阅读说明：本技术 通过硫醇烯反应制备含硫化合物或含硒化合物的方法 (Method for producing sulfur-containing compounds or selenium-containing compounds by reacting thiol alkenes ) 是由 维尔日妮·贝利埃巴卡 塞巴斯蒂安·佩德里奥 米勒娜·鲁迪尔 杰罗姆·蒙布仑 于 2020-04-02 设计创作，主要内容包括：本发明涉及制备式(I)[化学式I]的化合物的方法,其中X选自S、Se；R-(1)选自烷基、芳基、烷基芳基和杂芳基,任选地带有一个或多个官能团,R-(2)、R-(3)和R-(4)彼此独立地选自H和烷基、芳基和烷基芳基；或R-(2)和R-(4)一起形成C5-C10碳环；R-(5)选自H和烷基、芳基和烷基芳基,或代表烃基或烃链,其任选是官能化的,所述方法包括式(IV)[化学式IV]的化合物R-(1)-(X)-(m)-R-(21)与式(V)[化学式V]的化合物的反应,其中X选自S和Se；m＝1或2；R-(1)如以上对于化合物(I)所定义；并且如果m＝1,则R-(21)代表H；如果m＝2,则R-(21)选自烷基、芳基和烷基芳基；其中R-(2)、R-(3)、R-(4)和R-(5)如以上对于式(I)的化合物所定义,所述反应在带有选自醇、羧酸、硫醚和硒醚官能团的至少一种官能团的至少一种化合物的存在下,通过用波长为200至800nm的辐射照射进行。(The invention relates to a process for preparing compounds of formula (I) [ formula I ]]The method of (1), wherein X is selected from S, Se; r 1 Selected from alkyl, aryl, alkylaryl and heteroaryl, optionally bearing one or more functional groups, R 2 、R 3 And R 4 Independently of each other, selected from H and alkyl, aryl and alkylaryl groups; or R 2 And R 4 Together form a C5-C10 carbocyclic ring; r 5 Selected from H and alkyl, aryl and alkylaryl groups, or represents a hydrocarbon radical or chain, optionally functionalized, said process comprising the steps of formula (IV) [ formula IV ]]Compound R of (1) 1 ‑(X) m ‑R 21 And formula (V) [ chemical formula V ]]Wherein X is selected from S and Se; m is 1 or 2; r 1 As defined above for compound (I); and if m is 1, then R 21 Represents H; if m is 2, then R 21 Selected from alkyl, aryl and alkylaryl groups; wherein R is 2 、R 3 、R 4 And R 5 The reaction is carried out by irradiation with radiation having a wavelength of from 200 to 800nm, in the presence of at least one compound bearing at least one functional group chosen from alcohol, carboxylic acid, thioether and selenide functional groups, as defined above for the compound of formula (I).)

1. A process for the preparation of a compound of formula (I)

[ chemical formula I ]

Wherein

X is selected from S, Se;

R₁selected from alkyl, aryl, alkylaryl and heteroaryl, optionally bearing one or more functional groups selected from

Hydroxyl functional groups and their derived functional groups such as ether functional groups,

carbonyl functions such as ketone functions and aldehyde functions, and derived functions such as hemiacetal functions and acetal functions, and

carboxylic acid functional groups and their derived functional groups such as carboxylate functional groups;

R₂、R₃and R₄Independently of each other, selected from H and alkyl, aryl and alkylaryl groups; or R₂And R₄Together form a C5-C10 carbocyclic ring;

R₅selected from H and alkyl, aryl and alkylaryl groups,

or R₅Satisfaction formula (II)

[ chemical formula II ]

Wherein

n＝0-24

R₆And R₇Independently of one another, selected from H, alkyl, aryl and alkylaryl, OR₈And NR₈R₉Wherein R is₈And R₉Independently of each other, selected from H and alkyl, aryl, alkylaryl and acyl groups;

R₁₀selected from H, alkyl, aryl and alkylaryl, OR₁₁And NR₁₁R₁₂Wherein R is₁₁And R₁₂Independently of one another, selected from H, alkyl, aryl, alkylaryl and acyl,

or R₁₀Selected from CN and COR₁₃、COOR₁₃And CONR₁₃R₁₄Wherein R is₁₃And R₁₄Independently of one another, selected from H and alkyl, aryl and alkylaryl groups,

or R₁₀Represents CH₂OR₁₅Wherein R is₁₅Selected from H and alkyl, aryl, alkylaryl and acyl groups,

or R₅Satisfaction formula (III)

[ chemical formula III ]

Wherein

n’＝0-24

Y is selected from O and NR₁₆Wherein R is₁₆Selected from alkyl, aryl, alkylaryl, OR₁₄Wherein R is₁₄As defined above, the above-mentioned materials,

z is selected from H, alkyl, aryl, alkylaryl, CN,

COR₁₇Wherein R is₁₇Selected from the group consisting of H, alkyl, aryl, and alkylaryl; and OR₁₈、NR₁₈R₁₉Wherein R is₁₈、R₁₉And R₂₀Independently of each other, selected from H and alkyl, aryl and arylalkyl; and CH₂OR₂₀Wherein R is₂₀Selected from H and alkyl, aryl, alkylaryl and acyl groups, and

OR₁₈and NR₁₈R₁₉Wherein R is₁₈And R₁₉Independently of one another, selected from H and alkyl, aryl and arylalkyl,

the process comprising the reaction of a compound of formula (IV) with a compound of formula (V)

[ chemical formula IV ]

R₁-(X)_m-R₂₁

(IV)

Wherein

X is selected from S and Se;

m is 1 or 2;

R₁as defined above for compound (I), i.e. R₁Selected from alkyl, aryl, alkylaryl and heteroaryl, optionally bearing one or more functional groups selected from

Hydroxyl functional groups and their derived functional groups such as ether functional groups,

carbonyl functions such as ketone functions and aldehyde functions, and derived functions such as hemiacetal functions and acetal functions, and

carboxylic acid functional groups and their derived functional groups such as carboxylate functional groups; and is

If m is 1, then R₂₁Represents H;

if m is 2, then R₂₁Selected from alkyl, aryl and alkylaryl groups;

[ chemical formula V ]

Wherein R is₂、R₃、R₄And R₅As defined above for the compounds of formula (I),

the reaction is carried out by irradiation with radiation having a wavelength of 200 to 800nm in the presence of at least one compound having at least one functional group selected from the group consisting of alcohol, carboxylic acid, thioether and selenide functional groups, the compound being represented by formula (VI),

[ chemical formula VI ]

Wherein

X' is selected from S or Se;

p and t are independently of each other equal to 0 or 1;

q, r and s are independently of each other equal to 0 to 10;

provided that p + r + t is greater than or equal to 1, and p ≠ 0, while q + s ≠ 0;

if p is 0, then R₂₂Selected from H and alkyl, aryl and arylalkyl, R being R if p ═ 1₂₂Selected from alkyl, aryl and arylalkyl; and is

R₂₃、R₂₄、R₂₅、R₂₆And R₂₇Independently of one another, selected from H and alkyl, aryl and alkylaryl groups.

2. The method according to claim 1, characterized in that the radiation has a wavelength of 254 to 400nm, preferably 365nm ± 20 nm.

3. The process according to claim 1 or 2, characterized in that said compound (VI) comprises at least alkyl sulfides such as methyl sulfide and ethyl sulfide, propionic acid, butyric acid, lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 1-hydroxyhexanoic acid, 3-methylthiopropionic acid, 4-methylthiobutanol, 2, 4-hydroxybutyric acid (2,4-DHB), methylthiobutyric acid (MHA) and Methylthiobutanediol (MTBDO).

4. Process according to any one of the preceding claims, characterized in that the amount of compound (VI) is at least 0.1 equivalent, preferably at least 0.5 equivalent, and preferably at most 10 equivalents, even at most 5 equivalents, and even better at most 2 equivalents for 1 equivalent of compound (V).

5. A process according to any of the preceding claims, characterized in that a compound (IV) is reacted, said compound (IV) being selected from any alkyl thiol or alkyl selenol, such as methyl thiol, ethyl thiol, n-butyl thiol, t-butyl thiol, methyl selenol; any alkylthiol or alkylselenol bearing one or more hydroxyl, carbonyl, carboxylic acid or carboxylate functional groups, such as thioglycolic acid; or disulfides and diselenides, such as alkyl disulfides or alkyl diselenides, such as dimethyl disulfide or aryl disulfides, such as diphenyl disulfide and diphenyl diselenide.

6. The process according to any of the preceding claims, characterized in that a compound (V) is reacted, said compound (V) being selected from butene, pentene, hexene, 2, 3-dimethylbutene, but-3-enoic acid, but-2-enoic acid, but-3-en-2-ol, butenediol, cyclohexene, ethylene glycolic acid (VGA) and ethylene methyl glycolate (MVG).

7. The process according to claim 6, wherein compound (I) is selected from the group consisting of 4-methylthio-2-hydroxybutyric acid, 4-methylseleno-2-hydroxybutyric acid and esters thereof.

8. The process according to any of the preceding claims, characterized in that the molar ratio of compound (IV) to compound (V) is in the range of 1.1-15:1, even 1.2-10: 1.

9. The process according to any of the preceding claims, characterized in that the reaction is carried out in the presence of a type I or type II photoinitiator, preferably a type II photoinitiator such as thioxanthone and derivatives thereof or benzophenone and derivatives thereof.