WO2022076356A1

WO2022076356A1 - Method for making a dialdehyde

Info

Publication number: WO2022076356A1
Application number: PCT/US2021/053491
Authority: WO
Inventors: Matthew Allen BOONE; William Christopher KETCHIE; Jane Louise DEAN
Original assignee: Eastman Chemical Company
Priority date: 2020-10-06
Filing date: 2021-10-05
Publication date: 2022-04-14

Abstract

We have discovered that a di-epoxide can be converted to a dialdehyde using a zinc-derived Lewis acid. The method comprises contacting a di-epoxide mixed in an organic solvent with a zinc catalyst to form a solvent and dialdehyde reaction product mixture and separating said dialdehyde from said reaction mixture. The dialdehydes have utility as chemical intermediates, and particular utility in processes to make enol ether compounds which can be used in applications as crosslinkers, plasticizers, diluents, wetting agents, coalescing aids and as intermediates in chemical processes.

Description

METHOD OF MAKING A DIALDEHYDE

FIELD OF THE INVENTION

[0001] This application relates to chemistry generally. In particular, this application relates to a novel method of making dialdehydes from diepoxides.

BACKGROUND OF THE INVENTION

[0002] Mono-epoxide to mono-aldehyde rearrangements are well known in the chemical arts. However, di-epoxide rearrangement to di-aldehyde processes are less known. A Lewis acid - catalyzed rearrangement has now been discovered that offers unexpectedly superior selectivity to the previously disclosed processes.

[0003] Di-aldehydes are particularly useful as chemical intermediates to make material such as enol ethers. It would be desirable to have an efficient process to make dialdehydes directly from diepoxides.

SUMMARY OF THE INVENTION

[0004] The Invention is set forth in the appended claims.

In one embodiment the invention is a method of making a dialdehyde comprising contacting a di-epoxide with a zinc complex catalyst.

[0005] In another embodiment of the invention is a method of making a dialdehyde comprising: a. contacting a di-epoxide and an organic solvent with a zinc complex catalyst to form a solvent and dialdehyde reaction mixture; and b. separating said dialdehyde from said reaction mixture.

[0006] In another embodiment of the invention the diepoxide is selected from the group consisting of 1 ,3-bis(2-methyloxiran-2-yl)benzene, 1 ,4-bis(2- methyloxiran-2-yl)benzene, 1 ,3-di(oxiran-2-yl)benzene, 1 ,4-di(oxiran-2- yl)benzene 4, 4'-bis(2-methyloxiran-2-yl)-1 ,1 '-biphenyl, and 2,6-bis(2- methyloxiran-2-yl)naphthalene and mixtures thereof.

[0007] In another embodiment of the invention the di-epoxide is 1 ,3-bis(2- methyloxiran-2-yl)benzene, 1 ,4-bis(2-methyloxiran-2-yl)benzene.

[0008] In another embodiment of the invention the zinc complex catalyst is a zinc-halogen catalyst or a Simonkolleite catalyst.

[0009] In another embodiment of the invention the zinc complex catalyst is zinc chloride or zinc bromide.

[0010] In another embodiment of the invention the solvent is selected from the group consisting of heptane, toluene, chlorobenzene, para-xylene, metaxylene, ortho-xylene, 1 ,4-di-isopropyl benzene, 1 ,3 di-isopropyl benzene, ethyl acetate, butyl acetate, acetonitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof.

DETAILED DESCRIPTION

Definitions:

[0011] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings.

[0012] “Alcohol” means a chemical containing one or more hydroxyl groups.

[0013] “Aldehyde” means a chemical containing one or more -C(O)H groups.

[0014] As used herein, the terms “a,” “an,” and “the” mean one or more.

[0015] As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

[0016] As used herein, the terms “comprising,” “comprises,” and “comprise” are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject.

[0017] As used herein, the terms “including,” “includes,” and “include” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above.

[0018] “Chosen from” as used herein can be used with “or” or “and.” For example, Y is chosen from A, B, and C means Y can be individually A, B, or C. Alternatively, Y is chosen from A, B, or C means Y can be individually A, B, or C; or a combination of A and B, A and C, B and C, or A, B, and C.

[0019] Presented herein is a process to directly convert a diepoxide to a dialdehyde via novel synthesis methods

[0020] Mono-epoxide to mono-aldehyde rearrangements are well known. However, when attempting to extend the scope to di-aldehyde to from diepoxide rearrangement, there are few chemistry options. For example, common Lewis acids and Bronsted acids lead to oligomerization and the production of complex mixtures of products when a difunctional rearrangement is attempted. Synthesis methods utilizing tritylium tetrafluorborate, boron trifluoride, zinc chloride, methanesulfonic acid, solid supported acids (e.g. Amberlyst™ 15, Nation™ NR50) - all lead to complicated reaction mixtures. However, we have discovered that Zn-derived Lewis acids (such as zinc chloride, zinc bromide) can catalyze this transformation and do so with remarkable selectivity. We have now realized a significant advantage over using these Lewis-acids over the Si-AI material counterparts. This reaction is strongly influenced, but not limited to temperature, the particle size of the solid catalyst, and agitation rate.

[0021] Further we have discovered that the diepoxide to dialdehyde rearrangement can produce an allylic alcohol byproduct [3] (Scheme 1 ).

Scheme 1.

[0022] It is desirable to eliminate or greatly minimize the degree to which this allylic alcohol byproduct is formed - this represents a yield loss to the process, due to potential downstream consequences of the presence of an alcohol-functional small molecule in classical acid-catalyzed condensation reactions. Moreover, there is a propensity for the intermediate carbocation to undergo oligomerization-type side reactions. It is further desirable to suppress this pathway to increase the overall yield of the process.

[0023] We have discovered that a di-epoxide can be directly and cleanly converted to the dialdehyde using a zinc-derived catalyst while greatly minimizing the corresponding allylic alcohol production. In this respect, this Lewis acid - catalyzed process is superior to a Si-AI - catalyzed process. [0024] In one embodiment the method comprises: a. contacting a di-epoxide mixed in a solvent with a zinc complex catalyst to form a solvent and dialdehyde reaction product mixture; and b. separating said dialdehyde from said reaction mixture.

[0025] Di-epoxides suitable for the method include 1 ,3-bis(2-methyloxiran- 2-yl)benzene, 1 ,4-bis(2-methyloxiran-2-yl)benzene, 1 ,3-di(oxiran-2- yl)benzene, 1 ,4-di(oxiran-2-yl)benzene 4,4'-bis(2-methyloxiran-2-yl)-1 ,1 '- biphenyl, and 2,6-bis(2-methyloxiran-2-yl)naphthalene and mixtures thereof. [0026] Preferred di-epoxides for the method include 1 ,3-bis(2- methyloxiran-2-yl)benzene, 1 ,4-bis(2-methyloxiran-2-yl)benzene.

[0027] Zinc complex catalysts suitable for the method include zinc-Halogen catalysts such as zinc chloride and zinc bromide, and solid-supported versions of these materials. Simonkolleite structures (Zn5(OH)sCl2), both the hydrate and dehydrated forms, are also suitable for the method.

[0028] Solvents suitable for the method include heptane, toluene, chlorobenzene, para-xylene, meta-xylene, ortho-xylene, 1 ,4-di-isopropyl benzene, 1 ,3 di-isopropyl benzene, ethyl acetate, butyl acetate, acetonitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof. [0029] Preferred solvents for the method are toluene, chlorobenzene, xylenes, and di-isopropyl benzenes.

EXAMPLES

Abbreviations:

[0030] mL is milliliter; hrs or h is hour(s); mm is millimeter; m is meter; GC is gas chromatography; LC is liquid chromatogrpahy; °C is degree Celsius; min is minute; tR is retention time; g is gram; L is liter; pL is microliter; PSD is particle size distribution.

Example 1 : Preparation of 2,2'-(1,3-phenylene)dipropanal [2]

[0031] A solution of toluene (2500 mL) and pulverized zinc chloride (distributed by Sigma Aldrich (>98%)) (3.58g) was heated to 100°C in a 5L 4- neck Morton - style round-bottom flask fitted with an overhead stirrer, thermocouple and a reflux condenser. 1 ,3-bis(2-methyloxiran-2-yl)benzene [1] (250 g) was added dropwise over the course of 1 hr. An exotherm to 112 °C was observed toward the end of the addition.15 min after the addition finished, GC indicated complete conversion to 2,2'-(1 ,3-phenylene)dipropanal [2], Heating was stopped and the mixture was allowed to cool to 50°C. 500 mL H2O was added to flask and stirred. The mixture was transferred to a separatory funnel and separated. The organic layer was washed with 200 mL of saturated sodium bicarbonate solution and then dried using magnesium sulfate. The magnesium sulfate was removed via filtration through a 1 -micron glass fiber disc. The filtrate was concentrated under reduced pressure using a rotary evaporator. GC area percent : 96.7% [2], 0.5% [3], 2.8% oligomeric byproducts. GC-MS tR : [2] - 14.47 min (Exact mass: 190.10 m/z, found: 190.1 m/z), [3] 15.08 min (Exact mass: 190.10 m/z, found: 190.1 m/z).

Example 2: Preparation of 2,2'-(1,3-phenylene)dipropanal [2] oligomeric byproducts

[0032] A solution of toluene (400 mL) and silica-alumina grade 135 (distributed by Sigma-Aldrich as an amorphous catalyst support, ca. 6.5% Al, PSD - 100 mesh (99.3%)) (10g) was heated to reflux in a 1 L 4-neck roundbottom flask fitted with an overhead stirrer, thermocouple, and a Dean-Stark trap. After 4 hrs, water removal was complete. The mixture was then cooled to 100°C, whereupon 1 ,3-bis(2-methyloxiran-2-yl)benzene [1] (100g) was added dropwise over the course of 1 .5 hrs. After the addition was complete, GC indicated complete conversion to 2,2'-(1 ,3-phenylene)dipropanal [2], Heating was stopped, and the mixture was allowed to cool to ambient temperature. The silica-alumina was removed via filtration through a 1 -micron glass-fiber disc. The filtrate was concentrated under reduced pressure using a rotary evaporator. The crude material was then distilled at 1 mm Hg/150 °C to afford pure 2,2'-(1 ,3-phenylene)dipropanal [2], GC area percent : 86.4% [2], 9.37%[3], 4.24% oligomeric byproducts. GC-MS tR : [2] - 14.47 min (Exact mass: 190.10 m/z, found: 190.1 m/z), [3] 15.08 min (Exact mass: 190.10 m/z, found: 190.1 m/z). Example 3: Preparation of 2,2'-(1,3-phenylene)dipropanal [2]

[0033] A solution of toluene (10 mL) and zinc chloride (distributed by Sigma Aldrich (>98%)) (7.16 mg) was heated to 75°C in a 30 mL vial with magnetic stirring. 1 ,3-bis(2-methyloxiran-2-yl)benzene [1 ] (1 .0004 g) was added dropwise over the course of 2 min. At 1 hr GC indicated complete conversion to 2,2'-(1 ,3-phenylene)dipropanal [2], GC area percent : 92.61% [2], 0.47%[3], 6.92% oligomeric byproducts. GC-MS tR : [2] - 14.47 min (Exact mass: 190.10 m/z, found: 190.1 m/z), [3] 15.08 min (Exact mass: 190.10 m/z, found: 190.1 m/z).

Example 4: Preparation of 2,2'-(1,3-phenylene)dipropanal [2]

[0034] A solution of toluene (10 mL) and zinc chloride (distributed by Sigma Aldrich (>98%)) (7.16 mg) was added to a 30 mL vial with magnetic stirring at ambient temperature. 1 ,3-bis(2-methyloxiran-2-yl)benzene [1] (1 .0126 g) was added dropwise over the course of 2 min. The next day GC indicated complete conversion to 2,2'-(1 ,3-phenylene)dipropanal [2], GC area percent : 83.23% [2], 0.16%[3], 16.61% oligomeric byproduct. GC-MS tR : [2] - 14.47 min (Exact mass: 190.10 m/z, found: 190.1 m/z), [3] 15.08 min (Exact mass: 190.10 m/z, found: 190.1 m/z). LC Instrument Parameters -

[0035] Sample prep: 50 uL (weighed) sample diluted to 1 .5 mL with IPA. HPLC column:150 x 4.6 mm Zorbax SB-C8, 70:30 (v:v) methanol water (containing 0.1% trifluoroacetic acid) for 5 min, gradient to 100% methanol over 1 min, held at 100% methanol for 4 min, 220 nm detection), injection volume 0.2 uL: dialdehyde [3] tR= 2.37 min.

GC Instrument Parameters - Hewlett-Packard 5890 GO

[0036] Sample prep: 100 pL sample diluted to 1 mL with toluene; column: J&W DB-5, 30 m x 0.32 mm x 0.25 pm; Split ratio: 20:1 ; Carrier gas: helium; Oven Ramp: 0-3 mins at 100 °C; Ramp 15C/min to 300C, Hold 20 mins; Injector: Temperature - 240 °C.

GC-MS Instrument Parameters - Agilent 6890N GC with Agilent 5975B VL MSD

[0037] Sample Prep: 100 pL sample diluted to 1 mL with toluene; Column: DB-5 30 m x 0.25 mm x 0.25 pm; Oven Ramp: 0-4.5 mins at 40 °C; Ramp 20C/min to 280C, Hold 53.5 mins; Injector: Temperature - 250 °C; Split Flow - 65 mL/min; Carrier Flow Rate - 1 .3 mL/min; Volume - 1 .0 pL; MS: Transfer Line - 280 °C; Ion Source Temp - 230 °C; Mass Range - 34 -700 amu.

[0038] The invention has been described in detail with reference to the embodiments disclosed herein, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

CLAIMS We Claim:

1 . A method of making a dialdehyde comprising contacting a di-epoxide with a zinc complex catalyst.

2. A method of making a dialdehyde comprising: a. contacting a di-epoxide and an organic solvent with a zinc complex catalyst to form a solvent and dialdehyde reaction mixture; and b. separating said dialdehyde from said reaction mixture.

3. The method of claim 2 wherein said diepoxide is selected from the group consisting of 1 ,3-bis(2-methyloxiran-2-yl)benzene, 1 ,4-bis(2- methyloxiran-2-yl)benzene, 1 ,3-di(oxiran-2-yl)benzene, 1 ,4-di(oxiran-2- yl)benzene 4, 4'-bis(2-methyloxiran-2-yl)-1 ,1 '-biphenyl, and 2,6-bis(2- methyloxiran-2-yl)naphthalene and mixtures thereof.

4. The method of claim 2 wherein said di-epoxides is 1 ,3-bis(2- methyloxiran-2-yl)benzene, 1 ,4-bis(2-methyloxiran-2-yl)benzene.

5. The method of claim 2 wherein said zinc complex catalyst is a zinchalogen catalyst or a Simonkolleite catalyst.

6. The method of claim 5 wherein said Simonkolleite catalyst is Zn₅(OH)₈Cl2.

7. The method of claim 2 wherein said zinc complex catalyst is zinc chloride or zinc bromide.

8. The method of claim 2 wherein said solvent is selected from the group consisting of heptane, toluene, chlorobenzene, para-xylene, metaxylene, ortho-xylene, 1 ,4-di-isopropyl benzene, 1 ,3 di-isopropyl

9 benzene, ethyl acetate, butyl acetate, acetonitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof. The method of claim 1 wherein said zinc complex is selected from the group consisting of zinc-halogen catalysts and Simonkolleite catalysts. The method of claim 9 wherein said Simonkolleite catalyst is Zn₅(OH)₈Cl2.