3P111ᐦᗘỗ㛵ᩘἲ࡟ࡼࡿ࢔ࣝ࢟ࣝ࣋ࣥࢮࣥప㓟໬ࡢ཯ᛂ⤒㊰ゎᯒ㸦㛗ᒸ㧗ᑓ 1ࠊ㇏ᶫᢏ⛉኱ 2㸧‫ۑ‬ᮧୖ ⬟つ 1㸪ᑠཱྀ㐩ኵ 2࠙ᗎࠚඹ㬆Ᏻᐃ໬ᵓ㐀ࢆᣢࡘⰾ㤶⎔࡜┤㙐ᆺⅣ໬Ỉ⣲ࡀ⤖ྜࡋࡓ࢔ࣝ࢟ࣝ࣋ࣥࢮࣥ࡜㓟⣲ศᏊ࡜ࡢ཯ᛂࡣඹ㬆㒊఩࡜㠀ඹ㬆㒊఩࡬ࡢ㓟┤㙐㒊ศ䝥䝻䝢䝹䝧䞁䝊䞁䝖䝹䜶䞁㓟໬཯ᛂ䛾➇ྜ໬ࡀ➇ྜࡍࡿ⣔࡛࠶ࡾ⯆࿡῝࠸ࠋࡲࡓࠊࡇࢀࡽࡢ໬Ꮫ✀ࡣᐇ⏝⇞ᩱ࡟ྵࡲࢀࡿࡓࡵࠊ㓟⣲ศᏊ࡜ࡢ཯ᛂ⤒㊰ࡢゎᯒࡣ㔜せ࡛࠶ࡿ࡜࠸ࢃ䜶䝏䝹䝧䞁䝊䞁ᅗ1ⰾ㤶⎔ྛ✀࢔ࣝ࢟ࣝ࣋ࣥࢮࣥࡢศᏊᵓ㐀ࢀ࡚࠸ࡿࠋࡇࡇ࡛ࡣࠊࡑࡢ୰࡛ࡶ୍␒ࠊᇶᮏⓗ࡞ศᏊᵓ㐀ࢆᣢࡘ࣋ࣥࢪࣝ࠾ࡼࡧࢨ࢖ࣜࣝࣛࢪ࢝ࣝࢆྲྀࡾୖࡆࠊࡑࡢ㓟໬཯ᛂ⤒㊰ゎᯒࢆᐦᗘỗ㛵ᩘἲ࠾ࡼࡧRRKM/Master equationゎᯒ࡟ࡼࡾホ౯ࡋࡓ⤖ᯝࢆሗ࿌ࡍࡿࠋ
࠙ィ⟬ἲࠚࡍ࡭࡚ࡢィ⟬ࡣGaussian03࡟ࡼࡾ⾜࠸ࠊྛ✀ᏳᐃศᏊཬࡧ㑄⛣≧ែࡢᵓ㐀ࢆB3LYP/6311G(d, p)࡛᭱㐺໬ࡋࡓᚋࠊCBS-QB3ἲ࡟ࡼࡾ࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࡓࠋ㑄⛣≧ែ࡟ࡘ࠸࡚ࡣࡑࡢᵓ㐀࡟࠾࠸࡚᣺ືィ⟬࠾ࡼࡧIRCィ⟬ࢆ⾜࠺ࡇ࡜࡛☜ㄆࢆ⾜ࡗࡓࠋࡲࡓࠊ㏿ᗘᐃᩘࡢ⟬ฟ࡟ࡣ
Gilbertࡢ㛤ⓎࡋࡓUnimolࢥ࣮ࢻ[1] ࢆ⏝࠸ࡿࡇ࡜࡛⾜ࡗࡓࠋ࠙⤖ᯝ࠾ࡼࡧ⪃ᐹࠚᅗ 2 ࡟࣋ࣥࢪࣝ(C6H5CH2)

ࡇࢀࡽࡢ཯ᛂ୰㛫య࠾ࡼࡧ㑄⛣≧ែࡢᵓ㐀ࢆィ

CHCHO+ OHᵒɶ࣎‫׹‬ᢟᆆཞ७ᴾᴾᵲᵱᵆᵒᵋᶁᶃᶌᶒᵇOCH2-OOCH2O
H+ O2
benzylperoxybenzyl⟬ࡋࠊ࢚ࢿࣝࢠ࣮ࢲ࢖࢔ࢢ࣒ࣛࢆసᡂࡋࡓ⤖ᯝ

OCH2O+ CH2O
phenoxy

60
C6H5CH3O+O(39.9kcal)

40

TS(6-cent)(10.1kcal)

0

C6H4CH2O+OHTS(51.0kcal)(27.6kcal)

TS(4-cent)(16.4kcal)

20
C6H5CH2+O2TS(O2-add)(8.3kcal)C6H4CH2O(cyclic)+OH(-18.7kcal)

C6H5CH2OO(-22.2kcal)

ᛂࠊࡑࡋ࡚ࠊ4 ୰ᚰᆺࡢỈ⣲ᘬࡁᢤࡁ཯ᛂࡢ㏿ᗘ

-60

TS(16.5kcal)

C6H4CH2OOH
C6H5CH2OO(add)(6.81kcal)(3.9kcal)-20-40ḟ࡟ࠊࢨ࢖ࣜࣝࣛࢪ࢝ࣝ࡜㓟⣲ศᏊࡢ཯ᛂ࡟ᵲᵱ

C6H4CH2(triplet)+HO2(62.0kcal)⣲௜ຍࡢ཯ᛂ⤒㊰࡜ 6 ୰ᚰᆺࡢỈ⣲ᘬࡁᢤࡁ཯ࡣࡉࡽ࡟୍᱆࡯࡝㐜࠸ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ2)OCH2

ᅗ 2 ࣋ࣥࢪࣝࣛࢪ࢝ࣝ࡜㓟⣲ศᏊࡢ཯ᛂ⤒㊰Energy ( kcal / mol)せ࡞཯ᛂ㐣⛬࡛࠶ࡾࠊ2 ᱆࡯࡝㐜࠸㏿ᗘᐃᩘ࡛㓟

H2C+ OHᣠእ˄ьᢟᆆཞ७‒⁆⁅‚⁁․‟⁓⁖⁖‛

RRKM/Master equation ゎᯒࢆ⾜ࡗࡓࠋࡑࡢ⤖࣋ࣥࢪࣝࣛࢪ࢝ࣝ࡜㓟⣲ศᏊ࡟ᡠࡿ㏫཯ᛂࡀ୺

ᵲᵱ OOCH2ḟ࡟ࠊࡇࢀࡽࡢ཯ᛂ⤒㊰ࡢᐤ୚ࢆㄪ࡭ࡿࡓࡵࠊ࣋ࣥࢪࣝ࣌ࣝ࢜࢟ࢩࣛࢪ࢝ࣝࡀศゎࡋ࡚ࠊ෌ᗘࠊ

CH2OO⎔࡬ࡢ௜ຍ཯ᛂࡀ᭱ࡶ࢚ࢿࣝࢠ࣮ࡢప࠸཯ᛂ⤒ᯝࠊ࣋ࣥࢪࣝ࡜㓟⣲ศᏊࡢ௜ຍ཯ᛂ࡛⏕ᡂࡋࡓOH

ɶ࣎‫׹‬ᢟᆆཞ७‒⁆⁅‚ ‟⁕⁗⁠⁦‛ࡀᅗ 3 ࡛࠶ࡿࠋᅗ 3 ࡟♧ࡍࡼ࠺࡟ࠊ㓟⣲ࡢⰾ㤶㊰࡜࡞ࡗࡓࠋ

HO

benzaldehydeࣛࢪ࢝ࣝ࡜㓟⣲ศᏊࡢ཯ᛂ⣲㐣⛬࡛⪃៖ࡋࡓ཯ᛂ⣲㐣⛬ࡢᴫ␎ᅗࢆ♧ࡍࠋᐦᗘỗ㛵ᩘἲ࡟ࡼࡾO

C6H5CHO+OH(-51.3kcal)

C6H5O+CH2O(-65.4kcal)

ᅗ 3 C6H5CH2+O2 ࡢ཯ᛂࡢ࢚ࢿࣝࢠ࣮ࢲ࢖
࢔ࢢ࣒ࣛ⾲㸯࣋ࣥࢪࣝཬࡧࢨ࢖ࣜࣝࣛࢪ࢝ࣝ࡜㓟⣲ศᏊࡢ཯ᛂ࡟࠾ࡅࡿ㑄⛣≧ែ࠾ࡼࡧ⏕ᡂ≀ࡢ┦ᑐ࢚ࢿࣝࢠ࣮(kcal/mol)ࡘ࠸࡚ B3LYP ἲ࡟ࡼࡾ㑄⛣≧ែࡢᵓ㐀ࢆ᥈⣴ࡋࠊ
CBS-QB3 ἲ࡟ࡼࡾࡑࡢ཯ᛂ㞀ቨࡢ኱ࡁࡉࢆホ౯ࡋࡓࠋ⾲㸯࡟ࡑࡢ࢚ࢿࣝࢠ࣮ィ⟬ࡢ⤖ᯝࢆ♧ࡍࠋࢨ࢖ࣜࣝࣛࢪ࢝ࣝࡢᵓ㐀␗ᛶయࡢ✀㢮࡟࠿࠿ࢃࡽࡎࠊ཯ᛂ㞀ቨࡢ኱ࡁࡉࡣ⣙ 1 kcal/mol ௨ෆ࡛࡯ࡰ
➼ࡋ࠸ࡇ࡜ࡀࢃ࠿ࡿࠋ୍᪉ࠊ࢜ࣝࢺࢨ࢖ࣜࣝࣛࢪ

Reactionso-xylylm-xylylp-xylyl

RCH2 + O2

0.00.00.00.0RCH2OO

-22.4

-22.5

-22.3

-22.2

RCH2 O +O
TS1(O2-add)

39.9

39.1

41.7

39.9

6.2

7.8

7.4

8.3

2.1

3.4

3.0

3.9

9.3

9.4

9.4

10.1

5.8

6.5

6.2

6.8

16.7

16.1

16.2

16.4

-49.6

-51.7

-51.5

-51.3

RCH2 O2(adduct)
TS2(6-center)࢝ࣝ࡜㓟⣲ࡢ཯ᛂ࡟࠾࠸࡚ࡣᅗ 4 ࡢ 7 ୰ᚰᆺࡢ཯
ᛂ⤒㊰ࡀᏑᅾࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡽࡢ⤒㊰

R'CH2 OOH
(6-center)TS3(4-center)
OH (4center)࡟ᑐࡋࠊ࣋ࣥࢪࣝࣛࢪ࢝ࣝ࡜㓟⣲ศᏊࡢ཯ᛂ࡜ྠᵝࠊRRKM/Master equation ゎᯒࢆ⾜ࡗࡓࠋᅗ 4࡟♧ࡍࡼ࠺࡟ࠊ࣋ࣥࢪࣝࣛ
12ࢪ࢝ࣝ࡜㓟⣲ศᏊࡢ཯ᛂࡢゎᯒ⤖ᯝྠᵝࠊࢨ࢖ࣜࣝࣛ

10(a) 300K䚸1500 K

8(b)

155㼻
116㼻

(b) 䠓୰ᚰᆺ
1.39(c)41.40(d)(e)(c) O2௜ຍᆺ(d) 䠒୰ᚰᆺ

-2-4ᆺࡢᐤ୚ࡢ๭ྜ࡟ࡘ࠸࡚ࡣ

0.50

1.0

1.5

2.0

4

E / 10 cm

࣋ࣥࢪࣝࣛࢪ࢝ࣝ࡜ྠᵝࡢ(e) 䠐୰ᚰᆺ

2.5-1

ᅗ 4 ࢜ࣝࢺࢨ࢖ࣜࣝࣛࢪ࢝ࣝ࡜㓟⣲ศᏊࡢ཯ᛂ࡟࠾ࡅࡿࡓࠋ

࣑ࢡࣟ࢝ࣀࢽ࢝ࣝ࡞㏿ᗘᐃᩘ࡜ບ㉳࢚ࢿࣝࢠ࣮ࡢ㛵ಀ

᭱ᚋ࡟ࠊ7 ୰ᚰᆺxylylhydroperoxy
6 108ࡢ㑄⛣≧ែࢆ⤒⏤ࡋ
+ O2

xylyl
peroxyxylylศゎ⤒㊰࡟ࡘ࠸࡚࢚㑄⛣≧ែ䛾ᵓ㐀䚸䜶䝛䝹䜼䞊䛻䜘䜛ồ䜑䜙䜜䛯཯ᛂ㏿ᗘᐃᩘ

5 108

peroxy ࣛ ࢪ ࢝ ࣝ ࡢࡓࠋࡑࡢ⤖ᯝࠊxylyl

1.09
1.51

1.080

௜ຍᆺࠊ6 ୰ᚰᆺࠊ4 ୰ᚰᯒ࡟ࡼࡿ᳨ウࢆ⾜ࡗ

1.45

1.40

2

኱ࡁ࠸ࡇ࡜ࡀࢃ࠿ࡿࠋO2ㄽ࡟ࡼࡿ཯ᛂ㏿ᗘゎ

109㼻
121㼻 108㼻
120㼻

1.41 1.42

1.08

1.41

1.46

1.39

ࡢ཯ᛂ⤒㊰ࡢᐤ୚ࡶẚ㍑ⓗ࣒సᡂ࡜㑄⛣≧ែ⌮

1.08 121㼻

1.08ࡀ᭱ࡶ኱ࡁ࠸ࡀࠊ7 ୰ᚰᆺࢿࣝࢠ࣮ࢲ࢖࢔ࢢࣛ

1.18
1.39

6

ศゎࡍࡿ㏫཯ᛂ(a)ࡢᐤ୚

ࡓᚋࡢ xylyl hydro-(a) o-xylylOO䋻o-xylyl+O21.09

ࢪ࢝ࣝ࡜㓟⣲ศᏊ࡟෌ᗘࠊഴྥ ࢆᣢ ࡘࡇ ࡜ࡶ ศ࠿ࡗ

benzyl+ OH

82 108(c)(b)

phthalan3 10(d)(a)Channel (a)䛾䜏㐍⾜4 108+ OH

benzyl epoxide+ HO2Xylylene
+ HO2

1 108
0-1 108200

Benzocyclobutane

400600800 1000 1200 1400 1600

T/K

ᅗ 5 xylyl hydroperoxy ࣛࢪ࢝ࣝࡢ⇕ศゎ⤒㊰࡜㑄⛣≧ែ⌮ㄽ࡟ࡼࡿศゎ㏿ᗘࡢィ⟬⤖ᯝhydroperoxy ࣛࢪ࢝ࣝ࠿ࡽ phthalan ࡜ OH ࣛࢪ࢝ࣝࡀ⏕ᡂࡍࡿ཯ᛂ⤒㊰(a)ࡀ㔜せ࡛࠶ࡗࡓࠋOH ࣛࢪ࢝ࣝࡣ⇞↝࡟࠾ࡅࡿ㐃㙐ᢸయ࡛࠶ࡾࠊ࣓ࢱ࢟ࢩࣞࣥࡸࣃࣛ࢟ࢩࣞࣥ࡟ẚ࡭ࠊ࢜ࣝࢺ࢟ࢩࣞࣥࡀ╔ⅆᛶࡀ㧗࠸࡜࠸࠺ᐇ㦂஦ᐇ࡜ࡶᑐᛂࡍࡿࠋ3)࠙ཧ⪃ᩥ⊩ࠚ1) R.G.Gilbert, Unimol Program Suite, 1993 2) Y.Murakami, et al. J.Phys.Chem.A. 111,13200 (2007)
3) Y.Murakami et al., J.Phys.Chem.A, in press (2009)