DE2826065A1 - PROCESS FOR THE PRODUCTION OF ALDEHYDE, KETONE AND FATTY ACIDS BY OXYDATION OF ALIPHATIC ALCOHOLS OR GLYCOLS - Google Patents

Description

PATENT ADVOCATES A. GRÜNECKER

WL-INGL

W. STOCKMAIR

OH-INa ■ AeE (CALTECH

K. SCHUMANN

DB. RHI Ν * Π - M = L-PHTS

P. H. JAKOB

G. BEZOLD

OR RSl! SM- OFL-CHBUl

8 MUNICH

MAXIMILIANSTRASSE

June 14, 1978 P 12 689

KABUSHIKI KAISHA POLLUTIOE PREVENTING RESEARCH LABORATORY 8-15 5 Roppongi 6-chome, Minato-ku,

Tokyo, Japan

Process for the production of aldehydes, ketones and fatty acids by oxidation of aliphatic alcohols or

Glycols

The invention relates to a process for the oxidation of aliphatic alcohols or glycols using liquid nitrogen dioxide (N ₃ O ₄ ) as the reactant.

There are various methods of making acid and aldehyde (or ketone) from aliphatic alcohols or glycols known. These conventional techniques are as follows:

(1) catalytic oxidation using oxygen or air in vapor or liquid phase,

(2) Oxidation by means of ozone in the liquid phase,

(3) catalytic alkali melt,

(4) catalytic oxidation using hypochlorous acid,

88 ^ / 074 2

TELEPHONE (085)} aa 28 62 TELEX O0-28 380 TELEGRAMS MONAPAT TELEKOPIEREH

(5) carbon monoxide reaction under pressure,

(6) oxidation using nitric acid,

while acrolein and acrylic acid are produced by the catalytic oxidation of propylene.

US Pat. No. 2,298,387 describes an oxidation process for oxidizing certain oxygen-containing compounds such as alcohols, aldehydes and ketones to acids by means of oxides of nitrogen as the oxidizing agent. Each reaction noted was carried out in the vapor-liquid phase or the vapor-vapor phase at a temperature above 100.degree. Liquid N ₂ O. was introduced, but at the elevated temperature so that it was converted into gaseous oxides of nitrogen, ie a mixture of N ₃ O ₄ and NO ₂ (including N ₂ OJ, while the alcohols to be oxidized are converted into liquid or vapor state.

On the other hand, in the process _{according to the invention, liquid nitrogen dioxide (N 3} O ₄ ) reacts with liquid alcohols, so that this method is a liquid-liquid phase reaction and differs in terms of constitution from the method of US Pat. No. 2,298,387.

The invention proposes a first process for oxidizing aliphatic alcohols or glycols by adding them, directly or dissolved in an inert organic solvent or in this solvent and a denitrant, ie dimethyl sulfoxide, DMSO, to liquid nitrogen dioxide (N ₂ O ₄ ) or liquid nitrogen dioxide (N ₂ O ₄ ) in an inert organic solvent or in this solvent and denitrating agent, under essentially anhydrous conditions in the absence of catalysts. More specifically, the process relates to the oxidizing of aliphatic primary alcohols having from 1 to 12 carbon atoms (C 1 -C 3) t branched chain

809882/0742

primary alcohols with 5 to 8 carbon atoms (C ₅ -Cg), secondary alcohols with 3 to 7 carbon atoms (C ₃ -C ₇ ), glycols such as ethylene glycol to decamethylene glycol, halogen alcohol and unsaturated alcohols.

The invention also proposes a second process for oxidizing aliphatic alcohols or glycols by adding liquid nitrogen dioxide (N ₃ O ₄ ) or liquid nitrogen dioxide (N ₂ O ₄ ) in an inert organic solvent to the alcohol or to the Alcohols dissolved in an inert organic solvent or in the solvent and a denaturant under substantially anhydrous conditions in the absence of catalysts. In the second method, the order of addition is reversed compared to the first method.

As far as the liquid-liquid phase reaction between alcohols or glycols and the liquid nitrogen dioxide (N ₃ O ₄ ) is concerned, no relevant state of the art seems to exist.

According to the invention, therefore, a novel method is primarily intended for the production of fatty acid, aldehyde or ketone from aliphatic! Alcohol or glycol are created in which the reaction takes place without the use of a catalyst within a very short period of time, at a temperature at which liquid-liquid phase reaction is maintained under normal pressure, the process being simple Manner and a high rate of product yield.

In particular, the main aim of the invention is to create a novel process for the production of formaldehyde, acetaldehyde, acetone, fatty acids with 2 to 12 carbon atoms (C ₂ -C ₁₂ ) # ■ in particular of fatty acids with the odd number of carbons

809882/0742

atoms of 5, 7, 9 or 11, of adipic acid, acrolein or acrylic acid.

According to the invention are synthetic alcohols which are produced by the Oxo, Leppe or Tiegler (Alfor) process, applicable to the generation of the corresponding acids.

According to the invention it is possible to use the method for oxidizing Carry out alcohols or glycols either continuously or batchwise, with a product yield rate and procedural reliability, both of which are comparable to or exceed those of conventional methods.

Furthermore, according to the invention, it is possible to realize an effective utilization of NOx, which is a dangerous component in the combustion exhaust gas of mineral oil gas, natural gas, etc. According to the present method, cooled and liquefied N ₃ O ^ is used as the oxidizing agent, which has been generated from NO2, converted by oxidizing NOx according to the known method. Or else, as the source of nitrogen dioxide, NO gas is used, which has been generated by a nitric acid production apparatus which works according to the ammonia oxidation contact process. For this purpose, the NO gas is oxidized, cooled and in the form of Ν ~ Ο. liquefied.

The foregoing and other objects, as well as the reactions which take place in the process of the present invention, will be apparent from US Pat The following detailed description of the invention in connection with some preferred exemplary embodiments will become more apparent and understandable.

The following are hypothetical mechanisms of the invention Oxidation reaction of alcohols or glycols shown.

809882/07 ¹ U

Aliphatic primary alcohol

J »-

- OH +

₃ ti

R -

¹ +

C - OHNO I

NO.

NO ⁺ + NO.

phone reaction

Ion complex

Note: R is alkyl

The ion reaction takes place as follows:

no:

Τ> _Γ "_ΠΙΓ ^J

^K , ^UU -HNO,
H '

^H α. ^Η τιλγπ ^Η

IQN ₀ ⁺ ' ^IDr0 3'

R-C-C R-C-ONO ^ R-C-ONO,

I.

- ENT

Il

R-C-H

HN0 _o f ^ OH + NO?
^Ä

"1

R-C-H

OH

0 ^Θ ι

R-C-H I

OH

^N °

0N0 _r I ^£ RCH 1
OH

- ENT ..

80988

1 0 1Λ

II

-HN0

Ii

R-C-H

HN0 _o e> OH + NO

J R-CiH OH "

. i

o ©

RCH I
OH

ONO

RCH 1
OH

I-

ENT

O O Il Il R-C-OH R-C-OH

As for branched chain primary alcohol , secondary alcohol, glycol, haloalcohol and unsaturated alcohol, the same reaction mechanism can be assumed.

Each equation is represented generally as follows:

(2) R-OH + CH ₂ N ₂ O ₄ = RCOOH + H ₃ O + 2N0 j

R: branched chain alkyl "j

! H

(3) 2 R ₁ - CH ₂ -C-CH _{2 R 2} +

OH

R ₁ COOH + R ₂ CH ₂ COOH + R ₁ CH ₂ COOH + R ₂ COOH + 2H ₂ O + 8N0

R ₁ : alkyl R ₂ = _HO represents alkyl (4) HO (CH ₂ ) _n OH + 2N ₂ O ₄

(CH ₀ ) _ 1 . CH-.
N "0.-» _Λττ *> C0 + H "0 +
2 4 CH-. s 2 I.
i ^H 2 ° 3 (COOH) ₂ + 2H ₂ O + 4N0 or acrylic acid from allyl alcohol (5) Acetone from isopropyl alcohol + N_0. = CH ^ rCH-CHO + H. CH ₃
CH ₃ H
]> C - OH + + N ₀ O. = CH-CHCOOH + H. (6) Acrolein , 0 H-H ₂ O ₃ CH ₂ = CH-CH ₂ OH _? 0 + 2N0 CH ₂ = CH-CH ₂ OH

809882/0742

(7) Glycolic acid or oxalic acid from ethylene glycol

CH ₀ OH COOH

I ² + N ₀ O. = 1 + HO + 2NO

CH ₂ OH ^{2 4} CH ₂ OH

CH ₀ OH COOH

I ² + 2N _o 0. = I + 2HO + 4NO.

CH ₂ OH ^{2 4} COOH ■

(8) chloroacetic acid from ethylene chlorohydrin

ClCH ₂ CH ₂ OH + N ₃ O ₄ = ClCH ₂ COOH + H ₃ O + 2NO

As can be seen from the above, in the process according to the invention an alcohol or glycol is _{added or dropped to the liquid nitrogen dioxide (N 3} O ₄ ), an ion complex being formed in the liquid phase, followed by an ion reaction. This reaction is therefore a so-called liquid-liquid phase reaction. If the liquid nitrogen dioxide (N ₂ O ₄ ) is added to the alcohol or glycol (a second method according to the invention), it may be possible to carry out the ion reaction.

Since the oxidation reaction is also exothermic, it is necessary to remove the heat of reaction from the reaction system to make the main reaction while suppressing the side reaction itself to be carried out. Therefore, good thermal conductivity property of the reaction system is an important factor.

Taking into account that the thermal conductivity property of liquid nitrogen dioxide (N ₂ O ₄ ) is superior to that of the organic reacting substance, the first method of introducing the reactant into the liquid nitrogen dioxide (N ₂ O ₄ ) is operationally superior to the feeding method which is the opposite of the former, ie the addition of liquid nitrogen dioxide (N ₃ O ₄ ) to the

809882/0742
- 7 -

Reactants what the second method of the invention is.

Various reaction conditions in the present processes are: the molar ratio between the liquid nitrogen dioxide (N ₂ O ₄ ) and the alcohols or glycols which are to be reacted therewith; the reaction temperature; the rate of addition of the alcohols or glycols to be converted or the rate of addition of liquid nitrogen dioxide (N ₃ O ₄ ); Presence or absence of a solvent; Type of solvent; Presence of a denitrant; Presence or absence of impurities, etc. If it is necessary that the reaction should take place relatively smoothly, one can use the liquid nitrogen dioxide (N ₃ O ₄ ) dissolved in a suitable solvent, and / or one can use the alcohols or glycols to be reacted Apply dissolved in a suitable solvent.

According to the assumed reaction mechanism of the invention Method is the stoichiometric pick-up ratio of liquid NpO ^ to alcohol 1: 1 (to secondary alcohol 2: 1), while this ratio for glycol is 2: 1. The reaction according to the invention is also an exothermic reaction, so that it it is preferred to remove the heat of reaction quickly using a suitable medium with good thermal conductivity. to liquid IToO ^ can also be used for this purpose. at Using a large excess amount of liquid ITpO ^. is the control of the reaction temperature at a good one artificial cooling is much easier. For this reason, an amount above the stoichiometric view is expediently used Amount of liquid NoO ^

However, there would be a large excess amount of liquid TipO ^ certain lifting reactions go hand in hand with it. If the used Amount of liquid N ^ O ^ is less than the stoichiometric Amount, the product yield is reduced.

The reaction temperature is in a range in which

809882/0742

■ <

ORIGINAL

the reaction is carried out in the liquid-liquid phase. The area most preferred is between O ° C and 20 ⁰ C.

When the reactant or the liquid HoO ^ is dripped into the reaction sintering ^ ■ takes place through local heating a lifting reaction caused by the heat of reaction, which leads to a reduction in the yield of product.

Therefore, the reactant or the liquid NpO * be added dropwise very carefully.

The dropping time is generally within 30 minutes to 1 hour. DKSO (Dimethylsulf oxide) and its somolog is an aprotic solvent and inactive towards the reactant and the product, but could be mixed with liquid NpO *. form an addition compound so that it retards the reaction of aldehyde formation. On the other hand, IÜ ^ SO is also a denitrant ₇ and it is assumed that the acid formation reaction can be delayed. Other denitrants with similar properties to DMSO can also be used. The multiple effects of solvent and DMSO are not clear.

What, in summary, is the condition pn <3 of the method according to the invention As mentioned above, there are a variety of factors to consider. The best product yield is depending on the appropriate relationships between the factors.

In order to enable the person skilled in the art to use the inventive To carry out processes in practice, the following preferred exemplary embodiments are given. It should be noted, however, that this Examples are merely illustrative and the skilled person can make various changes, for example back

809882/0742

- 8 a -

visible to the various reaction conditions mentioned above, without thereby departing from the scope of the invention.

In each of the examples below, the reaction is carried out with agitation or shaking while cooling. Excess NpCK ^Λχη ^ solvents are removed and then identification is made.

A halogenated hydrocarbon such as chloroform, carbon tetrachloride, dichloromethane, bromoform can be used as the solvent etc. use. In addition, a chlorofluorocompound such as Flueon 113 and 114 (Trade Mark) can be used.

809882/0742

- 8b -

example 1 Synthesis of formaldehyde (HCHO) and formic acid (HCOOH)

(1) 4.94 m-mol of methanol is gradually added to 20 ml of ice-cold carbon tetrachloride solution at about ⁰ ° C., which contains 0.5 ml of liquid N ₃ O ₄ , and the mixture is allowed to react for two hours. 4.49 mol of formaldehyde and 0.34 mol of formic acid are obtained. The respective yields are 90.9% and 6.9%, respectively. In seven hours, 2.61 mol of formaldehyde and 1.83 mol of formic acid are also obtained in a yield rate of 52.8% and 37.0%, respectively. The identification takes place in each case by gas chromatography.

(2) The experiment is carried out under the same condition except that 0.5 ml of the carbon tetrachloride solution DMSO added. 3.93 m-moles of formaldehyde and 0.10 m-moles of formic acid are obtained in two hours. The respective yields are 79.6% and 2.0%, respectively.

In seven hours, 4.20 mol of formaldehyde and 0.33 mol of formic acid are obtained with yields of 85% and 6.7%, respectively. At the Comparison of (1) with (2) shows that DMSO delays the reaction and (1) results in a high yield of formaldehyde in scored two hours.

Example 2

Synthesis of acetic acid (CH ₃ COOH)

(1) To 9.84 m-mol of ethanel, 1 ml of liquid N ₂ O _{4 is} added and allowed to react for two hours at about 15 ° C. 3.07 m-mol of acetic acid are obtained with a yield of 31.2 % obtain. The acetic acid is identified by gas chromatography and infrared spectrum.

(2) The experiment is carried out under the same condition except for a reaction time of five hours. You get

809882/0742

5.20 m-mol acetic acid with a yield of 52.8%. The identification is done using the same method as above.

(3) 9.4 mol of ethanol are added dropwise to 1 ml of ice-cold N ₂ O ₄ at about ⁰ ° C. and allowed to react for two hours. 6.19 mol of acetic acid are obtained with a yield of 65.9%. This is identified using the same method as above.

(4) 9.84 m-mol of ethanol are added dropwise to 1 ml of ice-cold N ₃ O ₄ , about ⁰ ° C., and the mixture is left to react for five hours. 9.73 mol of acetic acid are obtained with a yield of 98.8%. It is identified using the same method as above.

Example 3

Synthesis of acetaldehyde (CH ₃ CHO) and acetic acid (CH ₃ COOH)

(1) 20 ml of carbon tetrachloride solution, which contains 17.3 m-mol of ethanol, is added dropwise to 20 ml of cooled carbon tetrachloride solution at about 10 ° C., which contains 1 ml of liquid N ₃ O ₄ , and the mixture is allowed to react for two hours .9 m-mol of acetaldehyde with a yield of 51.4%. Furthermore, acetaldehyde is obtained in approximately the same yield in six hours. The acetaldehyde is identified by gas chromatography.

(2) The experiment is carried out under the same condition with the exception of using 18.4 m-mol of ethanol in the Ofeffipersfcur of about 20 ^ CEs become 12.7 m-moles of acetaldehyde with a 69% yield obtained. In six hours, 17.7 m-moles of acetaldehyde and 0.1 m-moles of acetic acid are also obtained in one yield of 96.2% and 0.5%, respectively. Acetaldehyde and acetic acid are identified by gas chromatography. When comparing (1) with (2) one finds that the difference zvn. see the. Acetaldehyde yields. Ln 6 hours depending on the reaction temperature is.

- 10 -

«09882/0742

Example 4

Synthesis of caproic acid (C ₅ H ₁₁

(1) 2.39 m-mole of n-hexanol, are gradually added to 1 ml of ice-cooled liquid N ₂ O, at about 0 ⁰ C ttnl is allowed to react for six hours. 2.21 m-mol of caproic acid are obtained with a yield of 92.2%. Caproic acid is identified by the infrared spectrum and nuclear magnetic resonance.

(2) 2.39 mol of n-hexanol is gradually added to 1 ml of liquid N ₃ O ₄ at 18 to 20 ° C. and the reaction is allowed to take place over a period of three hours. 1.86 m-mol of caproic acid are obtained with a yield of 78%. The caproic acid is identified using the same method as above.

(3) To 5 ml of carbon tetrachloride solution, which contains 4.00 m-mol of n-hexanol, 2 ml of mixed solution of liquid N ₂ O ₄ and carbon tetrachloride (1: 1) are added at 18 to 20 ⁰ C and allowed in six Hours react. 3.92 m-mol of caproic acid are obtained with a yield of 98.5%. The caproic acid is identified using the same method as above.

Example 5

Synthesis of n-heptaldehyde (CgH ₁₃ CHO) and n-heptylic acid (CgH ₁₃ COOH)

(1) 1 ml of liquid N ₀ O- is added dropwise to 0.071 m-mole of ice-cold 1-heptanol at (JD C and the reaction is allowed for three hours. 0.005 m-mole of heptaldehyde and 0.039 m-mole of 1-heptylic acid are obtained with a Yield of 7% and 54.9%, respectively. In addition, about 24% of heptyl nitrate is detected. N-Heptaldehyde, n-heptyl acid and heptyl nitrate are identified by gas chromatography, infrared spectrum and nuclear magnetic resonance, respectively.

(2) The experiment is carried out under the same condition with the exception that the reaction temperature is 15 ° C. Man

80988.2 ^ 0742

receives 0.04 m-mol n-heptylaldehyde and 0.067 m-hol n-heptylic acid with a yield of 5.6% and 94.4%, respectively. When comparing (1) with (2) one finds that there is a difference between the two days n-heptylic acid is dependent on the reaction temperature and one

also finds that. Acid predominantly in the absence of solvent is formed.

Example 6

Synthesis of pelargonic acid (CgH, -COOH)

1.15 mol of n-nonanol (Nony! Alcohol) is gradually added to 1 ml of liquid N ₂ O ₄ at 18 to 20 ° C. and allowed to react in four hours. 0.86 m-mol of n-pelargonic acid are obtained with a yield of 74.8%. The pelargonic acid is identified by gas chromatography.

Example 7

Synthesis of nonylaldehyde (CgH ₁₇ CHO) and pelargonic acid (CgK ₁₇ COOH)

(1) 20 ml of carbon tetrachloride solution with a content of 0.013 m-mol of nonanol (nonyl alcohol) * is added dropwise to 2O ml of ice-cold carbon tetrachloride solution at 0 C, which has a content of 1 ml of liquid N ₂ O ₄ , and is allowed to react for two hours. 0.007 m-mol of nonylaldehyde and Ο, ΟΟΙ m-mol of pelargonic acid are obtained. The respective yields are 53.8% and 7.7%, respectively. Nonylaldehyde and pelargonic acid are identified by gas chromatography, infrared spectrum or nuclear magnetic resonance.

(2) A mixed solution of 20 ml of carbon tetrachloride and 0.5 ml of DMSO, which contains 5.74 mol of nonyl alcohol, is added dropwise to 20 ml of ice-cold carbon tetrachloride solution at about 10 ° C. which contains 1 ml of N ₃ O ₄ and the reaction is allowed to take place for two hours. 3.197 m-mol of nonylaldehyde are obtained with a yield of 55.7%. When comparing (1) with (2) it is found that the aldehyde yields approach one another, despite the different reaction temperatures, because of the influence of the DMSO.

809882/0742

- 12 -

Example 8

Synthesis of capric acid (C _g H.-COOH)

(1) 1.56 mol of n-decanol is gradually added to 1 ml of liquid N ₂ O ₄ at 18 to 20 ° C. and allowed to react for four hours. 1.26 m-mol of capric acid are obtained with a yield of 80.1%. The capric acid is identified by infrared spectrum.

_{(2) 2 ml of a mixed solution of liquid N 3} O ₄ and carbon tetrachloride (3: 1) are added to 5 ml of carbon tetrachloride solution containing 1.56 mol of n-decanol at 18 to 20 C and left for seven hours react. 1.33 m-mol are obtained

Capric acid in a yield of 85.2%. The reaction proceeds slowly in the presence of the solvent.

Example 9

Synthesis of undecanoic acid (C, H ₃ COOH)

0.96 m-mol of n-undecanol is _{gradually added to 1 ml of liquid N 3} O ₄ at 18 to 20 ° C. and allowed to react for four hours. 0.78 mole of undecanoic acid is obtained in a yield of 81.3%. The undecanoic acid is identified by gas chromatography.

Example IO

Synthesis of lauric acid (dodecanoic acid) C ₁ ^ H ₂₃ COOH

(1) To 5 ml of carbon tetrachloride solution containing 3.6 mol of n-dodecanol, 2 ml of a mixed solution of liquid N ₃ O ₄ and carbon tetrachloride (1: 1) are added at 18 to 20 ° C. and allowed to do so Hours react. 3.25 m-mol of lauric acid are obtained in a yield of 91%. Mp 42-44 ° C. The lauric acid is identified by infrared spectrum and nuclear magnetic resonance.

(2) 4.47 mol of 1-dodecanol are added to 1 ml of liquid N-O. at 15 to 20 ° C added, dissolves and allowed to react for three hours. 4.45 m-mol of lauric acid are obtained with a yield of 99.6%. the The reaction proceeds slowly in the presence of the solvent. the

809882/0742

Lauric acid is identified using the same method.

Example 11

Synthesis of isovaleric acid CH ₃ -CH ₂ CH (CH ₃ ) COOH

(1) 4.64 m-moles of 2-methylbutanol will gradually _{react to 1 ml of ice-cold liquid N 2} O ₄ at about O ⁰ G and it will react in four hours. 3.05 mol of isovaleric acid are obtained in a yield of 65.5%. Isovaleric acid is identified by nuclear magnetic resonance and gas chromatography.

(2) The experiment is carried out under the same conditions with the exception that the reaction time is two hours. 2.38 m-mol of isovaleric acid are obtained with a yield of 51.1%.

The isovaleric acid is made according to the same method as above identified.

Example 12

Synthesis of 2-ethylhexanoic acid CH ₃ (CH ₂ ) 3CH (C ₂ H

_{(1) 2 ml of mixed solution of N 2} O ₄ and carbon tetrachloride (1: 1) are added to 5 ml of ice-cold carbon tetrachloride ^{solution at about 0} ° C., which contains 3.22 mol of 2-ethylhexanol, and the mixture is allowed to react for four hours. 2.43 m-mol of crude 2-ethylhexanoic acid are obtained in a yield of 75.7% (with a content of 5.3% by-product). The 2-ethylhexanoic acid is identified by infrared spectrum and gas chromatography.

- 14 -

809882/0742

(2) 3.22 ΐϊΐ-mol of 2-ethylhexanol is added to 1 ml of ice-cold liquid N ₃ O ₄ at about O ⁰ quinzu and allowed to react for 4 hours. 2.94 mol of crude 2-ethylhexanoic acid are obtained in a yield of 91.6% (with a by-product content of 7.8%). The 2-ethylhexanoic acid is identified by the same method as above.

Example 13

Synthesis of isopelargonic acid CH ₃ C (CH ₃ ) ₂ CH ₂ CH (CH ₃ ) CH ₂ COOH

_{(1) 2 ml of a mixed solution of liquid N 2} O ₄ and carbon tetrachloride (1: 1) are added to 5 ml of ice-cold carbon tetrachloride solution at about 0 ° C., which contains 2.87 m mol of 3.5.5-trimethyl-1-hexanol and lets react for four hours. 2.24 mol of 3,5,5-trimethylhexanoic acid are obtained in a yield of 77.8%. Isopelargonic acid is identified by gas chromatography and nuclear magnetic resonance.

(2) 2.87 m-mol of 3,5,5-trimethyl-1-hexanol are added to 1 ml of ice-cold liquid N ₃ O ₄ at about ⁰ ° C. and the reaction is carried out for 4 hours. 2.25 m- Mol of 3,5,5-trimethylhexanoic acid (isopelargonic acid) in a yield of 78.1% The isopelargonic acid is identified by the same method as above.

In the process according to the invention, branched-chain aliphatic primary alcohols such as i-butanol, i-pentanol and i-octanol are oxidized to the corresponding fatty acids.

Example 14

Reaction of see-butyl alcohol CH ₃ CH ₂ CH (OH) CH ₃ with liquid N ₃ O ₄

_{(1) Add 2 ml mixed solution of liquid N 3} O ₄ and carbon tetrachloride (1: 1) to 5 ml of ice-cold carbon tetrachloride ^{solution at about O 0} C, which contains 5.46 m-mol of sea-butyl alcohol

- 15 -

809882/0742

added and left to react for four hours. 3.4 mol of acetic acid are obtained, 0.47 m-mole propionic acid and 0.46 m-mole formic acid in the yields of 62.3%, 8.6% and 8.5%, respectively. These acids are identified by gas chromatography.

(2) 5.46 m-mol of sec-butyl alcohol are added to 1 ml of ice-cold liquid N ₃ O ₄ at e% a ⁰ ° C. and the diaan is allowed to react for four hours. 3.32 m-moles of acetic acid, 0.41 m-moles of propionic acid and 0.40 m-moles of formic acid are obtained in yields of 60.9%, 7.4% and 7.5%, respectively.

Example 15

Reaction of marine amyl alcohol CH ₃ (CH ₂ J ₂ CH (OH) CH ₃ with liquid

2.32 m-mol of marine amyl alcohol is added to 1 ml of liquid N ₃ O ₄ at 18 to 20 ° C. and allowed to react for four hours. 0.36 m-mole of acetic acid, 0.54 m-mole of propionic acid, 0.24 m-mole of butylic acid *) and 0.24 m-mole of formic acid are obtained in yields of 15.4%, 23.2%, 10.2% % and 10.2%, respectively. These acids are identified by gas chromatography and infrared spectrum. ■ *) or butyric acid

Example 16

Reaction of see.-Octy! Alcohol CH ₃ (CH ₂ J ₅ CH (OH) CH ₃ with liquid

1.57 m-mole of sec-octyl alcohol are employed to 1 ml of liquid N ₃ O ₄ at 18 to 20 ⁰ C are added and allowed to react for two hours. 0.41 m-mole of hexanoic acid, 0.2 m-mole of heptanoic acid, 0.41 m-mole of acetic acid and 0.2 m-mole of formic acid are obtained in yields of 25.8%, 13.1%, 25.9% and 13.0%, respectively. 7.6% of unreacted sec-octyl alcohol is found. The acids are identified by infrared spectrum and gas chromatography.

- 16 -

809882/07 * 2

Example 17

Synthesis of succinic acid (CH ₂ ) ₂ (COOH) ₂

(1) To 5 ml of carbon tetrachloride solution containing 5.7 m-mol of tetramethylene glycol (1,4-butanediol) at 18 to 20 ° C., 2 ml of mixed solution of liquid N ₃ O. and carbon tetrachloride are added and the mixture is allowed to react for four hours. 5.1 mol of succinic acid are obtained with a yield of 89.2%. Mp 186-189 ° C. The succinic acid is identified by infrared spectrum.

(2) 5.65 mol of 1,4-butanediol is added to 1 ml of ice-cold liquid N ₃ O ₄ at efvra O ⁰ C and. lets react for 4 hours. 5.13 mol of succinic acid are obtained in a yield of 90.8%. Mp 186-189 ° C. The succinic acid is identified using the same method as above.

Example 18

Synthesis of glutaric acid (CH ₂ ) ₃ (COOH)

4.76 m-moles of pentamethylene glycol (1 _f 5-pentanediol) are gradually added to 1 ml of ice-cold liquid N ₃ O ₄ at about 0 ° G for a four hour reaction. 3.67 m-mol of glutaric acid are obtained in a yield of 77.3%. The proportion of unreacted 1,5-pentanediol is about 3.5%. The glutaric acid is identified by infrared spectrum.

Example 19

Synthesis of adipic acid (CH-). (COOH) -

0.85 mol of o (. IO 1,6-hexanediol (hexamethylene glycol) is added to 1 ml of ice-cold liquid N ₃ O ₄ and allowed to react for two hours. 0.81 mol of adipic acid is obtained in a yield of 95.3%. Mp. 151 C. The adipic acid is

- 17 -

809882/0742

graphy, infrared spectrum and nuclear magnetic resonance identified.

Example 20

Synthesis of sebacic acid (CH ₂ ) ₈ (COOH) ₂

(1) 2 ml of a mixed solution of liquid N ₃ O ₄ and CH ₂ Cl ₂ (1 : 1) and let react for six hours. 0.83 m-mol of sebacic acid is obtained in a yield of 76.3%. M.p. 130 to 132.5 ° C. The sebacic acid is identified by the infrared spectrum.

(2) 1.34 m-mol Ij10-decanediol is added to 1 ml of ice-cold liquid N ₂ O ₄ at about ⁰ ° C. and allowed to react for 6 hours. 1.32 m-mol of sebacic acid are obtained in a yield of 98.2%. Mp. 130 to 132.5 G. The sebacic acid is identified by the same method as above.

Example 21

Reaction of ethylene glycol with liquid nitrogen dioxide N _? 0.

To 1 ml of cooled liquid N ₃ O ₄ at about 15 ° C., 1.88 mol of ethylene glycol are added and the mixture is left to stand for one day. 0.84 mol of glycolic acid and 0.24 mol of oxalic acid are obtained in yields of 44.7% and 12.8%, respectively. These are identified by gas chromatography, infrared spectrum and nuclear magnetic resonance. The same products are also obtained by the reverse method of addition.

Example 22

Synthesis of monochloroacetic acid ClCH ₂ COOH

To 1 ml of cooled liquid N ₃ O ₄ at 15 ° C 6cwa non dropwise 1.8? in-col

- 18 -

809882/07 * 2

■ ι *

Epichlorohydrin and let stand eight hours. 1.09 is obtained m-mol of monochloroacetic acid in a yield of 58.3%. These is identified by gas chromatography, infrared spectrum and nuclear magnetic resonance.

The same product is also obtained by the reverse method of feeding.

Example 23

Synthesis of acetone (CH ₃ COCH ₃ )

_{0.5 ml of liquid N 2} O is added to a mixed solution of 20 ml of ice-cold carbon tetrachloride and 0.5 ml of DMSO bai containing about 0.12 VeLdBl, 29 mol of isopropyl alcohol, and the mixture is left to react for one hour. 0.97 m-mol of acetone is obtained in a yield of 75.2%. Furthermore, 1.2O m-mol of acetone are obtained in a yield of 93% in two hours. The acetone is identified by gas chromatography. No acid is formed due to the influence of solvents and DMSO. The yield increases after a reaction time of two hours.

Example 24

Synthesis of acrolein (CH ₂ = CH-CHO) and acrylic acid (CH ₂ = CH ^ COOH)

(1) To 1 ml of ice-cold liquid N ₃ O ₄ at etv. ^r a 0 ⁰ C, 1.93 ra mol of allyl alcohol are added and the mixture is left to react for two hours. 1.87 m-mol of acrolein are obtained in a yield of 96.9%. Furthermore, 0.98 m-mol of acrolein and 0.83 ία-mol of acrylic acid are obtained in a yield of 50.8% and 43.0%, respectively, in five hours. The acrolein as well as the acrylic acid are identified by gas chromatography.

(2) To 1.45 m-mole of allyl alcohol with ice-cooled / a 0 ⁰ C setzfcixri 1 ml of liquid ^ o ^ ^nto a ⁿ i ^{un <^} allowed to react for two hours etv.

0.81 m-mole of acrolein and 0.32 m-mole of acrylic acid are obtained in one

- 19 -

809882/0742

Yields of 55.9% and 22.1%, respectively. Also in five hours 0.62 m-mole of acrolein and 0.60 m-mole of acrylic acid were obtained in yields of 42.8% and 41.4%, respectively.

It can be seen from the foregoing that the first method is advantageous over the second method in terms of operation and product yield. Its ΐ ± ε & because of its large ratio from solvent to liquid ^ O. wiinä aldehyde predominantly while acid becomes the major product from the corresponding alcohol in the absence of solvent.

It is significant that many useful chemical substances can be produced by the process according to the invention, such as formaldehyde, acetaldehyde, acetone, acetic acid, acrolein, acrylic acid, adipic acid and fatty acids with an odd number of carbon atoms C ₅ , Cy, Cg, C, - ,, C -,. ,, other aliphatic aldehydes etc.

It should be noted that the process according to the invention can be carried out without a catalyst, which is not to say that a catalyst may be used if necessary.

- 20 -

809882/0742

Claims (13)

PAT Ξ N TA N W ALT Ξ Α. GRÜNECKER OPL-ING. H. KlNKELDEY 2 O 2 0 U 0 0 _w . STOCKMAIR DR-ING A «E (OUTECHl K. SCHUMANN OR. RER NAT. ■ DIPL-PHySL P. H. JAKOB D (PL-INQ. G. BEZOLD DR BER NAT QFL-CHEU. 8 MUNICH 22 MAXIMILIANSTRASSE 43 June 14, 1978 P 12 869 Claims lJ process for the preparation of aldehydes, ketones, and fatty acids from aliphatic alcohols or glycols, characterized in that oxidizes the alcohols or glycols with liquid nitrogen dioxide (N ₃ O _4). 2. The method according to claim 1 for the production of fatty acid, characterized in that aliphatic alcohols or glycols are oxidized by adding the compound to liquid nitrogen dioxide (N ₃ O ₄ ), the oxidation reaction taking place in the liquid-liquid phase and the compound ranks among the primary alcohols with 1 to 12 carbon atoms, among the branched-chain primary alcohols with 5 to 8 carbon atoms, among the secondary alcohols with 3 to 7 carbon atoms, among the glycols with a methylene number of 2 to 10, and among the halogen alcohols. 3. The method according to claim 1 for the production of fatty acid, characterized 809882/0742 TEtF-FON (Ί83) O32B62 TELEX O5-S33EO TELEGRAMS ΜΟΝΑΡΛΤ TELEKOPIER5EK characterized in that aliphatic alcohols or glycols are oxidized by adding liquid nitrogen dioxide (N ₂ O.) to this compound, the oxidation reaction taking place in the liquid-liquid phase and the connection to the primary alcohols having 1 to 12 carbon atoms, to the branched-chain primary alcohols with 5 to 8 carbon atoms, among the secondary alcohols with 3 to 7 carbon atoms, among the glycols with a methylene number of 2 to 10, among the halogen alcohols and among the unsaturated alcohols. 4. The method according to claim 2 and 3, characterized in that the liquid N-O. under essentially anhydrous conditions dissolves in an inert organic solvent. 5. The method according to claim 2 and 3, characterized in that the compound under substantially anhydrous conditions dissolves in an inert organic solvent. 6. The method according to claim 2 and 3, characterized in that the compound and the liquid N ₃ O _{4 are} each dissolved in an organic solvent under substantially anhydrous conditions. 7. The method according to claim 2 and 3, characterized in that the reaction is carried out in the absence of catalysts. 8. The method according to claim 1 for the preparation of aldehyde or ketone and aldehyde and fatty acid, characterized in that Aliphatic alcohols are oxidized by adding the compound to liquid nitrogen dioxide (N-O.), with the oxidation reaction is driven in liquid-liquid phase and the connection to the primary alcohols having 1 to 9 carbon atoms, to the secondary alcohols having 3 to 7 carbon atoms and one of the unsaturated alcohols. 809882/0742 9. The method according to claim 1 for the preparation of aldehyde or ketone and of aldehyde and fatty acid, characterized in that aliphatic alcohols are oxidized by adding liquid nitrogen dioxide (N ₂ O.) to the compound, the oxidation reaction in liquid-liquid Phase is driven and the compound is one of the primary alcohols with 1 to 12 carbon atoms, the secondary alcohols with 3 to 7 carbon atoms and the unsaturated alcohols. 10. The method according to claim 8 and 9, characterized in that liquid N ₂ O. is dissolved under substantially anhydrous conditions in an inert organic solvent or in this solvent and a denitrant. 11. The method according to claim 8 and 9, characterized in that under substantially anhydrous conditions, the compound dissolves in an inert organic solvent or in this solvent and a denitrant. 12. The method according to claim 8 and 9, characterized in that the compound and liquid N ₃ O _{4 are} each dissolved in an organic solvent under substantially anhydrous conditions. 13. The method according to claim 8 and 9, characterized in that the reaction is carried out in the absence of catalysts. 809882/0742