % , are valuable intermediate products for organic syntheses; in particular, a number of these compounds have a pheromori effect on a wide variety of Lepidoptera species.

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Compared to the previously known processes, the process according to the invention has the advantage that it can be carried out at roughness and that the work is technically complex
with liquid ammonia is not necessary.

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_ 5 -

Beis piel 1: Presentation of Ylldlösungen

Chopped up potassium is added to absolute HMPT under nitrogen. ”The resulting deep blue solution heats up after about 15 bins ₅ and the color changes to red-brown. All the potassium has dissolved in the compartment for 1 to 3 hours and a slurry of the equivalent amount of a phosphonluidsil of formula I in absolute HMPT is added to the base solution.

ice-octen- (4)

From 2j2g (55 mol) of potassium and 20.0 g (50 mmol) of triphenyl-n-butylphosphonium bromide, a Ylld solution in 100 ml of ΗΜΡΪ is prepared according to Example (1), which is then reacted with 4.0 g (55 mmol) of butyraldehyde. Each 12h can be distilled out, the formed oetene - (4) s.ras of the "reaction solution. It is taken up in pentane, washed with dilute sulfuric acid, sodium hydrogen sulfite and water and dried with sodium sulfate. The pentane is removed Tom octene (4 -) by distillation over a Vlgreux column. The remaining crude product is distilled «
_Bp . 76o = 120 ⁰ G, yield 4.5 g = 7β $,

Example 5: cis ~ octene - (4) by autoxidation

An ylide solution prepared analogously to Example (2) (2 _S 2 g of potassium, and 20.0 g of criphenyl-n-butyl-phosphonium broraide) is passed through dry oxygen for 1 hour and then worked on as in Example (2),

760

Yield 2 ₅ 0 g, 70 £. ' _{Bp vfin} = 120 ° C

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Representation of cis - ^ - Alkenol-i-acetateii

An ilide solution is prepared from 0.94 g (24 mmol) of chopped potassium in about 50 nil absolute HMPl ¹ and 24 roraol triphenyl-ethyl-phosphonium bromide. The dimethylamine thus formed is largely drawn off in a jet vacuum with the exclusion of moisture. After stirring for 4 hours, 20 mmol (4.0 g) of 9-acetoxynonanal are added dropwise while cooling with water _}, stir over laughing and pour the reaction mixture into ice water acidified with a little dilute sulfuric acid. The unsaturated Ister is through. Shake out with n-Eexan. isolated. To remove small amounts of HMPI, the combined Hexaixausauge are washed with dilute sulfuric acid. "Any unreacted aldehyde is removed via the hydrogen sulfite addition compound, and the iriphenylphosphine formed during the reaction as sphenyl-methyl"-piicsphoniuia; iodide from the unsaturated ester "" The (Drlphenylplxosphrrioxid co-extracted in small amounts by η-hexane crystallizes at about -25 C overfold and is suctioned off.

The yield is 2.2 g (50 $) cis-9 - undecenol ~ 1 ~ acetate bp. _{0> 01} 84 ° C -

According to this method, the following additional compounds with pheromone action in various species of spidoptera were produced with appropriate variation of R: eis-9-2) odeoeiiol-1-acetate Sdp. _N. 101-102 ° C

υ, ι

(R = n-Propyi) yield 2.5 g (51 ° h)

This connection is shown in male lyres of the pine bud moth Repellent effect and is the sex attractant of the males of Paralobesia viteana.

cis-9-tridecenol «1-acetate bp. _{Q Q1} 97 ° 0 (R = η-butyl) yield 2.6 g (54 ^)

cis-SJ-Ietradecenol-t-acetate Bp.Q _Q1 102-104 ° C (R = n-pentyl) Yield 2.6 g (51 ^c ß>)

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This connection is the sesual puck of the female 2Liere yon Spoöoptera frugiperda, as well as a component of the pheromone by Adoxophyes orana.

cis-g-Pentadeeenol-i-acetate Bp. _QQ | 118 ° C

(R = n-hexyl) yield 2.8 g (57 $)

Example 5? Representation of τοη eis-it-alkenol-i-acetates

Proceed as in example (4) and replace the 9-acetoxynonanal 4.6 g (20 mmol) of H-ethoxyundecanal a »PoI - gende Compounds with pheromone effects: are obtained:

cis-H-Sridecenol-i-acetate bp. _{Q Q1} : 101 ° C

(R = η-ethyl) yield 2.5 g (52 Ji)

cis-ii-i-detradecenol-i-acetate bp _ * k '· 103 ° C

(R = ti-Propyi) yield 2.3 g (45 $)

The connection is the sexual attractant of the female animals from Argyrotaenia velutinana, Choristoneura rosaceana, Ostrinia nublilalis, Ancylis spectrana, Zeiraplera diviana and one Component of the pheromone of Adoxophyes orana. She continues to show Attractant effect in the cabbage exile.

cis-H-hexadecenol-i-acetate Bp.Q ■■■ «.: ■ - 108 ° C

(R = ii-pentyl) yield 2.6 g (47 ^)

Example 6; cis-9-tetradecen-ol-i-formate

To a prepared according to Example (4) ylide solution of 0.94 g potassium _/ and are 9 "3 g n-Pentyltriphenyl bromide was 3J8 g ^ -SOrmyloxjrnoiaial U33A · operates on after stirring for 12 hours as in Example (4).

The yield is 2.5 g (52 ^) cis-9-Tetra.de.cen-ol-i-forraiat

Bp _{0> 01} : 97-100 ° C

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The connection shows attractant effects on the males by Heliothis zea.

2-methyl «-cis ~ 7" -oetadecene

To prepare the ilide solution, proceed according to example (4). 0.94 g (24 mmol) of finely chopped potassium in approx. 50 ml of absolute HKPiE are reacted with 10.92 g (24 mmol) of isooctylphenylphosphonium bromide isum corresponding ylide and this is reacted with 3 _S 8 g (20 niraol) of TIndecanal sum olefin. Work up as in example (4).

After two distillation, the yield is 2 g of (37 ^) 2-methyl ~ cis ~ 7-octadecene.
Sdp, 125-129 * 4 / 0.2 mm Hg.

When implementing this compound with m-chloroperbenzoic acid one obtains the corresponding cis-epoxy, that of the Sexüallocl: - substance of the great gypsy moth (lymantria dispar) is "

§I, representation of cis-9-trans-12-tetradecadienol ~ 1-acetate

Su an ylide solution prepared according to Example triphenylphosphonium bromide (4) using (E ~ 3-pentenyl) is slowly added dropwise ~ 4 O ₅ g Acetoxynonanal, then allowed for 12 hours at room temperature, stirring, and worked up as in Example 4. FIG. The yield is 2.1 g (45 5 ») cis-9" trans-12 ~ tetradecadie-

nol-1-acetate bp. Q ₀₄ 110-112 ⁰ G

The compound is the sexual attractant of the female animals of Plodia interpunctuella, Anagasta kühniella. and laphygma exigua. It is also a component of the pheromone of Cadra cutella and Prodenia eridiana.

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Claims (3)

HOE 73 / F 336 Patent claims: ί) Process for the production of cis-olefins, characterized in that that one dissolves an alkali or alkaline earth metal in Kexaalkylphosphorsäure-triamid, to this solution Phosphonium salt of the general formula ) Br are, wherein R represents a straight-chain or branched © (C ₁ -C ₁ alkyl or (C ₀ -C, _K) alkenyl group, the so & r ~ preserved reaction mixture with an aldehyde of formula R ¹ - C · "" II offset, where R is a straight-chain or branched (C.-C ₀ ) -alkyl or (C _p -C ₂ _) - alkenyl group, which is also in (3) - or a more distant position to the aldehyde group by a (C., -C.) - acyloxy group can be substituted x-t, and the resulting cis-olefin of the general formula HH ₁
RC = CR III isolated by methods known per se. 2) Method according to claim (1), characterized in that the metal is potassium and the riexaalkyl-phosphoric acid triamide Hexamethyl phosphoric acid triaraid used, 3) Process for the production of symmetrical cis-olsfine der formula HH
RC = CR IHa / 10 509837/0972 HOE 73 / p - OK - characterized in that oxygen is introduced into the ylide solution obtained according to claim (1) or (2) » ¹ I) ylid solutions obtained according to claims (1) to (3) 509837/0972