DE1964962A1 - Process for the preparation of alkan-1-al-7-ols - Google Patents

Description

6700 Ludwigshafen, 23rd district 1969

Process for the preparation of alkan-i-al-7-o.len

The present invention relates to a new method for Preparation of alkan-i-al-7-ols of the general formula I.

R ⁴ ° ^H R ⁵

R ⁵ -GH GH ₀ -GHO _T

GH ₀ . .GH

GH

1 4 2 3

in which R and R are methyl or ethyl groups, R and R are hydrogen or methyl groups and R is hydrogen or an alkyl group with 1 to 6 G atoms mean »

It is known that the important fragrance 3,7-dimethyloctane-ial-7-ol (Hydroxycj.tronellal) These methods of preparation are in two-step synthesis of the natural product Gitronellal or in multi-step process, starting from 2-Dehyd ^t rbl ^(£ nalool produce " but unsatisfactory in several respects, be it that one has to start from expensive natural substances, that the processes are expensive and cumbersome because of the large number of individual steps, or that they cannot be used for the production of homo-, Ipger compounds.

The invention was therefore based on the object of the hydroxycitronellal better and to make its homologues accessible for the first time;

It has been found that the alkan-i-al-7-ols of the general Formula I obtained in a remarkable response when one Alk-1-en-6-ols of the general formula IT

R ⁴ ? VH ⁵ . '' -

0
-.: ... ■■: ■: ■ - "- TP-OH CH ₂ BADORiGlNAL

GH ₀ .0. 1 ■

• ^ GH ^ ^ r ¹ 109827/1938

388/69 K2 ~ 2-

O.Z. 26 558

in the presence of rhodium or iridium catalysts "at .50 Ms 200

implements.

up to 200 ⁰ O and 100 to 1500 at with carbon oxide and water feöff,

5 The starting compounds II are new. If R is hydrogen * -so they are obtained by reducing 2-methylhept-1-en-6-one. or its derivatives under consideration here, and is the— "■ This radical is one of the defined alkyl groups, they are in also known per se by reacting these methylheptenones with organometallic compounds, ζ "B" * ■ G-rignard compounds, accessible. Particularly important starting compounds II are 2-methyl- and 2-ethylhept-1-en-6-ol, 2,6-dimethyl-hept-1-en-6-ol, 2,3,6-trimethylhept-1-en-6-ol; "> 2,5,6-trimethylhept-1-en-6-ol and 2,6 dirnethyloct-i-en-β-ol; ·

The procedure of the reaction according to the invention is similar to the known hydroformylation, which is also referred to as the oxo synthesis. Despite the same procedural measures, however, in the present case it is; _v With regard to the reaction result, a very remarkable variant "Contrary to the expectation supported by extensive literature, the eormyl group almost exclusively does not enter the 2-position, but rather the 1-position of 1-oleefin II"

Suitable as catalysts for the hydroformylation reaction especially finely divided metallic rhodium, rhodium carbonyls, Rhodium chloride, rhodium nitrate, rhodium sulfate, di-, rhodium tetracarbonyl dichloride and the complex compounds,,., which are obtained by reacting rhodium salts or rhodium carbonyl compounds with triphenylphosphine, olefins or diolefins receives. Instead of the rhodium catalysts you can also use the appropriate iridium catalysts. The amount the catalyst is from 0.00001 to 1, preferably 0.0001 - "; Up to 0.01 weight percent rhodium or iridium of the initial compound II. Smaller amounts slow down the implementation too much, larger ones no longer contribute much to the acceleration.

Carbon monoxide and hydrogen are preferably about

1Ö9827 / 19.38 -3-

.: /. - \. 1954962 'ΗΝ. '"■■■: cf.ζ, 26 538

is / fe m tljilieh, from each t | -Ms ail et ^ 4rfägh§tf öiäiäl? #L ii% öi? Ieküß zu ver

i dig t ^ iösföfiaftiistlöl tei 1Θ lia 150 ⁰ G

äüf old

± ti

d fifltti ill litfeif iiggtlgilöäff £ uf aig diverse dgf SafÄ i

fffiS I

oil, 1 QSf g B ^ i2il üiöd 120 i # lsi «li

Foy-oloootsi ^ i i5; ^ dieti-Rli, Gil «under föQ ät 33SUoIf einös reti iCöhietinioiiöxid-Wassesäteff-G-eiiiiaölies fftöf hours on 100 ^M Q tinä-works thereää pure Realctiöiisgeniigökltie vi | rodu1j: t in 90

| ⁵

Examples 2 to 5 In the manner indicated in Example 1, one obtains

• 2 * the 3 * 4,7-trimethylloctan-1-al-7-ol from 2,3,6-Ϊ rime thy I-he pt <1-en-6-ol in 70% yield; Kp = 92 to 96 ° G / 0.7 Torr? xiy = 1.4511 »Scent note: oyclamen with methol-like

3 * the 3,7 ⁱ -dimethylnonan-1-al-7-ol from 2j6-dimethyloct-1 ~ en ^ 6 · ^ o1 in 85% yield; Kp = 89 to 91 ° 0 / 0.7 Torr; ti? 2 S = 1.4513; Fragrance note: Fresh, early smell of oranges

and reminding mandarins «,

109827/1938

19-64982

■■ "■" ■ '~ ⁴ ~ ■ O.ζ. 26 558

4, the 3,7r8-trimethylnoBan-1-al-7-ol from 2,6,7-trimethylqct-

1-en-6-ol in 55% yield Bp = 94 ° G / O, 45 Torr}

25th
Dp-- 1.4564 * Fragrance note:! Fruity on apricots

reminding words

5. 3'-Metliyloctän-1-al-7-Ol from 2-Meth.yXliept-1-en-6-ol in

75% yield »bp = 78 to 810 / 0.01. iorr;

n-j - 1.4506; Fragrance note: Hydroxgrcitronellal-like with a pronounced green Fote.

Example 6
3,7-dimethylootan-1-al-7-ol

A solution of 250 g 2 _f 6 -]) iaietn.ylliept-1-en ^ 6-ol, 250 ml - cyclohexane, 200 mg of the Rliodiümverbindungen JjP (G ^ H ₅ ) ^ Rh (OO) Q! and 6 g of triphenylphosphine is below 700 at an equimolar BruDlc Kohleniiionoxid / Wasserstoff-Gemisoih.es heated for five hours at 100 ⁰ G and then aufgearbeiiöbc by distillation! give the pure Yerfahrensprodukt in 85% yield.

109827/193 8

Claims (5)

1864962 ■ ■ -5- -. 0 * 2. 26 - Claims 1 \ Process for the preparation of alkane-1-al-7-ols of the general Formula I. R ⁴ "OH R ⁵ 3 ^ O R -'- OH GH ₀ -GHO ; GH ₀ GH 1 4. · 2 "5 mean wherein R and R ^ are methyl or ethyl groups R and R is hydrogen or methyl groups and R is hydrogen or an alkyl group having 1 to 6 carbon atoms, characterized in that the alkane-1-al-7-ols of the general formula I is obtained in a remarkable reaction when alk-T-en-6- oils of the general formula II p4 nw τ? 5 It UrL ^ s Ά I S ^ I I! GH 2 yV ^ GH R ¹ in the presence of rhodium or iridium catalysts at 50 to 200 ⁰ G ι
material converts. 50 to 200 ⁰ G and 100 to 1500 at with carbon oxide and water 2. 5,4,7-trimethyloctan-1-al-7-ol. 3. 3,7-dimethylnonan-1-al-7-ol. 4. 3,7, S-trimethylnonan-i-al ^ -ol. 5. 3-Methyl0Gtan-1-al-7-ol. \. ._ U; Badisohe Anilin- & Soda-Fabrik AG 9,27,938 ■