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1. WO2020108913 - CATALYSED PROCESS OF PRODUCTION OF HYDROGEN FROM SILYLATED DERIVATIVES AS HYDROGEN CARRIER COMPOUNDS

Note: Text based on automatic Optical Character Recognition processes. Please use the PDF version for legal matters

[ EN ]

Claims

1. Method for producing hydrogen comprising the steps consisting in contacting a hydrogen carrier compound (C) comprising one or more Si-H bonds with a hydrogen release catalyst Y and an optional hydrogen release catalyst X wherein the hydrogen release catalyst Y is selected from formula


wherein Y is O or S, and

• XI, X2, are each independently selected from halogen, C1-C10 alkyl, C3-C10

cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR68, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI and X2 = -CRaRb form together with the carbon atom to which they are attached a 3 to 10-membered cycloalkyl, optionally substituted by one to three R9 groups and R\ Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI and X2 = NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6- C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8 and X2 = NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• X I and X2 = NRC form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups and Rc is selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6- C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI = -CRaRb with Ra, Rb are each independently selected from H, halogen, C 1 -C 10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10 and X2 = NRC form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups with Rc selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups wherein

R3 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl ;

R6, R7, R8 are each independently selected from H, OR3, C1-C6 alkyl, C6-C10 aryl, C6- C12 aralkyl;

R9 is selected from halogen, C1-C 0 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, N0 , NR1 'R12, CN, C(=0)R10, C(=0)OR10, S(=0)CH3, wherein said alkyl and aryl groups are optionally substituted by one or more halogen or C 1 -C 10 alkyl or OR3 ;

R10 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl ; and

R1 1, R12 are each independently selected from H, or C1-C10 alkyl, and

wherein the ratio between the sum of the moles of hydrogen release catalyst Y and the moles of the optional hydrogen release catalyst X relative to the moles of the hydrogen carrier compound (C) multiplied by the number of [Si-H] bonds of compound (C) is inferior or equal to 0.3, and/or

wherein the ratio between the sum of the mass of hydrogen release catalyst Y and the mass of the optional hydrogen release catalyst X relative to the mass of the hydrogen carrier compound (C) is inferior or equal to 0.2.

2. Method for producing hydrogen according to claim 1 wherein the ratio between the sum of the moles of hydrogen release catalyst Y and the moles of the optional hydrogen release catalyst X relative to the moles of the hydrogen carrier compound (C) multiplied by the number of [Si-H] bonds of compound (C) ranges from 0.005 to 0.3, and/or

wherein the ratio between the sum of the mass of hydrogen release catalyst Y and the mass of the optional hydrogen release catalyst X relative to the mass of the hydrogen carrier compound (C) is comprised between 0.01 and 0.2.

3. Method for producing hydrogen according to claim 2 wherein the ratio between the sum of the moles of hydrogen release catalyst Y and the moles of the optional hydrogen release catalyst X relative to the moles of the hydrogen carrier compound (C) multiplied by the number of [Si-H] bonds of compound (C) ranges from 0.01 to 0.1 , and/or

wherein the ratio between the sum of the mass of hydrogen release catalyst Y and the mass of the optional hydrogen release catalyst X relative to the mass of the hydrogen carrier compound (C) is comprised between 0.02 and 0.07.

4. Method for producing hydrogen according to any of the preceding claims wherein the compound (C) comprises one or more monomer unit of formulae:


wherein

R is a bond, Ci-Ce alkyl ene or (C1-C4 alkylene)q-Z-(C 1 -C4 alkylene)r ;

Z is O, NR10, S(0)y, CR10=CR10, CºC, C6-C10 arylene, 5-10 membered heteroarylene, or C3-C6 cycloalkylene ;

R1, R2 are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR3, NR4R5, SiR6R7R8, wherein said aryl groups are optionally substituted by one to three R9 groups ;

R1 , R2 are each independently selected from H, halogen, Cl -CIO alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR3, NR4R5, SiR6R7R8, wherein said aryl groups are optionally substituted by one to three R9 groups ;

R3 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl ;

R4, R5 are each independently selected from H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl ;

R6, R7, R8 are each independently selected from H, OR3, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl, Si¾ ;

R9 Is selected from halogen, C1-C10 alkyl, OR10, N0 , NRnR12, CN, C(=0)R10, C(=0)OR10, S(=0)CH3, wherein said alkyl group Is optionally substituted by one or more haloge ;

R10 is H, or C1-C3 alkyl ;

R11, R12 are each independently selected from H, or C1-C10 alkyl ;

q, r are 0 or 1 ;

y is 0, 1 or 2 ;

m, n and p are integers representing the number of repeating units, with n being superior or equal to 1, p being 0 or 1 and m being 0 or 1 ;

A, B are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, OSiR6R7R8, NR4R5, SiR6R7R8, CR13R!4R15 wherein said aryl groups are optionally substituted by one to three R9 groups ;

R13, R14, R15 are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, NR4R5, SiR6R7R8 ; and

wherein the compound (C) comprises at least one group Si-H.

5. Method for producing hydrogen according to claim 4 wherein, in the compound (C) formulae,

p = 0 and m = 1 ; and/or

R1 = Me or H ; and/or

R1 is Me and n is superior to 1 and inferior to 15 000; preferably inferior to 1000; for example between 20 and 500.

6. Method for producing hydrogen according to claim 5 wherein compound (C) is Polyhydromethylsiloxane.

7. Method for producing hydrogen according to any of claims 4 to 5 wherein the compound (C) comprises one or more monomer unit of formulae


wherein R1 is H and n is superior to 1.

8. Method for producing hydrogen according to any of claims 4 to 7 wherein, in the compound (C) formulae, A = SiMe3, Me or Si¾ and B = OMe, OSiMe3 or OS1H3.

9. Method for producing hydrogen according to claims 4 to 5 wherein, the compound (C) comprises one or more monomer unit of formula


wherein n is comprised between 1 and 30, preferably between 2 and 20.

10. Method for producing hydrogen comprising the steps consisting in contacting a hydrogen carrier compound (C) comprising one or more Si-H bonds with a hydrogen release catalyst Y and an optional hydrogen release catalyst X wherein the hydrogen release catalyst Y is selected from formula

Y

X1 X2

wherein Y is O or S, and

• XI , X2, are each independently selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI and X2 = -CRaRb form together with the carbon atom to which they are attached a 3 to 10-membered cycloalkyl, optionally substituted by one to three R9 groups and Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI and X2 = NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6- €12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8 and XI = NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI and X2 = NRC form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups and Rc is selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6- €12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI = -CRaRb with Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10 and X2 = NRC form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups with Rc selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, ORi0, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

wherein

R3 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl ;

R6, R7, R8 are each independently selected from H, OR3, C1-C6 alkyl, C6-C10 aryl, C6- C12 aralkyl;

R9 is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, N02, NR1 'R12, CN, C(=0)R10, C(=0)0Rl°, S(=0)CH3, wherein said alkyl and aryl groups are optionally substituted by one or more halogen or Cl-CIO alkyl or OR3 ;

R10 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl ; and

R11, R12 are each independently selected from H, or Cl -CIO alkyl, and

wherein the hydrogen carrier compounds (C) is selected amongst siloxane hydrogen carrier compounds comprising one or more units of formula (I):

H


H

formula (I)

wherein n is an integer superior or equal to 3 and inferior or equal to 500, and

wherein the molar ratio of the sum of the {claimed catalyst Y and catalyst X} relative to the [SiOHi] monomer units in compound (C) is lower than or equal to 0.6.

11. Method for producing hydrogen according to claim 10 wherein the molar ratio of the sum of the {claimed catalyst Y and catalyst X) relative to the [S1OH2] monomer units in compound (C) ranges from 0.01 to 0.5.

12. Method for producing hydrogen according to any of the preceding claims wherein Y is O in the catalyst formula.

13 Method for producing hydrogen according to any of the preceding claims wherein XI is -NRaRb tn the catalyst formula.

14. Method for producing hydrogen according to any of the preceding claims wherein XI and X2 are both selected from -NRaRb in the catalyst formula.

15. Method for producing hydrogen according to any of the preceding claims wherein the catalyst is selected from 1 ,3 -dimethyl-3 ,4,5 ,6-tetrahydro-2( 1 / )-pyrimidinone (DMPU), tetramethylurea, urea, N,N-dimethylacetamide, cyclohexanone, or mixtures thereof.

16. Method for producing hydrogen according to any of the preceding claims wherein the catalyst is supported.

17. Method for producing hydrogen according to any of claims 1 to 5 or 10 to 16 wherein the compound (C) comprises one or more monomer unit of formulae


wherein n is inferior to 500.

18. Method for producing hydrogen according to any claims 1 to 5 or 10 to 16 wherein the compound (C) is


wherein n is an integer superior or equal to one and inferior or equal to 32.

19. Method for producing hydrogen according to any of the preceding claims wherein the step of contacting the hydrogen carrier compound (C) with the claimed hydrogen release catalyst Y is performed in the absence of catalyst X.

20. Hydrogen release catalyst Y, which can be used in the method for producing hydrogen according to any of the preceding claims, wherein said catalyst Y is selected from formula


Wherein Y is O or S, and

• XI , X2, are each independently selected from halogen, C 1 -C 10 alkyl, C3-C10

cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI and X2 = -CRaRb form together with the carbon atom to which they are attached a 3 to 10-membered cycloalkyl, optionally substituted by one to three R9 groups and Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C 12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

• XI and X2 = NRaRb with Ra and Rb, each independently selected from H, halogen, Cl-CIO alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

• XI is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6- C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8 and X2 = NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

• XI and X2 = NRC form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups and Rc is selected from H, halogen, Cl -CIO alkyl, C3-C10 cycloalkyl, C6- C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups

Or

• XI = -CRaRbwith Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10 and X2 = NRC form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups with Rc selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups wherein

R3 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl ;

R6, R7, R8 are each independently selected from H, OR3, C1-C6 alkyl, C6-C10 aryl, C6- C12 aralkyl ;

R9 is selected from halogen, Cl -CIO alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, NO2, NRl lR12, CN, C(=0)R10, C(=0)OR10, S(=0)CH3, wherein said alkyl and aryl groups are optionally substituted by one or more halogen or C 1 -C 10 alkyl or OR3 ;

R10 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl ; and

R11, R12 are each independently selected from H, or C1-C10 alkyl.

21. Hydrogen release catalyst Y according to claim 18 wherein the catalyst Y is a Si-H bond cleavage catalyst.